JP2021109889A - 導電性接着剤、それを用いた接着構造体及び電子部品 - Google Patents
導電性接着剤、それを用いた接着構造体及び電子部品 Download PDFInfo
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- JP2021109889A JP2021109889A JP2020000812A JP2020000812A JP2021109889A JP 2021109889 A JP2021109889 A JP 2021109889A JP 2020000812 A JP2020000812 A JP 2020000812A JP 2020000812 A JP2020000812 A JP 2020000812A JP 2021109889 A JP2021109889 A JP 2021109889A
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- Prior art keywords
- meth
- acrylate
- conductive adhesive
- acid
- electronic component
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- 239000000853 adhesive Substances 0.000 title claims abstract description 94
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- 239000002245 particle Substances 0.000 claims abstract description 52
- 239000000178 monomer Substances 0.000 claims abstract description 50
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 21
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- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
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- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 8
- 229920005989 resin Polymers 0.000 abstract description 23
- 239000011347 resin Substances 0.000 abstract description 23
- 238000003860 storage Methods 0.000 abstract description 12
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- -1 acroyl group Chemical group 0.000 description 41
- 238000000034 method Methods 0.000 description 34
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- 229910052753 mercury Inorganic materials 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- 229910019142 PO4 Inorganic materials 0.000 description 3
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- 230000000996 additive effect Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
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- 239000010949 copper Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
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- 229910001507 metal halide Inorganic materials 0.000 description 3
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
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- GLZWNFNQMJAZGY-UHFFFAOYSA-N octaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCO GLZWNFNQMJAZGY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
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- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
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- 239000004800 polyvinyl chloride Substances 0.000 description 1
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- JTXAHXNXKFGXIT-UHFFFAOYSA-N propane;prop-1-ene Chemical group CCC.CC=C JTXAHXNXKFGXIT-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
