CN103424989B - 正型感光性树脂组合物及其应用 - Google Patents
正型感光性树脂组合物及其应用 Download PDFInfo
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- CN103424989B CN103424989B CN201310163929.1A CN201310163929A CN103424989B CN 103424989 B CN103424989 B CN 103424989B CN 201310163929 A CN201310163929 A CN 201310163929A CN 103424989 B CN103424989 B CN 103424989B
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- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-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
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
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- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 208000007578 phototoxic dermatitis Diseases 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- TVRGPOFMYCMNRB-UHFFFAOYSA-N quinizarine green ss Chemical compound C1=CC(C)=CC=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=CC=C(C)C=C1 TVRGPOFMYCMNRB-UHFFFAOYSA-N 0.000 description 1
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- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
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- 230000035945 sensitivity Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- SHBDDIJUSNNBLQ-UHFFFAOYSA-M sodium;3-[[4-[(2-chlorophenyl)-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]cyclohexa-2,5-dien-1-ylidene]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)Cl)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SHBDDIJUSNNBLQ-UHFFFAOYSA-M 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
- UWGCNDBLFSEBDW-UHFFFAOYSA-M sodium;4-[[4-(diethylamino)phenyl]-(4-diethylazaniumylidenecyclohexa-2,5-dien-1-ylidene)methyl]naphthalene-2,7-disulfonate Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C2=CC=C(C=C2C=C(C=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 UWGCNDBLFSEBDW-UHFFFAOYSA-M 0.000 description 1
- FHIODWDKXMVJGO-UHFFFAOYSA-N sodium;8-anilino-5-[[4-[(5-sulfonaphthalen-1-yl)diazenyl]naphthalen-1-yl]diazenyl]naphthalene-1-sulfonic acid Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1N=NC(C1=CC=CC=C11)=CC=C1N=NC(C1=CC=CC(=C11)S(O)(=O)=O)=CC=C1NC1=CC=CC=C1 FHIODWDKXMVJGO-UHFFFAOYSA-N 0.000 description 1
- LJFWQNJLLOFIJK-UHFFFAOYSA-N solvent violet 13 Chemical compound C1=CC(C)=CC=C1NC1=CC=C(O)C2=C1C(=O)C1=CC=CC=C1C2=O LJFWQNJLLOFIJK-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000006296 sulfonyl amino group Chemical group [H]N(*)S(*)(=O)=O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- XYRAEZLPSATLHH-UHFFFAOYSA-N trisodium methoxy(trioxido)silane Chemical compound [Na+].[Na+].[Na+].CO[Si]([O-])([O-])[O-] XYRAEZLPSATLHH-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- AODQPPLFAXTBJS-UHFFFAOYSA-M victoria blue 4R Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)=C(C=C1)C2=CC=CC=C2C1=[N+](C)C1=CC=CC=C1 AODQPPLFAXTBJS-UHFFFAOYSA-M 0.000 description 1
- ROVRRJSRRSGUOL-UHFFFAOYSA-N victoria blue bo Chemical compound [Cl-].C12=CC=CC=C2C(NCC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 ROVRRJSRRSGUOL-UHFFFAOYSA-N 0.000 description 1
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
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- H—ELECTRICITY
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- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- H01L27/1259—Multistep manufacturing methods
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Abstract
本发明有关一种正型感光性树脂组合物及其应用。该正型感光性树脂组合物包含:酚醛清漆树脂A;邻萘醌二迭氮磺酸类的酯化物B;染料C;及溶剂D;该酚醛清漆树脂A由甲酚类芳香族羟基化合物与醛类化合物聚缩合而得,基于凝胶渗透色层分析法所测得的酚醛清漆树脂A分子量的积分面积为100%,酚醛清漆树脂A中的甲酚二核体面积为0.5%至6%;染料C包含染料C-1及染料C-2,染料C-1选自由双偶氮系染料、蒽醌系染料及三价铬偶氮系染料所组成的群;染料C-2为三芳甲烷系染料。本发明的正型感光性树脂组合物具有蚀刻后颜色不脱落的优点。本发明还提供一种薄膜晶体管数组基板的制造方法、一种薄膜晶体管数组基板及一种液晶显示组件。
