TW200844660A - Alkali development type paste composition, method for conductive pattern and black matrix pattern formation using the same, and the conductive pattern and the black matrix pattern - Google Patents
Alkali development type paste composition, method for conductive pattern and black matrix pattern formation using the same, and the conductive pattern and the black matrix pattern Download PDFInfo
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- TW200844660A TW200844660A TW096143057A TW96143057A TW200844660A TW 200844660 A TW200844660 A TW 200844660A TW 096143057 A TW096143057 A TW 096143057A TW 96143057 A TW96143057 A TW 96143057A TW 200844660 A TW200844660 A TW 200844660A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
Abstract
Description
200844660 九、發明說明 【發明所屬之技術領域】 本發明係關於適用於薄型顯示器等導電性圖型及適用 於黑色矩陣圖型的形成之鹼顯影型糊料組成物，以及使用 其之導電性圖型及黑色矩陣圖型之形成方法，與其導電性 圖型及黑色矩陣圖型。此外以下指出導電性圖型與黑色矩 陣圖型雙方時，以圖型表示·，關於除此以外的情況，各自 以導電性圖型、黑色矩陣圖型表示。本發明更詳細而言， 係關於適用於使用最大波長爲3 5 0nm〜420nm的活性能量 線的雷射直接成像（Laser Direct Imaging)裝置，以及適合 有效率地形成精細的黑色矩陣圖型，而且保存安定性優異 的鹼顯影型糊料組成物；以及使用其之圖型的形成方法、 與其圖型。 【先前技術】 先前技術在薄型顯示器的玻璃基板等中，形成導電性 圖型作爲電極；此外，前面板係使用黑色矩陣圖型；然後 其形成方法，例如在玻璃基材上，塗佈乾燥圖型用的光阻 後作爲塗膜，透過經描繪電路或電極圖型的光罩，用活性 能量線對該塗膜進行曝光形成影像後，利用曝光部與非曝 光部的顯影液之溶解性差，藉由用鹼性水溶液進行顯影處 理’形成了對應於電路或電極圖型的光阻層，藉由燒成而 形成黏附於基板的圖型。 藉由作爲此活性能量線的雷射掃描進行感光、曝光的 -5- 200844660 組成物’提議含有特定的色素增感劑、及二茂鈦化合物等 之組合物（例如參考專利文獻〗、及專利文獻2)、或含有 特定的雙醯基膦氧化物之雷射感光性組成物（例如參考專 利文獻3) ’但此等組成物未能得到對於活性能量線之充 分的感度。 [專利文獻1]特開2002-3 5 1 07 1號公報（申請專利範圍） [專利文獻2]特開2002-35 1 072號公報（申請專利範圍） [專利文獻3]特開2004_45 596號公報（申請專利範圍） 【發明內容】 [發明所欲解決之課題] 本發明係鑑於上述問題所開發的發明，其主要目的係 提供對活性能量線的感度高、適合有效率地形成精細的圖 型之鹼顯影型糊料組成物，以及使用其之圖型的形成方 法’與其圖型。 [用以解決課題之手段] 爲了解決上述課題，本發明具備以下的構成。 (1)一種鹼顯影型糊料組成物，其特徵係含有（A)含羧 基之樹脂、（B)玻璃基質、（c)無機粉末、（D) 一分子內具 有至少一個以上的自由基聚合性不飽和基之化合物、及 (E-1)下述一般式⑴所表示之肟系光聚合起始劑、 -6 - 200844660 【化1】 …⑴ c=u—ο—c—R2 (式中，R1表示氫原子、碳數1-6的烷基、或苯基；R2表 示氫原子、碳數的院基。） 以及、（F)下述一般式（Π)所表示之硫化合物；[Technical Field] The present invention relates to an alkali-developing type paste composition suitable for use in a conductive pattern such as a thin display and a black matrix pattern, and a conductivity pattern using the same The formation method of the type and black matrix pattern, and its conductivity pattern and black matrix pattern. In addition, when both the conductivity pattern and the black matrix pattern are indicated below, the pattern is represented by the pattern, and the other cases are represented by the conductivity pattern and the black matrix pattern. More specifically, the present invention relates to a Laser Direct Imaging device suitable for use with an active energy ray having a maximum wavelength of 350 nm to 420 nm, and is suitable for efficiently forming a fine black matrix pattern, and An alkali-developing paste composition excellent in stability is stored; and a method of forming a pattern using the same, and a pattern thereof. [Prior Art] The prior art forms a conductive pattern as an electrode in a glass substrate or the like of a thin display; in addition, the front panel uses a black matrix pattern; and then a forming method thereof, for example, coating a dry image on a glass substrate After the resist for the type is used as a coating film, the coating film is exposed to light by an active energy ray through a mask of a drawing circuit or an electrode pattern, and the solubility of the developing solution in the exposed portion and the non-exposed portion is poor. A photoresist layer corresponding to a circuit or an electrode pattern is formed by developing treatment with an alkaline aqueous solution, and a pattern adhered to the substrate is formed by firing. A composition for sensitization and exposure by laser scanning as the active energy ray is proposed to contain a specific dye sensitizer, a composition of a titanocene compound, etc. (for example, refer to the patent literature, and patents) Document 2) or a laser photosensitive composition containing a specific bis-decylphosphine oxide (for example, refer to Patent Document 3) 'But these compositions fail to obtain sufficient sensitivity to the active energy ray. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2002-35 No. 072 (Patent Application) [Patent Document 3] JP-A-2004-45 596 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] [Problems to be Solved by the Invention] The present invention has been made in view of the above problems, and its main object is to provide a high sensitivity to an active energy ray and to form a fine map efficiently and efficiently. A type of alkali-developing paste composition, and a method of forming a pattern using the same, and a pattern thereof. [Means for Solving the Problem] In order to solve the above problems, the present invention has the following configuration. (1) An alkali-developing type paste composition characterized by comprising (A) a carboxyl group-containing resin, (B) a glass substrate, (c) an inorganic powder, and (D) at least one or more radical polymerization in one molecule. a compound of an unsaturated group, and (E-1) an oxime-based photopolymerization initiator represented by the following general formula (1), -6 - 200844660 (1) (1) c = u - ο - c - R2 (formula In the above, R1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group; R2 represents a hydrogen atom and a carbon number; and (F) a sulfur compound represented by the following general formula (Π);
【化2】 R3—NH R4—C=S[Chemical 2] R3—NH R4—C=S
R3—N R4—C—SH …⑴） (式中，R3表示烷基、芳基或取代芳基；R4表示氫原子或 烷基；此外，R3與R4表示互相鍵結後形成可含有選自 氧、硫及氮原子的雜原子之5員至7員環所必須的非金屬 原子群。） (2)如申請項（1)所記載的鹼顯影型糊料組成物，其中 該肟系聚合起始劑（E-1)，爲以下述式（III)所表示之申請 項1所記載的肟系光聚合起始劑， 【化3】 'R3—N R4—C—SH (1)) wherein R 3 represents an alkyl group, an aryl group or a substituted aryl group; R 4 represents a hydrogen atom or an alkyl group; further, R 3 and R 4 are bonded to each other to form a bond which may be selected from The alkali-developing type paste composition as described in the above-mentioned item (1), wherein the lanthanide polymerization is a non-metal atomic group of the hetero atom of the oxygen, sulfur, and nitrogen atoms. The initiator (E-1) is an oxime-based photopolymerization initiator described in the application formula 1 (III), which is represented by the following formula (III).
• _ » (II!) 200844660 (式中，1個或2個的R5爲下述式（I)所表示（惟，包括2個 R5爲一般式（I)所表示的情況、R5各自不同的情況），剩餘 的R5表示氫原子、甲基、苯基或鹵素原子（惟，包括各R5 各自不同的情況）。） 【化4】 R1 j) —C=N—0—C—R2 …⑴ 式中，R1表示氫原子、碳數1〜6的烷基、或苯基，R2表 示氫原子、碳數1〜6的烷基。 (3) 如（1)或（2)所記載之鹼顯影型糊料組成物，其中該 含羧基之樹脂（A)，係再含有（A-1)具有一個以上的自由基 聚合性不飽和基的含羧基之樹脂。 (4) 如（1)或（2)所記載之鹼顯影型糊料組成物，其係再 含有（E-2)下述一般式（IV)所表示的膦氧化物系光聚合起始 劑， 【化5】 R\ 1} 4—C一 …⑽ R7 0 式中，R6、R7各自獨立地表示碳數〗〜；!〇的直鏈狀或支鏈 狀的院基、環己基、環戊基、芳基、或者被鹵素原子、院 -8- 200844660 基或烷氧基取代的芳基，或者任一者爲碳數的羰 基。 (5) —種鹼顯影型糊料組成物，其特徵係在上述（4)中 所記載的組成物中，該~般式⑴所表示的肟系光聚合起 始劑（E-1)的摻合量，少於上述一般式（IV)所表示的膦氧化 物系光聚合起始劑（E-2)的摻合量。 (6) 如（1)或（2)所記載之鹼顯影型糊料組成物，其中再 含有（G)硼酸。 (7) 如（1)或（2)所記載之鹼顯影型糊料組成物，其中再 含有（H)下述一般式（V)或一般式（VI)所表示的磷化合物， 【化6】• _ » (II!) 200844660 (In the formula, one or two R5 are represented by the following formula (I) (except that two R5s are represented by the general formula (I) and R5 is different) Case), the remaining R5 represents a hydrogen atom, a methyl group, a phenyl group or a halogen atom (except that each R5 is different).) [Chemical 4] R1 j) — C=N—0—C—R2 (1) In the formula, R1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. (3) The alkali-developing type paste composition according to (1) or (2), wherein the carboxyl group-containing resin (A) further contains (A-1) one or more radical polymerizable unsaturated groups. a carboxyl group-containing resin. (4) The alkali-developing type paste composition according to (1) or (2), further comprising (E-2) a phosphine oxide-based photopolymerization initiator represented by the following general formula (IV) , [Chemical 5] R\ 1} 4—C— (10) R7 0 where R6 and R7 each independently represent a carbon number 〖~;!〇 linear or branched chain, cyclohexyl, ring A pentyl group, an aryl group, or an aryl group substituted by a halogen atom, a -8-200844660 group or an alkoxy group, or a carbonyl group having a carbon number. (5) The alkali-developing type paste composition which is characterized by the oxime-based photopolymerization initiator (E-1) represented by the above formula (1) in the composition described in the above (4) The blending amount is less than the blending amount of the phosphine oxide-based photopolymerization initiator (E-2) represented by the above general formula (IV). (6) The alkali-developing type paste composition according to (1) or (2), which further contains (G) boric acid. (7) The alkali-developing type paste composition according to (1) or (2) further comprising (H) a phosphorus compound represented by the following general formula (V) or general formula (VI); 】
♦ (8)一種鹼顯影型糊料組成物，其特徵係塗佈乾燥上 * 述（1)至（7)中任一項所記載之組成物之塗膜的膜厚，每1 的吸光度爲0.1〜〇.8。 (9) 如（1)或（2)所記載之鹼顯影型糊料組成物，其中該 (C)無機粉末爲黑色顏料或銀粉。 (10) —種圖型之形成方法，其特徵係使用上述（1)至（9) 中任一項所記載的組成物之圖型之形成方法，其係包括： (1) 藉由活性能量線進行圖型曝光之步驟、 (2) 藉由以稀鹼水溶液進行顯影而選擇性地形成圖型 -9- 200844660 之步驟、 (3)用400〜600°C燒成之步驟。 (1 1)如（1 0)所記載之圖型之形成方法，上述活性能量 線爲雷射振動光源或燈光源。 (12) —種圖型，其特徵係藉由上述（10)或（11)中任一 • 項所記載的圖型之形方法所得到。 (13) 如（12)所記載之圖型，其中上述圖型爲導電性圖 • 型。 (14) 如（12)或（13)所記載之圖型，其中該圖型含有黑 色矩陣圖型。 (1 5 ) —種電漿顯示面板，其特徵係含有使用上述 (I) 〜（9)中任一項所記載的鹼顯影型糊料組成物所形成的圖 型。 (16) —種電漿顯不面板’其特徵係含有上述（12)至（14) 中任一項所記載的圖型。 # (17)如（1)或（2)所記載之鹼顯影型糊料組成物，其中 - 上述一般式（I)所表不的膀系光聚合起始劑（E -1)的摻合 量，爲組成物總量的0 · 1〜1 · 0質量％。 [發明之效果] 本發明的鹼顯影型糊料組成物，藉由摻合上述一般式 (II) 所表不的硫化合物’對於活性能量線具有充分的感 度，且可形成高精度的圖型。 此外’上述糊料組成物因爲對於活性能量線具有充分 -10- 200844660 的感度，故可在短時間內進行曝光，藉由縮短曝光所需要 的時間，可提高圖型的製造效率。 而且，因爲對於最大波長爲3 50nm〜420nm的活性能 量線，顯示出優異的光硬化性，故可使用雷射直接成像裝 置作爲曝光裝置’可形成彳9頼性局的圖型。 [實施發明的最佳形態] 本發明的鹼顯影型糊料組成物，其特徵係含有（A)含 羧基之樹脂、（B)玻璃基質、（C)無機粉末、（D) —分子內 具有至少一個以上的自由基聚合性不飽和基之化合物、及 (E-1)上述一般式（I)所表示的肟系光聚合起始劑、（F)上述 一般式（Π)所表示的硫化合物，相對於活性能量線顯示出 優異的光硬化性。 而且，較佳的形態，係於上述組成物中含有（G)硼 酸，可提供保存安定性優異的.組成物；此外，含有（⑴磷 化合物，可提供保存安定性優異的組成物。 以下，詳細地說明本發明的鹼顯影型糊料組成物的各 構成成分。 (A)含有羧基之樹脂 本發明的鹼顯影型糊料組成物中所含有的含有竣基之 樹脂（A)，可使用分子中含有羧基之習知慣用的樹脂化合 物。 具體而言，可列舉如下述所列舉的樹脂。 (1 )藉由使（甲基）丙烯酸等之不飽和羧酸、與除此以外 -11 - 200844660 之具有不飽和雙鍵之化合物的1種以上，進行共聚而得到 的含羧基之樹脂； (2) 藉由使（甲基）丙烯酸等之不飽和羧酸、與除此以外 之具有不飽和雙鍵之化合物的1種以上的共聚物，藉由環 氧丙基（甲基）丙烯酸酯或3,4-環氧基環己基甲基（甲基）丙 烯酸酯等之具有環氧基及不飽和雙鍵之化合物或（甲基）丙 烯酸氯化物等，經由加成乙烯性不飽和基作爲側基而得到 的含羧基之感光性樹脂； (3) 使環氧丙基（甲基）丙烯酸酯或3,4-環氧基環己基甲 基（甲基）丙烯酸酯等之具有環氧基及不飽和雙鍵之化合 物、及除此以外之具有不飽和雙鍵之化合物的共聚物，與 (甲基）丙烯酸等之不飽和羧酸進行反應，使所生成的二級 的羥基與多元酸酐反應而得到的含羧基之感光性樹脂； (4) 使馬來酸酐等之具有不飽和雙鍵之酸酐、及除此 以外之具有不飽和雙鍵之化合物之共聚物，與具有2 -經 基乙基（甲基）丙烯酸酯等之羥基及具有不飽和雙鍵之化合 物進行反應而得到的含羧基之感光性樹脂； (5) 使多官能環氧化合物與不飽和單羧酸進行反應， 使所生成的羥基與飽和或不飽和多元酸酐進行反應而得到 的含羧基之感光性樹脂； (6) 使聚乙烯醇衍生物等之含有羥基的聚合物，與飽 和或不飽和多元酸酐反應後，使所生成的羧酸與一分子中 具有環氧基與不飽和雙鍵之化合物進行反應而得到的含有 羥基的含羧基之感光性樹脂； -12- 200844660 (7)使多官能環氧化合物、及不飽和單羧酸、及一分 子中具有至少1個的醇性羥基、及與環氧基反應之醇性羥 基以外的1個的反應性基之化合物之反應生成物，與飽和 或不飽和多元酸酐進行反應而得到的含羧基之感光性樹 脂； • (8)使一分子中具有至少2個的氧雜環丁烷環之多官 能氧雜環丁烷化合物，與不飽和單羧酸進行反應，相對於 φ 所得到的改性氧雜環丁烷樹脂中的第一級羥基，使飽和或 不飽和多元酸酐進行反應而得到的含羧基之感光性樹脂； 及 (9)使多官能環氧樹脂與不飽和單羧酸進行反應後， 使多元酸酐進行反應而得到含羧酸之感光性樹脂，再與分 子中具有1個的環氧乙烷環與1個以上的乙烯性不飽和基 之化合物進行反應而得到的含羧基之感光性樹脂等，但並 不限定於此等。 • 此等的樹脂中較佳者，爲上述（2)及（3)之分子中具有 . 乙烯性不飽和雙鍵之含羧基之感光性樹脂，由光硬化性、 硬化塗膜特性方面而言較佳。 再者，本說明書中，（甲基）丙烯酸酯之意，係丙烯酸 酯及甲基丙烯酸酯及此等混合物的總稱用語，關於其他的 類似表現亦相同。 如上述的含羧酸之樹脂（A)，因爲於骨架（backbone)· 聚合物的側鏈上具有多數的游離的羧基，故可藉由稀鹼水 溶液進行顯影。 -13- 200844660 此外，上述含羧酸之樹脂（A)的酸價，較佳爲在 40〜200mgKOH/g的範圍，更佳·爲在45〜1 20mgKOH/g的範 圍。含羧基之樹脂的酸價低於40mgKOH/g，則鹼顯影變 困難而較不佳；另一方面，超過200mgKOH/g，因爲顯影 液使曝光部的溶解增強，而使線條變得比所需要的更細， • 依情況的不同，會有曝光部與未曝光部在未區分下被顯影 , 液溶解剝離，而使正常的阻焊圖型的描繪變困難，故較不 • 佳。 此外，上述含羧基之樹脂（A)的重量平均分子量，依 樹脂骨架而有所不同，但一般爲2,000〜1 50,000，更佳爲 5，000〜100, 〇〇〇的範圍。重量平均分子量低於2,000，則會 有不黏（taek free)性能變差的狀況，以及曝光後的塗膜的 耐濕性變差而顯影時發生膜減少，解析度大幅度地變差的 狀況；另一方面，重量平均分子量超過1 50,000，則會有 顯影性顯著地變差的狀況，以及貯藏安定性變差的狀況。 # 如此的含羧基之樹脂（A)的摻合量，使用（C-1)黑色顏 . 料作爲（C)時，全組成物中，較佳爲10〜80質量％，更佳 ^ 爲15〜50質量％的範圍；此外使用使用（C-2)銀粉作爲（C) 時，全組成物中，較佳爲2〜50質量％，更佳爲4〜30質量 %的範圍。摻合量太少，則因爲塗膜強度降低而較不佳； 另一方面，摻合太多，則因爲塗佈性降低而較不佳。 (B)玻璃基質 本發明的鹼顯影型糊料組成物中所使用的玻璃基質 (B)，可使用軟化點爲3 00〜600°C的低熔點玻璃基質，以 -14- 200844660 氧化鉛、氧化鉍、或氧化鋅爲主成份者較適用。此外，由 解像度的觀點而言，使用平均粒徑20μιη以下者爲佳，較 佳爲使用5 μπι以下者。以氧化鉛爲主成份之玻璃粉末的 較佳例子’可列舉以氧化物基準的質量％而言，具有PbO 爲 48 〜82%、B2〇3 爲 〇·5 〜22%、Si02 爲 3 〜32%、Al2〇3 爲 0〜12%、BaO 爲 〇〜1〇%、ZnO 爲 0〜15%、Ti02 爲 0 〜2.5%、Bi203爲〇〜25%的組成，軟化點爲420〜590°C 之非結晶性基質。 此外，以氧化鉍作爲主成份之玻璃粉末的較佳例子， 可列舉以氧化物基準的質量％而言，具有Bi203爲35〜 88%、B2〇3 爲 5〜30%、Si02 爲 0〜20%、Al2〇3 爲 0〜 5%、BaO爲1〜25%、ZnO爲1〜20%的組成，軟化點爲 420〜590°C之非結晶性基質。 而且，以氧化鋅作爲主成份之玻璃粉末的較佳例子， 可列舉以氧化物基準的質量％而言，具有ZnO爲25〜 60%、K2〇 爲 2 〜15%、Β2〇3 爲 25 〜45%、Si02 爲 1 〜 7%、Al2〇3 爲 0〜10%、BaO 爲 0〜20%、MgO 爲 0〜10% 的組成，軟化點爲420〜5 90°C之非結晶性基質。 如此的玻璃基質的摻合量，全組成物中較佳爲1〜2 0 質量％，更佳爲2〜1 0質量％。摻合量太少則與基材的黏 附性差，摻合量太多則會有產生與組成物的增黏或凝膠化 之虞，此外，形成導電性圖型時，會有帶來燒成後的比電 阻値的上昇之虞，任何一方皆不佳。 (C)無機粉末 -15- 200844660 本發明的鹼顯影型糊料組成物所使用的（c)無機粉 末’包括黑色顔料（C-1)或銀粉（c-2)。 黑色顔料（C-1) 本發明的鹼顯影型糊料組成物所使用的成分（c)的黑 色顔料（C-l)，Cu、Fe、Cr、Mn、Co、Ru、La 等之單獨 的金屬氧化物及/或金屬元素2種以上所成的複合氧化物 可適用’其平均粒徑，由解析度的觀點而言，較佳爲使用 10 μιη以下，更佳爲使用2.5 μιη以下者。另一方面，由黑 色度的觀點而言，較適合者爲平均粒徑丨·〇μιη以下，更適 合者爲〇 · 6 μ m以下者。 如此的黑色顔料’特別佳爲使用比表面積在1 . 〇〜 20m2/g的範圍之四氧化三鈷（c〇3〇4)微粒子，其理由係因 爲此比表面積低於1.0m2/g，則經由曝光的圖型形成的精 度降低’且很難得到線邊緣的直線性、或充分程度黑色的 燒成皮膜。另一方面，超過20m2/g，則因爲粒子的表面 積變得太大而顯影時易產生下切（undercut)。 此外’黑色顔料（C-1)的摻合量，係相對於上述含羧 基之樹脂（A)每1〇〇質量份爲10〜100質量份的範圍較爲 適當。太少則燒成後無法得到充分程度的黑色而較不佳； 另一方面’太多則因爲光穿透性降低、易產生下切而較不 佳。 銀粉（C-2) 本發明的鹼顯影型糊料組成物所使用的成分（C)的銀 粉（C-2) ’係對糊料賦予導電性者，可使用習知慣用的銀 -16- 200844660 粉，但使用X線解析圖型中Ag(l 1 1)面波峰的半寬値顯示 出0.1 5以上者，較佳爲使用顯示出0. 1 9以上的値者這一 點，但由燒成性方面而較佳。此半寬値低於0.1 5的銀粉 (C-2)，則因爲銀粉的結晶化度高、不易引起粒子間的燒 結，而於620 °C以下的燒成溫度則電阻値不下降而較不 佳。此外，該半寬値爲1.0以下爲佳，半寬値超過1.0， 則因爲會有銀粉末的結晶化度降低、粒子間的黏合過度進 行，而線產生不規則的表面波紋或歪扭之虞，故較不佳。 如此的銀粉（C-2)，一般而言，藉由霧化法或化學還 原法等之方法而被製造。霧化法係將被熔融的銀藉由氣 體、水等的流體進行噴霧而得到銀粉末之方法，易得到球 狀的粒子，且量產性優異。化學還原法係將水溶性銀鹽使 用還原劑使其化學反應後得到銀粉末之方法，具體而言， 係使用硝酸銀作爲水溶性銀鹽，使用苛性鹼或銨鹽、肼等 之鹼作爲還原劑，析出金屬銀，接著將所得到的銀淤漿進 行水洗、乾燥後得到銀粉末之方法。 如此作法所得到的銀粉（C-2)，可使用球狀、片狀、 樹狀等各種形狀者，但若考慮光特性或分散性則使用球狀 者爲特別佳。此外，此銀粉（C-2)，係使用以電子顯微鏡 (SEM)用1 0,000倍進行觀察的隨機選擇的1〇個銀粉末的 平均粒徑爲0.1〜5μπι較佳，更佳爲使用〇·4〜2·0μπι大小 者。此平均粒徑低於〇 . 1 μιη時，光的穿透性變差、且很難 描繪高精細的圖型，另一方面，平均粒徑超過5 時， 因爲很難得到線邊緣的直線性而較不佳。再者’較佳爲使 -17- 200844660 用micro track所測量的平均粒徑爲0.5〜3.5 μηι大小者。 而且，此銀粉（C-2)，使用比表面積爲0.01〜2.〇m2/g 者爲佳，較佳爲使用〇·1〜1 .0m2/g者。此比表面積低於 0.01 m2/g時’保存時易引起沈降；另一方面，比表面積超 過2· 0m2/g時，因爲吸油量大而糊料的流動性受損，故較 不佳。 如此的銀粉（C-2)的摻合量，相對於鹼顯影型糊料組 成物100質量份，爲50〜90質量份較適當。銀粉的摻合 量太少，則由該相關的糊料所得到的導電性圖型無法得到 充分的導電性；另一方面，太多則因爲與基材的黏附性變 差而較不佳。 (D)—分子內具有至少一個以上的自由基聚合性不飽 和基之化合物 - 本發明所使用的上述一分子內具有至少一個以上的自 由基聚合性不飽和基之化合物（D)，可2 -羥基乙基丙烯酸 酯、2 -羥基丙基丙烯酸酯、季戊四醇三丙烯酸酯、二季戊 四醇五丙烯酸酯等之羥基烷基丙烯酸酯類；乙二醇、甲氧 基四乙二醇、聚乙二醇、丙二醇等之二醇的單或二丙烯酸 酯類；N，N-二甲基丙烯醯胺、N·羥甲基丙烯醯胺、N,N-二 甲基胺基丙基丙烯醯胺等之丙烯醯胺類；N，N-二甲基胺基 乙基丙烯酸酯、N，N-二甲基胺基丙基丙烯酸酯等之胺基烷 基丙烯酸酯類；己二醇、三羥甲基丙烷、季戊四醇、二季 戊四醇、參-羥基乙基三聚異氰酸酯等之多元醇或此等的 環氧乙烷加成物或環氧丙烷加成物等之多元丙烯酸酯類；(8) An alkali-developing type paste composition, which is characterized in that the film thickness of the coating film of the composition according to any one of (1) to (7) is applied, and the absorbance per one is 0.1~〇.8. (9) The alkali-developing type paste composition according to (1) or (2), wherein the (C) inorganic powder is a black pigment or a silver powder. (10) A method of forming a pattern, wherein the pattern forming method of the composition according to any one of the above (1) to (9), comprising: (1) by active energy The step of performing pattern exposure on the line, (2) the step of selectively forming the pattern of -9-200844660 by development with a dilute aqueous alkali solution, and (3) the step of firing at 400 to 600 °C. (1) The method for forming a pattern according to (10), wherein the active energy ray is a laser vibration light source or a light source. (12) A pattern obtained by the method of the pattern described in any one of the above items (10) or (11). (13) The pattern as described in (12), wherein the pattern is a conductivity pattern. (14) The pattern as described in (12) or (13), wherein the pattern contains a black matrix pattern. (1) A plasma display panel, which is characterized in that the alkali-developing paste composition according to any one of the above (1) to (9) is used. (16) A plasma display panel is characterized in that the pattern described in any one of the above (12) to (14) is contained. (A) The alkali-developing type paste composition according to (1) or (2), wherein - the blending of the above-mentioned general photopolymerization initiator (E-1) represented by the general formula (I) The amount is 0 · 1 to 1 · 0 mass % of the total amount of the composition. [Effects of the Invention] The alkali-developing type paste composition of the present invention has a sufficient sensitivity to the active energy ray by blending the sulfur compound represented by the above general formula (II), and can form a highly accurate pattern. . Further, since the paste composition has a sensitivity of -10-200844660 to the active energy ray, exposure can be performed in a short time, and the manufacturing efficiency of the pattern can be improved by shortening the time required for exposure. Further, since the active energy line having a maximum wavelength of 3 50 nm to 420 nm exhibits excellent photocurability, a laser direct imaging device can be used as an exposure device to form a pattern. [Best Mode for Carrying Out the Invention] The alkali-developing type paste composition of the present invention is characterized by comprising (A) a carboxyl group-containing resin, (B) a glass substrate, (C) an inorganic powder, and (D) - having intramolecular (A-1) a compound represented by the above formula (I) The compound exhibits excellent photocurability with respect to the active energy ray. Further, in a preferred embodiment, the composition contains (G) boric acid, and provides a composition excellent in storage stability; and (1) a phosphorus compound, which provides a composition excellent in storage stability. The constituent components of the alkali-developing paste composition of the present invention are described in detail. (A) Carboxyl group-containing resin The mercapto group-containing resin (A) contained in the alkali developing type paste composition of the present invention can be used. A resin compound which is a conventionally used resin having a carboxyl group in the molecule. Specific examples thereof include the resins listed below. (1) By using an unsaturated carboxylic acid such as (meth)acrylic acid or the like, 200844660 A carboxyl group-containing resin obtained by copolymerizing one or more compounds having an unsaturated double bond; (2) an unsaturated carboxylic acid such as (meth)acrylic acid or the like having an unsaturated state One or more kinds of copolymers of a compound having a double bond, having an epoxy group such as a glycidyl (meth) acrylate or a 3,4-epoxycyclohexylmethyl (meth) acrylate, and a compound that saturates a double bond or a carboxyl group-containing photosensitive resin obtained by adding an ethylenically unsaturated group as a pendant group, such as methyl acrylate chloride; (3) making epoxy propyl (meth) acrylate or 3, 4-epoxy a compound having an epoxy group and an unsaturated double bond, such as a cyclohexylmethyl (meth) acrylate, and a copolymer of a compound having an unsaturated double bond, and a (meth)acrylic acid or the like a carboxyl group-containing photosensitive resin obtained by reacting a saturated carboxylic acid to react a secondary hydroxyl group formed with a polybasic acid anhydride; (4) an acid anhydride having an unsaturated double bond such as maleic anhydride, and the like a copolymer containing a compound having an unsaturated double bond, a carboxyl group-containing photosensitive resin obtained by reacting a compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate or a compound having an unsaturated double bond; (5) a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid to react a generated hydroxyl group with a saturated or unsaturated polybasic acid anhydride; (6) a polyvinyl alcohol derivative or the like Hydroxyl a hydroxyl group-containing carboxyl group-containing photosensitive resin obtained by reacting a produced carboxylic acid with a compound having an epoxy group and an unsaturated double bond in a molecule after reacting with a saturated or unsaturated polybasic acid anhydride; -12- 200844660 (7) Reaction of a polyfunctional epoxy compound and an unsaturated monocarboxylic acid, and one of an alcoholic hydroxyl group having at least one molecule and an alcoholic hydroxyl group reactive with an epoxy group a reaction product of a compound based on a compound, a carboxyl group-containing photosensitive resin obtained by reacting with a saturated or unsaturated polybasic acid anhydride; (8) a polyfunctional compound having at least two oxetane rings in one molecule An oxetane compound, which is reacted with an unsaturated monocarboxylic acid, and which is obtained by reacting a saturated or unsaturated polybasic acid anhydride with respect to a first-order hydroxyl group in the modified oxetane resin obtained by φ a photosensitive resin of a carboxyl group; and (9) reacting a polyfunctional epoxy resin with an unsaturated monocarboxylic acid, and then reacting the polybasic acid anhydride to obtain a carboxylic acid-containing photosensitive resin, and having one ring in the molecule Oxygen B The carboxyl group-containing photosensitive resin obtained by reacting an alkane ring with a compound of one or more ethylenically unsaturated groups, etc., is not limited thereto. The preferred one of the resins is a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecules of the above (2) and (3), in terms of photocurability and cured film properties. Preferably. Further, in the present specification, the meaning of (meth) acrylate is the general term for acrylate and methacrylate and the like, and the other similar expressions are also the same. The carboxylic acid-containing resin (A) as described above can be developed by a dilute aqueous alkali solution because it has a large number of free carboxyl groups in the side chain of the backbone/polymer. Further, the acid value of the carboxylic acid-containing resin (A) is preferably in the range of 40 to 200 mgKOH/g, more preferably in the range of 45 to 1 20 mgKOH/g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, the alkali development becomes difficult and less preferable; on the other hand, it exceeds 200 mgKOH/g because the developer enhances the dissolution of the exposed portion, and the line becomes more desirable than necessary. It is finer. • Depending on the situation, the exposed portion and the unexposed portion are developed without distinction, and the liquid dissolves and peels off, making the drawing of the normal solder resist pattern difficult, so it is less preferable. Further, the weight average molecular weight of the carboxyl group-containing resin (A) varies depending on the resin skeleton, but is usually in the range of 2,000 to 150,000, more preferably 5,000 to 100, Å. When the weight average molecular weight is less than 2,000, the taek free performance may be deteriorated, and the moisture resistance of the coating film after exposure may be deteriorated, and the film may be reduced during development, and the resolution may be greatly deteriorated. On the other hand, when the weight average molecular weight exceeds 150,000, the developability is remarkably