CN103809373A - 感旋光性树脂组合物、其所形成的彩色滤光片及液晶显示装置 - Google Patents
感旋光性树脂组合物、其所形成的彩色滤光片及液晶显示装置 Download PDFInfo
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- CN103809373A CN103809373A CN201310511470.XA CN201310511470A CN103809373A CN 103809373 A CN103809373 A CN 103809373A CN 201310511470 A CN201310511470 A CN 201310511470A CN 103809373 A CN103809373 A CN 103809373A
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 12
- 239000011342 resin composition Substances 0.000 title abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 79
- 229920005989 resin Polymers 0.000 claims abstract description 79
- 150000001875 compounds Chemical class 0.000 claims abstract description 51
- 239000013522 chelant Substances 0.000 claims abstract description 32
- 239000000049 pigment Substances 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 230000003287 optical effect Effects 0.000 claims description 50
- 239000000178 monomer Substances 0.000 claims description 32
- 239000003513 alkali Substances 0.000 claims description 30
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 13
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001259 photo etching Methods 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 27
- 239000000758 substrate Substances 0.000 abstract description 22
- 229910052751 metal Inorganic materials 0.000 abstract description 10
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- 229910052782 aluminium Inorganic materials 0.000 description 17
- 238000012545 processing Methods 0.000 description 15
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 11
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- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
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- VBZYPJAXRLNOCG-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;oxepan-2-one Chemical compound O=C1CCCCCO1.OCC(CO)(CO)COCC(CO)(CO)CO VBZYPJAXRLNOCG-UHFFFAOYSA-N 0.000 description 7
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 125000005395 methacrylic acid group Chemical group 0.000 description 6
- 125000005920 sec-butoxy group Chemical group 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 5
- 229940093858 ethyl acetoacetate Drugs 0.000 description 5
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 5
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical compound [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 4
- 125000005595 acetylacetonate group Chemical group 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- YRMWCMBQRGFNIZ-UHFFFAOYSA-N ethyl 3-oxobutanoate;zirconium Chemical compound [Zr].CCOC(=O)CC(C)=O YRMWCMBQRGFNIZ-UHFFFAOYSA-N 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- SGNLDVYVSFANHW-UHFFFAOYSA-N pentane-2,4-dione;zirconium Chemical compound [Zr].CC(=O)CC(C)=O SGNLDVYVSFANHW-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- LCANECIWPMDASZ-UHFFFAOYSA-N 2-isocyanatoethanol Chemical class OCCN=C=O LCANECIWPMDASZ-UHFFFAOYSA-N 0.000 description 3
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N Lactic Acid Natural products CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 3
- PYHXGXCGESYPCW-UHFFFAOYSA-N diphenylacetic acid Chemical compound C=1C=CC=CC=1C(C(=O)O)C1=CC=CC=C1 PYHXGXCGESYPCW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- YMCDYRGMTRCAPZ-UHFFFAOYSA-N ethyl 2-acetyl-3-oxobutanoate Chemical compound CCOC(=O)C(C(C)=O)C(C)=O YMCDYRGMTRCAPZ-UHFFFAOYSA-N 0.000 description 3
- WIEGKKSLPGLWRN-UHFFFAOYSA-N ethyl 3-oxobutanoate;titanium Chemical compound [Ti].CCOC(=O)CC(C)=O WIEGKKSLPGLWRN-UHFFFAOYSA-N 0.000 description 3
