TWI597742B - Transparent conductive body and touch panel - Google Patents

Transparent conductive body and touch panel Download PDF

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TWI597742B
TWI597742B TW104144037A TW104144037A TWI597742B TW I597742 B TWI597742 B TW I597742B TW 104144037 A TW104144037 A TW 104144037A TW 104144037 A TW104144037 A TW 104144037A TW I597742 B TWI597742 B TW I597742B
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metal oxide
oxide layer
layer
film
metal
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TW104144037A
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TW201637028A (en
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Hiroshi Shingai
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Tdk Corp
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    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47K—SANITARY EQUIPMENT NOT OTHERWISE PROVIDED FOR; TOILET ACCESSORIES
    • A47K10/00—Body-drying implements; Toilet paper; Holders therefor
    • A47K10/24—Towel dispensers, e.g. for piled-up or folded textile towels; Toilet-paper dispensers; Dispensers for piled-up or folded textile towels provided or not with devices for taking-up soiled towels as far as not mechanically driven
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/02—Wrappers or flexible covers
    • B65D65/16—Wrappers or flexible covers with provision for excluding or admitting light
    • B65D65/18—Wrappers or flexible covers with provision for excluding or admitting light with some areas transparent and others opaque
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes, or webs of flexible sheet material, e.g. in folded wrappers
    • B65D75/52—Details
    • B65D75/522—Inspection openings or windows
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes, or webs of flexible sheet material, e.g. in folded wrappers
    • B65D75/52—Details
    • B65D75/58—Opening or contents-removing devices added or incorporated during package manufacture
    • B65D75/5816—Opening or contents-removing devices added or incorporated during package manufacture for tearing a corner or other small portion next to the edge, e.g. a U-shaped portion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/32—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging two or more different materials which must be maintained separate prior to use in admixture
    • B65D81/3261—Flexible containers having several compartments
    • B65D81/3266—Flexible containers having several compartments separated by a common rupturable seal, a clip or other removable fastening device
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47K—SANITARY EQUIPMENT NOT OTHERWISE PROVIDED FOR; TOILET ACCESSORIES
    • A47K10/00—Body-drying implements; Toilet paper; Holders therefor
    • A47K10/24—Towel dispensers, e.g. for piled-up or folded textile towels; Toilet-paper dispensers; Dispensers for piled-up or folded textile towels provided or not with devices for taking-up soiled towels as far as not mechanically driven
    • A47K10/32—Dispensers for paper towels or toilet-paper
    • A47K2010/3266—Wet wipes
    • A47K2010/3273—Wet wipes moistened just before use
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D2203/00—Decoration means, markings, information elements, contents indicators
    • B65D2203/12—Audible, olfactory or visual signalling means
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices

Description

透明導電體及觸控面板 Transparent conductor and touch panel

本發明係關於一種透明導電體以及使用其的觸控面板。 The present invention relates to a transparent conductor and a touch panel using the same.

透明導電體可以用作液晶顯示器(LCD)、電漿顯示面板(PDP)以及電致發光面板(有機EL、無機EL)等的顯示器、以及太陽能電池等的透明電極。又，除了這些以外，也可以用於電磁波遮蔽膜或抗紅外線膜等。作為透明導電體中的金屬氧化物層的材料，廣泛地使用在氧化銦(In2O3)中添加有錫(Sn)的ITO。 The transparent conductor can be used as a display of a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence panel (organic EL, inorganic EL), or the like, and a transparent electrode of a solar cell or the like. Moreover, in addition to these, it can also be used for an electromagnetic wave shielding film, an anti-infrared film, etc. As a material of the metal oxide layer in the transparent conductor, ITO in which tin (Sn) is added to indium oxide (In 2 O 3 ) is widely used.

近年來，智慧手機和平板終端等，具備觸控面板的終端正迅速普及。該等係具有在液晶面板上設置有觸控感測器部，在最外表面具備玻璃蓋板(cover glass)的構成。觸控感測器部在玻璃或薄膜基材的一面或兩面上，貼附有1片或2片藉由濺射法將ITO膜成膜後的薄膜而構成。 In recent years, terminals such as smart phones and tablet terminals that have touch panels are rapidly spreading. These systems have a configuration in which a touch sensor portion is provided on a liquid crystal panel and a cover glass is provided on the outermost surface. The touch sensor unit is formed by attaching one or two thin films on which one or two ITO films are formed by sputtering on one surface or both surfaces of a glass or a film substrate.

伴隨著觸控面板的大型化和觸控感測器功能的高精度化，尋求具有高穿透率並且低電阻的透明導電體。為了降低使用了ITO膜之透明導電體的電阻，需要加厚ITO膜的膜厚，或者藉由熱退火進行ITO膜的結晶化。然而，如果將ITO膜厚膜化，則穿透率降低。另外，通常難以在高溫下將薄膜基材熱退火。因此，設置在薄膜基材上的ITO膜，有難以維持高的穿透率並且降低電阻的情況。 With the increase in the size of the touch panel and the high precision of the touch sensor function, a transparent conductor having high transmittance and low resistance has been sought. In order to reduce the electric resistance of the transparent conductor using the ITO film, it is necessary to thicken the film thickness of the ITO film or to crystallize the ITO film by thermal annealing. However, if the ITO film is thickened, the transmittance is lowered. In addition, it is generally difficult to thermally anneal the film substrate at a high temperature. Therefore, the ITO film provided on the film substrate has a situation in which it is difficult to maintain high transmittance and reduce electric resistance.

在如此的情況下，提出有具有以氧化鋅為主成分的金屬氧化物層和金屬層的積層結構的透明導電膜(例如，專利文獻1)。 In such a case, a transparent conductive film having a laminated structure of a metal oxide layer containing a zinc oxide as a main component and a metal layer is proposed (for example, Patent Document 1).

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

專利文獻1：日本專利特開平9-291355號公報 Patent Document 1: Japanese Patent Laid-Open No. Hei 9-291355

觸控面板等的用途中，藉由將透明導電膜圖案化為導電部分和絕緣部分，進行觸碰位置的檢測。因此，在具有金屬氧化物層和金屬層的積層結構的透明導電體中，尋求能夠藉由蝕刻將金屬氧化物層和金屬層一起除去。然而，在將氧化鋅作為主成分的金屬氧化物層和金屬層的積層結構中，存在難以藉由蝕刻一起除去金屬氧化物層和金屬層的情況。 In the use of a touch panel or the like, the detection of the touch position is performed by patterning the transparent conductive film into a conductive portion and an insulating portion. Therefore, in a transparent conductor having a laminated structure of a metal oxide layer and a metal layer, it is sought to remove the metal oxide layer and the metal layer together by etching. However, in the laminated structure of the metal oxide layer and the metal layer containing zinc oxide as a main component, there is a case where it is difficult to remove the metal oxide layer and the metal layer by etching together.

因此，本案發明提供一種能夠容易地將金屬氧化物層和金屬層圖案化的透明導電體，上述透明導電體具有含有氧化鋅作為主成分的金屬氧化物層和金屬層的積層結構。另外，本案發明係藉由使用如此的透明導電體，而提供能夠容易地製造的觸控面板。 Therefore, the present invention provides a transparent conductor which can easily pattern a metal oxide layer and a metal layer, and the transparent conductor has a laminated structure of a metal oxide layer containing a zinc oxide as a main component and a metal layer. Further, the present invention provides a touch panel that can be easily manufactured by using such a transparent conductor.

本發明之一個態樣係提供一種透明導電體，上述透明導電體依序積層有透明樹脂基材、第1金屬氧化物層、含有銀合金的金屬層以及第2金屬氧化物層，第2金屬氧化物層含有ZnO作為主成分，並且含有In2O3、TiO2、Ga2O3以及GeO2作為副成分，TiO2的含量相對於ZnO、In2O3、TiO2、Ga2O3以及GeO2這5種成分的合計為 12mol%以下。 An aspect of the present invention provides a transparent conductor in which a transparent resin substrate, a first metal oxide layer, a metal layer containing a silver alloy, and a second metal oxide layer, a second metal, are sequentially laminated The oxide layer contains ZnO as a main component and contains In 2 O 3 , TiO 2 , Ga 2 O 3 , and GeO 2 as subcomponents, and the content of TiO 2 is relative to ZnO, In 2 O 3 , TiO 2 , Ga 2 O 3 . The total of the five components of GeO 2 is 12 mol% or less.

如此的透明導電體具有積層結構，上述積層結構具備：構成最外表面的第2金屬氧化物層和含有銀合金的金屬層。該第2金屬氧化物層和金屬層藉由蝕刻可以一起容易地被除去。另外，可以製成具有高透明性、高導電性、以及優異的耐腐蝕性的透明導電體。因此，可以適當地用於觸控面板等需要蝕刻的用途。 Such a transparent conductor has a laminated structure, and the laminated structure includes a second metal oxide layer constituting the outermost surface and a metal layer containing a silver alloy. The second metal oxide layer and the metal layer can be easily removed together by etching. In addition, a transparent conductor having high transparency, high conductivity, and excellent corrosion resistance can be produced. Therefore, it can be suitably used for applications requiring etching such as a touch panel.

在數個實施形態之中，在第2金屬氧化物層中，ZnO的含量相對於ZnO、In2O3、TiO2、Ga2O3以及GeO2這5種成分的合計可以為72~85mol%。In2O3的含量相對於上述5種成分的合計可以為4~13mol%。TiO2的含量相對於上述5種成分的合計可以為3~12mol%。Ga2O3的含量相對於上述5種成分的合計可以為3~9mol%。GeO2的含量相對於上述5種成分的合計可以為3~12mol%。藉由以上述的比例含有ZnO、In2O3、TiO2、Ga2O3以及GeO2，可以充分地提高第2金屬氧化物層的透明性、導電性、耐腐蝕性以及蝕刻性。 In a plurality of embodiments, the total content of ZnO in the second metal oxide layer may be 72 to 85 mol based on the total of the five components of ZnO, In 2 O 3 , TiO 2 , Ga 2 O 3 , and GeO 2 . %. The content of In 2 O 3 may be 4 to 13 mol% based on the total of the above five components. The content of TiO 2 may be 3 to 12 mol% based on the total of the above five components. The content of Ga 2 O 3 may be 3 to 9 mol% based on the total of the above five components. The content of GeO 2 may be 3 to 12 mol% based on the total of the above five components. By containing ZnO, In 2 O 3 , TiO 2 , Ga 2 O 3 , and GeO 2 in the above ratio, the transparency, conductivity, corrosion resistance, and etching property of the second metal oxide layer can be sufficiently improved.

另外，在數個實施形態之中，第2金屬氧化物層可以具有特定的結晶性。由此，第2金屬氧化物層除了蝕刻性以外還具有耐鹼性。藉由濕式法得到的透明導電膜的圖案化步驟中，使用光阻進行圖案形成，最後進行光阻剝離，在光阻剝離中使用鹼溶液。因此，在利用濕式法進行圖案化時，金屬氧化物層較佳為兼顧能夠溶解於酸中進行蝕刻和不溶解於鹼中的耐鹼性。 Further, in some embodiments, the second metal oxide layer may have specific crystallinity. Thereby, the second metal oxide layer has alkali resistance in addition to etching properties. In the patterning step of the transparent conductive film obtained by the wet method, patterning is performed using a photoresist, and finally, photoresist peeling is performed, and an alkali solution is used for resist stripping. Therefore, when patterning by the wet method, it is preferable that the metal oxide layer has both alkali resistance which can be dissolved in an acid to be etched and not dissolved in a base.

在數個實施形態之中，第1金屬氧化物層含有ZnO作為主成分，並且含有In2O3、TiO2、Ga2O3以及GeO2作為副成分，TiO2的含量相對於ZnO、In2O3、TiO2、Ga2O3以及GeO2這5種成分的合計 可以為12mol%以下。由此，可以藉由蝕刻一起容易地除去第1金屬氧化物層、第2金屬氧化物層以及金屬層。另外，可以製成具有高透明性、高導電性以及優異的耐腐蝕性的透明導電體。 In several embodiments, the first metal oxide layer contains ZnO as a main component, and contains In 2 O 3 , TiO 2 , Ga 2 O 3 , and GeO 2 as auxiliary components, and the content of TiO 2 is relative to ZnO and In. The total of the five components of 2 O 3 , TiO 2 , Ga 2 O 3 and GeO 2 may be 12 mol% or less. Thereby, the first metal oxide layer, the second metal oxide layer, and the metal layer can be easily removed by etching. In addition, a transparent electric conductor having high transparency, high electrical conductivity, and excellent corrosion resistance can be produced.

