WO2011024719A1 - Anisotropic conductive material, connection structure, and connection structure producing method - Google Patents

Anisotropic conductive material, connection structure, and connection structure producing method Download PDF

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WO2011024719A1
WO2011024719A1 PCT/JP2010/064077 JP2010064077W WO2011024719A1 WO 2011024719 A1 WO2011024719 A1 WO 2011024719A1 JP 2010064077 W JP2010064077 W JP 2010064077W WO 2011024719 A1 WO2011024719 A1 WO 2011024719A1
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anisotropic conductive
conductive material
compound
group
weight
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PCT/JP2010/064077
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French (fr)
Japanese (ja)
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茂雄 真原
敬士 久保田
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積水化学工業株式会社
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Priority to CN201080037248.5A priority Critical patent/CN102484326B/en
Priority to JP2011528764A priority patent/JP5602743B2/en
Publication of WO2011024719A1 publication Critical patent/WO2011024719A1/en

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    • H—ELECTRICITY
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    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
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    • H01R12/00—Structural associations of a plurality of mutually-insulated electrical connecting elements, specially adapted for printed circuits, e.g. printed circuit boards [PCB], flat or ribbon cables, or like generally planar structures, e.g. terminal strips, terminal blocks; Coupling devices specially adapted for printed circuits, flat or ribbon cables, or like generally planar structures; Terminals specially adapted for contact with, or insertion into, printed circuits, flat or ribbon cables, or like generally planar structures
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Abstract

Provided are an anisotropic conductive material including conductive particles, by which the reliability in conduction between electrodes which are electrically connected can be improved, and a connection structure using the anisotropic conductive material. The anisotropic conductive material contains a curable compound, a heat-curable agent, a light curing initiator, and conductive particles. In 100 wt% of the anisotropic conductive material, the content of the conductive particles ranges 1 to 19 wt%. the connection structure is comprised of a first member (2) to be connected, a second member (4) to be connected, and a connection portion (3) which connects the first and second members (2, 4). The connection portion (3) is formed by curing the anisotropic conductive material.

Description

異方性導電材料、接続構造体及び接続構造体の製造方法Anisotropic conductive material, connection structure, and manufacturing method of connection structure
　本発明は、複数の導電性粒子を含む異方性導電材料であって、例えば、フレキシブルプリント基板、ガラス基板及び半導体チップなどの様々な接続対象部材の電極間の電気的な接続に用いることができる異方性導電材料、並びに該異方性導電材料を用いた接続構造体及び接続構造体の製造方法に関する。 The present invention is an anisotropic conductive material including a plurality of conductive particles, and can be used for electrical connection between electrodes of various connection target members such as a flexible printed circuit board, a glass substrate, and a semiconductor chip. The present invention relates to an anisotropic conductive material, a connection structure using the anisotropic conductive material, and a method of manufacturing the connection structure.
　異方性導電ペースト、異方性導電インク及び異方性導電粘接着剤等の異方性導電材料が広く知られている。これらの異方性導電材料では、ペースト、インク又は樹脂中に複数の導電性粒子が分散されている。 Anisotropic conductive materials such as anisotropic conductive paste, anisotropic conductive ink and anisotropic conductive adhesive are widely known. In these anisotropic conductive materials, a plurality of conductive particles are dispersed in paste, ink, or resin.
　上記異方性導電材料は、例えば、フレキシブルプリント基板とガラス基板との接続（ＦＯＧ（Ｆｉｌｍ　ｏｎ　Ｇｌａｓｓ））、半導体チップとフレキシブルプリント基板との接続（ＣＯＦ（Ｃｈｉｐ　ｏｎ　Ｆｉｌｍ））、又は半導体チップとガラス基板との接続（ＣＯＧ（Ｃｈｉｐ　ｏｎ　Ｇｌａｓｓ））等に使用されている。 The anisotropic conductive material is, for example, a connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), a connection between a semiconductor chip and a flexible printed circuit board (COF (Chip on Film)), or a semiconductor chip. Used for connection to glass substrates (COG (Chip on Glass)) and the like.
　上記異方性導電材料の一例として、下記の特許文献１には、エポキシ樹脂と、ゴム状ポリマー粒子と、熱活性な潜在性エポキシ硬化剤と、高軟化点ポリマー粒子と、導電性粒子とを含有する異方性導電材料が開示されている。 As an example of the anisotropic conductive material, Patent Document 1 below includes an epoxy resin, rubber-like polymer particles, a thermally active latent epoxy curing agent, high softening point polymer particles, and conductive particles. An anisotropic conductive material is disclosed.
　また、下記の特許文献２には、２５℃及び２．５ｐｍでの粘度をη１、２５℃及び２０ｒｐｍでの粘度をη２としたときに、下記式（Ａ）及び（Ｂ）を満たす異方性導電接着剤が開示されている。
　５０Ｐａ・ｓ≦η２≦２００Ｐａ・ｓ　　・・・式（Ａ）
　１．５≦η１／η２≦４．３　　　　　　・・・式（Ｂ） Patent Document 2 below describes anisotropy satisfying the following formulas (A) and (B) when the viscosity at 25 ° C. and 2.5 pm is η1, and the viscosity at 25 ° C. and 20 rpm is η2. A conductive adhesive is disclosed.
50 Pa · s ≦ η2 ≦ 200 Pa · s Formula (A)
1.5 ≦ η1 / η2 ≦ 4.3 Formula (B)
特開２０００－３４５０１０号公報JP 2000-34010 A 特開２００３－０６４３３０号公報JP 2003-064330 A
　上記異方性導電材料により、例えば、半導体チップの電極とガラス基板の電極とを電気的に接続する際には、ガラス基板上に、導電性粒子を含む異方性導電材料を配置する。次に、半導体チップを積層して、加熱及び加圧する。これにより、異方性導電材料を硬化させて、かつ導電性粒子を介して電極間を電気的に接続し、接続構造体を得る。 For example, when the semiconductor chip electrode and the glass substrate electrode are electrically connected by the anisotropic conductive material, an anisotropic conductive material containing conductive particles is disposed on the glass substrate. Next, the semiconductor chips are stacked, and heated and pressurized. As a result, the anisotropic conductive material is cured, and the electrodes are electrically connected via the conductive particles to obtain a connection structure.
　特許文献１，２に記載のような従来の異方性導電材料では、上記電極間の電気的な接続の際に、ガラス基板上に塗布された異方性導電材料及び該異方性導電材料に含まれている導電性粒子が、硬化前に大きく流動することがある。このため、異方性導電材料により形成された硬化物層及び導電性粒子を特定の領域に配置できないことがある。さらに、接続されるべき上下の電極間に導電性粒子を配置できなかったり、接続されてはならない隣接する電極間が複数の導電性粒子を介して電気的に接続されたりすることがある。このため、得られた接続構造体の導通信頼性が低いことがある。 In the conventional anisotropic conductive materials described in Patent Documents 1 and 2, the anisotropic conductive material applied on the glass substrate at the time of electrical connection between the electrodes and the anisotropic conductive material In some cases, the conductive particles contained in the fluid flow largely before curing. For this reason, the hardened | cured material layer and electroconductive particle formed with the anisotropic electrically-conductive material may not be arrange | positioned to a specific area | region. Furthermore, the conductive particles may not be disposed between the upper and lower electrodes to be connected, or adjacent electrodes that should not be connected may be electrically connected via a plurality of conductive particles. For this reason, the conduction | electrical_connection reliability of the obtained connection structure may be low.
　本発明の目的は、導電性粒子を含む異方性導電材料であって、電極間の電気的な接続に用いられた場合に、導通信頼性を高めることができる異方性導電材料、並びに該異方性導電材料を用いた接続構造体及び接続構造体の製造方法を提供することである。 An object of the present invention is an anisotropic conductive material containing conductive particles, which can increase conduction reliability when used for electrical connection between electrodes, and the It is to provide a connection structure using an anisotropic conductive material and a method for manufacturing the connection structure.
　本発明の広い局面によれば、硬化性化合物と、熱硬化剤と、光硬化開始剤と、導電性粒子とを含有し、上記導電性粒子の含有量が１～１９重量％の範囲内である、異方性導電材料が提供される。 According to a wide aspect of the present invention, the composition contains a curable compound, a thermosetting agent, a photocuring initiator, and conductive particles, and the content of the conductive particles is within a range of 1 to 19% by weight. An anisotropic conductive material is provided.
　本発明に係る異方性導電材料のある特定の局面では、上記硬化性化合物は、エピスルフィド化合物を含む。 In a specific aspect of the anisotropic conductive material according to the present invention, the curable compound includes an episulfide compound.
　本発明に係る異方性導電材料の他の特定の局面では、上記硬化性化合物は、エポキシ基及びチイラン基の内の少なくとも一種の基と、（メタ）アクリロイル基とを有する硬化性化合物を含む。 In another specific aspect of the anisotropic conductive material according to the present invention, the curable compound includes a curable compound having at least one of an epoxy group and a thiirane group and a (meth) acryloyl group. .
　本発明に係る異方性導電材料の２５℃及び２．５ｒｐｍでの粘度は、２０～２００Ｐａ・ｓの範囲内であることが好ましい。 The viscosity of the anisotropic conductive material according to the present invention at 25 ° C. and 2.5 rpm is preferably in the range of 20 to 200 Pa · s.
　本発明に係る異方性導電材料の他の特定の局面では、光の照射により硬化が進行されて、Ｂステージ化した後の粘度が２０００～３５００Ｐａ・ｓの範囲内である。 In another specific aspect of the anisotropic conductive material according to the present invention, the viscosity after being cured by light irradiation and converted into a B stage is in the range of 2000 to 3500 Pa · s.
　本発明に係る異方性導電材料では、２５℃及び２．５ｒｐｍでの粘度をη１とし、かつ２５℃及び５ｒｐｍでの粘度をη２としたときに、上記η２が２０Ｐａ・ｓ以上２００Ｐａ・ｓ以下であり、かつ上記η１の上記η２に対する比（η１／η２）が０．９以上１．１以下であることが好ましい。 In the anisotropic conductive material according to the present invention, when the viscosity at 25 ° C. and 2.5 rpm is η1, and the viscosity at 25 ° C. and 5 rpm is η2, the η2 is 20 Pa · s or more and 200 Pa · s or less. And the ratio (η1 / η2) of η1 to η2 is preferably 0.9 or more and 1.1 or less.
　本発明に係る異方性導電材料の別の特定の局面では、上記硬化性化合物は、結晶性化合物を含む。 In another specific aspect of the anisotropic conductive material according to the present invention, the curable compound includes a crystalline compound.
　本発明に係る接続構造体は、第１の接続対象部材と、第２の接続対象部材と、該第１，第２の接続対象部材を電気的に接続している接続部とを備え、上記接続部が、本発明に従って構成された異方性導電材料を硬化させることにより形成されている。 A connection structure according to the present invention includes a first connection target member, a second connection target member, and a connection portion that electrically connects the first and second connection target members, and The connecting portion is formed by curing an anisotropic conductive material configured according to the present invention.
　さらに、本発明の広い局面によれば、第１の接続対象部材の上面に異方性導電材料を塗布し、異方性導電材料層を形成する工程と、該異方性導電材料層に光を照射することにより、上記異方性導電材料層の硬化を進行させて、粘度が２０００～３５００Ｐａ・ｓの範囲内となるように、上記異方性導電材料層をＢステージ化する工程と、Ｂステージ化された異方性導電材料層の上面に、第２の接続対象部材をさらに積層する工程とを備え、上記異方性導電材料として、硬化性化合物と、熱硬化剤と、光硬化開始剤と、導電性粒子とを含有し、上記導電性粒子の含有量が１～１９重量％の範囲内である異方性導電材料を用いる、接続構造体の製造方法が提供される。 Furthermore, according to a wide aspect of the present invention, an anisotropic conductive material is applied to the upper surface of the first connection target member to form an anisotropic conductive material layer, and light is applied to the anisotropic conductive material layer. To cure the anisotropic conductive material layer to form a B-stage of the anisotropic conductive material layer so that the viscosity is in the range of 2000 to 3500 Pa · s; And a step of further laminating a second connection target member on the upper surface of the B-staged anisotropic conductive material layer. As the anisotropic conductive material, a curable compound, a thermosetting agent, and photocuring There is provided a method for producing a connection structure using an anisotropic conductive material containing an initiator and conductive particles, wherein the content of the conductive particles is in the range of 1 to 19% by weight.
　本発明に係る異方性導電材料は、硬化性化合物と熱硬化剤と光硬化開始剤と導電性粒子とを含有するので、光の照射及び加熱により、異方性導電材料を硬化させることができる。例えば、異方性導電材料を光の照射又は加熱により半硬化させた後に、熱硬化又は光硬化させることで、異方性導電材料を硬化させることができる。このため、塗布後の適切な時期に異方性導電材料に光を照射又は熱を付与することにより、異方性導電材料及び該異方性導電材料に含まれている導電性粒子の流動を抑制できる。従って、異方性導電材料により形成された硬化物層及び導電性粒子を特定の領域に配置できる。 Since the anisotropic conductive material according to the present invention contains a curable compound, a thermosetting agent, a photocuring initiator, and conductive particles, the anisotropic conductive material can be cured by light irradiation and heating. it can. For example, after the anisotropic conductive material is semi-cured by light irradiation or heating, the anisotropic conductive material can be cured by thermosetting or photocuring. For this reason, the anisotropic conductive material and the conductive particles contained in the anisotropic conductive material can be flowed by irradiating the anisotropic conductive material with light or applying heat to the anisotropic conductive material at an appropriate time after coating. Can be suppressed. Therefore, the hardened | cured material layer and electroconductive particle formed with the anisotropic electrically-conductive material can be arrange | positioned in a specific area | region.
　さらに、本発明に係る異方性導電材料は、硬化性化合物と熱硬化剤と光硬化開始剤と導電性粒子とを含有し、更に上記導電性粒子の含有量が１～１９重量％の範囲内であるので、電極間の電気的な接続に用いられた場合に、導通信頼性を高めることができる。例えば、接続されるべき上下の電極間を導電性粒子により容易に接続でき、かつ接続されてはならない隣り合う電極間が複数の導電性粒子を介して接続されるのを抑制できる。 Furthermore, the anisotropic conductive material according to the present invention contains a curable compound, a thermosetting agent, a photocuring initiator, and conductive particles, and the content of the conductive particles is in the range of 1 to 19% by weight. Since it is inside, when it is used for the electrical connection between electrodes, conduction | electrical_connection reliability can be improved. For example, the upper and lower electrodes to be connected can be easily connected with conductive particles, and adjacent electrodes that should not be connected can be prevented from being connected via a plurality of conductive particles.
　本発明に係る接続構造体の製造方法では、異方性導電材料層に光を照射することにより、上記異方性導電材料層の硬化を進行させて、粘度が２０００～３５００Ｐａ・ｓの範囲内となるように、上記異方性導電材料層をＢステージ化するので、異方性導電材料層及び該異方性導電材料層に含まれている導電性粒子の流動を抑制できる。従って、異方性導電材料により形成された硬化物層及び導電性粒子を特定の領域に配置できる。このため、第１，第２の接続対象部材の電極間を電気的に接続した場合に、導通信頼性を高めることができる。例えば、接続されるべき上下の電極間を導電性粒子により容易に接続でき、かつ接続されてはならない隣り合う電極間が複数の導電性粒子を介して接続されるのを抑制できる。 In the method for manufacturing a connection structure according to the present invention, the anisotropic conductive material layer is cured by irradiating light to the anisotropic conductive material layer so that the viscosity is in the range of 2000 to 3500 Pa · s. Thus, the anisotropic conductive material layer is B-staged so that the flow of the anisotropic conductive material layer and the conductive particles contained in the anisotropic conductive material layer can be suppressed. Therefore, the hardened | cured material layer and electroconductive particle formed with the anisotropic electrically-conductive material can be arrange | positioned in a specific area | region. For this reason, conduction | electrical_connection reliability can be improved when the electrodes of the 1st, 2nd connection object member are electrically connected. For example, the upper and lower electrodes to be connected can be easily connected with conductive particles, and adjacent electrodes that should not be connected can be prevented from being connected via a plurality of conductive particles.
図１は、本発明の一実施形態に係る異方性導電材料を用いた接続構造体を模式的に示す部分切欠正面断面図である。FIG. 1 is a partially cutaway front sectional view schematically showing a connection structure using an anisotropic conductive material according to an embodiment of the present invention. 図２（ａ）～（ｃ）は、本発明の一実施形態に係る異方性導電材料を用いた接続構造体の製造方法の各工程を説明するための部分切欠正面断面図である。2 (a) to 2 (c) are partially cutaway front cross-sectional views for explaining each step of a method for manufacturing a connection structure using an anisotropic conductive material according to an embodiment of the present invention. 図３（ａ）及び（ｂ）は、本発明の一実施形態に係る異方性導電材料を用いた接続構造体の製造方法において、ディスペンサーと光照射装置とを備える複合装置を用いて、Ｂステージ化された異方性導電材料層を形成する方法を説明するための模式的な正面図である。3 (a) and 3 (b) show a method for manufacturing a connection structure using an anisotropic conductive material according to an embodiment of the present invention, using a composite device including a dispenser and a light irradiation device. It is a typical front view for demonstrating the method of forming the staged anisotropic conductive material layer. 図４（ａ）及び（ｂ）は、Ｂステージ化された異方性導電材料層を形成する方法の変形例を説明するための模式的な正面図である。FIGS. 4A and 4B are schematic front views for explaining a modification of the method of forming the B-staged anisotropic conductive material layer.
　以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
　本発明に係る異方性導電材料は、硬化性化合物と、熱硬化剤と、光硬化開始剤と、導電性粒子とを含有する。本発明に係る異方性導電材料１００重量％中、上記導電性粒子の含有量は１～１９重量％の範囲内である。 The anisotropic conductive material according to the present invention contains a curable compound, a thermosetting agent, a photocuring initiator, and conductive particles. In 100% by weight of the anisotropic conductive material according to the present invention, the content of the conductive particles is in the range of 1 to 19% by weight.
　先ず、本発明に係る異方性導電材料に含まれている各成分の詳細を説明する。 First, details of each component contained in the anisotropic conductive material according to the present invention will be described.
　（硬化性化合物）
　上記硬化性化合物は特に限定されない。上記硬化性化合物として、従来公知の硬化性化合物を用いることができる。上記硬化性化合物は１種のみが用いられてもよく、２種以上が併用されてもよい。 (Curable compound)
The curable compound is not particularly limited. As the curable compound, a conventionally known curable compound can be used. As for the said sclerosing | hardenable compound, only 1 type may be used and 2 or more types may be used together.
　上記硬化性化合物としては、光及び熱硬化性化合物、光硬化性化合物、並びに熱硬化性化合物が挙げられる。上記光及び熱硬化性化合物は、光硬化性と熱硬化性とを有する。上記光硬化性化合物は、例えば光硬化性を有し、かつ熱硬化性を有さない。上記熱硬化性化合物は、例えば光硬化性を有さず、かつ熱硬化性を有する。 Examples of the curable compound include light and thermosetting compounds, photocurable compounds, and thermosetting compounds. The light and thermosetting compounds have photocuring properties and thermosetting properties. The said photocurable compound has photocurability, for example, and does not have thermosetting. The said thermosetting compound does not have photocurability, for example, and has thermosetting.
　上記硬化性化合物は、光及び熱硬化性化合物を含むか、又は光硬化性化合物と熱硬化性化合物とを含む。上記硬化性化合物が上記光及び熱硬化性化合物を含む場合には、上記硬化性化合物は、光硬化性化合物及び熱硬化性化合物の内の少なくとも一種を含んでいなくてもよく、上記光及び熱硬化性化合物に加えて、光硬化性化合物及び熱硬化性化合物の内の少なくとも一種をさらに含んでいてもよい。上記硬化性化合物が上記光及び熱硬化性化合物を含まない場合には、上記硬化性化合物は、光硬化性化合物と熱硬化性化合物とを含む。 The curable compound includes light and a thermosetting compound, or includes a photocurable compound and a thermosetting compound. When the curable compound includes the light and the thermosetting compound, the curable compound may not include at least one of the photocurable compound and the thermosetting compound. In addition to the thermosetting compound, at least one of a photocurable compound and a thermosetting compound may be further included. When the said curable compound does not contain the said light and a thermosetting compound, the said curable compound contains a photocurable compound and a thermosetting compound.
