201220325 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種平版印刷用導電性膠漿。 【先前技術】 一般，就電子裝置之高精細配線圖型形成技術而言， 廣泛使用光微影蝕刻。但，光微影蝕刻係去除材料以形成 圖型之減法製程，故材料之使用效率低，步驟複雜，於濕 式製程等需要龐大的設備等之問題仍存在。 另外，就於所希望之處附加材料的加法製程，可舉例 如凹版印刷、凹版平版印刷等之印刷法。例如，若依凹版 平版印刷，使導電性膠漿供給·至凹版，再轉印至使用例如 聚矽氧等之彈性體的膠印滾筒，進一步，轉印至平台上的 基材，俾可形成配線圖型等之導電圖型（例如參照專利文 獻1等）。 在如此之凹版平版印刷等的平版印刷法中，從版介由 膠印滾筒而使導電性膠漿轉印至基材，故在各別之步驟要 求良好的轉印性。又，起因於導電性膠漿之拉絲或靜電， 抑制電氣特性劣化（短路不良）的原因之圖型的鬚缺陷等 圖型形狀不良亦成爲必要。因此，具有適當的流變特性， 要求印刷適性優異之導電性膠漿。 〔先前技術文獻〕 〔專利文獻〕 〔專利文獻1〕特開2 0 0 0 - 1 3 0 8 8號公報 -5- 201220325 【發明內容】 〔發明之槪要〕 〔發明欲解決之課題〕 如此地，在導電性膠漿中，要求轉印性等印刷適性之 提昇。在平版印刷中，形成於版上之圖型被轉印至膠印滾 筒上（Off步驟），進一步，從膠印滾筒被轉印至基材（ Set步驟）。此時，若導電性膠漿某種程度未乾燥，於膠 印滾筒上會殘存圖型。另外，若於膠印滾筒上太過乾燥， 此次無法轉印至基材上。因此，大大影響乾燥之導電性膠 漿中所含有的有機溶劑之選擇係很重要。 因此，本發明之目的在於提供一種具有轉印性等良好 之平版印刷適性，可形成高精細之導電圖型的平版印刷用 導電性膠漿。 〔用以解決課題之手段〕 .本實施形態之平版印刷用導電性膠漿，其特徵爲含有 :有機黏合劑樹脂、導電粉末與含有在760mmHg下之沸點 爲250〜3 30°C之高沸點溶劑30〜90質量％之有機溶劑。 藉由如此之構成，具有轉印性等良好之平版印刷適性 ，可形成高精細之配線圖型。 又，本實施形態之平版印刷用導電性膠漿中’有機黏 合劑樹脂係宜至少含有於一分子中包含2個以上羧基之含 羧酸的樹脂。 -6 - 201220325 藉由含有如此之含羧酸的樹脂，導電性膠漿之彈性會 提昇，故，在印刷步驟中轉印（off步驟、及Set步驟）時 ，很難引起膠漿之斷裂’可提昇良好的印刷適性。 又，在本實施形態之平版印刷用導電性膠漿中，宜爲 含有交聯劑。進一步在此交聯劑中宜含有至少於一分子中 含有2個以上縮水甘油基之環氧樹脂。 藉由含有如此之交聯劑，與有機黏合劑樹脂反應，形 成3次元網目鏈構造’可提昇所形成之圖型的耐溶劑性、 密著性。 進一步，宜使如此之平版印刷用導電性膠漿之圖型形 成於版上，將所形成之圖型施予一次轉印至膠印滾筒，將 經轉印之圖型施予二次轉印至基材表面，使經二次轉印之 圖型以80~200°C使其乾燥或硬化。 藉如此做法而形成導電圖型’具有良好的形狀且，可 得到高精細之導電圖型。 〔發明之效果〕 若依本發明之一態樣的平版印刷用導電性膠漿，具有 轉印性等良好的平版印刷適性，可形成高精細之導電圖型 〔用以實施發明之形態〕 以下，說明有關本實施形態之平版印刷用導電性膠漿 201220325 ' 本實施形態之平版印刷用導電性膠漿，其係含有：有 機黏合劑樹脂、導電粉末與含有在760mmHg下之沸點爲 2 5 0~33 0°C之範圍的高沸點溶劑30~90質量％之有機溶劑。 本實施形態之平版印刷用導電性膠漿中的有機黏合劑 樹脂係對膠漿賦予良好的印刷適性，殘存於導電圖型中， 用以賦予密著性或耐彎曲性、硬度等之物性所使用。如此 之有機黏合劑樹脂係只要爲可對膠漿賦予印刷適性者，無 特別限定，可舉例如聚酯樹脂、胺基甲酸酯改性聚酯樹脂 、環氧改性聚酯樹脂、丙烯酸改性聚酯樹脂等之各種改性 聚酯樹脂、聚醚胺基甲酸酯樹脂、聚碳酸酯胺基甲酸酯樹 脂、丙烯酸胺基甲酸酯樹脂、氯化乙烯·醋酸乙烯酯共聚 物、環氧樹脂、酚樹脂、苯氧樹脂、丙烯酸樹脂、聚乙烯 醇縮丁醛樹脂、聚醯胺醯亞胺、聚醯亞胺、聚醯胺、硝基 纖維素、纖維素·乙酸酯· 丁酸酯（CAB )、纖維素·乙 酸酯·丙酸酯（CAP )等之改性纖維素類等。 其中，尤宜至少含有於一分子中含有2個以上之羧基 之含羧酸的樹脂。如此之含羧酸的樹脂具體上可舉例如以 下列舉之樹脂，但不限定於此等。 (1) 一種含羧基之樹脂，其係藉由使（甲基）丙烯 酸等之不飽和羧酸、與具有其以外之不飽和雙鍵的化合物 之1種類以上共聚合所得到者。 (2) —種含羧基之樹脂，其係藉由使（甲基）丙烯 酸等之不飽和羧酸、與具有其以外之不飽和雙鍵的化合物 之1種類以上的共聚物加成丁基縮水甘油基醚、苯基縮水 -8- 201220325 甘油基醚等之單官能環氧化合物所得到者。 (3) —種含羧基之樹脂，其係具有縮水甘油基（甲 基）丙烯酸酯或3，4-環氧基環己基甲基（甲基）丙烯酸酯 等之環氧基與不飽和雙鍵之化合物、與具有其以外之不飽 和雙鍵的化合物之共聚物，使之與丙酸等之飽和羧酸反應 ，於所生成之二級的羥基使多鹼酸酐反應所得到者。 (4) 一種含羧基之樹脂，其係具有馬來酸酐等之不 飽和雙鍵的酸酐、與具有其以外之不飽和雙鍵的化合物之 共聚物，使之與具有丁醇等之羥基的化合物反應所得到者 〇 (5) —種含羧基之樹脂，其係使多官能環氧化合物 與飽和單羧酸反應，於所生成之羥基使飽和或不飽和多鹼 酸酐反應所得到者》 (6) —種含有羥基及羧基之樹脂，其係於聚乙烯醇 衍生物等之含有羥基的聚合物，使之與飽和或不飽和多鹼 酸酐反應所得到者。 (7) —種含羧基之樹脂，其係多官能環氧化合物、 飽和單羧酸、於一分子中至少1個的醇性羥基、與具有與 環氧基反應之醇性羥基以外的1個反應性基之化合物的反 應生成物，使之與飽和或不飽和多鹼酸酐反應所得到者。 (8) —種含羧基之樹脂，其係於1分子中至少具有2 個氧雜環丁烷環的多官能氧雜環丁烷化合物，使之與飽和 單羧反應，對所得到之改性氧雜環丁烷樹脂中的第1級羥 基使飽和或不飽和多鹼酸酐反應所得到者。 -9- 201220325 (9 ) 一種含羧基之樹脂，其係於多官能環氧樹脂使 飽和單羧酸反應後，使多鹼酸酐反應所得到之含羧基之樹 脂’進一步，於1分子中具有1個氧雜環丁烷環的化合物反 應所得到者。 此等之中，尤宜使用（1) 、 （2)及（3)之含有羧 基的樹脂。此等係可任意地調整分子量、玻璃轉移點，可 適宜控制膠漿之印刷適性的調整、或對基材之密著性。 又，如此之含有羧基的樹脂之酸價宜爲40~200mg KOH/g。