TW201306049A - Tabular silver particle, manufacturing method therefor, paste using same, and printed circuit using paste - Google Patents

Tabular silver particle, manufacturing method therefor, paste using same, and printed circuit using paste Download PDF

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TW201306049A
TW201306049A TW101115136A TW101115136A TW201306049A TW 201306049 A TW201306049 A TW 201306049A TW 101115136 A TW101115136 A TW 101115136A TW 101115136 A TW101115136 A TW 101115136A TW 201306049 A TW201306049 A TW 201306049A
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silver
sem
particle diameter
flat
particles
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TW101115136A
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TWI530963B (en
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Taro Nakanoya
Takashi Hinotsu
Hirotoshi Saito
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Dowa Electronics Materials Co
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    • 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
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0551—Flake form nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells

Abstract

Provided is a conductive paste that exhibits a low resistance even with thermal treatment at a low temperature of approximately 200 DEG C. Also provided is a tabular silver particle wherein: organic matter with a carbon number of 2-10 is attached on the surface thereof; and the average particle diameter in the thickness direction calculated with an SEM image (hereafter referred to as dSEM-T) is 10-200 nm. The silver particle is characterized by having an aspect ratio, which is the ratio (dSEM-L/dSEM-T) between the average particle diameter in the lengthwise direction (dSEM-L) and the dSEM-T, of 2-100.

Description

平板狀之銀微粒子和其製造方法，及使用其之糊膏和使用糊膏之印刷電路 Flat silver microparticles and a method for producing the same, and a paste using the same and a printed circuit using the paste

本發明係關於適用於微細佈線、接合體等的平板狀之銀微粒子和其製造方法、及含有該粒子的糊膏和使用該糊膏的印刷電路。 The present invention relates to a flat silver microparticle suitable for use in fine wiring, a bonded body, and the like, a method for producing the same, a paste containing the particles, and a printed circuit using the paste.

過去以來，為了形成電子零件的電極或電路，係使用使銀粒子分散於有機介質中的導電性糊膏。導電性糊膏所使用的銀粒子，較佳係使用銀粒子彼此間的接觸面積較大之平板狀銀粒子(例如參照專利文獻1)。 In the past, in order to form an electrode or an electric circuit of an electronic component, a conductive paste in which silver particles are dispersed in an organic medium is used. The silver particles used for the conductive paste are preferably plate-like silver particles having a large contact area between the silver particles (see, for example, Patent Document 1).

再者，近年隨電子機器的小型化演進，正指向佈線的微細化進展。特別係為達佈線的微細化，便必須在確保所描繪之佈線的導電性之前提下，使佈線更纖細地形成。因此，銀粒子本身亦朝微粒子化演進。專利文獻2揭示有利用濕式反應所獲得的平板狀之銀微粒子。 In addition, in recent years, with the miniaturization of electronic equipment, the progress of the miniaturization of the wiring is progressing. In particular, in order to miniaturize the wiring, it is necessary to lift the wiring before ensuring the conductivity of the drawn wiring, and to form the wiring finer. Therefore, the silver particles themselves are also evolving toward microparticles. Patent Document 2 discloses flat silver microparticles obtained by a wet reaction.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利第3874634號公報 [Patent Document 1] Japanese Patent No. 3874634

[專利文獻2]日本專利特開2009-13449號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-13449

依單純步驟獲得具有平板形狀之銀微粒子的手法，如先前 所示，可例示專利文獻2所記載的方法。但是，為了能以所製得之微粒子獲得具有導電性的膜，須有250℃的加熱。已知若銀微粒子微細化便可降低熔點，若需要進行該溫度的加熱，則難謂可充分享受將銀微細化的效果。結果，會有形成金屬佈線的基板種類亦受限制的問題。因此，期待提供能以更低溫呈現導電性的糊膏。 A method of obtaining silver particles having a flat shape in a simple step, as before The method described in Patent Document 2 can be exemplified. However, in order to obtain a film having conductivity from the obtained fine particles, heating at 250 ° C is required. It is known that if the silver fine particles are made fine, the melting point can be lowered, and if it is necessary to heat the temperature, it is difficult to sufficiently enjoy the effect of refining silver. As a result, there is a problem that the type of the substrate on which the metal wiring is formed is also limited. Therefore, it is expected to provide a paste which can exhibit electrical conductivity at a lower temperature.

本發明係有鑒於此種習知技術所存在的問題而完成，其目的在於提供：即便經由200℃左右的低溫熱處理，仍呈現低電阻值的導電性糊膏。 The present invention has been made in view of the problems of the prior art, and it is an object of the invention to provide a conductive paste having a low electrical resistance value even after heat treatment at a low temperature of about 200 °C.

本發明者等人為達成此目的，經深入鑽研，結果發現藉由使用以下所示的平板狀之銀微粒子、平板狀之銀微粒子之製造方法、及含有上述平板狀之銀微粒子的導電性糊膏，便可解決上述問題。 In order to achieve this object, the inventors of the present invention have intensively studied and found that the use of the flat silver microparticles, the flat silver microparticles, and the conductive paste containing the flat silver microparticles described above are used. , can solve the above problems.

本發明的粒子係平板狀之銀微粒子，在其表面上附著有碳數2~10的有機物，從SEM影像所計算出之厚度方向的粒徑平均值(以下記載為「dSEM-T」)係10~200nm，且長邊方向的粒徑平均值(dSEM-L)與上述厚度方向的粒徑平均值(dSEM-T)之比(dSEM-L/dSEM-T)的深寬比係2~100。 In the particle-shaped silver fine particles of the present invention, an organic substance having 2 to 10 carbon atoms is adhered to the surface of the particles, and the average particle diameter in the thickness direction calculated from the SEM image (hereinafter referred to as "d SEM-T ") 10 to 200 nm, and the ratio of the average particle diameter (d SEM-L ) in the longitudinal direction to the average particle diameter (d SEM-T ) in the thickness direction (d SEM-L /d SEM-T ) is deep. The width ratio is 2~100.

本發明的平板狀之銀微粒子之製造方法，係將水溶性銀化合物、水溶性錯合劑、碳數3~10的有機物、及由有機物所構成的還原劑添加至水中，而製作平板狀之銀微粒子。 In the method for producing flat silver microparticles of the present invention, a water-soluble silver compound, a water-soluble complexing agent, an organic substance having 3 to 10 carbon atoms, and a reducing agent composed of an organic substance are added to water to prepare a flat silver. Microparticles.

再者，平板狀之銀微粒子之製造方法中，係添加檸檬酸或其衍生物。 Further, in the method for producing flat silver microparticles, citric acid or a derivative thereof is added.

再者，平板狀之銀微粒子之製造方法中，由有機物所構成的還原劑係抗壞血酸或其衍生物或異構物。 Further, in the method for producing flat silver microparticles, the reducing agent composed of an organic substance is ascorbic acid or a derivative or an isomer thereof.

本發明的導電性糊膏係含有上述平板狀之銀微粒子。 The conductive paste of the present invention contains the above-mentioned flat silver fine particles.

再者，在導電性糊膏中，係共同混合有上述平板狀之銀微粒子，與從SEM影像所計算出之長邊方向的粒徑平均值(以下記載為「DSEM-L」)為2.5~15.0μm、且相對於上述平板狀之銀微粒子之dSEM-L為3~50倍範圍之銀粒子。 In addition, in the conductive paste, the above-mentioned flat silver fine particles are mixed, and the average particle diameter in the longitudinal direction calculated from the SEM image (hereinafter referred to as "D SEM-L ") is 2.5. ~15.0 μm, and the SEM-L of the flat silver microparticles is in the range of 3 to 50 times the silver particles.

再者，上述銀粒子的形狀係平板狀。 Further, the shape of the silver particles is a flat plate shape.

