JP6508062B2 - Pattern forming method, substrate with transparent conductive film, device and electronic device - Google Patents

Description

  The present invention relates to a pattern forming method for forming a coating film having a functional material deposited on an edge, a substrate with a transparent conductive film using the coating film formed by the coating film forming method, a device and an electronic device About.

  In recent years, with the advancement of devices with higher functionality and higher density, techniques for forming fine patterns including functional materials are required, and at the same time, cost reduction and simplification of manufacturing processes are also required.

  Patterning by a printing method has been proposed as the above-described pattern forming method. However, even if various printing methods are used, the formation of a pattern with a line width of about 20 μm is the limit, and it is difficult to cope with the required miniaturization.

  According to Patent Document 1, a finer electric wiring pattern can be formed compared to the size of the coating film by collecting the solid content contained in the liquid in the periphery of the coating film by utilizing the convection inside the liquid.

  On the other hand, with the recent increase in demand for flat-screen TVs and the like, various types of display technologies such as liquid crystal, plasma, organic electroluminescence, and field emission have been developed. The transparent electrode is an essential component in any of the displays having different display methods. In addition to televisions, transparent electrodes are an indispensable technology in touch panels, mobile phones, electronic papers, various solar cells, and various electroluminescent light control devices.

  Conventionally, as the transparent electrode, an ITO transparent electrode in which an indium-tin complex oxide (ITO) film is formed by sputtering on a transparent substrate such as glass or a transparent plastic film has been mainly used.

  However, indium used in ITO is a rare metal, and due to the increase in price, de-indium is desired. Furthermore, sputtering has problems such as long tact time and very low material usage efficiency, and there is a big problem that ITO transparent electrode is expensive.

  Therefore, development of a transparent electrode to replace the ITO transparent electrode is urgently needed.

  On the other hand, Patent Document 2 discloses a fine ring-like pattern of silver nanoparticles by collecting silver nanoparticles contained in the liquid in the periphery of the coating film by utilizing convection inside the liquid. Transparent conductive films connected to each other are described.

  Patent Document 3 discloses that a transparent carbon nanotube having a plurality of interconnected fine ring-like patterns made of carbon nanotubes is collected by using the convection inside the liquid to collect the carbon nanotubes contained in the liquid at the periphery of the coating film. Conductive films are described.

  In Non-Patent Documents 1 and 2, after droplets ejected by the inkjet method are united on a substrate to form a line-like liquid, silver nano-particles contained in the liquid are utilized using convection inside the liquid. A transparent conductive film is described in which fine fine line patterns made of silver nanoparticles are arranged in a mesh by collecting particles in the periphery of a line liquid.

Patent 4325343 WO2011 / 051952 JP 2011-502034 gazette V. Bromberg, S. Ma, T. J. Singler, Appl. Phys. Lett. 102, 214101 (2013) Z. Zhang, X, Zhang, Z. Xin, M. Deng, Y. Wen, Y. Song, Advanced Materials 2013 Vol: 25 (46): 6714-6718

  In the pattern formation method described in Patent Document 1 and Non-patent Document 1, when forming a long linear pattern, a bulge is generated due to the force to shrink spherically under the influence of the internal pressure of the liquid, resulting in a line liquid Part of or breaks the linearity. As a result, part of the pattern of the functional material deposited at the end of the line-like liquid is broken or the pattern shape becomes nonuniform, so there is a problem in the stability of pattern formation.

  In the techniques described in Patent Documents 2 and 3, in order to form a transparent electrode by a ring pattern, it is necessary to cross each ring with at least two rings to ensure electrical connection, as a result, A large number of connection points (intersection points) must be formed on the electrodes. Therefore, there is room for improvement in terms of shape stability of connection points and control of the number of connection points. Moreover, when the resistance value is reduced to a predetermined value, the problem that the transparency is also significantly reduced has not been sufficiently solved.

  In Non-Patent Document 2, since the droplet application amount of the line-like liquid is small, the intervals of the fine line patterns deposited on the edge become narrow. For this reason, there is a problem that the transparency is easily impaired when the thin line pattern is disposed in the plane so as to be the lowest in visibility.

