JP2017122818A - 感光性樹脂積層体 - Google Patents
感光性樹脂積層体 Download PDFInfo
- Publication number
- JP2017122818A JP2017122818A JP2016001382A JP2016001382A JP2017122818A JP 2017122818 A JP2017122818 A JP 2017122818A JP 2016001382 A JP2016001382 A JP 2016001382A JP 2016001382 A JP2016001382 A JP 2016001382A JP 2017122818 A JP2017122818 A JP 2017122818A
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- Prior art keywords
- photosensitive resin
- layer
- resin layer
- laminated body
- laminate
- Prior art date
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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
- 125000003944 tolyl group Chemical group 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- DWWMSEANWMWMCB-UHFFFAOYSA-N tribromomethylsulfonylbenzene Chemical compound BrC(Br)(Br)S(=O)(=O)C1=CC=CC=C1 DWWMSEANWMWMCB-UHFFFAOYSA-N 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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- JEVGKYBUANQAKG-UHFFFAOYSA-N victoria blue R Chemical compound [Cl-].C12=CC=CC=C2C(=[NH+]CC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 JEVGKYBUANQAKG-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
- G03F7/2053—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser
- G03F7/2055—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser for the production of printing plates; Exposure of liquid photohardening compositions
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/34—Imagewise removal by selective transfer, e.g. peeling away
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Materials For Photolithography (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
[1]
支持層と、前記支持層上に積層される感光性樹脂層と、前記感光性樹脂層上に積層されるカバー層とを含み、前記感光性樹脂層の厚みが60μm以上であり、かつ前記カバー層は、前記カバー層のMD方向に沿って縦20cm及び幅15cmに切り出した略矩形シートを前記MD方向端部が重なるように折り返して平板上に静置した際の最大高さが18mm以上である、感光性樹脂積層体。
[2]
前記カバー層の熱収縮率が1.5%以下である、[1]に記載の感光性樹脂積層体。
[3]
前記感光性樹脂層がアルカリ可溶性高分子成分とエチレン性不飽和二重結合含有成分を含有し、かつ前記アルカリ可溶性高分子成分とエチレン性不飽和二重結合含有成分との配合比が1.45未満である、[1]又は[2]に記載の感光性樹脂積層体。
[4]
前記アルカリ可溶性高分子成分が、100〜600の酸当量及び5,000〜500,000の重量平均分子量を有し、かつその側鎖に芳香族基を有する、[3]に記載の感光性樹脂積層体。
[5]
前記支持層の厚みが10〜30μmであり、かつヘーズが0.01〜1.5%である、[1]〜[4]のいずれか1項に記載の感光性樹脂積層体。
