JP7017158B2 - 異方性導電フィルム及びその製造方法 - Google Patents
異方性導電フィルム及びその製造方法 Download PDFInfo
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- JP7017158B2 JP7017158B2 JP2019222598A JP2019222598A JP7017158B2 JP 7017158 B2 JP7017158 B2 JP 7017158B2 JP 2019222598 A JP2019222598 A JP 2019222598A JP 2019222598 A JP2019222598 A JP 2019222598A JP 7017158 B2 JP7017158 B2 JP 7017158B2
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- resin layer
- conductive particles
- conductive
- insulating resin
- layer
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- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
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Description
第1転写型内の導電粒子が絶縁性樹脂層に転着している第1絶縁性樹脂層を形成する工程B、
複数の凹部が形成された第2転写型の凹部に導電粒子を入れる工程C、
第2転写型内の導電粒子が絶縁性樹脂層に転着している第2絶縁性樹脂層を形成する工程D、
第1絶縁性樹脂層の導電粒子の転着面と、第2絶縁性樹脂層の導電粒子の転着面とを対向させ、これらを積層一体化する工程E、
を有し、
各転写型において、隣り合う凹部の最近接距離が、該転写型に入れる導電粒子の平均粒子径の2倍以上である製造方法を提供する。
図1Aは、本発明の一実施例の異方性導電フィルム1Aの断面図であり、図1Bは、その異方性導電フィルム1Aの、導電粒子の配置を示す平面図である。この異方性導電フィルム1Aは、絶縁性樹脂層4に導電粒子2a、2bが分散しているものであって、異方性導電フィルム1Aのフィルム厚方向zの所定の深さに導電粒子2a(図中、濃色で示す)が分散している第1導電粒子層3aと、第1導電粒子層3aと異なる深さに導電粒子2b(図中、淡色で示す)が分散している第2導電粒子層3bを有している。
導電粒子2a、2bとしては、従来公知の異方性導電フィルムに用いられているものの中から適宜選択して使用することができる。例えばニッケル、コバルト、銀、銅、金、パラジウムなどの金属粒子、金属被覆樹脂粒子などが挙げられる。2種以上を併用することもできる。
弾性変形特性K20)は、良好な接続信頼性を得るために、好ましくは100~1000
kgf/mm2、より好ましくは200から500kgf/mm2である。また、第1導
電粒子層3aの導電粒子2aの粒子硬さと、第2導電粒子層3bの導電粒子2bの粒子硬
さは、同じでも異なっていても良い。
絶縁性樹脂層4としては、公知の異方性導電性フィルムで使用される絶縁性樹脂層を適宜採用することができる。例えば、(メタ)アクリレート化合物と光ラジカル重合開始剤とを含む光重合性樹脂から形成した樹脂層、(メタ)アクリレート化合物と熱ラジカル重合開始剤とを含む熱重合性樹脂から形成した樹脂層、エポキシ化合物と熱カチオン重合開始剤とを含む熱重合性樹脂から形成した樹脂層、エポキシ化合物と熱アニオン重合開始剤とを含む熱重合性樹脂から形成した樹脂層等を使用することができる。光ラジカル重合開始剤を使用する場合に、光ラジカル重合開始剤に加えて、熱ラジカル重合開始剤を使用してもよい。また、絶縁性樹脂層4を、複数の樹脂層から形成してもよい。
(i)概要
図1A、図1Bに示した異方性導電フィルム1Aは、概略、次のようにして製造することができる。
まず、図7Aに示すように、平面に複数の凹部11が開口した第1転写型10aの該凹部11に、導電粒子2aを入れる(工程A)。次に、第1転写型10a内の導電粒子2aを絶縁性樹脂層に転着させた第1絶縁性樹脂層4aを形成する(工程B)(図7B~図7E)。
