TW201319738A - 光可固化組成物,及使用彼之圖案化方法 - Google Patents
光可固化組成物,及使用彼之圖案化方法 Download PDFInfo
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- TW201319738A TW201319738A TW101138431A TW101138431A TW201319738A TW 201319738 A TW201319738 A TW 201319738A TW 101138431 A TW101138431 A TW 101138431A TW 101138431 A TW101138431 A TW 101138431A TW 201319738 A TW201319738 A TW 201319738A
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- photocurable composition
- ether
- meth
- acrylate
- mold
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- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
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- 125000000542 sulfonic acid group Chemical group 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
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 150000003568 thioethers Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 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
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- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
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- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- ZFEAYIKULRXTAR-UHFFFAOYSA-M triphenylsulfanium;chloride Chemical compound [Cl-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 ZFEAYIKULRXTAR-UHFFFAOYSA-M 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- FAYMLNNRGCYLSR-UHFFFAOYSA-M triphenylsulfonium triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FAYMLNNRGCYLSR-UHFFFAOYSA-M 0.000 description 1
- 125000002948 undecyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
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- B05D3/067—Curing or cross-linking the coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
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- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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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
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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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
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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- G—PHYSICS
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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
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- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
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- G—PHYSICS
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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
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- G—PHYSICS
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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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0014—Shaping of the substrate, e.g. by moulding
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0017—Etching of the substrate by chemical or physical means
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
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- Condensed Matter Physics & Semiconductors (AREA)
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- Plasma & Fusion (AREA)
- Mechanical Engineering (AREA)
- Polymerisation Methods In General (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
