TW201636203A - Substrate with conductive film and its manufacturing method and electro-conductive paste for polyimide substrate - Google Patents
Substrate with conductive film and its manufacturing method and electro-conductive paste for polyimide substrate Download PDFInfo
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- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- H—ELECTRICITY
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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Abstract
Description
本發明是涉及在聚醯亞胺基板上具備有導電膜之附導電膜之基板、其製造方法、及適合用於形成此導電膜之導電性糊。 The present invention relates to a substrate comprising a conductive film having a conductive film on a polyimide substrate, a method for producing the same, and a conductive paste suitable for forming the conductive film.
舉例來說，在形成電路基板之配線、形成電子零件之電極等所使用之導電性糊是由導電性粉末、樹脂結合劑、有機溶劑、及因應需要而含有之玻璃粉等之無機填料所成。此導電性糊大致分為可藉由在大概300(℃)以下之低溫施行熱處理而在基板上形成導體膜之熱硬化類型、及藉由在400(℃)以上溫度施行燒成處理而形成導體膜之燒成類型。 For example, a conductive paste used for forming a wiring of a circuit board, an electrode for forming an electronic component, or the like is formed of an inorganic filler such as a conductive powder, a resin binder, an organic solvent, and a glass powder contained as needed. . The conductive paste is roughly classified into a heat-curing type in which a conductor film can be formed on a substrate by heat treatment at a low temperature of about 300 (° C.) or less, and a conductor is formed by firing at a temperature of 400 (° C. or more). The type of film burned.
前者之熱硬化類型是使用熱硬化樹脂來作為樹脂結合劑，藉由熱處理令此熱硬化樹脂硬化而形成導電膜。此類型由於處理溫度低故具有基板材質不受限之優點，但導電性粉末只是在相互接觸之狀態下被樹脂結合劑所固定而已，而且，由於樹脂殘留故電阻值升高，另外， 而具有著耐熱性與長期之可靠性低之缺點。 The former is a type of thermal hardening in which a thermosetting resin is used as a resin binder, and the thermosetting resin is cured by heat treatment to form a conductive film. Since this type has an advantage that the substrate material is not limited because of the low processing temperature, the conductive powder is fixed only by the resin binder in a state of being in contact with each other, and the resistance value is increased due to resin residue, and It has the disadvantage of low heat resistance and low reliability in the long term.
另一方面，後者之燒成類型是藉由燒成處理令導電性粉末本身燒結或是加上玻璃粉燒結而形成導電膜。此類型由於是使樹脂燒掉並令導電性粉末燒結，故有著電阻值低、耐熱性與長期之可靠性高之優點，但因為需要高溫之燒成處理，故不適用於樹脂基板，有著製造成本亦變高之缺點。 On the other hand, the latter type of firing is to form a conductive film by sintering the conductive powder itself or by sintering the glass powder by a firing treatment. This type has the advantages of low electrical resistance, high heat resistance and long-term reliability because it burns off the resin and sinters the conductive powder. However, since it requires high-temperature firing treatment, it is not suitable for resin substrates. The disadvantage of higher costs.
專利文獻1：日本特開2006-310022號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2006-310022
專利文獻2：日本特開2011-252140號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 2011-252140
專利文獻3：日本特開2011-065783號公報 Patent Document 3: JP-A-2011-065783
話說，身為樹脂基板之一種之聚醯亞胺基板是因為耐熱性高且可撓性佳，故廣泛地被用在可移動終端其他電子機器之基板。關於對聚醯亞胺基板形成配線，主流之方法是將銅壓附並施行蝕刻來進行圖樣形成，但為了令導體配線低電阻化，有在檢討藉由網版印刷等而以厚膜形成。如前述，由於樹脂基板無法使用燒成類型之導電性糊，故從習知就在嘗試改善熱硬化類型之導電性糊，但並未獲得充分之導電性。 In other words, a polyimide substrate which is a resin substrate is widely used in substrates of other electronic devices of mobile terminals because of its high heat resistance and flexibility. In the method of forming a wiring on a polyimide substrate, a copper paste is pressed and etched to form a pattern. However, in order to reduce the resistance of the conductor wiring, a thick film is formed by screen printing or the like. As described above, since the baking paste type conductive paste cannot be used for the resin substrate, it has been conventionally attempted to improve the thermosetting type conductive paste, but sufficient conductivity has not been obtained.
舉例來說，有人提案在由導電性粉末與溶劑與 黏合劑所成之導電性糊，令此黏合劑是包含有從鋁化合物及矽烷耦合劑選出之一種或二種以上(參考專利文獻1。)。此導電性糊是藉由在200(℃)施行乾燥處理而形成導電膜，但比電阻為2.9×10-5(Ω‧cm)~6.1×10-5(Ω‧cm)左右，處於偏高之值。可以想到的是鋁化合物及矽烷耦合劑使導電性降低。 For example, a conductive paste made of a conductive powder, a solvent, and a binder is proposed, and the binder is one or more selected from the group consisting of an aluminum compound and a decane coupling agent (refer to Patent Document 1). ). This conductive paste is formed by drying at 200 (° C.) to form a conductive film, but the specific resistance is about 2.9×10 -5 (Ω·cm) to 6.1×10 -5 (Ω·cm), which is high. The value. It is conceivable that the aluminum compound and the decane coupling agent lower the conductivity.
另外，有人提案導電性墨是含有：導電性粒子，敲緊密度為1.0~10.0(g/cm3)，D50粒徑為0.3~5(μm)，BET比表面積0.3~5.0(m2/g)；環氧樹脂，數量平均分子量為10000~300000，羥值2~300(mgKOH/g)；金屬螯合物，可與該環氧樹脂中之羥基進行醇解反應，與該環氧樹脂100重量份相較之下為0.2~20重量份(參考專利文獻2。)。該導電性墨是用於印刷形成高精細之導電性圖樣，雖然有記載提到對聚醯亞胺基板之密接性佳，但與上述糊同樣為熱硬化類型，電阻率為5.0×10-5(Ω‧cm)左右之高，導電性不充分。 In addition, it has been proposed that the conductive ink contains: conductive particles, the knocking degree is 1.0 to 10.0 (g/cm 3 ), the D50 particle diameter is 0.3 to 5 (μm), and the BET specific surface area is 0.3 to 5.0 (m 2 /g). An epoxy resin having a number average molecular weight of 10,000 to 300,000 and a hydroxyl value of 2 to 300 (mgKOH/g); a metal chelate compound capable of undergoing an alcoholysis reaction with a hydroxyl group in the epoxy resin, and the epoxy resin 100 The parts by weight are 0.2 to 20 parts by weight in comparison (refer to Patent Document 2). The conductive ink is used for printing to form a high-precision conductive pattern. Although it is described that the adhesion to the polyimide substrate is good, it is the same as the above-mentioned paste, and the resistivity is 5.0×10 -5 . (Ω‧cm) is high and the conductivity is insufficient.
相較於這些，有人提案燒成類型之導電性糊，其是例如由金屬粉末成分、熱塑性樹脂、分散介質所成，與金屬、樹脂之合計質量相較之下之金屬之質量之比例為94~98%，金屬粉末成分是藉由平均一次粒徑為50(nm)以下之金屬粒子1之群、平均一次粒徑為100(nm)以上之金屬粒子2之群而構成(參考專利文獻3。)。據說，利用該導電性糊而在聚醯亞胺基板上藉由網版印刷等形成膜、以200(℃)左右之低溫進行燒成，可獲得導電性及密接性兼顧 之導電膜。 In contrast to this, a conductive paste of a firing type, which is formed, for example, from a metal powder component, a thermoplastic resin, or a dispersion medium, is used, and the ratio of the mass of the metal to the total mass of the metal and the resin is 94. ～98%, the metal powder component is composed of a group of metal particles 1 having an average primary particle diameter of 50 (nm) or less and a group of metal particles 2 having an average primary particle diameter of 100 (nm) or more (refer to Patent Document 3). .). It is said that the conductive paste is used to form a film on a polyimide substrate by screen printing or the like, and is fired at a low temperature of about 200 (° C.) to obtain both conductivity and adhesion. Conductive film.
