JP6767945B2 - Metal substrate for electronic devices - Google Patents
Metal substrate for electronic devices Download PDFInfo
- Publication number
- JP6767945B2 JP6767945B2 JP2017157512A JP2017157512A JP6767945B2 JP 6767945 B2 JP6767945 B2 JP 6767945B2 JP 2017157512 A JP2017157512 A JP 2017157512A JP 2017157512 A JP2017157512 A JP 2017157512A JP 6767945 B2 JP6767945 B2 JP 6767945B2
- Authority
- JP
- Japan
- Prior art keywords
- insulating layer
- metal substrate
- electronic device
- transparent conductive
- conductive film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052751 metal Inorganic materials 0.000 title claims description 118
- 239000002184 metal Substances 0.000 title claims description 118
- 239000000758 substrate Substances 0.000 title claims description 113
- 229920003002 synthetic resin Polymers 0.000 claims description 24
- 239000000057 synthetic resin Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 20
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- 229920005992 thermoplastic resin Polymers 0.000 claims description 14
- 229920001187 thermosetting polymer Polymers 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052719 titanium Inorganic materials 0.000 claims description 6
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- 238000005259 measurement Methods 0.000 description 18
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Electroluminescent Light Sources (AREA)
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Description
本発明は、電子デバイス用金属基板に関する。 The present invention relates to a metal substrate for an electronic device.
エレクトロルミネッセンス（以下、「ＥＬ」と略す）素子は、面発光する素子であり、このＥＬ素子としては、発光材料として無機化合物を用いる無機ＥＬ素子及び発光材料として有機化合物を用いる有機ＥＬ素子が存在する。無機ＥＬ素子は、液晶表示装置のバックライト、表示板等に用いられる。また、有機ＥＬ素子は、ディスプレイ、照明等に用いられる。ＥＬ素子の中でも、有機ＥＬ素子は、フルカラーでの自発光が可能であること、非常に薄い膜で構成されること、自在かつ精細な色表現が可能であること等から期待が大きい。 The electroluminescence (hereinafter abbreviated as "EL") element is an element that emits surface light, and the EL element includes an inorganic EL element that uses an inorganic compound as a light emitting material and an organic EL element that uses an organic compound as a light emitting material. To do. Inorganic EL elements are used for backlights, display boards, etc. of liquid crystal display devices. Further, the organic EL element is used for a display, lighting and the like. Among EL elements, organic EL elements are highly expected because they can emit light in full color, are composed of a very thin film, and can express colors freely and finely.
薄膜状のＥＬ素子は、発光材料からなる発光層を電極によって挟み込んだ構造を有している。このＥＬ素子の片側に配設される電極及びこの電極を支持する基板は、光を取り出すため、透明であることが必要とされる。しかしながら、このＥＬ素子は、屈折率の非整合性の影響で、発光層から発光された一部の光が電極を構成する透明導電膜で反射され、光を効率的に外部に取り出すことができない。また、このＥＬ素子は、発光角度が限定されることから、発光方向に不均一性が生じやすく、発光ムラや、眩しさを招来するおそれがある。そのため、この従来のＥＬ素子にあっては、何らかの方法によって光を散乱させて発光方向を広げることが求められる。 The thin-film EL element has a structure in which a light emitting layer made of a light emitting material is sandwiched between electrodes. The electrode arranged on one side of the EL element and the substrate supporting the electrode are required to be transparent in order to extract light. However, in this EL element, due to the influence of the inconsistency of the refractive index, a part of the light emitted from the light emitting layer is reflected by the transparent conductive film constituting the electrode, and the light cannot be efficiently taken out to the outside. .. Further, since the light emitting angle of this EL element is limited, non-uniformity is likely to occur in the light emitting direction, which may cause uneven light emission and glare. Therefore, in this conventional EL element, it is required to scatter light by some method to widen the light emitting direction.
ＥＬ素子の光取り出し率を向上する方法としては、透明導電膜を支持する基板に用いる材料の屈折率を調整する方法や、透明導電膜や上記基板表面に凹凸を形成する方法が知られている。材料の屈折率を調整する方法は、屈折率の異なる層を追加するもので、基板表面に凹凸を形成する方法は、基板表面を加工するもので、いずれも散乱効果によって光取り出し率を向上するものである。 As a method for improving the light extraction rate of the EL element, a method of adjusting the refractive index of the material used for the substrate supporting the transparent conductive film and a method of forming irregularities on the surface of the transparent conductive film and the substrate are known. .. The method of adjusting the refractive index of the material is to add layers having different refractive indexes, and the method of forming irregularities on the substrate surface is to process the surface of the substrate, both of which improve the light extraction rate by the scattering effect. It is a thing.
しかしながら、基板表面に凹凸を形成する場合や、基板に屈折率の異なる層を追加する場合にあっては、基板表面に意図しない凹凸が形成されることがある。一方、有機ＥＬ素子の膜厚は数十ｎｍから数百ｎｍ程度であることから、凹凸の形状が厳密に制御されないと、素子の膜厚に不均一が生じて、素子に短絡を生じるおそれがある。 However, when irregularities are formed on the surface of the substrate or when layers having different refractive indexes are added to the substrate, unintended irregularities may be formed on the surface of the substrate. On the other hand, since the film thickness of the organic EL element is about several tens of nm to several hundreds nm, if the shape of the unevenness is not strictly controlled, the film thickness of the element may be uneven and a short circuit may occur in the element. is there.
そのため、基板表面の凹凸は、短絡を生じないよう滑らかである必要がある。しかしながら、基板表面の凹凸を工業的に安価で精度よく作成することは容易ではない。このような点から、今日では適切な凹凸を形成するための多くの検討がなされている。 Therefore, the unevenness of the substrate surface needs to be smooth so as not to cause a short circuit. However, it is not easy to industrially inexpensively and accurately create irregularities on the substrate surface. From this point of view, many studies have been made today to form appropriate unevenness.
例えば、特開２０１１−３９３７５号公報では、ＴｉＯ２や、ＺｒＯ２等の無機微粒子を含有する樹脂から構成され、規則的に区切られた細胞状の凹凸構造を有する光散乱層を備える光散乱基板が提案されている。 For example, in Japanese Patent Application Laid-Open No. 2011-39375, a light scattering substrate composed of a resin containing inorganic fine particles such as TiO 2 and ZrO 2 and having a light scattering layer having a regularly partitioned cell-like uneven structure. Has been proposed.
また、特開２０１０−１５３４５７号公報では、フッ化ガスの反応ガスとアシストガスとをプラズマ化させてアルカリガラス基板の表面をエッチングすることで、表面に微細な凹凸パターンが形成されたテクスチャ付基板を製造する方法が提案されている。 Further, in Japanese Patent Application Laid-Open No. 2010-153457, a textured substrate in which a fine uneven pattern is formed on the surface of an alkaline glass substrate by plasma-forming a reaction gas of fluoride gas and an assist gas and etching the surface of the alkaline glass substrate. A method of manufacturing is proposed.
また、国際公開第２０１０／０９０１４２号では、透明性基板、下地層、第１の透明電極層及び第２の透明電極層がこの順で積層される構成において、下地層の透明電極側の表面にナノインプリンティング法で凹凸を形成し、さらに減圧ＣＶＤ法により形成される第２の透明電極層に下地層よりも小さな凹凸を形成する方法が提案されている。 Further, in International Publication No. 2010/090142, in a configuration in which a transparent substrate, a base layer, a first transparent electrode layer and a second transparent electrode layer are laminated in this order, the surface of the base layer on the transparent electrode side is formed. A method has been proposed in which irregularities are formed by the nanoimprinting method, and further, irregularities smaller than those of the underlying layer are formed in the second transparent electrode layer formed by the reduced pressure CVD method.
また、国際公開第２０１３／０５４８２０号では、ガラス基板に無機材料の散乱体を含有させた光散乱基板が提案されている。 Further, International Publication No. 2013/054820 proposes a light scattering substrate in which a glass substrate contains a scattering body of an inorganic material.
また、特開２０１４−１７０７３６号公報では、凹凸表面を有するガラス板の凹凸表面上にガラス粉末を塗布し、低温で焼成することにより形成された光散乱基板が提案されている。 Further, Japanese Patent Application Laid-Open No. 2014-170736 proposes a light scattering substrate formed by applying glass powder on the uneven surface of a glass plate having an uneven surface and firing at a low temperature.
また、特開２００９−７５６２１号公報では、樹脂、溶剤及び微粒子を含み、表面にベナードセル構造を有する塗料に含まれる上記樹脂を硬化させることで凹凸形状を形成する方法が提案されている。 Further, Japanese Patent Application Laid-Open No. 2009-75621 proposes a method of forming a concavo-convex shape by curing the resin contained in a coating material containing a resin, a solvent and fine particles and having a Benard cell structure on the surface.
このように、ＥＬ素子における透明導電膜や透明導電膜を支持する基板の表面に凹凸を付与することは光取り出し率を高めるうえで一定の効果がある。また、従来このような光取り出し率の向上は、光取り出し側の光散乱効果によって行われている。 As described above, imparting unevenness to the surface of the transparent conductive film in the EL element or the substrate supporting the transparent conductive film has a certain effect in increasing the light extraction rate. Further, conventionally, such improvement of the light extraction rate is performed by the light scattering effect on the light extraction side.
一般に、ＥＬ素子では、発光層から放出された光は、厚さ方向片側から外部に取り出される。一方、この発光層からは、厚さ方向他方側にも光が放出される。発光層から厚さ方向他方側に放出された光は、発光層の他方側に配設される電極等で反射され、上記発光層を透過した後に上記片側から取り出される。そのため、ＥＬ素子では、厚さ方向片側に配設される基板については透明であることが要求される一方、厚さ方向他方側に配設される基板については透明性が要求されない場合がある。また、上記他方側の基板に入射した光を散乱させることができれば、例えば上記片側に配設される基板での光散乱効果と相俟って、より光散乱効果を高めることができる。このような観点から、発光層の他方側に配設される基板として非透光性基板を用い、この基板に安価かつ簡便に所望の光散乱機能を付与することは工業上有益である。 Generally, in an EL element, the light emitted from the light emitting layer is taken out from one side in the thickness direction to the outside. On the other hand, light is emitted from this light emitting layer to the other side in the thickness direction. The light emitted from the light emitting layer to the other side in the thickness direction is reflected by an electrode or the like arranged on the other side of the light emitting layer, passes through the light emitting layer, and then is taken out from the one side. Therefore, in the EL element, the substrate arranged on one side in the thickness direction is required to be transparent, while the substrate arranged on the other side in the thickness direction may not be required to be transparent. Further, if the light incident on the substrate on the other side can be scattered, for example, the light scattering effect can be further enhanced in combination with the light scattering effect on the substrate arranged on one side. From such a viewpoint, it is industrially beneficial to use a non-transmissive substrate as a substrate disposed on the other side of the light emitting layer and to impart a desired light scattering function to this substrate inexpensively and easily.
