JP6549555B2 - Conductive adhesive and semiconductor device - Google Patents

Conductive adhesive and semiconductor device Download PDF

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JP6549555B2
JP6549555B2 JP2016505115A JP2016505115A JP6549555B2 JP 6549555 B2 JP6549555 B2 JP 6549555B2 JP 2016505115 A JP2016505115 A JP 2016505115A JP 2016505115 A JP2016505115 A JP 2016505115A JP 6549555 B2 JP6549555 B2 JP 6549555B2
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conductive adhesive
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silver
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JPWO2015129377A1 (en
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宜司 水村
宜司 水村
聡 齋藤
聡 齋藤
大樹 神田
大樹 神田
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Namics Corp
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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    • C09J11/04—Non-macromolecular additives inorganic
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    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0812—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0831—Gold
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/357—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
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    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives

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  • Chemical & Material Sciences (AREA)
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  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
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  • Adhesives Or Adhesive Processes (AREA)
  • Conductive Materials (AREA)

Description

本発明は、導電性接着剤に関し、特に、酸化膜を形成し易い金属を、低抵抗で接続可能な導電性接着剤に関する。   BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a conductive adhesive, and more particularly to a conductive adhesive capable of connecting a metal that easily forms an oxide film with low resistance.

半導体素子の電極部と基板の導電部とが接着された半導体装置は、非常に広範に使用されており、半導体素子の電極部と基板の導電部との接着には、導電性接着剤やはんだ付けが使用されている。導電性接着剤は、はんだ付けより低温で接着させることができる、という利点があるが、はんだよりバルク抵抗が高いため、導電性接着剤の低抵抗化が検討されている。   A semiconductor device in which an electrode portion of a semiconductor element and a conductive portion of a substrate are bonded is used in a wide range, and a conductive adhesive or solder is used to bond the electrode portion of the semiconductor element to the conductive portion of the substrate. Is used. The conductive adhesive has an advantage of being able to be bonded at a lower temperature than soldering, but since the bulk resistance is higher than that of the solder, lowering of the resistance of the conductive adhesive is being studied.

導電性接着剤のバルク抵抗を下げる手法として、導電性接着剤中の導電性フィラーの高充填化が広く知られている。しかし、基板の導電部の下地が、最表面に酸化膜を形成しやすい金属（ニッケル、銅、アルミニウム等）であるときに、導電性接着剤で接合すると、この金属の腐蝕によって接続抵抗値の上昇を招いてしまい、導電性接着剤中の導電性フィラーの高充填化では接続抵抗値の上昇を防止することができない。   As a method of reducing the bulk resistance of the conductive adhesive, it is widely known to increase the filling of the conductive filler in the conductive adhesive. However, when the base of the conductive portion of the substrate is a metal (such as nickel, copper, or aluminum) which easily forms an oxide film on the outermost surface, if it is joined by a conductive adhesive, the corrosion of this metal causes a connection resistance value. As a result, the increase in the connection resistance value can not be prevented by the high filling of the conductive filler in the conductive adhesive.

上記のような導電性接着剤を使用する場合の接続抵抗値の低抵抗化を目的とした既知の技術として、酸化皮膜を形成しやすい金属を導電性接着剤で接合するときに、導電性接着剤中に腐蝕防止剤として８−ヒドロキシキノリンを添加することが知られている。   As a known technique for reducing the connection resistance value when using a conductive adhesive as described above, when bonding a metal that easily forms an oxide film with a conductive adhesive, the conductive adhesive is used. It is known to add 8-hydroxyquinoline as an anticorrosion agent in the agent.

導電性接着剤中に腐蝕防止剤として８−ヒドロキシキノリンを添加する公知技術としては、（ａ）高分子樹脂、（ｂ）導電性充填剤、（ｃ）防食剤、（ｄ）所望により反応性または非反応性希釈剤、（ｅ）所望により不活性充填剤、および（ｆ）所望により接着促進剤を含むマイクロ電子デバイスに使用される組成物であって、前記防食剤が８−ヒドロキシキノリンである、前記組成物（特許文献１）；（ａ）ポリマー樹脂、（ｂ）導電性充填剤、（ｃ）所望により、反応性または非反応性希釈剤、（ｄ）所望により、不活性充填剤、および（ｅ）所望により、接着促進剤を含む、マイクロエレクトロニクスデバイス用組成物であって、酸素スカベンジャーもしくは腐蝕抑制剤または両者を添加することにより改良された組成物（特許文献２）；マイクロエレクトロニクスデバイスにおける使用のための組成物であって、（ａ）少なくとも１種のエポキシ樹脂と脂肪族アミンの混入剤を含む熱硬化性樹脂系、（ｂ）導電性充填剤、（ｃ）腐蝕抑制剤、（ｄ）硬化剤又は触媒、（ｅ）任意に、有機溶剤、並びに（ｆ）任意に、接着促進剤、フェノール樹脂、流動添加剤及びレオロジー改質剤からなる群の一つ以上を含み、そこでは該エポキシ樹脂中のエポキシド官能基の該脂肪族アミン中のアミン官能基に対する比が１より大きい、組成物（特許文献３）が挙げられる。   Known techniques for adding 8-hydroxyquinoline as a corrosion inhibitor in a conductive adhesive include (a) polymeric resin, (b) conductive filler, (c) anticorrosive, (d) optionally reactive Or a composition for use in a microelectronic device comprising a non-reactive diluent, (e) optionally an inert filler, and (f) optionally an adhesion promoter, wherein the corrosion inhibitor is 8-hydroxyquinoline (A) polymer resin, (b) conductive filler, (c) optionally reactive or non-reactive diluent, (d) optionally inert filler And (e) A composition for a microelectronic device, optionally comprising an adhesion promoter, wherein the composition is improved by the addition of an oxygen scavenger or a corrosion inhibitor or both. A composition for use in microelectronics devices, comprising (a) a thermosetting resin system comprising an admixture of at least one epoxy resin and an aliphatic amine, (b) a conductive filler, (c) Corrosion inhibitor, (d) curing agent or catalyst, (e) optionally, an organic solvent, and (f) optionally, one or more of the group consisting of an adhesion promoter, a phenolic resin, a flow additive and a rheology modifier U.S. Pat. No. 5,075,015, which includes a composition wherein the ratio of epoxide functional groups in the epoxy resin to amine functional groups in the aliphatic amine is greater than one.

特開２００２−３４８４８６号公報JP 2002-348486 A 特開２０００−２７３３１７号公報JP, 2000-273317, A 特表２００６−５２４２８６号公報Japanese Patent Application Publication No. 2006-524286

しかしながら、上記のような腐蝕防止剤として８−ヒドロキシキノリンを添加した導電性接着剤では、接続抵抗値の低下が十分ではなく、更なる接続抵抗値の低下が望まれている。   However, in the case of the conductive adhesive to which 8-hydroxyquinoline is added as the corrosion inhibitor as described above, the decrease in connection resistance is not sufficient, and a further decrease in connection resistance is desired.

