200923580 - 六、發明說明： 【發明所屬之技術領域】 . 本發明係有關含有在同一分子内具有複數巯基之多官 能性硫醇化合物的黑阻劑用感光性樹脂組成物，其為高感 度且在鹼性顯像時之細線圖案之線寬保持性優越妁黑阻劑 用感光性樹脂組成物。 【先前技術】 最近數年來’在彩色液晶顯不裝置（液晶電視、液晶監 ’ 視器、彩色液晶手機等）之所有領域中使用感光性組成物。 彩色液晶顯示裝置之構成要素為控制光透過量或反射量之 液晶部及濾色器。該濾色器的製造方法通常可使用例如在 玻璃、塑膠片等透明基板之表面形成黑矩陣，接著以條紋 狀或馬賽克狀等色圖案依序將紅、綠、藍之不同色相予以 形成之方法。圖案尺寸係依濾色器之用途或各種顏色而 異，但謀求紅、綠、藍之晝素從200至300 /zm變成100// m、黑矩陣從20 // m變成10 // m的細線化，因此，對感光性 樹脂組成物要求高的尺寸精確度。 圖案之形成係利用根據光反應性樹脂與光聚合引發劑 之反應之光硬化作用，水銀燈之線光譜之一的i線（365nm) 主要係作為用以使顏料分散系負型色阻劑硬化之曝光波長 而使用。紅、綠、藍及黑的感光性樹脂組成物係由於著色 材料本身會吸收紫外線且最近感光性樹脂組成物中之著色 材料之含有比例變多，故在曝光部，對於膜厚方向發生交 聯密度之差異，即使在塗膜表面充分光硬化，在基底部亦 4 320634 200923580 • 不易光硬化，而不易獲得顯像容限（development marg i η )、細線密著性、圖案邊緣形狀良好之濾色器。又， - 在未曝光部中，由於難溶於顯像液之顏料等著色材料係以 作為顯像殘渣而堆積在基板上，故在依序形成不同色相 時，導致背光之透過率降低，濾色器亮度降低。又，由於 塗膜與基板之間之密著性降低，有導致顯像容限或細線密 著性降低之慮。然後，該等問題尤其是在感光性樹脂組成 物之分光特性上、形成黑矩陣之遮光感光性樹脂組成物中 為特別顯著。 近年來，在濾色器之生產線上為了提昇生產性效率、 降低成本，母玻璃基板有逐年大型化之傾向，亦進行製造 超過lmxlm之母玻璃基板。又，為了降低產距時間（takt t i me)並提昇生產性效率，在曝光步驟中要求曝光時間短， 亦即要求用低曝光量進行光硬化之濾色器用感光性樹脂組 成物。如此，要求將著色材料之含有比例多、光硬化困難 之濾色器用感光性樹脂組成物在寬廣之顯像容限中以低曝 光量獲得圖案尺寸安定性、圖案密著性、圖案邊緣形狀之 銳利性良好的圖案，因此，感光性樹脂組成物之高感度化 是不可欠缺的。 根據該等狀況，對於濾色器用之感光性樹脂組成物要 求可用更低之能量進行硬化、更早硬化、形成更精細之圖 案者。惟，根據滤色器用之感光性樹脂組成物中所使用之 顏料種類，在光聚合引發，不能獲得充分之能量。尤其是 在黑矩陣要求高光學濃度之樹脂黑矩陣，感光性樹脂組成 5 320634 200923580 物中之碳黑等著色材料之含量變高，有不能獲得充分感度 之問題。對於該等問題，雖然有更大能量之照射或添加過 量之光聚合引發劑、設置氧遮斷膜以予以回避等種種方 法，但在節省能量、降低生產成本上並不妥當，要求感光 性更優越之組成物。 為了改良感光性樹脂組成物之感度，至今已提案有使 用在同一分子内具有複數巯基之多官能性硫醇化合物。 惟，至今已提案之使用多官能性硫醇化合物者有保存安定 性差之缺點。例如，關於在適用於形成黑矩陣之濾色器用 之光聚合性組成物中使用多官能性硫醇化合物，在專利文 獻1揭示含有多官能性硫醇之光聚合性組成物，惟，使用 多官能性硫醇，在高遮光下（CB濃度52%以上）若欲經由多 官能性硫醇達成高感度化，則有犧牲保存安定性之問題且 未達到在未使用增感劑下之高感度化。因此，要求開發在 高遮光下，為高感度·顯像性優越且保存.安定性優越之濾 色器用黑矩陣阻劑及該等中使用之感光性組成物。 [專利文獻1]日本特開2004-325733號公報 【發明内容】 [發明欲解決之課題] 因此，本發明之目的為提供即使在高遮光領域，亦為 高感度、良好圖案密著性且保存安定性寬廣之黑阻劑用感 光性樹脂組成物。又，本發明之另一目的為提供使用該濾 色器用感光性樹脂組成物而形成之濾色器用黑矩陣及濾色 器。 6 320634 200923580 . [解決課題之方法] 本發明人等為了解決上述課題進行研究之結果發現， . 只要依據以併用光聚合引發劑並調配特定硫醇化合物而成 之感光性樹脂組成物，即可解決上述之問題，因而完成本 發明。 亦即’本發明係提供一種黑阻劑用感光性樹脂組成 物，其含有下述（A)至（E)成分作為必須成分： (A) 鹼可溶性樹脂、 (B) 至少具有1個以上乙烯性不飽和鍵之光聚合性單體、 (C) 光聚合引發劑、 (D) 下述通式（I)表示之多官能性硫醇化合物200923580 - 6. Description of the Invention: [Technical Field of the Invention] The present invention relates to a photosensitive resin composition for a black resist containing a polyfunctional thiol compound having a complex fluorenyl group in the same molecule, which is high in sensitivity and The line width of the fine line pattern at the time of alkaline development is excellent, and the photosensitive resin composition for the black resist is excellent. [Prior Art] In recent years, photosensitive compositions have been used in all fields of color liquid crystal display devices (liquid crystal televisions, liquid crystal monitors, color liquid crystal mobile phones, etc.). The constituent elements of the color liquid crystal display device are a liquid crystal portion and a color filter that control the amount of light transmitted or reflected. In the method of manufacturing the color filter, for example, a black matrix is formed on the surface of a transparent substrate such as glass or a plastic sheet, and then different color phases of red, green, and blue are sequentially formed in a stripe or mosaic color pattern. . The size of the pattern varies depending on the purpose of the color filter or the color, but the red, green, and blue elements are changed from 200 to 300 /zm to 100//m, and the black matrix is changed from 20 // m to 10 // m. Thinning, therefore, requires high dimensional accuracy for the photosensitive resin composition. The pattern is formed by photohardening according to the reaction of the photoreactive resin and the photopolymerization initiator, and the i-line (365 nm) of one of the line spectra of the mercury lamp is mainly used as a hardening agent for the pigment dispersion negative color resist. Use at the exposure wavelength. In the photosensitive resin composition of red, green, blue, and black, since the coloring material itself absorbs ultraviolet rays and the content ratio of the coloring material in the photosensitive resin composition increases recently, cross-linking occurs in the film thickness direction in the exposed portion. The difference in density, even if the surface of the coating film is sufficiently light-hardened, it is also in the base portion. 4 320634 200923580 • It is not easy to be photohardened, and it is not easy to obtain development margin (development marg i η ), fine line adhesion, and good pattern edge shape. Color. Further, in the unexposed portion, a coloring material such as a pigment which is hardly soluble in the developing liquid is deposited on the substrate as a development residue, so that when the different hue is formed in sequence, the transmittance of the backlight is lowered, and the filter is lowered. The brightness of the colorizer is reduced. Further, since the adhesion between the coating film and the substrate is lowered, the development tolerance or the fineness of the fine line may be lowered. Then, these problems are particularly remarkable in the light-shielding photosensitive resin composition which forms a black matrix in the spectral characteristics of the photosensitive resin composition. In recent years, in order to increase productivity and reduce costs in the color filter production line, the mother glass substrate has been increasing in size year by year, and a mother glass substrate exceeding lmxlm has also been manufactured. Further, in order to reduce the production time and increase the productivity, the exposure time is required to be short in the exposure step, that is, a photosensitive resin composition for a color filter which is photocured with a low exposure amount is required. In this manner, it is required to obtain a pattern size stability, a pattern adhesion, and a pattern edge shape with a low exposure amount in a broad imaging tolerance in which a photosensitive resin composition for a color filter having a large content ratio of a coloring material and difficulty in photohardening is obtained. A sharp pattern is excellent, and therefore, the high sensitivity of the photosensitive resin composition is indispensable. According to these conditions, the photosensitive resin composition for a color filter is required to be hardened with a lower energy, hardened earlier, and formed into a finer pattern. However, depending on the kind of the pigment used in the photosensitive resin composition for the color filter, sufficient energy cannot be obtained by photopolymerization. In particular, in the case where a black matrix requires a resin black matrix having a high optical density, the content of a coloring material such as carbon black in the photosensitive resin composition 5 320634 200923580 becomes high, and there is a problem that sufficient sensitivity cannot be obtained. For these problems, although there are various methods such as irradiation with greater energy or addition of an excessive amount of photopolymerization initiator and provision of an oxygen barrier film to avoid it, it is not appropriate to save energy and reduce production cost, and it is required to have more photosensitivity. Superior composition. In order to improve the sensitivity of the photosensitive resin composition, a polyfunctional thiol compound having a complex fluorenyl group in the same molecule has been proposed so far. However, the use of polyfunctional thiol compounds which have been proposed so far has the disadvantage of poor preservation stability. For example, a polyfunctional thiol compound is used for a photopolymerizable composition for a color filter which is suitable for forming a black matrix, and Patent Document 1 discloses a photopolymerizable composition containing a polyfunctional thiol, but it is used in many cases. Functional thiol, under high light shielding (CB concentration of 52% or more), if high sensitivity is desired via polyfunctional thiol, there is a problem of sacrificing preservation stability and failing to achieve high sensitivity without sensitizer Chemical. For this reason, it is required to develop a black matrix resist for a color filter which is excellent in high sensitivity and development, and which has excellent storage stability and stability under high light shielding, and a photosensitive composition used in the above. [Problem to be Solved by the Invention] Therefore, an object of the present invention is to provide high sensitivity, good pattern adhesion, and preservation even in the field of high light shielding. A photosensitive resin composition for a black stabilizer having a wide stability. Further, another object of the present invention is to provide a black matrix for a color filter and a color filter which are formed using the photosensitive resin composition for a color filter. 