藉由使用本發明所示之糊膏形成佈線，便可形成即便經由200℃左右的低溫熱處理，仍呈現充分導電性的佈線，俾可擴大基板的選擇幅度。 By forming the wiring using the paste of the present invention, it is possible to form a wiring which exhibits sufficient conductivity even after heat treatment at a low temperature of about 200 ° C, and the selection range of the substrate can be increased.

以下，針對平板狀之銀微粒子、平板狀之銀微粒子之製造方法、及導電性糊膏的最佳形態進行說明。 Hereinafter, a description will be given of a method of producing flat silver microparticles, flat silver microparticles, and a conductive paste.

<平板狀之銀微粒子> <flat silver particles>

本發明的平板狀之銀微粒子係利用碳數2~10的有機物被覆表面。若利用碳數超過10的高分子有機物進行被覆，則在形成導電膜時，會導致較難於低溫使有機物進行熱分解。結果，無法充分降低電阻值，故而不佳。被覆表面的有機物 較佳係碳數2~8、更佳係碳數2~6的有機物。又，即便為碳數較少的有機物，若被覆量變多，便會產生如前述無法降低電阻值的問題。被覆量可為3.0質量%以下且0.1質量%以上，較佳係2.0質量%以下且0.1質量%以上、更佳係1.0質量%以下且0.1質量%以上。 The flat silver microparticles of the present invention are coated on the surface with an organic substance having 2 to 10 carbon atoms. When coating with a polymer organic substance having a carbon number of more than 10, it is difficult to thermally decompose the organic substance at a low temperature when the conductive film is formed. As a result, the resistance value cannot be sufficiently lowered, which is not preferable. Organic matter covering the surface It is preferably an organic substance having 2 to 8 carbon atoms and more preferably 2 to 6 carbon atoms. Moreover, even if the amount of coating is increased, the amount of coating is increased, and the problem that the resistance value cannot be lowered as described above occurs. The coating amount may be 3.0% by mass or less and 0.1% by mass or more, preferably 2.0% by mass or less and 0.1% by mass or more, more preferably 1.0% by mass or less and 0.1% by mass or more.

再者，本發明的平板狀之銀微粒子係dSEM-T為10~200nm。若厚度方向的粒徑有變化，則相對地粒子長邊方向大小亦會有變化，因而若逾越此範圍之外，便會如上述般因糊膏的黏度、填充性而產生不良情況。另外，dSEM-T值更佳係10~190nm。又，此處所謂「長邊方向大小」係指板狀形狀的板面部分之對角線中，所觀測到最長的長度。 Further, the flat silver fine particle system of the present invention has a d SEM-T of 10 to 200 nm. When the particle diameter in the thickness direction changes, the size of the particle in the longitudinal direction also changes. Therefore, if it exceeds this range, the viscosity and the filling property of the paste may cause defects as described above. Further, the d SEM-T value is more preferably 10 to 190 nm. Here, the term "size in the longitudinal direction" means the longest length observed in the diagonal of the plate-like portion of the plate shape.

再者，本發明的平板狀之銀微粒子係粒子深寬比(dSEM-L/dSEM-T)較佳為2~100、更佳為3~50。藉由將深寬比在此範圍內的平板狀之銀微粒子、與市售銀粒子進行混合，便可使塗佈膜的填充性呈良好，有效於降低電阻率。又，藉由增加接觸面積，亦有效於降低接觸電阻。此時，平板狀之銀微粒子係dSEM-L為60~2,000nm、更佳為105~1,900nm。 Further, the aspect ratio (d SEM-L /d SEM-T ) of the flat silver microparticle particles of the present invention is preferably 2 to 100, more preferably 3 to 50. By mixing the flat silver microparticles having an aspect ratio within this range with commercially available silver particles, the filling property of the coating film can be improved, and the electrical resistivity can be effectively reduced. Moreover, by increasing the contact area, it is also effective in reducing the contact resistance. At this time, the flat silver fine particle system d SEM-L is 60 to 2,000 nm, more preferably 105 to 1,900 nm.

<平板狀之銀微粒子之製造方法> <Method for Producing Flat Silver Particles>

本發明的平板狀之銀微粒子之製造法，係採用濕式還原法，利用銀離子分散液之調液步驟、銀之還原步驟、銀粒子之洗淨步驟、以及銀粒子之乾燥步驟，而獲得平板狀之銀微粒子。以下，針對本發明的銀微粒子之製造方法進行詳細說 明。 The method for producing the flat silver microparticles of the present invention is obtained by a wet reduction method using a liquid adjusting step of a silver ion dispersion, a silver reduction step, a silver particle washing step, and a silver particle drying step. Flat silver particles. Hereinafter, the method for producing silver fine particles of the present invention will be described in detail. Bright.

(銀離子分散液之調液步驟) (Step of adjusting the silver ion dispersion)

本步驟中，將銀化合物、錯合物、以及碳數3~10的有機物進行混合，而獲得銀離子分散液。針對本步驟所使用的物質，以下進行詳細說明。 In this step, a silver compound, a complex compound, and an organic substance having 3 to 10 carbon atoms are mixed to obtain a silver ion dispersion. The materials used in this step will be described in detail below.

(銀化合物) (silver compound)

從成本、安全性的觀點而言，本反應較佳係在水中實施，若成為原料的銀化合物亦屬於水溶性，從反應均勻性的觀點而言，係屬較佳。具體而言，對水呈現溶解性的銀化合物係可例示硝酸銀、醋酸銀等，從溶解容易度的觀點而言，較佳係硝酸銀。又，亦可利用銀本身經酸溶解的溶液。 From the viewpoint of cost and safety, the reaction is preferably carried out in water, and the silver compound which is a raw material is also water-soluble, and is preferred from the viewpoint of reaction uniformity. Specifically, a silver compound which is soluble in water can be exemplified by silver nitrate or silver acetate, and silver nitrate is preferred from the viewpoint of ease of dissolution. Further, a solution in which silver itself is dissolved by an acid can also be used.

(錯合劑) (missing agent)

所謂「錯合劑」係指與金屬離子相鍵結而使錯離子形成者。藉由使用錯合劑，便可安定地生成平板狀之銀微粒子。又，藉由使反應液成為酸性側，便可使將粒子形狀調整為平板狀之事較為容易。因此，較佳係在水溶液中使用酸性錯合劑。此種錯合劑係可例示如檸檬酸、酒石酸、葡萄糖酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、蘋果酸、反丁烯二酸、順丁烯二酸、伊康酸、酞酸、異酞酸、對酞酸等羧酸或氧基羧酸系錯合劑；以及EDTA(乙二胺四醋酸)、DTPA(二乙三胺五醋酸)、IDA(亞胺二醋酸)、NTA(氮基三醋酸)等胺羧酸系錯合劑。 The term "mismatching agent" refers to a bond that is bonded to a metal ion to form a wrong ion. By using a miscible agent, flat silver particles can be stably formed. Moreover, by making the reaction liquid acidic, it is easy to adjust the particle shape to a flat shape. Therefore, it is preferred to use an acidic complexing agent in an aqueous solution. Such a complexing agent can be exemplified by, for example, citric acid, tartaric acid, gluconic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, fumaric acid, maleic acid, and ikon. a carboxylic acid or oxycarboxylic acid-based complexing agent such as acid, citric acid, isophthalic acid or p-nonanoic acid; and EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), IDA (imine diacetate) An amine carboxylic acid-based complexing agent such as NTA (nitrotriacetic acid).

