TW201934677A - Transparent conductive film and method for producing same - Google Patents
Transparent conductive film and method for producing same Download PDFInfo
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Abstract
Description
本發明有關於透明基材之一面上形成之透明導電膜，尤其有關至少含有包含聚噻吩系化合物/聚苯乙烯磺酸之導電性高分子及包含矽烷化合物之無機系黏合劑之上述透明導電膜。The present invention relates to a transparent conductive film formed on one surface of a transparent substrate, and more particularly to the above-mentioned transparent conductive film containing at least a conductive polymer containing a polythiophene compound / polystyrene sulfonic acid and an inorganic adhesive containing a silane compound. .
噻吩系或苯胺系之高分子由於具有優異安定性及導電性，故而期待其作為有機導電性材料被活用。作為其活用之一，係於液晶顯示器、透明觸控面板等之各種裝置所用之透明電極及抗靜電膜中，利用使用有於上述高分子經附加摻雜劑之導電性高分子及無機系黏合劑之透明導電膜。Since thiophene-based or aniline-based polymers have excellent stability and electrical conductivity, they are expected to be utilized as organic conductive materials. As one of its uses, it is used in transparent electrodes and antistatic films used in various devices such as liquid crystal displays and transparent touch panels. It uses conductive polymers and inorganic adhesives that are used in the above polymers with additional dopants. Transparent conductive film.
透明導電膜就提高辨識性而言，要求如下特性：透過率高，塗佈偏差少，且如於裝置之製造步驟中搬送時不對塗膜造成損傷般之與無機系透明導電膜同等之擦傷性及硬度。近幾年來，對於各種裝置所用之透明電極及抗靜電膜之需求提高，對於透明導面膜亦要求效率良好地製造膜厚均一性優異之透明導電膜。In order to improve visibility, transparent conductive films are required to have the following characteristics: high transmittance, small coating variation, and scratch resistance equivalent to that of inorganic transparent conductive films, as the coating film is not damaged when transported in the device manufacturing process. And hardness. In recent years, the demand for transparent electrodes and antistatic films used in various devices has increased, and transparent conductive film has also been required to efficiently manufacture transparent conductive films with excellent film thickness uniformity.
例如，於專利文獻1中，記載有透明導電性薄片，其於透明基材上具備透明導電膜，前述透明導電膜包含導電性高分子及含矽烷化合物之粒子狀無機系黏合劑，前述導電性高分子配置於前述無機系黏合劑之粒子間。專利文獻1中，作為於透明基材上形成上述透明導電性薄片之方法之例，記載有使用透明導電膜形成用塗佈液之噴霧塗佈法。噴霧塗佈法由於可藉簡便裝置進行，可於短時間內廣範圍塗裝，故製造效率優異。 [先前技術文獻] [專利文獻]For example, Patent Document 1 describes a transparent conductive sheet having a transparent conductive film on a transparent substrate. The transparent conductive film includes a conductive polymer and a particulate inorganic adhesive containing a silane compound. The polymer is disposed between the particles of the inorganic adhesive. Patent Document 1 describes, as an example of a method for forming the transparent conductive sheet on a transparent substrate, a spray coating method using a coating liquid for forming a transparent conductive film. The spray coating method can be performed by a simple device, and can be applied in a wide range in a short period of time, so the manufacturing efficiency is excellent. [Prior Art Literature] [Patent Literature]
[專利文獻1] 日本特開2016-170914[Patent Document 1] Japanese Patent Laid-Open No. 2016-170914
[發明欲解決之課題][Questions to be Solved by the Invention]
使用含有作為導電性高分子之聚噻吩系化合物/聚苯乙烯磺酸(PEDOT/PSS)之透明導電膜形成用塗佈液，自透明導電膜形成用塗佈液製造透明導電性膜之情況下，透明導電膜平坦性差，於表面容易發生色偏差。又，透明導電膜之色偏差意指因塗膜中之厚度偏差而使塗膜之反射光譜變化故而反射色變化而見到所謂稱為虹彩模樣之塗膜虹色偏差般之狀態。透明導電膜表面之色偏差由於對裝置之辨識性造成不良影響故而欠佳。透明導電膜之色偏差問題，有時於使用噴霧塗佈法作為於透明基材上形成塗膜之方法之情況時發生。When a coating liquid for forming a transparent conductive film containing a polythiophene compound / polystyrenesulfonic acid (PEDOT / PSS) as a conductive polymer is used, and a transparent conductive film is produced from the coating liquid for forming a transparent conductive film , The transparent conductive film has poor flatness, and color deviation easily occurs on the surface. In addition, the color deviation of the transparent conductive film means a state in which the reflection color of the coating film changes due to the thickness deviation in the coating film and the reflection color changes, so that a so-called iridescent pattern of the coating film is seen. The color deviation on the surface of the transparent conductive film is not good because it adversely affects the visibility of the device. The problem of color deviation of a transparent conductive film sometimes occurs when a spray coating method is used as a method for forming a coating film on a transparent substrate.
本發明係解決上述問題者，以此為目的而提供平坦性優異、於表面難以發生色偏差之包含聚噻吩系化合物/聚苯乙烯磺酸之透明導電膜。 [用以解決課題之手段]The present invention solves the above problems, and provides a transparent conductive film containing a polythiophene compound / polystyrene sulfonic acid, which is excellent in flatness and hardly cause color deviation on the surface. [Means to solve the problem]
本發明提供一種透明導電膜，其係至少含有包含聚噻吩系化合物/聚苯乙烯磺酸之導電性高分子及包含矽烷化合物之無機系黏合劑且形成於透明基材之一面上之透明導電膜，且係 100~200nm厚， 將前述導電性高分子與前述無機系黏合劑之合計設為100時，具有7.5~15.0重量%之該導電性高分子含有率及 500~1500Ω/□之表面電阻值。The invention provides a transparent conductive film, which is a transparent conductive film formed at least on one side of a transparent substrate, which contains a conductive polymer containing at least a polythiophene compound / polystyrene sulfonic acid and an inorganic adhesive containing a silane compound. And it is 100 to 200 nm thick. When the total of the conductive polymer and the inorganic adhesive is set to 100, it has a content of the conductive polymer of 7.5 to 15.0% by weight and a surface resistance of 500 to 1500 Ω / □. value.
某一形態中，前述透明基材為透明玻璃基板， 前述透明導面膜於可見光區域波長380~780nm之範圍測定之反射光譜中，於450nm以上之範圍具有反射率之最低值。In a certain aspect, the transparent substrate is a transparent glass substrate, and the transparent guide film has the lowest reflectance in a range of 450 nm or more in a reflection spectrum measured in a wavelength range of 380 to 780 nm in the visible light region.
