TWI524826B - Method for manufacturing conductive pattern, conductive pattern, conductive film and transparent conductive film - Google Patents

Method for manufacturing conductive pattern, conductive pattern, conductive film and transparent conductive film Download PDF

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TWI524826B
TWI524826B TW102149113A TW102149113A TWI524826B TW I524826 B TWI524826 B TW I524826B TW 102149113 A TW102149113 A TW 102149113A TW 102149113 A TW102149113 A TW 102149113A TW I524826 B TWI524826 B TW I524826B
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substrate
groove
conductive
conductive ink
mixture
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TW201440594A (en
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鄭光春
柳志勳
李仁淑
成俊基
韓大尚
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印可得股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
    • H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
    • H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
    • H01L21/76817—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics using printing or stamping techniques
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
    • 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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • 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
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0108—Transparent
    • 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
    • H05K2203/0108—Male die used for patterning, punching or transferring
    • 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

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Manufacturing Of Electric Cables (AREA)

Description

導電圖案的形成方法、導電膜、導電圖案及透明導電膜 Method for forming conductive pattern, conductive film, conductive pattern, and transparent conductive film

本發明涉及一種導電圖案的形成方法、導電膜、導電圖案及透明導電膜；尤其涉及一種在基材的槽中填充導電墨從而形成導電圖案的導電圖案的形成方法、導電膜、導電圖案及透明導電膜，其中在所述導電圖案的形成方法中，是用蝕刻液溶解殘留在基材表面的導電墨，將其壓入並填充於基材的槽中，從而形成導電圖案。 The present invention relates to a method for forming a conductive pattern, a conductive film, a conductive pattern, and a transparent conductive film; and more particularly to a method for forming a conductive pattern in which a conductive ink is filled in a groove of a substrate to form a conductive pattern, a conductive film, a conductive pattern, and a transparent film In the conductive film, in the method of forming the conductive pattern, the conductive ink remaining on the surface of the substrate is dissolved with an etching solution, pressed into and filled in a groove of the substrate, thereby forming a conductive pattern.

最近，隨著電子產品的輕薄小型化的趨勢，要求將顯示器或電晶體等電子元件製成高密度、高集成的形式，於是，能夠用於電極或金屬排線(metallization lines)的，且能形成微細金屬圖案的技術備受矚目。 Recently, with the trend of thinness and miniaturization of electronic products, it is required to make electronic components such as displays or transistors into a high-density, high-integration form, so that it can be used for electrodes or metallization lines, and can Techniques for forming fine metal patterns have attracted attention.

迄今廣為人知的金屬的微細圖案的製作技術一般是通過與薄膜的真空沉積相結合的照相平版印刷工藝實現的。該方法在基材上沉積導電材料之後，為了形成微細圖案電路，在導電材料的表面上塗敷乾膜(Dry Film)或感光液後，照射紫外線(UV)進行固化，並使用顯影液進行顯影，之後使用化學蝕刻液形成需要實現的微細圖案。照相平版印刷工藝雖然具有能夠形成高解析度(resolution)圖案的優點，但具有設備費用昂貴，生產工藝複雜，由反復進行的蝕刻工藝產生過量的化學廢物的缺點。 The technique for fabricating fine patterns of metals which have hitherto been widely known is generally achieved by a photolithography process in combination with vacuum deposition of a film. After the method deposits a conductive material on a substrate, in order to form a fine pattern circuit, a dry film (Dry Film) or a photosensitive liquid is applied on the surface of the conductive material, and then cured by ultraviolet rays (UV), and developed using a developing solution. The chemical etching solution is then used to form the fine pattern that needs to be achieved. Although the photolithography process has the advantage of being able to form a high resolution pattern, it has the disadvantages of expensive equipment, complicated production process, and excessive chemical waste generated by repeated etching processes.

此外，最近隨著柔性電子元件的到來，能夠在低溫下進行大 面積化的構圖工藝的重要性被提出，且為了取代以高額設備以及高費用為特點的現有的照相平版印刷工藝，正在進行著尋找替代方法的諸多研究開發。例如有使用噴墨印刷的構圖、使用凹版膠印的構圖、使用反向平版印刷法的構圖以及使用雷射蝕刻的構圖等。 In addition, recently, with the advent of flexible electronic components, it is possible to carry out at low temperatures. The importance of the aread patterning process has been proposed, and in order to replace the existing photolithography processes characterized by high equipment and high cost, many research and developments are under way to find alternative methods. For example, there are composition using inkjet printing, patterning using gravure offset printing, patterning using reverse lithography, patterning using laser etching, and the like.

這些方式的優點為其是直接構圖方式，且部分方式還表現出相當大的技術進步性，但由於各自在微細線寬的實現性、可靠性和生產工藝速度上的局限性，仍無法代替照相平版印刷工藝。 The advantage of these methods is that they are direct patterning, and some methods also show considerable technological advancement, but due to their limitations in the realization of micro-line width, reliability and speed of production process, they are still not a substitute for photography. Lithographic process.

奈米壓印技術是為了彌補上述直接構圖方式的缺點，並解決照相平版印刷工藝的問題而提出的，該技術是在基材基板上塗敷光固化型樹脂或熱固化型樹脂後，將包含奈米至微米大小的凹凸的模具加壓於所述被塗敷的樹脂層上，並且施加紫外線或熱量，使其固化，從而將圖案轉印到基材基板的技術。與作為形成幾十微米(μm)線寬的線的技術而被應用的直接的圖案形成方法和照相平版印刷方法相比較時，上述的奈米壓印技術在製造單價和解析度方面，是兩種技術的中等程度，其在奈米和微米領域的橋樑作用的同時，部分地逐步取代上述兩種技術。 The nanoimprint technique is proposed to compensate for the shortcomings of the above direct patterning method and to solve the problem of the photolithography process, which is to apply a photocurable resin or a thermosetting resin to a substrate. A technique in which a mold of rice to micron size is pressed onto the applied resin layer, and ultraviolet rays or heat is applied to cure it, thereby transferring the pattern to the substrate. When compared with a direct pattern forming method and a photolithography method which are applied as a technique of forming a line having a line width of several tens of micrometers (μm), the above-described nanoimprint technique is two in terms of manufacturing unit price and resolution. The medium level of technology, in the role of bridges in the field of nanometers and micrometers, partially replaces the above two technologies.

最近，開發了很多種採用上述奈米壓印方法來形成一般微細圖案的技術，但用於電極或排線的低電阻超細圖案電極形成技術還需要進一步的開發。韓國公開專利第10-2007-0102263號涉及一種圖案形成方法，該方法在基材基板上塗敷能夠進行光固化或熱固化的導電性光刻膠層後採用模具進行加壓，之後對導電性光刻膠層進行蝕刻，從而形成圖案，但為了形成低電阻電極，需要導電性金屬層，但用上述方法實現則有一定的難度。此外，還有一種金屬微細圖案的形成方法，即在基材上沉積金屬層後，在其上面塗敷光固化或熱固化型樹脂層，並採用模具加壓而形成圖案，之後再對殘留的樹脂層進行蝕刻，但該方法的工藝非常繁雜，有生產效率較低的問題。韓國公開專利第10-2011-0100034號涉及一 種通過壓印工藝形成微槽，並將金屬層填充到上述槽中，從而形成金屬微細線寬的方法，但上述方法在實現亞微米線寬存在問題，且在形成低電阻電極上有一定的局限性。 Recently, many techniques for forming a general fine pattern using the above-described nanoimprint method have been developed, but further development is required for a low-resistance ultra-fine pattern electrode forming technique for electrodes or wires. Korean Laid-Open Patent Publication No. 10-2007-0102263 relates to a pattern forming method which applies a conductive photoresist layer capable of photocuring or heat curing on a substrate substrate, and then pressurizes with a mold, followed by conductive light. The engraved layer is etched to form a pattern, but in order to form a low-resistance electrode, a conductive metal layer is required, but it is difficult to achieve by the above method. In addition, there is a method of forming a fine metal pattern by depositing a metal layer on a substrate, applying a photocurable or thermosetting resin layer thereon, and pressing the mold to form a pattern, and then remaining the remaining layer. The resin layer is etched, but the process of the method is very complicated and has a problem of low production efficiency. Korean Patent No. 10-2011-0100034 relates to one A method of forming a microgroove by an imprint process and filling a metal layer into the above-mentioned groove to form a fine line width of the metal, but the above method has a problem in realizing a submicron line width, and has a certain degree in forming a low resistance electrode. limitation.

作為另一種形成金屬微細圖案的方法，本申請人的韓國授權專利第10-0922810號公開了採用雷射直接對樹脂層表面或者同時直接對樹脂層與基材進行蝕刻，形成微槽後填充金屬層，從而形成微細線寬的電極的技術。但該方法在形成奈米大小的微槽時，由於雷射光源的線寬實現性問題，具有一定的局限性。 As another method of forming a fine metal pattern, the applicant's Korean Patent No. 10-0922810 discloses that a resin is directly etched on the surface of the resin layer or directly on the surface of the resin layer by a laser to form a micro-groove and then filled with a metal. A technique of forming a layer of electrodes having a fine line width. However, this method has certain limitations when forming nanometer-sized microgrooves due to the line width realization problem of the laser light source.

雖然上述的先前技術公開了採用各種工藝形成金屬微細圖案電極的多種方法，但形成低電阻的超細圖案電極，仍存在一定的問題。 Although the above prior art discloses various methods of forming a metal fine pattern electrode by various processes, there is still a problem in forming a low-resistance ultra-fine pattern electrode.

本發明的目的在於，提供一種導電圖案的形成方法、導電膜、導電圖案及透明導電膜，所述導電圖案的形成方法在基材的槽中填充導電墨來形成導電圖案，其中用蝕刻液溶解殘留在基材表面的導電墨，並將所述導電墨推入並填充於基材的槽中，從而可形成採用先前技術難以實現的微細的低電阻導電圖案。 An object of the present invention is to provide a method for forming a conductive pattern, a conductive film, a conductive pattern, and a transparent conductive film. The method for forming the conductive pattern is filled with conductive ink in a groove of the substrate to form a conductive pattern, wherein the conductive pattern is dissolved. The conductive ink remaining on the surface of the substrate is pushed into and filled in the grooves of the substrate, so that a fine low-resistance conductive pattern which is difficult to achieve by the prior art can be formed.

本發明的一實施例提供一種導電圖案的形成方法，其特徵在於，包括步驟：a)在具有槽的基材的所述槽中填充導電墨；以及b)在填充所述導電墨時，用蝕刻液溶解殘留在所述基材表面的導電墨，並將所述導電墨引導至所述槽中，從而使所述槽中填充所述導電墨。 An embodiment of the present invention provides a method of forming a conductive pattern, comprising the steps of: a) filling a conductive ink in the groove of a substrate having a groove; and b) when filling the conductive ink, The etching solution dissolves the conductive ink remaining on the surface of the substrate, and guides the conductive ink into the groove, thereby filling the groove with the conductive ink.

在所述步驟a)之前，可進一步包括在所述基材上形成槽的步驟。 Prior to said step a), the step of forming a groove on the substrate may be further included.

在所述基材上形成槽的步驟中，可採用壓印法、雷射蝕刻法或照相平版印刷法在所述基材上形成槽，但是還可以應用在本領 域中能夠形成槽的所有方法，而並不僅限於此。 In the step of forming a groove on the substrate, a groove may be formed on the substrate by an imprint method, a laser etching method or a photolithography method, but it is also applicable to the method. All methods of forming a slot in a domain are not limited to this.

採用所述壓印法時，在所述基材上形成槽之前，可進一步包括塗敷UV固化樹脂或熱固化樹脂以形成樹脂層的步驟。其中，除了所述的樹脂之外，當然還可以採用能夠用於壓印法的所有樹脂。 When the imprint method is employed, a step of coating a UV curable resin or a thermosetting resin to form a resin layer may be further included before forming a groove on the substrate. Among them, in addition to the above-mentioned resins, it is of course possible to use all resins which can be used for the imprint method.

作為所述導電墨可使用包含金屬錯合物、金屬前體、球形金屬粒子、金屬薄片或奈米粒子的導電墨，但並不限於此。只要是能夠被蝕刻液溶解，且移動被引導，填充至槽中，從而形成導電圖案的物質均能適用。 As the conductive ink, a conductive ink containing a metal complex, a metal precursor, a spherical metal particle, a metal foil or a nano particle can be used, but is not limited thereto. Any substance that can be dissolved by the etching liquid and whose movement is guided and filled into the groove to form a conductive pattern can be applied.

在所述步驟a)中，可採用噴墨法、平板絲網印刷法、旋轉塗敷法、輥塗法、流動(flow)塗敷法、刮板塗敷法、滴塗法(dispensing)、凹版印刷法或柔版印刷法填充所述導電墨，但並不限於此。 In the step a), an inkjet method, a flat screen printing method, a spin coating method, a roll coating method, a flow coating method, a blade coating method, a dispensing method, or the like may be employed. The conductive ink is filled by a gravure printing method or a flexographic printing method, but is not limited thereto.

在所述步驟b)中，所述蝕刻液可包含選自氨基甲酸銨系、碳酸銨系、碳酸氫銨系、羧酸系、內酯系、內醯胺系、環狀酸酐系化合物、酸-鹼鹽複合物、酸-鹼-醇類複合物及巰基類化合物中的一種以上的物質和氧化劑。但並不限於此，只要是能夠溶解金屬物質的蝕刻液均可適用。 In the step b), the etching solution may be selected from the group consisting of ammonium carbamate, ammonium carbonate, ammonium hydrogencarbonate, carboxylic acid, lactone, lactam, cyclic anhydride, and acid. - one or more of an alkali salt complex, an acid-base-alcohol complex, and a mercapto compound, and an oxidizing agent. However, it is not limited thereto, and any etching liquid capable of dissolving a metal substance can be applied.

在所述步驟b)中，可採用平板絲網印刷法、旋轉塗敷法、輥塗法、流動塗敷法、刮板塗敷法、凹版印刷法或柔版印刷法塗敷所述蝕刻液，溶解殘留在所述基材表面上的導電墨，並將所述導電墨引導至所述槽中。但塗敷方法並不限於此。 In the step b), the etching solution may be applied by a flat screen printing method, a spin coating method, a roll coating method, a flow coating method, a blade coating method, a gravure printing method or a flexographic printing method. Dissolving a conductive ink remaining on the surface of the substrate and guiding the conductive ink into the groove. However, the coating method is not limited to this.

在所述步驟b)中，可在殘留有所述導電墨的所述基材的表面上塗敷所述蝕刻液，以溶解所述導電墨，並通過物理力將被所述蝕刻液溶解的所述導電墨推入並填充於所述槽中。 In the step b), the etching liquid may be applied on the surface of the substrate on which the conductive ink remains to dissolve the conductive ink, and dissolve the etching liquid by physical force. The conductive ink is pushed in and filled in the groove.

在所述步驟b)之後，可選擇性地進一步包括進行發黑處理的發黑步驟。 After the step b), the blackening step of performing the blackening treatment may be optionally further included.

在所述發黑步驟中，可通過使用酸或鹼溶液的化學處理法、 鍍覆法或者使用發黑組合物印刷表面的方法進行發黑處理。但並不限於此，只要是能夠使由導電墨形成的圖案發黑的方法，可適用各種方法。 In the blackening step, by chemical treatment using an acid or alkali solution, The blackening treatment is carried out by a plating method or a method of printing a surface using a blackening composition. However, it is not limited thereto, and various methods can be applied as long as it is a method capable of blackening a pattern formed of conductive ink.

所述使用發黑組合物印刷表面的方法可採用平板絲網印刷法、輥塗法、流動塗敷法、刮板塗敷法、凹版印刷法或柔版印刷法，但並不限於此。 The method of printing the surface using the blackening composition may be, for example, a flat screen printing method, a roll coating method, a flow coating method, a blade coating method, a gravure printing method or a flexographic printing method, but is not limited thereto.

所述發黑組合物可包括鈦系或鋯系錯合物，但並不限於此，只要是能夠使表面發黑的物質，均可適用。 The blackening composition may include a titanium-based or zirconium-based complex, but is not limited thereto, and any material can be used as long as it can blacken the surface.

本發明的另一實施例提供一種導電膜，包括：具有槽的基材；填充於所述槽內，並由導電墨形成的膜；以及填充於所述槽內的所述膜上，由蝕刻液和所述導電墨混合而形成的混合體。 Another embodiment of the present invention provides a conductive film comprising: a substrate having a groove; a film filled in the groove and formed of a conductive ink; and the film filled in the groove, etched A mixture of a liquid and the conductive ink mixed.

所述膜的厚度可小於所述槽的深度。 The thickness of the film can be less than the depth of the groove.

所述膜及混合體的厚度之和可等於或小於所述槽的深度。 The sum of the thicknesses of the film and the mixture may be equal to or less than the depth of the groove.

