JP7133047B2 - レーザにより離型可能な組成物、その積層体及びレーザによる離型方法 - Google Patents
レーザにより離型可能な組成物、その積層体及びレーザによる離型方法 Download PDFInfo
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Description
本発明によれば、基材密着性、貼付性、転写性及び耐溶剤性に優れたレーザにより離型可能な組成物が提供される。当該レーザにより離型可能な組成物は、アクリル樹脂、遮光材、添加剤及び溶剤を含む。以下、各成分について詳しく説明する。
上記目的を達成するために、本発明の一実施形態において、アクリル樹脂は、第三級アミノ基及び第二級アミノ基からなる群より選択される少なくとも1種を含む窒素含有有機基、環状エーテル基含有有機基、並びにヒドロキシル基含有有機基を含む。
本発明の遮光材は、前記レーザにより離型可能な組成物に、可視光線、赤外線若しくは紫外線のうちの少なくとも1つの波長域の光を吸収させ、又は可視光線、赤外線若しくは紫外線のうちの少なくとも1つの波長域の光の透過を遮断させる材料であればよい。遮光材の添加により、その特定の波長域に対応するレーザを使用してレーザにより離型可能な組成物で形成される膜と支持材とを分離することができる。遮光材の材料には、カーボンブラック、チタンブラック、酸化チタン、酸化鉄、窒化チタン、シリカフューム、有機顔料、無機顔料、染料又はそれらの組み合わせなどが含まれるが、これらに限定されない。
添加剤は、例えば密着促進剤、架橋剤などである。密着促進剤は、シラン類、シロキサン類の化合物又は界面活性剤であってもよい。好ましくは、密着促進剤は、エチレン性基、エポキシ基、アミノ基、酸無水物、チオール基又はイソシアネート基などを含むシロキサン化合物である。より好ましくは、密着促進剤は、エチレン性基を含むシロキサン化合物である。架橋剤は、好ましくは熱架橋剤である。熱架橋剤は、末端封止型又は非末端封止型イソシアネート基を有する化合物、例えば、ジビニルエーテルのようなアルケニルエーテル基を含む化合物、ハイドロカルビルオキシハイドロカルビルを含む化合物、ジ酸無水物基を含む化合物、ジチオール基を含む化合物、エポキシ樹脂、メラミン化合物、フェノール化合物などであってもよい。添加剤は、1種又は2種以上の組み合わせであってもよい。
溶剤は、アミド類、シクロアミド類、エステル類、エーテル類、アルコール類又はこれらの溶剤の任意比率での混合溶剤であってもよい。N-メチルピロリドン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルカプロラクタム、ジメチルスルホキシド、テトラメチル尿素、ヘキサメチルホスファミド、γ-ブチロラクトン、ピリジン、メタノール、エタノール、イソプロパノール、n-ブタノール、シクロヘキサノール、エチレングリコール、エチレングリコールメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチルエーテル、アセトン、メチルエチルケトン、シクロヘキサノン、酢酸メチル、酢酸エチル、テトラヒドロフラン、ジクロロメタン、クロロホルム、1,2-ジクロロエタン、ベンゼン、トルエン、キシレン、n-ヘキサン、n-ヘプタン、n-オクタンなどが挙げられるが、これらに限定されない。溶剤の比率は、本発明の密着性及び耐溶剤性に影響を与えず、塗布により成膜可能であれば、特に制限されない。
本発明のレーザにより離型可能な組成物は、転写機能を有する複合膜の形成にも適用できる。前記複合膜は、離型可能な支持膜と、本発明のレーザにより離型可能な組成物で形成される一時接着膜とを含む。一時接着膜は、離型可能な支持膜の一面に設けられる。具体的には、レーザにより離型可能な組成物を支持材の表面に塗布し、加熱により一部又は全部の溶剤を除去することで得られる。また、複合膜中の一時接着膜は、剥離可能である。
