TW202413553A - Transparent conductive film capable of being properly used in touch sensors due to bendability and high water resistance - Google Patents
Transparent conductive film capable of being properly used in touch sensors due to bendability and high water resistance Download PDFInfo
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Abstract
Description
本發明係關於一種透明導電膜,尤其是一種可彎折並具高阻水性能之含有奈米銀線的透明導電膜。The present invention relates to a transparent conductive film, in particular to a bendable transparent conductive film containing silver nanowires and having high water-blocking properties.
一直以來,包含奈米銀線層之透明導電膜可應用於觸控感測器的觸控感測電極中。Transparent conductive films containing silver nanowire layers have long been used in touch sensing electrodes for touch sensors.
舉例來說,TWI675895專利揭示了一種透明導電薄板,其係至少具備:作為導電性物質而使用金屬材料之導電層、和與所述導電層接觸之黏合劑層。又,前述黏合劑層包含作為共聚單體成分而含有親水性丙烯酸類單體的丙烯酸類共聚物、和選自由水分吸收劑和金屬離子捕捉劑所構成之群中的至少一種遷移抑制劑。For example, the patent TWI675895 discloses a transparent conductive sheet, which at least comprises: a conductive layer using a metal material as a conductive substance, and an adhesive layer in contact with the conductive layer. Furthermore, the adhesive layer comprises an acrylic copolymer containing a hydrophilic acrylic monomer as a copolymer component, and at least one migration inhibitor selected from the group consisting of a moisture absorbent and a metal ion scavenger.
藉此,TWI675895專利的透明導電薄板能夠抑制因為構成導電層的金屬材料之遷移而發生斷線或者短路。Thus, the transparent conductive sheet of TWI675895 patent can suppress the occurrence of disconnection or short circuit due to the migration of the metal material constituting the conductive layer.
然而,由於觸控感測電極的位置係存在於觸控面板之可視區中,故在例如TWI675895專利的先前技術中,黏合劑層的親水性單體濃度通常高達15%以上,會影響到電極的可視性(包含可見光穿透率以及霧度)。又,黏合劑層中所包含的水分吸收劑、金屬離子捕捉劑等,亦會影響到電極的可視性,而對整體觸控面板的可視性造成不良的影響。However, since the touch sensing electrode is located in the visible area of the touch panel, the concentration of the hydrophilic monomer in the adhesive layer is usually as high as 15% or more in the prior art such as the TWI675895 patent, which will affect the visibility of the electrode (including visible light transmittance and haze). In addition, the moisture absorber and metal ion capture agent contained in the adhesive layer will also affect the visibility of the electrode, thus adversely affecting the visibility of the entire touch panel.
除此之外,黏合劑層的厚度也與整體觸控電極的可視性相關。基此,如何在具有耐彎折的功能的同時,維持導電膜的電性並保持優良的可視性,就成了急需解決的問題。In addition, the thickness of the adhesive layer is also related to the visibility of the overall touch electrode. Therefore, how to maintain the electrical properties of the conductive film and maintain good visibility while having the function of bending resistance has become an urgent problem to be solved.
為了解決上述問題,本發明包含一態樣的透明導電膜,其係包含: 一基板; 一金屬奈米線層,設置於該基板上; 一阻水保護層,具有吸水性粒子,並設置於該金屬奈米線層上;其中, 針對該透明導電膜,使用傅立葉變換紅外光譜(FTIR, Fourier-transform infrared spectroscopy)檢測,於2750 cm -1-3000 cm -1波數區域中具有第一吸收波峰,於3000 cm -1-3750 cm -1波數區域中具有第二吸收波峰,該第一吸收波峰與第二吸收波峰的最大峰值強度比值(第二吸收波峰/第一吸收波峰)為0.18~0.50,且該透明導電膜之霧度值為1.7%以下。 To solve the above problems, the present invention includes a transparent conductive film in one embodiment, which includes: a substrate; a metal nanowire layer disposed on the substrate; a water-blocking protective layer having water-absorbing particles and disposed on the metal nanowire layer; wherein, the transparent conductive film has a first absorption peak in the wave number region of 2750 cm -1 -3000 cm -1 and a second absorption peak in the wave number region of 3000 cm -1 -3750 cm -1 using Fourier transform infrared spectroscopy (FTIR), the maximum peak intensity ratio of the first absorption peak to the second absorption peak (second absorption peak/first absorption peak) is 0.18-0.50, and the haze value of the transparent conductive film is less than 1.7%.