(被覆物用有機物) (organic matter for coatings)

碳數3~10的有機物係作為所還原析出之銀微粒子的立體障礙而發揮作用，防止粒子彼此間進行凝集。若碳數為1、2，便無法充分發揮作為立體障礙的作用，導致粒子呈粗大化。另一方面，若碳數大於10，因為較難以低溫使有機物進行熱分解，因而導致在成形為導電性膜時無法充分降低電阻值，故而不佳。較佳係碳數3~8、更佳係碳數3~6的有機物。 The organic substance having 3 to 10 carbon atoms functions as a steric hindrance of the precipitated silver fine particles, and prevents aggregation of the particles. When the carbon number is 1, 2, the effect as a steric obstacle cannot be fully exerted, and the particles are coarsened. On the other hand, when the carbon number is more than 10, since it is difficult to thermally decompose the organic substance at a low temperature, the resistance value cannot be sufficiently lowered when it is formed into a conductive film, which is not preferable. It is preferably an organic substance having a carbon number of 3 to 8, more preferably a carbon number of 3 to 6.

(銀之還原步驟) (silver reduction step)

本步驟中，係對上述調液步驟所製作的銀離子分散液，藉由添加還原劑而獲得銀微粒子。針對本步驟所使用的還原劑進行詳細說明。 In this step, silver fine particles are obtained by adding a reducing agent to the silver ion dispersion prepared in the above liquid adjustment step. The reducing agent used in this step will be described in detail.

(還原劑) (reducing agent)

為能獲得均勻的平板狀粒子，必須使用還原力較弱的還原劑。具體而言，較佳係由有機物所構成的還原劑。更具體係可例示如屬於具有醛基之有機物的甲酸、草酸、抗壞血酸、乙醛；屬於單糖類的葡萄糖(glucose)、果糖(fructose)；屬於二糖類的麥芽糖(maltose)、纖維雙糖、果糖。 In order to obtain uniform plate-like particles, it is necessary to use a reducing agent having a weak reducing power. Specifically, a reducing agent composed of an organic substance is preferred. More system can be exemplified by formic acid, oxalic acid, ascorbic acid, acetaldehyde belonging to an organic substance having an aldehyde group; glucose, fructose belonging to a monosaccharide; maltose, cellobiose, fructose belonging to a disaccharide .

(銀微粒子之回收及洗淨步驟) (Recovery and washing steps of silver particles)

在經過還原步驟而獲得的銀微粒子中，因為含有未受被覆的過剩有機物，因而在回收粒子之後必須將有機物予以洗淨。洗淨溶劑較佳係使用純水。回收及洗淨的方式係可舉例 如傾析法、壓濾法等，惟並不僅侷限於該等。 In the silver fine particles obtained by the reduction step, since the unretained excess organic matter is contained, the organic matter must be washed after the particles are recovered. The washing solvent is preferably pure water. Recycling and washing methods are examples Such as decantation, pressure filtration, etc., but not limited to these.

(銀微粒子之乾燥步驟) (drying step of silver particles)

因為經洗淨後的粒子會含有較多的水分，因而在使用前必須去除水分。水分除去的方法較佳係採取真空乾燥。溫度較佳係設為100℃以下，更佳係設為80℃以下。若過度施加熱，在乾燥的時點會導致粒子彼此間進行燒結，故而不佳。 Since the washed particles will contain more water, the water must be removed before use. The method of removing moisture is preferably vacuum drying. The temperature is preferably set to 100 ° C or lower, more preferably 80 ° C or lower. If heat is excessively applied, the particles may be sintered at the time of drying, which is not preferable.

<銀微粒子之評估方法> <Evaluation method of silver microparticles>

所製作的平板狀之銀微粒子係依照以下的方法，實施被覆物的附著量評估、被覆物的碳數評估、粒徑的評估。 The produced silvery silver plate particles were subjected to the following methods to evaluate the adhesion amount of the coating material, the carbon number evaluation of the coating material, and the evaluation of the particle diameter.

(被覆物的附著量) (the amount of adhesion of the covering)

被覆物的附著量係將銀微粒子以成為厚度1~2mm之方式裝入灰分測定用灰皿(方型50×30×10mm)中，將該灰分測定用灰皿利用蒙烰爐(Muffle Furnace)(YAMATO科學股份有限公司製FO310)進行燒成，再從該燒成前後的質量計算出。又，該燒成的條件係在大氣中依升溫速度10℃/min，從25℃升溫至700℃，然後再施行自然冷卻直到冷卻至室溫為止的條件。 The amount of adhesion of the coating material is such that the silver fine particles are placed in a ash measuring ash dish (square type 50 × 30 × 10 mm) so as to have a thickness of 1 to 2 mm, and the ash measuring ash dish is used in a Muffle Furnace (YAMATO) The chemical product company FO310) is fired and calculated from the mass before and after the firing. Further, the conditions for the firing were carried out in the air at a temperature elevation rate of 10 ° C/min, from 25 ° C to 700 ° C, and then natural cooling was carried out until cooling to room temperature.

(被覆物的碳數評估) (assessment of carbon number of the covering)

被覆物的碳數係例如藉由將所獲得銀粒子利用GC-MS施行有機物成分的確認而實施。本發明中，係使用GC-MS裝置(Aglent technologies股份有限公司製的7890A GC System及5975C inert XL EI/CI MSD)，在氦環境下，將銀粒子加熱 至350℃，再將氣化的氣體成分使用管柱(J&W Scientific公司製DB-5HT 123-5731，流量2.0ml/分鐘)施行分離、捕集，而實施被覆物的評估。 The carbon number of the coating material is carried out, for example, by confirming the obtained silver particles by GC-MS. In the present invention, silver particles are heated in a helium environment using a GC-MS apparatus (7890A GC System and 5975C inert XL EI/CI MSD manufactured by Aglent Technologies Co., Ltd.). The vaporized gas component was separated and collected using a column (DB-5HT 123-5731, manufactured by J&W Scientific Co., Ltd., flow rate: 2.0 ml/min) at 350 ° C, and the evaluation of the coating was carried out.

(粒徑評估) (particle size assessment)

再者，本發明中，長邊方向與厚度方向的粒徑計算方法係如下示。使用掃描式電子顯微鏡(日立高科技製S-4700)實施粒子表面的觀察。觀察時的放大倍率係當粒子尺寸大約為500nm以下時便設為30,000倍，當粒子尺寸大約為500~2,000nm時便設為10,000倍，當粒子尺寸大約為2,000nm以上時便設為3,000倍。針對經觀察所獲得之50個以上的任意粒子，利用影像解析軟體[旭化成工程股份有限公司製A像君(註冊商標)]計算出粒徑。 Further, in the present invention, the method of calculating the particle diameter in the longitudinal direction and the thickness direction is as follows. Observation of the particle surface was carried out using a scanning electron microscope (S-4700 manufactured by Hitachi High-Tech Co., Ltd.). The magnification at the time of observation is set to 30,000 times when the particle size is about 500 nm or less, 10,000 times when the particle size is about 500 to 2,000 nm, and 3,000 times when the particle size is about 2,000 nm or more. . The particle size was calculated using the image analysis software [A-Jun (registered trademark) manufactured by Asahi Kasei Engineering Co., Ltd.) for 50 or more arbitrary particles obtained by observation.

<含有平板狀之銀微粒子的糊膏> <paste containing flat silver microparticles>

針對使用本發明所記載之平板狀之銀微粒子而製作的導電性糊膏進行詳細說明。 The conductive paste produced by using the flat silver microparticles described in the present invention will be described in detail.

(銀粒子) (silver particles)

對於銀粒子，其特徵在於使用本發明所記載之平板狀之銀微粒子。又，亦可混合使用依公知方法所製作的銀粒子，一般而言，所混合銀粒子的形狀較佳係平板狀之銀粒子。 The silver particles are characterized in that the flat silver microparticles described in the present invention are used. Further, silver particles produced by a known method may be used in combination. In general, the shape of the mixed silver particles is preferably a flat silver particle.

