TW201736549A - Electroconductive adhesive - Google Patents
Electroconductive adhesive Download PDFInfo
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- TW201736549A TW201736549A TW106108284A TW106108284A TW201736549A TW 201736549 A TW201736549 A TW 201736549A TW 106108284 A TW106108284 A TW 106108284A TW 106108284 A TW106108284 A TW 106108284A TW 201736549 A TW201736549 A TW 201736549A
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- fine particles
- silver fine
- conductive adhesive
- protective layer
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Classifications
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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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- 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
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- 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
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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
- C09J1/00—Adhesives based on inorganic constituents
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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
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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
- H01B1/20—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
Abstract
Description
本發明係關於導電性黏著劑、其製造方法、該導電性黏著劑之燒結體及於構件間具有該燒結體之電路或電極。The present invention relates to a conductive adhesive, a method for producing the same, a sintered body of the conductive adhesive, and a circuit or electrode having the sintered body between members.
發明背景 以固晶(die bond)及晶粒黏著劑(die attach agent)為首之導電性黏著劑係使用於半導體、LED及功率半導體等之接合材料。作為其方式，一般來說，所知的有利用加壓及加熱之接合，或是於無加壓下藉由利用加熱等之燒結而使其與基材接合。近年來，基於製程之簡易度及效率之觀點，無加壓方式之接合材料的開發日益進步。BACKGROUND OF THE INVENTION Conductive adhesives, such as die bonds and die attach agents, are used in bonding materials for semiconductors, LEDs, and power semiconductors. As a general aspect, it is generally known that it is joined to a substrate by sintering by pressurization or heating or by sintering by heating or the like without pressure. In recent years, the development of bonding materials without pressure has been progressing on the basis of the simplicity and efficiency of the process.
作為無加壓方式之接合材料可舉一含有環氧樹脂之導電性黏著劑為例。該接合材料係以低溫處理使環氧樹脂硬化而作使用者，且可抑制空隙產生(void generation)及使與基材之接合強度提升(專利文獻1)。但是，由於環氧樹脂本身會成為電阻，故所得之導電性會變低。As the bonding material of the non-pressurizing method, a conductive adhesive containing an epoxy resin can be exemplified. In the bonding material, the epoxy resin is cured by low-temperature treatment, and the void generation (void generation) and the bonding strength with the substrate can be suppressed (Patent Document 1). However, since the epoxy resin itself becomes a resistor, the resulting conductivity becomes low.
另一方面，不含環氧樹脂之接合材料，可舉僅由銀構成之導電性黏著劑。該接合材料係使用微米銀或次微米銀(粒徑300~900nm) (專利文獻2)，但從容易發生空隙之觀點來看，以一般之燒結反應來說需於200~250℃下處理1小時，而尋求開發一種可以較低溫且短時間之處理獲得高剪切強度(接合性高之材料)且可抑制空隙發生的接合材料。On the other hand, a bonding material containing no epoxy resin is a conductive adhesive composed only of silver. The bonding material is micron silver or submicron silver (particle diameter: 300 to 900 nm) (Patent Document 2), but from the viewpoint of easy occurrence of voids, it is required to be treated at 200 to 250 ° C in general sintering reaction. In the meantime, it has been sought to develop a bonding material which can obtain high shear strength (high bonding property) and which can suppress the occurrence of voids, which can be processed at a relatively low temperature and for a short period of time.
近年來，銀奈米微粒子之開發與時俱進，且銀奈米微粒子具有容易以低溫且短時間之熱處理進行燒結之特徵。尤其是使用了粒徑為20nm左右之銀奈米微粒子時，可容易以較低溫(200℃以下)進行燒結，並形成緻密的膜。然而，於接合材料中摻混了許多20nm左右之粒子時，隨著膜厚變厚塗膜中會發生應力，其結果為產生龜裂及破裂。因此而尋求開發一種可抑制空隙發生且塗膜之應力少的材料。In recent years, the development of silver nanoparticles has progressed with the times, and the silver nanoparticles have the characteristics of being easily sintered by a low temperature and short time heat treatment. In particular, when silver nanoparticles having a particle diameter of about 20 nm are used, sintering can be easily performed at a relatively low temperature (200 ° C or lower) to form a dense film. However, when a large amount of particles of about 20 nm are blended in the bonding material, stress is generated in the coating film as the film thickness increases, and as a result, cracks and cracks are generated. Therefore, it has been sought to develop a material which can suppress the occurrence of voids and which has less stress on the coating film.
作為滿足此要求之材料，則提案有一種含有奈米大小之金屬奈米微粒子的導電性黏著劑(例如參閱專利文獻3)。 先前技術文獻 專利文獻As a material satisfying this requirement, a conductive adhesive containing nano-sized metal nanoparticles has been proposed (for example, see Patent Document 3). Prior Technical Literature Patent Literature
專利文獻1：國際公開2010/18712 專利文獻2：國際公開2014/104046 專利文獻3：日本特開2006-83377號公報Patent Document 1: International Publication No. 2010/18712 Patent Document 2: International Publication No. 2014/104046 Patent Document 3: Japanese Laid-Open Patent Publication No. 2006-83377
發明概要 發明欲解決之課題 含有奈米大小之金屬奈米微粒子的導電性黏著劑於配置在構件間之狀態下，經高溫(例如200℃以上)加熱、燒結成燒結體後可黏著構件間且同時發揮高導電性。SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The conductive adhesive containing nano-sized metal nano-particles can be adhered to a sintered body after being heated at a high temperature (for example, 200 ° C or higher) in a state of being disposed between members. At the same time, it exerts high conductivity.
但是，本案發明人經進行檢討後發現就含有奈米大小銀微粒子之習知的導電性黏著劑而言，於所得之燒結體會發生龜裂及破裂等，而使機械強度降低。特別是，基於更加提升導電性之觀點而增長燒結時之加熱時間或提高加熱溫度的話，會顯著地發生燒結體龜裂及破裂的問題。However, the inventors of the present invention have found that a conventional conductive adhesive containing nano-sized silver fine particles causes cracks, cracks, and the like in the obtained sintered body to lower the mechanical strength. In particular, when the heating time at the time of sintering is increased or the heating temperature is increased from the viewpoint of further improving the conductivity, the problem of cracking and cracking of the sintered body remarkably occurs.
於如此狀況下，本發明主要之目的即在於提供一種導電性黏著劑，其可製得不易發生因燒結所致之龜裂及破裂等且機械強度優異的燒結體。並且，本發明之目的亦在於提供導電性黏著劑之製造方法、導電性黏著劑之燒結體及於構件間具有該燒結體之電路或電極。 用以解決課題之手段Under such circumstances, the main object of the present invention is to provide a conductive adhesive which can produce a sintered body which is less likely to cause cracks and cracks due to sintering and which is excellent in mechanical strength. Further, an object of the present invention is to provide a method for producing a conductive adhesive, a sintered body of a conductive adhesive, and a circuit or electrode having the sintered body between members. Means to solve the problem
本案發明人為了解決前述課題曾進行鑽研檢討。結果發現藉由於導電性黏著劑中使用具有第1保護層且平均粒徑為10nm~30nm的第1銀微粒子A以及具有含羥基脂肪酸之第2保護層且平均粒徑為50nm~100nm的第2銀微粒子B，並且將第1銀微粒子A與前述第2銀微粒子B之質量比(A：B)設在5：95~40：60之特定範圍，可有效抑制導電性黏著劑之燒結體龜裂及破裂，並製得機械強度優異之燒結體。並且，亦發現像這樣的燒結體具有高導電性且接著性優異。本發明係基於前文所述之見解並且經由反覆檢討而完成者。The inventor of the present invention conducted a research review in order to solve the above problems. As a result, it was found that the first silver fine particle A having the first protective layer and having an average particle diameter of 10 nm to 30 nm and the second protective layer having a hydroxyl group-containing fatty acid and having an average particle diameter of 50 nm to 100 nm were used for the conductive adhesive. Silver fine particle B, and the mass ratio (A:B) of the first silver fine particle A to the second silver fine particle B is set to a specific range of 5:95 to 40:60, and the sintered body of the conductive adhesive can be effectively suppressed. Cracking and cracking, and producing a sintered body excellent in mechanical strength. Further, it has been found that such a sintered body has high conductivity and is excellent in adhesion. The present invention has been completed based on the findings described above and through repeated review.
