JP6007776B2 - Parallel line pattern forming method, manufacturing method of substrate with transparent conductive film, device and manufacturing method of electronic apparatus - Google Patents

Description

The present invention relates to a parallel line pattern forming method, a method for producing a substrate with a transparent conductive film having a transparent conductive film containing the parallel line pattern formed by the parallel line pattern forming method on the substrate surface, and the substrate with the transparent conductive film The present invention relates to a device having a material and a method for manufacturing an electronic apparatus including the device.

  In recent years, various types of display technologies such as liquid crystal, plasma, organic electroluminescence, and field emission have been developed in accordance with the increasing demand for thin TVs. In any of these displays having different display methods, the transparent electrode is an essential component. In addition to televisions, transparent electrodes are an indispensable technical element in touch panels, mobile phones, electronic paper, various solar cells, and various electroluminescence light control elements.

  Conventionally, a transparent electrode is mainly an ITO transparent electrode in which a composite oxide (ITO) film of indium-tin is formed on a transparent substrate such as glass or a transparent plastic film by a vacuum deposition method or a sputtering method. I came.

  However, indium used for ITO is a rare metal, and due to the rising price, indium removal is desired. Furthermore, the vacuum deposition method and the sputtering have a problem that the tact time is long and the material use efficiency is very bad, and the ITO transparent electrode has a large problem that the cost is high.

  Therefore, there is an urgent need to develop a transparent electrode that replaces the ITO transparent electrode.

  In US Pat. No. 6,057,059, there is a pattern of conductive traces formed of at least partially bonded nanoparticles, generally free of said partially bonded nanoparticles and generally transparent to light. A transparent electrode is described comprising a pattern defining a disordered shaped cell.

  Patent Document 2 describes a transparent conductive film having a plurality of ring-shaped patterns connected to each other, which are made of carbon nanotubes.

  Patent Document 3 describes a transparent conductive film having a plurality of ring-shaped patterns connected to each other made of silver nanoparticles.

Special table 2011-508424 gazette Special table 2011-502034 gazette WO2011 / 051952

  Since the pattern described in Patent Document 1 is disordered, there is a problem that the transparency and the resistance value vary and the stability is impaired. In addition, when the resistance value is lowered to a predetermined value, there is a problem that the transparency is greatly lowered.

  As in the techniques described in Patent Documents 2 and 3, in order to form a transparent electrode with a ring-shaped pattern, it is necessary to ensure electrical connection by intersecting each ring with at least two rings. As a result, a large number of connection points (intersection points) must be formed on the surface electrode. For this reason, there is room for improvement in terms of the shape stability of the connection points and the control of the number of connection points, and further, there is a problem that transparency is easily impaired by these many connection points. As a result, there is a problem that the transparency and the stability of the resistance value are impaired. Moreover, when the resistance value is lowered to a predetermined value, the problem that the transparency is greatly lowered has not been sufficiently solved.

  Accordingly, an object of the present invention is to provide a parallel line pattern forming method capable of improving transparency and stability of resistance value in a thin line pattern of a conductor.

Moreover, when compared with the same resistance value, the manufacturing method of the base material with a transparent conductive film (transparent electrode) of the outstanding characteristic which can improve transparency, the device which has this base material with a transparent conductive film, and this device were provided. The object is to provide a method of manufacturing an electronic device.

  Other problems of the present invention will become apparent from the following description.

  The above problems are solved by the following inventions.

1.
A parallel line pattern forming method for forming a parallel line pattern having at least one set of parallel lines including a conductive material on a substrate,
Forming a line-shaped liquid having a uniform line width including the conductive material on a substrate having a surface energy of 40 mN / m or more ;
Selectively depositing the conductive material on the edge of the line liquid by evaporating the line liquid while controlling the convection state of the line liquid;
The composition of the line-shaped liquid, the contact angle between the substrate and the line-shaped liquid, the concentration of the conductive material and the drying conditions are set so that the conductive material is selectively deposited on the edge of the line-shaped liquid. A method for forming a parallel line pattern, characterized in that:

2.
A parallel line pattern forming method for forming a parallel line pattern having at least one set of parallel lines including a conductive material on a substrate,
Forming a uniform line-shaped liquid having a line width containing the conductive material on a substrate;
Selectively depositing the conductive material on the edge of the line liquid by evaporating the line liquid while controlling the convection state of the line liquid;
When the contact angle between water and the substrate is θ _S (°) and the contact angle of the line liquid with respect to the substrate is θ _L (°), the line liquid is −20 ° ≦ θ Containing at least one organic solvent satisfying the relationship of _S −θ _L ≦ 5 °,
The parallel line pattern forming method, wherein the conductive material concentration and the drying conditions are selected so as to be in a convection state in which the conductive material is selectively deposited on an edge of the line-like liquid.