6 320634 200923580 . [Means for Solving the Problems] As a result of the investigation of the above-mentioned problems, the present inventors have found that a photosensitive resin composition obtained by mixing a specific thiol compound in combination with a photopolymerization initiator can be used. The above problems are solved, and thus the present invention has been completed. In other words, the present invention provides a photosensitive resin composition for a black resist which contains the following components (A) to (E) as essential components: (A) an alkali-soluble resin, and (B) at least one or more ethylene. A photopolymerizable monomer having an unsaturated bond, (C) a photopolymerization initiator, (D) a polyfunctional thiol compound represented by the following formula (I)
(式中’ R1表示炫基’ R2表示可含有碳原子以外之原子之η 價脂肪族基’ R不為氲原子而為烧基，η表示2至4)、及 (Ε)選自黑色有機顏料、混色有機顏料及遮光材料之1種以 上之著色材料； 其中，（Α)成分與（Β)成分之重量比（Α/Β)為60/40 至90/10，相對於（Α)成分與（Β)成分之合計100重量份， 含有（C)成分5至50重量份。 另外，本發明係提供一種濾色器用黑矩陣，其係藉由 在透明基板上塗抹上述黑阻劑用感光性樹脂組成物，在乾 燥後，歷經下述（a)至（c)各步驟而獲得者：（a)經由紫外線 7 320634 200923580 曝光裝置進行曝光、（b)經由鹼性水溶液進行顯像及（c)熱 鍛燒。 再者，本發明係提供具有上述黑矩陣之濾色器。 以下，對於本發明之黑阻劑用感光性樹脂組成物（以 下，有時亦簡稱為「感光性樹脂組成物」或「組成物」） 加以詳細說明。本發明之組成物含有上述（A)至（E)成分作 為必需成分。 (A)成分之鹼可溶性樹脂之理想例，只要是可進行鹼性 顯像且具有塗膜形成能力之高分子化合物即可，並無特別 限制，具體例可列舉如下之化合物。可例示如：1)聚乙烯、 聚丙烯、聚異丁烯等聚烯烴系聚合物、2)聚丁二烯、聚異 戊二烯等二烯系聚合物、3)聚乙炔系聚合物、聚伸苯基系 聚合物等具有共軛聚烯構造之聚合物、4)聚氯乙烯、聚苯 乙烯、聚乙酸乙烯i旨、聚乙婦醇、聚丙稀酸、聚丙稀酸醋、 聚丙烯醯胺、聚丙烯腈、聚乙烯基酚等乙烯聚合物、5)聚 苯醚、聚環氧乙烧（polyoxirane)、聚氧雜環丁燒 (polyoxetane)、聚四氫π夫喃、聚醚酮、聚醚驗酮、聚縮醒· 等聚醚、6)驗搭清漆樹脂（novolac resin)、曱階盼•樹脂 (reso 1 resiη)等紛樹脂、7)聚對苯二曱酸乙二醋、聚紛酉太 對苯二曱酸酯（polyphenol phthalein terephthalate)、 聚碳酸酯、醇酸樹脂、不飽和聚酯樹脂等聚酯、8)尼龍-6、 尼龍66、水溶性尼龍、聚苯醯胺等聚醯胺、9)明膠、酪蛋 白等多肽、10)驗醒:清漆環氧樹脂、雙驗環氧樹脂、紛搭清 漆環氧丙烯酸酯及經酸酐改性之改性樹脂等環氧樹脂及其 8 320634 200923580 -改性物、U)聚胺基甲酸酯（polyure^thane)、聚醯亞胺、三 聚氰胺樹脂、尿素樹脂、聚咪唑、聚卩萼唑、聚π比唑、聚笨 . 胺、多硫化物（P〇lysulfide)、聚颯、纖維素類等。 - 該等樹脂中，以在樹脂側鏈或主鏈具有羧基或酚性羥 . 基等者為較佳。又以具有羧基之樹脂，例如丙烯酸（共）聚 ’物、苯乙烯/馬來酸酐樹脂、酚醛清漆環氧丙烯酸酯之酸 酐改性樹脂等，由於具有高鹼性顯像性，故較佳。更進— π 步，丙烯酸系樹脂係由於顯像性優越故較佳，其共聚物係 由於可選擇各種單體而聚合，故從性能及製造控制之觀點 而言更佳。 更具體而言，含有羧基之丙烯酸系樹脂可列舉如：藉 由使（甲基）丙稀酸、馬來酸（酐）、巴豆酸、衣康酸、富馬 酉文專具有羧基之單體與苯乙烯、α—甲基苯乙烯、（甲基） 丙烯酸甲酯、（甲基）丙稀酸乙酯、（甲基）丙烯酸丙酯、（甲 基）丙稀酸異丙酯、（甲基）丙烯酸丁酯、乙酸乙烯酯、丙烯 L 腈、（甲基）丙烯醯胺、（甲基）丙烯酸縮水甘油酷、烯丙基 縮水甘油基醚、乙基丙烯酸縮水甘油酯、巴豆酸縮水甘油 基醚、（甲基）丙烯醯氯、（甲基）丙烯酸苯曱酯、（甲基）丙 烯酸羥乙酯、Ν-羥甲基丙烯醯胺、ν，Ν-二曱基丙烯醯胺、 Ν-甲基丙烯醯基嗎啉、（甲基）丙稀酸Ν，Ν_二甲基胺基乙 酯、Ν，Ν-二甲基胺基乙基丙烯醯胺等共聚單體（c〇m〇rK)mer) 進行共聚而成之聚合物。其中，較好為由至少含有（甲基） 丙稀酸或（甲基）丙烯酸烷基醚作為構成單體而成之丙烯酸 系樹酯’更好為含有（甲基）丙烯酸及苯乙烯之丙烯酸系樹 320634 9 200923580 脂0 該等具錢基之_酸錢财，亦可在樹脂侧鍵附 加乙烯性雙鍵。由於在樹脂側鏈賦予雙鍵而提高光硬化 性，故可更加提昇解像性、密著性，而較佳。 該等具有羧基之丙烯酸系樹脂之用GPC測定之重量平 均分子量較好之範圍為1000至100000，若超出此範圍， 則有顯像性降低之傾向。又’羧基較好之含量範圍係酸價 為5至200。酸價若在5以下，則不溶於鹼性顯像液，又， 若超過2000 ’則感度降低。 上述（A)成分之鹼可溶性樹脂中，較適用者係具有苐骨 架之環氧丙烯酸酯之酸酐縮聚物之丙二醇一甲基輕乙酸醋 溶液。 (B)成分之具有至少1個以上乙烯性不飽和鍵之光聚 合性單體，可使用經由光聚合引發劑所產生之自由基之作 用而進行自由基聚合之單體、及經由光聚合引發劑所產生 之酸之作用而進行加成縮合之單體等公知之任何一種單 體。前者之代表例可列舉如具有乙烯性雙鍵之單體。具體 而言，可列舉丙烯酸異丁酯、丙烯酸第三丁酯、丙烯酸月 桂酉曰、丙:酸録壤醋、丙細酸硬月旨g旨、丙烯酸環己醋、丙 細酸異冰片酯、丙稀酸苯甲酉旨,、丙稀酸2 __甲氧基乙醋、丙 烯酸3-甲氧基丁酯、乙基卡必醇丙烯酸酯、丙烯酸苯氧基 乙酯、丙烯酸四氫呋喃酯、苯氧基聚乙二醇丙烯酸酯、曱 氧基丙二醇丙烯酸酯、丙烯酸2-羥基乙酯、丙烯酸2_羥基 丙酯、氫鄰苯二曱酸2-丙烯醯氧基乙酯、氫鄰苯二甲酸2一 320634 10 200923580 丙烯酿氧基丙酯、四氫鄰苯二甲酸2一丙婦酿氧基丙醋、甲 基丙烯酸N-嗎《乙§旨、丙烯酸三氟乙自旨、甲基丙婦酸三 氣乙醋、（曱基）丙婦酸四說丙酿、（甲基）丙稀酸六敷丙醋、 (曱基）丙稀酸八氟戊S旨、丙稀酸十七敗月桂醋、甲基丙稀 酸二甲基矽烷氧基乙酯、U—丁二醇二丙烯酸酯、[6-己 二醇二丙婦酸酯、壬二醇二丙稀酸醋、新戊二醇二丙 烯酸酯、四乙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、丙 二醇二丙烯酸酯、丙三醇甲基丙烯酸酯丙烯酸酯、雙酚A 環氧乙烷加成物二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、 季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、三羥甲基丙 院環氧乙烧加成物三丙烯酸酯、丙三醇環氧丙烷加成物三 丙烯酸醋、伽三丙朗氧基乙g|、二季戊四醇六丙稀酸 酉曰、酚醛清漆環氧之丙烯酸改性物、酚醛清漆環氧之丙烯 酸及酸酐之改性物、N-乙烯基咣咯烷酮、N_乙烯基己内醯 胺、丙烯醯基化之異氰酸酯、二季戊四醇一羥基五丙烯酸 酯、胺基甲酸酯丙烯酸酯、不飽和聚酯丙烯酸酯等，該等 化合物可使用1種或2種以上。 該等單體中，關於丙烯酸系單體、尤其是具有3個以 上雙鍵之丙烯酸系單體，從提高光感度而言，以三羥甲基 丙烷三（甲基）丙稀酸酯、季戊四醇四（甲基）丙烯酸酯、二 季戊四醇六（甲基）丙烯酸酯等聚（曱基）丙烯酸酯更佳。該 等單體可單獨使用，亦可複數組合使用。 本發明之感光性樹脂組成物中，相對於（A)成分與（B) 成分合計100重量份’（B)成分係在1〇至4〇重量份之範圍 320634 11 200923580 中使用。⑻成分未滿Η)重量份時，在本發明之感光 脂組成物中占有之纽應性官能基之比例少，導致 不足，所形成之圖案會比目標之線寬細，圖案容易脫落二 另-方面，超過40重量份時，相對地，光感度太強，圖案 線寬對於®案遮罩成為太粗之形態，對於遮罩不能再現中、 實的線寬’又’由於顯像性變差，有㈣邊緣為鑛齒狀= 不能成為銳利狀的問題之慮。 (C)成分之光聚合引發劑雖是使用至少丨種光聚合引 發劑’惟’只要是可使具有乙烯性不飽和鍵且可加成聚合 之化合物開始聚合之化合物即可’並無特別限制。可列舉 例如苯乙酮（acetophenone)系化合物、三啡系化合物、苯 偶因系化合物、二苯甲酮系化合物、噻噸酮（th i 〇xan让〇狀） 系化合物、咪σ坐系化合物、醯基辟（acyl 〇xime)系化合物 等。 其中，苯乙酮系化合物可列舉例如二乙氧基苯乙酮、 2-羥基-2-甲基-1-苯基丙烷-1一酮、苯曱基二曱基縮酮、2_ 羥基-2-曱基-l-[4-(2-羥基乙氧基）苯基]丙烷一卜酮、卜 羥基環己基苯基酮、2-甲基-2-(N-嗎啉基）-1-(4-甲基硫苯 基）丙烷-1-酮、2-苯曱基-2-二曱胺基—1-(4-(N-嗎啉基） 苯基）丁烷-1-酮、2-羥基-2-曱基— 曱基乙烯基） 苯基]丙烷-1-酮之低聚物等。 三口井系化合物可列舉例如2, 4, 6-三（三氯曱基）-1，3， 5-三畊、2-曱基-4, 6-雙（三氯曱基）-1，3, 5-三畊、2-苯基 -4, 6-雙（三氯甲基）-1，3, 5-三畊、2-(4-氯苯基）-4, 6-雙 12 320634 200923580 (三氯甲基）-1，3, 5-三哄、2-(4-曱氧基苯基）—4, 6-雙（三氣 甲基）-1，3,5-三啡、2-(4-曱氧基萘基）_4,6一雙（三氯甲 基）_1，3,5-三畊、2-(4-甲氧基苯乙烯基）_4,6_雙（三氯甲 基）-1，3,5-三畊、2-(3,4,5-三曱氧基苯乙烯基）_4,6_雙 (三氯甲基）-1，3, 5-三畊、2-(4-甲硫基苯乙烯基）一4, 6_雙 (三氯甲基）-1，3’5-三啡、2-(向日葵基）一4,6_雙（三氣甲 基）-1，3,5-三畊等。 苯偶因系化合物可列舉例如苯偶因、苯偶因曱基醚、 苯偶因乙基醚、苯偶因異丙基醚、苯偶因異丁基醚等。 二苯甲酮系化合物可列舉例如二苯甲酮、^ _苯甲酿基 苯曱酸甲酯、4-苯基二苯曱酮、4__苯曱醯基_4，_曱基二苯 硫醚、3’3’，4,4’ -四（第三丁基過氧羰基)二苯甲酮、 2, 4, 6-三曱基二苯甲酮等。 噻細系化合物可列舉例如2-異丙基例酉同、4—里丙 基噻個、2’ 4-二乙基嗟噸酮、2, 4_二氯。塞噸酮、： 丙氧基噻噸酮等。' 鍋化合物可列舉例如2_(鄰'氯苯基Η ㈣2聚物、2普氯苯基）H卜甲氧’跡 2:㈣ 苯她2聚物、2,4,5-三芳基. 醞基朽糸化合物可列舉例如Η9_乙基一6— I釀基Η Η，♦坐I基]-二環庚基+ _ + = 酉曰、1普乙基+ 基苯甲酿基）H沐3其 320634 13 200923580 金剛烷基曱烷-1-酮肟一 〇—苯甲酸酯、1-[9 一乙基_6_(2_曱 基苯曱醯基)-9’ Η’ -咔唑一基]_金剛烷基曱烷_卜酮肟 -0-乙酸酯、1-[9-乙基_6_(2_甲基苯曱醯基）_9，Η，_咔唑 -3-基]-四氫呋喃基甲烷酮肟苯甲酸酯、丨_[9_乙基 -6-(2-甲基苯甲酿基）_9，Η，_Π卡唑_3_基卜四氫吱喃基甲 烷-1-酮肟-0-乙酸酯、丨一^—乙基—6_(2_甲基苯曱醯 基）-9，Η’-咔唑-3-基]一硫苯基甲烷酮肟一〇_苯曱酸 酯、1-[9-乙基-6 -（2-曱基苯曱醯基）_9,Η，_咔唑_3_基]_ 硫苯基曱烷-1-酮肟乙酸酯、一乙基_6_(2_曱基苯 曱醯基）-9, Η，-咔唑—3-基]-嗎啉基甲烷4 —酮肟一〇一苯曱 酸酯、1-[9-乙基-6-(2-甲基苯甲醯基）_9，Η，_咔唑_3_ 基]-嗎啉基甲烷-1-酮肟_〇_乙酸酯、Μ9-乙基_6_(2_曱 基苯曱醯基）-9, Η，-咔唑-3—基]_乙烷_丨-酮肟_〇_二環庚 烷羧酸酯、1-[9-乙基-6-(2-甲基苯.曱醯基）_9，Η，_咔唑 -3-基]-乙烷-1-酮肟_〇—三環癸烷羧酸酯、Μ9_乙基 -6-(2-曱基苯甲醯基）_9，Η，_咔唑_3_基]_乙烷_丨_酮肟 -0-金剛烷羧酸酯、1，2-辛二烯苯基硫）_2_⑺一苯 曱醯基两）](汽巴專業化學公司製造，製品名：Iragacure OXE01)、乙酮l-[9-乙基_6_(2_甲基苯甲醯基）_9H_咔唑 -3-基]-1-(0-乙醯基肟）（汽巴專業化學公司製造，製品 名：Irgacure OXE02)等。 (C)成分之光聚合引發劑亦可使用活性自由基產生劑 或酸產生劑。活性自由基產生劑可使用例如2,4,6_三曱基 苯甲醯基二苯基氧化膦、2,2，_雙（鄰_氯苯基)_4,4，， 14 320634 200923580 -5’5’ —四苯基— I，2，-聯咪唑、l〇-丁基—2-氯吖啶酮、2_ 乙基.惠醌、聯苯甲醯（benzil)、9, 10-菲醌、樟腦醌、苯基 ^乙醛酸甲酯、二茂鈦化合物等。酸產生劑可列舉例如對甲 ,苯磺酸4-羥基苯基二甲基毓鹽、六氟銻酸4_羥基苯基二甲 基毓鹽、對甲苯磺酸4-乙醯氧基苯基二甲基毓鹽、六氟銻 ’酸4-乙醯氧基苯基·甲基.苯甲基毓鹽、對甲苯磺酸三笨 基毓鹽、六氟锑酸三苯基銃鹽、對曱苯磺酸二苯基鎭鹽、 ,六氟銻酸二苯基錤鹽等鏽鹽類或硝基苯甲基曱苯磺酸鹽 類、苯偶因甲苯磺酸鹽類等。又，就活性自由基產生劑而 言，在上述之化合物中亦有同時產生活性自由基及酸之化 合物，例如三畊系化合物亦可作為酸產生劑使用。 (c)成分之光聚合引發劑可單獨使用，亦可混合2種以 上使用。其本身雖不作為光聚合引發劑或後述之增感劑作 用，但經由與上述.(c)成分之光聚合引發劑組合使用，即亦 可另外添加增大光聚合引發劑或增感劑能力之化合物。該 L等化合物可列舉例如若與二苯曱酮組合使用則具有效果之 胺系化合物。 該胺系化合物可列舉例如三乙醇胺、甲基二乙醇胺、 一異丙醇胺、4-二甲.胺基苯甲酸曱酯、4_二甲胺基苯曱酸 乙酯、4-二甲胺基苯甲酸異戊酯、苯甲酸2—二曱胺基乙 酉曰、4-二曱胺基苯甲酸2_乙基己酯、N,N_二甲基對曱苯 私4, 4雙（一曱胺基）二苯甲酮、4, 4’ -雙（二乙胺基） 二苯甲酮、4, 4’ -雙（乙基甲胺基）二苯曱嗣等。 上述（C)成分之光聚合引發劑中，較適用者係經導入三 320634 15 200923580 -氣甲基之三畊系光聚合引發劑、醯基肟系光聚合引發劑。 (c)成分光聚合引發劑之使用量’以作為樹脂成分之（a) 及（B)各成分之合計1〇〇重量份為基準，為5至5〇重量份， 較好為20至45重量份。（〇成分之調配比例若未滿5重量 份，則光聚合之速度變慢，感度降低，另一方面，若超過 50重置份，則感度變太強，圖案線寬相對於圖案遮罩成為 太粗之形態，相對於遮罩不能再現忠實的線寬，又，有圖 案邊緣成為鋸齒狀而不能成為銳利狀的問題之慮。 亦可在（C)成分之光聚合引發劑之外，另外調配增感 劑。增感劑可使用通常在光聚合引發劑中所使用之一般之 增感劑，為了更加提昇感度，較好係使用至少一種以上選 自一苯甲酮系化合物、噻噸酮系化合物及香豆素酮 (ketocoumar i η)系化合物所成組群中之化合物。 具體而言，可使用二苯甲酮、2, 4, 6一三甲基二苯甲酮、 4-苯基二苯曱酮、4-苯甲醯基一4，_曱基二苯硫醚、4,4，_ 雙（二甲胺基）二苯甲酮、4, 4，-雙（二乙胺基）二苯甲酮等 二苯甲酮系化合物；噻噸酮、二曱基噻噸酮、2,4_二甲基 噻噸酮、2, 4-二乙基噻噸酮、異丙基噻噸酮、2, 4—二異丙 基噻噸酮、2-氯噻噸酮等噻噸酮系化合物；3_乙醯基香豆 素、3-乙醯基-7-二乙胺基香豆素、3_苯曱醯基香豆素、3__ 苯甲醯基-7-二乙胺基香豆素、3_苯曱醯基_7_甲氧基香豆 素、3,3’ _羰基雙香豆素、3,3，_羰基雙（7_甲氧基香豆 素）、3, 3’ -羰基雙（5, 7-二曱氧基香豆素）等香豆素酮系化 合物。該等可使用1種或將2種以上混合使用。 16 320634 200923580 別限:對丄二增感劑之調配比例並無特 早乂灯你具在先聚合引發劑與增感劍之細 至40質量％，更好為1〇至 二里中為5 :太少，則感度降低，若太多二 == 本發明（D)成分之多宫能性硫醇化合物為在同—分子 内具有2個以上巯基（Si})者，可用下述通式（〗）表示：(wherein R1 represents a leuco group R2 represents an η-valent aliphatic group which may contain an atom other than a carbon atom, R is not a halogen atom, is a burnt group, η represents 2 to 4), and (Ε) is selected from a black organic group. One or more coloring materials of a pigment, a mixed color organic pigment, and a light-shielding material; wherein the weight ratio (Α/Β) of the (Α) component to the (Β) component is 60/40 to 90/10, relative to the (Α) component 100 parts by weight in total of the (Β) component, and 5 to 50 parts by weight of the component (C). Further, the present invention provides a black matrix for a color filter which is coated with a photosensitive resin composition for a black resist on a transparent substrate, and after drying, passes through the following steps (a) to (c). Obtained: (a) exposed by ultraviolet light 7 320634 200923580 exposure apparatus, (b) developed via an aqueous alkaline solution, and (c) hot calcined. Furthermore, the present invention provides a color filter having the above black matrix. In the following, the photosensitive resin composition for a black resist of the present invention (hereinafter, simply referred to as "photosensitive resin composition" or "composition") will be described in detail. The composition of the present invention contains the above components (A) to (E) as essential components. The polymer compound which can be subjected to alkaline development and has a coating film forming ability is not particularly limited as long as it is a compound of the alkali-soluble resin of the component (A), and specific examples thereof include the following compounds. For example, 1) a polyolefin-based polymer such as polyethylene, polypropylene or polyisobutylene; 2) a diene polymer such as polybutadiene or polyisoprene; 3) a polyacetylene polymer; a polymer having a conjugated polyene structure such as a phenyl polymer, 4) polyvinyl chloride, polystyrene, polyvinyl acetate, polyglycol, polyacrylic acid, polyacrylic acid vinegar, polypropylene decylamine , polyacrylonitrile, polyvinyl phenol and other ethylene polymers, 5) polyphenylene ether, polyoxirane (polyoxirane), polyoxetane (polyoxetane), polytetrahydropyrene, polyether ketone, Polyether ketone, poly-shrinking, etc., 6) varnish resin (novolac resin), 曱 盼 • resin (reso 1 resiη) and other resins, 7) poly-terephthalic acid ethane vinegar, Polyphenol phthalein terephthalate, polycarbonate, alkyd resin, unsaturated polyester resin, etc., 8) nylon-6, nylon 66, water-soluble nylon, polyphenylamine, etc. Polyamide, 9) gelatin, casein and other peptides, 10) wake up: varnish epoxy resin, double test epoxy resin, varnish epoxy acrylic Epoxy resin such as modified resin modified by acid anhydride and its 8 320634 200923580 - modified product, U) polyureate (polyure^thane), polyimine, melamine resin, urea resin, polyimidazole , polycarbazole, polypyridazole, polystyrene, amine, polysulfide (P〇lysulfide), polyfluorene, cellulose, and the like. - Among these resins, those having a carboxyl group or a phenolic hydroxyl group in the side chain or main chain of the resin are preferred. Further, a resin having a carboxyl group, for example, an acrylic (co)polymer, a styrene/maleic anhydride resin, a novolak epoxy acrylate-modified resin, or the like is preferred because it has high alkali developability. Further, in the π step, the acrylic resin is preferred because of its excellent developing property, and the copolymer is polymerized by selecting various monomers, so that it is more preferable from the viewpoint of performance and manufacturing control. More specifically, the acrylic resin containing a carboxyl group may, for example, be a monomer having a carboxyl group by using (meth)acrylic acid, maleic acid (anhydride), crotonic acid, itaconic acid, fumarine, and benzene. Ethylene, α-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, (methyl) Butyl acrylate, vinyl acetate, propylene L nitrile, (meth) acrylamide, glycidol (meth) acrylate, allyl glycidyl ether, glycidyl ethacrylate, glycidyl glycoether , (meth) acrylonitrile, phenyl methacrylate, hydroxyethyl (meth) acrylate, hydrazine-hydroxymethyl acrylamide, ν, Ν-dimercapto acrylamide, Ν-甲Co-monomers such as acryloylmorpholine, (meth)acrylic acid hydride, hydrazine-dimethylaminoethyl ester, hydrazine, hydrazine-dimethylaminoethyl acrylamide (c〇m〇rK ) mer) a polymer obtained by copolymerization. Among them, an acrylic resin which is preferably composed of at least (meth)acrylic acid or alkyl (meth)acrylate as a constituent monomer is more preferably an acrylic acid containing (meth)acrylic acid and styrene. Ties tree 320634 9 200923580 Grease 0 These are the money-based _ acid money, you can also add vinyl double bonds on the resin side bond. Since the double bond is imparted to the side chain of the resin to improve the photocurability, the resolution and the adhesion can be further improved, and it is preferable. The weight average molecular weight of the carboxyl group-containing acrylic resin measured by GPC is preferably in the range of 1,000 to 100,000. If it exceeds this range, the development property tends to be lowered. Further, the preferred range of the carboxyl group is in the range of 5 to 200. When the acid value is 5 or less, it is insoluble in the alkaline developing solution, and if it exceeds 2000 Å, the sensitivity is lowered. Among the alkali-soluble resins of the above component (A), a propylene glycol monomethyl vinegar acetate solution having an epoxy acrylate polycondensate of a ruthenium frame is preferred. The photopolymerizable monomer having at least one or more ethylenically unsaturated bonds of the component (B) can be subjected to radical polymerization using a radical generated by a photopolymerization initiator, and can be induced by photopolymerization. Any known monomer such as a monomer which is subjected to addition condensation by the action of an acid generated by the agent. Representative examples of the former include monomers having an ethylenic double bond. Specific examples thereof include isobutyl acrylate, tributyl acrylate, lauric acid acrylate, acrylic acid, chlorinated vinegar, acrylic acid, hexyl acrylate, and isobornyl acrylate. Benzo benzoic acid, 2, methoxyacetic acid, 3-methoxybutyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, tetrahydrofuran acrylate, benzene Oxypolyethylene glycol acrylate, decyloxypropylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-propenyloxyethyl hydrogen phthalate, hydrogen phthalic acid 2320634 10 200923580 Propylene oxypropyl ester, tetrahydrophthalic acid 2 propylene fondant oxypropyl vinegar, methacrylic acid N-? "B § purpose, acrylic trifluoroethylene from the purpose, methyl propyl women Acid three-gas vinegar, (mercapto) propylene follate four said propylene, (methyl) acrylic acid six