在一實施例中,該第一吸收波峰的光譜積分面積與該第二吸收波峰的光譜積分面積之比值為0.618~1.410。In one embodiment, a ratio of a spectral integration area of the first absorption peak to a spectral integration area of the second absorption peak is 0.618-1.410.
在一實施例中,該透明導電膜包含由金屬奈米線所形成的複數電極。In one embodiment, the transparent conductive film includes a plurality of electrodes formed of metal nanowires.
在一實施例中,該等複數電極之間的線距為30~200μm。In one embodiment, the line spacing between the plurality of electrodes is 30-200 μm.
在一實施例中,該透明導電膜在直流電與電壓5V,高溫高濕環境85℃/85%的測試條件下,當線距為x μm且通電y hr後,其線電阻變化率低於10%,其中x, y符合以下關係式:y=0.53179x+364.47977。In one embodiment, the transparent conductive film has a line resistance variation rate of less than 10% under the test conditions of direct current and voltage 5V, high temperature and high humidity environment 85°C/85%, when the line spacing is x μm and the power is on for y hr, wherein x and y satisfy the following relationship: y=0.53179x+364.47977.
在一實施例中,該透明導電膜在直流電與電壓5V,高溫高濕環境85℃/85%的測試條件下通電400hr後,其線電阻變化率低於10%。In one embodiment, after the transparent conductive film is powered on for 400 hours under the test conditions of direct current and voltage 5V, high temperature and high humidity environment 85℃/85%, its line resistance change rate is less than 10%.
在一實施例中,該透明導電膜之可見光穿透度為92~97%。In one embodiment, the visible light transmittance of the transparent conductive film is 92-97%.
在一實施例中,該透明導電膜之黃度(b*)為0.5以下。In one embodiment, the yellowness (b*) of the transparent conductive film is less than 0.5.
在一實施例中,該阻水保護層的厚度為1~15 μm。In one embodiment, the thickness of the water-blocking protective layer is 1-15 μm.
在一實施例中,該吸水性粒子占該阻水保護層的體積百分比為1~5%。In one embodiment, the volume percentage of the water-absorbing particles in the water-blocking protective layer is 1-5%.
藉由本發明的透明導電膜,能夠改善先前技術之透明導電膜之不耐彎折及可視性的問題,且因本發明的透明導電膜具有可彎折和高阻水等性能,故能夠適當地應用於觸控感應器中。The transparent conductive film of the present invention can improve the problems of the prior art transparent conductive film such as the inability to withstand bending and poor visibility. Moreover, since the transparent conductive film of the present invention has the properties of being bendable and highly water-resistant, it can be appropriately applied to touch sensors.
以下係藉由特定的具體實施例說明本發明之實施方式,熟習此技藝之人士可由本說明書所揭示之內容瞭解本發明之其他優點與功效。本發明也可藉由其他不同的具體實施例加以實施或應用,本說明書中的各項細節亦可基於不同觀點與應用,在不悖離本發明之精神下進行各種修飾與變更。The following is a description of the implementation of the present invention through specific embodiments. People skilled in the art can understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments. The details in this specification can also be modified and changed based on different viewpoints and applications without departing from the spirit of the present invention.
除非文中另有說明,否則說明書及所附申請專利範圍中所使用之單數形式「一」及「該」包括複數含義。Unless otherwise specified in the context, the singular forms "a", "an" and "the" used in the specification and the attached patent claims include plural meanings.
除非文中另有說明,否則說明書及所附申請專利範圍中所使用之術語「或」包括「及/或」之含義。Unless otherwise specified in the text, the term "or" used in the specification and the attached patent claims includes the meaning of "and/or".
除非文中另有說明,否則說明書及所附申請專利範圍中所使用之術語「A~B」係包括「A以上且B以下」之含義。例如,術語「30~150 μm」係包括「30 μm以上且150 μm以下」之含義。Unless otherwise specified in the text, the term "A~B" used in the specification and the attached patent application scope includes the meaning of "above A and below B". For example, the term "30~150 μm" includes the meaning of "above 30 μm and below 150 μm".
