TW201237555A - Black polymerizable composition and method for producing a black layer - Google Patents

Black polymerizable composition and method for producing a black layer Download PDF

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Publication number
TW201237555A
TW201237555A TW100135758A TW100135758A TW201237555A TW 201237555 A TW201237555 A TW 201237555A TW 100135758 A TW100135758 A TW 100135758A TW 100135758 A TW100135758 A TW 100135758A TW 201237555 A TW201237555 A TW 201237555A
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Taiwan
Prior art keywords
black
group
lens
light
polymerizable composition
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TW100135758A
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Chinese (zh)
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TWI546621B (en
Inventor
Kazuto Shimada
Satoru Murayama
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Fujifilm Corp
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Publication of TW201237555A publication Critical patent/TW201237555A/en
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Publication of TWI546621B publication Critical patent/TWI546621B/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/0006—Arrays
    • G02B3/0012—Arrays characterised by the manufacturing method
    • G02B3/0031—Replication or moulding, e.g. hot embossing, UV-casting, injection moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00278—Lenticular sheets
    • B29D11/00298—Producing lens arrays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00865—Applying coatings; tinting; colouring
    • 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
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C08F291/12—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to nitrogen-containing macromolecules
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/0006—Arrays
    • G02B3/0037—Arrays characterized by the distribution or form of lenses
    • G02B3/0056—Arrays characterized by the distribution or form of lenses arranged along two different directions in a plane, e.g. honeycomb arrangement of lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/0006—Arrays
    • G02B3/0037—Arrays characterized by the distribution or form of lenses
    • G02B3/0062—Stacked lens arrays, i.e. refractive surfaces arranged in at least two planes, without structurally separate optical elements in-between
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Ophthalmology & Optometry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Lens Barrels (AREA)

Abstract

The invention provides a black polymerizable composition having an excellent alkali developer resistance, a wafer level lens, and the like. The black polymerizable composition includes at least: (A) a black material; (B) a polymerization initiator; (C) a polymerizable compound; and (D) an alkali-soluble binder polymer having a weight average molecular weight of at least 30, 000 and a polymerizable group at a side chain thereof.

Description

201237555 39636pif 六、發明說明： 【發明所屬之技術領域] 本發明是關於一種包含特定鹼溶性黏合劑聚合物之 黑色可聚合組成物、詳言之用於形成於基板上排列多個透 鏡之晶圓級透鏡陣列（Wafer army )之遮光區 (light-shielding region)的黑色可聚合組成物，以及使用黑 色可聚合組成物製造黑色層之方法。 【先前技術】 近來，緊密且低輪廓（薄）成像單元被安裝於電子儀 态之行動終端（諸如行動電話或個人數位助理（Pers〇nal Digital Assistant ’ PDA))上。這些成像單元一般包含固態 成像裝置，諸如電荷耦合裝置（Charge c〇upled Device， CCD )型影像感測器或互補金屬氧化物半導體 (Complementary Metal-Oxide Semiconductor，CMOS )型影 像感測器，以及用於在固態成像裝置上形成目標影像的透 鏡。 隨著行動終端之尺寸及厚度減小且隨著行動終端之 廣泛使用，需要進一步減小行動終端上所安裝之成像單元 的尺寸及厚度，且亦需要改良其生產力。關於所述需要， 已知一種大量製造成像單元之方法，藉由所述方法將上面 形成多個透鏡之透鏡基板與上面形成多個固態成像裝置之 感測器基板整體組合，且切割透鏡基板及感測器基^以在 各切割部分中包含透鏡及固態成像裝置。 另外’採用於晶圓上形成透鏡之方法使得可執行各種 201237555 ^yOJOplf 簡單形成方法’包含例如於玻璃晶圓上僅製造透鏡之方 法，例如將玻璃晶圓切割至一定尺寸以組合個別透鏡與感 測器，繼而與預分離之成像裝置組合而得到個別成像單 元；使用模具僅由樹脂形成多個透鏡之方法，將所述透鏡 於感測器基板上組合，隨後切割；以及切割透鏡至一定尺 寸以與個別感測器組合，繼而與預分離之成像裝置組合而 得到個別成像單元之方法。 在本說明書下文中，於透鏡基板上形成之多個透鏡中 之每一者稱作晶圓級透鏡，且於透鏡基板上形成之透鏡組 (包含透鏡基板）稱作晶圓級透鏡陣列。 作為相關技術中之晶圓級透鏡陣列，已知一種晶圓級 透鏡陣列，其上藉由於由光透射材料（諸如玻璃）形成之 平行板（基板）之表面上逐滴施加可固化樹脂材料且使所 述樹脂材料在使用模具使其以指定形狀排列之狀態下固化 而形成多個透鏡（例如參見日本專利公開案第3926380號 及國際申請公開案第wo 2008/102648號）。在一些情況 下，可在除晶圓級透鏡之透鏡部分以外的區域中或透鏡之 一部分上形成例如由黑色膜或金屬膜形成之遮光部分以控 制穿過其中的光之量。遮光部分一般藉由塗佈遮光可固化 組成物或藉由沈積金屬而形成。 作為另一晶圓級透鏡陣列，亦已知一種晶圓級透鏡陣 列，其藉由以下步驟獲得：於矽基板上形成多個通孔於 個別通孔中配置已分別形成之球面透鏡材料，藉由焊接使 透鏡材料與基板接合，隨後拋光透鏡材料以形成多個透鏡 201237555 39636pif (參見美國專利第6426829號&gt; 在藉由此製造方法獲得之 透鏡中，可形成上述黑色膜或金屬膜以控制穿過其中的光 之量。 ,在遮光區藉由沈積金屬形成之情況下，出於存在諸如 製程複雜或沈積後透鏡彎曲（lens bending)之問題的觀 點’需要改良生產力與效能。 另一方面，已於塗佈方法中使用黑色可聚合組成物以 展現遮光特性（參見日本特許公開專利申請案（Jp_A)第 2010-8656 號及第 2006-276421 號）。 在黑色可聚合組成物在可見光區中具有足夠遮光特 性之情況下，作為用於使黑色可聚合組成物固化之曝光光 源的選自g射線、h射線、i射線及/或翻撤射線之放 射線的透射率不足。出於此賴，深部謂未經充分固化， 因此’在影像逐次曝光後，存在諸如以下_ :在驗顯影 步驟（其十將移除未曝光部分）中的膜剥落。 β因此，尚未充分進行關於涉及驗顯影劑抗性之所 ：«§的研究。 【發明内容】 本發明是鑒於上述態樣進行且是針對達成下述目的。 Τ即’本發狀-錄域供—種具梭顯影劑抗性 且因此具有極佳遮光特性之黑色可聚合組成物。 成物本發明之另—態樣提供能夠被塗之黑色可聚合級 本發明之另—態樣提供—種使用黑色可聚合組成物 5 201237555. 製造適用於晶圓級透鏡之遮光區的黑色層的方法。 一般而言，可固化組成物中使用含有羧酸作為鹼溶性 基團之樹脂。然而，在於相對嚴苛條件下進行顯影以移除 未曝光部分之殘餘物的情況下，存在諸如影像部分剝落之 問題。 同時，在使用用於透鏡孔隙之可固化組成物的情況 下，需要在可見光區至紅外區之寬泛範圍内的遮光特性。 在使用黑色可聚合組成物形成遮光膜〇ight-shielding film)之情況下，一般用25〇奈米至5〇〇奈米之光源進行 衫像逐次曝光，繼而使用驗顯影劑顯影。然而，因為可固 化組成物包含能夠在250奈米至500奈米之波長區遮光之 黑色材料，故曝光光源之透光率不足，因此，在一些情況 下，所形成膜之深部可能未經充分固化。因此，在於相對 嚴奇條件下進行顯影以防止殘餘膜減少的情況下，強酸性 竣酸可能造成顯影劑滲透至影像部分甲，且因此存在如下 困擾：影像部分之強度降低可能造成遮光膜（黑色膜）剝 落。 此外，在黑色可聚合組成物（或可固化組成物）用於 晶圓級透鏡之孔隙或其類似物的情況下，可使用將黑色可 聚合組成物塗佈於玻璃晶圓上且隨後在其上形成透鏡的方 去、在玻璃晶圓上形成透鏡且隨後將黑色可聚合組成物塗 佈於其上的方法或其類似方法。然而，尤其在形成透鏡後 塗佈黑色可聚合組成物之情況下，可有效藉由喷塗將黑色 可聚合組成物塗覆於結構基板上。 201237555 39636pif ^之，本發明之發明者已敍研究各種黑色可聚合 神i L從而發現—種具顯影劑抗性且因此具有極佳 2特性之黑色可聚合組成物。本發财亦發現一種 ΪΓ塗之黑色可聚合組成物。另外，本發明者發現一種使 …色可聚合組成物製造適用於晶圓級透鏡之遮光區 黑色層的方法。 本發明之特定例示性實施例如下。 &lt;1&gt;一種黑色可聚合組成物，其包含： (A) 黑色材料； (B) 聚合起始劑； (C) 可聚合化合物；以及 (D) 重量平均分子量為至少3〇〇〇〇且側鏈具有可聚 合基團之鹼溶性黏合劑聚合物。 &lt;2&gt;如&lt;1&gt;所述之黑色可聚合組成物，其中所述（A) 黑色材料為鈦黑。 &lt;3&gt;如&lt;1&gt;或&lt;2&gt;所述之黑色可聚合組成物，其中所述 (D)鹼溶性黏合劑聚合物為重量平均分子量為5〇,〇〇()至 100,000且側鏈具有可聚合基團之鹼溶性黏合劑聚合物。 &lt;4&gt;如&lt;1&gt;至&lt;3&gt;中任一項所述之黑色可聚合組成物’ 其用於形成晶圓級透鏡之遮光區。 &lt;5&gt;如&lt;1&gt;至&lt;4&gt;中任一項所述之黑色可聚合組成物， 其能夠被喷塗。 &lt;6&gt;如&lt;1&gt;至&lt;5&gt;中任一項所述之黑色可聚合組成物， 其中所述黑色可聚合組成物中之總固體含量為20質量％ 7 201237555 jyojopir 至35質量％。 &lt;7&gt;如&lt;1&gt;至&lt;6&gt;中任一項所述之黑色可聚合組成物， 其中所述（D)驗雜黏合卿合物中包含之所述可聚合 基團為丙烯基、甲基丙烯基、苯乙、稀丙基、丙烯醯 胺基團、甲基丙烯醯胺基團、乙烯基或乙烯鍵基。 &lt;8&gt;如&lt;1&gt;至&lt;7&gt;中任一項所述之黑色可聚合組成物， 其中所述（D)驗溶性黏合劑聚合物之含量以所述黑色可 聚合組成物之總固體含量計為5質量％至75質量％。 &lt;9&gt;種黑色層製造方法，所述方法包含： 藉由喷塗將如&lt;1&gt;至&lt;8&gt;中任一項所述之黑色可聚合 組成物塗覆於固體之表面上以形成黑色可聚合組成物層； 以及 向所形成之所述黑色可聚合組成物層施加能量以使 所形成之所述黑色可聚合組成物層固化。 &lt;10&gt;如&lt;9&gt;所述之黑色層製造方法，其中所述固體之 所述表面為晶圓級透鏡之周邊部分的表面，且所述黑色層 為在晶圓級透鏡之所述周邊部分中形成的遮光區。 曰 根據本發明之一態樣，提供一種具有鹼顯影劑抗性且 因此展現極佳遮光特性之黑色可聚合組成物。 此外，根據本發明之另一態樣，提供一種能夠被喷塗 之黑色可聚合組成物。 ' 另外，根據本發明之另一態樣，提供一種使用黑色可 聚合組成物製造適用於晶圓級透鏡之遮光區的黑色層的方 法0 8 201237555 39636pif 【實施方式】 下文將詳細描述本發明之黑色可聚合組成物。下述構 成要素之說明基於本發明之代表性實施例進行，但本發明 並不限於所述實施例。 在本說明書中，術語「步驟」或「製程」不僅為獨立 步驟，而且包含獲得步驟之預定作用的情況，即使在其不 能與其他步驟明確區別時。 此外，在本說明書中，藉由使用「至」（t〇)表達之數 值範圍表示包含「至」之前及之後描述之最小值及最大值 的範圍。 (D)鹼溶性黏合劑聚合物 本發明之黑色可聚合組成物包含重量平均分子量為 30,000且侧鏈具有可聚合基團之鹼溶性黏合劑聚合物。 構成本發明中所用之（D)鹼溶性黏合劑聚合物之主 鏈的聚合物的實例包含（曱基）丙烯酸聚合物、聚胺基甲酸 酯樹酯、聚乙烯醇樹脂、聚乙烯醇縮丁醛樹脂、聚乙烯醇 縮曱醛樹脂、苯乙烯樹脂、聚醯胺樹脂、聚酯樹脂、環氧 樹月曰以及紛糸樹脂（諸如盼搭清漆樹脂（n〇v〇lak resjn )或 甲階酚醛樹脂（res〇l resin))。特定言之，（曱基)丙烯酸聚 合物、苯乙烯樹脂以及酚系樹脂為較佳。此外，出於敏感 性及解析度之觀點，（曱基)丙烯酸聚合物及聚胺基曱酸酯 樹酯為較佳，且（曱基)丙烯酸聚合物為最佳。 在本發明中，「（曱基)丙烯酸聚合物」指具有（曱基)丙 烯酸、（曱基）丙烯酸酯（諸如烷酯、芳酯、烯丙酯或其類 201237555 jyojopir 似物）、（曱基）丙烯醯胺或（甲基)丙烯酸衍生物（諸如（甲基) 丙烯酿胺衍生物）作為聚合組分之共聚物。 在本說明書中，在描述「丙烯基」及「曱基丙埽其」 中任一者或兩者之情況下，在一些情況下可表示「（曱基) 丙稀基」。 在本發明中，「聚胺基曱酸酯樹酯」指由具有兩個或 兩個以上異氰酸酯基之化合物與具有兩個或兩個以上羥基 之化合物的縮合反應製備的聚合物。 土 在本發明中，「聚乙烯醇縮丁醛樹脂」指藉由使藉由 皂化聚乙酸乙烯酯之一部分或全部獲得之聚乙烯醇與丁醛 在酸性條件下進行反應（縮醛形成反應）而合成的聚合物， 以及藉由例如使剩餘羥基與具有酸基或其類似基團之化合 物反應的方法向其中引入酸基或其類似基團的聚合物。 二在本發明中，「苯乙烯樹脂」指藉由直接鍵聯有烯基 (諸如乙烯基）之芳族化合物（諸如苯、萘、蒽）或雜環與 (曱基）丙烯酸及/或（甲基）丙烯酸衍生物共聚合 (例如自由 基聚合）而獲得的聚合物。 芳族化合物可經例如羥基、羧基、齒素原子、烷基、 =基三炔基、胺基、羰基、醚基、烷氧羰基、氧羰基、氰 土、芳基、烷氧基、硫基、巯基或其類似基團取代。 s人關於聚合，可進行自由基聚合、陽離子聚合或陰離子 =合。另外，必要時，在聚合後進行鹼處理、酸處理或其 類似處理以獲得所要笨乙烯樹脂。 任一其他樹脂可用於構成本發明之鹼溶性黏合劑聚 201237555 39636pif 合物之主鏈的聚合物。可使用例如jp_A第2005-250438號 之第[0029]段至第[〇 1 〇8]段中所述之聚胺基曱酸酯樹酯、 JP-A第2010-39121號之第[0009]段至第[0019]段中所述之 在分子中具有醯胺及可聚合基團之樹脂以及其類似物，以 及JP-A第2000-191737號之第[0014]段至第[0015]段中所 述的藉由使具有丙烯酸及（曱基）丙烯酸酯作為主要組分之 樹脂與含環氧基之不飽和化合物反應而獲得的樹脂以及其 類似物。 ^ 較佳為抑制顯影期間於顯影劑中之經曝光部分的影 像部分溶離，本發明之驗溶性黏合劑聚合物較佳具有高分 子量’且具有可聚合基團以改良固化性。 本發明之鹼溶性黏合劑聚合物的重量平均分子量為 至少。當重量平均分子量小於30,000時，影像部; 對顯影劑之抗性不足。 另外，出於影像部分及非影像部分之顯影性的觀點， 鹼溶性黏合劑聚合物之重量平均分子量較佳為30 000至 500,000，更佳為40,000至200,000，且甚至更佳為％ 〇〇〇 至 100,000。 ’ 在本發明中，重量平均分子量指藉助於凝膠滲透層析 (Gel Permeation chromatography，GPC)方法依據笨乙稀 量測之值。 本發明之驗溶性黏合㈣合物錢合物之側鍵具有 可聚合基團。侧鏈中包含之可聚合基團 丙 基、甲基丙職、苯乙烯基、烯丙基、㈣軸基團^ 11 201237555 iy〇J〇pif 基丙烯醯胺基團、乙烯基以及乙烯醚基。出於穩定性及反 應性之觀點，丙烯基、甲基丙烯基以及烯丙基為較佳，且 曱基丙烯基為最佳。 侧鏈中包含之可聚合基團之量較佳為10莫耳％至8〇 莫耳％，以聚合物中各具有可聚合基團之所有單體單元 計，且出於敏感性、顯影性以及穩定性之觀點，更佳為30 莫耳％至60莫耳％。 … 在本文中’向驗溶性黏合劑聚合物中引入可聚合基團 之方法的實例包含：如JP-A第2000-187322號之第[0014] 段中所述的使黏合劑中羧酸之一部分與具有環醚及（甲基） 丙烯基之化合物（諸如曱基丙烯酸縮水甘油酯）反應以引 入可聚合基團的方法以及其類似方法；如jp_A第 2000-191737號中所述的使具有丙烯酸及（甲基）丙烯酸酯 作為主要組分之樹脂與含環氧基之不飽和化合物反應，以 及使具有羥基之單體用作共聚合組分之黏合劑與甲基丙烯 酸酐或丙烯酸酐或丙烯醯氯或甲基丙烯醯氣反應的方法； 或使具有羥基之單體用作共聚合組分之黏合劑與曱基丙烯 酸或丙烯酸共存且進行脫水/縮合的方法；以及如Jp_A第 2005-47947號之第[0028]段中所述的使側鏈具有曱基丙烯 酸衍生物及/或丙烯酸衍生物之單體聚合且用鹼進行處理 的方法以及其類似方法。 ^本發明之鹼溶性黏合劑聚合物具有表現鹼溶性之官 月b基。作為賦予黏合劑聚合物驗溶性之官能基，黏合劑聚 合物必需在其分子中具有酸基。較佳酸基之實例包含叛酸 12 201237555 39636pif 基團、罐酸基團、單磷_基團、雜基團、亞猶基團、 %醯胺基ϋ、崎基、硫醇基、乙醢基乙酸錢基團以及 其衍生物。 出於敏感性、穩定性以及顯影性之觀點，酸基較佳為 羧酸基團。 當本發明之鹼溶性黏合劑聚合物具有 鹼溶性基團 Β-三酸值較佳為5毫克ΚΟΗ/公克至15〇毫克ΚΟΗ/公克， 且最佳為30毫克ΚΟΗ/公克至100毫克K〇H/公克。 關於引入賦予黏合劑聚合物鹼溶性之官能基的方 =，當藉由自由基聚合執行聚合時，賦予黏合劑聚合物鹼 溶性之官能基可藉由使具有酸基及可聚合基團（諸如伸乙 基）之化合物（諸如曱基丙烯酸、丙烯酸、乙烯基苯曱酸 或乙烯基苯酚）聚合而引入。此外，官能基引入亦可藉由 使乙醯氧基乙烯基苯酚聚合繼而水解而達成。 在胺基曱酸酯黏合劑之情況下，可使用例如使具有繞 酸部分之二醇與二異氰酸酯化合物進行聚縮合反應以引入 酸基的方法。 當構成本發明之鹼溶性黏合劑聚合物之主鏈的聚合 物為（曱基）丙烯酸聚合物時，具有叛酸基團之聚合物可藉 由自由基聚合獲得。 可用於自由基聚合之含酸基之單體的實例包含丙稀 酸、甲基丙烯酸、衣康酸、丁烯酸、順丁烯二酸、反丁烯 二酸、丙烯酸鄰苯二曱酸單經基乙酯、ω-敌基-聚己内酯單 丙烯酸酯、丙烯酸β-羧基乙酯、2-丙烯醯氧基乙基丁二酸、 201237555 39636pif 敍^2&quot;&quot;丙_氧基乙®1、甲基丙-酸鄰苯二甲 ^酸（3-^Γ/ίΓ縣·聚己㈣旨單甲基_酸§|、甲基丙 丙烯醯甲基丙烯醯氧基乙基丁二酸、2-甲基 古·^ :乙基六氯鄰苯二甲酸以及4_羰基苯乙稀，且具 …之單體的實例包含無水順丁烯二酸。此外，可使用 其他可用單體。 能夠與含酸基之單體共聚合之單體的實例包含下述 ⑴至（12): (1)各具有脂族羥基之丙烯酸酯及曱基丙烯酸酯，諸 如丙烯酸2-羥基乙酯、丙烯酸2-羥基丙酯、丙烯酸3_羥基 丙酯、丙烯酸4-羥基丁酯、曱基丙烯酸2-羥基乙酯、甲基 丙烯酸2-羥基丙酯、甲基丙烯酸3-羥基丙酯或曱基丙烯酸 4-羥基丁酯； (2) 丙烯酸烷酯，諸如丙烯酸曱酯、丙烯酸乙酯、丙 烯酸丙酯、丙烯酸丁酯、丙烯酸異丁酯、丙烯酸戊酯、丙 稀酸己自旨、丙稀酸2-乙基己醋、丙稀酸辛醋、丙稀酸本甲 酯、丙烯酸2-氯乙酯、丙烯酸縮水甘油_、丙烯酸3,4-環 氧基環己基甲酯、丙烯酸乙烯酯、丙烯酸2_苯基乙烯酯、 丙烯酸1-丙烯酯、丙烯酸烯丙酯、丙烯酸2_烯丙氧基乙酯 或丙烯酸炔丙S旨； (3) 甲基丙烯酸烷酯，諸如甲基丙烯酸曱酯、曱基丙 烯酸乙酯、曱基丙烯酸丙酯、曱基丙烯酸丁酯、甲基丙烯 酸異丁酯、曱基丙烯酸戊酯、曱基丙烯酸己酯、曱基丙烯 酸2-乙基己酯、曱基丙烯酸環己酯、曱基丙烯酸苯甲酯、 201237555 39636pif 曱基丙烯酸2-氯乙酯、甲基丙烯酸縮水甘油酯、曱基丙婦 酸3,4-環氧基環己基甲酯 '曱基丙烯酸乙烯酯、甲基丙婦 酸2-苯基乙烯酯、曱基丙烯酸卜丙烯酯、曱基丙烯酸烯丙 酯、甲基丙烯酸2-烯丙氧基乙酯或甲基丙烯酸炔丙酯； (4) 丙烯醯胺或甲基丙烯醯胺，諸如丙烯醯胺、甲基 丙烯醯胺、N-羥曱基丙烯醯胺、N-乙基丙烯醯胺、N-己基 曱基丙烯醯胺、N-環己基丙烯醯胺、N-羥基乙基丙烯醯 胺、N-苯基丙烯醯胺、N_硝基苯基丙烯醯胺、N_乙基-N-苯基丙烯醯胺、乙烯基丙烯醯胺、乙烯基甲基丙烯醯胺、 N，N-二烯丙基丙烯醯胺、n，N-二烯丙基曱基丙烯醯胺、烯 丙基丙烯醯胺或烯丙基甲基丙烯醯胺； (5) 乙烯醚’諸如乙基乙烯醚、2·氣乙基乙烯醚、羥 基乙基乙烯醚、丙基乙烯醚、丁基乙烯轉、辛基乙婦醚或 苯基乙烯醚； (6) 乙烯酯’諸如乙酸乙烯酯、氣乙酸乙烯酯、丁酸 乙烯酯或苯曱酸乙烯酯； (7) 苯乙烯，諸如苯乙烯、α•曱基苯乙烯、曱基苯乙 烯、氣曱基苯乙烯或對乙醯氧基苯乙烯； (8) 乙烯基諸如甲基乙稀基酮、乙基乙稀基酮、 丙基乙烯基酮或苯基乙烯基酮； (9) 烯烴，諸如乙烯、丙烯、異丁烯、丁二烯或異戊 二烯； (10) Ν-乙烯基吡咯啶酮、丙烯腈、甲基丙烯腈以及 其類似物； 15 201237555 jy〇3〇pii (11) 不飽和酸亞胺，諸如順丁烯二醯亞胺、丙稀 醯基丙烯酿胺、N·乙縣甲基丙稀醯胺、N_丙雜甲基丙 稀醯胺或N-(對氣苯曱)甲基丙稀酿胺 ;以及 (12) 各具有雜原子鍵結於α位之曱基丙烯酸單體， 諸如JP-A第2002-309057號及第2002-311569號中所述之 化合物以及其類似物。 其其他適合實例包含側鏈各具有烯丙基或乙烯酯基 團及羧基之（曱基)丙烯酸聚合物，及如JP-A第2000-187322 號中所述之側鏈各具有雙鍵之鹼溶性樹脂，以及如JP-A 第2001-242612號中所述之側鏈各具有醯胺基之鹼溶性樹 脂。 鹼溶性黏合劑聚合物之最佳實例如下所示。201237555 39636pif VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a black polymerizable composition comprising a specific alkali-soluble binder polymer, in particular, a wafer for arranging a plurality of lenses formed on a substrate A black polymerizable composition of a light-shielding region of a Wafer army, and a method of producing a black layer using a black polymerizable composition. [Prior Art] Recently, a compact and low profile (thin) imaging unit is mounted on an electronic terminal of a mobile terminal such as a mobile phone or a Personal Digital Assistant (PDA). These imaging units generally include a solid-state imaging device, such as a Charge Coupled Device (CCD) type image sensor or a Complementary Metal-Oxide Semiconductor (CMOS) type image sensor, and A lens that forms a target image on a solid-state imaging device. As the size and thickness of the mobile terminal are reduced and with the widespread use of mobile terminals, it is necessary to further reduce the size and thickness of the imaging unit mounted on the mobile terminal, and also to improve its productivity. With regard to the need, a method for mass-manufacturing an imaging unit is known, by which a lens substrate on which a plurality of lenses are formed is integrally combined with a sensor substrate on which a plurality of solid-state imaging devices are formed, and the lens substrate is cut and The sensor base includes a lens and a solid-state imaging device in each of the cut portions. In addition, the method of forming a lens on a wafer enables various 201237555 ^yOJOplf simple forming methods to include, for example, a method of manufacturing only a lens on a glass wafer, such as cutting a glass wafer to a certain size to combine individual lenses and senses. a detector, which in turn is combined with a pre-separated imaging device to obtain individual imaging units; a method of forming a plurality of lenses from a resin using only a mold, combining the lenses on a sensor substrate, followed by cutting; and cutting the lens to a certain size A method of combining individual imaging units in combination with an individual sensor and then combining with a pre-separated imaging device. Hereinafter, each of a plurality of lenses formed on a lens substrate is referred to as a wafer level lens, and a lens group (including a lens substrate) formed on the lens substrate is referred to as a wafer level lens array. As a wafer level lens array in the related art, a wafer level lens array is known on which a curable resin material is applied dropwise by a surface of a parallel plate (substrate) formed of a light transmissive material such as glass. The resin material is cured in a state in which it is arranged in a prescribed shape using a mold (see, for example, Japanese Patent Laid-Open No. 3926380 and International Application Publication No. WO 2008/102648). In some cases, a light-shielding portion formed, for example, of a black film or a metal film may be formed in a region other than the lens portion of the wafer-level lens or a portion of the lens to control the amount of light passing therethrough. The light-shielding portion is generally formed by coating a light-shielding curable composition or by depositing a metal. As another wafer level lens array, a wafer level lens array is also known, which is obtained by forming a plurality of through holes on a germanium substrate and disposing the separately formed spherical lens materials in the individual through holes. The lens material is bonded to the substrate by soldering, and then the lens material is polished to form a plurality of lenses 201237555 39636pif (see U.S. Patent No. 6,426,829). In the lens obtained by the manufacturing method, the above black film or metal film can be formed to control The amount of light passing through it. In the case where the light-shielding region is formed by depositing metal, there is a need to improve productivity and efficiency in view of problems such as complicated process or lens bending after deposition. The black polymerizable composition has been used in the coating method to exhibit the light-shielding property (see Japanese Laid-Open Patent Application (Jp-A) No. 2010-8656 and No. 2006-276421). The black polymerizable composition is in the visible light region. In the case where there is sufficient light-shielding property, it is selected from g-rays, h as an exposure light source for curing the black polymerizable composition. Radiation of radiation, i-rays, and/or undulating rays is insufficient. Because of this, the deep part is not fully cured, so 'after the image is successively exposed, there are such as the following _: in the development step (the ten will The film peeling in the unexposed portion is removed. Therefore, the research on the resistance of the developer has not been sufficiently performed: «§ Research. [Invention] The present invention has been made in view of the above aspects and is directed to the following OBJECTIVE: The present invention provides a black polymerizable composition which is resistant to a shuttle developer and thus has excellent light-shielding properties. Polymerization Stage Another aspect of the invention provides a method of using a black polymerizable composition 5 201237555. A method of making a black layer suitable for use in a light-shielding region of a wafer level lens. In general, a carboxylic acid is used in the curable composition. As the resin of the alkali-soluble group, however, in the case where development is carried out under relatively severe conditions to remove the residue of the unexposed portion, there is a problem such as peeling of the image portion. In the case of using a curable composition for lens apertures, a light-shielding property in a wide range from the visible light region to the infrared region is required. In the case where a black polymerizable composition is used to form a light-shielding film 〇ight-shielding film, generally The shirt is imagewise exposed with a light source of 25 nanometers to 5 nanometers, and then developed using a developer. However, since the curable composition contains a black material capable of blocking light in a wavelength region of 250 nm to 500 nm, the light transmittance of the exposure light source is insufficient, and therefore, in some cases, the deep portion of the formed film may be insufficient. Cured. Therefore, in the case where development is carried out under relatively strict conditions to prevent the residual film from being reduced, the strongly acidic tannic acid may cause the developer to penetrate into the image portion A, and thus there is a problem that the strength of the image portion may be lowered to cause a light shielding film (black) Membrane) peeling off. Further, in the case where the black polymerizable composition (or curable composition) is used for the pores of the wafer level lens or the like, the black polymerizable composition may be applied onto the glass wafer and subsequently in the same A method of forming a lens, forming a lens on a glass wafer, and then applying a black polymerizable composition thereon, or the like. However, particularly in the case where a black polymerizable composition is coated after forming a lens, the black polymerizable composition can be effectively applied to the structural substrate by spraying. 201237555 39636pif ^, the inventors of the present invention have studied various black polymerizable polymers to find a black polymerizable composition which is developer-resistant and therefore has excellent properties. The Fortune has also found a black polymerizable composition of enamel. Further, the inventors have found a method of producing a black layer of a light-shielding region suitable for a wafer-level lens by using a color polymerizable composition. Specific exemplary embodiments of the invention are as follows. &lt;1&gt; A black polymerizable composition comprising: (A) a black material; (B) a polymerization initiator; (C) a polymerizable compound; and (D) a weight average molecular weight of at least 3 Å and The base chain has an alkali-soluble binder polymer of a polymerizable group. &lt;2&gt; The black polymerizable composition of &lt;1&gt;, wherein the (A) black material is titanium black. &lt;3&gt; The black polymerizable composition according to <1> or <2>, wherein the (D) alkali-soluble binder polymer has a weight average molecular weight of 5 Å, 〇〇() to 100,000 and The base chain has an alkali-soluble binder polymer of a polymerizable group. &lt;4&gt; The black polymerizable composition as described in any one of &lt;1&gt; to &lt;3&gt;, which is used to form a light-shielding region of a wafer level lens. <5> The black polymerizable composition according to any one of <1> to <4> which can be sprayed. The black polymerizable composition according to any one of <1> to <5>, wherein the total solid content in the black polymerizable composition is 20% by mass 7 201237555 jyojopir to 35 mass %. The black polymerizable composition according to any one of <1> to <6>, wherein the polymerizable group contained in the (D) miscellaneous binder composition is propylene. A group, a methacryl group, a phenethyl group, a dipropyl group, an acrylamide group, a methacrylamide group, a vinyl group or a vinyl bond group. The black polymerizable composition according to any one of <1> to <7>, wherein the content of the (D) gel-soluble binder polymer is the black polymerizable composition. The total solid content is from 5% by mass to 75% by mass. &lt;9&gt; A black layer manufacturing method, the method comprising: applying a black polymerizable composition according to any one of &lt;1&gt; to &lt;8&gt; to a surface of a solid by spraying Forming a black polymerizable composition layer; and applying energy to the formed black polymerizable composition layer to cure the formed black polymerizable composition layer. &lt;10&gt; The method of manufacturing a black layer according to <9>, wherein the surface of the solid is a surface of a peripheral portion of a wafer level lens, and the black layer is as described in a wafer level lens a light-shielding area formed in the peripheral portion. According to one aspect of the present invention, there is provided a black polymerizable composition having alkali developer resistance and thus exhibiting excellent light-shielding properties. Further, according to another aspect of the present invention, a black polymerizable composition capable of being sprayed is provided. In addition, according to another aspect of the present invention, there is provided a method of manufacturing a black layer suitable for a light-shielding region of a wafer level lens using a black polymerizable composition. 0 8 201237555 39636pif [Embodiment] Hereinafter, the present invention will be described in detail. Black polymerizable composition. The following description of the constituent elements is based on representative embodiments of the present invention, but the present invention is not limited to the embodiments. In the present specification, the term "step" or "process" is not only a separate step but also includes the case where the predetermined action of the step is obtained, even if it cannot be clearly distinguished from other steps. Further, in the present specification, the range of numerical values expressed by using "to" (t〇) indicates the range including the minimum and maximum values described before and after "to". (D) Alkali-soluble binder polymer The black polymerizable composition of the present invention comprises an alkali-soluble binder polymer having a weight average molecular weight of 30,000 and a side chain having a polymerizable group. Examples of the polymer constituting the main chain of the (D) alkali-soluble binder polymer used in the present invention include (mercapto)acrylic acid polymer, polyurethane resin, polyvinyl alcohol resin, polyvinyl alcohol Butyraldehyde resin, polyvinyl acetal resin, styrene resin, polyamide resin, polyester resin, epoxy resin, and bismuth resin (such as varnish resin (n〇v〇lak resjn) or nail Resin resin (res 〇l resin). In particular, (fluorenyl) acrylic polymer, styrene resin and phenolic resin are preferred. Further, from the viewpoints of sensitivity and resolution, (mercapto)acrylic polymers and polyaminophthalate resins are preferred, and (mercapto)acrylic polymers are preferred. In the present invention, "(fluorenyl)acrylic polymer" means having (mercapto)acrylic acid, (mercapto) acrylate (such as an alkyl ester, an aryl ester, an allyl ester or the like 201237555 jyojopir), (曱A copolymer of acrylamide or a (meth)acrylic acid derivative such as a (meth)acrylamide derivative as a polymerization component. In the present specification, in the case of describing either or both of "acrylic" and "mercaptopropyl", in some cases, "(indenyl) acryl" may be indicated. In the present invention, "polyaminophthalate resin" means a polymer prepared by a condensation reaction of a compound having two or more isocyanate groups with a compound having two or more hydroxyl groups. In the present invention, "polyvinyl butyral resin" means that polyvinyl alcohol obtained by partially or wholly saponifying polyvinyl acetate is reacted with butyraldehyde under acidic conditions (acetal formation reaction). And a synthetic polymer, and a polymer into which an acid group or the like is introduced by, for example, a method of reacting a residual hydroxyl group with a compound having an acid group or the like. In the present invention, "styrene resin" means an aromatic compound (such as benzene, naphthalene, anthracene) or a heterocyclic ring (meth)acrylic acid and/or (directly bonded) with an alkenyl group such as a vinyl group. A polymer obtained by copolymerization (for example, radical polymerization) of a methyl)acrylic acid derivative. The aromatic compound may be, for example, a hydroxyl group, a carboxyl group, a dentate atom, an alkyl group, a decyltriynyl group, an amine group, a carbonyl group, an ether group, an alkoxycarbonyl group, an oxycarbonyl group, a cyanogen, an aryl group, an alkoxy group, a thio group. Substituted with a thiol group or a similar group. Regarding polymerization, s can be subjected to radical polymerization, cationic polymerization or anion = combination. Further, if necessary, alkali treatment, acid treatment or the like is carried out after the polymerization to obtain the desired vinyl resin. Any other resin can be used as the polymer constituting the main chain of the alkali-soluble binder of the present invention, 201237555 39636pif. For example, the polyamino phthalate resin described in paragraph [0029] to paragraph [〇1 〇8] of jp_A No. 2005-250438, JP-A No. 2010-39121 [0009] can be used. a resin having a decylamine and a polymerizable group in a molecule as described in paragraph [0019] and analogs thereof, and paragraphs [0014] to [0015] of JP-A No. 2000-191737 A resin obtained by reacting a resin having acrylic acid and (fluorenyl) acrylate as a main component with an epoxy group-containing unsaturated compound, and the like, as described therein. Preferably, the image-soluble adhesive polymer of the present invention preferably has a high molecular weight & has a polymerizable group to improve curability, in order to suppress partial image elution of the exposed portion in the developer during development. The alkali-soluble binder polymer of the present invention has a weight average molecular weight of at least. When the weight average molecular weight is less than 30,000, the image portion; the resistance to the developer is insufficient. Further, the weight average molecular weight of the alkali-soluble binder polymer is preferably from 30,000 to 500,000, more preferably from 40,000 to 200,000, and even more preferably %, from the viewpoint of developability of the image portion and the non-image portion. To 100,000. In the present invention, the weight average molecular weight refers to a value measured by a gel permeation chromatography (GPC) method based on stupid ethylene. The side bond of the acid-soluble (tetra) compound of the present invention has a polymerizable group. Polymerizable group propyl group, methyl propyl group, styryl group, allyl group, (tetra) axis group contained in the side chain ^ 11 201237555 iy〇J〇pif-based acrylamide group, vinyl group and vinyl ether group . From the viewpoint of stability and reactivity, a propenyl group, a methacryl group and an allyl group are preferred, and a mercaptopropenyl group is preferred. The amount of the polymerizable group contained in the side chain is preferably from 10 mol% to 8 mol%, based on all the monomer units each having a polymerizable group in the polymer, and is sensitive and developable. And the stability point of view, more preferably 30% to 60% by mole. In the present invention, an example of a method of introducing a polymerizable group into a test-soluble binder polymer comprises: a carboxylic acid in a binder as described in paragraph [0014] of JP-A No. 2000-187322 a method of reacting a part with a compound having a cyclic ether and a (meth) propylene group such as glycidyl methacrylate to introduce a polymerizable group, and the like; and having a method as described in jp_A No. 2000-191737 A resin having acrylic acid and (meth) acrylate as a main component is reacted with an epoxy group-containing unsaturated compound, and a monomer having a hydroxyl group is used as a binder of a copolymerization component with methacrylic anhydride or acrylic anhydride or a method for reacting propylene ruthenium chloride or methacrylium oxime; or a method in which a binder having a hydroxyl group as a copolymerization component is coexisted with mercaptoacrylic acid or acrylic acid and subjected to dehydration/condensation; and, as Jp_A No. 2005- A method of polymerizing a monomer having a side chain having a mercaptoacrylic acid derivative and/or an acrylic acid derivative and treating it with a base, and a method similar thereto, as described in paragraph [0028] of 47947. The alkali-soluble binder polymer of the present invention has an alkali-soluble b group which exhibits alkali solubility. As a functional group that imparts solubility to the binder polymer, the binder polymer must have an acid group in its molecule. Examples of preferred acid groups include tracose 12 201237555 39636 pif group, can acid group, monophosphorus group, hetero group, arylene group, % guanidinium group, sulfinyl group, thiol group, acetamidine A group of acetic acid and its derivatives. The acid group is preferably a carboxylic acid group from the viewpoints of sensitivity, stability, and developability. When the alkali-soluble binder polymer of the present invention has an alkali-soluble group, the cerium-triacid value is preferably from 5 mg / g to 15 mg / g, and preferably from 30 mg / g to 100 mg / K H / gram. Regarding the introduction of a functional group which imparts alkali solubility to the binder polymer, when the polymerization is carried out by radical polymerization, the functional group which imparts alkali solubility to the binder polymer can have an acid group and a polymerizable group (such as A compound of ethylidene (such as methacrylic acid, acrylic acid, vinyl benzoic acid or vinyl phenol) is polymerized for introduction. Further, the introduction of the functional group can also be achieved by hydrolyzing the ethoxylated vinyl phenol followed by hydrolysis. In the case of an amino phthalate binder, for example, a method of subjecting a diol having a halogen moiety to a polycondensation reaction with a diisocyanate compound to introduce an acid group can be used. When the polymer constituting the main chain of the alkali-soluble binder polymer of the present invention is a (mercapto)acrylic polymer, a polymer having an acid-reducing group can be obtained by radical polymerization. Examples of the acid group-containing monomer which can be used for radical polymerization include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and phthalic acid phthalic acid. Ethyl ethyl ester, omega-enyl-polycaprolactone monoacrylate, β-carboxyethyl acrylate, 2-propenyloxyethyl succinic acid, 201237555 39636pif 〉2&quot;&quot; ® 1, methacrylic acid phthalic acid (3-^ Γ / Γ · 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚Examples of the acid, 2-methyl anhydrous: ethyl hexachlorophthalic acid and 4-carbonyl styrene, and the monomer having ... contains anhydrous maleic acid. Further, other usable monomers can be used. Examples of the monomer copolymerizable with the acid group-containing monomer include the following (1) to (12): (1) each of an aliphatic hydroxy group-containing acrylate and a mercapto acrylate such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxy methacrylate Propyl acrylate or 4-hydroxybutyl methacrylate; (2) alkyl acrylates such as decyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, acrylic acid Self-purpose, 2-ethylhexyl acrylate, octyl acrylate, methyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate _, 3,4-epoxycyclohexyl methyl acrylate, Vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate or acetyl acetyl acrylate; (3) alkyl methacrylate, such as Ethyl acrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl decyl acrylate, hexyl methacrylate, 2-ethyl methacrylate Ester, cyclohexyl methacrylate, benzyl methacrylate, 201237555 39636pif 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl methyl thioglycolate 'Mercapto vinyl acrylate, 2-phenyl vinyl methacrylate Alkyl acrylate, allyl methacrylate, 2-allyloxyethyl methacrylate or propargyl methacrylate; (4) acrylamide or methacrylamide, such as acrylamide, Methyl acrylamide, N-hydroxydecyl acrylamide, N-ethyl acrylamide, N-hexyl decyl acrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N -Phenyl acrylamide, N_nitrophenyl acrylamide, N_ethyl-N-phenyl acrylamide, vinyl acrylamide, vinyl methacrylamide, N, N-dienes Propyl acrylamide, n, N-diallyl decyl acrylamide, allyl acrylamide or allyl methacrylamide; (5) vinyl ether 'such as ethyl vinyl ether, 2 · Gas ethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl, octyl ethyl ether or phenyl vinyl ether; (6) vinyl esters such as vinyl acetate, ethylene vinyl acetate, butyl Vinyl acetate or vinyl benzoate; (7) styrene, such as styrene, α-mercaptostyrene, mercaptostyrene, gas styrene or p-ethoxylated styrene; a vinyl such as methyl ethyl ketone, ethyl vinyl ketone, propyl vinyl ketone or phenyl vinyl ketone; (9) an olefin such as ethylene, propylene, isobutylene, butadiene or isoprene (10) Ν-vinyl pyrrolidone, acrylonitrile, methacrylonitrile and its analogues; 15 201237555 jy〇3〇pii (11) unsaturated acid imines such as maleimide, propyl Dilute-based acrylamide, N.B. methyl acrylamide, N-propionylmethyl amide or N-(p-benzoquinone) methyl propylamine; and (12) each The hetero atom is bonded to a thiol acrylate monomer at the alpha position, such as the compounds described in JP-A Nos. 2002-309057 and 2002-311569, and analogs thereof. Other suitable examples thereof include a (fluorenyl)acrylic acid polymer having an allyl group or a vinyl ester group and a carboxyl group in the side chain, and a base having a double bond in the side chain as described in JP-A No. 2000-187322 A soluble resin, and an alkali-soluble resin each having a mercapto group as a side chain as described in JP-A No. 2001-242612. The best examples of the alkali-soluble binder polymer are shown below.

