JP5938869B2 - プリント配線板及びその製造方法並びに感光性樹脂組成物 - Google Patents
プリント配線板及びその製造方法並びに感光性樹脂組成物 Download PDFInfo
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- JP5938869B2 JP5938869B2 JP2011224339A JP2011224339A JP5938869B2 JP 5938869 B2 JP5938869 B2 JP 5938869B2 JP 2011224339 A JP2011224339 A JP 2011224339A JP 2011224339 A JP2011224339 A JP 2011224339A JP 5938869 B2 JP5938869 B2 JP 5938869B2
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- printed wiring
- wiring board
- pattern
- resin composition
- photosensitive resin
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- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
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Description
(I)導体回路を有するプリント配線板上に第一の感光性樹脂組成物からなる第一の層を形成後、当該第一の層に対して第一の露光処理及び現像処理を施して第一のパターンを形成する工程と、
(II)第一のパターンの少なくとも一部を覆うように、プリント配線板上に第二の感光性樹脂組成物からなる第二の層を形成後、第二の露光処理及び現像処理を施して第二のパターンを形成する工程と、
(III)第二のパターンに対して第一の紫外線硬化処理及び第一の熱硬化処理を施す工程と、
(IV)上記(III)工程における処理が施された第二のパターンをデスミア処理によって研削して第一のパターンを露出させる工程と、
(V)更なるデスミア処理によって第一のパターンを除去し、第二の感光性樹脂組成物の硬化物からなり且つプリント配線板の表面にまで至る開口を有するソルダーレジストを形成する工程と、を備える。
(A2)カルボキシル基とエチレン性不飽和基とを含有する光反応性樹脂と、
(B2)光重合開始剤と、
(C2)熱硬化剤と、
(D2)最大粒径が5μm以下であり且つ平均粒径が1μm以下である無機フィラーと、
を含有し、当該感光性樹脂組成物の全質量基準で、無機フィラーの含有率が20〜70質量%である感光性樹脂組成物を提供する。
(A1)バインダーポリマーと、
(B1)エチレン性不飽和結合を少なくとも1つ有する光重合性化合物と、
(C1)光重合開始剤と、
を含有することが好ましい。
(A2)カルボキシル基とエチレン性不飽和基とを含有する光反応性樹脂と、
(B2)光重合開始剤と、
(C2)熱硬化剤と
(D2)最大粒径が5μm以下であり且つ平均粒径が1μm以下である無機フィラーと、を含有し、
当該感応性樹脂組成物の全質量基準で、上記(D2)無機フィラーの含有率が20〜70質量%であることが好ましい。
同士、あるいはエポキシ化合物(a1)と不飽和モノカルボン酸(a2)との重合を防止するため、重合防止剤を使用することが好ましい。重合防止剤としては、例えば、ハイドロキノン、メチルハイドロキノン、ハイドロキノンモノメチルエーテル、カテコール、及びピロガロール等を用いることができる。重合防止剤の使用量は、エポキシ化合物(a1)と不飽和モノカルボン酸(a2)の合計100質量部に対して、0.01〜1質量部とすることが好ましい。第一の反応の反応温度は、60〜150℃が好ましく、80〜120℃がより好ましい。
上記(A2)成分の含有量は、(D2)成分を含めた無機フィラー成分を除く樹脂成分100重量部に対して、30〜90質量部であることが好ましく、40〜80質量部であることがより好ましい。
上記(B2)成分の含有量は、(D2)成分を含めた無機フィラー成分を除く樹脂成分100重量部に対して、0.1〜10質量部であることが好ましく、0.5〜5質量部であることがより好ましい。