3.
When the contact angle between water and the substrate is θ _S (°) and the contact angle of the line liquid with respect to the substrate is θ _L (°), the line liquid is −20 ° ≦ θ _2. The parallel line pattern forming method as described in 1 above, comprising at least one organic solvent satisfying a relationship of _S −θ _L ≦ 5 ° .

4).
4. The line liquid according to any one of 1 to 3, wherein the line liquid is formed by combining droplets containing a conductive material discharged by an ink jet method on the base material. Parallel line pattern forming method.

5.
5. The parallel line pattern forming method according to any one of 1 to 4, wherein the line liquid is formed by applying a liquid containing a conductive material on the substrate by a printing method.

6).
6. The parallel line pattern forming method according to any one of 1 to 5 , wherein the conductive liquid content of the line liquid is in a range of 0.1 wt% to 5 wt%.

7).
7. The parallel line pattern forming method as described in any one of 1 to 6 above, wherein a contact angle of the linear liquid with respect to the substrate is in a range of 5 ° to 50 °.

8).
8. The parallel line pattern forming method according to any one of 1 to 7, wherein the substrate is heated when the line liquid is dried.

9.
The method for producing a transparent conductive film-attached base material and forming a transparent conductive film including a pattern of parallel lines that will be formed by parallel lines pattern forming method according to any one of 1-8 to the substrate surface.

10.
A device manufacturing method Ru using a transparent conductive film-attached substrate produced by the production method of the transparent conductive film substrate with the 9 wherein.

11
Method of manufacturing an electronic apparatus using the device manufactured by the manufacturing method of the device of the tenth aspect.

  ADVANTAGE OF THE INVENTION According to this invention, the parallel line pattern formation method which can improve transparency and stability of resistance value can be provided in the fine wire pattern of a conductor.

Moreover, according to this invention, when compared by the same resistance value, the manufacturing method of the base material with a transparent conductive film (transparent electrode) of the outstanding characteristic which can improve transparency, The device which has this base material with a transparent conductive film And a method of manufacturing an electronic apparatus including the device.

The figure explaining an example of the parallel line pattern formation method which concerns on this invention Principle diagram for explaining an example of a parallel line pattern forming method according to the present invention The partial enlarged plan view which shows an example of the parallel line pattern formed by this invention Iv-iv line sectional view in FIG. 3 (vertical sectional view) The partially expanded plan view which shows the other example of the parallel line pattern formed by this invention The partially expanded plan view which shows the other example of the parallel line pattern formed by this invention The partially expanded plan view which shows the other example of the parallel line pattern formed by this invention

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

  In the parallel line pattern forming method according to the present invention, a parallel line pattern having at least one set of parallel lines including a conductive material is formed on a substrate, which will be described with reference to FIG.

  FIG. 1 is a diagram for explaining an example of a parallel line pattern forming method according to the present invention, and is a perspective view showing a longitudinal section of a substrate on which a parallel line pattern is formed.

  First, as shown in FIG. 1A, a line-shaped liquid 2 having a uniform line width and containing a conductive material is formed on a substrate 1.

  The line width of the line-shaped liquid is determined by the wettability of the liquid and the substrate and the amount of the liquid, and these variations cause a non-uniform line width. From this, the line-shaped liquid 2 having a uniform line width is formed by applying a uniform amount of liquid in the formation length direction of the line-shaped liquid 2 on the substrate 1 having a uniform surface energy. I can do it.

  The formation length of the line-like liquid 2 is preferably 5 times or more of the formation width, and more preferably 10 times or more.

  Next, in the process of drying the line-shaped liquid 2 on the substrate 1, the line-shaped liquid is selected by selecting the composition of the line-shaped liquid, the contact angle between the substrate and the line-shaped liquid, the conductive material concentration, and the drying conditions. By controlling the convection state of the liquid, the conductive material can be selectively deposited on the edge of the line liquid.

  FIG. 2 shows a convection state in which the conductive material can be selectively deposited on the edge of the line-like liquid 2 in the present invention. The drying of the line-shaped liquid 2 arranged on the substrate 1 is faster at the edge than the center part (FIG. 2A), and the solid concentration reaches a saturated concentration as the drying proceeds, and the line-shaped liquid 2 reaches the edge of the line-shaped liquid 2 Local precipitation of solids occurs (FIG. 2 (b)). The edge of the line-shaped liquid 2 is fixed by the deposited solid content, and shrinkage in the width direction of the line-shaped liquid 2 due to subsequent drying is suppressed. Due to this effect, the liquid of the line-shaped liquid 2 forms a convection from the central portion toward the edge so as to compensate for the liquid lost by evaporation at the edge (FIG. 2C).