即，本發明提供下述所載形態之發明。 (1)一種導電性黏著劑，含有： 第1銀微粒子A，其具有第1保護層且平均粒徑為10nm~30nm；及 第2銀微粒子B，其具有第2保護層且平均粒徑為50nm~100nm；其中， 前述第2保護層含有羥基脂肪酸； 並且，前述第1銀微粒子A與前述第2銀微粒子B之質量比(A：B)在5：95~40：60之範圍內。 (2)如(1)之導電性黏著劑，其中前述第1保護層含有脂肪酸及烷基胺中之至少一者。 (3)如(1)或(2)之導電性黏著劑，其中前述第1銀微粒子A與前述第2銀微粒子B之合計比率為80質量%以上。 (4)如(1)至(3)中任一項之導電性黏著劑，其更含有溶劑。 (5)一種導電性黏著劑之製造方法，具有下述步驟：將第1銀微粒子A與第2銀微粒子B以使第1銀微粒子A與第2銀微粒子B之質量比(A:B)在5：95~40：60之範圍內之方式進行混合，其中前述第1銀微粒子A具有第1保護層且平均粒徑為10nm~30nm，前述第2銀微粒子B具有含羥基脂肪酸之第2保護層且平均粒徑為50nm~100nm。 (6)一種導電性黏著劑之燒結體，該導電性黏著劑係如(1)至(4)中任一項之導電性黏著劑。 (7)一種電路或電極，具有構件間已藉由如(6)之燒結體黏結的部分。 發明效果That is, the present invention provides the invention of the form described below. (1) A conductive adhesive comprising: a first silver fine particle A having a first protective layer and having an average particle diameter of 10 nm to 30 nm; and a second silver fine particle B having a second protective layer and having an average particle diameter of 50 nm to 100 nm; wherein the second protective layer contains a hydroxy fatty acid; and the mass ratio (A:B) of the first silver fine particles A to the second silver fine particles B is in the range of 5:95 to 40:60. (2) The conductive adhesive according to (1), wherein the first protective layer contains at least one of a fatty acid and an alkylamine. (3) The conductive adhesive according to (1) or (2), wherein a total ratio of the first silver fine particles A to the second silver fine particles B is 80% by mass or more. (4) The conductive adhesive according to any one of (1) to (3), which further contains a solvent. (5) A method for producing a conductive adhesive, comprising the steps of: mass ratio of first silver fine particles A and second silver fine particles B to first silver fine particles A and second silver fine particles B (A: B) Mixing is carried out in a range of 5:95 to 40:60, wherein the first silver fine particles A have a first protective layer and have an average particle diameter of 10 nm to 30 nm, and the second silver fine particles B have a second hydroxyl group-containing fatty acid. The protective layer has an average particle diameter of 50 nm to 100 nm. (6) A sintered body of a conductive adhesive, which is the conductive adhesive according to any one of (1) to (4). (7) A circuit or electrode having a portion between members which has been bonded by a sintered body such as (6). Effect of the invention
依據本發明可提供一種導電性黏著劑，其可製得不易發生因燒結所致之龜裂及破裂等且機械強度(剪切強度)優異之燒結體。並且，依據本發明可提供該導電性黏著劑之製造方法、該導電性黏著劑之燒結體、及構件間具有該燒結體之電路或電極。According to the present invention, it is possible to provide a conductive adhesive which can produce a sintered body which is less likely to cause cracks and cracks due to sintering and which is excellent in mechanical strength (shear strength). Further, according to the present invention, a method for producing the conductive adhesive, a sintered body of the conductive adhesive, and a circuit or an electrode having the sintered body between the members can be provided.
用以實施發明之形態 本發明之導電性黏著劑之特徵在於含有：第1銀微粒子A，其具有第1保護層且平均粒徑為10nm~30nm；及第2銀微粒子B，其具有第2保護層且平均粒徑為50nm~100nm；其中，第2保護層含有羥基脂肪酸；並且，第1銀微粒子A與第2銀微粒子B之質量比(A:B)在5：95~40：60之範圍內。以下，就本發明之導電性黏著劑、該導電性黏著劑之製造方法、該導電性黏著劑之燒結體及構件間具有該燒結體之電路或電極進行詳細敘述。The conductive adhesive of the present invention is characterized by comprising: first silver fine particles A having a first protective layer and having an average particle diameter of 10 nm to 30 nm; and second silver fine particles B having a second The protective layer has an average particle diameter of 50 nm to 100 nm; wherein the second protective layer contains a hydroxy fatty acid; and the mass ratio (A:B) of the first silver fine particles A to the second silver fine particles B is 5:95 to 40:60 Within the scope. Hereinafter, the conductive adhesive of the present invention, the method for producing the conductive adhesive, the sintered body of the conductive adhesive, and the circuit or electrode having the sintered body between the members will be described in detail.
1.導電性黏著劑 本發明之導電性黏著劑係以預定之比率含有前述第1銀微粒子A及第2銀微粒子B(以下有將「第1銀微粒子A及第2銀微粒子B」總稱為「銀微粒子」的情形)。1. Conductive Adhesive The conductive adhesive of the present invention contains the first silver fine particles A and the second silver fine particles B in a predetermined ratio (hereinafter, "the first silver fine particles A and the second silver fine particles B" are collectively referred to as "the first silver fine particles A and the second silver fine particles B". The case of "silver particles").
第1銀微粒子A於由銀所構成之粒子(銀粒子)的表層具有第1保護層。作為形成第1保護層之材料只要為可形成銀粒子之表層且可作為保護層發揮機能者(比如抑制第1銀微粒子A及第2銀微粒子B凝集的層)，則並無特別限制，但從有效提升導電性黏著劑之燒結體的機械強度之觀點來看，可舉例如宜為脂肪酸、烷基胺及羥基脂肪酸等。保護層可由1種材料構成亦可由2種以上之材料構成。The first silver fine particles A have a first protective layer on the surface layer of the particles (silver particles) composed of silver. The material for forming the first protective layer is not particularly limited as long as it can form a surface layer of silver particles and can function as a protective layer (for example, a layer that suppresses aggregation of the first silver fine particles A and the second silver fine particles B). From the viewpoint of effectively increasing the mechanical strength of the sintered body of the conductive adhesive, for example, a fatty acid, an alkylamine, a hydroxy fatty acid, or the like is preferable. The protective layer may be composed of one type of material or two or more types of materials.
脂肪酸雖然並無特別限制，但可舉例如下：宜為烷基之碳數為3以上且18以下之脂肪酸，較佳為烷基之碳數為4以上且18以下之脂肪酸。作為脂肪酸之理想的具體例可舉醋酸、丙酸、酪酸、纈草酸、己酸、辛酸、2-乙基己酸、癸酸、月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸、油酸、亞麻油酸及α-亞麻酸等。又，作為脂肪酸之具體例亦可舉如環己烷羧酸之環烷基羧酸等。而於該等之中，從有效提升導電性黏著劑之燒結體的機械強度之觀點來看，以己酸、2-乙基己酸、油酸、亞麻油酸及α-亞麻酸為佳。脂肪酸可單獨使用1種，亦可組合2種以上來作使用。The fatty acid is not particularly limited, and may be, for example, a fatty acid having an alkyl group having 3 or more and 18 or less carbon atoms, preferably a fatty acid having 4 or more and 18 or less carbon atoms. Specific examples of the fatty acid include acetic acid, propionic acid, butyric acid, shikimic acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, citric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid. , linoleic acid and α-linolenic acid. Further, specific examples of the fatty acid may, for example, be a cycloalkylcarboxylic acid of a cyclohexanecarboxylic acid. Among these, hexanoic acid, 2-ethylhexanoic acid, oleic acid, linoleic acid, and α-linolenic acid are preferred from the viewpoint of effectively increasing the mechanical strength of the sintered body of the conductive adhesive. The fatty acid may be used singly or in combination of two or more.
烷基胺雖然並無特別限制，但可舉例如下：宜為烷基之碳數為3以上且18以下之烷基胺，較佳為烷基之碳數為4以上且12以下之烷基胺。另外，就本發明之導電性黏著劑而言，在銀微粒子A之第1保護層中含有烷基胺時，由於導電性黏著劑燒結時，該第1保護層中之烷基胺會自銀微粒子A之表面脫離，故不會對所得之燒結體之導電性帶來實質的影響。The alkylamine is not particularly limited, and may, for example, be an alkylamine having an alkyl group having 3 or more and 18 or less carbon atoms, preferably an alkylamine having an alkyl group having 4 or more and 12 or less carbon atoms. . Further, in the conductive adhesive of the present invention, when the alkylamine is contained in the first protective layer of the silver fine particles A, the alkylamine in the first protective layer is derived from silver when the conductive adhesive is sintered. Since the surface of the fine particles A is detached, it does not substantially affect the conductivity of the obtained sintered body.
