JP2006312743A - Anisotropic electro-conductive adhesive film - Google Patents

Anisotropic electro-conductive adhesive film Download PDF

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JP2006312743A
JP2006312743A JP2006141929A JP2006141929A JP2006312743A JP 2006312743 A JP2006312743 A JP 2006312743A JP 2006141929 A JP2006141929 A JP 2006141929A JP 2006141929 A JP2006141929 A JP 2006141929A JP 2006312743 A JP2006312743 A JP 2006312743A
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curing agent
layer
conductive adhesive
curing
adhesive film
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JP4896585B2 (en
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Yasuhiro Suga
保博 須賀
Takashi Ando
尚 安藤
Yukio Yamada
幸男 山田
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Dexerials Corp
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Sony Chemical and Information Device Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an anisotropic electro-conductive adhesive film capable of achieving high speed pressure bonding in a relatively low pressure-bonding temperature range to reduce the pressure bonding time while preventing a damage to a circuit board or an electronic component caused by the pressure bonding temperature. <P>SOLUTION: The anisotropic electro-conductive adhesive film comprises a principal component layer 1 comprising a thermosetting resin as a principal component laminated with a curing agent layer 2 comprising a curing agent as a principal component through an insulating layer 3, wherein electro-conductive particles 4 are incorporated into one of the three layers namely the principal component layer 1, curing agent layer 2, or insulating layer 3, and the thickness of the principal component layer 1, insulating layer 3, and curing agent layer 2 each are from 0.7 to 33 μm and the aggregate thickness of the insulating layer 3 and curing agent layer 2 is made greater than the thickness of the principal component layer 1. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、例えば液晶ディスプレイと回路基板とを電気的、機械的に接続するための異方導電性接着剤フィルムに関する。   The present invention relates to an anisotropic conductive adhesive film for electrically and mechanically connecting, for example, a liquid crystal display and a circuit board.

回路基板に液晶ディスプレイ等の電子部品を接続する方法としては、半田付け法や異方導電性接着剤フィルムを用いる方法等が挙げられる。しかし、回路がファインピッチである場合、半田付けだと選択性が悪く接続部同士でブリッジが生じてしまう虞れがあることから、異方導電性接着剤フィルムを用いる方法の方が有利である。   Examples of a method for connecting an electronic component such as a liquid crystal display to a circuit board include a soldering method and a method using an anisotropic conductive adhesive film. However, when the circuit has a fine pitch, the method using an anisotropic conductive adhesive film is more advantageous because the selectivity is poor and bridging may occur between connecting portions when soldering. .

異方導電性接着剤フィルムとは、ウレタン、ポリエステル、クロロプレン等の熱可塑性樹脂あるいはエポキシ等の熱硬化性樹脂に、導電性粒子としてニッケル、金、ハンダ等の金属粒子、又はプラスチックポリマ球状粒子に金等の導電層をコーティングした金属被覆プラスチック粒子を均一に分散混入させ、この混合物を、ポリエチレンテレフタレート(PET)等の剥離フィルム上に、フィルム形成してなるものである。   Anisotropic conductive adhesive film is a thermoplastic resin such as urethane, polyester, chloroprene, or a thermosetting resin such as epoxy, metal particles such as nickel, gold, or solder as conductive particles, or plastic polymer spherical particles. Metal-coated plastic particles coated with a conductive layer such as gold are uniformly dispersed and mixed, and this mixture is formed on a release film such as polyethylene terephthalate (PET).

この異方性導電性樹脂によって配線基板と電子部品とを接続するには、当該異方導電性接着剤フィルムを、配線基板と電子部品の接続端子同士の間に介在させ、熱を印加しつつ上下から圧力をかける。すると、フィルム内の導電性粒子が上下につぶれ、接続端子に対して面接触したかたちになる。その結果、配線基板と液晶ディスプレイの接続端子同士が電気的に接続された状態で一体固定されることになる。   In order to connect the wiring board and the electronic component with this anisotropic conductive resin, the anisotropic conductive adhesive film is interposed between the connection terminals of the wiring board and the electronic component, and heat is applied. Apply pressure from above and below. Then, the conductive particles in the film are crushed up and down and come into surface contact with the connection terminals. As a result, the connection terminals of the wiring board and the liquid crystal display are integrally fixed in a state where they are electrically connected.

このような異方導電性接着剤フィルムのうちでは、樹脂に熱硬化性樹脂を用いる熱硬化性タイプのものが接続信頼性に優れることから、主流を占めているのが現状である。   Among such anisotropically conductive adhesive films, the thermosetting type using a thermosetting resin as a resin is excellent in connection reliability, and is currently in the mainstream.

この熱硬化性タイプの異方導電性樹脂は、樹脂及び導電性粒子の他に、樹脂を硬化させるための硬化剤が含有される。この硬化剤としては、保存中に硬化反応が進行してしまうのを抑える都合上、硬化剤として潜在性硬化剤を用いることが例えば特開昭62−141083号公報に提案されている。   This thermosetting type anisotropic conductive resin contains a curing agent for curing the resin in addition to the resin and the conductive particles. As this curing agent, for the purpose of suppressing the progress of the curing reaction during storage, a latent curing agent is proposed as a curing agent, for example, in JP-A-62-141083.