<透明導電膜>
首先,請參照圖1,針對本發明一實施例的透明導電膜10進行說明。如圖1所示,透明導電膜10係包含:基板1、金屬奈米線層2及阻水保護層3。其中,金屬奈米線層2設置於基板1,且阻水保護層3設置於金屬奈米線層2上。
<Transparent conductive film>
First, please refer to FIG. 1 to explain a transparent
就基板1的材料而言,可選自由聚對苯二甲酸乙二酯(polyethylene terephthalate, PET)、環烯烴共聚物(Cyclic olefin copolymer, COP)、無色聚醯亞胺(Colorless Polyimide, CPI)、聚萘二甲酸乙二醇酯(Polyethylene naphthalate, PEN)、聚碳酸酯(Polycarbonate, PC)及聚醚碸(Polyethersulfone, PES)所組成之群組中任一者。又,就基板1的厚度而言,可為15~125 μm,較佳為25~100 μm,更佳為30~50 μm。此處,若基板1的厚度小於15 μm,則在製程上不易操作,張力不好控制也容易造成斷膜,增加工藝困難性;另一方面,若基板1的厚度大於125 μm,則會影響整體光學與可撓性。As for the material of the
接著,就金屬奈米線層2而言,其包含被覆蓋層所覆蓋之金屬奈米線,可使用任何金屬的奈米線,包括但不限於:銀、金、銅、鎳以及鍍金的銀。其中,就成本和導電性的觀點來看,較佳係銀奈米線,其製造方式可參照美國專利US8454721B2、US9672950B2,該等專利全文皆以引用方式併入本文中。其中,覆蓋層可為具有黏合劑高分子材料,例如可為環氧壓克力系、胺基甲酸酯壓克力系、聚酯壓克力系及聚醚壓克力系樹脂等的丙烯酸酯系樹脂,其目的為固定奈米銀線以形成金屬奈米線層2。又,金屬奈米線層2的厚度較佳為20~120 nm,更佳為30~100 nm,最佳為40~90 nm,且可藉由將金屬奈米線樣品切片後透過SEM剖面分析來量測金屬奈米線層2的厚度。藉由此厚度範圍的金屬奈米線層2,並搭配後述之阻水保護層能夠達成較佳的導電效果。Next, as for the
再者,就阻水保護層3的材料而言,其主要係由具有特定透水性區間的高分子材料所組成,例如壓克力膠、矽膠、聚烯烴膠、聚氨酯膠、橡膠、環氧膠等。又,阻水保護層3包含吸水性粒子4,且吸水性粒子4占該阻水保護層3的體積百分比較佳為1~5%,若可兼具吸水效果及可視性需求則無需對吸水性粒子相對體積進行限制。就該吸水性粒子4而言,可包含聚烯烴的醯氨基聚合物,包含且不限於聚醯亞胺嵌段共聚物改性之聚乙烯等。前述聚醯亞胺嵌段共聚物改性之聚乙烯的主要膠體結構為包含95~99%的聚烯烴鏈段,吸水性官能基則來自於能夠與水結合之胺基。且令人驚訝的,本發明所使用的吸水性粒子4僅需要阻水保護層3的1~5體積%即可達成同時兼具吸水性以避免金屬(例如銀)離子遷移造成的斷路、短路以及同時具備整體優良可視性的效果。Furthermore, as for the material of the water-blocking
相較於先前技術,本發明一實施例藉由將吸水性粒子的比例控制在阻水保護層的5體積%以下,可有效避免整體光學性質較差,尤其是霧度值過高的問題。若將吸水性粒子的比例大於阻水保護層的5體積%,則可能會降低保護層與金屬奈米線層的附著力,使得透明導電膜的整體結構在彎曲時產生剝離現象,進而導致斷路的產生。又,若吸水性粒子的比例小於阻水保護層的1體積%,則無法獲得理想的吸水效果。Compared with the prior art, an embodiment of the present invention can effectively avoid the problem of poor overall optical properties, especially excessive haze value, by controlling the proportion of water-absorbing particles to less than 5 volume % of the water-blocking protective layer. If the proportion of water-absorbing particles is greater than 5 volume % of the water-blocking protective layer, the adhesion between the protective layer and the metal nanowire layer may be reduced, causing the overall structure of the transparent conductive film to peel off when bent, thereby causing the generation of a short circuit. On the other hand, if the proportion of water-absorbing particles is less than 1 volume % of the water-blocking protective layer, the ideal water absorption effect cannot be obtained.
另外,阻水保護層的厚度也與透明導電膜的整體性質相關,若阻水保護層的厚度增加,則能夠提升層與層之間的附著力且避免剝離;然而,若阻水保護層的厚度太厚,則可能會影響透明導電膜之整體光學性質的表現。因此,阻水保護層的厚度較佳為1~15 μm,更佳為5~15 μm,特佳為5~10 μm。此處,若阻水保護層的厚度小於1 μm,則會使金屬奈米線層的金屬產生氧化現象,進而影響導電性;另一方面,若阻水保護層的厚度大於15 μm,則會造成接觸阻抗變高,阻礙電訊號傳遞。In addition, the thickness of the water barrier protective layer is also related to the overall properties of the transparent conductive film. If the thickness of the water barrier protective layer increases, the adhesion between the layers can be improved and peeling can be avoided; however, if the thickness of the water barrier protective layer is too thick, it may affect the overall optical properties of the transparent conductive film. Therefore, the thickness of the water barrier protective layer is preferably 1~15 μm, more preferably 5~15 μm, and particularly preferably 5~10 μm. Here, if the thickness of the water barrier protective layer is less than 1 μm, the metal of the metal nanowire layer will be oxidized, thereby affecting the conductivity; on the other hand, if the thickness of the water barrier protective layer is greater than 15 μm, the contact impedance will increase, hindering the transmission of electrical signals.
