JP4161677B2 - Colored photosensitive resin composition - Google Patents

Description

【００４４】
また、ベンジリデン骨格を有する化合物としては、式（ＩＩ）で示される化合物が挙げられる。
【００４５】

【００４６】
式（Ｉ）および式（ＩＩ）において、Ｑ¹〜Ｑ³はそれぞれ独立に、水素原子、水酸基、アルキル基またはアルコキシル基を示す。
式（ＩＩ）において、Ｑ⁴はアルキル基であり、Ｘはシアノ基またはアルコキシカルボニル基である。これらの定義におけるアルキル基、アルコキシル基およびアルコキシカルボニル基は、それぞれ炭素数１〜６であることができる。また式（ＩＩ）において、Ｘがアルコキシカルボニル基の場合、二つのエステル部分は同一でも相異なってもよい。式（ＩＩ）で示される不飽和カルボン酸エステル化合物のうち、Ｘがシアノ基である化合物は、対応するベンズアルデヒド類とシアノ酢酸エステル類との反応により製造することができる。またＸがアルコキシカルボニル基である化合物は、対応するベンズアルデヒド類とマロン酸ジエステル類との反応により製造することができる。
【００４７】
本発明で用いるのに好適なベンジリデン骨格を有する化合物として、具体的には、ベンジリデンマロン酸ジアルキル、４−ヒドロキシ−３−メトキシベンジリデンマロン酸ジアルキル、４−ヒドロキシベンジリデンマロン酸ジアルキル、２，４−ジヒドロキシベンジリデンマロン酸ジアルキル、２−シアノ−３−（４−ヒドロキシ−３−メトキシフェニル）プロペン酸アルキルなどを挙げることができる。
ベンジリデン骨格を有する化合物（Ｆ）の使用量は、感光性樹脂組成物の固形中、通常０．００１〜３質量％、好ましくは０．０１〜２質量％、さらに好ましくは０．１〜１質量％である。ベンジリデン骨格を有する化合物（Ｆ）の使用量が、前記の基準で０．００１〜３質量％であると、解像度および抜け性が良好になる傾向があり、好ましい。
【００４８】
本発明の着色感光性樹脂組成物には、必要に応じて、充填剤、他の高分子化合物、顔料分散剤、密着促進剤、酸化防止剤、紫外線吸収剤、凝集防止材などの添加剤（Ｇ）を混合使用することもできる。
【００４９】
充填剤として具体的には、ガラス、シリカ、アルミナなどが、他の高分子化合物として具体的には、ポリビニルアルコール、ポリアクリル酸、ポリエチレングリコールモノアルキルエーテル、ポリフルオロアルキルアクリレートなどを用いることができる。
【００５０】
顔料分散剤としては、市販の顔料分散剤を用いることができ、例えば、シリコーン系、フッ素系、エステル系、カチオン系、アニオン系、ノニオン系、両性などの界面活性剤などが挙げられ、それぞれ単独でまたは２種以上を組み合わせて用いられる。前記の界面活性剤の例としては、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリエチレングリコールジエステル類、ソルビタン脂肪酸エステル類、脂肪酸変性ポリエステル類、３級アミン変性ポリウレタン類、ポリエチレンイミン類等のほか、商品名でKP（信越化学工業（株）製）、ポリフロー（共栄化学（株）製）、エフトップ（トーケムプロダクツ社製）、メガファックス（大日本インキ化学工業（株）製）、フロラード（住友スリーエム（株）製）、アサヒガード、サーフロン（以上、旭硝子（株）製）、ソルスパース（ゼネカ（株）製）、EFKA(EFKA CHEMICALS社製)、PB821（味の素（株）製）などが挙げられる。
【００５１】
密着促進剤として具体的には、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２−メトキシエトキシ）シラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−クロロプロピルメチルジメトキシシラン、３−クロロプロピルトリメトキシシラン、３−メタクリロイロキシプロピルトリメトキシシラン、３−メルカプトプロピルトリメトキシシランなどが挙げられる。
【００５２】
酸化防止剤として具体的には、２，２′−チオビス（４−メチル−６−tert−ブチルフェノール）、２，６−ジ−tert−ブチル−４−メチルフェノールなどが挙げられる。
【００５３】
紫外線吸収剤として具体的には、２−（３−tert−ブチル−２−ヒドロキシ−５−メチルフェニル）−５−クロロベンゾトリアゾール、アルコキシベンゾフェノンなどが挙げられる。
【００５４】
また凝集剤として具体的には、ポリアクリル酸ナトリウムなどが挙げられる。
【００５５】
本発明の着色感光性樹脂組成物は、例えば、以下のようにして調製することができる。すなわち、着色剤（Ａ）を予め溶剤（Ｅ）と混合し、着色材料の平均粒子径が０.２μm以下程度となるまで、ビーズミルなどを用いて分散させる。この際、必要に応じて顔料分散剤が使用され、またバインダー樹脂（Ｂ）の一部又は全部が配合されることもある。得られた分散液（以下、ミルベースということがある。）に、バインダー樹脂（Ｂ）の残り、光重合性化合物（Ｃ）および光重合開始剤（Ｄ）、必要に応じて使用されるその他の成分、さらには必要により追加の溶剤（Ｅ）を、所定の濃度となるように添加し、目的の着色感光性樹脂組成物を得る。
【００５６】
こうして調製された着色感光性樹脂組成物は、基板または先に形成された着色感光性樹脂組成物の固形分からなる層の上に塗布し、塗布された着色感光性樹脂組成物層から揮発成分を除去し、フォトマスクを介して前記の層を露光し、現像することによりパターンを形成することができる。
具体的には、例えば、着色感光性樹脂組成物を以下のようにして基材上に塗布し、光硬化および現像を行って、ブラックマトリックス又は着色画像とすることができる。
まず、この組成物を基板（通常はガラス）上にスピンコートし、プリベークすることにより溶剤を除去して、平滑な塗膜を得る。このときの塗膜の厚さは、およそ１〜３μｍ程度である。
このようにして得られた塗膜に、目的のブラックマトリックス又は画像を形成するためのネガマスクを介して紫外線を照射する。この際、露光部全体に均一に平行光線が照射され、かつマスクと基板の正確な位置合わせが行われるよう、マスクアライナーなどの装置を使用するのが好ましい。
さらにこの後、硬化の終了した塗膜を希アルカリ水溶液に接触させて非露光部を溶解させ、現像することにより、目的とするブラックマトリックス又は画像が得られる。現像後、必要に応じて１５０〜２３０℃で１０〜６０分程度のポストベークを施すこともできる。
【００５７】