16 201237555 39636pif16 201237555 39636pif

O^NH 人O^NH people

Mw=39d00 &quot;^25重量％^(^Mw=39d00 &quot;^25wt%^(^

NHNH

so2nh2 50重量％So2nh2 50% by weight

Mw=52000Mw=52000

Mw=45000Mw=45000

_54000 201237555 3yb36pif_54000 201237555 3yb36pif

IWOQGdIWOQGd

Mw=37fl；00 201237555 39636pifMw=37fl;00 201237555 39636pif

0·人OH B&quot;1 (Mw 100,000)0·人 OH B&quot;1 (Mw 100,000)

B-2 (Mw 75.000)B-2 (Mw 75.000)

B-3 _ 60,000)B-3 _ 60,000)

在本發明中，鹼溶性黏合劑聚合物可單獨使用或以J 兩種或超過兩種之組合形式使用。 出於影像部分之良好強度及良好抗顯影劑抗性之| =黑土可聚合組成物之總固體含量計，鹼溶性黏合ί 量%至⑽㈣，且甚:=t%，更佳為1〇〗 本發明所用之「總固體含^，頁％至60質量％。 除溶劑以外之組分的總量。」日“、、色可聚合組成物^ (Α)黑色材料 本發明之黑色可聚合組成 本發明所用之（Α)黑色^含黑色材料。 黑色染料、紅色顏料、藍色料之實例包含黑色顏料、 撥色顏料、紫色顏料、青色顏料、'綠色顏料、黃色顏料、 及其類似材料之組合，或紅 洋紅色顏料、灰色顏料 ’卞;斗、藍色染料、綠色染料、 19 201237555 黃色染料、橙色染料、紫色染料、青色染料、洋紅色染料、 灰色染料及其類似材料之組合。出於遮光特性'、儲存穩定 性、安全性及其類似特性之觀點，較佳使用黑色顏料 黑色顏料之實例包含無機顏料，諸如鈦里踹愛。 碳黑㈤·顏料黑7)之市售產品之實例包含、石炭黑 ΜΑ-UK) R (商標名，由三菱化學株式會社（偷油細In the present invention, the alkali-soluble binder polymer may be used singly or in combination of two or more than two. For the good strength of the image portion and the good resistance to developer resistance | = the total solid content of the black soil polymerizable composition, the alkali-soluble adhesive weight % to (10) (four), and even: = t%, more preferably 1 〇 As used herein, "total solid content, % to 60% by mass. Total amount of components other than solvent." Day ", color polymerizable composition ^ (Α) black material The black polymerizable composition of the present invention The (Α) black ^ black material used in the present invention. Examples of black dye, red pigment, and blue material include black pigment, dial pigment, purple pigment, cyan pigment, 'green pigment, yellow pigment, and the like. Combination, or combination of red magenta pigment, gray pigment '卞; bucket, blue dye, green dye, 19 201237555 yellow dye, orange dye, purple dye, cyan dye, magenta dye, gray dye and the like. For the purpose of light-shielding properties, storage stability, safety, and the like, an example of preferably using a black pigment black pigment includes an inorganic pigment such as Titanium. Carbon black (5)·Pigment black 7) Examples of commercially available products contain, carbon black, stone ΜΑ-UK) R (trade name, manufactured by Mitsubishi Chemical Corporation (thin Touyou

Chemical Corporation)製造）。 除石反黑以外之無機顏料的特定實例包含金屬顏料、鈦 黑、鋅白（Chinese white)、鉛白、鋅鋇白（lith〇p〇ne)、 氧化鈦、氧化鉻、氧化鐵、沈澱硫酸鋇及重晶石粉、紅鉛 (red lead)、氧化鐵紅、鉻黃、鉻酸辞（諸如鉻酸鋅卸及四 (zinc tetroxy chromate)). (ultramarine blue)、普魯士藍（Prussian bhje)(亞鐵氰化鉀鐵）、锆灰 (zircon gray)、镨黃、鉻鈦黃、鉻綠、孔雀藍 '維多利亞 綠（Victoria green )、鐵藍（與普魯士藍無關係）、釩鍅藍、 鉻錫粉紅、錳粉紅及鮭魚粉紅（salmon pink)。 黑色無機顏料之實例包含含有由c〇、Cr、cu、Mn、Made by Chemical Corporation). Specific examples of inorganic pigments other than stone anti-black include metallic pigments, titanium black, white white, white, lith〇p〇ne, titanium oxide, chromium oxide, iron oxide, precipitated sulfuric acid.钡 and barite powder, red lead, red iron oxide, chrome yellow, chromic acid (such as zinc tetroxy chromate) (ultramarine blue), Prussian bhje (Prussian bhje) Potassium ferrocyanide, zircon gray, yttrium yellow, chrome titanium yellow, chrome green, peacock blue 'Victoria green', Victoria blue (no relationship with Prussian blue), vanadium indigo, chrome Tin pink, manganese pink and salmon pink. Examples of black inorganic pigments include c〇, Cr, cu, Mn,

Ru、^e、Ni、Sn、Ti及~組成之族群中選出的金屬元素 中之一種或兩種或超過兩種的金屬氧化物及金屬氮化物。 此等顏料可單藏用或以兩種或超過_之混合物形式使 用^ 洋δ之，這些顏料不僅可單獨使用，而且可以多種顏 ，之混合_式制，以在料光纽外光之寬波長區中 20 8 201237555 39636pif 出於遮光特性及固化特性之觀點，金屬顏料及鈦黑 較佳。 …… 金屬顏料較佳為含有銀、錫及其類似物中之至少一者 或銀與錫之混合物的金屬顏料。 出於在紫外光至紅外光範圍内之遮光特性的觀點， 黑為最佳。 —本發明所用之鈦黑為具有鈦原子之黑色粒子。其較佳 實例包含低價氧化鈦及氧氮化鈦。 鈦黑粒子可原樣使用，或其表面可出於例如改良分散 性及抑制聚集特性之觀點視情況進行改質。可用氧化矽、 氧化鈦、氧化鍺、氧化鋁、氧化鎂或氧化鉛塗佈鈦黑粒子。 或者，可如日本特許公開專利申請案（Jp_A)第2〇〇7_3〇2836 號中所述用拒水材料（water repeiient material)處理鈦黑 粒子。 此外，鈦黑可含有Cu、Fe、Μη、V、Ni及其類似物 之複合氧化物以及諸如氧化鈷、氧化鐵、碳黑或苯胺黑之 黑色顏料中之一種、或兩種或超過兩種之組合，以調節分 散性及染色性。在此情況下，鈦黑粒子佔（A)無機顏料 中之50質量％或超過5〇質量〇/0。 鈦黑之市售產品之實例包含鈦黑1〇s、12s、13R、 13M、13M-C、13R及13R_N (商標名，由（三菱材料株 式會社（Mitsubishi Material Corporation))製造）及 TILACK D (商標名，由赤穗化成株式會社（Ak〇KaseiCo.，Ltd.) 製造）。 21 201237555 jyojopif 欽黑可藉由例如如下方法製 I且在在&quot;溫下水解四氣域獲得超精細二氧化 還原二氧化鈦或氫氧化鈦/Λ 下在氛氣存在下 著於：氧化卩嫩化合物黏 原所得產物的綠（參❹在下還 本發明並不限於所述方法。A第61-2016H)號）’但 性之m娜及染色 至⑽奈米，=二奈米，更佳為ι〇奈米 米至2_奈米，，較佳為3奈 奈求至刚奈米。巧U至500奈米，且最佳為10 由拒:而，級在欽黑藉 平方二===_方公尺咖-公尺/公克。 為約〇平方公尺/公克至觸平方 米，且本出發^之^機^料的平均粒徑較佳為5奈米至_毫 X7i 、遮光紐輯日H沈降特性的觀點，One or two or more than two metal oxides and metal nitrides selected from the group consisting of Ru, ^e, Ni, Sn, Ti, and ~. These pigments can be used alone or in the form of a mixture of two or more than δ. These pigments can be used not only alone, but also in a variety of colors, mixed with a wide range of colors. In the wavelength region, 20 8 201237555 39636pif Metal pigments and titanium black are preferred from the viewpoint of light shielding properties and curing characteristics. The metallic pigment is preferably a metallic pigment containing at least one of silver, tin and the like or a mixture of silver and tin. Black is optimal from the viewpoint of the light-shielding property in the ultraviolet to infrared range. - The titanium black used in the present invention is a black particle having a titanium atom. Preferred examples thereof include low-valent titanium oxide and titanium oxynitride. The titanium black particles can be used as they are, or the surface thereof can be modified as appropriate, for example, from the viewpoint of improving dispersibility and suppressing aggregation characteristics. The titanium black particles may be coated with cerium oxide, titanium oxide, cerium oxide, aluminum oxide, magnesium oxide or lead oxide. Alternatively, the titanium black particles may be treated with a water repeiient material as described in Japanese Laid-Open Patent Application (Jp-A) No. 2-7_2836. Further, the titanium black may contain a composite oxide of Cu, Fe, Μ, V, Ni, and the like, and one of black pigments such as cobalt oxide, iron oxide, carbon black or aniline black, or two or more The combination is to adjust the dispersibility and dyeability. In this case, the titanium black particles account for 50% by mass or more than 5% by mass of (/0 in the (A) inorganic pigment. Examples of commercially available products of titanium black include titanium black 1 〇 s, 12 s, 13R, 13M, 13M-C, 13R, and 13R_N (trade name, manufactured by Mitsubishi Material Corporation) and TILACK D ( Trade name, manufactured by Akko Kasei Co., Ltd.). 21 201237555 jyojopif 钦黑 can be obtained by, for example, the following method and obtaining ultrafine redox dioxide or titanium hydroxide/ruthenium under the condition of "temperature hydrolysis of four gas domains": The green color of the product obtained by the viscous material (the present invention is not limited to the method described below. A No. 61-2016H)) 'but the mna and the dyed to (10) nanometer, = two nanometers, more preferably ι 〇Nami rice to 2_nano, preferably 3 Nana to the north. Qiao U to 500 nm, and the best is 10 by: but, the class is borrowed in Qinhe Square 2 ===_ square meters coffee - meters / gram. It is about 〇 square meters / gram to the square meter, and the average particle size of the machine is preferably from 5 nanometers to _ milli X7i, and the black sedimentation characteristics of the blackout day.

