TW201528291A - Transparent conductive laminate and touch panel - Google Patents
Transparent conductive laminate and touch panel Download PDFInfo
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- TW201528291A TW201528291A TW103138176A TW103138176A TW201528291A TW 201528291 A TW201528291 A TW 201528291A TW 103138176 A TW103138176 A TW 103138176A TW 103138176 A TW103138176 A TW 103138176A TW 201528291 A TW201528291 A TW 201528291A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
- B32B2255/205—Metallic coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
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Abstract
Description
本發明係有關於一種透明導電性積層體及具有該透明導電性積層體之觸控面板。 The present invention relates to a transparent conductive laminate and a touch panel having the transparent conductive laminate.
於透明之基材上積層有透明導電膜之透明導電性積層體，以具有導電性與光學上的透明性來說，係被當作透明電極膜、電磁波遮蔽膜、面狀發熱膜及反射防止膜等來使用，而近年來則是作為觸控面反用電極而受到矚目。觸控面板有電阻膜式、電容耦合式及光學式等存在有多樣的方式。而透明導電膜則可用於例如藉由上下電極接觸來特定觸控位置之電阻膜式、及可感知靜電容量變化之電容耦合式。用於電阻膜式之透明導電膜，以動作原理上透明導電膜彼此會機械式接觸來看則尋求高耐久性。 A transparent conductive laminated body in which a transparent conductive film is laminated on a transparent substrate, and is used as a transparent electrode film, an electromagnetic wave shielding film, a planar heat generating film, and reflection prevention in terms of conductivity and optical transparency. Films and the like have been used, and in recent years, they have attracted attention as counter electrodes for touch surfaces. There are various ways in which the touch panel has a resistive film type, a capacitive coupling type, and an optical type. The transparent conductive film can be used, for example, in a resistive film type in which a touch position is contacted by upper and lower electrodes, and a capacitive coupling type in which a change in electrostatic capacitance can be sensed. A transparent conductive film for a resistive film type seeks high durability in view of the fact that the transparent conductive films are mechanically contacted with each other.
為了賦予作為透明導電膜使用之透明導電性積層體所述之高耐久性，自以往即係在基材與銦錫氧化物等之透明導電膜之間設置氧化矽層來強化對基材之透明導電膜的黏著性。在此，於使用了SiO2層作為氧化矽層的情況 時，雖然可謀求某種程度之黏著性的提升，但黏著性及耐鹼性等之化學抗性卻不充分，故不可謂有滿足所求之耐久性。又，於使用了SiOx(x小於2)層的情況時，雖然可獲得高黏著性但以會招致透明導電膜之表面電阻變化的觀點來說卻有問題。 In order to impart high durability as described for the transparent conductive laminated body used as the transparent conductive film, a ruthenium oxide layer is conventionally provided between the substrate and a transparent conductive film such as indium tin oxide to enhance transparency to the substrate. Adhesion of the conductive film. Here, when the SiO 2 layer is used as the yttrium oxide layer, the adhesion can be improved to some extent, but the chemical resistance such as adhesion and alkali resistance is insufficient, so it is not satisfactory. The durability sought. Further, when a layer of SiO x (x is less than 2) is used, although high adhesion can be obtained, there is a problem in that the surface resistance of the transparent conductive film is changed.
因此，為了使黏著性與透明導電膜之電性的維持並存，舉例來說，於專利文獻1中記載有一透明導電性積層體之技術，該透明導電性積層體係自基材側起依序設置相對折射率在1.6~1.9之範圍的SiOx(x為1.5以上且小於2)與SiO2層，並於其上設有透明導電膜者。然而，以專利文獻1所載之透明導電性積層體來說，雖可兼顧黏著性與透明導電膜之電性的維持，但卻有會對透射光之色調帶來變化的情形，並且層的厚度厚，由此可知在生產性及光穿透性方面仍期望改善。 Therefore, in order to coexist the adhesion between the adhesiveness and the electrical properties of the transparent conductive film, for example, Patent Document 1 describes a technique of a transparent conductive laminated body which is sequentially disposed from the substrate side. The SiO x (x is 1.5 or more and less than 2) and the SiO 2 layer having a relative refractive index in the range of 1.6 to 1.9, and a transparent conductive film is provided thereon. However, in the transparent conductive laminated body disclosed in Patent Document 1, although the adhesion and the electrical properties of the transparent conductive film can be maintained, the color tone of the transmitted light is changed, and the layer is The thickness is thick, and it is understood that improvement is still desired in terms of productivity and light transmittance.
專利文獻1：日本專利第4508074號公報 Patent Document 1: Japanese Patent No. 4508074
本發明之目的在於提供一種透明導電性積層體，其於基材上積層有透明導電膜，該透明導電性積層體可確保基材與透明導電膜之黏著性之同時亦可保持透明導電膜之電性，並且光穿透特性良好且具有優異之化學抗 性。並且，本發明之目的在於提供一種具備有前述透明導電性積層體之可靠性高的觸控面板。 An object of the present invention is to provide a transparent conductive laminated body in which a transparent conductive film is laminated on a substrate, and the transparent conductive laminated body can ensure adhesion of the substrate to the transparent conductive film while maintaining the transparent conductive film. Electrical, and good light transmission characteristics and excellent chemical resistance Sex. Further, an object of the present invention is to provide a touch panel having high reliability including the transparent conductive laminate.
本發明之透明導電性積層體具有：透明基材；SiOx1層，其係設於前述透明基材之一側主面上且厚度為3~60nm(但是，x1為1.8以上且小於2.0)；SiOx2層，其係設於前述SiOx1層上且厚度為0.2~5nm(但是，x2為1.9以上且2.0以下，且大於x1)；及導電層，其係設於前述SiOx2層上且以銦錫氧化物為主體。 The transparent conductive laminated body of the present invention comprises: a transparent substrate; and a SiO x1 layer provided on one side main surface of the transparent substrate and having a thickness of 3 to 60 nm (however, x1 is 1.8 or more and less than 2.0); a SiO x2 layer which is provided on the SiO x1 layer and has a thickness of 0.2 to 5 nm (however, x2 is 1.9 or more and 2.0 or less and larger than x1); and a conductive layer is provided on the SiO x2 layer and Indium tin oxide is the main body.
又，本發明之觸控面板具備有前述本發明之透明導電性積層體。 Moreover, the touch panel of the present invention includes the transparent conductive laminated body of the present invention.
依據本發明可提供一種透明導電性積層體，其於基材上積層有透明導膜，該透明導電性積層體可於確保基材與透明導電膜之黏著性同時亦可保持有透明導電膜之電性，並且光穿透特性良好且具有優異之化學抗性。並且，依據本發明可提供一種具備有前述透明導電性積層體之可靠性高的觸控面板。 According to the present invention, it is possible to provide a transparent conductive laminated body in which a transparent conductive film is laminated on a substrate, and the transparent conductive laminated body can ensure adhesion of the substrate and the transparent conductive film while maintaining a transparent conductive film. Electrical, and good light transmission characteristics and excellent chemical resistance. Further, according to the present invention, it is possible to provide a touch panel having high reliability including the transparent conductive laminate.
10‧‧‧透明導電性積層體 10‧‧‧Transparent conductive laminate
4‧‧‧導電層 4‧‧‧ Conductive layer
1‧‧‧透明基材 1‧‧‧Transparent substrate
5a,5b‧‧‧樹脂層 5a, 5b‧‧‧ resin layer
2‧‧‧SiOx1層 2‧‧‧SiO x1 layer
3‧‧‧SiOx2層 3‧‧‧SiO x2 layer
圖1係顯示本發明透明導電性積層體之實施形態之一例的截面圖。 Fig. 1 is a cross-sectional view showing an example of an embodiment of a transparent conductive laminated body of the present invention.
圖2係顯示本發明透明導電性積層體之實施形態之另一例的截面圖。 Fig. 2 is a cross-sectional view showing another example of the embodiment of the transparent electroconductive laminate of the present invention.
以下，將一邊參照圖式一邊說明本發明之實施形態。另外，本發明非受限於下述說明而作解釋者。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. Further, the present invention is not limited by the following description.
