TWI666658B - Method for forming functional thin line pattern, method for forming transparent conductive film, method for manufacturing element, and method for manufacturing electronic device - Google Patents
Method for forming functional thin line pattern, method for forming transparent conductive film, method for manufacturing element, and method for manufacturing electronic device Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- 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
- H05K3/1241—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 ink-jet printing or drawing by dispensing
- H05K3/125—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 ink-jet printing or drawing by dispensing by ink-jet printing
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
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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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- 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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/05—Patterning and lithography; Masks; Details of resist
- H05K2203/0502—Patterning and lithography
- H05K2203/0545—Pattern for applying drops or paste; Applying a pattern made of drops or paste
Abstract
課題為，提供一種能夠高自由度而穩定地形成機能性細線之機能性細線圖樣前驅物的形成方法、機能性細線圖樣的形成方法、透明導電膜的形成方法、元件的製造方法及電子機器的製造方法、以及機能性細線圖樣、透明導電膜、元件及電子機器，係依下述方式解決，即，在基材(1)上，藉由含有機能性材料的線狀液體(2)，形成封閉的幾何圖形，將線狀液體(2)乾燥，令機能性材料沿著緣部(21，22)堆積，藉此形成由含有機能性材料的內側細線(31)與外側細線(32)所構成之機能性細線單元(3)，將機能性細線單元(3)並設1或複數個而形成機能性細線圖樣之方法；及，將機能性細線單元(3)用作為機能性細線圖樣前驅物，將由內側細線(31)及外側細線(32)所構成之細線的一部分予以除去，藉此，藉由未除去而被殘留之細線來形成機能性細線圖樣。 The subject is to provide a method for forming a functional thin line pattern precursor, a method for forming a functional thin line pattern, a method for forming a transparent conductive film, a method for manufacturing an element, and an electronic device that can form a functional thin line with high freedom and stably. The manufacturing method, the functional thin line pattern, the transparent conductive film, the device, and the electronic device are solved by forming the base material (1) with a linear liquid (2) containing a functional material. The closed geometric figure dries the linear liquid (2) so that the functional material is stacked along the edges (21, 22), thereby forming the inner thin line (31) and the outer thin line (32) containing the functional material. A functional thin line unit (3), a method of forming one or more functional thin line units (3) in parallel to form a functional thin line pattern; and using the functional thin line unit (3) as a precursor of the functional thin line pattern A part of the thin line composed of the inner thin line (31) and the outer thin line (32) is removed, whereby a functional thin line pattern is formed from the thin lines that are left without being removed.
Description
本發明有關能夠高自由度而穩定地形成機能性細線之機能性細線圖樣前驅物的形成方法、機能性細線圖樣的形成方法、透明導電膜的形成方法、元件的製造方法及電子機器的製造方法、以及機能性細線圖樣、附透明導電膜基材、元件及電子機器。 The present invention relates to a method for forming a functional thin line pattern precursor capable of forming a functional thin line with high freedom and stability, a method for forming a functional thin line pattern, a method for forming a transparent conductive film, a method for manufacturing a component, and a method for manufacturing an electronic device. And functional thin line patterns, substrates with transparent conductive film, components and electronic equipment.
專利文獻1~3中揭示以下技術，即，當將被賦予至基材上之含有導電性材料的液滴予以乾燥時，利用咖啡漬圈環現象(coffee stain phenomenon)，在該液滴的周緣部選擇性地令導電性材料堆積。專利文獻1，係將液滴以點(dot)狀賦予，藉此在該液滴的周緣部形成環狀的導電性細線。此外，專利文獻2、3，係將液滴以線狀賦予，藉此在該液滴的周緣部形成直線狀的導電性細線。 Patent Documents 1 to 3 disclose a technique in which, when a droplet containing a conductive material applied to a substrate is dried, a coffee stain phenomenon is used at the periphery of the droplet. The portion selectively deposits the conductive material. In Patent Document 1, a droplet is provided in a dot shape, thereby forming a ring-shaped conductive thin wire at a peripheral portion of the droplet. In addition, in Patent Documents 2 and 3, linear droplets are formed by applying droplets in a linear shape, thereby forming a linear conductive thin wire at the peripheral portion of the droplet.
[專利文獻1] WO2011/051952 [Patent Document 1] WO2011 / 051952
[專利文獻2] 日本特開2005-95787號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2005-95787
[專利文獻3] 日本特開2014-38992號公報 [Patent Document 3] Japanese Patent Application Publication No. 2014-38992
專利文獻1的技術中，為了將環狀的導電性細線的直徑增大，必須將以點狀被賦予之液滴的直徑增大。此外，專利文獻2的技術中，為了將直線狀的導電性細線的配置間隔增大，必須將以直線狀被賦予之液滴的線寬增大。其結果，為了形成液滴必須要賦予大量的液體，乾燥負荷會變大。若乾燥負荷變大，則難以穩定形成細線、或產距時間會變長。像這樣，依以往的技術，難以高自由度而穩定地形成細線。 In the technique of Patent Document 1, in order to increase the diameter of a ring-shaped conductive thin wire, it is necessary to increase the diameter of a droplet provided in a dot shape. In addition, in the technique of Patent Document 2, in order to increase the arrangement interval of the linear conductive thin wires, it is necessary to increase the line width of the droplets provided in the linear form. As a result, a large amount of liquid must be applied to form droplets, and the drying load becomes large. When the drying load becomes large, it becomes difficult to form a fine line stably, or the production time becomes longer. As such, it is difficult to form a thin line stably with a high degree of freedom by the conventional technology.
例如當藉由導電性細線的集合體來形成觸控面板感測器等中使用的透明導電膜時，如果能高自由度而穩定地形成導電性細線，則可實現透明導電膜的低電阻化，更可提升低視認性(導電性細線的視認困難性)。此外，不只是導電性細線，如果能高自由度而穩定地形成具有各種機能之機能性細線，則可良好地發揮該機能。 For example, when a transparent conductive film used in a touch panel sensor or the like is formed of an aggregate of conductive thin wires, if the conductive thin wire can be formed stably with a high degree of freedom, the resistance of the transparent conductive film can be reduced. , Can further improve low visibility (difficulty of conductive thin lines). In addition, not only conductive thin wires, but also high-degree-of-freedom and stable formation of functional thin wires with various functions, the function can be exhibited satisfactorily.
鑑此，本發明之課題在於提供一種能夠高自由度而穩定地形成機能性細線之機能性細線圖樣前驅物的形成方法、機能性細線圖樣的形成方法、透明導電膜的形成方法、元件的製造方法及電子機器的製造方法、以及機能性細線圖樣、附透明導電膜基材、元件及電子機器。 In view of this, it is an object of the present invention to provide a method for forming a functional thin line pattern precursor, a method for forming a functional thin line pattern, a method for forming a transparent conductive film, and device manufacturing that can form a functional thin line with high degree of freedom and stably. A method and a manufacturing method of an electronic device, a functional thin line pattern, a transparent conductive film substrate, a component, and an electronic device.
此外本發明的其他課題，將由以下記載而明朗。 In addition, the other subject of this invention will become clear from the following description.
上述課題，係藉由以下各發明而解決。 The above-mentioned problems are solved by the following inventions.
一種機能性細線圖樣前驅物的形成方法，其特徵為：在基材上，藉由含有機能性材料的線狀液體，形成封閉的幾何圖形，將前述線狀液體乾燥，令前述機能性材料沿著緣部堆積，藉此形成由含有前述機能性材料的內側細線與外側細線所構成之機能性細線圖樣前驅物。 A method for forming a functional thin line pattern precursor, which is characterized in that a closed geometric figure is formed on a substrate by a linear liquid containing a functional material, and the aforementioned linear liquid is dried so that the aforementioned functional material is formed along the substrate. The landing edge portions are stacked, thereby forming a functional thin line pattern precursor composed of an inner thin line and an outer thin line containing the aforementioned functional material.
如前述1所述之機能性細線圖樣前驅物的形成方法，其中，在基材上，藉由含有機能性材料的第1線狀液體，形成封閉的幾何圖形，將前述第1線狀液體乾燥，令前述機能性材料沿著緣部堆積，藉此形成由含有前述機能性材料的內側細線與外側細線所構成之第1機能性細線圖樣前 驅物， 接著，在前述基材上，藉由含有機能性材料的第2線狀液體，形成封閉的幾何圖形，將前述第2線狀液體乾燥，令前述機能性材料沿著緣部堆積，藉此形成由含有前述機能性材料的內側細線與外側細線所構成之第2機能性細線圖樣前驅物時，在至少一組的前述第1機能性細線圖樣前驅物與前述第2機能性細線圖樣前驅物中，以前述第1機能性細線圖樣前驅物的前述外側細線，和前述第2機能性細線圖樣前驅物的前述外側細線連接，且前述第1機能性細線圖樣前驅物的前述內側細線，和前述第2機能性細線圖樣前驅物的前述內側細線不連接之方式，來形成前述第1機能性細線圖樣前驅物及前述第2機能性細線圖樣前驅物。 The method for forming a functional thin line pattern precursor according to the above 1, wherein a closed geometric figure is formed on the substrate by the first linear liquid containing a functional material, and the first linear liquid is dried , The functional materials are stacked along the edges to form a first functional thin line pattern composed of an inner thin line and an outer thin line containing the functional material. Drive Next, a closed geometric figure is formed on the substrate by a second linear liquid containing a functional material, the second linear liquid is dried, and the functional material is deposited along the edges to form a closed geometry. When the second functional thin line pattern precursor is composed of the inner thin line and the outer thin line containing the functional material, at least one set of the first functional thin line pattern precursor and the second functional thin line pattern precursor are included. , Connecting the outer thin line of the first functional thin line pattern precursor to the outer thin line of the second functional thin line pattern precursor, and the inner thin line of the first functional thin line pattern precursor, and the first (2) The first thin functional line pattern precursor and the second functional thin line pattern precursor are formed in a manner that the inner thin lines of the functional thin line pattern precursor are not connected.
如前述2所述之機能性細線圖樣前驅物的形成方法，其中，將由前述第1線狀液體所構成之前述封閉的幾何圖形做成多角形，藉此形成各個多角形亦即由內側細線與外側細線所構成之第1機能性細線圖樣前驅物，將由前述第2線狀液體所構成之前述封閉的幾何圖形做成多角形，藉此形成各個多角形亦即由內側細線與外側細線所構成之第2機能性細線圖樣前驅物，在至少一組的前述第1機能性細線圖樣前驅物與前述第2機能性細線圖樣前驅物中，以前述第1機能性細線圖樣前驅物的多角形即前述外側細線，和前述第2機能性細 線圖樣前驅物的多角形即前述外側細線，令夾著多角形的頂點之兩邊彼此交錯而以2點的交點連接之方式，來形成前述第1機能性細線圖樣前驅物及前述第2機能性細線圖樣前驅物。 The method for forming a functional thin line pattern precursor as described in 2 above, wherein the closed geometric figure composed of the first linear liquid is made into a polygon, thereby forming each polygon, that is, the inner thin line and the The first functional thin line pattern precursor composed of the outer thin line is a polygon made of the closed geometric figure composed of the second linear liquid, thereby forming each polygon, that is, the inner thin line and the outer thin line The second functional thin line pattern precursor is a polygon of the first functional thin line pattern precursor in at least one of the first functional thin line pattern precursor and the second functional thin line pattern precursor. The outer thin line is thinner than the second function The polygon of the line pattern precursor is the aforementioned outer thin line, so that the two sides sandwiching the vertices of the polygon are connected to each other and connected at the intersection of two points to form the first functional thin line pattern precursor and the second function. Thin line pattern precursor.
如前述3所述之機能性細線圖樣前驅物的形成方法，其中，前述多角形，為相對於前述基材的長邊方向而言各邊呈傾斜之四角形。 The method for forming a functional thin line pattern precursor according to the above 3, wherein the polygon is a quadrangular shape whose sides are inclined relative to a long side direction of the substrate.
如前述2所述之機能性細線圖樣前驅物的形成方法，其中，將由前述第1線狀液體所構成之前述封閉的幾何圖形做成圓形，藉此形成各個圓形亦即由內側細線與外側細線所構成之第1機能性細線圖樣前驅物，將由前述第2線狀液體所構成之前述封閉的幾何圖形做成圓形，藉此形成各個圓形亦即由內側細線與外側細線所構成之第2機能性細線圖樣前驅物，在至少一組的前述第1機能性細線圖樣前驅物與前述第2機能性細線圖樣前驅物中，以前述第1機能性細線圖樣前驅物的圓形即前述外側細線，與前述第2機能性細線圖樣前驅物的圓形即前述外側細線，令圓形的圓周彼此交錯而以2點的交點連接之方式，來形成前述第1機能性細線圖樣前驅物及前述第2機能性細線圖樣前驅物。 The method for forming a functional thin line pattern precursor as described in the above 2, wherein the closed geometric figure composed of the first linear liquid is made into a circle, thereby forming each circle, that is, the inner thin line and the The first functional thin line pattern precursor composed of the outer thin line is formed into a circle by forming the closed geometric figure composed of the second linear liquid, thereby forming each circle, that is, the inner thin line and the outer thin line. The second functional thin line pattern precursor is at least one set of the aforementioned first functional thin line pattern precursor and the aforementioned second functional thin line pattern precursor. The circle of the aforementioned first functional thin line pattern precursor is The outer thin line and the circle of the second functional thin line pattern precursor, that is, the outer thin line, are formed by staggering the circumferences of the circles and connecting them at the intersection of two points to form the first functional thin line pattern precursor. And the aforementioned second functional thin line pattern precursor.
如前述2~5中任一者所述之機能性細線圖樣前驅物 的形成方法，其中，作為前述機能性材料係使用導電性材料，通過互相連接之由前述第1機能性細線圖樣前驅物的前述外側細線與前述第2機能性細線圖樣前驅物的前述外側細線所構成之通電路徑而通電，藉此對前述外側細線施加電解鍍覆。 Functional thin line pattern precursor as described in any of 2 to 5 above A method of forming wherein the functional material is a conductive material, and the outer thin line of the first functional thin line pattern precursor and the outer thin line of the second functional thin line pattern precursor are interconnected by the outer thin line of the first functional thin line pattern precursor. The conductive path is configured to be energized, whereby electrolytic plating is applied to the outer fine wires.
如前述1所述之機能性細線圖樣前驅物的形成方法，其中，在基材上，藉由含有機能性材料的第1線狀液體，形成封閉的幾何圖形，將前述第1線狀液體乾燥，令前述機能性材料沿著緣部堆積，藉此形成由含有前述機能性材料的內側細線與外側細線所構成之第1機能性細線圖樣前驅物，接著，在前述基材上，藉由含有機能性材料的第2線狀液體，形成封閉的幾何圖形，將前述第2線狀液體乾燥，令前述機能性材料沿著緣部堆積，藉此形成由含有前述機能性材料的內側細線與外側細線所構成之第2機能性細線圖樣前驅物時，在至少一組的前述第1機能性細線圖樣前驅物與前述第2機能性細線圖樣前驅物中，以前述第1機能性細線圖樣前驅物的前述內側細線及/或前述外側細線，和前述第2機能性細線圖樣前驅物的前述內側細線及/或前述外側細線連接之方式，來形成前述第1機能性細線圖樣前驅物及前述第2機能性細線圖樣前驅物。 The method for forming a functional thin line pattern precursor according to the above 1, wherein a closed geometric figure is formed on the substrate by the first linear liquid containing a functional material, and the first linear liquid is dried The first functional thin line pattern precursor composed of the inner thin line and the outer thin line containing the functional material is formed by stacking the functional material along the edge portion. Then, on the substrate, The second linear liquid of the functional material forms a closed geometric figure. The second linear liquid is dried, and the functional material is stacked along the edge, thereby forming the inner thin line and the outer side containing the functional material. When the second functional thin line pattern precursor is composed of thin lines, the first functional thin line pattern precursor is used in at least one set of the first functional thin line pattern precursor and the second functional thin line pattern precursor. The inner thin line and / or the outer thin line are connected to the inner thin line and / or the outer thin line of the second functional thin line pattern precursor to form a front. The first functional thin line pattern precursor and the second functional thin line pattern precursor are described.
