JP4244680B2 - Photosensitive alkali-soluble composition - Google Patents

Description

【００３５】
【化２】

【００３６】
トリシクロ環とエチレン性不飽和結合とを有する環式モノマーとしては、トリシクロ基として、トリシクロ[５.２.１.０^2,6]デカンから水素原子１つが除かれてなるトリシクロ[５.２.１.０^2,6]デカニル基（化学式（３）で表される基）、トリシクロ[５.２.１.０^2,6]−３−デセン（トリシクロ[５.２.１.０^2,6]−デカ−３−エン）から水素原子１つが除かれてなるトリシクロ[５.２.１.０^2,6]−３−デセニル基（化学式（４）で表される基であり、ジシクロペンテニル基とも称される。）を有し、エチレン性不飽和結合として（メタ）アクリロイル基を有する、環式モノマーが挙げられる。ここで、上記例示したトリシクロ基と（メタ）アクリロイル基とは、−Ｏ−又は−Ｏ−Ｒ−Ｏ−（Ｒはアルキレン基）を介して結合していることが好ましい。
【００３７】
【化３】

【００３８】
【化４】

【００３９】
トリシクロ環とエチレン性不飽和結合とを有する環式モノマーの具体例としては、アクリロイルオキシトリシクロ[５.２.１.０^2,6]デカン（日立化成工業社製、FANCRYL FA-513A）やメタクリロイルオキシトリシクロ[５.２.１.０^2,6]デカン（日立化成工業社製、FANCRYL FA-513M）等の（メタ）アクリロイルオキシトリシクロ[５.２.１.０^2,6]デカン、アクリロイルオキシトリシクロ[５.２.１.０^2,6]−デカ−３−エン（日立化成工業社製、FANCRYL FA-511A）等の（メタ）アクリロイルオキシトリシクロ[５.２.１.０^2,6]−デカ−３−エン、アクリロイルオキシエチルオキシトリシクロ[５.２.１.０^2,6]−３−デセン（日立化成工業社製、FANCRYL FA-512A）等の（メタ）アクリロイルオキシアルキルオキシトリシクロ[５.２.１.０^2,6]−デカ−３−エンが挙げられる。
【００４０】
カルボキシルモノマー：
ａ成分を構成するカルボキシルモノマーとしては、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマル酸、クロトン酸、シトラコン酸、メサコン酸、α−クロロアクリル酸等が挙げられる。これらのモノマーは単独で用いても２種類以上併用して使用してもよい。
【００４１】
Ｎ−置換マレイミド：
ａ成分を構成するＮ−置換マレイミドとしては、Ｎ−シクロヘキシルマレイミド、Ｎ−２−メチルヘキシルマレイミド、Ｎ−２−エチルシクロヘキシルマレイミド、Ｎ−２−クロロシクロヘキシルマレイミド等のＮ−シクロアルキルマレイミドや、Ｎ−フェニルマレイミド、Ｎ−２−メチルフェニルマレイミド、Ｎ−２−エチルフェニルマレイミド、Ｎ−２−クロロフェニルマレイミド等のＮ−アリールマレイミドが挙げられる。これらの中では、透明性及び溶解性の観点から、Ｎ−シクロヘキシルマレイミド及びＮ−２−メチルシクロヘキシルマレイミドが特に好ましい。なお、Ｎ−置換マレイミドは単独で用いても２種類以上併用してもよい。
【００４２】
ａ成分は、側鎖及び／又は末端にエチレン性不飽和結合を有する共重合体であることが好ましい。そして、当該エチレン性不飽和結合は（メタ）アクリロイル基に由来することが好ましい。
【００４３】
側鎖及び／又は末端にエチレン性不飽和結合を有するバインダーポリマーは、例えば、環式モノマーとカルボキシルモノマーとヒドロキシモノマーとＮ−置換マレイミドとを重合してなる重合物に、カルボキシル基及び／又は水酸基と反応し得る官能基とエチレン性不飽和結合とを有する化合物（以下「付加モノマー」という。）を反応させることにより得ることができる。
【００４４】
付加モノマーとしては、グリシジル（メタ）アクリレート、メチルグリシジル（メタ）アクリレート等のグリシジルモノマーや、（メタ）アクリロイルオキシアルキルイソシアナート（２-メタクリロイルオキシエチルイソシアナート等）等のイソシアネートモノマーが挙げられる。付加モノマーの付加量は、バインダーポリマーの重量（ｇ）を基準として、０.１〜５mmol/gが好ましく、より好ましくは０.２〜４mmol/gである。付加量が０.１mmol/g未満である場合は、光硬化部位の耐アルカリ性の向上が少なくなる傾向にあり、５mmol/gを超す場合は、光に対して感度が高くなりすぎて解像度の低下が生じる場合がある。
【００４５】
ａ成分のＭｗは３，０００〜２００，０００が好ましく、３，０００〜１００，０００がより好ましく、５，０００〜５０，０００が更に好ましい。Ｍｗが、３，０００未満では、耐アルカリ性が低下する傾向があり、２００，０００を超す場合は粘度が高くなり、スピンコート等で塗布する際の塗布性が低下する傾向がある。なお、本発明において、Ｍｗは、ゲルパーミエーションクロマトグラフィーによって測定し、標準ポリスチレンの検量線を用いて換算した値である。
【００４６】
ａ成分の含有比率は、感光性アルカリ可溶型組成物の全重量を基準として、５〜９０重量％が好ましく、７〜８５重量％がより好ましく、１０〜８０重量％が特に好ましい。含有比率が、５重量％未満である場合は、膜のフィルム性が低下し脆くなる傾向があり、９０重量％を超えると現像性が低下し、現像時間の超過、解像性低下などの不具合が発生するおそれがある。
【００４７】
（ｂ成分）
ｂ成分は、光重合性不飽和結合を１個以上有するモノマーであり、光照射により生じたｃ成分の活性種により重合する成分である。なお、ａ成分がエチレン性不飽和結合を有する場合は、ａ成分もｂ成分の重合に取り込まれ、両成分は結合を生じる。
【００４８】
ｂ成分としては、例えば、メチルメタクリレート、ベンジルメタクリレート、ブトキシエチルメタクリレート、ブトキシトリエチレングリコールアクリレート、ＥＣＨ（エピクロルヒドリン）変性ブチルアクリレート、ジシクロペンタニルアクリレート、ＥＯ（エチレンオキシド）変性ジシクロペンテニルアクリレート、Ｎ，Ｎ−ジメチルアミノエチルメタクリレート、エチルジエチレングリコールアクリレート、２−エチルヘキシルアクリレート、グリセロールメタクリレート、ヘプタデカフロロデシルアクリレート、２−ヒドロキシエチルメタクリレート、カプロラクトン変性−２−ヒドロキシエチルアクリレート、イソボルニルアクリレート、メトキシジプロピレングリコールアクリレート、メトキシ化シクロデカトリエンアクリレート、フェノキシヘキサエチレングリコールアクリレート、ＥＯ変性リン酸アクリレート、カプロラクトン変性テトラヒドロフルフリルアクリレート、ＥＯ変性ビスフェノールＡジアクリレート、ＥＣＨ変性ビスフェノールＡジアクリレート、ビスフェノールＡジメタクリレート、１，４−ブタンジオールジアクリレート、１，３−ブチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、グリセロールジメタクリレート、ネオペンチルグリコールジアクリレート、ＥＯ変性リン酸ジアクリレート、ＥＣＨ変性フタル酸ジアクリレート、ポリエチレングリコール４００ジアクリレート、ポリプロピレングリコール４００ジメタクリレート、テトラエチレングリコールジアクリレート、ＥＣＨ変性１，６−ヘキサンジオールジアクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ＥＯ変性リン酸トリアクリレート、ＥＯ変性トリメチロールプロパントリアクリレート、ＰＯ変性トリメチロールプロパントリアクリレート（ＰＯはプロピレンオキシドを意味する。以下同様）、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールペンタアクリレート等のアクリレート、これらに対応するメタクリレートなどが挙げられる。これらのモノマーは、単独で又は２種以上を組み合わせて用いることができる。
【００４９】
ｂ成分の含有比率は、感光性アルカリ可溶型組成物の全重量を基準として、０.５〜７０重量％が好ましく、１〜６８重量％がより好ましく、２〜６５重量％が特に好ましい。含有比率が、０.５重量％未満である場合は、光感度が低くなる傾向があり、７０重量％を超えると現像時間が長くなる傾向がある。
【００５０】
（ｃ成分）
ｃ成分は光開始剤であり、光照射によりラジカル等の活性種を発生してｂ成分の重合を生じせしめる化合物である。ｃ成分はｉ線（波長：３６５ｎｍ）で光ラジカル反応を生じ得る光開始剤であることが好ましい。
【００５１】
ｃ成分としては、例えば、ベンゾフェノン、Ｎ，Ｎ’−テトラエチル−４，４’−ジアミノベンゾフェノン、４−メトキシ−４’−ジメチルアミノベンゾフェノン、ベンジル、２，２−ジエトキシアセトフェノン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソブチルエーテル、ベンジルジメチルケタール、α−ヒドロキシイソブチルフェノン、チオキサントン、２−クロロチオキサントン、１−ヒドロキシシクロヘキシルフェニルケトン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−１−プロパン、ｔ−ブチルアントラキノン、１−クロロアントラキノン、２，３−ジクロロアントラキノン、３−クロル−２−メチルアントラキノン、２−エチルアントラキノン、１，４−ナフトキノン、９，１０−フェナントラキノン、１，２−ベンゾアントラキノン、１，４−ジメチルアントラキノン、２−フェニルアントラキノン、２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾール二量体等を挙げることができる。これらの光開始剤は、単独で又は２種以上を組み合わせて用いることが可能である。
【００５２】
ｃ成分の含有比率は、感光性アルカリ可溶型組成物の全重量を基準として、０.０１〜１０重量％が好ましく、０.０２〜８重量％がより好ましく、０.０５〜７重量％が特に好ましい。含有比率が、０.０１重量％未満の場合は、光感度が低くなる傾向があり、１０重量％を超えると、透明性及び得られるパターンの切れが低下する他、未露光部の現像残渣が発生する場合がある。
【００５３】
（ｄ成分）
ｄ成分は有機溶剤であり、感光性アルカリ可溶型組成物の粘度を塗布に適した値（３〜２００ｍＰａ・ｓが好ましい。）に保つために任意に添加される成分である。
【００５４】