然而，上述導電性糊仍未能取代銅壓附之配線，而被期待能進一步改善。導電性雖然在某程度上獲得改善但並非充分，而且，由於需要50(nm)以下之金屬微粉末，故成本高而操作性差。上述專利文獻3有記載僅使用平均粒徑為100(nm)以上之金屬粒子之導電性糊來作為導電性低之比較例，可以想到的原因是金屬粉末之燒結未充分進展。為了改善其燒結性，混合有50(nm)以下之微粉。 However, the above-mentioned conductive paste has not been able to replace the copper-embossed wiring, and is expected to be further improved. Although the conductivity is improved to some extent, it is not sufficient, and since a metal fine powder of 50 (nm) or less is required, the cost is high and the workability is poor. In the above-mentioned Patent Document 3, a conductive paste using only metal particles having an average particle diameter of 100 (nm) or more is used as a comparative example having low conductivity, and it is conceivable that the sintering of the metal powder is not sufficiently progressed. In order to improve the sinterability, fine powder of 50 (nm) or less is mixed.
本發明是以上述情事為背景而建構，其目的是提供具備有優異導電性與對聚醯亞胺基板之優異密接性之銀導電膜之附導電膜之基板、其製造方法、及可用在此附導電膜之基板之製造之聚醯亞胺基板用導電性糊。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a substrate having a conductive film having a silver conductive film having excellent conductivity and excellent adhesion to a polyimide substrate, a method for producing the same, and a method for producing the same. A conductive paste for a polyimide film having a substrate coated with a conductive film.
為了達成如此之目的，第1發明之要旨是一附導電膜之基板，該附導電膜之基板是在聚醯亞胺基板之一面具備有導電膜，且該導電膜包含銀作為導體成分；其中前述導電膜及前述聚醯亞胺基板之構成成分會越過其等界面並在該導電膜之厚度尺寸以下之範圍內相互侵入對方形成凹凸面，而以所形成之凹凸面作為其等界面。 In order to achieve such an object, the first invention is directed to a substrate having a conductive film, the substrate having the conductive film being provided with a conductive film on one side of the polyimide substrate, and the conductive film containing silver as a conductor component; The constituent elements of the conductive film and the polyimide substrate pass through the interface and form an uneven surface in the range of the thickness of the conductive film or less, and the formed uneven surface serves as the interface.
另外，用於達成前述目的之第2發明之要旨是一將包含銀作為導體成分之導電膜形成在聚醯亞胺基板上之附導電膜之基板之製造方法，其包含以下步驟：(a)糊塗布步驟，將含有銀粉末、樹脂結合劑及有機溶劑之導電性糊以預定圖樣塗布在前述聚醯亞胺基板上，其中該銀粉末在 表面附著有由松香、脂肪酸及胺類中之至少其中1種構成之預定量的塗佈劑；(b)燒成步驟，以250~300(℃)之最高溫度施行燒成處理，藉此使銀燒結而由前述導電性糊生成導電膜。 Further, a second invention for achieving the above object is a method for producing a substrate having a conductive film formed of a conductive film containing silver as a conductor component on a polyimide substrate, comprising the following steps: (a) a paste coating step of coating a conductive paste containing a silver powder, a resin binder, and an organic solvent on the polyimine substrate in a predetermined pattern, wherein the silver powder is a predetermined amount of a coating agent composed of at least one of rosin, a fatty acid, and an amine is adhered to the surface; (b) a baking step is performed at a maximum temperature of 250 to 300 (° C.), thereby making a baking treatment The silver is sintered to form a conductive film from the conductive paste.
另外，用於達成前述目的之第3發明之要旨是一用以在聚醯亞胺基板上形成導電膜而製造附導電膜之基板的聚醯亞胺基板用導電性糊，且其含有銀粉末、樹脂結合劑及有機溶劑；其中前述銀粉末是附著塗佈劑之銀粉末，且其是使由松香、脂肪酸及胺類中之至少其中1種構成之塗佈劑以相對於該銀粉末之質量比為2.3(%)以下之量附著在表面者。 In addition, the third invention for achieving the above object is a conductive paste for a polyimide film for producing a substrate having a conductive film on a polyimide film, and containing silver powder. a resin binder and an organic solvent; wherein the silver powder is a silver powder to which a coating agent is attached, and a coating agent composed of at least one of rosin, a fatty acid, and an amine is used in relation to the silver powder. A mass ratio of 2.3 (%) or less is attached to the surface.
根據前述第1發明，導電膜及聚醯亞胺基板是令其等之構成成分在導電膜之厚度尺寸以下之範圍內相互侵入對方，並將藉此形成之凹凸面作為其等界面，所以，導電性與密接性會伴隨接觸面積之增大而提高。因此，可獲得具備有高導電性與對聚醯亞胺基板之高密接性之導電膜之附導電膜之基板。 According to the first aspect of the invention, the conductive film and the polyimide substrate are formed such that the constituent components thereof enter each other within a range of the thickness of the conductive film or less, and the uneven surface formed thereby is used as the interface. Conductivity and adhesion are increased with an increase in contact area. Therefore, a substrate having a conductive film having a conductive film having high conductivity and high adhesion to a polyimide substrate can be obtained.
另外，根據前述第2發明，將導電膜形成在聚醯亞胺基板上而製造附導電膜之基板之際，於糊塗布步驟中塗布之導電性糊是使用令由松香、脂肪酸、或胺類構成之塗佈劑附著在表面的附著塗佈劑之銀粉末來作為銀粉末，所以，於燒成步驟中，即便以250~300(℃)之範圍內之低溫來施行燒成處理，燒結亦會充分進展，故可獲得具備有高 導電性與對聚醯亞胺基板之高密接性之導電膜之附導電膜之基板。若燒成溫度低於250(℃)，則燒結未充分進展，另一方面，超過300(℃)時，由於導電性、密接性並不會特別提升，故只是發生對聚醯亞胺基板賦予過剩之熱之不良效果。 Further, according to the second aspect of the invention, when the conductive film is formed on the polyimide substrate to produce the substrate with the conductive film, the conductive paste applied in the paste coating step is a rosin, a fatty acid, or an amine. Since the coating agent attached to the surface adheres to the silver powder of the coating agent as a silver powder, even in the baking step, the baking treatment is performed at a low temperature in the range of 250 to 300 (° C.), and the sintering is performed. Will make full progress, so you can get high A substrate with a conductive film attached to a conductive film having high conductivity to a polyimide substrate. When the baking temperature is lower than 250 (° C.), the sintering does not progress sufficiently. On the other hand, when the temperature exceeds 300 (° C.), the conductivity and the adhesion are not particularly improved, so that only the polyimide substrate is imparted. The adverse effect of excess heat.
