TW201807102A - Conductive ink - Google Patents

Abstract

A conductive ink that may be used for calcining a conductive film pattern with sufficient electrical conductivity and good adhesion to a substrate at a low temperature and is furthermore easy to operate and also exhibits excellent dispersivity is provided. The conductive ink is characterized by including a silver nanoparticle, a dispersing medium and a terpene resin attached to a surface of the silver nanoparticle or having a softening temperature of 90 C or more included in the dispersing medium.

Description

導電性墨水Conductive ink

本發明是有關於一種導電性墨水，其用於形成半導體積體電路等的配線或電極圖案，且可於有機薄膜電晶體基板形成配線或電極圖案。The present invention relates to a conductive ink for forming a wiring or an electrode pattern of a semiconductor integrated circuit or the like, and forming a wiring or an electrode pattern on the organic thin film transistor substrate.

由於包含銀奈米粒子的墨水調配物顯示出良好的印刷結果，因而，近來正在積極研究開發將銀奈米粒子技術用於印刷電子（Printed electronics）用途。Since ink formulations containing silver nanoparticles exhibit good printing results, recently, the use of silver nanoparticle technology for printed electronic applications has been actively researched and developed.

並且，近年來，所述印刷電子中，作為更簡便且廉價的導電膜圖案的形成方法，提出了使用凸版印刷法、凹版印刷法、網版印刷法或噴墨印刷法等印刷法的方法，進而，作為能夠形成更高精細的圖案的印刷方法，提出了使用反轉印刷法或微接觸印刷法等的方法，正在積極研究開發適合於該些印刷法的導電性墨水、絕緣性墨水及電阻墨水等各種墨水。Further, in the printed electronic device, a method of forming a conductive film pattern which is simpler and more inexpensive has been proposed in recent years, and a printing method such as a relief printing method, a gravure printing method, a screen printing method, or an inkjet printing method has been proposed. Further, as a printing method capable of forming a higher-definition pattern, a method using a reverse printing method or a micro-contact printing method has been proposed, and conductive inks, insulating inks, and resistors suitable for the printing methods are being actively researched and developed. Various inks such as ink.

例如，於專利文獻1（日本專利特開2011-044509號公報）中提出有於電極或電氣配線、尤其是太陽電池的集電極中，可實現電極寬度的進一步的細線化及低電阻化，另外即便為經細線化的窄密合面積亦具有充分的密合性，並且形成耐熱性及耐水性優異的可靠性高的電極的技術。更具體而言，揭示了「一種導電性墨水組成物，其含有導電性粒子、以及包含熱硬化性樹脂組成物、硬化劑及溶劑的有機系載體（vehicle），所述導電性墨水組成物的特徵在於：所述導電性粒子含有平均粒徑為1 nm以上且小於100 nm的奈米銀粒子、及平均薄片直徑為0.1 μm以下且3 μm以下的薄片狀銅粒子，所述導電性粒子以質量比例計，相較於所述奈米銀粒子而含有更多的所述薄片狀銅粒子」。For example, it is proposed in the electrode, the electric wiring, in particular, the collector of the solar cell, that the electrode width can be further thinned and the resistance is reduced, and the other is proposed in the patent document 1 (Japanese Patent Laid-Open Publication No. 2011-044509). Even if it is a thinned narrow contact area, it has sufficient adhesiveness, and the technique of the highly reliable electrode which is excellent in heat resistance and water resistance is formed. More specifically, "a conductive ink composition containing conductive particles and an organic vehicle containing a thermosetting resin composition, a curing agent, and a solvent, the conductive ink composition," The conductive particles include nano silver particles having an average particle diameter of 1 nm or more and less than 100 nm, and flaky copper particles having an average sheet diameter of 0.1 μm or less and 3 μm or less, wherein the conductive particles are The mass ratio meter contains more of the flaky copper particles than the nano silver particles.

另外，於專利文獻2（日本專利特開2012-184407號公報）中提出有一種於噴墨印刷等中，實現了咖啡環效應（coffee-ring effect）減少、對基材的接著性提高、印刷頭的脫蓋（decapping）時間或待機時間延長的墨水組成物。更具體而言，揭示有：「一種墨水組成物，其包含含銀的金屬奈米粒子、任意成分的樹脂、以及兩種以上的墨水媒劑，且所述墨水媒劑的至少一種為25℃下的蒸氣壓小於4 mmHg的脂肪族烴」。 [現有技術文獻] [專利文獻]In the inkjet printing or the like, it has been proposed to reduce the coffee-ring effect, improve the adhesion to the substrate, and print the ink in the inkjet printing and the like. The decapping time of the head or the ink composition of the extended standby time. More specifically, it is disclosed that "an ink composition comprising silver-containing metal nanoparticles, a resin having an optional component, and two or more kinds of ink vehicles, and at least one of the ink vehicles is 25 ° C The lower vapor pressure is less than 4 mmHg of aliphatic hydrocarbons." [Prior Art Document] [Patent Literature]

[專利文獻1]日本專利特開2011-044509號公報 [專利文獻2]日本專利特開2012-184407號公報[Patent Document 1] Japanese Patent Laid-Open No. 2011-044509 (Patent Document 2) Japanese Patent Laid-Open Publication No. 2012-184407

[發明所欲解決之課題][Problems to be solved by the invention]

然而，於現有的技術中，為了改善導電性材料對基材的密合性而利用塗敷液等對基材進行表面處理等，步驟增加且耗時耗力。 另外，所述專利文獻2的技術中，將萜烯樹脂後添加於溶媒中並於140℃下進行煅燒，所述專利文獻的技術中，將樹脂等混合而膏化的材料需要於200℃×30分鐘的高溫下進行煅燒，為了密合性而犧牲低溫燒結性，就兼具密合性與低溫燒結性的觀點而言，尚有改善的餘地。However, in the conventional technique, in order to improve the adhesion of the conductive material to the substrate, the substrate is subjected to surface treatment with a coating liquid or the like, and the steps are increased and time-consuming and labor-intensive. Further, in the technique of Patent Document 2, a terpene resin is added to a solvent and then calcined at 140 ° C. In the technique of the patent document, a material obtained by mixing a resin or the like is required to be at 200 ° C × Calcination is carried out at a high temperature of 30 minutes, and low-temperature sinterability is sacrificed for adhesion, and there is room for improvement from the viewpoint of both adhesion and low-temperature sinterability.

因此，本發明的目的是鑒於所述現有技術所具有的課題而形成，在於提供一種可將具有充分的導電性以及與基板的良好密合性的導電膜圖案於低溫下進行煅燒的導電性墨水，進而提供一種操作容易且分散性亦優異的導電性墨水。 [解決課題之手段]Accordingly, an object of the present invention is to provide a conductive ink capable of calcining a conductive film pattern having sufficient conductivity and good adhesion to a substrate at a low temperature in view of the problems of the prior art. Further, a conductive ink which is easy to handle and excellent in dispersibility is provided. [Means for solving the problem]

本發明者為了達成所述目的而反覆進行努力研究，結果發現，為了獲得可將具有充分的導電性以及與基板的良好密合性的導電膜圖案於低溫下進行煅燒的導電性墨水，進而獲得操作容易且分散性亦優異的導電性墨水，使用滿足特定條件的萜烯系樹脂在達成所述目的的方面極其有效，從而達成本發明。In order to achieve the above object, the inventors of the present invention have conducted intensive studies and found that a conductive ink capable of firing a conductive film pattern having sufficient conductivity and good adhesion to a substrate at a low temperature is obtained. The conductive ink which is easy to handle and which is excellent in dispersibility is extremely effective in achieving the above object by using a terpene-based resin which satisfies specific conditions, and the present invention has been achieved.

即，本發明提供一種導電性墨水，其特徵在於包含： 銀奈米粒子； 分散介質；以及 附著於所述銀奈米粒子的表面或所述分散介質中所含的軟化溫度為90℃以上的萜烯系樹脂。That is, the present invention provides a conductive ink comprising: silver nanoparticles; a dispersion medium; and a softening temperature of 90 ° C or more contained on a surface of the silver nanoparticles or in the dispersion medium Terpene resin.

所述本發明的導電性墨水中，較佳為所述萜烯系樹脂為選自由α-蒎烯聚合物、β-蒎烯聚合物、α-蒎烯/β-蒎烯共聚物、檸檬烯聚合物、松香、松香酯、改質松香、萜烯苯酚聚合物、氫化萜烯聚合物、芳香族改質萜烯聚合物及松香改質苯酚樹脂所組成的群組中的至少一種。In the conductive ink of the present invention, it is preferred that the terpene-based resin is selected from the group consisting of an α-pinene polymer, a β-pinene polymer, an α-pinene/β-pinene copolymer, and a limonene polymerization. At least one of the group consisting of rosin, rosin ester, modified rosin, terpene phenol polymer, hydrogenated terpene polymer, aromatic modified terpene polymer, and rosin modified phenol resin.

另外，本發明的導電性墨水中，較佳為所述分散介質中包含所述萜烯樹脂與高分子分散劑。Further, in the conductive ink of the present invention, it is preferable that the dispersion medium contains the terpene resin and a polymer dispersant.

進而，本發明的導電性墨水中，較佳為相對於銀固體成分，所述導電性墨水中所含的所述萜烯系樹脂為10重量%以下。 [發明的效果]Furthermore, in the conductive ink of the present invention, the terpene-based resin contained in the conductive ink is preferably 10% by weight or less based on the silver solid content. [Effects of the Invention]

依據本發明的導電性墨水，能夠實現一種可將具有充分的導電性及與基板的良好密合性的導電膜圖案於低溫下進行煅燒的導電性、進而操作容易且分散性亦優異的導電性墨水。According to the conductive ink of the present invention, it is possible to realize conductivity in which a conductive film pattern having sufficient conductivity and good adhesion to a substrate can be fired at a low temperature, and the conductivity is also easy to handle and excellent in dispersibility. ink.

以下，對（1）本發明的導電性墨水的較佳的一實施形態、（2）本發明的導電性墨水的製造方法的較佳的一實施形態、（3）使用本發明的導電性墨水的導電膜圖案以及其製造方法進行詳細說明。此外，於以下的說明中有時省略重覆的說明。Hereinafter, (1) a preferred embodiment of the conductive ink of the present invention, (2) a preferred embodiment of the method for producing a conductive ink of the present invention, and (3) using the conductive ink of the present invention. The conductive film pattern and its manufacturing method will be described in detail. In addition, in the following description, the repeated description may be omitted.

（1）導電性墨水 本實施形態的導電性墨水的特徵在於包含：銀奈米粒子（銀微粒子）、分散介質、以及附著於所述銀奈米粒子的表面或所述分散介質中所含的軟化溫度為90℃以上的萜烯系樹脂。另外，換言之，所述導電性墨水包含：以包含銀奈米粒子與有機成分的銀奈米粒子分散體（銀膠體（colloid）液）粒子作為主成分的固體成分、以及將該些固體成分進行分散的分散介質，此處包含所述萜烯系樹脂。其中，所述導電性墨水中，「分散介質」即便溶解所述固體成分的一部分亦無妨。(1) Conductive ink The conductive ink of the present embodiment includes silver nanoparticles (silver fine particles), a dispersion medium, and a surface attached to the silver nanoparticles or contained in the dispersion medium. A terpene-based resin having a softening temperature of 90 ° C or higher. In addition, in other words, the conductive ink includes a solid component containing a silver nanoparticle dispersion (silica colloidal liquid) particles containing silver nanoparticles and an organic component as a main component, and the solid components are subjected to the solid components. A dispersed dispersion medium containing the terpene-based resin herein. In the conductive ink, the "dispersion medium" may dissolve a part of the solid component.

依據此種銀膠體液，由於包含有機成分，故而可提高銀膠體液中的銀膠體粒子的分散性，因此，即便增加銀膠體液中的銀成分的含量，銀膠體粒子亦難以凝聚，能夠保持良好的分散穩定性。此外，此處所謂的「分散性」，是表示於剛製備銀屬膠體液後，該銀膠體液中的銀奈米粒子的分散狀態是否優異（是否均勻）者，所謂「分散穩定性」，是表示於調整銀膠體液且經過既定的時間後，該銀膠體液中的銀奈米粒子的分散狀態是否得以維持者，亦可稱為「低沈降凝聚性」或者「稀釋性」。Since the silver colloidal liquid contains an organic component, the dispersibility of the silver colloidal particles in the silver colloidal liquid can be improved. Therefore, even if the content of the silver component in the silver colloidal liquid is increased, the silver colloidal particles are hard to aggregate and can be maintained. Good dispersion stability. In addition, the term "dispersion" as used herein means whether the dispersion state of the silver nanoparticles in the silver colloidal liquid is excellent (whether or not) after the preparation of the silver colloidal liquid. It is shown that whether the dispersion state of the silver nanoparticles in the silver colloidal liquid is maintained after adjusting the silver colloidal liquid for a predetermined period of time is also referred to as "low sedimentation cohesiveness" or "dilution property".

此處，所述銀膠體液中，銀膠體粒子中的「有機成分」為實質上與所述金屬成分一併構成銀膠體粒子的有機物（其中，所述「附著於銀奈米粒子的表面或所述分散介質中所含的軟化溫度為90℃以上的萜烯系樹脂」除外）。該有機成分中不包含如銀中最初作為雜質而包含的微量有機物、於後述製造過程中混入的微量有機物附著於銀成分上的有機物、洗滌過程中未徹底去除的殘留還原劑、殘留分散劑等般，微量附著於銀成分上的有機物等。此外，所述「微量」，具體而言是指於銀膠體粒子中小於1質量%。Here, in the silver colloidal liquid, the "organic component" in the silver colloidal particles is an organic substance that substantially forms silver colloidal particles together with the metal component (wherein the "adhesion to the surface of the silver nanoparticle or The terpene-based resin having a softening temperature of 90 ° C or higher contained in the dispersion medium is excluded. The organic component does not include a trace amount of organic matter originally contained as an impurity in silver, an organic substance in which a trace amount of organic matter mixed in a production process described later adheres to a silver component, a residual reducing agent which is not completely removed during a washing process, a residual dispersant, and the like. Generally, a small amount of organic matter adhered to the silver component or the like. Further, the "minor amount" specifically means less than 1% by mass in the silver colloidal particles.

