TW201237551A - Polymerizable composition, and photosensitive layer, permanent pattern, wafer-level lens, solid-state imaging device and pattern forming method, each using the composition - Google Patents

Polymerizable composition, and photosensitive layer, permanent pattern, wafer-level lens, solid-state imaging device and pattern forming method, each using the composition Download PDF

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TW201237551A
TW201237551A TW100143976A TW100143976A TW201237551A TW 201237551 A TW201237551 A TW 201237551A TW 100143976 A TW100143976 A TW 100143976A TW 100143976 A TW100143976 A TW 100143976A TW 201237551 A TW201237551 A TW 201237551A
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compound
group
polymerizable composition
substrate
light
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TW100143976A
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Chinese (zh)
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TWI518451B (en
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Naotsugu Muro
Kimi Ikeda
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Fujifilm Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • 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
    • G03F7/0041—Photosensitive materials providing an etching agent upon exposure
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

There is provided a polymerizable composition exhibiting high light-blocking effect in the infrared region and high light transparency in the visible region and being capable of forming a pattern with excellent resolution by alkali development, and a photosensitive layer, a permanent pattern, a wafer-level lens, a solid-state imaging device and a pattern forming method, each using the composition; and the composition contains a polymerization initiator, a polymerizable compound, a tungsten compound, an alkali-soluble binder, and an inorganic filler.

Description

201237551 Λ J_/1.x 六 '發明說明： 【發明所屬之技術領域】 本發明是關於-種可聚合組成物，特別是關於一種適 用於形成阻焊劑（solder resist)之可聚合組成物，以及各 自使用所述組成物之感光層、永久圖案、晶圓級透鏡、固 態攝影元件及圖案形成方法。 【先前技術】 手機、數位相機、數位視訊、監視相機及其類似物中 所用之固態攝影元件（影像感測器）為—齡有使用半導 體元件製造技娜成之紐電_光電轉換元件。近年 來’隨著手機錄灿叙尺找„ 固態攝影元件。 ⑥狀、唯) 為縮小固態攝影元件，已提出一種應用貫通電極 th=gh-electrode )或薄化石夕晶圓之 ^辦·194396 (如本文所用之術m」意謂「未 薄化矽1Γ」）、可藉由拋光及藉此 ^ ^圓薄化’故波長為800奈 i^8〇〇t平之=之光易於透射，不過阻擔_奈米或低 之先===:固態攝影元件中所用 雍，日恭相料、“為奈米s i，200奈求之光起反 嫩娜品二 =超過_奈米之光的透明 元件具有以下組態:彩色濾光片以及透鏡鄰 近故置於光電二極體之—側；紅外截止滤光片（lnfraredcut 201237551 filter)存在於彩色濾光片或透鏡附近以截止波長為8〇〇奈 米至1，200奈米之光；以及金屬配線、阻焊劑及其類似物 存在於彩色濾光片之相對側。舉例而言，在許多情況下以 阻焊劑填充金屬配線之間的空間，但存在以下問題：無法 藉由阻焊劑截止諸如侵入手機、數位相機或其類似物内之 漏光的紅外光。為對付此問題，通常採用一種在不良於紅 外光擋光作用之阻焊劑之外侧上再設置紅外阻擋層紅外阻 擋層’從而確保紅外阻播作用（infrared_bi〇cking effect) 之技術。然而，阻焊劑上一般存在由配線或其類似物造成 之高度差且在具有高度差之基板表面上可能難以將紅外阻 擋層材料塗佈至均一厚度，其中高度差引起若薄的部分存 在’則會經此透射光之問題。 ❹ 為僅在所需部分設置紅外阻擋層，組成物較佳展現感 光性且具有藉由曝光來圖案化之光微影效能。具有光微影 效能之擋光性感光組成物包括使用LCD彩色濾光片之= 成所採用之碳黑的黑色抗蝕劑。碳黑在可見光區具有高擋 光巧用，但在紅外區展現低擋光作用，且當嘗試應用此^ 色抗颠劑作為阻焊劑時，若添加足夠大量之碳黑以確保在 紅外區中之所需擋光作用，則此舉會引起以下問題：可見 $區中之擒光作用變得過高；亦截止波長短於可見光區之 光（通常採用於成像且在曝光於高壓水銀燈、KrF、 或其類似物時使用）而導致敏感性降低，使得不可能^ 足夠的光固化性（light谓abi脚)；以及無法獲得極佳： 案，甚至是使用鹼性顯影劑之顯影步驟。 201237551 ~rw a a 上/ϋ ipq yr 外阻卿㈣糾設置紅 中，必須多次進行諸如塗佈、曝光、顯2阻指層之形成 驟，其導致製程朗且成錢冑 从加熱之步 且已賦予阻烊劑本身播光作用， 色著色劑、除黑色外之著色劑以及多 --2__257045)。然而，據滿足縣作 區中之擒光作用）與圖案可成形性之觀點來看寺=成物卜 由組合使用除黑色外之著色劑來保持低的黑 色者色劑含1，且所述含量實際上不足。 【發明内容】 此外 、 ㈤於在製造固態攝影元件之製程中由可見光感 測裔偵測半導縣板之位置之目的，經常在固態攝影元^ 之半導體基板的金屬配線以及阻焊劑側上之表面（亦即， 與彩色濾光片或透鏡相對之表面）上之預定位置設置突出 形式之對準標記。 在對紅外光缺乏擋光作用之阻焊劑之外側再設置紅 外阻擋層之上述組態的情況下，認為甚至當紅外阻擔層為 亦對可見光具有擋光作用之層時，此層之厚度無需為了紅 外阻擋之目的而如此大（因為紅外阻擋之目的可藉由較阻 焊層薄之膜達成），因此藉由可見光感測器進行之偵測並不 會面臨由紅外阻擋層覆蓋對準標記所引起之嚴重問題。然 而’尤其在如JP-A-2008-257045中，阻焊組成物含有黑色 201237551 著色劑以職予阻焊劑本身擋光作用之組態中，當可能由於 阻焊層之厚度而使阻烊層覆蓋對準標記時，易於更經常地 出現可見光感測器未偵測到對準標記之問題。 在這些情況下，目前需要確保紅外區中高擋光作用以 ' 及可見光區中高透光度且能夠藉由鹼性顯影形成極佳圖荦 之可聚合組成物。 八 附帶而言，JP-A-2009-205029揭露一種使用含無機近 紅外吸收劑之層作為影像顯示元件之近紅外吸收層的技 術，且在其工作實例中描述了例如含有可聚合化合物、聚 合起始劑以及近紅外吸收劑之用於近紅外吸收層形成之塗 佈溶液。 此外’ JP-A-2006_201463揭露一種使用含近紅外吸收 劑之層作為抗反射膜中之高折射率層的技術，且在其工作 實例中描述了例如含有活性能量射線可固化化合物、聚合 起始劑以及近紅外吸收劑之用於硬塗層形成之塗佈溶液。 然而，獲自這些塗佈溶液之層不經受經由曝光以及鹼 〇 性顯影進行之圖案形成。實際上，這一層（甚至在未曝光 區域中）對於鹼性顯影劑為溶解度不足且實質上不具有鹼 可顯影性。 ' 本發明已在考慮到這些當前情況下進行，且本發明之 任務在於解決彼等習知之各種問題且達成以下目標。 一亦即，本發明之一個目標在於提供在紅外區展現高擋 光作用且在可見光區展現高透光度且能夠藉由驗性顯影形 成具有極佳解析度之圖案的可聚合組成物，以及各自使用 7 201237551 所述組成物之感光層、永久圖案、晶圓級透鏡、固態攝影 元件及圖案形成方法。 本發明之另一目標在於提供一種可聚合組成物，所述 可聚合組成物確保當上方設置感光層之基板具有不均勻形 狀時’可形成具有成功地追蹤（follow)基板不均勻形狀 之形狀的感光層，以及各自使用所述組成物之感光層、永 久圖案、晶圓級透鏡、固態攝影元件及圖案形成方法。 本發明具有以下組態，且上述目標可藉由這些組態達 成。 (1) 一種可聚合組成物，其包括： 聚合起始劑、 可聚合化合物、 鶴化合物、 驗溶性黏合劑，以及 無機填料。 ⑵如上文（1)中所述之可聚合組成物，其中無機 填料為二氧化矽。 中⑺中所述之可聚合組成物’其 物 物 (4)如上文⑴至（3)中任一項所述之可聚合組成 其中酸基為紛經基或硫醇基。 項所述之可聚合組成 (6)如上文⑴至（5)中任1所述之可聚合組成 201237551 物，其中聚合起始劑為苯乙酮類化合物且可聚合組成物更 含有敏化劑（sensitizer)。 (7)如上文（1)至（6)中任一項所述之可聚合組成 物，其中鎢化合物由以下式（I)表示：201237551 Λ J_/1.x VI' invention description: [Technical field of the invention] The present invention relates to a polymerizable composition, and more particularly to a polymerizable composition suitable for forming a solder resist, and A photosensitive layer, a permanent pattern, a wafer level lens, a solid-state photographic element, and a pattern forming method of the composition are each used. [Prior Art] Solid-state photographic elements (image sensors) used in mobile phones, digital cameras, digital video cameras, surveillance cameras, and the like are manufactured by using a semiconductor element to generate a photo-electrical conversion element. In recent years, 'with the mobile phone recording can find „ solid-state photographic components. 6 shape, only) In order to reduce the solid-state photographic components, an application has been proposed to penetrate the electrode th=gh-electrode) or to thin the stone wafers of the 194396 (As used herein, m means "not thinned 矽 1"), can be polished and thinned by ^ ^, so the wavelength is 800 奈 i ^ 8 〇〇 t flat = light is easy to transmit , but the resistance _ nano or low first ===: used in solid-state photographic components, the same day, "for nano-si, 200 negotiable light from the anti-Nen Na 2 = more than _ nano The transparent component of the light has the following configuration: the color filter and the lens are disposed adjacent to the side of the photodiode; the infrared cut filter (Infraredcut 201237551 filter) exists near the color filter or the lens at a cutoff wavelength of 8 〇〇 nanometer to 1,200 nm light; and metal wiring, solder resist, and the like exist on the opposite side of the color filter. For example, in many cases, the metal wiring is filled with a solder resist Space, but the following problems: unable to pass the solder resist cutoff such as intrusion Light leakage in the machine, digital camera or the like. To deal with this problem, an infrared blocking layer infrared blocking layer is usually disposed on the outer side of the solder resist which is inferior to the infrared light blocking function to ensure infrared resistance. The technique of infrared_bi〇cking effect. However, there is generally a difference in height caused by wiring or the like on the solder resist and it may be difficult to apply the infrared barrier layer material to a uniform thickness on the surface of the substrate having the height difference, Where the height difference causes a thin portion to present a problem of transmitted light. ❹ In order to provide an infrared blocking layer only in a desired portion, the composition preferably exhibits photosensitivity and has a light lithography patterned by exposure. Performance. The light-blocking photosensitive composition with photolithographic performance includes a black resist using the LCD color filter = carbon black used. The carbon black has high light blocking in the visible light region, but in the infrared The area exhibits a low light blocking effect, and when attempting to apply this color resist as a solder resist, if a sufficient amount of carbon black is added to ensure the desired block in the infrared region Light action, this will cause the following problems: the visible light in the $ zone becomes too high; also the cut-off wavelength is shorter than the visible light (usually used for imaging and exposure to high-pressure mercury lamps, KrF, or the like) When used, it causes a decrease in sensitivity, making it impossible to have sufficient photocurability (light is abi foot); and it is not possible to obtain an excellent: case, even a development step using an alkaline developer. 201237551 ~rw aa /ϋ ipq yr External resistance (4) Correction of red, must be repeated for many times such as coating, exposure, display of the formation of the barrier layer, which leads to the process and the money from the heating step and has been given a barrier agent It has its own sowing effect, coloring agent, coloring agent other than black and multi--2__257045). However, from the viewpoint of satisfying the glare effect in the county area and the pattern formability, the temple is formed by using a colorant other than black to keep the black toner containing 1 and the said The content is actually insufficient. SUMMARY OF THE INVENTION In addition, (5) in the process of manufacturing a solid-state photographic element, the purpose of detecting the position of the semi-conducting plate by the visible light sensing person is often on the metal wiring of the semiconductor substrate of the solid-state imaging device and the solder resist side. A predetermined position on the surface (i.e., the surface opposite the color filter or lens) is provided with an alignment mark of the protruding form. In the case of the above configuration of the infrared blocking layer on the outer side of the solder resist which lacks the light blocking effect of the infrared light, it is considered that when the infrared resistive layer is a layer which also blocks the visible light, the thickness of the layer does not need to be It is so large for the purpose of infrared blocking (because the purpose of infrared blocking can be achieved by a thin film with a solder mask), the detection by the visible light sensor does not face the alignment mark covered by the infrared blocking layer. Serious problems caused. However, in particular, as in JP-A-2008-257045, the solder resist composition contains a black 201237551 colorant in the configuration of the solder resist itself, and the barrier layer may be formed due to the thickness of the solder resist layer. When the alignment mark is covered, it is easy to occur more frequently that the visible light sensor does not detect the alignment mark. Under these circumstances, it is currently required to ensure a high light blocking effect in the infrared region and a polymerizable composition which is highly transparent in the visible light region and which can form an excellent pattern by alkaline development. In addition, JP-A-2009-205029 discloses a technique of using a layer containing an inorganic near-infrared absorbing agent as a near-infrared absorbing layer of an image display element, and in its working example, for example, a polymerizable compound is contained, and polymerization is described. A coating solution for forming a near-infrared absorbing layer of a starter and a near-infrared absorbing agent. Further, JP-A-2006_201463 discloses a technique of using a layer containing a near-infrared absorbing agent as a high refractive index layer in an antireflection film, and in its working example, for example, an active energy ray-curable compound, polymerization initiation is described. And a coating solution for forming a hard coat layer of a near-infrared absorbing agent. However, the layers obtained from these coating solutions were not subjected to pattern formation by exposure and alkali development. In fact, this layer (even in the unexposed areas) is insufficiently soluble for alkaline developers and has substantially no alkali developability. The present invention has been made in consideration of these current circumstances, and the object of the present invention is to solve various problems of the prior art and achieve the following objectives. That is, it is an object of the present invention to provide a polymerizable composition which exhibits a high light blocking effect in the infrared region and exhibits high light transmittance in the visible light region and which can form a pattern having excellent resolution by verifiable development, and Each of the photosensitive layer, the permanent pattern, the wafer level lens, the solid-state imaging element, and the pattern forming method of the composition described in 7 201237551 is used. Another object of the present invention is to provide a polymerizable composition which ensures that when a substrate having a photosensitive layer disposed thereon has an uneven shape, a shape having a shape in which a substrate uneven shape is successfully traced can be formed. A photosensitive layer, and a photosensitive layer, a permanent pattern, a wafer level lens, a solid-state photographic element, and a pattern forming method each using the composition. The present invention has the following configurations, and the above objects can be achieved by these configurations. (1) A polymerizable composition comprising: a polymerization initiator, a polymerizable compound, a crane compound, a test-soluble binder, and an inorganic filler. (2) A polymerizable composition as described in (1) above, wherein the inorganic filler is cerium oxide. The polymerizable composition as described in any one of the above (1) to (3) wherein the acid group is a thiol group or a thiol group. The polymerizable composition of any one of the above (1) to (5), wherein the polymerization initiator is an acetophenone compound and the polymerizable composition further contains a sensitizer. (sensitizer). (7) The polymerizable composition according to any one of (1) to (6) above, wherein the tungsten compound is represented by the following formula (I):

MxWyOz ( I ) Ο Ο 其中Μ表不金屬’ W表不鶴，〇表示氧， O.OOlSx/ySl.l，且 2-2Sz/y$3.〇。 (8 )如上文（7)中所述之可聚合組成物，1 %為 鹼金屬。 八 你（甘9i如上文（1)至（8)中任一項所述之可聚合組成 物’其巾可聚合化合物為在分子内具有多個可聚合基團之 多官能可聚合化合物。 土 成物(，^如上文⑴i (9)中任—項所述之可聚合組 成物，其用於阻焊劑。 賊、+、（11) 一種感光層，其由上文⑴至（10)中任一項 所返之可聚合組成物形成。 τ任項 項所迷之奸合_物形成。 η 案為L1:層如上文(12)中所述之永久圖案，其中永久圖 案為紅外吨膜文（12)巾所述之永久圖案，其中永久圖 (15)—種晶ϋ級魏，其具有魏以及在透 鏡之圓 201237551 周邊緣部分中形成之上文（12)中所述之永久圖案。 (16) 一種固態攝影元件，其具有上文（12)至（15) 中任一項所述之永久圖案。 (17) —種固態攝影元件，其包括： 一個表面上形成有攝影元件部分之固態攝影元件基 板，以及 没置於固態攝影元件基板之另一表面側之紅外阻擋 膜， 其中紅外阻擋膜為上文（12)中所述之永久圖案。 (18) —種圖案形成方法，其依序包括形成上文（^) 中所述之感光層的步驟、圖案逐次曝光（patternwise exposing)所述感光層以固化曝光區域之步驟以及藉由鹼 性顯影移除未曝光區域以形成永久圖案之步驟。 根據本發明，可提供在紅外區展現高擋光作用且在可 見光區展現尚透光度且能夠藉由驗性顯影形成具有極佳解 析度之圖案的可聚合組成物，以及各自使用所述組成物之 感光層、永久圖案、晶圓級透鏡、固態攝影元件及圖案形 成方法。 此外，根據本發明，可提供確保當上方設置感光層之 基板具有不均勻形狀時，可形成具有成功地追蹤基板不均 勻形狀之形狀之感光層的可聚合組成物，以及各自使用所 述組成物之感光層、永久圖案、晶圓級透鏡、固態攝影元 件及圖案形成方法。 【實施方式】 201237551 下文詳述本發明之可聚合組成物。 在本發明之說明書中，當在未指定經取代或未嶝取代 下指示基團（原子團）時，所述基團包括不具有取代基之 基團與具有取代基之基團。舉例而言，「烷基」不僅包括不 •具有取代基之烷基（未經取代之烷基），而且包括具有取代 基之烷基（經取代之烷基）。此外，在本發明之說明書中， 黏度值表示在25°C下之值。 曰 本發明之可t合組成物含有聚合起始劑、可聚合化合 物、鎢化合物、鹼溶性黏合劑以及無機填料，且必要時可 含有除上述鎢化合物之紅外阻擋材料、分散劑、敏化劑、 交聯劑、固化促進劑、彈性體（elastomer)、界面活性劑以 及其他組分。 本發明之可聚合組成物例如為負性組成物且通常為 負性抗蝕劑組成物。下文描述此組成物之組態。 下文可基於本發明之代表性實施例來描述構成要求 (constituent requirement)，但本發明不限於這些實施例。 〇 附帶而言，在本發明之說明書中，由「（數值）至（數值）」 表不之範圍意謂包括在「至」之前及之後的分別作為下限 以及上限之數值的範圍。 在本發明之說明書中，術語「（甲基）丙烯酸酯」表示 丙烯酸酯以及甲基丙烯酸酯，術語「（甲基）丙烯基」表示 丙烯基以及甲基丙烯基，且術語「（曱基）丙烯醯基」表示 丙稀醯基以及甲基丙烯醯基。此外，在本發明之說明書中， 「單體物質（mon〇meric substance )」具有與「單體 11 201237551 (monomer)」相同之含義。如本發明中所用之「單體」與 寡聚物以及聚合物有區別，且表示質量平均分子量為2,〇〇〇 或低於2,000之化合物。在本發明之說明書中，術語「可 聚合化合物（polymerizable compound)」表示具有可聚合 基團之化合物且可為單體或聚合物。術語「可聚合基團 表示參與聚合反應之基團。 -1 [1]聚合起始劑 適用於本發明之可聚合組成物的聚合起始劑不受特 別限制，但較佳為可光聚合化合物（photopolymerizable compound)。在藉由光起始聚合之情況下，對來自紫外區 至可見光區之光具有感光性之化合物為較佳。最重要的 是，最佳為苯乙酮類化合物且在此情況下，較佳為使用該 化合物與隨後所述之敏化劑的組合。 下文描述適於本發明之聚合起始劑之實例，但本發明 並不限於此。 苯乙酮類化合物的特定實例包括2,2_二乙氧基苯乙 酮、對二曱胺基苯乙酮、2-羥基-2-曱基-1-苯基-丙-1-酮、 對二曱胺基苯乙酮、4’-異丙基-2-羥基_2-甲基-苯丙酮、1-羥基-環己基-苯基-酮、2-苯甲基_2_二甲胺基-l-(4-(N-嗎啉 基）苯基)-丁-1-酮、2-甲苯基-2-二甲胺基-i-(4-(N-嗎啉基) 苯基)-丁-1-酮、2_曱基曱硫基)苯基嗎啉基)丙 -1·酮、2·曱基-1-(4_甲基噻吩基)_2_(N_嗎啉基）丙酮、2_ 本甲基_2·一甲胺基_1_(4_(N_嗎琳基)苯基)_丁小酮、2_(二甲 胺基)-2-[(4-曱基苯基）曱基嗎啉基）苯基p卜丁酮 12 201237551 以及2-曱基-l-(4_甲基嗟吩基)_2_(N_嗎琳基)丙小嗣。 其中，α-胺基苯乙酮類化合物為較佳，且2_甲基小(4_ 曱基嗟吩基)-2-(Ν-嗎淋基)丙_1_酮為更佳。 .胺基苯乙酮類化合物的商品包括例如IRGACURE 907、腦八⑶拙369以及IRGACURE奶（商標，均由 曰本巴斯夫（BASF Japan )製造）。 可單獨使用-種聚合起始劑，或可組合使用兩種或超 過兩種聚合起始劑。 以本發明之可聚合組成物的全部固體含量（質量） 计，聚合起始劑之含量較佳為〇 〇1質量％至3〇質量％，更 佳為0.1質置％至20質量％ ’更佳為〇丨質量％至15質量 %。 [2]可聚合化合物 本發明之可聚合組成物含有可聚合化合物。本文所用 之可聚合化合物可為任何化合物，只要其為在分子中具有 ，夠藉由酸、自由基以及熱中至少一者之作用經歷反應之 ❹ 冑能基（在本發明之說明書中，此官能基有時稱作「可聚 合基團」）的化合物即可，且在分子中具有多個可聚合基團 之多官能可聚合化合物為較佳。 具有能夠與酸、自由基以及熱中至少一者反應之可聚 合官能基且可較佳用於本發明之可聚合化合物的實例包括 含烯系不飽和基團之具有諸如不飽和酯官能基、不飽和醯 胺基、乙烯越基以及婦丙基之烯系不飽和基團的化合物，· 羥甲基化合物；雙順丁烯二醯亞胺化合物；苯并環丁烯化 13 201237551 TUJ L^yLL· 合物、雙稀丙基萘二醯亞胺化合物（bisaiiyina(jiimide compound);以及苯并噁嗪化合物。 可較佳用於本發明之可聚合化合物包括一般自由基 可聚合化合物’且可在無任何特定限制下使用此工業領域 中廣泛稱為具有烯系不飽和雙鍵之化合物的化合物。 這些化合物具有例如單體、預聚物（亦即二聚體、三 聚體或养聚物）或其混合物或其共聚物之化學形式。 單體以及其共聚物之實例包括不飽和羧酸（諸如丙烯 酸、曱基丙烯酸、衣康酸'丁烯酸、異丁烯酸以及順丁烯 二酸）、其酯以及醯胺，以及其共聚物。較佳為使用不飽和 羧酸酯、不飽和缓酸之酯以及脂族多元醇化合物以及不飽 和羧酸之醯胺以及脂族多價胺基化合物。 特定言之，不飽和羧酸之酯以及脂族多元醇化合物可 在曝光區域產生高疏水性，且因為可藉由鹼性顯影輕易形 成具有所需輪廓（profile)之圖案，而且獲得具有高耐久 性之圖案（特定言之，當要求阻焊劑具有較高耐久性時， 例如當阻焊劑所覆蓋之金屬配線之配線密度較高時，上 作用顯著）而為較佳。 ^ =外，舉例而言，亦宜使用具有親核取代基（諸如羥 基、私基以及疏基）之不飽和叛酸酯或酿胺與單官能戋多 官能異氰酸酯或環氧樹脂的加成反應產物，以及與單宫= 或多官能羧酸之去水縮合反應產物。 此 具有親電子取代基（諸如異氰酸S旨基以及環氧基） 不飽和羧酸酯或醯胺與單官能或多官能醇、胺或硫^的^ 14 201237551 成反應產物’以及具有離去取代基（諸如鹵素基團以及曱 苯磺醯氧基）之不飽和羧酸酯或醯胺與單官能或多官能 醇、胺或硫醇之取代反應產物亦為較佳。作為另一實例， 亦可使用上述不飽和羧基酸經不飽和膦酸、苯乙烯或乙婦 醚置換之化合物。MxWyOz ( I ) Ο Ο where Μ is not metal ‘W is not a crane, 〇 indicates oxygen, O.OOlSx/ySl.l, and 2-2Sz/y$3.〇. (8) A polymerizable composition as described in (7) above, wherein 1% is an alkali metal. The polymerizable composition of any one of the above (1) to (8) wherein the towel polymerizable compound is a polyfunctional polymerizable compound having a plurality of polymerizable groups in the molecule. The polymerizable composition according to any one of the above items (1), which is used for a solder resist. Thieves, +, (11) A photosensitive layer which is obtained by (1) to (10) above Any of the returned polymerizable compositions are formed. τ any item of traits is formed. η Case is L1: layer as in the permanent pattern described in (12) above, wherein the permanent pattern is infrared ton film The permanent pattern described in the text (12), wherein the permanent pattern (15) - the seed crystal level Wei, which has Wei and the permanent pattern described in (12) above formed in the peripheral portion of the lens circle 201237551 (16) A solid-state photographic element having the permanent pattern according to any one of (12) to (15) above. (17) A solid-state photographic element comprising: a photographic element portion formed on a surface Solid-state photographic element substrate, and infrared blocking film not disposed on the other surface side of the solid-state photographic element substrate Wherein the infrared blocking film is the permanent pattern described in (12) above. (18) A pattern forming method comprising the steps of forming the photosensitive layer described in (^) above, and sequentially exposing the pattern ( Patternwise exposing) the step of curing the exposed areas by the photosensitive layer and the step of removing the unexposed areas by alkaline development to form a permanent pattern. According to the present invention, it is possible to provide a high light blocking effect in the infrared region and to exhibit in the visible light region. a polymerizable composition that is light transmissive and capable of forming a pattern having excellent resolution by inferior development, and a photosensitive layer, a permanent pattern, a wafer level lens, a solid-state photographic element, and a pattern forming each using the composition Further, according to the present invention, it is possible to provide a polymerizable composition capable of forming a photosensitive layer having a shape successfully tracking a non-uniform shape of a substrate when a substrate on which a photosensitive layer is disposed has an uneven shape, and each of which is used Photosensitive layer, permanent pattern, wafer level lens, solid state imaging element and pattern forming method of composition. [Embodiment] 201237551 The polymerizable composition of the present invention is described in detail. In the specification of the present invention, when a group (atomic group) is indicated under the unsubstituted or unsubstituted substitution, the group includes a group having no substituent and The group having a substituent. For example, the "alkyl group" includes not only an alkyl group having a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Further, in the specification of the present invention, the viscosity value indicates a value at 25 ° C. The composition of the present invention contains a polymerization initiator, a polymerizable compound, a tungsten compound, an alkali-soluble binder, and an inorganic filler. Further, if necessary, an infrared blocking material, a dispersing agent, a sensitizer, a crosslinking agent, a curing accelerator, an elastomer, an surfactant, and other components other than the above tungsten compound may be contained. The polymerizable composition of the present invention is, for example, a negative composition and is usually a negative resist composition. The configuration of this composition is described below. The constituent requirements may be described below based on representative embodiments of the present invention, but the present invention is not limited to the embodiments. Incidentally, in the specification of the present invention, the range from "(numerical) to (numerical)" means a range including the lower limit and the upper limit, respectively, before and after "to". In the specification of the present invention, the term "(meth) acrylate" means acrylate and methacrylate, and the term "(meth) propylene" means propylene and methacryl, and the term "(fluorenyl)" "Acryl fluorenyl" means acrylonitrile and methacryl fluorenyl. Further, in the specification of the present invention, "mon meric substance" has the same meaning as "monomer 11 201237551 (monomer)". The "monomer" as used in the present invention is distinguished from the oligomer and the polymer, and represents a compound having a mass average molecular weight of 2, 〇〇〇 or less than 2,000. In the specification of the present invention, the term "polymerizable compound" means a compound having a polymerizable group and may be a monomer or a polymer. The term "polymerizable group means a group which participates in the polymerization reaction. -1 [1] Polymerization initiator The polymerization initiator which is suitable for the polymerizable composition of the invention is not particularly limited, but is preferably a photopolymerizable compound. (photopolymerizable compound). In the case of photopolymerization, a compound having photosensitivity to light from the ultraviolet region to the visible region is preferred. Most importantly, it is preferably an acetophenone compound and is here. In the case, it is preferred to use a combination of the compound and a sensitizer described later. Examples of the polymerization initiator suitable for the present invention are described below, but the present invention is not limited thereto. Specific examples of the acetophenone compound Including 2,2-diethoxyacetophenone, p-diamylacetophenone, 2-hydroxy-2-mercapto-1-phenyl-propan-1-one, p-dianonylacetophenone , 4'-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-one, 2-benzyl-2 dimethylamino-l-(4- (N-morpholinyl)phenyl)-butan-1-one, 2-tolyl-2-dimethylamino-i-(4-(N-morpholinyl)phenyl)-butan-1-one , 2_fluorenylthio)phenylmorpholinyl)propan-1·one, 2 · Mercapto-1-(4-methylthienyl)_2_(N_morpholinyl)acetone, 2_benyl-2,monomethylamino-1_(4_(N_morphinyl)phenyl)_ Butanone, 2-((dimethylamino)-2-[(4-mercaptophenyl)indolylmorpholinyl)phenylpyrionone 12 201237551 and 2-mercapto-l-(4-methyl嗟 ) ) ) ) ) ) ) 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 嗣 嗣 嗣 嗣 嗣 嗣-Peperyl)propan-1-one is more preferred. Amino acetophenones include, for example, IRGACURE 907, Brain Eight (3) 拙 369, and IRGACURE Milk (trademarks, all manufactured by SFBASF Japan) The polymerization initiator may be used alone, or two or more polymerization initiators may be used in combination. The total amount of the polymerization initiator in the solid content (mass) of the polymerizable composition of the present invention. It is preferably from 1% by mass to 3% by mass, more preferably from 0.1% by mass to 20% by mass, more preferably from 〇丨% by mass to 15% by mass. [2] Polymerizable compound The polymerizable composition of the present invention Containing a polymerizable compound. The polymerizable compound used herein may be any The compound, as long as it is a ruthenium group which has a reaction in the molecule and which undergoes a reaction by at least one of an acid, a radical, and heat (in the specification of the present invention, the functional group is sometimes referred to as a "polymerizable group" The compound of the group ") is, and a polyfunctional polymerizable compound having a plurality of polymerizable groups in the molecule is preferred. Examples of the polymerizable compound having a polymerizable functional group capable of reacting with at least one of an acid, a radical, and heat, and preferably used in the present invention, include an ethylenically unsaturated group having, for example, an unsaturated ester functional group, a compound of a saturated amide group, an ethylene group and an ethylenically unsaturated group of a propyl group, a methylol compound; a bis-n-butenylene imine compound; a benzocyclobutene 13 201237551 TUJ L^yLL a compound, a bisaziiyina (jiimide compound), and a benzoxazine compound. The polymerizable compound which can be preferably used in the present invention includes a general radical polymerizable compound' Compounds widely known in the art as compounds having ethylenically unsaturated double bonds are used without any particular limitation. These compounds have, for example, monomers, prepolymers (i.e., dimers, trimers or oligomers). Or a chemical form of the mixture or copolymer thereof. Examples of the monomer and copolymer thereof include unsaturated carboxylic acids (such as acrylic acid, methacrylic acid, itaconic acid 'butenoic acid, methacrylic acid, and cis Oleic acid), its esters and decylamines, and copolymers thereof. It is preferred to use unsaturated carboxylic acid esters, unsaturated acid-lowering esters and aliphatic polyol compounds, and carboxylic amines of unsaturated carboxylic acids and aliphatic groups. Amine amine compounds. In particular, esters of unsaturated carboxylic acids and aliphatic polyol compounds can produce high hydrophobicity in exposed areas, and because patterns with desired profiles can be easily formed by alkaline development, Further, it is preferable to obtain a pattern having high durability (specifically, when a solder resist is required to have high durability, for example, when the wiring density of the metal wiring covered by the solder resist is high, the upper effect is remarkable). In addition, for example, it is also preferred to use an addition reaction product of an unsaturated tetamine or a captanamine having a nucleophilic substituent such as a hydroxyl group, a thiol group and a thiol group with a monofunctional fluorene polyfunctional isocyanate or epoxy resin. And a dehydration reaction product with a mono-; = or polyfunctional carboxylic acid. This has an electrophilic substituent (such as an isocyanate group and an epoxy group), an unsaturated carboxylic acid ester or a decylamine with a monofunctional or poly a functional alcohol, an amine or a sulphur; 14 201237551 to form a reaction product 'and an unsaturated carboxylic acid ester or a guanamine with a leaving substituent such as a halogen group and a fluorenyl sulfonyloxy group, and a monofunctional or polyfunctional alcohol A substituted reaction product of an amine or a thiol is also preferred. As another example, a compound in which the above unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, styrene or ethyl ether can also be used.