[透明導電性積層體] [Transparent Conductive Laminated Body]
圖1及圖2係分別顯示本發明透明導電性積層體之實施形態之一例及另一例的截面圖。 Fig. 1 and Fig. 2 are cross-sectional views showing an example of another embodiment of the transparent electroconductive laminate of the present invention and another example.
於圖1及圖2中，透明導電性積層體10具有：透明基材1；SiOx1層2，其係設於透明基材1之一側主面上且厚度為3~60nm(但是，x1為1.8以上且小於2.0)；SiOx2層3，其係設於SiOx1層2上且厚度為0.2~5nm(但是，x2為1.9以上且2.0以下，且大於x1)；及導電層4，其係設於SiOx2層3上且以銦錫氧化物為主體。 In FIGS. 1 and 2, the transparent conductive laminated body 10 has a transparent substrate 1 and a SiO x1 layer 2 which is provided on one side main surface of the transparent substrate 1 and has a thickness of 3 to 60 nm (however, x1) a SiO x 2 layer 3 which is provided on the SiO x1 layer 2 and has a thickness of 0.2 to 5 nm (however, x2 is 1.9 or more and 2.0 or less and larger than x1); and the conductive layer 4 It is provided on the SiO x2 layer 3 and is mainly composed of indium tin oxide.
圖2所示之透明導電性積層體10之構造如下：透明基材1於兩主面上具有樹脂層5a、5b，且於其中一側之樹脂層5a上依序設有SiOx1層2、SiOx2層3及導電層4。另外，於本發明之透明導電性積層體中，如圖2所示之樹脂層5a及5b般之樹脂層為可隨意設置之層。 The transparent conductive laminated body 10 shown in Fig. 2 has the following structure: the transparent substrate 1 has resin layers 5a and 5b on both main faces, and SiO x1 layer 2 is sequentially provided on one of the resin layers 5a. SiO x 2 layer 3 and conductive layer 4. Further, in the transparent conductive laminated body of the present invention, the resin layers like the resin layers 5a and 5b shown in Fig. 2 are arbitrarily arranged layers.
由於導電層4係透過前述構造之SiOx1層2及SiOx2層3而形成於透明基材1上，故與透明基材1牢固地緊密黏著而具有高耐久性。又，由於以銦錫氧化物為主體之導電層4是以與SiOx2層3相接之形式來形成，故可以與直接形成於透明基材1上之情況時相同之結晶狀態來形成。藉此，於導電層4，薄片電阻值等之電性可保持於預定的值。又，透明導電性積層體10具有可見光穿透率高且穿透光之色調變化少 等之良好的光穿透特性。 Since the conductive layer 4 is formed on the transparent substrate 1 by transmitting the SiO x1 layer 2 and the SiO x2 layer 3 having the above-described structure, it is strongly adhered to the transparent substrate 1 and has high durability. Further, since the conductive layer 4 mainly composed of indium tin oxide is formed in contact with the SiO x 2 layer 3, it can be formed in the same crystalline state as in the case of being directly formed on the transparent substrate 1. Thereby, the electrical properties of the sheet resistance value and the like in the conductive layer 4 can be maintained at a predetermined value. Further, the transparent conductive laminated body 10 has excellent light transmission characteristics such as high visible light transmittance and small change in color tone of transmitted light.
以下，將就構成透明導電性積層體10之各要素進行說明。 Hereinafter, each element constituting the transparent conductive laminated body 10 will be described.
作為透明基材1並無特別限制可使用通常用於透明導電性積層體之透明基材，例如由透明性高的材料構成之薄膜狀或板狀的基材。作為所述之透明基材1，舉例來說，宜為由選自如下之聚合物或共聚物所構成之塑膠薄膜：聚乙烯及聚丙烯等之聚烯；聚對酞酸乙二酯、聚對苯二甲酸丁二酯及聚萘二甲酸乙二醇酯等之聚酯；尼龍6及尼龍66等之聚醯胺；聚醯亞胺；聚芳香酯；聚碳酸酯；聚(甲基)丙烯酸酯；聚醚碸；及聚碸等。該塑膠薄膜可為經延伸之薄膜亦可為無延伸之薄膜。作為透明基材1，於該等之中又特別以由聚對酞酸乙二酯所構成之塑膠薄膜為宜。 The transparent substrate 1 is not particularly limited, and a transparent substrate which is generally used for a transparent conductive laminate, for example, a film-like or plate-shaped substrate made of a material having high transparency can be used. The transparent substrate 1 is, for example, preferably a plastic film composed of a polymer or a copolymer selected from the group consisting of polyethylene and polypropylene, polyethylene terephthalate, and poly(ethylene terephthalate). Polyesters such as butylene terephthalate and polyethylene naphthalate; polyamines such as nylon 6 and nylon 66; polyimine; polyaryl ester; polycarbonate; poly(methyl) Acrylate; polyether oxime; and polyfluorene. The plastic film may be an extended film or an unstretched film. As the transparent substrate 1, a plastic film composed of polyethylene terephthalate is particularly preferable among these.
另外，於本說明書中「(甲基)丙烯酸酯」係作為總稱丙烯酸酯與甲基丙烯酸酯之用語來使用。以下，「(甲基)丙烯醯…」係以同前述之意思來使用。 In addition, in the present specification, "(meth) acrylate" is used as a generic term for acrylate and methacrylate. Hereinafter, "(meth)acrylofluorene..." is used in the same sense as described above.
透明基材1之厚度係依據透明導電性積層體10所用之用途來適當地選擇。用於觸控面板的情況時，基於可撓性及耐久性等之觀點，透明基材1之厚度宜為10~200μm，且20~150μm較佳。 The thickness of the transparent substrate 1 is appropriately selected depending on the use of the transparent conductive laminated body 10. In the case of a touch panel, the thickness of the transparent substrate 1 is preferably from 10 to 200 μm, and preferably from 20 to 150 μm, from the viewpoints of flexibility and durability.
又，透明基材1其至少於配置有SiOx1層2之側的主面上，在使與SiOx1層2之黏著性提升等之目的下，亦可預先施有易接著處理、底漆處理及電暈處理等之表面處理。另外，該表面處理亦可施於透明基材1之兩側主面上。 Further, the transparent substrate 1 is disposed at least on the main surface side of the SiO 2 layer is x1, and in order to bring the like to enhance the adhesion of SiO x1 layer 2, the application may have previously easy adhesion treatment, primer treatment And surface treatment such as corona treatment. Further, the surface treatment may be applied to both main surfaces of the transparent substrate 1.
並且，透明基材1亦可依所需在無損本發明效果之範圍內，至少於配置有SiOx1層2之側的主面上具有樹脂層。另外，樹脂層亦可設於透明基材1之兩主面上。圖2係一顯示如所述之於透明基材1之兩主面上具有樹脂層5a及5b之透明導電性積層體10的截面圖者。作為樹脂層宜為具有可使SiOx1層2之黏著性提升之機能或光學調整之機能等之樹脂層或為透明且堅韌之樹脂層的硬塗層。 Further, the transparent substrate 1 may have a resin layer on at least the main surface on the side where the SiO x1 layer 2 is disposed, as long as the effect of the present invention is not impaired. Further, the resin layer may be provided on both main faces of the transparent substrate 1. Fig. 2 is a cross-sectional view showing the transparent conductive laminated body 10 having the resin layers 5a and 5b on both main surfaces of the transparent substrate 1 as described above. The resin layer is preferably a resin layer having a function of improving the adhesion of the SiO x1 layer 2 or a function of optical adjustment, or a hard coat layer which is a transparent and tough resin layer.
硬塗層之厚度宜為1~15μm，且1.5~10μm較佳。藉由將硬塗層之膜厚設在1μm以上，可藉由硬塗層之形成獲得所期待之效果。又，藉由將膜厚設在15μm以下，則於可抑制硬塗層之成膜效率降低的同時，還可抑制裂痕之發生。 The thickness of the hard coat layer is preferably from 1 to 15 μm, and preferably from 1.5 to 10 μm. By setting the film thickness of the hard coat layer to 1 μm or more, the desired effect can be obtained by the formation of the hard coat layer. Moreover, by setting the film thickness to 15 μm or less, it is possible to suppress the occurrence of cracks while suppressing the decrease in the film formation efficiency of the hard coat layer.
