JP6426152B2 - Method of forming blackened conductive pattern and blackened conductive ink composition - Google Patents

Description

  The present invention relates to a method of forming a blackening conductive pattern. More specifically, the conductive material and the blackening material are mixed to fill the groove of the substrate with the blackened conductive ink composition having excellent optical and electrical properties to form a single layer conductive pattern. On how to do it.

  Recently, due to the tendency of electronic products to be lighter, thinner and smaller, it is required to manufacture both electronic devices such as displays or transistors in a form of high density and high integration, and they are used for electrodes or metallization A technique for forming a fine metal pattern that can be used is attracting attention.

  In particular, in the technology for producing a transparent electrode which is essential for touch panels, a metal pattern formed by forming a fine pattern on a substrate and filling it with a metal conductive ink is very useful in resistance characteristics. . However, when the metal conductive ink is filled in the pattern on the substrate, the reflection property of the metal causes a problem of visibility.

  In order to solve this, a blackening treatment step is generally introduced after the filling of the metal conductive ink. The blackening treatment step improves the visibility of the film, but deteriorates the conductivity of the film, resulting in the problem of deteriorating the physical properties as an electrode.

  Although methods for forming fine metal pattern electrodes using various processes are known, the following problems are found in the prior art described later.

  Korean Published Patent Application No. 10-2006-0105914 describes a method of forming a black electroplated layer on a transparent polymer film by depositing a conductive metal as a seed, and patterning it in a mesh shape. ing. However, this method is an etching and etching process by patterning, and the process is complicated, and it is not only difficult to form a low resistance electrode, but it causes environmental problems.

  As another method, JP-A-2001-127485 describes a method of forming a transparent electromagnetic shielding material by sequentially laminating a mesh-like black metal oxide layer and a metal layer on a transparent substrate. It is done. However, this method also requires complicated steps of deposition and etching (etching).

  As another method, according to Korean Patent Publication No. 10-2007-0102263, a conductive resist layer which can be photocured or thermally cured is coated on a substrate and pressed with a mold. A method is described for forming layers by etching. However, since it is an etching (etching) process, the process is complicated, and there is a problem that the formation of a low resistance electrode is limited.

  As another method, in the invention described in Korean Patent Publication No. 10-2009-0061225, a resist layer is applied to a nonconductive substrate, and a fine pattern is formed on the resist layer using a laser, and the pattern The conductive material layer and the blackening material layer are stacked on the substrate to form a conductive pattern. According to the above-mentioned method, visibility is lowered and it is difficult to form a low resistance electrode.

  Therefore, while forming the blackening substance capable of maintaining the electrical properties while improving the optical properties such as the degree of blackening, and forming the fine pattern electrode having the optical, electrical and mechanical properties in a simple process It is necessary to develop a pattern method that can

  Accordingly, the object of the present invention is to solve such conventional problems, and by mixing a conductive substance with a blackening substance to improve the degree of blackening, without reducing the resistance. It is an object of the present invention to provide a method of forming a blackened conductive pattern capable of maintaining electrical characteristics.

  In addition, using a single blackening conductive ink composition in which a conductive substance and a blackening substance are mixed as a substance that satisfies the pattern, a single layer pattern is formed without undergoing a separate blackening process. It is an object of the present invention to provide a method of forming a blackened conductive pattern that can be

  Also provided is a method of forming a blackened conductive pattern capable of improving adhesion to a substrate groove and improving mechanical properties by forming a single layer pattern with the blackened conductive ink composition. It is to do.

  In addition, the blackened conductive ink on the surface of the substrate, which will remain when filling the pattern, is dissolved by etching, pressed into the groove and filled, and the fine black of low resistance, which is difficult to realize in the prior art. It is an object of the present invention to provide a method of forming a conductive conductive pattern.

  In order to achieve the above-mentioned subject, the formation method of the blackening conductive pattern concerning the example of the present invention fills the above-mentioned slot of the substrate which has a slot so that the blackening conductive ink composition may be filled up. And filling the blackening conductive ink composition into the grooves in the primary filling step, and dissolving the residual blackening conductive ink composition to be left on the surface of the substrate with an etching solution. The method may further include a secondary filling step of filling the groove with the residual blackening conductive ink composition.

  The blackening conductive ink composition may include a conductive material and a blackening material.

  The conductive material includes at least one of a metal complex compound, a metal precursor, spherical metal particles, metal flakes or nanoparticles, and the blackening material is titanium based, zirconium based, manganese based, antimony based or Any substance that can contain a vanadium-based complex compound or a combination of these complex compounds and can form a conductive pattern is applicable.

Preferably, the titanium-based complex compound is isopropyl titanate, ethyl titanate, n-butyl titanate, poly-N-butyl titanate, 2-ethylhexyl titanate, n-propyl titanate, octyl glycol titanate, tetraisooctyl titanate, cresyl A zirconium based complex compound containing at least one of titanate monomer, cresyl titanate polymer, triethanolamine titanate, titanium acetylacetonate, titanium isopropoxide, ethyl acetoacetate titanate, isostearoyl titanate or titanium lactate chelate Is triethanolamine zirconate, zirconium lactate, zirconium glycolate, n-butyl zirconate or n-propyl And the manganese-based complex compound containing at least one of the gluconates is manganese (III) acetylacetonate, manganese (III) acetylacetonate tetrahydrate, manganese (II) acetate, manganese (III) acetate dihydrate , Manganese (II) acetylacetonate, manganese (II) carbonate, manganese (II) carbonate hydrate, manganese (II) hexafluoroacetylacetonate trihydrate, manganese (II) chloride, manganese (II) nitrate tetralate Hydrate, Manganese (II) Sulfate Monohydrate, Manganese (II) Sulfide, Manganese (II) Nitrate Hydrate, Manganese (II) Sulfate Monohydrate, Manganese II) at least one of perchlorate hydrate, manganese (III) fluoride, manganese (II) sulfate hydrate, manganese (II) chloride hydrate or manganese (II) chloride monohydrate, and the above antimony system Of complex compounds of antimony (III) chloride, antimony (III) acetate, antimony (III) ethoxide, antimony (V) chloride, antimony (V) sulfide, antimony (III) methoxide antimony (III) sulfide, antimony (V) ) Containing at least one of fluoride, antimony (III) sulfide, antimony (III) butoxide, antimony (III) isopropoxide or antimony (III) propoxide be able to. Further, the vanadium-based complex compound is vanadium (III) acetylacetonate, vanadium (II) chloride, vanadium (III) chloride, vanadium (V) oxyl triethoxide, vanadium (V) oxychloride, vanadium (IV) Chloride, vanadium (V) oxyl tripropoxide, vanadium (V) oxyl fluoride, vanadium (IV) oxide sulfate hydrate, vanadium boride, vanadium (III) bromide, vanadium (III) iodide ( can be included.

  In the primary filling step, the blackened conductive ink is formed by an ink jet method, flat screen method, spin coating method, bar coater method, roll coating method, flow coating method, doctor blade, dispensing, gravure printing method or flexo printing method Although a composition can be filled, it is not limited to this.

  In the second filling step, a residual ink composition dissolving step of dissolving the residual blackening conductive ink composition with an etching solution, and filling the groove with the residual blackening conductive ink composition dissolved by the etching solution And a residual ink composition filling step.

  The etching solution may be applied to the surface of the substrate to dissolve the residual blackening conductive ink composition, and the method of applying the etching solution may be any method commonly used in the industry. , All applicable.