如前述1所述之機能性細線圖樣前驅物的形成方法，其中，在基材上，藉由含有機能性材料的第1線狀液體，形成封閉的幾何圖形，將前述第1線狀液體乾燥，令前述機能性材料沿著緣部堆積，藉此形成由含有前述機能性材料的內側細線與外側細線所構成之第1機能性細線圖樣前驅物，接著，在前述基材上，藉由含有機能性材料的第2線狀液體，形成封閉的幾何圖形，將前述第2線狀液體乾燥，令前述機能性材料沿著緣部堆積，藉此形成由含有前述機能性材料的內側細線與外側細線所構成之第2機能性細線圖樣前驅物時，在至少一組的前述第1機能性細線圖樣前驅物與前述第2機能性細線圖樣前驅物中，以前述第1機能性細線圖樣前驅物的前述外側細線，和前述第2機能性細線圖樣前驅物的前述外側細線不連接，且前述第1機能性細線圖樣前驅物的前述內側細線，和前述第2機能性細線圖樣前驅物的前述內側細線不連接之方式，來形成前述第1機能性細線圖樣前驅物及前述第2機能性細線圖樣前驅物。 The method for forming a functional thin line pattern precursor according to the above 1, wherein a closed geometric figure is formed on the substrate by the first linear liquid containing a functional material, and the first linear liquid is dried The first functional thin line pattern precursor composed of the inner thin line and the outer thin line containing the functional material is formed by stacking the functional material along the edge portion. Then, on the substrate, The second linear liquid of the functional material forms a closed geometric figure. The second linear liquid is dried, and the functional material is stacked along the edge, thereby forming the inner thin line and the outer side containing the functional material. When the second functional thin line pattern precursor is composed of thin lines, the first functional thin line pattern precursor is used in at least one set of the first functional thin line pattern precursor and the second functional thin line pattern precursor. The outer thin line of is not connected to the outer thin line of the second functional thin line pattern precursor, and the inner thin line of the first functional thin line pattern precursor, The inner side of the foregoing second thin wires functional thin line pattern of the precursor is not connected to first form the thin line pattern is functional precursor and the second precursor functional thin line pattern.
如前述2~5、7、8中任一者所述之機能性細線圖樣前驅物的形成方法，其中，將複數個前述第1機能性細線圖樣前驅物並設複數個，接著，將前述第2機能性細線圖樣前驅物，以被夾在 並設複數個的前述第1機能性細線圖樣前驅物之間之方式，予以並設複數個。 The method for forming a functional thin line pattern precursor as described in any one of 2 to 5, 7, and 8, wherein a plurality of the first functional thin line pattern precursors are set and a plurality of the first functional thin line pattern precursors are set, and then, the first 2 functional thin line pattern precursors to be sandwiched A plurality of the aforementioned first functional thin line pattern precursors are set in parallel, and a plurality of them are set in parallel.
如前述9所述之機能性細線圖樣前驅物的形成方法，其中，將複數個前述第1機能性細線圖樣前驅物、及複數個前述第2機能性細線圖樣前驅物，分別以規定間距形成。 The method for forming a functional thin line pattern precursor as described in 9 above, wherein a plurality of the first functional thin line pattern precursors and a plurality of the second functional thin line pattern precursors are formed at predetermined intervals, respectively.
如前述2~5、7、8中任一者所述之機能性細線圖樣前驅物的形成方法，其中，將前述第1機能性細線圖樣前驅物、與前述第2機能性細線圖樣前驅物，以相同形狀形成。 The method for forming a functional thin line pattern precursor according to any one of 2 to 5, 7, and 8, wherein the first functional thin line pattern precursor and the second functional thin line pattern precursor are formed, Formed in the same shape.
如前述2~5、7、8中任一者所述之機能性細線圖樣前驅物的形成方法，其中，形成前述第1機能性細線圖樣前驅物、及前述第2機能性細線圖樣前驅物，接著，將又1或複數個前述機能性細線圖樣前驅物，分成1或複數次形成。 The method for forming a functional thin line pattern precursor as described in any one of 2 to 5, 7, and 8, wherein the first functional thin line pattern precursor and the second functional thin line pattern precursor are formed, Then, one or a plurality of the aforementioned functional thin line pattern precursors are divided into one or a plurality of times to form.
如前述1~5、7、8中任一者所述之機能性細線圖樣前驅物的形成方法，其中，在前述基材的兩面分別形成前述機能性細線圖樣前驅物。 The method for forming a functional thin line pattern precursor according to any one of 1 to 5, 7, and 8, wherein the functional thin line pattern precursor is formed on both sides of the substrate, respectively.
如前述1~5、7、8中任一者所述之機能性細線圖樣 前驅物的形成方法，其中，藉由噴墨法將含有前述機能性材料之複數個液滴賦予至前述基材上，將複數個前述液滴在前述基材上合一，藉此形成前述線狀液體。 Functional thin line pattern as described in any of 1 to 5, 7, and 8 above A precursor formation method in which a plurality of droplets containing the functional material are applied to the substrate by an inkjet method, and the plurality of droplets are integrated on the substrate to form the line.状 液。 Liquid.
一種機能性細線圖樣的形成方法，其特徵為：將藉由前述1~5、7、8中任一者所述之機能性細線圖樣前驅物的形成方法而形成之由前述機能性細線圖樣前驅物的前述內側細線及前述外側細線所構成之細線的一部分予以除去，藉此，藉由未除去而被殘留之細線來形成機能性細線圖樣。 A method for forming a functional thin line pattern, characterized in that the functional thin line pattern precursor is formed by the method for forming a functional thin line pattern precursor described in any one of 1 to 5, 7, and 8 described above. A part of the thin line formed by the inner thin line and the outer thin line of the object is removed, and thereby a functional thin line pattern is formed by the thin line left without being removed.
如前述15所述之機能性細線圖樣的形成方法，其中，將前述內側細線予以除去，藉此，藉由未除去而被殘留之前述外側細線來形成機能性細線圖樣。 The method for forming a functional thin line pattern according to the above 15, wherein the inner thin line is removed, and thereby the functional thin line pattern is formed from the outer thin line that remains without being removed.
一種透明導電膜的形成方法，其特徵為：在基材上，形成由導電性細線的集合體所構成之透明導電膜時，在前述16所述之機能性細線圖樣的製造方法中藉由由使用導電性材料作為前述機能性材料而形成之前述機能性細線圖樣，來形成前述導電性細線的集合體。 A method for forming a transparent conductive film, characterized in that when a transparent conductive film composed of an assembly of conductive thin wires is formed on a substrate, the method for manufacturing a functional thin line pattern as described in 16 above is adopted by The functional thin line pattern formed by using a conductive material as the functional material to form the aggregate of the conductive thin lines.
一種元件的製造方法，其特徵為：製造具有透明導電膜之元件時，藉由前述17所述之透明導電膜的形成方法來形成前 述透明導電膜。 A method for manufacturing a device, characterized in that: when manufacturing a device having a transparent conductive film, The transparent conductive film is described.
一種電子機器的製造方法，其特徵為：製造具備具有透明導電膜的元件之電子機器時，藉由前述18所述之元件的製造方法來製造前述具有透明導電膜的元件。 An electronic device manufacturing method, characterized in that, when manufacturing an electronic device provided with an element having a transparent conductive film, the element having a transparent conductive film is manufactured by the method for manufacturing an element described in 18 above.
一種機能性細線圖樣，其特徵為：在基材上，含有機能性材料的多角形狀細線被二維地並設複數個，至少一組的多角形狀細線，令夾著多角形的頂點之兩邊彼此交錯而以2點的交點被連接。 A functional thin line pattern, characterized in that, on a substrate, a polygonal shape thin line containing a functional material is two-dimensionally arranged in parallel, at least one set of polygonal shape thin lines, so that two sides sandwiching a vertex of the polygon are mutually Staggered and connected at the intersection of 2 points.
如前述20所述之機能性細線圖樣，其中，互相連接之前述多角形狀細線的內部區域的重複面積，為各多角形狀細線的內部區域的面積的10分之1以下。 The functional thin line pattern according to the aforementioned 20, wherein the repeating area of the inner area of the polygonal thin lines connected to each other is 1/10 or less of the area of the inner area of each of the polygonal thin lines.
如前述20或21所述之機能性細線圖樣，其中，前述多角形狀細線，為三角形、四角形、六角形或八角形。 The functional thin line pattern according to the foregoing 20 or 21, wherein the polygonal thin line is a triangle, a quadrangle, a hexagon, or an octagon.
如前述22所述之機能性細線圖樣，其中，將相對於前述基材的長邊方向而言各邊呈傾斜之四角形即前述多角形狀細線，於該基材的長邊方向及寬度方向分別以規定間距並設複數個而成。 The functional thin line pattern according to the aforementioned 22, wherein the polygonal thin lines, each of which is inclined with respect to the long side direction of the base material, is a polygonal shape thin line, and the long side direction and the width direction of the base material are respectively It is provided by a predetermined distance and a plurality of them.
如前述20、21、23中任一者所述之機能性細線圖樣，其中，前述機能性材料為導電性材料。 The functional thin line pattern according to any one of 20, 21, and 23, wherein the functional material is a conductive material.
如前述20、21、23中任一者所述之機能性細線圖樣，其中，前述多角形狀細線被鍍覆層披覆。 The functional thin line pattern according to any one of the foregoing 20, 21, and 23, wherein the polygonal thin line is covered with a plating layer.
如前述20、21、23中任一者所述之機能性細線圖樣，其中，設於前述基材的兩面。 The functional thin line pattern according to any one of the aforementioned 20, 21, and 23, which is provided on both sides of the aforementioned substrate.
一種附透明導電膜基材，其特徵為：在基材表面具有由前述機能性材料為導電性材料的前述20、21、23中任一者所述之機能性細線圖樣所構成之透明導電膜。 A substrate with a transparent conductive film, characterized in that the substrate has a transparent conductive film composed of the functional thin line pattern described in any one of the aforementioned 20, 21, and 23 as a conductive material on the surface of the substrate. .
一種元件，其特徵為：具有前述27所述之附透明導電膜基材。 An element, comprising the substrate with a transparent conductive film as described in 27 above.
一種電子機器，其特徵為：具備前述28所述之元件。 An electronic device including the element described in 28 above.
一種機能性細線圖樣的形成方法，其特徵為：在基材上，藉由含有機能性材料的線狀液體，形成封閉的幾何圖形，將前述線狀液體乾燥，令前述機能性材料沿著緣部堆積，藉此形成由含有前述機能性材料的內側細線與外側細 線所構成之機能性細線單元，將前述機能性細線單元並設1或複數個而形成機能性細線圖樣。 A method for forming a functional thin line pattern, characterized in that a closed geometric figure is formed on a substrate by a linear liquid containing a functional material, and the aforementioned linear liquid is dried so that the aforementioned functional material is along the edge. The parts are stacked to form a thin inner line and an outer thin line containing the functional material. The functional thin line unit composed of lines is formed by arranging one or more functional thin line units as described above to form a functional thin line pattern.
一種機能性細線圖樣，係將機能性細線單元並設1或複數個而成，該機能性細線單元由：內側細線，含有在基材上以呈封閉的幾何圖形之方式設置之機能性材料；及外側細線，含有在前述基材上以呈圍繞前述內側細線的封閉的幾何圖形之方式設置之前述機能性材料；所構成。 A functional thin line pattern is formed by arranging one or more functional thin line units. The functional thin line unit is composed of: an inner thin line containing a functional material arranged in a closed geometric pattern on a substrate; The outer thin line includes the functional material provided on the base material so as to form a closed geometric pattern surrounding the inner thin line;
按照本發明，能夠提供一種能夠高自由度而穩定地形成機能性細線之機能性細線圖樣前驅物的形成方法、機能性細線圖樣的形成方法、透明導電膜的形成方法、元件的製造方法及電子機器的製造方法、以及機能性細線圖樣、附透明導電膜基材、元件及電子機器。 According to the present invention, it is possible to provide a method for forming a functional thin line pattern precursor capable of forming a functional thin line with high freedom and stability, a method for forming a functional thin line pattern, a method for forming a transparent conductive film, a method for manufacturing a device, and electronics. Method for manufacturing machine, functional thin line pattern, base material with transparent conductive film, element, and electronic device.
1‧‧‧基材 1‧‧‧ substrate
2‧‧‧第1線狀液體 2‧‧‧ 1st linear liquid
20‧‧‧未被賦予液體之區域 20‧‧‧ Area not given a liquid
21‧‧‧內側緣 21‧‧‧ inside edge
22‧‧‧外側緣 22‧‧‧ outside edge
3‧‧‧第1細線單元 3‧‧‧ 1st Thin Line Unit
31‧‧‧內側細線 31‧‧‧ thin inside
32‧‧‧外側細線 32‧‧‧ outside thin line
4‧‧‧第2線狀液體 4‧‧‧ 2nd linear liquid
40‧‧‧未被賦予液體之區域 40‧‧‧ Area not given a liquid
41‧‧‧內側緣 41‧‧‧ inside edge
42‧‧‧外側緣 42‧‧‧outer margin
5‧‧‧第2細線單元 5‧‧‧ 2nd Thin Line Unit
51‧‧‧內側細線 51‧‧‧ thin inside
52‧‧‧外側細線 52‧‧‧ outside thin line
[圖1]細線圖樣被形成之情形的說明立體圖。 [Fig. 1] An explanatory perspective view of a case where a thin line pattern is formed.
[圖2]將機能性材料搬運至液體的緣部之流動的說明圖，(a)為由封閉的幾何圖形所構成之線狀液體的情形示意圖，(b)為參考例，為非封閉的幾何圖形之液體的 情形示意圖。 [Figure 2] An explanatory diagram of the flow of a functional material to the edge of a liquid, (a) is a schematic diagram of a linear liquid composed of closed geometric figures, and (b) is a reference example, which is not closed Geometrical liquid Situation diagram.
[圖3]幾何圖形為四角形的情形下之機能性細線圖樣形成說明圖。 [Fig. 3] An explanatory diagram of the formation of a functional thin line pattern when the geometric figure is a quadrangle.
[圖4]幾何圖形為四角形的情形下之機能性細線圖樣形成說明圖。 [Fig. 4] An explanatory diagram of the formation of a functional thin line pattern when the geometric figure is a quadrangle.
[圖5]電解鍍覆處理之一例說明圖。 [Fig. 5] An explanatory diagram of an example of electrolytic plating treatment.
[圖6]受到電解鍍覆之機能性細線圖樣說明圖。 [Fig. 6] An explanatory diagram of a functional thin line pattern subjected to electrolytic plating.
[圖7]被除去了一部分細線之機能性細線圖樣說明圖。 [Fig. 7] A functional thin line pattern explanatory diagram with a part of thin lines removed.
[圖8]圖7的重要部位擴大圖。 [Fig. 8] An enlarged view of an important part of Fig. 7. [Fig.
[圖9]在基材的兩面形成機能性細線圖樣的情形之一例說明圖。 [FIG. 9] An explanatory diagram of an example of a case where a functional thin line pattern is formed on both sides of a base material.
[圖10]具備藉由機能性細線圖樣所構成之透明導電膜的觸控面板感測器之一例說明圖。 [Fig. 10] An explanatory diagram of an example of a touch panel sensor including a transparent conductive film composed of a functional thin line pattern.
[圖11]幾何圖形為三角形的情形下之機能性細線圖樣形成說明圖。 [Fig. 11] An explanatory diagram of the formation of a functional thin line pattern when the geometric figure is a triangle.
[圖12]幾何圖形為六角形的情形下之機能性細線圖樣形成說明圖。 [Fig. 12] An explanatory diagram of the formation of a functional thin line pattern when the geometric figure is a hexagon.
[圖13]幾何圖形為八角形的情形下之機能性細線圖樣形成說明圖。 [Fig. 13] An explanatory diagram of the formation of a functional thin line pattern when the geometric figure is an octagon.
[圖14]幾何圖形為圓形的情形下之機能性細線圖樣形成說明圖。 [Fig. 14] An explanatory diagram of the formation of a functional thin line pattern when the geometric figure is a circle.
[圖15]互相鄰接的細線單元的連接形態之另一例說明圖。 [FIG. 15] An explanatory diagram of another example of the connection form of the thin wire units adjacent to each other.
[圖16]幾何圖形之又另一例說明圖。 [Fig. 16] Another explanatory diagram of a geometric figure.
[圖17]形成於基材上的細線單元之一例示意立體圖。 17 A schematic perspective view of an example of a thin line unit formed on a substrate.