可進一步包括發黑部，所述發黑部由填充於所述槽內的所述膜及混合體中的至少一個上面的發黑組合物形成。 A blackening portion may be further included, the blackening portion being formed of a blackening composition on at least one of the film and the mixture filled in the groove.

所述發黑部可設置在所述槽的內表面與所述膜及混合體中的至少一個之間。 The blackening portion may be disposed between an inner surface of the groove and at least one of the film and the mixture.

本發明的另一實施例提供一種導電圖案，包括：一次圖案部，其由填充於具有槽的基材上的所述槽內的導電墨形成；以及二次圖案部，其通過採用蝕刻液溶解在形成所述一次圖案部時殘留在所述基材表面的導電墨，並將所述導電墨填充於所述槽中而形成。 Another embodiment of the present invention provides a conductive pattern comprising: a primary pattern portion formed of conductive ink filled in the groove on a substrate having a groove; and a secondary pattern portion which is dissolved by using an etching solution The conductive ink remaining on the surface of the substrate at the time of forming the primary pattern portion is formed by filling the conductive ink in the groove.

所述導電墨可為包含金屬錯合物、金屬前體、球形金屬粒子、金屬薄片或奈米粒子的導電墨。 The conductive ink may be a conductive ink comprising a metal complex, a metal precursor, a spherical metal particle, a metal flake or a nano particle.

所述蝕刻液可包含選自氨基甲酸銨系、碳酸銨系、碳酸氫銨系、羧酸系、內酯系、內醯胺系、環狀酸酐系化合物、酸-鹼鹽複合物、酸-鹼-醇類複合物及巰基類化合物中的一種以上的物質和氧化劑。 The etching solution may be selected from the group consisting of ammonium carbamate, ammonium carbonate, ammonium hydrogencarbonate, carboxylic acid, lactone, lactam, cyclic anhydride, acid-base complex, acid- One or more of an alkali-alcohol complex and a mercapto compound and an oxidizing agent.

所述二次圖案部可通過將所述蝕刻液塗敷於所述基材的表 面，溶解殘留在所述基材的表面上的導電墨，並通過物理力將被所述蝕刻液溶解的所述導電墨推入所述槽中而形成。 The secondary pattern portion may be coated on the substrate by applying the etching solution The surface dissolves the conductive ink remaining on the surface of the substrate, and is formed by physically pushing the conductive ink dissolved by the etching solution into the groove.

並且，可進一步包括由填充於所述槽中的發黑組合物形成的發黑部。 Also, a blackening portion formed of a blackening composition filled in the groove may be further included.

本發明的另一實施例提供一種透明導電膜，其特徵在於，包括：具有槽的基材；以及由填充於所述槽中的導電墨形成的導電圖案，且所述導電圖案包括：一次圖案部，其由一次填充於所述槽中的導電墨形成；以及二次圖案部，其通過採用蝕刻液溶解在進行所述一次填充時殘留在所述基材表面的導電墨，並將所述導電墨二次填充於所述槽中而形成。 Another embodiment of the present invention provides a transparent conductive film, comprising: a substrate having a groove; and a conductive pattern formed of conductive ink filled in the groove, and the conductive pattern includes: a primary pattern a portion formed of conductive ink once filled in the groove; and a secondary pattern portion that dissolves conductive ink remaining on the surface of the substrate when the primary filling is performed by using an etching solution, and A conductive ink is formed by being secondarily filled in the groove.

本發明的另一實施例提供一種透明導電膜，其特徵在於，包括：具有槽的基材；以及導電圖案，其在所述槽中一次填充導電墨，並採用蝕刻液溶解在進行所述導電墨的一次填充時殘留在所述基材的表面的導電墨，並將所述導電墨引導至所述槽中，從而在所述槽中二次填充所述導電墨而形成。 Another embodiment of the present invention provides a transparent conductive film, comprising: a substrate having a groove; and a conductive pattern filled with conductive ink at a time in the groove and dissolved by the etching solution to perform the conductive A conductive ink remaining on the surface of the substrate at the time of primary filling of the ink, and the conductive ink is guided into the groove to be formed by secondary filling the conductive ink in the groove.

所述導電墨可為包含金屬錯合物、金屬前體、球形金屬粒子、金屬薄片或奈米粒子的導電墨。 The conductive ink may be a conductive ink comprising a metal complex, a metal precursor, a spherical metal particle, a metal flake or a nano particle.

所述蝕刻液可包含選自氨基甲酸銨系、碳酸銨系、碳酸氫銨系、羧酸系、內酯系、內醯胺系、環狀酸酐系化合物、酸-鹼鹽複合物、酸-鹼-醇類複合物及巰基類化合物中的一種以上的物質和氧化劑。 The etching solution may be selected from the group consisting of ammonium carbamate, ammonium carbonate, ammonium hydrogencarbonate, carboxylic acid, lactone, lactam, cyclic anhydride, acid-base complex, acid- One or more of an alkali-alcohol complex and a mercapto compound and an oxidizing agent.

所述二次圖案部可通過將所述蝕刻液塗敷於所述基材的表面，溶解殘留在所述基材的表面上的導電墨，並通過物理力將被所述蝕刻液溶解的所述導電墨推入所述槽中而形成。 The secondary pattern portion may dissolve the conductive ink remaining on the surface of the substrate by applying the etching solution to the surface of the substrate, and dissolve the etching solution by physical force The conductive ink is formed by pushing into the groove.

所述導電圖案可通過將所述蝕刻液塗敷於所述基材的表面，溶解殘留在所述基材的表面上的導電墨，並通過物理力將被所述蝕刻液溶解的所述導電墨推入所述槽中，進行二次填充而形成。 The conductive pattern may dissolve the conductive ink remaining on the surface of the substrate by applying the etching solution to the surface of the substrate, and dissolve the conductive liquid by the etching liquid by physical force. The ink is pushed into the groove and formed by secondary filling.

並且，可進一步包括由填充於所述槽中的發黑組合物形成的 發黑部。 And, further comprising a blackening composition filled in the groove Black hair.

根據本發明，提供一種先前技術難以實現的低電阻超細圖案的形成方法，其是通過在基材的槽中填充導電墨形成導電圖案，並且採用蝕刻液溶解殘留在基材的表面的導電墨並將所述導電墨推入並填充於基材的槽中而實現的。並且，上述方法能夠提高基材的透明性和絕緣特性。 According to the present invention, there is provided a method of forming a low-resistance ultra-fine pattern which is difficult to realize in the prior art, which is formed by filling a conductive ink in a groove of a substrate to form a conductive pattern, and using an etching solution to dissolve a conductive ink remaining on a surface of the substrate This is achieved by pushing and filling the conductive ink into the grooves of the substrate. Further, the above method can improve the transparency and insulating properties of the substrate.

1‧‧‧基材 1‧‧‧Substrate

2‧‧‧第一膜 2‧‧‧First film

3‧‧‧導電膏 3‧‧‧Electrical paste

4‧‧‧模具 4‧‧‧Mold

7‧‧‧擠壓件 7‧‧‧Extrusion

8‧‧‧第四膜 8‧‧‧fourth film

21‧‧‧槽 21‧‧‧ slots

22‧‧‧上表面 22‧‧‧ upper surface

31‧‧‧第二膜 31‧‧‧Second film

32‧‧‧第三膜 32‧‧‧ Third film

33‧‧‧第一混合體 33‧‧‧ first hybrid

34‧‧‧第二混合體 34‧‧‧Second mixture

35‧‧‧第三混合體 35‧‧‧ third hybrid

41‧‧‧突出部 41‧‧‧Protruding

81‧‧‧第五膜 81‧‧‧ Fifth film

21'‧‧‧槽 21'‧‧‧ slot

41'‧‧‧突出部 41'‧‧‧Protruding

A‧‧‧步驟 A‧‧‧Steps

圖1a至圖1f為按順序表示本發明的一實施例的導電圖案形成方法的剖視圖。 1a to 1f are cross-sectional views showing, in order, a method of forming a conductive pattern according to an embodiment of the present invention.

圖2a至圖2g為按順序表示本發明的另一實施例的導電圖案形成方法的剖視圖。 2a to 2g are cross-sectional views showing, in order, a method of forming a conductive pattern according to another embodiment of the present invention.

圖3為圖2g的A部分的放大剖視圖。 Figure 3 is an enlarged cross-sectional view of a portion A of Figure 2g.

圖4a及圖4b為表示本發明的另一實施例的導電圖案形成方法的部分步驟的剖視圖。 4a and 4b are cross-sectional views showing a part of steps of a method of forming a conductive pattern according to another embodiment of the present invention.

圖5a至圖5c為表示本發明的另一實施例的導電圖案形成方法的部分步驟的剖視圖。 5a to 5c are cross-sectional views showing a part of steps of a method of forming a conductive pattern according to another embodiment of the present invention.

圖6a至圖6c為實施例1~36的掃描電子顯微鏡(SEM)圖片。 6a to 6c are scanning electron microscope (SEM) images of Examples 1 to 36.

本發明提供一種導電圖案的形成方法，其特徵在於，包括步驟：a)在具有槽的基材的所述槽中填充導電墨；以及b)在填充所述導電墨時，用蝕刻液溶解殘留在所述基材的表面的導電墨，並將所述導電墨引導至所述槽中，從而在所述槽中填充所述導電墨。 The present invention provides a method of forming a conductive pattern, comprising the steps of: a) filling a conductive ink in the groove of a substrate having a groove; and b) dissolving the residue in an etching solution when filling the conductive ink Conductive ink on the surface of the substrate and directing the conductive ink into the grooves to fill the grooves with the conductive ink.

在所述步驟a)中，基材的種類不受特別的限制。所述基材可由透明材質，例如塑膠薄膜或玻璃形成。所述塑膠薄膜可使用聚醯亞胺(PI)、聚對苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)、聚醚碸(PES)、尼龍(Nylon)、聚四氟乙烯(PTFE)、 聚醚醚酮(PEEK)、聚碳酸鹽(PC)或聚芳酯(PAR)。基材也可由不透明材質構成。例如，可採用表面經絕緣處理的金屬製板材，或者可適用不透明的塑膠薄膜、不透明的玻璃或不透明的玻璃纖維材料。如上所述，可使用塑膠薄膜或玻璃基板等，但並且不受限制。此外，可根據後述導電墨的熱處理溫度，可配合基材特性而選擇使用。 In the step a), the kind of the substrate is not particularly limited. The substrate may be formed of a transparent material such as a plastic film or glass. The plastic film can use polyimine (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether oxime (PES), nylon (Nylon). , polytetrafluoroethylene (PTFE), Polyetheretherketone (PEEK), polycarbonate (PC) or polyarylate (PAR). The substrate can also be constructed of an opaque material. For example, a metal plate having an insulating surface may be used, or an opaque plastic film, an opaque glass or an opaque fiberglass material may be used. As described above, a plastic film or a glass substrate or the like can be used, but is not limited. Further, it can be selected and used depending on the heat treatment temperature of the conductive ink to be described later.

如上所述，本發明的導電圖案的形成方法，可不僅在樹脂層，而且還可在玻璃或陶瓷等基材上用各種方法形成陰刻槽，填充導電墨而形成導電圖案後，用蝕刻液溶解未填充於槽中而殘留在表面上的填充物質，並且再次填充所述填充物質而製造導電圖案。其中，當基材為陶瓷時，可使用雷射進行蝕刻，或者採用壓印方式對可塑性陶瓷片進行擠壓成型，後進行熱處理而製造。例如，可在基材表面上形成絕緣物質的樹脂層，例如可採用UV固化型或熱固化型樹脂形成樹脂層。所述樹脂並不僅限於此，還可由無機膜、有機-無機混合膜、有機層壓膜、無機層壓膜、或者有機-無機複合層壓膜所構成。當所述基材為透明材質時，所述樹脂層優選由透明絕緣物質形成，但並不僅限於此。 As described above, the method for forming the conductive pattern of the present invention can form the negative groove by various methods not only on the resin layer but also on a substrate such as glass or ceramic, filling the conductive ink to form a conductive pattern, and then dissolving it with an etching solution. A filling substance that is not filled in the groove to remain on the surface, and the filling substance is again filled to produce a conductive pattern. Wherein, when the substrate is ceramic, the laser may be etched, or the plastic ceramic sheet may be extrusion-molded by embossing, and then heat-treated. For example, a resin layer of an insulating material may be formed on the surface of the substrate, and for example, a resin layer may be formed using a UV curable type or a thermosetting type resin. The resin is not limited thereto, and may be composed of an inorganic film, an organic-inorganic hybrid film, an organic laminate film, an inorganic laminate film, or an organic-inorganic composite laminate film. When the substrate is a transparent material, the resin layer is preferably formed of a transparent insulating material, but is not limited thereto.

如上所述，在所述步驟a)之前在所述基材上形成槽的步驟中，可根據所要實現的微細線寬的大小，選擇使用通過壓印工藝將UV固化樹脂或熱固化樹脂用模具壓印而形成的方法、通過雷射直接蝕刻基材而形成使用的方法或者通過照相平版印刷方式形成的方法等。 As described above, in the step of forming a groove on the substrate before the step a), depending on the size of the fine line width to be realized, it is possible to selectively use a mold for UV-curing resin or thermosetting resin by an imprint process. A method of forming by embossing, a method of directly etching a substrate by laser, a method of using it, a method of forming by photolithography, or the like.

其中，對壓印工藝具體說明如下。在壓印工藝中代表性的方式為通過熱工藝和由UV照射引起的固化的圖案轉印方式。首先，為了進行壓印工藝，需要圖章，所述圖章表面突出有所需的圖案，為了製造陽刻有這種圖案的圖章，一般通過電子束平印術(electron-beam lithography)和乾式蝕刻而製造。 Among them, the imprint process is specifically described as follows. A representative manner in the imprint process is a pattern transfer method of curing by a thermal process and by UV irradiation. First of all, in order to carry out the imprint process, a stamp is required, which protrudes from the surface with a desired pattern. In order to manufacture a stamp with such a pattern, it is generally manufactured by electron-beam lithography and dry etching. .

具體地說，是一種在基材上利用具有微細凹凸的模具壓印UV 固化樹脂或固化型樹脂的樹脂層，從而形成陰刻的微槽的工藝。上述工藝還可使用熱塑性基材，並將微細凹凸高溫加壓，從而形成陰刻的微槽。 Specifically, it is a method of imprinting UV on a substrate using a mold having fine concavities and convexities. A process of curing a resin layer of a resin or a curable resin to form an intaglio microgroove. The above process can also use a thermoplastic substrate and pressurize the fine concavo-convex at a high temperature to form an intaglio microgroove.

其次，在所述步驟a)中，例如作為包含金屬錯合物、金屬前體、球形金屬粒子、金屬薄片或奈米粒子的導電墨，可將導電膏填充於陰刻的槽中。 Next, in the step a), for example, as a conductive ink containing a metal complex, a metal precursor, a spherical metal particle, a metal foil or a nanoparticle, a conductive paste may be filled in an intaglio groove.

為了提高微槽中的填充性，可使用金屬錯合物或金屬前體。此外，也可將金屬錯合物或金屬前體還原，製備成奈米大小的金屬粒子，並作為混合物使用。如果使用該物質，能夠容易形成先前技術不能形成的奈米大小的微細導電圖案。除了這些混合物之外，也可根據需要包含如溶劑、穩定劑、分散劑、黏合劑樹脂(binder resin)、離型劑、還原劑、表面活性劑(surfactant)、潤濕劑(wetting agent)、觸變劑(thixotropic agent)、均化劑(levelling)或增黏劑的添加劑等。 In order to increase the filling property in the microgroove, a metal complex or a metal precursor can be used. Further, a metal complex or a metal precursor may be reduced to prepare nano-sized metal particles and used as a mixture. If this substance is used, it is possible to easily form a nano-sized fine conductive pattern which cannot be formed by the prior art. In addition to these mixtures, as needed, a solvent, a stabilizer, a dispersant, a binder resin, a release agent, a reducing agent, a surfactant, a wetting agent, or the like may be contained. A thixotropic agent, a levelling or an additive to a tackifier.

作為本發明中使用的金屬錯合物，通過與選自氨基甲酸銨系化合物、碳酸銨系化合物、碳酸氫銨系化合物、羧酸系化合物、內酯系化合物、內醯胺系化合物或環狀酸酐系化合物、酸-鹼鹽複合物和酸-鹼-醇系複合物中的一種或兩種以上的混合物進行反應，從而製備成能夠溶解於溶劑中的金屬錯合物而使用。 The metal complex used in the present invention is selected from a group consisting of an ammonium carbamate-based compound, an ammonium carbonate-based compound, an ammonium hydrogencarbonate-based compound, a carboxylic acid-based compound, a lactone-based compound, an intrinsic amine-based compound, or a cyclic ring. One or a mixture of two or more of an acid anhydride-based compound, an acid-base salt complex, and an acid-base-alcohol complex is reacted to prepare a metal complex which can be dissolved in a solvent.