本発明者らは、腐蝕防止剤としてモルホリン類（モルホリンおよびモルホリンと類似の構造を持つ化合物）を添加することにより、８−ヒドロキシキノリンで得られる接続抵抗値より低い接続抵抗値が得られ、また、保存中での増粘抑制によりポットライフの長い、導電性接着剤が得られることを見出した。   By adding morpholines (morpholine and a compound having a similar structure to morpholine) as a corrosion inhibitor, we can obtain a connection resistance value lower than that obtained with 8-hydroxyquinoline, and It has been found that a conductive adhesive having a long pot life can be obtained by the suppression of thickening during storage.

本発明は、腐蝕防止剤としてモルホリン類を添加することにより、低い接続抵抗値が得られ、かつ、保存中での増粘抑制によりポットライフの長い、導電性接着剤を提供することを目的とする。   The object of the present invention is to provide a conductive adhesive having a low connection resistance value by adding morpholines as a corrosion inhibitor, and having a long pot life by suppressing the thickening during storage. Do.

本発明は、以下の構成を有することによって上記問題を解決した導電性接着剤、および半導体装置に関する。
〔１〕（Ａ）エポキシ樹脂、
（Ｂ）アミン系硬化剤および／またはフェノール系硬化剤、
（Ｃ）モルホリン類還元剤、
（Ｄ）導電性充填剤、ならびに
（Ｅ）シランカップリング剤
を含有することを特徴とする、導電性接着剤。
〔２〕（Ｃ）成分が、モルホリン、２，６−ジメチルモルホリン、４−（３−ヒドロキシプロピル）モルホリン、４−メチルモルホリン、４−（４−アミノフェニル）モルホリン、チオモルホリンおよび１，１−ジオキソチオモルホリンからなる群より選択される少なくとも１種である、上記〔１〕記載の導電性接着剤。
〔３〕（Ｃ）成分が、（Ａ）〜（Ｅ）成分の合計１００質量部に対して、０．０５〜１．００質量部である、上記〔１〕または〔２〕記載の導電性接着剤。
〔４〕（Ｄ）成分が、銀、ニッケル、銅、金、パラジウム、白金、錫、アルミニウム、銀被覆銅、銀被覆アルミニウムおよび銀被覆樹脂からなる群から選択される少なくとも１種の粉末である、上記〔１〕〜〔３〕のいずれか記載の導電性接着剤。
〔５〕導電部を有する基板と、電極部を有する半導体素子とを含み、
上記〔１〕〜〔４〕のいずれか記載の導電性接着剤の硬化物で、基板の導電部と半導体素子の電極部とが接着された、半導体装置。
〔６〕基板の導電部がニッケル、アルミニウムまたは銅である、上記〔５〕記載の半導体装置。The present invention relates to a conductive adhesive and a semiconductor device in which the above problems are solved by having the following configuration.
[1] (A) Epoxy resin,
(B) amine curing agents and / or phenolic curing agents,
(C) morpholines reducing agent,
A conductive adhesive comprising: (D) a conductive filler, and (E) a silane coupling agent.
[2] Component (C) is morpholine, 2,6-dimethylmorpholine, 4- (3-hydroxypropyl) morpholine, 4-methylmorpholine, 4- (4-aminophenyl) morpholine, thiomorpholine and 1,1- The conductive adhesive according to the above [1], which is at least one selected from the group consisting of dioxothiomorpholine.
[3] The conductivity according to the above [1] or [2], wherein the component (C) is 0.05 to 1.00 parts by mass with respect to a total of 100 parts by mass of the components (A) to (E). adhesive.
[4] Component (D) is at least one powder selected from the group consisting of silver, nickel, copper, gold, palladium, platinum, tin, aluminum, silver-coated copper, silver-coated aluminum and silver-coated resin The conductive adhesive according to any one of the above [1] to [3].
[5] a substrate having a conductive portion, and a semiconductor element having an electrode portion,
The cured product of the conductive adhesive according to any one of the above [1] to [4], wherein the conductive portion of the substrate and the electrode portion of the semiconductor element are bonded.
[6] The semiconductor device according to the above [5], wherein the conductive portion of the substrate is nickel, aluminum or copper.

本発明〔１〕によれば、低い接続抵抗値が得られ、かつ、保存中での増粘抑制によりポットライフの長い、導電性接着剤を提供することができる。   According to the invention [1], a low connection resistance value can be obtained, and a conductive adhesive having a long pot life can be provided by the suppression of the thickening during storage.

本発明〔５〕によれば、半導体素子の電極部と基板の導電部との間の接続抵抗値が小さい高信頼性の半導体装置を得ることができる。   According to the invention [5], it is possible to obtain a highly reliable semiconductor device in which the connection resistance value between the electrode portion of the semiconductor element and the conductive portion of the substrate is small.

本発明の導電性接着剤は、
（Ａ）エポキシ樹脂、
（Ｂ）アミン系硬化剤および／またはフェノール系硬化剤、
（Ｃ）モルホリン類還元剤、
（Ｄ）導電性充填剤、ならびに
（Ｅ）シランカップリング剤
を含有することを特徴とする。The conductive adhesive of the present invention is
(A) Epoxy resin,
(B) amine curing agents and / or phenolic curing agents,
(C) morpholines reducing agent,
(D) A conductive filler, and (E) a silane coupling agent.

