200911523 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種乾膜、微透鏡及其製法、與具備微 透鏡之液晶顯示元件。 【先前技術】 於顯示元件之中，尤其是液晶顯示元件，由於具優越 之低消耗電力、高信賴性、能夠對應於廣泛尺寸之柔軟性、 其高精細之顯示特性、薄型輕量等之優越特徵，於平面面 板顯示器之中最被廣泛使用，隨著電腦、打字機等之〇A 機器、液晶電視、行動電話、投影機等之普及，近年來對 於其性能之要求變得越來越嚴格。因應於此等之要求，於 專利文獻1〜5中，有人提案藉由設置微透鏡陣列，使外部 光或背光之光予以聚光於開口部，使液晶顯示元件之亮度 或對比得以提高之方法。於此等方法之中，大多之情形， 由於從微透鏡存在之聚光層至液晶像素開口部的焦距距離 非常的短，必須採用擴大形成微透鏡之材料與平坦化膜的 折射率差，並且精密控制透鏡之曲率半徑。 形成如此液晶顯示元件用之微透鏡的方法，可列舉： 乾蝕刻玻璃基板後而使凹陷得以形成，再利用高折射率之 紫外線硬化型樹脂以塡滿此凹陷的方法；藉由形成透鏡圖 案後而進行加熱處理，使圖案予以溶融流動，於原狀態下 作爲透鏡利用的方法；藉由從感放射線性樹脂組成物，形 成圖案後而予以熔融流動，製作既定形狀之光罩，透過此 光罩而加以乾蝕刻，使既定之透鏡形狀轉印至基底之方法 200911523 等。但是，利用如此方法之任意情形下，微透鏡之形成製 程皆爲既繁雜且高價，工業上尙稱不上完備。 因此，強烈需求一種感放射線性樹脂組成物之開發， 其能夠符合微透鏡所要求之各種特性，例如，膜厚、解像 度'圖案形狀、透明性、耐熱性、耐溶劑性等，另外，保 存安定性爲良好的，並且利用簡便之方法即可以形成微透 鏡。 另外’於形成使用感放射線性樹脂組成物之液晶顯示 元件用微透鏡之方法中，其大多於樹脂組成物中含有有機 溶劑’將該組成物，依照旋轉塗布法或浸漬法、噴霧法等 之手法而使組成物層積層於基材上。於此等手法之中，爲 了得到既定膜厚之設定條件所需之時間爲必要的，另外溶 劑之揮發等環境面問題也已被發現。因而，也要求開發一 種使用感放射線性樹脂組成物之乾膜的微透鏡製法，與習 知微透鏡之製法相比較，僅是將薄膜積層於基材上，照射 既定量之放射線後而進行顯像，爲短時間且低成本。 於使用感放射線性樹脂組成物之乾膜的微透鏡製造 中’通常由於感放射線性樹脂組成物層係利用基層薄膜與 外部空氣予以遮斷之狀態下進行曝光步驟，感放射線性樹 脂組成物層之曝光部係於自由基聚合反應之際，不會受到 氧阻礙’而有極度硬化之傾向。因此，於後烘烤後具有適 度之熔融流動性、得到所希望之透鏡形狀，迄今仍爲困難 的0 如上所述’於使用簡易之乾膜法而以高良率大量製作 200911523 高精細之微透鏡的手法開發上，利用乾膜法時，強烈需求 能夠控制後烘烤後之透鏡形狀的感放射線性樹脂組成物層 之確立。 專利文獻1:日本專利特開2003-255318號公報 專利文獻2 :日本專利特開2 0 01 - 1 5 4 1 8 1號公報 專利文獻3 :日本專利特開2 0 0 1 - 1 1 7 1 1 4號公報 專利文獻4 :日本專利特開平1 1 - 1 〇 9 4 1 7號公報 專利文獻5 :日本專利特開平1 0 - 2 6 8 3 0 5號公報 【發明內容】 發明所欲解決之技術問頴 本發明係著眼於存在於習用技術之問題點所完成的。 其目的在於提供一種乾膜光阻，其係藉由在乾燥後之感放 射線性樹脂組成物層中具有充分之熔融流動性，可形成目 的之光阻形狀。 本發明之其他目的在於提供一種上述乾膜光阻之製 法。 本發明之另一其他目的在於提供一種使用上述乾膜光 阻之微透鏡及其製法。 本發明之另一其他目的在於提供一種具備上述微透鏡 之液晶顯不兀件。 本發明之其他目的及優點將可由下列之說明而變得明 確。 解決問題之技術丰段 爲了解決上述課題，本發明人發現：藉由使含有鏈轉 200911523 移劑之感放射線性樹脂組成物層積層於基層薄膜上，能夠 控制熔融流動性，達成本發明之感放射線性乾膜。 亦即，若根據本發明，本發明之上述目的及優點，第 1點係根據一種乾膜所達成，其特徵在於：由基層薄膜、 在基層薄膜上所積層的厚度爲2〜200μηι，每lm2無規地測 定10點之結果，最大與最小之差爲膜厚5%以內之均勻薄 膜的感放射線性樹脂組成物層與感放射線性樹脂組成物層 上所積層的覆膜所構成，上述感放射線性樹脂組成物層係 含有（A )鹼可溶性共聚物、（B )聚合性不飽和化合物、 (C )光聚合起始劑與（D )鏈轉移劑。 若根據本發明，本發明之上述目的及優點，第2點係 根據一種感放射線性乾膜之製法所達成，其特徵在於：在 可撓性之基層薄膜上塗布本發明之感放射線性樹脂組成 物’經乾燥後而形成感放射線性塗膜。 右根據本發明，本發明之上述目的及優點，第3點係 根據一種微透鏡所達成，其係使用本發明之乾膜所形成。 若根據本發明，本發明之上述目的及優點，第4點係 根據一種微透鏡之形成方法所達成，其特徵係至少含有下 列（i )〜（i v )的步驟： (i )從本發明之乾膜上剝離覆膜，將感放射線性樹脂 組成物層轉印至玻璃基板後而形成塗膜的步驟； (i i )在該塗膜之至少一部分照射放射線的步驟； (Hi )顯像照射後之塗膜的步驟；及 (1 v )加熱顯像後之塗膜的步驟。 200911523 若根據本發明，本發明之上述目的及優點，第5點係 根據一種液晶顯示元件所達成，其係具備本發明之微透鏡。 【實施方式】 實施發明之最佳形熊 以下，針對本發明詳加說明。 可使用於本發明之基層薄膜的厚度並未予以特別限 定，例如，適宜爲5〜125 μπι。更佳爲1〇〜50 μηι之厚度。 如此厚度之基層薄膜，例如，能夠取得下列市售品：PET 薄膜「R340G16」（三菱化學聚酯薄膜（股）製、16μιη厚）、 「Ε2」（帝人DUPONT薄膜（股）製）'「Χ83」（帝人DUPONT 薄膜（股）製）、DIAFOIL「R310」（三菱化學聚酯薄膜（股） 製、16μιη 厚）、COSMOSHINE「A4100」（東洋紡績（股） 製、50μιη厚）、「A4300」（東洋紡績（股）製、5〇μιη厚）、 DIAFOIL「Τ100Β25」（三菱化學聚酯薄膜（股）製、25, 厚）、「T100G38」（三菱化學聚酯薄膜（股）製、38^m厚） 等。 本發明之乾膜係於上述基層薄膜之上具有感放射線性 樹脂組成物層，覆膜進一步覆蓋此組成物層。 覆膜較宜使用，例如聚對苯二甲酸乙二醋（PET )薄膜 及聚乙烯（P E )薄膜。進一步更佳使用具有自黏性樹脂層 之PET及PE薄膜。 覆膜之厚度並未予以特別限定，例如’較佳爲5〜 2 0 0 μηι。 PET薄膜較佳爲離型處理後之物。市售品 200911523 處理的PET薄膜，例如，可列舉：PUREX FILM「A31」（帝 人 DUPONT FILM(股）製、25μηι 厚與 38μιη 厚）、PUREX FILM 「A54」（帝人 DUPONT FILM(股）製、25μπι 厚與 38μηι 厚）、 DIAFOIL「MRF」（三菱化學聚酯薄膜（股）製、25μιη厚與 38μιη厚）、「MRA50」（三菱化學聚酯薄膜（股）製、50μηι 厚）等。 另外，市售品之ΡΕ薄膜’例如’可列舉：「WAKO GREEN FILM PE」 （WAKO 樹脂（股）製、21μιη 厚與 40μιη 厚）、 「GF-1」（TAMAPOLY(股）製）、「GF-3」（TAMAPOLY(股） 製、30μιη 厚）、「PE-LD」（旭化成 CHEMICALS(股）製）、 「ΡΕ-HD」（旭化成CHEMICALS(股）製）等。 另外，具有自黏性樹脂層之覆膜，適合使用例如PE 薄膜「TORETEC 7721」（TORAY FILM 加工（股）製、60μπι 厚）等可以市售品方式取得。 接著，針對感放射線性樹脂組成物層之感放射線性樹 脂組成物加以說明。感放射線性樹脂組成物係含有：（A ) 鹼可溶性共聚物、（B )聚合性不飽和化合物、（C )光聚 合起始劑與（D )鏈轉移劑。 〜（A )鹼可溶性共聚物一 於本發明中之（A)成分係於製造微透鏡之際’相對於 其顯像處理步驟所用之顯像液的鹼顯像液具有可溶性’若 可見光波長之光良好穿透的話’則特別理想’並未予以特 別限定。尤其較佳爲由（a )分子內具有1個以上酸性官能 基之聚合性不飽和化合物（以下’稱爲「（ a )聚合性不飽 -10- 200911523 和化合物」。）5〜6 0重量％ ’及（b )其他之聚合性不飽 和化合物40〜95重量％ (但是’ （a) + (b) =100重量 % )所構成的鹼可溶性共聚物（以下，稱爲「（ A )共聚物」。）， 再者，（b )其他之聚合性不飽和化合物尤以含有N位-取 代之馬來醯亞胺的鹼可溶性共聚物特別理想。 (a )聚合性不飽和化合物之酸性官能基，例如，可列 舉：羧基、磺酸基等，尤以羧基特別理想。 具有殘基的（a)聚合性不飽和化合物（以下，稱爲「（ 31)BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dry film, a microlens, a method of manufacturing the same, and a liquid crystal display element having a microlens. [Prior Art] Among the display elements, in particular, liquid crystal display elements have excellent power consumption, high reliability, flexibility in response to a wide range of sizes, high-definition display characteristics, and thinness and lightness. Features are most widely used in flat panel displays. With the popularity of computers, typewriters, and other A-machines, LCD TVs, mobile phones, projectors, etc., their performance requirements have become more stringent in recent years. In order to meet such requirements, Patent Literatures 1 to 5 propose a method of concentrating external light or backlight light in an opening by providing a microlens array to improve brightness or contrast of a liquid crystal display element. . Among these methods, in many cases, since the focal length from the concentrating layer in which the microlens exists to the opening of the liquid crystal pixel is extremely short, it is necessary to adopt a refractive index difference between the material which expands the microlens and the planarizing film, and Precision control of the radius of curvature of the lens. The method of forming the microlens for a liquid crystal display element is as follows: a method of forming a recess after dry etching a glass substrate, and using a high refractive index ultraviolet curable resin to fill the recess; by forming a lens pattern The heat treatment is performed to melt and flow the pattern, and the film is used as a lens in the original state. After the pattern is formed from the radiation sensitive resin composition, the pattern is melted and flowed to form a mask of a predetermined shape, and the mask is passed through the mask. The method of dry etching to transfer a predetermined lens shape to a substrate is 200911523 and the like. However, in any case where such a method is used, the formation process of the microlens is both complicated and expensive, and the industrial nickname is not complete. Therefore, there is a strong demand for the development of a radiation sensitive resin composition which can meet various characteristics required for microlenses, such as film thickness, resolution 'pattern shape, transparency, heat resistance, solvent resistance, etc., and preservation stability The properties are good, and microlenses can be formed by a simple method. In addition, in the method of forming a microlens for a liquid crystal display element using a radiation sensitive resin composition, an organic solvent is often contained in a resin composition, and the composition is subjected to a spin coating method, a dipping method, a spray method, or the like. The composition is layered on the substrate. Among these methods, it is necessary to obtain the time required for setting conditions of a predetermined film thickness, and environmental problems such as volatilization of a solvent have also been found. Therefore, it is also required to develop a microlens method using a dry film of a radiation sensitive resin composition. Compared with the conventional microlens manufacturing method, only a thin film is laminated on a substrate, and a certain amount of radiation is irradiated for display. Like, for a short time and low cost. In the production of a microlens using a dry film of a radiation sensitive resin composition, the exposure step is performed in a state where the radiation sensitive resin composition layer is blocked by the base film and the outside air, and the radiation sensitive resin composition layer is formed. The exposed portion tends to be extremely hardened without being hindered by oxygen during the radical polymerization reaction. Therefore, it has been difficult to obtain a desired melt shape after post-baking to obtain a desired lens shape. As described above, the high-yield microlens of 200911523 is produced at a high yield with a simple dry film method. In the development of the method, when the dry film method is used, there is a strong demand for the establishment of a radiation-sensitive resin composition layer capable of controlling the shape of the lens after post-baking. Patent Document 1: Japanese Patent Laid-Open Publication No. 2003-255318 Patent Document 2: Japanese Patent Laid-Open No. 2 0 01 - 1 5 4 1 8 1 Patent Document 3: Japanese Patent Special Opening 2 0 0 1 - 1 1 7 1 Patent Document 4: Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. No. Hei. Technical Problem The present invention has been made in view of the problems existing in the conventional technology. It is an object of the invention to provide a dry film photoresist which can form a desired photoresist shape by having sufficient melt fluidity in the radiation-sensitive resin composition layer after drying. Another object of the present invention is to provide a method for producing the above dry film photoresist. Still another object of the present invention is to provide a microlens using the above dry film photoresist and a method of manufacturing the same. Another object of the present invention is to provide a liquid crystal display member comprising the above microlens. Other objects and advantages of the invention will be apparent from the description. In order to solve the above problems, the inventors have found that by laminating a radiation-sensitive resin composition containing a chain-transfer 200911523 transfer agent on a base film, it is possible to control the melt fluidity and achieve the feeling of the present invention. Radiation linear dry film. That is, according to the present invention, the above objects and advantages of the present invention, the first point is achieved according to a dry film, characterized in that the thickness of the layer deposited on the base film by the base film is 2 to 200 μm, per lm 2 As a result of randomly measuring 10 points, the difference between the maximum and the minimum is composed of a radiation-sensitive resin composition layer of a uniform film having a film thickness of 5% or less and a film deposited on the radiation-sensitive resin composition layer. The radiation-linear resin composition layer contains (A) an alkali-soluble copolymer, (B) a polymerizable unsaturated compound, (C) a photopolymerization initiator, and (D) a chain transfer agent. According to the present invention, the above objects and advantages of the present invention are achieved in accordance with a method for producing a radiation-sensitive dry film, characterized in that the radiation-sensitive resin composition of the present invention is coated on a flexible base film. The article 'after drying to form a radiation sensitive coating film. According to the present invention, the above objects and advantages of the present invention, the third point is achieved by a microlens, which is formed using the dry film of the present invention. According to the present invention, the above objects and advantages of the present invention are achieved in accordance with a method of forming a microlens, characterized by at least the following steps (i) to (iv): (i) from the present invention a step of peeling off the film on the dry film, transferring the radiation sensitive resin composition layer to the glass substrate to form a coating film; (ii) a step of irradiating at least a part of the coating film with radiation; (Hi) after the image irradiation a step of coating the film; and (1 v) a step of heating the film after development. According to the present invention, the above objects and advantages of the present invention are achieved in accordance with a liquid crystal display device comprising the microlens of the present invention. [Embodiment] The best shaped bear for carrying out the invention Hereinafter, the present invention will be described in detail. The thickness of the base film which can be used in the present invention is not particularly limited, and is, for example, suitably 5 to 125 μm. More preferably, the thickness is from 1 〇 to 50 μηι. For the base film having such a thickness, for example, the following commercially available products can be obtained: PET film "R340G16" (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., 16 μm thick), and "Ε2" (manufactured by Teijin DUPONT Film Co., Ltd.) "Χ83 (Dynasty DUPONT film (manufacturing)), DIAFOIL "R310" (Mitsubishi Chemical Polyester Film Co., Ltd., 16μιη thick), COSMOSHINE "A4100" (Toyo Textile Co., Ltd., 50μιη thick), "A4300" ( Toyo Textiles Co., Ltd., 5〇μιη厚), DIAFOIL “Τ100Β25” (Mitsubishi Chemical Polyester Film Co., Ltd., 25, thick), “T100G38” (Mitsubishi Chemical Polyester Film (Unit), 38^m Thick) and so on. The dry film of the present invention has a radiation-sensitive resin composition layer on the above-mentioned base film, and the film further covers the composition layer. The film is preferably used, such as a polyethylene terephthalate (PET) film and a polyethylene (P E ) film. Further, it is more preferable to use PET and PE films having a self-adhesive resin layer. The thickness of the film is not particularly limited, for example, 'preferably 5 to 2 0 0 μηι. The PET film is preferably a release-treated material. For example, PUREX FILM "A31" (manufactured by Teijin DUPONT FILM Co., Ltd., 25μηι thick and 38μιη thick), PUREX FILM "A54" (manufactured by Teijin DUPONT FILM), 25μπι Thickness and thickness of 38 μηι), DIAFOIL "MRF" (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., 25 μm thick and 38 μm thick), "MRA50" (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., 50 μηι thick). In addition, as for the ΡΕ film of the commercial product, for example, "WAKO GREEN FILM PE" (made of WAKO resin (stock), 21μιη thick and 40μιη thick), "GF-1" (made of TAMAPOLY), "GF" -3" (TAMAPOLY (stock), 30μιη thick), "PE-LD" (Asahi Kasei CHEMICALS), and "ΡΕ-HD" (Asahi Kasei CHEMICALS). In addition, a film having a self-adhesive resin layer can be suitably obtained by, for example, a PE film "TORETEC 7721" (manufactured by TORAY FILM Co., Ltd., 60 μm thick). Next, the radiation sensitive resin composition of the radiation sensitive resin composition layer will be described. The radiation sensitive resin composition contains: (A) an alkali-soluble copolymer, (B) a polymerizable unsaturated compound, (C) a photopolymerization initiator, and (D) a chain transfer agent. ~(A) alkali-soluble copolymer - (A) component in the present invention is soluble in the alkali imaging liquid of the developing liquid used in the developing process step when manufacturing the microlens. If the light is well penetrated, 'it is particularly desirable' is not particularly limited. In particular, (a) a polymerizable unsaturated compound having one or more acidic functional groups in the molecule (hereinafter referred to as "(a) polymerizable unsaturated-10-200911523 and a compound") 5 to 60 weight % ' and (b) 40 to 95% by weight of other polymerizable unsaturated compound (but '(a) + (b) = 100% by weight) is an alkali-soluble copolymer (hereinafter referred to as "(A) copolymerization Further, (b) the other polymerizable unsaturated compound is particularly preferably an alkali-soluble copolymer containing an N-substituted maleimide. (a) The acidic functional group of the polymerizable unsaturated compound may, for example, be a carboxyl group or a sulfonic acid group, and particularly preferably a carboxyl group. (a) a polymerizable unsaturated compound having a residue (hereinafter, referred to as "( 31)
