JP6406546B2 - Joining method - Google Patents
Joining method Download PDFInfo
- Publication number
- JP6406546B2 JP6406546B2 JP2015024701A JP2015024701A JP6406546B2 JP 6406546 B2 JP6406546 B2 JP 6406546B2 JP 2015024701 A JP2015024701 A JP 2015024701A JP 2015024701 A JP2015024701 A JP 2015024701A JP 6406546 B2 JP6406546 B2 JP 6406546B2
- Authority
- JP
- Japan
- Prior art keywords
- bonding
- joining
- particles
- composition
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000005304 joining Methods 0.000 title claims description 78
- 238000000034 method Methods 0.000 title claims description 51
- 239000000203 mixture Substances 0.000 claims description 83
- 239000002245 particle Substances 0.000 claims description 80
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 41
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 40
- 229910052709 silver Inorganic materials 0.000 claims description 34
- 239000004332 silver Substances 0.000 claims description 34
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- 238000012360 testing method Methods 0.000 description 20
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Landscapes
- Laminated Bodies (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
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- Powder Metallurgy (AREA)
- Manufacturing Of Electrical Connectors (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Description
本発明は、マイクロサイズ銀粒子を用いた接合方法に関する。 The present invention relates to a bonding method using micro-sized silver particles.
従来、例えばパワーデバイスにおける金属部品と金属部品とを機械的、電気的及び／又は熱的に接合するために、はんだ、導電性の接着剤、ペースト及びフィルム等の接合材が用いられている。なかでも、はんだ並びに金属からなる導電フィラーを含む接着剤、ペースト及びフィルムは、電気的な接続を必要とする部分の接合に用いられている。 2. Description of the Related Art Conventionally, bonding materials such as solder, conductive adhesives, pastes, and films have been used to mechanically, electrically and / or thermally bond metal parts and metal parts in power devices, for example. Especially, the adhesive agent, paste, and film containing the conductive filler which consists of solder and a metal are used for joining the part which needs an electrical connection.
近年、接合時におけるパワーデバイスの損傷を防ぐという観点から、低い接合温度（例えば３５０℃以下）で十分な接合強度を確保できる接合材が求められている。このような接合材として、銀、金などの貴金属を中心とするナノサイズの金属微粒子を用いた金属ペーストが知られている（例えば、特許文献１を参照）。 In recent years, from the viewpoint of preventing damage to power devices during bonding, there is a demand for a bonding material that can ensure sufficient bonding strength at a low bonding temperature (for example, 350 ° C. or lower). As such a bonding material, a metal paste using nano-sized metal fine particles centered on noble metals such as silver and gold is known (for example, see Patent Document 1).
しかしながら、特許文献１が開示する金属ペーストでは、接合時の金属微粒子の焼結によって得られる接合層に、金属微粒子の分散剤や溶媒として使用される有機物が残留してしまうことがある。このため、有機物が残留すると接合層にボイドが形成され、金属部品同士の接合強度を確保できないという問題があった。 However, in the metal paste disclosed in Patent Document 1, an organic substance used as a dispersant or a solvent for the metal fine particles may remain in the bonding layer obtained by sintering the metal fine particles during bonding. For this reason, when organic substance remained, a void was formed in the joining layer, and there was a problem that the joining strength of metal parts could not be secured.
また、金属部品同士を接合する際、少なくとも一方の金属部品に金属ペーストを塗布する必要があるが、ナノサイズの金属微粒子を含む金属ペーストは扱いが難しいうえ、塗布や接合の作業が煩雑になってしまうという問題があった。 In addition, when joining metal parts, it is necessary to apply a metal paste to at least one of the metal parts, but metal pastes containing nano-sized metal particles are difficult to handle and the work of application and joining becomes complicated. There was a problem that.
本発明は、上記に鑑みてなされたものであって、接合強度を確保しつつ、部材同士を確実かつ簡易に接合することができる接合方法を提供することを目的とする。 This invention is made | formed in view of the above, Comprising: It aims at providing the joining method which can join members reliably and simply, ensuring joining strength.
上述した課題を解決し、目的を達成するために、本発明にかかる接合方法は、接合すべき第１および第２の部材の少なくとも一方の部材の接合面に、金属系粒子又はセラミック系粒子を含んでなり、銀を結晶成長させる核物質、および放射状に延びる複数の凸部を有し、銀を含み、平均粒径が０．１〜２２μｍである金属粒子と、有機溶剤とを含む接合用組成物を塗布する塗布工程と、前記接合面に塗布された前記接合用組成物を無加圧下、２５０℃以下の予熱温度により加熱する加熱工程と、前記接合用組成物を介して前記第１および第２の部材を重ねた後、加圧下、および１５０℃以上３５０℃以下の温度条件下で前記第１および第２の部材を接合する接合工程と、を含むことを特徴とする。 In order to solve the above-mentioned problems and achieve the object, the joining method according to the present invention is a method in which metal-based particles or ceramic-based particles are provided on the joint surface of at least one of the first and second members to be joined. And a core material for crystal growth of silver, a plurality of protrusions extending radially, metal particles having an average particle diameter of 0.1 to 22 μm, and an organic solvent. An application step of applying a composition; a heating step of heating the bonding composition applied to the bonding surfaces at a preheating temperature of 250 ° C. or less under no pressure; and the first through the bonding composition. And a joining step of joining the first and second members under pressure and under a temperature condition of 150 ° C. or higher and 350 ° C. or lower after the second members are stacked.
また、本発明にかかる接合方法は、上記の発明において、前記接合工程は、さらに加圧を行うこと、を特徴とする。 Moreover, the joining method according to the present invention is characterized in that, in the above invention, the joining step further includes pressurization.
また、本発明にかかる接合方法は、上記の発明において、前記予熱温度は、前記有機溶剤の沸点に基づき設定されること、を特徴とする。 Moreover, the joining method according to the present invention is characterized in that, in the above invention, the preheating temperature is set based on a boiling point of the organic solvent.
また、本発明にかかる接合方法は、上記の発明において、前記接合用組成物における前記金属粒子の含有量が７０〜８０質量％であること、を特徴とする。 Moreover, the joining method according to the present invention is characterized in that, in the above invention, the content of the metal particles in the joining composition is 70 to 80% by mass.
また、本発明にかかる接合方法は、上記の発明において、前記凸部の形状が、針状、桿状、及び花弁状からなる群から選択される少なくとも一つの形状であること、を特徴とする。 In the joining method according to the present invention as set forth in the invention described above, the shape of the convex portion is at least one shape selected from the group consisting of a needle shape, a hook shape, and a petal shape.
本発明によれば、接合強度を確保しつつ、部材同士を確実かつ簡易に接合することができるという効果を奏する。 According to the present invention, there is an effect that the members can be reliably and easily joined while securing the joining strength.
以下、本発明を実施するための形態を図面と共に詳細に説明する。なお、以下の実施の形態により本発明が限定されるものではない。また、以下の説明において参照する各図は、本発明の内容を理解でき得る程度に形状、大きさ、および位置関係を概略的に示してあるに過ぎない。すなわち、本発明は各図で例示された形状、大きさ、および位置関係のみに限定されるものではない。 DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings. In addition, this invention is not limited by the following embodiment. The drawings referred to in the following description only schematically show the shape, size, and positional relationship so that the contents of the present invention can be understood. That is, the present invention is not limited only to the shape, size, and positional relationship illustrated in each drawing.
（１）接合用組成物
本発明の実施の形態にかかる接合用組成物は、異なる金属部材同士の間に介在し、両者を接合するために用いられる。接合用組成物は、金属粒子として、平均粒径が０．５〜２２μｍである毬栗状の導電粉（マイクロサイズ銀粒子）、および有機溶媒を少なくとも含む混合物であり、必要に応じて分散剤等を含有する。以下、これら各成分について説明する。
(1) Joining composition The joining composition concerning embodiment of this invention intervenes between different metal members, and is used in order to join both. The bonding composition is a mixture containing, as metal particles, at least a chestnut-shaped conductive powder (micro-sized silver particles) having an average particle size of 0.5 to 22 μm, and an organic solvent, and a dispersant or the like as necessary. Containing. Hereinafter, each of these components will be described.