vinegar, (mercapto) acrylic acid octafluoropenta S, acrylic acid seventeen laurel Vinegar, dimethyl decyloxyethyl methacrylate, U-butylene glycol diacrylate, [6-hexanediol dipropionate, decanediol diacrylic acid , neopentyl glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, propylene glycol diacrylate, glycerol methacrylate acrylate, bisphenol A ethylene oxide adduct diacrylate Ester, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylol propylene oxide ethylene oxide adduct triacrylate, glycerol propylene oxide adduct triacrylate vinegar , gamma-triamphoyloxyethyl g|, dipentaerythritol hexamethylene hexanoate, phenolic varnish epoxy acrylic acid modified, novolac epoxy acid and anhydride modified, N-vinylpyrrolidine a ketone, N-vinyl caprolactam, an acrylically decylated isocyanate, dipentaerythritol monohydroxy pentaacrylate, a urethane acrylate, an unsaturated polyester acrylate, etc., one of which may be used or 2 or more types. Among these monomers, an acrylic monomer, particularly an acrylic monomer having three or more double bonds, is trimethylolpropane tri(methyl) acrylate or pentaerythritol from the viewpoint of improving photosensitivity. A poly(fluorenyl) acrylate such as tetra(meth)acrylate or dipentaerythritol hexa(meth)acrylate is more preferable. These monomers may be used singly or in combination. In the photosensitive resin composition of the present invention, the total amount of the component (B) and the component (B) is 100 parts by weight. The component (B) is used in the range of from 1 to 4 parts by weight in the range of 320,634, and 11,123,580. (8) When the component is less than 5% by weight, the proportion of the functional group which is contained in the photosensitive resin composition of the present invention is small, resulting in insufficient, and the formed pattern is thinner than the target line, and the pattern is liable to fall off. On the other hand, when it exceeds 40 parts by weight, the light sensitivity is too strong, and the pattern line width becomes too thick for the mask of the ® case, and the line width of the mask cannot be reproduced, and the line width is changed. Poor, there are (four) edges are mineral teeth = can not be a sharp problem. The photopolymerization initiator of the component (C) is not particularly limited as long as it is a compound which can polymerize a compound having an ethylenic unsaturated bond and can be subjected to addition polymerization as long as it is a photopolymerization initiator. . For example, an acetophenone-based compound, a trimorphine-based compound, a benzoin-based compound, a benzophenone-based compound, a thioxanthone (th i 〇xan 〇-like) compound, and a stilbene-based compound can be mentioned. , acyl 〇xime compounds, and the like. Among them, examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzoguanidinyl ketal, and 2-hydroxy-2. - mercapto-l-[4-(2-hydroxyethoxy)phenyl]propane-propyl, hydroxycyclohexyl phenyl ketone, 2-methyl-2-(N-morpholinyl)-1- (4-methylthiophenyl)propan-1-one, 2-phenylmercapto-2-diamino-l-(4-(N-morpholinyl)phenyl)butan-1-one, An oligomer of 2-hydroxy-2-indenyl-nonylvinyl)phenyl]propan-1-one. The three well system compounds may, for example, be 2,4,6-tris(trichloroindenyl)-1,3,5-trin, 2-mercapto-4,6-bis(trichloroindenyl)-1,3 , 5-three tillage, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-(4-chlorophenyl)-4,6-double 12 320634 200923580 (trichloromethyl)-1,3,5-trianthene, 2-(4-decyloxyphenyl)-4,6-bis(trimethylmethyl)-1,3,5-trimorphine, 2 -(4-decyloxynaphthyl)_4,6-bis(trichloromethyl)_1,3,5-three tillage, 2-(4-methoxystyryl)_4,6-bis(trichloro Methyl)-1,3,5-three tillage, 2-(3,4,5-trimethoxyoxystyryl)_4,6-bis(trichloromethyl)-1,3, 5-trin , 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3'5-trimorphine, 2-(sunflower based)-4,6-bis (three gases) Methyl)-1,3,5-three tillage, etc. Examples of the benzoin-based compound include benzoin, benzoin decyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the benzophenone-based compound include benzophenone, methyl benzoyl benzoate, 4-phenyl benzophenone, and 4-phenylphenyl sulfonyl-4, fluorenyl diphenyl sulfonate. Ether, 3'3', 4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimercaptobenzophenone, and the like. The thiophene compound may, for example, be 2-isopropyl exemplified, 4- propylpropylthio, 2' 4-diethylxanthone or 2,4-dichloro. Sexone,: propoxy thioxanthone, and the like. The pot compound may, for example, be 2_(o-chlorophenyl sulfonium (tetra) 2 polymer, 2 chlorophenyl phenyl) H methoxy oxime 2: (4) Benzene 2 polymer, 2,4,5-triaryl. The ruthenium compound may, for example, be Η9_ethyl-6-I-based Η Η, ♦I-based]-bicycloheptyl + _ + = 酉曰, 1 puethyl + benzophenone) H Mu 3 320634 13 200923580 adamantyl-decane-1-one oxime-benzoate, 1-[9-ethyl-6_(2-mercaptophenyl)-9' Η'-carbazole _]adamantyl decane _ ketooxime-0-acetate, 1-[9-ethyl_6_(2-methylphenyl fluorenyl) -9, hydrazine, oxazol-3-yl] -tetrahydrofuranylmethane ketone benzoate, hydrazine _[9_ethyl-6-(2-methylbenzoyl)_9, hydrazine, _carbazole _3_ kib tetrahydrofurfuryl methane- 1-ketooxime-0-acetate, oxime-ethyl-6-(2-methylphenylhydrazino)-9, Η'-oxazol-3-yl]monothiomethane ketone oxime 〇_Phenyl phthalate, 1-[9-ethyl-6-(2-mercaptobenzoyl)_9, hydrazine, _carbazole _3_yl] thiophenyl decane-1-one oxime Acetate, monoethyl_6_(2- mercaptobenzoyl)-9, hydrazine, -carbazole-3-yl]-morpholinylmethane 4-one oxime Benzoate, 1-[9-ethyl-6-(2-methylbenzylidene)_9, hydrazine, _carbazole _3_yl]-morpholinylmethane-1-one oxime 〇 〇 Acid ester, Μ9-ethyl_6_(2- mercaptobenzoyl)-9, hydrazine, -carbazole-3-yl]-ethane_丨-ketooxime_〇_bicycloheptanecarboxylate , 1-[9-ethyl-6-(2-methylphenyl.indenyl)-9, indole, oxazol-3-yl]-ethane-1-one oxime 〇-tricyclodecane carboxy Acid ester, Μ9_ethyl-6-(2-mercaptobenzylidene)_9, hydrazine, _carbazole _3_yl]-ethane _ 丨 ketone oxime-0-adamantane carboxylate, 1 , 2-octadiene phenyl thio) 2_(7) phenyl fluorenyl 2)] (manufactured by Ciba Specialty Chemicals, product name: Iragacure OXE01), ethyl ketone 1-[9-ethyl_6_(2_methyl Benzopyridinyl)_9H_indazol-3-yl]-1-(0-ethenylhydrazine) (manufactured by Ciba Specialty Chemicals, product name: Irgacure OXE02). As the photopolymerization initiator of the component (C), an active radical generator or an acid generator can also be used. As the living radical generator, for example, 2,4,6-trimercaptobenzylidene diphenylphosphine oxide, 2,2,_bis(o-chlorophenyl)-4,4,14 320634 200923580 -5 can be used. '5' - tetraphenyl-I,2,-biimidazole, l-butyl- 2-chloroacridone, 2_ethyl. hydrazine, benzil, 9, 10-phenanthrene , camphorquinone, phenyl group; methyl glyoxylate, titanium titanate compound, and the like. The acid generator may, for example, be p-methyl, 4-hydroxyphenyl dimethyl sulfonate benzenesulfonate, 4-hydroxyphenyl dimethyl sulfonium hexafluoroantimonate, 4-ethenyloxyphenyl p-toluenesulfonate. Dimethyl sulfonium salt, hexafluoroantimony acid 4-acetoxyphenyl methyl peroxide benzyl sulfonium salt, triphenyl sulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, a rust salt such as diphenyl sulfonium sulfonate, a diphenyl sulfonium hexafluoroantimonate or a nitrobenzyl benzene sulfonate or a benzoin tosylate. Further, in the case of the above-mentioned compound, a compound which generates an active radical and an acid at the same time may be used as the active radical generator. For example, a tri-grain compound may be used as an acid generator. The photopolymerization initiator of the component (c) may be used singly or in combination of two or more. Although it does not act as a photoinitiator or a sensitizer mentioned later, it is used together