[圖18]由內側細線與外側細線所構成之實施例1的細線圖樣(1)的光學顯微鏡照片。 [Fig. 18] An optical microscope photograph of a thin line pattern (1) of Example 1 composed of an inner thin line and an outer thin line.
[圖19]在外側細線施加有鍍覆之實施例2的細線圖樣(2)的光學顯微鏡照片。 [Fig. 19] An optical microscope photograph of the thin line pattern (2) of Example 2 to which plating is applied on the outer thin line.
[圖20]被除去了內側細線之實施例3的細線圖樣(3)的光學顯微鏡照片。 [Fig. 20] An optical microscope photograph of the thin line pattern (3) of Example 3 from which the inner thin line has been removed.
本發明中，是在基材上，藉由含有機能性材料的線狀液體，形成封閉的幾何圖形，接著，將前述線狀液體乾燥，令前述機能性材料沿著緣部堆積，藉此形成由含有機能性材料的內側細線與外側細線所構成之機能性細線單元(以下亦簡稱為細線單元)。將細線單元在基材上並設1或複數個，藉此便能形成機能性細線圖樣。如此一來，可獲得能夠高自由度而穩定地形成機能性細線之效果。 In the present invention, a closed geometric figure is formed on a substrate by a linear liquid containing a functional material, and then the linear liquid is dried, so that the functional material is stacked along the edge, thereby forming A functional thin line unit (hereinafter also simply referred to as a thin line unit) composed of an inner thin line and an outer thin line containing a functional material. By placing one or more thin line units on the substrate, a functional thin line pattern can be formed. In this way, it is possible to obtain an effect that a functional thin line can be formed stably with a high degree of freedom.
又，本發明之較佳態樣中，該細線單元，係被用作為用來形成機能性細線圖樣之機能性細線圖樣前驅物(以下亦簡稱為前驅物)。亦即，將由構成前驅物的內側細線與外側細線所構成之機能性細線的一部分予以除去，藉此，藉由未除去而被殘留之細線，便能形成機能性 細線圖樣。如此一來，能夠更加提高圖樣形成的自由度，特別是可獲得能夠將構成機能性細線圖樣之細線的配置間隔予以高自由度地調整之效果。 Furthermore, in a preferred aspect of the present invention, the thin line unit is used as a functional thin line pattern precursor (hereinafter also simply referred to as a precursor) for forming a functional thin line pattern. That is, a part of the functional thin line composed of the inner thin line and the outer thin line constituting the precursor is removed, and thus, the functional thin line is left without being removed to form a functional line. Thin line pattern. In this way, it is possible to further increase the degree of freedom in pattern formation, and in particular, it is possible to obtain an effect that the arrangement interval of the thin lines constituting the functional thin line pattern can be adjusted with a high degree of freedom.
以下，參照圖面說明本實施方式。 Hereinafter, this embodiment will be described with reference to the drawings.
首先，參照圖1說明從線狀液體形成細線單元之製程。 First, a process for forming a thin wire unit from a linear liquid will be described with reference to FIG. 1.
如圖1(a)所示，在基材1上，藉由線狀液體2，形成封閉的幾何圖形。由線狀液體2所構成之幾何圖形，將未被賦予液體之區域20涵括於內部，藉此，就緣部而言具有互相獨立的內側緣21與外側緣22。內側緣21，為藉由線狀液體2而形成之封閉的幾何圖形的內側的緣部，為和未被賦予液體之區域20鄰接的緣部。外側緣22，為藉由線狀液體2而形成之封閉的幾何圖形的外側的緣部，和內側緣21並未連接。當令該液體2乾燥時，利用咖啡漬圈環現象，沿著緣部亦即內側緣21及外側緣22令機能性材料選擇性地堆積，藉此，如圖1(b)所示，分別會在和內側緣21相對應之位置形成內側細線31，在和外側緣22相對應之位置形成外側細線32。 As shown in FIG. 1 (a), a closed geometric figure is formed on the substrate 1 by the linear liquid 2. The geometrical figure composed of the linear liquid 2 encompasses the region 20 to which the liquid is not imparted, thereby having an inner edge 21 and an outer edge 22 that are independent from each other in terms of the edge portion. The inner edge 21 is an inner edge portion of the closed geometric figure formed by the linear liquid 2 and is an edge portion adjacent to the region 20 to which the liquid is not applied. The outer edge 22 is an outer edge portion of the closed geometric figure formed by the linear liquid 2 and is not connected to the inner edge 21. When the liquid 2 is dried, the coffee stain ring phenomenon is used to selectively stack functional materials along the edges, that is, the inner edge 21 and the outer edge 22, and as shown in FIG. An inner thin line 31 is formed at a position corresponding to the inner edge 21, and an outer thin line 32 is formed at a position corresponding to the outer edge 22.
像這樣，便形成由含有機能性材料的內側細線31與圍繞該內側細線31的外側細線32所構成之細線單元3。構成細線單元3之內側細線31與外側細線32並未互相連接而是獨立。內側細線31與外側細線32，相較於線狀液體2的線寬(線的粗度)而言十分地細。圖示例子中，線狀液體2，具有1個內側緣21與1個外側緣 22，形成由一對的內側細線31及外側細線32所構成之細線單元3。 In this manner, the thin-line unit 3 including the inner thin line 31 containing a functional material and the outer thin line 32 surrounding the inner thin line 31 is formed. The inner thin line 31 and the outer thin line 32 constituting the thin line unit 3 are not connected to each other but are independent. The inner thin line 31 and the outer thin line 32 are very thin compared to the line width (line thickness) of the linear liquid 2. In the example shown, the linear liquid 2 has one inner edge 21 and one outer edge. 22, forming a thin line unit 3 composed of a pair of inner thin lines 31 and outer thin lines 32.
參照圖2說明從線狀液體2形成細線單元3所造成之效果。 The effect of forming the thin wire unit 3 from the linear liquid 2 will be described with reference to FIG. 2.
如圖2(a)所示，被賦予至基材1上之線狀液體2的乾燥情況，相較於中央部而言在內側緣21及外側緣22較快，因此首先會沿著內側緣21及外側緣22發生機能性材料的局部性堆積。藉由堆積出的機能性材料，液體的緣會成為被固定化之狀態(接觸線的固定化)，而抑制往後的乾燥所伴隨之線狀液體2的粗度方向的收縮。在線狀液體2中，為了彌補因在內側緣21及外側緣22之蒸發而喪失之量的液體，會形成從中央部朝向內側緣21之流動、及從中央部朝向外側緣22之流動。圖中，流動的方向以箭頭概念性地表示。藉由此流動，機能性材料會進一步被搬運至內側緣21及外側緣22而堆積。其結果，在和內側緣21及外側緣22相對應之位置，會分別形成含有機能性材料之內側細線31及外側細線32。 As shown in FIG. 2 (a), the drying of the linear liquid 2 imparted to the substrate 1 is faster at the inner edge 21 and the outer edge 22 than at the center portion, so it will first follow the inner edge. 21 and the outer edge 22 have localized accumulation of functional materials. With the stacked functional materials, the edge of the liquid becomes fixed (fixation of the contact line), and the shrinkage in the thickness direction of the linear liquid 2 accompanying the subsequent drying is suppressed. In the linear liquid 2, in order to compensate for the amount of liquid lost by evaporation on the inner edge 21 and the outer edge 22, a flow from the central portion toward the inner edge 21 and a flow from the central portion toward the outer edge 22 are formed. In the figure, the direction of flow is conceptually indicated by arrows. As a result of this flow, the functional material is further transported to the inner edge 21 and the outer edge 22 to be stacked. As a result, the inner thin line 31 and the outer thin line 32 containing a functional material are formed at positions corresponding to the inner edge 21 and the outer edge 22, respectively.
對比如圖2(b)參考例所示般，在非封閉的幾何圖形之液體100的緣101令機能性材料選擇性地堆積之情形，圖2(a)所示之線狀液體2，是將未被賦予液體之區域20涵括於內部，藉此能夠削減液體的賦予量，能夠減低乾燥負荷。如此一來，能夠縮短產距時間而提升生產效率。 As shown in the reference example of Fig. 2 (b), in the case where the edge 101 of the liquid 100 of the non-closed geometry causes the functional materials to selectively accumulate, the linear liquid 2 shown in Fig. 2 (a) is By including the region 20 to which no liquid is applied, the amount of liquid applied can be reduced and the drying load can be reduced. In this way, production time can be shortened and production efficiency can be improved.
又，線狀液體2，將未被賦予液體之區域20 涵括於內部，藉此，液體的乾燥所伴隨之氣化熱的總量會變得相對較小。因此，會抑制乾燥所伴隨之基材溫度的變化或不均一化，能夠穩定地形成上述液流。 In addition, the linear liquid 2 is a region 20 to which no liquid is given. Contained inside, the total amount of heat of vaporization accompanying the drying of the liquid becomes relatively small. Therefore, it is possible to suppress the variation or non-uniformity of the temperature of the substrate accompanying the drying, and it is possible to form the liquid flow stably.
此外又，線狀液體2，將未被賦予液體之區域20涵括於內部，藉此，能夠縮短機能性材料藉由流動而到達至緣為止的平均移動距離。 In addition, the linear liquid 2 includes the region 20 to which the liquid is not provided, so that the average moving distance of the functional material from the flow to the edge can be shortened.
其結果，即使以相對較大的直徑形成線狀液體2的情形下，仍能穩定地顯現咖啡漬圈環現象，能使內側細線31及外側細線32的形成穩定化。如此一來，可獲得能夠高自由度而穩定地形成機能性細線亦即內側細線31及外側細線32之效果。 As a result, even when the linear liquid 2 is formed with a relatively large diameter, the coffee stain ring phenomenon can be stably developed, and the formation of the inner thin lines 31 and the outer thin lines 32 can be stabilized. In this way, it is possible to obtain an effect that a functional thin line, that is, an inner thin line 31 and an outer thin line 32 can be formed stably with a high degree of freedom.
較佳是，促進形成將機能性材料搬運至緣的流動。例如，藉由調整固態成分濃度、液體與基材的接觸角、液體的量、基材的加熱溫度、液體的配置密度、或溫度、濕度、氣壓這些環境因子等條件，能夠將液體的緣予以早期地固定化，或能增大液體中央部與緣的蒸發量之差距。如此一來，能夠促進形成將機能性材料搬運至緣的流動。 It is preferable to promote the flow which conveys a functional material to an edge. For example, by adjusting conditions such as the concentration of the solid component, the contact angle between the liquid and the substrate, the amount of liquid, the heating temperature of the substrate, the density of the liquid, or the environmental factors such as temperature, humidity, and air pressure, the margin of the liquid can be determined. Early immobilization may increase the difference in evaporation between the central part and the edge of the liquid. In this way, it is possible to promote the formation of a flow that transports the functional material to the edge.
線狀液體2對基材1上之賦予，能夠藉由噴墨法來進行。具體而言，令具備未圖示的液滴吐出元件之噴墨頭一面相對於基材做相對移動，一面從噴墨頭的噴嘴吐出含有機能性材料之墨水，令被吐出的墨水滴於基材上合一，便能形成線狀液體2。噴墨頭的液滴吐出方式並無特別限定，例如能夠使用壓電(piezoelectric)方式或熱 泡(thermal bubble)方式等。 The application of the linear liquid 2 to the substrate 1 can be performed by an inkjet method. Specifically, an inkjet head provided with a liquid droplet ejection element (not shown) is relatively moved with respect to the substrate, and ink containing a functional material is ejected from a nozzle of the inkjet head, so that the ejected ink is dropped on the substrate. When the material is united, a linear liquid 2 can be formed. The droplet discharge method of the inkjet head is not particularly limited. For example, a piezoelectric method or a thermal method can be used. Bubble (thermal bubble) method and so on.
藉由使用噴墨法，能夠藉由線狀液體2，以期望的形狀自在地形成封閉的幾何圖形。能夠和線狀液體2的內側緣21及外側緣22的形狀相對應，來將欲獲得之構成細線單元3的內側細線31及外側細線32的形狀，分別形成成為期望的封閉的幾何圖形。因此，藉由使用噴墨法，能夠更加高自由度地形成機能性細線。 By using the inkjet method, a closed geometric figure can be formed freely in a desired shape by the linear liquid 2. Corresponding to the shape of the inner edge 21 and the outer edge 22 of the linear liquid 2, the shape of the inner thin line 31 and the outer thin line 32 constituting the thin line unit 3 to be obtained can be respectively formed into desired closed geometric figures. Therefore, by using the inkjet method, it is possible to form a functional thin line with a higher degree of freedom.
以下，舉出在基材1上形成複數個細線單元3，並將該些複數個細線單元3使用作為前驅物，藉此形成由機能性細線圖樣所構成之透明導電膜的方法之具體例，以進一步詳細說明本發明。此處，作為機能性材料較佳是使用導電性材料，作為基材較佳是使用透明基材。 Hereinafter, a specific example of a method of forming a plurality of thin line units 3 on a base material 1 and using the plurality of thin line units 3 as a precursor to form a transparent conductive film composed of a functional thin line pattern, The present invention will be described in further detail. Here, a conductive material is preferably used as the functional material, and a transparent substrate is preferably used as the substrate.
首先，參照圖3~圖8，說明將由線狀液體所構成之封閉的幾何圖形做成四角形之態樣。 First, referring to FIGS. 3 to 8, a description will be given of a state in which a closed geometric figure made of a linear liquid is made into a quadrangle.
首先，如圖3(a)所示，在基材1上，藉由含有導電性材料的第1線狀液體2，形成四角形以作為封閉的幾何圖形。此處，在基材1上，將四角形的第1線狀液體2於基材的長邊方向(圖中，上下方向)及寬度方向(圖中，左右方向)以規定間距並設複數個。此處，為求簡便，圖示了4個第1線狀液體2。 First, as shown in FIG. 3 (a), a quadrangular shape is formed on the substrate 1 by the first linear liquid 2 containing a conductive material as a closed geometric figure. Here, on the substrate 1, a plurality of first rectangular linear liquids 2 are provided at a predetermined pitch in the longitudinal direction (upward and downward directions in the figure) and the width direction (leftward and right directions in the figure) of the substrate. Here, for simplicity, four first linear liquids 2 are shown.
被賦予至基材1上的第1線狀液體2，將未被賦予液體之區域20涵括於內部，藉此，具有互相獨立的內側緣21與外側緣22作為緣。 The first linear liquid 2 applied to the base material 1 includes a region 20 to which the liquid is not applied, and has an inner edge 21 and an outer edge 22 that are independent from each other as edges.
接著，當令第1線狀液體2乾燥時使咖啡漬 圈環現象發生，令導電性材料沿著線狀液體2的內側緣21及外側緣22選擇性地堆積。 Next, the coffee is stained when the first linear liquid 2 is dried. The looping phenomenon occurs, and the conductive material is selectively deposited along the inner edge 21 and the outer edge 22 of the linear liquid 2.
如此一來，如圖3(b)所示，便形成由內側細線31與外側細線32所構成之第1細線單元3。構成第1細線單元3之細線31、32，被形成為四角形狀。 In this way, as shown in FIG. 3 (b), the first thin line unit 3 composed of the inner thin line 31 and the outer thin line 32 is formed. The thin wires 31 and 32 constituting the first thin wire unit 3 are formed in a rectangular shape.
接著，如圖4(a)所示，在基材1上，藉由含有導電性材料的第2線狀液體4，形成四角形以作為封閉的幾何圖形。此處，在基材1上，將四角形的第2線狀液體4於基材的長邊方向及寬度方向以規定間距並設複數個。此處，為求簡便，圖示了5個第2線狀液體4。 Next, as shown in FIG. 4 (a), a quadrangular shape is formed on the substrate 1 by the second linear liquid 4 containing a conductive material as a closed geometric figure. Here, on the base material 1, a plurality of quadrangular second linear liquids 4 are provided at a predetermined pitch in the longitudinal direction and the width direction of the base material. Here, for the sake of simplicity, five second linear liquids 4 are shown.
被賦予至基材1上的第2線狀液體4，將未被賦予液體之區域40涵括於內部，藉此，具有互相獨立的內側緣41與外側緣42作為緣。 The second linear liquid 4 applied to the base material 1 includes a region 40 to which no liquid is applied, and has an inner edge 41 and an outer edge 42 that are independent from each other as edges.
