JP4076375B2 - Photosensitive film and insulating film - Google Patents

Description

【００１１】
（式中、Ａは炭素数１〜１０の２価のアルキレン基、−ＳＯ₂−、−ＳＯ−、−Ｓ−、−Ｏ−、または−ＣＯ−を示す。ａおよびｂは各々独立して０〜４の整数を示し、ｍは０または１の整数、ｎは１〜３の整数を示す。Ｒ₁〜Ｒ_６は、各々独立して、水素原子、炭素数１〜８のアルキル基、ハロゲン原子のいずれかを示し、Ｒ₁〜Ｒ₄の少なくとも１つは、炭素数１〜８のアルキル基である。）
【００１２】
本発明の式（Ｉ）において、Ａは炭素数１〜１０の２価のアルキレン基、−ＳＯ₂−、−ＳＯ−、−Ｓ−、−Ｏ−、または−ＣＯ−であれば特に限定されない。炭素数１〜１０の２価のアルキレン基としては、例として、メチレン基、エチレン基、プロピレン基等が挙げられる。
【００１３】
本発明の式（Ｉ）において、Ｒ₁〜Ｒ₆は、各々独立して、水素原子、炭素数１〜８のアルキル基、ハロゲン原子のいずれかを示し、Ｒ₁〜Ｒ₄の少なくとも１つは、炭素数１〜８のアルキル基であれば特に限定されない。
【００１４】
本発明の式（Ｉ）において、Ｒ₁〜Ｒ₆のより好ましい態様としては、例えば、水素原子、メチル基、エチル基、ｎ―プロピル基、イソプロピル基、炭素数４〜８のアルキル基等が挙げられる。
【００１５】
本発明の式（Ｉ）において、ａおよびｂは各々独立して０〜４の整数、ｍは０または１の整数、ｎは１〜３の整数であれば特に限定されない。
【００１６】
本発明において、芳香族ポリエーテル系重合体の対数粘度ηinhは、特に限定されるものではないが、好ましい対数粘度としては、０．１〜２．０ｄｌ／ｇであり、０．３〜１．８ｄｌ／ｇがより好ましく、０．５〜１．６ｄｌ／ｇがさらに好ましい。
【００１７】
芳香族ポリエーテル系重合体の対数粘度が低すぎると、一般に、感光性感度の低下により加工性が低下したり、加工後の製品の強度や靱性が低下して好ましくない場合がある。芳香族ポリエーテル系重合体の対数粘度が高すぎると、得られた芳香族ポリエーテル系重合体フィルムを回路基材を製造する目的でフォトリソグラフィー加工する際、現像工程時に精細なパターン加工ができない等、製品の信頼性が低下し、好ましくない場合がある。
【００１８】
芳香族ポリエーテル系重合体の対数粘度の評価方法は、特に限定されるものではないが、例えば、芳香族ポリエーテル系重合体０．５０ｇをＮ−メチル−２−ピロリドン１００ｍｌに溶解した後、３５℃において測定することができる。
【００１９】
本発明において用いられる、芳香族ポリエーテル系重合体は、上記一般式（Ｉ）で表される構造の繰返し単位成分以外に、各種ジオールおよびジハライド化合物を、各種物性、例えば耐熱性、吸湿性、熱膨張係数、誘電率、屈折率または複屈折率等を制御することを目的に、必要に応じて共重合させても良いが、一般式（Ｉ）で表わされる構造の芳香族ポリエーテル系重合体が組成物中に１０〜１００重量％含有するのが好ましい態様である。
【００２０】
本発明において用いられる、芳香族ポリエーテル系重合体は、いかなる方法で製造されたものであっても構わず、公知の方法を利用して製造可能である。式（Ｉ）の化合物の製造方法としては、例えば、特開昭５８−１６７６２２号公報記載の方法を挙げることができるが、これに限定されるものではない。
【００２１】
本発明において用いられる、支持基材は特に限定されないが、例えば銅及び銅合金基材、金及び金合金基材、アルミ及びアルミ合金基材、シリコンウエハ、ガラス基材および石英基材等を挙げることができる。
【００２２】
本発明の感光性フィルムは、いかなる方法で製造されたものであっても構わないが、一例を挙げると例えば、上記芳香族ポリエーテル系重合体を有機溶剤に溶解させ、これを支持基材上に塗布し、乾燥する方法を挙げることができる。
【００２３】
本発明の感光性フィルムを製造するにあたり、支持基材上に上記芳香族ポリエーテル系重合体を塗布する際、芳香族ポリエーテル系重合体を適当な有機溶媒に溶解させて塗布する方法が好ましい方法である。ここで用いられる溶媒は限定されるわけではないが、例えば、
【００２４】
（ａ） フェノール系溶媒である、