聚合性不飽和化合物」。），例如，可列舉：（甲基）丙 烯酸、丁烯酸、丙烯酸或丁烯酸之α -位被鹵院基、，院氧基、 鹵素原子、硝基、氰基等取代基所取代之化合物等之不飽 和單羧酸；馬來酸、馬來酸酐、富馬酸、檸康酸、中康酸、 依康酸等之不飽和二羧酸或其酸酐；上述不飽和二殘酸中 之一羧基的氫原子被甲基、 基、二級丁基、三級丁基、 乙基 '正丙基、異丙基、正丁 苯基 ' 鄰甲苯基 '間甲苯基、 對甲苯基等之取代基所取代之半酯；上述不飽和二羧酸中 之一羧基轉換成醯胺基的半醯胺；（甲基）丙烯酸_2_羥乙 S曰與琥珀酸之單酯化物、（甲基）肖烯酸_ 2 _羥乙酯與馬來 酸之單酯化物、（甲基）丙烯酸_2_羥乙酯與六氫化苯二甲 酸之單酯化物（以下，表示「（甲基）丙烯酸-2_單（六氫 等含羧基之（甲基）丙烯酸酯 化苯二甲醯氧基）乙酉旨 等。 此寺聚合性不飽和化合物之中，尤以（甲基） 丙嫌酸、（甲基）丙嫌酸_2-單（六氫化苯二甲酿氧基）乙 200911523 酯、ω-羧基聚氯內酯單（甲基）丙烯酸酯等特別理想。 於本發明中，（a )聚合性不飽和化合物能夠單獨地或 混合二種以上後而使用。尤以倂用（甲基）丙烯酸與（甲 基）丙烯酸-2 -單（六氫化苯二甲醯氧基）乙酯特別理想。 (A )共聚物中佔有之（a )聚合性不飽和化合物的含 率適宜爲5〜60重量％，更佳爲1〇〜50重量％，尤以15 〜4 0重量％特別理想。若（a )聚合性不飽和化合物的含 率低於5重量％時，擔憂所得的共聚物將變得難溶於鹼顯 像液，而在顯像後生成膜殘留，得到充分之解像度將變得 困難，另一方面，若超過60重量％時，相對於所得的共聚 物之鹼顯像液的溶解性將變得過大，放射線照射部之膜減 少將有變大之傾向。 (b )其他之聚合性不飽和化合物係主要以控制（A ) 共聚物機械特性之目的所使用之物。 (b )其他之聚合性不飽和化合物適宜爲於（A )共聚 物中含有5〜40重量％之N位-取代之馬來醯亞胺（以下， 稱爲「（ b -1 )聚合性不飽和化合物」。），更佳爲含有1 0 〜3 5重量％。 (b-1 )聚合性不飽和化合物，例如，可列舉：N-苯基 馬來醯亞胺、N-鄰羥苯基馬來醯亞胺、N-間羥苯基馬來醯 亞胺、N-對羥苯基馬來醯亞胺、N-苄基馬來醯亞胺、N-環 己基馬來醯亞胺、N-琥珀醯亞胺基-3-馬來醯亞胺苯甲酸 醋、N-琥珀醯亞胺基-4-馬來醯亞胺丁酸酯、N-琥珀醯亞胺 基-6-馬來醯亞胺己酸酯、N-琥珀醯亞胺基-3-馬來醯亞胺丙 -12- 200911523 酸醋、N -(吖啶基）馬來醯亞胺等。 此等（b -1 )聚合性不飽和化合物之中，尤以N _苯基馬 來醯.亞胺、N-環己基馬來醯亞胺特別理想。於（a )共聚物 中’（b -1 )聚合性不飽和化合物能夠單獨地或混合二種以 上後而使用。 N位-取代之馬來醯亞胺以外之（b )其他聚合性不飽 和化合物（以下，稱爲「（ b - 2 )聚合性不飽和化合物」。）， 例如’可列舉：（甲基）丙烯酸酯、不飽和羧酸胺基烷酯、 不飽和羧酸環氧丙酯、針對上述（a )聚合性不飽和化合物 所列舉之不飽和二羧酸的二酯、芳香族乙烯化合物、共軛 二烯烴、含有腈基之不飽和化合物、含有氯之不飽和化合 物、含有醯胺鍵之不飽和化合物、不飽和醯亞胺、不飽和 醚、脂肪酸乙烯酯、含有脂環式烴基之不飽和化合物、於 聚合物分子鏈末端含有單（甲基）丙烯醯基之巨單體等。 上述（甲基）丙烯酸酯，例如，可列舉：（甲基）丙 烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丙酯、 (甲基）丙烯酸異丙酯、（甲基）丙烯酸正丁酯、（甲基） 丙烯酸二級丁酯、（甲基）丙烯酸三級丁酯、（甲基）丙 烯酸異丁酯、（甲基）丙烯酸正戊酯、（甲基）丙烯酸新 戊酯、（甲基）丙烯酸-4 -異戊基己酯、（甲基）丙烯酸-2-羥乙酯、（甲基）丙烯酸-2-羥丙酯、（甲基）丙烯酸-3-羥丙酯、（甲基）丙烯酸-2 -羥丁酯、（甲基）丙烯酸-3 -羥丁酯、（甲基）丙烯酸-4-羥丁酯、（甲基）丙烯酸-2-甲氧基乙酯、（甲基）丙烯酸-2-苯氧基乙酯、（甲基）丙 -13- 200911523 烯酸甲氧基二乙二醇酯、（甲基）丙烯酸甲氧基三乙二醇 酯、（甲基）丙烯酸甲氧基丙二醇酯、（甲基）丙烯酸甲 氧基二丙二醇酯、（甲基）丙烯酸二環戊二烯酯、（甲基） 丙烯酸-2-羥基-3-苯氧基丙酯、單（甲基）丙烯酸丙三醇酯、 (甲基）丙烯酸烯丙酯、（甲基）丙烯酸炔丙酯、（甲基） 丙烯酸苯酯、（甲基）丙烯酸萘酯、（甲基）丙烯酸蒽酯、 (甲基）丙烯酸蒽醌酯、（甲基）丙烯酸胡椒酯、（甲基） 丙烯酸水楊酯、（甲基）丙烯酸苄酯、（甲基）丙烯酸苯 乙酯、（甲基）丙烯酸羥甲苯酯、（甲基）丙烯酸環氧丙 酯、（甲基）丙烯酸三苯基甲酯、（甲基）丙烯酸異丙苯 酯、（甲基）丙烯酸-2,2,2-三氟乙酯、（甲基）丙烯酸五 氟乙酯、（甲基）丙烯酸七氟正丙酯、（甲基）丙烯酸七 氟異丙酯、（甲基）丙烯酸-2- ( N，N-二甲胺基）乙酯、（甲 基）丙烯酸-3 - ( N，N -二甲胺基）丙酯、（甲基）丙烯酸呋 喃酯、（甲基）丙烯酸糠酯、（甲基）丙烯酸四氫糠酯、α-(甲基）丙烯醯氧基-γ_ 丁內酯、β-(甲基）丙烯醯氧基_γ-丁內酯等。 上述不飽和羧酸胺基烷酯，例如，可列舉：（甲基） 丙嫌酸-2-胺基乙酯、（甲基）丙稀酸-2-二甲胺基乙醋、（甲 基）丙稀酸-2 -胺基丙醋、（甲基）丙稀酸-2 -二甲胺基丙醋、 (甲基）丙烧酸-3-胺基丙酯、（甲基）丙稀酸_3_二甲胺基 丙酯等。 上述不飽和竣酸環氧丙酯，例如，可列舉：（甲基） 丙烯酸環氧丙酯。 -14- 200911523 上述不飽和二羧酸之二酯’例如，可列舉：馬來酸一 甲酯、馬來酸二乙酯、富馬酸二甲酯、富馬酸二乙醋、衣 康酸二甲酯、衣康酸二乙酯等。 上述芳香族乙烯化合物’例如’可列舉：苯乙稀' α_ 甲基苯乙烯、鄰甲基苯乙烯、間甲基苯乙烯、對甲基苯乙 烯、對甲氧基苯乙烯、苯甲酸乙烯酯等。 上述共軛二烯烴，例如’可列舉：1 ,3 - 丁二嫌、異戊 二烯、2,3-二甲基-1,3-丁二烯等。 上述含有腈基之不飽和化合物’例如，可列舉：（甲 基）丙烯腈、氰化亞乙烯、α-氯丙烯腈等。 上述含有氯之不飽和化合物，例如，可列舉：氯乙稀、 偏氯乙烯等。 上述含有醯胺鍵之不飽和化合物，例如，可列舉：（甲 基）丙烯醯胺、馬來酸二醯胺、富馬酸二醯胺、α-氯丙烯 酸胺、Ν-2-羥乙基（甲基）丙烯醯胺等。 上述不飽和醯亞胺，例如，可列舉：馬來醯亞胺等。 上述不飽和醚，例如，可列舉：乙烯基甲基醚、乙烯 ®乙基醚、烯丙基環氧丙基醚等。 上述脂肪酸乙烯酯，例如，可列舉：醋酸乙烯酯、丁 酸乙烯酯、丙酸乙烯酯等。 上述含有脂環式烴基之不飽和化合物，例如，可列舉· (甲基）丙烯酸環戊酯、（甲基）丙稀酸-丨_甲基環戊酯、 (甲基）丙烯酸-2-甲基環戊酯、（甲基）丙烯酸環己酯、 (甲基）丙烯酸-1-甲基環己酯、（甲基）丙烯酸_2_甲基瓌 -15- 200911523 己酯、（甲基）丙嫌酸異茨院酯、（甲基）丙稀酸三環癸 酯、（甲基）丙烯酸金剛烷酯、（甲基）丙烯酸-2-二環戊 氧乙酯等。 上述巨單體，例如，可列舉：聚苯乙烯、聚（甲基） 丙烯酸甲酯、聚（甲基）丙烯酸正丁酯、聚矽氧烷等之聚 合物分子鏈之末端具有單（甲基）丙烯醯基之化合物等。 此等（b - 2 )聚合性不飽和化合物之中，較佳爲（甲基） 丙烯酸甲酯、（甲基）丙烯酸-2-羥乙酯、單（甲基）丙烯 酸甘油酯、苯乙烯、α-甲基苯乙烯、（甲基）丙烯酸苄醋、 (甲基）丙烯酸異莰烷酯、（甲基）丙烯酸三環癸酯、〖，3 — 丁二烯、異戊二烯等。 於本發明中’（b-2 )聚合性不飽和化合物能夠單獨地 或混合二種以上後而使用。（A )共聚物之具體例，例如， 可列舉：（甲基）丙烯酸/(甲基）丙烯酸甲酯共聚物、（甲 基）丙烯酸/ (甲基）丙烯酸苄酯共聚物、（甲基）丙烯酸 /(甲基）丙烯酸-2-羥乙酯/ (甲基）丙烯酸苄酯共聚物、 (甲基）丙烯酸/苯乙烯/異戊二烯/(甲基）丙烯酸三環癸 酯/(甲基）丙烯酸-2-單（六氫化苯二甲醯氧基）乙酯共聚 物、（甲基）丙烯酸/苯乙烯/1,3-丁二烯/(甲基）丙烯酸三 環癸酯/ (甲基）丙烯酸-2-單（六氫化苯二甲醯氧基）乙酯 共聚物、（甲基）丙烯酸/苯乙烯/ (甲基）丙烯酸苄酯/ N-苯基馬來醯亞胺共聚物、（甲基）丙烯酸/(甲基）丙烯酸 苄酯/(甲基）丙烯酸-2-羥乙酯共聚物、（甲基）丙烯酸/ 苯乙烯/(甲基）丙烯酸苄酯/單（甲基）丙烯酸甘油酯/N_ 200911523 苯基馬來醯亞胺共聚物、（甲基）丙烯酸/單（甲基）丙烯 酸-ω-羧基聚氯內酯/苯乙烯/(甲基）丙烯酸苄酯/單（甲基） 丙烯酸甘油酯/Ν-苯基馬來醯亞胺共聚物等。 (A )共聚物中佔有之（b )其他之聚合性不飽和化合 物的含率適宜爲40〜95重量％，更佳爲50〜90重量％， 尤以6 0〜8 5重量％特別理想。 (A)共聚物之聚苯乙烯換算重量平均分子量（以下， 稱爲「1^评」。）適宜爲2,000~100,000，更佳爲5,000〜 f 50,000。若（A)共聚物之Mw低於2,000時，將有鹼顯像 性、殘膜率、圖案形狀、耐熱性等將降低之傾向，另一方 面，若超過1 00,000時，將有感度或圖案形狀將降低之傾 向。 另外，（A)共聚物之MW與聚乙烯換算數目平均分子 量（以下，稱爲「Μη」。）之比（Mw/Mn)適宜爲1.0〜 5.0，更佳爲1.0〜3.0。 (A )共聚物係藉由在適當之溶劑中，聚合（a )聚合 ί. 性不飽和化合物與（b )其他之聚合性不飽和化合物而能夠 加以製造。 上述聚合所用之溶劑，例如，可列舉：甲醇、乙醇、 雙丙酮醇等之醇；四氫呋喃、四氫吡喃、二噚烷等之醚； 乙二醇單甲基醚、乙二醇單乙基醚等之乙二醇單烷基醚； 乙二醇單甲基醚醋酸酯、乙二醇單乙基醚醋酸酯等之乙二 醇單烷基醚醋酸酯；二乙二醇單甲基醚、二乙二醇單乙基 醚、二乙二醇二甲基醚、二乙二醇乙基甲基醚、二乙二醇 -17- 200911523 二乙基醚等之二乙二醇烷基醚； 丙二醇單甲基醚、丙二醇單乙基醚、丙 醚、丙二醇單正丁基醚等之丙二醇單烷基醚 基醚醋酸酯、丙二醇單乙基醚醋酸酯、丙二 醋酸酯、丙二醇單正丁基醚醋酸酯等之丙二 酸酯；丙二醇單甲基醚丙酸酯、丙二醇單乙 丙二醇單正丙基醚丙酸酯、丙二醇單正丁基 丙二醇單烷基醚丙酸酯；甲苯、二甲苯等之 基乙基酮、甲基異丁基酮、2 -庚酮、環己酮 基-2 -戊酮等酮。 醋酸甲酯、醋酸乙酯、醋酸正丙酯、醋 基醋酸甲酯、羥基醋酸乙酯、羥基醋酸正丙 正丁酯、乳酸甲酯、乳酸乙酯、乳酸正丙酯、 3-羥基丙酸甲酯、3-羥基丙酸乙酯、3-羥基朽 羥基丙酸正丁酯、2-羥基-2-甲基丙酸甲酯、 丙酸乙酯、2 -羥基-3 -甲基丁酸甲酯、甲氧基 氧基醋酸乙酯、甲氧基醋酸正丙酯、甲氧基 乙氧基醋酸甲酯、乙氧基醋酸乙酯、乙氧基 乙氧基醋酸正丁酯、正丙氧基醋酸甲酯、正 酯、正丙氧基醋酸正丙酯、正丙氧基醋酸正 基醋酸甲酯、正丁氧基醋酸乙酯、正丁氧基 正丁氧基醋酸正丁酯、2 -甲氧基丙酸甲酯、 乙酯、2 -甲氧基丙酸正丙酯、2 -甲氧基丙酸2 基丙酸甲酯、2_乙氧基丙酸乙酯、2 -乙氧基 二醇單正丙基 ;丙二醇單甲 醇單正丙基醚 醇單烷基醚醋 基醚丙酸酯、 醚丙酸酯等之 芳香族烴；甲 、4 -羥基-4 -甲 酸正丁酯、羥 酯、羥基醋酸 乳酸正丁酯、 ί酸正丙酯、3 -2 -羥基-2 -甲基 醋酸甲酯、甲 醋酸正丁酯、 醋酸正丙酯、 丙氧基醋酸乙 丁酯、正丁氧 醋酸正丙酯、 2 -甲氧基丙酸 ΐ 丁酯、2 -乙氧 丙酸正丙酯、 -18- 200911523 2 -乙氧基丙酸正丁酯、2 -正丙氧基丙酸甲酯、2 -正丙氧基丙 酸乙酯、2 -正丙氧基丙酸正丙酯、2 -正丙氧基丙酸正丁酯、 2- 正丁氧基丙酸甲酯、2-正丁氧基丙酸乙酯、2-正丁氧基丙 酸正丙酯、2 -正丁氧基丙酸正丁酯、3 -甲氧基丙酸甲酯、 3- 甲氧基丙酸乙酯、3-甲氧基丙酸正丙酯、3-甲氧基丙酸正 丁酯、3 -乙氧基丙酸甲酯、3 -乙氧基丙酸乙酯、3 -乙氧基丙 酸正丙酯、3 -乙氧基丙酸正丁酯' 3 -正丙氧基丙酸甲酯、 3 -正丙氧基丙酸乙酯、3 -正丙氧基丙酸正丙酯、3 -正丙氧基 丙酸正丁酯、3-正丁氧基丙酸甲酯、3-正丁氧基丙酸乙酯、 3 -正丁氧基丙酸正丙酯、3 -正丁氧基丙酸正丁酯等之其他 酯。 此等溶劑能夠單獨地或混合二種以上後而使用。 上述自由基聚合起始劑，例如，可列舉：2,2 偶氮雙 異丁腈、2,2’-偶氮雙（2,4-二甲基戊腈）、2,2’-偶氮雙（4-甲氧基-2，4-二甲基戊腈）等之偶氮化合物；過氧化苯甲醯、 過氧化月桂醯、過氧化二甲基乙酸三級丁酯、1,1，-雙（過 氧化三級丁基）環己烷等之有機過氧化物或過氧化氫等。 自由基聚合起始劑使用過氧化物之情形下，也可以倂用還 原劑而作成氧化還原型起始劑。 於本發明中，（A )共聚物能夠單獨地或混合二種以上 後而使用。 -（B )聚合性不飽和化合物- 本發明中之（B )聚合性不飽和化合物係藉由（C )光 聚合起始劑存在下之放射線照射而進行聚合的化合物。 -19-Polymeric unsaturated compound". For example, the α-position of (meth)acrylic acid, crotonic acid, acrylic acid or crotonic acid may be replaced by a substituent such as a halogen-based group, a oxy group, a halogen atom, a nitro group or a cyano group. An unsaturated monocarboxylic acid such as a compound; an unsaturated dicarboxylic acid such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, mesaconic acid or isaconic acid or an anhydride thereof; and the above unsaturated di-residual acid One of the hydrogen atoms of the carboxyl group is a methyl group, a base, a secondary butyl group, a tertiary butyl group, an ethyl 'n-propyl group, an isopropyl group, a n-butylphenyl 'o-tolyl'-m-tolyl group, a p-tolyl group, etc. a half ester substituted with a substituent; a half decylamine in which one of the above unsaturated dicarboxylic acids is converted into a decylamino group; a monoester of (meth)acrylic acid 2-hydroxyethyl hydrazine and succinic acid, Methyl)co-enoic acid _ 2 hydroxyethyl ester with monoester of maleic acid, monoester of 2-hydroxyethyl (meth)acrylate and hexahydrophthalic acid (hereinafter, "(methyl) Acrylic acid-2_mono (carboxyl-containing (meth)acrylated benzyl oxime), etc. Among the compounds, (meth) propyl citrate, (methyl) propylene succinic acid 2 - mono (hexahydrophenyl methoxy) ethyl 200911523 ester, ω-carboxy polychlorolactone mono (A In the present invention, (a) the polymerizable unsaturated compound can be used singly or in combination of two or more kinds thereof, particularly (meth)acrylic acid and (meth)acrylic acid-2. - Mono(hexahydroxydimethoxy)ethyl ester is particularly preferable. (A) The content of the (a) polymerizable unsaturated compound is preferably 5 to 60% by weight, more preferably 1 〇. 50% by weight, particularly preferably 15 to 40% by weight, is particularly preferable. When the content of the (a) polymerizable unsaturated compound is less than 5% by weight, it is feared that the obtained copolymer will become insoluble in the alkali developing solution. On the other hand, when the film remains after development, it becomes difficult to obtain sufficient resolution. On the other hand, when it exceeds 60% by weight, the solubility of the alkali developing solution with respect to the obtained copolymer becomes too large, and radiation irradiation is performed. The film reduction of the part will tend to become larger. (b) Other polymerizable unsaturated compounds are the main The material used for the purpose of controlling the mechanical properties of the (A) copolymer. (b) Other polymerizable unsaturated compounds are suitably contained in the (A) copolymer in an amount of 5 to 40% by weight of the N-substituted Malayan. The imine (hereinafter referred to as "(b-1) polymerizable unsaturated compound") is more preferably contained in the range of 10 to 35 wt%. (b-1) The polymerizable unsaturated compound, for example, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-benzyl Maleic imine, N-cyclohexylmaleimide, N-succinimide-3-maleimidobenzoic acid vinegar, N-succinimide-4-maleimide Butyrate, N-succinimide-6-maleimide caproate, N-amber succinimide-3-maleimide C--12- 200911523 Sour vinegar, N-(吖Pyridyl) maleic imine and the like. Among these (b-1) polymerizable unsaturated compounds, N-phenylmalbenium imine and N-cyclohexylmaleimide are particularly preferred. In the (a) copolymer, the '(b-1) polymerizable unsaturated compound can be used singly or in combination of two or more. (b) other polymerizable unsaturated compound other than the N-substituted substituted maleimide (hereinafter referred to as "(b-2) polymerizable unsaturated compound"), for example, 'may be listed: (methyl) An acrylate, an aminoalkyl ester of an unsaturated carboxylic acid, a glycidyl acrylate of an unsaturated carboxylic acid, a diester of an unsaturated dicarboxylic acid exemplified for the above (a) a polymerizable unsaturated compound, an aromatic vinyl compound, and a conjugate Diolefin, unsaturated compound containing nitrile group, unsaturated compound containing chlorine, unsaturated compound containing guanamine bond, unsaturated quinone imine, unsaturated ether, vinyl ester of fatty acid, unsaturated compound containing alicyclic hydrocarbon group A macromonomer containing a mono(meth)acrylonitrile group at the end of the polymer molecular chain. Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (methyl). ) n-butyl acrylate, n-butyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, n-amyl (meth)acrylate, new (meth)acrylic acid Amyl Ester, 4-Isoamylhexyl (meth)acrylate, 2-Hydroxyethyl (meth)acrylate, 2-Hydroxypropyl (meth)acrylate, 3-Hydroxy (meth)acrylate Propyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-methoxyl (meth)acrylate Ethyl ester, 2-phenoxyethyl (meth)acrylate, (methyl)propene-13-200911523 oxydiethylene glycol olefinate, methoxytriethylene glycol (meth)acrylate , methoxypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, dicyclopentadienyl (meth)acrylate, (meth) propylene Acid-2-hydroxy-3-phenoxypropyl ester, glycerol mono(meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate , naphthyl (meth) acrylate, decyl (meth) acrylate, decyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, benzyl (meth) acrylate Benzyl (meth)acrylate, hydroxytoluene (meth)acrylate, glycidyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumene (meth)acrylate, (2,2,2-trifluoroethyl (meth)acrylate, pentafluoroethyl (meth)acrylate, heptafluoropropyl (meth)acrylate, heptafluoroisopropyl (meth)acrylate, ( 2-(N,N-dimethylamino)ethyl methacrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, furyl (meth) acrylate, ( Ethyl methacrylate, tetrahydrofurfuryl (meth) acrylate, α-(meth) propylene methoxy-γ-butyrolactone, β-(meth) propylene methoxy γ-butane Wait. The above-mentioned unsaturated amino acid alkyl carboxylate may, for example, be (meth)acrylic acid-2-aminoethyl ester, (meth)acrylic acid-2-dimethylaminoethyl acetate, (methyl group) Acetate-2-aminopropyl acetonate, (meth)acrylic acid-2-dimethylaminopropyl acetonate, (meth)propionic acid-3-aminopropyl ester, (meth) propylene Acid _3-dimethylaminopropyl and the like. The unsaturated glycidyl phthalate may, for example, be a glycidyl (meth)acrylate. -14- 200911523 The above-mentioned unsaturated dicarboxylic acid diester 'for example, may be mentioned: monomethyl maleate, diethyl maleate, dimethyl fumarate, diacetate fumarate, itaconic acid Dimethyl ester, diethyl itaconate, and the like. The above aromatic vinyl compound 'for example' may, for example, be styrene-α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene or vinyl benzoate. Wait. The conjugated diene may, for example, be 1,3-dibutyl, isoprene or 2,3-dimethyl-1,3-butadiene. Examples of the nitrile group-containing unsaturated compound' include, for example, (meth)acrylonitrile, vinyl cyanide, and α-chloroacrylonitrile. Examples of the chlorine-containing unsaturated compound include vinyl chloride and vinylidene chloride. Examples of the above-mentioned unsaturated compound containing a guanamine bond include (meth) acrylamide, diammonium maleate, diammonium fumarate, α-chloroacrylic acid amine, oxime-2-hydroxyethyl group. (Methyl) acrylamide and the like. Examples of the unsaturated quinoid imide include maleic imine and the like. Examples of the unsaturated ether include vinyl methyl ether, ethylene ethyl ether, and allyl epoxy propyl ether. The fatty acid vinyl ester may, for example, be vinyl acetate, vinyl butyrate or vinyl propionate. Examples of the unsaturated compound containing an alicyclic hydrocarbon group include, for example, cyclopentyl (meth)acrylate, (meth)acrylic acid-indole methylcyclopentyl ester, and (meth)acrylic acid-2-methyl. Cyclopentyl