　異方性導電材料の硬化を容易に制御する観点からは、上記硬化性化合物は、上記光及び熱硬化性化合物と、光硬化性化合物及び熱硬化性化合物の内の少なくとも一種とを含むか、又は光硬化性化合物と熱硬化性化合物とを含むことが好ましい。上記硬化性化合物は、光硬化性化合物と熱硬化性化合物とを含むことがより好ましい。 From the viewpoint of easily controlling the curing of the anisotropic conductive material, the curable compound includes the light and the thermosetting compound, and at least one of the photocurable compound and the thermosetting compound, Or it is preferable that a photocurable compound and a thermosetting compound are included. More preferably, the curable compound includes a photocurable compound and a thermosetting compound.
　上記硬化性化合物は特に限定されない。上記硬化性化合物としては、エポキシ化合物、エピスルフィド化合物、（メタ）アクリル化合物、フェノール化合物、アミノ化合物、不飽和ポリエステル化合物、ポリウレタン化合物、シリコーン化合物及びポリイミド化合物等が挙げられる。上記（メタ）アクリルは、アクリル又はメタクリルを意味する。 The curable compound is not particularly limited. Examples of the curable compound include epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenolic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds. The (meth) acryl means acryl or methacryl.
　光硬化性化合物と熱硬化性化合物とを併用する場合には、光硬化性化合物と熱硬化性化合物との使用量は、光硬化性化合物と熱硬化性化合物との種類に応じて適宜調整される。本発明に係る異方性導電材料は、光硬化性化合物と熱硬化性化合物とを重量比で、１：９９～９０：１０で含むことが好ましく、５：９５～６０：４０で含むことがより好ましく、２０：８０～４０：６０で含むことが更に好ましい。 When a photocurable compound and a thermosetting compound are used in combination, the usage amount of the photocurable compound and the thermosetting compound is appropriately adjusted according to the types of the photocurable compound and the thermosetting compound. The The anisotropic conductive material according to the present invention preferably contains the photocurable compound and the thermosetting compound in a weight ratio of 1:99 to 90:10, preferably 5:95 to 60:40. More preferably, it is more preferably included at 20:80 to 40:60.
　上記η２及び上記比（η１／η２）を上記範囲内に容易に制御する観点からは、上記硬化性化合物は、結晶性樹脂を含むことが好ましい。 From the viewpoint of easily controlling the η2 and the ratio (η1 / η2) within the above range, the curable compound preferably contains a crystalline resin.
　上記結晶性樹脂は、特に限定されず、結晶性を有していればよい。上記結晶性樹脂としては、例えば、ナフタレン骨格構造に上記光及び熱硬化性の官能基を有する樹脂、並びにレゾルシン骨格構造に上記光及び熱硬化性の官能基を有する樹脂等が挙げられる。 The crystalline resin is not particularly limited as long as it has crystallinity. Examples of the crystalline resin include a resin having the light and thermosetting functional groups in the naphthalene skeleton structure, and a resin having the light and thermosetting functional groups in the resorcin skeleton structure.
　上記η２及び上記比（η１／η２）を上記範囲内に容易に制御する観点からは、上記硬化性化合物１００重量部中、上記結晶性樹脂の含有量の好ましい下限は８０重量部、より好ましい下限は９０重量部である。 From the viewpoint of easily controlling the η2 and the ratio (η1 / η2) within the above range, a preferable lower limit of the content of the crystalline resin in 100 parts by weight of the curable compound is 80 parts by weight, and a more preferable lower limit. Is 90 parts by weight.
　［熱硬化性化合物］
　異方性導電材料の硬化を容易に制御したり、接続構造体の導通信頼性をより一層高めたりする観点からは、上記硬化性化合物は、エポキシ化合物及びエピスルフィド化合物（チイラン基含有化合物）の内の少なくとも一種を含むことが好ましく、エピスルフィド化合物を含むことがより好ましい。異方性導電材料の硬化性を高める観点からは、上記硬化性化合物１００重量部中、上記エピスルフィド化合物の含有量の好ましい下限は１０重量部、より好ましい下限は２０重量部、好ましい上限は５０重量部、より好ましい上限は４０重量部である。 [Thermosetting compound]
From the viewpoint of easily controlling the curing of the anisotropic conductive material and further enhancing the conduction reliability of the connection structure, the curable compound is an epoxy compound or an episulfide compound (thiirane group-containing compound). It is preferable that at least one of these is included, and it is more preferable that an episulfide compound is included. From the viewpoint of enhancing the curability of the anisotropic conductive material, in 100 parts by weight of the curable compound, the preferred lower limit of the content of the episulfide compound is 10 parts by weight, the more preferred lower limit is 20 parts by weight, and the preferred upper limit is 50 parts by weight. Parts, more preferred upper limit is 40 parts by weight.
　上記エポキシ化合物及び上記エピスルフィド化合物はそれぞれ、芳香族環を有することが好ましい。上記芳香族環としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、テトラセン環、クリセン環、トリフェニレン環、テトラフェン環、ピレン環、ペンタセン環、ピセン環及びペリレン環等が挙げられる。なかでも、上記芳香族環は、ベンゼン環、ナフタレン環又はアントラセン環であることが好ましく、ベンゼン環又はナフタレン環であることがより好ましい。 Each of the epoxy compound and the episulfide compound preferably has an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, tetracene ring, chrysene ring, triphenylene ring, tetraphen ring, pyrene ring, pentacene ring, picene ring and perylene ring. Especially, it is preferable that the said aromatic ring is a benzene ring, a naphthalene ring, or an anthracene ring, and it is more preferable that it is a benzene ring or a naphthalene ring.
　エピスルフィド化合物は、エポキシ基ではなくチイラン基を有するので、低温で速やかに硬化させることができる。すなわち、チイラン基を有するエピスルフィド化合物は、エポキシ基を有するエポキシ化合物と比較して、チイラン基に由来してより一層低い温度で硬化可能である。 Since the episulfide compound has a thiirane group instead of an epoxy group, it can be quickly cured at a low temperature. That is, the episulfide compound having a thiirane group can be cured at a lower temperature derived from the thiirane group as compared with the epoxy compound having an epoxy group.
　低温でより一層速やかに硬化させる観点からは、上記エピスルフィド化合物は、下記式（１）、（２）、（５）、（７）又は（８）で表される構造を有することが好ましく、下記式（１）又は（２）で表される構造を有することがより好ましい。 From the viewpoint of curing more rapidly at a low temperature, the episulfide compound preferably has a structure represented by the following formula (1), (2), (5), (7) or (8). It is more preferable to have a structure represented by the formula (1) or (2).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　上記式（１）中、Ｒ１及びＲ２はそれぞれ炭素数１～５のアルキレン基を表し、Ｒ３、Ｒ４、Ｒ５及びＲ６の４個の基の内の２～４個の基は水素を表し、Ｒ３、Ｒ４、Ｒ５及びＲ６の内の水素ではない基は下記式（３）で表される基を表す。 In the above formula (1), R1 and R2 each represent an alkylene group having 1 to 5 carbon atoms, 2 to 4 groups out of 4 groups of R3, R4, R5 and R6 represent hydrogen, and R3 , R4, R5 and R6 which are not hydrogen represent a group represented by the following formula (3).
　上記式（１）中のＲ３、Ｒ４、Ｒ５及びＲ６の４個の基の全てが水素であってもよい。Ｒ３、Ｒ４、Ｒ５及びＲ６の４個の基の内の１個又は２個が下記式（３）で表される基であり、かつＲ３、Ｒ４、Ｒ５及びＲ６の４個の基の内の下記式（３）で表される基ではない基は水素であってもよい。 All of the four groups R3, R4, R5 and R6 in the above formula (1) may be hydrogen. One or two of the four groups of R3, R4, R5 and R6 are groups represented by the following formula (3), and among the four groups of R3, R4, R5 and R6 The group that is not a group represented by the following formula (3) may be hydrogen.
Figure JPOXMLDOC01-appb-C000002
 　上記式（３）中、Ｒ７は炭素数１～５のアルキレン基を表す。
Figure JPOXMLDOC01-appb-C000002
 In the above formula (3), R7 represents an alkylene group having 1 to 5 carbon atoms.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　上記式（２）中、Ｒ５１及びＲ５２はそれぞれ炭素数１～５のアルキレン基を表し、Ｒ５３、Ｒ５４、Ｒ５５、Ｒ５６、Ｒ５７及びＲ５８の６個の基の内の４～６個の基は水素を表し、Ｒ５３、Ｒ５４、Ｒ５５、Ｒ５６、Ｒ５７及びＲ５８の内の水素ではない基は、下記式（４）で表される基を表す。 In the above formula (2), R51 and R52 each represents an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R53, R54, R55, R56, R57 and R58 are hydrogen. The group which is not hydrogen among R53, R54, R55, R56, R57 and R58 represents a group represented by the following formula (4).
　上記式（２）中のＲ５３、Ｒ５４、Ｒ５５、Ｒ５６、Ｒ５７及びＲ５８の６個の基の全てが水素であってもよい。Ｒ５３、Ｒ５４、Ｒ５５、Ｒ５６、Ｒ５７及びＲ５８の６個の基の内の１個又は２個が下記式（４）で表される基であり、かつＲ５３、Ｒ５４、Ｒ５５、Ｒ５６、Ｒ５７及びＲ５８の内の下記式（４）で表される基ではない基は水素であってもよい。 All of the six groups of R53, R54, R55, R56, R57 and R58 in the above formula (2) may be hydrogen. One or two of the six groups of R53, R54, R55, R56, R57 and R58 are groups represented by the following formula (4), and R53, R54, R55, R56, R57 and R58. Of these, the group that is not a group represented by the following formula (4) may be hydrogen.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　上記式（４）中、Ｒ５９は炭素数１～５のアルキレン基を表す。 In the above formula (4), R59 represents an alkylene group having 1 to 5 carbon atoms.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　上記式（５）中、Ｒ１０１及びＲ１０２はそれぞれ炭素数１～５のアルキレン基を表す。Ｒ１０３、Ｒ１０４、Ｒ１０５、Ｒ１０６、Ｒ１０７、Ｒ１０８、Ｒ１０９及びＲ１１０の８個の基の内の６～８個の基は水素を表す。 In the above formula (5), R101 and R102 each represent an alkylene group having 1 to 5 carbon atoms. Six to eight groups out of the eight groups R103, R104, R105, R106, R107, R108, R109 and R110 represent hydrogen.
　上記式（５）中のＲ１０３、Ｒ１０４、Ｒ１０５、Ｒ１０６、Ｒ１０７、Ｒ１０８、Ｒ１０９及びＲ１１０の内の水素ではない基は、下記式（６）で表される基を表す。Ｒ１０３、Ｒ１０４、Ｒ１０５、Ｒ１０６、Ｒ１０７、Ｒ１０８、Ｒ１０９及びＲ１１０の８個の基の全てが水素であってもよい。Ｒ１０３、Ｒ１０４、Ｒ１０５、Ｒ１０６、Ｒ１０７、Ｒ１０８、Ｒ１０９及びＲ１１０の８個の基の内の１個又は２個が下記式（６）で表される基であり、かつＲ１０３、Ｒ１０４、Ｒ１０５、Ｒ１０６、Ｒ１０７、Ｒ１０８、Ｒ１０９及びＲ１１０の内の下記式（６）で表される基ではない基は水素であってもよい。 The non-hydrogen group in R103, R104, R105, R106, R107, R108, R109, and R110 in the above formula (5) represents a group represented by the following formula (6). All of the eight groups of R103, R104, R105, R106, R107, R108, R109 and R110 may be hydrogen. One or two of the eight groups of R103, R104, R105, R106, R107, R108, R109 and R110 are groups represented by the following formula (6), and R103, R104, R105, R106 , R107, R108, R109 and R110, which is not a group represented by the following formula (6), may be hydrogen.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　上記式（６）中、Ｒ１１１は炭素数１～５のアルキレン基を表す。 In the above formula (6), R111 represents an alkylene group having 1 to 5 carbon atoms.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　上記式（７）中、Ｒ１及びＲ２はそれぞれ炭素数１～５のアルキレン基を表す。 In the above formula (7), R1 and R2 each represent an alkylene group having 1 to 5 carbon atoms.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　上記式（８）中、Ｒ３及びＲ４はそれぞれ炭素数１～５のアルキレン基を表す。 In the above formula (8), R3 and R4 each represent an alkylene group having 1 to 5 carbon atoms.
　上記式（１）又は（２）で表される構造を有するエピスルフィド化合物は、チイラン基（エピスルフィド基）を少なくとも２つ有する。また、チイラン基を有する基が、ベンゼン環又はナフタレン環に結合されている。このような構造を有するので、異方性導電材料を加熱することにより、異方性導電材料を低温で速やかに硬化させることができる。なお、本明細書において、低温とは２００℃以下の温度を意味する。 The episulfide compound having a structure represented by the above formula (1) or (2) has at least two thiirane groups (episulfide groups). In addition, a group having a thiirane group is bonded to a benzene ring or a naphthalene ring. Since it has such a structure, the anisotropic conductive material can be rapidly cured at a low temperature by heating the anisotropic conductive material. In this specification, low temperature means a temperature of 200 ° C. or lower.
　上記式（１）、（２）、（５）、（７）又は（８）で表される構造を有するエピスルフィド化合物は、上記式（１）、（２）、（５）、（７）又は（８）中のチイラン基がエポキシ基である化合物に比べて、反応性が高い。これは、チイラン基はエポキシ基よりも、開環しやすく、反応性が高いためである。上記式（１）、（２）、（５）、（７）又は（８）で表される構造を有するエピスルフィド化合物は反応性が高いので、異方性導電材料を低温で速やかに硬化させることができる。特に、上記式（１）又は（２）で表される構造を有するエピスルフィド化合物は反応性がかなり高いので、異方性導電材料を低温で速やかに硬化させることができる。 The episulfide compound having the structure represented by the above formula (1), (2), (5), (7) or (8) is represented by the above formula (1), (2), (5), (7) or The reactivity is high compared with the compound whose thiirane group in (8) is an epoxy group. This is because a thiirane group is easier to open a ring and has higher reactivity than an epoxy group. Since the episulfide compound having the structure represented by the above formula (1), (2), (5), (7) or (8) has high reactivity, the anisotropic conductive material is rapidly cured at a low temperature. Can do. In particular, since an episulfide compound having a structure represented by the above formula (1) or (2) has a considerably high reactivity, an anisotropic conductive material can be rapidly cured at a low temperature.
　上記式（１）中のＲ１及びＲ２、上記式（２）中のＲ５１及びＲ５２、上記式（３）中のＲ７、及び上記式（４）中のＲ５９、上記式（５）中のＲ１０１及びＲ１０２、上記式（６）中のＲ１１１、上記式（７）中のＲ１及びＲ２、上記式（８）中のＲ３及びＲ４は、炭素数１～５のアルキレン基である。該アルキレン基の炭素数が５を超えると、上記エピスルフィド化合物の硬化速度が遅くなる傾向がある。 R1 and R2 in the above formula (1), R51 and R52 in the above formula (2), R7 in the above formula (3), R59 in the above formula (4), R101 in the above formula (5) and R102, R111 in the above formula (6), R1 and R2 in the above formula (7), and R3 and R4 in the above formula (8) are alkylene groups having 1 to 5 carbon atoms. If the alkylene group has more than 5 carbon atoms, the curing rate of the episulfide compound tends to be slow.
　上記式（１）中のＲ１及びＲ２、上記式（２）中のＲ５１及びＲ５２、上記式（３）中のＲ７、及び上記式（４）中のＲ５９、上記式（５）中のＲ１０１及びＲ１０２、上記式（６）中のＲ１１１、上記式（７）中のＲ１及びＲ２、上記式（８）中のＲ３及びＲ４はそれぞれ、炭素数１～３のアルキレン基であることが好ましく、メチレン基であることがより好ましい。上記アルキレン基は直鎖構造を有するアルキレン基であってもよく、分岐構造を有するアルキレン基であってもよい。 R1 and R2 in the above formula (1), R51 and R52 in the above formula (2), R7 in the above formula (3), R59 in the above formula (4), R101 in the above formula (5) and R102, R111 in the above formula (6), R1 and R2 in the above formula (7), and R3 and R4 in the above formula (8) are each preferably an alkylene group having 1 to 3 carbon atoms. More preferably, it is a group. The alkylene group may be an alkylene group having a straight chain structure or an alkylene group having a branched structure.
　上記（１）で表される構造は、下記式（１Ａ）で表される構造であることが好ましい。下記式（１Ａ）で表される構造を有するエピスルフィド化合物は、硬化性に優れている。 The structure represented by the above (1) is preferably a structure represented by the following formula (1A). An episulfide compound having a structure represented by the following formula (1A) is excellent in curability.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　上記式（１Ａ）中、Ｒ１及びＲ２はそれぞれ炭素数１～５のアルキレン基を表す。 In the above formula (1A), R1 and R2 each represent an alkylene group having 1 to 5 carbon atoms.
　上記式（１）で表される構造は、下記式（１Ｂ）で表される構造であることがより好ましい。下記式（１Ｂ）で表される構造を有するエピスルフィド化合物は、硬化性により一層優れている。 The structure represented by the above formula (1) is more preferably a structure represented by the following formula (1B). An episulfide compound having a structure represented by the following formula (1B) is more excellent in curability.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　上記（２）で表される構造は、下記式（２Ａ）で表される構造であることが好ましい。下記式（２Ａ）で表される構造を有するエピスルフィド化合物は、硬化性に優れている。 The structure represented by the above (2) is preferably a structure represented by the following formula (2A). An episulfide compound having a structure represented by the following formula (2A) is excellent in curability.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　上記式（２Ａ）中、Ｒ５１及びＲ５２はそれぞれ炭素数１～５のアルキレン基を表す。 In the above formula (2A), R51 and R52 each represent an alkylene group having 1 to 5 carbon atoms.
　上記式（２）で表される構造は、下記式（２Ｂ）で表される構造であることがより好ましい。下記式（２Ｂ）で表される構造を有するエピスルフィド化合物は、硬化性により一層優れている。 The structure represented by the above formula (2) is more preferably a structure represented by the following formula (2B). An episulfide compound having a structure represented by the following formula (2B) is more excellent in curability.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　上記エポキシ化合物は特に限定されない。エポキシ化合物として、従来公知のエポキシ化合物を使用できる。上記エポキシ化合物は、１種のみが用いられてもよく、２種以上が併用されてもよい。 The epoxy compound is not particularly limited. A conventionally well-known epoxy compound can be used as an epoxy compound. As for the said epoxy compound, only 1 type may be used and 2 or more types may be used together.
　上記エポキシ化合物としては、エポキシ基を有するフェノキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビフェノール型エポキシ樹脂、ナフタレン型エポキシ樹脂、フルオレン型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、アントラセン型エポキシ樹脂、アダマンタン骨格を有するエポキシ樹脂、トリシクロデカン骨格を有するエポキシ樹脂、及びトリアジン核を骨格に有するエポキシ樹脂等が挙げられる。 Examples of the epoxy compound include phenoxy resin having an epoxy group, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, biphenol type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, phenol aralkyl type epoxy. Examples thereof include a resin, a naphthol aralkyl type epoxy resin, a dicyclopentadiene type epoxy resin, an anthracene type epoxy resin, an epoxy resin having an adamantane skeleton, an epoxy resin having a tricyclodecane skeleton, and an epoxy resin having a triazine nucleus in the skeleton.
　上記エポキシ化合物の具体例としては、例えばエピクロルヒドリンと、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂又はビスフェノールＤ型エポキシ樹脂等とから誘導されるビスフェノール型エポキシ樹脂、並びにエピクロルヒドリンとフェノールノボラック又はクレゾールノボラックとから誘導されるエポキシノボラック樹脂が挙げられる。グリシジルアミン、グリシジルエステル、並びに脂環式又は複素環式等の１分子内に２個以上のオキシラン基を有する各種のエポキシ化合物を用いてもよい。 Specific examples of the epoxy compound include, for example, epichlorohydrin and bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol D type epoxy resin and the like, bisphenol type epoxy resin, and epichlorohydrin and phenol novolac or cresol novolak. And epoxy novolac resins derived from Various epoxy compounds having two or more oxirane groups in one molecule such as glycidylamine, glycidyl ester, and alicyclic or heterocyclic may be used.
