JP4006907B2 - Photosensitive transfer film - Google Patents

Description

【００２４】
（式中、Ｒ¹ およびＲ⁴ は、それぞれ、同一または異なる炭素数１〜３０のアルキル基を示し、Ｒ² およびＲ³ は、それぞれ、同一または異なるメチレン基または炭素数２〜３０のアルキレン基を示し、ｓは０〜５の数であり、ｔは１〜１０の数である。）
【００２５】
【化２】

【００２６】
（式中、Ｒ⁵ は炭素数１〜３０のアルキル基またはアルケニル基を示す。）
【００２７】
上記式（１）において、Ｒ¹ またはＲ⁴ で示されるアルキル基、並びにＲ² またはＲ³ で示されるアルキレン基は、直鎖状であっても分岐状であってもよく、また、飽和基であっても不飽和基であってもよい。Ｒ¹ またはＲ⁴ で示されるアルキル基の炭素数は、１〜３０とされ、好ましくは２〜２０、さらに好ましくは４〜１０とされる。当該アルキル基の炭素数が３０を超える場合には、溶剤に対する可塑剤の溶解性が低下し、転写フィルムの良好な可撓性が得られない場合がある。
【００２８】
上記式（１）で示される化合物の具体例としては、ジブチルアジペート、ジイソブチルアジペート、ジ−２−エチルヘキシルアジペート、ジ−２−エチルヘキシルアゼレート、ジブチルセバケート、ジブチルジグリコールアジペートなどが挙げられる。好ましくは、ｎが２〜６で表される化合物である。
【００２９】
上記式（２）において、Ｒ⁵ で示されるアルキル基およびアルケニル基は、直鎖状であっても分岐状であってもよく、また、飽和基であっても不飽和基であってもよい。Ｒ⁵ で示されるアルキル基またはアルケニル基の炭素数は、１〜３０とされ、好ましくは２〜２０、さらに好ましくは１０〜１８とされる。
上記式（２）で示される化合物の具体例としては、プロピレングリコールモノラウレート、プロピレングリコールモノオレートなどが挙げられる。
【００３０】
感光性組成物における可塑剤の含有割合としては、無機粒子１００重量部に対して、０．１〜２０重量部であることが好ましく、さらに好ましくは０．５〜１０重量部とされる。
【００３１】
▲２▼接着助剤
接着助剤としては、下記式（３）で表される化合物などのシランカップリング剤〔飽和アルキル基含有（アルキル）アルコキシシラン〕が好適に用いられる。
【００３２】
【化３】

【００３３】
（式中、ｐは３〜２０の整数、ｍは１〜３の整数、ｎは１〜３の整数、ａは１〜３の整数である。）
【００３４】
上記式（３）において、飽和アルキル基の炭素数を示すｐは３〜２０の整数とされ、好ましくは４〜１６の整数とされる。
【００３５】
上記式（３）で表されるシランカップリング剤の具体例としては、ｎ−プロピルジメチルメトキシシラン、ｎ−ブチルジメチルメトキシシラン、ｎ−デシルジメチルメトキシシラン、ｎ−ヘキサデシルジメチルメトキシシラン、ｎ−イコサンジメチルメトキシシランなどの飽和アルキルジメチルメトキシシラン類（ａ＝１，ｍ＝１，ｎ＝１）；
ｎ−プロピルジエチルメトキシシラン、ｎ−ブチルジエチルメトキシシラン、ｎ−デシルジエチルメトキシシラン、ｎ−ヘキサデシルジエチルメトキシシラン、ｎ−イコサンジエチルメトキシシランなどの飽和アルキルジエチルメトキシシラン類（ａ＝１，ｍ＝１，ｎ＝２）；
ｎ−ブチルジプロピルメトキシシラン、ｎ−デシルジプロピルメトキシシラン、ｎ−ヘキサデシルジプロピルメトキシシラン、ｎ−イコサンジプロピルメトキシシランなどの飽和アルキルジプロピルメトキシシラン類（ａ＝１，ｍ＝１，ｎ＝３）；
ｎ−プロピルジメチルエトキシシラン、ｎ−ブチルジメチルエトキシシラン、ｎ−デシルジメチルエトキシシラン、ｎ−ヘキサデシルジメチルエトキシシラン、ｎ−イコサンジメチルエトキシシランなどの飽和アルキルジメチルエトキシシラン類（ａ＝１，ｍ＝２，ｎ＝１）；
ｎ−プロピルジエチルエトキシシラン、ｎ−ブチルジエチルエトキシシラン、ｎ−デシルジエチルエトキシシラン、ｎ−ヘキサデシルジエチルエトキシシラン、ｎ−イコサンジエチルエトキシシランなどの飽和アルキルジエチルエトキシシラン類（ａ＝１，ｍ＝２，ｎ＝２）；
ｎ−ブチルジプロピルエトキシシラン、ｎ−デシルジプロピルエトキシシラン、ｎ−ヘキサデシルジプロピルエトキシシラン、ｎ−イコサンジプロピルエトキシシランなどの飽和アルキルジプロピルエトキシシラン類（ａ＝１，ｍ＝２，ｎ＝３）；
ｎ−プロピルジメチルプロポキシシラン、ｎ−ブチルジメチルプロポキシシラン、ｎ−デシルジメチルプロポキシシラン、ｎ−ヘキサデシルジメチルプロポキシシラン、ｎ−イコサンジメチルプロポキシシランなどの飽和アルキルジメチルプロポキシシラン類（ａ＝１，ｍ＝３，ｎ＝１）；
ｎ−プロピルジエチルプロポキシシラン、ｎ−ブチルジエチルプロポキシシラン、ｎ−デシルジエチルプロポキシシラン、ｎ−ヘキサデシルジエチルプロポキシシラン、ｎ−イコサンジエチルプロポキシシランなどの飽和アルキルジエチルプロポキシシラン類（ａ＝１，ｍ＝３，ｎ＝２）；
ｎ−ブチルジプロピルプロポキシシラン、ｎ−デシルジプロピルプロポキシシラン、ｎ−ヘキサデシルジプロピルプロポキシシラン、ｎ−イコサンジプロピルプロポキシシランなどの飽和アルキルジプロピルプロポキシシラン類（ａ＝１，ｍ＝３，ｎ＝３）；
【００３６】
ｎ−プロピルメチルジメトキシシラン、ｎ−ブチルメチルジメトキシシラン、ｎ−デシルメチルジメトキシシラン、ｎ−ヘキサデシルメチルジメトキシシラン、ｎ−イコサンメチルジメトキシシランなどの飽和アルキルメチルジメトキシシラン類（ａ＝２，ｍ＝１，ｎ＝１）；
ｎ−プロピルエチルジメトキシシラン、ｎ−ブチルエチルジメトキシシラン、ｎ−デシルエチルジメトキシシラン、ｎ−ヘキサデシルエチルジメトキシシラン、ｎ−イコサンエチルジメトキシシランなどの飽和アルキルエチルジメトキシシラン類（ａ＝２，ｍ＝１，ｎ＝２）；
ｎ−ブチルプロピルジメトキシシラン、ｎ−デシルプロピルジメトキシシラン、ｎ−ヘキサデシルプロピルジメトキシシラン、ｎ−イコサンプロピルジメトキシシランなどの飽和アルキルプロピルジメトキシシラン類（ａ＝２，ｍ＝１，ｎ＝３）
ｎ−プロピルメチルジエトキシシラン、ｎ−ブチルメチルジエトキシシラン、ｎ−デシルメチルジエトキシシラン、ｎ−ヘキサデシルメチルジエトキシシラン、ｎ−イコサンメチルジエトキシシランなどの飽和アルキルメチルジエトキシシラン類（ａ＝２，ｍ＝２，ｎ＝１）；
ｎ−プロピルエチルジエトキシシラン、ｎ−ブチルエチルジエトキシシラン、ｎ−デシルエチルジエトキシシラン、ｎ−ヘキサデシルエチルジエトキシシラン、ｎ−イコサンエチルジエトキシシランなどの飽和アルキルエチルジエトキシシラン類（ａ＝２，ｍ＝２，ｎ＝２）；
ｎ−ブチルプロピルジエトキシシラン、ｎ−デシルプロピルジエトキシシラン、ｎ−ヘキサデシルプロピルジエトキシシラン、ｎ−イコサンプロピルジエトキシシランなどの飽和アルキルプロピルジエトキシシラン類（ａ＝２，ｍ＝２，ｎ＝３）；
ｎ−プロピルメチルジプロポキシシラン、ｎ−ブチルメチルジプロポキシシラン、ｎ−デシルメチルジプロポキシシラン、ｎ−ヘキサデシルメチルジプロポキシシラン、ｎ−イコサンメチルジプロポキシシランなどの飽和アルキルメチルジプロポキシシラン類 （ａ＝２，ｍ＝３，ｎ＝１）；
ｎ−プロピルエチルジプロポキシシラン、ｎ−ブチルエチルジプロポキシシラン、ｎ−デシルエチルジプロポキシシラン、ｎ−ヘキサデシルエチルジプロポキシシラン、ｎ−イコサンエチルジプロポキシシランなどの飽和アルキルエチルジプロポキシシラン類 （ａ＝２，ｍ＝３，ｎ＝２）；
ｎ−ブチルプロピルジプロポキシシラン、ｎ−デシルプロピルジプロポキシシラン、ｎ−ヘキサデシルプロピルジプロポキシシラン、ｎ−イコサンプロピルジプロポキシシランなどの飽和アルキルプロピルジプロポキシシラン類（ａ＝２，ｍ＝３，ｎ＝３）；
【００３７】
ｎ−プロピルトリメトキシシラン、ｎ−ブチルトリメトキシシラン、ｎ−デシルトリメトキシシラン、ｎ−ヘキサデシルトリメトキシシラン、ｎ−イコサントリメトキシシランなどの飽和アルキルトリメトキシシラン類（ａ＝３，ｍ＝１）；
ｎ−プロピルトリエトキシシラン、ｎ−ブチルトリエトキシシラン、ｎ−デシルトリエトキシシラン、ｎ−ヘキサデシルトリエトキシシラン、ｎ−イコサントリエトキシシランなどの飽和アルキルトリエトキシシラン類（ａ＝３，ｍ＝２）；
ｎ−プロピルトリプロポキシシラン、ｎ−ブチルトリプロポキシシラン、ｎ−デシルトリプロポキシシラン、ｎ−ヘキサデシルトリプロポキシシラン、ｎ−イコサントリプロポキシシランなどの飽和アルキルトリプロポキシシラン類（ａ＝３，ｍ＝３）などを挙げることができ、これらは、単独でまたは２種以上を組み合わせて使用することができる。
【００３８】
これらのうち、ｎ−ブチルトリメトキシシラン、ｎ−デシルトリメトキシシラン、ｎ−ヘキサデシルトリメトキシシラン、ｎ−デシルジメチルメトキシシラン、ｎ−ヘキサデシルジメチルメトキシシラン、ｎ−ブチルトリエトキシシラン、ｎ−デシルトリエトキシシラン、ｎ−ヘキサデシルトリエトキシシラン、ｎ−デシルエチルジエトキシシラン、ｎ−ヘキサデシルエチルジエトキシシラン、ｎ−ブチルトリプロポキシシラン、ｎ−デシルトリプロポキシシラン、ｎ−ヘキサデシルトリプロポキシシランなどが特に好ましい。
【００３９】
感光性組成物における接着助剤の含有割合としては、無機粒子１００重量部に対して、０．００１〜１０重量部であることが好ましく、さらに好ましくは０．００１〜５重量部とされる。
【００４０】
▲３▼分散剤
無機粒子の分散剤としては、脂肪酸が好ましく用いられる。特に、炭素数８〜３０の脂肪酸が好ましい。上記脂肪酸の好ましい具体例としては、オクタン酸、ウンデシル酸、ラウリン酸、ミリスチン酸、パルミチン酸、ペンタデカン酸、ステアリン酸、アラキン酸等の飽和脂肪酸；エライジン酸、オレイン酸、リノール酸、リノレン酸、アラキドン酸などの不飽和脂肪酸を挙げることができ、これらは、単独でまたは２種以上を組み合わせて使用することができる。
【００４１】
感光性組成物における分散剤の含有割合としては、無機粒子１００重量部に対して、０．００１〜１０重量部であることが好ましく、さらに好ましくは０．０１〜５重量部とされる。
【００４２】
パターンの形成方法
本発明の感光性転写フィルムは、高さが１０μｍ以下のパターンを形成するために特に好適に用いられる。
本発明の感光性転写フィルムを用いたパターンの形成方法においては、〔１〕感光性転写層の転写工程、〔２〕感光性転写層の露光工程、〔３〕感光性転写層の現像工程、〔４〕感光性転写層パターンの焼成工程 の各工程を有する。
