TWI734797B - Conductive paste and forming method of conductive pattern - Google Patents

Conductive paste and forming method of conductive pattern Download PDF

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TWI734797B
TWI734797B TW106120276A TW106120276A TWI734797B TW I734797 B TWI734797 B TW I734797B TW 106120276 A TW106120276 A TW 106120276A TW 106120276 A TW106120276 A TW 106120276A TW I734797 B TWI734797 B TW I734797B
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conductive paste
silver
organic solvent
conductive
conductive pattern
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TW106120276A
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TW201809158A (en
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新谷祐樹
外村卓也
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日商阪東化學股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns

Abstract

Provided are a conductive paste and a forming method of a conductive pattern for forming a fine conductive pattern having sufficient electrical conductivity and good adhesion to a substrate. More specifically, provided are a conductive paste and a forming method of a conductive pattern in which a conductive pattern having a line width of 5 μm or less is formed by using gravure offset printing. The conductive paste includes a silver microparticle and an organic solvent. The organic solvent includes an organic solvent with low swelling property that has a blanket swelling rate of 2.0% or less, wherein the content percentage of the organic solvent with low swelling property is 3.0 wt%～30 wt%.

Description

導電性糊及導電性圖案的形成方法Method for forming conductive paste and conductive pattern

本發明是有關於一種導電性糊及使用所述導電性糊的導電性圖案的形成方法，所述導電性糊用於形成半導體積體電路等的配線或電極圖案，且有助於導電性圖案的細線化。 The present invention relates to a conductive paste and a method for forming a conductive pattern using the conductive paste. The conductive paste is used to form wiring or electrode patterns of semiconductor integrated circuits and the like, and contributes to the conductive pattern Thinning.

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 show good printing results, recently, research and development of silver nanoparticle technology for printed electronics applications are actively being conducted.

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，正在積極研究開發適合於該些印刷法的導電性墨水或導電性糊等。 In addition, in recent years, in the printed electronics, as a simpler and cheaper method for forming conductive film patterns, methods using printing methods such as relief printing, gravure printing, screen printing, or inkjet printing have been proposed. Active research and development of conductive inks and conductive pastes suitable for these printing methods are underway.

此處，凹版平板印刷中，為了提高使用導電性糊時的印刷適應性，必須提高膠板(blanket)表面中的導電性糊的凝聚力或黏度並將使所述膠板膨潤的溶劑用作溶媒。 Here, in gravure lithography, in order to improve the printability when using a conductive paste, it is necessary to increase the cohesive force or viscosity of the conductive paste on the surface of the blanket and use the solvent that swells the blanket as a solvent. .

然而，膨潤性高的溶媒容易賦予印刷適應性，但另一方面尤其難以用於5μm以下的細線印刷。具體而言，作為極細線圖案而印刷的導電性糊中所含的溶媒量極少，因而於使用對於膠板 的膨潤率高的溶媒的情況下，迅速乾燥而產生對基材的轉印不良。 However, a solvent with a high swelling property is easy to impart printability, but on the other hand, it is particularly difficult to use for fine line printing of 5 μm or less. Specifically, the amount of solvent contained in the conductive paste printed as an ultra-fine line pattern is very small, so it is used for rubber sheets. In the case of a solvent with a high swelling rate, it dries quickly, resulting in poor transfer to the substrate.

相對於此，亦探討了著眼於溶媒的膠板膨潤率的導電性糊，例如專利文獻1(日本專利5610112號)中揭示了一種導電性糊，其為利用凹版平板印刷法的邊框圖案印刷用導電性糊，且含有導電性金屬粒子(A)、50℃下為固體且常壓下的沸點超過300℃的有機化合物(B)、50℃下為液體且常壓下的沸點超過300℃的有機化合物(C)、以及(B)與(C)以外的不具有(B)與(C)的反應性的常壓下的沸點為170℃~300℃的有機溶劑(D)，並且所述導電性糊的特徵在於：相對於(A)~(D)的合計，將(B)不揮發成分以質量換算計設為1.0%~3.0%，且以不揮發成分的質量換算計將有機化合物(B)與有機化合物(C)的合計使用量設為R，將導電性金屬粒子(A)的使用量設為P，將此時兩者的質量比R/P設為0.07~0.15。另外，揭示了所述導電性糊中，有機溶劑的較佳的膠板膨潤率為5%~20%。 In contrast to this, conductive pastes focusing on the swelling rate of the rubber sheet of the solvent have also been studied. For example, Patent Document 1 (Japanese Patent No. 5610112) discloses a conductive paste for frame pattern printing by gravure lithography. Conductive paste containing conductive metal particles (A), an organic compound (B) that is solid at 50°C and has a boiling point over 300°C under normal pressure, and is liquid at 50°C and has a boiling point over 300°C under normal pressure Organic compounds (C) and organic solvents (D) other than (B) and (C) that do not have the reactivity of (B) and (C) and have a boiling point of 170°C to 300°C under normal pressure, and The characteristic of the conductive paste is that the (B) non-volatile content is 1.0% to 3.0% in terms of mass, and the organic compound is calculated in terms of the mass of the non-volatile The total usage amount of (B) and the organic compound (C) is R, the usage amount of the conductive metal particles (A) is P, and the mass ratio R/P of the two at this time is 0.07 to 0.15. In addition, it is disclosed that in the conductive paste, the organic solvent has a preferable rubber sheet swelling rate of 5% to 20%.

設為所述專利文獻1中記載的邊框圖案印刷用導電性糊中，有機化合物(B)的不揮發成分含有率相對於導電性金屬粒子(A)~有機溶劑(D)這四種成分的合計較先前而言小，除此以外，亦將有機化合物(B)與有機化合物(C)的不揮發成分與導電性金屬粒子(A)的質量比R/P調整為較先前而言小，因而即便使用具有如邊框圖案般的複雜的凹部的凹版進行印刷，亦可發揮可獲得直線性優異、無斷線或短路等的所意圖的導電性圖案這一特別顯著的效果。 It is assumed that in the conductive paste for frame pattern printing described in Patent Document 1, the non-volatile content of the organic compound (B) is relative to the four components of the conductive metal particles (A) to the organic solvent (D) The total is smaller than before. In addition, the mass ratio R/P of the non-volatile components of the organic compound (B) and the organic compound (C) to the conductive metal particles (A) is adjusted to be smaller than before. Therefore, even if printing is performed using an intaglio plate having complicated recesses like a frame pattern, it is possible to obtain a particularly remarkable effect of obtaining a desired conductive pattern with excellent linearity and no disconnection or short circuit.

[現有技術文獻] [Prior Art Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利第5610112號說明書 [Patent Document 1] Japanese Patent No. 5610112 Specification

然而，即便使用所述專利文獻1中記載的邊框圖案印刷用導電性糊的情況下，亦無法充分應對近年來的導電性圖案的細線化。再者，所述專利文獻1中亦對溶媒的膠板膨潤率進行了考慮，但較佳的數值範圍的理由並不明確，難以說利用凹版平板印刷而形成的導電性圖案的細線化得到最佳化。 However, even when the conductive paste for frame pattern printing described in Patent Document 1 is used, it cannot sufficiently cope with the recent thinning of conductive patterns. Furthermore, the Patent Document 1 also considers the swelling rate of the rubber sheet of the solvent, but the reason for the preferable value range is not clear. Jiahua.

因此，本發明是鑒於所述現有技術所具有的課題而成者，本發明的目的在於提供一種可形成具有充分的導電性及與基板的良好的密接性的微細導電性圖案的導電性糊及導電性圖案的形成方法。更具體而言，本發明的目的在於提供一種可使用凹版平板印刷而形成線寬為5μm以下的導電性圖案的導電性糊及導電性圖案的形成方法。 Therefore, the present invention was made in view of the problems of the above-mentioned prior art. The object of the present invention is to provide a conductive paste and a conductive paste that can form a fine conductive pattern having sufficient conductivity and good adhesion to a substrate. The formation method of the conductive pattern. More specifically, the object of the present invention is to provide a conductive paste capable of forming a conductive pattern with a line width of 5 μm or less using gravure lithography, and a method for forming a conductive pattern.

本發明者為了達成所述目的而反覆進行研究，結果發現為了實現利用凹版平板印刷而形成的導電性圖案的細線化，將導電性糊中使用的溶媒的膠板膨潤率設定為極小的值，在達成所述目的的方面極其有效，從而實現了本發明。 The inventors of the present invention have made repeated studies in order to achieve the above-mentioned object. As a result, they have found that in order to achieve thinning of the conductive pattern formed by gravure lithography, the swelling rate of the solvent used in the conductive paste is set to an extremely small value. It is extremely effective in achieving the stated object, thereby achieving the present invention.

即，本發明提供一種導電性糊，其特徵在於： 包含銀微粒子及有機溶媒，所述有機溶媒包含膠板膨潤率成為2.0%以下的低膨潤性有機溶媒，所述低膨潤性有機溶媒的含有率為3.0wt%~30wt%。 That is, the present invention provides a conductive paste characterized by: It includes silver particles and an organic solvent, the organic solvent includes a low swelling organic solvent with a rubber sheet swelling rate of 2.0% or less, and the content of the low swelling organic solvent is 3.0 wt% to 30 wt%.

通常用於凹版平板印刷中的印刷版的最表面為矽酮製，所謂本發明中的「膠板膨潤率」，是指使矽酮橡膠浸漬於有機溶媒中時的膨潤率。此處，「膠板膨潤率」與使膠板(矽酮橡膠)浸漬於有機溶媒中時的所述浸漬前後的膠板(矽酮橡膠)的重量變化率為相同含意。 The outermost surface of the printing plate generally used in gravure lithography is made of silicone. The "swelling rate of the rubber sheet" in the present invention refers to the swelling rate when the silicone rubber is immersed in an organic solvent. Here, "the rubber sheet swelling rate" means the same meaning as the weight change rate of the rubber sheet (silicone rubber) before and after the immersion when the rubber sheet (silicone rubber) is immersed in an organic solvent.

再者，更具體而言，將膠板(矽酮橡膠)切出1cm見方並製成試驗片，於室溫條件下(25℃±5℃)使所述試驗片浸漬於有機溶媒中，於10小時後取出而求出浸漬前後的重量增加率，藉此可評價「膠板膨潤率」。實驗證明若為導電性糊印刷用途中標準使用的矽酮膠板，則對於特定的有機溶媒而測定的膨潤率大小差不多。 Furthermore, more specifically, the rubber sheet (silicone rubber) is cut out to a 1 cm square and made into a test piece, and the test piece is immersed in an organic solvent at room temperature (25°C ± 5°C). It was taken out after hours, and the weight increase rate before and after immersion was determined, and the "rubber sheet swelling rate" can be evaluated by this. Experiments have proved that if it is a standard silicone rubber sheet used in conductive paste printing, the swelling rate measured for a specific organic solvent is similar.

本發明的導電性糊中，藉由使用膠板膨潤率為2.0%以下的極低的低膨潤性有機溶媒，可減少膠板對有機溶媒的吸收，可大幅度抑制膠板表面的導電性糊的乾燥。於使用導電性糊印刷極細線的情況下，被印刷成極細線狀的導電性糊非常容易乾燥，難以形成良好的導電性圖案。相對於此，藉由將有機溶媒的膠板膨潤率設為2.0%以下，例如亦可應對線寬為5μm以下的極細線導電性圖案的形成。再者，更佳的膠板膨潤率為0.4%以下。 In the conductive paste of the present invention, by using a very low low-swelling organic solvent with a rubber sheet swelling rate of 2.0% or less, the absorption of the organic solvent by the rubber sheet can be reduced, and the conductive paste on the surface of the rubber sheet can be greatly suppressed The dryness. In the case of printing ultra-fine lines using a conductive paste, the conductive paste printed in the shape of the ultra-fine lines is very easy to dry, and it is difficult to form a good conductive pattern. In contrast, by setting the swelling rate of the rubber sheet of the organic solvent to 2.0% or less, for example, it is also possible to cope with the formation of an ultra-fine wire conductive pattern with a line width of 5 μm or less. Furthermore, the better rubber sheet swelling rate is 0.4% or less.

另外，本發明的導電性糊中，將低膨潤性有機溶媒的含有率設為3.0wt%~30wt%。藉由將低膨潤性有機溶媒的含有率設為3.0wt%以上，可對導電性糊賦予適當的塗佈性(流動性)，藉由設為30wt%以下，可對煅燒後的導電性糊賦予良好的導電性。再者，低膨潤性有機溶媒的更佳的含有率為3.0wt%~25.0wt%，最佳的含有率為3.0wt%~20.0wt%。 In addition, in the conductive paste of the present invention, the content of the low swelling organic solvent is set to 3.0 wt% to 30 wt%. By setting the content of the low swelling organic solvent to 3.0wt% or more, the conductive paste can be imparted with appropriate coating properties (fluidity), and by setting it to 30wt% or less, the calcined conductive paste can be improved Gives good conductivity. Furthermore, the better content rate of the low swelling organic solvent is 3.0wt%-25.0wt%, and the best content rate is 3.0wt%-20.0wt%.

另外，本發明的導電性糊中，較佳為所述銀微粒子為銀奈米粒子。於使用粗大的銀粒子的情況下，銀粒子彼此的燒結變得困難，無法對導電性圖案賦予良好的導電性。相對於此，藉由使用銀奈米粒子，可藉由銀粒子彼此的燒結或接觸而確保導電性。 In addition, in the conductive paste of the present invention, it is preferable that the silver fine particles are silver nanoparticles. When coarse silver particles are used, it becomes difficult to sinter the silver particles, and it is impossible to impart good conductivity to the conductive pattern. In contrast, by using silver nanoparticles, conductivity can be ensured by sintering or contacting the silver particles with each other.

