TW201409175A - 正型感光性樹脂組成物及其圖案形成方法 - Google Patents
正型感光性樹脂組成物及其圖案形成方法 Download PDFInfo
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- TW201409175A TW201409175A TW101131364A TW101131364A TW201409175A TW 201409175 A TW201409175 A TW 201409175A TW 101131364 A TW101131364 A TW 101131364A TW 101131364 A TW101131364 A TW 101131364A TW 201409175 A TW201409175 A TW 201409175A
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- 239000011342 resin composition Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 24
- -1 ortho-naphthoquinone diazide sulfonic acid ester Chemical class 0.000 claims abstract description 75
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
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- 238000011161 development Methods 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
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- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229910052747 lanthanoid Inorganic materials 0.000 description 4
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- 229910052725 zinc Inorganic materials 0.000 description 4
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- ZRDYULMDEGRWRC-UHFFFAOYSA-N (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O ZRDYULMDEGRWRC-UHFFFAOYSA-N 0.000 description 3
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 description 3
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 3
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- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- 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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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- 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
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
- G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- 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
- G03F7/20—Exposure; Apparatus therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Materials For Photolithography (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本發明係有關一種正型感光性樹脂組成物及其形成圖案的方法。此正型感光性樹脂組成物包含酚醛清漆樹脂(A)、鄰萘醌二疊氮磺酸類之酯化物(B)、染料(C)以及溶劑(D)。上述之酚醛清漆樹脂(A)包含羥基型酚醛清漆樹脂(A-1),其係由羥基苯甲醛類化合物與芳香族羥基化合物縮合而得。上述之染料(C)包含由雙偶氮系染料、蒽醌系染料及三價鉻偶氮系染料所組成的一群組中至少選自一種(C-1),及三芳甲烷系染料(C-2)。此正型感光性樹脂組成物可於金屬線路上形成細小顯色圖案,且在蝕刻後顏色不脫落,有利於遮蔽金屬線路的反射光線。
Description
本發明係有關於一種正型感光性樹脂組成物及其圖案形成方法,且特別是有關於一種用於半導體積體電路元件、薄膜電晶體(以下簡稱TFT)之液晶顯示元件或觸控面板之製程中,可於金屬線路上形成細小顯色圖案,且在蝕刻後顏色不脫落,利於遮蔽金屬線路的反射光線。
隨著生活中各種電子產品的微小化,各種智慧型手機、薄型電視以及高效能的微處理器對於高解析度之要求日益提高,致使光微影製程需要越來越精密,以形成較精細之線寬。
針對上述之目的,日本公開特許平11-143067揭示一種正型感光性樹脂組成物,該組成物包含酚醛清漆樹脂、可吸收紫外光之染料、光酸發生劑與藉由酸催化之架橋劑。該專利在合成酚醛清漆樹脂時,使用氘取代之二甲基亞碸溶液,可提升正型感光性樹脂組成物之感度與耐化性。
然而,前述之習知技術中,其金屬線路於蝕刻後,附著於金屬線路上之光阻圖案皆有光線遮蔽率不足或該圖案顏色易脫落之問題發生,導致光阻無法遮蔽金屬線路之反射光線。特別是在半導體積體電路元件、薄膜電晶體之液晶顯示元件或觸控面板之製程中,光阻圖案之光線遮蔽率不足或圖案顏色容易脫落,將使光阻無法遮蔽金屬線路之反射光線,進而降低後續相關之黃光製程之解析度。因此,正型感光性
樹脂組成物如何在蝕刻後維持顏色不脫落,已成為本技術領域中之一重要課題。
有鑑於此,亟需提出一種蝕刻後顏色不脫落之正型感光性樹脂組成物材料,以克服習知技術之種種問題。
因此,本發明之一態樣是在提供一種正型感光性樹脂組成物,其包含酚醛清漆樹脂(A)、鄰萘醌二疊氮磺酸類之酯化物(B)、染料(C)以及溶劑(D)。上述之酚醛清漆樹脂(A)包含羥基型酚醛清漆樹脂(A-1),其係由羥基苯甲醛類化合物與芳香族羥基化合物縮合而得。上述之染料(C)包含由雙偶氮系染料、蒽醌系染料及三價鉻偶氮系染料所組成的群組中至少選自一種(C-1),及三芳甲烷系染料(C-2)。