〔１〕感光性転写層の転写工程
転写工程では、本発明の感光性転写フィルムを使用し、当該感光性転写フィルムを構成する感光性転写層を基板上に転写する。
基板材料としては、例えばガラス、シリコーン、アルミナなどからなる板状部材が用いられ、ＰＤＰ用にはガラス基板が用いられる。この板状部材の表面に予め所望のパターンを形成したものを用いても差し支えない。基板表面に対しては、必要に応じて、シランカップリング剤などによる薬品処理；プラズマ処理；イオンプレーティング法、スパッタリング法、気相反応法、真空蒸着法などによる薄膜形成処理のような適宜の前処理を施していてもよい。
転写工程の一例を示せば以下のとおりである。必要に応じて使用される感光性転写フィルムの保護フィルムを剥離した後、基板上に、感光性転写層の表面が当接されるように感光性転写フィルムを重ね合わせ、この感光性転写フィルムを加熱ローラなどにより熱圧着する。これにより、基板上に感光性転写層が転写されて密着した状態となる。ここで、転写条件としては、例えば、加熱ローラの表面温度が２０〜１４０℃、加熱ローラによるロール圧が１〜５ｋｇ／ｃｍ² 、加熱ローラの移動速度が０．１〜１０．０ｍ／分を示すことができる。また、基板は予熱されていてもよく、予熱温度としては例えば４０〜１００℃とすることができる。
【００４３】
〔２〕感光性転写層の露光工程
露光工程においては、感光性転写層の表面に、露光用マスクを介して、放射線を選択的照射（露光）して、感光性転写層のパターンの潜像を形成する。なお、感光性転写層上の支持フィルムは露光工程の前に剥離除去してもよく、また、露光工程の後、後述する現像工程の前に剥離除去してもよい。感度上昇の観点から、感光性転写層上の支持フィルムは露光工程の後、後述する現像工程の前に剥離除去することが好ましい。
露光工程において放射線を選択的照射（露光）される放射線としては、可視光線、紫外線、遠紫外線、電子線あるいはＸ線等を含むものであり、好ましくは可視光線、紫外線および遠紫外線が用いられ、さらに好ましくは紫外線が用いられる。
露光用マスクの露光パターンは目的によって異なるが、例えば、１０〜５００μｍ幅のストライプが用いられる。
放射線照射装置としては、フォトリソグラフィー法で使用されている紫外線照射装置、半導体および液晶表示装置を製造する際に使用されている露光装置など特に限定されるものではない。
【００４４】
〔３〕感光性転写層の現像工程
現像工程においては、露光された感光性転写層を現像処理することにより、感光性転写層のパターン（潜像）を顕在化させる。
感光性転写層の現像工程で使用される現像液としては、アルカリ現像液を使用することができる。これにより、感光性転写層に含有されるアルカリ可溶性樹脂を容易に溶解除去することができる。
なお、感光性転写層に含有される無機粒子は、アルカリ可溶性樹脂により均一に分散されているため、バインダーであるアルカリ可溶性樹脂を溶解させ、洗浄することにより、無機粒子も同時に除去される。
アルカリ現像液の有効成分としては、例えば水酸化リチウム、水酸化ナトリウム、水酸化カリウム、リン酸水素ナトリウム、リン酸水素二アンモニウム、リン酸水素二カリウム、リン酸水素二ナトリウム、リン酸二水素アンモニウム、リン酸二水素カリウム、リン酸二水素ナトリウム、ケイ酸リチウム、ケイ酸ナトリウム、ケイ酸カリウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、ホウ酸リチウム、ホウ酸ナトリウム、ホウ酸カリウム、アンモニアなどの無機アルカリ性化合物；テトラメチルアンモニウムヒドロキシド、トリメチルヒドロキシエチルアンモニウムヒドロキシド、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノイソプロピルアミン、ジイソプロピルアミン、エタノールアミンなどの有機アルカリ性化合物などを挙げることができる。
感光性転写層の現像工程で使用されるアルカリ現像液は、前記アルカリ性化合物の１種または２種以上を水などに溶解させることにより調製することができる。ここに、アルカリ性現像液におけるアルカリ性化合物の濃度は、通常０．００１〜１０質量％とされ、好ましくは０．０１〜５質量％とされる。アルカリ現像液には、ノニオン系界面活性剤や有機溶剤などの添加剤が含有されていてもよい。なお、アルカリ現像液による現像処理がなされた後は、通常、水洗処理が施される。また、必要に応じて現像処理後に感光性転写層パターン側面および基板露出部に残存する不要分を擦り取る工程を含んでもよい。
ここに、現像処理条件としては、現像液の種類・組成・濃度、現像時間、現像温度、現像方法（例えば浸漬法、揺動法、シャワー法、スプレー法、パドル法）、現像装置などを適宜選択することができる。
この現像工程により、感光性転写層残留部と、感光性転写層除去部とから構成される感光性転写層パターン（露光用マスクに対応するパターン）が形成される。
【００４５】
〔４〕感光性転写層パターンの焼成工程
この工程においては、感光性転写層パターンを焼成処理して、パターンを形成する。これにより、感光性転写層残留部中の有機物質が焼失して、基板の表面に無機パターンを得ることができる。
ここに、焼成処理の温度としては、樹脂層残留部中の有機物質が焼失される温度であることが必要であり、通常、大気中、４００〜６００℃とされる。また、焼成時間は、通常１０〜９０分間とされる。
上記のようにして基板上に形成されるパターンの高さは０を含まない１０μｍ以下であり、好ましくは１〜８μｍであり、さらに好ましくは２〜６μｍである。
【００４６】
【実施例】
以下、本発明の実施例について説明するが、本発明はこれらによって限定されるものではない。なお、以下において「部」は「質量部」を示す。
また、重量平均分子量（Ｍｗ）は、東ソー株式会社製ゲルパーミィエーションクロマトグラフィー（ＧＰＣ）（商品名ＨＬＣ−８０２Ａ）により測定したポリスチレン換算の平均分子量である。
【００４７】
＜実施例１＞
（１）感光性組成物の調製：
（Ａ）無機粒子として、平均粒径１μｍのＡｇ粒子（粒状）１００部、平均粒径２μｍのＢｉ₂ Ｏ₃ −ＺｎＯ−Ｂ₂ Ｏ₃ −ＳｉＯ₂ −Ａｌ₂ Ｏ₃ 系低融点ガラスフリット（不定形、軟化点５２０℃）１０部、（Ｂ）アルカリ可溶性樹脂として、メタクリル酸ｎ−ブチル／メタクリル酸３−ヒドロキシプロピル／メタクリル酸＝６０／２０／２０（質量％）共重合体（Ｍｗ＝１００，０００）３０部、（Ｃ）エチレン性不飽和基含有化合物として、トリメチロールプロパントリアクリレート２０部、（Ｄ）光重合開始剤として、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタン−１−オン５部、（Ｅ）溶剤として、プロピレングリコールモノメチルエーテル１５０部および（Ｆ）分散剤として、オレイン酸１部をビーズミルで混練りした後、ステンレスメッシュ（２００メッシュ、２５μｍ径）でフィルタリングすることにより、感光性組成物を調製した。
【００４８】
（２）感光性転写フィルムの作製：
下記（イ）の操作により、感光性転写層が支持フィルム上に形成されてなる本発明の感光性転写フィルムを作製した。
（イ）感光性組成物を予め離型処理したＰＥＴフィルムよりなる支持フィルム（幅２００ｍｍ、長さ３０ｍ、厚さ３８μｍ）上にブレードコーターを用いて塗布し、塗膜を１００℃で５分間乾燥して溶剤を完全に除去し、厚さ１０μｍの感光性樹脂層を支持フィルム上に形成した。
【００４９】
感光性転写層の転写工程：
６インチパネル用のガラス基板の表面に、感光性転写層の表面が当接されるよう感光性転写フィルムを重ね合わせ、この感光性転写フィルムを加熱ローラにより熱圧着した。ここで、圧着条件としては、加熱ローラの表面温度を１２０℃、ロール圧を４ｋｇ／ｃｍ² 、加熱ローラの移動速度を０．５ｍ／分とした。これにより、ガラス基板の表面に感光性転写層が転写されて密着した状態となった。この感光性転写層について膜厚を測定したところ、１０μｍ±１μｍの範囲にあった。
【００５０】
感光性転写層の露光工程・現像工程：
感光性転写層に対して、露光用マスク（５０μｍ幅のストライプパターン）を介して、超高圧水銀灯により、ｉ線（波長３６５ｎｍの紫外線）を照射した。ここに、照射量は４００ｍＪ／ｃｍ²とした。
【００５１】
露光工程の終了後、感光性転写層より支持フィルムを剥離除去した後、露光処理された感光性転写層に対して、０．５質量％の炭酸ナトリウム水溶液（３０℃）を現像液とするシャワー法による現像処理を１分かけて行った。次いで超純水による水洗処理を行い、これにより、紫外線が照射されていない未硬化の感光性転写層を除去し、パターンを形成した。
【００５２】
感光性転写層パターンの焼成工程：
感光性転写層パターンが形成されたガラス基板を焼成炉内で６００℃の温度雰囲気下で３０分間にわたり焼成処理を行った。これにより、ガラス基板の表面に電極パターンが形成されてなるパネル材料が得られた。
得られたパネル材料における電極パターンについて、走査型電子顕微鏡を用いて、当該電極パターンのライン幅および高さの測定を行い、パターン幅の精度について、５０μｍ±５μｍの範囲にあるものを○、それ以外のものを×として評価した。また、パターンの欠落についての観察を行った。次いで、感光性転写層パターン焼成工程前後におけるパターン質量の測定を行い、質量損失を算出した。結果を表１に示す。
【００５３】
＜実施例２＞
（Ｂ）アルカリ可溶性樹脂として、メタクリル酸ｎ−ブチル／メタクリル酸３−ヒドロキシプロピル／メタクリル酸＝６０／２０／２０（質量％）共重合体（Ｍｗ＝１００，０００）６０部、（Ｃ）エチレン性不飽和基含有化合物として、トリメチロールプロパントリアクリレート４０部を用いたこと以外は実施例１と同様にして、感光性組成物を調製した。当該感光性組成物を用いたこと以外は実施例１と同様にして、厚さ１５μｍの感光性転写層が支持フィルム上に形成されてなる本発明の感光性転写フィルムを作製した。当該感光性転写フィルムを用いたこと以外は実施例１と同様にして、電極パターンが形成されてなるパネル材料を作製し、評価を行った。結果を表１に示す。
【００５４】
＜実施例３＞
（Ｂ）アルカリ可溶性樹脂として、メタクリル酸ｎ−ブチル／メタクリル酸３−ヒドロキシプロピル／メタクリル酸＝６０／２０／２０（質量％）共重合体（Ｍｗ＝１００，０００）９０部、（Ｃ）エチレン性不飽和基含有化合物として、トリメチロールプロパントリアクリレート６０部を用いたこと以外は実施例１と同様にして、感光性組成物を調製した。当該感光性組成物を用いたこと以外は実施例１と同様にして、厚さ２０μｍの感光性転写層が支持フィルム上に形成されてなる本発明の感光性転写フィルムを作製した。当該感光性転写フィルムを用いたこと以外は実施例１と同様にして、電極パターンが形成されてなるパネル材料を作製し、評価を行った。結果を表１に示す。