Ο 不飽和羧酸酯較佳為甲基丙烯酸酯，且其實例包括丁 二醇二甲基丙烯酸酯、三乙二醇二曱基丙烯酸酯、新戊二 醇二曱基丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、三羥 甲基乙烷二曱基丙烯酸酯、乙二醇二甲基丙烯酸酯、I〕· 丁二醇二曱基丙烯酸酯、己二醇二甲基丙烯酸酯、季戊四 醇二甲基丙烯酸酯、季戊四醇三曱基丙烯酸醋、季戊四醇 四甲基丙烯酸酯、二季戊四醇二曱基丙稀酸酷、二季戍四 醇六甲基丙烯酸S旨、山梨糖醇三甲基丙烯酸酯、山梨糖醇 四曱基丙烯酸醋、雙[對(3_甲基丙烯醯氧基_2_㈣氧基)苯 基]丙烧、雙[對（甲基丙婦醯氧基乙氧基)苯基]丙烧以及苴 EO( ethylene oxide)改質或 p〇(pr〇pylene〇xide)改質^ 產物。 、 不釔和羧駄ga亦較佳為衣康酸酯，且其 醇二衣康酸酯、丙二醇-衣唐酴_ ^ 】匕栝乙一 於+士 康酸旨、以丁二醇二衣康酸 動旨、丁二醇二衣康酸酿、季戊四 醉一衣康及山射轉四衣康_旨。 包括乙二，二丁賴、丁二醇二丁稀酸二:例 丁烯酸酯以及山梨糖醇四-二 早^四酵一 tetradicrotonate)。显丁烯萨萨 —夂曰（sorbitol ，、丁埽酸酯之實例包括乙二醇二異丁烯 15 201237551 異丁埽酸 ®曼酯、二 ·* 酯以及山 酸酯、季戊四醇二異丁烯酸酯以及山梨糖醇四 酯。順丁烯二酸酯之實例包括乙二醇二順丁稀_ 乙二醇二順丁烯二酸酯、季戊四醇二順丁烯二^ 梨糖醇四順丁烯二酸酯。 文 脂族多元醇化合物與不飽和羧酸之酯單 例包括乙二醇二丙烯酸醋、三乙二醇二丙婦實 二醇二丙烯酸酯、丁二醇二丙烯酸酯、丙二醇二^ ，3-丁 新戊二醇二丙烯酸醋、三羥甲基丙烷三丙烯心旨广 基丙烷三（丙烯醯基氧基丙基)醚、三羥曱基乙 一羥甲 酿、己二醇二丙_醋、己二醇二丙婦酸^丙= 亦丙烯酸醋、三環癸烷二甲醇二丙烯酸酿、三产 二曱醇二曱基丙稀酸si、季戊四醇二丙烯酸_ 三丙稀^旨、季細_丙烯_、二季戊 山梨糖醇三丙賊自旨、山籍曰五 基乙基)醋、聚醋丙稀酸醋寡聚物，以及這 改質或po改質之產物，作為（甲基)丙烯酸醋。 其中，二季戊四醇六丙婦酸醋以及三環癸烧二甲醇二 丙稀酸S旨為較佳，且三環癸烧二曱醇二丙烯酸g旨為更佳。 酉曰之其他較佳實例包括以及 JP-A-57-196231 +所述之脂族醇醋、Jp_A 5m奶、 JP-A-59-5241以及JP_A_2_226149中所述之具有芳族架構 的醋，以及JP-A-1-165613 +所述之具有胺基的酿。這些 16 201237551 醋單^亦可以混合物形式使用。 月曰麵多價胺化合物與不飽和羧酸之醯胺單體的特定 $例包括亞曱基雙丙烯醯胺、亞甲基雙甲基丙烯醯胺、1，6-八亞:基雙丙烯醯胺、丨，6-六亞曱基雙曱基丙烯醯胺、二 伸乙三，三丙烯醯胺、二甲苯雙丙烯醯胺以及二曱苯雙甲 基丙稀酸胺。醯胺類單體的其他較佳實例包括 JP-B-54-21726中所述之具有伸環己基結構的單體。 ❹ — > 藉由異氰酸酯與羥基之加成反應所製得的加成可聚 合氨基曱酸酯類（urethane-based)化合物亦為較佳，且其 对寸疋貝例包括母分子具有兩個或超過兩個可聚合乙稀基之 氨基甲酸乙烯酯化合物，其藉由將由以下式（E)表示之 含备基之乙烯系單體加成至每分子具有兩個或超過兩個異 氰酸醋基之聚異氰酸酯化合物來獲得（JP-B-48-41708中所 述）。 CH2=C(R4)COOCH2CH(R5)〇H (E) [其中R4以及R5各自獨立地表示η或CH3]。 〇 此外’JP_A_51-37193、JP-B-2-32293 以及 JP-B-2-16765 中所述之丙烯酸氨基曱酸酯，以及jp_B_58_4986〇、 P-B-56-17654、JP-B-62-39417 以及 JP-B-62-39418 中所述 之具有壞氧乙烧類架構的氨基曱酸g旨化合物亦為較佳。另 外’當使用 JP-A-63-277653、JP-A-63-260909 以及 JP-A-1-105238中所述之在分子中具有胺基結構或硫化物 結構之加成可聚合化合物時，可獲得感光性速度極佳之可· 光聚合組成物。 201237551 JP A 2貫例包括多官能丙婦酸醋或甲基丙烯酸酯，諸如 之聚μΓ3、】ρ_β_49-43191 以及 Jp_B-52_30490 中所述 歸酸醋，以及藉由環氧樹脂與(甲基)丙稀酸反應 =了之環氧丙烯_旨。其他實例亦包括τρ_Β_46·43946、 ==G337以及㈣小侧中所述之狀不飽和化合 -此样p士2-25493中所述之乙烯基膦酸類化合物。在 况下’宜使用；Ρ·Α_61·22()48巾所狀含全氟烧基 之…構。此外’亦可㈣日本接著學會諸UGUnlal of The AdheS10n Society 〇fJapan)，第 2〇 卷第 7 期第雙_細 頁（購4)中作為可光固化單體（ph〇t〇curablem_mer)以 及券聚物引入者。 在本發明中，當添加自由基可聚合化合物作為單體 時，較佳為使用含有2至6個烯系不飽和鍵之多官能可聚 合化合物，且其更佳為含有2至4個烯系不飽和鍵。最重 要的是，化合物較佳為含有兩個（曱基)丙烯酸酯結構。 除此之外，鑒於未曝光區域之固化敏感性以及可顯影 性’含有EO改質之產物的化合物為較佳，且鑒於曝光區 域之固化敏感性以及強度，較佳為使用含有胺基曱酸酯鍵 之化合物。另外，繁於圖案形成時之可顯影性，較佳為使 用具有酸基之化合物。 此外，具有酸基之稀系不飽和化合物亦為較佳，且其 市售產品之實例包括TO-756 ’其為東亞合成有限公司 (ToagoseiCo.，Ltd.)製造之含羧基之三官能丙烯酸酯，以 及TO-1382 ’其為含叛基之五官能（pentafuncti〇nai)丙缚 18 201237551 酸酯。 另外，高度财熱性可聚合化合物之實例包括苯并環丁 烯（BCB)、雙烯丙基萘二醯亞胺（BANI)、苯并噁嗪、三 聚氰胺以及其類似物。 可使用兩種或超過兩種化合物作為可聚合化合物。 以本發明之可聚合組成物的全部固體含量（質量） 計’可聚合化合物之含量較佳為3質量％至8〇質量％，更 佳為5質量％至50質量％。 附帶而言，可聚合化合物可與鹼溶性黏合劑相同或不 同。 更特定言之，在可聚合化合物為聚合物之情況下，可 聚合化合物可與隨後詳述之驗溶性黏合劑相同（亦即，可 聚合化合物與鹼溶性黏合劑可為相同組分）。在此實施例 中，以本發明之可聚合組成物的全部固體含量（質量）計， 可聚合化合物之含量較佳為3質量％至8〇質量％，更佳為 5質量％至60質量％。 ’ Ο [3]鶴化合物 本發明之可聚合組成物含有鶴化合物。 鎢化合物為紅外阻擋材料，其對紅外線（波長為約8〇〇 奈米至1，200奈米之光）展現高吸收（亦即，對紅外線之 擋光作用（遮蔽性質）較高）且對可見光展現低吸收。因 此:根據本發明之可聚合組成物，藉助於含有鎢化合物， 可形成在紅外區具有高擋光作用且在可見光區具有高透光 19 201237551 此外，鶴化合物對波長短於可見光區之光（用於成像 且在曝光於高壓水銀燈、KrF、ArF或其類似物時使用）展 現少吸收。因此，藉由組合鎢化合物與可聚合化合物以及 鹼溶性黏合劑’藉由鹼性顯影獲得具有極佳解析度之圖案。 鎢化合物包括例如氧化鎢類化合物、硼化鎢類化合物 以及硫化鎢類化合物，且較佳為由以下式（組成式）（工） 所表示之氧化鶴類化合物：The Ο unsaturated carboxylic acid ester is preferably a methacrylate, and examples thereof include butanediol dimethacrylate, triethylene glycol dimercapto acrylate, neopentyl glycol dimercapto acrylate, and trishydroxyl Propane trimethacrylate, trimethylolethane dimercapto acrylate, ethylene glycol dimethacrylate, I], butanediol dimercapto acrylate, hexanediol dimethacrylate, Pentaerythritol dimethacrylate, pentaerythritol tridecyl acrylate vinegar, pentaerythritol tetramethacrylate, dipentaerythritol dimercapto acrylate acid, diquaternary decyl alcohol hexamethacrylate S, sorbitol trimethacrylate , sorbitol tetradecyl acrylate vinegar, bis [p-(3-methylpropenyloxy-2-(tetra)oxy)phenyl]propanone, bis[p-(methyl propyl ethoxy ethoxy) phenyl) ] B-burning and 苴EO (ethylene oxide) modification or p〇(pr〇pylene〇xide) modification ^ product. , 钇 钇 駄 駄 駄 亦 亦 亦 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣Acidic purpose, butanediol, second itaconic acid, Jiwu four drunk one clothing Kang and Shantou four clothes Kang _ purpose. Including ethylene, dibutyl, butanediol dibutyl acid: an example of butenoate and sorbitol four-two early ^ four leave a tetradicrotonate). Examples of sorbitol, butyl phthalate include ethylene glycol diisobutylene 15 201237551 isobutyl phthalate® male ester, di-* ester and sorbate, pentaerythritol dimethacrylate and sorbus Examples of the tetraester of the sugar alcohol. Examples of the maleic acid ester include ethylene glycol di-butadiene-ethylene glycol dimaleate, pentaerythritol di-n-butyl sorbitol tetramaleate. Single examples of esters of a lipid polyol compound and an unsaturated carboxylic acid include ethylene glycol diacrylate vinegar, triethylene glycol dipropylene foscar diol diacrylate, butane diol diacrylate, propylene glycol bis, 3 - butyl neopentyl glycol diacrylate vinegar, trimethylolpropane tripropylene, the purpose of the broad-based propane tris(propylene decyloxypropyl) ether, trishydroxy thioglycolic acid, hexanediol dipropylene vinegar , hexanediol dipropylene acetoacetate ^ propylene = also acrylic vinegar, tricyclodecane dimethanol diacrylic acid brewing, trisyl didecyl dimercapto acrylic acid si, pentaerythritol diacrylic acid _ tripropylene thin, seasonal _ propylene _, two pentylene sorbitol tripropy thief from the purpose, mountain 曰 基 基 ) ) vinegar, vinegar vinegar It was modified, and this modified product of po or, as (meth) acrylic acid vinegar. Among them, dipentaerythritol hexa-propyl acetoacetate and tricycloanthracene dimethanol diacrylic acid S are preferred, and tricyclic fluorene diacetate diacrylate g is preferred. Other preferred examples of the oxime include the vinegar having an aromatic structure as described in JP-A-57-196231+, the aliphatic alcoholic vinegar described in JP-A-57-196231, Jp_A 5m milk, JP-A-59-5241, and JP_A_2_226149, and JP-A-1-165613 + described as having an amine group. These 16 201237551 vinegars can also be used in the form of a mixture. Specific examples of the ruthenium-faced polyvalent amine compound and the carboxylic acid monomer of the unsaturated carboxylic acid include fluorenylene bis acrylamide, methylene bis methacrylamide, 1,6- octa: bis propylene Indoleamine, hydrazine, 6-hexamethylene bis-mercapto acrylamide, diethylene glycol, tripropylene decylamine, xylene bis acrylamide, and dinonyl dimethyl methacrylate. Other preferred examples of the guanamine-based monomer include a monomer having a cyclohexylene structure as described in JP-B-54-21726. ❹ — > An addition polymerizable urethane-based compound prepared by an addition reaction of an isocyanate with a hydroxyl group is also preferred, and the parenteral molecule has two Or more than two polymerizable vinyl group vinyl carbamate compounds by adding a vinyl group-containing monomer represented by the following formula (E) to have two or more than two isocyanic groups per molecule A vinegar-based polyisocyanate compound is obtained (described in JP-B-48-41708). CH2=C(R4)COOCH2CH(R5)〇H (E) [wherein R4 and R5 each independently represent η or CH3]. Further, the urethane phthalate described in 'JP_A_51-37193, JP-B-2-32293, and JP-B-2-16765, and jp_B_58_4986〇, PB-56-17654, JP-B-62-39417, and The aminoguanidine acid-glysing compound having a bad oxygen-fired structure as described in JP-B-62-39418 is also preferred. In addition, when using an addition polymerizable compound having an amine structure or a sulfide structure in a molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, A photopolymerizable composition having excellent photosensitivity can be obtained. 201237551 JP A 2 examples include polyfunctional acetoacetate or methacrylate, such as poly sulfonate, ρ_β_49-43191 and Jp_B-52_30490, as well as acid vinegar, and by epoxy resin and (meth) The acrylic acid reaction = the epoxy propylene. Other examples also include τρ_Β_46·43946, ==G337, and (iv) the unsaturated combination described in the small side - the vinylphosphonic acid compound described in this type of p-2-25493. In the case of 'useful; Ρ·Α_61·22() 48 towel contains a perfluoroalkyl group. In addition, it can also be used as a photocurable monomer (ph〇t〇curablem_mer) and a voucher in the UGGlal of The AdheS10n Society 〇fJapan), the second volume of the second volume (purchase 4). Polymer introducer. In the present invention, when a radical polymerizable compound is added as a monomer, it is preferred to use a polyfunctional polymerizable compound having 2 to 6 ethylenically unsaturated bonds, and more preferably 2 to 4 olefinic groups. Unsaturated key. Most importantly, the compound preferably contains two (indenyl) acrylate structures. In addition, in view of the curing sensitivity of the unexposed regions and the developability of the compound containing the EO-modified product, and in view of the curing sensitivity and strength of the exposed region, it is preferred to use an amine-based citric acid. A compound of an ester bond. Further, in the case of developability at the time of pattern formation, it is preferred to use a compound having an acid group. Further, a rare unsaturated compound having an acid group is also preferable, and examples of the commercially available product thereof include TO-756 'which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd. , and TO-1382 'which is a pentafuncti〇nai cyanide 18 201237551 acid ester. Further, examples of the highly heat-generating polymerizable compound include benzocyclobutene (BCB), bisallyl naphthalene diimide (BANI), benzoxazine, melamine, and the like. Two or more than two compounds may be used as the polymerizable compound. The content of the polymerizable compound is preferably from 3% by mass to 8% by mass, more preferably from 5% by mass to 50% by mass based on the total solid content (mass) of the polymerizable composition of the present invention. Incidentally, the polymerizable compound may be the same as or different from the alkali-soluble binder. More specifically, in the case where the polymerizable compound is a polymer, the polymerizable compound may be the same as the test-solvent binder described later (i.e., the polymerizable compound and the alkali-soluble binder may be the same component). In this embodiment, the content of the polymerizable compound is preferably from 3% by mass to 8% by mass, more preferably from 5% by mass to 60% by mass based on the total solid content (mass) of the polymerizable composition of the present invention. . Ο [3] Crane compound The polymerizable composition of the present invention contains a crane compound. The tungsten compound is an infrared blocking material which exhibits high absorption to infrared rays (light having a wavelength of about 8 〇〇 to 1,200 nm) (that is, a light blocking effect (shielding property) for infrared rays) and Visible light exhibits low absorption. Therefore, the polymerizable composition according to the present invention, by containing a tungsten compound, can have a high light blocking effect in the infrared region and a high light transmission in the visible light region. 19 201237551 In addition, the crane compound has a wavelength shorter than the visible light region ( Used for imaging and when exposed to high pressure mercury lamps, KrF, ArF or the like) exhibits less absorption. Therefore, a pattern having excellent resolution is obtained by alkaline development by combining a tungsten compound with a polymerizable compound and an alkali-soluble binder. The tungsten compound includes, for example, a tungsten oxide compound, a tungsten boride compound, and a tungsten sulfide compound, and is preferably an oxidized crane compound represented by the following formula (composition formula):

MxWyOz (I) 其中Μ表示金屬，W表示鎢，〇表示氧， 0.001 苎x/yH，且 2.2$z/yS3.0。 金屬Μ包括鹼金屬、鹼土金屬、Mg、&、&、應、MxWyOz (I) where Μ represents metal, W represents tungsten, 〇 represents oxygen, 0.001 苎x/yH, and 2.2$z/yS3.0. Metal ruthenium includes alkali metal, alkaline earth metal, Mg, &, &

Fe、Ru、Co、Rh、ΙΓ、Ni、Pd、Pt、Cu、Ag、Au、Zn、 Cd、A卜 Ga、In、Ί1、Sn、Pb、Ti、Nb、V、Mo、Ta、Re、Fe, Ru, Co, Rh, yttrium, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Ab Ga, In, Ί1, Sn, Pb, Ti, Nb, V, Mo, Ta, Re,

Be、Hf、〇s以及Bi ’且較佳為驗金屬。金展m可為一種 金屬或兩種或超過兩種金屬。 Μ較佳為鹼金屬’更佳為Rb或Cs，更佳為Cs。 當x/y為0.001或超過0.001時，可充分阻擋紅外線， 且當其為1.1或低於1.1時，可較可靠地避免在鎢化合物 中產生雜質相。 當z/y為2.2或超過2.2時’作為材料之化學穩定性可 更加增強’且當其為3.0或低於3.0時，可充分阻擔紅外 線。 由式（I)表示之氧化鎢類化合物的特定實例包括 20 201237551 CS〇.33W03、Rb0.33W〇3、K〇 33W〇3 以及 Ba〇 33W〇3。化合物 較佳為 Cs〇_33W03 或 Rb033w〇3，更佳為 Cs〇33W〇3。 ΟBe, Hf, 〇s, and Bi' are preferably metal. The gold exhibition m can be one metal or two or more than two metals. Preferably, the hydrazine is more preferably Rb or Cs, more preferably Cs. When x/y is 0.001 or exceeds 0.001, the infrared ray is sufficiently blocked, and when it is 1.1 or lower than 1.1, the generation of the impurity phase in the tungsten compound can be more reliably prevented. When z/y is 2.2 or more than 2.2, the chemical stability as a material can be further enhanced' and when it is 3.0 or less, the infrared ray can be sufficiently blocked. Specific examples of the tungsten oxide-based compound represented by the formula (I) include 20 201237551 CS〇.33W03, Rb0.33W〇3, K〇33W〇3, and Ba〇33W〇3. The compound is preferably Cs〇_33W03 or Rb033w〇3, more preferably Cs〇33W〇3. Ο

鎢化合物較佳為細粒。鎢細粒之平均粒徑較佳為8〇〇 奈米或低於800，更佳為4〇〇奈米或低於奈米，更佳 為200奈米或低於200奈米。當平均粒徑在此範圍内時， 幾乎不會因為絲射峻鎢細粒阻擋可見光，以便可較成 功地確保可見光區中之透光度。自避免光散射之觀點來 看，平均粒錄佳較小，但為了在製造時料處理或其類 似因素之原m纟樣之平均粒徑通常為丨奈米或超過】 可使用兩種或超過兩種化合物作為鶴化合物。 鎢化口物可以疋市售產品，但當鎢化合物為例如氧化 物:Ϊ由在惰性氣體環境或還原氣體環境中 ==方法獲得氧倾類化合轉見曰本專 氧化鶴二化合物亦可以是例如鎢細粒分散液 μΙΤΓΓιThe tungsten compound is preferably fine particles. The average particle diameter of the tungsten fine particles is preferably 8 Å or less, more preferably 4 Å or less, more preferably 200 nm or less. When the average particle diameter is within this range, the visible light is hardly blocked by the filaments of the tungsten particles, so that the transmittance in the visible light region can be more successfully ensured. From the standpoint of avoiding light scattering, the average particle size is preferably small, but the average particle size of the original material in order to be processed or the like is usually 丨 nanometer or more. Two or more types can be used. Two compounds are used as crane compounds. The tungsten ester can be a commercially available product, but when the tungsten compound is, for example, an oxide: Ϊ is obtained by an oxygen gas or a reducing gas atmosphere == method, and the oxidized compound is transferred to the bismuth compound. For example, tungsten fine particle dispersion μΙΤΓΓι

Metal Industries, Ltd·)製造之 YMf_〇2 以本發明之可聚合組成物的全部固體含 計’鶴化合物之含量較佳為3質量％ = 5質量％至15質量。/。。 質/〇更佳為 [4]鹼溶性黏合劑 21 201237551 且可 ^中形成圖案時，可用驗性顯影劑移、 藉由驗性顯影形成極佳圖案。 ’、曝光區域， 鹼溶性黏合劑不受特別限制 可，且可根據目的來選擇適♦的 /、/、有鹼/谷性即 包括（甲基烯酸;〜黏合劑，但其實例 聚乙utru甲酸酿類樹脂、聚乙烯醇、 汆乙烯㈣丁鉍、聚乙烯甲醛、聚醯胺 二 基)丙烯酸樹脂為較佳。 及水S曰其中（甲 驗溶性黏合劑較佳具有酸基。 胺A H貌紐基、俩基、膦酸基、鬚基、綠醯 讀，且自可以可靠地形成具有成魏追縱基板不 之形狀之感光層的觀點來看，酸基較佳為酚羥基 或硫醇基，更佳為酚羥基。 & 物 含酸基之驗溶性黏合劑不受特別限制，但較佳為藉由 使用具有酸基之可聚合化合物作為單舰分所獲得之聚合 具有酸基之可聚合化合物不受❹㈣制且可根據目 的適當地卿，且其實他括_酸、f絲烯酸、衣康 酸、丁2酸、異丁烯酸、順丁烯二酸、對羧基苯乙婦以及 對羥基苯乙烯。其中，丙烯酸、甲基丙烯酸、對羧基苯乙 烯以及對經基苯乙烯為較佳，且對羥基苯乙稀為最佳。在 本文中，使用對經基苯乙稀獲得之聚合物為具有齡經基作 為酸基之聚合物。具有紛羥基之驗溶性黏合劑的實例包括 MARUtCA LYNCUR Μ、MARUKA LYNCUR MB (產品名 22 201237551 稱，由丸善石油化學有限公司（Maruzen Petrochemical Co.， Ltd.)製造）、VP-2500以及VP-12000(對乙烯苯酚聚合物， 產品名稱，由日本曹達有限公司（Nippon Soda Co.，Ltd.) 製造）。 具有此酸基之可聚合基團之酸解離常數pKa較佳為 4.0至11.0，更佳為6.0至11.0 ’更佳為8.0至11.0。 無酸基之可聚合化合物不受特別限制，但其較佳實例 包括（甲基）丙稀酸酯（諸如烧基酯、芳基酯以及芳院基 酉旨）。 (曱基）丙烯酸酯之烷基酯部分中之烷基可為直鏈或分 支鏈且較佳為碳數目為1至10之烷基，更佳為碳數目為i 至6之烷基。 、（曱基）丙烯酸酯之芳基酯部分中之芳基較佳為碳數目 為6至14之芳基，更佳為碳數目為6至10之芳基。 (甲基）丙烯酸酯之芳炫基酯部分中之芳烧基較佳為碳 數目為7至20之芳烷基，更佳為碳數目為7 关二 ❹ 基。 方沉 對應於含酸基之可聚合化合物之單體與對應於無 基之可聚合化合物之單體之間的莫耳比通常為199、、至 99:1，較佳為3〇:7〇至99:卜更佳為5〇:5〇至99卜 驗^性黏合财之含量衫㈣则，但較 0古5宅當篁/公克至4.0毫當量/公克，更佳為i 〇毫當量/公 ίί3二'當主量’公克。當含量為。.5亳當量/公克或超過05 毛虽池切，獲得令人滿意讀可崎彡性且可較可靠地 23 201237551 獲2極佳_。料，當含量為4。 毫當量/公克時，可以可Im、A 兄义低於4·0 房。 了#地避免水久圖案強度受損之憂 鹼溶性黏合劑較佳更具有交聯基，且特別佳地是均可 域之可固化性與未曝光區域之驗可顯影性且獲 之圖案（蚊言之，當需要阻焊劑具有較 了=性時’例如當阻焊劑所覆蓋之金屬配線之配線密度 ίΓ劫作用顯著）。如本文所用之交聯基表示當曝光 二口—自可聚合組成物之感光層時，能夠在感光層中進 打之聚合反應過程中交聯黏合舰合物之基團。交聯基不 文特別限制’只要其為具有此魏之基團即可，但能夠經 ，加成聚t反應之官祕的實地括_减和鍵基圈、 胺基以及環氧基。交聯基亦可為㈣在受到光照射時變成 自由基之官能基，且此交聯基之實例包括硫醇基以及鹵素 基團。最重要的是，烯系不飽和鍵基團為較佳。烯系不飽 和鍵基團較佳為苯乙烯基、（曱基)丙烯醯基或烯丙基，且 自滿足曝光之前的交聯基穩定性與永久圖案強度的觀點來 看，（曱基)丙烯酿基為更佳。 舉例而言，將自由基（聚合起始自由基或在可聚合化 t物之聚合過程中生長之自由基）加成至鹼溶性黏合劑之 父聯官能基中以在聚合物之間直接或經由玎聚合化合物之 聚合鏈產生加成聚合，因此，在聚合物分子之間形成交聯 且藉此實現固化。或者，聚合物中之原子（例如鄰接官能 可父聯基團之碳原子上之氫原子）經自由基吸引以產生聚 24 201237551 合物自由基’且聚合物自由基彼此組合以形成聚合物分子 之間的交聯，藉此實現固化。 驗溶性黏合劑中可交聯基團之含量不受特別限制，但 較佳為0.5毫當量/公克至3.0亳當量/公克，更佳為1〇毫 ' 當量/公克至3·0毫當量/公克，更佳為1.5毫當量/公克至 2.8毫當量/公克。當含量為〇·5毫當量/公克或超過〇 5毫 當量/公克時，固化反應量足夠大且獲得高敏感性，且當含 ❹ 量為毫當量/公克或低於3.0毫當量/公克時，可增強可 聚合組成物之儲存穩定性。 上述含置（毫當克/公克）可例如藉由碘值滴（i〇dine value titration )定來量測。 具有交聯基之驗溶性黏合劑詳述於jP_a_2〇〇3_262958 中，且本發明亦可使用此公開案中所述之化合物。 具有父聯基之驗溶性黏合劑較佳為具有酸基以及交 聯基之鹼溶性黏合劑，且如下為其代表性實例： (1) 含胺基甲酸酯改質之可聚合雙鍵之丙烯酸樹脂， 〇 其藉由使一種化合物與含羧基之丙烯酸樹脂反應來獲得， 所述化合物具有一個在異氰酸酯基與0H基團先前反應之 後允許保留的未反應之異氰酸醋基，且含有至少一個（曱基) 丙烯醯基； (2) 含不飽和基團之丙烯酸樹脂，其藉由使含羧基之 丙烯酸樹脂與在分子内具有環氧基與可聚合雙鍵之化合物 反應來獲得；以及 (3) 含可聚合雙鍵之丙烯酸樹脂，其藉由使含〇11基 25 201237551 團之丙烯酸樹脂與具有可聚合雙鍵之二元酸酐反應來獲 得。 其中，（1)以及（2)之樹脂為較佳。 具有酸基以及交聯基之鹼溶性黏合劑亦包括例如在 側鏈中具有酸基以及烯系不飽和鍵且具有雙酚Α型架構以 及雙酚F型架構之聚合物化合物、具有酸基以及烯系不飽 和鍵之紛裕樹脂（novolak resin)，以及可溶酚酸樹脂（res〇i resin)。可藉由 JP-A-11-240930 之段落[0008]至段落[0027] 中所述之技術獲得這些樹脂。 如上所述，鹼溶性黏合劑較佳為（甲基）丙烯酸樹脂， 且「（甲基）丙烯酸樹脂」較佳為具有以下作為聚合組分之 共聚物：（曱基）丙烯酸衍生物，諸如（曱基)丙烯酸、（曱基) 丙烯酸酯（例如烧基酯、芳基酯、芳烷基酯）、（甲基)丙稀 醯胺以及（曱基）丙烯醯胺衍生物。 (曱基）丙烯酸樹脂較佳為例如具有含酸基之重複單元 的共聚物。酸基之較佳實例包括上述酸基。較佳使用（曱基) 丙烯酸衍生之重複單元或由以下式表示之重複單元作 為含酸基之重複單元。 Λ 1 (I) 〇人A’R2、(COOH)n (在式（I)中，R1表示氫原子或曱基，R2表示單鍵或 26 201237551 A表示氧原子或·NR3·，R3表示氫原子或 成之群中的-或多個原:二：成ΐΐ=::; 團的原子數目較佳為i至8。。連接 „接基YMf_〇2 manufactured by Metal Industries, Ltd.) The content of the total solid content of the polymerizable composition of the present invention is preferably 3% by mass = 5% by mass to 15% by mass. /. . More preferably, the mass/〇 is [4] an alkali-soluble binder 21 201237551 and when a pattern is formed, an indispensable developer can be used to form an excellent pattern by an in-progressive development. ', the exposed area, the alkali-soluble binder is not particularly limited, and may be selected according to the purpose of / / /, with alkali / gluten, including (methic acid; ~ binder, but its example poly It is preferred that utru formic acid-based resin, polyvinyl alcohol, styrene-ethylene (tetra) butyl hydrazine, polyethylene formaldehyde, polyamidodiyl) acrylic resin. And water S 曰 where (a test soluble binder preferably has an acid group. Amine AH morphine, two bases, phosphonic acid groups, whiskers, green sputum, and can be reliably formed with a From the viewpoint of the photosensitive layer of the shape, the acid group is preferably a phenolic hydroxyl group or a thiol group, more preferably a phenolic hydroxyl group. The acid-containing test-soluble adhesive is not particularly limited, but is preferably by A polymerizable compound having an acid group obtained by using a polymerizable compound having an acid group as a single ship is not subjected to ruthenium (IV) and can be suitably clarified according to the purpose, and actually includes _acid, f-acid, itaconic acid , butyric acid, methacrylic acid, maleic acid, p-carboxyphenylene and p-hydroxystyrene. Among them, acrylic acid, methacrylic acid, p-carboxystyrene and p-vinyl styrene are preferred, and p-hydroxyl group Phenylethylene is the most preferred. In this paper, the polymer obtained by using p-phenylene bromide is a polymer having an aging group as an acid group. Examples of colloidal binders having a hydroxy group include MARUtCA LYNCUR Μ, MARUKA LYNCUR MB (product name 22 201237551 called Manufactured by Maruzen Petrochemical Co., Ltd., VP-2500 and VP-12000 (for ethylene phenol polymer, product name, manufactured by Nippon Soda Co., Ltd.) The acid dissociation constant pKa of the polymerizable group having this acid group is preferably from 4.0 to 11.0, more preferably from 6.0 to 11.0', still more preferably from 8.0 to 11.0. The acid group-free polymerizable compound is not particularly limited, but Preferred examples thereof include (meth) acrylate (such as a decyl ester, an aryl ester, and a aryl group). The alkyl group in the alkyl ester moiety of the (fluorenyl) acrylate may be linear or The branched chain is preferably an alkyl group having a carbon number of 1 to 10, more preferably an alkyl group having a carbon number of i to 6. The aryl group in the aryl ester portion of the (fluorenyl) acrylate is preferably a carbon number. An aryl group of 6 to 14, more preferably an aryl group having a carbon number of 6 to 10. The arylalkyl group in the aryl hexyl ester moiety of the (meth) acrylate is preferably an aralkyl group having a carbon number of 7 to 20. More preferably, the number of carbons is 7 Å. The square sink corresponds to the monomer of the polymerizable compound containing an acid group and corresponds to The molar ratio between the monomers of the non-polymerizable compound is usually from 199, to 99:1, preferably from 3:7 to 99: more preferably 5:5 to 99. ^ Sexual adhesion of the content of the shirt (four), but more than 0 ancient 5 house 篁 / gram to 4.0 meq / gram, more preferably i 〇 milli equivalent / public ίί3 two 'when the main amount 'gram. When the content is. 5 亳 equivalent / gram or more than 05 hair, although the pool is cut, it is satisfactorily read and can be more reliable. 23 201237551 is 2 excellent _. Material, when the content is 4. milliequivalent / gram, can be Im, A brother is less than 4·0 room. It is preferable that the alkali-soluble adhesive which is resistant to the deterioration of the strength of the water pattern has a cross-linking group, and particularly preferably is a curable property of the field and the developability of the unexposed area and the pattern is obtained ( Mosquitoes, when the solder resist is required to have a lower degree of 'such as when the solder wire covered by the solder resist has a significant wiring density. The cross-linking group as used herein means that when the photosensitive layer of the two-self-polymerizable composition is exposed, the group of the bonded hydrate can be crosslinked during the polymerization reaction in the photosensitive layer. The cross-linking group is not particularly limited as long as it is a group having such a Wei group, but can be subjected to the addition of a poly-t reaction to the official secrets of the ruthenium and the bond group, the amine group and the epoxy group. The crosslinking group may also be (d) a functional group which becomes a radical upon irradiation with light, and examples of the crosslinking group include a thiol group and a halogen group. Most importantly, an ethylenically unsaturated bond group is preferred. The ethylenically unsaturated bond group is preferably a styryl group, a (fluorenyl) acrylonitrile group or an allyl group, and from the viewpoint of satisfying the stability of the crosslinking group before exposure and the strength of the permanent pattern, (fluorenyl) The acryl base is better. For example, a free radical (a polymerization starting radical or a free radical grown during the polymerization of the polymerizable t) is added to the parent functional group of the alkali soluble binder to directly or between the polymers. The addition polymerization is produced via the polymer chain of the ruthenium polymer compound, and thus, crosslinking is formed between the polymer molecules and thereby curing is achieved. Alternatively, an atom in the polymer (eg, a hydrogen atom on a carbon atom adjacent to a functionally cleavable group) is free radically attracted to produce a poly 24 201237551 compound radical ' and polymer radicals are combined with one another to form a polymer molecule Crosslinking between them is achieved by curing. The content of the crosslinkable group in the test-soluble binder is not particularly limited, but is preferably from 0.5 meq/g to 3.0 亳/g, more preferably from 1 〇 ' / gram to 3.0 eq / The gram is more preferably 1.5 meq/g to 2.8 meq/g. When the content is 〇·5 meq/g or more than 毫5 meq/g, the curing reaction amount is sufficiently large and high sensitivity is obtained, and when the amount of ruthenium is milliequivalent/g or less than 3.0 meq/g It can enhance the storage stability of the polymerizable composition. The above-mentioned inclusions (milligrams/gram) can be measured, for example, by iodine value titration. A test-soluble adhesive having a cross-linking group is described in detail in jP_a_2〇〇3_262958, and the compounds described in the publication can also be used in the present invention. The test-soluble adhesive having a parent base is preferably an alkali-soluble binder having an acid group and a crosslinking group, and is a representative example thereof as follows: (1) A polymerizable double bond modified with a carbamate An acrylic resin obtained by reacting a compound with a carboxyl group-containing acrylic resin having an unreacted isocyanate group which is allowed to remain after the isocyanate group and the 0H group are previously reacted, and contains at least a (fluorenyl) acrylonitrile group; (2) an unsaturated group-containing acrylic resin obtained by reacting a carboxyl group-containing acrylic resin with a compound having an epoxy group and a polymerizable double bond in the molecule; (3) An acrylic resin containing a polymerizable double bond, which is obtained by reacting an acrylic resin containing a ruthenium 11 group 25 201237551 group with a dibasic acid anhydride having a polymerizable double bond. Among them, the resins of (1) and (2) are preferred. The alkali-soluble binder having an acid group and a crosslinking group also includes, for example, a polymer compound having an acid group and an ethylenically unsaturated bond in a side chain and having a bisphenol fluorene type structure and a bisphenol F type structure, having an acid group and A novolak resin of an ethylenically unsaturated bond, and a resole phenolic resin. These resins can be obtained by the technique described in paragraphs [0008] to [0027] of JP-A-11-240930. As described above, the alkali-soluble binder is preferably a (meth)acrylic resin, and the "(meth)acrylic resin" is preferably a copolymer having the following polymerizable component: (mercapto)acrylic acid derivative, such as ( Mercapto) acrylic acid, (fluorenyl) acrylate (eg, alkyl ester, aryl ester, aralkyl ester), (meth) acrylamide, and (mercapto) acrylamide derivatives. The (fluorenyl) acrylic resin is preferably, for example, a copolymer having a repeating unit containing an acid group. Preferable examples of the acid group include the above acid groups. It is preferred to use a (fluorenyl) acrylic-derived repeating unit or a repeating unit represented by the following formula as a repeating unit containing an acid group. Λ 1 (I) Deuterium A'R2, (COOH)n (In the formula (I), R1 represents a hydrogen atom or a fluorenyl group, R2 represents a single bond or 26 201237551 A represents an oxygen atom or NR3·, and R3 represents hydrogen - or more than one in the group of atoms or groups: two: ΐΐ = =:; The number of atoms in the group is preferably from i to 8.