（Ａ）成分は、導電性接着剤に、接着性、硬化性を付与し、硬化後の導電性接着剤に、耐久性、耐熱性を付与する。（Ａ）成分としては、液状ビスフェノールＡ型エポキシ樹脂、液状ビスフェノールＦ型エポキシ樹脂、液状ナフタレン型エポキシ樹脂、液状アミノフェノール型エポキシ樹脂、液状水添ビスフェノール型エポキシ樹脂、液状脂環式エポキシ樹脂、液状アルコールエーテル型エポキシ樹脂、液状環状脂肪族型エポキシ樹脂、液状フルオレン型エポキシ樹脂、液状シロキサン系エポキシ樹脂等が挙げられ、液状ビスフェノールＡ型エポキシ樹脂、液状ビスフェノールＦ型エポキシ樹脂、液状ナフタレン型エポキシ樹脂が、接着性、硬化性、耐久性、耐熱性の観点から好ましい。また、エポキシ当量は、粘度調整の観点から、８０〜２５０ｇ／ｅｑが好ましい。市販品としては、新日鉄住金化学製ビスフェノールＦ型エポキシ樹脂（品名：ＹＤＦ８１７０）、ＤＩＣ製ビスフェノールＡ型エポキシ樹脂（品名：ＥＸＡ−８５０ＣＲＰ）、新日鉄住金化学製ビスフェノールＦ型エポキシ樹脂（品名：ＹＤＦ８７０ＧＳ）、ＤＩＣ製ビスフェノールＡ型／ビスフェノールＦ型混合型エポキシ樹脂（品名：ＥＸＡ８３５ＬＶ）、ＤＩＣ製ナフタレン型エポキシ樹脂（品名：ＨＰ４０３２Ｄ）、三菱化学製アミノフェノール型エポキシ樹脂（グレード：ＪＥＲ６３０、ＪＥＲ６３０ＬＳＤ）、モメンティブ・パフォーマンス製シロキサン系エポキシ樹脂（品名：ＴＳＬ９９０６）、新日鉄住金化学製１，４−シクロヘキサンジメタノールジグリシジルエーテル（品名：ＺＸ１６５８ＧＳ）等が挙げられる。（Ａ）成分は、単独でも２種以上を併用してもよい。   The component (A) imparts adhesiveness and curability to the conductive adhesive, and imparts durability and heat resistance to the conductive adhesive after curing. As component (A), liquid bisphenol A epoxy resin, liquid bisphenol F epoxy resin, liquid naphthalene epoxy resin, liquid aminophenol epoxy resin, liquid hydrogenated bisphenol epoxy resin, liquid alicyclic epoxy resin, liquid Examples include alcohol ether type epoxy resin, liquid cyclic aliphatic type epoxy resin, liquid fluorene type epoxy resin, liquid siloxane type epoxy resin and the like, liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, liquid naphthalene type epoxy resin It is preferable from the viewpoints of adhesiveness, curability, durability, and heat resistance. Moreover, as for an epoxy equivalent, from a viewpoint of viscosity adjustment, 80-250 g / eq is preferable. Commercial products include Nippon Steel & Sumikin Chemical's bisphenol F-type epoxy resin (product name: YDF 8170), DIC's bisphenol A-type epoxy resin (product name: EXA-850CRP), Nippon Steel & Sumikin Chemical Co., bisphenol F-type epoxy resin (product name: YDF870GS) DIC's bisphenol A / bisphenol F mixed epoxy resin (product name: EXA 835LV), DIC's naphthalene type epoxy resin (product name: HP4032D), Mitsubishi Chemical's aminophenol epoxy resin (grade: JER630, JER630LSD), momentary performance Siloxane-based epoxy resin (product name: TSL 9906), 1,4-cyclohexanedimethanol diglycidyl ether (product name: ZX1658GS) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and the like can be mentioned. The component (A) may be used alone or in combination of two or more.

（Ｂ）成分は、導電性接着剤を硬化させる。（Ｂ）成分のアミン系硬化剤としては、エポキシ基と付加反応しうる活性水素を分子内に１個以上有するものであればよく、特に限定されない。アミン系硬化剤としては、ジエチレントリアミン、トリエチレンテトラミン、ｎ−プロピルアミン、２−ヒドロキシエチルアミノプロピルアミン、シクロヘキシルアミン、４，４'−ジアミノ−ジシクロヘキシルメタン等の脂肪族アミン化合物；４，４'−ジアミノジフェニルメタン、２−メチルアニリン等の芳香族アミン化合物；イミダゾール、２−メチルイミダゾール、２−エチルイミダゾール、２−イソプロピルイミダゾール等のイミダゾール化合物；イミダゾリン、２−メチルイミダゾリン、２−エチルイミダゾリン等のイミダゾリン化合物等が挙げられる。   The component (B) cures the conductive adhesive. The amine-based curing agent as the component (B) is not particularly limited as long as it has one or more active hydrogens capable of undergoing an addition reaction with an epoxy group in the molecule. Aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diamino-dicyclohexylmethane etc. as an amine curing agent; 4,4'- Aromatic amine compounds such as diaminodiphenylmethane and 2-methylaniline; imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole and 2-isopropylimidazole; and imidazoline compounds such as imidazoline, 2-methylimidazoline and 2-ethylimidazoline Etc.

（Ｂ）成分のアミン系硬化剤がイミダゾール化合物であるときには、マイクロカプセル化されていると好ましく、マイクロカプセル化イミダゾール化合物硬化剤としては、ウレタン樹脂などでマイクロカプセル化されたイミダゾール化合物硬化促進剤が、保存安定性の観点から好ましく、液状ビスフェノールＡ型等の液状エポキシ樹脂中に分散され、マスターバッチ化された、マイクロカプセル化イミダゾール化合物硬化促進剤が、作業性、硬化速度、保存安定性の点からより好ましい。マイクロカプセル化イミダゾール化合物硬化剤に含有されるイミダゾール硬化剤としては、２−メチルイミダゾール、２−ウンデシルイミダゾール、２−ヘプタデシルイミダゾール、２−エチル−４−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、２，４−ジアミノ−６−［２’−メチルイミダゾリル−（１’）］エチル−ｓ−トリアジン、２−フェニル−４，５−ジヒドロキシメチルイミダゾール、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、２，３−ジヒドロ−１Ｈ−ピロロ［１，２−ａ］ベンズイミダゾール等を挙げることができ、２，４−ジアミノ−６−［２’−メチルイミダゾリル−（１’）］エチル−ｓ−トリアジン、２，４−ジアミノ−６−［２’−ウンデシルイミダゾリル−（１）］−エチル−ｓ−トリアジン、２，４−ジアミノ−６−［２’−エチル−４’−メチルイミダゾリル−（１’）］−エチル−ｓ−トリアジン等が、硬化速度、作業性、耐湿性の観点から好ましい。   When the amine curing agent of the component (B) is an imidazole compound, it is preferable that it is microencapsulated, and as the microencapsulated imidazole compound curing agent, an imidazole compound curing accelerator microencapsulated with a urethane resin or the like is used. The microencapsulated imidazole compound curing accelerator dispersed in a liquid epoxy resin such as liquid bisphenol A type is preferable from the viewpoint of storage stability, and is a point of workability, curing speed, storage stability More preferred. As the imidazole curing agent contained in the microencapsulated imidazole compound curing agent, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenylimidazole Phenyl-4-methylimidazole, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4 And -methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole and the like, and 2,4-diamino-6- [2'-methylimidazolyl- 1 ')] Ethyl-s-triazine, 2,4-diamino-6- [2'-unde Cure rate, etc., as imidazolyl- (1)]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, etc. It is preferable from the viewpoint of workability and moisture resistance.