【００５５】
＜実施例４＞
（Ｂ）アルカリ可溶性樹脂として、メタクリル酸ｎ−ブチル／メタクリル酸３−ヒドロキシプロピル／メタクリル酸＝６０／２０／２０（質量％）共重合体（Ｍｗ＝１００，０００）１８部、（Ｃ）エチレン性不飽和基含有化合物として、トリメチロールプロパントリアクリレート１２部を用いたこと以外は実施例１と同様にして、感光性組成物を調製した。当該感光性組成物を用いたこと以外は実施例１と同様にして、厚さ１５μｍの感光性転写層が支持フィルム上に形成されてなる本発明の感光性転写フィルムを作製した。当該感光性転写フィルムを用いたこと以外は実施例１と同様にして、電極パターンが形成されてなるパネル材料を作製し、評価を行った。結果を表１に示す。
【００５６】
＜実施例５＞
（Ｂ）アルカリ可溶性樹脂として、メタクリル酸ｎ−ブチル／メタクリル酸３−ヒドロキシプロピル／メタクリル酸＝６０／２０／２０（質量％）共重合体（Ｍｗ＝１００，０００）２７部、（Ｃ）エチレン性不飽和基含有化合物として、トリメチロールプロパントリアクリレート１８部を用いたこと以外は実施例１と同様にして、感光性組成物を調製した。当該感光性組成物を用いたこと以外は実施例１と同様にして、厚さ２０μｍの感光性転写層が支持フィルム上に形成されてなる本発明の感光性転写フィルムを作製した。当該感光性転写フィルムを用いたこと以外は実施例１と同様にして、電極パターンが形成されてなるパネル材料を作製し、評価を行った。結果を表１に示す。
【００５７】
＜実施例６＞
（Ａ）無機粒子として、平均粒径０．３μｍのＣｕ−Ｆｅ−Ｍｎ複合酸化物粒子（球状）１００部、平均粒径２μｍのＢｉ₂ Ｏ₃ −ＺｎＯ−Ｂ₂ Ｏ₃ −ＳｉＯ₂ −Ａｌ₂ Ｏ₃ 系低融点ガラスフリット（不定形、軟化点５２０℃）１０部、（Ｂ）アルカリ可溶性樹脂として、メタクリル酸ｎ−ブチル／メタクリル酸３−ヒドロキシプロピル／メタクリル酸＝６０／２０／２０（質量％）共重合体（Ｍｗ＝１００，０００）１２０部、（Ｃ）エチレン性不飽和基含有化合物として、トリメチロールプロパントリアクリレート８０部を用いたこと以外は実施例１と同様にして、感光性組成物を調製した。当該感光性組成物を用いたこと以外は実施例１と同様にして、厚さ１０μｍの感光性転写層が支持フィルム上に形成されてなる本発明の感光性転写フィルムを作製した。当該感光性転写フィルムを用いたこと以外は実施例１と同様にして、ブラックマトリクスパターンが形成されてなるパネル材料を作製し、当該ブラックマトリクスパターンについて評価を行った。結果を表１に示す。
【００５８】
＜実施例７＞
（Ｂ）アルカリ可溶性樹脂として、メタクリル酸ｎ−ブチル／メタクリル酸３−ヒドロキシプロピル／メタクリル酸＝６０／２０／２０（質量％）共重合体（Ｍｗ＝１００，０００）１８０部、（Ｃ）エチレン性不飽和基含有化合物として、トリメチロールプロパントリアクリレート１２０部を用いたこと以外は実施例６と同様にして、感光性組成物を調製した。当該感光性組成物を用いたこと以外は実施例６と同様にして、厚さ１５μｍの感光性転写層が支持フィルム上に形成されてなる本発明の感光性転写フィルムを作製した。当該感光性転写フィルムを用いたこと以外は実施例６と同様にして、ブラックマトリクスパターンが形成されてなるパネル材料を作製し、評価を行った。結果を表１に示す。
【００５９】
＜実施例８＞
（Ｂ）アルカリ可溶性樹脂として、メタクリル酸ｎ−ブチル／メタクリル酸３−ヒドロキシプロピル／メタクリル酸＝６０／２０／２０（質量％）共重合体（Ｍｗ＝１００，０００）３６部、（Ｃ）エチレン性不飽和基含有化合物として、トリメチロールプロパントリアクリレート２４部を用いたこと以外は実施例６と同様にして、感光性組成物を調製した。当該感光性組成物を用いたこと以外は実施例６と同様にして、厚さ１０μｍの感光性転写層が支持フィルム上に形成されてなる本発明の感光性転写フィルムを作製した。当該感光性転写フィルムを用いたこと以外は実施例６と同様にして、ブラックマトリクスパターンが形成されてなるパネル材料を作製し、評価を行った。結果を表１に示す。
【００６０】
＜実施例９＞
（Ｂ）アルカリ可溶性樹脂として、メタクリル酸ｎ−ブチル／メタクリル酸３−ヒドロキシプロピル／メタクリル酸＝６０／２０／２０（質量％）共重合体（Ｍｗ＝１００，０００）６０部、（Ｃ）エチレン性不飽和基含有化合物として、トリメチロールプロパントリアクリレート４０部を用いたこと以外は実施例６と同様にして、感光性組成物を調製した。当該感光性組成物を用いたこと以外は実施例６と同様にして、厚さ１５μｍの感光性転写層が支持フィルム上に形成されてなる本発明の感光性転写フィルムを作製した。当該感光性転写フィルムを用いたこと以外は実施例６と同様にして、ブラックマトリクスパターンが形成されてなるパネル材料を作製し、評価を行った。結果を表１に示す。
【００６１】
＜実施例１０＞
（Ｂ）アルカリ可溶性樹脂として、メタクリル酸ｎ−ブチル／メタクリル酸３−ヒドロキシプロピル／メタクリル酸＝６０／２０／２０（質量％）共重合体（Ｍｗ＝１００，０００）９０部、（Ｃ）エチレン性不飽和基含有化合物として、トリメチロールプロパントリアクリレート６０部を用いたこと以外は実施例６と同様にして、感光性組成物を調製した。当該感光性組成物を用いたこと以外は実施例６と同様にして、厚さ２０μｍの感光性転写層が支持フィルム上に形成されてなる本発明の感光性転写フィルムを作製した。当該感光性転写フィルムを用いたこと以外は実施例６と同様にして、ブラックマトリクスパターンが形成されてなるパネル材料を作製し、評価を行った。結果を表１に示す。
【００６２】
＜比較例１＞
（Ｂ）アルカリ可溶性樹脂として、メタクリル酸ｎ−ブチル／メタクリル酸３−ヒドロキシプロピル／メタクリル酸＝６０／２０／２０（質量％）共重合体（Ｍｗ＝１００，０００）９部、（Ｃ）エチレン性不飽和基含有化合物として、トリメチロールプロパントリアクリレート６部を用いたこと以外は実施例１と同様にして、感光性組成物を調製した。当該感光性組成物を用いたこと以外は実施例１と同様にして、厚さ４μｍの感光性転写層が支持フィルム上に形成されてなる本発明の感光性転写フィルムを作製した。当該感光性転写フィルムを用いたこと以外は実施例１と同様にして、電極パターンが形成されてなるパネル材料を作製し、評価を行った。結果を表１に示す。
【００６３】
＜比較例２＞
（Ｂ）アルカリ可溶性樹脂として、メタクリル酸ｎ−ブチル／メタクリル酸３−ヒドロキシプロピル／メタクリル酸＝６０／２０／２０（質量％）共重合体（Ｍｗ＝１００，０００）６０部、（Ｃ）エチレン性不飽和基含有化合物として、トリメチロールプロパントリアクリレート４０部を用いたこと以外は実施例１と同様にして、感光性組成物を調製した。当該感光性組成物を用いたこと以外は実施例１と同様にして、厚さ４０μｍの感光性転写層が支持フィルム上に形成されてなる本発明の感光性転写フィルムを作製した。当該感光性転写フィルムを用いたこと以外は実施例１と同様にして、電極パターンが形成されてなるパネル材料を作製し、評価を行った。結果を表１に示す。
【００６４】
＜比較例３＞
（Ｂ）アルカリ可溶性樹脂として、メタクリル酸ｎ−ブチル／メタクリル酸３−ヒドロキシプロピル／メタクリル酸＝６０／２０／２０（質量％）共重合体（Ｍｗ＝１００，０００）３６部、（Ｃ）エチレン性不飽和基含有化合物として、トリメチロールプロパントリアクリレート２４部を用いたこと以外は実施例６と同様にして、感光性組成物を調製した。当該感光性組成物を用いたこと以外は実施例６と同様にして、厚さ４μｍの感光性転写層が支持フィルム上に形成されてなる本発明の感光性転写フィルムを作製した。当該感光性転写フィルムを用いたこと以外は実施例６と同様にして、ブラックマトリクスパターンが形成されてなるパネル材料を作製し、評価を行った。結果を表１に示す。
【００６５】
＜比較例４＞
（Ｂ）アルカリ可溶性樹脂として、メタクリル酸ｎ−ブチル／メタクリル酸３−ヒドロキシプロピル／メタクリル酸＝６０／２０／２０（質量％）共重合体（Ｍｗ＝１００，０００）１８０部、（Ｃ）エチレン性不飽和基含有化合物として、トリメチロールプロパントリアクリレート１２０部を用いたこと以外は実施例６と同様にして、感光性組成物を調製した。当該感光性組成物を用いたこと以外は実施例６と同様にして、厚さ４０μｍの感光性転写層が支持フィルム上に形成されてなる本発明の感光性転写フィルムを作製した。当該感光性転写フィルムを用いたこと以外は実施例６と同様にして、ブラックマトリクスパターンが形成されてなるパネル材料を作製し、評価を行った。結果を表１に示す。
【００６６】
【表１】

【００６７】
【発明の効果】
本発明の感光性転写フィルムによれば、基板への密着性に優れ、かつ寸法精度の高いパターンを簡便に形成することができる。本発明の感光性転写フィルムは、プラズマディスプレイパネルの電極、蛍光体、カラーフィルターおよびブラックマトリクス形成のために好適に使用することができる。
【図面の簡単な説明】
【図１】 交流型のプラズマディスプレイパネルの断面形状を示す模式図。
【符号の説明】
１ ガラス基板（前面基板） ２ ガラス基板（背面基板）
３ 隔壁 ４ 透明電極
５ バス電極 ６ アドレス電極
７ 蛍光体 ８ 誘電体層（前面基板）
９ 誘電体層（背面基板） １０ 保護膜[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photosensitive transfer film that can be suitably used to form a pattern with high dimensional accuracy, and more specifically, an electrode, a phosphor, a color filter, and a black matrix that constitute each display cell of a plasma display panel. The present invention relates to a photosensitive transfer film that can be suitably used to form a pattern with high dimensional accuracy.
