JP4075277B2 - Inorganic particle-containing photosensitive composition and photosensitive film - Google Patents

Description

【００２３】
（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。）
【００２４】
【化２】

【００２５】
（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。）
【００２６】
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、フィルムの良好な可撓性が得られない場合がある。
【００２７】
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。
【００２８】
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。
【００２９】
無機粒子含有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。
【００３０】
▲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。
【００３１】
【化３】

【００３２】
（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。）
【００３３】
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。
【００３４】
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）；
【００３５】
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）；
【００３６】
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。
【００３７】
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。
【００３８】
無機粒子含有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。
【００３９】
▲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。
【００４０】
無機粒子含有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、０．０１〜２０重量部であることが好ましく、さらに好ましくは０．１〜１０重量部とされる。
本発明の無機粒子含有感光性組成物は、（Ａ）無機粒子、（Ｂ）アルカリ可溶性樹脂、（Ｃ）特定メタクリレート化合物、（Ｄ）光重合開始剤、（Ｅ）溶剤 および必要に応じて（Ｆ）各種添加剤を、ロール混練機、ミキサー、ホモミキサー、ボールミル、ビーズミルなどの混練機を用いて混練することにより調製することができる。
上記のようにして調製される無機粒子含有感光性組成物は、塗布に適した流動性を有するペースト状の組成物であり、その粘度は、通常１０〜１００，０００ｍＰａ・ｓ^-1とされ、好ましくは５０〜１０，０００ｍＰａ・ｓ^-1、より好ましくは１００〜５，０００ｍＰａ・ｓ^-1とされる。
本発明の組成物は、以下に詳述する本発明の感光性フィルムを製造するために特に好適に使用することができる。
＜感光性フィルム＞
本発明の感光性フィルムは、通常、支持フィルムと、この上に形成された無機粒子含有感光性樹脂層とを有してなり、当該無機粒子含有感光性樹脂層の表面に保護フィルムが設けられていてもよい。
【００４１】
＜支持フィルムおよび保護フィルム＞
本発明の感光性フィルムを構成する支持フィルムは、耐熱性および耐溶剤性を有すると共に可撓性を有する樹脂フィルムであることが好ましい。支持フィルムが可撓性を有することにより、ロールコーター等によってペースト状組成物を塗布することによって無機粒子含有感光性樹脂層を形成することができ、感光性フィルムをロール状に巻回した状態で保存し、供給することができる。支持フィルムを形成する樹脂としては、例えばポリエチレンテレフタレート、ポリエステル、ポリエチレン、ポリプロピレン、ポリスチレン、ポリイミド、ポリビニルアルコール、ポリフロロエチレンなどの含フッ素樹脂、ナイロン、セルロースなどを挙げることができる。支持フィルムの厚さとしては、例えば２０〜１００μｍとされる。
支持フィルムの表面には離型処理が施されていてもよい。これにより、後述のパターンの形成工程において、支持フィルムの剥離操作を容易に行うことができる。
なお、保護フィルムについても、支持フィルムと同様のものを用いることができる。また、保護フィルムの表面には好ましくは離型処理が施され、保護フィルム／無機粒子含有感光性樹脂層間の剥離強度が、支持フィルム／無機粒子含有感光性樹脂層間の剥離強度よりも小さいことが必要である。
本発明の感光性フィルムは、本発明の無機粒子含有感光性組成物を支持フィルム上に塗布し、塗膜を乾燥して溶剤の一部又は全部を除去して無機粒子含有感光性樹脂層を形成し、通常、当該無機粒子含有感光性樹脂層上に保護フィルムを設ける（圧着する）ことにより製造することができる。
【００４２】
無機粒子含有感光性組成物を支持フィルム上に塗布し、無機粒子含有感光性樹脂層を得る方法としては、膜厚の均一性に優れた膜厚の大きい（例えば１μｍ以上）塗膜を効率よく形成することができるものであることが好ましく、具体的には、ロールコーターによる塗布方法、ブレードコーターによる塗布方法、スリットコーターによる塗布方法、カーテンコーターによる塗布方法、ワイヤーコーターによる塗布方法などを好ましいものとして挙げることができる。
塗膜の乾燥条件としては、５０〜１５０℃で０．５〜３０分間程度とされ、乾燥後における溶剤の残存割合（無機粒子含有感光性樹脂層中の含有率）は、通常、２質量％以下とされる。
上記のようにして支持フィルム上に形成される無機粒子含有感光性樹脂層の膜厚としては、無機粒子の含有率、部材の種類やサイズなどにより、適宜選択することができる。
【００４３】
部材の形成方法
本発明の無機粒子含有感光性組成物および感光性フィルムに関し、は、プラズマディスプレイパネルの各表示セルを構成する誘電体、電極、抵抗体、蛍光体、隔壁、カラーフィルターおよびブラックマトリクスの形成において、有機成分の熱分解性に優れ、精度の高いパターンを形成するために好適に使用することができる。
本発明の感光性フィルムを用いた部材の形成方法においては、少なくとも〔１〕無機粒子含有感光性樹脂層の転写工程、〔２〕無機粒子含有感光性樹脂層の露光工程、〔３〕無機粒子含有感光性樹脂層の現像工程および〔４〕無機粒子含有感光性樹脂層パターンの焼成工程の各工程を有する。
〔１〕無機粒子含有感光性樹脂層の転写工程
転写工程では、本発明の感光性フィルムを使用し、当該感光性フィルムを構成する無機粒子含有感光性樹脂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。必要に応じて設けられる感光性フィルムの保護フィルムを剥離した後、基板上に、無機粒子含有感光性樹脂層の表面が当接されるように感光性フィルムを重ね合わせ、この感光性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、基板上に無機粒子含有感光性樹脂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。
また、本発明の感光性フィルムから形成された無機粒子含有感光性樹脂層の上に、無機粒子を含有しない、感光性樹脂層（レジスト層）がさらに設けられても良い。この感光性樹脂層は、通常、後述する現像工程・焼成工程においてパターン上から消失する。