某一形態中，前述透明導面膜於可見光區域波長380~780nm之範圍測定之反射光譜中，不具有反射率峰值及反射率谷值兩者。In a certain aspect, the aforementioned transparent guide film does not have both a reflectance peak and a reflectance valley in a reflection spectrum measured in a wavelength range of 380 to 780 nm in the visible light region.
某一形態中，前述透明導電膜具有97%以上之透明基材作為參考而測定之全光線透過率。In a certain aspect, the transparent conductive film has a total light transmittance measured with a transparent substrate of 97% or more as a reference.
又，本發明提供一種前述任一透明導電膜之製造方法，其包含將含有包含聚噻吩系化合物/聚苯乙烯磺酸之導電性高分子、矽烷化合物及溶劑，且具有3%以下固體成分濃度之塗佈組成物噴霧塗佈於透明基材之一面上而形成塗膜之步驟。The present invention also provides a method for producing any of the foregoing transparent conductive films, which includes a conductive polymer including a polythiophene compound / polystyrene sulfonic acid, a silane compound, and a solvent, and has a solid content concentration of 3% or less. The step of spray coating the coating composition on one surface of a transparent substrate to form a coating film.
某一形態中，前述塗佈組成物進而含有選自由醌化合物、亞硝胺化合物及酚系化合物所成之群中之至少一種抗氧化劑。In a certain aspect, the coating composition further contains at least one antioxidant selected from the group consisting of a quinone compound, a nitrosamine compound, and a phenolic compound.
某一形態中，前述塗佈組成物進而含有選自由磷酸、鹽酸及硫酸所成之群中之至少一種無機酸。In one aspect, the coating composition further contains at least one inorganic acid selected from the group consisting of phosphoric acid, hydrochloric acid, and sulfuric acid.
某一形態中，前述抗氧化劑為醌化合物。In a certain aspect, the antioxidant is a quinone compound.
某一形態中，前述透明導電膜之製造方法進而包含使前述塗膜乾燥及硬化而成膜之步驟。In a certain aspect, the manufacturing method of the said transparent conductive film further includes the process of drying and hardening the said coating film, and forming a film.
又，本發明提供一種透明導電膜形成用塗佈組成物，其係使用於形成上述任一透明導電膜之用途，且至少含有包含聚噻吩系化合物/聚苯乙烯磺酸之導電性高分子、矽烷化合物及溶劑。 [發明效果]The present invention also provides a coating composition for forming a transparent conductive film, which is used for forming any of the above-mentioned transparent conductive films, and contains at least a conductive polymer containing a polythiophene compound / polystyrenesulfonic acid, Silane compounds and solvents. [Inventive effect]
依據本發明，提供平坦性優異、於表面難以發生色偏差之包含聚噻吩系化合物/聚苯乙烯磺酸之透明導電膜。According to the present invention, a transparent conductive film including a polythiophene compound / polystyrene sulfonic acid, which is excellent in flatness and hardly cause color deviation on the surface, is provided.
＜透明導電膜＞ 本發明一形態之透明導電膜係形成於透明基材之一面上之至少含有導電性高分子及無機系黏合劑者。<Transparent conductive film> (1) The transparent conductive film of one aspect of the present invention is formed on one surface of a transparent substrate and contains at least a conductive polymer and an inorganic adhesive.
導電性高分子係稱為Conductive Polymer (CPs)之高分子，係指於藉由摻雜劑之摻雜，形成聚自由基陽離子鹽或聚自由基陰離子鹽之狀態，其本身可發揮導電性之高分子。Conductive polymers are polymers called Conductive Polymers (CPs), which refer to the state where polyradical cation salts or polyradical anion salts are formed by doping with dopants. Polymer.
本發明之一形態，作為導電性高分子係使用包含聚噻吩系化合物與摻雜劑者。作為本發明一形態之導電性高分子，可使用包含作為聚噻吩系化合物之聚(3,4-乙二氧基噻吩)與作為摻雜劑之聚苯乙烯磺酸之混合物(亦稱為PEDOT/PSS)。PEDOT/PSS雖導電性、耐濕熱性及耐候性優異而有用，但於分散於溶劑中之情況下亦具有容易凝集及偏聚性質。One aspect of the present invention uses a polythiophene-based compound and a dopant as the conductive polymer system. As a conductive polymer according to one aspect of the present invention, a mixture containing poly (3,4-ethylenedioxythiophene) as a polythiophene compound and polystyrenesulfonic acid as a dopant (also referred to as PEDOT) can be used. / PSS). Although PEDOT / PSS is excellent in electrical conductivity, moisture and heat resistance, and weather resistance, it is also easy to aggregate and segregate when dispersed in a solvent.
作為無機系黏合劑，係使用透明性高、可構成粒子狀無機系黏合劑之包含矽烷化合物之黏合劑。藉由使無機系黏合劑形成為粒子狀，將導電性高分子配置於無機系黏合劑之粒子間，可提高透明導電性薄片之透明導電膜的電特性。所謂無機系黏合劑意指由氧化矽或氧化鋁之無機物所成之一般利用藉由與水之相互作用而陶瓷化之交聯作用的材料。As the inorganic adhesive, a silane compound-containing adhesive having high transparency and constituting a particulate inorganic adhesive is used. By forming the inorganic adhesive into particles and disposing the conductive polymer between the particles of the inorganic adhesive, the electrical characteristics of the transparent conductive film of the transparent conductive sheet can be improved. The inorganic binder refers to a material made of an inorganic substance such as silicon oxide or aluminum oxide, which generally uses a cross-linking action that is ceramicized by interaction with water.
透明導電膜之厚度為100~200nm。透明導電膜之厚度未達100nm時，由於有耐擦傷性降低之顧慮故而欠佳。透明導電膜之厚度超過200nm時，由於來自光譜形狀之光干涉所致之色偏差易變顯眼故而欠佳。且，透明導電膜之厚度若為超過200nm而較厚，則自大塊玻璃基板切出小片時有發生膜之毛邊或殘渣而作為異物混入之可能性，故而欠佳。透明導電膜之厚度較好為120~180nm，更好為130~170nm。The thickness of the transparent conductive film is 100 to 200 nm. When the thickness of the transparent conductive film is less than 100 nm, there is a concern that abrasion resistance may be reduced, which is not preferable. When the thickness of the transparent conductive film exceeds 200 nm, the color deviation due to the interference of light from the spectral shape tends to be noticeable, which is not preferable. In addition, if the thickness of the transparent conductive film is thicker than 200 nm, there is a possibility that burrs or residues of the film may be generated when foreign matter is mixed in when cutting a small piece from a large glass substrate, which is not preferable. The thickness of the transparent conductive film is preferably 120 to 180 nm, and more preferably 130 to 170 nm.