  Since this convection is caused by immobilization of the contact line of the line-shaped liquid 2 accompanying drying and a difference in evaporation amount between the central part and the edge of the line-shaped liquid 2, the solid content concentration, the contact between the line-shaped liquid 2 and the substrate 1 It changes according to the corner, the amount of the line liquid, the heating temperature of the substrate 1, the arrangement density of the line liquid 2, or the environmental factors of temperature, humidity, and atmospheric pressure, and can be controlled by adjusting these.

  In the present invention, the liquid composition species, the base, and the like are formed so that the line-shaped liquid 2 having a uniform line width is formed on the substrate 1 and the conductive material is selectively deposited on the edge of the line-shaped liquid 2. By selecting the contact angle of the material 1 and the line-like liquid 2, the conductive material concentration, and the drying conditions, the parallel lines 30 including the conductive material as shown in FIG. 1B are formed for the first time. That is, a set of parallel lines 30 including a conductive material is generated from one line-like liquid 2. One set of parallel lines 30 includes a conductive material and is composed of mutually parallel line segments 31 and 32 that are not on the same straight line.

  The parallel line pattern 3 of the present invention has at least one pair of parallel lines 30 formed in this way, and the line segments 31 and 32 constituting the parallel lines 30 are localized conductive. As an aggregate of materials, it can be formed much thinner and stably than the initial width of the line-shaped liquid 2, so that the transparency and resistance stability can be improved in the thin line pattern of the conductor. Is obtained.

  In particular, since the conductive material can be thinned to such an extent that it is difficult to visually recognize or not visible, an effect of excellent transparency can be obtained regardless of the transmittance of the conductive material itself in the visible light region and the like. As a result, the selection range of the conductive material that can be suitably used is widened, the cost can be reduced, and the conductive material can be selected by giving priority to the conductivity. An effect that is easy to ensure is obtained.

  Mathematically, “parallel lines” and “line segments” are defined as having length but not thickness. In the present invention, “parallel lines” and “line segments” are defined as Each of the lines referred to is a three-dimensional linear body having not only a length but also a thickness (width and height).

  Hereinafter, the parallel line pattern forming method according to the present invention will be described in more detail.

  In the present invention, the method of applying the line-shaped liquid 2 on the substrate 1 may be any method as long as the line-shaped liquid 2 can be formed in such a state that it has fluidity sufficient to generate convection in the drying process. For example, there is a printing method.

  As a printing method, a generally known method can be used, and a screen printing method, a relief printing method, an intaglio printing method, an offset printing method, a flexographic printing method and the like can be preferably exemplified.

  In the present invention, the line-like liquid 2 can be formed by bringing together droplets containing a conductive material ejected by an ink jet method on the base material 1. Since patterning can be performed, it is preferable in that it allows free design of transparency and conductivity.

  As the ink jet method, a generally known method can be used. A piezo method in which ink droplets are ejected by deforming an ink flow path by vibration of a piezoelectric element, and a heating element is provided in the ink flow path. The thermal system that generates heat and generates bubbles and discharges ink droplets in response to pressure changes in the ink flow path due to the air bubbles, electrostatically attracts ink by charging the ink in the ink flow path A preferable example is an electrostatic suction method for discharging ink droplets. In this specification, the expression “ink” may be used for the sake of convenience, but it is needless to say that it does not need to contain a pigment / dye and may be a liquid.

  In the present invention, a liquid containing a conductive material may be applied to the surface of the base material 1 to form a set of parallel lines 30 by convection associated with drying. A liquid containing a conductive material (first liquid) is applied to the liquid, and then the liquid is in the drying process or after drying, another liquid (second liquid) is applied in layers and dried. A set of parallel lines 30 may be formed by convection associated with. In this case, the linear liquid 2 is divided into a set of parallel lines 30 mainly by convection of the second liquid. The second liquid preferably has a composition different from that of the first liquid, and a liquid containing no conductive material can also be preferably used.

  In the present invention, the line-like liquid 2 preferably has a conductive material content in the range of 0.1 wt% to 5 wt%. Thereby, the effect which can satisfy | fill both transparency and electroconductivity suitably is acquired. If the content of the conductive material is less than 0.1% by weight, the transparency is excellent but the conductivity may be difficult to obtain. If the content exceeds 5% by weight, the conductivity is excellent but the transparency is difficult to obtain. There is a case.