在數個實施形態之中，金屬層的厚度可以為4~11nm。由此，可以充分地提高透明導電體的透明性，並且降低表面電阻。在數個實施形態之中，銀合金可以為Ag與選自Pd、Cu、Nd、In、Sn以及Sb中的至少1種金屬的合金。 In several embodiments, the metal layer may have a thickness of 4 to 11 nm. Thereby, the transparency of the transparent conductor can be sufficiently improved, and the surface resistance can be lowered. In some embodiments, the silver alloy may be an alloy of Ag and at least one metal selected from the group consisting of Pd, Cu, Nd, In, Sn, and Sb.

本發明之另一態樣提供一種觸控面板，上述觸控面板在面板上具有感測器薄膜，該感測器薄膜由上述透明導電體構成。如此的觸控面板由於具有由上述透明導電體構成的感測器薄膜，因此，可以容易地製造。 Another aspect of the present invention provides a touch panel having a sensor film on a panel, the sensor film being composed of the transparent conductor. Since such a touch panel has a sensor film composed of the above transparent conductor, it can be easily manufactured.

根據本案發明，可以提供一種在具有含有氧化鋅作為主成分的金屬氧化物層和金屬層的積層結構的透明導電體中，能夠容易地將金屬氧化物層和金屬層圖案化的透明導電體。另外，本案發明中可以提供藉由使用如此的透明導電體從而能夠容易地製造的觸控面板。 According to the invention, it is possible to provide a transparent conductor in which a metal oxide layer and a metal layer can be easily patterned in a transparent conductor having a laminated structure of a metal oxide layer containing a zinc oxide as a main component and a metal layer. Further, in the invention of the present invention, a touch panel which can be easily manufactured by using such a transparent conductor can be provided.

10‧‧‧透明樹脂基材 10‧‧‧Transparent resin substrate

12‧‧‧第1金屬氧化物層 12‧‧‧1st metal oxide layer

14‧‧‧第2金屬氧化物層 14‧‧‧2nd metal oxide layer

16‧‧‧金屬層 16‧‧‧metal layer

15a、15b‧‧‧感測器電極 15a, 15b‧‧‧ sensor electrodes

17、18‧‧‧光學膠 17, 18‧‧‧ optical glue

19‧‧‧玻璃蓋板 19‧‧‧ glass cover

20‧‧‧硬塗層 20‧‧‧hard coating

22‧‧‧第1硬塗層 22‧‧‧1st hard coat

24‧‧‧第2硬塗層 24‧‧‧2nd hard coat

50‧‧‧導體線路 50‧‧‧Conductor lines

70‧‧‧面板 70‧‧‧ panel

80‧‧‧電極 80‧‧‧ electrodes

90‧‧‧接黏劑 90‧‧‧Adhesive

92‧‧‧墊片 92‧‧‧shims

100、101‧‧‧透明導電體 100, 101‧‧‧ Transparent conductor

100a‧‧‧Y用感測器薄膜 100a‧‧‧Y sensor film

100b‧‧‧X用感測器薄膜 100b‧‧‧X sensor film

200‧‧‧觸控面板 200‧‧‧ touch panel

圖1係示意地表示透明導電體的一個實施形態的截面圖。 Fig. 1 is a cross-sectional view schematically showing an embodiment of a transparent conductor.

圖2係示意地表示透明導電體的另一實施形態的截面圖。 Fig. 2 is a cross-sectional view schematically showing another embodiment of a transparent conductor.

圖3係將觸控面板的一個實施形態的截面的一部分放大表示的示意截面圖。 3 is a schematic cross-sectional view showing a part of a cross section of an embodiment of a touch panel in an enlarged manner.

圖4(A)和圖4(B)是構成觸控面板的一個實施形態的感測器薄 膜的平面圖。 4(A) and 4(B) are thin sensor tubes constituting one embodiment of the touch panel Plan view of the membrane.

以下一邊參照附圖一邊詳細地說明本發明的較佳為的實施形態。但是，本發明並沒有被限定於以下的任何實施形態。另外，圖式中對同一或同等的元件賦予同一符號，根據情況省略重複的說明。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to any of the following embodiments. In the drawings, the same or equivalent elements are designated by the same reference numerals, and the repeated description is omitted as appropriate.

圖1是表示透明導電體的一個實施形態的示意截面圖。透明導電體100具有依序配置有薄膜狀的透明樹脂基材10、第1金屬氧化物層12、金屬層16和第2金屬氧化物層14的積層結構。 Fig. 1 is a schematic cross-sectional view showing an embodiment of a transparent conductor. The transparent conductor 100 has a laminated structure in which a film-shaped transparent resin substrate 10, a first metal oxide layer 12, a metal layer 16, and a second metal oxide layer 14 are sequentially disposed.

本說明書中的「透明」是指可見光穿透，也可以使光以某種程度散射。對於光的散射程度，根據透明導電體100的用途所要求的水準不同。有通常被稱為半透明般的光散射的情況也包含於本說明書中的「透明」的概念中。較佳為光的散射程度小，較佳為透明性高。透明導電體100整體的總透光率例如為80%以上，較佳為83%以上，進一步較佳為85%以上。該總透光率是使用積分球所求得的包含擴散透射光的穿透率，可以使用市售的霧度計進行測定。 "Transparent" in this specification means that visible light penetrates, and light can be scattered to some extent. The degree of scattering of light differs depending on the level required for the use of the transparent conductor 100. The case of what is commonly referred to as translucent light scattering is also included in the concept of "transparency" in this specification. It is preferred that the degree of scattering of light is small, and it is preferred that the transparency is high. The total light transmittance of the entire transparent conductor 100 is, for example, 80% or more, preferably 83% or more, and more preferably 85% or more. The total light transmittance is a transmittance including diffused transmitted light obtained by using an integrating sphere, and can be measured using a commercially available haze meter.

作為透明樹脂基材10，沒有特別地限定，可以是具有可撓性的有機樹脂薄膜。有機樹脂薄膜也可以是有機樹脂薄片。作為有機樹脂薄膜，例如可以列舉聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)等的聚酯薄膜、聚乙烯以及聚丙烯等的聚烯烴薄膜、聚碳酸酯薄膜、丙烯酸薄膜、降烯薄膜、聚芳酯薄膜、聚醚碸薄膜、二乙醯基纖維素薄膜、以及三乙醯基纖維素薄膜等。該等之中，較佳為聚對苯二甲酸乙二酯(PET)以及聚萘二甲酸乙二酯 (PEN)等的聚酯薄膜。 The transparent resin substrate 10 is not particularly limited, and may be a flexible organic resin film. The organic resin film may also be an organic resin sheet. Examples of the organic resin film include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films such as polyethylene and polypropylene, and polycarbonate. Film, acrylic film, drop An ene film, a polyarylate film, a polyether ruthenium film, a diethyl fluorene-based cellulose film, a triethylene fluorene-based cellulose film, or the like. Among these, a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) is preferable.

從剛性的觀點，透明樹脂基材10較佳為厚。另一方面，從將透明導電體100薄膜化的觀點，透明樹脂基材10較佳為薄。從如此的觀點，透明樹脂基材10的厚度例如為10~200μm。從製成光學特性優異的透明導電體的觀點，透明樹脂基材10的折射率例如為1.50~1.70。另外，本說明書中的折射率是在λ=633nm、溫度為20℃的條件下測定之值。 The transparent resin substrate 10 is preferably thick from the viewpoint of rigidity. On the other hand, from the viewpoint of thinning the transparent conductor 100, the transparent resin substrate 10 is preferably thin. From such a viewpoint, the thickness of the transparent resin substrate 10 is, for example, 10 to 200 μm. The refractive index of the transparent resin substrate 10 is, for example, from 1.50 to 1.70 from the viewpoint of producing a transparent conductor having excellent optical properties. Further, the refractive index in the present specification is a value measured under conditions of λ = 633 nm and a temperature of 20 °C.

透明樹脂基材10較佳為加熱時的尺寸穩定性高。通常在薄膜製作過程中，可撓性的有機樹脂薄膜藉由加熱產生由膨脹或收縮造成的尺寸變化。在單軸拉伸或雙軸拉伸時，可以製作低成本並且厚度薄的透明樹脂基材10。形成引出電極時，如果將透明導電體100加熱，則由於熱收縮而發生尺寸變化。該等尺寸變化可以按照ASTM D1204-02或JIS-C-2151來進行測定。加熱處理前後的尺寸變化率在將加熱前的尺寸設定為Lo、將加熱後的尺寸設定為L時用以下的式子求取。 The transparent resin substrate 10 preferably has high dimensional stability upon heating. The flexible organic resin film usually produces dimensional changes caused by expansion or contraction by heating during film formation. In the case of uniaxial stretching or biaxial stretching, a transparent resin substrate 10 which is low in cost and thin in thickness can be produced. When the extraction electrode is formed, if the transparent conductor 100 is heated, dimensional changes occur due to heat shrinkage. These dimensional changes can be measured in accordance with ASTM D1204-02 or JIS-C-2151. The dimensional change rate before and after the heat treatment was determined by the following formula when the size before heating was set to L o and the size after heating was set to L.

尺寸變化率(%)=100×(L-Lo)/Lo Dimensional change rate (%) = 100 × (LL o ) / L o

在尺寸變化率(%)為正數的情況下，表示藉由加熱處理發生了膨脹；在負數的情況下，表示藉由加熱處理發生了收縮。雙軸拉伸的透明樹脂基材10的尺寸變化率可以在拉伸時的進行方向(MD方向)和橫向(TD方向)兩者進行測定。透明樹脂基材10的尺寸變化率例如在MD方向中為-1.0~-0.3%，在TD方向中為-0.1~+0.1%。 In the case where the dimensional change rate (%) is a positive number, it indicates that expansion has occurred by heat treatment; in the case of a negative number, it indicates that shrinkage has occurred by heat treatment. The dimensional change rate of the biaxially stretched transparent resin substrate 10 can be measured in both the progress direction (MD direction) and the lateral direction (TD direction) at the time of stretching. The dimensional change rate of the transparent resin substrate 10 is, for example, -1.0 to -0.3% in the MD direction and -0.1 to +0.1% in the TD direction.

透明樹脂基材10也可以施以選自電暈放電處理、輝光放電處理、火焰處理、紫外線照射處理、電子射線照射處理以及臭氧處理中的至少一種表面處理。透明樹脂基材10可以是樹脂薄膜。 藉由使用樹脂薄膜，可以將透明導電體100製成柔軟性優異的導電體。因此，不限於觸控面板用途的透明導電體，也可以用作可撓性有機EL照明等的透明電極用或電磁波遮罩。 The transparent resin substrate 10 may be subjected to at least one surface treatment selected from the group consisting of corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, and ozone treatment. The transparent resin substrate 10 may be a resin film. By using a resin film, the transparent conductor 100 can be made into a conductor excellent in flexibility. Therefore, it is not limited to a transparent conductor used for a touch panel, and can also be used as a transparent electrode or an electromagnetic wave mask for flexible organic EL illumination or the like.

例如，在將透明導電體100用作構成觸控面板的感測器薄膜的情況下，透明樹脂基材10也可以使用具有可撓性的有機樹脂薄膜，以對於手指和筆等的外部輸入能夠適度地變形。 For example, in the case where the transparent conductor 100 is used as a sensor film constituting a touch panel, the transparent resin substrate 10 can also use a flexible organic resin film to enable external input to fingers, pens, and the like. Moderately deformed.