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- 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 3
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- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
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- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
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- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
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- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
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- 238000004904 shortening Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- DWWMSEANWMWMCB-UHFFFAOYSA-N tribromomethylsulfonylbenzene Chemical compound BrC(Br)(Br)S(=O)(=O)C1=CC=CC=C1 DWWMSEANWMWMCB-UHFFFAOYSA-N 0.000 description 1
- GAJQCIFYLSXSEZ-UHFFFAOYSA-L tridecyl phosphate Chemical compound CCCCCCCCCCCCCOP([O-])([O-])=O GAJQCIFYLSXSEZ-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Materials For Photolithography (AREA)
Abstract
本发明是公开一种感旋光性树脂组合物。此感旋光性树脂组合物至少包含碱可溶性树脂(A)、含乙烯性不饱和基的化合物(B)、光引发剂(C)、有机溶剂(D)、颜料(E)及金属螯合物(F)。在省略预烤的像素制程中,于感旋光性树脂组合物中添加金属螯合物(F),所形成的像素与基板具有良好的密着性。本发明还提供该感旋光性树脂组合物形成的彩色滤光片,及包括该彩色滤光片的液晶显示装置。
Description
技术领域
本发明是有关一种感旋光性树脂组合物(photosensitive resin composition)及其所形成的彩色滤光片。特别是提供一种无预烤过程仍可保持高密着性的感旋光性树脂组合物。
背景技术
已知使用感旋光性树脂组合物用以制造彩色滤光片的制造方法,是于基板或已形成遮光层图案的基板上,将感旋光性树脂组合物涂布其上,先经预烤形成一干燥涂膜,再进行曝光、显影而形成预定的图案形状,最终得到各色像素。如日本特许公开第平2-144502及平3-53201号所揭示制造各色像素的方法。
其次,近年来关于彩色滤光片的技术领域中,除了使用低曝光量来缩短制程时间,因应彩色液晶显示装置对于高对比、高色纯度的要求,感旋光性树脂组合物中颜料所占的比例有越来越高的趋势。在此状况下,制造彩色滤光片时,上述显影制程后的水洗步骤结束阶段,像素图案层上会出现不规则形状的色斑,且此不规则形状的色斑会延迟后续进行的检查制程,而凸显生产效率下降的问题。
再者,近年来,为了更进一步缩短制程时间,除了通过减少曝光量外,省略预烤制程的制法也已在业界进行研究,因此可适用于不需预烤制程且仍可保持优异特性的感旋光性树脂组合物的开发已具有强烈的需求性。
上述特定的感旋光性树脂组合物如日本专利第特开2009-180949号案所揭露,其乃使用含有环氧丙烷基的化合物与阳离子聚合引发剂并用的感旋光性树脂组合物,除可改善不规则形状的色斑,并可省略预烤制程。
然而,上述的技术所制得的感旋光性树脂组合物在省略预烤的像素制程中,仍有所形成的像素与基板的密着性不佳的情况发生,而无法令业界所接受。
有鉴于此,亟需提出一种感旋光性树脂组合物及其应用,藉以改善已知的感旋光性树脂组合物于省略预烤的像素制程中密着性不佳的缺点。
发明内容
本发明的目的之一在于能基本上改善现有技术于省略预烤的像素制程中密着性不佳的缺点的感旋光性树脂组合物。
因此,本发明的一个方面是提供一种感旋光性树脂组合物,该感旋光性树脂组合物至少包含碱可溶性树脂(A)、含乙烯性不饱和基的化合物(B)、光引发剂(C)、有机溶剂(D)、颜料(E)及金属螯合物(F)。
本发明的另一方面是提供一种彩色滤光片,其是利用上述感旋光性树脂组合物经光刻处理后所形成的像素着色层。
本发明的感旋光性树脂组合物包括碱可溶性树脂(A)、含乙烯性不饱和基的化合物(B)、光引发剂(C)、有机溶剂(D)、颜料(E)及金属螯合物(F),以下析述之。
碱可溶性树脂(A)
本发明的碱可溶性树脂(A)是具有含羧酸基的第一不饱和单体(a-1)、含脂环结构的第二不饱和单体(a-2)及第三不饱和单体(a-3)的混合物的聚合反应产物。
上述的第一不饱和单体(a-1)是选自于丙烯酸、甲基丙烯酸、2-甲基丙烯酰乙氧基丁二酸酯、丁烯酸、α-氯丙烯酸、乙基丙烯酸、肉桂酸、马来酸、马来酸酐、富马酸、衣康酸、衣康酸酐、柠康酸、柠康酸酐,或它们的组合。较佳地,第一不饱和单体(a-1)是选自于丙烯酸、甲基丙烯酸、2-甲基丙烯酰乙氧基丁二酸酯或它们的组合。
以所述混合物总重为100重量份计,第一不饱和单体(a-1)的含量是5重量份~50重量份,较佳是8重量份~45重量份,更佳则是10重量份~40重量份。当第一不饱和单体(a-1)的含量为5重量份~50重量份时,所述感旋光性树脂组合物在进行曝光、显影等光刻制程时,会有较佳的显影性。
第二不饱和单体(a-2)是选自于具双环戊基基团(dicyclopentanyl group)的不饱和化合物、具双环戊烯基团(dicyclopentenyl group)的不饱和化合物或它们的组合。
具体来说,第二不饱和单体(a-2)可以是双环戊基丙烯酸酯、双环戊基乙氧基丙烯酸酯、双环戊烯基丙烯酸酯、双环戊烯基乙氧基丙烯酸酯、双环戊基甲基丙烯酸酯、双环戊基乙氧基甲基丙烯酸酯、双环戊烯基甲基丙烯酸酯、双环戊烯基乙氧基甲基丙烯酸酯或它们的组合。
以所述混合物总重为100重量份计,第二不饱和单体(a-2)的含量是1重量份~20重量份,较佳是3重量份~18重量份,更佳则是5重量份~15重量份。当第二不饱和单体(a-2)的含量为1重量份~20重量份时,所述感旋光性树脂组合物在经由光刻制程后,所形成的像素着色层具有较佳的耐热性。
所述第三不饱和单体(a-3)是选自于苯乙烯、α-甲基苯乙烯、乙烯基甲苯、对氯苯乙烯、二乙烯基苯、苯甲基甲基丙烯酸酯、苯甲基丙烯酸酯、苯基甲基丙烯酸酯、苯基丙烯酸酯、2-硝基苯基丙烯酸酯、4-硝基苯基丙烯酸酯、2-硝基苯甲基丙烯酸酯、2-硝基苯甲基甲基丙烯酸酯、2-硝基苯基甲基丙烯酸酯、2-氯苯基甲基丙烯酸酯、4-氯苯基甲基丙烯酸酯、2-氯苯基丙烯酸酯、4-氯苯基丙烯酸酯、苯氧基乙基甲基丙烯酸酯、苯氧基聚乙二醇丙烯酸酯、苯氧基聚乙二醇甲基丙烯酸酯、壬基苯氧基聚乙二醇丙烯酸酯、壬基苯氧基聚乙二醇甲基丙烯酸酯、氮-苯基马来酰亚胺、氮-邻-羟基苯基马来酰亚胺、氮-间-羟基苯基马来酰亚胺、氮-对-羟基苯基马来酰亚胺、氮-邻-甲基苯基马来酰亚胺、氮-间-甲基苯基马来酰亚胺、氮-对-甲基苯基马来酰亚胺、氮-邻-甲氧基苯基马来酰亚胺、氮-间-甲氧基苯基马来酰亚胺、氮-对-甲氧基苯基马来酰亚胺、邻-乙烯基苯酚、间-乙烯基苯酚、对-乙烯基苯酚、2-甲基-4-乙烯基苯酚、3-甲基-4-乙烯基苯酚、邻-异丙烯基苯酚、间-异丙烯基苯酚、对-异丙烯基苯酚、2-乙烯基-1-萘酚、3-乙烯基-1-萘酚、1-乙烯基-2-萘酚、3-乙烯基-2-萘酚、2-异丙烯基-1-萘酚、3-异丙烯基-1-萘酚、邻-甲氧基苯乙烯、间-甲氧基苯乙烯、对-甲氧基苯乙烯、邻-甲氧基甲基苯乙烯、间-甲氧基甲基苯乙烯、对-甲氧基甲基苯乙烯、邻-(乙烯基苯甲基)环氧丙基醚、间-(乙烯基苯甲基)环氧丙基醚、对-(乙烯基苯甲基)环氧丙基醚、