JPWO2015005457A1 - Coating film forming method, substrate with transparent conductive film, device and electronic device - Google Patents

Abstract

An object of the present invention is to provide a coating film forming method capable of stably forming a pattern including a thin line having a thin line width and reducing solid content remaining outside a predetermined position of patterning of the thin line portion. When forming the coating film in which the functional material is selectively deposited on the edge by drying the pattern 2 formed by applying the liquid containing the material on the base material 1, the liquid has the function The functional material is deposited on the edge of the coating film by including a solvent having a high affinity with the functional material and a solvent having a low affinity with the functional material.

Description

  The present invention relates to a coating film forming method for forming a coating film in which a functional material is 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. Regarding equipment.

  In recent years, higher functionality and higher density of devices have been advanced, and a technique for forming a fine pattern including a functional material is required. At the same time, cost reduction and simplification of a manufacturing process are also required.

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

  Japanese Patent Laid-Open No. 2004-228561 describes that a fine electrical wiring pattern can be formed as compared with the size of the coating film by collecting solids contained in the liquid in the periphery of the coating film using convection inside the liquid.

  On the other hand, in recent years, various types of display technologies such as liquid crystal, plasma, organic electroluminescence, or 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 TVs, 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.

  On the other hand, Patent Document 2 uses a convection inside the liquid to collect silver nanoparticles contained in the liquid at the periphery of the coating film, thereby forming a fine ring-shaped pattern made of silver nanoparticles. Transparent conductive films connected to each other are described.

  Patent Document 3 discloses that transparent carbon nanotubes having a plurality of fine ring-shaped patterns connected to each other are collected by collecting the carbon nanotubes contained in the liquid at the periphery of the coating film using convection inside the liquid. A conductive film is described.

Japanese Patent No. 4325343 WO2011 / 051952 Special table 2011-502034 gazette

  In the pattern forming method described in Patent Document 1, it is difficult to further reduce the pattern line width, and when a long linear pattern is formed, there is a high possibility that a part of the pattern will be cut. There was a problem in sex. Furthermore, the solid content which was not conveyed by the convection also had the subject that it remained easily outside the patterning predetermined position of a thin wire | line part.

  In the pattern forming methods described in Patent Documents 2 and 3, it is difficult to further reduce the ring-shaped pattern line width, and solid content that has not been transported by convection remains outside the patterning predetermined position of the thin line portion. There was a problem that transparency and conductivity were lowered.

  Accordingly, an object of the present invention is to provide a coating film forming method capable of stably forming a pattern including a thin line having a thin line width and reducing solid residue remaining outside a predetermined patterning position of the thin line portion.

  Moreover, the further subject of this invention provides the base material with a transparent conductive film (transparent electrode) which has the outstanding characteristic which can improve transparency, when compared with the same resistance value, a device provided with this, and an electronic device There is to do.

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

  The above problems are solved by the following inventions.

1. When forming a coating film in which the functional material is selectively deposited on the edge by drying a pattern formed by applying a liquid containing the functional material on a substrate,
The liquid contains a solvent having a high affinity with the functional material and a solvent having a low affinity with the functional material, so that the functional material is deposited on the edge of the coating film. Film forming method.

  2. 2. The method of forming a coating film according to 1, wherein the solvent having a low affinity with the functional material has a higher boiling point than the solvent having a high affinity with the functional material.

  3. 3. The method for forming a coating film according to 1 or 2, wherein the content of the solvent having a low affinity with the functional material with respect to the total amount of the liquid is in the range of 10% by weight to 40% by weight.

  4). 4. The method for forming a coating film according to any one of 1 to 3, wherein the substrate is heated when the liquid is dried.

  5). The said coating film is a coating-film formation method in any one of said 1-4 formed by a printing system.

  6). The coating film forming method according to any one of 1 to 5, wherein the coating film is formed by a droplet discharge method.

  7). 7. The coating film forming method according to any one of 1 to 6, wherein the functional material is a conductive material or a conductive material precursor.

  8). When the functional material is contained in the liquid in an aqueous dispersion state, a solvent having high affinity with the functional material is selected from the group consisting of water, methanol, ethanol, 1-propanol, and isopropanol, and the function Solvents having a low affinity for volatile materials are N, N-dimethylformamide, N, N-dimethylacetamide, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol 8. The method for forming a coating film according to any one of 1 to 7 above, which is selected from the group consisting of propylene glycol monoethyl ether, 1,3-butanediol, 1,4-butanediol, and 1,2-hexanediol.

  9. The solvent having a high affinity with the functional material is water, and the solvent having a low affinity with the functional material is selected from the group consisting of diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, and 1,3-butanediol. 9. The method for forming a coating film according to 8 above.

  10. When the functional material is contained in the liquid in an organic solvent-based dispersion state, the solvent having high affinity with the functional material is hexane, heptane, octane, cyclohexane, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, A solvent selected from the group consisting of 1-butanol, 2-butanol, isobutanol, and 1-pentanol, having a low affinity with the functional material is nonane, decane, xylene, 1-octanol, 2-octanol, n- The coating according to any one of 1 to 7 above, which is selected from the group consisting of nonyl alcohol, tridecyl alcohol, ethylene glycol monobutyl ether acetate, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, cyclohexanone, phenol, and benzyl alcohol. Forming method.

11. The coating according to any one of 1 to 10, wherein a difference in SP value between a solvent having a high affinity with the functional material and a solvent having a low affinity with the functional material is 19 (MPa) ^1/2 or more. Film forming method.

  12 The base material with a transparent conductive film which has the transparent conductive film containing the said coating film formed by the coating-film formation method in any one of said 1-11 on the base-material surface.