  In the present invention, the liquid convection in the drying process is a liquid flow that divides the conductive material in the line-shaped liquid 2 so as to form a set of parallel lines 30 as described above. Since the physical phenomenon of convection is used, the influence of the physical properties of the liquid (or the physical properties of the substrate) is large. In particular, as a result of intensive studies, the present inventor has set the contact angle of the line-like liquid 2 to the base material 1, the surface energy of the base material 1 and the like within a specific range as described below. It was found that the effect becomes remarkable.

  In the present invention, the contact angle of the line liquid 2 with respect to the substrate 1 is preferably in the range of 5 ° to 50 °. If the contact angle is 5 ° or less, it is difficult to fix the contact line of the line-shaped liquid. If the contact angle is 50 ° or more, the difference in evaporation amount between the central portion of the line-shaped liquid and the edge is small, and the line-shaped liquid Convection from the center to the edge in the liquid is not promoted. In the contact angle range, the contact line of the line-shaped liquid is likely to be fixed, and the difference in the evaporation amount between the center of the line-shaped liquid and the edge also increases, so that convection from the center to the edge in the line-shaped liquid occurs. Promoted. As a result, the thinning of the parallel lines 30 is further promoted, and the effect of further improving the transparency is obtained.

  The contact angle referred to in the present invention is specifically a static contact angle for measuring the angle (θ) formed by dropping a droplet on the substrate 1 and making the tangent to the edge of the ink droplet and the substrate surface. For example, using a DM-500 manufactured by Kyowa Interface Science Co., Ltd., a droplet to be measured (about 5 μl) is placed on the substrate 1 from a syringe in an environment of 25 ° C. and 50% RH, and the end of the droplet It can obtain | require by measuring the angle ((theta)) which the tangent of and the base-material surface make.

  The contact angle of the line-shaped liquid 2 with respect to the substrate 1 can be easily adjusted by setting the composition of the line-shaped liquid 2 or the surface energy of the substrate 1.

  When adjusting the contact angle according to the composition of the line-shaped liquid 2, any method may be used. For example, a method of adding an additive such as a surfactant or an organic solvent to the line-shaped liquid 2 can be preferably exemplified. The surfactant is not particularly limited, but a silicon surfactant or the like can be used. Silicon-based surfactants are those in which the side chain or terminal of dimethylpolysiloxy acid is polyether-modified. For example, KF-351A and KF-642 manufactured by Shin-Etsu Chemical Co., Ltd. ing.

  Moreover, the surface energy of the base material 1 to which the line-like liquid 2 is applied can be easily set by selecting the material of the base material 1 or by surface treatment.

  In the present invention, the surface energy of the substrate 1 to which the line liquid 2 is applied is preferably 40 mN / m or more. If the surface energy is less than 40 mN / m, the contact angle of the line-shaped liquid 2 with respect to the substrate 1 tends to be high, and the difference in evaporation amount between the liquid center and the edge is small, so that the center of the line-shaped liquid 2 Convection from the part to the edge is not promoted. Although it is possible to change the composition of the line-shaped liquid 2 so as to reduce the contact angle, it is not preferable from the viewpoint of the degree of freedom in selecting the composition type. On the other hand, when the surface energy is 40 mN / m or more, the contact angle of the line-shaped liquid 2 with respect to the base material 1 tends to be low, and the difference in the amount of evaporation between the liquid central portion and the edge increases, so Convection from the center to the edge is promoted. As a result, the thinning of the parallel lines 30 is promoted, and the effect of further improving the transparency is obtained. Moreover, it is preferable also from a viewpoint of the freedom degree of a composition seed | species selection.

  The surface energy as used in the field of this invention is a value showing the wettability of the surface of the base material 1 measured using the contact angle method with water and diiodomethane as standard solutions. Specifically, using DM-500 manufactured by Kyowa Interface Science Co., Ltd., the contact angle between ultrapure water and diiodomethane can be measured, and the surface energy in a two-component system can be calculated.

  Furthermore, in the present invention, the line-like liquid 2 preferably contains at least one kind of water and an organic solvent that satisfies the following conditions. By controlling the wettability in drying the line-like liquid, the line-like liquid 2 It becomes easy to fix the contact line of the liquid. As a result, the thinning of the parallel lines 30 is further promoted, and the effect of further improving the transparency is obtained.

<Conditions>
When the contact angle of the organic solvent with respect to the substrate 1 is θ _S (°) and the contact angle of the linear liquid 2 (containing the organic solvent) with respect to the substrate is θ _L (°), −20 Satisfy the relationship of ° ≦ θ _S −θ _L ≦ 5 °

  In the present invention, the organic solvent contained in the linear liquid 2 is not particularly limited, but a solvent having a boiling point higher than that of water is preferable from the viewpoint of drying and wettability control, and 1,2-hexanediol, 2-methyl- Examples include alcohols such as 2,4-pentanediol, 1,3-butanediol, and propylene glycol, and ethers such as diethylene glycol diethyl ether and diethylene glycol monobutyl ether. It is preferable that the amount is appropriately selected and used.