（Ｂ）成分のフェノール系硬化剤としては、フェノールノボラック、クレゾールノボラック等が挙げられ、フェノールノボラックが好ましい。また、フェノール系硬化剤は、アミン系硬化剤より、反応性が低いのでポットライフを長くできる。導電性接着剤のポットライフをより長くしたい場合には、フェノール系硬化剤を併用して、導電性接着剤のポットライフを延長することができる。   Examples of the phenolic curing agent of the component (B) include phenol novolak, cresol novolak and the like, and phenol novolak is preferable. In addition, since the phenolic curing agent has lower reactivity than the amine curing agent, the pot life can be extended. When it is desired to make the pot life of the conductive adhesive longer, a phenolic curing agent can be used in combination to extend the pot life of the conductive adhesive.

（Ｂ）成分の市販品としては、日本化薬製アミン硬化剤（品名：カヤハードＡ−Ａ）、日本ファインケム製アジピン酸ジヒドラジド（品名：ＡＤＨ）、旭化成イーマテリアルズ製マイクロカプセル化イミダゾール化合物硬化剤（品名：ノバキュアＨＸ３９４１ＨＰ、ノバキュアＨＸ３０８８、ノバキュアＨＸ３７２２）、味の素ファインテクノ製アミンアダクト型硬化剤（品名：ＰＮ−４０Ｊ）、明和化成製フェノール硬化剤（品名：ＭＥＨ８０００、ＭＥＨ８００５）等が挙げられるが、（Ｂ）成分は、これら品名に限定されるものではない。（Ｂ）成分は、単独でも２種以上を併用してもよい。   Commercial products of component (B) include amine curing agents manufactured by Nippon Kayaku Co., Ltd. (product name: Kayahard A-A), adipic acid dihydrazide made by Nippon Finechem (product name: ADH), microencapsulated imidazole compound curing agents made by Asahi Kasei E-materials (Product name: Novacua HX3941HP, Novacua HX3088, Novacua HX3722), Ajinomoto Finetechno amine adduct type curing agent (product name: PN-40J), Meiwa Kasei Phenolic curing agent (product name: MEH8000, MEH8005), etc. The component B) is not limited to these product names. The component (B) may be used alone or in combination of two or more.

（Ｃ）成分の還元剤に使用されるモルホリン類とは、モルホリン、およびモルホリン構造を持つ化合物をいう。（Ｃ）成分は、硬化後の導電性接着剤の接続抵抗値を低下させることができる。（Ｃ）成分としては、モルホリン、２，６−ジメチルモルホリン、４−（３−ヒドロキシプロピル）モルホリン、４−メチルモルホリン、４−（４−アミノフェニル）モルホリン、チオモルホリン、１，１−ジオキソチオモルホリン等が挙げられる。   The morpholines used for the reducing agent of the component (C) refer to morpholine and compounds having a morpholine structure. The component (C) can reduce the connection resistance value of the conductive adhesive after curing. As component (C), morpholine, 2,6-dimethylmorpholine, 4- (3-hydroxypropyl) morpholine, 4-methylmorpholine, 4- (4-aminophenyl) morpholine, thiomorpholine, 1,1-dioxo Thiomorpholine etc. are mentioned.

（Ｃ）成分としては、下記の化学式（１）〜（７）で表されるモルホリン類からなる群より選択される少なくとも１種であると、接続抵抗値を低下させることができ、好ましい。
化学式（１）で表されるモルホリン：The connection resistance value can be reduced when the component (C) is at least one selected from the group consisting of morpholines represented by the following chemical formulas (1) to (7), which is preferable.
Morpholine represented by the chemical formula (1):

Figure 0006549555
Figure 0006549555

化学式（２）で表される２，６−ジメチルモルホリン： 2,6-Dimethylmorpholine represented by the chemical formula (2):

Figure 0006549555
Figure 0006549555

化学式（３）で表される４−（３−ヒドロキシプロピル）モルホリン： 4- (3-hydroxypropyl) morpholine represented by the chemical formula (3):

Figure 0006549555
Figure 0006549555

化学式（４）で表される４−メチルモルホリン： 4-methylmorpholine represented by the chemical formula (4):

Figure 0006549555
Figure 0006549555

化学式（５）で表される４−（４−アミノフェニル）モルホリン： 4- (4-aminophenyl) morpholine represented by the chemical formula (5):

Figure 0006549555
Figure 0006549555

化学式（６）で表されるチオモルホリン： Thiomorpholine represented by the chemical formula (6):

Figure 0006549555
Figure 0006549555

化学式（７）で表される１，１−ジオキソチオモルホリン（チオモルホリン１，１−ジオキシド）： 1,1-dioxothiomorpholine (thiomorpholine 1,1-dioxide) represented by the chemical formula (7):

Figure 0006549555
Figure 0006549555

（Ｃ）成分は、例えば、和光純薬工業、日本乳化剤、東京化成工業から市販されている試薬を使用すればよい。（Ｃ）成分は、単独でも２種以上を併用してもよい。なお、既知の技術で使用されている８−ヒドロキシキノリンは、モルホリン類に比べ還元力が弱いため、導電性接着剤の接続抵抗値を下げるためには、多量（例えば、導電性接着剤の２〜３質量％）含有させなければならないが、導電性接着剤に多量の８−ヒドロキシキノリンを含有させると、導電性接着剤の接着力が低下してしまう、という問題がある。これに対して、（Ｃ）モルホリン類還元剤は、高温での還元力が強いため、導電性接着剤の接着力を低下させない少量で導電性接着剤の接続抵抗値を下げることができ、かつ常温では反応しないため、導電性接着剤が増粘しない、すなわち、ポットライフを長くすることができる、という顕著な利点を有する。   As the component (C), for example, a reagent commercially available from Wako Pure Chemical Industries, Ltd., Japan emulsifier, Tokyo Chemical Industry may be used. The component (C) may be used alone or in combination of two or more. In addition, since 8-hydroxyquinoline used in known techniques has a reducing power lower than that of morpholines, a large amount (for example, 2 of conductive adhesives) can be used to lower the connection resistance value of the conductive adhesives. However, if the conductive adhesive contains a large amount of 8-hydroxyquinoline, there is a problem that the adhesion of the conductive adhesive is reduced. On the other hand, the (C) morpholines reducing agent has a strong reducing power at high temperature, so that the connection resistance value of the conductive adhesive can be reduced by a small amount that does not reduce the adhesion of the conductive adhesive, There is a remarkable advantage that the conductive adhesive does not thicken, that is, the pot life can be extended since it does not react at normal temperature.