茚、乙酰基萘、氮-环己基马来酰亚胺、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸仲丁酯、丙烯酸叔丁酯、丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、丙烯酸-3-羟基丙酯、丙烯酸-2-羟基丁酯、丙烯酸-3-羟基丁酯、丙烯酸-4-羟基丁酯、丙烯酸烯丙酯、丙烯酸三乙二醇甲氧酯、氮,氮-二甲基氨基丙烯酸乙酯、氮,氮-二乙基氨基丙烯酸丙酯、氮,氮-二丁基氨基丙烯酸丙酯、丙烯酸环氧丙基酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸仲丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基丙酯、甲基丙烯酸-3-羟基丙酯、甲基丙烯酸-2-羟基丁酯、甲基丙烯酸-3-羟基丁酯、甲基丙烯酸-4-羟基丁酯、甲基丙烯酸烯丙酯、甲基丙烯酸三乙二醇甲氧酯、甲基丙烯酸十二烷基酯、甲基丙烯酸十四烷基酯、甲基丙烯酸十六烷基酯、甲基丙烯酸十八烷基酯、甲基丙烯酸二十烷基酯、甲基丙烯酸二十二烷基酯、甲基丙烯酸氮,氮-二甲基氨基乙酯、氮,氮-二甲基氨基甲基丙烯酸丙酯、氮-异-丁基氨基甲基丙烯酸乙酯、甲基丙烯酸环氧丙基酯、乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、乙烯基甲醚、乙烯基乙醚、烯丙基环氧丙基醚、甲代烯丙基环氧丙基醚(methallyl glycidyl ether)、丙烯腈、甲基丙烯腈、α-氯丙烯腈、氰化亚乙烯、丙烯酰胺、甲基丙烯酰胺、α-氯丙烯酰胺、氮-羟乙基丙烯酰胺、氮-羟乙基甲基丙烯酰胺、1,3-丁二烯、异戊烯、氯化丁二烯或此等的一组合。其中,该第三不饱和单体(a-3)又以苯乙烯、α-甲基苯乙烯、苯基甲基丙烯酸酯、苯基丙烯酸酯、氮-苯基马来酰亚胺、氮-邻-羟基苯基马来酰亚胺、氮-间-羟基苯基马来酰亚胺、氮-对-羟基苯基马来酰亚胺、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸仲丁酯、丙烯酸叔丁酯、丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸仲丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基丙酯、甲基丙烯酸环氧丙基酯、乙酸乙烯酯、丙烯腈、甲基丙烯腈、1,3-丁二烯与异戊烯等为较佳。
以所述混合物总重100重量份计,第三不饱和单体(a-3)的含量是30重量份~94重量份,较佳是37重量份~89重量份,更佳是45重量份~85重量份。当第三不饱和单体(a-3)的含量为30重量份~94重量份时,所形成的彩色滤光片的像素着色层具有极佳耐溅镀性。
含乙烯性不饱和基的化合物(B)
本发明的含乙烯性不饱和基的化合物(B)是选自于一第一化合物(B-1)、一第二化合物(B-2)或它们的组合。
所述第一化合物(B-1)是由经己内酯改质的多元醇与(甲基)丙烯酸反应而得的(甲基)丙烯酸酯系化合物。
所述经己内酯改质的多元醇是由己内酯与具有4个官能基以上的多元醇反应而制得,其中,所述己内酯可以是γ-己内酯、δ-己内酯,或ε-己内酯,且以ε-己内酯为佳。所述具有4个官能基以上的多元醇可以是季戊四醇、二三羟甲基丙烷、二季戊四醇。较佳地,以具有4个官能基以上的多元醇的含量为1摩尔计,己内酯的含量范围为1~12摩尔。
所述第一化合物(B-1)是选自于季戊四醇己内酯改质的四(甲基)丙烯酸酯类化合物、二三羟甲基丙烷己内酯改质的四(甲基)丙烯酸酯类化合物、二季戊四醇己内酯改质的多(甲基)丙烯酸酯类化合物等,其中,所述二季戊四醇己内酯改质的多(甲基)丙烯酸酯类化合物可以是二季戊四醇己内酯改质的二(甲基)丙烯酸酯类化合物、二季戊四醇己内酯改质的三(甲基)丙烯酸酯类化合物、二季戊四醇己内酯改质的四(甲基)丙烯酸酯类化合物、二季戊四醇己内酯改质的五(甲基)丙烯酸酯类化合物、二季戊四醇己内酯改质的六(甲基)丙烯酸酯类化合物。
进一步地,上述的第一化合物(B-1)的结构可以式(I)表示:
式(I)中,R1及R2分别表示氢或甲基;m为1~2的整数;a为1~6的整数,b为0~5的整数,其中,a+b=2~6,较佳为a+b=3~6,更佳为a+b=5~6,最佳为a+b=6。
以所述碱可溶性树脂总重为100重量份计,第一化合物(B-1)的含量是5重量份~100重量份,较佳为8重量份~90重量份,更佳为10重量份~80重量份。藉由第一化合物(B-1)的己内酯结构,可以让液晶显示装置较无泡沫显示缺陷。当第一化合物(B-1)未使用时,显影性较差。
所述第二化合物(B-2)具有如式(II)所示的官能基:
式(II)中,R3表示氢或甲基。
所述第二化合物(B-2)可选自于丙烯酰胺、(甲基)丙烯酰吗啉、(甲基)丙烯酸-7-氨基-3,7-二甲基辛酯、异丁氧基甲基(甲基)丙烯酰胺、(甲基)丙烯酸异冰片基氧乙酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸-2-乙基己酯、乙基二甘醇(甲基)丙烯酸酯、叔辛基(甲基)丙烯酰胺、二丙酮(甲基)丙烯酰胺、(甲基)丙烯酸二甲氨基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸二环戊烯氧乙酯、(甲基)丙烯酸二环戊烯酯、氮,氮-二甲基(甲基)丙烯酰胺、(甲基)丙烯酸四氯苯酯、(甲基)丙烯酸-2-四氯苯氧基乙酯、(甲基)丙烯酸四氢糠酯、(甲基)丙烯酸四溴苯酯、(甲基)丙烯酸-2-四溴苯氧基乙酯、(甲基)丙烯酸-2-三氯苯氧基乙酯、(甲基)丙烯酸三溴苯酯、(甲基)丙烯酸-2-三溴苯氧基乙酯、(甲基)丙烯酸-2-羟乙酯、(甲基)丙烯酸-2-羟丙酯、乙烯基己内酰胺、氮-乙烯基皮酪烷酮、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸五氯苯酯、(甲基)丙烯酸五溴苯酯、聚单(甲基)丙烯酸乙二醇酯、聚单(甲基)丙烯酸丙二醇酯、(甲基)丙烯酸冰片酯、乙二醇二(甲基)丙烯酸酯、二(甲基)丙烯酸二环戊烯酯、三甘醇二丙烯酸酯、四甘醇二(甲基)丙烯酸酯、三(2-羟乙基)异氰酸酯二(甲基)丙烯酸酯、三(2-羟乙基)异氰酸酯三(甲基)丙烯酸酯、己内酯改质的三(2-羟乙基)异氰酸酯三(甲基)丙烯酸酯、三(甲基)丙烯酸三羟甲基丙酯、环氧乙烷(以下简称EO)改质的三(甲基)丙烯酸三羟甲基丙酯、环氧丙烷(以下简称PO)改质的三(甲基)丙烯酸三羟甲基丙酯、三甘醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、聚酯二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯(日本东亚合成株式会社制造的商品名为TO-1382的商品)、二季戊四醇四(甲基)丙烯酸酯、己内酯改质的二季戊四醇六(甲基)丙烯酸酯、EO改质的二季戊四醇六丙烯酸酯、己内酯改质的二季戊四醇五(甲基)丙烯酸酯、四(甲基)丙烯酸二三羟甲基丙酯、EO改质的双酚A二(甲基)丙烯酸酯、PO改质的双酚A二(甲基)丙烯酸酯、EO改质的氢化双酚A二(甲基)丙烯酸酯、PO改质的氢化双酚A二(甲基)丙烯酸酯、PO改质的甘油三丙酸酯、EO改质的双酚F二(甲基)丙烯酸酯、酚醛聚缩水甘油醚(甲基)丙烯酸酯。
较佳地,所述第二化合物(B-2)是选自于三丙烯酸三羟甲基丙酯、EO改质的三丙烯酸三羟甲基丙酯、PO改质的三丙烯酸三羟甲基丙酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇六丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇四丙烯酸酯、己内酯改质的二季戊四醇六丙烯酸酯、四丙烯酸二三羟甲基丙酯、PO改质的甘油三丙酸酯、日本东亚合成株式会社制造的商品名为TO-1382的商品或它们的组合。
以所述碱可溶性树脂总重为100重量份计,第二化合物(B-2)的含量是5重量份~400重量份,较佳为8重量份~350重量份,更佳为10重量份~300重量份,以让所述感旋光性树脂组合物呈现优异的显影性。
以所述碱可溶性树脂(A)总重为100重量份计,所述含乙烯性不饱和基的化合物(B)的含量是10重量份~500重量份,较佳为20重量份~450重量份,更佳为30重量份~400重量份,以让所述感旋光性树脂组合物具有良好的显影性。