硬塗層，舉例來說，係由會因游離輻射或熱而硬化之硬化性樹脂的硬化物所構成。會因游離輻射而硬化之硬化性樹脂可含有丙烯酸系材料，而亦可使用如多元醇之(甲基)丙烯酸酯之多官能的(甲基)丙烯酸酯化合物，以及如由二異氰酸酯與多元醇及(甲基)丙烯酸之羥酯等合成而成之多官能的胺甲酸酯(甲基)丙烯酸酯化合物。又，除該等之外，亦可使用具有丙烯酸酯系之官能基例如(甲基)丙烯醯基之聚醚樹脂、聚酯樹脂、環氧樹脂、醇酸樹脂、螺縮醛(spiroacetal)樹脂、聚丁二烯樹脂及聚硫醇多烯(polythiol polyene)樹脂等。又，亦可使用熱硬化型之聚矽氧烷樹脂等。 The hard coat layer is, for example, composed of a cured product of a curable resin which is hardened by free radiation or heat. The curable resin which is hardened by free radiation may contain an acrylic material, and a polyfunctional (meth) acrylate compound such as a polyol (meth) acrylate, and a diisocyanate and a polyhydric alcohol may also be used. A polyfunctional urethane (meth) acrylate compound synthesized by synthesizing a hydroxyester of (meth)acrylic acid or the like. Further, in addition to these, a polyether resin having an acrylate functional group such as a (meth) acrylonitrile group, a polyester resin, an epoxy resin, an alkyd resin, or a spiroacetal resin may be used. Polybutadiene resin and polythiol polyene resin. Further, a thermosetting polysiloxane resin or the like can also be used.
作為對透明基材之塗布面進行之前述硬化性樹脂之塗布方法係以濕式成膜法為宜，且以使用輥式塗佈 機、逆轉輥式塗佈機、凹版塗佈機、微凹版塗佈機、刀式塗佈機、棒式塗佈機、線棒塗佈機、模具式塗佈機、及浸沾式塗佈機之塗布方法為宜。 The method of applying the curable resin to the coated surface of the transparent substrate is preferably a wet film formation method, and is applied by roll coating. Machine, reverse roll coater, gravure coater, micro gravure coater, knife coater, bar coater, bar coater, die coater, and dip coating The coating method of the machine is suitable.
作為前述硬化性樹脂之硬化所用的游離輻射可使用例如紫外線及電子束。為紫外線硬化的情況時，可利用高壓水銀燈、低壓水銀燈、超高壓水銀燈、金屬鹵素燈、碳弧及氙弧等之光源。又，為電子束硬化的情況時則可利用自柯克勞夫-沃耳吞(Cockcroft-Walton)型、凡德格拉夫(Van de Graaff)型、共振變壓型、絕緣芯變壓器型、直線型、地那米(Dynamitron)型、高頻型等各種電子束加速器所釋出之電子束。 As the free radiation used for curing the curable resin, for example, ultraviolet rays and electron beams can be used. In the case of ultraviolet curing, a high-pressure mercury lamp, a low-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a carbon arc, and a xenon arc can be used. In addition, in the case of electron beam hardening, it can be used from the Cockcroft-Walton type, the Van de Graaff type, the resonant transformer type, the insulated core transformer type, and the straight line. An electron beam emitted by various electron beam accelerators such as a type, a Dynamitron type, and a high frequency type.
SiOx1層2(但是，x1為1.8以上且小於2.0)係配置於前述透明基材1之一側主面上且厚度為3~60nm的層。透明基材1如圖2所示具有前述硬塗層等之樹脂層的情況時，SiOx1層2係透過該樹脂層來配置，例如於圖2的情況時，係透過經配置於透明基材1之兩主面上之樹脂層5a及5b中之其中一側的樹脂層5a來配置。而如圖1所示當透明基材1不具有樹脂層的情況時，SiOx1層2係直接設置於透明基材1上。 The SiO x1 layer 2 (however, x1 is 1.8 or more and less than 2.0) is a layer which is disposed on one main surface of the transparent substrate 1 and has a thickness of 3 to 60 nm. When the transparent substrate 1 has a resin layer such as the hard coat layer as shown in FIG. 2, the SiO x1 layer 2 is disposed to pass through the resin layer. For example, in the case of FIG. 2, the transparent substrate 1 is disposed through the transparent substrate. The resin layer 5a on one of the resin layers 5a and 5b on the two main faces is disposed. On the other hand, when the transparent substrate 1 does not have a resin layer as shown in FIG. 1, the SiO x1 layer 2 is directly provided on the transparent substrate 1.
只要SiOx1層2之SiOx1之x1及SiOx1層2之厚度在前述範圍，則以所製得之透明導電性積層體來說，不但各層間可獲得充分之黏著性且同時光穿透特性會良好，並且耐鹼性亦會變得良好。 As long as the SiO 2 SiO x1 x1 x1 layer, and the layer thickness of the SiO 2 x1 in the aforementioned range, the system places the transparent conductive laminate is obtained of, not only between the layers of sufficient adhesion can be obtained while the light penetration characteristics Will be good, and alkali resistance will also become good.
進而言之，於透明導電性積層體被使用於各種用途之際，當於構成為透明導電性積層體與電光元件相接的 情況時，係對透明導電性積層體要求對水蒸氣及氧等具有良好之氣體障蔽性。只要SiOx1層2之SiOx1之x1及SiOx1層2之厚度在前述範圍，則於確保黏著性之同時氣體障蔽性亦會變得良好。 In other words, when the transparent conductive laminated body is used in various applications, when the transparent conductive laminated body is in contact with the electro-optical element, the transparent conductive laminated body is required to have water vapor, oxygen, or the like. Has good gas barrier properties. As long as the SiO 2 SiO x1 x1 x1 layer, and the thickness of the SiO 2 layer of x1 in the above range, the gas at the same time ensuring adhesion properties of vasospasm becomes also good.
透明導電性積層體之氣體障蔽性，舉例來說，針對水蒸氣障蔽性可將依以下方法測定之水蒸氣滲透率作為指標來評價。即，只要該水蒸氣滲透率較預定的值低，則可謂具有優異之水蒸氣障蔽性。水蒸氣滲透率可依據由JIS Z0208所規定之透濕度試驗(圓筒平板法(cup method))，或是，由JIS K7129 B法所規定之紅外線感測器法等來測定。透明導電性積層體之水蒸氣滲透率根據JIS K7129 B法，於溫度40℃且濕度90%RH下所測定之水蒸氣滲透率宜為1g/m2/day以下，更佳為0.5g/m2/day以下。 The gas barrier properties of the transparent conductive laminate are, for example, evaluated by the water vapor permeability measured by the following method as an index for the water vapor barrier property. That is, as long as the water vapor permeability is lower than a predetermined value, it is excellent in water vapor barrier properties. The water vapor permeability can be measured in accordance with the moisture permeability test (cup method) prescribed by JIS Z0208, or the infrared sensor method specified by the JIS K7129 B method. The water vapor permeability of the transparent conductive laminated body is preferably 1 g/m 2 /day or less, more preferably 0.5 g/m, in accordance with JIS K7129 B, at a temperature of 40 ° C and a humidity of 90% RH. 2 / day or less.
又，基於該等之觀點，SiOx1層2之SiOx1之x1宜為較SiOx2之x2更小的值而且在1.9以上且小於2.0之範圍內。且SiOx1層2之厚度宜為3~10nm，更佳則為4~7nm。 Further, based on these viewpoints, x1 of SiO x1 of the SiO x1 layer 2 is preferably a value smaller than x2 of SiO x2 and is in the range of 1.9 or more and less than 2.0. Further, the thickness of the SiO x1 layer 2 is preferably 3 to 10 nm, more preferably 4 to 7 nm.
在透明基材1之主面上形成SiOx1層2，係只要能形成前述厚度之SiOx1層則方法並無特別限制。可為乾式成膜法，亦可為濕式成膜法。SiOx1層2通常係以耐濕熱性優異之乾式成膜法來形成。乾式成膜法則以濺鍍法、離子鍍著法或真空蒸鍍法為宜，且濺鍍法特別理想。 The SiO x1 layer 2 is formed on the main surface of the transparent substrate 1, and the method is not particularly limited as long as the SiO x1 layer having the above thickness can be formed. It may be a dry film formation method or a wet film formation method. The SiO x1 layer 2 is usually formed by a dry film formation method which is excellent in moist heat resistance. The dry film formation method is preferably a sputtering method, an ion plating method or a vacuum evaporation method, and the sputtering method is particularly preferable.