若含有殘基的樹月旨之酸價未達々OmgKOH/g ,膠駿 之凝集力降低，印刷時易引起轉移不良。另外，若超過 200mgKOH/g，膠獎之黏度太高，必須調配大量之交聯劑 ，很難賦予印刷適性。更宜爲45~150mgKOH/g» 又，於基材使用樹脂薄膜時，從耐彎曲性與對於基材 之密著性的面，宜爲聚酯樹脂、丙烯酸樹脂、聚乙烯醇縮 丁醛樹脂、改性聚酯樹脂、氯化乙烯·醋酸乙烯酯共聚物 、共聚合聚酯樹脂等。 有機黏合劑樹脂係適宜數目平均分子量（Μη)爲 3000〜50000。若數目平均分子量未達3000，易產生印刷時 之轉移不良，很難形成良好的導電圖型。另外，若數目平 均分子量超過50000，起因於膠漿之拉絲之鬚缺陷或線條 的皺紋等易發生，印刷適性劣化。更佳係5000〜3 0000。 又，數目平均分子量係以凝膠滲透色層分析（GPC ) 所測定之標準聚苯乙烯換算的値。 本實施形態之平版印刷用導電性膠漿中的導電粉末係 •10· 201220325 只要可對所形成之導電圖型賦予導電性者即可。如此之 電粉末可舉例如 Ag、Au、Pt、Pd、Ni、Cu、A1、Sn、 、Zn、Fe、Ir、Os、Rh、W、Mo、Ru等。 此等之導電粉末係不限於以單體之形態使用者，亦 爲此等之任一者的合金、或以此等之任一者作爲核或被 層之多層體。進一步，亦可使用氧化錫（Sn02 )、氧化 (In2〇3) 、ITO ( Indium Tin Oxide)等之氧化物。 其形狀係可使用球狀、片狀、樹枝狀（dendrite ) 各種的形狀者，但，若特別考量印刷適性或分散性，宜 用球狀者作爲主體。 如此之導電粉末係以平版印刷用導電性膠漿之不揮 成分（在乾燥步驟不從膠漿中揮發，而殘存於膜中之成 )作爲基準，宜爲85〜95質量％。若未達85重量％，很難 到充分的導電性，若超過9 5質量％，很難得到充分的印 適性，或很難維持導電圖型的形狀。更佳係90〜94質量％ 導電粉末之粒徑係使用球狀之導電粉末時，使用電 顯微鏡（SEM)而以1 0000倍觀察的隨機10個之導電粉 的平均粒徑，宜爲0.1~5μιη。平均粒徑未達Ο.ίμιη時，很 引起導電粉末間之接觸，導電性降低。另外平均粒徑超 5 μπι時，很難得到印刷時之線邊緣的直進性。更佳 0 · 4〜2 μιη。 又，藉微軌跡所測定之平均粒徑中係宜使 0.5〜3·5μιη之大小者。 使用片狀之導電粉末時，使用電子顯微鏡（SEM ) 導 Pb 可 覆 銦 等 使 發 分 得 刷 〇 子 末 難 過 係 用 而 -11 - 201220325 以100 〇〇倍觀察的隨機10個之導電粉的平均粒徑，宜爲 0.1〜ΙΟμπι。平均粒徑未達Ο.ίμηι時，很難引起導電粉末間 之接觸，導電性降低。另外平均粒徑超過1 Ομηι時，很難得 到印刷時之線邊緣的直進性。更佳係0.4〜5 μηι。 又，藉微軌跡所測定之平均粒徑中係宜使用0.5〜7μιη 之大小者。 如此之導電粉末係宜爲銀粉末，其時，銀粉末宜比表 面積爲0.01~2m2/g。比表面積未達〇.〇1 m2/g時，保存時易 引起沈澱，另外，比表面積超過2 m2/g時，吸油量變大而 損及膠漿之流動性。更佳係0.5〜1.5 m2/g。 本實施形態之平版印刷用導電性膠紫中的有機溶劑係 用以賦予良好的印刷適性所使用。如此之有機溶劑係可使 用含有在760mmHg之沸點爲250〜3 3 0t的高沸點溶劑3〇〜9〇 質量％者。 高沸點溶劑係可使用在76〇mmHg之沸點爲25〇~33(rc 者。若沸點未達2 5 0 t，乾燥速度太快，很難轉印至基材 。另外，若超過3 3 0 T：，很難使用來作爲有機溶劑。更佳 係 250〜3〇〇。〇。 如此之高沸點溶劑係可舉例如二戊基苯（沸點 260〜28(TC)、三戊基苯（沸點3〇〇〜32〇<t)、正·201220325 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a conductive paste for lithography. [Prior Art] In general, photolithography etching is widely used in terms of high-definition wiring pattern formation technology of electronic devices. However, the photolithography etching removes the material to form a pattern subtraction process, so the use efficiency of the material is low, the steps are complicated, and problems such as a huge process such as a wet process still exist. Further, as an addition process for adding a material as desired, a printing method such as gravure printing, gravure lithography or the like can be exemplified. For example, if gravure printing is performed by gravure printing, the conductive paste is supplied to a gravure, transferred to an offset cylinder using an elastomer such as polyfluorene, and further, transferred to a substrate on the stage, and a wiring can be formed. A conductive pattern such as a pattern (for example, refer to Patent Document 1, etc.). In the lithography method such as gravure printing, the conductive paste is transferred from the plate to the substrate by the blanket cylinder, so that good transferability is required in the respective steps. In addition, due to the drawing or static electricity of the conductive paste, it is necessary to suppress the deterioration of the electrical characteristics (the short-circuit defect), such as the defect of the pattern, and the shape of the pattern. Therefore, it has a suitable rheological property and requires a conductive paste excellent in printability. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] JP-A-2000 - 1 3 0 8 8 - 5 - 201220325 [Summary of the Invention] [Problems to be Solved by the Invention] In the conductive paste, the printability such as transferability is required to be improved. In lithography, the pattern formed on the plate is transferred onto the blanket cylinder (Off step) and further transferred from the blanket cylinder to the substrate (Set step). At this time, if the conductive paste is not dried to some extent, the pattern remains on the blanket cylinder. In addition, if it is too dry on the blanket cylinder, it cannot be transferred to the substrate at this time. Therefore, it is important to greatly influence the selection of the organic solvent contained in the dried conductive paste. Accordingly, an object of the present invention is to provide a conductive paste for lithographic printing which has excellent lithographic suitability such as transferability and can form a high-precision conductive pattern. [Means for Solving the Problem] The conductive paste for lithographic printing of the present embodiment is characterized in that it contains an organic binder resin, a conductive powder, and a high boiling point of 250 to 3 30 ° C at 760 mmHg. The solvent is 30 to 90% by mass of an organic solvent. With such a configuration, it is possible to form a high-definition wiring pattern with good lithographic suitability such as transferability. Further, in the conductive paste for lithographic printing of the present embodiment, the "organic binder resin" preferably contains at least a carboxylic acid-containing resin containing two or more carboxyl groups in one molecule. -6 - 201220325 By containing such a carboxylic acid-containing resin, the elasticity of the conductive paste is increased, so that it is difficult to cause the breakage of the glue when transferring (off step, and set step) in the printing step. Improves printability. Further, in the conductive paste for lithographic printing of the embodiment, it is preferred to contain a crosslinking agent. Further, it is preferable that the crosslinking agent contains an epoxy resin containing at least two glycidyl groups in at least one molecule. By containing such a crosslinking agent and reacting with the organic binder resin to form a three-dimensional mesh chain structure, the solvent resistance and adhesion of the formed pattern can be improved. Further, it is preferable that the pattern