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- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
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- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000010490 three component reaction Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明の導電性接着剤は、(メタ)アクリレート(A)、光重合開始剤(B)、リン酸基含有モノマー(C)、有機溶剤に可溶なポリエステル樹脂(D)(以下、単に「ポリエステル樹脂(D)」という場合がある。)及び導電性粒子(E)を含有することを特徴とするものである。換言すれば、(メタ)アクリレート(A)、光重合開始剤(B)及びリン酸基含有モノマー(C)からなる紫外線硬化型樹脂(以下、単に「紫外線硬化型樹脂」という場合がある。)と、ポリエステル樹脂(D)と、導電性粒子(E)とを含有する導電性接着剤である。
本発明の導電性接着剤に係る(メタ)アクリレート(A)は、紫外可視光が照射されることにより硬化し、上記紫外線硬化型樹脂の主剤となるものであり、(メタ)アクロイル基を少なくとも1つ有する化合物である。(メタ)アクリレート(A)はモノマーであってもオリゴマーであってもよいが、モノマーであることが好ましい。
なお、本発明において、「(メタ)アクリレート」とは、アクリレート及びメタクリレート、すなわちアクリル酸エステル及びメタクリル酸エステルを包含する概念である。
また、これら(メタ)アクリレートのアルキレンオキサイド変性物も使用することもできる。
本発明の導電性接着剤に係る光重合開始剤(B)は、上記紫外線硬化型樹脂を効率的に光硬化させる成分である。本発明で用いることができる光重合開始剤(B)は特に制限されないが、例えば、2−ベンジル−2−ジメチルアミノ−1−(4−モルホリノフェニル)−1−ブタノン、2−(ジメチルアミノ)−2−[(4−メチルフェニル)メチル]−[4−(4−モルホリニル)フェニル]−1−ブタノン、2−メチル−1−[4−(メチルチオ)フェニル]−2−モルホリノプロパン−1−オン、ベンゾフェノン、メチルベンゾフェノン、o−ベンゾイル安息香酸、ベンゾイルエチルエーテル、2,2−ジエトキシアセトフェノン、2,4−ジエチルチオキサントン、ジフェニル−(2,4,6−トリメチルベンゾイル)ホスフィンオキシド、エチル−(2,4,6−トリメチルベンゾイル)フェニルホスフィネート、4,4’−ビス(ジエチルアミノ)ベンゾフェノン、1−ヒドロキシシクロヘキシル−フェニルケトン、2,2−ジメトキシ−1,2−ジフェニルエタン−1−オン、1−[4−(2−ヒドロキシエトキシ)−フェニル]−2−ヒドロキシ−2−メチル−1−プロパン−1−オン、2,2−ジメトキシ−2−フェニルアセトフェノール及び1−[4−(2−ヒドロキシエトキシ)−フェニル]−2−ヒドロキシ−2−メチル−1−プロパン−1−オン等のアルキルフェノン系光重合開始剤、ビス(2,4,6−トリメチルベンゾイル)−フェニルホスフィンオキサイド及びジフェニル(2,4,6−トリメチルベンゾイル)ホスフィンオキシド等のアシルフォスフィンオキサイド系光重合開始剤、1,2−オクタンジオン,1−[4−(フェニルチオ)−2−(O−ベンゾイルオキシム)]等のオキシムエステル系光重合開始剤、並びにスルホニウム塩系光重合開始剤等が挙げられる。これらの光重合開始剤は、1種のみを使用してもよく、2種以上を任意の割合で混合して使用することもできる。
本発明の導電性接着剤に係るリン酸基含有モノマー(C)は、上記紫外線硬化型樹脂の密着性向上に寄与する成分である。本発明で用いることができるリン酸基含有モノマー(C)は、特に制限されず、重合性を有し、かつリン酸基を有するモノマーであればよい。
本発明の導電性接着剤に係るポリエステル樹脂(D)は、上記紫外線硬化型樹脂と導電性粒子とを含む導電性接着剤に貯蔵安定性を付与する成分である。本発明者らは、有機溶剤に可溶なポリエステル樹脂(D)が、主成分となる(メタ)アクリレート(A)に対して溶解性や相溶性に優れ、更に上記紫外線硬化型樹脂と導電性粒子とを含む導電性接着剤に優れた貯蔵安定性を付与することができることを見出した。
本発明で用いることができるポリエステル樹脂は、有機溶剤に可溶なものであればよく、例えば、多価カルボン酸成分とグリコール成分との重合により得られる。
有機溶剤としては、例えば、メタノール、エタノール、イソプロピルアルコール等のアルコール系溶剤、酢酸エチル、酢酸ブチル、酢酸イソブチル、γ−ブチロラクトン等のエステル系溶剤、アセトン、シクロヘキサノン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル等のセロソルブ系溶剤、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のグリコールエステル系溶剤、ヘキサン、ヘプタン、シクロヘキサン、トルエン、キシレン等の炭化水素系溶剤、ジクロロメタン、クロロホルム、オルトジクロロベンゼン等のハロゲン系溶剤、テトラヒドロフラン、アセトニトリル、ジメチルスルホキシド、N,N−ジメチルアセトアミド、N,N−ジメチルホルムアミド、N−メチル−2−ピロリドン等が挙げられる。
非晶性ポリエステル樹脂としては、数平均分子量(Mw)が1,000〜40,000、好ましくは1,500〜30,000のものが、(メタ)アクリレート(A)に対する溶解性と、得られる導電性接着剤の密着性の観点から好ましい。
非晶性ポリエステルのガラス転移温度(Tg)は、−20℃〜50℃であることが好ましく、−10℃〜20℃のものが、密着性の観点からより好ましい。ガラス転移温度が過度に低いと粘着性が強くなるおそれがあり、ガラス転移温度が過度に高いと密着性が低下するおそれがある。