此外,在考慮阻水保護層厚度的同時,仍需與吸水性粒子的填充率一同考量,以免影響透明導電膜的可視性(例如霧度)等。具體來說,當阻水保護層的厚度小於1 μm時,可能會有無法充分發揮阻水保護功效的情況;另一方面,當阻水保護層的厚度大於15 μm時,則可能會影響透明導電膜之整體光學性質的表現。In addition, when considering the thickness of the water-blocking protective layer, it is still necessary to consider the filling rate of the water-absorbing particles together to avoid affecting the visibility of the transparent conductive film (such as haze). Specifically, when the thickness of the water-blocking protective layer is less than 1 μm, the water-blocking protective effect may not be fully exerted; on the other hand, when the thickness of the water-blocking protective layer is greater than 15 μm, it may affect the overall optical properties of the transparent conductive film.
[實施例] 以下,藉由實施例及比較例,具體地說明本發明。 [Examples] The present invention is described in detail below through examples and comparative examples.
<參考例> 使用PET(Toray公司製,U483)作為基板的材料,且基板的厚度為50 μm。接著,在基板上塗佈奈米銀線層,奈米銀線層的厚度為40 nm。於參考例中,在未塗佈阻水保護層的情況下,形成參考例的透明導電膜。 <Reference Example> PET (Toray, Inc., U483) was used as the substrate material, and the thickness of the substrate was 50 μm. Then, a nanosilver wire layer was coated on the substrate, and the thickness of the nanosilver wire layer was 40 nm. In the reference example, the transparent conductive film of the reference example was formed without coating a water-blocking protective layer.
(光學性質的測定) 可使用習知的量測方法,來測定透明導電膜的可見光穿透率(T%)、霧度(Haze)(%)和黃度(b*)。舉例來說,可分別使用桌上型穿透式霧度計(BYK Gardner公司製,Haze-guard plus)並藉由透射法來量測透明導電膜的光穿透率與霧度;並可藉由紫外光/可見光分光光譜儀(PerkinElmer公司製,Lambda 650)搭配150mm積分球進行穿透光譜量測,再藉由CIE標準觀察者函數的方程式計算出黃度(b*)。在本發明中,透明導電膜的霧度需為1.7%以下,且可見光穿透率(T%)以92~97%為佳,黃度(b*)以0.5以下為佳。 (Measurement of optical properties) The visible light transmittance (T%), haze (%) and yellowness (b*) of the transparent conductive film can be measured by known measurement methods. For example, a desktop transmission haze meter (BYK Gardner, Haze-guard plus) can be used to measure the light transmittance and haze of the transparent conductive film by the transmission method; and a UV/visible light spectrophotometer (PerkinElmer, Lambda 650) can be used with a 150mm integrating sphere to measure the transmission spectrum, and then the yellowness (b*) can be calculated by the equation of the CIE standard observer function. In the present invention, the haze of the transparent conductive film needs to be less than 1.7%, and the visible light transmittance (T%) is preferably 92~97%, and the yellowness (b*) is preferably less than 0.5.
接著,依據下述表1中吸水性粒子的含量和阻水保護層的厚度,於參考例的奈米銀線層上進一步塗佈阻水保護層,以製作實施例1~7和比較例1~2的透明導電膜;其中,各實施例和比較例的阻水保護層係為壓克力膠,且含有特定含量之聚醯亞胺嵌段共聚物改性之聚乙烯以作為吸水性粒子。之後,針對參考例、實施例1~7和比較例1~2的透明導電膜進行光學性質的測定,並將結果整理於下述表1。Then, according to the content of water-absorbing particles and the thickness of the water-blocking protective layer in Table 1 below, a water-blocking protective layer was further coated on the nanosilver wire layer of the reference example to prepare transparent conductive films of Examples 1 to 7 and Comparative Examples 1 to 2; wherein the water-blocking protective layer of each Example and Comparative Example is an acrylic glue and contains a specific content of polyethylene modified by polyimide block copolymer as water-absorbing particles. Afterwards, the optical properties of the transparent conductive films of the reference example, Examples 1 to 7 and Comparative Examples 1 to 2 were measured, and the results are summarized in Table 1 below.