烷基胺之理想的具體例可舉例如：乙胺、正丙胺、異丙胺、1,2‐二甲基丙胺、正丁胺、異丁胺、二級丁胺、三級丁胺、異戊胺、三級戊胺、3‐戊胺、正戊胺、正己胺、正庚胺、正辛胺、2‐辛胺、2‐乙基己胺、正壬胺、正胺基癸烷、正胺基十一烷、正十二胺、正十三胺、2‐十三胺、正十四胺、正十五胺、正十六胺、正十七胺、正十八胺、正油胺(n-oleylamine)、N‐乙基‐1,3‐二胺丙烷、N,N‐二異丙基乙基胺、N,N‐二甲胺丙烷、N,N‐二丁胺丙烷、N,N-二甲基-1,3-二胺丙烷、N,N-二乙基-1,3-二胺丙烷、N,N‐二異丁基‐1,3‐二胺丙烷及N‐月桂二胺丙烷等。還可舉例如為2級胺之二丁胺及為環烷基胺之環丙胺、環丁胺、環丙胺、環己胺、環庚胺及環辛胺等。而於該等之中，從有效提升導電性黏著劑之燒結體的機械強度之觀點來看，以正丙胺、異丙胺、環丙胺、正丁胺、異丁胺、二級丁胺、三級丁胺、環丁胺、正戊胺、正己胺、環己胺、正辛胺、2‐乙基己胺、正十二胺、正油胺、N,N-二甲基-1,3-二胺丙烷及N,N-二乙基-1,3-二胺丙烷為佳，較佳為正丁胺、正己胺、環己胺、正辛胺、正十二胺、N,N-二甲基-1,3-二胺丙烷及N,N-二乙基-1,3-二胺丙烷。烷基胺可單獨使用1種，亦可組合2種以上使用。Desirable specific examples of the alkylamine include, for example, ethylamine, n-propylamine, isopropylamine, 1,2-dimethylpropylamine, n-butylamine, isobutylamine, secondary butylamine, tertiary butylamine, and isoprene. Amine, tertiary pentylamine, 3-pentylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-octylamine, 2-ethylhexylamine, n-decylamine, n-aminodecane, positive Aminoundecane, n-dodecylamine, n-tridecylamine, 2-tridecanamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n-oleylamine (n-oleylamine), N-ethyl-1,3-diamine propane, N,N-diisopropylethylamine, N,N-dimethylaminepropane, N,N-dibutylaminepropane, N , N-dimethyl-1,3-diamine propane, N,N-diethyl-1,3-diamine propane, N,N-diisobutyl-1,3-diamine propane and N- Laurel diamine propane and the like. Further, for example, dibutylamine of a secondary amine and cyclopropylamine, cyclobutylamine, cyclopropylamine, cyclohexylamine, cycloheptylamine, and cyclooctylamine which are cycloalkylamines may be mentioned. Among these, n-propylamine, isopropylamine, cyclopropylamine, n-butylamine, isobutylamine, secondary butylamine, and tertiary grade are used from the viewpoint of effectively improving the mechanical strength of the sintered body of the conductive adhesive. Butylamine, cyclobutylamine, n-pentylamine, n-hexylamine, cyclohexylamine, n-octylamine, 2-ethylhexylamine, n-dodecylamine, n-oleylamine, N,N-dimethyl-1,3- Diamine propane and N,N-diethyl-1,3-diamine propane are preferred, preferably n-butylamine, n-hexylamine, cyclohexylamine, n-octylamine, n-dodecylamine, N,N-di Methyl-1,3-diaminepropane and N,N-diethyl-1,3-diaminepropane. The alkylamine may be used singly or in combination of two or more.
於第1保護層中，併用烷基胺與脂肪酸時，烷基胺與脂肪酸之莫耳比(烷基胺：脂肪酸)舉例來說宜為約90:10~約99.9:0.1之範圍，較佳為約95:5~約99.5:0.5之範圍。In the first protective layer, when the alkylamine and the fatty acid are used in combination, the molar ratio of the alkylamine to the fatty acid (alkylamine: fatty acid) is preferably in the range of about 90:10 to about 99.9:0.1, preferably. It is in the range of about 95:5 to about 99.5:0.5.
作為第1保護層中可能含有之羥基脂肪酸可舉與後述第2保護層中所含之羥基脂肪酸相同者。The hydroxy fatty acid which may be contained in the first protective layer may be the same as the hydroxy fatty acid contained in the second protective layer described later.
第1銀微粒子A中之第1保護層之比率(質量%)，雖然並無特別限制，然而從在保護第1銀微粒子A之表面的同時亦有效提高導電性黏著劑之燒結體的機械強度之觀點來看，可舉例如宜為0.1質量%~10質量%左右，較佳為1質量%~8質量%左右。The ratio (% by mass) of the first protective layer in the first silver fine particles A is not particularly limited, but the mechanical strength of the sintered body of the conductive adhesive is also effectively improved while protecting the surface of the first silver fine particles A. From the viewpoint of the above, it is preferably from about 0.1% by mass to about 10% by mass, preferably from about 1% by mass to about 8% by mass.
第1銀微粒子A之平均粒徑係在10nm~30nm之範圍。於本發明中，係以特定之摻混比來併用具有所述特定粒徑之第1銀微粒子A與後述之第2銀微粒子A，藉此可有效提高導電性黏著劑之燒結體的機械強度。基於相同觀點，第1銀微粒子A之平均粒徑宜在15~25nm之範圍。The average particle diameter of the first silver fine particles A is in the range of 10 nm to 30 nm. In the present invention, the first silver fine particles A having the specific particle diameter and the second silver fine particles A described later are used in combination with a specific blending ratio, whereby the mechanical strength of the sintered body of the conductive adhesive can be effectively improved. . From the same viewpoint, the average particle diameter of the first silver fine particles A is preferably in the range of 15 to 25 nm.
於本發明中，第1銀微粒子A之平均粒徑係在掃描式電子顯微鏡下所觀察之影像中所含30個以上之粒子之長邊長度的平均值。另外，於僅針對本發明之第1銀微粒子A以掃描式電子顯微鏡作觀察時，可令其為影像中所含任意30個以上之粒子之長邊長度的平均值。又，於針對混合了第1銀微粒子A與後述第2銀微粒子B的導電性黏著劑求取第1銀微粒子A之平均粒徑時，係依序選擇30個以上於掃描式電子顯微鏡下所觀察之影像中所含粒子之長邊短的粒子，並以此為針對該30個以上之粒子之長邊長度的平均值。In the present invention, the average particle diameter of the first silver fine particles A is an average value of the long side lengths of 30 or more particles contained in the image observed under a scanning electron microscope. Further, when only the first silver fine particles A of the present invention are observed by a scanning electron microscope, the average value of the long side lengths of any 30 or more particles contained in the image can be obtained. When the average particle diameter of the first silver fine particles A is obtained for the conductive adhesive in which the first silver fine particles A and the second silver fine particles B described later are mixed, 30 or more are sequentially selected under a scanning electron microscope. The particles having short sides of the particles contained in the observed image are averaged for the length of the long sides of the 30 or more particles.
第2銀微粒子B係於由銀所構成之粒子(銀粒子)的表層具有第2保護層。於本發明中，第2保護層含有羥基脂肪酸。The second silver fine particles B have a second protective layer on the surface layer of the particles (silver particles) made of silver. In the present invention, the second protective layer contains a hydroxy fatty acid.
羥基脂肪酸可使用碳數3~24且具羥基1個以上(例如1個)的化合物。羥基脂肪酸可舉例如2-羥基癸酸、2-羥基十二酸、2-羥基十四酸、2-羥基十六酸、2-羥基十八酸、2-羥基二十酸、2-羥基二十二酸、2-羥基二十三酸、2-羥基二十四酸、3-羥基己酸、3-羥基辛酸、3-羥基壬酸、3-羥基癸酸、3-羥基十一酸、3-羥基十二酸、3-羥基十三酸、3-羥基十四酸、3-羥基十六酸、3-羥基十七酸、3-羥基十八酸、ω-羥基-2-癸烯酸、ω-羥基十五酸、ω-羥基十七酸、ω-羥基二十酸、ω-羥基二十二酸、6-羥基十八酸、蓖麻油酸、12-羥基硬脂酸及[R-(E)]-12-羥基-9-十八烯酸等。其中又以碳數4~18且在ω位以外(尤其是12 位)具1個羥基之羥基脂肪酸為佳，較佳為蓖麻油酸及12-羥基硬脂酸。第2保護層中所含之羥基脂肪酸可為1種亦可為2種以上。As the hydroxy fatty acid, a compound having 3 to 24 carbon atoms and having one or more hydroxyl groups (for example, one) can be used. The hydroxy fatty acid may, for example, be 2-hydroxydecanoic acid, 2-hydroxydodecanoic acid, 2-hydroxytetradecanoic acid, 2-hydroxyhexadecanoic acid, 2-hydroxyoctadecanoic acid, 2-hydroxyicosanoic acid, 2-hydroxydicarboxylic acid. Dodecanoic acid, 2-hydroxytrisuccinic acid, 2-hydroxytetracosic acid, 3-hydroxycaproic acid, 3-hydroxyoctanoic acid, 3-hydroxydecanoic acid, 3-hydroxydecanoic acid, 3-hydroxyundecanoic acid, 3-hydroxydodecanoic acid, 3-hydroxytridecanoic acid, 3-hydroxytetradecanoic acid, 3-hydroxyhexadecanoic acid, 3-hydroxyhexadecanoic acid, 3-hydroxyoctadecanoic acid, ω-hydroxy-2-decene Acid, ω-hydroxy pentadecanoic acid, ω-hydroxyhexadecanoic acid, ω-hydroxyicosanoic acid, ω-hydroxytetracosic acid, 6-hydroxyoctadecanoic acid, ricinoleic acid, 12-hydroxystearic acid and [ R-(E)]-12-hydroxy-9-octadecenoic acid and the like. Among them, a hydroxy fatty acid having a carbon number of 4 to 18 and having a hydroxyl group other than the ω position (especially 12 positions) is preferred, and ricinoleic acid and 12-hydroxystearic acid are preferred. The hydroxy fatty acid contained in the second protective layer may be one type or two or more types.
第2保護層中包括羥基脂肪酸，還可更含有烷基胺及脂肪酸等。關於烷基胺及脂肪酸可舉與已在前述第1保護層所舉例說明的相同者。The second protective layer includes a hydroxy fatty acid, and may further contain an alkylamine, a fatty acid or the like. The alkylamine and the fatty acid may be the same as those exemplified in the first protective layer.