本発明は、このような事情に基づいてなされたもので、光散乱機能に優れる非透光性の光散乱基板を提供することを課題とする。 The present invention has been made based on such circumstances, and an object of the present invention is to provide a non-transmissive light scattering substrate having an excellent light scattering function.
上記課題を解決するためになされた本発明に係る電子デバイス用金属基板は、金属板の表面に、絶縁層及び透明導電膜がこの順で積層された電子デバイス用金属基板であって、上記透明導電膜の外面に微細凹凸形状が形成され、上記微細凹凸形状の凸部の頂点の平均ピッチが５μｍ以上５０μｍ以下で、かつ隣接する凸部の頂点及び凹部の底点の高さの差の平均値が５０ｎｍ以上３００ｎｍ以下である。 The metal substrate for an electronic device according to the present invention, which has been made to solve the above problems, is a metal substrate for an electronic device in which an insulating layer and a transparent conductive film are laminated in this order on the surface of the metal plate, and is transparent. A fine concavo-convex shape is formed on the outer surface of the conductive film, the average pitch of the apex of the convex portion of the fine concavo-convex shape is 5 μm or more and 50 μm or less, and the average difference in height between the apex of the adjacent convex portion and the bottom point of the concave portion. The value is 50 nm or more and 300 nm or less.
当該電子デバイス用金属基板は、透明導電膜の外面に形成される微細凹凸形状の凸部の頂点の平均ピッチ、並びに隣接する凸部の頂点及び凹部の底点の高さの差の平均値が上記範囲内であるので、上記透明導電膜の外面が、滑らかで、かつ十分な表面粗さを有する凹凸面として形成される。そのため、当該電子デバイス用金属基板は、光散乱機能に優れると共に厚さの不均一性に起因する素子の短絡を抑制することができる。 In the metal substrate for an electronic device, the average pitch of the vertices of the convex portions having a fine concave-convex shape formed on the outer surface of the transparent conductive film and the average value of the height differences between the vertices of the adjacent convex portions and the bottom points of the concave portions are the average values. Since it is within the above range, the outer surface of the transparent conductive film is formed as an uneven surface that is smooth and has sufficient surface roughness. Therefore, the metal substrate for an electronic device is excellent in light scattering function and can suppress a short circuit of an element due to non-uniformity of thickness.
上記絶縁層が合成樹脂を主成分とするとよい。このように、上記絶縁層が合成樹脂を主成分とすることによって、絶縁性の高い層を容易に形成することができる。 The insulating layer may contain a synthetic resin as a main component. As described above, when the insulating layer contains a synthetic resin as a main component, a layer having high insulating properties can be easily formed.
上記合成樹脂が熱硬化性樹脂であるとよい。このように、上記合成樹脂が熱硬化性樹脂であることによって、上記絶縁層の形成が容易となる。 The synthetic resin is preferably a thermosetting resin. As described above, when the synthetic resin is a thermosetting resin, the formation of the insulating layer becomes easy.
上記合成樹脂は熱可塑性樹脂であってもよい。上記合成樹脂が熱可塑性樹脂であることによって、上記絶縁層を比較的低コストで形成することができる。 The synthetic resin may be a thermoplastic resin. Since the synthetic resin is a thermoplastic resin, the insulating layer can be formed at a relatively low cost.
上記熱可塑性樹脂がポリエステルであり、上記絶縁層が硬化剤を含有するとよい。このように、上記熱可塑性樹脂がポリエステルであり、上記絶縁層が硬化剤を含有することによって、上記絶縁層を低コストで容易かつ確実に形成することができる。 It is preferable that the thermoplastic resin is polyester and the insulating layer contains a curing agent. As described above, when the thermoplastic resin is polyester and the insulating layer contains a curing agent, the insulating layer can be easily and surely formed at low cost.
上記熱可塑性樹脂がアクリル樹脂であり、上記絶縁層が硬化剤を含有することも好ましい。上記熱可塑性樹脂がアクリル樹脂であり、上記絶縁層が硬化剤を含有する場合でも、上記絶縁層を比較的低コストで容易かつ確実に形成することができる。 It is also preferable that the thermoplastic resin is an acrylic resin and the insulating layer contains a curing agent. Even when the thermoplastic resin is an acrylic resin and the insulating layer contains a curing agent, the insulating layer can be easily and surely formed at a relatively low cost.
上記金属板の主成分が、鉄、チタン、アルミニウム又は銅であるとよい。このように、上記金属板の主成分が、鉄、チタン、アルミニウム又は銅であることによって、当該電子デバイス用金属基板の機械的強度や耐性を容易かつ確実に高めることができる。 The main component of the metal plate is preferably iron, titanium, aluminum or copper. As described above, when the main component of the metal plate is iron, titanium, aluminum or copper, the mechanical strength and resistance of the metal substrate for the electronic device can be easily and surely increased.
当該電子デバイス用金属基板の入射角−５度とした場合の反射角１５度における拡散反射率としては５％以上が好ましく、かつ反射角２５度における拡散反射率としては１．５％以上が好ましい。このように、入射角−５度とした場合の反射角１５度における拡散反射率及び反射角２５度における拡散反射率が上記下限以上であることによって、例えばＥＬ素子の構成要素として用いられた場合にこのＥＬ素子の光取り出し率を容易かつ確実に高めることができる。 When the incident angle of the metal substrate for the electronic device is -5 degrees, the diffuse reflectance at a reflection angle of 15 degrees is preferably 5% or more, and the diffuse reflectance at a reflection angle of 25 degrees is preferably 1.5% or more. .. As described above, when the diffuse reflectance at a reflection angle of 15 degrees and the diffuse reflectance at a reflection angle of 25 degrees are equal to or higher than the above lower limit when the incident angle is −5 degrees, for example, when it is used as a component of an EL element. The light extraction rate of this EL element can be easily and surely increased.
上記金属板の絶縁層が積層される側の面に亜鉛めっき層をさらに備えるとよい。このように、上記金属板の絶縁層が積層される側の面に亜鉛めっき層をさらに備えることによって、当該電子デバイス用金属基板の防錆性を高めることができる。 It is preferable to further provide a galvanized layer on the surface on the side where the insulating layer of the metal plate is laminated. As described above, by further providing the zinc plating layer on the surface on the side where the insulating layer of the metal plate is laminated, the rust prevention property of the metal substrate for the electronic device can be enhanced.
当該電子デバイス用金属基板は、上述のように光散乱機能に優れると共に素子の短絡を抑制することができるので、有機ＥＬ照明又は有機太陽電池に好適に用いることができる。 As described above, the metal substrate for an electronic device is excellent in light scattering function and can suppress a short circuit of an element, so that it can be suitably used for organic EL lighting or an organic solar cell.
なお、本発明において、「主成分」とは、質量基準で最も含有割合の高い成分をいう。「凸部の頂点の平均ピッチ」及び「隣接する凸部の頂点及び凹部の底点の高さの差の平均値」は、１００μｍの評価長さにおいて測定される値の平均値をいう。「拡散反射率」とは、透明導電膜の外面で反射した５度以上８５度以下の全反射光に対する反射率をいう。 In the present invention, the "main component" refers to the component having the highest content ratio on a mass basis. The "average pitch of the vertices of the convex portion" and the "average value of the height difference between the apex of the adjacent convex portion and the bottom point of the concave portion" refer to the average value of the values measured at the evaluation length of 100 μm. "Diffuse reflectance" refers to the reflectance for total reflected light of 5 degrees or more and 85 degrees or less reflected on the outer surface of the transparent conductive film.
以上説明したように、本発明の電子デバイス用金属基板は光散乱機能に優れる。 As described above, the metal substrate for an electronic device of the present invention has an excellent light scattering function.
以下、図面を参照しつつ、本発明の実施の形態を詳説する。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
当該電子デバイス用金属基板は、金属板の表面に、絶縁層及び透明導電膜がこの順で積層される。当該電子デバイス用金属基板は、上記透明導電膜の外面（絶縁層と積層される側と反対側の面）に微細凹凸形状が形成され、上記微細凹凸形状の凸部の頂点の平均ピッチが５μｍ以上５０μｍ以下で、かつ隣接する凸部の頂点及び凹部の底点の高さの差の平均値が５０ｎｍ以上３００ｎｍ以下である。また、当該電子デバイス用金属基板は、上記金属板の絶縁層が積層される側の面に亜鉛めっき層をさらに備えることが好ましい。なお、「凸部の頂点」とは、原子間力顕微鏡（ＡＦＭ）で透明導電膜の外面の表面プロファイルを走査した場合に観測される上向き（外向き）ピーク部の最高点をいい、「凹部の底点」とは、ＡＦＭで表面プロファイルを走査した場合に観測される下向き（内向き）ピーク部の最低点をいう。 In the metal substrate for an electronic device, an insulating layer and a transparent conductive film are laminated in this order on the surface of the metal plate. In the metal substrate for an electronic device, a fine concavo-convex shape is formed on the outer surface of the transparent conductive film (the surface opposite to the side where the insulating layer is laminated), and the average pitch of the vertices of the convex portion of the fine concavo-convex shape is 5 μm. The average value of the height difference between the apex of the adjacent convex portion and the bottom point of the concave portion is 50 nm or more and 300 nm or less. Further, it is preferable that the metal substrate for an electronic device further includes a zinc plating layer on the surface on the side where the insulating layer of the metal plate is laminated. The "apex of the convex portion" refers to the highest point of the upward (outward) peak portion observed when the surface profile of the outer surface of the transparent conductive film is scanned by an atomic force microscope (AFM), and is a "concave portion". The "bottom point" means the lowest point of the downward (inward) peak portion observed when the surface profile is scanned by AFM.
