JP2014029857A - 絶縁性粒子付き導電性粒子、導電材料及び接続構造体 - Google Patents
絶縁性粒子付き導電性粒子、導電材料及び接続構造体 Download PDFInfo
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- JP2014029857A JP2014029857A JP2013139786A JP2013139786A JP2014029857A JP 2014029857 A JP2014029857 A JP 2014029857A JP 2013139786 A JP2013139786 A JP 2013139786A JP 2013139786 A JP2013139786 A JP 2013139786A JP 2014029857 A JP2014029857 A JP 2014029857A
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Images
Abstract
【解決手段】本発明に係る絶縁性粒子付き導電性粒子1は、導電部12を少なくとも表面に有する導電性粒子2と、導電性粒子2の表面上に配置された複数の絶縁性粒子3とを備える。導電部12の外表面は、防錆処理されている。導電性粒子2の表面積全体に占める絶縁性粒子3により被覆されている部分の面積である被覆率は60%以上である。
【選択図】図1
Description
図1に、本発明の第1の実施形態に係る絶縁性粒子付き導電性粒子を断面図で示す。
上記導電性粒子は、少なくとも表面に導電部を有していればよい。該導電部は導電層であることが好ましい。導電性粒子は、基材粒子と、基材粒子の表面上に配置された導電層を有する導電性粒子であってもよく、全体が導電部である金属粒子であってもよい。なかでも、コストを低減したり、導電性粒子の柔軟性を高くして、電極間の導通信頼性を高めたりする観点からは、基材粒子と、基材粒子の表面上に配置された導電部とを有する導電性粒子が好ましい。
上記絶縁性粒子は、絶縁性を有する粒子である。上記絶縁性粒子は、導電性粒子よりも小さい。絶縁性粒子付き導電性粒子を用いて電極間を接続すると、上記絶縁性粒子により、隣接する電極間の短絡を防止できる。具体的には、複数の絶縁性粒子付き導電性粒子が接触したときに、複数の絶縁性粒子付き導電性粒子における導電性粒子間には上記絶縁性粒子が存在するので、上下の電極間ではなく、横方向に隣り合う電極間の短絡を防止できる。なお、電極間の接続の際に、2つの電極で絶縁性粒子付き導電性粒子を加圧することにより、導電部と電極との間の上記絶縁性粒子を容易に排除できる。導電性粒子の表面に突起が設けられている場合には、導電部と電極との間の上記絶縁性粒子をより一層容易に排除できる。
本発明に係る導電材料は、本発明に係る絶縁性粒子付き導電性粒子と、バインダー樹脂とを含む。本発明に係る絶縁性粒子付き導電性粒子をバインダー樹脂中に分散させる際には、導電性粒子の表面から第1,第2の絶縁性粒子が脱離し難い。本発明に係る絶縁性粒子付き導電性粒子は、バインダー樹脂中に分散され、導電材料として用いられることが好ましい。上記導電材料は、異方性導電材料であることが好ましい。
上述した絶縁性粒子付き導電性粒子を用いて、又は該絶縁性粒子付き導電性粒子とバインダー樹脂とを含む導電材料を用いて、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。
(無電解めっき前処理工程)
テトラメチロールメタンテトラアクリレートとジビニルベンゼンとの共重合樹脂により形成された樹脂粒子(平均粒子径3μm)10gについて、水酸化ナトリウム水溶液によるアルカリ脱脂、酸中和、二塩化スズ溶液におけるセンシタイジングを行った。