潜在性硬化剤とは、硬化剤が被膜で被覆されてマイクロカプセル状になされているものであり、常温では不溶であるが、熱を加えることにより被膜内から硬化剤が溶出し、瞬時に硬化反応が開始されるようになされたものである。   The latent curing agent is a microcapsule that is coated with a coating and is insoluble at room temperature, but when heated, the curing agent elutes from the coating and cures instantly. The reaction is started.

ところで、以上のような熱硬化性タイプの異方導電性接着剤フィルムで接続を行う場合、樹脂を短時間で硬化させ、接続に要する時間を節約するには、熱圧着温度を160〜200℃と比較的高い温度に設定する必要がある。   By the way, when connecting with the thermosetting type anisotropic conductive adhesive film as described above, the thermocompression bonding temperature is set to 160 to 200 ° C. in order to cure the resin in a short time and save the time required for the connection. It is necessary to set a relatively high temperature.

しかし、熱圧着温度をこのように高く設定すると、その温度による液晶ディスプレイや回路基板へ与えるダメージが問題になってくる。また、熱膨張等によって寸法精度も損なわれ、特に回路がファインピッチである場合、影響が大きい。   However, when the thermocompression bonding temperature is set so high, damage to the liquid crystal display and circuit board due to the temperature becomes a problem. In addition, the dimensional accuracy is impaired by thermal expansion or the like, and the influence is great particularly when the circuit has a fine pitch.

このため、比較的低い圧着温度でも硬化反応が進行する速硬化性の硬化剤や樹脂の検討もなされている。しかし、一般に知られている速硬化性の硬化剤や樹脂は、混合すると5分以内でゲル化する。このため、この樹脂と硬化剤の混合物を、剥離フィルム上に塗布、乾燥してフィルム化しようとしても、乾燥のための熱によって、硬化反応が進行し製品とすることができない。   For this reason, studies have also been made on fast-curing curing agents and resins in which the curing reaction proceeds even at relatively low pressure bonding temperatures. However, generally known fast-curing curing agents and resins are gelled within 5 minutes when mixed. For this reason, even if it is going to apply | coat and dry this mixture of this resin and a hardening | curing agent on a peeling film and to make a film, a hardening reaction advances with the heat | fever for drying and it cannot be set as a product.

そこで、本発明はこのような従来の実情に鑑みて提案されたものであり、速硬化性の硬化剤や樹脂を用いることが可能であり、熱圧着温度を比較的低く設定した場合でも、短時間で接続が行える異方導電性接着剤フィルムを提供することを目的とする。   Therefore, the present invention has been proposed in view of such a conventional situation, and it is possible to use a fast-curing curing agent or resin, and even when the thermocompression bonding temperature is set relatively low, An object is to provide an anisotropic conductive adhesive film that can be connected in time.

上述の目的を達成するために、本発明の異方導電性接着剤フィルムは、熱硬化性樹脂を主成分とする主剤層と、硬化剤と熱可塑性樹脂を混合してなり、硬化剤を主成分とする硬化剤層とが、隔離層を介して積層され、上記主剤層、上記硬化剤層又は上記隔離層のいずれかに導電性粒子が含有され、上記主剤層、上記隔離層及び上記硬化剤層の厚みが、それぞれ0.7〜33μmであり、上記剥離層及び上記硬化剤層の厚みの合計が、上記主剤層の厚みよりも大きく形成したものである。   In order to achieve the above-mentioned object, the anisotropic conductive adhesive film of the present invention is composed of a main agent layer mainly composed of a thermosetting resin, a curing agent and a thermoplastic resin, and the curing agent is mainly used. A curing agent layer as a component is laminated via an isolation layer, and conductive particles are contained in any of the main agent layer, the curing agent layer, or the isolation layer, and the main agent layer, the isolation layer, and the curing are included. The thickness of the agent layer is 0.7 to 33 μm, respectively, and the total thickness of the release layer and the curing agent layer is larger than the thickness of the main agent layer.

また、上記主剤層の主成分である熱硬化性樹脂には、エポキシ樹脂が用いられ、上記硬化剤層の主成分である硬化剤には、上記熱硬化性樹脂と反応する速硬化性硬化剤として、BF3系硬化剤、ポリアミン系硬化剤、変性アミン系硬化剤及び芳香族チオエーテル系硬化剤のいずれか1以上を用いることが望ましい。   In addition, an epoxy resin is used for the thermosetting resin that is the main component of the main agent layer, and a fast-curing curing agent that reacts with the thermosetting resin is used for the curing agent that is the main component of the curing agent layer. It is desirable to use any one or more of a BF3-based curing agent, a polyamine-based curing agent, a modified amine-based curing agent, and an aromatic thioether-based curing agent.

