WO2014178640A1 - 흑화 전도성 패턴의 형성방법 및 흑화 전도성 잉크 조성물 - Google Patents

흑화 전도성 패턴의 형성방법 및 흑화 전도성 잉크 조성물 Download PDF

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WO2014178640A1
WO2014178640A1 PCT/KR2014/003832 KR2014003832W WO2014178640A1 WO 2014178640 A1 WO2014178640 A1 WO 2014178640A1 KR 2014003832 W KR2014003832 W KR 2014003832W WO 2014178640 A1 WO2014178640 A1 WO 2014178640A1
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Prior art keywords
blackening
ink composition
manganese
conductive ink
iii
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PCT/KR2014/003832
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English (en)
French (fr)
Korean (ko)
Inventor
정광춘
이인숙
김민희
유지훈
Original Assignee
주식회사 잉크테크
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Priority to JP2016511680A priority Critical patent/JP6426152B2/ja
Priority to CN201480037174.3A priority patent/CN105519242B/zh
Publication of WO2014178640A1 publication Critical patent/WO2014178640A1/ko

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0092—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive pigments, e.g. paint, ink, tampon printing
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1258—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by using a substrate provided with a shape pattern, e.g. grooves, banks, resist pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0364—Conductor shape
    • H05K2201/0376—Flush conductors, i.e. flush with the surface of the printed circuit
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/09—Shape and layout
    • H05K2201/09009—Substrate related
    • H05K2201/09036—Recesses or grooves in insulating substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/01—Tools for processing; Objects used during processing
    • H05K2203/0104—Tools for processing; Objects used during processing for patterning or coating
    • H05K2203/0139—Blade or squeegee, e.g. for screen printing or filling of holes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/14—Related to the order of processing steps
    • H05K2203/1476—Same or similar kind of process performed in phases, e.g. coarse patterning followed by fine patterning
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/107—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by filling grooves in the support with conductive material

Definitions

  • the present invention relates to a method for forming a blackening conductive pattern, and more particularly, by mixing a conductive material and a blackening material, filling a blackening conductive ink composition having excellent optical and electrical properties in a groove of a substrate, thereby forming a single layer conductive pattern. It relates to a method of forming.
  • a fine pattern is formed on a substrate and filled with a metal conductive ink, and the metal pattern is very useful in resistance characteristics.
  • filling the pattern on the substrate with the metal conductive ink causes a problem of visibility due to the reflective properties of the metal.
  • a blackening process is generally introduced after the filling of the metal conductive ink.
  • the blackening process improves the visibility of a film, there exists a problem of worsening the electroconductivity of a film and consequently deteriorating the physical property as an electrode.
  • a method of forming a metal fine pattern electrode using various processes is known, but the following conventional techniques are found in the following problems.
  • Korean Patent Laid-Open Publication No. 10-2006-0105914 discloses a method of depositing a conductive metal as a seed on a transparent polymer film, and forming a black electroplating layer thereon and patterning the same in a mesh form.
  • this method is not only difficult to form and low-resistance electrode by the patterning etching and etching process, but also causes environmental problems.
  • Japanese Laid-Open Patent Publication No. 2001-127485 describes a method of forming a transparent electromagnetic shielding material by sequentially laminating a mesh-shaped black metal oxide layer and a metal layer on a transparent substrate.
  • this method also requires a complicated process of deposition and etching.
  • Korean Patent Laid-Open Publication No. 10-2007-0102263 discloses a method of coating a conductive resist layer capable of photocuring or thermosetting on a substrate and pressing the mold with a mold, followed by etching the conductive resist layer. .
  • a conductive resist layer capable of photocuring or thermosetting
  • etching the conductive resist layer
  • the invention described in Korean Patent Laid-Open Publication No. 10-2009-0061225 discloses applying a resist layer to a non-conductive substrate, forming a fine pattern on the resist layer using a laser, and forming a conductive material layer and a blackening material on the pattern.
  • the layers are laminated to form a conductive pattern.
  • the method is poor in visibility and difficult to form low resistance electrodes.
  • an object of the present invention is to solve such a conventional problem, a method of forming a blackening conductive pattern that can maintain the electrical properties by mixing the blackening material in the conductive material to improve the blackening degree and at the same time do not lower the resistance In providing.
  • the present invention provides a method of forming a blackening conductive pattern that can form a single layer pattern without a separate blackening process by using a single blackening conductive ink composition in which a conductive material and a blackening material are mixed as a material to fill a pattern. have.
  • the present invention provides a method of forming a blackening conductive pattern capable of improving mechanical properties by forming a single layer pattern with a blackening conductive ink composition to improve adhesion to a substrate groove.
  • the method of forming a blackening conductive pattern in the first filling step, the first filling step of filling the grooves of the substrate having a groove filled with the blackening conductive ink composition And a second filling step in which the remaining blackening conductive ink composition is filled in the grooves while the blackening conductive ink composition is filled in the grooves, and the remaining blackening conductive ink composition remaining on the surface of the substrate is dissolved in an etching solution. It is done.
  • 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 a complex compound of titanium, zirconium, manganese, antimony or vanadium, or these Combinations of complexing compounds may be included, and any material capable of forming a conductive pattern is applicable.