附帶一提，關於包含銀粉末作為導體成分之導電性糊，若非如前述使用50(nm)以下之微粉般之特殊情形，通常，燒結在300(℃)以下之低溫並不會進展。因此，對聚醯亞胺基板等樹脂基板而言，一般是使用熱硬化型糊，但由於這只是在銀粉末相互接觸之狀態下藉由熱硬化樹脂予以固定，故得不到高導電性。然而，在本發明，並非熱硬化樹脂之固定，而是銀粉末本身燒結。如此地燒結性提升之理由尚不明確，可以想到的是隨著銀之燒結之進行，聚醯亞胺基板之表面與包含銀粉末之膜的接觸面積逐漸增大，附著在銀粉末之塗佈劑在該接觸界面作為接著劑或反應促進劑而發揮作用。 Incidentally, in the case where the conductive paste containing silver powder as a conductor component is not as special as the above-described fine powder of 50 (nm) or less, usually, sintering at a low temperature of 300 (° C. or less) does not progress. Therefore, in the case of a resin substrate such as a polyimide substrate, a thermosetting paste is generally used. However, since the silver powder is fixed by a thermosetting resin only in contact with each other, high conductivity is not obtained. However, in the present invention, not the fixing of the thermosetting resin, but the sintering of the silver powder itself. The reason why the sinterability is improved is not clear. It is conceivable that as the sintering of silver progresses, the contact area between the surface of the polyimide substrate and the film containing the silver powder gradually increases, and adhesion to the silver powder is applied. The agent acts as an adhesive or a reaction accelerator at the contact interface.
另外，根據前述第3發明，關於聚醯亞胺基板用之導電性糊，銀粉末是令由松香、脂肪酸、或胺類構成之塗佈劑在相對於銀粉末之質量比為2.3(%)以下之範圍附著的附著塗佈劑之銀粉末，所以，即便以300(℃)以下(宜為270(℃)以下)之低溫來施行燒成處理，銀粉末之燒結亦會充分進展，故可獲得高導電性與對聚醯亞胺基板之高密接性。附帶一提，即便在銀粉末只附著有少許塗佈劑，銀粉末之燒結性也會因應其量而增加，但超過2.3(%)而變得過 剩則會在燒成時變得不易燒穿，令膜密度降低，導電性降低。 Further, according to the third aspect of the invention, the conductive paste for the polyimide substrate has a silver powder such that the mass ratio of the coating agent composed of rosin, a fatty acid or an amine to the silver powder is 2.3 (%). Since the silver powder adhered to the coating agent adhered in the following range, even if the baking treatment is performed at a low temperature of 300 (° C. or less) (preferably 270 (° C. or less) or less, the sintering of the silver powder is sufficiently advanced, so that it can be sufficiently advanced. High conductivity and high adhesion to the polyimide substrate are obtained. Incidentally, even if only a small amount of the coating agent adheres to the silver powder, the sinterability of the silver powder increases in accordance with the amount thereof, but becomes more than 2.3 (%). When it is left, it becomes difficult to burn through at the time of baking, and the film density is lowered, and electrical conductivity is lowered.
在此，在前述第1發明宜為：前述導電膜是銀燒結而成者。亦即，第1發明之附導電膜之基板是使用燒成類型之導電性糊而在聚醯亞胺基板上形成導電膜。因此，由於導電膜中之導體成分之銀燒結，故具有高導電性。 Here, in the first invention, it is preferable that the conductive film is sintered by silver. In other words, in the substrate with a conductive film according to the first aspect of the invention, a conductive film is formed on the polyimide substrate by using a baking paste of a firing type. Therefore, since the silver of the conductor component in the conductive film is sintered, it has high conductivity.
另外，在前述第2發明宜為：在前述銀粉末表面附著之前述塗佈劑相對於該銀粉末之質量比為2.3(%)以下之量。即便只附著有少許塗佈劑，銀粉末之燒結性也會因應其量而改善，但超過2.3(%)而變得過剩則會在燒成時變得不易燒穿，令膜密度降低，導電性降低。 Further, in the second aspect of the invention, it is preferable that the mass ratio of the coating agent adhering to the surface of the silver powder to the silver powder is 2.3 (%) or less. Even if only a small amount of the coating agent is adhered, the sinterability of the silver powder is improved in accordance with the amount thereof. However, if it exceeds 2.3%, it becomes excessively burnt, and the film density is lowered and the film density is lowered. Reduced sex.
另外，在前述導電性糊宜為：前述銀粉末之平均粒徑為0.5(μm)以下。銀粒徑越大則燒結性越降低，當變成1(μm)以上則燒結顯著地不易進展，電阻值增大。 Further, in the conductive paste, the average particle diameter of the silver powder is preferably 0.5 (μm) or less. The larger the particle size of silver, the lower the sinterability. When it is 1 (μm) or more, the sintering is remarkably difficult to progress, and the resistance value is increased.
另外，前述導電性糊及前述導電膜宜為實質上不含玻璃。附帶一提，「實質上不含玻璃」在理想上是完全不包含玻璃的意思，但不對燒結性等特性賦予影響之程度是可容許。 Further, it is preferable that the conductive paste and the conductive film contain substantially no glass. Incidentally, "substantially no glass" means that glass is not contained at all, but it is acceptable to not affect the properties such as sinterability.
另外，在前述第2發明及前述第3發明宜為：前述樹脂結合劑之分解溫度為250(℃)以下，亦即，在比前述燒成溫度還低溫而燒穿。如此，由於在形成之導電膜中不易殘留有機物、碳化物，故可獲得導電膜之導電性進一步高且對聚醯亞胺基板之密接性進一步高之附導電膜之基板。若將印刷性、操作性亦考慮進去，則宜為壓克力樹 脂。舉例來說，甲基丙烯酸異丁酯之聚合物且平均分子量16萬之物。附帶一提，樹脂結合劑之分解溫度比燒成溫度還低並非必要。舉例來說，亦可以使用分解溫度為300(℃)以上之樹脂結合劑。即便在如此之情況下，根據本案發明則銀粉末之燒結充分進展，故即使在導電膜殘留有機物、碳化物，與習知相較之下是獲得充分地高之導電性。 Further, in the second invention and the third invention, it is preferable that the decomposition temperature of the resin binder is 250 (° C.) or less, that is, burnt at a lower temperature than the firing temperature. In this way, since the organic material and the carbide are less likely to remain in the formed conductive film, a substrate with a conductive film having a further high conductivity of the conductive film and a higher adhesion to the polyimide substrate can be obtained. If the printability and operability are taken into consideration, it is preferable to be an acrylic tree. fat. For example, a polymer of isobutyl methacrylate and having an average molecular weight of 160,000. Incidentally, it is not necessary that the decomposition temperature of the resin binder is lower than the firing temperature. For example, a resin binder having a decomposition temperature of 300 (° C. or more) can also be used. Even in such a case, according to the invention of the present invention, the sintering of the silver powder is sufficiently advanced, so that even if the organic film or the carbide remains in the conductive film, sufficiently high conductivity is obtained as compared with the conventional one.
10‧‧‧銀導電膜 10‧‧‧Silver conductive film
12‧‧‧聚醯亞胺基板 12‧‧‧ Polyimine substrate
14‧‧‧附導電膜之基板 14‧‧‧Substrate with conductive film
圖1是示意顯示本發明一實施例之聚醯亞胺基板之一面上形成有銀導電膜之附導電膜之基板的截面的圖。 1 is a view schematically showing a cross section of a substrate with a conductive film on which a silver conductive film is formed on one surface of a polyimide substrate according to an embodiment of the present invention.
圖2是圖1之附導電膜之基板的導電膜與基板之界面附近的截面照片。 2 is a cross-sectional photograph of the vicinity of the interface between the conductive film of the substrate with the conductive film of FIG. 1 and the substrate.
圖3是將圖2之截面之一部分擴大顯示的照片。 Fig. 3 is a photograph showing an enlarged portion of a section of Fig. 2;
圖4是比較例之附導電膜之基板的導電膜與基板之界面附近的截面照片。 4 is a cross-sectional photograph of the vicinity of the interface between the conductive film of the substrate with the conductive film of the comparative example and the substrate.