of the conductive paste for lithography is formed on the plate, the formed pattern is applied to the blanket cylinder at a time, and the transferred pattern is subjected to secondary transfer to The surface of the substrate is dried or hardened by a secondary transfer pattern at 80 to 200 °C. By doing so, the conductive pattern is formed to have a good shape and a high-precision conductive pattern can be obtained. [Effects of the Invention] The conductive paste for lithographic printing according to one aspect of the present invention has excellent lithographic suitability such as transferability, and can form a high-precision conductive pattern (for the form of the invention). The conductive paste for lithographic printing according to the present embodiment is described in the present invention. The conductive paste for lithographic printing according to the present embodiment contains an organic binder resin, a conductive powder, and a boiling point of 260 mmHg. ~33 0 ° C range of high boiling point solvent 30 ~ 90% by mass of organic solvent. The organic binder resin in the conductive paste for lithographic printing of the present embodiment imparts good printability to the paste, and remains in the conductive pattern to impart physical properties such as adhesion, bending resistance, and hardness. use. The organic binder resin is not particularly limited as long as it can impart printability to the paste, and examples thereof include a polyester resin, a urethane-modified polyester resin, an epoxy-modified polyester resin, and an acrylic acid modification. Various modified polyester resins such as polyester resins, polyether urethane resins, polycarbonate urethane resins, urethane acrylate resins, chlorinated ethylene vinyl acetate copolymers, Epoxy resin, phenol resin, phenoxy resin, acrylic resin, polyvinyl butyral resin, polyamidimide, polyimine, polyamine, nitrocellulose, cellulose acetate Modified cellulose such as butyrate (CAB), cellulose, acetate, propionate (CAP), and the like. Among them, it is particularly preferable to contain at least a carboxylic acid-containing resin containing two or more carboxyl groups in one molecule. Specific examples of the carboxylic acid-containing resin include, but are not limited to, the resins listed below. (1) A carboxyl group-containing resin obtained by copolymerizing one type or more of an unsaturated carboxylic acid such as (meth)acrylic acid with a compound having an unsaturated double bond other than the above. (2) A carboxyl group-containing resin obtained by adding a butyl group to a copolymer of one or more types of an unsaturated carboxylic acid such as (meth)acrylic acid or a compound having an unsaturated double bond other than A monofunctional epoxy compound such as glyceryl ether, phenyl shrinkage-8-201220325 