本發明提供所需脫模力小的光可固化組成物。本發明亦提供所需脫模力小的UV刻印法。該光可固化組成物含有可聚合的單體(A)、聚合反應引發劑(B)、和含氟的界面活性劑(C)。該光可固化組成物之光固化產物的水接觸角度為74度或更低。
Description
本發明係關於光可固化組成物,及使用該光可固化組成物之圖案化方法。
UV奈米刻印法係將其表面上具有細特定結構圖案的模具壓在經光阻物(光可固化組成物)塗覆的基板上以將特定結構圖案轉移至基板上的光阻膜之方法。
UV奈米刻印法中,重要的是減少模具自固化的光阻物脫模的力,即,脫模力。此因大脫模力會引發圖案缺陷或造成基板自台座浮起,造成對準精度(alignment precision)低之故。
用於光奈米刻印的已知光可固化組成物含有至少一種可聚合的單體、聚合反應引發劑、和氟化的界面活性劑。
PTL 1亦揭示全氟烷基鏈鍵結至烴鏈之氟化的界面活性劑或全氟烷基鏈鍵結至乙氧基鏈、甲氧基鏈、或矽氧烷之氟化的界面活性劑之用途。
PTL 2揭示所得光固化膜撥水且較佳地具有的水接觸角度在75至98度的範圍內。
PTL 1日本專利公開第2007-084625號
PTL 2國際公開WO 2006/114958
如上述者,已經知道氟化材料可加至組成物以賦予光固化膜表面撥水性及降低脫模力。但是,僅添加已知氟化材料不一定能提供介於模具表面和光固化膜表面間之界面,該界面對於減低脫模力有貢獻,且仍導致大脫模力。
鑑於與相關技術有關的此問題,本發明提供於圖案化方法中所需脫模力小的光可固化組成物。本發明亦提供所需脫模力小的圖案化方法。
欲解決上述問題,根據本發明的一方面之光可固化組成物含有可聚合的單體(A),聚合反應引發劑(B),和含氟的界面活性劑(C),其中該組成物之光固化產物的水接觸角度為74度或更低。
根據本發明之一方面的圖案化方法包括將光可固化組成物置於待加工的基板上,令該光可固化組成物與模具接觸,對該光可固化組成物照光,和在照光之後,令該光可固化組成物自模具脫模。
本發明提供所需脫模力小的光可固化組成物。本發明亦提供所需脫模力小的圖案化方法。
將以以下具體實施例進一步描述本發明。本發明不限於這些具體實施例。嫻於此技術者將瞭解在不背離本發明之要點的情況下,變體和修飾可用於這些具體實施例。亦欲使這些變體和修飾屬於本發明之範圍內。
此處所謂“圖案化方法”包括UV刻印法。UV刻印法較佳地定義為用以形成尺寸在1奈米至10毫米,更佳約10奈米至100微米,之範圍內的圖案之方法。形成奈米尺寸(1至100奈米)圖案(結構化的結構)的技巧通常被稱為光奈米刻印(photo-nanoimprint)。本發明包括光奈米刻印。
根據本發明之具體實施例的光可固化組成物含有可聚合的單體(A)、聚合反應引發劑(B)、和含氟的界面活性劑(C)。此光可固化組成物可含有另一添加劑組份。
含氟的界面活性劑(C)的一端可具有極性官能基。
控制含氟的界面活性劑(C)的量,使得根據本發明之具體實施例之光可固化組成物之光固化產物的水接觸角度為74度或更低。
如PTL 2中所揭示者,目前較佳者之光固化膜具撥水性且其水接觸角度在75至98度的範圍內。
致力於研究的結果是,本發明者發現該光可固化組成
物之光固化產物的水接觸角度為74度或更低時,其所需的脫模力小。
雖然根據本發明之具體實施例之組成物的接觸角度為74度或更低時,其所需脫模力小之原因未明,但推測為含氟的界面活性劑(C)集結於光固化產物表面上,而界面活性劑的末端官能基賦予光固化產物疏水性之故。當官能基接至模具表面,含氟的界面活性劑(C)的薄膜形成於模具和光阻物之間的界面處並藉此而降低脫模力。特別地,末端官能基具有高極性時,此可能有助於與模具表面形成極性鍵及形成薄膜。
此外,當含氟的界面活性劑(C)的一端具有全氟烷基鏈(C-a)和另一端具有極性官能基(C-c),且該全氟烷基鏈經由聚(環氧烷基)鏈(C-b1)和/或烷基鏈(C-b2)鏈結至該極性官能基時,推測極性官能基(C-c)與模具表面形成極性鍵,及模具和光阻物之間的界面處形成之含氟的界面活性劑(C)的薄膜可降低脫模力。
全氟烷基鏈(C-a)的特定例子包括,但不限於,經氟取代之具1至20個碳原子的直鏈烷基,如全氟甲基、全氟乙基、全氟丙基、全氟丁基、全氟戊基、全氟己基、全氟庚基、全氟辛基、全氟壬基、和全氟癸基。就環境安全的觀點,碳原子數可為7或更低。
極性官能基(C-c)的特定例子包括,但不限於,烷羥基、羧基、巰基、胺基、吡啶基、矽醇基、和磺酸基。
聚(環氧烷基)鏈(C-b1)的特定例子包括,但不限
於,具有1至100個重複單元的聚(環氧乙烷)鏈和具有1至100個重複單元的聚(環氧丙烷)鏈。
烷基鏈(C-b2)的特定例子包括,但不限於,具1至100個碳原子和直鏈或環結構的烷基。
(C-a)和(C-b1)、(C-a)和(C-b2)、(C-b1)和(C-c)、或(C-b2)和(C-c)可經由二價鏈結基團鏈結。二價鏈結基團的特定例子包括,但不限於,伸烷基、伸苯基、伸萘基、酯基、醚基、硫醚基、磺醯基、二級胺基、三級胺基、醯胺基、和胺甲酸基。
含氟的界面活性劑(C)可為至少一種具有以下通式(1)的化合物:〔式1〕F(CF2)6(CH2)m(OCH2CH2)nOH (1)其中m是1至3的整數,而n是1至100的整數。
含氟的界面活性劑(C)可以單獨使用或併用。
以可聚合的單體(A)量計,含氟的界面活性劑(C)可為0.001重量%至5重量%,較佳地0.002重量%至4重量%,更佳地0.005重量%至3重量%。如上述者,控制含氟的界面活性劑(C)的量,使得根據本發明之具體實施例之光可固化組成物的光固化產物的水接觸角度為74度或更低。
光固化產物的水接觸角度為74度或更低且為1度或
更高,較佳地為10度或更高。
特別地,此光固化產物的水接觸角度為70度或更低,或71度或更高且為74度或更低。
以下將描述測定根據本發明之光固化產物的水接觸角度之方法。
藉塗覆(如旋塗)而將根據本發明之具體實施例的光可固化組成物施於基板上,在惰性氣體(如氮氣)中,對該光可固化組成物照光以形成光固化膜,藉此可製得光固化產物。
可以市售接觸角度計,如全自動接觸角度計CA-W(Kyowa Interface Science Co.,Ltd.生產),測定水接觸角度。
本發明之光固化膜的水接觸角度定義為介於光固化膜表面和光固化膜上之1微升純水和光固化膜的交點處之切線之間的角度。水接觸角度可為於樣品上的不同位置進行多次測定的平均值。
根據本發明之具體實施例之光可固化組成物之可聚合的單體可為自由基可聚合的單體或陽離子可聚合的單體。
此自由基可聚合的單體可為具有至少一個丙烯醯基或甲基丙烯醯基的化合物。此陽離子可聚合的單體可為具有
至少一個乙烯醚基、乙氧基、或環氧丁基的化合物。
具有一個丙烯醯基或甲基丙烯醯基之單官能性(甲基)丙烯醯基化合物的例子包括,但不限於,(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸苯氧基-2-甲基乙酯、(甲基)丙烯酸苯氧基乙氧基乙酯、(甲基)丙烯酸3-苯氧基-2-羥丙酯、(甲基)丙烯酸2-苯基苯氧基乙酯、(甲基)丙烯酸4-苯基苯氧基乙酯、(甲基)丙烯酸3-(2-苯基苯基)-2-羥丙酯、經EO-改質的對-異丙苯基酚(甲基)丙烯酸酯、(甲基)丙烯酸2-溴苯氧基乙酯、(甲基)丙烯酸2,4-二溴苯氧基乙酯、(甲基)丙烯酸2,4,6-三溴苯氧基乙酯、經EO-改質的(甲基)丙烯酸苯氧酯、經PO-改質的(甲基)丙烯酸苯氧酯、聚環氧乙烷壬基苯基醚(甲基)丙烯酸酯、(甲基)丙烯酸異酯、(甲基)丙烯酸1-金剛酯、(甲基)丙烯酸2-甲基-2-金剛酯、(甲基)丙烯酸2-乙基-2-金剛酯、(甲基)丙烯酸酯、(甲基)丙烯酸三環癸酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸4-丁基環己酯、丙烯醯基嗎啉、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲
基)丙烯酸異丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸丁氧基乙酯、(甲基)丙烯酸乙氧基二乙二醇酯、單(甲基)丙烯酸聚(乙二醇)酯、單(甲基)丙烯酸聚(丙二醇)酯、(甲基)丙烯酸甲氧基乙二醇酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸甲氧基聚(乙二醇)酯、(甲基)丙烯酸甲氧基聚(丙二醇)酯、二丙酮(甲基)丙烯醯胺、(甲基)丙烯酸異丁氧基甲酯、N,N-二甲基(甲基)丙烯醯胺、三級辛基(甲基)丙烯醯胺、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯、(甲基)丙烯酸7-胺基-3,7-二甲基辛酯、N,N-二乙基(甲基)丙烯醯胺、和N,N-二甲胺基丙基(甲基)丙烯醯胺。
單官能性(甲基)丙烯醯基化合物可為,但不限於,以下產品:Aronix M101、M102、M110、M111、M113、M117、M5700、TO-1317、M120、M150、或M156(Toagosei Co.,Ltd.生產)、MEDOL 10、MIBDOL 10、CHDOL 10、MMDOL 30、MEDOL 30、MIBDOL 30、
CHDOL 30、LA、IBXA、2-MTA、HPA、或Viscoat #150、#155、#158、#190、#192、#193、#220、#2000、#2100、或#2150(Osaka Organic Chemical Industry Ltd.生產)、Light Acrylate BO-A、EC-A、DMP-A、THF-A、HOP-A、HOA-MPE、HOA-MPL、PO-A、P-200A、NP-4EA、或NP-8EA、或環氧酯M-600A(Kyoeisha Chemical Co.,Ltd.生產)、Kayarad TC110S、R-564、或R-128H(Nippon Kayaku Co.,Ltd.生產)、NK酯AMP-10G或AMP-20G(Shin Nakamura Chemical Co.,Ltd.生產)、FA-511A、512A、或513A(Hitachi Chemical Co.,Ltd.生產)、PHE、CEA、PHE-2、PHE-4、BR-31、BR-31M、或BR-32(Dai-ichi Kogyo Seiyaku Co.,Ltd.生產)、VP(BASF生產)、或ACMO、DMAA、或DMAPAA(Kohjin Co.,Ltd.生產)。
具有至少兩個丙烯醯基或甲基丙烯醯基的多官能性(甲基)丙烯醯基化合物的例子包括,但不限於,三羥甲基丙烷二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、經EO-改質的三羥甲基三(甲基)丙烯酸酯、經PO-改質的三羥甲基丙烷三(甲基)丙烯酸酯、經EO,PO-改質的三羥甲基丙烷三(甲基)丙烯酸酯、三(甲基)丙烯酸季戊四醇酯、四(甲基)丙烯酸季戊四醇酯、二(甲基)丙烯酸乙二醇酯、二(甲基)丙烯酸四(乙二醇)酯、二(甲基)丙烯酸聚(乙二醇)酯、二(甲基)丙烯酸聚(丙二醇)酯、二(甲基)丙烯酸1,4-丁二醇酯、二
(甲基)丙烯酸1,6-己二醇酯、二(甲基)丙烯酸新戊二醇酯、三(甲基)丙烯酸參(2-羥乙基)異氰尿酸酯、參(丙烯醯氧基)異氰脲酸酯、雙(羥甲基)三環癸烷二(甲基)丙烯酸酯、五(甲基)丙烯酸二季戊四醇酯、六(甲基)丙烯酸二季戊四醇酯、經EO-改質的2,2-雙(4-((甲基)丙烯醯氧基)苯基)丙烷、經PO-改質的2,2-雙(4-((甲基)丙烯醯氧基)苯基)丙烷、和經EO,PO-改質的2,2-雙(4-((甲基)丙烯醯氧基)苯基)丙烷。
多官能性(甲基)丙烯醯基化合物可為,但不限於,以下產品:Yupimer UV SA1002或SA2007(Mitsubishi Chemical Corp.生產)、Viscoat #195、#230、#215、#260、#335HP、#295、#300、#360、#700、GPT、或3PA(Osaka Organic Chemical Industry Ltd.生產)、Light Acrylate 4EG-A、9EG-A、NP-A、DCP-A、BP-4EA、BP-4PA、TMP-A、PE-3A、PE-4A、或D PE-6A(Kyoeisha Chemical Co.,Ltd.)、Kayarad PET-30、TMPTA、R-604、DPHA、DPCA-20、-30、-60、或-120、HX-620、D-310、或D-330(Nippon Kayaku Co.,Ltd.生產)、Aronix M208、M210、M215、M220、M240、M305、M309、M310、M315、M325、或M400(Toagosei Co.,Ltd.生產)、或Ripoxy VR-77、VR-60、或VR-90(Showa Highpolymer Co.,Ltd.生產)。
這些自由基可聚合的單體可以單獨使用或併用。此處所謂“(甲基)丙烯酸酯”是指丙烯酸酯和彼之對應的甲基
丙烯酸酯。此處所謂的“(甲基)丙烯醯基”是指丙烯醯基和彼之對應的甲基丙烯醯基。EO代表環氧乙烷,而經EO-改質的化合物具有環氧乙烷基的嵌段結構。PO代表環氧丙烷,而經PO-改質的化合物具有環氧丙烷基的嵌段結構。
具有一個乙烯醚基之化合物的例子包括,但不限於,甲基乙烯醚、乙基乙烯醚、丙基乙烯醚、正丁基乙烯醚、三級丁基乙烯醚、2-乙基己基乙烯醚、正壬基乙烯醚、月桂基乙烯醚、環己基乙烯醚、環己基甲基乙烯醚、4-甲基環己基甲基乙烯醚、苄基乙烯醚、二環戊烯基乙烯醚、2-二環戊烯氧基乙基乙烯醚、甲氧基乙基乙烯醚、乙氧基乙基乙烯醚、丁氧基乙基乙烯醚、甲氧基乙氧基乙基乙烯醚、乙氧基乙氧基乙基乙烯醚、甲氧基聚(乙二醇)乙烯醚、四氫糠基乙烯醚、2-羥乙基乙烯醚、2-羥丙基乙烯醚、4-羥丁基乙烯醚、4-羥甲基環己基甲基乙烯醚、二乙二醇單乙烯醚、聚(乙二醇)乙烯醚、氯乙基乙烯醚、氯丁基乙烯醚、氯乙氧基乙基乙烯醚、苯基乙基乙烯醚、和苯氧基聚(乙二醇)乙烯醚。
具有至少兩個乙烯醚基之化合物的例子包括,但不限於,二乙烯醚,如乙二醇二乙烯醚、二乙二醇二乙烯醚、聚(乙二醇)二乙烯醚、丙二醇二乙烯醚、丁二醇二乙烯醚、己二醇二乙烯醚、雙酚A環氧烷二乙烯醚、和雙酚F
環氧烷二乙烯醚;和多官能性乙烯醚,如三羥甲基乙烷三乙烯醚、三羥甲基丙烷三乙烯醚、二三羥甲基丙烷四乙烯醚、甘油三乙烯醚、季戊四醇四乙烯醚、二季戊四醇五乙烯醚、二季戊四醇六乙烯醚、三羥甲基丙烷三乙烯醚的環氧乙烷加合物、三羥甲基丙烷三乙烯醚的環氧丙烷加合物、二三羥甲基丙烷四乙烯醚的環氧乙烷加合物、二三羥甲基丙烷四乙烯醚的環氧丙烷加合物、季戊四醇四乙烯醚的環氧乙烷加合物、季戊四醇四乙烯醚的環氧丙烷加合物、二季戊四醇六乙烯醚的環氧乙烷加合物、和二季戊四醇六乙烯醚的環氧丙烷加合物。
具有一個環氧基的化合物的例子包括,但不限於,苯基環氧丙基醚、對-三級丁基苯基環氧丙基醚、丁基環氧丙基醚、2-乙基己基環氧丙基醚、烯丙基環氧丙基醚、1,2-環氧丁烷、1,3-丁二烯一氧化物、1,2-環氧癸烷、表氯醇、1,2-環氧基癸烷、苯乙烯化氧、環氧己烷、3-甲基丙烯醯氧基甲基環氧己烷、3-丙烯醯氧基甲基環氧己烷、和3-乙烯基環氧己烷。
具有至少兩個環氧基的化合物的例子包括,但不限於,雙酚A二環氧丙基醚、雙酚F二環氧丙基醚、雙酚S二環氧丙基醚、溴化的雙酚A二環氧丙基醚、溴化的雙酚F二環氧丙基醚、溴化的雙酚S二環氧丙基醚、環氧清漆樹脂、氫化的雙酚A二環氧丙基醚、氫化的雙酚F二環氧丙基醚、氫化的雙酚S二環氧丙基醚、3,4-環氧基環己基甲基-3’,4’-環氧基環己烷羧酸酯、2-(3,4-環氧基環己基-