所混合的銀粒子較佳係DSEM-L為2.5~15.0μm，且為本發明所記載平板狀之銀微粒子的dSEM-L之3~50倍。更佳係DSEM-L為3.0~10.0μm，且為平板狀之銀微粒子的dSEM-L之 5~20倍。藉由依此混合大小不同的2種銀粉末，便可使填充性呈良好，俾使電阻率與接觸電阻呈良好。 The silver particles to be mixed preferably have a D SEM-L of 2.5 to 15.0 μm, and are 3 to 50 times larger than the d SEM-L of the flat silver microparticles described in the present invention. More preferably, the D SEM-L is 3.0 to 10.0 μm, and is 5 to 20 times the d SEM-L of the flat silver microparticles. By mixing two kinds of silver powders having different sizes, the filling property is good, and the electrical resistivity and the contact resistance are good.

(分散媒) (dispersion medium)

本發明的導電性糊膏中所使用之分散媒，較佳係屬於極性溶劑。若選擇極性溶劑，因為蒸氣壓較低，就操作方面而言係較佳。特別係若使用與各種樹脂具有相溶性質者便不會有問題，較佳係使用酯系、醚系、酮系、醚酯系、醇系、烴系、胺系等有機溶劑。 The dispersion medium used in the conductive paste of the present invention is preferably a polar solvent. If a polar solvent is selected, since the vapor pressure is low, it is preferable in terms of handling. In particular, if it is compatible with various resins, there is no problem, and an organic solvent such as an ester system, an ether system, a ketone system, an ether ester system, an alcohol system, a hydrocarbon system or an amine system is preferably used.

(分散劑) (Dispersant)

在本發明的導電性糊膏中亦可添加能使銀粒子更良好分散的分散劑。藉由使用此種分散劑，在糊膏中便可確保粒子的獨立性。就其性質而言，只要是與粒子表面間具有親和性，且對分散媒亦具有親和性者便可，亦可使用市售通用物。例如不僅為單獨種類、亦可併用使用。其添加量係相對於銀粒子的質量為3.0質量%以下、較佳係1.0質量%以下、更佳係0.5質量%以下。 A dispersing agent capable of more effectively dispersing silver particles may be added to the conductive paste of the present invention. By using such a dispersant, the independence of the particles can be ensured in the paste. As far as the nature is concerned, as long as it has affinity with the surface of the particles and has affinity for the dispersion medium, a commercially available general product can also be used. For example, it may be used not only in a single type but also in combination. The amount of addition is 3.0% by mass or less, preferably 1.0% by mass or less, and more preferably 0.5% by mass or less based on the mass of the silver particles.

(樹脂) (resin)

在本發明的導電性糊膏中所應添加之樹脂，係可採用廣泛周知的熱硬化型或熱可塑型之任一種樹脂。作為具體例，就熱硬化性樹脂而言，可自酚樹脂、環氧樹脂、不飽和聚酯樹脂、異氰酸酯化合物、三聚氰胺樹脂、脲樹脂、聚矽氧樹脂等之中選擇。又，就熱可塑性樹脂而言，可自丙烯酸系樹脂、 聚酯樹脂、聚胺基甲酸酯樹脂等之中選擇。樹脂的添加量係相對於銀粒子的質量，可設為2~20質量%、較佳為2~15質量%。若所添加的樹脂量過多，則會導致經燒成後在佈線中殘留必要以上的樹脂，而對導電性造成大幅影響，故而不佳。另一方面，若添加量較少，則無法確保佈線與基板間之密接性，因而必須至少添加2質量%左右。 The resin to be added to the conductive paste of the present invention may be any of a wide range of well-known thermosetting or thermoplastic resins. As a specific example, the thermosetting resin can be selected from among a phenol resin, an epoxy resin, an unsaturated polyester resin, an isocyanate compound, a melamine resin, a urea resin, a polyoxymethylene resin, and the like. Moreover, in the case of a thermoplastic resin, it can be derived from an acrylic resin, It is selected among polyester resins, polyurethane resins, and the like. The amount of the resin added is 2 to 20% by mass, preferably 2 to 15% by mass, based on the mass of the silver particles. When the amount of the resin to be added is too large, a resin which is required to remain in the wiring after firing is caused to have a large influence on the conductivity, which is not preferable. On the other hand, when the amount of addition is small, the adhesion between the wiring and the substrate cannot be ensured, and therefore it is necessary to add at least about 2% by mass.

在導電性糊膏中，一般大多均有使用熱硬化型環氧樹脂，而在環氧樹脂中，從提高儲存安定性的觀點而言，較佳係多元環氧化合物。又，多元環氧樹脂之中，較佳係生產性壓倒性高的環氧丙基型環氧樹脂，從硬化物的接著性與耐熱性優異之觀點而言，更佳係多元酚類經施行環氧丙基化而成的環氧樹脂。依此，較佳係雙酚型環氧樹脂、特佳係將雙酚A施行環氧丙基化而成的環氧樹脂、以及將雙酚F施行環氧丙基化而成的環氧樹脂。 In the conductive paste, a thermosetting epoxy resin is generally used in many cases, and in the epoxy resin, a polyvalent epoxy compound is preferred from the viewpoint of improving storage stability. Further, among the polyvalent epoxy resins, a epoxy propylene type epoxy resin having high productivity and high overwhelming property is preferable, and from the viewpoint of excellent adhesion and heat resistance of the cured product, it is preferable that the polyphenols are subjected to execution. Epoxy resin obtained by epoxy propylation. Accordingly, a bisphenol type epoxy resin, an epoxy resin obtained by subjecting bisphenol A to epoxy propylation, and an epoxy resin obtained by performing epoxy propylation of bisphenol F are preferred. .

再者，樹脂的形態較佳係呈液狀。另外，環氧當量較佳係300以下。若環氧當量成為大於300的值，則組成物會變成固態，導致電阻值提高，且在使用之際會造成操作上的不便，故而不佳。 Further, the form of the resin is preferably liquid. Further, the epoxy equivalent is preferably 300 or less. If the epoxy equivalent becomes a value of more than 300, the composition becomes solid, resulting in an increase in the electric resistance value, and it is inconvenient in handling at the time of use, which is not preferable.

當樹脂係使用環氧樹脂的情況，便必須併用硬化劑，硬化劑的種類係可使用市售通用物。又，不僅可為單獨種類，亦可併用使用。硬化劑的種類係可舉例如：胺系硬化劑、酸酐系硬化劑、咪唑類、路易斯酸(Lewis acid)、布忍斯特酸 (Bronsted acid)、酚樹脂等。 When an epoxy resin is used as the resin, a hardener must be used in combination, and a commercially available general product can be used as the type of the hardener. Moreover, it can be used not only in a single type but also in combination. Examples of the type of the curing agent include an amine curing agent, an acid anhydride curing agent, an imidazole, a Lewis acid, and a Brilliant acid. (Bronsted acid), phenol resin, and the like.

<導電性糊膏之製造> <Manufacture of conductive paste>

將銀粒子、以及分散媒、樹脂等成分進行混合後，導入混練脫泡機中而形成該成分的混練物。然後，依情況施行機械性分散處理而形成糊膏。 The silver particles, the components such as a dispersion medium and a resin are mixed, and then introduced into a kneading defoaming machine to form a kneaded product of the components. Then, mechanical dispersion treatment is performed as appropriate to form a paste.

上述機械性分散處理中，在不會伴隨銀粒子明顯改質的條件下，亦可採用公知任一方法。具體而言，係可例示如：超音波分散、分散機、三輥研磨機、球磨機、珠磨機、雙軸捏合機、自公轉式攪拌機等，該等係可單獨使用、或亦可併用複數種。 In the above mechanical dispersion treatment, any known method may be employed without causing significant modification of the silver particles. Specifically, for example, an ultrasonic dispersion, a disperser, a three-roll mill, a ball mill, a bead mill, a biaxial kneader, a self-rotating mixer, etc. may be exemplified, and these may be used alone or in combination. Kind.

