JP6508911B2 - カラーフィルターの製造方法及びカラーフィルター - Google Patents
カラーフィルターの製造方法及びカラーフィルター Download PDFInfo
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- JP6508911B2 JP6508911B2 JP2014217289A JP2014217289A JP6508911B2 JP 6508911 B2 JP6508911 B2 JP 6508911B2 JP 2014217289 A JP2014217289 A JP 2014217289A JP 2014217289 A JP2014217289 A JP 2014217289A JP 6508911 B2 JP6508911 B2 JP 6508911B2
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical class OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
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- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- 239000005062 Polybutadiene Substances 0.000 description 1
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- 239000004793 Polystyrene Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
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- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
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- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
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- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000003431 cross linking reagent Substances 0.000 description 1
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 238000002845 discoloration Methods 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
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- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
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- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- XVTQAXXMUNXFMU-UHFFFAOYSA-N methyl 2-(3-oxo-2-pyridin-2-yl-1h-pyrazol-5-yl)acetate Chemical compound N1C(CC(=O)OC)=CC(=O)N1C1=CC=CC=N1 XVTQAXXMUNXFMU-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
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- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
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- 229920006122 polyamide resin Polymers 0.000 description 1
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- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
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- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 125000004076 pyridyl group Chemical group 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
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- 150000004053 quinones Chemical class 0.000 description 1
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- WPPDXAHGCGPUPK-UHFFFAOYSA-N red 2 Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=2C=3C4=CC=C5C6=CC=C7C8=C(C=9C=CC=CC=9)C9=CC=CC=C9C(C=9C=CC=CC=9)=C8C8=CC=C(C6=C87)C(C=35)=CC=2)C4=C1C1=CC=CC=C1 WPPDXAHGCGPUPK-UHFFFAOYSA-N 0.000 description 1