[表1]
首先,由表1可知,在未塗佈阻水保護層的情況下,參考例的透明導電膜具有最低的霧度(0.46%)。然而,因為奈米銀本身有先天性的電解離問題,尤其在通電與水氣的條件下容易發生銀離子遷移(silver migration)的現象,進而造成奈米銀的可靠度降低。因此,參考例的透明導電膜的壽命短(參照後述之銀遷移測試),需要在盡量不影響光學性質的情況下進一步塗佈阻水保護層。First, it can be seen from Table 1 that the transparent conductive film of the reference example has the lowest haze (0.46%) without a water-blocking protective layer. However, because nanosilver itself has an inherent electrolytic ionization problem, especially under the conditions of electricity and water vapor, silver ion migration is prone to occur, which in turn reduces the reliability of nanosilver. Therefore, the transparent conductive film of the reference example has a short life (refer to the silver migration test described later), and it is necessary to further apply a water-blocking protective layer without affecting the optical properties as much as possible.
其次,如表1所示,塗佈阻水保護層後,雖然阻水保護層對於可見光穿透率的影響不大,但對於霧度跟黃度有較大影響。由實施例1~6能夠得知,在吸水性粒子的含量為少(約為1±0.5體積%)或中(約為2.5±0.5體積%)的條件下,阻水保護層的厚度可為5~15 µm,皆能夠在可接受的情況下(霧度值為1.7%以下、黃度為0.5以下),抑制銀離子遷移的現象。Secondly, as shown in Table 1, after applying the water-blocking protective layer, although the water-blocking protective layer has little effect on the visible light transmittance, it has a greater effect on the haze and yellowness. It can be seen from Examples 1 to 6 that when the content of water-absorbing particles is low (about 1±0.5 volume %) or medium (about 2.5±0.5 volume %), the thickness of the water-blocking protective layer can be 5 to 15 µm, and the phenomenon of silver ion migration can be suppressed under acceptable conditions (haze value is less than 1.7% and yellowness is less than 0.5).
再者,由表1能夠得知,在吸水性粒子的含量為多(約為5±0.5體積%)的情況下,若阻水保護層的厚度為10 µm、15 µm(參照比較例1~2),則能夠發現霧度值急遽上升(大於1.7%),且在比較例2中亦觀察到黃度大於0.5的現象,故比較例1~2為不佳。此現象係因為吸水性粒子中-CH基與-NH基的極性不相容,比較例1~2中吸水性粒子的含量太高再加上阻水保護層過厚,造成分子間氫鍵增加,因此分子排列的混亂,進一步使得霧度和黃度快速增加。由此可知,在吸水性粒子的含量為1±0.5~2.5±0.5體積%的條件下,即使阻水保護層的厚度為15 µm,亦能夠符合本發明所欲的霧度值(1.7%以下);然而,在吸水性粒子的含量為5±0.5體積%的條件下,當阻水保護層的厚度為10 µm、15 µm時,即無法符合本發明所欲的霧度值。Furthermore, it can be seen from Table 1 that when the content of water-absorbing particles is high (about 5±0.5 volume %), if the thickness of the water-blocking protective layer is 10 µm or 15 µm (refer to Comparative Examples 1-2), the haze value rises sharply (greater than 1.7%), and the yellowness is also observed to be greater than 0.5 in Comparative Example 2, so Comparative Examples 1-2 are not good. This phenomenon is because the polarity of -CH group and -NH group in water-absorbing particles is incompatible. In Comparative Examples 1-2, the content of water-absorbing particles is too high and the water-blocking protective layer is too thick, resulting in an increase in intermolecular hydrogen bonds, so the molecular arrangement is disordered, which further causes a rapid increase in haze and yellowness. It can be seen that when the content of the water-absorbing particles is 1±0.5~2.5±0.5 volume %, even if the thickness of the water-blocking protective layer is 15 µm, the desired haze value (below 1.7%) of the present invention can be met; however, when the content of the water-absorbing particles is 5±0.5 volume %, when the thickness of the water-blocking protective layer is 10 µm or 15 µm, the desired haze value of the present invention cannot be met.
