JP5218828B2 - 感光性樹脂組成物、並びにこれを用いた感光性フィルム、レジストパターンの形成方法及び永久レジスト - Google Patents
感光性樹脂組成物、並びにこれを用いた感光性フィルム、レジストパターンの形成方法及び永久レジスト Download PDFInfo
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- JP5218828B2 JP5218828B2 JP2008128252A JP2008128252A JP5218828B2 JP 5218828 B2 JP5218828 B2 JP 5218828B2 JP 2008128252 A JP2008128252 A JP 2008128252A JP 2008128252 A JP2008128252 A JP 2008128252A JP 5218828 B2 JP5218828 B2 JP 5218828B2
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Images
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Description
また、本発明は、回路形成用基板上に上記感光性樹脂組成物からなる感光性樹脂組成物層を設け、当該感光性樹脂組成物層に直接描画方式により活性光線を画像状に照射し露光部を光硬化させ、未露光部を現像により除去する、レジストパターンの形成方法を提供する。
なお、式中、Aは酸価(mgKOH/g)を示し、Vfは0.1NのKOH水溶液の滴定量(mL)を示し、Wpは測定樹脂溶液重量(g)を示し、Iは測定樹脂溶液の不揮発分の割合(質量%)を示す。
アクリル共重合体は、例えば、(メタ)アクリル酸及び(メタ)アクリル酸アルキルエステル等を共重合成分としてラジカル重合させることにより得られる。特に、メタクリル酸及び(メタ)アクリル酸アルキルエステルを共重合成分として得られるビニル系共重合化合物が好ましい。
次いで、必要に応じて上述した感光性フィルムから保護フィルムを除去する除去工程を行い、マスクパターンを通して、感光性樹脂組成物層の所定部分に活性光線を照射し、照射部の感光性樹脂組成物層を光硬化させる露光工程を行う。このとき、一括露光方式の露光機を用いても露光工程は可能であるが、直接描画方式のLDI方式の露光工程を用いることが好ましい。本発明の感光性樹脂組成物を用いた場合、LDI方式の光源としては、355nm又は405nmのレーザ光線のいずれでも良く、i線及びh線混線タイプのLDI装置にも対応可能である。
上記ウエット現像の場合、現像液としては、アルカリ性水溶液、水系現像液、有機溶剤等の安全かつ安定であり操作性が良好なものが、感光性樹脂組成物の種類に対応して用いられる。また、現像方法としては、スプレー、揺動浸漬、ブラッシング、スクラッピング等の公知の方法が適宜採用される。
上記現像工程終了後、はんだ耐熱性及び耐薬品性等を向上させる目的で、高圧水銀ランプによる紫外線照射や加熱を行うことが好ましい。紫外線を照射させる場合は必要に応じてその照射量を調整することができ、例えば0.2〜10J/cm2程度の照射量で照射を行うことができる。また、レジストパターンを加熱する場合は、130〜200℃程度の範囲で15〜90分程行われることが好ましい。
上記ソルダーレジストは、例えば、基板に対し、めっきやエッチングを施す場合に、めっきレジストやエッチングレジストとして用いられる他、そのまま基板上に残されて、配線等を保護するための保護膜(感光性永久レジスト)として用いられる。
以下、実施例により本発明を更に具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
なお、これらの感光性樹脂組成物には、それぞれ希釈剤として、メチルエチルケトンを加えた。
12μm厚の銅箔をガラスエポキシ基材に積層したプリント配線板用基板(E−679、日立化成工業株式会社製、商品名)の銅表面を砥粒ブラシで研磨し、水洗後、乾燥した。このプリント配線板用基板上に連プレス式真空ラミネータ(MVLP−500、株式会社名機製作所製、商品名)を用いて、プレス熱板温度70℃、真空引き時間20秒、ラミネートプレス時間30秒、気圧4kPa以下、圧着圧力0.4MPaの条件の下、前記感光性フィルムの保護フィルムを剥離して積層し、評価用積層体を得た。
現像後、21段ステップタブレットの残存ステップ段数が8.0となる露光エネルギー量を感光性樹脂組成物層の感度(単位;mJ/cm2)とした。この数値が低いほど光感度が高いことを示す。
上記感度の評価と同様にして得られた評価用積層体を室温で1時間以上放置した後、直径80μmの開口パターンを有するデジタルデータを、オルボテック社製Paragon9000型露光機を使用して21段ステップタブレットの残存ステップ段数が8.0となるエネルギー量で、該評価用積層体の支持体上から直接描画露光した。