5,5-螺-3,4-環氧基)環己烷-間-二烷、雙(3,4-環氧基環己基甲基)己二酸酯、乙烯基環氧己烷、4-乙烯基環氧基環己酮、雙(3,4-環氧基-6-甲基環己基甲基)己二酸酯、3,4-環氧基-6-甲基環己基-3’,4’-環氧基-6’-甲基環己烷羧酸酯、伸甲基雙(3,4-環氧基環己烷)、二環戊二烯基二環氧化物、乙二醇二(3,4-環氧基環己基甲基)醚、伸乙基雙(3,4-環氧基環己烷羧酸酯)、酞酸環氧基六氫二辛酯、酞酸環氧基六氫二-2-乙基己酯、1,4-丁二醇二環氧丙基醚、1,6-己二醇二環氧丙基醚、甘油三環氧丙基醚、三羥甲基丙烷三環氧丙基醚、聚(乙二醇)二環氧丙基醚、聚(丙二醇)二環氧丙基醚、1,1,3-十四碳二烯二氧化物、檸檬烯二氧化物、1,2,7,8-二環氧基辛烷、和1,2,5,6-二環氧基環辛烷。
具有環氧丁基的化合物的例子包括,但不限於,3-乙基-3-羥甲基環氧丁烷、3-(間)烯丙氧基甲基-3-乙基環氧丁烷、(3-乙基-3-環氧丁基甲氧基)甲基苯、4-氟-〔1-(3-乙基-3-環氧丁基甲氧基)甲基〕苯、4-甲氧基-〔1-(3-乙基-3-環氧丁基甲氧基)甲基〕苯、〔1-(3-乙基-3-環氧丁基甲氧基)乙基〕苯基醚、異丁氧基甲基(3-乙基-3-環氧丁基甲基)醚、異基氧基乙基(3-乙基-3-環氧丁基甲基)醚、異基(3-乙基-3-環氧丁基甲基)醚、2-乙基己基(3-乙基-3-環氧丁基甲基)醚、乙基二乙二醇(3-乙基-3-環氧丁基甲基)醚、二環戊二烯(3-乙基-3-環氧丁基甲基)醚、二環戊烯氧基乙基(3-乙基-3-
環氧丁基甲基)醚、二環戊烯基(3-乙基-3-環氧丁基甲基)醚、四氫糠基(3-乙基-3-環氧丁基甲基)醚、四溴苯基(3-乙基-3-環氧丁基甲基)醚、2-四溴苯氧基乙基(3-乙基-3-環氧丁基甲基)醚、三溴苯基(3-乙基-3-環氧丁基甲基)醚、2-三溴苯氧基乙基(3-乙基-3-環氧丁基甲基)醚、2-羥乙基(3-乙基-3-環氧丁基甲基)醚、2-羥丙基(3-乙基-3-環氧丁基甲基)醚、丁氧基乙基(3-乙基-3-環氧丁基甲基)醚、五氯苯基(3-乙基-3-環氧丁基甲基)醚、五溴苯基(3-乙基-3-環氧丁基甲基)醚、和基(3-乙基-3-環氧丁基甲基)醚。
具有至少兩個環氧丁基的化合物的例子包括,但不限於,多官能性環氧丁烷,如3,7-雙(3-環氧丁基)5-氧-壬烷、3,3’-(1,3-(2-甲基)丙二基雙(氧伸甲基))雙-(3-乙基環氧丁烷)、1,4-雙〔(3-乙基-3-環氧丁基甲氧基)甲基〕苯、1,2-雙〔(3-乙基-3-環氧丁基甲氧基)甲基〕丙烷、1,3-雙〔(3-乙基-3-環氧丁基甲氧基)甲基〕丙烷、乙二醇雙(3-乙基-3-環氧丁基甲基)醚、二環戊烯基雙(3-乙基-3-環氧丁基甲基)醚、三(乙二醇)雙(3-乙基-3-環氧丁基甲基)醚、四(乙二醇)雙(3-乙基-3-環氧丁基甲基)醚、三環癸二基二伸甲雙(3-乙基-3-環氧丁基甲基)醚、三羥甲基丙烷參(3-乙基-3-環氧丁基甲基)醚、1,4-雙(3-乙基-3-環氧丁基甲氧基)丁烷、1,6-雙(3-乙基-3-環氧丁基甲氧基)己烷、季戊四醇參(3-乙基-3-環氧丁基甲基)醚、季戊四醇肆(3-乙基-3-環氧丁
基甲基)醚、聚(乙二醇)雙(3-乙基-3-環氧丁基甲基)醚、二季戊四醇陸(3-乙基-3-環氧丁基甲基)醚、二季戊四醇伍(3-乙基-3-環氧丁基甲基)醚、二季戊四醇肆(3-乙基-3-環氧丁基甲基)醚、經己內酯改質的二季戊四醇陸(3-乙基-3-環氧丁基甲基)醚、經己內酯改質的二季戊四醇伍(3-乙基-3-環氧丁基甲基)醚、二三羥甲基丙烷肆(3-乙基-3-環氧丁基甲基)醚、經EO-改質的雙酚A雙(3-乙基-3-環氧丁基甲基)醚、經PO-改質的雙酚A雙(3-乙基-3-環氧丁基甲基)醚、經EO-改質之氫化的雙酚A雙(3-乙基-3-環氧丁基甲基)醚、經PO-改質之氫化的雙酚A雙(3-乙基-3-環氧丁基甲基)醚、和經EO改質的雙酚F(3-乙基-3-環氧丁基甲基)醚。
這些陽離子可聚合的單體可以單獨使用或併用。EO代表環氧乙烷,而經EO-改質的化合物具有環氧乙烷基的嵌段結構。PO代表環氧丙烷,而經PO-改質的化合物具有環氧丙烷基的嵌段結構。此處所謂“氫化的”是指氫原子加至例如,苯環的C=C雙鍵。
當可聚合的單體(A)係自由基可聚合的單體時,聚合反應引發劑(B)藉光(紅外光、可見光、紫外光、遠紫外光、X-射線、帶電的粒子束(如電子束)或放射性射線)的作用而生成自由基。當可聚合的單體(A)為陽離子可聚合的單體時,此聚合反應引發劑(B)藉光的作用
而生成酸。
自由基生成劑的例子包括,但不限於,經任意取代的2,4,5-三芳基咪唑二聚物,如2-(鄰-氯苯基)-4,5-二苯基咪唑二聚物、2-(鄰-氯苯基)-4,5-二(甲氧基苯基)咪唑二聚物、2-(鄰-氟苯基)-4,5-二苯基咪唑二聚物、和2-(鄰-或對-甲氧基苯基)-4,5-二苯基咪唑二聚物;二苯基酮和二苯基酮衍生物,如N,N’-四甲基-4,4’-二胺基二苯基酮(Michler酮)、N,N’-四乙基-4,4’-二胺基二苯基酮、4-甲氧基-4’-二甲胺基二苯基酮、4-氯二苯基酮、4,4’-二甲氧基二苯基酮、和4,4’-二胺基二苯基酮;芳族酮衍生物,如2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮-1,2-甲基-1-〔4-(甲硫基)苯基〕-2-嗎啉基-丙-1-酮;醌,如2-乙基蒽醌、菲醌、2-三級丁基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-苯并蒽醌、2-苯基蒽醌、2,3-二苯基蒽醌、1-氯蒽醌、2-甲基蒽醌、1,4-萘醌、9,10-菲醌、2-甲基-1,4-萘醌、和2,3-二甲基蒽醌;苯偶因醚衍生物,如苯偶因甲醚、苯偶因乙醚、和苯偶因苯醚;苯偶因和苯偶因衍生物,如甲基苯偶因、乙基苯偶因、和丙基苯偶因;苄基衍生物,如苄基二甲縮酮;吖啶衍生物,如9-苯基吖啶和1,7-雙(9,9’-吖啶基)
庚烷;N-苯基甘油和N-苯基甘油衍生物;苯乙酮和苯乙酮衍生物,如3-甲基苯乙酮、苯乙酮苄基縮酮、1-羥基環己基苯基酮、和2,2-二甲氧基-2-苯基苯乙酮;9-氧硫(thioxanthone)和9-氧硫衍生物,如二乙基-9-氧硫、2-異丙基-9-氧硫、和2-氯-9-氧硫;氧蒽酮(xanthone)、茀酮(fluorenone)、苯甲醛、茀、蒽醌、三苯基胺、咔唑、1-(4-異丙基苯基)-2-羥基-2-甲基丙-1-酮、和2-羥基-2-甲基-1-苯基丙-1-酮;和2,4,6-三甲基苄醯基二苯基氧化膦、和雙-(2,6-二甲氧基苄醯基)-2,4,4-三甲基戊基氧化膦。這些自由基生成劑可以單獨使用或併用。
光誘發的自由基生成劑可為,但不限於,以下產品:Irgacure 184、369、651、500、819、907、784、2959、CGI-1700、-1750、或-1850、或CG24-61、或Darocur 1116或1173(Ciba Japan K.K.生產)、Lucirin TPO、LR8893、或LR8970(BASF生產)、或Ebecryl P36(UCB生產)。
作為藉光的作用而製造酸之聚合反應引發劑之化合物的例子包括,但不限於,鎓鹽化合物、碸化合物、磺酸酯化合物、磺醯亞胺化合物、和疊氮甲烷化合物。
鎓鹽化合物的例子包括,但不限於,碘鎓鹽、硫鎓
鹽、磷鎓鹽、疊氮鹽、銨鹽和吡啶鹽。鎓鹽的例子包括,但不限於,雙(4-三級丁基苯基)碘鎓全氟-正丁磺酸鹽、雙(4-三級丁基苯基)碘鎓三氟甲磺酸鹽、雙(4-三級丁基苯基)碘鎓2-三氟甲基苯磺酸鹽、雙(4-三級丁基苯基)碘鎓芘磺酸鹽、雙(4-三級丁基苯基)碘鎓正十二烷基磺酸鹽、雙(4-三級丁基苯基)碘鎓對-甲苯磺酸鹽、雙(4-三級丁基苯基)碘鎓苯磺酸鹽、雙(4-三級丁基苯基)碘鎓10-樟腦磺酸鹽、雙(4-三級丁基苯基)碘鎓正辛磺酸鹽、二苯基碘鎓全氟-正丁磺酸鹽、二苯基碘鎓三氟甲磺酸鹽、二苯基碘鎓2-三氟甲基苯磺酸鹽、二苯基碘鎓芘磺酸鹽、二苯基碘鎓正十二烷基苯磺酸鹽、二苯基碘鎓對-甲苯磺酸鹽、二苯基碘鎓苯磺酸鹽、二苯基碘鎓10-樟腦磺酸鹽、二苯基碘鎓正辛磺酸鹽、三苯基硫鎓全氟正丁磺酸鹽、三苯基硫鎓三氟甲磺酸鹽、三苯基硫鎓2-三氟甲基苯磺酸鹽、三苯基硫鎓芘磺酸鹽、三苯基硫鎓正十二烷基苯磺酸鹽、三苯基硫鎓對-甲苯磺酸鹽、三苯基硫鎓苯磺酸鹽、三苯基硫鎓10-樟腦磺酸鹽、三苯基硫鎓正辛磺酸鹽、二苯基(4-三級丁基苯基)硫鎓全氟-正丁磺酸鹽、二苯基(4-三級丁基苯基)硫鎓三氟甲磺酸鹽、二苯基(4-三級丁基苯基)硫鎓2-三氟甲基苯磺酸鹽、二苯基(4-三級丁基苯基)硫鎓芘磺酸鹽、二苯基(4-三級丁基苯基)硫鎓正十二烷基苯磺酸鹽、二苯基(4-三級丁基苯基)硫鎓對-甲苯磺酸鹽、二苯基(4-三級丁基苯基)硫鎓苯磺酸鹽、二苯基(4-三級丁基苯基)硫鎓10-樟腦磺酸