此處，於欲形成極細的導電性圖案的情況下，例如於在凹版平板印刷中使用的印刷版的表面所形成的2μm寬的凹部填充具有0.5μm±0.3μm的粒徑的銀次微米粒子的情況下，只能於凹部的寬度方向填充一個或兩個左右銀次微米粒子。即，銀次微米粒子各自的影響大，僅一個銀次微米粒子脫離便會帶來明顯損及細線的直線性的結果，除此以外，銀次微米粒子彼此的燒結變得困難。 Here, when an extremely fine conductive pattern is to be formed, for example, a 2μm wide recess formed on the surface of a printing plate used in gravure lithography is filled with silver submicron particles having a particle size of 0.5μm±0.3μm In this case, only one or two silver submicron particles can be filled in the width direction of the recess. That is, the influence of each of the silver submicron particles is large, and the detachment of only one silver submicron particle will result in a significant loss of the linearity of the fine line. In addition, sintering of the silver submicron particles becomes difficult.

另一方面，藉由使用銀奈米粒子，可於所述凹部緻密地填充大量的銀奈米粒子，銀奈米粒子彼此密集地相互重疊排列，因此容易使銀奈米粒子彼此燒結(頸縮(necking))。除此以外，由於粒徑極小，因而可大幅度減少一個銀奈米粒子對印刷品質帶來的影響。 On the other hand, by using silver nano-particles, a large number of silver nano-particles can be densely filled in the concave portion. The silver nano-particles are densely arranged on top of each other, so it is easy to sinter (neck) the silver nano-particles. (necking)). In addition, due to the extremely small particle size, the impact of one silver nanoparticle on printing quality can be greatly reduced.

關於銀奈米粒子的粒徑及形狀，只要無損本發明的效果，則並無特別限定，可使用先前公知的各種銀奈米粒子。具體而言，可使用平均粒徑未滿1μm的銀奈米粒子，更佳的平均粒徑為1nm~200nm，最佳的平均粒徑為2nm~100nm。若銀奈米粒子的平均粒徑為1nm以上，則銀微粒子具備良好的低溫燒結性且銀微粒子製造成本不會變高而實用。另外，若為200nm以下，則銀微粒子的分散性不易經時性變化而較佳。 The particle size and shape of the silver nanoparticle are not particularly limited as long as the effect of the present invention is not impaired, and various previously known silver nanoparticle can be used. Specifically, silver nanoparticles with an average particle size of less than 1 μm can be used, and the more preferable average particle size is 1 nm to 200 nm, and the most preferable average particle size is 2 nm to 100 nm. If the average particle diameter of the silver nanoparticle is 1 nm or more, the silver microparticles have good low-temperature sinterability and the production cost of the silver microparticles does not increase, making it practical. In addition, if it is 200 nm or less, the dispersibility of the silver fine particles is less likely to change over time, which is preferable.

此處，銀奈米粒子的粒徑亦可不固定。另外，如上所述，銀奈米粒子的平均粒徑較佳為200nm以下，但於導電性糊包含後述的分散劑等作為任意成分的情況下，若為不會產生凝聚，不會顯著損及本發明的效果的成分，則亦可包含所述具有超過200nm的平均粒徑的銀微粒子。除此以外，亦可視需要添加銀微小粒子。 Here, the particle size of the silver nanoparticles may not be fixed. In addition, as described above, the average particle diameter of silver nanoparticles is preferably 200 nm or less. However, when the conductive paste contains the dispersant described below as an optional component, if aggregation does not occur, it will not be significantly damaged. The component of the effect of the present invention may also include the aforementioned silver fine particles having an average particle diameter exceeding 200 nm. In addition, fine silver particles can also be added as needed.

進而，本發明的導電性糊中，較佳為所述低膨潤性有機溶媒的常壓下的沸點為200℃以上，且所述低膨潤性有機溶媒具有羥基。原因在於為如下傾向：藉由常壓下的沸點為200℃以上，凹版上的過度的乾燥得到抑制，藉由具有羥基，對奈米粒子的分散變得良好，且藉由極性提高而抑制對膠板的膨潤。 Furthermore, in the conductive paste of the present invention, it is preferable that the low swelling organic solvent has a boiling point at normal pressure of 200° C. or higher, and the low swelling organic solvent has a hydroxyl group. The reason lies in the following tendency: the boiling point at normal pressure is 200°C or higher, excessive drying on the intaglio plate is suppressed, the dispersion of nanoparticles becomes good by having hydroxyl groups, and the increase in polarity suppresses the Swelling of rubber sheet.

另外，本發明亦提供一種導電性圖案的形成方法，其特徵在於：使用利用了凹版的凹版平板印刷法，所述凹版具有於印刷面填充有印刷用導電性糊的凹部，所述凹部對應於線寬為10μm以下的細線圖案的印刷， 所述印刷用導電性糊使用第1發明~第3發明中任一發明所述的導電性糊。 In addition, the present invention also provides a method of forming a conductive pattern, which is characterized by using a gravure lithography method using an intaglio plate having a concave portion filled with a conductive paste for printing on a printing surface, and the concave portion corresponds to Printing of fine line patterns with a line width of 10μm or less, As the conductive paste for printing, the conductive paste according to any one of the first to third inventions is used.

本發明的導電性圖案的形成方法中，由於使用所述本發明的導電性糊進行凹版平板印刷，因此可極其良好地達成線寬成為10μm以下的細線圖案的印刷。 In the method for forming a conductive pattern of the present invention, since the conductive paste of the present invention is used for gravure lithography, printing of a fine line pattern with a line width of 10 μm or less can be achieved extremely well.

更具體而言，本發明的導電性糊包含膠板膨潤率為2.0%以下的極低的有機溶媒，因而膠板對有機溶媒的吸收減少，可大幅度抑制膠板表面的導電性糊的乾燥。於使用導電性糊印刷極細線的情況下，被印刷成極細線狀的導電性糊非常容易乾燥而難以形成良好的導電性圖案，但本發明的導電性糊中，由於有機溶媒的膠板膨潤率為2.0%以下，因而例如亦可應對線寬為5μm以下的極細線導電性圖案的形成。 More specifically, the conductive paste of the present invention contains an extremely low organic solvent with a rubber sheet swelling rate of 2.0% or less, so the absorption of the organic solvent by the rubber sheet is reduced, and the drying of the conductive paste on the surface of the rubber sheet can be greatly suppressed. . In the case of using a conductive paste to print ultra-fine lines, the conductive paste printed in the form of ultra-fine lines is very easy to dry and it is difficult to form a good conductive pattern. However, in the conductive paste of the present invention, the rubber sheet of the organic solvent swells. Since the rate is 2.0% or less, for example, it is also possible to cope with the formation of an ultra-fine line conductive pattern with a line width of 5 μm or less.

依據本發明的導電性糊，可形成具有充分的導電性及與基板的良好的密接性的微細導電性圖案。另外，依據本發明的導電性圖案的形成方法，可形成線寬為5μm以下的導電性圖案。 According to the conductive paste of the present invention, a fine conductive pattern having sufficient conductivity and good adhesion to the substrate can be formed. In addition, according to the method for forming a conductive pattern of the present invention, a conductive pattern having a line width of 5 μm or less can be formed.

以下，對(1)本發明的導電性糊的較佳的一實施形態、(2)本發明的導電性糊的製造方法的較佳的一實施形態、(3)本發明的導電性圖案的形成方法的較佳的一實施形態進行詳細說 明。再者，於以下的說明中有時省略重覆的說明。 Hereinafter, (1) a preferred embodiment of the conductive paste of the present invention, (2) a preferred embodiment of the method for producing the conductive paste of the present invention, and (3) the conductive pattern of the present invention A preferred embodiment of the forming method will be described in detail bright. In addition, repeated descriptions are sometimes omitted in the following descriptions.

(1)導電性糊 (1) Conductive paste

本實施形態的導電性糊為如下導電性糊，其特徵在於：包含銀微粒子及有機溶媒，所述有機溶媒包含膠板膨潤率成為2.0%以下的低膨潤性有機溶媒，所述低膨潤性有機溶媒的含有率為3.0wt%~30wt%。以下，對該些各成分等進行說明。 The conductive paste of this embodiment is a conductive paste characterized by containing silver particles and an organic solvent, the organic solvent including a low-swelling organic solvent having a rubber sheet swelling rate of 2.0% or less, and the low-swelling organic The solvent content is 3.0wt%~30wt%. Hereinafter, the respective components and the like will be described.

(1-1)銀微粒子 (1-1) Silver particles

本實施形態的導電性糊中的銀微粒子的平均粒徑若為無損本發明的效果的範圍，則並無特別限制，較佳為使用平均粒徑未滿1μm的銀奈米粒子。此處，較佳為具有如產生熔點下降般的平均粒徑者，更佳為例如平均粒徑為1nm~200nm，進而最佳為2nm~100nm。若銀微粒子的平均粒徑為1nm以上，則銀微粒子具備良好的低溫燒結性且銀微粒子製造成本不會變高而實用。另外，若為200nm以下，則銀微粒子的分散性不易經時性變化而較佳。 The average particle size of the silver fine particles in the conductive paste of the present embodiment is not particularly limited as long as it is in a range that does not impair the effect of the present invention. However, it is preferable to use silver nanoparticles having an average particle size of less than 1 μm. Here, it is preferable to have an average particle diameter such that the melting point is lowered, and the average particle diameter is more preferably, for example, 1 nm to 200 nm, and most preferably 2 nm to 100 nm. If the average particle diameter of the silver microparticles is 1 nm or more, the silver microparticles have good low-temperature sinterability, and the production cost of the silver microparticles does not increase, and it is practical. In addition, if it is 200 nm or less, the dispersibility of the silver fine particles is less likely to change over time, which is preferable.

另外，考慮到使用本發明的導電性糊而形成的導電性圖案的遷移的問題，亦可添加離子化序列比氫更惰性的金屬，即金、銅、鉑、鈀等的粒子。 In addition, in consideration of the problem of the migration of the conductive pattern formed using the conductive paste of the present invention, a metal whose ionization sequence is more inert than hydrogen, that is, particles of gold, copper, platinum, palladium, etc. may be added.

再者，本實施形態的導電性糊中的銀微粒子的粒徑亦可不固定。另外，於導電性糊包含後述的分散劑等作為任意成分的情況下，若為不會產生凝聚，不會顯著損及本發明的效果的成分，則亦可包含具有各種粒徑的金屬粒子成分。 In addition, the particle size of the silver fine particles in the conductive paste of this embodiment may not be fixed. In addition, when the conductive paste contains a dispersant described later as an optional component, if it is a component that does not cause aggregation and does not significantly impair the effect of the present invention, it may also contain a metal particle component having various particle diameters. .

另外，亦可視需要併用添加微米尺寸的銀粒子。所述情 況下，奈米尺寸的銀粒子在微米尺寸的銀粒子的周圍熔點下降，藉此可獲得良好的導電通道。 In addition, micron-sized silver particles can also be added together as needed. Stated In this case, the melting point of nanometer-sized silver particles decreases around micrometer-sized silver particles, so that a good conductive path can be obtained.

此處，本實施形態的導電性糊中的銀微粒子的粒徑可藉由動態光散射法、小角度X射線散射法、廣角X射線繞射法來測定。為了顯示出奈米尺寸的銀微粒子的熔點下降，適當的是藉由廣角X射線繞射法所求出的微晶直徑。例如廣角X射線繞射法中，更具體而言，可使用理學電機(股)製造的瑞恩特-尤體麻(RINT-Ultima)III，藉由繞射法於2θ為30°~80°的範圍內進行測定。所述情況下，試樣只要以於中央部具有深度為0.1mm~1mm左右的凹陷的玻璃板上表面變得平坦的方式薄薄地拉伸來進行測定即可。另外，只要使用理學電機(股)製造的JADE，將所獲得的繞射光譜的半寬度代入至下述的謝樂公式(Scherrer's equation)中，將藉此而算出的微晶直徑(D)設為粒徑即可。 Here, the particle size of the silver fine particles in the conductive paste of the present embodiment can be measured by a dynamic light scattering method, a small-angle X-ray scattering method, and a wide-angle X-ray diffraction method. In order to show that the melting point of nano-sized silver particles has decreased, it is appropriate to obtain the crystallite diameter by the wide-angle X-ray diffraction method. For example, in the wide-angle X-ray diffraction method, more specifically, RINT-Ultima III manufactured by Rigaku Denki Co., Ltd. can be used, and the 2θ is 30°~80° by the diffraction method. Measure within the range. In this case, the sample may be measured by stretching it thinly so that the surface of the glass plate having a depression with a depth of about 0.1 mm to 1 mm in the center becomes flat. In addition, as long as the JADE manufactured by Rigaku Denki Co., Ltd. is used, the half-width of the obtained diffraction spectrum is substituted into the following Scherrer's equation, and the crystallite diameter (D) calculated therefrom is set to Just be the particle size.

D=Kλ/Bcosθ D=Kλ/Bcosθ

此處，K：謝樂常數(0.9)，λ：X射線的波長，B：繞射線的半寬度，θ：布拉格角(Bragg angle)。 Here, K: Scherrer constant (0.9), λ: wavelength of X-rays, B: half-width of the surrounding ray, θ: Bragg angle (Bragg angle).

(1-2)有機成分 (1-2) Organic ingredients

本實施形態的導電性糊中，較佳為於銀微粒子的表面的至少一部分附著有有機成分。所述有機成分作為所謂的分散劑而與所述銀微粒子一同實質性地構成無機膠體粒子。所述有機成分的概 念不包括如最初作為雜質而包含於銀微粒子中的微量有機物，於後述的製造過程中混入並附著於銀微粒子上的微量有機物，於清洗過程中未完全去除的殘留還原劑、殘留分散劑等般，微量附著於銀微粒子上的有機物等。再者，所述「微量」具體而言是指於無機膠體粒子中未滿1質量%。 In the conductive paste of this embodiment, it is preferable that an organic component adheres to at least a part of the surface of silver microparticles|fine-particles. The organic component serves as a so-called dispersant and substantially constitutes inorganic colloidal particles together with the silver fine particles. Overview of the organic ingredients The concept does not include trace organic matter initially contained in silver particles as impurities, trace organic matter mixed in and attached to silver particles during the manufacturing process described later, residual reducing agent, residual dispersing agent, etc. that were not completely removed during the cleaning process. Generally, a small amount of organic matter attached to silver particles. In addition, the "minimum amount" specifically refers to less than 1% by mass in the inorganic colloidal particles.