22 201237555 39636pif 平句更佳為1〇奈米至1微米。 或其兩僅包含單種黑色材料 種之s。此外，如下所述，必要時， 二:二光=合^^ 計較佳為7 ^。二成::黑色材料之含量以總固體含量 質量％。質里/°至70質量％ ’且更佳為10質量％至50 顏料分散劑 成物^使Γί戶ί得(二2材料之顏料調配黑色可聚合組 顏料分散均一性之觀點’顏料較佳用已知 液顧先分散以製備顏料分散液，且摻合顏料分散 選擇文亦簡稱作「分散劑」)，可適當 知顏料分散劑或界面活性劑。 賴各種化合物可用作分散劑。其實例包含： 1 /舌性劑’諸如有機石夕氧院聚合物ΚΡ341 (商 才示名、，^信越化學I業株式會社（Shin-EtsuChemicdCo.， Ltd·;仏）、（曱基）丙烯酸⑻聚合物泊里富勞 POLYFLOW)第75號、第9〇號、第％號（商標名，由 共榮社化學株式會社（KyGeishaChemiealCG” Ltd )製造） 或穩1 (商標名，講自裕商株式會社（Yush。C。·, Ltd.)); 非離子型界面活性劑’諸如聚氧乙稀月桂鍵、聚氧乙稀硬 脂鍵、聚氧乙稀油鱗、聚氧乙稀辛基苯醚、聚氧乙烯壬基 23 201237555 39636pif 苯醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯或脫水 山梨糖醇脂肪酸酯；陰離子型界面活性劑，諸如w〇〇4、 W005或W017(商標名，由裕商株式會社（Yush〇 c〇，Ltd ) 製造）；聚合物分散劑，諸如埃弗卡（EFKA) _46、埃弗卡 -47、埃弗卡-47EA、埃弗卡聚合物1〇〇、埃弗卡聚合物4〇〇、 埃弗卡聚合物401、埃弗卡聚合物45〇 (商標名，由巴斯夫 公司（BASF Corporation)製造）、分散助劑（DISPERSE AID) 6、分散助劑8、分散助劑15或分散助劑9100 (商 標名’由聖諾普科有限公司（San Nopco Limited)製造）； 各種索斯帕思（SOLSPERSE )分散劑，諸如索斯帕思 3000、5000、9000、12000、13240、13940、17000、24000、 26000、28000、32000或36000(商標名，由路博潤公司（The Lubrizol Corporation)製造）；艾迪科普洛尼克（ADEKA PLURONIC) L31、F38、L42、L44、L6 卜 L64、F68、L72、 P95、F77、P84、F87、P94、L101、P103、F108、L121、 P-123 (商標名，由艾迪科株式會社（ADEKACorporation) 製造）；伊能特（IONET) S-20 (商標名，由三洋化成工業 株式會社（Sanyo Chemical Industries，Ltd.)製造）；及迪 斯畢克（DISPERBYK) 10卜 103、106、108、109、m、 112、116、130、140、142、162、163、164、166、167、 170、17卜 174、176、180、182、2000、20(H、2050、2150 (商標名，由畢克化學公司（BYK-Chemie)製造）。 另外，分散劑之其他實例包含在分子之末端或側鏈具 有極性基團之寡聚物及聚合物，諸如丙稀酸共聚物。22 201237555 39636pif The phrase is better from 1 nanometer to 1 micron. Or two of them contain only a single black material. Further, as described below, if necessary, two: two light = combined is preferably 7 ^. 20%:: The content of black material is the total solid content by mass%. In the texture / ° to 70% by mass 'and more preferably 10% by mass to 50% of the pigment dispersant ^ ^ 户 户 ί ( 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二The pigment dispersion liquid is prepared by dispersing with a known liquid, and the pigment dispersion is also referred to as a "dispersant", and a pigment dispersant or a surfactant may be appropriately known. Various compounds can be used as a dispersing agent. Examples thereof include: 1 / Tongue agent 'such as organic stone oxime polymer ΚΡ 341 (Shang dynasty name,, Shin-EtsuChemicd Co., Ltd.; 仏), (曱基) acrylic acid (8) Polymer Poriolf POLYFLOW) No. 75, No. 9 、, No. No. (trade name, manufactured by KyGeisha Chemieal CG" Ltd) or stable 1 (trade name, from Yushang Yush.C., Ltd.); Non-ionic surfactants such as polyoxyethylene laurel, polyoxyethylene hard fat, polyoxyethylene oil scale, polyoxyethylene octyl Phenyl ether, polyoxyethylene fluorenyl 23 201237555 39636pif phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate or sorbitan fatty acid ester; anionic surfactant, such as w〇 〇4, W005 or W017 (trade name, manufactured by Yushang Co., Ltd.); polymer dispersant, such as Efka (EFKA) _46, Evka-47, Evka - 47EA, Efka Polymer 1〇〇, Efka Polymer 4〇〇, Efka Polymer 401, Efka Polymer 4 5〇 (trade name, manufactured by BASF Corporation), dispersing aid (DISPERSE AID) 6, dispersing aid 8, dispersing aid 15 or dispersing aid 9100 (trade name 'by San Nopco Co., Ltd. (Manufactured by San Nopco Limited); various SOLSPERS dispersants, such as Sospers 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, 32000 or 36000 (trade names) , manufactured by The Lubrizol Corporation; ADEKA PLURONIC L31, F38, L42, L44, L6, L64, F68, L72, P95, F77, P84, F87, P94, L101 , P103, F108, L121, P-123 (trade name, manufactured by ADEKA Corporation); IONET S-20 (trade name, by Sanyo Chemical Industries, Ltd.) .))) and DISPERBYK 10, 103, 106, 108, 109, m, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 17 174 , 176, 180, 182, 2000, 20 (H, 2050, 2150 (trade name, by Manufactured by BYK-Chemie). Further, other examples of the dispersing agent include an oligomer having a polar group at a terminal or a side chain of a molecule, and a polymer such as an acrylic acid copolymer.

S 24 201237555 39636pif 另外，宜使用兩性（amphoteric)分散劑’諸如西諾 科特（HTNOACT) T-8000E (商標名’由川研精細化學株 式會社（Kawaken Fine Chemicals Co.，Ltd.)製造）。 出於分散性、顯影性以及沈降特性之觀點，如JP-A 第2010-106268號中所述，下文所示樹脂為較佳，特定言 之’出於分散性之觀點，側鏈具有聚酯鏈之聚合物分散劑 為較佳。出於分散性及藉由光微影術形成之圖案的解析度 的觀點，具有酸基及聚酯鏈之樹脂為較佳。作為顏料分散 劑中之較佳酸基，出於吸附性之觀點，pKa為6或低於6 之酸基為較佳’且敌酸、續酸或鱗酸為尤其較佳。出於在 为散/谷液中之溶解性、分散性以及顯影性的觀點，具有聚 己内酯側鏈作為聚酯鏈且具有羧酸基團之樹脂為最佳。 下文將說明如jP_A第2010_106268號中所述之分散 劑’其較佳用於本發明。 較佳分散劑為如下接枝共聚物：其分子中除氫原子以 40至10，_範圍内’其具有選自聚醋結構、 匕鼻及艰兩烯酸醋結構之接枝鏈，且其包含由下文所 (不1:)彳2、(4)表示之任一結構單元，且包含由下式 者表干St式(3Α)、式⑽及式(4)中之任-者表之、、構早元的接枝共聚物為更佳。 25 201237555 ^yo^opifS 24 201237555 39636pif Further, an amphoteric dispersant such as HTNOACT T-8000E (trade name 'Kawaken Fine Chemicals Co., Ltd.) is preferably used. From the viewpoints of dispersibility, developability, and sinking characteristics, as described in JP-A No. 2010-106268, the resin shown below is preferable, specifically, from the viewpoint of dispersibility, the side chain has a polyester. Chain polymeric dispersants are preferred. From the viewpoint of dispersibility and resolution of a pattern formed by photolithography, a resin having an acid group and a polyester chain is preferred. As the preferred acid group in the pigment dispersant, an acid group having a pKa of 6 or less is preferred from the viewpoint of adsorptivity, and a diacic acid, a sodling acid or a squaric acid is particularly preferable. From the viewpoint of solubility, dispersibility, and developability in the dispersion/trough liquid, a resin having a polycaprolactone side chain as a polyester chain and having a carboxylic acid group is preferred. The dispersant' as described in jP_A No. 2010_106268 is preferably described below for its use in the present invention. The preferred dispersant is a graft copolymer having a graft chain selected from the group consisting of a polyester vinegar structure, a sputum and an oleic acid vinegar structure, in addition to a hydrogen atom in the molecule of 40 to 10 Å. Containing any structural unit represented by (not 1:) 彳2, (4) below, and including the following formula: (Standard(3), Formula (10), and (4) The graft copolymer of the early structure is more preferred. 25 201237555 ^yo^opif

在式（1)至式（4)中，wi、 2 地表示氧原子或，且尤其較佳表:氧;及一 在式（1)至式（4)中，χ1、χ2、χ3子 ^ χ、χ、χ及χ各獨立地較佳表示氫原子或且有 個至12健肝之絲，更録示 ^ 較佳表示甲基。 了且尤$ 在式⑴至式⑷巾，/、〜3及¥4各獨朗 表3不一價鍵聯基團，且其結構不受特別限制。由γ1、γ1 Υ3及Υ4表示之二價鍵聯基團之特定實例包含由以下結榻 (Υ-1)至結構（Υ-21)表示之鍵聯基團。在以 、 至結構（Υ-21)中，Α分別表示式（1)至式_ γ; 與π、γ2與w2、γ3與w3以及/與W4之間的鍵，且b 分別表示式（1)至式（4)中Υ'Υ2、·^、γ4與存在於 W1、W2、W3、W4之相反位置的部分之間的鍵。^下文所In the formulae (1) to (4), wi, 2 represents an oxygen atom or, and particularly preferably represents: oxygen; and in the formulae (1) to (4), χ1, χ2, χ3 sub ^ Each of ruthenium, osmium, iridium and osmium preferably represents a hydrogen atom or has a filament of up to 12 hepatic livers, and further indicates that ^ is preferably a methyl group. And especially in the formula (1) to the formula (4), /, ~3, and ¥4 each of the three groups are not monovalently bonded, and the structure thereof is not particularly limited. Specific examples of the divalent linking group represented by γ1, γ1 Υ 3 and Υ 4 include a linking group represented by the following (Υ-1) to the structure (Υ-21). In the s, to the structure (Υ-21), Α denotes the bond between the formula (1) and the formula _ γ; and π, γ2 and w2, γ3 and w3, and / and W4, respectively, and b denotes the formula (1) To the bond between the portions of the formula (4) where Υ'Υ2, ·^, γ4 are present at the opposite positions of W1, W2, W3, and W4. ^The following

26 201237555 39636pif 示結構中，為易於合成，（Y-2)及（Y-13)之結構為更佳。26 201237555 39636pif The structure is better for easy synthesis, and the structures of (Y-2) and (Y-13) are better.

AA

B ο (Υ-1) (Υ-4) (Υ-7)： 〇 Η (Υ-2) .Α (Υ-5) Β (Υ-10) ΟB ο (Υ-1) (Υ-4) (Υ-7): 〇 Η (Υ-2) .Α (Υ-5) Β (Υ-10) Ο

(Υ-13)(Υ-13)

(Υ-14) S 巳 Η (Υ-3) a ^,a: (Υ-6) 巳 (Υ-9) Ο Ν人日 Η (Υ-12) &gt;ΟΗ(Υ-14) S 巳 Η (Υ-3) a ^,a: (Υ-6) 巳 (Υ-9) Ν 日人日 (Υ-12) &gt;ΟΗ

.QH ,ΟΗ cAo (Υ-Τ6) 0' 'Β (Υ-17) (Υ-15).QH ,ΟΗ cAo (Υ-Τ6) 0' 'Β (Υ-17) (Υ-15)

27 20123755527 201237555

(y-19)(y-19)

OHOH

(Y^20) (Y-21) 在式（1)至式（4)中，z1、z2、Z3及Z4久猫☆地矣 示單價有絲ffi ’且其轉不受_限制。其特定實例包 含烧基、祕、絲基、芳氧基或雜芳氧基、絲硫喊 團、芳基硫醚基團或雜芳基硫醚基團以及胺基。其中，作 為由Z1、Z2、Z3及z4表示之單價有機基團，出於改良分 散性之觀點，具有空間排斥特性之基團為尤其較佳。由Z1 至Z3表示之有機基團較佳各獨立地表示具有5個至24個 碳原子之烷基或具有5個至24個碳原子之烷氧基，且尤其 較佳表示含有具有5個至24個碳原子之分支鏈烷基的烷氧 基或含有具有5個至24個碳原子之環狀烷基的烷氧基。由 Z4表示之有機基團較佳為具有5個至24個碳原子之烷 基，且尤其較佳為具有5個至24個碳原子之分支鏈烷基或 具有5個至24個碳原子之環狀烷基。 在式（1)至式（4)中，n、m、p及q各為1至500 之整數。 在式（1)及式（2)中，j及让各獨立地表示2至8 之整數’且出於分散穩定性及顯影性之觀點，式（1)及式 (2)中之j及k較佳為4至6之整數，且最佳為5。(Y^20) (Y-21) In the formulas (1) to (4), z1, z2, Z3, and Z4 long cats ☆ 矣 示 单价 单价 单价 单价 单价 单价 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且Specific examples thereof include an alkyl group, a secret group, a silk group, an aryloxy group or a heteroaryloxy group, a sulphur group, an aryl sulfide group or a heteroaryl sulfide group, and an amine group. Among them, as the monovalent organic group represented by Z1, Z2, Z3 and z4, a group having a steric repellency property is particularly preferable from the viewpoint of improving the dispersibility. The organic groups represented by Z1 to Z3 preferably each independently represent an alkyl group having 5 to 24 carbon atoms or an alkoxy group having 5 to 24 carbon atoms, and particularly preferably contain 5 to An alkoxy group of a branched alkyl group of 24 carbon atoms or an alkoxy group having a cyclic alkyl group having 5 to 24 carbon atoms. The organic group represented by Z4 is preferably an alkyl group having 5 to 24 carbon atoms, and particularly preferably a branched alkyl group having 5 to 24 carbon atoms or having 5 to 24 carbon atoms. Cyclic alkyl group. In the formulae (1) to (4), n, m, p and q are each an integer of from 1 to 500. In the formulas (1) and (2), j and each of the integers 2 to 8 are independently indicated, and in the viewpoints of dispersion stability and developability, j in the formulas (1) and (2) k is preferably an integer from 4 to 6, and most preferably 5.

28 201237555 39636pif 式O)中之R3表示分支缝或直鍵（straight_chained) 伸烷基。式（3)中之R3較佳為具有丨個至1〇個碳原子之 伸烧基，且更佳為具有2個或3個碳原子之伸烧基。 式（4)中之R4表示氫原子或單價有機基團，且單價 有機基團之結構不受特別限制。式（4)中之R4之較佳實 例包含氫原子、烷基、芳基及雜芳基，且更佳為氫原子及 烷基。S式（4)中之R4為烧基時，烧基較佳為具有j個 至20個碳原子之直鏈烷基、具有3個至20個碳原子之分 支鏈烧基或具有5個至2G個碳原子之雜絲，更佳為具 有1個至20個碳原子之直鏈烷基，且尤其較佳 \ 個至6個碳原子之直鏈絲。此外，關於式⑷=r4， 兩種或超過兩種具有不同結構之r4可混合且用於接枝妓 聚物中。 ^ 在接枝共聚物中，由式（1)至式⑷絲之結構單 疋之含量（亦即總含量）以接枝共聚物之總f量計較佳在 =至90%範_，且更佳在3()%至7()%範_。當由式 )至式（4)表示之結構單元包含在這些範_時，顏料 之为散性很高，且當形成遮光膜時顯影性良好。〃 接枝可包含_或超過_具林⑽構之 出於分散穩定性及顯影性之觀點，由式 結構單从佳為由下式（1A)表示之結構^。）表不之 出於^穩定性及顯影性之觀點，由式⑴表示之 、、·。構早το更佳為由下式（2A)表示之結構單元。 29 201237555 jyo^opif28 201237555 39636pif R3 in formula O) stands for a branch or straight chain (straight_chained) alkyl group. R3 in the formula (3) is preferably a stretching group having from one to one carbon atoms, and more preferably an extending group having two or three carbon atoms. R4 in the formula (4) represents a hydrogen atom or a monovalent organic group, and the structure of the monovalent organic group is not particularly limited. Preferred examples of R4 in the formula (4) include a hydrogen atom, an alkyl group, an aryl group and a heteroaryl group, and more preferably a hydrogen atom and an alkyl group. When R4 in the formula (4) is a calcined group, the alkyl group is preferably a linear alkyl group having j to 20 carbon atoms, a branched chain having 3 to 20 carbon atoms or having 5 to The heterochromium of 2 G carbon atoms is more preferably a linear alkyl group having 1 to 20 carbon atoms, and particularly preferably a linear chain of from 1 to 6 carbon atoms. Further, with respect to the formula (4) = r4, two or more than two kinds of r4 having different structures may be mixed and used for grafting the ruthenium polymer. ^ In the graft copolymer, the content of the monoterpene of the filaments of the formula (1) to the formula (4) (i.e., the total content) is preferably from 0 to 90% in terms of the total amount of the graft copolymer, and Good in 3 ()% to 7 ()% _. When the structural unit represented by the formula (4) is contained in these formulas, the pigment is highly dispersible, and the developability is good when the light-shielding film is formed. 〃 Grafting may include or exceed the structure of the structure (1A) of the formula (1A) from the viewpoint of dispersion stability and developability. It is represented by the formula (1) from the viewpoint of stability and developability. The structure το is more preferably a structural unit represented by the following formula (2A). 29 201237555 jyo^opif

在式（1A)中，χ1、γ1 中之^、…及㈠目同之定卜分別具有與式。 實例及類似方面）亦相同。義，且其較佳範圍（包含 在式（2Α)中，χ2 2 中之Χ2、Υ2、Ζ2β 4 Υ、Ζ及111分別具有與式（2 Ζ及m相同之定義，且其較佳 其實例及類似方面）亦相同。 匕 出於分散穩定性及顯影性之觀點，由式 結構單元更佳為由下式（3A)或式（3B)表示之結構單元In the formula (1A), ^, ..., and (i) in the χ1, γ1 have the same formula. The examples and similar aspects are also the same. Meaning, and its preferred range (included in the formula (2Α), Χ2, Υ2, Ζ2β 4 Υ, Ζ and 111 in χ2 2 have the same definitions as the formulas (2 Ζ and m, respectively, and preferred examples thereof) And the like) is also the same. The structural unit is more preferably a structural unit represented by the following formula (3A) or (3B) from the viewpoint of dispersion stability and developability.

0^00^0

(3B) 30 201237555 39636pif 在式（3A)或式（3B)中，X3、Y3、Z3及p分別具 有與式（3)中之X3、Y3、Z3及p相同之定義，且其較佳 範圍（包含其實例及類似方面）亦相同。 接枝共聚物更佳具有由式（1A)表示之結構單元。 接枝共聚物之特定實例包含下文所示化合物。此外， 在下文所示例示性化合物中，與個別結構單元一起顯示之 數值表示相應結構單元之含量（質量％:適當地表示為（重 量 〇/〇 ))。 31 201237555. jyojopu(3B) 30 201237555 39636pif In the formula (3A) or the formula (3B), X3, Y3, Z3 and p have the same definitions as X3, Y3, Z3 and p in the formula (3), respectively, and a preferred range thereof (including its examples and similar aspects) are also the same. The graft copolymer more preferably has a structural unit represented by the formula (1A). Specific examples of the graft copolymer include the compounds shown below. Further, in the exemplified compounds shown below, the numerical values shown together with the individual structural units indicate the content of the corresponding structural unit (% by mass: suitably expressed as (weight 〇/〇)). 31 201237555. jyojopu

^ 20 , OH O 8 0 (重量％)^ 20 , OH O 8 0 (% by weight)

HN ίο γΟ^Ιχ/Ν/γ0&quot;) 〇 〇 (例示性化合物1)HN ίο γΟ^Ιχ/Ν/γ0&quot;) 〇 〇 (exemplary compound 1)

0 (例示性化合物2) 200 (exemplary compound 2) 20

(例示性化合物4) 32 201237555 39636pif(Exemplary Compound 4) 32 201237555 39636pif

v ό /2S (例示性化合物7)v ό /2S (exemplary compound 7)

33 201237555 jyo^opif33 201237555 jyo^opif

34 201237555 39636pif34 201237555 39636pif

ΟΟ

35 201237555 JVOJOpii35 201237555 JVOJOpii

ip (t 量。/〇) (例示性化合物21)Ip (t amount. /〇) (exemplary compound 21)

36 201237555 39636pif36 201237555 39636pif

OMeOMe

37 201237555、 jyooopn37 201237555, jyooopn

38 201237555 39636pif38 201237555 39636pif

2p2p

'7 0 _量％) \'7 0 _ quantity%) \

〇 〇 (例示性化合物30)〇 〇 (exemplary compound 30)

0 〇' Ν Ο ο (例示性化合物31) 39 201237555 jyojopn0 〇' Ν Ο ο (exemplary compound 31) 39 201237555 jyojopn

40 201237555 39636pif40 201237555 39636pif

(例示性化合物38)(exemplary compound 38)

41 201237555 jyojbpit41 201237555 jyojbpit

42 201237555 39636pif42 201237555 39636pif

43 201237555 ^yojopn43 201237555 ^yojopn

OH (例示性化合物49)OH (exemplary compound 49)

OHOH

44 201237555 39636pif44 201237555 39636pif

45 201237555.45 201237555.

46 201237555 39636pif46 201237555 39636pif

47 201237555.47 201237555.

48 201237555 39636pif48 201237555 39636pif

49 201237555 3y〇3bpif49 201237555 3y〇3bpif

(例示性化合物73) 作為本發明之分散劑，較佳使用具有聚酯鏈之化合物 (諸如例示性化合物72)。 用於製備本發明鋪分散液之分散賴含量以顏料 分散液中著㈣I (包含黑色顏料及其他著色船之總固體 =含物質量計較佳為i質量％至9G f量％，且更 質 量％至70質量％。 (B)聚合起始劑 本發明之黑色可聚合組成物包含聚合起始劑。 本發料聚合㈣财㈣之 限制，只要其能夠藉由施加光及熱中之任-者S二 50 201237555 39636pif 可聚合化合物之聚合即可，且可視目的而定來適當選擇。 然而，在藉由光起始聚合之情況下，較佳使用對紫外線區 至可見光範圍内之射線具有感光性之聚合起始劑。 另外’在藉由熱起始聚合之情況下，較佳使用在15〇t： 至250°C下分解之起始劑。 本發明所用之聚合起始劑較佳為具有至少一個芳族 基之化合物。其實例包含(雙)醯基膦氧化物或其酯、苯乙 酮化合物、α-胺基酮化合物、二笨甲酮化合物安息香醚 化^物、縮酮衍生物化合物、噻噸酮化合物、肟酯化合物、 六芳基聯味唾化合物、三鹵曱基化合物、偶氣化合物、有 機過氧化物、茂金屬化合物、鏽鹽化合物（諸如重氮鏽化 合物、錤化合物、銃化合物或吖嗪鑷（azinium)化合物）、 有機蝴鹽化合物以及二硬化合物。 出於敏感性之觀點，肟酯化合物、苯乙酮化合物、醯 基膦氧化物化合物、α_胺基酮化合物、三鹵曱基化合物、 六芳基聯咪唑化合物以及硫醇化合物為較佳，且醯基膦氧 化物化合物、肟酯化合物、α_胺基_化合物以及其類似物 為更佳。 較佳用於本發明中之聚合起始劑之實例如下所述，但 本發明並不限於所述實例。 苯乙酮化合物之特定實例包含2,2_二乙氧基苯乙酮、 對二甲基胺基笨乙酮、2-羥基-2-曱基苯基_丙_14同、對 一甲基胺基本乙_、4’-異丙基·2-經基_2_曱基苯丙_、I-沒基-環己基-本基-酮、2_苯曱基二曱基胺基_ι_(4-鳴你基 51 201237555 苯基)-丁酮-1、2-甲苯基-2-二甲基胺基-1-(4-嗎啉基苯基)_ 丁酮-1、2-甲基-1-[4-(甲基硫基)苯基]_2_嗎啉基丙酮_〗、2_ 甲基-1-(4-甲基硫基苯基)-2-嗎琳基丙-1-酮、2-苯甲基_2_二 甲基胺基-1-(4-嗎啉基苯基)_丁酮_ι、2_(二甲基胺基)_2_[(4_ 甲基笨基）甲基]-1-[4·(4-嗎啉基）苯基]_1_ 丁酮以及2_甲基 -1-(4-甲基硫基苯基)_2_嗎啉基丙酮。其中，較佳用於本 毛明中之2-曱基-1-(4-曱基硫基苯基)_2_嗎啉基丙_；μ酮可 以商標名「豔佳固（IRGACURE)9〇7」（由巴斯夫公司 (BASF)製造）購得。 三齒曱基化合物之更佳實例包含具有至少一個經單 鹵素、二齒素或三_素取代之曱基鍵結於s_三嗪環的s三 嗪衍^物。其特定實例包含2,4,6-三(單氣曱基)_s_三嗪、 2,4,6-二(二氣曱基)-s_三唤、2,4,6三(三氣曱基)三嗓、孓 :基-4^6-雙(二氣曱基)♦三嗪、2_正丙基_4,6雙(三氣甲 土!广三嗪、2-(α，α，Ρ-三氣乙基H，6-雙(三氣曱基)♦三嗪、 -笨基_4,6-雙(三氣甲基)_s_三嗪、2_(對曱氧基苯基)·4,6雙 氯Υ基)-s-三嗪、2_(3,4_環氧基苯基)_4 6_雙（三氣甲 土 Vs-三嗪、2_(對氣苯基M，6雙（三氯甲基h三嗪、 嗥1(對7氧基苯基)-2,4·丁二烯基]-4,6-雙(三氣曱基)_s_三 ?本乙稀基·4,6·雙(三氣曱基&gt;S•三嗓、2_(對曱氧基笨 =烯基H，6-雙(三氣甲基)+三唤、2侦異丙氧基苯乙歸 ^雙(三氣甲基)·δ_三嗅、2_(對曱苯基)_4,6_雙(三氣甲 二—s-二嗓、2_(4_甲氧基萘基)4 6雙(三氣甲基)s·三嗪、 本基硫基-4,6-雙(三氯甲基)_s_三唤、2_苯甲基硫基_4,6_(Exemplified Compound 73) As the dispersing agent of the present invention, a compound having a polyester chain (such as exemplified compound 72) is preferably used. The dispersion content of the dispersion liquid used in the preparation of the present invention is preferably in the pigment dispersion liquid (IV) I (including the total solid content of the black pigment and other coloring boats = mass% of the mass% to 9 G f%, and more mass%) Up to 70% by mass. (B) Polymerization initiator The black polymerizable composition of the present invention contains a polymerization initiator. The present invention polymerizes (4) the limitation of (4) as long as it can be applied by applying light and heat. 2 50 201237555 39636pif Polymerization of the polymerizable compound may be appropriately selected depending on the purpose. However, in the case of polymerization by light, it is preferred to use a light sensitive to radiation in the ultraviolet range to the visible range. Polymerization initiator. Further, in the case of polymerization by thermal initiation, it is preferred to use an initiator which decomposes at 15 Torr to 250 ° C. The polymerization initiator used in the present invention preferably has at least An aromatic group-containing compound, examples of which include (bis)decylphosphine oxide or an ester thereof, an acetophenone compound, an α-aminoketone compound, a dimercapto ketone compound, a benzoin ether compound, a ketal derivative compound Thioxanthone a compound, an oxime ester compound, a hexaaryl-linked salivary compound, a trihalofluorenyl compound, an azo compound, an organic peroxide, a metallocene compound, a rust salt compound (such as a diazonium rust compound, a hydrazine compound, a hydrazine compound or An azinium compound, an organic butterfly compound, and a di-hard compound. From the viewpoint of sensitivity, an oxime ester compound, an acetophenone compound, a mercaptophosphine oxide compound, an α-aminoketone compound, a trihalide A mercapto compound, a hexaarylbiimidazole compound, and a thiol compound are preferred, and a mercaptophosphine oxide compound, an oxime ester compound, an α-amino group compound, and the like are more preferred. Examples of the polymerization initiator in the following are as follows, but the present invention is not limited to the examples. Specific examples of the acetophenone compound include 2,2-diethoxyacetophenone, p-dimethylamino stupid Ketone, 2-hydroxy-2-indolylphenyl-propane-14, p-monomethylamine, basic B-, 4'-isopropyl-2-trans- 2,2-mercaptophenylene, I- Base-cyclohexyl-benyl-ketone, 2-phenylindolediylamino group_ι_(4-鸣你基51 201237555 Phenyl)-butanone-1, 2-tolyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl-1-[4- (methylthio)phenyl]_2_morpholinylacetone _, 2_methyl-1-(4-methylthiophenyl)-2-morphinylpropan-1-one, 2-phenyl Base 2_dimethylamino-1-(4-morpholinylphenyl)-butanone_ι, 2_(dimethylamino)_2_[(4-methylphenyl)methyl]-1- [4·(4-morpholinyl)phenyl]_1_butanone and 2-methyl-1-(4-methylthiophenyl)_2-morpholinylacetone. Among them, it is preferably used in the present invention. 2-Mercapto-1-(4-mercaptothiophenyl)_2_morpholinylpropanone; μketone can be traded under the trade name "IRGACURE 9〇7" (manufactured by BASF) Purchased. More preferred examples of the tridentate mercapto compound include an s-triazine derivative having at least one mercapto group substituted with a monohalogen, a bidentate or a tris-substrate bonded to the s_triazine ring. Specific examples thereof include 2,4,6-tris(monochamoyl)_s_triazine, 2,4,6-di(diqimethyl)-s_three, 2,4,6 three (three gases)曱基)三嗓,孓:基-4^6-double (diqi fluorenyl) ♦ triazine, 2_n-propyl _4,6 double (three gas carbaz! wide triazine, 2-(α, α,Ρ-tri-equivalent ethyl H,6-bis(trimethylsulfonyl)♦triazine,-stupyl-4,6-bis(trimethylmethyl)_s_triazine, 2_(p-methoxybenzene) Base)·4,6-dichloroindolyl)-s-triazine, 2_(3,4-epoxyphenyl)_4 6_bis (three gas methane Vs-triazine, 2_(p-phenylene M) , 6 bis (trichloromethyl h-triazine, 嗥 1 (p-7-oxyphenyl)-2,4.-butadienyl]-4,6-bis (trimethyl fluorenyl) _s_ three? Dilute base · 4,6 · double (three gas sulfhydryl groups &gt; S • triterpenoids, 2 _ (p-oxooxy stupid = alkenyl H, 6-bis (trimethyl) + triple call, 2 detective isopropoxy Benzophenone bis(trismethyl)·δ_trisole, 2_(p-phenylene)_4,6_bis (tris-methyl-di-s-dioxin, 2_(4-methoxynaphthyl) ) 4 6 bis(trimethyl) s triazine, thiol-4,6-bis(trichloromethyl)_s_tript, 2_benzylthio_4,6_