光引发剂(C)
本发明的光引发剂(C)可选自于苯乙酮系化合物(acetophenone)、二咪唑系化合物(biimidazole)、酰肟系化合物(acyl oxime)或它们的组合。
上述的苯乙酮系化合物是选自于对二甲胺苯乙酮(p-dimethylamino-acetophenone)、α,α’-二甲氧基氧化偶氮苯乙酮(α,α’-dimethoxyazoxy-acetophenone)、2,2’-二甲基-2-苯基苯乙酮(2,2’-dimethyl-2-phenyl-acetophenone)、对甲氧基苯乙酮(p-methoxy-acetophenone)、2-甲基-1-(4-甲基硫代苯基)-2-吗啉代-1-丙酮[2-methyl-1-(4-methylthio phenyl)-2-morpholino-1-propanone]、2-苄基-2-氮,氮-二甲胺-1-(4-吗啉代苯基)-1-丁酮[2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone]。
上述的二咪唑系化合物是选自于2,2’-双(邻-氯苯基)-4,4’,5,5’-四苯基二咪唑[2,2’-bis(o-chlorophenyl)-4,4’,5,5’-tetraphenyl-biimidazole]、2,2’-双(邻-氟苯基)-4,4,5,5’-四苯基二咪唑[2,2’-bis(o-fluorophenyl)-4,4’,5,5’-tetraphenyl-biimidazole]、2,2’-双(邻-甲基苯基)-4,4’,5,5’-四苯基二咪唑[2,2’-bis(o-methyl phenyl)-4,4’,5,5’-tetraphenyl-biimidazole]、2,2’-双(邻-甲氧基苯基)-4,4’,5,5’-四苯基二咪唑[2,2’-bis(o-methoxyphenyl)-4,4’,5,5’-tetraphenyl-biimidazole]、2,2’-双(邻-乙基苯基)-4,4’,5,5’-四苯基二咪唑[2,2’-bis(o-ethylphenyl)-4,4’,5,5’-tetraphenyl-biimidazole]、2,2’-双(对甲氧基苯基)-4,4’,5,5’-四苯基二咪唑[2,2’-bis(p-methoxyphenyl)-4,4’,5,5’-tetraphenyl-biimidazole]、2,2’-双(2,2’,4,4’-四甲氧基苯基)-4,4’,5,5’-四苯基二咪唑[2,2’-bis(2,2’,4,4’-tetramethoxyphenyl)-4,4’,5,5’-tetraphenyl-biimidazole]、2,2’-双(2-氯苯基)-4,4’,5,5’-四苯基二咪唑[2,2’-bis(2-chlorophenyl)-4,4’,5,5’-tetraphenyl-biimidazole]、2,2’-双(2,4-二氯苯基)-4,4’,5,5’-四苯基二咪唑[2,2’-bis(2,4-dichlorophenyl)-4,4’,5,5’-tetraphenyl-biimidazole]。
上述的酰肟系化合物是选自于乙烷酮,1-[9-乙基-6-(2-甲基苯甲酰基)-9氢-咔唑-3-取代基]-,1-(氧-乙酰肟)[Ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime),例如Ciba Specialty Chemicals制的品名为CGI-242者,其结构如下式(III)所示]、1-[4-(苯基硫代)苯基]-辛烷-1,2-二酮2-(O-苯酰基肟)[1-[4-(benzoyl)phenyl]-heptane-1,2-dione2-(O-benzoyloxime),例如Ciba Specialty Chemicals制造的商品名为CGI-124的商品,其结构如下式(IV)所示]、乙烷酮,1-[9-乙基-6-(2-氯-4-苯甲基-硫代-苯甲酰基)-9氢-咔唑-3-取代基]-,1-(氧-乙酰肟)[Ethanone,1-[9-ethyl-6-(2-cholro-4-benzyl-thio-benzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime),例如旭电化公司制,其结构如下式(V)所示]:
较佳地,所述光引发剂(C)是2-甲基-1-(4-甲基硫代苯基)-2-吗啉代-1-丙酮、2-苄基-2-氮,氮-二甲胺-1-(4-吗啉代苯基)-1-丁酮、2,2’-双(邻-氯苯基)-4,4’,5,5’-四苯基二咪唑、乙烷酮,1-[9-乙基-6-(2-甲基苯甲酰基)-9氢-咔唑-3-取代基]-,1-(氧-乙酰肟)或它们的组合。
本发明的光引发剂(C)可进一步添加下列的化合物:噻吨酮(thioxanthone)、2,4-二乙基噻吨酮(2,4-diethyl-thioxanthanone)、噻吨酮-4-砜(thioxanthone-4-sulfone)、二苯甲酮(benzophenone)、4,4’-双(二甲胺)二苯甲酮[4,4’-bis(dimethylamino)benzophenone]、4,4’-双(二乙胺)二苯甲酮[4,4’-bis(diethylamino)benzophenone]等的二苯甲酮(benzophenone)类化合物;苯偶酰(benzil)、乙酰基(acetyl)等的α-二酮(α-diketone)类化合物;二苯乙醇酮(benzoin)等的酮醇(acyloin)类化合物;二苯乙醇酮甲醚(benzoin methylether)、二苯乙醇酮乙醚(benzoin ethylether)、二苯乙醇酮异丙醚(benzoin isopropylether)等的酮醇醚(acyloin ether)类化合物;2,4,6-三甲基苯酰二苯基膦氧化物(2,4,6-trimethyl-benzoyl-diphenyl–phosphineoxide)、双-(2,6-二甲氧基苯酰)-2,4,4-三甲基苯基膦氧化物[bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethyl-benzyl-phosphineoxide]等的酰膦氧化物(acylphosphineoxide)类化合物;蒽醌(anthraquinone)、1,4-萘醌(1,4-naphthoquinone)等的醌(quinone)类化合物;苯酰甲基氯(phenacyl chloride)、三溴甲基苯砜(tribromomethyl-phenylsulfone)、三(三氯甲基)-s-三嗪[tris(trichloromethyl)-s-triazine]等的卤化物;以及二-叔丁基过氧化物(di-tertbutylperoxide)等的过氧化物。其中,以二苯甲酮(benzophenone)类化合物较佳,尤以4,4’-双(二乙胺)二苯甲酮为最佳。
以所述碱可溶性树脂(A)总重为100重量份计,光引发剂(C)的含量是2重量份~200重量份,较佳为3重量份~175重量份,更佳为5重量份~150重量份。
有机溶剂(D)
本发明的有机溶剂(D)能将所述碱可溶性树脂(A)、所述含乙烯性不饱和基的化合物(B)与所述光引发剂(C)溶解,且不会与其进行反应,并具有适当挥发性。
所述有机溶剂(D)可为乙二醇甲醚、乙二醇乙醚、二甘醇甲醚、二甘醇乙醚、二甘醇正丙醚、二甘醇正丁醚、三甘醇甲醚、三甘醇乙醚、丙二醇甲醚、丙二醇乙醚、一缩二丙二醇甲醚、一缩二丙二醇乙醚、一缩二丙二醇正丙醚、一缩二丙二醇正丁醚、二缩三丙二醇甲醚(tripropylene glycol monomethyl ether)、二缩三丙二醇乙醚(tripropylene glycol mono ethyl ether)等的(聚)亚烷基二醇单烷醚类溶剂;乙二醇甲醚醋酸酯、乙二醇乙醚醋酸酯、丙二醇甲醚醋酸酯、丙二醇乙醚醋酸酯等的(聚)亚烷基二醇单烷醚醋酸酯类溶剂;二甘醇二甲醚、二甘醇甲乙醚、二甘醇二乙醚、四氢呋喃等的其它醚类溶剂;甲乙酮、环己酮、2-庚酮、3-庚酮等的酮类溶剂;2-羟基丙酸甲酯、2-羟基丙酸乙酯等的乳酸烷酯类溶剂;2-羟基-2-甲基丙酸甲酯、2-羟基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基乙酸乙酯、羟基乙酸乙酯、2-羟基-3-甲基丁酸甲酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯、乙酸乙酯、乙酸正丁酯、乙酸正丙酯、乙酸异丙酯、乙酸正丁酯、乙酸异丁酯、乙酸正戊酯、乙酸异戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸异丙酯、丁酸正丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙酰乙酸甲酯、乙酰乙酸乙酯、2-氧基丁酸乙酯等的其它酯类溶剂;甲苯、二甲苯等的芳香族碳氢化合物类溶剂;以及氮-甲基吡咯烷酮、氮,氮-二甲基甲酰胺、氮,氮-二甲基乙酰胺等的羧酸酰胺类溶剂等。