[0002]
[Prior art]
In recent years, a plasma display has attracted attention as a flat fluorescent display. FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type plasma display panel (hereinafter also referred to as “PDP”). In the figure, reference numerals 1 and 2 denote glass substrates facing each other, 3 denotes a partition wall, and cells are partitioned by the glass substrate 1, the glass substrate 2, and the partition wall 3. 4 is a transparent electrode fixed on the glass substrate 1, 5 is a bus electrode formed on the transparent electrode for the purpose of reducing the resistance of the transparent electrode, 6 is an address electrode fixed on the glass substrate 2, and 7 is in the cell. The held phosphor, 8 is a dielectric layer formed on the surface of the glass substrate 1 so as to cover the transparent electrode 4 and the bus electrode 5, and 9 is formed on the surface of the glass substrate 2 so as to cover the address electrode 6. The dielectric layers 10 are protective films made of, for example, magnesium oxide. In a direct current type PDP, a resistor is usually provided between an electrode terminal (anode terminal) and an electrode lead (anode lead).
Further, in order to improve the contrast of the PDP, red, green and blue color filters, and a black matrix having a normal stripe shape or lattice shape are preferably used between the glass substrate 1 and the dielectric layer 8 or the dielectric material. It may be provided between the layer 8 and the protective film 10.
The pattern height of the PDP electrode, phosphor, color filter, and black matrix is preferably as low as possible without impairing the performance of each. When the pattern height is increased, the flatness of the dielectric layer and the protective film covering the electrodes, the color filter, and the black matrix is deteriorated, which may appear as luminance unevenness of the PDP. In addition, in the phosphor, the discharge space is reduced by the increase in the pattern height, and the luminance may be lowered.
[0003]
As a method for producing such a PDP electrode, phosphor, color filter, and black matrix, (1) screen printing is performed by screen-printing a non-photosensitive inorganic particle-containing paste on a substrate and firing the pattern. (2) A photosensitive inorganic particle-containing paste is screen-printed to form a film on the substrate, and this film is irradiated with ultraviolet rays through a photomask and developed to leave a pattern on the substrate, The photosensitive paste method etc. which bake this are known.
[0004]
[Problems to be solved by the invention]
However, the screen printing method has a problem that the positional accuracy of the pattern becomes very strict as the panel becomes larger and higher in definition, and cannot be handled by normal printing.
Although the photosensitive paste method is excellent in pattern positional accuracy, when forming a film on a substrate by screen printing, film thickness fluctuations and film defects are likely to occur depending on paste properties and printing conditions, and dimensional accuracy is high. There was a problem that process management for obtaining a pattern was difficult.
[0005]
The present invention has been made based on the above situation.
A first object of the present invention is to provide a photosensitive transfer film capable of forming a pattern through at least the steps of transfer, exposure, development, and baking.
The second object of the present invention is to provide a photosensitive transfer film that can easily form a pattern with high dimensional accuracy.
A third object of the present invention is to provide a photosensitive transfer film having excellent adhesion to a substrate.
[0006]
[Means for Solving the Problems]
  The photosensitive transfer film of the present invention (hereinafter also referred to as “the photosensitive transfer film of the present invention” or “the transfer film of the present invention”) comprises (A) inorganic particles, (B) an alkali-soluble resin, and (C) an ethylenic resin. Contains an unsaturated group-containing compound and (D) a photopolymerization initiator, and has a film thickness of 5 to 30 μmFurther, when the baking treatment is performed at 600 ° C., the mass loss is 25 to 75% by mass.And a photosensitive transfer layer. The photosensitive transfer film of the present invention isThe film thickness of the photosensitive transfer layer is 10-20 μmIt is preferable. Furthermore, the transfer film of the present invention has (A) inorganic particle content.25-75It is preferable to have a photosensitive transfer layer of mass%. The photosensitive transfer film of the present invention is suitably used for forming at least one member selected from a PDP electrode, a phosphor, a color filter, and a black matrix.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the details of the photosensitive transfer film of the present invention will be described.
Photosensitive transfer film
The photosensitive transfer film of the present invention is
(A) inorganic particles,
(B) an alkali-soluble resin,
(C) an ethylenically unsaturated group-containing compound and
(D) Photopolymerization initiator
And a photosensitive transfer layer having a film thickness of 5 to 30 μm is essential.
Moreover, the photosensitive transfer film of this invention has a support film and the photosensitive transfer layer formed on this, The protective film may be provided in the surface of the said photosensitive transfer layer.
[0008]
<Supporting film and protective film>
The support film constituting the photosensitive transfer film of the present invention is preferably a resin film having heat resistance and solvent resistance and flexibility. Since the support film has flexibility, a photosensitive transfer layer can be formed by applying a paste-like composition by a roll coater, and the photosensitive transfer layer is stored in a roll shape, Can be supplied. Examples of the resin forming the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyfluoroethylene and other fluorine-containing resins, nylon, and cellulose. The thickness of the support film is, for example, 20 to 100 μm.
The surface of the support film is preferably subjected to a release treatment. Thereby, the peeling operation of a support film can be easily performed in the formation process of the below-mentioned pattern.
In addition, about a protective film, the thing similar to a support film can be used. Further, the surface of the protective film is usually subjected to a release treatment, and the peel strength between the protective film / photosensitive transfer layer needs to be smaller than the peel strength between the support film / photosensitive transfer layer.
[0009]
<Photosensitive transfer layer>
The photosensitive transfer layer constituting the photosensitive transfer film of the present invention is usually
(A) inorganic particles,
(B) an alkali-soluble resin,
(C) an ethylenically unsaturated group-containing compound,
(D) a photopolymerization initiator,
(E) Solvent and as required
(F) It can form by apply | coating the paste-form photosensitive composition containing various additives on a support film, drying a coating film, and removing a part or all of a solvent.
[0010]
As a method of applying a photosensitive composition on a support film to obtain a photosensitive transfer layer, a film having a large thickness (for example, 1 μm or more) excellent in film thickness uniformity can be efficiently formed. Specifically, a coating method using a roll coater, a coating method using a blade coater, a coating method using a slit coater, a coating method using a curtain coater, a coating method using a wire coater, and the like can be mentioned as preferable examples.
The drying condition of the coating film is about 0.5 to 30 minutes at 50 to 150 ° C., and the residual ratio of the solvent after drying (content in the photosensitive transfer layer) is usually 2% by mass or less. The
The film thickness of the photosensitive transfer layer formed on the support film as described above is 5 to 30 μm, preferably 8 to 25 μm, and more preferably 10 to 20 μm.
[0011]
In the photosensitive transfer film of the present invention, the mass loss when the photosensitive transfer layer is baked at 600 ° C. is preferably 20 to 80% by mass. By setting the mass loss in the baking step of the photosensitive transfer layer to 20 to 80% by mass, it is possible to obtain a photosensitive transfer film that is more excellent in adhesion to the substrate and can form a pattern with high dimensional accuracy. it can. In addition, More preferably, the said mass loss is 25-75 mass%, Most preferably, it is 30-70 mass%.
[0012]
Moreover, as (A) inorganic particle content in a photosensitive transfer layer, Preferably it is 20-80 mass% with respect to the whole photosensitive transfer layer in a transfer film, More preferably, it is 25-75 mass%, Especially preferably, it is. 30 to 70% by mass. By having such a photosensitive transfer layer, it is possible to obtain a photosensitive transfer film that has excellent adhesion to the substrate and can form a pattern with high dimensional accuracy.
[0013]
<Photosensitive composition>
The photosensitive composition used for forming the photosensitive transfer layer constituting the photosensitive transfer film of the present invention comprises (A) inorganic particles, (B) an alkali-soluble resin, and (C) an ethylenically unsaturated group-containing compound. , (D) Photopolymerization initiator, (E) Solvent, and (F) Various additives, if necessary, prepared by kneading using a kneader such as a roll kneader, mixer, homomixer, ball mill, or bead mill. can do.
The photosensitive composition prepared as described above is a paste-like composition having fluidity suitable for coating, and its viscosity is usually 100 to 100,000 cp, preferably 500 to 10,000 cp. It is said.
Hereinafter, each component constituting the photosensitive composition will be described.
[0014]
(A) Inorganic particles
The inorganic particles used in the photosensitive composition vary depending on the type of forming material.