所述有機成分是可被覆銀微粒子來防止所述銀微粒子的凝聚，並且可形成無機膠體粒子的有機物，被覆的形態並無特別規定，但本實施形態中，就分散性及導電性等的觀點而言，較佳為包含胺及羧酸。再者，亦可考慮到當該些有機成分與無機粒子化學式地結合或物理式地結合時，變化成陰離子或陽離子的情況，本實施形態中，該些源自有機成分的離子或錯合物等亦包含於所述有機成分中。 The organic component is an organic substance that can coat silver microparticles to prevent aggregation of the silver microparticles, and can form inorganic colloidal particles. The coating form is not specifically defined, but in this embodiment, the viewpoints of dispersibility and conductivity are considered. In particular, it preferably contains an amine and a carboxylic acid. Furthermore, when these organic components are chemically or physically combined with inorganic particles, they may change into anions or cations. In this embodiment, the ions or complexes derived from organic components Etc. are also included in the organic ingredients.

作為胺，可為直鏈狀，亦可為支鏈狀，另外，亦可具有側鏈。例如可列舉：N-(3-甲氧基丙基)丙烷-1,3-二胺、1,2-乙烷二胺、2-甲氧基乙基胺、3-甲氧基丙基胺、3-乙氧基丙基胺、1,4-丁烷二胺、1,5-戊烷二胺、戊醇胺、胺基異丁醇等二胺或烷氧基胺，胺基醇，除此以外，丙基胺、丁基胺、戊基胺、己基胺等烷基胺(直鏈狀烷基胺，亦可具有側鏈)，環戊基胺、環己基胺等環烷基胺，苯胺、烯丙基胺等一級胺，二丙基胺、二丁基胺、哌啶、六亞甲基亞胺等二級胺，三丙基胺、二甲基丙烷二胺、環己基二甲基胺、吡啶、喹啉等三級胺等。 The amine may be linear or branched, and it may have a side chain. Examples include: N-(3-methoxypropyl)propane-1,3-diamine, 1,2-ethanediamine, 2-methoxyethylamine, 3-methoxypropylamine , 3-ethoxypropylamine, 1,4-butanediamine, 1,5-pentanediamine, pentanolamine, amino isobutanol and other diamines or alkoxyamines, amino alcohols, In addition, alkylamines such as propylamine, butylamine, pentylamine, and hexylamine (linear alkylamines may have side chains), cycloalkylamines such as cyclopentylamine and cyclohexylamine , Aniline, allyl amine and other primary amines, dipropyl amine, dibutyl amine, piperidine, hexamethylene imine and other secondary amines, tripropyl amine, dimethyl propane diamine, cyclohexyl diamine Tertiary amines such as methylamine, pyridine, quinoline, etc.

所述胺亦可為例如包含羥基、羧基、烷氧基、羰基、酯 基、巰基等胺以外的官能基的化合物。另外，所述胺分別可單獨使用，亦可併用兩種以上。除此以外，常壓下的沸點較佳為300℃以下，更佳為250℃以下。 The amine can also be, for example, a hydroxyl group, a carboxyl group, an alkoxy group, a carbonyl group, an ester Compounds with functional groups other than amines, such as sulfhydryl groups and mercapto groups. In addition, each of the amines may be used alone, or two or more of them may be used in combination. In addition, the boiling point under normal pressure is preferably 300°C or lower, more preferably 250°C or lower.

本實施形態的導電性糊中，只要是無損本發明的效果的範圍，則除了所述胺以外，亦可包含羧酸。羧酸的一分子內的羧基具有比較高的極性，容易產生由氫鍵所引起的相互作用，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。 In the conductive paste of this embodiment, as long as it is a range which does not impair the effect of this invention, you may contain a carboxylic acid in addition to the said amine. The carboxyl group in one molecule of the carboxylic acid has relatively high polarity and is likely to cause interaction caused by hydrogen bonding, but the parts other than these functional groups have relatively low polarity. Furthermore, the carboxyl group tends to exhibit acidic properties.

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、草酸、乙酸、己酸、丙烯酸、辛酸、油酸等。羧酸的一部分的羧基可與金屬離子形成鹽。再者，關於所述金屬離子，可包含兩種以上的金屬離子。 As the carboxylic acid, compounds having at least one carboxyl group can be widely used, and examples thereof include formic acid, oxalic acid, acetic acid, caproic acid, acrylic acid, caprylic acid, and oleic acid. A part of the carboxyl group of the carboxylic acid may form a salt with a metal ion. Furthermore, regarding the metal ions, two or more kinds of metal ions may be included.

所述羧酸亦可為例如包含胺基、羥基、烷氧基、羰基、酯基、巰基等羧基以外的官能基的化合物。所述情況下，羧基的數量較佳為羧基以外的官能基的數量以上。另外，所述羧酸分別可單獨使用，亦可併用兩種以上。除此以外，常壓下的沸點較佳為300℃以下，更佳為250℃以下。另外，胺與羧酸形成醯胺。所述醯胺基亦適度地吸附於銀微粒子表面，因此於有機成分中亦可包含醯胺基。 The carboxylic acid may be, for example, a compound containing a functional group other than a carboxyl group such as an amino group, a hydroxyl group, an alkoxy group, a carbonyl group, an ester group, and a mercapto group. In this case, the number of carboxyl groups is preferably more than the number of functional groups other than carboxyl groups. In addition, each of the carboxylic acids may be used alone, or two or more of them may be used in combination. In addition, the boiling point under normal pressure is preferably 300°C or lower, more preferably 250°C or lower. In addition, amines and carboxylic acids form amides. The amide group is also appropriately adsorbed on the surface of the silver particles, so the organic component may also contain the amide group.

本實施形態的導電性糊中的無機膠體中的有機成分的含量較佳為0.5質量%~50質量%。若有機成分含量為0.5質量%以上，則存在所獲得的接合用組成物的儲存穩定性變得良好的傾 向；若為50質量%以下，則存在導電性圖案的導電性良好的傾向。有機成分的更佳的含量為1質量%~30質量%，更佳的含量為2質量%~15質量%。 The content of the organic component in the inorganic colloid in the conductive paste of the present embodiment is preferably 0.5% by mass to 50% by mass. If the organic component content is 0.5% by mass or more, there is a tendency that the storage stability of the obtained bonding composition becomes good. If it is 50% by mass or less, the conductive pattern tends to have good conductivity. The more preferable content of the organic component is 1% by mass to 30% by mass, and the more preferable content is 2% by mass to 15% by mass.

作為併用胺與羧酸時的組成比(質量)，可於1/99~99/1的範圍內任意地選擇，但較佳為20/80~98/2，更佳為30/70~97/3。再者，胺或羧酸分別可使用多種胺或羧酸。 The composition ratio (mass) when amine and carboxylic acid are used in combination can be arbitrarily selected in the range of 1/99 to 99/1, but it is preferably 20/80 to 98/2, more preferably 30/70 to 97 /3. In addition, multiple amines or carboxylic acids can be used as amines or carboxylic acids, respectively.

本實施形態的導電性糊中，除了所述成分以外，為了賦予對應於使用目的的適度的黏性、密接性、乾燥性或印刷性等功能，亦可於無損本發明的效果的範圍內，添加高分子分散劑、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、增稠劑或表面張力調整劑等任意成分。作為所述任意成分，並無特別限定。 In the conductive paste of the present embodiment, in addition to the above-mentioned components, in order to impart appropriate functions such as viscosity, adhesion, drying properties, and printability corresponding to the purpose of use, it may be within a range that does not impair the effects of the present invention. Add a polymer dispersant, such as an oligomer component that functions as a binder, a resin component, an organic solvent (which can dissolve or disperse a part of the solid component), a surfactant, a thickener, or a surface tension regulator, etc. Element. There are no particular limitations on the optional component.

作為所述高分子分散劑，可使用市售的高分子分散劑。作為市售的高分子分散劑，例如作為所述市售品，例如可列舉：索思帕(SOLSPERSE)11200、索思帕(SOLSPERSE)13940、索思帕(SOLSPERSE)16000、索思帕(SOLSPERSE)17000、索思帕(SOLSPERSE)18000、索思帕(SOLSPERSE)20000、索思帕(SOLSPERSE)24000、索思帕(SOLSPERSE)26000、索思帕(SOLSPERSE)27000、索思帕(SOLSPERSE)28000(日本路博潤(Japan Lubrizol)(股)製造)；迪斯普畢克(DISPERBYK)-102、迪斯普畢克(DISPERBYK)110、迪斯普畢克(DISPERBYK)111、迪斯普畢克(DISPERBYK)170、迪斯普畢克(DISPERBYK)190、 迪斯普畢克(DISPERBYK)194N、迪斯普畢克(DISPERBYK)2015、迪斯普畢克(DISPERBYK)2090、迪斯普畢克(DISPERBYK)2096(日本畢克化學(BYK Chemie．Japan)(股)製造)；埃夫卡(EFKA)-46、埃夫卡(EFKA)-47、埃夫卡(EFKA)-48、埃夫卡(EFKA)-49(埃夫卡化學(EFKA Chemical)公司製造)；聚合物(Polymer)100、聚合物(Polymer)120、聚合物(Polymer)150、聚合物(Polymer)400、聚合物(Polymer)401、聚合物(Polymer)402、聚合物(Polymer)403、聚合物(Polymer)450、聚合物(Polymer)451、聚合物(Polymer)452、聚合物(Polymer)453(埃夫卡化學(EFKA Chemical)公司製造)；阿吉斯帕(Ajisper)PB711、阿吉斯帕(Ajisper)PA111、阿吉斯帕(Ajisper)PB811、阿吉斯帕(Ajisper)PW911(味之素(Ajinomoto)公司製造)；弗洛蘭(Florene)DOPA-15B、弗洛蘭(Florene)DOPA-22、弗洛蘭(Florene)DOPA-17、弗洛蘭(Florene)TG-730W、弗洛蘭(Florene)G-700、弗洛蘭(Florene)TG-720W(共榮社化學工業(股)製造)等，贏創(Evonik)公司的迪高迪斯帕斯(TEGO Dispers)系列中可列舉610、610S、630、651、655、750W、755W等，楠本化成的迪斯帕隆(Disparlon)系列中可列舉DA-375、DA-1200等，就低溫燒結性及分散穩定性的觀點而言，較佳為使用迪斯普畢克(DISPERBYK)-102、索思帕(SOLSPERSE)11200、索思帕(SOLSPERSE)13940、索思帕(SOLSPERSE)16000、索思帕(SOLSPERSE)17000、索思帕(SOLSPERSE)18000、索思帕 (SOLSPERSE)28000。 As the polymer dispersant, a commercially available polymer dispersant can be used. As a commercially available polymer dispersant, for example, the commercially available products include: SOLSPERSE 11200, SOLSPERSE 13940, SOLSPERSE 16000, SOLSPERSE ) 17000, Solsperse 18000, Solsperse 20000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000 (Made by Japan Lubrizol (Stock)); DISPERBYK-102, DISPERBYK 110, DISPERBYK 111, DISPERBYK Grams (DISPERBYK) 170, DISPERBYK (DISPERBYK) 190, DISPERBYK 194N, DISPERBYK 2015, DISPERBYK 2090, DISPERBYK 2096 (BYK Chemie. Japan) (Stock) Manufacturing); EFKA-46, EFKA-47, EFKA-48, EFKA-49 (EFKA Chemical) Manufactured by the company); Polymer 100, Polymer 120, Polymer 150, Polymer 400, Polymer 401, Polymer 402, Polymer ) 403, Polymer 450, Polymer 451, Polymer 452, Polymer 453 (manufactured by EFKA Chemical); Ajisper PB711, Ajisper PA111, Ajisper PB811, Ajisper PW911 (manufactured by Ajinomoto); Florene DOPA-15B, F Florene DOPA-22, Florene DOPA-17, Florene TG-730W, Florene G-700, Florene TG-720W (total Evonik’s TEGO Dispers series include 610, 610S, 630, 651, 655, 750W, 755W, etc., and Kusumoto Chemical’s The Disparlon series include DA-375, DA-1200, etc. From the viewpoint of low-temperature sinterability and dispersion stability, it is preferable to use DISPERBYK-102, Soth Solsperse 11200, Solsperse 13940, Solsperse 16000, Solsperse 17000, Solsperse 18000, Solsperse (SOLSPERSE) 28000.

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，則所獲得的接合用組成物的分散穩定性變得良好，但當含量過多時，分散穩定性會下降。就此種觀點而言，高分子分散劑的更佳的含量為0.03質量%~3質量%，進而更佳的含量為0.05質量%~2質量%。 The content of the polymer dispersant is preferably 0.1% by mass to 15% by mass. If the content of the polymer dispersing agent is 0.1% or more, the dispersion stability of the obtained bonding composition becomes good, but when the content is too large, the dispersion stability will decrease. From this point of view, the more preferable content of the polymer dispersant is 0.03% by mass to 3% by mass, and the more preferable content is 0.05% by mass to 2% by mass.

作為樹脂成分，例如可列舉：聚酯系樹脂、封閉型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、三聚氰胺系樹脂或萜烯系樹脂等，該些分別可單獨使用，亦可併用兩種以上。 As the resin component, for example, polyurethane resins such as polyester resins and blocked isocyanates, polyacrylate resins, polyacrylamide resins, polyether resins, melamine resins, or terpenes can be cited. For resins, etc., these may be used alone, or two or more of them may be used in combination.