烧基以及伸絲’且連接基®可具有多個上!二價i接^ 團經由軸鍵、畴、胺基甲酸賴、脲鍵以及酷鍵^ -者連接之結構。β較佳為單鍵、躲基❹個伸 由醯賴、_、祕甲_旨鍵、職以及賴中至少L 者連接之結構。 伸烷基之碳數目較佳為i至5，更佳為〗至3。 伸芳基之碳數目較佳為6至14，更佳為6至1〇。 伸烷基以及伸芳基可更具有取代基，且取代基之 包括除氫原子外之單價非金屬原子團且包括_素原子 (-F、-Br、-Cl、-I)、經基、氰基、烧氧基、芳氧基、疏基、 烷硫基、芳硫基、烷基羰基、芳基羰基、鲮基以及其共 鹼基、烷氧羰基、芳氧羰基、胺甲醯基、芳基、烯基以^ 炔基。 土 R3之烴基較佳具有丨至1〇之碳數目，更佳具有^至 5之碳數目，更佳具有1至3之碳數目。 R最佳為風原子或f基。 η較佳為1至3，更佳為i或2，且最佳為1。 鑒於可顯影性，在（甲基）丙烯酸樹脂之所有重複單元 27 201237551 I A. 組分中含酸基之重複單元所佔的比率（莫耳％ )較佳為〗〇 〇/〇 至90%，且鑒於均滿足永久圖案之可顯影性與強度，所述 比率更佳為50%至85%，更佳為60%至80〇/〇。 ^如已描述，（甲基）丙烯酸樹脂較佳更具有交聯基，且 父聯基之特定實例以及含量與上述相同。 除含酸基之聚合單元以及含交聯基之聚合單元外，用 於本發明之（曱基）丙烯酸系聚合物可含有（甲基）丙烯醯胺 或^针生物之聚合單元、α-羥甲基丙烯酸酯之聚合單元以 及笨乙缚仿生物之聚合單元。（甲基）丙烯酸烧基酯之炫基 較佳為碳數目為1至5之烧基，或碳數目為2至8之具有 上述取代基之烧基’更佳為甲基。（甲基）丙烯酸芳烷基酯 之實例包括（曱基)丙烯酸苯甲醋。（甲基)丙烯醯胺衍生物之 實$包括N-異丙基丙烯酿胺、N_苯基甲基丙稀酿胺、n_(4_ 曱氧基％基苯基)曱基丙稀酿胺、耶_二曱基丙稀醯胺以及 (N-嗎啉基)丙烯醯胺。α_羥曱基丙烯酸酯之實例包括…羥 甲基丙烯酸乙酯以及α_羥曱基丙烯酸環己酯 。苯乙烯衍生 物之實例包括苯乙烯以及4_第三丁基苯乙稀。 作為除了（曱基）丙烯酸樹脂外之鹼溶性黏合劑，例如 區;w州專利 993,966 以及 1，2〇4,〇〇〇 以及 JP_A_2001_318463 中所述的具錢基之祕改質聚乙烯醇娜合劑聚合物因 =強度與可顯f彡性之間的極佳平衡而為較佳。另外 ，諸如 ，乙烯吡咯啶酮以及聚氧化乙烯之水溶性線性有機聚合物 用的。此外，醇溶性耐綸、2,2-雙羥苯基)_丙烷與表 乳醇之聚醚’及其_物仙於提高眺膜強度。 28 201237551 最重要的是，[(曱基)丙烯酸苯曱酯/(曱基)丙烯酸/另一 加成可聚合乙烯系單體（必要時）]共聚物，以及[(甲基) 丙烯酸烯丙酯/(甲基）丙烯酸/另一加成可聚合乙烯系單體 (必要時）]共聚物因膜強度、敏感性以及可顯影性之間的 極佳平衡而為較佳。 可用於本發明之可聚合組成物中的黏合劑聚合物之 重量平均分子量較佳為3,00〇或超過3 〇〇〇，更佳為5,〇〇〇 ❹ 至3〇〇,〇00，且最佳為1〇,〇〇〇至30,000，且數目平均分子 — 量較佳為1,0⑻或超過1，〇〇〇，更佳為2,000至250,000。 多分散性（polydispersity)(重量平均分子量/數目平均分 子量）較佳為1或超過1，更佳為U至10。 黏合劑聚合物可為無規聚合物（random polymer )、嵌 段共聚物、接枝聚合物及其類似物中任一者。 可藉由習知方法合成驗溶性黏合劑。合成所用之溶劑 的實例包括四氫呋喃、二氯乙烷（ethylene dichl〇ride )、環 已酮、丙二醇單曱醚、丙二醇單曱醚乙酸酯以及乙酸丁酯。 〇 可單獨使用這些溶劑中的一者，或可混合並使用其兩者或 超過兩者。 可單獨使用這些鹼溶性黏合劑中的一者，或可組合使 用其兩者或超過兩者。 以本發明之可聚合組成物的全部固體含量（質量） 计、’鹼溶性黏合劑之含量較佳為5質量％至8〇質量％，更 佳為30質量％至6〇質量％。含量在此範圍内時，曝光敏 感陡良好，處理時間可較短，並獲得良好的TCT抗性。 29 201237551 [5]無機填料 八t發明之可聚合組成物含有無機填料作為基本組 分:操作機制並不顯而易知，但被認為是藉由使本發明之 可聚合組成物含有無機填料’當上方形成感光層之基板具 有不均勻形狀時，可聚合組成物可形成具有成功地追蹤基 板不均勻形狀之形狀的感光層。 舉例而言，如圖11之示意性截面圖中所示’在具有 不均勻形狀之基板（在下文中有時稱作「不均勻基板」，亦 即如下基板’其中在矽基板501之表面501a上以配線至配 線（wiring-t0_wiring )距離w設置多個配線（例如銅配線） 502)上形成由可聚合組成物形成之感光層5〇3。 在本文中，感光層503藉由將可聚合組成物溶液塗佈 於支撐物上且必要時熱處理所述塗層來形成。此時，尤其 當多個配線502之配線至配線距離w較小時（尤其當配線 至配線距離W為1〇〇微米或低於1〇〇微米時），儘管設置 於配線表面502a上之感光層的厚度為所需厚度，但配線間 區域（inter-wiring region) C中感光層之厚度有時比所需 厚度大得多。更特定言之，圖U之配線間區域c _之點 線部分表示以下狀態：其中配線間區域c中之感光層表面 之底部C2與石夕基板501之表面5〇la之間的距離，亦即配 線間區域C中感光層之厚度^比所需厚度大得多。推測此 可歸因於以下事實：在例如自設置於基板上之可聚合組成 物之塗層乾燥溶劑時，配線間區域C中塗層之表面升高。 然而，在由本發明之可聚合組成物形成之感光層中， 30 201237551 之線二’ 中感光層之厚度接近於所需厚度。更特定言 與嫩:===中感光層表面之底部C1 1接近於所需厚度。推測此是因為在例如 時叹本發==域中之可聚合組成物之塗層乾燥溶劑 區域c中之塗層i合組成物令所含之無機填料阻止配線間 j C中之塗層表面上升。以此 Ο Ο i物可形成具有成舰追《板不均勻表*之雜^光 光芦2可聚合組成物，因為配線間區域C中感 度=2度，所以當曝光區域包括配線間 配線間區域彻)可以可靠地到達 501之表面501a的1^殊。以例如接近感光層中石夕基板 因此，可Μ丨°卩）’且可藉由曝光達成充分固化。 著失敗的憂慮。分離或對不均勻基板上之基板之黏 以欲ΖΓί發明中之無機填料較佳為二氧化石夕，更佳為 以石夕烧輕合劑表面處理之球形二氧化石夕。 更佳為 具有圭含有填料，且較佳是獲得 時，例如當阻焊劑具有較高耐久性 作用顯著）。 覆 屬配線之配線密度較高時， 石夕合劑表面處理之球形一氧化 夕增強可聚合組成物之熱循環測試抗性以定 31 201237551 -rv/J ·ΐ 上 性，且甚至在經歷例如嚴峻環境（諸如熱循環測試）後仍 可維持與圖案形成後不久之形態相同之良好輪廓。 右粒子不為針狀、柱形或非晶形狀，但經圓化 (round)，則球形填料中之術語「球形」可為足夠的，且形 狀不一定為「真正球形（truly spherical)」。然而，典型「球 形」形狀為「真正球形」形狀。 填料是否為球形可藉由經由掃描電子顯微鏡 (scanning electron microscope，SEM)觀察其來確認。 無機填料之體積平均一次粒控（volume average pnmary particle diameter)不受特別限制且可根據目的來適 當地選擇，但較佳為〇.〇5微米至3微米，更佳為〇.1微米 至1微米。當填料之體積平均一次粒徑在上述範圍内時， 有利的是抑制了由產生搖變性（thiX〇tr〇py)造成之可加工 性受損且阻止了最大粒徑變大，因此可防止因外來物質附 著於所得固化膜或是因塗膜（coated film)不均一性所致 之缺陷產生。 無機填料之體積平均一次粒徑可藉由動態光散射粒 徑分佈量測裝置來量測。 無機填料可使用上述分散劑以及黏合劑來分散。如上 所述’鑒於可固化性，在側鏈中具有交聯基之鹼溶性黏合 劑為較佳。 -表面處理- 下文描述無機填料之表面處理。無機填料之表面處理 不受特別限制且可根據目的適當地選擇，但以矽烷耦合劑 32 201237551 覆蓋二氧化矽之處理為較佳。 -矽烷耦合劑_ 用於無機填料之表面處理的矽烷耦合劑不受特別限 制且y根據目的適當地選擇，但含有選擇自烷氧基矽烷 基、氣石夕燒基以及乙醯氧基矽烷基之群中的至少一個官能 基（在下文中有時稱作「第一官能基」）以及選擇自（曱基) 丙烯醯基、胺基以及環氧基之群中的至少一個官能基（在 0 了 有時稱作「第二官能基」）的石夕烧粞合劑為較佳。第 一 g旎基更佳為（曱基）丙烯醯基或胺基，且第二官能基更 佳為基)丙烯醯基。當第二官能基為（曱基)丙烯醯基時， 鑒於儲存穩定性以及TCT抗性方面是有利的。 較佳亦可使用JP-B-7-68256中所述之含有選擇自烷氧 基矽烷基、氣矽烷基以及乙醯氧基矽烷基之成員中的至少 一者作為第一官能基且含有選擇自咪唑基、炫基咪唑基以 及乙烯基咪唑基之成員中的至少一者作為第二官能基的耦 合劑。 〇 矽烷耦合劑不受特別限制，但其較佳實例包括γ-胺基 丙基二乙氧基矽烷、Ν-(β-胺基乙基)_γ_胺基丙基三甲氧基 石夕烧、Ν-(β-胺基乙基)个胺基丙基曱基二曱氧基矽烷、γ_ 縮水甘油氧基丙基三甲氧基矽烷、γ_縮水甘油氧基丙基曱 基二甲氧基矽烷、γ-曱基丙烯醯氧基丙基三乙氧基矽烷、γ_ 曱基丙烯醯氧基丙基甲基二甲氧基矽烷、α_[[3·(三曱氧基 矽烷基）丙氧基]曱基]-咪唑_1_乙醇（jP_B_7_68256中所 述）、2-乙基-4-曱基三甲氧基矽烷基)丙氧基]甲基]_ 33 201237551 -ΤΚ/^ ί 4^^ΛΛ. 咪唑-1-乙醇、4 7咕甘 基]+坐小乙醇ϋα-[[3-(4氧基石夕烧基)丙氧基]甲 以及翻、丄乙基-4-甲基咪唑丙基三甲氧基矽烷， 這些化合物以及分子間縮合物。可單獨使用 、 者，或可組合使用其兩者或超過兩者。 气於二T耦合劑表面處理球形二氧化矽可僅對球形二 i」)，或:SC下’在下文中有時稱作「預處 全部-起進ί 成物中所含之其他填料之一部分或 進仃預處理之方法不受特別限制，且方法之實例包括 乾法、水溶液法、有機溶劑法以及喷射法。進行預處理之 特別限制，但較佳為常溫（n〇rmaltemperature) 虽進行預處理時亦較佳添加催化劑。催化劑不受特別 限制且其實例包括酸、鹼、金屬化合物以及有機金屬化 合物。 在進行預處理之情況下，矽烷耦合劑之添加量不受特 別，制，但對於每UK) f量份球形二氧化碎，較佳為〇 〇1 質量份至50質量份，更佳為0 05質量份至5〇質量份。當 添加量處於此範圍内時，進行足以產生作用之表面處理: 且同時抑制處理後因球形二氧化矽聚集所引起之可操作性 降低。 因為第一官能基與基材表面、球形二氧化石夕表面以及 黏合劑中之活性基團反應，且第二官能基與黏合劑之羧基 以及稀系不飽和基團反應，所以上述矽烧耦合劑具有增強 34 201237551 基材與感来塵#The base and the filaments' and the linker® may have a plurality of structures on which the divalent i-bonds are linked via a backbone bond, a domain, a carbamic acid lysate, a urea bond, and a cool bond. β is preferably a single bond, which is a structure in which at least L is connected by 醯, _, 甲甲 _ key, job, and 赖. The number of carbons of the alkylene group is preferably from i to 5, more preferably from 3 to 3. The carbon number of the aryl group is preferably from 6 to 14, more preferably from 6 to 1 Å. The alkylene group and the extended aryl group may have a more substituent, and the substituent includes a monovalent non-metal atomic group other than a hydrogen atom and includes a _ atom (-F, -Br, -Cl, -I), a trans group, and a cyanogen group. Base, alkoxy group, aryloxy group, sulfhydryl group, alkylthio group, arylthio group, alkylcarbonyl group, arylcarbonyl group, fluorenyl group and its co-base, alkoxycarbonyl group, aryloxycarbonyl group, amine carbaryl group, An aryl group or an alkenyl group is an alkynyl group. The hydrocarbon group of the earth R3 preferably has a carbon number of from 1 to 3, more preferably from 0 to 5, more preferably from 1 to 3. R is preferably a wind atom or an f group. η is preferably from 1 to 3, more preferably i or 2, and most preferably 1. In view of developability, the ratio (mol%) of the repeating unit containing an acid group in all repeating units of the (meth)acrylic resin 27 201237551 I A. is preferably from 〇〇/〇 to 90%. And, in view of satisfying the developability and strength of the permanent pattern, the ratio is more preferably from 50% to 85%, more preferably from 60% to 80%/〇. As already described, the (meth)acrylic resin preferably has a crosslinking group, and the specific examples and contents of the parent group are the same as described above. The (mercapto)acrylic polymer used in the present invention may contain a polymerization unit of (meth) acrylamide or a needle, and an α-hydroxy group, in addition to a polymer unit containing an acid group and a polymerization unit containing a crosslinking group. A polymerization unit of methacrylate and a polymerization unit of a stupid compound. The stilbyl group of (meth)acrylic acid ester is preferably a group having a carbon number of 1 to 5, or a group having a carbon number of 2 to 8 and having a substituent of the above substituent is more preferably a methyl group. Examples of the aralkyl (meth)acrylate include benzyl acetate (mercapto)acrylate. The (meth) acrylamide derivative is composed of N-isopropylacrylamide, N-phenylmethylpropylamine, n_(4_decyloxyphenyl)mercaptopropylamine , yt-dimercapto acrylamide and (N-morpholinyl) acrylamide. Examples of the α-hydroxydecyl acrylate include ... hydroxyethyl methacrylate and α-hydroxydecyl methacrylate. Examples of the styrene derivative include styrene and 4_t-butylstyrene. As an alkali-soluble binder other than (fluorenyl) acrylic resin, for example, the region; the state of the art patent 993,966 and 1,2,4, 〇〇〇 and JP_A_2001_318463 The polymer is preferred because of the excellent balance between strength and visibility. Further, it is used for water-soluble linear organic polymers such as vinylpyrrolidone and polyethylene oxide. Further, the alcohol-soluble nylon, the polyether of 2,2-bishydroxyphenyl)-propane and galactitol, and the like, are used to increase the strength of the ruthenium film. 28 201237551 The most important is [(indenyl) phenyl acrylate / (mercapto) acrylic acid / another addition polymerizable vinyl monomer (if necessary)] copolymer, and [(meth)acrylic allylate The ester/(meth)acrylic acid/other addition polymerizable vinyl monomer (if necessary) copolymer is preferred because of an excellent balance between film strength, sensitivity, and developability. The weight average molecular weight of the binder polymer which can be used in the polymerizable composition of the present invention is preferably 3,00 Torr or more, more preferably 5, 〇〇〇❹ to 3 〇〇, 〇00, Preferably, it is 1 〇, 〇〇〇 to 30,000, and the number average molecular weight is preferably 1,0 (8) or more than 1, 〇〇〇, more preferably 2,000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably U to 10. The binder polymer may be any of a random polymer, a block copolymer, a graft polymer, and the like. The test-soluble adhesive can be synthesized by a conventional method. Examples of the solvent used in the synthesis include tetrahydrofuran, ethylene dichl〇ride, cyclohexanone, propylene glycol monoterpene ether, propylene glycol monoterpene ether acetate, and butyl acetate. 〇 One of these solvents may be used alone, or two or more of them may be mixed and used. One of these alkali-soluble binders may be used alone, or both or more may be used in combination. The content of the alkali-soluble binder is preferably from 5% by mass to 8% by mass, more preferably from 30% by mass to 6% by mass, based on the total solid content (mass) of the polymerizable composition of the present invention. When the content is within this range, the exposure sensitivity is steep, the treatment time can be short, and good TCT resistance is obtained. 29 201237551 [5] Inorganic fillers The polymerizable composition of the invention contains an inorganic filler as an essential component: the operation mechanism is not readily known, but it is considered that the polymerizable composition of the present invention contains an inorganic filler. When the substrate on which the photosensitive layer is formed has a non-uniform shape, the polymerizable composition can form a photosensitive layer having a shape that successfully tracks the uneven shape of the substrate. For example, as shown in the schematic cross-sectional view of FIG. 11, a substrate having an uneven shape (hereinafter sometimes referred to as "uneven substrate", that is, a substrate" on the surface 501a of the ruthenium substrate 501 is shown. The photosensitive layer 5〇3 formed of the polymerizable composition is formed on a plurality of wirings (for example, copper wiring) 502) by wiring to wiring (wiring-t0_wiring) distance w. Herein, the photosensitive layer 503 is formed by coating a solution of a polymerizable composition on a support and, if necessary, heat-treating the coating. At this time, particularly when the wiring of the plurality of wirings 502 to the wiring distance w is small (especially when the wiring to the wiring distance W is 1 〇〇 micrometer or less than 1 〇〇 micrometer), although the photosensitive layer is disposed on the wiring surface 502a The thickness of the layer is the desired thickness, but the thickness of the photosensitive layer in the inter-wiring region C is sometimes much larger than the desired thickness. More specifically, the dotted line portion of the inter-wiring area c_ of FIG. U indicates a state in which the distance between the bottom C2 of the surface of the photosensitive layer in the inter-wiring area c and the surface 5〇la of the XI XI substrate 501 is also That is, the thickness of the photosensitive layer in the wiring area C is much larger than the required thickness. It is presumed that this is attributable to the fact that the surface of the coating in the inter-wiring region C rises when, for example, the coating drying solvent of the polymerizable composition provided on the substrate. However, in the photosensitive layer formed of the polymerizable composition of the present invention, the thickness of the photosensitive layer in the line 2' of 30 201237551 is close to the desired thickness. More specifically and tender: === The bottom C1 1 of the surface of the photosensitive layer is close to the desired thickness. It is presumed that this is because the coating i in the coating drying solvent region c of the polymerizable composition in the domain === domain, for example, causes the inorganic filler contained in the coating to prevent the coating surface in the wiring compartment j C rise. Therefore, the Ο 物 i object can form a polymerizable composition having a smashing "plate unevenness table*", because the sensitivity in the wiring area C is 2 degrees, so when the exposure area includes the wiring room wiring closet The area can be reliably reached to the surface 501a of the 501. For example, it is close to the substrate of the photosensitive layer, so that it can be sufficiently cured by exposure. Worries about failure. Separating or adhering to the substrate on the uneven substrate. The inorganic filler in the invention is preferably a dioxide dioxide, more preferably a spherical silica dioxide surface treated with a stone-lighting mixture. More preferably, it has a filler, and is preferably obtained, for example, when the solder resist has a high durability effect. When the wiring density of the overlying wiring is high, the spherical oxidation-oxidation of the surface treatment of the Si Xi mixture enhances the thermal cycle test resistance of the polymerizable composition to be 31, 31,375,551 - rv / J · 上 upper, and even experienced severe A good profile that is identical to the shape immediately after patterning can still be maintained after the environment (such as thermal cycling test). The right particle is not acicular, cylindrical or amorphous, but the rounded, the term "spherical" in the spherical filler may be sufficient and the shape is not necessarily "truly spherical". However, a typical "spherical" shape is a "true spherical" shape. Whether or not the filler is spherical can be confirmed by observing it by a scanning electron microscope (SEM). The volume average pnmary particle diameter of the inorganic filler is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 〇. 5 μm to 3 μm, more preferably 〇. 1 μm to 1 Micron. When the volume average primary particle diameter of the filler is within the above range, it is advantageous to suppress the deterioration of workability caused by the occurrence of thixotropy and prevent the maximum particle size from becoming large, thereby preventing the cause Foreign substances adhere to the resulting cured film or defects due to coating film heterogeneity. The volume average primary particle diameter of the inorganic filler can be measured by a dynamic light scattering particle size distribution measuring device. The inorganic filler can be dispersed using the above dispersant and a binder. As described above, in view of curability, an alkali-soluble binder having a crosslinking group in a side chain is preferred. - Surface treatment - The surface treatment of the inorganic filler is described below. The surface treatment of the inorganic filler is not particularly limited and may be appropriately selected depending on the purpose, but it is preferred to cover the cerium oxide with the decane coupling agent 32 201237551. - decane couplant _ The decane coupling agent used for the surface treatment of the inorganic filler is not particularly limited and y is appropriately selected depending on the purpose, but contains a selected from alkoxy fluorenyl group, gas sulphide group and ethoxylated decyl group. At least one functional group in the group (hereinafter sometimes referred to as "first functional group") and at least one functional group selected from the group consisting of (fluorenyl) acryl fluorenyl group, amine group, and epoxy group (at 0) It is preferred that the Shi Xi simmering agent is sometimes referred to as "second functional group". The first g fluorenyl group is more preferably a (fluorenyl) acryl fluorenyl group or an amine group, and the second functional group is more preferably a acryl fluorenyl group. When the second functional group is a (fluorenyl) acrylonitrile group, it is advantageous in view of storage stability and TCT resistance. It is preferable to use at least one of the members selected from the group consisting of alkoxyalkyl, alkyl, and ethoxyalkyl decyl groups as described in JP-B-7-68256 as the first functional group and containing the selection. At least one of the members of the imidazolyl group, the leumoimidazolyl group, and the vinylimidazolyl group serves as a coupling agent for the second functional group. The decane coupling agent is not particularly limited, but preferred examples thereof include γ-aminopropyl diethoxy decane, Ν-(β-aminoethyl)_γ-aminopropyltrimethoxy sulphur, lanthanum -(β-aminoethyl)aminopropyl propyl decyl decyl oxane, γ-glycidoxypropyl trimethoxy decane, γ-glycidoxypropyl decyl dimethoxy decane, γ-Mercaptopropoxypropyltriethoxydecane, γ-mercaptopropenyloxypropylmethyldimethoxydecane, α_[[3·(tridecyloxydecyl)propoxy] Mercapto]-imidazole_1_ethanol (described in jP_B_7_68256), 2-ethyl-4-mercaptotrimethoxydecylalkyl)propoxy]methyl]_ 33 201237551 -ΤΚ/^ ί 4^^ΛΛ . Imidazole-1-ethanol, 4 7 咕-glycine] + sitting small ethanol ϋα-[[3-(4 oxetyl)propoxy]methyl and fluorenyl-ethyl-4-methylimidazolium Trimethoxydecane, these compounds and intermolecular condensates. They may be used alone or in combination of two or more. The surface treatment of spherical cerium oxide on the surface of the two T-coupling agent may be only for the spherical two i"), or: SC under 'sometimes hereinafter referred to as "pre-existing all-in-one of the other fillers contained in the material" The method of pretreatment is not particularly limited, and examples of the method include a dry method, an aqueous solution method, an organic solvent method, and a spray method. The pretreatment is particularly limited, but it is preferably a normal temperature (n〇rmaltemperature). It is also preferred to add a catalyst during the treatment. The catalyst is not particularly limited and examples thereof include an acid, a base, a metal compound, and an organometallic compound. In the case of pretreatment, the amount of the decane coupling agent added is not particularly limited, but for a quantity of spherical oxidized granules per UK), preferably from 1 part by mass to 50 parts by mass, more preferably from 0.05 parts by mass to 5 parts by mass. When the amount added is within this range, sufficient to effect Surface treatment: and at the same time inhibiting the operability caused by the aggregation of spherical cerium oxide after treatment, because the first functional group is on the surface of the substrate, the spherical sulphur dioxide surface and the binder The reactive group reacts, and the second functional group reacts with the carboxyl group of the binder and the rare unsaturated group, so the above-mentioned smoldering coupling agent has the enhancement 34 201237551 substrate and sense dust #

歷反應或失活（deactivation )， 或適用期（P〇t life)縮短。 從而使得存放期（shelflife) 具有高反應 中，則大部 …、而，當使用以矽烷耦合劑預處理之球形二氧化矽 ^ ’擴散作用受到抑制以大大地改良存放期或適用期的問 〇 題，且變得可能採取甚至單液體系統（cme-liquid system )。 此外在對球形一氧化石夕應用預處理之情況下，可自由選 擇諸如授拌條件、溫度條件以及使用催化劑之條件，以便 與士應用預處理之添加相比，可顯著提高石夕烧麵合劑之第 一官能基與球形二氧化矽中之活性基團的反應比率。因 此，就在諸如無電錢金（electroless gold plating)、無電焊 料電鍵（electroless solder plating )以及防潮性負載測試之 嚴峻條件下之所需特性而言獲得極好結果。此外，藉由進 行預處理’可減少矽烷耦合劑之使用量，且可更加改良存 〇 放期以及適用期。 可用於本發明中之以矽烷耦合劑表面處理之球形二 氧化矽的實例包括電氣化學工業株式會社（Denki KagakuThe cycle of reaction or deactivation, or the pot life (P〇t life) is shortened. Therefore, the shelf life has a high reaction, and most of them, when using a spherical cerium dioxide pretreated with a decane coupling agent, the diffusion is suppressed to greatly improve the shelf life or pot life. And become possible to adopt even a cme-liquid system. In addition, in the case of applying a pretreatment to the spherical nitric oxide, the conditions such as the mixing conditions, the temperature conditions, and the use of the catalyst can be freely selected, so as to significantly improve the Shi Xi Shao noodle mixture as compared with the addition of the pretreatment application. The ratio of the reaction of the first functional group to the reactive group in the spherical ceria. Therefore, excellent results are obtained in terms of desired characteristics under severe conditions such as electroless gold plating, electroless solder plating, and moisture-proof load testing. In addition, by using pretreatment, the amount of decane coupling agent used can be reduced, and the shelf life and pot life can be further improved. Examples of the spherical cerium oxide surface-treated with a decane coupling agent which can be used in the present invention include Denki Kagaku

Kogyo Kabushiki Kaisha)之FB以及SFP系列；龍森有限 公司（Tatsumori Ltd.)之1 -FX;東亞合成有限公司（Toagosei Co.，Ltd.)之HSP系列；以及扶桑化學有限公司（puso Chemical Co” Ltd.)之 SP 系列。 以可聚合組成物之全部固體含量（質量）計，無機填 35 201237551 料之含量較佳為1質量％至60質量％，更佳為2〇質量％ 至60#質量％，更佳為4〇質量％至6〇質量％。當添加量處 於此範圍内時’在上方設置感光層之基板具有不均句形狀 的情況下，可更加可靠地形成具有成功地追蹤基板不均勻 形狀之形狀的感光層。 [6]紫外線吸收劑（Ultravi〇letAbs〇rber) 本發明之可聚合組成物較佳含有紫外線吸收劑。 ，紫外線吸收劑併入例如阻焊劑之抗蝕劑組成物中 且在藉由將抗蝕劑組成物塗饰於固態攝影元件之半導體基 板j其中在表面上設置有對準標記）上形成感光層之後， 進行曝光以及顯影以形成阻焊層，藉此可更加可靠地製得 能夠滿足消_後所述之「由基板表面上之反射光造成之 問題」與藉由可見光感測器可靠地偵測對準標記之阻焊層。 在上方》又置有感光層之基板表面由具有高光反射性 (lightreflectivity)之材料（諸如金屬）形成的情況下，因 為在曝蕗於感光層時來自基板界面活性劑之反射光變得可 觀，所以所得圖案之截面形狀易於變成裙擺形狀（亦即， 截面形狀之矩形性易於受損）。另一方面，若在曝光劑量保 持較低以便減少反㈣n兄下，财有矩形截面形狀之 圖案可能因曝光劑量不足而難以形成。 然而，在本發明之可聚合組成物含有紫外線吸收劑之 情況下，甚至當用獲得具有矩形截面形狀之圖案所必需之 曝光劑量（在下文中有時稱作「適當曝光劑量」）進行照射 時，紫外線吸收劑吸收反射光且此舉使得易於形成具有矩 36 201237551 形截面形狀之圖案。 紫外線吸收劑較佳為不能藉由光或熱來起始可聚合 化合物之聚合的化合物（亦即並非來自聚合起始劑之化合 物）。如本文所用之表述「不能起始可聚合化合物之聚合」 意謂甚至當紫外線吸收劑接收光或熱能時，其仍不產生用 於起始可聚合化合物之聚合的活性物種。 更特定而言，紫外線吸收劑較佳為對紫外線或可見射 線（更特定s之’波長為300奈米至450奈米之光）不具 〇 有感光性（Photosensitivity)且對熱（更特定言之，例如在 150C至250C下之熱）不具有感溫性（thermosensitivity) 之化合物。如本文所用之術語「感光性」以及「感溫性」 意謂產生目標功能，同時因紫外線或可見射線或熱之作用 而涉及化學結構變化。 此外，紫外線吸收劑較佳為不僅不能起始可聚合化合 物之聚合，而且缺乏稍後所述之敏化劑性質。如本文所用， 術浯「敏化劑性質」表示將藉由敏化劑本身的光吸收獲得 ❹ 之能量轉移至另一材料（聚合起始劑）且藉此起始聚合之 性質。 σ 紫外線吸收劑較佳為最大吸收波長在300奈米與43〇 奈米之間的化合物，更佳為最大吸收波長在330奈米與42〇 奈朱之間的化合物。 紫外線吸收劑更佳具有至少在以下巾之—個範圍内 之最大吸收波長：⑴340奈米至380奈米之範圍，⑻ 380奈米至420奈米之範圍，以及（III) 420奈米至450 37 201237551 奈米之範圍。 在藉由對使用本發明之可聚合組成物形成之感光層 應用曝光以及顯影而形成圖案時，在曝光光源含有i線之 情況下，紫外線吸收劑之最大吸收波長較佳在上述波長範 圍（I)内。 在曝光光源含有h線之情況下，紫外線吸收劑之最大 吸收波長較佳在上述波長範圍（π)内。 在曝光光源含有g線之情況下，紫外線吸收劑之最大 吸收波長較佳在上述波長範圍（111)内。 可使用例如水楊酸酯類、二苯曱酮類、苯并三唑類、 經取代之丙烯腈類或三嗪類的紫外線吸收劑作為紫外線吸 收劑。 水揚酸酯類紫外線吸收劑的實例包括水楊酸苯酯、水 楊酸對辛基苯酯以及水揚酸對第三丁基苯酯。二苯甲酮類 备、外線吸收劑的實例包括2,2’-二經基-4-甲氧基二苯曱 _、2,2 -—赵基_4,4'·二曱氧基二苯曱酮、2,2，,4,4，-四經基二 苯甲酮、2·羥基-4-曱氧基二苯曱酮、2,4_二經’基二苯甲酮 以及2-經基-4-辛氧基一本曱_。苯并三唾類紫外線吸收劑 的實例包括2-(2’-羥基_3’，5，-二第三丁基苯基)·5_氯苯并三 唑、2-(2，-羥基-3，-第三丁基_5，_甲基苯基)_5、氯苯并三唑、 2-(2’-羥基_3，_第三戊基_5，_異丁基苯基)5氯苯并三唑、 羥基-3’_異丁基_5，_曱基苯基)_5_氯笨并三唑、2_(2，-經 基-3’-異丁基-5’-丙基苯基)-5-氯苯并三唑、2_(2,_經基_3，，5，_ 二第三丁基苯基)苯并三唑、2-(2，-羥基_5，_甲基苯基)苯并三 38 201237551 〇坐以及2-[2L經基_5，，-(1，1，3,3-四曱基)苯基]苯并三唑。 經取代之丙烯腈類紫外線吸收劑的實例包括2_氰基 -3,3-二苯基丙烯酸乙酯以及2_氰基_3,3_二苯基丙烯酸孓乙 基己醋。三嗪類紫外線吸收劑的實例包括單(羥苯基)三嗪 化合物，諸如2_[4_[(2_經基各十二烷氧基丙基)氧基]_2羥 苯基]-4,6-雙(2,4_二甲基苯基)+3,5:嗪、2_[4_[(2_經基_3_ 十二烧氧基丙基）氧基]-2-羥苯基]-4,6-雙(2,4-二甲基苯 〇 基)_1，3,5-三嗪以及2-(2,4-二羥苯基)-4,6·雙(2,4-二甲基苯 基)-1,3,5-二嗪；雙(經苯基)三嗪化合物，諸如2,4_雙(2_經 基-4-丙氧基苯基)_6_(2,4_二甲基苯基)三嗪、2,4_雙 (2-羥基-3-甲基丙氧基苯基)_6·(4_曱基苯基>13 5三嗪 以及2,4-雙(2-羥基_3_甲基_4_己氧基苯基)_6_(2,4二曱基苯 基)-1，3,5-二嗪；以及三(經苯基)三嗪化合物，諸如2,4雙(2_ 备基-4- 丁氧基苯基)_6_(24_二丁氧基苯基)_丨，3，5三嗪、 2,4,6_三(2-經基-4-辛氧基苯基)-1,3,5-三嗪以及2,4,6-三[2-羥基_4_(3_ 丁氧基-2_羥丙氧基)苯基]-1，3,5-三嗪。 〇 紫外線吸收劑較佳為由以下式（A)表示之化合物： 式（A):Kogyo Kabushiki Kaisha) FB and SFP series; Tatsumori Ltd.'s 1-FX; Toagosei Co., Ltd.'s HSP series; and Fuso Chemical Co. Ltd.) SP series. The content of the inorganic filler 35 201237551 is preferably from 1% by mass to 60% by mass, more preferably from 2% by mass to 60% by mass of the total solid content (mass) of the polymerizable composition. %, more preferably 4% by mass to 6% by mass. When the amount of addition is in this range, 'in the case where the substrate on which the photosensitive layer is disposed has an uneven sentence shape, the substrate can be successfully tracked more reliably. A photosensitive layer having a shape of a non-uniform shape. [6] Ultraviolet Absorber (Ultravi〇letAbs〇rber) The polymerizable composition of the present invention preferably contains an ultraviolet absorber. The ultraviolet absorber is incorporated into a resist composition such as a solder resist. Exposure and development are performed after forming a photosensitive layer on the semiconductor substrate j in which the resist composition is coated on the solid-state imaging element, in which the alignment mark is provided on the surface. Forming a solder resist layer, thereby making it possible to more reliably produce a "resistance caused by reflected light on the surface of the substrate" and a solder resist for reliably detecting alignment marks by the visible light sensor Floor. In the case where the surface of the substrate on which the photosensitive layer is placed is formed of a material having high light reflectivity such as metal, since the reflected light from the substrate surfactant becomes considerable when exposed to the photosensitive layer, Therefore, the cross-sectional shape of the resulting pattern tends to become a skirt shape (i.e., the rectangular shape of the cross-sectional shape is easily damaged). On the other hand, if the exposure dose is kept low to reduce the inverse (four) n brother, the pattern of the rectangular cross-sectional shape may be difficult to form due to insufficient exposure dose. However, in the case where the polymerizable composition of the present invention contains an ultraviolet absorber, even when irradiated with an exposure dose (hereinafter sometimes referred to as "appropriate exposure dose") necessary for obtaining a pattern having a rectangular sectional shape, The ultraviolet absorber absorbs the reflected light and this makes it easy to form a pattern having the shape of the moment 36 201237551. The ultraviolet absorber is preferably a compound which cannot initiate polymerization of a polymerizable compound by light or heat (i.e., a compound which is not derived from a polymerization initiator). The expression "incapable of initiating polymerization of a polymerizable compound" as used herein means that even when the ultraviolet absorber receives light or heat, it does not produce an active species for initiating polymerization of the polymerizable compound. More specifically, the ultraviolet absorber is preferably not photo-sensitized to ultraviolet rays or visible rays (more specific s' wavelengths of 300 nm to 450 nm) and is more specific to heat (more specifically, For example, heat at 150C to 250C) compounds that do not have thermodynamic sensitivity. The terms "sensitivity" and "temperature sensing" as used herein mean the production of a target function, and involve chemical structural changes due to the action of ultraviolet light or visible rays or heat. Further, the ultraviolet absorber is preferably not only incapable of initiating polymerization of the polymerizable compound but also lacking sensitizer properties described later. As used herein, the term "sensitizer property" means the property of transferring the energy of ❹ by the light absorption of the sensitizer itself to another material (polymerization initiator) and thereby starting polymerization. The σ ultraviolet absorber is preferably a compound having a maximum absorption wavelength between 300 nm and 43 Å, more preferably a compound having a maximum absorption wavelength between 330 nm and 42 Å Nai. Preferably, the ultraviolet absorber has a maximum absorption wavelength in at least the range of: (1) 340 nm to 380 nm, (8) 380 nm to 420 nm, and (III) 420 nm to 450 37 201237551 The range of nanometers. When a pattern is formed by applying exposure and development to a photosensitive layer formed using the polymerizable composition of the present invention, in the case where the exposure light source contains an i-line, the maximum absorption wavelength of the ultraviolet absorber is preferably in the above wavelength range (I )Inside. In the case where the exposure light source contains the h line, the maximum absorption wavelength of the ultraviolet absorber is preferably within the above wavelength range (π). In the case where the exposure light source contains the g line, the maximum absorption wavelength of the ultraviolet absorber is preferably within the above wavelength range (111). As the ultraviolet absorber, for example, a salicylate, a benzophenone, a benzotriazole, a substituted acrylonitrile or a triazine ultraviolet absorber can be used. Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based and external absorbents include 2,2'-di-trans--4-methoxydiphenyl hydrazine, 2,2-carbazyl-4,4'-dimethoxyl Phenyl ketone, 2,2,,4,4,-tetracarboxylic benzophenone, 2·hydroxy-4-decyloxybenzophenone, 2,4-di-perylene benzophenone, and 2 - a thiol-4-octyloxy group 曱 _. Examples of the benzotrisole ultraviolet absorber include 2-(2'-hydroxy-3',5,-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2,-hydroxy- 3,-t-butyl-5,-methylphenyl)_5, chlorobenzotriazole, 2-(2'-hydroxy-3,_t-pentyl-5,-isobutylphenyl)5 Chlorobenzotriazole, hydroxy-3'-isobutyl-5,-nonylphenyl)_5_chloro benzotriazole, 2_(2,-carbamic-3'-isobutyl-5'-propyl Phenyl)-5-chlorobenzotriazole, 2_(2,_carbyl-3,5,2-di-t-butylphenyl)benzotriazole, 2-(2,-hydroxy-5, _Methylphenyl)benzotriene 38 201237551 squat and 2-[2L via _5,,-(1,1,3,3-tetradecyl)phenyl]benzotriazole. Examples of the substituted acrylonitrile-based ultraviolet absorber include 2-cyano-3,3-diphenylacrylate ethyl ester and 2-cyano-3,3-diphenylacrylic acid hexyl hexanoic acid. Examples of the triazine-based ultraviolet absorber include a mono(hydroxyphenyl)triazine compound such as 2_[4_[(2-pyridyldodecyloxypropyl)oxy]_2hydroxyphenyl]-4,6 - bis(2,4-dimethylphenyl)+3,5:azine, 2_[4_[(2_carbyl_3_dodecyloxypropyl)oxy]-2-hydroxyphenyl]- 4,6-bis(2,4-dimethylphenylhydrazinyl)_1,3,5-triazine and 2-(2,4-dihydroxyphenyl)-4,6·bis(2,4-di Methylphenyl)-1,3,5-diazine; bis(phenyl)triazine compound, such as 2,4-bis(2-cyso-4-propoxyphenyl)_6_(2,4 _Dimethylphenyl)triazine, 2,4-bis(2-hydroxy-3-methylpropoxyphenyl)_6·(4-nonylphenyl)13 5 triazine and 2,4- Bis(2-hydroxy-3-methyl-4-indolyloxyphenyl)_6-(2,4-didecylphenyl)-1,3,5-diazine; and tris(phenyl)triazine compound , such as 2,4 bis(2_predyl-4-butoxyphenyl)_6_(24-dibutoxyphenyl)-indole, 3,5 triazine, 2,4,6_three (2- 4-octyloxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-yl-(3-butoxy-2-hydroxypropyloxy)phenyl]- 1,3,5-triazine. The 〇 ultraviolet absorbing agent is preferably a compound represented by the following formula (A): Formula (A):

在式中’ R01以及r62各自獨立地表示氫原子、烷基、 务基或藉由彼此組合形成5員環（5-membere(l ring)或6 39 201237551 A ^yxx 員環必需之非金屬原子團。此外，R01以及R62中^壬一者均 可與緊接於氮原子之次曱基組合形成5員環或6員環。χ_ 以及Y61各自獨立地表示氰基、_COOR63、_c〇NR63r 、 COR63、~S〇2R63 或-SO2R63R64 ’ 且 R63 以及 R64 各自獨立 地表示氫原子、烷基或芳基。Χό1與Yq可彼此組合形成5 員環或6員環。此外’ r61、r62、χ61以及γ6ι中任一者均 可與由式（A)表示之另一化合物中之以及 Y61中任~者組合形成二聚體。 下文說明由式（A)表示之化合物的特定實例，彳曰本 發明並不限於此。 CO^CgH,/' NS〇ihIn the formula, 'R01 and r62 each independently represent a hydrogen atom, an alkyl group, a diradical group or a non-metal atomic group necessary for forming a 5-membered ring (5-membere (l ring) or 6 39 201237551 A ^yxx member ring by combining with each other. In addition, one of R01 and R62 can be combined with a sulfhydryl group immediately adjacent to a nitrogen atom to form a 5-membered ring or a 6-membered ring. χ_ and Y61 each independently represent a cyano group, _COOR63, _c〇NR63r, COR63. , ~S〇2R63 or -SO2R63R64 ' and R63 and R64 each independently represent a hydrogen atom, an alkyl group or an aryl group. Χό1 and Yq may be combined with each other to form a 5-membered ring or a 6-membered ring. Further 'r61, r62, χ61 and γ6ι Any of them may be combined with any of the compounds represented by the formula (A) and any of Y61 to form a dimer. Hereinafter, a specific example of the compound represented by the formula (A) will be described. Not limited to this. CO^CgH,/' NS〇ih

CeH13CeH13

CNCN

N-CH=CH-CH=C CeHis CNN-CH=CH-CH=C CeHis CN

CN CH3 CCN CH3 C

My、 N-CH^H-CH^ N-CH=CH-CH=qMy, N-CH^H-CH^ N-CH=CH-CH=q

CzHs k〇2(pHC02C8H17·" CHa 、 ΓΜCzHs k〇2(pHC02C8H17·" CHa, ΓΜ

C4H? COCH3 .n^h=ch-ch=c C〇2p6H13n ISO-C3H7 C〇2 ;N-CH=CH-CH:C isoCgHy NS02PhC4H? COCH3 .n^h=ch-ch=c C〇2p6H13n ISO-C3H7 C〇2 ;N-CH=CH-CH:C isoCgHy NS02Ph

N-CH=CH-CH=C -ck N SOaPhN-CH=CH-CH=C -ck N SOaPh

CH-CH=(/ fcONHCW 在本發明中’可單獨使用這些各種紫外線吸收劑中一 者，或可組合使用其兩者或超過兩者。 本發明之可聚合組成物可能含有或可能不含有紫外 40 201237551 線吸收劑’但在含有紫外線吸收劑之情況下，以本發明之 物的全部固體含量（質量）計，其含量較佳為 0.001貝至1質量％，更佳為g g [6]除了鶴化合物之外之紅外阻播材料 · ^/° ΟCH-CH=(/fcONHCW In the present invention, one of these various ultraviolet absorbers may be used alone, or both or more may be used in combination. The polymerizable composition of the present invention may or may not contain ultraviolet rays. 40 201237551 Linear absorbent 'but in the case of containing a UV absorber, the content is preferably from 0.001 to 1% by mass, more preferably gg [6], based on the total solid content (mass) of the present invention. Infrared blocking material other than crane compound · ^/° Ο

本發明之可聚合組成物可含有在不損害本發明之作 用之範圍_除了氣合物之外之紅外阻㈣料以及金屬 蝴化物（在下文中有時稱作「其他紅外阻撞材料）」。其他 紅外阻擋材料較佳為在800奈米至12〇〇奈米之波長下具 有吸收且對曝光所用之光顯示良好透明度的化合物，且自、 此等觀點來看，其他紅外阻擋材料較佳是選擇自紅外吸收 染料（infrared-absorbing dyestuff)以及紅外吸收體無機顏 料（infrared-absorbent inorganic pigment)之中。 紅外吸收染料之實例包括花青染料（Cyanine dye )、酜 菁 ¥ 料（phthalocyanine dye)、秦駄菁染料（naphtlialocyanine dye )、亞胺鏽染料（immonium dye )、胺鑌染料（aminium dye )、喹琳鏽染料（quin〇iiurn dye )、正旅喃離子染料 (pyrylium dye )以及金屬錯合物染料，諸如Ni錯合物染料。 可用作紅外阻擋材料之染料亦可以是市售產品，且其 較佳實例包括以下市售染料： FEW 化學公司（FEW Chemicals)製造之 S0345、 S0389、S0450、S0253、S0322、S0585、S0402、S0337、 S0391、S0094、S0325、S0260、S0229、S0447、S0378、 S0306 以及 S0484 ; 美洲染料資源公司（American Dye Source，Inc.)製造 41 201237551The polymerizable composition of the present invention may contain an infrared resist (tetra) material and a metal halide (hereinafter sometimes referred to as "other infrared blocking material") in a range which does not impair the effects of the present invention. Other infrared blocking materials are preferably compounds which absorb at a wavelength of from 800 nm to 12 nm and which exhibit good transparency to light used for exposure, and from this point of view, other infrared blocking materials are preferably It is selected from infrared-absorbing dyestuffs and infrared-absorbent inorganic pigments. Examples of infrared absorbing dyes include Cyanine dye, phthalocyanine dye, naphtlialocyanine dye, imimium dye, aminium dye, quinoline rust. A quin〇iiurn dye, a pyrylium dye, and a metal complex dye such as a Ni complex dye. The dye which can be used as the infrared blocking material can also be a commercially available product, and preferred examples thereof include the following commercially available dyes: S0345, S0389, S0450, S0253, S0322, S0585, S0402, S0337 manufactured by FEW Chemicals. , S0391, S0094, S0325, S0260, S0229, S0447, S0378, S0306, and S0484; manufactured by American Dye Source, Inc. 41 201237551