第1転写型及び第2転写型としては、例えば、シリコン、各種セラミックス、ガラス、ステンレススチールなどの金属等の無機材料や、各種樹脂等の有機材料などに対し、フォトリソグラフ法等の公知の開口形成方法によって開口を形成したものを使用することができる。また、転写型は、板状、ロール状等の形状をとることができる。
第1転写型、第2転写型の凹部内に導電粒子2a、2bを収容する手法としては、特に限定されるものではなく、公知の手法を採用することができる。例えば、乾燥した導電粒子またはこれを溶媒中に分散させた分散液を、転写型の凹部の形成面上に散布または塗布し、ブラシやブレードなどを用いて凹部11の形成面をワイプすればよい。
導電粒子2aを転着させた第1絶縁性樹脂層4aを形成する工程B、導電粒子2bを転着させた第2絶縁性樹脂層4bを形成する工程D、それらを積層一体化する工程Eは、第1絶縁性樹脂層4aや第2絶縁性樹脂層4bを構成する絶縁性樹脂の種類に応じて種々の態様を取ることができる。
例えば、工程B、工程Dにおいて、第1絶縁性樹脂層4a及び第2絶縁性樹脂層4bをそれぞれ導電粒子に対して粘着性を有する粘着性樹脂から形成する場合、転写型に収容した導電粒子2a、2bに粘着性樹脂層を押圧し、その粘着性樹脂層を転写型から剥離するだけで導電粒子2a、2bが転着した第1、第2の絶縁性樹脂層4a、4bを得ることができる。
工程B、工程Dにおいて、第1絶縁性樹脂層4a及び第2絶縁性樹脂層4bを、それぞれ熱重合性樹脂を用いて形成する場合、工程Bにおける第1の方法として、第1転写型10aに収容した導電粒子2aに熱重合性樹脂層を押圧することにより、熱重合性樹脂層に導電粒子2aを付着させ、導電粒子2aが付着した熱重合性樹脂層を転写型から剥離し、次いで熱重合性樹脂層を加熱重合して熱重合樹脂層とし、導電粒子2aを熱重合樹脂層に固定する。あるいは、第2の方法として、第1転写型10aに収容した導電粒子2aに熱重合性樹脂層を押圧し、第1転写型10aに導電粒子2aが収容されている状態で熱重合性樹脂を加熱重合し、第1転写型10aから剥離することで導電粒子2aを転着させた第1絶縁性樹脂層4aを得る。
導電粒子2bが転着した第2絶縁性樹脂層4bを得る。
第1絶縁性樹脂層4aを、光重合性樹脂を用いて形成する場合、転写型に収容した導電粒子を転着させた第1絶縁性樹脂層を容易に製造することができるので好ましい。第1絶縁性樹脂層4aを、光重合性樹脂を用いて形成する方法としても、例えば、第1の方法として、(a1)第1転写型10a内の導電粒子2aに光重合性樹脂層を押圧することにより光重合性樹脂層に導電粒子を付着させ、(a2)その光重合性樹脂層を転写型から剥離することにより、導電粒子が転着した光重合性樹脂層を得、(a3)導電粒子が転着した光重合性樹脂層に紫外線を照射して光重合性樹脂を光重合樹脂とすることにより行う方法をあげることができる。
第1絶縁性樹脂層4a及び第2絶縁性樹脂層4bを、熱によっても光によっても重合する熱重合性及び光重合性の樹脂を用いて形成する場合も、上述の熱重合性樹脂又は光重合性樹脂を使用する場合に準じて導電粒子を転着させた絶縁性樹脂層を得ることができる。
(v-1)半硬化状態の絶縁性樹脂層の積層一体化
工程B又は工程Dにおいて、光重合性を有する樹脂を用いて、第1絶縁性樹脂層4a及び第2絶縁性樹脂層4bを半硬化状態に形成した場合、工程Eでは、第1絶縁性樹脂層4aの導電粒子2aの転着面と、第2絶縁性樹脂層4bの導電粒子2bの転着面とを対向させ(図7F)、これらを積層し、紫外線照射することにより積層一体化する(図7G)。こうして得られた積層体から剥離フィルム5a、5bを剥離することにより、図1Aに示した異方性導電フィルム1Aを得ることができる。
工程B又は工程Dにおいて、光重合性を有する樹脂を用いて、第1絶縁性樹脂層4a及び第2絶縁性樹脂層4bを完全硬化状態に形成した場合、工程Eでは、図9Aに示すように、第1絶縁性樹脂層4aと第2絶縁性樹脂層4bの間に、中間樹脂層として絶縁性接着剤層6を挟むことでこれらを一体化し、異方性導電フィルムを得てもよい。この場合、絶縁性接着剤層6は、液状接着性樹脂の塗布、フィルム状接着性樹脂の貼着等により設けることができる。
本発明の異方性導電フィルムは、ICチップ、ICモジュール、FPCなどの第1電子部品と、FPC、ガラス基板、リジッド基板、セラミック基板などの第2電子部品とを異方性導電接続する際に好ましく適用することができる。このようにして得られる接続構造体も本発明の一部である。