本發明之另一態樣是在提供一種圖案形成方法,其係由對上述之正型感光性樹脂組成物依序施予預烤處理、曝光處理、顯影處理以及後烤處理,藉以於基板上形成圖案。由於上述正型感光性樹脂組成物可於金屬線路上形成細小顯色圖案,且在蝕刻後顏色不脫落,有利於遮蔽金屬線路的反射光線。
本發明之又一態樣是在提供一種薄膜電晶體陣列基板(thin-film transistor;TFT),其包含上述之圖案。
本發明之再一態樣是在提供一種液晶顯示(liquid crystal display;LCD)元件,其包含上述之薄膜電晶體陣列基板。
關於本發明之正型感光性樹脂組成物、薄膜電晶體陣列基板及液晶顯示元件的結構及圖案形成方法,茲分述如下。
本發明之正型感光性樹脂組成物,其包含酚醛清漆樹脂(A)、鄰萘醌二疊氮磺酸類之酯化物(B)、染料(C)以及溶劑(D),以下依序闡述之。
本發明正型感光性樹脂組成物之酚醛清漆樹脂(A)包含羥基型酚醛清漆樹脂(A-1),並可選擇性地進一步包含其他酚醛清漆樹脂(A-2)。
上述之羥基型酚醛清漆樹脂(A-1)係由羥基苯甲醛類化合物與芳香族羥基化合物,在酸性觸媒存在下經縮合反應而得。
前述之羥基苯甲醛類化合物的具體例為:鄰-羥基苯甲醛、間-羥基苯甲醛、對-羥基苯甲醛等之羥基苯甲醛化合物;2,3-二羥基苯甲醛、2,4-二羥基苯甲醛、2,5-二羥基苯甲醛、3,4-二羥基苯甲醛、3,5-二羥基苯甲醛等之二羥基苯甲醛化合物;2,3,4-三羥基苯甲醛、2,4,5-三羥基苯甲醛、2,4,6-三羥基苯甲醛、3,4,5-三羥基苯甲醛等之三羥基苯甲醛化合物;鄰-羥甲基苯甲醛、間-羥甲基苯甲醛、對-羥甲基苯甲醛等之羥基烷基苯甲醛化合物。該羥基苯甲醛類化合物可單獨一種使用或混合複數種使用。其中,上述之羥基苯甲醛類化合物係以鄰-羥基苯甲醛、間-羥基苯甲醛、對-羥基苯甲醛、2,3-二羥基苯甲醛、2,4-二羥基苯甲醛、3,4-二羥基苯甲醛、2,3,4-三羥基苯甲醛、鄰-羥甲基苯甲醛為較佳。
其次,前述與上述羥基苯甲醛類化合物縮合反應之芳香族羥基化合物的具體例為:苯酚(phenol);間-甲酚(m-
cresol)、對-甲酚(p-cresol)、鄰-甲酚(o-cresol)等之甲酚(cresol)類;2,3-二甲苯酚、2,5-二甲苯酚、3,5-二甲苯酚、3,4-二甲苯酚等之二甲酚(xylenol)類;間-乙基苯酚、對-乙基苯酚、鄰-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-甲基苯酚等之烷基苯酚(alkyl phenol)類;對-甲氧基苯酚、間-甲氧基苯酚、對-乙氧基苯酚、間-乙氧基苯酚、對丙氧基苯酚、間-丙氧基苯酚等之烷氧基苯酚(alkoxy phenol)類;鄰-異丙烯基苯酚、對-異丙烯基苯酚、2-甲基-4-異丙烯基苯酚、2-乙基-4-異丙烯基苯酚等之異丙烯基苯酚(isopropenyl phenol)類;苯基苯酚(phenyl phenol)之芳基苯酚(aryl phenol)類;4,4'-二羥基聯苯、雙酚A、間-苯二酚(resorcinol)、對-苯二酚(hydroquinone)、1,2,3-苯三酚(pyrogallol)等之多羥基苯(polyhydroxyphenol)類等。前述芳香族羥基化合物可單獨一種使用或混合複數種使用。其中,上述之芳香族羥基化合物以鄰-甲酚、間-甲酚、對-甲酚、2,5-二甲苯酚、3,5-二甲苯酚、2,3,5-三甲基苯酚等為較佳。
前述酸性觸媒之具體例如:鹽酸、硫酸、甲酸、醋酸、草酸、對甲苯磺酸等。
基於酚醛清漆樹脂(A)100重量份,羥基型酚醛清漆樹脂(A-1)的使用量一般為30重量份至100重量份,較佳為40重量份至100重量份,更佳為50重量份至100重量份。當羥基型酚醛清漆樹脂(A-1)的使用量為30重量份至100重量份時,則有較佳之殘膜率特性。若無使用羥基型酚醛清漆樹脂
(A-1),則所得之正型感光性樹脂組成物形成細小顯色圖案後,會有蝕刻後顏色脫落及解析度較差問題。
至於其他酚醛清漆樹脂(A-2),一般係由前述之芳香族羥基化合物與非羥基苯甲醛類之醛類,在前述之酸性觸媒存在下經縮合反應而得。
前述之非羥基苯甲醛類之醛類的具體例為: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)、環己醛(cyclo hexanealdehyde)、呋喃甲醛(furfural)、呋喃基丙烯醛(furylacrolein)、苯甲醛、對苯二甲醛(terephthal aldehyde)、苯乙醛、α-苯基丙醛、β-苯基丙醛、鄰-甲基苯甲醛、間-甲基苯甲醛、對-甲基苯甲醛、鄰-氯苯甲醛、間-氯苯甲醛、對-氯苯甲醛、肉桂醛等。前述醛類可單獨一種使用或混合複數種使用。其中,非羥基苯甲醛類之醛類係以甲醛、苯甲醛為較佳。
前述之羥基型酚醛清漆樹脂(A-1)與其他酚醛清漆樹脂(A-2),皆可使用單一種類之酚醛清漆樹脂,亦可混合兩種或兩種以上不同種類之酚醛清漆樹脂。
本發明之鄰萘醌二疊氮磺酸類之酯化物(B)可選用習知經常使用者,並無特別的限制。在本發明之較佳具體例中,前述鄰萘醌二疊氮磺酸類之酯化物(B)可包括但不限於鄰萘醌二疊氮-4-磺酸、鄰萘醌二疊氮-5-磺酸、鄰萘醌二疊氮-6-磺酸等之鄰萘醌二疊氮磺酸與羥基化合物的酯化物,然以上述鄰
萘醌二疊氮磺酸與多元羥基化合物的酯化物為較佳。上述鄰萘醌二疊氮磺酸類之酯化物(B)可完全酯化或部份酯化。上述羥基化合物之種類可例如:(一)羥基二苯甲酮類、(二)式(XIII)的羥基芳基化合物、(三)式(XIV)的(羥基苯基)烴類化合物以及(四)其他芳香族羥基化合物,茲分述如下。
(一)羥基二苯甲酮類之具體例為2,3,4-三羥基二苯甲酮、2,4,4'-三羥基二苯甲酮、2,4,6-三羥基二苯甲酮、2,3,4,4'-四羥基二苯甲酮、2,2',4,4'-四羥基二苯甲酮、2,3',4,4',6-五羥基二苯甲酮、2,2',3,4,4'-五羥基二苯甲酮、2,2',3,4,5'-五羥基二苯甲酮、2,3',4,5,5'-五羥基二苯甲酮或2,3,3',4,4',5'-六羥基二苯甲酮。
(二)羥基芳基化合物之具體例為具有式(XIII)所示之結構:
在式(XIII)中,R24至R26為氫原子或低級之烷基(alkyl);R27至R32為氫原子、鹵素原子、低級之烷基、低級之烷氧基(alkoxy)、低級之脂烯基(alkenyl)以及環烷基(cycloalkyl);R33及R34表示氫原子、鹵素原子及低級之烷基;x、y及z為1至3的整數;以及n為0或1。
在本發明之較佳具體例中,具有式(XIII)所示之結構的羥基芳基化合物為三(4-羥基苯基)甲烷、雙(4-羥基-3,5-二甲基苯基)-4-羥基苯基甲烷、雙(4-羥基-3,5-二甲基苯基)-3-羥基苯