  • 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 , Tetra isooctyl titanate, xyl titanate monomer, xyl titanate polymer, thiethanolamine titanate, titanium acetyl acetonate, titanium isopropoxide, ethyl acetoacetic ester titanate, isosteroyl titanate or titanium At least one of lactate chelates, and the zirconium-based complex compound includes at least one of triethanolamine zirconate, zirconium lactate, zirconium glycorate, n-butyl zirconate, or n-propyl zirconate
  • the complex compound of manganese series is manganese (III) acetyl acetone Nitrate,
  • the vanadium-based complex compound is vanadium (III) acetylacetonate, vanadium (II) chloride, vanadium (III) chloride, vanadium (V) oxytriethoxide, vanadium (V) oxychloride, vanadium (IV) A) chloride, vanadium (V) oxytripropoxide, vanadium (V) oxyfluoride, vanadium (IV) oxide sulfate hydrate, vanadium boride, vanadium (III) bromide, vanadium (III) iodide have.
  • the first filling step, the blackening conductive ink composition by the inkjet 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 This may be filled in, but is not limited to this.
  • the secondary filling step may include a residual ink composition dissolving step of dissolving the residual blackening conductive ink composition with an etchant and a residual ink composition filling step of inducing the residual blackening conductive ink composition dissolved by the etching solution to be filled in the grooves. It is characterized by including.
  • the etchant can be applied to the surface of the substrate to dissolve the residual blackening conductive ink composition, and any method that can be commonly used in the industry can be applied to the method of applying the etchant.
  • the etching solution is ammonium carbamate series, ammonium carbonate series, ammonium bicarbonate series, carboxylic acid series, lactone series, lactam series, cyclic acid anhydride series compounds, acid-base salt complexes, acid-base alcohols It may include at least one of the complex or mercapto-based compound and the oxidizing agent.
  • the present invention is not limited thereto, and any etching solution capable of dissolving a metal material can be applied.
  • the secondary filling step includes pushing the dissolved residual blackening conductive ink composition into the grooves, thereby providing the residual blackening conductivity in the grooves.
  • the ink composition can be filled.
  • the dissolved residual blackening conductive ink composition may be pushed into the grooves using a doctor blade or a brush to fill the grooves, but the method is not limited thereto.
  • the method may further include a laminating step of laminating a blackening conductive ink composition on the blackening conductive pattern.
  • the blackening conductive ink composition filled in the groove may further include a drying step of drying at a temperature of 22 to 600 °C, the drying method may be various Applicable
  • the blackening conductive ink composition according to an embodiment of the present invention includes a conductive material and a blackening material
  • the blackening material is a complex compound of titanium-based, zirconium-based, manganese-based or antimony-based or these It is preferable to include a combination of complexing compounds, and any material capable of forming a blackening conductive pattern is not limited thereto.
  • the conductive material of the blackening conductive ink composition may include at least one of a metal complex compound, a metal precursor, spherical metal particles, metal flakes, or nanoparticles, but is not limited thereto.
  • the blackening material is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the conductive material.
  • the ink composition filled in the base groove is formed by adding an optimum blackening material to the conductive material, thereby simultaneously improving the optical, electrical, and mechanical properties of the conductive pattern.
  • the process is simplified and economical by using the ink composition by mixing the conductive material and the blackening material without forming a separate blackening layer, and the adhesion of the pattern is remarkably improved.
  • the blackening conductive ink composition when the blackening conductive ink composition is filled into the grooves of the substrate, the remaining blackening conductive ink composition is dissolved in an etching solution and refilled into the grooves, thereby forming a low resistance conductive pattern capable of realizing excellent performance. It is easy to form a fine conductive pattern.
  • FIG. 1 is a flowchart sequentially illustrating a method of forming a blackening conductive pattern according to an embodiment of the present invention.
  • FIGS. 2A to 2F are cross-sectional views sequentially illustrating a method of forming a blackening conductive pattern according to an embodiment of the present invention.
  • 3A is a graph showing specific resistance values measured by varying the content ratio of blackening material with respect to the blackening conductive ink composition.
  • 3B is a graph showing the degree of blackening (L *) measured by varying the content ratio of the blackening material with respect to the blackening conductive ink composition.
  • spatially relative terms below “, “ beneath “, “ lower”, “ above “, “ upper” It may be used to easily describe the correlation of components with other components. Spatially relative terms are to be understood as including terms in different directions of the component in use or operation in addition to the directions shown in the figures. For example, when flipping a component shown in the drawing, a component described as “below” or “beneath” of another component may be placed “above” the other component. Can be. Thus, the exemplary term “below” can encompass both an orientation of above and below. The components can be oriented in other directions as well, so that spatially relative terms can be interpreted according to the orientation.
  • each component is exaggerated, omitted, or schematically illustrated for convenience and clarity of description.
  • the size and area of each component does not necessarily reflect the actual size or area.
  • the blackening conductive pattern method includes a first filling step S10 and a second filling step S20 as shown in FIG. 1.
  • the blackening conductive ink composition is filled in the groove of the substrate having the groove, and the conductive material is filled in the groove of the intaglio.
  • the substrate may be formed of a transparent material such as a plastic film or glass.