第2金屬氧化物層14是包含氧化物的透明之層，含有ZnO作為主成分，並且含有In2O3、TiO2、Ga2O3以及GeO2作為副成分，TiO2的含量相對於ZnO、In2O3、TiO2、Ga2O3以及GeO2這5種成分的合計為12mol%以下。在此所說的主成分是在ZnO、In2O3、TiO2、Ga2O3以及GeO2這5種成分中，莫耳基準的含量最多的成分。副成分是上述5種成分中非主成分之成分。第2金屬氧化物層14由於含有ZnO作為主成分，因此，經濟性優異。另外，不使用ITO也可以形成兼具高的導電性和高的透明性的第2金屬氧化物層14。由此，即使不進行熱退火，也可以製成具有低的表面電阻的第2金屬氧化物層14。 The second metal oxide layer 14 is a transparent layer containing an oxide containing ZnO as a main component and containing In 2 O 3 , TiO 2 , Ga 2 O 3 , and GeO 2 as a subcomponent, and the content of TiO 2 is relative to ZnO. The total of the five components of In 2 O 3 , TiO 2 , Ga 2 O 3 and GeO 2 is 12 mol% or less. The main component referred to herein is a component having the highest molar content in the five components of ZnO, In 2 O 3 , TiO 2 , Ga 2 O 3 and GeO 2 . The accessory component is a component other than the above-mentioned five components. Since the second metal oxide layer 14 contains ZnO as a main component, it is excellent in economy. Further, the second metal oxide layer 14 having both high conductivity and high transparency can be formed without using ITO. Thereby, the second metal oxide layer 14 having a low surface resistance can be obtained without performing thermal annealing.

在此，在第2金屬氧化物層14中，TiO2的含量相對於上述5種成分的合計，從充分地提高蝕刻性的觀點，為12mol%以下，較佳為10mol%以下。另外，在第2金屬氧化物層14中，TiO2的含量相對於上述5種成分的合計，從充分地提高保存穩定性的觀點，較佳為3mol%以上，更較佳為4mol%以上。如果TiO2的含量過多，則第2金屬氧化物層14與金屬層16的積層結構變得不能蝕刻。另外，電阻值也惡化。另一方面，如果TiO2的含量過少，則上述積層結構的保存穩定性降低。 In the second metal oxide layer 14 , the content of the TiO 2 is 12 mol% or less, preferably 10 mol% or less, from the viewpoint of sufficiently improving the etching property. In addition, the content of the TiO 2 in the second metal oxide layer 14 is preferably 3 mol% or more, and more preferably 4 mol% or more from the viewpoint of sufficiently improving the storage stability. If the content of TiO 2 is too large, the laminated structure of the second metal oxide layer 14 and the metal layer 16 becomes impossible to etch. In addition, the resistance value also deteriorates. On the other hand, if the content of TiO 2 is too small, the storage stability of the above laminated structure is lowered.

在第2金屬氧化物層14中，ZnO的含量相對於上述5種成分的合計，從充分地提高穿透率和導電性的觀點，例如為72mol%以上，較佳為75mol%以上。在第2金屬氧化物層14中，ZnO的含量相對於上述5種成分的合計，從充分地提高保存穩定性的觀點，例如為85mol%以下，較佳為82mol%以下。如果ZnO的含量過多，則在高溫高濕環境下保存的情況下，有容易產生白濁的傾向。另一方面，如果ZnO的含量過少，則有穿透率和導電性降低的傾向。 In the second metal oxide layer 14 , the content of ZnO is, for example, 72 mol % or more, and preferably 75 mol % or more from the viewpoint of sufficiently improving the transmittance and conductivity from the total of the above five components. In the second metal oxide layer 14 , the content of ZnO is, for example, 85 mol % or less, preferably 82 mol % or less, from the viewpoint of sufficiently improving the storage stability with respect to the total of the above five components. When the content of ZnO is too large, it tends to cause white turbidity when stored in a high-temperature and high-humidity environment. On the other hand, if the content of ZnO is too small, the transmittance and conductivity tend to be lowered.

在第2金屬氧化物層14中，In2O3的含量相對於上述5種成分的合計，從充分地降低表面電阻並且充分地提高穿透率的觀點，例如為13mol%以下，較佳為11mol%以下。在第2金屬氧化物層14中，In2O3的含量相對於上述5種成分的合計，從充分地提高保存穩定性的觀點，例如為4mol%以上，較佳為6mol%以上。如果In2O3的含量過多，則有表面電阻變高的傾向、以及穿透率降低的傾向。另一方面，如果In2O3的含量過少，則在高溫高濕環境下保存的情況下有容易產生白濁，並且表面電阻變高的傾向。 In the second metal oxide layer 14 , the content of the In 2 O 3 is preferably 13 mol% or less from the viewpoint of sufficiently reducing the surface resistance and sufficiently increasing the transmittance. 11 mol% or less. In the second metal oxide layer 14 , the content of the In 2 O 3 is, for example, 4 mol% or more, and preferably 6 mol% or more from the viewpoint of sufficiently improving the storage stability. When the content of In 2 O 3 is too large, the surface resistance tends to be high and the transmittance tends to decrease. On the other hand, when the content of In 2 O 3 is too small, white turbidity tends to occur when stored in a high-temperature and high-humidity environment, and the surface resistance tends to be high.

在第2金屬氧化物層14中，Ga2O3的含量相對於上述5種成分的合計，從充分地降低表面電阻並且充分地提高穿透率的觀點，例如為9mol%以下，較佳為7mol%以下。在第2金屬氧化物層14中，Ga2O3的含量相對於上述5種成分的合計，從充分地提高保存穩定性的觀點，例如為3mol%以上，較佳為3.5mol%以上。如果Ga2O3的含量過多，則有表面電阻變高的傾向。另一方面，如果Ga2O3的含量過少，則在高溫高濕環境下保存的情況下有白濁容易產生，並且表面電阻變高的傾向。 In the second metal oxide layer 14 , the content of the Ga 2 O 3 is preferably 9 mol% or less from the viewpoint of sufficiently reducing the surface resistance and sufficiently increasing the transmittance. 7 mol% or less. In the second metal oxide layer 14 , the content of the Ga 2 O 3 is, for example, 3 mol% or more, and preferably 3.5 mol% or more, from the viewpoint of sufficiently improving the storage stability. When the content of Ga 2 O 3 is too large, the surface resistance tends to be high. On the other hand, when the content of Ga 2 O 3 is too small, white turbidity tends to occur when stored in a high-temperature and high-humidity environment, and the surface resistance tends to be high.

在第2金屬氧化物層14中，GeO2的含量相對於上述5 種成分的合計，從充分地降低表面電阻並且充分地提高穿透率的觀點，例如為12mol%以下，較佳為10mol%以下。在第2金屬氧化物層14中，GeO2的含量相對於上述5種成分的合計，從充分地提高保存穩定性的觀點，例如為3mol%以上，較佳為3.5mol%以上。如果GeO2的含量過多，則有表面電阻變高的傾向、以及穿透率降低的傾向。另一方面，如果GeO2的含量過少，則在高溫高濕環境下保存的情況下有表面電阻變高的傾向。 In the second metal oxide layer 14 , the content of the GeO 2 is, for example, 12 mol% or less, preferably 10 mol%, from the viewpoint of sufficiently reducing the surface resistance and sufficiently increasing the transmittance. the following. In the second metal oxide layer 14 , the content of the GeO 2 is preferably 3 mol% or more, and preferably 3.5 mol% or more from the viewpoint of sufficiently improving the storage stability with respect to the total of the above five components. When the content of GeO 2 is too large, the surface resistance tends to be high and the transmittance tends to decrease. On the other hand, when the content of GeO 2 is too small, the surface resistance tends to be high when stored in a high-temperature, high-humidity environment.

第2金屬氧化物層14較佳為具有特定的結晶性。藉由具有特定的結晶性，第2金屬氧化物層除了蝕刻性以外還具有耐鹼性。第2金屬氧化物層14的結晶性藉由對形成的第2金屬氧化物層14的薄膜進行X射線繞射(XRD)分析而得到，本發明中的特定的結晶性是指起因於ZnO的XRD的繞射峰的峰強度除以第2金屬氧化物層14的薄膜的膜厚(單位nm)得到的值成為50以上的結晶性。該值低於50的低結晶性的第2金屬氧化物層14不顯示充分的耐鹼性。 The second metal oxide layer 14 preferably has specific crystallinity. The second metal oxide layer has alkali resistance in addition to etching properties by having specific crystallinity. The crystallinity of the second metal oxide layer 14 is obtained by X-ray diffraction (XRD) analysis of the thin film of the formed second metal oxide layer 14, and the specific crystallinity in the present invention means that it is caused by ZnO. The value obtained by dividing the peak intensity of the diffraction peak of XRD by the film thickness (unit: nm) of the film of the second metal oxide layer 14 is 50 or more. The second crystalline metal oxide layer 14 having a low crystallinity of less than 50 does not exhibit sufficient alkali resistance.

第2金屬氧化物層14兼具光學特性的調節、金屬層16的保護以及導電性的確保的功能。第2金屬氧化物層14在不較大地損害其功能的範圍內，除了上述5種成分以外可以含有微量成分或不可避免的成分。但是，從製成具有充分高的特性的透明導電體100的觀點，較佳為第2金屬氧化物層14中該5種成分的合計比例高。該比例例如為95mol%以上，較佳為97mol%以上。另外，第2金屬氧化物層14較佳為不含ITO。 The second metal oxide layer 14 has a function of adjusting optical characteristics, protecting the metal layer 16, and ensuring conductivity. The second metal oxide layer 14 may contain a trace component or an unavoidable component in addition to the above five components within a range that does not greatly impair the function. However, from the viewpoint of producing the transparent conductor 100 having sufficiently high characteristics, it is preferable that the total ratio of the five components in the second metal oxide layer 14 is high. The ratio is, for example, 95 mol% or more, preferably 97 mol% or more. Further, the second metal oxide layer 14 is preferably free of ITO.

第1金屬氧化物層12和第2金屬氧化物層14在厚度、結構以及組成方面可以相同，也可以不同。關於第2金屬氧化物層14的組成的記載也可以直接適用於第1金屬氧化物層12。第1金屬氧化 物層12藉由具有與第2金屬氧化物層14相同的組成，從而可以藉由蝕刻一起除去第1金屬氧化物層12、金屬層16以及第2金屬氧化物層14。另外，可以進一步提高透明性以及耐腐蝕性。 The first metal oxide layer 12 and the second metal oxide layer 14 may be the same in thickness, structure, and composition, or may be different. The description of the composition of the second metal oxide layer 14 can be directly applied to the first metal oxide layer 12. First metal oxidation The material layer 12 has the same composition as that of the second metal oxide layer 14, so that the first metal oxide layer 12, the metal layer 16, and the second metal oxide layer 14 can be removed by etching. In addition, transparency and corrosion resistance can be further improved.

第1金屬氧化物層12也可以具有與第2金屬氧化物層14不同的組成。在該情況下，蝕刻僅除去第2金屬氧化物層14以及金屬層16，可以直接使第1金屬氧化物層12殘留。另外，對於第1金屬氧化物層12較佳為也具有特定的結晶性。 The first metal oxide layer 12 may have a different composition from the second metal oxide layer 14. In this case, only the second metal oxide layer 14 and the metal layer 16 are removed by etching, and the first metal oxide layer 12 can be directly left. Further, it is preferable that the first metal oxide layer 12 also has specific crystallinity.

第1金屬氧化物層12以及第2金屬氧化物層14的厚度，從成為適於各種觸控面板的厚度的觀點，例如為10~70nm。 The thickness of the first metal oxide layer 12 and the second metal oxide layer 14 is, for example, 10 to 70 nm from the viewpoint of being suitable for the thickness of various touch panels.

第1金屬氧化物層12以及第2金屬氧化物層14可以藉由真空蒸鍍法、濺射法、離子鍍膜法或者CVD法等真空成膜法來進行製作。這些中，從能夠將成膜室小型化的觀點以及成膜速度快的觀點，較佳為濺射法。作為濺射法，可以列舉DC磁控濺射。作為靶，可以使用氧化物靶、金屬或半金屬靶。 The first metal oxide layer 12 and the second metal oxide layer 14 can be produced by a vacuum film formation method such as a vacuum deposition method, a sputtering method, an ion plating method, or a CVD method. Among these, from the viewpoint of being able to downsize the film forming chamber and the film forming speed, a sputtering method is preferred. As the sputtering method, DC magnetron sputtering can be cited. As the target, an oxide target, a metal or a semimetal target can be used.

也可以在第2金屬氧化物層14上設置配線電極等。藉由後述的金屬層16的電流從設置於第2金屬氧化物層14上的配線電極等經由第2金屬氧化物層14導通。由此，第2金屬氧化物層14較佳為具有高的導電性。從如此觀點，第2金屬氧化物層14單膜的表面電阻值例如較佳為1.0×10+7Ω/□(=1.0E+7Ω/sq.)以下，進一步較佳為5.0×10+6Ω/□以下。 A wiring electrode or the like may be provided on the second metal oxide layer 14. The current of the metal layer 16 to be described later is conducted from the wiring electrode or the like provided on the second metal oxide layer 14 via the second metal oxide layer 14 . Therefore, the second metal oxide layer 14 preferably has high conductivity. From such a viewpoint, the surface resistance value of the single film of the second metal oxide layer 14 is, for example, preferably 1.0 × 10 + 7 Ω / □ (= 1.0E + 7 Ω / sq.) or less, and further preferably 5.0 × 10 + 6 Below Ω/□.