上記(C2)成分の含有量は、(D2)成分を含めた無機フィラー成分を除く樹脂成分100重量部に対して、1〜40質量部であることが好ましく、5〜30質量部であることがより好ましい。
上記(D2)成分の含有量は、無機フィラー成分を除く樹脂成分100重量部に対して、10〜300質量部であることが好ましく、50〜150質量部であることがより好ましい。
まず、厚さ12μmの銅箔2が両面に貼着された銅張積層体(日立化成工業株式会社製 MCL−E−679FG)を準備した。銅張積層体の厚さは400μmであった(図1(a)参照)。
次いで、図2に示すように、第一の感光性樹脂組成物としてドライフィルムレジスト(日立化成工業株式会社 Photec H−7025)を真空ラミネーターで両面に貼着し、第一の層8を形成した。第一の層8にパターンを形成したフォトツールを密着させ、オーク製作所社製EXM‐1201型露光機を使用して、50mJ/cm2のエネルギー量で露光を行った。次いで、30℃の1質量%炭酸ナトリウム水溶液で、90秒間スプレー現像を行い、第一の感光性樹脂組成物を開口させて第一のパターン8aを形成した(図3参照)。
プリント配線板のソルダーレジストの形成に使用する第二の感光性樹脂組成物として、以下に示すものを調製した。
(A2)カルボキシル基とエチレン性不飽和基とを含有する光反応性樹脂
酸変性したクレゾールノボラック型エポキシアクリレート(CCR−1219H、日本化薬株式会社製、商品名)70g、
(B2)光開始剤
2,4,6−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド(ダロキュアTPO、チバ・ジャパン社製、商品名)、エタノン,1−[9−エチル−6−(2−メチルベンゾイル)−9H−カルバゾール−3−イル]−,1−(o−アセチルオキシム)(イルガキュアOXE−02、チバ・ジャパン社製、商品名)4g、
(C2)熱硬化剤
ビフェノール型エポキシ樹脂(YX−4000、ジャパンエポキシレジン株式会社製、商品名)20g、
(d)無機フィラー成分
平均粒径が50nm、ビニルシランでシランカップリング処理したシリカフィラー60g(NV50%品)、を用いた。なお、(D2)無機フィラー成分は、樹脂分に対し、30質量%になるように配合した。分散状態は、動的光散乱式ナノトラック粒度分布計「UPA−EX150」(日機装社製)、及びレーザ回折散乱式マイクロトラック粒度分布計「MT−3100」(日機装社製)を用いて測定し、最大粒径が1μm以下となっていることを確認した。
また、その他の成分として、多官能アクリレートモノマであるジペンタエリスリトールヘキサアクリレート(DPHA、日本化薬社製、商品名)を10g配合した。
(A2)カルボキシル基とエチレン性不飽和基とを含有する光反応性樹脂、(B2)光開始剤、(C2)熱硬化剤は、感光性樹脂組成物Aと同様のものを用いた。(D2)無機フィラー成分としては、平均粒径が300nmの硫酸バリウムを、スターミルLMZ(アシザワファインテック株式会社製)で、直径1.0mmのジルコニアビーズを用い、周速12m/sにて3時間分散して調整した。分散状態を、感光性樹脂組成物Aと同様の方法で測定し、最大粒径が2μmであることを確認した。
(A2)カルボキシル基とエチレン性不飽和基とを含有する光反応性樹脂、(B2)光開始剤、(C2)熱硬化剤は、感光性樹脂組成物Aと同様のものを用いた。(D2)無機フィラー成分としては、平均粒径が1μmの結晶性シリカを、スターミルLMZ(アシザワファインテック株式会社製)で、直径1.0mmのジルコニアビーズを用い、周速12m/sにて3時間分散して調整した。分散状態を、感光性樹脂組成物Aと同様の方法で測定し、最大粒径が10〜15μmであることを確認した。
得られた感光性フィルムタイプのソルダーレジストを用いて、プリント配線板100の上に第二の層10を形成した(図4参照)。詳細には、まず、感光性樹脂組成物A,B又はCからなるフィルム状ソルダーレジストの保護フィルムのみを剥がし、プリント配線板100Aの表面にフィルム状ソルダーレジストを載置した。プレス式真空ラミネータ(MVLP−500、名機製作所製、商品名)を用いてプリント配線板100の表面にフィルム状ソルダーレジストを積層し、評価用積層体を形成した。プレス条件は、プレス熱板温度80℃、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とした。