フェノール、ｏ−クロロフェノール、ｍ−クロロフェノール、ｐ−クロロフェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、２，３−キシレノール、２，４−キシレノール、２，５−キシレノール、２，６−キシレノール、３，４−キシレノール、３，５−キシレノール、
【００２５】
（ｂ） 非プロトン性アミド系溶媒である、
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，Ｎ−ジエチルアセトアミド、Ｎ−メチル−２−ピロリドン、１，３−ジメチル−２−イミダゾリジノン、Ｎ−メチルカプロラクタム、ヘキサメチルホスホロトリアミド、
【００２６】
（ｃ） エーテル系溶媒である、
１，２−ジメトキシエタン、ビス（２−メトキシエチル）エーテル、１，２−ビス（２−メトキシエトキシ）エタン、テトラヒドロフラン、ビス［２−（２−メトキシエトキシ）エチル］エーテル、１，４−ジオキサン、
【００２７】
（ｄ） アミン系溶媒である、
ピリジン、キノリン、イソキノリン、α−ピコリン、β−ピコリン、γ−ピコリン、イソホロン、ピペリジン、２，４−ルチジン、２，６−ルチジン、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、
【００２８】
（ｅ） その他の溶媒である、
ジメチルスルホキシド、ジメチルスルホン、ジフェニルエーテル、スルホラン、ジフェニルスルホン、テトラメチル尿素、アニソール、水、ベンゼン、トルエン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン、クロロベンゼン、ｏ−ジクロロベンゼン、ｍ−ジクロロベンゼン、ｐ−ジクロロベンゼン、ブロモベンゼン、ｏ−ジブロモベンゼン、ｍ−ジブロモベンゼン、ｐ−ジブロモベンゼン、ｏ−クロロトルエン、ｍ−クロロトルエン、ｐ−クロロトルエン、ｏ−ブロモトルエン、ｍ−ブロモトルエン、ｐ−ブロモトルエン、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブタノール、ペンタン、ヘキサン、ヘプタン、シクロヘキサン、ジクロロメタン、クロロホルム、四塩化炭素、フルオロベンゼン、酢酸メチル、酢酸エチル、酢酸ブチル、蟻酸メチル、蟻酸エチル等が挙げられる。これらの溶媒は、単独または２種以上混合して用いても差し支えない。
【００２９】
これらの溶剤は、用いられる芳香族ポリエーテル系重合体１００重量部に対し、１００〜１００００重量部、更に好ましくは２００〜５０００重量部使用することが好ましい。
【００３０】
本発明の感光性フィルムを製造するにあたり、芳香族ポリエーテル系重合体の支持基材への塗布方法は特に限定されないが、例えば、スピンコーターを用いた塗布、スプレーコーターを用いた塗布、バーコーターを用いた塗布、噴霧、浸漬、印刷等を挙げることができる。塗布する量は特に限定されないが例えば、硬化後の最終膜厚が１μｍ〜５００μｍ、好ましくは５〜１００μｍとなるよう塗布する。
【００３１】
支持基材上に芳香族ポリエーテル系重合体を塗布した後、乾燥する工程において、乾燥時間及び乾燥温度は特に限定されないが、一般に２５℃〜２５０℃、１０分〜２４時間で充分である。乾燥は、空気雰囲気下で行っても構わないが、窒素雰囲気下または減圧下で行っても構わない。
【００３２】
本発明の感光性フィルムは、その組成成分として芳香族ポリエーテル系重合体が用いられ、更に、目的に応じて他のいかなる成分、例えば、増感剤、光重合開始剤、レベリング剤、カップリング剤、モノマー、オリゴマー、安定剤、湿潤剤、顔料、染料等を含有しても構わないが、芳香族ポリエーテル系重合体がフィルム中に１０〜１００重量％含有するのが好ましい態様である。
【００３３】
本発明の絶縁膜は、芳香族ポリエーテル系重合体を含有する、上記感光性フィルムから得られることを特徴とする。
本発明の絶縁膜のパターン形成方法は特に限定されず、例えば上記感光性フィルムを露光、現像処理してレリーフパターン状の絶縁膜を得ることができる。これら各工程においては公知の技術を用いることができる。
【００３４】
本発明の絶縁膜のパターン形成方法は、フォトマスクパターンを用い紫外線および／又は近紫外-可視光を照射する露光工程、未照射部を現像液で溶解除去する現像工程を含むことを特徴とする。
【００３５】
