TWI742147B - Photosensitive resin composition for forming low refractive index film, low refractive index film, optical device, and manufacturing method of low refractive index film - Google Patents

Photosensitive resin composition for forming low refractive index film, low refractive index film, optical device, and manufacturing method of low refractive index film Download PDF

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TWI742147B
TWI742147B TW106129098A TW106129098A TWI742147B TW I742147 B TWI742147 B TW I742147B TW 106129098 A TW106129098 A TW 106129098A TW 106129098 A TW106129098 A TW 106129098A TW I742147 B TWI742147 B TW I742147B
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refractive index
index film
low refractive
resin composition
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TW201818149A (en
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武內弘明
田村弘毅
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日商東京應化工業股份有限公司
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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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • 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
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

[課題] 提供可在基板上均勻塗佈，且即使低曝光量的曝光亦不產生殘渣，可形成經保護膠帶之黏貼及剝離表面亦不易粗糙之低折射率膜的低折射率膜形成用感光性樹脂組成物、使該低折射率膜形成用感光性樹脂組成物硬化而形成的低折射率膜、具備該低折射率膜的光學裝置、使用前述低折射率膜形成用感光性樹脂組成物之低折射率膜之製造方法。 　　[解決手段] 低折射率膜形成用感光性樹脂組成物，除樹脂(A)、光聚合性化合物(B)、光聚合起始劑(C)、與填料(D)外， 　　相對於樹脂(A)之質量與光聚合性化合物(B)之質量與填料(D)之質量之合計，摻混有0.05~3質量%的含氟之界面活性劑(E)。[Problem] Provide a photosensitive film for forming a low-refractive index film that can be uniformly coated on a substrate, does not produce residue even when exposed to a low exposure amount, and can form a low-refractive-index film that is not easy to be roughened through the adhesion and peeling of the protective tape A resin composition, a low refractive index film formed by curing the photosensitive resin composition for forming a low refractive index film, an optical device provided with the low refractive index film, and the aforementioned photosensitive resin composition for forming a low refractive index film The manufacturing method of low refractive index film. [Solution] The photosensitive resin composition for forming a low refractive index film, in addition to the resin (A), the photopolymerizable compound (B), the photopolymerization initiator (C), and the filler (D), ” The total mass of A) and the mass of the photopolymerizable compound (B) and the mass of the filler (D) are blended with 0.05-3% by mass of a fluorine-containing surfactant (E).

Description

低折射率膜形成用感光性樹脂組成物、低折射率膜、光學裝置及低折射率膜之製造方法Photosensitive resin composition for forming low refractive index film, low refractive index film, optical device, and manufacturing method of low refractive index film

[0001] 本發明係關於低折射率膜形成用感光性樹脂組成物、使該低折射率膜形成用感光性樹脂組成物硬化而形成的低折射率膜、具備該低折射率膜的光學裝置、與使用前述低折射率膜形成用感光性樹脂組成物之低折射率膜之製造方法。[0001] The present invention relates to a photosensitive resin composition for forming a low refractive index film, a low refractive index film formed by curing the photosensitive resin composition for forming a low refractive index film, and an optical device provided with the low refractive index film , And the manufacturing method of the low refractive index film using the aforementioned photosensitive resin composition for forming the low refractive index film.

[0002] 以往使用感光性樹脂組成物，形成絕緣膜、保護膜、防反射膜等之種種之機能性膜。 　　具體上，被覆圖像傳感器用微透鏡之低折射率膜或液晶顯示器、有機EL元件等中之防反射用的低折射率膜，使用感光性樹脂組成物圖型化為期望的形狀而形成。 　　[0003] 可形成可用作為上述防反射用之低折射率膜的經圖型化的硬化膜的感光性樹脂組成物方面，提案有含有中空或多孔質粒子、光聚合起始劑、具有鹼可溶性的聚合性化合物、與粒子分散劑的感光性樹脂組成物(專利文獻1)。 [先前技術文獻] [專利文獻] 　　[0004] 　　[專利文獻1]特開2009-271444號公報[0002] In the past, photosensitive resin compositions were used to form various functional films such as insulating films, protective films, and anti-reflection films. "Specifically, a low-refractive-index film for coating microlenses for image sensors, or a low-refractive-index film for antireflection in liquid crystal displays, organic EL elements, etc., is formed by patterning a photosensitive resin composition into a desired shape. [0003] In terms of a photosensitive resin composition that can form a patterned cured film that can be used as the low-refractive index film for anti-reflection, it is proposed to contain hollow or porous particles, a photopolymerization initiator, and have alkali solubility. The photosensitive resin composition of the polymerizable compound and the particle dispersant (Patent Document 1). [Prior Art Document] [Patent Document] 　　[0004] 　　 [Patent Document 1] JP 2009-271444 A

[發明所欲解決之課題] 　　[0005] 例如將形成於矽基板等之半導體基板上的RGB的著色膜上所形成的微透鏡的表面以硬化膜(低折射率膜)被覆時，有在低折射率膜之表面黏貼保護膠帶之狀態，進行半導體基板之研削之情形。 　　該研削後，從低折射率膜之表面將保護膠帶剝離，但因保護膠帶之剝離而低折射率膜之表面粗糙、低折射率膜之表面易粗面化。 　　使感光性樹脂組成物的塗佈膜曝光而使其硬化時，在低折射率膜之表面，抑制氧之硬化，而低折射率膜之表面的硬化度稍低。因此，認為上述保護膠帶之剝離導致低折射率膜之表面的粗面化。 　　由如此之理由，在使用專利文獻1記載之感光性樹脂組成物，形成低折射率膜時，亦有因對低折射率膜黏貼及剝離保護膠帶，而低折射率膜之表面粗糙之問題。使低折射率膜以低曝光量形成時，因保護膠帶所致之低折射率膜之表面粗面化問題變得明顯。 　　又，因為低折射率膜為光學機能層，當然希望其表面為平滑。因此，低折射率膜形成用的感光性樹脂組成物中，亦追求可在基板上均勻塗佈。 　　進一步，在圖像傳感器中微透鏡之被覆等，需要在指定位置以正確尺寸形成作為低折射率膜的硬化膜，使用專利文獻1記載之感光性組成物時，顯影後易於圖型附近產生殘渣，結果硬化膜之圖型的表觀上的尺寸有比期望的尺寸還要大之情形。 　　[0006] 本發明係有鑑於上述課題而成者，以提供可在基板上均勻塗佈且即使低曝光量的曝光亦無殘渣產生，可形成不易因保護膠帶之黏貼及剝離而表面易粗糙之低折射率膜的低折射率膜形成用感光性樹脂組成物、使該低折射率膜形成用感光性樹脂組成物硬化而形成的低折射率膜、具備該低折射率膜的光學裝置、與使用前述低折射率膜形成用感光性樹脂組成物之低折射率膜之製造方法為目的。 [用以解決課題之手段] 　　[0007] 本發明者們發現關於低折射率膜形成用感光性樹脂組成物，除了樹脂(A)、光聚合性化合物(B)、光聚合起始劑(C)、填料(D)， 　　藉由相對樹脂(A)之質量與光聚合性化合物(B)之質量與填料(D)之質量的合計，摻混0.05~3質量%的含氟之界面活性劑(E)，可解決上述課題而完成本發明。更具體上，本發明提供以下者。 　　[0008] 本發明之第1態樣為含有樹脂(A)、光聚合性化合物(B)、光聚合起始劑(C)、填料(D)、與含氟之界面活性劑(E)， 　　含氟之界面活性劑(E)之含量相對於樹脂(A)之質量與光聚合性化合物(B)之質量與填料(D)之質量之合計，為0.05~3質量%之低折射率膜形成用感光性樹脂組成物。 　　[0009] 本發明之第2態樣為使第1態樣之低折射率膜形成用感光性樹脂組成物硬化而形成的低折射率膜。 　　[0010] 本發明之第3態樣為具備第2態樣之低折射率膜的光學裝置。 　　[0011] 本發明之第4態樣為含有: 　　形成第1態樣之低折射率膜形成用感光性樹脂組成物的塗佈膜、 　　對塗佈膜因應指定圖型進行位置選擇性地曝光、 　　使經曝光的塗佈膜顯影之經圖型化的低折射率膜之製造方法。 [發明之效果] 　　[0012] 根據本發明，可提供可在基板上均勻塗佈且即使低曝光量的曝光亦不產生殘渣，且可形成經保護膠帶之黏貼及剝離表面亦不易粗糙的低折射率膜之低折射率膜形成用感光性樹脂組成物、使該低折射率膜形成用感光性樹脂組成物硬化而形成的低折射率膜、具備該低折射率膜的光學裝置、使用前述低折射率膜形成用感光性樹脂組成物之低折射率膜之製造方法。 [實施發明之最佳形態] 　　[0013] 以下關於本發明，根據適宜之實施形態進行說明。又，本發明說明書中之「~」若未特別限定下，表示以上(下限值)到以下(上限值)。 　　本發明說明書中，僅記載為「感光性樹脂組成物」之情形，若未特別說明，表示「低折射率膜形成用感光性樹脂組成物」。 　　本發明說明書中，「(甲基)丙烯酸酯」包含丙烯酸酯與甲基丙烯酸酯之兩者。 　　本發明說明書中，「(甲基)丙烯酸基」包含丙烯酸基與甲基丙烯酸基之兩者。 　　本發明說明書中，「(甲基)丙烯醯基」包含丙烯醯基與甲基丙烯醯基之兩者。 　　[0014] ≪低折射率膜形成用感光性樹脂組成物≫ 　　低折射率膜形成用感光性樹脂組成物，除樹脂(A)、光聚合性化合物(B)、光聚合起始劑(C)、填料(D)，相對於樹脂(A)之質量與光聚合性化合物(B)之質量與填料(D)之質量之合計，含有0.05~3質量%的含氟之界面活性劑(E)。 　　感光性樹脂組成物藉由含有上述指定範圍內之量的含氟之界面活性劑(E)，可將感光性樹脂組成物在基板上均勻塗佈，且即使低曝光量的曝光亦不產生殘渣，可形成經保護膠帶之黏貼及剝離表面亦不易粗糙的低折射率膜。 　　以下說明低折射率膜形成用感光性樹脂組成物所含有的必須或任意成分。 　　[0015] ＜樹脂(A)＞ 　　低折射率膜形成用感光性樹脂組成物含有樹脂(A)。樹脂(A)在圖型形成用感光性樹脂組成物中為賦予可形成塗膜及經圖型化的膜的製膜性之成分。 　　作為樹脂(A)，為以往摻混於圖型形成用感光性樹脂組成物的樹脂則不特別限定。作為樹脂(A)，由容易形成具有良好形狀的經圖型化的硬化膜，以鹼可溶性樹脂為佳。 　　含有鹼可溶性樹脂的感光性樹脂組成物對鹼顯影液為可溶，而經曝光的感光性樹脂組成物進行硬化。因此，將經位置選擇性地曝光的感光性樹脂組成物的塗佈膜使用鹼顯影液進行顯影，僅未曝光部溶於鹼顯影液，而硬化的曝光部殘存，經圖型化的硬化膜形成作為低折射率膜。 　　[0016] 鹼可溶性樹脂係指以樹脂濃度20質量%的樹脂溶液(溶劑:丙二醇單甲基醚乙酸酯)，在基板上形成膜厚1μm的樹脂膜，於濃度0.05質量%的四甲基氫氧化銨(TMAH)水溶液浸漬1分鐘時，膜厚溶解0.01μm以上者。 　　[0017] 鹼可溶性樹脂的較佳例，可舉例如具有Cardo構造的樹脂(A1)。藉由使用含有具有Cardo構造的樹脂(A1)作為鹼可溶性樹脂的感光性樹脂組成物，容易形成耐熱性、機械特性、耐溶劑性、化學藥品耐性等平衡的優之低折射率膜。 　　[0018] 具有Cardo構造的樹脂(A1)方面，不特別限制，可使用以往習知樹脂。其中，以下述式(a-1)所表示之樹脂為佳。 　　[0019]

Figure 02_image001
[0020] 上述式(a-1)中，Xa 為下述式(a-2)所表示之基。 　　[0021]
Figure 02_image003
[0022] 上述式(a-2)中，Ra1 各自獨立，為氫原子、碳原子數1~6的烴基或鹵素原子，Ra2 各自獨立，為氫原子或甲基，Wa 為單鍵或下述式(a-3)所表示之基。 　　[0023]
Figure 02_image005
[0024] 又，上述式(a-1)中，Ya 為從二羧酸酐除去酸酐基(-CO-O-CO-)的殘基。二羧酸酐之例，可舉例如馬來酸酐、琥珀酸酐、伊康酸酐、鄰苯二甲酸酐、四氫苯二甲酸酐、六氫苯二甲酸酐、甲基內亞甲基四氫鄰苯二甲酸酐、氯菌酸酐、甲基四氫鄰苯二甲酸酐、戊二酸酐等。 　　[0025] 又，上述式(a-1)中，Za 為從四羧酸二酐除去2個酸酐基的殘基。四羧酸二酐之例，可舉例如均苯四酸二酐、二苯甲酮四羧酸二酐、聯苯基四羧酸二酐、聯苯基醚四羧酸二酐等。 　　又，上述式(a-1)中，m為0~20的整數。 　　[0026] 具有Cardo構造的樹脂(A1)之質量平均分子量(Mw:膠體滲透層析法(GPC)之聚苯乙烯換算的測定值。本說明書中為相同。)以1000~40000為佳、2000~30000更佳。藉由在上述範圍，得到良好的顯影性同時可得到充分的耐熱性、膜強度。 　　[0027] 由容易形成機械強度或對基板之密著性優異的低折射率膜之觀點來看，至少聚合(a1)不飽和羧酸而成的共聚物(A2)亦可宜用作為鹼可溶性樹脂。 　　[0028] (a1)不飽和羧酸方面，可舉例如(甲基)丙烯酸、巴豆酸等之單羧酸；馬來酸、富馬酸、檸康酸、甲基延胡索酸、伊康酸等之二羧酸；此等二羧酸的酐；等。此等中，由共聚合反應性、得到的樹脂之鹼溶解性、取得容易性等之點來看，以(甲基)丙烯酸及馬來酸酐為佳。此等之(a1)不飽和羧酸可單獨或2種以上組合使用。 　　[0029] 共聚物(A2)可為(a1)不飽和羧酸與(a2)含脂環式環氧基之不飽和化合物的共聚物。(a2)含脂環式環氧基之不飽和化合物，為具有脂環式環氧基的不飽和化合物則不特別限定。構成脂環式環氧基的脂環式基可為單環亦可為多環。單環的脂環式基方面，可舉例如環戊基、環己基等。又，多環的脂環式基方面，可舉例如降冰片基、異冰片基、三環壬基、三環癸基、四環十二基等。此等之(a2)含脂環式環氧基之不飽和化合物可單獨或2種以上組合使用。 　　[0030] 具體上，(a2)含脂環式環氧基之不飽和化合物方面，可舉例如下述式(a2-1)~(a2-15)所表示之化合物。此等之中，為了使顯影性為適度者，以下述式(a2-1)~(a2-5)所表示之化合物為佳、下述式(a2-1)~(a2-3)所表示之化合物更佳。 　　[0031]
Figure 02_image007
[0032]
Figure 02_image009
[0033]
Figure 02_image011
[0034] 上述式中，Ra20 為氫原子或甲基，Ra21 為碳原子數1~6的2價脂肪族飽和烴基，Ra22 為碳原子數1~10的2價烴基，t為0~10的整數。Ra21 方面，為直鏈狀或分枝鏈狀的伸烷基，以例如亞甲基、伸乙基、伸丙基、四亞甲基、乙基伸乙基、五亞甲基、六亞甲基為佳。Ra22 以例如亞甲基、伸乙基、伸丙基、四亞甲基、乙基伸乙基、五亞甲基、六亞甲基、伸苯基、伸環己基、-CH2 -Ph-CH2 -(Ph為伸苯基)為佳。 　　[0035] 共聚物(A2)亦可為上述(a1)不飽和羧酸及(a2)上述含脂環式環氧基之不飽和化合物與不具有環氧基的(a3)含脂環式基之不飽和化合物共聚合而成者。 　　(a3)含脂環式基之不飽和化合物，為具有脂環式基的不飽和化合物則不特別限定。脂環式基可為單環亦可為多環。單環的脂環式基方面，可舉例如環戊基、環己基等。又，多環的脂環式基方面，可舉例如金剛烷基、降冰片基、異冰片基、三環壬基、三環癸基、四環十二基等。此等之(a3)含脂環式基之不飽和化合物可單獨或2種以上組合使用。 　　[0036] 具體上，(a3)含脂環式基之不飽和化合物方面，可舉例如下述式(a3-1)~(a3-7)所表示之化合物。此等之中，為了使顯影性為適度者，以下述式(a3-3)~(a3-8)所表示之化合物為佳、下述式(a3-3)，(a3-4)所表示之化合物更佳。 　　[0037]
Figure 02_image013
[0038] 上述式中，Ra23 為氫原子或甲基，Ra24 為單鍵或碳原子數1~6的2價脂肪族飽和烴基，Ra25 為氫原子或碳原子數1~5的烷基。Ra24 為單鍵、直鏈狀或分枝鏈狀的伸烷基，以例如亞甲基、伸乙基、伸丙基、四亞甲基、乙基伸乙基、五亞甲基、六亞甲基為佳。Ra25 方面，以例如甲基、乙基為佳。 　　[0039] 又，共聚物(A2)可為含有上述(a1)不飽和羧酸與不具有脂環式基的(a4)含環氧基之不飽和化合物的單體的聚合物。 　　該共聚物(A2)可為上述(a1)不飽和羧酸與(a4)含環氧基之不飽和化合物之共聚物， 　　亦可為上述(a1)不飽和羧酸與上述(a2)含脂環式環氧基之不飽和化合物與(a4)含環氧基之不飽和化合物之共聚物， 　　亦可為上述(a1)不飽和羧酸與上述(a3)含脂環式基之不飽和化合物與(a4)含環氧基之不飽和化合物之共聚物， 　　亦可為上述(a1)不飽和羧酸與上述(a2)含脂環式環氧基之不飽和化合物與上述(a3)含脂環式基之不飽和化合物與(a4)含環氧基之不飽和化合物之共聚物。 　　[0040] (a4)含環氧基之不飽和化合物方面，可舉例如縮水甘油基(甲基)丙烯酸酯、2-甲基縮水甘油基(甲基)丙烯酸酯、3,4-環氧基丁基(甲基)丙烯酸酯、6,7-環氧基庚基(甲基)丙烯酸酯等之(甲基)丙烯酸環氧基烷基酯類；α-乙基丙烯酸縮水甘油基酯、α-n-丙基丙烯酸縮水甘油基酯、α-n-丁基丙烯酸縮水甘油基酯、α-乙基丙烯酸6,7-環氧基庚基酯等之α-烷基丙烯酸環氧基烷基酯類；等。此等之中，由共聚合反應性、硬化後的樹脂的強度等之點來看，以縮水甘油基(甲基)丙烯酸酯、2-甲基縮水甘油基(甲基)丙烯酸酯、及6,7-環氧基庚基(甲基)丙烯酸酯為佳。此等之(a4)含環氧基之不飽和化合物可單獨或2種以上組合使用。 　　[0041] 又，共聚物(A2)可為含有上述(a1)不飽和羧酸與上述以外的其他化合物的單體的共聚物。 　　共聚物(A2)可為含有由上述(a1)不飽和羧酸、上述(a2)含脂環式環氧基之不飽和化合物、上述(a3)含脂環式基之不飽和化合物、及上述(a4)含環氧基之不飽和化合物所構成群組中選出的1種以上之單體、與上述以外的其他化合物的單體的共聚物。 　　[0042] 其他化合物方面，可舉例如(甲基)丙烯酸烷基酯、(甲基)丙烯酸羥基烷基酯、具有醚鍵的(甲基)丙烯酸酯、上述其他之(甲基)丙烯酸酯、(甲基)丙烯醯胺類、烯丙基化合物、乙烯基醚類、乙烯基酯類、苯乙烯類、二羧酸二酯類、共軛二烯烴、含腈之聚合性化合物、含氯之聚合性化合物等。此等之化合物可單獨或2種以上組合使用。 　　[0043] (甲基)丙烯酸烷基酯方面，可舉例如甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、n-丙基(甲基)丙烯酸酯、n-丁基(甲基)丙烯酸酯、戊基(甲基)丙烯酸酯、tert-辛基(甲基)丙烯酸酯等之直鏈狀或分支鏈狀的烷基(甲基)丙烯酸酯。 　　[0044] (甲基)丙烯酸羥基烷基酯方面，可舉例如2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、2-二甲基羥基丙基(甲基)丙烯酸酯、三羥甲基丙烷單(甲基)丙烯酸酯等。 　　[0045] 具有醚鍵的(甲基)丙烯酸酯方面，可舉例如2-甲氧基乙基(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、3-甲氧基丁基(甲基)丙烯酸酯、乙基卡必醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯、四氫糠基(甲基)丙烯酸酯，以2-甲氧基乙基(甲基)丙烯酸酯及甲氧基三乙二醇(甲基)丙烯酸酯為佳。 　　[0046] 上述其他之(甲基)丙烯酸酯方面，可舉例如氯乙基(甲基)丙烯酸酯、苄基(甲基)丙烯酸酯、苯基(甲基)丙烯酸酯。 　　[0047] (甲基)丙烯醯胺類方面，可舉例如(甲基)丙烯醯胺、N-烷基(甲基)丙烯醯胺、N-芳基(甲基)丙烯醯胺、N,N-二烷基(甲基)丙烯醯胺、N,N-芳基(甲基)丙烯醯胺、N-甲基-N-苯基(甲基)丙烯醯胺、N-羥基乙基-N-甲基(甲基)丙烯醯胺等。 　　[0048] 烯丙基化合物方面，可舉例如乙酸烯丙基酯、己酸烯丙基酯、辛酸烯丙基酯、月桂酸烯丙基酯、棕櫚酸烯丙基酯、硬脂酸烯丙基酯、安息香酸烯丙基酯、乙醯乙酸烯丙基酯、乳酸烯丙基酯等之烯丙基酯類；烯丙基氧基乙醇；等。 　　[0049] 乙烯基醚類方面，可舉例如己基乙烯基醚、辛基乙烯基醚、癸基乙烯基醚、乙基己基乙烯基醚、甲氧基乙基乙烯基醚、乙氧基乙基乙烯基醚、氯乙基乙烯基醚、1-甲基-2,2-二甲基丙基乙烯基醚、2-乙基丁基乙烯基醚、羥基乙基乙烯基醚、二乙二醇乙烯基醚、二甲基胺基乙基乙烯基醚、二乙基胺基乙基乙烯基醚、丁基胺基乙基乙烯基醚、苄基乙烯基醚、四氫糠基乙烯基醚等之烷基乙烯基醚；乙烯基苯基醚、乙烯基甲苯基醚、乙烯基氯苯基醚、乙烯基-2,4-二氯苯基醚、乙烯基萘基醚、乙烯基蒽基醚等之乙烯基芳基醚；等。 　　[0050] 乙烯基酯類方面，可舉例如乙烯基乙酸酯、乙烯基丁酸酯、乙烯基異丁酸酯、乙烯基三甲基乙酸酯、乙烯基二乙基乙酸酯、乙烯基戊酸酯、乙烯基己酸酯、乙烯基氯乙酸酯、乙烯基二氯乙酸酯、乙烯基甲氧基乙酸酯、乙烯基丁氧基乙酸酯、乙烯基苯基乙酸酯、乙醯乙酸乙烯酯、乙烯基乳酸酯、乙烯基-β-苯基丁酸酯、安息香酸乙烯基酯、水楊酸乙烯基酯、氯安息香酸乙烯基酯、四氯安息香酸乙烯基酯、萘甲酸酯乙烯基酯等。 　　[0051] 苯乙烯類方面，可舉例如苯乙烯；甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、二乙基苯乙烯、異丙基苯乙烯、丁基苯乙烯、己基苯乙烯、環己基苯乙烯、癸基苯乙烯、苄基苯乙烯、氯甲基苯乙烯、三氟甲基苯乙烯、乙氧基甲基苯乙烯、乙醯氧基甲基苯乙烯等之烷基苯乙烯；甲氧基苯乙烯、4-甲氧基-3-甲基苯乙烯、二甲氧基苯乙烯等之烷氧基苯乙烯；氯苯乙烯、二氯苯乙烯、三氯苯乙烯、四氯苯乙烯、五氯苯乙烯、溴苯乙烯、二溴苯乙烯、碘苯乙烯、氟苯乙烯、三氟苯乙烯、2-溴-4-三氟甲基苯乙烯、4-氟-3-三氟甲基苯乙烯等之鹵代苯乙烯；等。 　　[0052] 二羧酸二酯類方面，可舉例如馬來酸二乙基酯、富馬酸二丁基酯。 　　[0053] 共軛二烯烴方面，可舉例如丁二烯、異戊二烯。 　　[0054] 含腈基之聚合性化合物方面，可舉例如(甲基)丙烯腈。 　　[0055] 含氯之聚合性化合物方面，可舉例如氯化乙烯基酯、偏氯乙烯。 　　[0056] 關於共聚物(A2)，在含有上述(a1)不飽和羧酸與上述以外的其他化合物的單體的共聚物中，以含有上述(a1)不飽和羧酸與上述具有醚鍵的(甲基)丙烯酸酯的單體的共聚物為佳。 　　該場合，共聚物(A2)中所佔的來自具有醚鍵的(甲基)丙烯酸酯的構成單位之比例，以30~90質量%為佳、40~80質量%更佳。 　　[0057] 共聚物(A2)中所佔的來自上述(a1)不飽和羧酸的構成單位之比例，以1~50質量%為佳、5~45質量%更佳。 　　又，共聚物(A2)含有來自上述(a2)含脂環式環氧基之不飽和化合物的構成單位與來自上述(a4)含環氧基之不飽和化合物的構成單位之情形，共聚物(A2)中所佔的來自(a2)含脂環式環氧基之不飽和化合物的構成單位的比例與來自上述(a4)含環氧基之不飽和化合物的構成單位的比例之合計，以71質量%以上為佳、71~95質量%較佳、75~90質量%再更佳。尤其，共聚物(A2)中所佔的來自上述(a2)含脂環式環氧基之不飽和化合物的構成單位的比例以單獨在71質量%以上為佳、71~80質量%更佳。來自上述(a2)含脂環式環氧基之不飽和化合物的構成單位的比例藉由在上述範圍，可使感光性樹脂組成物的經時安定性更提升。 　　又，共聚物(A2)含有來自(a3)含脂環式基之不飽和化合物的構成單位之情形，共聚物(A2)中所佔的來自上述(a3)含脂環式基之不飽和化合物的構成單位之比例，以1~30質量%為佳、5~20質量%更佳。 　　[0058] 共聚物(A2)之質量平均分子量以2000~200000為佳、3000~30000更佳。藉由在上述範圍，有感光性樹脂組成物的膜形成能力、曝光後的顯影性容易得到平衡之傾向。 　　[0059] 又，鹼可溶性樹脂方面，亦可宜使用含有(A3)至少具有來自上述(a1)不飽和羧酸的構成單位與後述之具有可與光聚合性化合物(B)聚合之部位的構成單位的共聚物或(A4)至少具有來自上述(a1)不飽和羧酸的構成單位與上述(a2)含脂環式環氧基之不飽和化合物及/或來自(a4)含環氧基之不飽和化合物的構成單位與後述之具有可與光聚合性化合物(B)聚合之部位的構成單位的共聚物的樹脂。鹼可溶性樹脂含有共聚物(A3)或共聚物(A4)之情形，可提高使用感光性樹脂組成物所形成的膜之對基板之密著性或使用感光性樹脂組成物而得到的低折射率膜之機械強度。 　　[0060] 共聚物(A3)、及共聚物(A4)可為再共聚合共聚物(A2)中記載為其他化合物之(甲基)丙烯酸酯類、(甲基)丙烯醯胺類、烯丙基化合物、乙烯基醚類、乙烯基酯類、苯乙烯類等而成者。 　　[0061] 具有可與光聚合性化合物(B)聚合之部位的構成單位，以具有乙烯性不飽和基者作為可與光聚合性化合物(B)聚合之部位為佳。具有如此之構成單位的共聚物化，關於共聚物(A3)，可藉由使含有來自上述(a1)不飽和羧酸的構成單位的聚合物所含有的羧基的至少一部份與上述(a2)含脂環式環氧基之不飽和化合物及/或(a4)含環氧基之不飽和化合物進行反應來調製。又，共聚物(A4)可藉由使具有來自上述(a1)不飽和羧酸的構成單位與(a2)含脂環式環氧基之不飽和化合物及/或來自(a4)含環氧基之不飽和化合物的構成單位的共聚物中的環氧基的至少一部份與(a1)不飽和羧酸進行反應來調製。 　　[0062] 共聚物(A3)中之來自(a1)不飽和羧酸的構成單位之佔有比例以1~50質量%為佳、5~45質量%更佳。共聚物(A3)中之具有可與光聚合性化合物(B)聚合之部位的構成單位之佔有比例以1~45質量%為佳、5~40質量%更佳。共聚物(A3)以如此之比率含有各構成單位之情形，容易得到可形成與基板之密著性優異的低折射率膜的感光性樹脂組成物。 　　[0063] 共聚物(A4)中之來自(a1)不飽和羧酸的構成單位之佔有比例以1~50質量%為佳、5~45質量%更佳。共聚物(A4)中之來自(a2)含脂環式環氧基之不飽和化合物及/或(a4)含環氧基之不飽和化合物的構成單位之佔有比例以55質量%以上為佳、71質量%以上更佳、71~80質量%特別佳。 　　共聚物(A4)中之具有可與光聚合性化合物(B)聚合之部位的構成單位之佔有比例以1~45質量%為佳、5~40質量%更佳。共聚物(A4)以如此之比率含有各構成單位之情形，容易得到可形成與基板之密著性優異的低折射率膜的感光性樹脂組成物。 　　[0064] 共聚物(A3)、及共聚物(A4)之質量平均分子量以2000~50000為佳、5000~30000更佳。藉由在上述範圍，有感光性樹脂組成物的膜形成能力、曝光後的顯影性容易得到平衡之傾向。 　　[0065] 樹脂(A)的感光性樹脂組成物中之含量，相對於除去後述之填料(D)之質量與有機溶劑(S)之質量的感光性樹脂組成物的質量，以20~85質量%為佳、30~70質量%更佳。 [0066] ＜光聚合性化合物(B)＞ 　　光聚合性化合物(B)方面，可宜使用具有乙烯性不飽和基之單體。該具有乙烯性不飽和基之單體中，有單官能單體與多官能單體。 　　[0067] 單官能單體方面，可舉例如(甲基)丙烯醯胺、羥甲基(甲基)丙烯醯胺、甲氧基甲基(甲基)丙烯醯胺、乙氧基甲基(甲基)丙烯醯胺、丙氧基甲基(甲基)丙烯醯胺、丁氧基甲氧基甲基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、(甲基)丙烯酸、富馬酸、馬來酸、馬來酸酐、伊康酸、伊康酸酐、檸康酸、檸康酸酐、巴豆酸、2-丙烯醯胺-2-甲基丙烷磺酸、tert-丁基丙烯醯胺磺酸、甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、丁基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、環己基(甲基)丙烯酸酯、2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、2-羥基丁基(甲基)丙烯酸酯、2-苯氧基-2-羥基丙基(甲基)丙烯酸酯、2-(甲基)丙烯醯基氧基-2-羥基丙基苯二甲酸酯、甘油單(甲基)丙烯酸酯、四氫糠基(甲基)丙烯酸酯、二甲基胺基乙基(甲基)丙烯酸酯、縮水甘油基(甲基)丙烯酸酯、2,2,2-三氟乙基(甲基)丙烯酸酯、2,2,3,3-四氟丙基(甲基)丙烯酸酯、鄰苯二甲酸衍生物的半(甲基)丙烯酸酯等。此等之單官能單體可單獨或2種以上組合使用。 　　[0068] 另一方面，多官能單體方面，可舉例如乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己烷甘醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷改性三羥甲基丙烷三(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、2,2-雙(4-(甲基)丙烯醯氧基二乙氧基苯基)丙烷、2,2-雙(4-(甲基)丙烯醯氧基聚乙氧基苯基)丙烷、2-羥基-3-(甲基)丙烯醯基氧基丙基(甲基)丙烯酸酯、乙二醇二縮水甘油基醚二(甲基)丙烯酸酯、二乙二醇二縮水甘油基醚二(甲基)丙烯酸酯、鄰苯二甲酸二縮水甘油基酯二(甲基)丙烯酸酯、甘油三丙烯酸酯、甘油聚縮水甘油基醚聚(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯(即、甲苯二異氰酸酯、三甲基六亞甲基二異氰酸酯或六亞甲基二異氰酸酯等與2-羥基乙基(甲基)丙烯酸酯之反應物)、亞甲基雙(甲基)丙烯醯胺、(甲基)丙烯醯胺亞甲基醚、多元醇與N-羥甲基(甲基)丙烯醯胺之縮合物等之多官能單體或三丙烯酸基甲縮醛等。此等之多官能單體可單獨或2種以上組合使用。 　　[0069] 此等之具有乙烯性不飽和基之單體中，由有提高感光性樹脂組成物的對基板之密著性、感光性樹脂組成物的硬化後的強度之傾向點來看，以3官能以上之多官能單體為佳、4官能以上之多官能單體更佳、5官能以上之多官能單體又更佳。 　　[0070] 又，以光聚合性化合物(B)為含有6官能以上之多官能性化合物者特別佳。 　　感光性樹脂組成物含有含6官能以上之多官能性化合物的光聚合性化合物(B)，則曝光而硬化時，因為在低折射率膜之表面進行高度交聯，容易形成硬且緊密的低折射率膜。 　　因此，即使將保護膠帶從低折射率膜剝離，低折射率膜之表面不易粗糙。 　　[0071] 進一步，光聚合性化合物(B)同時含有6官能以上之多官能性化合物與未達6官能的光聚合性化合物者亦佳。 　　單獨使用6官能以上之多官能性化合物之情形，氧阻礙之影響少，可使膜表面之硬化度提升。但是該情況，藉由連鎖反應而硬化進行至未曝光部，雖為可容許程度，但有些容易產生顯影後殘渣、或圖型邊緣形狀容易產生搖晃。 　　相對於此，使用6官能以上之多官能性化合物以及未達6官能的光聚合性化合物，則容易取得膜表面的良好的硬化、顯影後的少殘渣量、平滑的圖型邊緣形狀之平衡。 　　[0072] 光聚合性化合物(B)的感光性樹脂組成物中之含量，相對於除去後述之填料(D)之質量與有機溶劑(S)之質量的感光性樹脂組成物的質量，以1~70質量%為佳、5~60質量%更佳。藉由在上述範圍，有容易取得感度、顯影性、解像性之平衡的傾向。 　　[0073] ＜光聚合起始劑(C)＞ 　　作為光聚合起始劑(C)，不特別限制，可使用以往習知光聚合起始劑。 　　[0074] 光聚合起始劑(C)方面，具體上，可舉例如1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-〔4-(2-羥基乙氧基)苯基〕-2-羥基-2-甲基-1-丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、1-(4-十二基苯基)-2-羥基-2-甲基丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、雙(4-二甲基胺基苯基)酮、2-甲基-1-〔4-(甲基硫基)苯基〕-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁烷-1-酮、O-乙醯基-1-[6-(2-甲基苯甲醯基)-9-乙基-9H-咔唑-3-基]乙酮肟、O-乙醯基-1-[6-(吡咯-2-基羰基)-9-乙基-9H咔唑-3-基]乙酮肟、(9-乙基-6-硝基-9H-咔唑-3-基)[4-(2-甲氧基-1-甲基乙氧基)-2-甲基苯基]甲酮O-乙醯基肟、2-(苯甲醯基氧基亞胺基)-1-[4-(苯基硫基)苯基]-1-辛酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、4-苯甲醯基-4’-甲基二甲基硫化物、4-二甲基胺基安息香酸、4-二甲基胺基安息香酸甲基酯、4-二甲基胺基安息香酸乙基酯、4-二甲基胺基安息香酸丁基酯、4-二甲基胺基-2-乙基己基安息香酸、4-二甲基胺基-2-異戊基安息香酸、苄基-β-甲氧基乙基縮醛、苄基二甲基縮酮、1-苯基-1,2-丙烷二酮-2-(O-乙氧基羰基)肟、o-苯甲醯基安息香酸甲基酯、2,4-二乙基噻噸酮、2-氯噻噸酮、2,4-二甲基噻噸酮、1-氯-4-丙氧基噻噸酮、硫雜蒽、2-氯硫雜蒽、2,4-二乙基硫雜蒽、2-甲基硫雜蒽、2-異丙基硫雜蒽、2-乙基蒽醌、八甲基蒽醌、1,2-苯並蒽醌、2,3-二苯基蒽醌、偶氮二異丁腈、苯甲醯基過氧化物、異丙苯過氧化氫、2-巰基苯並咪唑、2-巰基苯並噁唑、2-巰基苯並噻唑、2-(o-氯苯基)-4,5-二(m-甲氧基苯基)-咪唑基二聚物、二苯甲酮、2-氯二苯甲酮、p,p’-雙二甲基胺基二苯甲酮、4,4’-雙二乙基胺基二苯甲酮、4,4’-二氯二苯甲酮、3,3-二甲基-4-甲氧基二苯甲酮、苄基酯、安息香、安息香甲基醚、安息香乙基醚、安息香異丙基醚、安息香-n-丁基醚、安息香異丁基醚、安息香丁基醚、苯乙酮、2,2-二乙氧基苯乙酮、p-二甲基苯乙酮、p-二甲基胺基苯丙酮、二氯苯乙酮、三氯苯乙酮、p-tert-丁基苯乙酮、p-二甲基胺基苯乙酮、p-tert-丁基三氯苯乙酮、p-tert-丁基二氯苯乙酮、α,α-二氯-4-苯氧基苯乙酮、噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮、二苯並環庚酮、戊基-4-二甲基胺基苯甲酸酯、9-苯基吖啶、1,7-雙-(9-吖啶基)庚烷、1,5-雙-(9-吖啶基)戊烷、1,3-雙-(9-吖啶基)丙烷、p-甲氧基三嗪、2,4,6-參(三氯甲基)-s-三嗪、2-甲基-4,6-雙(三氯甲基)-s-三嗪、2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-s-三嗪、2-(4-乙氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三嗪、2-(4-n-丁氧基苯基)-4,6-雙(三氯甲基)-s-三嗪、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯基-s-三嗪、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯基-s-三嗪、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯乙烯基苯基-s-三嗪、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯乙烯基苯基-s-三嗪等。此等之光聚合起始劑可單獨或2種以上組合使用。 　　[0075] 此等之中，使用肟酯化合物作為光聚合起始劑(C)此點，在感度面上尤佳。肟酯化合物方面，較佳的化合物的例，可舉例如O-乙醯基-1-[6-(2-甲基苯甲醯基)-9-乙基-9H-咔唑-3-基]乙酮肟、O-乙醯基-1-[6-(吡咯-2-基羰基)-9-乙基-9H咔唑-3-基]乙酮肟、及、2-(苯甲醯基氧基亞胺基)-1-[4-(苯基硫基)苯基]-1-辛酮。 　　[0076] 使用肟酯化合物作為光聚合起始劑(C)時，亦宜併用肟酯化合物與肟酯化合物以外的其他光聚合起始劑。 　　併用肟酯化合物與其他光聚合起始劑時，容易將感光性樹脂組成物的感度調整為適當的範圍。因此，因為不易造成曝光所致之進行過度硬化，難以形成寬度大於期望寬度的經圖型化的低折射率膜。 　　與肟酯化合物併用的其他光聚合起始劑方面，以α-胺基烷基苯酮系的光聚合起始劑為佳。α-胺基烷基苯酮系的光聚合起始劑的較佳例，可舉例如2-甲基-1-〔4-(甲基硫基)苯基〕-2-嗎啉基丙烷-1-酮(IRGACURE907(IR-907)、商品名、BASF公司製)、及2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁烷-1-酮(IRGACURE369E(IR-369E)、商品名、BASF公司製)。 　　[0077] 又，肟酯化合物方面，亦宜使用下述式(c1)所表示之肟酯化合物。