基甲烷、雙(4-羥基-3,5-二甲基苯基)-2-羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-4-羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-3-羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-2-羥基苯基甲烷、雙(4-羥基-3,5-二甲基苯基)-3,4-二羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-3,4-二羥基苯基甲烷、雙(4-羥基-3,5-二甲基苯基)-2,4-二羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-2,4-二羥基苯基甲烷、雙(4-羥基苯基)-3-甲氧基-4-羥基苯基甲烷、雙(3-環己基-4-羥基苯基)-3-羥基苯基甲烷、雙(3-環己基-4-羥基苯基)-2-羥基苯基甲烷、雙(3-環己基-4-羥基苯基)-4-羥基苯基甲烷、雙(3-環己基-4-羥基-6-甲基芳基)-2-羥基苯基甲烷、雙(3-環己基-4-羥基-6-甲基苯基)-3-羥基苯基甲烷、雙(3-環己基-4-羥基-6-甲基苯基)-4-羥基苯基甲烷、雙(3-環己基-4-羥基-6-甲基苯基)-3,4-二羥基苯基甲烷、雙(3-環己基-6-羥基苯基)-3-羥基苯基甲烷、雙(3-環己基-6-羥基苯基)-4-羥基苯基甲烷、雙(3-環己基-6-羥基苯基)-2-羥基苯基甲烷、雙(3-環己基-6-羥基-4-甲基苯基)-2-羥基苯基甲烷、雙(3-環己基-6-羥基-4-甲基苯基)-4-羥基苯基甲烷、雙(3-環己基-6-羥基-4-甲基苯基)-3,4-二羥基苯基甲烷、1-[1-(4-羥基苯基)異丙基]-4-[1,1-雙(4-羥基苯基)乙基]苯或1-[1-(3-甲基-4-羥基苯基)異丙基]-4-[1,1-雙(3-甲基-4-羥基苯基)乙基]苯。
(三)(羥基苯基)烴類化合物之具體例為如下式(XIV)所示之結構:
在式(XIV)中,R35及R36為氫原子或低級烷基;以及x'與y'為1至3的整數。
在本發明之較佳具體例中,具有式(XIV)所示之結構式之(羥基苯基)烴類為2-(2,3,4-三羥基苯基)-2-(2',3',4'-三羥基苯基)丙烷、2-(2,4-二羥基苯基)-2-(2',4'-二羥基苯基)丙烷、2-(4-羥基苯基)-2-(4'-羥基苯基)丙烷、雙(2,3,4-三羥基苯基)甲烷或雙(2,4-二羥基苯基)甲烷。
(四)其他芳香族羥基化合物之具體例為苯酚、對-甲氧基苯酚、二甲基苯酚、對苯二酚、雙酚A、萘酚(naphthol)、鄰苯二酚(pyrocatechol)、1,2,3-苯三酚甲醚(pyrogallol monomethyl ether)、1,2,3-苯三酚-1,3-二甲基醚(pyrogallol-1,3-dimethyl ether)、3,4,5-三羥基苯甲酸(gallie acid)或部份酯化或部份醚化之3,4,5-三羥基苯甲酸。
前述羥基化合物較佳為2,3,4-三羥基二苯甲酮或2,3,4,4'-四羥基二苯甲酮。前述羥基化合物可單獨一種使用或混合數種使用。
根據本發明之正型感光性樹脂組成物中之鄰萘醌二疊氮磺酸類之酯化物(B),可使用含有醌二疊氮基的化合物,例如:鄰萘醌二疊氮-4(或5)-磺酸鹵鹽與上述(一)~(四)的羥基化合物經縮合反應,可完全酯化或部份酯化而得之化合物。前述縮合反應通常在二氧雜環己烷(dioxane)、N-吡咯烷酮(N-pyrrolidone)、乙醯胺(acetamide)等有機溶媒中進行,較佳為在三乙醇胺(triethanolamine)、鹼金屬碳酸鹽或鹼金屬碳酸氫鹽等鹼性縮合劑存在下進行。
在本發明之較佳具體例中,基於羥基化合物中之羥基總量100莫耳%;更佳為50莫耳%以上;尤佳為60莫耳%以上的羥基與鄰萘醌二疊氮-4(或5)磺酸鹵鹽縮合而成酯化物,亦即酯化度在50%以上;更佳為60%以上。
在本發明之具體例中,基於酚醛清漆樹脂(A)之使用量為100重量份,本發明之鄰萘醌二疊氮磺酸類之酯化物(B)之使用量通常為5重量份至50重量份,然以10重量份至40重量份為較佳,又以20重量份至30重量份為更佳。
本發明之染料(C)包含由雙偶氮系染料、蒽醌系染料及三價鉻偶氮系染料所組成的群組中至少選自一種(C-1),及三芳甲烷系染料(C-2)。
上述之雙偶氮系染料可以是本發明所屬技術領域中具通常知識者可選用者,並有許多市售雙偶氮系染料可供選擇,例如:C.I.Acid Black 1、C.I.Acid Black 24、C.I.Reactive Black 5、C.I.Solvent Black 3(商品名Sudan Black 141;中央合成化學製、商品名Neptun Black X60;BASF製)及根本特殊化學製之商品名Oil Black DA-411等。
上述之蒽醌系染料可以是本發明所屬技術領域中具通常知識者可選用者,並有許多市售蒽醌系染料可供選擇,例如:C.I.Solvent Red 52、C.I.Solvent Red 111、C.I.Solvent Red 149、C.I.Solvent Red 150、C.I.Solvent Red 151、C.I.Solvent Red 168、C.I.Solvent Red 191、C.I.Solvent Red 207、C.I.Solvent Blue 35、C.I.Solvent Blue
36、C.I.Solvent Blue 63、C.I.Solvent Blue 78、C.I.Solvent Blue 83、C.I.Solvent Blue 87、C.I.Solvent Blue 94、C.I.Solvent Blue 97、C.I.Solvent Blue 101、C.I.Solvent Green 3、C.I.Solvent Green 20、C.I.Solvent Green 28、C.I.Solvent Violet 13、C.I.Solvent Violet 14、C.I.Solvent Violet 36、C.I.Disperse Red 22、C.I.Disperse Red 60、C.I.Disperse Violet 31、C.I.Disperse Violet 28、C.I.Vat Black 27及日本化藥製之商品名Kayaset Black A-N等。
上述之三價鉻偶氮系染料可以是本發明所屬技術領域中具通常知識者可選用者,並有許多市售三價鉻偶氮系染料可供選擇,例如:Solvent Black 27(商品名Neozapon Black X51;BASF製、商品名Van CHAKU Black Z1-1500;玄玄化學製)、Solvent Black 29(商品名VALIFAST BLACK 3808;ORIENT CHEMICALS製)、C.I.Solvent Black 34(商品名VALIFAST BLACK 3804;ORIENT CHEMICALS製)等。
上述由雙偶氮系染料、蒽醌系染料及三價鉻偶氮系染料所組成的群組中至少選自一種(C-1)可單獨一種使用或混合多種使用。
其次,上述之三芳甲烷系染料(C-2)包含具有式(I)或式(II)所示之結構或其鹽類:該式(I)或式(II)所示之結構式之鹽類例如鈉、鉀等鹼金屬之鹽類或如三乙胺、2-乙基己基胺及1-胺基-3-苯基丁烷之胺鹽。此等鹽類亦可為與-SO3-所形成之鹽類。