さらに、本発明の無機粒子含有感光性樹脂組成物から得られる樹脂層以外の無機粒子含有樹脂層が、設けられてもよい。当該無機粒子含有樹脂層は、感光性であっても非感光性であってもよい。
【００４４】
〔２〕無機粒子含有感光性樹脂層の露光工程
露光工程においては、無機粒子含有感光性樹脂層の表面に、露光用マスクを介して、放射線を選択的照射（露光）して、無機粒子含有感光性樹脂層のパターンの潜像を形成する。なお、無機粒子含有感光性樹脂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、無機粒子含有感光性樹脂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。また、前述したレジスト層を設ける場合には、レジスト層の表面に露光用マスクを介して放射線を照射する。
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。
【００４５】
〔３〕無機粒子含有感光性樹脂層の現像工程
現像工程においては、露光された無機粒子含有感光性樹脂層を現像処理することにより、無機粒子含有感光性樹脂層のパターン（潜像）を顕在化させる。
無機粒子含有感光性樹脂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、無機粒子含有感光性樹脂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、無機粒子含有感光性樹脂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。
【００４６】
無機粒子含有感光性樹脂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無機粒子含有感光性樹脂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、無機粒子含有感光性樹脂層残留部と、無機粒子含有感光性樹脂層除去部とから構成される無機粒子含有感光性樹脂層パターン（露光用マスクに対応するパターン）が形成される。
【００４７】
〔４〕無機粒子含有感光性樹脂層パターンの焼成工程
この工程においては、無機粒子含有感光性樹脂層パターンを焼成処理して、部材を形成する。これにより、無機粒子含有感光性樹脂層残留部中の有機物質が焼失して、基板の表面に部材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。
なお、無機粒子含有感光性樹脂層パターンの焼成工程は、製造効率向上の観点から、目的とする部材の性能を著しく損なわない限り、他の部材の焼成工程と同時に行われることが好ましい。
【００４８】
【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。
【００４９】
＜実施例１＞
（１）無機粒子含有感光性組成物の調製：
（Ａ）無機粒子として、平均粒径０．５μｍのＣｒ−Ｃｕ複合酸化物粒子（粒状）６０部、平均粒径１μｍのＰｂＯ−Ｂ₂ Ｏ₃ −ＳｉＯ₂ 系低融点ガラスフリット（不定形、軟化点５００℃）４０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）４０部、（Ｃ）特定メタクリレート化合物として、トリメチロールプロパントリメタクリレート４０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アセテート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（５００メッシュ、２５μｍ径）でフィルタリングすることにより、無機粒子含有感光性組成物を調製した。
【００５０】
（２）感光性フィルムの作製：
下記（イ）、（ロ）の操作により、支持フィルム、無機粒子含有感光性樹脂層、保護フィルムが順に積層されてなる本発明の無機粒子含有フィルムを作製した。
（イ）無機粒子含有感光性組成物を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、平均膜厚１５μｍの無機粒子含有感光性樹脂層を支持フィルム上に形成した。
（ロ）上記（イ）で形成した無機粒子含有感光性樹脂層上に予め離型処理したＰＥＴフィルムよりなる保護フィルムを熱圧着し、支持フィルム、無機粒子含有感光性樹脂層、保護フィルムが順に積層された感光性フィルムを作製した。
【００５１】
（３）部材の形成
無機粒子含有感光性樹脂層の転写工程：
感光性フィルムより保護フィルムを剥離除去した後、６インチパネル用のガラス基板の表面に、無機粒子含有感光性樹脂層の表面が当接されるよう感光性フィルムを重ね合わせ、この感光性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無機粒子含有感光性樹脂層が転写されて密着した状態となった。
【００５２】
無機粒子含有感光性樹脂層の露光工程・現像工程：
無機粒子含有感光性樹脂層に対して、露光用マスク（４００μｍ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。
露光工程の終了後、無機粒子含有感光性樹脂層より支持フィルムを剥離除去した後、露光処理された無機粒子含有感光性樹脂層に対して、０．４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無機粒子含有感光性樹脂層を除去し、無機粒子含有感光性樹脂層パターンを形成した。
【００５３】
誘電体ペーストの印刷工程：
無機粒子含有感光性樹脂パターンが形成されたガラス基板上に、誘電体ペースト（旭硝子株式会社製ＹＰＴ０３０）をスクリーン印刷した後、１００℃で５分間乾燥を行い、平均膜厚３０μｍの誘電体ペースト膜を形成した。
【００５４】
無機粒子含有感光性樹脂層パターンおよび誘電体ペースト膜の焼成工程：
無機粒子含有感光性樹脂層パターン上に誘電体ペースト膜が形成されたガラス基板を焼成炉内で５８０℃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ブラックマトリックスパターンおよび誘電体層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ブラックマトリックスパターン上の誘電体層について、光学顕微鏡観察を行ったところ、誘電体層に直径２０μｍ以上の気泡は観測されなかった。
【００５５】
＜参考例１＞
（Ｃ）特定メタクリレート化合物として、トリプロピレングリコールジメタクリレート４０部を用いたこと以外は実施例１と同様にして、無機粒子含有感光性組成物を調製した。当該無機粒子含有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、感光性フィルムを作製した。当該感光性フィルムを用いたこと以外は実施例１と同様にして、無機粒子含有感光性樹脂層の転写工程および無機粒子含有感光性樹脂層の露光工程・現像工程を行い、無機粒子含有感光性樹脂層パターンを形成した。次いで、実施例１と同様にして、誘電体ペーストの印刷工程ならびに無機粒子含有感光性樹脂層パターンおよび誘電体ペースト膜の焼成工程を行い、これにより、ガラス基板の表面にブラックマトリックスパターンおよび誘電体層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ブラックマトリックスパターン上の誘電体層について、光学顕微鏡観察を行ったところ、誘電体層に直径２０μｍ以上の気泡は観測されなかった。
【００５６】
＜実施例３＞