52 201237555 39636pif 雙（三氣甲基)-s-三嗪、2,4,6-三（二溴甲基)-s_三嗪、2,4,6-三(三演曱基)_s_三嗪、2_曱基_4 6_雙(三漠曱基)_S·三嗪以及 2-曱氧基-4,6-雙(三溴甲基)-s-三嗪。 六芳基聯咪唑化合物之實例包含各種化合物’諸如例 如曰本專利申請公開案（jp_B)第6-29285號、美國專利 第3,479，185號、第4,311，783號以及第4,622,286號中所 述之各種化合物。其特定實例包含2,2 -雙（鄰氣笨 基)-4,4'，5,5·-四笨基聯σ米峻、2,2'-雙（鄰》臭本基)-4,4,5,5’-四 苯基聯咪唑、2,2'·雙(鄰,對-二氯苯基)-4,4'，5,5’-四苯基聯咪 唑、2,2，-雙(鄰氯苯基)_4,4'，5,5，-四（間甲氧基苯基)聯咪唑、 2,2，-雙(鄰，鄰，-二氯苯基)_4,4'，5,5，_四苯基聯咪唑、2,2’_雙(鄰 硝基苯基)-4,4，，5,5，-四苯基聯咪嗤、2,2'-雙（鄰甲基苯 基）-4,4，，5,5,四苯基聯咪唑以及2,2L雙（鄰三氟苯 基)-4,4'，5,5’-四笨基聯σ米。坐。 肟酯化合物之實例包含以下中所述之化合物：英國化 學會志:柏爾金匯刊第二輯（J. C. S. Perkin II) (1979)， 1653-1660 ;英國化學會志:柏爾金匯刊第二輯（J. C. S. Perkin II) (1979), 156-162 ;光聚合物科學與技術雜誌 (Journal of Photopolymer Science and Technology) (1995), 202-232 ; JP-A 第 2000-66385 號；JP-A 第 2000-80068 號； 及JP-T第2004-534797號。其市售產品之較佳實例包含豔 佳固OXE01 (1,2-辛二酮，1-[4-(苯基硫基)-，2-(鄰苯甲醯基 肟)])及豔佳固OXE 02 (乙酮，1-[9-乙基-6-(2-曱基苯曱醯 基)-9H-咔唑-3-基]-，1-(鄰乙醯基肟）），兩者均由巴斯夫公司 53 201237555 39636pif (BASF Coiporation )製造。 此外，亦宜使用JP-A第2007-231000號及第 2007-322744號中所述之環狀肟化合物。 醯基膦氧化物化合物之實例包含JP-A第5-345790號 中所述之化合物以及JP-A第6-298818號之第[0027]段中 所述之化合物。其特定實例包含雙(2,4,6-三曱基苯曱醯基） 異丁基膦氧化物、雙(2,6-二曱氧基苯曱醯基)_正丁基膦氧 化物以及2,6-二曱氧基苯曱醯基-2,4,6-三曱基苯曱醯基-正 丁基膦氧化物。此外，其市售產品之較佳實例包含達羅固 (DAROCURE ) TPO (商標名，由巴斯夫公司（BASF Corporation)製造）’亦即2,4,6-三曱基苯曱醯基-二苯基-膦氧化物。 α-胺基酮化合物之實例包含2-(二曱基胺基)-2-[(4-曱 基苯基）曱基]-1-[4_(4-嗎啉基)苯基]_1_丁酮，其可以商標名 「餘佳固379 (由巴斯夫公司（BASF Corporation)製造）」 購得。 聚合起始劑可單獨使用或以其兩種或超過兩種之組 合形式使用。 本發明黑色可聚合組成物中聚合起始劑之含量以黑 色可聚合組成物之總固體含量計較佳為〇〇1質量％至3〇 質量％ ’更佳為0.1質量％至20質量％，且尤其較佳為〇.1 質量％至15質量％。 (C)可聚合化合物 本發明之黑色可聚合組成物包含可聚合化合物。 54 201237555 39636pif 作為（C )可聚合化合物’較佳使用具有至少一個可 加成聚合之烯系不飽和基團且在正常壓力下沸點為1〇〇。〇 或高於100°c的化合物。 具有至少一個可加成聚合之烯系不飽和基團且在正 吊壓力下之’弗點為1〇〇C或高於i〇〇°c的化合物的實例包 含單官能丙烯酸酯及甲基丙烯酸酯，諸如聚乙二醇單（甲基) 丙烯SxS曰、聚丙二醇單（甲基)丙烯酸酯或（γ基)丙烯酸苯氧 基乙S曰，聚乙二醇二（曱基）丙烯酸酯、三羥甲基乙烧三（甲 基)丙烯酸酯、新戊二醇二（甲基)丙烯酸酯、季戊四醇三（甲 基）丙烯酸酯、季戊四醇四（曱基）丙烯酸酯、二季戊四醇六 (甲基)丙烯酸酯、己二醇（甲基)丙婦酸酯、三羥曱基丙烷2 (丙烯醯氧基丙基)趟、異氰尿酸三(丙烯醯氧基乙基彿、藉 由將壤氧乙院或環氧诚加成至乡官能醇（諸如甘油或三 羥甲基乙烧）中繼而將其（甲基）丙烯醯基化而獲得的化合 物、藉由將季戊四醇或二季戊四醇進行聚（曱基)丙烯醯基 ，而獲得的化合物、JP_B第48_41观號、JP B第5〇補4 號以及JP-A第51-37193號中所述之丙稀酸胺基甲酸醋、 JP-A 第 48-64183 號以及 JP_B 第 49·43191 號及 Jp_B 第 52-30490號中所述之聚醋丙婦酸醋，以及藉由環氧樹脂與 (曱基)丙烯酸反應製備的環氧丙烯酸酯。 此外，亦可使用日本接著學會志（J_al 〇f此 A— Society of Japan)，第 2〇 卷第 7 期，第通頁 至第308頁中作為光可固化單體及寡聚物所揭露之化合 55 201237555, ο^υ.?υριι 另外’亦可使用藉由將環氧乙烷或環氧丙烷加成至上 述多官能醇中繼而將其（甲基）丙烯醯基化 ((meth)aCrylati〇n)而獲得的化合物，所述化合物以及其特 定實例以由通式（1)及通式（2)表示之化合物形式描述 於 JP-A 第 10-62986 號中。 詳言之，二季戊四醇五（甲基）丙烯酸酯、二季戊四醇 六（曱基）丙烯酸酯以及丙烯醯基經由乙二醇或丙二醇殘基 結合之化合物為較佳。可使用這些化合物之寡聚物。 另外’如 JP-B 第 48-41708 號、JP-A 第 51-37193 號及 JP-B第2-32293號及JP-B第2-16765號中所述之丙烯酸胺 基甲酸酯；以及如JP-B第58-49860號、第56-17654號、 第62-39417號及第62-39418號中所述之具有環氧乙烧骨 架之胺基曱酸酯化合物亦較佳。此外，藉由使用JP-Α第 63-277653號、第63-260909號及第1-105238號中所述之 在分子中具有胺基或硫基結構的可加成聚合之化合物，可 獲得具有極高感光速度之黑色可聚合組成物。其市售產品 之實例包含胺基曱酸酯寡聚物UAS-10及UAB-140 (均為 商標名，由三洋國策製紙株式會社（Sanyo-Kokusaku Pulp Co.，Ltd.)製造）、UA-7200 (商標名，由新中村化學工業 株式會社（Shin-Nakamura Chemical Co.，Ltd.)製造）、 DPHA-40H(商標名，由日本化藥株式會社（Nippon Kayaku Co·，Ltd.)製造）、UA-306H、UA-306T、UA-306I、AH-600、 T-600及AI-600C商標名，由共榮社化學株式會社（Kyoeisha Chemical Co., Ltd.)製造）以及卡亞拉德（KAYARAD) 56 201237555 39636pif DPCA_20、卡亞拉德DPCA_3〇、卡亞拉德DPCA-60及卡 亞拉德DPCA-120(商標名’由日本化藥株式會社（Nipp〇n KayakuCo.，Ltd.)製造）。 另外，具有酸基之烯系不飽和化合物亦較佳。其市售 產品之實例包含TO-756 (其為含羧基之三官能丙烯酸酯） 以及Τ〇-1382 (其為含羧基之五官能丙烯酸酯）（均為商標 名由東亞合成株式會社（Toagosei Co·，Ltd·)製造）。 t此外，二季戊四醇六丙烯酸酯或二季戊四醇五丙烯酸 ^、季戊四醇三丙烯酸酯以及其類似物的經丁二酸修飾之 早體亦較佳。 作為本發明所用之可聚合化合物，四官能或四 上之丙烯酸酯化合物為更佳。52 201237555 39636pif bis(trismethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s_triazine, 2,4,6-tris(三曱曱基)_s_ Triazine, 2_fluorenyl_4 6_bis(tris-yl)-S-triazine and 2-decyloxy-4,6-bis(tribromomethyl)-s-triazine. Examples of the hexaarylbiimidazole compound include various compounds such as those described in, for example, the copending patent application publication (jp_B) No. 6-29285, U.S. Patent Nos. 3,479,185, 4,311,783, and 4,622,286. Various compounds. Specific examples thereof include 2,2-bis (o-stupyl)-4,4',5,5--tetraphenyl-based sigma-million, 2,2'-bis(o-), stinyl-4, 4,5,5'-tetraphenylbiimidazole, 2,2'.bis(o-,p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2, - bis(o-chlorophenyl)_4,4',5,5,-tetrakis(m-methoxyphenyl)biimidazole, 2,2,-bis(o-, o-,-dichlorophenyl)_4,4 ',5,5,_Tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4,4,5,5,-tetraphenylbiphenyl, 2,2'-double (o-methylphenyl)-4,4,5,5,tetraphenylbiimidazole and 2,2L bis(o-trifluorophenyl)-4,4',5,5'-tetraphenyl sigma Meter. sit. Examples of oxime ester compounds include the compounds described below: British Chemical Society: JC Perkin II (1979), 1653-1660; British Chemical Society: Berkin Journal JCS Perkin II (1979), 156-162; Journal of Photopolymer Science and Technology (1995), 202-232; JP-A No. 2000-66385; JP-A No. 2000-80068; and JP-T No. 2004-534797. Preferred examples of the commercially available product include Yanjiao OXE01 (1,2-octanedione, 1-[4-(phenylthio)-, 2-(o-benzylidene)) and Yanjia OXE 02 (ethanone, 1-[9-ethyl-6-(2-mercaptophenyl)-9H-indazol-3-yl]-, 1-(o-ethylindenyl)), Both are manufactured by BASF Corporation 53 201237555 39636pif (BASF Coiporation). Further, a cyclic anthraquinone compound described in JP-A Nos. 2007-231000 and 2007-322744 is also preferably used. Examples of the mercaptophosphine oxide compound include the compound described in JP-A No. 5-345790 and the compound described in paragraph [0027] of JP-A No. 6-298818. Specific examples thereof include bis(2,4,6-trimercaptophenyl) isobutylphosphine oxide, bis(2,6-dimethoxyphenyl)-n-butylphosphine oxide, and 2,6-Dimethoxybenzoinyl-2,4,6-trimercaptophenyl-n-butylphosphine oxide. Further, preferred examples of the commercially available product include DAROCURE TPO (trade name, manufactured by BASF Corporation), that is, 2,4,6-trimercaptobenzoyl-diphenyl. Base-phosphine oxide. Examples of the α-amino ketone compound include 2-(didecylamino)-2-[(4-indolylphenyl)indenyl]-1-[4-(4-morpholinyl)phenyl]_1_ Butanone, which is commercially available under the trade name "Yujiagu 379 (manufactured by BASF Corporation)". The polymerization initiators may be used singly or in combination of two or more kinds thereof. The content of the polymerization initiator in the black polymerizable composition of the present invention is preferably from 〇〇1% by mass to 3% by mass%, more preferably from 0.1% by mass to 20% by mass, based on the total solid content of the black polymerizable composition. It is particularly preferably from 0.1% by mass to 15% by mass. (C) Polymerizable Compound The black polymerizable composition of the present invention contains a polymerizable compound. 54 201237555 39636pif As the (C) polymerizable compound, it is preferred to use an ethylenically unsaturated group having at least one addition polymerizable group and having a boiling point of 1 Torr under normal pressure. 〇 or a compound higher than 100 ° C. Examples of compounds having at least one addition-polymerizable ethylenically unsaturated group and having a 'Focus' of 1 〇〇C or higher than i〇〇°c under positive hoisting pressure include monofunctional acrylates and methacrylic acid Ester, such as polyethylene glycol mono(meth) propylene SxS oxime, polypropylene glycol mono (meth) acrylate or (gamma) acryl phenoxy ethene, polyethylene glycol bis(indenyl) acrylate, Trimethylolethane tris(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetrakis(meth)acrylate, dipentaerythritol hexa(methyl) ) acrylate, hexanediol (methyl) propionate, trihydrocarbyl propane 2 (propylene oxypropyl) hydrazine, isocyanuric acid tris (propylene oxy oxy ethene, by the soil oxygen a compound obtained by thiolin-adding a cyclohexyl alcohol or dipentaerythritol to a compound obtained by relaying a (meth) propylene to a compound (such as glycerin or trimethylol bromide)曱 )) propylene sulfhydryl, and the compound obtained, JP_B 48_41 view number, JP B 5th 〇 4 And the acetoacetate described in JP-A No. 51-37193, JP-A No. 48-64183, JP-B No. 49-43191, and Jp-B No. 52-30490. Glycolic acid vinegar, and epoxy acrylate prepared by reacting epoxy resin with (mercapto)acrylic acid. In addition, it is also possible to use J_al 〇f this A- Society of Japan, Vol. 2 Phase 7, page through page 308 as a photocurable monomer and oligomer disclosed in the composition 55 201237555, ο^υ.?υριι, another 'can also be used by ethylene oxide or propylene oxide a compound obtained by the addition of the above polyfunctional alcohol to a (meth) propylene oxime ((meth)aCrylati〇n), the compound and specific examples thereof are represented by the general formula (1) and the general formula ( The compound form represented by 2) is described in JP-A No. 10-62986. In detail, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, and acryl oxime are via ethylene glycol or A compound in which a propylene glycol residue is bonded is preferred. Oligomers of these compounds can be used. 'Acrylic urethane amides as described in JP-B No. 48-41708, JP-A No. 51-37193 and JP-B No. 2-32293 and JP-B No. 2-16765; Amino phthalate compounds having an ethylene oxide skeleton as described in JP-B Nos. 58-49860, 56-17654, 62-39417, and 62-39418 are also preferred. It is possible to obtain extremely high sensitization by using an addition polymerizable compound having an amine group or a sulfur group structure in a molecule as described in JP-A-63-277653, No. 63-260909, and No. 1-105238. A black polymerizable composition of speed. Examples of the commercially available product thereof include amino phthalate oligomers UAS-10 and UAB-140 (all of which are trade names, manufactured by Sanyo-Kokusaku Pulp Co., Ltd.), UA- 7200 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (trade name, manufactured by Nippon Kayaku Co., Ltd.) , UA-306H, UA-306T, UA-306I, AH-600, T-600 and AI-600C brand names, manufactured by Kyoeisha Chemical Co., Ltd.) and Kayarad (KAYARAD) 56 201237555 39636pif DPCA_20, Kayad DPCA_3〇, Kayarad DPCA-60 and Kayarad DPCA-120 (trade name 'Nipp〇n Kayaku Co., Ltd.) Manufacturing). Further, an ethylenically unsaturated compound having an acid group is also preferred. Examples of commercially available products thereof include TO-756 (which is a carboxyl group-containing trifunctional acrylate) and Τ〇-1382 (which is a carboxyl group-containing pentafunctional acrylate) (all of which are trade names by Toagosei Co.) ·, Ltd.) Manufacturing). Further, the succinic acid-modified precursor of dipentaerythritol hexaacrylate or dipentaerythritol pentaacrylate, pentaerythritol triacrylate, and the like is also preferred. As the polymerizable compound used in the present invention, a tetrafunctional or tetravalent acrylate compound is more preferable.

• 丨u市·』’只要執行充分固化反應卽丌，伯甘，、，^• 丨u City·』’ As long as the full curing reaction is performed, Bergan, ,, ^

Hi:不同於(D)組分之結構的黏合劑聚合物 在黑色可聚合組成物中 類似目的’可視需要 、、且成物中，出於改良膜特徵之目的或其 要更使用不會減弱本發明黑色可聚合組 57 201237555Hi: a binder polymer different from the structure of the (D) component in a black polymerizable composition is similar to the purpose 'visual need, and in the product, for the purpose of improving the film characteristics or to be used more without diminishing Black polymerizable group 57 of the invention 201237555

J^OJDpiX 成物之特徵之範圍内的具有不同於 他黏合劑聚合物（下文亦簡稱作（）； =構的其 物）。 ）他黏合劑聚合 在本文中’較佳使用線性（ii_ 合劑聚合物。作為「線性有機聚合物」，物作為黏 仃的。所述線性有機聚合物之實例包子3衫為可 基團之自由基聚合物，諸如例如爪Α第59鏈44中=具有賴 第54-34327號、第58_12577號及第^ $、爪Β ^細號、第59_53836號及第597iG4c 上由基聚合物，亦即藉由使具錢基之單體均“斤^ 且隨後使酸酐單元水解、半醋果f均聚&quot;或共聚合 脂，以及藉由用不飽和單 次+酿胺化而獲得的樹 的環氧丙稀酸酯環氧樹脂而獲得 _、衣康酸、 二__，且編酐增的 類似地’可使用側鏈中具有_基團之酸 生物。此外，藉由添加環狀酸酐至具有經基之聚合 201237555 39636pif 獲得之物質及其類似物亦適用。 另外，如JP-B第7-12004號、第7-120041號、第 7-120042 號及第 8-12424 號、JP-A 第 63-287944 號、第 63-287947號及第1-271741號、日本專利申請案第 10-116232號中所述之含有酸基之胺基曱酸酯黏合劑聚合 物以及其類似物在低曝光適合性方面為適宜的，因為其具 有極高強度。 如歐洲專利（EP)第993966號及第1204000號、JP-A 第2001-318463號中所述之經縮醛修飾之具有酸基的聚乙 烯醇黏合劑聚合物以及其類似物由於膜強度與顯影性之間 的極佳平衡而為較佳。 作為其他水溶性線性有機聚合物，聚乙烯吡咯啶酮、 聚氧化乙烯或其類似物適用。為提高固化膜之強度，醇溶 性耐綸、2,2·雙-(4-羥基苯基)-丙烷與表氣醇之聚醚以及其 類似物亦適用。 以本發明黑色可聚合組成物之總固體含量計共存之 其他黏合劑聚合物之含量較佳為〇1質量％至7〇質量％， 且出於抑制®賴落與抑制顯影殘餘物之間的相容性 點，其更佳為0.3質量。/。至6.0質量％，且甚 質量%至5.0質量％。 主更佳為1.0 (E-2 )除（A )組分以外的著色劑 ，本發明中，必要時可另外使用不同於（A)組八 其他著色劑以展現所要遮光特性。 刀 可與⑷組分一起用作著色劑之有機顏料的實例包 59 201237555 jyojopit 含JP-A第2008-224982號之第[0030]段至第[0044]段中所 述之顏料、C.I.顏料綠58以及藉由將C. I.顏料藍79之C1 取代基變為OH取代基而獲得的著色劑。詳言之，可較佳 使用之顏料之實例包含： C. I.顏料黃 U、24、108、109、110、138、139、150、 151、154、167、180 及 185 ; C· I.顏料撥36 ; C. L顏料紅 122、150、171、175、177、209、224、 242、254 及 255 ; C. I.顏料紫 19、23、29 及 32 ; C. I.顏料藍 15:1、15:3、15:6、16、22、60 及 66 ; C· I，顏料綠7、36、37及58 ;以及 C.I.顏料黑1。 然而，可與（A)組分一 述著色劑。 起使用之著色劑並不限於上 可用U著色劑之染料不受特別限制，且可使用 自九已知染料之任何染料。染料之實例包含以下中所揭露 *枓.JP-A 第 64-90403 號、JP_A 第 6切腿 卜94301號、JP-A第號、日本專利 ，專利第導，則號、美國專利 &amp; ^ 號、JP-A 第 6-5出5 號、JKA 第 6·19The range of characteristics of the J^OJDpiX product is different from that of the other binder polymer (hereinafter also referred to as (); = structure). It is preferred to use a linear (ii_mixture polymer. As a "linear organic polymer") as a binder. The example of the linear organic polymer is a free radical. a base polymer, such as, for example, Xenopuma 59 chain 44 = having a base polymer, such as Lai Nos. 54-34327, No. 58_12577, and No., No. 59-53836, and No. 597iG4c, By obtaining a monomer having a money base and then hydrolyzing the acid anhydride unit, homogenizing the half-flavored fruit, or copolymerizing the lipid, and a tree obtained by amination with an unsaturated single-time Epoxy acrylate epoxy resin to obtain _, itaconic acid, bismuth, and the similarity of the anhydride can be used to use acid groups having a group in the side chain. In addition, by adding a cyclic anhydride Substances obtained by the polymerization of the base group 201237555 39636pif and the like are also applicable. In addition, as in JP-B Nos. 7-12004, Nos. 7-120041, Nos. 7-120042 and No. 8-12424, JP- A in No. 63-287944, No. 63-287947 and No. 1-271741, Japanese Patent Application No. 10-116232 The acid group-containing amine phthalate binder polymer and the like are suitable for low exposure suitability because of their extremely high strength. For example, European Patent (EP) No. 993966 and No. 1204000, JP The acetal-modified polyvinyl alcohol binder polymer having an acid group as described in the above-mentioned No. 2001-318463, and the like, are preferred because of an excellent balance between film strength and developability. Water-soluble linear organic polymer, polyvinylpyrrolidone, polyethylene oxide or the like. For improving the strength of the cured film, alcohol-soluble nylon, 2,2·bis-(4-hydroxyphenyl)-propane and The epithelial polyether and the analog thereof are also suitable. The content of the other binder polymer coexisting with the total solid content of the black polymerizable composition of the present invention is preferably from 〇1% by mass to 7% by mass, and It is more preferably from 0.3 mass% to 6.0 mass%, and from 5% by mass to 5.0 mass%, more preferably 1.0 (E-2), in terms of compatibility between the inhibition and the development residue. a coloring agent other than the component (A), in the present invention, if necessary Further, an other coloring agent different from the group (A) is used to exhibit the desired light-shielding property. An example of an organic pigment which the knife can be used as a coloring agent together with the component (4) 59 201237555 jyojopit, including JP-A No. 2008-224982 [ The pigment described in paragraph 0030] to paragraph [0044], CI Pigment Green 58 and a color former obtained by changing the C1 substituent of CI Pigment Blue 79 to an OH substituent. In detail, examples of pigments which can be preferably used include: CI Pigment Yellow U, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180 and 185; C·I. Pigment Dial 36 C. L Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254 and 255; CI Pigment Violet 19, 23, 29 and 32; CI Pigment Blue 15:1, 15:3, 15: 6, 16, 22, 60 and 66; C·I, Pigment Green 7, 36, 37 and 58; and CI Pigment Black 1. However, a coloring agent may be mentioned with the component (A). The coloring agent to be used is not limited to the dye which can be used with the U coloring agent, and any dye from nine known dyes can be used. Examples of the dye include the following: *枓.JP-A No. 64-90403, JP_A No. 6 cut leg, No. 94301, JP-A No., Japanese Patent, Patent No., No., U.S. Patent &amp; No., JP-A No. 6-5, No. 5, JKA No. 6.19

8_2出99 號、JP-A 第 4_24954 f = A …-函號”…二 201237555 39636pif 2001-4823 號、JP-A 第 8-15522 號、JP-A 第 8-29771 號、 JP-A 第 8-146215 號、JP-A 第 11-343437 號、JP-A 第 8-624168_2, No. 99, JP-A No. 4_24954 f = A ... - Letter "... 2 201237555 39636pif 2001-4823, JP-A No. 8-15522, JP-A No. 8-29771, JP-A No. 8 -146215, JP-A No. 11-343437, JP-A No. 8-62416

號、JP-A 第 2002-14220 號、JP-A 第 2002-14221 號、jP_A 第 2002-14222 號、JP-A 第 2002-14223 號、JP-A 第 8-302224 號、JP-A 第 8-73758 號、JP-A 第 8-179120 號及 JP_A 第 8-151531 號。 另外，亦可使用具有以下之化學結構的染料：吡唾偶 氮染料、苯胺基偶氮染料、三苯基曱烷染料、蒽醌染料、 蒽0比啶酮染料、苯亞曱基染料、氧喏染料、吡唑并三唑偶 氮染料、吼啶酮偶氮染料、花青染料、啡噻嗪染料、吡咯 并吡唑偶氮次甲基染料、咕噸染料、酞菁染料、苯并哌 染料、歆藍染料或其類似物。 (E-3)有機溶劑 y向本發明之黑色可聚合組成物中添加溶劑。有機溶 上不受特別限制’只要滿^各組分之溶解性及里色 It ΐ成物之塗佈特性即可，但較佳考慮欲使用之紫外 此外，特性及安全性進行選擇。 兩種有機溶劑。 色可n组成物’較佳含有至少 有機溶劑之較佳實例包含： 戍醋、乙乙酉旨、乙酸正丁醋、乙酸異丁醋、甲酸 丁酸乙r 酸異了目旨、丙酸獨、丁酸異丙醋、 9 文丁酯、乳酸甲酯、乳酸乙酯、氧美乙g曼烷 酯（例如氧基乙酸甲龄#甘 孔义乳暴乙酉夂烷 -曰、乳基乙酸乙酯、氧基乙酸丁酯（例 201237555 3yi)36pif 如曱氧基乙酸曱g旨、甲氧基乙酸乙|旨、曱氧基乙酸丁醋、 乙氧基乙酸曱酯及乙氧基乙酸乙酯））、3_氧基丙酸烷酯（例 如3-氧基丙酸曱酯及3-氧基丙酸乙酯（例如3·曱氧基丙酸 曱酯、3-曱氧基丙酸乙酯、3-乙氧基丙酸甲酯及3_乙氧基 丙酸乙酯））、2-氧基丙酸烷酯（例如2-氧基丙酸曱酯、2-氧基丙酸乙酯及2-氧基丙酸丙酯（例如2-甲氧基丙酸甲 酯、2·甲氧基丙酸乙酯、2_曱氧基丙酸丙酯、2-乙氧基丙 酸曱酯及2-乙氧基丙酸乙酯））、2-氧基_2·曱基丙酸曱酯及 2-氧基-2-曱基丙酸乙酯（例如2-甲氧基_2_曱基丙酸曱酯及 乙氧基-2-甲基丙酸乙醋）、丙嗣酸甲酯、丙酮酸乙醋、 丙_酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-侧氧基丁 酸甲酯、2-側氧基丁酸乙酯； 鱗’諸如二乙二醇二甲鱗、四氫吱喃、乙二醇單甲趟、 乙一* _•早乙鍵、乙一％曱喊乙酸酯（methyl cellosolve acetate)、乙二醇乙乙酸西曰（ethyl cellosolve acetate)、二 乙二醇單曱醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二 醇單曱醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯或 丙一醇單丙醚乙酸醋； 綱，諸如甲基乙基酮、環己酮、2-庚酮或3-庚酮；以 及 芳族烴，諸如曱苯或二甲苯。 出於紫外線吸收劑及鹼溶性樹脂之溶解性、改良塗佈 表，之輪廓的觀點以及其類似觀點，較佳將兩種或超過兩 種崦些有機溶劑混合。在所述情況下，使用包含選自以下No. 2002-14220, JP-A No. 2002-14221, jP_A No. 2002-14222, JP-A No. 2002-14223, JP-A No. 8-302224, JP-A No. 8 -73758, JP-A No. 8-179120 and JP_A No. 8-151531. In addition, a dye having the following chemical structure: a pyridazo dye, an anilino azo dye, a triphenyl decane dye, an anthraquinone dye, a quinone quinone dye, a benzoquinone dye, or an oxygen can also be used. Anthraquinone dye, pyrazolotriazole azo dye, acridone azo dye, cyanine dye, phenothiazine dye, pyrrolopyrazole azomethine dye, xanthene dye, phthalocyanine dye, benzopyrazine Dyes, indigo dyes or the like. (E-3) Organic solvent y A solvent is added to the black polymerizable composition of the present invention. The organic solvent is not particularly limited as long as the solubility of each component and the coating property of the color component are sufficient, but it is preferable to select the ultraviolet to be used, and the properties and safety are selected. Two organic solvents. Preferred examples of the composition of the color-a composition preferably containing at least an organic solvent include: vinegar, ethyl acetate, n-butyl acetate, isobutyl acetonate, formic acid butyric acid, propionic acid alone, Isopropyl succinate, 9 butyl butyl acrylate, methyl lactate, ethyl lactate, ethoxyethyl ethoxylate (such as oxyacetic acid ageing #甘孔义乳暴乙酉夂-曰, ethyl lactate, oxygen Butyl acetate (Example 201237555 3yi) 36pif, such as 曱 oxyacetic acid 曱g, methoxyacetic acid ethyl, methoxyacetic acid butyl vinegar, ethoxy ethoxyacetate and ethyl ethoxyacetate)), 3 - oxypropionic acid alkyl ester (for example, decyl 3-oxypropionate and ethyl 3-oxypropionate (for example, decyl methoxypropionate, ethyl 3-methoxypropionate, 3 - methyl ethoxypropionate and ethyl 3-ethoxypropionate)), alkyl 2-oxypropionate (eg, 2-oxopropionate, ethyl 2-oxypropionate and 2 -propyl oxypropionate (eg methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, decyl 2-ethoxypropionate and 2 -ethyl ethoxypropionate)), 2-oxo-2-propenyl decanoate and Ethyl 2-oxo-2-mercaptopropionate (for example, 2-methoxy-2-indolyl propionate and ethoxy-2-methylpropionic acid ethyl acetate), methyl propyl decanoate, Ethyl acetonate, propyl acrylate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate; scales such as diethylene glycol Dimethyl scale, tetrahydrofuran, ethylene glycol monomethyl hydrazine, ethyl ketone * methyl ketone acetate, ethyl cellosolve acetate, ethyl cellosolve acetate, Diethylene glycol monoterpene ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoterpene ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate or propanol monopropyl ether acetate Vinegar; such as methyl ethyl ketone, cyclohexanone, 2-heptanone or 3-heptanone; and aromatic hydrocarbons such as toluene or xylene. It is preferred to mix two or more organic solvents in view of the solubility of the ultraviolet absorber and the alkali-soluble resin, the viewpoint of improving the coating table, and the like. In the case, the use comprises a selection selected from the following