  13. 13. A device comprising the substrate with a transparent conductive film according to 12 above.

  14 14. An electronic apparatus comprising the device according to 13.

The figure explaining an example of the coating-film formation method which concerns on this invention The figure explaining an example of the principle of the coating-film formation concerning this invention The enlarged plan view which shows an example of the ring-shaped coating film formed by this invention Iv-iv line enlarged sectional view in FIG. The principal part enlarged plan view which shows an example of the parallel-line coating film formed by this invention Vi-vi sectional view in FIG. The figure explaining an Example The figure explaining an Example

  Below, the form for implementing this invention is demonstrated.

  In the method for forming a coating film according to the present invention, the affinity between the functional material and a solvent having a high affinity with the functional material (hereinafter sometimes referred to as a high affinity solvent) and the functional material is high. The functional material is selectively deposited on the edge by drying a pattern formed by applying a liquid containing at least a low solvent (hereinafter sometimes referred to as a low affinity solvent) onto a substrate. This will be described with reference to FIG.

  FIG. 1 is a diagram for explaining an example of a coating film forming method according to the present invention.

  Fig. 1 (a1) to Fig. 1 (a4) show how a ring-shaped coating film is formed as an example of the coating film forming method according to the present invention.

  FIG. 1 (a1) and FIG. 1 (a2) show the state of a pattern (coating pattern) formed of a liquid containing at least a functional material, a high affinity solvent, and a low affinity solvent. 1A1 is a plan view and FIG. 1A2 is a cross-sectional view.

  On the other hand, FIG. 1 (a3) and FIG. 1 (a4) show the state of the coating film formed by drying the liquid of FIG. 1 (a1). FIG. 1 (a3) is a plan view. 1 (a4) is a sectional view.

  In the present invention, as shown in the drawing, a circular pattern 2 is formed on the substrate 1 when viewed in plan, and when this pattern 2 is dried, the liquid is composed of a functional material and a high affinity solvent. And the low-affinity solvent are included to promote the deposition of the functional material at the edge, and the ring-shaped coating film 3a is formed with the functional material deposited selectively at the edge rather than at the center. Is done.

  Moreover, FIG.1 (b1)-FIG.1 (b4) have shown a mode that a parallel-line-shaped coating film is formed as an example of the coating-film formation method which concerns on this invention.

  1 (b1) and 1 (b2) show patterns (coating patterns) formed by applying a liquid containing at least a functional material, a high affinity solvent, and a low affinity solvent on a substrate. FIG. 1 (b1) is a plan view, and FIG. 1 (b2) is a cross-sectional view.

  On the other hand, FIG. 1 (b3) and FIG. 1 (b4) show the state of the coating film formed by drying the liquid of FIG. 1 (b1), and FIG. 1 (b3) is a plan view. 1 (b4) is a sectional view.

  In the present invention, as shown in the drawing, a linear pattern 2 is formed on the substrate 1 when viewed in plan, and when the pattern 2 is dried, the liquid is composed of a functional material and a high affinity solvent. And a low-affinity solvent to promote the deposition of the functional material at the edge, and the line-shaped parallel line coating film 3b in which the functional material is selectively deposited at the edge rather than at the center. Is formed.

  FIG. 2 is a diagram illustrating an example of the principle of coating film formation according to the present invention.

  In the present invention, when the pattern 2 contains a high affinity solvent and a low affinity solvent together with the functional material, in the process of drying the pattern 2 on the substrate 1, only the high affinity solvent is used. Compared with, the affinity with respect to the functional material of a liquid falls. At this time, since the drying of the pattern 2 arranged on the substrate 1 is faster at the edge than at the center (see FIG. 2A), the function that is excluded from the edge of the pattern 2 due to the decrease in affinity. The local deposition of the functional material is promoted (see FIG. 2B).

  Thereby, immobilization of the contact line (edge) of the pattern 2 occurs in the early stage of drying of the pattern 2, and the shrinkage of the pattern 2 in the substrate surface direction accompanying the subsequent drying is suppressed. By this effect, the liquid of the pattern 2 forms a convection from the central part toward the edge so as to compensate for the liquid lost by drying at the edge (see FIG. 2C).

  Since this convection is likely to occur in the early stage of drying, the functional material in the pattern 2 is smoothly conveyed to the edge, and further deposition is promoted. Thereby, thinning of the fine line part pattern of the functional material formed in the edge part and solid content residue outside the fine line part can be reduced. As a result, in the transparent conductive film, it is possible to obtain an effect capable of satisfying both transparency and conductivity.

  Furthermore, it is desirable to fix the edge of the pattern 2 in the early stage of drying in order to prevent a bulge generated due to a force that tends to shrink into a spherical shape due to the influence of the surface tension of the liquid in the drying process. Thereby, a fine line part pattern can be stably formed in a predetermined position, and it is particularly effective when forming a line-shaped parallel line coating film 3b in which a bulge is likely to be generated during the drying process. As a result, in forming the thin line portion pattern of the functional material, it is possible to achieve both the reduction of the line width and the stability.

  In the above explanation of the principle, the case where the solvent for forming the pattern 2 is only a high affinity solvent is given as a comparison object. Not played. In the case of only the low affinity solvent, the affinity between the functional material and the liquid is low regardless of the progress of drying, so that the state in which the functional materials are self-assembled is stabilized. As a result, problems such as self-assembly (deposition) occur in parts other than the edge of the coating film.

  In the present invention, the liquid forming the pattern 2 may contain the functional material as a dissolution system or a dispersion system.