（Ａ）無機粒子として、Ａｇ粒子（粒状）９５部、平均粒径３μｍ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℃）５部を用いたこと以外は実施例１と同様にして、無機粒子含有感光性組成物を調製した。当該無機粒子含有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、感光性フィルムを作製した。当該感光性フィルムを用いたこと以外は実施例１と同様にして、無機粒子含有感光性樹脂層の転写工程および無機粒子含有感光性樹脂層の露光工程・現像工程を行い、無機粒子含有感光性樹脂層パターンを形成した。
次いで、実施例１と同様にして、誘電体ペーストの印刷工程ならびに無機粒子含有感光性樹脂層パターンおよび誘電体ペースト膜の焼成工程を行い、これにより、ガラス基板の表面に電極パターンおよび誘電体層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上の誘電体層について、光学顕微鏡観察を行ったところ、誘電体層に直径２０μｍ以上の気泡は観測されなかった。
【００５７】
＜比較例１＞
（Ｃ）特定メタクリレート化合物の代わりに、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、無機粒子含有感光性組成物を調製した。当該無機粒子含有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、感光性フィルムを作製した。当該感光性フィルムを用いたこと以外は実施例１と同様にして、無機粒子含有感光性樹脂層の転写工程および無機粒子含有感光性樹脂層の露光工程・現像工程を行い、無機粒子含有感光性樹脂層パターンを形成した。
次いで、実施例１と同様にして、誘電体ペーストの印刷工程ならびに無機粒子含有感光性樹脂層パターンおよび誘電体ペースト膜の焼成工程を行い、これにより、ガラス基板の表面にブラックマトリックスパターンおよび誘電体層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ブラックマトリックスパターン上の誘電体層について、光学顕微鏡観察を行ったところ、誘電体層に直径２０μｍ以上の気泡が多数観測された。
【００５８】
＜比較例２＞
（Ｃ）特定メタクリレート化合物の代わりに、トリプロピレングリコールジアクリレート４０部を用いたこと以外は実施例１と同様にして、無機粒子含有感光性組成物を調製した。当該無機粒子含有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、感光性フィルムを作製した。当該感光性フィルムを用いたこと以外は実施例１と同様にして、無機粒子含有感光性樹脂層の転写工程および無機粒子含有感光性樹脂層の露光工程・現像工程を行い、無機粒子含有感光性樹脂層パターンを形成した。
次いで、実施例１と同様にして、誘電体ペーストの印刷工程ならびに無機粒子含有感光性樹脂層パターンおよび誘電体ペースト膜の焼成工程を行い、これにより、ガラス基板の表面にブラックマトリックスパターンおよび誘電体層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ブラックマトリックスパターン上の誘電体層について、光学顕微鏡観察を行ったところ、誘電体層に直径２０μｍ以上の気泡が観測された。
【００５９】
【発明の効果】
本発明の無機粒子含有感光性組成物および感光性フィルムによれば、有機成分の熱分解性に優れ、かつ精度の高いパターンを形成することができる。本発明の無機粒子含有感光性組成物および感光性フィルムは、プラズマディスプレイパネルの各表示セルを構成する誘電体、電極、抵抗体、蛍光体、隔壁、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 composition containing inorganic particles and a photosensitive film, and more specifically, formation of dielectrics, electrodes, resistors, phosphors, barrier ribs, color filters, and black matrices constituting each display cell of a plasma display panel. The present invention relates to an inorganic particle-containing photosensitive composition and a photosensitive film, which are excellent in thermal decomposability of organic components and can be suitably used to form a highly accurate pattern.
[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.
[0003]
As a method for forming such various members of PDP, (1) a screen printing method in which a non-photosensitive inorganic particle-containing paste is screen-printed on a substrate to obtain a pattern, and this is baked; (2) photosensitive A film of an inorganic particle-containing composition is formed on a substrate, and a pattern is left on the substrate by developing the film after irradiating ultraviolet rays through a photomask, and a photolithography method for firing the pattern. 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.
Further, the photolithography method has a problem that although the pattern positional accuracy is excellent, the thermal decomposability of the photosensitive organic component in the baking process is low.
[0005]
The present invention has been made based on the above situation.
The first object of the present invention is to provide an inorganic particle-containing photosensitive composition capable of forming a highly accurate pattern and having excellent thermal decomposability of organic components.
The second object of the present invention is to provide a photosensitive film having an inorganic particle-containing photosensitive resin layer capable of forming a highly accurate pattern and having excellent thermal decomposability of organic components.
