KR101779738B1 - Pattern formation method, substrate provided with transparent electroconductive film, device, and electronic instrument - Google Patents
Pattern formation method, substrate provided with transparent electroconductive film, device, and electronic instrument Download PDFInfo
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- KR101779738B1 KR101779738B1 KR1020167032486A KR20167032486A KR101779738B1 KR 101779738 B1 KR101779738 B1 KR 101779738B1 KR 1020167032486 A KR1020167032486 A KR 1020167032486A KR 20167032486 A KR20167032486 A KR 20167032486A KR 101779738 B1 KR101779738 B1 KR 101779738B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
Abstract
There is provided a pattern forming method capable of improving the degree of freedom of a pattern forming direction with respect to a substrate without deteriorating the productivity and a substrate, a device, and an electronic apparatus provided with the transparent conductive film obtained by the method. A liquid containing a functional material on the base material 1 from a plurality of nozzles 72a to 72f of the liquid droplet ejection apparatus 7 while moving the liquid droplet ejection apparatus 7 relative to the substrate 1 At least one set of droplets adjacent to each other on the base material (1) to be subjected to coalescence at the time of discharging the enemy is disposed in a gap in any direction among a relative movement direction (D) and a direction orthogonal to the relative movement direction (D) By drying the line-shaped liquid (2) formed by adjusting one or both of the droplet volume and the gap of the droplet and combining the droplets so as to unite these droplets And depositing a functional material on the edge of the line-like liquid 2 to form a pattern containing the functional material.
Description
The present invention relates to a pattern forming method, a substrate having a transparent conductive film, a device and an electronic apparatus, and more particularly, to a pattern forming method having a step of selectively depositing a functional material on the edge of a liquid by drying and patterning And a substrate, a device, and an electronic apparatus provided with the transparent conductive film obtained by the method.
As a method for forming a fine line pattern including a functional material, a method using photolithography has been widely used in the past. However, since the photolithography technique involves a lot of material loss and complicates the process, a method capable of improving these is being studied.
For example, there is a method in which droplets containing a functional material are continuously applied to a substrate by an ink-jet method or the like to form a thin line pattern. However, in the ordinary inkjet method, the width of the fine lines can not be made equal to or less than the diameter of the ejected droplets, and thus it is not possible to form a fine line pattern having a line width of several mu m.
As an attempt to form fine lines by an ink-jet method, a liquid repellent agent is applied to the entire surface of a substrate in advance, and a part of the liquid repellent agent is hydrophilized by irradiating a laser to form a pattern including a liquid repellent portion and a hydrophilic portion, There is a method of forming a thin line by applying a droplet to the hydrophilic portion with an ink jet. However, this method has a problem that the process becomes complicated because the liquid repellent agent is applied or patterned by a laser.
On the other hand, there is known a method in which a functional material, which is a solid component in a droplet, is deposited on a peripheral portion of a droplet by using convection inside the droplet to form a pattern having a finer width than the droplet (Patent Document 1). According to this method, it is possible to form a thin line having a width of several micrometers, which is not more than the diameter of the droplet, without requiring a special process.
However, in these methods, crossing points of rings are increased in order to make a conductive path, and transparency is lowered.
On the other hand, the applicant of the present invention has found out that a parallel line pattern including a pair of fine lines is formed by separating the conductive material in the liquid imparted in a line form into edge portions by the movement of the liquid, (Patent Document 3).
When a transparent conductive film containing a parallel line pattern is used as a transparent electrode for an image display apparatus, even if the pattern itself is difficult to visually recognize and has excellent transparency, Interference stripes) are sometimes observed.
On the other hand, it has been found that moire can be prevented by preventing the formation direction of the parallel line pattern from being the same as the formation direction of the pattern (for example, the pixel array pattern) of the image display apparatus.
In order to realize this specifically, it is conceivable to change the cutting direction of the base material on which the transparent conductive film including the parallel line pattern is formed. In this case, however, the efficiency of chamfering tends to be impaired.
On the other hand, it is also conceivable to change the forming direction of the parallel line pattern with respect to the substrate. However, when the line-shaped liquid is formed along the moving direction of the inkjet head as described in
If the degree of freedom in the pattern formation direction with respect to the substrate can be improved without damaging the productivity when forming the pattern including the parallel line pattern, problems such as moire can be preferably prevented.
SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a pattern forming method capable of improving the degree of freedom in a pattern forming direction on a substrate without impairing productivity and a substrate, a device, and an electronic apparatus provided with the transparent conductive film obtained by the method There is.
Further, another object of the present invention is clarified by the following description.
The above problems are solved by the following respective inventions.
One.
When a droplet containing a liquid containing a functional material is discharged from a plurality of nozzles of the liquid droplet ejecting apparatus while moving the liquid droplet ejecting apparatus relative to the base material, One set of droplets is disposed at a distance in either direction of a relative movement direction and a direction orthogonal to the relative movement direction and either or both of the droplet volume and the gap are adjusted so as to unite these droplets,
Wherein the line-shaped liquid formed by combining the liquid droplets is dried to deposit the functional material on the edge of the line-like liquid to form a pattern including the functional material.
2.
Wherein a plurality of sets of droplets imparted from a plurality of nozzles to a pixel set arranged in parallel to a nozzle array of the liquid ejection apparatus are provided in a direction intersecting with the nozzle arrays in the formation of the line- And the liquid droplet sets are combined to form the line-like liquid extending in a direction crossing the nozzle array.
3.
The method according to 1 or 2, wherein one or both of the droplet volume and the gap are adjusted so as to increase the linearity of the edge of the line-like liquid formed by combining the droplets.
4.
The total droplet volume V [pL] discharged from one of the nozzles to form one line-shaped liquid and the total droplet volume V [pL] of the plurality of nozzles in the direction perpendicular to the relative moving direction The pattern forming method according to any one of 1 to 3 above, wherein the product V · R [pL · npi] is adjusted within the range of 4.32 × 10 4 [pL · npi] to 5.18 × 10 5 [pL · npi]
5.
The pattern forming method according to any one of 1 to 4 above, wherein the droplet capacity is adjusted by adjusting the number of gradations.
6.
The pattern forming method according to any one of 1 to 5 above, wherein the contact angle of the droplet discharged from the droplet discharger is in the range of 10 [deg.] To 30 [deg.].
7.
The pattern forming method according to any one of 1 to 6 above, wherein one or a plurality of the line-like liquids are formed by one pass by the relative movement.
8.
When a plurality of the line-like liquids parallel to each other are formed by one pass by the relative movement, mutual interference at the time of drying the adjacent line-like liquids is suppressed by adjusting the intervals of applying the line- The pattern forming method according to any one of 1 to 7 above.
9.
Wherein a plurality of said line-shaped liquids which are parallel to each other in one pass by said relative movement are adjusted by adjusting a time interval of ejecting said droplets from each of said nozzles, The pattern forming method according to any one of 1 to 8 above, wherein the pattern forming method is carried out by adjusting one or both of the relative moving speed of the discharging device with respect to the base material.
10.
The method according to any one of 1 to 9 above, wherein the plurality of the line-like liquids parallel to each other are formed by one pass by the relative movement, wherein the interval of the line-like liquids is adjusted to 400 [ / RTI >
11.
The maximum ejection time difference DELTA tmax of the liquid containing the functional material individually discharged from the adjacent nozzles to form one line-like liquid is adjusted to 200 [ms] or less so as to promote the unification of the droplets The pattern forming method according to any one of 1 to 10 above.
12.
The first line-like liquid is applied onto the substrate, and the functional material is selectively deposited on the edge portion in the process of drying the first line-like liquid to form a first line-shaped liquid, which is composed of two line segments including the
Next, the second line-shaped liquid is applied on the substrate so as to intersect the formation region of the first parallel line pattern, and in the process of drying the second line-like liquid, the functional material is selectively deposited on the edge portion , And a second parallel line pattern composed of two line segments including the functional material is formed,
The pattern forming method according to any one of 1 to 11 above, wherein the first parallel line pattern and the second parallel line pattern form a pattern which intersects at least one intersection.
13.
The average spacing A in the formation region of the first parallel line pattern and the average spacing B in the region outside the formation region of the first parallel line pattern satisfy the following mathematical formula with respect to the interval between the two line segments constituting the second parallel line pattern, (1). ≪ / RTI >
14.
13. The method according to 13, wherein the difference between the surface energy in the formation region of the first parallel line pattern and the surface energy in the region outside the formation region of the first parallel line pattern is 5 mN / m or less, / RTI >
15.
Wherein the difference between the surface energy of the solid surface on which the functional material contained in the first line type liquid is applied and dried and the surface energy outside the region where the first parallel line pattern is formed is set to 5 mN / m. < / RTI >
16.
Wherein the contact angle of the second line-type liquid in the formation region of the first parallel line pattern and the contact angle of the second line-like liquid in the region outside the formation region of the first parallel line pattern, 13. The pattern forming method according to 13, wherein the difference in contact angle is 10 DEG or less.
17.
As an adjustment for satisfying the expression (1), the contact angle of the second line-like liquid on the solid surface on which the functional material contained in the first line-like liquid is applied and dried and the contact angle of the second line- Wherein the difference in the contact angle of the second line-like liquid is 10 DEG or less.
18.
The method according to the above 13, wherein the contact angle of the solvent having the highest boiling point among the solvents in the second line-like liquid outside the region where the first parallel line pattern is formed is set to 6or less, Of the functional pattern.
19.
Wherein the adjustment is made so as to satisfy the expression (1), wherein the liquid application amount per length of the second line-shaped liquid in the formation area of the first parallel line pattern and the liquid application amount per length of the second line- 13. A pattern forming method according to the above 13, wherein the applied amount of liquid per length of the line-shaped liquid is made different.
20.
Wherein, as an adjustment for satisfying the expression (1), after forming the first parallel line pattern and before applying the second line-shaped liquid, the step of cleaning the area including the formation area of the first parallel line pattern In the pattern forming method.
21.
The pattern forming method according to the above-mentioned 20, wherein the cleaning is carried out by combining at least one selected from cleaning by heating, cleaning by electromagnetic waves, cleaning with a solvent, cleaning with a gas, and cleaning with a plasma.
22.
21. The pattern forming method according to any one of 1 to 21 above, wherein the treatment for promoting drying is carried out at the time of drying the line-like liquid.
23.
The pattern forming method according to any one of 1 to 22 above, wherein the functional material content of the liquid discharged from the droplet discharger is in the range of 0.01 wt% to 1 wt%.
24.
The pattern forming method according to any one of 1 to 23 above, wherein the functional material is a conductive material or a conductive material precursor.
25.
A transparent conductive film having a transparent conductive film on a substrate surface, the transparent conductive film including a pattern formed by the pattern forming method according to any one of 1 to 24 above.
26.
26. A device having a substrate provided with the transparent conductive film according to 25 above.
27.
26. An electronic device having the device according to 26 above.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective sectional view conceptually illustrating a state in which a parallel line pattern is formed from a line-shaped liquid. FIG.
2 is a plan view conceptually illustrating an example (comparative example) of a method of forming a line-shaped liquid;
3 is a plan view conceptually illustrating an example (comparative example) of a method of forming a mesh-like pattern.
4 is a plan view conceptually explaining chamfering from a substrate on which a pattern is formed by the method shown in Fig. 3; Fig.