圖5是將圖4之截面之一部分擴大顯示的照片。 Fig. 5 is a photograph showing an enlarged portion of a section of Fig. 4;
圖6是將本發明一實施例之附導電膜之基板的導電膜之截面形狀依各燒成溫度而顯示的圖。 Fig. 6 is a view showing a cross-sectional shape of a conductive film of a substrate with a conductive film according to an embodiment of the present invention, according to each firing temperature.
圖7是本發明一實施例之附導電膜之基板的導電膜表面的SEM照片。 Fig. 7 is a SEM photograph of the surface of a conductive film of a substrate with a conductive film according to an embodiment of the present invention.
以下，參考圖面來詳細說明本發明一實施例。附帶一提，以下之實施例，圖是經適宜簡略化或變形，故各部分之尺寸比及形狀等並非一定是正確地描繪。 Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. Incidentally, in the following embodiments, the drawings are appropriately simplified or deformed, so that the dimensional ratios and shapes of the respective portions are not necessarily correctly drawn.
圖1是顯示本發明之聚醯亞胺基板12之一面上形成有銀導電膜10的附導電膜之基板14之截面的圖。此配線基板可在各種電子機器等當作具有可撓性之內部配線基板、或是將可動部分之端子與固定部分之端子連接之撓性配線基板等來使用。銀導電膜10舉例來說是具備有1.0~8.0(μm)左右之厚度尺寸之僅由銀所成之物，其具備有當聚醯亞胺基板12變形時隨其變形之柔軟性。 1 is a view showing a cross section of a substrate 14 with a conductive film on which a silver conductive film 10 is formed on one surface of a polyimide substrate 12 of the present invention. The wiring board can be used as a flexible wiring board or the like, or as a flexible wiring board in which a terminal of a movable portion and a terminal of a fixed portion are connected to each other. The silver conductive film 10 is, for example, a material made of only silver having a thickness of about 1.0 to 8.0 (μm), and has flexibility to be deformed when the polyimide substrate 12 is deformed.
上述附導電膜之基板14舉例來說是準備包含銀粉末、樹脂結合劑、有機溶劑之導電性糊，在聚醯亞胺基板12上藉由網版印刷、凹版印刷、平板印刷、或是噴墨印刷等適宜之印刷方法來形成膜，施行燒成處理，藉此生成銀導電膜10而製造。上述銀粉末是作為在表面附著有預定量之塗佈劑之附著塗佈劑之銀粉末而添加。塗佈劑是松香、脂肪酸、胺類之任一者。關於脂肪酸，舉例來說是硬脂酸、月桂酸、油酸、亞麻油酸、癸酸等。另外，關於胺類，舉歷來說是十二胺。 The substrate 14 with the conductive film is exemplified by a conductive paste containing silver powder, a resin binder, and an organic solvent, which is screen printed, gravure, lithographic, or sprayed on the polyimide substrate 12 . A film is formed by a suitable printing method such as ink printing, and a firing treatment is performed to produce a silver conductive film 10. The silver powder is added as a silver powder which adheres to a coating agent of a predetermined amount of a coating agent on the surface. The coating agent is any one of rosin, fatty acid, and amine. As the fatty acid, for example, stearic acid, lauric acid, oleic acid, linoleic acid, citric acid or the like can be mentioned. Further, regarding the amines, it is a dodecylamine.
如此之附著塗佈劑之銀粉末是依以下方式製作。關於銀粉末，使用藉由一般之濕式法所調製之市售產品。準備了平均粒徑0.07(μm)、0.10(μm)、0.5(μm)、0.8(μm)、0.9(μm)、1.0(μm)、1.4(μm)、3(μm)之球形狀之物。將其在例如燒杯分別取約100(g)，並追加異丙醇約1000(ml)而充分攪拌。將其放置一夜，接著，將上澄廢棄。進一步投入異丙醇約1000(ml)，攪拌後，放置一夜。反覆此洗淨操作3~5次。藉此，藉此，將附著在銀粉末之 有機物充分去除。 The silver powder to which the coating agent was attached was produced in the following manner. As the silver powder, a commercially available product prepared by a general wet method is used. Ball-shaped objects having an average particle diameter of 0.07 (μm), 0.10 (μm), 0.5 (μm), 0.8 (μm), 0.9 (μm), 1.0 (μm), 1.4 (μm), and 3 (μm) were prepared. This is, for example, about 100 (g) in a beaker, and about 1000 (ml) of isopropanol is added thereto, and the mixture is sufficiently stirred. Leave it for one night, then discard it. Further, about 1000 (ml) of isopropanol was added, and after stirring, it was allowed to stand overnight. Repeat this washing operation 3 to 5 times. Thereby, by this, it will adhere to the silver powder. The organic matter is completely removed.
接著，使塗佈劑溶解於異丙醇。以下，以使用松香來作為塗佈劑的情況而舉例說明。關於松香原料，使用例如荒川化學工業製之脂松香WW，將其取1.0~2.5(g)添加於500(ml)之異丙醇而攪拌。接著，將完成上述之洗淨操作之銀粉之上澄液廢棄，對其添加溶解了松香之異丙醇而充分攪拌。接著，將該混合物移到茄型燒瓶，使用蒸發器以55(℃)~60(℃)之溫水一面加溫一面減壓，藉此使異丙醇氣化。將如此而獲得之銀粉載於托盤，放置一夜。之後，使用200目之網版實施篩分，藉此準備了在表面附著有松香之銀粉粒子。 Next, the coating agent was dissolved in isopropyl alcohol. Hereinafter, the case where rosin is used as a coating agent is exemplified. For the rosin raw material, for example, a gum rosin WW manufactured by Arakawa Chemical Industries Co., Ltd. is used, and 1.0 to 2.5 (g) is added to 500 (ml) of isopropyl alcohol and stirred. Next, the supernatant of the silver powder which has been subjected to the above-described washing operation is discarded, and isopropyl alcohol in which rosin is dissolved is added thereto, followed by thorough stirring. Next, the mixture was transferred to an eggplant type flask, and the isopropyl alcohol was vaporized by heating with a warm water of 55 (° C.) to 60 (° C.) while using an evaporator. The silver powder thus obtained was placed on a tray and left for one night. Thereafter, sieving was carried out using a 200 mesh screen, thereby preparing silver powder particles having rosin adhered to the surface.
附帶一提，附著之松香量是將所獲得之銀粉藉由TG-DTA以昇溫速度10(℃/min)來測量至900(℃)為止而求出。亦即，以TG之50(℃)之質量與400(℃)之質量之差作為附著松香量。松香附著量是藉由使添加之脂松香WW之量改變而調整。舉例來說，粒徑0.1(μm)之銀粉的情況下，相較於脂松香量1.2(g)、1.7(g)、2.2(g)，松香量會是1.0(%)、1.6(%)、2.0(%)。 Incidentally, the amount of the rosin adhered was determined by measuring the silver powder obtained by TG-DTA at a temperature increase rate of 10 (° C./min) to 900 (° C.). That is, the difference between the mass of 50 (° C.) of TG and the mass of 400 (° C.) is taken as the amount of attached rosin. The rosin adhesion amount is adjusted by changing the amount of the added gum rosin WW. For example, in the case of a silver powder having a particle diameter of 0.1 (μm), the amount of rosin is 1.0 (%), 1.6 (%) compared to the amount of gum rosin 1.2 (g), 1.7 (g), and 2.2 (g). , 2.0 (%).