於第2保護層中併用烷基胺與脂肪酸時，以烷基胺與脂肪酸之莫耳比(烷基胺：脂肪酸)來說，可舉例如宜為約90:10~約99.9:0.1之範圍，較佳為約95:5~約99.8:0.2之範圍。When the alkylamine and the fatty acid are used in combination in the second protective layer, the molar ratio of the alkylamine to the fatty acid (alkylamine: fatty acid) may, for example, preferably range from about 90:10 to about 99.9:0.1. Preferably, it is in the range of from about 95:5 to about 99.8:0.2.
第2銀微粒子B中之第2保護層之比率(質量%)，雖然並無特別限制，然而基於在保護第2銀微粒子B之表面的同時亦有效提高導電性黏著劑之燒結體的機械強度之觀點，可舉例如宜為0.1質量%~10質量%左右，較佳為0.1質量%~5質量%左右。The ratio (% by mass) of the second protective layer in the second silver fine particles B is not particularly limited. However, the mechanical strength of the sintered body of the conductive adhesive is effectively improved while protecting the surface of the second silver fine particles B. The viewpoint is preferably, for example, about 0.1% by mass to 10% by mass, preferably about 0.1% by mass to about 5% by mass.
第2銀微粒子B之平均粒徑係在50nm~100nm之範圍。從有效提高導電性黏著劑之燒結體的機械強度之觀點來看，第2銀微粒子B之平均粒徑宜在65nm~90nm之範圍。The average particle diameter of the second silver fine particles B is in the range of 50 nm to 100 nm. The average particle diameter of the second silver fine particles B is preferably in the range of 65 nm to 90 nm from the viewpoint of effectively increasing the mechanical strength of the sintered body of the conductive adhesive.
於本發明中，第2銀微粒子B之平均粒徑係在掃描式電子顯微鏡下所觀察之影像中所含30個以上之粒子之長邊長度的平均值。另外，於僅針對本發明之第2銀微粒子B以掃描式電子顯微鏡作觀察時，可令其為影像中所含任意30個以上之粒子之長邊長度的平均值。又，於針對混合了第2銀微粒子B與前述第1銀微粒子A的導電性黏著劑求取第2銀微粒子B之平均粒徑時，係依序選擇30個以上於掃描式電子顯微鏡下所觀察之影像中所含粒子之長邊長的粒子，並以此為針對該30個以上之粒子之長邊長度的平均值。In the present invention, the average particle diameter of the second silver fine particles B is an average value of the long side lengths of 30 or more particles contained in the image observed under a scanning electron microscope. Further, when only the second silver fine particles B of the present invention are observed by a scanning electron microscope, the average value of the long side lengths of any 30 or more particles contained in the image can be obtained. Further, when the average particle diameter of the second silver fine particles B is determined for the conductive adhesive in which the second silver fine particles B and the first silver fine particles A are mixed, 30 or more are sequentially selected under a scanning electron microscope. The long-length particles of the particles contained in the observed image are averaged for the length of the long sides of the 30 or more particles.
就本發明之導電性黏著劑而言，第1銀微粒子A與第2銀微粒子B之質量比(A：B)係在5：95~40：60之範圍內。於本發明中，藉由以所述之質量比併用具有前述預定範圍之粒徑的第1銀微粒子A以及粒徑大於該第1銀微粒子A且具有特定保護層之第2銀微粒子A，可有效提高導電性黏著劑之燒結體的機械強度。該機制詳細雖然並不明確，但舉例來說可推測如下。即，吾人認為於本發明之導電性黏著劑燒結時，平均粒小的第1銀微粒子A會以填補第2銀微粒子B之縫隙之方式先行進行燒結，其後，因為經以羥基脂肪酸保護且粒徑大的第2銀微粒子B之燒結會穩定進行，故燒結時之龜裂及破裂會受到抑制，結果可獲得機械強度優異之燒結體。In the conductive adhesive of the present invention, the mass ratio (A:B) of the first silver fine particles A to the second silver fine particles B is in the range of 5:95 to 40:60. In the present invention, the first silver fine particles A having a particle diameter of the predetermined range and the second silver fine particles A having a specific protective layer having a particle diameter larger than the first silver fine particles A may be used in combination with the mass ratio. The mechanical strength of the sintered body of the conductive adhesive is effectively improved. Although the details of this mechanism are not clear, they can be speculated as follows. In other words, when the conductive adhesive of the present invention is sintered, the first silver fine particles A having a small average particle size are first sintered to fill the gap of the second silver fine particles B, and thereafter, because they are protected by hydroxy fatty acid. The sintering of the second silver fine particles B having a large particle diameter is stably performed, so that cracking and cracking during sintering are suppressed, and as a result, a sintered body excellent in mechanical strength can be obtained.
從有效提高導電性黏著劑之燒結體的機械強度之觀點來看，於本發明之導電性黏著劑中，第1銀微粒子A與第2銀微粒子B之質量比(A：B)可舉例如宜為10：90~40：60左右、20：80~40：60左右、5：95~30：70左右、10：90~30：70左右及20：80~30：70左右。In the conductive adhesive of the present invention, the mass ratio (A: B) of the first silver fine particles A to the second silver fine particles B can be, for example, from the viewpoint of effectively improving the mechanical strength of the sintered body of the conductive adhesive. It should be around 10:90~40:60, 20:80~40:60, 5:95~30:70, 10:90~30:70 and 20:80~30:70.
於本發明之導電性黏著劑中，第1銀微粒子A與前述第2銀微粒子B之合計比率，雖然並無特別限制，但可舉例如宜為80質量%以上，較佳為85質量%~95質量%左右。In the conductive adhesive of the present invention, the total ratio of the first silver fine particles A to the second silver fine particles B is not particularly limited, but is preferably, for example, 80% by mass or more, and preferably 85% by mass. 95% by mass or so.
本發明之導電性黏著劑包括第1銀微粒子A及第2銀微粒子B還宜更含有溶劑。因含有溶劑，會使得流動性增高，而會變得容易將本發明之導電性黏著劑配置於所欲之場所。The conductive adhesive of the present invention preferably further contains a solvent, including the first silver fine particles A and the second silver fine particles B. When the solvent is contained, the fluidity is increased, and the conductive adhesive of the present invention is easily disposed in a desired place.
作為溶劑只要為可分散第1銀微粒子A及第2銀微粒子B者則並無特別限制，但宜含有極性有機溶劑。極性有機溶劑可列舉：丙酮、乙醯丙酮及甲基乙基酮等之酮類；二乙基醚、二丙基醚、二丁基醚、四氫呋喃及1,4-二□烷等之醚類；1,2-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,2-己二醇、1,6-己二醇、1,2-戊二醇、1,5-戊二醇、2-甲基-2,4-戊二醇、3-甲基-1,5-戊二醇、1,2-辛二醇、1,8-辛二醇及2-乙基-1,3-己二醇等之二元醇類；甘油；碳數1~5之直鏈或分枝鏈的醇、環己醇、3-甲氧基-3-甲基-1-丁醇及3-甲氧基-1-丁醇等之醇類；乙酸乙酯、乙酸丁酯、丁酸乙酯及甲酸乙酯等之脂肪酸酯類；聚乙二醇、三甘醇單甲基醚、四甘醇單甲基醚、乙二醇單乙基醚、二乙二醇單乙基醚、二乙二醇二甲基醚、三甘醇二甲基醚、四甘醇二甲基醚、3-甲氧基乙酸丁酯、乙二醇單丁基醚、乙二醇單丁基醚乙酸酯、乙二醇單己基醚、乙二醇單辛基醚、乙二醇單-2-乙基己基醚、乙二醇單芐基醚、二乙二醇單甲基醚、二乙二醇單甲基醚乙酸酯、二乙二醇單乙基醚、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚、二乙二醇單丁基醚乙酸酯、聚丙二醇、丙二醇單丙基醚、丙二醇單丁基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單丙基醚、二丙二醇單丁基醚、三丙二醇單甲基醚、三丙二醇單乙基醚、三丙二醇單丙基醚、三丙二醇單丁基醚等之二醇或二醇醚類；N,N-二甲基甲醯胺；二甲基亞碸；萜品醇等之萜[烯]類；乙腈；γ-丁內酯；四氫吡咯酮-[2]；N-甲基吡咯啶酮；及N-(2-胺乙基)哌□等。而於該等之中，從更加有效提高導電性黏著劑之燒結體的機械強度之觀點來看，宜為碳數3~5之直鏈或分枝鏈的醇、3-甲氧基-3-甲基-1-丁醇、3-甲氧基-1-丁醇、二乙二醇單丁基醚、二乙二醇單丁基醚乙酸酯及萜品醇。The solvent is not particularly limited as long as it can disperse the first silver fine particles A and the second silver fine particles B, but it is preferable to contain a polar organic solvent. Examples of the polar organic solvent include ketones such as acetone, acetamidine acetone and methyl ethyl ketone; and ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran and 1,4-dioxane. ; 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-hexanediol, 1,6 - hexanediol, 1,2-pentanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 1,2 a glycol such as octanediol, 1,8-octanediol or 2-ethyl-1,3-hexanediol; glycerin; a linear or branched chain alcohol or ring having a carbon number of 1 to 5. Alcohols such as hexanol, 3-methoxy-3-methyl-1-butanol and 3-methoxy-1-butanol; ethyl acetate, butyl acetate, ethyl butyrate and ethyl formate Fatty acid esters such as polyethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethylene glycol Ethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 3-methoxyacetic acid butyl ester, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monohexyl ether, ethylene glycol monooctyl ether, ethylene glycol mono-2-ethylhexyl ether Ethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, polypropylene glycol, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, a diol or a glycol ether such as dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether or tripropylene glycol monobutyl ether ; N,N-dimethylformamide; dimethyl hydrazine; terpene alcohol, etc. [ene]; acetonitrile; γ-butyrolactone; tetrahydropyrrolidone-[2]; N-methyl Pyrrolidone; and N-(2-aminoethyl) piperidine. Among these, from the viewpoint of more effectively improving the mechanical strength of the sintered body of the conductive adhesive, it is preferably a linear or branched chain alcohol having a carbon number of 3 to 5, and 3-methoxy-3. -methyl-1-butanol, 3-methoxy-1-butanol, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, and terpineol.