露光工程においては１５０〜５００ｎｍの紫外線及び／または近紫外―可視光線を照射するが、特に３６５ｎｍの波長を中心とする波長領域が、高い効果が得られ望ましい。露光工程において、所望の形状のフォトマスクパターンを用いることができる。
【００３６】
現像工程において、未照射部を現像液で溶解除去することでレリーフパターン状の絶縁膜を得る。現像液としては、例えばシクロペンタノン、シクロヘキサノン、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，Ｎ−ジエチルアセトアミド、Ｎ−メチル−２−ピロリドン等の有機溶剤を用いることができる。また、例えば上記有機溶剤２種以上を混合して用いても良い。現像によって形成した絶縁膜は、例えばメタノールやエタノール、水等を用いてリンスしても構わない。最後に加熱処理等を行い、溶剤を除去する。加熱処理する場合の温度は、特に限定されないが、２５℃〜３００℃、より好ましくは４０℃〜３００℃で処理することが好ましい。
【００３７】
本発明の感光性フィルムから得られる絶縁膜は、支持基材との接着強度が極めて高く、また吸水率が低い。従って、該絶縁膜を例えば配線基板の表面保護膜や層間絶縁膜に用いた場合、パッケージ用封止樹脂との界面での剥離や、半導体パッケージへのクラック発生、半導体の電気不良等を抑えることができ、半導体の信頼性が著しく向上する。本発明の感光性フィルムから得られる絶縁膜は、表面保護膜や層間絶縁膜として高集積半導体装置、高集積多層配線基板等の用途に極めて有用である。
【００３８】
【実施例】
以下、本発明を実施例によりさらに詳細に説明するが、本発明はこれにより何等制限されるものではない。
〔評価方法〕
実施例中の試験の試験方法は次に示すとおりである。
（イ）芳香族エーテル系重合体もしくはポリイミドの対数粘度
芳香族エーテル系重合体もしくはポリイミド０．５０ｇをＮ−メチル−２−ピロリドン（以下、ＮＭＰと略記すことがある）１００ｍｌに溶解した後、３５℃において粘度計により測定した。
【００３９】
（ロ）フィルムの碁盤目密着性試験
フィルムの碁盤目密着性の評価はＪＩＳ−Ｋ５４００法に準拠し、フィルムに２ｍｍ幅、２５マスの碁盤目状の切り傷をカッターナイフで付け、傷の状態から評価点数をつけた。評価点数は、フィルムのはがれが無く接着強度が十分の場合が１０点、はがれが６５％以上の接着強度が不十分な場合が０点、その中間の接着強度については、はがれの度合いで段階的に８、６、４点を付す上記ＪＩＳ−Ｋ５４００法の評価に従った。
【００４０】
（ハ）吸水率評価
５０×５０mm、５０μm厚のフィルムの両面をメタノールで２回ずつ拭き取り、これを濾紙に包んで５０℃設定のオーブンにて２４時間乾燥させた。乾燥後、このフィルムを直ちにデシケータ内に移し２３℃-相対湿度５０％の恒温恒湿室にて秤量した（Ｗ１ｇ）。秤量後のフィルムをイオン交換水に浸積し、２４時間静置した。フィルムを水から引き上げ、直ちに表面の水を濾紙で拭き取り秤量した（Ｗ２）。吸水率は（Ｗ２−Ｗ１）／Ｗ１×１００[％]を算出することで求まった。なお、評価に際しては、各々３点ずつ測定を行い、これらの吸水率の平均値を示した。
【００４１】
実施例１
〔芳香族ポリエーテル系重合体を含有するフィルムの製造〕
式（II）で表される繰り返し単位を有する芳香族ポリエーテル系重合体を特開昭５８−１６７６２２号公報記載の方法、すなわち、２，２’−ビス（３，５―ジメチル−４−ヒドロキシフェニル）プロパンのクロロベンゼン／ＤＭＳＯ混合溶液を加熱し、窒素雰囲気下４４．８％水酸化カリウム水溶液を滴下した後、４，４’−ジフルオロベンゾフェノンの粉末を加えることにより合成した（ηinh ０．７５ｄｌ／ｇ）。この芳香族ポリエーテル系重合体２０ｇにＮＭＰ８０ｇを加えることで、２０ｗｔ％ＮＭＰ溶液１００ｇを得た。
【００４２】
【化３】

【００４３】
この芳香族ポリエーテル系重合体溶液を、３５μm厚銅箔 (三井金属（株）製：SQ−VLP)マット面上にバーコートにより塗布した。この際、用いるアプリケータのギャップを０．０２５ｍｍとした。これを窒素気流下８０℃で２０分間乾燥し感光性フィルムを得た。この時のフィルムの膜厚は５μｍであった。
得られた感光性フィルムについて碁盤目接着性評価を行った。結果を表１に示す。
【００４４】
実施例２