（１−１）導電粉（マイクロサイズ銀粒子）
本発明の実施の形態にかかる接合用組成物の金属粒子としては、平均粒径が０．５〜２２μｍである毬栗状の導電粉を用いることが好ましい。また、金属粒子の平均粒径は、が１〜１５μｍであることが好ましく、３〜１０μｍであることがさらに好ましい。平均粒径をマイクロサイズとすることで、ナノサイズの粒子と比較して分散性及び安定性が向上するため、分散性及び安定性を確保するために必要となる有機物の量を大幅に低減することができる。加えて、例えば平均粒径を１０μｍ以下とすることで、金属粒子間の接点等を確保するために十分な表面積を得ることができる。導電粉の平均粒径は、レーザー方式のパーティクルカウンターにより測定することができるし、あるいは電子顕微鏡写真から実測することもでき、さらには、当該電子顕微鏡写真から、画像処理装置を用いて算出することもできる。
(1-1) Conductive powder (micro-sized silver particles)
As the metal particles of the bonding composition according to the embodiment of the present invention, it is preferable to use a chestnut-shaped conductive powder having an average particle size of 0.5 to 22 μm. Further, the average particle diameter of the metal particles is preferably 1 to 15 μm, and more preferably 3 to 10 μm. By making the average particle size micro size, dispersibility and stability are improved compared to nano-size particles, so the amount of organic matter required to ensure dispersibility and stability is greatly reduced. be able to. In addition, for example, by setting the average particle size to 10 μm or less, it is possible to obtain a sufficient surface area to ensure contact points between the metal particles. The average particle size of the conductive powder can be measured with a laser type particle counter, or can be measured from an electron micrograph, and further calculated from the electron micrograph using an image processing apparatus. You can also.
また、本実施形態の接合用組成物の金属粒子として好ましいのは、以下の（ａ）、（ｂ）を備える導電粉である。
（ａ）導電材料としての銀を結晶成長させるための核物質であって、当該核物質として、金属系粒子又はセラミック系粒子を含んでなり、核物質の平均粒径が０．０１〜１０μｍである核物質
（ｂ）凹凸｛即ち、粒子（または核物質）の中心からみて放射状に延設された凸部（突起と称することがある）、及び当該凸部同士の間隙にある凹部（窪みと称することがある）｝
なお、核物質の平均粒径は、０．１〜５μｍであることが好ましく、０．５〜３μｍであればより好ましい。
Moreover, what is preferable as a metal particle of the composition for joining of this embodiment is a conductive powder provided with the following (a) and (b).
(A) A core material for crystal growth of silver as a conductive material, comprising metal particles or ceramic particles as the core material, and having an average particle size of 0.01 to 10 μm. Certain nuclear material (b) irregularities {that is, convex portions (sometimes referred to as projections) extending radially from the center of the particle (or nuclear material), and concave portions (indentations) between the convex portions. Sometimes called)}
In addition, it is preferable that the average particle diameter of a nuclear substance is 0.1-5 micrometers, and if it is 0.5-3 micrometers, it is more preferable.
この導電粉によれば、放射状に延設された凸部同士、及び放射状に延設された凸部と当該凸部の間隙の凹部とが良好に接触し、低温（１５０〜３５０℃）に保持することで当該接触部分から焼結が効果的に進行する。 According to this conductive powder, the projecting portions extending radially, and the projecting portions extending radially and the recesses in the gap between the projecting portions are in good contact with each other and kept at a low temperature (150 to 350 ° C.). By doing so, sintering effectively proceeds from the contact portion.
核物質は、金属系粒子又はセラミック系粒子（無機系粒子）であることが好ましい。この理由は、金属系粒子を使用することにより、比重や粒径の調整が容易になるばかりか、形状保持性や電気抵抗率の調整についても容易になるためである。さらに、セラミック系粒子を使用することにより、比重や粒径の調整が容易になるばかりか、形状保持性や耐熱性等の特性についてもさらに向上させることができるためである。 The core material is preferably metal particles or ceramic particles (inorganic particles). This is because the use of metal-based particles not only facilitates adjustment of specific gravity and particle diameter, but also facilitates adjustment of shape retention and electrical resistivity. Furthermore, the use of ceramic particles not only facilitates the adjustment of specific gravity and particle size, but also improves properties such as shape retention and heat resistance.
ここで、金属系粒子としては、銀粒子、金粒子、銅粒子、アルミニウム粒子、亜鉛粒子、半田粒子、錫粒子、ニッケル粒子等の一種単独又は二種以上の組合せが挙げられるが、銀粒子を用いることが好ましい。さらに、セラミック系粒子としては、シリカ粒子（ホワイトカーボン）、酸化チタン粒子、酸化ジルコニウム粒子、酸化アルミニウム粒子、酸化亜鉛粒子、酸化スズ粒子、酸化ニオブ粒子等の一種単独又は二種以上の組合せが挙げられる。特に、これらの粒子のうち、シリカ粒子（ホワイトカーボン）や酸化チタン粒子を使用することにより、比重や粒径、あるいは電気抵抗率の調整が容易になるばかりか、形状保持性等の特性についても著しく向上させることができることから、好ましい核物質である。 Here, as the metal-based particles, silver particles, gold particles, copper particles, aluminum particles, zinc particles, solder particles, tin particles, nickel particles, and the like may be used alone or in combination of two or more. It is preferable to use it. Furthermore, examples of the ceramic particles include silica particles (white carbon), titanium oxide particles, zirconium oxide particles, aluminum oxide particles, zinc oxide particles, tin oxide particles, niobium oxide particles and the like alone or in combination of two or more. It is done. In particular, among these particles, the use of silica particles (white carbon) or titanium oxide particles facilitates adjustment of specific gravity, particle size, or electrical resistivity, as well as properties such as shape retention. It is a preferred nuclear material because it can be significantly improved.
また、核物質の種類に関して、多孔質であるか、あるいは凝集粒子であることが好ましい。この理由は、多孔質や凝集粒子の核物質を中心として、放射状に凸部を均一に延設することができ、粒度分布がさらに狭く、かつ形状保持性に優れた導電粉を得ることができるためである。したがって、多孔質や凝集粒子からなる核物質に関して、ＢＥＴ表面積を０．０１〜５００ｍ２／ｇの範囲内の値とすることが好ましい。なお、核物質が多孔質、あるいは凝集粒子であるか否かは、電子顕微鏡観察によって、容易に確認することができる。 In addition, the kind of the nuclear material is preferably porous or agglomerated particles. This is because, with the core material of porous or aggregated particles as the center, it is possible to uniformly extend the protrusions radially, and to obtain a conductive powder with a narrower particle size distribution and excellent shape retention. Because. Therefore, it is preferable to set the BET surface area to a value within the range of 0.01 to 500 m 2 / g with respect to the core material composed of porous or aggregated particles. Whether or not the nuclear material is porous or aggregated particles can be easily confirmed by observation with an electron microscope.
核物質の添加量は、全体量に対して、０．０１〜３０重量％の範囲内の値とすることが好ましい。この理由は、かかる核物質の添加量が０．０１重量％未満の値になると、核物質を中心として、放射状に凸部を均一に延設することが困難になる場合があるためである。一方、かかる核物質の添加量が３０重量％を超えると、導電粉の電気抵抗率が著しく上昇する場合があるためである。したがって、核物質の添加量を、全体量に対して、０．１〜２０重量％の範囲内の値とすることがより好ましく、０．５〜１０重量％の範囲内の値とすることがさらに好ましい。なお、核物質の添加量は、所定量以上、例えば、１重量％以上であれば、一例として、電子線マイクロアナライザー（ＥＰＭＡ）を用いて測定することができる。 The addition amount of the nuclear material is preferably a value within the range of 0.01 to 30% by weight with respect to the total amount. This is because, when the amount of the nuclear material added is less than 0.01% by weight, it may be difficult to uniformly extend the protrusions radially around the nuclear material. On the other hand, if the amount of the nuclear material added exceeds 30% by weight, the electrical resistivity of the conductive powder may increase significantly. Therefore, it is more preferable that the addition amount of the nuclear material is a value within a range of 0.1 to 20% by weight, and a value within a range of 0.5 to 10% by weight with respect to the total amount. Further preferred. In addition, if the addition amount of a nuclear substance is more than predetermined amount, for example, 1 weight% or more, as an example, it can measure using an electron beam microanalyzer (EPMA).
導電粉の凸部の形状は、針状（若しくは繊維状）、桿状、及び花弁状からなる群から選択される少なくとも一つの形状であることが好ましい。更には、接合用組成物に、凸部の形状が針状からなる導電粉、凸部の形状が桿状からなる導電粉、及び凸部の形状が花弁状からなる導電粉を全て含むことが好ましい。 The shape of the convex portion of the conductive powder is preferably at least one shape selected from the group consisting of a needle shape (or fiber shape), a hook shape, and a petal shape. Furthermore, it is preferable that the bonding composition contains all of conductive powder having a convex shape of needle shape, conductive powder having a convex shape of bowl shape, and conductive powder having a convex shape of petal shape. .