ｄ成分としては、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル等のジエチレングリコールのモノ又はジアルキルエーテル、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノプロピルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート等のジエチレングリコールモノアルキルエーテルのアセチル化物、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノプロピルルエーテル、トリエチレングリコールモノブチルエーテル、トリエチレングリコールジメチルエーテル、トリエチレングリコールメチルエチルエーテル、トリエチレングリコールジエチルエーテル、トリエチレングリコールジプロピルエーテル、トリエチレングリコールジブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールメチルエチルエーテル、プロピレングリコールジプロピルエーテル、プロピレングリコールジブチルエーテル等のプロピレングリコールのモノ又はジアルキルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート等のプロピレングリコールモノアルキルエーテルのアセチル化物、β−ラクトン、γ−ラクトン、δ−ラクトン等のラクトンが好ましい。これらは単独で用いてもよく、２種類以上を併用して用いてもよい。
【００５５】
ｄ成分の含有比率は、感光性アルカリ可溶型組成物の全重量を基準として、１〜８０重量％が好ましく、５〜７５重量％がより好ましく、６〜７４重量％が更に好ましい。含有比率が１重量％未満の場合は、感光性アルカリ可溶型組成物の粘度が高く、塗布性の低下が生じる傾向にあり、８０重量％を超す場合は、硬化物（塗膜）の乾燥性が低下し、タック発生の原因となる。
【００５６】
（その他添加成分）
本発明の感光性アルカリ可溶型組成物においては、上記ａ〜ｄ成分の他に、暗反応を抑制するためのハイドロキノン、ハイドロキノンモノメチルエーテル、ピロガロール、ｔ−ブチルカテコール等の熱重合禁止剤；被着体（基材）との密着性を向上させるためのシランカップリング剤（ビニル基、エポキシ基、アミノ基、メルカプト基等の官能基と、アルコキシシリル基を有した化合物）やチタネート系カップリング剤（イソプロピルトリメタクリロイルチタネート、ジイソプロピルイソステアロイル−４−アミノベンゾイルチタネート等）；膜の平滑性を向上させるための界面活性剤（フッ素系、シリコーン系、炭化水素系等）；紫外線吸収剤；酸化防止剤；色素、顔料等の着色剤等を必要に応じて適宜添加することができる。
【００５７】
また、エポキシ樹脂、ウレタン樹脂、メラミン樹脂等のａ成分以外の樹脂を、ａ成分１００重量部に対して、５０重量部以下となるように添加することができる。この添加量が５０重量部を超えると、現像時間が長くなる原因となり解像性の低下原因ともなり得る。
【００５８】
（感光性アルカリ可溶型組成物の適用）
本発明の感光性アルカリ可溶型組成物を硬化することにより、高い透明性及び硬度を備え、硬化収縮の低減された硬化物を得ることができる。硬化物は、基材上にパターン化された薄膜（硬化物層）として形成させることが好ましい。パターン化された硬化物層は、基材上に感光性アルカリ可溶型組成物に由来する層を形成させる積層工程と、前記層の所定部分に活性光線を照射して露光部を形成せしめる露光工程と、該露光部以外の部分を除去する現像工程と、を備える方法により形成可能である。
【００５９】
積層工程において使用される基材としては、白板ガラス、青板ガラス、シリカコート青板ガラス等の透明ガラス基板；ポリエステル樹脂、ポリカーボネート樹脂、アクリル樹脂、塩化ビニル樹脂等の合成樹脂からなるシート、フィルム又は基板；アルミニウム板、銅板、ニッケル板、ステンレス板等の金属基板；セラミック基板；光電変換素子を有する半導体基板；表面に色材膜を備えるガラス基板等が挙げられる。
【００６０】
上記基材に感光性アルカリ可溶型組成物に由来する層を形成させる方法としては、感光性アルカリ可溶型組成物からなる感光液を基材に直接塗布する方法や、感光性エレメントを用いる方法が挙げられる。
【００６１】
ａ〜ｃ成分のみからなる感光性アルカリ可溶型組成物が流動性を有する場合は、感光性アルカリ可溶型組成物をそのまま感光液として使用できる。しかし、感光性アルカリ可溶型組成物にｄ成分を添加して低粘度化させて感光液として用いることが好ましい。なお、感光性アルカリ可溶型組成物がｄ成分を含有する場合であっても、ｄ成分として上記に例示した有機溶剤以外の有機溶剤（以下「後添加による有機溶剤」という。）を更に添加して、所定の粘度の感光液とすることも可能である。この場合において、感光性アルカリ可溶型組成物に含まれる有機溶剤の全重量のうち、後添加による有機溶剤の含有比率は、９０重量％以下が好ましく、５０重量％以下がより好ましい。この使用量が９０重量％を超えると、感光液の安定性が低下する傾向がある。
【００６２】
後添加による有機溶剤としては、例えば、ケトン系、セロソルブ系、アルコール系、芳香族系の有機溶剤が挙げられる。具体的には、アセトン、メチルエチルケトン、シクロヘキサノン、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルセロソルブアセテート、エチレングリコールモノプロピルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコールジメチルエーテル、３−メチル−３−メトキシブタノール、３−メチル−３−メトキシブチルアセテート、Ｎ−メチル−２−ピロリドン、Ｎ−ヒドロキシメチル−２−ピロリドン、メチルアルコール、エチルアルコール、イソプロピルアルコール、ｎ−ブチルアルコール、テトラヒドロフラン、ジオキサン、ベンゼン、トルエン、キシレン、酢酸エチル等の有機溶剤が例示可能である。
【００６３】
感光液を基材に直接塗布する塗布方法としては、ロールコーター塗布、スピンコーター塗布、スプレー塗布、ホエラー塗布、ディップコーター塗布、カーテンフローコーター塗布、ワイヤーバーコーター塗布、グラビアコーター塗布、エアナイフコーター塗布等が挙げられる。
【００６４】
感光性アルカリ可溶型組成物が有機溶剤等の揮発成分を含まない場合は、塗布した感光液がそのまま「感光性アルカリ可溶型組成物に由来する層」となる。感光性アルカリ可溶型組成物が有機溶剤等の揮発成分を含む場合は、上記塗布後に５０〜１３０℃の温度で１〜３０分乾燥させることにより、感光性アルカリ可溶型組成物の不揮発成分の薄膜を形成させ、「感光性アルカリ可溶型組成物に由来する層」を得る（乾燥工程）。
【００６５】
一方、感光性エレメントを用いて、基材に感光性アルカリ可溶型組成物からなる層を形成させる方法は以下のとおりである。
【００６６】
感光性エレメントは、支持体と、該支持体上に形成された上記感光性アルカリ可溶型組成物からなる感光性アルカリ可溶型組成物層（当該層の厚さは、０．１〜３００μｍが好ましく、０．２〜３０μｍがより好ましく、０．２〜１０μｍが更に好ましい。）と、を備えているが、かかる感光性エレメントは、支持体（ポリエステルフィルム、ポリイミドフィルム、ポリアミドイミドフィルム、ポリプロピレンフィルム、ポリスチレンフィルム等のフィルム）に感光性アルカリ可溶型組成物（又は感光液）を、ナイフコーター塗布、グラビアコーター塗布、ロールコーター塗布、スプレーコーター塗布等により塗布して、５０〜１３０℃の温度で１〜３０分間乾燥して作製することができる。
【００６７】
なお、感光性アルカリ可溶型組成物層の表面に塵等が付着するのを防ぐ目的で、感光性アルカリ可溶型組成物層の表面に剥離可能なカバーフィルム（ポリエチレンフィルム、テフロン（登録商標）フィルム、ポリプロピレンフィルム、表面処理した紙等）を積層することが好ましく、カバーフィルムは、感光性アルカリ可溶型組成物層と支持体との接着力よりも、感光性アルカリ可溶型組成物層とカバーフィルムとの接着力の方がより小さくなる素材からなることが好ましい。
【００６８】
このような感光性エレメントを用いて、基材上に「感光性アルカリ可溶型組成物に由来する層」を形成させる方法としては、感光性エレメントの感光性アルカリ可溶型組成物層を基材に圧着してラミネートする方法が挙げられる。なお、感光性エレメントがカバーフィルムを有するときはそれを剥がしながらラミネートを行い、ラミネートにあたっては、加熱圧着することが好ましく、雰囲気は常圧でも減圧下でもよい。これにより、感光性エレメントの感光性アルカリ可溶型組成物層が「感光性アルカリ可溶型組成物に由来する層」となる。
【００６９】
上述のようにして感光液又は感光性エレメントを使用して積層工程を実施した後、露光工程において、基材上の「感光性アルカリ可溶型組成物に由来する層」の所定部分に活性光線を照射し、当該層を硬化させて露光部を形成せしめる。所定部分に活性光線を照射する方法としては、フォトマスクを介したパターン露光や走査による直接描写等が挙げられる。
【００７０】
活性光線の照射は、カーボンアーク灯、超高圧水銀灯、高圧水銀灯、キセノンランプ、メタルハライドランプ、蛍光ランプ、タングステンランプ、可視光レーザー等を光源として行うことができ、積層工程で感光性エレメントを用いたときは、支持体上から露光してもよく、支持体を剥離した後に露光してもよい。一方、積層工程で感光液を用いた場合においては、層表面を直接露光してもよく、層表面にポリビニルアルコール等の酸素遮断膜を０．５〜３０μｍの厚みで形成した後、その上から露光してもよい。
【００７１】
現像工程においては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、メタケイ酸ナトリウム等の無機アルカリ、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、テトラメチルアンモニウムハイドロオキサイド、トリエチルアミン、ｎ−ブチルアミン等の有機塩基又はその塩を含む水溶液を、露光工程で得られた感光性アルカリ可溶型組成物に由来する層を備えた基材に吹き付けるか、当該基材を水溶液に浸漬するなどして未露光部を除去し、パターン化された硬化物層を得ることができる。この場合において、感光性エレメントの支持体を通して露光した場合には、支持体を剥離した後に現像を行う。
【００７２】
現像工程終了後においては、高圧水銀灯などを用いて０．５〜５J/cm²の光量で後露光するか、６０〜２６０℃の温度で１〜１２０分間、後加熱することが好ましい（後硬化工程）。これにより、パターン化された硬化物層をより強固にすることができる。
【００７３】
（積層体）
本発明は、基材と、該基材上に形成された上記発明の感光性アルカリ可溶型組成物の硬化物からなる硬化物層と、を備えることを特徴とする積層基材を提供する。なお、硬化物は、感光性アルカリ可溶型組成物が揮発成分を含まない場合は、感光性アルカリ可溶型組成物の硬化物をいい、揮発成分を含む場合は、当該揮発成分を除去したものの硬化物をいう（以下同様）。また、基材としては、上述したものと同様の基材を用いることができる。積層基材における硬化物層は、本発明の感光性アルカリ可溶型組成物を用いたものであるため、高い透明性及び膜硬度を有している。