パターニング露光後の現像に使用する現像液は、通常、アルカリ性化合物と界面活性剤を含む水溶液である。アルカリ性化合物は、無機および有機のアルカリ性化合物のいずれでもよい。
【００５８】
無機アルカリ性化合物の具体例としては、水酸化ナトリウム、水酸化カリウム、燐酸水素二ナトリウム、燐酸二水素ナトリウム、燐酸水素二アンモニウム、燐酸二水素アンモニウム、燐酸二水素カリウム、ケイ酸ナトリウム、ケイ酸カリウム、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、ホウ酸ナトリウム、ホウ酸カリウム、アンモニアなどが挙げられる。
【００５９】
また、有機アルカリ性化合物の具体例としては、テトラメチルアンモニウムヒドロキシド、２−ヒドロキシエチルトリメ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が挙げられる。これらの無機および有機アルカリ性化合物は、それぞれ単独で又は２種以上組み合わせて用いることができる。アルカリ現像液中のアルカリ性化合物の好ましい濃度は、０.０１〜１０質量％の範囲であり、より好ましくは０.０３〜５質量％である。
【００６０】
アルカリ現像液中の界面活性剤は、ノニオン系界面活性剤、アニオン系界面活性剤又はカチオン系界面活性剤のいずれでもよい。
【００６１】
ノニオン系界面活性剤の具体例としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアリールエーテル、ポリオキシエチレンアルキルアリールエーテル、その他のポリオキシエチレン誘導体、オキシエチレン／オキシプロピレンブロックコポリマー、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンアルキルアミンなどが挙げられる。
【００６２】
アニオン系界面活性剤の具体例としては、ラウリルアルコール硫酸エステルナトリウムやオレイルアルコール硫酸エステルナトリウムのような高級アルコール硫酸エステル塩類、ラウリル硫酸ナトリウムやラウリル硫酸アンモニウムのようなアルキル硫酸塩類、ドデシルベンゼンスルホン酸ナトリウムやドデシルナフタレンスルホン酸ナトリウムのようなアルキルアリールスルホン酸塩類などが挙げられる。
【００６３】
カチオン系界面活性剤の具体例としては、ステアリルアミン塩酸塩やラウリルトリメチルアンモニウムクロライドのようなアミン塩又は第四級アンモニウム塩などが挙げられる。
【００６４】
これらの界面活性剤は、それぞれ単独で用いることも、また２種以上組み合わせて用いることもできる。
アルカリ現像液中の界面活性剤の濃度は、通常０．０１〜１０質量％の範囲、好ましくは０．０５〜８質量％、より好ましくは０．１〜５質量％である。
【００６５】
以上のような感光性樹脂液の塗布、乾燥、得られる乾燥塗膜へのパターニング露光、そして現像という各操作を経て、感光性樹脂組成物中の着色材料の色に相当する画素又はブラックマトリックスが得られ、さらにこれらの操作を、カラーフィルタに必要とされる色の数だけ繰り返すことにより、カラーフィルタが得られる。すなわち、カラーフィルタは通常、ブラックマトリックス並びに、赤、緑および青の三原色画素を基板上に配置したものであるが、ある色に相当する着色材料を含む本発明の着色感光性樹脂組成物を用いて上記の操作を行うことにより、その色のブラックマトリックス又は画素を得て、他の色についても所望の色に相当する着色材料を含む本発明の着色感光性樹脂組成物を用いて同様の操作を行い、ブラックマトリックスおよび三原色画素を基板上に配置することができる。もちろん、ブラックマトリックスおよび三原色のうちいずれか一色、二色又は三色にのみ、本発明の感光性樹脂組成物を適用することも可能である。なお、遮光層であるブラックマトリックスは、例えば、クロム層などで形成されることもあるので、この場合にはブラックマトリックスの形成に本発明の着色感光性樹脂組成物を用いる必要はない。
【００６６】
そして、本発明の感光液を用いて製造されたカラーフィルタは、面内の膜厚差が小さく、例えば、１〜３μｍの膜厚において、面内膜厚差を０．１５μｍ以下、さらには０．０５μｍ以下とすることができる。したがって、こうして得られるカラーフィルタは、平滑性および透明性に優れたものであり、またこれをカラー液晶表示装置に組み込むことにより、優れた品質の液晶パネルを高い歩留りで製造することができる。
【００６７】
【実施例】
上記において、本発明の実施の形態について説明を行ったが、上記に開示された本発明の実施の形態は、あくまで例示であって、本発明の範囲はこれらの実施の形態に限定されない。本発明の範囲は、特許請求の範囲によって示され、さらに特許請求の範囲の記載と均等の意味および範囲内でのすべての変更を含むものである。以下、実施例によって本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。例中、含有量ないし使用量を表す％および部は、特にことわらないかぎり質量基準である。
【００６８】
本実施例で用いる成分は以下の通りで、以下、省略して表示することがある。
（ａ−１）Ｃ．Ｉ．ピグメントブルー１５：６
（ａ−２）Ｃ．Ｉ．ピグメントバイオレット２３
（ｂ−１）バインダー樹脂：メタクリル酸とベンジルメタクリレートとの共重合体〔メタクリル酸単位とベンジルメタクリレート単位との比は物質量比（モル比）で３０：７０、酸価は１１３、ポリスチレン換算重量平均分子量は２５，０００
（ｃ−１）光重合性化合物：ジペンタエリスリトールヘキサアクリレート(日本化薬（株）製 KAYARAD DPHA)
（ｃ−２）光重合性化合物：ジメチロール−トリシクロデカンジアクリレート（日本化薬（株）製 KAYARAD R-684）
（ｄ−１）光重合開始剤：２−メチル−２−モルホリノ−１−（４−メチルチオフェニル）プロパン−１−オン
（ｄ−２）光重合開始剤：２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）ブタン−１−オン
（ｄ−３）光重合開始剤：２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール(黒金化成（株）製)
（ｄ−４）光重合開始剤：ペンタエリスリトールテトラキスチオプロピオネート
（ｇ−１）光重合開始助剤：２，４−ジエチルチオキサントン
（ｇ−２）光重合開始助剤：４，４’−ビス（ジエチルアミノ）ベンゾフェノン
（ｈ）エポキシ化合物〔オルソクレゾールノボラック型エポキシ樹脂、「スミエポキシＥＳＣＮ−１９５ＸＬ−８０」（住友化学工業（株）製）〕