deteriorated, and the storage stability is deteriorated. # The blending amount of the carboxyl group-containing resin (A), when (C-1) is used as the (C), the total composition is preferably 10 to 80% by mass, more preferably 15 In the range of ～50% by mass or more, when (C-2) silver powder is used as the (C), the total composition is preferably in the range of 2 to 50% by mass, more preferably 4 to 30% by mass. If the blending amount is too small, it is less preferable because the coating film strength is lowered. On the other hand, if the blending is too much, it is less preferable because the coatability is lowered. (B) Glass substrate The glass substrate (B) used in the alkali-developing paste composition of the present invention may be a low-melting glass substrate having a softening point of 300 to 600 ° C, and lead oxide of -14-200844660, It is more suitable for cerium oxide or zinc oxide as the main component. Further, from the viewpoint of the resolution, those having an average particle diameter of 20 μm or less are preferably used, and those having a particle diameter of 5 μm or less are preferably used. A preferred example of the glass powder containing lead oxide as a main component is exemplified by the mass % of the oxide, which has a PbO of 48 to 82%, a B2〇3 of 〇·5 to 22%, and a SiO 2 of 3 to 32. %, Al2〇3 is 0~12%, BaO is 〇~1〇%, ZnO is 0~15%, Ti02 is 0~2.5%, Bi203 is 〇~25%, and the softening point is 420~590°C. A non-crystalline matrix. Further, preferred examples of the glass powder containing cerium oxide as a main component include, by mass% based on the oxide, 35 to 88% of Bi203, 5 to 30% of B2〇3, and 0 to 20% of SiO 2 . %, Al2〇3 is 0 to 5%, BaO is 1 to 25%, ZnO is 1 to 20%, and the softening point is 420 to 590 ° C. Further, preferred examples of the glass powder containing zinc oxide as a main component include ZnO of 25 to 60%, K2 〇 of 2 to 15%, and Β2〇3 of 25 〜 by mass% based on the oxide. 45%, SiO 2 is 1 to 7%, Al 2 〇 3 is 0 to 10%, BaO is 0 to 20%, MgO is 0 to 10%, and the softening point is 420 to 5 90 ° C. The blending amount of such a glass substrate is preferably from 1 to 20% by mass, more preferably from 2 to 10% by mass, based on the total composition. If the blending amount is too small, the adhesion to the substrate is poor. If the blending amount is too large, the composition may be sticky or gelled. Further, when the conductive pattern is formed, the firing may occur. After the rise of the specific resistance 値, neither party is poor. (C) Inorganic powder -15- 200844660 The (c) inorganic powder used in the alkali-developing type paste composition of the present invention 'includes a black pigment (C-1) or a silver powder (c-2). Black pigment (C-1) The black pigment (Cl) of the component (c) used in the alkali-developing paste composition of the present invention, and the individual metal oxidation of Cu, Fe, Cr, Mn, Co, Ru, La, etc. The composite oxide formed of two or more kinds of the compound and/or the metal element is applicable to the average particle diameter thereof, and from the viewpoint of the resolution, it is preferably 10 μm or less, more preferably 2.5 μm or less. On the other hand, from the viewpoint of blackness, it is more suitable for the average particle diameter 丨·〇μιη or less, and more suitable for 〇·6 μm or less. Such a black pigment is particularly preferably used in the range of .~20 m 2 /g of tricobalt tetroxide (c 〇 3 〇 4) fine particles because the specific surface area is less than 1.0 m 2 /g, then exposure The accuracy of pattern formation is reduced, and it is difficult to obtain linearity of the edge of the line or a sufficiently black burnt film. On the other hand, when it exceeds 20 m2/g, since the surface area of the particles becomes too large, undercut is liable to occur during development. Further, the blending amount of the black pigment (C-1) is preferably in the range of 10 to 100 parts by mass per 1 part by mass of the above-mentioned carboxyl group-containing resin (A). Too little is not good enough to obtain a sufficient degree of black after firing; on the other hand, 'too much" is less preferable because the light transmittance is lowered and the undercut is liable to occur. Silver powder (C-2) The silver powder (C-2) of the component (C) used in the alkali-developing paste composition of the present invention is a conventionally used silver-16- 200844660 powder, but the half-width Ag of the Ag(l 1 1) surface peak in the X-ray analysis pattern is 0.1 5 or more, and it is preferable to use the one that shows 0.1 or more, but by burning It is better in terms of adulthood. When the silver powder (C-2) having a half width of less than 0.15 is high, the degree of crystallization of the silver powder is high, and it is difficult to cause sintering between the particles. However, at a firing temperature of 620 ° C or lower, the resistance 値 does not decrease and is less. good. Further, the half width 値 is preferably 1.0 or less, and the half width 値 is more than 1.0, because the degree of crystallization of the silver powder is lowered, the adhesion between the particles is excessively performed, and the line is irregularly corrugated or twisted. Therefore, it is not good. Such a silver powder (C-2) is generally produced by a method such as an atomization method or a chemical reduction method. The atomization method is a method in which molten silver is sprayed by a fluid such as a gas or water to obtain a silver powder, and spherical particles are easily obtained, and the mass productivity is excellent. The chemical reduction method is a method in which a water-soluble silver salt is chemically reacted with a reducing agent to obtain a silver powder. Specifically, silver nitrate is used as a water-soluble silver salt, and a caustic or ammonium salt or a base such as hydrazine is used as a reducing agent. A method of precipitating metallic silver, followed by washing the obtained silver slurry with water to obtain a silver powder. The silver powder (C-2) obtained in this manner can be used in various shapes such as a spherical shape, a sheet shape, and a dendritic shape. However, it is particularly preferable to use a spherical shape in consideration of light characteristics or dispersibility. Further, the silver powder (C-2) is preferably used in an average particle diameter of 0.1 to 5 μm, which is preferably 1 to 5 μm, which is observed by an electron microscope (SEM) at a ratio of 10,000 times, more preferably 〇· 4~2·0μπι size. When the average particle diameter is less than 〇. 1 μιη, the light transmittance is deteriorated, and it is difficult to draw a high-definition pattern. On the other hand, when the average particle diameter exceeds 5, it is difficult to obtain the linearity of the line edge. It is not good. Further, it is preferable that the average particle diameter measured by the micro track of -17-200844660 is 0.5 to 3.5 μηι. Further, the silver powder (C-2) is preferably a specific surface area of 0.01 to 2. 〇m2/g, preferably 〇·1 to 1.0 m2/g. When the specific surface area is less than 0.01 m2/g, it is easy to cause sedimentation during storage. On the other hand, when the specific surface area exceeds 2.0 m2/g, the fluidity of the paste is impaired because of the large oil absorption, which is not preferable. The blending amount of the silver powder (C-2) is preferably 50 to 90 parts by mass based on 100 parts by mass of the alkali developing type paste composition. When the amount of the silver powder blended is too small, the conductive pattern obtained from the related paste cannot obtain sufficient conductivity; on the other hand, too much is less preferable because the adhesion to the substrate is deteriorated. (D) - a compound having at least one or more radically polymerizable unsaturated groups in the molecule - a compound (D) having at least one or more radical polymerizable unsaturated groups in the above-mentioned one molecule used in the present invention, which is 2 Hydroxyalkyl acrylates such as -hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc.; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol And mono or diacrylates of diols such as propylene glycol; N,N-dimethyl acrylamide, N-methylol acrylamide, N,N-dimethylaminopropyl acrylamide, etc. Acrylamides; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate; hexanediol, trimethylol a polyhydric alcohol such as propane, pentaerythritol, dipentaerythritol, cis-hydroxyethyl trimer isocyanate or the like, or an ethylene oxide adduct or a propylene oxide adduct or the like;
-18- 200844660 苯氧基丙烯酸酯、雙酚A二丙烯酸酯、及此等的苯酚類 之環氧乙烷加成物或環氧丙烷加成物等之丙烯酸酯類；甘 油二環氧丙基醚、甘油三環氧丙基醚、三羥甲基丙烷三環 氧丙基醚、三環氧丙基三聚異氰酸酯等之環氧丙基醚的丙 烯酸酯類；上述羥基烷基丙烯酸酯的異氰酸酯改性物之多 官能或單官能聚尿烷丙烯酸酯；及三聚氰胺丙烯酸酯、及 對應於上述丙烯酸酯之各（甲基）丙烯酸酯類、或者2-羥基 乙基丙烯酸酯、2-羥基丙基丙烯酸酯、季戊四醇三丙烯酸 酯、二季戊四醇五丙烯酸酯等之羥基烷基丙烯酸酯類；乙 二醇、甲氧基四乙二醇、聚乙二醇、丙二醇等之二醇的單 或二丙烯酸酯類；N，N-二甲基丙烯醯胺、N-羥甲基丙烯醯 胺、N，N-二甲基胺基丙基丙烯醯胺等的丙烯醯胺類；N，N-二甲基胺基乙基丙烯酸酯、N，N-二甲基胺基丙基丙烯酸酯 等之胺基烷基丙烯酸酯類；己二醇、三羥甲基丙烷、季戊 四醇、二季戊四醇、參-羥基乙基三聚異氰酸酯等之多元 醇或此等的環氧乙烷加成物或環氧丙烷加成物等之多価丙 烯酸酯類；苯氧基丙烯酸酯、雙酚A二丙烯酸酯、及此等 的苯酚類的環氧乙烷加成物或環氧丙烷加成物等之丙烯酸 酯類；甘油二環氧丙基醚、甘油三環氧丙基醚、三羥甲基 丙烷三環氧丙基醚、三環氧丙基三聚異氰酸酯等之環氧丙 基醚的丙烯酸酯類；上述羥基烷基丙烯酸酯的異氰酸酯改 性物之多官能或單官能聚尿烷丙烯酸酯；及三聚氰胺丙烯 酸酯、或對應於上述丙烯酸酯之各（甲基）丙烯酸酯類等， 此等可單獨使用或組合2種以上使用。此等之中，特別是 -19- 200844660 一分子内具有至少二個以上的自由基聚合性不飽和基之化 合物，例如季戊四醇三丙烯酸酯、二季戊四醇六丙嫌酸酯 等，因爲光硬化性優異而較佳。 再者，以下有將此化合物簡稱爲聚合性單體的情況。-18- 200844660 Acrylates of phenoxy acrylate, bisphenol A diacrylate, and such phenolic oxirane adducts or propylene oxide adducts; glycerol diepoxypropyl Acrylates of epoxy propyl ethers such as ether, glycerol triepoxypropyl ether, trimethylolpropane triepoxypropyl ether, triepoxypropyl trimer isocyanate; isocyanates of the above hydroxyalkyl acrylates a modified polyfunctional or monofunctional polyurethane acrylate; and melamine acrylate, and each (meth) acrylate corresponding to the above acrylate, or 2-hydroxyethyl acrylate, 2-hydroxypropyl a hydroxyalkyl acrylate such as acrylate, pentaerythritol triacrylate or dipentaerythritol pentaacrylate; a mono or diacrylate of a glycol such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol or propylene glycol; Alkylamines such as N,N-dimethylpropenamide, N-methylol acrylamide, N,N-dimethylaminopropyl acrylamide; N,N-dimethyl Aminoethyl acrylate, N,N-dimethylaminopropyl acrylate, etc. Aminoalkyl acrylates; polyols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, cis-hydroxyethyltrimeric isocyanate or the like or such ethylene oxide adducts or epoxies a polyhydric acrylate such as a propane adduct; an acrylate such as a phenoxy acrylate, a bisphenol A diacrylate, or an oxirane ethylene oxide adduct or a propylene oxide adduct; An acrylate of a epoxidized propyl ether such as glycerol diepoxypropyl ether, glycerol triepoxypropyl ether, trimethylolpropane triepoxypropyl ether or triepoxypropyl trimer isocyanate; a polyfunctional or monofunctional polyurethane acrylate of an isocyanate modified product of the above hydroxyalkyl acrylate; and a melamine acrylate or a (meth) acrylate corresponding to the above acrylate, etc., which may be used alone Use two or more types in combination. Among these, in particular, -19-200844660 has at least two or more radically polymerizable unsaturated groups in one molecule, such as pentaerythritol triacrylate, dipentaerythritol hexa-propyl acrylate, etc., because of excellent photocurability. Better. Further, the case where this compound is simply referred to as a polymerizable monomer will be described below.