３５μm厚銅箔の代わりにガラス板を用い、アプリケータのギャップを０．２５ｍｍとする以外は、実施例１と同様にして膜厚５０μｍの感光性フィルムを得た。
得られた感光性フィルムについて、ガラス板から剥離させた後、吸水率評価を行った。
また上記で得られた感光性フィルムについて、ガラス板から剥離させた後、紫外線照射装置（ＯＲＣ社製 ＨＭＷ−５３２Ｄ）にて露光した（１,０００ｍＪ／ｃｍ²）。このフィルムの吸水率評価を行った。これらの結果を表１に示す。
【００４５】
比較例１
〔感光性ポリイミドを含有するフィルムの製造〕
式（III）で表される繰り返し単位を有するネガ型感光性ポリイミドを特開昭５９−２１９３３０号公報記載の方法、すなわち２，３，５，６−テトラメチル−１，４−フェニレンジアミンのＮＭＰ溶液にベンゾフェノンテトラカルボン酸ジ無水物を加えた後、トリエチルアミンおよび無水酢酸を加え生成したポリアミド酸を環化してポリイミドにすることにより合成した（ηinh ０．８８ｄｌ／ｇ）。このポリイミド２０ｇにＮＭＰ８０ｇを加えることで、２０ｗｔ％ＮＭＰ溶液１００ｇを得た。
【００４６】
【化４】

【００４７】
このポリイミド溶液を、３５μm厚銅箔 (三井金属（株）製：SQ−VLP)マット面上にバーコートにより塗布した。この際、用いるアプリケータのギャップを０．０２５ｍｍとした。これを窒素気流下８０℃で２０分間乾燥し感光性フィルムを得た。この時のフィルムの膜厚は５μｍであった。
得られた感光性ポリイミドフィルムについて碁盤目接着性評価を行った。結果を表１に示す。
【００４８】
比較例２
３５μm厚銅箔の代わりにガラス板を用い、アプリケータのギャップを０．２５ｍｍとする以外は、比較例１と同様にして膜厚５０μｍの感光性フィルムを得た。
得られた感光性フィルムについて、ガラス板から剥離させた後、吸水率評価を行った。
また上記で得られた感光性フィルムについて、ガラス板から剥離させた後、紫外線照射装置（ＯＲＣ社製 ＨＭＷ−５３２Ｄ）にて露光した（１,０００ｍＪ／ｃｍ²）。このフィルムの吸水率評価を行った。結果を表１に示す。
【００４９】
【表１】

【００５０】
実施例３
〔絶縁膜のパターン形成〕
実施例１で得られた感光性フィルムに、フォトマスクをのせ紫外線照射装置（ＯＲＣ社製 ＨＭＷ−５３２Ｄ）にて露光した（１,０００ｍＪ／ｃｍ²）。シクロペンタノンを現像液として６０秒浸漬することによって露光部を溶解除去した後、メタノールで３０秒間リンスした。続いてオーブンにて８０℃で３０分間加熱乾燥した。その結果、良好なパターンが形成されていることが確認できた。この時の解像度は１０μｍであった。
【００５１】
【発明の効果】
本発明の感光性フィルムから得られる絶縁膜は、支持基材との接着強度が極めて高く、また吸水率が低い。従って、該絶縁膜を例えば配線基板の表面保護膜や層間絶縁膜に用いた場合、パッケージ用封止樹脂との界面での剥離や、半導体パッケージへのクラック発生、半導体の電気不良等を抑えることができ、半導体の信頼性が著しく向上する。本発明の感光性フィルムから得られる絶縁膜は、表面保護膜や層間絶縁膜として高集積半導体装置、高集積多層配線基板等の用途に極めて有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photosensitive film formed on a supporting substrate containing an aromatic polyether polymer. More specifically, a negative photosensitive aromatic polymer that exhibits excellent adhesion to the substrate, plus heat resistance, mechanical properties, high solvent solubility and low dielectric properties, or high sensitivity and high sensitivity. The present invention relates to a photosensitive film containing an ether polymer and an insulating film using the film.