在本發明中使用的金屬前體可由通式MnX表示，其中M表示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或Bi；n表示1~10的整數；X表示氧、硫磺、鹵素、氰基(cyano)、氰酸鹽、碳酸鹽、硝酸鹽、亞硝酸鹽、硫酸鹽、磷酸鹽、硫氰酸鹽、氯酸鹽、高氯酸鹽()、四氟硼酸鹽()、乙醯丙酮化物、巰基、醯胺、醇鹽或羧酸酯等。具體舉例來說，可以選擇使用一種以上的醋酸金、草酸鈀、2-乙基己酸銀、2-乙基己酸銅 、硬脂酸鐵、甲酸鎳或檸檬酸鋅等羧酸金屬、硝酸銀、氰化銅、碳酸鈷、氯化鉑、氯金酸、四丁氧基鈦、二甲氧基二氯化鋯、異 丙氧基 鋁、氧化 釩、甲醇 鉭、醋酸 鉍、 巰基金酸十二烷基酯()或乙醯丙酮 銦 等金屬化合物。 The metal precursor used in the present invention may be represented by the general formula MnX, wherein M represents 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 or Bi; n represents an integer of 1 to 10; X represents oxygen, sulfur, halogen, cyano, cyanic acid Salts, carbonates, nitrates, nitrites, sulfates, phosphates, thiocyanates, chlorates, perchlorates ( ), tetrafluoroborate ( ), acetoacetate, sulfhydryl, decylamine, alkoxide or carboxylate. For example, more than one type of carboxylic acid metal such as gold acetate, palladium oxalate, silver 2-ethylhexanoate, copper 2-ethylhexanoate, iron stearate, nickel formate or zinc citrate, silver nitrate may be used. , copper cyanide, cobalt carbonate, platinum chloride, chloroauric acid, titanium tetrabutoxide, dimethoxyzirconium dichloride, aluminum isopropoxide, vanadium oxide, methanol hydrazine, cesium acetate, hydrazine acid Dialkyl ester Or a metal compound such as acetonitrile indium.

常規的金屬奈米粒子的製備方法包括以物理方式研磨金屬塊從而進行製備的物理方法和以化學方式製備的方法。對化學方法進行具體說明，其包括：噴射高壓氣體製備粉末的氣溶膠法；使用金屬化合物和氣體還原劑，通過熱分解方式製備粉末的熱解法；對蒸發原料進行加熱蒸發，從而製備粉末的蒸發凝縮法；溶膠-凝膠法、水熱合成法、超聲波合成法、微乳液法和液相還原法等。利用分散劑和還原劑進行製備的液相還原法，由於容易控制奈米粒子的形成，且經濟效果最佳，因此是使用最為廣泛的方法。但在本發明中，只要能夠形成奈米粒子，所有方法均可使用。 The preparation method of the conventional metal nanoparticle includes a physical method of physically grinding a metal block to perform preparation and a method of chemically preparing. The chemical method is specifically described, which comprises: an aerosol method for preparing a powder by spraying a high-pressure gas; a pyrolysis method for preparing a powder by a thermal decomposition method using a metal compound and a gas reducing agent; and heating and evaporating the evaporated raw material to prepare evaporation of the powder Condensation method; sol-gel method, hydrothermal synthesis method, ultrasonic synthesis method, microemulsion method and liquid phase reduction method. The liquid phase reduction method prepared by using a dispersant and a reducing agent is the most widely used method because it is easy to control the formation of nanoparticles and has the best economic effect. However, in the present invention, all methods can be used as long as the nanoparticles can be formed.

在本申請人提出的韓國專利申請第2006-0074246號中記載了關於液相還原法製備奈米粒子的方法的具體說明。上述專利申請中記載的金屬奈米粒子具有粒子大小均勻，凝聚性降至最小化的優點，而含有上述金屬奈米粒子的導電墨具有即使在150℃以下的低溫條件下，進行短時間的燒成，也可輕易形成具有高導電率的均勻且緻密的薄膜或微細圖案的優點。 A detailed description of a method for preparing nanoparticles by a liquid phase reduction method is described in Korean Patent Application No. 2006-0074246 filed by the present applicant. The metal nanoparticles described in the above patent application have the advantages of uniform particle size and minimized cohesiveness, and the conductive ink containing the above metal nanoparticles has a short-time burning even at a low temperature of 150 ° C or lower. The advantage of a uniform and dense film or fine pattern having high conductivity can also be easily formed.

在所述步驟a)中用於導電墨的黏合劑樹脂優選與各種基材的具有優異的附著力的黏合劑樹脂。可使用的物質為有機高分子物質，例如可以是聚丙烯、聚碳酸鹽、聚丙烯酸酯、聚甲基丙烯酸甲酯、醋酸纖維素、聚氯乙烯、聚氨酯、聚酯、醇酸樹脂、環氧樹脂、苯氧樹脂、密胺樹脂、酚醛樹脂、酚醛改性醇酸樹脂、環氧改性醇酸樹脂、乙烯改性醇酸樹脂、矽改性醇酸樹脂、丙烯酸三聚氰胺樹脂()、聚異氰酸鹽樹脂和環氧酯樹脂等，只要符合本發明，就不限於此。在所述步驟a)中使用的導 電墨中，即使在沒有黏合劑的情況下也可使用Ag錯合物或奈米粒子，因此並不僅限於上述內容。 The binder resin for the conductive ink in the step a) is preferably an adhesive resin having excellent adhesion to various substrates. The substance that can be used is an organic high molecular substance, and may be, for example, polypropylene, polycarbonate, polyacrylate, polymethyl methacrylate, cellulose acetate, polyvinyl chloride, polyurethane, polyester, alkyd, epoxy. Resin, phenoxy resin, melamine resin, phenolic resin, phenolic modified alkyd resin, epoxy modified alkyd resin, ethylene modified alkyd resin, cerium modified alkyd resin, melamine acrylate resin ( The polyisocyanate resin, the epoxy ester resin, and the like are not limited thereto as long as they conform to the present invention. Among the conductive inks used in the step a), Ag complexes or nanoparticles can be used even in the absence of a binder, and thus are not limited to the above.

此外，為了形成均勻的薄膜，有時需要溶劑，可使用的溶劑，可以是乙醇、異丙醇或丁醇等醇類；乙二醇或丙三醇等二醇類；醋酸乙酯、醋酸丁酯、甲氧基乙酸丙酯、卡必醇醋酸酯或乙基卡必醇醋酸酯等醋酸酯類；甲基溶纖劑、丁基溶纖劑、二***、四氫呋喃或二氧雜環乙烷等醚類；甲乙酮、丙酮、二甲基甲醯胺或1-甲基-2-吡咯烷酮等酮類；己烷、庚烷、月桂烷、石蠟油或礦物油精等烴類；苯、甲苯或二甲苯等芳香族；以及氯仿、二氯甲烷或四氯化碳等鹵代溶劑；乙腈；二甲亞碸；或者上述物質的混合溶劑等。但溶劑的種類並不僅限於此。 Further, in order to form a uniform film, a solvent may be required, and a solvent which may be used may be an alcohol such as ethanol, isopropanol or butanol; a glycol such as ethylene glycol or glycerin; ethyl acetate or butyl acetate; Esters such as esters, propyl methoxyacetate, carbitol acetate or ethyl carbitol acetate; ethers such as methyl cellosolve, butyl cellosolve, diethyl ether, tetrahydrofuran or dioxane Ketones such as methyl ethyl ketone, acetone, dimethylformamide or 1-methyl-2-pyrrolidone; hydrocarbons such as hexane, heptane, decane, paraffin oil or mineral oil; benzene, toluene or xylene Equivalent aromatic; and halogenated solvent such as chloroform, dichloromethane or carbon tetrachloride; acetonitrile; dimethyl hydrazine; or a mixed solvent of the above. However, the type of solvent is not limited to this.

在所述步驟a)中，導電墨的填充方法例如可以使用平板絲網印刷、旋轉(spin)塗敷、輥(roll)塗、流動(flow)塗敷、刮板(doctor blade)塗敷、滴塗(dispensing)、凹版印刷或柔版(flexography)印刷方法，但並不僅限於此，且此時進行的填充次數可為一次或者反復填充多次。根據所述不同的填充方法，可能會導致填充特性互不相同，其需要調節導電墨的成分，使組合物的流變能力最適於填充方法，從而使導電墨適於各填充方法。根據不同的金屬組合物的金屬含量、溶劑含量及揮發溫度、黏度和觸變性的特性，可能會產生特性的差異。 In the step a), the filling method of the conductive ink may be, for example, a flat screen printing, a spin coating, a roll coating, a flow coating, a doctor blade coating, The method of dispensing, gravure printing or flexography printing is not limited thereto, and the number of fillings performed at this time may be one time or repeated multiple times. According to the different filling methods, the filling characteristics may be different from each other, and it is necessary to adjust the composition of the conductive ink so that the rheology of the composition is most suitable for the filling method, thereby making the conductive ink suitable for each filling method. Depending on the metal content, solvent content, and volatilization temperature, viscosity, and thixotropic properties of the different metal compositions, differences in characteristics may occur.

通過上述方法形成的導電圖案的厚度優選等於或小於陰刻的圖案深度，但並不限於此。根據後處理工藝條件，有時也可優選導電圖案的厚度厚於圖案的深度，從而提高與上部電路之間的接觸力。具體地說，優選為10μm以下，更加優選為0.1μm以上且5μm以下。根據所要實現的線寬、所需電阻及後處理條件，需要對導電圖案的厚度進行調節。導電圖案的乾燥溫度可為22~600℃，也可優選為80~400℃，但並不僅限於此。可根據基材種類，優選在不導致基材變形的溫度範圍內進行。 The thickness of the conductive pattern formed by the above method is preferably equal to or less than the depth of the intaglio pattern, but is not limited thereto. Depending on the post-processing conditions, it is sometimes preferable that the thickness of the conductive pattern is thicker than the depth of the pattern, thereby increasing the contact force with the upper circuit. Specifically, it is preferably 10 μm or less, and more preferably 0.1 μm or more and 5 μm or less. The thickness of the conductive pattern needs to be adjusted depending on the line width to be achieved, the required resistance, and post-processing conditions. The drying temperature of the conductive pattern may be 22 to 600 ° C, or preferably 80 to 400 ° C, but is not limited thereto. It can be carried out in a temperature range which does not cause deformation of the substrate, depending on the kind of the substrate.

所述步驟b)是使用蝕刻液溶解在所述步驟a)中填充導電墨時不可避免地殘留在所述基材表面上的導電墨，引導所述導電墨進入槽中，從而使留在基材表面的墨也都進入槽中形成導電圖案的步驟，不僅如此，還是去除留在基材表面的導電墨，從而洗淨表面的步驟。本步驟還是改善表面的透明性和絕緣性特性的同時，進一步使導電墨流入槽中，完成導電圖案，從而完成低電阻微細導電圖案的步驟。 The step b) is to use an etching solution to dissolve the conductive ink which inevitably remains on the surface of the substrate when the conductive ink is filled in the step a), and guide the conductive ink into the groove, thereby leaving the base The ink on the surface of the material also enters the groove to form a conductive pattern, and not only the step of removing the conductive ink remaining on the surface of the substrate, thereby washing the surface. This step is also a step of further improving the transparency and insulating properties of the surface while further flowing the conductive ink into the groove to complete the conductive pattern, thereby completing the low-resistance fine conductive pattern.

導電墨的蝕刻機制一般是反復執行一下過程而構成：即，由氧化劑對金屬表面進行氧化，形成金屬氧化物，並利用溶解上述金屬氧化物的化合物來溶解的過程和膨潤過程。 The etching mechanism of the conductive ink is generally constituted by repeatedly performing a process of oxidizing a metal surface by an oxidizing agent to form a metal oxide, and a process of dissolving and a swelling process by using a compound which dissolves the metal oxide.

作為最符合所述導電墨的蝕刻特性的蝕刻組合物，可包含氧化劑和能夠溶解金屬化合物的氨基甲酸銨系、碳酸銨系、碳酸氫銨系、羧酸系、內酯系、內醯胺系、環狀酸酐系化合物、酸-鹼鹽複合物、酸-鹼-醇系複合物或巰基類化合物等而製備。例如，可在沒有溶劑的常壓或加壓條件下，直接使氧化劑與一種以上的所述化合物及其混合物進行反應，或者在使用溶劑的情況下，可使用水；甲醇、異丙醇、丁醇或乙醇胺等醇類；乙二醇或丙三醇等二醇類；醋酸乙酯、醋酸丁酯或卡必醇醋酸酯等醋酸酯類；二***、四氫呋喃或二氧雜環乙烷等醚類；甲乙酮或丙酮等酮類；己烷或庚烷等烴類；苯或甲苯等芳香族；以及氯仿、二氯甲烷或四氯化碳等氯代溶劑；全氟化碳等氟類溶劑或者上述物質的混合溶劑等。在如壓力容器等的加壓狀態下還可使用低沸點的氟類溶劑或液化二氧化碳等。對本發明的蝕刻組合物的製備方法沒有特別的限制。即，只要符合本發明的目的，可使用任何習知的技術。 The etching composition which best satisfies the etching characteristics of the conductive ink may include an oxidizing agent and an ammonium carbamate-based, ammonium carbonate-based, ammonium hydrogencarbonate-based, carboxylic acid-based, lactone-based, or indoleamine-based system capable of dissolving a metal compound. It is prepared by a cyclic acid anhydride compound, an acid-base salt complex, an acid-base-alcohol complex, or a mercapto compound. For example, the oxidizing agent can be directly reacted with one or more of the compounds and mixtures thereof under normal or pressurized conditions without a solvent, or in the case of using a solvent, water; methanol, isopropanol, butyl Alcohols such as alcohol or ethanolamine; glycols such as ethylene glycol or glycerol; acetates such as ethyl acetate, butyl acetate or carbitol acetate; ethers such as diethyl ether, tetrahydrofuran or dioxane a ketone such as methyl ethyl ketone or acetone; a hydrocarbon such as hexane or heptane; an aromatic such as benzene or toluene; and a chlorinated solvent such as chloroform, dichloromethane or carbon tetrachloride; or a fluorine solvent such as perfluorocarbon or a mixed solvent of the above substances. A low boiling point fluorine-based solvent or liquefied carbon dioxide or the like can also be used under a pressurized state such as a pressure vessel. There is no particular limitation on the preparation method of the etching composition of the present invention. That is, any conventional technique can be used as long as it is in accordance with the purpose of the present invention.