適用濺鍍法的情況時，宜使用硼摻雜多晶矽靶材作為濺鍍靶材。而SiOx1層2之成膜，舉例來說可以下述方式進行：一邊將氬氣中混合有氧氣之混合氣體導入濺鍍裝置 內，一邊以0.1~0.8Pa之壓力來濺鍍硼摻雜多晶矽靶材。於前述濺鍍中，藉由調整功率密度與濺鍍時間，可將SiOx1層2之厚度調整至前述範圍內之預定的厚度，且可藉由電壓與氧氣流量調整x1。 In the case of sputtering, it is preferable to use a boron-doped polycrystalline target as a sputtering target. The film formation of the SiO x1 layer 2 can be carried out, for example, by sputtering a boron-doped polysilicon at a pressure of 0.1 to 0.8 Pa while introducing a mixed gas of oxygen mixed with argon into a sputtering apparatus. Target. In the above sputtering, by adjusting the power density and the sputtering time, the thickness of the SiO x1 layer 2 can be adjusted to a predetermined thickness within the above range, and x1 can be adjusted by the voltage and oxygen flow rate.
依此方式而得之SiOx1層2之SiOx1對波長550nm的光之折射率宜大致在1.43~1.55之範圍，且在1.46~1.53更佳。以下，折射率只要無特別之說明則係指對波長550nm的光之折射率。另外，SiOx1層2之SiOx1的折射率，會於進一步於SiOx1層2上形成SiOx2層3時受到影響而改變。於本說明書中，SiOx1層之SiOx1的折射率係指形成於透明基材1上，且於其上未形成有任何東西之狀態下的SiOx1層之SiOx1的折射率。 In this manner the obtained SiO x1 x1 SiO 2 layer to the refractive index of light of approximately 550nm wavelength should be in the range of 1.43 to 1.55, and more preferably at 1.46 to 1.53. Hereinafter, the refractive index means the refractive index of light having a wavelength of 550 nm unless otherwise specified. Further, SiO 2 layer of the refractive index of SiO x1 x1 is, at the time of SiO x2 will be further formed on the layer 3 of SiO 2 in the affected layer x1 changed. In the present specification, the refractive index of SiO SiO x1 x1 means the layers formed on the transparent substrate 1, and the refractive index of SiO thereon not have anything at the state of SiO x1 x1 layer is formed.
設置於SiOx1層2上之SiOx2層3係一厚度為0.2~5nm，且SiOx2之x2為1.9以上且2.0以下，並且x2大於x1的層。 The SiO x 2 layer 3 provided on the SiO x1 layer 2 has a thickness of 0.2 to 5 nm, and x2 of SiO x2 is 1.9 or more and 2.0 or less, and x2 is larger than x1.
只要SiOx2層3之SiOx2之x2及SiOx2層3之厚度在前述範圍，則以所製得之透明導電性積層體來說，不但各層間可獲得充分之黏著性且同時光穿透特性會變得良好。並且，可使形成於SiOx2層3上且以銦錫氧化物為主體之導電層4的成膜性與直接成膜於透明基材1上之情況相等，藉此可使導電層4之電性充分。 As long as the layer 3 of SiO SiO x2 x2 x2 of x2 and the thickness of the SiO layer 3 in the aforementioned range, places the transparent conductive laminate obtained is made of, not only between the layers of adhesion can be obtained while sufficient light penetration characteristics Will get better. Further, the film forming property of the conductive layer 4 mainly formed of the indium tin oxide on the SiO x2 layer 3 can be made equal to that of the direct formation on the transparent substrate 1, whereby the electric layer 4 can be electrically charged. Full of sex.
又，基於該等之觀點，SiOx2層3之SiOx2之x2宜為較SiOx1之x1更大的值而且在1.95~2.0之範圍內，且為2.0更佳。SiOx2層3之厚度宜為0.5~5nm，更佳則為1~3nm。 Further, based on these viewpoints, x2 of SiO x2 of SiO x2 layer 3 is preferably a value larger than x1 of SiO x1 and is in the range of 1.95 to 2.0, and more preferably 2.0. The thickness of the SiO x 2 layer 3 is preferably 0.5 to 5 nm, more preferably 1 to 3 nm.
在此，於透明導電性積層體10中，前述SiOx1層2之厚度與SiOx2層3之厚度合計宜在20nm以下，且10nm以下更佳。藉由SiOx1層2與SiOx2層3之合計厚度在該範圍可使透明導電性積層體10之光穿透特性變得更加良好。即，於透明導電性積層體10中，可達成可見光穿透率高且透射光之色調變化少的光穿透特性。又，SiOx1層2與SiOx2層3之合計厚度在前述範圍的話於生產性的觀點上亦是有利的。 Here, in the transparent conductive laminated body 10, the thickness of the SiO x1 layer 2 and the thickness of the SiO x2 layer 3 are preferably 20 nm or less in total, and more preferably 10 nm or less. The light transmittance characteristics of the transparent conductive laminated body 10 can be further improved by the total thickness of the SiO x1 layer 2 and the SiO x2 layer 3 in this range. In other words, in the transparent conductive laminated body 10, light transmittance characteristics in which the visible light transmittance is high and the color tone of the transmitted light is less changed can be achieved. Further, when the total thickness of the SiO x1 layer 2 and the SiO x2 layer 3 is within the above range, it is also advantageous from the viewpoint of productivity.
另外，透射光之色調可將依據JIS Z8729(2004年)之使用C光源之L*a*b*表色系統中之b*的值作為指標來進行評價。b*的值係被當作黄度之指標來使用。於本說明書中，將依據JIS Z8729(2004年)之使用C光源之L*a*b*表色系統中之b*的值僅稱「b*的值」。以本發明之透明導電性積層體來說，b*的值宜在1.5以下。 Further, the color tone of the transmitted light can be evaluated by using the value of b* in the L*a*b* color system using the C light source according to JIS Z8729 (2004) as an index. The value of b* is used as an indicator of yellowness. In the present specification, the value of b* in the L*a*b* color system using the C light source according to JIS Z8729 (2004) is simply referred to as "the value of b*". In the transparent conductive laminate of the present invention, the value of b* is preferably 1.5 or less.
SiOx2層3之形成，只要為能形成前述厚度之SiOx2層的方法則並無特別限制。可為乾式成膜法，亦可為濕式成膜法。SiOx2層3通常係以耐濕熱性優異之乾式成膜法來形成。乾式成膜法則以濺鍍法、離子鍍著法或真空蒸鍍法為宜，且特別以濺鍍法為佳。 The formation of the SiO x 2 layer 3 is not particularly limited as long as it is a method of forming the SiO x2 layer having the above thickness. It may be a dry film formation method or a wet film formation method. The SiO x 2 layer 3 is usually formed by a dry film formation method which is excellent in moist heat resistance. The dry film formation method is preferably a sputtering method, an ion plating method or a vacuum evaporation method, and particularly preferably a sputtering method.
適用濺鍍法的情況時，宜使用硼摻雜多晶矽靶材作為濺鍍靶材。而SiOx2層3之成膜，舉例來說可以下述方式來進行：一邊將於氬氣中混合有氧氣之混合氣體導入濺鍍裝置內，一邊以0.1~0.8Pa之壓力來濺鍍硼摻雜多晶矽靶材。於前述濺鍍中，藉由調整功率密度與濺鍍時間，可將SiOx2層3之厚度調整至前述範圍內之預定厚度。又，可藉由 調整電壓與氧氣流量來調整x2。 In the case of sputtering, it is preferable to use a boron-doped polycrystalline target as a sputtering target. The film formation of the SiO x 2 layer 3 can be carried out, for example, by introducing a mixed gas of oxygen mixed in argon gas into the sputtering apparatus and sputtering the boron doping at a pressure of 0.1 to 0.8 Pa. Heteropolycrystalline target. In the sputtering described above, the thickness of the SiO x 2 layer 3 can be adjusted to a predetermined thickness within the above range by adjusting the power density and the sputtering time. Also, x2 can be adjusted by adjusting the voltage and oxygen flow.