Figure 02_image015
(Rc1 為選自1價有機基、胺基、鹵素、硝基、及氰基所構成的群之基， 　　n1為0~4的整數， 　　n2為0或1， 　　Rc2 為可具有取代基的苯基或可具有取代基的咔唑基， 　　Rc3 為氫原子或碳原子數1~6的烷基。) 　　[0078] 式(c1)中，Rc1 在不阻礙本發明之目的範圍，不特別限制，從種種之有機基中適宜選擇。Rc1 為有機基時的較佳例，可舉例如烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、飽和脂肪族醯基氧基、烷氧基羰基、可具有取代基的苯基、可具有取代基的苯氧基、可具有取代基的苯甲醯基、可具有取代基的苯氧基羰基、可具有取代基的苯甲醯基氧基、可具有取代基的苯基烷基、可具有取代基的萘基、可具有取代基的萘氧基、可具有取代基的萘甲醯基、可具有取代基的萘氧基羰基、可具有取代基的萘甲醯基氧基、可具有取代基的萘基烷基、可具有取代基的雜環基、胺基、被1個或2個有機基取代的胺基、嗎啉-1-基、及哌嗪-1-基、鹵素、硝基、及氰基等。n1為2~4的整數時，Rc1 可為相同亦可為相異。又，取代基的碳原子數中不包含取代基再具有的取代基的碳原子數。 　　[0079] Rc1 為烷基時，以碳原子數1~20為佳、碳原子數1~6更佳。又，Rc1 為烷基時，可為直鏈亦可為分支鏈。Rc1 為烷基時的具體例，可舉例如甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、n-戊基、異戊基、sec-戊基、tert-戊基、n-己基、n-庚基、n-辛基、異辛基、sec-辛基、tert-辛基、n-壬基、異壬基、n-癸基、及異癸基等。又，Rc1 為烷基時，烷基為碳鏈中可含有醚鍵(-O-)。碳鏈中具有醚鍵的烷基的例，可舉例如甲氧基乙基、乙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙基氧基乙氧基乙基、及甲氧基丙基等。 　　[0080] Rc1 為烷氧基時，以碳原子數1~20為佳、碳原子數1~6更佳。又，Rc1 為烷氧基時，可為直鏈亦可為分支鏈。Rc1 為烷氧基時的具體例，可舉例如甲氧基、乙氧基、n-丙基氧基、異丙基氧基、n-丁基氧基、異丁基氧基、sec-丁基氧基、tert-丁基氧基、n-戊基氧基、異戊基氧基、sec-戊基氧基、tert-戊基氧基、n-己基氧基、n-庚基氧基、n-辛基氧基、異辛基氧基、sec-辛基氧基、tert-辛基氧基、n-壬基氧基、異壬基氧基、n-癸基氧基、及異癸基氧基等。又，Rc1 為烷氧基時，烷氧基為碳鏈中可含有醚鍵(-O-)。碳鏈中具有醚鍵的烷氧基的例，可舉例如甲氧基乙氧基、乙氧基乙氧基、甲氧基乙氧基乙氧基、乙氧基乙氧基乙氧基、丙基氧基乙氧基乙氧基、及甲氧基丙基氧基等。 　　[0081] Rc1 為環烷基或環烷氧基時，以碳原子數3~10為佳、碳原子數3~6更佳。Rc1 為環烷基時的具體例，可舉例如環丙基、環丁基、環戊基、環己基、環庚基、及環辛基等。Rc1 為環烷氧基時的具體例，可舉例如環丙基氧基、環丁基氧基、環戊基氧基、環己基氧基、環庚基氧基、及環辛基氧基等。 　　[0082] Rc1 為飽和脂肪族醯基或飽和脂肪族醯基氧基時，以碳原子數2~20為佳、碳原子數2~7更佳。Rc1 為飽和脂肪族醯基時的具體例，可舉例如乙醯基、丙醯基、n-丁醯基、2-甲基丙醯基、n-戊醯基、2,2-二甲基丙醯基、n-己醯基、n-庚醯基、n-辛醯基、n-壬醯基、n-癸醯基、n-十一醯基、n-十二醯基、n-十三醯基、n-十四醯基、n-十五醯基、及n-十六醯基等。Rc1 為飽和脂肪族醯基氧基時的具體例，可舉例如乙醯基氧基、丙醯氧基、n-丁醯基氧基、2-甲基丙醯氧基、n-戊醯基氧基、2,2-二甲基丙醯氧基、n-己醯氧基、n-庚醯基氧基、n-辛醯基氧基、n-壬醯基氧基、n-癸醯基氧基、n-十一醯基氧基、n-十二醯基氧基、n-十三醯基氧基、n-十四醯基氧基、n-十五醯基氧基、及n-十六醯基氧基等。 　　[0083] Rc1 為烷氧基羰基時，以碳原子數2~20為佳、碳原子數2~7更佳。Rc1 為烷氧基羰基時的具體例，可舉例如甲氧基羰基、乙氧基羰基、n-丙基氧基羰基、異丙基氧基羰基、n-丁基氧基羰基、異丁基氧基羰基、sec-丁基氧基羰基、tert-丁基氧基羰基、n-戊基氧基羰基、異戊基氧基羰基、sec-戊基氧基羰基、tert-戊基氧基羰基、n-己基氧基羰基、n-庚基氧基羰基、n-辛基氧基羰基、異辛基氧基羰基、sec-辛基氧基羰基、tert-辛基氧基羰基、n-壬基氧基羰基、異壬基氧基羰基、n-癸基氧基羰基、及異癸基氧基羰基等。 　　[0084] Rc1 為苯基烷基時，以碳原子數7~20為佳、碳原子數7~10更佳。又Rc1 為萘基烷基時，以碳原子數11~20為佳、碳原子數11~14更佳。Rc1 為苯基烷基時的具體例，可舉例如苄基、2-苯基乙基、3-苯基丙基、及4-苯基丁基。Rc1 為萘基烷基時的具體例，可舉例如α-萘基甲基、β-萘基甲基、2-(α-萘基)乙基、及2-(β-萘基)乙基。Rc1 為苯基烷基或萘基烷基時，Rc1 在苯基或萘基上可再具有取代基。 　　[0085] Rc1 為雜環基時，雜環基為含有1個以上之N、S、O的5員或6員的單環或該單環彼此或該單環與苯環縮合而成的雜環基。雜環基為縮合環時，為環數至3為止者。構成該雜環基的雜環方面，可舉例如呋喃、噻吩、吡咯、噁唑、異噁唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、***、吡啶、吡嗪、嘧啶、噠嗪、苯並呋喃、苯並噻吩、吲哚、異吲哚、吲哚嗪、苯並咪唑、苯並***、苯並噁唑、苯並噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞嗪、噌啉、及喹喔啉等。Rc1 為雜環基時，雜環基可再具有取代基。 　　[0086] Rc1 為被1個或2個有機基取代的胺基時，有機基的適宜之例，可舉例如碳原子數1~20的烷基、碳原子數3~10的環烷基、碳原子數2~20的飽和脂肪族醯基、可具有取代基的苯基、可具有取代基的苯甲醯基、可具有取代基的碳原子數7~20的苯基烷基、可具有取代基的萘基、可具有取代基的萘甲醯基、可具有取代基的碳原子數11~20的萘基烷基、及雜環基等。此等之適宜之有機基的具體例與Rc1 相同。被1個或2個有機基取代的胺基的具體例，可舉例如甲基胺基、乙基胺基、二乙基胺基、n-丙基胺基、二-n-丙基胺基、異丙基胺基、n-丁基胺基、二-n-丁基胺基、n-戊基胺基、n-己基胺基、n-庚基胺基、n-辛基胺基、n-壬基胺基、n-癸基胺基、苯基胺基、萘基胺基、乙醯基胺基、丙醯胺基、n-丁醯基胺基、n-戊醯基胺基、n-己醯胺基、n-庚醯基胺基、n-辛醯基胺基、n-癸醯基胺基、苯甲醯基胺基、α-萘甲醯基胺基、及β-萘甲醯基胺基等。 　　[0087] Rc1 所含有的苯基、萘基、及雜環基再具有取代基時的取代基方面，可舉例如碳原子數1~6的烷基、碳原子數1~6的烷氧基、碳原子數2~7的飽和脂肪族醯基、碳原子數2~7的烷氧基羰基、碳原子數2~7的飽和脂肪族醯基氧基、具有碳原子數1~6的烷基的單烷基胺基、具有碳原子數1~6的烷基的二烷基胺基、嗎啉-1-基、哌嗪-1-基、鹵素、硝基、及氰基等。Rc1 所含有的苯基、萘基、及雜環基再具有取代基時，該取代基的數在不阻礙本發明之目的範圍，不被限定，但以1~4為佳。Rc1 所含有的苯基、萘基、及雜環基具有複數取代基時，複數的取代基可為相同亦可為相異。 　　[0088] Rc1 中，由為化學安定或立體阻礙少且容易合成肟酯化合物等來看，以由碳原子數1~6的烷基、碳原子數1~6的烷氧基、及碳原子數2~7的飽和脂肪族醯基所構成的群選擇出的基為佳、碳原子數1~6的烷基更佳、甲基特別佳。 　　[0089] Rc1 鍵結於苯基的位置，關於Rc1 鍵結的苯基，以苯基與肟酯化合物的主骨架的鍵結鍵的位置為1位，以甲基的位置為2位時，以4位或5位為佳、5位更佳。又，n1以0~3的整數為佳、0~2的整數更佳、0或1特別佳。 　　[0090] Rc2 為可具有取代基的苯基或可具有取代基的咔唑基。又，Rc2 為可具有取代基的咔唑基時，咔唑基上的氮原子可被碳原子數1~6的烷基取代。 　　[0091] Rc2 中，苯基或咔唑基具有的取代基在不阻礙本發明之目的範圍，不特別限定。苯基或咔唑基在碳原子上可具有的適宜之取代基的例，可舉例如碳原子數1~20的烷基、碳原子數1~20的烷氧基、碳原子數3~10的環烷基、碳原子數3~10的環烷氧基、碳原子數2~20的飽和脂肪族醯基、碳原子數2~20的烷氧基羰基、碳原子數2~20的飽和脂肪族醯基氧基、可具有取代基的苯基、可具有取代基的苯氧基、可具有取代基的苯基硫基、可具有取代基的苯甲醯基、可具有取代基的苯氧基羰基、可具有取代基的苯甲醯基氧基、可具有取代基的碳原子數7~20的苯基烷基、可具有取代基的萘基、可具有取代基的萘氧基、可具有取代基的萘甲醯基、可具有取代基的萘氧基羰基、可具有取代基的萘甲醯基氧基、可具有取代基的碳原子數11~20的萘基烷基、可具有取代基的雜環基、可具有取代基的雜環羰基、胺基、被1個或2個有機基取代的胺基、嗎啉-1-基、及哌嗪-1-基、鹵素、硝基、及氰基等。 　　[0092] Rc2 為咔唑基時，咔唑基在氮原子上可具有的適宜之取代基的例，可舉例如碳原子數1~20的烷基、碳原子數3~10的環烷基、碳原子數2~20的飽和脂肪族醯基、碳原子數2~20的烷氧基羰基、可具有取代基的苯基、可具有取代基的苯甲醯基、可具有取代基的苯氧基羰基、可具有取代基的碳原子數7~20的苯基烷基、可具有取代基的萘基、可具有取代基的萘甲醯基、可具有取代基的萘氧基羰基、可具有取代基的碳原子數11~20的萘基烷基、可具有取代基的雜環基、及可具有取代基的雜環羰基等。在此等之取代基中，以碳原子數1~20的烷基為佳、碳原子數1~6的烷基更佳、乙基特別佳。 　　[0093] 苯基或咔唑基可具有的取代基的具體例，關於烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧基羰基、飽和脂肪族醯基氧基、可具有取代基的苯基烷基、可具有取代基的萘基烷基、可具有取代基的雜環基、及被1個或2個有機基取代的胺基方面，與Rc1 相同。 　　[0094] Rc2 中，苯基或咔唑基具有的取代基所含有的苯基、萘基、及雜環基再具有取代基時的取代基的例，可舉例如碳原子數1~6的烷基；碳原子數1~6的烷氧基；碳原子數2~7的飽和脂肪族醯基；碳原子數2~7的烷氧基羰基；碳原子數2~7的飽和脂肪族醯基氧基；苯基；萘基；苯甲醯基；萘甲醯基；被選自由碳原子數1~6的烷基、嗎啉-1-基、哌嗪-1-基、及苯基所構成的群之基取代的苯甲醯基；具有碳原子數1~6的烷基的單烷基胺基；具有碳原子數1~6的烷基的二烷基胺基；嗎啉-1-基；哌嗪-1-基；鹵素；硝基；氰基。苯基或咔唑基具有的取代基所含有的苯基、萘基、及雜環基再具有取代基時，該取代基的數在不阻礙本發明之目的範圍，不被限定，但以1~4為佳。苯基、萘基、及雜環基具有複數取代基時，複數的取代基可為相同亦可為相異。 　　[0095] Rc2 中，由容易得到感度優異的光聚合起始劑之點來看，以下述式(c2)或(c3)所表示之基為佳、下述式(c2)所表示之基更佳、下述式(c2)所表示之基且A為S之基特別佳。 　　[0096]
Figure 02_image017
(Rc4 為選自1價有機基、胺基、鹵素、硝基、及氰基所構成的群之基，A為S或O，n3為0~4的整數。) 　　[0097]
Figure 02_image019
(Rc5 及Rc6 各自為1價有機基。) 　　[0098] 式(c2)中之Rc4 為有機基時，在不阻礙本發明之目的範圍，可選自種種之有機基。式(c2)中Rc4 為有機基時的較佳例，可舉例如碳原子數1~6的烷基；碳原子數1~6的烷氧基；碳原子數2~7的飽和脂肪族醯基；碳原子數2~7的烷氧基羰基；碳原子數2~7的飽和脂肪族醯基氧基；苯基；萘基；苯甲醯基；萘甲醯基；被選自由碳原子數1~6的烷基、嗎啉-1-基、哌嗪-1-基、及苯基所構成的群之基取代的苯甲醯基；具有碳原子數1~6的烷基的單烷基胺基；具有碳原子數1~6的烷基的二烷基胺基；嗎啉-1-基；哌嗪-1-基；鹵素；硝基；氰基。 　　[0099] Rc4 中，以苯甲醯基；萘甲醯基；被選自由碳原子數1~6的烷基、嗎啉-1-基、哌嗪-1-基、及苯基所構成的群之基取代的苯甲醯基；硝基為佳、苯甲醯基；萘甲醯基；2-甲基苯基羰基；4-(哌嗪-1-基)苯基羰基；4-(苯基)苯基羰基更佳。 　　[0100] 又，式(c2)中，n3以0~3的整數為佳、0~2的整數更佳、0或1者特別佳。n3為1時，Rc4 之鍵結位置相對於Rc4 鍵結的苯基與氧原子或硫原子鍵結的鍵結鍵而言，以對位者為佳。 　　[0101] 式(c3)中之Rc5 在不阻礙本發明之目的範圍，可選自種種之有機基。Rc5 的較佳例，可舉例如碳原子數1~20的烷基、碳原子數3~10的環烷基、碳原子數2~20的飽和脂肪族醯基、碳原子數2~20的烷氧基羰基、可具有取代基的苯基、可具有取代基的苯甲醯基、可具有取代基的苯氧基羰基、可具有取代基的碳原子數7~20的苯基烷基、可具有取代基的萘基、可具有取代基的萘甲醯基、可具有取代基的萘氧基羰基、可具有取代基的碳原子數11~20的萘基烷基、可具有取代基的雜環基、及可具有取代基的雜環羰基等。 　　[0102] Rc5 中，以碳原子數1~20的烷基為佳、碳原子數1~6的烷基更佳、乙基特別佳。 　　[0103] 式(c3)中之Rc6 在不阻礙本發明之目的範圍，不特別限制，可選自種種之有機基。作為Rc6 適宜之基的具體例，可舉例如碳原子數1~20的烷基、可具有取代基的苯基、可具有取代基的萘基、及可具有取代基的雜環基。Rc6 方面，在此等之基中，以可具有取代基的苯基更佳、2-甲基苯基特別佳。 　　[0104] Rc4 、Rc5 或Rc6 所含有的苯基、萘基、及雜環基再具有取代基時的取代基方面，可舉例如碳原子數1~6的烷基、碳原子數1~6的烷氧基、碳原子數2~7的飽和脂肪族醯基、碳原子數2~7的烷氧基羰基、碳原子數2~7的飽和脂肪族醯基氧基、具有碳原子數1~6的烷基的單烷基胺基、具有碳原子數1~6的烷基的二烷基胺基、嗎啉-1-基、哌嗪-1-基、鹵素、硝基、及氰基等。Rc4 、Rc5 或Rc6 所含有的苯基、萘基、及雜環基再具有取代基時，該取代基的數在不阻礙本發明之目的範圍，不被限定，但以1~4為佳。Rc4 、Rc5 或Rc6 所含有的苯基、萘基、及雜環基具有複數取代基時，複數的取代基可為相同亦可為相異。 　　[0105] 式(c1)中之Rc3 為氫原子或碳原子數1~6的烷基。Rc3 方面，以甲基或乙基為佳、甲基更佳。 　　[0106] 式(c1)所表示之肟酯化合物，在p為0時，可藉由例如下述路徑1進行合成。具體上，將下述式(c1-1)所表示之芳香族化合物，使用下述式(c1-2)所表示之鹵代羰基化合物，藉由Friedel-Crafts反應進行醯基化，得到下述式(c1-3)所表示之酮化合物，使得到的酮化合物(c1-3)以羥基胺進行肟化，得到下述式(c1-4)所表示之肟化合物，接著使式(c1-4)的肟化合物中的羥基進行醯基化，可得到下述式(c1-7)所表示之肟酯化合物。作為醯基化劑，以使用下述式(c1-5)所表示之酸酐((Rc3 CO)2 O)或下述式(c1-6)所表示之酸鹵化物(Rc3 COHal、Hal為鹵素。)者為佳。又，下述式(c1-2)中，Hal為鹵素，下述式(c1-1)、(c1-2)、(c1-3)、(c1-4)、及(c1-7)中，Rc1 、Rc2 、Rc3 、及n1與式(c1)相同。 　　[0107] ＜路徑1＞
Figure 02_image021
[0108] 式(c1)所表示之肟酯化合物，在n2為1時，可藉由例如下述路徑2進行合成。具體上，使下述式(c2-1)所表示之酮化合物，在鹽酸存在下與下述式(c2-2)所表示之亞硝酸酯(RONO、R為碳原子數1~6的烷基。)進行反應，得到下述式(c2-3)所表示之酮肟化合物，接著，使下述式(c2-3)所表示之酮肟化合物中的羥基進行醯基化，可得到下述式(c2-6)所表示之肟酯化合物。作為醯基化劑，以使用下述式(c2-4)所表示之酸酐((Rc3 CO)2 O)或下述式(c2-5)所表示之酸鹵化物(Rc3 COHal、Hal為鹵素。)者為佳。又，下述式(c2-1)、(c2-3)、(c2-4)、(c2-5)、及(c2-6)中，Rc1 、Rc2 、Rc3 、及n1與式(c1)相同。 　　[0109] ＜路徑2＞
Figure 02_image023
[0110] 又，式(c1)所表示之肟酯化合物，在n2為1、Rc1 為甲基，且相對於Rc1 鍵結的苯環上鍵結的甲基而言，Rc1 鍵結於對位時，例如下述式(c2-7)所表示之化合物亦可以路徑1相同方法，藉由進行肟化、及醯基化來合成。又，下述式(c2-7)中，Rc2 與式(c1)相同。 　　[0111]
Figure 02_image025
[0112] 式(c1)所表示之肟酯化合物中，特別佳之化合物方面，可舉例如下述PI-1~PI-42。
Figure 02_image027
[0113]
Figure 02_image029
[0114]
Figure 02_image031
[0115]
Figure 02_image033
[0116]
Figure 02_image035
[0117]
Figure 02_image037
[0118] 又，下述式(c4)所表示之肟酯化合物亦宜作為光聚合起始劑。 　　[0119]
Figure 02_image039
(Rc7 為氫原子、硝基或1價有機基，Rc8 及Rc9 各自為可具有取代基的鏈狀烷基、可具有取代基的環狀有機基或氫原子，Rc8 與Rc9 相互鍵結可形成環，Rc10 為1價有機基，Rc11 為氫原子、可具有取代基的碳原子數1~11的烷基或可具有取代基的芳基，n4為0~4的整數，n5為0或1。) 　　[0120] 在此，用以製造式(c4)的肟酯化合物的肟化合物，以下式(c5)所表示之化合物為宜。 　　[0121]
Figure 02_image041
(Rc7 、Rc8 、Rc9 、Rc10 、n4、及n5與式(c4)相同。) 　　[0122] 式(c4)及(c5)中，Rc7 為氫原子、硝基或1價有機基。Rc7 在式(c4)中的茀環上，鍵結於與-(CO)n5 -所表示之基上鍵結的6員芳香環不同的6員芳香環。式(c4)中，Rc7 的對茀環之鍵結位置不特別限定。式(c4)所表示之化合物具有1個以上之Rc7 時，由容易合成式(c4)所表示之化合物之觀點等來看，以1個以上之Rc7 中的1個鍵結於茀環中的2位者為佳。Rc7 為複數時，複數的Rc7 可為相同亦可為相異。 　　[0123] Rc7 為有機基時，Rc7 在不阻礙本發明之目的範圍，不特別限制，從種種之有機基中適宜選擇。Rc7 為有機基時的較佳例，可舉例如烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、飽和脂肪族醯基氧基、烷氧基羰基、可具有取代基的苯基、可具有取代基的苯氧基、可具有取代基的苯甲醯基、可具有取代基的苯氧基羰基、可具有取代基的苯甲醯基氧基、可具有取代基的苯基烷基、可具有取代基的萘基、可具有取代基的萘氧基、可具有取代基的萘甲醯基、可具有取代基的萘氧基羰基、可具有取代基的萘甲醯基氧基、可具有取代基的萘基烷基、可具有取代基的雜環基、可具有取代基的雜環羰基、被1個或2個有機基取代的胺基、嗎啉-1-基、及哌嗪-1-基等。 　　[0124] Rc7 為烷基時，烷基的碳原子數，以1~20為佳、1~6更佳。又，Rc7 為烷基時，可為直鏈亦可為分支鏈。Rc7 為烷基時的具體例，可舉例如甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、n-戊基、異戊基、sec-戊基、tert-戊基、n-己基、n-庚基、n-辛基、異辛基、sec-辛基、tert-辛基、n-壬基、異壬基、n-癸基、及異癸基等。又，Rc7 為烷基時，烷基為碳鏈中可含有醚鍵(-O-)。碳鏈中具有醚鍵的烷基的例，可舉例如甲氧基乙基、乙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙基氧基乙氧基乙基、及甲氧基丙基等。 　　[0125] Rc7 為烷氧基時，烷氧基的碳原子數，以1~20為佳、1~6更佳。又，Rc7 為烷氧基時，可為直鏈亦可為分支鏈。Rc7 為烷氧基時的具體例，可舉例如甲氧基、乙氧基、n-丙基氧基、異丙基氧基、n-丁基氧基、異丁基氧基、sec-丁基氧基、tert-丁基氧基、n-戊基氧基、異戊基氧基、sec-戊基氧基、tert-戊基氧基、n-己基氧基、n-庚基氧基、n-辛基氧基、異辛基氧基、sec-辛基氧基、tert-辛基氧基、n-壬基氧基、異壬基氧基、n-癸基氧基、及異癸基氧基等。又，Rc7 為烷氧基時，烷氧基為碳鏈中可含有醚鍵(-O-)。碳鏈中具有醚鍵的烷氧基的例，可舉例如甲氧基乙氧基、乙氧基乙氧基、甲氧基乙氧基乙氧基、乙氧基乙氧基乙氧基、丙基氧基乙氧基乙氧基、及甲氧基丙基氧基等。 　　[0126] Rc7 為環烷基或環烷氧基時，環烷基或環烷氧基的碳原子數，以3~10為佳、3~6更佳。Rc7 為環烷基時的具體例，可舉例如環丙基、環丁基、環戊基、環己基、環庚基、及環辛基等。Rc7 為環烷氧基時的具體例，可舉例如環丙基氧基、環丁基氧基、環戊基氧基、環己基氧基、環庚基氧基、及環辛基氧基等。 　　[0127] Rc7 為飽和脂肪族醯基或飽和脂肪族醯基氧基時，飽和脂肪族醯基或飽和脂肪族醯基氧基的碳原子數以2~21為佳、2~7更佳。Rc7 為飽和脂肪族醯基時的具體例，可舉例如乙醯基、丙醯基、n-丁醯基、2-甲基丙醯基、n-戊醯基、2,2-二甲基丙醯基、n-己醯基、n-庚醯基、n-辛醯基、n-壬醯基、n-癸醯基、n-十一醯基、n-十二醯基、n-十三醯基、n-十四醯基、n-十五醯基、及n-十六醯基等。Rc7 為飽和脂肪族醯基氧基時的具體例，可舉例如乙醯基氧基、丙醯氧基、n-丁醯基氧基、2-甲基丙醯氧基、n-戊醯基氧基、2,2-二甲基丙醯氧基、n-己醯氧基、n-庚醯基氧基、n-辛醯基氧基、n-壬醯基氧基、n-癸醯基氧基、n-十一醯基氧基、n-十二醯基氧基、n-十三醯基氧基、n-十四醯基氧基、n-十五醯基氧基、及n-十六醯基氧基等。 　　[0128] Rc7 為烷氧基羰基時，烷氧基羰基的碳原子數，以2~20為佳、2~7更佳。Rc7 為烷氧基羰基時的具體例，可舉例如甲氧基羰基、乙氧基羰基、n-丙基氧基羰基、異丙基氧基羰基、n-丁基氧基羰基、異丁基氧基羰基、sec-丁基氧基羰基、tert-丁基氧基羰基、n-戊基氧基羰基、異戊基氧基羰基、sec-戊基氧基羰基、tert-戊基氧基羰基、n-己基氧基羰基、n-庚基氧基羰基、n-辛基氧基羰基、異辛基氧基羰基、sec-辛基氧基羰基、tert-辛基氧基羰基、n-壬基氧基羰基、異壬基氧基羰基、n-癸基氧基羰基、及異癸基氧基羰基等。 　　[0129] Rc7 為苯基烷基時，苯基烷基的碳原子數，以7~20為佳、7~10更佳。又，Rc7 為萘基烷基時，萘基烷基的碳原子數，以11~20為佳、11~14更佳。Rc7 為苯基烷基時的具體例，可舉例如苄基、2-苯基乙基、3-苯基丙基、及4-苯基丁基。Rc7 為萘基烷基時的具體例，可舉例如α-萘基甲基、β-萘基甲基、2-(α-萘基)乙基、及2-(β-萘基)乙基。Rc7 為苯基烷基或萘基烷基時，Rc7 在苯基或萘基上可再具有取代基。 　　[0130] Rc7 為雜環基時，雜環基為含有1個以上之N、S、O的5員或6員的單環或該單環彼此或該單環與苯環縮合而成的雜環基。雜環基為縮合環時，為環數至3為止者。雜環基可為芳香族基(雜芳基)，亦可為非芳香族基。構成該雜環基的雜環方面，可舉例如呋喃、噻吩、吡咯、噁唑、異噁唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、***、吡啶、吡嗪、嘧啶、噠嗪、苯並呋喃、苯並噻吩、吲哚、異吲哚、吲哚嗪、苯並咪唑、苯並***、苯並噁唑、苯並噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞嗪、噌啉、喹喔啉、哌啶、哌嗪、嗎啉、哌啶、四氫吡喃、及四氫呋喃等。Rc7 為雜環基時，雜環基可再具有取代基。 　　[0131] Rc7 為雜環羰基時，雜環羰基所含有的雜環基，與Rc7 為雜環基時相同。 　　[0132] Rc7 為被1個或2個有機基取代的胺基時，有機基的適宜之例，可舉例如碳原子數1~20的烷基、碳原子數3~10的環烷基、碳原子數2~21的飽和脂肪族醯基、可具有取代基的苯基、可具有取代基的苯甲醯基、可具有取代基的碳原子數7~20的苯基烷基、可具有取代基的萘基、可具有取代基的萘甲醯基、可具有取代基的碳原子數11~20的萘基烷基、及雜環基等。此等之適宜之有機基的具體例與Rc7 相同。被1個或2個有機基取代的胺基的具體例，可舉例如甲基胺基、乙基胺基、二乙基胺基、n-丙基胺基、二-n-丙基胺基、異丙基胺基、n-丁基胺基、二-n-丁基胺基、n-戊基胺基、n-己基胺基、n-庚基胺基、n-辛基胺基、n-壬基胺基、n-癸基胺基、苯基胺基、萘基胺基、乙醯基胺基、丙醯胺基、n-丁醯基胺基、n-戊醯基胺基、n-己醯胺基、n-庚醯基胺基、n-辛醯基胺基、n-癸醯基胺基、苯甲醯基胺基、α-萘甲醯基胺基、及β-萘甲醯基胺基等。 　　[0133] Rc7 所含有的苯基、萘基、及雜環基再具有取代基時的取代基方面，可舉例如碳原子數1~6的烷基、碳原子數1~6的烷氧基、碳原子數2~7的飽和脂肪族醯基、碳原子數2~7的烷氧基羰基、碳原子數2~7的飽和脂肪族醯基氧基、具有碳原子數1~6的烷基的單烷基胺基、具有碳原子數1~6的烷基的二烷基胺基、嗎啉-1-基、哌嗪-1-基、鹵素、硝基、及氰基等。Rc7 所含有的苯基、萘基、及雜環基再具有取代基時，該取代基的數在不阻礙本發明之目的範圍，不被限定，但以1~4為佳。Rc7 所含有的苯基、萘基、及雜環基具有複數取代基時，複數的取代基可為相同亦可為相異。 　　[0134] 以上說明之基中，Rc7 方面，為硝基或Rc12 -CO-所表示之基，則有感度提升傾向，故佳。Rc12 在不阻礙本發明之目的範圍，不特別限制，可選自種種之有機基。作為Rc12 適宜之基的例，可舉例如碳原子數1~20的烷基、可具有取代基的苯基、可具有取代基的萘基、及可具有取代基的雜環基。Rc12 方面，在此等之基中，以2-甲基苯基、噻吩-2-基、及α-萘基特別佳。 　　又，Rc7 為氫原子，則有透明性變良好之傾向，故佳。又，Rc7 為氫原子且Rc10 為後述式(c4a)或(c4b)所表示之基，則有透明性變更良好之傾向。 　　[0135] 式(c4)中，Rc8 及Rc9 各自為可具有取代基的鏈狀烷基、可具有取代基的環狀有機基或氫原子。Rc8 與Rc9 可相互鍵結形成環。在此等之基中，Rc8 及Rc9 方面，以可具有取代基的鏈狀烷基為佳。Rc8 及Rc9 為可具有取代基的鏈狀烷基時，鏈狀烷基可為直鏈烷基亦可為分支鏈烷基。 　　[0136] Rc8 及Rc9 為不具有取代基的鏈狀烷基時，鏈狀烷基的碳原子數，以1~20為佳、1~10更佳、1~6特別佳。Rc8 及Rc9 為鏈狀烷基時的具體例，可舉例如甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、n-戊基、異戊基、sec-戊基、tert-戊基、n-己基、n-庚基、n-辛基、異辛基、sec-辛基、tert-辛基、n-壬基、異壬基、n-癸基、及異癸基等。又，Rc8 及Rc9 為烷基時，烷基為碳鏈中可含有醚鍵(-O-)。碳鏈中具有醚鍵的烷基的例，可舉例如甲氧基乙基、乙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙基氧基乙氧基乙基、及甲氧基丙基等。 　　[0137] Rc8 及Rc9 為具有取代基的鏈狀烷基時，鏈狀烷基的碳原子數，以1~20為佳、1~10更佳、1~6特別佳。該場合，取代基的碳原子數不包含於鏈狀烷基的碳原子數。具有取代基的鏈狀烷基，以直鏈狀者為佳。 　　烷基可具有的取代基在不阻礙本發明之目的範圍，不特別限定。取代基的適宜之例，可舉例如氰基、鹵素原子、環狀有機基、及烷氧基羰基。鹵素原子方面，可舉例如氟原子、氯原子、溴原子、碘原子。在此等之中，以氟原子、氯原子、溴原子為佳。環狀有機基方面，可舉例如環烷基、芳香族烴基、雜環基。環烷基的具體例方面，與Rc7 為環烷基時的較佳例相同。芳香族烴基的具體例，可舉例如苯基、萘基、聯苯基、蒽基、及菲基等。雜環基的具體例方面，與Rc7 為雜環基時的較佳例相同。Rc7 為烷氧基羰基時，烷氧基羰基所含有的烷氧基可為直鏈狀亦可為分支鏈狀，以直鏈狀為佳。烷氧基羰基所含有的烷氧基的碳原子數，以1~10為佳、1~6更佳。 　　[0138] 鏈狀烷基具有取代基之情形，取代基的數不特別限定。較佳取代基的數因應鏈狀烷基的碳原子數而變。取代基的數典型上為1~20、以1~10為佳、1~6更佳。 　　[0139] Rc8 及Rc9 為環狀有機基時，環狀有機基可為脂環式基，亦可為芳香族基。環狀有機基方面，可舉例如脂肪族環狀烴基、芳香族烴基、雜環基。Rc8 及Rc9 為環狀有機基時，環狀有機基可具有的取代基與Rc8 及Rc9 為鏈狀烷基時相同。 　　[0140] Rc8 及Rc9 為芳香族烴基時，芳香族烴基以苯基、或複數的苯環透過碳-碳鍵進行鍵結而形成的基、或複數的苯環進行縮合而形成的基者為佳。芳香族烴基為苯基或複數的苯環進行鍵結或縮合而形成的基時，芳香族烴基所含有的苯環的環數不特別限制，以3以下為佳、2以下更佳、1特別佳。芳香族烴基的較佳具體例，可舉例如苯基、萘基、聯苯基、蒽基、及菲基等。 　　[0141] Rc8 及Rc9 為脂肪族環狀烴基時，脂肪族環狀烴基可為單環式亦可為多環式。脂肪族環狀烴基的碳原子數，雖不特別限制，以3~20為佳、3~10更佳。單環式的環狀烴基的例，可舉例如環丙基、環丁基、環戊基、環己基、環庚基、環辛基、降冰片基、異冰片基、三環壬基、三環癸基、四環十二基、及金剛烷基等。 　　[0142] Rc8 及Rc9 為雜環基時，雜環基為含有1個以上之N、S、O的5員或6員的單環或該單環彼此或該單環與苯環縮合而成的雜環基。雜環基為縮合環時，為環數至3為止者。雜環基可為芳香族基(雜芳基)，亦可為非芳香族基。構成該雜環基的雜環方面，可舉例如呋喃、噻吩、吡咯、噁唑、異噁唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、***、吡啶、吡嗪、嘧啶、噠嗪、苯並呋喃、苯並噻吩、吲哚、異吲哚、吲哚嗪、苯並咪唑、苯並***、苯並噁唑、苯並噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞嗪、噌啉、喹喔啉、哌啶、哌嗪、嗎啉、哌啶、四氫吡喃、及四氫呋喃等。 　　[0143] Rc8 與Rc9 可相互鍵結形成環。由Rc8 與Rc9 形成之環所構成的基，以環亞烷基者為佳。Rc8 與Rc9 鍵結而形成環亞烷基時，構成環亞烷基的環以5員環~6員環者為佳、5員環者更佳。 　　[0144] Rc8 與Rc9 鍵結而形成的基為環亞烷基時，環亞烷基可與1個以上之其他環縮合。可與環亞烷基縮合的環之例，可舉例如苯環、萘環、環丁烷環、環戊烷環、環己烷環、環庚烷環、環辛烷環、呋喃環、噻吩環、吡咯環、吡啶環、吡嗪環、及嘧啶環等。 　　[0145] 以上說明的Rc8 及Rc9 中適宜之基的例，可舉例如式-A1 -A2 所表示之基。式中，可舉例如A1 為直鏈伸烷基，A2 為烷氧基、氰基、鹵素原子、烷基鹵化物、環狀有機基或烷氧基羰基。 　　[0146] A1 之直鏈伸烷基的碳原子數，以1~10為佳、1~6更佳。A2 為烷氧基時，烷氧基可為直鏈狀亦可為分支鏈狀，以直鏈狀為佳。烷氧基的碳原子數，以1~10為佳、1~6更佳。A2 為鹵素原子時，以氟原子、氯原子、溴原子、碘原子為佳、氟原子、氯原子、溴原子更佳。A2 為烷基鹵化物時，烷基鹵化物所含有的鹵素原子，以氟原子、氯原子、溴原子、碘原子為佳、氟原子、氯原子、溴原子更佳。烷基鹵化物可為直鏈狀亦可為分支鏈狀，以直鏈狀為佳。A2 為環狀有機基時，環狀有機基的例與Rc8 及Rc9 具有的取代基之環狀有機基相同。A2 為烷氧基羰基時，烷氧基羰基的例與Rc8 及Rc9 具有的取代基之烷氧基羰基相同。 　　[0147] Rc8 及Rc9 的較佳具體例，可舉例如乙基、n-丙基、n-丁基、n-己基、n-庚基、及n-辛基等之烷基；2-甲氧基乙基、3-甲氧基-n-丙基、4-甲氧基-n-丁基、5-甲氧基-n-戊基、6-甲氧基-n-己基、7-甲氧基-n-庚基、8-甲氧基-n-辛基、2-乙氧基乙基、3-乙氧基-n-丙基、4-乙氧基-n-丁基、5-乙氧基-n-戊基、6-乙氧基-n-己基、7-乙氧基-n-庚基、及8-乙氧基-n-辛基等之烷氧基烷基；2-氰基乙基、3-氰-n-丙基、4-氰-n-丁基、5-氰-n-戊基、6-氰-n-己基、7-氰-n-庚基、及8-氰-n-辛基等之氰基烷基；2-苯基乙基、3-苯基-n-丙基、4-苯基-n-丁基、5-苯基-n-戊基、6-苯基-n-己基、7-苯基-n-庚基、及8-苯基-n-辛基等之苯基烷基；2-環己基乙基、3-環己基-n-丙基、4-環己基-n-丁基、5-環己基-n-戊基、6-環己基-n-己基、7-環己基-n-庚基、8-環己基-n-辛基、2-環戊基乙基、3-環戊基-n-丙基、4-環戊基-n-丁基、5-環戊基-n-戊基、6-環戊基-n-己基、7-環戊基-n-庚基、及8-環戊基-n-辛基等之環烷基烷基；2-甲氧基羰基乙基、3-甲氧基羰基-n-丙基、4-甲氧基羰基-n-丁基、5-甲氧基羰基-n-戊基、6-甲氧基羰基-n-己基、7-甲氧基羰基-n-庚基、8-甲氧基羰基-n-辛基、2-乙氧基羰基乙基、3-乙氧基羰基-n-丙基、4-乙氧基羰基-n-丁基、5-乙氧基羰基-n-戊基、6-乙氧基羰基-n-己基、7-乙氧基羰基-n-庚基、及8-乙氧基羰基-n-辛基等之烷氧基羰基烷基；2-氯乙基、3-氯-n-丙基、4-氯-n-丁基、5-氯-n-戊基、6-氯-n-己基、7-氯-n-庚基、8-氯-n-辛基、2-溴乙基、3-溴-n-丙基、4-溴-n-丁基、5-溴-n-戊基、6-溴-n-己基、7-溴-n-庚基、8-溴-n-辛基、3,3,3-三氟丙基、及3,3,4,4,5,5,5-七氟-n-戊基等之烷基鹵化物。 　　[0148] Rc8 及Rc9 方面，上述中適宜之基為乙基、n-丙基、n-丁基、n-戊基、2-甲氧基乙基、2-氰基乙基、2-苯基乙基、2-環己基乙基、2-甲氧基羰基乙基、2-氯乙基、2-溴乙基、3,3,3-三氟丙基、及3,3,4,4,5,5,5-七氟-n-戊基。 　　[0149] Rc10 的適宜之有機基的例方面，與Rc7 相同地，可舉例如烷基、烷氧基、環烷基、環烷氧基、飽和脂肪族醯基、烷氧基羰基、飽和脂肪族醯基氧基、可具有取代基的苯基、可具有取代基的苯氧基、可具有取代基的苯甲醯基、可具有取代基的苯氧基羰基、可具有取代基的苯甲醯基氧基、可具有取代基的苯基烷基、可具有取代基的萘基、可具有取代基的萘氧基、可具有取代基的萘甲醯基、可具有取代基的萘氧基羰基、可具有取代基的萘甲醯基氧基、可具有取代基的萘基烷基、可具有取代基的雜環基、可具有取代基的雜環羰基、被1個或2個有機基取代的胺基、嗎啉-1-基、及哌嗪-1-基等。此等之基的具體例與Rc7 中說明者相同。又，Rc10 方面，環烷基烷基、芳香環上可具有取代基的苯氧基烷基、芳香環上可具有取代基的苯基硫烷基亦佳。苯氧基烷基、及苯基硫烷基可具有的取代基與Rc7 所含有的苯基可具有的取代基相同。 　　[0150] 有機基中，Rc10 方面，以烷基、環烷基、可具有取代基的苯基或環烷基烷基、芳香環上可具有取代基的苯基硫烷基為佳。烷基方面，以碳原子數1~20的烷基為佳、碳原子數1~8的烷基更佳、碳原子數1~4的烷基特佳、甲基最佳。可具有取代基的苯基中，以甲基苯基為佳、2-甲基苯基更佳。環烷基烷基所含有的環烷基的碳原子數，以5~10為佳、5~8更佳、5或6特別佳。環烷基烷基所含有的伸烷基的碳原子數，以1~8為佳、1~4更佳、2特別佳。環烷基烷基中，以環戊基乙基為佳。芳香環上可具有取代基的苯基硫烷基所含有的伸烷基的碳原子數，以1~8為佳、1~4更佳、2特別佳。芳香環上可具有取代基的苯基硫烷基中，以2-(4-氯苯基硫基)乙基為佳。 　　[0151] 又，Rc10 方面，以-A3 -CO-O-A4 所表示之基亦佳。A3 為2價有機基，以2價烴基者為佳、伸烷基者為佳。A4 為1價有機基，以1價烴基者為佳。 　　[0152] A3 為伸烷基時，伸烷基可為直鏈狀亦可為分支鏈狀，以直鏈狀為佳。A3 為伸烷基時，伸烷基的碳原子數以1~10為佳、1~6更佳、1~4特別佳。 　　[0153] A4 的較佳例，可舉例如碳原子數1~10的烷基、碳原子數7~20的芳烷基、及碳原子數6~20的芳香族烴基。A4 的較佳具體例，可舉例如甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、n-戊基、n-己基、苯基、萘基、苄基、苯乙基、α-萘基甲基、及β-萘基甲基等。 　　[0154] 以-A3 -CO-O-A4 所表示之基的適宜之具體例，可舉例如2-甲氧基羰基乙基、2-乙氧基羰基乙基、2-n-丙基氧基羰基乙基、2-n-丁基氧基羰基乙基、2-n-戊基氧基羰基乙基、2-n-己基氧基羰基乙基、2-苄基氧基羰基乙基、2-苯氧基羰基乙基、3-甲氧基羰基-n-丙基、3-乙氧基羰基-n-丙基、3-n-丙基氧基羰基-n-丙基、3-n-丁基氧基羰基-n-丙基、3-n-戊基氧基羰基-n-丙基、3-n-己基氧基羰基-n-丙基、3-苄基氧基羰基-n-丙基、及3-苯氧基羰基-n-丙基等。 　　[0155] 以上已在Rc10 說明，但Rc10 方面，以下述式(c4a)或(c4b)所表示之基為佳。
Figure 02_image043