  In the present invention, it is preferable to heat the substrate 1 when the line liquid 2 is dried. By drying by heating, the drying of the line-shaped liquid 2 is promoted, the difference in evaporation amount between the central part and the edge is increased, and convection from the central part to the edge in the line-shaped liquid 2 is promoted. Thereby, the thinning of the parallel lines 30 is further promoted, so that an effect of increasing transparency can be obtained.

  Specifically, for example, in the drying process, the surface of the substrate 1 to which the line-shaped liquid 2 is applied is heated and dried, and / or the surface of the substrate 1 to which the line-shaped liquid 2 is applied is heated in advance. The method of drying in advance can be used. The surface temperature of the substrate 1 in the drying process is preferably 40 ° C. or higher and 150 ° C. or lower.

  The heating means used when heating the substrate 1 is not particularly limited, and examples thereof include a hot air blower, a hot plate, a heater such as a panel heater, or a device combining them. .

  Next, the substrate 1 to which the line liquid 2 is applied will be described in detail.

  In the present invention, the parallel lines 30 are formed by utilizing the convection of the line-shaped liquid 2 as described above, and the influence of the base material 1 on the liquid flow is great.

  If the substrate 1 absorbs the liquid, the liquid flow is hindered, which is not preferable. Therefore, it is preferable that the base material 1 does not absorb liquid.

Specifically, as the base material that does not absorb the liquid, the liquid absorption amount L by the base material after the base material is immersed in the liquid for 1 minute is in the range of 0 ≦ L ≦ 3 ml / m ² Can be preferably exemplified. Here, the absorption L is a value obtained by taking the difference between the weight of the base material before dipping in the liquid and the weight of the base material after the dipping, and dividing the increased weight by the density of the liquid. Further, it is defined as a value divided by the substrate surface area.

  Specific examples of the substrate 1 preferably used in the present invention are not particularly limited. For example, glass, plastic (polyethylene, polypropylene, acrylic, polyester, polyamide, etc.), metal (copper, nickel, aluminum, iron, etc.) Or an alloy), a ceramic, etc. can be mentioned.

  The substrate 1 is preferably transparent, but is not necessarily limited thereto. According to the present invention, the conductive film (parallel line pattern 3) provided on the substrate 1 is excellent in transparency, so that the substrate 1 can be used in various applications as a conductive optical material regardless of whether the substrate 1 is transparent / opaque. Can be used.

  In addition, as the substrate 1 of the present invention, a substrate having a coating layer that does not absorb liquid on the surface can be preferably used.

  In the present invention, the conductive material contained in the line-like liquid 2 is not particularly limited, but preferred examples include conductive fine particles and conductive polymers.

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

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

  Although it does not specifically limit as a conductive polymer, (pi) conjugated system conductive polymer can be mentioned preferably.

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

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

  The polyanion is a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, a substituted or unsubstituted polyester, and a copolymer thereof. It consists of a structural unit having a group and a structural unit having no anionic group.

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

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

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

  Moreover, the polyanion which has F (fluorine atom) in a compound may be sufficient. Specifically, Nafion (made by Dupont) containing a perfluorosulfonic acid group, Flemion (made by Asahi Glass Co., Ltd.) made of perfluoro vinyl ether containing a carboxylic acid group, and the like can be mentioned.

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

  Furthermore, among these, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethylsulfonic acid, and polyacrylic acid butylsulfonic acid are preferable. These polyanions have the effect of being excellent in conductivity.

  The degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.

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

  Next, the preferable aspect of the parallel line pattern 3 formed by the parallel line pattern formation method which concerns on this invention demonstrated above is demonstrated.

  FIG. 3 is a partially enlarged plan view showing an example of the parallel line pattern 3 formed according to the present invention. 4 is a cross-sectional view taken along the line iv-iv in FIG. 3, and is a cross-sectional view (longitudinal cross-sectional view) obtained by cutting a set of parallel lines 30 included in the parallel line pattern 3 in a direction orthogonal to the line segment direction. is there.

  In the present invention, the two line segments 31 and 32 constituting the parallel line 30 do not necessarily have an island shape completely independent of each other. As shown in the drawing, the two line segments 31 and 32 are connected by the thin film portion 33 formed between the line segments 31 and 32 at a height lower than the height of the line segments 31 and 32. It is also preferable in the present invention to be formed as a continuous body.