  • the plastic film may be polyimide (PI), polyethylene terephthalate (PET), polyethernaphthalate (PEN), polyethersulfone (PES), nylon (Nylon), polytetrafluoroethylene (PTFE), polyether ether Ketones (PEEK), polycarbonates (PC), or polyarylates (PAR) can be used. It may be provided with an opaque material. For example, a metal plate having an insulated surface may be used, or an opaque plastic film, an opaque glass, or an opaque glass fiber material may be applied. Thus, a plastic film, a glass substrate, etc. can be used, It is not limited to this.
  • the method of forming a groove in the substrate may be formed by a method commonly used in the industry, and preferably, a method of imprinting a UV curable resin or a thermosetting resin into a mold by an imprinting process, and etching the substrate directly with a laser. It can be selected and used according to the size of the fine line width to be implemented by using a method of forming and using, a method of forming using a photolithography method.
  • the blackening conductive ink composition comprises a conductive material and a blackening material.
  • the conductive material may be a metal complex compound, a metal precursor, spherical metal particles, metal flakes or nanoparticles, may be used by mixing two or more kinds according to the material of the conductive material.
  • Metal complex compounds or metal precursors may be used to improve fillability in the fine grooves.
  • the metal complex compound or metal precursor may be reduced to prepare nano-sized metal particles, which may be used as a mixture. Using this, it is possible to easily form a nano-conductive fine pattern that could not be formed in the prior art.
  • the metal precursor used in the present invention may be represented by the general formula M n 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 from 1 to 10, X is oxygen, sulfur, halogen, cyano, cyanate , Carbonates, nitrates, nitrates, sulfates, phosphates, thiocyanates, chlorates, picchlorates, tetrafluorophorates, acetylacetonates, mercaptos, amides, alkoxides, carbolates and the like.
  • carboxylic acid metals such as zinc citrate, silver nitrate, copper cyanide, cobalt carbonate, chloride
  • metal compound such as platinum, gold acid, tetrabutoxy titanium, dimethoxyzirconium dichloride, aluminum isopropoxide, vanadium oxide, tantalum methoxide, bismuth acetate, dodecyl mercaptoated gold, indium acetylacetonate, etc. Can be selected together and used together.
  • Typical metal nanoparticle manufacturing methods include a physical method of physically pulverizing a metal mass and a method of manufacturing using a chemical reaction.
  • the chemical method is described by aerosol method for the injection of high-pressure gas to powder, pyrolysis method for pyrolysis using metal compound and gas reducing agent, heat evaporation of evaporation material to produce powder Evaporative condensation, sol-gel, hydrothermal synthesis, ultrasonic synthesis, microemulsion, liquid phase reduction, and the like.
  • the liquid phase reduction method using the dispersing agent and the reducing agent which is said to be easy to control the formation of nanoparticles and is considered to be the most economical, is used the most. .
  • the method for producing the nanoparticles by the liquid-phase reduction method is described in Korean Patent Application No. 2006-0074246 filed by the present applicant and the metal nanoparticles described in the patent application has the advantage that the particle size is uniform and the cohesion is minimized
  • the conductive ink containing the metal nanoparticles has an advantage of easily forming a uniform and dense thin film or fine pattern having high conductivity even when fired at a low temperature of 150 ° C. or less for a short time.
  • the blackening material is mixed with the conductive material to form a blackening conductive ink composition.
  • the blackening material is preferably a titanium (Ti) -based, zirconium (Zr) -based, manganese (Mn) -based, antimony (Sb) -based or vanadium (V) -based complex compound, these complex compounds depending on the type of conductive material Can be used in combination.
  • Titanium-based, zirconium-based, manganese-based or antimony-based complex compounds have an excellent effect on improving visibility, and can control metal-specific reflection characteristics, increase light absorption, and improve adhesion to the substrate.
  • 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, tetra iso Octyl titanate, xyl titanate monomer, xyl titanate polymer, thiethanolamine titanate, titanium acetyl acetonate, titanium isopropoxide, ethyl acetoacetic ester titanate, isosteroyl titanate or titanium lactate chelate It is preferable to include at least one of.
  • the zirconium-based complex compound preferably includes at least one of triethanolamine zirconate, zirconium lactate, zirconium glycorate, n-butyl zirconate or n-propyl zirconate.
  • the complex compounds of manganese series are manganese (III) acetyl acetonate, manganese (III) acetyl acetonate tetrahydrate, manganese (II) acetate, manganese (III) acetate dihydrate, manganese (II) acetyl acetonate, manganese (II) ) Carbonate, manganese (II) carbonate hydrate, manganese (II) hexafluoroacetylacetonate trihydrate, manganese (II) chloride, manganese (II) nitrate tetrahydrate, manganese (II) sulfate monohydrate, manganese (II) Sulfide, manganese (II) nitrate hydrate, manganese (II) sulfate monohydrate, manganese (II) perchlorate hydrate, manganese (III) fluoride, manganese (II) sul
  • the antimony-based complex compounds include antimony antimony (III) chloride, antimony (III) acetate, antimony (III) ethoxide, antimony (V) chloride, antimony (V) sulfide, antimony (III) methoxide antimony (III) sulfide And at least one of antimony (V) fluoride, antimony (III) sulfide, antimony (III) butoxide, antimony (III) isoproposide or antimony (III) proposide.