本態樣中，將第2線狀液體4形成於被包夾在4個第1細線單元3之間的位置。由第2線狀液體4所構成之四角形的各頂點鄰近，配置成和鄰接之第1細線單元3的外側細線32接觸。由第2線狀液體4所構成之四角形的各頂點，配置於鄰接之第1細線單元3的內側細線31與外側細線32之間的區域。 In this aspect, the second linear liquid 4 is formed at a position sandwiched between the four first thin line units 3. The vertices of the quadrangle formed by the second linear liquid 4 are adjacent to each other, and are arranged in contact with the outer thin lines 32 of the adjacent first thin line unit 3. The vertices of the quadrangle formed by the second linear liquid 4 are arranged in a region between the inner thin line 31 and the outer thin line 32 adjacent to the first thin line unit 3.
接著，當令第2線狀液體4乾燥時使咖啡漬圈環現象發生，令導電性材料沿著第2線狀液體4的內側緣41及外側緣42選擇性地堆積。 Next, when the second linear liquid 4 is dried, the coffee stain ring phenomenon occurs, and the conductive material is selectively deposited along the inner edge 41 and the outer edge 42 of the second linear liquid 4.
如此一來，如圖4(b)所示，便能形成由內側細線51與外側細線52所構成之第2細線單元5。構成 第2細線單元5之細線51、52，被形成為四角形狀。 In this way, as shown in FIG. 4 (b), the second thin line unit 5 composed of the inner thin line 51 and the outer thin line 52 can be formed. Constitute The thin lines 51 and 52 of the second thin line unit 5 are formed in a rectangular shape.
本態樣中，在基材1上，將第1細線單元3與第2細線單元5，於基材的長邊方向及寬度方向交互地形成。將各細線單元3、5形成為，第1細線單元3的外側細線32與第2細線單元5的外側細線52係互相連接，而第1細線單元3的內側細線31與第2細線單元5的內側細線51則不互相連接。內側細線31、51，不僅未和其他的內側細線31、51連接，也未和其他的外側細線32、52連接。 In this aspect, the first thin line unit 3 and the second thin line unit 5 are alternately formed on the substrate 1 in the longitudinal direction and the width direction of the substrate. The thin line units 3 and 5 are formed such that the outer thin line 32 of the first thin line unit 3 and the outer thin line 52 of the second thin line unit 5 are connected to each other, and the inner thin line 31 of the first thin line unit 3 and the second thin line unit 5 are connected to each other. The inner thin wires 51 are not connected to each other. The inner thin wires 31 and 51 are not connected not only to other inner thin wires 31 and 51 but also to other outer thin wires 32 and 52.
如以上這樣，在基材1上，形成藉由外側細線32、52而互相連接之由細線單元3、5所構成之圖樣。 As described above, the substrate 1 is formed with the pattern composed of the thin line units 3 and 5 which are connected to each other by the outer thin lines 32 and 52.
接著，對獲得之圖樣施加電解鍍覆。參照圖5說明該電解鍍覆處理之一例。 Next, an electrolytic plating is applied to the obtained pattern. An example of this electrolytic plating process will be described with reference to FIG. 5.
如圖5所示，令供電構件6接觸未圖示之鍍覆浴內的由細線單元3、5所構成之圖樣而施加電解鍍覆。此時，由於外側細線32、52彼此互相連接，會以網目狀形成由複數個外側細線32、52所構成之通電路徑。從供電構件6通過該通電路徑而通電，藉此，對該通電路徑內的外側細線32、52施加電解鍍覆。 As shown in FIG. 5, the power supply member 6 is brought into contact with a pattern composed of thin wire units 3 and 5 in a plating bath (not shown) to apply electrolytic plating. At this time, since the outer thin wires 32 and 52 are connected to each other, a current path formed by the plurality of outer thin wires 32 and 52 is formed in a mesh shape. The current is supplied from the power feeding member 6 through the current passing path, whereby electrolytic plating is applied to the outer thin wires 32 and 52 in the current passing path.
另一方面，內側細線31、51，未和其他的內側細線31、51及外側細線32、52互相連接，而是各自獨立地形成，因此不會形成如上述外側細線32、52般的通電路徑。如圖示般，當存在與供電構件6直接接觸之內側細線31、51的情形下，可對內側細線31、51施加電解鍍 覆，但除此以外的內側細線31、51則不受通電，而不會被施加電解鍍覆。當不使供電構件6接觸內側細線31、51的情形下，任一內側細線31、51均不會被施加電解鍍覆。 On the other hand, the inner thin wires 31 and 51 are not connected to the other inner thin wires 31 and 51 and the outer thin wires 32 and 52, but are formed independently. Therefore, a current path like the outer thin wires 32 and 52 is not formed. . As shown in the figure, when there are inner thin wires 31 and 51 that are in direct contact with the power supply member 6, electrolytic plating may be applied to the inner thin wires 31 and 51. However, the other inner thin wires 31 and 51 are not energized and are not subjected to electrolytic plating. When the power feeding member 6 is not brought into contact with the inner thin wires 31, 51, neither of the inner thin wires 31, 51 is subjected to electrolytic plating.
像這樣，對外側細線32、52透過通電路徑而通電，藉此便能對該外側細線32、52選擇性地施加電解鍍覆。此處，所謂「選擇性地」，係指至少被施加電解鍍覆之外側細線32、52的條數，比被施加電解鍍覆之內側細線31、51的條數還多。 In this manner, the outer thin wires 32 and 52 are electrically energized through the current-carrying path, whereby electrolytic plating can be selectively applied to the outer thin wires 32 and 52. Here, "selectively" means that the number of at least the outer thin wires 32 and 52 to which electrolytic plating is applied is greater than the number of the inner thin wires 31 and 51 to which electrolytic plating is applied.
像這樣，如圖6所示，能夠使被施加了電解鍍覆之外側細線32、52的膜厚，比未被施加電解鍍覆之內側細線31、51還增大。如此一來，外側細線32、52會比內側細線31、51還被低電阻化，耐久性更加提升。 In this manner, as shown in FIG. 6, the film thickness of the outer thin wires 32 and 52 to which electrolytic plating is applied can be made larger than the inner thin wires 31 and 51 to which electrolytic plating is not applied. As a result, the outer thin wires 32 and 52 are lower in resistance than the inner thin wires 31 and 51, and the durability is further improved.
接著，使用細線單元3、5作為前驅物，形成機能性細線圖樣。 Next, using the thin line units 3 and 5 as precursors, a functional thin line pattern is formed.
本態樣中，是將細線單元3、5的內側細線31、51除去，藉此如圖7所示，藉由未除去而被殘留之互相連接的外側細線32、52，來形成機能性細線圖樣。 In this aspect, the inner thin lines 31 and 51 of the thin line units 3 and 5 are removed, and as shown in FIG. 7, the functional thin line patterns are formed by the outer thin lines 32 and 52 connected to each other without being removed. .
如上述般對外側細線32、52施加電解鍍覆預先使膜厚增大，藉此可獲得外側細線32、52變得不易被除去，而未被施加電解鍍覆之內側細線31、51則能夠相對容易地除去之效果。 Applying electrolytic plating to the outer thin wires 32 and 52 as described above increases the film thickness in advance, so that the outer thin wires 32 and 52 cannot be easily removed, while the inner thin wires 31 and 51 without electrolytic plating can be obtained. Effect of relatively easy removal.
除去細線之方法並無特別限定，但例如較佳是使用照射雷射光等這類能量線之方法、或化學性地蝕刻 處理之方法等。 The method of removing the fine line is not particularly limited, but for example, a method using an energy line such as laser light irradiation or chemical etching is preferred. Methods of treatment, etc.
此外，作為除去細線之較佳方法，亦能使用當對外側細線32、52施加電解鍍覆時，將內側細線31、51藉由鍍覆液予以除去之方法。在此情形下，作為鍍覆液，能夠使用可將構成作為除去對象之細線的導電性材料予以溶解或分解之物。 In addition, as a preferable method for removing the thin wires, when the electrolytic plating is applied to the outer fine wires 32 and 52, a method of removing the inner fine wires 31 and 51 with a plating solution can also be used. In this case, as the plating solution, a substance that can dissolve or decompose the conductive material constituting the thin wire to be removed can be used.
作為具體例，首先，使用銀奈米粒子作為導電性材料，形成由內側細線31、51及外側細線32、52所構成之細線單元3、5。然後，在外側細線32、52選擇性地設置銅鍍覆層作為第1電解鍍覆，接著，在該銅鍍覆層上設置鎳鍍覆層作為第2電解鍍覆。此時，藉由第2電解鍍覆(電解鎳鍍覆)的鍍覆液，能夠將未被施加第1電解鍍覆之由銀所構成之內側細線31、51予以溶解或分解而除去。像這樣，較佳是令對於外側細線32、52之電解鍍覆、及內側細線31、51之除去予以同時地進行。 As a specific example, first, silver nano particles are used as a conductive material, and the thin wire units 3 and 5 composed of the inner thin wires 31 and 51 and the outer thin wires 32 and 52 are formed. Then, a copper plating layer is selectively provided as the first electrolytic plating on the outer thin wires 32 and 52, and then a nickel plating layer is provided as the second electrolytic plating on the copper plating layer. At this time, the inner thin wires 31 and 51 made of silver, to which the first electrolytic plating is not applied, can be dissolved or decomposed and removed by the plating solution of the second electrolytic plating (electrolytic nickel plating). In this way, it is preferable to perform the electrolytic plating of the outer thin wires 32 and 52 and the removal of the inner thin wires 31 and 51 simultaneously.
此外，例如亦佳是，在停止用於電解鍍覆之供電後，令基材1浸漬於鍍覆液達充分足以除去作為除去對象的細線(較佳是內側細線31、51)之時間，較佳為1分鐘~30分鐘的時間。 In addition, for example, it is also preferable that, after the power supply for electrolytic plating is stopped, the substrate 1 is immersed in the plating solution for a time sufficient to remove the thin lines (preferably, the inner thin lines 31 and 51) to be removed, which is longer than The time is preferably 1 minute to 30 minutes.
如以上般，藉由除去內側細線31、51，能夠將未除去而被殘留之由外側細線32、52所構成之機能性細線圖樣中的細線的配置間隔予以高自由度地調整。細線的部分除去所造成之配置間隔的調整，在欲增大配置間隔的情形下特別有利。 As described above, by removing the inner thin lines 31 and 51, it is possible to adjust the arrangement interval of the thin lines in the functional thin line pattern composed of the outer thin lines 32 and 52 that are left unremoved, with a high degree of freedom. The adjustment of the arrangement interval caused by the removal of the thin lines is particularly advantageous in the case where the arrangement interval is to be increased.
藉由除去細線的一部分而增大細線的配置間隔，藉此，可獲得能夠良好地提升由機能性細線圖樣所構成之透明導電膜的透射率或低視認性之效果。 By removing a part of the thin line and increasing the arrangement interval of the thin line, the effect of improving the transmittance or low visibility of the transparent conductive film made of the functional thin line pattern can be obtained.
詳加說明如以上這樣獲得的機能性細線圖樣。 The functional thin line pattern obtained as described above will be explained in detail.
圖7所示之機能性細線圖樣，是在基材1上，將由外側細線32、52所構成之細線，亦即含有機能性材料之四角形狀細線，予以二維地並設複數個而成。四角形狀細線(外側細線32、52)，於該基材1的長邊方向及寬度方向各自以規定間距並設複數個。 The functional thin line pattern shown in FIG. 7 is formed by arranging a plurality of thin lines composed of outer thin lines 32 and 52 on the base material 1, that is, thin lines having a rectangular shape containing functional materials. A plurality of rectangular thin lines (outside thin lines 32, 52) are provided at a predetermined pitch in the longitudinal direction and the width direction of the base material 1, respectively.
如圖7所示，機能性細線圖樣中，四角形狀細線(外側細線32、52)，較佳為相對於基材1的長邊方向而言，各邊呈傾斜(圖示例子中為45°)之四角形。如此一來，可獲得能夠良好地防止當將由機能性細線圖樣所構成之附透明導電膜基材1裝入圖像顯示元件等元件時的摩爾紋(moiré)發生。 As shown in FIG. 7, in the functional thin line pattern, the rectangular thin lines (outside thin lines 32 and 52) are preferably inclined with respect to the long side direction of the substrate 1 (45 ° in the example shown in the figure). ) Of the quadrangle. In this way, it is possible to prevent the occurrence of moiré when the transparent conductive film-attached base material 1 composed of a functional thin line pattern is incorporated into an element such as an image display element.
所謂摩爾紋，係指當將由導電性細線的集合體所構成之附透明導電膜基材1裝入元件時，因導電性細線與元件中的其他要素之組合而導致視認出條紋的情況。摩爾紋，例如可能藉由構成透明導電膜之導電性細線、與元件中的圖像顯示元件所具備之像素陣列做光學性干涉等而產生。藉由防止摩爾紋，可獲得能夠鮮明地視認藉由圖像顯示元件而顯示的圖像之效果。 The moiré pattern refers to a case where a streak is visually recognized due to a combination of the conductive thin wire and other elements in the element when the transparent conductive film-attached base material 1 composed of an assembly of conductive thin wires is incorporated into the element. Moiré patterns may be caused, for example, by optically conducting thin wires that constitute a transparent conductive film, or by optically interfering with a pixel array included in an image display element in the element. By preventing moiré, it is possible to obtain an effect that an image displayed by the image display element can be clearly recognized.
該機能性細線圖樣中，鄰接之四角形狀細線 (外側細線32、52)，是令夾著四角形的頂點之兩邊交錯，而以2點的交點連接。亦即，如圖8擴大所示般，鄰接之四角形狀細線(外側細線32、52)，是令夾著一方的四角形狀細線(外側細線32)的頂點A之兩邊a1、a2，與夾著另一方的四角形狀細線(外側細線52)的頂點B之兩邊b1、b2交錯，藉此以2點的交點C、D連接。另，圖8中，為便於說明，僅揭示鄰接之1組的四角形狀細線(外側細線32、52)，但如圖7所示般，其他鄰接之四角形狀細線亦以同樣方式連接。像這樣將鄰接之四角形狀細線(外側細線32、52)以2點的交點連接，藉此，能夠將兩四角形狀細線確實地連接，特別是當使用導電性材料作為機能性材料的情形下，能夠實現確實的電性連接。如此一來，能夠實現透明導電膜的進一步低電阻化，亦可獲得能夠更加良好地防止電阻的不均一化之效果。 In this functional thin line pattern, the adjacent four-cornered thin lines (Outside thin lines 32, 52) are two sides intersected by the apex of the quadrangle, and are connected at the intersection of two points. That is, as shown in the enlarged view of FIG. 8, the adjacent rectangular thin lines (outside thin lines 32 and 52) are two sides a1 and a2 of the apex A sandwiching one of the rectangular thin lines (outside thin lines 32) and sandwiched therebetween. The two sides b1, b2 of the apex B of the other rectangular thin line (outside thin line 52) are intersected, thereby connecting at two intersections C and D. In addition, in FIG. 8, for convenience of explanation, only one set of adjacent four-cornered thin lines (outside thin lines 32 and 52) are disclosed. As shown in FIG. 7, other adjacent four-cornered thin lines are connected in the same manner. As described above, by connecting adjacent four-cornered thin lines (outer thin lines 32, 52) at the intersection of two points, the two four-cornered thin lines can be reliably connected, especially when a conductive material is used as a functional material. Able to achieve a reliable electrical connection. In this way, a further reduction in resistance of the transparent conductive film can be achieved, and the effect of preventing unevenness in resistance can be obtained more effectively.
此外，鄰接之四角形狀細線(外側細線32、52)的內部區域的重複面積，較佳是各四角形狀細線(外側細線32、52)的內部區域的面積的10分之1以下。此處，所謂重複面積，以圖示例子而言，係指以2個頂點A、B及2個交點C、D所構成之4點為頂點的四角形ADBC的面積。如此一來，能夠更確實地連接兩四角形狀細線，並且可獲得機能性細線圖樣變得不易被視認之效果。 The repeating area of the inner region of the adjacent rectangular thin lines (outer thin lines 32, 52) is preferably 1/10 or less of the area of the inner region of each of the rectangular thin lines (outer thin lines 32, 52). Here, the repeated area refers to an area of a quadrangular ADBC having four vertices constituted by two vertices A and B and two intersections C and D as an example. In this way, two quadrangular thin lines can be connected more reliably, and the effect that the functional thin line pattern becomes difficult to be recognized can be obtained.