[0002]
[Prior art]
Conventionally, as circuit board materials using photosensitive resins, many polyimides have been used for resins. Examples of photosensitive polyimide include Japanese Patent Application Laid-Open No. 59-219330 and a paper by Pfeifer et al. (Pfeifer, J. and Rohde, O., Polyimides: Synthesis, Characterization, and Application, Proc. 2nd. Int. Cond. Poly. 130-page (1985)) and the like have reported examples of photocrosslinking reaction between a benzophenone structure in a skeleton and an alkyl group.
[0003]
However, in general, polyimide has low adhesiveness to a supporting substrate, and thus peeling may occur. In addition, polyimide tends to cause shrinkage strain during heat treatment, which may cause curling and make it difficult to form fine circuits. Furthermore, since general polyimide has high water absorption, there are many problems in application to circuit board materials, such as causing poor insulation and corrosion of semiconductor solid elements.
[0004]
On the other hand, for example, those disclosed in JP-A No. 58-167622 are known as aromatic polyether polymers, and in addition to high heat resistance equivalent to polyimide, mechanical strength and dimensional stability are excellent. Since it has both flammability and electrical insulation, it is expected to be widely used in fields that require heat resistance, such as electrical and electronic equipment, aerospace equipment, and transportation equipment. However, there is little discussion on photosensitivity. Among aromatic polyether polymers, examples of photosensitive polymers include Mohanty, D. et al. K. et al. , Polym. Prepr. , 25 (2), 19-page (1984), etc., but application to a photosensitive film that is excellent in adhesion to a supporting substrate and useful for circuit board materials has not been known. .
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a photosensitive film excellent in adhesiveness to a supporting substrate and an insulating film obtained from the film.
[0006]
[Means for Solving the Problems]
As a result of diligent research, the present inventors have surprisingly demonstrated that high-adhesiveness and low stress with a supporting base material are obtained by using photosensitive aromatic polyether polymers, and a circuit board with low water absorption. The inventors have found that a photosensitive film useful as a material can be produced, and completed the present invention.
[0007]
That is, the present invention relates to a photosensitive film formed on a supporting substrate, comprising an aromatic polyether polymer, an insulating film comprising the photosensitive film, and a pattern forming method for the insulating film. It is.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The photosensitive film of the present invention is characterized by containing an aromatic polyether polymer.
[0009]
The aromatic polyether polymer used for the photosensitive film of the present invention is not particularly limited as long as it has photosensitivity.
[0010]
The aromatic polyether polymer of the present invention is preferably an aromatic polyether polymer having a repeating unit represented by the formula (I).
[Chemical 2]

[0011]
(In the formula, A represents a divalent alkylene group having 1 to 10 carbon atoms, —SO ₂ —, —SO—, —S—, —O—, or —CO—. A and b are each independently selected. An integer of 0 to 4, m is an integer of 0 or 1, n is an integer of _{1 to} 3. R _{1 to} R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, Represents any one of halogen atoms, and at least one of R _{1 to} R ₄ is an alkyl group having 1 to 8 carbon atoms.)
[0012]
In the formula (I) of the present invention, A is not particularly limited as long as A is a divalent alkylene group having 1 to 10 carbon atoms, —SO ₂ —, —SO—, —S—, —O—, or —CO—. . Examples of the divalent alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, and the like.
[0013]
In the formula (I) of the present invention, R _{1 to} R ₆ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom, and at least one of R _{1 to} R ₄ If it is a C1-C8 alkyl group, it will not specifically limit.
[0014]
In the formula (I) of the present invention, preferred examples of R _{1 to} R ₆ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an alkyl group having 4 to 8 carbon atoms. Can be mentioned.
[0015]
In the formula (I) of the present invention, a and b are each independently an integer of 0 to 4, m is an integer of 0 or 1, and n is an integer of 1 to 3.
[0016]
In the present invention, the logarithmic viscosity ηinh of the aromatic polyether polymer is not particularly limited, but a preferable logarithmic viscosity is 0.1 to 2.0 dl / g, and 0.3 to 1. 8 dl / g is more preferable, and 0.5 to 1.6 dl / g is more preferable.