The inorganic particle-containing photosensitive composition and photosensitive film of the present invention can be suitably used for forming members constituting each display cell of a plasma display panel.
[0006]
[Means for Solving the Problems]
The inorganic particle-containing photosensitive composition of the present invention is
(A) inorganic particles,
(B) an alkali-soluble resin,
(C) a compound having at least two methacryloyl groups in one molecule (hereinafter also referred to as “specific methacrylate compound”) and
(D) It contains a photopolymerization initiator.
Moreover, it is preferable that the inorganic particle containing photosensitive composition of this invention uses a trimethylol propane trimethacrylate as (C) specific methacrylate compound.
[0007]
The photosensitive film of this invention contains the inorganic particle containing photosensitive resin layer obtained from the said inorganic particle containing photosensitive composition, It is characterized by the above-mentioned.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the detail of the inorganic particle containing photosensitive composition of this invention is demonstrated.
[0009]
(A) Inorganic particles
The inorganic particles used in the inorganic particle-containing photosensitive composition vary depending on the type of forming material.
Examples of the inorganic particles used for the dielectric and partition wall forming material constituting the PDP include a low melting point glass frit. The low melting point glass frit preferably has a softening point in the range of 400 to 600 ° C.
When the softening point of the glass frit is less than 400 ° C., the glass frit is melted at a stage where the organic substance such as alkali-soluble resin is not completely decomposed and removed in the baking step of the photosensitive resin layer containing inorganic particles by the composition. Therefore, a part of the organic substance remains in the formed sintered body, and as a result, the sintered body is colored and its light transmittance tends to decrease. On the other hand, when the softening point of the glass frit exceeds 600 ° C., the glass substrate needs to be fired at a temperature higher than 600 ° C., so that the glass substrate is likely to be distorted.
Specifically, (1) lead oxide, boron oxide, silicon oxide (PbO-B₂O_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-SiO₂), (4) Zinc oxide, boron oxide, silicon oxide, aluminum oxide (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-SiO₂System), (9) Bismuth oxide, zinc oxide, boron oxide, silicon oxide, aluminum oxide system (Bi)₂O_Three-ZnO-B₂O_Three-SiO₂-Al₂O_ThreeGlass frit, etc.).
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 glass frit may be used alone or in combination of two or more low melting glass frits having different glass frit compositions, different softening points, different shapes, and different average particle sizes.
[0010]
The low melting point glass frit may be contained in a composition for forming components other than the dielectric and the barrier ribs (for example, an electrode, a resistor, a phosphor, a color filter, and a black matrix). The content of the low-melting glass frit in this case varies depending on the use, 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.
[0011]
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.
[0012]
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.
As inorganic particles used for the resistor forming material of PDP, RuO₂The particle | grains which consist of etc. can be mentioned.
[0013]
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.
[0014]
(B) Alkali-soluble resin
Various resins can be used as the alkali-soluble resin used in the inorganic particle-containing 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), monomer (a), monomer (b) and monomer (c): An acrylic resin such as
[0015]
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) acrylates other than monomer (A); 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) acrylate, poly (meth) acrylate benzyl, etc .:
[0016]
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.
[0017]
The molecular weight of the alkali-soluble resin constituting the inorganic particle-containing photosensitive composition is 5,000 to 5,000 as a weight average molecular weight in terms of polystyrene by GPC (hereinafter also simply referred to as “weight average molecular weight (Mw)”). , 000 is preferable, and more preferably 10,000 to 300,000.
As a content rate of alkali-soluble resin in an inorganic particle containing 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 an inorganic particle containing photosensitive composition.
[0018]
(C) Specific methacrylate compound
The inorganic particle-containing photosensitive composition of the present invention has a compound having at least two methacryloyl groups in one molecule. By containing a compound having at least two methacryloyl groups in one molecule as an ethylenically unsaturated group, a highly accurate pattern can be formed, and an inorganic particle-containing photosensitive composition excellent in thermal decomposability Can be provided.
Specific examples of such methacrylate compounds include: alkylene glycol dimethacrylates such as ethylene glycol and propylene glycol; polyalkylene glycol dimethacrylates such as polyethylene glycol and polypropylene glycol; both-end hydroxypolybutadiene, both-end hydroxypolyisoprene, both Dimethacrylates of both terminal hydroxylated polymers such as terminal hydroxypolycaprolactone;
Polymethacrylates of trihydric or higher polyhydric alcohols such as glycerin, 1,2,4-butanetriol, trimethylolalkane, tetramethylolalkane, pentaerythritol, dipentaerythritol; polyalkylene glycol of trihydric or higher polyhydric alcohol Polymethacrylates of adducts; polymethacrylates of cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzenediol; polyester methacrylate, epoxy methacrylate, urethane methacrylate, alkyd resin methacrylate, silicone resin methacrylate, spirane resin Examples include oligomethacrylates such as methacrylate.
Among these, alkylene glycol dimethacrylates such as ethylene glycol and propylene glycol; polyalkylene glycol dimethacrylates such as polyethylene glycol and polypropylene glycol; glycerin, 1,2,4-butanetriol, trimethylolalkane, tetramethylol Polymethacrylates of trihydric or higher polyhydric alcohols such as alkane, pentaerythritol, dipentaerythritol; polymethacrylates of polyalkylene glycol adducts of trihydric or higher polyhydric alcohols are preferred, ethylene glycol dimethacrylate, propylene glycol di Methacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, glycerin dimethacrylate, Li serine trimethacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetramethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol penta methacrylate and dipentaerythritol hexa methacrylate are more preferred, trimethylolpropane trimethacrylate are particularly preferred.