  In the dissolution step, the etching solution may be an ammonium carbamate type, ammonium carbonate type, ammonium bicarbonate type, carboxylic acid type, lactone type, lactam type, cyclic acid anhydride type compound, acid-base salt complex, acid-base -At least one of an alcohol complex or a mercapto compound and an oxidizing agent can be included. However, the present invention is not limited to this, and any etching solution capable of dissolving a metal substance is applicable. In the secondary filling step, the groove can be filled with the residual blackening conductive ink composition by pressing the dissolved residual blackening conductive ink composition into the groove.

  Here, the melted residual blackening conductive ink composition can be pressed into the groove to fill the groove using a doctor blade or a brush, but the method is not limited thereto.

  The method may further include laminating a blackening conductive ink composition on the blackening conductive pattern.

  The method may further include a drying step of drying the blackened conductive ink composition filled in the groove at a temperature of 22 to 600 ° C. after the primary filling step, the secondary filling step, or the laminating step. The drying method is variously applicable.

  In order to achieve the above object, the blackened conductive ink composition according to the embodiment of the present invention includes a conductive material and a blackened material, and the blackened material is titanium based, zirconium based, manganese based. It is preferable to include an antimony-based complex compound or a combination of these complex compounds, and it is not limited to this as long as it is a substance capable of forming a blackened conductive pattern.

  The conductive material of the blackening conductive ink composition may include, but is not limited to, at least one of a metal complex compound, a metal precursor, spherical metal particles, metal flakes or nanoparticles.

  The amount of the blackening substance is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the conductive substance.

  According to the method for forming a blackened conductive pattern of the present invention, one or more of the following effects are obtained.

  The ink composition filled in the substrate groove can be formed by adding an optimal blackening substance to the conductive substance, thereby simultaneously improving the optical, electrical and mechanical properties of the conductive pattern. .

  In addition, since an ink composition in which a conductive substance and a blackening substance are mixed is used without forming a separate blackening layer, the process is simple and economical, and the adhesion of the pattern is remarkably improved.

  Not only that, when the blackening conductive ink composition is filled in the grooves of the substrate, the blackening conductive ink composition that will remain is dissolved in the etching solution and refilled in the grooves, A low resistance conductive pattern capable of realizing excellent performance can be formed, and formation of a fine conductive pattern is easy.

  The effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned can be clearly understood by those skilled in the art from the description of the claims.

It is a flowchart which shows sequentially the method of forming the blackening electroconductive pattern which concerns on one Example of this invention. It is sectional drawing which shows sequentially the method of forming the blackening electroconductive pattern which concerns on one Example of this invention. It is sectional drawing which shows sequentially the method of forming the blackening electroconductive pattern which concerns on one Example of this invention. It is sectional drawing which shows sequentially the method of forming the blackening electroconductive pattern which concerns on one Example of this invention. It is sectional drawing which shows sequentially the method of forming the blackening electroconductive pattern which concerns on one Example of this invention. It is sectional drawing which shows sequentially the method of forming the blackening electroconductive pattern which concerns on one Example of this invention. It is sectional drawing which shows sequentially the method of forming the blackening electroconductive pattern which concerns on one Example of this invention. It is a graph which shows the specific-resistance value which changed and measured the content ratio of the blackening substance about a blackening electrically conductive ink composition. It is a graph which shows the degree of blackening (L *) measured by changing the content ratio of the blackening substance about the blackening conductive ink composition.

  The advantages and features of the present invention, and the manner in which they are achieved, will become clearer with reference to the embodiments described in detail below in conjunction with the attached drawings. However, the present invention is not limited to the embodiments disclosed below, but can be embodied in various forms different from one another, and the present embodiment merely makes the disclosure of the present invention complete. It is provided to fully inform the scope of the invention to those skilled in the art to which the present invention belongs, and the present invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

  Spatially relative terms such as "below", "below", "lower", "above", "upper" etc are shown in the figure. As such, it can be used to easily describe the correlation between one component and another. Spatially relative terms should be understood as terms that include different orientations of the components in use or operation in addition to the orientations shown in the figures. For example, if the component shown in the figure is turned over, the component described in the “below” or “beneath” of the other component is the “above” of the other component. ) Can be placed. Thus, the exemplary term "bottom" can include both bottom and top directions. The components can also be oriented in other directions, whereby spatially relative terms can be interpreted by orientation.

  The terms used in the present specification are for the purpose of describing the examples and do not limit the present invention. In the specification, the singular forms also include the plural unless specifically stated otherwise. As used herein, "comprising" and / or "including" does not exclude the presence of, or the addition of, the component mentioned, the step one or more other components, a step.

  In the drawings, the thickness and size of each component are exaggerated, omitted or schematically shown for the convenience and clarity of the description. Also, the size and area of each component do not totally reflect the actual size and area.

  The present invention will now be described by way of example with reference to the drawings in order to illustrate the blackening conductive pattern method according to an embodiment of the present invention.

  The blackening conductive pattern method according to an embodiment of the present invention comprises a primary filling step (S10) and a secondary filling step (S20) as shown in FIG.

Primary filling stage (S10)
In the primary filling step (S10), the grooves of the grooved substrate are filled with the blackening conductive ink composition, and the intaglio grooves are filled with a conductive material.

  The type of the substrate is not particularly limited. The substrate may be formed of a transparent material, such as a plastic film or glass. Examples of the plastic film include polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), nylon (Nylon), polytetrafluoroethylene (PTFE), and polyetheretherketone (PEEK). ), Polycarbonate (PC), or polyarylate (PAR) can be used. An opaque material can also be applied. For example, it is possible to use a metal plate whose surface is insulating, or to apply an opaque plastic film, an opaque glass or an opaque glass fiber material. Thus, although a plastic film, a glass substrate, etc. can be used, it is not limited to this.

  The groove may be formed on the substrate by any method commonly used in the industry, preferably by imprinting a UV curable resin or a thermosetting resin with a mold by an imprinting process. It is selected according to the size of the fine line width to be embodied using a method, a method in which a substrate is directly formed by laser etching and used, a method in which a photolithography method is used, or the like. It can be used.

  The blackening conductive ink composition comprises a conductive substance and a blackening substance.

  As the conductive material, metal complex compounds, metal precursors, spherical metal particles, metal flakes or nanoparticles can be used, and two or more kinds can be mixed and used according to the material of the conductive material. .

  A metal complex compound or a metal precursor can be used to improve the filling property of the microgrooves. In addition, the metal complex compound or the metal precursor can be reduced to produce metal particles of nano size and used as a mixture. Using this, it is possible to easily form nano-sized fine conductive patterns that could not be formed by the prior art.

The metal precursors used in the present invention can be represented by the general formula _Mn x, where M is Ag, Au, Cu, Ni, Co, Pd, Ti, V, Mn, Fe, Cr, Zr, Nb, Mo, W, Ru, Cd, Ta, Re, Os, Ir, Al, Ga, Ge, In, Sn, Sb, Pb, Bi, n is an integer of 1 to 10, X is oxygen, Sulfur, halogen, cyano, cyanate, carbonate, nitrate (Nitrate), sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, acetylacetonate, mercapto, amide, alkoxide, carboxylate and the like are shown. Specifically, for example, acetic acid gold, palladium oxalate, silver 2-ethylhexanoate, copper 2-ethylhexanoate, iron stearate, nickel formic acid, zinc citrate, and the like Such as metal carboxylate, silver nitrate, copper cyanide, cobalt carbonate, platinum chloride, chloroauric acid, tetrabutoxytitanium, dimethoxyzirconium dichloride, aluminum isopropoxide, vanadium oxide, tantalum (tantalum) methoxide, bismuth acetate, dodecyl mercaptoation One or more kinds of metal compounds such as gold and indium acetylacetonate can be selected and used together.