本實施形態中的銀膠體粒子由於包含有機成分，故而於銀膠體液中的分散穩定性高。因此，即便增大銀膠體液中的銀成分的含量，銀膠體粒子亦難以凝聚，其結果為保持良好的分散性。Since the silver colloidal particles in the present embodiment contain an organic component, the dispersion stability in the silver colloidal liquid is high. Therefore, even if the content of the silver component in the silver colloidal liquid is increased, the silver colloidal particles are less likely to aggregate, and as a result, good dispersibility is maintained.

另外，本實施形態中的銀膠體液的所謂「固體成分」，是指於使用二氧化矽凝膠等，自銀膠體液中去除分散介質後，例如於30℃以下的常溫（例如25℃）下乾燥24小時時所殘存的固體成分，通常包含銀奈米粒子、殘存有機成分及殘留還原劑、以及所述萜烯系樹脂等。此外，作為使用二氧化矽凝膠自銀膠體液中去除分散介質的方法，可採用各種方法，例如只要藉由在玻璃基板上塗佈銀膠體液，將帶有塗膜的玻璃基板於加入有二氧化矽凝膠的密閉容器中放置24小時以上而去除分散介質即可。In addition, the "solid content" of the silver colloidal liquid in the present embodiment means a normal temperature (for example, 25 ° C) of 30 ° C or lower after removing the dispersion medium from the silver colloidal liquid by using a cerium oxide gel or the like. The solid component remaining after drying for 24 hours usually contains silver nanoparticles, a residual organic component, a residual reducing agent, and the terpene-based resin. Further, as a method of removing a dispersion medium from a silver colloidal liquid using a ceria gel, various methods can be employed, for example, a glass substrate with a coating film is added by coating a silver colloidal liquid on a glass substrate. It is sufficient to leave the dispersion medium in a closed container of the cerium oxide gel for 24 hours or more.

本實施形態的銀膠體液中，較佳的固體成分的濃度為1質量%～60質量%。若固體成分的濃度為1質量%以上，則能夠確保導電性墨水中的銀的含量，導電效率不會降低。另外，若固體成分的濃度為60質量%以下，則銀膠體液的黏度不會增加，操作容易，於工業上有利，可形成平坦的薄膜。更佳的固體成分的濃度為5質量%～40質量%。In the silver colloidal liquid of the present embodiment, the concentration of the solid component is preferably from 1% by mass to 60% by mass. When the concentration of the solid component is 1% by mass or more, the content of silver in the conductive ink can be ensured, and the conductivity cannot be lowered. In addition, when the concentration of the solid component is 60% by mass or less, the viscosity of the silver colloidal liquid does not increase, the handling is easy, and industrially advantageous, a flat film can be formed. The concentration of the solid component is more preferably 5% by mass to 40% by mass.

此處，本實施形態的導電性墨水較佳為包含附著於所述銀奈米粒子的表面或所述分散介質中所含的軟化溫度為90℃以上的萜烯系樹脂。本發明者等人藉由使用該萜烯系樹脂，而實現了低溫燒結性及密合性以及分散性優異的導電性墨水。Here, the conductive ink of the present embodiment preferably contains a terpene-based resin having a softening temperature of 90 ° C or more contained on the surface of the silver nanoparticles or the dispersion medium. The present inventors have achieved a conductive ink excellent in low-temperature sinterability, adhesion, and dispersibility by using the terpene-based resin.

詳細情況將後述，本發明者等人發現：於本發明中，藉由將萜烯系樹脂不僅後添加於分散介質中，而且亦於銀奈米粒子合成前用作保護分散劑，而可同時改良所獲得的導電性墨水的分散性及密合性。另外確認到：雖然亦會因聚合度或種類而不同，但若萜烯系樹脂至少分子量為約800以上，則顯現出防止在如萜烯系樹脂溶解的分散介質中分子鏈伸長而粒子彼此凝聚的立體排斥效果，並且，該立體排斥效果發揮保護銀奈米粒子的作用，有助於對基材的密合性。The details will be described later, and the present inventors have found that in the present invention, the terpene-based resin can be used not only as a post-adding agent in the dispersion medium but also as a protective dispersing agent before the synthesis of the silver nanoparticles. The dispersibility and adhesion of the obtained conductive ink are improved. In addition, it is confirmed that the degree of polymerization or the type varies depending on the degree of polymerization. However, when the terpene-based resin has a molecular weight of at least 800 or more, it is prevented that the molecular chain is elongated and the particles are condensed in a dispersion medium in which the terpene-based resin is dissolved. The steric repulsion effect also serves to protect the silver nanoparticles and contribute to the adhesion to the substrate.

另外，萜烯系樹脂較佳為軟化溫度為90℃以上。較佳為「軟化溫度為90℃以上的萜烯系樹脂」的理由未必明確，但本發明者等人認為如下。萜烯系樹脂的玻璃轉移溫度為較該萜烯系樹脂的軟化溫度低約60℃左右的溫度已廣為人知。如此，例如軟化溫度為80℃以下的萜烯系樹脂的玻璃轉移溫度則為約20℃。因此認為，若軟化溫度過低，則玻璃轉移溫度甚至會低於室溫（例如25℃），從而分子的運動性急劇上升而呈非常鬆軟的性質，故而無法維持基材與導電層（塗佈導電性墨水所形成的層）間的密合力。即認為，為了維持基材與導電層間的密合力，應藉由將萜烯系樹脂的軟化溫度設為某種程度的高度，而將其玻璃轉移溫度設為室溫（25℃）以上，抑制分子的運動性而保持穩固的性質。Further, the terpene-based resin preferably has a softening temperature of 90 ° C or higher. The reason for the "decene-based resin having a softening temperature of 90 ° C or higher" is not necessarily clear, but the inventors of the present invention consider the following. The glass transition temperature of the terpene resin is widely known to be about 60 ° C lower than the softening temperature of the terpene resin. Thus, for example, the terpene-based resin having a softening temperature of 80 ° C or lower has a glass transition temperature of about 20 ° C. Therefore, if the softening temperature is too low, the glass transition temperature may be lower than room temperature (for example, 25 ° C), so that the mobility of the molecule sharply rises to be very soft, so that the substrate and the conductive layer cannot be maintained (coating) The adhesion between the layers formed by the conductive ink. In other words, in order to maintain the adhesion between the substrate and the conductive layer, the glass transition temperature of the terpene resin is set to a certain height, and the glass transition temperature is set to room temperature (25 ° C) or higher. The motility of the molecule maintains a stable nature.

此外，萜烯系樹脂的軟化溫度的上限只要大致為市售的萜烯系樹脂中具有最高軟化溫度的萜烯系樹脂的軟化溫度的程度即可，例如，若為160±5℃，則可更確實地獲得本申請案發明的作用效果。In addition, the upper limit of the softening temperature of the terpene-based resin may be approximately the softening temperature of the terpene-based resin having the highest softening temperature among the commercially available terpene-based resins. For example, if it is 160±5° C., The effect of the invention of the present application is obtained more surely.

另外，所述萜烯系樹脂較佳為選自由α-蒎烯聚合物、β-蒎烯聚合物、α-蒎烯/β-蒎烯共聚物、檸檬烯聚合物、松香、松香酯、改質松香、萜烯苯酚聚合物、氫化萜烯聚合物、芳香族改質萜烯聚合物及松香改質苯酚樹脂所組成的群組中的至少一種。其理由在於：與各種彈性體或有機溶媒非常良好地相容，發揮優異的黏著特性；而若為胡蘿蔔素（carotene）或天然橡膠般的聚萜烯，則顯著阻礙導電性，亦難以獲得黏著特性。Further, the terpene-based resin is preferably selected from the group consisting of an α-pinene polymer, a β-pinene polymer, an α-pinene/β-pinene copolymer, a limonene polymer, a rosin, a rosin ester, and a modification. At least one of the group consisting of rosin, terpene phenol polymer, hydrogenated terpene polymer, aromatic modified terpene polymer, and rosin modified phenol resin. The reason for this is that it is very compatible with various elastomers or organic solvents, and exhibits excellent adhesive properties. However, if it is a carotenoid or a natural rubber-like polydecene, it significantly hinders conductivity and is difficult to obtain adhesion. characteristic.

此外，本實施形態的導電性墨水中，出於需要於無損導電性的範圍內進行添加的理由考慮，所述導電性墨水中所含的所述萜烯系樹脂較佳為相對於銀固體成分而為10重量%以下。下限只要為1.0質量%左右即可。更佳為只要為1.0質量%～3.0質量%即可。Further, in the conductive ink of the present embodiment, the terpene-based resin contained in the conductive ink is preferably a solid component relative to silver, for the reason that it is required to be added in a range in which the conductivity is not impaired. It is 10% by weight or less. The lower limit may be about 1.0% by mass. More preferably, it is 1.0% by mass to 3.0% by mass.

本實施形態的導電性墨水較佳為表面張力為22 mN/m以下。藉由將表面張力充分降低至22 mN/m以下，可充分地擔保導電性墨水的潤濕性。可藉由調整導電性墨水的成分比來實現將表面張力設為22 mN/m以下的目的。表面張力的下限只要為13 mN/m左右即可。此外，本發明中所謂的表面張力是以板法（plate method）（威廉（Wilhelmy）法）的原理來測定而獲得，例如可利用協和界面科學（股）製造的全自動表面張力計CBVP-Z等來測定。The conductive ink of the present embodiment preferably has a surface tension of 22 mN/m or less. By sufficiently reducing the surface tension to 22 mN/m or less, the wettability of the conductive ink can be sufficiently ensured. The purpose of setting the surface tension to 22 mN/m or less can be achieved by adjusting the composition ratio of the conductive ink. The lower limit of the surface tension may be about 13 mN/m. Further, the so-called surface tension in the present invention is obtained by measuring the principle of a plate method (Wilhelmy method), for example, a fully automatic surface tension meter CBVP-Z manufactured by Concord Interface Science Co., Ltd. Wait for the measurement.

（1-1）銀奈米粒子（銀奈米粒子） 本實施形態中的銀奈米粒子分散體中所含的銀奈米粒子的平均粒徑只要為不損及本發明的效果的範圍，則並無特別限制，較佳為具有產生熔點下降的平均粒徑，例如只要為1 nm～400 nm即可。尤佳為1 nm～70 nm。若銀奈米粒子的平均粒徑為1 nm以上，則不僅銀奈米粒子具備良好的低溫燒結性，而且銀奈米粒子製造的成本不會變高，較為實用。另外，若為400 nm以下，則銀奈米粒子的分散性難以經時地變化，較佳。此外，使用本實施形態的銀奈米粒子分散體而獲得的導電性墨水中，銀膠體粒子（包含銀奈米粒子）的平均粒徑（中值粒徑）亦與該範圍大致相同（可近似）。(1-1) Silver Nanoparticles (Silver Nanoparticles) The average particle diameter of the silver nanoparticles contained in the silver nanoparticle dispersion of the present embodiment is not limited to the range of the effect of the present invention. There is no particular limitation, and it is preferred to have an average particle diameter at which a melting point is lowered, and for example, it is preferably 1 nm to 400 nm. Especially preferred is 1 nm to 70 nm. When the average particle diameter of the silver nanoparticles is 1 nm or more, not only the silver nanoparticles have good low-temperature sinterability, but also the cost of manufacturing the silver nanoparticles is not high, which is practical. Further, when it is 400 nm or less, the dispersibility of the silver nanoparticles is difficult to change with time, which is preferable. Further, in the conductive ink obtained by using the silver nanoparticle dispersion of the present embodiment, the average particle diameter (median diameter) of the silver colloidal particles (including silver nanoparticles) is substantially the same as the range (approximate ).

此外，銀奈米粒子分散體中的銀奈米粒子的粒徑隨著固體成分濃度而變動，並不限定為固定，亦可不固定。另外，於銀奈米粒子分散體包含後述分散劑等作為任意成分的情況下，存在包含平均粒徑超過400 nm的銀奈米粒子成分的情況，但若為不產生凝聚，不明顯損及本發明的效果的成分，則亦可包含所述具有超過400 nm的平均粒徑的銀奈米粒子成分。Further, the particle diameter of the silver nanoparticles in the silver nanoparticle dispersion varies depending on the solid content concentration, and is not limited to being fixed, and may not be fixed. In addition, when the silver nanoparticle dispersion contains an optional component such as a dispersant described later, the silver nanoparticle component having an average particle diameter of more than 400 nm may be contained. However, if the aggregation does not occur, the present invention is not significantly impaired. The component of the effect of the invention may also include the silver nanoparticle component having an average particle diameter of more than 400 nm.

此處，本實施形態的銀奈米粒子分散體中的銀奈米粒子的平均粒徑是藉由動態光散射法（多普勒（doppler）散射光解析）而得者，例如可由利用堀場製作所（股）製造的動態光散射式粒徑分佈測定裝置LB-550來測定的體積基準的中值粒徑（D50）來表示。具體而言，於10 mL的乙醇中滴加數滴的金屬膠體液，以手振動使其分散而製備測定用試樣。繼而，將3 mL的測定用試樣投入至堀場製作所（股）製造的動態光散射式粒徑分佈測定裝置LB-550的槽內，利用下述條件來測定。Here, the average particle diameter of the silver nanoparticles in the silver nanoparticle dispersion of the present embodiment is obtained by a dynamic light scattering method (Doppler scattered light analysis), and for example, it can be used by Horiba. The volume-based median diameter (D50) of the dynamic light scattering type particle size distribution measuring apparatus LB-550 manufactured by the (strand) was measured. Specifically, a few drops of the metal colloidal liquid were added dropwise to 10 mL of ethanol, and the sample for measurement was prepared by shaking by hand. Then, 3 mL of the sample for measurement was placed in a tank of a dynamic light scattering type particle size distribution measuring apparatus LB-550 manufactured by Horiba, Ltd., and measured under the following conditions.