【００７４】
（液晶表示装置用カラーフィルタ）
図１は、本発明の液晶表示装置用カラーフィルタの実施形態を模式的に示す断面図である。図１に示す液晶表示装置用カラーフィルタ１０は、ガラス基板１２と、ガラス基板１２上に二次元状に配列するように形成された、赤色材層Ｒ、緑色材層Ｇ及び青色材層Ｂと、ガラス基板１２上であってこれらの色材層間に少なくとも形成された遮光層１４と、赤色材層Ｒ、緑色材層Ｇ、青色材層Ｂ及び遮光層１４を覆うようにガラス基板１２上に形成された保護膜層１６と、保護膜層１６上に形成された導体層１８と、を備えている。
【００７５】
液晶表示装置用カラーフィルタの第１の実施形態によれば、保護膜層１６が本発明の感光性アルカリ可溶型組成物の硬化物である。また、第２の実施形態によれば、赤色材層Ｒ、緑色材層Ｇ、青色材層Ｂが、それぞれ、赤色材を含有する本発明の感光性アルカリ可溶型組成物の硬化物、緑色材を含有する本発明の感光性アルカリ可溶型組成物の硬化物、青色材を含有する本発明の感光性アルカリ可溶型組成物の硬化物である。なお、保護膜層１６、赤色材層Ｒ、緑色材層Ｇ及び青色材層Ｂの全てに本発明の感光性アルカリ可溶型組成物の硬化物を用いることもできる。
【００７６】
第１及び第２の実施形態によれば、保護膜層や色材層を、アルカリ現像時間の短い本発明の感光性アルカリ可溶型組成物を用いて作製するために、製造コストを下げることができ量産性を向上させることができる。また、本発明の感光性アルカリ可溶型組成物は硬化物の透明性が高いため、本発明の液晶表示装置用カラーフィルタを用いた液晶表示装置は、明瞭でシャープな画像を表示することが可能になる。更に、硬化物の硬度が高いために液晶表示装置用カラーフィルタ全体の強度が向上し、液晶表示装置の信頼性、耐久性が優れるようになる。そして、保護膜層上に高温でＩＴＯスパッタにより導体層を設ける場合であっても、保護膜層にしわやクラックが生じることがない。
【００７７】
（液晶セル用スペーサー）
図２は、本発明の実施形態にかかる液晶セル用スペーサーを適用した液晶セルを模式的に示す断面図である。図２に示す液晶セル２０中、対向する一対の透明基板２１は、それらの内側の面上に設けられた電極２２と、その上に印刷形成され配向処理が施された配向膜２３とを備えている。そして、透明基板２１と、透明基板２１周辺に形成されたシール層２４とにより規定される空間に液晶物質２５が封入されており、一対の透明基板２１を所定の間隔で対向させるために上記空間には液晶セル用スペーサ２６が形成されている。
【００７８】
図２に示された液晶セル２０においては、液晶セル用スペーサ２６が本発明の感光性アルカリ可溶型組成物の硬化物からなっている。ここで、液晶セル用スペーサー２０は、本発明の感光性アルカリ可溶型組成物を用いたリソグラフィ技術により液晶セル２０内の所望の場所に形成させている。したがって、従来の球状スペーサーで発生していた、ずれに基づく液晶表示装置における画素表面の傷の発生が効果的に防止される。
【００７９】
（液晶表示装置用反射板）
図３は、本発明の実施形態にかかる液晶表示装置用反射板を設けた液晶セルを模式的に示す断面図である。
【００８０】
図３に示す液晶表示装置用反射板３０は、ガラス板３４と、この上に断面が略三角形になるように設けられた樹脂層３３と、樹脂層３３を被覆する反射層３２と、を備えており、樹脂層３３は本発明の感光性アルカリ可溶型組成物の硬化物である。そして、液晶表示装置用反射板３０は液晶セル２０の一方の面側に、液晶表示装置用カラーフィルタ１０を介して配置されている。なお、図３における液晶セル２０及び液晶表示装置用カラーフィルタ１０は上記と同様の構成を有している。
【００８１】
液晶表示装置用反射板３０は片面に、膜硬度の高い本発明の感光性アルカリ化用型組成物の硬化物を備えているために、液晶表示装置に明瞭な画像を表示させることが可能になる。
【００８２】
本発明の感光性アルカリ可溶型組成物は、硬化物として上記以外の電子部品に用いることも可能である、例えば、液晶をスイッチングする電極が複数配列してなる液晶表示装置用電子素子基板であって、当該基板が、本発明の感光性アルカリ可溶型組成物の硬化物により平坦化されていることを特徴とする液晶表示装置用電子素子基板、を提供することが可能になる。具体的には、基板上にアレイ状に配列されたＴＦＴ素子上に設けられるＴＦＴ−ＬＣＤ用アレイ電極平坦化膜として、本発明の感光性アルカリ可溶型組成物の硬化物を用いることができる。以上の他、フラットパネルディスプレイの部材として適用することも可能である。
【００８３】
【実施例】
以下、本発明の好適な実施例についてさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
【００８４】
［バインダーポリマーの製造例］
（バインダーポリマー１）
（Ａ）１Ｌスケールの四つ口フラスコに２６４ｇのプロピレングリコールモノメチルエーテルアセテートと乳酸メチル６６gを秤取り、窒素でバブリングしながら、液温を９０℃に保った。
（Ｂ）１Ｌビーカー内で２４０ｇのプロピレングリコールモノメチルエーテルアセテート、乳酸メチル６０ｇ、メタクリロイルオキシトリシクロ[５.２.１.０^2,6]デカン（日立化成工業社製、FANCRYL FA-513M）８６．４ｇ、Ｎ−シクロヘキシルマレイミド３６．５ｇ、２−ヒドロキシエチルメタクリレート１０６．７ｇ、メタクリル酸４０．５ｇを混合し、窒素バブリングしながら溶解させた。Ｎ−シクロヘキシルマレイミドの溶解を確認した後、２，２’−アゾビスイソブチロニトリル３ｇを溶解させた。
【００８５】
（Ｂ）を（Ａ）に３時間かけて連続的に滴下し、その後３時間９０℃に保持した。３時間９０℃に保持している間、数回に分けて、４０ｇのジエチレングリコールジメチルエーテルの中にあらかじめ溶解させておいた２，２’−アゾビスイソブチロニトリル０．６ｇを残存モノマー低減のため添加した。合計６時間、９０℃で反応を行った後、１２０℃まで液温を上昇させ、その後１時間１２０℃に保ち自然冷却して、重合体（以下「重合体１」という。）の溶液を得た。
【００８６】
エチレン性不飽和結合（メタクリロイル基）を導入するために、得られた溶液に、２−メタクリロイルオキシエチルイソシアナートと錫系の触媒とを添加し８０℃で２〜３時間保持し、自然冷却して側鎖及び／又は末端にエチレン性不飽和結合を有するバインダーポリマー（バインダーポリマー１）の溶液を得た。なお、２−メタクリロイルオキシエチルイソシアナートは重合体１に対し、１．５ｍｍｏｌ／ｇとなるようにした。
【００８７】
（バインダーポリマー２）
（Ａ）１Ｌスケールの四つ口フラスコに２６４ｇのプロピレングリコールモノメチルエーテルアセテートと乳酸メチル６６gを秤取り、窒素でバブリングしながら、液温を９０℃に保った。
（Ｂ）１Ｌビーカー内で２４０ｇのプロピレングリコールモノメチルエーテルアセテート、乳酸メチル６０g、ベンジルメタクリレート８６．４ｇ、Ｎ−シクロヘキシルマレイミド３６．５ｇ、２−ヒドロキシエチルメタクリレート１０６．７ｇ、メタクリル酸４０．５ｇを混合し、窒素バブリングしながら溶解させた。Ｎ−シクロヘキシルマレイミドの溶解を確認した後、２，２’−アゾビスイソブチロニトリル３ｇを溶解させた。（Ｂ）を（Ａ）に３時間かけて連続的に滴下し、その後３時間９０℃に保たせた。
【００８８】
（Ｂ）を（Ａ）に３時間かけて連続的に滴下し、その後３時間９０℃に保持した。３時間９０℃に保持している間、数回に分けて、４０ｇのジエチレングリコールジメチルエーテルの中にあらかじめ溶解させておいた２，２’−アゾビスイソブチロニトリル０．６ｇを残存モノマー低減のため添加した。合計６時間、９０℃で反応を行った後、１２０℃まで液温を上昇させ、その後１時間１２０℃に保ち自然冷却して、重合体（以下「重合体２」という。）の溶液を得た。
【００８９】
エチレン性不飽和結合（メタクリロイル基）を導入するために、得られた溶液に、２−メタクリロイルオキシエチルイソシアナートと錫系の触媒とを添加し８０℃で２〜３時間保持し、自然冷却して側鎖及び／又は末端にエチレン性不飽和結合を有するバインダーポリマー（バインダーポリマー２）の溶液を得た。なお、２−メタクリロイルオキシエチルイソシアナートは重合体２に対し、１．５ｍｍｏｌ／ｇとなるようにした。
【００９０】
（バインダーポリマー３）
（Ａ）１Ｌスケールの四つ口フラスコに２８５ｇのプロピレングリコールモノメチルエーテルアセテートを秤取り、窒素バブリングしながら、液温を９０℃に保った。
（Ｂ）１Ｌビーカー内で３００ｇのプロピレングリコールモノメチルエーテルアセテート、ベンジルメタクリレート１４１．８ｇ、Ｎ−シクロヘキシルマレイミド６３．０ｇ、２−ヒドロキシエチルメタクリレート６３．０ｇ、メタクリル酸４７．３ｇを混合し、窒素バブリングしながら溶解させた後、２，２’−アゾビスイソブチロニトリル３ｇを溶解させた。
【００９１】
（Ｂ）を（Ａ）に３時間かけて連続的に滴下し、その後３時間９０℃に保持した。３時間９０℃に保持している間、数回に分けて、４０ｇのジエチレングリコールジメチルエーテルの中にあらかじめ溶解させておいた２，２’−アゾビスイソブチロニトリル０．６ｇを残存モノマー低減のため添加した。合計６時間、９０℃で反応を行った後、１２０℃まで液温を上昇させ、その後１時間１２０℃に保ち自然冷却して、バインダーポリマー３の溶液を得た。
【００９２】
（バインダーポリマー４）
（Ａ）１Ｌスケールの四つ口フラスコに２８５ｇのプロピレングリコールモノメチルエーテルアセテートを秤取り、窒素でバブリングしながら、液温を９０℃に保った。
（Ｂ）１Ｌビーカー内で３００ｇのプロピレングリコールモノメチルエーテルアセテート、ベンジルメタクリレート２６７．８ｇ、メタクリル酸４７．２ｇを混合し、窒素バブリングしながら溶解させた後、２，２’−アゾビスイソブチロニトリル３ｇを溶解させた。
【００９３】
（Ｂ）を（Ａ）に３時間かけて連続的に滴下し、その後３時間９０℃に保持した。３時間９０℃に保持している間、数回に分けて、４０ｇのジエチレングリコールジメチルエーテルの中にあらかじめ溶解させておいた２，２’−アゾビスイソブチロニトリル０．６ｇを残存モノマー低減のため添加した。合計６時間、９０℃で反応を行った後、１２０℃まで液温を上昇させ、その後１時間１２０℃に保ち自然冷却して、バインダーポリマー４の溶液を得た。
【００９４】
重合体１〜２、バインダーポリマー１〜４の組成及び特性（粘度及び分子量）について以下の表１及び表２にまとめて示す。
【００９５】
【表１】