（Ｄ）成分の導電性充填剤は、特に限定する必要はなく、（Ｄ）成分としては、銀、ニッケル、銅、金、パラジウム、白金、カーボンブラック、ビスマス、錫、ビスマス‐錫合金、炭素繊維、グラファイト、アルミニウム、インジウム錫酸化物、銀被覆銅、銀被覆アルミニウム、金属被覆ガラス球、銀被覆繊維、銀被覆樹脂、アンチモンドープ錫酸化錫、およびこれらの混合物が挙げられる。（Ｄ）成分が、銀、ニッケル、銅、錫、アルミニウム、銀被覆銅、銀被覆アルミニウムおよび銀被覆樹脂からなる群から選択される少なくとも１種の粉末であると、既知の技術では接続抵抗値の上昇を招くため、本発明の効果を発揮しやすく、好ましい。銀被覆繊維、銀被覆樹脂に使用される材質としては、アクリル樹脂、ポリエステル、スチレン樹脂が挙げられる。また、基板の導電部が、ニッケル、アルミニウムまたは銅のように腐蝕されやすい金属の場合には、（Ｃ）成分が基板の導電部の腐蝕防止剤としても作用するため、（Ｄ）成分として、金、パラジウム、白金等、バルク抵抗の小さな金属を用いると、接続抵抗値を小さくでき、好ましい。（Ｄ）成分の平均粒径は、０．１〜５０μｍであると、作業性及び低粘度化の観点から、より好ましい。ここで、（Ｄ）成分の平均粒径は、レーザー回折法によって測定した体積基準のメジアン径である。また、（Ｄ）成分の形状は、リン片状であると、低抵抗化の観点から、より好ましい。市販品としては、ＤＯＷＡエレクトロニクス製銀粉末（品名：ＦＡ６１８）、三井金属鉱業製銀粉末（品名：ＳＬ０２）が挙げられる。（Ｄ）成分は、単独でも２種以上を併用してもよい。   The conductive filler of the component (D) need not be particularly limited, and as the component (D), silver, nickel, copper, gold, palladium, platinum, carbon black, bismuth, tin, bismuth-tin alloy, carbon Fibers, graphite, aluminum, indium tin oxide, silver coated copper, silver coated aluminum, metal coated glass spheres, silver coated fibers, silver coated resin, antimony doped tin oxide, and mixtures thereof. In the known art, the connection resistance value is that the component (D) is at least one powder selected from the group consisting of silver, nickel, copper, tin, aluminum, silver-coated copper, silver-coated aluminum and silver-coated resin The effect of the present invention is easily exhibited and is preferred. Examples of materials used for silver-coated fibers and silver-coated resins include acrylic resins, polyesters, and styrene resins. When the conductive portion of the substrate is a metal which is easily corroded such as nickel, aluminum or copper, the component (C) also acts as a corrosion inhibitor for the conductive portion of the substrate. The use of a metal having a small bulk resistance, such as gold, palladium, platinum, or the like can reduce the connection resistance, which is preferable. The average particle diameter of the component (D) is more preferably 0.1 to 50 μm from the viewpoint of workability and viscosity reduction. Here, the average particle diameter of the component (D) is a volume-based median diameter measured by a laser diffraction method. Further, the shape of the component (D) is more preferably scaly from the viewpoint of resistance reduction. Examples of commercially available products include silver powder manufactured by Dowa Electronics (product name: FA618) and silver powder manufactured by Mitsui Mining & Smelting Co. (product name: SL02). The component (D) may be used alone or in combination of two or more.

（Ｅ）成分のカップリング剤は、導電性接着剤の密着性を向上させる。（Ｅ）成分としては、３−グリシドキシプロピルトリメトキシシラン、３−アミノプロピルトリメトキシシラン、ビニルトリメトキシシラン、ｐ−スチリルトリメトキシシラン、３−メタクリロキシプロピルメチルトリメトキシシラン、３−アクリロキシプロピルトリメトキシシラン、３−ウレイドプロピルトリエトキシシラン、３−メルカプトプロピルトリメトキシシラン、ビス（トリエトキシシリルプロピル）テトラスルフィド、３−イソシアネートプロピルトリエトキシシラン等が挙げられ、３−グリシドキシプロピルトリメトキシシラン、３−アミノプロピルトリメトキシシランが、導電性接着剤密着性の観点から好ましい。市販品としては、信越化学工業製シランカップリング剤（品名：ＫＢＭ４０３、ＫＢＥ９０３、ＫＢＥ９１０３）、日美商事製シランカップリング剤（品名：Ｓ５１０）等が挙げられるが、（Ｅ）成分は、これら品名に限定されるものではない。（Ｅ）成分は、単独でも２種以上を併用してもよい。   The coupling agent of component (E) improves the adhesion of the conductive adhesive. As component (E), 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyltrimethoxysilane, 3-acrylic Roxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, etc., and 3-glycidoxypropyl Trimethoxysilane and 3-aminopropyltrimethoxysilane are preferable from the viewpoint of conductive adhesive adhesion. Commercially available products include, but are not limited to, silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. (product names: KBM403, KBE903, KBE9103), silane coupling agents manufactured by Nichisho Co., Ltd. (product name: S510), etc. It is not limited to The component (E) may be used alone or in combination of two or more.

（Ａ）成分は、（Ａ）〜（Ｅ）成分の合計１００質量部に対して、６〜２４質量部であると好ましく、８〜２１質量部であると、より好ましい。   The amount of the component (A) is preferably 6 to 24 parts by mass, and more preferably 8 to 21 parts by mass, with respect to a total of 100 parts by mass of the components (A) to (E).

（Ｂ）成分は、良好な反応性、信頼性の観点から、（Ａ）〜（Ｅ）成分の合計１００質量部に対して、１〜１０質量部であると好ましく、１〜５質量部であると、より好ましい。   From the viewpoint of good reactivity and reliability, the component (B) is preferably 1 to 10 parts by mass, and 1 to 5 parts by mass with respect to 100 parts by mass in total of the components (A) to (E). If there is, it is more preferable.

（Ｃ）成分は、（Ａ）〜（Ｅ）成分の合計１００質量部に対して、０．０５〜１．００質量部であると好ましく、０．１〜０．８質量部であると、より好ましい。（Ｃ）成分が、導電性接着剤１００質量部に対して、０．０５質量部未満であると、接続抵抗値が増加しやすくなり、一方、１．００質量部を超えると、導電性接着剤のポットライフが短くなり易くなる。   The component (C) is preferably 0.05 to 1.00 parts by mass and 0.1 to 0.8 parts by mass with respect to a total of 100 parts by mass of the components (A) to (E). More preferable. When the amount of the component (C) is less than 0.05 parts by mass with respect to 100 parts by mass of the conductive adhesive, the connection resistance tends to increase, while when it exceeds 1.00 parts by mass, the conductive adhesion The pot life of the agent tends to be short.