~T\JU A 之 ADS795WS、ADS805WS、ADS819WS、ADS820WS、 ADS823WS、ADS830WS、ADS850WS、ADS845MC、 ADS870MC、ADS880MC、ADS890MC、ADS920MC、 ADS990MC、ADS805PI、ADSW805PP、ADS810CO、 ADS813MT、ADS815EI、ADS816EI、ADS818HT、 ADS819MT、ADS819MT、ADS821NH、ADS822MT、 ADS838MT、ADS840MT、ADS905AM、ADS956BP、 ADS1040P、ADS1040T、ADS1045P、ADS1040P、 ADS1050P、ADS1065A、ADS1065P、ADS1100T 以及 ADS1120F ； 山本化學工業有限公司（Yamamoto Chemical Industry Co., Ltd·)製造之 YKR-4010、YKR-3030、YKR-3070、 MIR-327、MIR-371、SIR-159、PA-1005、MIR-369、 MIR-379、SIR-128、PA-1006、YKR-2080、MIR-370、 YKR-3040、YKR-308卜 SIR-130、MIR-362、YKR-3080、 SIR-132 以及 PA-1001 ;以及 林原生物化學研究所（Hayashibara Biochemical Labs. Inc.)製造之 NK-123、NK-124、NK-1144、NK-2204、 NK-2268、NK-3027、NKX-113、NKX-1199、NK-2674、 NK-3508、NKX-114、NK-2545、NK-3555、NK-3509 以及 NK-3519。 在這些染料中，鑒於耐熱性，酜菁染料以及金屬錯合 物染料為較佳。 可單獨使用這些染料中的一者，或為了在800奈米至 42 201237551 1,200奈米之波長下產生良好擔光作用’根據此目的，可 混合並使用兩種或超過兩種染料。 可用作其他紅外阻擋材料之紅外吸收體無機顏料之 實例包括鋅華（zinc flower)、鉛白、鋅鋇白（lithop〇ne )、 乳化鈦氧化路、沈版硫酸鎖、重晶石粉（barite p〇wder )、 紅鉛（red lead)、氧化鐵紅、鉛黃、鋅黃（丨型鋅黃、2型 鋅黃）、群青（ultramarine blue)、普魯士藍（prussian blue ) 〇 (亞鐵氰化鐵/亞鐵氰化鉀）、锆石灰（zircon grey)、镨黃 (praseodymium yellow )、鉻鈦黃、鉻綠、孔雀藍（peac〇ck blue )、維多利亞綠（victoria green )、鐵藍（與普魯士藍無 關）、鈒·錯藍、鉻-錫紅（chrome_tin pink )、猛紅（manganese pink)以及橙紅（saimon pink)。此外，可使用例如各自含 有一種金屬元素或兩種或超過兩種金屬元素之金屬氧化 物、金屬氮化物或其混合物作為黑色顏料，所述金屬元素 是選擇自由 Co、Cr、Cu、Mn、Ru、Fe、Ni、Sn、Ti 以及 Ag所組成之族群中。 O 黑色顏料較佳為鈦黑，亦即含氮化鈦之黑色顏料，這 是因為其在800奈米至i，2〇〇奈米之波長下的紅外區中之 遮蔽性質良好。 鈦黑可藉由習知方法獲得，且可以是市售產品，可使 用例如由石原產業有限公司（Ishihara Sangyo Kaisha. Ltd.)、赤穗化成有限公司（Ak〇 Kasei c〇 , Ltd )、JEMC〇 公司（JEMCO Inc.)、三菱材料公司（Mitsubishi Materials Corp.)或二菱材料電子化學有限公司（Mitsubishi Materials 43 201237551~T\JU A's ADS795WS, ADS805WS, ADS819WS, ADS820WS, ADS823WS, ADS830WS, ADS850WS, ADS845MC, ADS870MC, ADS880MC, ADS890MC, ADS920MC, ADS990MC, ADS805PI, ADSW805PP, ADS810CO, ADS813MT, ADS815EI, ADS816EI, ADS818HT, ADS819MT, ADS819MT, ADS821NH, ADS822MT, ADS838MT, ADS840MT, ADS905AM, ADS956BP, ADS1040P, ADS1040T, ADS1045P, ADS1040P, ADS1050P, ADS1065A, ADS1065P, ADS1100T and ADS1120F; YKR-4010 manufactured by Yamamoto Chemical Industry Co., Ltd. , YKR-3030, YKR-3070, MIR-327, MIR-371, SIR-159, PA-1005, MIR-369, MIR-379, SIR-128, PA-1006, YKR-2080, MIR-370, YKR -3040, YKR-308, SIR-130, MIR-362, YKR-3080, SIR-132, and PA-1001; and NK-123, NK-124, manufactured by Hayashibara Biochemical Labs. Inc. , NK-1144, NK-2204, NK-2268, NK-3027, NKX-113, NKX-1199, NK-2674, NK-3508, NKX-114, NK-2545, NK-3555, NK-3509 and NK -3519. Among these dyes, phthalocyanine dyes and metal-based dyes are preferred in view of heat resistance. One of these dyes may be used alone or in order to produce a good light-supporting effect at a wavelength of 800 nm to 42 201237551 1,200 nm. According to this purpose, two or more dyes may be mixed and used. Examples of infrared absorber inorganic pigments which can be used as other infrared blocking materials include zinc flower, lead white, lithop〇ne, emulsified titanium oxide road, plated sulfuric acid lock, barite powder (barite) P〇wder ), red lead, red iron oxide, lead yellow, zinc yellow (yttrium zinc yellow, type 2 zinc yellow), ultramarine blue, prussian blue, ferrocyanide Iron (potassium ferrocyanide), zircon grey, praseodymium yellow, chrome titanium yellow, chrome green, peacock blue, victoria green, iron blue It has nothing to do with Prussian Blue), 鈒·Blue, chrome_tin pink, manganese, and saimon pink. Further, as the black pigment, for example, a metal oxide, a metal nitride or a mixture thereof each containing one metal element or two or more than two metal elements selected from free Co, Cr, Cu, Mn, Ru may be used. Among the groups of Fe, Ni, Sn, Ti, and Ag. The O black pigment is preferably titanium black, that is, a black pigment containing titanium nitride because of its good shielding properties in the infrared region at a wavelength of from 800 nm to 2 nm. Titanium black can be obtained by a conventional method, and can be a commercially available product, and can be used, for example, by Ishihara Sangyo Kaisha. Ltd., Akashi Kasei c〇, Ltd., JEMC. JEMCO Inc., Mitsubishi Materials Corp. or Mitsubishi Materials 43 201237551

Electronic Chemicals Co.，Ltd.)製造之鈦黑。 鈦f表示具有鈦原子之黑色粒子，且低階氧化欽 必要時，為了改良分散性、防止聚集或其類似目ft使 用經表面改質之粒子作為鈦黑粒子。 之 表面改質方法包括用選擇自氧化矽、氧化 :方Π*氧化鎂以及氧化錯中的一員或多員覆蓋表面 i=^m2(K)7_3()2836之段利咖]至段 洛[0027]中所述之防水物質處理表面。 又 ，造鈦黑之〒的實例包括（但不限於）藉由在還原 %〇兄中加熱來還原二氧化鈦與金屬鈦之混合物的方法 (JP-A專5432);在含有氫氣之還原性環 $ 溫水解四氣化鈦獲得之超細二氧化鈇之方ς (JP-A-57-205322);在高溫下在氨存在下 =化欽之方法(一咖、一 ，鈒化合物附著於二氧傾或躲錢，縣 氨存在下將其還原之方法（JP-A-61-201610)。同'皿 多性欽黑之粒徑不受制關，但11於分散性以及染 色i· (colomb山ty) ’粒徑較佳為3奈米至 佳為10奈米至500奈米。 ，_不米更 制，^積（specific surface area)不受特別限 制仁通W BET法量測之值較佳為大約5公 :公尺2/公克’更佳為大約20公尺2/公克至ι〇〇公尺2/ 么克，适是因為鈦黑在以防水劑表面處理後就防水性而言 44 201237551 可具有預定效能之故。 關於用作其他紅外阻擋材料之無機顏料的粒徑，平均 粒徑較佳為3奈米至0.01毫米，且鑒於分散性、擋光作用 以及隨著老化之沈澱，平均粒徑較佳為1〇奈米至i微米。Titanium black manufactured by Electronic Chemicals Co., Ltd.). Titanium f represents black particles having a titanium atom, and low-order oxidation, if necessary, uses surface-modified particles as titanium black particles in order to improve dispersibility, prevent aggregation, or the like. The surface modification method includes covering the surface i=^m2(K)7_3()2836 by the selection of auto-ruthenium oxide, oxidation: square Π*magnesium oxide, and one or more members of the oxidation fault] to Duan Luo [ The water repellent treatment surface described in 0027]. Further, examples of the titanium black ruthenium include, but are not limited to, a method of reducing a mixture of titanium oxide and titanium metal by heating in a reduced % ( brother (JP-A special 5432); in a reducing ring containing hydrogen Superfine cerium oxide obtained by warm hydrolysis of titanium tetrahydrate (JP-A-57-205322); at high temperature in the presence of ammonia = method of chemistry (one coffee, one, bismuth compound attached to dioxane Pour or hide money, the method of reducing it in the presence of ammonia in the county (JP-A-61-201610). The particle size of the same dish is not controlled, but 11 is dispersible and dyed i· (colomb mountain Ty) 'The particle size is preferably from 3 nm to preferably from 10 nm to 500 nm. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Preferably, it is about 5 mm: metric 2/m gram is more preferably about 20 ft 2 / gram to ι ft 2 / gram, because titanium black is water-repellent after surface treatment with water repellent. 44 201237551 may have a predetermined performance. Regarding the particle size of the inorganic pigment used as the other infrared blocking material, the average particle diameter is preferably from 3 nm to 0.01 mm, and Resistance, light-blocking effect as well as the aging of the precipitates, the average particle diameter is preferably 1〇 i microns to nanometers.

可聚合組成物可能含有或可能不含有其他紅外阻擋 材！!旦但在含有其他紅外阻擋材料之情況下，以鎢化合^ 之質量計，其含量較佳為5質量％至75質量％，更佳為1〇 質量％至40質量％。 ” [7]分散劑 在本發明中，尤其當鶴化合物為細粒時，可使用習知 分散劑來分散細粒以達成增強可聚合組成物中鎢化合物之 分散性以及分散穩定性之目的。 σ 作為分散劑，可適當地選擇及使用例如習知 界面活性劑。 刀双削4 言之’可使用多種化合物，且其實例包括陽離子 界面/舌性劑，諸如有機矽氧烷聚合物ΚΡ341 (由作越化學The polymerizable composition may or may not contain other infrared barriers! However, in the case of containing other infrared blocking materials, the content thereof is preferably from 5% by mass to 75% by mass, more preferably from 1% by mass to 40% by mass, based on the mass of the tungsten compound. [7] Dispersant In the present invention, especially when the crane compound is fine particles, a conventional dispersant may be used to disperse the fine particles for the purpose of enhancing the dispersibility and dispersion stability of the tungsten compound in the polymerizable composition. As the dispersing agent, σ, for example, a conventional surfactant can be appropriately selected and used. A plurality of compounds can be used, and examples thereof include a cationic interface/tongue agent such as an organic siloxane polymer ΚΡ341 ( Yuki Chemical

Chemical co-} 丰口物Polyflow 75號、90號以及95號（由共榮社化學有 (Kyodsha Chemical c。·，Ltd.)製造），以及 w〇〇i ΐ艮公司（偏製造）；非離子界面活 氧乙烯月桂_、聚氧乙稀十八烧細、聚 =乙、聚氧乙烯辛基苯麵、聚氧乙烯壬基苯基 山利二月桂_、聚乙二醇二硬脂酸S旨以及脫水 山木糖_曰肪酸醋；陰離子界面活性劑，諸如w〇〇4、w〇〇5 45 201237551 -rv/j 1 厶 pjixChemical co-} Polyport No. 75, No. 90 and No. 95 (manufactured by Kyodsha Chemical C., Ltd.), and w〇〇i ΐ艮 Company (partial manufacturing); Ion interface oxyethylene laurel _, polyoxyethylene eucalyptus burnt, poly = B, polyoxyethylene octyl benzene surface, polyoxyethylene decyl phenyl sulphate dilauric _, polyethylene glycol distearic acid S And dehydrated xylose _ fatty acid vinegar; anionic surfactants, such as w〇〇4, w〇〇5 45 201237551 -rv/j 1 厶pjix

以及W017 (由友松有限公司製造）；聚合物分散劑，諸如 EFKA-46、EFKA-47、EFKA-47EA、EFKA POLYMER 100、 EFKA POLYMER 400、EFKA POLYMER 401、EFKA POLYMER 450 (均由日本巴斯夫製造）；各種Solsperse分 散劑，諸如 SOLSPERSE 3000、5000、9000、12000、13240、 13940、17000、24000、26000、28000、32000 以及 36000 (由路博潤公司（Lubrizol Corporation )製造）；ADEKA PLURONIC L3 卜 F38、L42、L44、L6 卜 L64、F68、L72、 P95、F77、P84、F87、P94、LUU、P103、F108、L121 以 及P-123 (由ADEKA製造）、ISONET S-20 (由三洋化學 工業有限公司（Sanyo Chemical Industries，Ltd.)製造）， 以及 Disperbyk 10卜 103、106、108、109、111、112、116、 130、140、142、162、163、164、166、167、170、171、 174、176、180、182、2000、20(H、2050 以及 2150 (由日 本畢克化學公司（BYKChemie Japan)製造）。其他實例包 括在分子末端或側鏈中具有極性基之寡聚物或聚合物，諸 如丙晞酸共聚物。 鑒於分散性、可顯影性、沈澱，JP-A-2010-106268中 所述之以下樹脂為較佳，且尤其鑒於分散性，在側鏈中具 有聚酯鏈之聚合物分散劑為較佳。此外，鑒於藉由光微影 形成之圖案的分散性以及解析度，具有酸基以及聚酯鏈之 樹脂為較佳。作為分散劑中之酸基，鑒於吸附性質，pKa 為6或低於6之酸基為較佳，且羧酸、磺酸或磷酸為更佳。 下文描述JP-A-2010-106268中所述之分散劑樹脂，其 46 201237551 較佳是用於本發明。 分散劑樹脂較佳為在分子中含有接枝鏈之接枝共聚 物，所述接枝鏈具有數目為40至10,000之原子（除氫原 子外）且是選擇自聚酯結構、聚醚結構以及聚丙烯酸酯結 構中，所述共聚物為含有由以下式（1)至（5)中任一者 表示之結構單元的接枝共聚物。And W017 (manufactured by Yousong Co., Ltd.); polymer dispersants such as EFKA-46, EFKA-47, EFKA-47EA, EFKA POLYMER 100, EFKA POLYMER 400, EFKA POLYMER 401, EFKA POLYMER 450 (both manufactured by BASF, Japan) ; various Solsperse dispersants, such as SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, 32000, and 36000 (manufactured by Lubrizol Corporation); ADEKA PLURONIC L3 Bu F38, L42, L44, L6, L64, F68, L72, P95, F77, P84, F87, P94, LUU, P103, F108, L121 and P-123 (manufactured by ADEKA), ISONET S-20 (by Sanyo Chemical Industry Co., Ltd.) (manufactured by Sanyo Chemical Industries, Ltd.), and Disperbyk 10, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174 , 176, 180, 182, 2000, 20 (H, 2050, and 2150 (manufactured by BYK Chemie Japan). Other examples include oligomers or polymers having polar groups at the molecular end or side chain. , such as Propylene acid copolymer. In view of dispersibility, developability, precipitation, the following resins described in JP-A-2010-106268 are preferred, and in particular, in view of dispersibility, a polymer having a polyester chain in a side chain A dispersant is preferred. Further, in view of the dispersibility and resolution of the pattern formed by photolithography, a resin having an acid group and a polyester chain is preferred. As an acid group in the dispersant, pKa is considered in view of adsorption property. An acid group of 6 or less is preferred, and a carboxylic acid, a sulfonic acid or a phosphoric acid is more preferred. The dispersant resin described in JP-A-2010-106268 is described below, and 46 201237551 is preferably used for The dispersant resin is preferably a graft copolymer containing a graft chain having a number of atoms of 40 to 10,000 (except hydrogen atoms) and selected from a polyester structure, and polymerized. In the ether structure and the polyacrylate structure, the copolymer is a graft copolymer containing a structural unit represented by any one of the following formulas (1) to (5).

在式（1 )至式（5 )中，X1、X2、X3、X4、X5以及 X6各自獨立地表示氫原子或單價有機基團，且鑒於合成限 制，較佳為氫原子或碳數目為1至12之烷基，更佳為氫原 子或曱基，更佳為甲基。 47 201237551 在式（3)以及式（4)中，R’表示分支鏈或直鏈伸烷 基（碳數目較佳為1至10,更佳為2或3)且較佳為式（3) 中-ch2-ch(ch3)-表示之基團以及式（4)中-ch(ch3)-ch2-表示之基團。 在式（1)至式（5)中，Y1、Y2、Y3、Y4以及Y5各 自獨立地表示二價連接基團且結構不受特別限制。其特定 實例包括以下連接基團（Y-1)至連接基團（Y-20)。在以 下文結構中，A以及B分別表示在式（1)至式（5)中連 接至左末端基以及右末端基之鍵。在下文所示之結構中， 鑒於合成容易性，（Y-2)以及（Y-13)為較佳。 48 201237551In the formulae (1) to (5), X1, X2, X3, X4, X5 and X6 each independently represent a hydrogen atom or a monovalent organic group, and in view of synthesis limitation, preferably a hydrogen atom or a carbon number of 1 The alkyl group to 12 is more preferably a hydrogen atom or a fluorenyl group, more preferably a methyl group. 47 201237551 In the formula (3) and the formula (4), R' represents a branched chain or a linear alkyl group (the number of carbon is preferably from 1 to 10, more preferably 2 or 3) and is preferably the formula (3). a group represented by -ch2-ch(ch3)- and a group represented by -ch(ch3)-ch2- in the formula (4). In the formulae (1) to (5), Y1, Y2, Y3, Y4 and Y5 each independently represent a divalent linking group and the structure is not particularly limited. Specific examples thereof include the following linking group (Y-1) to a linking group (Y-20). In the following structures, A and B respectively represent a bond to the left terminal group and the right terminal group in the formulae (1) to (5). In the structure shown below, (Y-2) and (Y-13) are preferred in view of ease of synthesis. 48 201237551

ss

A'''/X^N 人 B H (Y-3)A'''/X^N person B H (Y-3)

A^BA^B

(Y-6) (Y-9)(Y-6) (Y-9)

OO

Α^Λ^Β (Y-15)Α^Λ^Β (Y-15)

(Y-16) (Y-17) (Y-18)(Y-16) (Y-17) (Y-18)

OH α〜Λ^β o (Y-19) (Y-20) 在式（1)至式（5)中，Z1、Z2、Z3、Z4以及Z5各自 49 201237551 獨立地表示氫原子或單價取代基，且 _。其特定實例包括絲、經基、貌氧基、== =氧^、絲硫醚基、芳基硫嶋、雜芳基硫喊以及胺 土。，、中，自增強分散性之觀點來看，具有立體排斥效應 n effeCt)者為較佳’且碳數目為5至24之 t ί ΪΪ岐’碳數目為5至24之分支鍵烧基 次厌數目為5至24之環狀烷基為較佳。 式（5)中…各自表示 至=:)二=’咖各自獨立地表示2 ,r?,,.鑒於刀放穩疋性以及可顯影性，式（1)以及 5 0 以及k各自較佳為4至6之整數，且最佳為 構不ίίϋ〖中’ r表示氣原子或單價有機基團且其結 更佳為氫#_^，但較佳為氩原子、絲、芳基或雜芳基， 為1 = 或烷基。當R為烷基時，烷基較佳為碳數目 或碳數目為之5錢絲、碳數目為3至2G之分支鏈烧基， 之直赫至2〇之環狀烷基，更佳為碳數目為1至20 二J)佳中為:炭數目為1至6之直鏈烧基。OH α~Λ^β o (Y-19) (Y-20) In the formulae (1) to (5), each of Z1, Z2, Z3, Z4 and Z5 49 201237551 independently represents a hydrogen atom or a monovalent substituent And _. Specific examples thereof include silk, mercapto, morphoxy, == = oxygen, thioether, aryl sulfonium, heteroaryl sulfonate, and amine earth. , , , from the standpoint of self-enhancing dispersibility, those having a steric repulsion effect n effeCt) are preferred 'and the number of carbons is 5 to 24, t ί ΪΪ岐' carbon number is 5 to 24 A cyclic alkyl group having a number of 5 to 24 is preferred. In the formula (5), each represents to =:) two = 'the coffees each independently represent 2, r?,., in view of the smoothness and developability of the knife, the formulas (1) and 50 and k are each preferably. It is an integer of 4 to 6, and preferably is not a structure. The middle r represents a gas atom or a monovalent organic group and the junction thereof is more preferably hydrogen #_^, but is preferably an argon atom, a wire, an aryl group or a hetero atom. Aryl, 1 = or alkyl. When R is an alkyl group, the alkyl group is preferably a carbon number or a branched carbon group having a carbon number of 3 to 2 G, a cyclic alkyl group of from 2 to 2 G, more preferably The number of carbons is from 1 to 20, and the second is: a linear alkyl group having a carbon number of 1 to 6.

可混合且用二定:二。兩個或超過兩個結構不同之R 構單可顯影性，由式⑴表示之結 此外，^由以下式（1A)表示之結構單元。 ，鑒於分散穩定性以及可顯影性，由式（2)表 50 201237551 示之結構單元較佳為由 以下式（2A)表示之結構單元。Can be mixed and used two: two. Two or more than two structurally different R-form developability, a junction represented by the formula (1) Further, a structural unit represented by the following formula (1A). In view of dispersion stability and developability, the structural unit represented by the formula (2) Table 50 201237551 is preferably a structural unit represented by the following formula (2A).

(2A) 在式（1A)中，χι、γ1、zl(2A) In the formula (1A), χι, γ1, zl

χ1、γ1、β以及n相同之 /及n具有與式⑴中 在式(2Α)中，χ2、3ζ2=佳範圍亦相同。 χ2、Y2、z2以月m z以及仿具有與式（2)中 最重要的θ，λ目5之含義’且較佳範圍亦相同。 之化合物為較ί。作么2表示之在側鏈中具有聚酯鏈 化&物71亦宜在本發明中用作分散劑。Χ1, γ1, β, and n are the same as / and n are the same as in formula (1) in formula (2Α), χ2, 3ζ2=good range. Χ2, Y2, and z2 have the same meaning as the most important θ, λ mesh 5 in the formula (2) and the preferred range. The compound is ί. It is also indicated that having a polyester chaining & 71 in the side chain is also useful as a dispersing agent in the present invention.

下文說明例示化合物丨關示化合物％作為適用於 本發明之分散劑’但本翻並不限於此。在下文說明之化 合物中，連接至各結構單元之數值（連接至主鏈之重複單 兀的數值）表示結構單元之含量[以質量計之％;表示為「重 量％」]。連接至側鏈之重複單元的數值表示重複單元之重 複數目。 51 201237551Hereinafter, the exemplified compound 丨 indicates the % of the compound as a dispersing agent suitable for the present invention', but the present invention is not limited thereto. In the compounds described below, the value attached to each structural unit (the value of the repeating unit attached to the main chain) indicates the content of the structural unit [% by mass; expressed as "% by weight"]. The value of the repeating unit connected to the side chain indicates the number of repeating units. 51 201237551

4#©H 6：a (重量％)4#©H 6:a (% by weight)

(例示化合物4) 52 201237551(Illustrated Compound 4) 52 201237551

(例示化合物7)(exemplary compound 7)

53 201237551 TV/*/ i53 201237551 TV/*/ i

(例示化合物9)(exemplary compound 9)

(例示化合物10) 54 201237551(Illustrated Compound 10) 54 201237551

(例示化合物13)(exemplary compound 13)

55 20123755155 201237551

O^OMe (例示化合物16) 56 201237551O^OMe (exemplified compound 16) 56 201237551

57 201237551 -tv/j ϋμΑ_ι57 201237551 -tv/j ϋμΑ_ι

58 20123755158 201237551

(例示化合物23)(exemplary compound 23)

(例示化合物24)(Illustrated Compound 24)

(例示化合物25)(Illustrated Compound 25)

(例示化合物26) 59 201237551 i 厶μιι(Illustrated Compound 26) 59 201237551 i 厶μιι

60 20123755160 201237551

(例示化合物31)(exemplary compound 31)

(例示化合物34)(exemplary compound 34)

OHOH

61 20123755161 201237551

62 20123755162 201237551

63 201237551 ^tVJJ ιζ,ριι63 201237551 ^tVJJ ιζ, ριι

(例示化合物44)(Illustrated Compound 44)

O^OMe 64 201237551O^OMe 64 201237551

:/识5重量％: / Sense 5 wt%

(例示化合物50) C5H10—4(Illustrated Compound 50) C5H10-4

鑒於分散性、可顯影性以及沈澱性質，分散劑較佳為 在侧鏈中具有聚醋鏈之樹脂，且鐾於分散性以及解析性 質，更具有酸基之樹脂為較佳。鑒於吸附性質，酸基較佳 為pKa為6或低於6之酸基，更佳為衍生自叛酸、續酸或 磷酸之酸基。 鑒於分散溶液中之溶解度以及分散性以及可顯影 性，具有羧酸基且其中聚酯鏈為聚己内酯侧鏈之樹脂為最 65 201237551 "TKf^ 佳。 諸如川研精化有限公司（Kawaken Fine Chemicals， Ltd·)製造之Hin〇act T_8〇〇〇E的兩性分散劑&叫&㈣ dispersant)亦可用作分散劑。 在使用分散劑之情況下，自增強分散性之觀點來看， 分散組成物較佳使用鎢化合物（必要時，以及其他紅外阻 擋材料）、分散劑以及適當溶劑來製備，接著摻合於可 組成物中。 σ 可聚合組成物可能含有或可能不含有分散劑，但在含 $散劑之情況下，以分散組成物情化合物之全部固體 含量（質量）計’或在使用其他紅外阻播材料且使用紅外 吸收體無機麟作為其他紅外阻#制之情況下，以嫣化 合物與紅外吸收體無機顏料之全部固體含量（質量）之和 j*，分散劑在分散組成物中之含量較佳為i質量％至質 置Λ，更佳為3質量％至7〇質量％。 、 [8]敏化劑 本發明之可聚合組成物較佳含有敏化劑以達成增強 ，合起始劑之自由基產生效率以及將感光波長位移至較長 L長侧之目的。可用於本發日种之敏化劑難為能夠藉由 =子轉移卿或能量轉移_綠化光聚合起始劑之敏化 可用於本發明中之敏化劑包㈣於下文列舉之化合物 奈米至45G奈米之波長區域中具有吸收波長的敏 化劑。 敏化劑之較佳實例包括屬於以下化合物且在330奈米 66 201237551 至450奈米之波長區域中具有吸收波長的敏化劑。 實例包括多核芳族化合物（例如菲、蒽、芘、花、聯 伸二本、9,10-一烧氧基恩）、二笨弁旅π南類化合物（例如 螢光素、伊紅（eosin)、紅螢素（erythrosine)、若丹明β (Rhodamine B)、孟加拉玫紅（R0se Bengal))、頓網 (thioxanthone)類化合物（例如異丙基噻噸酮、二乙基嗟 嘲酮、氯頓酮）、η丫咬酮（acrid〇ne)類化合物（例如。丫 啶酮、氯吖啶酮、N-曱基吖啶酮、N-丁基吖啶酮、1〇_正丁 基-2-氣吖啶酮）、花青（cyanine)類化合物（例如硫幾花 青（thiacarbocyanine)、氧羰花青（oxacarbocyanine))、部 花青（merocyanine)類化合物（例如部花青、羰部花青 (carbomerocyanine))、酞菁類化合物、噻嗪類化合物（例 如疏堇（thionine )、亞甲基藍（methylene blue )、曱苯胺藍 (toluidine blue ))、吖咬（acridine )類化合物（例如π丫咬撥 (acridine orange )、氯黃素（chloroflavin )、吖咬黃素 (acriflavin ))、蒽酿（anthraquinone )類化合物（例如蒽酿）、 芳酸菁（squarylium )類化合物（例如芳酸菁）、吖咬橙、 香豆素（coumarin)類化合物（例如香豆素、7-二乙胺基-4-甲基香豆素）、酮香豆素、啡°塞嗓（phenothiazine)類化合 物、吩嗓（phenazine)類化合物、苯乙烯基苯類化合物、 偶氮化合物、二苯基曱烷、三苯甲烷、二苯乙烯基苯類化 合物、叶嗤（carbazole)類化合物、〇卜淋（porphyrin)、螺 環化合物、啥°丫咬酮（quinacridone)、彀藍（indigo)、笨 乙烯基、正派喃離子化合物、β比11各亞甲基化合物 67 201237551 (pyromethene compound)、吼0坐并三0坐化合物、苯并嘆唾 化合物、巴比妥酸衍生物、硫代巴比妥酸衍生物、芳族g同 化合物（諸如苯乙酮、二苯f酮、噻噸酮以及米希勒鲷 (Michler’sketone))以及雜環化合物（諸如队芳基嗯唾〇定In view of dispersibility, developability, and precipitation properties, the dispersant is preferably a resin having a polyacetal chain in a side chain, and is preferably a resin having an acid group in view of dispersibility and analytical properties. In view of the adsorption property, the acid group is preferably an acid group having a pKa of 6 or less, more preferably an acid group derived from a tickic acid, a reductive acid or a phosphoric acid. In view of the solubility and dispersibility and developability in the dispersion solution, the resin having a carboxylic acid group and in which the polyester chain is a polycaprolactone side chain is preferably 65 201237551 "TKf^. An amphoteric dispersant & called & dispersant manufactured by Kawaken Fine Chemicals, Ltd. can also be used as a dispersing agent. In the case of using a dispersing agent, from the viewpoint of self-reinforcing dispersibility, the dispersion composition is preferably prepared by using a tungsten compound (and, if necessary, other infrared blocking materials), a dispersing agent, and a suitable solvent, followed by blending into a composition. In. The σ polymerizable composition may or may not contain a dispersing agent, but in the case of a powder containing, the total solid content (mass) of the compound of the dispersed constituents is used or other infrared blocking materials are used and infrared absorption is used. In the case where the inorganic inorganic lin is used as the other infrared resist, the total solid content (mass) of the bismuth compound and the infrared absorbing inorganic pigment is j*, and the content of the dispersing agent in the dispersed composition is preferably i% by mass. The texture is preferably 33% by mass to 7% by mass. [8] Sensitizer The polymerizable composition of the present invention preferably contains a sensitizer for the purpose of enhancing the radical generating efficiency of the initiator and shifting the photosensitive wavelength to the longer L long side. The sensitizer which can be used in the present invention is difficult to be used as a sensitizer package in the present invention by sensitization of a sub-transfer or energy transfer_green photopolymerization initiator (IV). A sensitizer having an absorption wavelength in a wavelength region of 45 G nm. Preferred examples of the sensitizer include sensitizers belonging to the following compounds and having an absorption wavelength in a wavelength region of 330 nm 66 201237551 to 450 nm. Examples include polynuclear aromatic compounds (eg, phenanthrene, anthracene, anthracene, flower, two-fold, 9,10-a-oxygen), and two abundances of π-Southern compounds (eg, luciferin, eosin) , erythrosine, rhodamine B, R0se Bengal, thioxanthone (eg isopropyl thioxanthone, diethyl sulfonate, chlorine) Anthraquinone), an acridone-like compound (for example, acridone, chloroacridone, N-decylacridone, N-butylacridone, 1〇-n-butyl- 2- gas acridone), cyanine compounds (such as thiacarbocyanine, oxacarbocyanine), merocyanine compounds (eg, merocyanine, carbonyl) Carbococyanine), phthalocyanine compounds, thiazine compounds (such as thionine, methylene blue, toluidine blue), acridine compounds (eg π丫) Acridine orange, chloroflavin, acriflavin, brewing Anthraquinone) compounds (eg, brewing), squarylium compounds (eg, aryl acid phthalocyanine), biting orange, coumarin compounds (eg, coumarin, 7-diethylamino) 4-methylcoumarin), ketocoumarin, phenothiazine compound, phenazine compound, styrylbenzene compound, azo compound, diphenyl decane, three Phenylmethane, distyrylbenzene compound, carbazole compound, porphyrin, spiro compound, quinacridone, indigo, stupid vinyl, decent An ionic compound, a β ratio of 11 methylene compounds 67 201237551 (pyromethene compound), a 吼0 sitting and a 30-seat compound, a benzopyrazine compound, a barbituric acid derivative, a thiobarbituric acid derivative, Aromatic g with the same compounds (such as acetophenone, diphenyl f ketone, thioxanthone and Michler'sketone) and heterocyclic compounds (such as the team aryl 〇 〇 〇 〇

Kg )。 實例更包括歐洲專利568,993、美國專利4,5〇8,811以 及 5,227,227、JP-A-2001-125255 以及 JP-A-11-271969 中所 述之化合物。 最重要的是，敏化劑較佳為選擇自噻噸酮類化合物、 吖啶酮類化合物以及香豆素類化合物中的至少—員，且噻 ，酮類化合物為更佳。藉由組合此敏化劑與上述聚合起始 劑，可更可靠地獲得高敏感性。 有敏射能含錢可料含有敏倾，但在含 更佳為至、為0.01質舰10質量％， [9]交聯劑 永久ί 目合^成物可更含有交聯劑以達成增強 物，制’只要其為具有交聯基之化合 基之特定較佳實似=f有兩個或超過兩個交聯基。交聯 酸酯基以及與對於氧雜％丁烷基（oxetanegr〇up)、氰 團相同的基團。其中二,合劑可具有之交聯基所述之基 晨氧基、氧雜環丁烧基以及氰酸醋 68 201237551 基為較佳。亦即，交聯基較佳為環氧化合物、氧 化合物或氰酸酯化合物。 / τ — 可在本發明中適用作交聯劑之環氧化合物的實例包 括每個分子含有至少兩個環氧乙燒基之環氧化合物，以及 每個分子含有至少兩個環氧基（各自在Ρ位置具有烧基） 之環氧化合物。 每個分子具有至少兩個環氧乙烷基之環氧化合物的 〇 實例包括（但不限於）二(二曱苯酚)型（bixyienol_type) 或聯苯酚型（biphenol-type)環氧化合物（例如「由曰本 環氧樹脂有限公司（Japan Epoxy Resins Co.，Ltd.)製造之 YX4000」）、其混合物、具有異氰尿酸酯架構或其類似物之 雜環環氧化合物（例如「由日產化學工業（Nissan Chemicals Industries，Ltd.)製造之TEPIC」、「由曰本巴斯夫製造之環 氧類樹脂PT810(ARALDITEPT810)」）、雙酚A型環氧化 合物、酚醛樹脂型環氧化合物、雙酚F型環氧化合物、氫 化雙酚A型環氧化合物、雙酚S型環氧化合物、苯酚酚醛 〇 樹脂型環氧化合物、曱酚酚醛樹脂型環氧化合物、鹵化環 氧化合物（諸如低溴化環氧化合物、高鹵化環氧化合物、 溴化苯酚盼搭樹脂型環氧化合物）、含烯丙基之雙紛A型 環氧化合物、三苯酚曱烷型環氧化合物、二苯基二曱醇型 環氧化合物、苯酚伸聯苯基型環氡化合物、二環戍二烯型 環氧化合物（例如「由大日本油墨化學公司（Dainippon Ink and Chemicals，Inc.)製造之 HP-7200、HP-7200H」）、縮水 甘油基胺型環氧化合物（諸如二胺基二苯曱烷型環氧化合 69 201237551 "TVw» 1 物、縮水甘油基苯胺以及三縮水甘油基胺基苯酚）、縮水甘 油基酯型環氧化合物（例如二縮水甘油基鄰苯二曱酸酯、 二縮水甘油基己二酸酯、二縮水甘油基六氫鄰苯二甲酸 酉旨、一細水甘油基二元脂肪酸（diglycidyl dimerate))、乙 内醯脲型（hydantoin-type)環氧化合物、脂環環氧化合物 (例如3’，4’-環氧基環己烷曱酸3,4-環氧基環己基甲基酯、 己二酸雙(3,4-環氧基環己基甲基)酯、二環戊二烯二環氧化 物、「由大賽璐化學工業有限公司（Daicel ChemicalKg). Examples include the compounds described in European Patent No. 568,993, U.S. Patent Nos. 4,5,8,811, and 5,227,227, JP-A-2001-125255, and JP-A-11-271969. Most importantly, the sensitizer is preferably selected from at least one of a thioxanthone compound, an acridone compound, and a coumarin compound, and a thiol compound is more preferred. By combining this sensitizer with the above polymerization initiator, high sensitivity can be obtained more reliably. The sensitizing energy can contain sensitive sensation, but in the case of better, it is 10% by mass of the 0.01 ship. [9] The cross-linking agent can be more viscous. The product, as long as it is a specific preferred compound of the compound having a crosslinking group, has two or more than two crosslinking groups. The acid ester group is crosslinked and the same group as the oxetanegr〇up, cyanide group. Among them, the mixture may have a base of the crosslinking group, a oxyalkylene group, and a cyanate vinegar 68 201237551 group. That is, the crosslinking group is preferably an epoxy compound, an oxygen compound or a cyanate compound. / τ - Examples of the epoxy compound which can be suitably used as a crosslinking agent in the present invention include an epoxy compound containing at least two epoxy group in each molecule, and at least two epoxy groups per molecule (each An epoxy compound having a burnt group at the oxime position. Examples of hydrazines having at least two oxirane-based epoxy compounds per molecule include, but are not limited to, dixyienol_type or biphenol-type epoxy compounds (eg, " YX4000" manufactured by Japan Epoxy Resins Co., Ltd., a mixture thereof, a heterocyclic epoxy compound having an isocyanurate structure or the like (for example, "from Nissan Chemical Co., Ltd." TEPIC manufactured by Nissan Chemicals Industries, Ltd., PT810 (ARALDITEPT810) manufactured by Ben BASF, bisphenol A epoxy compound, phenolic epoxy compound, bisphenol F Type epoxy compound, hydrogenated bisphenol A type epoxy compound, bisphenol S type epoxy compound, phenol novolac resin type epoxy compound, indophenol novolac type epoxy compound, halogenated epoxy compound (such as low bromination ring) Oxygen compound, highly halogenated epoxy compound, brominated phenol anti-resin epoxy compound), allyl-containing A-type epoxy compound, trisphenol decane type epoxy compound, diphenyl a sterol type epoxy compound, a phenol extended biphenyl type cyclic oxime compound, a bicyclo decadiene type epoxy compound (for example, "HP-7200 manufactured by Dainippon Ink and Chemicals, Inc." HP-7200H"), glycidylamine type epoxy compound (such as diaminodiphenylnonane type epoxide 69 201237551 "TVw»1, glycidyl aniline and triglycidylamino phenol), a glycidyl ester type epoxy compound (for example, diglycidyl phthalate, diglycidyl adipate, diglycidyl hexahydrophthalic acid, a fine glycerol binary) Dimethymid dimerate), hydantoin-type epoxy compound, alicyclic epoxy compound (eg 3', 4'-epoxycyclohexane decanoic acid 3,4-epoxy ring) Hexylmethyl ester, bis(3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, "Daicel Chemical"