此處，於被印刷物例如為聚對苯二甲酸乙二酯(Polyethylene Terephthalate，PET)的情況下，作為樹脂成分，較佳為使用選自由其自身對於PET的密接性良好的聚乙烯醇、聚乙烯吡咯啶酮、氯乙烯-乙酸乙烯酯共聚物、聚乙烯乙醯縮醛、聚乙烯丁醛所組成的群組中者。作為所述酮-甲醛縮聚物或其氫化物，可列舉日本贏創迪高沙(Evonik Degussa Japan)(股)迪高(TEGO)(註冊商標)巴里普斯(VariPlus)系列(SK、AP等)，作為氯乙烯-乙酸乙烯酯共聚物，可列舉日信化學工業股份有限公司製造的蘇魯賓(SOLBIN)(註冊商標)系列(蘇魯賓(SOLBIN)AL等)，作為聚乙烯乙醯縮醛、聚乙烯丁醛，可列舉積水化學工業股份有限公司製造的S-REC(註冊商標)系列(S-REC KS-1、S-REC BL-1等)。其中，聚乙烯吡咯啶酮對高極性多元醇(尤其 是二醇溶媒)的溶解性高，亦可良好地溶解於酯、酮等溶媒中，因此可較佳地使用。 Here, when the printed matter is, for example, polyethylene terephthalate (PET), as the resin component, it is preferable to use polyvinyl alcohol and polyvinyl alcohol, which have good adhesion to PET. Vinylpyrrolidone, vinyl chloride-vinyl acetate copolymer, polyvinyl acetal, polyvinyl butyraldehyde. Examples of the ketone-formaldehyde polycondensate or its hydride include Evonik Degussa Japan (Stock) TEGO (registered trademark) VariPlus series (SK, AP, etc.) ), as the vinyl chloride-vinyl acetate copolymer, the SOLBIN (registered trademark) series manufactured by Nissin Chemical Industry Co., Ltd. (SOLBIN AL, etc.), as polyvinyl acetal, poly Examples of vinyl butyraldehyde include S-REC (registered trademark) series manufactured by Sekisui Chemical Industry Co., Ltd. (S-REC KS-1, S-REC BL-1, etc.). Among them, polyvinylpyrrolidone has an effect on highly polar polyols (especially It is a glycol solvent) which has high solubility and can be well dissolved in solvents such as esters and ketones, so it can be preferably used.

作為增稠劑，可列舉例如黏土、膨土或鋰膨潤石等黏土礦物，例如聚酯系乳液樹脂、丙烯酸系乳液樹脂、聚胺基甲酸酯系乳液樹脂或嵌段異氰酸酯等的乳液，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等纖維素衍生物，三仙膠或瓜爾膠等多糖類等，該些分別可單獨使用，亦可併用兩種以上。 Examples of the thickener include clay minerals such as clay, bentonite, or lithium bentonite, such as polyester emulsion resins, acrylic emulsion resins, polyurethane emulsion resins, or blocked isocyanate emulsions. Cellulose derivatives such as cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose, polysaccharides such as sanxian gum or guar gum, etc., which are respectively It can be used alone, or two or more of them can be used in combination.

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，容易產生由乾燥時的揮發速度的不同所引起的被膜表面的粗糙及固體成分的偏集。藉由將界面活性劑添加至本實施形態的接合用組成物中，可抑制該些不利狀況，並獲得可形成均勻的導電性被膜的接合用組成物。 It is also possible to add a surfactant different from the organic component. In a multi-component solvent-based inorganic colloidal dispersion liquid, the roughness of the film surface and the segregation of solid content caused by the difference in the volatilization rate during drying are likely to occur. By adding a surfactant to the bonding composition of this embodiment, these disadvantages can be suppressed, and a bonding composition that can form a uniform conductive film can be obtained.

作為可用於本實施形態的界面活性劑，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種，例如可列舉烷基苯磺酸鹽、四級銨鹽等。較佳為氟系界面活性劑，其原因在於：能夠以少量的添加量獲得效果。 The surfactant that can be used in this embodiment is not particularly limited, and any of anionic surfactants, cationic surfactants, and nonionic surfactants can be used. For example, alkylbenzene sulfonates, Quaternary ammonium salt and so on. The fluorine-based surfactant is preferable because the effect can be obtained with a small amount of addition.

(1-3)有機溶媒(分散介質) (1-3) Organic solvent (dispersion medium)

本實施形態的導電性糊中，於分散介質中包含膠板膨潤率成為2%以下的低膨潤性有機溶媒。作為膠板膨潤率成為2%以下的低膨潤性有機溶媒，只要無損本發明的效果，則可使用各種溶媒。 此處，分散介質中僅使用膠板膨潤率成為2%以下的低膨潤性有機溶媒，為了調整乾燥性等，亦可與膠板膨潤率超過2%的溶媒混合而用作混合溶媒。再者，混合的組合並無特別限定，亦可混合多種以上的溶媒。 In the conductive paste of the present embodiment, a low swelling organic solvent having a swelling rate of the rubber sheet of 2% or less is contained in the dispersion medium. As a low-swelling organic solvent having a rubber sheet swelling rate of 2% or less, various solvents can be used as long as the effects of the present invention are not impaired. Here, only a low-swelling organic solvent having a rubber sheet swelling rate of 2% or less is used as a dispersion medium. In order to adjust dryness, etc., it may be mixed with a solvent having a rubber sheet swelling rate of more than 2% and used as a mixed solvent. In addition, the combination of mixing is not particularly limited, and multiple or more types of solvents may be mixed.

作為膠板膨潤率成為2%以下的低膨潤性有機溶媒，較佳為具有羥基作為官能基的溶媒，例如可列舉具有多個羥基的多元醇、或者其他一元醇溶媒等。該些溶媒分別可單獨使用，亦可併用兩種以上。 As a low-swelling organic solvent having a rubber sheet swelling rate of 2% or less, a solvent having a hydroxyl group as a functional group is preferred, and examples thereof include polyols having a plurality of hydroxyl groups or other monohydric alcohol solvents. These solvents may be used alone, respectively, or two or more of them may be used in combination.

本實施形態的導電性糊中，低膨潤性有機溶媒的含有率成為3.0wt%~30wt%。藉由將低膨潤性有機溶媒的含有率設為3.0wt%以上，例如可抑制如5μm以下般的極細線印刷時的乾燥，藉由設為30wt%以下，可防止印刷時的擴展。含有率為3.0wt%~25.0wt%，最佳的含有率為3.0wt%~20.0wt%。 In the conductive paste of the present embodiment, the content of the low swelling organic solvent is 3.0 wt% to 30 wt%. By setting the content of the low swelling organic solvent to be 3.0 wt% or more, for example, drying during printing of ultra-fine lines such as 5 μm or less can be suppressed, and by setting it to 30 wt% or less, spreading during printing can be prevented. The content rate is 3.0wt%~25.0wt%, and the best content rate is 3.0wt%~20.0wt%.

另外，本實施形態的導電性糊中，較佳為所述低膨潤性有機溶媒的常壓下的沸點為200℃以上，且所述低膨潤性有機溶媒具有羥基。原因在於為如下傾向：藉由常壓下的沸點為200℃以上，凹版上的過度的乾燥得到抑制，藉由具有羥基，對奈米粒子的分散變得良好，且藉由極性提高而抑制對膠板的膨潤。 In addition, in the conductive paste of the present embodiment, it is preferable that the low swelling organic solvent has a boiling point at normal pressure of 200° C. or higher, and the low swelling organic solvent has a hydroxyl group. The reason lies in the following tendency: the boiling point at normal pressure is 200°C or higher, excessive drying on the intaglio plate is suppressed, the dispersion of nanoparticles becomes good by having hydroxyl groups, and the increase in polarity suppresses the Swelling of rubber sheet.

(A)膠板膨潤率為2%以下的有機溶媒(低膨潤性有機溶媒) (A) An organic solvent with a swelling rate of 2% or less (low swelling organic solvent)

作為具有2個~3個羥基的多元醇，可列舉：甘油、1,2,4-丁三醇、1,2,6-己三醇、乙二醇、二乙二醇、1,2-丁二醇、丙二醇、 2-甲基戊烷-2,4-二醇等。 Examples of polyols having 2 to 3 hydroxyl groups include glycerin, 1,2,4-butanetriol, 1,2,6-hexanetriol, ethylene glycol, diethylene glycol, 1,2- Butylene glycol, propylene glycol, 2-Methylpentane-2,4-diol etc.

另外，作為為一元醇且膨潤率為2%以下的溶媒，可列舉：丁基三乙二醇、異丁基二乙二醇、2-丁氧基乙醇、3-甲氧基-3-甲基丁醇、2-(2-甲氧基乙氧基)乙醇、2-(2-己基氧基乙氧基)乙醇等，較佳為使用常壓下的沸點超過200℃的2,4-二乙基-1,5-戊二醇、3-甲基-1,5-戊二醇、2-乙基-1,3-己二醇、三丙二醇、三乙二醇、1,2-己二醇、1,3-丁二醇、1,3-丙二醇、二丙二醇、2-丁烯-1,4-二醇等二醇溶媒。 In addition, examples of solvents that are monohydric alcohols and have a swelling rate of 2% or less include: butyl triethylene glycol, isobutyl diethylene glycol, 2-butoxy ethanol, 3-methoxy-3-methyl Alkylbutanol, 2-(2-methoxyethoxy)ethanol, 2-(2-hexyloxyethoxy)ethanol, etc., it is preferable to use 2,4- Diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, tripropylene glycol, triethylene glycol, 1,2- Glycol solvents such as hexanediol, 1,3-butanediol, 1,3-propanediol, dipropylene glycol, and 2-butene-1,4-diol.

(B)膠板膨潤率超過2%的有機溶媒 (B) Organic solvents with rubber sheet swelling rate exceeding 2%

作為膠板膨潤率超過2%的膨潤率高的有機溶媒，可列舉：二醇醚、二醇酯、萜烯溶媒、烴溶媒、醇溶媒等，可分別單獨使用，亦可併用兩種以上。 Examples of organic solvents with a high swelling rate with a rubber sheet swelling rate exceeding 2% include glycol ethers, glycol esters, terpene solvents, hydrocarbon solvents, alcohol solvents, etc., which may be used alone or in combination of two or more.

作為膠板膨潤率超過2%的有機溶媒，例如可列舉：三丙二醇-正丁醚、丁基卡必醇、二乙二醇單甲醚、三丙二醇甲醚、二乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯、三乙二醇二甲醚、二丙二醇甲醚乙酸酯、二乙醇單己醚、二丙二醇甲醚、丙二醇二乙酸酯、1,4-丁二醇二乙烯醚、乙二醇單丁醚、乙二醇單甲醚乙酸酯。 Examples of organic solvents with a rubber sheet swelling rate exceeding 2% include: tripropylene glycol-n-butyl ether, butyl carbitol, diethylene glycol monomethyl ether, tripropylene glycol methyl ether, and diethylene glycol monoethyl ether acetic acid Ester, diethylene glycol monobutyl ether acetate, triethylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, diethanol monohexyl ether, dipropylene glycol methyl ether, propylene glycol diacetate, 1,4- Butylene glycol divinyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate.

另外，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。 In addition, examples of aliphatic hydrocarbons include tetradecane, octadecane, heptamethylnonane, tetramethylpentadecane, hexane, heptane, octane, nonane, decane, and tridecane. , Saturated aliphatic hydrocarbons or unsaturated aliphatic hydrocarbons such as methylpentane, normal paraffin, isoparaffin.

另外，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、二戊烯、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。 Moreover, as a cyclic hydrocarbon, toluene, xylene, etc. are mentioned, for example. Furthermore, as alicyclic hydrocarbons, for example, limonene, dipentene, terpinene, terpinene (also called terpinene), Nesol, Cinene, Orange flavor, terpinolene (terpinolene), terpinolene (also known as terpinolene), phellandrene, menthol diene, terebene, dihydroisopropyl toluene, scallopene ( Moslene, isoterpinene, isoterpinene (also known as isterpinene), γ-terpinene (Crithmene), Kautschin, cajeputene, limonene ( Eulimen), pinene, turpentine, menthane, pinane, terpene, cyclohexane, etc.

醇為分子結構中包含一個以上的羥基的化合物，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，羥基的一部分亦可衍生成乙醯氧基等。 Alcohol is a compound containing one or more hydroxyl groups in the molecular structure, and examples include aliphatic alcohols, cyclic alcohols, and alicyclic alcohols, each of which may be used alone or in combination of two or more. In addition, within a range that does not impair the effect of the present invention, a part of the hydroxyl group may be derivatized into an acetoxy group or the like.

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C6-30脂肪族醇或不飽和C6-30脂肪族醇等。 As aliphatic alcohols, for example, heptanol, octanol (1-octanol, 2-octanol, 3-octanol, etc.), decanol (1-decanol, etc.), lauryl alcohol, myristyl alcohol, decyl alcohol, etc. Saturated C 6-30 aliphatic alcohols or unsaturated C 6-30 aliphatic alcohols such as cetyl alcohol, 2-ethyl-1-hexanol, stearyl alcohol, hexadecenol, and oleyl alcohol.

作為環狀醇，例如可列舉：甲酚、丁香酚等。進而，作為如萜烯溶媒般的脂環式醇，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、馬鞭草烯醇等。 Examples of cyclic alcohols include cresol and eugenol. Furthermore, as alicyclic alcohols such as terpene solvents, for example, cycloalkanols such as cyclohexanol, terpineol (including α isomer, β isomer, γ isomer, or these Any mixture), terpene alcohols such as dihydroterpineol (monoterpene alcohol etc.), dihydroterpineol, myritol, sobrerol (sobrerol), menthol, ethnol, Perillyl alcohol, rosin Celery alcohol, verbena alcohol, etc.

本實施形態的導電性糊的黏度較佳為於凹版平板印刷用途中經調整。凹版平板印刷為可適應廣泛的黏度範圍的印刷方式，大多情況下在黏度為500cP~100000cP的範圍內使用，亦多以剪切黏度來表示。再者，黏度可藉由錐板型黏度計(例如，安東帕(Anton Paar)公司製造的流變儀MCR310)而測定。例如，可將測定溫度設為25℃，採用錐轉速為50rpm時的黏度。作為本實施形態的導電性糊的黏度，較佳為剪切速率(shear rate)1s-1下的糊黏度為100Pa．s以下，且剪切速率100s-1下的糊黏度為0.5Pa．s以上。 The viscosity of the conductive paste of this embodiment is preferably adjusted for gravure lithography applications. Gravure lithography is a printing method that can adapt to a wide range of viscosity. In most cases, it is used in the range of 500cP~100000cP, and it is also expressed by shear viscosity. Furthermore, the viscosity can be measured by a cone-plate type viscometer (for example, the rheometer MCR310 manufactured by Anton Paar). For example, the measurement temperature can be set to 25°C, and the viscosity when the cone rotation speed is 50 rpm can be used. As the viscosity of the conductive paste of the present embodiment, it is preferable that the viscosity of the paste at a shear rate of 1 s -1 is 100 Pa. s or less, and the paste viscosity at a shear rate of 100s -1 is 0.5Pa. s above.