(式(c4a)及(c4b)中，Rc13 及Rc14 ，各自為有機基，n6為0~4的整數，Rc13 及R8 存在於苯環上的相鄰位置時，Rc13 與Rc14 可相互鍵結形成環，n7為1~8的整數，n8為1~5的整數，n9為0~(n8+3)的整數，Rc15 為有機基。) 　　[0156] 關於式(c4a)中的Rc13 及Rc14 的有機基的例與Rc7 相同。Rc13 方面，以烷基或苯基為佳。Rc13 為烷基時，其碳原子數，以1~10為佳、1~5更佳、1~3特佳、1最佳。亦即，以Rc13 為甲基者最佳。Rc13 與Rc14 鍵結而形成環時，該環可為芳香族環，亦可為脂肪族環。為式(c4a)所表示之基，且Rc13 與Rc14 形成環之基的適宜之例，可舉例如萘-1-基或1,2,3,4-四氫萘-5-基等。上述式(c4a)中，n6為0~4的整數，以0或1者為佳、0者更佳。 　　[0157] 上述式(c4b)中，Rc15 為有機基。有機基，可舉例如與在Rc7 說明的有機基相同之基。有機基中，以烷基為佳。烷基可為直鏈狀亦可為分支鏈狀。烷基的碳原子數以1~10為佳、1~5更佳、1~3特別佳。Rc15 方面，較佳例為甲基、乙基、丙基、異丙基、丁基等，此等之中，甲基更佳。 　　[0158] 上述式(c4b)中，n8為1~5的整數，1~3的整數為佳、1或2更佳。上述式(c4b)中，n9為0~(n8+3)，以0~3的整數為佳、0~2的整數更佳、0特別佳。上述式(c4b)中，n7為1~8的整數，以1~5的整數為佳、1~3的整數更佳、1或2特別佳。 　　[0159] 式(c4)中，Rc11 為氫原子、可具有取代基的碳原子數1~11的烷基或可具有取代基的芳基。Rc11 為烷基時可具有的取代基方面，較佳例為苯基、萘基等。又，Rc7 為芳基時可具有的取代基方面，較佳例為碳原子數1~5的烷基、烷氧基、鹵素原子等。 　　[0160] 式(c4)中，Rc11 方面，較佳例為氫原子、甲基、乙基、n-丙基、異丙基、n-丁基、苯基、苄基、甲基苯基、萘基等，此等之中，甲基或苯基更佳。 　　[0161] 式(c4)所表示之化合物，藉由包含使前述式(c5)所表示之化合物所含有的肟基(＞C=N-OH)轉換為＞C=N-O-CORc11 所表示之肟酯基之步驟的方法來製造。Rc11 與式(c4)中的Rc11 相同。 　　[0162] 肟基(＞C=N-OH)的轉換為＞C=N-O-CORc11 所表示之肟酯基，係藉由使前述式(c5)所表示之化合物與醯基化劑反應而進行。 　　賦予-CORc11 所表示之醯基的醯基化劑方面，可舉例如(Rc11 CO)2 O所表示之酸酐或Rc11 COHal(Hal為鹵素原子)所表示之酸鹵化物。 　　[0163] 一般式(c4)所表示之化合物，在n5為0時，例如根據下述路徑3進行合成。在路徑3，使用下述式(c3-1)所表示之茀衍生物作為原料。Rc7 為硝基或1價有機基時，式(c3-1)所表示之茀衍生物可在9位被Rc8 及Rc9 取代的茀衍生物，以習知方法，導入取代基Rc7 而得到。9位以Rc8 及Rc9 取代的茀衍生物，例如Rc8 及Rc9 為烷基時，如特開平06-234668號公報記載，可在鹼金屬氫氧化物的存在下，非質子性極性有機溶劑中，使茀與烷基化劑反應而得到。又，藉由在茀之有機溶劑溶液中，添加烷基鹵化物般烷基化劑、鹼金屬氫氧化物的水溶液、碘化四丁基銨或叔丁醇鉀般相間移動觸媒，進行烷基化反應，可得到9,9-烷基取代茀。 　　[0164] 於式(c3-1)所表示之茀衍生物，藉由傅里德-克拉夫茨醯基化反應，導入-CO-Rc10 所表示之醯基，可得到式(c3-3)所表示之茀衍生物。為了導入-CO-Rc10 所表示之醯基用的醯基化劑可為鹵代羰基化合物，亦可為酸酐。醯基化劑方面，以式(c3-2)所表示之鹵代羰基化合物為佳。式(c3-2)中，Hal為鹵素原子。茀環上導入醯基的位置，可藉由適當變更Friedel-Crafts反應的條件、對被醯基化的位置之其他位置施以保護及脫保護之方法來選擇。 　　[0165] 接著，將得到的式(c3-3)所表示之茀衍生物中的-CO-Rc10 所表示之基變換為-C(=N-OH)-Rc10 所表示之基，得到式(c3-4)所表示之肟化合物。將-CO-Rc10 所表示之基變換為-C(=N-OH)-Rc10 所表示之基的方法雖不特別限制，以羥基胺之肟化為佳。使式(c3-4)的肟化合物與下式(c3-5)所表示之酸酐((Rc11 CO)2 O)或下述式(c3-6)所表示之酸鹵化物(Rc11 COHal、Hal為鹵素原子。)反應，可得到下述式(c3-7)所表示之化合物。 　　[0166] 又，式(c3-1)、(c3-2)、(c3-3)、(c3-4)、(c3-5)、(c3-6)、及(c3-7)中，Rc7 、Rc8 、Rc9 、Rc10 、及Rc11 與式(c4)相同。 　　[0167] 又，路徑3中，式(c3-2)、式(c3-3)、及式(c3-4)各自所含有的Rc10 ，可為相同亦可為相異。亦即，式(c3-2)、式(c3-3)、及式(c3-4)中的Rc10 在路徑3所示之合成過程中，可接受化學修飾。化學修飾之例，可舉例如酯化、醚化、醯基化、醯胺化、鹵素化、胺基中的氫原子經有機基之取代等。Rc10 可接受的化學修飾不限於此等。 　　[0168] ＜路徑3＞
Figure 02_image045
[0169] 式(c4)所表示之化合物，在n5為1時，例如依據下述路徑4進行合成。在路徑4，使用下述式(c4-1)所表示之茀衍生物作為原料。式(c4-1)所表示之茀衍生物，可藉由路徑3相同之方法，於式(c3-1)所表示之化合物，以Friedel-Crafts反應導入-CO-CH2 -Rc10 所表示之醯基而得到。醯基化劑方面，以式(c3-8):Hal-CO-CH2 -Rc10 所表示之羧酸鹵化物為佳。接著，使式(c4-1)所表示之化合物中的存在於Rc10 與羰基之間的亞甲基進行肟化，得到下式(c4-3)所表示之酮肟化合物。將亞甲基肟化之方法，雖不特別限制，以在鹽酸存在下使下述一般式(c4-2)所表示之亞硝酸酯(RONO、R為碳原子數1~6的烷基。)進行反應之方法為佳。接著，使下述式(c4-3)所表示之酮肟化合物與下述式(c4-4)所表示之酸酐(Rc11 CO)2 O)或下述式(c4-5)所表示之酸鹵化物(Rc11 COHal、Hal為鹵素原子。)進行反應，可得到下述式(c4-6)所表示之化合物。又，下述式(c4-1)、(c4-3)、(c4-4)、(c4-5)、及(c4-6)中，Rc7 、Rc8 、Rc9 、Rc10 、及Rc11 與式(c4)相同。 　　n5為1時，有可使在使用含有式(c4)所表示之化合物的感光性樹脂組成物所形成的圖型中異物的產生更降低之傾向。 　　[0170] 又，路徑4中，式(c3-8)、式(c4-1)、及式(c4-3)各自所含有的Rc10 ，可為相同亦可為相異。亦即，式(c3-8)、式(c4-1)、及式(c4-3)中的Rc10 在路徑4所示之合成過程中，可接受化學修飾。化學修飾之例，可舉例如酯化、醚化、醯基化、醯胺化、鹵素化、胺基中的氫原子經有機基之取代等。Rc10 可接受的化學修飾不限於此等。 　　[0171] ＜路徑4＞
Figure 02_image047
[0172] 式(c4)所表示之化合物的適宜之具體例，可舉例如以下之PI-43~PI-83。
Figure 02_image049
[0173]
Figure 02_image051
[0174] 光聚合起始劑(C)之含量，相對於除去後述之有機溶劑(S)之質量的感光性樹脂組成物的質量，以0.5~30質量%為佳、1~20質量%更佳。光聚合起始劑(C)之含量藉由在上述範圍，可得到硬化性良好、不易產生圖型形狀不良的感光性樹脂組成物。 　　[0175] 光聚合起始劑(C)方面，有併用肟酯化合物與肟酯化合物以外的其他光聚合起始劑之情形，肟酯化合物相對於光聚合起始劑(C)之質量的比率以50質量%以下為佳、1質量%以上50質量%以下更佳、3質量%以上30質量%以下特佳、5質量%以上20質量%以下最佳。 　　光聚合起始劑(C)含有該範圍內之量的肟酯化合物時，尤其難以形成寬度大於期望寬度的經圖型化的低折射率膜。 　　[0176] 光聚合起始劑(C)中可組合光起始助劑。光起始助劑方面，可舉例如三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基安息香酸甲基酯、4-二甲基胺基安息香酸乙基酯、4-二甲基胺基安息香酸異戊基酯、4-二甲基胺基安息香酸2-乙基己基酯、安息香酸2-二甲基胺基乙基酯、N,N-二甲基對-甲苯胺、4,4’-雙(二甲基胺基)二苯甲酮、9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二乙氧基蒽、2-乙基-9,10-二乙氧基蒽、2-巰基苯並噻唑、2-巰基苯並噁唑、2-巰基苯並咪唑、2-巰基-5-甲氧基苯並噻唑、3-巰基丙酸、3-巰基丙酸甲基酯、季戊四醇四巰基乙酸酯、3-巰基丙酸酯等之硫醇化合物等。此等之光起始助劑可單獨或2種以上組合使用。 　　[0177] ＜填料(D)＞ 　　感光性樹脂組成物，為了形成具有期望程度之低折射率的低折射率膜而含有填料(D)。填料(D)在不阻礙本發明之目的範圍，由以往低折射率膜之形成所使用的感光性樹脂組成物中摻混的填料中來適宜選擇。該填料(D)方面，以中空粒子或多孔質粒子為佳。 　　填料(D)方面，可使用1種類之粒子，亦可組合使用2種以上之粒子。又，填料(D)方面，可將中空粒子與多孔質粒子組合使用。 　　[0178] 中空粒子係指內部具有被外殼包圍的空洞之粒子。多孔質粒子係指內部具有許多空隙之多孔質的粒子。 　　中空粒子或多孔質粒子的空隙率，由填料(D)的耐久性為良好觀點與容易形成低折射率的低折射率觀點來看，以10~80%為佳、20~60%更佳、30~60%特別佳。 　　[0179] 在中空粒子與多孔質粒子，由容易使低折射率膜之折射率更低觀點來看，以中空粒子更佳。 　　例如中空二氧化矽粒子的折射率，比一般的二氧化矽之折射率1.46顯著低。此係因為中空二氧化矽粒子內部包含顯示1.0的低折射率之空氣。 　　[0180] 填料(D)的平均粒子徑在不阻礙本發明之目的範圍，不特別限定。填料(D)的平均粒子徑，以1~200nm為佳、10~100nm更佳。 　　填料(D)的平均粒子徑係由將分散的填料粒子以透過型電子顯微鏡觀察而得到的圖像求出。具體上，為以下之過程1)~3) 　　1)求出複數個之填料粒子各自之投影面積。 　　2)由求的得投影面積求出各填料粒子的等效圓直徑。 　　3)算出複數個之填料粒子的等效圓直徑的數平均值，作為填料(D)的平均粒子徑。 　　又，平均粒子徑的測定，典型上以300個以上之填料粒子為對象進行。 　　[0181] 填料(D)的比表面積，以10~2000m2 /g為佳、20~1800m2 /g更佳、50~1500m2 /g特別佳。 　　[0182] 填料(D)為中空粒子或多孔質粒子時，其折射率以1.10~1.40為佳、1.15~1.35更佳、1.15~1.30特別佳。在此之折射率為作為粒子全體的折射率，粒子為中空粒子時，非表示僅形成中空粒子的外殼之折射率者。粒子為多孔質粒子時，多孔質粒子的折射率可使用阿貝折射率計(ATAGO 公司製)進行測定。 　　[0183] 中空粒子或多孔質粒子的材質，由低折射率膜之低折射率化觀點來看，以無機材料者為佳。該無機材料方面，可舉例如氟化鎂或二氧化矽之粒子。無機材料可為結晶性材料亦可為非晶質材料。 　　由容易形成低折射率的低折射率膜、容易在感光性樹脂組成物中安定地分散、及便宜之觀點來看，無機材料所構成的中空粒子或多孔質粒子方面，以中空二氧化矽粒子或多孔質二氧化矽粒子為佳。 　　無機中空粒子或無機多孔質粒子的平均一次粒徑以1~100nm為佳、1~60nm更佳。 　　無機中空粒子或多孔質二氧化矽粒子，可為單分散粒子，亦可包含一次粒子凝集而成的凝集體。 　　[0184] 填料(D)為無機粒子時，以使填料(D)的分散液中或在感光性樹脂組成物中的填料(D)的分散安定性提升之目的或提高與樹脂(A)等之成分的親和性或鍵結性之目的，在無機粒子的表面，可施以電漿放電處理或電暈放電處理般物理性表面處理、界面活性劑或偶合劑等之化學性表面處理。 　　該表面處理中，以使用偶合劑的化學性表面處理為佳。 　　偶合劑方面，以鈦偶合劑、矽烷偶合劑等為佳、矽烷偶合劑更佳。 　　[0185] 例如將二氧化矽粒子以矽烷偶合劑處理，則藉由矽烷偶合劑與二氧化矽粒子表面之矽烷醇基的反應，有機矽烷基鍵結於二氧化矽粒子的表面。 　　經矽烷偶合劑之處理而導入的有機基方面，可舉例如可具有不飽和鍵的碳原子數1~18的烴基、可具有不飽和鍵的碳原子數1~18的鹵素化烴基等。 　　偶合劑之表面處理可在填料(D)之無機粒子摻混於感光性樹脂組成物前進行。又，亦可藉由將偶合劑添加至感光性樹脂組成物，進行填料(D)的表面處理。 　　[0186] 無機粒子等之填料(D)由防止凝集、在感光性組成物中的分散為容易之觀點來看，以調製感光性樹脂組成物前，預先在媒體中分散者為佳。 　　[0187] 作為填料(D)使用二氧化矽粒子時，可宜使用市售的二氧化矽粒子。 　　市售的二氧化矽粒子的具體例，可舉例如日揮觸媒化成(股)製的蘇利亞系列(異丙醇(IPA)分散液、4-甲基-2-戊酮(MIBK)分散液等)；日揮觸媒化成(股)製的OSCAL系列；日產化學(股)製的SNOWTEX系列(IPA分散液、乙二醇分散液、甲基乙基酮(MEK)分散液、二甲基乙醯胺分散液、MIBK分散液、丙二醇單甲基乙酸酯分散液、丙二醇單甲基醚分散液、甲醇分散液、乙酸乙基酯分散液、乙酸丁基酯分散液、二甲苯-n-丁醇分散液、甲苯分散液等)；日鐵礦業(股)製的Silinax；扶桑化學工業(股)製的PL系列(IPA分散液、甲苯分散液、丙二醇單甲基醚分散液、甲基乙基酮分散液等)；EVONIK公司製的AEROSIL系列(丙二醇乙酸酯分散液、乙二醇分散液、MIBK分散液等)。 　　[0188] 前述之填料(D)，以作為分散於媒體中的分散液，摻混於感光性樹脂組成物者為佳。 　　將二氧化矽粒子以分散液摻混於感光性樹脂組成物時，分散液中的二氧化矽粒子之含量以10~50質量%為佳、15~40質量%更佳、15~30質量%尤佳。 　　[0189] 將填料(D)分散於媒體中或感光性樹脂組成物中時，可使用分散劑。 　　分散劑的具體例，可舉例如聚醯胺胺、聚醯胺胺之鹽、聚羧酸、聚羧酸鹽、高分子量不飽和酸酯、改性聚胺基甲酸酯、改性聚酯、改性聚(甲基)丙烯酸酯、(甲基)丙烯酸系共聚物、及萘磺酸甲醛縮合物等之分散樹脂。 　　又，可使用聚氧化乙烯烷基磷酸酯、聚氧化乙烯烷基胺、烷醇胺等之化合物作為分散劑。 　　上述分散劑中，以分散樹脂為佳。分散樹脂由其構造，可分為直鏈狀高分子、末端改性型高分子、接枝型高分子、嵌段型高分子。 　　[0190] 分散樹脂具有吸附於填料粒子的表面，防止填料粒子的凝集之作用。因此，較佳可舉例如具有對填料粒子表面之錨部位的末端改性型高分子、接枝型高分子、嵌段型高分子。 　　[0191] 分散樹脂之質量平均分子量(以GPC法測定的聚苯乙烯換算值)以1000~200000為佳、2000~100000更佳、5000~50000特別佳。 　　[0192] 分散樹脂可以市售品取得。 　　市售之分散樹脂的具體例方面，可舉例如 　　BYKChemie公司製的Disperbyk-101(聚醯胺胺磷酸鹽)、Disperbyk-107(羧酸酯)、Disperbyk-110(含酸基之共聚合物)、Disperbyk-111(聚醯胺)、Disperbyk-130(聚醯胺)、Disperbyk-161(高分子共聚合物)、Disperbyk-162(高分子共聚合物)、Disperbyk-163(高分子共聚合物)、Disperbyk-164(高分子共聚合物)、Disperbyk-165(高分子共聚合物)、Disperbyk-166(高分子共聚合物)、Disperbyk-170(高分子共聚合物)、BYK-P104(高分子量不飽和聚羧酸)、BYK-P105(高分子量不飽和聚羧酸)； 　　EFKA公司製的EFKA4047(聚胺基甲酸酯)、EFKA4050~4010~4165(聚胺基甲酸酯)、EFKA4330~4340(嵌段共聚物)、EFKA4400~4402(改性聚丙烯酸酯)、EFKA5010(聚酯醯胺)、EFKA5765(高分子量聚羧酸鹽)、EFKA6220(脂肪酸聚酯)、EFKA6745(酞菁衍生物)、EFKA6750(偶氮顏料衍生物)； 　　味之素精細技術公司製的Ajisper PB821、Ajisper PB822； 　　共榮社化學公司製的Florene TG-710(胺基甲酸酯寡聚物)、polyflow No.50E(丙烯酸系共聚物)、polyflow No.300(丙烯酸系共聚物)； 　　楠本化成公司製的DISPARLON KS-860(高分子聚酯胺鹽)、DISPARLON KS-873SN(高分子聚酯胺鹽)、DISPARLON KS-874(高分子聚酯胺鹽)、DISPARLON 2150(脂肪族多價羧酸)、DISPARLON 7004(聚醚酯)、DISPARLON DA-703-50、DISPARLON DA-705、DISPARLON DA-725； 　　花王公司製的Demol RN(萘磺酸甲醛聚縮合物)、Demol N(萘磺酸甲醛聚縮合物)、Demol MS(芳香族磺酸甲醛聚縮合物)、Demol C(芳香族磺酸甲醛聚縮合物)、Demol SN-B(芳香族磺酸甲醛聚縮合物)、HOMOGENOL L-18(高分子聚羧酸)、EMULGEN 920(聚氧化乙烯壬基苯基醚)、EMULGEN 930(聚氧化乙烯壬基苯基醚)、EMULGEN 935(聚氧化乙烯壬基苯基醚)、EMULGEN 985(聚氧化乙烯壬基苯基醚)、Acetamine 86(硬脂醯基胺乙酸酯)； 　　Lubrizol 公司製的SOLSPERSE 5000(酞菁衍生物)、SOLSPERSE 22000(偶氮顏料衍生物)、SOLSPERSE 13240(聚酯胺)、SOLSPERSE 3000(末端改性聚合物)、SOLSPERSE 17000(末端改性聚合物)、SOLSPERSE 27000(末端改性聚合物)、SOLSPERSE 24000(接枝型高分子)、SOLSPERSE 28000(接枝型高分子)、SOLSPERSE 32000(接枝型高分子)、SOLSPERSE 38500(接枝型高分子)； 　　日光化學公司製的NIKKOL T106(聚氧化乙烯山梨糖醇酐單油酸酯)、MYS-IEX(聚氧化乙烯單硬脂酸酯)； 　　森下產業公司製的EFKA-46、EFKA-47、EFKA-47EA、EFKA聚合物100、EFKA聚合物400、EFKA聚合物401、EFKA聚合物450； 　　Sannopco公司製的DISPERSE AID 6、DISPERSE AID 8、DISPERSE AID 15、DISPERSE AID 9100。 　　[0193] 又，分散劑方面，可使用非離子性、陰離子性、陽離子性界面活性劑。此等之界面活性劑可以市售品取得。 　　市售之界面活性劑的具體例方面，可舉例如 　　EFKA公司製的EFKA-745； 　　信越化學工業公司製之有機矽氧烷聚合物KP341； 　　共榮社油脂化學工業公司製的聚合物polyflow No.75、聚合物polyflow No.90、聚合物polyflow No.95； 　　裕商公司製的W001、W004、W005、W017； 　　日本Lubrizol公司製的SOLSPERSE 3000、SOLSPERSE 5000、SOLSPERSE 9000、SOLSPERSE 12000、SOLSPERSE 13240、SOLSPERSE 13940、SOLSPERSE 17000、SOLSPERSE 24000、SOLSPERSE 26000、SOLSPERSE 28000； 　　ADEKA公司製的AdekaPluronicL31、AdekaPluronicF38、AdekaPluronicL42、AdekaPluronicL44、AdekaPluronicL61、AdekaPluronicL64、AdekaPluronicF68、AdekaPluronicL72、AdekaPluronicP95、AdekaPluronicF77、AdekaPluronicP84、AdekaPluronicF87、AdekaPluronicP94、AdekaPluronicL101、AdekaPluronicP103、AdekaPluronicF108、AdekaPluronicL121、AdekaPluronicP-123； 　　三洋化成公司製的Isonetto S-20； 　　Kawaken Fine Chemicals 公司製的HINOACT T-8000E； 　　青木油脂工業公司製的ELEBASE BA-100、ELEBASE BA-200、ELEBASE BCP-2、ELEBASE BUB-3、ELEBASE BUB-4、ELEBASE CP-800K、ELEBASE EDP-475、ELEBASE HEB-5、FINESURF 270、FINESURF 7045、FINESURF 7085、BLAUNON DSP-12.5、BLAUNON DT-03、BLAUNON L-205、BLAUNON LPE-1007、BLAUNON O-205、BLAUNON S-202、BLAUNON S-204、BLAUNON S-207、BLAUNON S-205T； 　　花王公司製的EMULGEN A-500、EMULGEN PP-290、AMIET 102、AMIET 105、AMIET 302、AMIET 320、AMINON PK-02S、EMANON CH-25、EMULGEN 104P、EMULGEN 108、EMULGEN 404、EMULGEN 408、EMULGEN A-60、EMULGEN A-90、EMULGEN B-66、EMULGEN LS-106、EMULGEN LS-114、RHEODOL 430V、RHEODOL 440V、RHEODOL 460V、RHEODOL TW-S106、RHEODOL TW-S120V、RHEODOL SUPER TW-L120、PHOSPHANOL ML-200、EMAL 20T、EMAL E-27、NEOPELEX GS、PELEX NBL、PELEX SS-H、PELEX SS-L、POIZ 532A、LATEMUL ASK、LATEMUL E-118B、LATEMUL E-150； 　　竹本油脂公司製的Newkalgen 3000S、Newkalgen FS-3PG、Newkalgen FE-7PG、Pionin D-6414、Pionin A-24-EA、Pionin A-28-B、Pionin A-29-M、Pionin A-44-B、Pionin A-44TW； 　　日信化學工業公司製的Dynol 604、Olfine PD-002W、SURFYNOL 2502、SURFYNOL 440、SURFYNOL 465、SURFYNOL 485、SURFYNOL 61； 　　Clariant公司製的EMULSOGEN COL-020、EMULSOGEN 070、EMULSOGEN 080、 　　第一工業製藥公司製的PLYSURF A208B、PLYSURF A210B、PLYSURF A210G、PLYSURF A219B、PLYSURF AL、Lavelin FC-45； 　　Nippon Surfactant 公司製的AKYPO RLM100NV、AKYPO RLM45、AKYPO RLM45NV、AKYPO ECT-3、AKYPO ECT-3NEX、AKYPO ECT-7、Phosten HLP、Phosten HLP-1、Phosten HLP-TEA。 　　此等之分散劑可單獨使用亦可2種以上組合使用。 　　[0194] 感光性樹脂組成物中之分散劑之含量，相對填料之質量，以1~100質量%為佳、5~80質量%更佳、10~60質量%特別佳。分散劑為分散樹脂時，分散劑的使用量，相對填料之質量，以5~100質量%為佳、10~80質量%更佳。 　　[0195] 感光性樹脂組成物含有填料(D)時，感光性樹脂組成物中之填料(D)的使用量在不阻礙本發明之目的範圍，不特別限定。感光性樹脂組成物中之填料(D)之含量，相對於除去後述之有機溶劑(S)之質量的感光性樹脂組成物的質量，以80質量%以下為佳、20~80質量%更佳、30~70質量%特別佳。 　　[0196] ＜含氟之界面活性劑(E)＞ 　　感光性樹脂組成物必須含有含氟之界面活性劑(E)。感光性樹脂組成物中之含氟之界面活性劑(E)之含量，相對於感光性樹脂組成物中的樹脂(A)之質量與光聚合性化合物(B)之質量與填料(D)之質量之合計而言，為0.05~3質量%。 　　感光性樹脂組成物藉由含有該範圍之量的含氟之界面活性劑(E)，可使感光性樹脂組成物在基板上均勻地塗佈，且即使低曝光量的曝光亦不產生殘渣，可形成經保護膠帶剝離而亦不易產生表面的粗糙之低折射率膜。 　　含氟之界面活性劑(E)為含有氟原子之界面活性劑，則不特別限制，可為陰離子性界面活性劑、陽離子性界面活性劑、及非離子性界面活性劑任一。 　　含氟之界面活性劑(E)可組合使用2種以上。 　　[0197] 含氟之界面活性劑的具體例方面，可舉例如BM-1000、BM-1100(皆為BM化學公司製)、MEGAFACF142D、MEGAFACF172、MEGAFACF173、MEGAFACF183(皆為大日本油墨化學工業公司製)、FluoradFC-135、FluoradFC-170C、FluoradFC-430、FluoradFC-431(皆為住友3M公司製)、SurflonS-112、SurflonS-113、SurflonS-131、SurflonS-141、SurflonS-145(皆為旭硝子公司製)、SH-28PA、SH-190、SH-193、SZ-6032、SF-8428(皆為東麗矽酮公司製)等之市售的氟系界面活性劑，但不限於此等。 　　[0198] 又，含氟之界面活性劑方面，側鏈具有氟烷基之化合物亦佳。 　　側鏈具有氟烷基的化合物方面，可舉例如下述式(e-1)~(e-3)所表示之化合物。 　　式(e-1)及式(e-2)中，x1為0~7的整數。 　　式(e-3)中，x2為0~8的整數。 　　式(e-4)中，x3為6~20的整數。
Figure 02_image053
Figure 02_image055
Figure 02_image057
[0199] 含氟之界面活性劑(E)之含量，相對於感光性組成物中的樹脂(A)之質量與光聚合性化合物(B)之質量與填料(D)之質量之合計而言，為0.05~3質量%、以0.05~2質量%為佳、0.10~1.5質量%更佳、0.15~1質量%最佳。 　　[0200] ＜聚合抑制劑(F)＞ 　　感光性樹脂組成物以因應必要含有聚合抑制劑(F)者為佳。感光性樹脂組成物藉由含有聚合抑制劑，容易抑制經圖型化的低折射率膜之寬度比指定尺寸要大。 　　聚合抑制劑(F)的種類不特別限制，可使用以往被使用來禁止具有不飽和雙鍵的化合物的聚合之聚合抑制劑的化合物。 　　[0201] 聚合抑制劑(F)方面，以分子量230~1500之受阻酚系化合物為佳。理由雖不明，但感光性樹脂組成物藉由含有具有上述指定範圍內之分子量的受阻酚系化合物作為聚合抑制劑(F)，在範圍廣泛的曝光量下，容易形成具有期望尺寸的良好形狀的圖型且無殘渣產生。 　　又，聚合抑制劑(F)的分子量過小，則圖型形成時容易產生殘渣。聚合抑制劑(F)的分子量過大，則在感光性樹脂組成物中，因聚合抑制劑(F)局部化，而有難以得到使用聚合抑制劑(F)所致之期望的效果之情形。 　　[0202] 受阻酚係指酚性羥基的2個鄰位之至少一者具有氫原子及甲基以外的大體積取代基者。大體積取代基方面，例如甲基以外的烷基、烯基、炔基、芳基、雜環式基、烷氧基、芳基氧基、取代胺基、硫烷基、硫基苯基等。 　　[0203] 分子量230~1500之受阻酚系化合物為具有指定範圍內的分子量，且具有作為聚合抑制劑之作用的受阻酚系化合物則不特別限定。 　　分子量230~1500之受阻酚系化合物的具體例，可舉例如2,5-雙(1,1,3,3-四甲基丁基)對苯二酚(334.5)、2,5-雙(1,1-二甲基丁基)對苯二酚(250.4)、季戊四醇肆[3-(3,5-二-tert-丁基-4-羥基苯基)丙酸酯](1177.6)、N,N’-己烷-1,6-二基雙[3-(3,5-二-tert-丁基-4-羥基苯基)丙醯胺](637.0)、1,3,5-參(3,5-二-tert-丁基-4-羥基苄基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮(784.1)、4,4’,4”-(1-甲基-3-亞丙基)參(6-tert-丁基-m-甲酚(544.8)、6,6’-二-tert-丁基-4,4’-亞丁基二-m-甲酚(382.6)、十八基 3-(3,5-二-tetr-丁基-4-羥基苯基)丙酸酯(530.9)、3,9-雙{2-[3-(3-tert-丁基-4-羥基-5-甲基苯基)丙醯基氧基]-1,1-二甲基乙基}-2,4,8,10-四氧雜螺[5.5]十一烷(741.0)、1,3,5-參(3,5-二-tert-丁基-4-羥基苯基甲基)-2,4,6-三甲基苯(775.2)、2,2’-硫基二乙基雙[3-(3,5-二-tert-丁基-4-羥基苯基)丙酸酯](642.9)、異辛基 3-(3,5-二-tetr-丁基-4-羥基苯基)丙酸酯(390.6)、鈣雙[3,5-二(tert-丁基)-4-羥基苄基(乙氧基)膦酸酯](692.8)、雙[3-(3-tert-丁基-4-羥基-5-甲基苯基)丙酸][乙烯雙(氧基乙烯)](586.8)、1,6-己二醇雙[3-(3,5-二-tert-丁基-4-羥基苯基)丙酸酯](638.9)、及4-[[4,6-雙(辛基硫基)-1,3,5-三嗪-2-基]胺基]-2,6-二-tert-丁基酚(589.0)。 　　各化合物名後括弧內的數值為各化合物的分子量。 　　聚合抑制劑(F)可組合含有2種以上之分子量230~1500之受阻酚系化合物。 　　[0204] 聚合抑制劑(F)亦可含有分子量230~1500之受阻酚系化合物以外的其他聚合抑制劑。 　　其他聚合抑制劑的具體例，可舉例如2,6-二-tert-丁基-p-甲酚(BHT)；對苯二酚、甲基對苯二酚、2,5-二-t-丁基對苯二酚、t-丁基對苯二酚等之對苯二酚化合物；p-苯醌、甲基-p-苯醌、t-丁基苯醌、2,5-二苯基-p-苯醌等之苯醌化合物；2-(2-羥基-5-甲基苯基)苯並***等之苯並***系化合物；N-亞硝基苯基羥基胺、N-亞硝基苯基羥基胺鋁鹽等之亞硝基胺系化合物；硫代二苯胺、二硫基苯甲醯基硫化物、二苄基四硫化物等之有機硫化合物；雙(1,2,2,6,6-五甲基-4-哌啶基)[{3,5-雙(1,1-二甲基乙基)-4-羥基苯基}甲基]丁基丙二酸酯等之受阻胺系化合物；p-苯二胺、N,N-二苯基-p-苯二胺等之芳香族胺；參(2,4-二-t-丁基苯基)亞磷酸酯、肆(2,4-二-tert-丁基苯基)[1,1-聯苯基]-4,4’-二基雙膦酸酯等之磷系化合物等。 　　聚合抑制劑(D)，可組合含有2種以上的分子量230~1500之受阻酚系化合物以外的其他聚合抑制劑。 　　[0205] 聚合抑制劑(F)中之分子量230~1500之受阻酚系化合物的含量，在不阻礙本發明之目的範圍，不特別限定。聚合抑制劑(F)中之分子量230~1500之受阻酚系化合物的含量，以70質量%以上為佳、80質量%以上更佳、90質量%以上特佳、100質量%者最佳。 　　[0206] 感光性樹脂組成物中之聚合抑制劑(F)之含量，在不阻礙本發明之目的範圍，不特別限定。聚合抑制劑(F)之含量，相對於除去填料(D)之質量與有機溶劑(S)之質量的感光性樹脂組成物的質量而言，以0.001~1質量%為佳、0.01~1質量%更佳。聚合抑制劑(F)之含量藉由在上述範圍，使感光性樹脂組成物的硬化性維持於良好的範圍，同時容易抑制經圖型化的低折射率膜之尺寸比期望的尺寸還要大。 　　[0207] ＜有機溶劑(S)＞ 　　感光性樹脂組成物為了塗佈性之改善或黏度調整，以含有有機溶劑(S)為佳。 　　[0208] 有機溶劑(S)方面，具體上，可舉例如甲醇、乙醇、n-丙醇、異丙醇、n-丁醇等之烷烴單醇；乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單-n-丙基醚、乙二醇單-n-丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單-n-丙基醚、二乙二醇單-n-丁基醚、三乙二醇單甲基醚、三乙二醇單乙基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單-n-丙基醚、丙二醇單-n-丁基醚、3-甲氧基-n-丁醇、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單-n-丙基醚、二丙二醇單-n-丁基醚、三丙二醇單甲基醚、三丙二醇單乙基醚等之(聚)烷二醇單烷基醚類；乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二乙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、丙二醇單甲基醚乙酸酯(PGMEA)、丙二醇單乙基醚乙酸酯等之(聚)烷二醇單烷基醚乙酸酯類；二乙二醇二甲基醚、二乙二醇甲基乙基醚、二乙二醇二乙基醚、四氫呋喃等之其他醚類；甲基乙基酮、環己酮、2-庚酮、3-庚酮等之酮類；2-羥基丙酸甲基酯、2-羥基丙酸乙基酯等之乳酸烷基酯類；2-羥基-2-甲基丙酸乙基酯、3-甲氧基丙酸甲基酯、3-甲氧基丙酸乙基酯、3-乙氧基丙酸甲基酯、3-乙氧基丙酸乙基酯、乙氧基乙酸乙基酯、羥基乙酸乙基酯、2-羥基-3-甲基丁烷酸甲基酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯、乙酸乙基酯、乙酸n-丙基酯、乙酸i-丙基酯、乙酸n-丁基酯、乙酸i-丁基酯、蟻酸n-戊基酯、乙酸i-戊基酯、乙酸苄基酯、丙酸n-丁基酯、丁酸乙基酯、丁酸n-丙基酯、丁酸i-丙基酯、丁酸n-丁基酯、丙酮酸甲基酯、丙酮酸乙基酯、丙酮酸n-丙基酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-側氧基丁烷酸乙基酯等之其他酯類；甲苯、二甲苯等之芳香族烴類；N-甲基-2-吡咯烷酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N,N-二甲基異丁基醯胺、N,N-二乙基乙醯胺、N,N-二乙基甲醯胺、N-甲基己內醯胺、1,3-二甲基-2-咪唑啉酮、吡啶、及N,N,N’,N’-四甲基脲等含氮極性有機溶劑；等。 　　[0209] 此等之中，以烷烴單醇、烷二醇單烷基醚類、烷二醇單烷基醚乙酸酯類、上述之其他醚類、乳酸烷基酯類、上述之其他酯類為佳、烷二醇單烷基醚乙酸酯類、上述之其他醚類、乙酸苄基酯等之上述之其他酯類更佳。 　　又，在各成分之溶解性等之點，有機溶劑(S)含有含氮極性有機溶劑者亦佳。含氮極性有機溶劑方面，可使用N,N,N’,N’-四甲基脲等。 　　此等之溶劑可單獨或2種以上組合使用。 　　[0210] 有機溶劑(S)之含量不特別限制，以可塗佈於基板等之濃度，因應塗佈膜厚適宜設定。例如感光性樹脂組成物的黏度以1~500cp為佳、1~50cp較佳、1~30cp再更佳。又，感光性樹脂組成物的固形分濃度以1~50質量%為佳、1~20質量%更佳。 　　[0211] ＜其他成分＞ 　　感光性樹脂組成物中，因應必要可含有前述含氟之界面活性劑以外的界面活性劑、光產酸劑、密著性提升劑、熱聚合抑制劑、消泡劑、著色劑、矽烷偶合劑等之添加劑。任一添加劑皆可使用以往已知者。 　　[0212] 使感光性樹脂組成物的塗佈膜曝光而使其硬化時，在低折射率膜之表面藉由阻礙氧之硬化，低折射率膜之表面的硬化度稍低。因此，在表面的硬化度稍低的低折射率膜之表面黏貼保護膠帶，則將保護膠帶剝離時，容易產生低折射率膜之表面的粗面化。 　　但是感光性樹脂組成物含有具有藉由環氧基等之酸的作用而可交聯的官能基的樹脂時，感光性樹脂組成物含有酸產生劑，則藉由曝光而產生之酸，交聯性基間的交聯即使在低折射率膜之表面亦進行，低折射率膜之表面充分地硬化。 　　因此，即使將保護膠帶由低折射率膜剝離，低折射率膜之表面亦不易粗糙。 　　[0213] 又，感光性樹脂組成物由容易形成形狀良好，且對基板之密著性優異的低折射率膜之觀點來看，以含有矽烷偶合劑者為佳。矽烷偶合劑方面，可無特別限制使用以往已知者。 　　[0214] 界面活性劑方面，可舉例如陰離子系、陽離子系、非離子系等之化合物，熱聚合抑制劑方面，可舉例如氫醌、氫醌單乙基醚等，消泡劑方面，可舉例如矽酮系、氟系化合物等。 　　[0215] ＜感光性樹脂組成物的調製方法＞ 　　以上說明的感光性樹脂組成物可藉由將上述各成分以各自指定量混合後，以攪拌機進行均勻混合而得到。又，為了使得到的混合物成為更均勻者，可使用過濾器進行過濾。 　　[0216] ≪低折射率膜之製造方法≫ 　　低折射率膜之製造方法方面，可無特別限定地採用使用含有(B)光聚合性化合物的感光性樹脂組成物的以往已知的低折射率膜之製造方法。 　　[0217] 低折射率膜的較佳製造方法方面，可舉例如包含 　　形成前述感光性樹脂組成物的塗佈膜、 　　使塗佈膜因應指定圖型進行位置選擇性地曝光、 　　使經曝光的塗佈膜顯影之方法。 　　[0218] 為了使用感光性樹脂組成物形成低折射率膜，首先將感光性樹脂組成物塗佈於因應低折射率膜之用途而選擇的基板上，形成塗佈膜。 　　基板方面，在形成圖像傳感器之情形，例如使用在矽等之半導體層上具備RGB的著色膜，在該著色膜上具備微透鏡之基板。 　　[0219] 塗佈膜之形成方法雖不特別限制，例如可使用輥式塗佈機、逆式塗佈機、棒塗佈機等之接觸轉印型塗佈裝置或旋塗機(旋轉式塗佈裝置)、淋幕式塗佈機等之非接觸型塗佈裝置進行。 　　[0220] 塗佈的感光性樹脂組成物，因應必要使其乾燥，構成塗佈膜。乾燥方法不特別限制，例如(1)以加熱板在80~120℃、較佳為90~100℃的溫度，進行60~120秒鐘使其乾燥之方法、(2)在室溫放置數小時~數日之方法、(3)置入溫風加熱器或紅外線加熱器中數十分鐘~數小時，將溶劑除去之方法等。 　　[0221] 接著對塗佈膜進行曝光。曝光係照射紫外線、準分子雷射光等之活性能量線來進行。曝光，例如藉由透過負型之遮罩，進行曝光之方法等，位置選擇性地進行。 　　[0222] 將塗佈膜位置選擇性地曝光後，藉由將曝光後的膜以顯影液進行顯影，未曝光部溶於顯影液而被除去，形成經圖型化的硬化膜。顯影方法不特別限制，例如可使用浸漬法、噴霧法等。顯影液係因應感光性樹脂組成物的組成而適宜選擇。顯影液方面，可使用例如氫氧化鈉、氫氧化鉀、碳酸鈉、氨、4級銨鹽等之鹼性的水溶液。 　　[0223] 接著，亦可對經圖型化的硬化膜進行烘烤(曝光後烘烤)。烘烤溫度雖不特別限制，以180~250℃為佳、220~230℃更佳。烘烤時間典型上為10~90分鐘、以20~60分鐘為佳。 　　如以上般藉由進行烘烤，可得到感光性樹脂組成物的硬化膜。 　　[0224] 如此而形成的硬化膜可宜用作為低折射率膜。硬化膜用作為低折射率膜時，低折射率膜之折射率(波長633nm、測定溫度25℃)以1.35以下為佳、1.23~1.34更佳、1.25~1.33特別佳。 　　又，低折射率膜之表面的對水之接觸角以比60°大者為佳。在該情形，尤其可不使低折射率膜之表面粗面化，而進行對低折射率膜之表面黏貼及剝離保護膠帶。 　　進一步，低折射率膜之表面粗度Ra以30nm以下者為佳。 　　[0225] 上述低折射率膜，例如可宜用在於圖像傳感器等之光學裝置中。圖像傳感器中，將上述低折射率膜用作為被覆RGB的著色膜上所形成的微透鏡之被覆層，則藉由改善入射至微透鏡之光的反射，抑制圖像傳感器中之眩光的產生。 　　[0226] 在上述光學裝置，較佳為在低折射率膜之表面黏貼保護膠帶。低折射率膜之表面具備保護膠帶。在具備保護膠帶的光學裝置，對位於與保護膠帶面相反側之面的半導體層施以研削加工。 　　上述光學裝置因為具備使用前述感光性樹脂組成物而形成的低折射率膜，研削加工後即使將保護膠帶剝離，仍維持低折射率膜之表面的平滑性。