  There is a difference between the dissolution system and the dispersion system whether the dispersion unit of the functional material is a molecular unit (single molecular unit or aggregate unit) or a fine particle unit. In common. In any system, when the affinity of the liquid to the functional material is high, the binding between the liquid and the functional material tends to be stabilized relative to the binding between the functional materials, It is easy to maintain a dispersed state. On the other hand, when the affinity of the liquid to the functional material is low, the connection between the liquid and the functional material tends to stabilize the connection between the functional materials, and the functional materials gather together. Easy to do. That is, if it is a dissolution system, it is easy to precipitate, and if it is a dispersion system, it is easy to aggregate.

  In the present invention, “a solvent having a high affinity with a functional material (high affinity solvent)” means a functional material dispersed in a molecular unit (single molecular unit or aggregate unit) or fine particle unit in the solvent. On the other hand, it means a solvent that can easily maintain its dispersion state (especially a dissolved state when dispersed in molecular units (single molecular unit or aggregate unit)). “Low solvent (low affinity solvent)” means a solvent that is difficult to maintain.

  In the present invention, the higher affinity solvent has a higher affinity with the functional material, and the lower affinity solvent has a lower affinity with the functional material.

When pattern 2 contains a functional material as a dissolution system,
(A) As a “high affinity solvent”, a dispersion state (dissolved state) of a functional material dispersed in molecular units (single molecular unit or aggregate unit) (that is, dissolved functional material) ) (A-1) solvent ”is easily used,
(B) As a “low affinity solvent”, a dispersion state (dissolved state) of a functional material dispersed in molecular units (single molecular unit or aggregate unit) (ie, dissolved functional material) ) (B-1) solvent ”is used.

  The solvent (A-1) has a higher solubility (25 ° C.) of the functional material than the solvent (B-1). Specifically, the solubility (25 ° C.) of the functional material (A-1) is preferably 30% by weight or more, more preferably 50% by weight or more, and further preferably 70% by weight or more.

  The solubility (25 ° C.) of the functional material (B-1) is preferably 5% by weight or less, more preferably 3% by weight or less, and still more preferably 1% by weight or less.

On the other hand, when the pattern 2 contains a functional material as a dispersion system,
(A) As the “high affinity solvent”, “(A-2) solvent that easily maintains its dispersed state with respect to the functional material dispersed in fine particle units” is used,
(B) As the “low affinity solvent”, “(B-2) solvent that is difficult to maintain its dispersed state with respect to the functional material dispersed in fine particle units” is used.

  The solvent (A-2) has a higher dispersibility of the fine particles of the functional material (the dispersed fine particles of the functional material are less likely to settle) than the solvent (B-2). Specifically, the solvent (A-2) is preferably 30% by weight or more, more preferably 50% by weight of the functional material fine particles (fine particles similar to those used for the coating liquid) in the solvent. More preferably, it is a solvent in which no precipitation can be confirmed within 1 hour at 25 ° C. after dispersion at 70% by weight or more.

  In addition, the solvent (B-2) contains fine particles of a functional material (fine particles similar to those used in the coating liquid) in the solvent, preferably 5% by weight or less, more preferably 3% by weight or less, More preferably, the solvent is 1% by weight or less, and after the dispersion, the solvent can be confirmed to settle at 25 ° C. within 1 hour.

  In the present invention, the low affinity solvent preferably has a higher boiling point than the high affinity solvent. Thereby, in the drying process of the pattern 2, since the high affinity solvent is dried prior to the low affinity solvent, the fixation of the contact line can be stably generated earlier, and the effect of the present invention is achieved. Can be obtained more remarkably. In the present invention, it is more preferable to use a solvent having a boiling point of 100 ° C. or lower as the high affinity solvent and a solvent having a boiling point of 150 ° C. or higher as the low affinity solvent.

  In the present invention, the content of the low affinity solvent is preferably in the range of 10 wt% to 40 wt% with respect to the total amount of the liquid forming the pattern 2. When the content of the low-affinity solvent is less than 10% by weight, in the process of drying the pattern 2 on the substrate 1, it is difficult for the lowering of affinity to occur at the edge of the pattern 2, and the functional material In some cases, local precipitation is not sufficiently promoted. When the content of the low-affinity solvent exceeds 40% by weight, in the process where the pattern 2 is dried on the substrate 1, the affinity is excessively lowered to the center of the pattern 2 and is caused by the fixation of the contact line. As a result, it becomes difficult for the functional material to be transported by convection, and the solid content may remain outside the patterning position of the fine line portion at the edge.

  As a result, local precipitation of the functional material may become unstable at the edge of the pattern 2. When the content of the low affinity solvent is in the range of 10% by weight or more and 40% by weight or less, a decrease in affinity is preferably caused as the drying progresses, and the functional material is locally present at the edge of the pattern 2. The effect of promoting the precipitation and the effect of reducing the solid content residue outside the fine line portion pattern position are more preferably compatible, and the effect of the present invention can be obtained more remarkably.

  In the present invention, the substrate 1 is preferably heated when the pattern 2 is dried. Drying of the pattern 2 is promoted by heat drying, and the difference in evaporation amount between the central portion and the edge portion, and the difference in evaporation amount between the high affinity solvent and the low affinity solvent become large, and the edge portion of the pattern 2 is fixed. Is promoted, and convection from the center to the edge of the coating is promoted. Thereby, the effect of this invention can be acquired more notably.

  In the present invention, it is particularly preferable that the pattern forming method satisfies all of the following conditions (a) to (d).

  (A) On the substrate, the liquid forming the pattern 2 contains at least a functional material, a high affinity solvent, and a low affinity solvent.

  (A) The low affinity solvent has a higher boiling point than the high affinity solvent.

  (C) The content of the low affinity solvent is in the range of 10% by weight to 40% by weight with respect to the total amount of the liquid.

  (D) The substrate is heated when the pattern 2 is dried.

