TW201546237A - Conductive adhesive and electronic part using the same - Google Patents
Conductive adhesive and electronic part using the same Download PDFInfo
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- TW201546237A TW201546237A TW104107901A TW104107901A TW201546237A TW 201546237 A TW201546237 A TW 201546237A TW 104107901 A TW104107901 A TW 104107901A TW 104107901 A TW104107901 A TW 104107901A TW 201546237 A TW201546237 A TW 201546237A
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
Abstract
Description
本發明係關於導電性接著劑及使用其之電子零件，尤其是關於電子製品之構件彼此之電連接有效之導電性接著劑。 The present invention relates to an electrically conductive adhesive and an electronic component using the same, and more particularly to an electrically conductive adhesive which is effective in electrical connection between members of an electronic article.
於配線基板上之電子零件等的安裝，以往均使用焊料，近年來由於顧慮到對人體或自然環境之影響，故無鉛焊料成為主流。 Soldering of electronic components and the like on a wiring board has conventionally been carried out using solder. In recent years, lead-free solder has become a mainstream because of the concern for the human body or the natural environment.
另一方面，近年來因隨著電子儀器的小型化且伴隨電子零件之高密度化、LSI演算速度提高等而使傳送速度高速化，使電子零件之發熱變大。又最近，於車用等之過度嚴苛之使用條件下使用之電子零件。 On the other hand, in recent years, with the miniaturization of electronic equipment, the increase in the density of electronic components, the increase in the LSI calculation speed, and the like, the transmission speed is increased, and the heat generation of electronic components is increased. Recently, electronic parts used under excessively harsh conditions such as automobiles.
因此，用焊料安裝之電子零件中，藉由冷熱循環而累積變形，其結果有於焊料接合部易產生龜裂的問題。 Therefore, in the electronic component mounted by the solder, the deformation is accumulated by the thermal cycle, and as a result, the solder joint portion is liable to be cracked.
相對於此，進行著取代焊料之導電性接著劑的開發，作為其一例提案有包含銀粉之混合物與特定之熱硬化性樹脂之導電性樹脂糊(專利文獻1)。 On the other hand, development of a conductive adhesive that replaces solder has been carried out. As an example, a conductive resin paste containing a mixture of silver powder and a specific thermosetting resin has been proposed (Patent Document 1).
[專利文獻1]特公平5-11365號 [Patent Document 1] Special Fair 5-11365
專利文獻1中，提案有藉由將對特定之熱硬化性樹脂使用2種類硬化劑的樹脂糊用於發光二極體用晶片黏接，而以快速之硬化速度進行良好接著之技術。 Patent Document 1 proposes a technique in which a resin paste using two types of curing agents for a specific thermosetting resin is used for bonding a wafer for a light-emitting diode, and is preferably adhered to at a rapid curing rate.
然而，專利文獻1之技術，必須在高溫下硬化以提高硬化速度。因而，有如塑膠基板之無法耐高溫之基板無法適用之問題。 However, the technique of Patent Document 1 must be hardened at a high temperature to increase the hardening speed. Therefore, there is a problem that a substrate which cannot withstand high temperatures such as a plastic substrate cannot be applied.
另外，隨著電子零件之高密度化而朝接著面縮小化進展，要求導電性接著劑之接著力進一步提高及低電阻化。 In addition, as the electronic component is increased in density, the reduction in the adhesion surface progresses, and the adhesion of the conductive adhesive is further increased and the resistance is lowered.
因此，本發明之目的係提供一種除了維持導電性接著劑原本必要之硬度以外，即使藉由較低溫之處理亦可強力接著以電子零件為代表之接著面積小的零件，且可進一步實現低電阻化之導電性接著劑。 SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a component having a small contact area which is strongly represented by an electronic component, and which can be further low-resistance, in addition to maintaining the hardness necessary for the conductive adhesive. A conductive adhesive.
本發明人們等，為解決上述課題而精心檢討 之結果，至於完成將以下內容作為主要構成之發明。 The inventors of the present invention have carefully reviewed the above problems. As a result, the invention having the following main components is completed.
亦即，本發明之導電性接著劑之特徵為有含：下述之導電性粉末與(B)與(C)，但不含有溶劑，含片狀之導電粉末(A-1)與具有該片狀之導電粉末(A-1)之3分之1以下的平均粒徑之導電粉末(A-2)的導電粉末，(B)縮水甘油醚化合物，(C)硬化劑。 That is, the conductive adhesive of the present invention is characterized in that it contains: the following conductive powder and (B) and (C), but does not contain a solvent, and contains a sheet-like conductive powder (A-1) and has the same An electrically conductive powder of the conductive powder (A-2) having an average particle diameter of one third or less of the sheet-like conductive powder (A-1), (B) a glycidyl ether compound, and (C) a curing agent.
本發明之導電性接著劑中，前述導電粉末(A-2)較好為選自片狀及球狀之至少1種的導電粉末。本發明之導電性接著劑中，(B)縮水甘油醚化合物較好為以下式(I)表示之化合物，
(式中R1表示烷基、芳基、烷基芳基或芳基烷基，m+n=0、1或2)，最佳為以下式(II)表示之化合物，
本發明之電子零件之特徵係使用上述本發明之導電性接著劑，使構件彼此電連接而成。 The electronic component of the present invention is characterized in that the members are electrically connected to each other by using the above-described conductive adhesive of the present invention.
依據本發明，可提供除了維持導電性接著劑原本必要之硬度以外，即使藉由較低溫處理亦可強力接著以電子零件為代表之接著面積小的零件，且可進一步實現低電阻化之導電性接著劑。 According to the present invention, it is possible to provide a part having a small adhesion area represented by an electronic component, and further reducing the electrical conductivity of the low-resistance, in addition to the hardness necessary for maintaining the conductive adhesive. Follow-up agent.
本發明之導電性接著劑由於不含溶劑，故不易發生硬化收縮，且可抑制其硬化物中氣泡之發生，故可強力導電接著。 Since the conductive adhesive of the present invention does not contain a solvent, it is less likely to cause hardening and shrinkage, and the occurrence of bubbles in the cured product can be suppressed, so that it can be strongly electrically conductive.