5 is a plan view conceptually explaining another example (comparative example) of a method of forming a mesh-like pattern.
Fig. 6 is a plan view schematically illustrating chamfering from 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 the pattern forming method of the present invention.
8 is a plan view for conceptually explaining an example of a droplet discharge condition from a droplet discharge device;
9 is a plan view for conceptually explaining another example of a droplet discharge condition from the droplet discharge device;
10 is a plan view for conceptually explaining another example of a droplet discharge condition from the droplet discharge device;
11 is an enlarged view of a portion indicated by (xi) in Fig. 10; Fig.
12 is a plan view for conceptually explaining an example of forming a plurality of line-shaped liquids by a plurality of passes;
13 is a plan view conceptually illustrating an example of forming a mesh-like pattern using the pattern forming method of the present invention.
14 is a plan view conceptually explaining another example of the case of forming a mesh-like pattern using the pattern forming method of the present invention.
15 is a plan view conceptually illustrating a configuration example of a drying apparatus;
16 is a plan view conceptually explaining another example of the pattern forming method of the present invention.
17 is a plan view conceptually illustrating another form of droplet application for forming a line-like liquid;
Fig. 18 is a plan view conceptually explaining a line-shaped liquid formed by the configuration of Fig. 17; Fig.
19 is a plan view conceptually illustrating a parallel line pattern formed from the line-shaped liquid shown in Fig. 18; Fig.
20 is a view for explaining a nozzle row;
21 is an explanatory view for explaining an example of a method of forming a mesh-type functional pattern;
22 is an explanatory view for explaining another example of a method of forming a mesh-type functional pattern;
23 is an explanatory view for explaining another example of a method of forming a mesh-type functional pattern;
Fig. 24 is an enlarged view of a main part showing an example of forming the intersection X. Fig.
25 is an optical microscope photograph of a functional pattern of a mesh type.
26 is a view for explaining an example of a method of measuring the average interval A and the average interval B;
27 is a partially enlarged plan view showing an example of a parallel line pattern formed on a substrate;
Fig. 28 is an explanatory diagram for explaining the cross-section of (a) - (a) in Fig. 27; Fig.
29 is a perspective view showing a part of a parallel line pattern formed on a substrate;
Hereinafter, the present invention will be described in detail with reference to the drawings.
1 is a perspective view for conceptually explaining a state in which a parallel line pattern is formed from a line-shaped liquid, and a section corresponds to a longitudinal section cut in a direction orthogonal to the forming direction of the line-like liquid.
1,
In Fig. 1 (a), a line-
As shown in Fig. 1 (b), when a line-
The coffee stain phenomenon can be caused by setting conditions for drying the line-
That is, the drying of the line-
As a result, as shown in Fig. 1 (c), a
The application of the line-like liquid onto the substrate can be carried out using a liquid drop ejecting apparatus. Specifically, a liquid containing a functional material is ejected from a nozzle of a liquid ejection apparatus while relatively moving the liquid ejection apparatus relative to a substrate, and the ejected liquid droplets are united on the substrate to form a line-like liquid containing a functional material can do. The liquid droplet ejecting apparatus can be constituted by, for example, an ink jet head included in the ink jet recording apparatus.
Here, the problems that the present inventors have found will be described in detail while exemplifying comparative examples.
2 is a plan view conceptually illustrating an example (comparative example) of a method of forming a line-shaped liquid.
In Fig. 2,
As shown in Fig. 2, a method of forming the line-
The liquid containing the functional material is supplied from the one
A plurality of line-shaped
The
By using such a method, it is possible to form a mesh-like pattern formed by crossing parallel line patterns.
3 is a plan view conceptually explaining an example (comparative example) of a method of forming a mesh-like pattern.
First, as shown in Fig. 3 (a), the droplet ejection apparatus (not shown in Fig. 3) is moved along the relative movement direction D relative to the
By drying the first line-shaped
Subsequently, the liquid droplet discharging device is rotated by 90 DEG relative to the substrate, and the relative movement direction D relative to the
3 (c), a plurality of second line-shaped
By drying these second line-shaped
In this manner, the mesh-
In the pattern forming method shown in Fig. 3, the following problems can be found.
4 is a plan view for conceptually explaining chamfering from a substrate on which a pattern is formed by the method shown in Fig.
The
First, as shown in Fig. 4 (a), it is conceivable to cut and use the
However, in this case, even if the
Here, the " forming direction of the
As the "pattern provided by the device", for example, a lattice pattern such as a pixel array in an image display apparatus can be preferably exemplified.
On the other hand, as shown in Fig. 4 (b), the
In the base material piece to be cut out, the forming direction of the
However, since the cutting direction of the base material piece is not along the side of the
Therefore, in the pattern forming method shown in Fig. 3, problems arise from the viewpoint of both achieving both prevention of moire and efficiency of chamfering.
Further, in the pattern forming method shown in Fig. 3, it is necessary to change the relative moving direction D of the liquid droplet ejecting apparatus relative to the substrate when applying the first line type liquid and when giving the second line type liquid. For example, there is a need to change the arrangement direction of the substrate or to change the arrangement direction of the liquid discharge device, and problems arise from the standpoint of productivity.
5 is a plan view for conceptually explaining another example (comparative example) of a method of forming a mesh-like pattern.
In the example of Fig. 5, the relative movement direction D of the liquid ejection apparatus (not shown in Fig. 5) is set to be inclined with respect to the side of the
First, as shown in Fig. 5 (a), the liquid droplet ejecting apparatus is moved along the relative movement direction D inclined at 45 degrees to the sides of the
By drying the first line-shaped
Subsequently, the liquid droplet discharging device is rotated by 90 DEG relative to the substrate, and the relative movement direction D relative to the
Next, as shown in Fig. 5 (c), the droplet ejection apparatus is moved along the modified relative movement direction D inclined with respect to the sides of the
By drying these second line-shaped
In this manner, the mesh-
6 is a plan view for conceptually explaining chamfering from a base material on which a pattern is formed by the method shown in Fig. 4, the cutting base line at the time of chamfering is indicated by a broken line C in the figure.
6, even if the
Thus, by forming the
However, in the method of forming a pattern shown in Fig. 5, as in the case of the method shown in Fig. 3, when applying the first
Hereinafter, the pattern forming method of the present invention will be described in detail.
7 is a plan view for conceptually explaining an example of the pattern forming method of the present invention.
7,
A droplet containing a liquid containing a functional material is ejected from the plurality of
In the following description, the angle (tilt angle) in the forming direction of the line-
Next, the sum of the droplets on the
8 is a plan view for conceptually explaining an example of a droplet discharge condition from the droplet discharge device.
In the illustrated example, 2a to 2f each indicate a landing position of a liquid droplet ejected from the
The landing positions 2a to 2f are arranged at intervals in the direction of the relative moving direction D and the direction perpendicular to the relative moving direction D. [ That is, by discharging droplets from the
The
One or both of the liquid droplet volume and the liquid droplet gap are adjusted so that the liquid droplets landed on the landing positions 2a to 2f and the adjacent liquid droplets on the
As a result of this adjustment, the line-
According to the present invention, for example, when setting the formation direction of the line-like liquid, the step of changing the arrangement angle of the liquid droplet ejection apparatus is not necessary, so that the productivity of the substrate can be improved. The effect of improving the degree of freedom can be obtained.
It is also preferable to adjust one or both of the liquid droplet volume and the droplet gap so as to enhance the linearity of the edge of the line-
As a preferred modification, the product V · R [pL · npi] of the total droplet capacity V [pL] given from one nozzle and the nozzle column resolution R [npi] to form one line- It is preferable to adjust the value to 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 to form one line-
As a method for adjusting the total droplet amount, a method of adjusting the capacity per one droplet, a method of adjusting the number of droplets to be landed at one landing position, and the like can be preferably exemplified. It is also preferable to use one or more of these methods in combination.
When adjusting the number of droplets to be landed at one landing position, it is preferable to use a liquid droplet ejecting apparatus provided with the number-of-gradation changing means. That is, the droplet capacity can be adjusted by adjusting the number of gradations. The number of gradations means the number of droplets to be landed per one dot (the unit is " dpd " (drops per dot)) and can be used as a numerical value corresponding to the number of droplets landed at the above- have.
Therefore, the total droplet capacity V [pL] can be expressed as V = V d · N when the droplet capacity per droplet is V d [pL] and the number of gradations is N [dpd].
Further, the nozzle row resolution R [npi] is the number of nozzles per inch in the direction perpendicular to the relative moving direction. (The pitch between the centers of the nozzles) in the direction orthogonal to the relative moving direction is constant, the inverse number of the nozzle interval [inch] is used as the numerical value corresponding to the nozzle column resolution R [npi] .
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 line-shaped liquid is more easily formed more linearly, . As a result, line segments constituting the parallel line pattern to be formed are more likely to be formed more linearly, and disconnection or the like can be preferably prevented. Therefore, when the conductive material is used as the functional material, the sheet resistance and the terminal resistance of the resulting pattern can be further improved.
It is preferable that the contact angle of the droplet containing the functional material discharged from the droplet discharge device on the substrate is in the range of 10 [deg.] To 30 [deg.].
The contact angle is a static contact angle. For example, using a DM-500 manufactured by Kyowa Chemical Industry Co., Ltd., the droplet (about 5 μl) to be measured is measured from a syringe It can be obtained by placing it on the
The contact angle can be appropriately adjusted by, for example, the composition of the liquid droplet including the functional material, the setting of the surface energy of the substrate, and the like.
When the contact angle is in the range of 10 [deg.] To 30 [deg.], The effect of further improving the transparency of the parallel line pattern to be formed can be obtained.
When the contact angle is in the range of 10 [deg.] To 30 [deg.], The line-like liquid is more easily formed linearly, and bulging can be preferably prevented. As a result, line segments constituting the parallel line pattern to be formed are more likely to be formed more linearly, and disconnection or the like can be preferably prevented. Therefore, when the conductive material is used as the functional material, the sheet resistance and the terminal resistance of the resulting pattern can be further improved.
8, each of the
An In, a line-type liquid droplet discharging apparatus and by an angle formed with respect to the relative movement direction D of the substrate, given spacing parallel to a line-type liquid together imparted by one pass M p to one aspect of the invention, It is possible to easily adjust it to a desired value.
That is, in the case where the line-shaped liquid is formed along the relative movement direction D of the liquid ejection apparatus and the substrate as in the comparative example described with reference to FIG. 2, the line-shaped liquid application interval M p Can be adjusted only in the unit of the nozzle interval of the liquid ejection apparatus. At this time, the selectable grant interval Mp becomes a stepwise (discontinuous) value of the unit of the nozzle interval.
By contrast, by forming the line-shaped liquid obliquely with respect to the relative movement direction D of the liquid ejection apparatus and the substrate, it is released from the restriction of the nozzle interval at the time of adjustment of the imparted interval M p . That is, the grant interval M p can be freely selected from a continuous range.
Grant interval of the line-type liquid imparted by one pass M p is (also referred to as pitch), a distance of a direction perpendicular to the forming direction of the line-type liquid (2, 2 ') as shown in Figure 8 is , And the center of the line-shaped
By forming the line-shaped liquid obliquely with respect to the relative movement direction D of the liquid droplet ejecting apparatus and the substrate, the giving interval M p is set to be shorter than the time interval for ejecting droplets from the
For example, by making the time difference for discharging the droplets from the
Further, for example, by making the relative moving speed of the liquid
In this manner, the grant interval M p can be easily adjusted to a desired value. As a result, the degree of freedom of patterning can be improved, and it becomes possible to enhance suitability to various devices and various electronic apparatuses.