·測定條件 資料讀入次數：100次 槽架內溫度：25℃ ·顯示條件 分佈形態：標準 反覆次數：50次 粒徑基準：體積基準 分散質的折射率：0.200-3.900i（銀的情況） 分散介質的折射率：1.36（乙醇為主成分的情況） ·系統條件設定 強度基準：動態（Dynamic） 散射強度範圍上限：10000.00 散射強度範圍下限：1.00· Measurement condition data reading times: 100 times in the rack temperature: 25 ° C · Display condition distribution pattern: standard repeat times: 50 times particle size basis: volume basis dispersity refractive index: 0.200-3.900i (in the case of silver) Refractive index of dispersion medium: 1.36 (in case of ethanol as main component) · System condition setting Strength reference: Dynamic (Dynamic) Upper limit of scattering intensity range: 10000.00 Lower limit of scattering intensity range: 1.00

（1-2）胺 本實施形態的銀奈米粒子分散體中，於銀奈米粒子的表面的至少一部分附著有胺（較佳為碳數為5以下的短鏈胺）。此外，於銀奈米粒子的表面，亦可附著有如原料中最初作為雜質而包含的微量有機物、後述製造過程中混入的微量有機物、洗滌過程中未徹底去除的殘留還原劑、殘留分散劑等般微量的有機物。(1-2) Amine In the silver nanoparticle dispersion of the present embodiment, an amine (preferably a short-chain amine having a carbon number of 5 or less) is attached to at least a part of the surface of the silver nanoparticles. Further, on the surface of the silver nanoparticles, a trace amount of organic substances which are initially contained as impurities in the raw material, a trace amount of organic substances mixed in a production process to be described later, a residual reducing agent which is not completely removed during the washing process, and a residual dispersant may be adhered thereto. Traces of organic matter.

作為所述胺，可使用各種胺，可為直鏈狀，亦可為分支鏈狀，另外亦可具有側鏈。若為碳數為5以下的短鏈胺則並無特別限定，作為該短鏈胺，例如可列舉：乙胺、丙胺、丁胺、N-(3-甲氧基丙基)丙烷-1,3-二胺、1,2-乙二胺、2-甲氧基乙胺、3-甲氧基丙胺、3-乙氧基丙胺、1,4-丁二胺、1,5-戊二胺、戊醇胺、胺基異丁醇等。As the amine, various amines may be used, and they may be linear or branched, or may have a side chain. The short-chain amine having a carbon number of 5 or less is not particularly limited, and examples of the short-chain amine include ethylamine, propylamine, butylamine, and N-(3-methoxypropyl)propane-1. 3-Diamine, 1,2-ethylenediamine, 2-methoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 1,4-butanediamine, 1,5-pentanediamine , pentanolamine, amine isobutanol and the like.

所述短鏈胺例如可為包含羥基、羧基、烷氧基、羰基、酯基、巰基等的胺以外的官能基的化合物。另外，所述胺可分別單獨使用，亦可併用兩種以上。除此以外，常壓下的沸點較佳為300℃以下，尤佳為250℃以下。The short-chain amine may be, for example, a compound having a functional group other than an amine such as a hydroxyl group, a carboxyl group, an alkoxy group, a carbonyl group, an ester group or a mercapto group. Further, the amines may be used alone or in combination of two or more. Other than this, the boiling point at normal pressure is preferably 300 ° C or lower, and particularly preferably 250 ° C or lower.

若為不損及本發明的效果的範圍，則本實施形態的銀粒子分散體除了包含所述碳數為5以下的短鏈胺以外，亦可包含羧酸。羧酸的一分子內的羧基具有比較高的極性，容易產生由氫鍵引起的相互作用，但該些官能基以外的部分具有比較低的極性。進而，羧基容易顯示出酸性的性質。另外，羧酸若於本實施形態的銀粒子分散體中局部存在（附著）於銀奈米粒子的表面的至少一部分中（即，若被覆銀奈米粒子的表面的至少一部分），則可使溶媒與銀奈米粒子充分地親和，可防止銀奈米粒子彼此的凝聚（提高分散性）。The silver particle dispersion of the present embodiment may contain a carboxylic acid in addition to the short-chain amine having 5 or less carbon atoms, insofar as it does not impair the effects of the present invention. A carboxyl group in one molecule of a carboxylic acid has a relatively high polarity, and an interaction caused by a hydrogen bond is apt to occur, but a portion other than the functional group has a relatively low polarity. Further, the carboxyl group is liable to exhibit acidic properties. Further, when the carboxylic acid is locally present (attached) to at least a part of the surface of the silver nanoparticles in the silver particle dispersion of the present embodiment (that is, if at least a part of the surface of the silver nanoparticles are coated), The solvent and the silver nanoparticles are sufficiently affinity to prevent aggregation of the silver nanoparticles (enhanced dispersibility).

作為羧酸，可廣泛使用具有至少一個羧基的化合物，例如可列舉：甲酸、乙二酸、乙酸、己酸、丙烯酸、辛酸、油酸等。羧酸的一部分的羧基亦可與金屬離子形成鹽。此外，關於該金屬離子，亦可包含兩種以上的金屬離子。As the carboxylic acid, a compound having at least one carboxyl group can be widely used, and examples thereof include formic acid, oxalic acid, acetic acid, caproic acid, acrylic acid, octanoic acid, and oleic acid. A carboxyl group of a part of the carboxylic acid may also form a salt with the metal ion. Further, two or more metal ions may be contained in the metal ion.

所述羧酸亦可為例如包含胺基、羥基、烷氧基、羰基、酯基、巰基等的羧基以外的官能基的化合物。該情況下，羧基的數量較佳為羧基以外的官能基的數量以上。另外，所述羧酸可分別單獨使用，亦可併用兩種以上。除此以外，常壓下的沸點較佳為300℃以下，尤佳為250℃以下。另外，胺與羧酸形成醯胺。該醯胺基亦適度地吸附於銀奈米粒子表面，因此於銀奈米粒子表面可附著有醯胺基。The carboxylic acid may be, for example, a compound containing a functional group other than a carboxyl group such as an amine group, a hydroxyl group, an alkoxy group, a carbonyl group, an ester group or a fluorenyl group. In this case, the number of carboxyl groups is preferably at least the number of functional groups other than the carboxyl group. Further, the carboxylic acids may be used alone or in combination of two or more. Other than this, the boiling point at normal pressure is preferably 300 ° C or lower, and particularly preferably 250 ° C or lower. Additionally, the amine forms a guanamine with the carboxylic acid. The guanamine group is also moderately adsorbed on the surface of the silver nanoparticles, so that a guanamine group can be attached to the surface of the silver nanoparticles.

（1-3）分散介質 本實施形態的銀奈米粒子分散體是於各種分散介質中分散有銀奈米粒子者。作為該分散介質，可於無損本發明的效果的範圍內使用各種分散介質，可列舉烴及醇等。此外，該分散介質中亦可溶解有所述萜烯系樹脂。(1-3) Dispersion medium The silver nanoparticle dispersion of the present embodiment is one in which silver nanoparticles are dispersed in various dispersion media. As the dispersion medium, various dispersion media can be used without departing from the effects of the present invention, and examples thereof include hydrocarbons and alcohols. Further, the terpene-based resin may be dissolved in the dispersion medium.

作為烴，可列舉脂肪族烴、環狀烴及脂環式烴等，分別可單獨使用，亦可併用兩種以上。作為脂肪族烴，例如可列舉：十四烷、十八烷、七甲基壬烷、四甲基十五烷、己烷、庚烷、辛烷、壬烷、癸烷、十三烷、甲基戊烷、正鏈烷烴、異鏈烷烴等飽和脂肪族烴或不飽和脂肪族烴。作為環狀烴，例如可列舉：甲苯、二甲苯等。進而，作為脂環式烴，例如可列舉：檸檬烯、雙戊烯、松油烯（terpinene）、萜品烯（亦稱為松油烯）、薴烯（Nesol）、松油精（Cinene）、橘子香料、異松油烯（terpinolene）、萜品油烯（亦稱為異松油烯）、水芹烯、薄荷二烯、松脂烴（terebene）、二氫異丙基甲苯、石薺烯（Moslene）、異松油烯（isoterpinene）、異萜品烯（亦稱為異松油烯）、γ-萜品烯（Crithmene）、薴（Kautschin）、白千層萜（cajeputene）、檸烯（Eulimen）、蒎烯、松節油（turpentine）、薄荷烷、蒎烷、萜烯、環己烷等。Examples of the hydrocarbons include aliphatic hydrocarbons, cyclic hydrocarbons, and alicyclic hydrocarbons, and they may be used alone or in combination of two or more. Examples of the aliphatic hydrocarbons include tetradecane, octadecane, heptamethylnonane, tetramethylpentadecane, hexane, heptane, octane, decane, decane, tridecane, and A. A saturated aliphatic hydrocarbon or an unsaturated aliphatic hydrocarbon such as a pentane, a normal paraffin or an isoparaffin. Examples of the cyclic hydrocarbon include toluene, xylene, and the like. Further, examples of the alicyclic hydrocarbon include limonene, dipentene, terpinene, terpinene (also known as terpinene), nesol (Nesol), and pinene (Cinene). Orange spice, terpinolene, terpinolene (also known as terpinolene), hydrocelene, menthene, terebene, dihydroisopropyltoluene, lindenene Moslene), isoterpinene, isodecene (also known as terpinolene), γ-terpinene (Crithmene), 薴 (Kautschin), 千 萜 (cajeputene), limene ( Eulimen), terpenes, turpentine, menthane, decane, decene, cyclohexane, and the like.

另外，醇為分子結構中含有一個以上的OH基的化合物，可列舉脂肪族醇、環狀醇及脂環式醇，分別可單獨使用，亦可併用兩種以上。另外，於無損本發明的效果的範圍內，OH基的一部分亦可衍生成乙醯氧基等。In addition, the alcohol is a compound having one or more OH groups in its molecular structure, and examples thereof include an aliphatic alcohol, a cyclic alcohol, and an alicyclic alcohol, and they may be used alone or in combination of two or more. Further, a part of the OH group may be derived from an ethoxy group or the like within the range which does not impair the effects of the present invention.

作為脂肪族醇，例如可列舉：庚醇、辛醇（1-辛醇、2-辛醇、3-辛醇等）、癸醇（1-癸醇等）、月桂醇、十四醇、十六醇（cetyl alcohol）、2-乙基-1-己醇、十八醇、十六碳烯醇、油醇等飽和C_6-30 脂肪族醇或不飽和C_6-30 脂肪族醇等。作為環狀醇，例如可列舉：甲酚、丁香酚等。進而，作為脂環式醇，例如可列舉：環己醇等環烷醇、松油醇（包含α異構體、β異構體、γ異構體、或該些的任意的混合物）、二氫松油醇等萜烯醇（單萜烯醇等）、二氫萜品醇、桃金孃烯醇、蘇伯樓醇（sobrerol）、薄荷醇、香旱芹醇、紫蘇醇、松香芹醇、蘇伯樓醇（sobrerol）、馬鞭草烯醇等。Examples of the aliphatic alcohol include heptanol, octanol (1-octanol, 2-octanol, 3-octanol, etc.), decyl alcohol (1-nonanol, etc.), lauryl alcohol, tetradecyl alcohol, and ten. A saturated C _6-30 aliphatic alcohol or an unsaturated C _6-30 aliphatic alcohol such as cetyl alcohol, 2-ethyl-1-hexanol, stearyl alcohol, hexadecenol or oleyl alcohol. Examples of the cyclic alcohol include cresol and eugenol. Further, examples of the alicyclic alcohol include a cycloalkanol such as cyclohexanol and terpineol (including an alpha isomer, a beta isomer, a γ isomer, or a mixture of any of these). Terpene alcohol such as hydrogen terpineol (monoterpene alcohol, etc.), dihydroterpineol, myrtenol, sobrerol, menthol, saramenol, perillyl alcohol, rosinol , Sobrerol, verbena, and the like.

（1-4）分散劑 本實施形態的銀粒子分散體中，更包含為了使銀奈米粒子分散而於銀奈米粒子合成後添加的分散劑。藉由使用所述分散劑，可提高溶媒中的銀奈米粒子的分散穩定性。此處，該分散劑的酸價更佳為5～200，且該分散劑尤佳為具有源自磷酸的官能基。(1-4) Dispersing Agent The silver particle dispersion of the present embodiment further contains a dispersing agent added after the silver nanoparticles are mixed in order to disperse the silver nanoparticles. By using the dispersant, the dispersion stability of the silver nanoparticles in the solvent can be improved. Here, the acid value of the dispersing agent is more preferably from 5 to 200, and the dispersing agent is particularly preferably a functional group derived from phosphoric acid.