針状の凸部を有する銀粉と、桿状の凸部を有する銀粉と、花弁状の凸部を有する銀粉とを組合せることにより、接点の形成が容易となって、低温焼結性がさらに向上する。より具体的には、導電粉の全体量を１００重量％としたときに、針状の凸部を有する銀粉を１０〜５０重量％、桿状の凸部を有する銀粉を１５〜５０重量％、及び花弁状の凸部を有する銀粉を２０〜５０重量％の範囲内で適宜混合使用することが好ましい。 Combining silver powder having needle-like convex parts, silver powder having bowl-like convex parts, and silver powder having petal-like convex parts facilitates contact formation and further improves low-temperature sinterability. To do. More specifically, when the total amount of the conductive powder is 100% by weight, the silver powder having a needle-like convex part is 10 to 50% by weight, the silver powder having a bowl-like convex part is 15 to 50% by weight, and It is preferable to appropriately mix and use silver powder having petal-like convex portions within a range of 20 to 50% by weight.
凸部の長さは、当該凸部の先端に接して囲む閉曲面の成す球の平均半径の４０％より大きいことが好ましい。この理由は、このような凸部であれば、適当な大きさを有することになり、凹部との嵌合連結がより確実なものとなり、嵌合部分の機械的安定性も向上するためである。 The length of the convex portion is preferably larger than 40% of the average radius of a sphere formed by a closed curved surface surrounding the tip of the convex portion. This is because such a convex portion has an appropriate size, and the fitting connection with the concave portion becomes more reliable, and the mechanical stability of the fitting portion is also improved. .
凹部は、凸部同士の間隙に設けられた窪み形状であって、断面方向横（粒子の中心を通過する平面を切断面とする断面における該断面と直交する方向）からみた場合に、異なる導電粉の凸部が入り込むことのできる形状（より理想的には、異なる導電粉の凸部がこの凹部に嵌合連結可能な形状）であればよい。この理由は、このように構成することにより、隣接する導電粉間で、凸部と凹部とが容易に嵌合連結することができるためである。また、凹部の深さ（大きさ）を導電粉に占める凹部の体積、すなわち凹部からなる空隙率で表すことが可能である。具体的には、凸部の先端を囲む閉曲線からなる球の体積を１００容量％としたときに、凹部からなる空隙率を４０容量％以上の値とすることが好ましい。この理由は、かかる凹部からなる空隙率が４０容量％未満の値となると、凸部と凹部との嵌合連結が不十分となる場合があるためである。一方、かかる凹部からなる空隙率が過度に大きくなると、導電粉の機械的強度が著しく低下する場合がある。したがって、凹部からなる空隙率を４２〜７０容量％の範囲内の値とすることがより好ましく、４５〜６０容量％の範囲内の値とすることがさらに好ましい。 The concave portion is a hollow shape provided in the gap between the convex portions, and has different conductivity when viewed from the side in the cross-sectional direction (direction perpendicular to the cross section in a cross section having a plane passing through the center of the particle as a cut surface). What is necessary is just the shape which the convex part of powder can penetrate | invade (more ideally, the convex part of different conductive powder can be fitted and connected to this concave part). The reason for this is that with this configuration, the convex portion and the concave portion can be easily fitted and connected between adjacent conductive powders. Further, the depth (size) of the recess can be represented by the volume of the recess that occupies the conductive powder, that is, the porosity of the recess. Specifically, when the volume of a sphere composed of a closed curve surrounding the tip of the convex part is 100% by volume, the porosity of the concave part is preferably set to a value of 40% by volume or more. The reason for this is that when the porosity of the recesses is less than 40% by volume, the fitting connection between the projections and the recesses may be insufficient. On the other hand, if the porosity of such concave portions is excessively large, the mechanical strength of the conductive powder may be significantly reduced. Therefore, it is more preferable to set the porosity of the concave portion to a value within the range of 42 to 70% by volume, and it is even more preferable to set the value within the range of 45 to 60% by volume.
接合用組成物における導電粉の含有量は７０〜８０質量％とすることが好ましく、７０〜７４質量％とすることがより好ましい。導電粉の含有量が７０質量％以上であると、被接合面に塗布した接合用組成物が加熱された際に導電粉同士の接触を担保することができ、十分な接合強度を得ることができ、８０質量％以下であると、被接合面に接合用組成物を均一に塗布しやすい。また、当該質量％の範囲内でより導電粉の含有量が少ない範囲、具体的には、７０〜７４質量％とすることで、比較的高価な導電粉の使用量をより低減させることができる（接合強度は維持される）。 The content of the conductive powder in the bonding composition is preferably 70 to 80% by mass, and more preferably 70 to 74% by mass. When the content of the conductive powder is 70% by mass or more, the contact between the conductive powders can be ensured when the bonding composition applied to the surfaces to be bonded is heated, and sufficient bonding strength can be obtained. If it is 80% by mass or less, it is easy to uniformly apply the bonding composition to the surfaces to be bonded. Moreover, the usage amount of a comparatively expensive electroconductive powder can be reduced more by setting it as the range with less content of electroconductive powder within the said mass% range, specifically 70-74 mass%. (Joint strength is maintained).
ここで、接合用組成物の導電粉の含有量が少なくなると導電粉同士の接点が少なくなり、接合強度が著しく低下するのが一般的である。これに対し、本発明の接合方法においては、導電粉として比較的大きなマイクロサイズ銀粒子を使用していることに加え、当該マイクロサイズ銀粒子は表面に放射状に延設された凸部を有していることから、接合用組成物中の導電粉の含有量が７０〜８０質量％と少ない場合であっても十分な接合強度を発現することができる。 Here, when the content of the conductive powder in the bonding composition decreases, the number of contacts between the conductive powders decreases, and the bonding strength generally decreases significantly. On the other hand, in the bonding method of the present invention, in addition to using relatively large micro-sized silver particles as the conductive powder, the micro-sized silver particles have convex portions extending radially on the surface. Therefore, even when the content of the conductive powder in the bonding composition is as small as 70 to 80% by mass, sufficient bonding strength can be expressed.
本実施の形態にかかる接合用組成物の金属粒子は、上述の特徴を有する導電粉（マイクロサイズ銀粒子）であれば特に制限されないが、例えば、化研テック株式会社製の導電粉を好適に用いることができる。 The metal particles of the bonding composition according to the present embodiment are not particularly limited as long as they are conductive powders (micro-sized silver particles) having the above-described characteristics. For example, conductive powders manufactured by Kaken Tech Co., Ltd. are preferably used. Can be used.
（１−２）有機溶剤
本実施の形態にかかる接合用組成物に用いる有機溶媒は、本発明の効果を損なわない範囲で種々の有機溶媒を用いることができる。有機溶剤としては、例えば、テルペン系溶剤、ケトン系溶剤、アルコール系溶剤、エステル系溶剤、エーテル系溶剤、脂肪族炭化水素系溶剤、芳香族炭化水素系溶剤、セロソルブ系溶剤、カルビトール系溶剤等が挙げられる。より具体的には、ターピネオール、メチルエチルケトン、アセトン、イソプロパノール、ブチルカービトール、デカン、ウンデカン、テトラデカン、ベンゼン、トルエン、ヘキサン、ジエチルエーテル、ケロシン等の有機溶媒を用いることができる。
(1-2) Organic solvent Various organic solvents can be used for the organic solvent used for the composition for joining concerning this Embodiment in the range which does not impair the effect of the present invention. Examples of the organic solvent include terpene solvents, ketone solvents, alcohol solvents, ester solvents, ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, cellosolve solvents, carbitol solvents, and the like. Is mentioned. More specifically, organic solvents such as terpineol, methyl ethyl ketone, acetone, isopropanol, butyl carbitol, decane, undecane, tetradecane, benzene, toluene, hexane, diethyl ether, and kerosene can be used.
（１−３）その他
本実施の形態にかかる接合用組成物には、上記の成分に加えて、本発明の効果を損なわない範囲で、使用目的に応じた適度な粘性、密着性、乾燥性又は印刷性等の機能を付与するために、分散媒や、例えばバインダーとしての役割を果たすオリゴマー成分、樹脂成分、有機溶剤（固形分の一部を溶解又は分散していてよい。）、界面活性剤、増粘剤又は表面張力調整剤等の任意成分を添加してもよい。かかる任意成分としては、特に限定されない。
(1-3) Others In addition to the above-described components, the bonding composition according to the present embodiment has an appropriate viscosity, adhesion, and drying property in accordance with the intended use within a range that does not impair the effects of the present invention. Alternatively, in order to impart functions such as printability, a dispersion medium, an oligomer component that serves as a binder, for example, a resin component, an organic solvent (a part of the solid content may be dissolved or dispersed), a surface activity. You may add arbitrary components, such as an agent, a thickener, or a surface tension modifier. Such optional components are not particularly limited.
任意成分のうちの分散媒としては、本発明の効果を損なわない範囲で種々のものを使用可能であり、例えば炭化水素及びアルコール等が挙げられる。 As the dispersion medium of the optional components, various types can be used as long as the effects of the present invention are not impaired, and examples thereof include hydrocarbons and alcohols.