with the photoinitiator of the component (c) mentioned above, and it can add the capability of a photo-initiator or sensitizer separately. Compound. The compound such as L may, for example, be an amine compound which is effective when used in combination with benzophenone. The amine compound may, for example, be triethanolamine, methyldiethanolamine, monoisopropanolamine, 4-dimethylammonium benzoate, ethyl 4-dimethylaminobenzoate or 4-dimethylamine. Isoamyl benzoate, 2-diguanylamino benzoate, 2-ethylhexyl 4-diguanylaminobenzoate, N,N-dimethyl-p-benzoquinone 4, 4 pairs (one Amidino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)diphenylhydrazine, and the like. Among the photopolymerization initiators of the above component (C), a three-pigmentation photopolymerization initiator and a mercaptoquinone-based photopolymerization initiator which are introduced into three 320634 15 200923580-gas methyl group are preferably used. The amount of the component (c) component photoinitiator used is 5 to 5 parts by weight, preferably 20 to 45 parts by weight based on 1 part by weight of the total of the components (a) and (B) as the resin component. Parts by weight. (If the mixing ratio of the bismuth component is less than 5 parts by weight, the speed of photopolymerization becomes slow, and the sensitivity is lowered. On the other hand, if it exceeds 50 parts, the sensitivity becomes too strong, and the pattern line width becomes relative to the pattern mask. In a form that is too thick, the faithful line width cannot be reproduced with respect to the mask, and the pattern edge is jagged and cannot be sharp. It may be in addition to the photopolymerization initiator of the component (C). The sensitizer may be used. The sensitizer may be a general sensitizer which is usually used in a photopolymerization initiator, and in order to further improve the sensitivity, it is preferred to use at least one selected from the group consisting of a benzophenone compound and a thioxanthone. a compound in a group of a compound and a ketocoumar i η compound. Specifically, benzophenone, 2,4,6-trimethyl benzophenone, 4-benzene can be used. Dibenzophenone, 4-benzylidene- 4,-mercaptodiphenyl sulfide, 4,4,_bis(dimethylamino)benzophenone, 4,4,-bis(diethylamine Benzophenone-based compound such as benzophenone; thioxanthone, dimercaptothioxanthone, 2,4-dimethylthioxanthone a thioxanthone compound such as 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone or 2-chlorothioxanthone; 3_ethylidene coumarin , 3-ethylindolyl-7-diethylamine coumarin, 3-phenylindole coumarin, 3__benzimidyl-7-diethylamine coumarin, 3-phenylhydrazinyl _7_methoxycoumarin, 3,3'-carbonyl dicoumarin, 3,3,-carbonyl bis(7-methoxycoumarin), 3,3'-carbonyl double (5, 7 a coumarin ketone-based compound such as a bis-oxocoumarin. These may be used alone or in combination of two or more. 16 320634 200923580 Others: The ratio of the sensitizer to the sensitizer is not particularly early. Xenon lamp, you have the first polymerization initiator and the sensation sword to 40% by mass, more preferably 1 to 2, and 5: too little, the sensitivity is reduced, if too much two == the invention (D) The multi-functional thiol compound of the composition is one having two or more sulfhydryl groups (Si} in the same molecule, and can be represented by the following formula (〖):
、 } ⑴ (式中，R1表示烷基，p表示可含有碳原子以外之原子之η 價脂肪族基，R°不為氫原子而為烷基，η表示2至4)。 上述通式（I)表示之多官能性硫醇化合物之具體例，可 列舉具有下述構造式之1，4-雙（3-酼基丁醯氧基）丁烷[式 (Π)]、1，3, 5-三（3_毓基丁氧基乙基5-三畊 -2’4’6(111’311，511)-三酮[式（111)]、及季戊四醇四（3-酼基 丁酸酯）[式（IV)]等。該等多官能性硫醇可使用1種，亦可 複數組合使用。 320634 17 200923580(1) (wherein R1 represents an alkyl group, p represents an η-valent aliphatic group which may contain an atom other than a carbon atom, R° is not a hydrogen atom and is an alkyl group, and η represents 2 to 4). Specific examples of the polyfunctional thiol compound represented by the above formula (I) include 1,4-bis(3-mercaptobutyloxy)butane [formula] having the following structural formula, 1,3,5-tris(3_mercaptobutoxyethyl 5-tricotin-2'4'6(111'311,511)-trione [formula (111)], and pentaerythritol tetrakis(3-) Mercaptobutyrate) [Formula (IV)], etc. These polyfunctional thiols may be used singly or in combination. 320634 17 200923580
(ir)(ir)
感光性樹脂組成物中之多官能性硫醇的調配量，相對 於除去溶劑之總固體成分，以在0. 3至8. 9重量％，較好 在0. 8至6. 4重量％之範圍添加較理想。調配比例若不在 上述之範圍内，則感光性樹脂組成物之安定性、臭氣、感 度、解像性、顯像性、密著性等會惡化。在低添加量時， 感度、密著性降低，在高添加量時，相對於硫醇化合物， 引發劑之比例變少，光聚合之速度變慢，感度降低，不易 固化且阻劑溶解性亦降低。 該等惡化確實之主要因素雖不明，惟，認為係有關於 多官能性硫醇為以自由基或離子在碳原子-碳原子雙鍵進 行anti-Markownikoff加成，亦即為可取得作為單體之作 18 320634 200923580 用之化合物。亦即，其作為單體之機能係由於比上述（B) 成分之理想丙烯酸單體低，故若添加與通常單體相同之添 加量，則會阻礙丙烯酸單體之機能，如上所述，經由如引 發劑般少量添加，而可發揮更高機能。 (E)成分之著色材料為選自屬於遮光性顏料之黑色有 機顏料、混色有機顏料或遮光材料之至少一種。黑色有機 顏料可列舉例如茈黑、花青素黑（cyanine black)等。混色 有機顏料可列舉例如將選自紅色、藍色、綠色、紫色、黃 色、花青色、洋紅等之至少2種以上之顏料混合並作成擬 似黑色化者。遮光材料可列舉例如碳黑、氧化鉻、氧化鐵、 鈦黑、苯胺黑、花青素黑。著色材料可適當選擇2種以上 使用，從遮光性、表面平滑性、分散安定性、與樹脂之相 溶性之觀點而言，以碳黑為較佳。 另外，（E)成分之著色材料可根據期望而與分散劑共同 使用。該等分散劑可列舉例如陽離子系、陰離子系、非離 子系、兩性離子系、聚石夕氧（si 1 icone)系、氟系等界面活 性劑。該界面活性劑之具體例可列舉聚氧伸乙基月桂醚、 聚氧伸乙基硬脂醚等聚氧伸乙基烷基醚類等。 關於（E)成分之著色材料之添加量，較佳係調配成使除 去感光性樹脂組成物之溶劑之固體成分濃度成為50%至 60%。該濃度若太低，則遮光性不充足，為了獲得理想之 對比，膜厚非變厚不可，而不易獲得黑矩陣之面平滑性。 相對地，添加量若太多，則含有（E)成分之黑矩陣用感光性 樹脂組成物之分散安定性降低，本來會成為黏合劑（binder) 19 320634 200923580 ‘之感光性樹脂之含量亦減少，有不能獲得良好的 之問題之慮。 ，、界付「玍 就（E)成分之調配比例而言，相對於由本發明組成物中 之（A)至（E)成分所組成之除去溶劑之固體成分，其重旦 率為40至70重量％，較好為50至6〇重量％。若少 重量％ ’則遮光性不；i ’若超過7〇重量％，則由於本來會 成為黏合劑之感光性樹脂之含量減少，而有損壞顯像特性 且同時亦使膜形成能受損之問題。 本發明之黑阻劑用感光性樹脂組成物中，除了上述（A) 至（E)成分以外，以使用溶劑為佳。溶劑可列舉例如^ 乙醇、正丙醇、異丙醇、乙二醇、丙二醇等醇類；i或沒 :帖品醇（万-terpinenol)等莊烯類；丙鲷、甲基乙基_、 王辰己酮、N-甲基-2-吡咯烷酮等酮類；甲茨、— + 一甲术、四甲 基苯等芳族烴類；溶纖劑、.甲基溶纖劑、乙基溶纖劑 必醇、甲基卡必醇、乙基卡必醇、丁基卡必醇、丙二醇一 ?基醚、丙二醇一乙基醚、二丙二醇一甲基醚、二丙 :乙基醚、三乙二醇一甲基醚、三乙二醇一乙基_等烷二 醇醚類；乙酸乙醋、乙酸丁酯、溶纖劑乙酸§旨n 劑乙酸酿、丁基溶纖劑乙酸醋、卡必醇乙酸醋、乙二卡必 醇乙酸酉旨、丁基卡必醇乙酸酯、丙二醇—甲朗乙^旨、 丙二醇-乙基_乙酸s旨等乙_類等；經由使用該等 而溶解、混合，即可作成均一溶液狀之板成4勿。 此外’本發明之黑阻綱感紐樹脂組成物中，必 時可調配硬化促進劑、熱聚合禁止劑、增塑劑、填充材料、 320634 20 200923580 溶劑、塗平劑、咕.治杰丨处、The 5% by weight, preferably from 0.8 to 6. 4% by weight, based on the total solids of the solvent. Range addition is ideal. When the blending ratio is out of the above range, the stability, odor, sensitivity, resolution, developability, and adhesion of the photosensitive resin composition are deteriorated. When the amount is low, the sensitivity and the adhesion are lowered. When the amount is high, the ratio of the initiator is small relative to the thiol compound, the rate of photopolymerization is slow, the sensitivity is lowered, the curing is difficult, and the solubility of the resist is also low. reduce. Although the main factors of such deterioration are unclear, it is considered that the polyfunctional thiol is an anti-Markownikoff addition of a double bond of a carbon atom and a carbon atom by a radical or an ion, that is, it can be obtained as a monomer. The compound used in 18 320634 200923580. That is, since the function as a monomer is lower than the ideal acrylic monomer of the above component (B), if the addition amount is the same as that of the usual monomer, the function of the acrylic monomer is inhibited, as described above. It can be added in a small amount like an initiator to achieve higher performance. The coloring material of the component (E) is at least one selected from the group consisting of a black organic pigment belonging to a light-shielding pigment, a mixed color organic pigment, and a light-shielding material. The black organic pigment may, for example, be black, cyanine black or the like. The mixed color organic pigment may, for example, be a mixture of at least two or more pigments selected from the group consisting of red, blue, green, purple, yellow, cyan, magenta, and the like, and which are similarly colored. Examples of the