金屬層16是包含銀合金作為主成分的層。藉由金屬層16具有高的導電性，從而可以充分地降低透明導電體100的表面電阻。作為構成銀合金的金屬元素，可以列舉Ag與選自Pd、Cu、Nd、In、Sn以及Sb中的至少1種。作為銀合金的例子，可以列舉Ag-Pd、 Ag-Cu、Ag-Pd-Cu、Ag-Nd-Cu、Ag-In-Sn以及Ag-Sn-Sb。 The metal layer 16 is a layer containing a silver alloy as a main component. Since the metal layer 16 has high conductivity, the surface resistance of the transparent conductor 100 can be sufficiently reduced. Examples of the metal element constituting the silver alloy include Ag and at least one selected from the group consisting of Pd, Cu, Nd, In, Sn, and Sb. As an example of the silver alloy, Ag-Pd, Ag-Cu, Ag-Pd-Cu, Ag-Nd-Cu, Ag-In-Sn, and Ag-Sn-Sb.

金屬層16除了銀合金以外也可以含有添加物。添加物較佳為藉由蝕刻液可以容易地被除去。金屬層16中的銀合金的含量例如可以為90質量%以上，也可以為95質量%以上。金屬層16的厚度例如為1~30nm。從充分地降低透明導電體100的表面電阻並且充分地提高總透光率的觀點，金屬層16的厚度較佳為4~11nm。如果金屬層16的厚度過大，則傾向於總透光率降低。另一方面，如果金屬層16的厚度過小，則有表面電阻變高的傾向。 The metal layer 16 may contain an additive in addition to the silver alloy. The additive is preferably easily removed by an etchant. The content of the silver alloy in the metal layer 16 may be, for example, 90% by mass or more, or may be 95% by mass or more. The thickness of the metal layer 16 is, for example, 1 to 30 nm. The thickness of the metal layer 16 is preferably from 4 to 11 nm from the viewpoint of sufficiently reducing the surface resistance of the transparent conductor 100 and sufficiently increasing the total light transmittance. If the thickness of the metal layer 16 is too large, the total light transmittance tends to decrease. On the other hand, if the thickness of the metal layer 16 is too small, the surface resistance tends to be high.

金屬層16具有調節透明導電體100的總透光率以及表面電阻的功能。金屬層16可以藉由真空蒸鍍法、濺射法、離子鍍膜法或者CVD法等真空成膜法來進行製作。這些中，從能夠將成膜室小型化的觀點以及成膜速度快的觀點，較佳為濺射法。作為濺射法，可以列舉DC磁控濺射。作為靶，可以使用金屬靶。 The metal layer 16 has a function of adjusting the total light transmittance and surface resistance of the transparent electric conductor 100. The metal layer 16 can be produced by a vacuum film formation method such as a vacuum deposition method, a sputtering method, an ion plating method, or a CVD method. Among these, from the viewpoint of being able to downsize the film forming chamber and the film forming speed, a sputtering method is preferred. As the sputtering method, DC magnetron sputtering can be cited. As the target, a metal target can be used.

透明導電體100中的第1金屬氧化物層12以及第2金屬氧化物層14的至少一部分以及金屬層16的至少一部分可以藉由蝕刻等除去。 At least a part of the first metal oxide layer 12 and the second metal oxide layer 14 and at least a part of the metal layer 16 in the transparent conductor 100 can be removed by etching or the like.

圖2是表示透明導電體的其它實施形態的示意截面圖。透明導電體101在以夾著透明樹脂基材10的方式具備一對硬塗層20的方面與透明導電體100不同。其它構成與透明導電體100相同。 Fig. 2 is a schematic cross-sectional view showing another embodiment of a transparent conductor. The transparent conductor 101 is different from the transparent conductor 100 in that a pair of hard coat layers 20 are provided so as to sandwich the transparent resin substrate 10 . The other configuration is the same as that of the transparent conductor 100.

透明導電體101作為一對硬塗層20在透明樹脂基材10的第1金屬氧化物層12側的主面上具備第1硬塗層22且在與透明樹脂基材10的第1金屬氧化物層12側相對側的主面上具備第2硬塗層24。即，透明導電體101具有依序積層有第2硬塗層24、透明樹脂基材10、第1硬塗層22、第1金屬氧化物層12、金屬層16以及第2金屬 氧化物層14而成的積層結構。第1硬塗層22和第2硬塗層24的厚度、結構以及組成可以相同，也可以不同。另外，也未必需要具備第1硬塗層22和第2硬塗層24兩者，也可以僅具備任一者。 The transparent conductor 101 is provided as a pair of hard coat layers 20 on the main surface of the transparent resin substrate 10 on the side of the first metal oxide layer 12, and is provided with the first hard coat layer 22 and oxidized on the first metal with the transparent resin substrate 10. The second hard coat layer 24 is provided on the main surface on the side opposite to the object layer 12 side. That is, the transparent conductor 101 has the second hard coat layer 24, the transparent resin substrate 10, the first hard coat layer 22, the first metal oxide layer 12, the metal layer 16, and the second metal laminated in this order. A laminated structure of the oxide layer 14. The thickness, structure, and composition of the first hard coat layer 22 and the second hard coat layer 24 may be the same or different. Further, it is not always necessary to provide both the first hard coat layer 22 and the second hard coat layer 24, and only one of them may be provided.

藉由設置硬塗層20，可以充分地抑制透明樹脂基材10上產生的傷。硬塗層20含有使樹脂組成物硬化而得到的樹脂硬化物。樹脂組成物較佳為包含選自熱硬化性樹脂組成物、紫外線硬化性樹脂組成物以及電子射線硬化性樹脂組成物中的至少一種。熱硬化性樹脂組成物可以包含選自環氧類樹脂、酚氧類樹脂、以及三聚氰胺類樹脂中的至少一種。 By providing the hard coat layer 20, the damage generated on the transparent resin substrate 10 can be sufficiently suppressed. The hard coat layer 20 contains a cured resin obtained by curing a resin composition. The resin composition preferably contains at least one selected from the group consisting of a thermosetting resin composition, an ultraviolet curable resin composition, and an electron beam curable resin composition. The thermosetting resin composition may contain at least one selected from the group consisting of an epoxy resin, a phenol oxygen resin, and a melamine resin.

樹脂組成物例如為含有具有(甲基)丙烯醯基、乙烯基等能量射線反應性基團的硬化性化合物的組成物。另外，(甲基)丙烯醯基的表述是指包括丙烯醯基和甲基丙烯醯基的至少一種。硬化性化合物較佳為包含在1個分子內含有2個以上、較佳為3個以上的能量射線反應性基團的多官能團單體或寡聚物。 The resin composition is, for example, a composition containing a curable compound having an energy ray-reactive group such as a (meth) acrylonitrile group or a vinyl group. Further, the expression of the (meth)acryl fluorenyl group means at least one of an acryloyl group and a methacryl group. The curable compound is preferably a polyfunctional monomer or oligomer containing two or more, preferably three or more, energy ray-reactive groups in one molecule.

硬化性化合物較佳為含有丙烯酸類單體。作為丙烯酸類單體，具體來說，可以列舉1,6-己二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、氧化乙烯改質雙酚A二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷氧化乙烯改質三(甲基)丙烯酸酯、三羥甲基丙烷氧化丙烯改質三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、雙三羥甲基丙烷四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、以及3-(甲基)丙烯醯氧基甘油單(甲基)丙烯酸酯等。但是，不一定限定於這些。例如，還可以列舉聚氨酯改質丙烯酸酯、以及環氧基改質丙烯酸酯等。 The curable compound preferably contains an acrylic monomer. Specific examples of the acrylic monomer include 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, and ethylene oxide-modified bisphenol A di(methyl). Acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide modified tri(meth)acrylate, trimethylolpropane propylene oxide modified tri(meth)acrylate , pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (methyl) Acrylate, 3-(meth)acryloxyglycerol mono(meth)acrylate, and the like. However, it is not necessarily limited to these. For example, a polyurethane modified acrylate, an epoxy modified acrylate, or the like can also be exemplified.

作為硬化性化合物，也可以使用具有乙烯基的化合物。作為具有乙烯基的化合物，例如可以列舉乙二醇二乙烯基醚、季戊四醇二乙烯基醚、1,6-己二醇二乙烯基醚、三羥甲基丙烷二乙烯基醚、氧化乙烯改質氫醌二乙烯基醚、氧化乙烯改質雙酚A二乙烯基醚、季戊四醇三乙烯基醚、二季戊四醇六乙烯基醚、以及雙三羥甲基丙烷聚乙烯基醚等。但是，不一定被限定於這些。 As the curable compound, a compound having a vinyl group can also be used. Examples of the compound having a vinyl group include ethylene glycol divinyl ether, pentaerythritol divinyl ether, 1,6-hexanediol divinyl ether, trimethylolpropane divinyl ether, and ethylene oxide modification. Hydroquinone divinyl ether, ethylene oxide modified bisphenol A divinyl ether, pentaerythritol trivinyl ether, dipentaerythritol hexavinyl ether, and ditrimethylolpropane polyvinyl ether. However, it is not necessarily limited to these.

在藉由紫外線使硬化性化合物硬化的情況下，樹脂組成物包含光聚合起始劑。作為光聚合起始劑，可以使用各種的物質。例如可以從苯乙酮類、苯偶姻類、二苯甲酮類、以及噻噸酮類等公知的化合物中適當選擇。更具體來說，可以列舉DAROCUR 1173、IRGACURE 651、IRGACURE 184、IRGACURE 907(以上都是商品名，Ciba Specialty Chemicals Inc.製造)、以及KAYACURE DETX-S(商品名，日本化藥股份有限公司製造)。 In the case where the curable compound is cured by ultraviolet rays, the resin composition contains a photopolymerization initiator. As the photopolymerization initiator, various substances can be used. For example, it can be suitably selected from well-known compounds, such as an acetophenone, a benzoin, a benzophenone, and a thioxanone. More specifically, DAROCUR 1173, IRGACURE 651, IRGACURE 184, IRGACURE 907 (all of which are trade names, manufactured by Ciba Specialty Chemicals Inc.), and KAYACURE DETX-S (trade name, manufactured by Nippon Kayaku Co., Ltd.) can be cited. .

光聚合起始劑相對於硬化性化合物的質量可以為0.01~20質量%或者0.5~5質量%左右。樹脂組成物也可以是在丙烯酸類單體中加入有光聚合起始劑的公知的樹脂組成物。作為在丙烯酸類單體中加入有光聚合起始劑的樹脂組成物，例如可以列舉作為紫外線硬化型樹脂的SD-318(商品名，Dainippon Ink and Chemicals Co.，製造)以及XNR5535(商品名，長瀨產業股份有限公司製造)等。 The mass of the photopolymerization initiator may be from 0.01 to 20% by mass or from 0.5 to 5% by mass based on the mass of the curable compound. The resin composition may also be a known resin composition in which a photopolymerization initiator is added to an acrylic monomer. Examples of the resin composition in which the photopolymerization initiator is added to the acrylic monomer include SD-318 (trade name, manufactured by Dainippon Ink and Chemicals Co.) and XNR5535 (trade name, which are ultraviolet curable resins). Changchun Industry Co., Ltd. manufactures) and so on.

為了提高塗膜的強度和/或調節折射率等，樹脂組成物也可以含有有機微粒子和/或無機微粒子。作為有機微粒子，例如可以列舉有機矽微粒子、交聯丙烯酸微粒子、以及交聯聚苯乙烯微粒子等。作為無機微粒子，例如可以列舉氧化矽微粒子、氧化鋁微粒子、氧化鋯微粒子、氧化鈦微粒子、以及氧化鐵微粒子等。其中， 較佳為氧化矽微粒子。 The resin composition may contain organic fine particles and/or inorganic fine particles in order to increase the strength of the coating film and/or adjust the refractive index and the like. Examples of the organic fine particles include organic fine particles, crosslinked acrylic fine particles, and crosslinked polystyrene fine particles. Examples of the inorganic fine particles include cerium oxide fine particles, alumina fine particles, zirconia fine particles, titanium oxide fine particles, and iron oxide fine particles. among them, Preferred are cerium oxide microparticles.