導電性高分子係以導電性高分子及無機系黏合劑之合計量為基準以7.5~15質量%之量使用。導電性高分子之使用量若為以導電性高分子及無機系黏合劑之合計量為基準未達7.5質量%，則獲得成為目標之500~1000Ω/□之表面電阻值而必要之膜厚變厚，於透明基材上形成塗膜時反射光譜形狀成為易受到反射色影響之形狀而可能因膜厚變動成為色偏差原因故而欠佳。導電性高分子之使用量若為以導電性高分子及無機系黏合劑之合計量為基準超過15質量%，則獲得成為目標之500~1000Ω/□之表面電阻值而必要之膜厚變薄，故使塗膜硬度或擦傷性降低，於塗佈或搬送之作業時塗膜容易損傷故而欠佳。導電性高分子之使用量若為以導電性高分子及無機系黏合劑之合計量為基準，較好為9~14質量%，更好為10~13.5質量%。The conductive polymer is used in an amount of 7.5 to 15% by mass based on the total amount of the conductive polymer and the inorganic adhesive. If the amount of the conductive polymer used is less than 7.5% by mass based on the total amount of the conductive polymer and the inorganic adhesive, the required film thickness of the target surface resistance value of 500 to 1000 Ω / □ will be obtained. When the coating film is formed on a transparent substrate, the shape of the reflection spectrum becomes a shape that is easily affected by the reflection color, which may be caused by the variation in film thickness and cause color deviation. If the amount of the conductive polymer used exceeds 15% by mass based on the total amount of the conductive polymer and the inorganic adhesive, a target surface resistance value of 500 to 1000 Ω / □ will be obtained and the necessary film thickness will be reduced. Therefore, the hardness or abrasion of the coating film is reduced, and the coating film is easy to be damaged during the coating or transportation operation, which is not good. If the amount of the conductive polymer used is based on the total amount of the conductive polymer and the inorganic adhesive, it is preferably 9 to 14% by mass, and more preferably 10 to 13.5% by mass.
透明導電膜之表面電阻值為500~1000Ω/□之範圍。表面電阻值成為500Ω/□以下時，一般為達成電阻值而必須使導電性聚合物以導電性高分子及無機系黏合劑之合計量為基準添加多於15質量%，或使透明導電膜之厚度厚於200nm，而使透明導電膜之透過率降低，作為裝置用途使用時之辨識性降低故而欠佳。表面電阻值為1000Ω/□以上時，無法獲得充分之雜訊遮蔽效果而欠佳。透明導電膜之表面電阻值較好為600~900Ω/□，更好為650~850Ω/□。The surface resistance value of the transparent conductive film is in the range of 500 ~ 1000Ω / □. When the surface resistance value is less than 500Ω / □, in order to achieve the resistance value, it is generally necessary to add more than 15% by mass of the conductive polymer based on the total amount of the conductive polymer and the inorganic adhesive, or make the transparent conductive film The thickness is greater than 200 nm, which lowers the transmittance of the transparent conductive film and reduces the visibility when used as a device application, which is not good. When the surface resistance value is 1000Ω / □ or more, a sufficient noise shielding effect cannot be obtained, which is not good. The surface resistance value of the transparent conductive film is preferably 600 to 900 Ω / □, and more preferably 650 to 850 Ω / □.
於透明玻璃基板上形成透明導電膜時，作為前述透明導電膜之於可見光區域波長380~780nm之範圍測定之反射光譜之形狀，反射率成為最低之波長較好為450nm以上。反射率之最低值存在於例如450~ 780nm之範圍，更好存在於500~ 780nm之範圍。反射率之最低值可為反射光譜之谷值，或可為上述範圍之兩端中減少途中之反射率。此實質上意指作為於380~780nm之可見光波長範圍內之反射光譜之形狀，不具有峰值(山峰)及谷值(山谷)兩者。作為於380~780nm之可見光波長範圍內之反射光譜之形狀具有峰值及谷值並無妨。When forming a transparent conductive film on a transparent glass substrate, as the shape of the reflection spectrum of the transparent conductive film measured in the visible light range of 380 to 780 nm, the wavelength at which the reflectance becomes the lowest is preferably 450 nm or more. The lowest value of the reflectance exists, for example, in a range of 450 to 780 nm, and more preferably exists in a range of 500 to 780 nm. The lowest value of the reflectance may be a valley value of the reflection spectrum, or may be a decrease in the reflectance in the middle of the above two ranges. This essentially means a shape that is a reflection spectrum in a visible light wavelength range of 380 to 780 nm, and does not have both a peak value (mountain peak) and a valley value (valley). It does not matter if the shape of the reflection spectrum in the visible light wavelength range of 380 to 780 nm has peaks and valleys.
尤其較好為於可見光區域波長內於人視感度高的550nm附近不具有反射率峰值般之膜厚設計。此係因為於視感度高的550nm附近存在反射率之峰值時，於透明導電膜之厚度產生變動時於光譜形狀變化時，即使稍有形狀變化，對反射色相之影響亦大而易使色偏差變顯眼。且，即使假設為於550nm附近無反射光譜之峰值，於可見光區域波長內具有峰值與谷值之形狀時，於因膜厚變動使光譜形狀變化時，亦有反射色資訊複雜影響而使色偏差顯眼之可能性。因此，基於光學觀點，透膜導電膜之厚度較好為200nm以下。It is particularly preferable that the film thickness is designed to have no reflectance peak at around 550 nm where human sensitivity is high in the wavelength of the visible light region. This is because when there is a peak of reflectance near 550nm with high visual sensitivity, when the thickness of the transparent conductive film changes, and when the spectral shape changes, even if there is a slight shape change, the influence on the reflection hue is large and the color deviation is easy Visible. In addition, even if it is assumed that there is no peak of the reflection spectrum near 550 nm, when there are peaks and valleys in the wavelength of the visible light region, when the shape of the spectrum changes due to film thickness variations, there is a complex effect of reflection color information and color deviation Outstanding possibilities. Therefore, from the optical viewpoint, the thickness of the transparent film conductive film is preferably 200 nm or less.
透明導電膜之全光線透過率較好為96%以上。全光線透過率越高表示越良好光學特性。透明導電膜之全光線透過率更好為97%以上，又更好為98%以上。The total light transmittance of the transparent conductive film is preferably 96% or more. Higher total light transmittance indicates better optical characteristics. The total light transmittance of the transparent conductive film is more preferably 97% or more, and more preferably 98% or more.
透明導電膜之濁度較好為0.5%以下。濁度越低表示透明性越高。透明導電膜之濁度更好為0.4%以下，又更好為0.3%以下。透明導電膜之全光線透過率・濁度可藉由濁度計例如日本電色工業公司製之“NDH2000”而測定。The turbidity of the transparent conductive film is preferably 0.5% or less. The lower the turbidity, the higher the transparency. The turbidity of the transparent conductive film is more preferably 0.4% or less, and still more preferably 0.3% or less. The total light transmittance and turbidity of the transparent conductive film can be measured with a haze meter such as "NDH2000" manufactured by Nippon Denshoku Industries, Ltd.