ester, cyclohexyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 2 -methyl hydrazine (meth) acrylate - 200911523 hexyl ester, (methyl) Amorphic acid isopropionate, trimethyl decyl (meth) acrylate, adamantyl (meth) acrylate, 2-dicyclopentyloxy (meth) acrylate, and the like. Examples of the macromonomer include polystyrene, poly(methyl) methacrylate, poly(methyl) acrylate, n-decane, and the like, and the polymer molecular chain has a single (methyl group) at the end. a compound of an acrylonitrile group or the like. Among these (b - 2 ) polymerizable unsaturated compounds, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycerol mono(meth)acrylate, styrene, and the like are preferable. Α-methylstyrene, benzyl methacrylate, isodecyl (meth)acrylate, tricyclodecyl (meth)acrylate, 1,3-butadiene, isoprene, and the like. In the present invention, the '(b-2) polymerizable unsaturated compound can be used singly or in combination of two or more kinds. Specific examples of the (A) copolymer include, for example, (meth)acrylic acid/methyl (meth)acrylate copolymer, (meth)acrylic acid/benzyl (meth)acrylate copolymer, (methyl) Acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylate / styrene / isoprene / tricyclodecyl (meth) acrylate / (A Acrylic acid-2-monohexa(hexahydrophthaloxy)ethyl ester copolymer, (meth)acrylic acid/styrene/1,3-butadiene/tricyclodecyl (meth)acrylate/ Methyl)acrylic acid-2-monohexa(hexahydrophthaloxy)ethyl ester copolymer, (meth)acrylic acid/styrene/benzyl (meth)acrylate/N-phenylmaleimide copolymerization , (meth)acrylic acid / benzyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylate / styrene / benzyl (meth) acrylate / single (A Glycerol acrylate/N_ 200911523 phenyl maleimide copolymer, (meth)acrylic acid/mono(meth)acrylic acid-ω-carboxypolychlorolactone/styrene/(meth)acryl Benzyl ester / mono (meth) acrylate / Ν- phenylmaleimide copolymer (PEI). (A) The content of the (b) other polymerizable unsaturated compound which is contained in the copolymer is suitably 40 to 95% by weight, more preferably 50 to 90% by weight, particularly preferably 60 to 8.5 % by weight. (A) The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "1" evaluation) of the copolymer is suitably 2,000 to 100,000, more preferably 5,000 to f 50,000. When the Mw of the (A) copolymer is less than 2,000, the alkali developability, the residual film ratio, the pattern shape, the heat resistance and the like tend to be lowered. On the other hand, if it exceeds 100,000, the sensitivity or pattern will be obtained. The tendency of the shape will decrease. Further, the ratio (Mw/Mn) of the MW of the (A) copolymer to the number average molecular weight (hereinafter referred to as "Μη") in terms of polyethylene is suitably 1.0 to 5.0, more preferably 1.0 to 3.0. (A) The copolymer can be produced by polymerizing (a) a polymerizable unsaturated compound and (b) another polymerizable unsaturated compound in a suitable solvent. Examples of the solvent used for the polymerization include alcohols such as methanol, ethanol, and diacetone alcohol; ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; ethylene glycol monomethyl ether and ethylene glycol monoethyl Ethylene glycol monoalkyl ether such as ether; ethylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate or ethylene glycol monoethyl ether acetate; diethylene glycol monomethyl ether , diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol-17- 200911523 diethyl ether and other diethylene glycol alkyl ether Propylene glycol monomethyl ether ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol acetate, propylene glycol mono-positive Malonate such as butyl ether acetate; propylene glycol monomethyl ether propionate, propylene glycol monoethylene glycol monopropyl ether propionate, propylene glycol mono-n-butyl propylene glycol monoalkyl ether propionate; toluene, A ketone such as a base ethyl ketone such as xylene, methyl isobutyl ketone, 2-heptanone or cyclohexanone-2-pentanone. Methyl acetate, ethyl acetate, n-propyl acetate, methyl acetate, ethyl hydroxyacetate, n-butyl hydroxyacetate, methyl lactate, ethyl lactate, n-propyl lactate, 3-hydroxypropionic acid Methyl ester, ethyl 3-hydroxypropionate, n-butyl 3-hydroxy-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl propionate, 2-hydroxy-3-methylbutyric acid Methyl ester, ethyl methoxyoxyacetate, n-propyl methoxyacetate, methyl methoxyethoxyacetate, ethyl ethoxyacetate, n-butyl ethoxyethoxyacetate, n-propyl Methyl oxyacetate, n-ester, n-propyl n-propoxyacetate, methyl n-propoxyacetate, methyl n-butoxyacetate, n-butyl n-butoxy n-butoxyacetate, 2 Methyl methoxypropionate, ethyl ester, n-propyl 2-methoxypropionate, methyl 2-propoxypropionate, ethyl 2-ethoxypropionate, 2-B Alkyl propylene glycol mono-n-propyl; propylene glycol monomethanol mono-n-propyl ether alcohol monoalkyl ether acetoxy ether propionate, ether propionate and other aromatic hydrocarbons; methyl 4-hydroxy-4-carboxylic acid n-butyl Ester, hydroxyester, hydroxyacetic acid N-butyl acrylate, n-propyl phthalate, methyl 3 -2 -hydroxy-2-methylacetate, n-butyl methacrylate, n-propyl acetate, ethyl butyl oxyacetate, n-butoxyacetic acid Ester, butyl 2-methoxypropionate, n-propyl 2-ethoxypropionate, -18- 200911523 2-n-butyl ethoxypropionate, methyl 2-n-propoxypropionate, 2 -ethyl n-propoxypropionate, n-propyl 2-n-propoxypropionate, n-butyl 2-n-propoxypropionate, methyl 2-n-butoxypropionate, 2-n-butoxy Ethyl propyl propionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, N-propyl 3-methoxypropionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropionic acid Propyl ester, n-butyl 3-ethoxypropionate, methyl 3-n-propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, 3- n-Butyl n-propoxypropionate, methyl 3-n-butoxypropionate, ethyl 3-n-butoxypropionate, n-propyl 3-n-butoxypropionate, 3-n-butoxy Propionic acid Butyl ester of the other. These solvents can be used singly or in combination of two or more kinds. The above radical polymerization initiator may, for example, be 2,2 azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azo An azo compound such as bis(4-methoxy-2,4-dimethylvaleronitrile); benzamidine peroxide, laurel peroxide, butyl peroxydiacetate, 1,1, An organic peroxide such as bis(tributylphosphonium peroxide) cyclohexane or hydrogen peroxide or the like. In the case where a peroxide is used as the radical polymerization initiator, a reducing agent may be used as a redox initiator. In the present invention, the (A) copolymer can be used singly or in combination of two or more. - (B) Polymerizable unsaturated compound - (B) The polymerizable unsaturated compound in the present invention is a compound which is polymerized by radiation irradiation in the presence of (C) a photopolymerization initiator. -19-
200911523 (B )聚合性不飽和化合物，例如，可列舉 個乙烯性不飽和鍵結之化合物、具有2個乙烯性 結之化合物、具有3個以上之乙烯性不飽和鍵結 等。 具有上述1個乙烯性不飽和鍵結之化合物， 列舉：1元醇或酚之單（甲基）丙烯酸酯，較佳爲 所示之化合物： CH2=CHC〇—(OC2H4)|〇 〔式（1)中，1係ο〜8之整數，R1係表示氫原子 〜9之直鏈狀、分枝狀或環狀之烷基。〕 式（1 )所示之化合物的具體例，可列舉： ARONIX M-101 ( 1=約 2、R^H) 、ARONIX Μ 約 4、R'sH)、ARONIX 1=約 1、R1:!!- 壬基、以下相同。）〕、ARONIX M-113〔1=約 n-C9H19)、ARONIX M-114〔 1=約 8、Ri=n-C9H]9) M-117〔 1=2.5、〔以上，東亞合成 (股）製〕、KAYARAD R-564 ( 1=約 2.3、R'sH) 藥（股）製〕等。 另外，式（1 )所示之化合物以外的具有1個 飽和鍵結之化合物，可列舉：商品名之KAYARAD KAYARAD TC-120S〔以上，日本化藥（股）製〕 V-2 311〔以上，大阪有機化學工業（股）製〕等。 :具有1 不飽和鍵 之化合物 例如，可 ，下式（1 ) (1) 1或碳數1 商品名之 -102(1= C 9 Η ! 9 (正 4、R 1 = 、ARONIX 化學工業 〔曰本化 丨乙烯性不 TC-110S 、 、V-15 8、 -20- 200911523 另外，具有上述以外1個乙烯性不飽和鍵結之化合 物，其他能夠使用：馬來酸二甲酯、馬來酸二乙酯等之不 飽和羧酸二酯等；相同於針對（A )共聚物之（a )聚合性 不飽和化合物及（b )其他之聚合性不飽和化合物所例示之 化合物。 接著，上述具有2個乙烯性不飽和鍵結之化合物，例 如，可列舉：2元醇或2元酚之二（甲基）丙烯酸酯，較 佳爲下式（2 )所示之化合物、下式（3 )所示之化合物及 下式（4 )所示之化合物等=200911523 (B) The polymerizable unsaturated compound may, for example, be a compound having an ethylenically unsaturated bond, a compound having two ethylene compounds, or three or more ethylenically unsaturated bonds. A compound having the above one ethylenically unsaturated bond, exemplified by a monohydric alcohol or a mono (meth) acrylate of a phenol, preferably a compound shown: CH2=CHC〇—(OC2H4)|〇[ In 1), 1 is an integer of ～8, and R1 represents a linear, branched or cyclic alkyl group having a hydrogen atom of ～9. Specific examples of the compound represented by the formula (1) include: ARONIX M-101 (1 = about 2, R^H), ARONIX Μ about 4, R'sH), ARONIX 1 = about 1, R1: !- 壬 base, the same as below. )], ARONIX M-113 [1=about n-C9H19), ARONIX M-114 [1=about 8, Ri=n-C9H]9) M-117 [1=2.5, [above, East Asia Synthetic (Shares) System], KAYARAD R-564 (1 = about 2.3, R'sH) medicine (stock) system, etc. In addition, the compound having one saturated bond other than the compound represented by the formula (1) may be, for example, KAYARAD KAYARAD TC-120S (manufactured by Nippon Kayaku Co., Ltd.) under the trade name V-2 311 (above, Osaka Organic Chemical Industry Co., Ltd., etc. : A compound having 1 unsaturated bond, for example, can be, the following formula (1) (1) 1 or a carbon number of 1 -102 (1 = C 9 Η ! 9 (positive 4, R 1 = , ARONIX chemical industry [曰 丨 丨 丨 TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC An unsaturated carboxylic acid diester such as diethyl acrylate; the same as those exemplified for the (a) polymerizable unsaturated compound of (A) copolymer and (b) other polymerizable unsaturated compound. The compound having two ethylenically unsaturated bonds, for example, a di(meth)acrylate of a dihydric alcohol or a divalent phenol, preferably a compound represented by the following formula (2), and the following formula (3) ) the compound shown and the compound represented by the following formula (4)
〔式（2)中，11與m分別爲〇〜8之整數，各R2係表示相 互獨立之氫原子或甲基。〕 式（2 )所示之化合物的具體例’可列舉：商品名之 ARONIX M-210(n =約 2、m =約 2、R2 = CH3 )〔日本東 亞合成化學工業（股）製〕、KAYARAD R-551( n+m =約4、 R2 = CH3 ) 、KAYARADR-712(n+m =約 4、R2=h)〔曰 本化藥（股）製〕等。 CH2=CHC〇〇——(R3-0)p一COCH=CH2 (3) 200911523 〔式（3)中’ R3係表示碳數2〜8之直鏈狀或分枝狀之伸 烷基，P係1〜10之整數。〕[In the formula (2), 11 and m are each an integer of 〇8, and each R2 represents a hydrogen atom or a methyl group which are independent of each other. Specific examples of the compound represented by the formula (2) include a trade name of ARONIX M-210 (n = about 2, m = about 2, R2 = CH3) [Japan East Asia Synthetic Chemical Industry Co., Ltd.], KAYARAD R-551 (n+m = about 4, R2 = CH3), KAYARADR-712 (n+m = about 4, R2 = h) [manufactured by Sakamoto Chemical Co., Ltd.]. CH2=CHC〇〇——(R3-0)p-COCH=CH2 (3) 200911523 [In the formula (3), R3 represents a linear or branched alkyl group having a carbon number of 2 to 8, P An integer from 1 to 10. 〕
式（3 )所示之化合物的具體例，可列舉：商品名之 ARONIX M-220 ( R3 = - ( CH2 ) 3-、p =約 3〕、ARONIX M-225〔 R3 = -（ CH2) 3-、p =約 7〕、ARONIX M-270 〔R3=— (CH2) a -、p =約 12〕> ARONIX M-240 [ R3 = -CH2CH2 -、P=約 4〕、ARONIX M-245〔 R3 = - CH2CH2 —、P =約9〕〔以上，東亞合成化學工業（股）製〕、KAYARAD HDD A ( R3 = - ( CH2 ) 6-、P= 1〕、KAYARAD NPGDA C R3 = ~ CH2C( CH3) 2CH2-、P = 1〕、KAYARAD TPGDA 〔R3 = — CH2CH( CH3) —、p = 1〕、KAYARAD PEG400DA 〔R3= — CH2CH2—、p =約 8〕、KAYARAD MANDA〔R3 =—CH2C ( CH3) 2CH2 -、p = 1〕、KAYARAD R-167〔 R3 =—CH2CH ( OH) CH2〇 ( CH2 ) 6 OCH2CH ( OH ) CH2 -、 p = 1)〔以上，日本化藥（股）製〕、LIGHT ACRYLATE 1.9-NDA〔 R3 = — ( CH2) 8—、P = 1〕等。 R4 R4 (4) CH2:==C~'COO—(M-N)q—M——OCOC=CH2 〔式（4)中，各R4係表示相互獨立之氫原子或甲基’Μ 係表示2元醇之殘基’Ν係表示2元酸之殘基’q係〇或1。〕 式（4 )所示之化合物的具體例，可列舉：商品名之 ARONIX M-6100 ' ARONIX M-6200 ' ARONIX M- 6 2 5 0 > ARONIX M-63 00、ARONIX M-6400、ARONIX M-65 00〔以 -22 - 200911523 上，東亞合成化學工業（股）製〕、LIGHT ESTER EG( q = 0、 Μ = - CH2CH2 -、R4=CH3)、LIGHT ESTER 2EG( q = 1、 M= - (CH2CH2)—、N= — O-、R4= CH3)、LIGHT ESTER 1.4BG( q = 0、M = - ( CH2)4 —、R4 = CH3)、LIGHT ESTER 1.6HX( q = 0' M二一（CH2)6 —、R4 = CH3) ' LIGHT ESTER 1.9ND( q = 0、M = -（ CH2)9 —、R4 = CH3)、LIGHT ESTER G-101P ( q = 0 ' M = - CH2CH ( OH) CH2—、R4=CH3)、 LIGHT ACRYLATE 3EG-A ( q = 2、M = - ( CH2CH2)-、 N= - O—、R4= H)、LIGHT ACRYLATE 4EG-A( q=約 3 ' M = —( CH2CH2) -、N = - O —、R4= H)、LIGHT ACRYLATE 9EG-A(q =約 8、M = - (CH2CH2) -、N=— O-、R4 = H)、LIGHT ACRYLATE 14EG-A( q =約 13、M = —( CH2CH2) —、N = -O—、R4=H) ' LIGHT ACRYLATE 1.6HX-A ( q =0、M = - ( CH2)6 -、R4 = H)、LIGHT ACRYLATE 1.9ND-A (q = 〇 ' M = — ( CH2) 9- ' R4= H)〔以上，共榮社化學 (股）製〕等。 1 再者，上述以外的具有2個乙烯性不飽和鍵結之化合 物，可列舉：下式（5 - 1 )所示之化合物〔商品名之KAYYARAD HX-220、日本化藥（股）製〕、下式（5-2)所示之化合物〔商 品名之KAYYARAD HX-620、日本化藥（股）製〕、或商品名 之 R-604〔日本化藥（股）製〕、V-260、V-312、V-335HP〔以 上，大阪有機化學工業（股）製〕等。 -23 - 200911523 ch2=chcoo— [(CH2)50]r-CH2C(CH3)2C00-j CH2C(CH3)2CH20-[C0(CH2)50]s CH2=CHC00——[(CH2)50]t—CH2C(CH3)2CO〇i CH2C(CH3)2CH20-[CO(CH2)4〇]u coch=ch2 (5-1) coch=ch2 (5-2) 〔式（5-1)中，r與s分別爲0〜2之整數，r+s=2。〕 〔式（5-2)中，t與u分別爲0〜4之整數，t+u=4。〕 接著，上述具有3個以上之乙烯性不飽和鍵結的化合 物，可列舉：具有3元以上之醇的聚（甲基）丙烯酸酯， 較佳爲下式（6 )所示之化合物、下式（7 )所示之化合物、 下式（8 )所示之化合物、下式（9 )所示之化合物等： [ch2=chco—(〇C3H6)v—OCH2-]3CCH2R5 (6) 〔式（6)中，V係0〜8之整數，R5係表示氫原子、羥基 或甲基。〕 (CH2=CHCOOCH2)3CCH2-R6—CH2C(CH2OC〇CH=CH2)3 (7) [式（7)中，R6係表示氫原子或亞甲基。〕 R7 R7 I R7 OCOC=CH〇 | △ CH2=C-CO〇-(X-Y)w—(OCOCH=CH2)2 (8) 〔式（8)中，各 R7係表示相互獨立之氫原子或甲基，X 係表示3元醇之殘基，Y係表示2元酸之殘基，w係0〜1 5 之整數。〕 -24 - 200911523 ch2〇— ch2〇一 •Ab ⑼ [A—(OC5H10CO)x-]a-|-〇CH2—C-CH2〇CH2C-CH2〇· I _ | CH20 — ch20一 〔式（9)中，A係表示CH2=CHCO—，x係1或2’ 3係 2〜6之整數，b係0〜4之整數，a+b=6。〕 式（6 )所示之化合物的具體例，可列舉：商品名之 ARONIX M-305( v = 0> R5 = OH) > ARONIX M-3〇9( v = 0 ' R5 = CH3)、ARONIX M-310( v =約 1、r5 = CH3)、AR0NIX M-320 ( v =約 2、R5=CH3)、ARONIX M-450 ( v = 〇、r5 =CH2CHCOO ) 、ARONIX M-402 ( v = 0、r5 = (CH2CHCOOCH2 ) 2 ( RaCH2〇 ) CCH2 - O -、Ra = ”H” 或”CO CH = CH2”）〔以上，東亞合成化學工業（股）製〕、 KAYARAD TMPTA(v=0、R5=CH3)〔日本化藥（股）製〕、 V-295 ( V - 0 ' R5 = CH3) > V- 3 0 0 ( v = 0 ' R5 = 〇H )〔以 上，大阪有機化學工業（股）製〕等。 另外，式（7 )所示之化合物的具體例，可列舉：商品 名之ARONIX M_400 (東亞合成化學工業（股）製）等。Specific examples of the compound represented by the formula (3) include a trade name of ARONIX M-220 (R3 = - (CH2) 3-, p = about 3), and ARONIX M-225 [R3 = -(CH2) 3 -, p = about 7], ARONIX M-270 [R3 = - (CH2) a -, p = about 12] > ARONIX M-240 [ R3 = -CH2CH2 -, P = about 4], ARONIX M-245 [ R3 = - CH2CH2 -, P = about 9] [above, East Asian Synthetic Chemical Industry Co., Ltd.], KAYARAD HDD A ( R3 = - ( CH2 ) 6-, P = 1], KAYARAD NPGDA C R3 = ~ CH2C (CH3) 2CH2-, P = 1], KAYARAD TPGDA [R3 = — CH2CH(CH3) —, p = 1], KAYARAD PEG400DA [R3= — CH2CH2—, p = about 8], KAYARAD MANDA [R3 =—CH2C (CH3) 2CH2 -, p = 1], KAYARAD R-167 [ R3 = -CH2CH ( OH) CH2 〇 ( CH2 ) 6 OCH2CH ( OH ) CH2 -, p = 1) [above, Nippon Chemical Co., Ltd. 