依據本發明之導電性接著劑，可提供使構件彼此強力導電接著之電子零件。 According to the conductive adhesive of the present invention, it is possible to provide an electronic component in which members are strongly electrically connected to each other.
本發明之導電性接著劑之特徵係包含：包含片狀之導電粉末(A-1)與具有該片狀(A-1)之導電粉末之3分之1以下之平均粒徑之導電粉末(A-2)的導電粉末、與(B)縮水甘油醚化合物、與(C)硬化劑，且不含溶劑。 The conductive adhesive of the present invention is characterized by comprising: a conductive powder containing a sheet-like conductive powder (A-1) and an average particle diameter of one-third or less of the conductive powder having the sheet (A-1) ( Conductive powder of A-2), (B) glycidyl ether compound, and (C) hardener, and does not contain a solvent.
此本發明之導電性接著劑中，所謂「未使用 溶劑」或「無溶劑」係指導電性接著劑實質上不含溶劑或稀釋劑等，且接著劑的150℃加熱30分鐘之質量減少與加熱前之質量比較，為1質量%以下者。 In the conductive adhesive of the present invention, the so-called "unused The solvent or the "solvent-free" means that the electrical adhesive is substantially free of a solvent or a diluent, and the mass of the adhesive which is heated at 150 ° C for 30 minutes is less than 1 mass % compared with the mass before heating.
以下，針對構成本發明之導電性接著劑之各成分加以說明。 Hereinafter, each component constituting the conductive adhesive of the present invention will be described.
本發明之導電粉末係包含片狀之導電粉末(A-1)與具有該片狀之導電粉末(A-1)之3分之1以下，較好5分之1至20分之1，更好為6分之1至10分之1之平均粒徑D50之導電粉末(A-2)。 The conductive powder of the present invention comprises one or more than one-third of the conductive powder (A-1) in the form of a sheet and the conductive powder (A-1) having the sheet shape, preferably from 1/20 to 1/20, more preferably It is preferably a conductive powder (A-2) having an average particle diameter D50 of from 1/1 to 1/1.
藉由使導電粉末成為該構成，可實現導電性接著劑之更低電阻化。其理由認為係藉由成為該構成而使導電粉末彼此之接觸更良好，而進一步提高導電性者。 By making the conductive powder into this configuration, it is possible to achieve lower resistance of the conductive adhesive. The reason for this is that the conductive powder is more preferably brought into contact with each other by this configuration, and the conductivity is further improved.
此外，藉由將導電粉末(A-1)之形狀設為片狀，可增加導電粉末彼此之接觸面積，而獲得充分之導電性。 Further, by setting the shape of the conductive powder (A-1) into a sheet shape, the contact area of the conductive powders with each other can be increased, and sufficient conductivity can be obtained.
作為導電粉末(A-2)可使用球狀、片狀、樹枝狀等各種形狀者，但較佳為選自片狀及球狀之至少1種，更佳為使用球狀之導電粉末。 As the conductive powder (A-2), various shapes such as a spherical shape, a sheet shape, and a dendritic shape can be used, but it is preferably at least one selected from the group consisting of a sheet shape and a spherical shape, and more preferably a spherical conductive powder.
又，作為本發明所用之導電粉末(A-1)或(A-2)列舉為例如金、銀、銅、鎳、鋁、鉑、鈀、錫、鉍、鋅、鐵、銦、銥、鋨、銠、鎢、鉬、釕等低電阻金屬及該等之合金，或氧化錫(SnO2)、氧化銦(In2O3)、 ITO等導電性氧化物、導電性碳等。其中，以銀粉較佳。 Further, the conductive powder (A-1) or (A-2) used in the present invention is exemplified by, for example, gold, silver, copper, nickel, aluminum, platinum, palladium, tin, antimony, zinc, iron, indium, antimony, bismuth. Low-resistance metals such as tantalum, tungsten, molybdenum, and niobium, and alloys thereof, or conductive oxides such as tin oxide (SnO 2 ), indium oxide (In 2 O 3 ), and ITO, and conductive carbon. Among them, silver powder is preferred.
以下，針對導電粉末(A-1)加以說明。 Hereinafter, the conductive powder (A-1) will be described.
導電粉末(A-1)之平均粒徑D50係自2.0μm~20μm，較佳5μm~15μm，更佳7μm~13μm之範圍適當選擇。 The average particle diameter D50 of the conductive powder (A-1) is appropriately selected from the range of 2.0 μm to 20 μm, preferably 5 μm to 15 μm, more preferably 7 μm to 13 μm.
若導電粉末(A-1)之平均粒徑D50為2μm以上，則導電粉末彼此之接點數變得更少，可抑制接觸電阻，而獲得充分之導電性。另一方面，藉由將導電粉末之平均粒徑D50設為20μm以下，可將導電性接著劑應用於微細部位而使接著強度變充分。 When the average particle diameter D50 of the conductive powder (A-1) is 2 μm or more, the number of contacts of the conductive powders becomes smaller, and the contact resistance can be suppressed to obtain sufficient conductivity. On the other hand, when the average particle diameter D50 of the conductive powder is 20 μm or less, the conductive adhesive can be applied to the fine portion to increase the bonding strength.
導電粉末(A-1)之敲實密度係自4.0g/cm3~7.0g/cm3，較佳自4.5g/cm3~6.4g/cm3，更佳自5.0g/cm3~6.0g/cm3之範圍適當選擇。 The tap density of the conductive powder (A-1) is from 4.0 g/cm 3 to 7.0 g/cm 3 , preferably from 4.5 g/cm 3 to 6.4 g/cm 3 , more preferably from 5.0 g/cm 3 to 6.0. The range of g/cm 3 is appropriately selected.
導電粉末(A-1)之敲實密度若為4.0g/cm3以上，則相對於導電粉末(A-1)之容量的密度充分，可在比較密實狀態下進行高填充，獲得充分之導電性。另一方面，敲實密度7.0g/cm3以下之導電粉末(A-1)於工業生產容易，導電性亦充分。 When the tap density of the conductive powder (A-1) is 4.0 g/cm 3 or more, the density with respect to the capacity of the conductive powder (A-1) is sufficient, and high filling can be performed in a relatively dense state to obtain sufficient conductivity. Sex. On the other hand, the conductive powder (A-1) having a tap density of 7.0 g/cm 3 or less is easy to be industrially produced and has sufficient conductivity.