微粒子較佳為其表面用矽烷偶聯劑進行了處理，並且(甲基)丙烯醯基和/或乙烯基等能量射線反應性基團在表面以膜狀存在。如果使用具有如此的反應性的微粒子，則在能量射線照射時微粒子彼此反應，或者微粒子與多官能團單體或寡聚物反應，從而可以增強膜的強度。較佳為使用以含有(甲基)丙烯醯基的矽烷偶聯劑處理後的氧化矽微粒子。 The microparticles are preferably treated with a decane coupling agent for their surfaces, and energy ray-reactive groups such as (meth)acryl fluorenyl groups and/or vinyl groups are present in a film form on the surface. If microparticles having such reactivity are used, the microparticles react with each other upon irradiation of the energy ray, or the microparticles react with the polyfunctional monomer or oligomer, so that the strength of the film can be enhanced. It is preferred to use cerium oxide microparticles treated with a decane coupling agent containing a (meth) acrylonitrile group.

微粒子的平均粒徑比硬塗層20的厚度小，從確保充分的透明性的觀點，可以為100nm以下，也可以為20nm以下。另一方面，從膠體溶液的製造上的觀點，可以為5nm以上，也可以為10nm以上。在使用有機微粒子和/或無機微粒子的情況下，有機微粒子和無機微粒子的合計量相對於100質量份的硬化性化合物例如為5~500質量份，也可以為20~200質量份。 The average particle diameter of the fine particles is smaller than the thickness of the hard coat layer 20, and may be 100 nm or less or 20 nm or less from the viewpoint of ensuring sufficient transparency. On the other hand, from the viewpoint of production of the colloidal solution, it may be 5 nm or more, or may be 10 nm or more. In the case of using the organic fine particles and/or the inorganic fine particles, the total amount of the organic fine particles and the inorganic fine particles may be, for example, 5 to 500 parts by mass, or may be 20 to 200 parts by mass, per 100 parts by mass of the curable compound.

如果使用以能量射線硬化的樹脂組成物，則藉由照射紫外線等能量射線，可以使樹脂組成物硬化。因此，從製造步驟上的觀點，也較佳為使用如此的樹脂組成物。 When a resin composition hardened by energy rays is used, the resin composition can be cured by irradiation with an energy ray such as ultraviolet rays. Therefore, it is also preferred to use such a resin composition from the viewpoint of the production steps.

第1硬塗層22可以將樹脂組成物的溶液或分散液塗佈於透明樹脂基材10的一個面上，乾燥並使樹脂組成物硬化來進行製作。此時的塗佈可以藉由公知的方法來進行。作為塗佈方法，例如可以列舉擠出噴嘴法、刮板塗佈法(blade method)、刮刀塗佈法(knife method)、棒塗法、接觸塗佈法、接觸式反轉塗佈法、凹版輥式塗佈法、浸漬法、逆轉輥塗佈法、直接輥塗法、簾式塗佈法以及擠壓法等。第2硬塗層24也與第1硬塗層22同樣地可以在透明樹脂基材10的另一個面上製作。 The first hard coat layer 22 can be produced by applying a solution or dispersion of a resin composition onto one surface of the transparent resin substrate 10, drying it, and curing the resin composition. The coating at this time can be carried out by a known method. Examples of the coating method include an extrusion nozzle method, a blade coating method, a knife method, a bar coating method, a contact coating method, a contact reverse coating method, and a gravure method. Roll coating method, dipping method, reverse roll coating method, direct roll coating method, curtain coating method, extrusion method, and the like. Similarly to the first hard coat layer 22, the second hard coat layer 24 can be formed on the other surface of the transparent resin substrate 10.

第1硬塗層22和第2硬塗層24的厚度例如為0.5~10μm。如果厚度超過10μm，則有容易發生厚度不均勻或皺紋等的傾向。另一方面，如果厚度低於0.5μm，則在透明樹脂基材10中含有相當量的增塑劑或寡聚物等低分子量成分的情況下，存在難以充分地抑制這些成分的滲出的情況。另外，從抑制彎曲的觀點，第1硬塗層22和第2硬塗層24的厚度較佳為相同程度。 The thickness of the first hard coat layer 22 and the second hard coat layer 24 is, for example, 0.5 to 10 μm. When the thickness exceeds 10 μm, thickness unevenness, wrinkles, and the like tend to occur. On the other hand, when the thickness is less than 0.5 μm, when the transparent resin substrate 10 contains a relatively small amount of a low molecular weight component such as a plasticizer or an oligomer, it may be difficult to sufficiently suppress the bleeding of these components. Further, from the viewpoint of suppressing the bending, the thicknesses of the first hard coat layer 22 and the second hard coat layer 24 are preferably the same.

第1硬塗層22和第2硬塗層24的折射率例如為1.40~1.60。透明樹脂基材10與第1硬塗層22的折射率的差的絕對值較佳為0.1以下。透明樹脂基材10與第2硬塗層24的折射率的差的絕對值也較佳為0.1以下。藉由降低第1硬塗層22和第2硬塗層24與透明樹脂基材10的折射率的差的絕對值，可以抑制由於第1硬塗層22和第2硬塗層24的厚度的不均勻而發生的干涉不均的強度。 The refractive indices of the first hard coat layer 22 and the second hard coat layer 24 are, for example, 1.40 to 1.60. The absolute value of the difference in refractive index between the transparent resin substrate 10 and the first hard coat layer 22 is preferably 0.1 or less. The absolute value of the difference in refractive index between the transparent resin substrate 10 and the second hard coat layer 24 is also preferably 0.1 or less. By reducing the absolute value of the difference in refractive index between the first hard coat layer 22 and the second hard coat layer 24 and the transparent resin substrate 10, the thickness of the first hard coat layer 22 and the second hard coat layer 24 can be suppressed. The intensity of uneven interference that occurs unevenly.

構成透明導電體100、101的各層的厚度可以按照以下的步驟進行測定。藉由聚焦離子束裝置(FIB，Focused Ion Beam)切斷透明導電體100、101得到截面。使用穿透式電子顯微鏡(TEM)觀察該截面，測定各層的厚度。測定較佳為在任意選擇的10個以上的位置進行測定，並求得其平均值。作為得到截面的方法，也可以使用切片機作為聚焦離子束裝置以外的裝置。作為測定厚度的方法，也可以使用掃描式電子顯微鏡(SEM)。另外，也可以使用螢光X射線裝置測定膜厚。 The thickness of each layer constituting the transparent conductors 100 and 101 can be measured by the following procedure. The transparent conductors 100, 101 were cut by a focused ion beam apparatus (FIB, Focused Ion Beam) to obtain a cross section. The cross section was observed using a transmission electron microscope (TEM), and the thickness of each layer was measured. The measurement is preferably carried out at 10 or more positions which are arbitrarily selected, and the average value thereof is determined. As a method of obtaining a cross section, a microtome can also be used as a device other than the focused ion beam device. As a method of measuring the thickness, a scanning electron microscope (SEM) can also be used. Alternatively, the film thickness can be measured using a fluorescent X-ray apparatus.

透明導電體100、101的厚度可以為200μm以下，也可以為150μm以下。只要為如此的厚度，就可以充分地滿足薄化的要求水準。透明導電體100、101的總透光率可以為例如85%以上的高的值。另外，透明導電體100、101的表面電阻值(4端子法)即使不進 行第1金屬氧化物層12和第2金屬氧化物層14的熱退火，也可以為例如30Ω/□以下，也可以為25Ω/□以下。 The thickness of the transparent conductors 100 and 101 may be 200 μm or less, or may be 150 μm or less. As long as it is such a thickness, the required level of thinning can be sufficiently satisfied. The total light transmittance of the transparent conductors 100, 101 may be a high value of, for example, 85% or more. In addition, the surface resistance value (4-terminal method) of the transparent conductors 100 and 101 does not advance even if The thermal annealing of the first metal oxide layer 12 and the second metal oxide layer 14 may be, for example, 30 Ω/□ or less, or may be 25 Ω/□ or less.

具備上述構成的透明導電體100、101具有積層有第1金屬氧化物層12、金屬層16以及第2金屬氧化物層14的積層結構。該積層結構使用通常的蝕刻液可以容易地一起除去。另外，具有高的穿透率，並且即使不進行熱退火也具有高的導電性。由此，可以較佳為用作觸控面板的感測器薄膜用。 The transparent conductors 100 and 101 having the above-described configuration have a laminated structure in which the first metal oxide layer 12, the metal layer 16, and the second metal oxide layer 14 are laminated. This laminated structure can be easily removed together using a usual etching liquid. In addition, it has a high transmittance and has high conductivity even without thermal annealing. Therefore, it can be preferably used as a sensor film for a touch panel.

圖3是放大表示具備一對感測器薄膜的觸控面板200的截面的一部分的示意截面圖。圖4(A)和圖4(B)是使用了上述透明導電體100的感測器薄膜100a和100b的平面圖。觸控面板200具備藉由光學膠18而相對配置的一對感測器薄膜100a、100b。觸控面板200以能夠將接觸體的觸碰位置作為平行於成為畫面的面板70的二維座標(X-Y座標)平面中的座標位置(橫向位置和縱向位置)算出的方式構成。 FIG. 3 is a schematic cross-sectional view showing a part of a cross section of the touch panel 200 including a pair of sensor films. 4(A) and 4(B) are plan views of the sensor films 100a and 100b using the above-described transparent conductor 100. The touch panel 200 includes a pair of sensor films 100a and 100b that are disposed to face each other by the optical glue 18. The touch panel 200 is configured such that the touch position of the contact body can be calculated as a coordinate position (lateral position and vertical position) in a plane parallel to the two-dimensional coordinate (X-Y coordinate) of the panel 70 that serves as the screen.

具體來說，觸控面板200具備藉由光學膠18貼附的縱向位置檢測用的感測器薄膜100a(以下稱為「Y用感測器薄膜」)和橫向位置檢測用的感測器薄膜100b(以下稱為「X用感測器薄膜」)。在X用感測器薄膜100b的下面側，在X用感測器薄膜100b與顯示裝置的面板70之間設置有墊片92。 Specifically, the touch panel 200 includes a sensor film 100a for longitudinal position detection (hereinafter referred to as "Y sensor film") attached to the optical adhesive 18, and a sensor film for lateral position detection. 100b (hereinafter referred to as "X sensor film"). On the lower surface side of the X sensor film 100b, a spacer 92 is provided between the X sensor film 100b and the panel 70 of the display device.

Y用感測器薄膜100a的上面側(與面板70側相對側)藉由光學膠17設置有玻璃蓋板19。即觸控面板200在面板70上具有從面板70側開始依序配置有X用感測器薄膜100b、Y用感測器薄膜100a以及玻璃蓋板19的積層結構。 The upper side of the Y sensor film 100a (the side opposite to the side of the panel 70) is provided with a glass cover 19 by the optical glue 17. In other words, the touch panel 200 has a laminated structure in which the X sensor film 100b, the Y sensor film 100a, and the cover glass 19 are arranged in this order from the panel 70 side.

檢測縱向位置的Y用感測器薄膜100a和檢測橫向位置 的X用感測器薄膜100b由上述透明導電體100構成。Y用感測器薄膜100a和X用感測器薄膜100b以與玻璃蓋板19相對的方式具有作為導電部的感測器電極15a和感測器電極15b。 Detecting the Y position sensor film 100a in the longitudinal position and detecting the lateral position The X sensor film 100b is composed of the above transparent conductor 100. The Y sensor film 100a and the X sensor film 100b have a sensor electrode 15a and a sensor electrode 15b as conductive portions in such a manner as to face the glass cover 19.

該感測器電極15a由第1金屬氧化物層12、第2金屬氧化物層14以及金屬層16構成。如圖4(A)所示，感測器電極15a以能夠檢測縱向(y方向)的觸碰位置的方式在縱向(y方向)上延伸有多個。多個感測器電極15a沿著縱向(y方向)互相平行排列地配置。感測器電極15a的一端藉由用銀膏形成的導體線路50與驅動用IC側的電極80連接。 The sensor electrode 15a is composed of a first metal oxide layer 12, a second metal oxide layer 14, and a metal layer 16. As shown in FIG. 4(A), the sensor electrode 15a extends in the longitudinal direction (y direction) in such a manner as to be able to detect the touch position in the longitudinal direction (y direction). The plurality of sensor electrodes 15a are arranged in parallel with each other in the longitudinal direction (y direction). One end of the sensor electrode 15a is connected to the electrode 80 on the side of the driving IC by a conductor line 50 formed of a silver paste.