（ｆ）４−ヒドロキシ−３−メトキシベンジリデンマロン酸ジエチル
溶剤（Ｅ）：プロピレングリコールモノメチルエーテルアセテート
【００６９】
実施例１
〔着色感光性樹脂組成物の調製〕
（ａ−１） ６．８６９質量部
（ａ−２） ０．１０５質量部
ポリエステル系顔料分散剤 ２．０９４質量部
（ｂ−１） ６．２４２質量部
（ｃ−１） ４．１６２質量部
（ｄ−３） ０．８３２質量部
（ｄ−４） ０．２０８質量部
（ｇ−２） ０．４１６質量部
（ｈ） １．０４０質量部
（ｆ） ０．０２２質量部
（ｅ） ７８．０００質量部
を混合して着色感光性樹脂組成物１を得た。
【００７０】
２インチ角のコーニング社製＃１７３７ガラス基板を、中性洗剤、水 およびアルコールで順次洗浄してから乾燥した。このガラス基板上に、上記の感光性樹脂組成物１をスピンコートし、次にクリーンオーブン中、１００℃で３分間プリベークした。冷却後、このレジスト塗布基板と石英ガラス製フォトマスク（透過率を１〜１００％の範囲で階段状に変化させるパターンと１ミクロンから５０ミクロンまでのライン／スペースパターンを有するフォトマスク１、及び、線幅３μｍ、４μｍ、５μｍ、６μｍ、７μｍ、８μｍ、９μｍ、１０μｍ、２０μｍ、３０μｍ、４０μｍ、５０μｍおよび１００μｍの線状の着色パターンを形成するためのフォトマスク２）との間隔を１００μｍとし、ウシオ電機（株）製の超高圧水銀ランプを用いて大気雰囲気下、５０ｍＪ／ｃｍ^２または１５０ｍＪ／ｃｍ^２の露光量で光照射した。その後、非イオン系界面活性剤０．１２％と水酸化カリウム０．０４％を含む水系現像液に上記塗膜を２３℃で８０秒間浸漬して現像し、水洗後、２２０℃で２０分間ポストベークを行った。
（評価）
フォトマスク１を用いてパターンが形成できる感度は２ｍＪ／ｃｍ^２で、フォトマスク２では、５０ｍＪ／ｃｍ^２露光、１５０ｍＪ／ｃｍ^２露光ともに順テーパであった。
【００７１】
実施例２
〔着色感光性樹脂組成物の調製〕
（ａ−１） ６．８６９質量部
（ａ−２） ０．１０５質量部
ポリエステル系顔料分散剤 ２．０９４質量部
（ｂ−１） ６．７３１質量部
（ｃ−１） ２．２４４質量部
（ｃ−２） １．１２２質量部
（ｄ−３） ０．８９７質量部
（ｄ−４） ０．３３７質量部
（ｇ−２） ０．４４９質量部
（ｈ） １．１２２質量部
（ｆ） ０．０２２質量部
（ｅ） ７８．０００質量部
を混合して着色感光性樹脂組成物２を得た。
【００７２】
（評価）
着色感光性樹脂組成物２を用いる以外は実施例１と同様にして、パターンを形成した。フォトマスク１を用いてパターンが形成できる感度は３ｍＪ／ｃｍ^２で、フォトマスク２では、５０ｍＪ／ｃｍ^２露光、１５０ｍＪ／ｃｍ^２露光ともに順テーパであった。
【００７３】
比較例１
〔着色感光性樹脂組成物の調製〕
（ａ−１） ６．８６９質量部
（ａ−２） ０．１０５質量部
ポリエステル系顔料分散剤 ２．０９４質量部
（ｂ−１） ４．６４４質量部
（ｃ−１） ５．４５２質量部
（ｄ−１） １．２１２質量部
（ｇ−１） ０．６０６質量部
（ｈ） １．０１０質量部
（ｅ） ７８．０００質量部
を混合して着色感光性樹脂組成物３を得た。
【００７４】
（評価）
着色感光性樹脂組成物３を用いる以外は実施例１と同様にして、パターンを形成した。フォトマスク１を用いてパターンが形成できる感度は５０ｍＪ／ｃｍ^２であったが、フォトマスク２では、５０ｍＪ／ｃｍ^２露光ではパターンが残らなかった。１５０ｍＪ／ｃｍ^２露光ではパターンが形成されていたが、角ありテーパであった。
【００７５】
比較例２
〔着色感光性樹脂組成物の調製〕
（ａ−１） ６．８６９質量部
（ａ−２） ０．１０５質量部
ポリエステル系顔料分散剤 ２．０９４質量部
（ｂ−１） ６．２６４質量部
（ｃ−１） ４．１６２質量部
（ｄ−３） ０．８３２質量部
（ｄ−４） ０．２０８質量部
（ｇ−２） ０．４１６質量部
（ｈ） １．０４０質量部
（ｅ） ７８．０００質量部
を混合して着色感光性樹脂組成物４を得た。
【００７６】
（評価）
着色感光性樹脂組成物４を用いる以外は実施例１と同様にして、パターンを形成した。フォトマスク１を用いてパターンが形成できる感度は２ｍＪ／ｃｍ^２で、フォトマスク２では、５０ｍＪ／ｃｍ^２露光、１５０ｍＪ／ｃｍ^２露光ともにパターンが抜けなかった。
【００７７】
比較例３
〔着色感光性樹脂組成物の調製〕
（ａ−１） ６．８６９質量部
（ａ−２） ０．１０５質量部
ポリエステル系顔料分散剤 ２．０９４質量部
（ｂ−１） ６．７５３質量部
（ｃ−１） ２．２４４質量部
（ｃ−２） １．１２２質量部
（ｄ−３） ０．８９７質量部
（ｄ−４） ０．３３７質量部
（ｇ−２） ０．４４９質量部
（ｈ） １．１２２質量部
（ｅ） ７８．０００質量部
を混合して着色感光性樹脂組成物５を得た。
【００７８】
（評価）
着色感光性樹脂組成物５を用いる以外は実施例１と同様にして、パターンを形成した。フォトマスク１を用いてパターンが形成できる感度は５ｍＪ／ｃｍ^２で、フォトマスク２では、５０ｍＪ／ｃｍ^２露光では順テーパであったが、１５０ｍＪ／ｃｍ^２露光ではパターンが抜けなかった。
【００７９】
【発明の効果】
本発明の着色感光性樹脂組成物は、感度に優れたものである。また、本発明の着色感光性樹脂組成物を用いて得られる着色画素は、パターン形状に優れる。したがって、本発明の着色感光性樹脂組成物を顔料分散レジストとして使用し、カラーフィルタを作製する場合、生産性に優れ、かつ高品質なカラーフィルタを得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photosensitive resin composition that is widely used in ultraviolet curable inks, photoresists, and the like, and in particular, a colored image (hereinafter referred to as a pixel) used in a color liquid crystal display device, an image sensor, or the like. In particular, the present invention relates to a colored photosensitive resin composition suitable for a resist for forming the above.