本発明に係る異方導電性接着剤フィルムは、熱硬化性樹脂を主成分とする主剤層と、硬化剤と熱硬化性樹脂を混合してなり、硬化剤を主成分とする硬化剤層とが、隔離層を介して積層され、主剤層、硬化剤層又は隔離層のいずれかに導電性粒子が含有されているので、硬化剤や熱硬化性樹脂として速硬化性のものを用いた場合でも製造工程や保存中に硬化反応が進行してしまうといったことがない。   An anisotropic conductive adhesive film according to the present invention includes a main agent layer mainly composed of a thermosetting resin, a curing agent layer mainly composed of a curing agent, and a mixture of a curing agent and a thermosetting resin. Is laminated via an isolation layer, and conductive particles are contained in either the main agent layer, the curing agent layer, or the isolation layer, so when a fast-curing agent is used as the curing agent or thermosetting resin However, the curing reaction does not proceed during the manufacturing process or storage.

したがって、硬化剤、熱硬化性樹脂として速硬化性のものを用いることが可能であり、そのような材料を用いることにより、例えば100℃以下の比較的低い圧着温度範囲でも高速圧着がなされ、圧着温度による配線基板や電子部品へのダメージを抑えながら圧着時間の短縮化を図ることが可能である。   Accordingly, it is possible to use a fast-curing material as a curing agent and a thermosetting resin, and by using such a material, high-speed pressure bonding is performed even in a relatively low pressure temperature range of, for example, 100 ° C. or less. It is possible to shorten the crimping time while suppressing damage to the wiring board and electronic components due to temperature.

本発明が適用された異方導電性接着剤フィルムは、図1に示すように、熱硬化性樹脂を主成分とする主剤層1と、硬化剤を主成分とする硬化剤層2とが、隔離層3を介して積層され、主剤層1、硬化剤層2又は隔離層3のいずれかに導電性粒子4が含有されて構成されている。   As shown in FIG. 1, the anisotropic conductive adhesive film to which the present invention is applied has a main agent layer 1 mainly composed of a thermosetting resin and a hardener layer 2 mainly composed of a curing agent. The conductive particles 4 are laminated through the isolation layer 3 and contain the conductive particles 4 in any of the main agent layer 1, the curing agent layer 2, or the isolation layer 3.

このような構成の異方導電性接着剤フィルムを製造するには、例えばポリエチレンテレフタレート(PET)等の剥離フィルム上に、熱硬化性樹脂よりなる主剤塗料を塗布、乾燥して主剤層を形成し、次いで樹脂を主成分とする隔離塗料を塗布、乾燥して隔離層を形成する。そして、この隔離層上に、さらに、硬化剤を主成分とする硬化剤塗料を塗布、乾燥して硬化剤層を形成する。   In order to produce an anisotropic conductive adhesive film having such a structure, for example, a main component paint made of a thermosetting resin is applied to a release film such as polyethylene terephthalate (PET) and dried to form a main component layer. Then, an isolation paint mainly composed of a resin is applied and dried to form an isolation layer. Then, a curing agent coating mainly containing a curing agent is applied onto the isolation layer and dried to form a curing agent layer.

このように、この異方性導電性接着剤フィルムは、熱硬化性樹脂と硬化剤とを混合する工程なしで製造され、製品となる前に熱硬化性樹脂と硬化剤とが接触することがない。このため、硬化剤や熱硬化性樹脂として速硬化性のものを用いても、製造工程で硬化反応が進行し、製品が製造できなくなるといった事がない。また、熱硬化性樹脂と硬化剤とが隔離層によって隔離された構成であるので、保存中に硬化反応が進行してしまうこともなく、十分な保存性が得られる。したがって、速硬化性の硬化剤や熱硬化性樹脂を用いることが可能である。   Thus, this anisotropic conductive adhesive film is manufactured without the step of mixing the thermosetting resin and the curing agent, and the thermosetting resin and the curing agent may come into contact before becoming a product. Absent. For this reason, even if a fast-curing agent is used as the curing agent or thermosetting resin, the curing reaction proceeds in the production process and the product cannot be produced. In addition, since the thermosetting resin and the curing agent are separated by the separating layer, the curing reaction does not proceed during storage, and sufficient storage stability is obtained. Therefore, it is possible to use a fast-curing curing agent or a thermosetting resin.

このような構成の異方導電性接着剤フィルムによって配線基板と電子部品とを接続するには、当該異方導電性接着剤フィルムを、配線基板と電子部品の接続端子同士の間に介在させ、熱を印加しつつ上下から圧力をかける。すると、異方導電性接着剤フィルムの隔離層が溶融し、ここで初めて主剤層と硬化剤層とが接触する。そして、これら主剤層の熱硬化性樹脂と硬化剤層の硬化剤とが熱溶融し、硬化反応が進行する。一方、フィルム内の導電性粒子は、圧着力によって上下につぶれ、接続端子に対して面接触したかたちになる。その結果、配線基板と液晶ディスプレイの接続端子同士が電気的に接続された状態で一体固定されることになる。   In order to connect the wiring board and the electronic component by the anisotropic conductive adhesive film having such a configuration, the anisotropic conductive adhesive film is interposed between the connection terminals of the wiring board and the electronic component, Apply pressure from above and below while applying heat. Then, the isolation layer of the anisotropic conductive adhesive film is melted, and the main agent layer and the curing agent layer are in contact with each other for the first time. And the thermosetting resin of these main ingredient layers and the hardening | curing agent of a hardening | curing agent layer heat-melt, and hardening reaction advances. On the other hand, the conductive particles in the film are crushed up and down by the crimping force and come into surface contact with the connection terminals. As a result, the connection terminals of the wiring board and the liquid crystal display are integrally fixed in a state where they are electrically connected.