(2)導電性糊的製造方法 (2) Manufacturing method of conductive paste

為了製造本實施形態的導電性糊，首先製備銀微粒子分散體。繼而，藉由將所述銀微粒子分散體與有機溶媒及所述各種成分混合，可獲得本實施形態的導電性糊。 In order to manufacture the conductive paste of this embodiment, first, a dispersion of silver fine particles is prepared. Then, by mixing the silver fine particle dispersion with an organic solvent and the various components, the conductive paste of the present embodiment can be obtained.

此處，銀微粒子分散體的製備包括：第1前步驟，製備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前步驟，藉由將所述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微粒子。 Here, the preparation of the silver microparticle dispersion includes: a first pre-step, preparing a mixture of silver compounds and amines that can be decomposed to produce metallic silver by reduction; and a second pre-step, by removing The silver compound is reduced to generate silver fine particles with amine attached to at least a part of the surface.

所述第1前步驟中，較佳為相對於1mol的金屬銀而添加2mol以上的胺。藉由將胺的添加量相對於1mol的金屬銀而設為2mol以上，可使適量的胺附著於藉由還原而生成的銀微粒子的表面，可對所述銀微粒子(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 previous step, it is preferable to add 2 mol or more of amine with respect to 1 mol of metallic silver. By setting the addition amount of amine to 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 particles generated by reduction, and the silver particles (silver nanoparticles) can be imparted For various dispersion media Excellent dispersibility and low temperature sintering.

再者，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微粒子的粒徑設為如產生熔點下降般的奈米尺寸，更佳為設為1nm~200nm。此處，視需要亦可包含微米尺寸的粒子。自所述第2前步驟中獲得的銀微粒子分散體中取出銀微粒子的方法並無特別限定，例如可列舉對所述銀微粒子分散體進行清洗的方法等。 Furthermore, according to the composition of the mixed solution in the first pre-step and the reduction conditions (such as heating temperature and heating time) in the second pre-step, it is preferable to set the particle size of the silver fine particles obtained It is a nanometer size that causes a drop in melting point, and it is more preferably 1 nm to 200 nm. Here, if necessary, micron-sized particles may also be included. The method of taking out the silver microparticles from the silver microparticle dispersion obtained in the second previous step is not particularly limited. For example, a method of washing the silver microparticle dispersion may be mentioned.

作為用以獲得由有機物(胺)所被覆的銀微粒子的起始材料，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、草酸銀、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，該些可單獨使用，亦可併用多種。 As a starting material for obtaining silver particles coated with organic substances (amines), various well-known silver compounds (metal salts or hydrates thereof) can be used, for example, silver nitrate, silver sulfate, silver chloride, and silver oxide. , Silver acetate, silver oxalate, silver formate, silver nitrite, silver chlorate, silver sulfide and other silver salts. These compounds are not particularly limited as long as they are reducible, and they can be dissolved in an appropriate solvent or used in a state of being dispersed in a solvent. In addition, these may be used alone, or multiple types may be used in combination.

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。 In addition, the method of reducing these silver compounds in the raw material liquid is not particularly limited, and examples include: a method of using a reducing agent; a method of irradiating light such as ultraviolet rays, electron beams, ultrasonic waves, or thermal energy; and a method of heating Wait. Among them, from the viewpoint of ease of handling, a method 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、草酸鐵、硫化鐵、乙酸錫、氯化錫、二磷酸錫、草酸錫、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. Hydrogen compounds such as carbon monoxide, sulfurous acid and other oxides; such as ferrous sulfate, iron oxide, iron fumarate, Iron lactate, iron oxalate, iron sulfide, tin acetate, tin chloride, tin diphosphate, tin oxalate, tin oxide, tin sulfate and other low-valent metal salts; such as ethylene glycol, glycerol, formaldehyde, hydroquinone, o- Sugars such as benzenetriol, tannins, tannic acid, salicylic acid, D-glucose, etc.; as long as they are soluble in the dispersion medium to reduce the metal salt, they are not particularly limited. In the case of using the reducing agent, light and/or heat may 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微粒子的具體方法，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，於所述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。 As a specific method of using the metal salt, organic component, solvent, and reducing agent to prepare silver particles coated with organic matter, for example, the following method can be cited: the metal salt is dissolved in an organic solvent (for example, toluene, etc.) To prepare a metal salt solution, an amine as a protective dispersant or a protective dispersant with an acid value is added to the metal salt solution, and then a solution in which the reducing agent is dissolved is slowly added dropwise.

於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微粒子的分散液中，除了銀微粒子以外，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，藉由對包含所述銀微粒子的溶液進行清洗而去除多餘的殘留物，可確實地獲得由有機物所被覆的銀微粒子。 In the dispersion liquid containing silver microparticles coated with amine or protective dispersant having an acid value obtained in the above manner, in addition to the silver microparticles, there are also counterions of metal salts, residues of reducing agents, or dispersants, There is a tendency for the electrolyte concentration or organic matter concentration of the entire liquid to be high. The liquid in this state is prone to coagulation and precipitation of metal particles due to high electrical conductivity and other reasons. Or, even if it does not precipitate, if the counterion of the metal salt, the residue of the reducing agent, or the excess dispersant more than the amount required for dispersion remains, there is a concern that the conductivity will deteriorate. Therefore, by washing the solution containing the silver fine particles to remove the excess residue, the silver fine particles covered with the organic matter can be obtained reliably.

作為所述清洗方法，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微粒子的分散液靜置一 定時間，去除所產生的上清液後，添加使銀微粒子沈澱的溶媒(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。藉由此種清洗而去除多餘的殘留物，並且去除有機溶媒，藉此可獲得表面的至少一部分由有機成分所被覆的銀微粒子。 As the cleaning method, for example, a method in which the following steps are repeated several times: a dispersion liquid containing silver particles coated with an organic component is allowed to stand still. After removing the generated supernatant for a fixed time, add a solvent (such as water, methanol, methanol/water mixed solvent, etc.) that precipitates the silver particles, stir again, and then remove the supernatant generated by standing for a certain period of time; Centrifugal separation is performed instead of the static method; the method of desalination using an ultrafiltration device or an ion exchange device, etc. By this cleaning, excess residues are removed and the organic solvent is removed, thereby obtaining silver fine particles whose surface is at least partially covered with organic components.

導電性糊可藉由使由所述有機成分所被覆的銀微粒子等分散於包含所述膠板膨潤率成為2%以下的低膨潤性有機溶媒的分散介質中(低膨潤性有機溶媒的含有率設為3.0wt%~30wt%)。所述銀微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，利用先前公知的方法來進行。利用刮勺之類者進行攪拌，或者亦可利用適當輸出功率的超音波均質器。 The conductive paste can be dispersed in a dispersion medium containing a low swelling organic solvent whose swelling rate of the rubber sheet is 2% or less (the content rate of the low swelling organic solvent). Set as 3.0wt%~30wt%). The mixing method of the silver fine particles and the dispersion medium is not particularly limited, and it can be performed by a conventionally known method using a stirrer, a stirrer, or the like. Use a spatula or the like for stirring, or an ultrasonic homogenizer with appropriate output power can also be used.

亦可藉由以下步驟來製造銀微粒子：第1步驟，製備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，藉由將所述混合液中的銀化合物還原而生成於表面的至少一部分附著有胺的銀微粒子。例如，可藉由對由包含銀的草酸銀等銀化合物與胺所生成的錯合化合物進行加熱，將所述錯合化合物中所含的草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微粒子。 Silver particles can also be produced by the following steps: the first step is to prepare a mixture of silver compounds and amines that can be decomposed to produce metallic silver by reduction; and the second step is to prepare the silver compound in the mixture The reduction produces silver fine particles with amine adhered to at least a part of the surface. For example, by heating a complex compound formed from a silver compound such as silver oxalate containing silver and an amine, the metal compound such as oxalate ion contained in the complex compound can be decomposed to make the generated atomic shape The silver aggregates to produce silver particles protected by a protective film of amine.

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微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，因此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變動所引起的反應的不均勻得到抑制，尤其是於以工業規模來製造大量的銀粉末時有利。 As described above, the metal amine complex is decomposed by thermally decomposing the complex compound of the silver compound in the presence of an amine to produce silver particles coated with the amine. In the method, the atomic silver is generated by the decomposition reaction of the silver amine complex as a single molecule. Therefore, the atomic silver can be uniformly generated in the reaction system, and the silver can be generated by the reaction of multiple components. Compared with the case of atoms, the unevenness of the reaction caused by the composition variation of the components constituting the reaction is suppressed, which is particularly advantageous when a large amount of silver powder is produced on an industrial scale.

另外推測：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，藉由配位於所述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。 In addition, it is speculated that in the metal amine complex decomposition method, amine molecules are coordinately bonded to the generated silver atoms, and the amine molecules coordinated on the silver atoms generate the movement of the silver atoms during aggregation. Get under control. As a result, according to the metal amine complex decomposition method, very fine metal particles with a narrow particle size distribution can be produced.

進而，大量的胺分子於所製造的銀微粒子的表面亦產生比較弱的力的配位鍵結，該些於銀微粒子的表面形成緻密的保護被膜，因此可製造保存穩定性優異的表面潔淨的有機被覆銀微粒子。另外，形成所述被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微粒子。 Furthermore, a large number of amine molecules also generate relatively weak coordination bonds on the surface of the produced silver particles, and these form a dense protective film on the surface of the silver particles. Therefore, it is possible to produce a clean surface with excellent storage stability. Organically coated silver particles. In addition, the amine molecules forming the film can be easily detached by heating or the like, so that silver fine particles that 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微粒子的被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，藉由混合所述胺來使用，可製造具有符合各種用途的特性的被覆銀微粒子。 In addition, when a solid silver compound is mixed with an amine to generate a complex compound such as a complex compound, the complex compound is easily generated by mixing an amine with a dispersant having an acid value for the coating film of the coated silver particles. It can be mixed in a short time to produce a composite compound. In addition, by mixing and using the amine, coated silver particles having characteristics suitable for various applications can be produced.

(3)導電性圖案(導電膜)及其形成方法 (3) Conductive pattern (conductive film) and its forming method

若使用本實施形態的導電性糊，可藉由使用了凹版的凹版平板印刷而形成精密的導電性圖案。更具體而言，藉由使用具有於 印刷面填充有印刷用導電性糊的凹部(對應於線寬為10μm以下的凹部)的凹版而印刷本實施形態的導電性糊，可形成具有充分的導電性及與基板的良好的密接性的微細導電性圖案。另外，藉由將所述凹部設為對應於線寬5μm以下的尺寸及形狀，可形成線寬為5μm以下的超微細導電性圖案。 If the conductive paste of this embodiment is used, a precise conductive pattern can be formed by gravure lithography using an intaglio plate. More specifically, by using The printed surface is filled with a concave portion of the conductive paste for printing (corresponding to a concave portion with a line width of 10 μm or less) intaglio, and the conductive paste of this embodiment is printed to form a substrate with sufficient conductivity and good adhesion to the substrate Fine conductive pattern. In addition, by setting the recesses to have a size and shape corresponding to a line width of 5 μm or less, an ultrafine conductive pattern with a line width of 5 μm or less can be formed.

本實施形態的導電性圖案可藉由如下的步驟而於基材的表面形成良好的導電性圖案：於基材上塗佈所述導電性糊的塗佈步驟、以及於未滿140℃(較佳為120℃以下)的溫度下對塗佈於基材上的導電性糊進行煅燒而形成導電性圖案的煅燒步驟。 The conductive pattern of this embodiment can form a good conductive pattern on the surface of the substrate by the following steps: the step of coating the conductive paste on the substrate, and the temperature less than 140°C (more Preferably, it is a firing step of firing the conductive paste applied on the substrate at a temperature of 120°C or less to form a conductive pattern.

作為所述塗佈步驟中的導電性圖案，若使用所述本實施形態的導電性糊，則即便於所述煅燒步驟中於未滿140℃的溫度下對塗佈於所述基材上的所述導電性墨水進行煅燒，亦可形成具有優異的導電性的導電性圖案。 As the conductive pattern in the coating step, if the conductive paste of the present embodiment is used, even at a temperature of less than 140° C. in the firing step, the coating on the substrate The conductive ink can also be calcined to form a conductive pattern having excellent conductivity.

塗佈步驟中，首先於膠板上塗佈導電性糊而形成導電性糊塗佈面。作為膠板，較佳為包含矽酮的矽酮膠板。再者，作為所述矽酮膠板，例如可列舉金陽公司的希爾布蘭(silblan)系列或藤倉橡膠工業的#700-STD等。 In the coating step, first, a conductive paste is applied to the rubber sheet to form a conductive paste coating surface. As the rubber sheet, a silicone rubber sheet containing silicone is preferred. In addition, as the silicone rubber sheet, for example, the silblan series of Jinyang Corporation, #700-STD of Fujikura Rubber Industry, and the like can be cited.