依此方式而得之SiOx2層3之SiOx2對波長550nm的光之折射率宜大致在1.46~1.54之範圍，且在1.47~1.52更佳。另外，SiOx2層之SiOx2的折射率與前述SiOx1層之SiOx1的折射率同樣地，係指形成於SiOx1層上，且於其上未形成有任何東西之狀態下之SiOx2層之SiOx2的折射率。 SiO obtained in this manner 3 layers of SiO x2 x2 refractive index of light of appropriate wavelength of 550nm is substantially in the range of 1.46 to 1.54, and more preferably 1.47 to 1.52. Further, the refractive index of SiO SiO x2 x2 refractive index layer of the SiO layer of SiO x1 where x1 Likewise, x1 means formed on the SiO layer, and SiO thereof have anything under the state of the layer is not formed x2 The refractive index of SiO x2 .
比較前述已說明之SiOx1的折射率與所述之SiOx2的折射率的話可知其差小。藉由SiOx1與SiOx2的折射率差小，SiOx1層2與SiOx2層3之界面的反射會受到抑制，而可將透明導電性積層體中之b*的值壓低。 When the refractive index of the above-described SiO x1 and the refractive index of the above SiO x2 are compared, the difference is small. By the difference in refractive index between SiO x1 and SiO x2 , the reflection at the interface between the SiO x1 layer 2 and the SiO x2 layer 3 is suppressed, and the value of b* in the transparent conductive laminate can be lowered.
設於SiOx2層3上且以銦錫氧化為主體之導電層4，作為透明導電膜，則為透明導電性積層體所用之以銦錫氧化為主體的層可無特別限制地使用。 The conductive layer 4 mainly composed of indium tin oxide is provided on the SiO x 2 layer 3, and as the transparent conductive film, a layer mainly composed of indium tin oxide used for the transparent conductive laminated body can be used without particular limitation.
於本發明之透明導電性積層體，舉例來說係於將以非晶質狀態之銦錫氧化物為主體之非晶質層積層於前述SiOx2層3之上後，利用熱處理(退火)使該非晶質層結晶化而獲得結晶性的透明導電膜，並將該結晶性的透明導電膜作為導電層4使用。以下，將就依此方式形成之導電層4進行說明。於以下之說明中，係將非晶質狀態之以銦錫氧化物為主體的非晶質層僅稱「非晶質層」。 In the transparent conductive laminate of the present invention, for example, an amorphous layer mainly composed of an indium tin oxide in an amorphous state is laminated on the SiO x 2 layer 3, and then heat-treated (annealed). The amorphous layer is crystallized to obtain a crystalline transparent conductive film, and the crystalline transparent conductive film is used as the conductive layer 4. Hereinafter, the conductive layer 4 formed in this manner will be described. In the following description, an amorphous layer mainly composed of indium tin oxide in an amorphous state is simply referred to as an "amorphous layer".
於此處，非晶質及結晶質係以電阻值變化率來作評價，該電阻值變化率係於浸漬於HCl溶液(濃度1.5mol/L)5分鐘之前後測定電阻值而求得者，具體來說，係由(浸漬後之電阻值/浸漬前之電阻值)×100(%)而求得者。該電阻值變 化率超過200%的情況時評價為「非晶質」，而電阻值變化率為200%以下的情況時則評價為「結晶質」。 Here, the amorphous and crystalline properties are evaluated by a change rate of the resistance value obtained by measuring the resistance value after immersing in a HCl solution (concentration: 1.5 mol/L) for 5 minutes. Specifically, it is determined by (resistance value after immersion/resistance value before immersion) × 100 (%). The resistance value changes When the conversion rate is more than 200%, it is evaluated as "amorphous", and when the resistance value is 200% or less, it is evaluated as "crystalline".
主要構成非晶質層或是該非晶質層經結晶化之導電層4的銦錫氧化物係銦與錫之氧化物，該氧化物可舉例如氧化銦及氧化錫之混合物、及氧化銦與氧化錫之複合氧化物。銦錫氧化物之組成不論於非晶質狀態下或於結晶化狀態下均不會有所改變。 The indium tin oxide-based indium and tin oxide mainly constituting the amorphous layer or the amorphous layer of the amorphous layer, and the oxide may, for example, be a mixture of indium oxide and tin oxide, and indium oxide and A composite oxide of tin oxide. The composition of indium tin oxide does not change in an amorphous state or in a crystallization state.
本發明所用之銦錫氧化物中之錫以氧化物換算計之含量，以SnO2換算計宜為5.5~10質量%。另外，以下，有將銦錫氧化物中之錫以氧化物換算(以SnO2換算)計之含量記為「錫氧化物含量」的情形。銦錫氧化物中之錫氧化物含量宜在5.8質量%以上，較佳為超過6質量%，且在6.5質量%以上更佳。又，該含量宜在8.9質量%以下，較佳為在8.5質量%以下，且在8.3質量%以下更佳。銦錫氧化物中之錫氧化物含量在前述範圍內的話，則容易自非晶質狀態利用熱處理來結晶化，而可製成一已使結晶化時之薄片電阻值低，且膜厚之增加亦已受抑制者。 The content of tin in the indium tin oxide used in the present invention is preferably from 5.5 to 10% by mass in terms of SnO 2 in terms of oxide. In addition, the content of tin in indium tin oxide in terms of oxide (in terms of SnO 2 ) is referred to as "tin oxide content". The tin oxide content in the indium tin oxide is preferably 5.8 mass% or more, preferably more than 6% by mass, and more preferably 6.5 mass% or more. Further, the content is preferably 8.9 mass% or less, preferably 8.5 mass% or less, and more preferably 8.3 mass% or less. When the content of the tin oxide in the indium tin oxide is within the above range, it is easy to crystallize from the amorphous state by heat treatment, and it is possible to obtain a sheet having a low sheet resistance and an increase in film thickness when crystallization is performed. Also suppressed.
導電層4係以銦錫氧化物為主體的層。「以銦錫氧化物為主體」具體來說係指導電層4之銦錫氧化物之含有比率在90質量%以上。即，非晶質層或導電層4亦可依所需且於不違反本發明宗旨之限度內，在10質量%以內之範圍含有銦錫氧化物以外之成分。銦錫氧化物以外之成分，可舉例如鋁、鋯、鎵、矽、鎢、鋅、鈦、鎂、鈰及鍺等之氧化物。非晶質層或導電層4中之該等銦錫氧化物以外之成分的 含量宜在5質量%以下，較佳在3質量%以下，更佳則在1質量%以下。而非晶質層或導電層4僅由銦錫氧化物構成尤佳。 The conductive layer 4 is a layer mainly composed of indium tin oxide. Specifically, the content of the indium tin oxide of the electric layer 4 is 90% by mass or more. In other words, the amorphous layer or the conductive layer 4 may contain components other than indium tin oxide within a range of 10% by mass or less, as long as it does not violate the gist of the present invention. Examples of the component other than the indium tin oxide include oxides of aluminum, zirconium, gallium, germanium, tungsten, zinc, titanium, magnesium, cerium, and lanthanum. a component other than the indium tin oxide in the amorphous layer or the conductive layer 4 The content is preferably 5% by mass or less, preferably 3% by mass or less, and more preferably 1% by mass or less. The amorphous layer or the conductive layer 4 is preferably composed only of indium tin oxide.
於此處，以銦錫氧化物為主體之非晶質層與導電層4之厚度係約略相同的。導電層4之厚度，從將非晶質層進行熱處理來結晶化時之容易度及穿透率等之光學特性之觀點來看，宜為10~50nm，更佳為15~35nm。 Here, the thickness of the amorphous layer mainly composed of indium tin oxide is approximately the same as the thickness of the conductive layer 4. The thickness of the conductive layer 4 is preferably from 10 to 50 nm, more preferably from 15 to 35 nm, from the viewpoints of optical properties such as ease of crystallizing the amorphous layer and crystallization.