如上述般地準備松香附著銀粉，藉由攪拌機等與樹脂結合劑及有機溶劑混合。關於樹脂結合劑，舉例來說使用壓克力樹脂(三菱麗陽製之EMB-002)，關於有機溶劑，舉例來說使用薄荷腦。將他們以預定量調合，使用三輥碾磨機進行分散處理而糊化，藉此獲得導電性糊。上述壓克力樹脂是在250(℃)以下燒穿之物，是已考慮網版印刷 性、處置性之平均分子量16萬左右之甲基丙烯酸異丁酯。在調製糊之際，為了令印刷性同等，舉例來說是以在25(℃)-20(rpm)下之黏度會成為180~200(Pa‧s)的方式調整。 The rosin-attached silver powder is prepared as described above, and mixed with a resin binder and an organic solvent by a stirrer or the like. As the resin binder, for example, an acrylic resin (EMB-002 manufactured by Mitsubishi Rayon Co., Ltd.) is used, and as the organic solvent, for example, menthol is used. They were blended in a predetermined amount, and subjected to dispersion treatment using a three-roll mill to be gelatinized, thereby obtaining a conductive paste. The above acrylic resin is burnt through below 250 (°C) and has been considered for screen printing. A suitable and disposable isobutyl methacrylate having an average molecular weight of about 160,000. In order to make the printability equivalent, for example, the viscosity is adjusted to be 180 to 200 (Pa ‧ s) at 25 (° C.) to 20 (rpm).
使用如此地準備之導電性糊，於聚醯亞胺基板施行厚膜網版印刷。印刷製版是SUS400製。另外，以令印刷膜之寬尺寸成為500(μm)的方式而設定印刷條件。乾燥後，以250~300(℃)之範圍內之溫度施行燒成處理，藉此，樹脂結合劑會燒穿並且銀粉末會燒結，獲得前述銀導電膜10。 Thick film screen printing was performed on the polyimide substrate using the conductive paste prepared in this manner. The printing plate is made of SUS400. Further, the printing conditions were set such that the width of the printing film was 500 (μm). After drying, the firing treatment is performed at a temperature in the range of 250 to 300 (° C.), whereby the resin binder is burned through and the silver powder is sintered to obtain the silver conductive film 10.
根據本實施例，由於如上述般地使用附著有松香、脂肪酸、或胺類之附著塗佈劑之銀粉末來作為銀粉末，故即便如上述之250~270(℃)之低溫，銀粉末之燒結亦可充分進展，所以，舉例來說，可獲得在聚醯亞胺基板12上具備有片電阻值為2~8(mΩ/□)左右之高導電性與高密接性之導電膜10之附導電膜之基板14。 According to the present embodiment, since silver powder to which an adhesion coating agent of rosin, a fatty acid, or an amine is adhered is used as the silver powder as described above, even at a low temperature of 250 to 270 (° C.) as described above, silver powder is used. Sintering can be sufficiently progressed. Therefore, for example, a conductive film 10 having a high electrical conductivity and high adhesion with a sheet resistance of about 2 to 8 (mΩ/□) can be obtained on the polyimide substrate 12 . A substrate 14 with a conductive film is attached.
圖2是上述附導電膜之基板14的導電膜10與聚醯亞胺基板12之界面附近之截面的SEM像，圖3是將其一部分更加擴大的SEM像。圖2之佔據上半部左右之淡色部分是導電膜10，位於其下側之濃色部分是聚醯亞胺基板12。如此SEM像所表示，導電膜10是充分地燒結而達到粒界消失之程度。而且，在導電膜10與基板12之界面形成有凹凸，如圖3所示之其境界部分之擴大，成為銀與聚醯亞胺相互侵入至對方之領域之狀態。 2 is an SEM image of a cross section of the vicinity of the interface between the conductive film 10 of the substrate 14 with the conductive film and the polyimide substrate 12, and FIG. 3 is an SEM image in which a part thereof is further enlarged. The light-colored portion occupying the left and right of the upper half of Fig. 2 is the conductive film 10, and the dark portion on the lower side thereof is the polyimide substrate 12. As shown by the SEM image, the conductive film 10 is sufficiently sintered to the extent that the grain boundary disappears. Further, irregularities are formed at the interface between the conductive film 10 and the substrate 12, and the boundary portion of the boundary between the conductive film 10 and the substrate 12 is expanded to become a state in which silver and polyimide are invaded into each other.
在此，說明對糊組成與膜形成條件進行各種改變而予以評價之試驗結果。下述之表1是將對塗佈劑之有無與種類、銀粒徑進行檢討之結果予以整理之表。在表1中，No.1、No.2、No.6、No.13是比較例，其他是實施例。另外，「組成」欄是將導電性糊之組成以質量百分比來表示，銀量取68~75(%)之範圍，玻璃量取0~2(%)之範圍，樹脂結合劑量取5~6(%)之範圍，有機溶劑量取20~24(%)之範圍。「樹脂/銀」是樹脂量相對於銀之百分比。另外，在「材料」欄中，「銀粒徑」是在各糊使用之將塗佈劑附著前之銀粉末之粒徑，「添加劑種類」是使用來作為銀粉末之塗佈劑之材料名，「附著量」是如前述般地藉由TG-DTA來測量所附著之塗佈劑量之結果，其是以相對於銀粉末之百分比來表示。另外，「玻璃」欄是在糊添加之玻璃粉末之組成系。另外，在「試驗條件.結果」欄中，「印刷版」是網目尺寸，「印刷厚度」是印刷.乾燥後之膜厚。另外，「處理溫度」是燒成處理之最高保持溫度，依各處理溫度而顯示試驗結果。「燒成厚度」是燒成後之膜厚，「電阻值」是在燒成後使用數位萬用表，基於一般之2端子法以端子間隔10(cm)、線寬500(μm)所測量之膜狀導體之電阻值。另外，「片電阻(mΩ/□)」是藉由下面之式子而由上述電阻值所算出之燒成後之片電阻值。附帶一提，換算厚度是10(μm)。 Here, the test results which are evaluated by various changes in the paste composition and the film formation conditions will be described. Table 1 below is a table in which the results of reviewing the presence or absence of the coating agent, the type of silver, and the particle size of silver are examined. In Table 1, No. 1, No. 2, No. 6, and No. 13 are comparative examples, and others are examples. In addition, the "composition" column is to express the composition of the conductive paste by mass percentage, the amount of silver is in the range of 68 to 75 (%), the amount of glass is in the range of 0 to 2 (%), and the resin binding dose is 5 to 6 In the range of (%), the amount of organic solvent is in the range of 20 to 24 (%). "Resin/silver" is the percentage of resin relative to silver. In the "Materials" column, "silver particle size" is the particle size of the silver powder before the coating agent is applied to each paste, and the "additive type" is the material name of the coating agent used as the silver powder. The "adhesion amount" is a result of measuring the applied coating amount by TG-DTA as described above, which is expressed as a percentage with respect to the silver powder. In addition, the "glass" column is a component of the glass powder added to the paste. In addition, in the "Test conditions. Results" column, "printing plate" is the mesh size, and "printing thickness" is the film thickness after printing and drying. Further, the "treatment temperature" is the highest holding temperature of the firing treatment, and the test results are displayed for each processing temperature. The "baked thickness" is the film thickness after firing, and the "resistance value" is a film which is measured by a two-terminal method at a terminal interval of 10 (cm) and a line width of 500 (μm) by using a digital multimeter after firing. The resistance value of the conductor. In addition, "sheet resistance (mΩ/□)" is a sheet resistance value after firing calculated from the above resistance value by the following formula. Incidentally, the converted thickness is 10 (μm).