Description
技术领域
本发明是有关一种正型感光性树脂组合物,详言之,是有关一种蚀刻后颜色不脱落的正型感光性树脂组合物及其应用。
背景技术
随着生活中各种电子产品走向轻、薄的趋势,各种智能型手机、薄型电视以及高效能微处理器已广泛使用,而其中所应用的光微影工艺越来越精密,且所形成的线宽亦越来越精细。
针对上述的目的,日本公开特许平11-143067,公开一种正型感光性组合物,该组合物包含酚醛清漆树脂、可吸收紫外光的染料、光酸发生剂与通过酸催化的架桥剂。该专利使用氘取代的二甲基亚砜溶液,进行酚醛清漆树脂的合成,可获得感度与耐化性提升的效果。
然而前述的公知技术中,其金属线路于蚀刻后,附着于金属线路上的光阻图案皆有光线遮蔽率不足或该图案颜色易脱落的问题发生。且因光线遮蔽率不足或颜色的脱落的原故,导致光阻无法遮蔽金属线路的反射光线,特别是在半导体集成电路组件、薄膜晶体管的液晶显示组件或触控面板的工艺中,使后续相关的黄光工艺中的分辨率降低。
有鉴于此,于本领域中有必要发展一种蚀刻后颜色不脱落的正型感光性树脂组合物材料,以克服公知技术的问题。
发明内容
为解决上述技术问题,本发明的目的在于提供一种正型感光性树脂组合物及其图案形成方法,以及该方法制得的薄膜晶体管数组基板和包含该薄膜晶体管数组基板的液晶显示组件。特别是提供一种使用在半导体集成电路组件、薄膜晶体管的液晶显示组件或触控面板的制造中,可于金属线路上形成细小图案的正型感光性树脂组合物,且该图案能显有颜色,并在蚀刻后颜色不脱落,利于遮蔽金属线路的反射光线。
为达上述目的,本发明提供一种正型感光性树脂组合物,其包含:
酚醛清漆树脂A;
邻萘醌二迭氮磺酸类的酯化物B;
染料C;及
溶剂D;
其中,该酚醛清漆树脂A是由甲酚类(cresol)芳香族羟基化合物与醛类化合物聚缩合而得,且基于凝胶渗透色层分析法所测得的酚醛清漆树脂A分子量的积分面积为100%,该酚醛清漆树脂A中的甲酚二核体面积为0.5%至6%;该染料C包含染料C-1及染料C-2,且该染料C-1是选自由双偶氮系染料、蒽醌系染料及三价铬偶氮系染料所组成的群;及该染料C-2为三芳甲烷系染料。
在本发明的正型感光性树脂组合物中,优选地,所述凝胶渗透色层分析法是将酚醛清漆树脂A分子量为200至150000的讯号作积分,并以分子量及累积重量百分率获得积分分子量分布曲线;其中所述凝胶渗透色层分析法是使用制的717plus进样仪;制的79911GP-501、79911GP-502、79911GP-503或79911GP-504管柱及制的2414RIDetector检出器;移动相:四氢呋喃;流量:1.0mL/min;注射量:100μL;测定温度:40℃;测定时间:60分钟;分子量标准品为聚苯乙烯。
在本发明的正型感光性树脂组合物中,优选地,基于酚醛清漆树脂A的使用量为100重量份,所述邻萘醌二迭氮磺酸类的酯化物B的使用量为5至50重量份。
在本发明的正型感光性树脂组合物中,优选地,所述染料C-2为具有下列式1或式2所示结构的化合物或其盐类:
式1
式2
式1中:
R1及R2是独立选自由氢原子、卤素原子及具1至5个碳数的烷基所组成的群;
R3、R4、R5及R6是独立选自由氢原子、具1至5个碳数的烷基、苯基及芐基所组成的群;及
R7是选自由式3、式4及式5所组成的群;
式3
式4
式5
其中:
R8至R10是独立选自由氢原子及-NR25R26所组成的群;
其中:
R25及R26是独立选自由氢原子、具1至5个碳数的烷基、芐基、苯基及p位包含具1至3个碳数的烷基或具1至3个碳数的烷氧基取代的苯基所组成的群;及
R11至R16是独立选自由氢原子、羟基及-SO3-所组成的群;
式2中:
R21及R22是独立选自由氢原子、卤素原子及具1至5个碳数的烷基所组成的群;及
R23是选自由氢原子、-SO3-、羧基、具1至3个碳数的烷基、具1至3个碳数的烷氧基及-NR25R26所组成的群;及
R24是选自由氢原子及-SO3-所组成的群。
在本发明的正型感光性树脂组合物中,优选地,基于酚醛清漆树脂A的使用量为100重量份,所述染料C的使用量为5至120重量份。
在本发明的正型感光性树脂组合物中,优选地,基于酚醛清漆树脂A的使用量为100重量份,所述染料C-1的使用量为2至30重量份;及所述染料C-2的使用量为1至10重量份。
在本发明的正型感光性树脂组合物中,优选地,所述染料C-1的使用量与所述染料C-2的使用量的重量比为1至10。
在本发明的正型感光性树脂组合物中,优选地,所述染料C进一步包含染料C-3,其中该染料C-3为酞菁系染料。
在本发明的正型感光性树脂组合物中,优选地,所述染料C-3为具有下列式6所示结构的化合物或其盐类:
式6
其中:
各个R27是分别独立选自由氢原子、卤素原子、氰基、硝基、醛基、羧基、磺基、具1至20个碳数的含取代或无取代的烷基、具6至14个碳数的含取代或无取代的芳基、具1至10个碳数的含取代或无取代的杂环基、具1至20个碳数的含取代或无取代的烷氧基、具6至14个碳数的含取代或无取代的芳氧基、具2至21个碳数的含取代或无取代的酰基、具1至20个碳数的含取代或无取代的烷基磺酰基、具6至14个碳数的含取代或无取代的芳基磺酰基、具1至10个碳数的含取代或无取代的杂环系磺酰基、具1至25个碳数的含取代或无取代的胺基甲酰基、具0至32个碳数的含取代或无取代的胺磺酰基、具2至20个碳数的含取代或无取代的烷氧羰基、具7至15个碳数的含取代或无取代的芳氧羰基、具2至21个碳数的含取代或无取代的酰胺基、具1至20个碳数的含取代或无取代的磺酰基胺基及具0至36个碳数的含取代或无取代的胺基所组成的群;
n表示1至8范围的整数;
M是选自由金属、金属氯化物、金属氧化物及金属氢氧化物所组成的群。
在本发明的正型感光性树脂组合物中,优选地,基于酚醛清漆树脂A的使用量为100重量份,所述染料C-3的使用量为3至50重量份。
在本发明的正型感光性树脂组合物中,优选地,基于酚醛清漆树脂A的使用量为100重量份,所述溶剂D的使用量为500至2000重量份。
本发明亦提供一种薄膜晶体管数组基板的制造方法,其中,该薄膜晶体管数组基板包含一基板及一图案,该方法包含以上述的正型感光性树脂组合物涂布于该基板上以形成该图案的步骤。
本发明还提供一种薄膜晶体管数组基板,其是由上述的薄膜晶体管数组基板的制造方法所制得的。
本发明又提供一种液晶显示组件,其包含上述的薄膜晶体管数组基板。
本发明的技术方案的详细说明如下所述。
本发明提供一种正型感光性树脂组合物,其包含:
酚醛清漆树脂A;
邻萘醌二迭氮磺酸类的酯化物B;
染料C;及
溶剂D;
其中该酚醛清漆树脂A是由甲酚类芳香族羟基化合物与醛类化合物聚缩合而得,且基于凝胶渗透色层分析法所测得的酚醛清漆树脂A分子量的积分面积为100%,该酚醛清漆树脂A中的甲酚二核体面积为0.5%至6%;该染料C包含染料C-1及染料C-2,且该染料C-1是选自由双偶氮系染料、蒽醌系染料及三价铬偶氮系染料所组成的群;及该染料C-2为三芳甲烷系染料。
本发明所述的酚醛清漆树脂A是指由甲酚类芳香族羟基化合物及醛类聚缩合而得。
在本发明的具体实施方式中,所述甲酚类芳香族羟基化合物包括:间-甲酚(m-cresol)、对-甲酚(p-cresol)、邻-甲酚(o-cresol)等的甲酚类;2,3-二甲苯酚、2,5-二甲苯酚、3,5-二甲苯酚、3,4-二甲苯酚等的二甲酚(xylenol)类。上述化合物可单独一种使用或组合几种使用。
在不影响正型感光性树脂组合物的物性下,本发明所述的酚醛清漆树脂A亦可由其它类的芳香族羟基化合物及醛类聚缩合而得。
在本发明的具体实施方式中,所述其它类的芳香族羟基化合物包括:苯酚(phenol);间-乙基苯酚、对-乙基苯酚、邻-乙基苯酚、2,3,5-三甲基苯酚、2,3,5-三乙基苯酚、4-第三丁基苯酚、3-第三丁基苯酚、2-第三丁基苯酚、2-第三丁基-4-甲基苯酚、2-第三丁基-5-甲基苯酚、6-第三丁基-3-甲基苯酚等的烷基苯酚(alkylphenol)类;对-甲氧基苯酚、间-甲氧基苯酚、对-乙氧基苯酚、间-乙氧基苯酚、对丙氧基苯酚、间-丙氧基苯酚等的烷氧基苯酚(alkoxyphenol)类;邻-异丙烯基苯酚、对-异丙烯基苯酚、2-甲基-4-异丙烯基苯酚、2-乙基-4-异丙烯基苯酚等的异丙烯基苯酚(isopropenylphenol)类;苯基苯酚(phenylphenol)的芳基苯酚(arylphenol)类;4,4'-二羟基联苯、双酚A、间-苯二酚(resorcinol)、对-苯二酚(hydroquinone)、1,2,3-苯三酚(pyrogallol)等的多羟基苯(polyhydroxyphenol)类等。