また、（Ｃ）成分は、導電性接着剤の硬化物の場合も、（Ａ）〜（Ｅ）成分の合計１００質量部に対して、０．０５〜１．００質量部であると好ましく、０．１〜０．８質量部であると、より好ましい。ここで、導電性接着剤が溶剤を含有しない場合（導電性接着剤から溶剤を揮発させた場合も含む）には、硬化時の質量減少が１％未満と少ないため、硬化物中での好ましい（Ｃ）成分の含有量は、硬化前の（Ａ）〜（Ｅ）成分中での含有量と同様である。ここで、（Ｃ）成分の定量分析は、イオンクロマトグラフ−質量分析装置で行う。なお、導電性接着剤が溶剤を含有する場合の導電性接着剤の硬化時の質量減少は、例えば、３〜５質量％である。   Also, in the case of the cured product of the conductive adhesive, the component (C) is preferably 0.05 to 1.00 parts by mass with respect to 100 parts by mass in total of the components (A) to (E), It is more preferable that it is 0.1-0.8 mass parts. Here, in the case where the conductive adhesive does not contain a solvent (including the case where the solvent is volatilized from the conductive adhesive), the mass loss at the time of curing is as small as less than 1%. The content of the component (C) is the same as the content in the components (A) to (E) before curing. Here, quantitative analysis of the component (C) is performed by an ion chromatograph-mass spectrometer. In addition, the mass reduction at the time of hardening of the conductive adhesive in case the conductive adhesive contains a solvent is 3-5 mass%, for example.

（Ｄ）成分は、導電性接着剤自体の電気抵抗値の観点から、（Ａ）〜（Ｅ）成分の合計１００質量部に対して、７０〜９０質量部であると好ましく、７４〜８６質量部であると、より好ましい。   The component (D) is preferably 70 to 90 parts by mass with respect to a total of 100 parts by mass of the components (A) to (E) from the viewpoint of the electric resistance value of the conductive adhesive itself, and 74 to 86 parts It is more preferable that it is a part.

また、（Ｄ）成分は、導電性接着剤の硬化物の場合も、（Ａ）〜（Ｅ）成分の合計１００質量部に対して、７０〜９０質量部であると好ましく、７４〜８６質量部であると、より好ましい。ここで、（Ｄ）成分の定量分析は、質量分析法で行う。   Also, in the case of the cured product of the conductive adhesive, the component (D) is preferably 70 to 90 parts by mass with respect to 100 parts by mass in total of the components (A) to (E), and 74 to 86 parts It is more preferable that it is a part. Here, quantitative analysis of the component (D) is performed by mass spectrometry.

（Ｅ）成分は、（Ａ）〜（Ｅ）成分の合計１００質量部に対して、好ましくは０．０５〜５質量部、より好ましくは０．１〜２質量部含有される。０．０５質量部以上であると、密着性が向上し、５質量部以下であると、導電性接着剤の発泡が抑制される。   The component (E) is preferably contained in an amount of 0.05 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the components (A) to (E). Adhesiveness improves that it is 0.05 mass part or more, and foaming of a conductive adhesive is suppressed as it is 5 mass parts or less.

本発明の導電性接着剤は、さらに、ポットライフ向上の観点から、ホウ酸化合物を含有させることができる。このホウ酸化合物は、（Ａ）〜（Ｅ）成分の合計１００質量部に対して、０．０３〜０．０６質量部であると好ましい。０．０３質量部より少ないと、ポットライフが短くなる場合があり、０．０６質量部より多いと導電性接着剤の硬化性が悪くなる場合がある。ホウ酸化合物の市販品としては、和光純薬製ホウ酸（品名：ＨＢＯ、有効成分：９９．５％以上）、東京化成工業ホウ酸トリイソプロピル（品名：ＴＩＰＢ）が、挙げられる。   The conductive adhesive of the present invention can further contain a boric acid compound from the viewpoint of improving the pot life. This boric acid compound is preferable in it being 0.03-0.06 mass part with respect to a total of 100 mass parts of (A)-(E) component. When the amount is less than 0.03 parts by mass, the pot life may be shortened, and when the amount is more than 0.06 parts by mass, the curability of the conductive adhesive may be deteriorated. Examples of commercially available boric acid compounds include boric acid (trade name: HBO, active ingredient: 99.5% or more) manufactured by Wako Pure Chemical Industries, Ltd., and triisopropyl borate from Tokyo Chemical Industry Co., Ltd. (trade name: TIPB).

本発明の導電性接着剤には、本発明の目的を損なわない範囲で、更に必要に応じ、レベリング剤、着色剤、イオントラップ剤、消泡剤、難燃剤、その他の添加剤等を配合することができる。   In the conductive adhesive of the present invention, a leveling agent, a coloring agent, an ion trap agent, an antifoaming agent, a flame retardant, other additives and the like are further added as needed within a range not to impair the object of the present invention. be able to.

本発明の導電性接着剤は、例えば、（Ａ）成分〜（Ｅ）成分およびその他添加剤等を同時にまたは別々に、必要により加熱処理を加えながら、撹拌、溶融、混合、分散させることにより得ることができる。これらの混合、撹拌、分散等の装置としては、特に限定されるものではないが、撹拌、加熱装置を備えたライカイ機、３本ロールミル、ボールミル、プラネタリーミキサー、ビーズミル等を使用することができる。また、これら装置を適宜組み合わせて使用してもよい。   The conductive adhesive of the present invention can be obtained, for example, by stirring, melting, mixing, and dispersing the components (A) to (E) and the other additives simultaneously or separately, with heat treatment as required. be able to. An apparatus for mixing, stirring, dispersing and the like is not particularly limited, but a lai-sea machine equipped with stirring and a heating device, a three-roll mill, a ball mill, a planetary mixer, a bead mill, etc. can be used. . Moreover, you may use combining these apparatuses suitably.

本発明の導電性接着剤は、温度：２５℃での粘度が１００００〜３００００ｍＰａ・ｓであると、注入性の観点から好ましい。ここで、粘度は、ブルックフィールド社製ＲＶ型粘度計で測定する。   It is preferable from the viewpoint of injectability that the conductive adhesive of the present invention has a viscosity of 10000 to 30000 mPa · s at a temperature of 25 ° C. Here, the viscosity is measured by a Brookfield RV RV viscometer.

本発明の導電性接着剤は、ディスペンサー、印刷等で、基板の導電部や、半導体素子の電極部等の電子部品の所望の位置に形成・塗布される。   The conductive adhesive of the present invention is formed and applied to a desired position of an electronic component such as a conductive portion of a substrate or an electrode portion of a semiconductor element by dispenser, printing or the like.

本発明の導電性接着剤の硬化は、８０〜３００℃が好ましい。   The curing of the conductive adhesive of the present invention is preferably 80 to 300 ° C.

本発明の導電性接着剤は、半導体素子の電極部と基板の導電部等の電子部品用接着剤として適している。   The conductive adhesive of the present invention is suitable as an adhesive for electronic parts such as the electrode part of a semiconductor element and the conductive part of a substrate.

