JP2012019203A - 光反射性異方性導電ペースト及び発光装置 - Google Patents
光反射性異方性導電ペースト及び発光装置 Download PDFInfo
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- JP2012019203A JP2012019203A JP2011118967A JP2011118967A JP2012019203A JP 2012019203 A JP2012019203 A JP 2012019203A JP 2011118967 A JP2011118967 A JP 2011118967A JP 2011118967 A JP2011118967 A JP 2011118967A JP 2012019203 A JP2012019203 A JP 2012019203A
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Abstract
【解決手段】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ペーストは、導電粒子及び光反射性絶縁粒子が熱硬化性樹脂組成物に分散されてなるものである。熱硬化性樹脂組成物は、エポキシ化合物と熱触媒型硬化剤とを含有する。
【選択図】図2
Description
ボキシレートを好ましく使用することができる。
式(2a)〜(2d)のスルホニウムアンチモネート錯体(合成方法は特開平10−245378号公報、特開2006−96742号公報参照)を酢酸エチルに溶解し、当該錯体の10質量%酢酸エチル溶液をそれぞれ調製した。これらとは別に式(3)のナトリウムボレート塩(合成方法は特開平10−310587号公報参照)の10質量%水溶液を調製した。
M+=281(スルホニウム残基)
M+=679(ボレート残基)
実測値 C;52.51 H;1.89
理論値 C;52.52 H;1.78
662(C−S)、776、980、1088、1276(Ar−F)、1300、1374、1464、1514、1583、1643、2881(C−H)、2981(C−H)、3107(O−H)
2.6(1H、(d))、3.3(3H、(a))、5.3(2H、(e))、6.9(2H、(c))、7.6(2H、(b))、7.2〜8.1(7H、(f),(g),(h),(i),(j),(k),(l))
M+=245(スルホニウム残基)
M+=679(ボレート残基)
実測値 C;50.39 H;1.77
理論値 C;50.60 H;1.80
662(C−S)、773、980、1088、1276(Ar−F)、1463、1514、1583、1644、2882(C−H)、2983(C−H)、3109(O−H)
2.3(3H、(j))、2.4(1H、(d))、3.3(3H、(a))、4.8(2H、(e))、7.0(2H、(c))、7.6(2H、(b))、7.0〜7.4(4H、(f),(g),(h),(i))
キシフェニル−ベンジル−メチルスルホニウム テトラキス(ペンタフルオロフェニル)ボレート]の分析結果
M+=289(スルホニウム残基)
M+=679(ボレート残基)
実測値が理論値に合致していた。
測定結果のIRチャートを図5に示す。式(1A)のスルホニウムボレート錯体の結合のIR特性吸収は、図5のIRチャートにおいて観察された。
測定結果の1H−NMRチャートを図6Aに示し、対照となる溶媒のTHFの1H−NMRチャートを図6Bに示す。図6Aの1H−NMRチャートにおいて、以下のプロトンが帰属できた。
表1に示す組成の成分を攪拌機を用いて均一に混合することにより、外観色が白色の光反射性異方性導電ペーストを得た。
脂環式エポキシ化合物(セロキサイド2021P、ダイセル化学工業(株))
ビスフェノールA型エポキシ化合物(YX8000、三菱化学(株))
<老化防止剤>
脂環式エポキシヒンダードフェノール系化合物(AO−60、ADEKA(株))
<粘度調整剤>
酸化ケイ素(球状平均粒径10〜20nm、R202、日本アエロジル(株))
<光反射性導電粒子>
金粒子(球状平均粒径5μm)
<光反射性絶縁粒子>
酸化亜鉛(球状平均粒径0.1〜1μm、堺化学(株))
<酸無水物系硬化剤>
メチルヘキサヒドロフタル酸無水物(MH−700、新日本理化(株))
<イミダゾール系硬化促進剤>
2−エチル−4−メチルイミダゾール(2E4MZ、四国化成(株))
<アミン系熱触媒型硬化剤>
2,4,6−トリスジメチルアミノメチルフェノール(DMP−30、日進BM(株))
<芳香族スルホニウム系熱触媒型硬化剤>
式(2b)、(2c)、(2d)、(1a)、(1b)、(1c)及び(1A)のスルホニウムアンチモネート錯体又はスルホニウムボレート錯体。なお、式(2b)、(2c)、(2d)のスルホニウムアンチモネート錯体は、それぞれ三新化成(株)より、商品名SI−60、SI−80、SI−100として市販されている。