Industries，Ltd.)製造之 GT-300、GT-400、ZEHPE3150」）、 醯亞胺型脂環環氧化合物、三經基苯基甲烧型環氧化合 物、雙酚A酚醛樹脂型環氧化合物、四苯酚乙烷型 (tetraphenylolethane-type)環氧化合物、縮水甘油基鄰苯 二曱酸酯化合物、四縮水甘油基二甲苯酚乙烧 (tetraglycidylxylenoylethane)化合物、含萘基之環氧化合 物（諸如萘酚芳烷基型環氧化合物、萘酚酚醛樹脂型環氧 化合物、四官能萘型環氧化合物，以及市售「由日本鋼鐵 化學有限公司（Nippon Steel Chemical Co., Ltd.)製造之 ESN-190、ESN-360」，以及「由大日本油墨化學公司製造 之 HP-4032、EXA-4750、EXA-4700」）、表氣醇與多 ^化 合物（藉由苯酚化合物與二烯烴化合物（諸如二乙稀笨以 及一環戊二烯）之間的加成反應獲得）之反應產物、用過 氧乙酸（peracetic acid)或其類似物環氧化之4_乙歸基環 己烯-1-氧化物開環聚合產物、具有直鏈含磷結構的環氧化 合物、具有環狀含磷:結構的環氧化合物、α_曱基民型液曰 201237551 環氧化合物、二苯甲醯氧基苯型液晶環氧化合物、偶氮基 本基型液晶壞乳化合物、曱亞胺苯基型（azomethine phenyl-type)液晶環氧化合物、聯萘型液晶環氧化合物、 σ丫嗪型環氧化合物、曱基丙烯酸縮水甘油g旨共聚物之環氧 類化合物（例如「由NOF公司（NOF Coloration)製造 之CP-50S、CP-50M」）、環己基順丁烯二醯亞胺與甲基丙 烯酸縮水甘油酯之共聚合環氧化合物、雙(縮水甘油氧基苯 ❹ ^苐型環氧化合物以及雙(縮水甘油氧基苯基)金剛烷型 裱氧化合物。可單獨使用這些環氧樹脂中一者，或可組合 使用其兩者或超過兩者。 ί 立置具ί烷基)之環氧化合物，且含有在μ:置GT-300, GT-400, ZEHPE3150" manufactured by Industries, Ltd.), yttrium imide alicyclic epoxy compound, trisyl phenyl-based epoxy compound, bisphenol A phenolic epoxy compound , a tetraphenylolethane-type epoxy compound, a glycidyl phthalate compound, a tetraglycidylxylenoylethane compound, a naphthyl-containing epoxy compound such as naphthalene A phenol aralkyl type epoxy compound, a naphthol phenol resin type epoxy compound, a tetrafunctional naphthalene type epoxy compound, and a commercially available "ESN-manufactured by Nippon Steel Chemical Co., Ltd." 190, ESN-360", and "HP-4032, EXA-4750, EXA-4700 manufactured by Dainippon Ink Chemical Co., Ltd.", surface gas alcohols and poly-compounds (by phenol compounds and diolefin compounds (such as two) a reaction product obtained by an addition reaction between ethylene and monocyclopentadiene), 4-epoxycyclohexene-1-oxide epoxidized with peracetic acid or the like Ring polymerization product An epoxy compound having a linear phosphorus-containing structure, an epoxy compound having a cyclic phosphorus-containing structure, an α-fluorene-based liquid liquid 201237551 epoxy compound, a diphenylmethyloxybenzene liquid crystal epoxy compound, Azo basic liquid crystal bad emulsion compound, azomethine phenyl-type liquid crystal epoxy compound, binaphthyl liquid crystal epoxy compound, σ-pyridazine epoxy compound, glycidyl methacrylate Epoxy compounds of copolymers (for example, "CP-50S, CP-50M manufactured by NOF Coloration"), copolymerized epoxy of cyclohexylmethyleneimine and glycidyl methacrylate a compound, a bis(glycidoxybenzoquinone oxime type epoxy compound, and a bis(glycidoxyphenyl)adamantane type oxime compound. One of these epoxy resins may be used alone, or two of them may be used in combination. Or more than both. ί Stand with an alkyl compound of ί alkyl) and contained in μ:

'氧雜環丁基甲氧基）甲基] ’且含有在β-位置之經 β-烧基取代之縮水甘油 201237551 苯、Μ·雙[(3_乙基冬氧雜環丁基甲氧基）甲基]笨 (3-曱基-3-氧雜環丁基）曱酯、丙烯酸(3_乙基氧雜浐美欠 甲醋、甲基丙烯酸(3-曱基-3-氧雜環丁基）甲酉旨^ ^ 酸(3-乙基錢雜環丁基）甲醋，以及其寡聚物或共^勿； 以及含氧雜環丁烷基之化合物的醚化合物以及含_美之樹 脂，諸如酚醛樹脂、聚（對羥基苯乙烯）、軸節^雙酚 (^也々?61)咏11_1)、杯芳烴（(;此咖116)、間苯二酚杯 芳烴（calixres〇rcinarene )以及倍半氧矽烷 (SilSeSqUi〇xane )。其他實例包括含氧雜環丁烷環之不飽和‘ 單體與（甲基)丙稀酸烧酯之共聚物。 雙順丁婦二醯亞胺化合物之實例包括4,4，_二苯基曱 烧雙，丁稀二醯亞胺、雙(3-乙基_5_曱基_4_順丁烯二醯亞 胺基苯基）甲烧以及2,2’_雙[4_(4_順丁婦二醯亞胺基苯氧基） 苯基]丙烷。 氰酸酯化合物之實例包括雙A型氰酸酯化合物（bis A-type cyanate compound)、雙F型氰酸酯化合物、甲酚酚 酿树知型氰酸酯化合物以及笨紛齡酸樹脂型氰酸酯化合 物。 可聚合組成物可能含有或可能不含有交聯劑，但在含 有交聯劑之情況下，以本發明之可聚合組成物的全部固體 含量（質量）計’其含量較佳為1質量％至4〇質量。/。，更 佳為3質量％至20質量％。 [10]固化促進劑 本發明之可聚合組成物可更含有固化促進劑以達成 72 201237551 促進交聯劑（諸如上述環氧化合物以及氧雜環丁烷化合物） 熱固化之目的。 可使用之固化促進劑之實例包括胺化合物（諸如二氰 二胺（dicyandiamide)、苯曱基二曱胺、‘(工甲胺基)_N N_ 二曱基苯甲胺、4-甲氧基-N，N-二甲基苯甲胺以及4_曱基 -N，N-二曱基苯甲胺）、四級錢鹽化合物（諸如氯化三乙基 苯甲基鈹）、嵌段異氰酸酯化合物（諸如二甲胺）' 咪唑衍 0 生物雙環肺化合物以及其鹽（諸如咪唾、2-甲基味唾、2_ 乙基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、4_苯基咪唑、 1-氰基乙基-2-苯基咪唑以及1 氰基乙基)_2_乙基_4_曱基 咪》坐）、填化合物（諸如三苯膦）、胍胺（guanamine)化二 物（諸如三聚氰胺、胍胺、乙醯胍胺以及苯并胍胺），以及 三嗪衍生物（諸如2,4-二胺基_6_曱基丙烯醯氧基乙基 二嗪、2-乙烯基-2,4-二胺基-S-三嗪、2-乙烯基_4,6_二胺基 _s-三嗪-異氰尿酸加合物、2,4_二胺基_6_甲基丙烯醯氧基乙 基各^唤-異氰尿酸加合物）。固化促進劑較佳為三聚氰胺 〇 或二氰二胺。其可單獨使用或組合使用。可單獨使用這些 化合物中的一者，或可組合使用其兩者或超過兩者。— 可聚合組成物可能含有或可能不含有固化促進劑，但 有固化促_之情況下，以可聚合組成物之全部固體 έ量計，其含量通常為0.01質量％至15質量〇/〇。 [11]彈性體 本發明之可聚合組成物可更含有彈性體。 藉由含有彈性體，當使用阻谭劑之可聚合組成物時， 73 201237551 -TVJ 1 對印刷線路板（printed wiring board )之導電層的黏著力可 更加改良，且同時，固化膜之耐熱性、抗熱^生（如福 ^ockresistance)、可撓性以及韌性（t〇ughness)可更加增 可用於本發明中之彈性體不受特別限制且可根據目 的適當選擇，且其實例包括苯乙烯類雜體、驗類彈性 體、胺基曱酸酯類彈性體、聚酯類彈性體、聚醯胺類彈性 體、丙烯酸系彈性體以及矽酮類彈性體。此彈性體由硬區 段組分以及軟區段組分構成，其中一般而言，前者有助於 耐熱性以及強度且後者有助於可撓性以及韌性。其中，鑒 於與其他材料之相容性，聚酯類彈性體為有利的。 苯乙烯類彈性體的實例包括苯乙烯_ 丁二烯_苯乙烯嵌 段共聚物、苯乙烯-異戊二烯-苯乙烯嵌段共聚物、苯乙烯_ 乙烯-丁烯-苯乙烯嵌段共聚物以及苯乙烯_乙烯_丙烯_苯乙 烯嵌段共聚物。作為構成苯乙烯類彈性體的組分，除了苯 乙稀之外，可使用苯乙烯衍生物，諸如α_曱基苯乙烯、3_ 曱基苯乙烯、4-丙基苯乙烯以及4-環己基苯乙烯。其特定 實例包括 TUFPRENE、SOLPRENE Τ、ASAPRENE Τ、 Tuftec (均由ADEKA製造）、彈性體AR (由安秀有限公 司（Aronkasei Co” Ltd.)製造）、Kraton G、Califlex (均 由曰本殼牌公司（81^11)製造）、了311-丁11、丁811-818、〇丫1^〇11 (均由JSR製造）、Denka STR (由電氣化學工業株式會社 (Denki Kagaku Kogyo K.K.)製造）、Quintac (由 ΖΕΟΝ 公 司（ΖΕΟΝ Corporation)製造）、TPE-SB系列（由住友化 74 201237551 學有限公司製造）、Rabalon (由三菱化學公司（Mitsubishi'oxetanylmethoxy)methyl]' and contains a β-alkyl substituted glycidyl group at the β-position 201237551 Benzene, bismuth [(3-ethyloxetyl methoxy)methyl) ] stupid (3-mercapto-3-oxetanyl) decyl ester, acrylic acid (3-ethyl oxime oxime), methacrylic acid (3-indolyl-3-oxetanyl) A hydrazine (3-ethyl hydroxy-heterobutyl) methyl vinegar, and an oligomer or a mixture thereof; and an ether compound of a compound containing an oxetane group, and a resin containing _ Such as phenolic resin, poly(p-hydroxystyrene), shaft bisphenol (^?? 61) 咏11_1), calixarene ((this coffee 116), resorcinol calixarene (calixres〇rcinarene) and Silsesquioxanes (SilSeSqUi〇xane). Other examples include copolymers of an oxetane ring-containing unsaturated 'monomer with a (meth) acrylate acid ester. Examples include 4,4,-diphenyl fluorenyl, butyl bisimide, bis(3-ethyl-5-indenyl-4-m-butylene iminophenyl), and 2 , 2'_double [4_(4_顺丁妇二醯iminophenoxy)benzene Propane. Examples of the cyanate ester compound include a bis A-type cyanate compound, a double F-type cyanate compound, a cresol phenolic cyanate compound, and a stupid acid. Resin type cyanate compound. The polymerizable composition may or may not contain a crosslinking agent, but in the case of containing a crosslinking agent, based on the total solid content (mass) of the polymerizable composition of the present invention It is preferably from 1% by mass to 4% by mass, more preferably from 3% by mass to 20% by mass. [10] Curing accelerator The polymerizable composition of the present invention may further contain a curing accelerator to achieve 72 201237551 The purpose of the bonding agent (such as the above epoxy compound and oxetane compound) for heat curing. Examples of curing accelerators that can be used include amine compounds (such as dicyandiamide, benzoguanidine diamine, ' (Methylamino)_N N_dimercaptobenzylamine, 4-methoxy-N,N-dimethylbenzylamine and 4-mercapto-N,N-dimercaptobenzylamine), four Grade salt compound (such as triethylbenzyl hydrazine chloride), block Acid ester compound (such as dimethylamine) 'imidazole derivative 0 biological bicyclic lung compound and its salt (such as sodium saliva, 2-methyl saliva, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- Phenyl imidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1 cyanoethyl)_2_ethyl_4_fluorenyl) sit-filled compound (such as triphenylphosphine) ), guanamine (such as melamine, guanamine, acetamide, and benzoguanamine), and triazine derivatives (such as 2,4-diamino-6-mercaptopropene oxime) Ethyldiazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-s-triazine-isocyanuric acid adduct, 2 , 4_diamino _6-methacryl oxiranyl ethyl group - isocyanuric acid adduct). The curing accelerator is preferably melamine or dicyandiamide. They can be used singly or in combination. One of these compounds may be used alone, or two or more of them may be used in combination. — The polymerizable composition may or may not contain a curing accelerator, but in the case of curing, the content is usually from 0.01% by mass to 15% by mass based on the total solids of the polymerizable composition. [11] Elastomer The polymerizable composition of the present invention may further contain an elastomer. By using an elastomer, when the polymerizable composition of the blocker is used, the adhesion of the 73 201237551 -TVJ 1 to the conductive layer of the printed wiring board can be further improved, and at the same time, the heat resistance of the cured film The heat resistance can be further increased, and the flexibility and toughness can be further increased. The elastomer which can be used in the present invention is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include styrene. A miscellaneous, an elastomer, an amine phthalate elastomer, a polyester elastomer, a polyamine elastomer, an acrylic elastomer, and an anthrone elastomer. The elastomer consists of a hard segment component and a soft segment component, wherein in general the former contributes to heat resistance and strength and the latter contributes to flexibility and toughness. Among them, polyester elastomers are advantageous in view of compatibility with other materials. Examples of the styrene elastomer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, and a styrene-ethylene-butylene-styrene block copolymer. And a styrene-ethylene-propylene-styrene block copolymer. As the component constituting the styrene elastomer, in addition to styrene, a styrene derivative such as α-mercaptostyrene, 3-decylstyrene, 4-propylstyrene, and 4-cyclohexyl group can be used. Styrene. Specific examples thereof include TUPPRENE, SOLPRENE®, ASAPRENE®, Tuftec (both manufactured by ADEKA), elastomer AR (manufactured by Aronkasei Co. Ltd.), Kraton G, Califlex (both by Sakamoto Shell Corporation ( 81^11) Manufactured, 311-Ding 11, Ding 811-818, 〇丫1^〇11 (all manufactured by JSR), Denka STR (manufactured by Denki Kagaku Kogyo KK), Quintac (Manufactured by ΖΕΟΝ Corporation), TPE-SB series (manufactured by Sumitomo Chemicals, Ltd., 201237551 Research Co., Ltd.), Rabalon (by Mitsubishi Chemical Corporation (Mitsubishi)

Chemical Corporation)製造）、Septon、HYBRAR (均由可 樂麗有限公司（KurarayCo.，Ltd.)製造）、Sumiflex (由住 友電木有限公司（Sumitomo Bakelite Co., Ltd.)製造）、 Leostomer以及Actymer (均由理研乙烯基工業有限公司 (Riken Vinyl Industry Co” Ltd.)製造）。 烯烴類彈性體為碳數目為2至20之α-烯烴（諸如乙 烯、丙烯、1-丁烯、1-己烯以及4-曱基-戊烯）之共聚物， 〇 且其實例包括乙烯-丙烯共聚物（EPR)以及乙烯-丙烯-二 烯共聚物（EPDM)。此外，烯烴類彈性體包括例如α_烯烴 與碳數目為2至20之非共軛二烯（諸如二環戊二烯、丨，4_ 己二烯、環辛二烯、亞曱基降冰片烯、亞乙基降冰片浠、 丁二烯以及異戊二烯，以及環氧化聚丁二烯）的共聚物。 烯煙類彈性體更包括例如藉由共聚合曱基丙烯酸與丁二烯 -丙烯腈共聚物獲得之羧基改質之NBR。烯烴類彈性體的 其他實例包括乙烯-α-烯烴共聚物橡膠、乙稀_α-稀烴-非共 Q 軛二烯共聚物橡膠、丙烯-α-烯烴共聚物橡膠以及丁烯-α_ 烯烴共聚物橡膠。 烯烴類彈性體的特定實例包括Milastomer (由三井石 化工業有限公司（Mitsui Petrochemical Industries，Ltd·)製 造）、EXACT (由埃克森化學（Exxon Chemical)製造）、 ENGAGE (由陶氏化學（Dow Chemical)製造）、氫化苯 乙烯·丁二烯橡膠「DYNABONHSBR」（由JSR製造）、丁 二烯-丙烯腈共聚物「NBR系列」（由JSR製造）、在兩個 75 201237551 末7均以具有交聯位點之羧基改質之丁二烯-丙烯猜共聚 物「XER系列」（由JSR製造），以及藉由部分環氧化聚丁 二烯獲得之環氧化聚丁二烯「BF-1000」（由日本曹達有限 公司製造）。 、 胺基甲酸酯類彈性體由結構單元組成，結構單元亦即 為由低分子（短鏈）二醇以及二異氰酸酯構成之硬區段， 以及由聚合物（長鏈）二醇以及二異氰酸酯構成之軟區段。 聚合物（長鏈）二醇之實例包括聚丙二醇、聚氧化四曱基 趟（polytetramethylene oxide )、聚（己二酸 1，4-伸丁 g旨）、聚 (己二酸伸乙基·1，4-伸丁酯）、聚己内酯、聚(碳酸丨，6-伸己 醋）以及聚（己二酸1,6-伸己基伸新戊酯）。聚合物（長鏈） 二醇之數目平均分子量較佳為5〇〇至1〇,〇〇〇。低分子（短 鏈）二醇之實例包括乙二醇、丙二醇、1，4_丁二醇以及雙 酚Α。短鏈二醇之數目平均分子量較佳為48至5〇〇。胺基 曱酸酯類彈性體的特定實例包括PANDEX T-2185以及 T-2983N (均由 DIC 公司（DIC Corporation)製造），以及 Shirakutoran E790。 藉由聚縮合二羧酸或其衍生物與二醇化合物或其衍 生物來獲得聚酯類彈性體。二羧酸之特定實例包括芳族二 羧酸’諸如對苯二甲酸、間苯二曱酸以及萘二曱酸；上述 芳環之氫原子經曱基、乙基、苯基或其類似基團取代之芳 族二羧酸；碳數目為2至20之脂族二叛酸，諸如己二酸、 癸二酸以及十二烷二甲酸；以及脂環二羧酸，諸如環己烷 二曱酸。可使用這些化合物中一者或其兩者或超過兩者。 76 201237551 二醇化合物之特定實例包括脂族或脂環二醇，諸如乙二 醇、1,3-丙二醇、1,4-丁二醇、1，6-己二醇、1，1〇_癸二醇以 及1，4-環己二醇、雙酚a、雙(4-羥苯基)-甲烷、雙(4-羥基 _3_曱基苯基)_丙烷以及間苯二酚。可使用這些化合物中的 一者或其兩者或超過兩者。可使用對於硬區段組分使用芳 族聚酯（例如聚對苯二曱酸丁二酯）部分且對於軟區段組 分使用脂族聚酯（例如聚丁二醇（polytetramethylene ❹ glycol))部分之多嵌段共聚物。根據硬區段與軟區段之種 類、比率以及分子量差異，聚酯類彈性體包括各種等級。 聚醋類彈性體的特定實例包括Hytrel (由杜邦東麗有限公 司（Du Pont-Toray Co” Ltd.)製造）、PELPRENE (由東洋 紡織有限公司（ToyoboCo.，Ltd.)製造）以及ESPEL (由 曰立化學有限公司（Hitachi Chemical Co.，Ltd.)製造）。 聚醯胺類彈性體由以下組成：由聚醯胺構成之硬區段 以及由聚醚或聚酯構成之軟區段，且粗略地分為兩種類 型’亦即聚醚嵌段醯胺類型以及聚醚酯嵌段類型。聚醯胺 〇 之實例包括聚醯胺-6、聚醯胺-11以及聚醯胺-12。聚醚之 實例包括聚氧乙烯、聚氧丙烯以及聚丁二醇。聚醯胺類彈 性體的特定實例包括UBE聚醯胺彈性體（由Ube工業有 限公司（Ube Industries，Ltd.)製造）、DAIAMID (由大赛 璐-赫斯（Daicel-Huels )製造）、PEBAX (由東麗工業公司 (Toray Industries，Inc.)製造）、Grilon ELY (曰本 EMS )、 Novamid (由三菱化學公司製造）以及Grilax .(由DIC公 司製造）。 77 201237551 tvj ι^μυ. 藉由共聚合丙稀酸酯（諸如丙稀酸乙酯、丙稀酸丁 酉旨、丙烯酸曱氧基乙醋以及丙稀酸乙氧基乙S旨）、含環氧基 之單體（諸如曱基丙烯酸縮水甘油酯以及烷基縮水甘油醚） 及/或乙烯基類單體（諸如丙稀腈以及乙烯）來獲得丙稀酸 系彈性體。丙烯酸系彈性體之實例包括丙烯腈-丙烯酸丁醋 共聚物、丙烯腈-丙烯酸丁酯-丙烯酸乙酯共聚物以及丙烯 腈-丙烯酸丁酯-曱基丙烯酸縮水甘油酯共聚物。 矽酮類彈性體主要由有機聚矽氧烷構成且可分為聚 二甲基矽氧烷型、聚甲基苯基矽氧烷型以及聚二苯基石夕氧 烷型。亦可使用以乙烯基、烷氧基或其類似基團部分改質 之有機聚矽氧烷。矽酮類彈性體的特定實例包括KE系列 (由信越化學有限公司製造）、SE系列' CY系列以及SH 系列（均由道康寧矽酮有限公司（D〇w c〇rning T〇ray Silicone Co” Ltd.)製造）。 —除了上述彈性體，可使用橡膠改質之環氧樹脂。如下 獲得橡膠改質之環氧樹脂：以例如兩個末端經緩酸改質之 =二烯-丙烯腈橡膠或一個末端經胺基改質之矽_橡膠改 ^述雙型環氧樹脂、雙齡A型環氧樹脂、柳搭型環 ^樹脂（saiiCyialdehyde_type ep〇xy resin)、苯盼祕樹脂 ㈣氧樹脂、曱__脂型環氧樹脂或其類似物 基之部分或全部。 端經中’料剪娜著力以及抗熱震性，兩個末 古^土 之丁二烯-丙烯腈共聚物以及espel(亦即且 有基之聚_彈性體，ESPEL 1612以及1620，由日立 78 201237551 化子^公司製造）以及環氧化聚丁二埽為較佳。 本發明之可聚合組成物可能含有 體，但在含有彈性體之情況下，以可含有弹性 體含量（質量）叶，A含詈不為牲=聚合組成物之全部固 一挥其3里不又特別限制且可根據目的適 。以固體含量言十，所述含量較佳為〇 5質量％至％ 貝1/。，更佳為：1質量％至10質量％，Chemical Corporation), Septon, HYBRAR (both manufactured by Kuraray Co., Ltd.), Sumiflex (manufactured by Sumitomo Bakelite Co., Ltd.), Leostomer, and Actymer ( Both are manufactured by Riken Vinyl Industry Co. Ltd.) The olefin elastomer is an α-olefin having a carbon number of 2 to 20 (such as ethylene, propylene, 1-butene, 1-hexene). And a copolymer of 4-mercapto-pentene, and examples thereof include an ethylene-propylene copolymer (EPR) and an ethylene-propylene-diene copolymer (EPDM). Further, the olefin elastomer includes, for example, an α-olefin. Non-conjugated dienes having a carbon number of 2 to 20 (such as dicyclopentadiene, anthracene, 4 hexadiene, cyclooctadiene, fluorenyl norbornene, ethylidene norbornene, butadiene) And a copolymer of isoprene and epoxidized polybutadiene. The olefinic elastomer further includes, for example, a carboxyl modified NBR obtained by copolymerizing a methacrylic acid and a butadiene-acrylonitrile copolymer. Other examples of olefinic elastomers include ethylene-α-olefins Rubber, ethylene-α-dilute hydrocarbon-non-co-Q conjugated diene copolymer rubber, propylene-α-olefin copolymer rubber, and butene-α-olefin copolymer rubber. Specific examples of olefin elastomers include Milastomer (by Manufactured by Mitsui Petrochemical Industries, Ltd., EXACT (manufactured by Exxon Chemical), ENGAGE (manufactured by Dow Chemical), hydrogenated styrene-butadiene Rubber "DYNABONHSBR" (manufactured by JSR), butadiene-acrylonitrile copolymer "NBR series" (manufactured by JSR), butadiene which is modified with a carboxyl group having a crosslinking site at the end of two 75 201237551 - A propylene-copolymer "XER series" (manufactured by JSR), and an epoxidized polybutadiene "BF-1000" (manufactured by Japan Soda Co., Ltd.) obtained by partially epoxidizing polybutadiene. The urethane elastomer is composed of structural units, that is, a hard segment composed of a low molecular (short chain) diol and a diisocyanate, and a polymer (long chain) diol and a diisocyanate. Soft section. Examples of the polymer (long-chain) diol include polypropylene glycol, polytetramethylene oxide, poly(adipic acid 1,4-extension), poly(adipic acid extension ethyl·1) , 4-butyl butyl ester), polycaprolactone, poly (barium carbonate, 6-extracted vinegar) and poly (adipate 1,6-extended hexyl neopentyl ester). The number average molecular weight of the polymer (long chain) diol is preferably from 5 Å to 1 Torr. Examples of the low molecular (short chain) diol include ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol quinone. The number average molecular weight of the short-chain diol is preferably from 48 to 5 Å. Specific examples of the amine phthalate elastomer include PANDEX T-2185 and T-2983N (both manufactured by DIC Corporation), and Shirakutoran E790. The polyester elastomer is obtained by polycondensing a dicarboxylic acid or a derivative thereof with a diol compound or a derivative thereof. Specific examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid; the hydrogen atom of the above aromatic ring is thiol, ethyl, phenyl or the like. Substituted aromatic dicarboxylic acid; aliphatic diteric acid having a carbon number of 2 to 20, such as adipic acid, sebacic acid, and dodecanedicarboxylic acid; and an alicyclic dicarboxylic acid such as cyclohexane dicarboxylic acid . One or both of these compounds or more may be used. 76 201237551 Specific examples of the diol compound include aliphatic or alicyclic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,1 〇 癸Glycol and 1,4-cyclohexanediol, bisphenol a, bis(4-hydroxyphenyl)-methane, bis(4-hydroxy-3-indolylphenyl)-propane, and resorcinol. One or both of these compounds or more may be used. It is possible to use an aromatic polyester (for example polybutylene terephthalate) moiety for the hard segment component and an aliphatic polyester (for example polytetramethylene ❹ glycol) for the soft segment component. Part of the multi-block copolymer. The polyester elastomer includes various grades depending on the type, ratio, and molecular weight difference between the hard segment and the soft segment. Specific examples of the polyacetal elastomer include Hytrel (manufactured by Du Pont-Toray Co. Ltd.), PELPRENE (manufactured by Toyobo Co., Ltd.), and ESPEL (by Manufactured by Hitachi Chemical Co., Ltd.) The polyamine elastomer consists of a hard segment composed of polyamine and a soft segment composed of a polyether or polyester, and There are roughly two types, namely, a polyether block guanamine type and a polyether ester block type. Examples of polyamidoxime include polyamido-6, polyamido-11, and polyamido-12. Examples of the polyether include polyoxyethylene, polyoxypropylene, and polytetramethylene glycol. Specific examples of the polyamine elastomer include UBE polyamine elastomer (manufactured by Ube Industries, Ltd.), DAIAMID (manufactured by Daicel-Huels), PEBAX (manufactured by Toray Industries, Inc.), Grilon ELY (Sakamoto EMS), Novamid (manufactured by Mitsubishi Chemical Corporation), and Grilax . (Manufactured by DIC Corporation) 77 201237551 tvj ι^μυ. by copolymerizing acrylates (such as ethyl acrylate, butyl acrylate, methoxy ethoxy acrylate and ethoxy ethoxy acetate), epoxy-containing singles An acrylic elastomer such as acrylonitrile, and/or a vinyl monomer such as acrylonitrile and ethylene, to obtain an acrylic elastomer. Examples of the acrylic elastomer include acrylonitrile. a butyl acrylate copolymer, an acrylonitrile-butyl acrylate-ethyl acrylate copolymer, and an acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer. The fluorenone elastomer is mainly composed of an organic polysiloxane. It can be divided into polydimethyl siloxane type, polymethyl phenyl oxane type and polydiphenyl oxalate type. It can also be modified with vinyl, alkoxy or the like. Organic polyoxane. Specific examples of anthrone-based elastomers include the KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), the SE series 'CY series, and the SH series (all by Dow Corning Anthraquinone Co., Ltd. (D〇wc〇rning T〇) Made by ray Silicone Co" Ltd.). - In addition to the above elastomers, rubber-modified epoxy resins can be used. A rubber-modified epoxy resin is obtained as follows: for example, a diene-acrylonitrile rubber modified with two ends and a diene-acrylonitrile rubber or a terminal modified by an amine group Part or all of the age-type A epoxy resin, the sai-type resin (saiiCyialdehyde_type ep〇xy resin), the benzene-preventive resin (iv) oxygen resin, the 曱__lipid epoxy resin or the like. In the end of the process, the material is sheared and heat-resistant, two butadiene-acrylonitrile copolymers and espel (also known as poly-elastomers, ESPEL 1612 and 1620, by Hitachi 78 201237551 Manufactured by the company, and epoxidized polybutadiene is preferred. The polymerizable composition of the present invention may contain a body, but in the case of containing an elastomer, the leaf may contain an elastomer content (mass), and the A-containing yttrium is not a solid component of the polymer composition. It is also particularly limited and can be adapted to the purpose. In terms of solid content, the content is preferably 〇 5 mass% to % shell 1. More preferably: 1% by mass to 10% by mass,

質量％。當含量處於此較佳範圍内日夺切黏、° 熱震性可有觀更加增強。 I雄者力以及抗 [12]界面活性齊j 自更加增強可塗佈性之觀點來看，可在本發明之感光 树月曰組成物巾添加各祕面活_。作為界祕性劑二可 tit種=活性劑’諸如含氟界面活_、非離子界面 活性劑、陽離子界祕_、陰離子界面 酮之界面活性劑。 ^ 乂汉3 /quality%. When the content is in this preferred range, the shear viscosity and the thermal shock resistance can be more enhanced. I male force and anti-[12] interface activity. From the viewpoint of further enhancing the coatability, it is possible to add the secret surface _ in the photosensitive tree composition of the present invention. As a secret agent, a titer = active agent such as a fluorine-containing interface, a nonionic surfactant, a cationic boundary, and an anionic interface ketone surfactant. ^ 乂汉3 /

關4發日狀可聚合成物含有含氟界面活 性劑時，所製備之塗佈驗之液體概（_是流動性） ，更力:增強’因此塗層厚度之均一性以及液體儲存效能 (liquid saving performance)可更加改良。 亦即’在藉由使用經應用含有含氟界面活性劑之可聚 合組成物的塗佈溶液來形成臈之情況下，待塗佈表面與塗 佈溶液之_界面張力降低，藉此改良待塗佈表面之可渴 性（wettability)且增強待塗佈表面上之可塗佈性。此舉有' 效之處在於甚至當以少量溶液形成大約若干微米之薄膜 時，可更成功地使制厚叙不均自性減小且使1且有均 79 201237551 -TV/-/ Α ί^γΐ-Λ. 一的厚度。 含氟界面活性劑之氟含量較佳為3質量％至4〇質量 %，更佳為5質量％至30質量％，更佳為7質量％至25質 量％。鑒於塗膜之厚度均一性或液體儲存效能，氟含量在 此範圍内之含氟界面活性劑為有效的，而且顯示在可聚合 組成物中之良好溶解度。 含氟界面活性劑之實例包括Megaface F171、Megaface F172、Megaface FI73、Megaface FI76、Megaface FI77、 Megaface F14 卜 Megaface F142、Megaface F143、Megaface F144、Megaface R30、Megaface F437、Megaface F475、 Megaface F479、Megaface F482、Megaface F554、Megaface F780、Megaface F781 (均由 DIC 公司製造）、Fluorad FC430、Fluorad FC431、Fluorad FC171 (均由住友 3M 有 限公司製造）、Surflon S-382、Surflon SC-101、Surflon SC-103、Surflon SC-104、Surflon SC-105、Surflon SC-1068、Surflon SC-381、Surflon SC-383、Surflon S-393、 Surflon KH-40 (均由旭玻璃有限公司（Asahi Glass Co.， Ltd.)製造）以及Solsperse20000 (由路博潤公司製造）。 非離子界面活性劑之特定實例包括丙三醇、三羥甲基 丙烷、三羥曱基乙烷、其乙氧基化物以及丙氧基化物（例 如丙三醇丙氧.基化物、丙三醇乙氧基化物）、聚氧乙烯月桂 基醚、聚氧乙烯十八烷基醚、聚氧乙烯油基醚、聚氧乙烯 辛基苯基醚、聚氧乙烯壬基苯基醚、聚乙二醇二月桂酸酯、 聚乙二醇二硬脂酸酯以及脫水山梨糖醇脂肪酸酯（諸如 201237551When the four-day polymerizable product contains a fluorosurfactant, the prepared coating liquid (_ is fluidity), more force: enhances 'the uniformity of the coating thickness and the liquid storage efficiency ( Liquid saving performance) can be improved. That is, in the case where ruthenium is formed by using a coating solution to which a polymerizable composition containing a fluorine-containing surfactant is applied, the interfacial tension between the surface to be coated and the coating solution is lowered, thereby improving the coating to be coated. The cloth surface is wettability and enhances the coatability on the surface to be coated. This has the effect that even when a film of about several micrometers is formed with a small amount of solution, it is more successful to reduce the thickness unevenness and make 1 and have an average of 79 201237551 -TV/-/ Α ί ^γΐ-Λ. The thickness of one. The fluorine content of the fluorine-containing surfactant is preferably from 3% by mass to 4% by mass, more preferably from 5% by mass to 30% by mass, still more preferably from 7% by mass to 25% by mass. In view of the thickness uniformity or liquid storage efficiency of the coating film, the fluorine-containing surfactant having a fluorine content within this range is effective and exhibits good solubility in the polymerizable composition. Examples of fluorosurfactants include Megaface F171, Megaface F172, Megaface FI73, Megaface FI76, Megaface FI77, Megaface F14, Megaface F142, Megaface F143, Megaface F144, Megaface R30, Megaface F437, Megaface F475, Megaface F479, Megaface F482, Megaface F554, Megaface F780, Megaface F781 (both manufactured by DIC), Fluorad FC430, Fluorad FC431, Fluorad FC171 (both manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (all manufactured by Asahi Glass Co., Ltd.) ) and Solsperse20000 (manufactured by The Lubrizol Corporation). Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trihydrocarbylethane, ethoxylates thereof, and propoxylates (e.g., glycerol propoxylate, glycerol) Ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene Alcohol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters (such as 201237551

Pluronic L10、L31、L61、L62、10R5、17R2 以及 25R2， 以及 Tetronic 304、7(M、704、901、904 以及 150IU，由 巴斯夫製造）。 陽離子界面活性劑之特定實例包括酞菁衍生物 (EFKA-745，商標，由森下產業公司（Morishita Sangyo K.K.)製造）、有機矽氧烷聚合物κρ^ι (由信越化學有限 公司製造）、（曱基)丙烯酸(共)聚合物POLYFLOW 75號、 90號以及95號（由共榮社化學有限公司製造）以及W001 〇 (由友松有限公司製造）。 陰離子界面活性劑之特定實例包括W004、W005以及 W017 (由友松有限公司製造）。 含矽酮之界面活性劑的實例包括「TORAY SILICONE DC3PA」、「TORAY SILICONE SH7PA」、「TORAY SILICONE DC11PA」、「TORAY SILICONE SH21PA」、 「TORAY SILICONE SH28PA」、「TORAY SILICONE SH29PA」、「TORAY SILICONE SH30PA」以及「TORAY 〇 SILICONE SH8400」（由道康寧矽酮有限公司製造）； 「TSF-4440」、「TSF-4300」、「TSF-4445」、「TSF-4460」以 及「TSF-4452」（由邁圖高新材料公司（Momentive Performance Materials Inc·)製造）；「KP341」、「KF6001」 以及「KF6002」（由信越梦酮（Shin-Etsu Silicone )製造）； 以及「BYK307」、「BYK-323」以及「BYK-330」（由畢克 化學製造）。 在這些界面活性劑中，含氟界面活性劑為更佳。 81 201237551 種界面活性劑作為界面活性劑。 可聚合組成物可能含有或 在含有界面活性劑之情況下，Pluronic L10, L31, L61, L62, 10R5, 17R2 and 25R2, and Tetronic 304, 7 (M, 704, 901, 904 and 150 IU, manufactured by BASF). Specific examples of the cationic surfactant include a phthalocyanine derivative (EFKA-745, trade mark, manufactured by Morishita Sangyo KK), an organic siloxane polymer κρ^ι (manufactured by Shin-Etsu Chemical Co., Ltd.),曱-based acrylic acid (co)polymer POLYFLOW No. 75, No. 90 and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 〇 (manufactured by Yousong Co., Ltd.). Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yousong Co., Ltd.). Examples of the ketone-containing surfactant include "TORAY SILICONE DC3PA", "TORAY SILICONE SH7PA", "TORAY SILICONE DC11PA", "TORAY SILICONE SH21PA", "TORAY SILICONE SH28PA", "TORAY SILICONE SH29PA", "TORAY SILICONE SH30PA" And "TORAY 〇SILICONE SH8400" (manufactured by Dow Corning Acne Ltd.); "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460" and "TSF-4452" "KP341", "KF6001" and "KF6002" (made by Shin-Etsu Silicone); and "BYK307" and "BYK-323", and manufactured by Momentive Performance Materials Inc. "BYK-330" (manufactured by BYK Chemicals). Among these surfactants, a fluorine-containing surfactant is more preferable. 81 201237551 A surfactant is used as a surfactant. The polymerizable composition may or may contain a surfactant,

可使用一種界面活性劑， 或可組合使用兩種或超過兩 可能不含有界面活性劑，但 以本發明之可聚合組成物的 其含量較佳為0.001質量％至1 在本發明之可聚合組成物卜除上述基本組分以及較 L添加斜，亦可根據目的衫損害本發明之仙的範圍 内適當選擇及使用其他組分。 可組合使用之其他組分的實例包括矽烷耦合劑、熱固 化促進劑、熱聚合抑制劑、增塑劑以及著色劑（有色顏料 或染料）。此外，亦可組合使用基板表面黏著促進劑以及其 他助劑（auxiliary agent)(例如導電粒子、填料、消泡劑、 阻燃劑、調平劑、脫模促進劑（release promoter)、抗氧化 劑、香料、表面張力調節劑（surface tensi〇n a(jjusting agent) 以及鏈轉移劑（chain transfer agent))。 藉由適當併入這些組分，可調節目標阻焊劑之性質， 諸如穩定性、攝影性質以及膜性質。特定言之，對於增強 基板黏著而言較佳為添加编合劑。 例如在JP-A-2008_250074之段落[0101]以及段落 [0102]中詳述熱聚合抑制劑。 例如在JP-A-2008-250074之段落[0103]以及段落 [0104]中詳述增塑劑。 82 201237551 例如在JP-A-2008-250074之段落[〇1〇5]以及段落 [0106]中以及jp_A-2009-205029之段落[〇〇38]以及段落 [0039]中詳述著色劑。 例如在 JP-A-2008-250074 之段落[01〇7]至段落[0109] 中詳述黏著促進劑。 這些公開案中所述之所有添加劑均可用於本發明之 可聚合組成物。 由此獲得之本發明之可聚合組成物的固體含量濃度 較佳為5質量％至9〇質量％，更佳為2〇質量％至80質量 %，且最佳為40質量％至60質量％。 較佳經由過濾器過濾本發明之可聚合組成物以達成 移除外來物質或減少缺陷之目的。過濾及其類似操作習用 之過濾器可在無任何特定限制之情況下使用。其實例包括 由以下形成之過滤器：氟樹脂（f[u〇r〇resin)，諸如PTfe (聚四氟乙烯）；聚醯胺類樹脂，諸如耐綸-6 (nylon-6)以 及耐綸6,6 ;以及聚烯烴樹脂（包括高密度聚烯烴以及超 高分子聚烯烴），諸如聚乙烯以及聚丙烯（PP)。在這些材 料中’聚丙烯（包括高密度聚丙烯）為較佳。 過濾器之孔徑（P〇re size)宜為大約〇〇1微米至7〇 微米，較佳為大約0·01微米至2.5微米，更佳為大約〇 〇1 微米至1.5微米。在此範圍内，可以可靠地移除混合於溶 解^料或其類似物中且在稍後步驟中抑制製備均一且光滑 之著色組成物的精細外來物質。 在使用過濾器時，可組合不同過濾器。在此情況下， 83 201237551A surfactant may be used, or two or more than two surfactants may be used in combination, but the polymerizable composition of the present invention preferably has a content of from 0.001% by mass to 1 in the polymerizable composition of the present invention. In addition to the above basic components and the addition of the L, the other components may be appropriately selected and used in accordance with the scope of the present invention. Examples of other components which can be used in combination include a decane coupling agent, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, and a coloring agent (colored pigment or dye). In addition, a substrate surface adhesion promoter and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release promoters, antioxidants, and the like) may be used in combination. Perfume, surface tension agent (jjusting agent, and chain transfer agent). By properly incorporating these components, the properties of the target solder resist can be adjusted, such as stability, photographic properties, and In particular, it is preferable to add a kneading agent for reinforcing the adhesion of the substrate. For example, the thermal polymerization inhibitor is detailed in paragraphs [0101] and [0102] of JP-A-2008-250074. For example, in JP-A Plasticizers are detailed in paragraphs [0103] and [0104] of paragraphs 2008-250074. 82 201237551 For example, paragraphs [〇1〇5] and paragraphs [0106] of JP-A-2008-250074 and jp_A-2009 The coloring agent is described in detail in paragraph [20538] and paragraph [0039]. Adhesion promoters are described in detail in paragraphs [01〇7] to [0109] of JP-A-2008-250074. All the additives mentioned in the case can be used in this case. The polymerizable composition of the present invention has a solid content concentration of the present invention preferably from 5% by mass to 9% by mass, more preferably from 2% by mass to 80% by mass, and most preferably 40% by weight. 5% by mass to 60% by mass. It is preferred to filter the polymerizable composition of the present invention through a filter for the purpose of removing foreign matter or reducing defects. Filters and similar filters can be used without any particular limitation. An example thereof includes a filter formed of a fluororesin (f[u〇r〇resin] such as PTfe (polytetrafluoroethylene)), a polyamide resin such as nylon-6 (nylon-6), and Nylon 6,6; and polyolefin resins (including high density polyolefins and ultra high molecular polyolefins) such as polyethylene and polypropylene (PP). In these materials, 'polypropylene (including high density polypropylene) is more Preferably, the filter has a pore size (P〇re size) of about 〇〇1 μm to 7 μm, preferably about 0·01 μm to 2.5 μm, more preferably about 〇〇1 μm to 1.5 μm. Within the range, the mixture can be reliably removed ^ Suppressing material or the like and preparing a uniform and smooth fine foreign matter of the coloring composition in a later step. When using a filter, different filters may be combined. In this case, 83201237551