较佳地,所述有机溶剂(D)可为丙二醇甲醚醋酸酯、3-乙氧基丙酸乙酯或混合多种使用。
以所述碱可溶性树脂(A)总重为100重量份计,有机溶剂(D)的含量是500重量份~5000重量份,较佳为800重量份~4000重量份。
颜料(E)
本发明的颜料(E)可为无机颜料、有机颜料或它们的组合。
上述的无机颜料为金属氧化物、金属络合物盐等金属化合物,其可选自于铁、钴、铝、镉、铅、铜、钛、镁、铬、亚铅、锑等金属的氧化物以及前述金属的复合氧化物。
上述的有机颜料可由以下列举者中择一单独使用或混合多种使用:C.I.颜料黄1,3,11,12,13,14,15,16,17,20,24,31,53,55,60,61,65,71,73,74,81,83,93,95,97,98,99,100,101,104,106,108,109,110,113,114,116,117,119,120,126,127,128,129,138,139,150,151,152,153,154,155,156,166,167,168,175;C.I.颜料橙1,5,13,14,16,17,24,34,36,38,40,43,46,49,51,61,63,64,71,73;C.I.颜料红1,2,3,4,5,6,7,8,9,10,11,12,14,15,16,17,18,19,21,22,23,30,31,32,37,38,40,41,42,48:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,53:1,57,57:1,57:2,58:2,58:4,60:1,63:1,63:2,64:1,81:1,83,88,90:1,97,101,102,104,105,106,108,112,113,114,122,123,144,146,149,150,151,155,166,168,170,171,172,174,175,176,177,178,179,180,185,187,188,190,193,194,202,206,207,208,209,215,216,220,224,226,242,243,245,254,255,264,265;C.I.颜料紫1,19,23,29,32,36,38,39;C.I.颜料蓝1,2,15,15:3,15:4,15:6,16,22,60,66;C.I.颜料绿7,36,37;C.I.颜料棕23,25,28;以及C.I.颜料黑1,7。
所述颜料的一次粒子的平均粒子径较佳为10nm~200nm,更佳为20nm~150nm,最佳为30nm~130nm。
以所述碱可溶性树脂(A)总重为100重量份计,颜料(E)的含量是100重量份~800重量份,较佳为120重量份~750重量份,更佳为150重量份~700重量份。
必要时,所述颜料(E)也能选择性使用分散剂,例如:阳离子系、阴离子系、非离子系、两性、聚硅氧烷系、氟系等表面活性剂。
上述的表面活性剂可以从以下列举者中择一单独使用或混合多种使用:聚环氧乙烷十二烷基醚、聚环氧乙烷硬脂酰醚、聚环氧乙烷油醚等聚环氧乙烷烷基醚类;聚环氧乙烷辛基苯醚、聚环氧乙烷壬基苯醚等的聚环氧乙烷烷基苯醚类表面活性剂;聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯等的聚乙二醇二酯类表面活性剂;山梨糖醇酐脂肪酸酯类表面活性剂;脂肪酸改质的聚酯类表面活性剂;三级胺改质的聚胺基甲酸酯类表面活性剂;信越化学工业制造的型号为KP的商品、Toray Dow Corning Silicon制造的商品名为SF-8427的商品、共荣社油脂化学工业制造的型号为Polyflow的商品、得克姆公司(Tochem Products Co.,Ltd.)制造的型号为F-Top的商品、大日本印墨化学工业制造的型号为Megafac的产品、住友3M制造的型号为Fluorade的产品、旭硝子制造的型号为Asahi Guard的商品及型号为Surflon的商品。
金属螯合物(F)
本发明的金属螯合物(F)如下式(VI)所示:
(R4)pM(OR5)j-p 式(VI)
于式(VI)中,M表示金属;R4表示螯合基;R5表示C2~C5的烷基或C6~C20的芳香基;p表示1~j的整数;j表示金属的价数;当R4或R5为多个,每个R4或每个R5为相同或不同。
所述的C2~C5的烷基包含但不限于乙基、丙基、异丙基或丁基。所述的C6~C20的芳香基包含但不限于苯基。
M表示金属,该金属包含但不限于铝、钛、锆、铍、钙、钴、铜、铁、铪、铱、钯、锰、钼、铌、镍、铂金、锡、钌、钽、钒、钨或锌。较佳地,所述金属是选自于铝、钛或锆。
较佳地,所述的螯合基(ligand)是选自于β-二酮类螯合基、β-酮酯类螯合基、胺类螯合基、磺酸类螯合基或磷酸类螯合基。
所述的β-二酮类螯合基包含但不限于乙酰丙酮(acetylacetonate)、二苯甲酰甲烷、2,2,6,6-四甲基-3,5-庚二酮(2,2,6,6-tetramethyl-3,5-heptanedionate)、苯甲酰丙酮(benzoyl acetonate)、1,3-二苯基-1,3-丙二酮(1,3-diphenyl-1,3-propanedionate)、四甲基庚二酮(tetramethylheptanedionate)、己二酮(hexanedionate)或庚二酮(heptanedionate)。
所述的β-酮酯类螯合基包含但不限于乙酰乙酸乙酯(ethyl acetoacetate)、乙酰乙酸甲酯(methyl acetoacetate)、苯甲酰基乙酰乙酸酯(benzoylacetoacetate)、甲基丙烯酰氧基乙基乙酸酯(methacryloxy ethyl acetate)、乙酰乙酸烯丙酯(allyl acetoacetate)、甲基苯甲酰基乙酸酯(methyl benzoyl acetate)、乙基苯甲酰基乙酸酯(ethyl benzoyl acetate)或苯甲酰基乙酸酯(benzoylacetate)。
所述的胺类螯合基包含但不限于三乙醇胺或氮-胺基乙基胺基乙基(N-aminoethyl aminoethyl)。
所述的磺酸类螯合基包含但不限于十二烷基苯磺酰酸(dodecylbenzenesulfonic acid)。
所述的磷酸类螯合基包含但不限于二辛基焦磷酸酯(dioctylpyrophosphate)、二辛基亚磷酸酯(dioctyl phosphate)或三癸基亚磷酸酯(tridecylphosphate)。
所述的金属螯合物(F)可单独或混合多种使用,且所述的金属螯合物(F)包含但不限于三(乙酰丙酮)铝[tris(acetylacetonato)aluminum]、三(乙酰乙酸乙酯)铝[tris(ethyl acetoacetato)aluminum]、(二异丙氧基)单乙酰丙酮铝[(di-i-propoxy)monoacetylacetonato aluminum]、(二异丙氧基)单乙酰乙酸甲酯铝[(di-i-propoxy)monomethylacetoacetato aluminum]、(二异丙氧基)单乙酰乙酸乙酯铝[(di-i-propoxy)monoethylacetoacetate aluminum]或二(乙酰乙酸乙酯)单乙酰丙酮铝[bis(ethyl acetoacetato)monoacetylacetonato aluminum]等的铝金属螯合物(aluminum chelate compound);三乙氧基单乙酰丙酮钛(triethoxymonoacetylacetonato titanium)、三丙氧基单乙酰丙酮钛(tri-n-propoxymonoacetylacetonato titanium)、三异丙氧基乙酰丙酮钛(tri-i-propoxymonoacetylacetonato titanium)、二异丙氧基二乙酰丙酮钛(di-i-propoxybisacetylacetonate