導電粉末(A-1)之BET比表面積係自0.1m2/g~1.0m2/g，較佳自0.2m2/g~0.6m2/g，更佳自0.2m2/g~0.3m2/g之範圍適當選擇。 Conductive powder (A-1) BET specific surface area of the system from 0.1m 2 /g~1.0m 2 / g, preferably from 0.2m 2 /g~0.6m 2 / g, more preferably from 0.2m 2 /g~0.3 The range of m 2 /g is appropriately selected.
導電粉末(A-1)之BET比表面積若為0.1m2/g以上，則相互之接觸面積增大，而獲得充分之導電性。另一方面，BET比表面積若為1m2/g以下，則即使 導電性接著劑中之導電粉末含量增大，黏度之調整亦容易，就導電性與操作性兩者均有意義。 When the BET specific surface area of the conductive powder (A-1) is 0.1 m 2 /g or more, the mutual contact area is increased to obtain sufficient conductivity. On the other hand, when the BET specific surface area is 1 m 2 /g or less, even if the content of the conductive powder in the conductive adhesive is increased, the adjustment of the viscosity is easy, and both conductivity and workability are significant.
該導電粉末(A-1)係利用濕式還原法、電解法、霧化法等習知方法製造。 The conductive powder (A-1) is produced by a conventional method such as a wet reduction method, an electrolysis method, or an atomization method.
尤其導電粉末之形狀作成片狀時，可於振動研磨、攪拌式粉碎機等之具有粉碎‧壓延效果之機械等使用粉碎介質而施加物理力藉此加工成片狀。 In particular, when the shape of the conductive powder is in the form of a sheet, it can be processed into a sheet shape by applying a physical force to a machine having a grinding and rolling effect such as a vibration grinding or a stirring mill using a grinding medium.
以下，針對導電粉末(A-2)加以說明。 Hereinafter, the conductive powder (A-2) will be described.
導電粉末(A-2)之平均粒徑D50係自0.1μm~10μm，較好自0.5μm~5.0μm，更好自1.0μm~2.0μm之範圍適當選擇。 The average particle diameter D50 of the conductive powder (A-2) is suitably selected from the range of 0.1 μm to 10 μm, preferably from 0.5 μm to 5.0 μm, more preferably from 1.0 μm to 2.0 μm.
若導電粉末(A-2)之平均粒徑D50為0.1μm以上，則可抑制導電性接著劑之增黏，獲得充分之塗佈性。另一方面，藉由將導電粉末(A-2)之平均粒徑D50設為10μm以下，可將導電性接著劑適用於微細部位且使接著強度充分。 When the average particle diameter D50 of the conductive powder (A-2) is 0.1 μm or more, the adhesion of the conductive adhesive can be suppressed, and sufficient coatability can be obtained. On the other hand, when the average particle diameter D50 of the conductive powder (A-2) is 10 μm or less, the conductive adhesive can be applied to the fine portion and the bonding strength can be made sufficient.
導電粉末(A-2)之敲實密度係自4.0g/cm3~7.0g/cm3，較佳自4.5g/cm3~6.5g/cm3，更佳自5.0g/cm3~6.0g/cm3之範圍適當選擇。 The tap density of the conductive powder (A-2) is from 4.0 g/cm 3 to 7.0 g/cm 3 , preferably from 4.5 g/cm 3 to 6.5 g/cm 3 , more preferably from 5.0 g/cm 3 to 6.0. The range of g/cm 3 is appropriately selected.
導電粉末(A-2)之敲實密度若為4.0g/cm3以上，則可以較密實之狀態高填充導電粉末(A-2)，獲得充分之導電性。另一方面，敲實密度7.0g/cm3以下之導電粉末(A-2)於工業生產容易，導電性亦充分。 When the tap density of the conductive powder (A-2) is 4.0 g/cm 3 or more, the conductive powder (A-2) can be filled in a relatively dense state to obtain sufficient conductivity. On the other hand, the conductive powder (A-2) having a tap density of 7.0 g/cm 3 or less is easy to be industrially produced and has sufficient conductivity.
導電粉末(A-2)之BET比表面積係自 0.5m2/g~1.5m2/g，較佳自0.7m2/g~1.3m2/g，更佳0.9m2/g~1.1m2/g之範圍適當選擇。 Conductive powder (A-2) BET specific surface area of the system from 0.5m 2 /g~1.5m 2 / g, preferably from 0.7m 2 /g~1.3m 2 / g, more preferably 0.9m 2 /g~1.1m The range of 2 / g is appropriately selected.
導電粉末(A-2)之BET比表面積若為0.5m2/g以上，則相互之接觸面積增大，而獲得充分之導電性。另一方面，BET比表面積若為1.5m2/g以下，則即使導電性接著劑之導電粉末含量增大，黏度之調整亦容易，就導電性與操作性兩者均有意義。 When the BET specific surface area of the conductive powder (A-2) is 0.5 m 2 /g or more, the mutual contact area is increased to obtain sufficient conductivity. On the other hand, when the BET specific surface area is 1.5 m 2 /g or less, even if the conductive powder content of the conductive adhesive is increased, the viscosity is easily adjusted, and both conductivity and workability are significant.
該導電粉末(A-2)係利用例如濕式還原法、電解法或霧化法等習知方法製造，亦可使用市售之球狀銀粉。 The conductive powder (A-2) is produced by a conventional method such as a wet reduction method, an electrolysis method, or an atomization method, and a commercially available spherical silver powder can also be used.
又，本實施形態中，導電粉末之平均粒徑D50係以雷射繞射散射式粒度分佈測定裝置或以利用雷射杜普勒法之粒度分佈測定裝置測定之值。 Further, in the present embodiment, the average particle diameter D50 of the conductive powder is a value measured by a laser diffraction scattering type particle size distribution measuring apparatus or a particle size distribution measuring apparatus by a laser Doppler method.
導電粉末之敲實度係依據JIS Z 2512，將規定量之粉末饋入容器內，使用敲實裝置，敲實至粉末之體積不再減少為止，且將粉末之質量除以敲實後之粉末體積所得之值。 The compactness of the conductive powder is based on JIS Z 2512, the specified amount of powder is fed into the container, and the compaction device is used to knock until the volume of the powder is no longer reduced, and the mass of the powder is divided by the powder after the compaction. The value obtained by volume.