<導電膜的評估> <Evaluation of Conductive Film>

作為所製作導電性糊膏的評估，係實施電阻率與接觸電阻的測定。 As an evaluation of the produced conductive paste, the measurement of the electrical resistivity and the contact resistance was carried out.

(電阻率) (resistivity)

使用膜厚30μm的金屬遮罩，依10mm□的圖案在氧化鋁基板上施行整面印刷。將所獲得印刷基板利用燒成爐(YAMATO科學股份有限公司製DKM400)，於大氣中施行200℃、60分鐘的熱處理，再施行電阻率計算。 A full-surface printing was performed on the alumina substrate in a 10 mm square pattern using a metal mask having a film thickness of 30 μm. The obtained printed circuit board was subjected to heat treatment at 200 ° C for 60 minutes in the air using a firing furnace (DKM400 manufactured by YAMATO Scientific Co., Ltd.), and the resistivity calculation was performed.

利用四端子型電阻率計(三菱化學股份有限公司製LORESTA GP MCP-T610型)，測定導電膜的表面電阻，並利用表面粗糙度計(東京精密股份有限公司製Surfcom 1500D型)，測定導電膜的厚度，且依下式(1)計算出電阻率。 The surface resistance of the conductive film was measured by a four-terminal type resistivity meter (LORESTA GP MCP-T610 type manufactured by Mitsubishi Chemical Corporation), and the surface roughness meter (Surfcom 1500D type manufactured by Tokyo Seimitsu Co., Ltd.) was used to measure the conductive film. The thickness is calculated, and the resistivity is calculated according to the following formula (1).

電阻率(μΩ‧cm)=表面電阻(Ω/□)×膜厚(μm)×100………(1) Resistivity (μΩ‧cm)=surface resistance (Ω/□)×film thickness (μm)×100...(1)

(接觸電阻) (Contact resistance)

使用網版印刷機(Micor Tec股份有限公司製MT-320T)，依照圖1的圖案，在ITO玻璃基板(GEOMATEC股份有限公司製0006)上進行印刷。所獲得印刷基板利用燒成爐(YAMATO科學股份有限公司製DKM400)，於大氣中施行200℃、60分鐘的熱處理，再實施接觸電阻的測定。因此，以下的實施例中，測定接觸電阻可視為能夠形成印刷電路。 Printing was performed on an ITO glass substrate (0006 manufactured by GEOMATEC Co., Ltd.) using a screen printing machine (MT-320T manufactured by Micor Tec Co., Ltd.) in accordance with the pattern of Fig. 1 . The obtained printed circuit board was subjected to heat treatment at 200 ° C for 60 minutes in the air using a firing furnace (DKM400 manufactured by YAMATO Scientific Co., Ltd.), and measurement of contact resistance was performed. Therefore, in the following embodiments, measuring the contact resistance can be regarded as being capable of forming a printed circuit.

如圖1所示之圖案，係分別相隔開(1)300μm、(2)500μm、(3)1,000μm、(4)2,000μm的間隔，藉由依間隔不同的圖案測定電阻值，而計算出接觸電阻。具體而言，在將圖案間隔設為橫軸，且將實測電阻值設為縱軸時，將所獲得圖形的Y軸截距的一半視為「接觸電阻」。 The pattern shown in FIG. 1 is separated by (1) 300 μm, (2) 500 μm, (3) 1,000 μm, and (4) 2,000 μm, and the resistance is calculated by measuring the resistance values in different patterns. resistance. Specifically, when the pattern interval is set to the horizontal axis and the measured resistance value is the vertical axis, half of the Y-axis intercept of the obtained pattern is regarded as "contact resistance".

[實施例] [Examples] <實施例1> <Example 1> (銀微粒子A之製作方法) (How to make silver microparticles A)

對純水1,000g，添加作為銀化合物的硝酸銀結晶(東洋化學工業股份有限公司製特級品)51.0g、作為錯合劑的檸檬酸一水合物(和光純藥工業股份有限公司製特級品)50.2g、以及作為被覆用有機物的山梨酸鉀(和光純藥工業股份有限公司製特級品)7.7g之後，加溫至50℃而獲得銀離子分散液。 51,000 g of a silver nitrate crystal (a special grade product manufactured by Toyo Chemical Industry Co., Ltd.) as a silver compound, and a citric acid monohydrate (a special grade product of Wako Pure Chemical Industries Co., Ltd.) 50.2 g as a silver compound And 7.7 g of potassium sorbate (special grade product of Wako Pure Chemical Industries, Ltd.) as an organic substance for coating, and then heating to 50 ° C to obtain a silver ion dispersion liquid.

其次，對純水1,000g，溶解作為還原劑的L(+)-抗壞血酸 (和光純藥工業股份有限公司製特級品)26.6g，加溫至50℃而獲得還原劑分散液。 Secondly, it dissolves L (+)-ascorbic acid as a reducing agent for 1,000 g of pure water. (Special grade manufactured by Wako Pure Chemical Industries Co., Ltd.) 26.6 g, and heated to 50 ° C to obtain a reducing agent dispersion.

在氮環境下，於攪拌上述銀離子分散液的狀態下，使用定量送液泵(東京理科器械股份有限公司製RP-2100)，依33ml/分鐘的速度添加還原劑分散液。然後，將液溫維持於50℃，經保持60分鐘後便獲得銀微粒子。 In the nitrogen atmosphere, the reducing agent dispersion was added at a rate of 33 ml/min using a quantitative liquid feeding pump (RP-2100 manufactured by Tokyo Science and Technology Co., Ltd.) while stirring the silver ion dispersion. Then, the liquid temperature was maintained at 50 ° C, and silver fine particles were obtained after being held for 60 minutes.

對所獲得的銀微粒子，一邊流動著純水，一邊藉由施行抽吸過濾而洗淨粒子，去除多餘的雜質。然後，在30℃施行12小時的真空乾燥，便獲得銀微粒子的乾燥粉。另外，銀微粒子A的製造方法及特性係示於表1。又，以下的銀微粒子(B至I)亦同樣示於表1。 The obtained silver fine particles are washed with pure water while flowing, and the particles are washed by suction filtration to remove excess impurities. Then, vacuum drying was carried out at 30 ° C for 12 hours to obtain a dry powder of silver fine particles. The method and characteristics of the silver fine particles A are shown in Table 1. Further, the following silver fine particles (B to I) are also shown in Table 1.

利用SEM觀察乾燥粉，結果係屬於平板狀之銀微粒子，且其dSEM-L為635nm、dSEM-T為142nm、深寬比為4.5。 The dry powder was observed by SEM, and as a result, it was a plate-like silver fine particle having a d SEM-L of 635 nm, a d SEM-T of 142 nm, and an aspect ratio of 4.5.

乾燥粉的GC-MS圖譜結果係示於圖2。所觀察到的尖峰可確認係屬於醋酸。橫軸係時間(秒)，縱軸係豐度(abundance)。 The GC-MS spectrum results of the dry powder are shown in Figure 2. The observed spikes were confirmed to belong to acetic acid. The horizontal axis is time (seconds) and the vertical axis is abundance.

<實施例2> <Example 2> (銀微粒子B之製作方法) (Manufacturing method of silver microparticle B)

除了對銀離子分散液，在pH調節之目的下添加60質量%硝酸(和光純藥工業股份有限公司製特級品)4.2g之外，其餘均進行與銀微粒子A的情況同樣的步驟。 The same procedure as in the case of the silver fine particles A was carried out except that 4.2 g of a 60% by mass nitric acid (a special grade manufactured by Wako Pure Chemical Industries, Ltd.) was added for the purpose of pH adjustment.