如此的一分子内具有至少一個以上的自由基聚合性不 飽和基（D)的摻合量，相對於上述的含羧基之樹脂（a)1 00 質量份，較佳爲5〜100質量份，更佳爲1〇〜70質量份的 比例。上述摻合量太少，則因爲光硬化性降低，活性能量 線照射後的鹼顯影，而造成圖型形成變困難，故較不佳 好；另一方面，太多則因爲對鹼水溶液的溶解性降低，而 使塗膜變脆，故較不佳。 (E-1)上述一般式（I)所表示的肟系光聚合起始劑的具 體例子，可列舉1，2-辛二酮-1-[4-(苯基硫代）-2-(0-苯甲醯 肟）]、乙酮- 乙基- 6·(2-甲基苯甲醯）-9H-昨唑-3-基]-1- (〇_乙醯肟）、及下記一般式（VII)所表示之The blending amount of at least one or more radically polymerizable unsaturated groups (D) in such a molecule is preferably from 5 to 100 parts by mass based on 100 parts by mass of the above carboxyl group-containing resin (a). More preferably, the ratio is from 1 70 to 70 parts by mass. If the amount of the above-mentioned blending is too small, the photohardenability is lowered, and the alkali after development by the active energy ray is difficult to form, which is difficult to form. On the other hand, too much is dissolved in the aqueous alkali solution. The property is lowered, and the coating film becomes brittle, so it is not preferable. (E-1) Specific examples of the oxime-based photopolymerization initiator represented by the above general formula (I) include 1,2-octanedione-1-[4-(phenylthio)-2-( 0-benzhydrazide)], ethyl ketone-ethyl-6(2-methylbenzhydrazide)-9H-oxazolyl-3-yl]-1-(〇_乙醯肟), and the following general Expressed by formula (VII)
化77
Ijlj—0—jj—CH3 C\ ο …（vu) 2-(乙醯氧基亞胺基甲基）噻噸-9-酮。此等之中，以上述式 (VII)所表示的化合物、2-(乙醯氧基亞胺基甲基）噻噸-9-酮爲特別佳，市售品有Ciba Specialty chemicals公司製 -20- 200844660 的 CGI-325 〇 如此的肟系光聚合起始劑（Ε-1)的摻合量，(C)使用（C-1)黑色顔料時，相對於上述含羧基之樹脂（A) 1〇〇質量份’ 較佳爲 〇·〇1〜20質量份，更佳爲 〇·〇1〜5質量份的比 例；此外，（C)使用（C-2)銀粉時，爲組成物整體的0.1〜 1.0質量％的比例較佳。又此情況下，以上述含羧基之樹 脂（Α)100質量份爲基準之肟系光聚合起始劑（Ε-1)的摻合 量’雖然依玻璃基質、銀粉、一分子中具有至少一^個以上 的自由基聚合性不飽和基之化合物、及有機溶劑的摻合量 而適當的範圍有所變化，但大槪是相對於上述含羧基之樹 脂（A) 100質量份，爲0.01〜20質量份‘，較佳爲0.05〜10 質量份，更佳爲0.5〜5.0質量份的比例。肟系光聚合起 始劑（E-1)的摻合量，相對於上述含羧基之樹脂（A)100質 量份，太少則因爲無法得到充分的光硬化性而較不佳；另 一方面，太多則因爲厚膜硬化性降低，造成製品的成本上 昇，故較不佳。 本發明的鹼顯影型糊料組成物，爲了更高感度化，摻 合含有上述一般式（IV)所表示的構造之膦氧化物系光聚合 起始劑（E-2)較佳。 如此的膦氧化物系光聚合起始劑（E-2)，可列舉2,4,6-三甲基苯甲醯二苯基膦氧化物、雙（2，4,6-三甲基苯甲醯）-苯基膦氧化物、雙（2,6-二甲氧基苯甲醯）-2,4,4-三甲基-戊 基膦氧化物等。 如此的膦氧化物系光聚合起始劑（E-2)的摻合量，相 200844660 對於上述含羧基之樹脂（A) 100質量份，爲60質量份以 下，較佳爲5 0質量份以下的比例。膦氧化物系光聚合起 始劑（E-2)的摻合量，超過60質量份時，因爲厚膜硬化性 降低，造成製品的成本上昇，故較不佳。 此外，上述一般式（I)所表示的肟系光聚合起始劑（E-1) 的摻合量，至少與上述一般式（IV)所表示的膦氧化物系光 聚合起始劑（E-2)的摻合量等量或更少，由得到高感度且 厚膜硬化性而言較佳。 本發明的鹼顯影型糊料組成物，再必要時可倂用習知 慣用的光聚合起始劑，具體而言，可列舉苯偶因、苯偶因 甲基醚、苯偶因乙基醚、苯偶因異丙基醚等之苯偶因與苯 偶因烷基醚類；苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、 2,2-二乙氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙 酮、1，1-二氯苯乙酮等之苯乙酮類；2-甲基-卜[4-(甲基硫 代）苯基]-2 -嗎啉代丙烷-1 -酮、2 ·苄基-2 -二甲基胺基-1 · (4 -嗎啉代苯基）-丁酮-1等之胺基苯乙酮類；2 -甲基蒽醌、2-乙基蒽醌、2-第三-丁基蒽醌、1-氯蒽醌等的蒽醌類；2,4-二甲基噻噸酮、2，4-二乙基噻噸酮、2-氯噻噸酮、2,4-二 異丙基噻噸酮等之噻噸酮類；苯乙酮二甲基縮酮、苄基二 甲基縮酮等之縮酮類；二苯甲酮等之二苯甲酮類；或咕噸 酮類；（2,6-二甲氧基苯甲醯）-254,4-戊基膦氧化物、雙 (2,4,6-三甲基苯甲醯）-苯基膦氧化物、2,4,6_三甲基苯甲 醯二苯基膦氧化物、乙基_2,4,6-三甲基苯甲醯苯基亞膦酸 酯等之膦氧化物類等。特別是倂用2,4-二甲基噻噸酮、Ijlj—0—jj—CH3 C\ ο (vu) 2-(ethenoxyiminomethyl) thioxan-9-one. Among these, the compound represented by the above formula (VII) and 2-(ethyloxyiminomethyl)thioxanthene-9-one are particularly preferred, and commercially available products are manufactured by Ciba Specialty Chemicals Co., Ltd.-20 - 200844660 CGI-325 掺 such a fluorene photopolymerization initiator (Ε-1) blending amount, (C) when (C-1) black pigment is used, relative to the above carboxyl group-containing resin (A) 1 The mass part ' is preferably 1 to 20 parts by mass of 〇·〇, more preferably 1 to 5 parts by mass of 〇·〇; and (C) when (C-2) silver powder is used, the composition is as a whole. A ratio of 0.1 to 1.0% by mass is preferred. In this case, the blending amount of the fluorene-based photopolymerization initiator (Ε-1) based on 100 parts by mass of the carboxyl group-containing resin (Α) is at least one based on the glass substrate, the silver powder, and one molecule. The range of the amount of the compound of the radically polymerizable unsaturated group and the amount of the organic solvent to be blended varies depending on the amount of the compound containing the carboxyl group-containing resin (A), and is 0.01% by mass based on 100 parts by mass of the carboxyl group-containing resin (A). 20 parts by mass ', preferably 0.05 to 10 parts by mass, more preferably 0.5 to 5.0 parts by mass. On the other hand, when the amount of the fluorene-based photopolymerization initiator (E-1) is too small, 100 parts by mass of the carboxyl group-containing resin (A) is too small, and it is not preferable because sufficient photocurability cannot be obtained. Too much, because the thick film hardenability is reduced, the cost of the product is increased, so it is not good. In the alkali-developing type paste composition of the present invention, it is preferred to incorporate a phosphine oxide-based photopolymerization initiator (E-2) having a structure represented by the above general formula (IV) for higher sensitivity. Such a phosphine oxide photopolymerization initiator (E-2) may, for example, be 2,4,6-trimethylbenzimidium diphenylphosphine oxide or bis(2,4,6-trimethylbenzene). Formamidine)-phenylphosphine oxide, bis(2,6-dimethoxybenzhydrazide)-2,4,4-trimethyl-pentylphosphine oxide, and the like. The blending amount of the phosphine oxide-based photopolymerization initiator (E-2), phase 200844660, is 60 parts by mass or less, preferably 50 parts by mass or less, based on 100 parts by mass of the carboxyl group-containing resin (A). proportion. When the amount of the phosphine oxide photopolymerization initiator (E-2) is more than 60 parts by mass, the thick film hardenability is lowered, and the cost of the product is increased, which is not preferable. Further, the blending amount of the oxime-based photopolymerization initiator (E-1) represented by the above general formula (I) is at least the phosphine-based photopolymerization initiator (E) represented by the above general formula (IV) The blending amount of -2) is equivalent or less, and is preferable from the viewpoint of obtaining high sensitivity and thick film hardenability. The alkali-developing type paste composition of the present invention may, if necessary, be a conventional photopolymerization initiator, and specific examples thereof include benzoin, benzoin methyl ether, and benzoin ethyl ether. Benzoin and benzoin alkyl ethers such as benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy Acetophenones such as benzyl-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc.; 2-methyl-bu [ 4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2 ·benzyl-2 -dimethylamino-1 · (4-morpholinophenyl)-butanone -1 amino acetophenones; 2 -methyl hydrazine, 2-ethyl hydrazine, 2-tri-butyl hydrazine, 1-chloroindole, etc.; 2,4- Thiophenones such as dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; acetophenone dimethyl condensate a ketal such as a ketone or a benzyl dimethyl ketal; a benzophenone such as a benzophenone; or a xanthone; (2,6-dimethoxybenzidine)-254,4 -amylphosphine oxide, bis(2,4,6-trimethylbenzhydrazide)-phenylphosphine Compounds, 2,4,6_ trimethyl benzoyl diphenyl phosphine oxide, ethyl _2,4,6- trimethyl benzoyl phenyl phosphonate, etc. phosphine oxide and the like. Especially with 2,4-dimethylthioxanthone,
-S -22- 200844660 2,4-二乙基噻噸酮、2-氯噻噸酮、2，4-二異丙基噻噸酮等 的噻噸酮系光聚合起始劑，或者雙（2，4,6-三甲基苯甲醯）-苯基膦氧化物、2,4,6-三甲基苯甲醯二苯基膦氧化物等之 膦氧化物系光聚合起始劑，由深部硬化性方面而言較佳。 如此的噻噸酮系光聚合起始劑或膦氧化物系光聚合起 始劑的摻合量，相對於上述含羧基之樹脂（A) 100質量 份’較佳爲3 0質量份以下，更佳爲20質量份以下的比 例’此等噻噸酮系光聚合起始劑的摻合量，太多則因爲厚 膜硬化性降低，而造成製品的成本上昇，故較不佳。 (F) 上述一般式（Π)所表示的硫化合物 藉由摻合硫化合物可提高組成物對雷射光的感度，但 本發明者推測其理由如下。於光照射部位中，隨著自由基 聚合反應的進行，很難引起聚合性單體（D)的擴散，會有 聚合速度或反應率的降低發生而未反應的聚合性單體（D) 殘留的情況’惟，認爲藉由添加硫化合物（F)作爲鏈轉移 劑作用’可有效率地進行聚合反應而提高反應率，其結果 可達成高感化。 (G) 硼酸 而且，本發明的鹼顯影型糊料組成物，爲了提高保存 女定性’加入砸酸（G)較佳。 如此的硼酸（G)，可使用經由噴磨機、球磨機、輥碎 機等進行微粉化之平均粒徑（D50)爲20μιη以下者，較佳 爲5μιη以下者。 經如此的微粉化者，因爲易吸濕·再凝聚，故粉碎後 -23- 200844660 儘速使用較佳’此外亦可與糊料中所含的樹脂或溶劑等一 起粉碎。 如此的硼酸（G)的摻合比例，相對於上述玻璃基質 (B)100質量份，以0·01〜10質量份較適當，更佳爲〇」〜 2質量份。硼酸的摻合比例，相對於上述玻璃基質（Β)1〇〇 * 質量份’太少則因爲保存安定性無提昇效果而較不佳。-S -22- 200844660 A thioxanthone photopolymerization initiator such as 2,4-diethylthioxanthone, 2-chlorothioxanthone or 2,4-diisopropylthioxanthone, or double a phosphine oxide photopolymerization initiator such as 2,4,6-trimethylbenzhydrazide)-phenylphosphine oxide or 2,4,6-trimethylbenzimidium diphenylphosphine oxide, It is preferred from the viewpoint of deep hardenability. The blending amount of the thioxanthone-based photopolymerization initiator or the phosphine oxide-based photopolymerization initiator is preferably 30 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin (A). It is preferable that the ratio of the amount of the thioxanthone-based photopolymerization initiator is too large, because the thick film hardenability is lowered, and the cost of the product is increased, which is not preferable. (F) Sulfur compound represented by the above general formula (Π) The sensitivity of the composition to laser light can be improved by blending a sulfur compound, but the inventors speculate that the reason is as follows. In the light-irradiated portion, as the radical polymerization proceeds, it is difficult to cause diffusion of the polymerizable monomer (D), and a decrease in polymerization rate or reaction rate occurs, and unreacted polymerizable monomer (D) remains. In the case of the addition of the sulfur compound (F) as a chain transfer agent, it is considered that the polymerization reaction can be efficiently carried out to increase the reaction rate, and as a result, a high effect can be achieved. (G) Boric acid Further, in the alkali-developing type paste composition of the present invention, it is preferred to add citric acid (G) in order to improve storage. The boric acid (G) may be an average particle diameter (D50) of 20 μm or less, preferably 5 μm or less, by micronization using a jet mill, a ball mill, a roller mill or the like. Since such a micronized one is easy to absorb moisture and re-agglomerate, it is preferably used as soon as possible after pulverization -23-200844660, or it may be pulverized together with a resin or a solvent contained in the paste. The blending ratio of the boric acid (G) is suitably from 0. 01 to 10 parts by mass, more preferably from 〇 to 2 parts by mass, per 100 parts by mass of the glass substrate (B). The blending ratio of boric acid is too small with respect to the above-mentioned glass substrate (〇〇) 1 〇〇 * parts by mass, which is less preferable because the preservation stability is not enhanced.