鹽、二苯基(4-三級丁基苯基)硫鎓正辛磺酸鹽、參(4-甲氧基苯基)硫鎓全氟正丁磺酸鹽、參(4-甲氧基苯基)硫鎓三氟甲磺酸鹽、參(4-甲氧基苯基)硫鎓2-三氟甲苯磺酸鹽、參(4-甲氧基苯基)硫鎓芘磺酸鹽、參(4-甲氧基苯基)硫鎓正十二烷基苯磺酸鹽、參(4-甲氧基苯基)硫鎓對-甲苯磺酸鹽、參(4-甲氧基苯基)硫鎓苯磺酸鹽、參(4-甲氧基苯基)硫鎓10-樟腦磺酸鹽、和參(4-甲氧基苯基)硫鎓正辛磺酸鹽。
碸化合物的例子包括,但不限於,β-酮基碸、β-磺醯基碸、和彼等的α-疊氮化合物。碸化合物的例子包括,但不限於,苯甲醯甲基苯基碸、2,4,6-三甲苯基苯甲醯甲基碸、雙(苯基磺醯基)甲烷、和4-參苯甲醯甲基碸。
磺酸酯化合物的例子包括,但不限於,烷基磺酸酯、鹵烷基磺酸酯、芳基磺酸酯、和亞胺基磺酸酯。磺酸酯化合物的特定例子包括,但不限於,α-羥甲基苯偶因全氟正丁磺酸酯、α-羥甲基苯偶因三氟甲磺酸酯、和α-羥甲基苯偶因2-三氟甲基苯磺酸酯。
磺醯亞胺化合物的特定例子包括,但不限於,N-(三氟甲基磺醯氧基)丁二醯亞胺、N-(三氟甲基磺醯氧基)酞醯亞胺、N-(三氟甲基磺醯氧基)二苯基馬來醯亞胺、N-(三氟甲基磺醯氧基)二環〔2.2.1〕庚-5-烯-2,3-二羧醯亞胺、N-(三氟甲基磺醯氧基)-7-氧二環〔2.2.1〕庚-5-烯-2,3-二羧醯亞胺、N-(三氟甲基磺醯氧基)二環〔2.2.1〕庚-5,6-氧-2,3-二羧醯亞胺、N-(三氟甲基磺醯
氧基)萘醯亞胺、N-(10-樟腦磺醯氧基)丁二醯亞胺、N-(10-樟腦磺醯氧基)酞醯亞胺、N-(10-樟腦磺醯氧基)二苯基馬來醯亞胺、N-(10-樟腦磺醯氧基)二環〔2.2.1〕庚-5-烯-2,3-二羧醯亞胺、N-(10-樟腦磺醯氧基)-7-氧雜二環〔2.2.1〕庚-5-烯-2,3-二羧醯亞胺、N-(10-樟腦磺醯氧基)二環〔2.2.1〕庚-5,6-氧-2,3-二羧醯亞胺、N-(10-樟腦磺醯氧基)萘醯亞胺、N-(4-甲基苯基磺醯氧基)丁二醯亞胺、N-(4-甲基苯基磺醯氧基)酞醯亞胺、N-(4-甲基苯基磺醯氧基)二苯基馬來醯亞胺、N-(4-甲基苯基磺醯氧基)二環〔2.2.1〕庚-5-烯-2,3-二羧醯亞胺、N-(4-甲基苯基磺醯氧基)-7-氧二環〔2.2.1〕庚-5-烯-2,3-二羧醯亞胺、N-(4-甲基苯基磺醯氧基)二環〔2.2.1〕庚-5,6-氧-2,3-二羧醯亞胺、N-(4-甲基苯基磺醯氧基)萘醯亞胺、N-(2-三氟甲基苯基磺醯氧基)丁二醯亞胺、N-(2-三氟甲基苯基磺醯氧基)酞醯亞胺、N-(2-三氟甲基苯基磺醯氧基)二苯基馬來醯亞胺、N-(2-三氟甲基苯基磺醯氧基)二環〔2.2.1〕庚-5-烯-2,3-二羧醯亞胺、N-(2-三氟甲基苯基磺醯氧基)-7-氧雜二環〔2.2.1〕庚-5-烯-2,3-二羧醯亞胺、N-(2-三氟甲基苯基磺醯氧基)二環〔2.2.1〕庚-5,6-氧-2,3-二羧醯亞胺、N-(2-三氟甲基苯基磺醯氧基)萘醯亞胺、N-(4-氟苯基磺醯氧基)丁二醯亞胺、N-(4-氟苯基磺醯氧基)酞醯亞胺、N-(4-氟苯基磺醯氧基)二苯基馬來醯亞胺、N-(4-氟苯基磺醯氧基)二環〔2.2.1〕庚-5-烯-2,3-二羧醯
亞胺、N-(4-氟苯基磺醯氧基)-7-氧雜二環〔2.2.1〕庚-5-烯-2,3-二羧醯亞胺、N-(4-氟苯基磺醯氧基)二環〔2.2.1〕庚-5,6-氧-2,3-二羧醯亞胺、和N-(4-氟苯基磺醯氧基)萘醯亞胺。
疊氮甲烷化合物的特定例子包括,但不限於,雙(三氟甲基磺醯基)疊氮甲烷、雙(環己基磺醯基)疊氮甲烷、雙(苯基磺醯基)疊氮甲烷、雙(對-甲苯磺醯基)疊氮甲烷、甲基磺醯基對-甲苯磺醯基疊氮甲烷、(環己基磺醯基)(1,1-二甲基乙基磺醯基)疊氮甲烷、和雙(1,1-二甲基乙基磺醯基)疊氮甲烷。
這些酸生成劑可以單獨使用或併用。
聚合反應引發劑(B)組份的量為可聚合的單體(A)量的0.01重量%或更多且10重量%或更少,較佳地0.1重量%或更多且7重量%或更少。低於0.01重量%會造成固化速率降低及反應效率低。另一方面,超過10重量%會造成光可固化組成物的固化產物之機械特性欠佳。
除了可聚合的單體(A)、聚合反應引發劑(B)、和含氟的界面活性劑(C)以外,根據本發明之光可固化組成物的具體實施例可含有其他添加劑組份,如敏化劑、抗氧化劑、溶劑、和/或聚合物組份,以於未損失本發明之優點的情況下用於各自目的。
敏化劑可促進聚合反應及改良反應轉化率。敏化劑可
為氫授體或敏化染料。
此氫授體能夠與自聚合反應引發劑(B)生成的引發劑自由基或傳播性自由基反應而形成更具反應性的自由基。當聚合反應引發劑(B)為光誘發的自由基生成劑時,可添加此氫授體。
氫授體的特定例子包括,但不限於,胺化合物,如N-丁胺、二正丁胺、三正丁膦、烯丙烯硫脲、s-苯甲基異硫脲-對-甲苯亞磺酸鹽、三乙胺、甲基丙烯酸二甲胺基乙酯、三伸乙四胺、4,4’-雙(二烷胺基)二苯基酮、N,N-二甲胺基苯甲酸乙酯、N,N-二甲胺基苯甲酸異戊酯、戊基-4-二甲胺基苯甲酸酯、三乙醇胺、和N-苯基甘油;和巰基化合物,如2-巰基-N-苯基苯并咪唑和巰基丙酸鹽。
敏化染料藉吸收具有特別波長的光而激發並作用於聚合反應引發劑(B)。此處所謂“作用於”是指自激發的敏化染料能量轉移或電子轉移至聚合反應引發劑(B)。
敏化染料的特定例子包括,但不限於,蒽衍生物、蒽醌衍生物、芘衍生物、苝衍生物、咔唑衍生物、苯乙酮衍生物、9-氧硫衍生物、氧蔥酮衍生物、9-氧硫衍生物、香豆素衍生物、啡噻(phenothiazine)衍生物、樟腦醯衍生物、吖啶衍生物、硫代吡喃鎓鹽(thiopyrylium salt)染料、部花青素(merocyanine)染料、喹啉染料、苯乙烯基喹啉染料、酮基香豆素染料、硫(thioxanthene)染料、(xanthene)染料、oxonol染料、靛青(cyanine)染料、玫紅(rhodamine)染料、和
吡喃鎓鹽染料。
此敏化劑可以單獨使用或併用。
根據本發明之具體實施例的光可固化組成物中之敏化劑的量以可聚合的單體(A)量計為0至20重量%,更佳為0.1重量%至5.0重量%,又更佳為0.2重量%至2.0重量%。敏化劑含量為0.1重量%或更高時,可有效地得到敏化劑的效果。敏化劑含量為5.0重量%或更低時,光固化產物可具有夠高的分子量,且可防止溶解度或儲存安定性受損。
光可固化組成物可於0℃至100℃的溫度範圍內混合和溶解。
根據本發明之具體實施例之光可固化組成物於無溶劑的23℃黏度較佳地在1至100 cP的範圍內,更佳地為5至50 cP,又更佳地為6至20 cP。黏度超過100 cP會造成組成物在模具上之微圖案壓平部分的充填時間長或因為在下述壓印步驟中的充填不足而造成圖案缺陷。黏度低於1 cP會造成下述塗覆步驟中的塗覆不均或組成物在下述壓印步驟中自模具外流。
根據本發明之具體實施例之光可固化組成物於無溶劑的23℃表面張力較佳地在5至70毫牛頓/米的範圍內,更佳地為7至35毫牛頓/米,又更佳地為10至32毫牛頓/米。
表面張力低於5毫牛頓/米造成組成物在下述接觸步驟中,在模具上的下凹和隆起部分的充填時間長。表面張力超過70毫牛頓/米造成表面平滑性欠佳。
欲防止可聚合的單體(A)的固化產物之下凹和隆起部分因微粒污染物而形成缺陷,組份混合之後,光可固化組成物可加壓通過孔尺寸在0.001至5.0微米範圍內的濾器。此過濾可以多步驟或多次進行。經過濾的液體可再度過濾。濾器材料可為,但不限於,聚乙烯樹脂、聚丙烯樹脂、氟聚合物、或尼龍樹脂。