在本发明的具体实施方式中,与所述甲酚类芳香族羟基化合物缩合的所述醛类包括:甲醛、多聚甲醛(paraformaldehyde)、三聚甲醛(trioxane)、乙醛、丙醛、丁醛、三甲基乙醛、丙烯醛(acrolein)、丁烯醛(crotonaldehyde)、环己醛(cyclohexanealdehyde)、呋喃甲醛(furfural)、呋喃基丙烯醛(furylacrolein)、苯甲醛、对苯二甲醛(terephthalaldehyde)、苯乙醛、α-苯基丙醛、β-苯基丙醛、邻-羟基苯甲醛、间-羟基苯甲醛、对-羟基苯甲醛、邻-甲基苯甲醛、间-甲基苯甲醛、对-甲基苯甲醛、邻-氯苯甲醛、间-氯苯甲醛、对-氯苯甲醛、肉桂醛等。上述醛类可单独一种使用或组合几种使用。其中,优选地,所述醛类为甲醛。
在本发明的具体实施方式中,优选地,所述酚醛清漆树脂A是在盐酸、硫酸、甲酸、醋酸、草酸、对甲苯磺酸等公知的有机酸及/或无机酸的催化剂(触媒)存在下,于常压下进行缩合反应,并经脱水及除去未反应的单体类而得。本发明所述的“甲酚二核体”是指二个m/p/o甲酚单体,透过亚甲基为键结,以m-m、o-o、p-p等结合方式而形成的产物。
在本发明的具体实施方式中,甲酚二核体的含量是以分馏技术或真空蒸馏法控制。分馏技术的一具体实施例是将合成的酚醛清漆树脂在良溶媒中溶解,然后放入贫溶媒中,使酚醛清漆树脂沉淀而成。此外,真空蒸馏法是在合成酚醛清漆树脂时,以230℃以上,优选大于250℃的温度,配合1.3kPa以下的压力,进行减压蒸馏而成。
本发明的酚醛清漆树脂A基于凝胶渗透色层分析法所测得的酚醛清漆树脂A分子量的积分面积为100%,所述酚醛清漆树脂A中的甲酚二核体面积为0.5%至6%,优选地为0.5%至5.5%,更优选地为0.5%至5.0%。若甲酚二核体面积小于0.5%时,则处理过程成本过高;若甲酚二核体面积大于6%时,会有蚀刻后颜色脱落及分辨率较差问题,虽不愿受理论所限制,但相信若树脂中低分子量的甲酚二核体含量过高,则不易包覆染料,且甲酚二核体易溶于碱性的显影液,会同时将颜料溶解带走,造成颜色脱落的问题,并进一步造成分辨率不佳的问题。
本发明的酚醛清漆树脂A分子量的测定方法并无限制,在本发明的具体实施方式中,所述凝胶渗透色层分析法是将酚醛清漆树脂A分子量为200至150,000的讯号作积分,并以分子量及累积重量百分率获得积分分子量分布曲线;其中,所述凝胶渗透色层分析法是使用制的717plus进样仪;制的79911GP-501、79911GP-502、79911GP-503或79911GP-504管柱及制的2414RIDetector检出器;移动相:四氢呋喃;流量:1.0mL/min;注射量:100μL;测定温度:40℃;测定时间:60分钟;分子量标准品为聚苯乙烯。
本发明所述的邻萘醌二迭氮磺酸类的酯化物B可选用公知经常使用者,并无特别的限制。在本发明的具体实施方式中,优选地,所述邻萘醌二迭氮磺酸类的酯化物B为邻萘醌二迭氮-4-磺酸、邻萘醌二迭氮-5-磺酸、邻萘醌二迭氮-6-磺酸等的邻萘醌二迭氮磺酸与羟基化合物的酯化物,更优选地为上述邻萘醌二迭氮磺酸与多元羟基化合物的酯化物。上述化合物可完全酯化或部份酯化。上述羟基化合物的种类可例如:(一)羟基二苯甲酮类、(二)式13所示的羟基芳基化合物、(三)式14所示的(羟基苯基)烃类化合物以及(四)其它芳香族羟基化合物,兹分述如下:
(一)羟基二苯甲酮类的具体例为2,3,4-三羟基二苯甲酮、2,4,4'-三羟基二苯甲酮、2,4,6-三羟基二苯甲酮、2,3,4,4'-四羟基二苯甲酮、2,2',4,4'-四羟基二苯甲酮、2,3',4,4',6-五羟基二苯甲酮、2,2',3,4,4'-五羟基二苯甲酮、2,2',3,4,5'-五羟基二苯甲酮、2,3',4,5,5'-五羟基二苯甲酮或2,3,3',4,4',5'-六羟基二苯甲酮;
(二)羟基芳基化合物的具体例为具有式13所示结构的化合物:
式13
其中:
R31至R33各自表示氢原子或低级的烷基(alkyl);
R34至R39各自表示氢原子、卤素原子、低级的烷基、低级的烷氧基(alkoxy)、低级的脂烯基(alkenyl)或环烷基(cycloalkyl);
R40及R41各自表示氢原子、卤素原子或低级的烷基;
x、y及z表示1至3的整数;及
n表示0或1。
在本发明的具体实施方式中,优选地,所述具有式13所示结构的羟基芳基化合物为三(4-羟基苯基)甲烷、双(4-羟基-3,5-二甲基苯基)-4-羟基苯基甲烷、双(4-羟基-3,5-二甲基苯基)-3-羟基苯基甲烷、双(4-羟基-3,5-二甲基苯基)-2-羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-4-羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-3-羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-2-羟基苯基甲烷、双(4-羟基-3,5-二甲基苯基)-3,4-二羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-3,4-二羟基苯基甲烷、双(4-羟基-3,5-二甲基苯基)-2,4-二羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-2,4-二羟基苯基甲烷、双(4-羟基苯基)-3-甲氧基-4-羟基苯基甲烷、双(3-环己基-4-羟基苯基)-3-羟基苯基甲烷、双(3-环己基-4-羟基苯基)-2-羟基苯基甲烷、双(3-环己基-4-羟基苯基)-4-羟基苯基甲烷、双(3-环己基-4-羟基-6-甲基芳基)-2-羟基苯基甲烷、双(3-环己基-4-羟基-6-甲基苯基)-3-羟基苯基甲烷、双(3-环己基-4-羟基-6-甲基苯基)-4-羟基苯基甲烷、双(3-环己基-4-羟基-6-甲基苯基)-3,4-二羟基苯基甲烷、双(3-环己基-6-羟基苯基)-3-羟基苯基甲烷、双(3-环己基-6-羟基苯基)-4-羟基苯基甲烷、双(3-环己基-6-羟基苯基)-2-羟基苯基甲烷、双(3-环己基-6-羟基-4-甲基苯基)-2-羟基苯基甲烷、双(3-环己基-6-羟基-4-甲基苯基)-4-羟基苯基甲烷、双(3-环己基-6-羟基-4-甲基苯基)-3,4-二羟基苯基甲烷、1-[1-(4-羟基苯基)异丙基]-4-[1,1-双(4-羟基苯基)乙基]苯或1-[1-(3-甲基-4-羟基苯基)异丙基]-4-[1,1-双(3-甲基-4-羟基苯基)乙基]苯。
(三)(羟基苯基)烃类化合物的具体例为具有式14所示结构的化合物:
式14
其中:
R42及R43各自表示氢原子或低级烷基;及
x'及y'表示1至3的整数。
在本发明的具体实施方式中,优选地,所述具有式14所示结构的(羟基苯基)烃类为2-(2,3,4-三羟基苯基)-2-(2',3',4'-三羟基苯基)丙烷、2-(2,4-二羟基苯基)-2-(2',4'-二羟基苯基)丙烷、2-(4-羟基苯基)-2-(4'-羟基苯基)丙烷、双(2,3,4-三羟基苯基)甲烷或双(2,4-二羟基苯基)甲烷。
(四)其它芳香族羟基化合物的具体例为苯酚、对-甲氧基苯酚、二甲基苯酚、对苯二酚、双酚A、萘酚(naphthol)、邻苯二酚(pyrocatechol)、1,2,3-苯三酚甲醚(pyrogallolmonomethylether)、1,2,3-苯三酚-1,3-二甲基醚(pyrogallol-1,3-dimethylether)、3,4,5-三羟基苯甲酸(gallicacid)或部份酯化或部份醚化的3,4,5-三羟基苯甲酸。
在本发明的具体实施方式中,优选地,所述羟基化合物为2,3,4-三羟基二苯甲酮或2,3,4,4'-四羟基二苯甲酮。上述羟基化合物可单独一种使用或组合几种使用。
根据本发明的具体实施方式,所述正型感光性树脂组合物中的邻萘醌二迭氮磺酸类的酯化物B,可使用含有醌二迭氮基的化合物,例如:邻萘醌二迭氮-4(或5)-磺酸卤盐与上述(一)-(四)的羟基化合物经缩合反应,完全酯化或部份酯化而得的化合物。上述缩合反应通常在二氧杂环己烷(dioxane)、N-吡咯烷酮(N-pyrrolidone)、乙酰胺(acetamide)等有机溶媒中进行,优选地为在三乙醇胺(triethanolamine)、碱金属碳酸盐或碱金属碳酸氢盐等碱性缩合剂存在下进行。
在本发明的具体实施方式中,基于羟基化合物中的羟基总量为100摩尔%;优选地为50摩尔%以上;更优选地为60摩尔%以上的羟基与邻萘醌二迭氮-4(或5)磺酸卤盐缩合而成酯化物,亦即酯化度在50%以上;更优选为60%以上。