ここで、この異方導電性フィルムでは、硬化剤や熱硬化性樹脂として速硬化性のものを用いることが可能であり、そのような材料を用いることにより、例えば100℃以下の比較的低い圧着温度でも硬化反応が速やかに進行し、圧着温度による配線基板や電子部品へのダメージを抑えながら圧着時間の短縮化が図れるようになる。   Here, in this anisotropic conductive film, it is possible to use a fast-curing material as a curing agent or a thermosetting resin, and by using such a material, for example, a relatively low pressure bonding of 100 ° C. or less. The curing reaction proceeds rapidly even at a temperature, and the crimping time can be shortened while suppressing damage to the wiring board and electronic components due to the crimping temperature.

なお、主剤層に用いる熱硬化性樹脂としては、エポキシ樹脂が用いられる。エポキシ樹脂には、EP1009(油化シェルエポキシ社製,商品名)、DT613(大都産業社製,商品名)があり、このうちDT613は速硬化性のエポキシ樹脂である。これらエポキシ樹脂はそれ単独で用いても2種類以上を混合して用いても良い。   An epoxy resin is used as the thermosetting resin used for the main agent layer. Epoxy resins include EP1009 (manufactured by Yuka Shell Epoxy Co., Ltd., trade name) and DT613 (manufactured by Daito Sangyo Co., Ltd., trade name), among which DT613 is a fast-curing epoxy resin. These epoxy resins may be used alone or in combination of two or more.

また、硬化剤層に用いる硬化剤には、速硬化性硬化剤としてAF020(BF3 系硬化剤;大都産業社製,商品名)、D101(ポリアミン系硬化剤;大都産業社製,商品名)、DSX1460(ポリアミン系硬化剤;ヘンケル社製,商品名)、バーサミンF19(変成アミン系硬化剤;ヘンケル社製,商品名)、バーサミン368(変成アミン系硬化剤;ヘンケル社製,商品名)、QX20(芳香族チオエーテル系硬化剤;油化シェルエポキシ社製,商品名)、QX11(芳香族チオエーテル系硬化剤;油化シェルエポキシ社製,商品名)、B002W(芳香族チオエーテル系硬化剤;油化シェルエポキシ社製,商品名)等が挙げられる。これら硬化剤も単独使用、混合使用のいずれでもよい。   In addition, the curing agent used for the curing agent layer is AF020 (BF3 curing agent; manufactured by Daito Sangyo Co., Ltd., trade name), D101 (polyamine curing agent; manufactured by Daito Sangyo Co., Ltd., trade name) as a fast curing curing agent, DSX1460 (polyamine-based curing agent: Henkel, trade name), Versamine F19 (modified amine-based curing agent; Henkel, trade name), Versamine 368 (modified amine-based curing agent: Henkel, trade name), QX20 (Aromatic thioether type curing agent; product name, manufactured by Yuka Shell Epoxy Co., Ltd.), QX11 (Aromatic thioether type curing agent; product name, manufactured by Yuka Shell Epoxy Co., Ltd., product name), B002W (Aromatic thioether type curing agent; Shell Epoxy, trade name) and the like. These curing agents may be used alone or in combination.

なお、硬化剤層と主剤層の厚さは、0.7〜33μmが適当である。これら各層の厚さが余り薄過ぎると接続強度が不足し、逆に、厚過ぎると接続部分からフィルムがはみ出してしまう。   In addition, 0.7-33 micrometers is suitable for the thickness of a hardening | curing agent layer and a main ingredient layer. If the thickness of each layer is too thin, the connection strength is insufficient. Conversely, if the thickness is too thick, the film protrudes from the connection portion.

一方、主剤層と硬化剤層とを隔離する隔離層としては、(1)成膜性があること、(2)100℃以下の圧着温度によって溶融するように、ガラス転位点Tgがその圧着温度よりも低いこと、(3)主剤層と硬化剤層とを一体化でき、主剤層や硬化剤層に対する相溶性が良いこと、といった条件を満たす樹脂を用いるのが望ましい。そのような樹脂としては、例えばポリエステル樹脂、ウレタン樹脂、フェノキシ樹脂等が挙げられ、これらは単独あるいは2種類以上を混合して用いてもいずれでも良い。   On the other hand, as a separating layer that separates the main agent layer and the curing agent layer, (1) having film formability, and (2) the glass transition point Tg is the bonding temperature so that it melts at a bonding temperature of 100 ° C. or less. It is desirable to use a resin that satisfies the following conditions: (3) the main agent layer and the curing agent layer can be integrated, and the compatibility with the main agent layer and the curing agent layer is good. Examples of such a resin include a polyester resin, a urethane resin, a phenoxy resin, and the like, and these may be used alone or in combination of two or more.