These specific methacrylate compounds can be used alone or in combination of two or more.
In the inorganic particle-containing photosensitive composition of the present invention, other ethylenically unsaturated group-containing compounds may be used in combination with the specific methacrylate compound. The other ethylenically unsaturated group-containing compound is not particularly limited as long as it is a compound that can undergo radical polymerization reaction with a photopolymerization initiator described later. For example, the methacryloyl group in the methacrylate compound described above was changed to an acryloyl group. Examples thereof include compounds and compounds shown in monomers (A), (B) and (C) constituting the binder resin described above.
The molecular weights of these specific methacrylate compounds and other ethylenically unsaturated group-containing compounds are not particularly limited, but usually the molecular weight is 5,000 or less.
As usage-amount of a specific methacrylate compound, it is 20-500 mass parts normally with respect to 100 mass parts of alkali-soluble resin, More preferably, it is 40-250 mass parts. Moreover, as the usage-amount of another ethylenically unsaturated compound, it is 100 mass parts or less normally with respect to 100 mass parts of alkali-soluble resin.
[0019]
(D) Photopolymerization initiator
The photopolymerization initiator constituting the inorganic particle-containing 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.
[0020]
(E) Solvent
The inorganic particle-containing photosensitive composition usually contains a solvent. As said solvent, (A) Affinity with inorganic particles and solubility of other organic components are good, can impart an appropriate viscosity to the inorganic particle-containing photosensitive composition, and is dried. It is preferable that it 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 inorganic particle-containing photosensitive composition can be appropriately selected within a range in which a favorable performance of forming the inorganic particle-containing photosensitive resin layer (fluidity or plasticity) can be obtained. A) It is 1-10,000 mass parts with respect to 100 mass parts of inorganic particles, Preferably it is 10-1,000 mass parts.
[0021]
(F) Various additives
In addition to the components (A) to (E), the inorganic particle-containing photosensitive composition includes a plasticizer, an adhesion assistant, a dispersant, a storage stabilizer, an antifoaming agent, an antioxidant, an ultraviolet absorber, Various additives such as a leveling agent and 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 inorganic particle-containing photosensitive resin 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 various members obtained.
[0022]
[Chemical 1]

[0023]
(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. )
[0024]
[Chemical formula 2]

[0025]
(Wherein R^Five Represents an alkyl or alkenyl group having 1 to 30 carbon atoms. )
[0026]
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 alkyl group has more than 30 carbon atoms, the solubility of the plasticizer in the solvent is lowered, and good film flexibility may not be obtained.
[0027]
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.
[0028]
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.
[0029]
The content ratio of the plasticizer in the inorganic particle-containing photosensitive composition is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the inorganic particles. The
[0030]
(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.
[0031]
[Chemical Formula 3]

[0032]
(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.)
[0033]
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.
[0034]
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 alkyldiethylpropoxysilanes 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);
[0035]
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);
[0036]
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.
[0037]
Among 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.
[0038]
As a content rate of the adhesion assistant in an inorganic particle containing 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. Is done.
[0039]
(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.
[0040]
The content ratio of the dispersant in the inorganic particle-containing photosensitive composition is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the inorganic particles. The
The inorganic particle-containing photosensitive composition of the present invention comprises (A) inorganic particles, (B) an alkali-soluble resin, (C) a specific methacrylate compound, (D) a photopolymerization initiator, (E) a solvent, and as necessary ( F) Various additives can be prepared by kneading using a kneader such as a roll kneader, a mixer, a homomixer, a ball mill, or a bead mill.
The inorganic particle-containing photosensitive composition prepared as described above is a paste-like composition having fluidity suitable for coating, and its viscosity is usually 10 to 100,000 mPa · s.^-1And preferably 50 to 10,000 mPa · s.^-1, More preferably 100 to 5,000 mPa · s^-1It is said.
The composition of the present invention can be particularly suitably used for producing the photosensitive film of the present invention described in detail below.
<Photosensitive film>
The photosensitive film of the present invention usually comprises a support film and an inorganic particle-containing photosensitive resin layer formed thereon, and a protective film is provided on the surface of the inorganic particle-containing photosensitive resin layer. It may be.
[0041]
<Supporting film and protective film>
The support film constituting the photosensitive film of the present invention is preferably a resin film having heat resistance and solvent resistance and flexibility. Since the support film has flexibility, an inorganic particle-containing photosensitive resin layer can be formed by applying the paste-like composition with a roll coater or the like, and the photosensitive film is wound in a roll shape. Can be stored and 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.
A release treatment may be performed on the surface of the support film. 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 preferably subjected to a release treatment, and the peel strength between the protective film / inorganic particle-containing photosensitive resin layer is smaller than the peel strength between the support film / inorganic particle-containing photosensitive resin layer. is necessary.
The photosensitive film of the present invention is obtained by applying the inorganic particle-containing photosensitive composition of the present invention on a support film, drying the coating film to remove part or all of the solvent, and forming an inorganic particle-containing photosensitive resin layer. Usually, it can manufacture by providing a protective film (press-bonding) on the said inorganic particle containing photosensitive resin layer.
[0042]
As a method of applying the inorganic particle-containing photosensitive composition on a support film to obtain an inorganic particle-containing photosensitive resin layer, a coating film having a large film thickness (for example, 1 μm or more) excellent in film thickness uniformity is efficiently obtained. Preferably, it can be 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, etc. Can be mentioned.