  • the vanadium-based complex compound is vanadium (III) acetylacetonate, vanadium (II) chloride, vanadium (III) chloride, vanadium (V) oxytriethoxide, vanadium (V) oxyyl chloride, vanadium (IV) chloride, At least one of vanadium (V) oxytripropoxide, vanadium (V) oxyfluoride, vanadium (IV) oxide sulfate hydrate, vanadium boride, vanadium (III) bromide or vanadium (III) iodide desirable.
  • the blackening material which consists of said metal complex compound or its combination has content of 0.01-10 weight part with respect to 100 weight part of conductive materials.
  • the blackening material is less than 0.01 part by weight, it is difficult to control the diffuse reflection of the metal, so that turbidity (haze) is significantly reduced. In addition, when it exceeds 10 parts by weight there is a problem that the electrical characteristics are reduced.
  • solvents such as solvents, stabilizers, dispersants, binder resins, release agents, reducing agents, surfactants, wetting agents, thixotropic agents or leveling agents, thickeners and Such additives may be included.
  • the said binder resin is excellent in the adhesive force with various base materials.
  • the materials that can be used are organic polymer materials such as polypropylene, polycarbonate, polyacrylate, polymethyl methacrylate, cellulose acetate, polyvinyl chloride, polyurethane, polyester, alkyd resin, epoxy resin, feoxy resin, melamine resin , Phenol resins, phenol modified alkyd resins, epoxy modified alkyd resins, vinyl modified alkyd resins, silicone modified alkyd resins, acrylic melamine resins, polyisocyanate resins, epoxy ester resins, and the like. Do not. In the blackening conductive ink used in the first filling step (S10), the silver (Ag) complex compound or nanoparticles may be used even when there is no binder, it is not limited to the above.
  • a solvent may be required to form a uniform thin film
  • solvents that may be used include ethanol, isopropanol, butanol, hexanol, alcohols, ethylene glycol, glycols such as glycerin, ethyl acetate, butyl acetate, and methoxy.
  • Acetates such as propyl acetate, carbitol acetate, ethyl carbitol acetate, methyl cersolve, butyl cellosolve, ethers such as diethyl ether, tetrahydrofuran, dioxane, methyl ethyl ketone, acetone, dimethylformamide Ketones such as 1-methyl-2-pyrrolidone, hexane, heptane, dodecane, paraffin oil, hydrocarbons such as mineral splits, aromatics such as benzene, toluene and xylene, and chloroform, methylene chloride, carbon tetrachloride Halogen substituted solvents such as acetonitrile, dimethyl sulfoxide or a mixed solvent thereof It can be used. However, the type of solvent is not limited thereto.
  • the method of filling the blackening conductive ink composition into the groove of the substrate is not limited, inkjet (inkjet) method, flat screen method, spin coating method, bar coater method, A roll coating method, a flow coating method, a doctor blade, a dispensing, a gravure printing method, or a flexography printing method are preferable.
  • the number of fillings at this time may be used repeatedly one or more times.
  • the filling properties may vary depending on the respective filling methods, but it is necessary to optimize the rheology of the composition by adjusting the components of the blackening conductive ink to be suitable for each filling method.
  • the thickness of the conductive pattern formed by the above method is preferably the same or lower than the pattern depth of the intaglio, but is not limited thereto.
  • the thickness of the conductive pattern may be thicker than the depth of the intaglio pattern, thereby increasing the contact force with the upper circuit. Specifically, it is preferably 10 ⁇ m or less, more preferably 0.1 ⁇ m or more and 5 ⁇ m or less.
  • the thickness of the conductive pattern needs to be adjusted according to the line width, required resistance, and post-treatment conditions.
  • the first filling step (S10) after filling the blackening conductive ink composition into the groove of the substrate, it is preferable to perform a drying step.
  • the drying of the conductive pattern may be 22 to 600 ° C, more preferably 80 to 400 ° C. It is not necessarily limited to the temperature range, it may be preferable to proceed in a temperature range that the substrate is not deformed according to the type of the substrate.
  • the secondary filling step (S20) is a step of further filling the grooves by treating the remaining blackening conductive ink composition remaining on the surface while the blackening conductive ink composition is filled in the grooves in the first filling step (S10). Thereby dissolving the residual blackening conductive ink composition and allowing the dissolved blackening conductive ink composition to be filled in the grooves.
  • the secondary filling step S20 may include a residual ink composition dissolving step S21 and a residual ink composition filling step S22, and may be filled in a groove in the process of dissolving the residual conductive ink composition.
  • Residual ink composition dissolving step (S21) is a step of dissolving the remaining blackening conductive ink composition remaining on the surface while the blackening conductive ink composition is filled in the groove in the first filling step (S10), the primary filling step ( In S10), the blackening conductive ink composition is inevitably left on the surface of the substrate while the blackening conductive ink composition is filled, and then dissolved with an etching solution to guide the grooves.
  • the etching mechanism of the blackening conductive ink composition may be achieved by repeatedly swelling and dissolving an oxidant to form a metal oxide by dissolving the metal surface and dissolving the metal oxide.
  • an etching solution can be applied to the surface of the substrate.
  • the coating method of the etching solution can be carried out by a conventional coating method.
  • the etching solution may be ammonium carbamate series, ammonium carbonate series, ammonium bicarbonate series, carboxylic acid series, lactone series, lactam series, cyclic acid anhydride series compounds, acid-base salt complexes, acid-base-alcohol complexes or mercapto ( It is preferred to include at least one of the mercapto series compounds and the oxidizing agent.