[Problems to be Solved by the Invention] [0005] For example, when the surface of a microlens formed on a coloring film of RGB formed on a semiconductor substrate such as a silicon substrate is coated with a cured film (low refractive index film), there may be a problem When the protective tape is pasted on the surface of the refractive index film, the semiconductor substrate is being ground. After the grinding, the protective tape is peeled off from the surface of the low refractive index film, but the surface of the low refractive index film is rough due to the peeling of the protective tape, and the surface of the low refractive index film is easily roughened. When the coating film of the photosensitive resin composition is exposed and cured, the surface of the low-refractive index film suppresses the curing of oxygen, and the surface of the low-refractive index film has a slightly lower degree of curing. Therefore, it is considered that the peeling of the protective tape causes the roughening of the surface of the low refractive index film. For this reason, when the photosensitive resin composition described in Patent Document 1 is used to form a low refractive index film, there is also a problem that the surface of the low refractive index film is rough due to the adhesion and peeling of the protective tape to the low refractive index film. When the low-refractive index film is formed with a low exposure amount, the problem of surface roughening of the low-refractive index film due to the protective tape becomes obvious. In addition, since the low refractive index film is an optically functional layer, it is of course desirable that the surface be smooth. Therefore, the photosensitive resin composition for forming a low-refractive-index film is also required to be uniformly coated on a substrate. Furthermore, for the coating of microlenses in image sensors, it is necessary to form a cured film as a low-refractive index film with the correct size at a specified position. When the photosensitive composition described in Patent Document 1 is used, residues are likely to be generated near the pattern after development. As a result, the apparent size of the pattern of the cured film may be larger than the expected size. [0006] The present invention is made in view of the above-mentioned problems to provide a substrate that can be uniformly coated on a substrate and has no residue even in low exposure exposure, and can form a surface that is not easy to be rough due to the adhesion and peeling of the protective tape. A photosensitive resin composition for forming a low refractive index film of a low refractive index film, a low refractive index film formed by curing the photosensitive resin composition for forming a low refractive index film, an optical device provided with the low refractive index film, and The objective is the manufacturing method of the low-refractive-index film using the said photosensitive resin composition for low-refractive-index film formation. [Means to Solve the Problem] [0007] The present inventors found that the photosensitive resin composition for forming a low refractive index film, in addition to the resin (A), the photopolymerizable compound (B), and the photopolymerization initiator (C) ), filler (D), by adding 0.05 to 3% by mass of a fluorine-containing surfactant based on the total mass of the resin (A), the photopolymerizable compound (B), and the mass of the filler (D) (E) The present invention can be completed by solving the above-mentioned problems. More specifically, the present invention provides the following. [0008] The first aspect of the present invention contains a resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a filler (D), and a fluorine-containing surfactant (E), The content of fluorine-containing surfactant (E) relative to the total of the mass of the resin (A), the mass of the photopolymerizable compound (B), and the mass of the filler (D) is a low refractive index film of 0.05 to 3% by mass Photosensitive resin composition for formation. [0009] The second aspect of the present invention is a low refractive index film formed by curing the photosensitive resin composition for forming a low refractive index film of the first aspect. [0010] The third aspect of the present invention is an optical device provided with the low refractive index film of the second aspect. [0011] The fourth aspect of the present invention is a coating film containing: forming the photosensitive resin composition for forming a low refractive index film of the first aspect, position-selectively exposing the coating film in response to a specified pattern, A method for manufacturing a patterned low refractive index film that develops an exposed coating film. [Effects of the Invention] [0012] According to the present invention, it is possible to provide a low refraction that can be uniformly coated on a substrate and does not generate residue even with low exposure exposure, and can form a protective tape adhered and peeled surface without being easy to be rough. The photosensitive resin composition for forming a low-refractive-index film of a low-refractive index film, a low-refractive-index film formed by curing the photosensitive resin composition for forming a low-refractive-index film, an optical device equipped with the low-refractive A method of manufacturing a low refractive index film of a photosensitive resin composition for forming a refractive index film. [Best Mode for Carrying Out the Invention] [0013] Hereinafter, the present invention will be described based on a suitable embodiment. In addition, the "~" in the specification of the present invention means from above (lower limit) to below (upper limit) unless it is particularly limited. In the specification of the present invention, only the case of "photosensitive resin composition" is described, and unless otherwise specified, it means "photosensitive resin composition for forming a low refractive index film". In the specification of the present invention, "(meth)acrylate" includes both acrylate and methacrylate. In the specification of the present invention, the "(meth)acrylic group" includes both an acrylic group and a methacrylic group. In the specification of the present invention, the "(meth)acryloyl group" includes both an acryloyl group and a methacryloyl group. [0014] ≪Photosensitive resin composition for forming low refractive index film≫ Photosensitive resin composition for forming low refractive index film, except for resin (A), photopolymerizable compound (B), and photopolymerization initiator (C) , Filler (D), relative to the total mass of resin (A), photopolymerizable compound (B) and filler (D), containing 0.05~3% by mass of fluorine-containing surfactant (E) . The photosensitive resin composition contains the fluorine-containing surfactant (E) in the above-specified range, so that the photosensitive resin composition can be uniformly coated on the substrate, and there is no residue even when exposed to low exposure. , Can form a low refractive index film that is adhered and peeled off by the protective tape, and the surface is not easy to be rough. The essential or optional components contained in the photosensitive resin composition for forming a low-refractive index film will be described below. [0015] <Resin (A)> The photosensitive resin composition for forming a low refractive index film contains a resin (A). The resin (A) is a component that imparts film-forming properties that can form a coating film and a patterned film in the photosensitive resin composition for pattern formation. As resin (A), it is not specifically limited if it is resin blended in the photosensitive resin composition for pattern formation conventionally. As the resin (A), a patterned cured film having a good shape can be easily formed, and an alkali-soluble resin is preferred. The photosensitive resin composition containing an alkali-soluble resin is soluble in an alkali developer, and the photosensitive resin composition exposed to light hardens. Therefore, the position-selectively exposed photosensitive resin composition coating film is developed using an alkali developer, and only the unexposed part is dissolved in the alkali developer, while the cured exposed part remains, and the patterned cured film Formed as a low refractive index film. [0016] Alkali-soluble resin refers to a resin solution with a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate), a resin film with a thickness of 1 μm is formed on a substrate, and a tetramethyl group with a concentration of 0.05% by mass is used. When immersed in an aqueous solution of ammonium hydroxide (TMAH) for 1 minute, a film thickness of 0.01 μm or more dissolved. [0017] A preferable example of the alkali-soluble resin includes, for example, a resin (A1) having a Cardo structure. By using a photosensitive resin composition containing a resin (A1) having a Cardo structure as an alkali-soluble resin, it is easy to form an excellent low refractive index film with a balance of heat resistance, mechanical properties, solvent resistance, and chemical resistance. [0018] The resin (A1) having a Cardo structure is not particularly limited, and conventionally known resins can be used. Among them, the resin represented by the following formula (a-1) is preferred. [0019]
Figure 02_image001
[0020] In the above formula (a-1), X a It is a group represented by the following formula (a-2). [0021]
Figure 02_image003
[0022] In the above formula (a-2), R a1 Each independently, is a hydrogen atom, a hydrocarbon group with 1 to 6 carbon atoms or a halogen atom, R a2 Each independently, is a hydrogen atom or a methyl group, W a It is a single bond or a group represented by the following formula (a-3). [0023]
Figure 02_image005
[0024] Furthermore, in the above formula (a-1), Y a It is the residue of the acid anhydride group (-CO-O-CO-) removed from the dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylendo-methylenetetrahydrophthalic anhydride. Dicarboxylic acid anhydride, chlorobacteric acid anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, etc. [0025] Furthermore, in the above formula (a-1), Z a It is the residue of two acid anhydride groups removed from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride. In addition, in the above formula (a-1), m is an integer of 0-20. [0026] The mass average molecular weight of the resin (A1) with the Cardo structure (Mw: measured value in terms of polystyrene conversion by colloidal permeation chromatography (GPC). The same in this specification.) 1000~40,000 is preferably, 2000 ~30000 is better. By being in the above range, good developability can be obtained and sufficient heat resistance and film strength can be obtained. [0027] From the viewpoint of easy formation of a low refractive index film with excellent mechanical strength and excellent adhesion to a substrate, a copolymer (A2) formed by polymerizing at least (a1) an unsaturated carboxylic acid can also be suitably used as alkali-soluble Resin. [0028] (a1) In terms of unsaturated carboxylic acids, for example, monocarboxylic acids such as (meth)acrylic acid and crotonic acid; among maleic acid, fumaric acid, citraconic acid, methylfumaric acid, itaconic acid, etc. Dicarboxylic acids; anhydrides of these dicarboxylic acids; etc. Among these, (meth)acrylic acid and maleic anhydride are preferred from the viewpoints of copolymerization reactivity, alkali solubility of the resin obtained, and ease of acquisition. These (a1) unsaturated carboxylic acids can be used alone or in combination of two or more kinds. [0029] The copolymer (A2) may be a copolymer of (a1) an unsaturated carboxylic acid and (a2) an unsaturated compound containing an alicyclic epoxy group. (a2) The unsaturated compound containing an alicyclic epoxy group is not particularly limited if it is an unsaturated compound having an alicyclic epoxy group. The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopentyl and cyclohexyl. In addition, examples of polycyclic alicyclic groups include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl. These (a2) alicyclic epoxy group-containing unsaturated compounds can be used alone or in combination of two or more kinds. [0030] Specifically, (a2) the unsaturated compound containing an alicyclic epoxy group includes, for example, compounds represented by the following formulas (a2-1) to (a2-15). Among these, in order to make the developability moderate, the compounds represented by the following formulas (a2-1)~(a2-5) are preferably represented by the following formulas (a2-1)~(a2-3) The compound is better. [0031]
Figure 02_image007
[0032]
Figure 02_image009
[0033]
Figure 02_image011
[0034] In the above formula, R a20 Is a hydrogen atom or a methyl group, R a21 It is a divalent aliphatic saturated hydrocarbon group with 1~6 carbon atoms, R a22 It is a divalent hydrocarbon group having 1 to 10 carbon atoms, and t is an integer of 0 to 10. R a21 On the one hand, it is a linear or branched alkylene group, such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, and hexamethylene. good. R a22 For example, methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH 2 -Ph-CH 2 -(Ph is phenylene) is preferred. [0035] The copolymer (A2) may be the above-mentioned (a1) unsaturated carboxylic acid and (a2) the above-mentioned alicyclic epoxy group-containing unsaturated compound and (a3) the above-mentioned alicyclic epoxy group-containing unsaturated compound. Copolymerization of unsaturated compounds. (a3) The unsaturated compound containing an alicyclic group is not particularly limited if it is an unsaturated compound having an alicyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopentyl and cyclohexyl. In addition, examples of polycyclic alicyclic groups include adamantyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclododecyl, and the like. These (a3) alicyclic group-containing unsaturated compounds can be used alone or in combination of two or more kinds. [0036] Specifically, (a3) an alicyclic group-containing unsaturated compound includes, for example, compounds represented by the following formulas (a3-1) to (a3-7). Among these, in order to make the developability moderate, the compounds represented by the following formulas (a3-3) to (a3-8) are preferably represented by the following formulas (a3-3) and (a3-4) The compound is better. [0037]
Figure 02_image013
[0038] In the above formula, R a23 Is a hydrogen atom or a methyl group, R a24 It is a single bond or a divalent aliphatic saturated hydrocarbon group with 1 to 6 carbon atoms, R a25 It is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R a24 It is a single bond, straight-chain or branched-chain alkylene, such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene Better. R a25 From the aspect, for example, methyl and ethyl are preferred. [0039] In addition, the copolymer (A2) may be a polymer containing a monomer of the above-mentioned (a1) unsaturated carboxylic acid and (a4) an epoxy group-containing unsaturated compound that does not have an alicyclic group. The copolymer (A2) may be a copolymer of the above-mentioned (a1) unsaturated carboxylic acid and (a4) an epoxy-containing unsaturated compound, or the above-mentioned (a1) unsaturated carboxylic acid and the above-mentioned (a2) fatty acid The copolymer of the unsaturated compound of cyclic epoxy group and (a4) the unsaturated compound containing epoxy group, it can also be the above (a1) unsaturated carboxylic acid and the above (a3) unsaturated compound containing alicyclic group Copolymers with (a4) epoxy-containing unsaturated compounds may also be the above (a1) unsaturated carboxylic acid and the above (a2) alicyclic epoxy-containing unsaturated compound and the above (a3) fat-containing Copolymer of unsaturated compound of cyclic group and (a4) unsaturated compound containing epoxy group. [0040] (a4) Regarding the epoxy group-containing unsaturated compound, for example, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxy Butyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate and other epoxy alkyl (meth)acrylates; α-ethyl glycidyl acrylate, α -n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, α-ethyl acrylate 6,7-epoxyheptyl ester, etc. α-alkyl acrylate epoxy alkyl Esters; etc. Among these, from the viewpoint of copolymerization reactivity and the strength of the cured resin, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and 6 , 7-epoxyheptyl (meth)acrylate is preferred. These (a4) epoxy-containing unsaturated compounds can be used alone or in combination of two or more kinds. [0041] In addition, the copolymer (A2) may be a copolymer containing monomers of the above-mentioned (a1) unsaturated carboxylic acid and other compounds other than the above. The copolymer (A2) may be an unsaturated compound containing an unsaturated carboxylic acid from the above (a1), the above (a2) an unsaturated compound containing an alicyclic epoxy group, the above (a3) an unsaturated compound containing an alicyclic group, and the above (a4) A copolymer of at least one monomer selected from the group consisting of an epoxy group-containing unsaturated compound and a monomer of another compound other than the above. [0042] In terms of other compounds, for example, alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, (meth)acrylates having ether linkages, the above-mentioned other (meth)acrylates, (Meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, dicarboxylic acid diesters, conjugated dienes, nitrile-containing polymerizable compounds, chlorine-containing Polymeric compounds, etc. These compounds can be used alone or in combination of two or more kinds. [0043] The alkyl (meth)acrylate, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl ( Linear or branched alkyl (meth)acrylates such as meth)acrylate, pentyl (meth)acrylate, tert-octyl (meth)acrylate, etc. [0044] Examples of hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-dimethylhydroxypropyl ( Meth)acrylate, trimethylolpropane mono(meth)acrylate, etc. [0045] Examples of (meth)acrylates having ether bonds include 2-methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and 3-methoxyethyl (meth)acrylate. Butyl butyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, tetrahydro Furfuryl (meth)acrylate is preferably 2-methoxyethyl (meth)acrylate and methoxytriethylene glycol (meth)acrylate. [0046] The above-mentioned other (meth)acrylates include, for example, chloroethyl (meth)acrylate, benzyl (meth)acrylate, and phenyl (meth)acrylate. [0047] In terms of (meth)acrylamides, for example (meth)acrylamide, N-alkyl(meth)acrylamide, N-aryl(meth)acrylamide, N, N-dialkyl(meth)acrylamide, N,N-aryl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide, N-hydroxyethyl- N-methyl(meth)acrylamide and the like. [0048] In terms of allyl compounds, for example, allyl