  Therefore, an object of the present invention is to provide a pattern forming method capable of stably forming a pattern including fine lines by suppressing a bulge generated when forming a line-like liquid, and achieving both high transparency and low visibility. is there.

  Moreover, the further subject of this invention is a base material with a transparent conductive film (transparent electrode) which has the outstanding characteristic which can improve transparency and visibility when compared by the same resistance value, a device provided with this, and an electron To provide equipment.

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

  The above problems are solved by the following inventions.

の条件を満たすように吐出を制御するパターン形成方法。1. Forming a line-like liquid containing the functional material by discharging a liquid containing the functional material by the droplet discharge device and coalescing the droplets discharged sequentially on the substrate; and the line-like liquid And allowing the functional material to be selectively deposited on the edge of the line-like liquid by evaporating and drying, wherein the droplet application amount of the line-like liquid is 4. The contact angle of the droplets discharged and controlled so as to be 5 × 10 ⁻¹⁰ [m ³ / m] or more and 5.5 × 10 ⁻⁹ [m ³ / m] or less on the substrate 10 [10 [ [D] [m], the diameter of a single landed droplet on the substrate of the droplet discharged and controlled to be not less than 45 ° and not less than 45 °, on the substrate of the discharged droplet When the discharge interval of the ink is p [m], the relationship with the discharge frequency f [1 / s] Is the following equation

The pattern formation method which controls discharge so that the conditions of 5 may be satisfied.

  2. 5. The pattern forming method according to 1 above, which uses a droplet discharge device provided with gradation number changing means.

  3. The method for forming a pattern according to the above 1 or 2, wherein the substrate is heated or a dryer is used to dry the linear liquid.

  4. 5. The pattern formation method according to any one of 1 to 3, wherein the functional material content of the liquid before the drying is in the range of 0.1% by weight to 5% by weight.

  5. The pattern forming method according to any one of the above 1 to 4, wherein the functional material is a conductive material or a conductive material precursor.

  6. The base material with a transparent conductive film which has a transparent conductive film containing the pattern formed by the pattern formation method in any one of said 1-5 on the base-material surface.

  7. The device which has a base material with a transparent conductive film of the said 6 description.

  8. The electronic device provided with the device of the said 7.

Conceptual diagram for explaining the pattern formation method according to the present invention The figure explaining the discharge condition of the pattern formation method concerning the present invention Principle diagram for explaining a pattern forming method according to the present invention The top view which shows the example of formation of the pattern by this invention A partial enlarged plan view showing an example of a pattern formed by the present invention The vi-vi line sectional view in FIG. 4 Diagram for explaining the embodiment

  Below, the form for implementing this invention is demonstrated.

  In the pattern formation method according to the present invention, the liquid containing the functional material is discharged by the droplet discharge method, and the linear liquid formed on the substrate is evaporated and dried, thereby providing functionality to the edge of the linear liquid. The material is selectively deposited to form a pattern, and a conceptual diagram is shown in FIG.

  In FIG. 1, H is a droplet discharge device. As a droplet discharge device, an ink jet head of a so-called ink jet recording device can be used, but it is not particularly limited as long as the discharge conditions of the present invention described later can be realized. The droplet discharge mechanism of the droplet discharge device is not particularly limited, but a thermal method, a piezo method, a continuous method or the like can be exemplified.

  1 is a substrate, 2 is a line-like liquid containing a functional material, and 3 is a pattern formed by selectively depositing the functional material on the edge of the line-like liquid 2.

  As shown in FIG. 1A, while the droplet discharge device H and the substrate 1 are relatively scanned, the droplet discharge device H discharges a liquid containing a functional material, and the droplets discharged in sequence Are united on the substrate to form a line-like liquid 2 containing a functional material.

  Then, as shown in FIG. 1 (b), the linear liquid 2 is evaporated and dried to selectively deposit the functional material on the edge of the linear liquid 2.

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

  The present invention is suitably used in order to achieve both high transparency and low visibility when forming such a pattern 3.

  In the present specification, “transparency” and “low visibility” are distinguished. "Transparency" is based on the transmission of light through the pattern. On the other hand, "low visibility" is based on the difficulty of recognizing patterns visually. It is excellent in low visibility so that the thin line which comprises a pattern can not be visually recognized. Even if the transparency is the same, a difference in low visibility may occur, and as will be described later with reference to FIG. 4, the present invention is effective not only in achieving transparency but also achieving low visibility. Used.