  In the present invention, the most prominent effect can be obtained by satisfying all the above conditions (a) to (d).

  When all of the above conditions (a) to (d) are satisfied, in the drying process, the high affinity solvent having a high drying rate evaporates in advance at the edge of the pattern 2 having a large evaporation amount. The composition ratio of the affinity solvent increases locally. As a result, the affinity for the functional material sharply decreases at the edge of the pattern 2, the functional material is deposited, and the fixation of the contact line of the pattern 2 occurs in the early stage of drying.

  As described above, when the low-affinity solvent is less than 10% by weight, the contact line of the pattern 2 is prioritized and the fixation of the contact line is difficult to be promoted as the affinity is lowered. On the other hand, when the low-affinity solvent exceeds 40% by weight, the affinity is lowered to the center of the pattern 2 to inhibit convection due to the end immobilization of the pattern 2, and the functional material becomes the pattern 2 It is difficult to be transported to the edge portion of the film, and solid content tends to remain outside the patterning position of the fine line portion of the edge portion.

  By selecting in the content range, local accumulation of solids is promoted at the edge of the pattern 2 and convection due to the end immobilization of the pattern 2 is not hindered. By being transported to the part, it is possible to suitably achieve both the thinning of the thin line width and the reduction of the solid content remaining outside the fine line part pattern position. Further, since the difference in evaporation amount between the center and the edge of the pattern 2 is increased by heating the substrate 1, the edge fixing by using the high affinity solvent and the low affinity solvent, and the pattern 2 Therefore, the effect of the present invention can be remarkably obtained.

  In the present invention, the functional material is not particularly limited, but preferred examples include semiconductor materials, dielectric materials, insulating materials, photoelectric conversion materials, optical materials, and the like. Preferred examples of the functional material for using the transparent conductive film include conductive materials such as conductive fine particles and conductive polymers, and conductive material precursors such as organometallic complexes, inorganic metal salts, and electroless plating catalysts.

  The high-affinity solvent and the low-affinity solvent used in the present invention are not particularly limited, and those that satisfy the above-described affinity conditions (solubility conditions or sedimentation conditions) in relation to the functional material are appropriately used. Can do. One or two or more solvents may be used in combination as the high affinity solvent, and one or two or more solvents may be used in combination as the low affinity solvent.

  For example, when the functional material is water-dispersed silver nanoparticles, water, methanol, ethanol, 1-propanol, isopropanol and the like can be preferably exemplified as the high affinity solvent, and N, N-dimethylformamide as the low affinity solvent. , N, N-dimethylacetamide, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 1,3-butanediol, 1,4 Preferred examples include -butanediol and 1,2-hexanediol. You may use these 1 type or in combination of 2 or more types.

  Also, for example, when the functional material is an organic solvent-based dispersed silver nanoparticle, as a high affinity solvent, hexane, heptane, octane, cyclohexane, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, 1-butanol, 2-butanol , Isobutanol, 1-pentanol, and the like. Preferred examples of the low affinity solvent include nonane, decane, xylene, 1-octanol, 2-octanol, n-nonyl alcohol, tridecyl alcohol, ethylene glycol monobutyl ether acetate, di Preferred examples include propylene glycol monobutyl ether, tripropylene glycol monobutyl ether, cyclohexanone, phenol and benzyl alcohol. You may use these 1 type or in combination of 2 or more types.

  Further, from the viewpoint of more stably achieving the effects of the present invention, in the pattern 2, it is preferable that the high affinity solvent and the low affinity solvent are mixed so as not to cause phase separation. Even when a combination of solvents that can inherently cause phase separation is selected, additives that mediate the affinity (for example, affinity for both high-affinity solvents and low-affinity solvents). If both solvents are mixed, for example, by adding a certain compound), it can be suitably used.

  When such an additive is included in the pattern 2, it is added in an amount that does not impair the effects of the present invention. From the viewpoint of preventing the additive from remaining on the substrate after drying, it is also preferable to use an additive that can be removed by drying or the like.

  The high affinity solvent and the low affinity solvent used in the present invention satisfy the above-described affinity conditions (solubility conditions or sedimentation conditions) in relation to the functional material, and the high affinity solvent is water. More preferably, the low affinity solvent is selected from organic solvents. As a result, the difference in the affinity of the solvent with respect to the functional material can be increased, and further, the difference in the amount of evaporation between the high affinity solvent and the low affinity solvent can be increased. Remarkably can be obtained.

  In addition, the affinity of the high affinity solvent and the low affinity solvent used in the present invention with the functional material matches the above-described affinity conditions (solubility conditions or sedimentation conditions) in relation to the functional materials. It can also be expressed using the solubility parameter (SP value) of the solvent.

The solvent solubility parameter (SP value) is a value represented by the square root of the molecular cohesive energy, and is described in detail in Polymer Hand Book (Second Edition) Chapter IV, Solubility Parameter Values. The unit is (MPa) ^1/2 , and indicates a value at 25 ° C. In addition, R.D. F. It can be calculated by the method described in Fedors, Polymer Engineering Science, 14, p147 (1967).

In the high affinity solvent and the low affinity solvent used in the present invention, the difference in SP value of each solvent is 19 (MPa) ^1/2 or more, more preferably 22 (MPa) ^1/2 or more, and further preferably 25. (MPa) The effect of this invention can be acquired more notably by selecting so that it may become ^1/2 or more.

Examples of the solvent species in which the difference in SP value between the high affinity solvent and the low affinity solvent according to the present invention is 19 (MPa) ^1/2 or more (hereinafter, the description of the unit of SP value is omitted). When water-based dispersed silver nanoparticles are used as the functional material, water (47.9) can be preferably exemplified as the high affinity solvent, and diethylene glycol monobutyl ether (20.9), triethylene glycol monomethyl ether as the low affinity solvent. (21.9) and 1,3-butanediol (23.7) can be preferably exemplified. You may use these 1 type or in combination of 2 or more types.