glyceryl ether or the like. (3) A carboxyl group-containing resin having an epoxy group and an unsaturated double bond such as glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate. A copolymer of a compound and a compound having an unsaturated double bond other than the above is reacted with a saturated carboxylic acid such as propionic acid to obtain a polybasic acid anhydride obtained by reacting the generated secondary hydroxyl group. (4) A carboxyl group-containing resin which is a copolymer of an acid anhydride having an unsaturated double bond such as maleic anhydride and a compound having an unsaturated double bond other than the compound having a hydroxyl group such as butanol The reaction product (5) is a carboxyl group-containing resin obtained by reacting a polyfunctional epoxy compound with a saturated monocarboxylic acid to react a saturated or unsaturated polybasic acid anhydride with a hydroxyl group formed (6) A resin containing a hydroxyl group and a carboxyl group, which is obtained by reacting a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative with a saturated or unsaturated polybasic acid anhydride. (7) A resin containing a carboxyl group, which is a polyfunctional epoxy compound, a saturated monocarboxylic acid, an alcoholic hydroxyl group having at least one molecule in one molecule, and one other than an alcoholic hydroxyl group having an epoxy group reaction. The reaction product of the reactive group compound is obtained by reacting it with a saturated or unsaturated polybasic acid anhydride. (8) A carboxyl group-containing resin which is a polyfunctional oxetane compound having at least two oxetane rings in one molecule, which is reacted with a saturated monocarboxylic acid to obtain a modified one. The first-stage hydroxyl group in the oxetane resin is obtained by reacting a saturated or unsaturated polybasic acid anhydride. -9- 201220325 (9) A carboxyl group-containing resin which is obtained by reacting a polybasic acid anhydride to a saturated monocarboxylic acid to react a polybasic acid anhydride to obtain a carboxyl group-containing resin. Further, it has 1 in 1 molecule. A compound obtained by reacting a compound of an oxetane ring. Among these, it is preferable to use the carboxyl group-containing resin of (1), (2) and (3). These can adjust the molecular weight and the glass transition point arbitrarily, and can appropriately control the adjustment of the printability of the paste or the adhesion to the substrate. Further, the acid value of such a carboxyl group-containing resin is preferably 40 to 200 mg KOH/g. If the acid value of the tree containing the residue does not reach 々OmgKOH/g, the cohesive force of the rubber is reduced, and the transfer is liable to cause poor transfer. In addition, if it exceeds 200 