導電粉末之BET比表面積係以BET法(氣體吸附法)，使氮(N2)吸附於導電粉末上，由其吸附量求出之值。 The BET specific surface area of the conductive powder is a value obtained by adsorbing the nitrogen (N 2 ) on the conductive powder by the BET method (gas adsorption method).
本發明之導電性接著劑中，導電粉末(A-1)與導電粉末(A-2)之調配比例(導電粉末(A-1)：導電粉末(A-2)(質量比例))係自95：5~40：60，較佳自90：10~50：50，更佳自82：18~58：42之範圍適當選 擇。 In the conductive adhesive of the present invention, the ratio of the conductive powder (A-1) to the conductive powder (A-2) (conductive powder (A-1): conductive powder (A-2) (mass ratio)) is 95:5~40:60, preferably from 90:10~50:50, better from 82:18~58:42 Choose.
且，導電性接著劑中之(A)導電粉末之調配比例係自80質量%~95質量%，較佳自85質量%~93質量%，更佳自89質量%~91質量%之範圍適當選擇。 Further, the ratio of the (A) conductive powder in the conductive adhesive is from 80% by mass to 95% by mass, preferably from 85% by mass to 93% by mass, more preferably from 89% by mass to 91% by mass. select.
本發明之導電性接著劑包含(B)縮水甘油醚化合物。 The conductive adhesive of the present invention contains (B) a glycidyl ether compound.
作為縮水甘油醚化合物可使用例如習知之環氧樹脂，但本發明中，為維持導電性接著劑之流動性，較好使用液狀，尤其於室溫之黏度為0.5~100dPa‧s，較佳1~10dPa‧s，更佳為1.5~5dPa‧s之範圍之化合物，且為一分子中具有2個以上環氧基之多官能環氧樹脂。 As the glycidyl ether compound, for example, a conventional epoxy resin can be used. However, in the present invention, in order to maintain the fluidity of the conductive adhesive, it is preferred to use a liquid, especially at room temperature, having a viscosity of 0.5 to 100 dPa ‧ s, preferably A compound having a range of from 1 to 10 dPa ‧ , more preferably from 1.5 to 5 dPa ‧ , and a polyfunctional epoxy resin having two or more epoxy groups in one molecule.
多官能環氧樹脂列舉為雙酚A型環氧樹脂、溴化環氧樹脂、酚醛清漆型環氧樹脂、雙酚F型環氧樹脂、氫化雙酚A型環氧樹脂、縮水甘油胺型環氧樹脂、受阻胺型環氧樹脂、脂環式環氧樹脂、三羥基苯基甲烷型環氧樹脂、聯二甲酚型或聯酚型環氧樹脂或該等之混合物、雙酚S型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、四羥苯基乙烷型環氧樹脂、雜環式環氧樹脂、二縮水甘油基鄰苯二甲酸酯樹脂、四縮水甘油基二甲苯基乙烷樹脂、含萘基之環氧樹脂、具有二環戊二烯骨架之環氧樹脂、縮水甘油基甲基丙烯酸酯共聚合系環氧樹脂、環己基馬來醯亞胺與縮水甘油基甲基丙烯酸酯之共聚合環氧樹脂、CTBN改 質之環氧樹脂等。 The polyfunctional epoxy resin is exemplified by bisphenol A type epoxy resin, brominated epoxy resin, novolak type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type ring Oxygen resin, hindered amine type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol type or biphenol type epoxy resin or a mixture thereof, bisphenol S type ring Oxygen resin, bisphenol A novolac type epoxy resin, tetrahydroxyphenylethane type epoxy resin, heterocyclic epoxy resin, diglycidyl phthalate resin, tetraglycidyl xylyl group Ethane resin, naphthalene-containing epoxy resin, epoxy resin having a dicyclopentadiene skeleton, glycidyl methacrylate copolymerized epoxy resin, cyclohexylmaleimide and glycidyl group Acrylate copolymerized epoxy resin, CTBN modified Epoxy resin, etc.
上述(B)縮水甘油醚化合物中，本發明中較好使用以下述式(I)表示之縮水甘油醚化合物：
若為該化合物，則硬化物之接著強度及硬度之任一者均獲得良好結果。且，可將接著劑對導電性之影響抑制至最小。 In the case of this compound, good results were obtained in either of the strength and hardness of the cured product. Moreover, the influence of the adhesive on conductivity can be minimized.
式(I)中，R1表示烷基、芳基、烷基芳基或芳基烷基，m+n=0、1或2。m+n≠0、1、2時，有無法獲得低彈性與低吸水性之均衡優異者之虞。 In the formula (I), R1 represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and m+n=0, 1 or 2. When m+n ≠ 0, 1, 2, there is a problem that the balance between low elasticity and low water absorption cannot be obtained.
以上述通式(I)表示之縮水甘油醚化合物中，m+n=1或2之化合物可為例如使用路易酸觸媒，使二環戊二烯二甲醇、與烷基單縮水甘油醚、芳基單縮水甘油醚、烷基芳基單縮水甘油醚或芳基烷基單縮水甘油醚反應，以鹼使觸媒失活後，在鹼及相間移動觸媒存在下使表氯醇與羥基部分反應而製造。 In the glycidyl ether compound represented by the above formula (I), the compound of m+n=1 or 2 may be, for example, a Lewis acid catalyst, dicyclopentadiene dimethanol, and an alkyl monoglycidyl ether. Reaction of an aryl monoglycidyl ether, an alkylaryl monoglycidyl ether or an arylalkyl monoglycidyl ether, and after deactivating the catalyst with a base, the epichlorohydrin and the hydroxyl group are present in the presence of a base and a phase-shifting catalyst. Made by partial reaction.
上述通式(I)中，以R1表示之烷基列舉為例如碳原子數1~18之烷基，例如甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、1-乙基丙基、1,1-二甲基丙基、1,2-二甲基丙基、2,2-二甲基丙基、己基、環 己基、庚基、環己基甲基、辛基、異辛基、2-乙基己基、第三辛基、壬基、癸基、異癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基等直鏈、分支或環狀之基，該等亦可含不飽和基。 In the above formula (I), the alkyl group represented by R1 is exemplified by, for example, an alkyl group having 1 to 18 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a second group. Butyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1 , 2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, ring Hexyl, heptyl, cyclohexylmethyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, decyl, isodecyl, undecyl, dodecyl, thirteen A straight-chain, branched or cyclic group such as an alkyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group or an octadecyl group, which may also contain an unsaturated group.