於使用先前的導電性墨水或導電性糊等的情況下，於在膠板的表面上形成導電性糊塗佈面後，藉由短時間的放置，低沸點溶劑揮發並吸收於膠板中，藉此導電性墨水的黏度上升。相對於此，本實施形態的導電性糊使用膠板膨潤率為2.0%以下的極低的有機溶媒，因而膠板對有機溶媒的吸收減少，可大幅度抑制膠 板表面的導電性糊的乾燥。於使用導電性糊而印刷極細線的情況下，被印刷成極細線狀的導電性糊非常容易乾燥，難以形成良好的導電性圖案，但本發明的導電性糊中，有機溶媒的膠板膨潤率成為2.0%以下，因而例如亦可應對線寬為5μm以下的極細線導電性圖案的形成。 In the case of using the previous conductive ink or conductive paste, after the conductive paste coating surface is formed on the surface of the rubber sheet, the low-boiling solvent volatilizes and is absorbed in the rubber sheet after a short period of time. The viscosity of this conductive ink increases. In contrast, the conductive paste of the present embodiment uses an extremely low organic solvent with a rubber sheet swelling rate of 2.0% or less, so the absorption of the organic solvent by the rubber sheet is reduced, and the glue can be greatly suppressed. Drying of the conductive paste on the surface of the board. In the case of printing ultra-fine lines using conductive paste, the conductive paste printed in the form of ultra-fine lines is very easy to dry and it is difficult to form a good conductive pattern. However, in the conductive paste of the present invention, the organic solvent rubber sheet swells Since the rate is 2.0% or less, for example, it is also possible to cope with the formation of an ultra-fine line conductive pattern with a line width of 5 μm or less.

將殘留於膠板上的濕潤狀態或者半乾燥狀態的導電性糊轉印於被印刷體上。此時，藉由導電性糊具有適度的凝聚性，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性圖案。 The conductive paste remaining in the wet state or semi-dry state on the rubber sheet is transferred to the printed body. At this time, since the conductive paste has moderate cohesiveness, peeling from the rubber sheet and adhesion to the printed body are surely performed, and poor residue on the rubber sheet is suppressed. As a result, on the to-be-printed body, a conductive pattern is formed with a pattern that is inverted with respect to the pattern formed on the relief plate.

作為本實施形態中可使用的基材，只要是可塗佈導電性糊，且藉由加熱進行煅燒而搭載導電性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，與先前的導電性墨水及導電性糊相比較，本實施形態的導電性糊即便於低溫下進行加熱而煅燒，亦可獲得具有充分的導電性的導電性圖案，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 that can be used in this embodiment is not particularly limited as long as it has at least one main surface that can be coated with a conductive paste and is calcined by heating to mount a conductive pattern, but it is preferably heat-resistant Excellent substrate. In addition, as described above, compared with the previous conductive inks and conductive pastes, the conductive paste of this embodiment can obtain a conductive pattern with sufficient conductivity even if it is heated and fired at a low temperature. In a temperature range higher than the low calcination temperature, a substrate with a lower heat resistance temperature than before is used.

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(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。基材的厚度亦可適宜選擇。出於黏接性或者密接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 materials constituting such a substrate include: polyamide (PA), polyimide (PI), polyamide imide (PAI), and polyterephthalic acid. Polyesters such as ethylene glycol (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polycarbonate (polycarbonate, PC), polyether sulfone (PES), vinyl resin, fluororesin, liquid crystal polymer, ceramic, glass or metal. In addition, 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. For the improvement of adhesiveness or adhesion, or for other purposes, a substrate on which a surface layer is formed or a substrate subjected to surface treatment such as hydrophilization treatment can be used.

藉由將以所述方式塗佈後的塗膜加熱至未滿140℃(較佳為120℃以下)的溫度而進行煅燒，可獲得導電性圖案(帶有導電性圖案的基材)。進行煅燒的方法並無特別限定，例如可藉由使用先前公知的齒輪烘箱(gear oven)等，以塗佈或描畫於基材上的所述導電性糊的溫度成為未滿140℃(較佳為120℃以下)的方式進行煅燒而形成導電性圖案。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性圖案的溫度，且可於無損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(亦可於無損本發明的效果的範圍內殘存一部分，但較佳為全部去除)。 By heating the coating film applied in the above manner to a temperature less than 140° C. (preferably 120° C. or lower) and calcining, a conductive pattern (a substrate with a conductive pattern) can be obtained. The method of firing is not particularly limited. For example, the temperature of the conductive paste applied or drawn on the substrate can be lower than 140°C (preferably, by using a previously known gear oven). It is calcined to form a conductive pattern by the method of 120°C or less. The lower limit of the firing temperature is not necessarily limited, but it is preferably a temperature at which a conductive pattern can be formed on the substrate, and the organic components and the like can be removed by evaporation or decomposition within a range that does not impair the effects of the present invention. Temperature (a part may remain within a range that does not impair the effect of the present invention, but it is preferable to remove all of it).

依據本實施形態的導電性糊，可形成於120℃左右的低溫加熱處理中亦表現出高導電性的導電性圖案，因此於比較不耐熱的基材上亦可形成導電性圖案。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性圖案。 According to the conductive paste of the present embodiment, a conductive pattern exhibiting high conductivity can be formed even in a low-temperature heat treatment at about 120°C. Therefore, a conductive pattern can also be formed on a relatively heat-resistant substrate. In addition, the firing time is not particularly limited, and a conductive pattern can be formed on the substrate according to the firing 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性圖案的密接性，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糊受容層的方法等。 In this embodiment, although it is basically unnecessary, in order to further improve the adhesion between the substrate and the conductive pattern, the surface of the substrate may be treated. reason. Examples of the surface treatment method include: corona treatment, plasma treatment, ultraviolet (ultraviolet, UV) treatment, electron beam treatment, and other dry treatment methods; a primer layer is provided on the substrate in advance Or the method of conductive paste-receiving layer, etc.

以所述方式所獲得的本實施形態的導電性圖案的膜厚例如為0.1μm~5μm左右，更佳為0.1μm~1μm。若使用本實施形態的導電性糊，則獲得即便厚度為0.1μm~5μm左右，亦具有充分的導電性的導電性圖案。再者，本實施形態的導電性圖案的體積電阻值為50μΩ．cm以下。 The film thickness of the conductive pattern of the present embodiment obtained as described above is, for example, about 0.1 μm to 5 μm, and more preferably 0.1 μm to 1 μm. If the conductive paste of this embodiment is used, a conductive pattern having sufficient conductivity even if the thickness is about 0.1 μm to 5 μm is obtained. Furthermore, the volume resistance value of the conductive pattern of this embodiment is 50μΩ. cm below.

再者，本實施形態的導電性圖案的厚度t例如可使用下述式來求出(導電性圖案的厚度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)。 In addition, the thickness t of the conductive pattern of the present embodiment can be obtained, for example, using the following formula (the thickness t of the conductive pattern can also be obtained using a laser microscope (for example, a laser microscope VK-9510 manufactured by Keyence) To determine).

式：t=m/(d×M×w) Formula: t=m/(d×M×w)

m：導電性圖案重量(利用電子天平來測定形成於載玻片上的導電性圖案的重量) m: Weight of the conductive pattern (measure the weight of the conductive pattern formed on the glass slide using an electronic balance)

d：導電性圖案密度(g/cm3)(銀的情況下為10.5g/cm3) d: Conductive pattern density (g/cm 3 ) (10.5 g/cm 3 in the case of silver)

M：導電性圖案長度(cm)(以相當於JIS1級的尺度來測定形成於載玻片上的導電性圖案的長度) M: Length of the conductive pattern (cm) (Measure the length of the conductive pattern formed on the glass slide with a scale equivalent to JIS1 level)

w：導電性圖案寬度(cm)(以相當於JIS1級的尺度來測定形成於載玻片上的導電性圖案的寬度) w: the width of the conductive pattern (cm) (measure the width of the conductive pattern formed on the glass slide with a scale equivalent to JIS1 level)

[實施例] [Example]

以下，列舉實施例及比較例，對本發明的導電性糊及導電性圖案的形成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, examples and comparative examples are cited to further describe the conductive paste and conductive pattern forming method of the present invention, but the present invention is not limited to these examples at all.

《實施例1》 "Example 1"

將9.0g的3-甲氧基丙基胺(和光純藥工業(股)製造的一級試劑)、及0.2g的作為高分子分散劑的迪斯普畢克(DISPERBYK)-102(畢克化學(BYK Chemie)公司製造)混合，利用磁力攪拌器充分攪拌，而生成胺混合液。繼而，一邊進行攪拌，一邊添加3.0g的草酸銀。添加草酸銀後，於室溫下繼續攪拌，藉此使草酸銀變化為具有黏性的白色物質，於確認到所述變化在外觀上結束的時刻結束攪拌。 Combine 9.0g of 3-methoxypropylamine (a primary reagent manufactured by Wako Pure Chemical Industries, Ltd.) and 0.2g of DISPERBYK-102 as a polymer dispersant. (Manufactured by BYK Chemie), and mixed thoroughly with a magnetic stirrer to produce an amine mixture. Then, while stirring, 3.0 g of silver oxalate was added. After the silver oxalate was added, the stirring was continued at room temperature, thereby changing the silver oxalate into a viscous white substance, and the stirring was terminated when it was confirmed that the change had ended in appearance.

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。 The obtained mixed liquid was transferred to an oil bath, and heated and stirred at 120°C. The reaction accompanied by the generation of carbon dioxide starts immediately after the start of the stirring, and then the stirring is performed until the generation of the carbon dioxide is completed, thereby obtaining a suspension of silver particles suspended in the amine mixture.

其次，為了置換所述懸浮液的分散介質，添加甲醇與水的混合溶媒10mL而進行攪拌後，藉由離心分離，使銀微粒子沈澱而分離，對於分離的銀微粒子，添加甲醇與水的混合溶媒10mL，並進行攪拌、離心分離，藉此使銀微粒子沈澱而精製分離，將進行了分離者於室溫下進行20分鐘的乾燥，而獲得銀奈米粒子漿料。對於銀奈米粒子漿料80重量份，添加使3重量份的作為樹 脂材的聚乙烯吡咯啶酮K30(和光純藥工業(股)製造的試劑)溶解於17重量份的作為有機溶媒的1,3-丁二醇(和光純藥工業(股)製造的一級試劑)中而得的混合溶液共計20重量份，利用攪拌棒進行混合，利用自轉.公轉混合機進行混料、消泡而獲得實施導電性糊1。 Next, in order to replace the dispersion medium of the suspension, 10 mL of a mixed solvent of methanol and water was added and stirred, and then centrifuged to precipitate and separate the silver particles. For the separated silver particles, a mixed solvent of methanol and water was added. 10 mL, stirring and centrifugal separation were performed to precipitate the silver fine particles for purification and separation, and the separated ones were dried at room temperature for 20 minutes to obtain a silver nanoparticle slurry. For 80 parts by weight of silver nanoparticle slurry, 3 parts by weight are added as a tree Polyvinylpyrrolidone K30 (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) as a fat material is dissolved in 17 parts by weight of 1,3-butanediol as an organic solvent (a primary reagent manufactured by Wako Pure Chemical Industries, Ltd.) A total of 20 parts by weight of the mixed solution obtained in) was mixed with a stir bar, mixed with a rotation-revolution mixer, and defoamed to obtain the conductive paste 1.

[評價試驗] [Evaluation Test]

關於所獲得的實施導電性糊1，進行凹版平板下的印刷適應性、分散性、稀釋性(剛結束後、經時穩定性)、體積電阻值、密接性試驗(拉脫法(pull-off method))的評價。除此以外，對所使用的有機溶媒測定膠板膨潤率。再者，導電性圖案的煅燒條件均設為120℃×30分鐘。 Regarding the obtained conductive paste 1, the printing suitability, dispersibility, dilution (immediately after completion, stability with time), volume resistance value, and adhesion test (pull-off method) under the intaglio plate were performed. method)) evaluation. In addition, the swelling rate of the rubber sheet was measured for the organic solvent used. In addition, the firing conditions of the conductive pattern were all 120° C.×30 minutes.

(1)膠板膨潤率的測定 (1) Determination of swelling rate of rubber sheet

凹版平板印刷法中，使用膠板。作為膠板，例如可列舉具有矽酮橡膠層、海綿層這樣的層結構的片材，通常在捲繞成被稱為膠板滾筒的具有剛性的圓筒的狀態下使用。若膠板膨潤率的測定中使用的膠板為導電性糊印刷時通常所使用的膠板，則不存在問題，所述膨潤率測定中，將金陽公司製造的「希爾布蘭(silblan)SP11-1、橡膠層t=0.6mm PET層0.25mm」作為「膠板A」。 In the gravure lithography method, an offset plate is used. The rubber sheet includes, for example, a sheet having a layer structure such as a silicone rubber layer and a sponge layer, and is usually used in a state of being wound into a rigid cylinder called a rubber sheet roll. If the rubber sheet used in the measurement of the swelling rate of the rubber sheet is a rubber sheet commonly used in conductive paste printing, there is no problem. In the measurement of the swelling rate, the "silblan (silblan) )SP11-1, rubber layer t=0.6mm, PET layer 0.25mm" as "plastic sheet A".

將表1所示的有機溶劑作為膠板膨潤率的評價對象，切出1cm見方，使測量後的膠板A完全浸漬於各種有機溶劑(20g)中，於10小時後將膠板自有機溶劑中取出，拭去所附著的溶劑，於一分鐘以內再次進行測量，而求出浸漬前後的重量增加率。將 所獲得的值示於表1中。再者，於室溫條件下(25℃±5℃)進行浸漬。另外，表1中亦示出了有機溶劑的沸點。 Take the organic solvents shown in Table 1 as the evaluation object of the rubber sheet swelling rate, cut out 1cm square, make the measured rubber sheet A completely immersed in various organic solvents (20g), and remove the rubber sheet from the organic solvent after 10 hours Take it out, wipe off the attached solvent, measure again within one minute, and obtain the weight increase rate before and after immersion. will The obtained values are shown in Table 1. Furthermore, the immersion is performed at room temperature (25°C ± 5°C). In addition, Table 1 also shows the boiling point of the organic solvent.