[0002]
[Prior art]
A color filter in a color liquid crystal display device or an image sensor is usually manufactured by forming red, green, and blue three primary color pixels on a substrate such as glass or a silicon wafer. A black matrix is usually provided in order to shield light between these pixels. In order to form the pixels of each color, a resist solution containing a pigment corresponding to each color is uniformly applied on a substrate on which a black matrix is formed by a spin coater, followed by heat drying (hereinafter referred to as pre-baking). The film is exposed to light, developed, and then heat-cured (hereinafter sometimes referred to as post-baking) if necessary. These operations are necessary for color filters. By repeating for each color, an image of each color is obtained. As such a resist, many compositions containing a photopolymerizable monomer and a photopolymerization initiator are used together with a pigment and a binder resin. Also, a resist containing a black pigment may be used for forming the black matrix.
[0003]
Since the photopolymerization initiator used in such a resist affects the characteristics and quality necessary for producing a color filter, the photopolymerization initiator has high sensitivity, the surface smoothness, pattern shape, and resistance of the produced color filter. Those with high chemical properties and reliability are being studied. For example, a colored photosensitive resin composition using a triazine compound, a mixture of a triazine compound and an imidazole compound, a mixture of a triazine compound, an imidazole compound, an aminoacetophenone compound, or a benzophenone is proposed. (For example, refer to Patent Documents 1-3). Further, regarding the enhancement of sensitivity, a polyfunctional thiol compound and a mixture comprising at least one selected from a biimidazole compound, a titanocene compound, a triazine compound and an oxadiazole compound, 2-piperonyl-4,6-bis (trichloromethyl) -s- Triazines and further mixtures comprising the above triazine compounds, biimidazole compounds and hydrogen donors have been proposed (see, for example, Patent Documents 4 and 5). Although the color filter formed using the colored photosensitive resin composition containing these photopolymerization initiators has the above-mentioned advantages, there is a problem that the shape of the formed color pixel is deteriorated as a disadvantage. there were.
[0004]
On the other hand, the compound having a benzylidene skeleton used in the present invention absorbs light in the region of 550 nm or less and absorbs light in the vicinity thereof to prevent reflection from the substrate. It is known that it is used as a light-absorbing agent for preventing (see, for example, Patent Document 6). Further, benzylidene compounds are known to improve the temporal stability of a photosensitizer (see, for example, Patent Document 7). However, both of the above-mentioned two applications relate to a photoresist, and are removed after a pattern is formed using the photoresist and then etched, and are not left in the final structure.
On the other hand, it has not been conventionally known that a benzylidene compound contributes to creating a pattern having a good shape in pattern formation.
[0005]
[Patent Document 1]
JP-A-6-201913, page 2, left column, lines 2-5
[Patent Document 2]
JP-A-6-324484, page 2, left column, lines 2-7
[Patent Document 3]
JP-A-7-261014, page 2, left column, lines 2-7
[Patent Document 4]
Japanese Patent Application Laid-Open No. 10-253815, page 2, left column, line 2-10
[Patent Document 5]
JP 2000-221675, page 2, left column, lines 2 to 29
[Patent Document 6]
JP-A-2-269346, page 2, right column, lines 9-13
[Patent Document 7]
JP-A-11-119425, page 2, right column, lines 15-21
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a colored photosensitive resin composition having a good shape and capable of producing a colored pixel pattern having a good shape, a method for forming a colored pixel pattern having a good shape, a color filter including a colored pixel pattern having a good shape, and a good shape An object of the present invention is to provide a liquid crystal display device having a color filter including a colored pixel pattern.
[0007]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that a colored photosensitive resin composition containing a specific photopolymerization initiator can solve the above-described problems, and have reached the present invention.
That is, the present invention contains a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E), and a compound (F) having a benzylidene skeleton. And the compound (F) having a benzylidene skeleton is diethyl 4-hydroxy-3-methoxybenzylidenemalonate The colored photosensitive resin composition, the colored photosensitive resin composition is applied onto a substrate or a layer made of a solid content of the previously formed colored photosensitive resin composition, and the applied colored photosensitive resin is applied. A pattern forming method for removing volatile components from a resin composition layer, exposing the layer through a photomask, and developing, a color filter including the pattern formed by the method, and a liquid crystal using the color filter A display device is provided.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0009]
The colored photosensitive resin composition of the present invention is mainly used as a pigment dispersion resist, in which a colorant (A) that is usually a pigment is dispersed in a solvent (E), and a binder resin ( B), the photopolymerizable compound (C), the photopolymerization initiator (D), the compound (F) having a benzylidene skeleton, and optionally other additives are dissolved or dispersed.
[0010]
The colorant (A) is usually a pigment, and can be an organic pigment or an inorganic pigment usually used for a pigment dispersion resist. Examples of inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and other metal compounds. Oxides or mixed metal oxides may be mentioned. Specific examples of the organic pigment include compounds classified as Pigment in the Color Index (published by The Society of Dyers and Colorists). More specifically, compounds having the following color index (C.I.) numbers may be mentioned, but the invention is not limited to these.
[0011]
Specific examples of organic pigments and inorganic pigments include compounds classified as Pigment by Color Index (published by The Society of Dyers and Colorists). Specifically, for example, C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 53, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 86, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 125, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 137, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 148, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 173, C.I. I. Pigment yellow 194, C.I. I. Yellow pigments such as CI Pigment Yellow 214;
C. I. Pigment orange 13, C.I. I. Pigment orange 31, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 42, C.I. I. Pigment orange 43, C.I. I. Pigment orange 51, C.I. I. Pigment orange 55, C.I. I. Pigment orange 59, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 65, C.I. I. Pigment orange 71, C.I. I. Orange pigments such as CI Pigment Orange 73;
C. I. Pigment red 9, C.I. I. Pigment red 97, C.I. I. Pigment red 105, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment Red 264, C.I. I. Red pigments such as CI Pigment Red 265;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Blue pigments such as CI Pigment Blue 60;
C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Violet color pigments such as CI Pigment Violet 38;
C. I. Pigment green 7, C.I. I. Green pigments such as CI Pigment Green 36;
C. I. Pigment brown 23, C.I. I. Brown pigments such as CI Pigment Brown 25;
C. I. Pigment black 1, C.I. I. And black pigments such as CI Pigment Black 7. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment red 177, C.I. I. Pigment red 209, C.I. I. Pigment red 254, C.I. I. Pigment red violet 23, C.I. I. Pigment blue 15: 6 and C.I. I. It is preferable that at least one pigment selected from CI Pigment Green 36 is contained.
[0012]
These colorants (A) can be used alone or in combination of two or more. The colorant (A) is usually used in the range of 5 to 60% by mass, preferably 10 to 55% by mass, based on the total solid content in the colored photosensitive resin composition. If the content of the colorant (A) is in the range of 5 to 50 parts by mass based on the above criteria, the color density of the pixel is sufficient even if it is a thin film, and the non-pixel part omission is reduced during development. Therefore, there is a tendency that a residue is hardly generated, which is preferable.