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 ratio in the inorganic particle-containing photosensitive resin layer) is usually 2% by mass. It is as follows.
The film thickness of the inorganic particle-containing photosensitive resin layer formed on the support film as described above can be appropriately selected depending on the content of inorganic particles, the type and size of the member, and the like.
[0043]
Member forming method
Regarding the inorganic particle-containing photosensitive composition and photosensitive film of the present invention, in the formation of dielectrics, electrodes, resistors, phosphors, barrier ribs, color filters and black matrix constituting each display cell of the plasma display panel, The organic component is excellent in thermal decomposability and can be suitably used for forming a highly accurate pattern.
In the method for forming a member using the photosensitive film of the present invention, at least [1] a transfer step of the photosensitive resin layer containing inorganic particles, [2] an exposure step of the photosensitive resin layer containing inorganic particles, [3] inorganic particles It has each process of the image development process of a containing photosensitive resin layer, and the baking process of [4] inorganic particle containing photosensitive resin layer pattern.
[1] Transfer process of inorganic particle-containing photosensitive resin layer
In the transfer step, the photosensitive film of the present invention is used and the inorganic particle-containing photosensitive resin layer constituting the photosensitive 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 peeling off the protective film of the photosensitive film provided as necessary, the photosensitive film is overlaid on the substrate so that the surface of the photosensitive resin layer containing inorganic particles is in contact with it, and the photosensitive film is heated. It is thermocompression bonded with a roller. As a result, the inorganic particle-containing photosensitive resin layer is transferred onto and closely adhered to the substrate. Here, as the 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.
Moreover, the photosensitive resin layer (resist layer) which does not contain an inorganic particle may be further provided on the inorganic particle containing photosensitive resin layer formed from the photosensitive film of this invention. This photosensitive resin layer usually disappears from the pattern in the development process and baking process described later.
Furthermore, an inorganic particle-containing resin layer other than the resin layer obtained from the inorganic particle-containing photosensitive resin composition of the present invention may be provided. The inorganic particle-containing resin layer may be photosensitive or non-photosensitive.
[0044]
[2] Exposure step of inorganic particle-containing photosensitive resin layer
In the exposure step, the surface of the inorganic particle-containing photosensitive resin layer is selectively irradiated (exposed) with radiation through an exposure mask to form a latent image of the inorganic particle-containing photosensitive resin layer pattern. In addition, the support film on the inorganic particle-containing photosensitive resin layer may be peeled and removed before the exposure step, or may be peeled and removed after the exposure step and before the developing step described later. From the viewpoint of increasing sensitivity, the support film on the inorganic particle-containing photosensitive resin layer is preferably peeled off after the exposure step and before the development step described below. When the resist layer described above is provided, the surface of the resist layer is irradiated with radiation through an exposure mask.
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.
[0045]
[3] Development process of inorganic particle-containing photosensitive resin layer
In the development step, the exposed inorganic particle-containing photosensitive resin layer is developed to reveal a pattern (latent image) of the inorganic particle-containing photosensitive resin layer.
An alkaline developer can be used as the developer used in the development step of the inorganic particle-containing photosensitive resin layer. Thereby, the alkali-soluble resin contained in the inorganic particle-containing photosensitive resin layer can be easily dissolved and removed.
Since the inorganic particles contained in the inorganic particle-containing photosensitive resin 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. The
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.
[0046]
The alkaline developer used in the developing step of the inorganic particle-containing photosensitive resin layer can be prepared by dissolving one or more of the alkaline compounds in water. 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 inorganic particle containing photosensitive resin layer pattern side surface and board | substrate exposed part as needed after image development processing.
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 step, an inorganic particle-containing photosensitive resin layer pattern (pattern corresponding to an exposure mask) composed of the inorganic particle-containing photosensitive resin layer remaining portion and the inorganic particle-containing photosensitive resin layer removal portion is formed. The
[0047]
[4] Firing process of inorganic particle-containing photosensitive resin layer pattern
In this step, the inorganic particle-containing photosensitive resin layer pattern is baked to form a member. Thereby, the organic substance in the inorganic particle containing photosensitive resin layer residual part burns down, and a member can be obtained on the surface of a board | 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.
In addition, it is preferable that the baking process of an inorganic particle containing photosensitive resin layer pattern is performed simultaneously with the baking process of another member, unless the performance of the target member is impaired significantly from a viewpoint of manufacturing efficiency improvement.
[0048]
【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).
[0049]
<Example 1>
(1) Preparation of inorganic particle-containing photosensitive composition:
(A) As inorganic particles, 60 parts of Cr—Cu composite oxide particles (granular) with an average particle size of 0.5 μm, PbO—B with an average particle size of 1 μm₂ O_Three -SiO₂ System low melting point glass frit (indefinite shape, softening point 500 ° C.) 40 parts, (B) alkali-soluble resin, n-butyl methacrylate / 3-hydroxypropyl methacrylate / methacrylic acid = 60/20/20 (mass%) 40 parts of copolymer (Mw = 100,000), (C) 40 parts of trimethylolpropane trimethacrylate as the specific methacrylate compound, (D) 2-benzyl-2-dimethylamino-1- ( 4 parts of 4-morpholinophenyl) -butan-1-one, (E) 150 parts of propylene glycol monomethyl ether acetate as a solvent, and (F) 1 part of oleic acid as a dispersant were kneaded in a bead mill, and then a stainless mesh By filtering with (500 mesh, 25 μm diameter), inorganic particle content Sex composition was prepared.