， 再者’摻合如此的硼酸（G)時，必須使用相對於25°C φ 的水l〇〇g的溶解度爲20g以下之疏水性溶劑，使用相對 於水的溶解度局的有機溶劑時，溶解於有機溶劑中的水， 因爲會成爲使玻璃基質中所含的金屬產生離子化、凝凝膠 化的原因，而較不佳。 (H)磷化合物 而且’爲了更提高本發明的鹼顯影型糊料組成物的保 存安定性，摻合上述一般式（V)或一般式（VI)所表示的磷 化合物（H)較佳。 φ 如此的磷化合物（H)，可列舉磷酸甲酯、磷酸乙酯、 _ 磷酸丙酯、磷酸丁酯、磷酸苯酯、磷酸二甲酯、磷酸二乙 酯、磷酸二丁酯、磷酸二丙酯、磷酸二苯酯、磷酸異丙 酯、磷酸二異丙酯、磷酸η 丁酯、亞磷酸甲酯、亞磷酸乙 酯、亞磷酸丙酯、亞磷酸丁酯、亞磷酸苯酯、亞磷酸二甲 酯、亞磷酸二乙酯、亞磷酸二丁酯、亞磷酸二丙酯、亞磷 酸二苯酯、亞磷酸異丙酯、亞磷酸二異丙醋、亞磷酸η 丁 基-2_乙基己基羥基乙撐二膦酸、腺嘌呤核苷三磷酸、腺 嘌哈核苷磷酸、單（2-甲基丙烯醯基氧基乙基）酸性磷酸 -24- 200844660 酯、單（2-丙烯醯基氧基乙基）酸性磷酸酯、二（2 -甲基丙烯 醯基氧基乙基）酸性磷酸酯、二（2-丙烯醯基氧基乙基）酸性 磷酸酯、乙基二乙基膦醯基乙酸酯、乙基酸性磷酸酯、丁 基酸性磷酸酯、丁基焦磷酸酯、丁氧基乙基酸性磷酸酯、 2-乙基己基酸性磷酸酯、油基酸性磷酸酯、二十四烷基酸 性磷酸酯、二乙二醇酸性磷酸酯、（2-羥基乙基）甲基丙烯 酸酯酸性磷酸酯等。此等之磷化合物，可單獨使用或組合 2種類以上。 此等磷化合物（H)的摻合量，相對於上述玻璃基質 (B)100質量份，爲1〇質量份以下，較佳爲〇·1〜5質量 份。磷化合物（Η)的摻合量，相對於上述玻璃基質（Β)100 質量份，超過1 0質量份時，因爲燒成性降低而較不佳。 (其他的摻合物） 本發明的鹼顯影型糊料組成物，爲了上述含羧基之樹 脂（A)的合成或組成物的調整，或爲了塗佈於基板或載體 薄膜的黏度調整，可使用有機溶劑。具體而言，可列舉甲 基乙基酮、環己酮等之酮類；甲苯、二甲苯、四甲基苯等 之芳香族烴類；溶纖劑、甲基溶纖劑、卡必醇、甲基卡必 醇、丁基卡必醇、丙二醇單甲基醚、二丙二醇單甲基醚、 二丙二醇單乙基醚、三乙二醇單乙基醚等之二醇醚類；乙 酸乙酯、乙酸丁酯、溶纖劑乙酸酯、丁基溶纖劑乙酸酯、 卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇單甲基醚乙酸 酯等之乙酸酯類；乙醇、丙醇、乙二醇、丙二醇、萜品醇 -25- 200844660 等之醇類；辛烷、癸烷等之脂肪族烴；石油醚、石油腦、 氫化石油腦、溶劑石油腦等之石油系溶劑，此等可單獨使 用或組合2種類以上使用。 本發明的鹼顯影型糊料組成物，再必要時，可摻合如 氫醌、氫醌單甲基醚、t -丁基兒茶酚、焦掊酚、吩噻嗪等 之習知慣用的熱聚合抑制劑、微粉二氧化矽、有機膨潤 土、蒙脫石等之習知慣用的增黏劑、聚矽氧系、氟系、高 分子系等之消泡劑及/或塗平劑、咪哩系、噻唑系、三唑 系等之矽烷偶合劑等之習知慣用的添加劑類。 (組成物的使用） 如以上説明的本發明的鹼顯影型糊料組成物，例如可 藉由用上述有機溶劑調整至適合塗佈方法的黏度，經由浸 漬塗佈法、流塗法、輥軋塗佈法、棒塗法、網版印刷法、 簾塗法等方法等方法塗佈於基板上，例如藉由以約60〜 120°C使其乾燥5〜40分鐘程度乾燥，形成不黏（tack free) 的塗膜。此外，將上述組成物塗佈於載體薄膜上，使其乾 燥後捲成薄膜者，藉由層壓於基板上，可形成不黏（tack free)塗膜。 再者，如此作法乾燥的塗膜的膜厚每1 μιη的吸光度 爲0.1〜0.8，由圖型形成性方面而言較佳。 然後，藉由接觸式（或非接觸方式），用活性能量線對 圖型進行選擇性地曝光，使未曝光部藉由稀鹼水溶液（例 如0.3〜3 %碳酸鈉水溶液）進行顯影後形成圖型。 •26- 200844660 上述活性能量線照射所使用的曝光機，可使用直接描 繪裝置（例如藉由來自電腦的CAD數據用直接雷射描繪畫 像之雷射直接成像裝置）。活性能量線源，可列舉發出最 大波長在350nm〜420ixm的範圍的雷射光之雷射二極管、 氣體雷射、固體雷射等，特別佳爲雷射二極管。 上述直接描繪裝置，可使用例如日本Orbotech公司 製、PENTAX公司製、日立 Via Mechanics公司製、Ball Semiconductor公司製等者，可使用任何一種裝置。 此外，上述直接描画裝置以外，亦可使用先前技術的 曝光機，作爲此光源，可使用鹵素燈、高壓水銀燈、雷射 光、金屬鹵素燈、黑燈、無電極燈等。 此外，上述顯影可使用噴霧法、浸漬法等，顯影液適 合使用氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、矽酸鈉等 之金屬鹼水溶液、及單乙醇胺、二乙醇胺、三乙醇胺、四 甲基銨氫氧化物等之胺水溶液，特別是約1 · 5質量％以下 的濃度的稀鹼水溶液較適合，但只要組成物中的含羧基之 樹脂（A)的羧基被凝膠化，及未硬化部（未曝光部）被去除 即可，並不限定於如上述的顯影液。此外，顯影後爲了去 除不需要的顯影液，進行水洗及酸中和較佳。 藉由上述顯影被形成圖型的基板，在空氣中或氮氣環 境下，藉由以約40 0〜600 °C進行燒成，可形成所望的圖 型。 【實施方式】 -27- 200844660 [實施例] 以下列舉出實施例及比較例以具體地說明本發明，但 本發明當然不限定於下述實施例。 合成例1 :含羧基之樹脂的合成 於具備溫度計、攪拌機、滴下漏斗、及迴流冷卻器之 燒瓶中，以 〇·87: 0.13的莫耳比裝入甲基甲基丙烯酸酯 與甲基丙烯酸，加入作爲溶劑之二丙二醇單甲基醚、作爲 觸媒之偶氮雙異丁腈，窒素雰圍氣下，以80°C攪拌6小 時，得到含羧基之樹脂溶液，此樹脂係重量平均分子量爲 約1〇,〇00，及酸價爲74mgKOH/g。再者，所得到的共聚 合樹脂的重量平均分子量的測定，係（株）島津製作所製泵 LC-6AD與昭和電工（株）製管柱 Shodex(註冊商標）1^ 804、KF-803、KF-802，藉由三根連在一起的高速液體層 析法進行測量，以下，將此含羧基之樹脂溶液稱爲A-1清 漆。 合成例2 :含羧基之感光性樹脂的合成 在具備溫度計、攪拌機、滴下漏斗、及迴流冷卻器之 燒瓶中，以莫耳比爲〇·76 : 0·24裝入甲基甲基丙烯酸酯 與甲基丙烯酸，加入作爲溶劑之二丙二醇單甲基醚、作爲 觸媒之偶氮雙異丁腈，在窒素雰圍氣下，以80°C攪拌6小 時，得到含羧基之樹脂溶液，冷卻此含羧基之樹脂溶液， 使用作爲聚合抑制劑之甲基氫醌、觸媒之四丁基錢溴化 -28- 200844660 物，使環氧丙基甲基丙烯酸酯，在以95〜105 °C進行16小 時的條件下，以上述相對於樹脂的羧基1莫耳爲〇 . 1 2莫 耳的比例的加成莫耳比進行加成反應，冷卻後取出。藉由 上述反應所成的含羧基之感光性樹脂的重量平均分子量約 1〇,〇〇〇、酸價爲59mgKOH/g、雙鍵當量爲950。以下，將 此含羧基之感光性樹脂溶液稱爲A-2清漆。 實施例1〜1 8及比較例1〜2 依表1及表2所表示的摻合成分使用上述合成例1、 2所得到的A-1清漆及A-2清漆，用3根輥碎機進行混 練，得到鹼顯影型糊料組成物。Further, when the boric acid (G) is blended, it is necessary to use a hydrophobic solvent having a solubility of water of 20 g or less and a solubility of 20 g or less, and when using an organic solvent having a solubility with respect to water, The water dissolved in the organic solvent is less likely to cause ionization and gelation of the metal contained in the glass matrix. (H) Phosphorus compound In order to further improve the storage stability of the alkali-developing type paste composition of the present invention, it is preferred to blend the phosphorus compound (H) represented by the above general formula (V) or general formula (VI). Examples of such a phosphorus compound (H) include methyl phosphate, ethyl phosphate, propyl propyl phosphate, butyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, and dipropyl phosphate. Ester, diphenyl phosphate, isopropyl phosphate, diisopropyl phosphate, η butyl phosphate, methyl phosphite, ethyl phosphite, propyl phosphite, butyl phosphite, phenyl phosphite, phosphorous acid Dimethyl ester, diethyl phosphite, dibutyl phosphite, dipropyl phosphite, diphenyl phosphite, isopropyl phosphite, diisopropyl phosphite, η butyl-2_B Hexyl hydroxyethylene diphosphonic acid, adenine nucleoside triphosphate, adenine nucleoside phosphate, mono(2-methylpropenyl methoxyethyl) acid phosphate-24- 200844660 ester, mono(2-propene Mercaptooxyethyl)acid phosphate, bis(2-methylpropenyloxyethyl) acid phosphate, bis(2-propenyl methoxyethyl) acid phosphate, ethyl diethyl Phosphonic acid acetate, ethyl acid phosphate, butyl acid phosphate, butyl pyrophosphate, butoxyethyl acid phosphate 2-Ethylhexyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, diethylene glycol acid phosphate, (2-hydroxyethyl) methacrylate acid phosphate, and the like. These phosphorus compounds may be used alone or in combination of two or more. The blending amount of the phosphorus compound (H) is 1 part by mass or less, preferably 1 to 5 parts by mass, per 100 parts by mass of the glass substrate (B). When the amount of the phosphorus compound (Η) is more than 10 parts by mass based on 100 parts by mass of the above glass substrate (yttrium), the calcinability is lowered. (Other Blend) The alkali-developing type paste composition of the present invention can be used for the synthesis of the carboxyl group-containing resin (A) or the adjustment of the composition, or for the viscosity adjustment applied to the substrate or the carrier film. Organic solvents. Specific examples thereof include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, and carbitol. Glycol ethers such as methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether; ethyl acetate Acetate of butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, etc.; Alcohols such as propanol, ethylene glycol, propylene glycol, terpineol-25-200844660; aliphatic hydrocarbons such as octane and decane; petroleum systems such as petroleum ether, petroleum brain, hydrogenated petroleum brain, solvent petroleum brain, etc. Solvents, these may be used individually or in combination of 2 or more types. The alkali-developing type paste composition of the present invention may be blended with a conventional one such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol or phenothiazine, if necessary. Thermal polymerization inhibitor, fine powder of cerium oxide, organic bentonite, montmorillonite, etc., conventionally used tackifiers, polyfluorene-based, fluorine-based, polymer-based antifoaming agents and/or coating agents, and microphones A conventionally used additive such as a decane coupling agent such as an oxime system, a thiazole system or a triazole system. (Use of the composition) The alkali-developing type paste composition of the present invention described above can be adjusted, for example, by the above-described organic solvent to a viscosity suitable for the coating method, via a dip coating method, a flow coating method, or a rolling method. A method such as a coating method, a bar coating method, a screen printing method, or a curtain coating method is applied to the substrate, for example, by drying at about 60 to 120 ° C for 5 to 40 minutes to form a non-sticky layer ( Tack free) film. Further, the above composition is applied onto a carrier film, dried, and wound into a film, and laminated on the substrate to form a tack free coating film. Further, the film thickness of the coating film thus dried is preferably from 0.1 to 0.8 per 1 μm, which is preferable in terms of pattern formability. Then, by contact (or non-contact method), the pattern is selectively exposed by an active energy ray, and the unexposed portion is developed by a dilute aqueous alkali solution (for example, 0.3 to 3% aqueous sodium carbonate solution) to form a pattern. type. • 26- 200844660 The exposure machine used for the above active energy ray irradiation can use a direct drawing device (for example, a laser direct imaging device that draws a picture with a direct laser by CAD data from a computer). Examples of the active energy ray source include laser diodes emitting laser light having a maximum wavelength in the range of 350 nm to 420 ixm, gas lasers, solid lasers, and the like, and particularly preferably laser diodes. As the direct drawing device, for example, any one of the devices can be used, for example, manufactured by Orbotech Co., Ltd., manufactured by PENTAX Corporation, manufactured by Hitachi Via Mechanics Co., Ltd., and manufactured by Ball Semiconductor. Further, in addition to the above-described direct drawing device, a prior art exposure machine may be used, and as the light source, a halogen lamp, a high pressure mercury lamp, a laser beam, a metal halide lamp, a black lamp, an electrodeless lamp or the like may be used. Further, the development may be carried out by a spray method, a dipping method or the like, and the developing solution is preferably a metal alkali aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium citrate, or monoethanolamine, diethanolamine or triethanolamine. An aqueous amine solution such as tetramethylammonium hydroxide or the like, particularly a dilute aqueous alkali solution having a concentration of about 5% by mass or less is suitable, but as long as the carboxyl group of the carboxyl group-containing resin (A) in the composition is gelated, The unhardened portion (unexposed portion) may be removed, and is not limited to the developer as described above. Further, it is preferred to carry out water washing and acid neutralization in order to remove an unnecessary developer after development. The substrate formed into a pattern by the above development can be formed by firing at about 40 to 600 ° C in the air or in a nitrogen atmosphere. [Embodiment] -27- 200844660 [Examples] Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is of course not limited to the following examples. Synthesis Example 1: Synthesis of a carboxyl group-containing resin In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, methyl methacrylate and methacrylic acid were charged at a molar ratio of 〇·87: 0.13. Dipropylene glycol monomethyl ether as a solvent and azobisisobutyronitrile as a catalyst were added, and the mixture was stirred at 80 ° C for 6 hours in an alizarin atmosphere to obtain a carboxyl group-containing resin solution having a weight average molecular weight of about 1 〇, 〇00, and the acid value was 74 mgKOH/g. In addition, the weight average molecular weight of the obtained copolymerized resin was measured by the pump LC-6AD manufactured by Shimadzu Corporation and the pipe column Shodex (registered trademark) 1^ 804, KF-803, KF manufactured by Showa Denko Co., Ltd. -802, measured by three high-speed liquid chromatography methods connected together. Hereinafter, the carboxyl group-containing resin solution is referred to as A-1 varnish. Synthesis Example 2: Synthesis of a carboxyl group-containing photosensitive resin In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux cooler, methyl methacrylate was charged at a molar ratio of 〇·76:0·24. To methacrylic acid, dipropylene glycol monomethyl ether as a solvent and azobisisobutyronitrile as a catalyst were added, and the mixture was stirred at 80 ° C for 6 hours in a halogen atmosphere to obtain a carboxyl group-containing resin solution, which was cooled. a resin solution of a carboxyl group, using methylhydroquinone as a polymerization inhibitor, tetrabutyl bromide bromide-28-200844660 as a polymerization inhibitor, and making a glycidyl methacrylate at a temperature of 95 to 105 ° C. Under the conditions of an hour, the addition reaction was carried out by adding the molar ratio of the carboxyl group of 1 mol to the carboxyl group of the resin, and after cooling, it was taken out. The carboxyl group-containing photosensitive resin formed by the above reaction had a weight average molecular weight of about 1 Å, a hydrazine, an acid value of 59 mgKOH/g, and a double bond equivalent of 950. Hereinafter, the carboxyl group-containing photosensitive resin solution is referred to as A-2 varnish. Examples 1 to 18 and Comparative Examples 1 to 2 The A-1 varnish and the A-2 varnish obtained in the above Synthesis Examples 1 and 2 were used according to the blending components shown in Tables 1 and 2, and 3 roller mills were used. The kneading was carried out to obtain an alkali developing type paste composition.