片電阻值(mΩ/□)=測量電阻值(Ω)×(導體寬(mm)/導體長度(mm))×(導體厚度(μm)/換算厚度(μm)) Sheet resistance value (mΩ/□) = measured resistance value (Ω) × (conductor width (mm) / conductor length (mm)) × (conductor thickness (μm) / converted thickness (μm))
另外，「膠帶強度」是在燒成後，以手指將NICHIBAN公司製之CT-15153P之膠帶(CELLOTAPE)按壓於形成在聚醯亞胺基板上之銀導電膜之表面而使其附著，將膠帶撕起而藉由目測來觀察在剝離之膠帶面所附著之銀導電膜之樣子而進行判定。進行如下之3階段評價：當在按壓之膠帶之幾乎整面完全未附著有銀導電膜、且形成在聚醯亞胺基板上之銀導電膜亦維持原樣地殘留，則為「○」，當在按壓之膠帶附著有銀導電膜之一部分、且形成在聚醯亞胺基板上之銀導電膜有一部分未殘留，則為「△」，當在按壓之膠帶附著有銀導電膜之90(%)以上、且形成在聚醯亞胺基板上之銀導電膜之90(%)以上未殘留，則為「×」。 In addition, after the baking, the tape of CT-15153P (CELLOTAPE) manufactured by NICHIBAN Co., Ltd. is pressed against the surface of the silver conductive film formed on the polyimide substrate by a finger, and the tape is attached. The tearing was carried out and the judgment was made by visually observing the state of the silver conductive film adhered to the peeled tape surface. The following three-stage evaluation was carried out: when the silver conductive film was not adhered to almost the entire surface of the pressed tape, and the silver conductive film formed on the polyimide substrate remained as it was, it was "○". When a part of the silver conductive film is adhered to the tape to be pressed, and a part of the silver conductive film formed on the polyimide substrate is not left, it is "Δ", and 90% of the silver conductive film is attached to the pressed tape. When 90% or more of the silver conductive film formed on the polyimide substrate is not left, it is "x".
在上述之表1中，如比較例No.1、No.2，無塗佈劑地使用銀粉末之例子因為未在聚醯亞胺基板上燒結，故結果是片電阻值高、膠帶強度亦低。尤其是使用粒徑1(μm)之銀粉末之No.1，即便以270(℃)燒成，片電阻值亦處於32.3(mΩ/□)之顯著地高之值。另外，比較例No.13雖然使用附著有十二硫醇來作為塗佈劑之銀粉末，但未獲得燒結性之改善效果，即便以270(℃)燒成，片電阻值亦處於65.1(mΩ/□)之高之值，且膠帶強度亦未獲得。 In Table 1 above, as in Comparative Examples No. 1, No. 2, an example in which a silver powder was used without a coating agent was not sintered on a polyimide substrate, and as a result, the sheet resistance was high and the tape strength was also low. In particular, No. 1 of silver powder having a particle diameter of 1 (μm) was used, and even when baked at 270 (° C.), the sheet resistance value was significantly higher than 32.3 (mΩ/□). Further, in Comparative Example No. 13, although silver powder to which dodecyl mercaptan was attached as a coating agent was used, the effect of improving the sinterability was not obtained, and even when baked at 270 (° C.), the sheet resistance value was 65.1 (mΩ). The value of /□) is high and the strength of the tape is not obtained.
相較於這些，實施例No.3~No.5、No.7~No.12是以松香、硬脂酸、月桂酸、油酸、亞麻油酸、癸酸、十二胺作為塗佈劑而分別在相對於銀之質量比為0.16~2.3(%)之範圍予以附著，但任一者皆可藉由在250~270(℃)施行燒成 處理而良好地燒結，獲得片電阻值為2.4~6.7(mΩ/□)之高導電性。另外，膠帶強度亦全部為「○」之結果。附帶一提，No.3、No.4皆使用松香，除了銀粒徑0.1(μm)、0.07(μm)之不同之外，其他相同，但評價之結果是粒徑大之No.3之導電性稍微較佳。可以想到的是，由於微粉之銀粉末是表面積大，故塗佈劑量需要多。附帶一提，No.6除了在糊中添加了2(%)玻璃粉末之外，其他與No.3為相同條件，結果，雖然獲得充分之導電性，但未獲得膠帶強度。銀導電膜本身雖然有燒結，但可能玻璃阻礙了對聚醯亞胺基板之密接性。 Compared with these, Examples No. 3 to No. 5 and No. 7 to No. 12 are rosin, stearic acid, lauric acid, oleic acid, linoleic acid, citric acid, and dodecylamine as coating agents. And the ratio of the mass ratio to silver is 0.16 to 2.3 (%), but either can be fired at 250 to 270 (° C.). The film was satisfactorily sintered to obtain a high electrical conductivity of sheet resistance of 2.4 to 6.7 (mΩ/□). In addition, the tape strength was also the result of "○". Incidentally, No. 3 and No. 4 use rosin, except for the difference in silver particle size of 0.1 (μm) and 0.07 (μm), the others are the same, but the result of the evaluation is the conductivity of No. 3 having a large particle diameter. Sex is slightly better. It is conceivable that since the silver powder of the fine powder has a large surface area, the coating dose is required to be large. Incidentally, No. 6 was the same as No. 3 except that 2 (%) glass powder was added to the paste, and as a result, although sufficient conductivity was obtained, the tape strength was not obtained. Although the silver conductive film itself is sintered, it is possible that the glass hinders the adhesion to the polyimide substrate.
附帶一提，圖4、圖5是上述實施例No.7在燒成溫度為230(℃)之情況下之截面照片，分別與前述圖2、圖3對應。由於燒成溫度為230(℃)會太低，燒結未進展，銀導電膜10與聚醯亞胺基板12之界面亦為平坦之狀態。因此，片電阻值會高，且亦未獲得膠帶強度。 Incidentally, Fig. 4 and Fig. 5 are cross-sectional photographs of the above-described Example No. 7 in the case where the firing temperature is 230 (°C), and correspond to Figs. 2 and 3, respectively. Since the firing temperature is 230 (° C.), the sintering is not progressed, and the interface between the silver conductive film 10 and the polyimide substrate 12 is also flat. Therefore, the sheet resistance value is high and the tape strength is not obtained.
另外，下述之表2是將進一步改變條件而進行評價之結果予以整理之表，No.14~No.16是對銀粉末之粒徑進行檢討之結果。使用粒徑為0.5~1(μm)之銀粉末之No.14、No.15是以250~270(℃)之燒成溫度獲得片電阻值3.5~5.4(mΩ/□)之高導電性，且膠帶強度亦為「○」，相較於此，使用粒徑為3(μm)之銀粉末之No.16是導電性比較差之結果。尤其，在250(℃)之燒成溫度下，片電阻值為10.5(mΩ/□)之大，膠帶強度亦為「×」。不過，若以270(℃)來燒成，則膠帶強度充分地高，且片電阻值雖然為 7.1(mΩ/□)之偏高，但也改善到可使用之程度。 In addition, Table 2 below is a table in which the results of the evaluation were further changed, and No. 14 to No. 16 are the results of reviewing the particle diameter of the silver powder. No. 14 and No. 15 using a silver powder having a particle diameter of 0.5 to 1 (μm) have a high electrical conductivity of a sheet resistance of 3.5 to 5.4 (mΩ/□) at a firing temperature of 250 to 270 (° C.). Further, the tape strength was also "○". In contrast, No. 16 using a silver powder having a particle diameter of 3 (μm) was a result of poor conductivity. In particular, at a firing temperature of 250 (° C.), the sheet resistance value was as large as 10.5 (mΩ/□), and the tape strength was also “×”. However, if it is baked at 270 (° C.), the tape strength is sufficiently high, and the sheet resistance value is 7.1 (mΩ/□) is too high, but it is also improved to the extent that it can be used.