[0050]
(2) Production of photosensitive film:
By the operations (b) and (b) below, an inorganic particle-containing film of the present invention in which a support film, an inorganic particle-containing photosensitive resin layer, and a protective film were sequentially laminated was produced.
(A) An inorganic particle-containing photosensitive composition was applied onto a support film (width 200 mm, length 30 m, thickness 38 μm) made of a PET film using a blade coater, and the coating film was dried at 100 ° C. for 5 minutes. The solvent was completely removed, and an inorganic particle-containing photosensitive resin layer having an average film thickness of 15 μm was formed on the support film.
(B) A protective film made of a PET film that has been preliminarily released on the inorganic particle-containing photosensitive resin layer formed in (a) above is thermocompression bonded, and the support film, the inorganic particle-containing photosensitive resin layer, and the protective film are in this order. A laminated photosensitive film was prepared.
[0051]
(3) Formation of members
Transfer process of inorganic particle-containing photosensitive resin layer:
After peeling off and removing the protective film from the photosensitive film, the photosensitive film is overlaid on the surface of the glass substrate for 6-inch panel so that the surface of the photosensitive resin layer containing inorganic particles comes into contact with the photosensitive film. Thermocompression bonding was performed 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 inorganic particle-containing photosensitive resin layer was transferred and adhered to the surface of the glass substrate.
[0052]
Exposure process and development process of inorganic particle-containing photosensitive resin layer:
The inorganic particle-containing photosensitive resin layer was irradiated with i rays (ultraviolet light having a wavelength of 365 nm) with an ultrahigh pressure mercury lamp through an exposure mask (a stripe pattern having a width of 400 μm). Here, the irradiation amount is 400 mJ / cm²It was.
After completion of the exposure step, the support film is peeled and removed from the inorganic particle-containing photosensitive resin layer, and then 0.4% by mass aqueous sodium carbonate solution (30 ° C.) with respect to the exposed inorganic particle-containing photosensitive resin layer. A developing process by a shower method using as a developing solution was performed for 1 minute. Subsequently, a water washing treatment with ultrapure water was performed, thereby removing the uncured inorganic particle-containing photosensitive resin layer that was not irradiated with ultraviolet rays to form an inorganic particle-containing photosensitive resin layer pattern.
[0053]
Dielectric paste printing process:
A dielectric paste (YPT030 manufactured by Asahi Glass Co., Ltd.) is screen-printed on a glass substrate on which an inorganic particle-containing photosensitive resin pattern is formed, then dried at 100 ° C. for 5 minutes, and a dielectric paste film having an average film thickness of 30 μm Formed.
[0054]
Baking process of inorganic particle-containing photosensitive resin layer pattern and dielectric paste film:
The glass substrate having the dielectric paste film formed on the inorganic particle-containing photosensitive resin layer pattern was baked for 30 minutes in a 580 ° C. temperature atmosphere in a baking furnace. Thereby, a panel material in which a black matrix pattern and a dielectric layer were formed on the surface of the glass substrate was obtained.
When the dielectric layer on the black matrix pattern in the obtained panel material was observed with an optical microscope, bubbles having a diameter of 20 μm or more were not observed in the dielectric layer.
[0055]
<Reference example 1>
(C) An inorganic particle-containing photosensitive composition was prepared in the same manner as in Example 1 except that 40 parts of tripropylene glycol dimethacrylate was used as the specific methacrylate compound. A photosensitive film was produced in the same manner as in Example 1 except that the inorganic particle-containing photosensitive composition was used. Except having used the said photosensitive film, it carries out similarly to Example 1, and performs the transfer process of an inorganic particle containing photosensitive resin layer, and the exposure process and image development process of an inorganic particle containing photosensitive resin layer, and inorganic particle containing photosensitive property A resin layer pattern was formed. Next, in the same manner as in Example 1, a dielectric paste printing process and an inorganic particle-containing photosensitive resin layer pattern and a dielectric paste film firing process were performed, whereby a black matrix pattern and a dielectric were formed on the surface of the glass substrate. A panel material formed with a layer was obtained. When the dielectric layer on the black matrix pattern in the obtained panel material was observed with an optical microscope, bubbles having a diameter of 20 μm or more were not observed in the dielectric layer.
[0056]
<Example 3>
(A) As inorganic particles, 95 parts of Ag particles (granular) and Bi having an average particle size of 3 μm₂ O_Three -ZnO-B₂ O_Three -SiO₂ -Al₂ O_Three An inorganic particle-containing photosensitive composition was prepared in the same manner as in Example 1 except that 5 parts of a low melting point glass frit (irregular shape, softening point 520 ° C.) was used. A photosensitive film was produced in the same manner as in Example 1 except that the inorganic particle-containing photosensitive composition was used. Except having used the said photosensitive film, it carries out similarly to Example 1, and performs the transfer process of an inorganic particle containing photosensitive resin layer, and the exposure process and image development process of an inorganic particle containing photosensitive resin layer, and inorganic particle containing photosensitive property A resin layer pattern was formed.
Next, in the same manner as in Example 1, a dielectric paste printing process and an inorganic particle-containing photosensitive resin layer pattern and a dielectric paste film firing process were performed, whereby an electrode pattern and a dielectric layer were formed on the surface of the glass substrate. A panel material formed of was obtained.
When the dielectric layer on the electrode pattern in the obtained panel material was observed with an optical microscope, bubbles having a diameter of 20 μm or more were not observed in the dielectric layer.