[6]
[1]〜[5]のいずれか1項に記載の感光性樹脂積層体が捲回されている感光性樹脂積層体ロール。
[7]
[1]〜[5]のいずれか1項に記載の感光性樹脂積層体又は[6]に記載の感光性樹脂積層体ロールの感光性樹脂層を支持体に積層するラミネート工程;
該感光性樹脂層を露光する露光工程;及び
該露光された感光性樹脂層を現像する現像工程;
を含むレジストパターンの形成方法。
[8]
[1]〜[5]のいずれか1項に記載の感光性樹脂積層体又は[6]に記載の感光性樹脂積層体ロールの感光性樹脂層を基板に積層するラミネート工程;
該感光性樹脂層を露光する露光工程;
該露光された感光性樹脂層を現像して、レジストパターンが形成された基板を得る現像工程;
該レジストパターンが形成された基板をエッチング又はめっきする導体パターン形成工程;及び
該レジストパターンを剥離する剥離工程;
を含む配線板の製造方法。
支持体に上述の感光性樹脂積層体又はそのロールを積層するラミネート工程;
感光性樹脂層を露光する露光工程;及び
露光された感光性樹脂層を現像する現像工程
を、好ましくはこの順に、含む。
なお、上述した各パラメータの値については特に断りのない限り、後述する実施例での測定方法に準じて測定される。
下記表1に記載された感光性樹脂層(B)を形成するための組成を有する感光性樹脂組成物を混合し、下記表1に記載された支持体(A)にバーコーターを用いて均一に塗布し、90℃の乾燥機中で7分間乾燥して感光性樹脂層(B)を形成した。感光性樹脂層(B)の厚みは、200μmであった。
上記(1)で作製した感光性樹脂積層体を3インチのABS樹脂製コアに巻きつけ、感光性樹脂積層体をロール形態とした。得られたロールを30℃及び50%の環境下に保管し、経時観察を行うことによって、ロール形態を持つフィルムの表面において、感光性樹脂積層体の外観について不均一部分の発生の有無を観察した。不均一部分の発生の有無については、下記基準に従ってランク分けした。
○:外観上、全く不均一部分が無い。
△:外観上、不均一部分が観察面積中1〜10%を占める。
×:外観上、不均一部分が観察面積中10%以上を占める。
先ず、保護層用カバーフィルムをMD方向に沿って縦20cm及び幅15cmに切り出して矩形シートを得る。得られた矩形シートを平板上に静置する。この際、静電気帯電が防止されており、且つ気温23℃及び湿度50%の環境下で、矩形シートを平板上に静置する。次に、矩形シートのMD方向の両端部(幅15cm)が一致して重なるように、矩形シートを折り返す。この際、折り返し部には荷重を掛けず、かつ両端部のみが重なるように、さらに矩形シートが折れ曲がったり、傷が付いたりしないように、矩形シートを折り返す。折り返し部位のシート間距離(垂直方向)が最大となる数値を最大高さ数値(a)として測定する。折り返し部位のシート間の鉛直方向距離は、L字型定規で測定される。カバーフィルム折り返し時の最大高さ数値(a)の測定場所は、静岡県富士市とする。
保護層(C)と対応するカバーフィルムの熱収縮率の測定は、下記の方法により行なった:
1)カバーフィルムをMD方向に沿って縦10mm及び幅3mmの短冊状シートとして切り出した。
2)熱機械的分析(Thermo mechanical Analysis、以下「TMA」と略記する)測定によって短冊状シートの熱収縮率を測定した。測定用治具を用いてチャックに短冊状シートを固定した。
TMA測定方法は下記の通りである。サンプルを装置にセット後、荷重を2gに設定し、室温から50℃まで10℃/分の昇温速度で昇温後、1時間保持し、10℃/分の降温速度で30℃まで降温後、2時間保持したときのTMA測定を行った。
フィルムに荷重を掛けて室温から約50℃に昇温後、1時間置いて安定化させ、続いて30℃に降温した際の50℃から30℃の変位量を元に、収縮率を測定して比較した。
ヘーズメーター(日本電色工業株式会社製、NDH4000、JIS K 7136)によって支持体(A)のヘーズ(曇り度)を測定した。
上記(1)で作製した感光性樹脂積層体を、厚み1000Åのチタン及び厚み1000Åの銅をスパッタ蒸着したシリコンウエハ(6インチサイズ)に、保護層を剥がしながら、手動ラミネーター(大成ラミネーター株式会社製、VA−400III)によりラミネートした。ロール温度は90℃、エアー圧力は0.25Mpaとし、ラミネート速度は0.30m/minとした。次に、クロムガラスフォトマスクを用いて、Ultratech Prisma ghiステッパー(ウルトラテック社製)を用いて、300mJ/cm2の露光量で露光を行なった。更に、ウエハ現像機(ミカサ株式会社製、AD−1200)を用いて、30℃の1質量%NaCO3水溶液を所定時間スプレーし、感光性樹脂層の未露光部分を溶解除去した。この場合に、未露光部分の感光性樹脂層が完全に溶解するのに要する最も少ない時間を最小現像時間とした。実際の現像時間については、最小現像時間の2倍で現像し、硬化レジストパターンを得た。