接著,針對上述現象,進行進一步的探討,請參照圖2及表2和表3。圖2係參考例與實施例1、4、7的透明導電膜之FTIR圖譜。又,藉由將吸收光譜強度進行歸一化之後,可自圖2計算出各自的波峰強度值,且藉由積分吸收光譜方法可自圖2計算出各自的光譜積分面積;將結果整理於以下的表2及表3。Next, for further discussion of the above phenomenon, please refer to Figure 2 and Tables 2 and 3. Figure 2 is the FTIR spectrum of the transparent conductive film of the reference example and Examples 1, 4, and 7. In addition, by normalizing the absorption spectrum intensity, the peak intensity value of each can be calculated from Figure 2, and the integrated absorption spectrum method can be used to calculate the integrated area of each spectrum from Figure 2; the results are summarized in the following Tables 2 and 3.
[表2]
如圖2所示,因為參考例並未塗佈阻水保護層,故未觀察到來自吸水性粒子的-CH基特徵峰與-NH基特徵峰。又,如圖2所示,實施例1、4、7皆可在約2945 cm -1的位置觀察到-CH基特徵峰,以及在約3450 cm -1的位置觀察到-NH基特徵峰。又,實施例1、4、7的-CH基特徵峰的最大強度為0.922~0.999,各實施例間較無差距;相對地,-NH基特徵峰的最大強度為0.173~0.378,各實施例間差異較大。 As shown in FIG2 , because the reference example does not apply a water-blocking protective layer, the characteristic peaks of -CH and -NH from the water-absorbing particles are not observed. Also, as shown in FIG2 , the characteristic peaks of -CH can be observed at about 2945 cm -1 in Examples 1, 4, and 7, and the characteristic peaks of -NH can be observed at about 3450 cm -1 . In addition, the maximum intensity of the characteristic peaks of -CH in Examples 1, 4, and 7 is 0.922-0.999, which is relatively similar among the Examples; in contrast, the maximum intensity of the characteristic peaks of -NH is 0.173-0.378, which is relatively different among the Examples.
又,圖2中-CH基特徵峰(2750 cm -1-3000 cm -1波數區域中的第一吸收波峰)與-NH基特徵峰(3000 cm -1-3750 cm -1波數區域中的第二吸收波峰)的最大峰值強度比值(第二吸收波峰/第一吸收波峰)係代表吸水的能力,若最大峰值強度比值(亦簡稱為強度比值)越大,則吸水能力越佳。在本發明中,第一吸收波峰與第二吸收波峰的最大峰值強度比值為0.18~0.50,若強度比值小於0.18,則因為N-H鍵的數量過低,無法達成充分的吸水/阻水效果;相對於此,若強度比值大於0.50,則光學性質可能會下降,即使在阻水保護層的厚度為低的情況(例如5 μm),霧度也可能會大於2%,不利透明導電膜的進一步應用。 In addition, the maximum peak intensity ratio (second absorption peak/first absorption peak) of the characteristic peak of the -CH group (the first absorption peak in the wave number region of 2750 cm - 1-3000 cm- 1 ) and the characteristic peak of the -NH group (the second absorption peak in the wave number region of 3000 cm - 1-3750 cm -1 ) in Figure 2 represents the ability to absorb water. The larger the maximum peak intensity ratio (also referred to as the intensity ratio), the better the water absorption ability. In the present invention, the maximum peak intensity ratio of the first absorption peak to the second absorption peak is 0.18~0.50. If the intensity ratio is less than 0.18, the number of NH bonds is too low to achieve sufficient water absorption/water blocking effect. In contrast, if the intensity ratio is greater than 0.50, the optical properties may decrease, and even when the thickness of the water-blocking protective layer is low (for example, 5 μm), the haze may be greater than 2%, which is not conducive to the further application of the transparent conductive film.
具體而言,由於本發明使用吸水粒子的主成分由聚醯亞胺所組成,聚醯亞胺是一種含有醯亞胺環(-CO-NH-CO-)的有機高分子材料,其分子鏈含有大量的芳香基(如苯環、醯亞胺鍵等)。因此,聚醯亞胺材料除了具有優良的熱安定性及機械、電氣及化學性質之外,也具有高吸水特性。Specifically, since the main component of the water-absorbing particles used in the present invention is composed of polyimide, which is an organic polymer material containing an imide ring (-CO-NH-CO-), and its molecular chain contains a large number of aromatic groups (such as benzene rings, imide bonds, etc.), the polyimide material not only has excellent thermal stability and mechanical, electrical and chemical properties, but also has high water absorption properties.