[0057]
<Comparative Example 1>
(C) An inorganic particle-containing photosensitive composition was prepared in the same manner as in Example 1 except that 40 parts of trimethylolpropane triacrylate was used instead of the specific methacrylate compound. A photosensitive film was produced in the same manner as in Example 1 except that the inorganic particle-containing photosensitive composition was used. Except having used the said photosensitive film, it carries out similarly to Example 1, and performs the transfer process of an inorganic particle containing photosensitive resin layer, and the exposure process and image development process of an inorganic particle containing photosensitive resin layer, and inorganic particle containing photosensitive property A resin layer pattern was formed.
Next, in the same manner as in Example 1, a dielectric paste printing process and an inorganic particle-containing photosensitive resin layer pattern and a dielectric paste film firing process were performed, whereby a black matrix pattern and a dielectric were formed on the surface of the glass substrate. A panel material formed with a layer was obtained.
When the dielectric layer on the black matrix pattern in the obtained panel material was observed with an optical microscope, many bubbles having a diameter of 20 μm or more were observed in the dielectric layer.
[0058]
<Comparative example 2>
(C) An inorganic particle-containing photosensitive composition was prepared in the same manner as in Example 1 except that 40 parts of tripropylene glycol diacrylate was used instead of the specific methacrylate compound. A photosensitive film was produced in the same manner as in Example 1 except that the inorganic particle-containing photosensitive composition was used. Except having used the said photosensitive film, it carries out similarly to Example 1, and performs the transfer process of an inorganic particle containing photosensitive resin layer, and the exposure process and image development process of an inorganic particle containing photosensitive resin layer, and inorganic particle containing photosensitive property A resin layer pattern was formed.
Next, in the same manner as in Example 1, a dielectric paste printing process and an inorganic particle-containing photosensitive resin layer pattern and a dielectric paste film firing process were performed, whereby a black matrix pattern and a dielectric were formed on the surface of the glass substrate. A panel material formed with a layer was obtained.
When the dielectric layer on the black matrix pattern in the obtained panel material was observed with an optical microscope, bubbles having a diameter of 20 μm or more were observed in the dielectric layer.
[0059]
【The invention's effect】
According to the inorganic particle-containing photosensitive composition and the photosensitive film of the present invention, a pattern with excellent thermal decomposability of the organic component and high accuracy can be formed. The inorganic particle-containing photosensitive composition and photosensitive film of the present invention are suitable for forming dielectrics, electrodes, resistors, phosphors, barrier ribs, color filters, and black matrices constituting each display cell of a plasma display panel. Can be used.
[Brief description of the drawings]
FIG. 1 is a schematic view 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 (8)

(A -1 ) Ag, Au, Al, Ni, Ag-Pd alloy, Cu, Cr inorganic particles or (A-2) Co, Cr, Cu, Fe, Mn, Ni and Ti Metal particles, metal oxide particles or composite oxide particles ,
(B) an alkali-soluble resin ;
(C) trimethylolpropane trimethacrylate ,
(D) a dye containing a photopolymerization initiator and represented by the following formula (1)
D ⁺ · ^A - (1)
An inorganic particle-containing photosensitive composition for forming a plasma display panel member, which does not contain (wherein D ⁺ is a cation part of a cationic dye and A ^- represents an anion) . Furthermore, the glass frit is contained, The inorganic particle containing photosensitive composition for plasma display panel member formation of Claim 1 characterized by the above-mentioned. The said plasma display panel member is an electrode or a black matrix, The inorganic particle containing photosensitive composition for plasma display panel member formation of Claim 1 or 2 characterized by the above-mentioned. A photosensitive film comprising an inorganic particle-containing photosensitive resin layer obtained from the inorganic particle-containing photosensitive composition for forming a plasma display panel member according to any one of claims 1 to 3 . [ 1 ] A step of transferring an inorganic particle-containing photosensitive resin layer on the glass substrate using the photosensitive film according to claim 4;
[ 2 ] A step of exposing the surface of the transferred inorganic particle-containing photosensitive resin layer to radiation through an exposure mask to form a latent image of the inorganic particle-containing photosensitive resin layer;
[ 3 ] Developing the exposed inorganic particle-containing photosensitive resin layer to form a pattern of the inorganic particle-containing photosensitive resin layer; and
[ 4 ] Firing the pattern of the inorganic particle-containing photosensitive resin layer;
A method for forming a plasma display panel member. 6. The method of forming a plasma display panel member according to claim 5, wherein the plasma display panel member is an electrode or a black matrix. The method for forming a plasma display panel member according to claim 5 or 6, wherein the firing step is performed simultaneously with a firing step of another member. [ 1 ] A step of transferring an inorganic particle-containing photosensitive resin layer on the glass substrate using the photosensitive film according to claim 4;
[ 2 ] A step of exposing the surface of the transferred inorganic particle-containing photosensitive resin layer to radiation through an exposure mask to form a latent image of the inorganic particle-containing photosensitive resin layer;
[ 3 ] Developing the exposed inorganic particle-containing photosensitive resin layer to form a pattern of the inorganic particle-containing photosensitive resin layer; and
[ 4 ] Forming a dielectric paste film on the glass substrate on which the pattern of the inorganic particle-containing photosensitive resin layer is formed;
[ 5 ] Baking the pattern of the inorganic particle-containing photosensitive resin layer and the dielectric paste film;
A method of forming a plasma display panel member, comprising:

Images