透明導電膜之硬度較好為鉛筆硬度2H以上。鉛筆硬度係基於日本工業規格(JIS) K5400之測定方法而決定。透明導電膜之硬度更好為鉛筆硬度3H以上。The hardness of the transparent conductive film is preferably a pencil hardness of 2H or more. The pencil hardness is determined based on the measurement method of Japanese Industrial Standard (JIS) K5400. The hardness of the transparent conductive film is more preferably a pencil hardness of 3H or more.
＜透明導電膜形成用塗佈組成物＞ 本發明一形態之透明導電膜係使用透明導電膜形成用塗佈組成物而形成。透明導電膜形成用塗佈組成物至少含有導電性高分子與無機系黏合劑之前驅物的矽烷化合物及溶劑。<Coating composition for forming a transparent conductive film> 透明 The transparent conductive film according to one aspect of the present invention is formed using the coating composition for forming a transparent conductive film. The coating composition for forming a transparent conductive film contains at least a silane compound and a solvent of a conductive polymer and a precursor of an inorganic adhesive.
矽烷化合物經水解及脫水縮合。矽烷化合物較好為烷氧基矽烷。且，作為烷氧基矽烷例示為選自由四烷氧基矽烷、三烷氧基矽烷、二烷氧基矽烷及烷氧基矽烷寡聚物所成之群中之至少一種烷氧基矽烷。Silane compounds undergo hydrolysis and dehydration condensation. The silane compound is preferably an alkoxysilane. The alkoxysilane is exemplified by at least one alkoxysilane selected from the group consisting of tetraalkoxysilane, trialkoxysilane, dialkoxysilane, and alkoxysilane oligomers.
作為四烷氧基矽烷之例舉例為四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、四異丙氧基矽烷、四第三丁氧基矽烷等之以碳數1~4之烷氧基四取代之矽烷。作為具體例舉例為信越化學公司製之“KBE-04”(商品名)等。Examples of tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetra-third-butoxysilane, etc., with carbon numbers of 1 to 4 Alkoxy tetra-substituted silane. A specific example is "KBE-04" (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.
作為三烷氧基矽烷之例舉例為三甲氧基矽烷、三乙氧基矽烷、三丙氧基矽烷、三丁氧基矽烷、三異丙氧基矽烷、三L-丁氧基矽烷等之以碳數1~4之烷氧基三取代之矽烷。Examples of trialkoxysilanes include trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane, triisopropoxysilane, and tri-L-butoxysilane. Alkoxy tri-substituted silanes having 1 to 4 carbon atoms.
作為二烷氧基矽烷之例舉例為二甲基二甲氧基矽烷、二苯基二甲氧基矽烷、二甲基二乙氧基矽烷、二苯基二乙氧基矽烷等。Examples of the dialkoxysilane include dimethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, and the like.
烷氧基矽烷寡聚物係具有烷氧基矽烷基之比較低分子的樹脂。作為具體例舉例為信越化學公司製之“X-40-2308”、“X-40-9225”、“X-40-9226”、“X-40-9238”、“X-40-9247”、“X-40-9250”、“KC-89S”、“KR-220LP”、“KR-401N”、“KR-500”、“KR-510”、“KR-9218”(商品名)、COLCOAT公司製之“矽酸乙酯40”、“矽酸乙酯48”、“矽酸甲酯51”、“矽酸甲酯53A”、“EMS-485”、“SS101”(商品名)等。The alkoxysilane oligomer is a relatively low molecular weight resin having an alkoxysilane group. Specific examples are "X-40-2308", "X-40-9225", "X-40-9226", "X-40-9238", "X-40-9247", manufactured by Shin-Etsu Chemical Co., Ltd., "X-40-9250", "KC-89S", "KR-220LP", "KR-401N", "KR-500", "KR-510", "KR-9218" (brand name), COLCOAT Corporation Made of "ethyl silicate 40", "ethyl silicate 48", "methyl silicate 51", "methyl silicate 53A", "EMS-485", "SS101" (trade name), etc.
且，作為烷氧基矽烷亦可使用乙烯基甲氧基矽烷、對-苯乙烯基甲氧基矽烷、甲基三甲氧基矽烷、二甲基二甲氧基矽烷、苯基三甲氧基矽烷、甲基三乙氧基矽烷、二甲基二乙氧基矽烷、苯基三乙氧基矽烷、己基三甲氧基矽烷、己基三乙氧基矽烷、癸基三甲氧基矽烷、三氟丙基三甲氧基矽烷等之烷氧基矽烷單體。In addition, as the alkoxysilane, vinylmethoxysilane, p-styrylmethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, Methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethylsilane An alkoxysilane monomer such as oxysilane.
且，可併用四烷氧基矽烷及三烷氧基矽烷。In addition, tetraalkoxysilane and trialkoxysilane can be used in combination.
作為烷氧基矽烷併用四烷氧基矽烷及三烷氧基矽烷時，四烷氧基矽烷與三烷氧基矽烷之莫耳比較好為9:1~5:5，更好為8:2~6:4。該莫耳比關係較好的理由係可防止透明導電膜之硬度降低，並且更不會有因經時變化於透明導面膜發生龜裂之危險性，且可更提高與透明基材之密著性之故。認為四烷氧基矽烷作用於展現高的膜硬度，三烷氧基矽烷作用於防止透明導電膜之龜裂發生、與透明基材之密著性。When using both tetraalkoxysilane and trialkoxysilane as the alkoxysilane, the molar ratio of tetraalkoxysilane and trialkoxysilane is preferably 9: 1 to 5: 5, and more preferably 8: 2. ~ 6: 4. The reason why the Morse ratio is better is to prevent the hardness of the transparent conductive film from being lowered, and there is no risk of cracks in the transparent conductive film due to changes over time, and the adhesion to the transparent substrate can be further improved. For sexual reasons. It is believed that tetraalkoxysilane acts to exhibit high film hardness, and trialkoxysilane acts to prevent cracking of the transparent conductive film and adhesion to the transparent substrate.
透明導電膜形成用塗佈組成物中之矽烷化合物含量，以塗佈組成物全體為基準為0.05~10質量%。矽烷化合物之含量未達0.05質量%時，鉛筆硬度降低，超過10質量%時，墨水保存性惡化。矽烷化合物含量，以塗佈組成物全體為基準，較好為0.1~5質量%，更好為0.3~3質量%。The content of the silane compound in the coating composition for forming a transparent conductive film is 0.05 to 10% by mass based on the entire coating composition. When the content of the silane compound is less than 0.05% by mass, the pencil hardness is reduced, and when it exceeds 10% by mass, the ink preservation property is deteriorated. The content of the silane compound is preferably 0.1 to 5% by mass, and more preferably 0.3 to 3% by mass based on the entire coating composition.