  In the present invention, the line widths W1 and W2 of the line segments 31 and 32 constituting the parallel line 30 are each preferably 20 μm or less. Furthermore, if it is 10 micrometers or less, since it will become a level which cannot be visually recognized normally, it is more preferable from a viewpoint of improving transparency. Considering the stability of the line segments 31 and 32, the line widths W1 and W2 of the line segments 31 and 32 are preferably in the range of 2 μm or more and 10 μm or less, respectively.

  In the present invention, the widths W1 and W2 of the line segments 31 and 32 are the height of the thinnest portion where the thickness of the conductive material is the thinnest between the line segments 31 and 32, and the Z Is defined as the widths of the line segments 31 and 32 at half the height of Y1 and Y2. For example, when the parallel line 30 has the thin film portion 33 described above, the height of the thinnest portion in the thin film portion 33 can be set to Z. When the height of the thinnest portion of the conductive material between the line segments 31 and 32 is 0, the line widths W1 and W2 of the line segments 31 and 32 are the line segments 31 and 32 from the surface of the substrate 1. Are defined as the widths of the line segments 31 and 32 at half the heights h1 and h2.

  In the present invention, since the line widths W1 and W2 of the line segments 31 and 32 constituting the parallel line 30 are extremely thin as described above, the base material 1 is used from the viewpoint of securing a cross-sectional area and reducing resistance. The heights h1 and h2 of the line segments 31 and 32 from the surface are preferably 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 parallel lines 30, the h1 / W1 ratio and the h2 / W2 ratio are preferably in the range of 0.05 or more and 1 or less, respectively.

  In addition, from the viewpoint of further improving the transparency of the parallel line pattern 3, the parallel line 30 is the height Z of the thinnest portion where the thickness of the conductive material is the thinnest between the line segments 31 and 32, specifically, The height Z of the thinnest portion of the thin film portion 33 is preferably in the range of 10 nm or less. Most preferably, the thin film portion 33 is provided in the range of 0 <Z ≦ 10 nm in order to achieve a balance between transparency and stability.

  Furthermore, in order to further reduce the resistance of the parallel line pattern 3 and improve the transparency, the h1 / Z ratio and the h2 / Z ratio in the parallel lines 30 are each preferably 5 or more, and preferably 10 or more. More preferably, it is particularly preferably 20 or more.

  The interval I between the line segments 31 and 32 can be adjusted as appropriate depending on the resistance value and transparency design, and is preferably adjusted in the range of 10 μm to 300 μm. In the present invention, the interval I between the line segments 31 and 32 is defined as the distance between the maximum protrusions of the line segments 31 and 32.

  Furthermore, in the present invention, the resistance values of the line segment 31 and the line segment 32 are reduced in the parallel line 30 from the viewpoint of reducing a load caused by currents having different magnitudes flowing between the line segment 31 and the line segment 32. Are preferably considered to be equal. For this purpose, it is preferable to give the same shape (similar cross-sectional area) to the line segment 31 and the line segment 32. Specifically, the heights h1 and h2 of the line segment 31 and the line segment 32 are set. A substantially equal value is preferable. Similarly, it is preferable that the line widths W1 and W2 of the line segment 31 and the line segment 32 are substantially equal values.

  In the present invention, “parallel lines” and “parallel” do not necessarily mean parallel in a strict sense, but the line segments 31 and 32 are coupled to each other at least over a certain length L in the line segment direction. Means not. 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 of the line segments 31 and 32 in the line segment direction is preferably 5 times or more of the interval I between 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 line-shaped liquid 2.

  The line segments 31 and 32 constituting the parallel line 30 have substantially the same line widths W1 and W2, and the line widths W1 and W2 are sufficiently narrower than the distance between the parallel lines (interval I). It is preferable that

  Furthermore, in the parallel line pattern 3 according to the present invention, the line segment 31 and the line segment 32 constituting the parallel line 30 are preferably formed at the same time.

  In the parallel line pattern 3 according to the present invention, as the parallel lines 30, it is particularly preferable that the line segments 31 and 32 constituting the parallel lines 30 have at least parallel lines that satisfy all of the following conditions (a) to (d). preferable.

(A) When the height of each line segment constituting the parallel lines is h1 and h2, and the height of the thinnest portion in each line segment is Z, 5 ≦ h1 / Z and 5 ≦ h2 / Z (B) W1 ≦ 10 μm and W2 ≦ 10 μm when the widths of the lines constituting the parallel lines are W1 and W2, respectively. (C) The distance between the lines constituting the parallel lines is I 10 μm ≦ I ≦ 200 μm (D) When the heights of the line segments constituting the parallel lines are h1 and h2, 50 nm <h1 <5 μm and 50 nm <h2 <5 μm about

  The shape of the parallel line pattern 3 according to the present invention can be controlled by selecting the composition of the line-shaped liquid 2, the contact angle between the substrate and the line-shaped liquid, the concentration of the conductive material, the drying conditions, and the like. it can.