  • alcohols such as water, methanol, propanol, isopropanol, butanol and ethanol amine
  • Glycols such as ethylene glycol, glycerin, ethyl acetate, butyl acetate, acetates such as carbitol acetate, diethyl ether, tetrahydrofuran, ethers such as dioxane, methyl ethyl ketone, ketones such as acetone, hexane, Hydrocarbons such as heptane, aromatics such as benzene and toluene, and halogen-substituted solvents such as chloroform, methylene chloride and carbon tetrachloride, fluorine-based solvents such as perfluorocarbon, or a mixed solvent thereof may be
  • a pressurized state such as a pressure vessel
  • a low boiling point fluorine-based solvent or liquefied carbon dioxide may be used. It is not necessary to specifically limit the etching solution production method of the present invention. That is, any method known in the art may be used as long as it satisfies the object of the present invention.
  • an oxidizing agent for example, an oxidizing gas such as oxygen, ozone, hydrogen peroxide, Na 2 O 2 , KO 2 , NaBO 3 , (NH 4 ) S 2 O 8 , H 2 SO 5 , (CH 3 ) 3 Peroxides such as CO 2 H, (C 6 H 5 CO 2 ) 2, etc., HCO 3 H, CH 3 CO 3 H, CF 3 CO 3 H, C 6 H 5 CO 3 H, m-ClC 6 H 5 -CO 3 Peroxyacids such as H, nitric acid, sulfuric acid, iodine (I 2 ), Fe (NO 3 ) 3 , Fe 2 (SO 4 ) 3 , K 3 Fe (CN) 6 , (NH 4 ) 2 Fe (SO 4 ) 2 , Ce (NH 4 ) 4 (SO 4 ) 4 , NaIO 4 , KMnO 4 , K 2 CrO 4 and the like generally known oxidative inorganic acids or metals,
  • an oxidizing gas
  • the etchant may be desirable to impart hydrophilic properties to the etchant composition in order to effectively dissolve the conductive ink remaining on the surface of the substrate without filling the groove of the substrate and to increase the refilling into the micro grooves.
  • Ammonium carbamate-based compounds, ammonium carbonate-based compounds and ammonium bicarbonate-based compounds herein are described in detail in Korean Patent No. 0727466 of the present applicant, and the carboxylic acid-based compounds are benzoic acid, oleic acid, propionic acid, malonic acid, hexane Acids, 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 and the like can be used.
  • the carboxylic acid-based compounds are benzoic acid, oleic acid, propionic acid, malonic acid, hexane Acids, octanoic acid, decanoic acid, neodecanoic acid, oxalic acid, citric acid, salicylic acid, stearic acid
  • the lactone-based compounds include ⁇ -propiolactone, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -thiobutyrolactone, ⁇ -methyl- ⁇ -butyrolactone, ⁇ -methyl- ⁇ -butyrolactone, and ⁇ -Valerolactone, ⁇ -caprolactone, ⁇ -octanoic lactone, ⁇ -valerolactone, 1,6-dioxaspiro [4,4] nonane-2,7-dione, ⁇ -methylene- ⁇ -butyro Lactone, ⁇ -methylene- ⁇ -butyrolactone, ⁇ -caprolactone, lactide, glycolide, tetronic acid, 2 (5H) -huranone, ⁇ -hydroxy- ⁇ -butyrolactone, mevalonic lantone , 5,6-dihydro-2H-pyran-2-pyran-2-one, ⁇ -valerolactone, ⁇ -caprolactone,
  • Lactam-based compounds are 2-azetidon, 2-pinolidinone, 5-methoxy-2-pyrrolidinone, 5-methyl-2-pyrrolidinone, N -methylcaprolactam, 2-azacyclononnanone, N Acetyl caprolactam can be used.
  • cyclic acid anhydride itaconic anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, octadecyl succinic anhydride, 2,2-dimethylsuccinic anhydride, 2-dodecene- 1-sequential anhydride, hexafluoroglutaric anhydride, 3,3-dimethylglutaric anhydride, 3-ethyl-3-methyl glutaric anhydride, 3,5-diacetyltetrahydro Pyran-2,4,6-trione, diglycolic anhydride and the like can be used.
  • Mercapto-based compounds include 1-methane siol, 1-ethanesilol, 2-butanesilol, 1-heptane siol, 1-octanesiol, 1-decane siol, 1-hexadecane siol, Acetic acid, 6-mercaptohexanoic acid, thiobenzoic acid, furfuryl mercaptan, cyclohexanecyol, 11-mercapto-1 undecanol, 2-mercaptoethanol, 3-mercapto-1-propanol, cyio Salicylic acid, 1-cyorlyserol, 2-naphthalenecyol, methyl 3-mercaptopropionate, ganmar mercapto propyltrimethoxysilane, and the like can be used.
  • the present invention is not limited thereto, and may be used as a single component or selected from the group consisting of two or more kinds of mixtures.
  • the etching rate of the etching composition is to adjust the deposition time of the etching solution during coating, or the oxidizing agent or ammonium carbamate-based, ammonium carbonate-based, ammonium bicarbonate-based, carboxylic acid-based, lactone-based, lactam-based, cyclic anhydride-based , Acid-base salt complex, acid-base-alcohol-based complex, it is preferable to control by controlling the concentration of the mercapto-based compound, it can be used repeatedly the etching process if necessary.