溶劑較好包含質子性極性溶劑與非質子性極性溶劑。藉由併用質子性極性溶劑與非質子性極性溶劑，可以比較低的乾燥溫度獲得透明性優異之透明導電膜。The solvent preferably includes a protic polar solvent and an aprotic polar solvent. By using a protic polar solvent and an aprotic polar solvent together, a transparent conductive film having excellent transparency can be obtained at a relatively low drying temperature.
所謂質子性極性溶劑意指具有質子供給性之溶劑。作為質子性極性溶劑舉例為例如水、乙醇、甲醇、正丙醇、異丙醇、正丁醇、異丁醇、乙二醇、丙二醇、乙酸等。所謂非質子性極性溶劑意指不具有質子供給性之溶劑。作為非質子性極性溶劑舉例為二甲基亞碸、N-甲基吡咯啶酮、N-乙基吡咯啶酮、N,N-二甲基甲醯胺、乙腈、丙酮、四氫呋喃等。特佳之溶劑為包含二甲基亞碸、水及乙醇者。基於乾燥性及電阻展現之觀點，現狀最適當係該3種之組合。The protic polar solvent means a solvent having a proton donating property. Examples of the protic polar solvent include water, ethanol, methanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, propylene glycol, and acetic acid. The aprotic polar solvent means a solvent having no proton donating property. Examples of the aprotic polar solvent include dimethylsulfinium, N-methylpyrrolidone, N-ethylpyrrolidone, N, N-dimethylformamidine, acetonitrile, acetone, and tetrahydrofuran. A particularly preferred solvent is one containing dimethyl sulfene, water and ethanol. From the viewpoints of dryness and resistance, the current situation is the most appropriate combination of these three types.
非質子性極性溶劑之含量，相對於溶劑全體，較好為1.0質量%以上50.0質量%以下。非質子性極性溶劑之含量，相對於溶劑全體，低於1.0質量%時，透明導電膜之光學特性降低，超過50.0質量%時，透明導電膜之耐濕熱性降低。The content of the aprotic polar solvent is preferably 1.0% by mass or more and 50.0% by mass or less with respect to the entire solvent. When the content of the aprotic polar solvent is less than 1.0% by mass relative to the entire solvent, the optical characteristics of the transparent conductive film are reduced, and when it exceeds 50.0% by mass, the moisture and heat resistance of the transparent conductive film is reduced.
溶劑含量並未特別限定，但相對於塗佈組成物全體，若為50.0質量%以上99.5質量%以下即可。且，溶劑中亦可包含無極性溶劑。The solvent content is not particularly limited, but may be 50.0% by mass or more and 99.5% by mass or less with respect to the entire coating composition. The solvent may include a non-polar solvent.
透明導電膜形成用塗佈組成物亦可進而含有有機系黏合劑。透明導電膜藉由含有有機系黏合劑，可提高透明導電膜與透明基材之密著性。尤其，使用塑膠膜等之撓性基材作為透明基材時，透明導電膜含有有機系黏合劑時，就透明導電膜與透明基材之密著性或追隨性之觀點較佳。The coating composition for forming a transparent conductive film may further contain an organic binder. The transparent conductive film can improve the adhesion between the transparent conductive film and the transparent substrate by containing an organic adhesive. In particular, when a flexible substrate such as a plastic film is used as the transparent substrate, and when the transparent conductive film contains an organic binder, the viewpoint of adhesion or followability of the transparent conductive film and the transparent substrate is preferred.
作為有機系黏合劑舉例為例如丙烯酸樹脂、三聚氰胺樹脂、聚酯樹脂、聚醯胺樹脂、聚碳酸酯樹脂、聚胺基甲酸酯樹脂、聚苯乙烯樹脂、聚氯乙烯樹脂、聚偏氯乙烯樹脂、聚乙酸乙烯酯樹脂、聚篇幅乙烯樹脂、羥基乙基纖維素、聚乙烯醇、聚乙二醇(PEG)、聚環氧乙烷、聚環氧丙烷、多糖類、其他光聚合性樹脂等。且作為有機系黏合劑之使用形態，可使用溶劑溶解型或乳液型。有機系黏合劑之含量過多時，由於無機系黏合劑之效果減少，故有機系黏合劑之含量限制於不產生該問題之範圍。透明導電膜形成用塗佈組成物亦可不含有有機系黏合劑。有機系黏合劑之含量於黏合劑量全體中，較好為10質量%以下，更好為5質量%以下，又更好為1質量%以下。Examples of the organic binder include acrylic resin, melamine resin, polyester resin, polyamide resin, polycarbonate resin, polyurethane resin, polystyrene resin, polyvinyl chloride resin, and polyvinylidene chloride. Resins, polyvinyl acetate resins, polyethylene resins, hydroxyethyl cellulose, polyvinyl alcohol, polyethylene glycol (PEG), polyethylene oxide, polypropylene oxide, polysaccharides, and other photopolymerizable resins Wait. In addition, as a use form of the organic adhesive, a solvent-soluble type or an emulsion type can be used. When the content of the organic-based adhesive is too much, the effect of the inorganic-based adhesive is reduced, so the content of the organic-based adhesive is limited to a range in which the problem is not caused. The coating composition for forming a transparent conductive film may not contain an organic binder. The content of the organic binder in the total amount of the binder is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.
透明導電膜形成用塗佈組成物中亦可含有無機酸。藉此，提高透明導電膜形成用塗佈組成物之保存安定性。作為無機酸係使用例如磷酸、鹽酸、硫酸等。特佳之無機酸為磷酸。The coating composition for forming a transparent conductive film may contain an inorganic acid. This improves the storage stability of the coating composition for forming a transparent conductive film. Examples of the inorganic acid include phosphoric acid, hydrochloric acid, and sulfuric acid. A particularly preferred inorganic acid is phosphoric acid.
無機酸較好以導電性高分子含量為基準以30質量%以下之量含有。無機酸之使用量以導電性高分子含量為基準超過30質量%時，由於無機酸與導電性高分子反應，故使透明導電膜之耐候性降低，使塗佈組成物之保存安定性降低。無機酸之使用量，以導電性高分子含量為基準，較好為未達30質量%、5重量%以上且未達30質量%，更好為7~25質量%。The inorganic acid is preferably contained in an amount of 30% by mass or less based on the content of the conductive polymer. When the amount of the inorganic acid used exceeds 30% by mass based on the content of the conductive polymer, the inorganic acid reacts with the conductive polymer, thereby reducing the weather resistance of the transparent conductive film and reducing the storage stability of the coating composition. The amount of the inorganic acid used is based on the content of the conductive polymer, and is preferably less than 30% by mass, 5% by weight or more and less than 30% by mass, and more preferably 7 to 25% by mass.