  In the present invention, the line segments 31 and 32 constituting the parallel line 30 only need to be parallel to each other, and are not limited to the linear body as shown in FIGS. It may be a body.

  In the present invention, the line segments 31 and 32 can be given a free shape connecting these linear and curved bodies. Therefore, in the present invention, the number of intersections can be freely controlled as compared with the cases of Patent Documents 2 and 3 in which the conductivity cannot be ensured unless the ring-shaped patterns are connected.

  In the present invention, the parallel line pattern 3 is not limited to the case where the parallel line pattern 3 is constituted by one set of parallel lines 30, and is preferably an aggregate obtained by collecting two or more sets of parallel lines 30. When the parallel line pattern 3 is constituted by a plurality of sets of parallel lines 30, the shape of each parallel line 30 may be the same or different.

  For example, the stripe-like parallel line pattern 3 may be formed by paralleling two or more sets of parallel lines 30 at intervals, or, as shown in FIG. A set of parallel lines 30 may be joined by one or more intersections 34 to form a parallel line pattern 3. In the example of FIG. 6, a plurality of parallel lines 30 intersect with each other at a plurality of intersections 34 to form a lattice pattern as a whole. 6 can be formed by, for example, forming one parallel line first and then forming the other parallel line so as to intersect it. .

  In the present invention, when one or a plurality of intersections are given to the parallel line pattern 3, it is also preferable to give a non-parallel line shape such as a ring shape or a loop shape at these intersection points. FIG. 7 is a plan view showing an example of the parallel line pattern 3 in which a non-parallel line shape is given to the intersection point 34. FIG. 7A shows a state in which three sets of parallel lines 30, 30, 30 intersect at a loop-shaped intersection 34. FIG. 7B shows a state in which four sets of parallel lines 30, 30, 30, 30 intersect at a ring-shaped intersection 34. Further, FIG. 7C shows a state in which two sets of parallel lines 30 and 30 and another two sets of parallel lines 30 and 30 intersect at a common loop-shaped intersection 34. Yes. Thus, in the present invention, the intersection of the parallel line pattern 3 can be a branch point or a connection point that connects a plurality of sets of parallel lines 30 to each other.

  Since the base material with a transparent conductive film according to the present invention has the transparent conductive film including the parallel line pattern 3 formed by the parallel line pattern forming method according to the present invention described above on the surface of the base material 1, the same resistance value is obtained. When compared with the above, it has excellent characteristics that can improve transparency.

The use of the substrate with a transparent conductive film according to the present invention is not particularly limited, but various types such as liquid crystal, plasma, organic electroluminescence, field emission, and the like can be obtained from the standpoint of significantly achieving the effects of the present invention. It can be suitably used as a transparent electrode for a display, or as a transparent electrode used in a touch panel, a mobile phone, electronic paper, various solar cells, various electroluminescence light control elements, and the like.
More specifically, the substrate with a transparent conductive film according to the present invention is suitably used as a transparent electrode of a device. Although it does not specifically limit as a device, For example, a touch panel etc. can be illustrated preferably. Moreover, although it does not specifically limit as an electronic device provided with these devices, For example, a smart phone, a tablet terminal, etc. can be illustrated preferably.

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

Example 1
Stripe a line-like liquid with a line width / space width = 100 μm / 200 μm on the clear hard coat layer of a PET film (base material) with a clear hard coat layer using an ink having the composition shown in Table 1 by flexographic printing. The coating was formed into a shape.

  Each line-shaped liquid became a set of parallel lines (silver thin lines) in the course of drying under the following drying conditions.

<Drying conditions>
-Substrate heating method: After forming the line-shaped liquid, the substrate is heated with a hot plate.
-Substrate surface temperature: 70 ° C

  Table 1 shows the results of measuring the total light transmittance and conductivity of the obtained pattern.

(Examples 2 to 14, Comparative Example 1)
An inkjet head (manufactured by Konica Minolta Co., Ltd.) is applied to the surface of the clear hard coat layer of the clear hard coat layer-coated PET film (base material) having different surface energy subjected to corona discharge treatment using PS-1M manufactured by Shinko Electric Instrument Co. KM512L "; standard droplet amount 42 pl), ink was deposited by one-pass printing with a nozzle array direction line pitch of 141 μm and scanning direction dot pitch of 60 μm using the ink having the composition shown in Table 1. The droplets were united on the substrate to form a striped line-like liquid similar to that in Example 1.