另外，No.17~No.19是使糊中之樹脂結合劑量在相對於銀之質量比為12.9~4.3(%)之範圍變化。不論哪一個條件，皆可藉由250~270(℃)之燒成而獲得片電阻值為2.7~5.4(mΩ/□)之高導電性、「○」評價之高膠帶強度。糊中之樹脂量是容許在較廣之範圍。 In addition, No. 17 to No. 19 change the resin binding amount in the paste in a range of 12.9 to 4.3 (%) with respect to the mass ratio of silver. In either case, high sheet conductivity of 2.7 to 5.4 (mΩ/□) and high tape strength of “○” evaluation can be obtained by firing at 250 to 270 (°C). The amount of resin in the paste is allowed to be in a wide range.
另外，No.20、No.21是將糊中之樹脂結合劑改變而進行評價，No.20是使用分解溫度高之壓克力樹脂(例如，分解溫度為300(℃)左右之三菱麗陽製之EMB-398)，No.21是使用乙基纖維素(例如分解溫度為450(℃)左右之陶氏化學製之EC-45)，任一者皆可藉由250~270(℃)之燒成溫度而獲得片電阻值為2.3~2.8(mΩ/□)之高導電性、高膠帶強度。附帶一提，由於上述2種是分解溫度高，故可想到的是在燒成後之銀導電膜10內以有機物或是碳化物而至少殘留有一部分，但根據上述評價結果，可得知即便是如此地分解溫度高亦毫無問題，樹脂結合劑非完全燒穿亦不致妨礙。 In addition, No. 20 and No. 21 are evaluated by changing the resin binder in the paste, and No. 20 is an acrylic resin having a high decomposition temperature (for example, Mitsubishi Riyang having a decomposition temperature of about 300 (° C.). EMB-398), No. 21 is ethyl cellulose (for example, EC-45 made by Dow Chemical with a decomposition temperature of 450 (°C)), either by 250~270 (°C) The firing temperature is high and the sheet resistance is 2.3 to 2.8 (mΩ/□). Incidentally, since the above two types have high decomposition temperatures, it is conceivable that at least a part of the silver conductive film 10 after firing is organic or carbide, but based on the above evaluation results, it is known The decomposition temperature is so high that there is no problem, and the resin binder is not completely prevented from being completely burned.
另外，No.22~No.24是使糊中之樹脂結合劑與有機溶劑之比例改變，並使印刷版改變成#400、#250、#165，而使印刷厚度在3.2~10.1(μm)之間改變。若印刷厚度變厚，則燒結性有稍微變差之傾向，在250~270(℃)之燒成溫度，印刷厚度為3.2(μm)之No.22與5.8(μm)之No.23是獲得片電阻值為2.7~3.7(mΩ/□)、膠帶強度為「○」之良好結果，相較於此，印刷厚度為10.1(μm)之No.24在250(℃)是膠帶強度變成「×」。不過，即便是No.24亦在270(℃)充 分地燒結，獲得片電阻值為4.8(mΩ/□)、膠帶強度為「○」之比No.22、No.23稍微差但良好之結果。另外，對此等No.22~No.24之試料以燒成溫度300(℃)亦進行了評價，結果片電阻值為2.4~2.5(mΩ/□)、膠帶強度「○」，任一者皆可確認到良好之結果。 Further, No. 22 to No. 24 change the ratio of the resin binder to the organic solvent in the paste, and change the printing plate to #400, #250, #165, and the printing thickness is 3.2 to 10.1 (μm). Change between. When the printing thickness is increased, the sinterability tends to be slightly deteriorated. At a firing temperature of 250 to 270 (° C.), No. 22 of a printing thickness of 3.2 (μm) and No. 23 of 5.8 (μm) are obtained. The sheet resistance value is 2.7 to 3.7 (mΩ/□), and the tape strength is a good result of "○". In contrast, the No. 24 having a printing thickness of 10.1 (μm) at 250 (° C.) is that the tape strength becomes "X". "." However, even No. 24 is charged at 270 (°C). Sintering was carried out to obtain a sheet having a sheet resistance of 4.8 (mΩ/□) and a tape strength of "○" which was slightly inferior but inferior to No. 22 and No. 23. In addition, the samples of No. 22 to No. 24 were also evaluated at a firing temperature of 300 (° C.), and the sheet resistance was 2.4 to 2.5 (mΩ/□), and the tape strength was “○”. Good results can be confirmed.
另外，No.25是令塗佈劑不附著在銀粉末而添加在糊中，但在250(℃)之燒成溫度，片電阻值為332(mΩ/□)之顯著地大，無法獲得導電性，膠帶強度亦變成「×」。可確認到為了改善在聚醯亞胺基板上之銀粉末之燒結性，需要有使塗佈劑附著於銀粉末之處理。 Further, No. 25 is such that the coating agent is added to the paste without adhering to the silver powder, but at a firing temperature of 250 (° C.), the sheet resistance value is 332 (mΩ/□), which is remarkably large, and conductivity cannot be obtained. Sex, the tape strength also becomes "X". It was confirmed that in order to improve the sinterability of the silver powder on the polyimide substrate, it is necessary to treat the coating agent to the silver powder.
在此，說明在上述之實施例對燒成後之銀導電膜10之表面形狀進行評價之結果。圖6是銀導電膜10之截面形狀圖。此截面形狀是使用東京精密製之SURFCOM 480A，以掃描速度1.5(mm/sec)、倍率10K、截取值0.8(mm)將所形成之500(μm)寬之配線圖樣於其寬方向橫截而測量。在圖6，縱方向是銀導電膜10之厚度方向，橫方向是其寬方向，中央部之產生凹凸之部分是銀導電膜10，其兩側之平坦之部分是聚醯亞胺基板12。另外，溫度是各評價試料之燒成溫度，250(℃)、270(℃)的部分是對前述實施例No.3之試料測量，300(℃)的部分是對前述實施例No.22之試料測量。附帶一提，雖然325(℃)之試料是使用與該等同樣之導電性糊，但此測量資料並未記載於前述表1、表2。 Here, the results of evaluating the surface shape of the silver conductive film 10 after firing in the above examples will be described. FIG. 6 is a cross-sectional view of the silver conductive film 10. This cross-sectional shape is a SURFCOM 480A manufactured by Tokyo Seiko Co., Ltd., and has a scanning width of 1.5 (mm/sec), a magnification of 10 K, and a cutoff value of 0.8 (mm) to form a 500 (μm) wide wiring pattern in the width direction thereof. measuring. In Fig. 6, the longitudinal direction is the thickness direction of the silver conductive film 10, the lateral direction is the width direction, and the portion where the central portion is uneven is the silver conductive film 10, and the flat portions on both sides are the polyimide substrate 12. Further, the temperature is the firing temperature of each of the evaluation samples, and the portion of 250 (° C.) and 270 (° C.) is measured for the sample of the above-described Example No. 3, and the portion of 300 (° C.) is the portion of the aforementioned Example No. Sample measurement. Incidentally, although the 325 (°C) sample uses the same conductive paste as the above, the measurement data is not described in Tables 1 and 2 above.