  Moreover, the pattern 2 may contain various additives, such as surfactant, in the range which does not impair the effect of this invention.

  By using the surfactant, for example, when the pattern 2 is formed by using a droplet discharge method, it is possible to stabilize the discharge by adjusting the surface tension or the like. 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. The addition amount of the surfactant is preferably 1% by weight or less with respect to the total amount of the liquid forming the pattern 2.

  The substrate 1 used in the present invention is not particularly limited. For example, glass, plastic (polyethylene, polypropylene, acrylic, polyester, polyamide, etc.), metal (copper, nickel, aluminum, iron, etc.), or These alloys) and ceramics can be mentioned.

  The substrate 1 is preferably transparent, but is not necessarily limited thereto. According to the present invention, the conductive film (for example, the ring-shaped coating film 3a, the parallel-line coating film 3b, or an aggregate composed of one or more of these) provided on the substrate 1 is excellent in transparency. It can be used for various purposes regardless of the transparency / opacity of 1.

In addition, as the base material 1 of the present invention, a material that hardly absorbs liquid can be preferably used from the viewpoint of not impeding liquid flow (convection). Specifically, the substrate that hardly absorbs the liquid has an absorption amount L of the liquid by the substrate after the substrate is immersed in the liquid for 1 minute in a range of 0 ≦ L ≦ 3 ml / m ² . What can be illustrated preferably. 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. As the substrate 1, one having a coating layer that does not absorb liquid on the surface can also be preferably used.

  In the present invention, the pattern 2 can be formed on the substrate 1 as long as the pattern 2 can be formed with a fluidity sufficient to generate convection in the drying process. For example, a printing method is preferable.

  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 pattern 2 is preferably formed by a droplet discharge method, and an ink jet method, a dispenser method, a spray method and the like can be preferably exemplified. Moreover, it is also possible to form the pattern 2 by uniting the ejected droplets on the substrate 1, thereby enabling digital patterning of the fine line pattern. Thereby, in the case where the pattern formed by the present invention is used as a transparent conductive film, an effect of allowing free design of transparency and conductivity is obtained.

  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 refers to a liquid for forming the pattern 2, and includes a liquid that does not contain a pigment / dye.

  In the present invention, the method for drying the coating film is not particularly limited. For example, the method of heating and drying the surface of the substrate 1 provided with the pattern 2 or the surface of the substrate 1 provided with the pattern 2 is used. Is heated in advance and dried by the heat stored on the surface of the substrate 1, and these may be combined. When heating a base material in a drying process, it is preferable that the surface temperature of the base material 1 is the range of 40 to 150 degreeC.

  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 preferable aspect of the ring-shaped coating film formed by the coating-film formation method which concerns on this invention demonstrated above is demonstrated.

  FIG. 3 is an enlarged plan view showing an example of a ring-shaped coating film formed on a substrate by the coating film forming method according to the present invention. 4 is an enlarged cross-sectional view taken along the line iv-iv in FIG. 3, and is a view in which a ring-shaped fine line portion included in the ring-shaped coating film is cut along a diameter in a direction perpendicular to the formation surface. .

  In the present invention, as shown in the drawing, the ring-shaped coating film 3a is constituted by a fine wire portion 31 formed by depositing a functional material on the edge portion and a slight amount of functional material remaining on the center side. It is also preferable in the present invention that the thin film portion 32 is formed.

  In this invention, it is preferable that the line width w of the thin wire | line part 31 which comprises the ring-shaped coating film 3a is 10 micrometers or less. 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 in a transparent conductive film. Considering the stability of the thin wire portion 31, the line width w of the thin wire portion 31 is preferably in the range of 2 μm to 10 μm.

  In the present invention, the width w of the thin wire portion 31 is defined as z, which is the height of the thinnest portion where the thickness of the functional material is the thinnest inside the thin wire portion, and the thin wire portion 31 protrudes from the z When the height is y, it is defined as the width of the thin line portion 31 at half the height of y. For example, when the ring-shaped coating film 3a has the thin film portion 32 described above, the height of the thinnest portion in the thin film portion 32 can be set to z. When the height of the thinnest portion of the functional material in the thin film portion 32 is 0, the line width w of the thin wire portion is half the height h of the thin wire portion 31 from the surface of the substrate 1. It is defined as the width of the thin line portion 31 in FIG.

  In the present invention, since the line width w of the thin line portion 31 constituting the ring-shaped coating film 3a is extremely thin as described above, from the viewpoint of securing a cross-sectional area in the transparent conductive film and reducing the resistance, The height h of the thin wire portion 31 from the surface of the material 1 is desirably higher. Specifically, the height h of the thin line portion 31 is preferably in the range of 50 nm or more and 5 μm or less.

  Furthermore, in the present invention, from the viewpoint of improving the stability of the ring-shaped coating film 3a, the h / w ratio is preferably in the range of 0.05 or more and 1 or less, respectively.

  Further, from the viewpoint of further improving the transparency of the ring-shaped coating film 3a in the transparent conductive film, the ring-shaped coating film 3a has a height z of the thinnest portion where the thickness of the functional material in the thin film portion 32 is the thinnest. Specifically, the height z of the thinnest portion of the thin film portion is preferably in the range of 10 nm or less. Most preferably, the thin film portion is provided in the range of 0 <z ≦ 10 nm in order to achieve a balance between transparency and stability.