【００９６】
【表２】

【００９７】
次いで、バインダーポリマー１〜４を用いて、感光性アルカリ可溶型組成物を作製した。
【００９８】
（実施例１）
感光性アルカリ可溶型組成物のａ成分としてバインダーポリマー１を３５ｇ、ｂ成分としてペンタエリスリトールテトラアクリレートを９ｇ、ｃ成分としてベンゾフェノン（１ｇ）及びＮ，Ｎ’−テトラエチル−４，４’−ジアミノベンゾフェノン（１ｇ）、ｄ成分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を５４ｇ秤取り、撹拌子とスターラーを用いて、ｃ成分が完全に溶解するまで撹拌し、感光性アルカリ可溶型組成物の溶液を得た。
【００９９】
（実施例２、参考例１）
バインダーポリマー１に代えて、バインダーポリマー２、バインダーポリマー３を用いた他は実施例１と同様にして、それぞれ実施例２、参考例１の感光性アルカリ可溶型組成物の溶液を得た。
【０１００】
（比較例１）
バインダーポリマー１に代えて、バインダーポリマー４を用いた他は実施例１と同様にして、比較例１の感光性アルカリ可溶型組成物の溶液を得た。
【０１０１】
次いで、以下に示す評価方法により、パターン形状形成時間（最少現像時間）、現像後の残膜率及び総収縮率、及び膜硬度を評価した。
【０１０２】
（パターン形状形成の時間（最少現像時間）の評価方法）
実施例１〜２、参考例１、比較例１で得られた感光性アルカリ可溶型組成物の溶液を、ガラス基板（コーニング社製、商品名７０５９）上にスピンコート法により塗布し、更に９０℃で５分間乾燥を行い、膜厚２．０μｍの膜を形成した。得られた膜に、ネガマスクを通して超高圧水銀灯により画像状に２００ｍＪ／ｃｍ^２の露光を行い、次いで、ポリオキシエチレンノニルフェニルエーテル（東邦化学株式社製、商品名ノナール９１２Ａ）を０．５重量％及び水酸化カリウムを０．３重量％含む水溶液により、現像液３０±１℃の液温で６０秒間現像を行った。かかる方法により現像を開始した時から、パターンが得られるまでの時間（秒）を測定した。
【０１０３】
（現像後の残膜率及び総収縮率の評価方法）
実施例１〜２、参考例１、比較例１で得られた感光性アルカリ可溶型組成物の溶液を、ガラス基板（コーニング社製、商品名７０５９）上にスピンコートで成膜し、ホットプレート上で９０℃、５分間焼成した後、上記と同様の条件で露光を行い、接触型表面粗さ測定器（Ｄｅｃｔａｋ）を用いて膜厚を測定した（得られた膜厚を膜厚１とする。）。次いで、上記と同様の方法により現像を行い、自然乾燥後、光を照射して硬化した部分の膜厚を測定した（得られた膜厚を膜厚２とする）。これに続いて、２３０℃の乾燥機内で３０分焼成を行い、光を照射して硬化した部分の膜厚を測定した（得られた膜厚を膜厚３とする）。そして、膜厚２及び膜厚３を膜厚１で除すことにより、現像後の残膜率及び総収縮率を算出した。
【０１０４】
（膜硬度の評価方法）
実施例１〜２、参考例１、比較例１で得られた感光性アルカリ可溶型組成物の溶液をガラス基板上にスピンコート法により塗布し、９０℃で５分間乾燥を行って、膜厚約５μｍの膜を形成した。そして、得られた膜に、ネガマスクを通して超高圧水銀灯により２００ｍＪ／ｃｍ^２の露光を行い、パターンを形成した。次いで、ポリオキシエチレンノニルフェニルエーテル（０．５重量％）と水酸化カリウム（０．３重量％）とを含む水溶液からなる現像液を用いて、液温３０±１℃にて６０秒間現像を行い、２３０℃で３０分乾燥して硬化物層を備えたガラス基板を得た。そしてかかる基板を用いて硬化膜の硬度（ビッカース硬さ）の評価を行った。硬度（ビッカース硬さ）の測定は、ジャパンハイテック社製ＭａｉｃｒｏｈａｒａｄｎｅｓｓＴｅｓｔｅｒ ＭＨＴ−４により、負荷荷重２０ｋｇｆ、負荷速度２０ｋｇｆ／秒、保持時間５秒の条件で行った。
【０１０５】
評価結果を以下の表３に示す。
【表３】

【０１０６】
【発明の効果】
以上説明したように、本発明によれば、樹脂酸価を極端に上げることなくアルカリ現像の時間を短縮することができ、硬化物の透明性及び膜硬度の向上を図ることも可能で、硬化に基づく収縮も低減された、感光性アルカリ可溶型組成物を提供することが可能になる。また、かかる感光性アルカリ可溶型組成物を用いた感光性エレメント、積層基材、液晶表示装置用カラーフィルタ、液晶セル用スペーサ及び液晶表示装置用反射板を提供することが可能になる。
本発明の感光性アルカリ可溶型組成物を用いることにより、ＬＣＤ用感光性スペーサー形成材料、カラーフィルタ保護層用材料、ＬＣＤ用コンタクトホール形成材料、ＴＦＴ−ＬＣＤ用アレイ電極平坦化膜形成材料、反射又は半透過型ＬＣＤ用反射層形成材料、フラットパネルディスプレイ用の各種材料等を作製することができる。
【図面の簡単な説明】
【図１】本発明の液晶表示装置用カラーフィルタの実施形態を模式的に示す断面図である。
【図２】本発明の実施形態にかかる液晶セル用スペーサーを適用した液晶セルを模式的に示す断面図である。
【図３】本発明の実施形態にかかる液晶表示装置用反射板を設けた液晶セルを模式的に示す断面図である。
【符号の説明】
１０…液晶表示装置用カラーフィルタ、１２…ガラス基板、Ｒ…赤色材層、Ｇ…緑色材層、Ｂ…青色材層、１４…遮光層、１６…保護膜層、１８…導体層、２０…液晶セル、２１…透明基板、２２…電極、２３…配向膜、２４…シール層、２５…液晶物質、２６…液晶セル用スペーサ、３０…液晶表示装置用反射板、３２…反射層、３３…樹脂層、３４・・・ガラス板。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photosensitive alkali-soluble composition, a photosensitive element, a laminated substrate, a color filter for a liquid crystal display device, a spacer for a liquid crystal cell, and a reflector for a liquid crystal display device.
[0002]
[Prior art]
In recent years, in the manufacture of semiconductors and liquid crystal display devices (LCDs), in view of the influence on the global environment, liquid saving of materials using organic solvents has been attempted. Moreover, in order to improve mass productivity, the manufacturing time of a product is shortened.
[0003]
A color panel used for an LCD includes a red color material layer (R layer), a green color material layer (G layer), and a blue color material layer (B layer) on a glass substrate. By repeating the same process three times, each color material layer is formed separately. That is, first, a photosensitive resin composition containing a red material is formed on a glass substrate, then exposed, further developed and baked to form an R layer having a predetermined pattern. Next, the formation of the G layer and the B layer is performed by the same process as the R layer. In this step, the firing temperature is generally 200 ° C. to 240 ° C., and the firing time is 30 minutes to 60 minutes.
[0004]
Therefore, it is conceivable to shorten the firing time by setting the firing temperature to a temperature higher than 240 ° C., but at such a temperature, coloring of the photosensitive resin composition and other materials used for forming the color material layer is possible. This causes a decrease in transmittance. On the other hand, there is a method in which the acid value of the resin composition is increased to improve the solubility of the alkali developer and shorten the development time. There is a problem that the solubility is improved based on the value, and the reduction of the film is increased.
[0005]
By the way, in recent years, LCDs are required to have higher definition, smaller size, and thinner thickness, and high reliability is required for photosensitive materials and the like.
[0006]
For example, the spherical spacer provided between the color filter and the array substrate may cause damage to the pixel surface due to vibration and misalignment between the color filter substrate side and the array substrate side, resulting in reduced display quality. It becomes. Therefore, there is a demand for a spacer that can be formed at an arbitrary place and does not cause scratches.
[0007]
In recent years, products using LCDs have been miniaturized, and a structure in which a chip is formed on the surface of the substrate with the miniaturization has been adopted. Therefore, it has been conventionally used as a protective film layer for color filters. The thermosetting material has a problem that the adhesiveness of the chip is weakened. For this reason, thermosetting materials In Instead, a photo-curing material (for example, a material disclosed in Patent Document 1 below) capable of removing a portion where a chip is formed has been studied.
[0008]
However, the conventional photocurable protective film has a problem that the transmittance, heat resistance and the like are insufficient. That is, according to the prior art, the addition amount of the photopolymerization initiator is increased in order to improve chemical resistance. As a result, not only the transmittance near 365 nm is lowered but also the transmittance around 400 nm is reduced. There was also a drawback of lowering. The protective layer of the color filter must have the characteristics that can withstand the sputtering of the transparent electrode (ITO). Na However, the conventional photo-curing type protective film has low film hardness, and wrinkles and cracks may occur in the film due to ITO sputtering at a high temperature. In addition to these, the photocurable protective film according to the prior art has a large shrinkage due to curing, and the function as a planarizing material is insufficient as compared with the thermosetting protective film.
[0009]
[Patent Document 1]
JP 2002-20442 A (Claim 2)
[0010]
[Problems to be solved by the invention]
The present invention has been made in order to improve the above-mentioned disadvantages of the prior art, and can shorten the alkali development time without extremely increasing the resin acid value, and can improve the transparency and film hardness of the cured product. It is an object of the present invention to provide a photosensitive alkali-soluble composition that can be improved and that shrinkage due to curing is reduced. Another object of the present invention is to provide a photosensitive element, a laminated substrate, a color filter for a liquid crystal display, a spacer for a liquid crystal cell, and a reflector for a liquid crystal display using the photosensitive alkali-soluble composition. To do.
[0011]
[Means for Solving the Problems]
In order to solve the above object, the present invention provides a photosensitive alkali-soluble composition comprising a binder polymer, a monomer having one or more photopolymerizable unsaturated bonds, and a photoinitiator, The binder polymer includes (1) a cyclic monomer having at least one ring selected from the group consisting of a benzene ring, a cyclo ring, a bicyclo ring and a tricyclo ring and an ethylenically unsaturated bond, and (2) a carboxyl group and an ethylenic group. It has a skeleton obtained by polymerizing a carboxyl monomer having an unsaturated bond, (3) a hydroxy monomer having a hydroxyl group and an ethylenically unsaturated bond, and (4) an N-substituted maleimide. Based on the total weight of the monomer, carboxyl monomer, hydroxy monomer and N-substituted maleimide, the content ratio of the cyclic monomer is 3 to 70 The amount% content ratio from 5 to 50 wt% of said carboxyl monomer content ratio is 5 to 70 wt% of the hydroxy monomer content ratio is 5 to 50 wt% der of the N- substituted maleimide The binder polymer is a polymer having an ethylenically unsaturated bond in the side chain and / or terminal. A photosensitive alkali-soluble composition is provided.
[0012]
The photosensitive alkali-soluble composition of the present invention uses a copolymer of a monomer containing a cyclic monomer, a carboxyl monomer, a hydroxy monomer, and an N-substituted maleimide as a binder polymer, and such a copolymer Since a monomer having at least one photopolymerizable unsaturated bond and a photoinitiator are combined, the alkali development time can be shortened without extremely increasing the resin acid value, and the transparency and film hardness of the cured product can be shortened. The shrinkage due to curing can be reduced.
[0013]
The binder polymer is a polymer having an ethylenically unsaturated bond in the side chain and / or terminal. But, A polymer having a weight average molecular weight of 3,000 to 200,000 is preferred. By using such a binder polymer, the film strength of the cured product of the photosensitive alkali-soluble composition of the present invention is further improved, and it contributes to the reduction of curing shrinkage.
[0014]
The present invention also includes a support, and a photosensitive alkali-soluble composition layer comprising the above-described photosensitive alkali-soluble composition of the present invention formed on the support. Provide sex elements. Such a photosensitive element can be suitably used when a photosensitive alkali-soluble composition having a predetermined thickness is laminated on a substrate.
[0015]