62 201237555 39636pif 二：種或超過兩種的混合溶液為尤其較佳： 甲酯、3-乙氧基兩酿7_ 孔基丙酸 一 田 S曰、乙二轉乙醚乙酸酯、乳酸乙酯、 一一醇一甲醚、乙酸丁酯、3_甲氧基丙酸 環己銅、乙基卡必醇乙酸酯、了基卡必醇乙_旨 甲醚以及丙二醇甲醚乙酸酯。 丙一私 出於塗佈特性之觀點，黑色可聚 之含量較佳紐得組絲之翻财料 7 質量%至60質量%且尤其較== 至50質量％的量。 買里/〇 (E-4)界面活性劑 出塗佈特性之觀點’可添加各種界面 色可聚合組成物中。作為界面活性 剤了使用各種界面活性劑，諸如含氟界面活性 _子财面活_、陽離子型界面|、 陰”活性劑或聚矽氧界面活性劑。 特定言之，當本發明之黑色可聚合組 ::時’可進一步改良使用黑色可聚合組成物 佈液體的液體特徵(尤其流動性)，從而可進一步改=均： 性或成膜雜。 換言之’當使用含有含氟界面活性劑之里色 成物的塗佈液體形成膜時，欲塗佈表面與塗佈液體之二的 界面張力降低’且欲塗佈表面之可祕改良，從而使得塗 佈液體對欲塗佈表面之可塗佈性改良。出於此原因，即使 在使用少量塗佈液财歧微米之薄料，雜佳形成具 63 201237555 39636pit' 有均一膜厚度且厚度差異小之膜。 性劑中之氟含量較佳為3質量％至4〇質量％， ==Γ質量%，且尤其較佳為7質量%至25 膜严二之妁H在延些範圍内之氟界面活性劑在塗佈 均-性及保液特性方面為有效的， 性組成物中之溶解性亦良好。 有巴α尤 氟界面活性劑之實例包含梅格範斯（MEGAFAC) ^、梅格範斯F172、梅格範斯F173、梅格範斯F176、 梅格範斯顯、梅格範斯F141、梅格範斯、梅格範 斯F143、梅格範斯F144、梅格範斯R3〇、梅格範斯F437、 梅格範斯F475、梅格範斯F479、梅格範斯料82、梅格範 斯F554、梅格範斯F780及梅格範斯F781 (均為商標名， 由DIC株式會社（DIC Corporation )製造）；弗洛拉 CFLUORAD) FC430、弗洛拉FC431及弗洛拉Fcm (均 為商標名’由住友3M株式會社（Sumitomo 3M Limited) 製造）；及舍弗隆（SURFLON) S_382、舍弗隆SC-101、 舍弗隆SC-103、舍弗隆SC-104、舍弗隆SC-105、舍弗隆 SC1068、舍弗隆SC-381、舍弗隆SC-383、舍弗隆S393及 舍弗隆KH-40 (均為商標名，由朝日玻璃株式會社（Asahi Glass Co.，Ltd.)製造）〇 非離子型界面活性劑之特定實例包含甘油、三經曱基 丙烧、三經曱基乙烧及其乙氧基化物及丙氧基化物（例如 甘油丙氧基化物或甘油乙氧基化物）、聚氧乙烯月桂醚、聚 氧乙烯硬脂醚、聚氧乙烯油醚、聚氧乙烯辛基苯醚、聚氧 64 201237555 39636pif 乙烯壬基苯醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸 酯及脫水山梨糖醇脂肪酸酯（諸如普洛尼克（PLURONIC ) L10、L31、L61、L62、10R5、17R2 及 25R2，特曲尼克 (TETRONIC) 304、7(Π、704、901、904 或 150R1 (商標 名’由巴斯夫公司（BASF Corporation)製造）以及索斯 帕思20000 (商標名，由日本路博潤公司（The Lubrizol Corporation，Japan )製造）° 陽離子型界面活性劑之特定實例包含酞菁衍生物（商 標名.埃弗卡-745 ’由森下仁丹株式會社（Morishita &amp; Co., Ltd.)製造）；有機矽氧烷聚合物κρ^ι (由信越化學工業 株式會社（Shin-EtsuChemicalCo.，Ltd.)製造）；（曱基)丙 稀酸(共)聚合物泊里富勞第75號、第90號及第95號（由 共榮社化學株式會社（Kyoeisha Chemical Co·, Ltd.)製 造）；以及W001(商標名’由裕商株式會社（Yush〇 c〇.，Ltd.) 製造）。 陰離子型界面活性劑之特定實例包含w〇〇4、w〇〇5 及W017 (商標名，由裕商株式會社（Yush〇c〇，ud )製 造）。 聚矽氧界面活性劑之實例包含東麗聚矽氧（T0RAY SILICONE) DC3PA、東麗聚矽氧SH7pA、東麗聚矽氧 ^CIIPA、東麗聚石夕氧SH21PA、東麗聚石夕氧SH28PA、東 麗聚矽氧SH29PA、東麗聚矽氧SH3〇pA及東麗聚矽氧 删4〇〇 (商標名，均由道康寧東麗有限公司（d〇w c〇rning62 201237555 39636pif II: Mixture solutions of more than one kind or more are especially preferred: methyl ester, 3-ethoxy two-branched 7_porous propionic acid, one field S曰, ethylene di-ethyl ether acetate, ethyl lactate, Monomethyl ether, butyl acetate, cyclohexyl methoxypropionate, ethyl carbitol acetate, carbitol B-methyl ether and propylene glycol methyl ether acetate. From the viewpoint of coating properties, the content of black polymerizable is preferably from 7% by mass to 60% by mass and especially from == to 50% by mass. Buy/〇 (E-4) Surfactant From the viewpoint of coating characteristics, various interface color polymerizable compositions can be added. As the interface activity, various surfactants are used, such as fluorine-containing interface activity, cationic interface, cationic active agent or polyoxyn surfactant. In particular, when the black of the present invention is available The polymerization group::time can further improve the liquid characteristics (especially fluidity) of the liquid using the black polymerizable composition cloth, so that it can be further changed to: uniformity or film formation. In other words, when using a fluorine-containing surfactant When the coating liquid of the chromogenic product forms a film, the interfacial tension between the surface to be coated and the coating liquid is lowered, and the secret of the surface to be coated is improved, so that the coating liquid can be coated on the surface to be coated. For this reason, even in the case of using a small amount of coating liquid, the fine material is formed into a film having a uniform film thickness and a small difference in thickness. The fluorine content in the agent is preferably 3% by mass to 4〇% by mass, ==Γ% by mass, and particularly preferably 7% by mass to 25% of the film 在H in the extended range of the fluorosurfactant in coating uniformity and protection Effective in terms of liquid properties, sexual The solubility in the product is also good. Examples of the Ba-Al-Fluorine surfactant include MEGAFAC (MEGAFAC) ^, Meg Vanes F172, Meg Vans F173, Meg Vans F176, Megfan Si Xian, Mege Vans F141, Meg Vans, Mege Vans F143, Meg Vans F144, Meg Vans R3, Meg Vans F437, Meg Vans F475, Meg Vans F479 , Meg Vans 82, Meg Vans F554, Meg Vans F780 and Meg Vans F781 (all trademark names, manufactured by DIC Corporation); Flora CFLUORAD) FC430, Eph Lola FC431 and Flora Fcm (both of which are manufactured by Sumitomo 3M Limited); and SURFLON S_382, Chevron SC-101, Chevron SC-103, Chevron SC-104, Chevron SC-105, Chevron SC1068, Chevron SC-381, Chevron SC-383, Chevron S393 and Chevron KH-40 (both are trademark names, Specific examples of the non-ionic surfactants manufactured by Asahi Glass Co., Ltd. include glycerin, tri-propyl mercapto, tri-sulfonyl-based ethidium and Oxide and propoxylate (eg glycerol propoxylate or glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, Polyoxygen 64 201237555 39636pif Vinyl phenyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate and sorbitan fatty acid esters (such as PLURONIC L10, L31, L61 , L62, 10R5, 17R2 and 25R2, TETRONIC 304, 7 (Π, 704, 901, 904 or 150R1 (trade name 'made by BASF Corporation) and Sospers 20000 (trade name) , manufactured by The Lubrizol Corporation, Japan) ° Specific examples of cationic surfactants include phthalocyanine derivatives (trade name Evka-745 'by Morishita &amp; Co., Ltd. (Morishita &amp; Co ., Ltd.); organic siloxane polymer κρ^ι (manufactured by Shin-Etsu Chemical Co., Ltd.); (mercapto) acrylic acid (co)polymer Pori Fu Lao No. 75, No. 90 and No. 95 ( Kyoeisha Chemical Co., Ltd. (Kyoeisha Chemical Co ·, Ltd.) manufactured); and W001 (trade name 'from the margin provider, Inc. (Yush〇 c〇, Ltd..) Manufacturing). Specific examples of the anionic surfactant include w〇〇4, w〇〇5 and W017 (trade name, manufactured by Yushang Co., Ltd.). Examples of polyfluorene surfactants include T0RAY SILICONE DC3PA, Toray Polyoxo SH7pA, Toray Polyoxynium CIIPA, Toray Juxis SH21PA, Toray Juxis SH28PA , Dongli Polyoxo SH29PA, Toray Polyoxo SH3〇pA and Toray Polyoxanium 4〇〇 (trade name, all by Dow Corning Dongli Co., Ltd. (d〇wc〇rning)

Toray Co” Ltd.)製造），TSF-4440、TSF-4300、TSF-4445、 65 201237555 TSF-4460及TSF-4452 (商標名，均由邁圖高新材料公司 (Momentive Performance Materials Inc·)製造）；KP341、 KF6001及KF6002 (商標名，均由信越化學工業株式會社 (Shin-Etsu Chemical Co.，Ltd.)製造）；及畢克（Βγκ)3〇7、 畢克323及畢克330 (商標名，由畢克化學公司 (BYK-Chemie)製造）。 界面活性劑可單獨使用或以其兩種或超過兩種之組 合形式使用。 以黑色可聚合組成物之總質量计，欲添加之界面活性 劑之量較佳為0.001質量％至2.0質量％，且更佳為〇 〇〇5 質量％至1.0質量％。 (E-5)敏化劑 出於改良聚合起始劑之自由基產生效率且在感光波 長方面獲得較長波長的目的’黑色可聚合組成物可更含有 敏化劑。 作為本發明所用之敏化劑，藉由電子轉移機制或能量 轉移機制敏化與其一起使用之聚合起始劑的敏化劑為較 佳。 敏化劑之較佳實例包含JP-A第2008-214395號之第 [0085]段至第[〇〇98]段中所述之化合物。 出於敏感性及儲存穩定性之觀點，以黑色可聚合組成 物之總固體質量計，敏化劑之含量較佳在〇1質量％至3〇 質量％範圍内，且更佳在1質量％至2〇質量％範圍内，且 甚至更佳在2質量％至15質量％範圍内。 66 201237555 39636pif (BA)聚合抑制劑 較佳添加少量聚合抑制劑至黑色可聚合組成物中以 =止可聚合化合物在組成物製備或儲存期間的不適宜熱聚 σ。，為聚合抑制劑，可使用已知熱聚合抑制劑。其實例 包含氫醌、對曱氧基苯酚、二第三丁基-對甲酚、連笨三酚、 第三丁基兒茶酚、苯醌、4,4，_硫雙(3_甲基_6•第三丁基苯 ，）、，2」2’-亞甲基雙(4_甲基各第三丁基苯齡)以及队亞石肖基 本基經基胺之飾鹽。 以黑色可聚合組成物之總固體含量計，欲添加之熱聚 合抑制劑之量較佳為約0.01質量％至約5重量。/。。… 此外，可添加高級脂肪酸或其衍生物（諸如二十一浐 酸或二十二烷酸醯胺）以使其在塗佈後之乾燥製程期間= 在於塗膜之表面上，以便抑制由氧氣所致之聚合抑制予 整個組成物計，欲添加之高級脂肪酸或其衍生物j。以 為約0.5質量％至約1〇質量％。 踅較佳 (E-7)黏著改良劑 可添加黏著改良劑至本發明黑色可聚合級成 改良對硬質材料（諸如支撐物）之表面的黏著性。黏=以 良劑之實例包含矽烷偶合劑及鈦偶合劑。 &amp;著改 乙氧 石夕烧偶合劑之較佳實例包含γ-曱基丙烯隨氣 三甲氧基矽烷、γ-曱基丙烯醯氧基丙基三乙氧基石夕^丙基 丙婦醯氧基丙基三曱氧基石夕院、γ_丙稀醯氧基丙烏-γ 基矽烷、γ-巯基丙基三曱氧基矽烷、γ_胺基丙基= 曱 矽烷、苯基三曱氧基矽烷以及3-曱基丙烯醯氧基内&amp; 67 201237555 氧基曱基矽烷。更佳實例包含3_甲基丙烯醯氧基丙基二甲 氧基曱基矽烷及γ-甲基丙烯醯氧基丙基三甲氧基矽烷。 以本發明黑色可聚合組成物之總固體含量計，欲添加 之黏著改良劑之量較佳為〇.5質量％至3〇質量％，且更佳 為0.7質量％至20質量〇/〇。 詳言之，當使用本發明之光阻（亦即黑色可聚合組成 物）在玻璃基板上形成透鏡時，出於改良敏感性之觀點， 較佳添加黏著改良劑至光阻中。 (Ε-8)其他添加劑 出於例如進一步改良敏化著色劑或起始劑對光化輻 射之敏感性或防止由氧氣所致之光可聚合化合物之聚合抑 制的目的’本發明之黑色可聚合組成物可更含有共敏化 劑。另外’缺I則化麵之物理特性，必要時可添加 已知添加劑’諸如界面活性劑、稀糊、增_或油敏化 劑。 本發明之黑色可聚合組成物至少含有上述（Α)黑色 ，二&amp;佳為含有顏料分散劑之顏料分散液組成物）、⑻ :::始劑、(C)可聚合化合物以及⑼鹼溶性黏合劑 有機溶劑 聚合物’且必要時可更含有各種添加劑中之任 有機々Μ ’且可藉由將這些組分與（必要時） 如界面活性劑）混合來製備。Toray Co" Ltd.), TSF-4440, TSF-4300, TSF-4445, 65 201237555 TSF-4460 and TSF-4452 (trade names, all manufactured by Momentive Performance Materials Inc.) ; KP341, KF6001 and KF6002 (trade names, all manufactured by Shin-Etsu Chemical Co., Ltd.); and BYK (Βγκ)3〇7, BYK 323 and BYK 330 (trademarks) Name, manufactured by BYK-Chemie. The surfactants may be used singly or in combination of two or more. The total mass of the black polymerizable composition, the interface to be added The amount of the active agent is preferably from 0.001% by mass to 2.0% by mass, and more preferably from 5% by mass to 1.0% by mass. (E-5) The sensitizer improves the radical generating efficiency of the polymerization initiator And the purpose of obtaining a longer wavelength in terms of the wavelength of light can further contain a sensitizer. As a sensitizer used in the present invention, sensitization by an electron transfer mechanism or an energy transfer mechanism is used together with the polymerization. A sensitizer of the starting agent is preferred. Preferred examples of the agent include the compounds described in paragraphs [0085] to [〇〇98] of JP-A No. 2008-214395. For the purpose of sensitivity and storage stability, black polymerizable The content of the sensitizer is preferably in the range of from 1% by mass to 3% by mass, and more preferably from 1% by mass to 2% by mass, and even more preferably at a mass of 2% by mass based on the total solid mass of the composition. In the range of % to 15% by mass. 66 201237555 39636pif (BA) polymerization inhibitor is preferably added with a small amount of polymerization inhibitor to the black polymerizable composition to suppress the unsuitable thermal polymerization of the polymerizable compound during preparation or storage of the composition. As the polymerization inhibitor, a known thermal polymerization inhibitor can be used, and examples thereof include hydroquinone, p-nonoxyphenol, di-tert-butyl-p-cresol, streptotriene, and tert-butylcatechol. , benzoquinone, 4,4, _ thiobis(3_methyl_6•t-butylbenzene,), 2"2'-methylene bis (4-methyl each butyl benzene) And the salt of the basic base of the team. The amount of the thermal polymerization inhibitor to be added is preferably from about 0.01% by mass to about 5 parts by weight based on the total solid content of the black polymerizable composition. /. . In addition, a higher fatty acid or a derivative thereof such as behenic acid or decyl ammonium behenate may be added so as to be on the surface of the coating film during the drying process after coating to suppress oxygen The resulting polymerization inhibition is based on the entire composition, the higher fatty acid or its derivative j to be added. It is about 0.5% by mass to about 1% by mass. Preferably (E-7) adhesion improver An adhesion improver may be added to the black polymerizable grade of the present invention to improve adhesion to the surface of a hard material such as a support. Viscosity = examples of good agents include decane coupling agents and titanium coupling agents. Preferred examples of the modified ethoxylate coupling agent include γ-mercaptopropene gas trimethoxy decane, γ-mercapto propylene oxypropyl triethoxy sulfonate Propyl tridecyloxy sylvestre, γ-acrylic propylene ketone-gamma decane, γ-mercaptopropyltrimethoxy decane, γ-aminopropyl = decane, phenyl trioxane Alkane and 3-mercaptopropenyloxy&amp; 67 201237555 Oxydecyl decane. More preferred examples include 3-methacryloxypropyldimethoxydecyldecane and γ-methylpropenyloxypropyltrimethoxydecane. The amount of the adhesion improver to be added is preferably from 5% by mass to 3% by mass, and more preferably from 0.7% by mass to 20% by mass, based on the total solid content of the black polymerizable composition of the present invention. In particular, when a lens is formed on a glass substrate by using the photoresist of the present invention (i.e., a black polymerizable composition), it is preferred to add an adhesion improver to the photoresist from the viewpoint of improving sensitivity. (Ε-8) Other additives For the purpose of, for example, further improving the sensitivity of the sensitizing colorant or the initiator to actinic radiation or preventing the polymerization inhibition of the photopolymerizable compound by oxygen, the black polymerizable of the present invention The composition may further contain a co-sensitizer. Further, the physical properties of the surface are reduced, and if necessary, a known additive such as a surfactant, a thin paste, an increase or an oil sensitizer may be added. The black polymerizable composition of the present invention contains at least the above (Α) black, two &amp; preferably a pigment dispersion composition containing a pigment dispersant), (8) ::: a starter, (C) a polymerizable compound, and (9) an alkali solubility. The binder organic solvent polymer 'and, if necessary, may further contain any of the various organic additives' and may be prepared by mixing these components with, if necessary, a surfactant.

聚合組成物適用於形成晶圓級透鏡之遮光區'。 一者及（Ε-3) 添加劑（諸 吳百所述組態時，可形 。出於此原因，黑色可 68 201237555 39636pif 此外’為形成遮光膜’較佳如下所述藉由喷霧塗佈將 黑色可聚合組成物塗覆於固體表面上。 因此，出於防止在將黑色可聚合組成物塗佈於曲面上 時液體排出之觀點，黑色可聚合組成物中之總固體含量較 佳為20質量％至35質量％，更佳為21質量％至33質量％， 且最佳為25質量％至30質量％。 晶圓級透鏡 本發明之晶圓級透鏡可包含由本發明黑色可聚合組 成物形成之遮光膜（亦即黑色層）。 下文將描述本發明之晶圓級透鏡。 圖1為顯不具有多個晶圓級透鏡之晶圓級透鏡陣列之 組態的一實例的平面圖。 如圖1所示，晶圓級透鏡陣列包含基板1〇及排列在 基板10上之透鏡12。在圖1中，多個透鏡12相對於基板 10呈二維排列’但其亦可呈一維排列。 圖2為圖1所示晶圓級透鏡陣列沿線A_A所取之 圖。 如圖2所示，在晶圓級透鏡陣列中，在基板1〇上排 列之多個透鏡12之間除透鏡12以外之區域中形成防止光 透射之遮光膜14。 本發明之晶圓級透鏡包含存在於基板10上之一透鏡 12及在透鏡之周邊部分上提供之遮光膜14。本發明之黑色 可固化組成物用於形成遮光膜14，從而形成遮光區。 下文將以實例之方式描述晶圓級透鏡陣列之組態，其 69 201237555 jyojopit 中多個透鏡12相對於基板10呈二維排列 ，如圖1所示。 透鏡12 一般由與基板10相同之材料形成，且可在基 板10上整體形成或可作為個別結構形成且固定於基板 上。本文引用本發明晶圓級透鏡之一實例，但本發明之晶 圓級透鏡並不限於所述實例，且可使用各種實施例，諸如 具有多層結構之晶圓級透鏡或藉由切割分隔成透鏡模組之 晶圓級透鏡。 形成透鏡12之材料的實例包含玻璃。存在各種玻璃， 且玻璃較佳用作具有高倍率（high p〇wer)之透鏡的材料 是因為可自各種玻璃選擇具有高折射率之玻璃。此外，玻 璃具有耐熱性極佳及能經受住在成像單元上回焊安裝之優 形成透鏡12之其他材料的實例包含樹脂。樹脂具有 極佳可加工性，且因透鏡之表面可使用例如模具（rnoid) 或硬模（die)來容易且廉價地形成而適合。 匕晶圓級透鏡較佳使用能量可固化（enery curable )樹 脂來形成。能量可固化樹脂可為能夠藉由加熱而固化之樹 脂或能夠藉由騎活性能量射線（例如熱施加、紫外線輕 射或電子束輻射）而固化之樹脂中之任一者。 田 考慮成像單元之回焊安裝，具有相對高軟化點（例如 200C或祕2〇〇。〇之樹脂為較佳，且軟化 高於25CTC之樹脂為更佳。 下文將描述作為透鏡材料之較佳樹脂。 紫外線可固化樹脂之實例包含紫外線可固化聚石夕氧 201237555 39636pif 外線可固化環氧樹脂以及紫外線可固化丙稀酸樹 曰σ於本發明之環氧樹脂的線性膨服係數（此邮 e— coefficient)為 4〇 [Μ,克耳文]至 8〇 [1〇_6/克耳 文]’且折射率為i.50至U且較佳為15〇至165。 ，固^樹脂之實例包含熱固性聚魏樹脂、熱固性環 氧树月曰、熱固㈣樹脂以及熱固性丙婦酸樹脂。舉例而言， 可使用之聚石夕氧樹脂的線性膨脹係數為3〇 [1〇_6/克 160 [10 /克耳文]，且折射率為14〇至！ 55。舉例而言， 可使用之環氧樹脂的線性膨脹係數為4() [1()_6/克耳至 80 [ΙΟ·6/克耳文]，且折射率為i 5〇至i 7〇，且較佳為i % 至1.65。可使用之酚樹脂的線性膨脹係數為3〇 〜克 文]至70 [10 6/克耳文]，且折射率為i 5〇至i 7〇。可使用 之丙烯酸樹脂的線性膨脹係數為2〇 [1〇·6/克耳文]至6〇 [ΙΟ—6/克耳文]，且折射率為L40至160，且較佳為t 5 1_60。 市售產品可用作熱固性樹脂。其特定實例包含 SMX-7852及SMX-7877(均為商標名，由富士聚合物工業 株式會社（Fuji Polymer Industries Co,，Ltd. ) f 造）、 IVSM-4500 (商標名，由東芝株式會社（ Corporation)製造）及SR-7010 (商標名，由道康寧東麗 有限公司（Dow Corning Toray Co.，Ltd.)製造）。 熱塑性樹脂之實例包含聚碳酸酯樹脂、聚職樹脂以及 聚酯礙樹脂。可使用之聚碳酸酯樹脂的線性膨脹係數為 [1〇·6/克耳文]至70[10·6/克耳文]，且折射率為14〇至L7〇, 71 201237555The polymeric composition is suitable for forming a light-shielding zone of a wafer level lens. One and (Ε-3) additive (formed by Wu Wubai, it can be shaped. For this reason, black can be 68 201237555 39636pif, in addition, 'for forming a light-shielding film' is preferably spray coated as follows The black polymerizable composition is applied to the solid surface. Therefore, the total solid content in the black polymerizable composition is preferably 20 in view of preventing liquid discharge when the black polymerizable composition is applied to the curved surface. The mass% to 35% by mass, more preferably 21% by mass to 33% by mass, and most preferably 25% by mass to 30% by mass. Wafer Level Lens The wafer level lens of the present invention may comprise the black polymerizable composition of the present invention. A light-shielding film (i.e., a black layer) is formed. A wafer-level lens of the present invention will be described hereinafter. Fig. 1 is a plan view showing an example of a configuration of a wafer-level lens array having a plurality of wafer-level lenses. As shown in FIG. 1, the wafer level lens array includes a substrate 1 and a lens 12 arranged on the substrate 10. In Fig. 1, the plurality of lenses 12 are arranged two-dimensionally with respect to the substrate 10, but they may also be arranged in one dimension. Figure 2 is the wafer level lens array shown in Figure 1. A view taken along line A_A As shown in Fig. 2, in the wafer level lens array, a light shielding film 14 for preventing light transmission is formed in a region other than the lens 12 between the plurality of lenses 12 arranged on the substrate 1A. The wafer level lens of the present invention comprises a lens 12 present on the substrate 10 and a light shielding film 14 provided on a peripheral portion of the lens. The black curable composition of the present invention is used to form the light shielding film 14, thereby forming a light shielding region. The configuration of the wafer level lens array will be described below by way of example, in which a plurality of lenses 12 in 2012 201255 jyojopit are arranged two-dimensionally with respect to the substrate 10, as shown in Fig. 1. The lens 12 is generally made of the same material as the substrate 10. Formed, and may be integrally formed on the substrate 10 or may be formed as an individual structure and fixed on the substrate. One example of the wafer level lens of the present invention is cited herein, but the wafer level lens of the present invention is not limited to the example, and Various embodiments may be used, such as wafer level lenses having a multilayer structure or wafer level lenses that are separated into lens modules by dicing. Examples of materials forming the lens 12 include glass. Glass, and glass is preferably used as a material having a high-pitch lens because glass having a high refractive index can be selected from various glasses. In addition, glass has excellent heat resistance and can withstand an imaging unit. Examples of other materials for forming the lens 12 by the upper reflow mounting include a resin. The resin has excellent workability, and the surface of the lens can be easily and inexpensively formed using, for example, a rnoid or a die. Suitable. The wafer level lens is preferably formed using an energic curable resin. The energy curable resin can be a resin that can be cured by heating or can be applied by riding an active energy ray (eg, heat application, ultraviolet light) Any of the resins cured by radiation or electron beam radiation. The field considers the reflow mounting of the image forming unit, and has a relatively high softening point (for example, 200 C or 2 〇〇. The resin of yttrium is preferable, and the resin softened by more than 25 CTC is more preferable. Hereinafter, the preferred one as the lens material will be described. Resin. Examples of UV curable resin include UV curable polyglycol 201237555 39636pif external curable epoxy resin and UV curable acrylic acid tree 曰 σ in the linear expansion coefficient of the epoxy resin of the present invention (this e — coefficient) is 4〇[Μ,克尔文] to 8〇[1〇_6/克尔文]' and the refractive index is i.50 to U and preferably 15〇 to 165. Examples include thermosetting polywei resin, thermosetting epoxy resin, thermosetting (tetra) resin, and thermosetting propylene oxide resin. For example, the linear expansion coefficient of the polysulfide resin that can be used is 3 〇 [1〇_6/克160 [10 / gram], and the refractive index is 14 〇 to ! 55. For example, the epoxy resin can be used with a linear expansion coefficient of 4 () [1 () _ 6 / gram to 80 [ΙΟ · 6 / gram], and the refractive index is i 5 〇 to i 7 〇, and preferably i % to 1.65. The linear expansion coefficient of the phenol resin is from 3 〇 to 克 [10 6 / gram], and the refractive index is i 5 〇 to i 7 〇. The linear expansion coefficient of the acrylic resin that can be used is 2 〇 [1〇 · 6 / gram of gram] to 6 〇 [ΙΟ - 6 / gram], and the refractive index is L40 to 160, and preferably t 5 1_60. Commercially available products can be used as thermosetting resins. Specific examples include SMX -7852 and SMX-7877 (both trademark names, manufactured by Fuji Polymer Industries Co., Ltd.), IVSM-4500 (trade name, manufactured by Toshiba Corporation) SR-7010 (trade name, manufactured by Dow Corning Toray Co., Ltd.) Examples of the thermoplastic resin include polycarbonate resin, poly-resin resin, and polyester resin. Polycarbonate which can be used The linear expansion coefficient of the ester resin is [1 〇 · 6 / gram] to 70 [10 · 6 / gram], and the refractive index is 14 〇 to L7 〇, 71 201237555