在本申請人的韓國授權專利第0727466號中，對其中的氨基甲酸銨系化合物、碳酸銨系化合物及碳酸氫銨系化合物進行了具體的說明。羧酸系化合物可使用苯甲酸、油酸、丙酸、丙二酸、己酸、辛酸、癸酸、新癸酸、草酸、檸檬酸、水楊酸、硬脂酸、 丙烯酸、琥珀酸、己二酸、乙醇酸、異丁酸或抗壞血酸等。巰基類化合物可使用1-甲硫醇(1-)、1-乙硫醇、2-丁硫醇、1-庚硫醇、1-辛硫醇、1-癸硫醇、1-十六烷基硫醇、硫代乙酸、6-巰基己酸、硫代苯甲酸、糠硫醇、環己硫醇、11-巰基-1十一醇、2-巰基乙醇、3-巰基-1-丙醇、硫代水楊酸、1-硫代甘油、2-萘硫酚、3-巰基丙酸甲酯或γ-巰基丙基三甲氧基矽烷等。內酯系化合物可使用β-丙酸內酯、γ-丙酸內酯、γ-丁酸內酯、γ-硫代丁酸內酯、α-甲基-γ-丁酸內酯、β-甲基-γ-丁酸內酯、γ-戊內酯、γ-己內酯、γ-辛酸內酯、δ-戊內酯、1,6-二氧雜螺[4.4]壬烷-2,7-二酮、α-亞甲基-γ-丁酸內酯、γ-亞甲基-γ-丁酸內酯、ε-己內酯、丙交酯、乙交酯、季酮酸、2(5氫)-呋喃酮、β-羥基-γ-丁酸內酯、甲瓦龍酸內酯、5,6-二氫-2H-吡喃-2-吡喃-2-酮、δ-戊內酯、ε-己內酯、γ-己內酯或γ-辛酸內酯等。內醯胺系化合物可使用2-氮雜環丁酮(2-)、2-吡咯烷酮、5-甲氧基-2-吡咯烷酮、5-甲基-2-吡咯烷酮、N-甲基已內醯胺、2-氮雜環壬酮(2-)或N-乙醯基己內醯胺等。环状酸酐可使用衣康酸酐、琥珀酸酐、馬來酸酐、戊二酸酐、十八烷基琥珀酸酐()、2,2-二甲基琥珀酸酐、2-十二烯-1-基丁二酸酐(2--1 )、六氟戊二酸酐、3,3-二甲基戊二酸酐、3-乙基-3-甲基戊二酸酐、3,5-二乙醯基四氫吡喃-2,4,6-三酮(3,5- -2,4,6-)或二乙醇酸酐等，但並不僅限於此，上述物質可以做為單一成分使用，也可以由兩種以上的混合物構成的組中選擇使用。 The ammonium carbamate-based compound, the ammonium carbonate-based compound, and the ammonium hydrogencarbonate-based compound are specifically described in the Korean Patent No. 0727466 of the present applicant. As the carboxylic acid compound, benzoic acid, oleic acid, propionic acid, malonic acid, caproic acid, caprylic acid, capric acid, neodecanoic acid, oxalic acid, citric acid, salicylic acid, stearic acid, acrylic acid, succinic acid, or the like can be used. Diacid, glycolic acid, isobutyric acid or ascorbic acid. 1-methyl mercaptan (1-methyl mercaptan can be used) ), 1-ethanethiol, 2-butanethiol, 1-heptanethiol, 1-octylthiol, 1-decyl mercaptan, 1-hexadecyl mercaptan, thioacetic acid, 6-mercaptohexanoic acid , thiobenzoic acid, decyl mercaptan, cyclohexyl mercaptan, 11-fluorenyl-1 undecyl alcohol, 2-mercaptoethanol, 3-mercapto-1-propanol, thiosalicylic acid, 1-thioglycerol, 2-naphthylthiophenol, methyl 3-mercaptopropionate or γ-mercaptopropyltrimethoxydecane. As the lactone compound, β-propionolactone, γ-propionolactone, γ-butyrolactone, γ-thiobutyrolactone, α-methyl-γ-butyrolactone, β- can be used. Methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-octanolactone, δ-valerolactone, 1,6-dioxaspiro[4.4]decane-2, 7-diketone, α-methylene-γ-butyrolactone, γ-methylene-γ-butyrolactone, ε-caprolactone, lactide, glycolide, quaternary acid, 2 (5H)-furanone, β-hydroxy-γ-butyrolactone, mevalonolactone, 5,6-dihydro-2H-pyran-2-pyran-2-one, δ-pentyl Lactone, ε-caprolactone, γ-caprolactone or γ-octanolactone. The internal amidoxime compound can be used as 2-azetidinone (2- ), 2-pyrrolidone, 5-methoxy-2-pyrrolidone, 5-methyl-2-pyrrolidone, N-methyl indoleamine, 2-azacyclononanone (2- Or N-ethinyl caprolactam and the like. The cyclic anhydride can be used with itaconic anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, octadecyl succinic anhydride ( ), 2,2-dimethylsuccinic anhydride, 2-dodecen-1-yl succinic anhydride (2- -1 ), hexafluoroglutaric anhydride, 3,3-dimethylglutaric anhydride, 3-ethyl-3-methylglutaric anhydride, 3,5-diethylindenyltetrahydropyran-2,4,6 -trione (3,5- -2,4,6- Or the like, but not limited thereto, the above substances may be used as a single component, or may be selected from the group consisting of two or more kinds of mixtures.

關於所述蝕刻液，作為蝕刻組合物的主成分之一的氧化劑，例如可包括：氧氣、臭氧等氧化性氣體；過氧化氫、Na2O2、KO2、NaBO3、(NH4)S2O8、H2SO5或(CH3)3CO2H,(C6H5CO2)2等過氧化物；HCO3H、CH3CO3H、CF3CO3H、C6H5CO3H或m-ClC6H5-CO3H等 過氧酸；硝酸、硫酸、I2、Fe(NO3)3、Fe2(SO4)3、K3Fe(CN)6、(NH4)2Fe(SO4)2、Ce(NH4)4(SO4)4、NaIO4、KMnO4或K2CrO4等常見的氧化性無機酸，或者金屬或非金屬化合物等。在使用這種氧化劑時，可以單獨使用或者也可混合至少一種以上的氧化劑使用。 The oxidizing agent as one of the main components of the etching composition may include, for example, an oxidizing gas such as oxygen or ozone; hydrogen peroxide, Na 2 O 2 , KO 2 , NaBO 3 , (NH 4 )S. a peroxide such as 2 O 8 , H 2 SO 5 or (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 Peroxyacid such as H 5 CO 3 H or m-ClC 6 H 5 -CO 3 H; nitric acid, sulfuric acid, I 2 , Fe(NO 3 ) 3 , Fe 2 (SO 4 ) 3 , K 3 Fe(CN) 6 a common oxidizing inorganic acid such as (NH 4 ) 2 Fe(SO 4 ) 2 , Ce(NH 4 ) 4 (SO 4 ) 4 , NaIO 4 , KMnO 4 or K 2 CrO 4 , or a metal or non-metal compound, etc. . When such an oxidizing agent is used, it may be used singly or in combination of at least one kind of oxidizing agent.

關於所述蝕刻組合物，為了有效地溶解未被填充到基材的槽中而殘留在基材表面的導電墨，並且提高對微槽的再填充性，優選對蝕刻液組合物賦予親水特性。優選通過調節氨基甲酸銨系、碳酸銨系、碳酸氫銨系、羧酸系、內酯系、內醯胺系、環狀酸酐系、酸-鹼鹽複合物、酸-鹼-醇系複合物或巰基類化合物的碳原子數來調節親水特性的程度。 In the etching composition, in order to effectively dissolve the conductive ink remaining on the surface of the substrate without being filled in the groove of the substrate, and to improve the refillability to the microgroove, it is preferred to impart a hydrophilic property to the etching liquid composition. Preferably, the ammonium carbamate-based, ammonium carbonate-based, ammonium hydrogencarbonate-based, carboxylic acid-based, lactone-based, indoleamine-based, cyclic acid anhydride-based, acid-base complex, and acid-base-alcohol complex are adjusted. Or the degree of carbon number of the fluorenyl compound to adjust the degree of hydrophilicity.

所述蝕刻組合物的塗敷方法可從常規的平板絲網印刷、輥塗、流動(flow)塗敷、刮板(doctor blade)塗敷、凹版印刷或柔版(flexography)印刷方法等中選擇使用。但只要符合本發明的特徵，對其沒有需特別的限制。 The coating method of the etching composition can be selected from conventional flat screen printing, roll coating, flow coating, doctor blade coating, gravure printing or flexography printing methods, and the like. use. However, it is not particularly limited as long as it conforms to the features of the present invention.

關於所述蝕刻組合物的蝕刻速度，優選通過調節塗敷時的蝕刻劑的沉積時間，或者通過調節蝕刻組合物的氧化劑或氨基甲酸銨系、碳酸銨系、碳酸氫銨系、羧酸系、內酯系、內醯胺系、環狀酸酐系、酸-鹼鹽複合物、酸-鹼-醇系複合物或巰基類化合物的濃度對其進行控制，且必要時可反復進行蝕刻過程。此外，當使用包含無機酸或鹼的蝕刻液時，可使用額外的水或有機溶劑進行洗滌而去除。例如，也可再包括一次洗滌工序，從而將基材表面的導電墨導入槽中。 Regarding the etching rate of the etching composition, it is preferable to adjust the deposition time of the etchant at the time of coating, or to adjust the oxidizing agent of the etching composition or ammonium carbamate, ammonium carbonate, ammonium hydrogencarbonate, carboxylic acid, The concentration of the lactone system, the intrinsic amine system, the cyclic acid anhydride system, the acid-base salt complex, the acid-base-alcohol complex, or the sulfhydryl compound is controlled, and the etching process can be repeated as necessary. Further, when an etching solution containing a mineral acid or a base is used, it may be removed by washing with an additional water or an organic solvent. For example, a washing process may be further included to introduce the conductive ink on the surface of the substrate into the groove.

在本發明的導電圖案的形成方法中，在所述步驟b)以後，可進一步包括使導電圖案的表面發黑的發黑步驟。該步驟可根據需要選擇性地進行。 In the method of forming a conductive pattern of the present invention, after the step b), a blackening step of blackening the surface of the conductive pattern may be further included. This step can be selectively performed as needed.

在所述發黑步驟中，可使用發黑組合物對填充到槽中的導電圖案的表面進行薄膜塗敷，以對表面進行發黑處理，從而能夠控制金屬固有的反射特性，並且還可提高與基材之間的貼緊力。 In the blackening step, the surface of the conductive pattern filled in the groove may be subjected to film coating using a blackening composition to blacken the surface, thereby controlling the inherent reflection characteristics of the metal, and also improving The adhesion between the substrate and the substrate.

金屬表面的發黑一般是出於提高可見性的目的，可以採用通過酸或鹼溶液處理金屬層表面的方法、鍍覆方法或通過印刷方式印刷至金屬層表面的方法等。 The blackening of the metal surface is generally for the purpose of improving visibility, and a method of treating the surface of the metal layer by an acid or alkali solution, a plating method, a method of printing to the surface of the metal layer by printing, or the like can be employed.

其中，關於印刷方法說明如下：可以將對金屬表面進行發黑處理的同時能夠提高與基材之間的附著力的發黑組合物，利用平板絲網印刷、輥塗、流動(flow)塗敷、刮板(doctor blade)塗敷、凹版印刷或柔版(flexography)印刷法填充到導電圖案的表面上並進行發黑處理。發黑組合物的乾燥溫度一般優選為22~600℃，可在不導致基材變形的溫度範圍內進行乾燥。 Here, the printing method will be described as follows: a blackening composition capable of improving the adhesion to a substrate while blackening the metal surface can be applied by flat screen printing, roll coating, or flow coating. A doctor blade coating, a gravure printing or a flexography printing method is applied to the surface of the conductive pattern and subjected to a blackening treatment. The drying temperature of the blackening composition is generally preferably from 22 to 600 ° C, and can be dried in a temperature range which does not cause deformation of the substrate.

在本發明中可使用的發黑組合物包括鈦系或鋯系錯合物、溶劑、均化劑和增黏劑，且如果需要也可包括所述步驟a)中的導電墨。鈦系或鋯系錯合物具體可使用鈦酸異丙酯、鈦酸乙酯、鈦酸正丁酯、聚 鈦 酸正丁酯(poly-N-butyl titanate)、 鈦酸-2-乙基己酯、 鈦 酸正丙酯、 鈦 酸辛二醇酯( )、鈦酸四異辛酯、鈦酸木糖酯()單 體、鈦 酸木糖酯()聚合物、三乙醇胺 鈦酸酯、四乙醯丙酮 絡 鈦 、乙基乙醯乙酸乙酯 鈦酸酯()、異硬脂醯基鈦酸酯()、乳酸 鈦螯合物()、三乙醇胺鋯酸酯、乳酸鋯、乙二醇 鋯()、 鋯 酸正丁酯或 鋯酸正丙酯等。必要時，可將兩種以上的錯合物混合使用。在上述發黑組合物中，可通過調節鈦系或鋯系錯合物的濃度而調節導電圖案的表面黑化度。 The blackening composition usable in the present invention includes a titanium-based or zirconium-based complex, a solvent, a leveling agent, and a tackifier, and may include the conductive ink in the step a) if necessary. For the titanium or zirconium complex, specifically, isopropyl titanate, ethyl titanate, n-butyl titanate, poly-N-butyl titanate, and titanate-2-ethyl Hexyl ester, n-propyl titanate, octanediol titanate ( ), tetraisooctyl titanate, titanyl titanate ( Monomer, titanyl ester ( ) polymer, triethanolamine titanate, tetraethylguanidinium acetate titanium, ethyl acetonitrile ethyl acetate titanate ( ), isostearyl decyl titanate ( ), titanium lactate chelate ( ), triethanolamine zirconate, zirconium lactate, zirconium glycol ( ), n-butyl zirconate or n-propyl zirconate. If necessary, two or more complex compounds may be used in combination. In the above blackening composition, the degree of surface blackening of the conductive pattern can be adjusted by adjusting the concentration of the titanium-based or zirconium-based complex.

下面，將參照附圖具體說明本發明。雖然參照附圖對本發明進行說明，但其僅是示例性的，本領域中具備通常知識的技術人員能夠理解可由此進行各種變形並且實施等同的其他實施例。因此，本發明真正的保護範圍僅由所附的申請專利範圍所確定。 Hereinafter, the present invention will be specifically described with reference to the drawings. While the present invention has been described with respect to the embodiments of the embodiments of the present invention, it is to be understood by those of ordinary skill in the art. Therefore, the true scope of the invention is to be determined only by the scope of the appended claims.

圖1a至圖1f為按順序表示本發明的一實施例的導電圖案形成方法的剖視圖。 1a to 1f are cross-sectional views showing, in order, a method of forming a conductive pattern according to an embodiment of the present invention.

如圖1a所示，在基材1上形成第一膜2以作為樹脂層，之後，準備具有陽刻圖案的突出部41、41’的模具4。 As shown in Fig. 1a, a first film 2 is formed on the substrate 1 as a resin layer, and thereafter, a mold 4 having projections 41, 41' of a positive pattern is prepared.

將所述模具4配置在所述第一膜2的上面，使所述突出部41、41’與所述第一膜2相對，之後通過所述模具4加壓所述第一膜2，從而在第一膜2上印出如圖1b所示的槽21、21’。此時，所述第一膜2優選至少應使其中的被所述突出部41加壓的部分未固化，或者使之成為假固化狀態，從而順利實現使用模具4的壓印。 Arranging the mold 4 on the upper surface of the first film 2 such that the protruding portions 41, 41' are opposed to the first film 2, and then pressurizing the first film 2 through the mold 4, thereby Grooves 21, 21' as shown in Fig. 1b are printed on the first film 2. At this time, it is preferable that the first film 2 should at least partially cure the portion pressed by the protruding portion 41 or to be in a pseudo-cured state, thereby smoothly achieving imprinting using the mold 4.

在使用所述模具4進行壓印之後，可使所述第一膜2固化，但並不僅限於此。 After the imprinting is performed using the mold 4, the first film 2 may be cured, but is not limited thereto.

如圖1a所示，所述突出部41、41’可包括一部分的側剖面為四邊形的突出部41和一部分的側剖面為三角形的突出部41’。如圖1a所示，一個模具4可以包括側剖面為四邊形的突出部41和側剖面為三角形的突出部41’，但並不僅限於此。一個模具4可以只具備側剖面為四邊形的突出部41，也可以只具備側剖面為三角形的突出部41’。突出部的形狀也並不僅限於此，可為多種形狀。 As shown in Fig. 1a, the projections 41, 41' may include a portion of a projection 41 having a side cross section of a quadrangle and a portion of a projection 41' having a triangular cross section. As shown in Fig. 1a, a mold 4 may include a projection 41 having a side cross section and a projection 41' having a triangular cross section, but is not limited thereto. One of the molds 4 may have only the projecting portion 41 having a quadrangular cross section, or may have only the projecting portion 41' having a triangular cross section. The shape of the protruding portion is not limited thereto, and may be of various shapes.

如圖1b所示，根據所述突出部41、41’的形狀，所述槽21、21’可包括一部分的側剖面為四邊形的槽21和一部分的側剖面為三角形的槽21’。如圖1b所示，在一個第一膜2上可以混合形成側剖面為四邊形的槽21和側剖面為三角形的槽21’，但並不僅限於此。在一個第一膜2上可以只形成側剖面為四邊形的槽21，也可以只形成側剖面為三角形的槽21’。槽的形狀與所述突出部的形狀對應，因此並不僅限於此，可為多種形狀。另外，雖然沒有圖示，所述槽21、21’的側壁及/或底面的至少一部可形成有規定的曲率。 As shown in Fig. 1b, according to the shape of the protruding portions 41, 41', the grooves 21, 21' may include a portion of a groove 21 having a side cross section of a quadrangle and a portion of a groove 21' having a triangular side cross section. As shown in Fig. 1b, a groove 21 having a side cross section and a groove 21' having a triangular side cross section may be mixed and formed on one first film 2, but it is not limited thereto. On the first film 2, only the groove 21 having a side cross section may be formed, or only the groove 21' having a triangular side cross section may be formed. The shape of the groove corresponds to the shape of the protruding portion, and therefore it is not limited thereto, and may have various shapes. Further, although not shown, at least one of the side walls and/or the bottom surface of the grooves 21, 21' may be formed with a predetermined curvature.