It is also preferable to suppress the mutual interference when drying the adjacent line-shaped
The value of the grant interval M p is not particularly limited, but is preferably 400 [mu m] or more. As a result, mutual interference at the time of drying the adjacent line-
It is preferable that the maximum ejection time difference DELTA tmax of the liquid containing the functional material discharged from the adjacent nozzles to form one line-
The maximum discharge time difference? T max will be described in detail first with reference to the example of Fig.
In Fig. 8, the liquid
The liquid droplet ejecting apparatus ejects the liquid from the
In the illustrated example, the
Other conditions for the maximum ejection time difference DELTA tmax will be described in more detail by way of example.
9 is a plan view for conceptually explaining another example of the droplet discharging condition from the droplet discharger.
In Fig. 9, the liquid
These two
In the
Under these conditions, the dispense time difference between the adjacent nozzles differs depending on the extraction method of two sets of adjacent nozzles. Under these conditions, the ejection time difference when two sets of adjacent nozzles are extracted so as to maximize the ejection time difference can be set as the maximum ejection time difference DELTA tmax .
10 and 11 are plan views for conceptually explaining still another example of the liquid discharge condition from the liquid discharge device. 11 is an enlarged view of a portion indicated by (xi) in Fig.
When the width of the pattern formation area on the
Even under these conditions, the dispense time difference between the adjacent nozzles differs depending on the extraction method of two sets of adjacent nozzles. Particularly, the influence due to the fact that the nozzles adjacent to each other exist in two different-row heads is large. Even under these conditions, the ejection time difference when two sets of adjacent nozzles are extracted so as to maximize the ejection time difference can be made the maximum ejection time difference DELTA tmax .
In the illustrated example, when the
12 is a plan view for conceptually explaining an example of forming a plurality of line-shaped liquids by a plurality of passes.
In the illustrated example, a plurality of line-shaped
It is preferable that a drying step for drying a line-shaped liquid formed in the previous pass to form a parallel line pattern is provided between the respective paths. Here, a drying process is provided between the first pass and the second pass. In the drying process, the line-
As described above, when forming a line-like liquid in a certain pass, it is preferable to dry the line-shaped liquid formed by the previous pass. This is common even in the case of forming line-like liquids in the same direction in each pass as shown or forming line-like liquids in different directions in each pass.
It is preferable that the application interval M p of the line-like liquid applied by one pass is larger than the application interval M of the line-shaped liquid finally applied. The line-shaped liquid finally applied refers to a line-shaped liquid in the same direction given by all passes (two passes in the illustrated example) for forming a line-shaped liquid in the same direction. As shown in the drawing, in measuring the interval of the finally provided line-shaped liquid, the line-shaped liquid may partially or completely be in a dried state, that is, a state in which it is in a parallel line pattern. The line-shaped liquid in a dried state may also be included in an object to be measured at a given interval M as a line-shaped liquid finally applied.
As shown in the figure, it is preferable that the line-shaped liquid in the same forming direction is formed by a plurality of passes. In the case of forming the line-shaped liquid in the same forming direction by a plurality of passes, in the second and subsequent passes, a gap between the adjacent two line-shaped liquids (which may be already dried) Type liquid. By providing a drying step between each pass, the number of line-type liquids to be dried at the same time can be reduced, and the interval between the line-shaped liquids can be easily ensured. Thus, the influence caused by drying can be reduced, It is possible to obtain more stabilized effect.
In the illustrated example, a plurality of line-shaped liquids are formed by two passes, but the above description can be used even in the case of three or more passes.
When a plurality of line-shaped liquids having the same forming direction are formed in n passes (where n is an integer of 2 or more), the line-shaped liquid application interval M p given by one pass is the line- N ".
In the present invention, by forming the line-shaped liquid at an angle with respect to the relative movement direction D of the liquid ejection apparatus and the substrate, the elongation speed of the line-shaped liquid can be made larger than the relative movement speed of the liquid ejection apparatus with respect to the substrate.
The elongation rate of the line-like liquid is a length per unit time in which the line-like liquid elongates in the direction of formation of the line-like liquid. The elongation velocity V L [占 퐉 / s] of the line-shaped liquid is represented by V H [占 퐉 / s] and the inclination angle of the line-shaped liquid with respect to the base is? In this case, V L = V H / | cos? |.
By forming the line-shaped liquid in a direction inclining with respect to the relative moving direction of the liquid discharge device with respect to the base material, the absolute value of cos &thetas; Thereby, the elongation rate V L of the line-like liquid can be made to be larger than the relative moving speed V H of the liquid discharge device with respect to the substrate, that is, V L > V H.
Thus, the formation of the line-shaped liquid can be speeded up, the droplet to be subjected to the coalescence can be prevented from drying in the droplet unit, and the coalescence of the droplets can be promoted.
By using the above-described pattern forming method of the present invention, it is possible to solve the problem of both achieving the efficiency of prevention of moir 辿 and the efficiency of chamfering, and the problem of productivity. That is, the effect of both achieving both the prevention of moire and the efficiency of chamfering and improving the productivity can be obtained. A specific example will be described below with respect to this point.
13 is a plan view for conceptually explaining an example of forming a mesh-like pattern using the pattern forming method of the present invention.
First, as shown in Fig. 13 (a), a liquid droplet discharging device (refer to Fig. 13 (a)) for the
By drying the first line-shaped
Subsequently, without changing the relative movement direction D at the time of forming the first line-shaped
By drying these second line-shaped
In this manner, the mesh-
The first
Therefore, even if the
The formation of the line-
Fig. 14 is a plan view for conceptually explaining another example of forming a mesh-like pattern using the pattern forming method of the present invention. In Fig. 14, the same reference numerals as those in Fig. 13 denote the same components as those in Fig. 13.
First, the first line-shaped
Then, the first line-shaped
Next, the relative movement direction D is set in a direction opposite to the relative movement direction D at the time of forming the first line-shaped
In this state, the second line-shaped
Then, the second line-shaped
In this manner, the mesh-
As described above, when the first line-like liquid (2) is provided and the second line-like liquid (4) is provided by forming a line-like liquid along the direction of inclination with respect to the relative movement direction D of the liquid drop ejecting apparatus relative to the substrate, ), It is possible to set the relative moving direction D of the liquid droplet ejecting apparatus relative to the substrate in the reverse direction.
Thereby, when the liquid droplet ejecting apparatus is reciprocated once on the
In the liquid droplet ejecting apparatus, it is relatively easy to eject liquid droplets by setting the relative movement direction D in the opposite direction as described above, and it is easy to carry out without requiring a step of resetting the arrangement angle of the liquid droplet ejection apparatus to the substrate can do.
When drying the line-like liquid, it is preferable to carry out a treatment for promoting drying. Thereby, the effect of stabilizing the formation of the parallel line pattern can be obtained.
As the treatment for promoting drying, for example, treatment such as heating, blowing, irradiation with energy rays, and the like may be mentioned, and one or two or more of these may be used in combination.
It is preferable to use a drying apparatus (also referred to as a dryer) for promoting the drying of the line-shaped liquid. The drying apparatus may be any one configured to be capable of performing the above-described drying treatment, and examples thereof include a heater, a blower, and an energy ray irradiating apparatus, and may be constructed by combining one or more of them.
15 is a plan view for conceptually explaining a configuration example of a drying apparatus.
It is preferable that the
Since the configuration shown in the drawing assumes the formation of a line-like liquid only in the forward path when the liquid
The drying device may be provided on the substrate side. For example, it is also preferable to provide a drying device such as a heater on a stage for mounting a substrate. It is also preferable to provide a drying device on the side of the liquid discharge device and on the side of the substrate, respectively.
In the above description, an example in which the liquid droplet ejecting apparatus is moved relative to the substrate is mainly described, in which the substrate is fixed and the liquid droplet ejecting apparatus is moved. The present invention is not limited to this example, and the substrate may be moved and the liquid discharge device may be fixed.
Further, in order to realize the relative movement, the substrate may be moved and the droplet ejection apparatus may be moved, but the control may become complicated. From the viewpoint of facilitating the control, it is preferable that one of the substrate and the liquid droplet ejection apparatus is fixed and the other is moved.
Hereinafter, an example in which the substrate is moved and the liquid ejection apparatus is fixed will be described.
16 is a plan view for conceptually explaining another example of the pattern forming method of the present invention.
In this example, as the liquid
In this example, two liquid
These
Each of the
First, the
Then, the region where the first line-shaped
Subsequently, the region in which the
Then, the region where the second line-shaped
As described above, there is a method of forming a line-like liquid along a direction inclined with respect to the relative moving direction D of the liquid droplet ejecting apparatus relative to the substrate, thereby forming a pattern under the condition that the substrate is moved and the liquid droplet ejecting apparatus is fixed , A method of forming a pattern using the line head as described above).
In the above description, when forming a line-like liquid by using a liquid droplet ejecting apparatus, a plurality of droplets, which are given from one nozzle per one pixel, are given in a direction intersecting with the nozzle array, A case of forming a line-like liquid extending in the direction intersecting with the heat is mainly described, but the present invention is not limited thereto. For example, when forming a line-like liquid using a liquid droplet ejecting apparatus, a set of droplets imparted from a plurality of nozzles to a pixel set arranged in parallel to the nozzle row of the liquid ejection apparatus is divided into a plurality of And a plurality of sets of the droplets are combined to form a line-shaped liquid extending in a direction crossing the nozzle array. This embodiment will be described with reference to Figs. 17 to 19. Fig.
17, the line-
That is, the
In the process of this relative movement, a plurality of
Subsequently, a plurality of pixels (b2, c2, d2) arranged in parallel with the direction N of the nozzle array (73) are included in a place where the liquid droplet ejection device (7) The
That is, in the illustrated example, when selecting the pixel set to which the
18, the
19, a
As described above, in the case of forming the line-
In the above description, the number of pixels constituting the pixel set is set to three pixels. However, the present invention is not limited to this, and the
In the examples shown in Figs. 17 to 19, the pixel set is used in the case of forming the line-shaped
In the above description, the case where the liquid droplet ejecting apparatus has a plurality of nozzles arranged in a row is shown, but the invention is not limited thereto. For example, as shown in Fig. 20, the liquid
Next, an adjustment for increasing the linearity of the fine lines in the pattern (mesh-shaped functional pattern) formed by crossing the parallel line patterns will be described.
When a mesh-type functional pattern is formed, it is advantageous in realizing distribution of a functional material on a substrate while maintaining low visibility.
Particularly, since the line segment constituting the parallel line pattern formed as described above can realize a line width of several micrometers, the fine line width allows the mesh-type functional pattern to be formed on the surface of the human eye , It appears as though it is transparent.
The shape of the fine line pattern of the functional material can be set by a device using the functional material. As an example of a device, a transparent surface electrode is used in a touch sensor used in a touch panel in order to detect a position with a finger or the like.
When a conductive material is used as a functional material in a mesh-type functional pattern, it can be preferably applied to a transparent surface electrode for a touch panel or the like. From the viewpoint of constituting the surface electrodes and the like, it is very effective in that the conductive path is increased by forming the mesh type by a plurality of parallel line patterns having different forming directions from each other.