〕, LIGHT ACRYLATE 1.9-NDA [ R3 = — ( CH2) 8 —, P = 1], etc. R4 R4 (4) CH2:==C~'COO—(MN)q—M——OCOC=CH2 In (4), each R4 represents a hydrogen atom or a methyl group which is independent of each other, and the residue of the dihydric alcohol represents a residue of the dibasic acid 'q system 〇 1. A specific example of the compound represented by the formula (4): ARONIX M-6100 ' ARONIX M-6200 ' ARONIX M- 6 2 5 0 > ARONIX M-63 00, ARONIX M-6400 , ARONIX M-65 00 [to -22 - 200911523, East Asian Synthetic Chemical Industry Co., Ltd.], LIGHT ESTER EG (q = 0, Μ = - CH2CH2 -, R4 = CH3), LIGHT ESTER 2EG (q = 1 , M= - (CH2CH2)—, N= — O—, R4= CH3), LIGHT ESTER 1.4BG (q = 0, M = - (CH2)4 —, R4 = CH3), LIGHT ESTER 1.6HX (q = 0' M two one (CH2)6 —, R4 = CH3) ' LIGHT ESTER 1.9ND ( q = 0, M = -( CH2)9 —, R4 = CH3), LIGHT ESTER G-101P ( q = 0 ' M = - CH2CH ( OH) CH2—, R4=CH3), LIGHT ACRYLATE 3EG-A ( q = 2, M = - (CH2CH2)-, N= - O—, R4= H), LIGHT ACRYLATE 4EG-A( q = about 3 ' M = —( CH2CH2) -, N = - O -, R4 = H), LIGHT ACRYLATE 9EG-A (q = about 8, M = - (CH2CH2) -, N = - O-, R4 = H), LIGHT ACRYLATE 14EG-A ( q = about 13, M = —( CH2CH2) —, N = -O—, R4=H) ' LIGHT ACRYLATE 1.6HX-A ( q =0, M = - ( CH2) 6 -, R4 = H), LIGHT ACRYLATE 1.9ND-A (q = 〇 ' M = — ( CH2) 9- ' R4 = H) [above, Gongrongshe Chemical (share) system]. In addition, the compound having two ethylenic unsaturated bonds other than the above may be a compound represented by the following formula (5-1) [manufactured by KAYYARAD HX-220, manufactured by Nippon Kayaku Co., Ltd.] a compound represented by the following formula (5-2) [manufactured by KAYYARAD HX-620, manufactured by Nippon Kayaku Co., Ltd.] or a product name of R-604 (manufactured by Nippon Kayaku Co., Ltd.), V-260 , V-312, V-335HP (above, Osaka Organic Chemical Industry Co., Ltd.) and the like. -23 - 200911523 ch2=chcoo— [(CH2)50]r-CH2C(CH3)2C00-j CH2C(CH3)2CH20-[C0(CH2)50]s CH2=CHC00——[(CH2)50]t— CH2C(CH3)2CO〇i CH2C(CH3)2CH20-[CO(CH2)4〇]u coch=ch2 (5-1) coch=ch2 (5-2) [in equation (5-1), r and s They are integers of 0 to 2, respectively, and r + s = 2. [In the formula (5-2), t and u are each an integer of 0 to 4, and t + u = 4. Next, the compound having three or more ethylenically unsaturated bonds may, for example, be a poly(meth)acrylate having an alcohol of 3 or more, preferably a compound represented by the following formula (6), and a compound represented by the formula (7), a compound represented by the following formula (8), a compound represented by the following formula (9), etc.: [ch2=chco—(〇C3H6)v—OCH2-]3CCH2R5 (6) In (6), V is an integer of 0 to 8, and R5 represents a hydrogen atom, a hydroxyl group or a methyl group. (CH2=CHCOOCH2)3CCH2-R6-CH2C(CH2OC〇CH=CH2)3 (7) [In the formula (7), R6 represents a hydrogen atom or a methylene group. 〕 R7 R7 I R7 OCOC=CH〇| △ CH2=C-CO〇-(XY)w—(OCOCH=CH2)2 (8) In the formula (8), each R7 represents a mutually independent hydrogen atom or a The group X represents a residue of a trihydric alcohol, the Y system represents a residue of a dibasic acid, and w is an integer of 0 to 15 . ] -24 - 200911523 ch2〇—ch2〇一•Ab (9) [A—(OC5H10CO)x-]a-|-〇CH2—C-CH2〇CH2C-CH2〇· I _ | CH20 — ch20一[式(9 In the formula A, CH2=CHCO-, x is 1 or 2'3 is an integer of 2 to 6, and b is an integer of 0 to 4, and a+b=6. Specific examples of the compound represented by the formula (6) include a trade name of ARONIX M-305 (v = 0> R5 = OH) > ARONIX M-3〇9 (v = 0 ' R5 = CH3), ARONIX M-310 (v = about 1, r5 = CH3), AR0NIX M-320 (v = about 2, R5 = CH3), ARONIX M-450 (v = 〇, r5 = CH2CHCOO), ARONIX M-402 (v = 0, r5 = (CH2CHCOOCH2) 2 (RaCH2〇) CCH2 - O -, Ra = "H" or "CO CH = CH2") [above, East Asian Synthetic Chemical Industry Co., Ltd.], KAYARAD TMPTA (v=0 , R5=CH3) [Nippon Chemical Co., Ltd.], V-295 (V - 0 ' R5 = CH3) > V- 3 0 0 ( v = 0 ' R5 = 〇H ) [above, Osaka Organic Chemistry Industrial (share) system, etc. In addition, specific examples of the compound represented by the formula (7) include ARONIX M_400 (manufactured by East Asia Synthetic Chemical Industry Co., Ltd.) and the like.
另外，式（8 )所示之化合物的具體例’可列舉：商品 名之 ARONIX M-7100 、 ARONIX M- 8 0 3 0 、 ARONIX M-8060、ARONIX M-8100、ARONIX M-9050 (東亞合成化 學工業（股）製）、KAYARAD T-1420( T) ( X = C ( CH2CH3 ) 一、Y= — (CH2OCH2)—)〔日本化藥（股）製〕等。 另外，式（9 )所示之化合物的具體例’可列舉：商品 名之 KAYARAD DPCA-20(x =約 1、a =約 2、b =約 4)、 -25 - 200911523 KAYARAD DPCA-30(x =約卜 a =約 3、b =約 3)、KAYARAD DPCA-6 0(x =約卜 a =約 6、b =約 0)、KAYARADDPCA-120 (x =約2、a =約6、b =約〇 )〔以上，日本化藥（股）製〕； V-360、V-GPT、V-3PA、V-400〔以上，大阪有機化學工業 (股）製〕等。 此等（B )聚合性不飽和化合物之中，適宜爲具有2 個乙烯性不飽和鍵結之化合物及具有3個以上之乙烯性不 飽和鍵結的化合物，更佳爲式（4 )所示之化合物及式（8 ) ξ 所示之化合物。 於本發明中，（Β )聚合性不飽和化合物能夠單獨地或 混合二種以上後而使用。 相對於（Α)共聚物100重量份，本發明中之（Β)聚 合性不飽和化合物的用量適宜爲3 0〜1 5 0重量份，更佳爲 5 0〜1 〇〇重量份。若（Β )聚合性不飽和化合物之用量低於 3 〇重量份時，放射線照射時之感度容易降低，另一方面， 若超過1 5 0重量份時，擔憂與（A )共聚物之相溶性將變差， V 在塗膜表面發生薄膜粗糙。 一（C)光聚合起始劑一 本發明中之（C )成分係藉由放射線之照射，可起始（B ) 聚合性不飽和化合物之聚合的活性種，例如，由產生自由 基等光聚合起始劑所構成。 如此之（C )光聚合起始劑’例如，可列舉：苄基、二 乙醯基等之α -二酮；苯偶因等之偶因；苯偶因甲基醚、苯 偶因乙基醚、苯偶因異丙基醚等之偶因醚；9 -氧硫D[Ij哩、 -26- 200911523 2，4 -二乙基-9 -氧硫卩山卩星、9 -氧硫_嗶-4 -磺酸等之9 -氧硫_ 喝類；二苯甲酮、4,4’-雙（二甲胺基）二苯甲酮、4，4’-雙 (二乙胺基）二苯甲酮等之二苯甲酮類；苯乙酮、對二甲 胺基苯乙酮、α，α’-二甲氧基乙醯氧基二苯甲酮、2，2’-二甲 氧基-2 -苯基苯乙酮、對甲氧基苯乙酮等之苯乙酮類；蒽醌、 1，4 -萘醌等之醌；苯甲醯氯甲烷、三溴甲基苯基颯、三（三 氯甲基）-s-三畊等之鹵化物；過氧化二（三級丁基）等之 過氧化物；氧化-2,4,6 -三甲基苯甲醯基二苯基膦等之氧化 醯基膦；1-( 9 -乙基-6-苯甲醯基- 9.Η.-咔唑-3-基）-壬烷-1,2-壬烷-2 -肟-〇-苯甲酸酯、1 - ( 9 -乙基-6 -苯甲醯基-9 . Η .-咔唑 -3-基）-壬烷-1,2-壬烷-2-肟-0-乙酸酯、1- ( 9-乙基-6-苯甲 醯基-9 . Η .-咔唑-3 -基）-戊烷-1，2 -戊烷-2 -肟-0 -乙酸酯' 1 -(9-乙基-6-苯甲醯基-9.Η.-咔唑-3-基）-辛烷-1-酮肟-0-乙 酸酯、1-〔 9 -乙基-6- (2 -甲基苯甲醯基）-9.Η·-咔唑-3 -基〕 -乙烷-1-酮肟-0-苯甲酸酯、1-〔 9-乙基-6- ( 2-甲基苯甲醯 基）-9 . Η .-咔唑-3 -基〕-乙烷-1 -酮肟-0 -乙酸酯、1 -〔 9 -乙基 -6-(1，3,5-三甲基苯甲醯基）-9.Η.-咔唑-3-基〕-乙烷-1-酮 肟-0-苯甲酸酯、1-〔9-丁基-6-(2-乙基苯甲醯基）-9.!1·-咔唑-3-基〕-乙烷-1-酮肟-◦-苯甲酸酯、1,2-辛二酮-1-〔 4-(苯硫）苯基〕-2_(〇 -苯甲醯基肟）、1,2 -丁二酮-1-〔4-(苯硫）苯基〕-2-(〇-苯甲醯基肟）、1，2-丁二酮-1-〔4-(苯硫）苯基〕-2-( ◦-乙醯基肟）、1，2-辛二酮-1-〔4-(甲 硫）苯基〕-2-(〇-苯甲醯基肟）、1,2 -辛二酮-1-〔4-(苯 硫）苯基〕-2-〔 0-(4-甲基苯甲醯基肟）〕等之0-醯基肟 -27 - 200911523 等。 另外，（C)光聚合起始劑之市售品，可列舉：商品名 之 IRGACURE 184、IRGACURE 500、IRGACURE 651、 IRGACURE 907 、 IRGACURE 369 、 IRGACURE 379 、 IRGACURE CG24-61 (以上，CIBA SPECIALITY CHEMICALS 公司製）、LUCIRIN LR8728、LUCIRIN TPO(以上，BASF 公司製）、DAROCURE 1116' DAROCURE 1173(以上， MERK 公司製）、UBECRYL p36 ( UCB 公司製）等。 此等（C )光聚合起始劑之中，較佳爲2-甲基〔4-(甲 硫）苯基〕-2-嗎啉基丙烷-1-酮' 2-苄基-2-二甲胺基-1- ( 4-嗎啉苯基）丁烷-1-酮等之苯乙酮類；或苯甲醯氯甲烷、三 溴甲基苯基楓、氧化-2，4,6 -三甲基苯甲醯基二苯基膦等。 (C )光聚合起始劑能夠單獨地或混合二種以上後而使 用，另外，也能夠倂用一種以上之放射線增感劑。 相對於（B )聚合性不飽和化合物1 〇 〇重量份，（C ) 光聚合起始劑之用量適宜爲0.01〜100重量份’更佳爲〇.01 〜50重量份，進一步更佳爲0.5〜重量份。若（c)光 聚合起始劑之用量低於〇. 〇 1重量份時’將有感度降低之傾 向，另一方面，若超過1〇〇重量份時’將有與（A)共聚物 或（B )聚合性不飽和化合物之相溶性將變差’所得的樹脂 組成物保存安定性降低之傾向。 一（D )鏈轉移劑一 本發明中之（D )鏈轉移劑係一種調節因放射線照射所 造成之（B )聚合性不飽和化合物的聚合度’控制後烘烤後 -28 - 200911523 之微透鏡形狀的成分。如此之（D)成分’例如’可列舉·· 乙酵、丙嗣、醋酸乙醋寺之鑛基化合物或竣酸醋；甲苯、 乙基苯、三級丁基苯、三苯基甲烷、2,4 -二苯基-4 -甲基-1-戊烯等之芳香族烴；對苯醌 '氫醌等之醌；氯仿、四氯化 碳、四溴化碳、溴三氯甲烷等之鹵化烴；硝基甲烷、三硝 基甲烷、1 , 1，1 -三硝基乙烷等之硝基化合物；對甲氧基酚、 2,3，4,6 -四甲基酚等之酚類；三乙胺、三正丙胺、三正丁胺、 Ν,Ν -二甲基苯胺、Ν,Ν -二乙烯基苯胺等之胺基化合物；辛 ^ 基硫醇、正丁基硫醇、正戊基硫醇、正十六烷基硫醇、正 十四烷基硫醇 '正十二烷基硫醇、三級十四烷基硫醇、三 級十二烷基硫醇等之硫醇；二硫化二甲基黃原、二硫化二 乙基黃原、二硫化二異丙基黃原等之二硫化黃原；二硫化 四甲胺甲硫醯、二硫化四乙胺甲硫醯、二硫化四丁胺甲硫 醯等之二硫化胺甲硫醯；五苯基乙烷、（X -甲基苯乙烯二聚 體等之烴：及丙烯醛、異丁烯醛、烯丙醇、锍基乙酸-2-乙 基己酯、蔥品油烯、α-萜品烯、γ-萜品烯、雙戊烯等。 " 此等鏈轉移劑之中，較佳爲2,4-二苯基-4-甲基-1-戊 烯、對甲氧基酚、三級十二烷基硫醇等。該鏈轉移劑能夠 單獨地或混合二種以上後而使用。 於本發明中，相對於（Α)共聚物100重量份，鏈轉移 劑之用量適宜爲〇.〇丨〜1〇重量份，更佳爲〇.〇5〜10重量 份’尤以0 · 1〜5重量份特別理想。若鏈轉移劑之用量低於 0.0 1重量份時，擔憂無法得到所希望之效果。另一方面， 若超過10重量份時，將有因曝光所造成之硬化並未充分進 -29 - 200911523 行，顯像後溶解性變得非常高之傾向。 一添加劑一 於感放射線性樹脂組成物中，能夠添加（E )矽烷偶合 劑。 (E )成分係發揮作爲用以使與基板的緊貼性提高之黏 著助劑的功能。 如此之（E )成分’例如，可列舉：較佳爲具有羧基、 甲基丙烯醯基、乙烯基、異氰酸酯基、環氧基等之反應性 f 取代基的矽烷偶合劑’更具體而言，可列舉：三甲氧基矽 烷基苯甲酸、γ -甲基丙烯醯氧丙基三甲氧基矽烷、乙烯基 三乙醯氧基矽烷、乙烯基三甲氧基矽烷、γ-異氰酸酯丙基 三乙氧基矽烷、3-甲基丙烯氧丙基三甲氧基矽烷、γ-環氧 丙氧丙基三甲氧基矽烷、β-(3,4-環氧環己基）乙基三甲氧 基砂院等。 此等之矽烷偶合劑能夠單獨地或混合二種以上後而使 用。 、 相對於（A )共聚物1 〇 〇重量份，矽烷偶合劑之添加量 適宜爲0.1〜30重量份’更佳爲1〜20重量份。 於感放射線性樹脂組成物中，經由加熱而聚合’能夠 添加不會根據放射線照射而聚合之（F )熱聚合性化合物° 如此之（F )熱聚合性化合物適宜於8 0〜2 5 〇 °C ’更佳 於8 0〜1 6 0 °C，尤以於1 〇 〇〜1 5 0 °C進行熱聚合特別理想。 於透鏡形成用感放射線性樹脂組成物中’尤其將加熱 處理之溫度設爲1 6 0 以下而形成透鏡之情形下’較佳爲 -30 - 200911523 添加（F )熱聚合性化合物。 一般而言，（F)熱聚合性化合物爲單體，其分子量並 未予以特別限制，也可以具有寡聚物程度之分子量。 (F )熱聚合性化合物，其分子內之熱聚合性官能基， 例如，可列舉：具有1個以上或一種以上之環氧基 '環硫 基、環氧丁烷基等之化合物。但是，於後述之黏著助劑之 中，具有環氧基之官能性矽烷耦合劑也包含具有環氧基之 熱聚合性化合物中。 (F)熱聚合性化合物之中，具有丨個環氧基之化合 物，例如，可列舉：甲基環氧丙基醚、乙基環氧丙基醚、 正丙基環氧丙基醚、異丙基環氧丙基醚、正丁基環氧丙基 醚、二級丁基環氧丙基醚、三級丁基環氧丙基醚等之烷基 環氧丙基醚；乙二醇單環氧丙基醚、丙二醇單環氧丙基醚、 1,4-丁二醇單環氧丙基醚、1,6-己二醇單環氧丙基醚等之伸 烷二醇單環氧丙基醚；聚乙二醇單環氧丙基醚、聚丙二醇 單環氧丙基醚等之聚伸烷二醇單環氧丙基醚；苯基環氧丙 基醚、鄰甲苯基環氧丙基醚、間甲苯基環氧丙基醚、對甲 苯基環氧丙基醚、鄰乙基苯基環氧丙基醚、間乙基苯基環 氧丙基醚、對乙基苯基環氧丙基醚等芳基環氧丙基醚等之 具有環氧丙基醚的化合物；或〔（3,4 -環氧環己基）甲基〕 甲基醚、〔（3，4-環氧環己基）甲基〕乙基醚、〔（3,4-環氧環己基）甲基〕正丙基醚、〔（3,4 -環氧環己基）甲 基〕異丙基醚' 〔（3,4 -環氧環己基）甲基〕正丁基醚' 〔（3,4-環氧環己基）甲基〕二級丁基醚、〔（3，4-環氧環 -31- 200911523 己基）甲基〕三級丁基醚等之〔（3,4 -環氧環己基）甲基〕 烷基醚；乙二醇單〔（3,4-環氧環己基）甲基〕醚、丙二 醇單〔（3,4-環氧環己基）甲基〕醚、1,4-丁二醇單〔（3,4-環氧環己基）甲基〕醚、1，6 -己二醇單〔（3,4 -環氧環己基） 甲基〕醚等之伸烷基二醇單〔（3,4-環氧環己基）甲基〕 醚；聚乙二醇單〔（3,4-環氧環己基）甲基〕醚、聚丙二 醇單〔（3,4-環氧環己基）甲基〕醚等之聚伸烷基二醇單 〔（3,4-環氧環己基）甲基〕醚；〔（3,4-環氧環己基）甲 基〕苯基醚、〔（3,4-環氧環己基）甲基〕鄰甲苯基醚、 〔（3,4-環氧環己基）甲基〕間甲苯基醚、〔（3,4-環氧環 己基）甲基〕對甲苯基醚、〔（3,4 -環氧環己基）甲基〕 鄰乙基苯基醚、〔（3,4 -環氧環己基）甲基〕間乙基苯基 醚、〔（3,4-環氧環己基）甲基〕對乙基苯基醚等〔（3,4_ 環氧環己基）甲基〕芳基醚等之具有3,4-環氧環己基的化 合物等。 另外，具有2個以上環氧基之化合物，例如，可列舉： 雙酚A二環氧丙基醚、雙酚F二環氧丙基醚、雙酚S二環 氧丙基醚、氫化雙酚A二環氧丙基醚、氫化雙酚F二環氧 丙基醚、氫化雙酚AD二環氧丙基醚、溴化雙酚A二環氧 丙基醚、溴化雙酚F二環氧丙基醚、溴化雙酚S二環氧丙 基醚等雙酚化合物之二環氧丙基醚；乙二醇二環氧丙基 醚、丙二醇二環氧丙基醚、1，4 -丁二醇二環氧丙基醚、1，6-己二醇二環氧丙基醚、丙三醇三環氧丙基醚、三羥甲基丙 烷三環氧丙基醚等多元醇之聚環氧丙基醚；聚乙二醇二環 -32 - 200911523 氧丙基醚、聚丙二醇二環氧丙基醚等之聚伸烷基二醇二環 氧丙基醚；藉由將一種或二種以上之環氧烷（例如，環氧 乙烷、環氧丙烷等）加成於乙二醇、丙二醇、丙三醇等之 脂肪族多元醇所得的聚醚聚醇之聚環氧丙基醚；雙酚A型 環氧樹脂；雙酚F型環氧樹脂；酚酚醛型環氧樹脂；甲酚 酚醛型環氧樹脂；聚酚型環氧樹脂；其他之脂環族環氧樹 脂、其他之脂環族聚環氧丙基醚、高級多元脂肪酸之聚環 氧丙基酯；環氧化大豆油、環氧化亞麻仁油；或下列雙酚 A型環氧樹脂：商品名之EPICOAT 825、828、834、1001、 1002、 1003、 1004、 1007、 1009' 1010、 8000、 8034 〔以 上，JAPAN EPOXY RES IN(股）製〕等；雙酚F型環氧樹脂： EPICOAT 807〔 JAPAN EPOXY RESIN(股）製〕等；酚酚醛 型環氧樹脂：EPICOAT 152、154、157S65〔以上，JAPAN EPOXY RESIN(股）製〕、EPPN201、202 (以上，日本化藥 (股）製）等；甲酚醛型環氧樹脂：EOCN 102、103S、104S、 1020、1025、102 7〔以上，日本化藥（股）製〕、EPICOAT 180S75 〔JAPAN EPOXY RESIN(股）製〕等；聚酚型環氧樹脂： EPICOAT 1032H60、XY-4000〔以上，JAPAN EPOXY RESIN(股）製〕等；其他之脂環族聚環氧樹脂：CY-175、177、 179、Araldite CY-182' 192、184〔以上，CIBA SPECIALITY CHEMICALS 公司製〕、ERL-4206、-4221、-42 3 4 ' -4299 (以上，u. C. C.公司製）、SHODYNE 509〔昭和電工（股） 製〕、EPICLON 200、400〔以上’大日本墨水（股）製〕' EPICOAT 871、872〔以上 ’ JAPAN EPOXY RESIN(股）製〕、 200911523 ED-5661、-5662〔以上，CELANESE COATING 公司製〕等； 其他之脂肪族聚環氧丙基醚：EPOLIGHT 100MF〔共榮社 化學（股）製〕、EPIOL TMP〔日本油脂（股）製〕等之外；具 有2個以上之3,4-環氧環己基之化合物可列舉：3,4-環氧環 己烷羧酸之〔（3,4-環氧環己基）甲基〕酯、2-(3,4-環氧 環己基-5,5-螺- 3,4-環氧）環己烷偏二噚烷、雙〔（3,4-環 氧環己基）甲基〕己二酸酯、雙〔（3,4-環氧-6-甲基環己 基）〕甲基〕己二酸酯、3,4-環氧-6-甲基環己烷羧酸之（3,4-環氧-6-甲基環己基）酯、亞甲基雙（3,4-環氧環己烷）、 二環戊二烯二環氧化物；乙二醇之雙〔（3,4_環氧環己基） 甲基〕醚、乙二醇之雙（3,4-環氧環己烷羧酸）酯、3,4-環氧環己烷羧酸之〔（3,4-環氧環己基）甲基〕酯與己內 酯之反應生成物等；具有環氧基與3,4 -環氧環己基之化合 物可列舉：1，2 : 8，9 -二環氧檸檬烯等。 另外，具有環硫基之化合物，例如，可列舉：例如依 照「J. Org. Chem·，Vol. 28，ρ· 229( 1963)」所示之方法， 將上述具有1個或2個以上之環氧基化合物中的環氧基轉 換成環硫基之化合物等。 另外，具有1個環氧丁烷基之化合物，例如，可列舉·· 3 -甲基-3-甲氧基甲基環氧丁烷、3_乙基_3_甲氧基甲基環氧 丁院、3 -甲基-3·乙氧基甲基環氧丁烷、3_乙基-3 -乙氧基甲 基環氧丁烷、3-甲基-3-羥甲基環氧丁烷、3-乙基-3-羥甲基 環氧丁烷、3-甲基-3-苯氧基甲基環氧丁烷、3-乙基-3-苯氧 基甲基環氧丁烷、3 -甲基-3-苄氧基甲基環氧丁烷、3 -乙基 -34 - 200911523 -3-苄氧基甲基環氧丁烷、3-甲基-3-〔 （2-乙基己氧基）甲 基〕環氧丁烷、3 -乙基-3-〔 （2 -乙基己氧基）甲基〕環氧 丁烷、3 -甲基-3- (N -正丁基醯胺甲氧基）環氧丁烷、3 -乙 基- 3-(N -正丁基醯胺甲氧基）環氧丁烷。 另外，具有2個以上環氧丁烷基之化合物，例如，可 列舉：3，7 -雙（3 -環氧丁烷基）-5 -氧化壬烷、3，3 ’ -〔 1，3 -(2 -亞甲基）丙烷二基雙（羥亞甲基）〕雙（3 -乙基環氧 丁烷）、：I，4 -雙〔（3 -乙基-3 -環氧丁烷基）甲氧基甲基〕 苯、雙〔（3 -乙基-3 -環氧丁烷基）甲基〕對苯二甲酸酯、 1，2 -雙〔（3_乙基-3-環氧丁烷基）甲氧基甲基〕乙烷、1,3-雙〔（3-乙基-3-環氧丁烷基）甲氧基甲基〕丙烷、乙二醇 雙〔（3-乙基-3-環氧丁烷基）甲基〕醚、二乙二醇雙〔（3-乙基-3 -環氧丁烷基）甲基〕醚、三乙二醇雙〔（3 -乙基-3-環氧丁烷基）甲基〕醚、四乙二醇雙〔（3-乙基-3-環氧丁 烷基）甲基〕醚' 二環戊烯基雙〔（3 -乙基-3-環氧丁烷基） 甲基〕醚、三環癸烷二基二亞甲基雙〔（3-乙基-3-環氧丁 烷基）甲基〕醚、三羥甲基丙烷三〔（3-乙基-3-環氧丁烷 基）甲基〕醚、1，4-雙〔（3-乙基-3-環氧丁烷基）甲氧基〕 丁烷、1,6-雙〔（3-乙基-3-環氧丁烷基）甲氧基〕己烷、 季戊四醇三〔（3-乙基-3-環氧丁烷基）甲基〕醚、季戊四 醇四〔（3 -乙基-3-環氧丁烷基）甲基〕醚、聚乙二醇雙〔（3-乙基-3-環氧丁烷基）甲基〕醚、二季戊四醇六〔（3-乙基 -3-環氧丁烷基）甲基〕醚、二季戊四醇五〔（3-乙基-3-環氧丁烷基）甲基〕醚、二季戊四醇四〔（3-乙基-3-環氧 -3 5 - 200911523 丁烷基）甲基〕醚、二季戊四醇六〔（3 -乙基-3 -環氧丁烷 基）甲基〕醚與己內酯之反應生成物、二季戊四醇五〔（3-乙基-3-環氧丁烷基）甲基〕醚與己內酯之反應生成物、二 (三羥甲基）丙烷四〔（3 -乙基-3 -環氧丁烷基）甲基〕醚、 雙酚A雙〔（3-乙基-3-環氧丁烷基）甲基〕醚與環氧乙烷 之反應生成物、雙酚A雙〔（3-乙基-3_環氧丁烷基）甲基〕 醚與環氧丙烷之反應生成物、氫化雙酚A雙〔（3 -乙基-3 -環氧丁烷基）甲基〕醚與環氧乙烷之反應生成物、氫化雙 酚A雙〔（3-乙基-3-環氧丁烷基）甲基〕醚與環氧丙烷之 反應生成物、雙酚F雙〔（3-乙基-3-環氧丁烷基）甲基〕 醚與環氧乙烷之反應生成物等。 此等（F )熱聚合性化合物之中，較佳爲雙酚A型環氧 樹脂、酚酚醛型環氧樹脂、3,4-環氧環己烷羧酸之〔（3,4-環氧環己基）甲基〕酯、雙〔（3-乙基-3-環氧丁烷基）甲 基〕對苯二甲酸酯等。 上述（F )熱聚合性化合物能夠單獨地或混合二種以上 後而使用。 相對於（A )共聚物1 0 0重量份，（F )熱聚合性化合 物之添加量適宜爲100重量份以下，更佳爲50重量份以 下。若（F )熱聚合性化合物超過1 0 0重量份時，擔憂所得 的樹脂組成物之顯像性將受損。 於本發明之感放射線性樹脂組成物中，爲了抑制因預 烘烤時之加熱所造成之顯像性降低，能夠添加熱聚合抑制 劑。 -36 - 200911523 醌、 醌、 4,4 5 - 如此之熱聚合抑制劑’例如，可列舉：焦掊酣、對苯 氫酷、亞甲藍、三級丁基鄰苯二酚、甲基氫醌、正戊 正戊醯氧基氫醌、正丁基酚'酚、氫醌單正丙基醚、 〔1-{4-( 1-〔4 -羥苯基〕_丨_甲基乙基）苯基}亞乙基〕 、1，1，3-二（2,5 -一甲基_4_徑苯基）_3_苯基丙院等。 此等之熱聚合抑制劑能夠單獨地或混合二種以上後而 使用。 相對於（F )熱聚合性化合物丨〇 0重量份，熱聚合抑制 劑之添加量適宜爲5重量份以下，更佳爲3重量份以下。 另外’於感放射線性樹脂組成物中，爲了使塗布性、 消泡性、平坦性等得以提高，能夠添加界面活性劑。 如此之界面活性劑’例如，可列舉：氟系界面活性劑、 矽氧烷系界面活性劑、陰離子系界面活性劑等。 上述氟系界面活性劑，例如，可列舉：商品名之 FTX-212D、FTX-218' FTX-208D(以上，NEOS 公司製）; BM-1000、BM-110 0(以上，BM CHIMIE 公司製）；MAGAFAC F142D、F172、F173、F183〔以上，大日本墨水化學工業（股） 製〕；FLORAD FC-135、FC-170C、FC-430、FC-431〔以 上，日本住友 3M(股）製〕；SURFLON S-112、S-H3、S-131、 S-141、 S-145、 S-382、 SC-101、 SC-102、 SC-103、 SC-104、 SC-105、SC-106〔以上，旭硝子（股）製〕等。 另外，上述矽氧烷系界面活性劑，例如，可列舉：商 品名之 SH-28PA ' SH-190 > SH-193、SZ-6032、SF-842 8 ' DC-57、-190〔以上，TORAY DOW CORNING SILICONE(股） -37 - 200911523 製〕、KP341〔信越化學工業（股）製〕、F-TOP EF301、EF303、 EF3 52〔以上，新秋田化成（股）製〕等。 另外’上述陰離子系界面活性劑，例如，可列舉：聚 氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚等 之聚氧乙烯烷基醚；聚氧乙烯正辛基苯基醚、聚氧乙烯正 壬基苯基醚等之聚氧乙儲芳基醚；聚氧乙儲二月桂酸酯、 聚氧乙烯二硬脂酸酯等之聚氧乙烯二烷基酯等。 再者，上述以外之界面活性劑，例如，可列舉：商品 名之POLYFLOW-No.57、No.9 0〔以上’曰本共榮社化學（股） 製〕等。 此等之界面活性劑能夠單獨地或混合二種以上後而使 用。 相對於（A )共聚物1 0 0重量份，界面活性劑之添加量 適宜爲5重量份以下，更佳爲2重量份以下。若界面活性 劑之添加量超過5重量份時，將有於塗布時變得容易發生 塗膜的膜粗糙之傾向。 於感放射線性樹脂組成物中，爲了調節對於（A )共聚 物之鹼顯像液的溶解性，能夠添加溶解促進劑或溶解控制 劑。亦即，對於（A )共聚物之鹼顯像液的溶解性過低之情 形，能夠摻合溶解促進劑劑以提高（A )共聚物之溶解性’ 具有使鹼顯像時之（A)共聚物的溶解速度得以適度增大之 作用。相反的，對於（A )共聚物之鹼顯像液的溶解性過高 之情形，能夠摻合溶解控制劑以控制（A )共聚物的溶解性’ 具有使鹼顯像時之（A )共聚物的溶解速度得以適度減少之 -38 - 200911523 作用。 上述溶解促進劑及溶解控制劑並未予以特別限定，較 佳爲在感放射線性樹脂組成物之預烘烤、曝光、顯像等之 步驟中，不會發生化學變化之化合物。 例如，溶解促進劑可列舉：苯環數約爲2〜6個之低分 子量酚性化合物。更具體而言，可列舉：雙酚類、三（羥 苯基）甲烷類等。 另外’溶解控制劑，例如，可列舉：萘、菲 '蒽、苊 等之芳香族烴；苯乙酮、二苯甲酮、苯基萘基酮等之酮； 甲基苯基颯、二苯基颯、二萘基颯等之碾等。 此等之溶解促進劑及溶解控制劑能夠分別單獨地或混 合二種以上後而使用。 溶解促進劑及溶解控制劑之添加量能夠因應於所使用 之（A )共聚物的種類來加以適宜調整，分別相對於（a ) 共聚物1〇〇重量份’適宜爲50重量份以下，更佳爲30重 量份以下。 爲了微調對於驗顯像液之溶解性，能夠於感放射線性 樹脂組成物中添加具有羧基及/或磺酸酐基之化合物（以 下，稱爲「羧酸系添加劑」）。 羧酸系添加劑，例如可列舉：醋酸、丙酸 '正丁酸、 異丁酸、正戊酸、異戊酸、苯甲酸、桂皮酸等之單羧酸類； 乳酸、2 -羥基丁酸、3 -羥基丁酸、水楊酸、間羥基苯甲酸、 對羥基苯甲酸、鄰羥基桂皮酸、間羥基桂皮酸、對羥基桂 皮酸、5-羥基間苯二甲酸、丁香苷酸等之羥基單羧酸類； -39 - 200911523 草酸、琥珀酸、戊二酸、己二酸、馬來酸、衣康酸、六氫 化苯二甲酸、苯二甲酸、間苯二甲酸 '對苯二甲酸、1，2-環己烷二羧酸、1，2,4-環己烷三羧酸、偏苯三酸、均苯四甲 酸、1，2,3,4-丁烷四羧酸、1，2,3,4-環戊烷四羧酸、1，2,5,8-萘四羧酸等之多元羧酸類；衣康酸酐、琥珀酸酐、檸康酸 酐、十二碳烯琥珀酸酐、三苯胺基甲酸酐、馬來酸酐、六 氫化苯二甲酸酐、甲基四氫化苯二甲酸酐、降莰烯二酸酐 (HIMIC酸酐）、苯二甲酸酐、均苯四甲酸酐、偏苯三酸 酐、1,2,3,4-丁烷四羧酸二酐、1,2,3，4-環戊烷四羧酸二酐、 3，4,3’，4’-二苯甲酮四羧酸二酐、乙二醇雙（偏苯三酸酯） =酐、甘油三（偏苯三酸酯）三酐等之酸酐。 此等之羧酸系添加劑能夠單獨地或混合二種以上後而 使用。 相對於（A )共聚物1 00重量份，羧酸系添加劑之添加 量適宜爲1 0重量份以下，更佳爲5重量份以下。 