在本发明的具体实施方式中,基于酚醛清漆树脂A的使用量为100重量份,本发明的邻萘醌二迭氮磺酸类的酯化物B的使用量通常为5至50重量份;优选地为10至40重量份;更优选地为20至30重量份。
本发明所述的染料C包含染料C-1及染料C-2,且所述染料C-1是选自由双偶氮系染料、蒽醌系染料及三价铬偶氮系染料所组成的群;及所述染料C-2为三芳甲烷系染料,当不使用染料C-1或染料C-2时,则有分辨率差,残膜率不足等问题。
根据本发明的具体实施方式,所述双偶氮系染料为本发明所属技术领域中一般技术人员可选用的,并有许多商用双偶氮系染料可供选择,例如:C.I.AcidBlack1、C.I.AcidBlack24、C.I.ReactiveBlack5、C.I.SolventBlack3(商品名SudanBlack141;中央合成化学株式会社制、商品名NeptunBlackX60;BASF制)及根本特殊化学制的商品名OilBlackDA-411等。
根据本发明的具体实施方式,所述蒽醌系染料为本发明所属技术领域中一般技术人员可选用的,并有许多商用蒽醌系染料可供选择,例如:C.I.SolventRed52、C.I.SolventRed111、C.I.SolventRed149、C.I.SolventRed150、C.I.SolventRed151、C.I.SolventRed168、C.I.SolventRed191、C.I.SolventRed207、C.I.SolventBlue35、C.I.SolventBlue36、C.I.SolventBlue63、C.I.SolventBlue78、C.I.SolventBlue83、C.I.SolventBlue87、C.I.SolventBlue94、C.I.SolventBlue97、C.I.SolventBlue101、C.I.SolventGreen3、C.I.SolventGreen20、C.I.SolventGreen28、C.I.SolventViolet13、C.I.SolventViolet14、C.I.SolventViolet36、C.I.DisperseRed22、C.I.DisperseRed60、C.I.DisperseViolet31、C.I.DisperseViolet28、C.I.VatBlack27及日本化药制的商品名KayasetBlackA-N等。
根据本发明的具体实施方式,所述三价铬偶氮系染料为本发明所属技术领域中一般技术人员可选用的,并有许多商用三价铬偶氮系染料可供选择,例如:SolventBlack27(商品名NeozaponBlackX51;BASF制、商品名VanCHAKUBlackZ1-1500;玄玄化学制)、SolventBlack29(商品名VALIFASTBLACK3808;ORIENTCHEMICALS制)、C.I.SolventBlack34(商品名VALIFASTBLACK3804;ORIENTCHEMICALS制)等。
根据本发明的具体实施方式,所述染料C-1可单独使用或组合几种使用。
根据本发明的具体实施方式,所述三芳甲烷系染料C-2为本发明所属技术领域中一般技术人员可选用的,优选地,所述三芳甲烷系染料C-2为具有下列式1或式2所示结构的化合物或其盐类:
式1
式2
式1中:
R1及R2是独立选自由氢原子、卤素原子及具1至5个碳数的烷基所组成的群;
R3、R4、R5及R6是独立选自由氢原子、具1至5个碳数的烷基、苯基及芐基所组成的群;及
R7是选自由式3、式4及式5所组成的群;
式3
式4
式5
其中:
R8至R10是独立选自由氢原子及-NR25R26所组成的群;
其中:
R25及R26是独立选自由氢原子、具1至5个碳数的烷基、芐基、苯基及p位包含具1至3个碳数的烷基或具1至3个碳数的烷氧基取代的苯基所组成的群;及
R11至R16是独立选自由氢原子、羟基及-SO3-所组成的群;
式2中:
R21及R22是独立选自由氢原子、卤素原子及具1至5个碳数的烷基所组成的群;及
R23是选自由氢原子、-SO3-、羧基、具1至3个碳数的烷基、具1至3个碳数的烷氧基及-NR25R26所组成的群;及
R24是选自由氢原子及-SO3-所组成的群。
根据本发明的具体实施方式,优选地,所述R8、R21、R22、R23、R25及R26中具1至3个碳数的烷基为甲基、乙基或丙基;R8及R23中具1至3个碳数的烷氧基为甲氧基、乙氧基或丙氧基;R25及R26中包含具1至3个碳数的烷氧基取代的苯基为p-甲氧苯基、p-乙氧苯基、p-丙氧苯基;
根据本发明的具体实施方式,优选地,所述三芳甲烷系染料可为式1或式2所示的化合物的盐类,例如钠、钾等碱金属的盐类或如三乙胺、2-乙基己基胺及1-胺基-3-苯基丁烷的胺盐。此类盐类亦可为与-SO3-所形成的盐类。
根据本发明的具体实施方式,所述三芳甲烷系染料C-2有许多商用染料可供选择,例如:C.I.AcidGreen3、C.I.AcidGreen9、C.I.AcidGreen16、C.I.AcidGreen50、C.I.AcidBlue7、C.I.AcidBlue83(商品名BrilliantBlueR;TrustChem制)、C.I.AcidBlue90、C.I.AcidBlue108、C.I.AcidViolet17(商品名CoomassieVioletR200;Sigma制)、C.I.AcidViolet49、C.I.SolventGreen15、C.I.SolventViolet8、C.I.BasicBlue1、C.I.BasicBlue5、C.I.BasicBlue7(商品名BasonylBlau636;BASF制)、C.I.BasicBlue8、C.I.BasicBlue26、C.I.SolventBlue5、C.I.SolventBlue38、C.I.BasicGreen1、C.I.BasicRed9、C.I.BasicViolet3、C.I.BasicViolet12、C.I.BasicViolet14、MethylViolet、CrystalViolet、VictoriaBlueB、OilBlue613(ORIENTCHEMICALS制)、VALIFASTBlue1621(ORIENTCHEMICALS制)、SBNBlue701(保土谷化学公司制造)及其衍生物等。
根据本发明的具体实施方式,所述三芳甲烷系染料C-2可单独使用或组合几种使用。
根据本发明的具体实施方式,优选地,所述染料C进一步包含染料C-3,其中,所述染料C-3为酞菁系染料。本发明所述的酞菁系染料优选地是具有式6所示结构的化合物或其盐类:
式6
其中:
R27表示取代基,优选地,其为下述式7中的Ra1至Ra8与Rb1至Rb8所示的取代基;及
n表示1至8的整数;优选地为1至6;更优选地为1至4。当n为2以上的整数时,多个存在的R27可以相同或不同。
M是选自由金属、金属氯化物、金属氧化物及金属氢氧化物所组成的群。优选地,所述金属是选自由锌、镁、硅、锡、铑、铂、钯、钼、锰、铅、铜、镍、钴及铁所组成的群;所述金属氯化物是选自由AlCl、InCl、FeCl、TiCl2、SnCl2、SiCl2及GeCl2所组成的群;所述金属氧化物是选自由TiO及VO所组成的群;所述金属氢氧化物为Si(OH)2;更优选地,M是选自由锌、钯、铜、镍、钴及VO所组成的群;尤为优选地,M是选自由锌、铜、钴及VO所组成的群;最优选地,M为铜。
根据本发明的具体实施方式,优选地,所述酞菁系染料为具有式7所示结构的化合物:
式7
其中:
Ra1至Ra8与Rb1至Rb8分别独立选自由氢原子、卤素原子、氰基、硝基、醛基(formyl)、羧基、磺基(sulfo)、具1至20个碳数的含取代或无取代的烷基、具6至14个碳数的含取代或无取代的芳基、具1至10个碳数的含取代或无取代的杂环基、具1至20个碳数的含取代或无取代的烷氧基、具6至14个碳数的含取代或无取代的芳氧基、具2至21个碳数的含取代或无取代的酰基、具1至20个碳数的含取代或无取代的烷基磺酰基(alkylsulfonyl)、具6至14个碳数的含取代或无取代的芳基磺酰基、具1至10个碳数的含取代或无取代的杂环系磺酰基(heterysulfonyl)、具1至25个碳数的含取代或无取代的胺基甲酰基(carbamoyl)、具0至32个碳数的含取代或无取代的胺磺酰基(sulfamoyl)、具2至20个碳数的含取代或无取代的烷氧羰基(alkoxycarbonyl)、具7至15个碳数的含取代或无取代的芳氧羰基(aryloxycarbonyl)、具2至21个碳数的含取代或无取代的酰胺基(acylamino)、具1至20个碳数的含取代或无取代的磺酰基胺基(sulfonylamino)及具0至36个碳数的含取代或无取代的胺基所组成的群;其中,胺基中包括苯胺基。另外,为得较理想的溶剂相溶性,优选地,Ra1至Ra8与Rb1至Rb8中至少8个为氢原子,Ra1至Ra8不全为氢原子。