〔半導体装置〕
本発明の半導体装置は、導電部を有する基板と、電極部を有する半導体素子とを含み、
上記導電性接着剤の硬化物で、基板の導電部と半導体素子の電極部とが接合される。[Semiconductor device]
A semiconductor device of the present invention includes a substrate having a conductive portion, and a semiconductor element having an electrode portion,
The conductive portion of the substrate and the electrode portion of the semiconductor element are bonded by the cured product of the conductive adhesive.

この半導体装置は、基板の導電部がニッケル、アルミニウムまたは銅であると、上記導電性接着剤の効果を発揮しやすい観点から、好ましい。ニッケル、アルミニウムまたは銅は、既知の技術では、金属の腐蝕によって接続抵抗値の上昇を招きやすいためである。   In the semiconductor device, the conductive portion of the substrate is preferably nickel, aluminum or copper from the viewpoint of easily exhibiting the effect of the conductive adhesive. This is because nickel, aluminum or copper is likely to cause an increase in connection resistance due to metal corrosion in the known art.

本発明の半導体装置は、半導体素子の電極部と基板の導電部との間の接続抵抗値が小さく、高信頼性である。   The semiconductor device of the present invention is highly reliable because the connection resistance value between the electrode portion of the semiconductor element and the conductive portion of the substrate is small.

本発明について、実施例により説明するが、本発明はこれらに限定されるものではない。なお、以下の実施例において、部、％はことわりのない限り、質量部、質量％を示す。   The present invention will be described by way of examples, but the present invention is not limited thereto. In the following examples, parts and% indicate parts by mass and% by mass unless otherwise specified.

〔評価用サンプルの作製〕
表１に示す割合で、（Ａ）成分のＤＩＣ製液状エポキシ樹脂（品名：ＥＸＡ８３５ＬＶ）と、（Ｅ）成分の日美商事製シランカップリング剤（品名：Ｓ５１０）と、（Ｄ）成分の銀粉末と、溶剤の丸善石油化学工業製ソルベントナフサ（ＳＷ１８００）：３．００質量部（表１に記載せず）と、ポットライフ向上のためのホウ酸化合物（和光純薬製、品名：ＨＢＯ）：０．０４質量部（表１に記載せず）とを、容器に計量し、３本ロールミルにて分散させた。[Preparation of sample for evaluation]
In the proportions shown in Table 1, DIC liquid epoxy resin (product name: EXA 835 LV) as component (A), Nichiseki silane coupling agent (product name: S510) as component (E), and silver as component (D) Powders and solvents Solvent naphtha (SW1800) manufactured by Maruzen Petrochemicals Co., Ltd .: 3.00 parts by mass (not shown in Table 1) and boric acid compounds for improving the pot life (Wako Pure Chemical Industries, product name: HBO) : 0.04 mass part (it does not describe in Table 1) was measured to the container, and was disperse | distributed with 3 roll mills.

次に、得られた分散品に、（Ｃ）モルホリン類還元剤を添加し、自転公転式の撹拌機にて撹拌した。ここで、モルホリンは、通常、液状であるため、ロール分散の必要がない。なお、モルホリン類で固形のもの（例えば、４−（３−ヒドロキシプロピル）モルホリン、４−（４−アミノフェニル）モルホリン、１,１−ジオキソチオモルホリン）は上記ロールミルにて分散させた。さらに、（Ａ）成分と（Ｂ）成分の混合物である旭化成イーマテリアルズ製マイクロカプセル化硬化剤（品名：ノバキュアＨＸ３７２２）を添加し、同様に自転公転式の撹拌機にて撹拌した。最後に、粘度が１００００〜３００００ｍＰａ・ｓになるように、上記ソルベントナフサを用いて粘度調整を行い、脱泡機で撹拌しながら、分散品内の泡を完全に除去し、導電性接着剤を得た。   Next, the (C) morpholines reducing agent was added to the obtained dispersion, and the mixture was stirred by a rotation and revolution stirrer. Here, morpholine is usually in the form of liquid, so there is no need for roll dispersion. In addition, solid morpholines (for example, 4- (3-hydroxypropyl) morpholine, 4- (4-aminophenyl) morpholine, 1,1-dioxothiomorpholine) were dispersed by the above roll mill. Furthermore, a microcapsulated curing agent (product name: Novaca HX3722) manufactured by Asahi Kasei E-Materials, which is a mixture of the (A) component and the (B) component, was added and similarly stirred using a rotation-revolution type stirrer. Finally, the solvent naphtha is used to adjust the viscosity so that the viscosity is 10000 to 30000 mPa · s, and while stirring with a defoamer, the foam in the dispersion is completely removed, and the conductive adhesive is removed. Obtained.

なお、比較例１では、（Ｃ）成分を使用しなかった。比較例２では、（Ｃ）成分の代わりに８−キノリノールを、比較例３では、（Ｃ）成分の代わりにアジピン酸を使用した。比較例４では、（Ｂ）成分の代わりに酸無水物系硬化剤を使用した。   In Comparative Example 1, the component (C) was not used. In Comparative Example 2, 8-quinolinol was used in place of the component (C), and in Comparative Example 3, adipic acid was used in place of the component (C). In Comparative Example 4, an acid anhydride curing agent was used instead of the component (B).

〔評価方法〕
〈接続抵抗値の測定〉
ＮｉめっきをしたＣｕリードフレーム（厚み：２００μｍ）上に、導電性接着剤を印刷し、３２１６サイズのＡｇＰｄ端面電極をマウントさせた。室温から８０℃まで６０分で昇温し、８０℃のオーブン中に６０分間保持して硬化させた後、リードフレームと電極との間の抵抗値を４端子法で測定し、接続抵抗値を得た。表１〜表２に結果を示す。〔Evaluation method〕
<Measurement of connection resistance value>
A conductive adhesive was printed on a Ni-plated Cu lead frame (thickness: 200 μm), and a 3216 size AgPd edge electrode was mounted. After raising the temperature from room temperature to 80 ° C in 60 minutes and holding in an oven at 80 ° C for 60 minutes for curing, the resistance between the lead frame and the electrode is measured by the four-terminal method, and the connection resistance is measured. Obtained. The results are shown in Tables 1 and 2.

〈ポットライフ〉
得られた導電性接着剤の粘度を、ブルックフィールド社製ＲＶＴ粘度計（１４号スピンドルを使用）を用い、１０ｒｐｍでの値を測定した。初期粘度を測定した後、２５℃／５０％ＲＨ環境下で２４時間放置し、再度粘度を測定し、粘度増加率を算出した。ここで、粘度増加率は、下記式：
粘度増加率＝〔（２４時間後の粘度）−（初期粘度）〕／（初期粘度）×１００
で算出した。粘度増加率が、５％未満のときを「◎」、５〜１５％のときを「○」、１５〜２０％のときを「△」、２０％以上のときを「×」とした。表１〜表２に、測定結果を示す。<Pot life>
The viscosity of the obtained conductive adhesive was measured at 10 rpm using a Brookfield RVT viscometer (using a No. 14 spindle). After measuring the initial viscosity, it was left for 24 hours in a 25 ° C./50% RH environment, the viscosity was measured again, and the viscosity increase rate was calculated. Here, the viscosity increase rate has the following formula:
Viscosity increase rate = [(viscosity after 24 hours)-(initial viscosity)] / (initial viscosity) x 100
Calculated with When the viscosity increase rate was less than 5%, "◎", 5-15% was "○", 15-20% was "Δ", and 20% or more was "X". Tables 1 and 2 show the measurement results.