炭化水素としては、脂肪族炭化水素、環状炭化水素及び脂環式炭化水素等が挙げられ、それぞれ単独で用いてもよく、２種以上を併用してもよい。 Examples of the hydrocarbon include aliphatic hydrocarbons, cyclic hydrocarbons and alicyclic hydrocarbons, and each may be used alone or in combination of two or more.
脂肪族炭化水素としては、例えば、テトラデカン、オクタデカン、ヘプタメチルノナン、テトラメチルペンタデカン、ヘキサン、ヘプタン、オクタン、ノナン、デカン、トリデカン、メチルペンタン、ノルマルパラフィン、イソパラフィン等の飽和又は不飽和脂肪族炭化水素が挙げられる。 Examples of the aliphatic hydrocarbon include saturated or unsaturated aliphatic hydrocarbons such as tetradecane, octadecane, heptamethylnonane, tetramethylpentadecane, hexane, heptane, octane, nonane, decane, tridecane, methylpentane, normal paraffin, and isoparaffin. Is mentioned.
環状炭化水素としては、例えば、トルエン、キシレン等が挙げられる。 Examples of the cyclic hydrocarbon include toluene and xylene.
脂環式炭化水素としては、例えば、リモネン、ジペンテン、テルピネン、ターピネン（テルピネンともいう。）、ネソール、シネン、オレンジフレーバー、テルピノレン、ターピノレン（テルピノレンともいう。）、フェランドレン、メンタジエン、テレベン、ジヒドロサイメン、モスレン、イソテルピネン、イソターピネン（イソテルピネンともいう。）、クリトメン、カウツシン、カジェプテン、オイリメン、ピネン、テレビン、メンタン、ピナン、テルペン、シクロヘキサン等が挙げられる。 Examples of the alicyclic hydrocarbon include limonene, dipentene, terpinene, terpinene (also referred to as terpinene), nesol, sinene, orange flavor, terpinolene, terpinolene (also referred to as terpinolene), ferrandylene, mentadiene, teleben, dihydrocymene. , Muslene, isoterpinene, isoterpinene (also referred to as isoterpinene), clitomen, kautsin, cajepten, oilimene, pinene, turpentine, menthane, pinane, terpene, cyclohexane and the like.
また、アルコールは、ＯＨ基を分子構造中に１つ以上含む化合物であり、脂肪族アルコール、環状アルコール及び脂環式アルコールが挙げられ、それぞれ単独で用いてもよく、２種以上を併用してもよい。また、ＯＨ基の一部は、本発明の効果を損なわない範囲でアセトキシ基等に誘導されていてもよい。 Alcohol is a compound containing one or more OH groups in the molecular structure, and examples thereof include aliphatic alcohols, cyclic alcohols and alicyclic alcohols, and each may be used alone or in combination of two or more. Also good. Moreover, a part of OH group may be induced | guided | derived to the acetoxy group etc. in the range which does not impair the effect of this invention.
脂肪族アルコールとしては、例えば、ヘプタノール、オクタノール（１−オクタノール、２−オクタノール、３−オクタノール等）、デカノール（１−デカノール等）、ラウリルアルコール、テトラデシルアルコール、セチルアルコール、２−エチル−１−ヘキサノール、オクタデシルアルコール、ヘキサデセノール、オレイルアルコール等の飽和又は不飽和Ｃ６−３０脂肪族アルコール等が挙げられる。 Examples of the aliphatic alcohol include heptanol, octanol (1-octanol, 2-octanol, 3-octanol, etc.), decanol (1-decanol, etc.), lauryl alcohol, tetradecyl alcohol, cetyl alcohol, 2-ethyl-1- Examples thereof include saturated or unsaturated C 6-30 aliphatic alcohols such as hexanol, octadecyl alcohol, hexadecenol and oleyl alcohol.
環状アルコールとしては、例えば、クレゾール、オイゲノール等が挙げられる。 Examples of the cyclic alcohol include cresol and eugenol.
脂環式アルコールとしては、例えば、シクロヘキサノール等のシクロアルカノール、テルピネオール（α、β、γ異性体、又はこれらの任意の混合物を含む。）、ジヒドロテルピネオール等のテルペンアルコール（モノテルペンアルコール等）、ジヒドロターピネオール、ミルテノール、ソブレロール、メントール、カルベオール、ペリリルアルコール、ピノカルベオール、ソブレロール、ベルベノール等が挙げられる。 Examples of alicyclic alcohols include cycloalkanols such as cyclohexanol, terpineols (including α, β, γ isomers, or any mixture thereof), terpene alcohols such as dihydroterpineol (monoterpene alcohols, etc.), Dihydroterpineol, myrtenol, sobrerol, menthol, carveol, perillyl alcohol, pinocarveol, sobrerol, berbenol and the like can be mentioned.
本実施の形態にかかる接合用組成物中に分散媒を含有させる場合の含有量は、粘度などの所望の特性によって調整すればよく、接合用組成物中の分散媒の含有量は、１〜３０質量％であるのが好ましい。分散媒の含有量が１〜３０質量％であれば、接合用組成物として使いやすい範囲で粘度を調整する効果を得ることができる。分散媒のより好ましい含有量は１〜２０質量％であり、更に好ましい含有量は１〜１５質量％である。 The content in the case where the dispersion medium is contained in the bonding composition according to the present embodiment may be adjusted according to desired properties such as viscosity, and the content of the dispersion medium in the bonding composition is 1 to It is preferably 30% by mass. If content of a dispersion medium is 1-30 mass%, the effect of adjusting a viscosity in the range which is easy to use as a joining composition can be acquired. A more preferable content of the dispersion medium is 1 to 20% by mass, and a more preferable content is 1 to 15% by mass.
樹脂成分としては、例えば、ポリエステル系樹脂、ブロックドイソシアネート等のポリウレタン系樹脂、ポリアクリレート系樹脂、ポリアクリルアミド系樹脂、ポリエーテル系樹脂、メラミン系樹脂又はテルペン系樹脂等を挙げることができ、これらはそれぞれ単独で用いてもよく、２種以上を併用してもよい。 Examples of the resin component include polyester resins, polyurethane resins such as blocked isocyanate, polyacrylate resins, polyacrylamide resins, polyether resins, melamine resins, and terpene resins. May be used alone or in combination of two or more.
有機溶剤としては、上記の分散媒として挙げられたものを除き、例えば、メチルアルコール、エチルアルコール、ｎ−プロピルアルコール、２−プロピルアルコール、１，３−プロパンジオール、１，２−プロパンジオール、１，４−ブタンジオール、１，２，６−ヘキサントリオール、１−エトキシ−２−プロパノール、２−ブトキシエタノール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、重量平均分子量が２００以上１，０００以下の範囲内であるポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、重量平均分子量が３００以上１，０００以下の範囲内であるポリプロピレングリコール、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、グリセリン又はアセトン等が挙げられ、これらはそれぞれ単独で用いてもよく、２種以上を併用してもよい。 As the organic solvent, except for those mentioned as the above dispersion medium, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, 2-propyl alcohol, 1,3-propanediol, 1,2-propanediol, 1 , 4-butanediol, 1,2,6-hexanetriol, 1-ethoxy-2-propanol, 2-butoxyethanol, ethylene glycol, diethylene glycol, triethylene glycol, weight average molecular weight in the range of 200 to 1,000 Polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol having a weight average molecular weight in the range of 300 to 1,000, N, N-dimethylformamide, dimethyl sulfoxide, N- Chill-2-pyrrolidone, N, N- dimethylacetamide, glycerin, or acetone and the like may be used each of which alone or in combination of two or more.
増粘剤としては、例えば、クレイ、ベントナイト又はヘクトライト等の粘土鉱物、例えば、ポリエステル系エマルジョン樹脂、アクリル系エマルジョン樹脂、ポリウレタン系エマルジョン樹脂又はブロックドイソシアネート等のエマルジョン、メチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース等のセルロース誘導体、キサンタンガム又はグアーガム等の多糖類等が挙げられ、これらはそれぞれ単独で用いてもよく、２種以上を併用してもよい。 Examples of the thickener include clay minerals such as clay, bentonite or hectorite, for example, emulsions such as polyester emulsion resins, acrylic emulsion resins, polyurethane emulsion resins or blocked isocyanates, methyl cellulose, carboxymethyl cellulose, and hydroxyethyl cellulose. , Cellulose derivatives such as hydroxypropylcellulose and hydroxypropylmethylcellulose, polysaccharides such as xanthan gum and guar gum, and the like. These may be used alone or in combination of two or more.
また、上記有機成分とは異なる界面活性剤を添加してもよい。多成分溶媒系の金属コロイド分散液においては、乾燥時の揮発速度の違いによる被膜表面の荒れ及び固形分の偏りが生じ易い。本実施の形態にかかる接合用組成物に界面活性剤を添加することによってこれらの不利益を抑制し、均一な導電性被膜を形成することができる接合用組成物が得られる。 Moreover, you may add surfactant different from the said organic component. In a multi-component solvent-based metal colloidal dispersion, roughness of the coating surface and uneven solid content are likely to occur due to differences in volatilization rate during drying. By adding a surfactant to the bonding composition according to the present embodiment, these disadvantages can be suppressed, and a bonding composition capable of forming a uniform conductive film can be obtained.