令用以製造半導體積體電路的光可固化組成物中之金屬雜質最少化以免抑制電路之操作。因此,根據本發明之具體實施例之光可固化組成物的金屬雜質濃度較佳地為10 ppm或更低,更佳地為100 ppb或更低。
根據本發明之具體實施例之圖案化方法含括將光可固
化組成物置於待加工的基板上的放置步驟(圖1A),令該光可固化組成物與模具接觸的接觸步驟(圖1B),在該光可固化組成物與模具接觸時,以光對該光可固化組成物照光的照光步驟(圖1C),和令該光可固化組成物自模具脫模的脫模步驟(圖1D)。
照光步驟中,該光可固化組成物可以光透過模具照射。
此方法可以另含括在脫模步驟之後,蝕刻光可固化組成物留在下凹部分的膜部分,以使得下凹部分中的基質表面外露的外露步驟(圖1E)。
下文將描述根據本發明之圖案化方法的各步驟。
本具體實施例中,將光可固化組成物置於待加工的基板上之放置步驟係塗覆步驟。根據本發明之具體實施例的光可固化組成物施於待加工的基板上。
待加工的基板可為基板,如矽晶圓。待加工的基板亦可為鋁、鈦-鎢合金、鋁-矽合金、鋁-銅-矽合金、氧化矽、或氮化矽製之用於半導體裝置的基板。待加工的基板可為經表面處理(如矽烷偶合處理、矽氮烷處理)或形成有機膜以改良對於光可固化組成物之黏著性的基板。
此光可固化組成物可藉噴墨法、浸塗法、氣刀塗覆法、簾塗法、線棒塗覆法(wire bar coating method)、照相凹版印刷塗覆法、壓出塗覆法、旋塗法、或縫隙掃描
法(slit scanning method)施用。光可固化組成物的膜厚度取決於應用且例如在0.01至100.0微米的範圍內。
在令光可固化組成物與模具接觸的模具接觸步驟中,在模具表面上的下凹和隆起部分(微圖案)充滿光可固化組成物。
模具製自透光材料,例如,玻璃、石英、透光樹脂(如PMMA或聚碳酸酯樹脂)、透明的金屬化膜、軟膜(如聚二甲基矽氧烷膜)、光固化膜、或金屬膜。
與光可固化組成物接觸的模具表面可具親水性,以有助於與含氟的界面活性劑(C)形成極性鍵。
根據本發明之具體實施例之圖案化方法所用模具可接受表面處理以改良光可固化組成物自模具脫模的脫模性。此表面處理含括使用矽烷偶合劑,如矽酮或氟化的偶合劑,例如,市售的塗料型脫模劑,如Daikin Industries,Ltd.生產的Optool DSX。
接觸壓力通常,但不限於,自0.1 Pa至100 Mpa的範圍內,較佳為0.1 Pa至50 Mpa,更佳為0.1 Pa至30 Mpa,又更佳為0.1 Pa至20 Mpa。接觸時間通常,但不限於,在1至600秒的範圍內,較佳為1至300秒,更佳為1至180秒,又更佳為1至120秒。
根據本發明之具體實施例之圖案化方法可於大氣中、在減低壓力下、或在惰性氣體中進行。惰性氣體的特定例
子包括,但不限於,氮、二氧化碳、氦、氬、各種氯氟化碳、和彼等之混合物。此壓力可以在0.0001至10大氣壓的範圍內。使用減低的壓力或惰性氣體可消除氧或水對光可固化組成物之影響。
照光步驟中,光可固化組成物與模具接觸的同時,光可固化組成物以光照射。此步驟中,在模具表面之下凹和隆起部分的光可固化組成物被固化。
未特別限制此光,其取決於根據本發明之具體實施例的光可固化組成物的敏感波長,且可為波長範圍約150至400奈米的紫外光、X-射線、或電子束。對紫外光敏感的各種光敏性化合物簡便地作為聚合反應引發劑(B)。紫外光源的例子包括,但不限於,高壓汞燈、超高壓汞燈、低壓汞燈、深UV燈、碳弧燈、化學燈、金屬鹵素燈、氙燈、KrF準分子雷射、ArF準分子雷射、和F2準分子雷射。這些光源可以單獨使用或併用。此光可固化組成物可以完全或部分以光照射。
可能的話,光可固化組成物可以進一步熱固化。未特別限制熱固化的加熱氣氛和加熱溫度且可為惰性氣氛或在減低壓力下及在40℃至200℃範圍內。加熱可以加熱板、烤箱、或爐進行。
脫模步驟中,自模具移出光可固化組成物。此步驟中,在模具表面上的下凹或隆起部分的相反圖案轉移至光可固化組成物的固化產物。
未特別限制脫模法,亦未特別限制各種條件。例如,待加工的基板可經固定而模具自待加工的基板移開,或模具可經固定而待加工的基板自模具移開,或待加工的基板和模具於相反方向移動。
根據本發明之具體實施例之圖案化方法可含括使用塗覆型脫模劑。更特定言之,塗覆性脫模劑層可以在壓印步驟之前形成於模具之圖案化表面上。
塗覆型脫模劑的例子包括,但不限於,矽酮脫模劑、氟化的脫模劑、聚乙烯脫模劑、聚丙烯脫模劑、石蠟脫模劑、褐煤蠟(montan)脫模劑、和棕櫚蠟(carnauba)脫模劑。此脫模劑可以單獨使用或併用。
外露步驟中,留在下凹部分的光可固化組成物膜部分經蝕刻以使下凹部分中的基板表面外露。
未特別限制此蝕刻法且可為慣用方法,如乾蝕法。已知乾蝕設備可用於乾蝕法中。用於乾蝕的來源氣體取決於待蝕刻的膜的元素組成且可為含氧氣體(如O2、CO、或CO2)、惰性氣體(如He、N2、或Ar)、氯氣(如Cl2或BCl3)、H2、或NH3。這些來源氣體可以單獨使用或併用。
在外露步驟中形成的圖案可被用來作為用於半導體元件(如LSI、系統LSI、DRAM、SDRAM、RDRAM、或D-RDRAM)的層間絕緣膜的膜,或製造半導體元件的光阻膜。
更特定言之,如圖1F所示者,外露步驟中的外露部分可接受蝕刻或離子植入以在待加工的基板上形成以光可固化組成物圖案為基礎的電路結構。用於半導體元件的電路板可經由這些步驟製得。
光可固化組成物圖案可自基板移除或留下作為構成元件的構件。
可作為光學組件的基板表面上具有結構化的圖案。更特定言之,此基板可以包括基板和光可固化組成物的固化產物位於基板上之物件形式提供。
將藉以下實例進一步描述本發明。但是,本發明之技術範圍不限於這些實例。除非特定指出,否則“份”和“%”係以重量計。
300毫升反應器中,於氮氣下,引入六(乙二醇)
(PEG6)(26.5克,93.9毫莫耳,1.0當量)、四氯化碳(CCl4)(36.1克,235毫莫耳,2.5當量)和四氫呋喃(THF)(106毫升)並冷卻至-30℃。以2小時,以THF(24毫升)稀釋的二甲胺基膦(15.3克,939毫莫耳,1.0當量)緩慢地添加至此溶液中。於此溫度攪拌30分鐘之後,移除冷卻浴,且此溶液於室溫攪拌2小時。在此淡黃色的懸浮液中添加自來水(250毫升)以將懸浮液分離成兩層(CCl4和含水層)。此含水層以異丙醚(IPE)(150毫升x2)清洗。分散於此溶液中之自來水(250毫升)中的六氟磷酸鉀(KPF6)(34.5克,188毫莫耳,2.0當量)加至含水層並充分攪拌。經二氯甲烷(200毫升x3)萃取的有機層以自來水(400毫升)和飽和的食鹽水(300毫升)清洗並以無水硫酸鎂加以乾燥。溶液經濃縮以得到淡棕色液體(C-1-a)(53克)。
500毫升反應器中引入1H,1H-全氟-1-庚醇(34.2克,97.7毫莫耳,1.2當量)和THF(120毫升)。NaH(60%)(3.9克,97.7毫莫耳,1.2當量)緩慢地加至此溶液,期間內並注意起泡情況。於50℃攪拌1小時之後,溶劑於減低壓力下蒸發。溶於無水二烷(600毫升)的液體(C-1-a)(53克)加至殘渣中並於60℃攪拌48小時。懸浮液經濃縮,自來水(300毫升)和乙酸乙酯(300毫升)加至所得殘渣中以便將殘渣分成兩層。含水層以乙酸乙酯(200毫升x2)萃取。有機層以自來水(400毫升)和飽和的食鹽水(400毫升)清洗並以無水硫酸鎂加
以乾燥。溶液經濃縮而得到棕色液體(59.1克)。此棕色液體進行管柱純化(SiO2:1.2公斤,僅乙酸乙酯=>乙酸乙酯/甲醇=10/1)及之後的管柱純化(SiO2:400克,氯仿/甲醇=15/1=>10/1)及在高真空下乾燥以得到含氟的界面活性劑(C-1),六(乙二醇)單-1H,1H-全氟庚醚(F(CF2)6CH2(OCH2CH2)6OH,19.2克,31.2毫莫耳,產率33%),其為無色液體。