利用SEM觀察乾燥粉，結果係屬於平板狀之銀微粒子， 且其dSEM-L為885nm、dSEM-T為176nm、深寬比為5.0。 The dry powder was observed by SEM, and as a result, it was a plate-like silver fine particle having a d SEM-L of 885 nm, a d SEM-T of 176 nm, and an aspect ratio of 5.0.

<實施例3> <Example 3> (銀微粒子C之製作方法) (How to make silver microparticles C)

除了對銀離子分散液，於pH調節之目的下添加60質量%硝酸(和光純藥工業股份有限公司製特級品)10.5g之外，其餘均進行與銀微粒子A的情況同樣的步驟。 The same procedure as in the case of the silver fine particles A was carried out except that 10.5 g of 60% by mass of nitric acid (a special grade manufactured by Wako Pure Chemical Industries, Ltd.) was added to the silver ion dispersion for the purpose of pH adjustment.

利用SEM觀察乾燥粉，結果係屬於平板狀之銀微粒子，且其dSEM-L為1132nm、dSEM-T為138nm、深寬比為8.2。 The dry powder was observed by SEM, and as a result, it was a plate-like silver fine particle having a d SEM-L of 1132 nm, a d SEM-T of 138 nm, and an aspect ratio of 8.2.

<實施例4> <Example 4> (銀微粒子D之製作方法) (How to make silver microparticles D)

除了在大氣環境下實施反應，並將還原劑添加後的保持時間設為3小時之外，其餘均進行與銀微粒子A的情況同樣的步驟。 The same procedure as in the case of the silver fine particles A was carried out except that the reaction was carried out in an atmospheric environment and the holding time after the addition of the reducing agent was set to 3 hours.

利用SEM觀察乾燥粉，結果係屬於平板狀之銀微粒子，且其dSEM-L為873nm、dSEM-T為46nm、深寬比為19.0。 The dry powder was observed by SEM, and as a result, it was a flat silver microparticle having a d SEM-L of 873 nm, a d SEM-T of 46 nm, and an aspect ratio of 19.0.

<實施例5> <Example 5> (銀微粒子E之製作方法) (How to make silver microparticles E)

除了將添加劑由山梨酸鉀變更為沒食子酸水合物(東京化成工業股份有限公司製特級品)之外，其餘均進行與銀微粒子A的情況同樣的步驟。 The same procedure as in the case of the silver fine particles A was carried out except that the additive was changed from potassium sorbate to gallic acid hydrate (special grade manufactured by Tokyo Chemical Industry Co., Ltd.).

利用SEM觀察乾燥粉，結果係屬於平板狀之銀微粒子，且其dSEM-L為280nm、dSEM-T為40nm、深寬比為7.2。 The dry powder was observed by SEM, and as a result, it was a flat silver microparticle having a d SEM-L of 280 nm, a d SEM-T of 40 nm, and an aspect ratio of 7.2.

<比較例1> <Comparative Example 1> (銀微粒子F之製作方法) (Manufacturing method of silver fine particles F)

除了將添加劑由山梨酸鉀變更為明膠(SIGMA-ALDRICH公司製)之外，其餘均進行與銀微粒子A的情況同樣的步驟。該銀微粒子的製作方法係與專利文獻2所記載之實施例相同。然而，本條件中，粒子對水的親和性非常良好，無法利用抽吸過濾施行洗淨與回收。其理由可認為因為明膠的主成分係蛋白質，因而具有多數的羧基、胺基之類的官能基之緣故。 The same procedure as in the case of the silver fine particles A was carried out except that the additive was changed from potassium sorbate to gelatin (manufactured by SIGMA-ALDRICH Co., Ltd.). The method for producing the silver fine particles is the same as the embodiment described in Patent Document 2. However, in this condition, the affinity of the particles for water is very good, and it is not possible to perform washing and recovery by suction filtration. The reason for this is considered to be that since the main component of gelatin is a protein, it has a plurality of functional groups such as a carboxyl group or an amine group.

<比較例2> <Comparative Example 2> (銀微粒子G之製作方法) (Method of Making Silver Particles G)

除了相對於銀粉F，將明膠的量變更為1/4之外，其餘均進行與銀微粒子A的情況同樣的步驟。本條件中，因為粒子表面上所吸附的明膠少於銀微粒子E，因而可施行回收。 The same procedure as in the case of the silver fine particles A was carried out except that the amount of gelatin was changed to 1/4 with respect to the silver powder F. In this condition, since the gelatin adsorbed on the surface of the particles is less than the silver fine particles E, it can be recovered.

利用SEM觀察乾燥粉，結果係屬於平板狀之銀微粒子，且其dSEM-L為628nm、dSEM-T為91nm、深寬比為6.9。 The dry powder was observed by SEM, and as a result, it was a flat silver microparticle having a d SEM-L of 628 nm, a d SEM-T of 91 nm, and an aspect ratio of 6.9.

利用GC-MS測定乾燥粉，結果如圖3所示可確認到數個尖峰。即，在添加劑中使用明膠的銀微粒子G，可確認到使用高分子保護劑。 The dry powder was measured by GC-MS, and as a result, several peaks were confirmed as shown in Fig. 3. That is, it was confirmed that a polymer protective agent was used by using the silver fine particles G of gelatin in the additive.

<比較例3> <Comparative Example 3> (銀微粒子H之製作方法) (Manufacturing method of silver fine particles H)

除了將添加劑由山梨酸鉀變更為醋酸(關東化學股份有限 公司製特級品)之外，其餘均進行與銀微粒子A的情況同樣的步驟。然而，本條件中，所獲得粒子係凝集粉，無法獲得目標之平板狀物。 In addition to changing the additive from potassium sorbate to acetic acid (Kantong Chemical Co., Ltd. The same steps as in the case of the silver fine particles A were carried out except for the company-made special grades. However, in the present condition, the obtained particles are agglomerated powder, and the target flat plate cannot be obtained.

<比較例4> <Comparative Example 4> (銀微粒子I之製作方法) (Manufacturing method of silver microparticles I)

除了將還原劑由抗壞血酸變更為肼(和光純藥工業股份有限公司製特級品)之外，其餘均進行與銀微粒子A的情況同樣的步驟。然而，本條件中，所獲得粒子係凝集粉，無法獲得目標之平板狀物。 The same procedure as in the case of the silver fine particles A was carried out except that the reducing agent was changed from ascorbic acid to hydrazine (a special grade product manufactured by Wako Pure Chemical Industries, Ltd.). However, in the present condition, the obtained particles are agglomerated powder, and the target flat plate cannot be obtained.

(糊膏評估) (stick evaluation)

使用表1所示銀微粒子A、G、H，實施糊膏的評估。 The evaluation of the paste was carried out using the silver fine particles A, G, and H shown in Table 1.

<實施例11> <Example 11>

分別添加作為分散溶劑的萜品醇(和光純藥工業股份有限公司製特級品)1.9g、作為分散劑的高分子系顏料分散劑AJISPER PA-111(Ajinomoto Fine-Techno股份有限公司製)0.1g、作為樹脂的雙酚F型環氧樹脂JER807(三菱化學股份有限公司製)4.6g、及作為硬化劑的三氟化硼單乙胺錯合物(和光純藥工業股份有限公司製)0.2g，並進行混合。進一步混合入銀微粒子A(93.2g)後，利用自公轉式真空攪拌混合機(EME股份有限公司製V-mini300)施行30秒攪拌。 1.9 g of terpineol (a special grade product of Wako Pure Chemical Industries Co., Ltd.) as a dispersing solvent and a polymer pigment dispersant AJISPER PA-111 (manufactured by Ajinomoto Fine-Techno Co., Ltd.) as a dispersing agent were added in an amount of 0.1 g. 2.6 g of a bisphenol F-type epoxy resin JER807 (manufactured by Mitsubishi Chemical Corporation) as a resin, and a boron trifluoride monoethylamine complex (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing agent 0.2 g And mix. After further mixing silver fine particles A (93.2 g), the mixture was stirred for 30 seconds using a self-revolving vacuum stirring mixer (V-mini 300 manufactured by EME Co., Ltd.).