　上記硬化性化合物は、上記式（１）、（２）、（５）、（７）又は（８）で表される構造におけるチイラン基をエポキシ基に置き換えた構造を有するエポキシ化合物を含んでいてもよい。この場合に、上記式（３）、（４）及び（６）で表される構造も、チイラン基をエポキシ基に置き換えた構造であることが好ましい。上記硬化性化合物は、下記式（１１）又は（１２）で表されるエポキシ化合物を含んでいてもよい。上記硬化性化合物は、上記式（１）又は（２）で表されるエピスルフィド化合物と、下記式（１１）又は（１２）で表されるエポキシ化合物とを含んでいることが好ましい。 The curable compound includes an epoxy compound having a structure in which the thiirane group in the structure represented by the formula (1), (2), (5), (7) or (8) is replaced with an epoxy group. Also good. In this case, the structures represented by the above formulas (3), (4) and (6) are also preferably structures in which the thiirane group is replaced with an epoxy group. The said curable compound may contain the epoxy compound represented by following formula (11) or (12). The curable compound preferably contains an episulfide compound represented by the above formula (1) or (2) and an epoxy compound represented by the following formula (11) or (12).
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　上記式（１１）中、Ｒ１１及びＲ１２はそれぞれ炭素数１～５のアルキレン基を表し、Ｒ１３、Ｒ１４、Ｒ１５及びＲ１６の４個の基の内の２～４個の基は水素を表し、Ｒ１３、Ｒ１４、Ｒ１５及びＲ１６の内の水素ではない基は下記式（１３）で表される基を表す。 In the above formula (11), R11 and R12 each represent an alkylene group having 1 to 5 carbon atoms, 2 to 4 groups out of 4 groups of R13, R14, R15 and R16 represent hydrogen, and R13 , R14, R15 and R16, which are not hydrogen, represent a group represented by the following formula (13).
　上記式（１１）中のＲ１３、Ｒ１４、Ｒ１５及びＲ１６の４個の基の全てが水素であってもよい。Ｒ１３、Ｒ１４、Ｒ１５及びＲ１６の４個の基の内の１個又は２個が下記式（１３）で表される基であり、かつＲ１３、Ｒ１４、Ｒ１５及びＲ１６の４個の基の内の下記式（１３）で表される基ではない基は水素であってもよい。 All four groups of R13, R14, R15, and R16 in the above formula (11) may be hydrogen. One or two of the four groups of R13, R14, R15 and R16 is a group represented by the following formula (13), and among the four groups of R13, R14, R15 and R16 The group that is not a group represented by the following formula (13) may be hydrogen.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　上記式（１３）中、Ｒ１７は炭素数１～５のアルキレン基を表す。 In the above formula (13), R17 represents an alkylene group having 1 to 5 carbon atoms.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　上記式（１２）中、Ｒ６１及びＲ６２はそれぞれ炭素数１～５のアルキレン基を表し、Ｒ６３、Ｒ６４、Ｒ６５、Ｒ６６、Ｒ６７及びＲ６８の６個の基の内の４～６個の基は水素を表し、Ｒ６３、Ｒ６４、Ｒ６５、Ｒ６６、Ｒ６７及びＲ６８の内の水素ではない基は、下記式（１４）で表される基を表す。 In the above formula (12), R61 and R62 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R63, R64, R65, R66, R67 and R68 are hydrogen. The group which is not hydrogen among R63, R64, R65, R66, R67 and R68 represents a group represented by the following formula (14).
　上記式（１２）中のＲ６３、Ｒ６４、Ｒ６５、Ｒ６６、Ｒ６７及びＲ６８の６個の基の全てが水素であってもよい。Ｒ６３、Ｒ６４、Ｒ６５、Ｒ６６、Ｒ６７及びＲ６８の６個の基の内の１個又は２個が下記式（１４）で表される基であり、かつＲ６３、Ｒ６４、Ｒ６５、Ｒ６６、Ｒ６７及びＲ６８の６個の基の内の下記式（１４）で表される基ではない基は水素であってもよい。 All of the six groups of R63, R64, R65, R66, R67 and R68 in the above formula (12) may be hydrogen. One or two of the six groups R63, R64, R65, R66, R67 and R68 are groups represented by the following formula (14), and R63, R64, R65, R66, R67 and R68. Of these six groups, a group that is not a group represented by the following formula (14) may be hydrogen.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　上記式（１４）中、Ｒ６９は炭素数１～５のアルキレン基を表す。 In the above formula (14), R69 represents an alkylene group having 1 to 5 carbon atoms.
　上記式（１１）中のＲ１１及びＲ１２、上記式（１２）中のＲ６１及びＲ６２、上記式（１３）中のＲ１７、及び上記式（１４）中のＲ６９は、炭素数１～５のアルキレン基である。該アルキレン基の炭素数が５を超えると、上記式（１１）又は（１２）で表されるエポキシ化合物の硬化速度が遅くなりやすい。 R11 and R12 in the formula (11), R61 and R62 in the formula (12), R17 in the formula (13), and R69 in the formula (14) are alkylene groups having 1 to 5 carbon atoms. It is. If the alkylene group has more than 5 carbon atoms, the curing rate of the epoxy compound represented by the above formula (11) or (12) tends to be slow.
　上記式（１１）中のＲ１１及びＲ１２、上記式（１２）中のＲ６１及びＲ６２、上記式（１３）中のＲ１７、及び上記式（１４）中のＲ６９はそれぞれ、炭素数１～３のアルキレン基であることが好ましく、メチレン基であることがより好ましい。上記アルキレン基は直鎖構造を有するアルキレン基であってもよく、分岐構造を有するアルキレン基であってもよい。 R11 and R12 in the above formula (11), R61 and R62 in the above formula (12), R17 in the above formula (13), and R69 in the above formula (14) are each an alkylene having 1 to 3 carbon atoms. It is preferably a group, more preferably a methylene group. The alkylene group may be an alkylene group having a straight chain structure or an alkylene group having a branched structure.
　上記（１１）で表される構造は、下記式（１１Ａ）で表される構造であることが好ましい。下記式（１１Ａ）で表される構造を有するエポキシ化合物は、市販されており、容易に入手できる。 The structure represented by the above (11) is preferably a structure represented by the following formula (11A). An epoxy compound having a structure represented by the following formula (11A) is commercially available and can be easily obtained.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　上記式（１１Ａ）中、Ｒ１１及びＲ１２はそれぞれ炭素数１～５のアルキレン基を表す。 In the above formula (11A), R11 and R12 each represent an alkylene group having 1 to 5 carbon atoms.
　上記式（１１）で表される構造は、下記式（１１Ｂ）で表される構造であることがより好ましい。下記式（１１Ｂ）で表される構造を有するエポキシ化合物は、レゾルシノールジグリシジルエーテルである。レゾルシノールジグリシジルエーテルは市販されており、容易に入手できる。 The structure represented by the above formula (11) is more preferably a structure represented by the following formula (11B). The epoxy compound having a structure represented by the following formula (11B) is resorcinol diglycidyl ether. Resorcinol diglycidyl ether is commercially available and can be easily obtained.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　上記（１２）で表される構造は、下記式（１２Ａ）で表される構造であることが好ましい。下記式（１２Ａ）で表される構造を有するエポキシ化合物は、容易に入手できる。 The structure represented by (12) is preferably a structure represented by the following formula (12A). An epoxy compound having a structure represented by the following formula (12A) can be easily obtained.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　上記式（１２Ａ）中、Ｒ６１及びＲ６２はそれぞれ炭素数１～５のアルキレン基を表す。 In the above formula (12A), R61 and R62 each represent an alkylene group having 1 to 5 carbon atoms.
　上記式（１２）で表される構造は、下記式（１２Ｂ）で表される構造であることがより好ましい。下記式（１２Ｂ）で表される構造を有するエポキシ化合物は、容易に入手できる。 The structure represented by the above formula (12) is more preferably a structure represented by the following formula (12B). An epoxy compound having a structure represented by the following formula (12B) can be easily obtained.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　上記式（１）又は（２）で表される構造を有するエピスルフィド化合物と、上記式（１１）又は（１２）で表されるエポキシ化合物との混合物（以下、混合物Ａと略記することがある）の合計１００重量％中、上記式（１）又は（２）で表される構造を有するエピスルフィド化合物の含有量が１０～５０重量％、かつ上記式（１１）又は（１２）で表されるエポキシ化合物の含有量が９０～５０重量％であることが好ましく、上記式（１）又は（２）で表される構造を有するエピスルフィド化合物の含有量が２０～３０重量％、かつ上記式（１１）又は（１２）で表されるエポキシ化合物の含有量が８０～７０重量％であることがより好ましい。 A mixture of an episulfide compound having a structure represented by the above formula (1) or (2) and an epoxy compound represented by the above formula (11) or (12) (hereinafter sometimes abbreviated as “mixture A”) In which the content of the episulfide compound having the structure represented by the formula (1) or (2) is 10 to 50% by weight, and the epoxy represented by the formula (11) or (12) The content of the compound is preferably 90 to 50% by weight, the content of the episulfide compound having a structure represented by the above formula (1) or (2) is 20 to 30% by weight, and the above formula (11) Alternatively, the content of the epoxy compound represented by (12) is more preferably 80 to 70% by weight.
　上記式（１）又は（２）で表される構造を有するエピスルフィド化合物の含有量が少なすぎると、上記混合物Ａの硬化速度が遅くなる傾向がある。上記式（１）又は（２）で表される構造を有するエピスルフィド化合物の含有量が多すぎると、上記混合物Ａの粘度が高くなりすぎたり、上記混合物Ａが固体になったりすることがある。 When the content of the episulfide compound having the structure represented by the above formula (1) or (2) is too small, the curing rate of the mixture A tends to be slow. When there is too much content of the episulfide compound which has a structure represented by the said Formula (1) or (2), the viscosity of the said mixture A will become high too much, or the said mixture A may become a solid.
　上記混合物Ａの製造方法は特に限定されない。この製造方法として、例えば、上記式（１１）又は（１２）で表されるエポキシ化合物を用意し、該エポキシ化合物の一部のエポキシ基をチイラン基に変換する製造方法が挙げられる。 The method for producing the mixture A is not particularly limited. Examples of the production method include a production method in which an epoxy compound represented by the above formula (11) or (12) is prepared and a part of the epoxy group of the epoxy compound is converted into a thiirane group.
　上記混合物Ａの製造方法は、硫化剤を含む第１の溶液に、上記式（１１）又は（１２）で表されるエポキシ化合物又は該エポキシ化合物を含む溶液を連続的又は断続的に添加した後、硫化剤を含む第２の溶液を連続的又は断続的にさらに添加する方法が好ましい。この方法により、上記エポキシ化合物の一部のエポキシ基をチイラン基に変換できる。この結果、上記混合物Ａを得ることができる。上記硫化剤としては、チオシアン酸塩類、チオ尿素類、ホスフィンサルファイド、ジメチルチオホルムアミド及びＮ－メチルベンゾチアゾール－２－チオン等が挙げられる。上記チオシアン酸塩類としては、チオシアン酸ナトリウム、チオシアン酸カリウム及びチオシアン酸ナトリウム等が挙げられる。 In the method for producing the mixture A, the epoxy compound represented by the above formula (11) or (12) or the solution containing the epoxy compound is continuously or intermittently added to the first solution containing the sulfurizing agent. A method in which the second solution containing the sulfurizing agent is further added continuously or intermittently is preferable. By this method, some epoxy groups of the epoxy compound can be converted into thiirane groups. As a result, the mixture A can be obtained. Examples of the sulfurizing agent include thiocyanates, thioureas, phosphine sulfide, dimethylthioformamide, N-methylbenzothiazole-2-thione, and the like. Examples of the thiocyanates include sodium thiocyanate, potassium thiocyanate, and sodium thiocyanate.
　上記硬化性化合物は、下記式（２１）で表される構造を有するエポキシ化合物の単量体、該エポキシ化合物が少なくとも２個結合された多量体、又は該単量体と該多量体との混合物を含んでいてもよい。 The curable compound is a monomer of an epoxy compound having a structure represented by the following formula (21), a multimer in which at least two epoxy compounds are bonded, or a mixture of the monomer and the multimer. May be included.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　上記式（２１）中、Ｒ１は炭素数１～５のアルキレン基を表し、Ｒ２は炭素数１～５のアルキレン基を表し、Ｒ３は水素原子、炭素数１～５のアルキル基又は下記式（２２）で表される構造を表し、Ｒ４は水素原子、炭素数１～５のアルキル基又は下記式（２３）で表される構造を表す。 In the above formula (21), R1 represents an alkylene group having 1 to 5 carbon atoms, R2 represents an alkylene group having 1 to 5 carbon atoms, R3 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the following formula ( 22), R4 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a structure represented by the following formula (23).
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　上記式（２２）中、Ｒ５は炭素数１～５のアルキレン基を表す。 In the above formula (22), R5 represents an alkylene group having 1 to 5 carbon atoms.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　上記式（２３）中、Ｒ６は炭素数１～５のアルキレン基を表す。 In the above formula (23), R6 represents an alkylene group having 1 to 5 carbon atoms.
　上記式（２１）で表される構造を有するエポキシ化合物は、不飽和二重結合と、少なくとも２個のエポキシ基とを有することを特徴とする。上記式（２１）で表される構造を有するエポキシ化合物の使用により、異方性導電材料を低温で速やかに硬化させることができる。 The epoxy compound having a structure represented by the above formula (21) has an unsaturated double bond and at least two epoxy groups. By using an epoxy compound having a structure represented by the above formula (21), the anisotropic conductive material can be rapidly cured at a low temperature.
　上記硬化性化合物は、下記式（３１）で表される構造を有する化合物の単量体、該化合物が少なくとも２個結合された多量体、又は該単量体と該多量体との混合物を含んでいてもよい。 The curable compound includes a monomer having a structure represented by the following formula (31), a multimer in which at least two of the compounds are bonded, or a mixture of the monomer and the multimer. You may go out.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　上記式（３１）中、Ｒ１は水素原子もしくは炭素数１～５のアルキル基又は下記式（３２）で表される構造を表し、Ｒ２は炭素数１～５のアルキレン基を表し、Ｒ３は炭素数１～５のアルキレン基を表し、Ｘ１は酸素原子又は硫黄原子を表し、Ｘ２は酸素原子又は硫黄原子を表す。 In the above formula (31), R1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms or a structure represented by the following formula (32), R2 represents an alkylene group having 1 to 5 carbon atoms, and R3 represents carbon X 1 represents an oxygen atom or a sulfur atom, and X 2 represents an oxygen atom or a sulfur atom.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　上記式（３２）中、Ｒ４は炭素数１～５のアルキレン基を表し、Ｘ３は酸素原子又は硫黄原子を表す。 In the above formula (32), R4 represents an alkylene group having 1 to 5 carbon atoms, and X3 represents an oxygen atom or a sulfur atom.
　上記式（３１）で表される構造を有する化合物に相当するエポキシ化合物は、例えば、以下のようにして合成できる。 The epoxy compound corresponding to the compound having the structure represented by the above formula (31) can be synthesized as follows, for example.
　原料化合物である、水酸基を有するフルオレン化合物と、エピクロルヒドリンと、水酸化ナトリウムと、メタノールとを混合し、冷却し、反応させる。その後、水酸化ナトリウム水溶液を滴下する。滴下の後、さらに反応させ、反応液を得る。次に、反応液に水とトルエンとを加え、トルエン層を取り出す。トルエン層を水で洗浄した後、乾燥し、水と溶媒とを除去する。このようにして、上記式（３１）で表される構造を有する化合物に相当するエポキシ化合物を容易に得ることができる。なお、原料化合物である、水酸基を有するフルオレン化合物は、例えばＪＦＥケミカル社等から市販されている。 A raw material compound, a fluorene compound having a hydroxyl group, epichlorohydrin, sodium hydroxide, and methanol are mixed, cooled, and reacted. Thereafter, an aqueous sodium hydroxide solution is dropped. After dripping, it is further reacted to obtain a reaction solution. Next, water and toluene are added to the reaction solution, and the toluene layer is taken out. The toluene layer is washed with water and then dried to remove water and the solvent. In this way, an epoxy compound corresponding to the compound having the structure represented by the formula (31) can be easily obtained. In addition, the fluorene compound which has a hydroxyl group which is a raw material compound is marketed, for example from JFE Chemical Company etc., for example.
　また、上記式（３１）で表される構造を有する化合物に相当するチイラン基含有化合物は、上記式（３１）で表される構造を有する化合物に相当するエポキシ化合物のエポキシ基を、チイラン基に変換することにより合成できる。例えば、上記硫化剤を含む溶液に、原料化合物であるエポキシ化合物又は該エポキシ化合物を含む溶液を添加した後、上記硫化剤を含む溶液をさらに添加することにより、エポキシ基をチイラン基に容易に変換できる。 Further, the thiirane group-containing compound corresponding to the compound having the structure represented by the above formula (31) has the epoxy group of the epoxy compound corresponding to the compound having the structure represented by the above formula (31) as a thiirane group. It can be synthesized by conversion. For example, an epoxy compound as a raw material compound or a solution containing the epoxy compound is added to the solution containing the sulfurizing agent, and then the solution containing the sulfurizing agent is further added to easily convert the epoxy group to a thiirane group. it can.
　上記硬化性化合物は、窒素原子を含む複素環を有するエポキシ化合物を含んでいてもよい。上記窒素原子を含む複素環を有するエポキシ化合物は、下記式（４１）で表されるエポキシ化合物、又は下記式（４２）で表されるエポキシ化合物であることが好ましい。このような硬化性化合物の使用により、異方性導電材料の硬化速度をより一層速くし、異方性導電材料の硬化物の耐熱性をより一層高めることができる。 The curable compound may include an epoxy compound having a heterocyclic ring containing a nitrogen atom. The epoxy compound having a heterocyclic ring containing a nitrogen atom is preferably an epoxy compound represented by the following formula (41) or an epoxy compound represented by the following formula (42). By using such a curable compound, the curing rate of the anisotropic conductive material can be further increased, and the heat resistance of the cured product of the anisotropic conductive material can be further enhanced.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　上記式（４１）中、Ｒ１～Ｒ３はそれぞれ炭素数１～５のアルキレン基を表し、Ｚはエポキシ基又はヒドロキシメチル基を表す。Ｒ２１～Ｒ２３は同一であってもよく、異なっていてもよい。 In the above formula (41), R1 to R3 each represent an alkylene group having 1 to 5 carbon atoms, and Z represents an epoxy group or a hydroxymethyl group. R21 to R23 may be the same or different.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　上記式（４２）中、Ｒ１～Ｒ３はそれぞれ炭素数１～５のアルキレン基を示し、ｐ、ｑ及びｒはそれぞれ１～５の整数を表し、Ｒ４～Ｒ６はそれぞれ炭素数１～５のアルキレン基を表す。Ｒ１～Ｒ３は同一であってもよく、異なっていてもよい。ｐ、ｑ及びｒは同一であってもよく、異なっていてもよい。Ｒ４～６は同一であってもよく、異なっていてもよい。 In the above formula (42), R1 to R3 each represents an alkylene group having 1 to 5 carbon atoms, p, q and r each represents an integer of 1 to 5, and R4 to R6 each represents an alkylene group having 1 to 5 carbon atoms. Represents a group. R1 to R3 may be the same or different. p, q and r may be the same or different. R4 to R6 may be the same or different.
　上記窒素原子を含む複素環を有するエポキシ化合物は、トリグリシジルイソシアヌレート、又はトリスヒドロキシエチルイソシアヌレートトリグリシジルエーテルであることが好ましい。これらの硬化性化合物の使用により、異方性導電材料の硬化速度をさらに一層速くすることができる。 The epoxy compound having a heterocyclic ring containing a nitrogen atom is preferably triglycidyl isocyanurate or trishydroxyethyl isocyanurate triglycidyl ether. By using these curable compounds, the curing rate of the anisotropic conductive material can be further increased.