(2)印刷適應性 (2) Printing adaptability

藉由利用手工印刷的簡易凹版平板印刷而進行評價。藉由刮刀將實施導電性糊1著墨於設置有寬度3μm或5μm、深度5μm的槽的平板巴拉德(Ballard)鍍敷凹版中後，按壓至將矽酮膠板(金陽公司製造的SP11-1)捲繞的橡膠輥並與之接觸，使所需的圖案轉移至膠板上。其後，將所述膠板上的塗膜按壓至單片的PET膜(厚度為100μm)上，進行轉印、印刷而製成線寬度約3μm與5μm的印刷圖案。關於所獲得的印刷圖案，將線的直線性特別優異、無斷線部位者評價為「◎」，將線的直線性優異、無斷線部位者評價為「○」，將線的直線性差、無斷線部位者評價為「△」，將線的直線性差、有斷線部位者評價為「×」。另外，將不存在線的擴展者設為「○」，將稍微存在線的擴展者設為「△」，將存在線的擴展而有明顯的線變粗者設為「×」。將所獲得的結果示於表2中。 Evaluation was performed by simple gravure lithography using hand printing. The conductive paste 1 is applied with a squeegee to a flat plate Ballard plated intaglio plate with grooves of 3μm or 5μm in width and 5μm in depth, and then pressed to the silicone rubber sheet (SP11 manufactured by Jinyang) -1) The wound rubber roller and contact with it, so that the required pattern is transferred to the rubber sheet. After that, the coating film on the rubber sheet was pressed onto a single PET film (100 μm in thickness), transferred and printed, and printed patterns with line widths of approximately 3 μm and 5 μm were formed. Regarding the obtained print pattern, the line with particularly excellent linearity and no broken line was evaluated as "◎", the line with excellent linearity and no broken line was evaluated as "○", and the line with poor linearity, Those with no broken thread were evaluated as "△", and those with poor linearity and broken wires were evaluated as "×". In addition, the extensions without lines are set to "○", the extensions with slightly existing lines are set to "△", and the lines with extensions and obvious thickening are set to "×". The obtained results are shown in Table 2.

(3)分散性 (3) Dispersibility

將實施導電性糊1利用分散溶媒稀釋為2倍並靜置於容器中，室溫1天後，以目視來觀察沈澱的有無及上清液的狀態，藉此評價實施導電性糊1的分散性。將於容器下基本上未確認到沈降物的情況評價為「○」，將確認到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確認到沈降物的情 況評價為「×」。將所獲得的結果示於表2中。 The conductive paste 1 was diluted twice with a dispersion solvent and left in a container. After 1 day at room temperature, the presence or absence of the precipitate and the state of the supernatant were visually observed to evaluate the dispersion of the conductive paste 1 sex. The case where almost no sediment is confirmed under the container is evaluated as "○", and the case where a small amount of sediment is confirmed is evaluated as "△". There is a significant difference in concentration above and below the container and the sediment is clearly confirmed. The condition is evaluated as "×". The obtained results are shown in Table 2.

(4)體積電阻值 (4) Volume resistance value

於PET基材上利用凹版平板印刷對銀微粒子分散體進行配線形成(寬度為1mm、長度為1.5cm)，於齒輪烘箱中於120℃.30分鐘的條件下進行加熱．煅燒，藉此使其燒結，而形成導電性圖案。利用三和電氣計器(股)製造的「數位多用表(Digital multimeter)PM-3」於印刷配線的兩端測量所述導電性圖案的電阻值，使用基恩斯(Keyencec)(股)製造的形狀測定雷射顯微鏡(laser microscope)「VK-X100」測定厚度。 The dispersion of silver particles was formed by gravure printing on the PET substrate (width 1mm, length 1.5cm), and heated in a gear oven at 120°C for 30 minutes. By firing, it is sintered to form a conductive pattern. The resistance value of the conductive pattern was measured at both ends of the printed wiring using the "Digital Multimeter PM-3" manufactured by Sanwa Electric Meter Co., Ltd., and measured using the shape manufactured by Keyencec Co., Ltd. The laser microscope (laser microscope) "VK-X100" measures the thickness.

具體而言，根據以下式子，由測定端子間距離與導電性被膜的厚度來換算體積電阻值。將體積電阻值為50μΩ．cm以下的情況評價為「○」，將100μΩ．cm以下的情況評價為「△」，將所述以上的值的情況評價為「×」。將所獲得的結果示於表2中。 Specifically, the volume resistance value is converted from the measurement of the distance between the terminals and the thickness of the conductive film according to the following formula. Set the volume resistance value to 50μΩ. The case below cm is evaluated as "○", and 100μΩ. The case of cm or less was evaluated as "△", and the case of the above-mentioned value was evaluated as "×". The obtained results are shown in Table 2.

式：(體積電阻值ρv)=(電阻值R)×(被膜寬度w)×(被膜厚度t)/(端子間距離L) Formula: (Volume resistance value ρv)=(Resistance value R)×(film width w)×(film thickness t)/(distance between terminals L)

(5)密接性試驗 (5) Adhesion test

將賽珞膠帶(Cellotape)(註冊商標)貼附於印刷適應性評價中使用的PET基板上的印刷配線上，以撕剝時的斷裂狀況進行評價。具體而言，對5處印刷配線用力摩擦賽珞膠帶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。將所獲得的結果示於表2中。 Cellotape (registered trademark) was affixed to the printed wiring on the PET substrate used in the evaluation of printing suitability, and the evaluation was performed based on the fracture state during peeling. Specifically, five printed wiring lines were strongly rubbed against the Cyro tape and peeled off strongly in the vertical direction for evaluation. The case where the number of peeled pieces is 0 to 1 is evaluated as "○", the case of 2 to 3 sheets was evaluated as "△", and the case of 4 to 5 sheets was evaluated as "×", even if it was not completely peeled but partially peeled, it was regarded as peeled and counted as 1 sheet. The obtained results are shown in Table 2.

《實施例2》 "Example 2"

對於與實施例1同樣地獲得的銀奈米粒子漿料80重量份，將所添加的有機溶媒自1,3-丁二醇(和光純藥工業(股)製造的一級試劑)變更為17重量份的2乙基-1,3-己二醇異構體混合物(和光純藥工業(股)製造的一級試劑)，除此以外，與實施例1同樣地獲得實施導電性糊2。另外，與實施例1同樣地進行實施導電性糊2的評價，將所獲得的結果示於表2中。 For 80 parts by weight of the silver nanoparticle slurry obtained in the same manner as in Example 1, the organic solvent added was changed from 1,3-butanediol (a primary reagent manufactured by Wako Pure Chemical Industries, Ltd.) to 17 parts by weight Except for 2 parts of 2 ethyl-1,3-hexanediol isomer mixture (a primary reagent manufactured by Wako Pure Chemical Industries, Ltd.), in the same manner as in Example 1, a conductive paste 2 was obtained. In addition, evaluation of the conductive paste 2 was performed in the same manner as in Example 1, and the obtained results are shown in Table 2.

《實施例3》 "Example 3"

對於次微米銀(稀有金屬材料研究所公司製造粒徑分佈0.2μm~1.0μm)80重量份，添加使3重量份的作為樹脂材的S-REC KS-10(積水化學工業(股)製造)、0.5重量份的作為觸變劑的庫里斯塔森(Crystasense)MP(庫奧德(CLODA)公司製造)、0.5重量份的作為高分子分散劑的素司潘斯(SOLSPERSE)41000(日本路博潤(Japan Lubrizol)公司製造)溶解於16重量份的2乙基-1,3-己二醇異構體混合物(和光純藥工業(股)製造的一級試劑)中而得的混合溶液共計20重量份，除此以外，與實施例1同樣地獲得實施導電性糊3。另外，與實施例1同樣地進行實施導電性糊3的評價，將所獲得的結果示於表2中。 To 80 parts by weight of submicron silver (particle size distribution 0.2μm~1.0μm manufactured by Rare Metal Materials Research Institute Co., Ltd.), 3 parts by weight of S-REC KS-10 (manufactured by Sekisui Chemical Industry Co., Ltd.) are added as a resin material. , 0.5 parts by weight of Crystasense MP (manufactured by CLODA) as a thixotropic agent, 0.5 parts by weight of SOLSPERSE 41000 as a polymer dispersant (Japan Road The total mixed solution obtained by dissolving Borun (Japan Lubrizol) in 16 parts by weight of 2 ethyl-1,3-hexanediol isomer mixture (a primary reagent manufactured by Wako Pure Chemical Industries, Ltd.) Except 20 parts by weight, in the same manner as in Example 1, a conductive paste 3 was obtained. In addition, the conductive paste 3 was evaluated in the same manner as in Example 1, and the obtained results are shown in Table 2.

《實施例4》 "Example 4"

使用與實施例1同樣地獲得的銀奈米粒子漿料60重量份與次微米銀(稀有金屬材料研究所公司製造粒徑分佈0.2μm~1.0μm)20重量份、合計80重量份，除此以外，與實施例3同樣地獲得實施導電性糊4。另外，與實施例1同樣地進行實施導電性糊4的評價，將所獲得的結果示於表2中。 60 parts by weight of the silver nanoparticle paste obtained in the same manner as in Example 1 and 20 parts by weight of submicron silver (a particle size distribution 0.2μm~1.0μm manufactured by the Rare Metal Materials Research Institute Co., Ltd.) were used for a total of 80 parts by weight. Except for the above, in the same manner as in Example 3, a conductive paste 4 was obtained. In addition, the conductive paste 4 was evaluated in the same manner as in Example 1, and the obtained results are shown in Table 2.

《實施例5》 "Example 5"

對於利用與實施例1同樣的方法而獲得的銀奈米粒子漿料82重量份，將所添加的有機溶媒自17重量份的2乙基-1,3-己二醇異構體混合物(和光純藥工業(股)製造的一級試劑)變更為3重量份的秋瓦吉魯(Kyowadiol)PD-9(KH新化(KH NeoChem)公司製造)與12重量份的萜品醇(安原化學(Yasuhara Chemical)公司製造)的混合溶媒，除此以外，與實施例2同樣地獲得實施導電性糊5。另外，與實施例1同樣地進行實施導電性糊5的評價，將所獲得的結果示於表2中。 For 82 parts by weight of the silver nanoparticle slurry obtained by the same method as in Example 1, the organic solvent was added from 17 parts by weight of the 2-ethyl-1,3-hexanediol isomer mixture (and The primary reagent manufactured by Kok Pure Chemical Industry Co., Ltd.) was changed to 3 parts by weight of Kyowadiol PD-9 (manufactured by KH NeoChem) and 12 parts by weight of terpineol (Anyuan Chemical Co., Ltd.) Except for the mixed solvent of Yasuhara Chemical Co., Ltd., the conductive paste 5 was obtained in the same manner as in Example 2. In addition, the conductive paste 5 was evaluated in the same manner as in Example 1, and the obtained results are shown in Table 2.

《實施例6》 "Example 6"

對於利用與實施例1同樣的方法而獲得的銀奈米粒子漿料66重量份，將所添加的有機溶媒設為使3重量份的作為樹脂材的聚乙烯吡咯啶酮K30(和光純藥工業(股)製造的試劑)、1重量份的作為觸變劑的庫里斯塔森(Crystasense)MP(庫奧德(CLODA)公司製造)溶解於30重量份的2乙基-1,3-己二醇異構體混合物(和光純藥工業(股)製造的一級試劑)中而得的混合溶液共計34重量份，除此以外，與實施例1同樣地獲得實施導電性糊6。另外， 與實施例1同樣地進行實施導電性糊6的評價，將所獲得的結果示於表2中。 For 66 parts by weight of silver nanoparticle slurry obtained by the same method as in Example 1, the organic solvent added was set to 3 parts by weight of polyvinylpyrrolidone K30 (Wako Pure Chemical Industries, Ltd.) as a resin material. (Stock) reagent), 1 part by weight of Crystasense MP (manufactured by CLODA) as a thixotropic agent was dissolved in 30 parts by weight of 2 ethyl-1,3-hexane Except that the mixed solution obtained in the glycol isomer mixture (the primary reagent manufactured by Wako Pure Chemical Industries, Ltd.) totaled 34 parts by weight, the same procedure as in Example 1 was carried out to obtain conductive paste 6. in addition, The conductive paste 6 was evaluated in the same manner as in Example 1, and the obtained results are shown in Table 2.

《實施例7》 "Example 7"

對於利用與實施例1同樣的方法而獲得的銀奈米粒子漿料80重量份，將所添加的有機溶媒自17重量份的2乙基-1,3-己二醇異構體混合物(和光純藥工業(股)製造的一級試劑)變更為17重量份的丁基三乙二醇(和光純藥工業(股)製造的試劑)，除此以外，與實施例2同樣地獲得實施導電性糊7。另外，與實施例1同樣地進行實施導電性糊7的評價，將所獲得的結果示於表2中。 For 80 parts by weight of the silver nanoparticle slurry obtained by the same method as in Example 1, the organic solvent was added from 17 parts by weight of the 2-ethyl-1,3-hexanediol isomer mixture (and Except that the primary reagent manufactured by Ko Pure Chemical Industries Co., Ltd. was changed to 17 parts by weight of butyl triethylene glycol (reagent manufactured by Wako Pure Chemical Industries, Ltd.), the conductivity was obtained in the same manner as in Example 2 except that Paste 7. In addition, the conductive paste 7 was evaluated in the same manner as in Example 1, and the obtained results are shown in Table 2.

《實施例8》 "Example 8"

對於利用與實施例1同樣的方法而獲得的銀奈米粒子漿料80重量份，將所添加的樹脂密接材自3.0重量份的聚乙烯吡咯啶酮K30(和光純藥工業(股)製造的試劑)變更為3.0重量份的S-REC KS-10(和光純藥工業(股)製造的試劑)，除此以外，與實施例2同樣地獲得實施導電性糊8。另外，與實施例1同樣地進行實施導電性糊8的評價，將所獲得的結果示於表2中。 For 80 parts by weight of the silver nanoparticle slurry obtained by the same method as in Example 1, the resin adhesion material added was 3.0 parts by weight of polyvinylpyrrolidone K30 (manufactured by Wako Pure Chemical Industries, Ltd.) Except that the reagent) was changed to 3.0 parts by weight of S-REC KS-10 (a reagent manufactured by Wako Pure Chemical Industries, Ltd.), in the same manner as in Example 2, a conductive paste 8 was obtained. In addition, the conductive paste 8 was evaluated in the same manner as in Example 1, and the obtained results are shown in Table 2.