  FIG. 2 is a view for explaining discharge conditions of the pattern forming method according to the present invention. FIG. 2 (a) shows the droplet discharge state in FIG. 1 (a) as viewed from the side, and FIG. 2 (b) shows it in plan view.

  As shown in FIG. 2, in the present embodiment, the droplet discharge device H and the substrate 1 are relatively scanned in the x direction, and droplets containing the functional material are sequentially discharged. The line-like liquid 2 is formed by combining the

  At this time, when the diameter of the landed droplet when the discharged droplet lands on the substrate 1 is D [m] and the discharge interval of the discharged droplet is p [m], the relationship represented by the following equation (1) At this time, the landed droplets are coalesced on the substrate 1 to form the line-like liquid 2.

Further, the diameter D [m] of the landed droplet may be calculated by the following equation (2) from the contact angle θ [rad] of the discharged droplet with the substrate and the discharged droplet amount V [m ³ ]. it can. The contact angle is a static contact angle. For example, using DM-500 manufactured by Kyowa Interface Science Co., Ltd., a syringe (about 5 μl) to be measured under an environment of 25 ° C. and 50% RH is syringed It can obtain | require by mounting | wearing on the base material 1, and measuring the angle which the tangent of a droplet end and a substrate surface make.

  When forming a line-like liquid by coalescing droplets sequentially discharged from the droplet discharge method on a substrate, a part of the line-like liquid is broken or the linearity is broken due to the occurrence of a bulge. was there. As a result, there has been a problem that a part of the pattern of the functional material deposited at the end of the line liquid is broken or the pattern shape becomes nonuniform.

  The inventor noted that such a bulge is generated when the landed droplet flows into the line-shaped liquid on the rear side in the scanning direction of the droplet discharge device, and the line shape on the rear side in the scanning direction from the landed droplet It has been found that the occurrence of bulge can be suppressed by supplying an amount of liquid equal to or greater than the amount of liquid flowing into the liquid by means of the discharge droplet.

In the diameter D [m] of a certain landed droplet selected by the composition of the liquid containing the functional material, the droplet discharge device, and the substrate type, as the discharge interval p [m] is decreased, The amount of liquid into which the landed droplets flow is increased. That is, the bulge can be suppressed by supplying a larger amount of liquid by the discharged droplet by an amount corresponding to the reduction of the discharge interval p [m]. In the pattern formation method of the present invention, the diameter of a single landed droplet on the substrate of the ejected droplet is D [m], and the ejection interval of the ejected droplet on the substrate is p [m] Control the discharge such that the relationship with the discharge frequency f [1 / s] satisfies the condition of the following equation (3), thereby forming a linear liquid with uniform line width and high linearity. be able to.

  Further, in the case of using a droplet discharge device which discharges a specified droplet amount, it is preferable to control the droplet amount by gradation driving. That is, it is preferable to use a droplet discharge device provided with gradation number changing means. The gradation number is the number of ink droplets to be ejected for one dot.

  FIG. 3 is a principle view for explaining a pattern forming method according to the present invention.

  In the process of drying the line-like liquid 2 on the substrate 1, the selection of the line-like liquid 2 by selecting the composition of the line-like liquid 2, the contact angle of the substrate 1 and the line-like liquid 2, the functional material concentration and the drying conditions The functional material can be selectively deposited on the edge of the line-like liquid 2 by controlling the convection state.

  The convective state in which the functional material can be selectively deposited on the edge of the linear liquid 2 in the present invention will be described with reference to FIG. Drying of the line liquid 2 disposed on the substrate 1 is quicker at the edge compared to the central part, and the solid concentration reaches a saturation concentration with the progress of drying, and the local precipitation of solid content at the edge of the line liquid 2 Happens. By the precipitated solid content, the edge of the line-like liquid 2 is fixed, and the contraction in the width direction of the line-like liquid 2 accompanying the subsequent drying is suppressed. Due to this effect, the liquid in the line liquid 2 forms a convection from the center to the edge so as to compensate for the liquid lost by evaporation at the edge.