  • the etching solution containing an inorganic acid or a base it can be removed by washing with a separate water or organic solvent.
  • the cleaning process may be further included to insert the conductive ink on the surface of the substrate into the groove.
  • the redissolution and filling rate of the residual conductive ink composition can be adjusted according to the ratio of the oxidizing agent and the etching liquid composition.
  • Filling the residual ink composition (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), leading to the residual blackening conductive ink composition into the grooves.
  • the method of inducing the residual blackening conductive ink composition into the groove is preferably pushed into the groove with a physical force to be filled.
  • a doctor blade or a brush can be used. More preferably, a brush is used.
  • the brush can effectively prevent scratches and ink loss of the substrate surface by reducing physical force.
  • filling may be performed one or more times, and various methods may be used in combination, in particular, a doctor blade and a brush.
  • the blackening conductive ink composition is filled in the grooves of the substrate, and at the same time, metal or organic substances, which are components of the blackening conductive ink composition remaining on the surface of the substrate, are removed. Can be.
  • Drying of the blackening conductive pattern may be 22 to 600 ° C, more preferably 80 to 400 ° C. It is not necessarily limited to the temperature range, it may be preferable to proceed in a temperature range that the substrate is not deformed according to the type of the substrate.
  • the etching solution is volatilized, so that the groove is formed with a single layer pattern composed of one material of the blackening conductive ink composition.
  • FIGS. 2A to 2F are cross-sectional views sequentially illustrating a method of forming a blackening conductive pattern according to an embodiment of the present invention.
  • a film 2 is formed on the substrate 1, and a groove 3 having a rectangular cross section is formed in the film 2.
  • the shape of the groove 3 is not necessarily limited to a quadrangle, and grooves of various shapes may be mixed and formed.
  • the groove 3 may have a depth smaller than the thickness of the film 2.
  • the film 2 may hydrophobicly treat the upper surface before the groove 3 is formed. Thereby, the process (filling and removal into a groove
  • This hydrophobic treatment on the top surface can be made possible by, for example, plasma treatment of the top surface of the film.
  • the blackening conductive ink composition 6 is filled in the groove 3.
  • the squeeze in the figure, is used to push the surface of the film 2 using the doctor blade 7 so that the blackening conductive ink composition 6 is filled in the groove 2.
  • the method of applying the blackening conductive ink composition 6 is not limited to the use of the doctor blade 7, but may be an inkjet method, a flat screen method, a spin coating method, a bar coater method, a roll coating method, a flow coating method, Doctor blades, dispensing, gravure printing or flexo printing can be used.
  • Application of the blackening conductive ink composition is not limited to one time, and may be repeated a plurality of times in some cases.
  • the blackening conductive ink composition 4 filled in the groove 3 by the above method may be equal to or lower than the depth of the groove.
  • the etching solution 8 is applied onto the film 2.
  • the etchant 8 dissolves the residual blackening conductive ink composition 5 on the surface of the film 2 which is inevitably generated and filled with the blackening conductive ink composition 6 in FIG. 2B.
  • the etching solution 6 may be hydrophilic in order to easily fill the groove 3 with the remaining blackening conductive ink composition 5 later.
  • ammonium carbamate series, ammonium carbonate series, ammonium bicarbonate series, carboxylic acid series, lactone series, lactam series, cyclic acid anhydride series compounds, acid-base salt complexes, acid-base-alcohol complexes or mercaptos It is effective to include family compounds.
  • the degree of hydrophilicity can be controlled by adjusting the carbon number.
  • the coating method of the etching solution 6 is a method commonly used in the industry, but a roll coating, flow coating, gravure printing, or flexo printing method is preferable.
  • the dissolved residual blackening conductive ink composition is pushed into the groove 3.
  • squeeze can be used, and the brush 9 is used in the drawing. This may be done more than once, and several types of squeeze may be used in combination.
  • the blackening conductive ink composition 6 can be more easily filled into the grooves 3.
  • the dissolved residual blackening conductive ink composition When the dissolved residual blackening conductive ink composition is filled in the grooves 3 by the brush 9, as shown in FIG. 2E, the dissolved residual blackening conductive ink composition is laminated on the blackening conductive ink composition 4 of FIG. 2B. do.
  • the dissolved residual blackening conductive ink composition contains an etchant to distinguish the layers.
  • the etching solution is subsequently removed through drying or firing to form a single layer conductive pattern made of one type of ink composition as shown in FIG. 2F.
  • the UV resin was coated on PET, imprinted by pressing with a mesh type mold having a fine line width of 3 ⁇ m, and the resin was cured and used as a substrate (ref.).
  • the conductive ink composition prepared in Preparation Example 1 was applied to the upper surface of the substrate with a conductive ink, and the process of baking for 1 minute at 120 ° C. was repeated several times.
  • the etching solution prepared in Preparation Example 12 was applied to a substrate filled with conductive ink, and the remaining metal material on the surface was dissolved to refill or remove fine grooves using a blade method.
  • the etchant was moistened with a brush to wipe off metal and organic substances remaining on the substrate surface.
  • the substrate filled with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.
  • the UV resin was coated on PET, imprinted by pressing with a mesh type mold having a fine line width of 3 ⁇ m, and the resin was cured to use as a substrate.