其原因在於：若分散劑的酸價為5以上，則與胺配位而開始產生因酸鹼相互作用造成的對粒子表面為鹼性的銀的吸附，其原因在於：若為200以下，則不會過度地具有吸附部位，故而以較佳的形態來吸附。另外，其原因在於：藉由分散劑具有源自磷酸的官能基，磷P經由氧O而與銀相互作用，因此對於與銀或銀化合物的吸附而言最有效果，能夠以必需最小限度的吸附量來獲得適當的分散性。The reason for this is that when the acid value of the dispersant is 5 or more, the adsorption of silver which is alkaline on the surface of the particles due to the acid-base interaction starts to occur in coordination with the amine, because if it is 200 or less, It does not excessively have an adsorption site, so it is adsorbed in a preferred form. Further, the reason is that since the dispersing agent has a functional group derived from phosphoric acid, and phosphorus P interacts with silver via oxygen O, it is most effective for adsorption with silver or a silver compound, and can be minimized. The amount of adsorption is used to obtain proper dispersibility.

此外，作為酸價為5～200的高分子分散劑，例如路博潤（Lubrizol）公司的索努帕斯（SOLSPERSE）系列中可列舉SOLSPERSE-16000、21000、41000、41090、43000、44000、46000、54000等，畢克化學（BYK-Chemie）公司的迪斯帕畢克（DISPERBYK）系列中可列舉DISPERBYK-102、110、111、170、190、194N、2015、2090、2096等，贏創（Evonik）公司的迪高迪斯帕（TEGO Dispers）系列中可列舉610、610S、630、651、655、750W、755W等，楠本化成（股）製造的帝司巴隆（Disparlon）系列中可列舉DA-375、DA-1200等，共榮化學工業（股）製造的弗洛蘭（Flowlen）系列中可例示WK-13E、G-700、G-900、GW-1500、GW-1640、WK-13E。Further, as a polymer dispersant having an acid value of 5 to 200, for example, Lubrizol's SOLSPERS series can be cited as SOLSPERSE-16000, 21000, 41000, 41090, 43000, 44000, 46000. , 54000, etc., BYK-Chemie's DISPERBYK series can be listed as DISPERBYK-102, 110, 111, 170, 190, 194N, 2015, 2090, 2096, etc., Evonik ( Evonik)'s TEGO Dispers series include 610, 610S, 630, 651, 655, 750W, 755W, etc., which can be listed in the Disparlon series manufactured by Nanben Chemical Co., Ltd. DA-375, DA-1200, etc., in the Flowlen series manufactured by Kyoei Chemical Industry Co., Ltd., can be exemplified as WK-13E, G-700, G-900, GW-1500, GW-1640, WK- 13E.

本實施形態的銀奈米粒子分散體中含有分散劑的情況下的含量只要根據黏度等所需的特性來調整即可，例如，於使用銀奈米粒子分散體作為銀墨水的情況下，較佳為將分散劑的含量設為0.5質量%～20質量%，於用作銀漿的情況下，較佳為將分散劑的含量設為0.1質量%～10質量%。The content in the case where the dispersing agent is contained in the silver nanoparticle dispersion of the present embodiment may be adjusted according to characteristics required for viscosity or the like. For example, when a silver nanoparticle dispersion is used as the silver ink, The content of the dispersant is preferably from 0.5% by mass to 20% by mass. When used as a silver paste, the content of the dispersant is preferably from 0.1% by mass to 10% by mass.

高分子分散劑的含量較佳為0.1質量%～15質量%。若高分子分散劑的含量為0.1%以上，則所獲得的銀奈米粒子分散體的分散穩定性變得良好，於含量過多的情況下，低溫燒結性下降。就此種觀點而言，高分子分散劑的更佳的含量為0.3質量%～10質量%，尤佳的含量為0.5質量%～8質量%。The content of the polymer dispersant is preferably from 0.1% by mass to 15% by mass. When the content of the polymer dispersant is 0.1% or more, the dispersion stability of the obtained silver nanoparticle dispersion becomes good, and when the content is too large, the low-temperature sinterability is lowered. From such a viewpoint, a more preferable content of the polymer dispersant is 0.3% by mass to 10% by mass, and a more preferable content is 0.5% by mass to 8% by mass.

本實施形態的銀奈米粒子分散體較佳為：對固體成分以10℃/min的升溫速度進行熱重量分析時的100℃～500℃下的重量損耗為15質量%以下。若將所述固形物加熱至500℃，則有機物等氧化分解，大部分氣化而消失。因此，因加熱至500℃而引起的減量可基本上相當於固體成分中的有機物的量。In the silver nanoparticle dispersion of the present embodiment, the weight loss at 100 ° C to 500 ° C when the solid component is subjected to thermogravimetric analysis at a temperature increase rate of 10 ° C / min is preferably 15% by mass or less. When the solid matter is heated to 500 ° C, the organic matter or the like is oxidatively decomposed, and most of the gasification disappears. Therefore, the amount of reduction due to heating to 500 ° C can substantially correspond to the amount of organic matter in the solid component.

所述重量損耗越多，銀奈米粒子分散體的分散穩定性越優異，若過多，則有機物作為雜質而殘留於導電性墨水中，使導電性下降。特別是為了藉由100℃左右的低溫下的加熱而獲得導電性高的導電膜圖案，所述重量損耗較佳為20質量%以下。另一方面，若所述重量損耗過少，則膠體狀態下的分散穩定性受損，因此較佳為0.1質量%以上。更佳的重量損耗為0.5質量%～15質量%。The more the weight loss is, the more excellent the dispersion stability of the silver nanoparticle dispersion is, and if it is too large, the organic substance remains as an impurity in the conductive ink, and the conductivity is lowered. In particular, in order to obtain a conductive film pattern having high conductivity by heating at a low temperature of about 100 ° C, the weight loss is preferably 20% by mass or less. On the other hand, when the weight loss is too small, the dispersion stability in the colloidal state is impaired, and therefore it is preferably 0.1% by mass or more. A more preferable weight loss is 0.5% by mass to 15% by mass.

（1-5）保護劑（保護分散劑） 本實施形態的銀奈米粒子分散體可更包含銀奈米粒子合成前所添加的作為保護劑的具有酸價的分散劑（保護分散劑）。此處所謂的「保護分散劑」可為與所述銀奈米粒子合成後所添加的所述分散劑（具有酸價的分散劑）相同種類者，亦可為不同種類者。(1-5) Protecting Agent (Protective Dispersing Agent) The silver nanoparticle dispersion of the present embodiment may further contain an acid value dispersing agent (protective dispersing agent) as a protective agent added before the synthesis of the silver nanoparticles. Here, the "protective dispersant" may be the same type as the dispersant (dispersant having an acid value) added after the synthesis of the silver nanoparticles, or may be of a different type.

（1-5）其他成分 本實施形態的銀奈米粒子分散體中，除了所述成分以外，亦可於不損及本發明的效果的範圍內，為了賦予符合使用目的的適度的黏性、密合性、乾燥性或者印刷性等功能，而添加例如發揮作為黏合劑的作用的寡聚物成分、樹脂成分、有機溶劑（可使固體成分的一部分溶解或分散）、界面活性劑、增黏劑或者表面張力調整劑等任意成分。所述任意成分並無特別限定。(1-5) Other components In the silver nanoparticle dispersion of the present embodiment, in addition to the above-described components, it is possible to impart an appropriate viscosity in accordance with the purpose of use, without impairing the effects of the present invention. For example, an oligomer component, a resin component, an organic solvent (a part of a solid component can be dissolved or dispersed), a surfactant, and a viscosity-increasing function, which functions as a binder, are added, such as adhesiveness, drying property, and printing property. Any component such as a agent or a surface tension adjuster. The optional component is not particularly limited.

作為樹脂成分，例如可列舉聚酯系樹脂、嵌段異氰酸酯等聚胺基甲酸酯系樹脂、聚丙烯酸酯系樹脂、聚丙烯醯胺系樹脂、聚醚系樹脂或者三聚氰胺系樹脂等，該些樹脂可分別單獨使用，亦可併用兩種以上。Examples of the resin component include a polyester resin, a polyurethane resin such as a blocked isocyanate, a polyacrylate resin, a polypropylene phthalamide resin, a polyether resin, or a melamine resin. The resins may be used singly or in combination of two or more.

作為增黏劑，例如可列舉黏土（clay）、膨潤土（bentonite）或鋰膨潤石（hectorite）等黏土礦物，例如：聚酯系乳膠樹脂、丙烯酸系乳膠樹脂、聚胺基甲酸酯系乳膠樹脂或者嵌段異氰酸酯等乳膠，甲基纖維素、羧基甲基纖維素、羥基乙基纖維素、羥基丙基纖維素、羥基丙基甲基纖維素的纖維素衍生物、三仙膠（xanthan gum）或者瓜爾膠（guar gum）等多糖類等，該些增黏劑可分別單獨使用，亦可併用兩種以上。Examples of the tackifier include clay minerals such as clay, bentonite, and hectorite, such as polyester latex resin, acrylic latex resin, and polyurethane resin latex resin. Or latex such as blocked isocyanate, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, cellulose derivative of hydroxypropylmethylcellulose, xanthan gum Or a polysaccharide such as guar gum or the like, and these tackifiers may be used alone or in combination of two or more.

亦可添加與所述有機成分不同的界面活性劑。多成分溶媒系的無機膠體分散液中，容易產生因乾燥時的揮發速度的差異而引起的覆膜表面的粗糙以及固體成分的偏差。藉由在本實施形態的銀奈米粒子分散體中添加界面活性劑，而抑制該些不利，獲得可形成均勻的導電性覆膜的銀奈米粒子分散體。A surfactant different from the organic component may also be added. In the multicomponent solvent-based inorganic colloidal dispersion, the surface roughness and the variation of the solid content due to the difference in the volatilization speed during drying tend to occur. By adding a surfactant to the silver nanoparticle dispersion of the present embodiment, the disadvantage is suppressed, and a silver nanoparticle dispersion capable of forming a uniform conductive film is obtained.

本實施形態中可使用的界面活性劑並無特別限定，可使用陰離子性界面活性劑、陽離子性界面活性劑、非離子性界面活性劑的任一者，例如可列舉烷基苯磺酸鹽、四級銨鹽等。其中，由於以少量的添加量而獲得效果，故而較佳為氟系界面活性劑、矽酮系界面活性劑。若界面活性劑的含量過少，則無法獲得效果，若過多，則於覆膜中成為殘量雜質，因此存在阻礙導電性的顧慮。相對於銀奈米粒子分散體的分散介質100質量份，較佳的界面活性劑的含量為0.01質量份～5質量份。The surfactant which can be used in the embodiment is not particularly limited, and any of an anionic surfactant, a cationic surfactant, and a nonionic surfactant can be used, and examples thereof include an alkylbenzenesulfonate. Quaternary ammonium salts and the like. Among them, a fluorine-based surfactant and an anthrone-based surfactant are preferable because an effect is obtained with a small amount of addition. When the content of the surfactant is too small, an effect cannot be obtained, and if it is too large, it becomes a residual impurity in the film, and thus there is a concern that conductivity is inhibited. The content of the surfactant is preferably from 0.01 part by mass to 5 parts by mass based on 100 parts by mass of the dispersion medium of the silver nanoparticle dispersion.

本實施形態中的銀奈米粒子分散體中，胺附著於銀奈米粒子的表面的至少一部分，進而萜烯系樹脂附著於銀奈米粒子的表面或分散（溶解）於分散介質中。如上所述，藉由使胺附著於銀奈米粒子的表面的至少一部分，且以任意形態而包含萜烯系樹脂，可對銀奈米粒子賦予對於各種溶媒優異的分散性及低溫燒結性。In the silver nanoparticle dispersion of the present embodiment, the amine adheres to at least a part of the surface of the silver nanoparticles, and further the terpene resin adheres to the surface of the silver nanoparticles or is dispersed (dissolved) in the dispersion medium. As described above, by attaching the amine to at least a part of the surface of the silver nanoparticles and including the terpene resin in an arbitrary form, the silver nanoparticles can be provided with excellent dispersibility and low-temperature sinterability for various solvents.

本實施形態的銀奈米粒子分散體的黏度理想為1 cps～100 cps的黏度範圍，更佳為1 cps～20 cps的黏度範圍。藉由設為該黏度範圍，可將銀奈米粒子分散體均勻地且以薄膜狀塗佈於矽酮樹脂上。塗佈的方法中可利用通用的塗佈方法，可例示：敷料器法、棒塗佈機法、毛細管塗佈機法、以及旋轉塗佈法等。The viscosity of the silver nanoparticle dispersion of the present embodiment is preferably in the range of 1 cps to 100 cps, more preferably in the range of 1 cps to 20 cps. By setting this viscosity range, the silver nanoparticle dispersion can be uniformly applied to the fluorenone resin in a film form. A general coating method can be used for the coating method, and examples thereof include an applicator method, a bar coater method, a capillary coater method, and a spin coating method.

本實施形態的銀奈米粒子分散體的黏度的調整可藉由固體成分濃度的調整、各成分的調配比的調整、增黏劑的添加等而進行。另外，可利用振動式黏度計（例如CBC（股）製造的VM-100A-L）來測定黏度。測定是對振盪器浸漬液體而進行，測定溫度只要設為常溫（20℃～25℃）即可。The adjustment of the viscosity of the silver nanoparticle dispersion of the present embodiment can be carried out by adjusting the solid content concentration, adjusting the blending ratio of each component, and adding an thickener. Further, the viscosity can be measured using a vibrating viscometer (for example, VM-100A-L manufactured by CBC). The measurement is performed by immersing the liquid in the shaker, and the measurement temperature may be set to a normal temperature (20 ° C to 25 ° C).

（2）導電性墨水的製造方法 為了製造本實施形態的導電性墨水，首先製備銀奈米粒子分散體（金屬膠體液）。繼而，藉由將該金屬膠體液、與所述各種成分進行混合，可獲得本實施形態的導電性墨水。其中，作為必需成分的萜烯系樹脂不僅可後添加於分散介質中，而且亦可於銀奈米粒子合成前作為保護分散劑而添加。(2) Method for Producing Conductive Ink In order to produce the conductive ink of the present embodiment, first, a silver nanoparticle dispersion (metal colloidal liquid) was prepared. Then, the conductive ink of the present embodiment can be obtained by mixing the metal colloidal liquid with the various components. Among them, the terpene-based resin as an essential component may be added not only to the dispersion medium but also as a protective dispersant before the synthesis of the silver nanoparticles.