The present invention further comprises a laminated substrate comprising: a substrate; and a cured product layer formed from the cured product of the photosensitive alkali-soluble composition of the present invention formed on the substrate. provide. Examples of such laminated base materials include the following color filters for liquid crystal display devices, spacers for liquid crystal cells, and reflectors for liquid crystal display devices.
[0016]
A transparent substrate, a plurality of color material layers formed so as to be two-dimensionally arranged on the transparent substrate, a light shielding layer formed on at least the color material layer on the transparent substrate, and the color material A color filter for a liquid crystal display device, comprising: a protective film layer formed on the transparent substrate so as to cover a layer and a light shielding layer; and a conductor layer formed on the protective film layer, wherein the protective film layer A color filter for a liquid crystal display device comprising a cured product of the photosensitive alkali-soluble composition of the present invention.
[0017]
A transparent substrate, a plurality of color material layers formed so as to be two-dimensionally arranged on the transparent substrate, a light shielding layer formed on at least the color material layer on the transparent substrate, and the color material A color filter for a liquid crystal display device, comprising: a protective film layer formed on the transparent substrate so as to cover a layer and a light shielding layer; and a conductor layer formed on the protective film layer, wherein the color material layer A color filter for a liquid crystal display device comprising a cured product of a composition comprising the photosensitive alkali-soluble composition of the present invention and a colorant.
[0018]
In a liquid crystal cell of a liquid crystal display device, a liquid crystal cell spacer is inserted between the transparent substrates to hold transparent substrates arranged opposite to each other at a predetermined interval, and the liquid crystal cell spacer includes: A spacer for a liquid crystal cell, comprising a cured product of the photosensitive alkali-soluble composition of the present invention.
[0019]
A reflection plate for a liquid crystal display device disposed on one surface side of a liquid crystal cell in a liquid crystal display device, the reflection plate for a liquid crystal display device comprising a reflection layer and a resin layer provided on at least one side of the layer And the resin layer comprises a cured product of the photosensitive alkali-soluble composition of the present invention.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
The photosensitive alkali-soluble composition of the present invention is a photosensitive alkali-soluble composition containing the following (a) to (c) as essential components, and the composition further comprises the following (d): May be included.
(A): A binder polymer obtained by polymerizing a cyclic monomer, a carboxyl monomer, a hydroxy monomer, and an N-substituted maleimide in the above content ratio (hereinafter referred to as “component a”).
(B): a monomer having one or more photopolymerizable unsaturated bonds (hereinafter referred to as “component b”).
(C): Photoinitiator (hereinafter referred to as “component c”).
(D): Organic solvent (hereinafter referred to as “d component”).
[0021]
The component a has a function of suitably maintaining the viscosity of the composition of the present invention, and also functions as a base material for maintaining the film shape in the photosensitive element. The component a has a skeleton obtained by polymerizing a specific amount of a cyclic monomer, a carboxyl monomer, a hydroxy monomer, and an N-substituted maleimide, and a functional group and a chemical structure derived from these monomers at a predetermined content ratio. Since it has in the molecule, the alkali development time can be shortened without extremely increasing the acid value of the photosensitive alkali-soluble composition of the present invention, and the transparency and film hardness of the cured product are improved. It is also possible to reduce shrinkage due to curing. Such an effect is obtained as the whole composition of the present invention, but high transparency is mainly attributed to the benzene ring, cyclo ring, bicyclo ring and tricyclo ring derived from the cyclic monomer, and good alkali development. It is considered that the property is attributed to the carboxyl monomer component. Moreover, it is thought that a carboxyl monomer component contributes also to the dispersibility improvement of other additive components, such as a pigment. And it is thought that the N-substituted maleimide component contributes to the improvement of the adhesion and heat resistance of the coating film, and the hydroxyl monomer component contributes to shortening the alkali development time.
[0022]
The component b has a function of polymerizing with the component c that generates active species (radicals, etc.) by light irradiation to give a cured product, and the component a is a functional group that can react with the component b (ethylenic) When it has an unsaturated bond, etc., it forms a crosslinked structure with the component a and contributes to further improvement in film hardness. Although component d is not an essential component for the photosensitive alkali-soluble composition, the addition of the photosensitive alkali-soluble composition can be facilitated by addition.
[0023]
(Component a)
The component a has a skeleton formed by polymerizing a cyclic monomer, a carboxyl monomer, a hydroxy monomer, and an N-substituted maleimide, and the content ratio of the cyclic monomer, the carboxyl monomer, the hydroxy monomer, and the N-substituted maleimide is Binder polymers that are 3 to 70 wt%, 5 to 50 wt%, 5 to 70 wt%, and 5 to 50 wt%, respectively, based on the total weight of monomers.
[0024]
The content ratios of cyclic monomer, carboxyl monomer, hydroxy monomer and N-substituted maleimide are 5 to 60% by weight, 5 to 45% by weight, 5 to 50% by weight and 5%, respectively, based on the total weight of these monomers. It is preferable that it is -45 weight%, and it is preferable that at least one part of the ethylenically unsaturated bond of these monomers originates in a (meth) acryloyl group. Here, (meth) acryloyl means methacryloyl or acryloyl, and is also synonymous with similar groups or compounds such as (meth) acryl.
[0025]
When the content ratio of the cyclic monomer is less than 3% by weight, the transparency of the photosensitive alkali-soluble composition of the present invention and this cured product becomes insufficient, and when it exceeds 70% by weight, Since the viscosity is improved, the handling property is lowered, and the dispersion stability when an additive component such as a dye is added becomes insufficient.
[0026]
When the content ratio of the carboxyl monomer is less than 5% by weight, alkali development failure occurs and a fine pixel pattern cannot be obtained. Further, when pigment dispersion is performed, aggregation occurs in a short time, and sufficient storage stability cannot be obtained. On the other hand, when the content ratio exceeds 50% by weight, not only the viscosity of the binder polymer becomes too high and the handling property deteriorates, but also the moisture resistance of the cured product decreases and the developer resistance becomes insufficient.
[0027]
When the content ratio of the hydroxyl monomer is less than 5% by weight, the pattern formation time is prolonged, and when it exceeds 70% by weight, the viscosity of the binder polymer is high, and white turbidity occurs when an organic solvent with low polarity is added. There is a case.
[0028]
When the content ratio of the N-substituted maleimide is less than 5% by weight, the adhesion to the substrate is insufficient when alkali development is performed and when a thermal history is applied. On the other hand, when the content ratio exceeds 50% by weight, the transparency of the photosensitive alkali-soluble composition and the cured product thereof becomes low, and when a coloring material such as a pigment is added, the cured product becomes brittle and the cured product is The resulting coating film may be chipped.
[0029]
Cyclic monomer:
The cyclic monomer constituting the component a is a monomer having at least one ring selected from the group consisting of a benzene ring, a cyclo ring, a bicyclo ring and a tricyclo ring and an ethylenically unsaturated bond.
[0030]
Examples of the cyclic monomer include a cyclic monomer having a benzene ring and an ethylenically unsaturated bond, a cyclic monomer having a cyclo ring and an ethylenically unsaturated bond, and a ring having a bicyclo ring and an ethylenically unsaturated bond. The cyclic monomer which has a formula monomer and a tricyclo ring and an ethylenically unsaturated bond is mentioned, The a component can have these 1 or 2 or more as a monomer unit.
[0031]
The number of ethylenically unsaturated bonds in the cyclic monomer is preferably 1. Further, the number of benzene rings, cyclo rings, bicyclo rings or tricyclo rings in the cyclic monomer is preferably 1.
[0032]
Examples of the cyclic monomer having a benzene ring and an ethylenically unsaturated bond include styrene, α-methylstyrene, and benzyl (meth) acrylate.
[0033]
Cyclic monomers having a cyclo ring and an ethylenically unsaturated bond include cyclic monomers such as cyclopentenyl (meth) acrylate, where the cyclo ring is a cycloalkane ring, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxy. Examples thereof include cyclic monomers in which the cyclo ring is a cycloalkene ring, such as ethyl (meth) acrylate. The cyclic monomer having a bicyclo ring and an ethylenically unsaturated bond includes a bornyl group (endo-1,7,7-trimethylbicyclo [2.2.1] hept-2-yl group, represented by the chemical formula (1)). Group) and a cyclic monomer having a (meth) acryloyl group (such as bornyl (meth) acrylate), an isobornyl group (exo-1,7,7-trimethylbicyclo [2.2.1] hept-2-yl group) And a cyclic monomer having a (meth) acryloyl group (such as isobornyl (meth) acrylate).
[0034]
[Chemical 1]