此外，特別是當使用導電性材料作為機能性 材料的情形下，四角形狀細線(外側細線32、52)被鍍覆層披覆，藉此能夠實現更確實的電性連接。 In addition, especially when using conductive materials as functional In the case of a material, the square-shaped thin lines (the outer thin lines 32 and 52) are covered with a plating layer, thereby enabling more reliable electrical connection.
以上說明中，揭示了在基材的一面形成機能性細線圖樣之情形，但在基材的兩面形成機能性細線圖樣亦佳。參照圖9說明在基材的兩面形成機能性細線圖樣的情形之一例。 In the above description, the case where the functional thin line pattern is formed on one side of the base material is described, but it is also preferable to form the functional thin line pattern on both sides of the base material. An example of a case where a functional thin line pattern is formed on both sides of a substrate will be described with reference to FIG. 9.
圖9例子中，在基材1的一面(表面)形成機能性細線圖樣，又，在基材1的另一面(背面)亦形成機能性細線圖樣。 In the example of FIG. 9, a functional thin line pattern is formed on one surface (front surface) of the substrate 1, and a functional thin line pattern is also formed on the other surface (back surface) of the substrate 1.
此處，各面的機能性細線圖樣，如同圖7所示者般，是藉由將細線單元3、5的內側細線31、51除去，而藉由未除去而被殘留之外側細線32、52來構成。 Here, as shown in FIG. 7, the functional thin line patterns on each side are removed by removing the inner thin lines 31 and 51 of the thin line units 3 and 5 and leaving the outer thin lines 32 and 52 unremoved. To constitute.
像這樣，當在基材1的兩面形成機能性細線圖樣的情形下，尤佳是，將構成一面及/或另一面的細線單元之細線的一部分予以除去而增大細線的配置間隔。 As described above, when a functional thin line pattern is formed on both sides of the substrate 1, it is particularly preferable to remove a part of the thin lines constituting the thin line unit on one side and / or the other side to increase the arrangement interval of the thin lines.
例如，使用透明基材作為基材，使用導電性材料作為令兩面的機能性細線圖樣含有之機能性材料，藉此，便能在透明基材的兩面形成由機能性細線圖樣所構成之透明導電膜。在此情形下，藉由細線的部分除去來增大細線的配置間隔，便能減緩表裏的圖樣的對位精度之高要求。亦即，即使表裏的圖樣的對位發生了些微偏差，由於細線間隔大，仍能良好地防止表裏的圖樣的干涉所造成之「見骨」情況。兩面設有透明導電膜之透明基材，例如能夠良好地用作為觸控面板感測器等。 For example, a transparent substrate is used as a substrate, and a conductive material is used as a functional material that contains a functional thin line pattern on both sides. Thus, a transparent conductive pattern composed of a functional thin line pattern can be formed on both sides of the transparent substrate. membrane. In this case, by increasing the arrangement interval of the thin lines by removing the thin line parts, it is possible to slow down the high requirements for the alignment accuracy of the patterns in the table. That is, even if there is a slight deviation in the alignment of the pattern on the surface, due to the large thin line spacing, it is still possible to prevent the "seeing bone" situation caused by the interference of the pattern on the surface. A transparent substrate with a transparent conductive film on both sides can be used as a touch panel sensor, for example.
圖10揭示具備藉由機能性細線圖樣而構成之透明導電膜的觸控面板感測器之一例。圖10(a)揭示從表面側觀看基材1之情形，圖10(b)則揭示從背面側觀看基材1之情形。 FIG. 10 illustrates an example of a touch panel sensor including a transparent conductive film formed by a functional thin line pattern. FIG. 10 (a) illustrates the case where the substrate 1 is viewed from the front side, and FIG. 10 (b) illustrates the case where the substrate 1 is viewed from the back side.
圖示之觸控面板感測器，如圖10(a)所示，是在透明的基材1的表面，並設有複數個帶狀的X電極7。複數個X電極7，分別由透明導電膜8所構成，該透明導電膜8藉由由外側細線32、52所構成之機能性細線圖樣所構成。 As shown in FIG. 10 (a), the touch panel sensor shown in the figure is provided on the surface of the transparent substrate 1 with a plurality of X-shaped electrodes 7 in a band shape. The plurality of X electrodes 7 are each composed of a transparent conductive film 8, and the transparent conductive film 8 is composed of a functional thin line pattern composed of outer thin lines 32 and 52.
構成各透明導電膜8之機能性細線圖樣中，鄰接之外側細線32、52互相連接。另一方面，構成一個透明導電膜8之外側細線32、52，和構成另一個透明導電膜8之外側細線32、52並未連接。像這樣，藉由存在未互相連接之外側細線32、52，能夠在基材1的表面，形成未互相電性連接而獨立之複數個X電極7。各X電極7，是藉由由互相電性連接之複數個外側細線32、52所構成之集合體所構成。圖中，符號9為引出配線，各X電極7藉由引出配線9而連接至未圖示之控制電路。 In the functional thin line pattern constituting each transparent conductive film 8, the adjacent outer thin lines 32 and 52 are connected to each other. On the other hand, the outer thin wires 32 and 52 constituting one transparent conductive film 8 and the outer thin wires 32 and 52 constituting the other transparent conductive film 8 are not connected. In this manner, by having the outer thin wires 32 and 52 not connected to each other, it is possible to form a plurality of independent X electrodes 7 on the surface of the substrate 1 which are not electrically connected to each other. Each X electrode 7 is composed of an assembly composed of a plurality of outer thin wires 32 and 52 which are electrically connected to each other. In the figure, reference numeral 9 is a lead-out wiring, and each X electrode 7 is connected to a control circuit (not shown) through the lead-out wiring 9.
另一方面，如圖10(b)所示，在透明的基材1的背面，並設有複數個帶狀的Y電極10。複數個Y電極10，分別如同上述X電極7般，由透明導電膜8所構成，該透明導電膜8藉由由外側細線32、52所構成之機能性細線圖樣所構成。帶狀的Y電極10，形成為其長邊方向和上述X電極的長邊方向交錯。各Y電極10藉由引 出配線9而連接至未圖示之控制電路。 On the other hand, as shown in FIG. 10 (b), a plurality of strip-shaped Y electrodes 10 are provided on the back surface of the transparent substrate 1. The plurality of Y electrodes 10 are each formed of a transparent conductive film 8 like the X electrode 7 described above, and the transparent conductive film 8 is formed of a functional thin line pattern composed of outer thin lines 32 and 52. The strip-shaped Y electrode 10 is formed such that the longitudinal direction of the strip-shaped Y electrode 10 and the longitudinal direction of the X electrode are staggered. Each Y electrode 10 is The wiring 9 is connected to a control circuit (not shown).
該些X電極7及Y電極10，設置成隔著透明的基材1而交錯(疊合)。此時，藉由上述細線的部分除去，構成由透明導電膜構成之X電極7及Y電極10的機能性細線圖樣中的細線的配置間隔變大，藉此，如參照圖9所說明般，能夠減緩表裏的圖樣的對位精度的高要求。 These X electrodes 7 and Y electrodes 10 are provided so as to be interlaced (stacked) with the transparent base material 1 interposed therebetween. At this time, by excluding a part of the thin lines described above, the arrangement interval of the thin lines in the functional thin line pattern constituting the X electrodes 7 and the Y electrodes 10 made of a transparent conductive film becomes larger, and as described with reference to FIG. It can alleviate the high requirement of the alignment accuracy of the patterns in the table.
具備了以上這樣構成的觸控面板感測器，例如能夠良好地用作為靜電容量方式等之觸控面板感測器。若為靜電容量方式的觸控面板，於操作時，利用當使用者的手指或導體等接近、接觸該些X電極7及Y電極10時產生的靜電容量變化所造成之感應電流，便能偵測手指或導體等的位置座標。 The touch panel sensor having the above-described configuration can be suitably used, for example, as a touch panel sensor of an electrostatic capacity method or the like. If it is a capacitive touch panel, during operation, it can detect the induced current caused by the change in the electrostatic capacity when the user's fingers or conductors approach or touch the X electrodes 7 and Y electrodes 10. Measure the position coordinates of fingers or conductors.
以上說明中，係設置從形成第1線狀液體至形成第1細線單元為止之工程、及從形成第2線狀液體至形成第2細線單元為止之工程，以分成2次來形成複數個細線單元，但並不限定於此。形成了第2細線單元後，亦可形成又1或複數個細線單元。又1或複數個細線單元，能夠分成1或複數次來形成。亦即，當在基材上形成複數個細線單元的情形下，能夠適當分成複數次來形成。此外，例如當不連接細線單元彼此的情形下，將複數個細線單元以1次形成亦佳。 In the above description, the process from the formation of the first linear liquid to the formation of the first thin line unit and the process from the formation of the second linear liquid to the formation of the second thin line unit are divided into two to form a plurality of thin lines. The unit is not limited to this. After the second thin line unit is formed, another 1 or a plurality of thin line units may be formed. One or more thin line units can be formed by dividing into one or more times. That is, in the case where a plurality of thin line units are formed on a base material, the thin line units can be appropriately divided into a plurality of times to be formed. In addition, for example, when the thin line units are not connected to each other, it is preferable to form a plurality of thin line units at one time.
以上說明中，揭示了將由線狀液體所構成之封閉的幾何圖形訂為四角形，來形成由四角形狀細線所構成之機能性細線圖樣的情形，但並不限定於此，能夠將由 線狀液體所構成之封閉的幾何圖形訂為多角形，來形成由多角形狀細線所構成之機能性細線圖樣。 In the above description, the case where the closed geometric figure composed of a linear liquid is set to a quadrangle to form a functional thin line pattern composed of a rectangular thin line is disclosed, but it is not limited to this. The closed geometric figure formed by the linear liquid is set as a polygon to form a functional thin line pattern composed of polygonal thin lines.
以下，作為四角形以外的其他多角形之例子，說明三角形、六角形、八角形之情形。 Hereinafter, the case of a triangle, a hexagon, and an octagon is described as an example of a polygon other than a quadrangle.
將由線狀液體所構成之封閉的幾何圖形訂為三角形，藉此，如圖11(a)所示，能夠形成由分別形成為三角形狀的內側細線31與外側細線32所構成之細線單元3。鄰接之外側細線32，是令夾著三角形的頂點之兩邊彼此交錯，而以2點的交點連接。 By closing the closed geometric figure made of the linear liquid into a triangle, as shown in FIG. 11 (a), a thin line unit 3 composed of an inner thin line 31 and an outer thin line 32 each formed in a triangular shape can be formed. Adjacent to the outer thin line 32, the two sides sandwiching the apex of the triangle are intersected with each other and connected at the intersection of two points.
藉由除去由該細線單元3所構成之機能性細線圖樣前驅物的內側細線31，如圖11(b)所示，便能形成由未除去而被殘留之外側細線32亦即三角形狀細線所構成之機能性細線圖樣。 By removing the inner thin line 31 of the functional thin line pattern precursor constituted by the thin line unit 3, as shown in FIG. 11 (b), it is possible to form the outer thin line 32, which is a triangle-shaped thin line, which is left without being removed. Functional thin line pattern of composition.
將由線狀液體所構成之封閉的幾何圖形訂為六角形，藉此，如圖12(a)所示，能夠形成由分別形成為六角形狀的內側細線31與外側細線32所構成之細線單元3。鄰接之外側細線32，是令夾著六角形的頂點之兩邊彼此交錯，而以2點的交點連接。 By closing the closed geometric figure made of the linear liquid into a hexagonal shape, as shown in FIG. 12 (a), it is possible to form a thin line unit 3 composed of an inner thin line 31 and an outer thin line 32 each formed in a hexagonal shape. . Adjacent to the outer thin line 32, the two sides sandwiching the apex of the hexagon are intersected with each other and are connected at the intersection of two points.
藉由除去由該細線單元3所構成之機能性細線圖樣前驅物的內側細線31，如圖12(b)所示，便能形成將未除去而被殘留之外側細線32亦即六角形狀細線予以二維地並設複數個而成之機能性細線圖樣。 By removing the inner thin line 31 of the functional thin line pattern precursor constituted by the thin line unit 3, as shown in FIG. 12 (b), it is possible to form a thin line of a hexagonal shape, which is left without being removed, but the outer thin line 32 A functional thin line pattern formed by arranging a plurality of two-dimensionally.
將由線狀液體所構成之封閉的幾何圖形訂為八角形，藉此，如圖13(a)所示，能夠形成由分別形成 為八角形狀的內側細線31與外側細線32所構成之細線單元3。鄰接之外側細線32，是令夾著八角形的頂點之兩邊彼此交錯，而以2點的交點連接。 By closing the closed geometric figure made of linear liquid into an octagon, as shown in FIG. 13 (a), it can be formed by The thin line unit 3 composed of an inner thin line 31 and an outer thin line 32 having an octagonal shape. Adjacent to the outer thin line 32, the two sides sandwiching the apex of the octagon are intersected with each other, and are connected at the intersection of two points.
藉由除去由該細線單元3所構成之機能性細線圖樣前驅物的內側細線31，如圖13(b)所示，便能形成將未除去而被殘留之外側細線32亦即八角形狀細線予以二維地並設複數個而成之機能性細線圖樣。 By removing the inner thin line 31 of the functional thin line pattern precursor constituted by the thin line unit 3, as shown in FIG. 13 (b), it is possible to form an octagonal thin line that is left without being removed and is left outside the thin line 32 A functional thin line pattern formed by arranging a plurality of two-dimensionally.
又，由線狀液體所構成之封閉的幾何圖形，不限定於多角形，例如亦可為圓形或橢圓形等般含有曲線要素者。圖14揭示將由線狀液體所構成之封閉的幾何圖形訂為圓形的情形之例子。 Further, the closed geometrical figure composed of a linear liquid is not limited to a polygon, and may include a curve element such as a circle or an ellipse, for example. FIG. 14 shows an example of a case where a closed geometric figure made of a linear liquid is made circular.
將由線狀液體所構成之封閉的幾何圖形訂為圓形，藉此，如圖14(a)所示，能夠形成由分別形成為圓形狀的內側細線31與外側細線32所構成之細線單元3。鄰接之外側細線32，是令圓形的圓周彼此交錯，而以2點的交點連接。 By closing the closed geometric figure made of the linear liquid to a circle, as shown in FIG. 14 (a), it is possible to form the thin line unit 3 composed of the inner thin line 31 and the outer thin line 32 each formed in a circular shape. . Adjacent to the outer thin lines 32, the circular circles are intersected with each other and connected at the intersection of two points.
藉由除去由該細線單元3所構成之機能性細線圖樣前驅物的內側細線61，如圖14(b)所示，便能形成將未除去而被殘留之外側細線62亦即圓形狀細線予以二維地並設複數個而成之機能性細線圖樣。 By removing the inner thin line 61 of the functional thin line pattern precursor constituted by the thin line unit 3, as shown in FIG. 14 (b), it is possible to form a thin round line 62 which is left without being removed and is left outside. A functional thin line pattern formed by arranging a plurality of two-dimensionally.
當藉由多角形狀細線(外側細線32)來構成機能性細線圖樣的情形下，多角形的1邊的長度，能夠自在地調整。例如，1邊的長度，較佳為50μm以上、100μm以上、200μm以上、300μm以上、400μm以上、 500μm以上、甚至1mm以上。即使形成這樣相對較大的多角形的情形下，藉由將線狀液體賦予成為封閉的幾何圖形，仍能實現穩定的細線形成。由於能夠不受大小影響而實現穩定的細線形成，因此1邊的長度上限並無特別限定，能夠因應用途適當設定。較佳是構成多角形之至少1個邊為上述範圍，更佳是所有的邊均為上述範圍。 When a functional thin line pattern is formed by a polygonal thin line (outside thin line 32), the length of one side of the polygon can be adjusted freely. For example, the length of one side is preferably 50 μm or more, 100 μm or more, 200 μm or more, 300 μm or more, 400 μm or more, 500 μm or more, or even 1 mm or more. Even in the case of forming such a relatively large polygon, by forming a linear liquid into a closed geometric figure, stable thin line formation can be achieved. Since stable thin line formation can be achieved regardless of size, the upper limit of the length of one side is not particularly limited, and can be appropriately set according to the application. Preferably, at least one side constituting the polygon is in the above range, and more preferably, all sides are in the above range.
此外，多角形不限定於正多角形，構成多角形之各邊的長度、或各內角的角度，亦可互相相異。 In addition, the polygon is not limited to a regular polygon, and the lengths of the sides constituting the polygon or the angles of the inner corners may be different from each other.