  The line-like liquids of Examples 2 to 14 became a set of parallel lines (silver thin lines) in the process of drying under the same drying conditions as in Example 1. On the other hand, Comparative Example 1 did not become a pair of parallel lines (silver thin lines) in the process of drying, but became a single line.

  Table 1 shows the results of measuring the total light transmittance and conductivity of the obtained pattern.

<Measurement method>
The total light transmittance shown in Table 1 is a value obtained by measuring the total light transmittance using AUTOMATIC ZEMETER (MODEL TC-HIIIDP) manufactured by Tokyo Denshoku. In addition, it is the value measured as a total light transmittance of the pattern film (transparent conductive film) which performed correction | amendment using the base material.

  The surface resistance shown in Table 1 is evaluated by using a hot plate and heating and baking at 120 ° C. for 1 h, and then taking out electrodes at right angles to the parallel thin wire direction and using CD770 manufactured by Sanwa Electric Instruments Co., Ltd. It calculated from the measured resistance value.

  The contact angles shown in Table 1 are obtained by placing a droplet to be measured (about 5 μl) from the syringe onto the substrate 1 using a DM-500 manufactured by Kyowa Interface Science Co., Ltd. in an environment of 25 ° C. and 50% RH. It was determined by measuring the angle (θ) formed by the tangent to the edge of the droplet one second after dropping and the substrate surface.

  The surface energy shown in Table 1 is obtained by using a DM-500 manufactured by Kyowa Interface Science Co., Ltd., and placing a drop of ultrapure water and diiodomethane (about 5 μl) on the substrate 1 from a syringe, and the contact angle after 1 second from dropping. By measuring the surface energy, the surface energy in the two-component system was calculated.

1: Substrate 2: Line-shaped liquid 3: Parallel line pattern 30: Parallel line 31, 32: Line segment 33: Thin film part 34: Intersection

Claims (11)

A parallel line pattern forming method for forming a parallel line pattern having at least one set of parallel lines including a conductive material on a substrate,
Forming a line-shaped liquid having a uniform line width including the conductive material on a substrate having a surface energy of 40 mN / m or more ;
Selectively depositing the conductive material on the edge of the line liquid by evaporating the line liquid while controlling the convection state of the line liquid;
The composition of the line-shaped liquid, the contact angle between the substrate and the line-shaped liquid, the concentration of the conductive material and the drying conditions are set so that the conductive material is selectively deposited on the edge of the line-shaped liquid. A method for forming a parallel line pattern, characterized in that: A parallel line pattern forming method for forming a parallel line pattern having at least one set of parallel lines including a conductive material on a substrate,
Forming a uniform line-shaped liquid having a line width containing the conductive material on a substrate;
Selectively depositing the conductive material on the edge of the line liquid by evaporating the line liquid while controlling the convection state of the line liquid;
When the contact angle between water and the substrate is θ _S (°) and the contact angle of the line liquid with respect to the substrate is θ _L (°), the line liquid is −20 ° ≦ θ Containing at least one organic solvent satisfying the relationship of _S −θ _L ≦ 5 °,
The parallel line pattern forming method, wherein the conductive material concentration and the drying conditions are selected so as to be in a convection state in which the conductive material is selectively deposited on an edge of the line-like liquid. When the contact angle between water and the substrate is θ _S (°) and the contact angle of the line liquid with respect to the substrate is θ _L (°), the line liquid is −20 ° ≦ θ parallel line pattern forming method according to claim 1, characterized in that it contains at least one kind of organic solvent satisfying the relationship of _{S -θ L} ≦ 5 °. The line-shaped liquid droplets together containing a conductive material discharged by the ink jet system, according to any of claims 1-3, characterized in that it is formed by coalescence on said substrate Parallel line pattern forming method. The parallel line pattern forming method according to any one of claims 1 to 4, wherein the line liquid is formed by applying a liquid containing a conductive material on the base material by a printing method. Parallel line pattern forming method according to any one of claims 1 to 5, wherein the conductive material content of the linear liquid, characterized in that it is in the range of 5 wt% or less than 0.1 wt%. Parallel line pattern forming method according to any one of claims 1 to 6, the contact angle, characterized in that it is in the range of 5 ° to 50 ° with respect to the base of the line-shaped liquid.   The parallel line pattern forming method according to claim 1, wherein the substrate is heated when the line liquid is dried. One parallel line pattern forming method with a transparent conductive film substrate manufacturing method, wherein a transparent conductive film including a pattern of parallel lines that will be formed to form the substrate surface by according to the claims 1-8. The method according to claim 9 with a transparent conductive film substrate device Ru using a transparent conductive film-attached substrate produced by the method according. Method of manufacturing an electronic apparatus using the device manufactured by the manufacturing method according to claim 10 of the device described.

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