將依此所獲得之混合物於三輥機(EXAKT Apparatebaus公司製M-80S型)通過5次，而製作導電性糊膏。將所獲得導電性糊膏印刷於基板上，依200℃、60分鐘的條件施行加熱處理而形成導電膜。 The mixture obtained in this manner was passed through a three-roller (M-80S type manufactured by EXAKT Apparatebaus Co., Ltd.) five times to prepare a conductive paste. The obtained conductive paste was printed on a substrate, and subjected to heat treatment at 200 ° C for 60 minutes to form a conductive film.

測定依此所獲得導電膜的電阻率與接觸電阻，結果電阻率係17.3μΩ‧cm、接觸電阻係0.161Ω。可獲得電阻率、接觸電阻均較低的導電膜。 The resistivity and contact resistance of the conductive film thus obtained were measured, and as a result, the resistivity was 17.3 μΩ·cm and the contact resistance was 0.161 Ω. A conductive film having a low resistivity and a low contact resistance can be obtained.

<比較例11> <Comparative Example 11>

在實施例11中，除了將所使用的銀微粒子設為銀微粒子G之外，其餘均重複施行實施例11。結果，所獲得導電膜的電阻率係35.1μΩ‧cm、接觸電阻係0.166Ω。 In Example 11, Example 11 was repeated except that the silver fine particles used were designated as silver fine particles G. As a result, the resistivity of the obtained conductive film was 35.1 μΩ·cm and the contact resistance was 0.166 Ω.

<比較例12> <Comparative Example 12>

在實施例11中，除了將所使用的銀微粒子設為銀微粒子H之外，其餘均重複施行實施例11。結果，所獲得導電膜的電阻率係32.6μΩ‧cm、接觸電阻係0.231Ω。 In Example 11, Example 11 was repeated except that the silver fine particles used were designated as silver fine particles H. As a result, the obtained conductive film had a specific resistance of 32.6 μΩ·cm and a contact resistance of 0.231 Ω.

藉此，當添加劑係使用如明膠之類的高分子時，會阻礙燒結性，導致電阻率提高。另一方面，若添加劑的碳數過少，則分散性會變差，而成為凝集粒子，因而經糊膏製作、印刷、硬化後的塗膜，會出現填充性變差，導致電阻率與接觸電阻變差。因此，為了製作非為凝集體而是具有低溫燒結性的平板狀之銀微粒子，添加劑較佳係使用碳數3~10者。 Thereby, when a polymer such as gelatin is used as an additive, sinterability is inhibited, resulting in an increase in electrical resistivity. On the other hand, when the carbon number of the additive is too small, the dispersibility is deteriorated and the aggregated particles become aggregated. Therefore, the coating film formed, printed, and cured by the paste may have poor filling properties, resulting in electrical resistivity and contact resistance. Getting worse. Therefore, in order to produce flat silver microparticles which are not aggregated but have low-temperature sinterability, the additive is preferably one having a carbon number of 3 to 10.

利用本發明所獲得的平板狀之銀微粒子係可單獨進行糊膏化，亦可藉由與公知銀粒子相混合而獲得電阻率、接觸電阻均較低的糊膏。此處記載與公知銀粒子相混合的混合糊膏之實施例。混合時所使用的公知銀粒子(銀粒子I至銀粒子L)係示於表2(另外，DSEM-L係從SEM影像所計算出之長邊方向的粒徑平均值，DSEM-T係從SEM影像所計算出之厚度方向的粒徑平均值，深寬比係由DSEM-L/DSEM-T所計算出的值)。 The flat silver microparticles obtained by the present invention can be separately paste-formed, or a paste having a low electrical resistivity and a low contact resistance can be obtained by mixing with known silver particles. Examples of mixed pastes mixed with known silver particles are described herein. The known silver particles (silver particles I to silver particles L) used in the mixing are shown in Table 2 (in addition, D SEM-L is the average particle diameter in the longitudinal direction calculated from the SEM image, D SEM-T The average particle diameter in the thickness direction calculated from the SEM image, and the aspect ratio is a value calculated by D SEM-L /D SEM-T ).

另外，銀粒子中亦可含有未必為板狀之物。當銀粒子的形狀非為板狀時，DSEM-L係從SEM影像所計算出的粒子長軸長度平均值，DSEM-T係從SEM影像所計算出的短軸長度平均值。 Further, the silver particles may contain a material that is not necessarily plate-shaped. When the shape of the silver particles is not a plate shape, D SEM-L is an average value of the major axis length calculated from the SEM image, and D SEM-T is an average value of the minor axis length calculated from the SEM image.

(糊膏製作) (make making)

使用表1、2所示之銀微粒子A至I、與銀粒子J至M，實施混合糊膏的評估。另外，統稱銀微粒子與銀粒子的情況、或僅稱其中一者的情況，均稱為「銀粉末」。 The evaluation of the mixed paste was carried out using the silver fine particles A to I shown in Tables 1 and 2 and the silver particles J to M. In addition, the case of collectively referred to as silver fine particles and silver particles, or the case of only one of them, is referred to as "silver powder".

<實施例12~17> <Examples 12 to 17>

在實施例11中，除了將所使用的銀粉末設為表3所記載的組合，並在實施例11中，將銀微粒子A 93.2g，變更為銀微粒子與銀粒子之混合量分別為46.6g，合計為93.2g之外，其餘均重複施行實施例11。所獲得的電阻率、接觸電阻合併記載於表3。 In Example 11, except that the silver powder to be used was a combination described in Table 3, in Example 11, 93.2 g of silver fine particles A was changed to a mixing amount of silver fine particles and silver particles of 46.6 g, respectively. Except for the total of 93.2 g, Example 11 was repeatedly carried out. The obtained specific resistance and contact resistance are collectively shown in Table 3.

<比較例13、14> <Comparative Examples 13, 14>

在實施例11中，除了將所使用的銀粉末變更為表3所記載的銀粉末(1種銀粒子)之外，其餘均重複施行實施例11。所獲得的電阻率、接觸電阻合併記載於表3。 In Example 11, Example 11 was repeated except that the silver powder used was changed to the silver powder (one type of silver particles) described in Table 3. The obtained specific resistance and contact resistance are collectively shown in Table 3.

<比較例15、16> <Comparative Examples 15, 16>

在實施例11中，除了將所使用的銀粉末設為表3所記載的組合，並將銀粉末的混合量分別設為46.6g，合計為93.2g 之外，其餘均重複施行實施例11。所獲得的電阻率、接觸電阻合併記載於表3。 In the eleventh embodiment, the silver powder to be used was used as the combination described in Table 3, and the amount of the silver powder was 46.6 g, which was 93.2 g in total. Except for the rest, Example 11 was repeatedly carried out. The obtained specific resistance and contact resistance are collectively shown in Table 3.

如比較例13與14所示，可知當單獨使用微米尺寸的銀粒子製作糊膏時，電阻率、接觸電阻均較高。相對於此，如實施例12~17與比較例15~16所示，藉由將大小不同的2種銀粉末相混合並糊膏化，便可獲得電阻率、接觸電阻均降低的結果。 As shown in Comparative Examples 13 and 14, it was found that when a paste was prepared using silver particles of a micron size alone, the electrical resistivity and the contact resistance were both high. On the other hand, as shown in Examples 12 to 17 and Comparative Examples 15 to 16, the results of the decrease in the resistivity and the contact resistance were obtained by mixing and pasting two kinds of silver powders having different sizes.