フェノキシ樹脂(新日鉄住金化学(株)、YP-50)60質量部、エポキシ樹脂(三菱化学(株)、jER828)40質量部、熱カチオン重合開始剤(潜在性硬化剤)(三新化学工業(株)、SI-60L)2質量部を含有する熱重合性の絶縁性樹脂を調製し、これをフィルム厚さ50μmのPETフィルム上に塗布し、80℃のオーブンにて5分間乾燥させ、PETフィルム上に厚み20μmの粘着性の絶縁性樹脂層を形成した。
実施例1~7及び比較例1~4の異方性導電フィルムについて、(a)初期導通抵抗、(b)導通信頼性、(c)ショート発生率をそれぞれ次のように評価した。結果を表1に示す。
各実施例及び比較例の異方性導電フィルムを、初期導通および導通信頼性の評価用ICとガラス基板の間に挟み、加熱加圧(180℃、80MPa、5秒)して各評価用接続物を得、この評価用接続物の導通抵抗を測定した。ここで、評価用ICとガラス基板は、それらの端子パターンが対応しており、サイズは次の通りである。
外径 0.7×20mm
厚み 0.2mm
Bump仕様 金メッキ、高さ12μm、サイズ15×100μm、バンプ間ギャップ15μm
ガラス材質 コーニング社製
外径 30×50mm
厚み 0.5mm
電極 ITO配線
(a)の評価用ICと各実施例及び比較例の異方性導電フィルムとの評価用接続物を温度85℃、湿度85%RHの恒温槽に500時間おいた後の導通抵抗を、(a)と同様に測定した。なお、この導通抵抗が5Ω以上であると、接続した電子部品の実用的な導通安定性の点から好ましくない。
ショート発生率の評価用ICとして次のIC(7.5μmスペースの櫛歯TEG(test element group))を用意した。
外径 1.5×13mm
厚み 0.5mm
Bump仕様 金メッキ、高さ15μm、サイズ25×140μm、Bump間Gap7.5μm
フェノキシ樹脂(新日鉄住金化学(株)、YP-50)60質量部、エポキシ樹脂(三菱化学(株)、jER828)40質量部、及び熱カチオン重合開始剤(潜在性硬化剤)(三新化学工業(株)、SI-60L)2質量部を含有する熱重合性の絶縁性樹脂を調製し、これをフィルム厚さ50μmのPETフィルム上に塗布し、80℃のオーブンにて5分間乾燥させ、PETフィルム上に厚み20μmの粘着性の絶縁性樹脂層を形成した。
ジビニルベンゼン、スチレン、ブチルメタクリレートの混合比を調整した溶液に、重合開始剤としてベンゾイルパーオキサイドを投入して高速で均一攪拌しながら加熱を行い、重合反応を行うことにより微粒子分散液を得た。前記微粒子分散液をろ過し減圧乾燥することにより微粒子の凝集体であるブロック体を得た。更に、前記ブロック体を粉砕・分級することにより、樹脂コアとして平均粒子径3、4又は5μmのジビニルベンゼン系樹脂粒子を得た。粒子の硬さはジビニルベンゼン、スチレン、ブチルメタクリレートの混合比を調整して行った。
次に、得られたジビニルベンゼン系樹脂粒子(5g)に、パラジウム触媒を浸漬法により坦持させた。次いで、この樹脂粒子に対し、硫酸ニッケル六水和物、次亜リン酸ナトリウム、クエン酸ナトリウム、トリエタノールアミン及び硝酸タリウムから調製された無電解ニッケルメッキ液(pH12、メッキ液温50℃)を用いて無電解ニッケルメッキを行い、表面金属層としてニッケルメッキ層を有するニッケル被覆樹脂粒子を作製した。
(ロ)平均粒子径3μm、粒子硬さ400kgf/mm2
(ハ)平均粒子径3μm、粒子硬さ500kgf/mm2
(ニ)平均粒子径4μm、粒子硬さ200kgf/mm2
(ホ)平均粒子径5μm、粒子硬さ50kgf/mm2
(ヘ)平均粒子径5μm、粒子硬さ200kgf/mm2
(ト)平均粒子径5μm、粒子硬さ300kgf/mm2
実施例8~13及び比較例5~9の異方性導電フィルムについて、(a)初期導通抵抗、(b)導通信頼性、(c)ショート発生率をそれぞれ次のように評価した。追加的に(d)バンプの圧痕状態を観察し評価した。結果を表2に示す。
各実施例又は比較例の異方性導電フィルムを、初期導通および導通信頼性の評価用ICとガラス基板の間に挟み、加熱加圧(170℃、60MPa、10秒)して各評価用接続物を得、この評価用接続物の導通抵抗を測定した。導通抵抗が5Ω未満である場合を非常に良好「A」と評価し、5Ω以上10Ω未満である場合を良好「B」と評価し、10Ω以上である場合を不良「C」と評価した。なお、評価用ICとガラス基板は、それらの端子パターンが対応しており、サイズは次の通りである。
外径: 1.8×20mm
厚み: 0.5mm
Bump仕様: 金メッキ、高さ14又は15μm、サイズ30×85μm