得られた光反射性異方性導電ペーストについて、以下に説明するように「揮発量」、「接着力」、「導通信頼性」、「光反射率」及び「LED実装サンプルにおける全光束量」を試験評価した。得られた結果を表1に示す。
実施例1〜16又は比較例1の光反射性異方性導電ペースト5gを、開口径50mmのアルミカップに入れ、異方性導電接続温度である180℃に設定されたホットプレートに置き、30秒間加熱し、室温まで放冷後、重量を測定し、その数値W(g)から揮発量(%)[={(5−W)/5}×100]を求めた。加熱時間を1分、5分に変えること以外、同様に揮発量を求めた。揮発量は0であることが理想的であるが、実用的には0.5%未満であることが望ましい。
Auメッキが施されたガラスエポキシ回路基板に、光反射性異方性導電ペーストを乾燥厚10μmとなるように塗布し、その上に、底面が6.3mm角のLEDチップを仮設置し、フリップチップボンダーを用いて、1N/チップ、180℃、30秒間の条件で加圧加熱して実装した。この実装品のLEDの剥離強度([N/chip]ダイシェア強度測定(PTR−1100、RHESCA(社)))について、実装直後(初期)室温下、実装後150℃環境に100時間放置後室温下、又は実装直後(初期)150℃下、ダイシェア速度20μm/sという条件で測定した。接着力は、70N/chip、少なくとも50N/chip以上であることが望ましい。
Auメッキが施されたガラスエポキシ回路基板に、光反射性異方性導電ペーストを乾燥厚10μmとなるように塗布し、その上に、底面が6.3mm角のICチップを仮設置し、フリップチップボンダーを用いて、1N/chip、180℃、30秒間の条件で加圧加熱して実装した。この実装品の初期導通抵抗を4端子法にて測定した。次に、この実装品に対し熱衝撃試験(TCT:−55℃、0.5hr←→125℃、0.5hrの500サイクル)行い、試験後導通抵抗を4端子法にて測定した。以下の基準に従って評価した。
G(good): 導通抵抗値が1Ω未満の場合
NG(not good): 導通抵抗値が1Ω以上の場合
得られた光反射性異方性導電ペーストを、セラミック製の白色板に乾燥厚で100μmとなるように塗布し、200℃で1分間加熱し、硬化させた。この硬化物について、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 K7105)を測定した。その結果、実施例1〜16及び比較例1の光反射性異方性導電ペーストにおける光反射率は、使用した光反射性導電粒子及び使用した光反射性絶縁粒子がそれぞれ同種類、同配合量であったため、いずれも40〜42%であった。反射率は、実用上30%以上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、カイジョー(株))を用いて15μm高の金バンプを形成した。この金バンプ付きエポキシ基板に、光反射性異方性導電ペーストを用いて、青色LED(Vf=3.2(If=20mA))を200℃、60秒、1Kg/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。
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
24 n電極
25 p電極
26 バンプ
100 光反射性異方性導電ペーストの硬化物
200 発光装置
Claims (15)
- 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ペーストであって、導電粒子及び光反射性絶縁粒子が熱硬化性樹脂組成物に分散されてなり、該熱硬化性樹脂組成物がエポキシ化合物と熱触媒型硬化剤とを含有することを特徴とする光反射性異方性導電ペースト。
- 熱触媒型硬化剤が、アミン系熱アニオン重合触媒型硬化剤又は芳香族スルホニウム系熱カチオン重合触媒型硬化剤である請求項1記載の光反射性異方性導電ペースト。
- 芳香族スルホニウム系化合物が、式(1A)のスルホニウムボレート錯体である請求項4記載の光反射性異方性導電ペースト。
- エポキシ化合物が、脂環式エポキシ化合物である請求項1〜5のいずれかに記載の光反射性異方性導電ペースト。
- 熱硬化性樹脂組成物中の熱触媒型硬化剤の配合量が、エポキシ化合物100質量部に対し、0.5〜3質量部である請求項1〜6のいずれかに記載の光反射性異方性導電ペースト。
- 光反射性絶縁粒子が、酸化チタン、窒化ホウ素、酸化亜鉛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1〜7のいずれかに記載の光反射性異方性導電ペースト。