  Common metal nanoparticle production methods include physical methods in which a mass of metal is physically finely pulverized and produced, and methods in which production is performed using a chemical reaction. More specifically, the chemical method includes an aerosol method of injecting a high pressure gas to produce a powder, a thermal decomposition method of producing a powder by thermal decomposition using a metal compound and a gaseous reducing agent, There are evaporation condensation method, sol-gel method, hydrothermal synthesis method, ultrasonic synthesis method, micro-emulsion method, liquid reduction method, etc. which heat and evaporate the evaporation raw material to produce powder. The liquid reduction method manufactured using a dispersant and a reducing agent, which is easy to control the formation of nanoparticles and evaluated as the most economical, is most often used, but in the present invention, the nanoparticles are used. All methods can be used if they can be formed. The specific description of the method of producing nanoparticles of liquid reduction method is described in Korean Patent Application No. 2006-0074246 filed by the applicant, and the metal nanoparticles described in the above patent application are particles of The conductive ink containing the metal nanoparticles has the advantages of uniform size and minimized aggregation, and the conductive ink containing the metal nanoparticles is uniform with high conductivity even when fired at a low temperature of 150 ° C. or less for a short time. It has the advantage that it is easy to form a dense thin film or a fine pattern.

  The blackening substance is mixed with the conductive substance to form a blackening conductive ink composition.

  The blackening substance is preferably a complex compound of titanium (Ti), zirconium (Zr), manganese (Mn), antimony (Sb) or vanadium (V), depending on the type of conductive substance. Thus, these complex compounds can be used in combination.

  Titanium-, zirconium-, manganese- or antimony-based complex compounds have excellent effects for improving visibility, control the reflection characteristics unique to metals, increase the degree of light absorption, and improve adhesion to substrates. It can be improved.

  The titanium-based complex compounds are isopropyl titanate, ethyl titanate, n-butyl titanate, poly-N-butyl titanate, 2-ethylhexyl titanate, n-propyl titanate, octyl glycol titanate, tetraisooctyl titanate, cresyl titanate monomer, It is preferred to include at least one of cresyl titanate polymer, triethanolamine titanate, titanium acetylacetonate, titanium isopropoxide, ethylacetoacetate titanate, isostearoyl titanate or titanium lactate chelate.

  The zirconium-based complex compound preferably contains at least one of triethanolamine zirconate, zirconium lactate, zirconium glycolate, n-butyl zirconate, and n-propyl zirconate.

  The manganese-based complex compounds are manganese (III) acetylacetonate, manganese (III) acetylacetonate tetrahydrate, manganese (II) acetate, manganese (III) acetate dihydrate, manganese (II) acetylacetonate, Manganese (II) carbonate, manganese (II) carbonate hydrate, manganese (II) hexafluoroacetylacetonate trihydrate, manganese (II) chloride, manganese (II) nitrate tetrahydrate, manganese (II) sulfate monobasic Hydrate, Manganese (II) Sulfide, Manganese (II) Nitrate Hydrate, Manganese (II) Sulfate Monohydrate, Manganese (II) Perchlorate Hydrate, Manga (III) fluoride, manganese (II) sulfate hydrate, it is preferable to include at least one of manganese (II) chloride hydrate or manganese (II) chloride monohydrate.

  The antimony-based complex compounds are antimony (III) chloride, antimony (III) acetate, antimony (III) ethoxide, antimony (V) chloride, antimony (V) sulfide, antimony (III) methoxide, antimony (III) sulfide, It is preferable to include at least one of antimony (V) fluoride, antimony (III) sulfide, antimony (III) butoxide, antimony (III) isopropoxide or antimony (III) propoxide.

  The vanadium-based complex compounds are vanadium (III) acetylacetonate, vanadium (II) chloride, vanadium (III) chloride, vanadium (V) oxyl triethoxide, vanadium (V) oxyl chloride, vanadium (IV) chloride, Vanadium (V) oxyl tripropoxide, vanadium (V) oxyl fluoride, vanadium (IV) oxide sulfate hydrate, vanadium boride, vanadium (III) bromide or vanadium (III) iodide Can be included.

  The content of the blackening substance comprising the metal complex compound or the combination thereof is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the conductive substance.

  If the amount of the blackening substance is less than 0.01 parts by weight, it is difficult to control the irregular reflection of the metal and the turbidity (haze) is significantly reduced. In addition, when it exceeds 10 parts by weight, there is a problem that the electrical characteristics decrease.

  In addition to these mixtures, if necessary, a solvent, a stabilizer, a dispersant, a binder resin, a mold release agent, a reducing agent, a surfactant, a wetting agent, and a thixotropic agent ( Thixotropic agents or leveling agents, additives such as thickeners, etc. can be included.

  The binder resin is preferably one having excellent adhesion to various substrates. Substances usable for this are organic polymer substances such as polypropylene, polycarbonate, polyacrylate, polymethyl methacrylate, cellulose acetate, polyvinyl chloride, polyurethane, polyester, alkyd resin, epoxy resin, phenoxy resin, melamine Resin, phenol resin, phenol modified alkyd resin, epoxy modified alkyd resin, vinyl modified alkyd resin, silicon modified alkyd resin, acrylic melamine resin, polyisocyanate resin, epoxy ester resin, etc. can be mentioned as an example, according to the present invention Not limited to this. In the case of the silver (Ag) complex compound and the nanoparticles in the blackening conductive ink used in the first filling step (S10), since it can be used even when there is no binder, it is limited to the contents described above It is not a thing.

  In addition, a solvent may be required to form a uniform thin film, and as the solvent that can be used at this time, alcohols such as ethanol, isopropanol, butanol and hexanol, and glycols such as ethylene glycol and glycerin can be used. Ethyl acetate, butyl acetate, methoxypropyl acetate, carbitol acetate, acetates such as ethyl carbitol acetate, methyl cellosolve, butyl cellosolve, diethyl ether, ethers such as tetrahydrofuran, dioxane, methyl ethyl ketone, acetone, dimethylformamide, 1 Ketones such as methyl-2-pyrrolidone, hexane, heptane, dodecane, paraffin oil, hydrocarbon such as mineral spirits, benzene, toluene, Aromatics such as down, and, chloroform, methylene chloride, halogen-substituted solvents such as carbon tetrachloride, acetonitrile, dimethyl sulfoxide or a mixed solvent thereof and the like can be used. However, the type of solvent is not limited to this.

  The method for filling the blackening conductive ink composition in the grooves of the substrate in the primary filling step (S10) is not limited, but the ink jet method, flat screen method, spin coating method, bar method (Bar) coater method, roll coating method, flow coating method, doctor blade, dispensing, gravure printing method or flexography printing method is preferred. At this time, the number of fillings may be repeated one or more times. Depending on the respective filling methods, differences in the filling properties may be observed, which adjust the components of the blackening conductive ink to match the respective filling methods and fill the rheology of the composition. Needs to be optimized.

  The thickness of the conductive pattern formed by the above method is preferably equal to or less than the pattern depth of the intaglio, but is not limited thereto. Depending on the conditions of the post-treatment process, it may be better to make the thickness of the conductive pattern thicker than the depth of the intaglio pattern to increase the contact force with the upper circuit. Specifically, it is preferably 10 μm or less, more preferably 0.1 μm to 5 μm. The thickness of the conductive pattern needs to be adjusted according to the line width to be embodied, the required resistance and the post-processing conditions.