[0013]
As the binder resin (B) used in the present invention, an acrylic copolymer can be used, and examples thereof include a carboxyl group-containing monomer and a copolymer with another monomer copolymerizable therewith.
[0014]
Examples of the carboxyl group-containing monomer include an unsaturated carboxylic acid having at least one carboxyl group in a molecule such as an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid such as an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid. Is mentioned. Here, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polyvalent carboxylic acid may be an acid anhydride thereof, specifically maleic anhydride, itaconic anhydride, citraconic anhydride and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester such as succinic acid mono (2-acryloyloxyethyl) or succinic acid mono (2-methacryloyloxy). Ethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends thereof, and may be, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, or the like. These carboxyl group-containing monomers can be used alone or in admixture of two or more.
[0015]
Examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, and o-methoxystyrene. , M-methoxystyrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl Aromatic vinyl compounds such as glycidyl ether and indene;
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl Methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl Acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxy Tyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, Toxipropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy- Unsaturated carboxylic esters such as 3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate;
2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl Unsaturated alkylaminoalkyl esters such as methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether;
Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamide;
Unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples include macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane. Can do. These monomers can be used alone or in admixture of two or more.
[0016]
The content of the carboxyl group-containing monomer unit in the copolymer is usually 10 to 50% by mass, preferably 15 to 40% by mass, and particularly preferably 25 to 40% by mass in terms of mass fraction. When the content of the carboxyl group-containing monomer unit is 10 to 50% by mass, the solubility in a developer is good, and a pattern tends to be formed accurately during development, which is preferable.
Examples of the acrylic polymer include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxy. Ethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl (meth) Acrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, ( (Meth) acrylic acid / 2-hydroxye (Meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer , (Meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / benzyl (meth) acrylate / N -Phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer (meth) acrylic acid / benzyl (meth) Acrylate / N-phenylmale De / styrene / such as glycerol mono (meth) acrylate copolymer. In addition, (meth) acrylate shows that it is an acrylate or a methacrylate.
[0017]
Among them, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl (meth) acrylate copolymer, ( A meth) acrylic acid / methyl (meth) acrylate / styrene copolymer is preferred.
[0018]
In the acrylic polymer, the weight average molecular weight in terms of polystyrene is usually 5,000 to 50,000, preferably 8,000 to 40,000, and particularly preferably 10,000 to 35,000. 000. When the molecular weight is 5,000 to 50,000, the coating film hardness is improved, the remaining film ratio is high, the solubility in the unexposed portion of the developer is good, and the resolution tends to be improved, which is preferable. In the acrylic polymer, the acid value is usually 50 to 150, preferably 60 to 140, particularly preferably 80 to 135. When the acid value is 50 to 150, the solubility in the developer is improved and the unexposed area is easily dissolved, and the sensitivity is increased so that the pattern of the exposed area remains during development and the remaining film ratio is improved. This is preferable. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration with an aqueous potassium hydroxide solution. .
[0019]
The binder resin is usually contained in the range of 5 to 90 mass%, preferably 10 to 70 mass%, based on the total solid content in the resist composition. When the binder resin (B) is 5 to 90% by mass based on the above-mentioned criteria, the solubility in the developer is sufficient, development residue is hardly generated on the non-pixel portion of the substrate, and the exposed portion during development It is preferable that the film thickness of the pixel portion is less likely to occur, and that the non-pixel portion is easily removed.
[0020]
The photopolymerizable compound (C) contained in the colored photosensitive resin composition of the present invention is a compound that can be polymerized by the action of light and a photopolymerization initiator described later. In addition to a monofunctional monomer, bifunctional, other It can be a polyfunctional monomer.
Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone and the like.
Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and bisphenol A. Bis (acryloyloxyethyl) ether, 3-methylpentanediol di (meth) acrylate, and the like.
Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( And (meth) acrylate. Of these, polyfunctional monomers having two or more functions are preferably used.
A photopolymerizable compound (C) is 1-60 mass parts normally with respect to 100 mass parts in total of binder resin (B) and a photopolymerizable compound (C) in a coloring photosensitive resin composition, Preferably it is 5-5. It is contained in the range of 50 parts by mass. When the content of the photopolymerizable compound (C) is in the range of 1 to 60 parts by mass based on the above criteria, the strength and smoothness of the pixel part tend to be favorable, which is preferable.
[0021]
Next, the photopolymerization initiator (D) contained in the colored photosensitive resin composition of the present invention contains at least one selected from the group consisting of a triazine compound, an acetophenone compound and a biimidazole compound and a polyfunctional thiol compound. Those are preferred. More preferably, a biimidazole compound and a polyfunctional thiol compound are included. The colored photosensitive resin composition containing the photopolymerization initiator (D) has higher sensitivity, and the film formed using the same has better pixel portion strength and surface smoothness. Furthermore, it is preferable to use a photopolymerization initiation assistant in combination because the resulting colored photosensitive resin composition has higher sensitivity, and the productivity in forming a color filter using this composition is improved.
[0022]
As a triazine compound contained in the photopolymerization initiator (D) of the colored photosensitive resin composition of the present invention, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5- Triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2 -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2 (4-Diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3 , 5-triazine and the like.
[0023]
Examples of the acetophenone compound contained in the photopolymerization initiator (D) of the colored photosensitive resin composition of the present invention include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzyldimethyl. Ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2 -Morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) And an oligomer of phenyl] propan-1-one.
[0024]
Furthermore, as a biimidazole compound contained in the photopolymerization initiator (D) of the colored photosensitive resin composition of the present invention, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′- Tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (see, for example, Patent Documents 8 and 9), 2,2 ′ -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) Biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′ , 5,5'-Tetra (Trialkoxy Phenyl) biimidazole (see, for example, Patent Documents 10 and 11), and an imidazole compound in which the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group (see, for example, Patent Document 12). Preferably, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole.
[0025]
The polyfunctional thiol compound is a compound having two or more thiol groups in the molecule, and an aliphatic polyfunctional thiol compound having a plurality of thiol groups in the aliphatic group is particularly preferable.
Examples of the aliphatic polyfunctional thiol used in the present invention include hexanedithiool, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bis Thioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis Thioglycolate, trishydroxyethyl tristhiopropionate, and other than these, thioglycolate of polyvalent hydroxy compound, thiopropionate and the like are preferable, Trimethylolpropane tris thiopropionate, trimethylolpropane tris thioglycolate and pentaerythritol tetrakis thiopropionate and the like, especially preferably pentaerythritol tetrakis thiopropionate.