acetate, allyl caproate, allyl octanoate, allyl laurate, allyl palmitate, and allyl stearate can be mentioned. Allyl esters such as allyl esters, allyl benzoate, allyl acetoacetate, allyl lactate, etc.; allyloxyethanol; etc. [0049] In terms of vinyl ethers, for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl Vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol Vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc. The alkyl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthracenyl ether Etc. of vinyl aryl ether; etc. [0050] In terms of vinyl esters, for example, vinyl acetate, vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, ethylene Ethyl valerate, vinyl hexanoate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl acetic acid Ester, acetyl vinyl acetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate Base ester, naphthoate vinyl ester, etc. [0051] In terms of styrenes, for example, styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl Styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy methyl styrene, acetoxy methyl benzene Alkylstyrene such as ethylene; Alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.; Chlorostyrene, dichlorostyrene, Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, Halogenated styrenes such as 4-fluoro-3-trifluoromethylstyrene; etc. [0052] Examples of dicarboxylic acid diesters include diethyl maleate and dibutyl fumarate. [0053] Examples of conjugated dienes include butadiene and isoprene. [0054] Examples of the nitrile group-containing polymerizable compound include (meth)acrylonitrile. [0055] Examples of the chlorine-containing polymerizable compound include chlorinated vinyl esters and vinylidene chloride. [0056] Regarding the copolymer (A2), in a copolymer containing the above-mentioned (a1) unsaturated carboxylic acid and a monomer of another compound other than the above, the above-mentioned (a1) unsaturated carboxylic acid and the above-mentioned ether bond Copolymers of (meth)acrylate monomers are preferred. In this case, the ratio of the structural unit derived from the (meth)acrylate having an ether bond in the copolymer (A2) is preferably 30 to 90% by mass, more preferably 40 to 80% by mass. [0057] The ratio of the structural unit derived from the unsaturated carboxylic acid (a1) in the copolymer (A2) is preferably 1-50% by mass, more preferably 5-45% by mass. In addition, when the copolymer (A2) contains a structural unit derived from the above-mentioned (a2) alicyclic epoxy-containing unsaturated compound and a structural unit derived from the above-mentioned (a4) epoxy-containing unsaturated compound, the copolymer ( The ratio of the constituent unit derived from (a2) alicyclic epoxy-containing unsaturated compound and the ratio of the constituent unit derived from the above-mentioned (a4) epoxy-containing unsaturated compound in A2) is calculated as 71 The mass% or more is preferable, 71 to 95 mass% is preferable, and 75 to 90 mass% is even more preferable. In particular, the ratio of the constituent unit derived from the above-mentioned (a2) alicyclic epoxy group-containing unsaturated compound in the copolymer (A2) is preferably 71% by mass or more, more preferably 71 to 80% by mass. When the ratio of the constituent unit derived from the aforementioned (a2) alicyclic epoxy group-containing unsaturated compound is within the aforementioned range, the stability of the photosensitive resin composition over time can be further improved. In the case where the copolymer (A2) contains a structural unit derived from the (a3) alicyclic group-containing unsaturated compound, the proportion of the copolymer (A2) is derived from the above-mentioned (a3) alicyclic group-containing unsaturated compound The ratio of the constituent units is preferably 1-30% by mass, more preferably 5-20% by mass. [0058] The mass average molecular weight of the copolymer (A2) is preferably 2,000 to 200,000, more preferably 3,000 to 30,000. By being in the above range, the film forming ability of the photosensitive resin composition and the developability after exposure tend to be easily balanced. [0059] In addition, for alkali-soluble resins, a configuration containing (A3) having at least a structural unit derived from the above-mentioned (a1) unsaturated carboxylic acid and a site capable of polymerizing with the photopolymerizable compound (B) described later can also be suitably used. The unit copolymer or (A4) has at least the structural unit derived from the above (a1) unsaturated carboxylic acid and the above (a2) alicyclic epoxy-containing unsaturated compound and/or derived from (a4) the epoxy-containing The resin of the copolymer of the structural unit of an unsaturated compound and the structural unit which has the site|part which can be polymerized with the photopolymerizable compound (B) mentioned later. When the alkali-soluble resin contains the copolymer (A3) or the copolymer (A4), the adhesion of the film formed using the photosensitive resin composition to the substrate can be improved, or the low refractive index obtained by using the photosensitive resin composition The mechanical strength of the film. [0060] The copolymer (A3) and the copolymer (A4) may be (meth)acrylates, (meth)acrylamides, and allyl compounds described as other compounds in the re-copolymerized copolymer (A2). Base compounds, vinyl ethers, vinyl esters, styrenes, etc. [0061] The structural unit having a site capable of polymerizing with the photopolymerizable compound (B) is preferably one having an ethylenically unsaturated group as the site capable of polymerizing with the photopolymerizable compound (B). The copolymerization with such a structural unit can be achieved by combining at least a part of the carboxyl group contained in the polymer containing the structural unit derived from the above-mentioned (a1) unsaturated carboxylic acid with the above-mentioned (a2) for the copolymer (A3). The alicyclic epoxy group-containing unsaturated compound and/or (a4) the epoxy group-containing unsaturated compound are prepared by reacting. In addition, the copolymer (A4) can be obtained by having a structural unit derived from the above-mentioned (a1) unsaturated carboxylic acid and (a2) an alicyclic epoxy-containing unsaturated compound and/or derived from (a4) an epoxy-containing At least a part of the epoxy group in the copolymer of the structural unit of the unsaturated compound is prepared by reacting with (a1) unsaturated carboxylic acid. [0062] The proportion of the constituent units derived from (a1) unsaturated carboxylic acid in the copolymer (A3) is preferably 1-50% by mass, more preferably 5-45% by mass. The occupancy ratio of the constituent unit having a site capable of polymerizing with the photopolymerizable compound (B) in the copolymer (A3) is preferably 1 to 45% by mass, more preferably 5 to 40% by mass. When the copolymer (A3) contains each structural unit in such a ratio, it is easy to obtain a photosensitive resin composition that can form a low-refractive-index film with excellent adhesion to the substrate. [0063] The proportion of the constituent units derived from (a1) unsaturated carboxylic acid in the copolymer (A4) is preferably 1-50% by mass, more preferably 5-45% by mass. The proportion of the constituent units derived from (a2) an alicyclic epoxy-containing unsaturated compound and/or (a4) an epoxy-containing unsaturated compound in the copolymer (A4) is preferably at least 55% by mass, It is more preferably 71% by mass or more, and particularly preferably 71 to 80% by mass. The occupancy ratio of the constituent unit having a site capable of polymerizing with the photopolymerizable compound (B) in the copolymer (A4) is preferably 1 to 45% by mass, more preferably 5 to 40% by mass. When the copolymer (A4) contains each structural unit in such a ratio, it is easy to obtain a photosensitive resin composition that can form a low-refractive-index film excellent in adhesion to a substrate. [0064] The mass average molecular weight of the copolymer (A3) and the copolymer (A4) is preferably 2,000 to 50,000, more preferably 5,000 to 30,000. By being in the above range, the film forming ability of the photosensitive resin composition and the developability after exposure tend to be easily balanced. [0065] The content of the photosensitive resin composition of the resin (A) is 20 to 85 mass relative to the mass of the photosensitive resin composition excluding the mass of the filler (D) and the mass of the organic solvent (S) described later % Is better, more preferably 30 to 70% by mass. [0066] <Photopolymerizable compound (B)> For the photopolymerizable compound (B), a monomer having an ethylenically unsaturated group can be suitably used. Among the monomers having ethylenic unsaturated groups, there are monofunctional monomers and polyfunctional monomers. [0067] Monofunctional monomers include, for example, (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, and ethoxymethyl (meth)acrylamide. Meth)acrylamide, propoxymethyl(meth)acrylamide, butoxymethoxymethyl(meth)acrylamide, N-methylol(meth)acrylamide, N -Hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2 -Acrylamide-2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-Ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (Meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloxy-2-hydroxypropyl phthalate, glycerol mono (Meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoro Ethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, semi-(meth)acrylate of phthalic acid derivative, etc. These monofunctional monomers can be used alone or in combination of two or more kinds. [0068] On the other hand, in terms of multifunctional monomers, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate can be mentioned. , Propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol Alcohol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, Pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2 -Bis(4-(meth)acryloyloxy diethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2-hydroxy -3-(Meth)acryloxypropyl(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether bis(methyl) )Acrylate, diglycidyl phthalate di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylic acid Ester (i.e., toluene diisocyanate, trimethylhexamethylene diisocyanate or hexamethylene diisocyanate, etc. and 2-hydroxyethyl (meth)acrylate reactants), methylene bis(methyl) Multifunctional monomers such as acrylamide, (meth)acrylamide methylene ether, polyol and N-methylol (meth)acrylamide condensate, etc., or triacrylate methylal. These multifunctional monomers can be used alone or in combination of two or more kinds. [0069] Among these monomers having an ethylenically unsaturated group, from the viewpoint of the tendency to improve the adhesion of the photosensitive resin composition to the substrate and the strength of the photosensitive resin composition after curing, Multifunctional monomers with three or more functions are preferable, multifunctional monomers with four or more functions are more preferable, and multifunctional monomers with five or more functions are even more preferable. [0070] Furthermore, it is particularly preferable that the photopolymerizable compound (B) is a polyfunctional compound containing six or more functions. The photosensitive resin composition contains a photopolymerizable compound (B) containing a polyfunctional compound with 6 or more functionalities. When exposed and cured, the surface of the low-refractive index film is highly cross-linked, making it easy to form a hard and dense low-refractive index film. Refractive index film. Therefore, even if the protective tape is peeled from the low-refractive index film, the surface of the low-refractive index film is not easily rough. [0071] Furthermore, it is also preferable that the photopolymerizable compound (B) contains both a polyfunctional compound having six or more functions and a photopolymerizable compound having less than six functions. When a polyfunctional compound with 6 or more functions is used alone, the influence of oxygen barrier is small, and the degree of hardening of the film surface can be improved. However, in this case, although the hardening proceeds to the unexposed part by a chain reaction, although it is tolerable, it is easy to produce residue after development in some cases, or the edge shape of the pattern is easy to shake. In contrast, the use of a polyfunctional compound with hexafunctional or more and a photopolymerizable compound with less than hexafunctional makes it easy to achieve a balance of good curing of the film surface, a small amount of residue after development, and a smooth pattern edge shape. [0072] The content of the photosensitive resin composition of the photopolymerizable compound (B) is 1 ~70% by mass is preferable, and 5-60% by mass is more preferable. By being in the above range, it tends to be easy to achieve a balance of sensitivity, developability, and resolution. [0073] <Photopolymerization initiator (C)> The photopolymerization initiator (C) is not particularly limited, and conventionally known photopolymerization initiators can be used. [0074] With regard to the photopolymerization initiator (C), specific examples include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[ 4-(2-Hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl Propane-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 2,2-dimethoxy-1,2-diphenylethyl Alkyl-1-one, bis(4-dimethylaminophenyl) ketone, 2-methyl-1-[4-(methylsulfanyl)phenyl]-2-morpholinopropan-1-one , 2-Benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, O-acetyl-1-[6-(2-methylbenzene (Formyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, O-acetyl-1-[6-(pyrrol-2-ylcarbonyl)-9-ethyl-9Hcarba Azol-3-yl]ethanone oxime, (9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2 -Methyl phenyl] ketone O-acetyloxime, 2-(benzyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, 2 , 4,6-Trimethylbenzyl diphenyl phosphine oxide, 4-benzyl-4'-methyl dimethyl sulfide, 4-dimethylaminobenzoic acid, 4-dimethyl 4-dimethylaminobenzoic acid methyl ester, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid butyl ester, 4-dimethylamino-2-ethylhexyl benzoic acid , 4-Dimethylamino-2-isopentylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione -2-(O-ethoxycarbonyl)oxime, o-benzylbenzoic acid methyl ester, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethyl Thioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-iso Propylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzyl anthraquinone Oxide, cumene hydroperoxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-bis(m- Methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethyl Amino benzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl ester, benzoin, benzoin methyl ether, benzoin Ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethyl Acetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert- Butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyl trichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4- Phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridine) Group) propane, p-methoxytriazine, 2,4,6-ginseng(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s- Triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2- Yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4, 6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s- Triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis (Trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-triazine Chloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)benzene -S-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloro Methyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine and the like. These photopolymerization initiators can be used alone or in combination of two or more kinds. [0075] Among these, the use of an oxime ester compound as the photopolymerization initiator (C) is particularly preferable in terms of sensitivity. As regards the oxime ester compound, examples of preferred compounds include O-acetyl-1-[6-(2-methylbenzyl)-9-ethyl-9H-carbazol-3-yl ]Ethanone oxime, O-acetyl-1-[6-(pyrrol-2-ylcarbonyl)-9-ethyl-9Hcarbazol-3-yl]ethanone oxime, and, 2-(benzyl oxime Oxyimino)-1-[4-(phenylthio)phenyl]-1-octanone. [0076] When using an oxime ester compound as the photopolymerization initiator (C), it is also suitable to use the oxime ester compound and a photopolymerization initiator other than the oxime ester compound in combination. When the oxime ester compound and other photopolymerization initiators are used in combination, it is easy to adjust the sensitivity of the photosensitive resin composition to an appropriate range. Therefore, it is difficult to form a patterned low refractive index film with a width larger than a desired width because it is difficult to cause excessive curing due to exposure. With regard to other photopolymerization initiators used in combination with the oxime ester compound, α-aminoalkylphenone-based photopolymerization initiators are preferred. Preferred examples of the photopolymerization initiator of the α-aminoalkylphenone series include, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane- 1-ketone (IRGACURE907 (IR-907), trade name, manufactured by BASF), and 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1- Ketone (IRGACURE369E (IR-369E), trade name, manufactured by BASF Corporation). [0077] Furthermore, as for the oxime ester compound, it is also preferable to use the oxime ester compound represented by the following formula (c1).