在式(I)中,R1及R2係獨立選自於由氫原子、鹵素原子及碳數1至5之烷基所組成之一族群,R3、R4、R5及R6係獨立選自於由氫原子、碳數1至5之烷基、苯基及芐基所組成之一族群,且R7之結構係選自於由式(III)、式(IV)及式(V)所組成之一族群:
在式(III)、式(IV)及式(V)中,R8至R10係選自於由氫原子及-NR17R18所組成之一族群,R17及R18係獨立選自於由氫原子、碳數1至5之烷基、芐基、苯基及p位包含碳數1至3之烷基或碳數1至3之烷氧基取代之苯基所組成之一族群,且R11至R16係獨立選自於由氫原子、羥基及-SO3-所組成之一族群。
上述式(II)之R19及R20係獨立選自於由氫原子、鹵素原子及碳數1至5之烷基所組成之一族群,R21係選自於由氫原子、-SO3-、羧基、碳數1至3之烷基、碳數1至3之烷氧基及-NR17R18所組成之一族群,且R22係選自由氫原子及-SO3-所組成之一族群。
較佳地,上述之R8、R19、R20、R21、R17及R18中碳數1至3之烷基為甲基、乙基或丙基;R8及R21中碳數1至3之烷氧基為甲氧基、乙氧基或丙氧基;以及R17及R18中包含碳數1至3之烷氧基取代之苯基為p-甲氧苯基、p-乙氧苯基、p-丙氧苯基。
本發明之三芳甲烷系染料(C-2)有許多市售染料可供選擇,例如:C.I.Acid Green 3、C.I.Acid Green 9、C.I.Acid Green 16、C.I.Acid Green 50、C.I.Acid Blue 7、C.I.Acid Blue 83(商品名Brilliant Blue R;Trust Chem製)、C.I.Acid Blue 90、C.I.Acid Blue 108、C.I.Acid Violet 17(商品名Coomassie Violet R200;Sigma製)、C.I.Acid Violet 49、C.I.Solvent Green 15、C.I.Solvent Violet 8、C.I.Basic Blue 1、C.I.Basic Blue 5、C.I.Basic Blue 7(商品名Basonyl Blau 636;BASF製)、C.I.Basic Blue 8、C.I.Basic Blue 26、C.I.Solvent Blue 5、C.I.Solvent Blue 38、C.I.Basic Green 1、C.I.Basic Red 9、C.I.Basic Violet 3、C.I.Basic Violet 12、C.I.Basic Violet 14、Methyl Violet、Crystal Violet、Victoria Blue B、Oil Blue 613(ORIENT CHEMICALS製)、VALIFAST Blue 1621
(ORIENT CHEMICALS製)、SBN Blue 701(保土谷化學公司製造)及其衍生物等。上述之三芳甲烷系染料(C-2)可單獨一種使用或混合多種使用。
基於酚醛清漆樹脂(A)為100重量份,由雙偶氮系染料、蒽醌系染料及三價鉻偶氮系染料所組成的群組中至少選自一種(C-1)的使用量為2重量份至30重量份,然以3至15重量份為較佳,又以5至10重量份為更佳;三芳甲烷系染料(C-2)的使用量為1重量份至10重量份,然以2至9重量份為較佳,又以3至8重量份為更佳。當正型感光性樹脂組成物未使用由雙偶氮系染料、蒽醌系染料及三價鉻偶氮系染料所組成的群組中至少選自一種(C-1)或三芳甲烷系染料(C-2)時,則後續形成之圖案會有解析度差、殘膜率不足等問題。
其次,由雙偶氮系染料、蒽醌系染料及三價鉻偶氮系染料所組成的群組中至少選自一種(C-1)之使用量與三芳甲烷系染料(C-2)之使用量之比值為1至10,然以2至9為較佳,又以3至7為更佳。當由雙偶氮系染料、蒽醌系染料及三價鉻偶氮系染料所組成的群組中至少選自一種(C-1)之使用量,與三芳甲烷系染料(C-2)之使用量,二者比值介於1至10之間時,則蝕刻後較不易產生顏色脫落。
再者,本案之染料(C)進一步更可包含酞菁系染料(C-3),其包含具有式(VI)所示之結構:
在式(VI)中,上述R23為取代基,然以下式(VII)之Ra1至Ra8與Rb1至Rb8所示之取代基為較佳。
在式(VI)中,上述n為1至8之整數,然以1至6為較佳,又以1至4為更佳。當n為2以上之整數時,多個存在的R27可以相同或不同。
在式(VI)中,上述M係選自於由金屬、金屬氯化物、金屬氧化物及金屬氫氧化物所組成之一族群。較佳地,適用於M之金屬為選自於由鋅、鎂、矽、錫、銠、鉑、鈀、鉬、錳、鉛、銅、鎳、鈷及鐵所組成之一族群,適用於M之金屬氯化物係選自於由AlCl、InCl、FeCl、TiCl2、SnCl2、SiCl2及GeCl2所組成之一族群,適用於M之金屬氧化物係選自於由TiO及VO所組成之一族群,且適用於M金屬氫氧化物為Si(OH)2。然而,M以選自於由鋅、鈀、銅、鎳、鈷及VO所組成之一族群為尤佳,然以選自於由鋅、銅、鈷及VO所組成之一族群為更佳,又以銅為甚佳。
又,上述之酞菁系染料(C-3)以具有下式(VII)之結構為較佳:
其中,上述式(VII)之Ra1至Ra8與Rb1至Rb8係分别獨立選自於由氫原子、鹵素原子、氰基、硝基、醛基(formyl)、羧基、磺基(sulfo)、碳數1至20之含取代或無取代之烷基、碳數6至14之含取代或無取代之芳基、碳數1至10之含取代或無取代之雜環基、碳數1至20之含取代或無取代之烷氧基、碳數6至14之含取代或無取代之芳氧基、碳數2至21之含取代或無取代之醯基、碳數1至20之含取代或無取代之烷基磺醯基(alkylsulfonyl)、碳數6至14之含取代或無取代之芳基磺醯基、碳數1至10之含取代或無取代之雜環系磺醯基(heterysulfonyl)、碳數1至25之含取代或無取代之胺基甲醯基(carbamoyl)、碳數0至32之含取代或無取代之胺磺醯基(sulfamoyl)、碳數2至20之含取代或無取代之烷氧羰基(alkoxycarbonyl)、碳數7至15之含取代或無取代之芳氧羰基(aryloxycarbonyl)、碳數2至21之含取代或無取代之醯胺基(acylamino)、碳數1至20之含取代或無取代之磺醯基胺基(sulfonylamino)及碳數0至36之含取代或無取代之胺基所組成之一族群,其中,前述之胺基包括苯胺基。另外,為得較佳之溶劑相溶性,Ra1至Ra8與Rb1至Rb8中以至少8個為氫原子為較佳,且Ra1至Ra8不全為氫原子。
較佳地,Ra1至Ra8與Rb1至Rb8係分别獨立選自由氫原子、鹵素原子、羧基、磺基、碳數1至16之含取代或無取代之烷基(例如:甲基、乙基、正丙基、異丙基)、碳數6至14之含取代或無取代之芳基(例如:苯基、p-甲氧基苯基、p-十八烷基苯基)、碳數1至16之含取代或無取代之烷氧基(例如:甲氧基、乙氧基、正辛氧基)、碳數6至10之含取代或
無取代之芳氧基(例如:苯氧基、p-乙氧基苯氧基)、碳數1至20之含取代或無取代之烷基磺醯基(例如:甲烷磺醯基、正丙基磺醯基、正辛基磺醯基)、碳數6至14之含取代或無取代之芳基磺醯基(例如:甲苯磺醯基、苯磺醯基)、碳數0至20之含取代或無取代之胺磺醯基(例如:甲基胺磺醯基、正丁基胺磺醯基)、碳數1至17之烷氧羰基(例如:甲氧羰基、正丁氧羰基)、碳數7至15之含取代或無取代之芳氧羰基(例如:苯氧羰基)、碳數2至21之含取代或無取代之醯胺基(例如:乙醯胺基、三甲基乙醯胺基)及碳數1至18之磺醯基胺基(例如:甲烷磺醯基胺基、正丁烷磺醯基胺基)所組成之一族群。