[0035]
[Chemical formula 2]

[0036]
Examples of the cyclic monomer having a tricyclo ring and an ethylenically unsaturated bond include tricyclo [5.2.1.0] as a tricyclo group. ^2,6 ] Tricyclo [5.2.1.0] in which one hydrogen atom is removed from decane ^2,6 ] Decanyl group (group represented by chemical formula (3)), tricyclo [5.2.1.0] ^2,6 ] -3-decene (tricyclo [5.2.1.0 ^2,6 ] -Dec-3-ene) tricyclo [5.2.1.0] in which one hydrogen atom is removed. ^2,6 ] -3-decenyl group (a group represented by the chemical formula (4), also referred to as a dicyclopentenyl group), and a (meth) acryloyl group as an ethylenically unsaturated bond Is mentioned. Here, the above-exemplified tricyclo group and (meth) acryloyl group are preferably bonded via —O— or —O—R—O— (R is an alkylene group).
[0037]
[Chemical 3]

[0038]
[Formula 4]

[0039]
Specific examples of the cyclic monomer having a tricyclo ring and an ethylenically unsaturated bond include acryloyloxytricyclo [5.2.1.0. ^2,6 ] Decane (manufactured by Hitachi Chemical Co., Ltd., FANCRYL FA-513A) and methacryloyloxytricyclo [5.2.1.0] ^2,6 ] (Meth) acryloyloxytricyclo [5.2.1.0] such as decane (manufactured by Hitachi Chemical Co., Ltd., FANCRYL FA-513M) ^2,6 ] Decane, acryloyloxytricyclo [5.2.1.0] ^2,6 ] -Deca-3-ene (manufactured by Hitachi Chemical Co., Ltd., FANCRYL FA-511A) and the like (meth) acryloyloxytricyclo [5.2.1.0] ^2,6 ] -Dec-3-ene, acryloyloxyethyloxytricyclo [5.2.1.0] ^2,6 ] -3-Decene (manufactured by Hitachi Chemical Co., Ltd., FANCRYL FA-512A) and other (meth) acryloyloxyalkyloxytricyclo [5.2.1.0] ^2,6 ] -Dec-3-ene.
[0040]
Carboxyl monomer:
Examples of the carboxyl monomer constituting the component a include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, citraconic acid, mesaconic acid, and α-chloroacrylic acid. These monomers may be used alone or in combination of two or more.
[0041]
N-substituted maleimide:
Examples of the N-substituted maleimide constituting the component a include N-cycloalkylmaleimide such as N-cyclohexylmaleimide, N-2-methylhexylmaleimide, N-2-ethylcyclohexylmaleimide, N-2-chlorocyclohexylmaleimide, N -N-arylmaleimides such as phenylmaleimide, N-2-methylphenylmaleimide, N-2-ethylphenylmaleimide, N-2-chlorophenylmaleimide and the like. Among these, N-cyclohexylmaleimide and N-2-methylcyclohexylmaleimide are particularly preferable from the viewpoints of transparency and solubility. N-substituted maleimides may be used alone or in combination of two or more.
[0042]
The component a is preferably a copolymer having an ethylenically unsaturated bond at the side chain and / or terminal. And it is preferable that the said ethylenically unsaturated bond originates in a (meth) acryloyl group.
[0043]
The binder polymer having an ethylenically unsaturated bond at the side chain and / or the terminal is, for example, a polymer obtained by polymerizing a cyclic monomer, a carboxyl monomer, a hydroxy monomer, and an N-substituted maleimide, into a carboxyl group and / or a hydroxyl group. It can be obtained by reacting a compound having a functional group capable of reacting with ethylenic unsaturated bond (hereinafter referred to as “addition monomer”).
[0044]
Examples of the addition monomer include glycidyl monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate, and isocyanate monomers such as (meth) acryloyloxyalkyl isocyanate (such as 2-methacryloyloxyethyl isocyanate). The addition amount of the addition monomer is preferably 0.1 to 5 mmol / g, more preferably 0.2 to 4 mmol / g, based on the weight (g) of the binder polymer. When the added amount is less than 0.1 mmol / g, the improvement in alkali resistance of the photocuring site tends to be small, and when it exceeds 5 mmol / g, the sensitivity to light becomes too high and the resolution is lowered. May occur.
[0045]
The Mw of the component a is preferably 3,000 to 200,000, more preferably 3,000 to 100,000, and still more preferably 5,000 to 50,000. When Mw is less than 3,000, the alkali resistance tends to decrease, and when it exceeds 200,000, the viscosity tends to increase, and the applicability when applied by spin coating or the like tends to decrease. In the present invention, Mw is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.
[0046]
The content ratio of the component a is preferably 5 to 90% by weight, more preferably 7 to 85% by weight, and particularly preferably 10 to 80% by weight based on the total weight of the photosensitive alkali-soluble composition. When the content ratio is less than 5% by weight, the film properties of the film tend to deteriorate and become brittle, and when it exceeds 90% by weight, the developability deteriorates, the development time is exceeded, and the resolution is lowered. May occur.
[0047]
(Component b)
The component b is a monomer having one or more photopolymerizable unsaturated bonds, and is a component that is polymerized by the active species of the component c generated by light irradiation. In addition, when a component has an ethylenically unsaturated bond, a component is also taken in by polymerization of b component, and both components produce a coupling | bonding.
[0048]
Examples of the component b include methyl methacrylate, benzyl methacrylate, butoxyethyl methacrylate, butoxytriethylene glycol acrylate, ECH (epichlorohydrin) modified butyl acrylate, dicyclopentanyl acrylate, EO (ethylene oxide) modified dicyclopentenyl acrylate, N, N -Dimethylaminoethyl methacrylate, ethyl diethylene glycol acrylate, 2-ethylhexyl acrylate, glycerol methacrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl methacrylate, caprolactone-modified-2-hydroxyethyl acrylate, isobornyl acrylate, methoxydipropylene glycol acrylate, Methoxylated cyclodecatriene acrylate , Phenoxyhexaethylene glycol acrylate, EO-modified phosphate acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, EO-modified bisphenol A diacrylate, ECH-modified bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1, 3-butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, EO-modified phosphoric acid diacrylate, ECH-modified phthalic acid diacrylate, polyethylene glycol 400 diacrylate, polypropylene glycol 400 dimethacrylate, tetraethylene glycol Diacrylate, ECH-modified 1,6-hexanediol Acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, EO-modified phosphoric acid triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate (PO means propylene oxide; the same applies hereinafter), pentaerythritol Examples thereof include acrylates such as tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate, and methacrylates corresponding to these. These monomers can be used alone or in combination of two or more.
[0049]
The content ratio of the component b is preferably 0.5 to 70% by weight, more preferably 1 to 68% by weight, and particularly preferably 2 to 65% by weight based on the total weight of the photosensitive alkali-soluble composition. When the content ratio is less than 0.5% by weight, the photosensitivity tends to be low, and when it exceeds 70% by weight, the development time tends to be long.
[0050]
(Component c)
Component c is a photoinitiator, and is a compound that generates active species such as radicals by light irradiation to cause polymerization of component b. The component c is preferably a photoinitiator capable of causing a photoradical reaction at i-line (wavelength: 365 nm).
[0051]
Examples of the component c include benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, and benzoin methyl ether. , Benzoin isobutyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1- Propane, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phena Torakinon, 1,2-anthraquinone, 1,4-dimethyl anthraquinone, 2-phenyl anthraquinone, mention may be made of 2- (o-chlorophenyl) -4,5-diphenyl imidazole dimer and the like. These photoinitiators can be used alone or in combination of two or more.
[0052]
The content ratio of the component c is preferably 0.01 to 10% by weight, more preferably 0.02 to 8% by weight, and more preferably 0.05 to 7% by weight based on the total weight of the photosensitive alkali-soluble composition. Is particularly preferred. When the content ratio is less than 0.01% by weight, the photosensitivity tends to be low. May occur.
[0053]
(D component)
The component d is an organic solvent, and is a component that is optionally added to maintain the viscosity of the photosensitive alkali-soluble composition at a value suitable for coating (preferably 3 to 200 mPa · s).
[0054]
As the d component, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether or the like mono- or dialkyl of diethylene glycol Diethylene glycol monoalkyl ethers such as ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate Acetylated product, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol methyl ethyl ether, triethylene glycol diethyl ether, triethylene glycol Ethylene glycol dipropyl ether, triethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol methyl ethyl Propylene glycol mono- or dialkyl ether such as ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc. Lactones such as an acetylated product of glycol monoalkyl ether, β-lactone, γ-lactone, and δ-lactone are preferred. These may be used alone or in combination of two or more.
[0055]
The content ratio of the d component is preferably 1 to 80% by weight, more preferably 5 to 75% by weight, and still more preferably 6 to 74% by weight based on the total weight of the photosensitive alkali-soluble composition. When the content ratio is less than 1% by weight, the viscosity of the photosensitive alkali-soluble composition tends to be high and the applicability tends to decrease. When the content ratio exceeds 80% by weight, the cured product (coating film) is dried. This will cause the tackiness to occur.
[0056]
(Other additive components)
In the photosensitive alkali-soluble composition of the present invention, in addition to the components a to d, thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, and t-butylcatechol for suppressing dark reaction; Silane coupling agents (compounds having a functional group such as vinyl group, epoxy group, amino group, mercapto group and alkoxysilyl group) and titanate coupling to improve adhesion to the substrate (base material) Agents (isopropyl trimethacryloyl titanate, diisopropylisostearoyl-4-aminobenzoyl titanate, etc.); surfactants for improving the smoothness of the film (fluorine-based, silicone-based, hydrocarbon-based, etc.); UV absorbers; antioxidants Agents: Colorants such as dyes and pigments can be added as necessary.
[0057]
In addition, a resin other than the component a such as an epoxy resin, a urethane resin, or a melamine resin can be added to 50 parts by weight or less with respect to 100 parts by weight of the component a. If this addition amount exceeds 50 parts by weight, it may cause the development time to become longer and the resolution to be lowered.
[0058]
(Application of photosensitive alkali-soluble composition)
By curing the photosensitive alkali-soluble composition of the present invention, a cured product having high transparency and hardness and reduced curing shrinkage can be obtained. The cured product is preferably formed as a patterned thin film (cured product layer) on the substrate. The patterned cured product layer is a layering step in which a layer derived from the photosensitive alkali-soluble composition is formed on a substrate, and exposure in which a predetermined portion of the layer is irradiated with actinic rays to form an exposed portion. It can be formed by a method comprising a step and a developing step for removing a portion other than the exposed portion.
[0059]
As the base material used in the lamination process, transparent glass substrates such as white plate glass, blue plate glass, silica coated blue plate glass; sheets, films or substrates made of synthetic resins such as polyester resin, polycarbonate resin, acrylic resin, vinyl chloride resin A metal substrate such as an aluminum plate, a copper plate, a nickel plate, or a stainless plate; a ceramic substrate; a semiconductor substrate having a photoelectric conversion element; a glass substrate having a color material film on the surface;
[0060]
As a method for forming a layer derived from the photosensitive alkali-soluble composition on the substrate, a method of directly applying a photosensitive solution comprising the photosensitive alkali-soluble composition to the substrate, or a photosensitive element is used. A method is mentioned.
[0061]
When the photosensitive alkali-soluble composition comprising only the components a to c has fluidity, the photosensitive alkali-soluble composition can be used as it is as a photosensitive solution. However, it is preferable to add the component d to the photosensitive alkali-soluble composition to lower the viscosity and use it as a photosensitive solution. Even when the photosensitive alkali-soluble composition contains the d component, an organic solvent other than the organic solvents exemplified above (hereinafter referred to as “organic solvent by post-addition”) is further added as the d component. Thus, a photosensitive solution having a predetermined viscosity can be obtained. In this case, of the total weight of the organic solvent contained in the photosensitive alkali-soluble composition, the content ratio of the organic solvent by post-addition is preferably 90% by weight or less, and more preferably 50% by weight or less. If the amount used exceeds 90% by weight, the stability of the photosensitive solution tends to decrease.
[0062]
Examples of the organic solvent by post-addition include ketone-based, cellosolve-based, alcohol-based and aromatic organic solvents. Specifically, acetone, methyl ethyl ketone, cyclohexanone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, 3-methyl- 3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, N-methyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, tetrahydrofuran, dioxane, Examples thereof include organic solvents such as benzene, toluene, xylene and ethyl acetate.
[0063]
Application methods for directly applying the photosensitive solution to the substrate include roll coater application, spin coater application, spray application, whaler application, dip coater application, curtain flow coater application, wire bar coater application, gravure coater application, air knife coater application, etc. Is mentioned.
[0064]
When the photosensitive alkali-soluble composition does not contain a volatile component such as an organic solvent, the applied photosensitive solution becomes a “layer derived from the photosensitive alkali-soluble composition” as it is. When the photosensitive alkali-soluble composition contains a volatile component such as an organic solvent, the photosensitive alkali-soluble composition can be dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes after the application, thereby forming a nonvolatile component of the photosensitive alkali-soluble composition. To form a “layer derived from the photosensitive alkali-soluble composition” (drying step).
[0065]
On the other hand, a method for forming a layer made of a photosensitive alkali-soluble composition on a substrate using a photosensitive element is as follows.
[0066]
The photosensitive element is a photosensitive alkali-soluble composition layer comprising a support and the photosensitive alkali-soluble composition formed on the support (the thickness of the layer is 0.1 to 300 μm). The photosensitive element is preferably a support (polyester film, polyimide film, polyamideimide film, polypropylene). A photosensitive alkali-soluble composition (or a photosensitive solution) is applied to a film, a film such as a polystyrene film, etc. by knife coater coating, gravure coater coating, roll coater coating, spray coater coating, etc. It can be produced by drying at a temperature for 1 to 30 minutes.
[0067]
For the purpose of preventing dust and the like from adhering to the surface of the photosensitive alkali-soluble composition layer, a cover film (polyethylene film, Teflon (registered trademark)) that can be peeled off from the surface of the photosensitive alkali-soluble composition layer. ) Film, polypropylene film, surface-treated paper, etc.) are preferably laminated, and the cover film has a photosensitive alkali-soluble composition rather than the adhesive strength between the photosensitive alkali-soluble composition layer and the support. It is preferable that the adhesive strength between the layer and the cover film is made of a material that is smaller.