  Since the convection is caused by the fixation of the contact line of the line liquid 2 and the difference in evaporation between the center part of the line liquid 2 and the edge due to drying, the solid concentration, the contact between the line liquid 2 and the substrate 1 It can be controlled by adjusting and adjusting according to the amount of horn, linear liquid 2, heating temperature of base material 1, arrangement density of linear liquid 2, or environmental factors of temperature, humidity and pressure. .

  In the present invention, the contact angle of the linear liquid 2 with respect to the substrate 1 is preferably in the range of 10 [°] to 45 [°]. If the contact angle is less than 10 °, fixation of the contact line of the linear liquid 2 hardly occurs, and if the contact angle exceeds 45 °, the difference in evaporation between the central portion of the linear liquid 2 and the edge Is small, and convection from the center to the edge in the linear liquid 2 is not promoted. In the contact angle range, fixation of the contact line of the line liquid 2 tends to occur, and the difference in evaporation between the center part of the line liquid 2 and the edge also becomes large. Convection is promoted. As a result, thinning is further promoted, and an effect of further enhancing transparency can be obtained. The contact angle of the linear liquid 2 with respect to the substrate 1 can be adjusted by setting the composition of the linear liquid 2 or the surface energy of the substrate 1.

  Further, the difference in evaporation between the central portion of the linear liquid 2 and the edge is influenced by the degree of diffusion of the gas formed on the surface of the droplet. From this, the droplet application amount of the linear liquid 2 largely contributes to the convection. When a plurality of line liquids 2 are formed at one time in a plane, if the droplet application amount of the line liquid 2 increases, the amount of evaporation of the line liquid 2 central portion and the edge due to the influence of the adjacent line liquids 2 And the convection that causes the functional material to be selectively deposited on the edge of the linear liquid 2 does not significantly occur. As a result, the width of the thin line becomes large, and the solid content remains outside the predetermined patterning position of the thin line portion, and the transparency is impaired.

From this, the droplet amount V [m ³ ] and the discharge interval p [m] are controlled so that the droplet application amount of the linear liquid 2 is not more than 5.5 × 10 ^-9 [m ³ / m]. By doing this, the convection can be generated significantly.

  As shown in the example of pattern formation in FIG. 4, in a plane, the spacing I between one set of two fine line patterns 31 and 32 of the pattern 3 formed by drying the line liquid 2 and the pattern 3 adjacent to each other In the case where the same number of thin lines are arranged by the same number by arranging the thin lines so that the intervals J between the thin line patterns 32 and 31 arranged on the near sides are substantially the same (the permeability becomes the same) An advantage is obtained that the visibility of the thin line is the lowest when compared. In the same thin line width, by forming the pattern so that the distance I between one set of two thin line patterns 31 and 32 is wide, the effect of the lowest visibility can be obtained while maintaining high transparency. .

The spacing I between one set of two fine line patterns 31 and 32 is determined by the line width I ′ of the linear liquid 2 selected from the contact angle of the liquid containing the functional material with the substrate 1 and the droplet application amount . In the contact angle range controlled by the pattern formation method of the present invention, the distance I between one set of two thin line patterns 31 and 32 is designed wide by maintaining the droplet application amount large, and high transparency is maintained As it is, the pattern can be formed such that the visibility of the thin line is the lowest. Specifically, it is preferable to select the droplet amount V [m ³ ] and the discharge interval p [m] so that the droplet application amount is 4.5 × 10 ⁻¹⁰ [m ³ / m] or more.

  According to the present invention, the interval I can be increased by increasing the droplet application amount or the like in a state in which the occurrence of the bulge is prevented. For example, for the value of the interval J set to an arbitrary value, A value close to, preferably substantially the same value as the value of the interval J can be given to the interval I as appropriate. That is, it is possible to obtain advantageous effects such as lowering the visibility by arranging the thin lines at desired intervals while maintaining the stability of the thin lines. As described above, even in the viewpoint of increasing the degree of freedom of fine line formation, a remarkable effect can be exhibited.

  As described above, according to the present invention, in the pattern forming method for forming a coating film in which the functional material is selectively deposited on the edge of the line-like liquid, it occurs when forming the line-like liquid By suppressing the bulge, a pattern with high uniformity of shape can be stably obtained, and high transparency and low visibility can be compatible.