当該電子デバイス用金属基板は、例えば金属板の表面に亜鉛めっき層を積層し、この亜鉛めっき層の外面に樹脂組成物を塗布及び乾燥させて絶縁層を積層し、さらにこの絶縁層の外面にＩＴＯ（Ｔｉｎ−ｄｏｐｅｄ Ｉｎｄｉｕｍ Ｏｘｉｄｅ）膜等の透明導電膜を積層することで形成される。当該電子デバイス用金属基板は、この透明導電膜の外面に滑らかで、かつ微細な凹凸形状が形成されることを特徴とする。まず、当該電子デバイス用金属基板に至った過程について説明する。 In the metal substrate for an electronic device, for example, a zinc plating layer is laminated on the surface of a metal plate, a resin composition is applied and dried on the outer surface of the zinc plating layer, and an insulating layer is laminated, and further on the outer surface of the insulating layer. It is formed by laminating a transparent conductive film such as an ITO (Tin-topped Indium Oxide) film. The metal substrate for an electronic device is characterized in that a smooth and fine uneven shape is formed on the outer surface of the transparent conductive film. First, the process of reaching the metal substrate for the electronic device will be described.
鋼板基板の表面に防錆処理として亜鉛めっき層を積層し、積層体を形成した。この積層体の亜鉛めっき層の外面のＡＦＭ観察像を図１に示す。亜鉛めっき層の外面は、めっき条件に基づく凹凸を有し得るが、この外面は亜鉛めっき特有の金属光沢を有しており、鏡面反射に近い状態にあるため、このままでは十分な光散乱機能を有しない。 A galvanized layer was laminated on the surface of the steel plate substrate as a rust preventive treatment to form a laminated body. An AFM observation image of the outer surface of the galvanized layer of this laminated body is shown in FIG. The outer surface of the galvanized layer may have irregularities based on the plating conditions, but since this outer surface has a metallic luster peculiar to galvanization and is in a state close to specular reflection, it has a sufficient light scattering function as it is. I don't have it.
次に、図１の積層体の亜鉛めっき層の外面に透明導電膜（ＩＴＯ膜）を積層した。この透明導電膜の外面のＡＦＭ観察像を図２に示す。図２に示すように、図１の亜鉛めっき層の外面に透明導電膜を積層しても、この透明導電膜の外面には凹凸形状はあまり形成されない。 Next, a transparent conductive film (ITO film) was laminated on the outer surface of the galvanized layer of the laminate of FIG. An AFM observation image of the outer surface of this transparent conductive film is shown in FIG. As shown in FIG. 2, even if the transparent conductive film is laminated on the outer surface of the galvanized layer of FIG. 1, the outer surface of the transparent conductive film does not have much uneven shape.
一方、図１の積層体の亜鉛めっき層の外面に絶縁層を積層する場合について検討する。この絶縁層は、例えば亜鉛めっき層の外面に樹脂組成物を塗布し乾燥させることで形成されるもので、鋼板基板と透明導電膜との間に介在することで鋼板基板と電極との間の絶縁性を確保する。この絶縁層は、通常１０μｍ〜１００μｍ程度の厚さを有しており、亜鉛めっき層の凹凸を覆い隠す。そのため、亜鉛めっき層の外面に絶縁層が積層された積層体にあっては、外面に絶縁層固有の凹凸が形成される。この絶縁層の外面のＡＦＭ観察像を図３に示す。図３に示すように、絶縁層の外面は、大部分がでこぼこしたうねった形状となっているが、一部に微小かつ急峻な突起が形成されている。この絶縁層の外面の凹凸は隣接する凸部の頂点及び凹部の底点の高さの差が不十分であるため、光散乱効果を十分に奏しない。また、絶縁層の外面に形成される上述の急峻な突起は、素子の短絡の原因となるため、有機ＥＬデバイス等を形成するうえで好ましくない。 On the other hand, a case where an insulating layer is laminated on the outer surface of the galvanized layer of the laminated body of FIG. 1 will be examined. This insulating layer is formed by, for example, applying a resin composition to the outer surface of a galvanized layer and drying it. By interposing between the steel sheet substrate and the transparent conductive film, the insulating layer is interposed between the steel sheet substrate and the electrode. Ensure insulation. This insulating layer usually has a thickness of about 10 μm to 100 μm and covers the unevenness of the galvanized layer. Therefore, in the laminated body in which the insulating layer is laminated on the outer surface of the galvanized layer, unevenness peculiar to the insulating layer is formed on the outer surface. An AFM observation image of the outer surface of this insulating layer is shown in FIG. As shown in FIG. 3, the outer surface of the insulating layer has a rugged and undulating shape in most parts, but minute and steep protrusions are formed in a part thereof. The unevenness of the outer surface of the insulating layer does not sufficiently exert the light scattering effect because the difference in height between the apex of the adjacent convex portion and the bottom point of the concave portion is insufficient. Further, the above-mentioned steep protrusions formed on the outer surface of the insulating layer cause a short circuit of the element, which is not preferable for forming an organic EL device or the like.
そこで、絶縁層の外面にポリッシングを行い、この絶縁層の外面の凹みがなくなる程度まで樹脂を削り、絶縁層の外面を平滑化した。平滑化された絶縁層の外面のＡＦＭ観察像を図４に示す。この状態では、絶縁層の外面は極めて平滑で、この外面に透明導電膜を積層した基板は、有機膜等の膜厚の均一化を図ることができるので、素子の短絡を抑制することができる。しかしながら、この構成によると、絶縁層の外面が平滑であるため、所望の光散乱効果を奏しない。 Therefore, the outer surface of the insulating layer was polished, and the resin was scraped to the extent that there were no dents on the outer surface of the insulating layer to smooth the outer surface of the insulating layer. An AFM observation image of the outer surface of the smoothed insulating layer is shown in FIG. In this state, the outer surface of the insulating layer is extremely smooth, and the substrate on which the transparent conductive film is laminated on the outer surface can make the film thickness of the organic film or the like uniform, so that a short circuit of the element can be suppressed. .. However, according to this configuration, since the outer surface of the insulating layer is smooth, the desired light scattering effect is not obtained.
このような事情のもと、本発明者らは、絶縁層の外面に透明導電膜を積層した状態で、透明導電膜の外面に滑らかで、かつ光散乱性に優れる凹凸形状を形成する方法について検討した。その結果、適切に絶縁層を形成し、かつ適切に透明導電膜形成条件を制御することで、滑らかで、かつ光散乱機能に優れる凹凸形状を透明導電膜の外面に形成することを実現した。本発明に係る電子デバイス用金属基板の透明導電膜の外面のＡＦＭ観察像を図５及び図６に示す。 Under such circumstances, the present inventors have described a method for forming a smooth and uneven shape having excellent light scattering properties on the outer surface of the transparent conductive film in a state where the transparent conductive film is laminated on the outer surface of the insulating layer. investigated. As a result, by appropriately forming the insulating layer and appropriately controlling the transparent conductive film forming conditions, it has been realized that a smooth and uneven shape having an excellent light scattering function can be formed on the outer surface of the transparent conductive film. 5 and 6 show AFM observation images of the outer surface of the transparent conductive film of the metal substrate for an electronic device according to the present invention.
図５及び図６に示すように、本発明に係る電子デバイス用金属基板の透明導電膜の外面には隣接する凸部の頂点及び凹部の底点の高さの差が比較的大きい凹凸形状が形成されている。また、凸部と凸部とは一方向側に連続して繋がって峰を形成し、峰と峰との間には比較的深い谷が形成されている。当該電子デバイス用金属基板にあっては、この峰と谷との高さの差が凸部と凹部の高さの差として規定される（つまり、峰及び谷におけるうねりの高低差は本発明の凸部と凹部の高さの差を意味しない）。また、隣接する峰のピッチが隣接する凸部のピッチとして規定される。当該電子デバイス用金属基板は、この連続する凸部の稜線によって区分される傾斜面を有しており、この傾斜面によって光を効果的に散乱することができる。また、この透明導電膜の外面にＥＬ素子等を積層する場合、透明導電膜の外面が滑らかであること、つまり凸部と凹部との間（上述の傾斜面）に急峻な突起や穴が形成されていないこと、が重要である。この点、図５及び図６に示すように、当該電子デバイス用金属基板はこのような急峻な突起や穴がない状態を実現することができる。 As shown in FIGS. 5 and 6, the outer surface of the transparent conductive film of the metal substrate for an electronic device according to the present invention has an uneven shape having a relatively large difference in height between the apex of the adjacent convex portion and the bottom point of the concave portion. It is formed. In addition, the convex portion and the convex portion are continuously connected in one direction to form a peak, and a relatively deep valley is formed between the peaks. In the metal substrate for electronic devices, the difference in height between the peak and the valley is defined as the difference in height between the convex portion and the concave portion (that is, the height difference between the peak and the valley is defined by the height difference of the present invention. It does not mean the difference in height between the convex and concave parts). Further, the pitch of adjacent peaks is defined as the pitch of adjacent convex portions. The metal substrate for an electronic device has an inclined surface classified by the ridgeline of the continuous convex portion, and the inclined surface can effectively scatter light. Further, when an EL element or the like is laminated on the outer surface of the transparent conductive film, the outer surface of the transparent conductive film is smooth, that is, steep protrusions or holes are formed between the convex portion and the concave portion (the above-mentioned inclined surface). It is important that it is not done. In this regard, as shown in FIGS. 5 and 6, the metal substrate for an electronic device can realize a state without such steep protrusions and holes.
（金属板）
上記金属板は、金属を主成分とする。上記金属板の主成分としては、上述の鋼の他、例えば鉄、チタン、アルミニウム、銅等が挙げられる。上記金属板は、１種の金属によって形成されてもよく、２種以上の金属の合金によって形成されてもよい。つまり、上記金属板は、鉄、チタン、アルミニウム又は銅を主成分とする合金から形成されてもよい。上記金属板が合金から形成される場合、他の合金成分としては、例えばシリコン、アルミニウム、マンガン、マグネシウム、ニッケル、クロム、モリブデン、亜鉛、銅、バナジウム等が挙げられる。上記金属板が鉄、チタン、アルミニウム又は銅を主成分とすることによって、当該電子デバイス用金属基板の機械的強度や耐性を容易かつ確実に高めることができる。
(Metal plate)
The metal plate contains metal as a main component. Examples of the main component of the metal plate include iron, titanium, aluminum, copper and the like in addition to the above-mentioned steel. The metal plate may be formed of one kind of metal or may be formed of an alloy of two or more kinds of metals. That is, the metal plate may be formed of an alloy containing iron, titanium, aluminum or copper as a main component. When the metal plate is formed from an alloy, examples of other alloy components include silicon, aluminum, manganese, magnesium, nickel, chromium, molybdenum, zinc, copper, vanadium and the like. When the metal plate contains iron, titanium, aluminum or copper as a main component, the mechanical strength and resistance of the metal substrate for the electronic device can be easily and surely increased.