  It is preferable to carry out a drying step after filling the blackening conductive ink composition in the grooves of the substrate in the primary filling step (S10). Drying of the conductive pattern is preferably 22 to 600 ° C., more preferably 80 to 400 ° C. The temperature range is not necessarily limited, and it is preferable to proceed in a temperature range in which the base material is not deformed according to the type of the base material.

Secondary filling stage (S20)
In the secondary filling step (S20), while filling the blackening conductive ink composition in the grooves in the primary filling step (S10), the residual blackening conductive ink composition to be left on the surface is treated And a step of additionally filling the groove, wherein the residual blackening conductive ink composition is dissolved with an etchant so that the groove is filled with the dissolved residual blackening conductive ink composition.

  The secondary filling step (S20) may include a residual ink composition dissolving step (S21) and a residual ink composition filling step (S22), and filling the grooves in the process of dissolving the residual conductive ink composition You can also.

Residual ink composition dissolution step (S21)
The residual ink composition dissolving step (S21) is a residual blackening conductive ink composition remaining on the surface while filling the grooves with the blackening conductive ink composition in the primary filling step (S10). Dissolving the blackening conductive ink composition in the primary filling step (S10) while inducing the blackening conductive ink composition to be left on the surface of the substrate in the grooves. In order to dissolve it with an etching solution.

  Generally, the etching mechanism of the blackening conductive ink composition is that the oxidizing agent oxidizes the metal surface to form a metal oxide and repeats the process of dissolving it with a compound that dissolves it and the swelling process. Can.

  An etchant may be applied to the surface of the substrate to dissolve the blackened conductive ink composition remaining on the surface of the substrate. The application method of etching liquid can be performed by the usual coating method.

  The etching solution may be ammonium carbamate type, ammonium carbonate type, ammonium bicarbonate type, carboxylic acid type, lactone type, lactam type, cyclic acid anhydride type compound, acid-base salt complex, acid-base-alcohol type complex or It is preferable to include at least one of mercapto compounds and an oxidizing agent.

  For example, an oxidizing agent and one or more of the above-mentioned compounds and a mixture thereof are directly reacted without a solvent at atmospheric pressure or under pressure, or when a solvent is used, water, methanol, propanol, isopropanol, Alcohols such as butanol, ethanolamine, ethylene glycol, glycols such as glycerin, ethyl acetate, butyl acetate, acetates such as carbitol acetate, ethers such as diethyl ether, tetrahydrofuran, dioxane, methyl ethyl ketone, acetone Ketones such as hexane, hydrocarbons such as hexane and heptane, aromatics such as benzene and toluene, and halogen-substituted solvents such as chloroform, methylene chloride and carbon tetrachloride, and perfluorocarbons. Etc. can be used fluorine-based solvent or a mixed solvent. In a pressurized state such as a pressure vessel, low boiling point fluorinated solvents and liquefied carbon dioxide can also be used. It is not necessary to restrict | limit the manufacturing method of the etching liquid of this invention in particular. That is, any known method may be used for the purpose of the present invention.

As the etching solution, the oxidizing agent is, for example, an oxidizing gas such as oxygen or ozone, hydrogen peroxide, Na ₂ O ₂ , KO ₂ , NaBO ₃ , (NH ₄ ) S ₂ O ₈ , H ₂ SO ₅ , Peroxides such as (CH ₃ ) ₃ CO ₂ H, (C ₆ H ₅ CO ₂ ) ₂ , HCO ₃ H, CH ₃ CO ₃ H, CF ₃ CO ₃ H, C ₆ H ₅ CO ₃ H , Peroxy acids such as m-ClC ₆ H ₅ -CO ₃ H, nitric acid, sulfuric acid, iodo (I ₂ ), Fe (NO ₃ ) ₃ , Fe ₂ (SO ₄ ) ₃ , K ₃ Fe (CN) ₆ , commonly known oxidations such as (NH ₄ ) ₂ Fe (SO ₄ ) ₂ , Ce (NH ₄ ) ₄ (SO ₄ ) ₄ , NaIO ₄ , KMnO ₄ , K ₂ CrO ₄ etc. Inorganic acids or metals, nonmetal compounds, etc. are included here. When using such oxidizing agents, one or at least one oxidizing agent may be mixed and used.

  In order to effectively dissolve the conductive ink remaining on the surface of the substrate without being filled in the grooves of the substrate, the etching solution is made hydrophilic to the composition of the etching solution in order to enhance the refillability into the fine grooves. It may be preferable to apply Ammonium carbamate type, ammonium carbonate type, ammonium bicarbonate type, carboxylic acid type, lactone type, lactam type, cyclic acid anhydride type, acid-base salt complex, acid-base-alcohol type complex, carbon of mercapto type compound Preferably, the number is adjusted to adjust the degree of hydrophilic character.

  Here, ammonium carbamate compounds, ammonium carbonate compounds and ammonium bicarbonate compounds are specifically described in the applicant's Korean Registration No. 0727466, and as carboxylic acid compounds, benzoic acid, olein Acid, propionic acid, malonic acid, hexanoic acid, octanoic acid, decanoic acid, neodecanoic acid, oxalic acid, citric acid, salicylic acid, stearic acid, acrylic acid, succinic acid, adipic acid, glycolic acid, isobutyric acid, ascorbic acid etc. It can be used.

  Examples of lactone compounds include β-propiolactone, γ-propiolactone, γ-butyrolactone, γ-thiobutyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, and γ- Caprolactone, γ-octanoic lactone, δ-valerolactone, 1,6-dioxaspiro [4,4] nonane-2,7-dione, α-methylene-γ-butyrolactone, γ-methylene-γ-butyrolactone, ε- Caprolactone, lactide, glycolide, tetronic acid, 2 (5H) -furanone, β-hydroxy-γ-butyrolactone, mevalonic lactone, 5,6-dihydro-2H-pyran-2-one, δ- Valerolactone, ε-caprolactone, γ-caprolactone, γ-octanoic Or the like can be used lactone (Octanoic lactone).

  As a lactam compound, 2-azetidone, 2-pyrrolidinone, 5-methoxy-2-pyrrolidinone, 5-methyl-2-pyrrolidinone, N-methylcaprolactam, 2-azacyclononanone, N-acetylcaprolactam etc. are used. be able to.

  As cyclic acid anhydride, itaconic anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, octadecyl succinic anhydride, 2, 2- dimethyl succinic anhydride, 2-dodecane-1-yl succinic anhydride Hexafluoroglutaric anhydride, 2,3-dimethylglutaric anhydride, 3-ethyl-3-methylglutaric anhydride, 3,5-diacetyltetrahydropyran-2,4,6-trione diglycolic anhydride Things can be used.

  As mercapto compounds, 1-methanethiol, 1-ethanethiol, 2-butanethiol, 1-heptanethiol, 1-octanethiol, 1-decanethiol, 1-hexadecanethiol, thioacetic acid, 6-mercaptohexanoic acid , Thiobenzoic acid, purpuryl mercaptan, cyclohexanethiol, 11-mercapto-1-undecanol, 2-mercaptoethanol, 3-mercapto-1-propanol, thiosalicylic acid, 1-thioglycerol, 2-naphthalenethiol, methyl 3- Mercaptopropionate, gamma mercaptopropyltrimethoxysilane and the like can be used. There is no limitation to this, and among these, a single component may be used, or one selected from a group consisting of a mixture of two or more types may be used.