As a method for forming such a mesh-type functional pattern, a method shown in Fig. 21 can be mentioned.
First, as shown in Fig. 21 (a), a line-
Then, by drying the line-shaped
At this time, as a result of the functional material contained in the line-
As a method for preventing the
In this example, as shown in Fig. 22 (a), in the method described in Fig. 21, the amount of ink at the portion of the intersection formed by the line-shaped
According to this method, it is possible to prevent the
At this time, since the amount of ink to the intersection X is increased, the intersection X becomes a ring shape having a larger diameter than the interval between the
The generation of such a ring-shaped portion is advantageous from the standpoint of preventing disconnection of the
As a method for preventing the
First, as shown in Fig. 23 (a), the line-
In the course of drying the line-
Then, as shown in Fig. 23C, the second line-type (second) line-type liquid crystal display device is formed in a second direction (in this example, a direction orthogonal to the first direction, The liquid (4) is applied. That is, the second line-shaped
In the course of drying the line-
As described above, a mesh-like functional pattern is formed by the first
According to this method, it is possible to prevent disconnection of the
Fig. 24 is an enlarged view of a main part showing an example of forming the intersection X. Fig.
In the example described with reference to Fig. 23, as shown in Figs. 24A and 24B, between the
It has been found that the convexity or narrowing between the
Particularly, in the case where the functional material is a conductive material, the convexity or narrowness causes the length of the conductive path to extend along the first parallel line pattern 3 (first direction) and the second parallel line pattern 5 (Second direction), and it is found that there is room for further improvement from the viewpoint of preventing the fluctuation of the resistance.
In order to improve these, as shown in Fig. 24 (c), in the example described using Fig. 23, the interval between the two
&Quot; (1) "
This makes it possible to prevent disconnection of line segments and improve low visibility in the obtained functional pattern of the mesh shape. In particular, when the functional material is a conductive material, Direction in the first direction and the second direction with high accuracy, and the effect that the variation of the resistance can be preferably suppressed can be obtained. FIG. 25 (b) shows an optical microscope photograph of the mesh-type functional pattern obtained by the above-mentioned adjustment.
The formation area of the first
The average spacing A in the formation region of the first
It is preferable that the measurement points of the plurality of points (n points) set to measure the average interval A are arranged at equal intervals along the second direction within the formation region of the
Specifically, the average interval A and the average interval B are preferably measured as follows.
26 is a view for explaining an example of a method of measuring the average interval A and the average interval B;
First, as shown in Fig. 26, the average interval A is calculated by dividing the
On the other hand, as shown in Fig. 26, the average spacing B is set so that the interval between the
In the illustrated example, the measurement points B 1 to B 5 of the average spacing B are set adjacent to the lower side of the measurement points A 1 to A 7 of the average spacing A in the figure, They may be set adjacent to each other. At this time, it is preferable to set the measurement points B 1 to B 5 of the average interval B on either the upper side (one side) or the lower side (the other side) so that the difference between the average interval A and the average interval B becomes larger.
In the example of Fig. 26, the case where two points A 1 and A 2 along the
In the example shown in Fig. 26, the case where five points A 3 to A 7 inside the
In the example of Fig. 26, the case where five points B 1 to B 5 outside the
The interval between the
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) - (a) cross-section in Fig. 27, and shows a cross section (longitudinal section) obtained by cutting one set of two fine lines included in the pattern in a direction orthogonal to the line segment direction .
The interval I between the
It is also possible to adjust one or a plurality of factors that may affect the ratio B / A of the average interval A and the average interval B, in order to satisfy the above-mentioned expression (1). These factors are not particularly limited and can be appropriately selected.
As a preferable form of adjustment for satisfying the above-described expression (1), the following can be exemplified.
In the first embodiment, the difference between the surface energy in the formation region of the first
Here, the surface energy in the formation region of the first
On the other hand, the surface energy outside the formation region of the first
The surface energy can be calculated from the Young-Fowkes equation.
By setting the difference in surface energy to 5 mN / m or less, it is possible to reduce the change in wettability with respect to the second line-
If the surface energy in the formation region of the first
On the other hand, in the second
The means for adjusting the surface energy difference between the inside and outside of the formation region of the first
As a method of performing the surface treatment on the region including the region outside the formation region of the first
In the case of changing the liquid composition of the first line-
In the second embodiment, the surface energy of the solid surface coated with the functional material contained in the first line-shaped
The term " solid surface " means a surface of a solid film formed by applying and drying a functional material contained in the first line-shaped
In the region between the
At this time, the surface energy of the solid surface coated with the functional material contained in the first line-
When the surface energy of the solid surface is larger than the area outside the area where the first
On the other hand, in the case where the surface energy of the solid surface is smaller than the area outside the formation area of the first
The means for adjusting the surface energy of the solid surface and the difference in surface energy outside the area where the first
In the third embodiment, the contact angle of the second line-shaped
Here, the contact angle in the formation region of the first
On the other hand, the contact angle outside the region in which the first
The measurement of the contact angle can be carried out using a contact angle measuring apparatus DM-501 manufactured by Kyowa Kaimengagaku KK. In the third embodiment, the contact angle is set to a value after 5 seconds after dropping a liquid having the same composition as that of the second line type liquid (4).
By making the difference in the contact angle to 10 degrees or less, the change in the wettability with respect to the second line-shaped
If the contact angle in the formation region of the first parallel line pattern is larger than the contact angle outside the formation region and the difference in the contact angle exceeds 10 DEG, The distance between the
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 DEG, the second parallel line pattern ( 5 becomes smaller than the outside of the forming region, resulting in a narrowed shape.
The means for adjusting the difference in contact angle is not particularly limited, and the means described as the means for adjusting the surface energy difference in the first aspect can be preferably used. Further, as the means for adjusting the difference in the contact angle, the liquid composition of the second line-
In the fourth embodiment, as an adjustment for satisfying the above-mentioned formula (1), the contact angle of the second line-like liquid (4) on the solid surface coated with the functional material contained in the first line- And the contact angle of the second line-shaped liquid (4) outside the region where the first parallel line pattern (3) is formed is set to 10 degrees or less. As for the "solid surface", the description in the second aspect is cited.
By making the difference in the contact angle to 10 degrees or less, the change in the wettability with respect to the second line-shaped
By adjusting the contact angle on the solid surface as an index so that the surface energy is the same as described above in the second embodiment, the reliability can be further improved.
When the contact angle on the solid surface is larger than the contact angle outside the region where the first
On the other hand, when the contact angle on the solid surface is smaller than the contact angle outside the region where the first
The means for adjusting the difference between the contact angle on the solid surface and the contact angle outside the region where the first
In the fifth embodiment, the contact angle of the solvent having the highest boiling point among the solvents in the second line-shaped
Here, the contact angle outside the region where the first
The measurement of the contact angle can be carried out using a contact angle measuring apparatus DM-501 manufactured by Kyowa Kaimengagaku KK. In the fifth embodiment, the contact angle is set to a value after 5 seconds after dropping the solvent having the highest boiling point among the solvents in the second line-shaped liquid (4).
By making the contact angle equal to or less than 6 degrees, the change in wettability with respect to the second line-shaped
The means for adjusting the contact angle is not particularly limited, and the means described as means for adjusting the surface energy difference in the first aspect can be preferably used.
In the sixth embodiment, as an adjustment for satisfying the above-described expression (1), the liquid application amount per length of the second line-shaped
For example, in the case where the wettability of the second line-shaped
If the wettability of the second line-shaped
In this manner, the interval between the
The difference in the amount of applied liquid between the inside and outside of the formation region of the first
In the seventh aspect, as an adjustment for satisfying the above-described equation (1), after the first
The first line-shaped liquid (not shown) which is not carried to the positions of the
Cleaning may be said to remove such residual components. At this time, depending on the cleaning condition, for example, the type of cleaning or strength setting, how much the residual component is removed is affected. Using this relationship, it is possible to eliminate the wettability difference of the second line-shaped
The cleaning may be performed only in the formation region of the first parallel line pattern, or may be performed in the region including the formation region of the first parallel line pattern and the region outside the formation region. It is also preferable to perform cleaning on the entire surface of the
In the case of cleaning only within the formation region of the first parallel line pattern, for example, irradiation with electromagnetic waves or the like may be performed while masking the outside of the formation region, or a cleaning solvent may be selectively provided within the formation region .
The washing method is not particularly limited, and for example, a washing method commonly used in industrial products can be used. For example, it is preferable to perform cleaning by combining one or two or more selected from cleaning by heating, cleaning by electromagnetic waves, cleaning with a solvent, cleaning with a gas, and cleaning with a plasma.
Examples of the cleaning method by heating include a continuous heating method using an infrared heater, an oven, a hot plate, or the like, or a momentary heating method using a xenon flash lamp or the like. The heating conditions (temperature, time) and the like are appropriately set in a range in which the interval between the
As an electromagnetic wave, a method of irradiating an electron beam, a gamma ray, an ultraviolet ray, or the like can be used. The irradiation conditions of the electromagnetic wave are appropriately set in a range in which the interval between the
The solvent used for washing with a solvent is not limited as long as it is a solvent that can satisfy the above-mentioned formula (1). However, it is preferable to select a solvent having little influence on the parallel line pattern formed by depositing the functional material. A solvent suitable for cleaning can be appropriately selected according to the kind of the functional material. For example, in the case of silver nanoparticles in a water dispersion system, an alcohol-based solvent or the like is preferable.
The plasma cleaning condition can be appropriately set in a range in which the interval between the
Next, the liquid containing the functional material discharged from the droplet ejection apparatus will be described in detail.
The content of the functional material in the liquid containing the functional material discharged from the droplet ejection apparatus is preferably in the range of 0.01 wt% or more and 1 wt% or less. The " liquid containing the functional material discharged from the droplet ejection apparatus " may be referred to as a liquid containing the functional material immediately before being applied on the substrate, before it is dried. When the content of the functional material is in the range of 0.01 wt% or more and 1 wt% or less, the effect of stabilizing the formation of the parallel line pattern 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. To give a specific function means, for example, when a conductive material is imparted to a substrate, the conductive material is used as a functional material, and when an insulating property is given, the insulating material is used as a functional material. As the functional material, for example, a conductive material such as conductive fine particles and a conductive polymer, an insulating material, a semiconductor material, an optical filter material, and a dielectric material can be preferably exemplified. In particular, the functional material is preferably a conductive material or a conductive material precursor. The conductive material precursor indicates that it can be changed into a conductive material by appropriately treating it.
That is, the pattern forming method of the present invention is particularly preferably used when forming a pattern constituted by fine lines (line segments) containing a conductive material.
As the conductive material, for example, conductive fine particles, conductive polymers and the like can be preferably exemplified.
The conductive fine particles are not particularly limited but may be selected from Au, Pt, Ag, Cu, Ni, Cr, Rh, Pd, Zn, Co, Mo, Ru, W, Os, Ir, Fe, Mn, Ge, Among them, metal fine particles such as Au, Ag and Cu are more preferable because they can form a circuit pattern which is low in electrical resistance and resistant to corrosion. From the viewpoints of cost and stability, metal fine particles containing Ag are most preferable. The average particle diameter of the metal fine particles is preferably in the range of 1 to 100 nm, more preferably in the range of 3 to 50 nm.