上記金属板の平均厚さとしては、特に限定されるものではなく、例えば０．１ｍｍ以上２．０ｍｍ以下とすることができる。 The average thickness of the metal plate is not particularly limited, and may be, for example, 0.1 mm or more and 2.0 mm or less.
（亜鉛めっき層）
上記金属板及び絶縁層は直接積層されていてもよいが、上述のように、上記金属板の絶縁層が積層される側の面には亜鉛めっき層が積層されていることが好ましい。当該電子デバイス用金属基板は、上記金属板の絶縁層が積層される側の面に亜鉛めっき層を備えることによって、防錆性を高めることができる。
(Galvanized layer)
The metal plate and the insulating layer may be directly laminated, but as described above, it is preferable that the zinc plating layer is laminated on the surface on the side where the insulating layer of the metal plate is laminated. The metal substrate for an electronic device can be improved in rust prevention by providing a galvanized layer on the surface on the side where the insulating layer of the metal plate is laminated.
上記亜鉛めっき層を形成する亜鉛めっきは、電気亜鉛めっき法によって形成されてもよく、溶融亜鉛めっき法によって形成されてもよい。上記亜鉛めっき層は、絶縁層との密着性を高めると共に、絶縁層の変形を吸収する機能を有している。上記亜鉛めっき層は、亜鉛以外の低融点の柔らかい金属を含んでいてもよく、例えばインジウム、アルミニウム、マグネシウム、錫及びこれらの合金等を含んでいてもよい。上記金属板及び亜鉛めっき層の積層構造の具体例としては、例えば溶融純亜鉛めっき鋼板（ＧＩ）、合金化溶融Ｚｎ−Ｆｅめっき鋼板（ＧＡ）、合金化溶融Ｚｎ−５％Ａｌめっき鋼板（ＧＦ）、電気純亜鉛めっき鋼板（ＥＧ）、電気Ｚｎ−Ｎｉめっき鋼板等が挙げられる。なお、上記亜鉛めっき層は、金属板の絶縁層が積層される側と反対側の面にも積層されていてもよい。 The zinc plating forming the zinc plating layer may be formed by an electrogalvanizing method or a hot-dip galvanizing method. The galvanized layer has a function of improving adhesion to the insulating layer and absorbing deformation of the insulating layer. The galvanized layer may contain a soft metal having a low melting point other than zinc, and may contain, for example, indium, aluminum, magnesium, tin and alloys thereof. Specific examples of the laminated structure of the metal plate and the galvanized layer include a hot-dip pure galvanized steel sheet (GI), an alloyed hot-dip Zn-Fe-plated steel sheet (GA), and an alloyed hot-dip Zn-5% Al-plated steel sheet (GF). ), Electric pure galvanized steel sheet (EG), electric Zn-Ni plated steel sheet and the like. The galvanized layer may also be laminated on the surface opposite to the side on which the insulating layer of the metal plate is laminated.
上記亜鉛めっき層の平均厚さは、後述の絶縁層と同程度かそれ以上であればよく、例えば１μｍ以上２００μｍ以下とすることができる。 The average thickness of the galvanized layer may be about the same as or greater than that of the insulating layer described later, and can be, for example, 1 μm or more and 200 μm or less.
（絶縁層）
上記絶縁層は絶縁性を有する。上記絶縁層は、合成樹脂を主成分とすることが好ましい。上記合成樹脂としては、熱硬化性樹脂、熱可塑性樹脂、光硬化性樹脂等が挙げられる。中でも、上記合成樹脂は、熱硬化性樹脂、又はその他の樹脂（例えば熱可塑性樹脂）と硬化剤とを組み合わせて用いることが好ましい。当該電子デバイス用金属基板は、上記絶縁層が合成樹脂を主成分とすることで、絶縁性の高い層を容易に形成することができる。また、上記合成樹脂が熱硬化性樹脂であることによって、上記絶縁層の形成が容易となる。一方、上記合成樹脂が熱可塑性樹脂であることで、上記絶縁層を比較的低コストで形成することができる。
(Insulation layer)
The insulating layer has an insulating property. The insulating layer preferably contains a synthetic resin as a main component. Examples of the synthetic resin include thermosetting resins, thermoplastic resins, and photocurable resins. Above all, it is preferable to use the synthetic resin in combination with a thermosetting resin or another resin (for example, a thermoplastic resin) and a curing agent. In the metal substrate for an electronic device, since the insulating layer contains a synthetic resin as a main component, a layer having high insulating properties can be easily formed. Further, since the synthetic resin is a thermosetting resin, the formation of the insulating layer becomes easy. On the other hand, since the synthetic resin is a thermoplastic resin, the insulating layer can be formed at a relatively low cost.
上記熱硬化性樹脂としては、特に限定されるものではなく、例えばフェノール樹脂、エポキシ樹脂、ユリア樹脂、メラミン樹脂、ジアリルフタレート樹脂等が挙げられる。 The thermosetting resin is not particularly limited, and examples thereof include phenol resin, epoxy resin, urea resin, melamine resin, diallyl phthalate resin and the like.
上記熱可塑性樹脂としては、ポリエステル、アクリル樹脂、ポリエチレン等が挙げられ、中でもポリエステル又はアクリル樹脂が好ましい。上記熱可塑性樹脂としてポリエステル又はアクリル樹脂を用いる場合、後述の硬化剤を添加することで、比較的安価に上記絶縁層を熱硬化性の樹脂組成物から形成することができる。 Examples of the thermoplastic resin include polyester, acrylic resin, polyethylene and the like, and polyester or acrylic resin is preferable. When polyester or acrylic resin is used as the thermoplastic resin, the insulating layer can be formed from the thermosetting resin composition at a relatively low cost by adding a curing agent described later.
ポリエステルは、二塩基酸等の多塩基酸と多価アルコール類との縮合反応によって得られるものである。ポリエステルの原料として用いられる多塩基酸（これらの誘導体を含む）としては、例えばマレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸等のα，β−不飽和二塩基酸；フタル酸、無水フタル酸、ハロゲン化無水フタル酸、イソフタル酸、テレフタル酸、テトラヒドロフタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロフタル酸、ヘキサヒドロイソフタル酸、ヘキサヒドロテレフタル酸、シクロペンタジエン−無水マレイン酸付加物、コハク酸、マロン酸、グルタル酸、アジピン酸、セバシン酸、１，１０−デカンジカルボン酸、２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、２，３−ナフタレンジカルボン酸、２，３−ナフタレンジカルボン酸無水物、４，４’−ビフェニルジカルボン酸、又はこれらのジアルキルエステル等の飽和二塩基酸などが挙げられるが、特に限定されるものではない。これらの多塩基酸は、１種類のみを用いてもよいし、適宜、２種類以上を混合して用いてもよい。 Polyester is obtained by a condensation reaction between a polybasic acid such as a dibasic acid and a polyhydric alcohol. Examples of polybasic acids (including derivatives of these) used as raw materials for polyester include α, β-unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic anhydride; phthalic acid. , Phthalic anhydride, phthalic acid halide, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, cyclopentadiene-maleic anhydride adduct, Succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,10-decandicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3 Examples thereof include −naphthalenedicarboxylic acid anhydride, 4,4′-biphenyldicarboxylic acid, and saturated dibasic acids such as dialkyl esters thereof, but the present invention is not particularly limited. Only one kind of these polybasic acids may be used, or two or more kinds may be mixed and used as appropriate.
ポリエステルの原料として用いられる多価アルコール類としては、例えばエチレングリコール、ジエチレングリコール、ポリエチレングリコール等のエチレングリコール類、プロピレングリコール、ジプロピレングリコール、ポリプロピレングリコール等のプロピレングリコール類、２−メチル−１，３−プロパンジオール、１，３−ブタンジオール、ビスフェノールＡとプロピレンオキシド又はエチレンオキシドとの付加物、グリセリン、トリメチロールプロパン、１，３−プロパンジオール、１，２−シクロヘキサングリコール、１，３−シクロヘキサングリコール、１，４−シクロヘキサングリコール、パラキシレングリコール、ビシクロヘキシル−４，４′−ジオール、２，６−デカリングリコール、トリス（２−ヒドロキシエチル）イソシアヌレートなどが挙げられるが、特に限定されるものではない。また、エタノールアミン等のアミノアルコール類を用いてもよい。これらの多価アルコール類は、１種類のみを用いてもよいし、適宜、２種類以上を混合してもよい。 Examples of polyhydric alcohols used as raw materials for polyester include ethylene glycols such as ethylene glycol, diethylene glycol and polyethylene glycol, propylene glycols such as propylene glycol, dipropylene glycol and polypropylene glycol, 2-methyl-1,3-. Propanediol, 1,3-butanediol, adduct of bisphenol A and propylene oxide or ethylene oxide, glycerin, trimethylpropane, 1,3-propanediol, 1,2-cyclohexaneglycol, 1,3-cyclohexaneglycol, 1 , 4-Cyclohexaneglycol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, tris (2-hydroxyethyl) isocyanurate and the like, but are not particularly limited. Further, amino alcohols such as ethanolamine may be used. Only one kind of these polyhydric alcohols may be used, or two or more kinds may be mixed as appropriate.
また、ポリエステルは、必要によりエポキシ樹脂、ジイソシアナート、ジシクロペンタジエン等による変性を行ってもよい。 Further, the polyester may be modified with an epoxy resin, diisocyanate, dicyclopentadiene or the like, if necessary.
上記絶縁層に用いる樹脂としては、種々の市販品を好適に用いることができ、特にポリエステルの市販品としては、例えばバイロン（登録商標）２３ＣＳ、バイロン（登録商標）２９ＣＳ、バイロン（登録商標）２９ＸＳ、バイロン（登録商標）２０ＳＳ、バイロン（登録商標）２９ＳＳ（以上、東洋紡社製）等を挙げることができる。 As the resin used for the insulating layer, various commercially available products can be preferably used. In particular, as commercially available polyester products, for example, Byron (registered trademark) 23CS, Byron (registered trademark) 29CS, Byron (registered trademark) 29XS , Byron (registered trademark) 20SS, Byron (registered trademark) 29SS (all manufactured by Toyobo Co., Ltd.) and the like.