JbfOJOpif 上U 1 Μ5。可使狀聚__線性膨脹係數 ”’、 /克耳文]至60 [1(Γ6/克耳文]，且折射率為〗63。 可使用之聚醚砜樹脂的線性膨脹係數為2〇 [1〇-6/克耳文 60 [1〇6/克耳文]，且折射率為1.65。 外’光學麵—般在贼下之雜雜係數為4 9 [/克耳文]至14.3 [10·6/克耳文]，且在589.3奈米之波長 M至η。另外，石英玻璃之線性膨服係數為 .[克耳文]至0.5[1〇·6/克耳文]，且折射率為約丨衫。 At出於成形性（諸如模具形狀之轉移適合性）之觀點， 能夠用於形成透鏡之可固化樹脂組成物較佳在固化前具有 ，合流動性。特定言之，可固化樹脂組成物較佳在正Ϊ溫 度下為液體且黏度為約L000毫帕.秒至約5〇，_毫帕秒。 另一方面，能夠用於形成透鏡之可固化樹脂組成物較 佳具有财熱性’以使其在固化後不會因回焊製程而遭受熱 Ί。出於這些觀點，固化材料之玻璃轉化溫度較佳為 2〇〇ΐ或高於2GG〇C，更佳為2贼或高於2贼且尤其較 佳為300。(：或高於3〇(TC。為賦予樹脂組成物所述高耐熱 性，必須抑制分子層面之遷移率。其有效方法之實例包含 1)增加每單位體積之交聯密度，⑴使用具有剛性環狀 結構之樹脂（例如具有脂環族結構（諸如環己烧、降冰片 烧或四環十二烧）、芳族結構（諸如苯或蔡）、轴節（card0) 、…構（諸如9,9·聯苯苐）或螺（spir〇)結構（諸如螺聯茚 ，（spirobiindane))之樹脂，尤其例如 Jp_A 第 9137〇43 喊、第 10-67970 號、第 2003-55316 號、第 2007-334018JbfOJOpif on U 1 Μ 5. It can be used to form a __ linear expansion coefficient "', / gram" to 60 [1 (Γ6 / gram), and a refractive index of 63. The polyether sulfone resin that can be used has a linear expansion coefficient of 2 〇. [1〇-6/克尔文60 [1〇6/克耳文], and the refractive index is 1.65. The external 'optical surface' is usually under the thief of 4 9 [/ gram] to 14.3 [10·6/Kelvin], and at a wavelength of 589.3 nm, M to η. In addition, the linear expansion coefficient of quartz glass is [Kelvin] to 0.5 [1〇·6/gram], Further, the refractive index is about 丨. At the viewpoint of formability (such as transfer suitability of a mold shape), the curable resin composition which can be used for forming a lens preferably has a fluidity before curing. The curable resin composition is preferably liquid at a positive temperature and has a viscosity of from about L000 mPa.s to about 5 Å, _mPas. On the other hand, the curable resin composition which can be used to form the lens is more Good fortune' so that it will not be entangled by the reflow process after curing. From these points of view, the glass transition temperature of the cured material is preferably 2 〇〇ΐ or higher than 2 GG C More preferably, it is 2 thieves or more than 2 thieves and particularly preferably 300. (: or higher than 3 〇 (TC. In order to impart high heat resistance to the resin composition, it is necessary to suppress mobility at the molecular level. Examples include 1) increasing the crosslink density per unit volume, and (1) using a resin having a rigid cyclic structure (for example, having an alicyclic structure (such as cyclohexene, norborne burn or tetracyclic dodecan), an aromatic structure. a resin (such as benzene or Tsai), a shaft (card0), a structure (such as 9,9·biphenyl) or a spir〇 structure (such as spirobiindane), especially such as Jp_A No. 9137 〇43 shouting, No. 10-67970, No. 2003-55316, 2007-334018

72 201237555 39636pif 號及第細7_238883號中所述之樹脂及其類似樹脂），以及 使向Tg材料（諸如無機細粒，例如Jp_A第5_2〇9〇27 唬^第10-298265號中所述之材料）均勻分散。這些方法 可單獨使用或以多種之組合形式使用，且較佳在不會減弱 其他特性（諸如流動性、收縮率或折射率）之範圍内調節。 出於形狀轉移精密度之觀點，藉由固化反應展現低體 積收縮率之可固化樹脂組成物為較佳。本發明所用之樹脂 組成物的固化收縮率較佳為10%或低於1〇%，更佳為5% 或低於5% ’且尤其較佳為3%或低於3%。 具有低固化收縮率之樹脂組成物的實例包含以下（i ) 至（6): (1) 含有高分子量固化劑（例如預聚物）之樹脂組成 物（例如如 JP-A 第 2001-19740 號、JP-Α 第 2004-302293 说及JP-A第2007-211247號中所述之組成物），其中高分 子量固化劑之數目平均分子量較佳在200至1〇〇,〇〇〇範圍 内，更佳在500至50,000範圍内且尤其較佳在1，〇〇〇至 20,000範圍内；且藉由計算固化劑之數目平均分子量/固化 劑中固化反應性基團數而獲得之值較佳在50至10,000範 圍内，更佳在100至5,000範圍内且尤其較佳在200至3,000 範圍内； (2) 含有非反應性材料（例如有機細粒、無機細粒或 非反應性樹脂）之樹脂組成物（例如如JP-Α第6-298883 號、JP-Α 第 2001-247793 號及 JP-Α 第 2006-225434 號中所 述之組成物）； 73 201237555 (3 )含有如下相對低收縮-交聯反應性基團之樹脂組成 物，例如開環可聚合基團，諸如環氧基（例如JP_A第 2004- 210932號中所述之組成物）、氧雜環丁烷基（〇xetanyi group)(例如JP-A第8-134405號中所述之組成物）、環硫 基（迎lfide group)(例如JP-A第2002-105110號中所述 之組成物）、環狀石炭酸g旨基團（例如jp_A第7-62065號中 所述之組成物）、烯/硫醇固化基團（例如jp_A第2003-20334 號中所述之組成物）、矽氫化固化基團（例如JP_A第 2005- 15666號中所述之組成物）； (4) 含有具有剛性骨架（例如苐、金剛烧或異佛酮） 之樹脂的樹脂組成物（例如JP-Α第9-137043號中所述之 組成物）； (5) 含有具有不同可聚合基團之兩種單體且形成互穿 網狀結構（亦即IPN結構）的樹脂組成物（例如Jp_A第 2006- 131868號中所述之組成物）；以及 (6 )含有可知脹材料之樹脂組成物（例如jp-a第 2004-2719號及JP-Α第2008-238417號中所述之組成物）。 此外，出於使物理特性達最佳之觀點，較佳使用固化收縮 降低方法中之兩者或超過兩者的組合（例如含有含開環可 聚合基團及細粒之預聚物的樹脂組成物）β 為幵&gt;成本發明之晶圓級透鏡，兩種或超過兩種分別具 有不同局阿貝數（Abbe number )及低阿貝數的樹脂組成物 為較佳。 在具有相對鬲阿貝數之樹脂中，阿貝數（^d)較佳72 201237555 39636pif and the resin described in detail No. 7-238883, and similar resins thereof, and to Tg materials (such as inorganic fine particles, for example, Jp_A 5-2〇9〇27 唬^10-298265) Material) uniformly dispersed. These methods may be used singly or in combination of plural kinds, and are preferably adjusted within a range that does not impair other characteristics such as fluidity, shrinkage or refractive index. From the viewpoint of the shape transfer precision, a curable resin composition exhibiting a low volume shrinkage by a curing reaction is preferred. The curing shrinkage of the resin composition used in the present invention is preferably 10% or less, more preferably 5% or less, and particularly preferably 3% or less. Examples of the resin composition having a low curing shrinkage ratio include the following (i) to (6): (1) a resin composition containing a high molecular weight curing agent (for example, a prepolymer) (for example, JP-A No. 2001-19740) JP-A No. 2004-302293, the composition described in JP-A No. 2007-211247, wherein the number average molecular weight of the high molecular weight curing agent is preferably in the range of 200 to 1 Torr, More preferably in the range of 500 to 50,000 and particularly preferably in the range of 1, 〇〇〇 to 20,000; and the value obtained by calculating the number average curing molecular weight of the curing agent / the number of curing reactive groups in the curing agent is preferably In the range of 50 to 10,000, more preferably in the range of 100 to 5,000 and particularly preferably in the range of 200 to 3,000; (2) a resin containing a non-reactive material such as organic fine particles, inorganic fine particles or non-reactive resin The composition (for example, a composition as described in JP-A No. 6-298883, JP-A No. 2001-247793, and JP-A No. 2006-225434); 73 201237555 (3) contains the following relatively low shrinkage - a resin composition of a cross-linking reactive group, such as a ring-opening polymerizable group, An epoxy group (for example, a composition described in JP-A No. 2004-210932), an oxetanyl group (for example, a composition described in JP-A No. 8-134405), and an epoxide A group (for example, a composition described in JP-A No. 2002-105110), a cyclic carbolic acid group (for example, a composition described in jp_A No. 7-62065), an alkene/sulfur An alcohol-curing group (for example, a composition described in jp_A No. 2003-20334), a hydrogenation-curing group (for example, a composition described in JP-A No. 2005-15666); (4) containing a rigid skeleton (for example) a resin composition of a resin of ruthenium, adamant or isophorone (for example, a composition described in JP-A No. 9-137043); (5) containing two monomers having different polymerizable groups and forming a resin composition interpenetrating a network structure (that is, an IPN structure) (for example, a composition described in Jp_A No. 2006-131868); and (6) a resin composition containing a swellable material (for example, jp-a 2004) The composition described in No. -2719 and JP-A No. 2008-238417). Further, from the viewpoint of optimizing physical properties, it is preferred to use two or more combinations of curing shrinkage reduction methods (for example, a resin composition containing a prepolymer having a ring-opening polymerizable group and fine particles) β) is a wafer-level lens of the invention, and two or more resin compositions each having a different Abbe number and a low Abbe number are preferred. In the resin having a relative Abbe number, the Abbe number (^d) is preferred.

74 201237555 3yW6pif 為50或大於50，更佳為55或大於55，且尤其較佳為6〇 或大於60°樹脂之折射率（nd)較佳為i 52或大於i 52， 更佳為1.55或大於1.55且尤其較佳為157或大於157。 樹脂較佳為脂族樹脂，且更佳為具有脂環族結構之樹 脂（例如具有環狀結構（諸如環己烷、降冰片烷、金剛烷、 二裱癸烷或四環十二烷）之樹脂，尤其例如Jp_A第 10-152551 號、JP-A 第 2002-212500 號、JP-A 第 2003-20334 號、JP-A 第 2004-210932 號、JP-A 第 2006-199790 號、JP-A 第 2007-2144 號、JP_a 第 2007-284650 號及 JP-A 第 2008-105999號中所述之樹脂）。 在具有相對低阿貝數之樹脂中，阿貝數（ud)較佳 為30或小於30，更佳為25或小於25，且尤其較佳為20 或小於20。樹脂之折射率（nd)較佳為丨6〇或大於丨6〇， 更佳為1.63或大於ι·63且尤其較佳為1.65或大於1.65。 樹脂較佳為具有芳族結構之樹脂，且更佳為例如含有 9,9’-二芳基第、萘、苯并嗟嗤、苯并三唾或其類似物之結 構的樹脂（尤其例如JP-Α第60-38411號、JP-A第10-67977 號、JP-A 第 2002-47335 號、JP-A 第 2003-238884 號、JP-A 第 2004-83855 號、JP_A 第 2005-325331 號、jp_A 第 2007-238883 號、WO 2006/095610 及日本專利第 2537540 號中所述之樹脂）。 出於提高折射率或調節阿貝數之觀點，在用於形成晶 圓級透鏡之樹脂組成物中，較佳使用含有分散於基質中之 無機細粒的有機或無機複合材料。 75 201237555 乃 ojopu 有機或無機複合材料巾域細粒之實例包 細粒、硫化物細粒、錢物細粒以及碲化物纟樣。 實例包含氧化錯、氧化鈦、氧化鋅、氧化錫、氧化起特ί γ、氧化!S、氧化鑭、氧化紀、硫化辞或其類似物之細 無機細粒可單獨㈣或以其兩種或超過兩 形式使用。此外，無機細粒可由多種組分之複合物、σ 為降低例如光催化活性及水吸收，無機細粒可經里暫 金屬摻雜，或其表面層可用異f金屬氧化物（諸如二= 石夕或氧化!S)塗佈’或其表面可使用⑨㈣合劑、紙酸㊉ 偶合劑、有機酸（例如羧酸、磺酸、磷酸以及膦酸 有機酸基團之分散劑或其類似物改質。 無機細粒之數目平均一次粒度一般可為約i奈米至 1，000奈米。當粒度過小時，存在物理特性改變之情j兄。 當粒度過大時’瑞利散射（Rayleigh scattering)之作用明 顯。就此而言’數目平均一次粒度較佳為丨奈米至15奈米， 更佳為2奈米至1〇奈米且尤其較佳為3奈米至7奈米。此 外，無機細粒之較窄粒度分佈為較佳。單分散粒子具有各 種定義，且例如’如JP-A第2006-160992號中所述之值之 指定範圍對應於較佳粒度分佈範圍。 上述數目平均一次粒度可使用例如X射線繞射（x_ray diffraction，XRD)設備、透射電子顯微鏡（transmissi〇n electron microscope，TEM)或其類似物量測。 在22°C下且在589.3奈米波長下，無機細粒之折射率74 201237555 3yW6pif is 50 or more, more preferably 55 or more, and particularly preferably 6 〇 or more, the refractive index (nd) of the resin is preferably i 52 or greater than i 52 , more preferably 1.55 or It is more than 1.55 and particularly preferably 157 or more than 157. The resin is preferably an aliphatic resin, and more preferably a resin having an alicyclic structure (for example, having a cyclic structure such as cyclohexane, norbornane, adamantane, dioxane or tetracyclododecane) Resins, for example, Jp_A No. 10-152551, JP-A No. 2002-212500, JP-A No. 2003-20334, JP-A No. 2004-210932, JP-A No. 2006-199790, JP-A Resin described in No. 2007-2144, JP-A No. 2007-284650, and JP-A No. 2008-105999. In the resin having a relatively low Abbe number, the Abbe number (ud) is preferably 30 or less, more preferably 25 or less, and particularly preferably 20 or less. The refractive index (nd) of the resin is preferably 丨6〇 or more than 丨6〇, more preferably 1.63 or more than ι·63 and particularly preferably 1.65 or more than 1.65. The resin is preferably a resin having an aromatic structure, and more preferably a resin containing a structure of 9,9'-diaryl, naphthalene, benzopyrene, benzotrisine or the like (especially, for example, JP) - Α 60-38411, JP-A No. 10-67977, JP-A No. 2002-47335, JP-A No. 2003-238884, JP-A No. 2004-83855, JP-A No. 2005-325331 , the resin described in jp_A No. 2007-238883, WO 2006/095610, and Japanese Patent No. 2537540). From the viewpoint of increasing the refractive index or adjusting the Abbe number, in the resin composition for forming a crystal-level lens, an organic or inorganic composite material containing inorganic fine particles dispersed in a matrix is preferably used. 75 201237555 乃 ojopu Examples of fine particles of organic or inorganic composite materials. Fine particles, sulfide fine particles, fine particles of fine materials and bismuth compounds. Examples of fine inorganic fine particles comprising oxidative oxidization, titanium oxide, zinc oxide, tin oxide, oxidized γ γ, oxidized !S, cerium oxide, oxidized particles, sulfurized or the like may be used alone (d) or in two or More than two forms are used. In addition, the inorganic fine particles may be reduced by a composite of a plurality of components, σ such as photocatalytic activity and water absorption, the inorganic fine particles may be doped with a temporary metal, or the surface layer thereof may be an iso-f metal oxide (such as bis = stone) Even oxidized! S) coating 'or its surface may be modified with a 9 (tetra) mixture, a paper acid coupling agent, an organic acid (for example, a dispersant of a carboxylic acid, a sulfonic acid, a phosphoric acid, and a phosphonic acid organic acid group or the like) The average primary particle size of the inorganic fine particles may generally be from about 1 nm to 1,000 nm. When the particle size is too small, there is a change in physical properties. When the particle size is too large, Rayleigh scattering The effect is obvious. In this regard, the number average primary particle size is preferably from 丨 nanometer to 15 nanometers, more preferably from 2 nanometers to 1 nanometer nanometer and particularly preferably from 3 nanometers to 7 nanometers. The narrower particle size distribution of the particles is preferred. The monodisperse particles have various definitions, and the specified range of values such as those described in JP-A No. 2006-160992 corresponds to a preferred particle size distribution range. For example, X-ray diffraction can be used (x _ray diffraction, XRD) apparatus, transmission electron microscopy (TEM) or its analog measurement. Refractive index of inorganic fine particles at 22 ° C and at a wavelength of 589.3 nm