  Further, in order to further reduce the resistance and improve the transparency of the ring-shaped coating film 3a in applications such as a transparent conductive film, the h / z ratio in the thin wire portion 31 is preferably 5 or more, respectively. More preferably, it is particularly preferably 20 or more.

  The diameter R of the ring-shaped coating film 3a can be adjusted, for example, according to the formation range of the pattern 2, and is preferably adjusted in the range of 10 μm to 300 μm. In the present invention, the diameter R is defined as the distance between the maximum protrusions of the thin line portion 31.

  Moreover, it is preferable that the thin wire | line part 31 which comprises the ring-shaped coating film 3a is sufficiently thin compared with the diameter R in line width w.

  It is particularly preferable that the ring-shaped coating film 3a according to the present invention has at least a pattern that satisfies all of the following conditions (a) to (d).

  (A) When the height of the thin wire portion 31 is h and the height of the thinnest portion of the central portion of the ring-shaped coating film 3a is z, 5 ≦ h / z.

  (B) When the width of the thin line portion 31 is w, w ≦ 10 μm

  (C) When the diameter of the ring-shaped coating film 3a is R, 10 μm ≦ R ≦ 300 μm

  (D) When the height of the thin wire portion 31 is h, 50 nm <h <5 μm

  Next, the preferable aspect of the parallel-line coating film formed by the coating-film formation method which concerns on this invention mentioned above is demonstrated.

  FIG. 5 is an enlarged plan view of an essential part showing an example of a parallel line coating film formed on a substrate by the coating film forming method according to the present invention. FIG. 6 is a cross-sectional view taken along the line vi-vi in FIG. 5 and is a diagram in which a set of parallel lines included in the parallel line coating film is cut in a direction perpendicular to the line segment direction.

  In the present invention, the two line segments (thin line portions) 34 and 35 constituting the parallel line 33 in the parallel line coating film 3b do not necessarily have to be islands completely independent of each other. As shown in the figure, the two line segments 34 and 35 are connected by a thin film portion 36 formed between the line segments 34 and 35 at a height lower than the height of the line segments 34 and 35. 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 34 and 35 constituting the parallel line 33 are preferably 10 μm or less, respectively. If it is 10 micrometers or less, since it becomes 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 34 and 35, the line widths W1 and W2 of the line segments 34 and 35 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 34 and 35 are the height of the thinnest portion where the thickness of the functional material is the thinnest between the line segments 34 and 35, and the Z Are defined as the widths of the line segments 34 and 35 at half the height of Y1 and Y2. For example, when the parallel line 33 has the thin film portion 36 described above, the height of the thinnest portion in the thin film portion 36 can be Z. When the height of the thinnest portion of the functional material between the line segments 34 and 35 is 0, the line widths W1 and W2 of the line segments 34 and 35 are the line segments 34 and 35 from the surface of the substrate 1. Are defined as the widths of the line segments 34 and 35 at half the heights h1 and h2.

  In the present invention, since the line widths W1 and W2 of the line segments 34 and 35 constituting the parallel line 33 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 34 and 35 from the surface are preferably higher. Specifically, the heights h1 and h2 of the line segments 34 and 35 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 33, the h1 / W1 ratio and the h2 / W2 ratio are preferably in the range of 0.05 or more and 1 or less, respectively.

  Further, from the viewpoint of further improving the thinning of the parallel-line coating film 3b, the parallel line 33 is the height Z of the thinnest part where the thickness of the functional material is the thinnest between the line segments 34 and 35, specifically The height Z of the thinnest portion of the thin film portion 36 is preferably in the range of 10 nm or less. Most preferably, the thin film portion 36 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 improve the thinning of the parallel line coating film 3b, the h1 / Z ratio and the h2 / Z ratio in the parallel line 33 are each preferably 5 or more, more preferably 10 or more, It is especially preferable that it is 20 or more.

  The interval I between the line segments 34 and 35 can be adjusted as appropriate, and is preferably adjusted in the range of 10 μm to 300 μm. In the present invention, the interval I between the line segments 34 and 35 is defined as the distance between the maximum protrusions of the line segments 34 and 35.

  Furthermore, in the present invention, it is preferable to give the same shape (similar cross-sectional area) to the line segment 34 and the line segment 35, and specifically, the height h1 of the line segment 34 and the line segment 35. And h2 are preferably set to substantially equal values. Similarly, the line widths W1 and W2 of the line segment 34 and the line segment 35 are preferably set to substantially the same value.

  In the present invention, “parallel lines” and “parallel” do not necessarily mean parallel in a strict sense, but the line segments 34 and 35 are connected at least over a certain length L in the line segment direction. Means not. Preferably, the line segments 34 and 35 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 34 and 35 in the line segment direction is preferably at least 5 times the interval I between the line segments 34 and 35, and more preferably at least 10 times. The length L and the interval I can be set corresponding to the formation length and formation width of the pattern (line-shaped liquid) 2.

  The line segments 34 and 35 constituting the parallel line 33 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 coating film 3b which concerns on this invention, it is preferable that the line segment 34 and the line segment 35 which comprise the parallel line 33 are formed simultaneously.

  The parallel-line coating film 3b according to the present invention has at least parallel lines that satisfy all of the following conditions (a) to (d) as the parallel lines 33. Particularly preferred.

  (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 There is

  (A) W1 ≦ 10 μm and W2 ≦ 10 μm when the widths of the lines constituting the parallel lines are W1 and W2.

  (C) When the distance between the lines constituting the parallel lines is I, 10 μm ≦ I ≦ 300 μm

  (D) When the heights of the lines constituting the parallel lines are h1 and h2, 50 nm <h1 <5 μm and 50 nm <h2 <5 μm.