以R1表示之芳基列舉為例如苯基、萘基等之基。 The aryl group represented by R1 is exemplified by a group such as a phenyl group, a naphthyl group or the like.
以R1表示之烷基芳基列舉為以上述之烷基取代之苯基或萘基。 The alkylaryl group represented by R1 is exemplified by a phenyl group or a naphthyl group substituted with the above alkyl group.
以R1表示之芳基烷基列舉為例如苄基、α-甲基苄基、α,α-二甲基苄基等之基。 The arylalkyl group represented by R1 is exemplified by a group such as a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group or the like.
至於R1，該等中以具有碳原子數4~18之烷基者較佳，藉此獲得低吸水性與低彈性取得均衡者。 As for R1, those having an alkyl group having 4 to 18 carbon atoms are preferred, whereby a balance between low water absorption and low elasticity is obtained.
本發明中，較佳使用式(I)之縮水甘油醚化合物中，m+n=0之化合物，亦即以式(II)表示之化合物：
式(II)之縮水甘油醚化合物可為例如在鹼觸媒及相間移動觸媒存在下，使表氯醇與二環戊二烯二甲醇之羥基部分反應而製造。 The glycidyl ether compound of the formula (II) can be produced, for example, by reacting epichlorohydrin with a hydroxyl group of dicyclopentadiene dimethanol in the presence of a base catalyst and a phase shifting catalyst.
式(I)之縮水甘油醚化合物中，式(II)之 化合物獲得黏度低、導電性黏著劑之操作性提高、且硬化物之表面特性、接著強度及硬度均良好之結果。且，藉由使用式(II)之縮水甘油醚化合物，可將導電性接著劑之導電性之下降抑制至最小。 In the glycidyl ether compound of the formula (I), the formula (II) The compound has low viscosity, improved workability of the conductive adhesive, and good surface properties, adhesion strength, and hardness of the cured product. Further, by using the glycidyl ether compound of the formula (II), the decrease in conductivity of the conductive adhesive can be minimized.
導電性接著劑中之(B)縮水甘油醚化合物之調配比例係自1質量%以上~30質量%，較佳自5質量%~15質量%，更佳自8%~12%之範圍適當選擇。 The proportion of the (B) glycidyl ether compound in the conductive adhesive is from 1% by mass to 30% by mass, preferably from 5% by mass to 15% by mass, more preferably from 8% to 12%. .
本發明之導電性接著劑中包含(C)硬化劑。 The (C) hardener is contained in the conductive adhesive of the present invention.
硬化劑可使用例如二伸乙基三胺、三伸乙基三胺、四伸乙基五胺等鏈狀脂肪族多胺系硬化劑、1,2-二胺基環己烷、1,4-二胺基-3,6-二乙基環己烷、異佛爾酮二胺等脂環式多胺系硬化劑、間-二甲苯二胺、二胺基二苯基甲烷、二胺基二苯基碸等芳香族多胺系硬化劑、哌啶等二級胺系硬化劑、N,N-二甲基哌嗪、三伸乙基二胺、2,4,6-參(二甲胺基甲基)酚、苄基二甲基胺(BDMA)、2-(二甲胺基甲基)酚(DMP-10)等三級胺系硬化劑、及2-甲基咪唑、2-乙基-4-甲基咪唑、1,2-二甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰乙基-2-甲基咪唑、1-氰乙基-2-乙基-4-甲基咪唑、1-氰乙基-2-十一烷基咪唑、1-氰乙基-2-苯基咪唑、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙 基-s-三嗪之異氰尿酸加成物(異氰尿酸加成於咪唑之1位之N上)等之咪唑系硬化劑、甲基四氫鄰苯二甲酸酐、四氫鄰苯二甲酸酐、甲基納迪酸酐、六氫鄰苯二甲酸酐及甲基六氫鄰苯二甲酸酐等酸酐。 As the hardener, for example, a chain aliphatic polyamine-based hardener such as di-ethyltriamine, tri-ethyltriamine or tetra-extended ethylpentamine, 1,2-diaminocyclohexane, 1,4 can be used. - an alicyclic polyamine-based hardener such as diamino-3,6-diethylcyclohexane or isophorone diamine, m-xylylenediamine, diaminodiphenylmethane, or diamine Aromatic polyamine curing agent such as diphenylanthracene, secondary amine curing agent such as piperidine, N,N-dimethylpiperazine, tri-ethylenediamine, 2,4,6-gin (dimethyl) a tertiary amine hardener such as aminomethyl)phenol, benzyldimethylamine (BDMA) or 2-(dimethylaminomethyl)phenol (DMP-10), and 2-methylimidazole, 2- Ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methyl Imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2,4-di Amino-6-[2'-methylimidazolyl-(1')]-B Imidazole-based hardener, methyltetrahydrophthalic anhydride, tetrahydroortylene phthalate, etc. of isocyanuric acid addition product of s-triazine (addition of isocyanuric acid to N at the position of imidazole) Anhydride such as formic anhydride, methyl nadiic anhydride, hexahydrophthalic anhydride or methylhexahydrophthalic anhydride.
另外，亦可使用潛在性硬化劑例如三氟化硼-胺錯合物、雙氰胺(dicyandiamide)、有機酸醯肼(hydrazide)、光‧紫外線硬化劑等。 Further, a latent curing agent such as boron trifluoride-amine complex, dicyandiamide, hydrazide, light ‧ ultraviolet curing agent or the like can also be used.
該等硬化劑中，較好使用咪唑系硬化劑、三級胺系硬化劑，最好使用咪唑系硬化劑。若使用該等硬化劑，則可在較穩定之反應速度下確實地獲得硬化狀態。 Among these hardeners, an imidazole-based curing agent and a tertiary amine-based curing agent are preferably used, and an imidazole-based curing agent is preferably used. If such a hardener is used, the hardened state can be surely obtained at a relatively stable reaction rate.