优选地,Ra1至Ra8与Rb1至Rb8分别独立选自由氢原子、卤素原子、羧基、磺基、具1至16个碳数的含取代或无取代的烷基(例如:甲基、乙基、正丙基、异丙基)、具6至14个碳数的含取代或无取代的芳基(例如:苯基、p-甲氧基苯基、p-十八烷基苯基)、具1至16个碳数的含取代或无取代的烷氧基(例如:甲氧基、乙氧基、正辛氧基)、具6至10个碳数的含取代或无取代的芳氧基(例如:苯氧基、p-乙氧基苯氧基)、具1至20个碳数的含取代或无取代的烷基磺酰基(例如:甲烷磺酰基、正丙基磺酰基、正辛基磺酰基)、具6至14个碳数的含取代或无取代的芳基磺酰基(例如:甲苯磺酰基、苯磺酰基)、具0至20个碳数的含取代或无取代的胺磺酰基(例如:甲基胺磺酰基、正丁基胺磺酰基)、具1至17个碳数的烷氧羰基(例如:甲氧羰基、正丁氧羰基)、具7至15个碳数的含取代或无取代的芳氧羰基(例如:苯氧羰基)、具2至21个碳数的含取代或无取代的酰胺基(例如:乙酰胺基、三甲基乙酰胺基)及具1至18个碳数的磺酰基胺基(例如:甲烷磺酰基胺基、正丁烷磺酰基胺基)所组成的群。
更优选地,Ra1至Ra8与Rb1至Rb8分别独立选自由氢原子、卤素原子、羧基、磺基、具1至16个碳数的含取代或无取代的烷基、具1至16个碳数的含取代或无取代的烷氧基、具1至20个碳数的含取代或无取代的烷基磺酰基、具6至14个碳数的含取代或无取代的芳基磺酰基、具2至20个碳数的含取代或无取代的胺磺酰基、具1至13个碳数的烷氧羰基、具2至21个碳数的含取代或无取代的酰胺基及具1至18个碳数的磺酰基胺基所组成的群。
尤为优选地,Ra1至Ra8分别独立选自由氢原子、卤素原子、磺基、具1至16个碳数的含取代或无取代的烷氧基、具1至20个碳数的含取代或无取代的烷基磺酰基、具6至14个碳数的含取代或无取代的芳基磺酰基、具2至20个碳数的含取代或无取代的胺磺酰基、具2至21个碳数的含取代或无取代的酰胺基及具1至18个碳数的磺酰基胺基所组成的群;Rb1至Rb8为氢原子或卤素原子。
最优选地,Ra1至Ra8分别独立选自由氢原子、磺基、具1至20个碳数的无取代的烷基磺酰基、具6至14个碳数的无取代的芳基磺酰基及具7至20个碳数的无取代的胺磺酰基所组成的群;Rb1至Rb8为氢原子。
另外,为得较理想的溶剂相溶性,优选地,Ra1和Ra2中的任意一方、Ra3和Ra4中的任意一方、Ra5和Ra6中的任意一方以及Ra7和Ra8中的任意一方中,四个不同时为氢原子。
当Ra1至Ra8和Rb1至Rb8所示各基团具有取代基时,该取代基的具体例如下:
具1至20个碳数的链状或环状含取代或无取代的烷基(例如:甲基、乙基、异丙基、环己基、苄基、苯乙基)、具6至18个碳数的含取代或无取代的芳基(例如:苯基、氯苯基、2,4-二第三丁基苯基、1-萘基)、具2至20个碳数的含取代或无取代的烯基(例如:乙烯基、2-甲基乙烯基)、具2至20个碳数的含取代或无取代的炔基(例如:乙炔基、2-甲基乙炔基、2-苯基乙炔基)、卤素原子(例如:氟、氯、溴、碘)、氰基、羟基、羧基、具2至20个碳数的含取代或无取代的酰基(例如:乙酰基、苯甲酰基、水杨酰基、三甲基乙酰基)、具1至20个碳数的含取代或无取代的烷氧基(例如:甲氧基、丁氧基、环己氧基)、具6至20个碳数的含取代或无取代的芳氧基(例如:苯氧基、1-萘氧基、p-甲氧基苯氧基)、具1至20个碳数的含取代或无取代的烷硫基(例如:甲硫基、丁硫基、苄硫基、3-甲氧基丙基硫基)、具6至20个碳数的含取代或无取代的芳硫基(例如:苯硫基、4-氯苯硫基)、具1至20个碳数的含取代或无取代的烷基磺酰基(例如:甲烷磺酰基、丁烷磺酰基)、具6至20个碳数的含取代或无取代的芳基磺酰基(例如:苯磺酰基、对甲苯磺酰基)、具1至17个碳数的含取代或无取代的胺基甲酰基(例如:无取代的胺基甲酰基、甲基胺基甲酰基、乙基胺基甲酰基、正丁基胺基甲酰基、二甲基胺基甲酰基)、具1至16个碳数的含取代或无取代酰胺基(例如:乙酰胺基、苯甲酰胺基)、具2至20个碳数的含取代或无取代酰氧基(例如:乙酰氧基、苯甲酰氧基)、具2至20个碳数的含取代或无取代的烷氧羰基(例如:甲氧羰基、乙氧羰基)、5或6元的含取代或无取代的杂环基(例如:吡啶基、噻吩基、呋喃基、噻唑基、咪唑基、吡唑基等芳香族杂环基;吡咯烷环、哌啶环、吗啉环、吡喃环、硫代吡喃环、二恶烷环、二硫戊环等非芳香族杂环基)。
优选地,Ra1至Ra8与Rb1至Rb8各基团中的取代基是选自由具1至16个碳数的链状或环状含取代或无取代的烷基、具6至14个碳数的芳基、具1至16个碳数的烷氧基、具6至14个碳数的芳氧基、卤素原子、具2至17个碳数的烷氧羰基、具1至10个碳数的胺基甲酰基及具1至10个碳数的酰胺基所组成的群。
更优选地,其是选自由具1至10个碳数的链状或环状的烷基、具6至10个碳数的芳基、具1至10个碳数的烷氧基、具6至10个碳数的芳氧基、氯原子、具2至11个碳数的烷氧羰基、具1至7个碳数的胺基甲酰基及具1至8个碳数的酰胺基所组成的群。
尤为优选地地;其是选自由具1至8个碳数的链状或环状无取代的烷基、具1至8个碳数的无取代的烷氧基、具3至9个碳数的无取代的烷氧羰基、苯基及氯原子所组成的群。最优选地,其为具1至6个碳数的无取代的烷氧基。
根据本发明的具体实施方式,式6或7所示的化合物可在任意位置结合形成聚合物,此时各单元可相同或不同,亦可与聚苯乙烯、聚甲基丙烯酸酯、聚乙烯醇、纤维素等聚合物链相结合。
根据本发明的具体实施方式,式6或7所示的化合物可单独使用特定的化合物,也可以将几种结构不同的化合物组合使用。优选地,其是使用取代基的取代位置不同的异构体的组合物。
根据本发明的具体实施方式,优选地,所述酞菁系染料C-3具有式8、式9、式10、式11或式12所示的结构。
式8
式9
式10
式11
式12
根据本发明的具体实施方式,所述酞菁系染料C-3有许多商用染料可供选择,例如:C.I.AcidBlue249、C.I.SolventBlue25、C.I.SolventBlue55、SolventBlue64(商品名NeptunBlue698)、SolventBlue67、C.I.SolventBlue70(商品名NeozaponBlue807;BASF制)、C.I.DirectBlue199、C.I.DirectBlue86(商品名TurquoiseBlue;ItaliaIncorporation制)等。
使用酞菁系染料C-3时,则可进一步提升分辨率。
在本发明的具体方式中,优选地,所述正型感光性树脂组合物可依需要进一步包含紫环酮系(perinone)染料、苝系(perylene)染料、偶氮系(azo)染料、甲川系(methine)染料、喹啉系(quinoline)染料、吖嗪系(azine)染料、葱醌系(anthraquinone)染料、靛蓝系(indigo)染料、类菁系(oxonol)染料、噻嗪系(thiazine)染料、蒽吡啶酮系(anthrapyridone)染料、二苯骈派喃系(xanthene)染料或苯并吡喃系(benzopyran)染料等染料。
在本发明的具体方式中,优选地,基于酚醛清漆树脂A的使用量为100重量份,所述染料C的使用量为5至120重量份,优选地为10至100重量份,更优选地为15至80重量份。
在本发明的具体方式中,优选地,基于酚醛清漆树脂A的使用量为100重量份,所述染料C-1的使用量为2至30重量份,优选地为3至15重量份,更优选地为5至10重量份;所诉染料C-2的使用量为1至10重量份,优选地为2至9重量份,更优选地为3至8重量份;所述染料C-3的使用量为5至30重量份,优选地为7至28重量份,更优选地为10至25重量份。
在本发明的具体方式中,染料C-1的使用量与染料C-2的使用量的重量比为1至10,优选地为2至9,更优选地为3至7。当染料C-1的使用量与染料C-2的使用量的重量比为1至10时,则较不易产生蚀刻后颜色脱落。
本发明所述的溶剂D是指较易与其它有机成分互相溶解但又不与上述成分相互反应的有机溶剂。