本実施の形態において用いることのできる界面活性剤としては、特に限定されず、アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤の何れを用いることができ、例えば、アルキルベンゼンスルホン酸塩、４級アンモニウム塩等が挙げられる。少量の添加量で効果が得られるので、フッ素系界面活性剤が好ましい。 The surfactant that can be used in the present embodiment is not particularly limited, and any of an anionic surfactant, a cationic surfactant, and a nonionic surfactant can be used. For example, alkylbenzenesulfonic acid Salt, quaternary ammonium salt and the like. Since the effect can be obtained with a small addition amount, a fluorosurfactant is preferable.
なお、有機成分量を所定の範囲に調整する方法は、加熱を行って調整するのが簡便である。また、導電粉を作製する際に添加する有機成分の量を調整することで行ってもよい。加熱はオーブンやエバポレーターなどで行うことができ、減圧下で行ってもよい。常圧下で行う場合は、大気中でも不活性雰囲気中でも行うことができる。更に、有機成分量の微調整のために、アミン（及びカルボン酸）を後で加えることもできる。 In addition, it is easy to adjust the method of adjusting the amount of organic components in a predetermined range by heating. Moreover, you may carry out by adjusting the quantity of the organic component added when producing electroconductive powder. Heating can be performed with an oven or an evaporator, and may be performed under reduced pressure. When performed under normal pressure, it can be performed in air or in an inert atmosphere. Furthermore, amines (and carboxylic acids) can be added later for fine adjustment of the amount of organic components.
本実施の形態にかかる接合用組成物の粘度は、固形分の濃度は本発明の効果を損なわない範囲で適宜調整すればよいが、例えば０．０１〜５０００Ｐａ・ｓの粘度範囲であればよく、０．１〜１０００Ｐａ・ｓの粘度範囲がより好ましく、１〜１００Ｐａ・ｓの粘度範囲であることが特に好ましい。当該粘度範囲とすることにより、被接合材に接合用組成物を塗布する方法として幅広い方法を適用することができる。 The viscosity of the bonding composition according to the present embodiment may be adjusted as appropriate so that the solid content does not impair the effects of the present invention. For example, the viscosity may be in the range of 0.01 to 5000 Pa · s. The viscosity range of 0.1 to 1000 Pa · s is more preferable, and the viscosity range of 1 to 100 Pa · s is particularly preferable. By setting it as the said viscosity range, a wide method is applicable as a method of apply | coating the composition for joining to a to-be-joined material.
粘度の調整は、導電粉の粒径の調整、有機物の含有量の調整、分散媒その他の成分の添加量の調整、各成分の配合比の調整、増粘剤の添加等によって行うことができる。接合用組成物の粘度は、例えば、コーンプレート型粘度計（例えばアントンパール社製のレオメーターＭＣＲ３０１）により測定することができる。 The viscosity can be adjusted by adjusting the particle size of the conductive powder, adjusting the content of organic matter, adjusting the addition amount of the dispersion medium and other components, adjusting the blending ratio of each component, and adding a thickener. . The viscosity of the bonding composition can be measured, for example, with a cone plate viscometer (for example, a rheometer MCR301 manufactured by Anton Paar).
本発明の接合方法で用いる接合用組成物は、上述の導電粉及び有機溶媒等を従来公知の種々の方法で均一に混合することにより得ることができる。なお、混合方法は、乾式混合であってもよいし、溶媒等を用いて湿式混合を実施してもよい。 The bonding composition used in the bonding method of the present invention can be obtained by uniformly mixing the above-described conductive powder, organic solvent, and the like by various conventionally known methods. The mixing method may be dry mixing or wet mixing using a solvent or the like.
（２）接合方法
本実施形態の金属接合用組成物を用いれば、加熱を伴う部材同士の接合において高い接合強度を得ることができる。図１は、本実施の形態にかかるマイクロサイズ銀粒子を含む接合用組成物を用いた部材の接合方法を示すフローチャートである。図２〜４は、本実施の形態にかかるマイクロサイズ銀粒子を含む接合用組成物を用いた部材の接合方法を説明する模式図である。まず、上述した金属接合用組成物Ｐを第１の被接合部材１００に塗布する（ステップＳ１：接合用組成物塗布工程）。ステップＳ１では、図２に示すように、第１の被接合部材１００の上面にペースト状の金属接合用組成物Ｐを塗布する。
(2) Joining method If the composition for metal joining of this embodiment is used, high joining strength can be obtained in joining of members accompanied by heating. FIG. 1 is a flowchart showing a member bonding method using a bonding composition containing micro-sized silver particles according to the present embodiment. FIGS. 2-4 is a schematic diagram explaining the joining method of the member using the composition for joining containing the microsize silver particle concerning this Embodiment. First, the metal bonding composition P described above is applied to the first member to be bonded 100 (step S1: bonding composition application step). In step S1, as shown in FIG. 2, a paste-like metal bonding composition P is applied to the upper surface of the first member to be bonded 100.
ここで、「塗布」とは、金属接合用組成物Ｐを面状に塗布する場合も線状に塗布（描画）する場合も含む概念である。塗布されて、加熱により焼成される前の状態の金属接合用組成物からなる塗膜の形状は、所望する形状にすることが可能である。したがって、金属接合用組成物Ｐは、面状の接合層及び線状の接合層のいずれも含む概念であり、これら面状の接合層及び線状の接合層は、連続していても不連続であってもよく、連続する部分と不連続の部分とを含んでいてもよい。 Here, the term “application” is a concept that includes a case where the metal bonding composition P is applied in a planar shape and a case where it is applied (drawn) linearly. The shape of the coating film made of the composition for metal bonding before being applied and fired by heating can be made into a desired shape. Therefore, the metal bonding composition P is a concept including both a planar bonding layer and a linear bonding layer, and these planar bonding layers and linear bonding layers are discontinuous even if continuous. It may be a continuous part and a discontinuous part.
金属接合用組成物を被接合部材に塗布する工程では、種々の方法を用いることが可能であるが、上述のように、例えば、ディッピング、スクリーン印刷、スプレー式、バーコート式、スピンコート式、インクジェット式、ディスペンサー式、ピントランスファー法、刷毛による塗布方式、流延式、フレキソ式、グラビア式、又はシリンジ式等のなかから適宜選択して用いることができる。また、予め被接合部材表面に界面活性剤又は表面活性剤等を塗布しておくことも可能である。 In the step of applying the metal bonding composition to the bonded members, various methods can be used. As described above, for example, dipping, screen printing, spraying, bar coating, spin coating, The ink jet method, the dispenser method, the pin transfer method, the brush application method, the casting method, the flexo method, the gravure method, the syringe method, and the like can be appropriately selected and used. It is also possible to apply a surface active agent or a surface active agent to the surface of the member to be joined in advance.
第１の被接合部材１００に接合用組成物Ｐを塗布した後、無加圧下、所定の予熱温度（例えば２５０℃以下、好ましくは１１０〜１５０℃）および所定の時間（例えば１０分）で、第１の被接合部材１００上の接合用組成物Ｐを加熱する（ステップＳ２：加熱工程）。ステップＳ２では、粒子同士の焼結を抑制しつつ、接合用組成物Ｐに含まれる有機溶剤を蒸発させる。ステップＳ２における温度は、例えば接合用組成物Ｐに含まれる有機溶剤の沸点程度であって、マイクロサイズ銀粒子同士が接合しない程度の温度に設定される。ステップＳ２により、第１の被接合部材１００に接合用組成物Ｐがプリコートされた成形体を得ることができる。 After applying the bonding composition P to the first bonded member 100, under no pressure, at a predetermined preheating temperature (for example, 250 ° C. or less, preferably 110 to 150 ° C.) and a predetermined time (for example, 10 minutes), The bonding composition P on the first bonded member 100 is heated (step S2: heating step). In step S2, the organic solvent contained in the bonding composition P is evaporated while suppressing the sintering of the particles. The temperature in step S2 is set to a temperature that is, for example, about the boiling point of the organic solvent contained in the bonding composition P and does not bond the micro-sized silver particles. By step S2, the molded object by which the composition P for joining was precoated on the 1st to-be-joined member 100 can be obtained.