如上述測量結果之截面形狀所示，藉由在 250~300(℃)之溫度範圍施行燒成處理而形成銀導電膜10，如前述圖2、圖3所示，銀導電膜10及聚醯亞胺基板12之構成成分相互侵入對方而形成凹凸形狀之界面，結果，銀導電膜10之表面是如圖6所示，成為凹凸劇烈之截面形狀。如比例尺所示，此凹凸之大小是銀導電膜10之厚度尺寸以下、亦即2(μm)左右。 As shown in the cross-sectional shape of the above measurement results, The silver conductive film 10 is formed by firing in a temperature range of 250 to 300 (° C.), and as shown in FIGS. 2 and 3 , the constituent components of the silver conductive film 10 and the polyimide substrate 12 invade each other to form a bump. As a result of the interface of the shape, as shown in Fig. 6, the surface of the silver conductive film 10 has a sharp cross-sectional shape. As shown by the scale, the size of the unevenness is equal to or less than the thickness of the silver conductive film 10, that is, about 2 (μm).
相較於此，以325(℃)燒成的情況下，聚醯亞胺基板12顯著地受到銀導電膜10所浸食，形成之凹處之深度是銀導電膜10之膜厚尺寸以上。此時，推定聚醯亞胺基板12之構成成分可能亦在銀導電膜10側遍及膜厚方向整體而侵入，片電阻值亦變高。如此，因為聚醯亞胺基板12在燒成溫度325(℃)會發生破掉等不良情況，明顯無法使用，故前述表1、表2省略記載。 On the other hand, in the case of baking at 325 (° C.), the polyimide substrate 12 is significantly impregnated by the silver conductive film 10, and the depth of the recess formed is equal to or larger than the thickness of the silver conductive film 10. At this time, it is estimated that the constituent components of the polyimide substrate 12 may also enter the entire thickness of the silver conductive film 10 in the film thickness direction, and the sheet resistance value also becomes high. As described above, since the polyimine substrate 12 is broken at the firing temperature of 325 (° C.), it is obviously unusable, and therefore, Tables 1 and 2 are omitted.
附帶一提，圖7是銀導電膜10的表面SEM照片。如該照片所示，在銀導電膜10之表面發生多數小孔。可以想到的是如此之孔亦是在前述圖6出現之凹凸之原因，但在考量膜厚、構成成分之侵入深度時，無視起因於此孔之凹凸。 Incidentally, FIG. 7 is a SEM photograph of the surface of the silver conductive film 10. As shown in the photograph, many small holes are formed on the surface of the silver conductive film 10. It is conceivable that such a hole is also the cause of the unevenness appearing in the above-mentioned Fig. 6, but the thickness of the film and the depth of penetration of the constituent component are considered, regardless of the unevenness of the hole.
如以上之說明，根據本實施例，銀導電膜10及聚醯亞胺基板12是令其等之構成成分在銀導電膜10之厚度尺寸以下之範圍相互侵入對方，以藉此所形成之凹凸面作為其等之界面，所以，導電性與密接性會伴隨接觸面積之增大而提高。因此，可獲得具備有高導電性與對聚醯亞胺基板12之高密接性之銀導電膜10之附導電膜之基板14。 As described above, according to the present embodiment, the silver conductive film 10 and the polyimide substrate 12 are formed such that the constituent components thereof enter each other within a range of the thickness of the silver conductive film 10 or less. Since the surface serves as the interface between them, the conductivity and the adhesion are improved with an increase in the contact area. Therefore, the substrate 14 having the conductive film with the silver conductive film 10 having high conductivity and high adhesion to the polyimide substrate 12 can be obtained.
另外，根據本實施例，將銀導電膜10形成在聚醯亞胺基板12上而製造附導電膜之基板14之際，於糊塗布步驟中塗布之導電性糊是使用令由松香、脂肪酸、或胺類構成之塗佈劑附著在表面的附著塗佈劑之銀粉末來作為銀粉末，所以，於燒成步驟中，即便以250~300(℃)之範圍內之低溫來施行燒成處理，燒結亦會充分進展，故可獲得具備有高導電性與對聚醯亞胺基板12之高密接性之銀導電膜10之附導電膜之基板14。 Further, according to the present embodiment, when the silver conductive film 10 is formed on the polyimide substrate 12 to produce the substrate 14 with the conductive film, the conductive paste applied in the paste coating step is made of rosin, fatty acid, Since the coating agent made of an amine adheres to the silver powder of the coating agent adhering to the surface as a silver powder, in the baking step, the baking treatment is performed even at a low temperature in the range of 250 to 300 (° C.). Further, the sintering progresses sufficiently, so that the substrate 14 having the conductive film of the silver conductive film 10 having high conductivity and high adhesion to the polyimide substrate 12 can be obtained.
另外，根據本實施例，關於導電性糊，銀粉末是使用令由松香、脂肪酸、或胺類所成之塗佈劑在相對於銀粉末之質量比為2.3(%)以下之範圍附著之附著塗佈劑之銀粉末，所以，即便以300(℃)以下之低溫來施行燒成處理，銀粉末之燒結亦會充分進展，故可獲得高導電性與對聚醯亞胺基板12之高密接性。 Further, according to the present embodiment, in the conductive paste, the silver powder is attached so that the coating agent made of rosin, a fatty acid, or an amine is attached in a range of 2.3 (%) or less with respect to the mass ratio of the silver powder. Since the silver powder of the coating agent is subjected to the baking treatment at a low temperature of 300 (° C. or lower), the sintering of the silver powder is sufficiently advanced, so that high conductivity and high adhesion to the polyimide substrate 12 can be obtained. Sex.
以上雖然是參考圖面來詳細說明本發明，但本發明可進一步藉由其他之態樣來實施，可在不超脫其主旨之範圍施加各種變更。 The present invention has been described in detail with reference to the drawings. However, the present invention may be embodied in other forms and various modifications may be made without departing from the spirit thereof.
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| JP2015078076A JP6263146B2 (en) | 2015-04-06 | 2015-04-06 | Substrate with conductive film, method for producing the same, and conductive paste for polyimide substrate |
| JP2015-078076 | 2015-04-06 |
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| JP2006310022A (en) * | 2005-04-27 | 2006-11-09 | Mitsui Mining & Smelting Co Ltd | Electrically conductive paste, and flexible printed wiring board obtained using the same |
| JP5164239B2 (en) * | 2006-09-26 | 2013-03-21 | Ｄｏｗａエレクトロニクス株式会社 | Silver particle powder, dispersion thereof, and method for producing silver fired film |
| JP5139659B2 (en) * | 2006-09-27 | 2013-02-06 | Ｄｏｗａエレクトロニクス株式会社 | Silver particle composite powder and method for producing the same |
| JP2008108569A (en) * | 2006-10-25 | 2008-05-08 | Sekisui Chem Co Ltd | Sintering conductive paste |
| JP4986745B2 (en) * | 2007-07-05 | 2012-07-25 | Ｄｏｗａエレクトロニクス株式会社 | Silver paste |
| KR100935168B1 (en) * | 2007-09-21 | 2010-01-06 | 삼성전기주식회사 | Nonaqueous conductive nanoink composition |
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| JP2010287434A (en) * | 2009-06-11 | 2010-12-24 | Dowa Electronics Materials Co Ltd | Substrate with silver conductive film and method for manufacturing same |
| JP2011065783A (en) * | 2009-09-15 | 2011-03-31 | Dowa Electronics Materials Co Ltd | Conductive paste and wiring board employing the same |
| JP4702499B1 (en) * | 2010-02-05 | 2011-06-15 | 東洋インキＳｃホールディングス株式会社 | Conductive ink, laminate with conductive pattern and method for producing the same |
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| JP2013139589A (en) * | 2011-12-28 | 2013-07-18 | Toda Kogyo Corp | Silver fine particles, method for producing the same, and conductive paste, conductive film, and electronic device containing the silver fine particles |
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| TWI687320B (en) | 2020-03-11 |
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