　上記硬化性化合物は、芳香族環を有するエポキシ化合物を含むことが好ましい。芳香族環を有するエポキシ化合物の使用により、異方性導電材料の硬化速度をより一層速くし、異方性導電材料を塗布しやすくすることができる。異方性導電材料の塗布性をより一層高める観点からは、上記芳香族環は、ベンゼン環、ナフタレン環又はアントラセン環であることが好ましい。上記芳香族環を有するエポキシ化合物としては、レゾルシノールジグリシジルエーテル又は１，６－ナフタレンジグリシジルエーテルが挙げられる。なかでも、上記式（１１Ｂ）で表される構造を有するレゾルシノールジグリシジルエーテルが特に好ましい。レゾルシノールジグリシジルエーテルの使用により、異方性導電材料の硬化速度を速くし、異方性導電材料を塗布しやすくすることができる。 The curable compound preferably contains an epoxy compound having an aromatic ring. By using an epoxy compound having an aromatic ring, the curing rate of the anisotropic conductive material can be further increased and the anisotropic conductive material can be easily applied. From the viewpoint of further improving the applicability of the anisotropic conductive material, the aromatic ring is preferably a benzene ring, a naphthalene ring or an anthracene ring. Examples of the epoxy compound having an aromatic ring include resorcinol diglycidyl ether and 1,6-naphthalenediglycidyl ether. Among these, resorcinol diglycidyl ether having a structure represented by the above formula (11B) is particularly preferable. By using resorcinol diglycidyl ether, the curing rate of the anisotropic conductive material can be increased and the anisotropic conductive material can be easily applied.
　［光硬化性化合物］
　本発明に係る硬化性化合物は、光の照射によっても硬化するように、光硬化性化合物を含有していてもよい。光の照射により硬化性化合物を半硬化させ、硬化性化合物の流動性を低下させることができる。 [Photocurable compound]
The curable compound according to the present invention may contain a photocurable compound so as to be cured by light irradiation. The curable compound can be semi-cured by light irradiation, and the fluidity of the curable compound can be reduced.
　上記光硬化性化合物としては特に限定されず、（メタ）アクリル樹脂及び環状エーテル基含有樹脂等が挙げられる。 The photocurable compound is not particularly limited, and examples thereof include (meth) acrylic resins and cyclic ether group-containing resins.
　上記（メタ）アクリル樹脂として、例えば、（メタ）アクリル酸と水酸基を有する化合物とを反応させて得られるエステル化合物、（メタ）アクリル酸とエポキシ化合物とを反応させて得られるエポキシ（メタ）アクリレート、イソシアネートに水酸基を有する（メタ）アクリル酸誘導体を反応させて得られるウレタン（メタ）アクリレート等が好適に用いられる。 Examples of the (meth) acrylic resin include an ester compound obtained by reacting (meth) acrylic acid and a compound having a hydroxyl group, and an epoxy (meth) acrylate obtained by reacting (meth) acrylic acid and an epoxy compound. Urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with isocyanate is preferably used.
　上述した光硬化性化合物以外の光硬化性化合物が含まれる場合には、該光硬化性化合物は、架橋性化合物であってもよく、非架橋性化合物であってもよい。 When a photocurable compound other than the photocurable compounds described above is included, the photocurable compound may be a crosslinkable compound or a non-crosslinkable compound.
　上記架橋性化合物の具体例としては、例えば、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、グリセリンメタクリレートアクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパントリメタクリレート、（メタ）アクリル酸アリル、（メタ）アクリル酸ビニル、ジビニルベンゼン、ポリエステル（メタ）アクリレート、及びウレタン（メタ）アクリレート等が挙げられる。 Specific examples of the crosslinkable compound include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, (poly ) Ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, glycerol methacrylate acrylate, pentaerythritol tri (meth) acrylate, tri Examples include methylolpropane trimethacrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, polyester (meth) acrylate, and urethane (meth) acrylate.
　上記非架橋性化合物の具体例としては、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート及びテトラデシル（メタ）アクリレート等が挙げられる。 Specific examples of the non-crosslinkable compound include ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) ) Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (Meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, and the like.
　［光及び熱硬化性化合物］
　上記硬化性化合物が例えば熱硬化性化合物及び光重合性化合物を含む場合には、異方性導電材料の硬化を容易に制御したり、接続構造体の導通信頼性をより一層高めたりする観点からは、上記硬化性化合物は、エポキシ基及びチイラン基の内の少なくとも一種の基と、（メタ）アクリロイル基とを有する光及び熱硬化性化合物を含むことが好ましい。上記硬化性化合物は、エポキシ基と、（メタ）アクリロイル基とを有する光及び熱硬化性化合物（以下、部分（メタ）アクリレート化エポキシ樹脂ともいう）を含むことが好ましい。上記（メタ）アクリロイルは、アクリロイル又はメタクリロイルを意味する。上記（メタ）アクリレートは、アクリレート又はメタクリレートを意味する。 [Light and thermosetting compounds]
In the case where the curable compound contains, for example, a thermosetting compound and a photopolymerizable compound, from the viewpoint of easily controlling the curing of the anisotropic conductive material or further improving the conduction reliability of the connection structure. The curable compound preferably contains a light and thermosetting compound having at least one of an epoxy group and a thiirane group and a (meth) acryloyl group. It is preferable that the said curable compound contains the light and thermosetting compound (henceforth a partial (meth) acrylated epoxy resin) which has an epoxy group and a (meth) acryloyl group. The (meth) acryloyl means acryloyl or methacryloyl. The (meth) acrylate means acrylate or methacrylate.
　上記部分（メタ）アクリレート化エポキシ樹脂は、例えば、エポキシ樹脂と（メタ）アクリル酸とを、常法に従って塩基性触媒の存在下で反応することにより得られる。エポキシ基の２０％以上が（メタ）アクリロイル基に変換され（転化率）、部分（メタ）アクリル化されていることが好ましい。エポキシ基の５０％が（メタ）アクリロイル基に変換されていることがより好ましい。 The partial (meth) acrylated epoxy resin can be obtained, for example, by reacting an epoxy resin and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method. It is preferable that 20% or more of the epoxy groups are converted to (meth) acryloyl groups (conversion rate) and partially (meth) acrylated. More preferably, 50% of the epoxy groups are converted to (meth) acryloyl groups.
　異方性導電材料の硬化性を高める観点からは、上記硬化性化合物１００重量％中、上記部分（メタ）アクリレート化エポキシ樹脂の含有量の好ましい下限は０．１重量％、より好ましい下限は０．５重量％、好ましい上限は２重量％、より好ましい上限は１．５重量％である。 From the viewpoint of increasing the curability of the anisotropic conductive material, the preferable lower limit of the content of the partially (meth) acrylated epoxy resin is 0.1% by weight and the more preferable lower limit is 0 in 100% by weight of the curable compound. 0.5 wt%, the preferred upper limit is 2 wt%, and the more preferred upper limit is 1.5 wt%.
　上記エポキシ（メタ）アクリレートとしては、ビスフェノール型エポキシ（メタ）アクリレート、クレゾールノボラック型エポキシ（メタ）アクリレート、カルボン酸無水物変性エポキシ（メタ）アクリレート、及びフェノールノボラック型エポキシ（メタ）アクリレート等が挙げられる。 Examples of the epoxy (meth) acrylate include bisphenol type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, carboxylic acid anhydride-modified epoxy (meth) acrylate, and phenol novolac type epoxy (meth) acrylate. .
　（熱硬化剤）
　上記熱硬化剤は特に限定されない。上記熱硬化剤として、従来公知の熱硬化剤を用いることができる。上記熱硬化剤としては、イミダゾール硬化剤、アミン硬化剤、フェノール硬化剤、ポリチオール硬化剤及び酸無水物等が挙げられる。上記熱硬化剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。 (Thermosetting agent)
The said thermosetting agent is not specifically limited. A conventionally known thermosetting agent can be used as the thermosetting agent. Examples of the thermosetting agent include imidazole curing agents, amine curing agents, phenol curing agents, polythiol curing agents, and acid anhydrides. As for the said thermosetting agent, only 1 type may be used and 2 or more types may be used together.
　異方性導電材料を低温でより一層速やかに硬化させることができるので、上記熱硬化剤は、イミダゾール硬化剤、ポリチオール硬化剤又はアミン硬化剤であることが好ましい。また、異方性導電材料の保存安定性を高めることができるので、潜在性の硬化剤が好ましい。該潜在性の硬化剤は、潜在性イミダゾール硬化剤、潜在性ポリチオール硬化剤又は潜在性アミン硬化剤であることが好ましい。上記熱硬化剤は、ポリウレタン樹脂又はポリエステル樹脂等の高分子物質で被覆されていてもよい。 Since the anisotropic conductive material can be cured more rapidly at a low temperature, the thermosetting agent is preferably an imidazole curing agent, a polythiol curing agent or an amine curing agent. In addition, a latent curing agent is preferable because the storage stability of the anisotropic conductive material can be improved. The latent curing agent is preferably a latent imidazole curing agent, a latent polythiol curing agent or a latent amine curing agent. The thermosetting agent may be coated with a polymer material such as polyurethane resin or polyester resin.
　上記イミダゾール硬化剤としては、特に限定されず、２－メチルイミダゾール、２－エチル－４－メチルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－シアノエチル－２－フェニルイミダゾリウムトリメリテート、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン及び２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジンイソシアヌル酸付加物等が挙げられる。 The imidazole curing agent is not particularly limited, and 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine and 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s- Examples include triazine isocyanuric acid adducts.
　上記ポリチオール硬化剤としては、特に限定されず、トリメチロールプロパン　トリス－３－メルカプトプロピオネート、ペンタエリスリトール　テトラキス－３－メルカプトプロピオネート及びジペンタエリスリトール　ヘキサ－３－メルカプトプロピオネート等が挙げられる。 The polythiol curing agent is not particularly limited, and examples include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate. .
　上記アミン硬化剤としては、特に限定されず、ヘキサメチレンジアミン、オクタメチレンジアミン、デカメチレンジアミン、３，９－ビス（３－アミノプロピル）－２，４，８，１０－テトラスピロ［５．５］ウンデカン、ビス（４－アミノシクロヘキシル）メタン、メタフェニレンジアミン及びジアミノジフェニルスルホン等が挙げられる。 The amine curing agent is not particularly limited, and hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5]. Examples include undecane, bis (4-aminocyclohexyl) methane, metaphenylenediamine, and diaminodiphenylsulfone.
　上記熱硬化剤の含有量は特に限定されない。上記硬化性化合物の合計１００重量部に対して、上記熱硬化剤の含有量の好ましい下限は５重量部、より好ましい下限は１０重量部、好ましい上限は３０重量部、より好ましい上限は２０重量部である。上記熱硬化剤の含有量が上記好ましい下限及び上限を満たすと、異方性導電材料を充分に熱硬化させることができる。 The content of the thermosetting agent is not particularly limited. A preferable lower limit of the content of the thermosetting agent is 5 parts by weight, a more preferable lower limit is 10 parts by weight, a preferable upper limit is 30 parts by weight, and a more preferable upper limit is 20 parts by weight with respect to a total of 100 parts by weight of the curable compound. It is. If content of the said thermosetting agent satisfy | fills the said preferable minimum and upper limit, an anisotropic conductive material can fully be thermosetted.
　（光硬化開始剤）
　上記光硬化開始剤は特に限定されない。上記光硬化開始剤として、従来公知の光硬化開始剤を用いることができる。上記光硬化開始剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。 (Photocuring initiator)
The photocuring initiator is not particularly limited. A conventionally known photocuring initiator can be used as the photocuring initiator. As for the said photocuring initiator, only 1 type may be used and 2 or more types may be used together.
　上記光硬化開始剤としては、特に限定されず、アセトフェノン光硬化開始剤、ベンゾフェノン光硬化開始剤、チオキサントン、ケタール光硬化開始剤、ハロゲン化ケトン、アシルホスフィノキシド及びアシルホスフォナート等が挙げられる。 The photocuring initiator is not particularly limited, and examples thereof include acetophenone photocuring initiator, benzophenone photocuring initiator, thioxanthone, ketal photocuring initiator, halogenated ketone, acyl phosphinoxide, and acyl phosphonate. .
　上記アセトフェノン光硬化開始剤の具体例としては、４－（２－ヒドロキシエトキシ）フェニル（２－ヒドロキシ－２－プロピル）ケトン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、メトキシアセトフェノン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、及び２－ヒドロキシ－２－シクロヘキシルアセトフェノン等が挙げられる。上記ケタール光硬化開始剤の具体例としては、ベンジルジメチルケタール等が挙げられる。 Specific examples of the acetophenone photocuring initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, methoxy Examples include acetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-2-cyclohexylacetophenone. Specific examples of the ketal photocuring initiator include benzyldimethyl ketal.
　上記光硬化開始剤の含有量は特に限定されない。上記硬化性化合物の合計１００重量部に対して、上記光硬化開始剤の含有量の好ましい下限は０．１重量部、より好ましい下限は０．２重量部、好ましい上限は２重量部、より好ましい上限は１重量部である。上記光硬化開始剤の含有量が上記好ましい下限及び上限を満たすと、異方性導電材料を適度に光硬化させることができる。異方性導電材料に光を照射し、Ｂステージ化することにより、異方性導電材料の流動を抑制できる。また、異方性導電材料に光を照射し、半硬化させることにより、異方性導電材料の流動を抑制できる。 The content of the photocuring initiator is not particularly limited. The preferable lower limit of the content of the photocuring initiator is 0.1 parts by weight, the more preferable lower limit is 0.2 parts by weight, and the preferable upper limit is 2 parts by weight with respect to the total of 100 parts by weight of the curable compound. The upper limit is 1 part by weight. If content of the said photocuring initiator satisfy | fills the said preferable minimum and upper limit, an anisotropic conductive material can be photocured moderately. By irradiating the anisotropic conductive material with light to form a B stage, the flow of the anisotropic conductive material can be suppressed. Moreover, the flow of the anisotropic conductive material can be suppressed by irradiating the anisotropic conductive material with light and semi-curing the light.
　（導電性粒子）
　本発明に係る異方性導電材料に含まれている導電性粒子として、例えば、電極間を電気的に接続できる従来公知の導電性粒子が用いられる。上記導電性粒子は、外表面に導電層を有する粒子であることが好ましい。上記導電性粒子は、導電層の表面に絶縁粒子が付着していたり、導電層の表面が絶縁層により被覆されていたりしてもよい。この場合には、電極の接続の際の加圧により、絶縁粒子又は絶縁層が取り除かれる。 (Conductive particles)
As the conductive particles contained in the anisotropic conductive material according to the present invention, for example, conventionally known conductive particles capable of electrically connecting the electrodes are used. The conductive particles are preferably particles having a conductive layer on the outer surface. The conductive particles may have insulating particles attached to the surface of the conductive layer, or the surface of the conductive layer may be covered with an insulating layer. In this case, the insulating particles or the insulating layer is removed by pressurization when the electrodes are connected.
　上記導電性粒子としては、例えば、有機粒子、無機粒子、有機無機ハイブリッド粒子、もしくは金属粒子等の表面が導電層で被覆された導電性粒子、並びに実質的に金属のみで構成される金属粒子等が挙げられる。上記導電層は特に限定されない。上記導電層としては、金層、銀層、銅層、ニッケル層、パラジウム層又は錫を含有する導電層等が挙げられる。 Examples of the conductive particles include organic particles, inorganic particles, organic-inorganic hybrid particles, or conductive particles whose surfaces are covered with a conductive layer, and metal particles that are substantially composed of only metal. Is mentioned. The conductive layer is not particularly limited. Examples of the conductive layer include a gold layer, a silver layer, a copper layer, a nickel layer, a palladium layer, or a conductive layer containing tin.
　上記異方性導電材料１００重量％中、上記導電性粒子の含有量は１～１９重量％の範囲内である。上記導電性粒子の含有量の好ましい下限は５重量％、好ましい上限は１５重量％、より好ましい上限は１０重量％である。上記導電性粒子の含有量が上記範囲内にある場合には、接続されるべき上下の電極間に導電性粒子を容易に配置できる。さらに、接続されてはならない隣接する電極間が複数の導電性粒子を介して電気的に接続され難くなる。すなわち、隣り合う電極間の短絡を防止できる。 In 100% by weight of the anisotropic conductive material, the content of the conductive particles is in the range of 1 to 19% by weight. The minimum with preferable content of the said electroconductive particle is 5 weight%, a preferable upper limit is 15 weight%, and a more preferable upper limit is 10 weight%. When the content of the conductive particles is within the above range, the conductive particles can be easily arranged between the upper and lower electrodes to be connected. Furthermore, it becomes difficult to electrically connect adjacent electrodes that should not be connected via a plurality of conductive particles. That is, a short circuit between adjacent electrodes can be prevented.
　（他の成分）
　本発明に係る異方性導電材料は、溶剤を含有していてもよい。該溶剤の使用により、異方性導電材料の粘度を容易に調整できる。さらに、例えば、上記硬化性化合物が固形である場合に、固形の硬化性化合物に溶剤を添加し、溶解させることにより、硬化性化合物の分散性を高めることができる。上記溶剤としては、例えば、酢酸エチル、メチルセロソルブ、トルエン、アセトン、メチルエチルケトン、シクロヘキサン、ｎ－ヘキサン、テトラヒドロフラン及びジエチルエーテル等が挙げられる。 (Other ingredients)
The anisotropic conductive material according to the present invention may contain a solvent. By using the solvent, the viscosity of the anisotropic conductive material can be easily adjusted. Furthermore, for example, when the curable compound is solid, the dispersibility of the curable compound can be increased by adding a solvent to the solid curable compound and dissolving it. Examples of the solvent include ethyl acetate, methyl cellosolve, toluene, acetone, methyl ethyl ketone, cyclohexane, n-hexane, tetrahydrofuran and diethyl ether.
　異方性導電材料の硬化物の接着力を高めることができるので、本発明に係る異方性導電材料は、接着力調整剤を含有することが好ましい。接着力をより一層高める観点からは、上記接着力調整剤は、シランカップリング剤であることが好ましい。 Since the adhesive strength of the cured product of the anisotropic conductive material can be increased, the anisotropic conductive material according to the present invention preferably contains an adhesive strength adjusting agent. From the viewpoint of further increasing the adhesive strength, the adhesive strength modifier is preferably a silane coupling agent.
　本発明に係る異方性導電材料は、フィラーを含有することが好ましい。該フィラーの使用により、異方性導電材料の硬化物の潜熱膨張を抑制できる。 The anisotropic conductive material according to the present invention preferably contains a filler. By using the filler, latent heat expansion of the cured product of the anisotropic conductive material can be suppressed.
　上記η２及び上記比（η１／η２）を好適な範囲に制御するために、フィラーは、表面処理されていることが好ましく、親水性フィラーであることが好ましい。 In order to control the η2 and the ratio (η1 / η2) within a suitable range, the filler is preferably surface-treated, and is preferably a hydrophilic filler.
　上記フィラーは特に限定されない。上記フィラーとしては、シリカ、窒化アルミニウム及びアルミナ等が挙げられる。上記フィラーは１種のみが用いられてもよく、２種以上が併用されてもよい。 The filler is not particularly limited. Examples of the filler include silica, aluminum nitride, and alumina. As for the said filler, only 1 type may be used and 2 or more types may be used together.
　上記親水性フィラーとは、表面が親水基で覆われているフィラーを示す。該親水基としては、水酸基、アミノ基、アミド基、カルボキシレート基及びカルボキシル基等の極性基、並びにカルボキシレートイオン基、スルホン酸イオン基及びアンモニウムイオン基等のイオン性基等が挙げられる。上記親水性フィラーとしては、従来の上記フィラーが親水性表面処理剤で表面処理された親水性フィラーが挙げられる。 The hydrophilic filler is a filler whose surface is covered with a hydrophilic group. Examples of the hydrophilic group include polar groups such as hydroxyl group, amino group, amide group, carboxylate group and carboxyl group, and ionic groups such as carboxylate ion group, sulfonate ion group and ammonium ion group. Examples of the hydrophilic filler include a hydrophilic filler obtained by surface-treating the conventional filler with a hydrophilic surface treatment agent.
　上記親水性表面処理剤としては、例えば、シランカップリング剤、チタネート系カップリング剤、アルミニウム系カップリング剤、ジルコアルミネート系カップリング剤、Ａｌ２Ｏ３、ＴｉＯ２、ＺｒＯ２、シリコーン及びステアリン酸アルミニウム等が挙げられる。中でも、上記親水性表面処理剤として、シランカップリング剤が好ましく用いられる。 Examples of the hydrophilic surface treatment agent include silane coupling agents, titanate coupling agents, aluminum coupling agents, zircoaluminate coupling agents, Al 2 O 3 , TiO 2 , ZrO 2 , silicone, and stearin. An aluminum acid etc. are mentioned. Among these, a silane coupling agent is preferably used as the hydrophilic surface treatment agent.