パラジウム触媒が付与された樹脂粒子10gをイオン交換水300mLに分散させ、分散液を作製した。分散液に金属ニッケル粒子(平均粒子径50nm)1gを3分間かけて添加し、金属ニッケル粒子が付着した樹脂粒子を作製した。
次に、イオン交換水500mLにコハク酸ナトリウムを溶解させたコハク酸ナトリウム1重量%溶液を調製した。この溶液に金属ニッケル粒子とパラジウムが付着された樹脂粒子10gを加え、混合し、スラリーを調製した。スラリーに硫酸を添加し、スラリーのpHを5に調整した。
4ツ口セパラブルカバー、攪拌翼、三方コック、冷却管及び温度プローブを取り付けた1000mLセパラブルフラスコに、メタクリル酸グリシジル45mmol、メタクリル酸メチル380mmol、ジメタクリル酸エチレングリコール13mmol、アシッドホスホオキシポリオキシエチレングリコールメタクリレート0.5mmol、及び2,2’−アゾビス{2−[N−(2−カルボキシエチル)アミジノ]プロパン}1mmolを含むモノマー組成物を入れた。該モノマー組成物を固形分が10重量%となるように蒸留水を添加した後、300rpmで攪拌し、窒素雰囲気下80℃で24時間重合を行った。反応終了後、凍結乾燥して、アシッドホスホオキシポリオキシエチレングリコールメタクリレートに由来するP−OH基を表面に有する絶縁性粒子を得た。
上記で得られた絶縁性粒子を超音波照射下で蒸留水に分散させ、絶縁性粒子の10重量%水分散液を得た。得られた導電性粒子A10gを蒸留水500mLに分散させ、絶縁性粒子の水分散液5gを添加し、室温で8時間攪拌した。メッシュフィルターで濾過した後、更にメタノールで洗浄、乾燥し、絶縁性粒子付き導電性粒子を得た。
絶縁性粒子の粒径を下記の表1に示すように設定したこと、金属ニッケル粒子の平均粒子径をかえて突起の高さを下記の表1に示すように設定したこと、並びに絶縁性粒子の添加量をかえて上記被覆率を下記の表1に示すように設定したこと以外は実施例1と同様にして、絶縁性粒子付き導電性粒子を得た。
処理前絶縁性粒子として、ゾルゲル法により作製されたシリカ粒子(粒径50nm)を準備した。シランカップリング剤を用いてシリカ粒子の表面にビニル基を導入した。4ツ口セパラブルカバー、攪拌翼、三方コック、冷却管及び温度プローブを取り付けた1000mLセパラブルフラスコに、蒸留水500ml、上記のビニル基を導入したシリカ粒子0.1重量部、メタクリル酸メチル38mmol、ジメタクリル酸エチレングリコール1.3mmol、アシッドホスホオキシポリオキシエチレングリコールメタクリレート0.05mmol、及び2,2’−アゾビス{2−[N−(2−カルボキシエチル)アミジノ]プロパン}0.1mmolを含むモノマー組成物を入れ、超音波照射機で十分乳化した後、300rpmで攪拌し、窒素雰囲気下80℃で24時間重合を行った。反応終了後、凍結乾燥して、アシッドホスホオキシポリオキシエチレングリコールメタクリレートに由来するP−OH基を表面に有するシリカ粒子含有ポリマーコーティング絶縁性粒子を得た。
処理前絶縁性粒子として、粒径が異なるゾルゲル法により作製されたシリカ粒子(粒径100nm)を準備し、この処理前絶縁性粒子を用いたこと以外は実施例9と同様にして、アシッドホスホオキシポリオキシエチレングリコールメタクリレートに由来するP−OH基を表面に有するシリカ粒子含有ポリマーコーティング絶縁性粒子を得た。
導電性粒子の表面を防錆処理しなかったこと以外は実施例1と同様にして、絶縁性粒子付き導電性粒子を得た。
(1)導電性粒子の表面積全体に占める絶縁性粒子により被覆されている部分の合計の面積である被覆率
SEMでの観察により、20個の絶縁性粒子付き導電性粒子を観察した。導電性粒子の表面積全体に占める絶縁性粒子により被覆されている部分の合計の投影面積である被覆率を求めた。20個の被覆率の平均値を被覆率とした。