- 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8記載の光反射性異方性導電ペースト。
- 光反射性絶縁粒子が、鱗片状又は球状銀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請求項1〜7のいずれかに記載の光反射性異方性導電ペースト。
- 熱硬化性樹脂組成物100質量部における光反射性絶縁粒子の配合量が、40〜120質量部である請求項1〜10のいずれかに記載の光反射性異方性導電ペースト。
- 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粒子、酸化亜鉛粒子又は酸化アルミニウム粒子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1〜11のいずれかに記載の光反射性異方性導電ペースト。
- 熱硬化性樹脂組成物100質量部に対する光反射性導電粒子の配合量が、1〜100質量部である請求項12記載の光反射性異方性導電ペースト。
- 請求項1〜13のいずれかに記載の光反射性異方性導電ペーストを介して、発光素子を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、発光ダイオード素子である請求項14記載の発光装置。
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JP2011118967A JP5914987B2 (ja) | 2010-06-09 | 2011-05-27 | 光反射性異方性導電ペースト及び発光装置 |
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WO2013146604A1 (ja) * | 2012-03-26 | 2013-10-03 | 積水化学工業株式会社 | 導電材料及び接続構造体 |
JP5323284B1 (ja) * | 2012-03-26 | 2013-10-23 | 積水化学工業株式会社 | 導電材料及び接続構造体 |
CN103443868A (zh) * | 2012-03-26 | 2013-12-11 | 积水化学工业株式会社 | 导电材料及连接结构体 |
KR101380454B1 (ko) * | 2012-03-26 | 2014-04-01 | 세키스이가가쿠 고교가부시키가이샤 | 도전 재료 및 접속 구조체 |
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KR102032414B1 (ko) * | 2012-06-15 | 2019-10-16 | 데쿠세리아루즈 가부시키가이샤 | 광 반사성 이방성 도전 접착제 및 발광 장치 |
JP2014037528A (ja) * | 2012-07-19 | 2014-02-27 | Dexerials Corp | 光反射性異方性導電接着剤及び発光装置 |
JP2014031451A (ja) * | 2012-08-03 | 2014-02-20 | Asahi Kasei E-Materials Corp | 熱カチオン発生剤組成物、熱硬化性組成物、及び異方導電性接続材料 |
WO2015133343A1 (ja) * | 2014-03-07 | 2015-09-11 | 積水化学工業株式会社 | 導電ペースト、接続構造体及び接続構造体の製造方法 |
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Also Published As
Publication number | Publication date |
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TW201202368A (en) | 2012-01-16 |
US20120248495A1 (en) | 2012-10-04 |
EP2581955A4 (en) | 2015-12-30 |
KR20130088003A (ko) | 2013-08-07 |
WO2011155348A1 (ja) | 2011-12-15 |
EP2581955A1 (en) | 2013-04-17 |
CN102934243A (zh) | 2013-02-13 |
CN102934243B (zh) | 2018-08-31 |
US8710662B2 (en) | 2014-04-29 |
KR101829475B1 (ko) | 2018-02-14 |
TWI624516B (zh) | 2018-05-21 |
JP5914987B2 (ja) | 2016-05-11 |
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