此外,如圖2和下述表3所示,在第一吸收波峰的光譜積分面積與第二吸收波峰的光譜積分面積之比值(第二吸收波峰的光譜積分面積/第一吸收波峰的光譜積分面積)為0.618~1.410的情況下,亦能夠在吸水特性和光學性質之間達到適當的平衡。In addition, as shown in FIG. 2 and Table 3 below, when the ratio of the spectral integration area of the first absorption peak to the spectral integration area of the second absorption peak (spectral integration area of the second absorption peak/spectral integration area of the first absorption peak) is 0.618~1.410, a proper balance can be achieved between the water absorption characteristics and the optical properties.
[表3]
接著,藉由以下的樣品製造方法,佐證本發明能夠抑制奈米銀遷移機制的發生。Then, the following sample preparation method was used to prove that the present invention can inhibit the occurrence of nanosilver migration mechanism.
(樣品製造方法)
首先,依據圖4的流程,分別基於參考例與實施例1製作銀遷移測試的樣品。具體來說,樣品的製作包含奈米銀與銅墊圖案化製程(S1~S6)和銅開窗製程(S7~S10)。
S1:於參考例的透明導電膜之金屬奈米層(奈米銀線層)2上濺鍍上一層約200 nm厚度之金屬銅層5。又,於實施例1的透明導電膜之阻水保護層(未圖示)上濺鍍上一層約200 nm厚度之金屬銅層5。
S2:接續於S1,於各自的銅層5上塗佈一層光阻6。
S3:接續於S2,利用第一道光罩進行曝光顯影製程,定義奈米銀線層與銅墊(層)之線路與電極圖案。
S4:接續於S3,使用銅蝕刻液進行銅蝕刻,完成銅線路與電極製作。
S5:接續於S4,使用銀蝕刻液進行奈米銀蝕刻,完成奈米銀線電極製作。
S6:接續於S5,使用剝膜液將光阻進行剝膜去除,完成奈米銀線層與銅墊(層)圖案化製程。
S7:接續於S6,再塗佈一層光阻6’於奈米銀與銅墊圖案化後之透明導電膜上。
S8:接續於S7,利用第二道光罩進行曝光顯影製程,定義銅開窗圖案。
S9:接續於S8,利用銅蝕刻液進行銅蝕刻。
S10:最後使用剝膜液將經過S9後之光阻6’進行剝膜去除,即完成銅開窗製程,獲得銀遷移測試的樣品。
(Sample manufacturing method)
First, according to the process of Figure 4, samples for silver migration test are prepared based on the reference example and Example 1 respectively. Specifically, the sample preparation includes nanosilver and copper pad patterning process (S1~S6) and copper window opening process (S7~S10).
S1: A
將各銀遷移測試的樣品置放在高溫高濕(85℃/85%)的環境下,並且通以直流電(DC)與電壓5伏特,以此測試條件下追蹤奈米銀線層中的奈米銀線阻隨著時間的變化;其中,奈米銀線電極的寬度為100 μm,奈米銀線電極之間的間距(線距)為50 μm。銀遷移測試的結果請參照圖3和圖5。又,奈米銀線電極之間的線距可在30~200μm之間調整。The samples for silver migration test were placed in a high temperature and high humidity environment (85℃/85%), and a direct current (DC) and a voltage of 5V were applied to track the change of the resistance of the nanosilver wire in the nanosilver wire layer over time under these test conditions; the width of the nanosilver wire electrode was 100 μm, and the spacing (line spacing) between the nanosilver wire electrodes was 50 μm. Please refer to Figures 3 and 5 for the results of the silver migration test. In addition, the line spacing between the nanosilver wire electrodes can be adjusted between 30~200μm.
圖3係參考例與實施例1之銀遷移測試圖。如圖3所示,參考例的透明導電膜在通電約45小時(hr)後,線電阻變化率即大於10%;相對於此,實施例1的透明導電膜在通電約450小時後,線電阻變化率才大於10%。由此可知,相較於參考例的透明導電膜,實施例1的透明導電膜在嚴苛的銀遷移測試條件下(DC直流電與電壓5V,高溫高濕環境85℃/85%),其壽命(線電阻變化率升高至大於10%為止的時間點)可延展將近10倍左右,由45小時拉長至450小時。此外,實施例1的透明導電膜在通電400小時後,線電阻變化率僅約為8%左右。FIG3 is a graph of silver migration test of the reference example and Example 1. As shown in FIG3, the line resistance change rate of the transparent conductive film of the reference example is greater than 10% after about 45 hours (hr) of power-on; in contrast, the line resistance change rate of the transparent conductive film of Example 1 is greater than 10% after about 450 hours of power-on. It can be seen that, compared with the transparent conductive film of the reference example, the transparent conductive film of Example 1 can extend its life (the time point when the line resistance change rate increases to greater than 10%) by nearly 10 times, from 45 hours to 450 hours under the strict silver migration test conditions (DC direct current and voltage 5V, high temperature and high humidity environment 85℃/85%). In addition, the line resistance change rate of the transparent conductive film of Example 1 is only about 8% after being powered on for 400 hours.