更佳地,Ra1至Ra8與Rb1至Rb8為係分別獨立選自由氫原子、鹵素原子、羧基、磺基、碳數1至16之含取代或無取代之烷基、碳數1至16之含取代或無取代之烷氧基、碳數1至20之含取代或無取代之烷基磺醯基、碳數6至14之含取代或無取代之芳基磺醯基、碳數2至20之含取代或無取代之胺磺醯基、碳數1至13之烷氧羰基、碳數2至21之含取代或無取代之醯胺基及碳數1至18之磺醯基胺基所組成之一族群。
尤佳地,Ra1至Ra8係分別獨立選自於由氫原子、鹵素原子、磺基、碳數1至16之含取代或無取代之烷氧基、碳數1至20之含取代或無取代之烷基磺醯基、碳數6至14之含取代或無取代之芳基磺醯基、碳數2至20之含取代或無取代之胺磺醯基、碳數2至21之含取代或無取代之醯胺基及碳數1至18之磺醯基胺基所組成之一族群,而Rb1至Rb8為氫原子或鹵素原子。
甚佳地,Ra1至Ra8係分別獨立選自於由氫原子、磺基、碳數1至20之無取代之烷基磺醯基、碳數6至14之無取代之芳基磺醯基及碳數7至20之無取代之胺磺醯基所組成之一族群,而Rb1至Rb8為氫原子。另外,為得較佳之溶劑相溶性,Ra1與Ra2之任一者、Ra3與Ra4之任一者、Ra5與Ra6之任一者以及Ra7與Ra8之任一者中,四者不同時為氫原子為較佳。
當Ra1至Ra8和Rb1至Rb8所示各基團具有取代基時,該取代基之具體例如:碳數1至20之鍊狀或環狀含取代或無取代之烷基(例如:甲基、乙基、異丙基、環己基、苄基、苯乙基)、碳數6至18之含取代或無取代之芳基(例如:苯基、氯苯基、2,4-二第三丁基苯基、1-萘基)、碳數2至20之含取代或無取代之烯基(例如:乙烯基、2-甲基乙烯基)、碳數2至20之含取代或無取代之炔基(例如:乙炔基、2-甲基乙炔基、2-苯基乙炔基)、鹵素原子(例如:氟、氯、溴、碘)、氰基、羥基、羧基、碳數2至20之含取代或無取代之醯基(例如:乙醯基、苯甲醯基、水楊醯基、三甲基乙醯基)、碳數1至20之含取代或無取代之烷氧基(例如:甲氧基、丁氧基、環己氧基)、碳數6至20之含取代或無取代之芳氧基(例如:苯氧基、1-萘氧基、p-甲氧基苯氧基)、碳數1至20之含取代或無取代之烷硫基(例如:甲硫基、丁硫基、苄硫基、3-甲氧基丙基硫基)、碳數6至20之含取代或無取代之芳硫基(例如:苯硫基、4-氯苯硫基)、碳數1至20之含取代或無取代之烷基磺醯基(例如:甲烷磺醯基、丁烷磺醯基)、碳數6至20之含取代或無取代之芳基磺醯基(例如:苯磺醯基、對甲苯磺醯
基)、碳數1至17之含取代或無取代之胺基甲醯基(例如:無取代之胺基甲醯基、甲基胺基甲醯基、乙基胺基甲醯基、正丁基胺基甲醯基、二甲基胺基甲醯基)、碳數1至16之含取代或無取代醯胺基(例如:乙醯胺基、苯甲醯胺基)、碳數2至20之含取代或無取代醯氧基(例如:乙醯氧基、苯甲醯氧基)、碳數2至20之含取代或無取代之烷氧羰基(例如:甲氧羰基、乙氧羰基)、5或6員之含取代或無取代之雜環基(例如:吡啶基、噻吩基、呋喃基、噻唑基、咪唑基、吡唑基等芳香族雜環基;吡咯烷環、哌啶環、嗎啉環、吡喃環、硫代吡喃環、二噁烷環、二硫戊環等非芳香族雜環基)。
較佳地,Ra1至Ra8與Rb1至Rb8各基團中之取代基係選自於由具碳數1至16之鏈狀或環狀含取代或無取代之烷基、碳數6至14之芳基、碳數1至16之烷氧基、碳數6至14之芳氧基、鹵素原子、碳數2至17之烷氧羰基、碳數1至10之胺基甲醯基及碳數1至10之醯胺基所組成之一族群。
更佳地,Ra1至Ra8與Rb1至Rb8各基團中之取代基係選自於由碳數1至10之鏈狀或環狀之烷基、碳數6至10之芳基、碳數1至10之烷氧基、碳數6至10之芳氧基、氯原子、碳數2至11之烷氧羰基、碳數1至7之胺基甲醯基及碳數1至8之醯胺基所組成之一族群。
尤佳地,Ra1至Ra8與Rb1至Rb8各基團中之取代基係選自由碳數1至8之鏈狀或環狀無取代之烷基、碳數1至8之無取代之烷氧基、碳數3至9之無取代之烷氧羰基、苯基及氯原子所組成之一族群。甚佳地,Ra1至Ra8與Rb1至Rb8各基團中之取代基為碳數1至6之無取代之烷氧基。
本發明之式(VI)或(VII)所示之酞菁系染料(C-3)可在任意位置結合形成聚合物,此時各單元可相同或不同,亦可與聚苯乙烯、聚甲基丙烯酸酯、聚乙烯醇、纖維素等聚合物鏈相結合。
本發明之式(VI)或(VII)所示之酞菁系染料(C-3)可單獨使用特定的化合物,也可以將多種結構不同的化合物混合使用。較佳地,其係使用取代基之取代位置不同的異構體的混合物。
於本發明之較佳具體例中,酞菁系染料(C-3)亦可包含具有式(VIII)、式(IX)、式(X)、式(XI)或式(XII)所示之結構:
本發明之酞菁系染料(C-3)有許多市售染料可供選擇,例如:C.I.Acid Blue 249、C.I.Solvent Blue 25、C.I.Solvent Blue 55、Solvent Blue 64(商品名Neptun Blue 698;BASF製)、Solvent Blue 67、C.I.Solvent Blue 70(商品名Neozapon Blue 807;BASF製)、C.I.Direct Blue 199、C.I.Direct Blue 86(商品名Turquoise Blue;Italia Incorporation製)等。
當正型感光性樹脂組成物使用酞菁系染料(C-3)時,可進一步提升後續形成之圖案的解析度。
基於酚醛清漆樹脂(A)為100重量份,酞菁系染料(C-3)的使用量為3重量份至60重量份,然以4重量份至55重量份為較佳,又以5重量份至50重量份為更佳。
在其他實施例中,本發明之正型感光性樹脂組成物可依需要進一步包含紫環酮系(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、蒽醌系(anthraquinone)染料、靛藍系(indigo)染料、類菁系(oxonol)染料、噻嗪系
(thiazine)染料、蒽吡啶酮系(anthrapyridone)染料、二苯駢派喃系(xanthene)染料或苯并吡喃系(benzopyran)染料等染料。
本發明正型感光性樹脂組成物所使用的溶劑(D)係指較易與其他有機成分互相溶解但又不與上述成分相互反應之有機溶劑。
在本發明之具體例中,該溶劑(D)為乙二醇單甲醚、乙二醇單乙醚、二乙二醇單乙醚、二乙二醇單正丙醚、二乙二醇單正丁醚、三乙二醇單甲醚、三乙二醇單乙醚、丙二醇單甲醚、丙二醇單乙醚、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單正丙醚、二丙二醇單正丁醚、三丙二醇單甲醚、三丙二醇單乙醚等之(聚)亞烷基二醇單烷醚類;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之(聚)亞烷基二醇單烷醚醋酸酯類;二乙二醇二甲醚、二乙二醇甲基乙醚、二乙二醇二乙醚、四氫呋喃等之其他醚類;甲乙酮、環己酮、2-庚酮、3-庚酮等之酮類;2-羥基丙酸甲酯、2-羥基丙酸乙酯(乳酸乙酯)等乳酸烷酯類;2-羥基-2-甲基丙酸甲酯、2-羥基-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、羥基醋酸乙酯、2-羥基-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、醋酸異丙酯、醋酸正丁酯、醋酸異丁酯、醋酸正戊酯、醋酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸
甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯醋酸甲酯、乙醯醋酸乙酯、2-氧基丁酸乙酯等之其他酯類;甲苯、二甲苯等之芳香族烴類;N-甲基吡咯烷酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等之羧酸胺類。上述溶劑(D)可一種單獨使用或混合複數種使用。較佳地,該溶劑(D)為丙二醇單乙醚、丙二醇甲醚醋酸酯或乳酸乙酯。
在本發明之具體例中,基於酚醛清漆樹脂(A)之使用量為100重量份,上述溶劑(D)之使用量通常為500至2,000重量份;較佳為500至1,500重量份;更佳為1,000至1,500重量份。
本發明之正型感光性樹脂組成物可選擇性包含添加劑(E),可包括但不限於:密著助劑、表面平坦劑、稀釋劑以及增感劑等。
上述密著助劑可包括但不限於三聚氰胺(melamine)化合物及矽烷系(silane)化合物,以增加正型感光性樹脂組成物與附著基板間的密著性。前述三聚氰胺之具體例如:市售之Cymel-300、Cymel-303(CYTEC製造)、MW-30MH、MW-30、MS-11、MS-001、MX-750或MX-706(三和化學製)市售品。前述矽烷(silane)系化合物之具體例如:乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-環氧丙氧基丙
基三甲氧基矽烷、3-環氧丙氧基二甲基甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-巰丙基三甲氧基矽烷或雙-1,2-(三甲氧基矽基)乙烷。
在本發明之具體例中,基於酚醛清漆樹脂(A)之使用量為100重量份,前述三聚氰胺化合物之密著助劑之使用量一般為0重量份至20重量份,然以0.5重量份至18重量份為較佳,又以1.0重量份至15重量份為更佳;前述矽烷系化合物之密著助劑之使用量一般為0重量份至2重量份,然以0.001重量份至1重量份為較佳,又以0.005重量份至0.8重量份為更佳。
上述表面平坦劑可包括但不限於氟系界面活性劑或矽系界面活性劑。前述氟系界面活性劑之具體例如:市售之Flourate FC-430、FC-431(3M製)或F top EF122A、122B、122C、126、BL20(Tochem product製)。前述矽系界面活性劑之具體例如:市售之SF8427或SH29PA(Toray Dow Corning Silicone製)。
在本發明之具體例中,基於酚醛清漆樹脂(A)之使用量為100重量份,前述界面活性劑之使用量一般為0重量份至1.2重量份,然以0.025重量份至1.0重量份為較佳,又以0.050重量份至0.8重量份為更佳。
上述稀釋劑之具體例如:市售之RE801或RE802(帝國Ink製)等。
上述增感劑之具體例如: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(日本本州化學工業製),其中較佳為TPPA-600-3M6C或TPPA-MF。前述之增感劑可單獨一種使用或者混合複數種使用。
於本發明之具體例中,基於酚醛清漆樹脂(A)之使用量為100重量份,前述增感劑之使用量通常為0重量份至20重量份,然以0.5重量份至18重量份為較佳,又以1.0重量份至15重量份為更佳。
此外,本發明亦可依需要再添加其他的添加劑,例如:可塑劑、安定劑等。
其中,上述之添加劑(E)可單獨一種或混合複數種使用。
本發明之正型感光性樹脂組成物的製備,一般係將上述酚醛清漆樹脂(A)、鄰萘醌二疊氮磺酸類之酯化物(B)、染料(C)以及溶劑(D),於習知的攪拌器中攪拌,使其均勻混合成溶液狀態,並可視需要加入各種添加劑(E),即可製得正型感光性樹脂組成物。
上述所得之正型感光性組成物可羥由依序施予預烤(prebake)步驟、曝光步驟、顯影步驟及後烤(postbake)處理步驟後,而於基板形成圖案。
申言之,本發明使用前述正型感光性樹脂組成物形成圖案的方法,是藉由旋轉塗佈、流延塗佈或輥式塗佈等塗佈方法,將前述正型感光性樹脂組成物塗佈在基板上,並
於塗佈後,以預烤方式去除溶劑,而形成一預烤塗膜。其中,預烤之條件,依各成分之種類、配合比率而異,通常為溫度在70至110℃間,進行1至15分鐘。
預烤後,將該塗膜於指定之光罩下進行曝光,然後於23±2℃的溫度下浸漬於顯影液中,歷時15秒至5分鐘,藉此將不要之部分除去而形成特定的圖案。曝光所使用之光線,以g線、h線、i線等之紫外線為佳,而紫外線照射裝置可為(超)高壓水銀燈及金屬鹵素燈。
本發明所使用顯影液的具體例為氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸氫鈉、碳酸鉀、碳酸氫鉀、矽酸鈉、甲基矽酸鈉、氨水、乙胺、二乙胺、二甲基乙醇胺、氫氧化四甲胺、氫氧化四乙銨、膽鹼、吡咯、哌啶或1,8-二氮雜二環-[5,4,0]-7-十一烯之鹼性化合物。
較佳地,顯影液之濃度係0.001重量%至10重量%;更佳係0.005重量%至5重量%;尤佳係0.01重量%至1重量%。
使用前述鹼性化合物所構成之顯影液時,通常於顯影後以水洗淨,再以壓縮空氣或壓縮氮氣風乾前述塗膜。接著,使用熱板或烘箱等加熱裝置對前述塗膜進行後烤處理。後烤溫度通常為100至250℃,其中,使用熱板之加熱時間為1至60分鐘,使用烘箱之加熱時間為5至90分鐘。羥過以上之處理步驟後,即可於基板形成圖案。
本發明之薄膜電晶體陣列基板係以前述之方法所製得。簡言之,可利用旋轉塗佈、流延塗佈或輥式塗佈等塗佈方式,將本發明之正型感光性樹脂組成物塗佈於一含有鋁、鉻、氮化矽或非結晶矽等之薄膜的玻璃基板或塑膠基板上,而形成一正型光阻劑層。接著,經過預烤、曝光、顯影及後烤處理形成感光性樹脂圖案之後,進行蝕刻及光阻剝離。重複上述步驟後,即可製得含多個薄膜電晶體或電極之薄膜電晶體陣列基板。
請參閱第1圖,其係繪示根據本發明一實施例之液晶顯示(LCD)元件用TFT陣列基板的部分剖面示意圖。首先,於玻璃基板101上的鋁薄膜等處設置閘極102a及儲存電容Cs電極102b。其次,於閘極102a上覆蓋氧化矽膜(SiOx)103或氮化矽膜(SiNx)104等而形成絕緣膜,並於此絕緣膜上形成作為半導體活性層的非晶矽層(a-Si)105。接著,為了降低接面阻抗,可設置摻雜氮不純物的非晶矽層106於非晶矽層105上。之後,使用鋁等金屬,形成汲極107a及源極107b,其中汲極107a連接於資料訊號線(圖未繪示)上,而源極107b則連接於畫素電極(或子畫素電極)109上。而後,為保護作為半導體活性層的非晶矽層105、汲極107a或源極107b等,設置氮化矽膜等作為保護膜108。
本發明之液晶顯示元件至少包括上述之TFT陣列基板,並可依需要包含有其他的部件。