It is also preferable to use carbon fine particles as the conductive fine particles. As the carbon fine particles, graphite fine particles, carbon nanotubes, fullerenes and the like can be preferably exemplified.
The conductive polymer is not particularly limited, but a π conjugated conductive polymer is preferably used.
The? -conjugated conductive polymer is not particularly limited and includes polythiophenes, polypyrroles, polyindols, polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylene, polyparaphenylene vinylene , Polyparaphenylenesulfides, polyarylenes, polyisothianaphthenes, polythiazoles, and the like can be used. Of these, polythiophene and polyaniline are preferable because high conductivity can be obtained. Most preferred is polyethylene dioxythiophene.
The conductive polymer used in the present invention more preferably comprises the above-mentioned? -Conjugated conductive polymer and a polyanion. Such a conductive polymer can be easily produced by chemical oxidation polymerization of a precursor monomer for forming a pi conjugated system conductive polymer with an appropriate oxidizing agent and an oxidation catalyst in the presence of a polyanion.
The polyanion may be a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, a substituted or unsubstituted polyester, and a copolymer thereof , And includes a constituent unit having an anion group and a constituent unit having no anion group.
This polyanion is a solubilized polymer which solubilizes a? -Conjugated conductive polymer in a solvent. Further, the anionic group of the polyanion functions as a dopant for the? -Conjugated conductive polymer and improves the conductivity and heat resistance of the? -Conjugated conductive polymer.
The anion group of the polyanion may be a functional group capable of causing chemical oxidation dope to the? -Conjugated conductive polymer. From the viewpoint of easiness in production and stability, a mono-substituted sulfate group, A phosphoric acid group, a carboxyl group, a sulfo group and the like are preferable. Further, from the viewpoint of the doping effect of the functional group on the? -Conjugated conductive polymer, a sulfo group, a monosubstituted sulfate group and a carboxyl group are more preferable.
Specific examples of the polyanion include polyvinylsulfonic acid, polystyrenesulfonic acid, polyallylsulfonic acid, polyacrylic acid ethylsulfonic acid, polyacrylic acid butylsulfonic acid, poly-2-acrylamide-2-methylpropanesulfonic acid, polyisoprenesulfonic acid, polyvinylcarboxylic acid, Polymethacrylic acid, polystyrene carboxylic acid, polyallylcarboxylic acid, polyacrylic carboxylic acid, polymethacrylic carboxylic acid, poly-2-acrylamide-2-methylpropanecarboxylic acid, polyisoprenecarboxylic acid, . These may be homopolymers or copolymers of two or more.
Further, a polyanion having F (fluorine atom) in the compound may be used. Specific examples thereof include Nafion (manufactured by Dupont) containing a perfluorosulfonic acid group, and Plemion (manufactured by Asahi Glass Co., Ltd.) containing a perfluorinated vinyl ether containing a carboxylic acid group.
Among them, a compound having a sulfonic acid is more preferable in that ink injection stability is particularly good when an inkjet printing method is used, and high conductivity is obtained.
Among these, polystyrenesulfonic acid, polyisoprenesulfonic acid, polyacrylic acid ethylsulfonic acid and polyacrylic acid butylsulfonic acid are preferable. These polyanions exert the effect of excellent conductivity.
The polymerization degree of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 in terms of solvent solubility and conductivity.
Commercially available materials can also be preferably used as the conductive polymer. For example, a conductive polymer (abbreviated as PEDOT / PSS) comprising poly (3,4-ethylenedioxythiophene) polystyrene sulfonic acid is commercially available as CLEVIOS series from HCS Tarck, PEDOT-PASS483095,560598 from Aldrich, It is commercially available as Denatron series from Nagase Chemtex. Also, polyaniline is commercially available as ORMECON series from Nissan Chemical Industries, Ltd.
As the liquid containing the functional material, water, an organic solvent or the like may be used alone or in combination of two or more.
The organic solvent is not particularly limited, and examples thereof include alcohols such as 1,2-hexanediol, 2-methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol and propylene glycol, And ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether and dipropylene glycol monoethyl ether. have.
The liquid containing the functional material may contain various additives such as a surfactant within the range not impairing the effect of the present invention.
When the surfactant is used, for example, in the case of forming the line-
The substrate is not particularly limited, and examples thereof include glass, plastic (polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, acrylic, polyester, polyamide and the like), metals (copper, nickel, Etc.), ceramics, and the like. These may be used alone or in a bonded state. Of these, plastics are preferable, and polyethylene terephthalate and polyolefins such as polyethylene and polypropylene are preferable.
29 is a partially cutaway perspective view showing an example of a parallel line pattern formed on a substrate, and a cross section corresponds to a longitudinal section cut in a direction orthogonal to the formation direction of the parallel line pattern.
One set of two fine lines (line segments) 31 and 32 of the
It is preferable that the line widths W1 and W2 of the
The widths W1 and W2 of the
Since the line widths W1 and W2 of the
From the viewpoint of improving the stability of the
In order to further improve the thinning of the
In order to further improve the thinning of the
The range of arrangement intervals I of the
The arrangement interval I of the
More specifically, the height H1 and the height H2 of the
The
The length L of the
The
It is also preferable that the
It is preferable that the
It is particularly preferable that each of the
(A) When the height of each
(B) W1? 10 占 퐉 and W2? 10 占 퐉, where W1 and W2 are the widths of the
(C) Having 50 nm <H1 <5 μm and 50 nm <H2 <5 μm, where H1 and H2 are the heights of the
As described above, the
In the above description, the inclination angle [theta] in the direction of forming the line-like liquid with respect to the relative movement direction D of the liquid droplet ejecting apparatus with respect to the substrate is mainly shown in the case of 45 DEG and -45 DEG, It is not. The formation direction of the line-like liquid can be set to any arbitrary tilt angle as long as it is not in a direction parallel to the relative movement direction D, and is not perpendicular to the relative movement direction D.
In the above description, an example of forming a mesh-type pattern mainly including a parallel line pattern as the finally formed pattern has been described, but the present invention is not limited thereto. According to the present invention, by forming a line-like liquid along a direction inclined with respect to the relative movement direction D of the liquid droplet ejecting apparatus with respect to the substrate, the degree of patterning freedom in forming various patterns including parallel line patterns is improved. Therefore, when various patterns are formed, it is possible to perform flexible patterning, to prevent moire, and to improve chamfering efficiency. Further, the burden of resetting the arrangement angle of the inkjet head and the substrate can be reduced, and productivity can be improved.
A substrate having a transparent conductive film has a transparent conductive film on the substrate surface including a pattern formed by the above-described pattern forming method. Even when the functional material (conductive material) itself contained therein is not transparent, it may be said that the transparent conductive film makes the pattern difficult to visually recognize by changing the line-shaped liquid into a parallel line pattern and thinning it.
The use of a substrate having a transparent conductive film is not particularly limited, and can be used for various devices provided in various electronic apparatuses.
A preferable use of the substrate having the transparent conductive film according to the present invention is not limited to a display of various types such as a liquid crystal, a plasma, an organic electroluminescence, a field emission or the like, from the viewpoint of remarkably exerting the effect of the present invention And can be preferably used as a transparent electrode for use as a transparent electrode for a touch panel, a cellular phone, an electronic paper, various solar cells, various electroluminescent light control devices, and the like.
More specifically, the substrate provided with the transparent conductive film according to the present invention is preferably used as a transparent electrode of a device. The device is not particularly limited, but for example, a touch panel sensor and the like can be preferably exemplified. The electronic device having these devices is not particularly limited, and for example, a smart phone, a tablet terminal, and the like can be preferably exemplified.
In the above description, the configuration described for one form can be suitably applied to another form.
Example
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.
1. Pattern formation method
(Example 1)
<Description>
As the substrate, a PET substrate subjected to a surface treatment so as to have a contact angle of 20.3 占 of a liquid containing a functional material was prepared. As the surface treatment, corona discharge treatment was carried out using " PS-1M " manufactured by Shinko Denki Kaisha.
<Droplet Discharge Apparatus>
As the droplet ejection apparatus, an ink jet head of "KM1024iLHE-30" (
<Composition of Ink>
As the ink (liquid containing a functional material), the following composition was prepared.
Silver nanoparticles (average particle diameter: 20 nm): 0.16 wt%
Surfactant (" BYK348 " manufactured by Big-Chemie): 0.05 wt%
Diethylene glycol monobutyl ether (abbreviation: DEGBE) (dispersion medium): 20 wt%
· Water (dispersion medium): Remaining amount
≪ Formation of pattern &
Ink was ejected from a plurality of nozzles of the liquid ejection apparatus while moving the liquid ejection apparatus relative to the base material to form a line-like liquid along the X-axis direction inclined by 45 ° with respect to the relative movement direction D. At this time, the relative movement direction D is the direction along the width direction of the substrate.
The line-shaped liquid along the X-axis direction was evaporated and dried, whereby a functional material was selectively deposited on the edge of the line-like liquid to form a parallel line pattern along the X-axis direction. Here, a pattern is formed on a substrate placed on a stage heated at 70 占 폚 to promote the drying of the line-like liquid.
Then, while the liquid droplet ejecting apparatus was moved relative to the substrate, ink was ejected from a plurality of nozzles of the liquid droplet ejecting apparatus to form a line-shaped liquid along the Y-axis direction inclined at -45 [deg.] With respect to the relative movement direction D. Here, the Y-axis direction is a direction orthogonal to the above-described X-axis direction.
The line-shaped liquid along the Y-axis direction was evaporated and dried, whereby a functional material was selectively deposited on the edge of the line-like liquid to form a parallel line pattern along the Y-axis direction. Here, a pattern is formed on a substrate placed on a stage heated at 70 占 폚 to promote the drying of the line-like liquid.
In the pattern formation, relative arrangement angles of the liquid droplet ejecting apparatuses with respect to the substrate were not changed at the time of imparting the line-shaped liquid along the X-axis direction and at the time of imparting the line-shaped liquid along the Y-axis direction. That is, the relative movement directions D of the droplet ejection apparatus with respect to the substrate are the same when the line-shaped liquid along the X-axis direction is given and when the line-shaped liquid along the Y-axis direction is given, to be.
As described above, a mesh-like pattern in which a parallel line pattern along the X-axis direction and a parallel line pattern along the Y-axis direction cross each other was obtained.
In the pattern formation described above, the ink ejection by the liquid ejection apparatus when forming the line-shaped liquid along the X-axis direction and the line-shaped liquid along the Y-axis direction was controlled as follows.
<Ink Discharge Control>
· Droplet capacity per droplet V d = 30 [pL]
Number of gradations N = 8 [dpd]
The total droplet capacity V (= V d [ p L] × N [dpd]) given from one nozzle to form one line type liquid = 240 [pL]
· Nozzle resolution R = 360 [npi]
· Product V · R = 8.64 × 10 4 [pL · npi]
Maximum discharge time difference DELTA tmax = 81.0 [ms] of the liquid containing the functional material discharged from the nozzles adjacent to each other to form one line-shaped liquid.