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- 238000007613 slurry method Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Optical Filters (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
- Liquid Crystal (AREA)
Description
本発明の製造方法は、感光性樹脂組成物を硬化させた第1の色のカラーフィルター部が形成されている基材に、第1の色とは異なる第2の色のカラーフィルター用の感光性樹脂組成物を塗布する工程を含む。色相の異なる複数の感光性樹脂組成物を使用してカラーフィルターを形成することは広く行われており、典型的には赤色、緑色、青色の3種類の感光性樹脂組成物を用いて画素が形成される。また、必要に応じて黄色、橙色、紫色、シアン色、マゼンタ色等も使用されるほか、画面の明るさの改善のために透明色の画素を付加することも行われている。更に、黒色ないし遮光性の感光性樹脂組成物を用いて、画面の周辺部や画素間の遮光のための構造物(ブラックマトリクスともいう)を形成することも一般的である。本発明で使用する感光性樹脂組成物の色相は特に制限されるものではなく、上述した色相以外であってもよい。
A−1〜3:合成例1〜3で合成した成分(50%溶液の固形分)
AX−1:合成例4で合成した成分(50%溶液の固形分)
B−1:ジペンタエリスリトールヘキサアクリレート
B−2:ペンタエリスリトールテトラアクリレート
C−1:1−[4−(フェニルスルファニル)フェニル]オクタン−1,2−ジオン=2−O−ベンゾイルオキシム
C−2:1−[9−エチル−6−(2−メチルベンゾイル)カルバゾール−3−イル]エタノン=O−アセチルオキシム
C−3:1−[7−(2−メチルベンゾイル)−9,9−ジプロピル−9H−フルオレン−2−イル]エタノン=O−アセチルオキシム (一般式(2)において、R1・R3・R4・R5・R6・R8=水素原子、R2・R11=メチル基、R7=2−メチルフェニル基、R9・R10=プロピル基である化合物)
D−1:微粒化されたピグメント・レッド177(BET法による比表面積70m2/g)
D−2:微粒化されたピグメント・レッド254(BET法による比表面積85m2/g)
D−3:微粒化されたピグメント・グリーン36(BET法による比表面積65m2/g)
D−4:微粒化されたピグメント・グリーン58(BET法による比表面積75m2/g)
D−5:微粒化されたピグメント・イエロー138(BET法による比表面積70m2/g)
D−6:微粒化されたピグメント・ブルー15:6(BET法による比表面積90m2/g)
D−7:微粒化されたピグメント・バイオレット23(BET法による比表面積50m2/g)
E−1:味の素ファインテクノ社製「アジスパーPB822」
S−1:メタクリル酸及びメタクリル酸ベンジルのランダム共重合体(酸価100mgKOH/g、重量平均分子量1万、プロピレングリコールモノメチルエーテルアセテートの35%溶液として合成されたものの固形分)
S−2:ダイセル社製「EHPE3150」
S−3:東レ・ダウコーニング社製「FZ−2122」
Z−1:プロピレングリコールモノメチルエーテルアセテート
Z−2:プロピレングリコールジアセテート
ここで、「A−」「B−」「C−」「D−」「E−」「Z−」はそれぞれ本発明のA、B、C、D、E、Z成分に該当することを示し、「S−」は必要に応じて用いられるその他の成分を示す。また「AX−」は本発明のA成分の構造を有しないことを示す。
一般式(1)で表されるビスフェノールフルオレン型エポキシ化合物(エポキシ当量255)510g、アクリル酸(エチレン性不飽和結合基含有カルボン酸)2.0モル、トリフェニルホスフィン(触媒)0.10モル、BHT(重合禁止剤)0.05モルをプロピレングリコールモノメチルエーテルアセテート255gに溶解させ、乾燥空気をバブリングさせながら100℃で反応させた。エポキシ基とカルボキシ基の反応率が99モル%に達したところでビフェニル−3,3′,4,4′−テトラカルボン酸二無水物(環状酸無水物)0.50モル及びシクロヘキセン−4,5−ジカルボン酸無水物(環状酸無水物)0.50モルを添加し、更に反応させた。赤外分光法で酸無水物基の消費を確認した後、プロピレングリコールモノメチルエーテルアセテートで希釈して室温に冷却し、A−1成分の固形分濃度50%溶液を得た。A−1成分の酸価は96mgKOH/g、重量平均分子量は4千であった。
一般式(1)で表されるビスフェノールフルオレン型エポキシ化合物(エポキシ当量315)630g、アクリル酸(エチレン性不飽和結合基含有カルボン酸)2.0モル、トリフェニルホスフィン(触媒)0.10モル、BHT(重合禁止剤)0.05モルをプロピレングリコールモノメチルエーテルアセテート315gに溶解させ、乾燥空気をバブリングさせながら100℃で反応させた。エポキシ基とカルボキシ基の反応率が99モル%に達したところでビフェニル−3,3′,4,4′−テトラカルボン酸二無水物(環状酸無水物)0.50モル及びシクロヘキセン−4,5−ジカルボン酸無水物(環状酸無水物)0.50モルを添加し、更に反応させた。赤外分光法で酸無水物基の消費を確認した後、プロピレングリコールモノメチルエーテルアセテートで希釈して室温に冷却し、A−2成分の固形分濃度50%溶液を得た。A−2成分の酸価は84mgKOH/g、重量平均分子量は6千であった。