その後、有機溶剤が蒸発した接合用組成物Ｐ上に第２の被接合部材１０１を載置し（図３参照）、所望の温度（例えば１５０℃以上３５０℃以下、例えば３００℃）および所望の圧力（例えば１０ＭＰａ）下で焼成して接合する（ステップＳ３：接合工程）。これにより、接合用組成物Ｐを介して第１の被接合部材１００と第２の被接合部材１０１とを接合することができる（図４参照）。この際、外部から加圧するほか、第２の被接合部材１０１の自重圧下のみで接合用組成物Ｐを加圧するようにしてもよい。また、焼成を行う際、段階的に温度を上げたり下げたりすることもできる。なお、接合工程の温度が、加熱工程の予熱温度より下回る場合があるが、加熱工程は無加圧下で行っているため、例えば予熱温度を２５０℃としても接合用組成物Ｐ同士の接合（焼結）や、接合用組成物Ｐと第１の被接合部材１００または第２の被接合部材１０１との接合が進行することはない。一方、接合用組成物Ｐをナノサイズとすると、例えば無加圧下で予熱温度を２５０℃とした場合に接合用組成物Ｐ同士の接合（焼結）が進行するため、接合用組成物がプリコートされた成形体を得ることはできない。 Thereafter, the second member to be bonded 101 is placed on the bonding composition P in which the organic solvent has evaporated (see FIG. 3), and the desired temperature (for example, 150 ° C. or higher and 350 ° C. or lower, for example, 300 ° C.) and the desired Firing and joining under pressure (for example, 10 MPa) (step S3: joining process). Thereby, the 1st to-be-joined member 100 and the 2nd to-be-joined member 101 can be joined via the composition P for joining (refer FIG. 4). At this time, in addition to pressurization from the outside, the bonding composition P may be pressed only under the self-weight pressure of the second bonded member 101. In addition, when firing, the temperature can be raised or lowered stepwise. In addition, although the temperature of a joining process may be lower than the preheating temperature of a heating process, since the heating process is performed under no pressure, for example, even if the preheating temperature is set to 250 ° C., the joining composition P can be joined (fired). ) And the bonding of the bonding composition P to the first bonded member 100 or the second bonded member 101 does not proceed. On the other hand, when the bonding composition P is nano-sized, for example, when the preheating temperature is 250 ° C. under no pressure, bonding (sintering) between the bonding compositions P proceeds, so the bonding composition is precoated. It is not possible to obtain a molded product.
本実施形態において用いることのできる第１の被接合部材及び第２の被接合部材としては、金属接合用組成物を塗布して加熱により焼成して接合することのできるものであればよく、特に制限はないが、接合時の温度により損傷しない程度の耐熱性を具備した部材であるのが好ましい。 The first member to be joined and the second member to be joined that can be used in the present embodiment may be any member that can be applied by applying a metal joining composition and firing it by heating to join. Although there is no restriction | limiting, It is preferable that it is a member provided with the heat resistance of the grade which is not damaged by the temperature at the time of joining.
このような被接合部材を構成する材料としては、例えば、ポリアミド（ＰＡ）、ポリイミド（ＰＩ）、ポリアミドイミド（ＰＡＩ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンナフタレート（ＰＥＮ）等のポリエステル、ポリカーボネート（ＰＣ）、ポリエーテルスルホン（ＰＥＳ）、ビニル樹脂、フッ素樹脂、液晶ポリマー、セラミクス、ガラス又は金属等を挙げることができるが、なかでも、金属製の被接合部材が好ましい。金属製の被接合部材が好ましいのは、耐熱性に優れているとともに、無機粒子が金属である本発明の金属接合用組成物との親和性に優れているからである。 Examples of the material constituting such a member to be joined include polyamide (PA), polyimide (PI), polyamideimide (PAI), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN). Examples thereof include polyester, polycarbonate (PC), polyethersulfone (PES), vinyl resin, fluororesin, liquid crystal polymer, ceramics, glass, metal and the like, and among them, a metal joined member is preferable. The metal bonded member is preferable because it is excellent in heat resistance and has excellent affinity with the metal bonding composition of the present invention in which the inorganic particles are metal.
また、被接合部材は、例えば板状又はストリップ状等の種々の形状であってよく、リジッドでもフレキシブルでもよい。基材の厚さも適宜選択することができる。接着性若しくは密着性の向上又はその他の目的ために、表面層が形成された部材や親水化処理等の表面処理を施した部材を用いてもよい。 The member to be joined may have various shapes such as a plate shape or a strip shape, and may be rigid or flexible. The thickness of the substrate can also be selected as appropriate. In order to improve adhesion or adhesion, or for other purposes, a member on which a surface layer is formed or a member subjected to a surface treatment such as a hydrophilic treatment may be used.
上記のようにプリコート後の塗膜を、被接合部材を損傷させない範囲で、例えば３５０℃以下の温度で加熱することにより焼成し、本実施形態の接合体を得ることができる。本実施形態においては、先に述べたように、本実施形態の金属接合用組成物を用いるため、被接合部材に対して優れた密着性を有する接合層が得られ、強い接合強度がより確実に得られる。 As described above, the pre-coated film is baked by heating at a temperature of 350 ° C. or less, for example, within a range that does not damage the member to be bonded, and the bonded body of this embodiment can be obtained. In the present embodiment, as described above, since the metal bonding composition of the present embodiment is used, a bonding layer having excellent adhesion to a member to be bonded is obtained, and strong bonding strength is more reliable. Is obtained.
以上説明した実施の形態によれば、金属接合用組成物塗布工程での金属接合用組成物として、上述した本実施の形態の金属接合用組成物を用いるとともに、予熱工程において第１の被接合部材１００に接合用組成物Ｐがプリコートされた成形体を作製するようにしたので、第１の被接合部材１００と第２の被接合部材１０１とを接合する作業者が、プリコートされた成形体を用いて第１の被接合部材１００と第２の被接合部材１０１とを接合することで、比較的低い接合温度であっても接合強度を確保しつつ、部材同士を確実かつ簡易に接合することができる。 According to the embodiment described above, the metal bonding composition of the present embodiment described above is used as the metal bonding composition in the metal bonding composition coating process, and the first bonded object is used in the preheating process. Since the molded body in which the bonding composition P is pre-coated on the member 100 is produced, the molded body in which the operator who joins the first bonded member 100 and the second bonded member 101 is pre-coated. By joining the first member to be joined 100 and the second member to be joined 101 by using the members, the members can be reliably and simply joined while securing the joining strength even at a relatively low joining temperature. be able to.
また、上述した実施の形態によれば、予熱工程において接合用組成物Ｐの有機溶剤を蒸発させるようにしたので、接合用組成物Ｐにおける金属粒子が高密度となり、部材同士を確実かつ簡易に接合することができる。 Further, according to the above-described embodiment, since the organic solvent of the bonding composition P is evaporated in the preheating step, the metal particles in the bonding composition P become high in density, and the members are surely and easily connected. Can be joined.
また、従来のようなナノサイズの導電粉を用いる場合は有機物の蒸発により、接合中の体積変化が大きくなってしまうという問題が存在するが、上述した実施の形態ではマイクロサイズの導電粉を用いるようにしたので、ナノサイズの導電粉を用いる場合と比して接合中の体積変化を抑制することができる。 In addition, when using nano-sized conductive powder as in the past, there is a problem that the volume change during bonding becomes large due to evaporation of organic matter, but in the above-described embodiment, micro-sized conductive powder is used. Since it did in this way, the volume change in joining can be suppressed compared with the case where a nanosized electrically conductive powder is used.
なお、上述した実施の形態において、金属接合用組成物がバインダー成分を含む場合は、接合層の強度向上及び被接合部材間の接合強度向上等の観点から、バインダー成分も焼結することになるが、場合によっては、各種印刷法へ適用するために接合用組成物の粘度を調整することをバインダー成分の主目的として、焼成条件を制御してバインダー成分を全て除去してもよい。 In addition, in embodiment mentioned above, when the composition for metal joining contains a binder component, a binder component will also sinter from viewpoints, such as the improvement of the intensity | strength of a joining layer, and the joining strength between to-be-joined members. However, in some cases, the binder component may be mainly used to adjust the viscosity of the bonding composition for application to various printing methods, and the binder condition may be controlled to remove all of the binder component.
上記焼成を行う方法は特に限定されるものではなく、例えば従来公知のオーブン等を用いて、被接合部材上にプリコートされた金属接合用組成物の温度が、例えば３５０℃以下となるように焼成することによって接合することができる。上記焼成の温度の下限は必ずしも限定されず、被接合部材同士を接合できる温度であって、かつ、本発明の効果を損なわない範囲の温度であることが好ましい。ここで、上記焼成後の金属接合用組成物においては、なるべく高い接合強度を得るという点で、有機物の残存量は少ないほうがよいが、本発明の効果を損なわない範囲で有機物の一部が残存していても構わない。 The method for performing the firing is not particularly limited. For example, using a conventionally known oven or the like, firing is performed so that the temperature of the metal bonding composition pre-coated on the member to be bonded is 350 ° C. or less, for example. Can be joined. The lower limit of the firing temperature is not necessarily limited, and is preferably a temperature at which the members to be joined can be joined and does not impair the effects of the present invention. Here, in the metal bonding composition after firing, it is better that the residual amount of the organic matter is small in terms of obtaining as high a bonding strength as possible, but a part of the organic matter remains within the range not impairing the effect of the present invention. It does not matter.