得られた硬化レジストの円孔パターンを走査線電子顕微鏡(株式会社日立ハイテクフィールディング社製、S−3400N)にて観察し、レジストサイドウォール形状を以下のようにランク付けをした。
○:形成されたレジストサイドウォールにガタツキがほとんど無い。
△:形成されたレジストサイドウォールに僅かにガタツキが存在する。
×:形成されたレジストサイドウォールの所々にガタツキが存在する。
実施例1〜6及び比較例1〜3の評価結果を下記表1に示す。表1中の材料成分の名称を下記表2に示す。なお、表1中の感光性樹脂層(B)を形成するための成分の配合量は、質量部を表し、かつ表1中の記号「B/M比」は、エチレン性不飽和二重結合含有成分(E成分)の含有量に対するアルカリ可溶性高分子成分(D成分)の含有量の比を表す。
Claims (8)
- 支持層と、前記支持層上に積層される感光性樹脂層と、前記感光性樹脂層上に積層されるカバー層とを含み、前記感光性樹脂層の厚みが60μm以上であり、かつ前記カバー層は、前記カバー層のMD方向に沿って縦20cm及び幅15cmに切り出した略矩形シートを前記MD方向端部が重なるように折り返して平板上に静置した際の最大高さが18mm以上である、感光性樹脂積層体。
- 前記カバー層の熱収縮率が1.5%以下である、請求項1に記載の感光性樹脂積層体。
- 前記感光性樹脂層がアルカリ可溶性高分子成分とエチレン性不飽和二重結合含有成分を含有し、かつ前記アルカリ可溶性高分子成分とエチレン性不飽和二重結合含有成分との配合比が1.45未満である、請求項1又は2に記載の感光性樹脂積層体。
- 前記アルカリ可溶性高分子成分が、100〜600の酸当量及び5,000〜500,000の重量平均分子量を有し、かつその側鎖に芳香族基を有する、請求項3に記載の感光性樹脂積層体。
- 前記支持層の厚みが10〜30μmであり、かつヘーズが0.01〜1.5%である、請求項1〜4のいずれか1項に記載の感光性樹脂積層体。
- 請求項1〜5のいずれか1項に記載の感光性樹脂積層体が捲回されている感光性樹脂積層体ロール。
- 請求項1〜5のいずれか1項に記載の感光性樹脂積層体又は請求項6に記載の感光性樹脂積層体ロールの感光性樹脂層を支持体に積層するラミネート工程;
該感光性樹脂層を露光する露光工程;及び
該露光された感光性樹脂層を現像する現像工程;
を含むレジストパターンの形成方法。 - 請求項1〜5のいずれか1項に記載の感光性樹脂積層体又は請求項6に記載の感光性樹脂積層体ロールの感光性樹脂層を基板に積層するラミネート工程;
該感光性樹脂層を露光する露光工程;
該露光された感光性樹脂層を現像して、レジストパターンが形成された基板を得る現像工程;
該レジストパターンが形成された基板をエッチング又はめっきする導体パターン形成工程;及び
該レジストパターンを剥離する剥離工程;
を含む配線板の製造方法。
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JPH1138631A (ja) * | 1997-07-16 | 1999-02-12 | Hitachi Chem Co Ltd | 感光性エレメント |
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JP2012234091A (ja) * | 2011-05-06 | 2012-11-29 | Hitachi Chem Co Ltd | 感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法 |
CN104834182A (zh) * | 2015-05-20 | 2015-08-12 | 杭州福斯特光伏材料股份有限公司 | 一种具有高分辨率和优异掩孔性能的感光干膜 |
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JPH1138631A (ja) * | 1997-07-16 | 1999-02-12 | Hitachi Chem Co Ltd | 感光性エレメント |
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JP2012234091A (ja) * | 2011-05-06 | 2012-11-29 | Hitachi Chem Co Ltd | 感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法 |
CN104834182A (zh) * | 2015-05-20 | 2015-08-12 | 杭州福斯特光伏材料股份有限公司 | 一种具有高分辨率和优异掩孔性能的感光干膜 |
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