Inorganic particles used for electrode forming materials such as PDP, LCD, organic EL element, printed circuit board, multilayer circuit board, multichip module and LSI include Ag, Au, Al, Ni, Ag-Pd alloy, Cu, Cr etc. can be mentioned. Among these, it is preferable to use Ag that is relatively inexpensive because it does not cause a decrease in conductivity due to oxidation even when baked in the air. The shape of the inorganic particles used for the electrode forming material is not particularly limited, such as granular, spherical, and flaky shapes, and may be used alone or by mixing two or more types of inorganic particles. The average particle diameter is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm, and inorganic particles having different average particle diameters can be mixed and used.
Inorganic particles used for transparent electrode forming materials such as PDP, LCD and organic EL elements include indium oxide, tin oxide, tin-containing indium oxide (ITO), antimony-containing tin oxide (ATO), and fluorine-added indium oxide (FIO). ), Fluorine-added tin oxide (FTO), fluorine-added zinc oxide (FZO), and zinc oxide fine particles containing one or more metals selected from Al, Co, Fe, In, Sn and Ti Can be mentioned.
The inorganic particles used in the PDP phosphor-forming material are Y for red.₂ O_Three : Eu³⁺, Y₂ SiO_Five : Eu³⁺, Y_Three Al_Five O₁₂: Eu³⁺, YVO_Four : Eu³⁺, (Y, Gd) BO_Three : Eu³⁺, Zn_Three (PO_Four )₂ : Zn for green, such as Mn₂ SiO_Four : Mn, BaAl₁₂O₁₉: Mn, BaMgAl₁₄O_{twenty three}: Mn, LaPO_Four : (Ce, Tb), Y_Three (Al, Ga)_Five O₁₂: Y for blue, such as Tb₂ SiO_Five : Ce, BaMgAl_TenO₁₇: Eu²⁺, BaMgAl₁₄O_{twenty three}: Eu²⁺, (Ca, Sr, Ba)_Ten(PO_Four )₆ Cl₂ : Eu²⁺, (Zn, Cd) S: Ag and the like.
Inorganic particles used in color filter forming materials such as PDP, LCD and organic EL elements are Fe for red.₂ O_Three For green use, Cr₂ O_Three CoO / Al for blue₂ O_Three And so on.
Examples of inorganic particles used in black stripe (matrix) forming materials such as PDP, LCD, and organic EL elements include metals such as Co, Cr, Cu, Fe, Mn, Ni, Ti, and Zn, and oxides thereof. Examples thereof include composite oxides, carbides, nitrides, sulfides, silicides, borides, carbon black, and graphite. These can be used alone or in admixture of two or more. Among these, preferable inorganic particles include metal particles, metal oxide particles, and composite oxide particles selected from the group of Co, Cr, Cu, Fe, Mn, Ni, and Ti. Moreover, as an average particle diameter, Preferably it is 0.01-10 micrometers, More preferably, it is 0.05-5 micrometers, Most preferably, it is 0.1-2 micrometers.
Note that low melting point glass frit may be used in combination as inorganic particles in the forming material of the electrode, phosphor, color filter, and black stripe (matrix). As the low melting point glass frit composition, for example, (1) lead oxide, boron oxide, silicon oxide (PbO-B)₂O_Three-SiO₂System), (2) Lead oxide, boron oxide, silicon oxide, aluminum oxide system (PbO-B)₂O_Three-SiO₂-Al₂O_Three), (3) zinc oxide, boron oxide, silicon oxide (ZnO-B)₂O_Three-SiO₂System), (4) zinc oxide, boron oxide, silicon oxide, aluminum oxide system (ZnO-B)₂O_Three-SiO₂-Al₂O_Three), (5) Lead oxide, zinc oxide, boron oxide, silicon oxide (PbO-ZnO-B)₂O_Three-SiO₂System), (6) lead oxide, zinc oxide, boron oxide, silicon oxide, aluminum oxide system (PbO-ZnO-B)₂O_Three-SiO₂-Al₂O_Three), (7) bismuth oxide, boron oxide, silicon oxide (Bi)₂O_Three-B₂O_Three-SiO₂System), (8) Bismuth oxide, boron oxide, silicon oxide, aluminum oxide system (Bi)₂O_Three-B₂O_Three-SiO₂-Al₂O_Three), (9) bismuth oxide, zinc oxide, boron oxide, silicon oxide (Bi)₂O_Three-ZnO-B₂O_Three-SiO₂), (9) bismuth oxide, zinc oxide, boron oxide, silicon oxide, aluminum oxide (Bi)₂O_Three-ZnO-B₂O_Three-SiO₂-Al₂O_ThreeSystem). Among these low-melting glass frits, it is preferable to use a lead-free glass frit from the viewpoint of the environment, and it is particularly preferable to use a lead-free glass frit mainly composed of bismuth oxide from the viewpoint of the temporal stability of the photosensitive composition. . The softening point of the low melting point glass frit is usually 650 ° C. or lower, preferably 400 to 600 ° C. Moreover, it does not specifically limit as a shape of the said low melting glass frit, As an average particle diameter, Preferably it is 0.1-10 micrometers, More preferably, it is 0.5-5 micrometers. The low melting point glass frit can be used alone or in combination of two or more kinds of low melting point glass frits having different glass frit compositions, different softening points, different shapes, and different average particle sizes. The content of the low-melting glass frit in this case varies depending on the application, but is usually 70 parts by mass or less, preferably 50 parts by mass or less, with respect to 100 parts by mass of the total amount of inorganic particles including the low-melting glass frit. More preferably, it is 30 parts by mass or less.
[0015]
(B) Alkali-soluble resin
Various resins can be used as the alkali-soluble resin used in the photosensitive composition. Here, “alkali-soluble” refers to the property of being dissolved in an alkaline developer and having a solubility to such an extent that the intended development processing is performed.
Specific examples of such alkali-soluble resins include (meth) acrylic resins, hydroxystyrene resins, novolac resins, and polyester resins.
Among such alkali-soluble resins, particularly preferred are the following copolymer of monomer (a) and monomer (c), copolymer of monomer (a), monomer (b) and monomer (c): An acrylic resin such as
[0016]
Monomer (a): Carboxyl group-containing monomers
Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, succinic acid mono (2- (meth) acryloyloxyethyl), ω-carboxy-polycaprolactone mono (Meth) acrylate and the like.
Monomer (b): OH-containing monomers
Hydroxyl-containing monomers such as (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, and (meth) acrylic acid 3-hydroxypropyl; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene Such as phenolic hydroxyl group-containing monomers.
Monomer (C): Other copolymerizable monomers
Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, n-lauryl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl ( (Meth) acrylates and other (meth) acrylic esters other than (a) monomers; aromatic vinyl monomers such as styrene and α-methylstyrene; conjugated dienes such as butadiene and isoprene; polystyrene and poly (meth) acrylic Macromonomers having a polymerizable unsaturated group such as a (meth) acryloyl group at one end of a polymer chain such as methyl acrylate, poly (meth) ethyl acrylate, and poly (meth) acrylate benzyl:
[0017]
The copolymer of the monomer (a) and the monomer (c) or the copolymer of the monomer (a), the monomer (b) and the monomer (c) is the phenol of the monomer (a) and / or the monomer (b). Due to the presence of the copolymer component derived from the polymerizable hydroxyl group-containing monomer, it becomes alkali-soluble. Among these, a copolymer of monomer (a), monomer (b) and monomer (c) is particularly preferable from the viewpoint of (A) dispersion stability of inorganic particles and solubility in an alkali developer described later. The content of the copolymer component derived from the monomer (a) in this copolymer is preferably 1 to 50% by mass, particularly preferably 5 to 30% by mass, and the content of the copolymer component derived from the monomer (b) The content is preferably 1 to 50% by mass, particularly preferably 5 to 30% by mass. Moreover, as a monomer (b) component, hydroxyl-containing monomers, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, are preferable.
[0018]
The molecular weight of the alkali-soluble resin constituting the photosensitive composition is 5,000 to 5,000,000 as a weight average molecular weight in terms of polystyrene by GPC (hereinafter also simply referred to as “weight average molecular weight (Mw)”). It is preferable that there is, more preferably 10,000 to 300,000.
As content rate of alkali-soluble resin in a photosensitive composition, it is 1-500 mass parts normally with respect to 100 mass parts of inorganic particles, Preferably it is 10-200 mass parts. In addition, you may contain resin other than alkali-soluble resin in the photosensitive composition.
[0019]
(C) Ethylenically unsaturated group-containing compound
The ethylenically unsaturated group-containing compound constituting the photosensitive composition is not particularly limited as long as it is a compound that contains an ethylenically unsaturated group and can undergo a radical polymerization reaction with a photopolymerization initiator described later. , (Meth) acrylate compounds are used.
Specific examples of such (meth) acrylate compounds include di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol; di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; Di (meth) acrylates of both end hydroxylated polymers such as polybutadiene, both end hydroxy polyisoprene, both end hydroxy polycaprolactone;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, 1,2,4-butanetriol, trimethylolalkane, tetramethylolalkane, pentaerythritol, dipentaerythritol; Poly (meth) acrylates of polyalkylene glycol adducts; Poly (meth) acrylates of cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzenediol; Polyester (meth) acrylates, Epoxy (meth) Examples thereof include oligo (meth) acrylates such as acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spiraline resin (meth) acrylate. In addition, you may use the compound shown by monomer (a), (b), and (c) which comprises alkali-soluble resin mentioned above.
These (meth) acrylate compounds can be used alone or in combination of two or more, and are usually 20 to 500 parts by mass, more preferably 40 to 250 parts per 100 parts by mass of the aforementioned alkali-soluble resin. Used in parts by mass.
[0020]
(D) Photopolymerization initiator
The photopolymerization initiator that constitutes the photosensitive composition is not particularly limited as long as it is a compound that generates radicals in the exposure step described later and initiates the polymerization reaction of the above-described ethylenically unsaturated group-containing compound.
Specific examples of such photopolymerization initiators include benzyl, benzoin, benzophenone, Michler ketone, 4,4′-bisdiethylaminobenzophenone, camphorquinone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- [4 ′-(methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- ( Carbonyl compounds such as 4-morpholinophenyl) -butan-1-one, 2,4-diethylthioxanthone, isopropylthioxanthone; bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis ( 2,4,6-trime Phosphine oxide compounds such as benzoyl) -phenylphosphine oxide; azo compounds or azide compounds such as azoisobutyronitrile and 4-azidobenzaldehyde; organic sulfur compounds such as mercaptan disulfide; benzoyl peroxide, di-tert-butyl peroxide , Organic peroxides such as tert-butyl hydroperoxide, cumene hydroperoxide, and paraffin hydroperoxide; 2,4-bis (trichloromethyl) -6- (2′-chlorophenyl) -1,3,5-triazine, Trihalomethanes such as 2- [2- (2-furanyl) ethylenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine; 2,2′-bis (2-chlorophenyl) -4, 5,4 ', 5'-tetra Eniru 1,2' the like can be illustrated imidazole dimer such biimidazole, these may be used alone or in combination of two or more kinds. Moreover, you may use together a sensitizer, a sensitization adjuvant, a hydrogen donor, and a chain transfer agent.