溶劑包括極性有機溶劑還可含有非極性或疏水性溶劑。非極性有機溶劑可列舉：己烷、庚烷、辛烷、壬烷、癸烷、2-乙基己烷及環己烷等之直鏈、分枝或環狀的飽和烴；碳數6以上之直鏈或分枝鏈之醇等之醇類；苯、甲苯、苯甲腈等之芳香族化合物；二氯甲烷、氯仿及二氯乙烷等之鹵化烴類；甲基正戊基酮；甲基乙基酮肟；及甘油三乙酸酯等。而於該等之中，又以飽和烴及碳數6以上之直鏈或分枝鏈之醇類為佳，較佳為己烷、辛烷、癸烷、辛醇、癸醇及十二醇。溶劑可單獨使用1種，或是混合2種以上作使用。The solvent includes a polar organic solvent and may also contain a non-polar or hydrophobic solvent. The nonpolar organic solvent may, for example, be a linear, branched or cyclic saturated hydrocarbon such as hexane, heptane, octane, decane, decane, 2-ethylhexane or cyclohexane; An alcohol such as a linear or branched chain alcohol; an aromatic compound such as benzene, toluene or benzonitrile; a halogenated hydrocarbon such as dichloromethane, chloroform or dichloroethane; methyl n-amyl ketone; Methyl ethyl ketone oxime; and triacetin. Among these, it is preferred to use a saturated hydrocarbon and a linear or branched chain alcohol having 6 or more carbon atoms, preferably hexane, octane, decane, octanol, decyl alcohol and dodecanol. . The solvent may be used singly or in combination of two or more.
含有極性有機溶劑與非極性有機溶劑雙方時，相對於溶劑總量極性有機溶劑之比率宜為5容量%以上，較佳為10容量%以上，更佳為15容量%以上。又，可設為60容量%以下，亦可設為55容量%以下，且亦可設為50容量%以下。溶劑亦可令其為僅由極性有機溶劑構成者。本發明之導電性黏著劑像這樣含有許多極性有機溶劑時，第1銀微粒子A及第2銀微粒子B之分散性亦良好。When both the polar organic solvent and the non-polar organic solvent are contained, the ratio of the polar organic solvent to the total amount of the solvent is preferably 5% by volume or more, preferably 10% by volume or more, and more preferably 15% by volume or more. Further, it may be 60% by volume or less, or may be 55% by volume or less, or may be 50% by volume or less. The solvent may also be composed of only a polar organic solvent. When the conductive adhesive of the present invention contains a plurality of polar organic solvents as described above, the dispersibility of the first silver fine particles A and the second silver fine particles B is also good.
就本發明之導電性黏著劑而言，溶劑之比率雖然並無特別限制，但可舉例如宜為20質量%以下，較佳為5質量%~15質量%左右。In the conductive adhesive of the present invention, the ratio of the solvent is not particularly limited, and is, for example, preferably 20% by mass or less, preferably about 5% by mass to 15% by mass.
於本發明之導電性黏著劑中亦可添加通常於導電性黏著劑中所含之添加劑。An additive which is usually contained in the conductive adhesive may be added to the conductive adhesive of the present invention.
2.導電性黏著劑之製造方法 本發明之導電性黏著劑可利用具有下述步驟之方法簡便地製造，該步驟係將第1銀微粒子A與第2銀微粒子B以使前述第1銀微粒子A與第2銀微粒子B之質量比(A:B)在5：95~40：60之範圍內之方式進行混合，其中該第1銀微粒子A具有第1保護層且平均粒徑為10nm~30nm，該第2銀微粒子B具有含羥基脂肪酸之第2保護層且平均粒徑為50nm~100nm。於此處，關於第1銀微粒子A及第2銀微粒子B之詳細說明係如已於前述「1. 導電性黏著劑」中所詳加敘述的。2. Method for Producing Conductive Adhesive The conductive adhesive of the present invention can be easily produced by a method having the following steps: the first silver fine particles A and the second silver fine particles B are made of the first silver fine particles The mass ratio (A:B) of A to the second silver fine particles B is mixed in a range of 5:95 to 40:60, wherein the first silver fine particles A have a first protective layer and an average particle diameter of 10 nm. At 30 nm, the second silver fine particles B have a second protective layer containing a hydroxy fatty acid and have an average particle diameter of 50 nm to 100 nm. Here, the detailed description of the first silver fine particles A and the second silver fine particles B is as described in detail in the above "1. Conductive adhesive".
於本發明之導電性黏著劑之製造方法中，第1銀微粒子A與第2銀微粒子B之混合宜藉由混合第1銀微粒子A之分散液與第2銀微粒子B之分散液來進行。第1銀微粒子A之平均粒徑為10nm~30nm，第2銀微粒子B之平均粒徑為50nm~100nm，由於兩粒子皆具有奈米大小之粒徑，故可稱若不將其等以已分散在溶劑中之狀態下進行混合的話，難以製得該等粒子均勻分散之導電性黏著劑。另外，溶劑宜為已於前述「1. 導電性黏著劑」中所舉例說明者。In the method for producing a conductive adhesive of the present invention, the mixing of the first silver fine particles A and the second silver fine particles B is preferably carried out by mixing a dispersion of the first silver fine particles A and a dispersion of the second silver fine particles B. The average particle diameter of the first silver fine particles A is 10 nm to 30 nm, and the average particle diameter of the second silver fine particles B is 50 nm to 100 nm. Since both particles have a particle size of a nanometer size, it can be said that if they are not When mixing is carried out in a state of being dispersed in a solvent, it is difficult to obtain a conductive adhesive in which the particles are uniformly dispersed. Further, the solvent is preferably exemplified in the above "1. Conductive adhesive".
第1銀微粒子A及第2銀微粒子B之製造方法並無特別限制，可分別利用眾所周知之方法來製造。作為該等之製造方法，可舉例如日本特開2015-40319號公報所載之方法等。以下揭示第1銀微粒子A及第2銀微粒子B之製造方法之一例。The method for producing the first silver fine particles A and the second silver fine particles B is not particularly limited, and they can be produced by a known method. As such a production method, for example, the method disclosed in JP-A-2015-40319 can be mentioned. An example of a method for producing the first silver fine particles A and the second silver fine particles B will be described below.
首先，準備用以製造第1銀微粒子A或是第2銀微粒子B之組成物(銀微粒子調製用組成物)。具體來說，係準備會成為銀微粒子之原料的銀化合物(宜為草酸銀等)、構成第1保護層或第2保護層之成分(前述之脂肪酸、烷基胺及羥基脂肪酸等)及有機溶劑。接著，混合該等各成分以製得銀微粒子調製用組成物。該組成物中之各成分的比率只要適當調製成以使成為前述第1銀微粒子A及第2銀微粒子B之構成即可。譬如，組成物中之草酸銀的含量相對於組成物之總量宜設為20~70質量%左右。又，第1保護層中使用脂肪酸時，脂肪酸之含量相對於組成物總量宜設為0.1質量%~20質量%左右。於第1保護層中使用烷基胺時，烷基胺之含量相對於組成物總量宜設為5質量%~55質量%左右。於第2保護層中使用羥基脂肪酸時，羥基脂肪酸之含量相對於組成物總量宜設為0.1質量%~15質量%左右。First, a composition (silver fine particle modulating composition) for producing the first silver fine particles A or the second silver fine particles B is prepared. Specifically, a silver compound (preferably silver oxalate or the like) which is a raw material of silver fine particles, a component constituting the first protective layer or the second protective layer (such as the above-mentioned fatty acid, alkylamine, hydroxy fatty acid, etc.) and organic are prepared. Solvent. Next, the components are mixed to prepare a composition for preparing silver fine particles. The ratio of each component in the composition may be appropriately adjusted so as to be the first silver fine particles A and the second silver fine particles B. For example, the content of silver oxalate in the composition is preferably about 20 to 70% by mass based on the total amount of the composition. When a fatty acid is used in the first protective layer, the content of the fatty acid is preferably about 0.1% by mass to 20% by mass based on the total amount of the composition. When the alkylamine is used in the first protective layer, the content of the alkylamine is preferably about 5% by mass to about 55% by mass based on the total amount of the composition. When a hydroxy fatty acid is used for the second protective layer, the content of the hydroxy fatty acid is preferably from about 0.1% by mass to about 15% by mass based on the total amount of the composition.