在本发明的具体方式中,所述溶剂D为乙二醇单甲醚、乙二醇单乙醚、二乙二醇单乙醚、二乙二醇单正丙醚、二乙二醇单正丁醚、三乙二醇单甲醚、三乙二醇单乙醚、丙二醇单甲醚、丙二醇单乙醚、二丙二醇单甲醚、二丙二醇单乙醚、二丙二醇单正丙醚、二丙二醇单正丁醚、三丙二醇单甲醚、三丙二醇单乙醚等的(聚)亚烷基二醇单烷醚类;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;二乙二醇二甲醚、二乙二醇甲基乙醚、二乙二醇二乙醚、四氢呋喃等的其它醚类;甲乙酮、环己酮、2-庚酮、3-庚酮等的酮类;2-羟基丙酸甲酯、2-羟基丙酸乙酯(乳酸乙酯)等乳酸烷酯类;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、乙氧基醋酸乙酯、羟基醋酸乙酯、2-羟基-3-甲基丁酸甲酯、3-甲基-3-甲氧基丁基醋酸酯、3-甲基-3-甲氧基丁基丙酸酯、醋酸乙酯、醋酸正丙酯、醋酸异丙酯、醋酸正丁酯、醋酸异丁酯、醋酸正戊酯、醋酸异戊酯、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、乙酰醋酸甲酯、乙酰醋酸乙酯、2-氧基丁酸乙酯等的其它酯类;甲苯、二甲苯等的芳香族烃类;N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺等的羧酸胺类。上述溶剂D可一种单独使用或组合几种使用。优选地,所述溶剂D为丙二醇单乙醚、丙二醇甲醚醋酸酯或乳酸乙酯。
在本发明的具体方式中,基于酚醛清漆树脂A的使用量为100重量份,上述溶剂D的使用量通常为500至2000重量份;优选地为600至1800重量份;更优选地为700至1500重量份。
根据本发明的具体实施方式,优选地,所述正型感光性树脂组合物进一步包含添加剂E。优选地,所述添加剂E包括但不限于:密着助剂、表面平坦剂、稀释剂以及增感剂等。
根据本发明的具体实施方式,所述密着助剂的具体例为三聚氰胺(melamine)化合物及/或硅烷系(silane)化合物,其作用在于增加正型感光性树脂组合物与附着基板间的密着性,其中,所述三聚氰胺的具体例为市售的Cymel-300、Cymel-303(CYTEC制造)、MW-30MH、MW-30、MS-11、MS-001、MX-750或MX-706(三和化学制)市售品。所述硅烷(silane)系化合物的具体例为乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、3-丙烯酰氧基丙基三甲氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基硅烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基硅烷、3-胺基丙基三乙氧基硅烷、3-环氧丙氧基丙基三甲氧基硅烷、3-环氧丙氧基丙基甲基二甲氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷、3-氯丙基甲基二甲氧基硅烷、3-氯丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-巯丙基三甲氧基硅烷或双-1,2-(三甲氧基硅基)乙烷。上述密着助剂可单独一种使用或者组合几种使用。
在本发明的具体方式中,基于酚醛清漆树脂A的使用量为100重量份,三聚氰胺化合物的密着助剂的使用量一般为0重量份至20重量份;优选地为0.5重量份至18重量份;更优选地为1.0重量份至15重量份;硅烷系化合物的密着助剂的使用量一般为0重量份至2重量份;优选地为0.001重量份至1重量份;更优选地为0.005重量份至0.8重量份。
根据本发明的具体实施方式,所述表面平坦剂的具体例为氟系界面活性剂或硅系界面活性剂。所述氟系界面活性剂的具体例为FlourateFC-430、FC-431(3M制)或FtopEF122A、122B、122C、126、BL20(Tochemproduct制)市售品。硅系界面活性剂的具体例为SF8427或SH29PA(TorayDowCorningSilicone制)市售品。上述表面平坦剂可单独一种使用或者组合几种使用。
在本发明的具体实施方式中,基于酚醛清漆树脂A的使用量为100重量份,上述界面活性剂的使用量一般为0重量份至1.2重量份;优选地为0.025重量份至1.0重量份;更优选地为0.050重量份至0.8重量份。
根据本发明的具体实施方式,所述稀释剂的具体例如为RE801或RE802(帝国Ink制)等市售品。上述稀释剂可单独一种使用或者组合几种使用。
根据本发明的具体实施方式,所述增感剂的具体例为TPPA-1000P、TPPA-100-2C、TPPA-1100-3C、TPPA-1100-4C、TPPA-1200-24X、TPPA-1200-26X、TPPA-1300-235T、TPPA-1600-3M6C或TPPA-MF市售品(日本本州岛化学工业制),其中,优选地为TPPA-600-3M6C或TPPA-MF。上述增感剂可单独一种使用或者组合几种使用。
在本发明的具体实施方式中,基于酚醛清漆树脂A的使用量为100重量份,所述增感剂的使用量通常为0至20重量份;优选地为0.5至18重量份;更优选地为1.0至15重量份。
此外,本发明亦可依需要再添加其它的添加剂,例如:可塑剂、安定剂等。
根据本发明的具体实施方式,所述正型感光性树脂组合物的制备为本发明所属技术领域中一般技术人员可实施的,具体言之,其是将上述酚醛清漆树脂A、邻萘醌二迭氮磺酸类的酯化物B、染料C以及溶剂D于搅拌器中搅拌,使其均匀混合成溶液状态,并可视需要添加密着助剂、表面平坦剂、稀释剂、可塑剂、安定剂、增感剂等添加剂E。
本发明亦提供一种薄膜晶体管数组基板的制造方法,其中,该薄膜晶体管数组基板包含一基板及一图案,该方法包含以上述的正型感光性树脂组合物涂布于该基板上以形成该图案的步骤。
在本发明的具体实施方式中,所述正型感光性组合物可经由依序施予预烤(prebake)步骤、曝光步骤、显影步骤及后烤(postbake)处理步骤后,而于基板形成图案。
申言之,本发明使用上述正型感光性树脂组合物形成图案的方法,是通过旋转涂布、流延涂布或辊式涂布等涂布方法,将上述正型感光性树脂组合物涂布在基板上,并于涂布后,以预烤方式去除溶剂,而形成一预烤涂膜。其中,预烤的条件,依各成分的种类、配合比率而异,通常为温度在70至110℃间,进行1至15分钟。
预烤后,将所述涂膜于指定的光罩下进行曝光,然后于23±2℃的温度下浸渍于显影液中,历时15秒至5分钟,由此将不要的部分除去而形成特定的图案。曝光所使用的光线,优选地,为g线、h线、i线等的紫外线,而紫外线照射装置可为(超)高压水银灯及金属卤素灯。
本发明所使用显影液的具体例为氢氧化钠、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、氢氧化四甲胺、氢氧化四乙铵、胆碱、吡咯、哌啶或1,8-二氮杂二环-[5,4,0]-7-十一烯的碱性化合物。
根据本发明的具体实施方式,优选地,所述显影液的浓度为0.001重量%至10重量%;更优选地为0.005重量%至5重量%;尤为优选地为0.01重量%至1重量%。
使用前述碱性化合物所构成的显影液时,通常于显影后以水洗净,再以压缩空气或压缩氮气风干前述涂膜。接着,使用热板或烘箱等加热装置对前述涂膜进行后烤处理。后烤温度通常为100至250℃,其中,使用热板的加热时间为1至60分钟,使用烘箱的加热时间为5至90分钟。经过以上的处理步骤后,即可于基板形成图案。
本发明还提供一种薄膜晶体管数组基板,其是由上述的方法所制得。
在本发明的具体实施方式中,其是将本发明的正型感光性树脂组合物以旋转涂布、流延涂布或辊式涂布等涂布方式涂布于一含有铝、铬、氮化硅或非结晶硅等的薄膜的玻璃基板或塑料基板上而形成一正型光阻剂层,接着经过预烤、曝光、显影及后烤处理形成感光性树脂图案之后,进行蚀刻及光阻剥离;重复上述步骤即可制得一含多数薄膜晶体管或电极的薄膜晶体管数组基板。
请参阅图1,其为本发明的一实施例的液晶显示屏(LCD)用薄膜晶体管(TFT)数组基板的部分剖面示意图。首先,于玻璃基板101上的铝薄膜等处设置闸极102a及储存电容Cs电极102b。其次,于闸极102a上覆盖氧化硅(SiOx)膜103或氮化硅(SiNx)膜104等而形成绝缘膜,并于此绝缘膜上形成作为半导体活性层的非晶硅(a-Si)层105。接着,为了降低接面阻抗,可设置掺杂氮不纯物的非晶硅层106于非晶硅层105上。之后,使用铝等金属,形成汲极107a及源极107b,其中汲极107a连接于数据讯号线(图未显示)上,而源极107b则连接于像素电极(或子像素电极)109上。而后,为保护作为半导体活性层的非晶硅层105、汲极107a或源极107b等,设置氮化硅膜等作为保护膜108。
本发明又提供一种液晶显示组件,其包含上述的薄膜晶体管数组基板。
根据本发明的具体实施方式,优选地,所述液晶显示组件可依需要包含其它的部材。