[0026]
[Patent Document 8]
JP-A-6-75372, page 3, left column, lines 28-41
[Patent Document 9]
JP-A-6-75373, page 2, left column, lines 2 to 41
[Patent Document 10]
Japanese Examined Patent Publication No. 48-38403, page 2, left column, line 17-right column, line 44
[Patent Document 11]
JP, A, 62-174204, page 2, upper right column, line 12-page 3, upper left column, line 9
[Patent Document 12]
JP, 7-10913, A page 2 left column 12th line-26th line
[0027]
Moreover, as long as the effect of the present invention is not impaired, a photopolymerization initiator or the like usually used in this field can be used in combination. For example, benzoin, benzophenone, thioxanthone, anthracene, and others Of the initiator. More specifically, the following compounds can be mentioned, and these can be used alone or in combination of two or more.
[0028]
(A) Benzoin series
Benzoin,
Benzoin methyl ether,
Benzoin ethyl ether,
Benzoin isopropyl ether,
Benzoin isobutyl ether.
[0029]
(B) Benzophenone series
Benzophenone,
methyl o-benzoylbenzoate,
4-phenylbenzophenone,
4-benzoyl-4'-methyldiphenyl sulfide,
3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone,
2,4,6-trimethylbenzophenone and the like.
[0030]
(C) Thioxanthone series
2-isopropylthioxanthone,
4-isopropylthioxanthone,
2,4-diethylthioxanthone,
2,4-dichlorothioxanthone,
1-chloro-4-propoxythioxanthone and the like.
[0031]
(D) Anthracene series
9,10-dimethoxyanthracene,
2-ethyl-9,10-dimethoxyanthracene,
9,10-diethoxyanthracene,
2-ethyl-9,10-diethoxyanthracene and the like.
[0032]
(E) Other
2,4,6-trimethylbenzoyldiphenylphosphine oxide,
2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
10-butyl-2-chloroacridone,
2-ethylanthraquinone,
Benzyl,
9,10-phenanthrenequinone,
Camphorquinone,
Methyl phenylglyoxylate,
Titanocene compounds.
[0033]
Further, a photopolymerization initiator can be used in combination with a photopolymerization initiator. Examples of photopolymerization initiation assistants include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.
[0034]
Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4 ′ -Bis (ethylmethylamino) benzophenone is mentioned, among which 4,4'-bis (diethylamino) benzophenone is preferred.
[0035]
Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and the like. .
[0036]
Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
[0037]
The photopolymerization initiator may be used alone or in combination. Moreover, a commercially available thing can also be used as a photoinitiation adjuvant. Examples of commercially available photopolymerization initiation assistants include trade name “EAB-F” (manufactured by Hodogaya Chemical Co., Ltd.).
[0038]
Examples of the combination of the photopolymerization initiator and the photopolymerization initiation assistant in the colored photosensitive resin composition of the present invention include diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone, 2-methyl-2-morpholino-1- (4-Methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4,4′-bis (diethylamino) benzophenone Benzyldimethyl ketal / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one / 4,4′-bis ( Diethylamino) benzophenone, 1-hydroxycyclohexyl phenyl ketone / 4,4′-bis ( Ethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer / 4,4′-bis (diethylamino) benzophenone, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone, and the like, preferably 2-methyl-2-morpholino-1- (4- And a combination of methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone.
[0039]
In the photopolymerization initiator (D), the total amount of the photopolymerization initiator (D) is usually 0.1 to 40 parts by mass with respect to 100 parts by mass in total of the binder resin (B) and the photopolymerizable compound (C). The total amount of the photopolymerization initiation aid is preferably 0.1 to 50 parts by weight, and preferably 1 to 40 parts by weight, based on the above criteria.
When the total amount of the photopolymerization initiator (D) is in the above range, the colored photosensitive resin composition becomes highly sensitive, and the strength of the pixel portion formed using the colored photosensitive resin composition, The smoothness on the surface of the pixel tends to be good, which is preferable. In addition to the above, when the amount of the photopolymerization initiation assistant is within the above range, the sensitivity of the resulting colored photosensitive resin composition is further increased, and a color filter formed using the colored photosensitive resin composition The productivity tends to be improved.
[0040]
As the solvent (E), various solvents used in this field can be used. Specific examples of the solvent (E) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether;
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;
Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate;
Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone;
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin;
Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate;
and cyclic esters such as γ-butyrolactone. Of these, propylene glycol monomethyl ether acetate is preferable.
[0041]
These solvents (E) can be used alone or in combination of two or more.
The usage-amount of a solvent (E) is 60-90 mass% normally with respect to the whole coloring photosensitive resin composition containing it, Preferably it is 70-85 mass%. When the content of the solvent (E) is in the range of 60 to 90% by mass based on the above criteria, the coating property tends to be good, which is preferable.
[0042]
Examples of the benzylidene skeleton of the compound (F) having a benzylidene skeleton used in the present invention include structures represented by the formula (I).
[0043]

[0044]
Examples of the compound having a benzylidene skeleton include compounds represented by the formula (II).
[0045]

[0046]
In formula (I) and formula (II), Q ¹ ~ Q ^Three Each independently represents a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxyl group.
In formula (II), Q ^Four Is an alkyl group, and X is a cyano group or an alkoxycarbonyl group. The alkyl group, alkoxyl group and alkoxycarbonyl group in these definitions can each have 1 to 6 carbon atoms. In the formula (II), when X is an alkoxycarbonyl group, the two ester moieties may be the same or different. Of the unsaturated carboxylic acid ester compounds represented by the formula (II), a compound in which X is a cyano group can be produced by a reaction between a corresponding benzaldehyde and a cyanoacetic acid ester. A compound in which X is an alkoxycarbonyl group can be produced by reacting a corresponding benzaldehyde with malonic acid diesters.
[0047]
Specific examples of the compound having a benzylidene skeleton suitable for use in the present invention include benzylidene malonate dialkyl, 4-hydroxy-3-methoxybenzylidene malonate dialkyl, 4-hydroxybenzylidene malonate dialkyl, 2,4-dihydroxy. Examples include dialkyl benzylidene malonate and alkyl 2-cyano-3- (4-hydroxy-3-methoxyphenyl) propenoate.
The usage-amount of the compound (F) which has a benzylidene skeleton is 0.001-3 mass% normally in solid of the photosensitive resin composition, Preferably it is 0.01-2 mass%, More preferably, it is 0.1-1 mass. %. When the amount of the compound (F) having a benzylidene skeleton is 0.001 to 3% by mass on the basis of the above, it tends to improve the resolution and detachability, which is preferable.
[0048]
In the colored photosensitive resin composition of the present invention, if necessary, additives such as fillers, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation materials ( G) can also be used in combination.