　上記フィラーの含有量は特に限定されない。上記硬化性化合物の合計１００重量部に対して、上記フィラーの含有量の好ましい下限は５重量部、より好ましい下限は１５重量部、好ましい上限は７０重量部、より好ましい上限は５０重量部である。上記フィラーの含有量が上記好ましい下限及び上限を満たすと、異方性導電材料の硬化物の潜熱膨張を充分に抑制でき、更に異方性導電材料中にフィラーを充分に分散させることができる。 The content of the filler is not particularly limited. The preferable lower limit of the filler content is 5 parts by weight, the more preferable lower limit is 15 parts by weight, the preferable upper limit is 70 parts by weight, and the more preferable upper limit is 50 parts by weight with respect to the total of 100 parts by weight of the curable compound. . When content of the said filler satisfy | fills the said preferable minimum and upper limit, the latent thermal expansion of the cured | curing material of an anisotropic conductive material can fully be suppressed, and also a filler can fully be disperse | distributed in an anisotropic conductive material.
　（異方性導電材料の他の詳細）
　本発明に係る異方性導電材料の製造方法としては、特に限定されず、上記硬化性化合物と、上記熱硬化剤と、上記光硬化開始剤と、上記導電性粒子と、必要に応じて添加される他の成分とを配合し、遊星式攪拌機等を用いて充分に混合する製造方法が挙げられる。 (Other details of anisotropic conductive material)
It does not specifically limit as a manufacturing method of the anisotropic electrically-conductive material which concerns on this invention, Adds the said sclerosing | hardenable compound, the said thermosetting agent, the said photocuring initiator, the said electroconductive particle, as needed. And other components to be mixed and sufficiently mixed using a planetary stirrer or the like.
　本発明に係る異方性導電材料の２５℃及び２．５ｒｐｍでの粘度は、２０～２００Ｐａ・ｓの範囲内であることが好ましい。すなわち、塗布前の上記異方性導電材料の２５℃及び２．５ｒｐｍでの粘度は、２０～２００Ｐａ・ｓの範囲内であることが好ましい。この場合には、例えば基板等の塗布対象部材（第１の接続対象部材）上に異方性導電材料を塗布した後に、硬化前の異方性導電材料の流動をより一層抑制できる。さらに、電極と導電性粒子との間の樹脂成分を容易に取り除くことができ、電極と導電性粒子との接触面積を大きくすることができる。さらに、塗布対象部材（第１の接続対象部材）の表面が凹凸である場合に、該凹凸の表面に異方性導電材料を充分に充填させることができ、硬化後にボイドが生じ難くなる。また、異方性導電材料中において導電性粒子が沈降し難くなり、導電性粒子の分散性を高めることができる。 The viscosity of the anisotropic conductive material according to the present invention at 25 ° C. and 2.5 rpm is preferably in the range of 20 to 200 Pa · s. That is, the viscosity of the anisotropic conductive material before coating at 25 ° C. and 2.5 rpm is preferably in the range of 20 to 200 Pa · s. In this case, for example, the flow of the anisotropic conductive material before curing can be further suppressed after applying the anisotropic conductive material on the application target member (first connection target member) such as a substrate. Furthermore, the resin component between the electrode and the conductive particles can be easily removed, and the contact area between the electrode and the conductive particles can be increased. Furthermore, when the surface of the application target member (first connection target member) is uneven, the surface of the unevenness can be sufficiently filled with an anisotropic conductive material, and voids are less likely to occur after curing. Further, it becomes difficult for the conductive particles to settle in the anisotropic conductive material, and the dispersibility of the conductive particles can be improved.
　本発明に係る異方性導電材料について、光の照射により硬化が進行されて、Ｂステージ化した後の粘度（以下、η３’と略記することがある）は２０００～３５００Ｐａ・ｓの範囲内であることが好ましい。異方性導電材料層及び導電性粒子の流動をより一層抑制する観点からは、上記粘度η３’のより好ましい下限は２２５０Ｐａ・ｓ、より好ましい上限は３２５０Ｐａ・ｓである。上記粘度η３’の測定温度の好ましい下限は２０℃、好ましい上限は３０℃である。上記粘度η３’の測定温度は２５℃であることが特に好ましい。 With respect to the anisotropic conductive material according to the present invention, the viscosity after being cured by light irradiation to be B-staged (hereinafter sometimes abbreviated as η3 ′) is in the range of 2000 to 3500 Pa · s. Preferably there is. From the viewpoint of further suppressing the flow of the anisotropic conductive material layer and the conductive particles, the more preferable lower limit of the viscosity η3 'is 2250 Pa · s, and the more preferable upper limit is 3250 Pa · s. The preferable lower limit of the measurement temperature of the viscosity η3 'is 20 ° C, and the preferable upper limit is 30 ° C. The measurement temperature of the viscosity η3 ′ is particularly preferably 25 ° C.
　本発明に係る異方性導電材料は、２５℃及び２．５ｒｐｍでの粘度をη１とし、かつ２５℃及び５ｒｐｍでの粘度をη２としたときに、上記η２が２０Ｐａ・ｓ以上２００Ｐａ・ｓ以下であり、かつ上記η１の上記η２に対する比（η１／η２）が０．９以上１．１以下であることが好ましい。すなわち、本発明に係る異方性導電材料は、下記式（Ｘ）及び（Ｙ）をいずれも満たすことが好ましい。
　２０Ｐａ・ｓ≦η２≦２００Ｐａ・ｓ　　・・・式（Ｘ）
　０．９≦η１／η２≦１．１　　　　　　・・・式（Ｙ） In the anisotropic conductive material according to the present invention, when the viscosity at 25 ° C. and 2.5 rpm is η1, and the viscosity at 25 ° C. and 5 rpm is η2, the η2 is 20 Pa · s or more and 200 Pa · s or less. And the ratio (η1 / η2) of η1 to η2 is preferably 0.9 or more and 1.1 or less. That is, the anisotropic conductive material according to the present invention preferably satisfies both the following formulas (X) and (Y).
20 Pa · s ≦ η2 ≦ 200 Pa · s Formula (X)
0.9 ≦ η1 / η2 ≦ 1.1 Formula (Y)
　特開２００３－０６４３３０号公報に記載のような従来の異方性導電材料を、ディスペンサー等により塗布対象部材に塗布する際に、安定に塗布できないことがある。特許文献２に記載のような粘度特性を示す異方性導電材料では、塗布の開始直後に粘度が大きく低下し、異方性導電材料が部分的に多量に塗布されることがある。このため、塗布幅が一定にならず、結果として、異方性導電材料により形成された硬化物層の幅又は厚みにばらつきが生じやすい。これに対して、本発明に係る異方性導電材料において、上記η２及び上記比（η１／η２）が特定の上記範囲内にあることにあることによって、異方性導電材料を、ディスペンサー等により塗布対象部材に塗布する際に、より一層安定にかつ均一に塗布できる。さらに、塗布の開始直後に粘度が大きく低下することなく、異方性導電材料が部分的に多量に塗布されるのを抑制できる。このため、塗布幅を一定にすることができ、結果として、異方性導電材料により形成された硬化物層の幅又は厚みにばらつきが生じ難くなる。 When a conventional anisotropic conductive material as described in JP-A-2003-064330 is applied to a member to be applied with a dispenser or the like, it may not be applied stably. In the anisotropic conductive material having viscosity characteristics as described in Patent Document 2, the viscosity is greatly reduced immediately after the start of coating, and the anisotropic conductive material may be partially applied in large quantities. For this reason, the coating width is not constant, and as a result, the width or thickness of the cured product layer formed of the anisotropic conductive material tends to vary. On the other hand, in the anisotropic conductive material according to the present invention, when the η2 and the ratio (η1 / η2) are within the specific range, the anisotropic conductive material is dispensed by a dispenser or the like. When applying to the application target member, it can be applied more stably and uniformly. Furthermore, it is possible to prevent the anisotropic conductive material from being partially applied in a large amount without greatly reducing the viscosity immediately after the start of the application. For this reason, the coating width can be made constant, and as a result, variations in the width or thickness of the cured product layer formed of the anisotropic conductive material are less likely to occur.
　異方性導電材料をより一層均一に塗布する観点からは、上記η２の好ましい下限は５０Ｐａ・ｓ、より好ましい下限は１００Ｐａ・ｓ、好ましい上限は１８０Ｐａ・ｓ、より好ましい上限は１５０Ｐａ・ｓである。 From the viewpoint of more uniformly applying the anisotropic conductive material, the preferable lower limit of η2 is 50 Pa · s, the more preferable lower limit is 100 Pa · s, the preferable upper limit is 180 Pa · s, and the more preferable upper limit is 150 Pa · s. .
　上記η２及び上記比（η１／η２）は、硬化性化合物として結晶性樹脂を用いたり、親水性を高めるために表面処理されたフィラーを用いたりすることにより、調整可能である。上記η２及び上記比（η１／η２）を上記範囲内に容易に制御する観点からは、上記硬化性化合物は、結晶性樹脂を含むことが好ましい。 The above η2 and the above ratio (η1 / η2) can be adjusted by using a crystalline resin as the curable compound or by using a filler that has been surface-treated to enhance hydrophilicity. From the viewpoint of easily controlling the η2 and the ratio (η1 / η2) within the above range, the curable compound preferably contains a crystalline resin.
　本発明に係る異方性導電材料を硬化させる方法としては、異方性導電材料に光を照射した後、異方性導電材料を加熱する方法、並びに異方性導電材料を加熱した後、異方性導電材料に光を照射する方法が挙げられる。また、光硬化の速度及び熱硬化の速度が異なる場合などには、光の照射と加熱とを同時に行ってもよい。なかでも、異方性導電材料に光を照射した後、異方性導電材料を加熱する方法が好ましい。光硬化と熱硬化との併用により、異方性導電材料を短時間で硬化させることができる。 As a method for curing the anisotropic conductive material according to the present invention, after the anisotropic conductive material is irradiated with light, the anisotropic conductive material is heated, and after the anisotropic conductive material is heated, the anisotropic conductive material is heated. A method of irradiating the anisotropic conductive material with light can be given. In addition, when the photocuring speed and the thermosetting speed are different, light irradiation and heating may be performed simultaneously. Especially, the method of heating an anisotropic conductive material after irradiating light to an anisotropic conductive material is preferable. The anisotropic conductive material can be cured in a short time by the combined use of photocuring and heat curing.
　（接続構造体及び接続構造体の製造方法）
　本発明に係る異方性導電材料を用いて、接続対象部材を接続することにより、接続構造体を得ることができる。 (Connecting structure and manufacturing method of connecting structure)
A connection structure can be obtained by connecting the connection target members using the anisotropic conductive material according to the present invention.
　上記接続構造体は、第１の接続対象部材と、第２の接続対象部材と、該第１，第２の接続対象部材を電気的に接続している接続部とを備えており、該接続部が上記異方性導電材料により形成されていることが好ましい。上記接続部は、上記異方性導電材料が硬化した硬化物層である。 The connection structure includes a first connection target member, a second connection target member, and a connection portion that electrically connects the first and second connection target members. The part is preferably formed of the anisotropic conductive material. The connection portion is a cured product layer obtained by curing the anisotropic conductive material.
　次に、図面を参照しつつ、本発明の一実施形態に係る異方性導電材料を用いた接続構造体、及び該接続構造体の製造方法をより詳細に説明する。 Next, a connection structure using an anisotropic conductive material according to an embodiment of the present invention and a method for manufacturing the connection structure will be described in more detail with reference to the drawings.
　図１に、本発明の一実施形態に係る異方性導電材料を用いた接続構造体の一例を模式的に部分切欠正面断面図で示す。 FIG. 1 schematically shows an example of a connection structure using an anisotropic conductive material according to an embodiment of the present invention in a partially cutaway front sectional view.
　図１に示す接続構造体１は、第１の接続対象部材２の上面２ａに、硬化物層３を介して、第２の接続対象部材４が接続された構造を有する。硬化物層３は接続部である。硬化物層３は硬化性化合物と熱硬化剤と光硬化開始剤と導電性粒子５とを含む異方性導電材料を硬化させることにより形成されている。上記異方性導電材料は、複数の導電性粒子５を含む。第１の接続対象部材２の上面２ａには、複数の電極２ｂが設けられている。第２の接続対象部材４の下面４ａには、複数の電極４ｂが設けられている。電極２ｂと電極４ｂとが、１つ又は複数の導電性粒子５により電気的に接続されている。 1 has a structure in which a second connection target member 4 is connected to an upper surface 2a of a first connection target member 2 via a cured product layer 3. The connection structure 1 shown in FIG. The cured product layer 3 is a connection part. The cured product layer 3 is formed by curing an anisotropic conductive material including a curable compound, a thermosetting agent, a photocuring initiator, and conductive particles 5. The anisotropic conductive material includes a plurality of conductive particles 5. A plurality of electrodes 2 b are provided on the upper surface 2 a of the first connection target member 2. A plurality of electrodes 4 b are provided on the lower surface 4 a of the second connection target member 4. The electrode 2b and the electrode 4b are electrically connected by one or a plurality of conductive particles 5.
　接続構造体１では、第１の接続対象部材２としてガラス基板が用いられており、第２の接続対象部材４として半導体チップが用いられている。第１，第２の接続対象部材は、特に限定されない。第１，第２の接続対象部材としては、具体的には、半導体チップ、コンデンサ及びダイオード等の電子部品、並びにプリント基板、フレキシブルプリント基板及びガラス基板等の回路基板等が挙げられる。 In the connection structure 1, a glass substrate is used as the first connection target member 2, and a semiconductor chip is used as the second connection target member 4. The first and second connection target members are not particularly limited. Specific examples of the first and second connection target members include electronic components such as semiconductor chips, capacitors, and diodes, and circuit boards such as printed boards, flexible printed boards, and glass boards.
　図１に示す接続構造体１は、例えば、以下のようにして得ることができる。 The connection structure 1 shown in FIG. 1 can be obtained as follows, for example.
　図２（ａ）に示すように、電極２ｂを上面２ａに有する第１の接続対象部材２を用意する。次に、第１の接続対象部材２の上面２ａに、複数の導電性粒子５を含む異方性導電材料を塗布し、第１の接続対象部材２の上面２ａに異方性導電材料層３Ａを形成する。このとき、電極２ｂ上に、１つ又は複数の導電性粒子５が配置されていることが好ましい。 As shown in FIG. 2A, a first connection target member 2 having an electrode 2b on the upper surface 2a is prepared. Next, an anisotropic conductive material including a plurality of conductive particles 5 is applied to the upper surface 2a of the first connection target member 2, and the anisotropic conductive material layer 3A is applied to the upper surface 2a of the first connection target member 2. Form. At this time, it is preferable that one or a plurality of conductive particles 5 be disposed on the electrode 2b.
　次に、図２（ｂ）に示すように、異方性導電材料層３Ａに光を照射することにより、異方性導電材料層３Ａの硬化を進行させる。異方性導電材料層３Ａの硬化を進行させて、異方性導電材料層３ＡをＢステージ化する。第１の接続対象部材２の上面２ａに、Ｂステージ化された異方性導電材料層３Ｂを形成する。 Next, as shown in FIG. 2B, the anisotropic conductive material layer 3A is cured by irradiating the anisotropic conductive material layer 3A with light. By curing the anisotropic conductive material layer 3A, the anisotropic conductive material layer 3A is B-staged. A B-staged anisotropic conductive material layer 3B is formed on the upper surface 2a of the first connection target member 2.
　異方性導電材料層３Ａの硬化を進行させて、異方性導電材料層３ＡをＢステージ化する際には、Ｂステージ化された異方性導電材料層３Ｂの粘度（以下、η３と略記することがある）が２０００～３５００Ｐａ・ｓの範囲内であるように、異方性導電材料層３ＡをＢステージ化することが好ましい。上記粘度η３を上記範囲内にすることにより、異方性導電材料層の流動を充分に抑制できる。このため、電極２ｂ，４ｂ間に、導電性粒子５が配置されやすくなる。さらに、第１の接続対象部材２又は第２の接続対象部材４の外周面よりも側方の領域に、異方性導電材料層が意図せずに流動するのを抑制できる。 When the anisotropic conductive material layer 3A is hardened and the anisotropic conductive material layer 3A is B-staged, the viscosity of the B-staged anisotropic conductive material layer 3B (hereinafter abbreviated as η3). The anisotropic conductive material layer 3A is preferably B-staged so that it is within the range of 2000 to 3500 Pa · s. By setting the viscosity η3 within the above range, the flow of the anisotropic conductive material layer can be sufficiently suppressed. For this reason, it becomes easy to arrange the conductive particles 5 between the electrodes 2b and 4b. Furthermore, it is possible to suppress the anisotropic conductive material layer from flowing unintentionally in a region lateral to the outer peripheral surface of the first connection target member 2 or the second connection target member 4.
　異方性導電材料層及び導電性粒子５の流動をより一層抑制する観点からは、上記粘度η３のより好ましい下限は２２５０Ｐａ・ｓ、より好ましい上限は３２５０Ｐａ・ｓである。上記粘度η３の測定温度の好ましい下限は２０℃、好ましい上限は３０℃である。上記粘度η３の測定温度は２５℃であることが特に好ましい。 From the viewpoint of further suppressing the flow of the anisotropic conductive material layer and the conductive particles 5, a more preferable lower limit of the viscosity η3 is 2250 Pa · s, and a more preferable upper limit is 3250 Pa · s. The preferable lower limit of the measurement temperature of the viscosity η3 is 20 ° C., and the preferable upper limit is 30 ° C. The measurement temperature of the viscosity η3 is particularly preferably 25 ° C.
　第１の接続対象部材２の上面２ａに、異方性導電材料を塗布しながら、異方性導電材料層３Ａに光を照射することが好ましい。さらに、第１の接続対象部材２の上面２ａへの異方性導電材料の塗布と同時に、又は塗布の直後に、異方性導電材料層３Ａに光を照射することも好ましい。塗布と光の照射とが上記のように行われた場合には、異方性導電材料層の流動をより一層抑制できる。このため、得られた接続構造体１の導通信頼性をより一層高めることができる。第１の接続対象部材２の上面２ａに異方性導電材料を塗布してから光を照射するまでの時間は、０～３秒の範囲内であることが好ましく、０～２秒の範囲内であることがより好ましい。 It is preferable to irradiate the anisotropic conductive material layer 3A with light while applying the anisotropic conductive material to the upper surface 2a of the first connection target member 2. Furthermore, it is also preferable to irradiate the anisotropic conductive material layer 3 </ b> A simultaneously with the application of the anisotropic conductive material to the upper surface 2 a of the first connection target member 2 or immediately after the application. When application and light irradiation are performed as described above, the flow of the anisotropic conductive material layer can be further suppressed. For this reason, the conduction | electrical_connection reliability of the obtained connection structure 1 can be improved further. The time from application of the anisotropic conductive material to the upper surface 2a of the first connection target member 2 until irradiation with light is preferably within a range of 0 to 3 seconds, and within a range of 0 to 2 seconds. It is more preferable that
　第１の接続対象部材２の上面２ａに、異方性導電材料を塗布しながら、異方性導電材料層３Ａに光を照射することが好ましい。さらに、第１の接続対象部材２の上面２ａへの異方性導電材料の塗布と同時に、又は塗布の直後に、異方性導電材料層３Ａに光を照射することも好ましい。塗布及び光の照射が上記のように行われた場合には、異方性導電材料層の流動をより一層抑制できる。このため、得られた接続構造体１の導通信頼性をより一層高めることができる。第１の接続対象部材２の上面２ａに異方性導電材料を塗布してから光を照射するまでの時間は、０～３秒の範囲内であることが好ましく、０～２秒の範囲内であることがより好ましい。 It is preferable to irradiate the anisotropic conductive material layer 3A with light while applying the anisotropic conductive material to the upper surface 2a of the first connection target member 2. Furthermore, it is also preferable to irradiate the anisotropic conductive material layer 3 </ b> A simultaneously with the application of the anisotropic conductive material to the upper surface 2 a of the first connection target member 2 or immediately after the application. When application and light irradiation are performed as described above, the flow of the anisotropic conductive material layer can be further suppressed. For this reason, the conduction | electrical_connection reliability of the obtained connection structure 1 can be improved further. The time from application of the anisotropic conductive material to the upper surface 2a of the first connection target member 2 until irradiation with light is preferably within a range of 0 to 3 seconds, and within a range of 0 to 2 seconds. It is more preferable that
　光の照射により異方性導電材料層３ＡをＢステージ化させる場合には、異方性導電材料層３Ａの硬化を適度に進行させるための光照射強度は、例えば、０．１～１００ｍＷ／ｃｍ２程度である。 When the anisotropic conductive material layer 3A is B-staged by light irradiation, the light irradiation intensity for appropriately proceeding curing of the anisotropic conductive material layer 3A is, for example, 0.1 to 100 mW / cm. It is about 2 .