又，各成分之混合手段亦無特別限制，舉例來說，可用機械攪拌器、磁攪拌器、旋渦混合器、行星式磨機、球磨機、三輥磨機、管路型混合器(LINE MIXER)、行星式混合機及溶解器等之通用的裝置來進行混合。因混合時之溶解熱及摩擦熱等之影響，組成物之溫度會上升，為了避免銀微粒子開始熱分解反應宜一面將組成物之溫度抑制在例如60℃以下，特別是在40℃以下一面進行混合。Further, the mixing means of the respective components is not particularly limited, and for example, a mechanical stirrer, a magnetic stirrer, a vortex mixer, a planetary mill, a ball mill, a three-roll mill, a line type mixer (LINE MIXER) can be used. Mixing with a universal device such as a planetary mixer and a dissolver. The temperature of the composition increases due to the influence of the heat of dissolution and the frictional heat during mixing. In order to prevent the silver fine particles from starting the thermal decomposition reaction, the temperature of the composition is preferably suppressed to, for example, 60 ° C or lower, particularly at 40 ° C or lower. mixing.
其次，使銀微粒子調製用組成物於反應容器內進行反應，通常係藉由供至利用加熱之反應而引發銀化合物之熱分解反應而生成銀微粒子。反應時可將組成物導入於已預先加熱過之反應容器內，亦可於已將組成物導入反應容器內之後再進行加熱。Next, the composition for preparing a silver fine particle is reacted in a reaction vessel, and usually, silver fine particles are generated by a thermal decomposition reaction of a silver compound by a reaction to be heated. In the reaction, the composition may be introduced into a reaction vessel which has been previously heated, or may be heated after the composition has been introduced into the reaction vessel.
反應溫度只要為會進行熱分解反應並生成銀微粒子之溫度即可，可舉例如50~250℃左右。又，反應時間僅需配合所欲平均粒徑之大小及與其相應之組成物之組成來適當選擇即可。反應時間可舉例如1分鐘~100小時。The reaction temperature may be a temperature at which a thermal decomposition reaction is carried out to form silver fine particles, and may be, for example, about 50 to 250 °C. Further, the reaction time may be appropriately selected in accordance with the size of the desired average particle diameter and the composition of the composition corresponding thereto. The reaction time is, for example, 1 minute to 100 hours.
藉由熱分解反應生成之銀微粒子因作為一含未反應原料之混合物而得，故宜將銀微粒子進行精製。精製方法石可舉固液分離法以及利用了銀微粒子與有機溶劑等未反應原料之比重差的沈澱方法等。固液分離法可舉濾器過濾、離心分離、旋風式或是傾析器等方法。為了使精製時之處理容易，可以丙酮及甲醇等低沸點溶劑稀釋含有銀微粒子之混合物來調整其黏度。Since the silver fine particles formed by the thermal decomposition reaction are obtained as a mixture containing unreacted raw materials, it is preferred to purify the silver fine particles. The method of the purification method may be a solid-liquid separation method or a precipitation method using a difference in specific gravity between unreacted raw materials such as silver fine particles and an organic solvent. The solid-liquid separation method may be a filter filtration, a centrifugal separation, a cyclone or a decanter. In order to facilitate the treatment at the time of purification, the mixture containing silver fine particles may be diluted with a low boiling point solvent such as acetone or methanol to adjust the viscosity.
可藉由調整銀微粒子製造用組成物之組成及反應調件來調整所得銀微粒子之平均粒徑。The average particle diameter of the obtained silver fine particles can be adjusted by adjusting the composition of the composition for producing silver fine particles and the reaction modifier.
3.導電性黏著劑之燒結體 本發明之導電性黏著劑之燒結體可藉由將已於前述「1.導電性黏著劑」詳述之本發明之導電性黏著劑進行燒結而製得。就本發明之導電性黏著劑之燒結體而言，構成導電性黏著劑之第1保護層及第2保護層之成分大部分會因燒結時之高熱而脫離，所以燒結體實質上係由銀所構成。3. Sintered body of the conductive adhesive The sintered body of the conductive adhesive of the present invention can be obtained by sintering the conductive adhesive of the present invention which has been described in detail in the above "1. Conductive adhesive". In the sintered body of the conductive adhesive of the present invention, most of the components of the first protective layer and the second protective layer constituting the conductive adhesive are separated by high heat during sintering, so that the sintered body is substantially made of silver. Composition.
燒結溫度雖然並無特別限制，但從所得之燒結體在發揮高導電性及高黏著力之同時亦有效提高機械強度之觀點來看，可舉例如宜為150℃~200℃左右，較佳為150℃~185℃左右。基於相同之觀點，燒結時間可舉例如宜為0.4小時~2.0小時左右，較佳為0.5小時~1.2小時左右。燒結可於大氣及惰性氣體(氮氣及氬氣)等氣體環境下進行。燒結手段並無特別限制，可舉烘箱、熱風式乾燥爐、紅外線乾燥爐、雷射照射、閃光燈照射及微波等。The sintering temperature is not particularly limited, but is preferably from about 150 ° C to about 200 ° C from the viewpoint of exhibiting high electrical conductivity and high adhesion while exhibiting high electrical conductivity and high adhesion. 150 ° C ~ 185 ° C or so. From the same viewpoint, the sintering time is preferably, for example, about 0.4 hours to 2.0 hours, preferably about 0.5 hours to 1.2 hours. Sintering can be carried out in a gaseous environment such as the atmosphere and an inert gas (nitrogen and argon). The sintering means is not particularly limited, and examples thereof include an oven, a hot air drying oven, an infrared drying oven, laser irradiation, flash lamp irradiation, and microwave.
4.電路或電極 本發明之電路或電極分別具有構件間已藉由本發明之燒結體黏結的部分。即，本發明之電路或電極係將已於前述「1.導電性黏著劑」詳述之本發明之導電性黏著劑配置於電路或電極之構件間，且使導電性黏著劑燒結而將構件間黏結者。4. Circuit or Electrode The circuit or electrode of the present invention respectively has a portion between members which has been bonded by the sintered body of the present invention. In other words, in the circuit or the electrode of the present invention, the conductive adhesive of the present invention, which has been described in detail in the above "1. Conductive adhesive", is disposed between members of a circuit or an electrode, and the conductive adhesive is sintered to form the member. Bonding.
如前所述，本發明之燒結體由於在發揮高導電性及高黏著力之同時機械強度亦有效提高，所以即便就具有此燒結體之電路或電極而言，構件間亦會具有優異之之導電性及密著性，且機械強度亦優異。 實施例As described above, since the sintered body of the present invention is effective in improving the mechanical strength while exhibiting high electrical conductivity and high adhesion, even in the circuit or electrode having the sintered body, the members can be excellent. Electrical conductivity and adhesion, and excellent mechanical strength. Example
於以下之實施例中更具體說明本發明，但本發明並不侷限於該等例。The invention is more specifically illustrated in the following examples, but the invention is not limited to the examples.
於實施例中所使用之各成分之詳細如下。 ･草酸銀((COOAg)2 )是以專利文獻1(日本專利第5574761號公報)所載之方法合成。 ･蓖麻油酸(東京化成工業股份有限公司製) ･油酸(和光純藥工業股份有限公司製) ･N,N-二甲基-1,3-二胺丙烷(和光純藥工業股份有限公司製) ･環己胺(和光純藥工業股份有限公司製) ･正十二胺(和光純藥工業股份有限公司製) ･正丁胺(和光純藥工業股份有限公司製) ･丁醇(和光純藥工業股份有限公司製) ･正辛胺(和光純藥工業股份有限公司製)The details of the components used in the examples are as follows.・Silver oxalate ((COOAg) 2 ) is synthesized by the method described in Patent Document 1 (Japanese Patent No. 5574761). - ricinoleic acid (made by Tokyo Chemical Industry Co., Ltd.) ・Oleic acid (made by Wako Pure Chemical Industries Co., Ltd.) ・N,N-Dimethyl-1,3-diaminepropane (Wako Pure Chemical Industries Co., Ltd.) )] Cyclohexylamine (manufactured by Wako Pure Chemical Industries, Ltd.) ・N-butylamine (manufactured by Wako Pure Chemical Industries, Ltd.) ・N-butylamine (manufactured by Wako Pure Chemical Industries, Ltd.) ・ Butanol (and Wako Pure Chemical Industries Co., Ltd.) ・N-octylamine (made by Wako Pure Chemical Industries Co., Ltd.)