  • the blackening conductive ink composition prepared in Preparation Example 2 was applied to the top of the substrate as blackening improvement ink, and the process of baking twice at a temperature of 120 ° C. for 1 minute was repeated twice by a blade method.
  • the etching solution prepared in Preparation Example 12 was applied to the substrate filled with the blackening conductive ink composition, and the residual metal material on the surface was dissolved to refill or remove fine grooves using a blade method.
  • the etchant was moistened with a brush to wipe off metal and organic substances remaining on the surface of the substrate.
  • the substrate filled with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.
  • the UV resin was coated on PET, imprinted by pressing with a mesh type mold having a fine line width of 3 ⁇ m, and the resin was cured to use as a substrate.
  • the blackening conductive ink composition prepared in Preparation Example 3 was applied to the top of the substrate as blackening improvement ink, and the filling process was repeated twice by baking in a blade method for 1 minute at 120 ° C.
  • the etching solution prepared in Preparation Example 12 was applied to the substrate filled with the blackening conductive ink composition, and the residual metal material on the surface was dissolved to refill or remove fine grooves using a blade method.
  • the etchant was moistened with a brush to wipe off metal and organic substances remaining on the surface of the substrate.
  • the substrate filled with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.
  • the UV resin was coated on PET, imprinted by pressing with a mesh type mold having a fine line width of 3 ⁇ m, and the resin was cured to use as a substrate.
  • the blackening conductive ink composition prepared in Preparation Example 4 was applied to the top of the substrate as blackening improvement ink, and the filling process was repeated twice by baking in a blade method for 1 minute at 120 ° C.
  • the etching solution prepared in Preparation Example 12 was applied to the substrate filled with the blackening conductive ink composition, and the residual metal material on the surface was dissolved to refill or remove fine grooves using a blade method.
  • the etchant was moistened with a brush to wipe off metal and organic substances remaining on the surface of the substrate.
  • the substrate filled with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.
  • the UV resin was coated on PET, imprinted by pressing with a mesh type mold having a fine line width of 3 ⁇ m, and the resin was cured to use as a substrate.
  • the blackening conductive ink composition prepared in Preparation Example 5 was applied to the top of the substrate as blackening improvement ink, and the process of baking twice at a temperature of 120 ° C. for two minutes was filled by a blade method.
  • the etching solution prepared in Preparation Example 12 was applied to the substrate filled with the blackening conductive ink composition, and the residual metal material on the surface was dissolved to refill or remove fine grooves using a blade method.
  • the etchant was moistened with a brush to wipe off metal and organic substances remaining on the surface of the substrate.
  • the substrate filled with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.
  • the UV resin was coated on PET, imprinted by pressing with a mesh type mold having a fine line width of 3 ⁇ m, and the resin was cured to use as a substrate.
  • the blackening conductive ink composition prepared in Preparation Example 6 was applied to the top of the substrate as blackening improvement ink, and the filling process was repeated twice by baking in a blade method for 1 minute at 120 ° C.
  • the etching solution prepared in Preparation Example 12 was applied to the substrate filled with the blackening conductive ink composition, and the residual metal material on the surface was dissolved to refill or remove fine grooves using a blade method.
  • the etchant was moistened with a brush to wipe off metal and organic substances remaining on the surface of the substrate.
  • the substrate filled with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.
  • the UV resin was coated on PET, imprinted by pressing with a mesh type mold having a fine line width of 3 ⁇ m, and the resin was cured to use as a substrate.
  • a conductive paste (manufactured by Ink Tech Co., Ltd.) made of micro-grade metal particles as a conductive ink was applied to the upper surface of the substrate, and filled twice with a blade method and baked at 120 ° C. for 1 minute.
  • the etching solution prepared in Preparation Example 12 was applied to the substrate filled with the blackening conductive ink composition, and the residual metal material on the surface was dissolved to refill or remove fine grooves using a blade method.
  • the etchant was moistened with a brush to wipe off metal and organic substances remaining on the surface of the substrate.
  • the substrate filled with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.
  • the UV resin was coated on PET, imprinted by pressing with a mesh type mold having a fine line width of 3 ⁇ m, and the resin was cured to use as a substrate.
  • the blackening conductive ink composition prepared in Preparation Example 7 was applied to the top of the substrate as blackening improvement ink, and the process of baking twice at a temperature of 120 ° C. for 1 minute was repeated twice by a blade method.
  • the etching solution prepared in Preparation Example 12 was applied to the substrate filled with the blackening conductive ink composition, and the residual metal material on the surface was dissolved to refill or remove fine grooves using a blade method.
  • the etchant was moistened with a brush to wipe off metal and organic substances remaining on the surface of the substrate.
  • the substrate filled with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.
  • the UV resin was coated on PET, imprinted by pressing with a mesh type mold having a fine line width of 3 ⁇ m, and the resin was cured to use as a substrate.
  • the blackening conductive ink composition prepared in Preparation Example 8 was applied to the top of the substrate as blackening improvement ink, and the filling process was repeated twice by baking in a blade method for 1 minute at 120 ° C.
  • the etching solution prepared in Preparation Example 12 was applied to the substrate filled with the blackening conductive ink composition, and the residual metal material on the surface was dissolved to refill or remove fine grooves using a blade method.
  • the etchant was moistened with a brush to wipe off metal and organic substances remaining on the surface of the substrate.