- Grant interval of line type liquid given by one pass M p = 797.6 [占 퐉]
The interval of the finally provided line-shaped liquid is M = 398.8 [占 퐉]
· Total number of passes
The number of passes for forming the line-shaped liquid along the X-axis direction was two, and the number of the paths for forming the line-shaped liquid along the Y-axis direction was two. The total number of passes, which is the total number of these passes, is four. 1 and a line-type liquid given interval M p which is given by the conference path, in consideration of the given interval M of the line-shaped liquid that is eventually granted, and setting the number of passes.
(Example 2)
A pattern was formed in the same manner as in Example 1, except that the PET substrate subjected to the surface treatment was used as the base material in Example 1 so that the contact angle of the liquid containing the functional material was 8.7 °. The surface treatment was corona discharge treatment using " PS-1M " manufactured by Shinko Denki Keisa Co., as in Example 1, and the treatment strength was adjusted so that the above contact angle was obtained.
(Example 3)
A pattern was formed in the same manner as in Example 1, except that the PET substrate having been subjected to the surface treatment so as to have a contact angle of 10.4 占 of the liquid containing the functional material was used as the base material in Example 1. The surface treatment was corona discharge treatment using " PS-1M " manufactured by Shinko Denki Keisa Co., as in Example 1, and the treatment strength was adjusted so that the above contact angle was obtained.
(Example 4)
A pattern was formed in the same manner as in Example 1 except that a PET substrate subjected to a surface treatment was used as the base material in Example 1 so that the contact angle of the liquid containing the functional material was 29.7 °. The surface treatment was corona discharge treatment using " PS-1M " manufactured by Shinko Denki Keisa Co., as in Example 1, and the treatment strength was adjusted so that the above contact angle was obtained.
(Example 5)
A pattern was formed in the same manner as in Example 1 except that a PET substrate subjected to a surface treatment was used as the base material in Example 1 so that the contact angle of the liquid containing the functional material was 32.3 °. The surface treatment was corona discharge treatment using " PS-1M " manufactured by Shinko Denki Keisa Co., as in Example 1, and the treatment strength was adjusted so that the above contact angle was obtained.
(Example 6)
In Example 1, the number of gradations N was changed to 3 [dpd], and the product V · R was set to 3.24 × 10 4 [pL · npi].
The concentration of silver nanoparticles in the ink was adjusted to 0.42 wt%. Thus, the applied amount of silver nanoparticles per unit length of the line-like liquid was set to a value close to that of Example 1. [
A pattern was formed in the same manner as in Example 1 except for the above point.
(Example 7)
In Example 1, the number of gradations N was changed to 4 [dpd], and the product V · R was set to 4.32 × 10 4 [pL · npi].
The concentration of silver nanoparticles in the ink was adjusted to 0.32 wt%. Thus, the applied amount of silver nanoparticles per unit length of the line-like liquid was set to a value close to that of Example 1. [
A pattern was formed in the same manner as in Example 1 except for the above point.
(Example 8)
In Example 1, the number of gradations N was changed to 12 [dpd], and the product V · R was set to 1.30 × 10 5 [pL · npi].
The concentration of silver nanoparticles in the ink was adjusted to 0.11 wt%. Thus, the applied amount of silver nanoparticles per unit length of the line-like liquid was set to a value close to that of Example 1. [
A pattern was formed in the same manner as in Example 1 except for the above point.
(Example 9)
In Example 1, the number of gradations N was changed to 16 [dpd], and the product V · R was set to 1.73 × 10 5 [pL · npi].
The concentration of the silver nanoparticles in the ink was adjusted to 0.08 wt%. Thus, the applied amount of silver nanoparticles per unit length of the line-like liquid was set to a value close to that of Example 1. [
A pattern was formed in the same manner as in Example 1 except for the above point.
(Example 10)
A pattern was formed in the same manner as in Example 1 except that the moving speed of the inkjet head was changed to set the maximum ejection time difference t max to 101.3 [ms].
(Example 11)
A pattern was formed in the same manner as in Example 1 except that the moving speed of the ink jet head was changed to set the maximum ejection time difference t max to 192.4 [ms].
(Example 12)
A pattern was formed in the same manner as in Example 1 except that the moving speed of the inkjet head was changed to set the maximum ejection time difference t max to 222.8 [ms].
(Example 13)
A pattern was formed in the same manner as in Example 1 except that the application interval M p of the line-like liquid applied by one pass was 398.8 [ms] and the total number of passes was 2 circuits in Example 1 .
In this case, the total number of passes is two, by performing one circuit for forming the line-shaped liquid along the X-axis direction and one circuit for forming the line-shaped liquid along the Y-axis direction.
(Example 14)
A pattern was formed in the same manner as in Example 1 except that the application interval M p of the line-like liquid applied by one pass was 1196.4 [ms] and the total number of passes was 6 circuits in Example 1 .
In this case, the total number of passes was six by three circuits for forming the line-shaped liquid along the X-axis direction and three lines for forming the line-shaped liquid along the Y-axis direction.
(Example 15)
In Example 1, the number of gradations N was changed to 32 [dpd], and the product V · R was set to 3.45 × 10 5 [pL · npi]. With the increase in the width of the second improvement, the application interval M p of the line-shaped liquid applied by one pass is 1595.2 [mu m], and the interval M of application of the line-shaped liquid finally applied is 797.6 [ Respectively.
The concentration of silver nanoparticles in the ink was adjusted to 0.04 wt%. Thus, the applied amount of silver nanoparticles per unit length of the line-like liquid was set to a value close to that of Example 1. [
(Example 16)
In Example 1, the number of gradations N was changed to 48 [dpd], and the product V · R was set to 5.18 × 10 5 [pL · npi]. With the increase in the width of the second improvement, the application interval M p of the line-shaped liquid applied by one pass is 1595.2 [mu m], and the interval M of application of the line-shaped liquid finally applied is 797.6 [ Respectively.
The concentration of silver nanoparticles in the ink was adjusted to 0.027 wt%. Thus, the applied amount of silver nanoparticles per unit length of the line-like liquid was set to a value close to that of Example 1. [
(Example 17)
In Example 1, the number of gradations N was changed to 54 [dpd], and the product V · R was set to 5.83 × 10 5 [pL · npi]. With the increase in the width of the second improvement, the application interval M p of the line-shaped liquid applied by one pass is 1595.2 [mu m], and the interval M of application of the line-shaped liquid finally applied is 797.6 [ Respectively.
The concentration of silver nanoparticles in the ink was adjusted to 0.024 wt%. Thus, the applied amount of silver nanoparticles per unit length of the line-like liquid was set to a value close to that of Example 1. [
(Example 18)
As described with reference to Figs. 17 to 19, when forming a line-like liquid in the first embodiment, a set of droplets imparted from a plurality of nozzles to a pixel set arranged parallel to the nozzle row of the droplet ejection apparatus A plurality of sets are provided in a direction intersecting with the nozzle array and a plurality of sets of the droplets are combined to form a line-like liquid extending in a direction crossing the nozzle array. Specifically, the number of pixels constituting the pixel row set in the nozzle row direction (the number of adjacent pixels) is 2. Also, the number of gradations N was set to 4 [dpd]. The product V · R was 8.64 × 10 4 [pL · npi].
(Example 19)
In Example 18, the number of pixels constituting the pixel set in the nozzle row direction was 8. In addition, the number of gradations N was set to 6 [dpd]. The product V · R was 5.18 × 10 5 [pL · npi]. With the increase in the width of the second improvement, the application interval M p of the line-shaped liquid applied by one pass is 1595.2 [mu m], and the interval M of application of the line-shaped liquid finally applied is 797.6 [ Respectively.
The concentration of silver nanoparticles in the ink was adjusted to 0.027 wt%. Thus, the applied amount of silver nanoparticles per unit length of the line-like liquid was set to a value close to that of Example 18. [
(Comparative Example 1)
The composition of the substrate, the liquid droplet ejection apparatus, and the ink used in Comparative Example 1 is the same as that in Example 1. [
In Comparative Example 1, pattern formation was performed as follows.
≪ Formation of pattern &
While the liquid droplet ejecting apparatus is moved relative to the substrate, ink is continuously ejected from the nozzles of the liquid droplet ejecting apparatus to form a line-shaped liquid along the X-axis direction which is the same direction as the relative movement direction D. At this time, the relative movement direction D is the direction along the width direction of the substrate.
The line-shaped liquid along the X-axis direction was evaporated and dried, whereby a functional material was selectively deposited on the edge of the line-like liquid to form a parallel line pattern along the X-axis direction. Here, a pattern is formed on a substrate placed on a stage heated at 70 占 폚 to promote the drying of the line-like liquid.
Subsequently, the substrate was rotated by 90 DEG with respect to the liquid droplet ejecting apparatus to change the relative arrangement angle of the liquid droplet ejecting apparatus relative to the substrate. That is, the relative moving direction of the liquid droplet ejecting apparatus relative to the substrate was changed. Therefore, the relative movement direction D of the liquid droplet ejecting apparatus after the change corresponds to the forming direction of the previously formed parallel line pattern, that is, the direction orthogonal to the X-axis direction, i.e., the Y-axis direction. The relative movement direction D after the arrangement is changed is a direction along the longitudinal direction of the substrate.
After changing the arrangement as described above, ink was ejected from the nozzles of the liquid ejection apparatus while relatively moving the liquid ejection apparatus relative to the substrate to form a line-shaped liquid along the Y-axis direction in the same direction as the relative movement direction D .
The line-shaped liquid along the Y-axis direction was evaporated and dried, whereby a functional material was selectively deposited on the edge of the line-like liquid to form a parallel line pattern along the Y-axis direction. Here, a pattern is formed on a substrate placed on a stage heated at 70 占 폚 to promote the drying of the line-like liquid.
As described above, a mesh-like pattern in which a parallel line pattern along the X-axis direction and a parallel line pattern along the Y-axis direction cross each other was obtained.
In the pattern formation described above, the ink ejection by the liquid ejection apparatus when forming the line-shaped liquid along the X-axis direction and the line-shaped liquid along the Y-axis direction was controlled as follows.
<Ink Discharge Control>
· Droplet capacity per droplet V d = 30 [pL]
Number of gradations N = 8 [dpd]
- Grant interval of line type liquid given by one pass M p = 797.6 [占 퐉]
The interval of the finally provided line-shaped liquid is M = 398.8 [占 퐉]
· Total number of passes
The number of passes for forming the line-shaped liquid along the X-axis direction was two, and the number of the paths for forming the line-shaped liquid along the Y-axis direction was two. The total number of passes, which is the total number of these passes, is four.
2. Evaluation Method
Pattern characteristics and physical property values were evaluated for the patterns formed in each of the Examples and Comparative Examples.
(1) Pattern property
As the pattern property, the following items (anti-bulge property, 2 improvement width and narrow line width) were evaluated.
· Anti-bulge property
In the two-reflex properties shown in Tables 1 to 5, one set of two fine lines was observed over an area of 50 mm in the fine line formation direction by an optical microscope observation, and the anti-bulge property was evaluated by the following evaluation criteria.
<Evaluation Criteria>
A: No bulge occurred
B: Bulge occurred (3 places or less)
C: Bulge occurred (more than 4 places)
· 2 improvement width
2 Improvement width (탆) is the distance between one set of two fine lines measured by an optical microscope. The measured value corresponds to the interval I described above.