[0017]
If the logarithmic viscosity of the aromatic polyether polymer is too low, in general, the processability may decrease due to a decrease in photosensitivity, and the strength and toughness of the product after processing may be unfavorable. If the logarithmic viscosity of the aromatic polyether polymer is too high, fine pattern processing cannot be performed during the development process when the obtained aromatic polyether polymer film is photolithography processed for the purpose of producing a circuit substrate. In some cases, the reliability of the product decreases, which is not preferable.
[0018]
The method for evaluating the logarithmic viscosity of the aromatic polyether polymer is not particularly limited. For example, after dissolving 0.50 g of the aromatic polyether polymer in 100 ml of N-methyl-2-pyrrolidone, It can be measured at 35 ° C.
[0019]
The aromatic polyether polymer used in the present invention contains various diols and dihalide compounds in addition to the repeating unit component having the structure represented by the general formula (I), and various physical properties such as heat resistance, hygroscopicity, For the purpose of controlling the thermal expansion coefficient, dielectric constant, refractive index, birefringence, etc., it may be copolymerized as necessary. However, the aromatic polyether type polymer having the structure represented by the general formula (I) In a preferred embodiment, the coalescence is contained in the composition in an amount of 10 to 100% by weight.
[0020]
The aromatic polyether polymer used in the present invention may be produced by any method, and can be produced using a known method. Examples of the method for producing the compound of formula (I) include, but are not limited to, the method described in JP-A No. 58-167622.
[0021]
The support substrate used in the present invention is not particularly limited, and examples thereof include copper and copper alloy substrates, gold and gold alloy substrates, aluminum and aluminum alloy substrates, silicon wafers, glass substrates and quartz substrates. be able to.
[0022]
The photosensitive film of the present invention may be produced by any method. For example, for example, the aromatic polyether polymer is dissolved in an organic solvent, and this is dissolved on a supporting substrate. The method of apply | coating to and drying can be mentioned.
[0023]
In producing the photosensitive film of the present invention, when the aromatic polyether polymer is applied on a support substrate, a method of applying the aromatic polyether polymer dissolved in an appropriate organic solvent is preferable. Is the method. The solvent used here is not limited, but for example,
[0024]
(A) a phenolic solvent,
Phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6 -Xylenol, 3,4-xylenol, 3,5-xylenol,
[0025]
(B) an aprotic amide solvent,
N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, hexamethylphosphorotri Amide,
[0026]
(C) an ether solvent,
1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2-methoxyethoxy) ethyl] ether, 1,4-dioxane ,
[0027]
(D) an amine solvent,
Pyridine, quinoline, isoquinoline, α-picoline, β-picoline, γ-picoline, isophorone, piperidine, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine,
[0028]
(E) other solvent,
Dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetramethyl urea, anisole, water, benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p -Dichlorobenzene, bromobenzene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, p-bromo Toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentane, hexane, Heptane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, fluorobenzene, methyl acetate, ethyl acetate, butyl acetate, methyl formate, ethyl formate and the like. These solvents may be used alone or in combination of two or more.
[0029]
These solvents are preferably used in an amount of 100 to 10000 parts by weight, more preferably 200 to 5000 parts by weight, based on 100 parts by weight of the aromatic polyether polymer used.
[0030]
In producing the photosensitive film of the present invention, the method for applying the aromatic polyether polymer to the supporting substrate is not particularly limited. For example, application using a spin coater, application using a spray coater, bar coater Application, spraying, dipping, printing and the like using can be mentioned. The amount to be applied is not particularly limited, but for example, it is applied so that the final film thickness after curing is 1 μm to 500 μm, preferably 5 to 100 μm.
[0031]
In the step of drying after applying the aromatic polyether polymer on the support substrate, the drying time and drying temperature are not particularly limited, but generally 25 ° C. to 250 ° C., 10 minutes to 24 hours is sufficient. Drying may be performed in an air atmosphere, but may be performed in a nitrogen atmosphere or under reduced pressure.
[0032]
In the photosensitive film of the present invention, an aromatic polyether polymer is used as a composition component, and any other component such as a sensitizer, a photopolymerization initiator, a leveling agent, a coupling is used depending on the purpose. Although it may contain an agent, a monomer, an oligomer, a stabilizer, a wetting agent, a pigment, a dye, etc., it is a preferred embodiment that the aromatic polyether polymer is contained in the film in an amount of 10 to 100% by weight.
[0033]
The insulating film of the present invention is obtained from the above photosensitive film containing an aromatic polyether polymer.
