JP7846894B2 - 感光性樹脂組成物及び表示装置 - Google Patents
感光性樹脂組成物及び表示装置Info
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- JP7846894B2 JP7846894B2 JP2022091720A JP2022091720A JP7846894B2 JP 7846894 B2 JP7846894 B2 JP 7846894B2 JP 2022091720 A JP2022091720 A JP 2022091720A JP 2022091720 A JP2022091720 A JP 2022091720A JP 7846894 B2 JP7846894 B2 JP 7846894B2
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- C—CHEMISTRY; METALLURGY
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
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- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
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- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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- H10K59/122—Pixel-defining structures or layers, e.g. banks
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Description
ダーを含むことによって、現像時における残渣を改善し、メルティングフローを改善でき、高いテーパー角度を有するパターン層を形成できる感光性樹脂組成物を提供することができる。
また、前記R、R’、R”及びR’”はそれぞれ独立して、1~20の炭素数を有するアルキル基、1~20の炭素数を有するアルケニル基、6~30の炭素数を有するアリール基、3~30の炭素数を有するヘテロ環基であり得、例えば、前記アリール基は、フェニル、ビフェニル、ナフタレン、アントラセン又はフェナントレンであり得、前記ヘテロ環基は、ピロール、フラン、チオフェン、ピラゾール、イミダゾール、トリアゾール、ピリジン、ピリミジン、ピリダジン、ピラジン、トリアジン、インドール、ベンゾフラン、キナゾリン又はキノキサリンであり得る。例えば、前記置換されたフルオレニル基及びフルオレニレン基はそれぞれ、9,9-ジメチルフルオロN、9,9-ジフェニルフルオロN及び9,9’-スピロビ[9H-フルオレン]の1価官能基又は2価官能基であり得る。
本出願で使われる用語“環”は、単一環及び多環を含み、炭化水素環はもとより、少なくとも一つのヘテロ原子を含むヘテロ環を含み、芳香族及び非芳香族環を含むことができる。
ここで、aが0である場合、置換基R1は不存在し、aが1である場合、一つの置換基R1は、ベンゼン環を形成する炭素のいずれか一つの炭素に結合し、aが2又は3である場合、それぞれ、次のように結合し、この時、R1は相互に同一でも異なってもよく、aが4~6の整数である場合、これと類似の方式でベンゼン環の炭素に結合し、一方、ベンゼン環を形成する炭素に結合した水素の表示は省略できる。
(化学式6の9,9-Bis[4-(glycidyloxy)phenyl]fluorineの製造)
9,9’-ビスフェノールフルオレン20g(Sigma aldrich社)、グリシジルクロリド(Sigma aldrich社)8.67g、無水炭酸カリウム30gをジメチルホルムアミド100mlと蒸留管が備えられている300ml三口丸底フラスコに入れ、80℃に昇温して4時間反応後に温度を25℃に下げて反応液を濾過後、濾過液を1000ml水に撹拌して滴加後に、析出された粉末を濾過して水で洗浄して40℃で減圧乾燥させ、化学式6の9,9-ビス[4-(グリシジロキシ)フェニル]フルオリンを25g得た。得られた粉末は、HPLCで純度分析の結果、98%の純度を示した。