[0049]
Specific examples of the filler include glass, silica, and alumina, and specific examples of other polymer compounds include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. .
[0050]
As the pigment dispersant, commercially available pigment dispersants can be used, and examples thereof include surfactants such as silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, non-ionic, and amphoteric, Or a combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), Megafax (manufactured by Dainippon Ink & Chemicals, Inc.) ), FLORARD (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Geneca Corporation), EFKA (manufactured by EFKA CHEMICALS), PB821 (manufactured by Ajinomoto Co., Inc.) ) And the like.
[0051]
Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Examples include ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.
[0052]
Specific examples of the antioxidant include 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, and the like.
[0053]
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.
[0054]
Specific examples of the flocculant include sodium polyacrylate.
[0055]
The colored photosensitive resin composition of the present invention can be prepared, for example, as follows. That is, the colorant (A) is preliminarily mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the coloring material is about 0.2 μm or less. At this time, a pigment dispersant is used as necessary, and a part or all of the binder resin (B) may be blended. In the obtained dispersion (hereinafter sometimes referred to as mill base), the remainder of the binder resin (B), the photopolymerizable compound (C) and the photopolymerization initiator (D), and other used as necessary Ingredients and, if necessary, an additional solvent (E) are added so as to have a predetermined concentration to obtain a desired colored photosensitive resin composition.
[0056]
The colored photosensitive resin composition thus prepared is applied onto a substrate or a layer made of a solid content of the colored photosensitive resin composition previously formed, and volatile components are applied from the applied colored photosensitive resin composition layer. The pattern can be formed by removing, exposing the layer through a photomask, and developing.
Specifically, for example, a colored photosensitive resin composition can be applied onto a substrate as described below, and photocured and developed to form a black matrix or a colored image.
First, the composition is spin-coated on a substrate (usually glass), and the solvent is removed by pre-baking to obtain a smooth coating film. At this time, the thickness of the coating film is about 1 to 3 μm.
The coating film thus obtained is irradiated with ultraviolet rays through a target black matrix or a negative mask for forming an image. At this time, it is preferable to use an apparatus such as a mask aligner so that parallel light rays are uniformly irradiated on the entire exposure portion and the mask and the substrate are accurately aligned.
Further, after this, the cured coating film is brought into contact with a dilute alkaline aqueous solution to dissolve the non-exposed portion and developed to obtain the intended black matrix or image. After the development, post-baking can be performed at 150 to 230 ° C. for about 10 to 60 minutes as necessary.
[0057]
The developer used for development after patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or organic alkaline compound.
[0058]
Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, Examples thereof include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia.
[0059]
Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Etc. These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The preferable concentration of the alkaline compound in the alkaline developer is in the range of 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.
[0060]
The surfactant in the alkaline developer may be any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.
[0061]
Specific examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Examples thereof include oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.
[0062]
Specific examples of anionic surfactants include higher alcohol sulfate salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.
[0063]
Specific examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride.
[0064]
These surfactants can be used alone or in combination of two or more.
The concentration of the surfactant in the alkali developer is usually in the range of 0.01 to 10% by mass, preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass.
[0065]
The pixel or black matrix corresponding to the color of the coloring material in the photosensitive resin composition is subjected to operations such as application of the photosensitive resin liquid, drying, patterning exposure to the resulting dried coating film, and development. Further, by repeating these operations for the number of colors required for the color filter, a color filter is obtained. That is, the color filter is usually a black matrix and pixels of three primary colors of red, green and blue arranged on the substrate, but the colored photosensitive resin composition of the present invention containing a coloring material corresponding to a certain color is used. By performing the above operation, a black matrix or pixel of that color is obtained, and the same operation is performed using the colored photosensitive resin composition of the present invention containing the coloring material corresponding to the desired color for the other colors. And the black matrix and the three primary color pixels can be arranged on the substrate. Of course, it is also possible to apply the photosensitive resin composition of the present invention to only one, two or three of the black matrix and the three primary colors. In addition, since the black matrix which is a light shielding layer may be formed, for example by a chromium layer etc., in this case, it is not necessary to use the coloring photosensitive resin composition of this invention for formation of a black matrix.
[0066]
The color filter manufactured using the photosensitive solution of the present invention has a small in-plane film thickness difference. For example, in a film thickness of 1 to 3 μm, the in-plane film thickness difference is 0.15 μm or less, and further 0 .05 μm or less. Therefore, the color filter obtained in this way is excellent in smoothness and transparency, and an excellent quality liquid crystal panel can be manufactured with a high yield by incorporating it into a color liquid crystal display device.
[0067]
【Example】
Although the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and includes the meaning equivalent to the description of the claims and all modifications within the scope. EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.
[0068]
The components used in this example are as follows, and may be omitted below.
(A-1) C.I. I. Pigment Blue 15: 6
(A-2) C.I. I. Pigment Violet 23
(B-1) Binder resin: Copolymer of methacrylic acid and benzyl methacrylate [ratio of methacrylic acid unit and benzyl methacrylate unit is 30:70 by mass ratio (molar ratio), acid value is 113, polystyrene equivalent weight The average molecular weight is 25,000
(C-1) Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)
(C-2) Photopolymerizable compound: dimethylol-tricyclodecane diacrylate (KAYARAD R-684, manufactured by Nippon Kayaku Co., Ltd.)
(D-1) Photopolymerization initiator: 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one
(D-2) Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one
(D-3) Photopolymerization initiator: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (manufactured by Kurokin Kasei Co., Ltd.)
(D-4) Photopolymerization initiator: pentaerythritol tetrakisthiopropionate
(G-1) Photopolymerization initiation assistant: 2,4-diethylthioxanthone
(G-2) Photopolymerization initiation assistant: 4,4′-bis (diethylamino) benzophenone
(H) Epoxy compound [orthocresol novolac type epoxy resin, “SUMI Epoxy ESCN-195XL-80” (manufactured by Sumitomo Chemical Co., Ltd.)]
(F) Diethyl 4-hydroxy-3-methoxybenzylidenemalonate
Solvent (E): Propylene glycol monomethyl ether acetate
[0069]
Example 1
[Preparation of colored photosensitive resin composition]
(A-1) 6.869 parts by mass
(A-2) 0.105 parts by mass
Polyester pigment dispersant 2.094 parts by mass
(B-1) 6.242 parts by mass
(C-1) 4.162 parts by mass
(D-3) 0.832 parts by mass
(D-4) 0.208 parts by mass
(G-2) 0.416 parts by mass
(H) 1.040 parts by mass
(F) 0.022 parts by mass
(E) 78.000 parts by mass
Were mixed to obtain a colored photosensitive resin composition 1.