其中，本實施形態的銀奈米粒子分散體包括：生成銀奈米粒子的步驟；以及於所述銀奈米粒子中添加·混合用以使所述銀奈米粒子分散的具有酸價的分散劑的步驟。進而，較佳為包括：第1前步驟，調整可藉由還原而分解生成金屬銀的銀化合物、與分配係數logP為-1.0～1.4的短鏈胺的混合液；以及第2前步驟，藉由將該混合液中的所述銀化合物還原而生成於表面的至少一部分附著有胺的銀奈米粒子。The silver nanoparticle dispersion of the present embodiment includes a step of producing silver nanoparticle particles, and an acid value dispersion in which the silver nanoparticle particles are added and mixed to disperse the silver nanoparticle particles. The steps of the agent. Furthermore, it is preferable to include: a first pre-step, adjusting a mixture of a silver compound which can be decomposed to form metallic silver by reduction, and a short-chain amine having a partition coefficient logP of -1.0 to 1.4; and a second pre-step A silver nanoparticle having an amine attached to at least a part of the surface formed by reducing the silver compound in the mixed solution.

於所述第1前步驟中，較佳為相對於1 mol的金屬銀而添加2 mol以上的胺。藉由將胺的添加量相對於1 mol的金屬銀而設為2 mol以上，可使適量的胺附著於藉由還原而生成的銀奈米粒子的表面，可對該銀奈米粒子賦予對於各種分散介質優異的分散性及低溫燒結性。In the first pre-step, it is preferred to add 2 mol or more of an amine to 1 mol of metallic silver. By setting the amount of the amine to be 2 mol or more with respect to 1 mol of metallic silver, an appropriate amount of amine can be attached to the surface of the silver nanoparticle produced by reduction, and the silver nanoparticle can be imparted to the silver nanoparticle. Excellent dispersibility and low-temperature sinterability of various dispersion media.

此外，根據所述第1前步驟中的混合液的組成以及所述第2前步驟中的還原條件（例如加熱溫度以及加熱時間等），較佳為將所獲得的銀奈米粒子的粒徑設為產生熔點下降的奈米尺寸，更佳為設為1 nm～200 nm。此處，視需要亦可包含微米尺寸的粒子。自所述第2前步驟中獲得的銀奈米粒子分散體中取出銀奈米粒子的方法並無特別限定，例如可列舉對所述銀奈米粒子分散體進行洗滌的方法等。Further, according to the composition of the mixed liquid in the first preceding step and the reducing conditions (for example, the heating temperature and the heating time) in the second preceding step, the particle diameter of the obtained silver nanoparticle is preferably used. It is set to have a nanometer size at which the melting point is lowered, and more preferably set to 1 nm to 200 nm. Here, micron-sized particles may also be included as needed. The method of extracting the silver nanoparticles from the silver nanoparticle dispersion obtained in the second pre-step is not particularly limited, and examples thereof include a method of washing the silver nanoparticle dispersion and the like.

作為用以獲得由有機物（胺）所被覆的銀奈米粒子的起始材料，可使用各種公知的銀化合物（金屬鹽或其水合物），例如可列舉：硝酸銀、硫酸銀、氯化銀、氧化銀、乙酸銀、乙二酸銀、甲酸銀、亞硝酸銀、氯酸銀、硫化銀等銀鹽。該些化合物只要可還原，則並無特別限定，可溶解於適當的溶媒中，亦可以分散於溶媒中的狀態來使用。另外，該些化合物可單獨使用，亦可併用多種。As a starting material for obtaining silver nanoparticles coated with an organic substance (amine), various known silver compounds (metal salts or hydrates thereof) can be used, and examples thereof include silver nitrate, silver sulfate, and silver chloride. A silver salt such as silver oxide, silver acetate, silver oxalate, silver formate, silver nitrite, silver chlorate or silver sulfide. These compounds are not particularly limited as long as they can be reduced, and they can be dissolved in a suitable solvent or used in a state of being dispersed in a solvent. Further, these compounds may be used singly or in combination of two or more.

另外，於所述原料液中將該些銀化合物還原的方法並無特別限定，例如可列舉：使用還原劑的方法；照射紫外線等光、電子束、超音波或者熱能量的方法；加熱的方法等。其中，就操作容易的觀點而言，較佳為使用還原劑的方法。Further, the method for reducing the silver compounds in the raw material liquid is not particularly limited, and examples thereof include a method using a reducing agent, a method of irradiating light such as ultraviolet rays, an electron beam, ultrasonic waves or thermal energy, and a heating method. Wait. Among them, from the viewpoint of easy handling, a method of using a reducing agent is preferred.

作為所述還原劑，可列舉：例如二甲基胺基乙醇、甲基二乙醇胺、三乙醇胺、菲尼酮（phenidone）、肼（hydrazine）等胺化合物；例如硼氫化鈉、碘化氫、氫氣等氫化合物；例如一氧化碳、亞硫酸等氧化物；例如硫酸亞鐵、氧化鐵、反丁烯二酸鐵、乳酸鐵、乙二酸鐵、硫化鐵、乙酸錫、氯化錫、二磷酸錫、乙二酸錫、氧化錫、硫酸錫等低原子價金屬鹽；例如乙二醇、甘油、甲醛、對苯二酚、鄰苯三酚、單寧、單寧酸、水楊酸、D-葡萄糖等糖等；只要是可溶解於分散介質中而將所述金屬鹽還原者，則並無特別限定。於使用所述還原劑的情況下，亦可施加光及/或熱而促進還原反應。Examples of the reducing agent include amine compounds such as dimethylaminoethanol, methyldiethanolamine, triethanolamine, phenidone, and hydrazine; for example, sodium borohydride, hydrogen iodide, and hydrogen. An isohydrogen compound; for example, an oxide such as carbon monoxide or sulfurous acid; for example, ferrous sulfate, iron oxide, iron fumarate, iron lactate, iron oxalate, iron sulfide, tin acetate, tin chloride, tin diphosphate, Low valence metal salts such as tin oxalate, tin oxide, tin sulfate; for example, ethylene glycol, glycerin, formaldehyde, hydroquinone, pyrogallol, tannin, tannic acid, salicylic acid, D-glucose The sugar or the like is not particularly limited as long as it is soluble in the dispersion medium and the metal salt is reduced. In the case of using the reducing agent, light and/or heat may also be applied to promote the reduction reaction.

作為使用所述金屬鹽、有機成分、溶媒及還原劑來製備由有機物所被覆的銀奈米粒子的具體方法，例如可列舉如下的方法等：將所述金屬鹽溶解於有機溶媒（例如甲苯等）中而製備金屬鹽溶液，於該金屬鹽溶液中添加作為保護分散劑的胺或具有酸價的保護分散劑，繼而，向其中緩緩地滴加溶解有還原劑的溶液。Specific examples of the method for preparing the silver nanoparticles coated with the organic material using the metal salt, the organic component, the solvent, and the reducing agent include, for example, a method in which the metal salt is dissolved in an organic solvent (for example, toluene or the like). A metal salt solution is prepared, and an amine or a protective dispersant having an acid value as a protective dispersant is added to the metal salt solution, and then a solution in which a reducing agent is dissolved is gradually added dropwise thereto.

以所述方式獲得的包含由胺或具有酸價的保護分散劑所被覆的銀奈米粒子的分散液中，除了銀奈米粒子以外，還存在金屬鹽的抗衡離子、還原劑的殘留物或分散劑，存在液體整體的電解質濃度或有機物濃度高的傾向。此種狀態的液體由於電導度高等原因，容易產生金屬粒子的凝析而沈澱。或者，即便不沈澱，若金屬鹽的抗衡離子、還原劑的殘留物、或者分散所需要的量以上的過剩的分散劑殘留，則存在使導電性惡化的顧慮。因此，藉由對包含所述銀奈米粒子的溶液進行洗滌而去除多餘的殘留物，可確實地獲得由有機物所被覆的銀奈米粒子。In the dispersion obtained by the above-described silver nanoparticle coated with an amine or a protective dispersant having an acid value, in addition to the silver nanoparticle, there is a counter ion of the metal salt, a residue of the reducing agent or The dispersant tends to have a high electrolyte concentration or a high organic concentration of the liquid. The liquid in this state is likely to cause segregation of metal particles and precipitation due to high electrical conductivity. Alternatively, even if it does not precipitate, if the counter ion of the metal salt, the residue of the reducing agent, or the excess amount of the dispersing agent required for the dispersion remains, there is a concern that the conductivity is deteriorated. Therefore, the silver nanoparticle coated with the organic substance can be surely obtained by washing the solution containing the silver nanoparticle to remove excess residue.

作為所述洗滌方法，例如可列舉：將以下步驟重覆若干次的方法：將包含由有機成分所被覆的銀奈米粒子的分散液靜置一定時間，去除所產生的上清液後，添加使銀奈米粒子沈澱的溶媒（例如水、甲醇、甲醇/水混合溶媒等），再次攪拌，將進而靜置一定期間而產生的上清液去除；進行離心分離來代替所述靜置的方法；利用超濾裝置或離子交換裝置等來進行脫鹽的方法等。藉由此種洗滌而去除多餘的殘留物，並且去除有機溶媒，藉此可獲得本實施形態的由「短鏈胺或具有酸價的分散劑」所被覆的金屬粒子。Examples of the washing method include a method of repeating the following steps several times: a dispersion containing silver nanoparticles coated with an organic component is allowed to stand for a predetermined period of time, and the resulting supernatant is removed, and then added. A solvent (for example, water, methanol, methanol/water mixed solvent, etc.) in which silver nanoparticles are precipitated is stirred again, and the supernatant obtained by standing still for a predetermined period of time is removed; and centrifugation is performed instead of the standing method. A method of performing desalination using an ultrafiltration device, an ion exchange device, or the like. By removing such excess residue by such washing and removing the organic solvent, the metal particles coated with "short-chain amine or acid-valent dispersant" of the present embodiment can be obtained.

本實施形態中，銀奈米粒子分散體（銀膠體分散液）是藉由將所述中獲得的由胺或保護分散劑（包含所述萜烯系樹脂的情況）所被覆的銀奈米粒子、與所述本實施形態中所說明的分散介質進行混合而獲得。所述由胺或保護分散劑所被覆的金屬粒子與分散介質的混合方法並無特別限定，可使用攪拌機或攪拌器（stirrer）等，利用現有公知的方法來進行。利用刮勺之類者進行攪拌，或亦可利用適當功率的超音波均質器。In the present embodiment, the silver nanoparticle dispersion (silver colloidal dispersion) is a silver nanoparticle coated with an amine or a protective dispersant (in the case where the terpene-based resin is included) obtained as described above. It is obtained by mixing with the dispersion medium described in the above embodiment. The method of mixing the metal particles coated with the amine or the protective dispersant and the dispersion medium is not particularly limited, and it can be carried out by a conventionally known method using a stirrer, a stirrer or the like. Stirring with a spatula or the like, or using an ultrasonic mixer of appropriate power.

亦可藉由以下步驟來製造銀奈米粒子：第1步驟，調整可藉由還原而分解生成金屬銀的銀化合物與胺的混合液；以及第2步驟，藉由將該混合液中的所述銀化合物進行還原，而生成於表面的至少一部分附著有胺的銀奈米粒子。例如，可藉由對由包含銀的乙二酸銀等銀化合物與胺所生成的錯合化合物進行加熱，將該錯合化合物中所含的乙二酸根離子等金屬化合物分解，使所生成的原子狀的銀凝聚，來製造由胺的保護膜所保護的銀粒子。The silver nanoparticle can also be produced by the following steps: in the first step, adjusting a mixture of a silver compound and an amine which can be decomposed to form metallic silver by reduction; and a second step, by using the mixture in the mixture The silver compound is reduced to form silver nanoparticles in which at least a part of the surface is attached with an amine. For example, a metal compound such as an oxalate ion contained in the conjugated compound can be decomposed by heating a conjugated compound formed of a silver compound such as silver oxalate containing silver and an amine to form a metal compound. The atomic silver is agglomerated to produce silver particles protected by an amine protective film.

如上所述，於藉由將銀化合物的錯合化合物於胺的存在下進行熱分解來製造由胺所被覆的銀奈米粒子的金屬胺錯合物分解法中，由於藉由作為單一種的分子的銀胺錯合物的分解反應而生成原子狀銀，故而可於反應系統內均勻地生成原子狀銀，與藉由多種成分間的反應而生成銀原子的情況相比較，由構成反應的成分的組成搖晃所引起的反應的不均勻得到抑制，特別是於以工業規模來製造大量的銀粉末時有利。As described above, in the metal amine complex decomposition method of producing silver nanoparticle coated with an amine by thermally decomposing a compound of a silver compound in the presence of an amine, since it is a single type The atomic silver is formed by the decomposition reaction of the molecular silveramine complex, so that atomic silver can be uniformly formed in the reaction system, and the reaction is formed by a reaction between a plurality of components to form a silver atom. The unevenness of the reaction caused by the shaking of the composition of the components is suppressed, and it is particularly advantageous when a large amount of silver powder is produced on an industrial scale.

另外推測：於金屬胺錯合物分解法中，於所生成的銀原子上配位鍵結有胺分子，藉由配位於該銀原子上的胺分子的作用，產生凝聚時的銀原子的運動得到控制。其結果為：依據金屬胺錯合物分解法，可製造非常微細且粒度分佈狹窄的金屬粒子。It is also presumed that in the metal amine complex decomposition method, an amine molecule is coordinately bonded to the generated silver atom, and the movement of the silver atom at the time of aggregation is generated by the action of the amine molecule located on the silver atom. Get control. As a result, according to the metal amine complex decomposition method, metal particles having a very fine particle size and a narrow particle size distribution can be produced.