再者，於不損及感放射線性樹脂組成物的原本特性之 ® ’較佳使合計添加量成爲所得的整個組成物之5 〇重量 〇以下之範圍’也能夠在感放射線性樹脂組成物中添加塡 充材、著色劑、黏度調整劑等。 上述塡充材，例如’可列舉：二氧化矽、氧化鋁、滑 石 '卷土、矽酸鍩、粉末玻璃等。 此等之塡充材能夠單獨地或混合二種以上後而使用。 另外，上述著色劑，例如，可列舉·礬土白、黏土、 碳酸_、硫酸鋇等之塡充顏料；鋅白、鉛白、鉛丹、群青、 -40 - 200911523 普魯士藍、氧化欽、鉻酸鋅、氧化鐵紅、碳黑等之無機顏 料’·繫胭脂紅6B、永久紅6B、永久紅R、聯苯胺黃、酞菁 藍、酞菁綠等之有機顏料；洋紅 '若丹明等之鹼性染料； 直接猩紅、直接橙等之直接染料；羅色靈（Rocelline)、 米塔尼爾黃等之酸性染料等。 此等之著色劑能夠單獨地或混合二種以上後而使用。 另外，上述黏度調整劑，例如，可列舉：皂土、矽膠、 鋁粉末等。 此等之黏度調整劑能夠單獨地或混合二種以上後而使 用。 感放射線性樹脂組成物係均勻混合（A )鹼可溶性共聚 物、（B )聚合性不飽和化合物、（C )光聚合起始劑、（D ) 鏈轉移劑及必要時所使用之添加劑，另外，基於使在基板 上之塗布作業成爲容易之目的下，較佳爲利用有機溶劑加 以稀釋後而作成液狀組成物。 上述有機溶劑較佳爲能夠使構成感放射線性樹脂組成 物之各成分得以均勻溶解或分散’不與該各成分反應’具 有適度之揮發性。 如此之有機溶劑’例如’針對與製造上述（A )鹼可溶 性共聚物之聚合所例示之溶劑同樣的有機溶劑之外，尙可 列舉：N -甲基甲醯胺、Ν，Ν·二甲基甲醯胺' N -甲基甲醯苯 胺、Ν-甲基乙醯胺、Ν，Ν-二甲基乙醯胺、Ν-甲基吡咯烷酮、 二甲基亞颯、苄基乙基醚、二己基醚、丙酮基丙酮、異佛 酮、己酸、辛酸、1_辛醇、1_壬醇、节醇、醋酸辛醋、苯 -41- 200911523 甲酸乙酯、草酸二乙酯、馬來酸二乙酯、γ -丁內酯、碳酸 乙烯、碳酸丙烯、乙二醇單苯基醚醋酸酯等之高沸點溶劑。 基於溶解性、與各成分之反應性及塗膜形成之容易 性，此等有機溶劑之中，較佳爲乙二醇單乙基醚、二乙二 醇單甲基醚等之多元醇的烷基醚；乙二醇單乙基醚醋酸酯 等多元醇之烷基醚醋酸酯；乳酸乙酯、3 -甲氧基丙酸甲酯、 3 -乙氧基丙酸乙酯等之其他酯；二丙酮醇等之酮等。 上述有機溶劑能夠單獨地或混合二種以上後而使用。 有機溶劑之使用量能夠按照感放射線性樹脂組成物之 具體用途、塗布方法等加以適當選擇。 於調製感放射線性樹脂組成物之際，未添加塡充材或 顏料之情形，可以僅利用通常之方法來攪拌混合；添加塡 充材或顏料之情形，最好使用溶解器、均質攪拌機、3輥 硏磨機等之分散機而予以分散混合。另外，於調製後，感 放射線性樹脂組成物必要時也可以藉由篩網、膜濾器等’ 過瀘後而提供使用。 乾膜之製法 本發明之乾膜係藉由將感放射線性樹脂組成物塗布於 該基層薄膜之表面上，然後，乾燥後而積層該感放射線性 樹脂組成物之層’接著，利用覆膜以覆蓋該層而能夠製造。 如第1圖所示’本發明優越之感放射線性乾膜具有在基層 薄膜上積層有感放射線性樹脂組成物層2〜2 〇 〇 μιη之厚 度’然後’進一步利用覆膜覆蓋後而予以一體化之構造。 於塗膜之形成中，例如使用塗布器、桿式塗布機、輥 -42 - 200911523 式塗布機、淋幕塗布機等。 若乾燥溫度過低時，乾燥上將費時；若過高時， 薄膜之熱收縮或感放射線性樹脂組成物之氣化等將發 乾燥溫度於4 0〜1 8 0 °C之範圍爲適當的，更佳爲6 0〜 °C。 覆膜能夠於室溫下貼附於感放射線性樹脂組成 上’也能夠一面加熱至約4 0〜6 0 °C的同時，也加以貼 微透鏡之製法 本發明之乾膜可使用於微透鏡之形成。 本發明之微透鏡係以各種Ο A機器、液晶電視、 電話、投影機等之液晶顯示元件爲主，能夠極適用於 機、電子複印機、固體攝影元件等之單晶片（on-Chip 色濾光片之成像光學系、光纖連接器等。 微透鏡之形成係由下列（i )〜（i v )之步驟所構 (i )將本發明之乾膜的感放射線性樹脂組成物層 至玻璃基板，將塗膜形成於基板上的步驟。 (i i )將放射線照射於該塗膜之至少一部分（以 稱爲「曝光j 。）的步驟。 (i i i )將曝光後之塗膜加以顯像的步驟。 (i v )加熱顯像後之塗膜（以下，稱爲「烘烤」 的步驟。 以下，針對此等之步驟加以說明。 —(i )步驟一 於此步驟中’依照上述之乾膜製程，在可撓性之 基層 生。 -1 3 0 物層 附。 行動 傳真 )彩 成： 轉印 下， 基層 -43 - 200911523 薄膜上，進行微透鏡形成用感放射線性樹脂組成物之預先 塗布、乾燥後而形成感放射線性之塗膜（感放射線性樹脂 組成物層），再將此塗膜貼附於基板後而使用。 使用製得的乾膜之情形，首先’去除覆膜’例如採用 常壓熱輥壓黏法、真空熱輥壓黏法、真空熱壓縮壓黏法等 之壓黏手法，施加適當之熱與壓力的同時，將乾膜轉印至 基板上。 所形成的塗膜之膜厚適宜約爲3〜50 μιη，更佳約爲1〇 〜3 0 μ m 〇 能夠使用之基板種類，可列舉：玻璃基板、矽晶圓、 或於此等表面上形成有各種金屬層之基板等。 將本發明之感放射線性樹脂組成物層塗布於基板之$ 法，除了從製作乾膜後而貼附於基板之方法以外，例如， 可列舉：旋轉塗布法、噴霧法、輥塗布法、桿式塗布法等 之適宜方法。 —(i i )步驟一 於此步驟中，在所形成的塗膜之至少一部分進行曝 光。在塗膜之一部分進行曝光之際，透過既定圖案之光罩 而進行曝光。 雖然曝光所用之放射線並未予以特別限定，按照所使 用之感放射線性聚合起始劑之種類等，例如，適宜選擇g 線（波長4 3 6nm) 、i線（波長3 6 5 n m )等之紫外線；K r F 準分子雷射等之遠紫外線；同步加速器放射線等之χ線、 電子線等之荷電粒子線等。 -44- 200911523 此等放射線之中，較佳爲紫外線，尤以含有g線及/或 i線之放射線特別理想。 另外，曝光量較佳約爲50〜1〇, 〇〇〇 J/m2。 於（i )步驟中，使用乾膜法之時，感放射線性轉印層 上之基層薄膜可以於曝光步驟前加以剝離去除，另外，也 可以於曝光步驟之後、於顯像步驟之前加以剝離去除。 一（iii)步驟— 於此步驟中，藉由利用顯像液，較佳爲鹼顯像液進行 所曝光之塗膜的顯像，去除未曝光部而形成既定形狀之圖 案。 例如，該顯像液可列舉：氫氧化鈉、氫氧化鉀、碳酸 鈉、矽酸鈉 '偏矽酸鈉、氨、乙胺、正丙胺、二乙胺、二 乙胺基乙醇、二正丙胺、三乙胺、甲基二乙胺、二甲基乙 醇胺、三乙醇胺、四甲基銨氫氧化物、四乙基銨氫氧化物、 毗咯、哌啶、1,8-二氮雜雙環〔5. 4. 0〕-7-十一烯、1，5-二氮雜雙環〔4_ 3. 0〕-5-壬烯等之鹼性化合物的水溶液。 於該鹼性化合物的水溶液中，也能夠適當量添加甲 醇、乙醇等之水溶性有機溶劑或界面活性劑。 還有，利用鹼顯像液以顯像之後，通常，例如，經由 水洗等加以洗淨。 另外，不含有顏料或塡充材等不溶性成分之感放射線 性樹脂組成物之情形下，也能夠將溶解構成該組成物之各 種有機溶劑作爲顯像液使用。 例如，顯像方法能夠採用盛液法、浸漬法、搖動浸漬 -45 - 200911523 法、淋幕法等之適宜方法。 雖然顯像時間係根據感放射線性樹脂組成物之組成而 有所不同，通常，常溫下約爲30〜300秒鐘。本發明所用 之感放射線性樹脂組成物之情形，藉由將顯像液之溫度約 設爲3 0〜3 5 °C，即使縮短顯像時間，也能夠形成良好之圖 案與微透鏡，基於製程時間（t a c t t i m e )縮短之方面爲有 利的。 微透鏡形成所用之習知感放射線性樹脂組成物之情 形，若顯像時間超過最適條件約20〜25秒鐘時，由於所形 成的圖案中發生剝離，必須嚴密控制顯像時間，本發明之 感放射線性樹脂組成物之情形，即使超過最適顯像時間約 3 0秒鐘以上，也能夠形成良好之圖案，基於製品良率方面 爲有利的。 一（i v )步驟一 於此步驟中，例如，藉由利用熱板、烘箱等之加熱裝 置以烘烤顯像後之塗膜，使該圖案予以熔融、硬化後而得 到透鏡形狀。 雖然烘烤條件也根據構成感放射線性樹脂組成物之各 成分之種類或使用比例、所希望之圖案形狀、加熱裝置等 而有所不同’熱板之情形，例如，於1 5 0〜2 4 0 °C下、約1 0 〜3 0分鐘左右；烘箱之情形，例如，於1 5 0〜2 4 0 °C下、約 3 0〜9 0分鐘左右。另外，於烘烤之際，也能夠採用進行2 次以上加熱處理之步驟烘烤法等。另外，也能夠採用後曝 光法，其係於烘烤前或烘烤後，將顯像後所得的圖案加以 -46- 200911523 曝光。 如上所述，本發明所用之感放射線性樹脂組成物能夠 形成解像度爲高的，具優越之保存安定性、塗布性等’具 有優越之特性均衡的高精細微透鏡及微透鏡陣列。 另外，本發明之微透鏡係具優越之膜厚、解像度 '圖 案形狀、透明性、耐熱性、耐熱變色性、耐溶劑性等之特 性均衡，尤其能夠極適合使用於各種OA機器、液晶電視、 行動電話、投影機等之液晶顯示元件。 另外，若根據本發明之乾膜製法及微透鏡製法時’能 夠以使用感放射線性乾膜之簡易製程而形成具有優越特性 之高精細微透鏡及微透鏡陣列。 【實施例】 以下，顯示實施例與比較例，更具體說明本發明’但 是本發明並不受以下之實施例所限定。 合成例1 氮氣置換燒瓶之後，進料作爲自由基聚合起始劑之 2，2 ’ -偶氮二異丁腈3 g與作爲溶劑之3 -甲氧基丙酸甲酯 1 00g，攪拌至自由基聚合起始劑溶解爲止。之後，進料甲 基丙烯酸19g、甲基丙烯酸-2-單（六氫化苯二甲醯氧基） 乙酯15g、苯乙烯15g及甲基丙烯酸三環癸酯46g後而開始 慢慢攪拌，進一步添加異戊二烯5 g。之後，使反應溶液之 溫度上升至80°C，於此溫度下進行4小時聚合，得到甲基 丙烯酸/2-單（六氫化苯二甲醯氧基）乙酯/苯乙烯/甲基丙 烯酸三環癸酯/異戊二烯之共聚物（共聚合重量比= -47 - 200911523 19/15/15/46/5、Mw=13,000、Mn = 8,000)。將此共聚物設爲 共聚物（A 1 )。 合成例2 相同於合成例1，使甲基丙烯酸/苯乙烯/甲基丙烯酸苄 酯/單（甲基）丙烯酸甘油酯/N -苯基馬來醯亞胺予以共聚合 (共聚合重量比=15/15/35/10/25、Mw = 7,000、Mn = 4,000)， 得到共聚物（A2 )。 調製顯示於下表1之組成的感放射線性光阻組成物溶 液。將此溶液設爲（S-1 )。 【表1】 (S-1) 摻合成分 摻合量 (A )成分 * 共聚物（A1 ) 80重量份 共聚物 *共聚物（A2) 20重量份 (B )成分 • ARONIX M-402 20重量份 聚合性不飽和化合物 • ARONIX M-309 10重量份 • ARONIX M-113 30重量份 (C)成分 • 氧化-2,4,6-三甲基苯甲醯基二 22重量份 光聚合起始劑 苯膦（商品名LUCIRIN TPO) • IRGACURE 651 12重量份 (D)成分 • 2,4-二苯基-4-甲基-1-戊烯 0.5重量份 鏈轉移劑 實施例1 乾膜之製作與覆膜之剝離、轉印、曝光係如1^ $ 行。 -48 - 200911523 在聚對苯二甲酸乙二酯（PET)薄膜之 COSMOSHINE 「A4100-50」（東洋紡（股）製）上，使用塗布器以均勻塗 布表1之感放射線性樹脂組成物（S - 1 )，於1 2 0°C加熱塗 膜8分鐘，形成厚度2 0 μηι之感放射線性樹脂組成物層， 從其上方，於室溫下、利用壓黏法以使感放射線性樹脂組 成物層與自黏性樹脂層得以接觸之方式，來使具有自黏性 樹脂層之聚乙烯（ΡΕ)製薄膜的TORETEC 7721 (薄膜Α、 TORAY加工（股）製）得以緊貼後而製得乾膜。接著，剝離 覆膜，將感放射線性樹脂組成物層之表面與玻璃基板之表 面相接觸，利用熱壓黏法以將感放射線性乾膜轉印至玻璃 基板上。 接著’透過既定圖案之光罩，在所得的基板上進行波 長3 6 5 nm之強度爲2 0 0 W/m2之紫外線的5秒鐘曝光。之後， 從基板上之感放射線性乾膜剝離去除基層薄膜，於2 5 °C， 經由0.3重量％氫氧化鉀水溶液，顯像2分鐘之後，利用 純水洗淨1分鐘後而形成圖案，得到膜厚丨8.7 μηι之圖案狀 薄膜。之後，藉由於1 5 0 °C之烘箱中，烘烤塗膜6 0分鐘後 而予以熔融與硬化，形成微透鏡。所得的微透鏡之評估係 利用下列之要領進行。將結果顯示於表7。 -殘膜率之評估一 針對顯像後之膜厚，殘膜率超過8 0 %之情形評估爲 〇；7 〇 %以上、低於8 0 %之情形評估爲△;低於7 0 %之情 形評估爲X。 -解像度之評估- -49 - 200911523 針對顯像後之圖案狀薄膜’線/間隙=1 〇 μ m /1 0 μ m之圖 案能夠解像之情形評估爲〇；線/間隙=2 0 ^ m / 2 0 ^ m之圖案 能夠解像之情形評估爲△;二者之圖案未能解像之情形評 估爲X。 -透鏡形狀之評估- 針對後烘烤後之己形成微透鏡的薄膜’利用穿透型電 子顯微鏡以觀察線/間隙=5〇μΠΐ/5〇μηι或之圖 案，評估是否符合第2圖之任意形狀。將如（a )之半球形 且透鏡形狀爲良好之情形設爲〇’特別理想之情形設爲 ◎。如（b )之熔融不足’無法成爲透鏡形狀’爲顛倒碟狀 之情形設爲△:如（c )之未完全熔融’成方形形狀之情形 設爲X。 實施例2 調製顯示於下表2之組成的感放射線性光阻組成物之 溶液。將此溶液設爲（S-2 )。 依照實施例1，將（S - 2 )塗布於基層薄膜上後而將覆 膜A壓黏於感放射線性樹脂組成物層上，進行乾膜製作、 剝離、轉印、曝光、顯像後而圖案形成、加熱處理。相同 於實施例1以進行所得的微透鏡之評估，將結果顯示於表 Ί。 -50 - 200911523 【表2】 (S-2) 摻合成分 摻合量 (A)成分 * 共聚物（A1) 80重量份 共聚物 * 共聚物（A2) 20重量份 (B)成分 參 ARONIX M-402 20重量份 聚合性不飽和化合物 • ARONIX M-309 10重量份 • ARONIX M-113 30重量份 (C)成分 • 氧化-2,4,6-三甲基苯甲醯基二 22重量份 光聚合起始劑 苯膦（商品名LUCIRIN TPO) ----- • IRGACURE 651 12重量份 (D)成分 春2,4-一苯基·4·甲基-1-戊儲 5重量份 移劑 實施例3 調製顯示於下表3之組成的感放射線性光阻組成物之 溶液。將此溶液設爲（S-3 )。 依照實施例1，將（S-3 )塗布於基層薄膜上後而將覆 膜A壓黏於感放射線性樹脂組成物層上，進行乾膜製作、 剝離、轉印、曝光、顯像後而圖案形成、加熱處理。相同 於實施例1以進行所得的微透鏡之評估，將結果顯示於表 200911523 【表3】 (S-3) 摻合成分 摻合量 (A )成分 * 共聚物（A1) 100重量份 共聚物 (B)成分 • ARONIX M-402 25重量份 聚合性不飽和化合物 • ARONIX M-309 15重量份 • ARONIX M-113 20重量份 (C)成分 • 氧化-2,4,6-三甲基苯甲醯基二 22重量份 光聚合起始劑 苯膦（商品名LUCIRIN TPO) • IRGACURE 651 12重量份 (D)成分 ♦ 2,4-—本基-4-甲基-1-戊燒 1重量份 鏈轉移劑 實施例4 調製顯示於下表4之組成的感放射線性光阻組成物之 溶液。將此溶液設爲（S-4 )。 依照實施例1，將（S -4 )塗布於基層薄膜上後而將覆 膜A壓黏於感放射線性樹脂組成物層上’進行乾膜製作、 剝離、轉印、曝光、顯像後而圖案形成、加熱處理。相同 於實施例1以進行所得的微透鏡之評估’將結果顯示於表 -52 - 200911523 【表4】 (S-4) 摻合成分 摻合量 (A )成分 * 共聚物（A1) 80重量份 共聚物 * 共聚物（A2) 20重量份 (B)成分 • ARONIX M-402 25重量份 聚合性不飽和化合物 • ARONIX M-309 15重量份 • ARONIX M-113 20重量份 (C)成分 • 氧化-2,4,6-三甲基苯甲醯基二 22重量份 光聚合起始劑 苯膦（商品名LUCIRIN TPO) • IRGACURE 651 12重量份 (D)成分 • 2,4-二苯基-4-甲基-1-戊烯 10重量份 鏈轉移劑 比較例1 調製顯示於下表5之組成的感放射線性光阻組成物之 溶液。將此溶液設爲（S - 5 )。 依照實施例1，將（S - 5 )塗布於基層薄膜上後而將覆 膜A壓黏於感放射線性樹脂組成物層上，進行乾膜製作、 剝離、轉印、曝光、顯像後而圖案形成、加熱處理。相同 於實施例1以進行所得的微透鏡之評估，將結果顯示於表 Ί。 200911523 【表5】 (S-5) 摻合成分 摻合量 (A)成分 * 共聚物（A1) 80重量份 共聚物 * 共聚物（A2) 20重量份 (B)成分 參 ARONIX M-402 25重量份 聚合性不飽和化合物 • ARONIX M-309 15重量份 參 ARONIX M-113 20重量份 (C )成分 參氧化-2,4,6-三甲基苯甲醯基二 22重量份 光聚合起始劑 苯膦（商品名LUCIRIN TPO) • IRGACURE 651 12重量份 比較例2 調製顯示於下表6之組成的感放射線性光阻組成物之 溶液。將此溶液設爲（S-6)。 依照實施例1，將（S - 6 )塗布於基層薄膜上後而將覆 膜A壓黏於感放射線性樹脂組成物層上，進行乾膜製作、 剝離、轉印、曝光、顯像後而圖案形成、加熱處理。相同 於實施例1以進行所得的微透鏡之評估，將結果顯示於表 -54- 200911523 【表6】 (S-6) 摻合成分 摻合量 (A)成分 * 共聚物（A1 ) 100重量份 共聚物 (B)成分 • ARONIX M-8100 40重量份 聚合性不飽和化合物 • ARONIX M-309 10重量份 (C)成分 • 氧化-2,4,6-三甲基苯甲醯基二 22重量份 光聚合起始劑 苯膦（商品名LUCIRIN TPO) • IRGACURE 651 12重量份 【表7】 殘膜率 解像度 透鏡形狀 實施例1 〇 〇 ◎ 實施例2 〇 〇 ◎ 實施例3 〇 〇 〇 實施例4 Δ 〇 ◎ 比較例1 〇 〇 Δ 比較例2 〇 〇 Δ 【圖式簡單說明】 第1圖係本發明之感放射線性乾膜之層構造的說明 圖。 第2圖係顯示透鏡剖面形狀之示意圖。 【元件符號說明】 4E 。 -55 -Further, specific examples of the compound represented by the formula (8) include: ARONIX M-7100, ARONIX M-8 0 0 0 , ARONIX M-8060, ARONIX M-8100, ARONIX M-9050 (East Asia Synthesis) Chemical industry (stock) system, KAYARAD T-1420 (T) (X = C (CH2CH3) I, Y = - (CH2OCH2) -) [Nippon Chemical Co., Ltd.] and so on. Further, specific examples of the compound represented by the formula (9) include: KAYARAD DPCA-20 under the trade name (x = about 1, a = about 2, b = about 4), -25 - 200911523 KAYARAD DPCA-30 ( x = about a = a 3, b = about 3), KAYARAD DPCA-6 0 (x = about a = about 6, b = about 0), KAYARADDPCA-120 (x = about 2, a = about 6, b = about 〇) [above, Nippon Kayaku Co., Ltd.]; V-360, V-GPT, V-3PA, V-400 (above, Osaka Organic Chemical Industry Co., Ltd.). Among these (B) polymerizable unsaturated compounds, a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds are preferable, and more preferably, it is represented by the formula (4). The compound and the compound of the formula (8) ξ. In the present invention, the (Β) polymerizable unsaturated compound can be used singly or in combination of two or more kinds. The amount of the (Β) polymerizable unsaturated compound in the present invention is suitably from 30 to 150 parts by weight, more preferably from 50 to 1 part by weight, based on 100 parts by weight of the (?) copolymer. When the amount of the (Β) polymerizable unsaturated compound is less than 3 parts by weight, the sensitivity at the time of radiation irradiation is liable to lower. On the other hand, if it exceeds 150 parts by weight, the compatibility with the (A) copolymer is feared. It will deteriorate, and V will be rough on the surface of the coating film. (C) Photopolymerization Initiator - The component (C) in the present invention is an active species which initiates (B) polymerization of a polymerizable unsaturated compound by irradiation of radiation, for example, by generating a radical or the like It is composed of a polymerization initiator. Examples of the (C) photopolymerization initiators include, for example, α-diketones such as a benzyl group and a diethyl fluorenyl group; an acetoin or the like; benzoin methyl ether and benzoin ethyl group; Ether ether, benzoin isopropyl ether, etc.; 9-oxosulfur D[Ij哩, -26- 200911523 2,4-diethyl-9-oxosulfonate, comet, 9-oxosulfur 9-oxosulfuric acid such as 哔-4-sulfonic acid _ drinking; benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino) Benzophenones such as benzophenone; acetophenone, p-dimethylaminoacetophenone, α,α'-dimethoxyacetoxybenzophenone, 2,2'-dimethyl Acetophenones such as oxy-2-phenylacetophenone and p-methoxyacetophenone; hydrazine, 1,4-naphthoquinone, etc.; benzamidine methyl chloride, tribromomethylphenyl a halide such as ruthenium, tris(trichloromethyl)-s-three tillage, or a peroxide such as di(tertiary butyl) peroxide; oxidized-2,4,6-trimethylbenzhydryl Phenylphosphine oxide, etc.; 1-(9-ethyl-6-benzylidene-yl- 9. Hey. -oxazol-3-yl)-nonane-1,2-decane-2-indole-indole-benzoate, 1-(9-ethyl-6-benzylidene-9). Oh. -carbazole-3-yl)-nonane-1,2-decane-2-indole-0-acetate, 1-(9-ethyl-6-benzylidene-9. Oh. -carbazole-3-yl)-pentane-1,2-pentane-2-indole-0-acetate ' 1 -(9-ethyl-6-benzamide-9. Hey. -oxazol-3-yl)-octane-1-one oxime-0-acetate, 1-[9-ethyl-6-(2-methylbenzhydryl)-9. Η·-carbazole-3-yl]-ethane-1-one oxime-0-benzoate, 1-[9-ethyl-6-(2-methylbenzylidene)-9. Oh. -carbazole-3-yl]-ethane-1-ketooxime-0-acetate, 1-[9-ethyl-6-(1,3,5-trimethylbenzylidene)-9 . Hey. -oxazol-3-yl]-ethane-1-one oxime-0-benzoate, 1-[9-butyl-6-(2-ethylbenzylidene)-9. !1·-oxazol-3-yl]-ethane-1-one oxime-indole-benzoate, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2_( 〇-benzylidene hydrazide), 1,2-butanedione-1-[4-(phenylthio)phenyl]-2-(indolyl-benzhydrylhydrazine), 1,2-butanedione- 1-[4-(phenylthio)phenyl]-2-(indo-ethenylhydrazine), 1,2-octanedione-1-[4-(methylthio)phenyl]-2-(indole- 0-醯 such as benzamidine oxime), 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-[0-(4-methylbenzhydrylhydrazine)] Base -27 - 200911523 and so on. Further, (C) a commercially available product of a photopolymerization initiator may, for example, be IRGACURE 184, IRGACURE 500, IRGACURE 651, IRGACURE 907, IRGACURE 369, IRGACURE 379, IRGACURE CG24-61 (above, CIBA SPECIALITY CHEMICALS) )), LUCIRIN LR8728, LUCIRIN TPO (above, manufactured by BASF Corporation), DAROCURE 1116' DAROCURE 1173 (above, manufactured by MERK Corporation), UBECRYL p36 (manufactured by UCB Corporation), and the like. Among these (C) photopolymerization initiators, preferred is 2-methyl[4-(methylthio)phenyl]-2-morpholinylpropan-1-one '2-benzyl-2-di Acetophenones such as methylamino-1-(4-morpholinylphenyl)butan-1-one; or benzamidine methyl chloride, tribromomethylphenyl maple, oxidized-2,4,6- Trimethylbenzhydryldiphenylphosphine, and the like. (C) The photopolymerization initiator may be used singly or in combination of two or more kinds, and one or more kinds of radiation sensitizers may be used. The amount of the (C) photopolymerization initiator is suitably 0. The amount of the (C) photopolymerization initiator is 0. 01 to 100 parts by weight, more preferably 〇. 01 to 50 parts by weight, further preferably 0. 5 to parts by weight. If (c) the amount of photopolymerization initiator is lower than 〇. When 1 part by weight is used, the sensitivity will be lowered. On the other hand, if it exceeds 1 part by weight, 'the compatibility with the (A) copolymer or (B) polymerizable unsaturated compound will be deteriorated' The obtained resin composition tends to lower the stability. (D) chain transfer agent - (D) chain transfer agent in the invention is a kind of adjustment of the degree of polymerization of (B) polymerizable unsaturated compound caused by radiation irradiation 'after control baking -28 - 200911523 The composition of the lens shape. Such a component (D) can be exemplified by an amine-based compound of acetonitrile, acetamidine, acetamidine acetate or citric acid vinegar; toluene, ethylbenzene, tert-butylbenzene, triphenylmethane, 2 An aromatic hydrocarbon such as 4-diphenyl-4-methyl-1-pentene; a quinone hydrazine or the like; chloroform, carbon tetrachloride, carbon tetrabromide, bromochloromethane, etc. Halogenated hydrocarbon; nitro compound such as nitromethane, trinitromethane, 1,1,1-trinitroethane; phenol such as p-methoxyphenol, 2,3,4,6-tetramethylphenol An amine compound such as triethylamine, tri-n-propylamine, tri-n-butylamine, hydrazine, hydrazine-dimethylaniline, anthracene, fluorene-divinylaniline, octyl thiol, n-butyl thiol, Sulfur of n-pentyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan 'n-dodecyl mercaptan, tertiary tetradecyl mercaptan, tertiary dodecyl mercaptan Alcohol; dimethyl xanthogen disulfide, diter yellow disulfide disulfide, diisopropyl xanthogen disulfide, etc.; dimethyl sulfide methyl disulfide, tetraethylammonium disulfide disulfide , disulfide methyl sulfonium dithiocyanate, etc. Pentaphenylethane, (X-methylstyrene dimer, etc. hydrocarbons: and acrolein, methacrolein, allyl alcohol, thioglycolic acid 2-ethylhexyl ester, onion oleyl, α-萜Terpene, γ-terpinene, dipentene, etc. " Among these chain transfer agents, 2,4-diphenyl-4-methyl-1-pentene, p-methoxyphenol is preferred The tertiary chain thiol thiol, etc. The chain transfer agent can be used singly or in combination of two or more. In the present invention, the amount of the chain transfer agent is suitably 100 parts by weight based on the (Α) copolymer. Hey. 