具體地說，作為樹脂層形成於第一膜2上的槽，以剖面形狀為基準，可形成選自梯形形狀、三角形形狀、正方形形狀、矩形 形狀、具有不同斜角的斜面連續連接的多邊形形狀及半圓形形狀中的至少一種形狀。例如，可以只形成選自上述形狀中的一種形狀，也可以將所選的兩種以上的形狀混合形成。 Specifically, the groove formed as the resin layer on the first film 2 may be selected from a trapezoidal shape, a triangular shape, a square shape, and a rectangular shape based on the cross-sectional shape. At least one of a shape, a polygonal shape in which the inclined faces having different oblique angles are continuously connected, and a semicircular shape. For example, only one shape selected from the above shapes may be formed, or a selected two or more shapes may be mixed.

另外，以對第一膜2的平面圖為基準，從上方觀察第一膜2的槽時，有可能呈現為多個線排列的形狀，這可以配置成多個線相互交叉的網目圖案形狀，也可以以多個線互不交叉，且彼此間隔開距離地反復或者不規則的形狀配置，這些槽的配置可以有多種組合。 Further, when the groove of the first film 2 is viewed from above with respect to the plan view of the first film 2, there may be a shape in which a plurality of lines are arranged, which may be arranged in a mesh pattern shape in which a plurality of lines intersect each other. The configuration may be such that the plurality of lines do not intersect each other and are repeatedly or irregularly spaced apart from each other, and the arrangement of the grooves may be variously combined.

如圖1b所示，所述槽21、21’的深度可以小於所述第一膜2的厚度。 As shown in Fig. 1b, the depth of the grooves 21, 21' may be smaller than the thickness of the first film 2.

另一方面，在形成所述槽21、21’之前可對所述第一膜2的上表面22進行疏水性處理。由此，如在後面所述，能夠更加容易地從第一膜2的上表面22去除導電膏。這種對上表面22的疏水性處理，例如可通過對第一膜2的上表面22進行等離子處理而實現。 On the other hand, the upper surface 22 of the first film 2 can be subjected to a hydrophobic treatment before the grooves 21, 21' are formed. Thereby, the conductive paste can be removed from the upper surface 22 of the first film 2 more easily as will be described later. This hydrophobic treatment of the upper surface 22 can be achieved, for example, by plasma treatment of the upper surface 22 of the first film 2.

接下來，如圖1c所示，在如上的第一膜2上塗敷作為導電墨的導電膏3之後，在所述槽21、21’中填充所述導電膏3。通過擠壓件7推動第一膜2的上表面22，將位於第一膜2的上表面22上的導電膏3填充到槽21、21’內。此時，在所述第一膜2的上表面22不規則地排列有導電膏的殘留物。因此，所述導電膏3包括填充到所述槽21、21’內的第二膜31和殘留在所述第一膜2的上表面22的第三膜32。 Next, as shown in Fig. 1c, after the conductive paste 3 as a conductive ink is applied onto the first film 2 as above, the conductive paste 3 is filled in the grooves 21, 21'. The upper surface 22 of the first film 2 is pushed by the pressing member 7, and the conductive paste 3 on the upper surface 22 of the first film 2 is filled into the grooves 21, 21'. At this time, residues of the conductive paste are irregularly arranged on the upper surface 22 of the first film 2. Therefore, the conductive paste 3 includes the second film 31 filled into the grooves 21, 21' and the third film 32 remaining on the upper surface 22 of the first film 2.

然後，可以使所述導電膏一次固化，但並不僅限於此。 Then, the conductive paste can be cured once, but is not limited thereto.

作為塗敷所述導電膏的方法，可以採用平板絲網印刷法、旋轉(spin)塗敷法、輥(roll)塗法、流動(flow)塗敷法、刮板(doctor blade)塗敷法、滴塗法(dispensing)、凹版印刷法或柔版(flexography)印刷法填充所述導電墨。導電膏的塗敷不僅限於一次，而是可以反復進行多次。 As a method of applying the conductive paste, a flat screen printing method, a spin coating method, a roll coating method, a flow coating method, or a doctor blade coating method may be employed. The conductive ink is filled by a dispensing, gravure or flexography printing method. The application of the conductive paste is not limited to one time, but may be repeated a plurality of times.

根據上述不同的塗敷方法，導電膏向槽21、21’內的填充特性有可能不同，但其需要調節導電膏中的成分，使組合物的流變能力最適於填充方法，從而使導電膜適於各種填充方法。根據不同的金屬組合物的金屬含量、溶劑含量及揮發溫度、黏度和觸變性的特性，所述填充特性有可能不同。 According to the different coating methods described above, the filling characteristics of the conductive paste into the grooves 21, 21' may be different, but it is necessary to adjust the components in the conductive paste so that the rheology of the composition is most suitable for the filling method, thereby making the conductive film Suitable for a variety of filling methods. The filling characteristics may vary depending on the metal content, solvent content, and volatilization temperature, viscosity, and thixotropic properties of the different metal compositions.

通過上述方法一次填充於所述槽21、21’內而形成的一次圖案部即第二膜31的厚度可以等於或小於槽21、21’的深度。例如，所述第二膜31的厚度可為10μm以下，更詳細地可為0.1μm以上且5μm以下，該厚度可根據所要實現的線寬及所需電阻條件進行調節。 The thickness of the primary pattern portion, i.e., the second film 31, which is formed by filling the grooves 21, 21' once by the above method, may be equal to or smaller than the depth of the grooves 21, 21'. For example, the thickness of the second film 31 may be 10 μm or less, and more specifically 0.1 μm or more and 5 μm or less, which may be adjusted according to the line width to be realized and the required resistance conditions.

所述導電膏的一次固化溫度，可根據所述導電膏的成分及/或基材的材質而選擇，可在25~600℃溫度條件下，不導致所述基材變形的溫度範圍內進行。 The primary curing temperature of the conductive paste may be selected according to the composition of the conductive paste and/or the material of the substrate, and may be performed within a temperature range of 25 to 600 ° C without causing deformation of the substrate.

接下來，在所述第一膜2上塗敷規定的溶液。 Next, a predetermined solution is applied to the first film 2.

所述溶液是能夠溶解一次固化的所述導電膏的溶液，例如可使用蝕刻液，將其塗敷在形成於所述第一膜2上的經過一次固化的導電膏3上。因此，所述溶液被塗敷在填充於所述槽21、21’內的第二膜31及在第一膜2的上表面22上殘留的第三膜32上。 The solution is a solution capable of dissolving the once-cured conductive paste, and may be applied, for example, to an over-cured conductive paste 3 formed on the first film 2 using an etching solution. Therefore, the solution is applied to the second film 31 filled in the grooves 21, 21' and the third film 32 remaining on the upper surface 22 of the first film 2.

從而如圖1d所示，所述溶液與一次固化的導電膏3反應，從而可在所述槽21、21’內與所述第二膜31的至少一部分混合而形成第一混合體33，並可在所述第一膜2的上表面22與所述第三膜32混合而形成第二混合體34。 Thereby, as shown in FIG. 1d, the solution is reacted with the primary cured conductive paste 3 so as to be mixed with at least a portion of the second film 31 in the grooves 21, 21' to form the first mixture 33, and The second mixture 34 may be formed by mixing the upper surface 22 of the first film 2 with the third film 32.

所述溶液可具有親水特性，從而能夠有效地溶解所述第三膜32並形成第二混合體34，且還可將所述第二混合體34很好地填充到槽21、21’內。例如，當所述溶液6包含氨基甲酸銨系、碳酸銨系或碳酸氫銨系化合物時，可通過調節其碳原子數來調節親水特性。 The solution may have a hydrophilic property so that the third film 32 can be effectively dissolved and the second mixture 34 is formed, and the second mixture 34 can also be well filled into the grooves 21, 21'. For example, when the solution 6 contains an ammonium carbamate-based, ammonium carbonate-based or ammonium hydrogencarbonate-based compound, the hydrophilic property can be adjusted by adjusting the number of carbon atoms thereof.

所述溶液的塗敷方法可從平板絲網印刷、輥(roll)塗、流動 (flow)塗敷、刮板(doctor blade)塗敷、凹版印刷或柔版(flexography)印刷法等中選擇使用。 The coating method of the solution can be screen printed from a flat plate, rolled, and flowed. It is selected for use in a coating, a doctor blade coating, a gravure printing or a flexography printing method.

所述溶液對所述導電膏3的蝕刻速度可通過調節在塗敷溶液時溶液的沉積時間進行控制，或者通過調節溶液的氧化劑或銨系化合物的濃度進行控制，必要時可反復進行塗敷過程。 The etching rate of the solution to the conductive paste 3 can be controlled by adjusting the deposition time of the solution when the solution is applied, or by adjusting the concentration of the oxidizing agent or the ammonium compound in the solution, and the coating process can be repeated if necessary. .

如上所述，通過溶液的塗敷，在所述第一膜2的上表面22上形成的第二混合體34二次填充到槽21、21’內。 As described above, the second mixture 34 formed on the upper surface 22 of the first film 2 is secondarily filled into the grooves 21, 21' by the application of the solution.

為了將所述第二混合體34填充到所述槽21、21’內，例如，如圖1e所示，可通過擠壓件7額外的推動第一膜2的上表面22，使位於第一膜2的上表面22的第二混合體34填充到槽21、21’內，並與第一混合體33混合，從而形成如圖1f所示的第三混合體35。除此之外，可對將所述第二混合體34填充到槽21內的方法進行多種變形。例如，對整個基材1另行施加振盪及/或搖動，從而使第二混合體34填充到槽21、21’內，或者可以採用利用空氣的方法。 In order to fill the second mixing body 34 into the grooves 21, 21', for example, as shown in Fig. 1e, the upper surface 22 of the first film 2 can be additionally pushed by the pressing member 7, so that it is located at the first The second mixture 34 of the upper surface 22 of the membrane 2 is filled into the grooves 21, 21' and mixed with the first mixture 33 to form a third mixture 35 as shown in Fig. 1f. In addition to this, various modifications can be made to the method of filling the second mixture 34 into the groove 21. For example, the entire substrate 1 is additionally subjected to oscillation and/or shaking so that the second mixture 34 is filled into the grooves 21, 21', or a method using air can be employed.

此時，如前所述，當第一膜2的上表面22被施以疏水性處理時，所述第二混合體34能夠更加順利地從所述上表面22填充到所述槽21、21’內。 At this time, as described above, when the upper surface 22 of the first film 2 is subjected to the hydrophobic treatment, the second mixture 34 can be more smoothly filled from the upper surface 22 to the grooves 21, 21 'Inside.

如上所述，通過使用蝕刻液溶解殘留的導電膏32，並將其推入槽21、21’內而進行二次填充，其中，所述殘留的導電膏32為將導電膏3一次填充於21、21’時，殘留於第一膜2的上表面22的第三膜32。更具體地說，如圖1f所示，通過將第二混合體34填充到槽21、21’內，第一膜2的上表面22的導電膏已是去除的狀態，且在第一膜2的槽21、21’內，已是作為一次圖案部的第二膜31和作為二次圖案部的第三混合體35構成層壓結構的狀態。在此狀態下，對所述導電膏3進行二次固化，從而形成填充於槽21、21’內的微細導電圖案。 As described above, the remaining conductive paste 32 is dissolved by using an etching solution, and is pushed into the grooves 21, 21' for secondary filling, wherein the residual conductive paste 32 is filled with the conductive paste 3 at one time. At 21', the third film 32 remains on the upper surface 22 of the first film 2. More specifically, as shown in FIG. 1f, by filling the second mixture 34 into the grooves 21, 21', the conductive paste of the upper surface 22 of the first film 2 is in a removed state, and in the first film 2 In the grooves 21, 21', the second film 31 as the primary pattern portion and the third mixture 35 as the secondary pattern portion constitute a laminated structure. In this state, the conductive paste 3 is subjected to secondary curing to form a fine conductive pattern filled in the grooves 21, 21'.

所述導電膏3的二次固化溫度可根據所述導電膏的成分及/或 基材的材質而選擇，可在25~600℃溫度條件下，不導致所述基材變形的溫度範圍內進行。在圖1f中表示槽21、21’內的導電膏3由第二膜31和第三混合體35構成層壓結構，而在二次固化之後這種層壓結構消失，已固化的導電膏3作為單層的導電圖案存在。 但是並不僅限於此，在二次固化之後，填充於槽21、21’內的導電膏3可呈兩層層壓結構。 The secondary curing temperature of the conductive paste 3 may be according to the composition of the conductive paste and/or The material of the substrate is selected and can be carried out at a temperature of 25 to 600 ° C without causing deformation of the substrate. The conductive paste 3 in the grooves 21, 21' is shown in Fig. 1f to constitute a laminated structure by the second film 31 and the third mixture 35, and after the secondary curing, the laminated structure disappears, and the cured conductive paste 3 is cured. A conductive pattern exists as a single layer. However, it is not limited thereto, and after the secondary curing, the conductive paste 3 filled in the grooves 21, 21' may have a two-layer laminated structure.

通過上述方法製造的本發明的一實施例的導電圖案部件，由於將已經形成的導電膏再次溶解並在微槽內形成導電圖案，因此能夠提高所述導電圖案的導電性。尤其是，當所述導電膏包含金屬時，通過對一次固化的導電膏的再次溶解，產生金屬粒子的重新排列及/或重新形成，因此可進一步提高導電圖案的導電性，從而實現微細導電圖案的低電阻化。 In the conductive pattern member of one embodiment of the present invention manufactured by the above method, since the conductive paste which has been formed is dissolved again and a conductive pattern is formed in the microgroove, the conductivity of the conductive pattern can be improved. In particular, when the conductive paste contains a metal, re-dissolving and/or reforming of the metal particles is caused by re-dissolving the primary-cured conductive paste, so that the conductivity of the conductive pattern can be further improved, thereby realizing a fine conductive pattern. Low resistance.

另外，使基材及/或第一膜2透明時，通過從第一膜2的上表面22去除導電膏，可提高整個裝置的透明性，因此能夠製造透明導電膜。不僅如此，當所述基材及/或第一膜2具有絕緣性時，通過從第一膜2的上表面22去除導電膏，可提高第一膜2的絕緣性。 Further, when the substrate and/or the first film 2 are made transparent, the conductive paste can be removed from the upper surface 22 of the first film 2, whereby the transparency of the entire device can be improved, and thus the transparent conductive film can be manufactured. Moreover, when the substrate and/or the first film 2 have insulating properties, the insulation of the first film 2 can be improved by removing the conductive paste from the upper surface 22 of the first film 2.

圖2a至圖2g為按順序表示本發明的另一實施例的導電圖案形成方法的剖視圖。 2a to 2g are cross-sectional views showing, in order, a method of forming a conductive pattern according to another embodiment of the present invention.

按照圖2a至圖2f，在槽21、21’中填充導電膏3。在所述槽21、21’內填充導電膏3的方法與前述圖1a至圖1f的方法相同，因此省略詳細的說明。 According to Figs. 2a to 2f, the conductive paste 3 is filled in the grooves 21, 21'. The method of filling the conductive paste 3 in the grooves 21, 21' is the same as the method of the above-mentioned Figs. 1a to 1f, and thus detailed description is omitted.

接下來，如圖2g所示，在所述二次固化的導電膏3上可進一步形成不透明的發黑部即第四膜8。當所述二次固化的導電膏3包含金屬時，可將不透明的第四膜8形成在二次固化的導電膏3上，從而控制二次固化的導電膏3的反射特性。 Next, as shown in FIG. 2g, an opaque blackening portion, that is, a fourth film 8, may be further formed on the secondary cured conductive paste 3. When the secondary cured conductive paste 3 contains a metal, the opaque fourth film 8 may be formed on the secondary cured conductive paste 3, thereby controlling the reflection characteristics of the secondary cured conductive paste 3.

如圖2g所示，可根據需要在二次固化的導電膏3上塗敷發黑組合物來形成所述第四膜8，在塗敷到第一膜2的上表面22之後，可擦除塗敷在第一膜2的上表面22的發黑組合物。從第一膜2的 上表面22去除發黑組合物的方法可適用前述的通過擠壓件推出的方法，但並不僅限於此，還可用空氣或刷子等各種方式擦除。 As shown in FIG. 2g, the blackening composition may be applied to the secondary cured conductive paste 3 as needed to form the fourth film 8, which is erasable after application to the upper surface 22 of the first film 2. A blackening composition applied to the upper surface 22 of the first film 2. From the first film 2 The method of removing the blackening composition from the upper surface 22 can be applied to the aforementioned method of pushing out by the extrusion member, but is not limited thereto, and can be erased by various means such as air or brush.

通過調節所述發黑組合物中鈦系或鋯系錯合物的濃度，可調節二次固化的導電膏3的表面的黑化度。 The degree of blackening of the surface of the secondary cured conductive paste 3 can be adjusted by adjusting the concentration of the titanium-based or zirconium-based complex in the blackening composition.