以上，就已使以銦錫氧化物為主體之非晶質層結晶化之導電層進行了說明，但是，以本發明之透明導電性積層體來說，亦可依所需將經如前述積層之以銦錫氧化物為主體之非晶質層於未熱處理狀態下作為導電層使用來當作透明導電性積層體。 As described above, the conductive layer in which the amorphous layer mainly composed of indium tin oxide has been crystallized has been described. However, in the case of the transparent conductive laminated body of the present invention, it is also possible to laminate as described above. The amorphous layer mainly composed of indium tin oxide is used as a conductive layer in a non-heat treated state as a transparent conductive laminated body.
將以銦錫氧化物為主體之非晶質層利用熱處理以使結晶化來作為導電層的情況時，所使用之非晶質層之薄片電阻值，基於結晶化之容易度的觀點，宜為200~500Ω/□，更佳為300~450Ω/□。又，將如所述之以銦錫氧化物為主體之非晶質層進行結晶化所得之導電層的薄片電阻值宜為50~200Ω/□，更佳為70~160Ω/□。 When the amorphous layer mainly composed of indium tin oxide is heat-treated to be crystallized as a conductive layer, the sheet resistance value of the amorphous layer to be used is preferably based on the easiness of crystallization. 200~500Ω/□, more preferably 300~450Ω/□. Further, the conductive layer obtained by crystallizing the amorphous layer mainly composed of indium tin oxide as described above preferably has a sheet resistance value of 50 to 200 Ω/□, more preferably 70 to 160 Ω/□.
本發明之透明導電性積層體中之導電層的薄片電阻值，基於抑制隨著觸控面板等電子機器大型化之操作時的傳輸速度降低之觀點，則宜為50~500Ω/□，更佳為70~450Ω/□。又，據此亦可使蝕刻性良好。而前述理想之導電層薄片抵抗值之範圍中，係包含前述能利用熱處理來製成導電層之非晶質層的薄片抵抗值。因此，以本發明之 透明導電性積層體來說，係可將該非晶質層本身作為導電層使用。 The sheet resistance value of the conductive layer in the transparent conductive laminated body of the present invention is preferably 50 to 500 Ω/□, more preferably 50 to 500 Ω/□, from the viewpoint of suppressing a decrease in the transmission speed when an electronic device such as a touch panel is enlarged. It is 70~450Ω/□. Further, according to this, the etching property can be improved. In the range of the above-mentioned ideal conductive layer sheet resistance values, the sheet resistance value of the amorphous layer which can be formed into a conductive layer by heat treatment is included. Therefore, in the present invention In the transparent conductive laminate, the amorphous layer itself can be used as a conductive layer.
為了形成已將以銦錫氧化物為主體之非晶質層結晶化之導電層4，首先係於上述已說明之SiOx2層3上成膜非晶質狀態之以銦錫氧化物為主體之非晶質層。成膜方法雖然未限制，但宜為濺鍍法、離子鍍著法或真空蒸鍍法，且以濺鍍法尤佳。 In order to form the conductive layer 4 in which the amorphous layer mainly composed of indium tin oxide is crystallized, firstly, indium tin oxide is mainly formed on the SiO x2 layer 3 described above. Amorphous layer. Although the film formation method is not limited, it is preferably a sputtering method, an ion plating method, or a vacuum evaporation method, and is preferably a sputtering method.
適用濺鍍法的情況時，宜使用由下述銦錫氧化物之燒結體構成之濺鍍靶材，該銦錫氧化物之燒結體係混合氧化錫(SnO2)與氧化銦(In2O3)並經燒結而成者。非晶質層之成膜宜使用該濺鍍靶材，並譬如一邊將已於氬氣中混合有0.5~10體積%之氧氣、且宜為混合有0.8~6體積%之氧氣的混合氣體導入濺鍍裝置內，一邊進行濺鍍。藉由一邊將所述之混合氣體導入一邊進行濺鍍，可成膜一非晶質、且容易利用熱處理來結晶化，並且於已使結晶化時的薄片電阻值低之非晶質層。 In the case of the sputtering method, a sputtering target composed of a sintered body of indium tin oxide which is mixed with tin oxide (SnO 2 ) and indium oxide (In 2 O 3 ) is preferably used. ) and sintered. The sputtering of the amorphous layer is preferably carried out by using the sputtering target, and for example, introducing a mixed gas having 0.5 to 10% by volume of oxygen mixed in argon and preferably mixing 0.8 to 6% by volume of oxygen. Sputtering is performed in the sputtering apparatus. By performing sputtering while introducing the mixed gas, it is possible to form an amorphous layer which is amorphous and which is easily crystallized by heat treatment and which has a low sheet resistance value when crystallization is performed.
又，在非晶質層成膜之前，宜設為下述氣體環境：進行排氣使濺鍍裝置內之真空度成為至5×10-4Pa以下，且宜為9×10-5Pa以下，並去除濺鍍裝置內之水分或是自透明基材等產生之水分或有機氣體等之雜質。藉由減低成膜中之水分及有機氣體之存在，可易獲得一容易利用熱處理來結晶化，且於已使結晶化時的薄片電阻值低之非晶質層。 Further, before the film formation of the amorphous layer, it is preferable to use a gas atmosphere in which the degree of vacuum in the sputtering apparatus is 5 × 10 -4 Pa or less, and preferably 9 × 10 -5 Pa or less. And removing moisture in the sputtering device or impurities such as moisture or organic gas generated from a transparent substrate or the like. By reducing the presence of moisture and organic gas in the film formation, an amorphous layer which is easily crystallized by heat treatment and has a low sheet resistance value when crystallization is obtained can be easily obtained.
成膜非晶質層時之氧氣的流量，相對於結晶化後之薄片電阻值成為最低值時之流量宜在0.6~1.4倍之範圍， 較佳為0.7~1.3倍之範圍，且特別以0.8~1.2倍之範圍為佳。因此，於實際之非晶質層之成膜中，宜事先依所述方式求出結晶化後之薄片電阻值成為最低值之時的氧氣流量，並以使相對於該氧氣流量可在前述範圍內之方式來調整氧氣之流量。由最佳流量亦會因成膜裝置而有些許不同來看，則特別藉由依據所述之方法可有效成膜結晶化後之薄片電阻值低的非晶質層。 When the amorphous layer is formed into a film, the flow rate of oxygen is preferably in the range of 0.6 to 1.4 times with respect to the sheet resistance value after crystallization becomes the lowest value. It is preferably in the range of 0.7 to 1.3 times, and particularly preferably in the range of 0.8 to 1.2 times. Therefore, in the film formation of the actual amorphous layer, it is preferable to determine the oxygen flow rate at the time when the sheet resistance value after crystallization becomes the lowest value in advance as described above, so that the flow rate relative to the oxygen gas can be in the foregoing range. The way to adjust the flow of oxygen. In view of the fact that the optimum flow rate is slightly different depending on the film forming apparatus, the amorphous layer having a low sheet resistance after crystallization can be effectively formed by the method described above.
依所述方式成膜之非晶質層之薄片電阻值，大致會在前述非晶質層之理想範圍內，且亦可依所需將以下未施行熱處理所得之非晶質層本身作為導電層。於如所述般將非晶質層本身作為導電層的情況時，無須實行將於以下作說明之熱處理，即可製得透明導電性積層體。 The sheet resistance of the amorphous layer formed in the above manner is substantially within the ideal range of the amorphous layer, and the amorphous layer obtained by the following heat treatment may be used as a conductive layer as needed. . When the amorphous layer itself is used as the conductive layer as described above, the transparent conductive laminated body can be obtained without performing heat treatment as will be described below.
已將非晶質層結晶化之導電層4，可藉由將所述之非晶質層進行熱處理並使結晶化來製成結晶性透明導電膜。熱處理，舉例來說，宜於大氣中在100~150℃下進行10~180分鐘。藉由將熱處理溫度設在100℃以上，並且將熱處理時間設在10分鐘以上，可有效地使非晶質層結晶化。又，藉由將熱處理溫度設在150℃以下，並且將熱處理時間設在180分鐘以下，可充分地結晶化，且藉由設在此以下可抑制透明基材等的損傷，又可使生產性提升。另外，經結晶化之銦錫氧化物宜具有氧化銦(In2O3)之結晶構造，且銦的位置宜取代成錫。 The conductive layer 4 in which the amorphous layer has been crystallized can be formed into a crystalline transparent conductive film by heat-treating the amorphous layer and crystallizing the amorphous layer. The heat treatment, for example, is preferably carried out at 100 to 150 ° C for 10 to 180 minutes in the atmosphere. By setting the heat treatment temperature to 100 ° C or higher and the heat treatment time to 10 minutes or longer, the amorphous layer can be effectively crystallized. In addition, by setting the heat treatment temperature to 150 ° C or lower and the heat treatment time to 180 minutes or less, the crystals can be sufficiently crystallized, and the damage of the transparent substrate or the like can be suppressed and the productivity can be improved. Upgrade. Further, the crystallized indium tin oxide preferably has a crystal structure of indium oxide (In 2 O 3 ), and the position of indium is preferably substituted with tin.