titanium)、二异丙氧基二(乙酰乙酸乙酯)钛[di-i-propoxybis(ethyl acetoacetato)titanium]、三丁氧基单乙酰丙酮钛(tri-n-butoxymonoacetylacetonato titanium)、三(仲丁氧基)单乙酰丙酮钛(tri-sec-butoxymonoacetylacetonato titanium)、三(叔丁氧基)单乙酰丙酮钛(tri-t-butoxymonoacetylacetonato titanium)、二乙氧基二乙酰丙酮钛(diethoxybisacetylacetonato titanium)、二丙氧基二乙酰丙酮钛(di-n-propoxybisacetylacetonato titanium)、二异丙氧基二乙酰丙酮钛(di-i-propoxybisacetylacetonato titanium)、二丁氧基二乙酰丙酮钛(di-n-butoxybisacetylacetonato titanium)、二(仲丁氧基)二乙酰丙酮钛(di-sec-butoxybisacetylacetonato titanium)、二(叔丁氧基)二乙酰丙酮钛(di-t-butoxybisacetylacetonato titanium)、单乙氧基三乙酰丙酮钛(monoethoxytrisacetylacetonato titanium)、单丙氧基三乙酰丙酮钛(mono-n-propoxytrisacetylacetonato titanium)、单异丙氧基三乙酰丙酮钛(mono-i-propoxytrisacetylacetonato titanium)、单丁氧基三乙酰丙酮钛(mono-n-butoxytrisacetylacetonato titanium)、单仲丁氧基三乙酰丙酮钛(mono-sec-butoxytrisacetylacetonato titanium)、单叔丁氧基三乙酰丙酮钛(mono-t-butoxytrisacetylacetonato titanium)、四乙酰丙酮钛[tetrakis(acetylacetonato)titanium]、三乙氧基单乙酰乙酸乙酯钛(triethoxy monoethyl acetoacetato titanium)、三丙氧基单乙酰乙酸乙酯钛(tri-n-propoxy monoethyl acetoacetato titanium)、三异丙氧基单乙酰乙酸乙酯钛(tri-i-propoxy monoethyl acetoacetato titanium)、三丁氧基单乙酰乙酸乙酯钛(tri-n-butoxy monoethyl acetoacetato titanium)、三仲丁氧基单乙酰乙酸乙酯钛(tri-sec-butoxy monoethyl acetoacetato titanium)、三叔丁氧基单乙酰乙酸乙酯钛(tri-t-butoxy monoethyl acetoacetato titanium)、二乙氧基二乙酰乙酸乙酯钛(diethoxy bisethyl acetoacetato titanium)、二丙氧基二乙酰乙酸乙酯钛(di-n-propoxy bisethyl acetoacetato titanium)、二异丙氧基二乙酰乙酸乙酯钛(di-i-propoxy bisethyl acetoacetato titanium)、二丁氧基二乙酰乙酸乙酯钛(di-n-butoxy bisethyl acetoacetato titanium)、二(仲丁氧基)二乙酰乙酸乙酯钛(di-sec-butoxy bisethyl acetoacetato titanium)、二(叔丁氧基)二乙酰乙酸乙酯钛(di-t-butoxy bisethyl acetoacetato titanium)、单乙氧基三乙酰乙酸乙酯钛(monoethoxy trisethyl acetoacetato titanium)、单丙氧基三乙酰乙酸乙酯钛(mono-n-propoxy trisethyl acetoacetato titanium)、单异丙氧基三乙酰乙酸乙酯钛(mono-i-propoxy trisethyl acetoacetato titanium)、单丁氧基三乙酰乙酸乙酯钛(mono-n-butoxy trisethyl acetoacetato titanium)、单仲丁氧基三乙酰乙酸乙酯钛(mono-sec-butoxy trisethyl acetoacetato titanium)、单叔丁氧基三乙酰乙酸乙酯钛(mono-t-butoxy trisethyl acetoacetato titanium)、四乙酰乙酸乙酯钛(tetrakisethyl acetoacetato titanium)、单乙酰丙酮三乙酰乙酸乙酯钛(monoacetylacetonato trisethyl acetoacetate titanium)、二乙酰丙酮二乙酰乙酸乙酯钛(bisacetylacetonate bisethyl acetoacetato titanium)、三乙酰丙酮单乙酰乙酸乙酯钛(trisacetylacetonato monoethyl acetoacetate titanium)、二丙氧基二(三乙醇胺)钛[di-n-propoxy bis(triethanolamine)titanium]、二丁氧基二(三乙醇胺)钛[di-n-butoxy bis(triethanolamine)titanium]、异丙基三(十二烷基苯磺酰基)钛(isopropyl tris(dodecylbenzenesulfonyl)titanium)、异丙基三(十二烷基苯磺酰基)钛酸酯(isopropyl tris(dodecylbenzenesulfonyl)titanate)、异丙基三(二辛基焦磷酸酰氧基)钛酸酯[isopropyl tris(dioctyl pyrophosphate)titanate]、四异丙基二(二辛基亚磷酸酰氧基)钛酸酯[tetraisopropyl bis(dioctyl phosphate)titanate]、四辛基二(二-三癸基亚磷酸酰氧基)钛酸酯[tetraoctyl bis(di-tridecyl phosphate)titanate]、四(2,2-二烯丙氧基甲基-1-丁基)二(二-三癸基亚磷酸酰氧基)钛酸酯[tetra(2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl)phosphate titanate]、二(二辛基焦磷酸酰氧基)钛酸乙酸酯([bis(dioctyl pyrophosphate)oxyacetate titanate]、二(二辛基焦磷酸酰氧基)钛酸乙二酯[bis(di-octyl pyrophosphate)ethylenetitanate]、异丙基三(二辛基亚磷酸酰氧基)钛酸酯[isopropyl tri(dioctyl phosphate)titanate]或异丙基三(氮-胺基乙基胺基乙基)钛酸酯[isopropyl tri(N-aminoethylaminoethyl)titanate]等的钛金属螯合物(titanium chelate compound);三乙氧基单乙酰丙酮锆(triethoxy monoacetylacetonato zirconium)、三丙氧基单乙酰丙酮锆(tri-n-propoxy monoacetylacetonato zirconium)、三异丙氧基单乙酰丙酮锆(tri-i-propoxy monoacetylacetonato zirconium)、三丁氧基单乙酰丙酮锆(tri-n-butoxy monoacetylacetonato zirconium)、三(仲丁氧基)单乙酰丙酮锆(tri-sec-butoxy monoacetylacetonato zirconium)、三(叔丁氧基)单乙酰丙酮锆(tri-t-butoxy monoacetylacetonato zirconium)、二乙氧基二乙酰丙酮锆(diethoxybisacetylacetonato zirconium)、二丙氧基二乙酰丙酮锆(di-n-propoxybisacetylacetonato zirconium)、二异丙氧基二乙酰丙酮锆(di-i-propoxybisacetylacetonato zirconium)、二丁氧基二乙酰丙酮锆(di-n-butoxybisacetylacetonato