上記絶縁層は有機溶媒には溶解しないものとするが、成形時に用いる溶媒が層内に浸入して膨潤等の変質が生じるおそれがある。これを抑制するため、合成樹脂として熱硬化性樹脂を使用する場合も所定量の硬化剤を含有させることによって、上記絶縁層の硬化度（架橋密度）を高めることが有効となる。 The insulating layer is not soluble in an organic solvent, but the solvent used during molding may infiltrate into the layer and cause deterioration such as swelling. In order to suppress this, even when a thermosetting resin is used as the synthetic resin, it is effective to increase the degree of curing (crosslink density) of the insulating layer by containing a predetermined amount of a curing agent.
上記硬化剤としては、特に限定されるものではないが、ポリエステルや熱硬化性樹脂との相溶性がよく、ポリエステルや熱硬化性樹脂を架橋させることができ、更に液安定性のよい熱硬化剤が好ましい。このような熱硬化剤としては、例えばイソシアネート系では、ミリオネート（登録商標）Ｎ、コロネート（登録商標）Ｔ、コロネート（登録商標）ＨＬ、コロネート（登録商標）２０３０、スプラセック３３４０、ダルトセック１３５０、ダルトセック２１７０、ダルトセック２２８０（以上、日本ポリウレタン工業社製）等、メラミン樹脂系では、ニカラック（登録商標）ＭＳ−１１、ニカラック（登録商標）ＭＳ２１（以上、三和ケミカル社製）、スーパーベッカミン（登録商標）Ｌ−１０５−６０、スーパーベッカミン（登録商標）Ｊ−８２０−６０（以上、ＤＩＣ社製）、エポキシ系では、ハードナーＨＹ９５１、ハードナーＨＹ９５７（以上、ＢＡＳＦ社製）、スミキュアーＤＴＡ、スミキュアーＴＴＡ（以上、住友化学社製）等を挙げることができる。 The curing agent is not particularly limited, but is a thermosetting agent having good compatibility with polyester and a thermosetting resin, capable of cross-linking polyester and a thermosetting resin, and further having good liquid stability. Is preferable. Examples of such thermosetting agents include Millionate (registered trademark) N, Coronate (registered trademark) T, Coronate (registered trademark) HL, Coronate (registered trademark) 2030, Sprasec 3340, Daltsec 1350, and Daltsec 2170 in the case of isocyanate-based agents. , Dartsec 2280 (above, manufactured by Nippon Polyurethane Industry Co., Ltd.), etc. For melamine resins, Nicarac (registered trademark) MS-11, Nicarac (registered trademark) MS21 (above, manufactured by Sanwa Chemical Co., Ltd.), Super Beccamin (registered trademark) ) L-105-60, Super Beccamin (registered trademark) J-820-60 (above, manufactured by DIC), Hardener HY951, Hardener HY957 (above, manufactured by BASF), SumiCure DTA, SumiCure TTA (above, manufactured by DIC) As mentioned above, Sumitomo Chemical Co., Ltd.) and the like can be mentioned.
上記絶縁層における合成樹脂の含有率の下限としては、２６．５質量％が好ましく、３６．０質量％がより好ましい。一方、合成樹脂の含有率の上限としては８０．０質量％が好ましく、５６．３質量％がより好ましい。このような合成樹脂の含有率とすることで、当該電子デバイス用金属基板に好適な絶縁層を形成することができる。なお、合成樹脂の含有率は、上記絶縁層中の固形分（合成樹脂、硬化剤等）の合計質量に対する合成樹脂の含有量の比率を指す。後述の硬化剤等の含有率も同様である。 The lower limit of the content of the synthetic resin in the insulating layer is preferably 26.5% by mass, more preferably 36.0% by mass. On the other hand, the upper limit of the content of the synthetic resin is preferably 80.0% by mass, more preferably 56.3% by mass. By setting the content of such a synthetic resin, an insulating layer suitable for the metal substrate for the electronic device can be formed. The synthetic resin content refers to the ratio of the synthetic resin content to the total mass of the solid content (synthetic resin, curing agent, etc.) in the insulating layer. The content of the curing agent and the like described later is also the same.
上記絶縁層における硬化剤は、後述の透明導電膜の外面に形成される凹凸形状を制御するために重要である。上記絶縁層における硬化剤の含有率の下限としては、１０．０質量％が好ましく、２０．０質量％がより好ましい。一方、上記硬化剤の含有率の上限としては、５０．０質量％が好ましい。このような硬化剤の含有率とすることで、透明導電膜の外面の凹凸形状を適切に制御することができる。 The curing agent in the insulating layer is important for controlling the uneven shape formed on the outer surface of the transparent conductive film described later. The lower limit of the content of the curing agent in the insulating layer is preferably 10.0% by mass, more preferably 20.0% by mass. On the other hand, the upper limit of the content of the curing agent is preferably 50.0% by mass. By setting the content of such a curing agent, the uneven shape of the outer surface of the transparent conductive film can be appropriately controlled.
上記絶縁層における合成樹脂に対する硬化剤の質量比の下限としては、０．３０が好ましく、０．４０がより好ましく、０．６５がさらに好ましい。一方、上記質量比の上限としては、１．０が好ましい。 The lower limit of the mass ratio of the curing agent to the synthetic resin in the insulating layer is preferably 0.30, more preferably 0.40, and even more preferably 0.65. On the other hand, the upper limit of the mass ratio is preferably 1.0.
上記絶縁層がポリエステルや熱硬化性樹脂を含む場合、硬化時に体積収縮が生じたり溶剤揮発ガス成分の影響で表面形状が大きくうねったり、急峻な凹凸ができたりする場合がある。そこで、顔料を上記絶縁層に混合することで、合成樹脂の収縮の抑制や溶剤ガス脱離を促進することができるため所望の表面形状を得やすい。一方で、顔料の添加により、表面粗さが大きくなって表面に突起や窪みが多く形成され得る。そのため、混合する顔料の粒径や添加量を調整してもよい。 When the insulating layer contains polyester or a thermosetting resin, volume shrinkage may occur during curing, the surface shape may be greatly undulated due to the influence of the solvent volatile gas component, or steep irregularities may be formed. Therefore, by mixing the pigment with the insulating layer, it is possible to suppress the shrinkage of the synthetic resin and promote the desorption of the solvent gas, so that it is easy to obtain a desired surface shape. On the other hand, the addition of the pigment may increase the surface roughness and form many protrusions and dents on the surface. Therefore, the particle size and the amount of the pigment to be mixed may be adjusted.
上記絶縁層の平均厚さの下限としては、１μｍが好ましく、１０μｍがより好ましい。一方、上記絶縁層の平均厚さの上限としては、１００μｍが好ましく、８０μｍがより好ましい。上記絶縁層の平均厚さが上記下限より小さいと、絶縁性が不十分となるおそれがある。逆に、上記絶縁層の平均厚さが上記上限を超えると、当該電子デバイス用金属基板の可撓性が不十分となるおそれがある。 As the lower limit of the average thickness of the insulating layer, 1 μm is preferable, and 10 μm is more preferable. On the other hand, the upper limit of the average thickness of the insulating layer is preferably 100 μm, more preferably 80 μm. If the average thickness of the insulating layer is smaller than the lower limit, the insulating property may be insufficient. On the contrary, if the average thickness of the insulating layer exceeds the upper limit, the flexibility of the metal substrate for the electronic device may be insufficient.
（透明導電膜）
上記透明導電膜の具体的構成としては、特に限定されるものではないが、例えば少なくともＩｎ及びＳｎを含む酸化物からなる透明導電膜（ＩＴＯ；Ｉｎ−Ｓｎ−Ｏ）、少なくともＩｎ及びＺｎを含む酸化物からなる透明導電膜（ＩＺＯ；Ｉｎ−Ｚｎ−Ｏ）、少なくともＩｎ及びＧａを含む酸化物からなる透明導電膜（ＩＧＯ；Ｉｎ−Ｇａ−Ｏ）、少なくともＺｎを含む酸化物からなる透明導電膜（ＺｎＯ；Ｚｎ−Ｏ）、又は少なくともＡｌ及びＺｎを含む酸化物からなる透明導電膜（ＡｌＺｎＯ；Ａｌ−Ｚｎ−Ｏ）等が挙げられる。
(Transparent conductive film)
The specific configuration of the transparent conductive film is not particularly limited, but includes, for example, a transparent conductive film (ITO; In—Sn—O) composed of an oxide containing at least In and Sn, and at least In and Zn. A transparent conductive film made of an oxide (IZO; In—Zn—O), a transparent conductive film made of an oxide containing at least In and Ga (IGO; In—Ga—O), and a transparent conductive film made of an oxide containing at least Zn. Examples thereof include a film (ZnO; Zn—O) or a transparent conductive film (AlZnO; Al—Zn—O) made of an oxide containing at least Al and Zn.
上述のように、上記透明導電膜の外面には微細凹凸形状が形成されている。この微細凹凸形状の凸部の頂点の平均ピッチの下限としては、上述のように５μｍであり、８μｍが好ましく、１０μｍがより好ましい。一方、上記平均ピッチの上限としては、上述のように５０μｍであり、３０μｍが好ましく、２０μｍがより好ましい。上記平均ピッチが上記下限より小さいと、急峻な凸部及び急峻な凹部が形成されることで、素子の短絡を招来するおそれがある。一方、上記平均ピッチが上記上限を超えると、光散乱機能が不十分となるおそれがある。 As described above, a fine uneven shape is formed on the outer surface of the transparent conductive film. As described above, the lower limit of the average pitch of the vertices of the convex portions of the fine concavo-convex shape is 5 μm, preferably 8 μm, and more preferably 10 μm. On the other hand, the upper limit of the average pitch is 50 μm as described above, preferably 30 μm, and more preferably 20 μm. If the average pitch is smaller than the lower limit, a steep convex portion and a steep concave portion are formed, which may lead to a short circuit of the element. On the other hand, if the average pitch exceeds the upper limit, the light scattering function may be insufficient.
また、隣接する凸部の頂点及び凹部の底点の高さの差の平均値の下限としては、上述のように５０ｎｍであり、７０ｎｍが好ましく、１５０ｎｍがより好ましい。一方、上記平均値の上限としては、上述のように３００ｎｍであり、２５０ｎｍが好ましい。上記平均値が上記下限より小さいと、光散乱機能が不十分となるおそれがある。逆に、上記平均値が上記上限を超えると、急峻な凸部及び急峻な凹部が形成されることで、素子の短絡を招来するおそれがある。 Further, the lower limit of the average value of the height difference between the apex of the adjacent convex portion and the bottom point of the concave portion is 50 nm, preferably 70 nm, and more preferably 150 nm as described above. On the other hand, the upper limit of the average value is 300 nm as described above, preferably 250 nm. If the average value is smaller than the lower limit, the light scattering function may be insufficient. On the contrary, when the average value exceeds the upper limit, a steep convex portion and a steep concave portion are formed, which may cause a short circuit of the element.