—Γ、/·/ !· ▲* 上^ 裊 A 經由第一過濾器過濾可僅進行一次或可進行兩次或超過兩 次。在藉由使用不同過遽器之組合來進行兩次或超過兩次 過》慮之情況下’第一次過渡以及後績過遽中之孔徑較佳大 於第一次過滤之孔徑。此外，可組合在上述範圍内孔徑不 同之第一過濾器。對於如本文所用之孔徑’可參考過渡器 製造商之標稱值。關於市售過濾器，過濾器可選擇自例如 由曰本巴爾公司（Nihon Pall Corporation )、曰本東洋有限 公司（Advantec Toyo Kaisha，Ltd.)、日本英特格公司（Nih〇n Entegris K.K.)(先前為日本密科理公司（Nih〇n Mykr〇lis Corporation ))以及北澤微濾器（Kkz Micr〇mter Corporation)中所提供之各種過濾器。 可使用由與第一過濾器相同之材料或其類似物形成 之過濾器作為第二微濾器。第二過濾器之孔徑宜為大約〇 5 微米至7.0微米，較佳為大約2.5微米至7.〇微米，更佳為 大約4.5微米至6.0微米。在此樹脂内，可移除混合於混 合/谷液中且在稱後步驟中抑制製備均一且光滑之可聚合組 成物的外來物質，同時保留混合溶液中所含之組分粒 ^舉例而言，可能藉由僅使用液體分散液經由第一過濾 器進行過濾且在混合其他組分之後經由第二過滤器進行過 澈。 本發明之可聚合組成物的使用應用不受特別限制，但 其實例包括阻焊劑、用於固態攝影元件中石夕基板之後表面 (backspace)的遮光膜（light_shieldingfUm)，以及用於 晶圓級透鏡之遮光膜，其中阻焊劑為較佳。 84 201237551 在將本發明之可聚合組成物用於阻悍劑之情況下，為 形成具有相對較大厚度之塗膜，固體含量濃度較俨為3〇 質量％至80質量％，更佳為35質量％至7〇質量％，且 佳為40質量％至60質量％。 本發明之可聚合組成物的黏度較佳為〗毫帕.秒至 3,〇〇〇宅帕.秒’更佳為10毫帕·秒至2，_毫帕秒且 為100毫帕·秒至1,500毫帕.秒。 ❹ 在將本發明之可聚合組成物用於阻焊劑之情況下，鑒 於厚膜可成形性以及均一可塗佈性，黏度較佳為1〇毫帕. 秒至3,000毫帕.秒，更佳為5〇〇毫帕.秒至15〇〇毫帕秒， 且最佳為700毫帕.秒至ι，4〇〇毫帕.秒。 本發明亦’由本發明之可聚合組成物形成的感光 層。此感，層由本發明之可聚合組成物形成，因此為在紅 外區顯示高擔光作用且在可見光區顯示高透光度且能夠藉 由驗性顯影形成具有極佳解析度之圖案的感光層。此外， 纟上方設置感光層之基板具有不均勻形狀之情況下，本發 〇 %之感光層為㈣具有成魏追蹤基板不均自形狀之形狀 的感光層。 本發Τ亦關於使用本發明之可聚合組成物形成的永 久圖案。藉由對由本發明之可聚合組成物形成之感光層應 用曝光以及驗性顯影來獲得本發明之永久圖案，且藉助於 使用本發明之可聚合組成物，此圖案為在紅外區顯示高擔 光作用且在可見光區顯示高透光度並藉由 驗性顯影而使得 解析度極佳之圖案。此外，如上所述，本發明之感光層具 85 201237551 = ====，不論基板位置 =步彳之，達到基==中= 圖案= 咸二二=敗二=明之圖案為 藉由使用本發明之可聚合’其依序包括 逐次曝光所述感光層以固化曝光區==::生 顯影移除未曝光區域以形成永久圖案之^ 下文藉由參考例如圖案化阻 發明之可聚合組成物形成永久圖1來1错由使用本 ==、r步驟或其他步驟及== 述不限於對阻焊劑之應用。在本 之 用可聚合組成物來形成感光層(可聚 -感光層_ =成圖案化阻焊劑（阻烊圖案），首先使用本胸 =可t口組成物形成感光層。感光層不受特別 其為藉由含村聚合域物卿奴層即可，戶、、 taates一)及其類似參數可根據二來 形成感光層之方法包括如下方法，其包 可聚合組絲溶解、乳化或分散於水絲劑 86 201237551 以及乾燥塗層以 溶液，將塗佈溶液直接塗覆於支撐物上 形成感光層。—Γ, /·/ !· ▲* 上^ 袅 A Filtering through the first filter can be performed only once or twice or more than twice. In the case where two or more passes are made by using a combination of different filters, the aperture in the first transition and the after-period is preferably larger than the aperture in the first filtration. Further, the first filter having a different pore diameter within the above range may be combined. For the aperture 'as used herein, reference is made to the nominal value of the transitioner manufacturer. Regarding commercially available filters, filters can be selected, for example, from Nihon Pall Corporation, Advantec Toyo Kaisha, Ltd., and Nih〇n Entegris KK ( Previously, various filters were provided by Nih〇n Mykr〇lis Corporation and Kkz Micr〇mter Corporation. A filter formed of the same material as the first filter or the like may be used as the second microfilter. The second filter preferably has a pore diameter of from about 〇 5 μm to 7.0 μm, preferably from about 2.5 μm to about 7. μm, more preferably from about 4.5 μm to 6.0 μm. In this resin, the foreign matter mixed in the mixed/column solution and inhibiting the preparation of the uniform and smooth polymerizable composition in the subsequent step can be removed while retaining the component particles contained in the mixed solution. It is possible to filter through the first filter by using only the liquid dispersion and to pass the second filter after mixing the other components. The use of the polymerizable composition of the present invention is not particularly limited, but examples thereof include a solder resist, a light-shielding film (light_shielding fUm) for a backspace of a solid-state photographic element, and a wafer-level lens. A light-shielding film in which a solder resist is preferable. 84 201237551 In the case where the polymerizable composition of the present invention is used for a barrier, in order to form a coating film having a relatively large thickness, the solid content concentration is from 3% to 80% by mass, more preferably 35. The mass% to 7〇% by mass, and preferably 40% by mass to 60% by mass. The viscosity of the polymerizable composition of the present invention is preferably from MPa to sec., and from 2 to 3, preferably from 10 mPa·s to 2, _mPas and 100 mPa·s. Up to 1,500 mPa. seconds. ❹ In the case where the polymerizable composition of the present invention is used for a solder resist, the viscosity is preferably from 1 μmPas to 3,000 mPas, preferably in view of thick film formability and uniform coatability. It is 5 〇〇 mPa. sec to 15 〇〇 millipascal seconds, and the best is 700 mPa. sec to ι, 4 〇〇 mPa. sec. The present invention also relates to a photosensitive layer formed of the polymerizable composition of the present invention. In this sense, the layer is formed of the polymerizable composition of the present invention, and thus is a photosensitive layer which exhibits a high light-receiving effect in the infrared region and exhibits high transmittance in the visible light region and can form a pattern having excellent resolution by inferior development. . Further, in the case where the substrate on which the photosensitive layer is disposed has an uneven shape, the photosensitive layer of the present invention has (4) a photosensitive layer having a shape in which the substrate is unevenly oriented. The present invention also relates to a permanent pattern formed using the polymerizable composition of the present invention. The permanent pattern of the present invention is obtained by applying exposure and verifiable development to the photosensitive layer formed of the polymerizable composition of the present invention, and by using the polymerizable composition of the present invention, the pattern exhibits high light load in the infrared region. A pattern that exhibits excellent resolution by exhibiting high transmittance in the visible light region and by developability. In addition, as described above, the photosensitive layer of the present invention has a function of 2012 201251 51 = ====, regardless of the substrate position = step, reaches the base == medium = pattern = salty two = defeat two = bright pattern by using this The polymerizable composition of the invention includes sequentially exposing the photosensitive layer to cure the exposed region ==:: bio-developing to remove the unexposed regions to form a permanent pattern, hereinafter, by reference, for example, a polymerizable composition of the invention Forming a permanent pattern 1 to 1 error is not limited to the application of the solder resist by using the ==, r step or other steps and ==. In the present invention, a polymerizable layer is formed by using a polymerizable composition (a condensable-photosensitive layer _ = a patterned solder resist (resistance pattern), and a photosensitive layer is first formed using the present chest = a composition of a t-port. The photosensitive layer is not particularly The method for forming a photosensitive layer according to the second embodiment of the present invention includes the following method: the method comprises the following method, wherein the polymerizable group is dissolved, emulsified or dispersed. The water-curing agent 86 201237551 and the dried coating are applied as a solution, and the coating solution is directly applied to the support to form a photosensitive layer.

的自備塗脑狀溶财受㈣限敎可根據目 ν广夠句一溶解或分散本發明之可聚合組成物之 2溶劑適t選擇。其實例包括醇，諸如甲醇、乙醇、正 及正己i丙醇正丁醇、第二丁醇(sec〇ndarybutan〇i)以 =，_ ’諸如丙酮、甲基乙基酮、甲基異丁基酉同、 =以及二異丁基酮（diis〇butyiket〇ne);酯，諸如乙酸 曰田乙酸丁醋、乙酸正戊酯、硫酸甲醋、丙酸乙酯、鄰 I酸二甲醋、苯甲酸乙酯、丙二醇單甲喊乙酸醋以及 w 土乙酸丙酯（meth〇xy propyl acetate);芳族烴，諸如 甲苯、二甲苯、苯以及乙基苯；•代烴’諸如四‘化碳、 ^氣^^烯、氯仿、Μ，1-三氯乙烷、二氣曱烷以及一氯笨； _，諸如四氫呋喃、乙醚、乙二醇單曱醚、乙二醇單乙醚、 曱氧基-2-丙醇以及丙二醇單甲醚；二曱基曱醯胺、二曱 基乙醯胺、二甲亞砜以及環丁颯。可單獨使用這些溶劑中 一者，或可組合使用其兩者或超過兩者。此外，可添加習 知界面活性劑。 將塗佈溶液塗覆於支撐物上之方法不受特別限制且 可根據目的適當選擇，且其實例包括使用旋塗機（spin C〇ater )、縫隙旋塗機（slit spin coater )、滾塗機（r〇11 C〇ater)、模塗機（die coater)或簾塗機（curtain coater) 之塗佈法。 乾燥塗層時之條件視個別組分、溶劑種類、所用比率 87 201237551 及其類似因素而變，但通常為⑼乞至15〇<5(：之溫度以及3〇 秒至15分鐘。 感光層厚度不受特別限制且可根據目的適當選擇，但 例如較佳為1微米至1〇〇微米，更佳為2微米至5〇微米， 更佳為4微米至3〇微米。 (阻浑圖案形成方法） 日藉由使用本發明之阻焊劑之可聚合組成物來形成阻 =永久圖案的方法包括至少—個曝光步驟且通常更包括在 而要時之適當選擇之條件下的顯影步驟 ，以及其他步驟。 如本發a月中所用之術語「曝光」不僅包括在各種波長下曝 光，而且包括用輻射（諸如電子束以及X射線）進行照射。 <曝光步驟> 曝光步驟為使由可聚合組成物層形成之感光層經由 遮罩曝光之步驟，且在此步驟中，僅受到光照射之區域固 化。 曝光較佳藉由用輻射進行照射來進行，且可用於曝光 之輻射的實例包括可見射線、紫外線、遠紫外線、電子束 以及X射線。輻射較佳為電子束、KrF、ArF、紫外線（諸 如g線、h線以及i線）或可見光。其中，g線、^線以及 i線為較佳。 曝光糸統包括例如步進器曝光（stepper exposure )以 及使用高壓水銀燈之曝光。 曝光劑量較佳為5毫焦/公分2至3,000毫焦/公分2， 更佳為10毫焦/公分2至2,〇〇〇毫焦/公分2，且最佳為5〇 88 201237551 毫焦/公分2至1,000毫焦/公分2。 <其他步驟> 目的適當選擇。其實 驟、固化處理步驟以 其他步驟不受特別限制且可根據 例包括表面處理基材之步驟、顯影步 及後曝光步驟（p〇st-exposurestep)。 <顯影步驟>The self-prepared brain-like solution can be selected according to the conditions of the solvent of the polymerizable composition of the present invention. Examples thereof include alcohols such as methanol, ethanol, n- and n-propanol n-butanol, and second butanol (sec〇ndarybutan〇i) to =, _ 'such as acetone, methyl ethyl ketone, methyl isobutyl hydrazine, = and diisobutyl ketone (diis〇butyiket〇ne); esters, such as acetic acid vinegar acetic acid butyl vinegar, n-amyl acetate, methyl vinegar, ethyl propionate, o-acid dimethyl acetonate, ethyl benzoate , propylene glycol monomethyl acetate and meth xy propyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene and ethylbenzene; • hydrocarbons such as tetra' carbon, gas ^ Alkene, chloroform, hydrazine, 1-trichloroethane, dioxane, and monochlorobenzene; _, such as tetrahydrofuran, diethyl ether, ethylene glycol monoterpene ether, ethylene glycol monoethyl ether, decyloxy-2-propanol Alcohol and propylene glycol monomethyl ether; dimethyl decylamine, dimethyl acetamide, dimethyl sulfoxide and cyclobutyl hydrazine. One of these solvents may be used alone, or two or more of them may be used in combination. In addition, conventional surfactants can be added. The method of applying the coating solution to the support is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include using a spin coater, a slit spin coater, and a roll coater. Coating method of machine (r〇11 C〇ater), die coater or curtain coater. The conditions for drying the coating vary depending on the individual components, the type of solvent, and the ratio used, 87 201237551 and the like, but are usually (9) 乞 to 15 〇 < 5 (: temperature and 3 sec to 15 min. The thickness is not particularly limited and may be appropriately selected depending on the purpose, but is, for example, preferably from 1 μm to 1 μm, more preferably from 2 μm to 5 μm, still more preferably from 4 μm to 3 μm. Method) A method of forming a resistive permanent pattern by using a polymerizable composition of the solder resist of the present invention includes at least one exposure step and usually further includes a development step under conditions appropriately selected, and other The term "exposure" as used in the month of the present invention includes not only exposure at various wavelengths but also irradiation with radiation such as electron beam and X-rays. <Exposure step> Exposure step is made by polymerizable The photosensitive layer formed by the composition layer is exposed through the mask, and in this step, only the region irradiated with the light is cured. The exposure is preferably performed by irradiation with radiation, and can be used for Examples of the radiation of light include visible rays, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays. The radiation is preferably an electron beam, KrF, ArF, ultraviolet rays (such as g-line, h-line, and i-line) or visible light. The ^ line and the i line are preferred. The exposure system includes, for example, stepper exposure and exposure using a high pressure mercury lamp. The exposure dose is preferably 5 mJ/cm 2 to 3,000 mJ/cm 2 , more Preferably, 10 mJ/cm 2 to 2, 〇〇〇mJ/cm 2, and the best is 5〇88 201237551 mJ/cm 2 to 1,000 mJ/cm 2. <Other Steps> In other words, the curing step is not particularly limited in other steps and may include a step of surface treating the substrate, a developing step, and a post exposure step (p〇st-exposure step) according to an example. <Developing step>

=光倾錢，騎雜顯影 使在曝光步驟巾未叫照射 此 液中。因此，僅保留光固化部具== 圖案化阻焊劑。 战具純光作用之 (underlying circuit) > ^ 〇 20〇c^ ；〇^7 間為10秒至180秒。 王叫U且顯衫時 關於顯影劑中所用之鹼走 驗性化合物（諸如氨^ 4純水將有機 胺、-甲美r植脫(—咖amm〇nia)、乙胺、二乙 Ϊ :: 四甲基銨氫氧化物、四乙基銨氫氧化 烯）鞴勤>/ ，氮雙環伐4,0]·7·十一碳 ^稀釋至—般為_!質量％至ίο質量％，較佳A 0 = 1質量％之濃度所獲得的驗性水溶液。在=由 叙顯影義情況下，-㈣純水洗務^ <固化處理步驟> 採廡η處理步料錢賴影步雜，必要時將固化處 理應用於所形成圖案中之感光層，且藉由進行:二ί 89 201237551 強永久圖案之機械強度之步鄉。 I 口^5理步驟不X特別限制且可根據目的適當選 擇’但，、貫例包括整個表面曝光處理以及整個表面加熱處 理。 用於整個表面曝光處理之方法包括例如一種在顯影 A ti有所形成之圖案化感光層之層壓物 切法。藉錄録轉光，促進 之可聚合組成物中之聚合組分的固化，且使 =久圖案之固化進-步進彳f，藉此改良機械強度以及耐久 性。 »g 編限制且可根 壓水銀燈。例包括UV曝光機，諸如超高 用於整個表面加熱處理之方法包括一 之圖案化感光層之層壓物的整:= 方法。糟由整個表面加熱，圖案之膜強度得到提高。 整個表面加熱中之加熱溫度較佳為12(TC至250X：， 1佳為14=至220°C。當加熱溫度為_或_ _ 時，膜強^精由加熱處理得到提高，且當其為靴或低 變:防止膜品質因可光聚合組成… 鐘，===間較佳為3分鐘… 用於進行整個表面加熱之裂置不受特別限制且可根 90 201237551 據目的自習知裝置適當選擇。其實例包括烘箱（_ oven)、熱板（hotplate)以及说加熱器。 由此形成之圖案化抗蝕劑具有極佳之紅外阻擋作 用，因此具有廣泛應用範圍。本發明之可聚合組成物在紅 外區具有極錄光個且對可見光區具有斜線透光度， 因此可形成具有極佳形態之圖案。同時，所形成之圖案（固 化膜）具有極佳紅外阻擔作用，奴適用於形成用於具有 甚至對紅外區具有敏感性之光電二極體之元件（特別是固 態攝影元件）的阻焊劑。 如上所述，本發明之可聚合組成物適用於不僅形成阻 焊劑，而且形成固態攝影元件中矽基板之後表面的擋光 膜，或晶圓級透鏡之擋光膜。 以此方式，本發明亦關於一種具有由本發明之可聚合 組成物形成之永久圖案的固態攝影元件。 下文藉由參考圖1以及圖2來描述根據本發明一實施 例之固態攝影元件，但本發明不限於以下特定實例。 附▼而5 ’共同數字標號（c〇mm〇n numerical reference)用於圖1與圖2之間的共同部分。 此外，在說明書中’「頂部（top )」、「在…上方（ab〇ve)」 以及「上側（upper Side )」表示遠離矽基板10之侧，且「底 部（bottom )」、「在…下方（below )」以及「下側（l〇wer side )」 表示接近矽酮基板1〇之側。 圖1為展示具有根據上述一個實施例之一特定實例之 固恕攝影元件的相機模組（camera module)之組態的示意 201237551 -TV/d i 性截面圖。 在圖1中，經由作為連接構件之焊球（s〇lderball) 6〇 將相„ 200連接至呈封裝基板形式之電路基板7〇。 洋言之，相機模組2〇〇經組態以包括在矽基板之第一 ，要表面上具有攝影元件部分之固祕影元件基板1〇〇、 女置在固態攝影元件基板100之第一主要表面上方之玻璃 基板30 (光透射基板）、安置在玻璃基板3〇上方之紅外截 止渡光片42、安置在玻璃基板3〇以及紅外截止渡光片42 上方且在内部空間具有攝影透鏡4〇之透鏡架（匕仍 50，以及安置為包圍固態攝影元件基板1〇〇以及玻璃基板 30之周邊的擂光及電磁遮蔽44。各構件經由黏著劑2〇、 4卜43或45結合。 在相機模組200中，入射光hv自外部依次穿過攝影 透鏡40、紅外截止濾光片42以及玻璃基板3〇且達至固態 攝影元件基板1〇〇之攝影元件部分。 此外，相機模組200經由固態攝影元件基板1〇〇之第 二主要表面側之焊球60 (連接材料）連接至電路基板7〇。 圖2為展示圖1中之固態攝影元件基板1〇〇的放大比 例截面圖。 固態攝影元件基板100經組態以包括作為基體（base body)之碎基板1〇、攝影元件12、層間絕緣膜（interiayer insulating film ) 13、基層（base layer ) 14、紅色濾光片 15R、 綠色濾光片15G、藍色濾光片15B、外塗層16、微透鏡17、 擋光膜18、絕緣膜22、金屬電極23、阻焊層24、内部電 92 201237551 極26以及元件表面電極27。 可省略阻焊層24。 首先’主要描述固態攝影元件基板100之第一主要表 面側之組態。 如圖2中所示’將二維排列諸如CCD以及CMOS之 多個攝影元件12的攝影元件部分設置於作為固態攝影元 件基板100之基體的矽基板10之第一主要表面側。= light dumping, riding hybrid development so that the exposure step is not called to illuminate this liquid. Therefore, only the photocuring member is retained == patterned solder resist. Underlying circuit > ^ 〇 20〇c^ ; 〇^7 is between 10 seconds and 180 seconds. When the king calls U and the shirt is used, the alkali-testing compound used in the developer (such as ammonia ^ 4 pure water will be organic amine, - Jiamei r planting (-caffe amm〇nia), ethylamine, diethyl hydrazine: : tetramethylammonium hydroxide, tetraethylammonium hydroxide, hydrazine>/, nitrogen double-ringed 4,0]·7·11 carbon^diluted to - _!% by mass to ίο% by mass An aqueous solution obtained by a concentration of A 0 = 1% by mass is preferred. In the case of = development, - (4) pure water washing ^ < curing treatment step > 庑 处理 processing step money, and if necessary, the curing treatment is applied to the photosensitive layer in the formed pattern, and By proceeding: 2 ί 89 201237551 Strong permanent pattern of mechanical strength of the town. The I step is not particularly limited and may be appropriately selected depending on the purpose. However, the entire example includes the entire surface exposure treatment and the entire surface heat treatment. The method for the entire surface exposure treatment includes, for example, a laminate cut method in which a patterned photosensitive layer formed by developing A ti is formed. By recording the light, the curing of the polymeric component in the polymerizable composition is promoted, and the curing of the pattern is advanced to step 彳f, thereby improving mechanical strength and durability. »g is limited and can be used to pressure mercury lamps. Examples include UV exposure machines, such as ultra-high methods for the entire surface heat treatment including a laminate of a patterned photosensitive layer: = method. The grain is heated by the entire surface, and the film strength of the pattern is improved. The heating temperature in the entire surface heating is preferably 12 (TC to 250X:, 1 is preferably 14 = to 220 ° C. When the heating temperature is _ or _ _, the film strength is improved by heat treatment, and when For the boot or low change: prevent the film quality from being photopolymerizable... Clock, === is preferably 3 minutes... The crack for the whole surface heating is not particularly limited and can be rooted 90 201237551 Suitable examples include ovens, hotplates, and heaters. The patterned resist thus formed has excellent infrared blocking and thus has a wide range of applications. The composition has a polar recording in the infrared region and a diagonal transmittance to the visible region, so that a pattern with an excellent morphology can be formed. At the same time, the formed pattern (cured film) has an excellent infrared blocking effect, and is suitable for slave use. A solder resist for forming an element (particularly a solid-state photographic element) having a photodiode sensitive to an infrared region. As described above, the polymerizable composition of the present invention is suitable for forming not only a solder resist but also a solder resist. And forming a light blocking film on the surface of the back surface of the solid state photographic element, or a light blocking film of the wafer level lens. In this manner, the present invention also relates to a solid state photographic element having a permanent pattern formed by the polymerizable composition of the present invention. Hereinafter, a solid-state imaging element according to an embodiment of the present invention will be described with reference to FIG. 1 and FIG. 2, but the present invention is not limited to the following specific examples. With the addition of a common numerical number (c〇mm〇n numerical reference) In the description, "top", "above" and "upper side" indicate the side away from the substrate 10 And "bottom", "below", and "lower side" mean the side close to the fluorene ketone substrate 1 。. Fig. 1 is a view showing one of the above embodiments. A schematic diagram of the configuration of a camera module of a forgotten photographic element of a specific example 201237551 - TV/di cross-sectional view. In Fig. 1, the phase is passed through a solder ball (s〇lderball) as a connecting member. „ 200 Connected to the circuit substrate 7 in the form of a package substrate. In other words, the camera module 2 is configured to be included in the first of the 矽 substrate, and the phantom element substrate having the photographic element portion on the surface 〇〇 a female glass substrate 30 (light transmitting substrate) disposed above the first main surface of the solid-state imaging device substrate 100, an infrared cut-off light-receiving sheet 42 disposed above the glass substrate 3, a glass substrate 3, and an infrared cut-off Above the light sheet 42 and in the inner space, there is a lens holder of the photographic lens 4, and a light and electromagnetic shield 44 disposed to surround the solid-state photographic element substrate 1 〇〇 and the periphery of the glass substrate 30. Each member is bonded via an adhesive 2, 4, 43 or 45. In the camera module 200, the incident light hv sequentially passes through the photographic lens 40, the infrared cut filter 42, and the glass substrate 3 from the outside and reaches the photographic element portion of the solid-state photographic element substrate 1A. Further, the camera module 200 is connected to the circuit board 7A via solder balls 60 (connection materials) on the second main surface side of the solid-state imaging element substrate 1A. Fig. 2 is a cross-sectional view showing an enlarged ratio of the solid-state imaging element substrate 1A of Fig. 1. The solid-state photographic element substrate 100 is configured to include a substrate 1 as a base body, a photographic element 12, an elementary insulating film 13, a base layer 14, a red filter 15R, and a green Filter 15G, blue filter 15B, overcoat layer 16, microlens 17, light blocking film 18, insulating film 22, metal electrode 23, solder resist layer 24, internal electricity 92 201237551 pole 26 and element surface electrode 27 . The solder resist layer 24 can be omitted. First, the configuration of the first main surface side of the solid-state imaging element substrate 100 is mainly described. As shown in Fig. 2, a photographic element portion in which two photographic elements 12 such as CCD and CMOS are two-dimensionally arranged is disposed on the first main surface side of the ruthenium substrate 10 which is a base of the solid-state photographic element substrate 100.

在攝影元件部分中之攝影元件12上形成層間絕緣膜 13，且在層間絕緣膜13上形成基層14。此外，將紅色濾 光片15R、綠色濾光片15G以及藍色濾光片15B(下文有 時統稱為「彩色濾光片15」）安置於基層14上以對應於個 別攝影元件12。 可將未圖示之擔光膜設置於紅色濾光片15R、綠色濾 光片15G以及藍色濾光片15B之邊界中以及設置於攝影元 件部分之周邊。此擋光膜可例如藉由使用習知之黑色^ 劑來製造。 在於色遽光片15上形成外塗層16,且在外塗層μ上 形成微透鏡17以對應於攝影元件12 (彩色濾光片θ15)。 將周邊電路（未圖示）以及内部電極26設置於第一 主要表面側之攝影元件部分之周邊，且經由周邊電路 部電極26電連接至攝影元件12。 此外，經由層間絕緣膜13在内部電極％上形成元 表面電極27’且在内部電極26肖元件表面電極27之 層間絕緣膜13巾，形成胁電性連接㈣電極之接觸塞 93 201237551An interlayer insulating film 13 is formed on the photographic element 12 in the photographic element portion, and a base layer 14 is formed on the interlayer insulating film 13. Further, a red color filter 15R, a green color filter 15G, and a blue color filter 15B (hereinafter collectively referred to as "color filter 15") are disposed on the base layer 14 to correspond to the individual photographic elements 12. A light-shielding film (not shown) may be provided in the boundary between the red color filter 15R, the green color filter 15G, and the blue color filter 15B, and provided around the image element portion. The light-blocking film can be produced, for example, by using a conventional black agent. An overcoat layer 16 is formed on the color grading sheet 15, and a microlens 17 is formed on the overcoat layer μ to correspond to the photographic element 12 (color filter θ15). A peripheral circuit (not shown) and an internal electrode 26 are provided on the periphery of the photographic element portion on the first main surface side, and are electrically connected to the photographic element 12 via the peripheral circuit portion electrode 26. Further, the element surface electrode 27' is formed on the internal electrode % via the interlayer insulating film 13, and the interlayer insulating film 13 of the surface electrode 27 of the internal electrode 26 is formed on the internal electrode 26 to form a contact plug of the (four) electrode.

L元極_27上形成基層14,且在基層14 電壓或讀取通The base layer 14 is formed on the L-element _27, and the voltage or read-through is performed at the base layer 14.

設置於攝影元件部分之周邊’且嶋攝影元件基板 100與玻璃基板30經由黏著劑2〇結合。 此外，矽基板10具有穿透矽基板10之通孔（thr〇ugh hole) ’且在通孔内設置作為金屬電極23之一部分的貫通 電極（through-electrode)。攝影元件部分與電路基板7〇藉 由貫通電極來電連接。 下文主要描述固態攝影元件基板1〇〇之第二主要表面 側之組態。 在第二主要表面側，在自第二主要表面至通孔内壁之 區域上形成絕緣膜22。 將經圖案化以自矽基板10之第二主要表面上之區域 延伸至通孔内的金屬電極23設置於絕緣膜22上。金屬電 極2 3為用於在固態攝影元件基板丨〇 〇中之攝影元件部分與 電路基板70之間進行連接之電極。 在此金屬電極23外，在通孔内形成之部分為貫通電 94The photographic element substrate 100 and the glass substrate 30 are bonded to each other via the adhesive 2'. Further, the ruthenium substrate 10 has a through hole which penetrates the ruthenium substrate 10 and a through-electrode which is a part of the metal electrode 23 is provided in the through hole. The photographic element portion is electrically connected to the circuit substrate 7 by a through electrode. The configuration of the second main surface side of the solid-state imaging element substrate 1 is mainly described below. On the second main surface side, an insulating film 22 is formed on a region from the second main surface to the inner wall of the through hole. A metal electrode 23 patterned to extend from a region on the second main surface of the substrate 10 to the via hole is provided on the insulating film 22. The metal electrode 23 is an electrode for connecting between the photographic element portion in the solid-state imaging element substrate 与 and the circuit substrate 70. Outside the metal electrode 23, the portion formed in the through hole is a through-current 94.

件之焊球⑼設置於㈣光之金屬_ 匕、攝衫兀件基板100之金屬電極23與電路美 反〇之未圖示連接電極經由焊球6〇來電性連接。 A在上文中，描述了固態元件基板100之組態，但除固 態攝影兀件基板觸之撞光膜18外之各部分可藉由諸如以 下之習知方法形成：Jp-a-2009-158863之段落0033至段落 201237551 極。貝通電極穿透秒某、 到内部電極26之下方h &以及層間絕緣臈之—部分以達 此外，在第二主要矣電性連接至内部電極26。 緣膜），其覆蓋切形成金^2^層24 (保護性絕 具有部分金屬電極23 —主要表面’且 另外，在篦-士©± 方形成阻焊層24之第_ &置擔域18 ’其覆蓋上 23之-部分的開放部分·：要表面，料有曝光金屬電極 之擋擔域18與阻焊層24統一成單層 管擋=及由二明2::f合組成物形成，或⑺儘 發明之為個观，域_ 18可由本 阻二ir形成(在此情況下，阻焊層可由習知 邻八’在圖2中，擋光膜18經圖案化以覆蓋一 屬 ==:=:分’但可經圖案化以曝光金 (Π樣適用於阻烊層24之圖案化）。 此外’可省略阻烊層％，或擒光M is可直 金屬電極23之第二主要表面上形成。 在$成 95 201237551 0068中所述之方法，以及JP-A-2009-99591之段落〇〇36 至段落0065中所述之方法。The solder ball (9) of the piece is placed on the (4) metal of the light _ 匕, the metal electrode 23 of the photographic board substrate 100 and the circuit. The connection electrode (not shown) is electrically connected via the solder ball 6 。. A In the above, the configuration of the solid-state element substrate 100 is described, but portions other than the solid-state photographic element substrate touching the light-impinging film 18 can be formed by a conventional method such as the following: Jp-a-2009-158863 Paragraph 0033 to paragraph 201237551 Extreme. The Beton electrode penetrates the second, to the lower portion of the internal electrode 26, h & and the interlayer insulating layer, in addition, the second main crucible is electrically connected to the internal electrode 26. a rim film), which covers the dicing layer 2 (protectively has a part of the metal electrode 23 - the main surface) and additionally forms the first layer of the solder resist layer 24 in the 篦-士©± square 18 'It covers the open part of the part of 23 -: The surface is covered with the exposed metal electrode and the solder resist layer 24 is unified into a single layer of tube block = and the composition of the two: 2::f Forming, or (7) by way of the invention, the domain _ 18 may be formed by the present resistor ir (in this case, the solder resist layer may be by the conventional neighbor VIII) in FIG. 2, the light blocking film 18 is patterned to cover one Genus ==:=: minute 'but can be patterned to expose gold (the sample is suitable for the patterning of the barrier layer 24). In addition, the % of the barrier layer can be omitted, or the blue electrode can be straight metal electrode 23 The method described in US Pat. No. 95, 2012, 375, 051, and the method described in paragraphs 36 to 9556 of JP-A-2009-99591.