76 201237555 39636pif 較佳為1.90至3.00，更佳為至2 7〇，且尤 2.00 至 2.70。 ’、 4 出於透明度及較高折射率之觀點，以作為無機細粒之 基質的樹脂計，有機-無機複合材料中無機細粒之含量為5 質量％或超過5質量％，更佳為1〇質量％至7〇質量％，且 尤其較佳為30質量％至60質量〇/〇。 充當有機-無機複合材料中所用之基質的樹脂的實例 包含上文作為晶圓級透鏡材料所述之具有相對高阿貝數的 紫外線可固化樹脂、熱固性樹脂、熱塑性樹脂以及具有相 對低阿貝數之樹脂。此外’樹脂之實例包含折射率高於丨6 〇 之樹脂，諸如JP-A第2007-93893號中所述之樹脂；由疏 水性區段及親水性區段組成之嵌段共聚物，諸如Jp_A第 2〇〇7_2出64號巾所狀毅共聚物；在聚合物之末端或 侧鏈具有能夠與無機細粒形成任意化學鍵之官能基的樹 脂，諸如JP-A第2007-238929號、日本專利申請案第 2008-12645 號、第 2008-208427 號、第 2008-229629 號及 第2008-219952號中所述之樹脂；以及曰本專利申請案第 2008-197054號及第2008-198878號中所述之熱塑性樹脂。 此外，必要時，可添加添加劑（諸如增塑劑或分散劑） 至有機-無機複合材料中。 就此而言’作為基質之樹脂與無機細粒之較佳組合如 下。 亦即’當如上所述具有相對高阿貝數之樹脂用作基質 時，較佳將氧化鑭、氧化鋁、氧化錯或其類似物之細粒作 77 201237555 vjpn 為無機細粒分散於樹脂中。當具有相對低阿貝數之樹脂用 作基質時’較佳將氧化鈦、氧化錫、氧化錯或其類似物之 細粒作為無機細粒分散於樹脂中。 為使無機細粒均勻分散，較佳適當使用例如含有對形 成基質之樹脂早體具有反應性之官能基的分散劑（例如於 JP-A第2007-238884號之實例部分中所述之分散劑及其類 似物）；由疏水性區段及親水性區段形成之嵌段共聚物（例 如JP-A第2007-211164號中所述之嵌段共聚物）；或在高 分子之末端或側鏈中具有能夠與無機細粒形成任意化學鍵 之官能基的樹脂（例如JP-A第2007-238929號及第 2007-238930號中所述之樹脂及其類似物）。 用於形成本發明晶圓級透鏡之樹脂組成物宜與諸如 以下添加劑摻合：已知脫模劑，諸如矽化合物、含氟化合 物或含長鏈燒基之化合物；或抗氧化劑，諸如受阻紛。 必要時’用於形成本發明晶圓級透鏡之樹脂組成物可 與固化催化劑或起始劑摻合。其特定實例包含如jp_A第 2005-92099號之第[0065]段至第[〇〇66]段中所述的藉由熱 或活性能量射線之作用促進固化反應（自由基聚合或離子 聚合）的化合物。欲添加之固化反應促進劑之量可視催化 劑或起始劑之類型或固化反應性部分之類型而變化，因此 ，里不能無條件設定。然而，以樹脂組成物之總固體含量 计，所述量較佳為約〇丨質量％至15質量％，且更佳為約 〇·5質量％至5質量〇/〇。 用於製備本發明晶圓級透鏡之樹脂組成物可藉由適 78 201237555 39636pif 當摻合上述組分製備。此時，#除液紐低分子量單體（反 應性稀釋劑）以外之組分可溶解於所述單體中時，不需要 添加個別溶劑’而在組分不溶解於液驗低分子量單體中 之情況下’個別組分可使用溶劑溶解，從而 物。可用於樹脂組成物之溶劑不受特別限制，且可適;^ 擇，只要在所得組成物中不產生沈殿且達成均質溶解I分 散即可。溶劑之特定實例包含調(例如丙嗣、== ^甲基異丁基酮）、酿（例如乙酸乙醋及乙酸丁 土例 如四氫。夫喃二魏）、醇（例如甲醇、乙醇、異丙醇、】 I醇及乙二醇）、芳族煙（例如甲苯及二曱苯）以及水。合 =脂組成物含有溶劑時，較麵組成物輯於基板及/或； -上’且錢鋪，临藉峨具雜進行轉移操作二、 基^)可由與透鏡12之模歸料相同之材料形成。 3臭==不同於透鏡12之模製材料的材料形成， =要基板U)輯可見光透明之㈣（諸如麵） ^在此航下，胁軸絲1G之材騎 具有㈣或實^朗鱗轉脹係數2 10之材料相ί 材㈣祕雜紐與胁形成基板 造mi 上時在加熱期間由於線性膨脹率不同而 成的，鏡12變形或破裂得以抑制。 儘管圖1及圖2中未示，但可在基板1G之光 、面上形成紅外濾光片（IR濾光片）。 下文將參看圖3至圖8C，藉由提及製造晶圓級透鏡 79 201237555 jyo^opn 陣列之方法特別描述晶圓級透鏡之組態及製造。 晶圓級透鏡之組態及製造（1) 形成透鏡 首先，參看圖3及圖4A至圖4C，描述一種在基板1〇 上形成透鏡12之方法。 Α 在本文中，圖3為顯示於基板10上提供作為用於形 成透鏡之樹脂組成物的模製材料（圖3中稱作「Μ = 態的視圖。 」 狀 圖4Α至圖4C為顯示使用模具6〇於基板1〇 鏡12之程序的示意圖。 俱展透 如圖3所示，使用分配器（出叩⑼⑽）％於基板 之上面欲形成透鏡12之區域上逐滴施加模製材料Μ 之各區域上提供形成-透鏡12所必需之量的 如圖4Α所π ’在向基板1〇提供模製材料Μ後 之ί 之模具6〇配置在上面已提供模製材料Μ 之暴板10的表面上。 用於ί本文中，根據透鏡12之所要數目，模具6G中提供 用於轉移透鏡12之形狀的多個凹面部分62。 隨後’如® 4B所示’財6〇壓向基板1〇上之模製 p '以使付模製材料M根據凹面部分62之形狀變形。 C去:模製^料M為熱固性樹脂或紫外線可固化樹脂 射^妙具60壓向模製材料M時藉由自模具60之外部照 射熱或紫外光使模製材料M固化。 201237555 39636pif 如圖4c所示，模製材料M固化後，自模具6〇釋放 基板10及透鏡12。 形成遮光膜 參看圖5A至圖5C ’將描述在透鏡12之周邊部分中 形成遮光膜14之方法。 在本文中，《5Α至圖5C為顯示在上面已形成透鏡 12之基板H)上形成遮光膜Μ之製程的示意性剖面圖。 形成遮光膜14之方法至少包含： 於基板10上塗覆本發明之黑色可固化組成物以形成 遮光塗層14Α (其可稱作「遮光塗層形成製矛呈」）（參見圖 5Α)； 使遮光塗層14Α經由光罩70進行圖案曝光（其可稱 作「曝光製程」）（參見圖5Β);及 曝光後使遮光塗層14Α顯影，隨後移除未固化部分， 形成圖案化遮光膜14 (其可稱作「顯影製程」）（參見圖 5C)。 遮光膜14可在製造透鏡12之前或之後任意形成。在 下文中將詳細描述在製造透鏡12後形成圖案化遮光膜之 方法。 、 下文將描述形成遮光膜14之方法的個別步驟。 遮光塗層形成製程 如圖5Α所示，在遮光塗層形成製程中，於基板1〇及 透鏡12上塗佈黑色可固化組成物以形成由黑色可固化組 成物形成的具有低光反射率之遮光塗層14Α。在此情況 81 201237555 iyi)36pif 下，形成遮光塗層14A以覆蓋基板10之表面以及透鏡12 之透鏡表面12a及周邊部分12b之表面中之全部。 亦可用於此製程之基板10不受特別限制且其實例包 含鈉玻璃（soda glass)、非驗性玻璃、派熱克斯（pyreX) (註冊商標）玻璃、石英玻璃以及透明樹脂。 在一實施例中，本文所述之基板10指包含透鏡12與 基板10之組態，其中透鏡12及基板1〇是整體形成。 必要時’可在基板10上提供底塗層，以改良與上層 之黏者’防止材料擴散或基板1〇之表面平坦化（變平）。 於基板10及透鏡12上塗覆黑色可固化組成物之方法 的實例包含各種塗佈方法，諸如隙縫塗佈、噴塗、喷墨法、 旋塗、鑄塗、滚塗或網版印刷法。 出於塗膜之厚度均一性及易於乾燥塗佈溶劑之觀 塗覆黑色可固化組成物後之即刻膜厚度較佳為〇1微 米至10微米，更佳為0 2微米至5微米，且甚至 〇·2微米至3微米。 基板10上所塗佈之遮光塗層14A的乾燥（預烘烤: 可使用熱板、烘箱或其類似物在50。(：至14〇t之溫度下^ 行10秒至300秒。 「黑色可固化組成物乾燥後之塗膜厚度（下文亦簡稱作 乾膜厚度」）可根據所要效能（諸如遮光特性）任意選擇， 且般在約0.1微米至小於5〇微米範圍内。 曝光製裎 在曝光製程中，賊錄層形成製程中所形成之遮光76 201237555 39636pif is preferably 1.90 to 3.00, more preferably 2 to 7 inches, and especially 2.00 to 2.70. ', 4 From the viewpoint of transparency and a higher refractive index, the content of the inorganic fine particles in the organic-inorganic composite material is 5% by mass or more, more preferably 5% by mass, based on the resin as the matrix of the inorganic fine particles. 〇% by mass to 7% by mass, and particularly preferably from 30% by mass to 60% by mass. Examples of the resin serving as a substrate used in the organic-inorganic composite material include the ultraviolet curable resin having a relatively high Abbe number as described above as a wafer-level lens material, a thermosetting resin, a thermoplastic resin, and having a relatively low Abbe number Resin. Further, examples of the 'resin include a resin having a refractive index higher than 丨6 ,, such as a resin described in JP-A No. 2007-93893; a block copolymer composed of a hydrophobic segment and a hydrophilic segment, such as Jp_A The second copolymer of the No. 64 towel of No. 64 is a resin having a functional group capable of forming an arbitrary chemical bond with the inorganic fine particles at the end or side chain of the polymer, such as JP-A No. 2007-238929, Japanese Patent The resins described in the application Nos. 2008-12645, 2008-208427, 2008-229629, and 2008-219952; and in the patent applications Nos. 2008-197054 and 2008-198878 Said thermoplastic resin. Further, an additive such as a plasticizer or a dispersant may be added to the organic-inorganic composite material as necessary. In this regard, the preferred combination of the resin as the matrix and the inorganic fine particles is as follows. That is, when a resin having a relatively high Abbe number as described above is used as a substrate, it is preferred to use fine particles of cerium oxide, aluminum oxide, oxidized or its analog as 77 201237555 vjpn as inorganic fine particles dispersed in the resin. . When a resin having a relatively low Abbe number is used as a substrate, it is preferred to disperse fine particles of titanium oxide, tin oxide, oxidized or the like as inorganic fine particles in the resin. In order to uniformly disperse the inorganic fine particles, it is preferred to suitably use, for example, a dispersing agent containing a functional group reactive with the resin-forming precursor of the matrix (for example, the dispersing agent described in the example section of JP-A No. 2007-238884 And an analog thereof; a block copolymer formed of a hydrophobic segment and a hydrophilic segment (for example, a block copolymer described in JP-A No. 2007-211164); or at the end or side of the polymer A resin having a functional group capable of forming an arbitrary chemical bond with an inorganic fine particle (for example, a resin described in JP-A Nos. 2007-238929 and 2007-238930, and the like). The resin composition for forming the wafer level lens of the present invention is preferably blended with an additive such as a known release agent such as a bismuth compound, a fluorine-containing compound or a compound containing a long-chain alkyl group; or an antioxidant such as a hindrance . The resin composition for forming the wafer level lens of the present invention may be blended with a curing catalyst or an initiator as necessary. Specific examples thereof include the promotion of a curing reaction (radical polymerization or ionic polymerization) by the action of heat or active energy rays as described in paragraphs [0065] to [〇〇66] of jp_A No. 2005-92099 Compound. The amount of the curing reaction accelerator to be added may vary depending on the type of the catalyst or the initiator or the type of the curing reactive portion, and therefore, it cannot be unconditionally set. However, the amount is preferably from about 〇丨% by mass to 15% by mass, and more preferably from about 5% by mass to about 5 % by mass based on the total solid content of the resin composition. The resin composition used to prepare the wafer level lens of the present invention can be prepared by blending the above components by the method of 2012 20125555 39636pif. At this time, when the components other than the liquid low molecular weight monomer (reactive diluent) are soluble in the monomer, it is not necessary to add an individual solvent', and the component is not dissolved in the liquid low molecular weight monomer. In the case of 'individual components can be dissolved using a solvent, thus. The solvent which can be used for the resin composition is not particularly limited, and may be appropriately selected as long as no precipitate is formed in the obtained composition and a homogeneous dissolution I dispersion is achieved. Specific examples of the solvent include a modulating (for example, propyl hydrazine, == ^methyl isobutyl ketone), a brewing (for example, ethyl acetate and butyl acetate, such as tetrahydrogen, fumonic di Wei), and an alcohol (for example, methanol, ethanol, and iso). Propanol, I alcohol and ethylene glycol), aromatic smoke (such as toluene and diphenyl), and water. When the fat composition contains a solvent, the surface composition is compiled on the substrate and/or; - on the 'b', and the transfer operation is performed on the substrate, and the base can be the same as the mold of the lens 12. Material formation. 3 odor == different from the material of the molding material of the lens 12, = the substrate U) the visible light transparent (four) (such as the surface) ^ Under this navigation, the flank of the flank wire 1G has (four) or real lang scale The material with a coefficient of expansion of 2 10 is the material of the material (4), and the deformation or crack of the mirror 12 is suppressed during the heating due to the difference in linear expansion ratio during heating. Although not shown in Fig. 1 and Fig. 2, an infrared filter (IR filter) can be formed on the light and surface of the substrate 1G. Referring now to Figures 3 through 8C, the configuration and fabrication of wafer level lenses is specifically described by reference to the method of fabricating wafer level lenses 79 201237555 jyo^opn arrays. Configuration and Fabrication of Wafer Level Lens (1) Forming a Lens First, referring to Fig. 3 and Figs. 4A to 4C, a method of forming a lens 12 on a substrate 1A will be described. Α Herein, FIG. 3 is a view showing a molding material which is provided as a resin composition for forming a lens on a substrate 10 (referred to as a "Μ = state in FIG. 3". FIG. 4A to FIG. 4C are used for display. A schematic view of the procedure of the mold 6 on the substrate 1 of the mirror 12. As shown in Fig. 3, the dispenser (the exit pupil (9) (10))% is used to apply the molding material dropwise on the area of the substrate on which the lens 12 is to be formed. Each of the regions is provided with the amount necessary for forming the lens 12, as shown in FIG. 4', and the mold 6 is provided after the molding material is supplied to the substrate 1A, and the dummy sheet 10 on which the molding material has been provided is disposed. In the present invention, a plurality of concave portions 62 for transferring the shape of the lens 12 are provided in the mold 6G according to the desired number of the lenses 12. Subsequently, as shown in Fig. 4B, the financial substrate is pressed toward the substrate 1 The molding p' is molded so that the molding material M is deformed according to the shape of the concave portion 62. C: The molding material M is a thermosetting resin or an ultraviolet curable resin, and the molding material M is pressed against the molding material M. The molding material M is cured by irradiating heat or ultraviolet light from the outside of the mold 60. 201 237555 39636pif As shown in Fig. 4c, after the molding material M is cured, the substrate 10 and the lens 12 are released from the mold 6〇. Forming a light-shielding film Referring to Figs. 5A to 5C, the formation of the light-shielding film 14 in the peripheral portion of the lens 12 will be described. In the present invention, "5" to 5C is a schematic cross-sectional view showing a process of forming a light-shielding film on the substrate H on which the lens 12 has been formed. The method of forming the light shielding film 14 comprises at least: coating the black curable composition of the present invention on the substrate 10 to form a light-shielding coating 14 (which may be referred to as "a light-shielding coating to form a spear") (see FIG. 5A); The light-shielding coating 14 is patterned by the mask 70 (which may be referred to as "exposure process") (see FIG. 5A); and after the exposure, the light-shielding coating 14 is developed, and then the uncured portion is removed to form the patterned light-shielding film 14 (It may be referred to as "development process") (see Figure 5C). The light shielding film 14 can be arbitrarily formed before or after the lens 12 is manufactured. A method of forming a patterned light-shielding film after the lens 12 is manufactured will be described in detail hereinafter. The individual steps of the method of forming the light shielding film 14 will be described below. The light-shielding coating forming process is as shown in FIG. 5A. In the light-shielding coating forming process, the black curable composition is coated on the substrate 1 and the lens 12 to form a low light reflectance formed by the black curable composition. The light-shielding coating 14Α. In this case 81 201237555 iyi) 36pif, a light-shielding coating 14A is formed to cover the surface of the substrate 10 and all of the surfaces of the lens surface 12a and the peripheral portion 12b of the lens 12. The substrate 10 which can also be used in this process is not particularly limited and examples thereof include soda glass, non-innovative glass, pyreX (registered trademark) glass, quartz glass, and transparent resin. In one embodiment, substrate 10 as described herein refers to a configuration comprising lens 12 and substrate 10, wherein lens 12 and substrate 1 are integrally formed. If necessary, an undercoat layer may be provided on the substrate 10 to improve the adhesion to the upper layer to prevent material diffusion or flattening (flattening) the surface of the substrate. Examples of the method of coating the black curable composition on the substrate 10 and the lens 12 include various coating methods such as slit coating, spray coating, ink jet method, spin coating, cast coating, roll coating or screen printing. The film thickness immediately after coating the black curable composition for the thickness uniformity of the coating film and the ease of drying the coating solvent is preferably from 1 μm to 10 μm, more preferably from 0 μm to 5 μm, and even 〇·2 microns to 3 microns. Drying of the light-shielding coating 14A applied on the substrate 10 (pre-baking: a hot plate, an oven or the like can be used at 50. (: to a temperature of 14 〇t for 10 seconds to 300 seconds. The thickness of the coating film after drying of the curable composition (hereinafter also referred to as dry film thickness) can be arbitrarily selected according to the desired performance (such as light-shielding property), and is generally in the range of about 0.1 μm to less than 5 μm. In the exposure process, the thief recording layer forms the shading formed in the process

82 201237555 39636pif 塗層14A進行圖案逐次（patternwise)曝光。圖案逐次曝 光可藉由掃描曝光執行，但如圖5B所示，經由具有預定 光罩圖案之光罩70曝光為較佳。 在此製程之曝光中，塗層14A經由具有預定光罩圖案 之光罩曝光’從而僅使塗層14A中用光照射之部分固化。 使用光罩圖案’經由所述光罩圖案用光照射透鏡周邊部分 12b之表面及基板10 t存在於透鏡12之間的表面。因此， 僅除透鏡表面12a以外之區域中存在的遮光塗層14A藉由 光照射固化，且固化區形成遮光膜14。 作為可用於曝光之放射線，較佳使用紫外線，諸如g 射線、h射線或i射線。放射線可來自單波長之光源或可 來自包含所有波長之光源，諸如高壓汞燈。 顯影製程 隨後，藉由執行鹼顯影處理（顯影製程），在曝光期 1未、、玉光照射之部分（亦即遮光塗層之未固化部分） 於驗水^中溶離’而僅保留藉由光照射固化之部分。 觀旦 1疋S之，當使如圖5B所示之經曝光之遮光塗層14A =日，、，僅移除於透鏡表面12a上形成之遮光塗層 14A， 14，二^二仏以外之其他區域中形成固化遮光膜 驗試下中Si顯|劑=即驗水溶液）中所含的 路之可能性的觀點損害周邊電 化成本發明之遮光獏中較佳使用有 83 201237555 機驗顯影劑。 顯影劑中所用之鹼試劑之 即有機鹼試劑），諸如氨水'乙胺、機鹼化合物（亦 氫氧化四曱銨、氫氧化四乙銨？膽:乙胺、二曱基乙醇胺、 二氮雜雙環-[5.4.0K7-十—破梳.^ 、吡咯、哌啶或1，8-機鹼試劑)’諸如氫氧化鈉、氫氧：：無機化合物（亦即無 鉀。較佳使用藉由用純水稀氫納或碳酸氮 濃度而獲得的鹼水溶液作為顯影劑。 質里/〇之 -般而言，在2吖至耽之溫 時間為20秒至90秒。 延仃扇办，顯β 當使用由鹼水溶液形成之顯影劑時 分-般藉賴移除，繼而職水_(沖洗 :影處理後，麟水滿意地衫且移除過麵影劑，隨 後執行乾燥步驟。 此外，必要時，在執行遮光塗層形成製程、曝光 及顯影製程後，製造方法可更包含藉由加熱（亦即後供烤） 及/或曝光使所形成之遮光膜（亦即遮光圖案）固化之步驟。 後烘烤為出於完全固化之目的，在顯影後執行之加熱 ，理，且—般為在loot至250〇c下進行之熱固化處理。^ 供，之條件（諸如溫度及時間） 可視基板10或透鏡_12之 材料而適當設定。舉例而言，當基板12為玻璃時，後離 ▲度較佳為180。(：至240。(：。 、每由顯影形成之遮光膜14的後烘烤處理可在連續系 84 201237555 39636pif 統或分批系統中使用加熱設備（諸如熱板、對流烘箱（熱 空氣循環乾燥器）或射頻加熱設備）在上述條件下執行。 在上述程序中，描述透鏡12具有凹面形狀之實施例。 然而’透鏡之形狀並非特別限制於此，且透鏡可具有凸面 或非球面表面。另外，在上述程序中，描述在基板1〇之一 側形成多個透鏡12之晶圓級透鏡的實施例。然而，本發明 之晶圓級透鏡可具有在基板1〇之兩側形成多個透鏡12的 組態，且在此情況下，在基板10之兩侧在除透鏡表面以外 之區域中形成遮光層14。 晶圓級透鏡之組態及製造（2) 圖6為顯示晶圓級透鏡陣列之另一組態實例的視圖。 圖6中所示之晶圓級透鏡陣列具有基板1〇及透鏡12 使用相同模製材料同時形成之組態（單片型）。 用於形成所述晶圓級透鏡陣列之模製材料的實例與 上述模製材料相同。在此實施例中，在基板1〇之一側（在 圖中為上侧）形成多個凹透鏡12，且在基板之另一側（在 圖中為下侧）形成多個凸透鏡2G。在基板1G之除透鏡表 面仏以外的區域中在上面形成多個凹透鏡12之侧形成圖 案化遮光膜14;卿在基板1G之表面及透鏡周邊部分⑶ 之表面上形成圖案化遮光膜14。作為用於 之圖案化方法，可使用上述任一方法。 疋兀 晶圓級透鏡之組態及製造（3 ) 下文將參看圖7A至圖7C及圖8A至圖犯描述晶圓 級透鏡陣列之另一組態實例及其製造程序。 85 201237555 ^yo^opn 在本文中，®I 7A至圖7C為顯示形成圖案化遮光膜 14之製程的另一實施例的示意圖。 此外，圖8A至圖8C為顯示在形成圖案化遮光膜14 後模製透鏡12之製程的示意圖。 在圖3至圖6中所示之晶圓級透鏡陣列的實施例中， 在上面已形成透鏡12之基板1〇上形成圖案化遮光膜14。 相比之下，在下述實施例中，首先在基板1〇上形成圖案化 遮光膜14，隨後在基板10上模製透鏡I〗。 形成遮光膜 首先，如圖7A所示，執行遮光塗層形成製程，盆中 於基板ίο上塗佈黑色可固化組成物以形成遮光塗層ma。 之後，使用熱板、烘箱或其類似物在5〇它至14〇。〇之 溫度下乾燥基板10上所塗佈之遮光塗層14A持續1〇秒至 300秒。黑色可固化組成物之乾膜厚度可根據所要效能（諸 如遮光特性）任意選擇，且在約αι微米至小於5〇微米之 範圍内。 ’ ” 隨後，如圖7Β所示，經由光罩70對遮光塗層形成製 程中所形成的遮光塗層14Α進行圖案曝光。光罩7〇具有 預定光罩圖案。 ~ 在此曝光步驟中，對遮光塗層14進行圖案曝光，從 而使遮光塗層14Α中僅經光照射之部分固化。在此實施例 中，使用特定光罩圖案，其使得能夠在遮光塗層14八之除 特定區域以外之區域中的部分中進行光照射，所述特定區 域在後續製程_模製透鏡12時充當透鏡12之透鏡孔隙82 201237555 39636pif Coating 14A is subjected to patternwise exposure. The sequential exposure of the pattern can be performed by scanning exposure, but as shown in Fig. 5B, exposure through the mask 70 having a predetermined mask pattern is preferred. In the exposure of this process, the coating 14A is exposed via a reticle having a predetermined reticle pattern to cure only the portion of the coating 14A that is irradiated with light. The surface of the lens peripheral portion 12b and the surface of the substrate 10 t present between the lenses 12 are irradiated with light through the reticle pattern using the reticle pattern. Therefore, only the light-shielding coating layer 14A existing in the region other than the lens surface 12a is cured by light irradiation, and the curing region forms the light-shielding film 14. As the radiation which can be used for exposure, ultraviolet rays such as g rays, h rays or i rays are preferably used. The radiation may be from a single wavelength source or may be from a source comprising all wavelengths, such as a high pressure mercury lamp. The developing process is followed by performing an alkali developing treatment (developing process), and the portion irradiated with the jade light (that is, the uncured portion of the light-shielding coating) is dissolved in the water test by the exposure period of 1 and is only retained by The part that is cured by light. When the exposed light-shielding coating 14A = day, as shown in FIG. 5B, only the light-shielding coating 14A, 14, 2, 2, which is formed on the lens surface 12a, is removed. The viewpoint of the possibility of forming a path contained in a cured light-shielding film under the test of a cured light-shielding film in other areas is impaired in peripheral light-emitting costs. 83 201237555 Machine-developed developer is preferably used. The alkali reagent used in the developer is an organic base reagent, such as ammonia water, ethylamine, organic base compound (also tetraammonium hydroxide, tetraethylammonium hydroxide, gallium: ethylamine, dimercaptoethanolamine, diazapine). Bicyclo-[5.4.0K7-ten-breaking.^, pyrrole, piperidine or 1,8-base reagent) 'such as sodium hydroxide, hydroxide: inorganic compound (ie no potassium). An aqueous alkali solution obtained by dilute hydrogen or sodium carbonate concentration in pure water is used as a developer. In the case of mass, it is generally 20 seconds to 90 seconds in the temperature range of 2 Torr to 耽. β When using a developer formed from an aqueous alkali solution, it is removed by the usual means, and then the water is _ (flushing: after the shadow treatment, Linshui satisfactorily and removes the masking agent, and then performs the drying step. If necessary, after performing the light-shielding coating forming process, the exposure and development process, the manufacturing method may further comprise curing the formed light-shielding film (ie, the light-shielding pattern) by heating (ie, baking) and/or exposure. Step. Post-baking is the heating performed after development for the purpose of complete curing, Generally, the heat curing treatment is performed at a temperature of 25 to 250 ° C. The conditions (such as temperature and time) can be appropriately set depending on the material of the substrate 10 or the lens _12. For example, when the substrate 12 is glass Preferably, the post-degree ▲ degree is 180. (: to 240. (:, each post-baking treatment of the light-shielding film 14 formed by development may use a heating device in the continuous system 84 201237555 39636pif system or a batch system (such as A hot plate, a convection oven (hot air circulation dryer) or a radio frequency heating device is performed under the above conditions. In the above procedure, an embodiment in which the lens 12 has a concave shape is described. However, the shape of the lens is not particularly limited thereto, and The lens may have a convex or aspherical surface. Further, in the above procedure, an embodiment in which a wafer level lens of a plurality of lenses 12 is formed on one side of the substrate 1 is described. However, the wafer level lens of the present invention may have A configuration of a plurality of lenses 12 is formed on both sides of the substrate 1 and, in this case, a light shielding layer 14 is formed on both sides of the substrate 10 in a region other than the lens surface. Configuration and System of Wafer Level Lenses (2) Fig. 6 is a view showing another configuration example of a wafer level lens array. The wafer level lens array shown in Fig. 6 has a configuration in which a substrate 1 and a lens 12 are simultaneously formed using the same molding material ( Monolithic type) An example of a molding material for forming the wafer level lens array is the same as the above molding material. In this embodiment, one side of the substrate 1 (upper side in the drawing) is formed. A plurality of concave lenses 12 are formed, and a plurality of convex lenses 2G are formed on the other side (lower side in the drawing) of the substrate. Patterning is formed on the side of the substrate 1G except for the surface of the lens except for the surface of the plurality of concave lenses 12 The light-shielding film 14 is formed with a patterned light-shielding film 14 on the surface of the substrate 1G and the surface of the lens peripheral portion (3). As the patterning method for use, any of the above methods can be used.组态 Configuration and Fabrication of Wafer Level Lens (3) Another configuration example of a wafer level lens array and its manufacturing procedure will be described below with reference to Figs. 7A to 7C and Fig. 8A to Fig. 8A. 85 201237555 ^yo^opn In this document, ® I 7A through 7C are schematic views showing another embodiment of a process for forming the patterned light-shielding film 14. In addition, FIGS. 8A to 8C are schematic views showing a process of molding the lens 12 after forming the patterned light shielding film 14. In the embodiment of the wafer level lens array shown in FIGS. 3 through 6, a patterned light shielding film 14 is formed on the substrate 1 on which the lens 12 has been formed. In contrast, in the following embodiments, the patterned light-shielding film 14 is first formed on the substrate 1 and then the lens I is molded on the substrate 10. Forming a light-shielding film First, as shown in Fig. 7A, a light-shielding coating forming process is performed in which a black curable composition is coated on a substrate to form a light-shielding coating ma. Thereafter, it is used at 5 Torr to 14 Torr using a hot plate, an oven or the like. The light-shielding coating 14A applied on the dried substrate 10 at a temperature of 〇 is continued for 1 second to 300 seconds. The dry film thickness of the black curable composition can be arbitrarily selected depending on the desired performance (e.g., light-shielding property), and is in the range of from about 1 μm to less than 5 μm. Then, as shown in FIG. 7A, the light-shielding coating 14A formed in the light-shielding coating forming process is patterned by the mask 70. The mask 7 has a predetermined mask pattern. ~ In this exposure step, The light-shielding coating 14 is patterned to expose a portion of the light-shielding coating 14 that is only irradiated with light. In this embodiment, a specific mask pattern is used, which enables the light-shielding coating 14 to be excluded from a specific region. Light is irradiated in a portion of the region that acts as a lens aperture of the lens 12 in the subsequent process_molding of the lens 12.

86 201237555 3y636pif 14a。以此方式，遮光塗層14A藉由光照射固化，除其中 成為透鏡12之透鏡孔隙14a之部分以外。可用於曝光讀 射線的實例難包含如上述程序巾之紫 線、h射線或i射線。 8 ^ 隨後，藉由執行鹼顯影處理（顯影製程），遮光塗層 =中僅對應於透鏡12之透鏡孔隙14a的區域經驗水溶i 洛離，所述區域為圖案曝光中遮光塗層14A之未固化區。 $時’如圖7C所示，除用於透鏡12之透鏡孔隙14&amp;之區 成==化遮光塗層14A保留於基板10上，從而形 例與劑之驗水溶液中之驗性試劑的實 乾燥隨後’在顯影處理後’洗務且移除過量顯影劑，繼而 在本發明之實施例中，在執行遮光塗層 行藉由上述後_ 形成透鏡 步驟隨後，描述在形成遮光臈14後執行的形成透鏡Η之 光乂圖二所示，使用分配器5〇於上面已形成圖宰化遮 先膜14之基板10上逐滴施加透鏡^ ⑽茶化遮 供透鏡之模製材料Μ以覆蓋對應於透===。提 ⑷的區域’且亦覆蓋遮光膜14中與孔隙相鄰之末^ 87 201237555. 在向基板10提供模製材料心，在基板^ 模製材料Μ之铺驗形錢鏡之模具 ^ 上，如圖8Β所示。模具80根據透鏡12之所要數 多個凹面部分82以轉移透鏡12之形狀。 具有 隨後，模具80壓向基板1〇上存在的 得模製材料Μ根據凹面部分之形狀變形。當模製材料^ 為熱固性樹脂或紫外線可固化翻旨時，在模具⑽壓向 材料Μ日料由自模具外部照射熱或紫外光使模製材料= 固化。86 201237555 3y636pif 14a. In this manner, the light-shielding coating 14A is cured by light irradiation, except that it becomes a portion of the lens aperture 14a of the lens 12. Examples that can be used to expose the reading radiation are difficult to include the purple line, h-ray or i-ray as described above. 8 ^ Subsequently, by performing an alkali development treatment (developing process), the area of the light-shielding coating=only corresponding to the lens aperture 14a of the lens 12 is empirically water-soluble, and the area is the light-shielding coating 14A in the pattern exposure. Curing zone. When the time is 'as shown in Fig. 7C, except for the lens aperture 14&amp; for the lens 12, the opaque coating layer 14A remains on the substrate 10, thereby realizing the test reagent in the aqueous solution of the form and the agent. Drying followed by 'cleaning after the development treatment' and removing excess developer, and then in the embodiment of the present invention, performing the light-shielding coating line by the above-described forming of the lens step, subsequently, the description is performed after the formation of the light-shielding layer 14 The light forming the lens is shown in FIG. 2, and the lens is applied to the substrate 10 on which the patterned film 14 has been formed by using a dispenser 5 to apply a lens to the lens. Corresponds to penetration ===. The region of (4) is also covered with the end of the light-shielding film 14 adjacent to the aperture. ^ 87 201237555. The core of the molding material is provided to the substrate 10, and on the mold of the substrate ^ molding material As shown in Figure 8Β. The mold 80 is in the shape of the transfer lens 12 in accordance with the plurality of concave portions 82 of the lens 12. Then, the mold material 80 is pressed against the substrate 1 to be deformed by the shape of the concave portion. When the molding material is a thermosetting resin or an ultraviolet curable, the molding material is cured by irradiating heat or ultraviolet light from the outside of the mold to the material (10).