本発明によれば、積層体がさらに提供される。本発明の積層体は、支持材と、支持材上に前記レーザにより離型可能な組成物で形成される一時接着膜とを含む。具体的には、レーザにより離型可能な組成物を支持材の表面に塗布し、加熱により一部又は全部の溶剤を除去して得られる。前記複合膜を転写により支持材の表面に形成させることもできる。
本発明によれば、レーザによる離型方法がさらに提供される。この方法は、支持材1を提供するS1と、前記レーザにより離型可能な組成物を前記支持材上に塗布し、硬化して膜2を形成するステップS2と、膜2に加工素子3を形成するステップS3と、レーザにより支持材1を除去するステップS4と、を含む。
アクリル樹脂の合成
1L反応釜において、温度計、ビュレット、窒素ガス入口及び撹拌棒装置を組み込む。まず、150gプロピレングリコールメチルエーテルアセテート(PGMEA)を釜底に入れ、回転速度200rpmで撹拌しながら85℃に昇温し、次いで、重量比が異なるモノマー及び0.005molのアゾビスイソブチロニトリルを150gのPGMEAに混合し、滴定により反応釜に滴下し、さらに温度を保持しながら4時間撹拌した後、室温に降温して反応を終了させることで固形分含有量が40%の樹脂が得られる。
まず、密着促進剤及び架橋剤を20%のN,N-ジエチルホルムアミド(DEF)及び80%プロピレングリコールメチルエーテルアセテート(PGMEA)を含む混合溶剤に入れ、均一に混合し、樹脂を加えて均一に混合した後、遮光材(達興材料から購入、PK260)を加えて1時間撹拌することで固形分含有量が20%の組成物が得られる。
表1~表3に示される比率の組成物を、厚さが1.3μmの膜が形成可能な回転速度で、ガラス支持体にスピンコートし、50℃及び90℃でそれぞれ5分間プリベークして溶剤を除去し、膜表面が乾いた後、230℃で30分間加熱し、硬化して成膜することで、積層体が形成される。
80℃でフォトレジスト除去剤(AT7880P、品化から購入)を浸漬し、異なる時点で碁盤目試験を行う。試験方法は、ASTM D3359に従って剥離状況を判断する。AT7880P組成は、ジメチルスルホキシド、エタノールアミン及びテトラメチルアンモニウムヒドロキシドである。表において、◎は浸漬時間が10分間を超え、碁盤目試験の結果が5Bである場合を示す。Oは浸漬時間が10分間であり、碁盤目試験の結果が5Bである場合を示す。△は浸漬時間が5分間であり、碁盤目試験の結果が5Bである場合を示す。Xは浸泡時間にかかわらず、5Bに達さない場合を示す。
引張試験機を用いて引張試験(Pull off test)を行う。まず、フレーム接着剤(723K1、AUOから購入)を用いて試験片に定量的にスポットし、上層にガラスを接着し、355nmのUVランプで169秒照射することで光硬化ステップを行い、120℃で1時間熱硬化し、最後に引張試験を行い、塗層からの剥離に必要な力を確認し、フレーム接着剤の面積で割り、引張応力(tensile stress)を得る。ここで、接着シートに対するガラスの引張応力の数値を標準として2N/mm2と定義し、全ての試験片の引張応力を正規化することで数値が得られる。
1ワット又はそれ以上の355nmレーザにより連続走査した後、粘着紙(protect film)で剥離可能な材料を、レーザによる離型可能な材料と称する。
OXMA:オキセタンメタクリレート、GMA:グリシジルメタクリレート、ACMO:アクリロイルモルフォリン、HEMA:メタクリル酸ヒドロキシエチル、FA513M: メタクリル酸トリシクロ[5.2.1.02,6]デカン-8-イル、EM2105:o-フェニルフェノキシエチルアクリレート、EM50:スチレン、A174:メタクリルアクリロイルオキシプロピルトリメトキシシラン、DMAEMA:アクリルジメチルアミノエチル。
X-12-1050:2つ以上のアクリル官能基を有するシロキサン聚合物(信越から購入)、Alink:3-イソシアネートプロピルトリメトキシシラン、AD124:[3-(2,3-エポキシプロポキシ)-プロピル]トリメトキシシラン、N740:フェノールエポキシ樹脂、TMOM-BP:3,3’,5,5’-テトラメトキシメチルビフェノール、HMMM:ヘキサメトキシメチルメラミン。