可藉由用於本發明之擂光膜之上述製造方法來形成 擋光膜18。 X 藉由錢鍍、CVD (化學氣相沈積）或其類似方法形成 層間絕緣膜13 ’例如作為si〇2膜或SiN膜。 例如藉由光微影，使用習知彩色抗蝕劑來形成彩色濾 光片15。 … 例如藉由光微影，使用用於有機層間膜形成之習知 餘劑來形成外塗層16以及基層14。 几 例如藉由光微影，使用苯乙烯類樹脂或其類 成微透鏡17。 & 在阻焊層24與擋光層㈣合形成單層形式的播光阻 焊層之情況下，所述層較佳由本發明之可聚合組成物形成。 另一方面，當阻焊層24以及檔光臈18為個別層 阻焊層24較佳例如藉由級影，使用含有盼系樹脂:聚納 亞胺類樹脂或胺類樹脂的習知阻焊劑來形成。 ’ 例如使用Sn-Pb (共熔（eutectic ) )、95pb Sn (古金… 熔點焊料）或無Pb焊料（諸如Sn_Ag、Sn_Cu以及Sn_ ^ ^而 來形成焊球6G。使焊球6〇形成為例如直#為⑽微U 1，〇〇〇微米（直徑較佳為150微米至7〇〇微米）之球體、 例如藉由CMP (化學機械減）、光微影紐内 部電極26以及元件表面電極27形成為金屬電極，諸如^内 例如藉由濺鍍、光微影、餘刻或電解電鍛使金屬電極 96 201237551 23形成為金屬電極，諸如Cu、Au、^、n ?化合物、W化合物以及M〇化合物。、Mo、 單層組態或由兩層或超過兩層組成之多層組电。23可呈 金屬電極23之膜厚度為例如0.1微米至^ 佳為〇·1微米至10微米）。石夕基板1〇不受特=米（較 使用藉由削刮（牆ing )基板後表面@ 制，=The light-blocking film 18 can be formed by the above-described manufacturing method for the calender film of the present invention. X The interlayer insulating film 13' is formed by, for example, money plating, CVD (Chemical Vapor Deposition) or the like, for example, as a Si〇2 film or a SiN film. The color filter 15 is formed by, for example, photolithography using a conventional color resist. The overcoat layer 16 and the base layer 14 are formed, for example, by photolithography using a conventional agent for organic interlayer film formation. For example, a styrene-based resin or a microlens 17 thereof is used by photolithography. & In the case where the solder resist layer 24 and the light blocking layer (4) are combined to form a single layer of the light-shielding solder resist layer, the layer is preferably formed of the polymerizable composition of the present invention. On the other hand, when the solder resist layer 24 and the light-shielding layer 18 are individual layer solder resist layers 24, it is preferable to use a conventional solder resist containing a resin: a polyimine resin or an amine resin, for example, by leveling. To form. For example, solder ball 6G is formed using Sn-Pb (eutectic), 95pb Sn (old gold... melting point solder) or no Pb solder (such as Sn_Ag, Sn_Cu, and Sn_^^). For example, straight # is (10) micro U 1, 〇〇〇 micron (preferably 150 micrometers to 7 micrometers in diameter) spheres, for example, by CMP (chemical mechanical subtraction), photolithography internal electrode 26, and element surface electrodes 27 is formed as a metal electrode, such as by sputtering, photolithography, engraving or electrolytic forging, to form metal electrode 96 201237551 23 as a metal electrode, such as Cu, Au, ^, n? compounds, W compounds and M〇 compound, Mo, single layer configuration or multi-layer electricity consisting of two or more layers. 23 may have a film thickness of the metal electrode 23 of, for example, 0.1 μm to ^ 1 μm to 10 μm) . Shixi substrate 1〇 is not subject to special = m (more than using scraping (wall ing) substrate back surface @ system, =

板。基板厚度衫關，但使關如厚度 微米（較佳為30微米至15〇微米）之石夕晶圓。未至 例如藉由光微影以及RJE彳反岸& 基板H)之軌。 以紐料_0形成石夕 +在^别各頁中’藉由參考圖1以及圖2來描述作為上 述-個實施例之-特定實例的職、攝影元件基板ι〇〇，但 所述-個實_不限_ !以及圖2之_，且實施例之 組怨不文特別限制’只要其為在録面㈣i具有金屬電極 以及擋光膜之組態即可。 接著’下文藉由參考圖式來描述將使用本發明之可聚 合組成物獲得之永久圖案應用於晶圓級透鏡之擋光膜的實 例。 圖3為展示具有多個晶圓級透鏡之晶圓級透鏡陣列的 組態之一個實例的平面圖。 如圖3中所示，晶圓級透鏡陣列具有基板410以及排 列於基板410上之透鏡412。在本文中，在圖3中，多個 透鏡412相對於基板41〇二維排列，但所述透鏡亦可一維 排列。 97 201237551 -τν/*/ i 圖4為沿圖3中線A-A之截面圖。 如圖4中所示’在晶圓級透鏡陣列中，在排列於基板 410上之多個透鏡412之間設置用於防止光透射穿過除透 鏡412外之部分的擋光膜414。 晶圓級透鏡由存在於基板410上之一個透鏡412以及 β又置於其圓周邊中之擔光膜414構成。本發明之可聚合組 成物用於形成此擋光膜414。 下文藉由參考例如圖3中所示之多個透鏡412相對於 基板410二維排列之組態來描述晶圓級透鏡。 透鏡412 —般由與基板410相同之材料構成且整體模 製於基板410上或經模製為個別結構且固定於基板上。在 本文中，描述了一實例，但晶圓級透鏡不限於此實施例， 且可採用各種實施例，諸如具有多層結構之晶圓級透鏡， 或藉由切割（dicing)分成透鏡模組之晶圓級透鏡。 形成透鏡412之材料包括例如玻璃。存在豐富種類之 玻璃，且因為可選擇具有高折射率之玻璃，所以此材料適 用作透鏡材料。此外，玻璃耐熱性極佳且具有經受得住安 裝於攝影單元或其類似物上之回焊（refl〇w)的優勢。 用於形成透鏡412之其他材料包括樹脂。樹脂可加工 性（Pr〇CeSSability)極佳且適用於藉由模具或其類似物簡 單且廉價地形成透鏡表面。 在此情況下，能量可固化樹脂（enefgy__blefesin) 較佳用於形成透鏡412。能量可固化樹脂可為能夠藉由埶 固化之樹脂或能夠藉由以活性能量射線照射（例如以熱了 98 201237551 紫外線或電子束進行照射）來固化之樹脂。 作為能量可固化樹脂，可使用所有習知樹脂，但考慮 到攝影單元之回焊安褒，軟化點（softeningpoint)相對車^ 高（例如軟化點為20(TC或超過20(rc )之樹脂為較佳 化點為25〇C或超過250°C之樹脂更佳。 下文藉由參考例如基於圖5至圖1〇之晶圓級透鏡陣 列之製造方法來特定描述晶圓級透鏡之模式以及製造。 [晶圓級透鏡之模式以及製造（1)] 〇 -形成透鏡- 藉由參考圖5以及圖6A至圖6C來描述在基板410 上形成透鏡412之方法。 圖5為展不如何將作為用於透鏡形成之樹脂組成物的 模製材料（在圖5中由Μ表示）供應至基板410之圖。 此外’圖6Α至圖6C為展示藉由使用模具46〇將透鏡 412模製於基板41〇上之程序的圖。 如圖5中所示’藉由使用分配器45〇將模製材料μ滴 〇 於基板41〇之透鏡412模製部位上。在本文中，將對應於 一個透鏡412之量的模製材料Μ供應至待饋料之一個部 位。 一在將模製材料Μ供應至基板41〇之後，如圖6Α中所 示，將用於模製透鏡412之模具460安置於經供應模製材 料Μ之基板410表面側。 在模具460中，根據透鏡412之所需數目設置用於轉 印透鏡412形狀之凹面（c〇ncave) 462。 99 201237551 壓桓罝二f) 不’在基板410上與模製材料Μ相抵擠 f I 460以使模製材料Μ沿凹面啦形狀之線變形。在 ”杈製材料Μ相抵擠壓模具桐之狀態中 =::rr線可_脂時，以熱=二 ,，、、射板具460以使模製材料M固化。 、在模製材料Μ固化之後，如圖6C中所示，使基板· 以及透鏡412與模具460分離。 形成播光膜- 下文藉由參考圖7A至圖7C來描述在透鏡412之圓周 邊形成擋光膜414之方法。 圖7A至圖7C為展示在上方模製有透鏡412之基板 410上設置擋光膜414之製程的示意性截面圖。 形成擋光膜414之方法包括在基板41〇上塗佈本發明 之可聚合組成物以形成擋光塗層414A之播光塗層形成步 驟（參見圖7A)、經由遮罩470使擋光塗層414A圖案曝 光之曝光步驟（參見圖7B)，以及在曝光後使擋光塗層 414A顯影以移除未固化區域且形成圖案化擋光膜414之 顯影步驟（參見圖7C)。 附帶而言’形成擋光膜414可在製造透鏡412之前或 在製造透鏡412之後任意進行，但在本文中，詳述在製造 透鏡412之後進行所述形成之方法。 下文描述方法中形成擋光膜414之步驟。 <擋光塗層形成步驟> 在擋光塗層形成步驟中，如圖7A中所示，將可聚合 100 201237551 組成物塗佈於基板410上以形成具有低光學反射率且由可 聚合組成物構成之擋光塗層414A。此時，形成擋光塗層 414A以覆蓋所有基板410表面以及透鏡412之透鏡表面 412a以及透鏡邊緣412b表面。 可用於此步驟中之基板410不受特別限制。其實例包 括納玻璃（soda glass )、無驗玻璃（alkali-free glass )、Pyrex (註冊商標）玻璃、石英玻璃以及透明樹脂。 ◎ 在整體形成透鏡412與基板410之情況下，如本文所 用之基板410表示含有透鏡412與基板410之實施例。 在基板410上，必要時，可設置底塗層（underc〇at layer)以便改良對覆蓋層之黏著力、防止材料擴散，或使 基板410表面變平。 作為將可聚合組成物塗佈於基板41〇以及透鏡412上 之方法，可應用各種塗佈法，諸如縫隙塗佈（slit c〇ating )、 喷霧塗佈（spray coating )、喷墨印刷（inkjet printing )、旋 轉塗佈（spin coating)、流延塗佈（cast coating)、輥式塗 〇 佈（ro11 mating )以及網板印刷（screen printing )。 鑒於塗膜之厚度均一性以及塗佈溶劑之乾燥容易 性，在塗佈可聚合組成物後不久之膜厚度較佳為微米 至10 Μ米，更佳為〇 2微米至5微米，更佳為〇 2微米多 3微米。 塗佈於基板410上之檔光塗層414Α之乾燥（預熳） 可使用熱板、烘箱或其類似物在5〇它至14〇。〇之溫度下進 行10秒至300秒。 ’里又 101 201237551 "τ ν/w» J. 在乾燥可聚合組成物之後，塗膜厚度（下文有時稱作 「乾厚（dry thickness)」）可在考慮到效能（諸如所需擋光 作用）之情況下任意選擇，且一般為〇1微米至小於5〇微 米。 <曝光步驟> 在曝光步驟中，將在擋光塗層形成步驟中形成之擋光 塗層414A圖案曝光（patterned-exposed)。圖案曝光可為 掃描曝光（scanning exposure)，但如圖7B中所示，較佳 為經由具有預定遮罩圖案之遮罩470進行曝光的一實施 例。 關於此步驟中之曝光，藉由經由預定遮罩圖案曝光來 進行擋光塗層414A之圖案曝光，其中在擋光塗層414A外 僅受光照射之部分藉由曝光固化。在此曝光中，使用允許 光照射於透鏡邊緣412b表面以及透鏡412之間的基板410 表面上之遮罩圖案。藉由使用此遮罩圖案，藉由光照射來 固化僅在除透鏡表面412a外之區域中的擔光塗層414a， 且固化區域形成擋光膜414。 匕可用於曝光之輻射較佳為諸如g線、h線以及i線之 紫外線。對於此騎，可使用具有單-波長之光源，或可 使用含有所有波長之光源，諸如高壓水銀燈。 <顯影步驟> 為、隨後，進行鹼性顯影（顯影步驟），藉此在曝光中未 文光照射之部分（亦即擋光塗層414A之未固化區域）溶 解出進入驗性水溶液，且僅留下藉由光照射固化之區域。 102 201237551 414Α=/之’藉由使如® 7Β中所示曝紋擋光塗層 成之幹3^·’思如圖7C中所示，僅移除在透鏡表面12a上形 二tr A，且在其他區域中形成固化擋光膜414。 Ο Ο 之驗H步驟帽用之顯影劑（驗性水溶液）中所含 ::Lr吏用所有的有機驗性劑、無機驗性劑以及其 不“二二財讀光卿成’目為有機齡劑幾乎 二才目鄰電路或其類似物’所以較佳使用有機鹼性劑。 (有機例包括有機祕化合物 L>, Β, 0 ^ 土坟虱礼化物、膽鹼、吡咯、哌 ΐ機驗環似㈣十—碳烯，叹減化合物 諸！:氫氧仙、氫氧简、做氫納以及 乂佳將藉由以純水將此驗性劑稀釋至_1質 I。至10質量％ (較佳為〇〇1質量％至i質量之片 所獲得的鹼性水溶液用作顯影劑。 、 '又 顯影溫度通常為貌至3(rc，且顯影 90秒。 在使用由此鹼性水溶液構成之顯影劑的情況下， 顯影劑移除麵之未曝光區域之後，―如純水洗條（沖 ΐ二亦I，影之後’以純水充分洗細移除過 里‘、、、員衫背j，接者進一步進行乾燥步驟。 附帶而言，在進行上述擒光塗層形成步驟、曝光步驟 以及顯影步驟之後，必要時可提供藉由加熱（後培）及/ 或曝光來所形成讀細（料贿）的@化步驟。 103 201237551 。後培為在顯影後達成完全固化之加熱處理，且通常在 100 C，25〇t下進行熱固化處理。後焙之條件（諸如溫度 以及4間）可根據基板410或透鏡412之材料來適當設定。 舉例而5，當基板412為玻璃時，在上述溫度範圍外， 佳使用180。(：至24(rc之溫度。 此後焙處理應用於在顯影後所形成之擋光膜414，且 可在連續系統或分批系統中藉由使用加熱元件（諸如熱 板、對流烘箱（熱空缝環乾雜）以及高頻加熱器）以、 建立上述條件來進行。 藉由苓考例如透鏡412具有凹面形狀（但形狀不受特 別限制且可為凸面（c〇nvex)或非球面（aspheric))之情 況來4田述上述私序。此外，藉由參考例如將多個透鏡Μ〗 ，製於基板41G之-個表面上之晶圓級透鏡來描述上述程 序’但亦可採用將多個透鏡412模製於基板41〇之兩個表 面上的組態，且在此情況下，树透絲面外之區域十之 兩個表面上均形成圖案化擋光膜414。 [晶圓級透鏡之模式以及製造（2)] 圖8為展示晶圓級透鏡陣列之另—組態實例的圖。 圖8中所示之晶圓級透鏡呈以下組態（單體型） 中使用相同模製材料同時模製基板彻與透鏡犯。、 作為用於製備此晶圓級透鏡之模製材料，可使用血上 述模製材料㈣之模製材料。❹卜，在此實例中，在基板 410之-個表面（在圖中上侧之表面）上形成多個凹透鏡 (議隱⑻0412’且在另—表面（在圖中下側之表面） 104 201237551 上形成多個凸透鏡（convex !ens) 420。此外，在除基板 410之透鏡表面412a外的區域中形成（亦即在基板41〇表 面以及透鏡邊緣412b表面上形成）圖案化擋光膜414。可 應用上述程序作為形成擋光膜414時之圖案化方法。 [晶圓級透鏡之模式以及製造（3)] 下文藉由參考圖9A至圖9C以及圖10A至圖10C來 描述晶圓級透鏡陣列之又一組態實例以及其製造程序。 圖9A至圖9C為展示形成圖案化擋光膜414之另一製 程的不意圖。 圖10A至圖i〇c為展示首先形成圖案化擋光膜414 以及接著模製透鏡412之製程的示意圖。 在圖5至圖8中所示之晶圓級透鏡陣列的實例中，在 上方設置有透鏡412之基板410上形成圖案化擋光膜 414’但在以下程序中，首先在基板41〇上形成圖案化擋光 膜414，接著在基板41〇上模製透鏡412。 -形成擋光膜- 如圖9A中所示，首先進行將可聚合組成物塗佈於基 板410上以形成擋光塗層414人之擋光塗層形成步驟。 此後，使用熱板、烘箱或其類似物在5〇。〇至14(TC之 度下進行在基板41〇上形成之擋光塗層414A的乾燥川 矜，300秒。可根據效能（諸如所需擔光作用）任意選擇 可聚合^成物之乾厚，但其一般為0.1微米至小於50微米。 ，接著，如圖9B中所示，進行將在擋光塗層形成步驟 中形成之擋光塗層414A經由遮罩47〇來圖案逐次曝光的 105 201237551board. The thickness of the substrate is off, but it is such as a thickness of micron (preferably 30 micrometers to 15 micrometers). For example, by the light lithography and the RJE 彳 counter & substrate H) track. The formation of the photographic element ι 作为 作为 以 石 + + + + + + + + + + + + + + + + + + + + + + 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉实 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Next, an example of applying a permanent pattern obtained by using the polymerizable composition of the present invention to a light-blocking film of a wafer-level lens will be described hereinafter with reference to the drawings. 3 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. 3, the wafer level lens array has a substrate 410 and a lens 412 arranged on the substrate 410. Herein, in Fig. 3, a plurality of lenses 412 are two-dimensionally arranged with respect to the substrate 41, but the lenses may also be arranged in one dimension. 97 201237551 -τν/*/ i Figure 4 is a cross-sectional view taken along line A-A of Figure 3. As shown in Fig. 4, in the wafer level lens array, a light blocking film 414 for preventing light from transmitting through a portion other than the lens 412 is disposed between the plurality of lenses 412 arranged on the substrate 410. The wafer level lens is composed of a lens 412 existing on the substrate 410 and a light-receiving film 414 which is placed in the periphery of the circle. The polymerizable composition of the present invention is used to form the light-blocking film 414. Wafer level lenses are described below by reference to a configuration in which, for example, the plurality of lenses 412 shown in FIG. 3 are two-dimensionally arranged relative to the substrate 410. Lens 412 is generally constructed of the same material as substrate 410 and is integrally molded onto substrate 410 or molded into individual structures and secured to the substrate. Herein, an example is described, but the wafer level lens is not limited to this embodiment, and various embodiments may be employed, such as a wafer level lens having a multilayer structure, or a crystal divided into lens modules by dicing Round lens. The material forming the lens 412 includes, for example, glass. There are a wide variety of glasses, and since a glass having a high refractive index can be selected, this material is suitable as a lens material. Further, the glass is excellent in heat resistance and has the advantage of being able to withstand reflow (refl〇w) mounted on a photographing unit or the like. Other materials used to form lens 412 include resins. The resin processability (Pr〇CeSSability) is excellent and is suitable for forming a lens surface simply and inexpensively by a mold or the like. In this case, an energy curable resin (enefgy__blefesin) is preferably used to form the lens 412. The energy curable resin may be a resin which can be cured by hydrazine or a resin which can be cured by irradiation with an active energy ray (for example, irradiation with ultraviolet rays or electron beams of 98 201237551). As the energy curable resin, all conventional resins can be used, but in consideration of the reflow soldering of the photographing unit, the softening point is relatively high (for example, the softening point is 20 (TC or more than 20 (rc) resin). Preferably, the resin having a preference of 25 〇 C or more than 250 ° C is more specifically described below by referring to a manufacturing method of a wafer level lens array based on, for example, FIGS. 5 to 1 . [Mode and Fabrication of Wafer Level Lens (1)] 〇-Forming Lens - A method of forming the lens 412 on the substrate 410 will be described with reference to Fig. 5 and Figs. 6A to 6C. Fig. 5 shows how the exhibition will be performed A molding material for a resin composition for lens formation (indicated by Μ in Fig. 5) is supplied to the substrate 410. Further, Fig. 6A to Fig. 6C show that the lens 412 is molded on the substrate by using the mold 46. A diagram of the procedure of 41. As shown in Fig. 5, the molding material μ is dropped onto the molded portion of the lens 412 of the substrate 41 by using the dispenser 45. In this document, it corresponds to a lens. 412 amount of molding material is supplied to one part of the material to be fed After the molding material Μ is supplied to the substrate 41, as shown in FIG. 6A, the mold 460 for molding the lens 412 is placed on the surface side of the substrate 410 to which the molding material is supplied. The concave surface 462 for transferring the shape of the lens 412 is set according to the required number of the lenses 412. 99 201237551 Pressure 桓罝 two f) does not "compact with the molding material 在 on the substrate 410 f I 460 In order to deform the molding material Μ along the line of the concave shape. In the state that the 杈 material is pressed against the squeezing die, the =:: rr line can be _ fat, with heat = two,,,, and the plate 460 To cure the molding material M. After the molding material Μ is cured, as shown in Fig. 6C, the substrate·and the lens 412 are separated from the mold 460. Forming a light-emitting film - hereinafter by referring to Figs. 7A to 7C A method of forming the light-blocking film 414 around the circumference of the lens 412 is described. Figures 7A to 7C are schematic cross-sectional views showing a process of providing the light-blocking film 414 on the substrate 410 on which the lens 412 is molded. The method of 414 includes coating the polymerizable composition of the present invention on a substrate 41 to form a light blocking coating. The glazing coating forming step of layer 414A (see FIG. 7A), the exposure step of patterning the light-blocking coating 414A via mask 470 (see FIG. 7B), and developing the light-blocking coating 414A after exposure to remove The uncured region and the development step of forming the patterned light-blocking film 414 (see FIG. 7C). Incidentally, the formation of the light-blocking film 414 may be arbitrarily performed before the lens 412 is manufactured or after the lens 412 is manufactured, but in this context, The method of forming is performed after the lens 412 is manufactured. The step of forming the light blocking film 414 in the method is described below. <Light-blocking coating forming step> In the light-blocking coating forming step, as shown in Fig. 7A, a polymerizable 100 201237551 composition is coated on the substrate 410 to form a film having low optical reflectivity and being polymerizable The composition constitutes a light blocking coating 414A. At this time, a light-blocking coating 414A is formed to cover the surfaces of all the substrates 410 and the lens surface 412a of the lens 412 and the surface of the lens edge 412b. The substrate 410 that can be used in this step is not particularly limited. Examples thereof include soda glass, alkali-free glass, Pyrex (registered trademark) glass, quartz glass, and transparent resin. ◎ In the case where the lens 412 and the substrate 410 are integrally formed, the substrate 410 as used herein denotes an embodiment including the lens 412 and the substrate 410. On the substrate 410, if necessary, an undercoat layer may be provided in order to improve adhesion to the cover layer, prevent diffusion of the material, or flatten the surface of the substrate 410. As a method of applying the polymerizable composition to the substrate 41 and the lens 412, various coating methods such as slit coating, spray coating, and inkjet printing can be applied ( Inkjet printing), spin coating, cast coating, ro11 mating, and screen printing. In view of the uniformity of the thickness of the coating film and the ease of drying of the coating solvent, the film thickness after the application of the polymerizable composition is preferably from micrometers to 10 mm, more preferably from 2 μm to 5 μm, more preferably 〇 2 microns more than 3 microns. The drying (pre-twisting) of the gloss coating 414 applied to the substrate 410 can be carried out using a hot plate, an oven or the like at 5 Torr to 14 Torr. The temperature is 10 seconds to 300 seconds. '里又101 201237551 "τ ν/w» J. After drying the polymerizable composition, the film thickness (hereinafter sometimes referred to as "dry thickness") can be considered in terms of performance (such as required block) The case of light action is arbitrarily selected, and is generally from 1 μm to less than 5 μm. <Exposure Step> In the exposure step, the light-blocking coating 414A formed in the light-blocking coating forming step is patterned-exposed. The pattern exposure may be a scanning exposure, but as shown in Fig. 7B, an embodiment of exposure through a mask 470 having a predetermined mask pattern is preferred. With regard to the exposure in this step, the pattern exposure of the light-blocking coating 414A is performed by exposure through a predetermined mask pattern in which only the portion irradiated with light outside the light-blocking coating 414A is cured by exposure. In this exposure, a mask pattern that allows light to be incident on the surface of the lens edge 412b and the surface of the substrate 410 between the lenses 412 is used. By using this mask pattern, the light-holding coating 414a in the region other than the lens surface 412a is cured by light irradiation, and the cured region forms the light-blocking film 414. The radiation that can be used for exposure is preferably ultraviolet rays such as g-line, h-line, and i-line. For this ride, a single-wavelength source can be used, or a source containing all wavelengths, such as a high pressure mercury lamp, can be used. <Developing Step> After, followed by alkaline development (developing step), whereby the portion which is not irradiated with light during the exposure (i.e., the uncured region of the light-blocking coating 414A) is dissolved into the aqueous test solution, And only the area that is cured by light irradiation is left. 102 201237551 414 Α / 之 藉 藉 藉 藉 藉 藉 曝 曝 曝 曝 曝 曝 曝 曝 曝 曝 曝 曝 曝 曝 曝 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如And a curing light blocking film 414 is formed in other regions. Ο Ο The H-step cap developer (acceptable aqueous solution) contained in the test:: Lr吏 uses all organic organic agents, inorganic test agents, and The ageing agent is almost the same as the adjacent circuit or its analog. Therefore, it is preferred to use an organic alkaline agent. (Organic examples include organic secret compound L>, Β, 0 ^ earth tomb ritual, choline, pyrrole, piperazine machine The ring is like (4) deca-carbene, sighing compounds!: Hydroxanthin, hydrogen oxygen, hydrogen hydride, and 乂 稀释 will dilute this test agent to _1 mass I by pure water. to 10 mass % (preferably an alkaline aqueous solution obtained by 〇〇1% by mass to i mass of the sheet is used as a developer. 'The development temperature is usually from 3 to rc, and developed for 90 seconds. In the case of a developer composed of an aqueous solution, after the unexposed area of the developer removal surface, such as a pure water-washing strip (after smashing, I also after the shadow, it is thoroughly washed with pure water and removed), The back of the shirt is followed by a drying step. In addition, the step of forming the calender coating layer, the exposing step, and After the development step, if necessary, a @化步骤 formed by heating (post-culture) and/or exposure may be provided. 103 201237551. The post-peeling is a heat treatment for achieving complete curing after development, and The heat curing treatment is usually carried out at 100 C, 25 〇 t. The conditions of the post-baking (such as temperature and 4) can be appropriately set according to the material of the substrate 410 or the lens 412. For example, when the substrate 412 is glass, Outside the above temperature range, it is preferable to use 180. (: to 24 (temperature of rc.) The post-baking treatment is applied to the light-blocking film 414 formed after development, and can be used in a continuous system or a batch system by using a heating element ( For example, a hot plate, a convection oven (hot air slit), and a high frequency heater are used to establish the above conditions. By way of example, the lens 412 has a concave shape (but the shape is not particularly limited and may be convex ( The case of c〇nvex) or aspheric is described in the above-mentioned private order. Further, by describing, for example, a plurality of lenses, wafer-level lenses formed on the surface of the substrate 41G are described. The above procedure 'but also A configuration in which a plurality of lenses 412 are molded on both surfaces of the substrate 41 can be employed, and in this case, a patterned light-blocking film 414 is formed on both surfaces of the area outside the surface of the tree. [Mode and Fabrication of Wafer Level Lens (2)] Fig. 8 is a view showing another configuration example of a wafer level lens array. The wafer level lens shown in Fig. 8 has the following configuration (single type) The same molding material is used to simultaneously mold the substrate and the lens. As a molding material for preparing the wafer level lens, a molding material of the above molding material (4) may be used. In this example, Forming a plurality of concave lenses on the surface of the substrate 410 (the surface on the upper side in the drawing) (concealing (8) 0412' and forming a plurality of convex lenses on the other surface (the surface on the lower side in the drawing) 104 201237551 (convex !ens) 420. Further, a patterned light-blocking film 414 is formed in a region other than the lens surface 412a of the substrate 410 (i.e., formed on the surface of the substrate 41 and the surface of the lens edge 412b). The above procedure can be applied as a patterning method when the light-blocking film 414 is formed. [Mode and Fabrication of Wafer Level Lens (3)] A further configuration example of a wafer level lens array and a manufacturing procedure thereof will be described below by referring to Figs. 9A to 9C and Figs. 10A to 10C. 9A through 9C are schematic views showing another process of forming the patterned light blocking film 414. 10A through iC are schematic views showing a process of first forming a patterned light blocking film 414 and then molding the lens 412. In the example of the wafer level lens array shown in FIGS. 5 to 8, a patterned light blocking film 414' is formed on the substrate 410 on which the lens 412 is disposed, but in the following procedure, first formed on the substrate 41. The light blocking film 414 is patterned, and then the lens 412 is molded on the substrate 41. - Formation of light-blocking film - As shown in Fig. 9A, a light-blocking coating forming step of applying a polymerizable composition to a substrate 410 to form a light-blocking coating 414 is first performed. Thereafter, a hot plate, an oven or the like is used at 5 Torr. The drying of the light-blocking coating 414A formed on the substrate 41A is performed at a temperature of TC of 300 sec. 300 seconds. The dry thickness of the polymerizable compound can be arbitrarily selected according to the performance (such as the required light-receiving effect). However, it is generally from 0.1 μm to less than 50 μm. Next, as shown in FIG. 9B, 105 is sequentially exposed by the pattern of the light-blocking coating 414A formed in the light-shielding coating forming step via the mask 47〇. 201237551

TV/-» A 曝光步驟。遮罩470具有預定遮罩圖案。 在此步驟之曝光中，將擂光塗層414圖案曝光，藉此 在擔光塗層414A外僅受光照射之部分固化。在本文中， 當在梢後步驟中模製透鏡412時，使用僅在除為透鏡412 之透鏡開口 414a製作出之部位外的區域中之擋光塗層 414A上允許受光照射之遮罩圖案。藉由此方法，藉由光照 射來固化僅在除為透鏡412之透鏡開口 414a製作出之部位 外的區域中之擋光塗層414A。關於可用於曝光之輻射，類 似於先前所述之程序，較佳使用諸如g線、h線以及丨線 之紫外線。 隨後，進行鹼性顯影（顯影步驟），藉此僅在對應於 透鏡412之透鏡開口 414a的區域（其為在上述圖案曝光中 未固化之擋光塗層414A區域）中之擋光塗層414A溶解 出，進入鹼性水溶液。此時，如圖9C中所示，除透鏡412 之透鏡開口 414a之區域外的區域中之光固化擔光塗層 414A保留於基板410上且形成擋光膜414。 關於作為顯影劑之驗性水溶液中之鹼性劑，可使用與 先前所述程序中相同之驗性劑。 顯影之後’藉由洗滌移除過量顯影劑，接著乾燥膜。 亦在此實施例中，在進行上述擋光塗層形成步驟、曝 光步驟以及顯影步驟之後，必要時可提供藉由後焙及/或^ 光來固化所形成之擔光膜的固化步驟。 ’ 甚至當本發明之可聚合組成物附著於例如在塗佈裝 置之排出口處之喷嘴、塗佈裝置之管道區域或塗佈裝置^ 106 201237551 部時，亦可用習知清潔液（cleaning solution)輕易清潔及 移除。在此情況下，為更有效地進行清潔以及移除，較佳 將上文描述為本發明之可聚合組成物中所含之溶劑的溶劑 用於清潔液。TV/-» A exposure step. The mask 470 has a predetermined mask pattern. In the exposure of this step, the calender coating 414 is patterned to be exposed, whereby only the portion irradiated with light outside the light-carrying coating 414A is cured. Herein, when the lens 412 is molded in the tipping step, a mask pattern that allows light to be irradiated is applied to the light-blocking coating 414A in a region other than the portion made of the lens opening 414a of the lens 412. By this method, the light-blocking coating 414A in the region other than the portion created by the lens opening 414a of the lens 412 is cured by illumination. Regarding the radiation that can be used for exposure, similar to the procedure previously described, ultraviolet rays such as g-line, h-line, and rifling are preferably used. Subsequently, an alkaline development (development step) is performed whereby the light-blocking coating 414A is only in the region corresponding to the lens opening 414a of the lens 412, which is the region of the light-blocking coating 414A that is not cured in the above-described pattern exposure. Dissolve and enter an alkaline aqueous solution. At this time, as shown in Fig. 9C, the photo-curable light-carrying coating layer 414A in the region other than the region of the lens opening 414a of the lens 412 remains on the substrate 410 and forms the light-blocking film 414. As the alkaline agent in the aqueous test solution as the developer, the same test agent as in the previously described procedure can be used. After development, excess developer was removed by washing, followed by drying of the film. Also in this embodiment, after the above-described light-blocking coating forming step, exposure step, and development step, a curing step of curing the formed light-supporting film by post-baking and/or light can be provided as necessary. ' Even when the polymerizable composition of the present invention is attached to, for example, a nozzle at the discharge port of the coating device, a pipe region of the coating device, or a coating device ^ 106 201237551, a cleaning solution can be used. Easy to clean and remove. In this case, in order to perform cleaning and removal more efficiently, the solvent described above as the solvent contained in the polymerizable composition of the present invention is preferably used for the cleaning liquid.

此外，例如 JP-A-7-128867、JP-A-7-146562、 JP-A-8-278637、JP-A-2000-273370、JP_a_2006-85140、 吓-八-20〇6-29119卜汗-八-2007-21〇1、邛_入-2007-2102 以及 JP-A-2007-281523中所述之清潔液亦宜用作清潔及移除本 發明之可聚合組成物的清潔液。 較佳使用烧二醇單烧醚甲酸酯或烧二醇單烧醚作為 清潔液。 •耆，或可 可早獨使用可用作清潔液之這些溶劑中的 混合並使用其兩者或超過兩者。 在混合兩種或超過兩種溶劑之情況下，藉由混合含羥 基溶劑與無羥基溶劑獲得之混合溶劑為較佳。含羥基溶劑 與無羥基溶劑之間的質量比為1/99至99/1，較佳為1〇/9〇 至90/10 ’更佳為2〇/8〇至8〇/2〇。混合溶劑較佳為丙二醇 單甲醚乙酸酯（PGMEA，另一名稱：卜曱氧基_2_乙醯氧基 丙烷）與丙二醇單甲醚（PGME，另一名 丙醇）呈6〇/40比率之混合溶劑。 T乳土 附帶而言’為增強清潔液至可聚合組成物中之渗透 祕Ιϊί文描料可併人可聚合組成物中之界面活性劑 的界面活性劑添加至清潔液中。 ••形成透鏡- 107 201237551 § \^ ^/ Λ Μ. 下文描述在形成擋光膜414後形成透鏡412之步驟。 如圖10Α中所示，藉由分配器450將構成透鏡412之 模製材料Μ滴於上方形成有圖案化擋光膜414之基板410 上。供應模製材料Μ以覆蓋對應於透鏡412之透鏡開口 414a的區域，包括鄰接開口之擋光膜414邊緣之一部分。 在將模製材料Μ供應至基板410之後，如圖10B中 所示，將用於模製透鏡412之模具480安置於經供應模製 材料Μ之基板410表面侧。在模具480中，根據透鏡412 之所需數目設置用於轉印透鏡412形狀之凹面482。 在基板410上與模製材料μ相抵擠壓模具480以使模 製材料Μ沿凹面形狀之線變形。在與模製材料Μ相抵擠 壓模具480之狀態中，當模製材料μ為熱固性樹脂或紫外 線可固化樹脂時，以熱或紫外線外部照射模具以固化模製 材料Μ。 在固化模製材料Μ之後，將基板41〇以及透鏡412 與模具480分離以獲得如圖10C中所示在基板41〇上具有 圖案化擋光膜414之晶圓級透鏡。 以此方式，晶圓級透鏡可能不僅具有如圖7中所示之 在除透鏡412之透鏡表面412a外的區域中設置圖案化擒光 膜414之組態，而且具有如圖10C中所示在除透鏡412之 透鏡開口 414a外的區域中設置擔光膜414之組態。 在晶圓級透鏡中’在基板410之至少一個表面上圖案 逐次形成之擋光膜414在除412之透鏡表面412&或透鏡開 口 414a外之區域中充分播光且同時抑制反射光產生。因 108 201237551 此，當將晶圓級透鏡應用於具有固態攝影元件之攝影模組 時，可防止在攝影期間出現與反射光相關之諸如幻影 (ghost)或閃爍（flare)之問題。 此外’在基板表面上設置擋光膜414，從而消除在晶 圓級透鏡上固定個別擒光構件或其類似物之需要，且可抑 制製造成本提高。 附帶而言，在透鏡周圍設置具有不均勻表面之結構之 ❹ 組悲的情況下’諸如幻影（ghost)之問題可能因入射於所 述結構上之光的反射或擴散而出現。為擺脫此問題，當採 用如圖7中所示之在除透鏡412之透鏡表面412a外之區域 中設置圖案化播光膜414的組態時，除透鏡表面412a以外 可以擋光，且可改良光學效能。 [實例] 下文藉由參考實例來描述本發明，但本發明不以任何 方式限於這些實例。 <製備黏合劑溶液A> Ο 向i，000毫升體積三頸燒瓶中饋入159公克卜曱氧基 -2-丙醇且在氮氣流下加熱至85。〇且在2小時内向其中逐 滴添加藉由將63.4公克甲基丙浠酸苯曱酯、72.3公克甲基 丙烯酸（pKa = 4.8)以及4.15公克V-601 (由和光純藥化 學工業有限公司（Wako Pure Chemical Industries, Ltd.)製 造）添加至159公克1-甲氧基_2_丙醇中所製備之溶液。逐 滴添加完成之後’進一步加熱混合物5小時且藉此反應。 隨後’停止加熱’且獲得曱基丙烯酸苯曱酯/甲基丙烯 109 201237551 -T\JU 1 酸共聚物（以莫耳計為30/70)。 此後’將120.0公克之共聚物溶液轉移至300亳升體 積二頸燒瓶中，且添加16.6公克曱基丙烯酸縮水甘油酯以 及〇.16公克對曱氧基苯酚並攪拌溶解。溶解之後，添加 3.0公克三笨膦，且將混合物加熱至1〇〇它，藉此進行加成 反應。藉由氣相層析確認曱基丙烯酸縮水甘油酯消失，且 停止加熱。此外，添加38公克1-曱氧基-2-丙醇以製備酸 基含量為2亳當量/公克（酸值：112毫克KOH/公克）、交 聯基含量為2.23毫當量/公克、質量平均分子量為24,〇〇〇 (就聚苯乙烯而言，藉由GPC方法）且固體含量為46質量 %之黏合劑溶液A。 <製備黏合劑溶液B> 將VP-2500 [由曰本曹達有限公司製造之聚(對乙烯苯 酚）（質量平均分子量：3,500 ’多分散性：1.39)](對乙 稀苯齡之pKa : 9.9)溶解於丙二醇單甲_乙酸酯中以製備 固體含量為46質量％之黏合劑溶液B。 <製備黏合劑溶液C> 將1-曱氧基-2-丙醇另外添加至CYCLOMER P ACA230AA [由大賽璐化學工業有限公司製造之具有羧基 以及不飽和基團之丙烯基聚合物（質量平均分子量： 14,000，酸值：21毫克KOH/公克）之1-曱氡基_2-丙醇溶 液（固體含量：55質量％);單體之pKa對應於丙烯基聚 合物中之含羧基重複單元：4.8]中以製備固體含量為46質 量％之黏合劑溶液C。 110 201237551 <製備黏合劑溶液D> 向1，〇0〇毫升體積三頸燒瓶中饋入159公克丨甲， -2-丙醇且在氮氣流下加熱至85。〇，且在2小時内向其=土 滴添加藉由將63.4公克甲基丙烯酸苯曱酯、72.3公弟' 、 丙烯酸以及4.15公克V-601 (由和光純藥化學工業 二 司製造）添加至159公克1-曱氧基-2-丙醇中所製備 液。逐扃添加完成之後，進一步加熱混合物5小時+ ' 反應。 精此 Ο / 隨後，停止加熱，且獲得甲基丙烯酸苯曱酯/甲基丙 酸共聚物（以莫耳計為30/70)。 ^ 此後，將120.0公克之共聚物溶液轉移至3〇〇亳升體 積三頸燒瓶中，且添加48.6公克甲基丙烯酸縮水甘油酯以 及0_16公克對甲氧基苯紛並攪拌溶解。溶解之後，添加 3.0公克二苯膦，且將混合物加熱至，藉此進行加成 反應。藉由量測酸值來確認反應的進展，且當酸值變成〇 時，停止加熱。另外，添加1_甲氧基_2_丙醇以製備酸基含 Ο 量為〇毫當量/公克（酸值：0毫克KOH/公克）且固體含 量為46質量％之黏合劑溶液D。 <製備無機填料液體分散液1> 預先混合30質量份二氧化矽（s〇_ci，由豐田自動車 有限公司（Admatechs Company Limited)製造）（無機填 料）與48.2質量份黏合劑溶液A，且藉由馬達研磨機M-50 (由艾格爾（Eiger)製造）在9公尺/秒之圓周速度下使用 直徑為1.0毫米之氧化锆珠粒分散所得混合物1.5小時以 111 201237551 製備無機填料液體分散液1。 <製備無機填料液體分散液2> 預先混合30質量份二氧化矽（s〇_cl，由豐田自動車 有=公司製造）（無機填料）與48.2質量份黏合劑溶液c， 且藉由馬達研磨機M-50 (由艾格爾製造）在9公尺/秒之 圓周速度下使用直徑為L0毫米之氧化锆珠粒分散所‘混 合物1.5小時以製備無機填料液體分散液2。 奶 <製備無機填料液體分散液3>In addition, for example, JP-A-7-128867, JP-A-7-146562, JP-A-8-278637, JP-A-2000-273370, JP_a_2006-85140, scare-eight-20〇6-29119 The cleaning liquid described in pp.-2007-21, 1, 邛---2007-2102, and JP-A-2007-281523 is also preferably used as a cleaning liquid for cleaning and removing the polymerizable composition of the present invention. It is preferred to use a burnt diol mono-burning ether formate or a glycerol mono-burning ether as a cleaning liquid. • 耆, or may use a mixture of these solvents that can be used as a cleaning solution and use both or more. In the case of mixing two or more solvents, a mixed solvent obtained by mixing a hydroxyl group-containing solvent with a hydroxyl group-free solvent is preferred. The mass ratio between the hydroxyl group-containing solvent and the hydroxyl group-free solvent is from 1/99 to 99/1, preferably from 1〇/9〇 to 90/10', more preferably from 2〇/8〇 to 8〇/2〇. The mixed solvent is preferably propylene glycol monomethyl ether acetate (PGMEA, another name: diterpoxy 2 - ethoxypropane) and propylene glycol monomethyl ether (PGME, another propanol) is 6 〇 / 40 ratio of mixed solvent. T-Cells Incidentally, in order to enhance the penetration of the cleaning liquid into the polymerizable composition, the surfactant of the surfactant in the polymerizable composition can be added to the cleaning liquid. • Forming a lens - 107 201237551 § \^ ^/ Λ Μ. The step of forming the lens 412 after forming the light-blocking film 414 is described below. As shown in Fig. 10A, the molding material constituting the lens 412 is dropped onto the substrate 410 on which the patterned light-blocking film 414 is formed by the dispenser 450. The molding material is supplied to cover a region corresponding to the lens opening 414a of the lens 412, including a portion of the edge of the light blocking film 414 adjacent the opening. After the molding material Μ is supplied to the substrate 410, as shown in Fig. 10B, the mold 480 for molding the lens 412 is placed on the surface side of the substrate 410 to which the molding material is supplied. In the mold 480, a concave surface 482 for transferring the shape of the lens 412 is provided in accordance with the required number of lenses 412. The mold 410 is pressed against the molding material μ on the substrate 410 to deform the molding material Μ along the line of the concave shape. In a state in which the molding material 抵 is pressed against the pressing die 480, when the molding material μ is a thermosetting resin or an ultraviolet curable resin, the mold is externally irradiated with heat or ultraviolet rays to cure the molding material Μ. After curing the molding material crucible, the substrate 41A and the lens 412 are separated from the mold 480 to obtain a wafer level lens having a patterned light blocking film 414 on the substrate 41A as shown in Fig. 10C. In this manner, the wafer level lens may have not only the configuration in which the patterned phosphor film 414 is disposed in the region other than the lens surface 412a of the lens 412 as shown in FIG. 7, but also has the configuration as shown in FIG. 10C. The configuration of the light-loading film 414 is disposed in a region other than the lens opening 414a of the lens 412. In the wafer level lens, the light blocking film 414 which is successively formed on at least one surface of the substrate 410 is sufficiently broadcasted in a region other than the lens surface 412 & or the lens opening 414a of 412 while suppressing generation of reflected light. According to 108 201237551, when a wafer level lens is applied to a photographic module having a solid-state photographic element, problems such as ghost or flare associated with reflected light occur during photographing. Further, the light-blocking film 414 is provided on the surface of the substrate, thereby eliminating the need to fix the individual light-receiving members or the like on the crystal-level lens, and the manufacturing cost can be suppressed. Incidentally, in the case where a structure having a non-uniform surface is provided around the lens, a problem such as ghost may occur due to reflection or diffusion of light incident on the structure. To get rid of this problem, when the configuration of the patterned light-span film 414 is provided in a region other than the lens surface 412a of the lens 412 as shown in FIG. 7, the lens surface 412a can block light and can be improved. Optical performance. [Examples] Hereinafter, the present invention is described by reference to examples, but the present invention is not limited to these examples in any manner. <Preparation of binder solution A> 159 159 g of dipoxyloxy-2-propanol was fed into an i,000 ml volume three-necked flask and heated to 85 under a nitrogen stream. And 63.4 g of phenyl methacrylate, 72.3 g of methacrylic acid (pKa = 4.8) and 4.15 g of V-601 (by Wako Pure Chemical Industry Co., Ltd.) were added dropwise thereto within 2 hours. Wako Pure Chemical Industries, Ltd.) was added to a solution prepared in 159 g of 1-methoxy-2-propanol. After the dropwise addition was completed, the mixture was further heated for 5 hours and the reaction was thereby carried out. Then 'stop heating' and obtain phenyl decyl acrylate/methacryl 109 201237551 -T\JU 1 acid copolymer (30/70 in terms of moles). Thereafter, 120.0 g of the copolymer solution was transferred to a 300 liter volume two-necked flask, and 16.6 g of glycidyl methacrylate and 1616 g of p-methoxyphenol were added and dissolved by stirring. After the dissolution, 3.0 g of triphenylphosphine was added, and the mixture was heated to 1 Torr, whereby an addition reaction was carried out. The disappearance of glycidyl methacrylate was confirmed by gas chromatography, and heating was stopped. Further, 38 g of 1-decyloxy-2-propanol was added to prepare an acid group content of 2 亳 equivalent / gram (acid value: 112 mg KOH / gram), a crosslinking group content of 2.23 milli equivalents / gram, mass average The binder solution A having a molecular weight of 24, ruthenium (in terms of polystyrene, by GPC method) and a solid content of 46% by mass. <Preparation of Binder Solution B> VP-2500 [Poly(p-vinylphenol) manufactured by Sakamoto Soda Co., Ltd. (mass average molecular weight: 3,500 'polydispersity: 1.39)] (pKa for ethylene benzene age: 9.9) Dissolved in propylene glycol monomethyl acetate to prepare a binder solution B having a solid content of 46% by mass. <Preparation of binder solution C> Additional addition of 1-nonoxy-2-propanol to CYCLOMER P ACA230AA [Propylene average polymer having carboxyl group and unsaturated group manufactured by Daicel Chemical Industry Co., Ltd. Molecular weight: 14,000, acid value: 21 mg KOH/g) 1-mercapto-2-propanol solution (solid content: 55 mass%); pKa of monomer corresponds to carboxyl group-containing repeating unit in propylene-based polymer In 4.8], a binder solution C having a solid content of 46% by mass was prepared. 110 201237551 <Preparation of binder solution D> A 159 gram volume three-necked flask was fed with 159 g of armor, 2-propanol and heated to 85 under a nitrogen stream. 〇, and added to the soil drop within 2 hours by adding 63.4 grams of phenyl methacrylate, 72.3 male's, acrylic acid, and 4.15 grams of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) to 159. A solution prepared in grams of 1-nonoxy-2-propanol. After the completion of the enthalpy addition, the mixture was further heated for 5 hours + 'reaction. Fine Ο / Subsequently, the heating was stopped, and a benzoyl methacrylate/methylpropionic acid copolymer (30/70 in terms of mole) was obtained. ^ Thereafter, 120.0 g of the copolymer solution was transferred to a 3-liter volume three-necked flask, and 48.6 g of glycidyl methacrylate and 0-16 g of p-methoxybenzene were added and dissolved. After the dissolution, 3.0 g of diphenylphosphine was added, and the mixture was heated to thereby carry out an addition reaction. The progress of the reaction was confirmed by measuring the acid value, and when the acid value became 〇, the heating was stopped. Further, 1-methoxy-2-propanol was added to prepare a binder solution D having an acid group content of 〇 meq/g (acid value: 0 mgKOH/g) and a solid content of 46% by mass. <Preparation of inorganic filler liquid dispersion 1> 30 parts by mass of cerium oxide (s〇_ci, manufactured by Admatechs Company Limited) (inorganic filler) and 48.2 parts by mass of binder solution A were mixed in advance, and The inorganic filler liquid dispersion was prepared by a motor grinder M-50 (manufactured by Eiger) using a zirconia bead having a diameter of 1.0 mm at a peripheral speed of 9 m/sec to disperse the resulting mixture for 1.5 hours at 111 201237551. Liquid 1. <Preparation of inorganic filler liquid dispersion 2> 30 parts by mass of cerium oxide (s〇_cl, manufactured by Toyota Auto Co., Ltd.) (inorganic filler) and 48.2 parts by mass of binder solution c were mixed in advance, and were ground by a motor Machine M-50 (manufactured by Eiger) was used to disperse the mixture of oxidized zirconium beads having a diameter of L0 at a peripheral speed of 9 m/sec for 1.5 hours to prepare an inorganic filler liquid dispersion 2. Milk <Preparation of inorganic filler liquid dispersion 3>