此外，當藉由圓形狀細線(外側細線32)來構成機能性細線圖樣的情形下，圓形的直徑能夠自在地調整。例如，直徑，較佳為50μm以上、100μm以上、200μm以上、300μm以上、400μm以上、500μm以上、甚至1mm以上。即使形成這樣相對較大的圓形的情形下，藉由將線狀液體賦予成為封閉的幾何圖形，仍能實現穩定的細線形成。由於能夠不受大小影響而實現穩定的細線形成，因此直徑的上限並無特別限定，能夠因應用途適當設定。 In addition, when the functional thin line pattern is constituted by a circular thin line (outside thin line 32), the diameter of the circle can be adjusted freely. For example, the diameter is preferably 50 μm or more, 100 μm or more, 200 μm or more, 300 μm or more, 400 μm or more, 500 μm or more, or even 1 mm or more. Even in the case where such a relatively large circle is formed, stable line formation can be achieved by providing a linear liquid as a closed geometric figure. Since stable thin wire formation can be achieved regardless of size, the upper limit of the diameter is not particularly limited and can be appropriately set according to the application.
此外，當藉由橢圓形狀細線(外側細線32)來構成機能性細線圖樣的情形下，能夠將上述直徑的較佳範圍，適用作為長徑的較佳範圍。 In addition, when the functional thin line pattern is constituted by an elliptical thin line (outside thin line 32), the preferable range of the diameter can be applied as the preferable range of the long diameter.
以上說明中，主要說明了當在基材上形成複數個細線單元時，將該些複數個細線單元以規定間距形成之情形，但並不限定於此。 In the above description, when a plurality of thin line units are formed on a substrate, the case where the plurality of thin line units are formed at a predetermined pitch is mainly explained, but it is not limited thereto.
以上說明中，主要揭示了當連接細線單元 時，將外側細線彼此連接，而不使內側細線和其他內側細線及外側細線連接之情形，但並不限定於此。亦能令構成細線單元之任一機能性細線互相接觸而連接。例如，能夠將第1細線單元的內側細線及或外側細線、與第2細線單元的內側細線及或外側細線連接。以下參照圖15，說明細線單元的連接形態之另一例。 In the above description, it is mainly disclosed that when connecting thin wire units In this case, the outer thin lines are connected to each other without connecting the inner thin lines with other inner thin lines and outer thin lines, but it is not limited to this. It is also possible to connect any of the functional thin wires constituting the thin wire unit to each other. For example, the inner thin line and / or outer thin line of the first thin line unit can be connected to the inner thin line and / or outer thin line of the second thin line unit. Hereinafter, another example of the connection form of the thin wire unit will be described with reference to FIG. 15.
圖15(a)例子中，互相鄰接之細線單元3、5，係外側細線32、52彼此被連接，內側細線31、51彼此未被連接。本例中，構成一方的細線單元3之內側細線31，和構成另一方的細線單元5之外側細線52連接。同樣地，構成另一方的細線單元5之內側細線51，和構成一方的細線單元3之外側細線32連接。 In the example of FIG. 15 (a), the thin wire units 3 and 5 adjacent to each other are connected with the outer thin wires 32 and 52 and the inner thin wires 31 and 51 are not connected with each other. In this example, the inner thin wire 31 constituting one thin wire unit 3 is connected to the outer thin wire 52 constituting the other thin wire unit 5. Similarly, the inner thin wire 51 constituting the other thin wire unit 5 is connected to the outer thin wire 32 constituting the one thin wire unit 3.
圖15(b)例子中，互相鄰接之細線單元3、5，係外側細線32、52彼此被連接，內側細線31、51彼此亦被連接。本例中，構成一方的細線單元3之內側細線31，和構成另一方的細線單元5之外側細線52連接。同樣地，構成另一方的細線單元5之內側細線51，和構成一方的細線單元3之外側細線32連接。 In the example of FIG. 15 (b), the thin wire units 3 and 5 adjacent to each other are connected to the outer thin wires 32 and 52 and the inner thin wires 31 and 51 are also connected to each other. In this example, the inner thin wire 31 constituting one thin wire unit 3 is connected to the outer thin wire 52 constituting the other thin wire unit 5. Similarly, the inner thin wire 51 constituting the other thin wire unit 5 is connected to the outer thin wire 32 constituting the one thin wire unit 3.
藉由運用圖15(a)、(b)所示之連接形態，例如能夠將上述電解鍍覆不僅施加至外側細線還良好地施加至內側細線。 By using the connection form shown in FIGS. 15 (a) and (b), for example, the above-mentioned electrolytic plating can be applied not only to the outer thin wires but also to the inner thin wires.
當形成複數個互相連接之細線單元的情形下，它們可藉由同一連接形態而被連接，亦可有各種連接形態混雜。又，一部分的細線單元，亦可以均未和內側細 線及外側細線連接之狀態來並設。 When a plurality of thin line units connected to each other are formed, they may be connected by the same connection form, or various connection forms may be mixed. In addition, some thin line units may not be thinner than the inner side. The lines and outer thin lines are connected to each other.
以上說明中，主要揭示了令構成機能性細線圖樣之機能性細線彼此以2點交錯而連接之情形，但並不限定以2點連接。例如，亦可令機能性細線彼此以1點接觸而連接。將2點交錯與1點接觸予以適當組合，而以3點以上連接，就確保導電性之觀點而言亦佳。 In the above description, the case where the functional thin lines constituting the functional thin line pattern are connected to each other at two points has been disclosed, but it is not limited to the two points. For example, functional thin wires may be connected to each other at one point. It is also preferable from the viewpoint of ensuring conductivity that a combination of two-point interleaving and one-point contact be appropriately combined and connected at three or more points.
參照圖16說明由線狀液體所構成之封閉的幾何圖形之又另一例。 Referring to Fig. 16, another example of a closed geometric figure made of a linear liquid will be described.
例如，如圖16(a)所示，藉由線狀液體2而形成之封閉的幾何圖形，藉由鋸齒狀要素而構成亦佳。藉由將其乾燥，在和鋸齒狀的內側緣21及外側緣22相對應之位置，能夠形成由鋸齒狀要素所構成之內側細線及外側細線。又，雖未圖示，但亦可訂為波浪線狀要素來取代鋸齒狀要素，或亦可將鋸齒狀要素與波浪線狀要素組合。當將由鋸齒狀要素或波浪線狀要素所構成之機能性細線這樣的非正多角形之機能性細線予以彼此連接的情形下，雖亦可以1點或2點來連接，但較佳是能夠使用上述3點以上之連接。作為上述非正多角形之機能性細線，例如較佳能夠舉出1個以上的內角大於180°之多角形的機能性細線。 For example, as shown in FIG. 16 (a), the closed geometrical figure formed by the linear liquid 2 is preferably constituted by a sawtooth-like element. By drying this, it is possible to form the inner thin line and the outer thin line composed of the zigzag elements at positions corresponding to the zigzag inner edge 21 and the outer edge 22. Also, although not shown, a wavy line-shaped element may be set instead of a zigzag-shaped element, or a zigzag-shaped element and a wavy-lined element may be combined. In the case of connecting non-regular polygonal functional thin lines such as functional thin lines composed of sawtooth-like elements or wavy line-like elements, although they may be connected at one or two points, it is preferable to be able to use them. The connection above 3 points. As the functional thin line of the non-regular polygon, preferably, for example, one or more functional thin lines having a polygonal shape with an internal angle greater than 180 ° can be mentioned.
此外，如圖16(b)所示，藉由線狀液體2而形成之封閉的幾何圖形，能夠涵括未被賦予液體之2個區域20a、20b。如此一來，幾何圖形，能夠具有複數個內側緣21a、21b。藉由將其乾燥，能夠在和外側緣22相對應之位置形成1個外側細線，並且在和2個內側緣21a、 21b相對應之位置形成2個內側細線。亦可將線狀液體2中涵括之未被賦予液體之區域訂為3個以上，如此一來，能夠形成和該區域的數量相對應之條數的內側細線。 In addition, as shown in FIG. 16 (b), the closed geometry formed by the linear liquid 2 can include the two regions 20a and 20b to which no liquid is given. In this way, the geometric figure can have a plurality of inner edges 21a, 21b. By drying it, one outer thin line can be formed at a position corresponding to the outer edge 22, and two outer edges 21a, Two inner thin lines are formed at positions corresponding to 21b. It is also possible to set three or more regions in the linear liquid 2 to which no liquid is given, so that a number of inner thin lines corresponding to the number of the regions can be formed.
又此外，如圖16(c)所示，藉由線狀液體2而形成之封閉的幾何圖形，亦可具備突出部23。突出部23，例如如圖示般，可為相對於封閉的幾何圖形而言僅以一端連接之線段。 Furthermore, as shown in FIG. 16 (c), the closed geometrical figure formed by the linear liquid 2 may be provided with the protruding portion 23. For example, as shown in the figure, the protruding portion 23 may be a line segment connected with only one end with respect to the closed geometric figure.
此外，內側緣的形狀與外側緣的形狀，可互相同一(即相似)亦可相異。藉由令它們的形狀相異，能夠令獲得的細線單元中的內側細線的形狀與外側細線的形狀相異。 In addition, the shape of the inner edge and the shape of the outer edge may be the same (that is, similar) or different from each other. By making them different in shape, the shape of the inner thin line and the shape of the outer thin line in the obtained thin line unit can be made different.
此外，亦可藉由設於基材上之複數個線狀液體，來形成複數種的互相相異之幾何圖形。如此一來，便能形成將由複數種的互相相異之幾何圖形所構成之機能性細線予以組合而成之機能性細線圖樣。例如，上述第1線狀液體與第2線狀液體，較佳為同一形狀，但並不限定於此，亦可為相似，或亦可為例如四角形與圓形的組合般相異之形狀。 In addition, a plurality of mutually different geometric figures can also be formed by a plurality of linear liquids provided on a substrate. In this way, a functional thin line pattern can be formed by combining functional thin lines composed of a plurality of mutually different geometric figures. For example, the first linear liquid and the second linear liquid preferably have the same shape, but are not limited thereto, and may be similar or different shapes such as a combination of a quadrangle and a circle.
以上說明中，揭示了將構成細線單元的內側細線予以除去，藉此，藉由未除去而被殘留之外側細線來形成機能性細線圖樣之情形，但並不限定於此。將由構成細線單元的內側細線及外側細線所構成之細線的其中一部分予以除去，藉此，藉由未除去而被殘留之細線，便能形成機能性細線圖樣。例如，將構成細線單元的外側細線予 以除去，藉此，藉由未除去而被殘留之內側細線，來形成機能性細線圖樣亦佳。 In the above description, the case where the inner thin line constituting the thin line unit is removed and the outer thin line is left without being removed to form a functional thin line pattern has been disclosed, but it is not limited to this. By removing a part of the thin lines composed of the inner thin line and the outer thin line constituting the thin line unit, a functional thin line pattern can be formed by the thin lines remaining without being removed. For example, the outer thin lines that make up the thin line unit are It is also preferable to form a functional thin line pattern by removing the inner thin lines that are left without removing.
此外，如特別參照圖1及圖2所說明般，構成細線單元之內側細線及外側細線，能夠高自由度而穩定地形成，因此不限於進行細線的部分除去之情形，作為機能性細線圖樣，使用將該細線單元在基材上並設1或複數個而成之物亦佳。 In addition, as explained in particular with reference to FIGS. 1 and 2, the inner and outer thin lines constituting the thin line unit can be formed with high degree of freedom and stability. Therefore, it is not limited to the case where the thin lines are partially removed. It is also preferable to use a thing in which one or a plurality of the thin wire units are provided on the substrate.
以上說明中，主要說明了對構成細線單元之外側細線選擇性地施加電解鍍覆之情形，但並不限定於此。例如，對內側細線及外側細線雙方施加電解鍍覆亦佳。 In the above description, the case where the electrolytic plating is selectively applied to the thin wires outside the constituent thin wire unit has been mainly described, but it is not limited to this. For example, it is also preferable to apply electrolytic plating to both the inner thin wire and the outer thin wire.
此外，將構成細線單元之內側細線除去後對外側細線施加電解鍍覆，或是，將構成細線單元之外側細線除去後對內側細線施加電解鍍覆亦佳。 In addition, it is also preferable to apply electrolytic plating to the outer fine wires after removing the inner fine wires constituting the fine wire unit, or to apply electrolytic plating to the inner fine wires after removing the outer fine wires constituting the fine wire unit.
電解鍍覆中使用的鍍覆金屬並無特別限定，但例如較佳是使用銅或鎳等。對細線層積複數層的鍍覆層亦佳。在此情形下，施加令鍍覆金屬相異之複數次的電解鍍覆。例如，較佳能夠舉出，作為第1電解鍍覆係在細線上設置銅鍍覆層以使導電性提升，接著作為第2電解鍍覆係在銅鍍覆層上設置鎳鍍覆層以使耐候性提升之方法等。 The plating metal used in electrolytic plating is not particularly limited, but for example, copper or nickel is preferably used. It is also preferable to laminate a plurality of layers with thin wires. In this case, electrolytic plating is applied a plurality of times to make the plating metal different. For example, it is preferable to provide a copper plating layer on a thin wire as a first electrolytic plating system to improve conductivity, and a second electrolytic plating system to provide a nickel plating layer on a copper plating layer so that How to improve weather resistance.
此外，不限於電解鍍覆，使用無電解鍍覆亦佳。如此一來，即使機能性材料為非導電性材料的情形下，仍能在細線上設置鍍覆層。 In addition, it is not limited to electrolytic plating, and electroless plating is also preferable. In this way, even when the functional material is a non-conductive material, a plating layer can be provided on the thin wire.
用來形成線狀液體之液體(墨水)中含有的 機能性材料，只要是用來對基材賦予特定機能的材料則無特別限定。所謂賦予特定機能，係指例如運用導電性材料對基材賦予導電性，或運用絕緣性材料對基材賦予絕緣性。機能性材料，較佳是和構成供該機能性材料賦予之基材表面的材料為相異材料。作為機能性材料，例如較佳能夠示例出導電性材料、絕緣性材料、半導體材料、光學濾波材料、介電體材料等。特別是機能性材料較佳為導電性材料或導電性材料前驅物。導電性材料前驅物，係指藉由施加適宜處理能使其變化成導電性材料者。 Contained in a liquid (ink) used to form a linear liquid The functional material is not particularly limited as long as it is a material for imparting a specific function to a substrate. The specific function imparting refers to, for example, imparting conductivity to a substrate using a conductive material, or imparting insulation to a substrate using an insulating material. The functional material is preferably a material different from the material constituting the surface of the substrate to which the functional material is provided. As the functional material, for example, a conductive material, an insulating material, a semiconductor material, an optical filter material, and a dielectric material can be exemplified. In particular, the functional material is preferably a conductive material or a precursor of a conductive material. The precursor of a conductive material is one which can be changed into a conductive material by applying a suitable treatment.
作為導電性材料，例如較佳可示例出導電性微粒子、導電性聚合物等。 As the conductive material, for example, conductive fine particles, a conductive polymer, and the like are preferably exemplified.
作為導電性微粒子雖無特別限定，但較佳能夠示例出Au、Pt、Ag、Cu、Ni、Cr、Rh、Pd、Zn、Co、Mo、Ru、W、Os、Ir、Fe、Mn、Ge、Sn、Ga、In等的微粒子，其中，若使用Au、Ag、Cu這樣的金屬微粒子，則能形成電阻低且耐腐蝕之細線，故較佳。由成本及穩定性的觀點看來，含有Ag之金屬微粒子最佳。該些金屬微粒子的平均粒徑，較佳為1~100nm的範圍，更佳為3~50nm的範圍。平均粒徑，為體積平均粒徑，能夠藉由Malvern公司製ZETASIZER 1000HS來測定。 Although the conductive fine particles are not particularly limited, examples thereof include Au, Pt, Ag, Cu, Ni, Cr, Rh, Pd, Zn, Co, Mo, Ru, W, Os, Ir, Fe, Mn, and Ge. Fine particles such as Al, Sn, Ga, and In are preferably metal fine particles such as Au, Ag, and Cu because they can form thin wires with low resistance and corrosion resistance. From the viewpoint of cost and stability, metal fine particles containing Ag are the best. The average particle diameter of these metal fine particles is preferably in the range of 1 to 100 nm, and more preferably in the range of 3 to 50 nm. The average particle diameter is a volume average particle diameter and can be measured by ZETASIZER 1000HS manufactured by Malvern.