  Further, according to the present invention, a substrate with a transparent conductive film (transparent electrode) having excellent characteristics capable of improving transparency and visibility when compared at the same resistance value, a device and an electronic apparatus provided with the same. Can be provided.

  FIG. 5 is a partially enlarged plan view showing an example of a pattern formed on a substrate by the pattern forming method according to the present invention. 6 is a cross-sectional view taken along the line vi-vi in FIG. 5, and is a cross-sectional view (longitudinal cross-sectional view) obtained by cutting one set of two thin wires included in the pattern in a direction orthogonal to the line segment direction.

  In the present invention, one set of two thin lines (line segments) 31 and 32 of the pattern 3 generated from one line-like liquid does not necessarily have to be islands completely independent of each other. As illustrated, the two line segments 31 and 32 are connected by a thin film portion 30 formed between the line segments 31 and 32 at a height lower than the height of the line segments 31 and 32. Forming as a continuous body is also preferred in the present invention.

  In the present invention, the line widths W1 and W2 of the line segments 31 and 32 of the pattern 3 are preferably 10 μm or less. If it is 10 μm or less, the level is usually not visible, which is more preferable from the viewpoint of improving the transparency. In consideration of the stability of the line segments 31 and 32, the line widths W1 and W2 of the line segments 31 and 32 are preferably in the range of 2 μm to 10 μm.

  In the present invention, the widths W1 and W2 of the line segments 31 and 32 refer to the height of the thinnest portion at which the thickness of the functional material is the thinnest between the line segments 31 and 32, as Z. When the projecting heights of the line segments 31 and 32 from Y.sub.1 and Y.sub.2 are Y1 and Y2, respectively, they are defined as the widths of the line segments 31 and 32 at half the height of Y1 and Y2. For example, when the pattern 3 includes the thin film portion 30 described above, the height of the thinnest portion of the thin film portion 30 can be Z. When the height of the thinnest portion of the functional material between the line segments 31 and 32 is 0, the line widths W1 and W2 of the line segments 31 and 32 are line segments 31 and 32 from the surface of the base material 1. Is defined as the width of line segments 31 and 32 at half height of heights h1 and h2.

  In the present invention, since the line widths W1 and W2 of the line segments 31 and 32 constituting the pattern 3 are extremely thin as described above, the surface of the base material 1 is ensured in view of securing a cross-sectional area and reducing resistance. It is desirable that the heights h1 and h2 of the line segments 31 and 32 from are higher. Specifically, the heights h1 and h2 of the line segments 31 and 32 are preferably in the range of 50 nm to 5 μm.

  Furthermore, in the present invention, from the viewpoint of improving the stability of the pattern 3, the h1 / W1 ratio and the h2 / W2 ratio are each preferably in the range of 0.01 or more and 1 or less.

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

  Furthermore, in order to further improve the thinning of the pattern 3, the h1 / Z ratio and the h2 / Z ratio are preferably 5 or more, more preferably 10 or more, and particularly preferably 20 or more. preferable.

  The interval I between the line segments 31 and 32 can be adjusted as appropriate, and is preferably adjusted to a range of 10 μm to 300 μm. Further, as described above, the interval I is preferably adjusted to a value close to the interval J described with reference to FIG. 4, and most preferably adjusted to a value substantially equal to the interval J. In the present invention, the interval I between the line segments 31 and 32 is defined as the distance between the maximum protruding portions of the line segments 31 and 32.

  Furthermore, in the present invention, it is preferable to give the line segments 31 and 32 the same shape (similar cross-sectional area), and more specifically, the height h1 of the line segments 31 and 32 It is preferable to make h2 and h2 have substantially equal values. Similarly, the line widths W1 and W2 of the line segment 31 and the line segment 32 preferably have substantially equal values.

  In the present invention, the line segments 31 and 32 do not necessarily have to be parallel, and it is sufficient if the line segments 31 and 32 do not connect over at least a certain length L in the line segment direction. Preferably, the line segments 31 and 32 are substantially parallel over at least a certain length L in the line segment direction.