《實施例9》 "Example 9"

對於利用與實施例5同樣的方法而獲得的銀奈米粒子漿料80重量份，將所添加的有機溶媒自12重量份的萜品醇(安原化學(Yasuhara Chemical)公司製造)變更為12.0重量份的泰魯斯部(Terusolve)TOE-100(日本萜烯化學公司製造)，除此以外，與實施例2同樣地獲得實施導電性糊9。另外，與實施例1同樣地進 行實施導電性糊9的評價，將所獲得的結果示於表2中。 For 80 parts by weight of the silver nanoparticle slurry obtained by the same method as in Example 5, the added organic solvent was changed from 12 parts by weight of terpineol (manufactured by Yasuhara Chemical Co., Ltd.) to 12.0 parts by weight. Except that part of Terusolve TOE-100 (manufactured by Nippon Terpene Chemical Co., Ltd.), in the same manner as in Example 2, a conductive paste 9 was obtained. In addition, proceed in the same way as in Example 1. Conductive paste 9 was evaluated, and the obtained results are shown in Table 2.

《比較例1》 "Comparative Example 1"

對於利用與實施例1同樣的方法而獲得的銀奈米粒子漿料80重量份，將所添加的有機溶媒自17重量份的2乙基-1,3-己二醇異構體混合物(和光純藥工業(股)製造的一級試劑)變更為17重量份的辛醇(和光純藥工業(股)製造的試劑)，除此以外，與實施例2同樣地獲得比較導電性糊1。另外，與實施例1同樣地進行比較導電性糊1的評價，將所獲得的結果示於表3中。 For 80 parts by weight of the silver nanoparticle slurry obtained by the same method as in Example 1, the organic solvent was added from 17 parts by weight of the 2-ethyl-1,3-hexanediol isomer mixture (and Except that the primary reagent manufactured by Ko Pure Chemical Industries, Ltd. was changed to 17 parts by weight of octanol (reagent manufactured by Wako Pure Chemical Industries, Ltd.), the comparative conductive paste 1 was obtained in the same manner as in Example 2 except that it was changed to 17 parts by weight. In addition, the comparative conductive paste 1 was evaluated in the same manner as in Example 1, and the obtained results are shown in Table 3.

《比較例2》 "Comparative Example 2"

對於利用與實施例1同樣的方法而獲得的銀奈米粒子漿料80重量份，將所添加的有機溶媒自17重量份的2乙基-1,3-己二醇異構體混合物(和光純藥工業(股)製造的一級試劑)變更為17重量份的萜品醇(安原化學(Yasuhara Chemical)公司製造)，除此以外，與實施例2同樣地獲得比較導電性糊2。另外，與實施例1同樣地進行比較導電性糊2的評價，將所獲得的結果示於表3中。 For 80 parts by weight of the silver nanoparticle slurry obtained by the same method as in Example 1, the organic solvent was added from 17 parts by weight of the 2-ethyl-1,3-hexanediol isomer mixture (and Except that the primary reagent manufactured by Ko Pure Chemical Industries, Ltd. was changed to 17 parts by weight of terpineol (manufactured by Yasuhara Chemical Co., Ltd.), a comparative conductive paste 2 was obtained in the same manner as in Example 2 except that it was changed to 17 parts by weight. In addition, the comparative conductive paste 2 was evaluated in the same manner as in Example 1, and the obtained results are shown in Table 3.

《比較例3》 "Comparative Example 3"

對於利用與實施例1同樣的方法而獲得的銀奈米粒子漿料80重量份，將所添加的有機溶媒自17重量份的2乙基-1,3-己二醇異構體混合物(和光純藥工業(股)製造的一級試劑)變更為17重量份的泰魯斯部(Terusolve)TOE-100(日本萜烯化學公司製造)，除此以外，與實施例2同樣地獲得比較導電性糊3。另外，與實施例1同樣地進行比較導電性糊3的評價，將所獲得的結果示於表3 中。 For 80 parts by weight of the silver nanoparticle slurry obtained by the same method as in Example 1, the organic solvent was added from 17 parts by weight of the 2-ethyl-1,3-hexanediol isomer mixture (and The primary reagent manufactured by Ko Pure Chemical Industries Co., Ltd.) was changed to 17 parts by weight of Terusolve TOE-100 (manufactured by Nippon Terpene Chemical Co., Ltd.), and the comparative conductivity was obtained in the same manner as in Example 2 except that Paste 3. In addition, the comparative conductive paste 3 was evaluated in the same manner as in Example 1, and the obtained results are shown in Table 3. middle.

《比較例4》 "Comparative Example 4"

將利用與實施例1同樣的方法而獲得的銀奈米粒子漿料66重量份變更為65重量份，將所添加的有機溶媒自2乙基-1,3-己二醇異構體混合物(和光純藥工業(股)製造的一級試劑)30重量份變更為31重量份，除此以外，與實施例6同樣地獲得比較導電性糊4。另外，與實施例1同樣地進行比較導電性糊4的評價，將所獲得的結果示於表3中。 The silver nanoparticle slurry obtained by the same method as in Example 1 was changed from 66 parts by weight to 65 parts by weight, and the organic solvent added was changed from the 2-ethyl-1,3-hexanediol isomer mixture ( Except that 30 parts by weight of the primary reagent manufactured by Wako Pure Chemical Industries, Ltd. was changed to 31 parts by weight, the comparative conductive paste 4 was obtained in the same manner as in Example 6. In addition, the comparative conductive paste 4 was evaluated in the same manner as in Example 1, and the obtained results are shown in Table 3.

《比較例5》 "Comparative Example 5"

對於利用與實施例1同樣的方法而獲得的銀奈米粒子漿料80重量份，將所添加的有機溶媒自17重量份的2乙基-1,3-己二醇異構體混合物(和光純藥工業(股)製造的一級試劑)變更為17重量份的2-甲基-2,4-戊二醇(和光純藥工業(股)製造的一級試劑)，除此以外，與實施例2同樣地獲得比較導電性糊5。另外，與實施例1同樣地進行比較導電性糊5的評價，將所獲得的結果示於表3中。 For 80 parts by weight of the silver nanoparticle slurry obtained by the same method as in Example 1, the organic solvent was added from 17 parts by weight of the 2-ethyl-1,3-hexanediol isomer mixture (and The primary reagent manufactured by Ko Pure Chemical Industries Co., Ltd.) was changed to 17 parts by weight of 2-methyl-2,4-pentanediol (the primary reagent manufactured by Wako Pure Chemical Industries Co., Ltd.). In addition, the same as the examples 2 In the same manner, a comparative conductive paste 5 was obtained. In addition, the comparative conductive paste 5 was evaluated in the same manner as in Example 1, and the obtained results are shown in Table 3.

《比較例6》 "Comparative Example 6"

對於利用與實施例1同樣的方法而獲得的銀奈米粒子漿料82重量份，使用將秋瓦吉魯(Kyowadiol)PD-9(KH新化(KH NeoChem)公司製造)自3重量份變更為2重量份且將萜品醇(安原化學(Yasuhara Chemical)公司製造)自12重量份變更為13重量份而得的混合溶媒，除此以外，與實施例6同樣地獲得比較 導電性糊6。另外，與實施例1同樣地進行比較導電性糊6的評價，將所獲得的結果示於表3中。 For 82 parts by weight of silver nanoparticle slurry obtained by the same method as in Example 1, Kyowadiol PD-9 (manufactured by KH NeoChem) was changed from 3 parts by weight. It is a mixed solvent obtained by changing 2 parts by weight of terpineol (manufactured by Yasuhara Chemical Co., Ltd.) from 12 parts by weight to 13 parts by weight, and comparison is obtained in the same manner as in Example 6 except that Conductive paste 6. In addition, the comparative conductive paste 6 was evaluated in the same manner as in Example 1, and the obtained results are shown in Table 3.

Figure 106120276-A0305-02-0039-1
Figure 106120276-A0305-02-0039-1

Figure 106120276-A0305-02-0040-2
Figure 106120276-A0305-02-0040-2

Figure 106120276-A0305-02-0041-3
Figure 106120276-A0305-02-0041-3

根據表1~表3所示的結果可知：膠板膨潤率不會因膠板的種類而明顯地發生變化。再者，實施例1~實施例9及比較例1~比較例6中使用的膠板與「膠板A」相同，因而表2的膠板膨潤率顯示出與所述膠板相對應的值。 According to the results shown in Table 1 to Table 3, it can be seen that the rubber sheet swelling rate does not change significantly depending on the type of rubber sheet. Furthermore, the rubber sheets used in Examples 1 to 9 and Comparative Examples 1 to 6 are the same as "Paper A", so the rubber sheet swelling rate in Table 2 shows a value corresponding to the rubber sheet .

根據表2及表3所示的結果，作為本發明的導電性糊的實施導電性糊1~實施導電性糊9具有良好的分散性，除此以外，藉由使用該些導電性糊，可獲得線寬為5μm以下(5μm及3μm)的導電性圖案。另外，所述導電性圖案具有與基材的優異的密接性及高導電性。 According to the results shown in Table 2 and Table 3, as the conductive paste of the present invention, the conductive paste 1 to the conductive paste 9 have good dispersibility. In addition, by using these conductive pastes, A conductive pattern with a line width of 5 μm or less (5 μm and 3 μm) is obtained. In addition, the conductive pattern has excellent adhesion to the substrate and high conductivity.

另外，根據實施例3及實施例4可知：不僅於僅使用銀奈米粒子的情況下，而且即便於單獨使用比較大的銀次微米粒子、或者與銀奈米粒子混合使用的情況下，亦可獲得良好的導電性圖案。 In addition, according to Examples 3 and 4, it can be seen that not only in the case of using only silver nanoparticles, but also in the case of using relatively large silver submicron particles alone or in combination with silver nanoparticles. A good conductive pattern can be obtained.

另外，根據實施例5與實施例6的比較可知：即便於使用了溶媒的膠板膨潤率超過2.0%的溶媒的情況下，藉由含有3.0wt%以上的膠板膨潤率為2.0%以下的溶媒，而可進行細線印刷。 In addition, a comparison between Example 5 and Example 6 shows that even in the case of using a solvent with a rubber sheet swelling rate exceeding 2.0%, by containing 3.0wt% or more of rubber sheet swelling rate of 2.0% or less Solvent, and fine line printing can be performed.

另外，根據實施例6與比較例4的比較可知：若添加30wt%的膠板膨潤率為2.0%以下的溶媒，則即便於在對導電性的影響小的範圍內加入觸變劑的情況下，黏度亦稍稍下降，且稍微確認到線的擴展，但可進行細線印刷；相對於此，若所述添加量超過31.0wt%，則線的擴展變得更大，而發生線變寬。 In addition, from the comparison between Example 6 and Comparative Example 4, it can be seen that if 30 wt% of a solvent with a swelling rate of 2.0% or less is added, even when the thixotropic agent is added in the range where the influence on the conductivity is small , The viscosity is also slightly decreased, and the line expansion is slightly confirmed, but fine line printing can be performed; on the contrary, if the addition amount exceeds 31.0wt%, the line expansion becomes larger, and the line becomes wider.

另外，根據比較例1~比較例3可知若溶媒的膠板膨潤 率為2.0%以上，則無法應對細線印刷，根據比較例2及比較例3可知即便於使用了高沸點溶劑的情況下，若膠板膨潤率超過2.0%，則細線印刷困難。 In addition, according to Comparative Example 1 to Comparative Example 3, it can be seen that if the rubber sheet of the solvent swells If the rate is 2.0% or more, fine line printing cannot be handled. According to Comparative Example 2 and Comparative Example 3, even when a high-boiling point solvent is used, if the swelling rate of the rubber sheet exceeds 2.0%, fine line printing is difficult.

進而，根據比較例5可知：即便於使用了膠板膨潤率為2.0%以下的溶媒的情況下，若沸點低於200℃，則無法應對線寬為3μm的細線印刷。 Furthermore, according to Comparative Example 5, even in the case of using a solvent having a rubber sheet swelling rate of 2.0% or less, if the boiling point is lower than 200° C., the printing of fine lines with a line width of 3 μm cannot be applied.

Claims (4)

一種導電性糊，包含：銀微粒子及有機溶媒，所述有機溶媒包含膠板膨潤率成為2.0%以下的低膨潤性有機溶媒，所述低膨潤性有機溶媒的含有率為3.0wt%~30wt%，所述銀微粒子的表面至少一部分附著有3-甲氧基丙基胺。 A conductive paste, comprising: silver particles and an organic solvent, the organic solvent comprising a low-swelling organic solvent with a rubber sheet swelling rate of 2.0% or less, and the content of the low-swelling organic solvent is 3.0wt%-30wt% , 3-methoxypropylamine is attached to at least a part of the surface of the silver fine particles. 如申請專利範圍第1項所述的導電性糊，其中所述銀微粒子為銀奈米粒子。 The conductive paste described in the first item of the scope of patent application, wherein the silver fine particles are silver nano particles. 如申請專利範圍第1項或第2項所述的導電性糊，其中所述低膨潤性有機溶媒的常壓下的沸點為200℃以上，所述低膨潤性有機溶媒具有羥基。 The conductive paste described in item 1 or item 2 of the scope of patent application, wherein the low swelling organic solvent has a boiling point at normal pressure of 200° C. or more, and the low swelling organic solvent has a hydroxyl group. 一種導電性圖案的形成方法，其特徵在於：使用利用了凹版的凹版平板印刷法，所述凹版具有於印刷面填充有印刷用導電性糊的凹部，所述凹部對應於線寬為10μm以下的細線圖案的印刷，所述印刷用導電性糊使用如申請專利範圍第1項至第3項中任一項所述的導電性糊。A method for forming a conductive pattern, which is characterized by using a gravure lithography method using an intaglio plate having a concave portion filled with a conductive paste for printing on a printing surface, and the concave portion corresponds to a line width of 10 μm or less For printing of fine line patterns, the conductive paste for printing uses the conductive paste described in any one of items 1 to 3 in the scope of the patent application.
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