· Line width
The line width (占 퐉) is obtained by measuring the width of one set of two fine lines by optical microscope observation. The measured values correspond to the widths W1 and W2 described above. Further, since the widths of the two fine lines were substantially the same, the fine line width (占 퐉) was taken as the measurement value of one fine line.
(2) Property value
The following items (transmittance, sheet resistance and terminal resistance) were evaluated as physical properties.
Transmittance (total light transmittance)
The transmittance (total light transmittance) (% T) is the total light transmittance measured using AUTOMATICHAZEMETER (MODEL TC-HIIIDP) manufactured by Tokyo Denshoku Co., Further, correction was performed using a pattern-free substrate, and the total light transmittance of the prepared pattern was measured.
· Sheet resistance
The sheet resistance (Ω / □) was measured using a Loresta EP (MODEL MCP-T360 type) in-line four probe probe (ESP) manufactured by Diage Instruments.
Prior to the measurement, the substrate was heated on a hot plate at 120 DEG C for 1 hour, whereby the pattern was subjected to a heat baking treatment.
· Terminal resistance
The terminal resistance (Ω) is a value obtained by forming a pattern in a rectangular area of 100 mm × 5 mm and measuring the resistance value between the terminals (ie, between the both ends in the longitudinal direction of the rectangular area).
Prior to the measurement, the substrate was heated on a hot plate at 120 DEG C for 1 hour, whereby the pattern was subjected to a heat baking treatment.
3. Evaluation
(1) Influence of contact angle
Table 1 shows the results of Examples 1 to 5. Examples 1 to 5 differ in the contact angle of the liquid containing the functional material.
From Table 1, it can be seen that when the contact angle is in the range of 10 [deg.] To 30 [deg.], The effect of further improving the transparency of the parallel line pattern to be formed can be obtained.
When the contact angle is in the range of 10 [deg.] To 30 [deg.], It can be seen that the line-like liquid is more easily formed linearly and bulging can be preferably prevented. As a result, the line segments constituting the parallel line pattern to be formed are more likely to be formed more linearly, and the occurrence of disconnection can be preferably prevented. Thus, it can be seen that when the conductive material is used as the functional material, the sheet resistance and the terminal resistance of the resulting pattern can be further improved.
(2) Effect of product V · R
Table 2 shows the results of Examples 1, 6 to 9 and 15 to 17. Examples 1, 6 to 9 and 15 to 17 differ from the total droplet capacity V given from one nozzle to form one line-shaped liquid and the product V · R of the nozzle row resolution R. More specifically, the product V · R is varied by adjusting the number of gradations N. Further, by adjusting the concentration of silver nanoparticles in the ink, the amount of silver nanoparticles to be imparted per unit length of the line-like liquid is set to a value close to that of the first embodiment.
It can be seen from Table 2 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 line- , It can be seen that bulging can be preferably prevented. As a result, the line segments constituting the parallel line pattern to be formed are more likely to be formed more linearly, and the occurrence of disconnection can be preferably prevented. Thus, it can be seen that when the conductive material is used as the functional material, the sheet resistance and the terminal resistance of the resulting pattern can be further improved.
(3) Influence of maximum discharge time difference t max
Table 3 shows the results of Examples 1, 10 to 12. In Examples 1 and 10 to 12, the maximum ejection time difference DELTA tmax of the liquid containing the functional material discharged from the nozzles adjacent to each other in order to form one line-shaped liquid is made different.
It can be seen from Table 3 that the terminal resistance can be preferably improved by controlling the maximum ejection time difference DELTA tmax to 200 [ms] or less.
(4) Influence of the application interval M p of the line-shaped liquid
Table 4 shows the results of Examples 1, 13 and 14. In
From Table 4, it can be seen that, by setting the line-shaped liquid application interval M p given by one pass to 400 [mu m] or more, It is understood that the effect of reducing the influence and stabilizing the formation of the parallel line pattern can be obtained. As a result, it is found that the effect of further improving the bulge prevention property and transparency is obtained. It is also understood that, if the functional material is a conductive material, the sheet resistance and the terminal resistance of the resulting pattern can be further improved.
(5) Influence of the number of adjacent pixels
Table 5 shows the results of Examples 1, 18 and 19. In
From Table 5, it can be seen that the effects of the present invention are exerted even when the number of adjacent pixels is plural. Further, as shown in the result of Example 19, even when the droplet application amount per length of the line-like liquid is large, that is, when the number of gradations N [dpd] and the number of adjacent pixels is large, the maximum ejection time difference DELTA tmax Can be preferably suppressed. The maximum ejection time difference DELTA tmax [ms] in Embodiment 19 is significantly shortened compared with the maximum ejection time difference DELTA tmax [ms] of Embodiment 16 which is an equivalent liquid droplet application amount, . As a result, it is understood that the sheet resistance and the terminal resistance of the resulting pattern can be further improved.
(6) Comparison of Examples and Comparative Examples
The results of Example 1 and Comparative Example 1 are shown in Table 6.
It can be seen from Table 6 that in the first embodiment in which the line-shaped liquid is formed obliquely with respect to the relative movement direction of the liquid droplet ejecting apparatus and the substrate, it is not necessary to change the arrangement of the substrates in the X- , Productivity can be improved.
In Comparative Example 1, since the relative movement direction D of the droplet ejection apparatus is set in the direction along the sides of the substrate, it is impossible to prevent both moiré and chamfering efficiency.
In addition, it can be seen that Example 1 is also excellent in anti-bulge property in comparison with Comparative Example 1. It is also understood that when the functional material is a conductive material, the effect of improving the sheet resistance and terminal resistance of the obtained pattern can be obtained.
(Example 20)
1. Preparation of ink
Silver dispersion of silver nanoparticles 1 (silver nanoparticles: 40 wt%): 1.75 wt%
Silicone surfactant (BYK-348 manufactured by BICK CHEMICAL CO., LTD.): 0.01 wt%
· Pure water: the remainder
2. Preparation of substrate
As the substrate, a
3. Measurement of surface energy and contact angle
Before forming the mesh-type functional pattern, the surface energy in the formation region of the first parallel line pattern formed by the
(1) Measurement of surface energy
To the
(2) Measurement of the contact angle of the second line type liquid
end. Measurement of the contact angle of the second line-shaped liquid in the formation region of the first parallel line pattern To the polyethylene terephthalate (PET) base material to which the easy-to-adhere processing was applied so that the contact angle with respect to the
I. Measurement of the contact angle of the second line-type liquid outside the region where the first parallel line pattern is formed
3 占 잉크 of the
4. Formation of patterns
<Droplet Discharge Apparatus>
As the droplet ejection apparatus, an ink jet head of "KM1024iLHE-30" (
≪ Formation of pattern &
Ink was ejected from a plurality of nozzles of the liquid ejection apparatus while moving the liquid ejection apparatus relative to the base material to form a line-like liquid along the X-axis direction inclined by 45 ° with respect to the relative movement direction D. At this time, the relative movement direction D is the direction along the width direction of the substrate.
The line-shaped liquid along the X-axis direction was evaporated and dried, whereby a functional material was selectively deposited on the edge of the line-like liquid to form a parallel line pattern along the X-axis direction. Here, a pattern is formed on a substrate placed on a stage heated at 70 占 폚 to promote the drying of the line-like liquid.
Then, while the liquid droplet ejecting apparatus was moved relative to the substrate, ink was ejected from a plurality of nozzles of the liquid droplet ejecting apparatus to form a line-shaped liquid along the Y-axis direction inclined at -45 [deg.] With respect to the relative movement direction D. Here, the Y-axis direction is a direction orthogonal to the above-described X-axis direction.
The line-shaped liquid along the Y-axis direction was evaporated and dried, whereby a functional material was selectively deposited on the edge of the line-like liquid to form a parallel line pattern along the Y-axis direction. Here, a pattern is formed on a substrate placed on a stage heated at 70 占 폚 to promote the drying of the line-like liquid.
In the pattern formation, relative arrangement angles of the liquid droplet ejecting apparatuses with respect to the substrate were not changed at the time of imparting the line-shaped liquid along the X-axis direction and at the time of imparting the line-shaped liquid along the Y-axis direction. That is, the relative movement directions D of the droplet ejection apparatus with respect to the substrate are the same when the line-shaped liquid along the X-axis direction is given and when the line-shaped liquid along the Y-axis direction is given, to be.
As described above, a mesh-like pattern in which a parallel line pattern along the X-axis direction and a parallel line pattern along the Y-axis direction cross each other was obtained.
In the pattern formation described above, the ink ejection by the liquid ejection apparatus when forming the line-shaped liquid along the X-axis direction and the line-shaped liquid along the Y-axis direction was controlled as follows.
<Ink Discharge Control>
· Droplet capacity per droplet V d = 30 [pL]
Number of gradations N = 3 [dpd]
The total droplet capacity V (= V d [ p L] × N [dpd]) given from one nozzle to form one line-shaped liquid = 90 [pL]
· Nozzle resolution R = 360 [npi]
· Product V · R = 3.24 × 10 4 [pL · npi]
Application interval of line type liquid = 282 [占 퐉]
· Total number of passes
The number of passes for forming the line-shaped liquid along the X-axis direction is 1, and the number of passes for forming the line-shaped liquid along the Y-axis direction is 1.
Thus, a mesh-type functional pattern was formed in which the first parallel line pattern and the second parallel line pattern crossed at right angles. The overall size of the mesh-type functional pattern is 50 mm x 50 mm.
(Example 21)
1. Preparation of ink
Silver dispersion of silver nanoparticles 2 (silver nanoparticles: 40 wt%): 1.75 wt%
Silicone surfactant (BYK-348 manufactured by BICK CHEMICAL CO., LTD.): 0.01 wt%
· Pure water: the remainder
Further, the
2. Preparation of substrate
Substrate 1 (surface energy E = 52 mN / m) was used as the substrate.
3. Measurement of surface energy and contact angle
The
4. Formation of patterns
A mesh type functional pattern was formed in the same manner as in Example 20 except that
(Example 22)
1. Preparation of ink
2. Preparation of substrate
As the substrate, a
3. Measurement of surface energy and contact angle
The surface energy C in the formation region of the first parallel line pattern is 56 mN / m, and the ratio of the surface energy C in the formation region of the first parallel line pattern The contact angle F of the two-line type liquid was 17 占 and the contact angle G of the second line-type liquid outside the region where the first parallel line pattern was formed was 28 占.
4. Formation of patterns
In Example 20, the substrate on which the first parallel line pattern was formed was placed on a hot plate at 120 占 폚 and was cleaned by heating for one hour.
After cleaning by heating, the second line-shaped liquid was applied and dried in the same manner as in Example 20 to form a second parallel line pattern.
Thus, a mesh-type functional pattern was formed in which the first parallel line pattern and the second parallel line pattern crossed at right angles. The overall size of the mesh-type functional pattern is 50 mm x 50 mm.
(Example 23)
A mesh-like pattern was formed in the same manner as in Example 22 except that the cleaning by heating was changed to the cleaning by the following electromagnetic wave.
<Cleaning by Electromagnetic Wave>
As the cleaning with electromagnetic waves, cleaning with a xenon flash lamp was performed.
Xenon flash lamp device " SINTERON 2000 " manufactured by Xenon was used to irradiate xenon flash once with a pulse width of 500 microseconds and an applied voltage of 3.8 kV to clean the area including the formation area of the first parallel line pattern.