進而，大量的胺於所製造的銀奈米粒子的表面亦產生比較弱的力的配位鍵結，該些於銀奈米粒子的表面形成緻密的保護覆膜，因此可製造保存穩定性優異的表面潔淨的被覆銀奈米粒子。另外，形成該覆膜的胺分子可藉由加熱等而容易脫離，因此可製造能於非常低的溫度下進行燒結的銀奈米粒子。Further, a large amount of amines also form a relatively weak force coordination bond on the surface of the produced silver nanoparticles, and these dense silver oxide coatings form a dense protective film on the surface of the silver nanoparticles, thereby producing excellent storage stability. The surface of the clean coated silver nanoparticles. Further, since the amine molecules forming the coating film can be easily separated by heating or the like, silver nanoparticle which can be sintered at a very low temperature can be produced.

另外，當將固體狀的銀化合物與胺混合而生成錯合化合物等複合化合物時，藉由對於構成被覆銀奈米粒子的覆膜的具有酸價的分散劑，混合胺來使用，而容易生成錯合化合物等複合化合物，並能以短時間的混合來製造複合化合物。另外，藉由混合該胺來使用，可製造具有符合各種用途的特性的被覆銀奈米粒子。In addition, when a solid silver compound is mixed with an amine to form a composite compound such as a complex compound, it is easy to form by mixing an amine with a dispersant having an acid value for a coating film constituting the coated silver nanoparticles. A composite compound such as a compound is mixed, and a composite compound can be produced by mixing for a short period of time. Further, by mixing the amine, it is possible to produce coated silver nanoparticles having characteristics suitable for various uses.

（3）導電層（導電膜）圖案及其製造方法 若使用本實施形態的導電性墨水，則可藉由將所述導電性墨水塗佈於基材上的導電性墨水塗佈步驟、將塗佈於所述基材上的所述導電性墨水於小於140℃（較佳為120℃以下）的溫度下進行煅燒而形成導電膜圖案的導電膜圖案形成步驟，來製造包含基材、以及形成於所述基材的表面的至少一部分上的導電膜圖案的帶有導電膜圖案的基板。(3) Conductive layer (conductive film) pattern and method for producing the same using the conductive ink of the present embodiment, the conductive ink can be applied by applying the conductive ink to the substrate The conductive ink coated on the substrate is calcined at a temperature of less than 140 ° C (preferably 120 ° C or lower) to form a conductive film pattern forming step of the conductive film pattern, to fabricate the substrate, and to form a substrate with a conductive film pattern of a conductive film pattern on at least a portion of the surface of the substrate.

本發明者反覆進行了努力研究，結果發現：若使用所述的本實施形態的導電性墨水作為所述導電性墨水塗佈步驟中的導電性墨水，則於導電膜圖案形成步驟中，即便將塗佈於所述基材上的所述導電性墨水於小於140℃的溫度下進行煅燒，亦確實地獲得具有優異導電性的導電膜圖案。As a result of intensive studies, the inventors have found that the conductive ink of the present embodiment described above is used as the conductive ink in the conductive ink coating step, even in the conductive film pattern forming step. The conductive ink coated on the substrate is calcined at a temperature of less than 140 ° C, and a conductive film pattern having excellent conductivity is also surely obtained.

於將本實施形態的導電性墨水設為轉印印刷用的情況下，於轉印印刷法中的反轉印刷法中，首先於膠板（blanket）上塗佈轉印印刷用導電性墨水而形成導電性墨水塗佈面。作為膠板，較佳為包含矽酮的矽酮膠板。藉由在膠板的表面形成導電性墨水塗佈面後，放置既定時間，低沸點溶劑揮發以及被吸收於膠板中，藉此，導電性墨水的黏度上升。When the conductive ink of the present embodiment is used for transfer printing, in the reverse printing method in the transfer printing method, first, a conductive ink for transfer printing is applied onto a blanket. A conductive ink coated surface is formed. As the rubber sheet, an anthrone board containing an anthrone is preferred. After the conductive ink-coated surface is formed on the surface of the rubber sheet, it is left for a predetermined period of time, and the low-boiling solvent is volatilized and absorbed in the rubber sheet, whereby the viscosity of the conductive ink rises.

若於所述導電性墨水塗佈面上按壓形成有與既定的圖案相符的版的凸版，則與該凸版接觸的部分的導電性墨水自膠板上去除。此時，藉由導電性墨水具有適度的凝聚性，導電性墨水的結構不會破壞，確實地進行自膠板的剝離、以及於凸版上的附著，於膠板上的欠佳的殘留得到抑制。其結果為：藉由殘留於膠板上的導電性墨水，與凸版的圖案相符的導電性墨水的圖案被形成於膠板上。When a relief having a plate conforming to a predetermined pattern is pressed on the conductive ink application surface, the conductive ink in contact with the relief is removed from the adhesive sheet. In this case, since the conductive ink has moderate cohesiveness, the structure of the conductive ink is not broken, and the peeling of the self-adhesive sheet and the adhesion to the relief are reliably performed, and the poor residue on the rubber sheet is suppressed. . As a result, a pattern of the conductive ink conforming to the pattern of the relief is formed on the rubber sheet by the conductive ink remaining on the rubber sheet.

將殘留於膠板上的濕潤狀態或者半乾燥狀態的導電性墨水轉印於被印刷體上。此時，藉由導電性墨水具有適度的凝聚性，而確實地進行自膠板的剝離、以及於被印刷體上的附著，於膠板上的欠佳的殘留得到抑制。其結果為：於被印刷體上，由相對於形成於凸版上的圖案而反轉的圖案來形成導電膜圖案。The conductive ink remaining in the wet state or the semi-dry state is transferred onto the object to be printed. At this time, since the conductive ink has moderate cohesiveness, the peeling of the self-adhesive sheet and the adhesion to the object to be printed are reliably performed, and the poor residue on the rubber sheet is suppressed. As a result, a conductive film pattern is formed on the object to be printed by a pattern reversed with respect to the pattern formed on the relief.

作為本實施形態中可使用的基材，只要是可塗佈導電性墨水，且藉由加熱進行煅燒而搭載導電膜圖案的具有至少一個主面者，則並無特別限制，但較佳為耐熱性優異的基材。另外，如上所述，與現有的導電性墨水相比較，本實施形態的轉印印刷用導電性墨水即便於低的溫度下進行加熱而煅燒，亦可獲得具有充分的導電性的導電膜圖案，因此可在高於所述低煅燒溫度的溫度範圍內使用較先前而言耐熱溫度低的基材。The substrate which can be used in the present embodiment is not particularly limited as long as it has at least one main surface on which a conductive ink can be applied and is baked by heating, and is preferably heat-resistant. Excellent substrate. In addition, as described above, the conductive ink for transfer printing of the present embodiment can be obtained by heating and baking at a low temperature, and a conductive film pattern having sufficient conductivity can be obtained. It is therefore possible to use a substrate having a lower heat-resistant temperature than previously described in a temperature range higher than the low calcination temperature.

作為構成此種基材的材料，例如可列舉：聚醯胺（polyamide，PA）、聚醯亞胺（polyimide，PI）、聚醯胺醯亞胺（polyamide imide，PAI）、聚對苯二甲酸乙二酯（polyethylene terephthalate，PET）、聚對苯二甲酸丁二酯（polybutylene terephthalate，PBT）、聚萘二甲酸乙二酯（polyethylene naphthalate，PEN）等聚酯，聚碳酸酯（polycarbonate，PC）、聚醚碸（polyether sulfone，PES）、乙烯基系樹脂、氟樹脂、液晶聚合物、陶瓷、玻璃或者金屬等。另外，基材可為例如板狀或者帶狀等各種形狀，可為剛性，亦可為柔性。基材的厚度亦可適當選擇。出於黏接性或者密合性的提高或者其他的目的，可使用形成有表面層的基材或實施了親水化處理等表面處理的基材。Examples of the material constituting such a substrate include polyamide (PA), polyimide (PI), polyamide imide (PAI), and poly (terephthalic acid). Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and other polyesters, polycarbonate (PC) Polyether sulfone (PES), vinyl resin, fluororesin, liquid crystal polymer, ceramic, glass or metal. Further, the substrate may have various shapes such as a plate shape or a belt shape, and may be rigid or flexible. The thickness of the substrate can also be appropriately selected. A substrate on which a surface layer is formed or a substrate subjected to surface treatment such as hydrophilization treatment may be used for the purpose of improving adhesion or adhesion or other purposes.

藉由將以所述方式塗佈後的塗膜加熱至小於140℃（較佳為120℃以下）的溫度而進行煅燒，可獲得本實施形態的導電膜圖案（帶有導電膜圖案的基材）。進行煅燒的方法並無特別限定，例如可藉由使用現有公知的齒輪烘箱（gear oven）等，以塗佈或描畫於基材上的所述導電性墨水的溫度成為小於140℃（較佳為120℃以下）的方式進行煅燒而形成導電膜圖案。所述煅燒的溫度的下限未必限定，較佳為可於基材上形成導電膜圖案的溫度，且可於不損及本發明的效果的範圍內使所述有機成分等藉由蒸發或分解而去除的溫度（亦可於不損及本發明的效果的範圍內殘存一部分，但理想為全部去除）。The conductive film pattern (substrate with a conductive film pattern) of the present embodiment can be obtained by heating the coating film coated in the above manner to a temperature of less than 140 ° C (preferably 120 ° C or lower). ). The method of performing the calcination is not particularly limited. For example, the temperature of the conductive ink applied or drawn on the substrate can be less than 140 ° C by using a conventionally known gear oven or the like (preferably The conductive film pattern is formed by calcination in a manner of 120 ° C or lower. The lower limit of the calcination temperature is not necessarily limited, and is preferably a temperature at which a conductive film pattern can be formed on a substrate, and the organic component or the like can be evaporated or decomposed without departing from the effects of the present invention. The temperature to be removed (may also remain in part within the range that does not impair the effects of the present invention, but is preferably all removed).

依據本實施形態的導電性墨水，可形成於120℃左右的低溫加熱處理中以表現出高導電性的導電膜圖案，因此於比較不耐熱的基材上亦可形成導電膜圖案。另外，煅燒時間並無特別限定，可根據煅燒溫度而於基材上形成導電膜圖案。According to the conductive ink of the present embodiment, a conductive film pattern having high conductivity can be formed in a low-temperature heat treatment at about 120 ° C. Therefore, a conductive film pattern can be formed on a substrate which is relatively heat-resistant. Further, the calcination time is not particularly limited, and a conductive film pattern can be formed on the substrate in accordance with the calcination temperature.

本實施形態中，雖然基本上不需要，但為了進一步提高所述基材與導電膜圖案的密合性，亦可進行所述基材的表面處理。作為所述表面處理方法，例如可列舉：進行電暈處理（corona treatment）、電漿處理、紫外線（ultraviolet，UV）處理、電子束處理等乾式處理的方法；於基材上預先設置底塗層或導電性墨水受容層的方法等。In the present embodiment, although it is basically unnecessary, in order to further improve the adhesion between the substrate and the conductive film pattern, the surface treatment of the substrate may be performed. Examples of the surface treatment method include a method of performing dry treatment such as corona treatment, plasma treatment, ultraviolet (UV) treatment, and electron beam treatment; and a primer layer is previously provided on the substrate. Or a method in which a conductive ink receives a layer or the like.

以所述方式可獲得本實施形態的導電膜圖案（帶有導電膜圖案的基材）。以所述方式所獲得的本實施形態的導電膜圖案例如為0.1 μm～5 μm左右，更佳為0.1 μm～1 μm。若使用本實施形態的導電性墨水，則獲得即便厚度為0.1 μm～5 μm左右，亦具有充分的導電性的導電膜圖案。此外，本實施形態的導電膜圖案的體積電阻值為15 μΩ·cm以下。The conductive film pattern (substrate with a conductive film pattern) of the present embodiment can be obtained in the above manner. The conductive film pattern of the present embodiment obtained as described above is, for example, about 0.1 μm to 5 μm, more preferably 0.1 μm to 1 μm. When the conductive ink of the present embodiment is used, a conductive film pattern having sufficient conductivity even when the thickness is about 0.1 μm to 5 μm is obtained. Further, the conductive film pattern of the present embodiment has a volume resistance value of 15 μΩ·cm or less.

此外，本實施形態的導電膜圖案的厚度t例如可使用下述式來求出（導電膜圖案的厚度t亦可利用雷射顯微鏡（例如基恩斯（Keyence）製造的雷射顯微鏡VK-9510）來測定）。 式：t=m/（d×M×w） m：導電膜圖案重量（利用電子天平來測定形成於載玻片上的導電膜圖案的重量） d：導電膜圖案密度（g/cm³ ）（銀的情況下為10.5 g/cm³ ） M：導電膜圖案長度（cm）（以相當於JIS1級的尺度來測定形成於載玻片上的導電膜圖案的長度） w：導電膜圖案寬度（cm）（以相當於JIS1級的尺度來測定形成於載玻片上的導電膜圖案的寬度） [實施例]Further, the thickness t of the conductive film pattern of the present embodiment can be obtained, for example, by the following formula (the thickness t of the conductive film pattern can also be obtained by a laser microscope (for example, a laser microscope VK-9510 manufactured by Keyence). Determination). Formula: t=m/(d×M×w) m: conductive film pattern weight (measurement of the weight of the conductive film pattern formed on the glass slide using an electronic balance) d: conductive film pattern density (g/cm ³ ) ( In the case of silver, it is 10.5 g/cm ³ ) M: conductive film pattern length (cm) (the length of the conductive film pattern formed on the glass slide is measured on a scale equivalent to JIS 1 level) w: conductive film pattern width (cm (measuring the width of the conductive film pattern formed on the glass slide at a scale equivalent to JIS 1 level) [Example]

以下，列舉實施例及比較例，對本發明的導電性墨水以及使用該導電性墨水的導電膜圖案（帶有導電膜圖案的基材）的製造方法進一步進行說明，但本發明不受該些實施例的任何限定。Hereinafter, the conductive ink of the present invention and a conductive film pattern (substrate having a conductive film pattern) using the conductive ink will be further described by way of examples and comparative examples, but the present invention is not affected by the above-described embodiments. Any definition of the example.