As a content rate of a photoinitiator, it is 0.1-100 mass parts normally with respect to 100 mass parts of total amounts of the said alkali-soluble resin and an ethylenically unsaturated group containing compound, Preferably it is 1-50 masses. Part.
[0021]
(E) Solvent
The photosensitive composition usually contains a solvent. Examples of the solvent include (A) affinity with inorganic particles, (B) an alkali-soluble resin, (C) an ethylenically unsaturated group-containing compound, (D) a photopolymerization initiator, and, if necessary, described later. (F) It is preferable that various additives have good solubility, can impart an appropriate viscosity to the photosensitive composition, and can be easily removed by evaporation.
Specific examples of such solvents include ketones such as diethyl ketone, methyl butyl ketone, dipropyl ketone, and cyclohexanone; alcohols such as n-pentanol, 4-methyl-2-pentanol, cyclohexanol, and diacetone alcohol; Ether-based alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; saturated aliphatic monocarboxylic acid alkyl such as n-butyl acetate and amyl acetate Esters; Lactic acid esters such as ethyl lactate and lactic acid-n-butyl; methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether Seteto, ethyl 3-ethoxypropionate can be exemplified and ether-based esters such as these can be used alone or in combination of two or more.
The content ratio of the solvent in the photosensitive composition can be appropriately selected within a range in which good photosensitive transfer layer forming performance (fluidity or plasticity) is obtained. Usually, (A) 100 parts by mass of inorganic particles The amount is 1 to 10,000 parts by mass, preferably 10 to 1,000 parts by mass.
[0022]
(F) Various additives
In addition to the components (A) to (E), the photosensitive composition includes a plasticizer, an adhesion assistant, a dispersant, a storage stabilizer, an antifoaming agent, an antioxidant, an ultraviolet absorber, a leveling agent, Various additives such as a development accelerator may be contained as optional components.
(1) Plasticizer
The plasticizer is added in order to develop good flexibility and combustibility in the formed photosensitive transfer layer. Specifically, the compound represented by the following formula (1) or (2) is preferably used because it is easily decomposed and removed by heat and does not adversely affect the performance of the resulting pattern.
[0023]
[Chemical 1]

[0024]
(Wherein R¹ And R^Four Each represents the same or different alkyl group having 1 to 30 carbon atoms, R² And R^Three Each represents the same or different methylene group or an alkylene group having 2 to 30 carbon atoms, s is a number from 0 to 5, and t is a number from 1 to 10. )
[0025]
[Chemical 2]

[0026]
(Wherein R^Five Represents an alkyl group or alkenyl group having 1 to 30 carbon atoms. )
[0027]
In the above formula (1), R¹ Or R^Four An alkyl group represented by² Or R^Three The alkylene group represented by may be linear or branched, and may be a saturated group or an unsaturated group. R¹ Or R^Four The number of carbon atoms of the alkyl group represented by is 1 to 30, preferably 2 to 20, and more preferably 4 to 10. When the number of carbon atoms of the alkyl group exceeds 30, the solubility of the plasticizer in the solvent may be reduced, and good transfer film flexibility may not be obtained.
[0028]
Specific examples of the compound represented by the above formula (1) include dibutyl adipate, diisobutyl adipate, di-2-ethylhexyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, dibutyl diglycol adipate and the like. Preferably, n is a compound represented by 2-6.
[0029]
In the above formula (2), R^Five The alkyl group and alkenyl group represented by may be linear or branched, and may be a saturated group or an unsaturated group. R^Five The carbon number of the alkyl group or alkenyl group represented by is 1-30, preferably 2-20, more preferably 10-18.
Specific examples of the compound represented by the formula (2) include propylene glycol monolaurate and propylene glycol monooleate.
[0030]
As a content rate of the plasticizer in a photosensitive composition, it is preferable that it is 0.1-20 weight part with respect to 100 weight part of inorganic particles, More preferably, it is 0.5-10 weight part.
[0031]
(2) Adhesion aid
As the adhesion assistant, a silane coupling agent [saturated alkyl group-containing (alkyl) alkoxysilane] such as a compound represented by the following formula (3) is preferably used.
[0032]
[Chemical 3]

[0033]
(In the formula, p is an integer of 3 to 20, m is an integer of 1 to 3, n is an integer of 1 to 3, and a is an integer of 1 to 3.)
[0034]
In the above formula (3), p indicating the carbon number of the saturated alkyl group is an integer of 3 to 20, and preferably an integer of 4 to 16.
[0035]
Specific examples of the silane coupling agent represented by the above formula (3) include n-propyldimethylmethoxysilane, n-butyldimethylmethoxysilane, n-decyldimethylmethoxysilane, n-hexadecyldimethylmethoxysilane, n- Saturated alkyldimethylmethoxysilanes such as icosanedimethylmethoxysilane (a = 1, m = 1, n = 1);
Saturated alkyldiethylmethoxysilanes such as n-propyldiethylmethoxysilane, n-butyldiethylmethoxysilane, n-decyldiethylmethoxysilane, n-hexadecyldiethylmethoxysilane, n-icosanediethylmethoxysilane (a = 1, m = 1, n = 2);
Saturated alkyldipropylmethoxysilanes such as n-butyldipropylmethoxysilane, n-decyldipropylmethoxysilane, n-hexadecyldipropylmethoxysilane, n-icosanedipropylmethoxysilane (a = 1, m = 1, n = 3);
Saturated alkyldimethylethoxysilanes such as n-propyldimethylethoxysilane, n-butyldimethylethoxysilane, n-decyldimethylethoxysilane, n-hexadecyldimethylethoxysilane, n-icosanedimethylethoxysilane (a = 1, m = 2, n = 1);
Saturated alkyldiethylethoxysilanes such as n-propyldiethylethoxysilane, n-butyldiethylethoxysilane, n-decyldiethylethoxysilane, n-hexadecyldiethylethoxysilane, n-icosanediethylethoxysilane (a = 1, m = 2, n = 2);
Saturated alkyldipropylethoxysilanes (a = 1, m = 2, n-butyldipropylethoxysilane, n-decyldipropylethoxysilane, n-hexadecyldipropylethoxysilane, n-icosanedipropylethoxysilane) n = 3);
Saturated alkyldimethylpropoxysilanes such as n-propyldimethylpropoxysilane, n-butyldimethylpropoxysilane, n-decyldimethylpropoxysilane, n-hexadecyldimethylpropoxysilane, n-icosanedimethylpropoxysilane (a = 1, m = 3, n = 1);
Saturated alkyl diethylpropoxysilanes such as n-propyldiethylpropoxysilane, n-butyldiethylpropoxysilane, n-decyldiethylpropoxysilane, n-hexadecyldiethylpropoxysilane, n-icosanediethylpropoxysilane (a = 1, m = 3, n = 2);
Saturated alkyldipropylpropoxysilanes such as n-butyldipropylpropoxysilane, n-decyldipropylpropoxysilane, n-hexadecyldipropylpropoxysilane, n-icosanedipropylpropoxysilane (a = 1, m = 3 n = 3);
[0036]
Saturated alkylmethyldimethoxysilanes such as n-propylmethyldimethoxysilane, n-butylmethyldimethoxysilane, n-decylmethyldimethoxysilane, n-hexadecylmethyldimethoxysilane, n-icosanemethyldimethoxysilane (a = 2, m = 1, n = 1);
Saturated alkylethyldimethoxysilanes such as n-propylethyldimethoxysilane, n-butylethyldimethoxysilane, n-decylethyldimethoxysilane, n-hexadecylethyldimethoxysilane, n-icosaneethyldimethoxysilane (a = 2, m = 1, n = 2);
Saturated alkylpropyldimethoxysilanes such as n-butylpropyldimethoxysilane, n-decylpropyldimethoxysilane, n-hexadecylpropyldimethoxysilane, n-icosanepropyldimethoxysilane (a = 2, m = 1, n = 3)
Saturated alkylmethyldiethoxysilanes such as n-propylmethyldiethoxysilane, n-butylmethyldiethoxysilane, n-decylmethyldiethoxysilane, n-hexadecylmethyldiethoxysilane, n-icosanemethyldiethoxysilane (A = 2, m = 2, n = 1);
Saturated alkylethyldiethoxysilanes such as n-propylethyldiethoxysilane, n-butylethyldiethoxysilane, n-decylethyldiethoxysilane, n-hexadecylethyldiethoxysilane, n-icosaneethyldiethoxysilane (A = 2, m = 2, n = 2);
Saturated alkylpropyldiethoxysilanes (a = 2, m = 2) such as n-butylpropyldiethoxysilane, n-decylpropyldiethoxysilane, n-hexadecylpropyldiethoxysilane, n-icosanepropyldiethoxysilane , N = 3);
Saturated alkylmethyldipropoxysilanes such as n-propylmethyldipropoxysilane, n-butylmethyldipropoxysilane, n-decylmethyldipropoxysilane, n-hexadecylmethyldipropoxysilane, n-icosanemethyldipropoxysilane (A = 2, m = 3, n = 1);
Saturated alkylethyldipropoxysilanes such as n-propylethyldipropoxysilane, n-butylethyldipropoxysilane, n-decylethyldipropoxysilane, n-hexadecylethyldipropoxysilane, n-icosaneethyldipropoxysilane (A = 2, m = 3, n = 2);
Saturated alkylpropyl dipropoxysilanes such as n-butylpropyldipropoxysilane, n-decylpropyldipropoxysilane, n-hexadecylpropyldipropoxysilane, n-icosanepropyldipropoxysilane (a = 2, m = 3) , N = 3);
[0037]
Saturated alkyltrimethoxysilanes such as n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-icosanetrimethoxysilane (a = 3, m = 1);
Saturated alkyltriethoxysilanes such as n-propyltriethoxysilane, n-butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, n-icosanetriethoxysilane (a = 3, m = 2);
Saturated alkyltripropoxysilanes such as n-propyltripropoxysilane, n-butyltripropoxysilane, n-decyltripropoxysilane, n-hexadecyltripropoxysilane, n-icosanetripropoxysilane (a = 3, m = 3) etc. can be mentioned, These can be used individually or in combination of 2 or more types.
[0038]
Of these, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-decyldimethylmethoxysilane, n-hexadecyldimethylmethoxysilane, n-butyltriethoxysilane, n- Decyltriethoxysilane, n-hexadecyltriethoxysilane, n-decylethyldiethoxysilane, n-hexadecylethyldiethoxysilane, n-butyltripropoxysilane, n-decyltripropoxysilane, n-hexadecyltripropoxy Silane and the like are particularly preferable.