(Example 24)
A mesh-like pattern was formed in the same manner as in Example 22 except that the cleaning by heating was changed to the cleaning by the following solvent.
≪ Cleaning by Solvent >
2 propanol for 10 minutes to clean the area including the formation region of the first parallel line pattern.
(Example 25)
1. Preparation of ink
2. Preparation of substrate
Substrate 2 (surface energy E = 48 mN / m) was used as the substrate.
3. Measurement of surface energy and contact angle
The surface energy C in the formation region of the first parallel line pattern is 56 mN / m, and the ratio of the surface energy C in the formation region of the first parallel line pattern The contact angle F of the two-line type liquid was 17 占 and the contact angle G of the second line-type liquid outside the region where the first parallel line pattern was formed was 28 占.
4. Formation of patterns
The liquid application amount per length of the second line type liquid in the formation area of the first parallel line pattern was set to be 70 times the liquid application amount outside the formation area of the first parallel line pattern in Example 20, %, And the coating was carried out in the same manner as in Example 20.
Thus, a mesh-type functional pattern was formed in which the first parallel line pattern and the second parallel line pattern crossed at right angles. The overall size of the mesh-type functional pattern is 50 mm x 50 mm.
(Example 26)
1. Preparation of ink
2. Preparation of substrate
As the substrate, a
3. Measurement of surface energy and contact angle
First, an
The surface energy C in the formation region of the first parallel line pattern was 56 mN / m. As a result, in the region where the first parallel line pattern was formed Contact angle F of the second line-like liquid of the first line-shaped liquid was 15 °, and the contact angle G of the second line-shaped liquid outside the region where the first parallel line pattern was formed was 19 °.
4. Formation of patterns
A mesh type functional pattern was formed in the same manner as in Example 20 except that the
(Example 27)
1. Preparation of ink
An
Silver dispersion of silver nanoparticles 1 (silver nanoparticles: 40 wt%): 1.75 wt%
Diethylene glycol monobutyl ether: 20 wt%
· Pure water: the remainder
2. Preparation of substrate
Substrate 1 (surface energy E = 52 mN / m) was used as the substrate.
3. Measurement of contact angle
The contact angle of diethylene glycol monobutyl ether (boiling point 231 ° C) outside the region where the first parallel line pattern was formed was measured using a contact angle measuring apparatus "DM-501" manufactured by Kyowa Chemical Co., Was 5 °. Further, diethylene glycol monobutyl ether was set to a value after 5 seconds from the dropwise addition.
4. Formation of patterns
A mesh-type functional pattern was formed in the same manner as in Example 20 except that
(Example 28)
1. Preparation of ink
2. Preparation of substrate
Substrate 2 (surface energy E = 48 mN / m) was used as the substrate.
3. Measurement of surface energy and contact angle
The surface energy C in the formation region of the first parallel line pattern is 56 mN / m, and the ratio of the surface energy C in the formation region of the first parallel line pattern The contact angle F of the two-line type liquid was 17 占 and the contact angle G of the second line-type liquid outside the region where the first parallel line pattern was formed was 28 占.
4. Formation of patterns
A mesh type functional pattern was formed in the same manner as in Example 20 except that the
(Comparative Example 2)
1. Preparation of ink
Silver dispersion of silver nanoparticles 3 (silver nanoparticles: 40 wt%): 1.75 wt%
Silicone surfactant (BYK-348 manufactured by BICK CHEMICAL CO., LTD.): 0.01 wt%
· Pure water: the remainder
Also, the
2. Preparation of substrate
Substrate 2 (surface energy E = 48 mN / m) was used as the substrate.
3. Measurement of surface energy and contact angle
As a result of measurement in the same manner as in Example 20, the
4. Formation of patterns
A mesh type functional pattern was formed in the same manner as in Example 20 except that
(Example 29)
1. Preparation of ink
2. Preparation of substrate
Substrate 2 (surface energy E = 48 mN / m) was used as the substrate.
3. Measurement of contact angle
The contact angle of diethylene glycol monobutyl ether (boiling point 231 ° C) outside the region where the first parallel line pattern was formed was measured using a contact angle measuring apparatus "DM-501" manufactured by Kyowa Chemical Co., Was 8 °. Further, diethylene glycol monobutyl ether was set to a value after 5 seconds from the dropwise addition.
4. Formation of patterns
A mesh type functional pattern was formed in the same manner as in Example 27 except that the
≪ Measurement of average interval A and average interval B >
The average spacing A in the formation region of the first parallel line pattern with respect to the interval between the two line segments constituting the second parallel line pattern in the functional patterns of the mesh type obtained in Examples 20 to 30 is set to be As the average value of the intervals measured at the seven measurement points A 1 to A 7 . The average interval B outside the region where the first parallel line pattern is formed is measured with respect to the interval between the two line segments constituting the second parallel line pattern at the measurement points B 1 to B 5 at the five positions described in Fig. As an average value of one interval. From the values of the average interval A and the average interval B, the value of B / A in the above-mentioned formula (1) was obtained.
By determining the value of B / A, it is possible to determine whether or not the above-described expression (1) is satisfied. That is, it may be possible to determine whether adjustment for satisfying the above-mentioned expression (1) has been achieved or not.
<Evaluation method>
· Evaluation method of low visibility
The functional patterns of the mesh type obtained in Examples 20 to 30 were visually observed and evaluated according to the following evaluation criteria.
[Evaluation standard]
A: You can not see things like periodic patterns and they look uniform throughout
B: You can see something like a periodic pattern
· Evaluation method of direction unevenness of resistance value
With respect to the mesh-type functional patterns obtained in Examples 20 to 30, unevenness in direction of the resistance value was evaluated by the following method.
A rectangle having a length of 50 mm and a width of 10 mm was cut parallel to the direction of the first parallel line pattern (first direction), and electrodes for measurement using silver paste were attached to both ends of the long side . Similarly, in a rectangle having a length of 50 mm and a width of 10 mm in parallel with the direction of the second parallel line pattern (second direction), the resistance between terminals was measured with a tester, and the ratio of resistance in the first direction and the second direction was evaluated. Specifically, the ratio of the resistances is expressed as a value obtained by dividing the absolute value of the difference between the "resistance in the second direction" and the "resistance in the first direction" by the "resistance in the first direction" as 100 parts.
As a certain criterion, it is practically preferable that the ratio of the resistivity is 10% or less. When the ratio of the resistance exceeds 10%, it can be estimated that it is practically undesirable.
The results are shown in Table 7.
<Evaluation>
From Table 7, in Examples 20 to 27 in which the adjustment was made such that the average interval A and the average interval B satisfied the expression (1) " 0.9 B / A &le; 1.1 ", low visibility was excellent, It can be seen that On the other hand, in Examples 28 to 30 in which such adjustment was not carried out, low visibility was deteriorated and it was found that the unevenness of the resistance value could not be sufficiently prevented.
25 (b) and 25 (a) show optical microscope photographs of the functional pattern of the mesh type of Example 22 and the functional pattern of the mesh type of Example 29, respectively. In each photograph, the direction from the upper left to the lower right is the first direction (the direction of the first parallel line pattern), and the direction from the lower left to the upper right is the second direction (direction of the second parallel line pattern). From the contrast of these photographs, it can be seen that according to the present invention, the low visibility is excellent. In addition, it can be seen that the difference in the lengths of the conductive paths in the first direction and the second direction is not seen, and the non-uniformity of the resistance value can be prevented.
From the above results, it can be seen that the adjustment of the average interval A and the average interval B to satisfy the expression (1) " 0.9 B / A &le; 1.1 "
In Examples 20 and 21, "adjustment of 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 to 5 mN / m or less" Alternatively, the difference between the contact angle F of the second line-like liquid in the formation region of the first parallel line pattern and the contact angle G of the second line-type liquid in the region outside the formation region of the first parallel line pattern is 10 degrees or less , The average interval A and the average interval B satisfy the expression (1) " 0.9 B / A &le; 1.1 ". Here, as an example, examples in which the surface energy and the contact angle are adjusted by surface treatment of the base material and setting of the ink composition are shown.
In Examples 22 to 24, by adjusting the " cleaning the area including the inside of the formation area of the first parallel line pattern before applying the second line type liquid after forming the first parallel line pattern " A and the average spacing B satisfy the following expression (1): 0.9? B / A? 1.1. In Example 22, washing with heating was used. In Example 23, washing with electromagnetic waves was used. In Example 24, washing with a solvent was used, respectively.
In Example 25, the amount of liquid applied per length of the second line-shaped liquid in the formation region of the first parallel line pattern and the amount of liquid applied per length of the second line-shaped liquid outside the formation region of the first parallel line pattern The average interval A and the average interval B satisfy the following expression (1): 0.9? B / A? 1.1.
In Example 26, the adjustment was made so that "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" The difference between the contact angle F of the second line type liquid in the formation area of one parallel line pattern and the contact angle G of the second line type liquid outside the formation area of the first parallel line pattern is 10 DEG or less & , The difference (? DE |) between the surface energy D of the solid surface formed by applying and drying a liquid having the same composition as that of the first line type liquid and the surface energy E outside the region where the first parallel line pattern is formed is set to 5 mN / m or less The average interval A and the average interval B satisfy the expression (1) " 0.9 B / A &le; 1.1 "
In Example 27, the average interval A and the average interval B were adjusted by adjusting "the contact angle of the solvent having the highest boiling point among the solvents in the second line-type liquid outside the formation region of the first parallel line pattern to 6 degrees or less" 0.9? B / A? 1.1 "in Equation (1).
1: substrate
2: first line type liquid
20: droplet
3: first parallel line pattern
31, 32: Segments (fine lines)
4: second line type liquid
5: 2nd parallel line pattern
51, 52: Line segment (fine line)
6: pattern
7: Droplet ejection device
71: ink jet head
72: nozzle
8: Drying device
9: Carriage
D: relative movement direction of the liquid droplet ejecting apparatus to the substrate
E: transport direction of the substrate
X: intersection
Claims (27)
Wherein the line-shaped liquid formed by combining the liquid droplets is dried to deposit the functional material on the edge of the line-like liquid to form a pattern including the functional material.
Next, the second line-shaped liquid is applied on the substrate so as to intersect the formation region of the first parallel line pattern, and in the process of drying the second line-like liquid, the functional material is selectively deposited on the edge portion , And a second parallel line pattern composed of two line segments including the functional material is formed,
Wherein the first parallel line pattern and the second parallel line pattern intersect at at least one intersection point.
&Quot; (1) "
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| PCT/JP2015/068429 WO2015199204A1 (en) | 2014-06-25 | 2015-06-25 | Pattern formation method, substrate provided with transparent electroconductive film, device, and electronic instrument |
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| JP6406078B2 (en) * | 2015-03-14 | 2018-10-17 | コニカミノルタ株式会社 | Pattern forming apparatus and pattern forming method |
| JP6862041B2 (en) * | 2016-08-10 | 2021-04-21 | 住友重機械工業株式会社 | Membrane forming method and film forming apparatus |
| CN106782748B (en) * | 2017-03-03 | 2018-04-24 | 东南大学 | A kind of method for making nano silver wire flexible transparent conductive film |
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| WO2015111731A1 (en) | 2014-01-24 | 2015-07-30 | コニカミノルタ株式会社 | Pattern formation method, substrate provided with transparent electroconductive film, device, and electronic instrument |
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