  At the time of coating, the etching rate of the etching composition controls the deposition time of the etching solution, or the oxidizing agent of the etching solution or the ammonium carbamate type, ammonium carbonate type, ammonium carbonate type, ammonium bicarbonate type, carboxylic acid type, lactone type, lactam It is preferable to adjust and control the concentration of a system, cyclic acid anhydride type, acid-base salt complex, acid-base-alcohol type complex, and mercapto type compound, and the etching process can be repeated as necessary. . In the case of an etching solution containing an inorganic acid or a base, the etching solution can be removed by washing with an additional water or an organic solvent. For example, the conductive ink on the surface of the substrate can be put in the groove by further including a washing step.

  The re-dissolution and filling rate of the residual conductive ink composition can be adjusted according to the ratio of the above-mentioned oxidizing agent and etching solution composition.

Residual ink composition filling step (S22)
The residual ink composition filling step (S22) is to fill the grooves of the substrate with the residual blackening conductive ink composition dissolved in the residual ink composition dissolving step (S21), and the residual blackening conductive ink The composition is introduced into the groove.

  As a method of guiding the residual blackening conductive ink composition to the groove, it is preferable to push the groove into the groove with a physical force so as to be filled.

  There is no limitation on the method of pushing in the melted residual blackening conductive ink composition or the processing member to push in, but a doctor blade or brush can be used. More preferably, a brush is used. The brush can effectively prevent the surface of the substrate from being scratched and the ink being lost by reducing the physical force.

  Also, the filling can be carried out once or more and various methods can be used, in particular by mixing a doctor blade and a brush.

  A blackening conductive ink remaining on the surface of the substrate while filling the grooves of the substrate with the blackening conductive ink composition while pushing in the residual blackening conductive ink composition dissolved using a doctor blade or a brush It is possible to remove the metal substance or the organic substance which is a component of the composition.

  In addition, in order to fill the groove with the residual blackening conductive ink composition which has been dissolved, additional vibration and / or shaking, air can be used.

  In the secondary filling step (S20), it is preferable to carry out a drying step after treating the residual blackening conductive ink composition dissolved on the substrate surface. Drying of the blackening conductive pattern is preferably 22 to 600 ° C., more preferably 80 to 400 ° C. It is not necessarily limited to the said temperature range, and it is preferable to be performed in the temperature range which a base material does not deform | transform according to the kind of base material.

  The etchant evaporates from the dissolved residual blackening conductive ink composition filled in the grooves, and a pattern of a single layer consisting of one substance of the blackening conductive ink composition is formed in the grooves.

  Hereinafter, the present invention will be specifically described with reference to FIG.

  FIGS. 2a to 2f are sectional views sequentially illustrating the method of forming a blackening conductive pattern according to an embodiment of the present invention.

  As shown in FIG. 2a, a membrane 2 is formed on a substrate 1, and the membrane 2 is formed with a groove 3 having a square side cross section. The form of the groove 3 is not necessarily limited to a square, and various forms of grooves may be mixed and formed. The grooves 3 can be made to have a depth smaller than the thickness of the film 2.

  The membrane 2 can be subjected to a hydrophobic treatment on its top surface before the grooves 3 are formed. This makes it easier to process (fill and remove grooves) the blackening conductive ink composition described later. Such hydrophobic treatment on the upper surface is possible, for example, by plasma treatment on the upper surface of the film.

  In FIG. 2 b, after applying the blackening conductive ink composition 6 on the film 2, the blackening conductive ink composition 6 is filled in the grooves 3. In the corresponding drawing, the surface of the film 2 is pushed using the doctor blade 7 so that the blackening conductive ink composition 6 is filled in the groove 2.

  The method for applying the blackened conductive ink composition 6 is not limited to the use of the doctor blade 7 and may be an inkjet method, flat screen method, spin coating method, bar coater method, roll coating method, flow coating method Methods such as doctor blade, dispensing, gravure printing or flexographic printing can be used. The application of the blackening conductive ink composition is not limited to one time, and may be repeated several times in some cases.

  The blackening conductive ink composition 4 filled in the grooves 3 by the above method can be made equal to or lower than the depth of the grooves.

  Next, as shown in FIG. 2 c, an etchant 8 is applied onto the film 2. The etching solution 8 dissolves the residual blackening conductive ink composition 5 on the surface of the film 2 which is filled with the blackening conductive ink composition 6 in FIG. 2 b and inevitably occurs.

  The etching solution 6 can be made hydrophilic to allow the residual blackening conductive ink composition 5 to easily fill the grooves 3 thereafter. Preferably, ammonium carbamate type, ammonium carbonate type, ammonium bicarbonate type, carboxylic acid type, lactone type, lactam type, cyclic acid anhydride type compound, acid-base salt complex, acid-base-alcohol type complex or mercapto It is effective to contain the compound of the system. In the case of containing an ammonium carbamate type, ammonium carbonate type or ammonium bicarbonate type compound, the carbon number can be adjusted to control the degree of hydrophilicity.

  The method of applying the etching solution 6 is by methods commonly used in the industry, but roll coating, flow coating, gravure printing or flexographic printing is preferred.

  Thereafter, as shown in FIG. 2 d, the melted residual blackening conductive ink composition is pushed into the groove 3. For this purpose, a squeeze can be used, in which the brush 9 is used. This can be done one or more times, and can be used in combination with various types of squeeze.

  At this time, when the surface of the film 2 is subjected to hydrophobic treatment, the blackening conductive ink composition 6 can be more easily filled in the grooves 3.

  When the residual blackening conductive ink composition dissolved is filled in the groove 3 by the brush 9, as shown in FIG. 2e, the residual blackening conductive ink composition dissolved is the blackening conductive ink composition 4 of FIG. 2b. Stacked on top.

  In FIG. 2e, the dissolved residual blackening conductive ink composition contains an etchant and there is a layer distinction. After drying or baking, the etching solution is removed to form a single layer conductive pattern of one ink composition, as shown in FIG. 2f.

  Hereinafter, the present invention will be specifically described by way of examples. The scope of the present invention is not limited to the examples.

Production Example 1
19.05 g of conductive paste (manufactured by Ink Tech) and 0.45 g of hexanol are mixed with 10.5 g of a coating ink (manufactured by Ink Tech), and paste paste (manufactured by DAE WHA Tech) is used at 1000 rpm for 6 minutes. The mixture was stirred to produce a conductive ink composition.

Production Example 2
30 g of the conductive ink composition prepared according to Preparation Example 1 and 0.5 g of 2-ethylhexyl titanate are mixed, and the mixture is stirred at 1000 rpm for 3 minutes using a paste mixer (manufactured by DAE WHA Tech Co., Ltd.). A conductive ink composition was produced.

[Production Example 3]
30 g of the conductive ink composition produced according to Production Example 1 and 0.5 g of ethyl acetoacetic acid ester titanate are mixed, and the composition is stirred at 1000 rpm for 3 minutes using a paste mixer (manufactured by DAE WHA Tech) to make a blackened conductive ink composition Made things.

Production Example 4
30 g of the conductive ink composition produced according to Production Example 1 and 0.5 g of manganese (III) acetate dihydrate are mixed, and stirred using a paste mixer (manufactured by DAE WHA Tech Co., Ltd.) for 3 minutes at 1000 rpm for black A conductive ink composition was produced.