  In the present invention, the length L in the line segment direction of the line segments 31 and 32 is preferably 5 times or more of the interval I of the line segments 31 and 32, and more preferably 10 times or more. The length L and the interval I can be set corresponding to the formation length and formation width of the pattern (line-like liquid) 2.

  In the present invention, the line segments 31 and 32 are connected at the formation start point and the end point of the line-like liquid 2 (the start point and the end point across a certain length L of the line segment direction) to form a continuous body. It is preferable in the invention.

  The line segments 31 and 32 preferably have substantially equal line widths W1 and W2, and the line widths W1 and W2 are preferably sufficiently smaller than the distance between two lines (interval I).

  Furthermore, it is preferable that the line segment 31 and the line segment 32 which comprise the pattern 3 produced | generated from one linear liquid be formed simultaneously.

  As for the pattern 3 which concerns on this invention, it is especially preferable that each line segment 31, 32 satisfy | fills all the conditions of following (a)-(e).

  (A) When the heights of the line segments 31 and 32 are h1 and h2 and the height of the thinnest part in each line is Z, 5 ≦ h1 / Z and 5 ≦ h2 / Z.

  (A) W1 ≦ 10 μm and W2 ≦ 10 μm, where W1 and W2 are the widths of the line segments 31 and 32, respectively.

  (C) Assuming that the distance between the line segments 31 and 32 is I, 10 μm ≦ I ≦ 300 μm.

  (D) Assuming that the heights of the line segments 31 and 32 are h1 and h2, 50 nm <h1 <5 μm and 50 nm <h2 <5 μm.

  The substrate with a transparent conductive film including at least the pattern formed on the surface of the substrate by the pattern forming method according to the present invention has excellent properties capable of improving the transparency and low visibility when compared at the same resistance value. .

  Although the base material used in the present invention is not particularly limited, for example, glass, plastic (polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, acrylic, polyester, polyamide etc.), metal (copper, nickel, aluminum, iron etc.) Or alloys), ceramics, etc., and these may be used alone or in a bonded state. Among them, plastic is preferable, and polyethylene terephthalate, and polyolefin such as polyethylene and polypropylene are preferable.

  The functional material used in the present invention is preferably, but not limited to, a conductive material or a conductive material precursor. The conductive material precursor refers to one that can be changed to a conductive material by performing appropriate processing.

  As a conductive material, a conductive fine particle, a conductive polymer, etc. can be illustrated preferably, for example.

  The conductive particles are not particularly limited, but Au, Pt, Ag, Cu, Ni, Cr, Rh, Pd, Zn, Co, Mo, Ru, W, Os, Ir, Fe, Mn, Ge, Sn, Ga Fine particles of In, etc. can be preferably exemplified. Among them, metal fine particles such as Au, Ag and Cu are more preferable because they can form a circuit pattern having low electric resistance and resistance to corrosion. From the viewpoint of cost and stability, metal fine particles containing Ag are most preferable. The average particle diameter of these metal fine particles is preferably in the range of 1 to 100 nm, more preferably in the range of 3 to 50 nm.

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

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

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

  More preferably, the conductive polymer used in the present invention comprises the π-conjugated conductive polymer described above and a polyanion. Such a conductive polymer can be easily produced by chemical oxidation polymerization of a precursor monomer forming a π-conjugated conductive polymer in the presence of a polyanion with an appropriate oxidizing agent and an oxidation catalyst.

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

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

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

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

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

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

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

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

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

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

  The organic solvent is not particularly limited, but, for example, alcohols such as 1,2-hexanediol, 2-methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol, propylene glycol, etc. Ethers, such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, etc. can be illustrated.

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

  By using a surfactant, for example, when forming the linear liquid 2 using a droplet discharge device, it becomes possible to adjust the surface tension and the like to stabilize the discharge. The surfactant is not particularly limited, but a silicon surfactant or the like can be used. The silicone surfactant is a polyether-modified side chain or terminal of dimethylpolysiloxane, and commercially available products such as KF-351A and KF-642 manufactured by Shin-Etsu Chemical, BYK 347 and BYK 348 manufactured by Big Chemie, etc. are commercially available. ing. The amount of surfactant added is preferably 1% by weight or less based on the total amount of the liquid forming the line-like liquid 2.