[0068]
As a method for forming a “layer derived from a photosensitive alkali-soluble composition” on a substrate using such a photosensitive element, the method is based on the photosensitive alkali-soluble composition layer of the photosensitive element. A method of laminating by pressing to a material is mentioned. In addition, when the photosensitive element has a cover film, it laminates, peeling off, and in laminating, it is preferable to heat-press and the atmosphere may be normal pressure or pressure reduction. Thereby, the photosensitive alkali-soluble composition layer of the photosensitive element becomes a “layer derived from the photosensitive alkali-soluble composition”.
[0069]
After carrying out the laminating process using the photosensitive solution or the photosensitive element as described above, in the exposure process, an actinic ray is applied to a predetermined portion of the “layer derived from the photosensitive alkali-soluble composition” on the substrate. , And the layer is cured to form an exposed portion. Examples of the method of irradiating the predetermined portion with actinic rays include pattern exposure through a photomask and direct drawing by scanning.
[0070]
Irradiation with actinic rays can be performed using a carbon arc lamp, ultra-high pressure mercury lamp, high-pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, visible light laser, etc. as a light source. In some cases, the exposure may be performed on the support, or after the support is peeled off. On the other hand, when the photosensitive solution is used in the laminating step, the layer surface may be directly exposed, and after forming an oxygen blocking film such as polyvinyl alcohol with a thickness of 0.5 to 30 μm on the layer surface, from above You may expose.
[0071]
In the development process, inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium metasilicate, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide , An aqueous solution containing an organic base such as triethylamine or n-butylamine or a salt thereof is sprayed on a base material provided with a layer derived from the photosensitive alkali-soluble composition obtained in the exposure step, or the base material is an aqueous solution. It is possible to obtain a patterned cured product layer by removing the unexposed portion by immersing in, for example. In this case, when the exposure is performed through the support of the photosensitive element, development is performed after the support is peeled off.
[0072]
After the development process is completed, use a high-pressure mercury lamp, etc. to 0.5 to 5 J / cm ² It is preferable to carry out post-exposure with a light amount of 1 ° C. or post-heat at 60 to 260 ° C. for 1 to 120 minutes (post-curing step). Thereby, the patterned hardened | cured material layer can be strengthened more.
[0073]
(Laminate)
The present invention provides a laminated substrate comprising: a substrate; and a cured product layer formed from the cured product of the photosensitive alkali-soluble composition of the present invention formed on the substrate. . The cured product refers to a cured product of the photosensitive alkali-soluble composition when the photosensitive alkali-soluble composition does not contain a volatile component. When the photosensitive alkali-soluble composition contains a volatile component, the volatile component is removed. This refers to the cured product (the same shall apply hereinafter). Moreover, as a base material, the same base material as what was mentioned above can be used. Since the hardened | cured material layer in a laminated base material uses the photosensitive alkali-soluble type composition of this invention, it has high transparency and film | membrane hardness.
[0074]
(Color filters for liquid crystal display devices)
FIG. 1 is a cross-sectional view schematically showing an embodiment of a color filter for a liquid crystal display device of the present invention. A color filter 10 for a liquid crystal display device shown in FIG. 1 includes a glass substrate 12, a red material layer R, a green material layer G, and a blue material layer B formed so as to be two-dimensionally arranged on the glass substrate 12. On the glass substrate 12 so as to cover the light shielding layer 14 formed on at least the color material layer on the glass substrate 12 and the red material layer R, the green material layer G, the blue material layer B, and the light shielding layer 14. The formed protective film layer 16 and the conductor layer 18 formed on the protective film layer 16 are provided.
[0075]
According to the first embodiment of the color filter for a liquid crystal display device, the protective film layer 16 is a cured product of the photosensitive alkali-soluble composition of the present invention. Moreover, according to 2nd Embodiment, the red material layer R, the green material layer G, and the blue material layer B are respectively the hardened | cured material of the photosensitive alkali-soluble type composition of this invention containing a red material, and green. A cured product of the photosensitive alkali-soluble composition of the present invention containing a material, and a cured product of the photosensitive alkali-soluble composition of the present invention containing a blue material. In addition, the hardened | cured material of the photosensitive alkali-soluble type composition of this invention can also be used for all of the protective film layer 16, the red material layer R, the green material layer G, and the blue material layer B.
[0076]
According to the first and second embodiments, since the protective film layer and the color material layer are produced using the photosensitive alkali-soluble composition of the present invention having a short alkali development time, the production cost is reduced. And mass productivity can be improved. Further, since the photosensitive alkali-soluble composition of the present invention has high transparency of the cured product, the liquid crystal display device using the color filter for the liquid crystal display device of the present invention can display a clear and sharp image. It becomes possible. Furthermore, since the hardness of the cured product is high, the strength of the entire color filter for liquid crystal display devices is improved, and the reliability and durability of the liquid crystal display device are improved. Even when the conductor layer is provided on the protective film layer by ITO sputtering at a high temperature, no wrinkles or cracks are generated in the protective film layer.
[0077]
(Liquid crystal cell spacer)
FIG. 2 is a cross-sectional view schematically showing a liquid crystal cell to which the spacer for liquid crystal cell according to the embodiment of the present invention is applied. In the liquid crystal cell 20 shown in FIG. 2, a pair of opposing transparent substrates 21 includes an electrode 22 provided on an inner surface thereof, and an alignment film 23 that is printed thereon and subjected to an alignment process. ing. A liquid crystal material 25 is sealed in a space defined by the transparent substrate 21 and a seal layer 24 formed around the transparent substrate 21, and the space is used to make the pair of transparent substrates 21 face each other at a predetermined interval. A liquid crystal cell spacer 26 is formed on the substrate.
[0078]
In the liquid crystal cell 20 shown in FIG. 2, the liquid crystal cell spacer 26 is made of a cured product of the photosensitive alkali-soluble composition of the present invention. Here, the spacer 20 for liquid crystal cells is formed at a desired location in the liquid crystal cell 20 by a lithography technique using the photosensitive alkali-soluble composition of the present invention. Accordingly, it is possible to effectively prevent the occurrence of scratches on the pixel surface in the liquid crystal display device based on the shift, which has occurred in the conventional spherical spacer.
[0079]
(Reflector for liquid crystal display)
FIG. 3 is a cross-sectional view schematically showing a liquid crystal cell provided with a reflection plate for a liquid crystal display device according to an embodiment of the present invention.
[0080]
A reflection plate 30 for a liquid crystal display device shown in FIG. 3 includes a glass plate 34, a resin layer 33 provided on the glass plate 34 so as to have a substantially triangular cross section, and a reflection layer 32 covering the resin layer 33. The resin layer 33 is a cured product of the photosensitive alkali-soluble composition of the present invention. The liquid crystal display device reflector 30 is arranged on one surface side of the liquid crystal cell 20 via the liquid crystal display device color filter 10. Note that the liquid crystal cell 20 and the color filter 10 for the liquid crystal display device in FIG. 3 have the same configuration as described above.
[0081]
Since the reflection plate 30 for a liquid crystal display device has a cured product of the photosensitive alkalizing mold composition of the present invention having a high film hardness on one side, it is possible to display a clear image on the liquid crystal display device. Become.
[0082]
The photosensitive alkali-soluble composition of the present invention can be used as a cured product for electronic parts other than those described above, for example, an electronic element substrate for a liquid crystal display device in which a plurality of electrodes for switching liquid crystals are arranged. Thus, it is possible to provide an electronic element substrate for a liquid crystal display device, characterized in that the substrate is planarized with a cured product of the photosensitive alkali-soluble composition of the present invention. Specifically, a cured product of the photosensitive alkali-soluble composition of the present invention can be used as a TFT-LCD array electrode planarizing film provided on TFT elements arranged in an array on a substrate. . In addition to the above, it can be applied as a member of a flat panel display.
[0083]
【Example】
EXAMPLES Hereinafter, although the preferable Example of this invention is described in detail, this invention is not limited to these Examples.
[0084]
[Example of production of binder polymer]
(Binder polymer 1)
(A) 264 g of propylene glycol monomethyl ether acetate and 66 g of methyl lactate were weighed into a 1 L scale four-necked flask, and the liquid temperature was kept at 90 ° C. while bubbling with nitrogen.
(B) 240 g of propylene glycol monomethyl ether acetate, 60 g of methyl lactate, methacryloyloxytricyclo [5.2.1.0] in a 1 L beaker. ^2,6 ] 86.4 g of decane (manufactured by Hitachi Chemical Co., Ltd., FANCRYL FA-513M), 36.5 g of N-cyclohexylmaleimide, 106.7 g of 2-hydroxyethyl methacrylate, and 40.5 g of methacrylic acid were mixed and dissolved while bubbling nitrogen. It was. After confirming dissolution of N-cyclohexylmaleimide, 3 g of 2,2′-azobisisobutyronitrile was dissolved.
[0085]
(B) was continuously added dropwise to (A) over 3 hours, and then maintained at 90 ° C. for 3 hours. While maintaining at 90 ° C. for 3 hours, 0.6 g of 2,2′-azobisisobutyronitrile previously dissolved in 40 g of diethylene glycol dimethyl ether was reduced in order to reduce the residual monomer. Added. After reacting at 90 ° C. for a total of 6 hours, the liquid temperature was raised to 120 ° C., and then kept at 120 ° C. for 1 hour and naturally cooled to obtain a polymer (hereinafter referred to as “polymer 1”) solution. It was.
[0086]
In order to introduce an ethylenically unsaturated bond (methacryloyl group), 2-methacryloyloxyethyl isocyanate and a tin-based catalyst were added to the obtained solution and kept at 80 ° C. for 2 to 3 hours. Thus, a solution of a binder polymer (binder polymer 1) having an ethylenically unsaturated bond at the side chain and / or terminal was obtained. The 2-methacryloyloxyethyl isocyanate was adjusted to 1.5 mmol / g with respect to the polymer 1.
[0087]
(Binder polymer 2)
(A) 264 g of propylene glycol monomethyl ether acetate and 66 g of methyl lactate were weighed into a 1 L scale four-necked flask, and the liquid temperature was kept at 90 ° C. while bubbling with nitrogen.
(B) In a 1 L beaker, 240 g of propylene glycol monomethyl ether acetate, methyl lactate 60 g, benzyl methacrylate 86.4 g, N-cyclohexylmaleimide 36.5 g, 2-hydroxyethyl methacrylate 106.7 g, and methacrylic acid 40.5 g were mixed. And dissolved with nitrogen bubbling. After confirming dissolution of N-cyclohexylmaleimide, 3 g of 2,2′-azobisisobutyronitrile was dissolved. (B) was continuously added dropwise to (A) over 3 hours, and then kept at 90 ° C. for 3 hours.
[0088]
(B) was continuously added dropwise to (A) over 3 hours, and then maintained at 90 ° C. for 3 hours. While maintaining at 90 ° C. for 3 hours, 0.6 g of 2,2′-azobisisobutyronitrile previously dissolved in 40 g of diethylene glycol dimethyl ether was reduced in order to reduce the residual monomer. Added. After reacting at 90 ° C. for a total of 6 hours, the liquid temperature was raised to 120 ° C., and then kept at 120 ° C. for 1 hour and naturally cooled to obtain a polymer (hereinafter referred to as “polymer 2”) solution. It was.
[0089]
In order to introduce an ethylenically unsaturated bond (methacryloyl group), 2-methacryloyloxyethyl isocyanate and a tin-based catalyst were added to the obtained solution and kept at 80 ° C. for 2 to 3 hours. Thus, a solution of a binder polymer (binder polymer 2) having an ethylenically unsaturated bond at the side chain and / or terminal was obtained. The 2-methacryloyloxyethyl isocyanate was adjusted to 1.5 mmol / g with respect to the polymer 2.
[0090]
(Binder polymer 3)
(A) 285 g of propylene glycol monomethyl ether acetate was weighed into a 1 L-scale four-necked flask and the liquid temperature was maintained at 90 ° C. while bubbling with nitrogen.
(B) In a 1 L beaker, 300 g of propylene glycol monomethyl ether acetate, 141.8 g of benzyl methacrylate, 63.0 g of N-cyclohexylmaleimide, 63.0 g of 2-hydroxyethyl methacrylate, and 47.3 g of methacrylic acid were mixed and bubbled with nitrogen. Then, 3 g of 2,2′-azobisisobutyronitrile was dissolved.
[0091]
(B) was continuously added dropwise to (A) over 3 hours, and then maintained at 90 ° C. for 3 hours. While maintaining at 90 ° C. for 3 hours, 0.6 g of 2,2′-azobisisobutyronitrile previously dissolved in 40 g of diethylene glycol dimethyl ether was reduced in order to reduce the residual monomer. Added. After reacting at 90 ° C. for a total of 6 hours, the liquid temperature was raised to 120 ° C., and then kept at 120 ° C. for 1 hour and naturally cooled to obtain a solution of binder polymer 3.
[0092]
(Binder polymer 4)
(A) 285 g of propylene glycol monomethyl ether acetate was weighed in a 1 L-scale four-necked flask, and the liquid temperature was kept at 90 ° C. while bubbling with nitrogen.
(B) In a 1 L beaker, 300 g of propylene glycol monomethyl ether acetate, benzyl methacrylate 267.8 g, and 47.2 g of methacrylic acid were mixed and dissolved while bubbling nitrogen, and then 2,2′-azobisisobutyronitrile. 3 g was dissolved.
[0093]
(B) was continuously added dropwise to (A) over 3 hours, and then maintained at 90 ° C. for 3 hours. While maintaining at 90 ° C. for 3 hours, 0.6 g of 2,2′-azobisisobutyronitrile previously dissolved in 40 g of diethylene glycol dimethyl ether was reduced in order to reduce the residual monomer. Added. After reacting at 90 ° C. for a total of 6 hours, the liquid temperature was raised to 120 ° C., and then kept at 120 ° C. for 1 hour and naturally cooled to obtain a solution of binder polymer 4.
[0094]
The compositions and properties (viscosity and molecular weight) of the polymers 1 and 2 and the binder polymers 1 to 4 are summarized in Table 1 and Table 2 below.
[0095]
[Table 1]