模製材料Μ固化後，使基板10及透鏡12自模具8C 釋放，從而獲得基板U)上包含圖案化遮光膜14之晶圓級 透鏡陣列，如圖8C所示。 如上所述，晶圓級透鏡中包含的圖案化遮光膜14不 僅如圖5A至圖5C所示在除透鏡12之透鏡表面仏以外 的區域中形成’而且如圖8C所示遮光膜14可在除透鏡I) 之透鏡孔隙14a以外的區域中提供。 因為晶圓級透鏡具有光反射率低且在基板1〇之至少 一側上逐次圖案形成之遮光膜14，故當在除透鏡12之透 f表面12a或透鏡孔隙14a以外的區域中光經充分遮蔽時 可抑制反射光產生。因此，當所述晶圓級透鏡施加於具有 固體成像裝置之成像模組時，可防止諸如在成像期間由反 射光所致之疊影或閃光的缺陷。 另外’因為在基板表面上提供遮光膜14,故其他遮光 構件無需置於晶圓級透鏡中，且可抑制製造成本增加。 .Q 、 88 201237555 39636pif f1上述國際巾♦公開案第WO 2GG8/1G2648號中所述 二、且L中田圍繞透鏡之表面具有凹面及凸面結構時，結 上之入射光反射或擴散，因此存在發生諸如疊影之缺陷 、風險:尤此而5 ’如圖5A至圖5C所示，當在除透鏡 =之透鏡表面12a以外之區域中提供圖案化遮光膜14 日、’在除透鏡表面12a卩外之其他區域中光經遮蔽，且可 改良光學效能。 實例 ，在下文中，在不背離本發明之精神的情況下，參考實 例詳細描述本發明，但本發明並不限於以下實例。此外， 除非另外規定，否則「％」及「份數」以質量計。 製備鈦黑分散液（TB-1分散液） 使用雙滾筒對以下組成物I中所示之組分進行高黏度 分散處理，從而獲得分散液。此分散液之黏度為4〇 〇〇〇毫 帕·秒。 此外，在高黏度分散處理前可使用捏合機捏合組分3〇 分鐘。 (組成物I) .平均一次粒徑為75奈米之鈦黑13 M-C(由三菱材料 電子化學株式會杜（Mitsubishi Materials Electronic Chemicals Co” Ltd.)製造）（顏料黑 35 ) 4〇 份 •甲基丙烯酸苯曱酯（BzMA) /曱基丙烯酸（MAA) 共聚物（BzMA/MAA = 60/40 (莫耳比），Mw : 30,000，固 體含量：40質量％)之丙二醇單曱醚乙酸酯溶液 8份 89 201237555 jyo^opu .索斯帕思5000 (由路博潤公司（The Lubriz〇i Corporation)製造） “ 2份 向由此獲得之分散液中添加以下組成物π中所示之 組分’繼而使用均質器在3,000轉/分鐘之條件下_ 3小 時三使用分散n (商標名：迪普馬特（dispermat)，由 格次曼公司（Getzmann)製造）彻直徑為Q 3毫米之氧 化錯珠粒對φ此麟之混合騎進行精細分散處理4小 時，從而獲得鈦黑分散液（下文表示為分散液）。 TB-1分散液之黏度為6.8毫帕.秒。 (組成物II) .甲基丙烯酸苯曱酯（BzMA) /甲基丙烯酸（Maa) 共聚物（BzMA/MAA = 70/30 (莫耳比），偷：3〇，_，固 體含量：40質量％)之丙二醇單曱醚乙酸酯溶液忉份 •丙二醇單曱醚乙酸酯 2〇〇份 製備鈦黑分散液（TB-2分散液） 使用雙滾筒對以下組成物III中所示之組分進行高黏 度分散處理，從而獲得分散液。此分散液之黏度為4〇,〇〇〇 毫帕·秒。 此外，在高黏度分散處理前可使用捏合機捏合組分3〇 分鐘。 (組成物III) .平均一次粒徑為40奈米之鈦黑（由三菱材料電子化 子株式會社（Mitsubishi Materials Electronic Chemicals Co. 40份After the molding material is cured, the substrate 10 and the lens 12 are released from the mold 8C, thereby obtaining a wafer-level lens array including the patterned light-shielding film 14 on the substrate U), as shown in Fig. 8C. As described above, the patterned light-shielding film 14 included in the wafer-level lens is formed not only in the region other than the lens surface 仏 of the lens 12 as shown in FIGS. 5A to 5C but also the light-shielding film 14 can be as shown in FIG. 8C. Provided in a region other than the lens aperture 14a of the lens I). Since the wafer level lens has the light-shielding film 14 which is low in light reflectivity and sequentially patterned on at least one side of the substrate 1 ,, when the light-transmissive film 14 is removed in the region other than the transmissive surface 12a or the lens aperture 14a of the lens 12 The generation of reflected light can be suppressed during shadowing. Therefore, when the wafer level lens is applied to an imaging module having a solid-state imaging device, defects such as ghosting or flashing caused by reflected light during imaging can be prevented. Further, since the light shielding film 14 is provided on the surface of the substrate, other light shielding members need not be placed in the wafer level lens, and an increase in manufacturing cost can be suppressed. .Q, 88 201237555 39636pif f1 The above-mentioned international towel ♦ Publication No. WO 2GG8/1G2648, and the surface of the L-field has a concave and convex structure around the surface of the lens, and the incident light on the junction is reflected or diffused, so that it occurs. Defects such as ghosting, risk: in particular, 5', as shown in Figs. 5A to 5C, when the patterning light-shielding film 14 is provided in a region other than the lens surface 12a of the lens =, 'on the lens surface 12a' Light is shielded in other areas and the optical performance is improved. In the following, the invention will be described in detail with reference to examples without departing from the spirit of the invention, but the invention is not limited to the following examples. In addition, "%" and "parts" are by mass unless otherwise stated. Preparation of Titanium Black Dispersion (TB-1 Dispersion) The components shown in the following Composition I were subjected to high viscosity dispersion treatment using a double cylinder to obtain a dispersion. The viscosity of this dispersion was 4 〇 MPa. Further, the component may be kneaded using a kneader for 3 minutes before the high viscosity dispersion treatment. (Composition I). Titanium black 13 MC having an average primary particle diameter of 75 nm (manufactured by Mitsubishi Materials Electronic Chemicals Co. Ltd.) (Pigment Black 35) 4 〇 part • A Benzoyl methacrylate (BzMA) / mercaptoacrylic acid (MAA) copolymer (BzMA / MAA = 60 / 40 (mole ratio), Mw: 30,000, solid content: 40% by mass) of propylene glycol monoterpene ether acetate Solution 8 parts 89 201237555 jyo^opu . Sospers 5000 (manufactured by The Lubriz〇i Corporation) "2 parts added to the dispersion thus obtained, the group shown in the following composition π In turn, use a homogenizer at 3,000 rpm. _ 3 hours 3 use dispersion n (trade name: dispermat, manufactured by Getzmann) with a diameter of 3 mm The oxidized wrong beads were subjected to fine dispersion treatment for a mixed ride of φ this lining for 4 hours to obtain a titanium black dispersion (hereinafter referred to as a dispersion). The viscosity of the TB-1 dispersion was 6.8 mPa.s. (Composition II) . Phenyl methacrylate (BzMA) / methacrylic acid (Maa) copolymer (BzMA / MAA = 70/30 (Morbi), steal: 3 〇, _, solid content: 40 mass %) propylene glycol monoterpene ether acetate solution • propylene glycol monoterpene ether acetate 2 制备 part preparation titanium black dispersion (TB-2 dispersion) using a double roller pair of the group shown in the following composition III The dispersion was subjected to high viscosity dispersion treatment to obtain a dispersion. The viscosity of this dispersion was 4 〇, 毫 mPa·s. Further, the component may be kneaded using a kneader for 3 minutes before the high viscosity dispersion treatment. (Composition III). Titanium black having an average primary particle diameter of 40 nm (by Mitsubishi Materials Electronic Chemicals Co. 40)

Ltd.)製造） ’ 201237555 39636pif 化5物72 5份 β由此獲件之分散液中添加以下组成物IV中所示之 組分’繼而使用均質ϋ在3，_轉/分鐘之條件下攪拌3小 時十使用分散器（商標名：迪普馬特⑽弧應⑷，由 格茨曼公司（Getzmann)製造）利用直徑為G3毫米之氧 粒對由祕狀混合溶㈣行精細分散處理4小 日、彳火而獲得鈦黑分散液（下文表示為TB-2分散液）。 TB-2分散液之黏度為6.8亳帕.秒。 (組成物IV) •例示性化合物72 •丙二醇單曱醚乙酸酯Ltd.) Manufactured] '201237555 39636pif 5 Articles 72 5 parts of β The component shown in the following composition IV was added to the dispersion of the obtained part, and then the mixture was stirred under conditions of 3, _ rpm. 3-hour ten-use disperser (trade name: Dipmat (10) arc should be (4), manufactured by Getzmann) using a particle size of G3 mm to prepare a fine dispersion of the secret mixture (four) A titanium black dispersion (hereinafter referred to as a TB-2 dispersion) was obtained by day and bonfire. The viscosity of the TB-2 dispersion was 6.8 kPa. (Composition IV) • Exemplary Compound 72 • Propylene glycol monoterpene ether acetate

5份 200份5 servings of 200 servings

$0重量％$0% by weight

合成例示性化合物72之方法 例示性化合物72可根據jp_A第2〇1〇1〇6268號之第 [0338]段至第[0340]段中所述之製備方法合成。 製備奴黑分散液（CB分散液） 碳黑分散液（CB分散液）藉由用相同質量之碳黑（碳 黑MA-100 R，由二菱化學株式會社（腕—碰Chemical Corporation)製造）替代TB-1分散液之鈦黑獲得。 91 201237555, 製備銀錫分散液（ST分散液） 在維持在60。(：之溫度下將藉由使15公克錫膠體（平 均粒徑·· 20奈米，固體含量：2〇%，由住友大阪水泥株式 會社（Sumitomo 〇saka Cement Co” Ltd.)製造）、60 公克 銀膠體（平均粒徑：7奈米，固體含量：2〇重量％，由住 友大阪水泥株式會社（Sumit〇m〇 〇saka Cement c〇，Ltd.) 製造）及0.75公克聚乙烯吡咯啶酮溶解於1〇〇毫升水中而 獲得之溶液添加至2〇〇 mL純水中，從而獲得膠體溶液。 t隨後，在維持在6(TC之溫度下攪拌膠體溶液6〇分鐘， 繼=施加超音波5分鐘。隨後，藉由離d轉體溶液， 獲=具有25%固體含量之混合溶液。賴藉由冷魏燥法 乾燥混合液體，從而獲得粉末樣品。 / ^藉由用相同質量之由此獲得之粉末樣品替換TB-1分 散液^之鈦黑來獲得銀錫分散液（ST分散液）。 貫例1至實例5以及比較實例1及比較實例2 1.製備黑色可聚合組成物 使用授拌器混合以下組成物A_i之組分以製備實例1 至實例5以及比較實例1及比較實例2中所用的各里色可 聚合組成物。 …、巴] (組成物A-1) • (D)表1中所述之鹼溶性黏合劑聚合物 2 5份 • (C)可聚合化合物：二季戊四醇六丙烯酸酯2〇份 • (C)可聚合化合物：季戊四醇三丙烯酸酯丨〇份 • (B)表1中所述之聚合起始劑 二 92 201237555 39636pif •表1中所述之含有（A)黑色顏料之分散液24份 .丙二醇單甲醚乙酸酯 ⑺份 .環己酮 8^ 2.製造及評估遮光膜（遮光區） 藉由鉍塗於玻璃晶圓上塗覆如上獲得之各黑色可聚 合組成物，且於熱板上在12〇它之溫度下加熱2分鐘，從 而獲得黑色可聚合組成物塗層。 隨後’使用i射線步進器使由此獲得之塗層在5〇〇毫 焦/平方公分之量下曝光。 在23°C之溫度下’使用〇.3〇/0氫氧化四曱銨水溶液使 曝光後之塗層重複進行槳式顯影（paddle development)五 次，持續60秒。隨後，使用旋轉喷淋沖洗塗層且用純水進 一步洗滌，從而獲得圖案化遮光膜。 對於由此獲得之遮光膜圖案，使用光學顯微鏡確定當 發現曝光部分剝落時重複顯影之次數，且其結果顯示於表 1中。 當重複顯影次數為4次或超過4次時，估計輪顯影劑 抗性良好。 ^ 93 201237555 jyojopif 表1 分散液 (D)鹼溶性黏合劑 (B)聚合起始劑 顯影次數 實例1 TB-1 B-1 1-1 5 實例2 TB-2 B-2 1-1 5或超過5 實例3 TB-2 B-2 1-2 5或超過5 實例4 CB B-3 1-1 4 實例5 ST B-3 1-3 4 比較實例1 CB HB-1 1-1 2 比較實例2 CB HB-3 1-1 2 表1及表2中所述之化合物B-l至化合物B-3以及化 合物HB-1至化合物HB-3之結構如下所示。以下結構中組 成比率之數值表示結構單元之含量（質量％ (重量％))。 亦顯示聚合起始劑1-1至聚合起始劑1-3之結構。 B-3 (Mw 60t000) B-1 (Mw 100,000)Method of synthesizing exemplary compound 72 Exemplary compound 72 can be synthesized according to the preparation method described in paragraphs [0338] to [0340] of jp_A No. 2, 1 〇 1 〇 6268. Preparation of a black dispersion (CB dispersion) The carbon black dispersion (CB dispersion) is made of the same quality of carbon black (carbon black MA-100 R, manufactured by Mitsubishi Chemical Corporation (Watch-Chemical Corporation)) It is obtained by replacing titanium black of the TB-1 dispersion. 91 201237555, Preparation of silver tin dispersion (ST dispersion) maintained at 60. (: at a temperature of 15 g of tin colloid (average particle size · 20 nm, solid content: 2% by weight, manufactured by Sumitomo 〇saka Cement Co. Ltd.), 60 Glucose colloid (average particle size: 7 nm, solid content: 2% by weight, manufactured by Sumit〇m〇〇saka Cement c〇, Ltd.) and 0.75 g of polyvinylpyrrolidone The solution obtained by dissolving in 1 ml of water was added to 2 mL of pure water to obtain a colloidal solution. t Subsequently, the colloidal solution was stirred at a temperature of 6 (TC for 6 minutes, followed by application of ultrasonic waves). 5 minutes. Subsequently, by mixing the solution from d, a mixed solution having a solid content of 25% was obtained. The mixed liquid was dried by cold-wet drying method to obtain a powder sample. The obtained powder sample was replaced with titanium black of the TB-1 dispersion to obtain a silver tin dispersion (ST dispersion). Example 1 to Example 5 and Comparative Example 1 and Comparative Example 2 1. Preparation of a black polymerizable composition was used. The mixer mixes the components of the following composition A_i To prepare the respective color polymerizable compositions used in Examples 1 to 5 and Comparative Example 1 and Comparative Example 2, ..., bar] (composition A-1) • (D) the alkali-soluble bond described in Table 1. Polymer 2 5 parts • (C) polymerizable compound: dipentaerythritol hexaacrylate 2 parts • (C) polymerizable compound: pentaerythritol triacrylate oxime • (B) polymerization initiation as described in Table 1. Agent 2 92 201237555 39636pif • 24 parts dispersion containing (A) black pigment as described in Table 1. Propylene glycol monomethyl ether acetate (7) parts. Cyclohexanone 8^ 2. Manufacture and evaluation of light-shielding film (shading area) Each of the black polymerizable compositions obtained above was coated on a glass wafer by ruthenium coating and heated on a hot plate at a temperature of 12 Torr for 2 minutes to obtain a black polymerizable composition coating. The ray stepper exposes the coating thus obtained at an amount of 5 Å/60 cm. At a temperature of 23 ° C, the exposure is carried out using an aqueous solution of 〇.3〇/0 tetrahydric ammonium hydroxide. The coating was repeated for paddle development five times for 60 seconds. The spray coating was rinsed and further washed with pure water to obtain a patterned light-shielding film. For the light-shielding film pattern thus obtained, the number of times of repeated development when the exposed portion was peeled off was determined using an optical microscope, and the results are shown in the table. 1. When the number of times of repeated development is 4 or more times, it is estimated that the developer resistance is good. ^ 93 201237555 jyojopif Table 1 Dispersion (D) alkali-soluble binder (B) Polymerization initiator development times Example 1 TB-1 B-1 1-1 5 Example 2 TB-2 B-2 1-1 5 or more than 5 Example 3 TB-2 B-2 1-2 5 or more than 5 Example 4 CB B-3 1-1 4 Example 5 ST B-3 1-3 4 Comparative Example 1 CB HB-1 1-1 2 Comparative Example 2 CB HB-3 1-1 2 Compounds B1 to B-3 and compounds described in Tables 1 and 2 The structure of HB-1 to compound HB-3 is shown below. The numerical value of the composition ratio in the following structure indicates the content (% by mass) of the structural unit. The structure of the polymerization initiator 1-1 to the polymerization initiators 1-3 is also shown. B-3 (Mw 60t000) B-1 (Mw 100,000)

B-2 (Hw 75.000)B-2 (Hw 75.000)

ΟΟ

〇〇

OHOH

COOHCOOH

0^'CH3 coov 201237555 jywopif HB—1 陳 60,000)0^'CH3 coov 201237555 jywopif HB-1 Chen 60,000)

HB-2 (Mw 15,000)HB-2 (Mw 15,000)

HB-3 m 28,000)HB-3 m 28,000)

9595

201237555 Ji/〇J〇piI 聚合耜始劊201237555 Ji/〇J〇piI Aggregation start line

盤佳固OXE01 ^ 由巴斯夫公司（BASF Corporation)製造） 化合物1-2 化合物1-3Panjiagu OXE01 ^ manufactured by BASF Corporation Compound 1-2 Compound 1-3

盤佳固OXE02 ▼ $ j由巴斯夫公司（BASF Corporation)製造Panjiagu OXE02 ▼ $ j manufactured by BASF Corporation

α 盤佳固379 〇ν^* (由巴斯夫公司（BASF Corporation)锄冶、 如表1之結果所示，具有由本發明黑色可聚合組成物 &gt;成之遮光膜的晶圓級透鏡具有極佳鹼顯影劑抗性。 實例6至實例1〇及比較實例3 L製備黑色可聚合組成物 得實混合下述組成物A_2之岭，從而分別獲 至貫例1G及比較實例3之黑色可聚合組成 (組成物Α-2) • (D)表2中所述之驗溶性黏合劑聚合物25产 ，(二:聚合化合物:經丁二酸修飾之二醇六 .(C)可聚合化合物:季戊四醇三丙烯酸』::：α 盘 佳 佳 379 ^ ^ ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Alkali-developer resistance. Example 6 to Example 1 and Comparative Example 3 L. A black polymerizable composition was prepared and the following composition A_2 was mixed to obtain the black polymerizable composition of Example 1G and Comparative Example 3, respectively. (Composition Α-2) • (D) The test-solvent binder polymer 25 described in Table 2, (2: Polymer compound: diol modified with succinic acid 6. (C) Polymerizable compound: pentaerythritol Triacrylate 』:::

96 201237555 39636pif •3-甲基丙烯醯氧基丙基二曱氧基曱基矽烷〇丨份 • (B)表2中所述之聚合起始劑 〇 4份 .表1中所述之含有（A)黑色顏料之分散液24f= .丙二醇單曱醚乙酸酯96 201237555 39636pif • 3-Methyl propylene methoxy propyl di decyl decyl decane • • (B) The polymerization initiator described in Table 2 〇 4 parts. The content described in Table 1 ( A) Black pigment dispersion 24f = . Propylene glycol monoterpene ether acetate

川TO .環己調 8份 2.製造及評估遮光膜（遮光區） 米 光 於f璃，圓上塗佈以下組成物V至膜厚度為15微 ，且藉由高壓汞燈❹5G微米孔鮮騎贿逐次曝 ，得到50微米之圓柱直徑，從而形成具有⑽微米直押 之圓柱形孔的透明樹脂層。隨後，於熱板上在細。c之二 層5分鐘’從而獲得包含上‘ 之晶圓隨明樹脂層 獲侍之各黑色可聚合組成物且在12(TC If無2》鐘’從而獲得平均膜厚度為3微米之里色可聚 i、=面發現由此形成之黑色可聚合組成物層可在玻 二層之表面上均勻形成，甚至對於 合以層之⑽成紐鮮之孔部分彼此結 光罩使用為5g微米之遮光孔部分的 光量下自乂 物在以⑻毫焦/平方公分之曝 光，除孔聚合組成物層之頂部進行曝光。藉由曝 化，且孔n外之區域中的黑色可聚合組成物層固 孔化成區之黑色可聚合組成物層由於 97 201237555 ^^υ^υιμιι 固化狀態存在。 (組成物V) .曱基丙烯酸烯丙 70/30 ;Mw = 5〇,〇〇〇)曰甲基丙烯酸共聚物（莫耳比 ==心(。)一物);: .豔佳固〇XE-〇i f i C)可聚合化合物）1.〇份 1由^VSF公司（BASF)製造） 〇.3份 5份 0.3%氫氧化四曱銨水溶液使 衫持續60秒。隨後，使用旋 步洗滌，從而獲得圖案化遮 .丙二醇單甲醚乙酸酯 在23°C之溫度下，使用 曝光後之塗層重複進行槳式顯 轉噴淋沖洗塗層邱純水進一 光膜。 。估計顯影次 ，察到剝落時之《次數顯示於表2中 數愈高表日猶⑽彡敝性愈佳。 物顯影兩次， 「A」且發現 #外’使圓柱形透明樹脂層部分之殘餘 分別將未發現殘餘物之情況在表2中表示為 殘餘物之情況在表2中表示為「B」。 結果顯示於表2中。 98 201237555 39636pif 表2 分散液 〔D)鹼溶性黏合劑 、B)聚合起始劑 殘餘物 顯影次數 實例6 TB-1 B-1 1-1 A 5 實例7 TB-2 B-2 1-2 A 6或超過6 實例8 TB-2 B-2 1-3 A 6或超過6 實例9 CB B-3 1-2 A 4 實例10 ST B-3 1-1 A 3 比較實例3 CB HB-2 1-1 B 2 由上表2之結果顯而易見，在具有由本發明黑色可聚 合組成物形成之遮光膜的晶圓級透鏡中，非影像部分之殘 餘物量減少，且影像部分之剝落受到抑制，此意謂鹼顯影 劑抗性極佳。此外，發現本發明之黑色可聚合組成物能夠 被噴塗。 根據上述結果，發現本發明之黑色可聚合組成物具有 巧佳驗顯影劑抗性。亦發現提供—種能夠被喷塗之黑色可 ^^合組成物。 號併案第2__2251。°號及第 標4:月公開案、專利申請案及技術 同。月案域缺準經特定及個職明併人本案供參考相 【圖式簡單說明】 圓日級透鏡陣列之—實例的平面圖。 圖。圖為圖！所不晶圓級透鏡陣列沿線“所取之剖面 圖3 為顯示提供模製材料以於基板上形成透鏡之狀態 99 201237555 j^ojopn 的視圖。 程的if至圖扣為顯示使賴具於基板上形成透鏡之製 宰化物雜上面職透狀純上形成圖 案化遮核之製程的示賴。 〜取圆 圖6為顯示晶圓級透鏡陣列之一實例的視圖。 7A至圖7C為顯示形成遮光膜之製程之另一實施例 的不思圖。 圖8A至圖8C為顯示於具有圖案化遮光膜之基板上形 成透鏡之製程的示意圖。 【主要元件符號說明】 10:基板 U :透鏡/凹透鏡 12a ·透鏡表面 12b ·透鏡周邊部分 14 :遮光膜/圖案化遮光膜 14A :遮光塗層 14a :透鏡孔隙 20 :凸透鏡 50 :分配器 60 =模具 62 :凹面部分 70 :光罩 80 =模具 82 :凹面部分 Μ:模製材料川TO. Cyclohexane has 8 parts. 2. Manufacture and evaluation of light-shielding film (light-shielding area). The light is applied to the glass, and the following composition V is applied to the film thickness to 15 micrometers, and the high-pressure mercury lamp ❹ 5G micro hole is used for riding. The bribe was exposed one by one to obtain a cylindrical diameter of 50 microns, thereby forming a transparent resin layer having a cylindrical hole of (10) micrograms. Then, it is fine on the hot plate. The second layer of c is 5 minutes 'to obtain the black polymerizable composition containing the upper wafer with the clear resin layer and at 12 (TC If no 2 clock) to obtain an average film thickness of 3 micrometers It can be found that the black polymerizable composition layer thus formed can be uniformly formed on the surface of the glass layer, even for the hole portions of the layer (10) which are combined with each other, the photomask is used for 5g micron. The amount of light in the light-shielding portion is exposed to (8) mJ/cm 2 from the top of the hole-polymerized composition layer, and the black polymerizable composition layer in the region outside the hole n is exposed by exposure. The black polymerizable composition layer of the solidified region is present in the cured state of 97 201237555 ^^υ^υιμιι. (Composition V). Mercaptoacrylic acid allyl 70/30; Mw = 5〇, 〇〇〇) 曰 methyl Acrylic copolymer (Morby == heart (.) one);: Yanjiao 〇XE-〇ifi C) polymerizable compound) 1. 11 1 manufactured by ^SFSF (BASF) 〇.3 A portion of 5 parts of a 0.3% aqueous solution of tetraammonium hydroxide was used to hold the shirt for 60 seconds. Subsequently, spin-washing was used to obtain a patterned masking propylene glycol monomethyl ether acetate. At a temperature of 23 ° C, a paddle-type spray-spraying rinse coating of Qiu pure water into the film was repeated using the exposed coating. . Estimated development time, the number of times when peeling is observed is shown in Table 2. The higher the number, the better the 彡敝. The material was developed twice, and "A" was found and the residue of the portion of the cylindrical transparent resin layer was found to be the residue of the portion of the cylindrical transparent resin layer, and the case where the residue was not found in Table 2 as the residue is shown as "B" in Table 2. The results are shown in Table 2. 98 201237555 39636pif Table 2 Dispersion [D) Alkali-Soluble Binder, B) Polymerization Initiator Residue Development Times Example 6 TB-1 B-1 1-1 A 5 Example 7 TB-2 B-2 1-2 A 6 or more than 6 Examples 8 TB-2 B-2 1-3 A 6 or more 6 Examples 9 CB B-3 1-2 A 4 Example 10 ST B-3 1-1 A 3 Comparative Example 3 CB HB-2 1 -1 B 2 As apparent from the results of the above Table 2, in the wafer-level lens having the light-shielding film formed of the black polymerizable composition of the present invention, the amount of residue of the non-image portion is reduced, and the peeling of the image portion is suppressed, The alkali developer is excellent in resistance. Further, it was found that the black polymerizable composition of the present invention can be sprayed. From the above results, it was found that the black polymerizable composition of the present invention has a good developer resistance. It has also been found that a black composition that can be sprayed is provided. No. 2__2251. ° and the standard 4: monthly disclosure, patent application and technology. The case of the moon case is not specified by the specific and individual duties. The case is for reference. [Simplified illustration] Plane of the circle lens array. Figure. The picture is a picture! The non-wafer-level lens array along the line "takes the cross-sectional view of Figure 3 to provide a view of the molding material to form a lens on the substrate 99 201237555 j^ojopn. The if to buckle of the process is displayed on the substrate A process for forming a patterned nucleation on the surface of the lens is formed. The drawing is a view showing an example of a wafer level lens array. 7A to 7C are display formations. FIG. 8A to FIG. 8C are schematic views showing a process of forming a lens on a substrate having a patterned light-shielding film. [Description of Main Components] 10: Substrate U: Lens/ Concave lens 12a · Lens surface 12b · Lens peripheral portion 14 : Light shielding film / patterned light shielding film 14A : Light shielding coating 14a : Lens aperture 20 : Convex lens 50 : Dispenser 60 = Mold 62 : Concave portion 70 : Photomask 80 = Mold 82 : concave part Μ: molding material

100100

Claims (1)

^237555 39636pif 七、申讀專利範圍： 種黑色可聚合組成物，其包括： A)黑色材料； (色）聚合起始劑； (C)可聚合化合物；以及 合基H重量平均分子量為至少3M(K)且_具有可％ 备團之驗溶性黏合劑聚合物。 /、有了承 物，中請專利範圍第1項所述之黑色可聚合也成 ^中所述⑷黑色材料包括鈦黑。 ^且成 物，其=申請專利範圍帛1項所述之黑色可聚合組成 子量為所述（D)驗溶性黏合劑聚合物包括重量平均分 勒合^°^勿〇至1〇〇，_且側鏈具有可聚合基團之驗溶性 如申請專利範圍第1項所述之黑色可聚合組成 “用於形成晶圓級透鏡之遮光區。 5·如申請專利範圍第1項所述之黑色可聚合組成 物，其能夠被噴塗。 6. 如申請專利範圍第1項所述之黑色可聚合組成 其中所述黑色可聚合組成物中之總固體含量為20質量 二％質量%。 7. 妒申請專利範圍第1項所述之黑色可聚合組成 ，其中戶斤述（D)驗溶性黏合劑聚合物中所包含之所述 物嘴舍基團包括丙烯基、曱基丙稀基、苯乙稀基、烯丙基、 鱗胺基團、曱基丙烯醯胺基團、乙烯基或乙烯醚基。 101 201237555 =Μ請專利範圍第！ i勿’其中所述⑼鹼溶性黏合劑聚合物:成 色可聚合組成物之總固體含量計為5質量黑 =一種黑色造方法，所述方法包括：質置‘ 藉由嘴塗將如申請專利範圍第i項中任 :::合組成物塗覆於固體之表面上以斤= 成物層；以及 〇』不口組 向所形成之所述黑色可聚合組成物層施加能量以使 所形成之所述黑色可聚合組成物層固化。 10.如申請專利範圍第9項所述之黑色層製造方法， 其中所述固體之所述表面為晶圓級透鏡之周邊部分的表 面’且所述黑色層為在晶圓級透鏡之所述周邊部分中形成 的遮光區。 102^237555 39636pif VII. Application Patent Range: A black polymerizable composition comprising: A) a black material; a (color) polymerization initiator; (C) a polymerizable compound; and a base H weight average molecular weight of at least 3M (K) and _ have a testable binder polymer which can be prepared. /, With the material, the black polymerizable material described in the first item of the patent scope is also described in (4) The black material includes titanium black. ^, and the object of the patent, the black polymerizable component amount described in item 1 is (D) the test-soluble binder polymer includes a weight average of 2 ° ^ do not 〇 to 1 〇〇, And the side chain has a polymerizable group, and the black polymerizable composition as described in claim 1 is "a light-shielding region for forming a wafer-level lens. 5. As described in claim 1 A black polymerizable composition which can be sprayed. 6. The black polymerizable composition according to claim 1 wherein the total solid content of the black polymerizable composition is 20% by mass and 2.7% by mass. The black polymerizable composition described in claim 1 wherein the compound contained in the (D) gel-soluble binder polymer comprises a propylene group, a mercaptopropyl group, and a benzene group. Ethyl, allyl, quaternary amine group, mercapto acrylamide group, vinyl or vinyl ether group. 101 201237555 = 专利 patent scope! i not 'the one described therein (9) alkali soluble binder polymer : the total solid content of the color forming polymerizable composition is 5 mass = a method of making black, the method comprising: texture - by mouth coating, as in the scope of claim i::: the composition is applied to the surface of the solid to the mass of the layer; and The black layer manufacturing method is applied to the black polymerizable composition layer to form the black polymerizable composition layer, as described in claim 9. Wherein the surface of the solid is a surface of a peripheral portion of the wafer level lens and the black layer is a light blocking region formed in the peripheral portion of the wafer level lens.
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