檢測橫向位置的X用感測器薄膜100b在與Y用感測器薄膜100a的相對面具有感測器電極15b。該感測器電極15b由第1金屬氧化物層12、第2金屬氧化物層14以及金屬層16構成。如圖4(B)所示，感測器電極15b以能夠檢測橫向(x方向)的觸碰位置的方式在橫向(x方向)上延伸有多個。多個感測器電極15b沿著橫向(x方向)互相平行排列地配置。感測器電極15b的一端藉由用銀膏形成的導體線路50與驅動用IC側的電極80連接。 The X-sensor film 100b for detecting the lateral position has a sensor electrode 15b on the opposite side to the Y-sensor film 100a. The sensor electrode 15b is composed of a first metal oxide layer 12, a second metal oxide layer 14, and a metal layer 16. As shown in FIG. 4(B), the sensor electrode 15b extends in the lateral direction (x direction) so as to be able to detect the lateral (x-direction) touch position. The plurality of sensor electrodes 15b are arranged in parallel with each other in the lateral direction (x direction). One end of the sensor electrode 15b is connected to the electrode 80 on the side of the driving IC by a conductor line 50 formed of a silver paste.

Y用感測器薄膜100a和X用感測器薄膜100b在從Y用感測器薄膜100a和X用感測器薄膜100b的積層方向看時以各個感測器電極15a、15b相互正交的方式藉由光學膠18進行重疊。Y用感測器薄膜100a在與X用感測器薄膜100b側相對側藉由光學膠17設置有玻璃蓋板19。光學膠17、18、玻璃蓋板19以及面板70可以使用通常的物質。 The sensor tube film 100a for Y and the sensor film 100b for X are orthogonal to each other when viewed from the stacking direction of the sensor film 100a for Y and the sensor film 100b for X, with the respective sensor electrodes 15a, 15b. The method is overlapped by the optical glue 18. The Y sensor film 100a is provided with a glass cover 19 on the side opposite to the X sensor film 100b side by the optical glue 17. The optical glues 17, 18, the glass cover 19, and the panel 70 can use a usual substance.

圖4(A)、(B)中的導體線路50以及電極80可以由金屬(例如Ag)等的導電性材料構成。導體線路50以及電極80可以藉由例 如網版印刷來進行圖案形成。 The conductor line 50 and the electrode 80 in FIGS. 4(A) and (B) may be made of a conductive material such as metal (for example, Ag). The conductor line 50 and the electrode 80 can be exemplified by Such as screen printing for patterning.

各感測器薄膜100a、100b中的感測器電極15a、15b的形狀和數量不限定於圖3、圖4(A)以及圖4(B)所示的形態。例如，也可以增加感測器電極15a、15b的數量來提高觸碰位置的檢測精度。 The shape and number of the sensor electrodes 15a and 15b in each of the sensor films 100a and 100b are not limited to those shown in Figs. 3, 4(A) and 4(B). For example, the number of the sensor electrodes 15a, 15b can also be increased to improve the detection accuracy of the touch position.

X用感測器薄膜100b在與Y用感測器薄膜100a側相對側藉由墊片92設置有面板70。墊片92可以設置於對應於感測器電極15a、15b的形狀的位置和包圍感測器電極15a、15b的整體的位置。墊片92可以由具有透光性的材料，例如PET(聚對苯二甲酸乙二酯)樹脂形成。墊片92的一端藉由光學膠或者丙烯酸類或環氧類等具有透光性的接黏劑90而黏接於X用感測器薄膜100b的下面。墊片92的另一端藉由接黏劑90黏接於顯示裝置的面板70。如此，藉由經由墊片92將X用感測器薄膜100b和面板70相對配置，從而可以在X用感測器薄膜100b和顯示裝置的面板70之間設置縫隙S。 The X sensor film 100b is provided with a panel 70 on the side opposite to the Y sensor film 100a side by a spacer 92. The spacer 92 may be disposed at a position corresponding to the shape of the sensor electrodes 15a, 15b and a position surrounding the entirety of the sensor electrodes 15a, 15b. The spacer 92 may be formed of a light transmissive material such as PET (polyethylene terephthalate) resin. One end of the spacer 92 is bonded to the lower surface of the X sensor film 100b by an optical adhesive or a light-transmitting adhesive 90 such as acrylic or epoxy. The other end of the spacer 92 is adhered to the panel 70 of the display device by an adhesive 90. As described above, by arranging the X sensor film 100b and the face plate 70 via the spacer 92, the slit S can be provided between the X sensor film 100b and the panel 70 of the display device.

在電極80上電連接有控制部(IC)。分別測定由於指尖與觸控面板200的Y用感測器薄膜100a之間的靜電容量的變化而產生的各感測器電極15a、15b的容量變化。控制部可以基於測定結果將接觸體的觸碰位置作為座標位置(X軸方向的位置和Y軸方向的位置的交點)而算出。另外，感測器電極的驅動方法以及座標位置的算出方法除了上述以外還可以採用公知的各種方法。 A control unit (IC) is electrically connected to the electrode 80. The change in capacity of each of the sensor electrodes 15a and 15b due to a change in electrostatic capacitance between the fingertip and the Y sensor film 100a of the touch panel 200 is measured. The control unit can calculate the touch position of the contact body as a coordinate position (the intersection of the position in the X-axis direction and the position in the Y-axis direction) based on the measurement result. Further, in addition to the above, various methods known in the art for driving the sensor electrodes and calculating the coordinate position may be employed.

觸控面板200可以按照以下的順序進行製造。在準備了透明導電體100之後，進行第1金屬氧化物層12、金屬層16以及第2金屬氧化物層14的蝕刻，進行圖案化。具體來說，使用光刻的技術在第2金屬氧化物層14的表面藉由旋轉塗佈來塗佈光阻材料。其後，為了提高密著性，也可以進行預烘烤。接著，配置遮罩圖案並 進行曝光，用顯影液顯影，由此形成光阻圖案。光阻圖案的形成不限定於光刻法，也可以藉由網版印刷等來形成。 The touch panel 200 can be manufactured in the following order. After the transparent conductor 100 is prepared, the first metal oxide layer 12, the metal layer 16, and the second metal oxide layer 14 are etched and patterned. Specifically, the photoresist is applied on the surface of the second metal oxide layer 14 by spin coating using a photolithography technique. Thereafter, in order to improve the adhesion, prebaking may be performed. Next, configure the mask pattern and Exposure is carried out and developed with a developing solution, thereby forming a photoresist pattern. The formation of the photoresist pattern is not limited to the photolithography method, and may be formed by screen printing or the like.

接著，在酸性蝕刻液中浸漬形成有光阻圖案的透明導電體100，溶解除去沒有形成光阻圖案的部分中的第1金屬氧化物層12、第2金屬氧化物層14以及金屬層16。其後，除去光阻劑，從而可以得到形成有感測器電極15a的Y用感測器薄膜100a和形成有感測器電極15b的X用感測器薄膜100b。 Next, the transparent conductor 100 in which the photoresist pattern is formed is immersed in the acidic etching solution, and the first metal oxide layer 12, the second metal oxide layer 14, and the metal layer 16 in the portion where the photoresist pattern is not formed are dissolved and removed. Thereafter, the photoresist is removed, whereby the Y sensor film 100a on which the sensor electrode 15a is formed and the X sensor film 100b on which the sensor electrode 15b is formed can be obtained.

使第1金屬氧化物層12和第2金屬氧化物層14為不同的組成，如果使第1金屬氧化物層12為沒有被蝕刻除去的組成，則對金屬層16和第2金屬氧化物層14一起蝕刻，在蝕刻後也可以直接殘留第1金屬氧化物層12。作為蝕刻液，可以使用無機酸類的蝕刻液。例如，較佳為磷酸類的蝕刻液。 When the first metal oxide layer 12 and the second metal oxide layer 14 have different compositions, if the first metal oxide layer 12 is made of a composition that is not removed by etching, the metal layer 16 and the second metal oxide layer are formed. 14 is etched together, and the first metal oxide layer 12 may be directly left after etching. As the etching liquid, an etching solution of an inorganic acid can be used. For example, a phosphoric acid-based etching solution is preferred.

接著，塗佈例如銀合金糊膏等的金屬糊膏，形成導體線路50和電極80。由此，將控制部(未圖示)和感測器電極15a、15b電連接。接著，使用光學膠18將Y用感測器薄膜100a和X用感測器薄膜100b以各個感測器電極15a、15b向著同一方向的方式貼附。在該情況下，在從Y用感測器薄膜100a和X用感測器薄膜100b的積層方向來看時，以感測器電極15a、15b相互正交的方式貼附。然後，使用光學膠17貼附玻璃蓋板19和Y用感測器薄膜100a。由此，可以製造觸控面板200。 Next, a metal paste such as a silver alloy paste is applied to form a conductor line 50 and an electrode 80. Thereby, the control unit (not shown) and the sensor electrodes 15a and 15b are electrically connected. Next, the Y sensor film 100a and the X sensor film 100b are attached to the same direction with the respective sensor electrodes 15a and 15b using the optical glue 18. In this case, when viewed from the stacking direction of the Y sensor film 100a and the X sensor film 100b, the sensor electrodes 15a and 15b are attached to each other so as to be orthogonal to each other. Then, the glass cover 19 and the Y sensor film 100a are attached using the optical glue 17. Thereby, the touch panel 200 can be manufactured.

觸控面板200中，作為Y用感測器薄膜100a和X用感測器薄膜100b使用透明導電體100。透明導電體100可以藉由蝕刻一起除去第1金屬氧化物層12、第2金屬氧化物層14以及金屬層16。由此，可以簡略觸控面板200的製造過程，從而容易地製造觸控面板200。 In the touch panel 200, the transparent conductor 100 is used as the Y sensor film 100a and the X sensor film 100b. The transparent conductor 100 can remove the first metal oxide layer 12, the second metal oxide layer 14, and the metal layer 16 by etching. Thereby, the manufacturing process of the touch panel 200 can be simplified, and the touch panel 200 can be easily manufactured.

另外，對於Y用感測器薄膜100a和X用感測器薄膜100b兩者不需要都使用透明導電體100，任意一者也可以使用其它的透明導電體。即使是如此的觸控面板，也可以使顯示充分清晰。另外，作為感測器薄膜也可以不是透明導電體100而使用透明導電體101。 Further, it is not necessary to use the transparent conductor 100 for both the Y sensor film 100a and the X sensor film 100b, and any other transparent conductor may be used. Even with such a touch panel, the display can be made sufficiently clear. Further, as the sensor film, the transparent conductor 101 may be used instead of the transparent conductor 100.

如此，可以較佳為將透明導電體100、101用於觸控面板用。但是，其用途不限定於觸控面板，例如，可以將第1金屬氧化物層12、第2金屬氧化物層14以及金屬層16藉由蝕刻加工成特定形狀，形成具有第1金屬氧化物層12、第2金屬氧化物層14以及金屬層16的部分(導電部)和不具有第1金屬氧化物層12、第2金屬氧化物層14以及金屬層16的部分(非導電部)，在液晶顯示器(LCD)、電漿顯示面板(PDP)、電致發光面板(有機EL、無機EL)、電致變色元件、以及電子紙等各種顯示裝置中用作透明電極用、防靜電用、電磁波遮罩用。另外，也可以作為天線使用。 Thus, the transparent conductors 100 and 101 can be preferably used for a touch panel. However, the use thereof is not limited to the touch panel. For example, the first metal oxide layer 12, the second metal oxide layer 14, and the metal layer 16 may be processed into a specific shape by etching to form the first metal oxide layer. 12. The second metal oxide layer 14 and the portion (the conductive portion) of the metal layer 16 and the portion (non-conductive portion) not including the first metal oxide layer 12, the second metal oxide layer 14, and the metal layer 16 are Used for transparent electrodes, antistatic, electromagnetic waves in various display devices such as liquid crystal displays (LCDs), plasma display panels (PDPs), electroluminescent panels (organic EL, inorganic EL), electrochromic devices, and electronic paper. For masks. In addition, it can also be used as an antenna.