Figure 02_image015
(R c1 Is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group, n1 is an integer from 0 to 4, n2 is 0 or 1, R c2 Is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent, R c3 It is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ) [0078] In the formula (c1), R c1 It is not particularly limited within a range that does not hinder the purpose of the present invention, and is appropriately selected from various organic groups. R c1 Preferred examples when it is an organic group include, for example, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyloxy group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, which may be substituted Phenyl group, optionally substituted phenoxy group, optionally substituted benzyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzyloxy group, optionally substituted group Phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyloxy, optionally substituted naphthyloxy, optionally substituted naphthoxycarbonyl, optionally substituted naphthyl Aminooxy, naphthylalkyl which may have substituents, heterocyclic groups which may have substituents, amino groups, amino groups substituted by one or two organic groups, morpholin-1-yl, and piperazine -1-yl, halogen, nitro, and cyano, etc. When n1 is an integer from 2 to 4, R c1 It can be the same or different. In addition, the number of carbon atoms of the substituent that the substituent further has is not included in the number of carbon atoms of the substituent. [0079] R c1 In the case of an alkyl group, the number of carbon atoms is preferably 1 to 20, and the number of carbon atoms is more preferably 1 to 6. Again, R c1 When it is an alkyl group, it may be a straight chain or a branched chain. R c1 Specific examples of the alkyl group include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, Isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl , N-decyl, and isodecyl, etc. Again, R c1 When it is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of alkyl groups having ether bonds in the carbon chain include, for example, methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propyloxyethyl Oxyethyl, and methoxypropyl, etc. [0080] R c1 In the case of an alkoxy group, the number of carbon atoms is preferably 1 to 20, and the number of carbon atoms is more preferably 1 to 6. Again, R c1 When it is an alkoxy group, it may be a straight chain or a branched chain. R c1 Specific examples when it is an alkoxy group include, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, and sec-butyl Oxy, tert-butyloxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyl基oxy etc. Again, R c1 When it is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having ether bonds in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, Propyloxyethoxyethoxy, and methoxypropyloxy, etc. [0081] R c1 In the case of a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably 3-10, and more preferably the number of carbon atoms is 3-6. R c1 Specific examples in the case of cycloalkyl include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. R c1 Specific examples in the case of a cycloalkoxy group include, for example, a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group. [0082] R c1 When it is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably 2 to 20, and more preferably the number of carbon atoms is 2 to 7. R c1 Specific examples when it is a saturated aliphatic group include, for example, acetyl group, propionyl group, n-butyryl group, 2-methylpropionyl group, n-pentanyl group, and 2,2-dimethylpropionyl group. , N-hexyl, n-heptanyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-fourteen yin base, n-fifteen yin base, n-sixteen yin base and so on. R c1 Specific examples of saturated aliphatic anoyloxy groups include, for example, acetyloxy, propanoyloxy, n-butanoyloxy, 2-methylpropanoyloxy, n-pentanoyloxy, 2,2-Dimethylpropanoyloxy, n-hexyloxy, n-heptanoyloxy, n-octanoyloxy, n-nonanoyloxy, n-decanoyloxy, n -Undecanoyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanoyloxy, and n-hexadecanoyloxy基oxy etc. [0083] R c1 In the case of an alkoxycarbonyl group, the number of carbon atoms is preferably 2 to 20, and the number of carbon atoms is more preferably 2 to 7. R c1 Specific examples in the case of an alkoxycarbonyl group include, for example, methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxy Carbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyl Oxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, isodecyloxycarbonyl, etc. [0084] R c1 In the case of a phenylalkyl group, the number of carbon atoms is preferably 7-20, and more preferably the number of carbon atoms is 7-10. R again c1 In the case of a naphthylalkyl group, the number of carbon atoms is preferably 11 to 20, and more preferably the number of carbon atoms is 11 to 14. R c1 Specific examples in the case of phenylalkyl include, for example, benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. R c1 Specific examples in the case of naphthylalkyl include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl. R c1 When it is phenylalkyl or naphthylalkyl, R c1 The phenyl group or the naphthyl group may further have a substituent. [0085] R c1 In the case of a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing at least one N, S, and O, or a heterocyclic group formed by condensing the monocyclic rings or the monocyclic ring with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is up to 3. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, Pyridazine, benzofuran, benzothiophene, indole, isoindole, indoleazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquine Quinoline, quinazoline, phthalazine, cinnoline, and quinoxaline, etc. R c1 When it is a heterocyclic group, the heterocyclic group may further have a substituent. [0086] R c1 When it is an amino group substituted with one or two organic groups, suitable examples of the organic group include, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 2 carbon atoms. ~20 saturated aliphatic aliphatic group, optionally substituted phenyl group, optionally substituted benzyl group, optionally substituted C7-20 phenylalkyl group, optionally substituted naphthalene A group, a naphthyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group, and the like. Specific examples of these suitable organic bases and R c1 same. Specific examples of the amino group substituted with one or two organic groups include, for example, a methylamino group, an ethylamino group, a diethylamino group, an n-propylamino group, and a di-n-propylamino group. , Isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, phenylamino, naphthylamino, acetylamino, acrylamino, n-butyrylamino, n-pentylamino, n -Hexylamino, n-heptanylamino, n-octylamino, n-decylamino, benzylamino, α-naphthylamino, and β-naphthylamino Amino groups and so on. [0087] R c1 When the contained phenyl, naphthyl, and heterocyclic groups have further substituents, the substituents include, for example, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and the number of carbon atoms. Saturated aliphatic acyl groups of 2 to 7, alkoxycarbonyl groups of 2 to 7 carbon atoms, saturated aliphatic oxy groups of 2 to 7 carbon atoms, and monoalkanes with alkyl groups of 1 to 6 carbon atoms Amino group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, halogen, nitro, and cyano, etc. R c1 When the contained phenyl group, naphthyl group, and heterocyclic group further have substituents, the number of the substituents is not limited in a range that does not hinder the object of the present invention, but 1 to 4 are preferred. R c1 When the phenyl group, naphthyl group, and heterocyclic group contained have plural substituents, the plural substituents may be the same or different. [0088] R c1 Among them, it is chemically stable or has little steric hindrance and is easy to synthesize oxime ester compounds. It is composed of an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, and 2 to 7 carbon atoms. The group selected from the group consisting of saturated aliphatic aliphatic groups is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and a methyl group is particularly preferred. [0089] R c1 Bonded to the phenyl position, about R c1 For the bonded phenyl group, the position of the bonding bond between the phenyl group and the main skeleton of the oxime ester compound is the 1-position, and when the methyl position is the 2-position, the 4-position or the 5-position is preferable, and the 5-position is more preferable. In addition, n1 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and 0 or 1 is particularly preferable. [0090] R c2 It is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent. Again, R c2 In the case of a carbazolyl group which may have a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms. [0091] R c2 Among them, the substituents of the phenyl group or the carbazolyl group are not particularly limited as long as they do not hinder the object of the present invention. Examples of suitable substituents that a phenyl or carbazolyl group may have on a carbon atom include, for example, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 3 to 10 carbon atoms. Cycloalkyl groups with 3 to 10 carbon atoms, saturated aliphatic aliphatic groups with 2 to 20 carbon atoms, alkoxycarbonyl groups with 2 to 20 carbon atoms, saturated aliphatic groups with 2 to 20 carbon atoms Aliphatic acyloxy group, optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted phenylthio group, optionally substituted benzyl group, optionally substituted benzene group An oxycarbonyl group, an optionally substituted benzyloxy group, an optionally substituted phenylalkyl group having 7 to 20 carbon atoms, an optionally substituted naphthyl group, an optionally substituted naphthyloxy group, An optionally substituted naphthylmethyl group, an optionally substituted naphthyloxycarbonyl group, an optionally substituted naphthyloxy group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, Substituent heterocyclic group, optionally substituted heterocyclic carbonyl group, amino group, amino group substituted by one or two organic groups, morpholin-1-yl, piperazin-1-yl, halogen, Nitro, and cyano, etc. [0092] R c2 In the case of a carbazolyl group, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 2-20 saturated aliphatic aliphatic groups, carbon 2-20 alkoxycarbonyl groups, optionally substituted phenyl groups, optionally substituted benzyl groups, optionally substituted phenoxycarbonyl groups, An optionally substituted phenylalkyl group with 7 to 20 carbon atoms, an optionally substituted naphthyl group, an optionally substituted naphthylmethyl group, an optionally substituted naphthoxycarbonyl group, an optionally substituted naphthyl group A naphthyl alkyl group having 11 to 20 carbon atoms, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, and the like. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an ethyl group is particularly preferred. Specific examples of the substituent that the phenyl group or the carbazolyl group may have are alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, and saturated aliphatic acyl groups R c1 same. [0094] R c2 In the case where the phenyl group, the naphthyl group, and the heterocyclic group contained in the substituent group of the phenyl group or the carbazolyl group further have a substituent group, examples of the substituent group include, for example, an alkyl group having 1 to 6 carbon atoms; carbon Alkoxy group with 1 to 6 atoms; saturated aliphatic acyl group with 2 to 7 carbon atoms; alkoxycarbonyl group with 2 to 7 carbon atoms; saturated aliphatic acyloxy group with 2 to 7 carbon atoms; Phenyl; naphthyl; benzyl; naphthyl; selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, and phenyl A benzyl group substituted by the group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholin-1-yl; Piperazin-1-yl; halogen; nitro; cyano. When the phenyl group, the naphthyl group, and the heterocyclic group contained in the substituent of the phenyl group or the carbazolyl group further have a substituent, the number of the substituent is not limited in the range that does not hinder the object of the present invention, but is 1 ~4 is better. When the phenyl group, the naphthyl group, and the heterocyclic group have plural substituents, the plural substituents may be the same or different. [0095] R c2 Among them, from the viewpoint of easily obtaining a photopolymerization initiator with excellent sensitivity, the group represented by the following formula (c2) or (c3) is preferred, and the group represented by the following formula (c2) is more preferred. The group represented by the formula (c2) and the group where A is S is particularly preferred. [0096]
Figure 02_image017
(R c4 It is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group, A is S or O, and n3 is an integer of 0-4. ) [0097]
Figure 02_image019
(R c5 And R c6 Each is a monovalent organic group. ) [0098] R in formula (c2) c4 When it is an organic group, it can be selected from various organic groups within a range that does not hinder the purpose of the present invention. R in formula (c2) c4 Preferred examples of the organic group include, for example, an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; and 2 carbon atoms. ~7 alkoxycarbonyl group; saturated aliphatic aliphatic oxy group having 2 to 7 carbon atoms; phenyl; naphthyl; benzyl; naphthyl; Benzyl substituted with the group consisting of morpholin-1-yl, morpholin-1-yl, piperazin-1-yl, and phenyl; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group of an alkyl group having 1 to 6 carbon atoms; morpholin-1-yl; piperazin-1-yl; halogen; nitro; cyano. [0099] R c4 Among them, benzyl; naphthyl; substituted with a group selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, and phenyl The benzyl; nitro group is better, benzyl; naphthyl; 2-methylphenylcarbonyl; 4-(piperazin-1-yl)phenylcarbonyl; 4-(phenyl)benzene A carbonyl group is more preferred. [0100] In the formula (c2), n3 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When n3 is 1, R c4 The position of the bond is relative to R c4 As for the bonding bond between the bonded phenyl group and the oxygen atom or the sulfur atom, the para-position is preferred. R in formula (c3) c5 It can be selected from various organic groups within a range that does not hinder the purpose of the present invention. R c5 Preferable examples include, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic aliphatic group having 2 to 20 carbon atoms, and an alkane having 2 to 20 carbon atoms. An oxycarbonyl group, a phenyl group that may have a substituent, a benzyl group that may have a substituent, a phenoxycarbonyl group that may have a substituent, a phenylalkyl group with 7 to 20 carbon atoms that may have a substituent, and Substituent naphthyl, optionally substituted naphthyl methanoyl, optionally substituted naphthyloxycarbonyl, optionally substituted naphthyl alkyl with 11 to 20 carbon atoms, optionally substituted hetero A cyclic group, a heterocyclic carbonyl group which may have a substituent, and the like. [0102] R c5 Among them, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an ethyl group is particularly preferred. R in formula (c3) c6 It is not particularly limited within the scope that does not hinder the purpose of the present invention, and it can be selected from various organic groups. As R c6 Specific examples of suitable groups include, for example, an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclic group which may have a substituent. R c6 On the other hand, among these groups, a phenyl group which may have a substituent is more preferable, and a 2-methylphenyl group is particularly preferable. [0104] R c4 , R c5 Or R c6 When the contained phenyl, naphthyl, and heterocyclic groups have further substituents, the substituents include, for example, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and the number of carbon atoms. Saturated aliphatic acyl groups of 2 to 7, alkoxycarbonyl groups of 2 to 7 carbon atoms, saturated aliphatic oxy groups of 2 to 7 carbon atoms, and monoalkanes with alkyl groups of 1 to 6 carbon atoms Amino group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, halogen, nitro, and cyano, etc. R c4 , R c5 Or R c6 When the contained phenyl group, naphthyl group, and heterocyclic group further have substituents, the number of the substituents is not limited in a range that does not hinder the object of the present invention, but 1 to 4 are preferred. R c4 , R c5 Or R c6 When the phenyl group, naphthyl group, and heterocyclic group contained have plural substituents, the plural substituents may be the same or different. R in formula (c1) c3 It is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R c3 On the one hand, methyl or ethyl is preferred, and methyl is more preferred. [0106] The oxime ester compound represented by the formula (c1), when p is 0, can be synthesized by, for example, the following route 1. Specifically, the aromatic compound represented by the following formula (c1-1) is acylated by the Friedel-Crafts reaction using the halogenated carbonyl compound represented by the following formula (c1-2) to obtain the following The ketone compound represented by the formula (c1-3) is subjected to oximation of the obtained ketone compound (c1-3) with hydroxylamine to obtain the oxime compound represented by the following formula (c1-4), and then the formula (c1- The hydroxyl group in the oxime compound of 4) is acylated to obtain the oxime ester compound represented by the following formula (c1-7). As the acylating agent, an acid anhydride represented by the following formula (c1-5) ((R c3 CO) 2 O) or the acid halide represented by the following formula (c1-6) (R c3 COHal and Hal are halogens. ) Is better. In addition, in the following formula (c1-2), Hal is halogen, and in the following formulas (c1-1), (c1-2), (c1-3), (c1-4), and (c1-7) , R c1 , R c2 , R c3 , And n1 are the same as formula (c1). [0107] <Path 1>
Figure 02_image021
[0108] The oxime ester compound represented by the formula (c1), when n2 is 1, can be synthesized by, for example, the following route 2. Specifically, the ketone compound represented by the following formula (c2-1) is combined with the nitrite (RONO, R is an alkane having 1 to 6 carbon atoms) represented by the following formula (c2-2) in the presence of hydrochloric acid. Group.) The reaction is carried out to obtain the ketoxime compound represented by the following formula (c2-3), and then the hydroxyl group in the ketoxime compound represented by the following formula (c2-3) is acylated to obtain the following The oxime ester compound represented by the formula (c2-6). As the acylating agent, an acid anhydride represented by the following formula (c2-4) ((R c3 CO) 2 O) or the acid halide represented by the following formula (c2-5) (R c3 COHal and Hal are halogens. ) Is better. In addition, in the following formulas (c2-1), (c2-3), (c2-4), (c2-5), and (c2-6), R c1 , R c2 , R c3 , And n1 are the same as formula (c1). [0109] <Path 2>
Figure 02_image023
[0110] In addition, the oxime ester compound represented by the formula (c1), where n2 is 1, R c1 Is methyl, and relative to R c1 For the methyl group bonded on the bonded benzene ring, R c1 When bonding to the para position, for example, the compound represented by the following formula (c2-7) can also be synthesized by performing oximation and acylation in the same manner as in Route 1. In addition, in the following formula (c2-7), R c2 Same as formula (c1). [0111]
Figure 02_image025
[0112] Among the oxime ester compounds represented by the formula (c1), particularly preferred compounds include the following PI-1 to PI-42.
Figure 02_image027
[0113]
Figure 02_image029
[0114]
Figure 02_image031
[0115]
Figure 02_image033
[0116]
Figure 02_image035
[0117]
Figure 02_image037
[0118] In addition, the oxime ester compound represented by the following formula (c4) is also suitable as a photopolymerization initiator. [0119]
Figure 02_image039
(R c7 Is a hydrogen atom, a nitro group or a monovalent organic group, R c8 And R c9 Each is a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent or a hydrogen atom, R c8 With R c9 Mutual bonding can form a ring, R c10 It is a monovalent organic group, R c11 It is a hydrogen atom, a C1-C11 alkyl group which may have a substituent, or an aryl group which may have a substituent, n4 is an integer of 0-4, and n5 is 0 or 1. [0120] Here, the oxime compound used to produce the oxime ester compound of the formula (c4) is preferably a compound represented by the following formula (c5). [0121]
Figure 02_image041
(R c7 , R c8 , R c9 , R c10 , N4, and n5 are the same as formula (c4). ) [0122] In formulas (c4) and (c5), R c7 It is a hydrogen atom, a nitro group or a monovalent organic group. R c7 In formula (c4), the ring is bonded with -(CO) n5 -A 6-membered aromatic ring that is different from the 6-membered aromatic ring bonded to the indicated group. In formula (c4), R c7 The bonding position of the ring is not particularly limited. The compound represented by formula (c4) has more than 1 R c7 When, from the viewpoint of easy synthesis of the compound represented by formula (c4), one or more R c7 One of the bonds in the ring is preferably 2 in the ring. R c7 When it is a plural number, the R of the plural number c7 It can be the same or different. [0123] R c7 When it is an organic base, R c7 It is not particularly limited within a range that does not hinder the purpose of the present invention, and is appropriately selected from various organic groups. R c7 Preferred examples when it is an organic group include, for example, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyloxy group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, which may be substituted Phenyl group, optionally substituted phenoxy group, optionally substituted benzyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzyloxy group, optionally substituted group Phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyloxy, optionally substituted naphthyloxy, optionally substituted naphthoxycarbonyl, optionally substituted naphthyl Aminooxy, naphthylalkyl which may have substituents, heterocyclic groups which may have substituents, heterocyclic carbonyl groups which may have substituents, amino groups substituted by one or two organic groups, morpholine-1 -Base, piperazin-1-yl and the like. [0124] R c7 When it is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-6. Again, R c7 When it is an alkyl group, it may be a straight chain or a branched chain. R c7 Specific examples of the alkyl group include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, Isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl , N-decyl, and isodecyl, etc. Again, R c7 When it is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of alkyl groups having ether bonds in the carbon chain include, for example, methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propyloxyethyl Oxyethyl, and methoxypropyl, etc. [0125] R c7 When it is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1-20, more preferably 1-6. Again, R c7 When it is an alkoxy group, it may be a straight chain or a branched chain. R c7 Specific examples when it is an alkoxy group include, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, and sec-butyl Oxy, tert-butyloxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyl基oxy etc. Again, R c7 When it is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having ether bonds in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, Propyloxyethoxyethoxy, and methoxypropyloxy, etc. [0126] R c7 When it is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or a cycloalkoxy group is preferably 3-10, more preferably 3-6. R c7 Specific examples in the case of cycloalkyl include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. R c7 Specific examples in the case of a cycloalkoxy group include, for example, a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group. [0127] R c7 When it is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2-21, more preferably 2-7. R c7 Specific examples when it is a saturated aliphatic group include, for example, acetyl group, propionyl group, n-butyryl group, 2-methylpropionyl group, n-pentanyl group, and 2,2-dimethylpropionyl group. , N-hexyl, n-heptanyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-fourteen yin base, n-fifteen yin base, n-sixteen yin base and so on. R c7 Specific examples of saturated aliphatic anoyloxy groups include, for example, acetyloxy, propanoyloxy, n-butanoyloxy, 2-methylpropanoyloxy, n-pentanoyloxy, 2,2-Dimethylpropanoyloxy, n-hexyloxy, n-heptanoyloxy, n-octanoyloxy, n-nonanoyloxy, n-decanoyloxy, n -Undecanoyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanoyloxy, and n-hexadecanoyloxy基oxy etc. [0128] R c7 In the case of an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2-20, more preferably 2-7. R c7 Specific examples in the case of an alkoxycarbonyl group include, for example, methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxy Carbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyl Oxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, isodecyloxycarbonyl, etc. [0129] R c7 When it is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7-20, more preferably 7-10. Again, R c7 When it is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11-20, more preferably 11-14. R c7 Specific examples in the case of phenylalkyl include, for example, benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. R c7 Specific examples in the case of naphthylalkyl include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl. R c7 When it is phenylalkyl or naphthylalkyl, R c7 The phenyl group or the naphthyl group may further have a substituent. [0130] R c7 In the case of a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing at least one N, S, and O, or a heterocyclic group formed by condensing the monocyclic rings or the monocyclic ring with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is up to 3. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, Pyridazine, benzofuran, benzothiophene, indole, isoindole, indoleazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquine Morpholine, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran, etc. R c7 When it is a heterocyclic group, the heterocyclic group may further have a substituent. [0131] R c7 When it is a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group and R c7 It is the same when it is a heterocyclic group. [0132] R c7 When it is an amino group substituted with one or two organic groups, suitable examples of the organic group include, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 2 ~21 saturated aliphatic aliphatic group, optionally substituted phenyl group, optionally substituted benzyl group, optionally substituted C7-20 phenylalkyl group, optionally substituted naphthalene A group, a naphthyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group, and the like. Specific examples of these suitable organic bases and R c7 same. Specific examples of the amino group substituted with one or two organic groups include, for example, a methylamino group, an ethylamino group, a diethylamino group, an n-propylamino group, and a di-n-propylamino group. , Isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, phenylamino, naphthylamino, acetylamino, acrylamino, n-butyrylamino, n-pentylamino, n -Hexylamino, n-heptanylamino, n-octylamino, n-decylamino, benzylamino, α-naphthylamino, and β-naphthylamino Amino groups and so on. [0133] R c7 When the contained phenyl, naphthyl, and heterocyclic groups have further substituents, the substituents include, for example, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and the number of carbon atoms. Saturated aliphatic acyl groups of 2 to 7, alkoxycarbonyl groups of 2 to 7 carbon atoms, saturated aliphatic oxy groups of 2 to 7 carbon atoms, and monoalkanes with alkyl groups of 1 to 6 carbon atoms Amino group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, halogen, nitro, and cyano, etc. R c7 When the contained phenyl group, naphthyl group, and heterocyclic group further have substituents, the number of the substituents is not limited in a range that does not hinder the object of the present invention, but 1 to 4 are preferred. R c7 When the phenyl group, naphthyl group, and heterocyclic group contained have plural substituents, the plural substituents may be the same or different. [0134] In the above description, R c7 Aspect, nitro or R c12 The base represented by -CO- has a tendency to increase sensitivity, so it is good. R c12 It is not particularly limited within the scope that does not hinder the purpose of the present invention, and it can be selected from various organic groups. As R c12 Examples of suitable groups include, for example, an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclic group which may have a substituent. R c12 In terms of these groups, 2-methylphenyl, thiophen-2-yl, and α-naphthyl are particularly preferred. Again, R c7 If it is a hydrogen atom, the transparency tends to become better, so it is better. Again, R c7 Is a hydrogen atom and R c10 If it is the base represented by the formula (c4a) or (c4b) described later, the transparency tends to be improved. In the formula (c4), R c8 And R c9 Each is a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R c8 With R c9 Can be bonded to each other to form a ring. In this base, R c8 And R c9 On the other hand, a chain alkyl group which may have a substituent is preferable. R c8 And R c9 In the case of a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group. [0136] R c8 And R c9 In the case of a chain alkyl group having no substituents, the number of carbon atoms of the chain alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and particularly preferably from 1 to 6. R c8 And R c9 Specific examples when it is a chain alkyl group include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl Base, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, iso Nonyl, n-decyl, and isodecyl, etc. Again, R c8 And R c9 When it is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of alkyl groups having ether bonds in the carbon chain include, for example, methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propyloxyethyl Oxyethyl, and methoxypropyl, etc. [0137] R c8 And R c9 In the case of a chain alkyl group having a substituent, the number of carbon atoms of the chain alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and particularly preferably from 1 to 6. In this case, the carbon number of the substituent is not included in the carbon number of the chain alkyl group. The chain alkyl group having a substituent is preferably a linear one. The substituent which the alkyl group may have is not particularly limited in a range that does not hinder the purpose of the present invention. Suitable examples of the substituent include, for example, a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. The halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferred. The cyclic organic group includes, for example, a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclic group. In terms of specific examples of cycloalkyl, the same as R c7 Preferred examples for cycloalkyl are the same. Specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl. In terms of specific examples of heterocyclic groups, the same as R c7 When it is a heterocyclic group, the preferred examples are the same. R c7 In the case of an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1-10, more preferably 1-6. When the chain alkyl group has a substituent, the number of substituents is not particularly limited. The number of preferred substituents varies depending on the number of carbon atoms of the chain alkyl group. The number of substituents is typically 1-20, preferably 1-10, and more preferably 1-6. [0139] R c8 And R c9 When it is a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. The cyclic organic group includes, for example, an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. R c8 And R c9 When it is a cyclic organic group, the substituents that the cyclic organic group may have are the same as R c8 And R c9 It is the same when it is a chain alkyl group. [0140] R c8 And R c9 In the case of an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably a phenyl group, or a group formed by bonding a plurality of benzene rings through a carbon-carbon bond, or a group formed by condensing a plurality of benzene rings. When the aromatic hydrocarbon group is a group formed by bonding or condensing phenyl or plural benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, and 3 or less is preferable, 2 or less is more preferable, and 1 is particularly good. Preferred specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl. [0141] R c8 And R c9 When it is an aliphatic cyclic hydrocarbon group, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. Although the number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, it is preferably 3-20, more preferably 3-10. Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclic Cyclodecyl, tetracyclododecyl, adamantyl, etc. [0142] R c8 And R c9 In the case of a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing at least one N, S, and O, or a heterocyclic group formed by condensing the monocyclic rings or the monocyclic ring with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is up to 3. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, Pyridazine, benzofuran, benzothiophene, indole, isoindole, indoleazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquine Morpholine, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran, etc. [0143] R c8 With R c9 Can be bonded to each other to form a ring. By R c8 With R c9 The group formed by the formed ring is preferably a cycloalkylene group. R c8 With R c9 When bonding to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a 5-membered ring to a 6-membered ring, and more preferably a 5-membered ring. [0144] R c8 With R c9 When the group formed by bonding is a cycloalkylene group, the cycloalkylene group may be condensed with one or more other rings. Examples of the ring that can be condensed with a cycloalkylene ring include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, and a thiophene ring. Ring, pyrrole ring, pyridine ring, pyrazine ring, and pyrimidine ring, etc. [0145] R described above c8 And R c9 Examples of suitable bases in the middle, for example, formula -A 1 -A 2 The base expressed. In the formula, for example, A 1 It is a straight chain alkylene group, A 2 It is an alkoxy group, a cyano group, a halogen atom, an alkyl halide, a cyclic organic group, or an alkoxycarbonyl group. [0146] A 1 The number of carbon atoms of the straight-chain extended alkyl group is preferably 1~10, more preferably 1~6. A 2 When it is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group is preferably 1-10, more preferably 1-6. A 2 When it is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a fluorine atom, a chlorine atom, and a bromine atom are more preferable. A 2 In the case of an alkyl halide, the halogen atom contained in the alkyl halide is preferably a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and more preferably a fluorine atom, a chlorine atom, and a bromine atom. The alkyl halide may be linear or branched, preferably linear. A 2 When it is a cyclic organic group, the examples of the cyclic organic group are the same as R c8 And R c9 The cyclic organic groups of the substituents are the same. A 2 When it is an alkoxycarbonyl group, the examples of the alkoxycarbonyl group are the same as R c8 And R c9 The alkoxycarbonyl groups of the substituents are the same. [0147] R c8 And R c9 Preferred specific examples of, include, for example, ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl alkyl groups; 2-methoxyethyl, 3 -Methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy-n- Heptyl, 8-methoxy-n-octyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5-ethoxy- Alkoxyalkyl groups such as n-pentyl, 6-ethoxy-n-hexyl, 7-ethoxy-n-heptyl, and 8-ethoxy-n-octyl; 2-cyanoethyl Group, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl, 6-cyano-n-hexyl, 7-cyano-n-heptyl, and 8-cyano -n-octyl and other cyanoalkyl groups; 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6 -Phenyl-n-hexyl, 7-phenyl-n-heptyl, 8-phenyl-n-octyl and other phenylalkyl groups; 2-cyclohexylethyl, 3-cyclohexyl-n-propane Group, 4-cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6-cyclohexyl-n-hexyl, 7-cyclohexyl-n-heptyl, 8-cyclohexyl-n-octyl , 2-cyclopentylethyl, 3-cyclopentyl-n-propyl, 4-cyclopentyl-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n- Cycloalkylalkyl groups such as hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl; 2-methoxycarbonylethyl, 3-methoxycarbonyl-n- Propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl, 6-methoxycarbonyl-n-hexyl, 7-methoxycarbonyl-n-heptyl, 8-Methoxycarbonyl-n-octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl-n-propyl, 4-ethoxycarbonyl-n-butyl, 5-ethoxy Alkoxycarbonyl alkyl such as carbonyl-n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-heptyl, and 8-ethoxycarbonyl-n-octyl ; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl , 8-chloro-n-octyl, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl , 7-bromo-n-heptyl, 8-bromo-n-octyl, 3,3,3-trifluoropropyl, and 3,3,4,4,5,5,5-heptafluoro-n- Alkyl halides such as pentyl. [0148] R c8 And R c9 On the one hand, suitable groups in the above are ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl, 2- Cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, and 3,3,4,4,5,5, 5-Heptafluoro-n-pentyl. [0149] R c10 For examples of suitable organic bases, and R c7 Similarly, examples include alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic oxy, optionally substituted phenyl, A substituted phenoxy group, a substituted benzyl group, a substituted phenoxycarbonyl group, a substituted benzyloxy group, a substituted phenylalkyl group, The naphthyl group that may have a substituent, the naphthyloxy group that may have a substituent, the naphthyloxycarbonyl group that may have a substituent, the naphthyloxycarbonyl group that may have a substituent, the naphthyloxy group that may have a substituent, and the Substituent naphthylalkyl, optionally substituted heterocyclic group, optionally substituted heterocyclic carbonyl group, amino group substituted by one or two organic groups, morpholin-1-yl, and piperazine -1-base etc. Specific examples of these foundations and R c7 The description in the same. Again, R c10 On the other hand, a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylsulfanyl group which may have a substituent on the aromatic ring are also preferable. Phenoxyalkyl and phenylsulfanyl may have substituents and R c7 The phenyl groups contained may have the same substituents. In the organic group, R c10 On the other hand, an alkyl group, a cycloalkyl group, a phenyl group or a cycloalkylalkyl group which may have a substituent, and a phenylsulfanyl group which may have a substituent on the aromatic ring are preferable. As for the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, an alkyl group having 1 to 4 carbon atoms is particularly preferred, and a methyl group is most preferred. Among the phenyl groups that may have a substituent, a methylphenyl group is preferred, and a 2-methylphenyl group is more preferred. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5-10, more preferably 5-8, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the cycloalkylalkyl groups, cyclopentylethyl is preferred. The number of carbon atoms of the alkylene group contained in the phenylsulfanyl group which may have a substituent on the aromatic ring is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the phenylsulfanyl groups that may have a substituent on the aromatic ring, 2-(4-chlorophenylsulfanyl)ethyl is preferred. [0151] Again, R c10 Aspect, with -A 3 -CO-OA 4 The indicated base is also good. A 3 It is a divalent organic group, preferably a divalent hydrocarbon group, and an alkylene group. A 4 It is a monovalent organic group, preferably a monovalent hydrocarbon group. [0152] A 3 In the case of an alkylene group, the alkylene group may be linear or branched, preferably linear. A 3 When it is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1-10, more preferably 1-6, and particularly preferably 1-4. [0153] A 4 Preferred examples of, include, for example, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. A 4 Preferred specific examples of, include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n- Hexyl, phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl, etc. [0154] With -A 3 -CO-OA 4 Suitable specific examples of the represented group include, for example, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propyloxycarbonylethyl, 2-n-butyloxy 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methyl Oxycarbonyl-n-propyl, 3-ethoxycarbonyl-n-propyl, 3-n-propyloxycarbonyl-n-propyl, 3-n-butyloxycarbonyl-n-propyl , 3-n-pentyloxycarbonyl-n-propyl, 3-n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl, and 3-phenoxycarbonyl -n-propyl and so on. [0155] The above has been in R c10 Description, but R c10 On the other hand, the group represented by the following formula (c4a) or (c4b) is preferable.