(なお、バンプ高さの「14又は15μm」は、一つのバンプ中で1μmの高低差があることを示している。高さ14μmの部分をバンプ凹部とし、高さ15μmの部分をバンプ凸部とした。)
ガラス材質 コーニング社製
外径 30×50mm
厚み 0.5mm
電極 ITO配線
(a)の評価用ICと各実施例又は比較例の異方性導電フィルムとの評価用接続物を温度85℃、湿度85%RHの恒温槽に500時間おいた後の導通抵抗を、(a)と同様に測定した。導通抵抗が10Ω未満である場合、導通信頼性が非常に良好「A」と評価し、10Ω以上20Ω未満である場合を良好「B」と評価し、20Ω以上である場合を不良「C」と評価した。
ショート発生率の評価用ICとして次のIC(7.5μmスペースの櫛歯TEG(test element group))を用意した。
外径: 1.5×13mm
厚み: 0.5mm
Bump仕様: 金メッキ、高さ15μm、サイズ25×140μm、Bumpスペース10μm、Bump間Gap7.5μm、ギャップ数16セット(1セット当たり10カ所)
外径 30×50mm
厚み 0.5mm
電極 ITO配線
初期導通抵抗評価で使用した評価用接続物について、ガラス基板側からバンプの圧痕を倍率20倍の光学顕微鏡で10個のバンプを観察し、観察された圧痕の数が10箇所以上である場合を非常に良好「A」と評価し、8又は9個の圧痕が観察された場合を良好「B」と評価し、観察された圧痕が7個以下の場合を不良「C」と評価した。バンプ凸部と凹部のいずれかがA又はB評価であれば実用上問題はないと評価できる。
2a、2b 導電粒子
3a 第1導電粒子層
3b 第2導電粒子層
4 絶縁性樹脂層
4a 第1絶縁性樹脂層
4b 第2絶縁性樹脂層
5a 剥離フィルム
6 絶縁性接着剤層
7 応力緩和層
8 中間樹脂層
10a 転写型
11 凹部
20 電子部品
21 端子
22 電子部品
23 端子
Da 第1導電粒子層における導電粒子の平均粒子径
Db 第2導電粒子層における導電粒子の平均粒子径
La 第1導電粒子層における導電粒子の最近接距離
Lb 第2導電粒子層における導電粒子の最近接距離
Lc 異方性導電フィルムの平面視における導電粒子の最近接距離
Pa 第1導電粒子層における導電粒子の中心線
Pb 第2導電粒子層における導電粒子の中心線
S 第1導電粒子層の導電粒子の中心線と第2導電粒子層の導電粒子の中心線との距
離
z フィルム厚方向
Claims (15)
- 複数の凹部が形成された第1転写型の凹部に導電粒子を入れる工程A、
第1転写型内の導電粒子が絶縁性樹脂層に転着している第1絶縁性樹脂層を形成する工程B、
複数の凹部が形成された第2転写型の凹部に導電粒子を入れる工程C、
第2転写型内の導電粒子が絶縁性樹脂層に転着している第2絶縁性樹脂層を形成する工程D、
第1絶縁性樹脂層の導電粒子の転着面と、第2絶縁性樹脂層の導電粒子の転着面とを対向させ、これらを積層一体化する工程E、
を有する異方性導電フィルムの製造方法であって、
各転写型において、隣り合う凹部の最近接距離が、該転写型に入れる導電粒子の平均粒子径の2倍以上であり、
工程Eにおいて、第1絶縁性樹脂層と第2絶縁性樹脂層とを積層一体化させる際に、第1絶縁性樹脂層の導電粒子と第2絶縁性樹脂層の導電粒子とが平面視でずれるように積層する製造方法。 - 工程Eにおいて、第1絶縁性樹脂層と第2絶縁性樹脂層とを積層一体化させる際に、第1絶縁性樹脂層の導電粒子と第2絶縁性樹脂層の導電粒子とが平面視で重ならないように積層する請求項1記載の製造方法。
- 工程B及び工程Dのそれぞれにおいて、
(a1)転写型内の導電粒子に光重合性樹脂層を押圧することにより光重合性樹脂層に導電粒子を付着させ、
(a2)その光重合性樹脂層を転写型から剥離することにより、導電粒子が転着した光重合性樹脂層を得、
(a3)導電粒子が転着した光重合性樹脂層を光重合することにより、導電粒子が転着している光重合樹脂層を形成する請求項1または2記載の製造方法。 - 工程B及び工程Dのそれぞれにおいて、
(b1)転写型内の導電粒子に光重合性樹脂層を押圧し、
(b2)その光重合性樹脂層を光重合して導電粒子が保持された光重合樹脂層を形成し、
(b3)導電粒子が保持された光重合性樹脂層を転写型から剥離することにより、導電粒子が転着している光重合樹脂層を形成する請求項1または2記載の製造方法。 - 工程B及び工程Dにおいて、絶縁性樹脂層を半硬化状態に形成し、