所述發黑組合物的塗敷方法可從平板絲網印刷、旋轉(spin)塗敷、輥(roll)塗、流動(flow)塗敷、刮板(doctor blade)塗敷、滴塗(dispensing)、凹版印刷或柔版(flexography)印刷方法等方法中選擇使用。 The coating method of the blackening composition can be from flat screen printing, spin coating, roll coating, flow coating, doctor blade coating, and dispensing (dispensing). ), gravure printing or flexography printing methods are used.

可在25~600℃條件下，對所述發黑組合物進行乾燥。 The blackening composition can be dried at 25 to 600 °C.

另一方面，如圖2g所示，當所述發黑組合物塗敷於槽21內的二次固化的導電膏3的表面時，如圖3所示，發黑組合物可浸入二次固化的導電膏3和槽21的內表面之間，從而在二次固化的導電膏3和槽21的內表面之間形成薄的第五膜81。所述第五膜81與第四膜8為同一組分的物質，可從第四膜8連續及/或不連續地延伸。雖然沒有圖示，所述第五膜81也可連續及/或不連續地設置於所述第二膜31和第三混合體35之間。 On the other hand, as shown in Fig. 2g, when the blackening composition is applied to the surface of the secondary cured conductive paste 3 in the groove 21, as shown in Fig. 3, the blackening composition can be immersed in the secondary curing. The conductive paste 3 is interposed between the inner surface of the groove 21, thereby forming a thin fifth film 81 between the secondary cured conductive paste 3 and the inner surface of the groove 21. The fifth film 81 and the fourth film 8 are the same component and may extend continuously and/or discontinuously from the fourth film 8. Although not shown, the fifth film 81 may be disposed continuously and/or discontinuously between the second film 31 and the third mixture 35.

如上所述，發黑組合物浸入二次固化的導電膏3和槽21的內表面之間並固化，能夠進一步提高二次固化的導電膏3和槽21的內表面之間的貼緊力，從而可進一步提高微細導電圖案的耐剝離特性。 As described above, the blackening composition is immersed between the secondary cured conductive paste 3 and the inner surface of the groove 21 and cured, and the adhesion between the secondary cured conductive paste 3 and the inner surface of the groove 21 can be further improved. Thereby, the peeling resistance of the fine conductive pattern can be further improved.

另一方面，所述二次固化的導電膏3的表面發黑並不僅限於前述方法，還可適用將酸性溶液或鹼性溶液塗敷於二次固化的導電膏3的表面而進行處理的方法、將不透明物質鍍覆於二次固化的導電膏3的表面的方法或將不透明物質直接印刷於二次固化的導電膏3的表面的方法。 On the other hand, the blackening of the surface of the secondary cured conductive paste 3 is not limited to the above method, and a method of applying an acidic solution or an alkaline solution to the surface of the secondary cured conductive paste 3 may be applied. A method of plating an opaque substance on the surface of the secondary-cured conductive paste 3 or a method of directly printing an opaque substance on the surface of the secondary-cured conductive paste 3.

在前述實施例中，所述槽21、21’的深度淺於第一膜2的厚度，但本發明並不僅限於此，如圖4a及圖4b所示，第一膜2’的厚度和槽21、21’的深度也可以相同。 In the foregoing embodiment, the depth of the grooves 21, 21' is shallower than the thickness of the first film 2, but the present invention is not limited thereto, as shown in Figs. 4a and 4b, the thickness and groove of the first film 2'. The depth of 21, 21' can also be the same.

此外，所述槽可通過多種方法形成。 Furthermore, the grooves can be formed by a variety of methods.

例如，如圖5a所示，在基材1上形成第一膜2之後，從第一膜2的上部照射雷射光束，從而如圖5b所示，去除所述第一膜2的部分，使與所述槽21"的圖案相對應。此時，如圖5a所示，可在不使用額外的遮光罩的情況下照射所述雷射光束，但並不僅限於此。也可將遮光罩配置在所述第一膜2上的狀態下照射雷射光束而進行蝕刻，其中，所述遮光罩具有與所述槽21"的圖案相對應的開口。 For example, as shown in FIG. 5a, after the first film 2 is formed on the substrate 1, the laser beam is irradiated from the upper portion of the first film 2, thereby removing the portion of the first film 2 as shown in FIG. 5b, so that Corresponding to the pattern of the groove 21". At this time, as shown in FIG. 5a, the laser beam can be irradiated without using an additional hood, but it is not limited thereto. Etching is performed by irradiating a laser beam in a state on the first film 2, wherein the hood has an opening corresponding to the pattern of the groove 21".

如圖5b所示，可使通過照射雷射光束形成的槽21"僅形成在第一膜2上，但並不僅限於此，如圖5c所示，也可以形成具有延伸到基材1的深度的槽21’"。 As shown in FIG. 5b, the groove 21" formed by irradiating the laser beam may be formed only on the first film 2, but is not limited thereto, and may have a depth extending to the substrate 1 as shown in FIG. 5c. Slot 21'".

在如此形成的槽21"、21’"中填充導電膏的方法與前述的圖1c至圖1f相同。 The method of filling the conductive paste in the grooves 21", 21'" thus formed is the same as that of Figs. 1c to 1f described above.

所述槽可通過另一種方法形成。 The trough can be formed by another method.

首先，在基材上形成第一膜後，在所述第一膜上配置感光膜。然後，使用具有與所述槽的圖案對應的遮光圖案的光罩進行曝光及灰化，從而在所述感光膜上形成與所述槽的圖案對應的開口。通過蝕刻去除由上述開口露出的所述第一膜的部分，從而在第一膜上形成槽，之後去除所述感光膜。 First, after the first film is formed on the substrate, a photosensitive film is disposed on the first film. Then, exposure and ashing are performed using a photomask having a light-shielding pattern corresponding to the pattern of the groove, thereby forming an opening corresponding to the pattern of the groove on the photosensitive film. A portion of the first film exposed by the opening is removed by etching to form a groove on the first film, and then the photosensitive film is removed.

除此之外，如上的槽還可用多種方法形成。例如，在所述基材上形成所述第一膜的步驟中，可在所述基材上配置與所述槽的圖案對應的掩模後形成第一膜，從而形成包含槽的第一膜。 In addition to this, the above grooves can be formed in a variety of ways. For example, in the step of forming the first film on the substrate, a first film may be formed by disposing a mask corresponding to the pattern of the groove on the substrate, thereby forming a first film including a groove .

以下，將通過實施例具體說明本發明，但本發明的範圍並不限於實施例。 Hereinafter, the present invention will be specifically described by way of examples, but the scope of the invention is not limited to the examples.

[製備例1](400CAM蝕刻劑) [Preparation Example 1] (400 CAM etchant)

在200ml燒杯中加入18g的氨基甲酸異丁酯、70g的異丁胺、2g的95%2-氨基-2-甲基-1-丙醇之後，使用超聲波破碎儀(Sonicator)充分溶解20分鐘，後緩慢地添加10g的30%過氧化 氫，攪拌10分鐘製備蝕刻劑。 18 g of isobutyl carbamate, 70 g of isobutylamine, and 2 g of 95% 2-amino-2-methyl-1-propanol were placed in a 200 ml beaker, and then thoroughly dissolved using a sonicator for 20 minutes. Slowly add 10g of 30% peroxidation Hydrogen was stirred for 10 minutes to prepare an etchant.

[製備例2](400-800CAM蝕刻劑) [Preparation Example 2] (400-800 CAM etchant)

在200ml燒杯中加入10g的氨基甲酸異丁酯和氨基甲酸2-乙基己酯(兩者的摩爾比為1：1)、78g的2-乙基己胺、2g的95%2-氨基-2-甲基-1-丙醇之後，使用超聲波破碎儀(Sonicator)充分溶解20分鐘，後緩慢地添加10g的30%過氧化氫，攪拌10分鐘製備蝕刻劑。 10 g of isobutyl carbamate and 2-ethylhexyl carbamate (1:1 molar ratio), 78 g of 2-ethylhexylamine, 2 g of 95% 2-amino- were added to a 200 ml beaker. After 2-methyl-1-propanol, it was sufficiently dissolved using a sonicator for 20 minutes, and then 10 g of 30% hydrogen peroxide was slowly added thereto, and the etchant was prepared by stirring for 10 minutes.

[製備例3](800CAM蝕刻劑) [Preparation Example 3] (800 CAM etchant)

在200ml燒杯中加入15g的氨基甲酸2-乙基己酯、73g的異丁胺、2g的95%2-氨基-2-甲基-1-丙醇之後，使用超聲波破碎儀(Sonicator)充分溶解20分鐘，然後緩慢地添加10g的30%過氧化氫之後，攪拌10分鐘製備蝕刻劑。 After adding 15 g of 2-ethylhexyl carbamate, 73 g of isobutylamine, and 2 g of 95% 2-amino-2-methyl-1-propanol in a 200 ml beaker, it was thoroughly dissolved using a sonicator (Sonicator). After 20 minutes, 10 g of 30% hydrogen peroxide was slowly added, and the etchant was prepared by stirring for 10 minutes.

[製備例4](400CAM蝕刻劑(7%過氧化氫)) [Preparation Example 4] (400 CAM etchant (7% hydrogen peroxide))

在200ml燒杯中加入18g的氨基甲酸異丁酯、79g的異丁胺、2g的95%2-氨基-2-甲基-1-丙醇之後，使用超聲波破碎儀(Sonicator)充分溶解20分鐘，後緩慢地添加7g的30%過氧化氫之後，攪拌10分鐘製備蝕刻劑。 18 g of isobutyl carbamate, 79 g of isobutylamine, and 2 g of 95% 2-amino-2-methyl-1-propanol were placed in a 200 ml beaker, and then thoroughly dissolved using a sonicator for 20 minutes. After slowly adding 7 g of 30% hydrogen peroxide, the etchant was prepared by stirring for 10 minutes.

[製備例5](400CAM蝕刻劑(5%過氧化氫)) [Preparation Example 5] (400 CAM etchant (5% hydrogen peroxide))

在200ml燒杯中加入18g的氨基甲酸異丁酯、79g的異丁胺、2g的95%2-氨基-2-甲基-1-丙醇之後，使用超聲波破碎儀(Sonicator)充分溶解20分鐘，然後緩慢地添加5g的30%過氧化氫之後，攪拌10分鐘製備蝕刻劑。 18 g of isobutyl carbamate, 79 g of isobutylamine, and 2 g of 95% 2-amino-2-methyl-1-propanol were placed in a 200 ml beaker, and then thoroughly dissolved using a sonicator for 20 minutes. Then, 5 g of 30% hydrogen peroxide was slowly added, and the etchant was prepared by stirring for 10 minutes.

[製備例6](氨基甲酸銨蝕刻劑) [Preparation Example 6] (ammonium carbamate etchant)

除了用氨基甲酸銨取代氨基甲酸異丁酯之外，與製備例5相同的方法製備蝕刻劑。 An etchant was prepared in the same manner as in Production Example 5 except that ammonium carbamate was substituted for isobutyl carbamate.

[製備例7](碳酸銨蝕刻劑) [Preparation Example 7] (ammonium carbonate etchant)

除了用碳酸銨取代氨基甲酸異丁酯之外，通過與製備例5相同的方法製備蝕刻劑。 An etchant was prepared by the same method as Preparation Example 5 except that ammonium carbonate was used instead of isobutyl carbamate.

[製備例8](新癸酸(Neodecanoic acid)蝕刻劑) [Preparation Example 8] (Neodecanoic acid etchant)

除了用新癸酸取代氨基甲酸異丁酯之外，通過與製備例5相同的方法製備蝕刻劑。 An etchant was prepared by the same method as Preparation Example 5 except that neodecanoic acid was replaced with neodecanoic acid.

[製備例9](巰基蝕刻劑) [Preparation Example 9] (sulfhydryl etchant)

除了用正辛硫醇取代氨基甲酸異丁酯之外，通過與製備例5相同的方法製備蝕刻劑。 An etchant was prepared by the same method as Preparation Example 5 except that n-butyl carbamic acid was replaced with n-octyl thiol.

[製備例10](內酯蝕刻劑) [Preparation Example 10] (lactone etchant)

除了用γ-丁內酯取代氨基甲酸異丁酯之外，通過與製備例5相同的方法製備蝕刻劑。 An etchant was prepared by the same method as Preparation Example 5 except that butyl-butyrolactone was used instead of isobutyl carbamate.

[製備例11](苯甲酸蝕刻劑) [Preparation Example 11] (benzoic acid etchant)

除了用苯甲酸取代氨基甲酸異丁酯之外，通過與製備例5相同的方法製備蝕刻劑。 An etchant was prepared by the same method as Preparation Example 5 except that benzoic acid was used instead of isobutyl carbamate.

[製備例12](銅膏墨) [Preparation Example 12] (copper paste ink)

在22g的乙基卡必醇醋酸酯中浸漬8g的聚酯樹脂(SKC公司)，攪拌12小時進行溶解後，在完成的組合物中浸漬具有2μm平均粒度的球形銅粒子70g，並且以15bar的壓力使之通過三輥式軋機(艾卡特(EXAKT)公司製造)三次以製備導電膏。 8 g of a polyester resin (SKC Co., Ltd.) was immersed in 22 g of ethyl carbitol acetate, and after stirring for 12 hours to dissolve, 70 g of spherical copper particles having an average particle size of 2 μm were immersed in the completed composition, and 15 bar was used. The pressure was passed through a three-roll mill (manufactured by EXAKT Co., Ltd.) three times to prepare a conductive paste.

[製備例13](銅錯合物) [Preparation Example 13] (copper complex)

在配有攪拌器的50ml舒倫克(Schlenk)燒瓶中，在具有黏性的2-乙基己基銨2-乙基己基氨基甲酸酯9.52g(31.48mmol)與10ml甲醇的混合溶液中添加氫氧化銅3.07g(31.48mmol)，並在常溫下使其反應兩個小時。隨著反應的進行，起初深綠色的懸浮液(Slurry)的顏色逐漸變淺，最後獲得藍色的透明溶液。在真空條件下，去除上述反應溶液中的全部溶劑，則獲得藍色的銅錯合物12.6g。 In a 50 ml Schlenk flask equipped with a stirrer, added in a mixed solution of viscous 2-ethylhexyl ammonium 2-ethylhexyl carbamate 9.52 g (31.48 mmol) and 10 ml of methanol. Copper hydroxide (3.07 g, 31.48 mmol) was allowed to react at room temperature for two hours. As the reaction progressed, the color of the initially dark green suspension (Slurry) gradually became lighter, and finally a blue transparent solution was obtained. Under the vacuum condition, all the solvents in the above reaction solution were removed, and 12.6 g of a blue copper complex was obtained.

[製備例14](銅膏+銅錯合物) [Preparation Example 14] (copper paste + copper complex)

在30g的PA-30NT(印可得株式會社(Inktec Co.,Ltd)製造)中浸漬具有2μm平均粒度的球形銅粒子70g，使用調糊機 (DAE-WHA TECH CO.LTD)以1000rpm的速度攪拌20分鐘，製備導電膏。 70 g of spherical copper particles having an average particle size of 2 μm were impregnated in 30 g of PA-30NT (manufactured by Inktec Co., Ltd.) using a paste mixer (DAE-WHA TECH CO. LTD) was stirred at 1000 rpm for 20 minutes to prepare a conductive paste.

[實施例1] [Example 1]

將UV樹脂塗敷於聚對苯二甲酸乙二醇酯(PET)之後，用模具壓印，並用紫外線固化而形成3μm大小的凹陷的微槽，將其作為基材使用。在基材上塗敷作為導電墨的PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用刮板方式初步塗敷製備例1中製備的蝕刻劑，用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to polyethylene terephthalate (PET), it was embossed with a mold, and cured with ultraviolet rays to form a pit having a size of 3 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco), which is a conductive ink, was applied to the substrate, and filled in a microchannel having a size of 3 μm by means of a blade, and baked at 120 ° C for one minute to form. Metal layer. As a next step, the etchant prepared in Preparation Example 1 is initially applied by a squeegee method, and the residual metal substance on the surface dissolved or dispersed by the etchant is again pressed and pushed in the direction of the substrate by the squeegee, thereby The residual metal species on the surface of the substrate is again filled in the microchannel or removed. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例2] [Embodiment 2]

將UV樹脂塗敷於PET之後，用模具壓印，並用紫外線固化而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold, and cured with ultraviolet rays to form a depressed microgroove of 3 μm in size, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 1, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例3] [Example 3]

將UV樹脂塗敷於PET之後，用模具壓印而形成20μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於20μm 大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to the PET, it was embossed with a mold to form a depressed microgroove having a size of 20 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco Co., Ltd.) was applied to the substrate, and the film was filled in a squeegee (Blade) at 20 μm. The size of the microgrooves was fired at 120 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 1, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例4] [Example 4]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，並且用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並且反復推動兩次，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 1, preliminary coating was performed by a squeegee method, and the residual metal substance on the surface dissolved or dispersed by the etchant was scraped along the substrate. The direction is again applied and pushed twice repeatedly to refill the residual metal material on the surface of the substrate in the microchannel or to remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例5] [Example 5]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，並且用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並且反復推動三次，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材 乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 1, preliminary coating was performed by a squeegee method, and the residual metal substance on the surface dissolved or dispersed by the etchant was scraped along the substrate. The direction is again applied and pushed three times repeatedly to refill the residual metal material on the surface of the substrate in the microchannel or to remove it. As a next step, at 120 ° C, the imprinted substrate filled with a metal substance Dry for five minutes to form an electrode with a fine line width.