light-shielding material include carbon black, chromium oxide, iron oxide, titanium black, nigrosine, and anthocyanin black. The coloring material can be appropriately selected from two or more types, and carbon black is preferred from the viewpoints of light blocking properties, surface smoothness, dispersion stability, and compatibility with a resin. Further, the coloring material of the component (E) can be used together with the dispersing agent as desired. Examples of such a dispersing agent include surfactants such as a cationic system, an anionic system, a nonionic system, a zwitterionic system, a polysulfonium (si 1 icone) system, and a fluorine-based surfactant. Specific examples of the surfactant include polyoxyethylene ethyl ethers such as polyoxyethylene ethyl laurate and polyoxyethylene ethyl stearyl ether. The amount of the coloring material added to the component (E) is preferably adjusted so that the solid content of the solvent in which the photosensitive resin composition is removed is 50% to 60%. If the concentration is too low, the light-shielding property is insufficient. In order to obtain a desired contrast, the film thickness is not thick, and the surface smoothness of the black matrix is not easily obtained. On the other hand, if the amount of addition is too large, the dispersion stability of the photosensitive resin composition for the black matrix containing the component (E) is lowered, and the content of the photosensitive resin which is originally a binder (also known as binder) 19 320634 200923580' is also reduced. There are concerns about not getting good questions. And the ratio of the proportion of the component (E) to the solid content of the solvent-removed component composed of the components (A) to (E) in the composition of the present invention, the weight ratio of 40 to 70 The weight % is preferably 50 to 6 % by weight. If the weight % is less, the light shielding property is not; if i ' exceeds 7 % by weight, the content of the photosensitive resin which is originally a binder is reduced, and the content is damaged. In addition to the above components (A) to (E), it is preferred to use a solvent in the photosensitive resin composition for a black resist of the present invention. For example, alcohols such as ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; i or not: sterols such as sterol (ter-terpinenol); propyl hydrazine, methyl ethyl ketone, and wangchen hexanone , ketones such as N-methyl-2-pyrrolidone; aromatic hydrocarbons such as methyl ketone, - + one-methyl, tetramethylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve , methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monoether ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl Ether, dipropylene: ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and other alkyl glycol ethers; acetic acid ethyl acetate, butyl acetate, cellosolve acetic acid § n agent acetic acid Stuffed, butyl cellosolve acetate vinegar, carbitol acetate vinegar, ethane carbitol acetate, butyl carbitol acetate, propylene glycol - ketone, propylene glycol - ethyl acetate s _ class, etc.; by dissolving and mixing by using these, it can be made into a uniform solution-like board. In addition, the black retardation-sensitive resin composition of the present invention can be adjusted with a hardening accelerator and thermal polymerization. Prohibition agent, plasticizer, filling material, 320634 20 200923580 Solvent, leveling agent, 咕.治杰丨,
‘泡劑專添加劑。献聚A 氫靦一甲基w ”、、禁止劑可列舉氫醌、 、居、梧酚（pyr〇gall〇i)、钕 _ ^ 嗟哄等。增_可列舉鄰苯二甲酸二丁丁基兒茶驗、吩 酯、磷酸三甲贫. 一丁酉日、鄰苯二甲酸二辛 列舉玻璃纖維、-曰^聰印1 Ph〇Sphate)等。填充材料可 、一氧化石夕、雲母、惫儿z * 劑可列舉例如功么> ± / 軋化鋁萼。消泡劑或塗平 糸、氟素系、丙婦酸系 本發明之里阳m * '、之化合物。 …、阻劑用感光性樹月旨έ (Ε)成分或該箄#^#^ 曰、、'且成物含有上述（A)至 Λ z寺成分及溶劑作為主成分。 分（固體成分包含#### 1 77除去溶劑之固體成 刀包3硬化後成為固體成分 成分合計以含有8〇重量％以上 =):，⑷至⑻ 較佳。、玄硎少上 3有90重罝％以上 旱又佳各副之罝係根據目標之黏度而變 賠细忐你击人‘ JU 雙化’以在感光性樹 月曰、，且成物中3有在7〇至9G重量％|㉘者較佳。 本，黑阻劑用感光性樹脂組成物係作為黑矩陣形 成用之樹脂組成物為優越。又，本發明之黑矩陣係使用本 發明之黑阻劑用感光性樹脂組成物，並經由例如光微影法 (photolithography method)而形成。可列舉如下述之方 法.其製造步驟為首先將感光性樹脂組成物作成溶^，塗 抹在基板表面，接著將溶劑乾燥（預烘烤）後，在由此操作 而獲得之被膜上蓋光罩，照射紫外線將曝光部硬化，用驗 性水溶液將未曝光部溶出’進行顯像，形成圖案後再進行 後再烘烤（熱鍛燒）而予以後乾燥。 塗抹本發明組成物溶液之基板，可使用在玻璃、透明 膜（例如聚碳酸酯、聚對苯二甲酸乙二酯、聚醚礙等）上經 蒸鍍或圖案化有ΙΤ0、金等透明電極者等。 320634 21 200923580 將該組成物之溶液塗抹在基板上之方法，除了公知之 溶液浸潰法、喷霧法之外，亦可採用使用滾筒塗覆機、刀 背塗覆機（1 and coater)或旋轉塗覆機之方法等任何一種 方法。根據該等方法，在塗抹所期待的厚度後，經由除去 溶劑（預烘烤）而形成被膜。預烘烤可經由烤箱、熱盤等加 熱手段而進行，預烘烤之加熱溫度及加熱時間係對應使用 之溶劑而適當選擇，可在例如80至120°C之溫度進行1至 10分鐘。 在預烘烤後所進行之曝光係經由曝光機進行，藉由隔 著光罩曝光，而只將對應圖案之部分之阻劑進行感光。適 當選擇曝光機及其曝光照射條件，例如使用超高壓水銀 燈、高壓水銀燈、金屬鹵化物燈、遠紫外線燈等光源進行 曝光且截切短波長（313nm、334nm以下），將塗膜中之黑阻 劑用樹脂組成物進行光硬化。 曝光後之鹼性顯像係以除去未曝光部分之阻劑為目的 而進行，經由該顯像而形成期待之圖案。適用於該鹼性顯 像之顯像液可列舉例如驗金屬或驗土金屬之碳酸鹽水溶 液、鹼金屬之氫氧化物水溶液等，其中，較佳係使用含有 碳酸納、碳酸_、碳酸經等碳酸鹽0. 0 5至3重量％之弱驗 性水溶液，在20至30°C之溫度進行顯像，並可使用市售 之顯像機或超音波洗淨機等精密地形成微細之圖像。 進行該等顯像後，在180至250°C之溫度及20至60 分鐘之條件下進行熱處理（後烘烤）。該後烘烤係以提高經 圖案化之黑矩陣與基板之密著性等為目的而進行。其係與 22 320634 200923580 預烘烤相同，經由烤箱、熱盤等加熱手段而進行。本發明 之經圖案化之黑矩陣係根據以上之光微影法，並經過各步 驟而形成。 本發明之組成物如前所述，適用於經由曝光、驗性顯 像等操作而形成微細之圖案’但即使經由以往之網版印刷 形成圖案，亦可獲得同樣的遮光性、密著性、電絶緣性、 耐熱性、耐藥品性優越之黑矩陣。 本發明之黑阻劑用感光性樹脂組成物可作為塗覆材料 使用，尤其在液晶顯示裝置或攝影元件中所使用之濾色器 用油墨及經由該等所形成之遮光膜可作為濾色器、液晶投 射用之黑矩陣等使用。 本發明之濾色器可藉由在設置有上述黑矩陣之基板上 將各色油墨塗抹成各色預定之圖案，並顯像、硬化，更進 一步形成保護膜等之公知方法而獲得。 [發明之效果] 本發明之黑阻劑用感光性樹脂組成物即使為例如著色 材料之含有比例多之光硬化困難之遮光感光性樹脂組成 物，亦可在寬廣之顯像容限中獲得無顯像殘渣且圖案尺寸 安定性、圖案密著性、圖案邊緣形狀之銳利性良好的圖案， 賦予良好之遮光膜。 【實施方式】 以下，以實施例及比較例為基礎而對本發明之實施形 態做具體的說明，惟，本發明不只限於該等例。此處，在 實施例、比較例之黑矩陣之製造中所使用之原料及略號為 23 320634 200923580 • 如下所述。 (A) :具有苐骨架之環氧丙烯酸酯之酸酐縮聚物之丙二醇一 曱基醚乙酸酯溶液（樹脂固體成分濃度= 56. 1重量％，新曰 鐵化學（股）公司製造，商品名V259ME) (B) :三羥曱基丙烷三丙烯酸酯（曰本Sartomer(股）公司製 造，商品名SR351S) (C) -l:乙酮1-[9-乙基-6-(2-曱基苯曱醯基）-9H-咔唑-3-基]-l-(0-乙醯基肟）（汽巴專業化學公司製造，製品名： Irgacure OXE02) (C) -2 : 4-(4’ -乙基聯苯基）-4,6-雙（三氯甲基）-l，3,5-三啡（Respe化學公司製造，商品名STR-2BP) (D) -l : 1，4-雙（3-M基丁醯氧基）丁烷（商品名：Karenz MT BD1 (以下簡稱為BD1 :昭和電工（股）公司製造） (D)-2 : 1，3, 5-三（3-M基丁氧基乙基）-1，3, 5-三哄-2, 4, 6 (1H，3H, 5H)-三酮（商品名：Karenz MT NR1(以下簡稱為 NR1 :昭和電工（股）公司製造） (D)-3 ··季戊四醇四（3-魏基丁酸酯）（商品名：Karenz MT PE1(以下簡稱為PE1 :昭和電工（股）公司製造） (D) -4:季戊四醇四硫代丙酸酯（商品名：PETP(淀化學（股） 公司製造） (E) :碳黑濃度20重量％、高分子分散劑濃度4. 0重量％ 之丙二醇一甲基醚乙酸酯分散液（固體成分24. 0%) (F) -l :丙二醇一甲基醚乙酸酯 (F)-2 :環己酮 24 320634 200923580 * [實施例] 將上述調配成分以表1記載的比例進行調配，調製實 施例1至10及比較例！至6(阻劑）。在表J中，⑷成分 之（）内之數字表示固體成分量，（E)成分之（）内之數字表 示顏料（著色材料）所占有之固體成分量。 將表1記载的各成分均一混合而獲得之實施例1至10 及比較例1至6中之各黑阻劑用感光性樹脂組成物，使用 彡疋轉塗覆機塗抹在125mmx 125mm之玻璃基板上（康寧 1737)，使後烘烤後之膜厚成為1. 1 # ^，在80°C進行2分 鐘之預烘烤。然後，將曝光間隙調整為80 Am，在乾燥塗 膜上蓋上線/間隙=10 # m/ ΙΟαπι及20/zm/20/zm之負型 光罩，用i線照度30mW/cm2之超高壓水銀燈照射80mj/ cm2之紫外線，進行感光部分之光硬化反應。‘Foaming agent special additives. Concentrating A hydroquinone monomethyl w ”, and the inhibiting agent may be hydroquinone, hydrazine, pyrogallol (pyr〇gall〇i), 钕_^ 嗟哄, etc., _ can be cited as dibutyl butyl phthalate Tea test, phenethyl ester, triglyceride phosphate. A diced day, dioctyl phthalate listed glass fiber, -曰^聪印1 Ph〇Sphate), etc. Filling materials, oxidized stone, mica, 惫The z* agent may, for example, be a work of > ± / rolled aluminum ruthenium. An antifoaming agent or a sputum sputum, a fluorinated system, a propyl benzoate, a compound of the present invention, and a compound for the resist. Sexual tree έ έ Ε Ε 成分 或 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ The solids obtained by removing the solvent are solidified into a knife package 3 and become a solid component. The total amount of the solid component is 8% by weight or more = (4) to (8) is preferred.