≪實施例1≫ 將1.7 g的丁胺（和光純藥工業（股）製造的試劑一級，碳數：4）、3.5 g的己胺（和光純藥工業（股）製造的試劑一級，碳數：6）、及0.2 g的作為高分子分散劑的SOLSPERSE21000（日本路博潤（股）製造）混合，利用磁力攪拌器充分攪拌，製備胺混合液。繼而，一邊進行攪拌，一邊添加3.0 g的乙二酸銀。添加乙二酸銀後，於室溫下繼續攪拌，藉此使乙二酸銀變化為具有黏性的白色物質，以目視來確認該變化在外觀上結束，且於該時刻結束攪拌（第1步驟）。 將所獲得的混合液轉移至油浴中，於120℃下進行加熱攪拌。攪拌開始後即刻開始伴隨二氧化碳的產生的反應，然後，進行攪拌直至二氧化碳的產生完畢，藉此獲得銀微粒子懸浮於胺混合物中的懸浮液（第2步驟）。 繼而，為了置換該懸浮液的分散介質，添加甲醇與丙酮的混合溶媒10 mL而進行攪拌後，藉由離心分離，使銀微粒子沈降而分離，對於分離的銀微粒子，添加10 mL的丙酮，並進行攪拌、離心分離，藉此使銀微粒子沈降而分離，使其分散於將0.04 g（相對於銀固體成分為2.0重量%）的萜烯樹脂YS樹脂（YS RESIN）PX1150（安原化學（Yasuhara Chemical）（股）製造、軟化溫度115±5℃）添加於1.5 g的二氫乙酸萜品酯（dihydroterpinyl acetate）並加以混合溶解所得者中，從而獲得銀奈米粒子分散體1。≪Example 1≫ 1.7 g of butylamine (a reagent manufactured by Wako Pure Chemical Industries Co., Ltd., carbon number: 4), 3.5 g of hexylamine (a reagent manufactured by Wako Pure Chemical Industries, Ltd.), carbon number :6), and 0.2 g of SOLSIPERSE 21000 (manufactured by Lubrizol, Japan) as a polymer dispersant, and thoroughly stirred by a magnetic stirrer to prepare an amine mixed solution. Then, 3.0 g of silver oxalate was added while stirring. After adding silver oxalate, stirring was continued at room temperature, whereby silver oxalate was changed to a viscous white substance, and it was visually confirmed that the change ended in appearance, and stirring was completed at the time (first step). The obtained mixed liquid was transferred to an oil bath, and heated and stirred at 120 °C. The reaction accompanying the generation of carbon dioxide is started immediately after the start of the stirring, and then stirring is performed until the generation of carbon dioxide is completed, whereby a suspension in which the silver fine particles are suspended in the amine mixture is obtained (second step). Then, in order to replace the dispersion medium of the suspension, 10 mL of a mixed solvent of methanol and acetone was added and stirred, and then the silver fine particles were sedimented and separated by centrifugation, and 10 mL of acetone was added to the separated silver fine particles. The stirring and centrifugation were carried out, whereby the silver fine particles were sedimented and separated, and dispersed in a terpene resin YS resin (YS RESIN) PX1150 (Yasuhara Chemical) containing 0.04 g (2.0% by weight relative to the silver solid content). (manufacturing, softening temperature: 115 ± 5 ° C) was added to 1.5 g of dihydroterpinyl acetate and mixed and dissolved to obtain silver nanoparticle dispersion 1.

[評價試驗] 對於所獲得的銀奈米粒子分散體1，進行分散性、稀釋性（剛結束後、經時穩定性）、體積電阻值、密合性試驗（拉脫法（pull-off method））的評價。此外，導電性覆膜的煅燒條件均設為120℃×30分鐘。[Evaluation Test] The obtained silver nanoparticle particle dispersion 1 was subjected to dispersibility, dilution (just after completion, stability over time), volume resistance value, and adhesion test (pull-off method). ))evaluation of. Further, the calcination conditions of the electroconductive film were all set to 120 ° C × 30 minutes.

（1）分散性 將銀奈米粒子分散體1靜置於容器中，室溫1天後，以目視來觀察沈澱的有無及上清液的狀態，藉此評價分散性。將於容器下基本上未辨認出沈降物的情況評價為「○」，將辨認出少量沈降物的情況評價為「△」，將於容器上下明顯存在濃度差且清晰地辨認出沈降物的情況評價為「×」。將結果示於表1中。(1) Dispersibility The silver nanoparticle dispersion 1 was allowed to stand in a container, and after 1 day at room temperature, the presence or absence of precipitation and the state of the supernatant were visually observed to evaluate the dispersibility. The case where the sediment was not recognized substantially under the container was evaluated as "○", and the case where a small amount of sediment was recognized was evaluated as "△", and the difference in concentration between the upper and lower sides of the container was clearly observed and the sediment was clearly recognized. The evaluation is "X". The results are shown in Table 1.

（2）稀釋性 藉由目視來評價將銀奈米粒子分散體1在分散介質中稀釋100倍時的分散性。將分散了的情況評價為「○」，將一部分凝聚或可見到銀鏡的情況評價為「△」，將產生凝聚、沈澱的情況評價為「×」。(2) Dilution The dispersibility when the silver nanoparticle dispersion 1 was diluted 100-fold in a dispersion medium was evaluated by visual observation. The case where the dispersion was evaluated was evaluated as "○", and the case where a part of the particles were aggregated or visible was observed as "△", and the case where aggregation or precipitation occurred was evaluated as "x".

（3）體積電阻值 將銀奈米粒子分散體1刷毛塗佈於載玻片而形成塗膜，在齒輪烘箱中，以120℃×30分鐘的條件進行加熱、煅燒，藉此使其燒結，而形成導電性覆膜。使用橫川計＆儀器（INSTRUMENTS）（股）製造的直流精密測定器「便攜式雙電橋2769」測定所述覆膜的體積電阻值。具體而言，根據以下式子，由測定端子間距離與導電性覆膜的厚度來換算體積電阻值。將體積電阻值為20 μΩ·cm以下的情況評價為「○」，將30 μΩ·cm以下的情況評價為「△」，將所述以上的值的情況評價為「×」。將結果示於表1中。 式：（體積電阻值ρv）= （電阻值R）×（覆膜寬度w）×（覆膜厚度t）/（端子間距離L）(3) Volume resistance value The silver nanoparticle dispersion 1 was applied to a glass slide to form a coating film, and heated and calcined in a gear oven at 120 ° C for 30 minutes to be sintered. A conductive film is formed. The volume resistivity of the film was measured using a DC precision measuring device "Portable Double Bridge 2769" manufactured by Yokogawa & Instruments (INSTRUMENTS). Specifically, the volume resistance value is converted from the distance between the measurement terminals and the thickness of the conductive film according to the following formula. The case where the volume resistance value was 20 μΩ·cm or less was evaluated as “○”, the case where 30 μΩ·cm or less was evaluated as “Δ”, and the case where the above value was evaluated as “×”. The results are shown in Table 1. Formula: (volume resistance value ρv) = (resistance value R) × (film width w) × (film thickness t) / (inter-terminal distance L)

（4）密合性試驗 藉由旋轉塗佈（2000 rpm/20秒）將銀奈米粒子分散體1於2.5 cm見方的載玻片上形成塗膜，在齒輪烘箱中，以120℃×30分鐘的條件進行加熱、煅燒，藉此使其燒結，而形成導電性覆膜。作為附著性試驗，藉由拉脫法而將賽珞膠帶（Cellotape）貼附於玻璃基板上的薄膜，以撕剝結果的斷裂狀況進行評價。使用5片載玻片來製作5片帶有覆膜的樣品，對5片分別使賽珞膠帶用力蹭觸皮膜並於垂直方向上用力撕剝而進行評價。將剝離片數為0片～1片的情況評價為「○」，將2片～3片的情況評價為「△」，將4片～5片的情況評價為「×」，即便未完全剝離而部分剝離亦視為剝離並計數為1片。將結果示於表1中。(4) Adhesion test The silver nanoparticle dispersion 1 was formed into a coating film on a 2.5 cm square slide by spin coating (2000 rpm/20 seconds) in a gear oven at 120 ° C for 30 minutes. The conditions are heated, calcined, and thereby sintered to form a conductive film. As a adhesion test, a film in which a cellophane tape (Cellotape) was attached to a glass substrate by a pull-off method was evaluated by the fracture state of the peeling result. Five slides were used to make five samples with a film, and five pieces of the celluloid tape were forcefully rubbed against the film and peeled off in the vertical direction. The case where the number of peeling sheets was 0 pieces to 1 piece was evaluated as "○", the case of 2 pieces to 3 pieces was evaluated as "Δ", and the case of 4 pieces to 5 pieces was evaluated as "×", even if it was not completely peeled off. Partial peeling was also considered to be stripped and counted as 1 tablet. The results are shown in Table 1.

（5）銀奈米粒子分散液中的樹脂量測定（樹脂成分測定） 利用熱重量分析法來測定銀奈米粒子分散體1中所含的有機成分的含量。具體而言，以10℃/分鐘的升溫速度對銀奈米粒子分散體的固體成分進行加熱，作為200℃～500℃的重量減少量，減去高分子分散劑的重量損失成分來確定樹脂成分的含量。將結果示於表1中。(5) Measurement of Resin Amount in Silver Nanoparticle Dispersion (Measurement of Resin Component) The content of the organic component contained in the silver nanoparticle dispersion 1 was measured by a thermogravimetric analysis method. Specifically, the solid component of the silver nanoparticle dispersion is heated at a temperature increase rate of 10 ° C /min, and the weight loss component of the polymer dispersant is subtracted from the weight loss amount of 200 ° C to 500 ° C to determine the resin component. The content. The results are shown in Table 1.

《實施例2》 使用0.04 g（相對於銀固體成分為2.0重量%）的萜烯苯酚樹脂YS保里斯達（YS Polystar）T160（安原化學（股）製造、軟化溫度160±5℃）來代替YS RESIN PX1150，除此以外，以與實施例1相同的方式製備銀奈米粒子分散液2並進行評價試驗。將結果示於表1中。<<Example 2>> Using 0.04 g (2.0% by weight of silver solid content) of terpene phenol resin YS Polystar T160 (manufactured by Anwar Chemical Co., Ltd., softening temperature 160 ± 5 ° C) was used instead. Silver nanoparticle dispersion liquid 2 was prepared in the same manner as in Example 1 except for YS RESIN PX1150, and an evaluation test was conducted. The results are shown in Table 1.

《實施例3》 使用0.04 g（相對於銀固體成分為2.0重量%）的改質萜烯樹脂YS RESIN TO115（安原化學（股）製造、軟化溫度115±5℃）來代替YS RESIN PX1150，除此以外，以與實施例1相同的方式製備銀奈米粒子分散液3並進行評價試驗。將結果示於表1中。<<Example 3>> A modified terpene resin YS RESIN TO115 (manufactured by Anwar Chemical Co., Ltd., softening temperature 115 ± 5 ° C) was used in place of YS RESIN PX1150, except 0.04 g (2.0% by weight based on the solid content of silver). Otherwise, the silver nanoparticle dispersion 3 was prepared in the same manner as in Example 1 and subjected to an evaluation test. The results are shown in Table 1.

《實施例4》 使用0.04 g（相對於銀固體成分為2.0重量%）的萜烯樹脂YS RESIN PX1000（安原化學（股）製造、軟化溫度100±5℃）來代替YS RESIN PX1150，除此以外，以與實施例1相同的方式製備銀奈米粒子分散液4並進行評價試驗。將結果示於表1中。<<Example 4>> In place of YS RESIN PX1150, 0.04 g (2.0% by weight of silver solid content) terpene resin YS RESIN PX1000 (manufactured by Anwara Chemical Co., Ltd., softening temperature: 100 ± 5 ° C) was used instead. Silver nanoparticle dispersion 4 was prepared in the same manner as in Example 1 and subjected to an evaluation test. The results are shown in Table 1.

《實施例5》 使用0.04 g（相對於銀固體成分為2.0重量%）的萜烯系淡色松香酯KE-311（荒川化學工業（股）製造、軟化溫度95±5℃）來代替YS RESIN PX1150，除此以外，以與實施例1相同的方式製備銀奈米粒子分散液5並進行評價試驗。將結果示於表1中。<<Example 5>> In place of YS RESIN PX1150, 0.04 g (2.0% by weight of silver solid content) terpene-based pale rosin ester KE-311 (manufactured by Arakawa Chemical Industries Co., Ltd., softening temperature: 95 ± 5 ° C) was used instead of YS RESIN PX1150. Except for this, a silver nanoparticle dispersion liquid 5 was prepared in the same manner as in Example 1 and subjected to an evaluation test. The results are shown in Table 1.