当該電子デバイス用金属基板の入射角−５度とした場合の反射角１５度における拡散反射率の下限としては、５％が好ましく、６％がより好ましい。また、当該電子デバイス用金属基板の入射角−５度とした場合の反射角２５度における拡散反射率の下限としては、１．５％が好ましく、１．７％がより好ましい。上記拡散反射率が上記下限に満たないと、例えば当該電子デバイス用金属基板をＥＬ素子の構成要素として用いた場合に、このＥＬ素子の光取り出し率を十分に高めることができないおそれがある。なお、当該電子デバイス用金属基板の入射角−５度とした場合の反射角１５度における拡散反射率の上限としては、特に限定されないが、例えば１０％とすることができる。また、当該電子デバイス用金属基板の入射角−５度とした場合の反射角２５度における拡散反射率の上限としては、特に限定されないが、例えば５．０％とすることができる。 The lower limit of the diffuse reflectance at a reflection angle of 15 degrees when the incident angle of the metal substrate for an electronic device is −5 degrees is preferably 5%, more preferably 6%. Further, the lower limit of the diffuse reflectance at a reflection angle of 25 degrees when the incident angle of the metal substrate for an electronic device is −5 degrees is preferably 1.5%, more preferably 1.7%. If the diffuse reflectance does not reach the lower limit, for example, when the metal substrate for an electronic device is used as a component of the EL element, the light extraction rate of the EL element may not be sufficiently increased. The upper limit of the diffuse reflectance at a reflection angle of 15 degrees when the incident angle of the metal substrate for an electronic device is −5 degrees is not particularly limited, but may be, for example, 10%. Further, the upper limit of the diffuse reflectance at a reflection angle of 25 degrees when the incident angle of the metal substrate for an electronic device is −5 degrees is not particularly limited, but may be, for example, 5.0%.
当該電子デバイスは、例えば上記透明導電膜の外面が有機ＥＬ素子の有機発光層に積層された状態で用いることができる。この場合、上記有機発光層の当該電子デバイス用金属基板の積層面と反対側の面には透明な電子デバイス用金属基板が積層され、光取り出し側の面を構成することが好ましい。このように、当該電子デバイス用金属基板は、有機ＥＬ照明に用いられることで、ＥＬ素子の光取り出し率を向上することができる。 The electronic device can be used, for example, in a state where the outer surface of the transparent conductive film is laminated on the organic light emitting layer of the organic EL element. In this case, it is preferable that a transparent metal substrate for an electronic device is laminated on the surface of the organic light emitting layer opposite to the laminated surface of the metal substrate for the electronic device to form a surface on the light extraction side. As described above, the metal substrate for an electronic device can be used for organic EL lighting to improve the light extraction rate of the EL element.
また、当該電子デバイスは、上記透明導電膜の外面が有機太陽電池の電子供与体に積層された状態で用いられてもよい。つまり、当該電子デバイス用金属基板は、有機太陽電池に用いられてもよい。 Further, the electronic device may be used in a state where the outer surface of the transparent conductive film is laminated on the electron donor of the organic solar cell. That is, the metal substrate for the electronic device may be used for an organic solar cell.
＜製造方法＞
当該電子デバイス用金属基板の製造方法は、例えば金属板を用意する工程（金属板用意工程）と、金属板の表面に亜鉛めっきを施す工程（亜鉛めっき工程）と、上記亜鉛めっき工程で形成された亜鉛めっき層の外面に絶縁層を積層する工程（絶縁層積層工程）と、上記絶縁層積層工程で積層された絶縁層の外面に透明導電膜を積層する工程（透明導電膜積層工程）とを備える。なお、当該電子デバイス用金属基板が亜鉛めっき層を有しない場合、上記亜鉛めっき工程は省略することが可能である。
<Manufacturing method>
The method for manufacturing the metal substrate for an electronic device is formed by, for example, a step of preparing a metal plate (metal plate preparation step), a step of performing zinc plating on the surface of the metal plate (zinc plating step), and the above-mentioned zinc plating step. A step of laminating an insulating layer on the outer surface of the zinc plating layer (insulating layer laminating step) and a step of laminating a transparent conductive film on the outer surface of the insulating layer laminated in the above insulating layer laminating step (transparent conductive film laminating step). To be equipped. If the metal substrate for the electronic device does not have a galvanized layer, the galvanized step can be omitted.
（亜鉛めっき工程）
上記亜鉛めっき工程は、公知の電気亜鉛めっき法又は溶融亜鉛めっき法によって行うことができる。
(Galvanization process)
The zinc plating step can be performed by a known electrogalvanization method or hot-dip galvanization method.
（絶縁層積層工程）
上記絶縁層積層工程は、上記亜鉛めっき層の外面への絶縁層形成用組成物の塗布及び加熱により塗膜を形成する工程（塗膜形成工程）と、上記塗膜形成工程によって得られた塗膜の外面を平滑化する工程（平滑化工程）とを有する。なお、上記絶縁層形成用組成物は液状であることが好ましい。つまり、上記絶縁層形成用組成物は溶媒を含むことが好ましい。
(Insulation layer laminating process)
The insulating layer laminating step includes a step of forming a coating film by applying and heating the composition for forming an insulating layer on the outer surface of the zinc plating layer (coating film forming step), and a coating obtained by the coating film forming step. It has a step of smoothing the outer surface of the film (smoothing step). The composition for forming an insulating layer is preferably liquid. That is, it is preferable that the composition for forming an insulating layer contains a solvent.
上記絶縁層形成用組成物に用いる溶媒は、絶縁層形成用組成物が含有すべき各成分を溶解又は分散させ得るものであれば、特に制限はない。上記溶媒としては、例えばメタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール、エチレングリコール等のアルコール類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；トルエン、ベンゼン、キシレン、ソルベッソ（登録商標）１００（エクソンモービル社製）、ソルベッソ（登録商標）１５０（エクソンモービル社製）等の芳香族炭化水素類；ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素類；酢酸エチル、酢酸ブチル等のエステル類などが挙げられる。上記絶縁層形成用組成物は、これらの溶媒を用いて固形分濃度を調整することができる。 The solvent used in the insulating layer forming composition is not particularly limited as long as it can dissolve or disperse each component to be contained in the insulating layer forming composition. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and ethylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; toluene, benzene and xylene. Aromatic hydrocarbons such as Solvesso (registered trademark) 100 (manufactured by Exxon Mobile) and Solvesso (registered trademark) 150 (manufactured by Exxon Mobile); aliphatic hydrocarbons such as hexane, heptane and octane; ethyl acetate, acetate Examples thereof include esters such as butyl. The solid content concentration of the insulating layer forming composition can be adjusted by using these solvents.
上記絶縁層形成用組成物の固形分濃度の下限としては、２０質量％が好ましく、４０質量％がより好ましい。一方、上記絶縁層形成用組成物の固形分濃度の上限としては、８０質量％が好ましく、７０質量％がより好ましい。上記固形分濃度が上記下限より小さい場合、すなわち溶媒が多すぎる場合、加熱時に溶媒が大量に蒸発し、その結果、金属板の表面近傍において気化した溶媒による対流が発生しやすくなり、上記絶縁層の外面の平滑性が損なわれやすくなるおそれがある。逆に、上記固形分濃度が上記上限を超えると、上記絶縁層形成用組成物の塗布が困難になるおそれがある。 The lower limit of the solid content concentration of the insulating layer forming composition is preferably 20% by mass, more preferably 40% by mass. On the other hand, the upper limit of the solid content concentration of the insulating layer forming composition is preferably 80% by mass, more preferably 70% by mass. When the solid content concentration is smaller than the above lower limit, that is, when the amount of solvent is too large, a large amount of solvent evaporates during heating, and as a result, convection due to the vaporized solvent is likely to occur near the surface of the metal plate, and the insulating layer The smoothness of the outer surface of the solvent may be easily impaired. On the contrary, if the solid content concentration exceeds the upper limit, it may be difficult to apply the composition for forming an insulating layer.
〔塗膜形成工程〕
上記絶縁層形成用組成物の塗布及び加熱（乾燥並びに焼付）方法は、特に制限されず、既知の方法を適宜採用することができる。上記塗布方法としては、例えばバーコーター法、ロールコーター法、カーテンフローコーター法、スプレー法、スプレーリンガー法等を挙げることができ、これらの中でも、コスト等の観点からバーコーター法、ロールコーター法、及びスプレーリンガー法が好ましい。
[Coating film forming process]
The method of applying and heating (drying and baking) the composition for forming an insulating layer is not particularly limited, and a known method can be appropriately adopted. Examples of the coating method include a bar coater method, a roll coater method, a curtain flow coater method, a spray method, a spray ringer method, and the like. Among these, the bar coater method, the roll coater method, and the like from the viewpoint of cost and the like. And the spray ringer method is preferred.
上記絶縁層形成用組成物の加熱温度の下限としては、１９０℃が好ましく、２００℃がより好ましい。一方、上記加熱温度の上限としては、２５０℃が好ましく、２４０℃がより好ましい。上記加熱温度が上記下限より低いと、絶縁層の強度が不十分となるおそれがある。逆に、上記加熱温度が上記上限を超えると、溶媒を激しく蒸発させないようにすることによって、金属板の表面近傍において気化した溶媒による対流が発生しやすくなり、絶縁層の表面の平滑性が損なわれるおそれがある。また、上記加熱温度が上記上限を超えると、樹脂が硬化し過ぎることで、透明導電膜積層時の樹脂の変形が妨げられ、透明導電膜の外面に所望の凹凸形状を形成し難くなるおそれがある。なお、加熱温度とは、到達板温（Ｐｅａｋ Ｍｅｔａｌ Ｔｅｍｐｅｒａｔｕｒｅ：ＰＭＴ）を指す。 The lower limit of the heating temperature of the composition for forming an insulating layer is preferably 190 ° C., more preferably 200 ° C. On the other hand, the upper limit of the heating temperature is preferably 250 ° C., more preferably 240 ° C. If the heating temperature is lower than the lower limit, the strength of the insulating layer may be insufficient. On the contrary, when the heating temperature exceeds the above upper limit, convection due to the vaporized solvent is likely to occur in the vicinity of the surface of the metal plate by preventing the solvent from evaporating violently, and the smoothness of the surface of the insulating layer is impaired. There is a risk of Further, if the heating temperature exceeds the above upper limit, the resin may be excessively cured, which may prevent deformation of the resin during laminating the transparent conductive film and make it difficult to form a desired uneven shape on the outer surface of the transparent conductive film. is there. The heating temperature refers to the reaching plate temperature (Peek Metal Temperature: PMT).