ポリエステル樹脂(D)の配合量は、リン酸基含有モノマー(C)100質量部に対して10〜2000質量部が好ましく、50〜400質量部とすることが、貯蔵安定性及び密着性の観点から、より好ましい。
本発明の導電性接着剤に係る導電性粒子(E)は、導電性を付与する成分である。本発明においては、導電性粒子(E)として、導電性接着剤、異方性導電膜、異方導電性接着剤に使用されている公知のものを用いることができる。導電性粒子(E)としては、例えば、金、銀、銅、ニッケル、パラジウム、ハンダ等の金属粒子、カーボン粒子のようなそれ自体で導電性を有するもの、芯材粒子の表面を導電性金属で被覆処理した導電性粒子等が挙げられる。
フィルムや紙のような基板1の一方の面である表面1a上に、電極であるアルミアンテナ2が形成されている。表面1aには、少なくともアルミアンテナ2の全体を含む範囲に、本発明の導電性接着剤3が塗布され紫外可視光により硬化されている。基板1には、表面1a上に、金属電極5を有する電子部品、すなわち半導体であるICチップ4が、金属電極5がアルミアンテナ2の上方に位置するように載置されている。ICチップ4は、本発明の導電性接着剤3(導電性粒子6を含む)によって基板1の表面1a側に接着されている。なお、アルミアンテナ2と、金属電極5すなわちICチップ4とは、導電性粒子6を介して通電するように構成されている。
図2の電子部品を実装する装置30は、基板1を載置すると共に基板1を加熱する加熱部材であるヒートテーブル31と、紫外可視光を照射する照射部材32と、照射部材32をヒートテーブル31に向かってあるいはヒートテーブル31から離れるように移動させる駆動装置33と、制御部34とを備えている。制御部34は、ヒートテーブル31と、照射部材32と、駆動装置33とのそれぞれに電気的に接続されている。
ICチップ4の平面形状は任意の形状でよいが、ここでは、図4に示されるような楕円形状を有するものとして説明する。なお、基板1に実装されたICチップ4は、ICカードやICタグなどのRFID関連製品に用いられる。また、基板1に実装された発光ダイオード14は、発光電子部品に用いられる。
(メタ)アクリレート(A)は、下記の市販のものを使用した。
光重合開始剤(B)は、下記の市販のものを使用した。
リン酸基含有モノマー(C)は、下記の市販のものを使用した。
ポリエステル樹脂(D)は、下記の市販のものを使用した。これらはいずれもメチルエチルケトン100質量部に対して25℃で5質量部以上溶解した。
導電性粒子は、球状の樹脂粒子の表面に金−ニッケルの導電層を有する平均粒子径が3.0μmである金めっき粒子(日本化学工業製)を用いた。
表5に示す組成で、(メタ)アクリレート(A)、光重合開始剤(B)、リン酸基含有モノマー(C)、ポリエステル樹脂(D)及び添加剤としてアエロジルRX200(チキソ性付与剤:日本アエロジル製)を、自転・公転式真空ミキサーを用いて25℃で1時間混合し、実施例1〜8及び比較例1〜2の導電性接着剤を調製した。
導電性接着剤5gを容器に入れ、その容器を30℃に保ち、1日後及び3日後の状態を目視で観察し、その状態を評価した。結果を表5に併記した。
なお、表中の貯蔵安定性の評価結果は下記のことを示す。
×:1日後には硬化している。
〇:1日後は状態に変化なし、3日後にはゲルが観察される。
◎:1日後及び3日後も状態に変化なし。
PETフィルム上にアルミニウム配線が形成された基板(サイズ:縦2.5cm、横8cm)上のアルミ配線の全体を含む範囲に、実施例及び比較例で調製した導電性接着剤を、硬化後の厚さが50μmとなるようにディスペンス法で塗布し、金パンプを有するICを載置した。温度25℃、1N/mm2の加圧下で、紫外可視光(波長365nm、照度5,000mW/cm2)を2秒間照射して導電性接着剤を硬化させることにより、評価用の接着構造体を作製した。なお、用いた導電性接着剤は調製して2時間以内のものを使用した。
作製した接着構造体について、導電性接着剤のダイシェア強度を測定した。ダイシェア強度は、基板からICチップを剥離する際の強度(N/mm2)を、デジタルフォースゲージを用いて測定した。結果を表5に併記した。なお、表中のダイシェア強度結果は下記のことを示す。
○:20N/mm2以上
×:20N/mm2未満
1a (基板の)表面
1b (基板の)底面
2 アルミアンテナ(電極)
3 導電性接着剤
4 ICチップ(半導体、電子部品)
5 金属電極
6 導電性粒子
14 発光ダイオード(電子部品)
20 外接矩形
21 (外接矩形の)長辺
22 (外接矩形の)短辺
23 非照射領域
30 装置
31 ヒートテーブル(加熱部材)
32 照射部材
33 駆動装置
34 制御部
35 接触面
36 板部材
37 光源
Claims (10)
- (メタ)アクリレート(A)、光重合開始剤(B)、リン酸基含有モノマー(C)、有機溶剤に可溶なポリエステル樹脂(D)及び導電性粒子(E)を含有する導電性接着剤。
- リン酸基含有モノマー(C)が、リン酸基含有(メタ)アクリレートである請求項1に記載の導電性接着剤。
- リン酸基含有モノマー(C)の含有量が、(メタ)アクリレート(A)100重量部に対して1〜50質量部である請求項1に記載の導電性接着剤。
- ポリエステル樹脂(D)が、非晶質ポリエステル樹脂である請求項1に記載の導電性接着剤。
- ポリエステル樹脂(D)の配合量が、リン酸基含有モノマー(C)100質量部に対して10〜2000質量部である請求項1に記載の導電性接着剤。
- 導電性粒子(E)が、芯材粒子の表面を導電性金属で被覆した導電性粒子である請求項1に記載の導電性接着剤。
- 異方導電性接着剤である請求項1〜6のいずれか1項に記載の導電性接着剤。
- 請求項1〜7のいずれか1項に記載の導電性接着剤を介して被接着部材同士が接着されている接着構造体。
- 請求項1〜7のいずれか1項に記載の導電性接着剤を用いた電子部品。
- 電子部品が、ICカード、ICタグ及び発光電子部品から選ばれる請求項9に記載の電子部品。
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