zirconium)、二(仲丁氧基)二乙酰丙酮锆(di-sec-butoxybisacetylacetonato zirconium)、二(叔丁氧基)二乙酰丙酮锆(di-t-butoxybisacetylacetonato zirconium)、乙氧基三乙酰丙酮锆(monoethoxytrisacetylacetonato zirconium)、丙氧基三乙酰丙酮锆(mono-n-propoxytrisacetylacetonato zirconium)、异丙氧基三乙酰丙酮锆(mono-i-propoxy trisacetylacetonato zirconium)、丁氧基三乙酰丙酮锆(mono-n-butoxytrisacetylacetonato zirconium)、仲丁氧基三乙酰丙酮锆(mono-sec-butoxytrisacetylacetonato zirconium)、叔丁氧基三乙酰丙酮锆(mono-t-butoxytrisacetylacetonato zirconium)、四乙酰丙酮锆(tetrakisacetylacetonatozirconium)、三乙氧基单乙酰乙酸乙酯锆(triethoxy monoethyl acetoacetatozirconium)、三丙氧基单乙酰乙酸乙酯锆(tri-n-propoxy monoethyl acetoacetatozirconium)、三异丙氧基单乙酰乙酸乙酯锆(tri-i-propoxy monoethyl acetoacetatozirconium)、三丁氧基单乙酰乙酸乙酯锆(tri-n-butoxy monoethyl acetoacetatozirconium)、三(仲丁氧基)单乙酰乙酸乙酯锆(tri-sec-butoxy monoethylacetoacetato zirconium)、三(叔丁氧基)单乙酰乙酸乙酯锆(tri-t-butoxymonoethyl acetoacetato zirconium)、二乙氧基二乙酰乙酸乙酯锆(diethoxybisethyl acetoacetato zirconium)、二丙氧基二乙酰乙酸乙酯锆(di-n-propoxybisethyl acetoacetato zirconium)、二异丙氧基二乙酰乙酸乙酯锆(di-i-propoxybisethyl acetoacetato zirconium)、二丁氧基二乙酰乙酸乙酯锆(di-n-butoxybisethyl acetoacetato zirconium)、二(仲丁氧基)二乙酰乙酸乙酯锆(di-sec-butoxybisethyl acetoacetato zirconium)、二(叔丁氧基)二乙酰乙酸乙酯锆(di-t-butoxy-bisethyl acetoacetato zirconium)、乙氧基三乙酰乙酸乙酯锆(monoethoxytrisethyl acetoacetato zirconium)、单丙氧基三乙酰乙酸乙酯锆(mono-n-propoxytrisethyl acetoacetato zirconium)、单异丙氧基三乙酰乙酸乙酯锆(mono-i-propoxy trisethyl acetoacetato zirconium)、单丁氧基三乙酰乙酸乙酯锆(mono-n-butoxy trisethyl acetoacetato zirconium)、单仲丁氧基三乙酰乙酸乙酯锆(mono-sec-butoxy trisethyl acetoacetato)zirconium)、单叔丁氧基三乙酰乙酸乙酯锆(mono-t-butoxy-trisethyl acetoacetato zirconium)、三乙酰乙酸乙酯锆(tetrakisethyl acetoacetato zirconium)、单乙酰丙酮三乙酰乙酸乙酯锆(monoacetylacetonate trisethyl acetoacetato zirconium)、二乙酰丙酮二乙酰乙酸乙酯锆(bisacetylacetonate bisethyl acetoacetato zirconium)或三乙酰丙酮单乙酰乙酸乙酯锆(trisacetylacetonato monoethyl acetoacetate zirconium)等的锆金属螯合物(zirconium chelate compound)。
以所述碱可溶性树脂(A)的总重为100重量份,金属螯合物(F)的含量是1重量份~50重量份,较佳为2重量份~45重量份,更佳为3重量份~40重量份。
当所述感旋光性树脂组合物未使用金属螯合物(F)时,所述感旋光性树脂组合物于无预烤的像素制程中,所形成的像素与基板的密着性较差。
但若添加过量的金属螯合物(F),则易发生显影性不佳的情况。于此情形下,若同时添加第一化合物(B-1)作为含乙烯性不饱和基的化合物,则可解决显影性不佳的缺点。
彩色滤光片用感旋光性树脂组合物
本发明的彩色滤光片用感旋光性树脂组合物,一般是将上述碱可溶性树脂(A)、含乙烯性不饱和基的化合物(B)、光引发剂(C)、有机溶剂(D)、颜料(E)及金属螯合物(F)放置于搅拌器中搅拌,使其均匀混合成溶液状态,必要时亦可添加填充剂、抗氧化剂、紫外线吸收剂、防凝集剂及表面活性剂等添加剂。
彩色滤光片的像素着色层的形成方式
本发明的彩色滤光片包含一由该感旋光性树脂组合物经光刻处理后所形成的像素着色层。
在进行所述像素着色层的制作成形时,可藉由回转涂布、流延涂布或辊式涂布等涂布方式,将上述呈溶液状态的本发明感旋光性树脂组合物涂布在一基板上。所述基板可以是用于液晶显示装置的无碱玻璃、钠钙玻璃、硬质玻璃(派勒斯玻璃)、石英玻璃或附着有透明导电膜的上述玻璃,或是用于光电变换装置(例如固体摄影装置)的基板(例如硅基板)。此外,在将所述感旋光性树脂组合物涂布在基板上之前,已预先将能隔离红、绿、蓝等像素着色层的遮光用黑色矩阵(black matrix)加工成形于所述基板上。
涂布后,以减压干燥方式去除所述感旋光性树脂组合物所含大部分的有机溶剂。减压干燥的操作条件是依各成份的种类、配合比率而异,通常,减压干燥是在0mmHg~200mmHg的压力下进行1秒钟~60秒钟。
减压干燥后,以具有特定图案的一掩模对涂膜进行曝光。在曝光过程中所使用的光线,以g线、b线、i线等紫外线为佳,而用以发出紫外线的设备可为(超)高压水银灯及金属卤素灯。
曝光后,将所述涂膜浸渍于温度是23±2℃的一显影液中,进行约15秒~5分钟的显影,去除所述涂膜的不需要的部分,以于所述基板上形成预定的图案。所使用的显影液可以是由氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、硅酸钠、甲基硅酸钠、氨水、乙胺、二乙胺、二甲基乙醇胺、氢氧化四甲铵、氢氧化四乙铵、胆碱、吡咯、哌啶,或1,8-二氮杂二环-(5,4,0)-7-十一烯等碱性化合物所构成的碱性水溶液,其浓度一般是0.001重量%~10重量%,较佳为0.005重量%~5重量%,更佳为0.01重量%~1重量%。
之后,用水将基板上的图案洗净,再用压缩空气或压缩氮气将所述图案风干,最后以热板或烘箱等加热装置对所述图案进行加热处理(post-bake),加热温度设定在150℃~250℃,使用热板时的加热时间为5分钟~60分钟,使用烘箱时的加热时间则为15分钟~150分钟,藉以使所述图案固定、成形为一像素着色层。
重复上述步骤,便能依序在基板上形成红、绿、蓝等像素着色层。
彩色滤光片的形成方式
在温度为220℃~250℃的真空环境下,于上述的像素着色层的表面溅镀形成一ITO保护膜,必要时,对所述ITO保护膜施行蚀刻暨布线,再于所述ITO保护膜表面涂布一配向膜,便能制作出本发明的彩色滤光片。
液晶显示元件的形成方式
本发明的液晶显示元件(例如液晶面板),包含上述的彩色滤光片。首先,取一镶嵌有薄膜晶体管(Thin Film Transistor;TFT)且已涂布上一配向膜的玻璃基板,在前述的彩色滤光片与玻璃基板之间介入间隙作对向配置,再于所述间隙注入液晶分子,随后分别在彩色滤光片与玻璃基板的一外表面贴合一偏光板,即能制得所述液晶显示装置。
已经证实,本发明的感旋光性树脂组合物在省略预烤的像素制程中,当使用金属螯合剂时,所制得的彩色滤光片(像素)与基板具有良好的密着性;且当碱可溶性树脂的共聚合用单体具有第一不饱和单体时,所制得的彩色滤光片具有较佳的显影性,而碱可溶性树脂的共聚合用单体具有第二不饱和单体时,所制得的彩色滤光片具有较佳的耐热性;即基本上已改善已知的感旋光性树脂组合物于省略预烤的像素制程中密着性不佳的缺点。