一般式(1)で表されるビスフェノールフルオレン型エポキシ化合物(エポキシ当量255)510g、アクリル酸(エチレン性不飽和結合基含有カルボン酸)2.0モル、トリフェニルホスフィン(触媒)0.10モル、BHT(重合禁止剤)0.05モルをプロピレングリコールモノメチルエーテルアセテート255gに溶解させ、乾燥空気をバブリングさせながら100℃で反応させた。エポキシ基とカルボキシ基の反応率が99モル%に達したところでビフェニル−3,3′,4,4′−テトラカルボン酸二無水物(環状酸無水物)0.65モル及びシクロヘキセン−4,5−ジカルボン酸無水物(環状酸無水物)0.02モルを添加し、更に反応させた。赤外分光法で酸無水物基の消費を確認した後、プロピレングリコールモノメチルエーテルアセテートで希釈して室温に冷却し、A−3成分の固形分濃度50%溶液を得た。A−3成分の酸価は87mgKOH/g、重量平均分子量は9千であった。
ビスフェノールA型エポキシ化合物(エポキシ当量185)370g、アクリル酸(エチレン性不飽和結合基含有カルボン酸)2.0モル、トリフェニルホスフィン(触媒)0.10モル、BHT(重合禁止剤)0.05モルをプロピレングリコールモノメチルエーテルアセテート185gに溶解させ、乾燥空気をバブリングさせながら100℃で反応させた。エポキシ基とカルボキシ基の反応率が99モル%に達したところでビフェニル−3,3′,4,4′−テトラカルボン酸二無水物(環状酸無水物)0.50モル及びシクロヘキセン−4,5−ジカルボン酸無水物(環状酸無水物)0.50モルを添加し、更に反応させた。赤外分光法で酸無水物基の消費を確認した後、プロピレングリコールモノメチルエーテルアセテートで希釈して室温に冷却し、AX−1成分の固形分濃度50%溶液を得た。AX−1成分の酸価は114mgKOH/g、重量平均分子量は3千であった。
(カラーフィルター用感光性樹脂組成物の調製例1)
A−1成分の固形分濃度50%溶液(合成例1で得た溶液)10.0部、D−1成分6.0部、D−2成分6.0部、E−1成分3.0部、及びZ−1成分75.0部を混合し、冷却水で30℃以下の状態に保ちながら、直径0.3mmのジルコニアビーズを80%充填した内容積600mLのビーズミルで安定状態となるまで周速8.5m/sで分散して分散液を得た。次にA−1成分10.0部、B−1成分2.0部、B−2成分2.0部、C−1成分0.4部、S−2成分0.5部、S−3成分0.1部、Z−1成分20.0部及びZ−2成分15.0部を上記分散液に配合し、ミキサーを用いて室温で3時間撹拌混合した。最後に濾過精度0.6μmのメンブレンフィルターを用いて圧力0.05MPaで加圧濾過を行い、赤色のカラーフィルター用感光性樹脂組成物を得た。
調製例1の作製条件を表1に示すようにそれぞれ変更し、その他は調製例1と同様にして、調製例2〜9のカラーフィルター用感光性樹脂組成物の作製を行った。
(カラーフィルターの作製)
ガラス基板に保持したPENフィルム上に、調製例1のカラーフィルター用感光性樹脂組成物を硬化後の膜厚が1.0μmとなるような回転数でスピンコートし(工程(ア))、90℃のホットプレートで2分間乾燥させて(工程(イ))試験片を作製した。次に、カラーフィルターの画素のテストパターン形状を有するフォトマスクを介して照度30mW/cm2の超高圧水銀ランプで150mJ/cm2の紫外線(数値はi線基準)を照射し、画像露光を行った(工程(ウ))。その後、試験片を25℃の水酸化カリウム系アルカリ現像液(新日鉄住金化学社製「NSID」の100倍希釈液)で1分間処理し、更に水洗を行って画像を現像した(工程(エ))。最後に試験片に照度10mW/cm2の低圧水銀ランプで1500mJ/cm2の紫外線(数値は254nm基準)を照射し、ポスト露光を行った(工程(オ))。こうして赤色の色相のカラーフィルター用感光性樹脂組成物の硬化膜(1色目の画素)を得た。
実施例1で使用した調製例1の組成物を調製例4に、調製例2の組成物を調製例5に、調製例3の組成物を調製例6にそれぞれ変更し、その他は実施例1と同様にして、赤色・緑色・青色の鮮明な3色の画素を有するカラーフィルターを作製した。
実施例1で使用した調製例1の組成物を調製例7に、調製例2の組成物を調製例8に、調製例3の組成物を調製例9にそれぞれ変更し、その他は実施例1と同様にしてカラーフィルターの作製を行った。2色目の画素を形成しようとすると、調製例8の組成物の溶剤で1色目の画素(調製例7の組成物の硬化膜)が侵されて色が滲み出し、鮮明な画素を得ることができなくなった。画素の色相を形成する順番を変更し、1色目の画素を調製例8又は調製例9の組成物で形成しても、2色目の画素を形成する際に同様に色の滲み出しが観察され、鮮明な画素を得ることはできなかった。
Claims (4)
- 感光性樹脂組成物を硬化させた第1の色のカラーフィルター部が形成されている基材に、第1の色とは異なる第2の色のカラーフィルター用の感光性樹脂組成物を塗布し硬化させる工程を含む、カラーフィルターを製造する方法であって、前記感光性樹脂組成物は、(A)ビスフェノールフルオレン型エポキシ化合物とエチレン性不飽和結合基含有カルボン酸とを反応させたヒドロキシ基含有化合物に対して環状酸無水物を反応させて得られた化合物、(B)少なくとも1個のエチレン性不飽和結合を有する重合性モノマー、及び(C)光重合開始剤を含有し、前記基材の耐熱温度は150℃以下であり、前記基材の耐熱温度を超えない環境温度下で行われることを特徴とするカラーフィルターの製造方法。
- (ア)感光性樹脂組成物を基材に塗布する工程、(イ)感光性樹脂組成物を乾燥させる工程、(ウ)感光性樹脂組成物を画像露光する工程、(エ)感光性樹脂組成物を現像する工程、及び(オ)感光性樹脂組成物をポスト露光する工程を順に含む請求項1に記載のカラーフィルターの製造方法。
- 赤色、緑色及び青色の感光性樹脂組成物をそれぞれ使用する請求項1又は2に記載のカラーフィルターの製造方法。
- 請求項1〜3のいずれか1項に記載の方法で製造されたカラーフィルター。
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