mgKOH/g, the viscosity of the glue is too high, and a large amount of a crosslinking agent must be formulated, which makes it difficult to impart printability. More preferably, it is 45 to 150 mg KOH/g». When the resin film is used as the substrate, the surface of the film which is resistant to bending and adhesion to the substrate is preferably a polyester resin, an acrylic resin, or a polyvinyl butyral resin. A modified polyester resin, a vinyl chloride-vinyl acetate copolymer, a copolymerized polyester resin, or the like. The organic binder resin has a suitable number average molecular weight (??) of from 3,000 to 50,000. If the number average molecular weight is less than 3,000, it tends to cause poor transfer during printing, and it is difficult to form a good conductive pattern. Further, if the number average molecular weight exceeds 50,000, the defects such as the whisker of the glue or the wrinkles of the lines are liable to occur, and the printability is deteriorated. Better system 5000~3 0000. Further, the number average molecular weight is a standard polystyrene equivalent of ruthenium measured by gel permeation chromatography (GPC). The conductive powder in the conductive paste for lithographic printing of the present embodiment is required to provide conductivity to the formed conductive pattern. Such an electric powder may, for example, be Ag, Au, Pt, Pd, Ni, Cu, A1, Sn, Zn, Fe, Ir, Os, Rh, W, Mo, Ru or the like. These conductive powders are not limited to those which are used in the form of a single body, or an alloy of any of them, or a multilayer of the core or the layer. Further, an oxide such as tin oxide (SnO 2 ), oxidized (In 2 〇 3 ), or ITO (Indium Tin Oxide) may be used. The shape may be a spherical shape, a sheet shape, or a dendrite shape. However, if the printability or dispersibility is particularly considered, it is preferable to use a spherical body as a main body. Such a conductive powder is preferably 85 to 95% by mass based on the non-volatile component of the conductive paste for lithography (which is not volatilized from the dope in the drying step and remains in the film). If it is less than 85% by weight, it is difficult to obtain sufficient conductivity, and if it exceeds 95% by mass, it is difficult to obtain sufficient printability, or it is difficult to maintain the shape of the conductive pattern. More preferably, 90 to 94% by mass of the conductive powder. When the spherical conductive powder is used, the average particle diameter of the random 10 conductive powders observed by an electron microscope (SEM) at 1,000 times is preferably 0.1~ 5μιη. When the average particle diameter is less than Ο. ίμιη, the contact between the conductive powders is caused, and the conductivity is lowered. When the average particle diameter exceeds 5 