得られた絶縁性粒子付き導電性粒子を含有量が10重量%となるように、三井化学社製「ストラクトボンドXN−5A」に添加し、分散させ、異方性導電ペーストを得た。
○:凝集した導電性粒子が沈降していない
△:小さな凝集した導電性粒子がわずかに沈降している
×:凝集した導電性粒子が多く沈降している
得られた絶縁性粒子付き導電性粒子を含有量が10重量%となるように、三井化学社製「ストラクトボンドXN−5A」に添加し、分散させ、異方性導電ペーストを得た。
○○:抵抗値が5Ω以下の接続構造体の個数の割合が90%以上
○:抵抗値が5Ω以下の接続構造体の個数の割合が80%以上、90%未満
△:抵抗値が5Ω以下の接続構造体の個数の割合が60%以上、80%未満
×:抵抗値が5Ω以下の接続構造体の個数の割合が60%未満
上記(3)導通性の評価で得られた20個の接続構造体において、隣接する電極間のリークの有無を、テスターで抵抗を測定することにより評価した。絶縁性を下記の基準で判定した。
○○:抵抗値が108Ω以上の接続構造体の個数の割合が80%以上
○:抵抗値が108Ω以上の接続構造体の個数の割合が70%以上、80%未満
△:抵抗値が108Ω以上の接続構造体の個数の割合が60%以上、70%未満
×:抵抗値が108Ω以上の接続構造体の個数の割合が60%未満
2…導電性粒子
3…絶縁性粒子
11…基材粒子
12…導電部
21…絶縁性粒子付き導電性粒子
22…導電性粒子
26…導電部
27…芯物質
28…突起
31…絶縁性粒子付き導電性粒子
32…導電性粒子
36…導電部
37…突起
81…接続構造体
82…第1の接続対象部材
82a…第1の電極
83…第2の接続対象部材
83a…第2の電極
84…接続部
Claims (10)
- 導電部を少なくとも表面に有する導電性粒子と、
前記導電性粒子の表面上に配置された複数の絶縁性粒子とを備え、
前記導電部の外表面が防錆処理されており、
前記導電性粒子の表面積全体に占める前記絶縁性粒子により被覆されている部分の面積である被覆率が60%以上である、絶縁性粒子付き導電性粒子。 - 前記導電性粒子が、前記導電部の外表面に突起を有する、請求項1に記載の絶縁性粒子付き導電性粒子。
- 前記導電性粒子が、前記導電部の外表面に突起を有し、
前記絶縁性粒子の粒子径が、前記突起の高さの1倍以下である、請求項2に記載の絶縁性粒子付き導電性粒子。 - 前記突起の高さが、100nm以上である、請求項2又は3に記載の絶縁性粒子付き導電性粒子。
- 前記絶縁性粒子の粒子径が、前記突起の高さの0.1倍以上、1倍以下である、請求項2〜4のいずれか1項に記載の絶縁性粒子付き導電性粒子。
- 前記被覆率が70%を超える、請求項1〜5のいずれか1項に記載の絶縁性粒子付き導電性粒子。
- 前記絶縁性粒子の粒子径の前記導電性粒子の粒子径に対する比が1/1000以上、1/3以下である、請求項1〜6のいずれか1項に記載の絶縁性粒子付き導電性粒子。
- 前記導電性粒子の表面に、化学結合を介して、前記絶縁性粒子が付着している、請求項1〜7のいずれか1項に記載の絶縁性粒子付き導電性粒子。
- 請求項1〜8のいずれか1項に記載の絶縁性粒子付き導電性粒子と、バインダー樹脂とを含む、導電材料。
- 第1の電極を表面に有する第1の接続対象部材と、
第2の電極を表面に有する第2の接続対象部材と、
前記第1の接続対象部材と、前記第2の接続対象部材を接続している接続部とを備え、
前記接続部が、請求項1〜8のいずれか1項に記載の絶縁性粒子付き導電性粒子により形成されているか、又は前記絶縁性粒子付き導電性粒子とバインダー樹脂とを含む導電材料により形成されており、
前記第1の電極と前記第2の電極とが、前記絶縁性粒子付き導電性粒子における前記導電性粒子により電気的に接続されている、接続構造体。
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