本發明所用之咪唑系硬化劑之市售品之例可列舉出2MZ、2MZ-P、2PZ、2PZ-PW、2P4MZ、C11Z-CNS、2PZ-CNS、2PZCNS-PW、2MZ-A、2MZA-PW、C11Z-A、2E4MZ-A、2MA-OK、2MAOK-PW、2PZ-OK、2MZ-OK、2PHZ、2PHZ-PW、2P4MHZ、2P4MHZ-PW、2E4MZ‧BIS、VT、VT-OK、MAVT、MAVT-OK(SHIKOKU CHEMICALS CORPORATION製)。 Examples of commercially available imidazole-based hardeners used in the present invention include 2MZ, 2MZ-P, 2PZ, 2PZ-PW, 2P4MZ, C11Z-CNS, 2PZ-CNS, 2PZCNS-PW, 2MZ-A, and 2MZA-PW. , C11Z-A, 2E4MZ-A, 2MA-OK, 2MAOK-PW, 2PZ-OK, 2MZ-OK, 2PHZ, 2PHZ-PW, 2P4MHZ, 2P4MHZ-PW, 2E4MZ‧BIS, VT, VT-OK, MAVT, MAVT -OK (manufactured by SHIKOKU CHEMICALS CORPORATION).
尤其，使用由1-氰乙基-2-苯基咪唑(2PZ-CN：SHIKOKU CHEMICALS CORPORATION製)及2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪異氰尿酸加成物(2MA-OK：SHIKOKU CHEMICALS CORPORATION製)選出之至少1種時，就硬化狀態及保存安定性之觀點而言係較佳。硬化劑可為1種，但亦可併用2種以上。 In particular, 1-cyanoethyl-2-phenylimidazole (2PZ-CN: manufactured by SHIKOKU CHEMICALS CORPORATION) and 2,4-diamino-6-[2'-methylimidazolyl-(1')] are used. When at least one selected from the group consisting of ethyl-s-triazine isocyanuric acid (2MA-OK: manufactured by SHIKOKU CHEMICALS CORPORATION) is preferable from the viewpoint of the hardened state and the storage stability. The curing agent may be used alone or in combination of two or more.
該硬化劑之調配比例相對於縮水甘油醚化合物為1質量%~12質量%，較好為3質量%~9質量%，更好為5質量%~7質量%。 The blending ratio of the curing agent is from 1% by mass to 12% by mass based on the glycidyl ether compound, preferably from 3% by mass to 9% by mass, more preferably from 5% by mass to 7% by mass.
如以上說明之本發明之導電性接著劑可視需要調配消泡劑或調平劑等添加劑。 The conductive adhesive of the present invention as described above may be formulated with an additive such as an antifoaming agent or a leveling agent as needed.
如以上說明之本發明之導電性接著劑在150℃加熱30分鐘之質量減少相較於加熱前之質量較好為0.7質量%以下，更好為0.5質量%以下，又更好為0.3質量%以下。據此，可確實抑制氣泡之結果，可提供量產時具有安定之接著強度之導電性接著劑。 The mass reduction of the conductive adhesive of the present invention heated at 150 ° C for 30 minutes as described above is preferably 0.7% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.3% by mass, compared with the mass before heating. the following. According to this, it is possible to surely suppress the result of the bubbles, and it is possible to provide a conductive adhesive having a stable adhesive strength at the time of mass production.
本發明之導電性接著劑由於可藉由混合上述各成分以一液型接著劑製造，故操作性優異。另外，本發明之導電性接著劑之保存安定性亦優異。 Since the conductive adhesive of the present invention can be produced by mixing the above components with a one-component adhesive, it is excellent in handleability. Further, the conductive adhesive of the present invention is also excellent in storage stability.
以本發明之導電性接著劑使構件彼此之接著可例如下述般進行。 The bonding of the members to each other with the conductive adhesive of the present invention can be carried out, for example, as follows.
藉由利用網篩或金屬罩之圖型印刷、或佈膠機等塗佈裝置之塗佈將接著劑塗佈於印刷電路基板等接著構件之接著部位上。 The adhesive is applied to the subsequent portion of the member such as a printed circuit board by patterning using a mesh screen or a metal cover or coating by a coating device such as a cloth dispenser.
確認接著劑充分供給於接著部位後，將被接著構件(零件)載置於接著構件(基板)之接著部位，以100℃~180℃，較好120℃~160℃之範圍、15分鐘~50分鐘，較好20分鐘~40分鐘之條件加熱、硬化。 After confirming that the adhesive is sufficiently supplied to the subsequent portion, the member to be attached (part) is placed on the subsequent portion of the member (substrate) at a temperature of 100 ° C to 180 ° C, preferably 120 ° C to 160 ° C, and 15 minutes to 50 ° In minutes, it is better to heat and harden under the conditions of 20 minutes to 40 minutes.
藉此，使接著劑中之縮水甘油醚化合物與硬化劑反應而硬化，使接著構件(基板)與載置於其上之被 接著構件(零件)牢固地導電接著。 Thereby, the glycidyl ether compound in the adhesive is reacted with the hardener to be hardened, and the member (substrate) and the member placed thereon are hardened. The component (part) is then electrically conductively followed.
本發明之導電性接著劑較好用於電子零件之接著，不管接著面積如何均顯示優異之接著性。 The conductive adhesive of the present invention is preferably used for the subsequent bonding of electronic parts, and exhibits excellent adhesion regardless of the area to be bonded.
以下，以實施例具體說明本發明，但本發明並不限於該等。又，以下只要無特別指明，則「份」、「%」均為質量基準。 Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited thereto. In addition, unless otherwise specified, "parts" and "%" are the quality standards.
以下述表1所示之調配比例(質量比)調配各成分，攪拌並混合之後，用三軸輥混練機分散。藉此獲得本發明之導電性接著劑及比較用之導電性接著劑。 The components were blended in the blending ratio (mass ratio) shown in Table 1 below, stirred and mixed, and then dispersed by a triaxial roll kneader. Thereby, the conductive adhesive of the present invention and the conductive adhesive for comparison were obtained.