-29- 200844660-29- 200844660
比較例 〇 1 〇 1 1 I 1 ο 1 1 Η~ 脈 隹 m - w w 丑· » m 靼 稍 S ffi-P 鲥 ^ 11 U κ S ^ s g IS φ m i , 研 ^ f b g ^ 鹋 i m u s _ ¢3 _ i ^ ^ i 键嫲 £ § a 七 ^ f S κ 〇 1 ^? ¥ <2 1 ik 鎏 ^ ® ϊ^ι i | l?l !fl i ^ ft g i g S1 S ζ . fr 齡 〇 S N3 d ，餵满ά 11 £ f稍 ! s載K懷Μ 1 V &麗 ό ^ |Η 11] ΐί ά ™ 2： ^ ^ ^ _ 4< S幽’丨丨丨權_働煦 耻 § ιβ β !S 匾 $ 1 ϊ β 甲 喊3蜜槲3ν] 3 — N m 寸…vd 卜 oo 〇\ 2 ※ ※※※※※※※※※ 實施例 as 〇 H ! 〇 in (N in ο Ο m *Λ) d 1 d oo 〇 1 1 (Ν Ο m o 1 〇 1—! 卜 〇 1 〇 (N 1 ο m d 1 1 o I 〇 (N 1 ο m O 1 d r-Η 〇 T—< 1 (N I 沄 in o 1 〇 1 寸 I o 〇 »〇 (N 1 ο cn ό d i r—I d 1 m 0 1 4 1 (N 1 ο m CD 1 d I (N 〇 r-H i CN 1 ο m O 1 1 1 o 1 ΓΜ 1 1 d 1 i 1 A-l清漆 A-2清漆 玻璃基質※1 黑色顏料※2 聚合物單體※3 光聚合起始劑(E-1^4 光聚合起始劑(Ε-1)Χ5 光聚合起始劑(E-2)※6 硫化合物※7 比較的光聚合起始劑※8 硼酸※9 磷化合物※10 擊舻 -30- 200844660Comparative Example 〇1 I1 1 I 1 ο 1 1 Η~ 隹m - ww ugly · » m 靼 S Sfifi-P 鲥^ 11 U κ S ^ sg IS φ mi , 研^ fbg ^ 鹋imus _ ¢3 _ i ^ ^ i key 嫲 £ § a 七 ^ f S κ 〇 1 ^? ¥ <2 1 ik 鎏^ ® ϊ^ι i | l?l !fl i ^ ft gig S1 S ζ . fr Age 〇S N3 d, feed full ά 11 £ f slightly! s containing K Huai Μ 1 V & 丽ό ^ |Η 11] ΐί ά TM 2: ^ ^ ^ _ 4< S 幽 '丨丨丨权_働煦羞§ Ιβ β !S 匾$ 1 ϊ β A shout 3 candied 3ν] 3 — N m inch...vd oo 〇 2 2 2 ※ ※※※※※※※※※ Example as 〇H ! 〇in (N in ο Ο m *Λ) d 1 d oo 〇1 1 (Ν Ο mo 1 〇1—! 卜〇1 〇(N 1 ο md 1 1 o I 〇(N 1 ο m O 1 d r-Η 〇T—< 1 (NI 沄in o 1 〇 1 inch I o 〇»〇(N 1 ο cn ό dir—I d 1 m 0 1 4 1 (N 1 ο m CD 1 d I (N rH i CN 1 ο m O 1 1 1 o 1 ΓΜ 1 1 d 1 i 1 Al varnish A-2 varnish glass substrate*1 Black pigment*2 Polymer monomer*3 Photopolymerization initiator (E-1^4 photopolymerization initiator ( Ε-1)Χ5 Guangju Initiator (E-2) ※ 6 ※ 7 Comparative sulfur compound photopolymerization initiator borate ※ 9 ※ 8 ※ 10 strike the phosphorus compound henashi -30-200844660
rsl撇 比較例 ο 1 (Ν 寸 ο ! I 1 i 〇 1 1 链 S u m s P 5 si 绝 s I 澎 b r-H X | I M 綠 un - 疆 s ^ i 〇 in nw^ 篆 ί <Λ ψ i ϊ i Is 5 f J?1 ：1 1? itfl i fi s| IgSi ^1^11 nigs BllfSlpIl g 擗驭挺舀譲’稍nJ_礮塑 蜜載降賴Ά N3 A 5 A昍：？ * ο — (Nm 寸 《〇^〇卜〇〇〇\ — ※ ※※※※迻※※※※ 〇〇 ο 1 (Ν ο in CN d cn ο ο 1—Η 1 〇 卜 Ο 1 CN ο 寸 1 (N ΓΛ Ο 1 1 τ··Η Ο VO F—^ Ο 1 (Ν ο »η ν〇 m 1 m ο 1 1 〇 »r> 1—H Ο 1 04 寸 ν〇 1 rn Ο ( 1 ^-Η Ο τ-Η 寸 Ψ ·Η ο 1—Η 1 ΙΟ (Ν ο JT) (Ν 1 Ο 1 1 1 * m Ο Τ—Η ! ιτ> (Ν ο (Ν 1 ΓΠ Ο 1 1 ο r—Η 1 ο Γ^ϊ ο (Ν 1 ΓΠ ο 1 1 1 τ—Η ο t A 1 Ό (Ν ο 〇 <Ν 1 m ο 1 1 t-H 1 ο Ο Η 1 们 (Ν ο 〇 (Ν 1 m Ο 1 1 1 1 Α-1清漆 Α-2清漆 玻璃基質※1 銀粉※2 聚合物單體※3 1光聚合起始劑珥)※々 光聚合起始劑氏)※5 硫化合物※6 其他的光聚合起始劑※7 比較的光聚合起始劑※8 硼酸※9 磷化合物※10 IS妒 200844660 使用上述表1實施例1〜9及比較例1的鹼顯影型的 黑色糊料組成物，使用3 00網眼的聚酯篩全面地塗佈於玻 璃基板上，接著，使用熱風循環式乾燥爐，以90°C乾燥 ~ 20分鐘後形成指觸乾燥性優良的皮膜。接下來，使用線 寬爲1 ΟΟμιη、間距寬爲1 50μιη之條紋狀的CAD數據，用 • 具有中心波長爲405nm的藍紫色雷射作爲光源之雷射直 . 接成像曝光裝置（PENTAX公司製 DI-μΙΟ)，進行曝光而 φ 使組成物上的積算光量成爲40mJ/cm2。然後，使用液溫 3 0°C的0.4wt°/〇Na2CO3水溶液顯影20秒，進行水洗，最後 使用電氣爐在空氣中燒成。 再者，燒成係進行以5°C/分鐘的昇溫速度從室溫昇溫 至590°C，於590°C保持10分鐘，然後放冷至室溫之步 評估關於如此作法所得到的各基板的各種特性的結 果，列示於表3。 # 再者，表3中的評估方法如下述。 • (1)吸光度的測量 於鹼石灰玻璃形成乾燥膜厚5μπι及ΙΟμπι的塗膜之評 估基板的吸光度，使用紫外可見分光光度計測量，由所得 到的數據，算出在4 05nm之厚度每Ιμπι的吸光度。 (2)雷射感光性的評估 使L / S = 1 0 0 /1 5 0 μ m的線用積算光量5 0 m J / c m 2進行曝 光，使用液溫30°C的〇.4wt%Na2C03水溶液進行20秒顯 影’用光學顯微鏡評估線是否被形成，評估基準如下。 -32- 200844660 〇：完全看不到缺損。 △:看到些許的缺損。 X:線無法形成。 (3)算出最低曝光量 改變積算光量後進行曝光，測量L/S = 100/15C^m的線 * 可在無缺損下形成之最小的曝光量，再者，比較例因爲雷 . 射的曝光時間變長而不實用，故未實施以後的試驗。 φ (4)圖型形成後的線形狀 以上述的最低曝光量進行曝光時，以顯微鏡觀察於驗 顯影型的黑色糊料組成物之顯影後的圖型，以線是否有不 規則的偏差、是否有歪斜等進行評估，評估基準如下。 〇：無不規則的偏差、無歪斜等。 △:有些許不規則的偏差、歪斜等。 X:有不規則的偏差、歪斜等。 (5) 燒成後的線形狀 • 燒成後的線形狀，用顯微鏡觀察直到燒成結束的圖 . 型，以線是否有不規則的偏差、是否有歪斜等進行評估， 評估基準如下。 〇：無不規則的偏差、無歪斜等。 △:有些許不規則的偏差、歪斜等。 X :有不規則的偏差、歪斜等。 (6) 黏附性 黏附性係藉由賽璐玢黏著紙帶進行剝離，評估是否有 圖型的剝離，評估基準如下。 -33- 200844660Rsl撇Comparative example ο 1 (Ν inchο! I 1 i 〇1 1 chain S ums P 5 si 绝 s I 澎b rH X | IM 绿 un - 疆 s ^ i 〇in nw^ 篆ί <Λ ψ i ϊ i Is 5 f J?1 :1 1? itfl i fi s| IgSi ^1^11 nigs BllfSlpIl g 擗驭挺舀譲'Slightly nJ_礮塑蜜载降赖Ά N3 A 5 A昍:? * ο — (Nm inch “〇^〇卜〇〇〇\ — ※※※※※※※※※※ 〇〇ο 1 (Ν ο in CN d cn ο ο 1—Η 1 〇卜Ο 1 CN ο inch 1 ( N ΓΛ Ο 1 1 τ··Η Ο VO F—^ Ο 1 (Ν ο »η ν〇m 1 m ο 1 1 〇»r> 1—H Ο 1 04 〇ν〇1 rn Ο ( 1 ^-Η Ο τ-Η Ψ Ψ ·Η ο 1—Η 1 ΙΟ (Ν ο JT) (Ν 1 Ο 1 1 1 * m Ο Τ—Η ! ιτ> (Ν ο (Ν 1 ΓΠ Ο 1 1 ο r—Η 1 ο ΓΠ^ϊ ο (Ν 1 ΓΠ ο 1 1 1 τ—Η ο t A 1 Ό (Ν ο 〇<Ν 1 m ο 1 1 tH 1 ο Ο Η 1 (( Ν 〇 Ν (Ν 1 m Ο 1 1 1 1 Α-1 varnish Α-2 varnish glass substrate*1 Silver powder*2 Polymer monomer*3 1 Photopolymerization initiator 珥) ※々光聚聚合剂)*5 Sulfur compound ※6 Other light Aggregation start *7 Comparative photopolymerization initiator*8 Boric acid*9 Phosphorus compound*10 IS妒200844660 The alkali-developing type black paste composition of Examples 1 to 9 and Comparative Example 1 of Table 1 above was used, and 300 mesh was used. The polyester sieve is entirely coated on the glass substrate, and then dried at 90 ° C for 20 minutes using a hot air circulating drying oven to form a film having excellent dryness to the touch. Next, a line width of 1 ΟΟ μιη is used. Stripe-shaped CAD data with a pitch of 1 50 μm, with a laser with a blue-violet laser with a center wavelength of 405 nm as a light source. Connected to an image exposure apparatus (DI-μΙΟ made by PENTAX) for exposure and φ composition The amount of integrated light on the object was 40 mJ/cm 2 , and then developed with a 0.4 wt ° / 〇 Na 2 CO 3 aqueous solution at a liquid temperature of 30 ° C for 20 seconds, washed with water, and finally fired in the air using an electric furnace. Further, the firing system was carried out by raising the temperature from room temperature to 590 ° C at a temperature elevation rate of 5 ° C /min, holding at 590 ° C for 10 minutes, and then cooling to room temperature to evaluate the respective substrates obtained in this manner. The results of the various characteristics are listed in Table 3. # Again, the evaluation methods in Table 3 are as follows. • (1) Measurement of absorbance The absorbance of the substrate was evaluated by forming a coating film having a dry film thickness of 5 μm and ΙΟμπι in soda-lime glass, and measured by an ultraviolet-visible spectrophotometer. From the obtained data, the thickness at 0.45 nm was calculated per Ιμπι. Absorbance. (2) Evaluation of laser sensitivity The line with L / S = 1 0 0 /1 50 μm was exposed with an integrated light amount of 50 m J / cm 2 using a liquid temperature of 30 ° C 〇.4 wt% Na2C03 The aqueous solution was developed for 20 seconds. The optical line was used to evaluate whether the line was formed, and the evaluation criteria were as follows. -32- 200844660 〇: No defects are visible at all. △: I saw a few defects. X: The line cannot be formed. (3) Calculate the minimum exposure amount, change the integrated light amount, and then perform exposure. Measure the line with L/S = 100/15C^m*. The minimum exposure that can be formed without defect. Furthermore, the comparison is due to the exposure of Ray. The time became longer and not practical, so the subsequent tests were not implemented. When the line shape after the formation of the φ (4) pattern is exposed at the minimum exposure amount described above, the developed pattern of the black paste composition of the development type is observed under a microscope, and whether the line has an irregular deviation, Whether there is a skew or the like is evaluated, and the evaluation criteria are as follows. 〇: No irregular deviation, no skew, etc. △: Some irregular deviations, skews, etc. X: There are irregular deviations, skews, etc. (5) Shape of the wire after firing • The shape of the wire after firing is observed with a microscope until the end of the firing. The type is evaluated by whether the wire has irregular deviation or skew or not. The evaluation criteria are as follows. 〇: No irregular deviation, no skew, etc. △: Some irregular deviations, skews, etc. X: There are irregular deviations, skews, etc. (6) Adhesive Adhesiveness was peeled off by a cellophane adhesive tape to evaluate the peeling of the pattern, and the evaluation criteria were as follows. -33- 200844660
〇：無圖型的剝離。 △:有些許圖型的剝離。 X :常有圖型的剝離。 -34- 200844660 比較例 τ—Η d X 1 1 1 實施例 as 0.38 〇 〇 〇 〇 00 0.36 〇 ο 〇 〇 〇 卜 0.38 ___1 〇 〇 〇 〇 0.38 * 〇 〇 〇 〇 0.36 〇 〇 〇 〇 〇 寸 0.38 〇 〇 〇 〇 m 0.37 〇 〇 〇 〇 (N 0.39 〇 § 〇 〇 〇 0.41 § 〇 〇 〇 吸光度 雷射感光性 i 曝光量(mJ/cm2) 圖型形成後的線形狀 燒成後的線形狀 黏附性〇: No pattern peeling. △: Peeling of some patterns. X: There is often a pattern peeling. -34- 200844660 Comparative Example τ - Η d X 1 1 1 Example as 0.38 〇〇〇〇00 0.36 〇ο 〇〇〇卜 0.38 ___1 〇〇〇〇0.38 * 〇〇〇〇0.36 〇〇〇〇〇inch 0.38 〇〇〇〇m 0.37 〇〇〇〇(N 0.39 〇§ 〇〇〇0.41 § 〇〇〇 Absorbance laser sensitivity i exposure amount (mJ/cm2) Line shape adhesion after pattern formation after pattern formation Sex
-35- 200844660 由表3所示的結果可以很清楚地知道’本發明的鹼顯 影型的黑色糊料組成物，對活性能量線具有充分的感度’ 可形成高精細的圖型，而且，燒成後的線形狀無不規則的 偏差，與基材的黏附性亦優異者。 再者，燒成後的黑色程度亦令人滿意，保存安定性亦 優異。 接著，亦使用黑色糊料組成物，實施燈式曝光的圖型 形成，使用上述實施例1〜9及比較例1的鹼顯影型的黑 色糊料組成物，使用3 00網眼的聚酯篩全面地塗佈於玻璃 基板上。接下來，使用熱風循環式乾燥爐，以9〇°C乾燥 20分鐘後形成指觸乾燥性優良的皮膜，接著，使用形成 有線寬爲1 〇 〇 μιη、間距寬爲1 5 0 μιη之條紋狀的負型圖型 之玻璃乾板作爲光罩，使用具備超高壓水銀燈作爲光源之 曝光裝置（伯東公司製 MAT-5 3 0 1 )進行曝光使糊料上的積 算光量達到50mJ/cm2，然後，使用液溫30°C的〇·4質量 %Na2C03水溶液進行20秒間顯影，進行水洗，最後使用 電氣爐於空氣中進行燒成。 再者，燒成係進行以5°C/分鐘的昇溫速度從室溫昇溫 至5 90 °C，於5 90 °C保持10分鐘，然後放冷至室溫之步 驟。 評估如此作法所得到的各基板的各種特性的結果，列 示於表5，再者，表5中的評估方法如下。 (1)感光性的評估 使L/S = 100/15(^m的線用積算光量50mJ/cm2進行曝-35- 200844660 It is clear from the results shown in Table 3 that 'the alkali-developing type black paste composition of the present invention has sufficient sensitivity to the active energy ray' to form a high-definition pattern, and There is no irregular deviation in the shape of the wire after the formation, and the adhesion to the substrate is also excellent. Furthermore, the degree of blackness after firing is also satisfactory, and the preservation stability is also excellent. Next, a pattern of lamp exposure was also formed using a black paste composition, and the alkali-developing type black paste composition of the above Examples 1 to 9 and Comparative Example 1 was used, and a mesh sieve of 300 mesh was used. Fully coated on a glass substrate. Next, using a hot air circulation type drying oven, after drying at 9 ° C for 20 minutes, a film excellent in finger-drying property was formed, and then, a stripe having a line width of 1 〇〇 μηη and a pitch width of 150 μm was formed. The glass plate of the negative type is used as a photomask, and an exposure device (MAT-5 3 0 1 manufactured by Bodong Co., Ltd.) having an ultrahigh pressure mercury lamp as a light source is used for exposure so that the integrated light amount on the paste reaches 50 mJ/cm 2 , and then, The 〇·4 mass% Na 2 CO 3 aqueous solution having a liquid temperature of 30° C. was developed for 20 seconds, washed with water, and finally fired in the air using an electric furnace. Further, the firing system was carried out by raising the temperature from room temperature to 5 90 ° C at a temperature elevation rate of 5 ° C / min, holding at 5 90 ° C for 10 minutes, and then allowing to cool to room temperature. The results of evaluating various characteristics of each of the substrates obtained in this manner are shown in Table 5. Further, the evaluation methods in Table 5 are as follows. (1) Evaluation of sensitivity The exposure of L/S = 100/15 (^m line is 50mJ/cm2)
< S -36- 200844660 光，使用液溫30°C的〇.4wt%Na2C03水溶液進行20秒間 顯影，以光學顯微鏡評估線是否可被形成，評估基準如下 述。 〇：全完看不到缺。 △:可看到些許的缺損。 • X :線無法形成。 、 （2)算出最低曝光量 Φ 改變積算光量進行曝光，測量L/S = 100/15(^m的線可 在無缺損下形成之最小的曝光量。 (3)圖型形成後的線形狀 以上述的最低曝光量進行曝光時，以顯微鏡觀察於鹼 顯影型的黑色糊料組成物之顯影後的圖型，以線是否有不 規則的偏差、是否有歪斜等進行評估，評估基準如下。 〇：無不規則的偏差、無歪斜等。 △:有些許不規則的偏差、歪斜等。 • X :有不規則的偏差、歪斜等。 、 （4)燒成後的線形狀 ^ 燒成後的線形狀，用顯微鏡觀察直到燒成結束的圖 型，以線是否有不規則的偏差、是否有歪斜等進行評估， 評估基準如下。 〇：無不規則的偏差、無歪斜等。 △:有些許不規則的偏差、歪斜等。 X :有不規則的偏差、歪斜等。 (5)黏附性 -37- 200844660 黏附性係藉由賽璐玢黏著紙帶進行剝離，評估是否有 圖型的剝離，評估基準如下。 〇·無圖型的剝離。 △:有些許圖型的剝離。 X:常有圖型的剝離。<S-36- 200844660 Light was developed by using a 4 wt% Na2C03 aqueous solution at a liquid temperature of 30 ° C for 20 seconds to evaluate whether a line could be formed by an optical microscope, and the evaluation criteria were as follows. 〇: I can't see the lack of it. △: A few defects can be seen. • X: The line cannot be formed. (2) Calculate the minimum exposure amount Φ Change the integrated light amount for exposure, and measure the minimum exposure amount that L/S = 100/15 (^m line can be formed without defect. (3) Line shape after pattern formation When the exposure was carried out at the lowest exposure amount as described above, the pattern after development of the alkali-developing type black paste composition was observed under a microscope, and whether the line was irregularly uneven or not, and the evaluation was performed as follows. The evaluation criteria were as follows. 〇: There are no irregular deviations, no skews, etc. △: Some irregular deviations, skews, etc. • X: Irregular deviations, skews, etc., (4) Line shape after firing ^ After firing The shape of the line is observed with a microscope until the end of firing, and the line is evaluated for irregular deviation and skew. The evaluation criteria are as follows: 〇: No irregular deviation, no skew, etc. △: Some Irregular deviations, skews, etc. X: Irregular deviations, skews, etc. (5) Adhesion -37- 200844660 Adhesiveness is peeled off by celluloid adhesive tape to evaluate whether there is pattern peeling The evaluation criteria are as follows. 〇·There is no pattern peeling. △: Some patterns are peeled off. X: There is often pattern peeling.