＜合成例1＞ 於已放入有磁攪拌件之50mL玻璃製離心管投入蓖麻油酸(0.03g)、N,N-二甲基-1,3-二胺丙烷(2.6g)及丁醇(4.8g)，並在攪拌了1分鐘左右之後投入草酸銀(3.2g)且予以攪拌約10分鐘，藉此製得銀微粒子調製用組成物。其後，將該等玻璃製離心管豎立設置於具有鋁磚之熱攪拌器(小池精密機器製作所製HHE-19G-U)上，且在40℃之水浴中攪拌30分鐘，並進一步於90℃之油浴中攪拌30分鐘。於輻射冷卻後取出磁攪拌件，且於各組成物中添加1.5g甲醇並以旋渦混合器攪拌後，以離心分離機(日立工機股份有限公司製CF7D2)於3000rpm(約1600×G)下實施1分鐘的離心沈澱操作，並藉由使離心管傾斜將上清液去除。重複2次添加15g之甲醇、攪拌、離心分離及去除上清液之步驟並回收所製得之銀微粒子。<Synthesis Example 1> A sesame oleic acid (0.03 g), N,N-dimethyl-1,3-diaminepropane (2.6 g), and butanol were placed in a 50 mL glass centrifuge tube into which a magnetic stirring member was placed. (4.8 g), after stirring for about 1 minute, silver oxalate (3.2 g) was put and stirred for about 10 minutes, thereby preparing a silver fine particle preparation composition. Thereafter, the glass centrifuge tubes were erected on a hot stirrer (HHE-19G-U manufactured by Koike Precision Machinery Co., Ltd.) having aluminum bricks, and stirred in a water bath at 40 ° C for 30 minutes, and further at 90 ° C. Stir in the oil bath for 30 minutes. After the radiant cooling, the magnetic stirring member was taken out, and 1.5 g of methanol was added to each composition and stirred with a vortex mixer, followed by a centrifugal separator (CF7D2 manufactured by Hitachi Kogyo Co., Ltd.) at 3000 rpm (about 1600 × G). A 1 minute centrifugation operation was carried out, and the supernatant was removed by tilting the centrifuge tube. The steps of adding 15 g of methanol, stirring, centrifuging, and removing the supernatant were repeated twice and the obtained silver fine particles were recovered.
＜合成例2＞ 於已放入有磁攪拌件之50mL玻璃製離心管投入油酸(0.06g)、正辛胺(1.40g)、N,N-二甲基-1,3-二胺丙烷(0.43g)、正十二胺(0.16g)、環己胺(0.12g)及正丁胺(0.64g)，並在攪拌了1分鐘左右之後投入草酸銀(3.2g)且予以攪拌約10分鐘，藉此製得銀微粒子調製用組成物。其後，將該等玻璃製離心管豎立設置於具有鋁磚之熱攪拌器(小池精密機器製作所製HHE-19G-U)上，且在40℃之水浴中攪拌30分鐘，並進一步於90℃之油浴中攪拌30分鐘。於輻射冷卻後取出磁攪拌件，且於各組成物中添加15g之甲醇並以旋渦混合器攪拌後，以離心分離機(日立工機股份有限公司製CF7D2)於3000rpm(約1600×G)下實施1分鐘的離心沈澱操作，並藉由使離心管傾斜將上清液去除。重複2次添加15g之甲醇、攪拌、離心分離及去除上清液之步驟並回收所製得之銀微粒子。<Synthesis Example 2> Oleic acid (0.06 g), n-octylamine (1.40 g), and N,N-dimethyl-1,3-diaminepropane were placed in a 50 mL glass centrifuge tube into which a magnetic stirrer was placed. (0.43 g), n-dodecylamine (0.16 g), cyclohexylamine (0.12 g) and n-butylamine (0.64 g), and after stirring for about 1 minute, silver oxalate (3.2 g) was added and stirred for about 10 In minutes, a composition for modulating silver fine particles was obtained. Thereafter, the glass centrifuge tubes were erected on a hot stirrer (HHE-19G-U manufactured by Koike Precision Machinery Co., Ltd.) having aluminum bricks, and stirred in a water bath at 40 ° C for 30 minutes, and further at 90 ° C. Stir in the oil bath for 30 minutes. After the radiant cooling, the magnetic stirring member was taken out, and 15 g of methanol was added to each composition and stirred by a vortex mixer, followed by a centrifugal separator (CF7D2 manufactured by Hitachi Kogyo Co., Ltd.) at 3000 rpm (about 1600 × G). A 1 minute centrifugation operation was carried out, and the supernatant was removed by tilting the centrifuge tube. The steps of adding 15 g of methanol, stirring, centrifuging, and removing the supernatant were repeated twice and the obtained silver fine particles were recovered.
＜合成例3＞ 於已放入有磁攪拌件之50mL玻璃製離心管投入油酸(0.1g)、N,N-二甲基-1,3-二胺丙烷(3.25g)及丁醇(6.0g)，並在攪拌了1分鐘左右之後投入草酸銀(4.0g)且予以攪拌約10分鐘，藉此製得銀微粒子調製用組成物。其後，將該等玻璃製離心管豎立設置於具有鋁磚之熱攪拌器(小池精密機器製作所製HHE-19G-U)上，且在40℃之水浴中攪拌30分鐘，並進一步於90℃之油浴中攪拌30分鐘。於輻射冷卻後取出磁攪拌件，且於各組成物中添加15g之甲醇並以旋渦混合器攪拌後，以離心分離機(日立工機股份有限公司製CF7D2)於3000rpm(約1600×G)下實施1分鐘的離心沈澱操作，並藉由使離心管傾斜將上清液去除。重複2次添加15g之甲醇、攪拌、離心分離及去除上清液之步驟並回收所製得之銀微粒子。<Synthesis Example 3> Oleic acid (0.1 g), N,N-dimethyl-1,3-diaminepropane (3.25 g), and butanol were placed in a 50 mL glass centrifuge tube into which a magnetic stirring member was placed. 6.0 g), after stirring for about 1 minute, silver oxalate (4.0 g) was put and stirred for about 10 minutes, thereby preparing a silver fine particle preparation composition. Thereafter, the glass centrifuge tubes were erected on a hot stirrer (HHE-19G-U manufactured by Koike Precision Machinery Co., Ltd.) having aluminum bricks, and stirred in a water bath at 40 ° C for 30 minutes, and further at 90 ° C. Stir in the oil bath for 30 minutes. After the radiant cooling, the magnetic stirring member was taken out, and 15 g of methanol was added to each composition and stirred by a vortex mixer, followed by a centrifugal separator (CF7D2 manufactured by Hitachi Kogyo Co., Ltd.) at 3000 rpm (about 1600 × G). A 1 minute centrifugation operation was carried out, and the supernatant was removed by tilting the centrifuge tube. The steps of adding 15 g of methanol, stirring, centrifuging, and removing the supernatant were repeated twice and the obtained silver fine particles were recovered.
(平均粒徑之測定) 將合成例1~3所得之各銀微粒子以掃描式電子顯微鏡(Hitachi High-Technologies Corporation製S-4500)進行觀察，並予以測定影像中所含任意30個粒子之邊長長度且求出平均值。並將結果示於表1。(Measurement of the average particle diameter) Each of the silver fine particles obtained in Synthesis Examples 1 to 3 was observed by a scanning electron microscope (S-4500, manufactured by Hitachi High-Technologies Corporation), and the side of any 30 particles contained in the image was measured. The length is long and the average value is obtained. The results are shown in Table 1.
[表1] [Table 1]
(實施例1~5及比較例1~5) 將合成例1所得之銀微粒子以及合成例2所得之銀微粒子以表2所示之預定比例進行混合，並予以添加相當於總重量之10%的萜品醇而獲得分散液。使用KURABO INDUSTRIES LTD.製之MAZERUSTAR將該液於2次攪拌優先模式下進行混合而調製出各導電性黏著劑。(Examples 1 to 5 and Comparative Examples 1 to 5) The silver fine particles obtained in Synthesis Example 1 and the silver fine particles obtained in Synthesis Example 2 were mixed at a predetermined ratio shown in Table 2, and added to 10% of the total weight. The terpineol is obtained to obtain a dispersion. Each of the conductive adhesives was prepared by mixing the liquid in a second stirring priority mode using MAZERUSTAR manufactured by KURABO INDUSTRIES LTD.
其次，準備於銅板上施有0.5μm之無電電鍍銀之基材，於其上將各導電性黏著劑勻均地進行塗膜以使塗膜厚度成為50μm，而且將背面(與導電性黏著劑接觸的面)施有鍍金或金濺鍍處理之矽晶片(尺寸2mm×2mm)載置於其上。並藉由乾燥器(循環式)使此物於預定溫度(150℃、175℃)下加熱60分鐘而製得各導電性黏著劑已燒結之塗膜。Next, a 0.5 μm electroless silver-plated substrate was prepared on a copper plate, and each of the conductive adhesives was uniformly coated to have a film thickness of 50 μm, and the back surface (with a conductive adhesive) Contacted surface) A wafer (size 2 mm x 2 mm) coated with gold or gold plating was placed thereon. The coated film of each of the conductive adhesives was prepared by heating the article at a predetermined temperature (150 ° C, 175 ° C) for 60 minutes by means of a dryer (circulating type).
(機械強度之評價) 各實施例所得之各塗膜的剪切強度係使用黏結強度試驗機(西進商事股份有限公司製SS30-WD)實施晶片剪切試驗(die shear test)進行測定。並將結果示於表2。(Evaluation of Mechanical Strength) The shear strength of each of the coating films obtained in each of the examples was measured by a die shear test using a bonding strength tester (SS30-WD manufactured by Sejin Corporation). The results are shown in Table 2.
(塗膜之龜裂及破裂之評價) 以目視觀察各實施例所得之各塗膜的表面，並予以評價有無塗膜之龜裂及破裂。將結果示於表2。(Evaluation of Cracking and Cracking of Coating Film) The surface of each coating film obtained in each of the examples was visually observed, and the presence or absence of cracking and cracking of the coating film was evaluated. The results are shown in Table 2.
