JP5888023B2 - 光反射性異方性導電接着剤及び発光装置 - Google Patents
光反射性異方性導電接着剤及び発光装置 Download PDFInfo
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- JP5888023B2 JP5888023B2 JP2012056858A JP2012056858A JP5888023B2 JP 5888023 B2 JP5888023 B2 JP 5888023B2 JP 2012056858 A JP2012056858 A JP 2012056858A JP 2012056858 A JP2012056858 A JP 2012056858A JP 5888023 B2 JP5888023 B2 JP 5888023B2
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- ZXQPRTUUOOOZAS-UHFFFAOYSA-N oxiran-2-yl(oxiran-2-ylmethoxy)methanamine Chemical compound C1OC1C(N)OCC1CO1 ZXQPRTUUOOOZAS-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- QFJIELFEXWAVLU-UHFFFAOYSA-H tetrachloroplatinum(2+) dichloride Chemical compound Cl[Pt](Cl)(Cl)(Cl)(Cl)Cl QFJIELFEXWAVLU-UHFFFAOYSA-H 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
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- 238000000411 transmission spectrum Methods 0.000 description 1
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Description
アリルグリシジルエーテル(アリルグリシジルエーテル−S、四日市合成(株))1gと、ビニルシクロヘキサン(Acros社)1gとを採取し、トルエン3gに投入して溶解させた。このトルエン溶液に、メチルハイドロジェンシロキサン・ジメチルシロキサンコポリマー(HMS−082、Gelect社)を、メチルハイドロジェンシロキサン・ジメチルシロキサンコポリマー/アリルグリシジルエーテル/ビニルシクロヘキサンの当量比が1/0.5/0.5となるように滴下し、反応溶液を得た。
導電粒子と光反射性絶縁粒子とを除く表1に示す配合量(質量部)の成分を、一般的な卓上型撹拌機を用いて均一に混合することにより熱硬化性樹脂組成物を調製した。この熱硬化性樹脂組成物に、Au粒子10phr[parts per hundred resin]と、光反射性絶縁粒子30phrとを添加し、卓上型攪拌機を用いて均一に混合することにより外観が白色の光反射性異方性導電接着剤を得た。
攪拌機つきフラスコに粒状銀粒子(平均粒径1.0μm)5gとトルエン50mlとを投入し、攪拌しながらフラスコにシランカップリング剤(3−メタクリロキシプロピルトリエトキシシラン)0.25gを投入し、25℃で60分間攪拌した。次に、この混合物に、メタクリル酸メチル2gとメタクリル酸−2−ヒドロキシエチル2gとベンゾイルパーオキサイド0.04gと2,4−トリレンジイソシアネート1gとを投入し、80℃で12時間攪拌することにより、光反射性絶縁粒子として絶縁被覆銀粒子を得た。絶縁被覆を含めた光反射性絶縁粒子の平均粒径は5.0μmであった。
平均粒子径0.5μmの酸化チタン粉末と、外観色が茶色の平均粒径5μmのAu被覆樹脂導電粒子(平均粒径4.6μmの球状アクリル樹脂粒子に0.2μm厚の無電解金メッキを施した粒子)とを、メカノフュージョン装置に投入し、導電粒子の表面に酸化チタン粒子からなる約0.5μm厚の光反射層を成膜することにより、光反射性導電粒子を得た。この光反射性導電粒子の外観色は灰色であった。
得られた光反射性異方性導電接着剤について、以下に説明するように光反射率測定、全光束量測定、ダイシェア強度測定、導通発光確認試験をそれぞれ行った。
光反射性異方性導電接着剤をセラミック製の白色板に塗布し、200℃で30秒間加熱することにより厚さ1mmの硬化物を得た。この硬化物を1cm角に切り出し、光反射率測定用サンプルとした。このサンプルを150℃のオーブン内に1000時間放置した。この放置前(初期)と放置後(エージング後)のサンプルについて、分光光度計(U3300、日立製作所(株))を用いて、波長450nmの光に対する反射率(JIS K7150)を測定した。得られた結果を表1に示す。光反射率は、実用上30%以上であり、また、エージング前後の光反射率の減少率が20%以下であることが望まれる。