根据本发明的具体实施方式,所述液晶显示组件的基本构成形态的具体例为(1)将TFT等的驱动组件与像素电极(导电层)经排列所形成的上述本发明的TFT数组基板(驱动基板),与由彩色滤光片及对电极(导电层)所构成的彩色滤光片基板间介入间隔体并且对向配置,最后于间隙部份封入液晶材料而构成。或者,(2)将于上述本发明的TFT数组基板上直接形成彩光滤光片的彩色滤光片一体型TFT数组基板,与配置了对电极(导电层)的对向基板间介入间隔体并且对向配置,最后于间隙部份封入液晶材料而构成等,其中前述使用的液晶材料可为任何一种液晶化合物或液晶组合物,此处并未特别限定。
根据本发明的具体实施方式,所述导电层的具体例为ITO膜;铝、锌、铜、铁、镍、铬、钼等的金属膜;或二氧化硅等的金属氧化膜。优选地,其为具透明性的膜层;更优选地为ITO膜。
根据本发明的具体实施方式,所述本发明的TFT数组基板、彩色滤光片基板及对向基板等所使用的基材,其具体例为钠钙玻璃、低膨胀玻璃、无碱玻璃或石英玻璃的公知玻璃,另外,也可采用由塑料膜等构成的基板。
附图说明
图1为本发明一实施例的液晶显示屏用薄膜晶体管数组基板的部分剖面示意图。
主要组件符号说明:
101玻璃基板
102a闸极
102bCs电极
103氧化硅膜
104氮化硅膜
105非晶硅层
106掺杂氮不纯物的非结晶硅层
107a汲极
107b源极
108保护膜
109像素电极
具体实施方式
兹以下列实施例予以详细说明本发明,但并不意味本发明仅局限于此类实施例所揭示的内容。
依下表1及表2所示的成分合成酚醛清漆树脂A。
表1
表2
酚醛清漆树脂A-1的合成
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所示用量加入进料组合物,上述进料组合物包括:间-甲酚0.7摩尔、对-甲酚0.3摩尔、甲醛0.65摩尔、草酸0.02摩尔。搅拌四颈锥瓶的内容物,并将油浴温度提升至100℃。聚缩合过程的反应温度维持100℃,聚缩合时间6小时。聚缩合完成后,将溶剂脱挥,可得酚醛清漆树脂A-1。
酚醛清漆树脂A-2及A-3的合成
同酚醛清漆树脂A-1的操作方法,不同之处是改变芳香族羟基化合物的种类及混合用量、醛类的用量、酸性触媒的用量,以及反应温度,其配方及反应条件记载于表1。
酚醛清漆树脂A-4的合成
将前述所得酚醛清漆树脂A-1,100重量份溶于溶剂丙二醇甲醚醋酸酯300重量份中,于室温下持续搅拌至完全溶解。之后注入于乙苯(Ethylbenzene)2000重量份之中,同时持续搅拌30分钟后,取出沉淀物,将溶剂脱挥后,可得酚醛清漆树脂A-4。
酚醛清漆树脂A-5的合成
将前述所得酚醛清漆树脂A-1,100重量份溶于溶剂丙二醇单甲醚醋酸酯300重量份中,于室温下持续搅拌至完全溶解。之后注入于异丙苯3000重量份之中,同时持续搅拌30分钟后,取出沉淀物,将溶剂脱挥后,可得酚醛清漆树脂A-5。
酚醛清漆树脂A-6的合成
将前述所得酚醛清漆树脂A-2,100重量份溶于溶剂丙二醇单甲醚醋酸酯300重量份中,于室温下持续搅拌至完全溶解。之后注入于异丙苯2000重量份之中,同时持续搅拌30分钟后,取出沉淀物,将溶剂脱挥后,重复上述溶解、沉淀、脱挥的步骤,可得酚醛清漆树脂A-6。
酚醛清漆树脂A-7的合成
将前述所得酚醛清漆树脂A-3,100重量份溶于溶剂丙二醇单甲醚醋酸酯300重量份中,于室温下持续搅拌至完全溶解。之后注入于乙苯2000重量份及异丙苯1000重量份之中,同时持续搅拌30分钟后,取出沉淀物,将溶剂脱挥后,重复上述溶解、沉淀、脱挥的步骤,可得酚醛清漆树脂A-7。
酚醛清漆树脂A中的甲酚二核体面积
以凝胶渗透色层分析法的操作方式将酚醛清漆树脂A的分子量介于200至150,000的讯号作积分,并以分子量及累积重量百分率获得积分分子量分布曲线;其中该凝胶渗透色层分析法是使用制的717plus进样仪;制的79911GP-501、79911GP-502、79911GP-503或79911GP-504管柱及制的2414RIDetector检出器;移动相:四氢呋喃;流量:1.0mL/min;注射量:100μL;测定温度:40℃;测定时间:60分钟;分子量标准品为聚苯乙烯。
基于凝胶渗透色层分析法所测得的酚醛清漆树脂A的分子量的积分面积为100%,测得该酚醛清漆树脂A中的甲酚二核体面积占多少百分比。
其结果示于表1及表2。
依下表3及表4的比例配制正型感光性树脂组合物。
实施例1
依表3所示的100重量份的酚醛清漆树脂A-4、25重量份的2,3,4-三羟基二苯甲酮与1,2-萘醌二迭氮-5-磺酸的酯化物(平均酯化度为85%,以下简称B-1)、5重量份的2,3,4,4’-四羟基二苯甲酮与1,2-萘醌二迭氮-5-磺酸的酯化物(平均酯化度85%,以下简称B-2)、2重量份的C.I.SolventBlack3(商品名SudanBlack141;中央合成化学制,以下简称C-1-1)、1重量份的C.I.AcidViolet17(商品名CoomassieVioletR200;Sigma制,以下简称C-2-1)溶解于丙二醇甲醚醋酸酯1000重量份溶剂中,即可制得正型感光性树脂组合物。
实施例2至13及比较例1至6
实施例2至13及比较例1至6是以与实施例1相同的步骤来制备正型感光性树脂组合物,不同的地方在于:改变原料的种类及其使用量,该原料的种类及其使用量如表3及表4所示。
表3
B-12,3,4-三羟基二苯甲酮与1,2-萘醌二迭氮-5-磺酸的酯化物
B-22,3,4,4'-四羟基二苯甲酮与1,2-萘醌二迭氮-5-磺酸的酯化物
C-1-1C.I.SolventBlack3(商品名SudanBlack141;中央合成化学制)
C-1-2C.I.SolventBlack34(商品名VALIFASTBlack3804;ORIENTCHEMICAL制)
C-1-3C.I.SolventBlack27(商品名NeozaponBlackX51;BASF制)
C-2-1C.I.AcidViolet17(商品名CoomassieVioletR200;Sigma制)
C-2-2C.I.BasicBlue7(商品名BasonylBlau636;BASF制)
C-2-3C.I.AcidBlue83(商品名BrilliantBlueR;TrustChem制)
C-3-1C.I.DirectBlue86(商品名TurquoiseBlue;ItaliaIncorporation制)
C-3-2C.I.SolventBlue70(商品名NeozaponBlue807;BASF制)
C-3-3C.I.SolventBlue64(商品名NeptunBlue698;BASF制)
D-1丙二醇甲醚醋酸酯(PGMEA,propyleneglycolmonomethyletheracetate)
D-2乳酸乙酯(EL,ethyllactate)
D-3丙二醇单乙醚(PGEE,propyleneglycolmonoethylether)
E-1界面活性剂:商品名SF8427;TorayDowCorningSilicone制
E-2密着助剂:商品名Cymel-303;CYTEC制
表4
B-12,3,4-三羟基二苯甲酮与1,2-萘醌二迭氮-5-磺酸的酯化物
B-22,3,4,4'-四羟基二苯甲酮与1,2-萘醌二迭氮-5-磺酸的酯化物
C-1-1C.I.SolventBlack3(商品名SudanBlack141;中央合成化学制)
C-1-2C.I.SolventBlack34(商品名VALIFASTBlack3804;ORIENTCHEMICAL制)
C-1-3C.I.SolventBlack27(商品名NeozaponBlackX51;BASF制)
C-2-1C.I.AcidViolet17(商品名CoomassieVioletR200;Sigma制)
C-2-2C.I.BasicBlue7(商品名BasonylBlau636;BASF制)
C-2-3C.I.AcidBlue83(商品名BrilliantBlueR;TrustChem制)
C-3-1C.I.DirectBlue86(商品名TurquoiseBlue;ItaliaIncorporation制)
C-3-2C.I.SolventBlue70(商品名NeozaponBlue807;BASF制)
C-3-3C.I.SolventBlue64(商品名NeptunBlue698;BASF制)
D-1丙二醇甲醚醋酸酯(PGMEA,propyleneglycolmonomethyletheracetate)
D-2乳酸乙酯(EL,ethyllactate)
D-3丙二醇单乙基醚(PGEE,propyleneglycolmonoethylether)
E-1界面活性剂:商品名SF8427;TorayDowCorningSilicone制