〔平滑化工程〕
上記平滑化工程では、例えば研磨処理によって絶縁層の外面を研磨してもよく、絶縁層の外面に平滑化膜を形成してもよい。上記研磨処理を施す場合の研磨方法としては、化学研磨（ＣＭＰ）、電解研磨、機械研磨等が挙げられる。これらの中でも、微細な凹凸を除去する観点から、研磨剤に例えばシリカ、アルミナ、セリア、チタニア、ジルコニア、ゲルマニア等を用いた化学電解研磨法が好ましい。
[Smoothing process]
In the smoothing step, the outer surface of the insulating layer may be polished by, for example, a polishing treatment, or a smoothing film may be formed on the outer surface of the insulating layer. Examples of the polishing method when performing the above polishing treatment include chemical polishing (CMP), electrolytic polishing, mechanical polishing and the like. Among these, from the viewpoint of removing fine irregularities, a chemical electropolishing method using, for example, silica, alumina, ceria, titania, zirconia, germania or the like as an abrasive is preferable.
（透明導電膜積層工程）
上記透明導電膜積層工程では、得られる透明導電膜の外面の凹凸形状を制御しつつ上記絶縁層の外面に透明導電膜を積層する。上記透明導電膜積層工程では、例えばＤＣマグネトロンスパッタリング法によって上記絶縁層の外面に透明導電膜を積層する。上記透明導電膜積層工程では、スパッタリングを行う成膜パワーを制御することで透明導電膜の外面の凹凸形状を制御することができる。上記成膜パワーの下限としては、２．０Ｗ／ｃｍ２が好ましく、３．０Ｗ／ｃｍ２がより好ましい。一方、上記成膜パワーの上限としては、５．０Ｗ／ｃｍ２が好ましく、４．５Ｗ／ｃｍ２がより好ましい。上記成膜パワーが上記下限に満たないと、透明導電膜の外面に十分な凹凸形状を付与することができないおそれがある。逆に、上記成膜パワーが上記上限を超えると、上記透明導電膜の外面の凹凸が大きくなり過ぎて、素子の短絡を招来するおそれがある。
(Transparent conductive film laminating process)
In the transparent conductive film laminating step, the transparent conductive film is laminated on the outer surface of the insulating layer while controlling the uneven shape of the outer surface of the obtained transparent conductive film. In the transparent conductive film laminating step, the transparent conductive film is laminated on the outer surface of the insulating layer by, for example, a DC magnetron sputtering method. In the transparent conductive film laminating step, the uneven shape of the outer surface of the transparent conductive film can be controlled by controlling the film forming power for sputtering. As the lower limit of the film forming power, 2.0 W / cm 2 is preferable, and 3.0 W / cm 2 is more preferable. On the other hand, as the upper limit of the film forming power, 5.0 W / cm 2 is preferable, and 4.5 W / cm 2 is more preferable. If the film forming power does not reach the lower limit, it may not be possible to impart a sufficient uneven shape to the outer surface of the transparent conductive film. On the contrary, if the film forming power exceeds the upper limit, the unevenness of the outer surface of the transparent conductive film becomes too large, which may cause a short circuit of the element.
＜利点＞
当該電子デバイス用金属基板は、上記透明導電膜の外面に形成される微細凹凸形状の凸部の頂点の平均ピッチ、並びに隣接する凸部の頂点及び凹部の底点の高さの差の平均値が上記範囲内であるので、上記透明導電膜の外面が、滑らかで、かつ十分な表面粗さを有する凹凸面として形成される。そのため、当該電子デバイス用金属基板は、光散乱機能に優れると共に厚さの不均一性に起因する素子の短絡を抑制することができる。
<Advantage>
The metal substrate for an electronic device has an average value of the average pitch of the vertices of the convex portions having a fine concave-convex shape formed on the outer surface of the transparent conductive film, and the average value of the height differences between the vertices of the adjacent convex portions and the bottom points of the concave portions. Is within the above range, the outer surface of the transparent conductive film is formed as an uneven surface that is smooth and has sufficient surface roughness. Therefore, the metal substrate for an electronic device is excellent in light scattering function and can suppress a short circuit of an element due to non-uniformity of thickness.
当該電子デバイス用金属基板の製造方法は、光散乱機能に優れると共に厚さの不均一性に起因する素子の短絡を抑制可能な電子デバイス用金属基板を容易かつ確実に製造することができる。 The method for manufacturing a metal substrate for an electronic device can easily and surely manufacture a metal substrate for an electronic device which is excellent in light scattering function and can suppress a short circuit of an element due to non-uniformity of thickness.
以下、実施例を挙げて本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
［実施例］
（Ｎｏ．１〜Ｎｏ．３）
キシレン（沸点：１４０℃）とシクロヘキサノン（沸点：１５６℃）とを等量ずつ混合した溶媒に、ポリエステル（東洋紡社の「バイロン（登録商標）２００」（ガラス転移点Ｔｇ：５３℃、数平均分子量Ｍｎ：３０００））を固形分換算で７５質量部、メラミン樹脂（ＤＩＣ社の「スーパーベッカミン（登録商標）Ｊ−８２０−６０」）を固形分換算で２５質量部加えて、塗料Ａを得た。なお、ポリエステルとメラミン樹脂との合計固形分が５８質量％となるようにキシレンとシクロヘキサノンとの混合溶媒の量を調整した。
[Example]
(No. 1 to No. 3)
Polyester (Toyobo's "Byron (registered trademark) 200" (glass transition point Tg: 53 ° C., number average molecular weight) in a solvent in which xylene (boiling point: 140 ° C.) and cyclohexanone (boiling point: 156 ° C.) are mixed in equal amounts. Mn: 3000)) was added in 75 parts by mass in terms of solid content, and melamine resin (DIC's "Super Beccamin (registered trademark) J-820-60") was added in 25 parts by mass in terms of solid content to obtain paint A. It was. The amount of the mixed solvent of xylene and cyclohexanone was adjusted so that the total solid content of the polyester and the melamine resin was 58% by mass.
板厚０．８ｍｍの金属板を用意し、この金属板の両面に各面当たりの亜鉛めっき付着量が２０ｇ／ｍ２となるよう電気亜鉛めっき法により亜鉛めっき層を積層した。一方の亜鉛めっき層の外面に上記塗料Ａをバーコーターで塗布し、到達板温（ＰＭＴ）が２２０℃となるように２分間加熱し、平均厚さが１５μｍの絶縁層を積層した。 A metal plate having a plate thickness of 0.8 mm was prepared, and zinc plating layers were laminated on both sides of the metal plate by an electrogalvanization method so that the amount of zinc plating adhered to each surface was 20 g / m 2 . The coating material A was applied to the outer surface of one of the galvanized layers with a bar coater, heated for 2 minutes so that the ultimate plate temperature (PMT) was 220 ° C., and an insulating layer having an average thickness of 15 μm was laminated.
次に、化学機械研磨行うことによって、絶縁層の外面を平滑にした。具体的には、研磨装置の基板取り付け用吸着パッドを貼り付けたホルダーに金属板、亜鉛めっき層及び絶縁層からなる積層体をセットし、絶縁層を下側にして研磨装置の定盤に取り付けた研磨パッドの上にセットした。研磨剤として粒状のアルミナ（平均粒径は約１００ｎｍ）を用い、圧力６５ｇ／ｃｍ２、１周当たりの回転距離を１ｍ、上記積層体と定盤との各回転速度を５０ｒｐｍとし、１０分間化学機械研磨を行った。研磨深さは、研磨量換算で６μｍとした。 Next, the outer surface of the insulating layer was smoothed by performing chemical mechanical polishing. Specifically, a laminate consisting of a metal plate, a galvanized layer, and an insulating layer is set in a holder to which a suction pad for mounting a substrate of the polishing device is attached, and the laminated body is attached to the surface plate of the polishing device with the insulating layer facing down. It was set on the polishing pad. Granular alumina (average particle size is about 100 nm) is used as an abrasive, the pressure is 65 g / cm 2 , the rotation distance per circumference is 1 m, the rotation speed between the laminate and the surface plate is 50 rpm, and chemical treatment is performed for 10 minutes. Mechanical polishing was performed. The polishing depth was 6 μm in terms of polishing amount.
研磨後、スパッタ装置を用いて、絶縁層の外面に平均厚さ２００ｎｍのＩＴＯ膜を成膜し、Ｎｏ．１〜Ｎｏ．３の電子デバイス用金属基板を得た。成膜装置としては、島津製作所製の「ＨＭＳ−５５２」を用い、背圧は１．０×１０−６Ｔｏｒｒ以下、プロセスガスにはＡｒを用い、プロセスガス圧は２ｍＴｏｒｒとした。ＩＴＯと絶縁層との極間距離は５０ｍｍ、成膜温度は室温（２５℃）とした。成膜パワーは、Ｎｏ．１では３．８Ｗ／ｃｍ２、Ｎｏ．２では３．１Ｗ／ｃｍ２、Ｎｏ．３では２．５Ｗ／ｃｍ２とした。 After polishing, an ITO film having an average thickness of 200 nm was formed on the outer surface of the insulating layer using a sputtering device. 1-No. 3 metal substrates for electronic devices were obtained. As the film forming apparatus, "HMS-552" manufactured by Shimadzu Corporation was used, the back pressure was 1.0 × 10-6 Torr or less, Ar was used as the process gas, and the process gas pressure was 2 mTorr. The distance between the electrodes of ITO and the insulating layer was 50 mm, and the film formation temperature was room temperature (25 ° C.). The film formation power is No. In 1, 3.8 W / cm 2 , No. In 2, 3.1 W / cm 2 , No. In 3, it was set to 2.5 W / cm 2 .
＜外面形状＞
Ｎｏ．１〜Ｎｏ．３の電子デバイス用金属基板のＩＴＯ膜の外面の形状をＳＩＩナノテクノロジー社製の原子間力顕微鏡（「ＳＰＩ４０００」）を用いて評価長さ１００μｍで測定した。この測定結果を図７〜図９に示す。
<Outer surface shape>
No. 1-No. The shape of the outer surface of the ITO film of the metal substrate for electronic devices of No. 3 was measured with an evaluation length of 100 μm using an atomic force microscope (“SPI4000”) manufactured by SII Nanotechnology. The measurement results are shown in FIGS. 7 to 9.