100μmピッチの銅配線にNi/Au(5.0μm厚/0.3μm厚)メッキ処理した配線を有するガラスエポキシ基板に、バンプボンダー(FB700、(株)カイジョー)を用いて15μm高の金バンプを形成した。この金バンプ付きガラスエポキシ基板に、光反射性異方性導電接着剤を用いて、青色LED(Vf=3.2(If=20mA))を200℃、30秒、100gf/チップという条件でフィリップチップ実装し、テスト用LEDモジュールを得た。このテスト用LEDモジュールを85℃、85%RHの環境下で1000時間発光させ、発光の初期及び1000時間発光後(エージング後)におけるその全光束量を、全光束測定システム(積分全球)(LE−2100、大塚電子株式会社)を用いて測定した(測定条件 If=20mA(定電流制御))。得られた結果を表1に示す。全光束量は、実用上、初期において250mlm以上であることが望まれる。また、エージング前後の全光束量の減少率が15%以下であることが望まれる。
全光束量測定で作成したものと同じテスト用LEDモジュールを新たに作成し、それを85℃、85%RHの環境下で1000時間発光(If=20mA(定電流制御))させ、発光の初期及び1000時間発光後(エージング後)における光反射性異方性導電接着剤のダイシェア強度を、ダイシェア強度測定機(PTR−1100、RHESCA社)を用いて20μm/secという剪断速度で測定した。得られた結果を表1に示す。ダイシェア強度は、実用上70N/chip以上であることが望まれる。また、エージング前後のダイシェア強度の減少率が10%以下であることが望まれる。
全光束量測定で作成したものと同じテスト用LEDモジュールを新たに作成し、それを85℃、85%RHの環境下で3000時間発光(If=20mA(定電流制御))させ、発光の初期及び3000時間発光後(エージング後)において異常(導通不良等)の発生の有無を目視確認した。異常が発生しない場合を“OK”と評価し、発生した場合を“NG”と評価した。得られた結果を表1に示す。
2 無機粒子
3 光反射層
4 熱可塑性樹脂
10、20 光反射性導電粒子
11 熱硬化性樹脂組成物の硬化物
21 基板
22 接続端子
23 LED素子
24 n電極
25 p電極
26 バンプ
100 光反射性異方性導電接着剤の硬化物
200 発光装置
Claims (23)
- 発光素子を配線板に異方性導電接続するために使用する光反射性異方性導電接着剤であって、シリコーン樹脂と硬化剤とを含有する熱硬化性樹脂組成物、導電粒子及び光反射性絶縁粒子を含有する光反射性異方性導電接着剤において、
該シリコーン樹脂が、グリシジルオキシアルキル・アリサイクリックアルキル変性オルガノポリシロキサンであり、
光反射性絶縁粒子の形状が鱗片状であり、その長径が0.1〜100μmであり、短径が0.01〜10μmであり、厚みが0.01〜10μmである
光反射性異方性導電接着剤。 - 光反射性絶縁粒子が、酸化チタン、窒化ホウ素、酸化亜鉛、酸化ケイ素及び酸化アルミニウムからなる群より選択される少なくとも一種の無機粒子である請求項1記載の光反射性異方性導電接着剤。
- 光反射性絶縁粒子が、酸化チタン粒子である請求項2記載の光反射性異方性導電接着剤。
- 光反射性絶縁粒子の屈折率(JIS K7142)が、熱硬化性樹脂組成物の硬化物の屈折率(JIS K7142)よりも大きい請求項1〜3のいずれかに記載の光反射性異方性導電接着剤。
- 光反射性絶縁粒子の屈折率(JIS K7142)が、熱硬化性樹脂組成物の硬化物の屈折率(JIS K7142)よりも少なくとも0.02程度大きい請求項4記載の光反射性異方性導電接着剤。
- 発光素子を配線板に異方性導電接続するために使用する光反射性異方性導電接着剤であって、シリコーン樹脂と硬化剤とを含有する熱硬化性樹脂組成物、導電粒子及び光反射性絶縁粒子を含有する光反射性異方性導電接着剤において、
該シリコーン樹脂が、グリシジルオキシアルキル・アリサイクリックアルキル変性オルガノポリシロキサンであり、
光反射性絶縁粒子が、鱗片状又は球状金属粒子の表面を絶縁性樹脂で被覆した樹脂被覆金属粒子である光反射性異方性導電接着剤。 - 光反射性絶縁粒子が、鱗片状銀粒子の表面を絶縁性樹脂で被覆した樹脂被覆銀粒子である請求項6記載の光反射性異方性導電接着剤。
- 光反射性絶縁粒子の形状が球状である場合、その粒径が0.02〜20μmである請求項6記載の光反射性異方性導電接着剤。
- 光反射性絶縁粒子の形状が鱗片状である場合、その長径が0.1〜100μmであり、短径が0.01〜10μmであり、厚みが0.01〜10μmである請求項6又は7記載の光反射性異方性導電接着剤。