(下記化学式7の低分子量カルド系バインダー樹脂の製造:A-1)
合成例1で得た化合物1 25g(54mmol)、アクリル酸8g(大井化金社)、ベンジルトリエチルアンモニウムクロリド0.2g(大井化金社)、ヒドロキノン0.2g(大井化金社)をプロピレングリコールメチルエーテルアセテート52g(Sigma aldrich社)と蒸留管が備えられている300ml三口丸底フラスコに入れて110℃で6時間撹拌した。反応終了後、ビフェニルテトラカルボキシル酸二無水物8g(Mitsubishi Gas社)、テトラヒドロフタル酸1.8g(Sigma aldrich社)を追加後、さらに110℃で6時間撹拌した。反応終了後、反応液を回収して分析した結果、重量平均分子量4,500の化学式7のような構造の固形分45%であるカルド系バインダー樹脂が得られた。
前記合成例1と同一に実験して得た化合物1 25g(54mmol)、アクリル酸8g(大井化金社)、ベンジルトリエチルアンモニウムクロリド0.2g(大井化金社)、ヒドロキノン0.2g(大井化金社)をプロピレングリコールメチルエーテルアセテート52g(Sigma aldrich社)と蒸留管が備えられている300ml三口丸底フラスコに入れて110℃で6時間撹拌した。反応終了後、ビフェニルテトラカルボキシル酸二無水物10g(Mitsubishi Gas社)、テトラヒドロフタル酸0.8g(Sigma aldrich社)を追加後、さらに110℃で6時間撹拌した。反応終了後、反応液を回収して分析した結果、重量平均分子量8,500の上記化学式7のような構造の固形分44%であるカルド系バインダー樹脂が得られた。
合成例4(化合物1-1’:6-(Trimethoxysilyl)-1-hexanethiolの製造)
シラン24g(0.1mol)とナトリウムメトキシド(Aldrich社)8g(0.15mol)、硫化水素THF溶液(0.8M濃度)187ml(0.15mol)、メタノール100mlをオートクレーブに入れて100℃で2時間反応を行った。反応液を冷却後、常温でメタノール中の塩化水素(1.25M濃度)100mlを30分間滴加し、生成された塩を濾過して除去後に減圧蒸留し、6-(トリメトキシシリル)-1-ヘキサンチオールが23g得られた。
合成例10-1:カルド系バインダー樹脂の製造(ポリマーB)
前記合成例1と同一に実験して得た化合物1 25g(54mmol)、アクリル酸8g(大井化金社)、ベンジルトリエチルアンモニウムクロリド0.2g(大井化金社)、ヒドロキノン0.2g(大井化金社)をプロピレングリコールメチルエーテルアセテート52g(Sigma aldrich社)と蒸留管が備えられている300ml三口丸底フラスコに入れて110℃で6時間撹拌した。反応終了後、ビフェニルテトラカルボキシル酸二無水物8.5g(Mitsubishi Gas社)、テトラヒドロフタル酸1.55g(Sigma aldrich社)を追加後、さらに110℃で6時間撹拌した。反応終了後、反応液を回収して分析した結果、重量平均分子量5,500の上記化学式7のような構造の固形分40%であるカルド系バインダー樹脂が得られた。
合成例10-1で得たカルド系バインダー溶液に6-(トリメトキシシリル)-1-ヘキサンチオール(Compound 1-1’)を8.1g(34mmol)入れて60℃に昇温後に4時間撹拌し、化学式9のようなシランが置換されたカルド系バインダー樹脂B-2が得られた。
合成例10-1で得たカルド系バインダー溶液に6-(トリエトキシシリル)-1-ヘキサンチオール(Compound 1-4’)を9.53g(34mmol)入れて60℃に昇温後に4時間撹拌し、化学式10のようなシランが置換されたカルド系バインダー樹脂B-3が得られた。
ポリマーC(ポリイミド/Mw:3,200)
(1)塗布及び塗膜形成段階
前述した黒色感光性樹脂組成物を、洗浄した10cm*10cmガラス基板に、スピンコーターを用いて1.5μm厚に塗布した後、100℃の温度で1分間加熱して溶剤を除去することによって、塗膜を形成する。
(2)露光段階
前記得られた塗膜に必要なパターン形成のために所定形態のマスクを介在した後、190nm~500nmの活性線を照射する。露光機はMA-6(SUSS社)、露光量は100mJ/cm2にして照射した。
(3)現像段階
前記露光段階に続いて、AZEM社AX 300 MIF現像液に25℃で1分間浸漬方法で現像後、水で洗浄して非露光部分を溶解、除去して露光部分だけを残存させることで、画像パターンを形成する。