透明導電膜形成用塗佈組成物中亦可含有抗氧化劑。因此，提高透明導電膜之耐濕熱性及耐候性，進而提高塗佈組成物之保存安定性。作為抗氧化劑，係使用醌化合物、亞硝胺化合物、酚系抗氧化劑等。The coating composition for forming a transparent conductive film may contain an antioxidant. Therefore, the moisture and heat resistance and weather resistance of the transparent conductive film are improved, and the storage stability of the coating composition is further improved. As the antioxidant, a quinone compound, a nitrosamine compound, a phenolic antioxidant, or the like is used.
作為醌化合物，舉例為例如氫醌、氫醌單甲醚、甲基氫醌、4-第三丁基鄰苯二酚第三丁基氫醌、1,4-苯醌、二丁基羥基甲苯、1,1-二苯基-2-三硝基苯肼游離基、甲氧酚、吩噻嗪、4-羥基TEMPO等。 作為亞硝胺化合物舉例為例如N-亞硝基-N-苯基羥基胺、N-亞硝基-N-苯基羥基胺鋁鹽、N-亞硝基-N-苯基羥基胺鈰鹽等。Examples of the quinone compound include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, 4-tert-butylcatechol tert-butylhydroquinone, 1,4-benzoquinone, and dibutylhydroxytoluene. , 1,1-diphenyl-2-trinitrophenylhydrazine free radical, methoxyphenol, phenothiazine, 4-hydroxy TEMPO, etc. Examples of the nitrosamine compound include N-nitroso-N-phenylhydroxylamine, N-nitroso-N-phenylhydroxylamine aluminum salt, and N-nitroso-N-phenylhydroxylamine cerium salt. Wait.
作為酚系抗氧化劑舉例為例如2,6-二-第三丁基-4-甲基苯酚、沒食子酸丙酯、2,4,6-三羥基丁醯苯正二氫癒創酸、丁基羥基苯甲醚、沒食子酸辛酯、二丁基羥基甲苯、沒食子酸十二烷酯等。Examples of the phenol-based antioxidant include 2,6-di-tertiary-butyl-4-methylphenol, propyl gallate, 2,4,6-trihydroxybutyrophenylbenzene dihydroguaiaretic acid, butane Hydroxyanisole, octyl gallate, dibutyl hydroxytoluene, dodecyl gallate and the like.
特佳之抗氧化劑為氫醌、氫醌單甲醚、甲基氫醌。抗氧化劑以導電性高分子含量為基準以20質量%以下之量含有。抗氧化劑之使用量以導電性高分子含量為基準超過20質量%時，由於無機系黏合劑之比率變少，塗膜硬度降低，故抗氧化劑之使用量以導電性高分子含量為基準較好為1~15質量%，更好為2~10質量%。Particularly preferred antioxidants are hydroquinone, hydroquinone monomethyl ether, and methylhydroquinone. The antioxidant is contained in an amount of 20% by mass or less based on the content of the conductive polymer. When the amount of the antioxidant exceeds 20% by mass based on the content of the conductive polymer, the ratio of the inorganic adhesive decreases and the hardness of the coating film decreases. Therefore, the amount of the antioxidant used is better based on the content of the conductive polymer It is 1 to 15 mass%, more preferably 2 to 10 mass%.
透明導電膜形成用塗佈組成物中亦可含有表面調整劑。作為表面調整劑，可使用矽系表面調整劑，例如使用矽氧烷系表面調整劑等。表面調整劑以塗佈組成物全體為基準以0.01~10質量%之量使用。藉由將表面調整劑之使用量調節於上述範圍，可使透明導電膜，尤其是噴霧皮膜厚度均一化。表面調整劑之使用量以塗佈組成物全體為基準較好為0.02~5質量%，更好為0.05~0.3質量%。The coating composition for forming a transparent conductive film may contain a surface modifier. As the surface conditioner, a silicon-based surface conditioner can be used, and for example, a siloxane-based surface conditioner is used. The surface modifier is used in an amount of 0.01 to 10% by mass based on the entire coating composition. By adjusting the amount of the surface modifier used in the above range, the thickness of the transparent conductive film, especially the spray coating film can be made uniform. The amount of the surface modifier used is preferably 0.02 to 5% by mass, and more preferably 0.05 to 0.3% by mass based on the entire coating composition.
塗佈組成物可藉由習知方法將導電性高分子、矽烷化合物、無機酸、表面調整劑及溶劑等適當混合而製造。例如各成分可藉由球磨機、砂磨機、微分散機、塗料調合機等之經由介質之機械處理，或藉由超音波分散機、均質機、分散機、噴射磨機等之無介質處理，予以混合、分散。The coating composition can be produced by appropriately mixing a conductive polymer, a silane compound, an inorganic acid, a surface modifier, a solvent, and the like by a known method. For example, each component can be processed by media through ball mills, sand mills, micro-dispersers, paint blenders, etc., or by medium-free processing by ultrasonic dispersers, homogenizers, dispersers, jet mills, etc. Mix and disperse.
又，各成分之添加順序亦未特別限制，例如可於由導電性高分子與溶劑所成之溶液中，添加矽烷化合物與無機酸，或分別製作由導電性高分子與溶劑所成之溶液及由矽烷化合物與無機酸與溶劑所成之溶液後，混合各溶液。The order of adding the components is not particularly limited. For example, a silane compound and an inorganic acid can be added to a solution made of a conductive polymer and a solvent, or a solution made of a conductive polymer and a solvent can be separately prepared. After a solution of a silane compound, an inorganic acid, and a solvent, the solutions are mixed.
塗佈組成物之固體成分濃度較好以塗佈組成物全體為基準，為3重量%以下。塗佈組成物之固體成分濃度以塗佈組成物全體為基準，超過3重量%時，塗佈組成物之黏度變高，於噴霧中導電性高分子凝集容易產生塗膜缺陷。塗佈組成物之固體成分濃度以以塗佈組成物全體為基準，更好為2.5重量%以下。所謂塗佈組成物之固體成分意指不揮發性成分。塗佈組成物之固體成分中，典型上包含導電性高分子、矽烷化合物、酸觸媒、抗氧化劑及表面調整劑。The solid content concentration of the coating composition is preferably 3% by weight or less based on the entire coating composition. The solid content concentration of the coating composition is based on the entire coating composition. When it exceeds 3% by weight, the viscosity of the coating composition becomes high, and the conductive polymer aggregates during spraying, and coating film defects are likely to occur. The solid content concentration of the coating composition is more preferably 2.5% by weight or less based on the entire coating composition. The solid content of the coating composition means a non-volatile content. The solid content of the coating composition typically includes a conductive polymer, a silane compound, an acid catalyst, an antioxidant, and a surface modifier.