The insulating film pattern forming method of the present invention is not particularly limited. For example, a relief pattern insulating film can be obtained by exposing and developing the photosensitive film. In each of these steps, a known technique can be used.
[0034]
The insulating film pattern forming method of the present invention includes an exposure step of irradiating ultraviolet rays and / or near ultraviolet-visible light using a photomask pattern, and a developing step of dissolving and removing unirradiated portions with a developer. .
[0035]
In the exposure step, ultraviolet rays of 150 to 500 nm and / or near-ultraviolet-visible light are radiated, and a wavelength region centering around a wavelength of 365 nm is particularly desirable because a high effect is obtained. In the exposure step, a photomask pattern having a desired shape can be used.
[0036]
In the development step, a relief pattern-like insulating film is obtained by dissolving and removing unirradiated portions with a developer. As the developer, for example, an organic solvent such as cyclopentanone, cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, or N-methyl-2-pyrrolidone can be used. Further, for example, two or more organic solvents may be mixed and used. The insulating film formed by development may be rinsed using, for example, methanol, ethanol, water or the like. Finally, heat treatment or the like is performed to remove the solvent. Although the temperature in the case of heat-processing is not specifically limited, It is preferable to process by 25 to 300 degreeC, More preferably, it is 40 to 300 degreeC.
[0037]
The insulating film obtained from the photosensitive film of the present invention has extremely high adhesive strength with the support substrate and low water absorption. Therefore, when this insulating film is used, for example, as a surface protection film or an interlayer insulating film of a wiring board, it suppresses peeling at the interface with the sealing resin for the package, generation of cracks in the semiconductor package, semiconductor electrical failure, etc. And the reliability of the semiconductor is significantly improved. The insulating film obtained from the photosensitive film of the present invention is extremely useful for applications such as highly integrated semiconductor devices and highly integrated multilayer wiring boards as surface protective films and interlayer insulating films.
[0038]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited at all by this.
〔Evaluation methods〕
The test methods of the tests in the examples are as follows.
(A) After dissolving 0.50 g of an aromatic ether polymer or polyimide logarithmic viscosity aromatic ether polymer or polyimide in 100 ml of N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP), It was measured with a viscometer at 35 ° C.
[0039]
(B) Cross-cut adhesion test of film Cross-cut adhesion evaluation of the film is based on the JIS-K5400 method, and a 2 mm wide, 25 square cross cut is attached to the film with a cutter knife. An evaluation score was assigned. The evaluation score is 10 points when there is no peeling of the film and the adhesive strength is sufficient, 0 points when the adhesive strength is 65% or more, and the intermediate adhesive strength is graded according to the degree of peeling. According to the evaluation of the above JIS-K5400 method, with 8, 6 and 4 points.
[0040]
(C) Evaluation of water absorption rate Both sides of a 50 × 50 mm, 50 μm thick film were wiped twice with methanol, wrapped in filter paper, and dried in an oven set at 50 ° C. for 24 hours. After drying, this film was immediately transferred into a desiccator and weighed in a constant temperature and humidity chamber at 23 ° C. and a relative humidity of 50% (W1 g). The weighed film was immersed in ion exchange water and allowed to stand for 24 hours. The film was pulled up from the water, and the surface water was immediately wiped off with filter paper and weighed (W2). The water absorption was obtained by calculating (W2−W1) / W1 × 100 [%]. In the evaluation, three points were measured for each, and the average value of these water absorption rates was shown.
[0041]
Example 1
[Production of Film Containing Aromatic Polyether Polymer]
An aromatic polyether polymer having a repeating unit represented by the formula (II) is obtained by the method described in JP-A No. 58-167622, that is, 2,2′-bis (3,5-dimethyl-4-hydroxy). This was synthesized by heating a chlorobenzene / DMSO mixed solution of phenyl) propane and dropping 44.8% aqueous potassium hydroxide solution under a nitrogen atmosphere, and then adding 4,4′-difluorobenzophenone powder (ηinh 0.75 dl / g). By adding 80 g of NMP to 20 g of this aromatic polyether polymer, 100 g of a 20 wt% NMP solution was obtained.
[0042]
[Chemical 3]

[0043]
This aromatic polyether polymer solution was applied to a 35 μm thick copper foil (Mitsui Metals Co., Ltd. product: SQ-VLP) mat surface by bar coating. At this time, the gap of the applicator used was set to 0.025 mm. This was dried at 80 ° C. for 20 minutes under a nitrogen stream to obtain a photosensitive film. The film thickness at this time was 5 μm.