上述液晶顯示元件的基本構成形態之具體例為(1)將TFT等之驅動元件與畫素電極(導電層)經排列所形成的上述本發明之TFT陣列基板(驅動基板),與由彩色濾光片及對電極(導電層)所構成的彩色濾光片基板間介入間隔體並且對向配置,最後於間隙部份封入液晶材料而構成。另一種方式,(2)將於上述本發明之TFT陣列基板上直接形成彩光濾光片之彩色濾光片一體型TFT陣列基板,與配置了對電極(導電層)之對向基板間介入間隔體並且對向配置,最後於間隙部份封入液晶材料而構成等,其中前述使用的液晶材料可為任何一種液晶化合物或液晶組成物,此處並未特別限定。
上述導電層之具體例為ITO膜;鋁、鋅、銅、鐵、鎳、鉻、鉬等之金屬膜;或二氧化矽等之金屬氧化膜。較佳地,其係為具透明性之膜層;更佳為ITO膜。
本發明之TFT陣列基板、彩色濾光片基板及對向基板等所使用之基材,其具體例為鈉鈣玻璃、低膨脹玻璃、無鹼玻璃或石英玻璃之習知玻璃,另外,也可採用由塑膠膜等構成的基板。
以下利用數個實施方式以說明本發明之應用,然其並非用以限定本發明,本發明技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾。
以下係根據第1表製備合成例A-1-1至A-1-6之羥基型酚醛清漆樹脂(A-1)。
在一容積1000毫升之四頸錐瓶上設置氮氣入口、攪拌器、加熱器、冷凝管及溫度計,導入氮氣後添加間-甲酚0.70莫耳、對-甲酚0.30莫耳、3,4-二羥基苯甲醛0.5莫耳及草酸0.020莫耳。緩慢攪拌使反應溶液昇溫至100℃,並於此溫度下聚縮合6小時。然後,將反應溶液昇溫至180℃,以10mmHg之壓力進行減壓乾燥,將溶劑脫揮後可得羥基型酚醛清漆樹脂(A-1-1)。
同合成例A-1之羥基型酚醛清漆樹脂的合成方法,不同處在於合成例A-1-2至A-1-6係改變羥基型酚醛清漆樹脂(A-1)中反應物的種類及使用量,其配方如第1表之所示,此處不另贅述。
同合成例A-1之羥基型酚醛清漆樹脂的合成方法,不同處在於合成例A-2-1至A-2-3係改變其他酚醛清漆樹脂(A-2)中反應物的種類及使用量,其配方如第1表之所示,此處不另贅述。
以下係根據第2表與第3表製備實施例1至13及比較例1至6之正型感光性組成物。
將100重量份由合成例A-1-1所得的羥基型酚醛清漆樹
脂(A-1-1)、25重量份的2,3,4-三羥基二苯甲酮與1,2-萘醌二疊氮-5-磺酸之酯化物(B-1)(平均酯化度85%)、5重量份的2,3,4,4'-四羥基二苯甲酮與1,2-萘醌二疊氮-5-磺酸之酯化物(B-2)、2重量份的C.I.Solvent Black 3(商品名Sudan Black 141;中央合成化學製)(C-1-1)、1重量份的C.I.Acid Violet 17(商品名Coomassie Violet R200;Sigma製)(C-2-1),加入1000重量份的丙二醇甲醚醋酸酯(PGMEA,propylene glycol monomethyl ether acetate)的溶劑(D-1)中,以搖動式攪拌器攪拌使上述混合物溶解於溶劑中,即可製得本發明的正型感光性樹脂組成物。所得之正型感光性樹脂組成物以下列各評價方式進行評估,其結果如第2表所述,其中蝕刻後脫色、解析度以及殘膜率的檢測方法容後再述。
同實施例1之正型感光性樹脂組成物的製備方法,不同處在於實施例2至13係改變正型感光性樹脂組成物中原料的種類及使用量,其配方以及檢測結果如第2表所示,此處不另贅述。
同實施例1之正型感光性樹脂組成物的製備方法,不同處在於比較例1至3係改變正型感光性樹脂組成物中原料的種類及使用量,其配方以及檢測結果亦如第3表所示。
將實施例1至13以及比較例1至6之正型感光性樹脂組成物,於玻璃基板上以旋轉塗佈方式塗佈,在110℃下預烤160秒鐘,可得到約1.5 μm之預烤塗膜。將該預烤塗膜介於指定光阻底下,利用300 mJ/cm2的紫外光(曝光機型號AG500-4N;M&R Nano Technology製)進行照射後,再以2.38% TMAH水溶液,於23℃下予以顯影1分鐘,將基板上曝光部份的塗膜除去,然後以純水洗淨得到圖案。以220℃溫度後烤40分鐘後,再於30℃以鋁酸蝕刻,製得一含圖案之玻璃基版,並以透光率測定儀(透光率測定儀型號NCPD-300;大塚科技股份有限公司製),測量含圖案之玻璃基版的透光頻譜(頻譜波長範圍為400nm~780nm),並以不含圖案之玻璃基版的透光頻譜作為基礎值,便可由透光率測定儀計算出透光率,比率範圍為0%至100%之間。
◎:透光率≦15%
○:15%<透光率≦40%
×:40%<透光率
將實施例1至13以及比較例1至6之正型感光性樹脂組成物,於玻璃基板上以旋轉塗佈方式塗佈後,在110℃下預烤160秒鐘,可得到約1.5 μm之預烤塗膜。接著,將該預烤塗膜介於線與間距(line and space)之光罩(日本Filcon製),利用300 mJ/cm2的紫外光(曝光機型號AG500-4N;M&R Nano Technology製)進行照射後,再以2.38%TMAH水溶液,於23℃下予以顯影1分鐘。然後,將基板上曝光部份的
塗膜除去,並以純水洗淨,其形成的線條幅度的最小值定為解析度。
◎:線幅<2μm
○:2μm≦線幅<3μm
△:3μm≦線幅<5μm
×:線幅≧5μm
於前述檢測項目「解析度」中所得之預烤塗膜上任取一測定點測得一膜厚(δd1),接著浸於23℃之顯影液(2.38%之TMAH水溶液)予以顯影1分鐘後,在相同的測定點測得另一膜厚(δd2)。最後,經下式(XIII)計算可得到殘膜率。
殘膜率(%)=[(δd2)/(δd1)]×100 (XIII)
◎:殘膜率>95%
○:95%>殘膜率>90%
△:90%>殘膜率>85%
×:殘膜率≦85%
上述實施例與比較例所得之正型感光性樹脂組成物,其蝕刻後脫色、解析度以及殘膜率之評估結果如第2表與第3表所示。
由第2表與第3表之結果可知,當正型感光性樹脂組成物使用羥基型酚醛清漆樹脂(A-1)時,所製得之圖案經蝕刻後不易脫色且具有較佳的解析度。其次,當正型感光性樹脂組成物同時使用由雙偶氮系染料、蒽醌系染料及三價鉻偶氮系染料所組成的一群組中至少選自一種(C-1)以及三芳甲烷系染料(C-2)時,由此製得之圖案可具有較佳的解析度以及較佳的殘膜率,而且再併用酞菁系染料(C-3)時,會有解析度佳的優點,故確實可達到本發明之目的。
需補充的是,本發明雖以特定的化合物、組成、反應條件、製程、分析方法或特定儀器作為例示,說明本發明之正型感光性樹脂組成物及其圖案形成方法,惟本發明所屬技術領域中任何具有通常知識者可知,本發明並不限於此,在不脫離本發明之精神和範圍內,本發明之正型感光性樹脂組成物及其圖案形成方法亦可使用其他的化合物、組成、反應條件、製程、分析方法或儀器進行。
雖然本發明已以實施方式揭露如上,然其並非用以限定本發明,在本發明所屬技術領域中任何具有通常知識者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
101‧‧‧玻璃基板液晶顯示元件
102a‧‧‧閘極
102b‧‧‧儲存電容Cs電極
103‧‧‧氧化矽膜
104‧‧‧氮化矽膜
105‧‧‧非晶矽層
106‧‧‧非晶矽層
107a‧‧‧汲極
107b‧‧‧源極
108‧‧‧保護膜