　光を照射する際に用いる光源は特に限定されない。該光源としては、例えば、波長４２０ｎｍ以下に充分な発光分布を有する光源等が挙げられる。また、光源の具体例としては、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯、及びメタルハライドランプ等が挙げられる。 The light source used when irradiating light is not particularly limited. Examples of the light source include a light source having a sufficient light emission distribution at a wavelength of 420 nm or less. Specific examples of the light source include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, and a metal halide lamp.
　次に、図２（ｃ）に示すように、Ｂステージ化された異方性導電材料層３Ｂの上面３ａに、第２の接続対象部材４を積層する。第１の接続対象部材２の上面２ａの電極２ｂと、第２の接続対象部材４の下面４ａの電極４ｂとが対向するように、第２の接続対象部材４を積層する。 Next, as shown in FIG. 2C, the second connection target member 4 is laminated on the upper surface 3a of the B-staged anisotropic conductive material layer 3B. The second connection target member 4 is laminated so that the electrode 2b on the upper surface 2a of the first connection target member 2 and the electrode 4b on the lower surface 4a of the second connection target member 4 face each other.
　さらに、第２の接続対象部材４の積層の際に、異方性導電材料層３Ｂに熱を付与することにより、異方性導電材料層３Ｂをさらに硬化させ、硬化物層３を形成する。ただし、第２の接続対象部材４の積層の前に、異方性導電材料層３Ｂに熱を付与してもよい。さらに、第２の接続対象部材４の積層の後に、異方性導電材料層３Ｂに熱を付与し完全に硬化させることが好ましい。 Furthermore, when the second connection target member 4 is laminated, the anisotropic conductive material layer 3B is further cured by applying heat to the anisotropic conductive material layer 3B, thereby forming the cured product layer 3. However, heat may be applied to the anisotropic conductive material layer 3B before the second connection target member 4 is laminated. Furthermore, it is preferable to apply heat to the anisotropic conductive material layer 3B and completely cure it after the second connection target member 4 is laminated.
　熱の付与により異方性導電材料層３Ｂを硬化させる場合には、異方性導電材料層３Ｂを充分に硬化させるための加熱温度の好ましい下限は１６０℃、好ましい上限は２５０℃、より好ましい上限は２００℃である。 When the anisotropic conductive material layer 3B is cured by applying heat, the preferable lower limit of the heating temperature for sufficiently curing the anisotropic conductive material layer 3B is 160 ° C, the preferable upper limit is 250 ° C, and the more preferable upper limit. Is 200 ° C.
　異方性導電材料層３Ｂを硬化させる際に、加圧することが好ましい。加圧によって電極２ｂと電極４ｂとで導電性粒子５を圧縮することにより、電極２ｂ，４ｂと導電性粒子５との接触面積を大きくすることができる。このため、導通信頼性を高めることができる。 It is preferable to apply pressure when the anisotropic conductive material layer 3B is cured. By compressing the conductive particles 5 with the electrodes 2b and 4b by pressurization, the contact area between the electrodes 2b and 4b and the conductive particles 5 can be increased. For this reason, conduction reliability can be improved.
　異方性導電材料層３Ｂを硬化させることにより、第１の接続対象部材２と第２の接続対象部材４とが、硬化物層３を介して接続される。また、電極２ｂと電極４ｂとが、導電性粒子５を介して電気的に接続される。このようにして、図１に示す接続構造体１を得ることができる。本実施形態では、光硬化と熱硬化とが併用されているため、異方性導電材料を短時間で硬化させることができる。 The first connection target member 2 and the second connection target member 4 are connected via the cured product layer 3 by curing the anisotropic conductive material layer 3B. Further, the electrode 2 b and the electrode 4 b are electrically connected through the conductive particles 5. In this way, the connection structure 1 shown in FIG. 1 can be obtained. In this embodiment, since photocuring and thermosetting are used together, the anisotropic conductive material can be cured in a short time.
　接続構造体１を得る際に、異方性導電材料層３Ａに光を照射し、Ｂステージ化された異方性導電材料層３Ｂを形成した後、異方性導電材料層３Ｂに熱を付与することが好ましい。 When obtaining the connection structure 1, the anisotropic conductive material layer 3A is irradiated with light to form a B-staged anisotropic conductive material layer 3B, and then heat is applied to the anisotropic conductive material layer 3B. It is preferable to do.
　異方性導電材料層３Ａを形成し、該異方性導電材料層３ＡをＢステージ化する際に、図３（ａ）に示す複合装置が好適に用いられる。 When the anisotropic conductive material layer 3A is formed and the anisotropic conductive material layer 3A is B-staged, the composite apparatus shown in FIG. 3A is preferably used.
　図３（ａ）に示す複合装置１１は、ディスペンサー１２と、該ディスペンサー１２に接続された光照射装置１３とを備える。ディスペンサー１２は、内部に異方性導電材料を充填するためのシリンジ１２ａと、該シリンジ１２ａの外周面を把持している把持部１２ｂとを備える。光照射装置１３は、光照射装置本体１３ａと、光照射部１３ｂとを備える。複合装置１１では、把持部１２ｂと光照射装置本体１３ａとが接続されている。従って、ディスペンサー１２と光照射装置１３との距離を小さくすることができ、すなわち、ディスペンサー１２の吐出部と、光照射部１３ｂとの距離を小さくすることができる。さらに、ディスペンサー１２と光照射装置１３とを同じ速度で容易に移動させることができる。なお、シリンジ１２ａと光照射装置本体１３ａとが直接接続されていてもよい。 3 (a) includes a dispenser 12 and a light irradiation device 13 connected to the dispenser 12. The dispenser 12 includes a syringe 12a for filling the inside with an anisotropic conductive material, and a grip portion 12b that grips the outer peripheral surface of the syringe 12a. The light irradiation device 13 includes a light irradiation device main body 13a and a light irradiation unit 13b. In the composite apparatus 11, the grip part 12b and the light irradiation apparatus main body 13a are connected. Therefore, the distance between the dispenser 12 and the light irradiation device 13 can be reduced, that is, the distance between the discharge part of the dispenser 12 and the light irradiation part 13b can be reduced. Furthermore, the dispenser 12 and the light irradiation device 13 can be easily moved at the same speed. In addition, the syringe 12a and the light irradiation apparatus main body 13a may be directly connected.
　図３（ａ）に示すように、塗布及び光の照射の際には、複合装置１１を矢印Ａの方向に移動させながら、第１の接続対象部材２の上面２ａに、シリンジ１２ａから異方性導電材料を塗布し、異方性導電材料層３Ａを形成する。また、塗布しながら、ディスペンサー１２に接続された光照射装置１３の光照射部１３ｂから、矢印Ｂで示すように異方性導電材料層３Ａに光を照射する。 As shown in FIG. 3A, when applying and irradiating light, while moving the composite device 11 in the direction of arrow A, the syringe 12a is anisotropically moved from the syringe 12a to the upper surface 2a of the first connection target member 2. A conductive conductive material is applied to form the anisotropic conductive material layer 3A. Further, the anisotropic conductive material layer 3 </ b> A is irradiated with light from the light irradiation unit 13 b of the light irradiation device 13 connected to the dispenser 12 as indicated by an arrow B while being applied.
　第１の接続対象部材２の上面２ａに形成された異方性導電材料層３Ａ及び該異方性導電材料層３Ａに含まれている導電性粒子５の流動をより一層抑制する観点からは、ディスペンサー１２と光照射装置１３とを移動させながら、塗布と光の照射とが行われることが好ましい。さらに、光の照射までの時間を高精度に制御する観点からは、ディスペンサー１２と光照射装置１３とは同じ速度で移動されることが好ましい。ただし、複合装置１１を移動させずに、台３１を矢印Ａの方向に移動させてもよい。 From the viewpoint of further suppressing the flow of the anisotropic conductive material layer 3A formed on the upper surface 2a of the first connection target member 2 and the conductive particles 5 contained in the anisotropic conductive material layer 3A, It is preferable that application and light irradiation are performed while moving the dispenser 12 and the light irradiation device 13. Furthermore, it is preferable that the dispenser 12 and the light irradiation device 13 are moved at the same speed from the viewpoint of controlling the time until the light irradiation with high accuracy. However, the table 31 may be moved in the direction of the arrow A without moving the composite apparatus 11.
　図４（ａ）に示すように、ディスペンサー１２と、該ディスペンサー１２に接続されていない光照射装置２１とを用いてもよい。光照射装置２１は、光照射装置１３と同様に、光照射装置本体２１ａと、光照射部２１ｂとを備える。光照射装置２１は、光照射装置１３よりも、広い領域に光を照射することができるように構成されている。 As shown in FIG. 4A, a dispenser 12 and a light irradiation device 21 that is not connected to the dispenser 12 may be used. Similar to the light irradiation device 13, the light irradiation device 21 includes a light irradiation device main body 21 a and a light irradiation unit 21 b. The light irradiation device 21 is configured to irradiate light over a wider area than the light irradiation device 13.
　ディスペンサー１２と、該ディスペンサー１２に接続されていない光照射装置２１とを用いる場合には、例えば、図４（ａ）に示すように、第１の接続対象部材２の上方に光照射装置２１を配置する。次に、第１の接続対象部材２と光照射装置２１との間においてディスペンサー１２を矢印Ａの方向に移動させながら、第１の接続対象部材２の上面２ａに、シリンジ１２ａから異方性導電材料を塗布し、異方性導電材料層３Ａを形成する。次に、図４（ｂ）に示すように、異方性導電材料の塗布が終了した後、第１の接続対象部材２の上方に配置された光照射装置２１の光照射部２１ｂから、異方性導電材料層３Ａに光を照射する。光の照射は、例えば異方性導電材料の塗布と同時又は塗布の直後に行われる。 When using the dispenser 12 and the light irradiation device 21 not connected to the dispenser 12, for example, as shown in FIG. 4A, the light irradiation device 21 is placed above the first connection target member 2. Deploy. Next, while the dispenser 12 is moved in the direction of the arrow A between the first connection target member 2 and the light irradiation device 21, anisotropic conduction is performed from the syringe 12 a to the upper surface 2 a of the first connection target member 2. The material is applied to form the anisotropic conductive material layer 3A. Next, as shown in FIG. 4 (b), after the application of the anisotropic conductive material is completed, the light irradiation unit 21b of the light irradiation device 21 disposed above the first connection target member 2 is different from the first irradiation target member 2. The isotropic conductive material layer 3A is irradiated with light. The light irradiation is performed, for example, simultaneously with the application of the anisotropic conductive material or immediately after the application.
　光照射装置２１は、塗布の際に、第１の接続対象部材２の上方に配置されていることが好ましい。この場合には、塗布の後に、光を速やかに照射できる。塗布の後に、異方性導電材料層３Ａの全領域に一括して光を照射することが好ましい。この場合には、異方性導電材料層３Ａをより一層均一にＢステージ化することができる。 It is preferable that the light irradiation device 21 is disposed above the first connection target member 2 at the time of application. In this case, light can be irradiated quickly after application. After the application, it is preferable to irradiate the entire region of the anisotropic conductive material layer 3A all together. In this case, the anisotropic conductive material layer 3A can be made B-stage even more uniformly.
　図３（ａ）又は図４（ａ）に示す装置の使用により、第１の接続対象部材２の上面２ａへの異方性導電材料の塗布と同時に、又は塗布の直後に、異方性導電材料層３Ａに光を容易に照射できる。 By using the apparatus shown in FIG. 3 (a) or FIG. 4 (a), the anisotropic conductive material is applied simultaneously or immediately after the application of the anisotropic conductive material to the upper surface 2a of the first connection target member 2. The material layer 3A can be easily irradiated with light.
　本発明に係る接続構造体の製造方法で用いられる異方性導電材料は、硬化性化合物と、熱硬化剤と、光硬化開始剤と、導電性粒子とを含有するので、第１の接続対象部材２の上面２ａに塗布された異方性導電材料又は該異方性導電材料に含まれている導電性粒子の流動を充分に抑制することができる。 The anisotropic conductive material used in the method for manufacturing a connection structure according to the present invention contains a curable compound, a thermosetting agent, a photocuring initiator, and conductive particles. The flow of the anisotropic conductive material applied to the upper surface 2a of the member 2 or the conductive particles contained in the anisotropic conductive material can be sufficiently suppressed.
　本発明に係る異方性導電材料及び接続構造体の製造方法は、例えば、フレキシブルプリント基板とガラス基板との接続（ＦＯＧ（Ｆｉｌｍ　ｏｎ　Ｇｌａｓｓ））、半導体チップとフレキシブルプリント基板との接続（ＣＯＦ（Ｃｈｉｐ　ｏｎ　Ｆｉｌｍ））、又は半導体チップとガラス基板との接続（ＣＯＧ（Ｃｈｉｐ　ｏｎ　Ｇｌａｓｓ））等に使用できる。なかでも、本発明に係る異方性導電材料及び接続構造体の製造方法は、ＣＯＧ用途に好適である。本発明に係る異方性導電材料及び接続構造体の製造方法は、半導体チップとガラス基板との接続に好適に用いられる。ただし、本発明に係る異方性導電材料及び接続構造体の製造方法の用途は、上述した用途に限定されない。 The anisotropic conductive material and the connection structure manufacturing method according to the present invention include, for example, connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), connection between a semiconductor chip and a flexible printed circuit board (COF ( (Chip on Film)) or a connection between a semiconductor chip and a glass substrate (COG (Chip on Glass)) or the like. Especially, the manufacturing method of the anisotropic electrically-conductive material and connection structure which concern on this invention is suitable for a COG use. The manufacturing method of the anisotropic conductive material and the connection structure according to the present invention is suitably used for the connection between the semiconductor chip and the glass substrate. However, the use of the anisotropic conductive material and the connection structure manufacturing method according to the present invention is not limited to the above-described use.
　ＣＯＧ用途では、特に、半導体チップとガラス基板との電極間を、異方性導電材料の導電性粒子により確実に接続することが困難なことが多い。例えば、ＣＯＧ用途の場合には、半導体チップの隣り合う電極間、及びガラス基板の隣り合う電極間の間隔が１０～２０μｍ程度であることがあり、微細な配線が形成されていることが多い。微細な配線が形成されていても、本発明に係る異方性導電材料及び接続構造体の製造方法により、半導体チップとガラス基板との電極間を高精度に接続することができ、導通信頼性を高めることができる。 In COG applications, in particular, it is often difficult to reliably connect the electrodes of the semiconductor chip and the glass substrate with conductive particles of an anisotropic conductive material. For example, in the case of COG use, the distance between adjacent electrodes of a semiconductor chip and the distance between adjacent electrodes of a glass substrate may be about 10 to 20 μm, and fine wiring is often formed. Even if fine wiring is formed, the anisotropic conductive material and the manufacturing method of the connection structure according to the present invention can connect the electrodes of the semiconductor chip and the glass substrate with high accuracy, and the conduction reliability. Can be increased.
　さらに、ＣＯＧ用途の場合には、異方性導電材料中の導電性粒子の含有量を多くしなければならないことがある。従って、圧着の際に、導通接点が多くなって導電性粒子の反発力が大きくなり、圧着時の圧力を高くする必要があることがある。このため、電極又は導電性粒子がつぶれて、導通信頼性が低くなりやすい。しかしながら、本発明に係る異方性導電材料及び接続構造体の製造方法の使用により、導通信頼性を充分に高めることができる。 Furthermore, in the case of COG use, it may be necessary to increase the content of conductive particles in the anisotropic conductive material. Therefore, during crimping, there are cases where the number of conductive contacts increases and the repulsive force of the conductive particles increases, and it is necessary to increase the pressure during crimping. For this reason, an electrode or electroconductive particle is crushed and conduction reliability tends to be lowered. However, the use of the anisotropic conductive material and the manufacturing method of the connection structure according to the present invention can sufficiently improve the conduction reliability.
　以下、本発明について、実施例および比較例を挙げて具体的に説明する。本発明は、以下の実施例のみに限定されない。 Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. The present invention is not limited only to the following examples.
　（実施例１）
　（１）エピスルフィド化合物含有混合物の調製
　攪拌機、冷却機及び温度計を備えた２Ｌの容器内に、エタノール２５０ｍＬと、純水２５０ｍＬと、チオシアン酸カリウム２０ｇとを加え、チオシアン酸カリウムを溶解させ、第１の溶液を調製した。その後、容器内の温度を２０～２５℃の範囲内に保持した。次に、２０～２５℃に保持された容器内の第１の溶液を攪拌しながら、該第１の溶液中に、レゾルシノールジグリシジルエーテル１６０ｇを５ｍＬ／分の速度で滴下した。滴下後、３０分間さらに攪拌し、エポキシ化合物含有混合液を得た。 Example 1
(1) Preparation of episulfide compound-containing mixture In a 2 L vessel equipped with a stirrer, a cooler and a thermometer, ethanol 250 mL, pure water 250 mL, and potassium thiocyanate 20 g were added to dissolve potassium thiocyanate, One solution was prepared. Thereafter, the temperature in the container was kept within the range of 20 to 25 ° C. Next, 160 g of resorcinol diglycidyl ether was added dropwise at a rate of 5 mL / min to the first solution while stirring the first solution in a container maintained at 20 to 25 ° C. After dropping, the mixture was further stirred for 30 minutes to obtain an epoxy compound-containing mixed solution.
　次に、純水１００ｍＬと、エタノール１００ｍＬとを含む溶液に、チオシアン酸カリウム２０ｇを溶解させた第２の溶液を用意した。得られたエポキシ基含有混合液に、得られた第２の溶液を５ｍＬ／分の速度で添加した後、３０分攪拌した。攪拌後、純水１００ｍＬとエタノール１００ｍＬとを含む溶液に、チオシアン酸カリウム２０ｇを溶解させた第２の溶液をさらに用意し、該第２の溶液を５ｍＬ／分の速度で容器内にさらに添加し、３０分間攪拌した。その後、容器内の温度を１０℃に冷却し、２時間攪拌し、反応させた。 Next, a second solution in which 20 g of potassium thiocyanate was dissolved in a solution containing 100 mL of pure water and 100 mL of ethanol was prepared. The obtained second solution was added to the obtained epoxy group-containing mixed solution at a rate of 5 mL / min, and then stirred for 30 minutes. After stirring, a second solution in which 20 g of potassium thiocyanate is dissolved in a solution containing 100 mL of pure water and 100 mL of ethanol is further prepared, and the second solution is further added to the container at a rate of 5 mL / min. And stirred for 30 minutes. Thereafter, the temperature in the container was cooled to 10 ° C., and stirred for 2 hours to be reacted.
　次に、容器内に飽和食塩水１００ｍＬを加え、１０分間攪拌した。攪拌後、容器内にトルエン３００ｍＬをさらに加え、１０分間攪拌した。その後、容器内の溶液を分液ロートに移し、２時間静置し、溶液を分離させた。分液ロート内の下方の溶液を排出し、上澄み液を取り出した。取り出された上澄み液にトルエン１００ｍＬを加え、攪拌し、２時間静置した。更に、トルエン１００ｍＬをさらに加え、攪拌し、２時間静置した。 Next, 100 mL of saturated saline was added to the container and stirred for 10 minutes. After stirring, 300 mL of toluene was further added to the container and stirred for 10 minutes. Thereafter, the solution in the container was transferred to a separating funnel and allowed to stand for 2 hours to separate the solution. The lower solution in the separatory funnel was discharged, and the supernatant was taken out. 100 mL of toluene was added to the removed supernatant, stirred, and allowed to stand for 2 hours. Further, 100 mL of toluene was further added, stirred and allowed to stand for 2 hours.