また、本発明の接合方法で用いる金属接合用組成物には、有機物が含まれているが、従来の例えばエポキシ樹脂等の熱硬化を利用したものと異なり、有機物の作用によって焼成後の接合強度を得るものではなく、上述したように融着した導電粉の融着によって十分な接合強度が得られるものである。このため、接合後において、接合温度よりも高温の使用環境に置かれて残存した有機物が劣化ないし分解・消失した場合であっても、接合強度が低下するおそれはなく、したがって耐熱性に優れている。 In addition, the metal bonding composition used in the bonding method of the present invention contains an organic substance, but unlike conventional ones that use thermosetting, such as an epoxy resin, the bonding strength after firing due to the action of the organic substance. However, sufficient bonding strength can be obtained by fusing the conductive powder fused as described above. For this reason, even after bonding, even if the remaining organic matter is deteriorated or decomposed / disappeared in a use environment higher than the bonding temperature, there is no possibility that the bonding strength is lowered, and therefore, the heat resistance is excellent. Yes.
本発明の接合方法で用いる金属接合用組成物によれば、例えば１５０〜２５０℃程度の低温加熱による焼成でも高い導電性を発現する接合層を有する接合を実現することができるため、比較的熱に弱い被接合部材同士を接合することができる。また、焼成時間は特に限定されるものではなく、焼成温度に応じて、接合できる焼成時間であればよい。 According to the metal bonding composition used in the bonding method of the present invention, it is possible to realize a bonding having a bonding layer that exhibits high conductivity even by firing at a low temperature of about 150 to 250 ° C. Members to be welded can be joined to each other. Further, the firing time is not particularly limited, and may be any firing time that can be bonded according to the firing temperature.
本実施形態においては、上記被接合部材と接合層との密着性を更に高めるため、上記被接合部材の表面処理を行ってもよい。上記表面処理方法としては、例えば、コロナ処理、プラズマ処理、ＵＶ処理、電子線処理等のドライ処理を行う方法、基材上にあらかじめプライマー層や導電性ペースト受容層を設ける方法等が挙げられる。 In this embodiment, in order to further improve the adhesion between the member to be bonded and the bonding layer, a surface treatment of the member to be bonded may be performed. Examples of the surface treatment method include a method of performing dry treatment such as corona treatment, plasma treatment, UV treatment, and electron beam treatment, and a method of previously providing a primer layer and a conductive paste receiving layer on a substrate.
接合工程の雰囲気は特に制限されず、大気中、不活性ガス雰囲気下、減圧下等で行うことができる。 The atmosphere in the bonding step is not particularly limited, and can be performed in the air, under an inert gas atmosphere, under reduced pressure, or the like.
また、上述した実施の形態では、毬栗状の導電粉を用いるものとして説明したが、毬栗状の導電粉に加え、球状の導電粉を含んでいてもよい。球状の導電粉は、毬栗状の導電粉同士の焼結により生じた導電粉間の間隙に収容または嵌合可能な径（例えば数μｍ程度）を有することが好ましい。 Moreover, in embodiment mentioned above, although demonstrated as what uses a chestnut-shaped electroconductive powder, in addition to an ocher-shaped electroconductive powder, you may contain spherical electroconductive powder. The spherical conductive powder preferably has a diameter (for example, about several μm) that can be accommodated or fitted in a gap between the conductive powders produced by sintering the chestnut-shaped conductive powders.
以上、本発明の代表的な実施形態について説明したが、本発明はこれらのみに限定されるものではない。例えば、上記実施形態においては、導電粉としてマイクロサイズ銀粒子のみを使用した場合について説明したが、例えば、接合用組成物にナノ粒子等を適宜添加して使用することもできる。 As mentioned above, although typical embodiment of this invention was described, this invention is not limited only to these. For example, in the above-described embodiment, the case where only micro-sized silver particles are used as the conductive powder has been described. However, for example, nanoparticles or the like can be appropriately added to the bonding composition and used.
以下、本発明のマイクロサイズ銀粒子を用いた接合方法の実施例について詳細に説明する。 Hereinafter, the Example of the joining method using the micro size silver particle of this invention is described in detail.
≪接合体の作製≫
化研テック株式会社製の微細な突起を有する銀粒子と有機溶剤（テルピネオール）とを混合し、銀粒子の含有量が７７質量％であるペースト状の接合用組成物１を得た。図５に、用いたマイクロサイズ銀粒子のＳＥＭ写真を示す。銀粒子の平均粒径は約３μｍであり、放射状に伸びた微細な突起部と中心部に結晶成長させるための核物質とを含むような独特な形状をしていることが確認できる。
≪Preparation of joined body≫
Silver particles having fine protrusions manufactured by Kaken Tech Co., Ltd. and an organic solvent (terpineol) were mixed to obtain a paste-like bonding composition 1 having a silver particle content of 77% by mass. In FIG. 5, the SEM photograph of the used microsize silver particle is shown. The average particle diameter of the silver particles is about 3 μm, and it can be confirmed that the silver particles have a unique shape including fine protrusions extending radially and a core material for crystal growth at the center.
接合体は、無酸素銅からなる接合試験片同士、または金メッキからなる試験片同士を接合用組成物により接合することにより得た。接合に用いた無酸素銅からなる接合試験片、または金メッキが施された接合試験片は、例えば図３，４に示した形状をなす。それぞれの試験片の接合面はＲｍａｘ＝３．２Ｓとなるように旋盤加工により仕上げ、アセトン中での超音波洗浄と塩酸中での酸洗浄とを行った後、水洗と乾燥を経て試験に供した。大きい方の円板試験片（第１の被接合部材１００）の接合面に接合用組成物Ｐを一定量塗布し、無加圧下で予熱を与えること（加熱工程）によって接合用組成物Ｐの銀粒子がプリコートされた成形体をそれぞれ形成した。本実施例では、窒素雰囲気下において予熱温度を１１０℃、１３０℃、１５０℃、１７０℃、１９０℃、２１０℃、２３０℃および２５０℃にそれぞれ設定した予熱を行った。また、予熱時間は、１０分とした。図６に、１５０℃に設定した予熱工程後のマイクロサイズ銀粒子のＳＥＭ写真を示す。図６に示すように、加熱工程後のマイクロサイズ銀粒子においては、各粒子同士の焼結が生じていない。これにより、予熱工程では、有機溶剤が蒸発し、マイクロサイズ銀粒子が円板試験片上にプリコートされた成形体が形成されたことが分かる。 The joined body was obtained by joining joining test pieces made of oxygen-free copper or test pieces made of gold plating with a joining composition. A joining test piece made of oxygen-free copper used for joining or a joining test piece subjected to gold plating has, for example, the shape shown in FIGS. The joint surface of each test piece is finished by lathe processing so that Rmax = 3.2S, subjected to ultrasonic cleaning in acetone and acid cleaning in hydrochloric acid, and then subjected to water washing and drying. did. A predetermined amount of the bonding composition P is applied to the bonding surface of the larger disk specimen (first bonded member 100), and preheating is performed under no pressure (heating process). Each molded body was precoated with silver particles. In this example, preheating was performed in a nitrogen atmosphere with preheating temperatures set to 110 ° C, 130 ° C, 150 ° C, 170 ° C, 190 ° C, 210 ° C, 230 ° C, and 250 ° C, respectively. The preheating time was 10 minutes. In FIG. 6, the SEM photograph of the microsize silver particle after the preheating process set to 150 degreeC is shown. As shown in FIG. 6, in the microsize silver particles after the heating step, the respective particles are not sintered. Thereby, it can be seen that in the preheating step, the organic solvent was evaporated, and a molded body in which micro-sized silver particles were precoated on the disk specimen was formed.
接合用組成物Ｐの導電粉がプリコートされた成形体を形成後、小さい方の試験片（第２の被接合部材１０１）を接合用組成物Ｐに重ねて接合試験片を調整した。当該試験片を、窒素雰囲気下において３００℃の接合温度（本加熱）で接合試験を行なった。接合に際しては、加圧力１０ＭＰａで加圧を行い、接合時間は１０分とした。なお、試験後は試験片を装置内で徐冷し、徐冷後、試験片を装置外に取り出した。 After forming the molded body in which the conductive powder of the bonding composition P was pre-coated, the smaller test piece (second bonded member 101) was superimposed on the bonding composition P to adjust the bonding test piece. The test piece was subjected to a bonding test at a bonding temperature of 300 ° C. (main heating) in a nitrogen atmosphere. In joining, pressurization was performed at a pressure of 10 MPa, and the joining time was 10 minutes. In addition, after the test, the test piece was gradually cooled in the apparatus, and after the slow cooling, the test piece was taken out of the apparatus.