Production Example 5
30 g of the conductive ink composition prepared according to Preparation Example 1 and 0.5 g of antimony (III) isopropoxide were mixed, and stirred using a paste mixer (manufactured by DAE WHA Tech Co., Ltd.) for 3 minutes at 1000 rpm for blackening. A conductive ink composition was produced.

Production Example 6
30 g of the conductive ink composition prepared according to Preparation Example 1 and 0.5 g of titanium tetraisooctyl titanate are mixed, and the mixture is stirred at 1000 rpm for 3 minutes using a paste mixer (manufactured by DAE WHA Tech Co., Ltd.) to conduct blackening conductivity. An ink composition was produced.

Production Example 7
30 g of conductive paste (manufactured by Ink Tech Co., Ltd.) and 0.5 g of 2-ethylhexyl titanate are mixed, and the mixture is stirred at 1000 rpm for 3 minutes using a paste mixer (manufactured by DAE WHA Tech) to obtain a blackened conductive ink composition Manufactured.

Production Example 8
30 g of conductive paste (manufactured by Ink Tech Co., Ltd.) and 0.5 g of ethyl acetoacetic acid ester titanate are mixed and stirred at 1000 rpm for 3 minutes using a paste mixer (manufactured by DAE WHA Tech) to obtain a blackened conductive ink composition Manufactured.

Production Example 9
30 g of conductive paste (manufactured by Ink Tech Co., Ltd.) and 0.5 g of manganese (III) acetate dihydrate are mixed, and stirred with 1000 rpm for 3 minutes using a paste mixer (manufactured by DAE WHA Tech) to make blackened conductive Ink composition was prepared.

Production Example 10
30 g of conductive paste (manufactured by Ink Tech Co., Ltd.) and 0.5 g of antimony (III) isopropoxide are mixed, and stirred at 1000 rpm for 3 minutes using a paste mixer (manufactured by DAE WHA Tech) to achieve blackening conductivity. An ink composition was produced.

Production Example 11
30 g of conductive paste (manufactured by Ink Tech Co., Ltd.) and 0.5 g of tetraisooctyl titanate are mixed, and stirred at 1000 rpm for 3 minutes using a paste mixer (manufactured by DAE WHA Tech) to obtain a blackened conductive ink composition Manufactured.

Production Example 12
After adding 5 g of isobutyl carbamate, 83 g of isobutyl amine, and 2 g of a 95% solution of 2-amino-2-methyl-1-propanol, 10 g of 30% hydrogen peroxide was slowly added, and then stirred for 5 hours to produce an etching solution. did.

Production Example 13
After adding 10 g of isobutyl carbamate, 83 g of isobutyl amine, 2 g of a 95% solution of 2-amino-2-methyl-1-propanol, 5 g of 30% hydrogen peroxide was slowly added, and then stirred for 5 hours to prepare an etching solution. did.

Example [Example 1]
Using the PET film surface-modified by plasma treatment as a substrate, the conductive ink composition produced according to Production Example 1 was screen-printed on the upper side of the substrate. The film having the printed conductive pattern was baked at 120 ° C. for 5 minutes.

Example 2
A PET film surface-modified by plasma treatment was used as a substrate, and screen printing was performed on the upper side of the substrate with the blackened conductive ink composition produced according to Production Example 2. The film having the printed conductive pattern was baked at 120 ° C. for 5 minutes.

[Example 3]
A PET film surface-modified by plasma treatment was used as a substrate, and screen printing was performed on the upper side of the substrate using the blackened conductive ink composition produced according to Production Example 3. The film having the printed conductive pattern was baked at 120 ° C. for 5 minutes.

Example 4
A PET film surface-modified by plasma treatment was used as a substrate, and screen printing was performed on the upper side of the substrate with the blackened conductive ink composition produced according to Production Example 4. The film having the printed conductive pattern was baked at 120 ° C. for 5 minutes.

[Example 5]
A PET film surface-modified by plasma treatment was used as a substrate, and screen printing was performed on the upper side of the substrate with the blackened conductive ink composition produced according to Production Example 5. The film having the printed conductive pattern was baked at 120 ° C. for 5 minutes.

[Example 6]
A PET film surface-modified by plasma treatment was used as a substrate, and screen printing was performed on the upper side of the substrate with the blackened conductive ink composition produced according to Production Example 6. The film having the printed conductive pattern was baked at 120 ° C. for 5 minutes.

[Example 7]
A PET film surface-modified by plasma treatment was used as a substrate, and screen printing was performed on the upper side of the substrate with a conductive paste (manufactured by Ink Tech Co., Ltd.) ink composed of micro-sized metal particles. The film having the printed conductive pattern was baked at 120 ° C. for 5 minutes.

[Example 8]
A PET film surface-modified by plasma treatment was used as a substrate, and screen printing was performed on the upper side of the substrate with the blackened conductive ink composition produced according to Production Example 7. The film having the printed conductive pattern was baked at 120 ° C. for 5 minutes.

[Example 9]
A PET film surface-modified by plasma treatment was used as a substrate, and screen printing was performed on the upper side of the substrate with the blackened conductive ink composition produced according to Production Example 8. The film having the printed conductive pattern was baked at 120 ° C. for 5 minutes.

[Example 10]
A PET film surface-modified by plasma treatment was used as a substrate, and screen printing was performed on the upper side of the substrate with the blackened conductive ink composition produced according to Production Example 9. The film having the printed conductive pattern was baked at 120 ° C. for 5 minutes.

[Example 11]
A PET film surface-modified by plasma treatment was used as a substrate, and screen printing was performed on the upper side of the substrate with the blackened conductive ink composition produced according to Production Example 10. The film having the printed conductive pattern was baked at 120 ° C. for 5 minutes.

[Example 12]
A PET film surface-modified by plasma treatment was used as a substrate, and screen printing was performed on the upper side of the substrate with the blackened conductive ink composition produced according to Production Example 11. The film having the printed conductive pattern was baked at 120 ° C. for 5 minutes.

[Example 13]
After the UV resin was coated on PET, it was imprinted by pressing with a 3 μm fine line width mesh type mold, and the resin was cured and used as a substrate (ref.). The conductive ink composition prepared according to Preparation Example 1 as the conductive ink was coated on the upper side of the substrate, filled by a blade method, and the process of baking at 120 ° C. for 1 minute was repeated several times. In the next step, the etching solution prepared according to Preparation Example 12 is applied to the substrate filled with the conductive ink, the residual metal substance on the surface is dissolved, and the fine grooves are refilled or removed using the blade system. did. In the next step, the etching solution was dipped in a brush to wipe away metal and organic substances remaining on the substrate surface. In the next step, the substrate loaded with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.

Example 14
After coating a UV resin on PET, it was pressed with a 3 μm fine line width mesh type mold for imprinting, and the resin was cured and used as a substrate. The blackened conductive ink composition prepared according to Preparation Example 2 as a blackening improving ink is applied to the upper side of the substrate, filled twice by blade method, and fired several times at 120 ° C. for 1 minute. The In the next step, the etching solution prepared according to Preparation Example 12 is applied to the substrate filled with the blackening conductive ink composition, the residual metal substance on the surface is dissolved, and the fine grooves are formed using a blade system. It was refilled or removed. In the next step, the etching solution was dipped in a brush to wipe off metal and organic substances remaining on the substrate surface. In the next step, the substrate loaded with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.