如此一來，即可製得圖1所示之於透明基材1之一側主面上依序積層有SiOx1層2、SiOx2層3及導電層4的透明 導電性積層體10，或是，圖2所示之於透明基材1之兩主面上具有樹脂層5a、5b，且於樹脂層5a上依序積層有SiOx1層2、SiOx2層3及導電層4的透明導電性積層體10。 In this way, the transparent conductive laminated body 10 in which the SiO x1 layer 2, the SiO x2 layer 3 and the conductive layer 4 are sequentially laminated on one main surface of the transparent substrate 1 as shown in FIG. 1 can be obtained, or 2, the resin layers 5a, 5b are provided on the two main surfaces of the transparent substrate 1, and the transparent conductive layers of the SiO x1 layer 2, the SiO x2 layer 3, and the conductive layer 4 are sequentially laminated on the resin layer 5a. Sexual layer body 10.
以上，就圖1及圖2所示之透明導電性積層體10進行了說明，但本發明之透明導電性積層體並不受限於此。於無脫離本發明主旨及範圍之情況的範圍內可將透明導電性積層體10進行變更或變形。本發明之透明導電性積層體適宜用於電子機器。電子機器可舉液晶顯示器、電漿顯示器及觸控面板等，且觸控面板特別理想。 Although the transparent conductive laminated body 10 shown in FIG. 1 and FIG. 2 has been described above, the transparent conductive laminated body of the present invention is not limited thereto. The transparent conductive laminated body 10 can be modified or modified without departing from the spirit and scope of the invention. The transparent conductive laminate of the present invention is suitably used in an electronic device. The electronic device can be a liquid crystal display, a plasma display, a touch panel, etc., and the touch panel is particularly desirable.
[觸控面板] [Touch Panel]
本發明之觸控面板具備有前述本發明之透明導電性積層體。觸控面板，舉例來說，具有顯示部與配置於該顯示部前面的觸控面板部。透明導電性積層體則係作為所述之觸控面板部中具有透明電極的透明電極基板來使用。觸控面板部可為藉由上下電極之接觸來特定觸控位置之電阻膜式，或可偵測靜電容量變化之靜電容量耦合方式中之任一者。 The touch panel of the present invention includes the transparent conductive laminate of the present invention. The touch panel has, for example, a display portion and a touch panel portion disposed on the front surface of the display portion. The transparent conductive laminated body is used as a transparent electrode substrate having a transparent electrode in the touch panel portion. The touch panel portion may be a resistive film type that specifies a touch position by contact of the upper and lower electrodes, or an electrostatic capacitance coupling method that can detect a change in electrostatic capacitance.
以下，將舉實施例來具體說明本發明之實施形態。另外，本發明不受該等實施例限制。又，例1為實施例，例2及例3則為比較例。而厚度係自光學特性或自濺鍍成膜速率與濺鍍時間所求出的值，並非實際測出的厚度。另外，厚度係幾何學上的厚度。 Hereinafter, embodiments of the present invention will be specifically described by way of examples. In addition, the invention is not limited by the embodiments. Further, Example 1 is an example, and Examples 2 and 3 are comparative examples. The thickness is a value obtained from optical characteristics or from the sputtering rate and the sputtering time, and is not the actually measured thickness. In addition, the thickness is a geometric thickness.
(例1) (example 1)
使用兩面具有硬塗層(壓克力樹脂層，8μm)之合計厚度100μm的聚對酞酸乙二酯(PET)薄膜作為附硬塗層之透明基材。於該附硬塗層之透明基材的硬塗層上，形成了厚度7nm的SiOx1層(x1=1.95)。SiOx1層係使用硼摻雜多晶矽靶材，且一邊導入已於氬氣中混合有氧氣的混合氣體，一邊以0.2Pa之壓力進行AC磁控濺鍍而形成。另外，SiOx1層之厚度的調整係調整功率密度及濺鍍時間來進行，而x1之調整則係調整電壓與氧氣流量來進行。 A polyethylene terephthalate (PET) film having a total thickness of 100 μm having a hard coat layer (acrylic resin layer, 8 μm) on both sides was used as a transparent substrate with a hard coat layer. On the hard coat layer of the hard-coated transparent substrate, a SiO x1 layer (x1 = 1.95) having a thickness of 7 nm was formed. The SiO x1 layer was formed by using a boron-doped polycrystalline ruthenium target and introducing a mixed gas of oxygen mixed with argon gas under AC magnetron sputtering at a pressure of 0.2 Pa. Further, the adjustment of the thickness of the SiO x1 layer is performed by adjusting the power density and the sputtering time, and the adjustment of x1 is performed by adjusting the voltage and the oxygen flow rate.
於前述SiOx1層上形成厚度3nm之SiOx2層(x2=2.0)。SiOx2層係使用硼摻雜多晶矽靶材，且一邊導入已於氬氣中混合有氧氣的混合氣體，一邊以0.2Pa之壓力進行AC磁控濺鍍而形成。SiOx2層之厚度的調整係調整功率密度及濺鍍時間來進行，而x2之調整則係調整電壓與氧氣流量來進行。 A SiO x2 layer (x2 = 2.0) having a thickness of 3 nm was formed on the aforementioned SiO x1 layer. The SiO x 2 layer was formed by using a boron-doped polycrystalline ruthenium target and introducing a mixed gas of oxygen mixed with argon gas while performing AC magnetron sputtering at a pressure of 0.2 Pa. The adjustment of the thickness of the SiO x2 layer is performed by adjusting the power density and the sputtering time, and the adjustment of x2 is performed by adjusting the voltage and the oxygen flow rate.
於前述已形成有SiOx1層及SiOx2層之PET薄膜的SiOx2層上，使用由銦錫氧化物構成之靶材，一邊導入已於氬氣中混合有1.4體積%之氧氣的混合氣體，一邊以0.25Pa之壓力進行DC磁控濺鍍而形成了厚度23nm之非晶質層。銦錫氧化物靶材係由混合了10質量%之氧化錫(SnO2)與90質量%之氧化銦(In2O3)並經燒結而成之燒結體所構成。又，非晶質層之厚度的調整，係調整功率密度及濺鍍時間來進行。另外，非晶質層中之錫以氧化物換算計之含量推算大約為10質量%。 Has been formed on the SiO layer and a PET film SiO X1 x2 x2 layers on a SiO layer, a target composed of indium tin oxide, while introducing an argon gas was mixed with a mixed gas of 1.4% by volume of oxygen, An amorphous layer having a thickness of 23 nm was formed by DC magnetron sputtering at a pressure of 0.25 Pa. The indium tin oxide target is composed of a sintered body obtained by mixing 10% by mass of tin oxide (SnO 2 ) and 90% by mass of indium oxide (In 2 O 3 ) and sintering it. Moreover, the adjustment of the thickness of the amorphous layer is performed by adjusting the power density and the sputtering time. Further, the content of tin in the amorphous layer is estimated to be about 10% by mass in terms of oxide.
將所得之積層體切割成100nm×100nm之尺寸，且 以後述之方法測出薄片電阻值。雖然可將所得之積層體直接作為透明導電性積層體，但於本例中，係對該積層體於大氣中進行150℃下且30分鐘之熱處理而製出透明導電性積層體。 The resulting laminate is cut into a size of 100 nm × 100 nm, and The sheet resistance value was measured by a method described later. Although the obtained laminated body can be directly used as the transparent conductive laminated body, in the present example, the laminated body is heat-treated at 150 ° C for 30 minutes in the air to produce a transparent conductive laminated body.