[實施例6] [Embodiment 6]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PSP-009(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PSP-009 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 1, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例7] [Embodiment 7]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PSP-010(印可得株式會社製造)導電墨，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. A conductive ink of PSP-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by means of a blade, and fired at 120 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 1, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例8] [Embodiment 8]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為 下一個步驟，用製備例1中製備的蝕刻劑沉積10秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. As In the next step, after depositing for 10 seconds with the etchant prepared in Preparation Example 1, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is applied along the substrate direction by the squeegee. The pressure is applied again and pushed to refill the residual metal material on the surface of the substrate in the microchannel or to remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例9] [Embodiment 9]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例1中製備的蝕刻劑沉積30秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. As the next step, after deposition for 30 seconds using the etchant prepared in Preparation Example 1, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例10] [Embodiment 10]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例2中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 2, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface of the etchant dissolved or dispersed is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例11] [Example 11]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例3中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. As the next step, after depositing for five seconds with the etchant prepared in Preparation Example 3, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例12] [Embodiment 12]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式在3μm大小的微槽中反復填充兩次，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, and was repeatedly filled twice in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal. Floor. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 1, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例13] [Example 13]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式在3μm大小的微槽中反復填充三次，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後， 用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, and it was repeatedly filled three times in a microchannel of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. . As the next step, after deposition for five seconds with the etchant prepared in Preparation Example 1, The preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is again pressed and pushed in the direction of the substrate by the squeegee, thereby refilling the residual metal substance on the surface of the substrate. In the microchannel or removed. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例14] [Embodiment 14]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用棒塗(Bar coating)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, and the mixture was filled in a microchannel having a size of 3 μm by Bar coating, and fired at 120 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 1, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例15] [Example 15]

用熱壓縮成型模具對PET進行壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 The PET was embossed with a hot compression molding die to form a recessed microgroove of 3 μm size, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 1, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例16] [Example 16]

使用UV雷射器(EO技術有限公司製造)，以5W皮秒脈衝(PICO PULSE)、365nm波長在玻璃上形成25μm的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於25μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 Using a UV laser (manufactured by EO Technology Co., Ltd.), a 25 μm-recessed microgroove was formed on the glass at a wavelength of 365 nm using a 5 W picosecond pulse (PICO PULSE), and used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, and filled in a microchannel having a size of 25 μm by means of a blade, and baked at 120 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 1, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例17] [Example 17]

使用UV雷射器(EO技術有限公司製造)，以5W皮秒脈衝(PICO PULSE)、365nm波長在玻璃上形成25μm的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式在25μm大小的微槽中反復填充兩次，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 Using a UV laser (manufactured by EO Technology Co., Ltd.), a 25 μm-recessed microgroove was formed on the glass at a wavelength of 365 nm using a 5 W picosecond pulse (PICO PULSE), and used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, and was repeatedly filled twice in a microchannel of 25 μm by a blade method, and fired at 120 ° C for one minute to form a metal. Floor. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 1, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例18] [Embodiment 18]

使用UV雷射器(EO技術有限公司製造)，以5W皮秒脈衝(PICO PULSE)、365nm波長在玻璃上形成25μm的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式在25μm大小的微槽中反復填 充三次，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 Using a UV laser (manufactured by EO Technology Co., Ltd.), a 25 μm-recessed microgroove was formed on the glass at a wavelength of 365 nm using a 5 W picosecond pulse (PICO PULSE), and used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, and was repeatedly filled in a microchannel of 25 μm by a blade method. It was charged three times and baked at 120 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 1, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例19] [Embodiment 19]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，在將製備例6中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. As the next step, after the etchant prepared in Preparation Example 6 was deposited for five seconds, preliminary coating was performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant was scraped along the base. The material direction is again pressed and pushed to refill the residual metal material on the surface of the substrate in the microchannel or to remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例20] [Example 20]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例7中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分 鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. As the next step, after depositing for five seconds with the etchant prepared in Preparation Example 7, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, dry the metal substrate filled with the metal material at 120 ° C for five minutes Clock to form an electrode with a fine line width.

[實施例21] [Example 21]

將UV樹脂塗敷於玻璃上之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例8中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在200℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied onto the glass, it was embossed with a mold to form a depressed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 8, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 200 ° C for five minutes to form an electrode having a fine line width.

[實施例22] [Example 22]

將UV樹脂塗敷於玻璃上之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例9中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在200℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied onto the glass, it was embossed with a mold to form a depressed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. As the next step, after depositing for five seconds with the etchant prepared in Preparation Example 9, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 200 ° C for five minutes to form an electrode having a fine line width.

[實施例23] [Example 23]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在80g的甲醇中添加20g的80%水合肼並進行攪拌，在基材的整個表面上塗敷上述溶液後，在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮 板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. 20 g of 80% hydrazine hydrate was added to 80 g of methanol and stirred, and after applying the above solution to the entire surface of the substrate, PA-010 (manufactured by Inco Corporation) conductive paste was applied onto the substrate, and scraped. The sheet was filled in a microchannel having a size of 3 μm, and fired at 120 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 1, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例24] [Example 24]

將UV固化樹脂塗敷於PET之後，使用壓印用陽刻模具壓印並進行紫外線固化而形成3μm大小的凹陷的微槽，並將其作為壓印基材使用。在80g的甲醇中添加20g的80%水合肼並進行攪拌，在基材的整個表面上塗敷上述溶液後，在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV curable resin was applied to PET, a micro-groove having a recess of 3 μm size was formed by imprinting with a positive-working mold for imprinting and ultraviolet curing, and used as an imprint substrate. 20 g of 80% hydrazine hydrate was added to 80 g of methanol and stirred, and after applying the above solution to the entire surface of the substrate, a conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, and a squeegee was used. The Blade method was filled in a microchannel having a size of 3 μm and fired at 120 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 1, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例25] [Example 25]

將UV樹脂塗敷於玻璃上之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在80g的異丙醇中添加20g的葡萄糖並進行攪拌，在基材的整個表面上塗敷上述溶液後，在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶 解或者分散的表面的殘留金屬物質沿著基材方向進行施再次壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在250℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied onto the glass, it was embossed with a mold to form a depressed microgroove having a size of 3 μm, which was used as a substrate. 20 g of glucose was added to 80 g of isopropyl alcohol and stirred, and the solution was applied to the entire surface of the substrate, and then PA-010 (manufactured by Inco Corporation) conductive paste was applied to the substrate to form a blade (Blade). The method was filled in a microchannel having a size of 3 μm, and fired at 120 ° C for one minute to form a metal layer. As the next step, after deposition for five seconds using the etchant prepared in Preparation Example 1, preliminary coating was carried out by means of a squeegee method, and then the etchant was dissolved by a squeegee. The residual metal species on the surface of the solution or dispersion is recompressed and pushed in the direction of the substrate, thereby refilling or removing the residual metal species on the surface of the substrate. As a next step, the imprinted substrate filled with the metal substance was dried at 250 ° C for five minutes to form an electrode having a fine line width.

[實施例26] [Example 26]

用熱壓縮成型模具對PET進行壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。在99g的異丙醇中添加1g的Tazor TE(杜邦公司製備)而形成發黑組合物，將其以刮板方式塗敷在金屬層上，並在150℃條件下乾燥三分鐘。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 The PET was embossed with a hot compression molding die to form a recessed microgroove of 3 μm size, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. 1 g of Tazor TE (manufactured by DuPont) was added to 99 g of isopropyl alcohol to form a blackening composition, which was applied to the metal layer by a squeegee method, and dried at 150 ° C for three minutes. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 1, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例27] [Example 27]

用熱壓縮成型模具對PET進行壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。在99g的異丙醇中添加1g的乙醯丙酮錳(Aldrich公司製造)而形成發黑組合物，將其以刮板方式塗敷在金屬層上，並在150℃條件下乾燥三分鐘。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。 作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 The PET was embossed with a hot compression molding die to form a recessed microgroove of 3 μm size, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. 1 g of manganese acetoacetate (manufactured by Aldrich Co., Ltd.) was added to 99 g of isopropyl alcohol to form a blackening composition, which was applied to the metal layer by a squeegee method, and dried at 150 ° C for three minutes. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 1, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例28] [Example 28]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例10中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 10, preliminary coating was performed by a squeegee method, and then the residual metal substance on the surface of the etchant dissolved or dispersed was scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例29] [Example 29]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式填充於3μm大小的微槽中，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例11中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 11, preliminary coating was performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant was scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例30] [Example 30]

使用UV雷射器(EO技術有限公司製造)，以5W皮秒脈衝(PICO PULSE)、365nm波長在由Al2O3燒結的基材上形成25μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010 (印可得株式會社製造)導電膏，用刮板(Blade)方式在25μm大小的微槽中填充一次，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例1中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 Using a UV laser (manufactured by EO Technology Co., Ltd.), a 25 μm-sized depressed microgroove was formed on a substrate sintered from Al 2 O 3 at a wavelength of 365 nm with a 5 W picosecond pulse (PICO PULSE), and was used as a base. Material use. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled once in a microchannel of 25 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 1, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例31] [Example 31]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式在3μm大小的微槽中填充一次，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例4中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在120℃條件下，對填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. As the next step, after depositing for five seconds with the etchant prepared in Preparation Example 4, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例32] [Example 32]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-010(印可得株式會社製造)導電膏，用刮板(Blade)方式在3μm大小的微槽中填充一次，並在120℃條件下燒成一分鐘以形成金屬層。作為下一個步驟，用製備例5中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下 一個步驟，在120℃條件下，將填充有金屬物質的壓印基材乾燥五分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PA-010 (manufactured by Inco) was applied to the substrate, filled in a microchannel having a size of 3 μm by a blade method, and fired at 120 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 5, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As below In one step, the imprinted substrate filled with the metal substance was dried at 120 ° C for five minutes to form an electrode having a fine line width.

[實施例33] [Example 33]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷PA-M010(印可得株式會社製造)導電膏，用刮板(Blade)方式在3μm大小的微槽中填充一次，並在120℃條件下乾燥五分鐘以形成金屬層。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. A conductive paste of PA-M010 (manufactured by Inco) was applied to the substrate, filled once in a microchannel having a size of 3 μm by means of a blade, and dried at 120 ° C for five minutes to form a metal layer.

[實施例34] [Example 34]

使用UV雷射器(EO技術有限公司製造)，以5W皮秒脈衝(PICO PULSE)、365nm波長在玻璃上形成25μm的凹陷的微槽，並將其作為基材使用。在基材上塗敷在製備例12中製備的導電膏，用刮板(Blade)方式在25μm大小的微槽中填充一次，並在140℃條件下燒成20分鐘以形成金屬層。作為下一個步驟，在60g的甲醇中添加40g的80%水合肼並進行攪拌而形成溶液，將其塗敷在基材上，沿著基材方向對刮板施壓並推動而去除基材表面的殘留金屬物質。作為下一個步驟，在140℃條件下，對填充有金屬物質的壓印基材乾燥十分鐘，以形成微細線寬的電極。 Using a UV laser (manufactured by EO Technology Co., Ltd.), a 25 μm-recessed microgroove was formed on the glass at a wavelength of 365 nm using a 5 W picosecond pulse (PICO PULSE), and used as a substrate. The conductive paste prepared in Preparation Example 12 was coated on the substrate, filled in a microchannel having a size of 25 μm by a blade method, and fired at 140 ° C for 20 minutes to form a metal layer. As a next step, 40 g of 80% hydrazine hydrate was added to 60 g of methanol and stirred to form a solution, which was coated on a substrate, and the squeegee was pressed and pushed along the direction of the substrate to remove the surface of the substrate. Residual metal species. As a next step, the imprinted substrate filled with the metal substance was dried at 140 ° C for ten minutes to form an electrode having a fine line width.

[實施例35] [Example 35]

將UV樹脂塗敷於PET之後，用模具壓印而形成3μm大小的凹陷的微槽，並將其作為基材使用。在基材上塗敷在製備例13中製備的導電墨，用刮板(Blade)方式在3μm大小的微槽中填充一次，並在140℃條件下乾燥一分鐘以形成金屬層。作為下一個步驟，用製備例8中製備的蝕刻劑沉積五秒鐘後，用刮板方式進行初步塗敷，然後用刮板對被蝕刻劑溶解或者分散的表面的殘留金屬物質沿著基材方向進行再次施壓並推動，從而將基材表面上的殘留金屬物質再次填充於微槽中或者去除。作為下一個步驟，在140℃條件下，對填充有金屬物質的壓印基材乾燥20分鐘，以形成微細線寬的電極。 After the UV resin was applied to PET, it was embossed with a mold to form a recessed microgroove having a size of 3 μm, which was used as a substrate. The conductive ink prepared in Preparation Example 13 was coated on the substrate, filled once in a microchannel having a size of 3 μm by a blade method, and dried at 140 ° C for one minute to form a metal layer. As a next step, after depositing for five seconds with the etchant prepared in Preparation Example 8, preliminary coating is performed by a squeegee method, and then the residual metal substance on the surface dissolved or dispersed by the etchant is scraped along the substrate. The direction is again pressed and pushed to refill the residual metal material on the surface of the substrate or remove it. As a next step, the imprinted substrate filled with the metal substance was dried at 140 ° C for 20 minutes to form an electrode having a fine line width.

[實施例36] [Example 36]

使用UV雷射器(EO技術有限公司製造)，以5W皮秒脈衝(PICO PULSE)、365nm波長在玻璃上形成25μm的凹陷的微槽，並將其作為基材使用。在基材上塗敷製備例14中製備的導電膏，用刮板(Blade)方式在25μm大小的微槽中填充一次，並在140℃條件下燒成20分鐘以形成金屬層。作為下一個步驟，在60g的甲醇中添加40g的80%水合肼並進行攪拌而形成溶液，將其塗敷在基材上，並沿著基材方向對刮板施壓並推動而去除基材表面的殘留金屬物質。作為下一個步驟，在140℃條件下，對填充有金屬物質的壓印基材乾燥十分鐘，以形成微細線寬的電極。 Using a UV laser (manufactured by EO Technology Co., Ltd.), a 25 μm-recessed microgroove was formed on the glass at a wavelength of 365 nm using a 5 W picosecond pulse (PICO PULSE), and used as a substrate. The conductive paste prepared in Preparation Example 14 was coated on the substrate, filled in a microchannel having a size of 25 μm by a blade method, and fired at 140 ° C for 20 minutes to form a metal layer. As a next step, 40 g of 80% hydrazine hydrate is added to 60 g of methanol and stirred to form a solution, which is coated on a substrate, and the squeegee is pressed and pushed along the direction of the substrate to remove the substrate. Residual metallic material on the surface. As a next step, the imprinted substrate filled with the metal substance was dried at 140 ° C for ten minutes to form an electrode having a fine line width.

在下述表1中示出了根據實施例1至實施例36製備的微細線寬電極的方塊電阻、透射率、霧度和黃色指數結果，並且在圖6a至圖6c中示出實施例1至實施例36的SEM結果。 The sheet resistance, transmittance, haze, and yellowness index results of the fine line width electrodes prepared according to Examples 1 to 36 are shown in Table 1 below, and Example 1 is shown in FIGS. 6a to 6c. The SEM results of Example 36.

如上所述，本發明可提供如表1以及圖6a至圖6c所示的，先前技術很難實現的低電阻超細導電圖案的形成方法，所述方法通過在基材的槽中填充導電墨而形成導電圖案，並且用蝕刻液溶解殘留在基材表面的導電墨，將其推入並填充於基材的槽中。本發明尤其能夠提供先前技術難以實現的幾十奈米至幾十微米線寬(例如50nm~50μm線寬)的低電阻超細導電圖案。並且，本發明還能夠提高基材的透明性和絕緣特性。 As described above, the present invention can provide a method of forming a low-resistance ultra-fine conductive pattern which is difficult to realize in the prior art as shown in Table 1 and FIGS. 6a to 6c by filling a conductive ink in a groove of a substrate. A conductive pattern is formed, and the conductive ink remaining on the surface of the substrate is dissolved with an etching solution, which is pushed in and filled in the groove of the substrate. The present invention is particularly capable of providing a low-resistance ultra-fine conductive pattern of a line width of several tens of nanometers to several tens of micrometers (for example, a line width of 50 nm to 50 μm) which is difficult to achieve by the prior art. Further, the present invention can also improve the transparency and insulating properties of the substrate.