使用100重量份二丙烯酸1,6-己二醇酯(Osaka Organic Chemical Industry Ltd.生產)作為(A)組份、3重量份Irgacure 369(Ciba Japan K.K.生產)作為(B)組份、和0.125重量份含氟的界面活性劑(C-1)作為(C)組份,製得混合溶液。此混合溶液通過0.2微米四氟乙烯濾器以得到根據實例1的光可固化組成物(a-1)。
光可固化組成物(a-1)的表面張力為31.5毫牛頓/米,此係以自動表面張力計CBVP-A3(Kyowa Interface Science Co.,Ltd.生產)測得。
光可固化組成物(a-1)的黏度為6.4 cP,此係以錐-和-板黏度計RE-85L(Toki Sangyo Co.,Ltd.生產)測得。
藉旋塗法,光可固化組成物(a-1)在矽晶圓上形成
厚度約1微米的膜。
光可固化組成物(a-1)的膜以來自配備250瓦超高壓汞燈的UV光源EX250(Hoya Candeo Optronics Corp.生產)的光,在氮氣中透過干擾濾器VPF-50C-10-25-36500(Sigmakoki Co.,Ltd.生產)照射而製得光固化膜。波長為365奈米時,膜上的照度為25毫瓦/平方公分。照光時間為100秒。
在光可固化組成物(a-1)的光固化膜上之1微升純水的接觸角度為69度,此係以全自動接觸角度計CA-W(Kyowa Interface Science Co.,Ltd.生產)測得。
脫模力之測定
15微升(a-1)以微吸量管滴在具有60奈米厚的黏著促進層作為黏著層的4英吋矽晶圓上。
未經表面處理且無圖案的40x40毫米石英模具壓印在矽晶圓上。
配備200瓦汞氙燈的UV光源EXECURE 3000(Hoya Candeo Optronics Corp.生產)作為照光光源。干擾濾器VPF-50C-10-25-36500(Sigmakoki Co.,Ltd.生產)置於光源和石英模具之間。石英模具下之365奈米波長的直接照度是1毫瓦/平方公分。
在這些條件下,進行為時60秒的照光步驟。
脫模步驟中,石英模具以0.5毫米/秒上升。
以衝擊張力/壓縮測力計LUR-A-200NSA1(Kyowa Electronic Instruments Co.,Ltd.生產)測定脫模力。在相
同條件下之四次測定的平均脫模力為149牛頓。
以與實例1相同的方式製造光可固化組成物(a-2),但使用0.5重量份含氟的界面活性劑(C-1)作為(C)組份。
以與實例1相同的方式測定,光可固化組成物(a-2)的表面張力和黏度分別為25.5毫牛頓/米和6.4 cP。
水接觸角度之測定
以與實例1中相同的方式製得光可固化組成物(a-2)的光固化膜之水接觸角度為64度。
脫模力之測定
以與實例1中相同的方式測定,光可固化組成物(a-2)的平均脫模力為128牛頓。
以與實例1相同的方式製造光可固化組成物(a-3),但使用2.0重量份含氟的界面活性劑(C-1)作為(C)組份。
以與實例1相同的方式測定,光可固化組成物(a-3)的表面張力和黏度分別為21.0毫牛頓/米和6.5 cP。
水接觸角度之測定
以與實例1中相同的方式製得光可固化組成物(a-3)的光固化膜之水接觸角度為29度。
脫模力之測定
以與實例1中相同的方式測定,光可固化組成物(a-3)的平均脫模力為88牛頓。
自(A)組份:61.6重量份丙烯酸異酯(IB-XA,Kyoeisha Chemical Co.,Ltd.生產)、10重量份丙烯酸(2-甲基-2-乙基-1,3-二戊烷-4-基)甲酯(MEDOL-10,Osaka Organic Chemical Industry Ltd.生產)和22.4重量份二丙烯酸己二醇酯(Viscoat #230,Osaka Organic Chemical Industry Ltd.生產),(B)組份:3重量份Irgacure 369(Ciba Japan K.K.生產)和(C)組份:2.2重量份十五(乙二醇)單-1H,1H,2H,2H-全氟辛醚(F(CF2)6CH2CH2(OCH2CH2)15OH,DIC生產),製得混合溶液。此混合溶液通過0.2微米四氟乙烯濾器以得到根據實例4的光可固化組成物(a-4)。
以與實例1相同的方式測定,光可固化組成物(a-4)的表面張力和黏度分別是24.9毫牛頓/米和7.1 cP。
水接觸角度之測定
以與實例1中相同的方式製得光可固化組成物(a-4)的光固化膜之水接觸角度為64度。
脫模力之測定
以與實例1中相同的方式測定,光可固化組成物(a-4)的平均脫模力為99牛頓。
以與實例4相同的方式製造光可固化組成物(a-5),但(C)組份為1.3重量份二十(乙二醇)單-1H,1H,2H,2H-全氟辛醚(F(CF2)6CH2CH2(OCH2CH2)20OH,DIC生產)。
以與實例1相同的方式測定,光可固化組成物(a-5)的表面張力和黏度分別為27.2毫牛頓/米和7.0 cP。
水接觸角度之測定
以與實例1中相同的方式製得光可固化組成物(a-5)的光固化膜之水接觸角度為72度。
脫模力之測定
以與實例1中相同的方式測定,光可固化組成物(a-5)的平均脫模力為118牛頓。
自(A)組份:61.6重量份丙烯酸異酯(IB-XA,Kyoeisha Chemical Co.,Ltd.生產)、10重量份丙烯酸(2-甲基-2-乙基-1,3-二戊烷-4-基)甲酯(MEDOL-10,Osaka Organic Chemical Industry Ltd.生產)和22.4重量份二丙烯酸己二醇酯(Viscoat #230,Osaka Organic Chemical Industry Ltd.生產),(B)組份:3重量份2,2-二甲氧基-2-苯基苯乙酮(Irgacure 651,BASF生產)和(C)組份:1.1重量份十五(乙二醇)單-1H,1H,2H,2H-全氟辛醚
(F(CF2)6CH2CH2(OCH2CH2)15OH,DIC生產),製得混合溶液。
此混合溶液通過0.2微米四氟乙烯濾器以得到根據實例6的光可固化組成物(a-6)。
以與實例1相同的方式測定,光可固化組成物(a-6)的表面張力和黏度分別是26.1毫牛頓/米和6.6 cP。
水接觸角度之測定
以與實例1中相同的方式製得光可固化組成物(a-6)的光固化膜之水接觸角度為58度。
脫模力之測定
光源為超高壓汞燈。干擾濾器置於光源和石英模具之間。波長313±5奈米的光選擇性地通過干擾濾器。石英模具下之313奈米波長的直接照度為38.5毫瓦/平方公分。
藉噴墨法,11微微升光可固化組成物(a-6)的1440個液滴實質上均勻地滴在具有3奈米厚的黏著促進層作為黏著層之300毫米矽晶圓的26x33毫米區上。
令未經表面處理且無圖案的26x33毫米石英模具與此矽晶圓接觸。
30秒之後,照光5秒。
照光之後,移開石英模具。以測力計測定脫模力。在相同條件下的三次測定之平均脫模力為48.7牛頓。此脫模力低於下述的比較例3中者。
以與實例6相同的方式製造光可固化組成物(a-7),但(C)組份為2.2重量份十五(乙二醇)單-1H,1H,2H,2H-全氟辛醚(F(CF2)6CH2CH2(OCH2CH2)15OH,DIC生產)。
以與實例1相同的方式測定,光可固化組成物(a-7)的表面張力和黏度分別為23.9毫牛頓/米和6.7 cP。
水接觸角度之測定
以與實例1中相同的方式製得光可固化組成物(a-7)的光固化膜之水接觸角度為9度。
脫模力之測定
以與實例6中相同的方式測定,光可固化組成物(a-7)的平均脫模力為49.1牛頓。此脫模力低於下述的比較例3中者。
以與實例6相同的方式製造光可固化組成物(a-8),但(B)組份為3重量份2-甲基-1-〔4-(甲硫基)苯基〕-2-嗎啉基丙-1-酮(Irgacure 907,BASF生產)。
以與實例1相同的方式測定,光可固化組成物(a-8)的表面張力和黏度分別為26.5毫牛頓/米和6.7 cP。
水接觸角度之測定
以與實例1中相同的方式製得光可固化組成物(a-8)的光固化膜之水接觸角度為42度。
脫模力之測定
以與實例6中相同的方式測定,光可固化組成物(a-8)的平均脫模力為55.3牛頓。此脫模力低於下述的比較例3中者。