この隔離層の厚さも、0.7〜33μmが適当である。隔離層の厚さが0.5μm未満では、フィルムに少しの応力がかけられただけでも当該隔離層が破断し、十分な保存性が得られない。また、隔離層の厚さが30μmより厚い場合には、圧着した時に当該隔離層が破断せず、エポキシ層と硬化剤層との接触、反応が生じなくなる。   An appropriate thickness of this isolation layer is 0.7 to 33 μm. When the thickness of the isolation layer is less than 0.5 μm, even if a slight stress is applied to the film, the isolation layer breaks, and sufficient storage stability cannot be obtained. In addition, when the thickness of the isolation layer is greater than 30 μm, the isolation layer does not break when pressed, and contact and reaction between the epoxy layer and the curing agent layer do not occur.

本発明の異方性導電性樹脂において、導電性粒子が含有されるのは、主剤層、硬化剤層又は隔離層のいずれであっても良い。導電性粒子としては、ニッケル、半田等の金属粒子、樹脂粒子に金、合金等の導電性材料を被覆したもの等が挙げられる。   In the anisotropic conductive resin of the present invention, the conductive particles may be contained in any of the main agent layer, the curing agent layer, and the isolation layer. Examples of the conductive particles include metal particles such as nickel and solder, and resin particles coated with a conductive material such as gold and alloy.

また、以上のような異方導電性接着剤フィルムの製造方法は、その一例を先に説明したがこれに限らない。たとえば、塗布の順序を、先の説明とは逆に硬化剤塗料、隔離塗料、主剤塗料の順にしても良い。また、PET等のフィルム上にそれぞれ主剤層、隔離層、硬化剤層を形成しておき、ラミネート法によって1シートにしても良い。   Moreover, although the example of the manufacturing method of the above anisotropic conductive adhesive films was demonstrated previously, it is not restricted to this. For example, the order of application may be in the order of hardener paint, isolation paint, and main paint, contrary to the above description. Alternatively, a main agent layer, a separating layer, and a curing agent layer may be formed on a film such as PET, and one sheet may be formed by a laminating method.

熱硬化性樹脂を主成分とする主剤層と、硬化剤と熱可塑性樹脂を混合してなり、硬化剤を主成分とする硬化剤層とが、隔離層を介して積層され、主剤層、硬化剤層又は隔離層のいずれかに導電性粒子が含有されている異方導電性接着剤フィルムは、熱硬化性樹脂と硬化剤とを混合する工程なしで製造され、製品となる前に熱硬化性樹脂と硬化剤とが接触してしまうことがない。このため、硬化剤や熱硬化性樹脂として速硬化性のものを用いても、製造工程で硬化反応が進行し、製品が製造できないといった事がない。また、熱硬化性樹脂と硬化剤とが隔離層によって隔離された構成であるので、保存中に硬化反応が進行してしまうこともなく、十分な保存性が得られる。   A main agent layer mainly composed of a thermosetting resin, and a curing agent and a thermoplastic resin are mixed, and a curing agent layer mainly composed of a curing agent is laminated via an isolation layer. An anisotropic conductive adhesive film containing conductive particles in either the agent layer or the separator layer is manufactured without mixing the thermosetting resin and the curing agent, and is thermoset before becoming a product. The adhesive resin and the curing agent do not come into contact with each other. For this reason, even if a fast-curing agent is used as the curing agent or thermosetting resin, the curing reaction proceeds in the production process, and the product cannot be produced. In addition, since the thermosetting resin and the curing agent are separated by the separating layer, the curing reaction does not proceed during storage, and sufficient storage stability is obtained.

したがって、硬化剤や熱硬化性樹脂として速硬化性のものを用いることが可能であり、そのような材料を用いることにより、例えば100℃以下の比較的低い圧着温度範囲でも硬化反応が速やかに進行し、圧着温度による配線基板や電子部品へのダメージを抑えながら圧着時間の短縮化が図れるようになる。   Accordingly, it is possible to use a fast-curing agent as a curing agent or a thermosetting resin, and by using such a material, the curing reaction proceeds rapidly even in a relatively low pressure bonding temperature range of, for example, 100 ° C. or less. In addition, it is possible to shorten the crimping time while suppressing damage to the wiring board and electronic components due to the crimping temperature.

本発明の好適な実施例について実験結果に基づいて説明する。
本実施例では、3層構成の異方導電性接着剤フィルムを作成し、その保存性、熱圧着性を評価した。
A preferred embodiment of the present invention will be described based on experimental results.
In this example, an anisotropic conductive adhesive film having a three-layer structure was prepared, and its preservability and thermocompression bonding were evaluated.