The resulting photosensitive film was subjected to cross-cut adhesion evaluation. The results are shown in Table 1.
[0044]
Example 2
A photosensitive film having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that a glass plate was used instead of the 35 μm thick copper foil and the gap of the applicator was set to 0.25 mm.
About the obtained photosensitive film, after making it peel from a glass plate, water absorption evaluation was performed.
Moreover, after making it peel from the glass plate about the photosensitive film obtained above, it exposed with the ultraviolet irradiation device (HMW-532D by ORC) (1,000mJ / cm < ² >). The water absorption rate of this film was evaluated. These results are shown in Table 1.
[0045]
Comparative Example 1
[Production of film containing photosensitive polyimide]
A negative photosensitive polyimide having a repeating unit represented by the formula (III) is obtained by the method described in JP-A-59-219330, that is, NMP of 2,3,5,6-tetramethyl-1,4-phenylenediamine. After adding benzophenone tetracarboxylic dianhydride to the solution, triethylamine and acetic anhydride were added and the resulting polyamic acid was cyclized into a polyimide (ηinh 0.88 dl / g). By adding 80 g of NMP to 20 g of this polyimide, 100 g of a 20 wt% NMP solution was obtained.
[0046]
[Formula 4]

[0047]
This polyimide solution was applied by bar coating on a 35 μm thick copper foil (Mitsui Metals Co., Ltd. product: SQ-VLP) mat surface. At this time, the gap of the applicator used was set to 0.025 mm. This was dried at 80 ° C. for 20 minutes under a nitrogen stream to obtain a photosensitive film. The film thickness at this time was 5 μm.
The cross section adhesion evaluation was performed about the obtained photosensitive polyimide film. The results are shown in Table 1.
[0048]
Comparative Example 2
A photosensitive film having a film thickness of 50 μm was obtained in the same manner as in Comparative Example 1 except that a glass plate was used instead of the 35 μm thick copper foil and the gap of the applicator was 0.25 mm.
About the obtained photosensitive film, after making it peel from a glass plate, water absorption evaluation was performed.
Moreover, after making it peel from the glass plate about the photosensitive film obtained above, it exposed with the ultraviolet irradiation device (HMW-532D by ORC) (1,000mJ / cm < ² >). The water absorption rate of this film was evaluated. The results are shown in Table 1.
[0049]
[Table 1]

[0050]
Example 3
[Insulating film pattern formation]
The photosensitive film obtained in Example 1 was put on a photomask and exposed with an ultraviolet irradiation device (HMW-532D manufactured by ORC) (1,000 mJ / cm ² ). The exposed portion was dissolved and removed by immersing cyclopentanone as a developer for 60 seconds, and then rinsed with methanol for 30 seconds. Subsequently, it was dried in an oven at 80 ° C. for 30 minutes. As a result, it was confirmed that a good pattern was formed. The resolution at this time was 10 μm.
[0051]
【The invention's effect】
The insulating film obtained from the photosensitive film of the present invention has extremely high adhesive strength with the support substrate and low water absorption. Therefore, when this insulating film is used, for example, as a surface protection film or an interlayer insulating film of a wiring board, it suppresses peeling at the interface with the sealing resin for the package, generation of cracks in the semiconductor package, semiconductor electrical failure, etc. And the reliability of the semiconductor is significantly improved. The insulating film obtained from the photosensitive film of the present invention is extremely useful for applications such as highly integrated semiconductor devices and highly integrated multilayer wiring boards as surface protective films and interlayer insulating films.

Claims (3)

Formula (I)

(In the formula, A represents a divalent alkylene group having 1 to 10 carbon atoms, —SO ₂ —, —SO—, —S—, —O—, or —CO—. A and b are each independently selected. N represents an integer of 0 to 4, m represents an integer of 0 or 1, n represents an integer of _{1 to} 3. R _{1 to} R ₆ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, A halogen atom, and at least one of R _{1 to} R ₄ is an alkyl group having 1 to 8 carbon atoms.) Containing an aromatic polyether polymer having a repeating unit represented by: A photosensitive film formed on a supporting substrate characterized by the above. An insulating film obtained from the photosensitive film according to claim 1 . 3. The insulating film pattern formation according to claim 2 , further comprising: an exposure step of irradiating ultraviolet rays and / or near ultraviolet-visible light using a photomask pattern; and a developing step of dissolving and removing unirradiated portions with a developer. Method.