塗佈組成物之黏度較好為20cps以下。塗佈組成物之黏度超過20cps時，噴霧中導電性高分子凝集容易產生塗膜缺陷。塗佈組成物之黏度更好為150cps以下，又更好為10cps以下。The viscosity of the coating composition is preferably 20 cps or less. When the viscosity of the coating composition exceeds 20 cps, the conductive polymer aggregates during spraying tends to cause coating film defects. The viscosity of the coating composition is more preferably 150 cps or less, and even more preferably 10 cps or less.
＜透明導電膜之形成＞ 透明導電膜係將透明導電膜形成用塗佈組成物塗佈於透明基材上，形成塗膜後，使上述塗膜乾燥或硬化而成膜。<Formation of transparent conductive film> Transparent conductive film is formed by coating a transparent conductive film-forming coating composition on a transparent substrate, forming a coating film, and drying or curing the coating film.
作為透明基材可使用包含例如塑膠、橡膠、玻璃、陶瓷等之各種透明材料。透明基材較好為透明玻璃基材。透明基材具有例如未達1mm，較好0.2~0.8mm之厚度。As the transparent substrate, various transparent materials including, for example, plastic, rubber, glass, ceramic, and the like can be used. The transparent substrate is preferably a transparent glass substrate. The transparent substrate has a thickness of, for example, less than 1 mm, and preferably 0.2 to 0.8 mm.
塗佈組成物之塗佈，基於塗佈效率良好之觀點，使用噴霧塗佈法。噴霧塗佈係使用0.05~0.35MPa之噴霧壓而進行。噴霧器之噴嘴較好使用淋洗霧化器。淋洗霧化器係於噴嘴內部具有渦流室，產生喇叭狀廣角噴霧之霧化器。For coating the coating composition, a spray coating method is used from the viewpoint of good coating efficiency. Spray coating is performed using a spray pressure of 0.05 to 0.35 MPa. The spray nozzle is preferably a spray atomizer. The shower atomizer is an atomizer with a vortex chamber inside the nozzle to generate a horn-shaped wide-angle spray.
噴霧器之噴嘴使用淋洗霧化器時，噴霧塗佈係使用0.05~0.40MPa之霧化壓及0.05~0.40MPa之淋洗壓而進行。所謂霧化壓係指對墨水流吹附噴射空氣而微粒化、霧化時之空氣壓。所謂淋洗壓係指繞著汽缸中心軸之橫渦空氣壓。霧化壓或淋洗壓未達0.05MPa時，透明導電膜之平坦性降低，容易發生色偏差，霧化壓或淋洗壓高過0.40MPa時，導電性高分子凝集，容易發生塗膜中之塊狀物。When a spray atomizer is used as the nozzle of the sprayer, spray coating is performed using an atomization pressure of 0.05 to 0.40 MPa and a shower pressure of 0.05 to 0.40 MPa. The so-called atomizing pressure refers to the air pressure at the time of atomizing and atomizing the jet of air by spraying it with air. The so-called shower pressure refers to the transverse vortex air pressure around the central axis of the cylinder. When the atomization pressure or the rinse pressure is less than 0.05 MPa, the flatness of the transparent conductive film is reduced, and color deviation is easy to occur. When the atomization pressure or the rinse pressure is higher than 0.40 MPa, the conductive polymer aggregates, and the coating film is liable to occur. Lumps.
本發明一形態中使用之透明導電膜形成用塗佈組成物具有適於藉由噴霧塗佈法塗佈之黏度。又，本發明一形態中使用之透明導電膜形成用塗佈組成物具有優異之保存安定性。因此，填充於噴霧塗佈器後至完成塗佈之整個時間內維持適於塗佈之黏度，可於基材表面全體形成膜厚均一之塗膜。The coating composition for forming a transparent conductive film used in one aspect of the present invention has a viscosity suitable for coating by a spray coating method. In addition, the coating composition for forming a transparent conductive film used in one aspect of the present invention has excellent storage stability. Therefore, the viscosity suitable for coating can be maintained in the entire time after filling in the spray coater until the coating is completed, and a uniform coating film can be formed on the entire surface of the substrate.
將塗佈組成物噴霧塗佈於基材表面後，藉由加熱去除溶劑，使矽烷化合物脫水縮合而成膜。根據需要，亦可對塗膜照射UV光或EB光使塗膜硬化。使用本發明一形態之塗佈組成物及噴霧塗佈法形成塗膜，使該塗膜乾燥及硬化而成膜之皮膜可謂為導電性噴霧皮膜。After the coating composition is spray-coated on the surface of the substrate, the solvent is removed by heating to dehydrate and condense the silane compound to form a film. If necessary, the coating film may be irradiated with UV light or EB light to harden the coating film. A coating film is formed by using the coating composition and spray coating method of one aspect of the present invention, and the coating film formed by drying and curing the coating film can be referred to as a conductive spray coating film.
塗佈後之加熱只要為使塗佈組成物之溶劑成分蒸發之條件即可，較好在100~150℃進行5~60分鐘。藉由加熱，矽烷化合物藉由水解及脫水縮合反應成為包含聚矽氧烷之粒子狀無機系黏合劑，於無機系黏合劑之粒子間配置導電性高分子，於透明導電膜中形成三次元之導電通道。作為加熱方法可藉由例如熱風乾燥法、加熱乾燥法、真空乾燥法、自然乾燥法等進行。且，根據需要，亦可對塗膜照射UV光或EB光使塗膜硬化，形成透明導電膜。The heating after coating may be performed under conditions that evaporate the solvent component of the coating composition, and it is preferably performed at 100 to 150 ° C. for 5 to 60 minutes. By heating, the silane compound becomes a particulate inorganic adhesive containing polysiloxane by hydrolysis and dehydration condensation reaction. A conductive polymer is arranged between the particles of the inorganic adhesive to form a three-dimensional polymer in a transparent conductive film. Conductive channel. The heating method can be performed by, for example, a hot air drying method, a heating drying method, a vacuum drying method, a natural drying method, or the like. In addition, if necessary, the coating film may be irradiated with UV light or EB light to harden the coating film to form a transparent conductive film.
以下使用實施例具體說明本發明一形態。但，本發明並非限定於以下實施例。於未特別指明之情況，下述中，「份」及「%」為質量基準。 [實施例]Hereinafter, an embodiment of the present invention will be specifically described using examples. However, the present invention is not limited to the following examples. Unless otherwise specified, "parts" and "%" are the quality basis in the following. [Example]
＜透明導電膜形成用塗佈組成物之製造＞ 準備以下成分，以成為表1所示組成之量混合，製造透明導電膜形成用塗佈組成物。<Production of a coating composition for forming a transparent conductive film> (1) The following components were prepared and mixed in an amount of the composition shown in Table 1 to produce a coating composition for forming a transparent conductive film.