　次に、トルエンが加えられた上澄み液に、硫酸マグネシウム５０ｇを加え、５分間攪拌した。攪拌後、ろ紙により硫酸マグネシウムを取り除いて、溶液を分離した。真空乾燥機を用いて、分離された溶液を８０℃で減圧乾燥することにより、残存している溶剤を除去した。このようにして、エピスルフィド化合物含有混合物を得た。 Next, 50 g of magnesium sulfate was added to the supernatant liquid to which toluene was added and stirred for 5 minutes. After stirring, magnesium sulfate was removed with a filter paper to separate the solution. The remaining solvent was removed by drying the separated solution under reduced pressure at 80 ° C. using a vacuum dryer. In this way, an episulfide compound-containing mixture was obtained.
　クロロホルムを溶媒として、得られたエピスルフィド化合物含有混合物の１Ｈ－ＮＭＲの測定を行った。この結果、エポキシ基の存在を示す６．５～７．５ｐｐｍの領域のシグナルが減少し、エピスルフィド基の存在を示す２．０～３．０ｐｐｍの領域にシグナルが現れた。これにより、レゾルシノールジグリシジルエーテルの一部のエポキシ基がエピスルフィド基に変換されていることを確認した。また、１Ｈ－ＮＭＲの測定結果の積分値より、エピスルフィド化合物含有混合物は、レゾルシノールジグリシジルエーテル７０重量％と、上記式（１Ｂ）で表される構造を有するエピスルフィド化合物３０重量％とを含有することを確認した。 The resulting episulfide compound-containing mixture was subjected to 1 H-NMR measurement using chloroform as a solvent. As a result, the signal in the 6.5 to 7.5 ppm region indicating the presence of the epoxy group decreased, and the signal appeared in the 2.0 to 3.0 ppm region indicating the presence of the episulfide group. This confirmed that some epoxy groups of resorcinol diglycidyl ether were converted into episulfide groups. From the integral value of the measurement result of 1 H-NMR, the episulfide compound-containing mixture contains 70% by weight of resorcinol diglycidyl ether and 30% by weight of the episulfide compound having the structure represented by the above formula (1B). It was confirmed.
　（２）異方性導電ペーストの調製
　得られたエピスルフィド化合物含有混合物３０重量部に、熱硬化剤としてのアミンアダクト（味の素ファインテクノ社製「ＰＮ－２３Ｊ」）５重量部と、光硬化性化合物としてのエポキシアクリレート（ダイセル・サイテック社製「ＥＢＥＣＲＹＬ３７０２」）５重量部と、光重合開始剤としてのアシルホスフィンオキサイド系化合物（チバ・ジャパン社製「ＤＡＲＯＣＵＲ　ＴＰＯ」）０．１重量部と、硬化促進剤としての２－エチル－４－メチルイミダゾール１重量部と、フィラーとしての平均粒子径０．２５μｍのシリカ２０重量部及び平均粒子径０．５μｍのアルミナ２０重量部とを配合し、さらに平均粒子径３μｍの導電性粒子を配合物１００重量％中での含有量が１０重量％となるように添加した後、遊星式攪拌機を用いて２０００ｒｐｍで５分間攪拌することにより、配合物を得た。 (2) Preparation of anisotropic conductive paste 30 parts by weight of the resulting episulfide compound-containing mixture, 5 parts by weight of an amine adduct (“PN-23J” manufactured by Ajinomoto Fine Techno Co.) as a thermosetting agent, and a photocurable compound 5 parts by weight of epoxy acrylate ("EBECRYL 3702" manufactured by Daicel-Cytec), 0.1 parts by weight of acylphosphine oxide compound ("DAROCUR TPO" manufactured by Ciba Japan) as a photopolymerization initiator, and curing acceleration 1 part by weight of 2-ethyl-4-methylimidazole as an agent, 20 parts by weight of silica having an average particle diameter of 0.25 μm and 20 parts by weight of alumina having an average particle diameter of 0.5 μm are blended, and average particles Conductive particles having a diameter of 3 μm were added so that the content in 100% by weight of the composition was 10% by weight. , By stirring for 5 minutes at 2000rpm using a planetary mixing machine to obtain a formulation.
　なお、用いた上記導電性粒子は、ジビニルベンゼン樹脂粒子の表面にニッケルめっき層が形成されており、かつ該ニッケルめっき層の表面に金めっき層が形成されている金属層を有する導電性粒子である。 The conductive particles used are conductive particles having a metal layer in which a nickel plating layer is formed on the surface of divinylbenzene resin particles and a gold plating layer is formed on the surface of the nickel plating layer. is there.
　得られた配合物を、ナイロン製ろ紙（孔径１０μｍ）を用いてろ過することにより、導電性粒子の含有量が１０重量％である異方性導電ペーストを得た。 The obtained composition was filtered using a nylon filter paper (pore diameter: 10 μm) to obtain an anisotropic conductive paste having a conductive particle content of 10% by weight.
　（３）接続構造体の作製
　Ｌ／Ｓが３０μｍ／３０μｍのＩＴＯ電極パターンが上面に形成された透明ガラス基板を用意した。また、Ｌ／Ｓが３０μｍ／３０μｍの銅電極パターンが下面に形成された半導体チップを用意した。 (3) Production of Connection Structure A transparent glass substrate having an ITO electrode pattern with an L / S of 30 μm / 30 μm formed on the upper surface was prepared. Further, a semiconductor chip was prepared in which a copper electrode pattern having L / S of 30 μm / 30 μm was formed on the lower surface.
　上記透明ガラス基板上に、得られた異方性導電ペーストを厚さ３０μｍとなるように塗工し、異方性導電ペースト層を形成した。次に、異方性導電ペースト層に紫外線照射ランプを用いて紫外線を照射し、光重合によって異方性導電ペースト層を半硬化させ、Ｂステージ化した。次に、異方性導電ペースト層上に上記半導体チップを、電極同士が対向するように積層した。その後、異方性導電ペースト層の温度が１８５℃となるようにヘッドの温度を調整しながら、半導体チップの上面に加圧加熱ヘッドを載せ、３ＭＰａの圧力をかけて異方性導電ペースト層を１８５℃で完全硬化させ、接続構造体を得た。 The obtained anisotropic conductive paste was applied on the transparent glass substrate so as to have a thickness of 30 μm to form an anisotropic conductive paste layer. Next, the anisotropic conductive paste layer was irradiated with ultraviolet rays using an ultraviolet irradiation lamp, and the anisotropic conductive paste layer was semi-cured by photopolymerization to form a B stage. Next, the semiconductor chip was stacked on the anisotropic conductive paste layer so that the electrodes face each other. Then, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer becomes 185 ° C., a pressure heating head is placed on the upper surface of the semiconductor chip, and the pressure of 3 MPa is applied to apply the anisotropic conductive paste layer. Completely cured at 185 ° C. to obtain a connection structure.
　（実施例２）
　異方性導電ペーストの調製の際に、導電性粒子を上記配合物１００重量％中での含有量を５重量％となるように用いたこと以外は実施例１と同様にして、導電性粒子の含有量が５重量％である異方性導電ペーストを得た。得られた異方性導電ペーストを用いたこと以外は実施例１と同様にして、接続構造体を得た。 (Example 2)
In the preparation of the anisotropic conductive paste, the conductive particles were used in the same manner as in Example 1 except that the conductive particles were used so that the content in 100% by weight of the blend was 5% by weight. An anisotropic conductive paste having a content of 5% by weight was obtained. A connection structure was obtained in the same manner as in Example 1 except that the obtained anisotropic conductive paste was used.
　（実施例３）
　異方性導電ペーストの調製の際に、導電性粒子を上記配合物１００重量％中での含有量を１５重量％となるように用いたこと以外は実施例１と同様にして、導電性粒子の含有量が１５重量％である異方性導電ペーストを得た。得られた異方性導電ペーストを用いたこと以外は実施例１と同様にして、接続構造体を得た。 (Example 3)
In the preparation of the anisotropic conductive paste, the conductive particles were used in the same manner as in Example 1 except that the conductive particles were used so that the content in 100% by weight of the blend was 15% by weight. An anisotropic conductive paste having a content of 15% by weight was obtained. A connection structure was obtained in the same manner as in Example 1 except that the obtained anisotropic conductive paste was used.
　（実施例４）
　異方性導電ペーストの調製の際に、導電性粒子を上記配合物１００重量％中での含有量を１重量％となるように用いたこと以外は実施例１と同様にして、導電性粒子の含有量が１重量％である異方性導電ペーストを得た。得られた異方性導電ペーストを用いたこと以外は実施例１と同様にして、接続構造体を得た。 Example 4
In the preparation of the anisotropic conductive paste, the conductive particles were used in the same manner as in Example 1 except that the conductive particles were used so that the content in 100% by weight of the composition was 1% by weight. An anisotropic conductive paste having a content of 1 wt% was obtained. A connection structure was obtained in the same manner as in Example 1 except that the obtained anisotropic conductive paste was used.
　（比較例１）
　異方性導電ペーストの調製の際に、光硬化性化合物としてのエポキシアクリレートと、光重合開始剤としてのアシルホスフィンオキサイド系化合物とを用いなかったこと以外は実施例１と同様にして、異方性導電ペーストを得た。得られた異方性導電ペースト１００重量％中、導電性粒子の含有量は１０重量％であった。得られた異方性導電ペーストを用いたこと以外は実施例１と同様にして、接続構造体を得た。 (Comparative Example 1)
Anisotropic conductive paste was prepared in the same manner as in Example 1 except that epoxy acrylate as a photocurable compound and acylphosphine oxide compound as a photopolymerization initiator were not used. Conductive paste was obtained. In 100% by weight of the obtained anisotropic conductive paste, the content of conductive particles was 10% by weight. A connection structure was obtained in the same manner as in Example 1 except that the obtained anisotropic conductive paste was used.
　（比較例２）
　異方性導電ペーストの調製の際に、導電性粒子を上記配合物１００重量％中での含有量を２０重量％となるように用いたこと以外は実施例１と同様にして、導電性粒子の含有量が２０重量％である異方性導電ペーストを得た。得られた異方性導電ペーストを用いたこと以外は実施例１と同様にして、接続構造体を得た。 (Comparative Example 2)
In the preparation of the anisotropic conductive paste, the conductive particles were used in the same manner as in Example 1 except that the conductive particles were used so that the content in 100% by weight of the blend was 20% by weight. An anisotropic conductive paste having a content of 20 wt% was obtained. A connection structure was obtained in the same manner as in Example 1 except that the obtained anisotropic conductive paste was used.
　（比較例３）
　異方性導電ペーストの調製の際に、導電性粒子を上記配合物１００重量％中での含有量を０．１重量％となるように用いた以外は実施例１と同様にして、導電性粒子の含有量が０．１重量％である異方性導電ペーストを得た。得られた異方性導電ペーストを用いたこと以外は実施例１と同様にして、接続構造体を得た。 (Comparative Example 3)
In the preparation of the anisotropic conductive paste, the conductive particles were used in the same manner as in Example 1 except that the conductive particles were used so that the content in 100% by weight of the blend was 0.1% by weight. An anisotropic conductive paste having a particle content of 0.1% by weight was obtained. A connection structure was obtained in the same manner as in Example 1 except that the obtained anisotropic conductive paste was used.
　（実施例１～４及び比較例１～３の評価）
　（１）粘度
　Ｅ型粘度計（東機産業社製）を用いて、２５℃及び２．５ｒｐｍの条件で、得られた異方性導電ペースト（塗布前の異方性導電ペーストの粘度）の粘度を測定した。 (Evaluation of Examples 1 to 4 and Comparative Examples 1 to 3)
(1) Viscosity Using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) under the conditions of 25 ° C. and 2.5 rpm, the obtained anisotropic conductive paste (viscosity of the anisotropic conductive paste before application) The viscosity was measured.
　（２）リークの有無
　得られた接続構造体を用いて、隣り合う電極２０個においてリークが生じているか否かを、テスターで測定した。 (2) Presence or absence of leakage Using the obtained connection structure, whether or not leakage occurred in 20 adjacent electrodes was measured with a tester.
　（３）ボイドの有無
　得られた接続構造体において、異方性導電ペースト層により形成された硬化物層にボイドが生じているか否かを、透明ガラス基板の下面側から目視により観察した。 (3) Presence / absence of voids In the obtained connection structure, whether or not voids were generated in the cured product layer formed of the anisotropic conductive paste layer was visually observed from the lower surface side of the transparent glass substrate.
　結果を下記の表１に示す。 The results are shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
　上記表１に示すように、実施例１～４の異方性導電ペーストでは、リークが無く、ボイドも見られなかった。 As shown in Table 1 above, the anisotropic conductive pastes of Examples 1 to 4 had no leaks and no voids.
　比較例１の異方性導電ペーストでは、紫外線の照射時に光重合により半硬化しなかったため、加圧及び加熱時に異方性導電ペーストが半導体チップの外周面よりも側方に多く流れた。このため、ガラス基板と半導体チップとの間における異方性導電ペーストの充填が不十分であり、ボイドが見られた。 In the anisotropic conductive paste of Comparative Example 1, since it was not semi-cured by photopolymerization when irradiated with ultraviolet rays, the anisotropic conductive paste flowed more to the side than the outer peripheral surface of the semiconductor chip during pressurization and heating. For this reason, the anisotropic conductive paste was insufficiently filled between the glass substrate and the semiconductor chip, and voids were observed.
　比較例２では、導電性粒子の含有量が多すぎたため、接続されてはならい隣り合う電極間が複数の導電性粒子を介して接続され、リークが発生したと考えられる。 In Comparative Example 2, since the content of conductive particles was too much, it was considered that adjacent electrodes that should not be connected were connected via a plurality of conductive particles, and a leak occurred.
　比較例３の異方性導電ペーストでは、リーグが無く、ボイドも見られなかった。しかし、導電性粒子の含有量が少なすぎたため、電極間に導電性粒子が配置されていない箇所が多くみられた。 In the anisotropic conductive paste of Comparative Example 3, there was no league and no void was seen. However, since the content of the conductive particles was too small, there were many places where the conductive particles were not arranged between the electrodes.
　（実施例５）
　実施例１で得られた異方性導電材料を用意した。 (Example 5)
The anisotropic conductive material obtained in Example 1 was prepared.
　Ｌ／Ｓが３０μｍ／３０μｍのＩＴＯ電極パターンが上面に形成された透明ガラス基板を用意した。また、Ｌ／Ｓが３０μｍ／３０μｍの銅電極パターンが下面に形成された半導体チップを用意した。 A transparent glass substrate having an ITO electrode pattern with an L / S of 30 μm / 30 μm formed on the upper surface was prepared. Further, a semiconductor chip was prepared in which a copper electrode pattern having L / S of 30 μm / 30 μm was formed on the lower surface.
　また、図３（ａ）に示すようなディスペンサーと、該ディスペンサーに接続された光照射装置としての紫外線照射ランプとを備える複合装置を用意した。 Further, a composite apparatus including a dispenser as shown in FIG. 3A and an ultraviolet irradiation lamp as a light irradiation apparatus connected to the dispenser was prepared.
　複合装置を移動させながら、上記透明ガラス基板の上面に、ディスペンサーのシリンジから、得られた異方性導電ペーストを厚さ３０μｍとなるように塗布し、異方性導電ペースト層を形成した。さらに、複合装置を移動させて、異方性導電ペーストを塗布しながら、異方性導電ペースト層に紫外線照射ランプを用いて、４２０ｎｍの紫外線を光照射強度が５０ｍＷ／ｃｍ２となるように照射し、光重合によって異方性導電ペースト層をＢステージ化した。塗布してから、すなわち塗布された異方性導電ペーストが上記透明ガラス基板に接したときから、異方性導電ペースト層に光が照射されるまでの時間Ｔは、０．５秒であった。 While moving the composite device, the anisotropic conductive paste obtained was applied from the syringe of the dispenser to the upper surface of the transparent glass substrate so as to have a thickness of 30 μm to form an anisotropic conductive paste layer. Further, while moving the composite device and applying the anisotropic conductive paste, using the ultraviolet irradiation lamp on the anisotropic conductive paste layer, the ultraviolet irradiation of 420 nm is irradiated so that the light irradiation intensity becomes 50 mW / cm 2. Then, the anisotropic conductive paste layer was B-staged by photopolymerization. The time T from the time when the anisotropic conductive paste was applied to the transparent glass substrate to the time when the anisotropic conductive paste layer was irradiated with light was 0.5 seconds. .
　次に、Ｂステージ化された異方性導電ペースト層の上面に上記半導体チップを、電極同士が対向するように積層した。その後、異方性導電ペースト層の温度が１８５℃となるようにヘッドの温度を調整しながら、半導体チップの上面に加圧加熱ヘッドを載せ、３ＭＰａの圧力をかけて、Ｂステージ化された異方性導電ペースト層を１８５℃で完全硬化させ、接続構造体を得た。 Next, the semiconductor chip was stacked on the upper surface of the B-staged anisotropic conductive paste layer so that the electrodes face each other. Then, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer becomes 185 ° C., a pressure heating head is placed on the upper surface of the semiconductor chip, and a pressure of 3 MPa is applied to make the B-staged difference. The isotropic conductive paste layer was completely cured at 185 ° C. to obtain a connection structure.
　（実施例６）
　異方性導電ペーストの調製の際に、エポキシアクリレートをウレタンアクリレート（ダイセル・サイテック社製「ＥＢＥＣＲＹＬ８８０４」）に変更したこと以外は実施例１と同様にして、異方性導電ペーストを得た。 (Example 6)
An anisotropic conductive paste was obtained in the same manner as in Example 1 except that the epoxy acrylate was changed to urethane acrylate ("EBECRYL8804" manufactured by Daicel-Cytec Co., Ltd.) during the preparation of the anisotropic conductive paste.
　得られた異方性導電ペーストを用いたこと以外は実施例５と同様にして接続構造体を得た。 A connection structure was obtained in the same manner as in Example 5 except that the obtained anisotropic conductive paste was used.
　（実施例７）
　実施例１で得られた異方性導電材料を用意した。 (Example 7)
The anisotropic conductive material obtained in Example 1 was prepared.
　図３（ａ）に示す複合装置にかえて、図４（ａ）に示すディスペンサーと、該ディスペンサーに接続されていない光照射装置としての紫外線照射ランプとを用いて、異方性導電ペーストの塗布が終了した直後に光を照射したこと以外は実施例５と同様にして、接続構造体を得た。塗布してからに光が照射されるまでの時間Ｔは、２秒であった。 An anisotropic conductive paste is applied using a dispenser shown in FIG. 4A and an ultraviolet irradiation lamp as a light irradiation device not connected to the dispenser, instead of the composite device shown in FIG. A connection structure was obtained in the same manner as in Example 5 except that the light was irradiated immediately after the completion of. The time T from application to irradiation with light was 2 seconds.
　（比較例４）
　比較例１で得られた異方性導電材料を用意した。 (Comparative Example 4)
The anisotropic conductive material obtained in Comparative Example 1 was prepared.
　Ｌ／Ｓが３０μｍ／３０μｍのＩＴＯ電極パターンが上面に形成された透明ガラス基板を用意した。また、Ｌ／Ｓが３０μｍ／３０μｍの銅電極パターンが下面に形成された半導体チップを用意した。 A transparent glass substrate having an ITO electrode pattern with an L / S of 30 μm / 30 μm formed on the upper surface was prepared. Further, a semiconductor chip was prepared in which a copper electrode pattern having L / S of 30 μm / 30 μm was formed on the lower surface.
　上記透明ガラス基板の上面に、ディスペンサーのシリンジから、得られた異方性導電ペーストを厚さ３０μｍとなるように塗布し、異方性導電ペースト層を形成した。塗布の際及び塗布の後に光を照射しなかった。 The obtained anisotropic conductive paste was applied on the upper surface of the transparent glass substrate from a syringe of a dispenser so as to have a thickness of 30 μm to form an anisotropic conductive paste layer. No light was applied during and after application.
　次に、異方性導電ペースト層の上面に上記半導体チップを、電極同士が対向するように積層した。その後、異方性導電ペースト層の温度が１８５℃となるようにヘッドの温度を調整しながら、半導体チップの上面に加圧加熱ヘッドを載せ、３ＭＰａの圧力をかけて異方性導電ペースト層を１８５℃で完全硬化させ、接続構造体を得た。 Next, the semiconductor chip was laminated on the upper surface of the anisotropic conductive paste layer so that the electrodes face each other. Then, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer becomes 185 ° C., a pressure heating head is placed on the upper surface of the semiconductor chip and a pressure of 3 MPa is applied to form the anisotropic conductive paste layer. Completely cured at 185 ° C. to obtain a connection structure.