Figure 02_image043
(In formulas (c4a) and (c4b), R c13 And R c14 , Each is an organic group, n6 is an integer from 0 to 4, R c13 And R 8 When existing in adjacent positions on the benzene ring, R c13 With R c14 Can be bonded to each other to form a ring, n7 is an integer from 1 to 8, n8 is an integer from 1 to 5, n9 is an integer from 0 to (n8+3), R c15 For the organic base. ) [0156] Regarding R in formula (c4a) c13 And R c14 Examples of organic groups with R c7 same. R c13 On the one hand, an alkyl group or a phenyl group is preferred. R c13 When it is an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and 1 is the best. That is, with R c13 The methyl group is the best. R c13 With R c14 When a ring is formed by bonding, the ring may be an aromatic ring or an aliphatic ring. Is the base represented by formula (c4a), and R c13 With R c14 Suitable examples of the ring-forming group include naphth-1-yl or 1,2,3,4-tetrahydronaphthalen-5-yl. In the above formula (c4a), n6 is an integer from 0 to 4, preferably 0 or 1, and more preferably 0. In the above formula (c4b), R c15 For the organic base. Organic groups, for example, with the R c7 The organic base described is the same base. Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably from 1 to 10, more preferably from 1 to 5, and particularly preferably from 1 to 3. R c15 On the other hand, preferred examples are methyl, ethyl, propyl, isopropyl, butyl, etc. Among these, methyl is more preferred. [0158] In the above formula (c4b), n8 is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2. In the above formula (c4b), n9 is 0 to (n8+3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0. In the above formula (c4b), n7 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2. In the formula (c4), R c11 It is a hydrogen atom, a C1-C11 alkyl group which may have a substituent, or an aryl group which may have a substituent. R c11 When it is an alkyl group, preferable examples are a phenyl group and a naphthyl group. Again, R c7 When it is an aryl group, preferable examples are an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom. In the formula (c4), R c11 On the other hand, preferable examples are hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group, etc. Among these, a A group or a phenyl group is more preferable. The compound represented by the formula (c4) converts the oxime group (>C=N-OH) contained in the compound represented by the aforementioned formula (c5) into>C=NO-COR by including c11 It is produced by the method of the step of the oxime ester group shown. R c11 And R in formula (c4) c11 same. [0162] Conversion of oxime group (>C=N-OH) to>C=NO-COR c11 The oxime ester group represented is carried out by reacting the compound represented by the aforementioned formula (c5) with an acylating agent. Give-cor c11 As regards the acylating agent of the acyl group, for example (R c11 CO) 2 Anhydride represented by O or R c11 An acid halide represented by COHal (Hal is a halogen atom). The compound represented by the general formula (c4), when n5 is 0, is synthesized according to the following route 3, for example. In route 3, a stilbene derivative represented by the following formula (c3-1) is used as a raw material. R c7 When it is a nitro group or a monovalent organic group, the fluorine derivative represented by formula (c3-1) can be R c8 And R c9 Substituted stilbene derivatives, using conventional methods, introduce the substituent R c7 And get. 9 digits with R c8 And R c9 Substituted Tungsten derivatives, such as R c8 And R c9 When it is an alkyl group, as described in JP 06-234668 A, it can be obtained by reacting stilbene with an alkylating agent in an aprotic polar organic solvent in the presence of an alkali metal hydroxide. Furthermore, by adding an alkylating agent such as an alkyl halide, an aqueous solution of an alkali metal hydroxide, an interphase moving catalyst such as tetrabutylammonium iodide, or potassium tert-butoxide to the organic solvent solution of the alkane Alkylation reaction can give 9,9-alkyl substituted sulphur. [0164] In the formula (c3-1), the phosphonium derivative represented by the Friedel-Crafts acylation reaction introduces -CO-R c10 The represented acyl group can be used to obtain the quince derivative represented by the formula (c3-3). In order to import -CO-R c10 The acylating agent for the acylated group may be a halogenated carbonyl compound or an acid anhydride. As for the acylating agent, the halogenated carbonyl compound represented by formula (c3-2) is preferred. In formula (c3-2), Hal is a halogen atom. The position where the glycan group is introduced on the ring can be selected by appropriately changing the conditions of the Friedel-Crafts reaction, and protecting and deprotecting the other positions of the glycated position. [0165] Next, the obtained -CO-R c10 The represented base is transformed into -C(=N-OH)-R c10 The represented group yields the oxime compound represented by formula (c3-4). Will-CO-R c10 The represented base is transformed into -C(=N-OH)-R c10 Although the method of the represented group is not particularly limited, the oximation of hydroxylamine is preferred. Make the oxime compound of formula (c3-4) and the acid anhydride represented by the following formula (c3-5) ((R c11 CO) 2 O) or the acid halide represented by the following formula (c3-6) (R c11 COHal and Hal are halogen atoms. ) By reaction, the compound represented by the following formula (c3-7) can be obtained. In addition, in formulas (c3-1), (c3-2), (c3-3), (c3-4), (c3-5), (c3-6), and (c3-7), R c7 , R c8 , R c9 , R c10 , And R c11 Same as formula (c4). In addition, in Route 3, R contained in each of formula (c3-2), formula (c3-3), and formula (c3-4) c10 , Can be the same or different. That is, R in formula (c3-2), formula (c3-3), and formula (c3-4) c10 In the synthesis process shown in Route 3, chemical modification is acceptable. Examples of chemical modification include, for example, esterification, etherification, acylation, amination, halogenation, substitution of hydrogen atoms in amine groups with organic groups, and the like. R c10 Acceptable chemical modifications are not limited to these. [0168] <Path 3>
Figure 02_image045
The compound represented by the formula (c4), when n5 is 1, is synthesized according to the following route 4, for example. In Route 4, a stilbene derivative represented by the following formula (c4-1) is used as a raw material. The sulphur derivative represented by the formula (c4-1) can be introduced into the compound represented by the formula (c3-1) by Friedel-Crafts reaction by the same method as in Route 3 -CO-CH 2 -R c10 It is obtained from the expressed 醯基. Regarding the acylating agent, the formula (c3-8): Hal-CO-CH 2 -R c10 The carboxylic acid halide represented is preferred. Next, the compound represented by formula (c4-1) is present in R c10 The methylene group between the carbonyl group is oximated to obtain the ketoxime compound represented by the following formula (c4-3). Although the method for oximating the methylene group is not particularly limited, the nitrite (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by the following general formula (c4-2) in the presence of hydrochloric acid. ) The method of reaction is better. Next, the ketoxime compound represented by the following formula (c4-3) and the acid anhydride represented by the following formula (c4-4) (R c11 CO) 2 O) or the acid halide represented by the following formula (c4-5) (R c11 COHal and Hal are halogen atoms. ) The reaction is carried out to obtain a compound represented by the following formula (c4-6). In addition, in the following formulas (c4-1), (c4-3), (c4-4), (c4-5), and (c4-6), R c7 , R c8 , R c9 , R c10 , And R c11 Same as formula (c4). When n5 is 1, there is a tendency that the generation of foreign matter in the pattern formed using the photosensitive resin composition containing the compound represented by formula (c4) can be further reduced. [0170] Furthermore, in Route 4, R contained in each of formula (c3-8), formula (c4-1), and formula (c4-3) c10 , Can be the same or different. That is, R in formula (c3-8), formula (c4-1), and formula (c4-3) c10 In the synthetic process shown in Route 4, chemical modification is acceptable. Examples of chemical modification include, for example, esterification, etherification, acylation, amination, halogenation, substitution of hydrogen atoms in amine groups with organic groups, and the like. R c10 Acceptable chemical modifications are not limited to these. [0171] <Path 4>
Figure 02_image047
Suitable specific examples of the compound represented by the formula (c4) include the following PI-43 to PI-83.
Figure 02_image049
[0173]
Figure 02_image051
[0174] The content of the photopolymerization initiator (C) is preferably 0.5 to 30% by mass, and more preferably 1 to 20% by mass relative to the mass of the photosensitive resin composition excluding the mass of the organic solvent (S) described later. good. When the content of the photopolymerization initiator (C) is within the above-mentioned range, a photosensitive resin composition having good curability and less likely to produce pattern defects can be obtained. [0175] With regard to the photopolymerization initiator (C), there are cases where an oxime ester compound and a photopolymerization initiator other than the oxime ester compound are used in combination, and the ratio of the oxime ester compound to the mass of the photopolymerization initiator (C) It is preferably 50 mass% or less, more preferably 1 mass% or more and 50 mass% or less, particularly preferably 3 mass% or more and 30 mass% or less, and most preferably 5 mass% or more and 20 mass% or less. When the photopolymerization initiator (C) contains the oxime ester compound in an amount within this range, it is particularly difficult to form a patterned low refractive index film having a width larger than a desired width. [0176] A photoinitiator auxiliary may be combined with the photopolymerization initiator (C). In terms of photo-initiating aids, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl ester, 4-dimethylaminobenzoic acid ethyl ester, 4-Dimethylaminobenzoic acid isoamyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, benzoic acid 2-dimethylaminoethyl ester, N,N-dimethyl P-toluidine, 4,4'-bis(dimethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5 -Methoxybenzothiazole, 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl ester, pentaerythritol tetramercaptoacetate, 3-mercaptopropionate and other mercaptan compounds, etc. These photo-initiating assistants can be used alone or in combination of two or more kinds. [0177] <Filler (D)> The photosensitive resin composition contains a filler (D) in order to form a low refractive index film having a desired degree of low refractive index. The filler (D) is appropriately selected from the filler blended in the photosensitive resin composition used in the formation of the conventional low-refractive index film within a range that does not hinder the object of the present invention. As for the filler (D), hollow particles or porous particles are preferred. For the filler (D), one type of particles can be used, or two or more types of particles can be used in combination. In addition, as for the filler (D), hollow particles and porous particles can be used in combination. [0178] A hollow particle refers to a particle with a cavity surrounded by an outer shell. Porous particles refer to porous particles with many voids inside. The porosity of the hollow particles or porous particles, from the viewpoint of good durability of the filler (D) and low refractive index, which is easy to form a low refractive index, is preferably 10 to 80%, more preferably 20 to 60%. 30~60% is particularly good. [0179] As for hollow particles and porous particles, from the viewpoint of making it easier to lower the refractive index of the low refractive index film, hollow particles are more preferable. For example, the refractive index of hollow silica particles is significantly lower than the refractive index of ordinary silica, which is 1.46. This is because the hollow silica particles contain air with a low refractive index of 1.0. [0180] The average particle diameter of the filler (D) is within a range that does not hinder the purpose of the present invention, and is not particularly limited. The average particle diameter of the filler (D) is preferably 1~200nm, more preferably 10~100nm. The average particle diameter system of the filler (D) is determined from an image obtained by observing the dispersed filler particles with a transmission electron microscope. Specifically, it is the following process 1)~3) 1) Calculate the projected area of each of the plural filler particles. 2) Calculate the equivalent circle diameter of each filler particle from the calculated projected area. 3) Calculate the number average value of the equivalent circle diameters of a plurality of filler particles and use it as the average particle diameter of the filler (D). In addition, the measurement of the average particle diameter is typically performed for 300 or more filler particles. [0181] The specific surface area of the filler (D) is 10~2000m 2 /g is better, 20~1800m 2 /g is better, 50~1500m 2 /g is particularly good. [0182] When the filler (D) is hollow particles or porous particles, the refractive index is preferably 1.10 to 1.40, more preferably 1.15 to 1.35, and particularly preferably 1.15 to 1.30. The refractive index here is the refractive index of the entire particle. When the particle is a hollow particle, it does not mean the refractive index that forms only the outer shell of the hollow particle. When the particles are porous particles, the refractive index of the porous particles can be measured using an Abbe refractometer (manufactured by ATAGO). [0183] The material of the hollow particles or porous particles is preferably an inorganic material from the viewpoint of lowering the refractive index of the low refractive index film. In terms of the inorganic material, for example, particles of magnesium fluoride or silicon dioxide can be mentioned. The inorganic material can be a crystalline material or an amorphous material. From the standpoints of easy formation of low refractive index film with low refractive index, easy dispersion in photosensitive resin composition, and low cost, hollow particles or porous particles made of inorganic materials are made of hollow silica particles. Or porous silica particles are preferred. The average primary particle size of the inorganic hollow particles or inorganic porous particles is preferably 1-100nm, more preferably 1-60nm. Inorganic hollow particles or porous silica particles may be monodisperse particles or may include aggregates formed by agglomeration of primary particles. [0184] When the filler (D) is an inorganic particle, for the purpose of improving the dispersion stability of the filler (D) in the dispersion of the filler (D) or in the photosensitive resin composition, or to improve the dispersion stability of the filler (D) with the resin (A), etc. For the purpose of the affinity or bonding of the components, the surface of the inorganic particles can be treated with physical surface treatment such as plasma discharge treatment or corona discharge treatment, chemical surface treatment such as surfactants or coupling agents. In this surface treatment, a chemical surface treatment using a coupling agent is preferred. In terms of coupling agents, titanium coupling agents, silane coupling agents, etc. are preferred, and silane coupling agents are more preferred. [0185] For example, when the silicon dioxide particles are treated with a silane coupling agent, the organosilane groups are bonded to the surface of the silicon dioxide particles by the reaction of the silane coupling agent with the silanol groups on the surface of the silicon dioxide particles. The organic group introduced by the treatment with the silane coupling agent includes, for example, a hydrocarbon group having 1 to 18 carbon atoms that may have an unsaturated bond, and a halogenated hydrocarbon group having 1 to 18 carbon atoms that may have an unsaturated bond. The surface treatment of the coupling agent can be performed before the inorganic particles of the filler (D) are blended with the photosensitive resin composition. In addition, the surface treatment of the filler (D) may be performed by adding a coupling agent to the photosensitive resin composition. [0186] The filler (D) such as inorganic particles is preferably dispersed in a medium before preparing the photosensitive resin composition from the viewpoint of preventing aggregation and easy dispersion in the photosensitive composition. [0187] When silica particles are used as the filler (D), commercially available silica particles can be suitably used. Specific examples of commercially available silicon dioxide particles include, for example, Nikkei Catalytic Chemicals Co., Ltd.'s Sulia series (isopropanol (IPA) dispersion, 4-methyl-2-pentanone (MIBK) dispersion Liquid, etc.); OSCAL series manufactured by Nissan Chemical Co., Ltd.; SNOWTEX series manufactured by Nissan Chemical Co., Ltd. (IPA dispersion, ethylene glycol dispersion, methyl ethyl ketone (MEK) dispersion, dimethyl Acetamide dispersion, MIBK dispersion, propylene glycol monomethyl acetate dispersion, propylene glycol monomethyl ether dispersion, methanol dispersion, ethyl acetate dispersion, butyl acetate dispersion, xylene-n -Butanol dispersion, toluene dispersion, etc.); Silinax manufactured by Nippon Steel Mining Co., Ltd.; PL series manufactured by Fuso Chemical Industry Co., Ltd. (IPA dispersion, toluene dispersion, propylene glycol monomethyl ether dispersion, Methyl ethyl ketone dispersion, etc.); AEROSIL series manufactured by EVONIK (propylene glycol acetate dispersion, ethylene glycol dispersion, MIBK dispersion, etc.). [0188] The aforementioned filler (D) is preferably blended with the photosensitive resin composition as a dispersion liquid dispersed in a medium. When silica particles are blended into the photosensitive resin composition as a dispersion, the content of silica particles in the dispersion is preferably 10-50% by mass, more preferably 15-40% by mass, and 15-30% by mass Especially good. [0189] When dispersing the filler (D) in a medium or a photosensitive resin composition, a dispersant can be used. Specific examples of the dispersant include, for example, polyamide, polyamide salt, polycarboxylic acid, polycarboxylate, high molecular weight unsaturated acid ester, modified polyurethane, and modified polyester , Modified poly(meth)acrylate, (meth)acrylic copolymer, and naphthalenesulfonic acid formaldehyde condensate and other dispersing resins. In addition, compounds such as polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine, and alkanolamine can be used as a dispersant. Among the above-mentioned dispersants, dispersing resins are preferred. Dispersed resins can be classified into linear polymers, terminal modified polymers, grafted polymers, and block polymers based on their structure. [0190] The dispersing resin has the effect of adsorbing on the surface of the filler particles to prevent aggregation of the filler particles. Therefore, preferably, for example, a terminal modified polymer having an anchor site to the surface of the filler particle, a graft type polymer, and a block type polymer are used. [0191] The mass average molecular weight of the dispersing resin (a polystyrene conversion value measured by the GPC method) is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and particularly preferably 5,000 to 50,000. [0192] The dispersion resin can be obtained as a commercially available product. Specific examples of commercially available dispersion resins include, for example, Disperbyk-101 (polyamide phosphate), Disperbyk-107 (carboxylate), and Disperbyk-110 (acid group-containing copolymer) manufactured by BYKChemie. , Disperbyk-111 (polyamide), Disperbyk-130 (polyamide), Disperbyk-161 (polymer copolymer), Disperbyk-162 (polymer copolymer), Disperbyk-163 (polymer copolymer) ), Disperbyk-164 (polymer copolymer), Disperbyk-165 (polymer copolymer), Disperbyk-166 (polymer copolymer), Disperbyk-170 (polymer copolymer), BYK-P104 ( High molecular weight unsaturated polycarboxylic acid), BYK-P105 (high molecular weight unsaturated polycarboxylic acid); EFKA4047 (polyurethane) manufactured by EFKA, EFKA4050-4010-4165 (polyurethane), EFKA4330-4340 (block copolymer), EFKA4400-4402 (modified polyacrylate), EFKA5010 (polyester amide), EFKA5765 (high molecular weight polycarboxylate), EFKA6220 (fatty acid polyester), EFKA6745 (phthalocyanine) Derivatives), EFKA6750 (Azo pigment derivatives); Ajisper PB821 and Ajisper PB822 manufactured by Ajinomoto Fine Technology Co., Ltd.; Florene TG-710 (urethane oligomer) manufactured by Kyoeisha Chemical Co., Ltd., polyflow No.50E (acrylic copolymer), polyflow No.300 (acrylic copolymer); DISPARLON KS-860 (polymer polyester amine salt), DISPARLON KS-873SN (polymer polyester amine salt) manufactured by Kusumoto Chemical Co., Ltd. ), DISPARLON KS-874 (polymer polyester amine salt), DISPARLON 2150 (aliphatic polyvalent carboxylic acid), DISPARLON 7004 (polyether ester), DISPARLON DA-703-50, DISPARLON DA-705, DISPARLON DA-725 ; Demol RN (naphthalenesulfonic acid formaldehyde polycondensate), Demol N (naphthalenesulfonic acid formaldehyde polycondensate), Demol MS (aromatic sulfonic acid formaldehyde polycondensate), Demol C (aromatic sulfonic acid formaldehyde polycondensate) manufactured by Kao Polycondensate), Demol SN-B (aromatic sulfonic acid formaldehyde polycondensate), HOMOGENOL L-18 (polymer polycarboxylic acid), EMULGEN 920 (polyoxyethylene nonylphenyl ether) , EMULGEN 930 (polyoxyethylene nonyl phenyl ether), EMULGEN 935 (polyoxyethylene nonyl phenyl ether), EMULGEN 985 (polyoxyethylene nonyl phenyl ether), Acetamine 86 (stearyl amine acetic acid Ester); SOLSPERSE 5000 (phthalocyanine derivative), SOLSPERSE 22000 (azo pigment derivative), SOLSPERSE 13240 (polyester amine), SOLSPERSE 3000 (terminal modification polymer), SOLSPERSE 17000 (terminal modification) manufactured by Lubrizol Polymer), SOLSPERSE 27000 (terminally modified polymer), SOLSPERSE 24000 (grafted polymer), SOLSPERSE 28000 (grafted polymer), SOLSPERSE 32000 (grafted polymer), SOLSPERSE 38500 (grafted polymer) Polymer); NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) manufactured by Nikko Chemical Co.; EFKA-46, EFKA- manufactured by Morishita Sangyo Co., Ltd. 47. EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450; DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID 9100 manufactured by Sannopco. [0193] In addition, as a dispersant, nonionic, anionic, and cationic surfactants can be used. These surfactants can be obtained commercially. Specific examples of commercially available surfactants include EFKA-745 manufactured by EFKA; organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.; polymer polyflow No. manufactured by Kyoeisha Oil and Chemical Industry Co., Ltd. 75. Polymer polyflow No. 90, polymer polyflow No. 95; W001, W004, W005, W017 manufactured by Yushang Company; SOLSPERSE 3000, SOLSPERSE 5000, SOLSPERSE 9000, SOLSPERSE 12000, SOLSPERSE 13240, SOLSPERSE manufactured by Lubrizol, Japan 13940, SOLSPERSE 17000, SOLSPERSE 24000, SOLSPERSE 26000, SOLSPERSE 28000; ADEKA Corporation's AdekaPluronicL31, AdekaPluronicF38, AdekaPluronicL42, AdekaPluronicL44, AdekaPluronicL61, AdekaPluronicL64, AdekaPluronicF68, AdekaPluronicL72, AdekaPluronicP95, AdekaPluronicF77, AdekaPluronicP84, AdekaPluronicF87, AdekaPluronicP94, AdekaPluronicL101, AdekaPluronicP103, AdekaPluronicF108, AdekaPluronicL121, AdekaPluronicP-123; Isonetto S-20 manufactured by Sanyo Chemicals Co., Ltd.; HINOACT T-8000E manufactured by Kawaken Fine Chemicals Co., Ltd.; ELEBASE BA-100, ELEBASE BA-200, ELEBASE BCP-2, ELEBASE BUB manufactured by Aoki Oil & Fat Co., Ltd. -3, ELEBASE BUB-4, ELEBASE CP-800K, ELEBASE EDP-475, ELEBASE HEB-5, FINESURF 270, FINESURF 7045, FINESURF 7085, BLAUNON DSP-12.5, BLAUNON DT-03, BLAUNON L-205, BLAUNON LPE- 1007, BLAUNON O-205, BLAUNON S-202, BLAUNON S-204, BLAUNON S-207, BLAUNON S-205T; EMULGEN A-500, EMULGEN PP-290, AMIET 102, AMIET 105, AMIET 302, AMIET 320, AMINON PK-02S, EMANON CH-25, manufactured by Kao EMULGEN 104P, EMULGEN 108, EMULGEN 404, EMULGEN 408, EMULGEN A-60, EMULGEN A-90, EMULGEN B-66, EMULGEN LS-106, EMULGEN LS-114, RHEODOL 430V, RHEODOL 440V, RHEODOL 460V, RHEODOL TW-S106 , RHEODOL TW-S120V, RHEODOL SUPER TW-L120, PHOSPHANOL ML-200, EML 20T, EML E-27, NEOPELEX GS, PELEX NBL, PELEX SS-H, PELEX SS-L, POIZ 532A, LATEMUL ASK, LATEMUL E- 118B, LATEMUL E-150; Newkalgen 3000S, Newkalgen FS-3PG, Newkalgen FE-7PG, Pionin D-6414, Pionin A-24-EA, Pionin A-28-B, Pionin A-29-M manufactured by Takemoto Oil , Pionin A-44-B, Pionin A-44TW; Dynol 604, Olfine PD-002W, SURFYNOL 2502, SURFYNOL 440, SURFYNOL 465, SURFYNOL 485, SURFYNOL 61 manufactured by Nissin Chemical Industry Co.; EMULSOGEN COL- manufactured by Clariant 020, EMULSOGEN 070, EMULSOGEN 080, PLYSURF A208B, PLYSURF A210B, PLYSURF A210G, PLYSURF A219B, PLYSURF AL, Lavelin FC-45 manufactured by Daiichi Kogyo Pharmaceutical; AKYPO RLM100NV, AKYPO RLM45, AKYPO RLM45, AKYPO RLM45, AKYPO RLM45, AKYPO manufactured by Nippon Surfactant ECT-3, AKYPO ECT-3NEX, AKYPO ECT-7, Phote n HLP, Photen HLP-1, Photen HLP-TEA. These dispersants can be used alone or in combination of two or more kinds. [0194] The content of the dispersant in the photosensitive resin composition is preferably from 1 to 100% by mass, more preferably from 5 to 80% by mass, and particularly preferably from 10 to 60% by mass relative to the mass of the filler. When the dispersant is a dispersing resin, the amount of dispersant used is preferably 5-100% by mass, more preferably 10~80% by mass, relative to the quality of the filler. [0195] When the photosensitive resin composition contains the filler (D), the amount of the filler (D) used in the photosensitive resin composition is within a range that does not hinder the purpose of the present invention, and is not particularly limited. The content of the filler (D) in the photosensitive resin composition is preferably 80% by mass or less, more preferably 20 to 80% by mass, relative to the mass of the photosensitive resin composition excluding the mass of the organic solvent (S) described later , 30~70% by mass is particularly good. [0196] <Fluorine-containing surfactant (E)> The photosensitive resin composition must contain a fluorine-containing surfactant (E). The content of the fluorine-containing surfactant (E) in the photosensitive resin composition is relative to the mass of the resin (A) and the mass of the photopolymerizable compound (B) and the filler (D) in the photosensitive resin composition The total mass is 0.05 to 3% by mass. The photosensitive resin composition contains the fluorine-containing surfactant (E) in an amount in this range, so that the photosensitive resin composition can be uniformly coated on the substrate, and there is no residue even when exposed to a low exposure amount. It can form a low-refractive-index film that is peeled off by the protective tape and is not easy to produce surface roughness. The fluorine-containing surfactant (E) is a surfactant containing fluorine atoms, and is not particularly limited, and may be any of anionic surfactants, cationic surfactants, and nonionic surfactants. Two or more types of fluorine-containing surfactants (E) can be used in combination. [0197] Specific examples of the fluorine-containing surfactant include BM-1000, BM-1100 (all manufactured by BM Chemical Co., Ltd.), MEGAFACF142D, MEGAFACF172, MEGAFACF173, and MEGAFACF183 (all manufactured by Dainippon Ink Chemical Industry Co., Ltd.) ), FluoradFC-135, FluoradFC-170C, FluoradFC-430, FluoradFC-431 (all manufactured by Sumitomo 3M), SurflonS-112, SurflonS-113, SurflonS-131, SurflonS-141, SurflonS-145 (all are Asahi Glass subsidiaries) Fluorine-based surfactants such as SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone Co.), but not limited to these. [0198] Furthermore, as for the fluorine-containing surfactant, a compound having a fluoroalkyl group in the side chain is also preferable. As for the compound which has a fluoroalkyl group in a side chain, the compound represented by following formula (e-1)-(e-3) is mentioned, for example. In formula (e-1) and formula (e-2), x1 is an integer of 0-7. In formula (e-3), x2 is an integer of 0-8. In formula (e-4), x3 is an integer of 6-20.