まず、2種類のエポキシ樹脂,EP1009(油化シェルエポキシ社製,商品名)とDT613(大都産業社製,商品名)を50重量部ずつ混合し、これに粒径5μmの樹脂粒子にニッケル、金を被覆した導電粒子を、5重量部添加することで主剤塗料を調製した。そして、この主剤塗料をPET(ポリエチレンテレフタレート)上に塗布、乾燥することで厚さ15μmの主剤層を形成した。   First, 50 parts by weight of two types of epoxy resins, EP1009 (manufactured by Yuka Shell Epoxy Co., Ltd., trade name) and DT613 (manufactured by Daito Sangyo Co., Ltd., trade name) are mixed, and nickel, The main agent paint was prepared by adding 5 parts by weight of conductive particles coated with gold. And this main ingredient paint was applied on PET (polyethylene terephthalate) and dried to form a main ingredient layer having a thickness of 15 μm.

次に、この主剤層上に、ガラス転位点Tgが45℃のポリエステル樹脂(ユニチカ社製,商品名UE3210)を100重量部含有する隔離塗料を塗布、乾燥して厚さ3μmの隔離層を形成した。   Next, an isolation coating containing 100 parts by weight of a polyester resin (product name: UE3210, manufactured by Unitika Co., Ltd.) having a glass transition point Tg of 45 ° C. is applied onto this main material layer and dried to form an isolation layer having a thickness of 3 μm. did.

そして、この隔離層上に、フィルム形成剤となるYP50(フェノキシ樹脂;東都化成社製,商品名)と、硬化剤となるAF020(BF3 系硬化剤;大都産業社製,商品名)を混合した硬化剤塗料を塗布、乾燥することで厚さ15μmの硬化剤層を形成し、異方導電性接着剤フィルム(実施例フィルム)を作成した。   And on this isolation layer, YP50 (phenoxy resin; manufactured by Toto Kasei Co., Ltd., trade name) serving as a film forming agent and AF020 (BF3-based curing agent; manufactured by Daito Sangyo Co., Ltd., trade name) serving as a curing agent were mixed. A curing agent layer having a thickness of 15 μm was formed by applying and drying a curing agent paint, and an anisotropic conductive adhesive film (Example film) was prepared.

以上のようにして作成された異方導電性接着剤フィルムについて保存性を調べるとともに、温度100℃、圧力40kgf/cm2 の条件で、熱圧着を20秒間行い、硬化度、ピール強度及びはみ出し性を調べた。その結果を表1に示す。   The anisotropic conductive adhesive film prepared as described above was examined for storability, and was subjected to thermocompression bonding for 20 seconds under the conditions of a temperature of 100 ° C. and a pressure of 40 kgf / cm 2, and the degree of cure, peel strength and protrusion property were confirmed. Examined. The results are shown in Table 1.

なお、保存性は、熱圧着前の異方導電性接着剤フィルムを温度40℃のオーブン中に20日間放置した後、メチルエチルケトン(MEK)に対する溶解性を調べることで評価した。表中、◎、○、△、×はそれぞれ以下の場合を表す。   Storage stability was evaluated by examining the solubility in methyl ethyl ketone (MEK) after leaving the anisotropic conductive adhesive film before thermocompression bonding in an oven at a temperature of 40 ° C. for 20 days. In the table, ◎, ○, Δ, and x represent the following cases, respectively.