(4)後処理段階
前記現像によって得られた画像パターンを、耐熱性、耐光性、密着性、耐クラック性、耐化学性、高強度、保持安定性などの面に優れたパターンを得るために、230℃で30分間ポストベークする。
以上のような段階を経て得られたパターンに対して、光学顕微鏡(Nicon)を用いてパターンイメージを図示し、SEM(Hitachi)を用いてパターンのテーパー角度を比較した。
flow)とテーパー角度の差が発生するためと見られる。
実施例4~実施例6:ポリマーA-1(低分子)とA-2(高分子)の比率による性能(テーパー角度)評価
Claims (10)
- (A)下記化学式1で表示される反復単位を含み、相互に重量平均分子量が異なる2種のカルド系バインダーと、(B)反応性不飽和化合物と、(C)顔料と、(D)開始剤と、(E)溶媒と、を含む感光性樹脂組成物:
1)”*”は、反復単位で結合が連結される部分を表し、
2)R1及びR2は、それぞれ独立して、重水素;ハロゲン基;C1~C20のアルキル基;からなる群から選択され、
3)R3~R6は、それぞれ独立して、水素;重水素;ハロゲン基;C1~C20のアルキル基;からなる群から選択され、
4)R7は、水素;重水素;C1~C20のアルキル基;からなる群から選択され、
5)m及びnは、それぞれ独立して、0~4の整数であり、
6)X2は、酸無水物残基又は酸二無水物残基であり、
7)X1は、下記化学式2で表示され、
8)Y1及びY2は、それぞれ独立して、水素;重水素;下記化学式3;及び下記化学式4からなる群から選ばれる:
9)R8及びR9は、それぞれ独立して、重水素;ハロゲン基;C1~C20のアルキル基;からなる群から選択され、
10)o及びpは、それぞれ独立して、0~4の整数であり、oが2以上の場合、隣接したR8は相互に結合して単一環又は多環の環を形成可能であり、pが2以上の場合、隣接したR9は相互に結合して単一環又は多環の環を形成可能である:
11)L1~L3は、それぞれ独立して、単一結合;C1~C60のアルキレン基;及びC6~C60のアリーレン基からなる群から選択され、
12)R10~R12は、それぞれ独立して、水素;重水素;ハロゲン基;C1~C20のアルキル基;からなる群から選択され、
13)Z1は、S又はOであり、
14)q及びrは、それぞれ独立して、0~3の整数であり、q+r=3であり、
前記2種のカルド系バインダーは、重量平均分子量が3000~4800である第1カルド系バインダー、及び重量平均分子量が7000~8800である第2カルド系バインダーを有する混合物で構成され、
前記第1カルド系バインダーの質量と前記第2カルド系バインダーの質量との和に対して前記第1カルド系バインダーを70重量%~80重量%で含む。 - 3種目のカルド系バインダーをさらに含み、
前記3種目のカルド系バインダーは、Y1及びY2の少なくとも一つが前記化学式4であり、重量平均分子量が5000~7000である、請求項1に記載の感光性樹脂組成物。 - 前記2種のカルド系バインダーは、Y1及びY2の少なくとも一つが前記化学式3である、請求項1に記載の感光性樹脂組成物。
- アクリルバインダー及びポリイミドバインダーの少なくとも一つをさらに含む、請求項1に記載の感光性樹脂組成物。
- 前記アクリルバインダーは、重量平均分子量が9000~13000であり、
前記ポリイミドバインダーは、重量平均分子量が1500~3900である、請求項4に記載の感光性樹脂組成物。 - 前記2種のカルド系バインダー(A)を1重量%~30重量%、前記反応性不飽和化合物(B)を1重量%~40重量%、前記顔料(C)を1重量%~30重量%、及び前記開始剤(D)を0.01重量%~10重量%で含む、請求項1に記載の感光性樹脂組成物。
- 前記開始剤は、光重合開始剤及びラジカル重合開始剤の少なくとも一つを含む、請求項1に記載の感光性樹脂組成物。
- 請求項1の感光性樹脂組成物の重合反応物を含むパターン層を備えた表示装置。
- 前記表示装置は、複数のサブピクセルを含み、
前記パターン層は、前記複数のサブピクセルを区分する画素定義層である、請求項8に記載の表示装置。 - 前記パターン層は、傾斜角が20°~40°である傾斜部を含む、請求項8に記載の表示装置。
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