〇丨~1〇 by weight, more preferably 〇. It is particularly preferable that 〇 5 to 10 parts by weight is particularly preferably 0. 1 to 5 parts by weight. If the amount of chain transfer agent is less than 0. At 0 parts by weight, there is concern that the desired effect cannot be obtained. On the other hand, when it exceeds 10 parts by weight, the hardening due to exposure does not sufficiently proceed to -29 - 200911523, and the solubility tends to be very high after development. As an additive, an (E) decane coupling agent can be added to the radiation sensitive resin composition. The component (E) functions as an adhesion aid for improving the adhesion to the substrate. As the component (E), for example, a decane coupling agent having a reactive f substituent such as a carboxyl group, a methacryl group, a vinyl group, an isocyanate group or an epoxy group is preferable. More specifically, Mention may be made: trimethoxydecyl benzoic acid, γ-methyl propylene oxypropyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ-isocyanate propyl triethoxy Decane, 3-methacryloxypropyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxy sand or the like. These decane coupling agents can be used singly or in combination of two or more. The amount of the decane coupling agent added is suitably 0. 1 part by weight of the (A) copolymer. 1 to 30 parts by weight is more preferably 1 to 20 parts by weight. In the radiation sensitive linear resin composition, it is polymerized by heating to be able to add (F) a thermally polymerizable compound which is not polymerized according to radiation irradiation. Thus, the (F) thermal polymerizable compound is suitable for 80 to 2 5 〇° C 'better than 8 0 to 1 60 ° C, especially at 1 〇〇 ~ 1 50 ° C for thermal polymerization is particularly desirable. In the case of the radiation-sensitive resin composition for lens formation, in the case where the temperature of the heat treatment is set to 160 or less to form a lens, it is preferable to add -30 to 200911523 to add (F) a thermally polymerizable compound. In general, the (F) thermally polymerizable compound is a monomer, and the molecular weight thereof is not particularly limited, and may have a molecular weight of an oligomer level. (F) A thermally polymerizable compound, and a thermopolymerizable functional group in the molecule, for example, a compound having one or more or more epoxy groups, an epoxy group, a cyclobutylene group or the like. However, among the adhesion promoters to be described later, the functional decane coupling agent having an epoxy group also contains a thermally polymerizable compound having an epoxy group. (F) Among the thermopolymerizable compounds, a compound having an epoxy group, for example, methyl epoxypropyl ether, ethyl epoxypropyl ether, n-propyl epoxypropyl ether, and the like Alkyl epoxy propyl ether such as propyl epoxypropyl ether, n-butyl epoxypropyl ether, secondary butyl epoxypropyl ether, tertiary butyl epoxypropyl ether; ethylene glycol single An alkylene glycol monoepoxy such as epoxidized propyl ether, propylene glycol monoepoxypropyl ether, 1,4-butanediol monoepoxypropyl ether or 1,6-hexanediol monoepoxypropyl ether Propyl ether; polyalkylene glycol monoepoxypropyl ether such as polyethylene glycol monoepoxypropyl ether, polypropylene glycol monoepoxypropyl ether; phenylepoxypropyl ether, o-tolyl epoxy Propyl ether, m-tolyl-epoxypropyl ether, p-tolyl-epoxypropyl ether, o-ethylphenylepoxypropyl ether, m-ethylphenylepoxypropyl ether, p-ethylphenyl ring a compound having a glycidyl ether such as an aryl epoxypropyl ether such as oxypropyl ether; or [(3,4-epoxycyclohexyl)methyl]methyl ether, [(3,4-epoxy) Cyclohexyl)methyl]ethyl ether, [(3,4-epoxycyclohexyl)) ] n-propyl ether, [(3,4-epoxycyclohexyl)methyl]isopropyl]'[(3,4-epoxycyclohexyl)methyl]n-butyl ether' [(3,4- [(3,4-epoxycyclohexyl) such as epoxycyclohexyl)methyl]secondary butyl ether or [(3,4-epoxy-31-200911523 hexyl)methyl]terternary butyl ether Methyl]alkyl ether; ethylene glycol mono[(3,4-epoxycyclohexyl)methyl]ether, propylene glycol mono[(3,4-epoxycyclohexyl)methyl]ether, 1,4-butyl Alkylene glycol monobutyl [(3,4-epoxycyclohexyl)methyl]ether, 1,6-hexanediol mono[(3,4-epoxycyclohexyl)methyl]ether [(3,4-epoxycyclohexyl)methyl]ether; polyethylene glycol mono[(3,4-epoxycyclohexyl)methyl]ether, polypropylene glycol mono[(3,4-epoxycyclohexyl) a polyalkylene glycol mono[(3,4-epoxycyclohexyl)methyl]ether such as methyl]ether; [(3,4-epoxycyclohexyl)methyl]phenyl ether, [( 3,4-epoxycyclohexyl)methyl]-o-tolyl ether, [(3,4-epoxycyclohexyl)methyl]m-tolyl ether, [(3,4-epoxycyclohexyl)methyl] Toluene Ether, [(3,4-epoxycyclohexyl)methyl]-o-ethylphenyl ether, [(3,4-epoxycyclohexyl)methyl]-m-ethylphenyl ether, [(3,4- A compound having a 3,4-epoxycyclohexyl group such as [(3,4-epoxycyclohexyl)methyl] aryl ether such as epoxycyclohexyl)methyl]p-ethylphenyl ether. Further, examples of the compound having two or more epoxy groups include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and hydrogenated bisphenol. A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F epoxide Di-epoxypropyl ether of bisphenol compound such as propyl ether, brominated bisphenol S diglycidyl ether; ethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, 1,4-butane Polycyclic ring of polyol such as diol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, glycerol triepoxypropyl ether, trimethylolpropane triepoxypropyl ether Oxypropyl propyl ether; polyethylene glycol bicyclo-32 - 200911523 polyalkylene glycol diepoxypropyl ether of oxypropyl ether, polypropylene glycol diepoxypropyl ether, etc.; by one or two a polyepoxy propyl ether of a polyether polyol obtained by adding the above alkylene oxide (for example, ethylene oxide, propylene oxide, etc.) to an aliphatic polyol such as ethylene glycol, propylene glycol or glycerin; Bisphenol A type epoxy resin; bisphenol F Epoxy resin; phenolic novolac type epoxy resin; cresol novolac type epoxy resin; polyphenol type epoxy resin; other alicyclic epoxy resin, other alicyclic polyepoxypropyl ether, advanced polybasic fatty acid Polyepoxypropyl ester; epoxidized soybean oil, epoxidized linseed oil; or the following bisphenol A type epoxy resin: trade name EPICOAT 825, 828, 834, 1001, 1002, 1003, 1004, 1007, 1009 '1010, 8000, 8034 (above, JAPAN EPOXY RES IN system), etc.; bisphenol F type epoxy resin: EPICOAT 807 [JAPAN EPOXY RESIN (manufactured by the company)]; phenol novolac type epoxy resin: EPICOAT 152 154, 157S65 [above, JAPAN EPOXY RESIN (share) system], EPPN201, 202 (above, Nippon Chemical Co., Ltd.), etc.; cresol novolac epoxy resin: EOCN 102, 103S, 104S, 1020, 1025, 102 7 [above, Nippon Kayaku Co., Ltd.], EPICOAT 180S75 [JAPAN EPOXY RESIN (manufactured by the company)], polyphenol type epoxy resin: EPICOAT 1032H60, XY-4000 (above, JAPAN EPOXY RESIN) 〕etc; other alicyclic polyepoxy resin: CY-175, 177 179, Araldite CY-182 '192,184 [the above, CIBA SPECIALITY CHEMICALS Co., Ltd.], ERL-4206, -4221, -42 3 4' -4299 (above, u. C. C. Company system), SHODYNE 509 [Showa Denko (share) system], EPICLON 200, 400 [above 'Greater Japan Ink (share) system'' EPICOAT 871, 872 [above 'JAPAN EPOXY RESIN (share) system), 200911523 ED- 5661, -5662 (above, CELANESE COATING company), etc.; other aliphatic polyepoxypropyl ether: EPOLIGHT 100MF [Kyoeisha Chemical Co., Ltd.], EPIOL TMP [Japan Oils and Fats Co., Ltd.], etc. Further, a compound having two or more 3,4-epoxycyclohexyl groups may be exemplified by [(3,4-epoxycyclohexyl)methyl]ester of 3,4-epoxycyclohexanecarboxylic acid, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexanedioxane, bis[(3,4-epoxycyclohexyl)methyl]adipate , bis[(3,4-epoxy-6-methylcyclohexyl)]methyl] adipate, 3,4-epoxy-6-methylcyclohexanecarboxylic acid (3,4-ring Oxy-6-methylcyclohexyl)ester, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide; ethylene glycol double [(3,4_epoxy) Cyclohexyl) methyl]ether, bis(3,4-epoxycyclohexanecarboxylic acid) ester of ethylene glycol, 3,4-ring a reaction product of [(3,4-epoxycyclohexyl)methyl]-cyclohexanecarboxylic acid and caprolactone; a compound having an epoxy group and a 3,4-epoxycyclohexyl group: 1 , 2: 8,9 - Diepoxylimene and the like. Further, examples of the compound having an episulfide group include, for example, "J. Org. Chem·, Vol. In the method of 28, ρ. 229 (1963), the above-mentioned compound having one or two or more epoxy groups is converted into an epoxy group. Further, as the compound having one butylene oxide group, for example, 3-methyl-3-methoxymethylbutylene oxide, 3-ethyl-3-methoxymethyl epoxy Ding Yuan, 3-methyl-3·ethoxymethylbutylene oxide, 3-ethyl-3-ethoxymethylbutylene oxide, 3-methyl-3-hydroxymethylepoxy Alkane, 3-ethyl-3-hydroxymethylbutylene oxide, 3-methyl-3-phenoxymethylbutylene oxide, 3-ethyl-3-phenoxymethylbutylene oxide , 3-methyl-3-benzyloxymethylbutylene oxide, 3-ethyl-34 - 200911523 -3-benzyloxymethylbutylene oxide, 3-methyl-3-[(2- Ethylhexyloxy)methyl]butylene oxide, 3-ethyl-3-[(2-ethylhexyloxy)methyl]butylene oxide, 3-methyl-3-(N-positive) Butyl decyl methoxy) butylene oxide, 3-ethyl 3-(N-n-butyl decyl methoxy) butylene oxide. Further, as the compound having two or more epoxycycloalkyl groups, for example, 3,7-bis(3-butoxybutyl)-5-oxydecan, 3,3'-[ 1,3 - (2-methylene)propanediylbis(hydroxymethylene)]bis(3-ethylbutylene oxide), :I,4-bis[(3-ethyl-3-butylene oxide) Methoxymethyl]benzene, bis[(3-ethyl-3-butylenebutyl)methyl]terephthalate, 1,2-bis[(3-ethyl-3-ring) Oxybutyryl)methoxymethyl]ethane, 1,3-bis[(3-ethyl-3-butylenebutyl)methoxymethyl]propane, ethylene glycol bis[(3- Ethyl-3-epoxybutylalkyl)methyl]ether, diethylene glycol bis[(3-ethyl-3-butylene oxide)methyl]ether, triethylene glycol bis[(3 - Ethyl-3-butylenebutyl)methyl]ether, tetraethylene glycol bis[(3-ethyl-3-butylenebutyl)methyl]ether dicyclopentenyl bis[(3) -ethyl-3-butylenebutyl)methyl]ether, tricyclodecanediyldimethylenebis[(3-ethyl-3-butylenebutyl)methyl]ether, trihydroxyl Methylpropane tris[(3-ethyl-3-butylenebutyl)A Ether, 1,4-bis[(3-ethyl-3-butylenebutyl)methoxy]butane, 1,6-bis[(3-ethyl-3-butylenebutyl) Methoxy]hexane, pentaerythritol tris[(3-ethyl-3-butylenebutyl)methyl]ether, pentaerythritol tetrakis[(3-ethyl-3-butylenebutyl)methyl]ether , polyethylene glycol bis[(3-ethyl-3-butylenebutyl)methyl]ether, dipentaerythritol hexa[(3-ethyl-3-butylenebutyl)methyl]ether, two Pentaerythritol penta[(3-ethyl-3-butylenebutyl)methyl]ether, dipentaerythritol tetrakis[(3-ethyl-3-epoxy-3 5 - 200911523 butanyl)methyl]ether, Reaction product of dipentaerythritol hexa[(3-ethyl-3-butylene oxide)methyl]ether with caprolactone, dipentaerythritol penta[(3-ethyl-3-butylenebutyl)) Reaction product of ether and caprolactone, bis(trimethylol)propanetetrakis((3-ethyl-3-butylene oxide)methyl]ether, bisphenol A bis[(3-ethyl) Reaction product of benzyl-3-butylene)methyl]ether with ethylene oxide, bisphenol A bis[(3-ethyl-3-butylene oxide)methyl]ether and ring a reaction product of oxypropane, a reaction product of hydrogenated bisphenol A bis[(3-ethyl-3-butylene oxide)methyl]ether and ethylene oxide, hydrogenated bisphenol A bis [(3- Reaction product of ethyl-3-butylbutylene)methyl]ether with propylene oxide, bisphenol F bis[(3-ethyl-3-butylenebutyl)methyl]ether and epoxy A reaction product of ethane or the like. Among these (F) thermally polymerizable compounds, bisphenol A type epoxy resin, phenol novolak type epoxy resin, and 3,4-epoxycyclohexanecarboxylic acid [(3,4-epoxy) are preferred. Cyclohexyl)methyl]ester, bis[(3-ethyl-3-butylenebutyl)methyl]terephthalate, and the like. The above (F) thermally polymerizable compound can be used singly or in combination of two or more kinds. The amount of the (F) thermally polymerizable compound to be added is preferably 100 parts by weight or less, more preferably 50 parts by weight or less based on 100 parts by weight of the (A) copolymer. When (F) the thermally polymerizable compound exceeds 100 parts by weight, the development of the obtained resin composition may be impaired. In the radiation sensitive resin composition of the present invention, a thermal polymerization inhibitor can be added in order to suppress a decrease in developability due to heating during prebaking. -36 - 200911523 醌, 醌, 4, 4 5 - such a thermal polymerization inhibitor 'for example, 焦掊酣, p-phenylhydrogen, methylene blue, tert-butyl catechol, methyl hydrogen醌, n-pentylpentyloxyhydroquinone, n-butylphenol 'phenol, hydroquinone mono-n-propyl ether, [1-{4-( 1-[4-hydroxyphenyl]_丨_methylethyl Phenyl}ethylidene, 1,1,3-bis(2,5-monomethyl-4)phenyl)-3-phenylpropane and the like. These thermal polymerization inhibitors can be used singly or in combination of two or more. The amount of the thermal polymerization inhibitor added is preferably 5 parts by weight or less, more preferably 3 parts by weight or less based on 0 parts by weight of the (F) thermally polymerizable compound. Further, in the radiation sensitive resin composition, a surfactant can be added in order to improve coatability, defoaming property, flatness, and the like. Examples of such a surfactant are, for example, a fluorine-based surfactant, a siloxane-based surfactant, an anionic surfactant, and the like. Examples of the fluorine-based surfactant include FTX-212D and FTX-218' FTX-208D (manufactured by NEOS Co., Ltd.) under the trade names; BM-1000 and BM-110 0 (above, BM CHIMIE) ;MAGAFAC F142D, F172, F173, F183 [above, Dainippon Ink Chemical Industry Co., Ltd.]; FLORAD FC-135, FC-170C, FC-430, FC-431 [above, Sumitomo 3M (share) system] ;SURFLON S-112, S-H3, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 [ Above, Asahi Glass Co., Ltd., etc. In addition, examples of the above-mentioned oxane-based surfactant include SH-28PA 'SH-190 > SH-193, SZ-6032, SF-842 8 'DC-57, -190 (above, TORAY DOW CORNING SILICONE (shares -37 - 200911523), KP341 [Shin-Etsu Chemical Industry Co., Ltd.], F-TOP EF301, EF303, EF3 52 [above, New Akita Chemicals Co., Ltd.]