  The application of the substrate with a transparent conductive film according to the present invention is not particularly limited, and can be used for various devices provided in various electronic devices.

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

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

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

(Examples 1 to 13, Comparative Examples 1 to 8)
An inkjet head ("KM 512L" manufactured by Konica Minolta, Inc .; standard droplet volume) on the surface of a PET film, glass or COP film (base material) treated with corona discharge using PS-1M manufactured by Shinko Electric Instruments Co., Ltd. 42pl, "KM512M"; standard droplet size 14pl, or "KM512S"; standard droplet size 4pl), ink with composition shown in Tables 1 to 5 and discharge condition so that the pitch between the nozzle row direction is 423μm Drops were discharged to form a linear liquid in the form of stripes. The pattern was dried and solids were deposited on the edge to form a plurality of one set of two thin line patterns. After rotating the substrate on which the pattern is formed by 90 ° with respect to the scanning direction of the inkjet head, a plurality of fine line patterns of two sets are formed again under the same conditions, and a mesh as shown in FIG. 7 It formed a letter-like pattern.

  7A shows the case where the interval I described with reference to FIG. 4 is small and smaller than the interval J, and FIG. 7B shows the case where the interval I is large and close to the interval J. It shows. In the present embodiment, the pitch of the line liquid is 423 μm, and the distance I (measured value of “two line width” described later) between the thin wires 31 and 32 in the pattern 3 formed from one line liquid is A state sufficiently smaller than (423 μm / 2 =) 212 μm is approximated in FIG. 7A, and a state close to 212 μm is approximated in FIG. 7B.

(Comparative example 9)
Ink jet printer (Fujifilm DMP-2831 printer; standard droplet volume: 10 pl) on the glass substrate surface treated with corona discharge using PS-1M manufactured by Shinko Electric Instruments Co., Ltd., ink of the composition shown in Table 5, discharge condition The liquid droplets were discharged so as to have a pitch of 423 μm in the nozzle row direction, to form a linear liquid in a stripe shape. The pattern was dried and solids were deposited on the edge to form a plurality of one set of two thin line patterns. After rotating the substrate on which the pattern is formed by 90 ° with respect to the scanning direction of the inkjet head, a plurality of fine line patterns of two sets are formed again under the same conditions, and a mesh as shown in FIG. 7 It formed a letter-like pattern.

  In the above Examples 1 to 13 and Comparative Examples 1 to 9, the following drying conditions and firing conditions were applied.

<Drying conditions>
-Substrate heating method: The substrate was heated with a hot plate after forming the liquid application part.
· Substrate surface temperature: 70 ° C

<Firing conditions>
-Firing method: After drying the liquid application part, the substrate was heated with a hot plate.
· Substrate surface temperature: 120 ° C, 1 hour

  With respect to the obtained pattern, the bulge resistance, the two line widths, the total light transmittance, the low visibility and the sheet resistance value were measured. The results are shown in Tables 1-5.

<Measurement method, evaluation method>
-Bulge prevention property The double line | wire property shown to Tables 1-5 observed the thin wire | line of 1 set 2 by optical microscope observation, and confirmed the bulge prevention property. Those in which the bulge occurred were evaluated as "x", and those in which the bulge did not occur were evaluated as "o".

Two Line Widths The two line widths (μm) shown in Tables 1 to 5 are obtained by measuring the distance between one set of two thin lines by observation with an optical microscope. The measured value corresponds to the interval I described above.

・ Transmittance (total light transmittance)
The transmittance (total light transmittance) (% T) shown in Tables 1 to 5 is a value obtained by measuring total light transmittance using AUTOMATICAZEMETER (MODEL TC-HIIIDP) manufactured by Tokyo Denshoku Co., Ltd. In addition, it is the value which measured as a total light transmittance of the pattern (transparent conductive film) which correct | amended using the base material without a pattern (transparent conductive film).

-Low visibility The low visibility shown in Tables 1 to 5 is such low visibility that the samples according to Examples 1 to 13 and Comparative Examples 1 to 9 are viewed from a position 50 cm away on the light table and the thin line can not be seen In particular, “A” indicates that the thin line can not be recognized, “B” indicates that the thin line can be recognized slightly but there is no practical problem, and “C” indicates that the thin line can be clearly recognized. It was evaluated.