實用性 Practicality

本發明可適用於具有微細導電圖案的各種電子產品等。 The present invention is applicable to various electronic products and the like having a fine conductive pattern.

1‧‧‧基材 1‧‧‧Substrate

2‧‧‧第一膜 2‧‧‧First film

4‧‧‧模具 4‧‧‧Mold

41‧‧‧突出部 41‧‧‧Protruding

41'‧‧‧突出部 41'‧‧‧Protruding

Claims (30)

一種導電圖案的形成方法，包括步驟：a)在具有槽的基材的所述槽中一次填充導電墨；b)在具有槽的所述基材的整個表面上塗敷蝕刻液以溶解一次填充所述槽中的所述導電墨及在所述一次填充期間殘留在所述基材的表面上的導電墨；以及c)二次填充所述槽，其是通過使用物理力將殘留在所述基材的表面上的被所述蝕刻液溶解的所述導電墨推入所述槽中，其中，在步驟b)中，通過一次填充所述槽中的所述導電墨的至少一部分與在所述槽中塗敷的所述蝕刻液之混合體形成第一混合體；及通過殘留在所述基材的表面上的所述導電墨與在所述基材的表面上塗敷的所述蝕刻液之混合物形成第二混合體；在步驟c)中，所述第二混合體被推入填充所述第一混合體的所述槽中。 A method of forming a conductive pattern, comprising the steps of: a) filling a conductive ink once in the groove of a substrate having a groove; b) applying an etching solution on the entire surface of the substrate having the groove to dissolve the primary filling The conductive ink in the groove and the conductive ink remaining on the surface of the substrate during the primary filling; and c) secondary filling of the groove, which is left at the base by using physical force The conductive ink dissolved on the surface of the material by the etching solution is pushed into the groove, wherein in step b), at least a portion of the conductive ink in the groove is filled once and at the a mixture of the etching liquid applied in the groove forms a first mixture; and a mixture of the conductive ink remaining on a surface of the substrate and the etching liquid applied on a surface of the substrate Forming a second mixture; in step c), the second mixture is pushed into the trough filling the first mixture. 如請求項1所述的導電圖案的形成方法，其中，在所述步驟a)之前，進一步包括在所述基材上形成槽的步驟。 The method of forming a conductive pattern according to claim 1, wherein before the step a), further comprising the step of forming a groove on the substrate. 如請求項2所述的導電圖案的形成方法，其中，在所述基材上形成槽的步驟中，採用壓印法、雷射蝕刻法或者照相平版印刷法在所述基材上形成槽。 The method of forming a conductive pattern according to claim 2, wherein in the step of forming a groove on the substrate, a groove is formed on the substrate by an imprint method, a laser etching method or a photolithography method. 如請求項3所述的導電圖案的形成方法，其中，在採用所述壓印法時，在所述基材上形成槽之前，進一步包括塗敷紫外線固化樹脂或熱固化樹脂以形成樹脂層的步驟。 The method of forming a conductive pattern according to claim 3, wherein, when the stamping method is employed, before forming the groove on the substrate, further comprising applying an ultraviolet curable resin or a thermosetting resin to form a resin layer step. 如請求項1所述的導電圖案的形成方法，其中，作為所述導電墨使用包含金屬錯合物、金屬前體、球形金屬粒子、金屬薄片或奈米粒子的導電墨。 The method of forming a conductive pattern according to claim 1, wherein a conductive ink containing a metal complex, a metal precursor, a spherical metal particle, a metal flake or a nano particle is used as the conductive ink. 如請求項1所述的導電圖案的形成方法，其中，在所述步驟a)中，採用噴墨法、平板絲網印刷法、旋轉塗敷法、輥塗法、流動塗敷法、刮板塗敷法、滴塗法、凹版印刷法或柔版印刷法填 充所述導電墨。 The method of forming a conductive pattern according to claim 1, wherein in the step a), an inkjet method, a flat screen printing method, a spin coating method, a roll coating method, a flow coating method, a squeegee Coating method, drop coating method, gravure printing method or flexographic printing method The conductive ink is charged. 如請求項1所述的導電圖案的形成方法，其中，在所述步驟b)中，所述蝕刻液包含選自氨基甲酸銨系、碳酸銨系、碳酸氫銨系、羧酸系、內酯系、內醯胺系、環狀酸酐系化合物、酸-鹼鹽複合物、酸-鹼-醇類複合物及巰基類化合物中的一種以上的物質和氧化劑。 The method for forming a conductive pattern according to claim 1, wherein in the step b), the etching solution comprises a component selected from the group consisting of ammonium carbamate, ammonium carbonate, ammonium hydrogencarbonate, carboxylic acid, lactone One or more substances and an oxidizing agent, a mesamine, a cyclic acid anhydride compound, an acid-base salt complex, an acid-base-alcohol complex, and a mercapto compound. 如請求項1所述的導電圖案的形成方法，其中，在所述步驟b)中，採用平板絲網印刷法、旋轉塗敷法、輥塗法、流動塗敷法、刮板塗敷法、凹版印刷法或柔版印刷法塗敷所述蝕刻液，溶解殘留在所述基材的表面上的導電墨，並將所述導電墨引導至所述槽中。 The method for forming a conductive pattern according to claim 1, wherein in the step b), a flat screen printing method, a spin coating method, a roll coating method, a flow coating method, a blade coating method, The etching solution is applied by a gravure printing method or a flexographic printing method to dissolve the conductive ink remaining on the surface of the substrate and guide the conductive ink into the groove. 如請求項1所述的導電圖案的形成方法，其中，在所述步驟b)中，將所述蝕刻液塗敷在殘留有所述導電墨的所述基材的表面上，溶解所述導電墨，並且通過物理力將被所述蝕刻液溶解的所述導電墨推入並填充於所述槽中。 The method of forming a conductive pattern according to claim 1, wherein in the step b), the etching solution is applied on a surface of the substrate on which the conductive ink remains, to dissolve the conductive Ink, and the conductive ink dissolved by the etching liquid is pushed in and filled in the groove by physical force. 如請求項1所述的導電圖案的形成方法，其中，在所述步驟b)之後，進一步包括進行發黑處理的發黑步驟。 The method of forming a conductive pattern according to claim 1, wherein after the step b), the blackening step of performing a blackening process is further included. 如請求項10所述的導電圖案的形成方法，其中，在所述發黑步驟中，通過使用酸或鹼溶液的化學處理法、鍍覆法或者使用發黑組合物對表面進行印刷的方法進行發黑處理。 The method of forming a conductive pattern according to claim 10, wherein in the blackening step, a method of printing a surface by a chemical treatment method using an acid or an alkali solution, a plating method, or using a blackening composition is performed. Blackening. 如請求項11所述的導電圖案的形成方法，其中，所述使用發黑組合物對表面進行印刷的方法採用平板絲網印刷法、輥塗法、流動塗敷法、刮板塗敷法、凹版印刷法或柔版印刷法。 The method for forming a conductive pattern according to claim 11, wherein the method of printing the surface using the blackening composition employs a flat screen printing method, a roll coating method, a flow coating method, a blade coating method, Gravure printing or flexographic printing. 如請求項12所述的導電圖案的形成方法，其中，所述發黑組合物包括鈦系或鋯系錯體化合物。 The method of forming a conductive pattern according to claim 12, wherein the blackening composition comprises a titanium-based or zirconium-based compound. 一種導電膜，包括：具有槽的基材；一次填充於所述槽內的導電墨形成的膜；以及 二次填充於所述槽內的所述膜上，及由蝕刻液和所述導電墨混合而形成的混合體，其中，所述混合體包含第一混合體，其是一次填充於所述槽內的所述導電墨的至少一部分與在所述槽中塗敷的所述蝕刻液形成的混合體；以及第二混合體，其是在所述導電墨之一次填充期間殘留在所述基材的表面上的導電墨與在所述基材的表面上塗敷的所述蝕刻液形成的混合體。 A conductive film comprising: a substrate having a groove; a film formed of conductive ink once filled in the groove; Secondaryly filling the film in the tank, and a mixture formed by mixing an etchant and the conductive ink, wherein the mixture comprises a first mixture, which is filled in the tank at a time a mixture of at least a portion of the conductive ink and the etching liquid applied in the groove; and a second mixture remaining on the substrate during a filling of the conductive ink A mixture of conductive ink on the surface and the etchant applied on the surface of the substrate. 如請求項14所述的導電膜，其中，所述膜的厚度小於所述槽的深度。 The conductive film of claim 14, wherein the film has a thickness smaller than a depth of the groove. 如請求項14所述的導電膜，其中，所述膜及混合體的厚度之和等於或小於所述槽的深度。 The conductive film according to claim 14, wherein a sum of thicknesses of the film and the mixture is equal to or smaller than a depth of the groove. 如請求項14至16中任一項所述的導電膜，其中，進一步包括發黑部，所述發黑部由填充於所述槽內的所述膜及混合體中的至少一個上面的發黑組合物形成。 The conductive film according to any one of claims 14 to 16, further comprising a blackening portion, the blackening portion being filled by at least one of the film and the mixture filled in the groove The black composition is formed. 如請求項17所述的導電膜，其中，所述發黑部設置在所述槽的內表面與所述膜及混合體中的至少一個之間。 The conductive film according to claim 17, wherein the blackened portion is disposed between an inner surface of the groove and at least one of the film and the mixture. 一種導電圖案，包括：一次圖案部，其由一次填充於具有槽的基材上的所述槽內的導電墨形成；以及二次圖案部，其通過二次填充於具有導電墨與蝕刻液之混合體的所述槽而形成，其中，所述混合體包含第一混合體，其是一次填充於所述槽內的所述導電墨的至少一部分與在所述槽中塗敷的所述蝕刻液形成的混合體；以及第二混合體，其是在所述導電墨之一次填充期間殘留在所述基材的表面上的導電墨與在所述基材的表面上塗敷的所述蝕刻液形成的混合體。 A conductive pattern comprising: a primary pattern portion formed of conductive ink filled in the groove on a substrate having a groove at a time; and a secondary pattern portion which is secondarily filled with a conductive ink and an etchant Forming the groove of the mixture, wherein the mixture comprises a first mixture that is at least a portion of the conductive ink that is once filled in the groove and the etchant applied in the groove a mixed body formed; and a second mixture formed by conductive ink remaining on a surface of the substrate during a filling of the conductive ink and the etching liquid applied on a surface of the substrate a mixture of. 如請求項19所述的導電圖案，其中，所述導電墨為包含金屬錯合物、金屬前體、球形金屬粒子、金屬薄片或奈米粒子的 導電墨。 The conductive pattern according to claim 19, wherein the conductive ink is a metal-containing complex, a metal precursor, a spherical metal particle, a metal foil or a nano particle. Conductive ink. 如請求項19所述的導電圖案，其中，所述蝕刻液包含選自氨基甲酸銨系、碳酸銨系、碳酸氫銨系、羧酸系、內酯系、內醯胺系、環狀酸酐系化合物、酸-鹼鹽複合物、酸-鹼-醇類複合物及巰基系化合物中的一種以上的物質和氧化劑。 The conductive pattern according to claim 19, wherein the etching solution comprises a group selected from the group consisting of ammonium carbamate, ammonium carbonate, ammonium hydrogencarbonate, carboxylic acid, lactone, lactam, and cyclic acid anhydride. One or more substances and an oxidizing agent among the compound, the acid-base salt complex, the acid-base-alcohol complex, and the fluorenyl compound. 如請求項19所述的導電圖案，其中，所述二次圖案部通過將所述蝕刻液塗敷於所述基材的表面，溶解殘留在所述基材的表面上的導電墨，並且通過物理力將被所述蝕刻液溶解的所述導電墨推入所述槽中而形成。 The conductive pattern according to claim 19, wherein the secondary pattern portion dissolves conductive ink remaining on a surface of the substrate by applying the etching solution to a surface of the substrate, and passes A physical force is formed by pushing the conductive ink dissolved by the etching solution into the groove. 如請求項19所述的導電圖案，其中，進一步包括由填充於所述槽中的發黑組合物形成的發黑部。 The conductive pattern according to claim 19, further comprising a blackened portion formed of a blackening composition filled in the groove. 一種透明導電膜，包括：具有槽的基材；以及由填充於所述槽中的導電墨形成的導電圖案，其中，所述導電圖案包括：一次圖案部，其由一次填充於具有槽的所述基材中的導電墨形成；及二次圖案部，其通過二次填充於具有導電墨與蝕刻液之混合體的所述槽中而形成；所述混合體包含第一混合體，其是一次填充於所述槽內的所述導電墨的至少一部分與在所述槽中塗敷的所述蝕刻液形成的混合體；以及第二混合體，其是在所述導電墨之一次填充期間殘留在所述基材的表面上的導電墨與在所述基材的表面上塗敷的所述蝕刻液形成的混合體。 A transparent conductive film comprising: a substrate having a groove; and a conductive pattern formed of conductive ink filled in the groove, wherein the conductive pattern comprises: a pattern portion that is once filled in a grooved portion a conductive ink in the substrate; and a secondary pattern portion formed by secondary filling in the groove having a mixture of conductive ink and etching solution; the mixture comprising a first mixture, which is a mixture of at least a portion of the conductive ink filled in the groove and the etching liquid applied in the groove; and a second mixture that remains during one filling of the conductive ink A mixture of conductive ink on the surface of the substrate and the etchant applied on the surface of the substrate. 一種透明導電膜，包括：具有槽的基材；及導電圖案，其通過在所述槽中一次填充導電墨，及在具有蝕刻液與導電墨之混合體的所述槽中二次填充而形成，其中，所述混合體包含第一混合體，其是一次填充於所述槽內的所述導電墨的至少一部分與在所述槽中塗敷的所述蝕刻液形 成的混合體；以及第二混合體，其是在所述導電墨之一次填充期間殘留在所述基材的表面上的導電墨與在所述基材的表面上塗敷的所述蝕刻液形成的混合體。 A transparent conductive film comprising: a substrate having a groove; and a conductive pattern formed by first filling a conductive ink in the groove and secondary filling in the groove having a mixture of an etchant and a conductive ink Wherein the mixture comprises a first mixture that is at least a portion of the conductive ink that is once filled in the groove and the etched liquid applied in the groove a mixed body; and a second mixture formed by conductive ink remaining on a surface of the substrate during a filling of the conductive ink and the etching liquid applied on a surface of the substrate a mixture of. 如請求項24或25所述的透明導電膜，其中，所述導電墨為包含金屬錯合物、金屬前體、球形金屬粒子、金屬薄片或奈米粒子的導電墨。 The transparent conductive film according to claim 24, wherein the conductive ink is a conductive ink comprising a metal complex, a metal precursor, a spherical metal particle, a metal foil or a nano particle. 如請求項24或25所述的透明導電膜，其中，所述蝕刻液包含選自氨基甲酸銨系、碳酸銨系、碳酸氫銨系、羧酸系、內酯系、內醯胺系、環狀酸酐系化合物、酸-鹼鹽複合物、酸-鹼-醇類複合物及巰基系化合物中的一種以上的物質和氧化劑。 The transparent conductive film according to claim 24, wherein the etching solution is selected from the group consisting of ammonium carbamate, ammonium carbonate, ammonium hydrogencarbonate, carboxylic acid, lactone, lactam, and ring. One or more of an acid anhydride-based compound, an acid-base salt complex, an acid-base-alcohol complex, and an anthracene-based compound, and an oxidizing agent. 如請求項24所述的透明導電膜，其中，所述二次圖案部通過將所述蝕刻液塗敷於所述基材的表面，溶解殘留在所述基材的表面上的導電墨，並且通過物理力將被所述蝕刻液溶解的所述導電墨推入所述槽中而形成。 The transparent conductive film according to claim 24, wherein the secondary pattern portion dissolves conductive ink remaining on a surface of the substrate by applying the etching solution to a surface of the substrate, and The conductive ink dissolved by the etching liquid is pushed into the groove by physical force. 如請求項25所述的透明導電膜，其中，所述導電圖案通過將所述蝕刻液塗敷於所述基材的表面，溶解殘留在所述基材的表面上的導電墨，並且通過物理力將被所述蝕刻液溶解的所述導電墨推入所述槽中，進行二次填充而形成。 The transparent conductive film according to claim 25, wherein the conductive pattern dissolves conductive ink remaining on a surface of the substrate by applying the etching solution to a surface of the substrate, and passes through a physics The force is formed by pushing the conductive ink dissolved by the etching solution into the groove and performing secondary filling. 如請求項24或25所述的透明導電膜，其中，進一步包括由填充於所述槽中的發黑組合物形成的發黑部。 The transparent conductive film according to claim 24 or 25, further comprising a blackened portion formed of a blackening composition filled in the groove.
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