關於進行混合的微粒子，在如比較例15般使用平板狀之銀粒子的情況，雖可降低電阻率，但難謂接觸電阻充分降低。又，在如比較例16般使用球狀之銀粒子的情況，雖可降低接觸電阻，但難謂電阻率充分降低。 Regarding the fine particles to be mixed, when the flat silver particles were used as in Comparative Example 15, although the electrical resistivity was lowered, it was difficult to sufficiently reduce the contact resistance. Further, in the case where spherical silver particles were used as in Comparative Example 16, the contact resistance was lowered, but it was difficult to sufficiently reduce the resistivity.

如實施例12~17，藉由將進行混合的微粒子設為本說明書所記載的平板狀之銀微粒子，便可使電阻率、接觸電阻均降低。又，如實施例17般將進行混合的微米尺寸銀粒子設為 球狀時，亦同樣均可降低電阻率、接觸電阻。此結果係以圖表顯示於圖4。 In the examples 12 to 17, by using the fine particles to be mixed as the flat silver microparticles described in the present specification, both the electrical resistivity and the contact resistance can be lowered. Further, the micron-sized silver particles to be mixed as in Example 17 were set to In the case of a spherical shape, the resistivity and contact resistance can also be reduced. This result is shown graphically in Figure 4.

圖4係顯示電阻率與接觸電阻間的關係之圖。縱軸係接觸電阻(Ω)，橫軸係電阻率(μΩ‧cm)。另外，橫軸係對數軸。黑色菱形係實施例，白色四角形係比較例。黑色菱形的實施例係電阻率與接觸電阻均降低，而白色四角形的比較例則係呈現其中任一者或二者的特性較高之結果。 Figure 4 is a graph showing the relationship between resistivity and contact resistance. The vertical axis is the contact resistance (Ω), and the horizontal axis is the resistivity (μΩ‧ cm). In addition, the horizontal axis is the logarithmic axis. Black diamond embodiment, white square is a comparative example. The examples of the black diamond are both reduced in electrical resistivity and contact resistance, while the comparative examples of white squares are the result of exhibiting higher characteristics of either or both.

(產業上之可利用性) (industrial availability)

根據本發明，可獲得平板狀之銀微粒子、及含有銀微粒子的導電性糊膏，且以200℃左右的處理溫度，可獲得電阻率值、接觸電阻值均良好的導電膜。此等係適用於太陽電池、電容器、RFID(無線射頻識別系統，Radio Frequency Identification)等領域中的佈線描繪、電極形成。 According to the present invention, flat silver microparticles and a conductive paste containing silver microparticles can be obtained, and a conductive film having a good resistivity value and a contact resistance value can be obtained at a treatment temperature of about 200 °C. These are suitable for wiring drawing and electrode formation in the fields of solar cells, capacitors, RFID (Radio Frequency Identification), and the like.

圖1係為了測定接觸電阻所使用的圖案之圖。 Figure 1 is a diagram of a pattern used to determine contact resistance.

圖2係顯示GC-MS圖譜之圖。 Figure 2 is a diagram showing the GC-MS spectrum.

圖3係顯示GC-MS圖譜之圖。 Figure 3 is a diagram showing the GC-MS spectrum.

圖4係顯示接觸電阻與電阻率的相關性之圖。 Figure 4 is a graph showing the correlation between contact resistance and resistivity.

Claims (8)

一種平板狀之銀微粒子粉末，其特徵為，被覆表面的有機物為碳數2~10的有機物，從SEM影像所計算出之厚度方向的粒徑平均值(dSEM-T)為10~200nm，且長邊方向的粒徑平均值(dSEM-L)與上述厚度方向的粒徑平均值(dSEM-T)之比(dSEM-L/dSEM-T)的深寬比係2~100。 A flat silver microparticle powder characterized in that the organic substance on the surface of the coating is an organic substance having a carbon number of 2 to 10, and the average particle diameter (d SEM-T ) in the thickness direction calculated from the SEM image is 10 to 200 nm. The aspect ratio of the average particle diameter in the longitudinal direction (d SEM-L ) to the average particle diameter (d SEM-T ) in the thickness direction (d SEM-L /d SEM-T ) is 2~ 100. 一種銀粒子粉末之製造方法，係將水溶性銀化合物、水溶性錯合劑、及由碳數3~10之有機物所構成的添加劑添加至水中，並添加由有機物所構成的還原劑，而生成平板狀之銀微粒子。 A method for producing a silver particle powder by adding a water-soluble silver compound, a water-soluble complexing agent, and an additive composed of an organic substance having 3 to 10 carbon atoms to water, and adding a reducing agent composed of an organic substance to form a flat plate Silver particles. 如申請專利範圍第2項之銀粒子粉末之製造方法，其中，上述錯合劑係檸檬酸鹽。 The method for producing a silver particle powder according to claim 2, wherein the above-mentioned complexing agent is citrate. 如申請專利範圍第2或3項之銀粒子粉末之製造方法，其中，上述還原劑係抗壞血酸或其衍生物或異構物。 The method for producing a silver particle powder according to the second or third aspect of the invention, wherein the reducing agent is ascorbic acid or a derivative or an isomer thereof. 一種銀糊膏，係含有平板狀之銀微粒子粉末，該平板狀之銀微粒子粉末之特徵為，被覆表面的有機物為碳數2~10的有機物，從SEM影像所計算出之厚度方向的粒徑平均值(dSEM-T)為10~200nm，且長邊方向的粒徑平均值(dSEM-L)與上述厚度方向的粒徑平均值(dSEM-T)之比(dSEM-L/dSEM-T)的深寬比係2~100。 A silver paste containing a flat silver fine particle powder, wherein the flat silver fine particle powder is characterized in that the organic material on the coated surface is an organic substance having a carbon number of 2 to 10, and the particle diameter in the thickness direction calculated from the SEM image The average value (d SEM-T ) is 10 to 200 nm, and the ratio of the average particle diameter in the longitudinal direction (d SEM-L ) to the average particle diameter in the thickness direction (d SEM-T ) (d SEM-L) /d SEM-T ) has an aspect ratio of 2 to 100. 一種銀糊膏，係將平板狀之銀微粒子粉末，與長邊方向的粒徑平均值(DSEM-L)為2.5~15.0μm、且相對於申請專利範 圍第1項之平板狀之銀微粒子粉末的dSEM-L為3~50倍大的銀粒子共同混合而成；該平板狀之銀微粒子粉末之特徵為，被覆表面的有機物為碳數2~10的有機物，從SEM影像所計算出之厚度方向的粒徑平均值(dSEM-T)為10~200nm，且長邊方向的粒徑平均值(dSEM-L)與上述厚度方向的粒徑平均值(dSEM-T)之比(dSEM-L/dSEM-T)的深寬比係2~100。 A silver paste which is a flat silver-like fine particle powder having a mean particle diameter (D SEM-L ) of 2.5 to 15.0 μm in the longitudinal direction and a flat silver particle in relation to the first item of the patent application. The d SEM-L of the powder is a mixture of 3 to 50 times larger silver particles; the flat silver microparticle powder is characterized in that the organic matter on the surface is an organic substance having a carbon number of 2 to 10, which is calculated from the SEM image. The average particle diameter in the thickness direction (d SEM-T ) is 10 to 200 nm, and the average value of the particle diameter in the longitudinal direction (d SEM-L ) and the average particle diameter in the thickness direction (d SEM-T ) The aspect ratio (d SEM-L /d SEM-T ) is 2 to 100. 如申請專利範圍第6項之銀糊膏，其中，銀粒子的形狀係平板狀。 The silver paste of claim 6, wherein the silver particles have a flat shape. 一種印刷電路，係使用申請專利範圍第5至7項中任一項之銀糊膏，利用印刷法而形成。 A printed circuit formed by a printing method using the silver paste of any one of claims 5 to 7.
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