Sheet resistance The sheet resistance (Ω / □) shown in Tables 1 to 5 is a value obtained by measuring the sheet resistance value using a Loresta EP (MODEL MCP-T360 type) in-line four probe probe (ESP) manufactured by Dia Instruments Co., Ltd. It is.

  In Tables 1 to 5 above, “DEGBE” is diethylene glycol monobutyl ether, “PET” is polyethylene terephthalate, and “COP” is an abbreviation of cycloolefin polymer.

<Evaluation>
In Examples 1 to 13, it can be seen that both the bulge preventing property, the two line widths, the total light transmittance, the low visibility, and the sheet resistance value are excellent.

  On the other hand, Comparative Example 1 in which the in-plane droplet application amount (droplet application amount in the scanning direction of the droplet discharge device) does not reach the range of the present invention is inferior in low visibility and exceeds the range of the present invention It is understood that Comparative Example 2 is inferior to the total light transmittance, the low visibility, and the sheet resistance value.

（上記式において、Ｄ［ｍ］は、吐出した液滴の基材上における単一着弾液滴の直径、ｐ［ｍ］は、吐出した液滴の基材上の吐出間隔、ｆ［１／ｓ］は、吐出周波数を表す。）Moreover, it turns out that it is inferior to a sheet resistance value in the comparative examples 3 and 4 which do not satisfy | fill the conditions of Formula (3) which concerns on this invention.

(In the above equation, D [m] is the diameter of a single landed droplet on the substrate of the ejected droplet, p [m] is the ejection interval of the ejected droplet on the substrate, f [1 / s] represents the ejection frequency.)

  Furthermore, Comparative Example 5 in which the contact angle is less than the range of the present invention and Comparative Example 6 in which the range of the present invention is exceeded are inferior to the total light transmittance, low visibility and sheet resistance.

  Furthermore, in Comparative Examples 7 and 8 which do not satisfy the condition of the above equation (3), the sheet resistance value is inferior, and the in-plane droplet deposition amount (droplet deposition amount in the scanning direction of the droplet discharge device) It can be seen that Comparative Example 9 which does not satisfy the range is inferior in low visibility. These Comparative Examples 7 to 9 are based on the conditions described in Non-Patent Documents 1 and 2.

1: base material 2: linear liquid 3: pattern 30: thin film portion 31, 32: fine wire H: droplet discharge device

Claims (8)

Forming a linear liquid containing the functional material by discharging the liquid containing the functional material by the droplet discharge device and coalescing the droplets sequentially discharged on the substrate;
And d) selectively depositing the functional material on the edge of the line-like liquid by evaporating the line-like liquid and drying it.
The liquid controlled and discharged so that the droplet application amount of the line-like liquid is not less than 4.5 × 10 ⁻¹⁰ [m ³ / m] and not more than 5.5 × 10 ⁻⁹ [m ³ / m] The contact angle of the droplet on the substrate is controlled to be 10 ° to 45 °, and the diameter of a single landed droplet on the substrate of the ejected droplet is D m When the discharge interval of the discharged droplets on the substrate is p [m], the relationship with the discharge frequency f [1 / s] is

The pattern formation method which controls discharge so that the conditions of 5 may be satisfied.   2. The pattern forming method according to claim 1, wherein a droplet discharge device provided with gradation number changing means is used.   The pattern formation method according to claim 1 or 2, wherein the substrate is heated or a dryer is used to dry the linear liquid.   The pattern formation method according to any one of claims 1 to 3, wherein the functional material content of the liquid before the drying is in the range of 0.1 wt% to 5 wt%.   The pattern forming method according to any one of claims 1 to 4, wherein the functional material is a conductive material or a conductive material precursor. The manufacturing method of the base material with a transparent conductive film which has a transparent conductive film containing the pattern formed by the pattern formation method in any one of Claims 1-5 on the base-material surface. Method of manufacturing a device having Claim 6 with a transparent conductive film substrate produced by the method described. Method of manufacturing an electronic apparatus provided with a device manufactured by the manufacturing method according to claim 7.

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