以上說明了本發明的較佳為的實施形態，但是本發明不限定於上述的實施形態。例如，上述的透明導電體101具有一對硬塗層20，但是也可以僅具備第1硬塗層22和第2硬塗層24中的任意一者。另外，也可以在透明樹脂基材10的一個面上設置有硬塗層，在另一個面上藉由塗佈設置多個光學調節層。在該情況下，第1金屬氧化物層12、金屬層16以及第2金屬氧化物層14也可以設置於該光學調節層上。進一步，透明導電體100、101可以在不大大損害其功能的範圍內除了上述層以外在任意的位置設置任意的層。 The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments. For example, the transparent conductor 101 described above has a pair of hard coat layers 20, but may be provided with only one of the first hard coat layer 22 and the second hard coat layer 24. Further, a hard coat layer may be provided on one surface of the transparent resin substrate 10, and a plurality of optical adjustment layers may be provided on the other surface by coating. In this case, the first metal oxide layer 12, the metal layer 16, and the second metal oxide layer 14 may be provided on the optical adjustment layer. Further, the transparent conductors 100, 101 may be provided with any layer at any position other than the above layers within a range that does not greatly impair the function.

[實施例] [Examples]

以下列舉實施例以及比較例，更具體地說明本發明，但是本發明不限定於這些實施例。 The present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited to these examples.

[實施例1~18] [Examples 1 to 18] (透明導電體101的製作) (Production of Transparent Conductor 101)

製作如圖2所示的透明導電體。透明導電體具有依序積層有被一對硬塗層夾著的透明樹脂基材、第1金屬氧化物層、金屬層以及第2金屬氧化物層的積層結構。按照以下的要領製作各實施例的透明導電體。 A transparent conductor as shown in Fig. 2 was produced. The transparent conductor has a laminated structure in which a transparent resin substrate sandwiched between a pair of hard coat layers, a first metal oxide layer, a metal layer, and a second metal oxide layer are laminated in this order. The transparent conductors of the respective examples were produced in the following manner.

準備厚度為100μm的聚對苯二甲酸乙二酯薄膜(Toray Industries,Inc.製作，型號：U48)。將該PET薄膜用作透明樹脂基材。按照以下的順序調製第1硬塗層、以及第2硬塗層製作用的塗料。 A polyethylene terephthalate film (manufactured by Toray Industries, Inc., model: U48) having a thickness of 100 μm was prepared. This PET film was used as a transparent resin substrate. The first hard coat layer and the second hard coat layer preparation paint were prepared in the following order.

首先，準備以下的原材料。 First, prepare the following raw materials.

．反應性基團改質矽酸膠(分散介質：丙二醇單甲基醚乙酸酯，不 揮發成分：40重量%)：100重量份 . Reactive group modified phthalic acid gel (dispersion medium: propylene glycol monomethyl ether acetate, no Volatile component: 40% by weight): 100 parts by weight

．二季戊四醇六丙烯酸酯：48重量份 . Dipentaerythritol hexaacrylate: 48 parts by weight

．1,6-己二醇二丙烯酸酯：12重量份 . 1,6-hexanediol diacrylate: 12 parts by weight

．光聚合起始劑(1-羥基環己基苯基甲酮)：2.5重量份 . Photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone): 2.5 parts by weight

用溶劑(丙二醇單甲基醚(PGMA))將上述原材料稀釋並混合，使各成分分散於溶劑中。由此，調製不揮發成分(NV)為25.5重量%的塗料。將由此得到的塗料用作第1硬塗層和第2硬塗層製作用的塗料。 The above raw materials were diluted and mixed with a solvent (propylene glycol monomethyl ether (PGMA)) to disperse the components in a solvent. Thus, a coating material having a nonvolatile content (NV) of 25.5% by weight was prepared. The coating thus obtained was used as a coating material for the first hard coat layer and the second hard coat layer.

在透明樹脂基材的一個面上塗佈第1硬塗層製作用的塗料，製作塗佈膜。在設定為80℃的熱風乾燥爐中除去塗佈膜中的溶劑之後，使用UV處理裝置照射累計光量為400mJ/cm2的紫外線， 使塗佈膜硬化。由此，在透明樹脂基材的一個面上製作厚度為5μm的第1硬塗層。同樣地在透明樹脂基材的另一個面上製作厚度為5μm的第2硬塗層。 A coating material for producing a first hard coat layer was applied to one surface of a transparent resin substrate to prepare a coating film. After removing the solvent in the coating film in a hot air drying oven set at 80 ° C, ultraviolet rays having an integrated light amount of 400 mJ/cm 2 were irradiated with a UV treatment apparatus to cure the coating film. Thus, a first hard coat layer having a thickness of 5 μm was formed on one surface of the transparent resin substrate. Similarly, a second hard coat layer having a thickness of 5 μm was formed on the other surface of the transparent resin substrate.

在第1硬塗層上藉由DC磁控濺射依序形成第1金屬氧化物層、金屬層以及第2金屬氧化物層。第1金屬氧化物層以及第2金屬氧化物層使用具有表1所示的組成的ZnO-In2O3-TiO2-Ga2O3-GeO2靶形成。各個實施例中的第1金屬氧化物層以及第2金屬氧化物層使用具有相同組成的靶形成。各實施例中的第1金屬氧化物層以及第2金屬氧化物層的組成如表1所示。各實施例中的第1金屬氧化物層以及第2金屬氧化物層的厚度為50nm。 The first metal oxide layer, the metal layer, and the second metal oxide layer are sequentially formed on the first hard coat layer by DC magnetron sputtering. The first metal oxide layer and the second metal oxide layer were formed using a ZnO-In 2 O 3 —TiO 2 —Ga 2 O 3 —GeO 2 target having the composition shown in Table 1. The first metal oxide layer and the second metal oxide layer in each of the examples are formed using targets having the same composition. The composition of the first metal oxide layer and the second metal oxide layer in each of the examples is shown in Table 1. The thickness of the first metal oxide layer and the second metal oxide layer in each of the examples was 50 nm.

在表1所示的全部的實施例中，金屬層使用AgPdCu(Ag：Pd：Cu=99.0：0.5：0.5(質量%))靶形成。金屬層16的厚度為5nm。 In all of the examples shown in Table 1, the metal layer was formed using a target of AgPdCu (Ag: Pd: Cu = 99.0: 0.5: 0.5 (% by mass)). The metal layer 16 has a thickness of 5 nm.

(透明導電體101的評價) (Evaluation of Transparent Conductor 101)

按照以下的順序評價蝕刻特性。首先，準備含有磷酸、乙酸、硝酸的PAN系蝕刻液。在該蝕刻液中在室溫下浸漬各實施例的透明導電體1分鐘，進行蝕刻。其後，進行總透光率測定，判定第1金屬氧化物層、金屬層以及第2金屬氧化物層是否溶解。具體來說，將蝕刻後的樣品的總透光率僅與透明樹脂基材的總透光率一致的情況判定為「A」，將不一致的情況判定為「B」。總透光率(穿透率)使用霧度計(商品名：NDH-7000，日本電色工業公司製造)來測定。評價結果如表1所示。 The etching characteristics were evaluated in the following order. First, a PAN-based etching solution containing phosphoric acid, acetic acid, and nitric acid is prepared. The transparent conductor of each example was immersed in the etching solution at room temperature for 1 minute, and etched. Thereafter, the total light transmittance was measured to determine whether or not the first metal oxide layer, the metal layer, and the second metal oxide layer were dissolved. Specifically, the total light transmittance of the sample after etching was determined to be "A" only when the total light transmittance of the transparent resin substrate was matched, and the case where the inconsistency was determined as "B". The total light transmittance (transmittance) was measured using a haze meter (trade name: NDH-7000, manufactured by Nippon Denshoku Industries Co., Ltd.). The evaluation results are shown in Table 1.

使用4端子電阻率計(商品名：Loresta GP，三菱化學 股份有限公司製造)測定各實施例的表面電阻。將結果示於表1中。在表1中，「表面電阻(1)」是將透明導電體在85℃、85%RH(相對濕度85%)的環境下保存50小時前的表面電阻值，「表面電阻(2)」是在上述環境下保存後的表面電阻值。 Use 4-terminal resistivity meter (trade name: Loresta GP, Mitsubishi Chemical The surface resistance of each of the examples was measured. The results are shown in Table 1. In Table 1, "surface resistance (1)" is a surface resistance value obtained by preserving a transparent conductor in an environment of 85 ° C and 85% RH (relative humidity: 85%) for 50 hours, and "surface resistance (2)" is The surface resistance value after storage in the above environment.

將各實施例的透明導電體在85℃、85%RH的環境下保存之後，藉由目視進行保存穩定性的評價。將在透明導電體中看到白濁的情況判定為「B」，將沒有看到的情況判定為「A」。結果如表1所示。 After the transparent conductor of each example was stored in an environment of 85 ° C and 85% RH, the storage stability was evaluated by visual observation. The case where white turbidity was observed in the transparent conductor was judged as "B", and the case where it was not seen was judged as "A". The results are shown in Table 1.

如表1所示，在全部的實施例中蝕刻特性的評價為「A」。由此確認了，實施例1~18的透明導電體中的金屬氧化物層和金屬層可以容易地除去。實施例13、14的透明導電體總透光率最高，但保存穩定性的評價為B。對於該保存穩定性，只要是不尋求如此高的水準的透明性的例如雜訊片等用途(例如，雜訊遮罩等)就 是能夠充分使用的水準。另外，實施例15、16的透明導電體的總透光率稍低，這是由於In2O3的含有率高，因此，吸收率增加的緣故。然而，如果是該總透光率，在不需要第2金屬氧化物層上安裝配線電極使之導通的用途中，實用上沒有問題。進一步，實施例17、18的透明導電體其總透光率也稍低，這是由於GeO2的含有率高，因此，吸收率增加的緣故。 As shown in Table 1, the evaluation of the etching characteristics was "A" in all the examples. From this, it was confirmed that the metal oxide layer and the metal layer in the transparent conductors of Examples 1 to 18 can be easily removed. The transparent conductors of Examples 13 and 14 had the highest total light transmittance, but the storage stability was evaluated as B. For the storage stability, for example, a noise mask such as a noise mask that does not seek such a high level of transparency (for example, a noise mask or the like) is a level that can be sufficiently used. Further, the total light transmittance of the transparent conductors of Examples 15 and 16 was slightly lower because the content of In 2 O 3 was high, and thus the absorption rate was increased. However, in the case of the total light transmittance, there is no problem in practical use in the case where the wiring electrode is not required to be electrically connected to the second metal oxide layer. Further, the transparent conductors of Examples 17 and 18 had a slightly lower total light transmittance, which was because the content of GeO 2 was high, and thus the absorption rate was increased.

為了評價金屬氧化物層的特性，與上述的順序同樣地製作僅金屬氧化物層(單層)的樣品。與上述的順序同樣地進行該樣品的評價。將評價的結果示於表2中。另外，表2的吸收率是使用以分光器測得的穿透率和反射率的測定結果以100-穿透率-反射率=吸收率的式子求取之值。該吸收率是波長380nm下的值。 In order to evaluate the characteristics of the metal oxide layer, a sample of only a metal oxide layer (single layer) was produced in the same manner as described above. The evaluation of the sample was carried out in the same manner as described above. The results of the evaluation are shown in Table 2. In addition, the absorptivity of Table 2 is a value obtained by the equation of 100-penetration-reflectance=absorption rate using the measurement result of the transmittance and the reflectance measured by the spectroscope. This absorption rate is a value at a wavelength of 380 nm.

如表2所示，確認了各實施例的金屬氧化物層的吸收率充分低。另外，確認了即使含有ZnO作為主成分，藉由含有In2O3、 TiO2、Ga2O3以及GeO2作為副成分，並且為特定的TiO2含有率，從而也可以提高蝕刻特性以及導電性。 As shown in Table 2, it was confirmed that the absorption rate of the metal oxide layer of each Example was sufficiently low. Further, it has been confirmed that even if ZnO is contained as a main component, by containing In 2 O 3 , TiO 2 , Ga 2 O 3 , and GeO 2 as subcomponents, and having a specific TiO 2 content, etching characteristics and conductivity can be improved. Sex.