Figure 02_image053
Figure 02_image055
Figure 02_image057
[0199] The content of the fluorine-containing surfactant (E) is relative to the total of the mass of the resin (A) in the photosensitive composition, the mass of the photopolymerizable compound (B), and the mass of the filler (D) , 0.05 to 3% by mass, preferably 0.05 to 2% by mass, more preferably 0.10 to 1.5% by mass, and most preferably 0.15 to 1% by mass. [0200] <Polymerization inhibitor (F)> The photosensitive resin composition preferably contains a polymerization inhibitor (F) as necessary. By containing the polymerization inhibitor, the photosensitive resin composition easily suppresses the patterned low refractive index film from being larger than the specified size. The type of the polymerization inhibitor (F) is not particularly limited, and a compound of a polymerization inhibitor conventionally used to inhibit the polymerization of a compound having an unsaturated double bond can be used. [0201] As for the polymerization inhibitor (F), a hindered phenol compound with a molecular weight of 230 to 1500 is preferred. Although the reason is not clear, the photosensitive resin composition contains a hindered phenol compound having a molecular weight within the above-specified range as a polymerization inhibitor (F), and it is easy to form a good shape with a desired size under a wide range of exposure doses. Pattern and no residue. In addition, if the molecular weight of the polymerization inhibitor (F) is too small, residues are likely to be generated during pattern formation. If the molecular weight of the polymerization inhibitor (F) is too large, the polymerization inhibitor (F) is localized in the photosensitive resin composition, and it may be difficult to obtain the desired effect due to the use of the polymerization inhibitor (F). [0202] A hindered phenol refers to a phenolic hydroxyl group having a bulky substituent other than a hydrogen atom and a methyl group in at least one of the two ortho positions. Bulk substituents, such as alkyl groups other than methyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, substituted amino groups, sulfanyl groups, thiophenyl groups, etc. . [0203] A hindered phenol-based compound having a molecular weight of 230 to 1500 is a hindered phenol-based compound having a molecular weight within a specified range and having a function as a polymerization inhibitor, there is no particular limitation. Specific examples of hindered phenol compounds with a molecular weight of 230 to 1500 include 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone (334.5), 2,5-bis( 1,1-Dimethylbutyl) hydroquinone (250.4), pentaerythritol 4 [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (1177.6), N ,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide](637.0), 1,3,5-see (3,5-Di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (784.1), 4,4 ',4”-(1-methyl-3-propylene) ginseng (6-tert-butyl-m-cresol (544.8), 6,6'-di-tert-butyl-4,4' -Butylenedi-m-cresol (382.6), octadecyl 3-(3,5-di-tetr-butyl-4-hydroxyphenyl)propionate (530.9), 3,9-bis{2 -[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanyloxy]-1,1-dimethylethyl}-2,4,8,10-tetra Oxaspiro[5.5]undecane (741.0), 1,3,5-ginseng (3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethyl Benzene (775.2), 2,2'-thiodiethyl bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (642.9), isooctyl 3- (3,5-bis-tetr-butyl-4-hydroxyphenyl)propionate (390.6), calcium bis[3,5-bis(tert-butyl)-4-hydroxybenzyl (ethoxy) Phosphonate](692.8), Bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylene bis(oxyethylene)](586.8), 1,6 -Hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate](638.9), and 4-[[4,6-bis(octylthio) -1,3,5-Triazin-2-yl]amino]-2,6-di-tert-butylphenol (589.0). The value in parentheses after each compound name is the molecular weight of each compound. Polymerization inhibitor (F) It is possible to combine two or more kinds of hindered phenol compounds with a molecular weight of 230 to 1500. [0204] The polymerization inhibitor (F) may also contain other polymerization inhibitors other than the hindered phenol compound with a molecular weight of 230 to 1500. Other polymerizations Specific examples of inhibitors include, for example, 2,6-di-tert-butyl-p-cresol (BHT); hydroquinone, methylhydroquinone, 2,5-di-t-butyl Hydroquinone, t-butyl hydroquinone and other hydroquinone compounds; p-benzoquinone, methyl-p-benzoquinone, t-butyl benzoquinone , 2,5-Diphenyl-p-benzoquinone and other benzoquinone compounds; 2-(2-hydroxy-5-methylphenyl)benzotriazole and other benzotriazole compounds; N-nitros Nitrosylamine compounds such as phenylhydroxylamine, N-nitrosophenylhydroxylamine aluminum salt, etc.; organic Sulfur compound; bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[{3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl} Hindered amine compounds such as methyl]butylmalonate; aromatic amines such as p-phenylenediamine and N,N-diphenyl-p-phenylenediamine; see (2,4-di-t -Butylphenyl) phosphite, Si (2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diyl bisphosphonate, etc. Compound etc. The polymerization inhibitor (D) can be combined with two or more kinds of polymerization inhibitors other than hindered phenol compounds with a molecular weight of 230 to 1500. [0205] The content of the hindered phenolic compound with a molecular weight of 230 to 1500 in the polymerization inhibitor (F) is not particularly limited within a range that does not hinder the purpose of the present invention. The content of the hindered phenolic compound with a molecular weight of 230 to 1500 in the polymerization inhibitor (F) is preferably 70% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and 100% by mass. [0206] The content of the polymerization inhibitor (F) in the photosensitive resin composition is not particularly limited as long as it does not hinder the object of the present invention. The content of the polymerization inhibitor (F) is preferably 0.001 to 1 mass%, 0.01 to 1 mass relative to the mass of the photosensitive resin composition excluding the mass of the filler (D) and the mass of the organic solvent (S) % Is better. When the content of the polymerization inhibitor (F) is in the above range, the curability of the photosensitive resin composition is maintained in a good range, and at the same time, it is easy to prevent the patterned low refractive index film from being larger than the desired size. . [0207] <Organic Solvent (S)> The photosensitive resin composition preferably contains an organic solvent (S) in order to improve coatability or adjust viscosity. [0208] In terms of the organic solvent (S), specific examples include alkane monoalcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono -n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Mono-n-propyl ether, propylene glycol mono-n-butyl ether, 3-methoxy-n-butanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl Ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether and other (poly)alkylene glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl (Poly)alkyl ether acetate and other (poly)alkylene glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran Other ethers such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; lactic acid such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Alkyl esters; 2-hydroxy-2-methylpropionic acid ethyl ester, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester Ester, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutanoic acid methyl ester, 3-methoxybutyl ethyl Ester, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-acetate Propyl ester, n-butyl acetate, i-butyl acetate, n-pentyl formic acid, i-pentyl acetate, benzyl acetate, n-butyl propionate, ethyl butyrate , N-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetylacetate , Ethyl Acetate, Ethyl 2-Oxybutanoate, etc.; Aromatic Hydrocarbons such as Toluene and Xylene; N-Methyl-2-pyrrolidone, N,N-Dimethyl N,N-dimethylacetamide, N,N-dimethylacetamide, N,N-dimethylisobutylacetamide, N,N-diethylacetamide, N,N-diethylformamide , N-methylcaprolactam, 1,3-dimethyl-2-imidazolinone, pyridine, and N,N,N',N'-tetramethylurea and other nitrogen-containing polar organic solvents; etc. [0209] Among these, alkane monools, alkanediol monoalkyl ethers, alkanediol monoalkyl ether acetates, the above-mentioned other ethers, lactate alkyl esters, and the above-mentioned other esters Preferably, the alkanediol monoalkyl ether acetates, the above-mentioned other ethers, and the above-mentioned other esters such as benzyl acetate are more preferable. In addition, in terms of the solubility of each component, the organic solvent (S) is preferably a nitrogen-containing polar organic solvent. For nitrogen-containing polar organic solvents, N,N,N',N'-tetramethylurea, etc. can be used. These solvents can be used alone or in combination of two or more kinds. [0210] The content of the organic solvent (S) is not particularly limited, and is appropriately set at a concentration that can be applied to a substrate or the like according to the thickness of the coating film. For example, the viscosity of the photosensitive resin composition is preferably 1 to 500 cp, preferably 1 to 50 cp, and even more preferably 1 to 30 cp. In addition, the solid content concentration of the photosensitive resin composition is preferably 1-50% by mass, more preferably 1-20% by mass. [0211] <Other components> The photosensitive resin composition may contain surfactants other than the aforementioned fluorine-containing surfactants, photoacid generators, adhesion enhancers, thermal polymerization inhibitors, and defoamers as necessary. , Coloring agent, silane coupling agent, etc. additives. Any of the additives can be those known in the past. [0212] When the coating film of the photosensitive resin composition is exposed and cured, the surface of the low-refractive-index film inhibits the curing of oxygen, and the degree of curing of the surface of the low-refractive-index film is slightly lower. Therefore, when a protective tape is attached to the surface of a low-refractive-index film with a slightly lower degree of surface hardening, when the protective tape is peeled off, the surface of the low-refractive-index film is likely to be roughened. However, when the photosensitive resin composition contains a resin having a functional group that can be crosslinked by the action of an acid such as an epoxy group, and the photosensitive resin composition contains an acid generator, the acid generated by exposure is cross-linked The crosslinking between the sexual groups proceeds even on the surface of the low refractive index film, and the surface of the low refractive index film is sufficiently hardened. Therefore, even if the protective tape is peeled off from the low-refractive index film, the surface of the low-refractive index film is not easily roughened. [0213] In addition, from the viewpoint that the photosensitive resin composition is easily formed into a low-refractive index film having a good shape and excellent adhesion to a substrate, a silane coupling agent is preferably contained. Regarding the silane coupling agent, conventionally known ones can be used without particular limitation. [0214] Surfactants include, for example, anionic, cationic, and nonionic compounds, thermal polymerization inhibitors include, for example, hydroquinone, hydroquinone monoethyl ether, etc., and defoamers can be Examples include silicone-based and fluorine-based compounds. [0215] <Method for preparing photosensitive resin composition> The photosensitive resin composition described above can be obtained by mixing the above-mentioned components in respective prescribed amounts and then uniformly mixing them with a mixer. In addition, in order to make the obtained mixture more uniform, a filter can be used for filtration. [0216] ≪Method for producing low refractive index film≫ As for the method for producing low refractive index film, a conventionally known low refractive index using a photosensitive resin composition containing (B) a photopolymerizable compound can be used without particular limitation The manufacturing method of the film. [0217] A preferable manufacturing method of the low refractive index film includes, for example, a coating film including the formation of the aforementioned photosensitive resin composition, position-selective exposure of the coating film in response to a specified pattern, and exposure of the exposed coating film. Method of developing cloth film. [0218] In order to form a low refractive index film using the photosensitive resin composition, first, the photosensitive resin composition is coated on a substrate selected according to the use of the low refractive index film to form a coating film. Regarding the substrate, when forming an image sensor, for example, a coloring film provided with RGB on a semiconductor layer such as silicon and a substrate provided with microlenses on the coloring film is used. [0219] Although the method of forming the coating film is not particularly limited, for example, a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, or a spin coater (rotary coater) can be used. Cloth device), curtain coating machine and other non-contact coating devices. [0220] The coated photosensitive resin composition is dried as necessary to form a coating film. The drying method is not particularly limited. For example, (1) a heating plate is dried at a temperature of 80 to 120°C, preferably 90 to 100°C, for 60 to 120 seconds, and (2) placed at room temperature for several hours ~A few days, (3) Put it in a warm air heater or infrared heater for tens of minutes to several hours to remove the solvent, etc. [0221] Next, the coated film is exposed. Exposure is performed by irradiating active energy rays such as ultraviolet rays and excimer laser light. Exposure, for example, through a negative mask, exposure method, etc., is performed selectively. [0222] After selectively exposing the position of the coating film, by developing the exposed film with a developing solution, the unexposed portion is dissolved in the developing solution and removed to form a patterned cured film. The development method is not particularly limited, and for example, a dipping method, a spray method, etc. can be used. The developer system is appropriately selected according to the composition of the photosensitive resin composition. As for the developer, for example, alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts can be used. [0223] Next, the patterned cured film may also be baked (post-exposure baking). Although the baking temperature is not particularly limited, it is preferably 180~250°C, more preferably 220~230°C. The baking time is typically 10 to 90 minutes, preferably 20 to 60 minutes. By baking as described above, a cured film of the photosensitive resin composition can be obtained. [0224] The cured film thus formed can be suitably used as a low refractive index film. When the cured film is used as a low refractive index film, the refractive index of the low refractive index film (wavelength 633nm, measurement temperature 25°C) is preferably 1.35 or less, 1.23~1.34 is more preferred, and 1.25~1.33 is particularly preferred. In addition, the contact angle of the surface of the low refractive index film to water is preferably greater than 60°. In this case, the surface of the low-refractive index film can be adhered to and peeled off the protective tape without roughening the surface of the low-refractive index film. Furthermore, the surface roughness Ra of the low refractive index film is preferably 30 nm or less. [0225] The aforementioned low-refractive index film can be suitably used, for example, in optical devices such as image sensors. In the image sensor, the above-mentioned low refractive index film is used as the coating layer of the microlens formed on the RGB coloring film. By improving the reflection of the light incident on the microlens, the generation of glare in the image sensor is suppressed . [0226] In the above-mentioned optical device, it is preferable to stick a protective tape on the surface of the low refractive index film. The surface of the low refractive index film is equipped with a protective tape. In an optical device equipped with a protective tape, a grinding process is applied to the semiconductor layer on the surface opposite to the surface of the protective tape. Since the above-mentioned optical device includes the low-refractive index film formed using the photosensitive resin composition, even if the protective tape is peeled off after the grinding process, the smoothness of the surface of the low-refractive index film is maintained.

[實施例] 　　[0227] 以下以實施例將本發明更具體地說明，但本發明之範圍不限於此等之實施例。 　　[0228] 〔實施例1~11、及比較例1~3〕 　　將表1記載之種類及量的樹脂(A)、表1記載之種類及量的光聚合性化合物(B)、表1記載之種類及量的光聚合起始劑(C)、表1記載之量的下述填料(D)、表1記載之量的含氟之界面活性劑(E)、表1記載之量的聚合抑制劑(F)混合於有機溶劑(S)，得到各實施例及比較例的感光性樹脂組成物。 　　[0229] 在實施例1~3、實施例5、實施例11、及比較例1，有機溶劑(S)方面，使用由丙二醇單甲基醚92.7質量%、3-甲氧基丁基乙酸酯3.3質量%、3-甲氧基-n-丁醇3.3質量%、與甲醇0.7質量%所構成的混合溶劑，以固形分濃度成為13.5質量%之方式，調製感光性樹脂組成物。 　　在實施例4、實施例6~10、比較例2、及比較例3，有機溶劑(S)方面，使用由丙二醇單甲基醚96.3質量%、丙二醇單甲基醚乙酸酯3.0質量%、與甲醇0.7質量%所構成的混合溶劑，以固形分濃度成為10.90質量%之方式，調製感光性樹脂組成物。 　　[0230] 在實施例4、實施例6~10、比較例2、及比較例3，於感光性樹脂組成物的調製時再加入為密著增強劑之3-環氧丙氧基丙基三甲氧基矽烷1質量份。 　　[0231] 實施例、及比較例中，作為樹脂((A)成分)，使用下述A1及A2。 　　[0232] 　　A1:

Figure 02_image059
[0233] 　　A2:
Figure 02_image061
[0234] 光聚合性化合物((B)成分)方面，使用以下之B1及B2。 　　B1:環氧乙烷改性三羥甲基丙烷三丙烯酸酯(環氧乙烷3莫耳加成) 　　B2:二季戊四醇六丙烯酸酯 　　[0235] 光聚合起始劑((C)成分)方面，使用以下之C1及C2。 　　C1:2-甲基-1-〔4-(甲基硫基)苯基〕-2-嗎啉基丙烷-1-酮 　　C2:2-(苯甲醯基氧基亞胺基)-1-[4-(苯基硫基)苯基]-1-辛酮 　　C3:1-羥基-環己基-苯基-酮 　　[0236] 填料((D)成分)方面，使用A2SL-03TO(製品名、日揮觸媒化成(股)製、平均一次粒徑60nm的中空二氧化矽粒子的分散液、固形分濃度20質量%)。 　　[0237] 界面活性劑((E)成分)方面，使用下述氟系界面活性劑。
Figure 02_image063
[0238] 聚合抑制劑((F)成分)方面，使用以下之F1。 　　F1:季戊四醇肆[3-(3,5-二-tert-丁基-4-羥基苯基)丙酸酯](分子量:1177.6)、 　　[0239]
Figure 02_image065
[0240] 使用得到的各實施例及比較例的感光性樹脂組成物，依據下述方法，製造低折射率膜。測定得到的低折射率膜之折射率，使用任一實施例及比較例的感光性樹脂組成物所形成的硬化膜，折射率之值皆在1.32~1.40的範圍內。 (折射率的測定) 　　將感光性樹脂組成物在矽晶圓上使用旋轉塗佈機，以塗佈膜厚成為800nm之方式進行塗佈。使形成的塗佈膜以加熱板在90℃進行2分鐘加熱後，使用i線步進機以500mJ/cm2 進行位置選擇性地曝光。 　　使曝光後的塗佈膜在濃度0.2質量%的四甲基氫氧化銨水溶液進行1分鐘顯影。使顯影而得到的經圖型化的膜以加熱板，在220℃進行5分鐘加熱，得到低折射率膜。將得到的低折射率膜之折射率使用折射率測定裝置(光譜式橢圓儀)J.A.Woollam公司製 VUV-VASE VU-302進行測定。 　　[0241] 又，使用各實施例及比較例的感光性樹脂組成物，依據以下之方法，評估50μm解像性、殘膜率、未產生殘渣之曝光量、可剝離保護膠帶之曝光量、及塗佈均勻性。此等之評估結果如表2。 　　[0242] (50μm解像性評估) 　　以與折射率的測定相同方法形成圖型，可使線寬50μm的線圖型解像之情形為○、無法解像之情形為×。 　　[0243] (殘膜率評估) 　　以與折射率的測定相同方法形成圖型，以預烤後的膜厚為100%時之顯影後的膜厚作為殘膜率。 　　[0244] (未產生殘渣之曝光量評估) 　　除改變曝光量之外，以與折射率的測定相同之方法，形成圖型，求出不產生殘渣而可使圖型顯影之最大曝光量。 　　例如實施例1之情形，以175mJ/cm2 以上進行曝光則產生殘渣，但以175mJ/cm2 以下進行曝光，則無殘渣產生。 　　[0245] (可剝離保護膠帶之曝光量) 　　[0246] 除改變曝光量之外，以與折射率的測定相同之方法，形成圖型，硬化後，於硬化膜黏貼保護膠帶後剝離時，求出膜不黏附於膠帶的最小曝光量。 　　[0247] (塗佈均勻性) 　　將各實施例、及比較例的感光性樹脂組成物在Si基板上進行旋轉塗佈，形成塗佈膜。將形成的塗佈膜以目視及顯微鏡觀察，未觀察到放射狀的條紋或色不均而均勻地塗佈時為○、其以外為×。 　　又，關於比較例1的感光性樹脂組成物，因形成之塗佈膜為顯著不均勻，對塗佈均勻性以外未進行詳細評估。 　　又，關於比較例2、及比較例3的感光性樹脂組成物，因為形成之塗佈膜有條紋或不均產生，故未進行可剝離保護膠帶之曝光量的詳細評估。 　　[0248]
Figure 02_image067
[0249] 由表2可知道，相對於樹脂(A)之質量與光聚合性化合物(B)之質量與填料(D)之質量之合計，含有0.05~3質量%的含氟之界面活性劑(F)之實施例的感光性樹脂組成物，可在基板上良好地塗佈，且即使以低曝光量的曝光，可形成即使經保護膠帶之黏貼及剝離表面仍不易粗糙之硬化膜。 　　又，在實施例，皆未產生殘渣之曝光量的上限值比可剝離保護膠帶之曝光量的下限值大，可知藉由在可剝離保護膠帶之曝光量的下限值與未產生殘渣之曝光量的上限值間的曝光量進行曝光，抑制顯影時之殘渣產生同時可形成經保護膠帶之黏貼及剝離表面亦不易粗糙之硬化膜。 　　[0250] 另一方面，可知相對於樹脂(A)之質量與光聚合性化合物(B)之質量與填料(D)之質量之合計，不含0.05~3質量%的含氟之界面活性劑(F)的比較例的感光性樹脂組成物，在探討是否可形成經保護膠帶之黏貼及剝離表面仍不易粗糙之硬化膜問題以前，其難以在基板上均勻塗佈。 　　又，在比較例1雖進行了未產生殘渣之曝光量的上限值與可剝離保護膠帶之曝光量的下限值之比較，但未產生殘渣之曝光量的上限值比可剝離保護膠帶之曝光量的下限值小。亦即，在比較例1的感光性樹脂組成物，不存在有兼具殘渣產生良好被抑制、與形成經保護膠帶之黏貼及剝離表面仍不易粗糙之硬化膜的曝光量範圍。[Examples] [0227] Hereinafter, the present invention will be explained more specifically with examples, but the scope of the present invention is not limited to these examples. [Examples 1 to 11 and Comparative Examples 1 to 3] The type and amount of resin (A) described in Table 1, the type and amount of photopolymerizable compound (B) described in Table 1, and Table 1 The type and amount of the photopolymerization initiator (C), the following filler (D) in the amount described in Table 1, the fluorine-containing surfactant (E) in the amount described in Table 1, and the amount of polymerization described in Table 1. The inhibitor (F) was mixed with the organic solvent (S) to obtain the photosensitive resin composition of each Example and Comparative Example. [0229] In Examples 1 to 3, Example 5, Example 11, and Comparative Example 1, in terms of the organic solvent (S), 92.7% by mass of propylene glycol monomethyl ether and 3-methoxybutyl acetic acid were used. A mixed solvent composed of 3.3% by mass of ester, 3.3% by mass of 3-methoxy-n-butanol, and 0.7% by mass of methanol was prepared to prepare a photosensitive resin composition so that the solid content concentration became 13.5% by mass. In Example 4, Examples 6 to 10, Comparative Example 2, and Comparative Example 3, the organic solvent (S) uses 96.3% by mass of propylene glycol monomethyl ether, 3.0% by mass of propylene glycol monomethyl ether acetate, The mixed solvent composed of 0.7% by mass of methanol and the photosensitive resin composition was prepared so that the solid content concentration became 10.90% by mass. [0230] In Example 4, Examples 6 to 10, Comparative Example 2, and Comparative Example 3, 3-glycidoxypropyltrimethyl as an adhesion enhancer was added during the preparation of the photosensitive resin composition 1 part by mass of oxysilane. [0231] In Examples and Comparative Examples, the following A1 and A2 were used as the resin ((A) component). [0232] A1:
Figure 02_image059
[0233] A2:
Figure 02_image061
[0234] For the photopolymerizable compound ((B) component), the following B1 and B2 were used. B1: Ethylene oxide modified trimethylolpropane triacrylate (3 mol addition of ethylene oxide) B2: Dipentaerythritol hexaacrylate [0235] In terms of photopolymerization initiator ((C) component), Use the following C1 and C2. C1: 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one C2: 2-(benzyloxyimino)-1- [4-(Phenylthio)phenyl]-1-octanone C3:1-hydroxy-cyclohexyl-phenyl-ketone [0236] For the filler ((D) component), A2SL-03TO (product name, A dispersion of hollow silica particles with an average primary particle size of 60nm made by Nikkei Catalytic Chemicals (stock), with a solid content concentration of 20% by mass). [0237] Regarding the surfactant (component (E)), the following fluorine-based surfactant was used.
Figure 02_image063
[0238] For the polymerization inhibitor (component (F)), the following F1 was used. F1: pentaerythritol 4 [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (molecular weight: 1177.6), [0239]
Figure 02_image065
[0240] Using the obtained photosensitive resin compositions of the respective Examples and Comparative Examples, a low refractive index film was produced according to the following method. The refractive index of the obtained low refractive index film was measured, and the cured film formed using the photosensitive resin composition of any one of the examples and the comparative example had a refractive index value in the range of 1.32 to 1.40. (Measurement of Refractive Index) The photosensitive resin composition was coated on a silicon wafer using a spin coater, and the coating film thickness was 800 nm. After heating the formed coating film with a hot plate at 90° C. for 2 minutes, position selective exposure was performed at 500 mJ/cm 2 using an i-line stepper. The coated film after exposure was developed in an aqueous solution of tetramethylammonium hydroxide having a concentration of 0.2% by mass for 1 minute. The patterned film obtained by the development was heated on a hot plate at 220° C. for 5 minutes to obtain a low refractive index film. The refractive index of the obtained low refractive index film was measured using a refractive index measuring device (spectroscopic ellipsometer) VUV-VASE VU-302 manufactured by JA Woollam Corporation. [0241] In addition, using the photosensitive resin composition of each of the Examples and Comparative Examples, the 50 μm resolution, residual film rate, exposure to no residue, exposure to peelable protective tape, and the following methods were used to evaluate Coating uniformity. The results of these evaluations are shown in Table 2. [0242] (50 μm Resolvability Evaluation) The pattern is formed in the same method as the measurement of the refractive index, and the resolution of the line pattern with a line width of 50 μm can be set as ○, and the resolution can be set as ×. (Evaluation of residual film rate) A pattern was formed in the same method as the measurement of the refractive index, and the film thickness after development when the film thickness after prebaking was 100% was used as the residual film rate. [0244] (Evaluation of exposure without residues) Except for changing the exposure, the same method as the measurement of refractive index was used to form a pattern, and the maximum exposure at which the pattern could be developed without generating residues was determined. For example, in the case of Example 1, the exposure at 175 mJ/cm 2 or more produced residues, but the exposure at 175 mJ/cm 2 or less produced no residues. [0245] (Exposure Amount of Peelable Protective Tape) [0246] Except for changing the exposure, use the same method as the refractive index measurement to form a pattern. After curing, when the cured film is peeled off after sticking the protective tape, determine The minimum amount of exposure at which the film does not adhere to the tape. [0247] (Coating Uniformity) The photosensitive resin composition of each Example and Comparative Example was spin-coated on a Si substrate to form a coating film. When the formed coating film was observed visually and under a microscope, no radial streaks or color unevenness were observed and it was uniformly coated, and it was rated as ○, and the other cases were rated as x. In addition, regarding the photosensitive resin composition of Comparative Example 1, since the formed coating film was significantly uneven, no detailed evaluation was performed except for coating uniformity. In addition, regarding the photosensitive resin composition of Comparative Example 2 and Comparative Example 3, since the formed coating film had streaks or unevenness, detailed evaluation of the exposure amount of the peelable protective tape was not performed. [0248]
Figure 02_image067
[0249] From Table 2, it can be seen that the total of the mass of the resin (A) and the mass of the photopolymerizable compound (B) and the mass of the filler (D) contains 0.05 to 3% by mass of the fluorine-containing surfactant The photosensitive resin composition of the embodiment of (F) can be well coated on the substrate, and even if exposed with a low exposure amount, it can form a cured film that is not easy to be rough even after the adhesion and peeling of the protective tape. In addition, in the examples, the upper limit of the exposure amount where no residue is generated is greater than the lower limit of the exposure amount of the peelable protective tape. Exposure is performed at an exposure level between the upper limit of the exposure level to suppress the generation of residues during development and at the same time form a hardened film that is not easy to be roughened by the adhesion and peeling of the protective tape. [0250] On the other hand, it can be seen that the sum of the mass of the resin (A) and the mass of the photopolymerizable compound (B) and the mass of the filler (D) does not contain 0.05 to 3% by mass of the fluorine-containing surfactant The photosensitive resin composition of the comparative example of (F) was difficult to be uniformly coated on the substrate before the problem of whether it was possible to form a cured film that was not easy to be rough after the adhesive and peeling surface of the protective tape could be formed. Also, in Comparative Example 1, the upper limit of the exposure amount without residue and the lower limit of the exposure amount of the peelable protective tape were compared, but the upper limit of the exposure amount without residue was compared with the upper limit of the peelable protective tape. The lower limit of the exposure is small. That is, in the photosensitive resin composition of Comparative Example 1, there is no exposure range that has both the excellent suppression of residue generation and the formation of a cured film that is difficult to be roughened on the adhesive and peeled surface of the protective tape.

Claims (9)

一種低折射率膜形成用感光性樹脂組成物，其特徵係含有樹脂(A)、光聚合性化合物(B)、光聚合起始劑(C)、填料(D)、與含氟之界面活性劑(E)，前述含氟之界面活性劑(E)之含量，相對於前述樹脂(A)之質量與前述光聚合性化合物(B)之質量與前述填料(D)之質量的合計，為0.05~3質量%，前述填料(D)含有中空粒子，前述光聚合性化合物(B)含有具有6個以上之聚合性官能基之化合物與具有未達6個聚合性官能基之化合物。 A photosensitive resin composition for forming a low refractive index film, which is characterized by containing resin (A), photopolymerizable compound (B), photopolymerization initiator (C), filler (D), and fluorine-containing interface activity Agent (E), the content of the aforementioned fluorine-containing surfactant (E), relative to the total of the mass of the resin (A), the mass of the photopolymerizable compound (B), and the mass of the filler (D), is 0.05-3% by mass, the filler (D) contains hollow particles, and the photopolymerizable compound (B) contains a compound having 6 or more polymerizable functional groups and a compound having less than 6 polymerizable functional groups. 如請求項1記載之低折射率膜形成用感光性樹脂組成物，其係含有聚合抑制劑(F)。 The photosensitive resin composition for forming a low refractive index film as described in Claim 1, which contains a polymerization inhibitor (F). 如請求項1或2記載之低折射率膜形成用感光性樹脂組成物，其中，前述光聚合起始劑(C)含有肟酯化合物。 The photosensitive resin composition for forming a low refractive index film according to claim 1 or 2, wherein the photopolymerization initiator (C) contains an oxime ester compound. 一種低折射率膜，其特徵係由請求項1~3中任1項記載之低折射率膜形成用感光性樹脂組成物硬化而形成。 A low refractive index film characterized by being formed by curing the photosensitive resin composition for forming a low refractive index film described in any one of claims 1 to 3. 如請求項4記載之低折射率膜，其係經圖型化且表面粗度Ra為30nm以下。 The low refractive index film described in claim 4 is patterned and has a surface roughness Ra of 30 nm or less. 如請求項4或5記載之低折射率膜，其對水之接觸角比 60°大。 For the low refractive index film described in claim 4 or 5, the ratio of its contact angle to water 60° big. 一種光學裝置，其特徵係具備請求項4~6中任1項記載之低折射率膜。 An optical device characterized by comprising the low refractive index film described in any one of claims 4 to 6. 如請求項7記載之光學裝置，其在前述低折射率膜上具備保護膠帶。 The optical device according to claim 7, which includes a protective tape on the low refractive index film. 一種經圖型化的低折射率膜之製造方法，其特徵係包含：形成請求項1~3中任1項記載之低折射率膜形成用感光性樹脂組成物的塗佈膜，使前述塗佈膜因應指定圖型進行位置選擇性地曝光，將經曝光的前述塗佈膜顯影。 A method for producing a patterned low-refractive-index film, characterized by comprising: forming a coating film of the photosensitive resin composition for forming a low-refractive-index film described in any one of Claims 1 to 3, and coating the aforementioned The cloth film is selectively exposed in position according to the designated pattern, and the exposed coating film is developed.
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