  • the substrate filled with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.
  • the UV resin was coated on PET, imprinted by pressing with a mesh type mold having a fine line width of 3 ⁇ m, and the resin was cured to use as a substrate.
  • the blackening conductive ink composition prepared in Preparation Example 9 was applied to the top of the substrate as blackening improving ink, and the filling process was repeated twice by baking in a blade method for 1 minute at 120 ° C.
  • the etching solution prepared in Preparation Example 12 was applied to the substrate filled with the blackening conductive ink composition, and the residual metal material on the surface was dissolved to refill or remove fine grooves using a blade method.
  • the etchant was moistened with a brush to wipe off metal and organic substances remaining on the surface of the substrate.
  • the substrate filled with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.
  • the UV resin was coated on PET, imprinted by pressing with a mesh type mold having a fine line width of 3 ⁇ m, and the resin was cured to use as a substrate.
  • the blackening conductive ink composition prepared in Preparation Example 10 was applied to the top of the substrate as a blackening improvement ink, and the process of baking twice at a temperature of 120 DEG C for 1 minute was repeated twice by a blade method.
  • the etching solution prepared in Preparation Example 12 was applied to the substrate filled with the blackening conductive ink composition, and the residual metal material on the surface was dissolved to refill or remove fine grooves using a blade method.
  • the etchant was moistened with a brush to wipe off metal and organic substances remaining on the surface of the substrate.
  • the substrate filled with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.
  • the UV resin was coated on PET, imprinted by pressing with a mesh type mold having a fine line width of 3 ⁇ m, and the resin was cured to use as a substrate.
  • the blackening conductive ink composition prepared in Preparation Example 11 was applied to the top of the substrate as blackening improvement ink, and the process of baking twice at a temperature of 120 ° C. for 1 minute was repeated twice by a blade method.
  • the etching solution prepared in Preparation Example 12 was applied to the substrate filled with the blackening conductive ink composition, and the residual metal material on the surface was dissolved to refill or remove fine grooves using a blade method.
  • the etchant was moistened with a brush to wipe off metal and organic substances remaining on the surface of the substrate.
  • the substrate filled with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.
  • the UV resin was coated on PET, imprinted by pressing with a mesh type mold having a fine line width of 3 ⁇ m, and the resin was cured to use as a substrate.
  • a conductive paste (manufactured by Ink Tech Co., Ltd.) made of micro-grade metal particles as a conductive ink was applied to the upper surface of the substrate, and filled twice with a blade method and baked at 120 ° C. for 1 minute.
  • the etching solution prepared in Preparation Example 13 was applied to the substrate filled with the blackening conductive ink composition, and the remaining metal material on the surface was dissolved to refill or remove fine grooves using a blade method.
  • the etchant was moistened with a brush to wipe off metal and organic substances remaining on the surface of the substrate.
  • the substrate filled with the metal material was dried at 120 ° C. for 5 minutes to form a fine line width electrode.
  • Table 1 describes the results of sheet resistance, specific resistance, blackness, transmittance, turbidity, and adhesion of the fine line width electrodes prepared according to Examples 1 to 25.
  • an ink composition may be formed by adding an optimal blackening material to the conductive material, thereby forming a conductive pattern, thereby realizing an electrode having a conductive pattern having excellent electrical, optical, and mechanical properties. Since there is no separate blackening treatment, a simple conductive pattern can be manufactured.
  • the blackening conductive ink composition is filled in the grooves of the substrate, and the remaining blackening conductive ink composition remaining on the surface of the substrate is dissolved in an etching solution to refill the grooves of the substrate. It is possible to provide a low resistance ultra fine conductive pattern ranging from nm to 50 ⁇ m line width.
  • 3A and 3B are graphs showing specific resistance values and blackening degrees by varying the content ratio of the blackening material with respect to the blackening conductive ink composition.
  • the hybrid ink (a conductive ink composition in which a coating ink, a conductive paste, and hexanol is mixed) improves blackening characteristics and increases electrical specificity by increasing the content of blackening material.
  • the blackening conductive ink composition is mixed by increasing the content of the blackening material in the conductive paste, the electrical and blackening characteristics are improved.
  • the blackening material when present in an amount of 0.1 to 2 parts by weight with respect to the conductive material, it can be seen that a low specific resistance value can realize a pattern with excellent electrical characteristics and remarkably improved blackening.
  • the content of blackening material may be adjusted according to the type of conductive material.
  • the present invention it is possible not only to form a low-resistance ultra-fine conductive pattern that was difficult to implement in the prior art, but also to form an ink composition by mixing a blackening material and a conductive material to form a single-layer conductive pattern. It is possible to provide a pattern forming method having excellent mechanical properties.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Conductive Materials (AREA)
  • Manufacturing Of Electric Cables (AREA)
PCT/KR2014/003832 2013-04-30 2014-04-30 흑화 전도성 패턴의 형성방법 및 흑화 전도성 잉크 조성물 WO2014178640A1 (ko)

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JP7375294B2 (ja) * 2017-07-28 2023-11-08 Tdk株式会社 導電性基板、電子装置及び表示装置の製造方法
CN111511121A (zh) * 2020-05-15 2020-08-07 深圳市百柔新材料技术有限公司 立体导电线路及其制备方法

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KR101553439B1 (ko) 2015-10-01
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