E-2密着助剂:商品名Cymel-303;CYTEC制
评价方式:
蚀刻后脱色
将各实施例及比较例的正型感光性树脂组合物于玻璃基板上以旋转涂布方式涂布,在110℃下预烤160秒钟,可得到约1.5μm的预烤涂膜。将该预烤涂膜置于指定光阻底下,利用300mJ/cm2的紫外光(曝光机型号AG500-4N;M&RNanoTechnology制)进行照射后,再以2.38%氢氧化四甲基铵溶液(tetramethylammoniumhydroxide,简称TMAH)水溶液,于23℃下予以显影1分钟,将基板上曝光部份的涂膜除去,然后以纯水洗净得到图案。以220℃温度后烤40分钟后,再于30℃以铝酸蚀刻,制得一含图案的玻璃基版,并以透光率测定仪(透光率测定仪型号NCPD-300;大冢科技股份有限公司制),测量含图案的玻璃基版的透光频谱(频谱波长范围为400nm至780nm),并以不含图案的玻璃基版的透光频谱作为基础值,便可由透光率测定仪计算出透光率,比率范围为0%-100%。
表3及表4中的符号所代表的意义如下所述:
◎:透光率≤15%;
○:15%<透光率≤40%;
×:40%<透光率。
分辨率评价
将各实施例及比较例的正型感光性树脂组合物,于玻璃基板上以旋转涂布方式涂布,在110℃下预烤160秒钟,可得到约1.5μm的预烤涂膜。将该预烤涂膜置于线与间距(lineandspace)的光罩下(日本Filcon制),利用300mJ/cm2的紫外光(曝光机型号AG500-4N;M&RNanoTechnology制)进行照射后,再以2.38%TMAH水溶液,于23℃下予以显影1分钟,将基板上曝光部份的涂膜除去,然后以纯水洗净,其形成的线条幅度的最小值定为分辨率。
表3及表4中的符号所代表的意义如下所述:
◎:线幅<2μm;
○:2μm≤线幅<3μm;
△:3μm≤线幅<5μm;
×:线幅≥5μm。
残膜率
于前述检测项目“分辨率”中所的预烤涂膜上任取一测定点测得一膜厚(δd1),接着浸于23℃的显影液(2.38%的TMAH水溶液)予以显影1分钟后,在相同的测定点测得另一膜厚(δd2)。最后,经下式计算可得到残膜率:
残膜率(%)=[(δd2)/δd1)]×100。
表3及表4中的符号所代表的意义如下所述:
◎:残膜率>95%;
○:95%>残膜率>90%;
△:90%>残膜率>85%;
×:残膜率≤85%。
上述检测的结果示于表3及表4。可知与比较例相较,本发明的实施例具有蚀刻后颜色不脱落的优点且分辨率及残膜率均佳。
上述实施例仅为说明本发明的原理及其功效,而非限制本发明。所属领域一般技术人员对上述实施例所做的修改及变化仍不违背本发明的精神。
Claims (14)
1.一种正型感光性树脂组合物,其包含:
酚醛清漆树脂A;
邻萘醌二迭氮磺酸类的酯化物B;
染料C;及
溶剂D;
其中该酚醛清漆树脂A是由甲酚类芳香族羟基化合物与醛类化合物聚缩合而得,且基于凝胶渗透色层分析法所测得的酚醛清漆树脂A分子量的积分面积为100%,该酚醛清漆树脂A中的甲酚二核体面积为0.5%至6%;该染料C包含染料C-1及染料C-2,且该染料C-1是选自由双偶氮系染料、蒽醌系染料及三价铬偶氮系染料所组成的群;及该染料C-2为三芳甲烷系染料;
基于酚醛清漆树脂A的使用量为100重量份,所述染料C的使用量为10至100重量份;所述染料C-1的使用量为3至15重量份;所述染料C-2的使用量为2至9重量份。
2.根据权利要求1所述的正型感光性树脂组合物,其中,所述凝胶渗透色层分析法是将酚醛清漆树脂A分子量为200至150000的讯号作积分,并以分子量及累积重量百分率获得积分分子量分布曲线;其中所述凝胶渗透色层分析法是使用制的717plus进样仪;制的79911GP-501、79911GP-502、79911GP-503或79911GP-504管柱及制的2414RIDetector检出器;移动相:四氢呋喃;流量:1.0mL/min;注射量:100μL;测定温度:40℃;测定时间:60分钟;分子量标准品为聚苯乙烯。
3.根据权利要求1所述的正型感光性树脂组合物,其中,基于酚醛清漆树脂A的使用量为100重量份,所述邻萘醌二迭氮磺酸类的酯化物B的使用量为5至50重量份。
4.根据权利要求1所述的正型感光性树脂组合物,其中,所述染料C-2为具有下列式1或式2所示结构的化合物:
式1中:
R1及R2独立选自由氢原子、卤素原子及具1至5个碳数的烷基所组成的群;
R3、R4、R5及R6独立选自由氢原子、具1至5个碳数的烷基、苯基及苄基所组成的群;及
R7选自由式3、式4及式5所组成的群;
其中:
R8至R10独立选自由氢原子及-NR25R26所组成的群;
其中:
R25及R26独立选自由氢原子、具1至5个碳数的烷基、苄基、苯基及p位包含具1至3个碳数的烷基或具1至3个碳数的烷氧基取代的苯基所组成的群;及
R11至R16独立选自由氢原子、羟基及-SO3 -所组成的群;
式2中:
R21及R22独立选自由氢原子、卤素原子及具1至5个碳数的烷基所组成的群;及
R23选自由氢原子、-SO3 -、羧基、具1至3个碳数的烷基、具1至3个碳数的烷氧基及-NR25R26所组成的群;及
R24选自由氢原子及-SO3 -所组成的群。
5.根据权利要求4所述的正型感光性树脂组合物,其中,所述染料C-2为具有式1或式2所示结构的化合物的盐类。
6.根据权利要求1所述的正型感光性树脂组合物,其中,所述染料C-1的使用量与所述染料C-2的使用量的重量比为1至10。
7.根据权利要求1所述的正型感光性树脂组合物,其中,所述染料C进一步包含染料C-3,其中该染料C-3为酞菁系染料。
8.根据权利要求1所述的正型感光性树脂组合物,其中,所述染料C-3为具有下列式6所示结构的化合物:
其中:
各个R27分别独立选自由氢原子、卤素原子、氰基、硝基、醛基、羧基、磺基、具1至20个碳数的含取代或无取代的烷基、具6至14个碳数的含取代或无取代的芳基、具1至10个碳数的含取代或无取代的杂环基、具1至20个碳数的含取代或无取代的烷氧基、具6至14个碳数的含取代或无取代的芳氧基、具2至21个碳数的含取代或无取代的酰基、具1至20个碳数的含取代或无取代的烷基磺酰基、具6至14个碳数的含取代或无取代的芳基磺酰基、具1至10个碳数的含取代或无取代的杂环系磺酰基、具1至25个碳数的含取代或无取代的胺基甲酰基、具0至32个碳数的含取代或无取代的胺磺酰基、具2至20个碳数的含取代或无取代的烷氧羰基、具7至15个碳数的含取代或无取代的芳氧羰基、具2至21个碳数的含取代或无取代的酰胺基、具1至20个碳数的含取代或无取代的磺酰基胺基及具0至36个碳数的含取代或无取代的胺基所组成的群;
n表示1至8的整数;
M选自由金属、金属氯化物、金属氧化物及金属氢氧化物所组成的群。
9.根据权利要求8所述的正型感光性树脂组合物,其中,所述染料C-3为具有式6所示结构的化合物的盐类。
10.根据权利要求1所述的正型感光性树脂组合物,其中,基于酚醛清漆树脂A的使用量为100重量份,所述染料C-3的使用量为3至50重量份。
11.根据权利要求1所述的正型感光性树脂组合物,其中,基于酚醛清漆树脂A的使用量为100重量份,所述溶剂D的使用量为500至2000重量份。
12.一种薄膜晶体管数组基板的制造方法,其中,所述薄膜晶体管数组基板包含一基板及一图案,所述方法包含以权利要求1至11中任一项所述的正型感光性树脂组合物涂布于所述基板上以形成该图案的步骤。
13.一种薄膜晶体管数组基板,其是由权利要求12所述的薄膜晶体管数组基板的制造方法所制得的。
14.一种液晶显示组件,其包含权利要求13所述的薄膜晶体管数组基板。
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US9784965B2 (en) * | 2014-03-04 | 2017-10-10 | Jsr Corporation | Display element, photosensitive composition and electrowetting display |
TWI537683B (zh) * | 2014-09-16 | 2016-06-11 | 奇美實業股份有限公司 | 正型感光性樹脂組成物及其應用 |
US10866512B2 (en) | 2015-10-21 | 2020-12-15 | Showa Denko K.K. | Positive photosensitive resin composition |
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