. Further, the above-mentioned anionic surfactant may, for example, be a polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or polyoxyethylene oleyl ether; polyoxyethylene n-octyl group; Polyoxyethylene storage aryl ether such as phenyl ether or polyoxyethylene n-nonylphenyl ether; polyoxyethylene dialkyl ester such as polyoxyethylene storage dilaurate or polyoxyethylene distearate. Further, examples of the surfactant other than the above may be exemplified by the trade name POLYFLOW-No. 57. No. 9 0 [above] Sakamoto Kyorisha Chemical (share) system, etc. These surfactants can be used singly or in combination of two or more. The amount of the surfactant added is preferably 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight of the (A) copolymer. When the amount of the surfactant added exceeds 5 parts by weight, the film of the coating film tends to be rough at the time of coating. In the radiation sensitive resin composition, in order to adjust the solubility in the alkali imaging solution of the (A) copolymer, a dissolution promoter or a dissolution controlling agent can be added. That is, in the case where the solubility of the alkali imaging solution of the (A) copolymer is too low, the dissolution promoter can be blended to improve the solubility of the (A) copolymer, (A) when the alkali is developed (A) The dissolution rate of the copolymer is moderately increased. Conversely, in the case where the solubility of the alkali imaging solution of the (A) copolymer is too high, the dissolution controlling agent can be blended to control the solubility of the (A) copolymer, which has the (A) copolymerization when the alkali is developed. The dissolution rate of the substance is moderately reduced -38 - 200911523. The dissolution promoter and the dissolution controlling agent are not particularly limited, and are preferably compounds which do not undergo chemical changes in the steps of prebaking, exposure, development, and the like of the radiation sensitive resin composition. For example, the dissolution promoter may be a low molecular weight phenolic compound having a benzene ring number of about 2 to 6. More specifically, examples thereof include bisphenols and tris(hydroxyphenyl)methanes. Further, the 'solubility controlling agent' may, for example, be an aromatic hydrocarbon such as naphthalene, phenanthrene or anthracene; a ketone such as acetophenone, benzophenone or phenylnaphthyl ketone; methylphenyl hydrazine or diphenyl; Grinding of base quinone, dinaphthyl hydrazine, etc. These dissolution promoters and dissolution control agents can be used singly or in combination of two or more kinds. The amount of the dissolution promoter and the dissolution control agent to be added can be appropriately adjusted depending on the type of the (A) copolymer to be used, and is preferably 50 parts by weight or less based on 1 part by weight of the (a) copolymer. It is preferably 30 parts by weight or less. In order to finely adjust the solubility in the image forming liquid, a compound having a carboxyl group and/or a sulfonic acid anhydride group (hereinafter referred to as "carboxylic acid additive") can be added to the radiation sensitive resin composition. Examples of the carboxylic acid-based additive include monocarboxylic acids such as acetic acid, propionic acid 'n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; lactic acid, 2-hydroxybutyric acid, and 3 - Hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, o-hydroxycinnamic acid, m-hydroxycinnamic acid, p-hydroxycinnamic acid, 5-hydroxyisophthalic acid, syringic acid, etc. Acids; -39 - 200911523 Oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid 'terephthalic acid, 1,2 -cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, trimellitic acid, pyromellitic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,3 a polycarboxylic acid such as 4-cyclopentane tetracarboxylic acid or 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecene succinic anhydride, triphenylamine group A Anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, norbornene dianhydride (HIMIC anhydride), phthalic anhydride, pyromellitic anhydride, trimellitic anhydride 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,4,3',4'-benzophenone tetracarboxylic acid Anhydrides such as dianhydride, ethylene glycol bis(trimellitic acid ester) = anhydride, triglyceride (trimellitic acid ester) trihydride, and the like. These carboxylic acid-based additives can be used singly or in combination of two or more kinds. The amount of the carboxylic acid-based additive to be added is preferably 10 parts by weight or less, more preferably 5 parts by weight or less based on 100 parts by weight of the (A) copolymer. In addition, in the radiation-sensitive resin composition, the product of the original characteristics of the radiation-sensitive resin composition is not damaged, and the total addition amount is preferably in the range of 5 〇 weight 〇 or less of the entire composition obtained. Add enamel, colorant, viscosity modifier, and the like. Examples of the above-mentioned enamel filler include cerium oxide, aluminum oxide, talc, earth strontium silicate, powdered glass, and the like. These crucibles can be used singly or in combination of two or more. Further, examples of the coloring agent include cerium white, clay, carbonic acid, barium sulfate, and the like; zinc white, lead white, lead dan, ultramarine blue, -40 - 200911523 Prussian blue, oxidized chin, chromium Inorganic pigments such as zinc acid, iron oxide red, carbon black, etc., organic pigments such as carmine red 6B, permanent red 6B, permanent red R, benzidine yellow, phthalocyanine blue, phthalocyanine green, etc.; Basic dyes; direct dyes such as direct scarlet, direct orange; acid dyes such as Rocelline and Mitanier Yellow. These coloring agents can be used singly or in combination of two or more kinds. Further, examples of the viscosity adjusting agent include bentonite, silicone, aluminum powder and the like. These viscosity modifiers can be used singly or in combination of two or more. The radiation sensitive linear resin composition uniformly mixes (A) an alkali-soluble copolymer, (B) a polymerizable unsaturated compound, (C) a photopolymerization initiator, (D) a chain transfer agent, and an additive used as necessary, and For the purpose of facilitating the coating operation on the substrate, it is preferably diluted with an organic solvent to prepare a liquid composition. The organic solvent is preferably one which is capable of uniformly dissolving or dispersing the components constituting the radiation sensitive resin composition, and does not react with the respective components, and has a moderate volatility. Such an organic solvent 'for example' is an organic solvent similar to the solvent exemplified for the polymerization of the above-mentioned (A) alkali-soluble copolymer, and examples thereof include N-methylformamide, hydrazine, hydrazine dimethyl Formamide ' N -methylformamide, Ν-methylacetamide, hydrazine, hydrazine-dimethylacetamide, hydrazine-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, two Hexyl ether, acetonylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-decanol, hexyl alcohol, acetic acid vinegar, benzene-41- 200911523 ethyl formate, diethyl oxalate, maleic acid A high boiling point solvent such as diethyl ester, γ-butyrolactone, ethylene carbonate, propylene carbonate or ethylene glycol monophenyl ether acetate. Among these organic solvents, those of the polyols such as ethylene glycol monoethyl ether and diethylene glycol monomethyl ether are preferred because of solubility, reactivity with each component, and ease of formation of a coating film. An alkyl ether acetate of a polyhydric alcohol such as ethylene glycol monoethyl ether acetate; an ester of ethyl lactate, methyl 3-methoxypropionate or ethyl 3-ethoxypropionate; A ketone or the like such as diacetone alcohol. These organic solvents can be used singly or in combination of two or more kinds. The amount of the organic solvent to be used can be appropriately selected in accordance with the specific use of the radiation-sensitive resin composition, the coating method, and the like. When the radiation sensitive resin composition is modulated, when the ruthenium material or the pigment is not added, the mixture can be stirred and mixed by only the usual method; in the case of adding the ruthenium material or the pigment, it is preferable to use a dissolver, a homomixer, and 3 A disperser such as a roll honing machine is dispersed and mixed. Further, after the preparation, the radiation-sensitive linear resin composition may be used after being passed through a screen, a membrane filter or the like. Method for producing dry film The dry film of the present invention is obtained by applying a radiation sensitive resin composition onto the surface of the base film and then drying the layer of the radiation sensitive resin composition. It can be manufactured by covering this layer. As shown in Fig. 1, the superior radiation-releasing dry film of the present invention has a thickness of the photosensitive resin composition layer 2 to 2 〇〇μιη laminated on the base film, and then is further covered by the film. Structure. In the formation of the coating film, for example, an applicator, a bar coater, a roll-42 - 200911523 type coater, a curtain coater, or the like is used. If the drying temperature is too low, the drying will take time; if it is too high, the heat shrinkage of the film or the vaporization of the radiation-sensitive resin composition will be suitable for the drying temperature in the range of 40 to 180 °C. More preferably 6 0~ °C. The film can be attached to the radiation-sensitive resin composition at room temperature, and can also be heated to about 40 to 60 ° C while also applying a microlens. The dry film of the present invention can be used for microlenses. Formation. The microlens of the present invention is mainly used for liquid crystal display elements such as various A-devices, liquid crystal televisions, telephones, projectors, etc., and can be suitably applied to single-chip (on-Chip color filter) such as a machine, an electronic copying machine, and a solid-state imaging device. An imaging optical system, an optical fiber connector, etc. The microlens is formed by the following steps (i) to (iv): (i) the radiation sensitive resin composition layer of the dry film of the present invention is applied to a glass substrate. a step of forming a coating film on a substrate. (ii) a step of irradiating radiation to at least a part of the coating film (referred to as "exposure j.") (iii) a step of developing the coating film after exposure. (iv) a step of heating the developed coating film (hereinafter referred to as "baking". Hereinafter, the steps will be described. - (i) Step 1 in this step 'According to the dry film process described above, Produced in a flexible base layer. -1 3 0 layer attached. Action Fax) Coloring: Under transfer, base layer -43 - 200911523 On the film, pre-coating and drying the radiation-sensitive resin composition for microlens formation Forming radiation A linear coating film (radiation-sensitive resin composition layer) is used after attaching the coating film to the substrate. In the case of using the obtained dry film, first, 'removing the coating film', for example, using a normal pressure heat roller Method, vacuum heat roll pressure bonding method, vacuum heat compression pressure bonding method, etc., applying appropriate heat and pressure, and transferring the dry film onto the substrate. The film thickness of the formed coating film is suitably about 3 to 50 μm, more preferably about 1 to 3 0 μm. The types of substrates that can be used include glass substrates, germanium wafers, and substrates on which various metal layers are formed on the surface. The method of applying the radiation-sensitive resin composition layer of the invention to the substrate is not limited to a method of attaching the substrate to the substrate after the dry film is formed, and examples thereof include a spin coating method, a spray method, a roll coating method, and a rod coating method. A suitable method such as a method, etc. - (ii) Step 1 In this step, at least a part of the formed coating film is exposed. When one of the coating films is exposed, the exposure is performed through a mask of a predetermined pattern. Exposure The ray is not particularly limited, and for example, an ultraviolet ray such as a g-line (wavelength of 4 3 6 nm) or an i-line (wavelength of 365 nm) may be selected depending on the type of the radiation-based polymerization initiator to be used, and the like; Far ultraviolet rays such as excimer lasers; charged particle lines such as synchrotron radiation, etc., etc. -44- 200911523 Among these radiations, ultraviolet rays are preferred, especially g lines and/or The radiation of the i-line is particularly desirable. Further, the exposure amount is preferably about 50 to 1 〇, 〇〇〇J/m2. In the step (i), when the dry film method is used, the base layer on the radiation-sensitive linear transfer layer is used. The film may be removed by peeling before the exposure step, or may be removed by peeling after the exposure step and before the development step. Step (iii) - In this step, the development of the exposed coating film is carried out by using a developing solution, preferably an alkali developing solution, to remove the unexposed portion to form a pattern having a predetermined shape. For example, the developing solution may be exemplified by sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate 'sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine. , triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[ 5. 