[Example 15]
After coating a UV resin on PET, it was pressed with a 3 μm fine line width mesh type mold for imprinting, and the resin was cured and used as a substrate. The blackened conductive ink composition prepared according to Preparation Example 3 is applied to the upper side of the substrate as the blacking improvement ink, filled twice by blade method, and repeated several times the process of baking at 120 ° C. for 1 minute The In the next step, the etching solution prepared according to Preparation Example 12 is applied to the substrate filled with the blackening conductive ink composition, the residual metal substance on the surface is dissolved, and the fine grooves are formed using a blade system. It was refilled or removed. In the next step, the etching solution was dipped in a brush to wipe off metal and organic substances remaining on the substrate surface. In the next step, the substrate loaded with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.

[Example 16]
After coating a UV resin on PET, it was pressed with a 3 μm fine line width mesh type mold for imprinting, and the resin was cured and used as a substrate. The blackened conductive ink composition prepared according to Preparation Example 4 is applied to the upper side of the substrate as the blacking improvement ink, filled twice by blade method, and repeated several times the process of baking at 120 ° C. for 1 minute. The In the next step, the etching solution prepared according to Preparation Example 12 is applied to the substrate filled with the blackening conductive ink composition, the residual metal substance on the surface is dissolved, and the fine grooves are formed using a blade system. It was refilled or removed. In the next step, the etching solution was dipped in a brush to wipe off metal and organic substances remaining on the substrate surface. In the next step, the substrate loaded with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.

[Example 17]
After coating a UV resin on PET, it was pressed with a 3 μm fine line width mesh type mold for imprinting, and the resin was cured and used as a substrate. The blackened conductive ink composition prepared according to Preparation Example 5 is applied to the upper side of the substrate as the blacking improvement ink, filled twice by blade method, and the process of baking at 120 ° C. for 1 minute is repeated several times. The In the next step, the etching solution prepared according to Preparation Example 12 is applied to the substrate filled with the blackening conductive ink composition, the residual metal substance on the surface is dissolved, and the fine grooves are formed using a blade system. It was refilled or removed. In the next step, the etching solution was dipped in a brush to wipe off metal and organic substances remaining on the substrate surface. In the next step, the substrate loaded with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.

[Example 18]
After coating a UV resin on PET, it was pressed with a 3 μm fine line width mesh type mold for imprinting, and the resin was cured and used as a substrate. The blackened conductive ink composition prepared according to Preparation Example 6 as a blackening improvement ink is applied to the upper side of the base, filled twice by blade method, and fired several times at 120 ° C. for 1 minute. The In the next step, the etching solution prepared according to Preparation Example 12 is applied to the substrate filled with the blackening conductive ink composition, the residual metal substance on the surface is dissolved, and the fine grooves are formed using a blade system. It was refilled or removed. In the next step, the etching solution was dipped in a brush to wipe off metal and organic substances remaining on the substrate surface. In the next step, the substrate loaded with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.

[Example 19]
After coating a UV resin on PET, it was pressed with a 3 μm fine line width mesh type mold for imprinting, and the resin was cured and used as a substrate. Apply conductive paste (manufactured by Ink Tech Co., Ltd.) consisting of micro-class metal particles as conductive ink on the upper side of the substrate, fill it twice with blade method, and bake several times at 120 ° C for 1 minute I repeated it. In the next step, the etching solution prepared according to Preparation Example 12 is applied to the substrate filled with the blackening conductive ink composition, the residual metal substance on the surface is dissolved, and the fine grooves are formed using a blade system. It was refilled or removed. In the next step, the etching solution was dipped in a brush to wipe off metal and organic substances remaining on the substrate surface. In the next step, the substrate loaded with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.

[Example 20]
After coating a UV resin on PET, it was pressed with a 3 μm fine line width mesh type mold for imprinting, and the resin was cured and used as a substrate. The blackened conductive ink composition prepared according to Preparation Example 7 as a blackening improving ink is applied to the upper side of the base, filled twice by blade method, and fired several times at 120 ° C. for 1 minute. The In the next step, the etching solution prepared according to Preparation Example 12 is applied to the substrate filled with the blackening conductive ink composition, the residual metal substance on the surface is dissolved, and the fine grooves are formed using a blade system. It was refilled or removed. In the next step, the etching solution was dipped in a brush to wipe off metal and organic substances remaining on the substrate surface. In the next step, the substrate loaded with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.

[Example 21]
After coating a UV resin on PET, it was pressed with a 3 μm fine line width mesh type mold for imprinting, and the resin was cured and used as a substrate. The blackened conductive ink composition prepared according to Preparation Example 8 as a blackening improvement ink is applied to the upper side of the substrate, filled twice by blade method, and fired several times at 120 ° C. for 1 minute. The In the next step, the etching solution prepared according to Preparation Example 12 is applied to the substrate filled with the blackening conductive ink composition, the residual metal substance on the surface is dissolved, and the fine grooves are formed using a blade system. It was refilled or removed. In the next step, the etching solution was dipped in a brush to wipe off metal and organic substances remaining on the substrate surface. In the next step, the substrate loaded with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.

Example 22
After coating a UV resin on PET, it was pressed with a 3 μm fine line width mesh type mold for imprinting, and the resin was cured and used as a substrate. The process of applying the blackened conductive ink composition prepared according to Preparation Example 9 as the blackening improvement ink on the upper side of the base, filling twice with a blade method, and baking it at 120 ° C. for 1 minute was repeated several times . In the next step, the etching solution prepared according to Preparation Example 12 is applied to the substrate filled with the blackening conductive ink composition, the residual metal substance on the surface is dissolved, and the fine grooves are formed using a blade system. It was refilled or removed. In the next step, the etching solution was dipped in a brush to wipe off metal and organic substances remaining on the substrate surface. In the next step, the substrate loaded with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.

[Example 23]
After coating a UV resin on PET, it was pressed with a 3 μm fine line width mesh type mold for imprinting, and the resin was cured and used as a substrate. The process of applying the blackened conductive ink composition prepared according to Preparation Example 10 as the blackening improvement ink to the upper side of the base, filling twice with a blade method, and baking it at 120 ° C. for 1 minute was repeated several times . In the next step, the etching solution prepared according to Preparation Example 12 is applied to the substrate filled with the blackening conductive ink composition, the residual metal substance on the surface is dissolved, and the fine grooves are formed using a blade system. It was refilled or removed. In the next step, the etching solution was dipped in a brush to wipe off metal and organic substances remaining on the substrate surface. In the next step, the substrate loaded with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.

[Example 24]
After coating a UV resin on PET, it was pressed with a 3 μm fine line width mesh type mold for imprinting, and the resin was cured and used as a substrate. The blackened conductive ink composition prepared according to Preparation Example 11 as a blackening improvement ink is applied to the upper side of the base, filled twice by blade method, and fired several times at 120 ° C. for 1 minute. The In the next step, the etching solution prepared according to Preparation Example 12 is applied to the substrate filled with the blackening conductive ink composition, and the residual metal substance on the surface is dissolved and re-into the fine grooves using a blade system. Filled or removed. In the next step, the etching solution was dipped in a brush to wipe off metal and organic substances remaining on the substrate surface. In the next step, the substrate loaded with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.

[Example 25]
After coating a UV resin on PET, it was pressed with a 3 μm fine line width mesh type mold for imprinting, and the resin was cured and used as a substrate. Apply conductive paste (manufactured by Ink Tech Co., Ltd.) consisting of micro-class metal particles as conductive ink on the upper side of the substrate, fill it twice with blade method, and bake several times at 120 ° C for 1 minute I repeated it. In the next step, the etching solution prepared according to Preparation Example 13 is applied to the substrate filled with the blackening conductive ink composition, the residual metal substance on the surface is dissolved, and the fine grooves are formed using a blade system. It was refilled or removed. In the next step, the etching solution was dipped in a brush to wipe off metal and organic substances remaining on the substrate surface. In the next step, the substrate loaded with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.