  The ring-shaped coating film and the parallel-line coating film have been mainly described above, but the shape of the coating film formed by the present invention is not limited to these. According to this invention, the coating film which has arbitrary patterns in the edge part can be formed by giving arbitrary shapes to the pattern 2. FIG.

  The base material with a transparent conductive film including at least a coating film formed on the surface of the base material by the coating film forming method according to the present invention has excellent characteristics that can improve transparency when compared with the same resistance value.

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

  The preferred use of the substrate with a transparent conductive film according to the present invention is, for example, as a transparent electrode for displays of various types such as liquid crystal, plasma, organic electroluminescence, field emission, etc. from the viewpoint of remarkably exhibiting the effects of the present invention. Or it can use suitably as a transparent electrode used for a touch panel, a mobile phone, electronic paper, various solar cells, various electroluminescence light control elements, etc.

  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 sensor etc. can be illustrated preferably. Moreover, although it does not specifically limit as an electronic device provided with these devices, For example, a smart phone, a tablet terminal, etc. can be illustrated preferably.

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

<Solvent>
Abbreviations and boiling points of the solvents used in the following examples and comparative examples are as follows. The affinity of these solvents for functional materials is shown in Tables 1 and 2.
・ Water: 100 ℃
Diethylene glycol monobutyl ether (DEBE): boiling point 213 ° C
Triethylene glycol monomethyl ether (TEGME): boiling point 245 ° C
1,3-butanediol (1,3-BD): boiling point 208 ° C.
・ Ethylene glycol (EG): Boiling point 197 ° C

(Examples 1-6, Comparative Example 1)
An ink jet head ("KM512L" manufactured by Konica Minolta Co., Ltd.); standard solution on the surface of the clear hard coat layer with a clear hard coat layer (base material) subjected to corona discharge treatment using PS-1M manufactured by Shinko Electric Instrument Co., Ltd. With a drop volume of 42 pl), droplets were deposited using ink having the composition shown in Table 1 to form a circular pattern (coating pattern). The pattern was dried and a solid content was deposited on the edge to form a large number of fine ring-shaped patterns (coating films) having a diameter of 70 μm. These ring-shaped patterns were arranged in a lattice pattern with an interval of 282 μm so as to form the entire pattern (FIG. 7). Here, the adjacent ring-shaped patterns overlap each other at the edge portion and are combined.

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

(Example 7)
Table 2 shows the surface of the clear hard coat layer with a clear hard coat layer (corresponding to corona discharge treatment using PS-1M manufactured by Shinko Electric Instrumentation Co., Ltd.). A stripe pattern (coating pattern) was formed with line width / space width = 70 μm / 211 μm using the ink having the composition shown. The pattern was dried, and a solid content was deposited on the edge to form a fine stripe pattern (coating film) (FIG. 8).

  Table 2 shows the results of measuring the total light transmittance and conductivity of the obtained pattern.

(Examples 8 to 13, Comparative Example 2)
An ink jet head ("KM512L" manufactured by Konica Minolta Co., Ltd.); standard solution on the surface of the clear hard coat layer with a clear hard coat layer subjected to corona discharge treatment using PS-1M manufactured by Shinko Electric Instrument Co., Ltd. With a drop volume of 42 pl), droplets were deposited using an ink having the composition shown in Table 1 with a nozzle row direction pitch of 211 μm and a scanning direction dot pitch of 50 μm. The droplets were combined on the substrate to form a stripe pattern (coating pattern) similar to that in Example 7. The pattern was dried, and a solid content was deposited on the edge to form a fine stripe pattern (coating film) (FIG. 8).

  Table 2 shows the results of measuring the total light transmittance and conductivity of the obtained pattern.

<Drying conditions>
-Substrate heating method: After forming the coating film, the substrate was heated with a hot plate.
-Substrate surface temperature: 70 ° C

<Measurement method>
The transmittance (total light transmittance) shown in Tables 1 and 2 is a value obtained by measuring the total light transmittance using AUTOMATIC ZEMETER (MODEL TC-HIIIDP) manufactured by Tokyo Denshoku. In addition, it corrects using the base material without a pattern film (transparent conductive film), and is the value measured as the total light transmittance of the created pattern film (transparent conductive film).

  Evaluation of the sheet resistance (surface resistance) shown in Tables 1 and 2 was performed by heating and baking at 120 ° C. for 1 hour using a hot plate, then placing the takeout electrode and using CD770 manufactured by Sanwa Electric Instruments Co., Ltd. It was measured.

  The evaluation of the disconnection ratio shown in Table 2 is based on the result of observing the ratio of occurrence of disconnection of fine lines using an optical microscope by randomly selecting 1000 thin line patterns between the extraction electrodes.

1: base material 2: pattern 3: coating film 3a: ring-shaped coating film 31: fine line part 32: thin film part 3b: parallel line coating film 33: (a pair of) parallel lines 34, 35: line segment (thin line part)
36: Thin film part