〈総合評価〉
総合評価を行った。接続抵抗値が３０００ｍΩ以下であり、かつポットライフが◎または○のときに、総合評価を「◎」、接続抵抗値が３０００ｍΩ以下であり、かつポットライフが△のときに、総合評価を「○」、接続抵抗値が３０００ｍΩ以下であり、かつポットライフが×のときに、総合評価を「△」、接続抵抗値が３０００ｍΩより高いときに、総合評価を「×」とした。表１〜表２に、測定結果を示す。<Comprehensive evaluation>
We made a comprehensive evaluation. When the connection resistance value is 3000 mΩ or less and the pot life is ◎ or 、, the comprehensive evaluation is "◎", the connection resistance value is 3000 mΩ or less, and the pot life is △, the comprehensive evaluation is "○ When the connection resistance value is 3000 mΩ or less and the pot life is x, the comprehensive evaluation is “Δ”, and when the connection resistance value is higher than 3000 mΩ, the comprehensive evaluation is “x”. Tables 1 and 2 show the measurement results.

Figure 0006549555
Figure 0006549555

Figure 0006549555
Figure 0006549555

表１〜表２からわかるように、実施例１〜１５の全てで、接続抵抗値が３０００ｍΩ以下と低く、ポットライフが悪くなく、総合評価も良好であった。特に、実施例１、２、６〜８、１５では、接続抵抗値が低く、ポットライフが非常に良好で、総合評価も非常に良好であった。これに対して、（Ｃ）成分を使用しなかった比較例１では、接続抵抗値が非常に高く、総合評価も悪かった。（Ｃ）成分の代わりに８−キノリノールを使用した比較例２では、接続抵抗値が高く、総合評価も悪かった。（Ｃ）成分の代わりにアジピン酸を使用した比較例３では、接続抵抗値が高く、ポットライフが短く、総合評価も悪かった。（Ｂ）成分の代わりに酸無水物系硬化剤を使用した比較例４では、接続抵抗値が高く、総合評価も悪かった。   As understood from Tables 1 and 2, in all of Examples 1 to 15, the connection resistance value was as low as 3000 mΩ or less, the pot life was not bad, and the overall evaluation was also good. In particular, in Examples 1, 2, 6 to 8, and 15, the connection resistance value was low, the pot life was very good, and the overall evaluation was also very good. On the other hand, in Comparative Example 1 in which the component (C) was not used, the connection resistance value was very high and the comprehensive evaluation was also bad. In Comparative Example 2 in which 8-quinolinol was used instead of the component (C), the connection resistance value was high, and the comprehensive evaluation was also poor. In Comparative Example 3 in which adipic acid was used instead of the component (C), the connection resistance value was high, the pot life was short, and the overall evaluation was also poor. In Comparative Example 4 in which an acid anhydride curing agent was used instead of the component (B), the connection resistance value was high, and the comprehensive evaluation was also poor.

上記のように、本発明の導電性接着剤は、ポットライフが長く、硬化後に低い接続抵抗値を得ることができる。   As described above, the conductive adhesive of the present invention has a long pot life and can obtain low connection resistance after curing.

本発明は、腐蝕防止剤としてモルホリン類を添加することにより、低い接続抵抗値が得られ、かつ、保存中での増粘抑制によりポットライフの長い、導電性接着剤であり、特に、基板の導電部と半導体素子の電極部との接着に非常に有用である。   The present invention is a conductive adhesive in which a low connection resistance value is obtained by adding morpholines as a corrosion inhibitor, and the pot life is long due to the suppression of thickening during storage, and in particular, it is possible to use a substrate It is very useful for adhesion between the conductive part and the electrode part of the semiconductor element.

Claims (5)

（Ａ）エポキシ樹脂、
（Ｂ）アミン系硬化剤および／またはフェノール系硬化剤、
（Ｃ）モルホリン類還元剤、
（Ｄ）導電性充填剤、ならびに
（Ｅ）シランカップリング剤
を含有し、（Ｃ）成分が、（Ａ）〜（Ｅ）成分の合計１００質量部に対して、０．０５〜１．００質量部であることを特徴とする、導電性接着剤。 (A) Epoxy resin,
(B) amine curing agents and / or phenolic curing agents,
(C) morpholines reducing agent,
(D) The conductive filler, and (E) the silane coupling agent are contained, and the (C) component is 0.05 to 1.00 with respect to a total of 100 parts by mass of the (A) to (E) components. Conductive adhesive characterized in that it is part by mass . （Ｃ）成分が、モルホリン、２，６−ジメチルモルホリン、４−（３−ヒドロキシプロピル）モルホリン、４−メチルモルホリン、４−（４−アミノフェニル）モルホリン、チオモルホリンおよび１，１−ジオキソチオモルホリンからなる群より選択される少なくとも１種である、請求項１記載の導電性接着剤。   Component (C) is morpholine, 2,6-dimethylmorpholine, 4- (3-hydroxypropyl) morpholine, 4-methylmorpholine, 4- (4-aminophenyl) morpholine, thiomorpholine and 1,1-dioxothio The conductive adhesive according to claim 1, which is at least one selected from the group consisting of morpholine. （Ｄ）成分が、銀、ニッケル、銅、金、パラジウム、白金、錫、アルミニウム、銀被覆銅、銀被覆アルミニウムおよび銀被覆樹脂からなる群から選択される少なくとも１種の粉末である、請求項１または２記載の導電性接着剤。 The component (D) is at least one powder selected from the group consisting of silver, nickel, copper, gold, palladium, platinum, tin, aluminum, silver-coated copper, silver-coated aluminum and silver-coated resin. The conductive adhesive according to 1 or 2 . 導電部を有する基板と、電極部を有する半導体素子とを含み、
請求項１〜３のいずれか１項記載の導電性接着剤の硬化物で、基板の導電部と半導体素子の電極部とが接着された、半導体装置。 A substrate having a conductive portion, and a semiconductor element having an electrode portion,
A semiconductor device according to any one of claims 1 to 3 , wherein the conductive portion of the substrate and the electrode portion of the semiconductor element are bonded. 基板の導電部がニッケル、アルミニウムまたは銅である、請求項４記載の半導体 The semiconductor according to claim 4 , wherein the conductive portion of the substrate is nickel, aluminum or copper.
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