預先混合30質量份二氧化矽（s〇 cl，由豐田自動 有限公司製造）（無機賴）與48.2 f量份黏合劑溶液D， 且藉由馬達研磨機M-50 (由艾格爾製造）在9公尺/秒之 圓周速度下使用直徑為1.0毫米之氧化锆珠粒分散所得混 合物1.5小時以製備無機填料液體分散液3。 此 〈製備無機填料液體分散液4>Premix 30 parts by mass of cerium oxide (s〇cl, manufactured by Toyota Automation Co., Ltd.) (inorganic lye) with 48.2 f parts of binder solution D, and by motor grinder M-50 (manufactured by Eiger) The resulting mixture was dispersed using a zirconia bead having a diameter of 1.0 mm at a peripheral speed of 9 m/sec for 1.5 hours to prepare an inorganic filler liquid dispersion 3. [Preparation of inorganic filler liquid dispersion 4 >

預先混合30質量份二氧化矽（s〇_cl，由豐田自動 有限公司製造）（無機填料）與48.2質量份黏合劑溶液B， 且藉由馬達研磨機M-50 (由艾格爾製造）在9公尺/秒之 圓周速度下使用直徑為1.0毫米之氧化锆珠粒分散所得混 合物1.5小時以製備無機填料液體分散液4。 此 <製備可聚合組成物溶液> (實例1 ) …混合以下配方巾之組分，且經由第—磁器過遽且隨 後故由弟一過濾器過澹所述混合物以獲得實例1之可取人 組成物溶液。 來0 112 201237551 由日本巴爾公司製造之Profile Star (聚丙烯，過濾精 確度· 1.5微米）用於第一過濾、器，且由日本巴爾公司製 造之HDCII (高密度聚丙烯，過濾精確度：6.0微米）用 於第二過濾器。 黏合劑溶液A (驗溶性黏合劑） 14.9質量份 二季戊四醇六丙烯酸酯（KAYARAD DPHA，商標， 由曰本化藥有限公司（Nippon Kayaku Co.，Ltd.)製造）（可 聚合化合物） 7.72質量份 、30 parts by mass of cerium oxide (s〇_cl, manufactured by Toyota Automation Co., Ltd.) (inorganic filler) and 48.2 parts by mass of binder solution B were premixed, and by a motor grinder M-50 (manufactured by Eiger) The resulting mixture was dispersed using a zirconia bead having a diameter of 1.0 mm at a peripheral speed of 9 m/sec for 1.5 hours to prepare an inorganic filler liquid dispersion 4. This <Preparation of a polymerizable composition solution> (Example 1) ...mixing the components of the following formula, and passing the mixture through the first magnet and then passing the mixture through a filter to obtain the preferable example 1 Human composition solution. To 0 112 201237551 Profile Star (polypropylene, filtration accuracy · 1.5 μm) manufactured by Barr, Japan, used in the first filter, HDCII manufactured by Barr, Japan (high-density polypropylene, filtration accuracy: 6.0 Micron) for the second filter. Binder solution A (test soluble binder) 14.9 parts by mass of dipentaerythritol hexaacrylate (KAYARAD DPHA, trademark, manufactured by Nippon Kayaku Co., Ltd.) (polymerizable compound) 7.72 parts by mass ,

Irgacure907 (由日本巴斯夫製造之苯乙酮類化合物） (聚合起始劑） 2.03質量份Irgacure907 (acetophenone compound manufactured by BASF, Japan) (polymerization initiator) 2.03 parts by mass

Kayacure DETX-S (由日本化藥有限公司製造之噻噸 酮類化合物）（敏化劑） 0.43質量份 無機填料液體分散液1 (無機填料） 45.09質量份 Megaface F-780 (由DIC公司製造）（界面活性劑） 0.14質量份 YMF-02 (由住友金屬採礦有限公司（Sumit〇m〇 Metai 〇 MiningCo.，Ltd.)製造’氧化鉋鎢（CSq 33w〇3 (平均分散 粒徑：800奈米或低於800奈米）之18.5質量％液體分散 液）） 26.97質量份 (實例2) 以與實例1中相同之方式，但再向實例1之可聚合組 成物溶液中添加5.〇質量份ESPEL 9940A (由日立化學有 限公司製造之彈性體）來製備實例2之組成物。 (實例3) 113 201237551 以與實例2中相同之方式，但將實例2中之黏合劑溶 液A改為黏合劑溶液c來製備實例3之組成物。 (實例4) 以與實例2中相同之方式，但將實例2中之黏合劑溶 液A改為黏合劑溶液B來製備實例4之組成物。 (實例5) 以與實例3中相同之方式，但將實例3中之無機填料 液體分散液1改為無機填料液體分散液2來製備實例5之 組成物。 (實例6) 混合以下組成以獲得實例6之可聚合組成物溶液。 黏合劑溶液C (鹼溶性黏合劑） 14.9質量份 三環癸烷二甲醇二丙烯酸酯（A-DCP，商標，製造商： 新中村化學有限公司（Shin-Nakamura Chemical Co.，Ltd.)) (可聚合化合物） 7.72質量份Kayacure DETX-S (thioxanthone compound manufactured by Nippon Kayaku Co., Ltd.) (sensitizer) 0.43 parts by mass of inorganic filler liquid dispersion 1 (inorganic filler) 45.09 parts by mass Megaface F-780 (manufactured by DIC Corporation) (surfactant) 0.14 parts by mass of YMF-02 (manufactured by Sumit〇m〇Metai 〇 Mining Co., Ltd.) oxidized planing tungsten (CSq 33w〇3 (average dispersed particle size: 800 nm) Or less than 800 nm) 18.5 mass% liquid dispersion)) 26.97 parts by mass (Example 2) In the same manner as in Example 1, but further adding 5. 〇 by mass to the polymerizable composition solution of Example 1. The composition of Example 2 was prepared by ESPEL 9940A (elastomer manufactured by Hitachi Chemical Co., Ltd.). (Example 3) 113 201237551 The composition of Example 3 was prepared in the same manner as in Example 2 except that the binder solution A in Example 2 was changed to the binder solution c. (Example 4) The composition of Example 4 was prepared in the same manner as in Example 2 except that the binder solution A in Example 2 was changed to the binder solution B. (Example 5) A composition of Example 5 was prepared in the same manner as in Example 3 except that the inorganic filler liquid dispersion 1 in Example 3 was changed to the inorganic filler liquid dispersion 2. (Example 6) The following composition was mixed to obtain a polymerizable composition solution of Example 6. Binder solution C (alkali-soluble binder) 14.9 parts by mass of tricyclodecane dimethanol diacrylate (A-DCP, trademark, manufacturer: Shin-Nakamura Chemical Co., Ltd.) Polymerizable compound) 7.72 parts by mass

Irgacure 907 (由日本巴斯夫製造之苯乙酮類化合物） (聚合起始劑） 2.03質量份Irgacure 907 (acetophenone compound manufactured by BASF, Japan) (polymerization initiator) 2.03 parts by mass

Kayacure DETX-S (由日本化藥有限公司製造之噻噸 酮類化合物）（敏化劑） 0.43質量份 無機填料液體分散液2 (無機填料）45.09質量份 Megaface F-780 (由DIC公司製造）（界面活性劑） 0.14質量份 YMF-02 (由住友金屬採礦有限公司製造，氧化鉋鎢 (Cs〇.33W〇3 (平均分散粒徑·· 8〇〇奈米或低於8〇〇奈米）之 114 201237551 18.5質量％液體分散液）） 26.97質量份 , 矽烷耦合劑（KBM_5〇3，由信越化學公司製造） 3.5質量份 紫外線吸收劑（CAS號：98835-90-6，由大東化學有 限公司（Daito Chemical Co·, Ltd.)製造）0.15 質量份 (實例7) 以與實例6中相同之方式，但將實例6中之黏合劑溶 液C改為黏合劑溶液B來製備實例7之組成物。 I (實例8) 以與實例7中相同之方式，但將實例7中之無機填料 液體分散液2改為無機填料液體分散液4來製備實例8之 組成物。 (比較實例1) 以與實例1中相同之方式，但將實例1中之黏合劑溶 液A改為黏合劑溶液D且將實例1中之無機填料液體分散 液1改為無機填料液體分散液3來製備比較實例1之組成 〇 物。 (比較實例2) 以與實例1申相同之方式，但移除實例1中之YMF-02 (氧化铯鎢之液體分散液）來製備比較實例2之組成物。 (比較實例3) 根據與實例1中相同之配方，但將YMF-02 (氧化铯 鎢之液體分散液）改為下文之碳黑液體分散液A來製備比 較實例3之組成物。 115 201237551 (製備碳黑液體分散液A)Kayacure DETX-S (thioxanthone compound manufactured by Nippon Kayaku Co., Ltd.) (sensitizer) 0.43 parts by mass of inorganic filler liquid dispersion 2 (inorganic filler) 45.09 parts by mass Megaface F-780 (manufactured by DIC Corporation) (surfactant) 0.14 parts by mass YMF-02 (manufactured by Sumitomo Metal Mining Co., Ltd., oxidized planing tungsten (Cs〇.33W〇3 (average dispersed particle size · 8 〇〇 nanometer or less than 8 〇〇 nanometer) 114 201237551 18.5 mass% liquid dispersion)) 26.97 parts by mass, decane coupling agent (KBM_5〇3, manufactured by Shin-Etsu Chemical Co., Ltd.) 3.5 parts by mass of ultraviolet absorber (CAS number: 98835-90-6, by Dadong Chemical Co., Ltd.) (manufactured by Daito Chemical Co., Ltd.) 0.15 parts by mass (Example 7) The composition of Example 7 was prepared in the same manner as in Example 6, except that the binder solution C in Example 6 was changed to the binder solution B. Things. I (Example 8) The composition of Example 8 was prepared in the same manner as in Example 7, except that the inorganic filler liquid dispersion 2 in Example 7 was changed to the inorganic filler liquid dispersion 4. (Comparative Example 1) In the same manner as in Example 1, except that the binder solution A in Example 1 was changed to the binder solution D and the inorganic filler liquid dispersion 1 in Example 1 was changed to the inorganic filler liquid dispersion 3 The composition of Comparative Example 1 was prepared. (Comparative Example 2) The composition of Comparative Example 2 was prepared in the same manner as in Example 1 except that YMF-02 (liquid dispersion of lanthanum oxytide) in Example 1 was removed. (Comparative Example 3) A composition of Comparative Example 3 was prepared according to the same formulation as in Example 1, except that YMF-02 (liquid dispersion of lanthanum oxytide) was changed to the following carbon black liquid dispersion A. 115 201237551 (Preparation of carbon black liquid dispersion A)

在下文藉由雙輥製程（twin-roll process)對組成物I 進行高黏度分散處理以獲得分散液。此時，分散液黏度為 70,000毫帕·秒。 此後’將下文組成物II之混合物添加至上文所得之分 月欠液中’且糟由使用均备機在3,000轉/分鐘之條件下擾掉 所得混合物3小時。在分散器（DISPERMAT，商標，由浩 美設備有限公司（GETZMANN GmbH )製造）中使用直捏 為0.3毫米之氧化銼珠粒對所得混合溶液進行精細分散處 理4小時，以製備碳黑液體分散液A。 (組成物I) 平均一次粒徑為15奈米之碳黑（顏料黑7 (pigment Black 7)) 23 質量份 曱基丙烯酸苯曱酯/曱基丙烯酸共聚物（曱基丙烯酸苯 甲酯單元/甲基丙烯酸單元= 67/33 (莫耳〇/〇)，Mw: 28,〇〇〇) 之丙二醇單曱醚乙酸酯45質量％溶液 22晳吾你The composition I was subjected to a high viscosity dispersion treatment by a twin-roll process to obtain a dispersion. At this time, the viscosity of the dispersion was 70,000 mPa·s. Thereafter, the mixture of the following composition II was added to the effluent obtained above, and the resulting mixture was disturbed by using a homogenizer at 3,000 rpm for 3 hours. The resulting mixed solution was subjected to fine dispersion treatment for 4 hours in a disperser (DISPERMAT, trademark, manufactured by GETZMANN GmbH) using a ruthenium oxide bead of 0.3 mm to prepare a carbon black liquid dispersion A. . (Composition I) Carbon black having an average primary particle diameter of 15 nm (pigment black 7) 23 parts by mass of phenyl decyl acrylate/mercaptoacrylic acid copolymer (benzyl methacrylate unit / Methacrylic acid unit = 67/33 (mole/〇), Mw: 28, 〇〇〇) propylene glycol monoterpene ether acetate 45 mass% solution 22

Solsperse 5000 (由日本路博潤有限公司（Lubriz〇1 1.2質量份Solsperse 5000 (by Lubriz 〇 1 1.2 parts by volume)

Japan Ltd.)製造） (組成物II) 甲基丙烯酸本曱i旨/曱基丙烯酸共聚物（曱基丙烯酸苯 曱酯單元/曱基丙烯酸單元=67/33 (莫耳％ )，Mw : 28,000 ) 22質量份 200質量份 之丙二醇單曱醚乙酸酯45質量％溶液 丙二醇單甲醚乙酸酯 <評估可聚合組成物> 116 201237551 (評估梯級可追鞭性（St印Foll〇Wability)) Ο Ο 如下製造不均勻基板··在矽基板上設置高度為20 米（對應於圖11中配線502之厚度）且寬度或間隙為5〇 微米、（對應於圖11中之配線至配線距離w)之線，且 由旋塗法在於平坦矽基板上形成厚度為1〇微米之膜^ 件下將實例以及比較實例之各可聚合組成物塗佈於不二、 基板上，接著在loot：下加熱（預焙）12〇秒且進一 UV曝光機ML_5〇聽（由牛尾公司（Ushk)ine = 進行uv固化。對不均勻部分之截面SEM攝影，且量测凹 ，部分之最薄部分（對應於圖u中之配線間區域c)的】 厚度以評估梯級可追雜。假定1Q微米之目標厚、 =藉由相對值評估最薄部分之臈厚度。接近⑽^ 追雜較高且感光層形狀較成功地追縱基板 (形成抗蝕劑圖案以及評估敏感性） 塗你走鬥塗:去將實例以及比較實例之各可聚合組成物 f2 到25微米之财度，接著在熱板上在 120 C下加熱2 7刀鐘以獲得感光層。 藉由使用i線步進器，經由具 形圖案的光遮罩，同時以5㈣隹/八」]為微未之方 ^ ^ 2,000 i ^ 所得感光層。、、”之範圍内改變曝光劑量來照射 溶液Ϊ二藉4=質二甲基職化物水 devd°p_t)4^ 嶋吻 117 201237551 • v 一 為 一^ 沖洗且再以純水洗滌以獲得紅外阻擋性阻焊圖案。量測用 於當進行顯影步驟60秒時獲得一側為1〇〇微米之方形圖案 t最小曝光劑量（敏感性）且將其用作圖案可成形性之指 心數值愈小，判斷敏感性愈高。 (5平估紅外線阻擋作用以及可見光透明度）(Manufactured by Japan Ltd.) (Composition II) methacrylic acid 旨 旨 / methacrylic acid copolymer (phenyl decyl acrylate unit / mercapto acrylate unit = 67 / 33 (mole %), Mw: 28,000 22 parts by mass of 200 parts by mass of propylene glycol monoterpene ether acetate, 45 mass% solution, propylene glycol monomethyl ether acetate <evaluation of polymerizable composition> 116 201237551 (evaluation of step-up whipability (St.Foll〇Wability) )) 制造 制造 Manufacture of uneven substrate as follows: • Set the height on the 矽 substrate to 20 m (corresponding to the thickness of the wiring 502 in Fig. 11) and the width or gap is 5 μm (corresponding to the wiring to wiring in Fig. 11) The distance from the line w), and each of the polymerizable compositions of the examples and the comparative examples is coated on the substrate by a spin coating method to form a film having a thickness of 1 μm on the flat substrate, followed by loot : Lower heating (prebake) for 12 〇 seconds and enter a UV exposure machine ML_5 ( (by Usk) in uv curing. SEM photography of the section of the uneven portion, and measuring the concave, the thinnest part of the part (corresponding to the wiring area c in Figure u) It is estimated that the steps can be chased. It is assumed that the target thickness of 1Q micron is thick, and the thickness of the thinnest part is evaluated by the relative value. The (10)^ is highly chaotic and the shape of the photosensitive layer is more successfully traced to the substrate (forming a resist pattern and Evaluate Sensitivity) Apply the smear: apply the polymerizable composition f2 of the examples and comparative examples to a 25 micron financial value, and then heat the plate for 2 7 knives at 120 C on a hot plate to obtain the photosensitive layer. By using an i-line stepper, through a light mask of a tangible pattern, at the same time, 5 (four) 隹 / 八"] is used as a micro-notch ^ ^ 2,000 i ^ to obtain a photosensitive layer, and the exposure dose is changed within the range of Solution Ϊ 2 borrowed 4 = dimethylated dimethylated water devd °p_t) 4^ 嶋 kiss 117 201237551 • v one for one ^ rinse and then washed with pure water to obtain infrared blocking solder mask pattern. Measurement used when The minimum exposure dose (sensitivity) of a square pattern t of 1 μm on one side was obtained in the development step for 60 seconds, and the smaller the value of the centroid used as the pattern formability, the higher the sensitivity was judged. Estimate infrared blocking and visible light transparency)

在上述條件下將可聚合組成物旋塗於玻璃基板上以 形成膜厚度為25微米之感光層（可聚合組成物層）塗層， 且使用紫外線_可見光-近紅外線分光光度計UV3600 (Ultraviolet-Visible-Near Infrared Spectrophotometer UV3600)(由島津公司（ShimadzuC〇rp〇rati〇n)製造）量 1塗層在1，2GG奈米波長下之透射率。數值愈小，判斷紅 外阻擋作用愈高。當透射率為2%或低於2%時，可稱所述 塗層實務上展現良好的紅外阻擔作用。 此外，使用备、外線_可見光-近紅夕卜 咖刪（由島津公司製造）量測上述塗層在55=^ =透射率。數值較A，_可見光透明度愈高。當可見 光透射率為30%或超過3〇%時，可稱所述塗岸 良好的可見光透明度。 曰、 、 (解析度評估） 在最小曝光㈣（敏感性）下進行曝光處理以及鮮 ，理’所述最小曝光劑量是在與藉由使用光遮罩（且有U 線與空間圖案（line-and-space pattern)，線办 Γ .八.. 為1〇〇微米）來形成抗触劑圖案以獲得線、linewidtl1 線與空間圖案之抗蝕劑圖案時相同的仪二1〇〇微米之 性時加以計算。使用電子顯微鏡（s_48、、下评估敏感 υυ ’由日立高技梯 118 201237551 公司（Hitachi High-Technologies Corporation)製造）觀察 所形成之圖案的線性且根據以下級別來分等級。 等級5 :圖案線性良好’且橫截面為矩形且處於良好 程度。 等級4 ·圖案直線地實負上良好’且橫截面實質上為 矩形且處於沒問題之程度。 等級3 :圖案直線地以及橫戴面矩形性稍差，但處於 實務上沒問題之程度。 等級2 :圖案線性顯著較差且橫截面偏離矩形。 等級1 :圖案線性與橫截面矩形性均明顯較差。 上文評估之結果展示於下表中。 表1 紅外阻擋作 用 〇200J-^) 可見光透 明度 (550奈米） 敏感性 (毫焦/公分2) 梯級可 追蹤性 解析 度 貫例1 _實例2 實例3 實例4 <ί%~~~ 53% 450 150 3 52% 450 140 3 52% 400 130 4 實例5 __ 〆1 Λ / 52% 350 125 4 實例6 52% 400 130 4 實例7 --- '___ 52% 400 110 5 —實例8 比較實例1 52% 300 105 卜5 <-Ί η / Η 52% 300 100 5 比較實例2 - 53% 75% Ϊ法解析圖案。 150 比較實例3 200 125 5 如自圖 <1% 無法解析圖案。 170 ’可 占、、it ηThe polymerizable composition was spin-coated on the glass substrate under the above conditions to form a photosensitive layer (polymerizable composition layer) having a film thickness of 25 μm, and an ultraviolet-visible-near-infrared spectrophotometer UV3600 (Ultraviolet- Visible-Near Infrared Spectrophotometer UV3600) (manufactured by Shimadzu Corporation) (Shimadzu C〇rp〇rati〇n) The transmittance of the coating of the amount 1 at a wavelength of 1,2 GG nanometer. The smaller the value, the higher the blocking effect of the red. When the transmittance is 2% or less, it can be said that the coating actually exhibits a good infrared blocking effect. Further, the above coating was measured at 55 = ^ = transmittance using a standby, an external line - visible light - near red coffee (manufactured by Shimadzu Corporation). The value is higher than A, _ visible light transparency. When the visible light transmittance is 30% or more than 3%, the coated visible light transparency can be referred to.曰, , (resolution evaluation) Exposure treatment under minimum exposure (four) (sensitivity) and fresh, the minimum exposure dose is in use with a light mask (and has a U-line and space pattern (line- And-space pattern), the line is Γ 八.. is 1 〇〇 micron) to form the anti-contact agent pattern to obtain the same line of the line, the linewidtl1 line and the space pattern resist pattern Calculated when. The linearity of the formed pattern was observed by an electron microscope (s_48, under evaluation of sensitivity ’ ' by Hitachi High Technics 118 201237551 (manufactured by Hitachi High-Technologies Corporation) and classified according to the following levels. Level 5: The pattern is linear ' and the cross section is rectangular and in good condition. Level 4 • The pattern is straight and solid and the cross section is substantially rectangular and is no problem. Level 3: The pattern is slightly inferior in rectangular shape and horizontally worn, but it is practically no problem. Level 2: The pattern is significantly less linear and the cross section is offset from the rectangle. Level 1: Both the linearity of the pattern and the rectangularity of the cross section are significantly worse. The results of the above assessment are shown in the table below. Table 1 Infrared blocking effect 〇200J-^) Visible light transparency (550 nm) Sensitivity (milli-joule/cm 2) Step traceability resolution Example 1 _Example 2 Example 3 Example 4 <ί%~~~ 53 % 450 150 3 52% 450 140 3 52% 400 130 4 Example 5 __ 〆1 Λ / 52% 350 125 4 Example 6 52% 400 130 4 Example 7 --- '___ 52% 400 110 5 — Example 8 Comparative example 1 52% 300 105 Bu 5 <-Ί η / Η 52% 300 100 5 Comparative Example 2 - 53% 75% The pattern is resolved. 150 Comparative Example 3 200 125 5 As shown in the figure <1%, the pattern cannot be resolved. 170 ‘可占,,it η

所述要求亦即為（1) '足所有要求之圖案， 119 201237551 外區中之擔光作用較高，⑵可見光區中之透光度較高， 以及（3)藉由驗性顯影達成之解析度較高。此外，可見可 形成具有成功地追縱不均勻基板之不均勻形狀之形狀的感 光層。 另一方面，在比較實例1以及比較實例3中，圖案無 法解析。因此’無法對比較實例1以及比較實例3之組成 物#平估敏感性以及解析度。在比較實例2中，未獲得紅外 區中之擋光作用。 工業適用性 根據本發明，可提供在紅外區展現高擋光作用且在可 見光區展現尚透光度且能夠藉由鹼性顯影形成具有極佳解 析度之圖案的可聚合組成物，以及各自使用所述組成物之 感光層、永久圖案、晶圓級透鏡、固態攝影元件及圖案形 成方法。 此外，根據本發明，可提供確保當上方設置感光層之 基板具有不均勻形狀時，可形成具有成功地追蹤基板不均 勻形狀之形狀的感光層的可聚合組成物，以及各自使用所 述組成物之感光層、永久圖案、晶圓級透鏡、固態攝影元 件及圖案形成方法。 本申請案基於2010年11月30日申請之日本專利申 請案（曰本專利申請案第2010—267889號），且其内容以引 用的方式併入本文t。 【圖式簡單說明】 圖1為展示配備有根據本發明之一個實施例之固態攝 220 201237551 影疋件的4目機模組之組態之*意性截面圖。 的根據本發明之-個實施例之固態攝影元件 =j展示晶圓級透鏡陣列之—個實例的平面圖。 圖為沿圖3中線A-A之截面圖。 之圖圖5為展示如何將透鏡製作出之模製材料供應至基板The requirements are also (1) 'all required patterns, 119 201237551 higher light load in the outer zone, (2) higher transmittance in the visible region, and (3) achieved by verinable development The resolution is higher. Further, it can be seen that a photosensitive layer having a shape that successfully traces the uneven shape of the uneven substrate can be formed. On the other hand, in Comparative Example 1 and Comparative Example 3, the pattern could not be resolved. Therefore, it is impossible to evaluate the sensitivity and the resolution for the composition of Comparative Example 1 and Comparative Example 3. In Comparative Example 2, the light blocking effect in the infrared region was not obtained. Industrial Applicability According to the present invention, it is possible to provide a polymerizable composition which exhibits a high light blocking effect in the infrared region and which exhibits a light transmittance in the visible light region and which can form a pattern having excellent resolution by alkaline development, and each of which is used. A photosensitive layer, a permanent pattern, a wafer level lens, a solid-state photographic element, and a pattern forming method of the composition. Further, according to the present invention, it is possible to provide a polymerizable composition capable of forming a photosensitive layer having a shape for successfully tracking a non-uniform shape of a substrate when a substrate on which a photosensitive layer is disposed has an uneven shape, and each of the compositions is used Photosensitive layer, permanent pattern, wafer level lens, solid state imaging element and pattern forming method. The present application is based on a Japanese patent application filed on Nov. 30, 2010, the disclosure of which is incorporated herein by reference. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing the configuration of a 4-mesh machine module equipped with a solid-state camera 201237551 shadow member according to an embodiment of the present invention. A solid state photographic element according to an embodiment of the present invention = j shows a plan view of an example of a wafer level lens array. The figure is a cross-sectional view taken along line A-A of Fig. 3. Figure 5 is a diagram showing how the lens-made molding material is supplied to the substrate.

b ^A至圖6C為展* #由使祕具料賴製於基板 上之程序的圖。 至圖7C為展絲上方模製有透鏡之基板上形成 圖案化擋光膜之製程的示意圖。 圖8為展示晶圓級透鏡陣列之一個實例的截面圖。 一圖9A至圖9C為展示形成擔光膜之製程之另一實施例 的示意圖。 圖10A至圖l〇c為展示在上方具有圖案化擋光膜之基 板上模製透鏡之製程的示意圖。 圖11為展示在具有不均勻形狀之基板上設置感光層 之狀態的示意性截面圖。 【主要元件符號說明】 10、501 : ；δ夕基板 12 :攝影元件 13 :層間絕緣膜 14 :基層 121 201237551 ι^μιι. 15 :彩色濾光片 15R :紅色濾光片 15G :綠色濾光片 15B :藍色濾光片 16 :外塗層 17 :微透鏡 18 :遮光膜 20、41、43、45 :黏著劑 22 :絕緣膜 23 :金屬電極 24 :阻焊層 26 :内部電極 27 :元件表面電極 30 :玻璃基板 40 :攝影透鏡 42 :紅外截止濾光片 44 :擋光及電磁遮蔽 50 :透鏡架 60 :焊球 70 :電路基板 100 :固態攝影元件基板 200 :相機模組 410 :基板 412、420 :透鏡 122 201237551 412a :透鏡表面 412b :透鏡邊緣 414 :遮光膜 414A :遮光塗層 414a :透鏡開口 450:分配器 460、480 :模具 462、482 :凹面 ❹ 470 :遮罩 501a :矽基板表面 502 :配線 502a :配線表面 503 :感光層 C :配線間區域 C1 :感光層表面之底部 C2 :感光層表面之底部 〇 hv :入射光 Μ:模製材料 tl :配線間區域C中感光層之厚度 t2 :配線間區域C中感光層之厚度 W:配線至配線距離 123b ^A to Fig. 6C are diagrams showing the procedure for making the secret material on the substrate. Fig. 7C is a schematic view showing a process of forming a patterned light-blocking film on a substrate on which a lens is molded over a wire. Figure 8 is a cross-sectional view showing an example of a wafer level lens array. 9A to 9C are schematic views showing another embodiment of a process for forming a light-supporting film. 10A through 10C are schematic views showing a process of molding a lens on a substrate having a patterned light-blocking film thereon. Fig. 11 is a schematic cross-sectional view showing a state in which a photosensitive layer is provided on a substrate having a non-uniform shape. [Description of main component symbols] 10, 501 : ; δ 夕 substrate 12 : photographic element 13 : interlayer insulating film 14 : base layer 121 201237551 ι ^ μιι. 15 : color filter 15R : red filter 15G : green filter 15B: blue filter 16: outer coat 17: microlens 18: light shielding film 20, 41, 43, 45: adhesive 22: insulating film 23: metal electrode 24: solder resist 26: internal electrode 27: component Surface electrode 30: Glass substrate 40: Photographic lens 42: Infrared cut filter 44: Light blocking and electromagnetic shielding 50: Lens holder 60: Solder ball 70: Circuit substrate 100: Solid-state imaging element substrate 200: Camera module 410: Substrate 412, 420: lens 122 201237551 412a: lens surface 412b: lens edge 414: light shielding film 414A: light shielding coating 414a: lens opening 450: dispenser 460, 480: mold 462, 482: concave surface 470: mask 501a: 矽Substrate surface 502: Wiring 502a: Wiring surface 503: Photosensitive layer C: Inter-wiring area C1: Bottom of photosensitive layer surface C2: Bottom of photosensitive layer surface 〇hv: Incident aperture: Molding material tl: Sensing in wiring area C Thickness of layer t2: photosensitive layer in wiring area C The thickness W: wiring 123 to the wiring distance

Claims (1)

201237551 TV/^/ Α ^^±Λ. 七、申請專利範圍·· 1. 一種可聚合組成物，包括·· 聚合起始劑、 可聚合化合物、 鶴化合物、 驗溶性黏合劑，以及 無機填料。 2.如申請專利範圍第1 所述無機填料為二氧化石夕。 項所述之可聚合組成物，其中201237551 TV/^/ Α ^^±Λ. VII. Patent Application Range 1. A polymerizable composition, including a polymerization initiator, a polymerizable compound, a crane compound, a test-soluble binder, and an inorganic filler. 2. The inorganic filler according to the first aspect of the patent application is sulphur dioxide. The polymerizable composition of the item, wherein 3.如申請專利範圍第i項所述之可聚 所述鹼溶性黏合劑具有酸基。 σ、'’ 〜、 4·如申請專利範圍第3項所述之可 所述酸基為酚羥基或硫醇基。 成物，、 5·如申請專利範圍第1項所述之可聚合组成物，豆中 所述鹼溶性黏合劑具有交聯基。3. Polymerizable as described in claim i, wherein the alkali-soluble binder has an acid group. σ, ''~, 4· The acid group described in the third paragraph of the patent application is a phenolic hydroxyl group or a thiol group. The polymerizable composition according to claim 1, wherein the alkali-soluble binder has a crosslinking group. 、=如申請專利範圍第1項所述之可聚合組成物，其中 所述聚合起始劑為笨乙酮類化合物且所述可聚合組成物更 含有敏化劑。 7.如申請專利範圍第1項所述之可聚合組成物，其中 所述鎢化合物由以下式（I)表示： MxWy〇z ⑴ 其中Μ表示金屬，w表示鎢，〇表示氧， 0,001$x/y$l.l，且 2.2<z/y<3.〇 〇 124 201237551 8.如申請專利範圍第7項所述之可聚 Μ為鹼金屬。 Τ 张、+、9.如^專她圍第1項所述之可聚合組成物，其中 =迷可聚合化合物為在分子㈣有多财聚合基圈 月巨可聚合化合物。 用於物細1項所物嫩成物，其 Ο Ο 可^組=^層’其由如申請專職圍第1項所述之 之ϋ—種水久圖案，其由如申請專職圍第1項所述 之可聚合組成物形成。 13.如申請專利範圍帛12項所述之永 述水久圖案為阻焊層。 /、甲所 14·如申請專利範㈣12項所述之永久圖案，其中所 述水久圖案為紅外線阻擋膜。 圓周ΙΓ/Ϊί®1級透鏡’其具有透鏡以及在所述透鏡之 久=成之如中請專利範圍第12項所述之永 項所:之攝影元件’其具有如申請專利範圍第12 7. 種固恶攝影元件’包括： 件部$ 轉基板，其在其—個表面上形成有攝影元 紅外阻播膜，其設置於所述固態攝影元件基板之另一 125 201237551 表面側 其中所述紅外線阻擋臈為如申請專利範圍第12項所 述之永久圖案。 範圍trmtr其料包㈣齡申請專利 層以固化曝光區域之步驟以及藉由鹼性顯;;=先 域以形成永久圖案之步驟。 4办移除未曝光區 126The polymerizable composition according to claim 1, wherein the polymerization initiator is a acetophenone compound and the polymerizable composition further contains a sensitizer. 7. The polymerizable composition according to claim 1, wherein the tungsten compound is represented by the following formula (I): MxWy〇z (1) wherein Μ represents a metal, w represents tungsten, 〇 represents oxygen, 0,001$x /y$ll, and 2.2 <z/y<3.〇〇124 201237551 8. The polycondensable oxime described in claim 7 is an alkali metal. Τ Zhang, +, 9. For example, she is a polymerizable composition according to Item 1, wherein the polymerizable compound is a polymerizable compound in the molecular (four) polycondensation base. It is used for the fine objects of the item 1 item, and the Ο Ο can be grouped = ^ layer ', which is applied for the ϋ 种 种 种 种 种 种 第 , 种 种 种 种 种 种 种 种 种The polymerizable composition described in the section is formed. 13. The permanent water pattern as described in claim 12 is a solder resist layer. /, A Institute 14 · As claimed in the patent (4) 12 permanent pattern, wherein the water pattern is an infrared barrier film. Circumferential ΙΓ/Ϊί® Class 1 lens 'having a lens and a permanent element as described in claim 12 of the lens, as described in claim 12 The invention relates to: a solid-state photographic element comprising: a substrate-transferring substrate having a photographic element infrared blocking film formed on a surface thereof, which is disposed on another surface of the solid-state photographic element substrate, 125 201237551 The infrared ray barrier is a permanent pattern as described in claim 12 of the patent application. The range trmtr is a step of applying a patent layer to cure the exposed area and a step of forming a permanent pattern by alkali; 4 remove the unexposed area 126
TW100143976A 2010-11-30 2011-11-30 Polymerizable composition, and photosensitive layer, permanent pattern, wafer-level lens, solid-state imaging device and pattern forming method, each using the composition TWI518451B (en)

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