以下利用数个实施方式以说明本发明的应用,然其并非用以限定本发明,本发明技术领域中具有通常知识者,在不脱离本发明的精神和范围内,当可作各种的更动与润饰。
具体实施方式
制备碱可溶性树脂(A)
以下是根据表1制备合成例A-1至A-6的碱可溶性树脂。
合成例A-1
在一容积1000毫升的四颈锥瓶上设置氮气入口、搅拌器、加热器、冷凝管及温度计,并导入氮气且依表1所示成分种类与使用比例,准备用以合成所述碱可溶性树脂所需的第一不饱和单体、第二不饱和单体、第三不饱和单体、聚合用引发剂与溶剂等成分。
进行聚合时,先将5重量份的2-甲基丙烯酰乙氧基丁二酸酯(2-methacryloyloxyethyl succinate monoester,以下简称HOMS)、5重量份的双环戊烯基丙烯酸酯(dicyclopentenyl acrylate,以下简称FA-511A)、40重量份的苯乙烯(styrene monomer,以下简称SM)以及50重量份的甲基丙烯酸甲酯(methyl methacrylate,以下简称MMA)加入四颈锥瓶中,并予以搅拌混合,同时将四颈锥瓶的油浴温度提升至100℃;另将6重量份的2,2’-偶氮双-2-甲基丁腈(2,2’-azobis-2-methyl butyronitrile,以下简称AMBN)溶解于200重量份的3-乙氧基丙酸乙酯(ethyl 3-ethoxypropionate,以下简称EEP)中,并分成五等份量,每间隔一小时添加一等份量到该四颈锥瓶中。整个聚合过程的反应温度维持在100℃,且聚合时间持续6小时。聚合完成后,将聚合产物自该四颈锥瓶中取出,并把溶剂脱挥,便可制得所述碱可溶性树脂(A-1)。
合成例A-2至A-6
同合成例A-1的碱可溶性树脂的制作方法,不同处在于合成例A-2至A-6是改变碱可溶性树脂中原料的种类及使用量,其配方如表1所示。
制备彩色滤光片用的感旋光性树脂组合物
以下是根据表2制备实施例1至7及比较例1至4的彩色滤光片用的感旋光性树脂组合物。
实施例1
将前述100重量份的合成例A-1所得的碱可溶性树脂组合物、5重量份的DPCA-120(日本化药株式会社制造,以下简称B-1-1)、200重量份的二季戊四醇六丙烯酸酯(Dipentaerythritol hexaacrylate;DPHA,以下简称B-2-1)、3重量份的2-甲基-1-(4-甲基硫代苯基)-2-吗啉代-1-丙酮(以下简称C-1)、5重量份的2,2’-双(2,4-二氯苯基)-4,4’-5,5’-四苯基二咪唑(以下简称C-2)、150重量份的C.I.Pigment R254/C.I.Pigment Y139=80/20(以下简称E-1)以及1重量份的三(乙酰乙酸乙酯)铝(以下简称F-1)加入1000重量份的丙二醇甲醚醋酸酯(以下简称D-1)中,并藉由摇动式搅拌器加以溶解混合,即可制得彩色滤光片用的感旋光性树脂组合物。所得的彩色滤光片用的感旋光性树脂组合物以下列各评价方式进行评价,其结果如表2所示,其中显影性、耐热性以及密着性的检测方法容后再述。
实施例2至7及比较例1至4
实施例2至7及比较例1至4是使用与实施例1彩色滤光片用感旋光性树脂组合物制作方法相同的操作方法,不同的处在于实施例2至7及比较例1至4是改变彩色滤光片用感旋光性树脂组合物中原料的种类及使用量,其配方及下列的评价结果如表2所示。
评价方式
1.显影性
将所制得的感旋光性树脂组合物,以旋转涂布的方式涂布在一100mm×100mm的玻璃基板上,先进行压力为100mmHg、时间为30秒钟的减压干燥,使其形成一膜厚为2.5μm的涂膜。
然后,取2重量百分比的氢氧化钾水溶液2ml,滴在该涂膜上,测量该涂膜溶解所需的时间t,即相当于显影时间,并根据下列标准进行评价:
○:t≦10秒。
╳:10秒<t。
2.耐热性
将前述评价方式1的膜厚为2.5μm的涂膜以紫外光(曝光机Canon PLA-501F)100mJ/cm2的光量照射后,再浸渍于23℃的显影液1分钟,以纯水洗净,再以235℃烘烤30分钟,即可在玻璃基板上形成一膜厚2.0μm的像素着色层。其次,以色度计(大冢电子公司制,型号MCPD)测定其色度(L*,a*,b*),然后于250℃中放置60分钟后,再次测定其色度变化,并根据下式(VII)计算其色度变化ΔEab*,并以下述的基准评价:
ΔEab*=[(ΔL)2+(Δa)2+(Δb)2]1/2 (VII)
○:色度变化ΔEab*<3。
△:3≦色度变化ΔEab*<6。
╳:6≦色度变化ΔEab*。
3.密着性
将前述评价方式1的膜厚为2.5μm的涂膜以紫外光(曝光机Canon PLA-501F)100mJ/cm2的光量照射后,再浸渍于23℃的显影液1分钟,以纯水洗净,再以235℃烘烤30分钟,即可在玻璃基板上形成一膜厚2.0μm的像素着色层。
接着,根据JIS.5400(1900)8.5密着性试验法中的8.5.2的基盘目法测定,将上述像素着色层,以小刀割成100个基盘目,再以胶带沾粘后撕下,观察基盘目残留的情形,并以下述基准作为评价:
○:5B~4B;及
╳:3B~0B;
其中,5B,无任何基盘目脱落;
4B,0%<脱落的基盘目数量≦5%;
3B,5%<脱落的基盘目数量≦15%;
2B,15%<脱落的基盘目数量≦35%;
1B,35%<脱落的基盘目数量≦65%;
0B,65%<脱落的基盘目数量≦100%。
前述实施例所得的感旋光性树脂组合物,其显影性、耐热性以及密着性的评估结果如表2所示。
由表2的结果可知,在省略预烤的像素制程中,当使用金属螯合剂(F)时,所制得的彩色滤光片与基板仍具有良好的密着性。其次,当碱可溶性树脂(A)的共聚合用单体具有第一不饱和单体(a-1)时,所制得的彩色滤光片具有较佳的显影性,而碱可溶性树脂(A)的共聚合用单体具有第二不饱和单体(a-2)时,所制得的彩色滤光片具有较佳的耐热性,故确实可达到本发明的目的。
需补充的是,本发明虽以特定的化合物、组成、反应条件、制程、分析方法或特定仪器作为例示,说明本发明的感旋光性树脂组合物及其应用,惟本发明所属技术领域中任何具有通常知识者可知,本发明并不限于此,在不脱离本发明的精神和范围内,本发明的感旋光性树脂组合物及其应用亦可使用其它的化合物、组成、反应条件、制程、分析方法或仪器进行。
虽然本发明已以实施方式揭露如上,然其并非用以限定本发明,在本发明所属技术领域中任何具有通常知识者,在不脱离本发明的精神和范围内,当可作各种的更动与润饰,因此本发明的保护范围当视后附的权利要求书所界定的范围为准。
表2
Claims (10)
1.一种感旋光性树脂组合物,包含:
一碱可溶性树脂(A);
一含乙烯性不饱和基的化合物(B);
一光引发剂(C);
一有机溶剂(D);
一颜料(E);以及
一金属螯合物(F),且
其中所述含乙烯性不饱和基的化合物(B)包含一第一化合物,且所述第一化合物是由己内酯改质的多元醇与(甲基)丙烯酸反应而得。
4.根据权利要求1所述的感旋光性树脂组合物,其中以所述碱可溶性树脂(A)的总重为100重量份计,所述含乙烯性不饱和基的化合物(B)的含量是10重量份~500重量份,所述光引发剂(C)的含量是2重量份~200重量份,所述有机溶剂(D)的含量是500重量份~5000重量份,所述颜料(E)的含量是100重量份~800重量份,且所述金属螯合物(F)的含量是1重量份~50重量份。
5.根据权利要求1所述的感旋光性树脂组合物,其中以所述碱可溶性树脂(A)的总重为100重量份计,所述第一化合物的含量是5重量份~100重量份。
6.根据权利要求3所述的感旋光性树脂组合物,其中以所述碱可溶性树脂(A)的总重为100重量份计,所述第二化合物的含量是5重量份~400重量份。
7.根据权利要求1所述的感旋光性树脂组合物,其中所述碱可溶性树脂(A)是具有含羧酸基的第一不饱和单体、含脂环结构的第二不饱和单体及第三不饱和单体的混合物的聚合反应产物。
8.根据权利要求7所述的感旋光性树脂组合物,其中以所述混合物的总重为100重量份计,所述第一不饱和单体的含量是5重量份~50重量份,所述第二不饱和单体的含量是1重量份~20重量份,而且所述第三不饱和单体的含量是30重量份~94重量份。
9.一种彩色滤光片,包含由权利要求1至8项中任一项所述的感旋光性树脂组合物经光刻处理后所形成的一像素着色层。
10.一种液晶显示装置,包含权利要求9所述的该彩色滤光片。
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