◎:フィルムがMEKによって完全に溶解する場合
○:フィルムがMEKによってほぼ溶解する場合
△:溶解は生じないが、フィルムがポロポロくずれる状態になる場合
×:フィルムが溶解せず、フィルム状を維持する場合(ゲル化)
硬化度は、異方導電接着剤フィルムを熱圧着した後、MEKに対する溶解性を調べることで評価した。表中、◎、○、△、×はそれぞれ以下の場合を表す。
◎:フィルムが溶解せず、フィルム状を維持する場合
○:フィルムがほとんど溶解せず、フィルム状をほぼ維持する場合
△:溶解は生じないが、フィルムがポロポロくずれる状態になる場合
×:フィルムが溶解し、MEKが白濁する場合
ピール強度は、引張り試験機(オリエンチック社製,商品名UCT−2.5T)を用い、以下の条件で測定した。
被着体:25μmユーピレックス基材 18μmCu 0.2mmピッチ150本パターン/ITOベタガラス
測定方法:90°
ピール測定条件:25℃
また、表中、◎、○、△、×はそれぞれ以下の場合を表す。
◎:ピール強度が1000g/cm以上である場合
○:ピール強度が500g/cm以上1000g/cm未満である場合
△:ピール強度が200g/cm以上500g/cm未満である場合
×:ピール強度が200g/cm未満である場合
はみ出し性は、圧着部からはみ出したフィルムのはみ出し量xを測定することで評価した。表中、◎、○、△、×はそれぞれ以下の場合を表す。
◎:はみ出し量xがx=0mmである場合
○:はみ出し量xが0mm<x≦1mmである場合
△:はみ出し量xが1mm<x≦3mmである場合
×:はみ出し量xが3mm<xである場合
また、比較として1層中に熱硬化性樹脂、硬化剤、導電性粒子が含有されている、従来のタイプの異方導電性接着剤フィルム〔CP7131(膜厚25μm);比較例フィルム〕についても同様にして、保存性及び熱圧着後の硬化度、ピール強度、はみ出し性を調べた。その結果も表1に併せて示す。なお、比較例フィルムについては、参考のため温度170℃、圧力40kgf/cm、圧着時間20秒間の条件で熱圧着を行った場合についても評価を行った。
◎: When the film is completely dissolved by MEK ○: When the film is almost dissolved by MEK △: When dissolution does not occur, but the film is in a state where it is crushed ×: The film does not dissolve and maintains the film shape Case (gelation)
The degree of cure was evaluated by examining the solubility in MEK after thermocompression bonding of the anisotropic conductive adhesive film. In the table, ◎, ○, Δ, and x represent the following cases, respectively.
A: When the film is not dissolved and the film shape is maintained. ○: When the film is hardly dissolved and the film shape is substantially maintained. Δ: When the film is not dissolved, but the film is in a state where it is broken. When dissolved and MEK becomes cloudy The peel strength was measured under the following conditions using a tensile tester (trade name UCT-2.5T manufactured by Orientic Co., Ltd.).
Substrate: 25 μm Upilex substrate 18 μm Cu 0.2 mm pitch 150 pattern / ITO solid glass Measuring method: 90 °
Peel measurement conditions: 25 ° C
In the table, ◎, ○, Δ, and x represent the following cases, respectively.
◎: When peel strength is 1000 g / cm or more ○: When peel strength is 500 g / cm or more and less than 1000 g / cm Δ: When peel strength is 200 g / cm or more and less than 500 g / cm ×: Peel strength is 200 g When it is less than / cm, the protruding property was evaluated by measuring the protruding amount x of the film protruding from the crimping part. In the table, ◎, ○, Δ, and x represent the following cases, respectively.
A: When the protrusion amount x is x = 0 mm ○: When the protrusion amount x is 0 mm <x ≦ 1 mm Δ: When the protrusion amount x is 1 mm <x ≦ 3 mm ×: The protrusion amount x is 3 mm <x In some cases, a conventional type anisotropic conductive adhesive film [CP7131 (film thickness: 25 μm); comparative example film] containing a thermosetting resin, a curing agent, and conductive particles in one layer as a comparison. In the same manner, the storage stability, the degree of cure after thermocompression bonding, the peel strength, and the protruding property were examined. The results are also shown in Table 1. The comparative film was also evaluated for thermocompression bonding under the conditions of a temperature of 170 ° C., a pressure of 40 kgf / cm 2 , and a pressure bonding time of 20 seconds for reference.

Figure 2006312743
Figure 2006312743


表1からわかるように、単層構成の比較例フィルムは、熱圧着温度が170℃であれば良好な熱圧着が行えるが、熱圧着温度が100℃と低くなると、硬化度、ピール強度が不十分になり良好な圧着が行われない。
一方、3層構成の実施例フィルムは、速硬化性の硬化剤を用いているが十分な保存性が得られており、また熱圧着温度が100℃であっても、十分な硬化度、ピール強度が得られる。
このことから、異方導電性接着剤フィルムを、熱硬化性樹脂よりなる主剤層、隔離層、硬化剤層の3層で構成すると、硬化剤として速硬化性のものを用いることが可能になり、100℃程度の圧着温度であっても十分に圧着が行えるようになることがわかった。
3層構成の異方導電性接着剤フィルムの層厚の検討
主剤層、隔離層、硬化剤層の厚さを表2に示すように変えたこと以外は実施例フィルムと同様にして異方導電性接着剤フィルム(実験例フィルム1〜実験例フィルム5、比較例フィルム1〜4)

As can be seen from Table 1, the comparative film having a single-layer structure can perform good thermocompression bonding when the thermocompression bonding temperature is 170 ° C., but when the thermocompression bonding temperature is lowered to 100 ° C., the degree of cure and peel strength are poor. It will be sufficient and good pressure bonding will not be performed.
On the other hand, the example film having a three-layer structure uses a fast-curing curing agent, but has sufficient storage stability, and even when the thermocompression bonding temperature is 100 ° C., sufficient curing degree and peel Strength is obtained.
From this, when the anisotropic conductive adhesive film is composed of three layers of a main agent layer made of a thermosetting resin, a separating layer, and a curing agent layer, it becomes possible to use a fast curing one as the curing agent. It was found that sufficient pressure bonding can be achieved even at a temperature of about 100 ° C.
Examination of layer thickness of three-layer anisotropic conductive adhesive film Anisotropic conductive film in the same manner as the example film except that the thicknesses of the main agent layer, the separating layer and the curing agent layer were changed as shown in Table 2. Adhesive film (Experimental film 1 to Experimental film 5, Comparative film 1 to 4)

Figure 2006312743
Figure 2006312743


以上のようにして作成された異方導電性接着剤フィルムについて、上述と同様にして保存性を調べるとともに、温度100℃、圧力40kgf/cmの条件で熱圧着を20秒間行い、硬化度、ピール強度及びはみ出し性を調べた。評価結果を表3に示す。

For the anisotropic conductive adhesive film prepared as described above, the storage stability was examined in the same manner as described above, and thermocompression bonding was performed for 20 seconds under the conditions of a temperature of 100 ° C. and a pressure of 40 kgf / cm 2 , The peel strength and the protruding property were examined. The evaluation results are shown in Table 3.