  Table 1 below shows the results of the surface resistance, the specific resistance, the degree of blackening, the transmittance, the turbidity, and the adhesion of the fine line width electrodes manufactured according to Examples 1 to 25.

  Thus, according to the present invention, an optimum blackening substance is added to a conductive substance to form an ink composition, which is used to form a conductive pattern, to form an electrical, optical, or mechanical pattern. Since an electrode having a conductive pattern excellent in characteristics can be realized and there is no separate blackening treatment, the conductive pattern can be easily manufactured. Not only that, in forming the conductive pattern, the groove of the substrate is filled with the blackening conductive ink composition, and the residual blackening conductive ink composition that will remain on the substrate surface is dissolved with the etching solution Since the grooves of the substrate are refilled, it is possible to provide a low resistance ultrafine conductive pattern ranging from 50 nm to 50 μm line width.

  FIGS. 3a and 3b are graphs showing the specific resistance value and the degree of blackening measured for the blackening conductive ink composition by changing the content ratio of the blackening substance.

  According to FIG. 3a, the hybrid ink (coating ink, conductive ink composition mixed with conductive paste and hexanol) has improved blackening properties as the content of the blackening substance is increased and the electrical properties are also excellent. I understand that

  According to FIG. 3b, the conductive paste is mixed with increasing the content of the blackening substance, and it is confirmed that the electrical property and the blackening property are improved as the blackening conductive ink composition is formed. be able to.

  As a result, the blackening substance has a low specific resistance value when the content of the blackening substance is 0.1 to 2 parts by weight with respect to the conductive substance, so that the degree of blackening is also remarkably improved while the electrical properties are excellent It can be seen that the pattern can be embodied. The content of the blackening substance can be adjusted according to the type of conductive substance.

  The scope of the present invention is not limited to the embodiments described above, and can be embodied in various forms within the scope of the appended claims. The scope of the claims of the present invention is as diverse as any person skilled in the art to which the present invention belongs can be modified without departing from the scope of the present invention as claimed in the claims. Is considered to be within the scope of

  According to the present invention, it is possible not only to form a low resistance ultrafine conductive pattern which is difficult to realize in the prior art, but also to mix an blackening substance and a conductive substance to form an ink composition, and to form a single layer. The conductive pattern can be formed to provide a pattern formation method having excellent electrical and mechanical properties.

Claims (15)

A first filling step of filling the grooves of the base material having grooves with the blackening conductive ink composition containing the conductive material and the blackening material; and the blackening conductive ink in the first filling step The residual blackening conductive ink composition which will remain on the surface of the substrate while filling the groove into the groove is made of ammonium carbamate, ammonium carbonate, ammonium bicarbonate, carboxylic acid, lactone, etc. , lactam, cyclic acid anhydride-based compounds, acid - base salt complex, acid - base - Ru dissolved with an etching solution containing at least one and the oxidizing agent of alcohol complex or mercapto compounds, residual ink A step of dissolving the composition, and the groove by forcing the residual blackening conductive ink composition dissolved by the etchant into the groove Said residual blackening conductive ink composition is filled, the secondary filling phase containing residual ink composition filling phase; method of forming blackened conductive pattern, which comprises a.   The method for forming a blackened conductive pattern according to claim 1, further comprising a surface treatment step of treating the surface of the substrate with a hydrophobicity before the primary filling step.   The method for forming a blackened conductive pattern according to claim 2, wherein the surface treatment of the substrate is a plasma treatment. The conductive material is a metal complex compound, a metal precursor, a spherical metal particles, the method of forming the blackened conductive pattern according to claim 1, characterized in that it comprises at least one of a metal flake or nanoparticles . The formation of a blackened conductive pattern according to claim 1 , wherein the blackened material comprises a titanium-based, zirconium-based, manganese-based, antimony-based or vanadium-based complex compound or a combination of these complex compounds. Method. The titanium-based complex compounds are isopropyl titanate, ethyl titanate, n-butyl titanate, poly-N-butyl titanate, 2-ethylhexyl titanate, n-propyl titanate, octyl glycol titanate, tetraisooctyl titanate, cresyl titanate monomer, 6. The method according to claim 5 , further comprising at least one of cresyl titanate polymer, triethanolamine titanate, titanium acetylacetonate, titanium isopropoxide, ethylacetoacetic acid ester titanate, isostearoyl titanate or titanium lactate chelate. Of forming a blackened conductive pattern. The zirconium-based complex compound according to claim 5 , characterized in that it contains at least one of triethanolamine zirconate, zirconium lactate, zirconium glycolate, n-butyl zirconate or n-propyl zirconate. Of forming a blackened conductive pattern. The manganese-based complex compounds are manganese (III) acetylacetonate, manganese (III) acetylacetonate tetrahydrate, manganese (II) acetate, manganese (III) acetate dihydrate, manganese (II) acetylacetonate, Manganese (II) carbonate, manganese (II) carbonate hydrate, manganese (II) hexafluoroacetylacetonate trihydrate, manganese (II) chloride, manganese (II) nitrate tetrahydrate, manganese (II) sulfate monobasic Hydrate, Manganese (II) Sulfide, Manganese (II) Nitrate Hydrate, Manganese (II) Sulfate Monohydrate, Manganese (II) Perchlorate Hydrate, Manga (III) fluoride, manganese (II) sulfate hydrate, black according to claim 5, characterized in that it comprises at least one of manganese (II) chloride hydrate or manganese (II) chloride monohydrate Method of forming a conductive pattern. The antimony-based complex compounds are antimony (III) chloride, antimony (III) acetate, antimony (III) ethoxide, antimony (V) chloride, antimony (V) sulfide, antimony (III) methoxide antimony (III) sulfide, 6. The method according to claim 5 , further comprising at least one of antimony (V) fluoride, antimony (III) sulfide, antimony (III) butoxide, antimony (III) isopropoxide or antimony (III) propoxide. Of forming a blackened conductive pattern. The vanadium-based complex compounds are vanadium (III) acetylacetonate, vanadium (II) chloride, vanadium (III) chloride, vanadium (V) oxyl triethoxide, vanadium (V) oxyl chloride, vanadium (IV) chloride, Vanadium (V) oxyl tripropoxide, vanadium (V) oxyl fluoride, vanadium (IV) oxide sulfate hydrate, vanadium boride, vanadium (III) bromide or vanadium (III) iodide The method for forming a blackened conductive pattern according to claim 5 , comprising at least one of the following.   In the primary filling step, the blackened conductive ink is formed by an ink jet method, flat screen method, spin coating method, bar coater method, roll coating method, flow coating method, doctor blade, dispensing, gravure printing method or flexo printing method The method for forming a blackened conductive pattern according to claim 1, wherein the composition is filled.   The method according to claim 1, wherein the etching solution is applied to the surface of the substrate to dissolve the residual blackening conductive ink composition. The method for forming a blackened conductive pattern according to claim 1 , wherein the dissolved residual blackened conductive ink composition is pressed into the groove using a doctor blade or a brush.   The method of claim 1, further comprising: drying the blackening conductive ink composition filled in the grooves at a temperature of 22 ° C to 600 ° C. The blackening conductive ink composition according to claim 1 , wherein a content of the blackening substance is 0.01 to 10 parts by weight with respect to 100 parts by weight of the conductive substance. Method of forming a blackening conductive pattern .

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