本発明のレーザにより離型可能な組成物、及びその積層体は、半導体パッケージング分野での応用以外、任意の支持材又は材料を一時キャリアを介して担持し、次いで1つ又は複数の工程を行い、最後にレーザによりキャリアと支持材又は材料とを分離する必要があれば、いずれも本発明の提供可能な範囲に含まれる。例えば、軟性支持材又は太陽電池の製造も本発明の提供可能な範囲に含まれる。
S2 ステップ2
S3 ステップ3
S4 ステップ4
1 支持材
2 膜
3 加工素子
Claims (13)
- アクリル樹脂、遮光材、添加剤及び溶剤を含む組成物であって、当該組成物から形成された硬化膜がレーザにより剥離可能な組成物であり、
前記アクリル樹脂は、第三級アミノ基及び第二級アミノ基からなる群より選択される少なくとも1種を含む窒素含有有機基、環状エーテル基含有有機基、並びにヒドロキシル基含有有機基を含み、
前記添加剤は、少なくとも1種の密着促進剤を含む、組成物。 - 請求項1に記載の組成物であって、
前記アクリル樹脂において、前記環状エーテル基含有有機基と前記窒素含有有機基との重量比は、1:0.015~1:10であり、
前記環状エーテル基含有有機基と前記ヒドロキシル基含有有機基との重量比は、1:0.015~1:25であり、
前記窒素含有有機基と前記ヒドロキシル基含有有機基との重量比は、1:0.02~1:60である、組成物。 - 請求項1に記載の組成物であって、
前記アクリル樹脂の酸価は4mg/g未満である、組成物。 - 請求項1から3のいずれか1項に記載の組成物であって、
前記密着促進剤は、エチレン性基、エポキシ基及びイソシアネート基からなる群より選択される少なくとも1種のシロキサン化合物を含む、組成物。 - 請求項1から3のいずれか1項に記載の組成物であって、
前記第三級アミノ基及び第二級アミノ基からなる群より選択される少なくとも1種を含む窒素含有有機基は、2-(ハイドロカルビル)アミノハイドロカルビルエステル基、ジハイドロカルビルアミノハイドロカルビルエステル基、ウレタン基、ピリジン基、ピペラジニル基及びモルホリニル基のうちの少なくとも1種であり、
前記ハイドロカルビルにおけるいずれかの-CH2-は、それぞれ独立して-NH-、-O-又は-S-で置換されていてもよく、各置換基は互いに結合しない、組成物。 - 請求項1から3のいずれか1項に記載の組成物であって、
前記アクリル樹脂は、炭素数が異なる環を有する環状エーテル基を少なくとも2種含む、組成物。 - 請求項1から3のいずれか1項に記載の組成物であって、
前記環状エーテル基は、オキセタニル基、グリシジル基又はそれらの組み合わせである、組成物。 - 請求項1から3のいずれか1項に記載の組成物であって、
前記遮光材は、前記組成物に、可視光線、赤外線若しくは紫外線のうちの少なくとも1つの波長域の光を吸収させ、又は可視光線、赤外線若しくは紫外線のうちの少なくとも1つの波長域の光の透過を遮断させる材料である、組成物。 - 請求項1から3のいずれか1項に記載の組成物であって、
前記添加剤は、架橋剤をさらに含む、組成物。 - 支持材と、
前記支持材上に請求項1又は2に記載の組成物で形成される膜と、
を含む、積層体。 - 離型可能な支持膜と、
請求項1から3のいずれか1項に記載の組成物で形成される一時接着膜と、
を含み、
前記一時接着膜は、前記離型可能な支持膜の一面に設けられる、複合膜。 - 支持材を提供するステップと、
請求項1から3のいずれか1項に記載の組成物で形成される一時接着膜を前記支持材の一面に転写するステップと、
レーザにより前記支持材を除去するステップと、
を含むレーザによる離型方法。 - 支持材を提供するステップと、
請求項1から3のいずれか1項に記載の組成物を前記支持材上に塗布し、硬化させて膜を形成するステップと、
レーザにより前記支持材を除去するステップと、
を含む、レーザによる離型方法。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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