於基板上打開2mm寬之間隙，用透明膠帶施以遮蔽，以刮刀塗佈實施例1~4、比較例1及2所得之導電性接著劑。 A gap of 2 mm width was opened on the substrate, and masking was applied with a transparent tape, and the conductive adhesives obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were applied by a doctor blade.
塗佈後，剝離透明膠帶，使用熱風循環式乾燥爐，在150℃加熱30分鐘而硬化，獲得測定用試驗片。 After the application, the transparent tape was peeled off, and the mixture was heated at 150 ° C for 30 minutes using a hot air circulating drying oven to obtain a test piece for measurement.
針對所得試驗片，使用表面粗糙度測量機(Kosaka Laboratory Ltd.製SE-30H)測定導電性接著劑之圖型膜厚，且使用MEASURING MICROSCOPE(OLYMPUS Corporation製STM-MJS)測定圖型寬度。另外，使用測試機(HIOKI E.E.Corporation製mΩ HiTESTER 3540)測定圖型長度5cm之電阻值R。 For the obtained test piece, a surface roughness measuring machine (Kosaka) was used. SE-30H manufactured by Laboratory Ltd.) The film thickness of the conductive adhesive was measured, and the pattern width was measured using MEASURING MICROSCOPE (STM-MJS manufactured by OLYMPUS Corporation). Further, a resistance value R of a pattern length of 5 cm was measured using a tester (mΩ HiTESTER 3540 manufactured by HIOKI E.E. Corporation).
由上述測定之膜厚、圖型寬度、圖型長度(5cm)、電阻值，藉下述式算出比電阻值(Ω‧cm)。 The specific resistance value (Ω‧ cm) was calculated from the film thickness, the pattern width, the pattern length (5 cm), and the resistance value measured as described above by the following formula.
ρ(Ω‧cm)=R(Ω)‧A(cm2)/L(cm) ρ (Ω‧cm)=R(Ω)‧A(cm 2 )/L(cm)
ρ：比電阻值 ρ: specific resistance value
R：電阻值 R: resistance value
A：剖面積 A: sectional area
L：長度 L: length
所得結果示於表1。 The results obtained are shown in Table 1.
在玻璃環氧樹脂貼銅基板(基材FR4，銅厚度35μm)上以空出約10mm寬之間隙以透明膠帶施以遮蔽，以刮刀塗佈實施例1~4、比較例1及2所得之導電性接著劑。 On a glass epoxy resin-coated copper substrate (substrate FR4, copper thickness: 35 μm), a transparent tape was masked with a gap of about 10 mm wide, and the coatings of Examples 1 to 4 and Comparative Examples 1 and 2 were applied by doctor blade. Conductive adhesive.
塗佈後，剝離透明膠帶，配置鍍金之M3螺帽(二面寬：5.5mm，對角距離：6.4mm，高度：2.4mm，1種)之無倒角之有孔之面作為接著面，使用熱風循環式乾燥爐，在150℃加熱30分鐘進行接著。藉此獲得測定用 試驗片。 After coating, the scotch tape was peeled off, and a gold-plated M3 nut (two-sided width: 5.5 mm, diagonal distance: 6.4 mm, height: 2.4 mm, one type) of a non-chamfered perforated surface was used as a joint surface. The mixture was heated at 150 ° C for 30 minutes using a hot air circulating drying oven. Thereby obtaining measurement Test piece.
對所得試驗片之經接著之鍍金M3螺帽之側面，以對於基板面平行之方式施加剪斷速度5mm/min之剪斷力，使用數位測力計(日本NIDEC-SHIMPO股份有限公司製之FGP-50，電動立式FCS-TV)，測定鍍金M3螺帽與基板之接著面之剪斷強度。將測定之剪斷強度除以鍍金M3螺帽之接著面積算出接著強度。 A shearing force of a cutting speed of 5 mm/min was applied to the side of the obtained gold-plated M3 nut of the obtained test piece in parallel with the substrate surface, and a digital dynamometer (FGP manufactured by NIDEC-SHIMPO Co., Ltd., Japan) was used. -50, electric vertical FCS-TV), measuring the shear strength of the gold-plated M3 nut and the substrate. The subsequent strength was calculated by dividing the measured shear strength by the area of the gold-plated M3 nut.
所得結果一併示於表1。 The results obtained are shown together in Table 1.
關於塗佈狀態對於塗佈導電性接著劑之塗膜以目視確認有無模糊不清或滲出，且確認均無問題。 Regarding the coating state, it was visually confirmed whether or not the coating film of the conductive adhesive was applied, and it was confirmed that there was no problem.
對各樣品之接著劑硬化部分測定鉛筆硬度(根據JIS K 5600之試驗方法)。確認所有樣品均為8H以上之鉛筆硬度。 The pencil hardness (measured according to JIS K 5600) was measured for the adhesive hardening portion of each sample. Confirm that all samples are pencil hardness of 8H or more.
於直徑5cm之鋁盤上分別取樣2g之實施例1~4、比較例1及2所得之導電性接著劑，以熱風循環式乾燥爐，在150℃加熱30分鐘，測定加熱後之質量。比較加熱前後之各接著劑之質量，質量減少均為0.3質量%以下。 2 g of the conductive adhesives of Examples 1 to 4 and Comparative Examples 1 and 2 were sampled on an aluminum disk having a diameter of 5 cm, and heated in a hot air circulating drying oven at 150 ° C for 30 minutes to measure the mass after heating. The mass of each of the adhesives before and after heating was compared, and the mass reduction was 0.3% by mass or less.
上述表1中之材料如下。 The materials in Table 1 above are as follows.