109‧‧‧畫素電極
為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂,所附圖式之說明如下:
第1圖係繪示根據本發明一實施例之液晶顯示元件用TFT陣列基板的部分剖面示意圖。
Claims (12)
- 一種正型感光性樹脂組成物,包含:酚醛清漆樹脂(A),其中該酚醛清漆樹脂(A)包含羥基型酚醛清漆樹脂(A-1),且該羥基型酚醛清漆樹脂(A-1)係由羥基苯甲醛類化合物與芳香族羥基化合物縮合而得;鄰萘醌二疊氮磺酸類之酯化物(B);染料(C),其中該染料(C)包含由雙偶氮系染料、蒽醌系染料及三價鉻偶氮系染料所組成之一群組中至少選自一種(C-1),及三芳甲烷系染料(C-2);以及溶劑(D)。
- 如申請專利範圍第1項所述之正型感光性樹脂組成物,其中基於該酚醛清漆樹脂(A)為100重量份,該羥基型酚醛清漆樹脂(A-1)之使用量為30重量份至100重量份。
- 如申請專利範圍第1項所述之正型感光性樹脂組成物,其中基於該酚醛清漆樹脂(A)為100重量份,該鄰萘醌二疊氮磺酸類之酯化物(B)的使用量為5重量份至50重量份,該染料(C)的使用量為10重量份至150重量份,且該溶劑(D)的使用量為500重量份至2000重量份。
- 如申請專利範圍第1項所述之正型感光性樹脂組成物,其中基於該酚醛清漆樹脂(A)為100重量份,該由雙偶氮系染料、蒽醌系染料及三價鉻偶氮系染料所組成之一群組中至少選自一種(C-1)的使用量為2重量份至30重量份,且該 三芳甲烷系染料(C-2)的使用量為1重量份至10重量份。
- 如申請專利範圍第1項所述之正型感光性樹脂組成物,其中該由雙偶氮系染料、蒽醌系染料及三價鉻偶氮系染料所組成之一群組中至少選自一種(C-1)之使用量與該三芳甲烷系染料(C-2)之使用量之比值為1至10。
- 如申請專利範圍第1項所述之正型感光性樹脂組成物,其中該三芳甲烷系染料(C-2)包含具有式(I)或式(II)所示之結構或其鹽類:
- 如申請專利範圍第1項所述之正型感光性樹脂組成物,其中該染料(C)更包含酞菁系染料(C-3)。
- 如申請專利範圍第7項所述之正型感光性樹脂組成物,其中基於該酚醛清漆樹脂(A)為100重量份,該酞菁系染料(C-3)的使用量為3重量份至60重量份。
- 如申請專利範圍第7項所述之正型感光性樹脂組成物,其中該酞菁系染料(C-3)包含具有式(VI)所示之結構:
- 一種圖案形成方法,其係由對如申請專利範圍第1項至第9項任一項所述之正型感光性樹脂組成物依序施予一預烤處理、一曝光處理、一顯影處理以及一後烤處理,藉以於一基板上形成一圖案。
- 一種薄膜電晶體陣列基板,其包含如申請專利範圍第10項所述之圖案。
- 一種液晶顯示元件,其包含如申請專利範圍第11項所述之薄膜電晶體陣列基板。
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US13/970,611 US9188859B2 (en) | 2012-08-29 | 2013-08-20 | Positive photosensitive resin composition and method for forming patterns by using the same |
CN201310368638.6A CN103676482A (zh) | 2012-08-29 | 2013-08-22 | 正型感光性树脂组合物及其图案形成方法 |
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CN107406590B (zh) * | 2015-01-27 | 2020-08-04 | 东丽株式会社 | 树脂、感光性树脂组合物及使用了它们的电子部件、显示装置 |
KR101856051B1 (ko) * | 2015-10-14 | 2018-05-09 | 삼성에스디아이 주식회사 | 감광성 수지 조성물, 이를 이용한 감광성 수지막 및 컬러필터 |
US10866512B2 (en) * | 2015-10-21 | 2020-12-15 | Showa Denko K.K. | Positive photosensitive resin composition |
WO2019068355A1 (en) | 2017-10-06 | 2019-04-11 | Alfa Instruments S.R.L. | BLUE GLYING (BBG) COLOR DERIVATIVES AND COLORING COMPOUNDS COMPRISING THEM FOR SELECTIVELY COLORING BIOLOGICAL SUBSTRATES |
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US5151339A (en) * | 1989-09-08 | 1992-09-29 | Ocg Microelectronic Materials, Inc. | Photoresist composition containing diazoquinone photosensitizer and novalak resin characterized by the complete and selective removal of dimeric species from the novolak resin |
US5346799A (en) * | 1991-12-23 | 1994-09-13 | Ocg Microelectronic Materials, Inc. | Novolak resins and their use in radiation-sensitive compositions wherein the novolak resins are made by condensing 2,6-dimethylphenol, 2,3-dimethylphenol, a para-substituted phenol and an aldehyde |
US5821345A (en) * | 1996-03-12 | 1998-10-13 | Shipley Company, L.L.C. | Thermodynamically stable photoactive compound |
JP3724159B2 (ja) | 1997-11-04 | 2005-12-07 | コニカミノルタホールディングス株式会社 | 感光性組成物 |
TWI333127B (en) * | 2003-04-07 | 2010-11-11 | Toray Industries | Positive-type photosensitive resin composition |
JP4657147B2 (ja) * | 2006-05-24 | 2011-03-23 | 住友化学株式会社 | 着色感光性樹脂組成物、カラーフィルタ、イメージセンサおよびカメラシステム |
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