又,如圖5所示,由於電極的線寬一般不會影響銀離子的遷移,因此在固定線寬為100μm,線距(Gap Distance)分別為30μm、50μm、100μm和200μm的條件下分別進行測試,通過測試的情況分別為380hr、390hr、420hr、470hr時的電阻變化率小於10%。因此,可知線距與壽命(Life time)呈線性關係,其關係式可表示為 y=0.53179x+364.47977(x= gap distance, y= Life time)。As shown in Figure 5, since the line width of the electrode generally does not affect the migration of silver ions, the test was conducted under the conditions of fixed line width of 100μm and line distance (Gap Distance) of 30μm, 50μm, 100μm and 200μm respectively. The resistance change rate at 380hr, 390hr, 420hr and 470hr was less than 10%. Therefore, it can be seen that the line distance and life (Life time) are linearly related, and the relationship can be expressed as y=0.53179x+364.47977 (x= gap distance, y= Life time).
由上述結果可知,本發明的透明導電膜藉由覆蓋阻水保護層,其信賴性被大幅提升,能夠進一步提高奈米銀線層在電子產品性能的穩定性。From the above results, it can be seen that the reliability of the transparent conductive film of the present invention is greatly improved by covering the water-blocking protective layer, which can further improve the stability of the performance of the nanosilver wire layer in electronic products.
本發明的透明導電膜可應用於觸控感測器的觸控感測電極中。此外,還可應用於平面/柔性觸控的顯示器、有機光伏(OPV, organic photovoltaic)、OLED照明、智能窗戶等可能會包含透明導電膜之產品。The transparent conductive film of the present invention can be applied to the touch sensing electrode of a touch sensor. In addition, it can also be applied to flat/flexible touch displays, organic photovoltaics (OPV), OLED lighting, smart windows and other products that may contain transparent conductive films.
綜合上述,本發明之透明導電膜及其應用至少具有下列優良的技術效果: 1. 本發明之透明導電膜具有可彎折的效果,並且在於不減損導電層導電性的狀態下可維持層間附著力。 2. 本發明之透明導電膜能夠在嚴苛環境下抑制銀離子的遷移,並能夠在不減損導電性的狀態下兼具了優良的可視性效果,尤其是霧度的特性甚為明顯。 In summary, the transparent conductive film of the present invention and its application have at least the following excellent technical effects: 1. The transparent conductive film of the present invention has a bendable effect, and can maintain interlayer adhesion without reducing the conductivity of the conductive layer. 2. The transparent conductive film of the present invention can inhibit the migration of silver ions in harsh environments, and can have excellent visibility without reducing the conductivity, especially the haze characteristics are very obvious.
本發明並不限定於上述各實施形態,可在請求項所示之範圍內做各種的變更,且將不同的實施形態中所揭示之技術手段適宜地組合而得之實施形態亦包含在本發明的技術範圍內。The present invention is not limited to the above-mentioned embodiments, and various modifications can be made within the scope indicated in the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.
1:基板 2:金屬奈米線層 3:阻水保護層 10:透明導電膜 4:吸水性粒子 5:銅層 6:光阻 S1~S10:步驟 1: Substrate 2: Metal nanowire layer 3: Water-blocking protective layer 10: Transparent conductive film 4: Water-absorbing particles 5: Copper layer 6: Photoresist S1~S10: Steps
圖1係本發明一實施例的透明導電膜之示意圖。
圖2係參考例與實施例1、4、7的透明導電膜之FTIR圖譜。
圖3係參考例與實施例1之銀遷移測試圖。
圖4係銀遷移測試樣品的製作流程圖。
圖5係銀遷移測試樣品的線距與壽命之關係圖。
FIG1 is a schematic diagram of a transparent conductive film of an embodiment of the present invention.
FIG2 is an FTIR spectrum of the transparent conductive film of the reference example and
1:基板 1: Substrate
2:金屬奈米線層 2: Metal nanowire layer
3:阻水保護層 3: Water-blocking protective layer
4:吸水性粒子 4: Water-absorbent particles
10:透明導電膜 10: Transparent conductive film
Claims (10)
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TW111134930A TWI850767B (en) | 2022-09-15 | Transparent conductive film |
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TW111134930A TWI850767B (en) | 2022-09-15 | Transparent conductive film |
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TWI850767B TWI850767B (en) | 2024-08-01 |
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