[0039]
As a content rate of the adhesion promoter in a photosensitive composition, it is preferable that it is 0.001-10 weight part with respect to 100 weight part of inorganic particles, More preferably, it is 0.001-5 weight part.
[0040]
(3) Dispersant
A fatty acid is preferably used as the dispersant for the inorganic particles. In particular, fatty acids having 8 to 30 carbon atoms are preferred. Preferable specific examples of the above fatty acids include saturated fatty acids such as octanoic acid, undecyl acid, lauric acid, myristic acid, palmitic acid, pentadecanoic acid, stearic acid, arachidic acid; elaidic acid, oleic acid, linoleic acid, linolenic acid, arachidone An unsaturated fatty acid such as an acid can be mentioned, and these can be used alone or in combination of two or more.
[0041]
As a content rate of the dispersing agent in a photosensitive composition, it is preferable that it is 0.001-10 weight part with respect to 100 weight part of inorganic particles, More preferably, it is 0.01-5 weight part.
[0042]
Pattern formation method
The photosensitive transfer film of the present invention is particularly preferably used for forming a pattern having a height of 10 μm or less.
In the method for forming a pattern using the photosensitive transfer film of the present invention, [1] a photosensitive transfer layer transfer step, [2] a photosensitive transfer layer exposure step, [3] a photosensitive transfer layer development step, [4] Each step of baking process of photosensitive transfer layer pattern.
[1] Photosensitive transfer layer transfer process
In the transfer step, the photosensitive transfer film of the present invention is used, and the photosensitive transfer layer constituting the photosensitive transfer film is transferred onto the substrate.
As the substrate material, for example, a plate member made of glass, silicone, alumina or the like is used, and a glass substrate is used for PDP. A plate having a desired pattern previously formed on the surface of the plate member may be used. For the substrate surface, an appropriate chemical treatment such as silane coupling agent; plasma treatment; thin film formation treatment by ion plating, sputtering, gas phase reaction, vacuum deposition, etc., as necessary Pretreatment may be performed.
An example of the transfer process is as follows. After removing the protective film of the photosensitive transfer film used as necessary, the photosensitive transfer film is overlaid on the substrate so that the surface of the photosensitive transfer layer is in contact with the photosensitive transfer film. Thermocompression bonding with a heating roller. As a result, the photosensitive transfer layer is transferred onto and in close contact with the substrate. Here, as transfer conditions, for example, the surface temperature of the heating roller is 20 to 140 ° C., and the roll pressure by the heating roller is 1 to 5 kg / cm.² The moving speed of the heating roller can be 0.1 to 10.0 m / min. Moreover, the board | substrate may be preheated and can be 40-100 degreeC as preheating temperature, for example.
[0043]
[2] Exposure process of photosensitive transfer layer
In the exposure step, the surface of the photosensitive transfer layer is selectively irradiated (exposed) with radiation through an exposure mask to form a latent image of the pattern of the photosensitive transfer layer. The support film on the photosensitive transfer layer may be peeled off before the exposure step, or may be peeled off after the exposure step and before the development step described later. From the viewpoint of increasing sensitivity, the support film on the photosensitive transfer layer is preferably peeled off after the exposure step and before the development step described below.
The radiation that is selectively irradiated (exposed) with radiation in the exposure step includes visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc., preferably visible light, ultraviolet light, and far ultraviolet light are used, More preferably, ultraviolet rays are used.
Although the exposure pattern of the exposure mask varies depending on the purpose, for example, a stripe having a width of 10 to 500 μm is used.
The radiation irradiation apparatus is not particularly limited, such as an ultraviolet irradiation apparatus used in a photolithography method, an exposure apparatus used when manufacturing a semiconductor and a liquid crystal display device.
[0044]
[3] Photosensitive transfer layer development process
In the development step, the exposed photosensitive transfer layer is developed to reveal the pattern (latent image) of the photosensitive transfer layer.
As the developer used in the development process of the photosensitive transfer layer, an alkali developer can be used. Thereby, the alkali-soluble resin contained in the photosensitive transfer layer can be easily dissolved and removed.
Since the inorganic particles contained in the photosensitive transfer layer are uniformly dispersed by the alkali-soluble resin, the inorganic particles are simultaneously removed by dissolving and washing the alkali-soluble resin as the binder.
As an active ingredient of the alkaline developer, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate , Inorganic such as potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia Alkaline compounds; tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropyl Triethanolamine, and organic alkaline compounds such as ethanol amine.
The alkaline developer used in the development process of the photosensitive transfer layer can be prepared by dissolving one or more of the alkaline compounds in water or the like. Here, the concentration of the alkaline compound in the alkaline developer is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass. The alkaline developer may contain additives such as nonionic surfactants and organic solvents. In addition, after the development process with an alkali developer is performed, a washing process is usually performed. Moreover, you may include the process of scraping the unnecessary part which remain | survives in the photosensitive transfer layer pattern side surface and board | substrate exposed part after a development process as needed.
Here, as development processing conditions, the type / composition / concentration of developer, development time, development temperature, development method (for example, dipping method, rocking method, shower method, spray method, paddle method), developing device, etc. are appropriately selected. You can choose.
By this development process, a photosensitive transfer layer pattern (pattern corresponding to an exposure mask) composed of a photosensitive transfer layer remaining portion and a photosensitive transfer layer removal portion is formed.
[0045]
[4] Photosensitive transfer layer pattern firing step
In this step, the photosensitive transfer layer pattern is baked to form a pattern. Thereby, the organic substance in the photosensitive transfer layer residual part burns away, and an inorganic pattern can be obtained on the surface of the substrate.
Here, the temperature of the baking treatment needs to be a temperature at which the organic substance in the resin layer residual portion is burned off, and is usually 400 to 600 ° C. in the atmosphere. The firing time is usually 10 to 90 minutes.
The height of the pattern formed on the substrate as described above is 10 μm or less, not including 0, preferably 1 to 8 μm, and more preferably 2 to 6 μm.
[0046]
【Example】
Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following, “part” means “part by mass”.
Moreover, a weight average molecular weight (Mw) is an average molecular weight of polystyrene conversion measured by Tosoh Corporation gel permeation chromatography (GPC) (brand name HLC-802A).
[0047]
<Example 1>
(1) Preparation of photosensitive composition:
(A) As inorganic particles, 100 parts of Ag particles (granular) having an average particle diameter of 1 μm and Bi having an average particle diameter of 2 μm₂ O_Three -ZnO-B₂ O_Three -SiO₂ -Al₂ O_Three Low melting point glass frit (indefinite shape, softening point 520 ° C.) 10 parts, (B) alkali-soluble resin, n-butyl methacrylate / 3-hydroxypropyl methacrylate / methacrylic acid = 60/20/20 (mass%) 30 parts of copolymer (Mw = 100,000), (C) 20 parts of trimethylolpropane triacrylate as an ethylenically unsaturated group-containing compound, (D) 2-benzyl-2-dimethylamino as a photopolymerization initiator After kneading 5 parts of -1- (4-morpholinophenyl) -butan-1-one, 150 parts of propylene glycol monomethyl ether as (E) solvent and 1 part of oleic acid as (F) dispersant in a bead mill The photosensitive composition was prepared by filtering with a stainless mesh (200 mesh, 25 μm diameter).
[0048]
(2) Production of photosensitive transfer film:
The photosensitive transfer film of the present invention in which a photosensitive transfer layer was formed on a support film was prepared by the following operation (a).
(B) A support film (width: 200 mm, length: 30 m, thickness: 38 μm) made of a PET film obtained by releasing the photosensitive composition in advance was applied using a blade coater, and the coating film was dried at 100 ° C. for 5 minutes Then, the solvent was completely removed, and a photosensitive resin layer having a thickness of 10 μm was formed on the support film.
[0049]
Photosensitive transfer layer transfer process:
A photosensitive transfer film was superposed on the surface of a glass substrate for a 6-inch panel so that the surface of the photosensitive transfer layer was in contact with the glass substrate, and the photosensitive transfer film was thermocompression bonded with a heating roller. Here, as pressure bonding conditions, the surface temperature of the heating roller is 120 ° C., and the roll pressure is 4 kg / cm.² The moving speed of the heating roller was 0.5 m / min. As a result, the photosensitive transfer layer was transferred and adhered to the surface of the glass substrate. The film thickness of this photosensitive transfer layer was measured and found to be in the range of 10 μm ± 1 μm.
[0050]
Exposure process and development process of photosensitive transfer layer:
The photosensitive transfer layer was irradiated with i-line (ultraviolet light having a wavelength of 365 nm) with an ultrahigh pressure mercury lamp through an exposure mask (50 μm wide stripe pattern). Here, the irradiation amount is 400 mJ / cm²It was.
[0051]
After completion of the exposure process, the support film is peeled off from the photosensitive transfer layer, and then a shower using a 0.5% by mass aqueous sodium carbonate solution (30 ° C.) as a developer with respect to the exposed photosensitive transfer layer. The development process by the method was performed over 1 minute. Subsequently, a water washing treatment with ultrapure water was performed, whereby the uncured photosensitive transfer layer not irradiated with ultraviolet rays was removed to form a pattern.
[0052]
Baking process of photosensitive transfer layer pattern:
The glass substrate on which the photosensitive transfer layer pattern was formed was baked in a baking furnace in a temperature atmosphere of 600 ° C. for 30 minutes. Thereby, the panel material by which an electrode pattern was formed in the surface of a glass substrate was obtained.
For the electrode pattern in the obtained panel material, the line width and height of the electrode pattern are measured using a scanning electron microscope, and the accuracy of the pattern width is within a range of 50 μm ± 5 μm. Those other than were evaluated as x. In addition, an observation was made about missing patterns. Subsequently, the pattern mass was measured before and after the photosensitive transfer layer pattern baking step, and the mass loss was calculated. The results are shown in Table 1.
[0053]
<Example 2>
(B) As alkali-soluble resin, n-butyl methacrylate / 3-hydroxypropyl methacrylate / methacrylic acid = 60/20/20 (mass%) copolymer (Mw = 100,000) 60 parts, (C) ethylene A photosensitive composition was prepared in the same manner as in Example 1 except that 40 parts of trimethylolpropane triacrylate was used as the compound containing the unsaturated group. A photosensitive transfer film of the present invention in which a photosensitive transfer layer having a thickness of 15 μm was formed on a support film was produced in the same manner as in Example 1 except that the photosensitive composition was used. A panel material on which an electrode pattern was formed was prepared and evaluated in the same manner as in Example 1 except that the photosensitive transfer film was used. The results are shown in Table 1.