[實施例19~29] [Examples 19 to 29]

除了改變製作金屬層時的靶的組成，並且如表3所示變更金屬層的組成和/或變更金屬層的厚度以外，與實施例1同樣地製作透明導電體。即，在實施例19~25中改變了金屬層的厚度。在實施例26中，使用AgNdCu(Ag：Nd：Cu=99.0：0.5：0.5(質量%))靶來形成金屬層。在實施例27中，使用AgInSn(Ag：In：Sn=99.0：0.5：0.5(質量%))靶來形成金屬層。在實施例28中，使用AgSnSb(Ag：Sn：Sb=99.0：0.5：0.5(質量%))靶來形成金屬層。在實施例29中，使用AgCu(Ag：Cu=99.5：0.5(質量%))靶來形成金屬層。 A transparent conductor was produced in the same manner as in Example 1 except that the composition of the target when the metal layer was formed was changed, and the composition of the metal layer was changed and/or the thickness of the metal layer was changed as shown in Table 3. That is, the thickness of the metal layer was changed in Examples 19 to 25. In Example 26, a metal layer was formed using an AgNdCu (Ag:Nd:Cu=99.0:0.5:0.5 (% by mass)) target. In Example 27, a metal layer was formed using an AgInSn (Ag:In:Sn=99.0:0.5:0.5 (% by mass)) target. In Example 28, a metal layer was formed using an AgSnSb (Ag:Sn:Sb=99.0:0.5:0.5 (% by mass)) target. In Example 29, a metal layer was formed using an AgCu (Ag: Cu = 99.5: 0.5 (% by mass)) target.

與實施例1同樣地進行制得的實施例19~29的透明導電體的評價。評價結果如表3所示。另外，實施例19~29的金屬氧化物層的組成以及厚度與實施例1相同。 The evaluation of the transparent conductors of Examples 19 to 29 obtained in the same manner as in Example 1 was carried out. The evaluation results are shown in Table 3. Further, the compositions and thicknesses of the metal oxide layers of Examples 19 to 29 were the same as in Example 1.

根據表3所示的結果，任一的實施例中蝕刻特性的評 價都為「A」。由此確認了，實施例19~29的透明導電體中的金屬氧化物層和金屬層可以容易地除去。另外，如果金屬層的厚度變大，則確認有表面電阻變小的傾向，並且有總透光率降低的傾向。另外，在銀合金含有Pd的情況下，確認保存穩定性特別優異。 According to the results shown in Table 3, the evaluation of etching characteristics in any of the examples The price is "A". From this, it was confirmed that the metal oxide layer and the metal layer in the transparent conductors of Examples 19 to 29 can be easily removed. In addition, when the thickness of the metal layer is increased, it is confirmed that the surface resistance tends to be small, and the total light transmittance tends to decrease. In addition, when the silver alloy contains Pd, it is confirmed that the storage stability is particularly excellent.

[實施例30~32] [Examples 30 to 32]

在實施例30中，在第1硬塗層上藉由DC磁控濺射依序形成第1金屬氧化物層、金屬層以及第2金屬氧化物層時，第1金屬氧化物層和第2金屬氧化物層使用具有表4所示的組成的ZnO-In2O3-TiO2-Ga2O3-GeO2靶，除此以外與實施例1同樣，同樣地濺射氣體僅使用氬。而且，在實施例31以及32中，第1金屬氧化物層和第2金屬氧化物層使用具有與實施例30相同的組成的靶，並且濺射氣體使用如表4所示的氬與氧的混合氣體來形成。 In the embodiment 30, when the first metal oxide layer, the metal layer, and the second metal oxide layer are sequentially formed by DC magnetron sputtering on the first hard coat layer, the first metal oxide layer and the second metal oxide layer In the same manner as in Example 1, except that the ZnO-In 2 O 3 -TiO 2 -Ga 2 O 3 -GeO 2 target having the composition shown in Table 4 was used as the metal oxide layer, argon was used only for the sputtering gas. Further, in Examples 31 and 32, the first metal oxide layer and the second metal oxide layer used the target having the same composition as that of Example 30, and the sputtering gas used argon and oxygen as shown in Table 4. Mixed gas is formed.

對於各實施例中的透明導電體，按照以下的順序評價耐鹼性。準備濃度為3wt%的KOH溶液。在該鹼溶液中在室溫下將各實施例的透明導電體浸漬2分鐘。其後，進行總透光率測定，判定第1金屬氧化物層、金屬層以及第2金屬氧化物層是否溶解。具體來說，將鹼溶液浸漬後的樣品的總透光率與浸漬前的總透光率一致的情況判定為「A」，將不一致的情況判定為「B」。總透光率(穿透率)使用霧度計(商品名：NDH-7000，日本電色工業公司製造)來測定。評價結果如表4所示。 With respect to the transparent conductors in the respective examples, alkali resistance was evaluated in the following order. A KOH solution having a concentration of 3 wt% was prepared. The transparent conductors of the respective examples were immersed in the alkali solution at room temperature for 2 minutes. Thereafter, the total light transmittance was measured to determine whether or not the first metal oxide layer, the metal layer, and the second metal oxide layer were dissolved. Specifically, the case where the total light transmittance of the sample immersed in the alkali solution coincides with the total light transmittance before immersion is determined as "A", and the case where the sample does not match is determined as "B". The total light transmittance (transmittance) was measured using a haze meter (trade name: NDH-7000, manufactured by Nippon Denshoku Industries Co., Ltd.). The evaluation results are shown in Table 4.

另外，分別準備與實施例30~32中的第2金屬氧化物層同樣的單層的第2金屬氧化物層(厚度為70nm)，測定起因於ZnO的2θ=32.2deg附近的XRD峰強度。將其測定結果、XRD峰強度除以第 2金屬氧化物層得到的值、以及XRD峰的半高寬示於表4中。如此，具備具有特定的結晶性的金屬氧化物的透明導電體除了優異的蝕刻性以外，還具有良好的耐鹼性。 Further, a single-layer second metal oxide layer (thickness: 70 nm) similar to the second metal oxide layer in Examples 30 to 32 was prepared, and the XRD peak intensity in the vicinity of 2θ = 32.2 deg of ZnO was measured. Divide the measurement result and the XRD peak intensity by the first The values obtained for the 2 metal oxide layer and the full width at half maximum of the XRD peak are shown in Table 4. As described above, the transparent conductor having the metal oxide having specific crystallinity has excellent alkali resistance in addition to excellent etching properties.

[比較例1~2] [Comparative Examples 1 to 2]

除了作為形成第1金屬氧化物層以及第2金屬氧化物層時的靶使用具有表5所示的組成的靶以外，與實施例1同樣地製作比較例1~2的透明導電體。在各個比較例中，第1金屬氧化物層和第2金屬氧化物層使用具有相同的組成的靶形成。各比較例中的第1金屬氧化物層和第2金屬氧化物層的組成如表5所示。與實施例1同樣地評價了各比較例的透明導電體的各個特性。結果如表5所示。 The transparent conductors of Comparative Examples 1 and 2 were produced in the same manner as in Example 1 except that the target having the composition shown in Table 5 was used as the target for forming the first metal oxide layer and the second metal oxide layer. In each of the comparative examples, the first metal oxide layer and the second metal oxide layer were formed using targets having the same composition. The composition of the first metal oxide layer and the second metal oxide layer in each comparative example is shown in Table 5. The respective characteristics of the transparent conductor of each comparative example were evaluated in the same manner as in the first embodiment. The results are shown in Table 5.

如表5所示，確認了具有雖然含有ZnO-In2O3-TiO2-Ga2O3-GeO2這五種成分，但是TiO2的含有率在本申請發明的範圍外的金屬氧化物層的透明導電體不能充分地進行蝕 刻。 As shown in Table 5, it was confirmed that the metal oxide having a content of TiO 2 outside the range of the present invention has five components including ZnO-In 2 O 3 -TiO 2 -Ga 2 O 3 -GeO 2 . The transparent conductor of the layer is not sufficiently etched.

(產業上之可利用性) (industrial availability)

根據本公開的內容，可以提供能夠容易地將金屬氧化物層和金屬層圖案化的透明導電體。另外，根據本公開的內容，藉由使用如此的透明導電體，可以提供能夠容易地製造的觸控面板。 According to the disclosure, a transparent electric conductor capable of easily patterning a metal oxide layer and a metal layer can be provided. In addition, according to the content of the present disclosure, by using such a transparent conductor, a touch panel that can be easily manufactured can be provided.

10‧‧‧透明樹脂基材 10‧‧‧Transparent resin substrate

12‧‧‧第1金屬氧化物層 12‧‧‧1st metal oxide layer

14‧‧‧第2金屬氧化物層 14‧‧‧2nd metal oxide layer

16‧‧‧金屬層 16‧‧‧metal layer

100‧‧‧透明導電體 100‧‧‧Transparent conductor

Claims (4)

一種透明導電體，其係依序積層：透明樹脂基材、第1金屬氧化物層、包含銀合金的金屬層、以及第2金屬氧化物層；上述第1金屬氧化物層含有ZnO作為主成分，並且含有In2O3、TiO2、Ga2O3以及GeO2作為副成分，TiO2的含量相對於ZnO、In2O3、TiO2、Ga2O3以及GeO2之5種成分的合計為12mol%以下；上述銀合金為Ag與選自Pd、Cu、Nd、In、Sn以及Sb中的至少1種金屬的合金；上述第2金屬氧化物層係含有ZnO作為主成分，並且含有In2O3、TiO2、Ga2O3以及GeO2作為副成分，TiO2的含量相對於ZnO、In2O3、TiO2、Ga2O3以及GeO2之5種成分的合計為12mol%以下；在上述第1金屬氧化物層與上述第2金屬氧化物層之各層之中，ZnO的含量相對於ZnO、In2O3、TiO2、Ga2O3以及GeO2之5種成分的合計為72~85mol%，In2O3的含量相對於上述5種成分的合計為4~13mol%，TiO2的含量相對於上述5種成分的合計為3~12mol%，Ga2O3的含量相對於上述5種成分的合計為3~9mol%，GeO2的含量相對於上述5種成分的合計為3~12mol%。 A transparent conductor comprising a transparent resin substrate, a first metal oxide layer, a metal layer containing a silver alloy, and a second metal oxide layer; wherein the first metal oxide layer contains ZnO as a main component And containing In 2 O 3 , TiO 2 , Ga 2 O 3 , and GeO 2 as subcomponents, and the content of TiO 2 is relative to five components of ZnO, In 2 O 3 , TiO 2 , Ga 2 O 3 , and GeO 2 . a total of 12 mol% or less; the silver alloy is an alloy of Ag and at least one metal selected from the group consisting of Pd, Cu, Nd, In, Sn, and Sb; and the second metal oxide layer contains ZnO as a main component and contains in 2 O 3, TiO 2, Ga 2 O 3 and GeO 2 as an accessory component, TiO 2 content with respect to the 2 O 3, TiO 2, Ga 2 O 3 and GeO 2 of the five components ZnO, in the total of 12mol % or less; among the layers of the first metal oxide layer and the second metal oxide layer, the content of ZnO is five components of ZnO, In 2 O 3 , TiO 2 , Ga 2 O 3 and GeO 2 the total of 72 ~ 85mol%, the content of in 2 O 3 with respect to the total of five components is 4 ~ 13mol%, TiO 2 content with respect to the five kinds of It divided the total of 3 ~ 12mol%, the content of Ga 2 O 3 with respect to the total of five components 3 ~ 9mol%, GeO 2 content with respect to the total of five components 3 ~ 12mol%. 如請求項1之透明導電體，其中，上述第2金屬氧化物層係具有特定的結晶性，該特定的結晶性係指起因於ZnO的XRD的繞射峰的峰強度除以第2金屬氧化物層的薄膜的膜厚(單位nm)之值為50以上的結晶性。 The transparent conductor according to claim 1, wherein the second metal oxide layer has a specific crystallinity, and the specific crystallinity is a peak intensity of a diffraction peak due to XRD of ZnO divided by a second metal oxide. The film thickness (unit nm) of the film of the object layer has a crystallinity of 50 or more. 如請求項1或2之透明導電體，其中，上述金屬層的厚度為4~11nm。 The transparent conductor of claim 1 or 2, wherein the metal layer has a thickness of 4 to 11 nm. 一種觸控面板，係在面板上具有感測器薄膜者，上述感測器薄膜係由請求項1至3中任一項之透明導電體構成。 A touch panel is provided with a sensor film on a panel, and the sensor film is composed of a transparent conductor of any one of claims 1 to 3.
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