縮水甘油醚化合物：ADEKA Corporation製EP-4088L(二環戊二烯二甲醇型環氧樹脂，環氧當量：165g/eq，黏度：2.3dPa‧s，總氯：0.09質量%) Glycidyl ether compound: EP-4088L (dicyclopentadiene dimethanol type epoxy resin, epoxy equivalent: 165 g/eq, viscosity: 2.3 dPa‧s, total chlorine: 0.09 mass%) manufactured by ADEKA Corporation
導電粉末1：片狀銀粉(METALOR Corporation製EA-0101，比表面積：0.32m2/g，敲實密度：5.5g/cm3，平均粒徑5.5μm) Conductive powder 1: flake silver powder (EA-0101, manufactured by METALLOR Corporation, specific surface area: 0.32 m 2 /g, tapping density: 5.5 g/cm 3 , average particle diameter: 5.5 μm)
導電粉末2：片狀銀粉(DOWA Electronic Corporation製FA-D-6，比表面積：0.24m2/g，敲實密度：5.3g/cm3，平均粒徑9.6μm) Conductive powder 2: flake silver powder (FA-D-6 manufactured by DOWA Electronic Corporation, specific surface area: 0.24 m 2 /g, tapping density: 5.3 g/cm 3 , average particle diameter: 9.6 μm)
導電粉末3：片狀銀粉(DOWA Electronic Corporation製FA-S-12，比表面積：0.96m2/g，敲實密度：5.2g/cm3，平均粒徑2.1μm) Conductive powder 3: flake silver powder (FA-S-12 manufactured by DOWA Electronic Corporation, specific surface area: 0.96 m 2 /g, tapping density: 5.2 g/cm 3 , average particle diameter 2.1 μm)
導電粉末4：片狀銀粉(DOWA Electronic Corporation製AA-4703，比表面積：1.01m2/g，敲實密度：3.5g/cm3，平均粒徑4μm) Conductive powder 4: flake silver powder (AAWA703 manufactured by DOWA Electronic Corporation, specific surface area: 1.01 m 2 /g, tapping density: 3.5 g/cm 3 , average particle diameter 4 μm)
導電粉末5：球狀銀粉(METALOR Corporation製K-0082P，比表面積：0.99m2/g，敲實密度：5.4g/cm3，平均粒徑1.5μm) Conductive powder 5: spherical silver powder (K-0082P manufactured by METALLOR Corporation, specific surface area: 0.99 m 2 /g, tapping density: 5.4 g/cm 3 , average particle diameter: 1.5 μm)
硬化劑：2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪異氰尿酸加成物(SHIKOKU CHEMICALS CORPORATION製2MAOK-PW) Hardener: 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct (2MAOK-PW, manufactured by SHIKOKU CHEMICALS CORPORATION)
導電粉末(A-1)：在各實施例/比較例中混合使用，大粒徑之銀粉 Conductive powder (A-1): mixed in each of the examples/comparative examples, large-sized silver powder
導電粉末(A-2)：在各實施例/比較例中混合使用，小粒徑之銀粉 Conductive powder (A-2): mixed in each of the examples/comparative examples, small-sized silver powder
無法測定：意指電阻值過大而無法測定。 Unable to measure: means that the resistance value is too large to be measured.
由表1可了解，實施例1~4之導電性接著劑之硬化物係比電阻較小，同時具有優異之接著強度者。相對於此，比較例1及2之導電性接著劑確認電阻值非常大。 As can be seen from Table 1, the cured adhesives of the conductive adhesives of Examples 1 to 4 have a small specific resistance and excellent adhesion strength. On the other hand, the conductive adhesives of Comparative Examples 1 and 2 confirmed that the resistance value was extremely large.
又，本發明之導電性接著劑在塗佈狀態、硬度、質量減少方面均不比比較例之組成物遜色，具有優良之品質。 Further, the conductive adhesive of the present invention is inferior to the composition of the comparative example in terms of coating state, hardness, and mass reduction, and has excellent quality.
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| JP6636874B2 (en) * | 2016-07-28 | 2020-01-29 | 京セラ株式会社 | Resin composition for bonding electronic components, bonding method for electronic components, and electronic component mounting substrate |
| KR102387641B1 (en) * | 2017-06-07 | 2022-04-18 | 다나카 기킨조쿠 고교 가부시키가이샤 | Thermally conductive conductive adhesive composition |
| WO2019111778A1 (en) * | 2017-12-04 | 2019-06-13 | 住友ベークライト株式会社 | Pasty adhesive composition and semiconductor device |
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| JP2950670B2 (en) * | 1991-12-10 | 1999-09-20 | マルコン電子株式会社 | Solid electrolytic capacitors |
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| JP2974902B2 (en) * | 1993-12-24 | 1999-11-10 | 住友ベークライト株式会社 | Conductive resin paste |
| JP3588400B2 (en) * | 1996-04-18 | 2004-11-10 | ナミックス株式会社 | Conductive resin composition and method of forming conductor |
| JP2003129017A (en) * | 2001-10-25 | 2003-05-08 | Sumitomo Bakelite Co Ltd | Conductive adhesive film and semiconductor device using the same |
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| JP4569109B2 (en) * | 2004-01-08 | 2010-10-27 | 住友ベークライト株式会社 | Metal-containing paste and semiconductor device |
| JP4363340B2 (en) * | 2004-03-12 | 2009-11-11 | 住友電気工業株式会社 | Conductive silver paste and electromagnetic wave shielding member using the same |
| JP2008174577A (en) * | 2007-01-16 | 2008-07-31 | Kyocera Chemical Corp | Die bonding paste and semiconductor device using the same |
| TWI405519B (en) * | 2007-04-23 | 2013-08-11 | Panasonic Corp | A conductive paste composition for hole filling, a printed circuit board using the same, and a method for manufacturing the same |
| GB0710425D0 (en) * | 2007-06-01 | 2007-07-11 | Hexcel Composites Ltd | Improved structural adhesive materials |
| JP4935592B2 (en) * | 2007-09-13 | 2012-05-23 | 昭栄化学工業株式会社 | Thermosetting conductive paste |
| JP5257574B2 (en) * | 2007-12-10 | 2013-08-07 | 福田金属箔粉工業株式会社 | Solvent-free conductive adhesive |
| KR20110025836A (en) * | 2008-07-03 | 2011-03-11 | 헨켈 코포레이션 | Silver coated flaky material filled conductive curable composition and the application in die attach |
| US8749076B2 (en) * | 2010-06-17 | 2014-06-10 | Hitachi Chemical Company, Ltd. | Resin paste composition |
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| CN102013281A (en) * | 2010-12-11 | 2011-04-13 | 广东风华高新科技股份有限公司 | Conductive silver adhesive for high-power LED |
| JP2015042696A (en) * | 2011-12-22 | 2015-03-05 | 味の素株式会社 | Conductive adhesive |
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| JP6255664B2 (en) | 2012-11-22 | 2018-01-10 | 富士電機機器制御株式会社 | Thermal overload relay |
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