[表2] [Table 2]
(比較例6) 將合成例1所得之銀微粒子以及合成例3所得之銀微粒子以使銀微粒子之含量比率(重量)成為30：70之方式進行混合，並添加相當於總重量之10%的萜品醇而獲得分散液。使用KURABO INDUSTRIES LTD.製之MAZERUSTAR將該液於2次攪拌優先模式下進行混合而調製出各導電性黏著劑。(Comparative Example 6) The silver fine particles obtained in Synthesis Example 1 and the silver fine particles obtained in Synthesis Example 3 were mixed so that the content ratio (weight) of the silver fine particles was 30:70, and 10% of the total weight was added. A terpineol is obtained to obtain a dispersion. Each of the conductive adhesives was prepared by mixing the liquid in a second stirring priority mode using MAZERUSTAR manufactured by KURABO INDUSTRIES LTD.
其次，準備於銅板上施有0.5μm之無電電鍍銀之基材，並於其上將各導電性黏著劑勻均地進行塗膜以使塗膜厚度成為50μm，而且將背面(與導電性黏著劑接觸的面)施有鍍金或金濺鍍處理之矽晶片(尺寸2mm×2mm)載置於其上。並藉由乾燥器(循環式)使此物於預定溫度下加熱60分鐘而製得各導電性黏著劑已燒結之塗膜。針對所得之塗膜依與實施例1~5及比較例1~5同樣之方式，進行機械強度之評價及塗膜之龜裂及破裂之評價。並將結果示於表3。Next, a 0.5 μm electroless silver-plated substrate was prepared on a copper plate, and each of the conductive adhesives was uniformly coated thereon so that the thickness of the coating film became 50 μm, and the back surface (adhered to conductivity) The surface to which the agent is contacted is placed on the wafer (gold size or gold sputtered) (the size of 2 mm × 2 mm) is placed thereon. The coated film of each of the conductive adhesives was prepared by heating the article at a predetermined temperature for 60 minutes by means of a dryer (circulating type). The evaluation of the mechanical strength and the evaluation of the crack and crack of the coating film were carried out in the same manner as in Examples 1 to 5 and Comparative Examples 1 to 5 on the obtained coating film. The results are shown in Table 3.
[表3] [table 3]
如從表2所示之結果清楚得知，以質量比5：95~40：60之混合比率來含有將油酸用於保護層之銀微粒子(20nm)與將蓖麻油酸用於保護層之銀微粒子(80nm)的實施例1~5之導電性黏著劑，在燒成溫度為150℃及175℃中之任一溫度下，其等與設為該混合比率範圍外之比較例1~5相較之下，塗膜之剪切強度皆高且亦無塗膜之龜裂及破裂。另外，於質量比45：55(比較例2)及50：50(比較例3)之情況下，塗膜之剪切強度雖亦可獲得與實施例同程度的值，但塗膜卻有龜裂及破裂。推測此乃是因為20nm粒子之含量一多便會對燒結後之塗膜施加應力的緣故。又，於比較例6中，雖然是以質量70：30之混合比率含有將油酸用於保護層之銀微粒子(70nm)與將蓖麻油酸用於保護層之銀微粒子(80nm)，但與實施例1~5相較下塗膜之剪切強度低，且有塗膜龜裂及破裂。As is clear from the results shown in Table 2, silver fine particles (20 nm) using oleic acid as a protective layer and ricinoleic acid for a protective layer were mixed at a mass ratio of 5:95 to 40:60. Silver granules (80 nm) of the conductive adhesives of Examples 1 to 5, at any of the firing temperatures of 150 ° C and 175 ° C, and the comparative examples 1 to 5 which were outside the range of the mixing ratio In contrast, the shear strength of the coating film is high and there is no cracking or cracking of the coating film. Further, in the case of the mass ratio of 45:55 (Comparative Example 2) and 50:50 (Comparative Example 3), the shear strength of the coating film can be obtained to the same degree as in the examples, but the coating film has a turtle. Cracked and broken. It is presumed that this is because the content of the 20 nm particles is too large to stress the film after sintering. Further, in Comparative Example 6, silver fine particles (70 nm) using oleic acid as a protective layer and silver fine particles (80 nm) using ricinoleic acid as a protective layer were contained in a mixing ratio of 70:30 by mass, but In Examples 1 to 5, the shear strength was lower than that of the undercoat film, and the coating film was cracked and broken.
(比較例7~14) 將合成例2所得之銀微粒子以及合成例3所得之銀微粒子以表4所示預定之比率進行混合，並添加相當於總重量之10%的萜品醇而獲得分散液。使用KURABO INDUSTRIES LTD.製之MAZERUSTAR將該液於2次攪拌優先模式下進行混合而調製出各導電性黏著劑。(Comparative Examples 7 to 14) The silver fine particles obtained in Synthesis Example 2 and the silver fine particles obtained in Synthesis Example 3 were mixed at a predetermined ratio shown in Table 4, and 10% by weight of terpineol was added to obtain dispersion. liquid. Each of the conductive adhesives was prepared by mixing the liquid in a second stirring priority mode using MAZERUSTAR manufactured by KURABO INDUSTRIES LTD.
其次，準備於銅板上施有0.5μm之無電電鍍銀之基材，於其上將各導電性黏著劑勻均地進行塗膜以使塗膜厚度成為50μm，而且將背面(與導電性黏著劑接觸的面)施有鍍金或金濺鍍處理之矽晶片(尺寸2mm×2mm)載置於其上。並藉由乾燥器(循環式)使此物於預定溫度(150℃、175℃)下加熱60分鐘而製得各導電性黏著劑已燒結之塗膜。針對所得之塗膜依與實施例1~5及比較例1~5同樣之方式，進行機械強度之評價及塗膜之龜裂及破裂之評價。並將結果示於表4。Next, a 0.5 μm electroless silver-plated substrate was prepared on a copper plate, and each of the conductive adhesives was uniformly coated to have a film thickness of 50 μm, and the back surface (with a conductive adhesive) Contacted surface) A wafer (size 2 mm x 2 mm) coated with gold or gold plating was placed thereon. The coated film of each of the conductive adhesives was prepared by heating the article at a predetermined temperature (150 ° C, 175 ° C) for 60 minutes by means of a dryer (circulating type). The evaluation of the mechanical strength and the evaluation of the crack and crack of the coating film were carried out in the same manner as in Examples 1 to 5 and Comparative Examples 1 to 5 on the obtained coating film. The results are shown in Table 4.
[表4]如從表4所示之結果清楚得知，於混合了將油酸用於保護層之銀微粒子(20nm)與將油酸用於保護層之銀微粒子(70nm)之比較例7~14中，不論於任一混合比率下塗膜之剪切強度皆低且皆有塗膜之龜裂及破裂。[Table 4] As is clear from the results shown in Table 4, in Comparative Examples 7 to 14 in which silver fine particles (20 nm) using oleic acid as a protective layer and silver fine particles (70 nm) using oleic acid as a protective layer were mixed, The coating film has a low shear strength at any mixing ratio and has cracks and cracks in the coating film.
(無)(no)
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| CN102438776A (en) * | 2009-07-16 | 2012-05-02 | 应用纳米粒子研究所株式会社 | Composite nanometal paste of two-metallic-component type, bonding method, and electronic part |
| WO2011155055A1 (en) * | 2010-06-11 | 2011-12-15 | Ｄｏｗａエレクトロニクス株式会社 | Low-temperature-sintering bonding material and bonding method using the bonding material |
| EP2805783B1 (en) * | 2012-01-20 | 2018-12-05 | DOWA Electronics Materials Co., Ltd. | Bonding material and bonding method in which said bonding material is used |
| JP5509283B2 (en) * | 2012-09-13 | 2014-06-04 | ニホンハンダ株式会社 | Heat-sinterable metal fine particle production method, paste-like metal fine particle composition, solid metal or solid metal alloy production method, metal member joining method, printed wiring board production method, and electrical circuit connection bump production Method |
| WO2014185073A1 (en) * | 2013-05-16 | 2014-11-20 | バンドー化学株式会社 | Composition for metal bonding |
| JP6029719B2 (en) * | 2014-07-31 | 2016-11-24 | Ｄｏｗａエレクトロニクス株式会社 | Silver powder, method for producing the same, and conductive paste |
-
2017
- 2017-03-06 CN CN201780010239.9A patent/CN108699397B/en active Active
- 2017-03-06 JP JP2018508866A patent/JP6962318B2/en active Active
- 2017-03-06 WO PCT/JP2017/008729 patent/WO2017169534A1/en active Application Filing
- 2017-03-06 KR KR1020187021678A patent/KR20180127313A/en not_active Application Discontinuation
- 2017-03-14 TW TW106108284A patent/TWI726071B/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI716760B (en) * | 2017-10-31 | 2021-01-21 | 南韓商ＬＳ Ｎｉｋｋｏ銅製鍊股份有限公司 | Conductive paste for solar cell's electrode and solar cell using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20180127313A (en) | 2018-11-28 |
| CN108699397B (en) | 2021-07-27 |
| TWI726071B (en) | 2021-05-01 |
| WO2017169534A1 (en) | 2017-10-05 |
| CN108699397A (en) | 2018-10-23 |
| JP6962318B2 (en) | 2021-11-05 |
| JPWO2017169534A1 (en) | 2019-02-28 |
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