《實施例6》 使用0.04 g（相對於銀固體成分為2.0重量%）的萜烯系松香樹脂KE-604（荒川化學工業（股）製造、軟化溫度129±5℃）來代替KE-311，除此以外，以與實施例5相同的方式製備銀奈米粒子分散液6並進行評價試驗。將結果示於表1中。<<Example 6>> Using keene-based rosin resin KE-604 (manufactured by Arakawa Chemical Industry Co., Ltd., softening temperature: 129±5 ° C) was used in place of KE-311, using 0.04 g (2.0% by weight of the silver solid content). Except for this, a silver nanoparticle dispersion liquid 6 was prepared in the same manner as in Example 5 and subjected to an evaluation test. The results are shown in Table 1.

《實施例7》 添加1.7 g的丁胺（和光純藥工業（股）製造的試劑一級，碳數：4）、3.5 g的己胺（和光純藥工業（股）製造的試劑一級，碳數：6）、0.2 g的作為高分子分散劑的SOLSPERSE21000（日本路博潤（股）製造）、及0.08 g（相對於銀固體成分為4.0重量%）的萜烯樹脂YS RESIN PX1150（安原化學（股）製造、軟化溫度115±5℃）加以混合，利用磁力攪拌器充分攪拌，生成胺混合液。繼而，一邊進行攪拌，一邊添加3.0 g的乙二酸銀。添加乙二酸銀後，於室溫下繼續攪拌，藉此使乙二酸銀變化為具有黏性的白色物質，以目視來確認該變化在外觀上結束，且於該時刻結束攪拌（第1步驟）。 將所獲得的混合液轉移至油浴中，於120℃下進行加熱攪拌。攪拌開始後即刻開始伴隨二氧化碳的產生的反應，然後，進行攪拌直至二氧化碳的產生完畢，藉此獲得銀奈米粒子懸浮於胺混合物中的懸浮液（第2步驟）。 繼而，為了置換該懸浮液的分散介質，添加甲醇與丙酮的混合溶媒10 mL而進行攪拌後，藉由離心分離，使銀奈米粒子沈降而分離，對於分離的銀奈米粒子，添加10 mL的丙酮，並進行攪拌、離心分離，藉此使銀奈米粒子沈降而分離，使其分散於1.5 g的二氫乙酸萜品酯中，從而獲得銀奈米粒子分散液7。以與實施例1相同的方式進行評價試驗，將結果示於表1中。Example 7: 1.7 g of butylamine (a reagent manufactured by Wako Pure Chemical Industries, Ltd., carbon number: 4), 3.5 g of hexylamine (a reagent manufactured by Wako Pure Chemical Industries, Ltd.), carbon number : 6), 0.2 g of SOLSPERSE 21000 (manufactured by Lubrizol, Japan), and 0.08 g (4.0% by weight of silver solids) of terpene resin YS RESIN PX1150 (Ansei Chemicals Co., Ltd.) The product was produced and softened at a temperature of 115 ± 5 ° C. The mixture was stirred and thoroughly stirred by a magnetic stirrer to form an amine mixture. Then, 3.0 g of silver oxalate was added while stirring. After adding silver oxalate, stirring was continued at room temperature, whereby silver oxalate was changed to a viscous white substance, and it was visually confirmed that the change ended in appearance, and stirring was completed at the time (first step). The obtained mixed liquid was transferred to an oil bath, and heated and stirred at 120 °C. Immediately after the start of the stirring, the reaction accompanying the generation of carbon dioxide is started, and then the stirring is performed until the generation of carbon dioxide is completed, whereby a suspension in which the silver nanoparticles are suspended in the amine mixture is obtained (second step). Then, in order to replace the dispersion medium of the suspension, 10 mL of a mixed solvent of methanol and acetone was added and stirred, and then the silver nanoparticles were sedimented and separated by centrifugation, and 10 mL of the separated silver nanoparticles were added. The acetone was stirred and centrifuged, whereby the silver nanoparticles were sedimented and separated, and dispersed in 1.5 g of terpene dihydroacetate to obtain a silver nanoparticle dispersion 7. Evaluation tests were carried out in the same manner as in Example 1, and the results are shown in Table 1.

《實施例8》 於調配時不使用SOLSPERSE21000，除此以外，以與實施例7相同的方式製備銀奈米粒子分散液8並進行評價試驗。將結果示於表1中。[Example 8] A silver nanoparticle dispersion liquid 8 was prepared in the same manner as in Example 7 except that SOLSPERSE 21000 was not used in the preparation, and an evaluation test was carried out. The results are shown in Table 1.

《實施例9》 於調配時使用0.20 g（相對於銀固體成分為10.0重量%）的萜烯樹脂YS RESIN PX1150，除此以外，以與實施例7相同的方式製備銀奈米粒子分散液9並進行評價試驗。將結果示於表1中。<<Example 9>> A silver nanoparticle dispersion liquid 9 was prepared in the same manner as in Example 7 except that 0.20 g (10.0% by weight of the solid content of silver) of the terpene resin YS RESIN PX1150 was used for the preparation. And conduct evaluation tests. The results are shown in Table 1.

《實施例10》 使用0.02 g（相對於銀固體成分為1.0重量%）的YS RESIN PX1150，除此以外，以與實施例7相同的方式製備銀奈米粒子分散液10並進行評價試驗。將結果示於表1中。[Example 10] A silver nanoparticle dispersion 10 was prepared in the same manner as in Example 7 except that 0.02 g (1.0% by weight of the silver solid component) of YS RESIN PX1150 was used, and an evaluation test was carried out. The results are shown in Table 1.

[表1] [Table 1]

《比較例1》 於調配時不添加作為高分子分散劑的SOLSPERSE21000與萜烯樹脂YS RESIN PX1150，除此以外，以與實施例7相同的方式進行合成，但無法獲得銀奈米粒子分散液。Comparative Example 1 A synthesis was carried out in the same manner as in Example 7 except that SOLSPERSE 21000 as a polymer dispersant and decene resin YS RESIN PX1150 were not added at the time of preparation, but a silver nanoparticle dispersion liquid could not be obtained.

《比較例2》 於調配時不添加萜烯樹脂YS RESIN PX1150，除此以外，以與實施例8相同的方式製備銀奈米粒子分散液11並進行評價試驗。將結果示於表2中。Comparative Example 2 A silver nanoparticle dispersion 11 was prepared in the same manner as in Example 8 except that the terpene resin YS RESIN PX1150 was not added at the time of preparation, and an evaluation test was carried out. The results are shown in Table 2.

《比較例3》 將添加至1.5 g的二氫乙酸萜品酯中的樹脂變更為以固體成分換算計為0.04 g（相對於銀固體成分為2.0重量%）的作為聚酯樹脂溶液的阿拉奇得（ARAKYD）7046（荒川化學（股）製造），除此以外，以與實施例1相同的方式製備銀奈米粒子分散液12並進行評價試驗。將結果示於表2中。Comparative Example 3 The resin added to 1.5 g of the terpene dihydroacetate was changed to 0.04 g (2.0% by weight based on the solid content of the silver) of the resin as a polyester resin solution. Silver nanoparticle dispersion liquid 12 was prepared in the same manner as in Example 1 except that (ARAKYD) 7046 (manufactured by Arakawa Chemical Co., Ltd.), and an evaluation test was carried out. The results are shown in Table 2.

《比較例4》 將添加至1.5 g的二氫乙酸萜品酯中的樹脂變更為以固體成分換算計為0.04 g（相對於銀固體成分為2.0重量%）的作為胺基甲酸酯改質丙烯酸聚合物溶液的阿庫利特（ACRIT）8UA-140（大成精細化學（股）製造），除此以外，以與實施例1相同的方式製備銀奈米粒子分散液13並進行評價試驗。將結果示於表2中。Comparative Example 4 The resin added to 1.5 g of the terpene dihydroacetate was changed to 0.04 g (2.0% by weight based on the solid content of the silver) in terms of solid content, and the urethane was modified. A silver nanoparticle dispersion liquid 13 was prepared and evaluated in the same manner as in Example 1 except that the acrylic polymer solution was obtained by using Akulite (ACRIT) 8UA-140 (manufactured by Daisei Fine Chemical Co., Ltd.). The results are shown in Table 2.

《比較例5》 將添加至1.5 g的二氫乙酸萜品酯中的樹脂變更為以固體成分換算計為0.04 g（相對於銀固體成分為2.0重量%）的萜烯樹脂YS RESIN PX800（安原化學（股）製造、軟化溫度80±5℃），除此以外，以與實施例1相同的方式製備銀奈米粒子分散液14並進行評價試驗。將結果示於表2中。Comparative Example 5 The resin to be added to 1.5 g of the terpene dihydroacetate was changed to 0.04 g (2.0% by weight based on the solid content of the silver) of the terpene resin YS RESIN PX800 (Anyuan) A silver nanoparticle dispersion 14 was prepared in the same manner as in Example 1 except that the chemical (manufacturing) and the softening temperature were 80 ± 5 ° C), and an evaluation test was carried out. The results are shown in Table 2.

《比較例6》 將添加至1.5 g的二氫乙酸萜品酯中的樹脂變更為以固體成分換算計為0.04 g（相對於銀固體成分為2.0重量%）的萜烯樹脂YS RESIN PX300N（安原化學（股）製造、軟化溫度30±5℃），除此以外，以與實施例1相同的方式製備銀奈米粒子分散液15並進行評價試驗。將結果示於表2中。Comparative Example 6 The resin to be added to 1.5 g of the terpene dihydroacetate was changed to 0.04 g (2.0% by weight based on the solid content of the silver) of the terpene resin YS RESIN PX300N (Anyuan) Silver nanoparticle dispersion liquid 15 was prepared in the same manner as in Example 1 except that the chemical (manufacturing) and the softening temperature were 30 ± 5 ° C), and an evaluation test was carried out. The results are shown in Table 2.

[表2] [Table 2]

根據實施例1～實施例6可知：若為萜烯系樹脂，則可廣泛地應用蒎烯聚合物、萜烯苯酚樹脂、松香、松香酯等。另外，根據實施例8可知：較佳為與高分子分散劑併用，但若於合成時預先添加萜烯系樹脂，則可合成奈米粒子。此外，比較例1中，並無高分子分散劑及萜烯系樹脂此兩者，故而無法合成奈米粒子。 另外，根據實施例9可知：若萜烯樹脂相對於銀固體成分的調配量為10質量%以下，則能夠導通。According to Examples 1 to 6, it is understood that a terpene polymer, a terpene phenol resin, a rosin, a rosin ester or the like can be widely used as the terpene resin. Further, according to Example 8, it is preferable to use the polymer dispersant in combination. However, if a terpene-based resin is added in advance at the time of synthesis, the nanoparticles can be synthesized. Further, in Comparative Example 1, since neither the polymer dispersant nor the terpene resin was present, the nanoparticles were not synthesized. Further, according to Example 9, it is understood that the content of the terpene resin with respect to the silver solid content is 10% by mass or less.

進而，根據實施例7～實施例9可知：即便不是後添加於分散介質中，而是於奈米粒子形成時將萜烯系樹脂用作保護分散劑（附著於銀奈米粒子表面），亦可獲得效果。Further, according to Examples 7 to 9, it is understood that the terpene-based resin is used as a protective dispersant (attached to the surface of the silver nanoparticles) even when it is not added to the dispersion medium, but also when the nanoparticles are formed. Get results.

另外，根據比較例2可知：於不使用萜烯系樹脂的情況下無法密合於玻璃基材，進而，根據比較例3及比較例4可知：即便加入聚酯樹脂或丙烯酸樹脂等萜烯系樹脂以外的樹脂，亦無法兼具密合性與導電性。根據比較例5及比較例6亦可知：若萜烯系樹脂的軟化溫度低於90℃，則無法顯現密合性。Further, according to Comparative Example 2, it was found that the terpene-based resin could not be adhered to the glass substrate, and further, according to Comparative Example 3 and Comparative Example 4, it was found that a terpene system such as a polyester resin or an acrylic resin was added. Resins other than resins do not have both adhesion and electrical conductivity. According to Comparative Example 5 and Comparative Example 6, it is also known that when the softening temperature of the terpene-based resin is less than 90 ° C, the adhesion cannot be exhibited.

無no

無no

Claims (4)

一種導電性墨水，其特徵在於包含： 銀奈米粒子； 分散介質；以及 附著於所述銀奈米粒子的表面或所述分散介質中所含的軟化溫度為90℃以上的萜烯系樹脂。A conductive ink comprising: silver nanoparticles; a dispersion medium; and a terpene-based resin adhered to the surface of the silver nanoparticles or a softening temperature of 90 ° C or higher contained in the dispersion medium. 如申請專利範圍第1項所述的導電性墨水，其中 所述萜烯系樹脂為選自由α-蒎烯聚合物、β-蒎烯聚合物、α-蒎烯/β-蒎烯共聚物、檸檬烯聚合物、松香、松香酯、改質松香、萜烯苯酚聚合物、氫化萜烯聚合物、芳香族改質萜烯聚合物及松香改質苯酚樹脂所組成的群組中的至少一種。The conductive ink according to claim 1, wherein the terpene-based resin is selected from the group consisting of an α-pinene polymer, a β-pinene polymer, an α-pinene/β-pinene copolymer, At least one of the group consisting of limonene polymer, rosin, rosin ester, modified rosin, terpene phenol polymer, hydrogenated terpene polymer, aromatic modified terpene polymer, and rosin modified phenol resin. 如申請專利範圍第1項或第2項所述的導電性墨水，其中 所述分散介質中包含所述萜烯樹脂與高分子分散劑。The conductive ink according to claim 1 or 2, wherein the dispersion medium contains the terpene resin and a polymer dispersant. 如申請專利範圍第1項至第3項中任一項所述的導電性墨水，其中 相對於銀固體成分，所述導電性墨水中所含的所述萜烯系樹脂為10重量%以下。The conductive ink according to any one of the items 1 to 3, wherein the terpene-based resin contained in the conductive ink is 10% by weight or less based on the silver solid content.