[0096]
[Table 2]

[0097]
Subsequently, the photosensitive alkali-soluble type composition was produced using the binder polymers 1-4.
[0098]
Example 1
35 g of binder polymer 1 as component a of the photosensitive alkali-soluble composition, 9 g of pentaerythritol tetraacrylate as component b, benzophenone (1 g) and N, N′-tetraethyl-4,4′-diaminobenzophenone as component c (1 g), 54 g of propylene glycol monomethyl ether acetate as a component d was weighed and stirred using a stir bar and a stirrer until the component c was completely dissolved to obtain a solution of a photosensitive alkali-soluble composition.
[0099]
Example 2 Reference example 1 )
Example 2 was used in the same manner as in Example 1 except that binder polymer 2 and binder polymer 3 were used instead of binder polymer 1. Reference example 1 A solution of the photosensitive alkali-soluble composition was obtained.
[0100]
(Comparative Example 1)
A solution of the photosensitive alkali-soluble composition of Comparative Example 1 was obtained in the same manner as in Example 1 except that the binder polymer 4 was used in place of the binder polymer 1.
[0101]
Subsequently, the pattern shape formation time (minimum development time), the remaining film rate and total shrinkage after development, and the film hardness were evaluated by the following evaluation methods.
[0102]
(Evaluation method of pattern shape formation time (minimum development time))
Example 1 2. Reference example 1 The solution of the photosensitive alkali-soluble composition obtained in Comparative Example 1 was applied on a glass substrate (Corning, product name 7059) by spin coating, and further dried at 90 ° C. for 5 minutes. A film having a thickness of 2.0 μm was formed. The obtained film was passed through a negative mask and imaged with an ultrahigh pressure mercury lamp at 200 mJ / cm. ² Next, a developer 30 ± 1 was developed with an aqueous solution containing 0.5% by weight of polyoxyethylene nonylphenyl ether (trade name Nonal 912A, manufactured by Toho Chemical Co., Ltd.) and 0.3% by weight of potassium hydroxide. Development was performed for 60 seconds at a liquid temperature of ° C. The time (seconds) from the start of development by this method until the pattern was obtained was measured.
[0103]
(Evaluation method of residual film ratio and total shrinkage after development)
Example 1 2. Reference example 1 The solution of the photosensitive alkali-soluble composition obtained in Comparative Example 1 was spin-coated on a glass substrate (Corning Corporation, trade name 7059), and baked on a hot plate at 90 ° C. for 5 minutes. Then, exposure was performed under the same conditions as described above, and the film thickness was measured using a contact-type surface roughness measuring device (Dectak) (the obtained film thickness is defined as film thickness 1). Next, development was performed by the same method as described above, and after natural drying, the film thickness of the cured part was measured by irradiating light (the film thickness obtained was defined as film thickness 2). Following this, baking was performed in a dryer at 230 ° C. for 30 minutes, and the film thickness of the cured part was measured by irradiating light (the film thickness obtained was defined as film thickness 3). Then, the remaining film ratio and the total shrinkage ratio after development were calculated by dividing the film thickness 2 and the film thickness 3 by the film thickness 1.
[0104]
(Evaluation method of film hardness)
Example 1 2. Reference example 1 The solution of the photosensitive alkali-soluble composition obtained in Comparative Example 1 was applied onto a glass substrate by spin coating, and dried at 90 ° C. for 5 minutes to form a film having a thickness of about 5 μm. The obtained film was passed through a negative mask with an ultra-high pressure mercury lamp to 200 mJ / cm. ² Then, a pattern was formed. Next, development is performed for 60 seconds at a liquid temperature of 30 ± 1 ° C. using a developer composed of an aqueous solution containing polyoxyethylene nonylphenyl ether (0.5 wt%) and potassium hydroxide (0.3 wt%). And dried at 230 ° C. for 30 minutes to obtain a glass substrate provided with a cured product layer. And the hardness (Vickers hardness) of the cured film was evaluated using this board | substrate. The measurement of hardness (Vickers hardness) was performed under the conditions of a load of 20 kgf, a load speed of 20 kgf / second, and a holding time of 5 seconds using a MicroharadnessTester MHT-4 manufactured by Japan High-Tech.
[0105]
The evaluation results are shown in Table 3 below.
[Table 3]

[0106]
【The invention's effect】
As described above, according to the present invention, the alkali development time can be shortened without extremely increasing the resin acid value, and it is possible to improve the transparency and film hardness of the cured product. It is possible to provide a photosensitive alkali-soluble composition having reduced shrinkage based on the above. In addition, it is possible to provide a photosensitive element, a laminated substrate, a color filter for a liquid crystal display, a spacer for a liquid crystal cell, and a reflector for a liquid crystal display using the photosensitive alkali-soluble composition.
By using the photosensitive alkali-soluble composition of the present invention, a photosensitive spacer forming material for LCD, a color filter protective layer material, a contact hole forming material for LCD, an array electrode planarizing film forming material for TFT-LCD, A reflective layer forming material for a reflective or transflective LCD, various materials for a flat panel display, and the like can be produced.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view schematically showing an embodiment of a color filter for a liquid crystal display device of the present invention.
FIG. 2 is a cross-sectional view schematically showing a liquid crystal cell to which a liquid crystal cell spacer according to an embodiment of the present invention is applied.
FIG. 3 is a cross-sectional view schematically showing a liquid crystal cell provided with a reflection plate for a liquid crystal display device according to an embodiment of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 10 ... Color filter for liquid crystal display devices, 12 ... Glass substrate, R ... Red material layer, G ... Green material layer, B ... Blue material layer, 14 ... Light-shielding layer, 16 ... Protective film layer, 18 ... Conductive layer, 20 ... Liquid crystal cell, 21 ... Transparent substrate, 22 ... Electrode, 23 ... Alignment film, 24 ... Seal layer, 25 ... Liquid crystal substance, 26 ... Liquid crystal cell spacer, 30 ... Reflector for liquid crystal display device, 32 ... Reflective layer, 33 ... Resin layer, 34... Glass plate.

Claims (8)

A photosensitive alkali-soluble composition comprising a binder polymer, a monomer having one or more photopolymerizable unsaturated bonds, and a photoinitiator,
The binder polymer is
A cyclic monomer having at least one ring selected from the group consisting of a benzene ring, a cyclo ring, a bicyclo ring and a tricyclo ring and an ethylenically unsaturated bond;
A carboxyl monomer having a carboxyl group and an ethylenically unsaturated bond;
A hydroxy monomer having a hydroxyl group and an ethylenically unsaturated bond;
Having a skeleton obtained by polymerizing N-substituted maleimide;
Based on the total weight of the cyclic monomer, carboxyl monomer, hydroxy monomer and N-substituted maleimide, the content ratio of the cyclic monomer is 3 to 70% by weight, the content ratio of the carboxyl monomer is 5 to 50% by weight, content ratio of 5 to 70 wt% of the hydroxy monomers, Ri content ratio 5 to 50 wt% der of the N- substituted maleimide,
The photosensitive alkali-soluble composition, wherein the binder polymer is a polymer having an ethylenically unsaturated bond at a side chain and / or a terminal . The binder polymer is photosensitive alkali-soluble composition of claim 1 Symbol placement, wherein the weight-average molecular weight of polymer of from 3,000 to 200,000. A photosensitive material comprising: a support; and a photosensitive alkali-soluble composition layer comprising the photosensitive alkali-soluble composition according to claim 1 or 2 formed on the support. element. A laminated base material comprising: a base material; and a cured product layer formed of a cured product of the photosensitive alkali-soluble composition according to claim 1 or 2 formed on the base material. A transparent substrate, a plurality of color material layers formed so as to be two-dimensionally arranged on the transparent substrate, a light shielding layer formed on at least the color material layer on the transparent substrate, and the color material A color filter for a liquid crystal display device comprising: a protective film layer formed on the transparent substrate so as to cover the layer and the light shielding layer; and a conductor layer formed on the protective film layer,
The protective layer is, according to claim 1 or 2, characterized in that a cured product of the photosensitive alkali-soluble composition according to the color filter for a liquid crystal display device. A transparent substrate, a plurality of color material layers formed so as to be two-dimensionally arranged on the transparent substrate, a light shielding layer formed on at least the color material layer on the transparent substrate, and the color material A color filter for a liquid crystal display device comprising: a protective film layer formed on the transparent substrate so as to cover the layer and the light shielding layer; and a conductor layer formed on the protective film layer,
A color filter for a liquid crystal display device, wherein the color material layer comprises a cured product of a composition comprising the photosensitive alkali-soluble composition according to claim 1 or 2 and a color material. In a liquid crystal cell of a liquid crystal display device, a spacer for a liquid crystal cell inserted between the transparent substrates to hold transparent substrates arranged opposite to each other at a predetermined interval,
The said spacer for liquid crystal cells consists of the hardened | cured material of the photosensitive alkali-soluble type composition of Claim 1 or 2 , The spacer for liquid crystal cells characterized by the above-mentioned. A liquid crystal display reflector disposed on one side of a liquid crystal cell in a liquid crystal display,
The reflective plate for a liquid crystal display device includes a reflective layer and a resin layer provided on at least one side of the layer, and the resin layer is formed of the photosensitive alkali-soluble composition according to claim 1 or 2 . A reflector for a liquid crystal display device, comprising a cured product.

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