- 光反射性絶縁粒子の屈折率(JIS K7142)が、熱硬化性樹脂組成物の硬化物の屈折率(JIS K7142)よりも大きい請求項6〜9のいずれかに記載の光反射性異方性導電接着剤。
- 光反射性絶縁粒子の屈折率(JIS K7142)が、熱硬化性樹脂組成物の硬化物の屈折率(JIS K7142)よりも少なくとも0.02程度大きい請求項10記載の光反射性異方性導電接着剤。
- 絶縁性樹脂が、イソシアネート系架橋剤で架橋されたアクリル系樹脂である請求項6〜11のいずれかに記載の光反射性異方性導電接着剤。
- アクリル系樹脂が、メタクリル酸メチルとメタクリル酸2−ヒドロキシエチルとをラジカル共重合させたものである請求項12に記載の光反射性異方性導電接着剤。
- 熱硬化性樹脂組成物に対する光反射性絶縁粒子の配合量が、1〜50体積%である請求項1〜13のいずれかに記載の光反射性異方性導電接着剤。
- 該グリシジルオキシアルキル・アリサイクリックアルキル変性オルガノポリシロキサンが、アルキルハイドロジェンポリシロキサンに対し、アルケニルグリシジルエーテルとアルケニルシクロアルカンとをハイドロシリレーションさせて得られたものであり、該硬化剤が酸無水物系硬化剤である請求項1〜14のいずれかに記載の光反射性異方性導電接着剤。
- 該グリシジルオキシアルキル・アリサイクリックアルキル変性オルガノポリシロキサンが、重量平均分子量300以上70000以下のアルキルハイドロジェンポリシロキサン1当量に対し、合計で0.7〜1.3当量のアルケニルグリシジルエーテルとアルケニルシクロアルカンとを、アルケニルグリシジルエーテル1モルに対しアルケニルシクロアルカンが0.3〜2モルとなるようにハイドロシリレーションさせて得られたものである請求項15記載の光反射性異方性導電接着剤。
- アルキルハイドロジェンポリシロキサンがメチルハイドロジェンポリシロキサンであり、アルケニルグリシジルエーテルがアリルグリシジルエーテルであり、アルケニルシクロアルカンがビニルシクロヘキサンである請求項15又は16記載の光反射性異方性導電接着剤。
- 導電粒子が、金属材料で被覆されているコア粒子と、その表面に酸化チタン、窒化ホウ素、酸化亜鉛、酸化ケイ素又は酸化アルミニウムから選択された少なくとも一種の無機粒子から形成された光反射層とからなる光反射性導電粒子である請求項1〜17のいずれかに記載の光反射性異方性導電接着剤。
- コア粒子の粒径に対する光反射層の厚みが0.5〜50%である請求項18記載の光反射性異方性導電接着剤。
- 光反射層を構成する無機粒子の粒径が、0.02〜4μmである請求項18又は19記載の光反射性異方性導電接着剤。
- 熱硬化性樹脂組成物に対する光反射性導電粒子の配合量が、5〜30体積%である請求項18記載の光反射性異方性導電接着剤。
- 請求項1〜21のいずれかに記載の光反射性異方性導電接着剤を介して、発光素子がフリップチップ方式で配線板に実装されている発光装置。
- 発光素子が、発光ダイオードである請求項22記載の発光装置。
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KR20090108550A (ko) * | 2008-04-11 | 2009-10-15 | 신에쓰 가가꾸 고교 가부시끼가이샤 | 반도체 소자용 실리콘 접착제 |
JP5499448B2 (ja) | 2008-07-16 | 2014-05-21 | デクセリアルズ株式会社 | 異方性導電接着剤 |
JP5644759B2 (ja) | 2009-03-11 | 2014-12-24 | 信越化学工業株式会社 | 太陽電池セル電極の接続用シート、太陽電池モジュールの製造方法及び太陽電池モジュール |
CN101851478B (zh) * | 2010-04-29 | 2012-11-21 | 黄文迎 | 一种快速固化导电胶粘剂组合物及其制备方法 |
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EP2584015A1 (en) | 2013-04-24 |
CN103415585A (zh) | 2013-11-27 |
KR101995599B1 (ko) | 2019-07-02 |
TW201242118A (en) | 2012-10-16 |
US8852462B2 (en) | 2014-10-07 |
WO2012124724A1 (ja) | 2012-09-20 |
CN103415585B (zh) | 2015-04-29 |
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