-38- 200844660 比較例 X 300 〇 〇 〇 實施例 〇 〇 〇 〇 〇〇 〇 〇 〇 〇 〇 卜 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 寸 〇 〇 〇 〇 〇 〇 〇 〇 (N 〇 § 〇 〇 〇 1-H <] 〇 〇 〇 感光性 必要曝光量(m/cm2) 圖型形成後的線形狀 燒成後的線形狀 黏附性-38- 200844660 Comparative Example X 300 〇〇〇Example 〇〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇 (N 〇 § 〇〇〇1-H <] 〇〇〇Photosensitive necessary exposure (m/cm2) Line shape adhesion after pattern formation after pattern formation
-39- 200844660 由表4所表示的結果可以很清楚地知道，本發明的鹼 顯影型的黑色糊料組成物，即使使用超高壓水銀燈作爲光 源’亦具有充分的感度，可形成高精細的圖型。 使用上述實施例10〜18及比較例2的鹼顯影型的銀 糊料組成物，使用3 00網眼的聚酯篩全面地塗佈於玻璃基 板上’接著，使用熱風循環式乾燥爐，以9 0。(：乾燥2 0分 鐘後形成指觸乾燥性優良的皮膜。接下來，使用線寬爲 5 0μιη、間距寬爲200μιη之條紋狀的CAD數據，用具有中 心波長爲405nm的藍紫色雷射作爲光源之雷射直接成像 曝光裝置（PENTAX公司製 ϋΙ_μ10)，進行曝光而使組成 物上的積算光量成爲40mJ/cm2。然後，使用液溫30°C的 0.4wt%Na2CO3水溶液顯影20秒，進行水洗，最後使用電 氣爐在空氣中燒成。 再者，燒成係進行以5°C/分鐘的昇溫速度從室溫昇溫 至5 90°C，於5 90°C保持1〇分鐘，然後放冷至室溫之步 驟。 評估關於如此作法所得到的各基板的各種特性的結 果，列示於表5。 再者，表5中的評估方法如下述。 (1) 吸光度的測量 於鹼石灰玻璃形成乾燥膜厚5μπι及ΙΟμηι的塗膜之評 估基板的吸光度，使用紫外可見分光光度計測量，由所得 到的數據，算出在405 nm之厚度每Ιμπι的吸光度。 (2) 雷射感光性的評估 -40- 200844660 使L/S = 50/20(^m的線用積算光量50mJ/cm2進行曝 光，使用液溫30°C的〇.4wt%Na2C03水溶液進行20秒顯 影，用光學顯微鏡評估線是否被形成，評估基準如下。 〇：完全看不到缺損。 △:看到些許的缺損。 • X :線無法形成。 . (3)算出最低曝光量 馨改變積算光量後進行曝光，測量L/S = 50/2〇Mm的線 可在無缺損下形成之最小的曝光量，再者，比較例因爲雷 射的曝光時間變長而不實用，故未實施之後的試驗。 (4) 圖型形成後的線形狀 以上述的最低曝光量進行曝光時，以顯微鏡觀察於鹼 顯影型的銀色糊料組成物之顯影後的圖型，以線是否有不 規則的偏差、是否有歪斜等進行評估，評估基準如下。 〇：無不規則的偏差、無歪斜等。 • △:有些許不規則的偏差、歪斜等。 . X :有不規則的偏差、歪斜等。 (5) 燒成後的線形狀 燒成後的線形狀，用顯微鏡觀察直到燒成結束的圖 型’以線是否有不規則的偏差、是否有歪斜等進行評估， 評估基準如下。 〇：無不規則的偏差、無歪斜等。 △:有些許不規則的偏差、歪斜等。 X :有不規則的偏差、歪斜等。-39- 200844660 It is clear from the results shown in Table 4 that the alkali-developing type black paste composition of the present invention has sufficient sensitivity even when an ultrahigh pressure mercury lamp is used as a light source, and a high-definition pattern can be formed. type. Using the alkali-developing type silver paste composition of the above Examples 10 to 18 and Comparative Example 2, a 300-mesh polyester sieve was applied to the glass substrate in its entirety. Next, a hot air circulation type drying furnace was used. 9 0. (: After drying for 20 minutes, a film having excellent dryness to the touch was formed. Next, stripe-shaped CAD data having a line width of 50 μm and a pitch width of 200 μm was used, and a blue-violet laser having a center wavelength of 405 nm was used as a light source. The laser direct imaging exposure apparatus (manufactured by PENTAX Co., Ltd., ϋΙμ10) was exposed to light so that the amount of integrated light on the composition was 40 mJ/cm 2 , and then developed with a 0.4 wt% Na 2 CO 3 aqueous solution having a liquid temperature of 30 ° C for 20 seconds, and washed with water. Finally, it is fired in the air using an electric furnace. Further, the firing system is heated from room temperature to 5 90 ° C at a temperature increase rate of 5 ° C / min, held at 5 90 ° C for 1 , minutes, and then allowed to cool to The procedure of evaluating the various characteristics of each substrate obtained by such a method is shown in Table 5. Furthermore, the evaluation method in Table 5 is as follows. (1) Measurement of absorbance is formed in soda lime glass. The absorbance of the substrate was evaluated by a film thickness of 5 μm and ΙΟμηι, and measured by an ultraviolet-visible spectrophotometer, and the absorbance at a thickness of 405 nm per Ιμπι was calculated from the obtained data. (2) Laser sensitivity Evaluation-40- 200844660 L/S = 50/20 (^m line was exposed with 50 mJ/cm2 of integrated light, and developed with a 4 wt% Na2C03 aqueous solution at a liquid temperature of 30 ° C for 20 seconds to evaluate the line with an optical microscope. Whether it is formed or not, the evaluation criteria are as follows. 〇: The defect is not seen at all. △: Some defects are seen. • X: The line cannot be formed. (3) Calculate the minimum exposure amount, change the integrated light amount, and then perform exposure, measure L/ The line with S = 50/2 〇 Mm can be formed with the minimum exposure without defects. Furthermore, the comparative example is not practical because the exposure time of the laser becomes long. Therefore, the subsequent test is not performed. (4) Pattern When the formed line shape is exposed at the minimum exposure amount described above, the developed pattern of the alkali-developing type silver paste composition is observed under a microscope, and whether the line has irregular deviation or skew or the like is evaluated. The evaluation criteria are as follows: 〇: No irregular deviation, no skew, etc. • △: Some irregular deviations, skews, etc. X: Irregular deviation, skew, etc. (5) Line after firing The shape of the wire after the shape is burned, using a microscope The evaluation is based on whether the pattern of the end of the firing is evaluated by whether the line has irregular deviation or skew or not. 〇: There are no irregular deviations, no skew, etc. △: Some irregular deviations and skews Etc. X: There are irregular deviations, skews, etc.
-41 - ( S 200844660 (6) 黏附性 黏附性係藉由賽璐玢黏著紙帶進行剝離，評估是否有 圖型的剝離，評估基準如下。 〇：無圖型的剝離。 △:有些許圖型的剝離。 X :常有圖型的剝離。 (7) 比電阻値的測定 除了使用圖型尺寸〇.4cmxlOcm的CAD數據進行曝光 以外，其餘與上述（燒成後的線形狀）的評估相同作法製作 試驗基板，關於如此作法所得到的試驗基板，使用 m i 11 i 〇 h m s h i t e s t e r測量燒成皮膜的電阻値，接著，使用表 面粗度測量器測量燒成皮膜的膜厚’算出燒成皮膜的比電 阻値。-41 - ( S 200844660 (6) Adhesive adhesion is peeled off by cellophane adhesive tape to evaluate whether there is pattern peeling. The evaluation criteria are as follows. 〇: No pattern peeling. △: Some drawings Type: Peeling. X: Peeling of pattern is often performed. (7) Measurement of specific resistance 値 is the same as the above evaluation (line shape after firing) except for exposure using CAD data of a pattern size of 44 cmxlOcm. In the test substrate, the test substrate obtained by the above method was used, and the resistance 値 of the fired film was measured using a mi 11 i 〇hmshitester, and then the film thickness of the fired film was measured using a surface roughness measuring instrument to calculate the ratio of the fired film. Resistance 値.
-42- 200844660-42- 200844660
比較例 (N 0.14 X 300 1 1 1 1 實施例 00 0.20 〇 〇 〇 〇 m cn 卜 0.14 〇 〇 〇 〇 m* Ό 0.35 〇 〇 〇 〇 〇 (N cn 0.19 〇 〇 〇 〇 〇 寸 ΓΛ 寸 0.14 〇 〇 〇 〇 m* m 0.15 〇 〇 〇 〇 cn 0.15 〇 〇 〇 〇 寸 rn r-H 0.16 〇 〇 〇 〇 m rn ο 0.16 〇 〇 〇 〇 (N rn 吸光度 1 雷射感光性 曝光量(mJ/cm2) 圖型形成後的線形狀 燒成後的線形狀 黏附性 比電阻値(χ1〇_6Ω · cm) -43- 200844660 接著，亦使用銀糊料組成物，實施燈式曝光的圖型形 成，使用上述實施例1 0〜1 8及比較例2的鹼顯影型的銀 糊料組成物，使用3 00網眼的聚酯篩全面地塗佈於玻璃基 板上。接下來，使用熱風循環式乾燥爐，以90°C乾燥20 分鐘後形成指觸乾燥性優良的皮膜，接著，使用形成有線 寬爲50μηι、間距寬爲200μιη之條紋狀的負型圖型之玻璃 乾板作爲光罩，使用具備超高壓水銀燈作爲光源之曝光裝 置（伯東公司製 MAT-5301)進行曝光使糊料上的積算光量 達到40mJ/cm2，然後，使用液溫30°C的0.4質量％Na2C03 水溶液進行20秒間顯影，進行水洗，最後使用電氣爐於 空氣中進行燒成。 再者，燒成係進行以5°C/分鐘的昇溫速度從室溫昇溫 至5 90 °C，於590 °C保持1〇分鐘，然後放冷至室溫之步 驟。 評估如此作法所得到的各基板的各種特性的結果，列 示於表6，再者，表6中的評估方法如下。 (1)感光性的評估 使L/S = 50/200pm的線用積算光量 50mJ/cm2進行曝 光，使用液溫30°C的〇.4wt%Na2C03水溶液進行20秒間 顯影，以光學顯微鏡評估線是否可被形成，評估基準如下 述。 〇：全完看不到缺損。 △:可看到些許的缺損。 X :線無法形成。 -44- 200844660 (2)算出最低曝光量 改變積算光量進行曝光，測量L/S = 50/200pm的線可 在無缺損下形成之最小的曝光量。 ^ (3)圖型形成後的線形狀 以上述的最低曝光量進行曝光時，以顯微鏡觀察於鹼 、 顯影型的銀色糊料組成物之顯影後的圖型，以線是否有不 規則的偏差、是否有歪斜等進行評估，評估基準如下。 φ 〇：無不規則的偏差、無歪斜等。 △:有些許不規則的偏差、歪斜等。 X :有不規則的偏差、歪斜等。 (4) 燒成後的線形狀 燒成後的線形狀，用顯微鏡觀察直到燒成結束的圖 型，以線是否有不規則的偏差、是否有歪斜等進行評估， 評估基準如下。 〇：無不規則的偏差、無歪斜等。 • △:有些許不規則的偏差、歪斜等。 ^ X :有不規則的偏差、歪斜等。 (5) 黏附性 黏附性係藉由賽璐玢黏著紙帶進行剝離，評估是否有 圖型的剝離，評估基準如下。 〇：無圖型的剝離。 △:有些許圖型的剝離。 X :常有圖型的剝離。 -45- 200844660 300 (N X 1 1 1 00 〇 〇 〇 〇 卜 〇 〇 〇 〇 MD 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 辑 2 〇 〇 〇 〇 U m 〇 〇 〇 〇 〇 〇 〇 〇 τ—Η 〇 〇 〇 〇 ο 〇 〇 〇 〇 鹱 旦 S _ 寒 链 制 _ 激 a 酿 Η -46- 200844660 由表6所表示的結果可以很清楚地知道，本發明的鹼 顯影型的銀色糊料組成物，即使使用超高壓水銀燈作爲光 源，亦具有充分的感度，可形成高精細的圖型。 實施例1 9〜2 6及比較例3 依表5所表示的摻合成分使用上述合成例所得到的 A-1清漆及A-2清漆，用3根輥碎機進行混練，得到鹼顯 影型糊料組成物。Comparative Example (N 0.14 X 300 1 1 1 1 Example 00 0.20 〇〇〇〇m cn 卜 0.14 〇〇〇〇m* Ό 0.35 〇〇〇〇〇 (N cn 0.19 〇〇〇〇〇 inch ΓΛ inch 0.14 〇 〇〇〇m* m 0.15 〇〇〇〇cn 0.15 〇〇〇〇inch rn rH 0.16 〇〇〇〇m rn ο 0.16 〇〇〇〇(N rn absorbance 1 laser photosensitive exposure (mJ/cm2) The linear shape adhesion after the formation of the linear shape after the formation of the resistance 値 (χ1〇_6 Ω · cm) -43- 200844660 Next, the silver paste composition is also used to form the pattern of the lamp exposure, using the above The alkali-developing type silver paste composition of Example 1 0 to 1 8 and Comparative Example 2 was entirely applied to a glass substrate using a 300-mesh polyester sieve. Next, a hot air circulation type drying furnace was used. After drying at 90 ° C for 20 minutes, a film having excellent dryness to the touch was formed, and then a glass dry plate having a negative pattern of a line width of 50 μm and a width of 200 μm was used as a mask, and an ultrahigh pressure mercury lamp was used. Exposure device as a light source ( MAT-5301, manufactured by Bodang Co., Ltd., was exposed to a volume of 40 mJ/cm2 on the paste, and then developed with a 0.4 mass% Na2CO3 aqueous solution at a liquid temperature of 30 ° C for 20 seconds, washed with water, and finally an electric furnace was used in the air. The firing was carried out by heating from room temperature to 5 90 ° C at a temperature increase rate of 5 ° C /min, holding at 590 ° C for 1 Torr, and then allowing to cool to room temperature. The results of various characteristics of each substrate obtained by the method are shown in Table 6. Further, the evaluation methods in Table 6 are as follows. (1) Evaluation of photosensitivity The line-accumulated light amount of L/S = 50/200 pm is 50 mJ. /cm2 was exposed, and development was carried out for 20 seconds using a 〇.4 wt% Na2C03 aqueous solution having a liquid temperature of 30 ° C, and the line was evaluated by optical microscopy. The evaluation criteria were as follows. 〇: No defects were observed at all. △: See a slight defect. X: Line cannot be formed. -44- 200844660 (2) Calculate the minimum exposure amount to change the integrated light amount for exposure, and measure the minimum exposure amount of the line with L/S = 50/200 pm without defect. ^ (3) The shape of the line after the pattern is formed is as described above When the exposure is performed at the lowest exposure amount, the developed pattern of the alkali-developing silver paste composition is observed under a microscope, and whether the line has irregular deviation or skew or the like is evaluated. The evaluation criteria are as follows. Φ 〇: no irregular deviation, no skew, etc. △: Some irregular deviations, skews, etc. X: There are irregular deviations, skews, etc. (4) Shape of the wire after firing The shape of the wire after firing is observed with a microscope until the end of the firing, and the wire is evaluated for irregular deviation and skew. The evaluation criteria are as follows. 〇: No irregular deviation, no skew, etc. • △: Some irregular deviations, skews, etc. ^ X: There are irregular deviations, skews, etc. (5) Adhesive adhesion The peeling was carried out by a cellophane adhesive tape to evaluate whether or not the pattern was peeled off, and the evaluation criteria were as follows. 〇: No pattern peeling. △: Peeling of some patterns. X: There is often a pattern peeling. -45- 200844660 300 (NX 1 1 1 00 〇〇〇〇 〇〇〇〇 〇〇〇〇〇〇〇〇〇〇 MD 〇〇〇〇〇〇〇〇〇〇 2 〇〇〇〇U m 〇〇〇〇〇〇〇〇τ—Η 〇〇〇〇ο 〇〇〇〇鹱 S S 寒 _ _ Η Η 46 -46- 200844660 From the results shown in Table 6, it can be clearly seen that the alkali-developing type silver paste composition of the present invention Even if an ultrahigh pressure mercury lamp is used as the light source, it has sufficient sensitivity to form a high-definition pattern. Example 1 9 to 2 6 and Comparative Example 3 The doped composition shown in Table 5 was obtained by using the above synthesis example. A-1 varnish and A-2 varnish were kneaded by a three-roller to obtain an alkali-developing paste composition.