罝 变 根据 根据 根据 根据 根据 根据 根据 根据 根据 JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU JU The photosensitive resin composition for a resist is excellent as a resin composition for forming a black matrix. Further, the black matrix of the present invention uses the photosensitive resin composition for a black resist of the present invention, and is, for example, photolithographic. It is formed by a photolithography method. The manufacturing method is as follows: the photosensitive resin composition is first dissolved, applied to the surface of the substrate, and then the solvent is dried (prebaked), thereby operating thereby The obtained film is covered with a mask, and the exposed portion is cured by irradiation with ultraviolet rays, and the unexposed portion is eluted with an aqueous solution to perform development, and a pattern is formed, followed by post-baking (hot calcination) and post-drying. The substrate of the composition solution can be used for vapor deposition or patterning of a transparent electrode such as ruthenium or gold on a glass or a transparent film (for example, polycarbonate, polyethylene terephthalate, or polyether). 320634 21 200923580 The method of applying the solution of the composition on the substrate can be carried out by using a roller coating machine or a knife backing method in addition to the known solution dipping method and spraying method. Any method such as a method of coating a coater or a spin coater. According to these methods, after applying the desired thickness, a film is formed by removing a solvent (prebaking). Prebaking can be performed via an oven. The heating means such as a hot plate is carried out, and the heating temperature and the heating time of the prebaking are appropriately selected depending on the solvent to be used, and can be carried out, for example, at a temperature of 80 to 120 ° C for 1 to 10 minutes. The exposure is performed by an exposure machine, and only a part of the resist of the corresponding pattern is exposed by exposure through a photomask. The exposure machine and its exposure and irradiation conditions are appropriately selected, for example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide. Light sources such as an object lamp and a far-ultraviolet lamp are exposed and cut at a short wavelength (313 nm, 334 nm or less), and the resin composition for a black resist in the coating film is photocured. The alkaline development after exposure is performed for the purpose of removing the resist of the unexposed portion, and a desired pattern is formed by the development. Examples of the developing solution suitable for the alkaline development include a carbonate aqueous solution of a metal test or a soil test metal, an aqueous hydroxide solution of an alkali metal, and the like. Among them, sodium carbonate, carbonic acid, carbonic acid, etc. are preferably used. A weak aqueous solution of 0.5 to 5% by weight of carbonate is developed at a temperature of 20 to 30 ° C, and a fine pattern can be precisely formed using a commercially available image forming machine or an ultrasonic cleaner. image. After the development, heat treatment (post-baking) is carried out at a temperature of 180 to 250 ° C and for 20 to 60 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned black matrix and the substrate. It is the same as the pre-baking of 22 320634 200923580, and is carried out by heating means such as an oven or a hot plate. The patterned black matrix of the present invention is formed by the above photolithography method and through various steps. As described above, the composition of the present invention is suitable for forming a fine pattern by operation such as exposure or visual imaging. However, even if a pattern is formed by conventional screen printing, the same light-shielding property, adhesion, and the like can be obtained. Black matrix with excellent electrical insulation, heat resistance and chemical resistance. The photosensitive resin composition for a black resist of the present invention can be used as a coating material, and particularly, a color filter ink used in a liquid crystal display device or a photographic element, and a light shielding film formed therethrough can be used as a color filter. It is used for black matrix for liquid crystal projection. The color filter of the present invention can be obtained by applying a predetermined pattern of inks of respective colors on a substrate provided with the above-mentioned black matrix, developing and curing the film, and further forming a protective film or the like. [Effects of the Invention] The photosensitive resin composition for a black resist of the present invention can obtain a light-shielding photosensitive resin composition which is difficult to be photohardened, for example, in a coloring material, and can be obtained in a wide range of development tolerances. A pattern having good development of pattern residue, pattern adhesion, and sharpness of pattern edge shape is imparted to a good light-shielding film. [Embodiment] Hereinafter, embodiments of the present invention will be specifically described based on the embodiments and comparative examples, but the present invention is not limited to the examples. Here, the raw materials and the abbreviations used in the manufacture of the black matrix of the examples and the comparative examples are 23 320634 200923580 • as described below. (A): a propylene glycol monodecyl ether acetate solution of an epoxy acrylate polycondensate having an anthracene skeleton (resin solid content concentration = 56. 1% by weight, manufactured by Shinco Steel Chemical Co., Ltd., trade name V259ME) (B): Trihydroxydecylpropane triacrylate (manufactured by Sartomer Co., Ltd., trade name SR351S) (C) -l: Ethylketone 1-[9-ethyl-6-(2-oxime (Benzene fluorenyl)-9H-carbazol-3-yl]-l-(0-ethenyl hydrazine) (manufactured by Ciba Specialty Chemicals, Inc., product name: Irgacure OXE02) (C) -2 : 4-( 4'-Ethylbiphenyl)-4,6-bis(trichloromethyl)-l,3,5-trimorphine (manufactured by Respe Chemical Co., trade name STR-2BP) (D) -l : 1, 4-bis(3-M-butylbutoxy)butane (trade name: Karenz MT BD1 (hereinafter referred to as BD1: manufactured by Showa Denko Co., Ltd.) (D)-2 : 1,3, 5-three ( 3-M-butoxyethyl)-1,3,5-tris-2,4,6 (1H,3H, 5H)-trione (trade name: Karenz MT NR1 (hereinafter referred to as NR1: Showa Denko) (manufactured by the company) (D)-3 · pentaerythritol tetrakis(3-weisylbutyrate) (trade name: Karenz MT PE1 (hereinafter referred to as PE1: Showa Denko) (manufactured by the company) (D) -4: pentaerythritol tetrathiopropionate (trade name: PETP (made by the company) (E): carbon black concentration 20% by weight, polymer dispersant concentration 4. 0% by weight of propylene glycol monomethyl ether acetate dispersion (solid content 24.0%) (F) -l : propylene glycol monomethyl ether acetate (F)-2: cyclohexanone 24 320634 200923580 * [ EXAMPLES The above-mentioned formulation components were blended in the ratios shown in Table 1, and Examples 1 to 10 and Comparative Examples! to 6 (resistance) were prepared. In Table J, the number in () of the component (4) indicates the amount of solid components. The number in the (E) component () indicates the amount of the solid component occupied by the pigment (coloring material). The components 1 to 10 and the comparative examples 1 to 6 obtained by uniformly mixing the components described in Table 1 were obtained. The photosensitive resin composition for each black resist was applied to a 125 mm x 125 mm glass substrate (Corning 1737) using a twist coater, and the film thickness after post-baking was 1. 1 # ^ at 80 ° C. Pre-bake for 2 minutes. Then, adjust the exposure gap to 80 Am, and cover the dry film with line/gap = 10 # m/ ΙΟαπι 20 / zm / 20 / zm of a negative mask, an ultrahigh pressure mercury lamp / cm2 of irradiation with ultraviolet rays of 80 mJ / cm2 of i-line illumination with 30mW, the photosensitive portion of the light hardening reaction.