　（比較例５）
　異方性導電ペーストの作製の際に、エポキシアクリレートをナフタレン型エポキシ樹脂（結晶性樹脂、ＤＩＣ社製「ＨＰ－４０３２」）に変更したこと、並びに光重合開始剤としてのアシルホスフィンオキサイド系化合物を用いなかったこと以外は実施例１と同様にして、異方性導電ペーストを得た。 (Comparative Example 5)
In the preparation of the anisotropic conductive paste, the epoxy acrylate was changed to a naphthalene type epoxy resin (crystalline resin, “HP-4032” manufactured by DIC), and an acylphosphine oxide compound as a photopolymerization initiator was used. An anisotropic conductive paste was obtained in the same manner as Example 1 except that it was not used.
　Ｌ／Ｓが３０μｍ／３０μｍのＩＴＯ電極パターンが上面に形成された透明ガラス基板を用意した。また、Ｌ／Ｓが３０μｍ／３０μｍの銅電極パターンが下面に形成された半導体チップを用意した。 A transparent glass substrate having an ITO electrode pattern with an L / S of 30 μm / 30 μm formed on the upper surface was prepared. Further, a semiconductor chip was prepared in which a copper electrode pattern having L / S of 30 μm / 30 μm was formed on the lower surface.
　上記透明ガラス基板の上面に、ディスペンサーのシリンジから、得られた異方性導電ペーストを厚さ３０μｍとなるように塗布し、異方性導電ペースト層を形成した。塗布の際及び塗布の後に光を照射せず、かつ熱重合せず、異方性導電材料層をＢステージ化しなかった。 The obtained anisotropic conductive paste was applied on the upper surface of the transparent glass substrate from a syringe of a dispenser so as to have a thickness of 30 μm to form an anisotropic conductive paste layer. During application and after application, light was not irradiated, thermal polymerization was not performed, and the anisotropic conductive material layer was not B-staged.
　次に、Ｂステージ化していない異方性導電ペースト層の上面に上記半導体チップを、電極同士が対向するように積層した。その後、異方性導電ペースト層の温度が１８５℃となるようにヘッドの温度を調整しながら、半導体チップの上面に加圧加熱ヘッドを載せ、３ＭＰａの圧力をかけて異方性導電ペースト層を１８５℃で完全硬化させ、接続構造体を得た。 Next, the semiconductor chip was laminated on the upper surface of the anisotropic conductive paste layer that was not B-staged so that the electrodes face each other. Then, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer becomes 185 ° C., a pressure heating head is placed on the upper surface of the semiconductor chip and a pressure of 3 MPa is applied to form the anisotropic conductive paste layer. Completely cured at 185 ° C. to obtain a connection structure.
　（実施例５～７及び比較例４～５の評価）
　実施例１～４及び比較例１～３と同様に、上記（１）粘度、上記（２）リークの有無及び上記（３）ボイドの有無について評価を実施した。また、下記の（４）Ｂステージ化された異方性導電ペースト層の粘度についても評価を実施した。 (Evaluation of Examples 5 to 7 and Comparative Examples 4 to 5)
In the same manner as in Examples 1 to 4 and Comparative Examples 1 to 3, the above (1) viscosity, (2) presence or absence of leakage, and (3) presence or absence of voids were evaluated. In addition, the viscosity of the following (4) B-staged anisotropic conductive paste layer was also evaluated.
　（４）Ｂステージ化された異方性導電ペースト層の粘度
　光重合によって異方性導電ペースト層をＢステージ化させた後であって、Ｂステージ化された異方性導電ペースト層の上面に半導体チップを積層する直前のＢステージ化された異方性導電ペースト層の粘度を、レオメーター（Ａｎｔｏｎ　Ｐａａｒ社製）を用いて、２５℃及び２．５ｒｐｍの条件で測定した。 (4) Viscosity of the B-staged anisotropic conductive paste layer After the anisotropic conductive paste layer is B-staged by photopolymerization, on the upper surface of the B-staged anisotropic conductive paste layer The viscosity of the B-staged anisotropic conductive paste layer immediately before stacking the semiconductor chips was measured using a rheometer (manufactured by Anton Paar) at 25 ° C. and 2.5 rpm.
　結果を下記の表２に示す。 The results are shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000029
　（実施例８）
　レゾルシノール型エポキシ樹脂（結晶性樹脂、ナガセケムテックス社製「ＥＸ－２０１」）１６重量部に、ナフタレン型エポキシ樹脂（結晶性樹脂、ＤＩＣ社製「ＨＰ－４０３２」）１４重量部と、熱硬化剤としてのアミンアダクト（味の素ファインテクノ社製「ＰＮ－２３Ｊ」）５重量部と、光硬化性樹脂としてのエポキシアクリレート（ダイセル・サイテック社製「ＥＢＥＣＲＹＬ３７０２」）５重量部と、光硬化開始剤としてのアシルホスフィンオキサイド系化合物（チバ・ジャパン社製「ＤＡＲＯＣＵＲ　ＴＰＯ」）０．１重量部と、硬化促進剤としての２－エチル－４－メチルイミダゾール１重量部と、フィラーとしての平均粒子径０．２５μｍのシリカ３０重量部とを配合し、さらに平均粒子径３μｍの導電性粒子を配合物中での含有量が１０重量％となるように添加した後、遊星式攪拌機を用いて２０００ｒｐｍで５分間攪拌することにより、配合物を得た。 (Example 8)
Resorcinol type epoxy resin (crystalline resin, “EX-201” manufactured by Nagase ChemteX Corporation), 16 parts by weight, naphthalene type epoxy resin (crystalline resin, “HP-4032” manufactured by DIC), 14 parts by weight, and thermosetting 5 parts by weight of an amine adduct (“PN-23J” manufactured by Ajinomoto Fine Techno Co.) as an agent, 5 parts by weight of an epoxy acrylate (“EBECRYL 3702” manufactured by Daicel-Cytech) as a photocurable resin, 0.1 part by weight of an acylphosphine oxide compound (“DAROCUR TPO” manufactured by Ciba Japan), 1 part by weight of 2-ethyl-4-methylimidazole as a curing accelerator, and an average particle size of 0. 30 parts by weight of 25 μm silica, and further conductive particles having an average particle diameter of 3 μm in the blend After the chromatic amount is added so that the 10 wt%, by stirring for 5 minutes at 2000rpm using a planetary mixing machine to obtain a formulation.
　なお、用いた上記導電性粒子は、ジビニルベンゼン樹脂粒子の表面にニッケルめっき層が形成されており、かつ該ニッケルめっき層の表面に金めっき層が形成されている金属層を有する導電性粒子である。 The conductive particles used are conductive particles having a metal layer in which a nickel plating layer is formed on the surface of divinylbenzene resin particles and a gold plating layer is formed on the surface of the nickel plating layer. is there.
　得られた配合物を、ナイロン製ろ紙（孔径１０μｍ）を用いてろ過することにより、異方性導電ペーストを得た。得られた異方性導電ペーストを用いたこと以外は実施例１と同様にして、接続構造体を得た。 The obtained composition was filtered using nylon filter paper (pore diameter: 10 μm) to obtain an anisotropic conductive paste. A connection structure was obtained in the same manner as in Example 1 except that the obtained anisotropic conductive paste was used.
　（実施例９）
　レゾルシノール型エポキシ樹脂の添加量を１６重量部から２５重量部に変更し、かつナフタレン型エポキシ樹脂１４重量部をビスフェノールＡ型エポキシ樹脂（ＪＥＲ社製「エピコート１００１」）５重量部に変更したこと以外は実施例８と同様にして、異方性導電ペーストを得た。得られた異方性導電ペーストを用いたこと以外は実施例１と同様にして、接続構造体を得た。 Example 9
Other than changing the addition amount of resorcinol type epoxy resin from 16 parts by weight to 25 parts by weight and changing 14 parts by weight of naphthalene type epoxy resin to 5 parts by weight of bisphenol A type epoxy resin (“Epicoat 1001” manufactured by JER) Obtained an anisotropic conductive paste in the same manner as in Example 8. A connection structure was obtained in the same manner as in Example 1 except that the obtained anisotropic conductive paste was used.
　（比較例６）
　ビスフェノールＡ型エポキシ樹脂（ＪＥＲ社製「ｊＥＲ１００１」）３０重量部に、ポリグリシジルアミン（東都化成社製「ＹＨ－４３４」）３０重量部と、熱硬化剤としてのジシアンジアミド（ＪＥＲ社製「ＤＩＣＹ－７」）１０重量部と、硬化促進剤として２－エチル－４－メチルイミダゾール１重量部と、フィラーとしてのシリカ（日本アエロジル工業社製「アエロジルＲＹ２００」）５重量部とを配合し、さらに実施例８と同じ導電性粒子を配合物中での含有量が１０重量％となるように添加した後、遊星式攪拌機を用いて２０００ｒｐｍで５分間攪拌することにより、配合物を得た。 (Comparative Example 6)
30 parts by weight of a bisphenol A type epoxy resin (“JER1001” manufactured by JER), 30 parts by weight of polyglycidylamine (“YH-434” manufactured by Tohto Kasei Co., Ltd.), and dicyandiamide (“DICY-” manufactured by JER) 7 ") 10 parts by weight, 1 part by weight of 2-ethyl-4-methylimidazole as a curing accelerator and 5 parts by weight of silica (" Aerosil RY200 "manufactured by Nippon Aerosil Kogyo Co., Ltd.) as a filler After adding the same electroconductive particle as Example 8 so that content in a formulation might be 10 weight%, the formulation was obtained by stirring for 5 minutes at 2000 rpm using a planetary stirrer.
　得られた配合物を、ナイロン製ろ紙（孔径１０μｍ）を用いてろ過することにより、異方性導電ペーストを得た。得られた異方性導電ペーストを用いたこと以外は実施例１と同様にして、接続構造体を得た。 The obtained composition was filtered using nylon filter paper (pore diameter: 10 μm) to obtain an anisotropic conductive paste. A connection structure was obtained in the same manner as in Example 1 except that the obtained anisotropic conductive paste was used.
　（実施例８～９及び比較例６の評価）
　実施例１～４及び比較例１～３と同様に、上記（２）リークの有無及び上記（３）ボイドの有無について評価を実施した。また、下記の（１Ａ）粘度、（５）塗布幅のばらつき及び（６）硬化物層の厚みについても評価を実施した。 (Evaluation of Examples 8 to 9 and Comparative Example 6)
In the same manner as in Examples 1 to 4 and Comparative Examples 1 to 3, the above (2) presence / absence of leakage and (3) presence / absence of voids were evaluated. In addition, the following (1A) viscosity, (5) coating width variation, and (6) cured product layer thickness were also evaluated.
　（１Ａ）粘度
　Ｅ型粘度計（東機産業社製）を用いて、得られた異方性導電ペーストの２５℃及び２．５ｒｐｍでの粘度η１と、２５℃及び５ｒｐｍでの粘度η２とを測定した。 (1A) Viscosity Using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.), the viscosity η1 at 25 ° C. and 2.5 rpm of the obtained anisotropic conductive paste, and the viscosity η2 at 25 ° C. and 5 rpm are obtained. It was measured.
　（５）塗布幅のばらつき
　得られた異方性導電ペーストをノズル径１．１ｍｍのシリンジに充填し、ディスペンサーを用いて、圧力３００Ｐａ、塗布厚み３０μｍ、移動スピード１０ｍｍ／ｓ、塗布ライン距離２０ｍｍ及び塗布幅１ｍｍの条件で、異方性導電ペーストをガラス基板上に塗布した。 (5) Variation in coating width The obtained anisotropic conductive paste was filled into a syringe having a nozzle diameter of 1.1 mm, and using a dispenser, the pressure was 300 Pa, the coating thickness was 30 μm, the moving speed was 10 mm / s, the coating line distance was 20 mm, and An anisotropic conductive paste was applied on a glass substrate under the condition of an application width of 1 mm.
　異方性導電ペーストの塗布開始地点から２ｍｍの距離、５ｍｍの距離、１０ｍｍの距離の各地点での塗布幅を、測長機能付きのマイクロスコープで測定した。 The coating width at each point of 2 mm, 5 mm, and 10 mm from the application start point of the anisotropic conductive paste was measured with a microscope with a length measuring function.
　（６）硬化物層の高さ（厚み）
　上記（５）の評価と同様にして、異方性導電ペーストをガラス基板上に塗布した。塗布の直後に紫外線を照射し、異方性導電ペーストの光硬化を開始させた。さらに、紫外線の照射から１０秒後に、異方性導電ペーストが塗布されたガラス基板を１５０℃のオーブン内に５分間入れ、異方性導電ペーストを熱硬化させた。異方性導電ペーストの硬化により形成された硬化物層の高さを、マイクロメーターで測定した。 (6) Height (thickness) of cured product layer
An anisotropic conductive paste was applied on a glass substrate in the same manner as in the evaluation of (5) above. Immediately after the application, ultraviolet rays were irradiated to initiate photocuring of the anisotropic conductive paste. Furthermore, 10 seconds after the irradiation of the ultraviolet rays, the glass substrate coated with the anisotropic conductive paste was placed in an oven at 150 ° C. for 5 minutes to thermally cure the anisotropic conductive paste. The height of the cured product layer formed by curing the anisotropic conductive paste was measured with a micrometer.
　結果を下記の表３に示す。 The results are shown in Table 3 below.
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000030
　実施例８～９の異方性導電ペーストは、安定的に塗布でき、塗布幅はほぼ一定であった。さらに、実施例８の異方性導電ペーストでは、塗布時に異方性導電ペーストの流れが抑制されたため、得られた硬化物層の厚みが３０μｍであった。 The anisotropic conductive pastes of Examples 8 to 9 could be applied stably and the application width was almost constant. Furthermore, in the anisotropic conductive paste of Example 8, since the flow of the anisotropic conductive paste was suppressed at the time of application, the thickness of the obtained cured product layer was 30 μm.
　比較例６の異方性導電ペーストでは、塗布圧力が一定であるにもかかわらず、塗布量が変化し、塗布幅にばらつきが生じた。 In the anisotropic conductive paste of Comparative Example 6, the coating amount varied and the coating width varied even though the coating pressure was constant.
　１…接続構造体
　２…第１の接続対象部材
　２ａ…上面
　２ｂ…電極
　３…硬化物層（接続部）
　３ａ…上面
　３Ａ…異方性導電材料層
　３Ｂ…Ｂステージ化された異方性導電材料層
　４…第２の接続対象部材
　４ａ…下面
　４ｂ…電極
　５…導電性粒子
　１１…複合装置
　１２…ディスペンサー
　１２ａ…シリンジ
　１２ｂ…把持部
　１３…光照射装置
　１３ａ…光照射装置本体
　１３ｂ…光照射部
　２１…光照射装置
　２１ａ…光照射装置本体
　２１ｂ…光照射部
　３１…台 DESCRIPTION OF SYMBOLS 1 ... Connection structure 2 ... 1st connection object member 2a ... Upper surface 2b ... Electrode 3 ... Hardened | cured material layer (connection part)
3a ... Upper surface 3A ... Anisotropic conductive material layer 3B ... B-staged anisotropic conductive material layer 4 ... Second connection target member 4a ... Lower surface 4b ... Electrode 5 ... Conductive particles 11 ... Composite device 12 ... Dispenser DESCRIPTION OF SYMBOLS 12a ... Syringe 12b ... Grasp part 13 ... Light irradiation apparatus 13a ... Light irradiation apparatus main body 13b ... Light irradiation part 21 ... Light irradiation apparatus 21a ... Light irradiation apparatus main body 21b ... Light irradiation part 31 ... Stand

Claims (10)

  1. 　硬化性化合物と、熱硬化剤と、光硬化開始剤と、導電性粒子とを含有し、
    　前記導電性粒子の含有量が１～１９重量％の範囲内である、異方性導電材料。     Containing a curable compound, a thermosetting agent, a photocuring initiator, and conductive particles,
    An anisotropic conductive material having a content of the conductive particles in the range of 1 to 19% by weight.
  2. 　前記硬化性化合物が、エピスルフィド化合物を含む、請求項１に記載の異方性導電材料。 The anisotropic conductive material according to claim 1, wherein the curable compound contains an episulfide compound.
  3. 　前記硬化性化合物が、エポキシ基及びチイラン基の内の少なくとも一種の基と、（メタ）アクリロイル基とを有する硬化性化合物を含む、請求項１に記載の異方性導電材料。 The anisotropic conductive material according to claim 1, wherein the curable compound includes a curable compound having at least one group selected from an epoxy group and a thiirane group and a (meth) acryloyl group.
  4. 　前記硬化性化合物が、エポキシ基及びチイラン基の内の少なくとも一種の基と、（メタ）アクリロイル基とを有する硬化性化合物を含む、請求項２に記載の異方性導電材料。 The anisotropic conductive material according to claim 2, wherein the curable compound includes a curable compound having at least one group out of an epoxy group and a thiirane group and a (meth) acryloyl group.
  5. 　２５℃及び２．５ｒｐｍでの粘度が、２０～２００Ｐａ・ｓの範囲内である、請求項１～４のいずれか１項に記載の異方性導電材料。 The anisotropic conductive material according to any one of claims 1 to 4, wherein the viscosity at 25 ° C and 2.5 rpm is in the range of 20 to 200 Pa · s.
  6. 　光の照射により硬化が進行されて、Ｂステージ化した後の粘度が２０００～３５００Ｐａ・ｓの範囲内である、請求項１～４のいずれか１項に記載の異方性導電材料。 The anisotropic conductive material according to any one of claims 1 to 4, wherein the viscosity after being cured by light irradiation and having a B-stage is in a range of 2000 to 3500 Pa · s.
  7. 　２５℃及び２．５ｒｐｍでの粘度をη１とし、かつ２５℃及び５ｒｐｍでの粘度をη２としたときに、前記η２が２０Ｐａ・ｓ以上２００Ｐａ・ｓ以下であり、かつ前記η１の前記η２に対する比（η１／η２）が０．９以上１．１以下である、請求項１～４のいずれか１項に記載の異方性導電材料。 When the viscosity at 25 ° C. and 2.5 rpm is η1, and the viscosity at 25 ° C. and 5 rpm is η2, the η2 is 20 Pa · s or more and 200 Pa · s or less, and the ratio of the η1 to the η2 The anisotropic conductive material according to any one of claims 1 to 4, wherein (η1 / η2) is 0.9 or more and 1.1 or less.
  8. 　前記硬化性化合物が、結晶性化合物を含む、請求項７に記載の異方性導電材料。 The anisotropic conductive material according to claim 7, wherein the curable compound includes a crystalline compound.
  9. 　第１の接続対象部材と、第２の接続対象部材と、該第１，第２の接続対象部材を電気的に接続している接続部とを備え、
    　前記接続部が、請求項１～４のいずれか１項に記載の異方性導電材料を硬化させることにより形成されている、接続構造体。     A first connection target member, a second connection target member, and a connection part that electrically connects the first and second connection target members;
    A connection structure in which the connection portion is formed by curing the anisotropic conductive material according to any one of claims 1 to 4.
  10. 　第１の接続対象部材の上面に異方性導電材料を塗布し、異方性導電材料層を形成する工程と、
    　前記異方性導電材料層に光を照射することにより、前記異方性導電材料層の硬化を進行させて、粘度が２０００～３５００Ｐａ・ｓの範囲内となるように、前記異方性導電材料層をＢステージ化する工程と、
    　Ｂステージ化された異方性導電材料層の上面に、第２の接続対象部材をさらに積層する工程とを備え、
    　前記異方性導電材料として、硬化性化合物と、熱硬化剤と、光硬化開始剤と、導電性粒子とを含有し、前記導電性粒子の含有量が１～１９重量％の範囲内である異方性導電材料を用いる、接続構造体の製造方法。     Applying an anisotropic conductive material to the upper surface of the first connection target member to form an anisotropic conductive material layer;
    By irradiating the anisotropic conductive material layer with light, the anisotropic conductive material layer is cured so that the viscosity is in the range of 2000 to 3500 Pa · s. B-stage the layer;
    A step of further laminating a second connection object member on the upper surface of the B-staged anisotropic conductive material layer,
    The anisotropic conductive material contains a curable compound, a thermosetting agent, a photocuring initiator, and conductive particles, and the content of the conductive particles is in the range of 1 to 19% by weight. A method for manufacturing a connection structure using an anisotropic conductive material.
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