此外，作為導電性微粒子，使用碳微粒子亦佳。作為碳微粒子，較佳能夠示例出石墨微粒子、奈米碳管、富勒烯等。 It is also preferable to use carbon fine particles as the conductive fine particles. As the carbon fine particles, graphite fine particles, nano carbon tubes, fullerene, and the like can be preferably exemplified.
作為導電性聚合物雖無特別限定，但較佳能 夠舉出π共軛系導電性高分子。 Although it is not particularly limited as the conductive polymer, it is preferably One example is a π-conjugated conductive polymer.
作為π共軛系導電性高分子，例如能夠利用聚噻吩類、聚吡咯類、聚吲哚類、聚咔唑類、聚苯胺類、聚乙炔類、聚呋喃類、聚對伸苯基類、聚對伸苯基伸乙烯基類、聚對伸苯基硫醚類、聚薁(azulene)類、聚苯並噻吩(isothianaphthene)類、聚硫氮(thiazyl)類等的鏈狀導電性聚合物。其中，就可獲得高導電性的觀點而言，聚噻吩類或聚苯胺類較佳。最佳為聚乙烯二氧基噻吩。 As the π-conjugated conductive polymer, for example, polythiophenes, polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylenes, Chain-shaped conductive polymers such as polyparaphenylene vinylene, polyparaphenylene sulfide, polyazulene, isothianaphthene, and thiazyl. Among them, polythiophenes or polyanilines are preferred from the viewpoint of obtaining high conductivity. Most preferred is polyethylene dioxythiophene.
導電性聚合物，更佳是，包含上述π共軛系導電性高分子與多價陰離子而成。這樣的導電性聚合物，能夠藉由將形成π共軛系導電性高分子之前驅物單分子(monomer)，在適當的氧化劑與氧化觸媒、及多價陰離子的存在下做化學氧化聚合而容易地製造出。 The conductive polymer is more preferably composed of the π-conjugated conductive polymer and a polyvalent anion. Such a conductive polymer can be chemically oxidized and polymerized in the presence of an appropriate oxidizing agent, an oxidation catalyst, and a polyvalent anion by forming a monomer of a precursor of a π-conjugated conductive polymer, Easily manufactured.
導電性聚合物亦能良好地利用市售材料。例如，由聚(3,4-乙烯二氧基噻吩)與聚苯乙烯磺酸所構成之導電性聚合物(簡寫為PEDOT/PSS)，有H.C.Starck公司以CLEVIOS系列，Aldrich公司以PEDOT-PASS483095、560598，Nagase Chemtex公司以Denatron系列的名義市售。此外，聚苯胺，有日產化學公司以ORMECON系列的名義市售。 The conductive polymer can also make good use of commercially available materials. For example, for the conductive polymer (abbreviated as PEDOT / PSS) composed of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid, there are CLEVIOS series by HCStarck and PEDOT-PASS483095 by Aldrich. , 560598, Nagase Chemtex is commercially available under the name of Denatron series. In addition, polyaniline is commercially available from Nissan Chemical Company under the name of the ORMECON series.
被賦予至基材1上之線狀液體2中的機能性材料的含有率，較佳為對於線狀液體2的全量而言在0.01重量%以上1重量%以下的範圍。含有率，為線狀液體2剛被賦予至基材1上之後而被乾燥之前的值。機能性材料 的含有率，在0.01重量%以上1重量%以下的範圍，藉此，咖啡漬圈環現象所造成之細線形成會更加穩定化。 The content of the functional material in the linear liquid 2 imparted to the substrate 1 is preferably in a range of 0.01% by weight or more and 1% by weight or less for the entire amount of the linear liquid 2. The content rate is a value immediately after the linear liquid 2 is applied to the substrate 1 and before the linear liquid 2 is dried. Functional materials The content rate of Nb is in the range of 0.01% by weight to 1% by weight, whereby the formation of fine lines caused by the coffee stain ring phenomenon is more stabilized.
作為使含有機能性材料之液體，例如能夠組合使用水或有機溶劑等的1種或2種以上。有機溶劑，雖無特別限定，但例如能夠示例出1,2-己二醇、2-甲基-2,4-戊二醇、1,3-丁二醇、1,4-丁二醇、丙二醇等醇類、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丁基醚、參乙二醇單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚等醚類等。 As the liquid containing a functional material, for example, one or two or more of them can be used in combination. The organic solvent is not particularly limited, but examples thereof include 1,2-hexanediol, 2-methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol, Alcohols such as propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ginseng ethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol Ethers such as monoethyl ether.
此外，使含有機能性材料之液體，在不損及本發明之功效的範圍內，亦可含有界面活性劑等各種添加劑。藉由使用界面活性劑，例如當使用液滴吐出元件在基材1上形成線狀液體2這樣的情形等下，可調整表面張力等而謀求吐出的穩定化等。作為界面活性劑，雖無特別限定，但能夠使用矽氧系界面活性劑等。所謂矽氧系界面活性劑，為將二甲基聚矽氧烷的側鏈或末端予以聚醚變性而成之物，例如有信越化學工業製之KF-351A、KF-642或BYK公司製之BYK347、BYK348等市售。界面活性劑的含有率，較佳是相對於線狀液體2的全量而言在1重量%以下。 In addition, the liquid containing a functional material may contain various additives such as a surfactant as long as the effect of the present invention is not impaired. By using a surfactant, for example, in the case where a linear liquid 2 is formed on the substrate 1 using a droplet discharge element, the surface tension and the like can be adjusted to stabilize the discharge. Although it does not specifically limit as a surfactant, a siloxane-type surfactant, etc. can be used. The so-called siloxane-based surfactants are obtained by denaturing the side chain or end of dimethyl polysiloxane with polyether, such as KF-351A, KF-642, or BYK manufactured by Shin-Etsu Chemical Co., Ltd. BYK347 and BYK348 are commercially available. The content of the surfactant is preferably 1% by weight or less based on the total amount of the linear liquid 2.
供含有機能性材料的液體賦予之基材，雖無特別限定，但例如能夠舉出玻璃、塑膠(聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯(PBT)、聚乙烯、聚丙烯、丙烯酸、聚酯、聚醯胺等)、金屬(銅、鎳、 鋁、鐵等，或合金)、陶瓷等，它們可單獨使用，亦可在貼合的狀態下使用。其中，塑膠較佳，合適為聚對苯二甲酸乙二酯、或聚乙烯、聚丙烯這樣的聚烯烴等。 The base material to which the liquid containing a functional material is applied is not particularly limited, but examples thereof include glass, plastic (polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Polyethylene, polypropylene, acrylic, polyester, polyamide, etc.), metals (copper, nickel, Aluminum, iron, etc., or alloys), ceramics, etc., can be used alone or in a laminated state. Among them, plastic is preferable, and suitable is polyethylene terephthalate, or polyolefin such as polyethylene and polypropylene.
接著，參照圖17說明細線單元3的形狀。 Next, the shape of the thin line unit 3 will be described with reference to FIG. 17.
圖17為形成於基材上之細線單元的模型示意立體圖。係揭示由內側細線31及外側細線32所構成之細線單元3的一部分，揭示成直線狀僅是為求簡便。此外，此處說明的細線單元3，為藉由咖啡漬圈環現象而剛形成後者。藉由鍍覆或細線的部分除去等後置處理，可變化細線單元3的形狀等，這點已如上述。 FIG. 17 is a schematic perspective view of a model of a thin line unit formed on a substrate. A part of the thin line unit 3 composed of the inner thin line 31 and the outer thin line 32 is disclosed, and the straight line is disclosed only for simplicity. It should be noted that the thin wire unit 3 described here has just formed the latter by the coffee stain ring phenomenon. As described above, the shape and the like of the thin wire unit 3 can be changed by post-processing such as plating or partial thin wire removal.
內側細線31及外側細線32的配置間隔I之範圍並無特別限定，例如，較佳是訂為10μm以上~1000μm以下的範圍，更佳是訂為10μm以上~500μm以下的範圍，最佳是訂為10μm以上300μm以下的範圍。另，所謂內側細線31及外側細線32的配置間隔I，為藉由咖啡漬圈環現象而剛形成後(未施加鍍覆或細線的部分除去這些後置處理之狀態)的內側細線31及外側細線32的各最大突出部間的距離，是和賦予至基材1上之線狀液體的線寬相對應而決定。較佳是縮小線狀液體的線寬，以縮小配置間隔I。如此一來會減輕乾燥負荷，能夠使內側細線31及外側細線32的形成穩定化，更能縮短產距時間。即使像這樣縮小配置間隔I的情形下，仍能如上述般容易地除去由內側細線31及外側細線32所構成之細線的一部分，因此能夠對未除去而被殘留之細線高自由度地設 定期望的配置間隔。像這樣運用細線的部分除去，便能一面維持內側細線31及外側細線32的穩定形成，一面容易地設定例如50μm以上、100μm以上、200μm以上、300μm以上、400μm以上、500μm以上、甚至1mm以上這樣大的配置間隔。 The range of the arrangement interval I of the inner thin wires 31 and the outer thin wires 32 is not particularly limited. For example, it is preferably set to a range of 10 μm to 1,000 μm, more preferably set to a range of 10 μm to 500 μm, and most preferably set. The range is from 10 μm to 300 μm. In addition, the arrangement interval I of the inner thin line 31 and the outer thin line 32 is the inner thin line 31 and the outer side immediately after the formation of the coffee stain ring phenomenon (the state where the plating is not applied or the thin line is removed from these post-processing). The distance between the largest protrusions of the thin wires 32 is determined in accordance with the line width of the linear liquid applied to the base material 1. It is preferable to reduce the line width of the linear liquid so as to reduce the arrangement interval I. In this way, the drying load can be reduced, the formation of the inner thin wires 31 and the outer thin wires 32 can be stabilized, and the production time can be further shortened. Even in the case where the arrangement interval I is reduced as described above, a part of the thin line composed of the inner thin line 31 and the outer thin line 32 can be easily removed as described above. Therefore, it is possible to set a high degree of freedom for the thin line remaining without removal. Set the desired configuration interval. By using the thin line removal in this way, it is possible to easily set, for example, 50 μm or more, 100 μm or more, 200 μm or more, 300 μm or more, 400 μm or more, 500 μm or more, and even 1 mm or more while maintaining the stable formation of the inner and outer thin lines 31 and 32. Large configuration interval.
構成細線單元3之內側細線31及外側細線32，未必一定要是互相完全獨立的島狀。如圖示般，內側細線31及外側細線32，亦佳是形成為，藉由橫亘該內側細線31及外側細線32間而以比該內側細線31及外側細線32的高度還低的高度形成之薄膜部30而連接成之連續體。在內側細線31及外側細線32間機能性材料的厚度成為最薄之最薄部分的高度Z，具體而言即薄膜部30的最薄部分的高度Z，較佳為10nm以下的範圍。最佳為，為謀求兼顧透明性與穩定性之平衡，以0<Z≦10nm的範圍具備薄膜部30。即使運用導電性材料作為機能性材料的情形下，因薄膜部30為極高電阻而實質性地成為絕緣體，因此透過薄膜部30而連接之內側細線31與外側細線32，會成為被電性絕緣之狀態。是故，能夠良好地施加上述選擇性的電解鍍覆。 The inner thin line 31 and the outer thin line 32 constituting the thin line unit 3 do not necessarily have to be island shapes that are completely independent from each other. As shown in the figure, the inner thin line 31 and the outer thin line 32 are preferably formed so as to be formed at a height lower than the height of the inner thin line 31 and the outer thin line 32 by crossing the inner thin line 31 and the outer thin line 32. The thin film portion 30 is connected to a continuous body. The thickness of the functional material between the inner thin line 31 and the outer thin line 32 is the height Z of the thinnest and thinnest portion, specifically, the height Z of the thinnest portion of the thin film portion 30, preferably in a range of 10 nm or less. Preferably, in order to achieve a balance between transparency and stability, the thin film portion 30 is provided in a range of 0 <Z ≦ 10 nm. Even when a conductive material is used as a functional material, the thin film portion 30 is substantially an insulator due to its extremely high resistance. Therefore, the inner thin wires 31 and the outer thin wires 32 connected through the thin film portion 30 are electrically insulated. Of the state. Therefore, the selective electrolytic plating described above can be favorably applied.
細線單元3的內側細線31及外側細線32的線寬W1、W2，較佳是各自為10μm以下。若為10μm以下，則為一般無法視認之水準，故由提升透明性的觀點看來更佳。考量內側細線31及外側細線32的穩定性，線寬W1、W2，較佳是各自為2μm以上10μm以下的範圍。 另，所謂內側細線31及外側細線32的寬度W1、W2，當將在該內側細線31及外側細線32間機能性材料的厚度成為最薄之最薄部分的高度訂為Z，又將從該Z起算的內側細線31及外側細線32的突出高度訂為Y1、Y2時，係訂為在Y1、Y2的一半高度之內側細線31及外側細線32的寬度。例如，當細線單元3具有上述薄膜部30的情形下，能夠將該薄膜部30中的最薄部分的高度訂為Z。另，當內側細線31及外側細線32間的機能性材料的最薄部分的高度為0時，內側細線31及外側細線32的線寬W1、W2，係訂為從基材1表面起算的在內側細線31及外側細線32的高度H1、H2的一半高度之內側細線31及外側細線32的寬度。 The line widths W1 and W2 of the inner thin line 31 and the outer thin line 32 of the thin line unit 3 are each preferably 10 μm or less. If it is 10 μm or less, it is generally unrecognizable, so it is more preferable from the viewpoint of improving transparency. In consideration of the stability of the inner thin line 31 and the outer thin line 32, the line widths W1 and W2 are each preferably in a range of 2 μm or more and 10 μm or less. The widths W1 and W2 of the inner thin line 31 and the outer thin line 32 are set to Z as the height of the thinnest part of the functional material between the inner thin line 31 and the outer thin line 32. When the protruding height of the inner thin line 31 and the outer thin line 32 from Z is set to Y1 and Y2, the widths of the inner thin line 31 and the outer thin line 32 are set to be half of the height of Y1 and Y2. For example, when the thin wire unit 3 has the thin film portion 30 described above, the height of the thinnest portion in the thin film portion 30 can be set to Z. In addition, when the height of the thinnest part of the functional material between the inner thin line 31 and the outer thin line 32 is 0, the line widths W1 and W2 of the inner thin line 31 and the outer thin line 32 are set to be from the surface of the substrate 1. The widths of the inner thin lines 31 and the outer thin lines 32 which are half the heights H1 and H2 of the inner thin lines 31 and the outer thin lines 32.
構成細線單元3之內側細線31及外側細線32的線寬W1、W2，如上述般為極細之物，因此就確保截面積而謀求低電阻化的觀點而言，理想是從基材1表面起算的內側細線31及外側細線32的高度H1、H2較高。具體而言，內側細線31及外側細線32的高度H1、H2，較佳為50nm以上5μm以下的範圍。又，由提升細線單元3的穩定性之觀點看來，H1/W1比、H2/W2比，較佳是各自為0.01以上1以下的範圍。 The line widths W1 and W2 of the inner thin wire 31 and the outer thin wire 32 constituting the thin wire unit 3 are extremely thin as described above. Therefore, from the viewpoint of ensuring a cross-sectional area and reducing resistance, it is desirable to start from the surface of the substrate 1 The heights H1 and H2 of the inner thin line 31 and the outer thin line 32 are relatively high. Specifically, the heights H1 and H2 of the inner thin lines 31 and the outer thin lines 32 are preferably in a range of 50 nm to 5 μm. From the viewpoint of improving the stability of the thin wire unit 3, the H1 / W1 ratio and the H2 / W2 ratio are each preferably in a range of 0.01 or more and 1 or less.
又，為了進一步提升細線單元3的細線化，H1/Z比、H2/Z比，較佳是各自為5以上，更佳是10以上，特佳是20以上。 In order to further improve the thinning of the thin wire unit 3, the H1 / Z ratio and the H2 / Z ratio are each preferably 5 or more, more preferably 10 or more, and particularly preferably 20 or more.
以上，有關細線單元3所做的說明，針對細 線單元5或另行追加設置之細線單元亦能援用。 Above, the description about the thin line unit 3 The wire unit 5 or a thin wire unit additionally provided can also be used.