25 320634 200923580 [表1 ] b〇 φΗ ΒΓ CD 2.20 (1-24) CO 2 m 2 § t2.40 (2*48) 1 CD O) I 61.54 LO 220 (1-24) CO s in u? d o § 14.55 5? 守 2*20 (1.24) s o g d IS C) 16.12! (3.22) to <D Cd σ> rr 687.50 S CO CM 2.20 (1.24) rt O <〇 PJ 〇 16.12 {Z22) Γ5 <D <d CD o 293.75 S 3.10 (1.75) CD CO O’ 12.40 (2.48) 〇> C0 功· π o o o r^· 叶二 n 2 i 16.t2 (352) s CO CD δ o δ 實施例（調配量g) | 〇 σι s o o 12.40 (2.48) & Ok ¢0 〇 32.84 导 Si o 〇 g § 16.12 (3.22) o CO ec> CO 〇> V tr> m ri δ 〇d 卜 荇 o ci Φ o 16.12 (3.22} to ID to CD 09 14.55 β 2.20 (1.24) CO s 1 09 2 m2 (3.22) 〇 (D 孕 162.50 Β CD 2.20 (1.24) C9 s d 1 16.12 <3.22) CO CO <D CD O) 一 100.00 δ in c? 2.20 (1.24) § en Q s d 16.12 (3·22> CO CD <〇 61.54 S §1 o 〇 C0 s 16.12 (3.22) CO <0 5 134.04 δ § IS 〇· g 11 CD 〇 CC> <〇 β» — 4A S cvi i 1 g 〇‘ 16.12 (3*22) eo «ί <〇 CD a? — esi δ ?? d d 1 16.12 (3.22) s (O <D σ> s g CCH (0-2 T § (D)-2 (D)—3 (D)-4 @ y-- i «w* (F)-2 X mm 1 ΓΜ: li •fi- 噠 額S' 回S S-M3 驟齧噠Φ 26 320634 200923580 接著，將該經曝光後之塗板（將感光性樹脂組成物塗抹 於玻璃基板上，使感光部分光硬化者）在23 、〇 〇4%气 氧化鉀水溶液中，在lkgf/cm2之喷淋顯像壓下，從圖案 開始出現之顯像時間（間斷時間=BT (break t丨me ))再+ 3 〇秒 之顯像後’進行5kgf/cm2之喷霧水洗，除去塗膜之末曝 光部分，在玻璃基板上形成晝素圖案。然後，使用熱風乾 無機在230°C進行30分鐘之後烘烤後’對於各個光罩寬測 定線寬及飽和曝光量。結果表示於表2。 [表2] OD/^m 線寬線)|線寬(20i<m線) 飽和曝光量(mJ) 實施例i 4.6 9.0 18.9 75 實施例2 4.6 9.4 19.3 59 實施例3 4.6 10.0 20.2 42 貫施例4 4.6 13.3 23.9 33 .實施例5 4.6 14.6 25.1 26 實施例6 4.5 15.5 26.5 26 貫施例7 4.5 15.6 25.8 26 實施例色 4.6 9.3 19.6 33 ，施你丨9 4.6 一 9.6 19.8 33 實施例1C 3.7 9.4 19.3 47 jtte 例 1 4.6 8.1 18.0 83 3.9 5.7 14.9 100> It較例3 4.5 16Ό 24.1 53 --比較俐4 Γ 4.5 1〇〇> Spiis 4.6 9.2 19.3 67 4.5 10.7 20.8 53 將實施例1至10及比較例1至6之各黑阻劑用感光性 樹脂組成物在室溫（22°C至24t)保存2星期及1個月者， 使用線/間隙=20 // m/ 20//m之負型光罩進行相同之曝 光、顯像操作，評估線寬、線寬減少率及表面之外觀。結 果表示於表3。 27 320634 200923580 * [表 3]25 320634 200923580 [Table 1] b〇φΗ ΒΓ CD 2.20 (1-24) CO 2 m 2 § t2.40 (2*48) 1 CD O) I 61.54 LO 220 (1-24) CO s in u? do § 14.55 5? 守2*20 (1.24) sogd IS C) 16.12! (3.22) to <D Cd σ> rr 687.50 S CO CM 2.20 (1.24) rt O <〇PJ 〇16.12 {Z22) Γ5 < D <d CD o 293.75 S 3.10 (1.75) CD CO O' 12.40 (2.48) 〇> C0 work·π ooor^· YE 2 n 2 i 16.t2 (352) s CO CD δ o δ Example ( The amount of preparation g) | 〇σι soo 12.40 (2.48) & Ok ¢0 〇32.84 Guide Si o 〇g § 16.12 (3.22) o CO ec> CO 〇> V tr> m ri δ 〇d 荇o ci Φ o 16.12 (3.22} to ID to CD 09 14.55 β 2.20 (1.24) CO s 1 09 2 m2 (3.22) 〇 (D Pregnancy 162.50 Β CD 2.20 (1.24) C9 sd 1 16.12 <3.22) CO CO <D CD O) a 100.00 δ in c? 2.20 (1.24) § en Q sd 16.12 (3·22> CO CD <〇61.54 S §1 o 〇C0 s 16.12 (3.22) CO <0 5 134.04 δ § IS 〇· g 11 CD 〇CC><〇β» — 4A S cvi i 1 g 〇' 16.12 (3*22) eo «ί <〇CD a? — esi δ ?? dd 1 16.12 (3.22) s (O <D σ> sg CCH (0-2 T § (D)-2 (D)—3 (D)-4 @ y-- i «w* (F)-2 X mm 1 ΓΜ: li •fi- 哒S' back S S-M3 哒 哒 Φ 26 320634 200923580 Next, The exposed coated plate (the photosensitive resin composition is applied to the glass substrate to lightly cure the photosensitive portion) is sprayed at lkgf/cm2 in 23, 〇〇4% potassium oxide aqueous solution. Next, the development time from the start of the pattern (interruption time = BT (break t丨me)) and then + 3 sec. after the development of '5 kgf / cm 2 spray, remove the exposed portion of the film at the end, in A halogen pattern is formed on the glass substrate. Then, using hot air drying inorganic after baking at 230 ° C for 30 minutes, the line width and the saturated exposure amount were measured for each mask width. The results are shown in Table 2. [Table 2] OD/^m line width line)|Line width (20i<m line) Saturated exposure amount (mJ) Example i 4.6 9.0 18.9 75 Example 2 4.6 9.4 19.3 59 Example 3 4.6 10.0 20.2 42 Example 4 4.6 13.3 23.9 33. Example 5 4.6 14.6 25.1 26 Example 6 4.5 15.5 26.5 26 Example 7 4.5 15.6 25.8 26 Example color 4.6 9.3 19.6 33 , application 丨 9 4.6 9.6 19.8 33 Example 1C 3.7 9.4 19.3 47 jtte Example 1 4.6 8.1 18.0 83 3.9 5.7 14.9 100> It Comparative Example 3 4.5 16Ό 24.1 53 --Comparative 俐4 Γ 4.5 1〇〇> Spiis 4.6 9.2 19.3 67 4.5 10.7 20.8 53 Examples 1 to 10 And the photosensitive resin composition for each black resist of Comparative Examples 1 to 6 was stored at room temperature (22 ° C to 24 t) for 2 weeks and 1 month, using line / gap = 20 // m / 20 / / m The negative mask performs the same exposure and development operations, and evaluates the line width, the line width reduction rate, and the appearance of the surface. The results are shown in Table 3. 27 320634 200923580 * [Table 3]
貫施例及比較例獲得之黑矩陣之評估項目及方法如下 所述，結果表示於表2及表3。 線寬從圖案開始出現之顯像時間（間斷時間）再+3〇秒而 "貝像後用測長顯微鏡（Nik〇n(股）公司商品名xd-20)測 定。 〇D .換算成厚lyUm時之光學濃度 表面之^觀：顯像、鍛燒後之塗膜之表面粗度（Ra)值未滿 150 A時評估為〇< 良好》在150 A以上時評估為X〈不良〉。 ^ 2將添加1級硫醇化合物之比較例5、6及添加2級硫 醇化口物之貫施例1至1〇予以比較時，添加1級硫醇化合 物者在、、二時期間為2星期之情形下，從間斷時間再+30秒， 从111圖案顯示大幅度之細線化，在為個月之情形 -p 2 Q 4 ^ “m圖案則未殘留。惟，添加2級硫醇化合物者在 '二寺J間為2星期、1個月之情形下皆可殘留良好的線寬。 28 320634 200923580 « 此外，在相對於引發劑而過剩添加硫醇化合物之比較例3 中，經時安定性不良，在添加過剩量之比較例4，圖案形 成本身即變得困難。 如表2及表3之結果所示，相較於未添加硫醇化合物 之比較例1、2，根據實施例1至10之結果可明瞭，經由 添加多官能性硫醇化合物，可更大幅度地提昇線寬。 【圖式簡單說明】 無 ^ 【主要元件符號說明】 無 29 320634The evaluation items and methods of the black matrix obtained by the examples and the comparative examples are as follows, and the results are shown in Tables 2 and 3. The line width from the beginning of the pattern to the development time (intermittent time) is +3 sec. and "Bei image" is measured with a length measuring microscope (Nik〇n company name xd-20). 〇D. The optical density surface when converted to a thickness of lyUm: when the surface roughness (Ra) of the film after calcination and calcination is less than 150 A, it is evaluated as 〇 < Good" at 150 A or more The evaluation was X <bad>. ^ 2 When Comparative Examples 5 and 6 in which a 1-stage thiol compound was added and 1 to 1 〇 in which a 2-stage thiolated mouth was added, the addition of a 1-stage thiol compound was carried out at 2 hours. In the case of the week, from the intermittent time of +30 seconds, from the 111 pattern, the sharpness is greatly reduced. In the case of the month - p 2 Q 4 ^ "m pattern is not left. However, the addition of the second-order thiol compound A good line width can be left in the case of 'two temples' for two weeks and one month. 28 320634 200923580 « In addition, in Comparative Example 3 in which a thiol compound is excessively added with respect to the initiator, the elapsed time The stability was poor, and in the comparative example 4 in which the excess amount was added, the pattern formation itself became difficult. As shown by the results of Table 2 and Table 3, compared with Comparative Examples 1 and 2 in which the thiol compound was not added, according to Examples As a result of 1 to 10, it is clear that the line width can be increased more greatly by adding a polyfunctional thiol compound. [Simple description of the drawing] No ^ [Main component symbol description] No 29 320634