工程Eにおいて、第1絶縁性樹脂層と第2絶縁性樹脂層を積層後、これらを硬化させて一体化する請求項1~4のいずれかに記載の製造方法。 - 工程Eにおいて、第1絶縁性樹脂層の導電粒子の転着面と、第2絶縁性樹脂層の導電粒子の転着面とを、中間樹脂層を介して積層し一体化する請求項1~5のいずれかに記載の製造方法。
- 異方性導電フィルムを平面視した場合に第1導電粒子層の導電粒子と第2導電粒子層の導電粒子の位置が重なっていない請求項1~6のいずれかに記載の製造方法。
- 各導電粒子層において、導電粒子の最近接粒子間距離が、導電粒子の平均粒子径の2倍以上50倍以下である請求項1~7のいずれかに記載の製造方法。
- 第1導電粒子層の導電粒子と第2導電粒子層の導電粒子とが、平均粒子径及び/又は粒子硬さの点で互いに相違している請求項1~8のいずれかに記載の製造方法。
ム。 - 異方性導電フィルムのフィルム厚の方向につき、第1導電粒子層の中心と第2導電粒子層の中心との距離が導電粒子の平均粒子径の1/5以上である請求項1~9のいずれかに記載の製造方法。
- 各導電粒子層において、導電粒子が格子状に配列している請求項1~10のいずれかに記載の製造方法。
- 第1導電粒子層と第2導電粒子層の導電粒子の配列が等しい請求項1~11のいずれかに記載の製造方法。
- 絶縁性樹脂層が、光重合樹脂で形成されている請求項1~12のいずれかに記載の製造方法。
- 絶縁性樹脂層が、重合性樹脂で形成された第1絶縁性樹脂層と、重合開始剤を含有しない中間樹脂層と、重合性樹脂で形成された第2絶縁性樹脂層の積層構造を有し、
第1導電粒子層の各導電粒子は、少なくとも一部が第1絶縁性樹脂層に埋入し、
第2導電粒子層の各導電粒子は、少なくとも一部が第2絶縁性樹脂層に埋入し、
第1導電粒子層の導電粒子と、第2導電粒子層の導電粒子との間に中間樹脂層が存在する請求項1~13のいずれかに記載の製造方法。 - 同一の導電粒子層に存在する任意の方向における導電粒子間距離が等しい請求項1~14のいずれかに記載の製造方法。
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JP7274811B2 (ja) | 2016-05-05 | 2023-05-17 | デクセリアルズ株式会社 | 異方性導電フィルム |
WO2017191781A1 (ja) * | 2016-05-05 | 2017-11-09 | デクセリアルズ株式会社 | 異方性導電フィルム |
KR102549530B1 (ko) * | 2016-06-21 | 2023-06-30 | 삼성디스플레이 주식회사 | 전자 장치의 제조 방법 및 전자 장치 |
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WO2018079365A1 (ja) * | 2016-10-24 | 2018-05-03 | デクセリアルズ株式会社 | 異方性導電フィルム |
JP7035370B2 (ja) * | 2016-10-31 | 2022-03-15 | デクセリアルズ株式会社 | フィラー含有フィルム |
CN109843992B (zh) * | 2016-10-31 | 2022-04-26 | 迪睿合株式会社 | 含填料膜 |
JP7256351B2 (ja) * | 2016-11-30 | 2023-04-12 | デクセリアルズ株式会社 | 導電粒子配置フィルム、その製造方法、検査プローブユニット、導通検査方法 |
JP7039883B2 (ja) * | 2016-12-01 | 2022-03-23 | デクセリアルズ株式会社 | 異方性導電フィルム |
JP7274815B2 (ja) | 2016-12-01 | 2023-05-17 | デクセリアルズ株式会社 | 異方性導電フィルム |
TWI624918B (zh) * | 2017-07-11 | 2018-05-21 | 異向性導電薄膜的製作方法 | |
US20190355277A1 (en) * | 2018-05-18 | 2019-11-21 | Aidmics Biotechnology (Hk) Co., Limited | Hand-made circuit board |
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US20170103959A1 (en) | 2017-04-13 |
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