細線中含有之機能性材料，如上述般較佳為導電性材料。藉由運用導電性材料，能夠將由該細線的集合體所構成之圖樣良好地用作為透明導電膜(亦稱為電極膜或透明電極)。 The functional material contained in the thin wire is preferably a conductive material as described above. By using a conductive material, a pattern composed of an assembly of the thin wires can be favorably used as a transparent conductive film (also referred to as an electrode film or a transparent electrode).
附透明導電膜基材之用途，雖無特別限定，但能用於各種電子機器所具備之各種元件。就顯著發揮本發明之功效的觀點而言，例如能夠良好地用作為液晶、電漿、有機電激發光、場發射等各種方式的顯示器用透明電極，或是用作為觸控面板或行動電話、電子紙、各種太陽能電池、各種電激發光調光元件等中使用之透明電極。特佳是使用附透明導電膜基材作為智慧型手機、平板終端等這樣的電子機器之觸控面板感測器。當用作為觸控面板感測器的情形下，作為透明基材的兩面的透明導電膜(X電極及Y電極)，較佳是使用上述細線圖樣。 Although the application of the substrate with a transparent conductive film is not particularly limited, it can be used for various elements included in various electronic devices. From the viewpoint of significantly exerting the effects of the present invention, for example, it can be suitably used as a transparent electrode for a display of various methods such as liquid crystal, plasma, organic electro-excitation light, and field emission, or as a touch panel or a mobile phone, Transparent electrodes used in electronic paper, various solar cells, and various electro-active light dimming elements. Particularly good is to use a substrate with a transparent conductive film as a touch panel sensor for electronic devices such as smart phones and tablet terminals. When used as a touch panel sensor, the transparent conductive films (X electrodes and Y electrodes) on both sides of the transparent substrate are preferably the thin line patterns described above.
以上說明中，針對一個態樣說明之構成，能夠適當適用於其他態樣。 In the above description, the structure described for one aspect can be appropriately applied to other aspects.
以下，說明本發明之實施例，但本發明並非由該實施例所限定。 Hereinafter, examples of the present invention will be described, but the present invention is not limited by the examples.
作為墨水(含有機能性材料之液體)，調製了以下組成之物。 As the ink (a liquid containing a functional material), the following composition was prepared.
‧銀奈米粒子(平均粒徑：20nm)：0.23重量% ‧Silver nano particles (average particle size: 20nm): 0.23% by weight
‧界面活性劑(BYK公司製「BYK348」)：0.05重量% ‧Surface active agent ("BYK348" manufactured by BYK): 0.05% by weight
‧二乙二醇單丁基醚(簡稱：DEGBE)(分散媒)：20重量% ‧Diethylene glycol monobutyl ether (abbreviation: DEGBE) (dispersion medium): 20% by weight
‧水(分散媒)：餘量 ‧Water (dispersed medium): balance
作為基材，準備了被施加表面處理以使含有機能性材料之液體的接觸角成為20.3°之PET基材。作為表面處理，使用信光電氣計裝公司製「PS-1M」進行了電暈放電處理。 As a base material, a PET base material was prepared that was subjected to a surface treatment such that the contact angle of a liquid containing a functional material was 20.3 °. As the surface treatment, a corona discharge treatment was performed using "PS-1M" manufactured by Shinko Denso Co., Ltd.
令噴墨頭(柯尼卡美能達公司製「KM1024iLHE-30」(標準液滴容量30pL))一面對基材相對移動一面從該噴墨頭吐出墨水，如圖3(a)所示，在基材上，藉由含有機能性材料之第1線狀液體2形成複數個具有內側緣與外側緣之封閉的幾何圖形。幾何圖形，為相對於基材的長邊方向而言各邊以45°傾斜之四角形。 The inkjet head ("KM1024iLHE-30" (standard droplet capacity 30pL) manufactured by Konica Minolta) was ejected from the inkjet head while the substrate was relatively moved, as shown in Fig. 3 (a). On the substrate, a plurality of closed geometric figures having an inner edge and an outer edge are formed by the first linear liquid 2 containing a functional material. The geometric figure is a quadrangle in which each side is inclined at 45 ° with respect to the long side direction of the substrate.
令該些第1線狀液體2乾燥，藉此，在該第1 線狀液體2的內側緣21及外側緣22使機能性材料選擇性地堆積，如圖3(b)所示，形成複數個由內側細線31及外側細線32所構成之第1細線單元3。得到的各第1細線單元3之內側細線31及外側細線32，為相對於基材的長邊方向而言各邊以45°傾斜之四角形。此四角形，沿著內側細線31及外側細線32的中間的線而測定出之1邊的長度為0.75mm。 The first linear liquids 2 are dried, whereby the first linear liquid 2 is dried. The inner edge 21 and the outer edge 22 of the linear liquid 2 selectively deposit functional materials. As shown in FIG. 3 (b), a plurality of first thin line units 3 composed of an inner thin line 31 and an outer thin line 32 are formed. The inner thin line 31 and the outer thin line 32 of each of the obtained first thin line units 3 have a rectangular shape with each side inclined at 45 ° with respect to the long side direction of the base material. The length of one side of this quadrangle measured along the line between the inner thin line 31 and the outer thin line 32 was 0.75 mm.
接著，令噴墨頭一面對基材相對移動一面從該噴墨頭吐出墨水，如圖4(a)所示，在基材上，藉由含有機能性材料之第2線狀液體4形成複數個具有內側緣與外側緣之封閉的幾何圖形。幾何圖形，為相對於基材的長邊方向而言各邊以45°傾斜之四角形。第2線狀液體4的形成位置，係設定成，第2線狀液體4的四角形的頂點鄰近，會覆蓋先前形成之第1細線單元3的外側細線32的四角形的頂點。 Next, the inkjet head ejects ink from the inkjet head while moving it relatively to the substrate. As shown in FIG. 4 (a), the ink is formed on the substrate by the second linear liquid 4 containing a functional material. A plurality of closed geometric figures having inside and outside edges. The geometric figure is a quadrangle in which each side is inclined at 45 ° with respect to the long side direction of the substrate. The formation position of the second linear liquid 4 is set such that the vertexes of the quadrangle of the second linear liquid 4 are adjacent to each other and cover the vertexes of the quadrangle of the outer thin line 32 of the first thin line unit 3 previously formed.
令該些第2線狀液體4乾燥，藉此，在該第2線狀液體4的內側緣41及外側緣42使機能性材料選擇性地堆積，如圖4(b)所示，形成複數個由內側細線51及外側細線52所構成之第2細線單元5。得到的各第2細線單元5之內側細線51及外側細線52，為相對於基材的長邊方向而言各邊以45°傾斜之四角形。此四角形，沿著內側細線51及外側細線52的中間的線而測定出之1邊的長度為0.75mm。 The second linear liquid 4 is dried, and thereby functional materials are selectively deposited on the inner edge 41 and the outer edge 42 of the second linear liquid 4 as shown in FIG. 4 (b), forming a plurality of The second thin line unit 5 is composed of an inner thin line 51 and an outer thin line 52. The inner thin line 51 and the outer thin line 52 of each of the obtained second thin line units 5 are quadrangular in which each side is inclined at 45 ° with respect to the longitudinal direction of the base material. The length of one side of this quadrangle measured along the line between the inner thin line 51 and the outer thin line 52 was 0.75 mm.
第1細線單元3的外側細線32，與第2細線 單元5的外側細線52互相連接，第1細線單元3的內側細線31，與第2細線單元5的內側細線51未互相連接而獨立。 The outer thin line 32 of the first thin line unit 3 and the second thin line The outer thin line 52 of the unit 5 is connected to each other, and the inner thin line 31 of the first thin line unit 3 is independent of the inner thin line 51 of the second thin line unit 5 without being connected to each other.
以上工程中，是在配置於被加熱至70℃之平台上的基材將線狀液體圖樣化，藉此促進線狀液體的乾燥。此外，對形成的細線，在130℃的烤箱中，施以10分鐘的燒成處理。 In the above process, the linear liquid is patterned on the substrate disposed on a platform heated to 70 ° C, thereby promoting the drying of the linear liquid. The formed fine wires were subjected to a firing treatment in an oven at 130 ° C for 10 minutes.
像這樣得到的細線圖樣(1)的光學顯微鏡照片如圖18所示。由圖18所示照片可知，由內側細線與外側細線所構成之細線單元形成了複數個。 An optical microscope photograph of the thin line pattern (1) obtained in this manner is shown in FIG. 18. As can be seen from the photograph shown in FIG. 18, a plurality of thin line units composed of the inner thin line and the outer thin line are formed.
對實施例1中得到的構成機能性細線圖樣(1)之細線單元3、5的外側細線32、52選擇性地施加銅電解鍍覆，而得到了如同圖6所示者之機能性細線圖樣(2)。銅電解鍍覆係依下述鍍覆條件進行。 The outer thin wires 32, 52 constituting the functional thin line pattern (1) obtained in Example 1 were selectively subjected to copper electrolytic plating, and a functional thin line pattern as shown in FIG. 6 was obtained. (2). Copper electrolytic plating is performed under the following plating conditions.
從裁斷成70×140mm之形成有實施例1的機能性細線圖樣(1)之基材的導電面供電，在下述鍍覆浴內進行了電解鍍覆。將陽極與鍍覆用銅板連接，在鍍覆浴內將基材設置於和銅板距30mm之位置。以0.2A的定電流做1分鐘鍍覆處理。鍍覆結束後，將基材水洗，使其乾燥。 Electric power was supplied from the conductive surface of the substrate on which the functional thin line pattern (1) of Example 1 was cut to 70 × 140 mm, and electrolytic plating was performed in the following plating bath. The anode was connected to a copper plate for plating, and the substrate was set in a plating bath at a distance of 30 mm from the copper plate. Do plating for 1 minute at a constant current of 0.2A. After the plating is completed, the substrate is washed with water and dried.
將硫酸銅五水合物20g、1N鹽酸1.3g、賦光澤劑(Meltex公司製「ST901C」)5g，以離子交換水調製成為1000mL。 20 g of copper sulfate pentahydrate, 1.3 g of 1N hydrochloric acid, and 5 g of a gloss-imparting agent ("ST901C" manufactured by Meltex) were prepared into 1000 mL with ion-exchanged water.
像這樣得到的機能性細線圖樣(2)的光學顯微鏡照片如圖19所示。由圖19所示照片可知，在互相電性連接之外側細線選擇性地被施加了鍍覆(此處為銅鍍覆)。另，圖19所示照片為灰階化者，在彩色照片中，能夠確認受到銅鍍覆之外側細線係被著色成銅色。 An optical microscope photograph of the functional thin line pattern (2) obtained in this manner is shown in FIG. 19. As can be seen from the photograph shown in FIG. 19, the thin wires outside the electrical connection are selectively plated (here, copper plating). In addition, the photograph shown in FIG. 19 is a grayscale person, and in the color photograph, it can be confirmed that the thin wires outside the copper plating are colored to a copper color.
對構成實施例2中得到的機能性細線圖樣(2)之外側細線32、52選擇性地施加鎳電解鍍覆，並且藉由鍍覆液除去內側細線31、51，而得到了如同圖7所示者之機能性細線圖樣(3)。鎳電解鍍覆係依下述鍍覆條件進行。 Nickel electrolytic plating was selectively applied to the outer thin wires 32 and 52 constituting the functional thin line pattern (2) obtained in Example 2, and the inner thin wires 31 and 51 were removed by the plating solution. As shown in FIG. 7 Functional thin line drawing of the shower (3). Nickel electrolytic plating is performed under the following plating conditions.
從形成有實施例2的機能性細線圖樣(2)之基材的導電面供電，在下述鍍覆浴內進行了電解鍍覆。將陽極與鍍覆用鎳板連接，在鍍覆浴內將基材設置於和鎳板距30mm之位置。以0.2A的定電流做30秒鍍覆處理。為了藉由鍍覆液將內側細線31、51充分除去，於鍍覆結束後，將基材於鍍覆浴內放置了10分鐘後，水洗，使其乾燥。 Power was supplied from the conductive surface of the substrate on which the functional thin line pattern (2) of Example 2 was formed, and electrolytic plating was performed in the plating bath described below. The anode was connected to a nickel plate for plating, and the substrate was set in a plating bath at a distance of 30 mm from the nickel plate. The plating process was performed at a constant current of 0.2A for 30 seconds. In order to sufficiently remove the inner thin wires 31 and 51 by the plating solution, after the plating is completed, the substrate is left in the plating bath for 10 minutes, and then washed with water and dried.
將硫酸鎳240g、氯化鎳45g、硼酸30g，以離子交換水調製成1000mL。 240 g of nickel sulfate, 45 g of nickel chloride, and 30 g of boric acid were prepared to 1000 mL with ion-exchanged water.
像這樣得到的機能性細線圖樣(3)的光學顯微鏡照片如圖20所示。由圖20所示照片可知，在互相電性連接之外側細線32、52選擇性地被施加了鍍覆(此處為鎳鍍覆)。另，圖20所示照片為灰階化者，在彩色照片中，能夠確認外側細線從銅色變化成了無色(鎳所致之銀色)。此外，可知內側細線31、51選擇性地被除去。 An optical microscope photograph of the functional thin line pattern (3) obtained in this manner is shown in FIG. 20. It can be seen from the photograph shown in FIG. 20 that the outer thin wires 32 and 52 are selectively plated (here, nickel plating) on the outer side of the electrical connection. In addition, the photograph shown in FIG. 20 is a grayscale person, and in the color photograph, it can be confirmed that the outer thin line has changed from copper to colorless (silver due to nickel). In addition, it can be seen that the inner thin wires 31 and 51 are selectively removed.
細線寬[μm]，為將構成細線單元之外側細線的線寬藉由顯微鏡觀察而測定之值。 The thin line width [μm] is a value measured by observing the line width of the thin lines outside the thin line unit by a microscope.
透射率[%]，為使用東京電色公司製AUTOMATIC HAZEMETER(MODEL TC-H III DP)測定出之全光線透射率[%]。另，運用沒有圖樣的基材(膜)進行修正，以測定作為作成的圖樣的全光線透射率。 The transmittance [%] is the total light transmittance [%] measured using AUTOMATIC HAZEMETER (MODEL TC-H III DP) manufactured by Tokyo Denshoku Corporation. In addition, correction was performed using a base material (film) without a pattern to measure the total light transmittance of the pattern to be created.
片電阻值[Ω/□]，為使用DIA INSTRUMENTS公司製 LORESTA EP(MODEL MCP-T360型)直列4探針針測儀(ESP)測定出之值。 Chip resistance [Ω / □], using DIA INSTRUMENTS LORESTA EP (MODEL MCP-T360) in-line 4-probe needle probe (ESP) measured value.
將樣本從燈桌(light table)上距50cm之位置目視，細線愈無法視認則愈評估為低視認性優良，具體而言依下述評估基準評估。另，以下評估基準中，若為B評估以上，則能在作為透明導電膜之用途中良好地使用。 The sample was visually observed from a light table at a distance of 50 cm, and the thinner the line was, the more difficult it was to recognize it, and the lower the visibility was, the more it was evaluated. Specifically, it was evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, if it is B evaluation or more, it can be used favorably for the use as a transparent conductive film.
A：細線無法視認 A: Thin lines cannot be recognized
B：細線能略微視認 B: Thin lines can be recognized slightly
C：細線能明顯視認(無符合者) C: Thin lines can be clearly recognized (no match)
以上結果如表1所示。 The above results are shown in Table 1.
實施例1~3中，藉由使用由含有機能性材料的內側 細線與外側細線所構成之細線單元，能夠高自由度而穩定地形成細線圖樣。 In Examples 1 to 3, by using an inner side containing a functional material, A thin line unit composed of a thin line and an outer thin line can form a thin line pattern stably with a high degree of freedom.
由表1的實施例2、3之結果可知，藉由對細線單元的外側細線施加鍍覆，能夠使片電阻值更良好地降低。此外，由實施例3之結果可知，藉由除去細線單元的內側細線，增大細線的配置間隔，能夠更良好地提升透射率與低視認性。 From the results of Examples 2 and 3 in Table 1, it can be seen that by applying plating to the outer thin wires of the thin wire unit, the sheet resistance value can be further reduced. In addition, from the results of Example 3, it can be seen that by removing the inner thin lines of the thin line unit and increasing the arrangement interval of the thin lines, the transmittance and low visibility can be improved better.
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