以與實例1相同的方式製造光可固化組成物(b-1),但未添加(C)組份。
以與實例1相同的方式測定,光可固化組成物(b-1)的表面張力和黏度分別為35.9毫牛頓/米和6.3 cP。
水接觸角度之測定
以與實例1中相同的方式製得光可固化組成物(b-1)的光固化膜之水接觸角度為79度。
脫模力之測定
以與實例1中相同的方式測定,光可固化組成物(b-1)的平均脫模力為158牛頓,此高於實例1至3中者。
以與實例4相同的方式製造光可固化組成物(b-2),但未添加(C)組份。
以與實例1相同的方式測定,光可固化組成物(b-2)的表面張力和黏度分別為31.5毫牛頓/米和6.8 cP。
水接觸角度之測定
以與實例1中相同的方式製得光可固化組成物(b-
2)的光固化膜之水接觸角度為81度。
脫模力之測定
以與實例1中相同的方式測定,光可固化組成物(b-2)的平均脫模力為143牛頓,此高於實例4和5中者。
以與實例6相同的方式製造光可固化組成物(b-3),但未添加(C)組份。
以與實例1相同的方式測定,光可固化組成物(b-3)的表面張力和黏度分別為28.1毫牛頓/米和6.4 cP。
水接觸角度之測定
以與實例1中相同的方式製得光可固化組成物(b-3)的光固化膜之水接觸角度為94度。
脫模力之測定
以與實例6中相同的方式測定,光可固化組成物(b-3)的平均脫模力為56.5牛頓,此高於實例6至8中者。
已經以參考例示具體實施例的方式描述本發明,瞭解本發明不限於所揭示的具體實施例。以下申請專利範圍之範圍賦予最廣闡釋,以含括所有的此修飾和對等結構及作用。
圖1A至1F係說明圖案化方法之截面圖。
Claims (12)
- 一種光可固化組成物,包含:可聚合的單體(A);聚合反應引發劑(B);和含氟的界面活性劑(C),其中該光可固化組成物之光固化產物的水接觸角度為74度或更低。
- 如申請專利範圍第1項之光可固化組成物,其中該光可固化組成物之光固化產物的水接觸角度為70度或更低。
- 如申請專利範圍第1或2項之光可固化組成物,其中該含氟的界面活性劑(C)的一端具有極性官能基。
- 如申請專利範圍第3項之光可固化組成物,其中該含氟的界面活性劑(C)的一端具有全氟烷基鏈(C-a)和另一端具有極性官能基(C-c),且該全氟烷基鏈經由聚(環氧烷基)鏈(C-b1)或烷基鏈(C-b2)鏈結至該極性官能基。
- 如申請專利範圍第3項之光可固化組成物,其中該含氟的界面活性劑(C)係至少一種具有以下通式(1)的化合物:F(CF2)6(CH2)m(OCH2CH2)nOH (1)其中m是1至3的整數,而n是1至100的整數。
- 如申請專利範圍第1項之光可固化組成物,其中該聚合反應引發劑(B)是2,2-二甲氧基-2-苯基乙醯苯。
- 如申請專利範圍第1項之光可固化組成物,其中該聚合反應引發劑(B)是2-甲基-1-〔4-(甲硫基)苯基〕-2-嗎啉丙-1-酮。
- 一種圖案化方法,包含:將如申請專利範圍第1至7項中任一項之光可固化組成物置於待加工的基板上;令該光可固化組成物與模具接觸;對該光可固化組成物照光;和在照光而使得該光可固化組成物在待加工的基板上形成圖案之後,令該光可固化組成物自模具脫模。
- 如申請專利範圍第8項之圖案化方法,其中與該光可固化組成物接觸之該模具表面以石英製得。
- 如申請專利範圍第8或9項之圖案化方法,其中該照光含括該光可固化組成物以光線透過其表面上具有下凹和隆起部分的模具照射。
- 一種製造電路板之方法,包含:根據藉如申請專利範圍第8至10項中任一項之圖案化方法所形成的圖案,將離子蝕刻或植入基板中,藉此形成電路構造。
- 一種物件,包含:基板;和在基板上的固化產物,該固化產物具有如申請專利範圍第1至7項中任一項之光可固化組成物的圖案。
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2012
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- 2012-10-19 JP JP2012232177A patent/JP6202800B2/ja active Active
- 2012-10-24 KR KR1020147014505A patent/KR101605282B1/ko active IP Right Grant
- 2012-10-24 CN CN201280055066.XA patent/CN103930448B/zh active Active
- 2012-10-24 WO PCT/JP2012/078082 patent/WO2013069511A1/en active Application Filing
- 2012-10-24 US US14/357,542 patent/US20140349086A1/en not_active Abandoned
- 2012-10-24 EP EP12847152.1A patent/EP2760894B1/en active Active
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US10338467B2 (en) | 2013-09-18 | 2019-07-02 | Canon Kabushiki Kaisha | Method of producing film |
US10182500B2 (en) | 2014-02-26 | 2019-01-15 | Canon Kabushiki Kaisha | Curable composition for photoimprint, cured product, and method of producing film having pattern, optical component, circuit board, or electronic component using the composition |
TWI666512B (zh) * | 2014-02-26 | 2019-07-21 | 日商佳能股份有限公司 | 用於光壓印之可固化組成物、經固化之產物、以及使用該組成物製造具有圖案之膜、光學組件、電路板、或電子組件之方法 |
TWI643893B (zh) * | 2014-03-26 | 2018-12-11 | 日商富士軟片股份有限公司 | 光壓印用硬化性組成物、圖案形成方法及圖案 |
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EP2760894B1 (en) | 2018-12-12 |
TWI471693B (zh) | 2015-02-01 |
WO2013069511A1 (en) | 2013-05-16 |
JP2017141456A (ja) | 2017-08-17 |
JP6202800B2 (ja) | 2017-09-27 |
KR101605282B1 (ko) | 2016-03-21 |
JP6490128B2 (ja) | 2019-03-27 |
CN103930448B (zh) | 2017-11-17 |
CN103930448A (zh) | 2014-07-16 |
KR20140099560A (ko) | 2014-08-12 |
JP2013122044A (ja) | 2013-06-20 |
US20140349086A1 (en) | 2014-11-27 |
US20200123343A1 (en) | 2020-04-23 |
EP2760894A1 (en) | 2014-08-06 |
EP2760894A4 (en) | 2015-05-27 |
US11332597B2 (en) | 2022-05-17 |
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