(1)導電性高分子分散液(HERAEUS公司製，商品名“CREBIOS PH1000”，導電性高分子：PEDOT/PSS，固體成分濃度：1.12質量%，溶劑：水) (2)矽烷化合物：烷氧基矽烷(信越化學工業公司製，商品名“X-40-2308”) (3)非質子性極性溶劑(二甲基亞碸) (4)酸觸媒(磷酸) (5)抗氧化劑(氫醌) (6)表面調整劑(聚矽氧烷系) (7)水 (8)質子性極性溶劑(乙醇)(1) Conductive polymer dispersion (made by HERAEUS, trade name "CREBIOS PH1000", conductive polymer: PEDOT / PSS, solid content concentration: 1.12% by mass, solvent: water) (2) silane compound: alkoxy Silane (trade name "X-40-2308", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (3) Aprotic polar solvent (dimethyl sulfene) (4) Acid catalyst (phosphoric acid) (5) Antioxidant (hydrogen Quinone) (6) Surface modifier (polysiloxane series) (7) Water (8) Protonic polar solvent (ethanol)
＜透明導電膜之製造＞ 使用厚0.7mm之10cm見方之無鹼玻璃(全光線透過率：91.2%)作為基板，於基板之一面上藉由噴霧塗佈法塗佈上述透明導電膜形成用塗佈液，形成塗膜。噴霧塗佈器係使用NORDSON公司製之噴霧槍(淋洗噴嘴，口徑：1.0mm)。塗佈條件如下述。亦即，噴霧槍速度500mm/秒，塗佈間距10mm，槍高度10cm，霧化壓0.1MPa，淋洗壓0.1MPa。隨後於120℃加熱1小時。藉此，製作於一面上形成透明導電膜之透明導電性薄片。＜ Production of transparent conductive film ＞ 碱 Using 0.7mm thick 10cm square alkali-free glass (total light transmittance: 91.2%) as a substrate, the above-mentioned transparent conductive film forming coating is applied by spray coating on one surface of the substrate. The cloth liquid forms a coating film. As the spray coater, a spray gun (rinsing nozzle, caliber: 1.0 mm) manufactured by NORDSON was used. The coating conditions are as follows. That is, the spray gun speed is 500 mm / second, the coating pitch is 10 mm, the gun height is 10 cm, the atomizing pressure is 0.1 MPa, and the shower pressure is 0.1 MPa. It was then heated at 120 ° C for 1 hour. Thereby, a transparent conductive sheet in which a transparent conductive film is formed on one surface is produced.
其次，針對上述透明導電膜，進行以下所示各評價。透明導電膜之組成及評價結果示於表2。Next, each evaluation shown below was performed about the said transparent conductive film. The composition and evaluation results of the transparent conductive film are shown in Table 2.
＜表面電阻＞ 使用三菱化學分析公司製之電阻率測定裝置“Loresta-GP”(MCP-T610型)與LSP探針測定透明導電膜之表面電阻值(Ω/□)。<Surface resistance> 测定 The surface resistance value (Ω / □) of the transparent conductive film was measured using a resistivity measuring device "Loresta-GP" (MCP-T610) manufactured by Mitsubishi Chemical Analysis Co., Ltd. and an LSP probe.
＜膜厚・反射光譜之測定＞ 針對透明導電膜以反射分光膜厚計“FE-3000”(大塚電子公司製)測定反射光譜。測定結果示於圖1。自所測定之反射光譜由n-Cauchy之式進行代入，測定膜厚。<Measurement of film thickness and reflection spectrum> 反射 The reflection spectrum was measured on a transparent conductive film with a reflection spectrometer "FE-3000" (manufactured by Otsuka Electronics Co., Ltd.). The measurement results are shown in FIG. 1. The measured reflection spectrum was substituted by the formula of n-Cauchy, and the film thickness was measured.
＜濁度・全光線透過率＞ 使用日本電色工業公司製之濁度計“NDH2000”測定透明導電膜之濁度及全光線透過率(%)。<Haze and total light transmittance> The turbidity and total light transmittance (%) of the transparent conductive film were measured using a turbidimeter "NDH2000" manufactured by Nippon Denshoku Industries, Ltd.
＜鉛筆硬度＞ 基於以日本工業規格(JIS) K5400規定之鉛筆硬度測定方法，使用新東科學公司製之表面性試驗機“HEIDON-14DR”測定。<Pencil hardness> Measured based on a pencil hardness measurement method specified in Japanese Industrial Standards (JIS) K5400, using a surface property testing machine "HEIDON-14DR" manufactured by Shinto Scientific.
＜外觀(色偏差)＞ 於3波長螢光燈下目視觀察透明導電膜，以3階段判斷色偏差是否顯眼。<Appearance (color deviation)> 观察 Visually observe the transparent conductive film under a 3-wavelength fluorescent lamp, and judge whether the color deviation is noticeable in three stages.
○：幾乎未辨識到作為透明導電膜之色偏差 △：稍可辨識到作為透明導電膜之色偏差 ×：可容易辨識到作為透明導電膜之色偏差○: Color deviation as a transparent conductive film is hardly recognized △: Color deviation as a transparent conductive film is slightly recognized: Color deviation as a transparent conductive film is easily recognized
關於實施例1~3，成為關於全光線透過率或濁度之光學特性、鉛筆硬度及外觀之色偏差全部為良好之透明導電膜。另一方面，關於比較例1，PEDOT含率低如5%而為了獲得目的之表面電阻值必須使膜厚為200nm以上，故所得透明導電膜成為作為外觀色偏差顯眼者。關於比較例2，為了以與比較例1同等PEDOT含率將厚度抑制於150nm左右，而使所得透明導電膜之電阻值變高。關於比較例3，由於PEDOT含率設為20%，故由於以透明導電膜厚度為75nm左右獲得目標電阻值者之膜厚較薄故而成為鉛筆硬度稍差之結果。Examples 1 to 3 were all transparent conductive films having good optical characteristics regarding total light transmittance or turbidity, pencil hardness, and color deviation in appearance. On the other hand, regarding Comparative Example 1, the PEDOT content was as low as 5%, and in order to obtain the surface resistance value for the purpose, the film thickness must be 200 nm or more. Therefore, the obtained transparent conductive film became a prominent color deviation. Regarding Comparative Example 2, in order to suppress the thickness to about 150 nm with the same PEDOT content as Comparative Example 1, the resistance value of the obtained transparent conductive film was increased. Regarding Comparative Example 3, since the PEDOT content was set to 20%, the thickness of a person who obtained the target resistance value with a transparent conductive film thickness of about 75 nm was thin, which resulted in slightly inferior pencil hardness.
圖1係顯示實施例及比較例製造之透明導電膜之反射光譜之圖表。FIG. 1 is a graph showing a reflection spectrum of a transparent conductive film manufactured in Examples and Comparative Examples.
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