4. 0]-7-undecene, 1,5-diazabicyclo[4_ 3. An aqueous solution of a basic compound such as 0]-5-pinene. A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous solution of the basic compound in an appropriate amount. Further, after development by an alkali developing solution, it is usually washed, for example, by washing with water or the like. Further, in the case of a radiation-sensitive resin composition which does not contain an insoluble component such as a pigment or a chelating material, various organic solvents constituting the composition can be used as a developing liquid. For example, the development method can be carried out by a liquid-filling method, a dipping method, a shaking impregnation method of -45 - 200911523, a showering method, or the like. Although the development time varies depending on the composition of the radiation-sensitive resin composition, it is usually about 30 to 300 seconds at normal temperature. In the case of the radiation sensitive resin composition used in the present invention, by setting the temperature of the developing liquid to about 30 to 35 ° C, a good pattern and a microlens can be formed even if the development time is shortened, based on the process. The aspect of shortening the time (tacttime) is advantageous. In the case of a conventional radiation-sensitive resin composition used for microlens formation, if the development time exceeds the optimum condition by about 20 to 25 seconds, the development time must be strictly controlled due to the occurrence of peeling in the formed pattern, and the present invention In the case of the radiation sensitive resin composition, even if the optimum development time exceeds the optimum development time by about 30 seconds, a favorable pattern can be formed, which is advantageous in terms of product yield. First (i v) Step 1 In this step, for example, a heating film using a hot plate, an oven or the like is used to bake the developed coating film, and the pattern is melted and hardened to obtain a lens shape. Although the baking conditions are also different depending on the kind or use ratio of each component constituting the radiation-sensitive resin composition, the desired pattern shape, the heating device, etc., for example, in the case of 1 50 to 2 4 At 0 °C, about 10 to 30 minutes; in the case of an oven, for example, at about 150 to 240 ° C, about 30 to 90 minutes. Further, in the case of baking, a step baking method in which two or more heat treatments are performed can be employed. Further, it is also possible to employ a post-exposure method in which the pattern obtained after development is exposed to -46 to 200911523 before or after baking. As described above, the radiation-sensitive resin composition used in the present invention can form a high-definition microlens and a microlens array having a high degree of resolution and excellent balance of storage stability and coating properties. Further, the microlens of the present invention has a superior film thickness, resolution 'pattern shape, transparency, heat resistance, heat discoloration resistance, solvent resistance and the like, and is particularly suitable for use in various OA machines, liquid crystal televisions, and the like. A liquid crystal display element such as a mobile phone or a projector. Further, according to the dry film production method and the microlens manufacturing method of the present invention, high-definition microlenses and microlens arrays having superior characteristics can be formed by a simple process using a radiation-sensitive dry film. [Examples] Hereinafter, the present invention will be described more specifically by way of examples and comparative examples, but the present invention is not limited by the following examples. Synthesis Example 1 After a nitrogen-substituted flask, 3 g of 2,2 '-azobisisobutyronitrile as a radical polymerization initiator and 100 g of methyl 3-methoxypropionate as a solvent were stirred until free. The base polymerization initiator is dissolved. Thereafter, 19 g of methacrylic acid, 15 g of 2-methyl(hexahydrohexyloxy)ethyl methacrylate, 15 g of styrene, and 46 g of tricyclodecyl methacrylate were fed, and stirring was started slowly. Add 5 g of isoprene. Thereafter, the temperature of the reaction solution was raised to 80 ° C, and polymerization was carried out at this temperature for 4 hours to obtain methacrylic acid/2-mono(hexahydrohexyloxy)ethyl ester/styrene/methacrylic acid three. Copolymer of cyclodecyl ester / isoprene (copolymerization weight ratio = -47 - 200911523 19/15/15/46/5, Mw = 13,000, Mn = 8,000). This copolymer was used as a copolymer (A 1 ). Synthesis Example 2 In the same manner as in Synthesis Example 1, methacrylic acid/styrene/benzyl methacrylate/mono(meth)acrylate/N-phenylmaleimide was copolymerized (copolymerization weight ratio = 15/15/35/10/25, Mw = 7,000, Mn = 4,000), the copolymer (A2) was obtained. The radiation-sensitive photoresist composition solution of the composition shown in Table 1 below was prepared. This solution was set to (S-1). [Table 1] (S-1) Doping amount of compound (A) * Copolymer (A1) 80 parts by weight of copolymer * Copolymer (A2) 20 parts by weight of (B) component • ARONIX M-402 20 weight Partially polymerizable unsaturated compound • ARONIX M-309 10 parts by weight • ARONIX M-113 30 parts by weight (C) • Oxidized-2,4,6-trimethylbenzhydryl 2 22 parts by weight photopolymerization start Phenylphosphine (trade name LUCIRIN TPO) • IRGACURE 651 12 parts by weight (D) • 2,4-diphenyl-4-methyl-1-pentene. 5 parts by weight of chain transfer agent Example 1 Preparation of dry film and peeling, transfer, and exposure of the film were performed as follows. -48 - 200911523 On a polyethylene terephthalate (PET) film, COSMOSHINE "A4100-50" (manufactured by Toyobo Co., Ltd.), an applicator was used to uniformly coat the radiation-sensitive resin composition of Table 1 (S). - 1), heating the coating film at 120 ° C for 8 minutes to form a radiation-sensitive resin composition layer having a thickness of 20 μm, from above, at room temperature, using a pressure-bonding method to make a radiation-sensitive resin composition The material layer and the self-adhesive resin layer are brought into contact with each other to form a film of a polyethylene film made of a self-adhesive resin layer, which is made of TORETEC 7721 (film Α, TORAY processing). Dry film. Next, the film was peeled off, and the surface of the radiation-sensitive resin composition layer was brought into contact with the surface of the glass substrate, and the radiation-sensitive dry film was transferred onto the glass substrate by a thermocompression bonding method. Next, a 5 second exposure of ultraviolet rays having a wavelength of 3 6 5 nm and an intensity of 200 W/m 2 was carried out on the obtained substrate through a mask of a predetermined pattern. Thereafter, the base film is removed from the radiation-sensitive dry film on the substrate at 25 ° C, via 0. A 3 wt% potassium hydroxide aqueous solution was developed for 2 minutes, and then washed with pure water for 1 minute to form a pattern to obtain a film thickness of 丨8. 7 μηι pattern film. Thereafter, the film was baked and cured by baking the film for 60 minutes in an oven at 150 ° C to form a microlens. The evaluation of the obtained microlens was carried out using the following methods. The results are shown in Table 7. - Evaluation of residual film rate - For the film thickness after development, the residual film rate exceeds 80%, and the evaluation is 〇; 7 〇% or more, less than 80%, the evaluation is △; below 70% The situation is evaluated as X. - Evaluation of resolution - -49 - 200911523 For the pattern-like film after development, the pattern of line/gap=1 〇μ m /1 0 μ m can be evaluated as 〇; line/gap = 2 0 ^ m The case where the pattern of / 2 0 ^ m can be solved is evaluated as Δ; the case where the pattern of the two cannot be solved is evaluated as X. - Evaluation of the shape of the lens - For the film of the microlens that has been formed after the post-baking, use a transmission electron microscope to observe the line/gap = 5 〇μΠΐ/5〇μηι or the pattern, and evaluate whether it conforms to the pattern of FIG. shape. The case where the hemispherical shape of (a) and the lens shape are good is 〇' is particularly preferable, and it is set as ◎. The case where the melting of (b) is insufficient, and the case where the lens shape is not reversed is set to Δ: if (c) is not completely melted, the shape is square. Example 2 A solution of the radiation-sensitive photoresist composition of the composition shown in Table 2 below was prepared. This solution was set to (S-2). According to Example 1, after (S - 2 ) was applied onto the base film, the film A was pressure-bonded to the radiation-sensitive resin composition layer, and dry film production, peeling, transfer, exposure, and development were performed. Pattern formation, heat treatment. The evaluation of the obtained microlens was carried out in the same manner as in Example 1, and the results are shown in Table 1. -50 - 200911523 [Table 2] (S-2) Blending amount of compound (A) * Copolymer (A1) 80 parts by weight of copolymer * Copolymer (A2) 20 parts by weight of component (B) ARONIX M -402 20 parts by weight of polymerizable unsaturated compound • ARONIX M-309 10 parts by weight • ARONIX M-113 30 parts by weight (C) • Oxidized-2,4,6-trimethylbenzhydryl 2 22 parts by weight Photopolymerization initiator phenylphosphine (trade name LUCIRIN TPO) ----- • IRGACURE 651 12 parts by weight of component (D) spring 2,4-phenyl-4-methyl-1-pentane 5 parts by weight Agent Example 3 A solution of the radiation-sensitive photoresist composition of the composition shown in Table 3 below was prepared. This solution was set to (S-3). According to Example 1, after (S-3) was applied onto the base film, the film A was pressure-bonded to the radiation-sensitive resin composition layer, and dry film production, peeling, transfer, exposure, and development were performed. Pattern formation, heat treatment. The same procedure as in Example 1 was carried out to evaluate the obtained microlens, and the results are shown in Table 200911523 [Table 3] (S-3) Doping composition (A) component * Copolymer (A1) 100 parts by weight of copolymer (B) Ingredients • ARONIX M-402 25 parts by weight of polymerizable unsaturated compound • ARONIX M-309 15 parts by weight • ARONIX M-113 20 parts by weight (C) • Oxidized-2,4,6-trimethylbenzene Methylidene 22 parts by weight photopolymerization initiator phenylphosphine (trade name LUCIRIN TPO) • IRGACURE 651 12 parts by weight (D) Ingredients ♦ 2,4-Benzyl-4-methyl-1-pentane 1 weight Part Chain Transfer Agent Example 4 A solution of the radiation sensitive photoresist composition of the composition shown in Table 4 below was prepared. This solution was set to (S-4). According to Example 1, after (S -4 ) was applied onto the base film, the film A was pressure-bonded to the radiation-sensitive resin composition layer. After dry film production, peeling, transfer, exposure, and development, Pattern formation, heat treatment. The same as in Example 1 to carry out the evaluation of the obtained microlens'. The results are shown in Table-52 - 200911523 [Table 4] (S-4) Doping composition (A) component * Copolymer (A1) 80 weight Copolymer* Copolymer (A2) 20 parts by weight of component (B) • ARONIX M-402 25 parts by weight of polymerizable unsaturated compound • ARONIX M-309 15 parts by weight • ARONIX M-113 20 parts by weight (C) • Oxidized-2,4,6-trimethylbenzimidyl 22 parts by weight photopolymerization initiator phenylphosphine (trade name LUCIRIN TPO) • IRGACURE 651 12 parts by weight (D) • 2,4-diphenyl 4-Methyl-1-pentene 10 parts by weight chain transfer agent Comparative Example 1 A solution of the radiation sensitive photoresist composition of the composition shown in Table 5 below was prepared. This solution was set to (S - 5 ). According to Example 1, after (S - 5 ) was applied onto the base film, the film A was pressure-bonded to the radiation-sensitive resin composition layer, and dry film production, peeling, transfer, exposure, and development were performed. Pattern formation, heat treatment. The evaluation of the obtained microlens was carried out in the same manner as in Example 1, and the results are shown in Table 1. 200911523 [Table 5] (S-5) Dosing amount of compound (A) * Copolymer (A1) 80 parts by weight of copolymer * Copolymer (A2) 20 parts by weight of component (B) ARONIX M-402 25 Parts by weight of polymerizable unsaturated compound • ARONIX M-309 15 parts by weight of ginseng ARONIX M-113 20 parts by weight of component (C) oxidized-2,4,6-trimethylbenzhydryl 2 22 parts by weight of photopolymerization Starting agent phenylphosphine (trade name: LUCIRIN TPO) • IRGACURE 651 12 parts by weight Comparative Example 2 A solution of the radiation sensitive photoresist composition of the composition shown in Table 6 below was prepared. This solution was set to (S-6). According to Example 1, after (S - 6 ) was applied onto the base film, the film A was pressure-bonded to the radiation-sensitive resin composition layer, and dry film production, peeling, transfer, exposure, and development were performed. Pattern formation, heat treatment. The evaluation was carried out in the same manner as in Example 1 to obtain the obtained microlens, and the results are shown in Table-54-200911523 [Table 6] (S-6) Doping composition (A) component * Copolymer (A1) 100 weight Copolymer (B) component • ARONIX M-8100 40 parts by weight of polymerizable unsaturated compound • ARONIX M-309 10 parts by weight (C) • Oxidized-2,4,6-trimethylbenzhydryl 2 Parts by weight photopolymerization initiator phenylphosphine (trade name: LUCIRIN TPO) • IRGACURE 651 12 parts by weight [Table 7] Residual film rate resolution lens shape Example 1 〇〇 ◎ Example 2 〇〇 ◎ Example 3 〇〇〇 Example 4 Δ 〇 ◎ Comparative Example 1 〇〇 Δ Comparative Example 2 〇〇 Δ [Brief Description of the Drawing] Fig. 1 is an explanatory view showing the layer structure of the radiation sensitive dry film of the present invention. Figure 2 is a schematic view showing the cross-sectional shape of the lens. [Component Symbol Description] 4E. -55 -