[0070]
A 2 inch square Corning # 1737 glass substrate was sequentially washed with a neutral detergent, water and alcohol and then dried. The photosensitive resin composition 1 was spin-coated on this glass substrate, and then prebaked at 100 ° C. for 3 minutes in a clean oven. After cooling, this resist-coated substrate and a quartz glass photomask (a photomask 1 having a pattern in which the transmittance is changed stepwise in the range of 1 to 100% and a line / space pattern from 1 micron to 50 microns, and The distance from the photomask 2) for forming linear colored patterns having a line width of 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm and 100 μm is set to 100 μm. 50 mJ / cm in an air atmosphere using an ultra-high pressure mercury lamp manufactured by Denki Co., Ltd. ² Or 150 mJ / cm ² It was irradiated with light at an exposure amount of. Thereafter, the coating film was immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide for 80 seconds at 23 ° C., developed, washed with water, and post-treated at 220 ° C. for 20 minutes. Bake was done.
(Evaluation)
The sensitivity with which the pattern can be formed using the photomask 1 is 2 mJ / cm. ² In the photomask 2, 50 mJ / cm ² Exposure, 150mJ / cm ² Both exposures were forward tapered.
[0071]
Example 2
[Preparation of colored photosensitive resin composition]
(A-1) 6.869 parts by mass
(A-2) 0.105 parts by mass
Polyester pigment dispersant 2.094 parts by mass
(B-1) 6.731 parts by mass
(C-1) 2.244 parts by mass
(C-2) 1.122 parts by mass
(D-3) 0.897 parts by mass
(D-4) 0.337 parts by mass
(G-2) 0.449 parts by mass
(H) 1.122 parts by mass
(F) 0.022 parts by mass
(E) 78.000 parts by mass
Were mixed to obtain a colored photosensitive resin composition 2.
[0072]
(Evaluation)
A pattern was formed in the same manner as in Example 1 except that the colored photosensitive resin composition 2 was used. The sensitivity with which the pattern can be formed using the photomask 1 is 3 mJ / cm. ² In the photomask 2, 50 mJ / cm ² Exposure, 150mJ / cm ² Both exposures were forward tapered.
[0073]
Comparative Example 1
[Preparation of colored photosensitive resin composition]
(A-1) 6.869 parts by mass
(A-2) 0.105 parts by mass
Polyester pigment dispersant 2.094 parts by mass
(B-1) 4.644 parts by mass
(C-1) 5.452 parts by mass
(D-1) 1.212 parts by mass
(G-1) 0.606 parts by mass
(H) 1.010 parts by mass
(E) 78.000 parts by mass
Were mixed to obtain a colored photosensitive resin composition 3.
[0074]
(Evaluation)
A pattern was formed in the same manner as in Example 1 except that the colored photosensitive resin composition 3 was used. The sensitivity with which the pattern can be formed using the photomask 1 is 50 mJ / cm. ² However, in the photomask 2, it is 50 mJ / cm. ² No pattern remained after exposure. 150 mJ / cm ² A pattern was formed by exposure, but it was cornered and tapered.
[0075]
Comparative Example 2
[Preparation of colored photosensitive resin composition]
(A-1) 6.869 parts by mass
(A-2) 0.105 parts by mass
Polyester pigment dispersant 2.094 parts by mass
(B-1) 6.264 parts by mass
(C-1) 4.162 parts by mass
(D-3) 0.832 parts by mass
(D-4) 0.208 parts by mass
(G-2) 0.416 parts by mass
(H) 1.040 parts by mass
(E) 78.000 parts by mass
Were mixed to obtain a colored photosensitive resin composition 4.
[0076]
(Evaluation)
A pattern was formed in the same manner as in Example 1 except that the colored photosensitive resin composition 4 was used. The sensitivity with which the pattern can be formed using the photomask 1 is 2 mJ / cm. ² In the photomask 2, 50 mJ / cm ² Exposure, 150mJ / cm ² The pattern did not come off with exposure.
[0077]
Comparative Example 3
[Preparation of colored photosensitive resin composition]
(A-1) 6.869 parts by mass
(A-2) 0.105 parts by mass
Polyester pigment dispersant 2.094 parts by mass
(B-1) 6.753 parts by mass
(C-1) 2.244 parts by mass
(C-2) 1.122 parts by mass
(D-3) 0.897 parts by mass
(D-4) 0.337 parts by mass
(G-2) 0.449 parts by mass
(H) 1.122 parts by mass
(E) 78.000 parts by mass
Were mixed to obtain a colored photosensitive resin composition 5.
[0078]
(Evaluation)
A pattern was formed in the same manner as in Example 1 except that the colored photosensitive resin composition 5 was used. The sensitivity with which the pattern can be formed using the photomask 1 is 5 mJ / cm. ² In the photomask 2, 50 mJ / cm ² The exposure was forward taper, but 150 mJ / cm ² The pattern was not lost by exposure.
[0079]
【The invention's effect】
The colored photosensitive resin composition of the present invention is excellent in sensitivity. Moreover, the colored pixel obtained using the colored photosensitive resin composition of this invention is excellent in a pattern shape. Therefore, when producing the color filter using the colored photosensitive resin composition of the present invention as a pigment dispersion resist, it is possible to obtain a color filter having excellent productivity and high quality.

Claims (8)

Colorant (A),
Binder resin (B),
Photopolymerizable compound (C),
Photopolymerization initiator (D),
A solvent (E) and a compound (F) having a benzylidene skeleton ,
A compound having a benzylidene skeleton (F) is 4-hydroxy-3-methoxy benzylidene malonate der Ru colored photosensitive resin composition. Colored solids in 100 parts by weight of the photosensitive resin composition, a compound having a benzylidene skeleton (F) a colored photosensitive resin composition according to claim 1, wherein the inclusion 0.001 mass%. The photopolymerization initiator (D) is a triazine compound, an acetophenone compound and coloring according to claim 1 or 2, wherein Ru photoinitiator der comprising at least one polyfunctional thiol compound selected from the group consisting of biimidazole compounds Photosensitive resin composition. The photopolymerization initiator (D) is, biimidazole compounds and a polyfunctional thiol compound and colored photosensitive resin composition according to any one of claims 1 to 3 Ru photoinitiator der including. Further, the colored photosensitive resin composition according to any one of claims 1-4 which contains a photopolymerization initiator auxiliary agent. The colored photosensitive resin composition according to any one of claims 1 to 5 , wherein the colored photosensitive resin composition according to any one of claims 1 to 5 is applied onto a substrate or a layer made of a solid content of the previously formed colored photosensitive resin composition. A method of forming a pattern in which a volatile component is removed from a physical layer, the layer is exposed through a photomask, and developed. A color filter comprising a pattern formed by the method according to claim 6 . A liquid crystal display device using the color filter according to claim 7 .