作製した感光性フィルムを遮光性のブラックシートで梱包し、23℃で20日間放置した後、上記レジスト形状の評価と同様の条件で露光、現像、UV照射、加熱工程を経て永久マスクレジストパターンを形成させ、実体顕微鏡で観察し次の基準で評価した。すなわち、未露光部分に樹脂残りが認められないものを「○」とし、未露光部分に樹脂残りが認められたものを「×」とした。
上記レジスト形状の評価と同様にして得た永久マスクレジストパターン表面の鉛筆硬度を、JIS K5600−5−4に準拠して測定し、レジスト表面におけるきずの有無を目視で観察した。測定には硬さ4Hの鉛筆(三菱鉛筆株式会社製)を用いた。表面硬度の評価は、4Hでレジスト表面にきずが生じないもの、すなわち鉛筆硬度が4H以上であるものを「○」とし、4Hでレジスト表面にきずが生じたもの、すなわち鉛筆硬度が3H以下であるものを「×」とした。
上記感度の評価と同様にして得られた評価用積層体を室温で1時間以上放置した後、2mm角の開口パターンを有するデジタルデータを、オルボテック社製Paragon9000型露光機を使用して21段ステップタブレットの残存ステップ段数が8.0となるエネルギー量で、該評価用積層体の支持体上から直接描画露光した。
次いで、室温で1時間静置した後、該積層体上のポリエチレンテレフタレートを剥離し、30℃の1質量%炭酸ナトリウム水溶液で、最小現像時間(未露光部が現像される最小時間)の1.5倍の時間でスプレー現像した。スプレー現像後、株式会社オーク製作所製の紫外線照射装置を使用して1J/cm2の紫外線照射を行い、さらに160℃、60分間で加熱処理し、2mm角の開口部を有するソルダーレジストが形成された評価基板を得た。
上記はんだ耐熱性の評価と同様にして得た永久マスクレジストを形成させた評価基板を、−65℃の大気中に15分間晒した後、180℃/分の昇温速度で昇温し、次いで、150℃の大気中に15分間晒した後、180℃/分の降温速度で降温する熱サイクルを100回繰り返した。試験後、評価基板の永久レジスト膜のクラック及び剥離程度を100倍の金属顕微鏡により観察し、次の基準で評価した。すなわち、永久レジスト膜のクラック及び剥離を観察されなかったものは「○」とし、それらのいずれかを確認されたものは「×」とした。
12μm厚の銅箔をガラスエポキシ基材に積層したプリント配線板用基板(E−679、日立化成工業株式会社製、商品名)の銅表面にエッチング処理を施し、ライン/スペースが50μm/50μmのくし型電極を形成した。この基板を評価基板とし、基板上に上記はんだ耐熱性の評価と同様にして永久マスクレジストを形成させ、130℃、85%RH、20V条件下に100時間晒した。試験後、マイグレーションの発生の程度を、100倍の金属顕微鏡により観察し、次の基準で評価した。すなわち、永久レジスト膜にマイグレーションが発生しなかったものは「○」とし、マイグレーションが発生したものは「×」とした。マイグレーションとは、銅電極からソルダーレジストへ銅が溶出し、析出することにより、電極周辺のソルダーレジストの変色や絶縁抵抗の低下が起こる現象である。
結果を表3及び表4に示す。
Claims (7)
- (a)カルボキシル基及びエチレン性不飽和基を有する感光性プレポリマー、(b)エチレン性不飽和基を有する光重合性モノマー、(c)光重合開始剤、及び(d)熱硬化剤を含有する感光性樹脂組成物であって、
前記(a)カルボキシル基及びエチレン性不飽和基を有する感光性プレポリマーが、分子内に2つ以上の水酸基及びエチレン性不飽和基を有するエポキシアクリレート化合物と、ジイソシアネート化合物と、カルボキシル基を有するジオール化合物と、を反応させて得られるポリウレタン化合物を含有し、
前記(d)熱硬化剤が、下記一般式(1)で表されるマレイミド化合物を含有する、感光性樹脂組成物。
- (e)バインダーポリマーとして、アクリル共重合体を更に含有する、請求項1に記載の感光性樹脂組成物。
- 前記(c)光重合開始剤がアクリジン誘導体を含む、請求項1又は2に記載の感光性樹脂組成物。
- 支持体と、該支持体上に塗布、乾燥して形成された請求項1〜3のいずれか一項に記載の感光性樹脂組成物からなる感光性樹脂組成物層と、を備える感光性フィルム。
- 回路形成用基板上に請求項1〜3のいずれか一項に記載の感光性樹脂組成物からなる感光性樹脂組成物層を設け、当該感光性樹脂組成物層に活性光線を画像状に照射し露光部を光硬化させ、未露光部を現像により除去する、レジストパターンの形成方法。
- 回路形成用基板上に請求項1〜3のいずれか一項に記載の感光性樹脂組成物からなる感光性樹脂組成物層を設け、当該感光性樹脂組成物層に直接描画方式により活性光線を画像状に照射し露光部を光硬化させ、未露光部を現像により除去する、レジストパターンの形成方法。
- 請求項5又は6に記載のレジストパターンの形成方法により形成される永久レジスト。
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