1. When forming a coating film in which the functional material is selectively deposited on the edge by drying a pattern formed by applying a liquid containing the functional material on a substrate,
The liquid contains a solvent having a high affinity with the functional material and a solvent having a low affinity with the functional material, so that the functional material is deposited on the edge of the coating film. Film forming method.
2. 2. The coating film forming method according to 1, wherein a coating film having a line segment at least partially is formed as the coating film.
3. 2. The coating film forming method according to 1 above, wherein a coating film having parallel lines at least partially is formed as the coating film.
4). 4. The method for forming a coating film according to 3 above, wherein the pattern is formed by an inkjet method.
5). 5. The method for forming a coating film according to any one of 1 to 4 , wherein the solvent having a low affinity with the functional material has a boiling point higher than that of the solvent having a high affinity with the functional material.
6). The method for forming a coating film according to any one of 1 to 5, wherein the content of the solvent having a low affinity with the functional material is in the range of 10% by weight to 40% by weight with respect to the total amount of the liquid. .
7). The coating film forming method according to any one of 1 to 6 , wherein the substrate is heated when the liquid is dried.
8). The coating film forming method according to any one of 1 to 7 , wherein the coating film is formed by a printing method.
9. The coating film forming method according to any one of 1 to 8 , wherein the coating film is formed by a droplet discharge method.
10. 10. The coating film forming method according to any one of 1 to 9 , wherein the functional material is a conductive material or a conductive material precursor.
11. When the functional material is contained in the liquid in an aqueous dispersion state, a solvent having high affinity with the functional material is selected from the group consisting of water, methanol, ethanol, 1-propanol, and isopropanol, and the function Solvents having a low affinity for volatile materials are N, N-dimethylformamide, N, N-dimethylacetamide, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol 11. The method for forming a coating film according to any one of 1 to 10 above, which is selected from the group consisting of propylene glycol monoethyl ether, 1,3-butanediol, 1,4-butanediol, and 1,2-hexanediol.
12 The solvent having a high affinity with the functional material is water, and the solvent having a low affinity with the functional material is selected from the group consisting of diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, and 1,3-butanediol. 12. The method for forming a coating film according to 11 above.
13. When the functional material is contained in the liquid in an organic solvent-based dispersion state, the solvent having high affinity with the functional material is hexane, heptane, octane, cyclohexane, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, A solvent selected from the group consisting of 1-butanol, 2-butanol, isobutanol, and 1-pentanol, having a low affinity with the functional material is nonane, decane, xylene, 1-octanol, 2-octanol, n- nonyl alcohol, tridecyl alcohol, ethylene glycol monobutyl ether acetate, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, cyclohexanone, phenol, according to any of the 1-10 selected from the group consisting of benzyl alcohol Film forming method.
14 The coating according to any one of 1 to 13 , wherein a difference in SP value between a solvent having a high affinity with the functional material and a solvent having a low affinity with the functional material is 19 (MPa) ^1/2 or more. Film forming method.
15. The coating film with a transparent conductive film substrate with a transparent conductive film on the substrate surface including the formed by the coating film forming method according to any of the 1-14.
16. 16. A device comprising the substrate with a transparent conductive film according to 15 above.
17. An electronic apparatus comprising the device according to 16 above.

By using the surfactant, for example, when the pattern 2 is formed by using a droplet discharge method, it is possible to stabilize the discharge by adjusting the surface tension or the like. The surfactant is not particularly limited, but a silicon surfactant or the like can be used. The silicone surfactant is obtained by polyether-modified side chains or terminal dimethylpolysiloxane siloxane, for example, manufactured by Shin-Etsu Chemical Co. of KF-351A, such as KF-642 and BYK-made BYK347, BYK348 are commercially available ing. The addition amount of the surfactant is preferably 1% by weight or less with respect to the total amount of the liquid forming the pattern 2.

Claims (14)

When forming a coating film in which the functional material is selectively deposited on the edge by drying a pattern formed by applying a liquid containing a functional material in a dispersed or dissolved state on a substrate.
The liquid contains a solvent having a high affinity with the functional material and a solvent having a low affinity with the functional material, so that the functional material is deposited on the edge of the coating film. Film forming method.   The coating film forming method according to claim 1, wherein the solvent having a low affinity with the functional material has a higher boiling point than the solvent having a high affinity with the functional material.   The coating film forming method according to claim 1 or 2, wherein the content of the solvent having low affinity with the functional material is in the range of 10 wt% to 40 wt% with respect to the total amount of the liquid.   The coating film forming method according to claim 1, wherein the substrate is heated when the liquid is dried.   The coating film forming method according to claim 1, wherein the coating film is formed by a printing method.   The coating film forming method according to claim 1, wherein the coating film is formed by a droplet discharge method.   The coating material forming method according to claim 1, wherein the functional material is a conductive material or a conductive material precursor.   When the functional material is contained in the liquid in an aqueous dispersion state, a solvent having high affinity with the functional material is selected from the group consisting of water, methanol, ethanol, 1-propanol, and isopropanol, and the function Solvents having a low affinity for volatile materials are N, N-dimethylformamide, N, N-dimethylacetamide, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol The method for forming a coating film according to any one of claims 1 to 7, which is selected from the group consisting of propylene glycol monoethyl ether, 1,3-butanediol, 1,4-butanediol, and 1,2-hexanediol.   The solvent having a high affinity with the functional material is water, and the solvent having a low affinity with the functional material is selected from the group consisting of diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, and 1,3-butanediol. The method for forming a coating film according to claim 8.   When the functional material is contained in the liquid in an organic solvent-based dispersion state, the solvent having high affinity with the functional material is hexane, heptane, octane, cyclohexane, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, A solvent selected from the group consisting of 1-butanol, 2-butanol, isobutanol, and 1-pentanol, having a low affinity with the functional material is nonane, decane, xylene, 1-octanol, 2-octanol, n- The nonyl alcohol, tridecyl alcohol, ethylene glycol monobutyl ether acetate, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, cyclohexanone, phenol, and benzyl alcohol according to any one of claims 1 to 7. Film forming method. The difference in SP value between a solvent having a high affinity with the functional material and a solvent having a low affinity with the functional material is 19 (MPa) ^1/2 or more. Coating film forming method.   The base material with a transparent conductive film which has the transparent conductive film containing the said coating film formed by the coating-film formation method in any one of Claims 1-11 on a base-material surface.   The device which has a base material with a transparent conductive film of Claim 12. An electronic apparatus comprising the device according to claim 13.

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