○:空隙なく埋め込みが良好。
×:開口部への埋め込みが不充分。
○:観察されなかったもの。
△:一部観察されたもの。
×:多数観察されたもの。
○:デスミア処理後にソルダーレジストがはく離しないもの。
×:デスミア処理後にソルダーレジストがはく離したもの。
○:直径50μm以下で開口できたもの。
△:直径70μm以下で開口できたもの。
×:直径90μm以下で開口できたもの。
××:直径90μm以下で開口できないもの。
○:壁面が平滑なもの。
×:壁面にフィラーの欠落や段差があるもの。
○:銅表面にドライフィルムレジスト(第一の層)の残渣がなく、はく離及び除去できているもの。
×:ドライフィルムレジストの残渣があるもの。
○:平滑に全面めっきされているもの。
×:開口部の銅表面にめっきむらがあるもの。
−:ソルダーレジストがはく離して、その後の評価ができないもの。
Claims (11)
- 開口を有するソルダーレジストを表面に備えるプリント配線板の製造方法であって、
導体回路を有するプリント配線板上に第一の感光性樹脂組成物からなる第一の層を形成後、当該第一の層に対して第一の露光処理及び現像処理を施して第一のパターンを形成する第一の工程と、
前記第一のパターンの少なくとも一部を覆うように、前記プリント配線板上に第二の感光性樹脂組成物からなる第二の層を形成後、第二の露光処理及び現像処理を施して第二のパターンを形成する第二の工程と、
前記第二のパターンに対して第一の紫外線硬化処理及び第一の熱硬化処理を施す第三の工程と、
前記第三の工程における処理が施された前記第二のパターンを膨潤処理した後、デスミア処理液を用いて、前記第二のパターンを研削して前記第一のパターンを露出させると共に、前記第一のパターンを除去し、前記第二の感光性樹脂組成物の硬化物からなり且つ前記プリント配線板の表面にまで至る開口を有するソルダーレジストを形成する第四の工程と、を備えるプリント配線板の製造方法。 - 前記第一の紫外線硬化処理における、第一の紫外線照射量が600mJ/cm2以上である、請求項1記載のプリント配線板の製造方法。
- 前記第一の熱硬化処理が、温度150℃〜250℃であり且つ硬化時間30分〜300分で施される、請求項1又は2記載のプリント配線板の製造方法。
- 前記第一の層の厚さT1は2μm〜50μmである、請求項1〜3のいずれか一項記載のプリント配線板の製造方法。
- 前記第二の層の厚さT2は、2μm以上であり且つ前記第一の層の厚さT1に対する第二の層比(T2/T1)が1.0〜2.0である、請求項1〜4のいずれか一項記載のプリント配線板の製造方法。
- 前記第一の熱硬化処理は不活性ガスの雰囲気で行われる、請求項1〜5のいずれか一項記載のプリント配線板の製造方法。
- 前記デスミア処理液は、過マンガン酸ナトリウム液、水酸化ナトリウム液、過マンガン酸カリウム液、クロム液及び硫酸からなる群から選ばれる少なくとも一種である、請求項1〜6のいずれか一項記載のプリント配線板の製造方法。
- 前記第四の工程後、前記ソルダーレジストに対して第二の紫外線硬化処理及び第二の熱硬化処理の少なくとも一方を施す工程を更に備える、請求項1〜7のいずれか一項記載のプリント配線板の製造方法。
- 前記ソルダーレジストが有する開口の直径が60μm以下である、請求項1〜8のいずれか一項に記載のプリント配線板の製造方法。
- 前記ソルダーレジストが有する最小直径の開口において当該開口の直径Rminに対する当該開口の深さDの比(D/Rmin)が0.1〜1.0である、請求項9記載のプリント配線板の製造方法。
- 請求項1〜8のいずれか一項記載の方法において第二の感光性樹脂組成物として使用される感光性樹脂組成物であって、
(A2)カルボキシル基とエチレン性不飽和基とを含有する光反応性樹脂と、
(B2)光重合開始剤と、
(C2)熱硬化剤と、
(D2)最大粒径が5μm以下であり且つ平均粒径が1μm以下である無機フィラーと、
を含有し、
当該感光性樹脂組成物の全質量基準で、前記無機フィラーの含有率が20〜70質量%である、感光性樹脂組成物。
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