≪せん断強度測定試験≫
接合試験により得られた接合体について、ボンドテスターを用いてせん断試験を行い、接合強度を求めた。図７は、本発明の実施例により得られた接合体のせん断強度を示すグラフであって、無酸素銅からなる接合試験片同士を接合した接合体のせん断強度を示している。図８は、本発明の実施例により得られた接合体のせん断強度を示すグラフであって、金メッキが施された接合試験片同士を接合した接合体のせん断強度を示している。なお、本実施例では、予熱温度の異なる８つの接合体（予熱温度：１１０℃〜２５０℃）を作製し、それぞれの接合体についてせん断強度を測定するせん断試験を行った。なお、図７，８では、各予熱温度において４回の測定結果の平均、最大値および最小値を示している。
≪Shear strength measurement test≫
About the joined body obtained by the joining test, the shear test was done using the bond tester, and joining strength was calculated | required. FIG. 7 is a graph showing the shear strength of the joined body obtained by the example of the present invention, and shows the shear strength of the joined body in which the joining test pieces made of oxygen-free copper are joined together. FIG. 8 is a graph showing the shear strength of the joined body obtained by the example of the present invention, and shows the shear strength of the joined body obtained by joining the test pieces subjected to gold plating. In this example, eight joined bodies having different preheating temperatures (preheating temperature: 110 ° C. to 250 ° C.) were produced, and a shear test was performed to measure the shear strength of each joined body. 7 and 8 show the average, maximum value, and minimum value of four measurement results at each preheating temperature.
図７に示すとおり、無酸素銅からなる接合試験片同士を接合した接合体は、各予熱温度において、いずれも良好な接合強度を示している。具体的には、予熱温度が１１０℃でせん断強度（平均）が１９．６ＭＰａ、予熱温度が１３０℃でせん断強度（平均）が１９．２ＭＰａ、予熱温度が１５０℃でせん断強度（平均）が１９．９ＭＰａ、予熱温度が１７０℃でせん断強度（平均）が１８．８ＭＰａ、予熱温度が１９０℃でせん断強度（平均）が２３．９ＭＰａ、予熱温度が２１０℃でせん断強度（平均）が２７．８ＭＰａ、予熱温度が２３０℃でせん断強度（平均）が２７．２ＭＰａ、予熱温度が２５０℃でせん断強度（平均）が２８．１ＭＰａである。いずれの場合においても、平均値で２０ＭＰａ程度のせん断強度を示している。特に、予熱温度が１９０°以上の場合は、平均値が２０ＭＰａを超えている。一般的な高温はんだ（例えばＰｂ−５Ｓｎ）を用いた場合のせん断強度が２０ＭＰａ程度であり、本発明の接合方法においては、用いる銀粒子がマイクロサイズであっても十分な接合強度が得られるといえる。 As shown in FIG. 7, the joined bodies obtained by joining the joining test pieces made of oxygen-free copper show good joint strength at each preheating temperature. Specifically, the preheating temperature is 110 ° C., the shear strength (average) is 19.6 MPa, the preheating temperature is 130 ° C., the shear strength (average) is 19.2 MPa, the preheating temperature is 150 ° C., and the shear strength (average) is 19 1.9 MPa, preheating temperature of 170 ° C. and shear strength (average) of 18.8 MPa, preheating temperature of 190 ° C. and shear strength (average) of 23.9 MPa, preheating temperature of 210 ° C. and shear strength (average) of 27.8 MPa The preheating temperature is 230 ° C., the shear strength (average) is 27.2 MPa, the preheating temperature is 250 ° C., and the shear strength (average) is 28.1 MPa. In any case, the average value shows a shear strength of about 20 MPa. In particular, when the preheating temperature is 190 ° or more, the average value exceeds 20 MPa. When a general high-temperature solder (for example, Pb-5Sn) is used, the shear strength is about 20 MPa. In the joining method of the present invention, sufficient joining strength can be obtained even if the silver particles used are micro-sized. I can say that.
また、図８に示すとおり、金メッキが施された接合試験片同士を接合した接合体においても、各予熱温度において、いずれも良好な接合強度を示している。具体的には、予熱温度が１１０℃でせん断強度（平均）が２１．４ＭＰａ、予熱温度が１３０℃でせん断強度（平均）が２２．６ＭＰａ、予熱温度が１５０℃でせん断強度（平均）が２２．７ＭＰａ、予熱温度が１７０℃でせん断強度（平均）が２２．３ＭＰａ、予熱温度が１９０℃でせん断強度（平均）が２９．１ＭＰａ、予熱温度が２１０℃でせん断強度（平均）が３０．３ＭＰａ、予熱温度が２３０℃でせん断強度（平均）が３０．１ＭＰａ、予熱温度が２５０℃でせん断強度（平均）が３３．０ＭＰａである。いずれの場合においても、平均値で２０ＭＰａ以上のせん断強度を示している。特に、予熱温度が２１０°以上の場合は、平均値が３０ＭＰａを超えている。上述したように、一般的な高温はんだと比しても、本発明の接合方法により、用いる銀粒子がマイクロサイズであっても十分な接合強度が得られるといえる。 Moreover, as shown in FIG. 8, also in the joined body which joined the joining test pieces with which gold plating was given, all have shown favorable joining strength in each preheating temperature. Specifically, the preheating temperature is 110 ° C., the shear strength (average) is 21.4 MPa, the preheating temperature is 130 ° C., the shear strength (average) is 22.6 MPa, the preheating temperature is 150 ° C., and the shear strength (average) is 22 0.7 MPa, preheating temperature 170 ° C. and shear strength (average) 22.3 MPa, preheating temperature 190 ° C. and shear strength (average) 29.1 MPa, preheating temperature 210 ° C. and shear strength (average) 30.3 MPa The preheating temperature is 230 ° C., the shear strength (average) is 30.1 MPa, the preheating temperature is 250 ° C., and the shear strength (average) is 33.0 MPa. In any case, the average value shows a shear strength of 20 MPa or more. In particular, when the preheating temperature is 210 ° or more, the average value exceeds 30 MPa. As described above, it can be said that sufficient bonding strength can be obtained by the bonding method of the present invention even if the silver particles to be used are micro-sized, compared with general high-temperature solder.
ここで、予熱温度の上昇に伴い接合強度が上昇する傾向にある理由としては、接合状態までの進行度の差によるものと考えられ、予熱温度が高い方が、焼結作用が働く状態に近くなるため、接合工程において速やかに焼結状態に移行でき、接合強度が高まると考えられる。 Here, the reason why the bonding strength tends to increase as the preheating temperature increases is considered to be due to the difference in the degree of progress to the bonding state, and the higher the preheating temperature is closer to the state where the sintering action works. Therefore, it can be considered that the joining process can be promptly shifted to a sintered state and the joining strength is increased.
以上のように、本発明にかかる接合方法は、接合強度を確保しつつ、部材同士を確実かつ簡易に接合する点で有用である。 As described above, the joining method according to the present invention is useful in that the members are reliably and easily joined while securing the joining strength.
１００ 第１の被接合部材
１０１ 第２の被接合部材
Ｐ 接合用組成物
100 First member to be joined 101 Second member to be joined P Composition for joining
Claims (3)
前記接合面に塗布された前記接合用組成物を無加圧下、２５０℃以下の予熱温度であって、前記有機溶剤の沸点を含む該沸点近傍の温度である予熱温度により加熱する加熱工程と、
前記接合用組成物を介して前記第１および第２の部材を重ねた後、加圧下、および１５０℃以上３５０℃以下の温度条件下で前記第１および第２の部材を接合する接合工程と、
を含むことを特徴とする接合方法。 The bonding surface of at least one of the members of the first and second members to be joined, a nuclear material ing include metal-based particles or ceramic particles, extends silver nuclear material to crystal growth, and radially comprises silver have a plurality of convex portions, the metal particles having an average particle diameter of 0.1～22Myuemu, a coating step of applying the bonding composition containing an organic solvent,
A heating step of heating the bonding composition applied to the bonding surface at a preheating temperature of 250 ° C. or less under no pressure and a preheating temperature that is a temperature near the boiling point including the boiling point of the organic solvent ;
A joining step of joining the first and second members under pressure and under a temperature condition of 150 ° C. or more and 350 ° C. or less after the first and second members are stacked via the joining composition; ,
A bonding method comprising:
を特徴とする請求項１に記載の接合方法。 The content of the metal particles in the bonding composition is 70 to 80% by mass,
The bonding method according to claim 1 , wherein:
を特徴とする請求項１または２に記載の接合方法。 The shape of the convex portion is at least one shape selected from the group consisting of needle shape, hook shape, and petal shape,
The bonding method according to claim 1 or 2, characterized in.
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