[0054]
<Example 3>
(B) As alkali-soluble resin, n-butyl methacrylate / 3-hydroxypropyl methacrylate / methacrylic acid = 60/20/20 (mass%) copolymer (Mw = 100,000) 90 parts, (C) ethylene A photosensitive composition was prepared in the same manner as in Example 1 except that 60 parts of trimethylolpropane triacrylate was used as the compound containing a polymerizable unsaturated group. A photosensitive transfer film of the present invention in which a photosensitive transfer layer having a thickness of 20 μm was formed on a support film was produced in the same manner as in Example 1 except that the photosensitive composition was used. A panel material on which an electrode pattern was formed was prepared and evaluated in the same manner as in Example 1 except that the photosensitive transfer film was used. The results are shown in Table 1.
[0055]
<Example 4>
(B) As alkali-soluble resin, n-butyl methacrylate / 3-hydroxypropyl methacrylate / methacrylic acid = 60/20/20 (mass%) copolymer (Mw = 100,000) 18 parts, (C) ethylene A photosensitive composition was prepared in the same manner as in Example 1 except that 12 parts of trimethylolpropane triacrylate was used as the polymerizable unsaturated group-containing compound. A photosensitive transfer film of the present invention in which a photosensitive transfer layer having a thickness of 15 μm was formed on a support film was produced in the same manner as in Example 1 except that the photosensitive composition was used. A panel material on which an electrode pattern was formed was prepared and evaluated in the same manner as in Example 1 except that the photosensitive transfer film was used. The results are shown in Table 1.
[0056]
<Example 5>
(B) As alkali-soluble resin, n-butyl methacrylate / 3-hydroxypropyl methacrylate / methacrylic acid = 60/20/20 (mass%) copolymer (Mw = 100,000) 27 parts, (C) ethylene A photosensitive composition was prepared in the same manner as in Example 1 except that 18 parts of trimethylolpropane triacrylate was used as the compound containing the unsaturated group. A photosensitive transfer film of the present invention in which a photosensitive transfer layer having a thickness of 20 μm was formed on a support film was produced in the same manner as in Example 1 except that the photosensitive composition was used. A panel material on which an electrode pattern was formed was prepared and evaluated in the same manner as in Example 1 except that the photosensitive transfer film was used. The results are shown in Table 1.
[0057]
<Example 6>
(A) As inorganic particles, 100 parts of Cu—Fe—Mn composite oxide particles (spherical) having an average particle size of 0.3 μm, Bi having an average particle size of 2 μm₂ O_Three -ZnO-B₂ O_Three -SiO₂ -Al₂ O_Three Low melting point glass frit (indefinite shape, softening point 520 ° C.) 10 parts, (B) alkali-soluble resin, n-butyl methacrylate / 3-hydroxypropyl methacrylate / methacrylic acid = 60/20/20 (mass%) Photosensitive composition as in Example 1, except that 120 parts of copolymer (Mw = 100,000) and (C) 80 parts of trimethylolpropane triacrylate were used as the ethylenically unsaturated group-containing compound. Was prepared. A photosensitive transfer film of the present invention in which a photosensitive transfer layer having a thickness of 10 μm was formed on a support film was produced in the same manner as in Example 1 except that the photosensitive composition was used. A panel material on which a black matrix pattern was formed was prepared in the same manner as in Example 1 except that the photosensitive transfer film was used, and the black matrix pattern was evaluated. The results are shown in Table 1.
[0058]
<Example 7>
(B) As alkali-soluble resin, n-butyl methacrylate / 3-hydroxypropyl methacrylate / methacrylic acid = 60/20/20 (mass%) copolymer (Mw = 100,000) 180 parts, (C) ethylene A photosensitive composition was prepared in the same manner as in Example 6 except that 120 parts of trimethylolpropane triacrylate was used as the polymerizable unsaturated group-containing compound. A photosensitive transfer film of the present invention in which a photosensitive transfer layer having a thickness of 15 μm was formed on a support film was produced in the same manner as in Example 6 except that the photosensitive composition was used. A panel material on which a black matrix pattern was formed was prepared and evaluated in the same manner as in Example 6 except that the photosensitive transfer film was used. The results are shown in Table 1.
[0059]
<Example 8>
(B) As alkali-soluble resin, n-butyl methacrylate / 3-hydroxypropyl methacrylate / methacrylic acid = 60/20/20 (mass%) copolymer (Mw = 100,000) 36 parts, (C) ethylene A photosensitive composition was prepared in the same manner as in Example 6 except that 24 parts of trimethylolpropane triacrylate was used as the compound containing a polymerizable unsaturated group. A photosensitive transfer film of the present invention in which a photosensitive transfer layer having a thickness of 10 μm was formed on a support film was produced in the same manner as in Example 6 except that the photosensitive composition was used. A panel material on which a black matrix pattern was formed was prepared and evaluated in the same manner as in Example 6 except that the photosensitive transfer film was used. The results are shown in Table 1.
[0060]
<Example 9>
(B) As alkali-soluble resin, n-butyl methacrylate / 3-hydroxypropyl methacrylate / methacrylic acid = 60/20/20 (mass%) copolymer (Mw = 100,000) 60 parts, (C) ethylene A photosensitive composition was prepared in the same manner as in Example 6 except that 40 parts of trimethylolpropane triacrylate was used as the compound containing the unsaturated group. A photosensitive transfer film of the present invention in which a photosensitive transfer layer having a thickness of 15 μm was formed on a support film was produced in the same manner as in Example 6 except that the photosensitive composition was used. A panel material on which a black matrix pattern was formed was prepared and evaluated in the same manner as in Example 6 except that the photosensitive transfer film was used. The results are shown in Table 1.
[0061]
<Example 10>
(B) As alkali-soluble resin, n-butyl methacrylate / 3-hydroxypropyl methacrylate / methacrylic acid = 60/20/20 (mass%) copolymer (Mw = 100,000) 90 parts, (C) ethylene A photosensitive composition was prepared in the same manner as in Example 6 except that 60 parts of trimethylolpropane triacrylate was used as the polymerizable unsaturated group-containing compound. A photosensitive transfer film of the present invention in which a photosensitive transfer layer having a thickness of 20 μm was formed on a support film was produced in the same manner as in Example 6 except that the photosensitive composition was used. A panel material on which a black matrix pattern was formed was prepared and evaluated in the same manner as in Example 6 except that the photosensitive transfer film was used. The results are shown in Table 1.
[0062]
<Comparative Example 1>
(B) As alkali-soluble resin, n-butyl methacrylate / 3-hydroxypropyl methacrylate / methacrylic acid = 60/20/20 (mass%) copolymer (Mw = 100,000) 9 parts, (C) ethylene A photosensitive composition was prepared in the same manner as in Example 1 except that 6 parts of trimethylolpropane triacrylate was used as the compound containing a polymerizable unsaturated group. A photosensitive transfer film of the present invention in which a photosensitive transfer layer having a thickness of 4 μm was formed on a support film was produced in the same manner as in Example 1 except that the photosensitive composition was used. A panel material on which an electrode pattern was formed was prepared and evaluated in the same manner as in Example 1 except that the photosensitive transfer film was used. The results are shown in Table 1.
[0063]
<Comparative example 2>
(B) As alkali-soluble resin, n-butyl methacrylate / 3-hydroxypropyl methacrylate / methacrylic acid = 60/20/20 (mass%) copolymer (Mw = 100,000) 60 parts, (C) ethylene A photosensitive composition was prepared in the same manner as in Example 1 except that 40 parts of trimethylolpropane triacrylate was used as the compound containing the unsaturated group. A photosensitive transfer film of the present invention in which a photosensitive transfer layer having a thickness of 40 μm was formed on a support film was produced in the same manner as in Example 1 except that the photosensitive composition was used. A panel material on which an electrode pattern was formed was prepared and evaluated in the same manner as in Example 1 except that the photosensitive transfer film was used. The results are shown in Table 1.
[0064]
<Comparative Example 3>
(B) As alkali-soluble resin, n-butyl methacrylate / 3-hydroxypropyl methacrylate / methacrylic acid = 60/20/20 (mass%) copolymer (Mw = 100,000) 36 parts, (C) ethylene A photosensitive composition was prepared in the same manner as in Example 6 except that 24 parts of trimethylolpropane triacrylate was used as the compound containing a polymerizable unsaturated group. A photosensitive transfer film of the present invention in which a photosensitive transfer layer having a thickness of 4 μm was formed on a support film was produced in the same manner as in Example 6 except that the photosensitive composition was used. A panel material on which a black matrix pattern was formed was prepared and evaluated in the same manner as in Example 6 except that the photosensitive transfer film was used. The results are shown in Table 1.
[0065]
<Comparative example 4>
(B) As alkali-soluble resin, n-butyl methacrylate / 3-hydroxypropyl methacrylate / methacrylic acid = 60/20/20 (mass%) copolymer (Mw = 100,000) 180 parts, (C) ethylene A photosensitive composition was prepared in the same manner as in Example 6 except that 120 parts of trimethylolpropane triacrylate was used as the polymerizable unsaturated group-containing compound. A photosensitive transfer film of the present invention in which a photosensitive transfer layer having a thickness of 40 μm was formed on a support film was produced in the same manner as in Example 6 except that the photosensitive composition was used. A panel material on which a black matrix pattern was formed was prepared and evaluated in the same manner as in Example 6 except that the photosensitive transfer film was used. The results are shown in Table 1.
[0066]
[Table 1]

[0067]
【The invention's effect】
According to the photosensitive transfer film of the present invention, a pattern having excellent adhesion to a substrate and high dimensional accuracy can be easily formed. The photosensitive transfer film of the present invention can be suitably used for forming electrodes, phosphors, color filters and black matrices of plasma display panels.
[Brief description of the drawings]
FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type plasma display panel.
[Explanation of symbols]
1 Glass substrate (front substrate) 2 Glass substrate (back substrate)
3 Bulkhead 4 Transparent electrode
5 Bus electrode 6 Address electrode
7 Phosphor 8 Dielectric layer (front substrate)
9 Dielectric layer (Back substrate) 10 Protective film

Claims (4)

(A) inorganic particles, (B) an alkali-soluble resin, (C) an ethylenically unsaturated group-containing compound and (D) a photopolymerization initiator, having a film thickness of 5 to 30 μm , and firing at 600 ° C. A photosensitive transfer film comprising a photosensitive transfer layer having a mass loss of 25 to 75% by mass when processed . The film thickness of the photosensitive transfer layer is characterized 10~20μm der Rukoto, photosensitive transfer film of claim 1, wherein. (A) It has a photosensitive transfer layer whose inorganic particle content is 25-75 mass%, The photosensitive transfer film of Claim 1 or 2 characterized by the above-mentioned. 4. The photosensitive transfer film according to claim 1 , wherein the photosensitive transfer film is used for forming at least one member selected from an electrode, a phosphor, a color filter, and a black matrix of a plasma display panel.

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