光散乱性に優れ、有機ＥＬ素子が短絡なく形成されるためには、電子デバイス用金属基板のＩＴＯ膜の外面が十分な表面粗さを有しつつ、滑らかに形成されることが重要である。この点に関し、十分な表面粗さ、及び表面の滑らかさは以下の指標により評価することができる。即ち、まず表面粗さを原子間力顕微鏡等の測定装置によって評価長さ１００μｍで測定する。ここで、表面粗さは、数ｎｍから１μｍ程度の評価領域となる。この表面粗さの測定結果から、凹凸の程度と滑らかさの程度とを評価する。凹凸の程度の評価指標としては、隣接する凸部の頂点及び凹部の底点の高さの差の平均値を用いる。また、滑らかさの程度の評価指標としては、凸部の頂点の平均ピッチを用いる。上記測定結果に基づくＮｏ．１〜Ｎｏ．３の電子デバイス用金属基板のＩＴＯ膜の外面の凸部の頂点の平均ピッチ、及び隣接する凸部の頂点及び凹部の底点の高さの差の平均値を表１に示す。 In order to have excellent light scattering properties and to form an organic EL element without a short circuit, it is important that the outer surface of the ITO film of the metal substrate for an electronic device is smoothly formed while having sufficient surface roughness. .. In this regard, sufficient surface roughness and surface smoothness can be evaluated by the following indexes. That is, first, the surface roughness is measured with an evaluation device such as an atomic force microscope with an evaluation length of 100 μm. Here, the surface roughness is in the evaluation region of about several nm to 1 μm. From the measurement result of the surface roughness, the degree of unevenness and the degree of smoothness are evaluated. As an evaluation index of the degree of unevenness, the average value of the height difference between the apex of the adjacent convex portion and the bottom point of the concave portion is used. Further, as an evaluation index of the degree of smoothness, the average pitch of the vertices of the convex portion is used. No. based on the above measurement results. 1-No. Table 1 shows the average pitch of the vertices of the convex portions on the outer surface of the ITO film of the metal substrate for electronic devices 3 and the average value of the height differences between the vertices of the adjacent convex portions and the bottom points of the concave portions.
＜拡散反射率＞
次に、分光光度計（日本分光社製の「Ｖ−５７０分光光度計」）を用いて、入射角−５度として波長５５０ｎｍの光を入射し、反射角を変えながら反射光の強度を測定した。さらに、５度〜８５度の反射光の合計が１００となるように反射光の相対反射率を求めた。この測定結果を図１０に示す。この測定結果から、反射角１５度及び反射角２５度の反射率を求めた。この測定結果を図１１及び図１２に示す。
<Diffuse reflectance>
Next, using a spectrophotometer (“V-570 spectrophotometer” manufactured by JASCO Corporation), light with a wavelength of 550 nm is incident at an incident angle of -5 degrees, and the intensity of the reflected light is measured while changing the reflection angle. did. Further, the relative reflectance of the reflected light was determined so that the total of the reflected light of 5 to 85 degrees was 100. The measurement result is shown in FIG. From this measurement result, the reflectance of a reflection angle of 15 degrees and a reflection angle of 25 degrees was determined. The measurement results are shown in FIGS. 11 and 12.
［比較例］
（Ｎｏ．４）
成膜パワーを１．９Ｗ／ｃｍ２とした以外は、Ｎｏ．１〜Ｎｏ．３と同様にして、Ｎｏ．４の電子デバイス用金属基板を得た。
[Comparison example]
(No. 4)
No. except that the film formation power was set to 1.9 W / cm 2 . 1-No. In the same manner as in No. 3. 4 metal substrates for electronic devices were obtained.
（Ｎｏ．５）
Ｎｏ．１〜Ｎｏ．３と同様の金属板を用意し、この金属板両面にＮｏ．１〜Ｎｏ．３と同様の亜鉛めっき層を積層することでＮｏ．５の電子デバイス用金属基板を得た。
(No. 5)
No. 1-No. Prepare the same metal plate as in No. 3 and No. 2 on both sides of this metal plate. 1-No. By laminating the same galvanized layer as in No. 3, No. 5 metal substrates for electronic devices were obtained.
（Ｎｏ．６）
亜鉛めっき層の外面に直接ＩＴＯ膜を成膜した以外はＮｏ．２と同様にしてＮｏ．６の電子デバイス用金属基板を得た。
(No. 6)
No. except that the ITO film was directly formed on the outer surface of the galvanized layer. No. 2 in the same manner as in 2. 6 metal substrates for electronic devices were obtained.
＜外面形状＞
Ｎｏ．４及びＮｏ．６の電子デバイス用金属基板のＩＴＯ膜の外面の形状、並びにＮｏ．５の電子デバイス用金属基板の亜鉛めっき層の外面の形状をＮｏ．１〜Ｎｏ．３と同様の原子間力顕微鏡を用い、評価長さ１００μｍで測定した。この測定結果を図１３〜図１５に示す。また、上記測定結果に基づくＮｏ．４及びＮｏ．６の電子デバイス用金属基板のＩＴＯ膜の外面、並びにＮｏ．５の電子デバイス用金属基板の亜鉛めっき層の外面の凸部の頂点の平均ピッチ、及び隣接する凸部の頂点及び凹部の底点の高さの差の平均値を表１に示す。
<Outer surface shape>
No. 4 and No. The shape of the outer surface of the ITO film of the metal substrate for electronic devices of No. 6 and No. The shape of the outer surface of the galvanized layer of the metal substrate for electronic devices of No. 5 is No. 1-No. Using the same atomic force microscope as in No. 3, the measurement was performed with an evaluation length of 100 μm. The measurement results are shown in FIGS. 13 to 15. In addition, No. based on the above measurement results. 4 and No. The outer surface of the ITO film of the metal substrate for electronic devices of No. 6 and No. Table 1 shows the average pitch of the apex of the convex portion on the outer surface of the galvanized layer of the metal substrate for electronic devices 5 and the average value of the height difference between the apex of the adjacent convex portion and the bottom point of the concave portion.
＜拡散反射率＞
Ｎｏ．１〜Ｎｏ．３と同様の分光光度計を用いて、入射角−５度として波長５５０ｎｍの光を入射し、反射角を変えながら反射光の強度を測定した。さらに、５度〜８５度の反射光の合計が１００となるように反射光の相対反射率を求めた。この測定結果を図１６に示す。この測定結果から、反射角１５度及び反射角２５度の反射率を求めた。この測定結果を図１７及び図１８に示す。
<Diffuse reflectance>
No. 1-No. Using the same spectrophotometer as in No. 3, light having a wavelength of 550 nm was incident at an incident angle of -5 degrees, and the intensity of the reflected light was measured while changing the reflection angle. Further, the relative reflectance of the reflected light was determined so that the total of the reflected light of 5 to 85 degrees was 100. The measurement result is shown in FIG. From this measurement result, the reflectance of a reflection angle of 15 degrees and a reflection angle of 25 degrees was determined. The measurement results are shown in FIGS. 17 and 18.
［評価結果］
表１に示すように、Ｎｏ．１〜Ｎｏ．３の電子デバイス用金属基板は、凸部の頂点の平均ピッチが５μｍ以上であり、隣接する凸部の頂点及び凹部の底点の高さの差の平均値が５０ｎｍ以上である。これにより、Ｎｏ．１〜Ｎｏ．３の電子デバイス用金属基板は、１５度方向に反射される光強度が５．６％以上、２５度方向に反射される光強度が１．５％以上であり、優れた拡散反射機能を有している。
[Evaluation results]
As shown in Table 1, No. 1-No. In the metal substrate for electronic devices No. 3, the average pitch of the apex of the convex portion is 5 μm or more, and the average value of the height difference between the apex of the adjacent convex portion and the bottom point of the concave portion is 50 nm or more. As a result, No. 1-No. The metal substrate for electronic devices 3 has an excellent diffuse reflection function, having a light intensity reflected in the 15-degree direction of 5.6% or more and a light intensity reflected in the 25-degree direction of 1.5% or more. are doing.
これに対し、Ｎｏ．４〜Ｎｏ．６の電子デバイス用金属基板は、凸部の頂点の平均ピッチが５μｍ未満であり、隣接する凸部の頂点及び凹部の底点の高さの差の平均値が５０ｎｍ未満である。これにより、Ｎｏ．４〜Ｎｏ．６の電子デバイス用金属基板は、１５度方向に反射される光強度が２．１％以下、２５度方向に反射される光強度が０．６％以下であり、拡散反射機能が不十分となっている。 On the other hand, No. 4 to No. In the metal substrate for electronic devices No. 6, the average pitch of the apex of the convex portion is less than 5 μm, and the average value of the height difference between the apex of the adjacent convex portion and the bottom point of the concave portion is less than 50 nm. As a result, No. 4 to No. The metal substrate for electronic devices No. 6 has a light intensity of 2.1% or less reflected in the 15-degree direction and a light intensity of 0.6% or less reflected in the 25-degree direction, and the diffuse reflection function is insufficient. It has become.
以上説明したように、本発明の電子デバイス用金属基板は、透明導電膜の外面が滑らかであるため素子の短絡を抑制することができると共に、優れた拡散反射機能を有しているので、種々の面発光デバイスの基板として用いられる。 As described above, the metal substrate for an electronic device of the present invention has a smooth outer surface of the transparent conductive film, so that short circuits of elements can be suppressed, and the metal substrate has an excellent diffuse reflection function. It is used as a substrate for surface emitting devices.
Claims (10)
上記透明導電膜の外面に微細凹凸形状が形成され、
上記微細凹凸形状の凸部の頂点の平均ピッチが５μｍ以上５０μｍ以下で、かつ隣接する凸部の頂点及び凹部の底点の高さの差の平均値が５０ｎｍ以上３００ｎｍ以下である電子デバイス用金属基板。 A metal substrate for an electronic device in which an insulating layer and a transparent conductive film are laminated in this order on the surface of a metal plate.
A fine uneven shape is formed on the outer surface of the transparent conductive film,
Metal for electronic devices in which the average pitch of the vertices of the convex portion of the fine uneven shape is 5 μm or more and 50 μm or less, and the average value of the height difference between the apex of the adjacent convex portion and the bottom point of the concave portion is 50 nm or more and 300 nm or less. substrate.
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