(例2) (Example 2)
在與例1相同之透明基材上，形成厚度10nm的SiOx1層(x1=1.95)。SiOx1層係使用硼摻雜多晶矽靶材，且一邊導入已於氬氣中混合有氧氣的混合氣體，一邊以0.2Pa之壓力進行AC磁控濺鍍而形成。另外，SiOx1層之厚度的調整係調整功率密度及濺鍍時間來進行，而x1之調整則係以調整電壓與氧氣流量來進行。於SiOx1層之上，不形成SiOx2層而是直接依與例1同樣方式形成以銦錫氧化物為主體之導電層。 On the same transparent substrate as in Example 1, a SiO x1 layer (x1 = 1.95) having a thickness of 10 nm was formed. The SiO x1 layer was formed by using a boron-doped polycrystalline ruthenium target and introducing a mixed gas of oxygen mixed with argon gas under AC magnetron sputtering at a pressure of 0.2 Pa. Further, the adjustment of the thickness of the SiO x1 layer is performed by adjusting the power density and the sputtering time, and the adjustment of x1 is performed by adjusting the voltage and the oxygen flow rate. On the SiO x1 layer, a conductive layer mainly composed of indium tin oxide was formed in the same manner as in Example 1 except that the SiO x 2 layer was not formed.
於形成導電層之際，係與例1同樣地在將以銦錫氧化物為主體之非晶質層進行熱處理前將其切割成100nm×100nm之尺寸，並於測定薄片電阻值之後，進行熱處理而製造出透明導電性積層體。 In the same manner as in Example 1, except that the amorphous layer mainly composed of indium tin oxide was subjected to heat treatment, it was cut into a size of 100 nm × 100 nm, and the sheet was subjected to heat treatment after measuring the sheet resistance value. A transparent conductive laminate is produced.
(例3) (Example 3)
在與例1相同之透明基材上，不形成SiOx1層而直接形成厚度10nm之SiOx2層(x2=2.0)。SiOx2層係使用硼摻雜多晶矽靶材，且一邊導入已於氬氣中混合有氧氣的混合氣體，一邊以0.2Pa之壓力進行AC磁控濺鍍而形成。SiOx2層之厚度的調整係調整功率密度及濺鍍時間來進行，而x2之調整則係調整放電電壓與氧氣流量來進行。並於SiOx2層上依與例1同樣方式形成以銦錫氧化物為主體之導電層。 On the same transparent substrate as in Example 1, an SiO x2 layer (x2 = 2.0) having a thickness of 10 nm was directly formed without forming a SiO x1 layer. The SiO x 2 layer was formed by using a boron-doped polycrystalline ruthenium target and introducing a mixed gas of oxygen mixed with argon gas while performing AC magnetron sputtering at a pressure of 0.2 Pa. The adjustment of the thickness of the SiO x2 layer is performed by adjusting the power density and the sputtering time, and the adjustment of x2 is performed by adjusting the discharge voltage and the oxygen flow rate. A conductive layer mainly composed of indium tin oxide was formed on the SiO x 2 layer in the same manner as in Example 1.
於形成導電層之際，係與例1同樣地在將以銦錫氧化物為主體之非晶質層熱處理前將其切割成100nm×100nm之尺寸，並於測定薄片電阻值之後，進行熱處理而製造出透明導電性積層體。 In the same manner as in Example 1, except that the amorphous layer mainly composed of indium tin oxide was cut into a size of 100 nm × 100 nm, and the sheet resistance value was measured, heat treatment was performed. A transparent conductive laminate is produced.
針對於前述各例中所製得之透明導電性積層體進行以下之評價。並將結果示於表1。 The following evaluations were made for the transparent conductive laminated body obtained in each of the above examples. The results are shown in Table 1.
(b*值) (b* value)
根據JIS Z8729(2004年)，使用分光光度計(Tokyo Denshoku Co.,Ltd.製，TC-1800 MK Ⅲ)測定利用C光源自透明導電性積層體之導電層側入射的光的透射光譜(380~780nm)，而算出L*a*b*值。並將b*值示於表1。 According to JIS Z8729 (2004), a transmission spectrum of light incident from the side of the conductive layer of the transparent conductive laminate using a C light source was measured using a spectrophotometer (manufactured by Tokyo Denshoku Co., Ltd., TC-1800 MK III) (380) ~780nm), and calculate the L*a*b* value. The b* values are shown in Table 1.
(薄片電阻值) (sheet resistance value)
將尺寸100mm×100mm之各透明導電性積層體使用Lorester(三菱化學公司製，商品名稱)，依據四探針法測出薄片電阻值。 Each of the transparent conductive laminates having a size of 100 mm × 100 mm was measured for sheet resistance by a four-probe method using Lorester (trade name, manufactured by Mitsubishi Chemical Corporation).
(耐鹼性) (alkaline resistance)
將各透明導電性積層體浸漬於5.6質量%之氫氧化鉀水溶液(40℃)3分鐘後，以目視確認透明導電性積層體之導電層側表面有無裂痕，並依以下之基準進行判定。 Each of the transparent conductive laminates was immersed in a 5.6 mass% potassium hydroxide aqueous solution (40 ° C) for 3 minutes, and the presence or absence of cracks on the side of the conductive layer side of the transparent conductive laminate was visually observed and determined based on the following criteria.
○：完全未確認有裂痕。 ○: There was no crack at all.
×：即便少亦確認有裂痕。 ×: Cracks were confirmed even if they were small.
(水蒸氣障蔽性) (water vapor barrier)
使用水蒸氣滲透率測定裝置(MOCON公司製，製品名稱「PERMATRAN-W 3/33MG」)，並按照JIS K7129 B法(紅 外線感測器法)於溫度40℃且濕度90%RH之氣體環境下測定各透明導電性積層體之水蒸氣滲透率。另外，對透明導電性積層體之濕度調節係水蒸氣自成膜面側朝基材側滲透之方向。只要水蒸氣滲透率在0.5g/m2/day以下，則可謂具有良好之水蒸氣障蔽性。 A water vapor permeability measuring device (manufactured by MOCON Co., Ltd., product name "PERMATRAN-W 3/33MG") was used, and in accordance with JIS K7129 B method (infrared sensor method), a gas atmosphere having a temperature of 40 ° C and a humidity of 90% RH was used. The water vapor permeability of each of the transparent conductive laminates was measured. Moreover, the humidity of the transparent conductive laminated body is the direction in which the water vapor permeates from the film formation side toward the substrate side. As long as the water vapor permeability is 0.5 g/m 2 /day or less, it has a good water vapor barrier property.
從表1可明白例1之透明導電性積層體，其色調、電阻值、耐鹼性及水蒸氣障蔽性中之任一者均得到良好之結果。另外，關於水蒸氣障蔽性，即便氧化矽層之總膜厚同為10nm，具有SiOx1層與SiOx2層之積層構造的透明導電性積層體(例1)結果最為良好。氧化矽層原本以如例3所示般成為完全之氧化物(SiO2)會具有較優異之蔽障性，但於使障蔽性以及與基材之黏著性二者兼顧的情況時，則SiOx(x<2)從結果上來看會變得較佳。因此，可推測SiOx1層與SiOx2層之積層體黏著性最高，且具有優異之障蔽性。 As is clear from Table 1, the transparent conductive laminated body of Example 1 gave good results in any of color tone, electric resistance value, alkali resistance, and water vapor barrier property. In addition, the water vapor barrier property was the best when the total thickness of the yttrium oxide layer was 10 nm, and the transparent conductive laminate having the laminated structure of the SiO x1 layer and the SiO x2 layer (Example 1) was the best. The ruthenium oxide layer originally has a superior oxide (SiO 2 ) as shown in Example 3, and has excellent barrier properties, but when both the barrier property and the adhesion to the substrate are taken into consideration, SiO x (x < 2) will be better in terms of results. Therefore, it is presumed that the SiO x1 layer and the SiO x2 layer have the highest adhesion and excellent barrier properties.
10‧‧‧透明導電性積層體 10‧‧‧Transparent conductive laminate
1‧‧‧透明基材 1‧‧‧Transparent substrate
2‧‧‧SiOx1層 2‧‧‧SiO x1 layer
3‧‧‧SiOx2層 3‧‧‧SiO x2 layer
4‧‧‧導電層 4‧‧‧ Conductive layer
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