-47- 200844660-47- 200844660
比較例 m 〇 1 〇 VO 〇 m 1 1 1 ! 〇 t 1 緘 丑· a m s 權 P a- xri Dml 寸 瓣 寸 氍 « η 瘦 κ 迨 111 s 迄 m B m <r € ^ b f 1 ^ 泛 m u ; 筚 rf 癒1 疆 1 g琴 S 祕 £ ^ i i S ε ? i < m ^ M 4 ^ 〇 5- 遯蔭 _。_載 ϊ gSm s ε S ^ m Λ2 E ^ ^ II is^l 舞春 ill ^ifs sil®! Κ9^||£|| £&圈超®i：r齧+蠢g a μ ^ 3nJ^Sg 蜜#奸紫寒跡；ίκι艺 — (Nm 寸》ην〇 卜 oo〇n2 二 % ※※ ※※※※※※※迻 實施例 Ό (N 〇 ! ο *η 〇 〇 m (N 1 〇 〇 1 1 (N Ο 1 〇 1 (N 〇 1 1 ο Ο τ—( 1 〇 〇 m (N 1 T-H I 1 1 ^-Η m (N ο ι—Η 1 〇 (N 1 〇 1 1 1 (N Ο ^Η 1 〇 ν〇 〇 m (N 1 〇 1 1 T—( d 1 ο 〇 S ο m (N 1 〇 1 1 d 1 ο 1 〇 VD ο (N 1 〇 1 1 5 1 T—K ο 1 〇 VO ο m CN 1 〇 1 1 1 1 Α-1清漆 Α-2清漆 玻璃基質※1 1 銀粉※2 黑色顏料※3 聚合物單體※4 |光聚合起始劑(E)《5 光聚合起始劑(E)※6 硫化合物※7 其他的光聚合起始劑※8 |比較的光聚合起始劑※9 硼酸※10 磷化合物※11 擊渺 -48- 200844660 進行含有作爲無機成份之黑色顏料與銀粉雙方之鹼顯 影型的黑色銀糊料組成物的評估。使用上述實施例丨9〜 26及比較例3的黑色銀糊料組成物，使用3 00網眼的聚 酯篩全面地塗佈於玻璃基板上。接下來，使用熱風循環式 乾燥爐，以90 °C乾燥20分鐘後形成指觸乾燥性優良的皮 膜，接著，使用形成有線寬爲50μπι、間距寬爲200μπι之 條紋狀的負型圖型之玻璃乾板作爲光罩，使用具備超高壓 水銀燈作爲光源之曝光裝置（伯東公司製 MAT-5 3 0 1 )進行 曝光使糊料上的積算光量達到40mJ/cm2，然後，使用液 溫3 0°C的0.4質量％Na2C03水溶液進行20秒間顯影，進 行水洗，最後使用電氣爐於空氣中進行燒成。 再者，燒成係進行以5°C/分鐘的昇溫速度從室溫昇溫 至5 9(TC，於5 90°C保持10分鐘，然後放冷至室溫之步 評估如此作法所得到的各基板的各種特性的結果，列 示於表8，再者，表8中的評估方法如下。 (1) 吸光度的測量 於鹼石灰玻璃形成乾燥膜厚5μιη及ΙΟμπι的塗膜之評 估基板的吸光度，使用紫外可見分光光度計測量，由所得 到的數據，算出在405nm之厚度每ΐμηι的吸光度。 (2) 感光性的評估 使L/S = 50/20(^m的線用積算光量 50mJ/cm2進行曝 光，使用液溫30°〇的〇.4wt%Na2C03水溶液進行20秒顯 影，用光學顯微鏡評估線是否被形成，評估基準如下° -49- 200844660 〇··完全看不到缺損。 △:看到些許的缺損。 X :線無法形成。 (3)算出最低曝光量 改變積算光量後進行曝光，測量L/S = 50/200，m的線 、 可在無缺損下形成之最小的曝光量，再者，比較例因爲雷 v 射的曝光時間變長而不實用，故未實施以後的試驗。 φ (4)圖型形成後的線形狀 以上述的最低曝光量進行曝光時，以顯微鏡觀察於鹼 顯影型的黑色糊料組成物之顯影後的圖型，以線是否有不 規則的偏差、是否有歪斜等進行評估，評估基準如下。 〇：無不規則的偏差、無歪斜等。 △:有些許不規則的偏差、歪斜等。 X.有不規則的偏差、歪斜等。 (5) 燒成後的線形狀 β 燒成後的線形狀，用顯微鏡觀察直到燒成結束的圖 ， 型，以線是否有不規則的偏差、是否有歪斜等進行評估， 評估基準如下。 〇：無不規則的偏差、無歪斜等。 △:有些許不規則的偏差、歪斜等。 X :有不規則的偏差、歪斜等。 (6) 黏附性 黏附性係藉由賽璐玢黏著紙帶進行剝離，評估是否有 圖型的剝離，評估基準如下。 -50- 200844660 〇：無圖型的剝離。 △:有些許圖型的剝離。 X :常有圖型的剝離。 (7)比電阻値的測定 除了使用形成圖型尺寸〇.4cmxlOcm的圆型的光罩進 行曝光以外，其餘與上述（燒成後的線形狀）的評估相同作 法製作試驗基板，關於如此作法所得到的試驗基板，使用 milliohms hitester測量燒成皮膜的電阻値，接著，使用表 面粗度測量器測量燒成皮膜的膜厚，算出燒成皮膜的比電 阻値。Comparative example m 〇1 〇VO 〇m 1 1 1 ! 〇t 1 缄 · · ams weight P a- xri Dml inch inch inch 氍 « η thin κ 迨 111 s m b m <r € ^ bf 1 ^ pan Mu; 筚rf 越1 疆1格琴S 秘 £ ^ ii S ε ? i < m ^ M 4 ^ 〇5- 遁 shade _. _载ϊ gSm s ε S ^ m Λ2 E ^ ^ II is^l 舞春ill ^ifs sil®! Κ9^||£|| £& circle super®i:r bit + stupid ga μ ^ 3nJ^Sg Honey #奸紫寒迹; ίκι艺—(Nm inch) ην〇卜oo〇n2 2% ※※ ※※※※※※※※移实施例Ό (N 〇! ο *η 〇〇m (N 1 〇〇 1 1 (N Ο 1 〇1 (N 〇1 1 ο Ο τ—( 1 〇〇m (N 1 TH I 1 1 ^-Η m (N ο ι—Η 1 〇(N 1 〇1 1 1 (N Ο ^Η 1 〇ν〇〇m (N 1 〇1 1 T—( d 1 ο 〇S ο m (N 1 〇1 1 d 1 ο 1 〇VD ο (N 1 〇1 1 5 1 T—K ο 1 〇VO ο m CN 1 〇1 1 1 1 Α-1 varnish Α-2 varnish glass substrate*1 1 Silver powder*2 Black pigment*3 Polymer monomer*4 |Photopolymerization initiator (E) "5 light Polymerization initiator (E)*6 Sulfur compound*7 Other photopolymerization initiator*8 |Comparative photopolymerization initiator*9 Boric acid*10 Phosphorus compound*11 Killing-48- 200844660 Containing as an inorganic component Evaluation of the alkali-developed black silver paste composition of both the black pigment and the silver powder. Using the above examples 丨9 to 26 and the ratio The black silver paste composition of Example 3 was entirely coated on a glass substrate using a 300 mesh polyester sieve. Next, a hot air circulating drying oven was used, and dried at 90 ° C for 20 minutes to form a dry touch. An excellent film is used, and a glass dry plate having a negative pattern of a line width of 50 μm and a width of 200 μm is used as a mask, and an exposure apparatus having an ultrahigh pressure mercury lamp as a light source is used (MAT-5 manufactured by Bodong Co., Ltd.). 3 0 1 ) Exposure was carried out so that the integrated light amount on the paste reached 40 mJ/cm 2 , and then developed with a 0.4 mass % Na 2 CO 3 aqueous solution having a liquid temperature of 30 ° C for 20 seconds, washed with water, and finally burned in the air using an electric furnace. Furthermore, the firing system was heated from room temperature to 5 9 (TC at a temperature increase rate of 5 ° C / min, held at 5 90 ° C for 10 minutes, and then allowed to cool to room temperature to evaluate the procedure. The results of various characteristics of each substrate are shown in Table 8. Further, the evaluation methods in Table 8 are as follows: (1) Measurement of absorbance in a soda lime glass to form a coating film of a dry film thickness of 5 μm and ΙΟμπι Suck Degrees, measured using an ultraviolet-visible spectrophotometer, from the obtained data, calculating the absorbance of each ΐμηι thickness of 405nm. (2) Evaluation of the sensitivity The L/S = 50/20 (^m line was exposed with an integrated light amount of 50 mJ/cm2, and developed with a liquid temperature of 30 ° 〇. 4 wt% Na2C03 aqueous solution for 20 seconds, using an optical microscope Whether the evaluation line is formed or not, the evaluation criteria are as follows: -49- 200844660 〇··There is no defect at all. △: Some defects are seen. X: The line cannot be formed. (3) Calculate the minimum exposure amount and change the integrated light amount. , measuring the line of L/S = 50/200, m, the minimum exposure that can be formed without defect, and the comparative example is not practical because the exposure time of the lightning v is long, so the subsequent test is not implemented. When the line shape after the formation of the φ (4) pattern is exposed at the minimum exposure amount described above, the pattern after development of the alkali-developing type black paste composition is observed under a microscope, and whether the line has irregular deviation Whether or not there is a skew, etc., the evaluation criteria are as follows. 〇: There are no irregular deviations, no skew, etc. △: Some irregular deviations, skews, etc. X. Irregular deviations, skews, etc. (5) Line shape after firing, the shape of the line after firing, used The micro-mirror is observed until the end of the firing, and the type is evaluated by whether the line has irregular deviation or skew. The evaluation criteria are as follows: 〇: No irregular deviation, no skew, etc. △: Some irregularities Deviation, skew, etc. X: Irregular deviation, skew, etc. (6) Adhesive adhesion is peeled off by the celluloid adhesive tape to evaluate whether there is pattern peeling. The evaluation criteria are as follows. - 200844660 〇: Peeling without pattern. △: Peeling of some patterns. X: Peeling of patterns often. (7) Measurement of specific resistance 除了 In addition to the formation of circular light with a pattern size of 44cmxlOcm The test substrate was produced in the same manner as the above (the shape of the wire after firing) except for the exposure of the cover. For the test substrate obtained in this way, the resistance 値 of the fired film was measured using milliohms hitester, and then the surface roughness was used. The measuring device measures the film thickness of the fired film, and calculates the specific resistance 烧 of the fired film.
-51 - 200844660 比較例 m 0.50 X 300 〇 〇 〇 ON rn 實施例 Ό (Ν 0.59 〇 ο 〇 〇 〇 in Cs| 0.53 〇 〇 〇 〇 (N — 艺 0.56 〇 ο 〇 〇 〇 Ο — m CN 0.55 〇 〇 〇 〇 ο 04 (N 0.50 〇 〇 〇 〇 (Ν 04 0.51 〇 〇 〇 〇 (Ν 宕 0.52 〇 〇 〇 〇 (Ν — Os 0.50 〇 〇 〇 〇 Ο 寸 吸光度 感光性 必要曝光量(m/cm2) 圖型形成後的線形狀 燒成後的線形狀 黏附性 比電阻値-51 - 200844660 Comparative Example m 0.50 X 300 〇〇〇ON rn Example Ό (Ν 0.59 〇ο 〇〇〇in Cs| 0.53 〇〇〇〇(N — 艺 0.56 〇ο 〇〇〇Ο — m CN 0.55 〇 〇〇〇ο 04 (N 0.50 〇〇〇〇 (Ν 04 0.51 〇〇〇〇 (Ν 宕 0.52 〇〇〇〇 (Ν — Os 0.50 〇〇〇〇Ο absorbance sensitivity necessary exposure (m/cm2) Line shape adhesion specific resistance after firing of the line shape after pattern formation 値
-52- 200844660-52- 200844660
由表8所表示的結果可以很清楚地知道，本發明的鹼 顯影型的黑色銀糊料組成物，具有充分的感度，可形成高 精細的圖型。 -53-As is apparent from the results shown in Table 8, the alkali-developing type black silver paste composition of the present invention has sufficient sensitivity to form a high-definition pattern. -53-
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| JP5236557B2 (en) * | 2009-03-31 | 2013-07-17 | 太陽ホールディングス株式会社 | Pattern formation method using laser |
| JP5561989B2 (en) * | 2009-10-02 | 2014-07-30 | 太陽ホールディングス株式会社 | Pattern formation method using laser |
| KR101277020B1 (en) * | 2010-09-30 | 2013-06-24 | 다이요 홀딩스 가부시키가이샤 | Photosensitive conductive paste |
| JP5825963B2 (en) * | 2011-09-30 | 2015-12-02 | 太陽ホールディングス株式会社 | Photosensitive conductive resin composition, photosensitive conductive paste, and conductor pattern |
| JP6058890B2 (en) * | 2012-01-11 | 2017-01-11 | 株式会社Adeka | Curable resin composition |
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| JP2000338322A (en) * | 1999-05-26 | 2000-12-08 | Mitsubishi Chemicals Corp | Photopolymerizable composition for color filter and color filter |
| JP2004198542A (en) * | 2002-12-16 | 2004-07-15 | Showa Denko Kk | Color filter black matrix resist composition and photosensitive composition used for same composition |
| JP4489566B2 (en) * | 2003-11-27 | 2010-06-23 | 太陽インキ製造株式会社 | Curable resin composition, cured product thereof, and printed wiring board |
| TW200519535A (en) * | 2003-11-27 | 2005-06-16 | Taiyo Ink Mfg Co Ltd | Hardenable resin composition, hardened body thereof, and printed circuit board |
| JP4830310B2 (en) * | 2004-02-23 | 2011-12-07 | 三菱化学株式会社 | Oxime ester-based compound, photopolymerizable composition, and color filter using the same |
| JP4556479B2 (en) * | 2004-04-27 | 2010-10-06 | Ｊｓｒ株式会社 | Radiation-sensitive composition for forming colored layer, color filter, and liquid crystal display panel |
| JP2006268027A (en) * | 2005-02-23 | 2006-10-05 | Jsr Corp | Method for manufacturing plasma display panel and transfer film |
| JP4253306B2 (en) * | 2005-03-01 | 2009-04-08 | 太陽インキ製造株式会社 | Photosensitive paste and fired product pattern formed using the same |
| JP2006309157A (en) * | 2005-04-01 | 2006-11-09 | Jsr Corp | Radiation-sensitive resin composition, protrusion and spacer formed of the same, and liquid crystal display element equipped with them |
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| CN101183219B (en) | 2012-07-04 |
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