Figure 2006312743
Figure 2006312743


表3からわかるように、まず主剤層や硬化剤層の厚さが比較的薄い比較例フィルム3ではピール強度が不足する。逆にこれらの厚さが比較的厚い比較例フィルム4では、硬化度やピール強度は優れているが圧着部分からフィルムがはみ出してしまう。圧着部分からのフィルムのはみ出しを抑えながら、十分な接続強度を得るには、主剤層や硬化剤層の厚さは0.7〜33μmが適当である。

As can be seen from Table 3, first, the comparative film 3 in which the thickness of the main agent layer and the curing agent layer is relatively thin has insufficient peel strength. On the contrary, in comparative example film 4 having a relatively large thickness, the degree of cure and peel strength are excellent, but the film protrudes from the crimped portion. In order to obtain sufficient connection strength while suppressing the protrusion of the film from the crimped portion, the thickness of the main agent layer and the curing agent layer is suitably 0.7 to 33 μm.

一方、隔離層の厚さが比較的薄い比較例フィルム1では、保存中に硬化反応が進行してしまい保存性が悪い。逆に、この厚さが比較的厚い比較例フィルム2では、圧着に際して硬化反応が十分に進行せず、硬化度、ピール強度が不足する。保存性を確保しながら、十分な接着強度を確保するには、隔離層の厚さは0.7〜33μmが適当である。   On the other hand, in the comparative film 1 in which the thickness of the isolation layer is relatively thin, the curing reaction proceeds during storage and the storage stability is poor. On the other hand, in the comparative film 2 having a relatively large thickness, the curing reaction does not proceed sufficiently at the time of pressure bonding, and the curing degree and peel strength are insufficient. In order to secure sufficient adhesive strength while ensuring storage stability, the thickness of the isolation layer is suitably 0.7 to 33 μm.

本発明を適用した異方導電性接着剤フィルムの1例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the anisotropically conductive adhesive film to which this invention is applied.

符号の説明Explanation of symbols

1 主剤層、 2 硬化剤層、 3 隔離層   1 main agent layer, 2 hardener layer, 3 isolation layer

Claims (3)

熱硬化性樹脂を主成分とする主剤層と、硬化剤と熱可塑性樹脂を混合してなり、硬化剤を主成分とする硬化剤層とが、隔離層を介して積層され、
上記主剤層、上記硬化剤層又は上記隔離層のいずれかに導電性粒子が含有され、
上記主剤層、上記隔離層及び上記硬化剤層の厚みが、それぞれ0.7〜33μmであり、
上記剥離層及び上記硬化剤層の厚みの合計が、上記主剤層の厚みよりも大きく形成されていることを特徴とする異方導電性接着剤フィルム。
A main agent layer mainly composed of a thermosetting resin, a curing agent and a thermoplastic resin are mixed, and a curing agent layer mainly composed of a curing agent is laminated via an isolation layer,
Conductive particles are contained in any of the main agent layer, the curing agent layer, or the isolation layer,
The thicknesses of the main agent layer, the isolation layer and the curing agent layer are 0.7 to 33 μm, respectively.
The anisotropic conductive adhesive film characterized in that the total thickness of the release layer and the curing agent layer is larger than the thickness of the main agent layer.
上記主剤層の主成分である熱硬化性樹脂には、エポキシ樹脂が用いられ、
上記硬化剤層の主成分である硬化剤には、上記熱硬化性樹脂と反応する速硬化性硬化剤として、BF3系硬化剤、ポリアミン系硬化剤、変性アミン系硬化剤及び芳香族チオエーテル系硬化剤のいずれか1以上が用いられることを特徴とする請求項1記載の異方導電性接着剤フィルム。
The thermosetting resin that is the main component of the main agent layer is an epoxy resin,
The curing agent that is the main component of the curing agent layer includes a BF3 curing agent, a polyamine curing agent, a modified amine curing agent, and an aromatic thioether curing as a fast curing agent that reacts with the thermosetting resin. Any one or more of an agent is used, The anisotropic conductive adhesive film of Claim 1 characterized by the above-mentioned.
上記隔離層は、その圧着温度よりもガラス転位点Tgの低い樹脂層であることを特徴とする請求項1記載の異方導電性接着剤フィルム。   2. The anisotropic conductive adhesive film according to claim 1, wherein the isolation layer is a resin layer having a glass transition point Tg lower than the pressure bonding temperature.
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JP7017036B2 (en) 2015-10-07 2022-02-08 大日本印刷株式会社 How to manufacture adhesive sheet sets and articles
US11578237B2 (en) 2015-10-07 2023-02-14 Dai Nippon Printing Co., Ltd. Adhesive sheet set and method for producing product
JP2018176545A (en) * 2017-04-12 2018-11-15 大日本印刷株式会社 Method for manufacturing article

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