μm, it is difficult to obtain the straightness of the line edge at the time of printing. More preferably 0 · 4~2 μιη. Further, it is preferable that the average particle diameter measured by the microtrajectory is 0.5 to 3 · 5 μmη. When using a sheet-shaped conductive powder, use an electron microscope (SEM) to guide Pb to cover indium, etc., so that the hair is distributed to the end of the tweezers. -11 - 201220325 Random 10 conductive powders observed at 100 〇〇 times The average particle diameter is preferably 0.1 to ΙΟμπι. When the average particle diameter is less than Ο. ίμηι, it is difficult to cause contact between the conductive powders, and the conductivity is lowered. When the average particle diameter exceeds 1 Ομηι, it is difficult to obtain the straightness of the edge of the line at the time of printing. More preferably 0.4 to 5 μηι. Further, it is preferable to use a size of 0.5 to 7 μm in the average particle diameter measured by the microtrajectory. Such a conductive powder is preferably a silver powder, and the silver powder preferably has a surface area of 0.01 to 2 m 2 /g. When the specific surface area is less than 〇1 m2/g, precipitation tends to occur during storage. When the specific surface area exceeds 2 m2/g, the oil absorption increases and the fluidity of the paste is impaired. More preferably 0.5 to 1.5 m2/g. The organic solvent in the conductive paste purple for lithographic printing of the present embodiment is used to impart good printability. Such an organic solvent can be used in a high boiling point solvent having a boiling point of 250 to 30,000 at 760 mmHg of 3 〇 to 9 〇 by mass. The high-boiling solvent can be used at a boiling point of 76〇mmHg of 25〇~33 (rc. If the boiling point is less than 250t, the drying speed is too fast and it is difficult to transfer to the substrate. In addition, if it exceeds 3 3 0 T: It is difficult to use as an organic solvent. More preferably, it is 250 to 3 Torr. 如此. Such a high boiling point solvent may, for example, be dipentylbenzene (boiling point 260~28 (TC), triamylbenzene (boiling point) 3〇〇~32〇<t), 正·
、四乙二醇 醇（沸點2 5 5〜2 5 9 t : 、二乙二醇單乙酸酯（沸點25〇t )、三乙 °c)、三乙二醇單乙基醚（沸點256 t ), 基醚（沸點2 7 1 °C )、四乙二醇（她社1 9 7 3 -12- 201220325 單丁基醚（沸點304 °C )、三丙二醇（沸點26 7 t：)、 2,2,4-三甲基-1,3-戊二醇單異丁酸酯（沸點253 t )等。又 ，石油系烴類可舉例如新日本石油公司製AF Solvent 4號 (沸點 240~265 °C ) 、5號（沸點=275〜306°C ) ' 6號（沸 點 296〜317°C ) 、7號（沸點 259〜282°C )、及 0號 Solvent Η (沸點245~265°C )等。此等係可單獨或混合2種以上而 使用》 其中，從有機黏合劑樹脂之溶解性等的觀點，可適宜 使用三乙二醇衍生物或三丙二醇衍生物。 如此之高沸點沸劑係有機溶劑中含有3 0〜9 0質量％。若 未達30質量％，膠漿之乾燥速度太快，很難得到良好的轉 印性等之印刷適性。另外，若超過90質量％，膠漿很難乾 燥，殘存於膠印滾筒上等印刷適性劣化。更佳係30〜60質 量％。 又，此等高沸點溶劑以外之有機溶劑係只要爲可溶解 有機黏合劑樹脂者即可，可使用公知者。可舉例如甲苯、 二甲苯、醋酸乙酯、醋酸丁酯、甲醇、乙醇、異丙醇、異 丁醇、1-丁醇、二丙酮醇、乙二醇單丁基醚、丙二醇單甲 基醚、丙二醇單乙基醚、丙二醇單甲基醚乙酸酯、萜烯醇 、甲乙酮、卡必醇、卡必醇乙酸酯、丁基卡必醇等。此等 係可單獨或混合2種以上而使用。 本實施形態之平版印刷用導電性膠漿係藉由含有如此 之高沸點溶劑之有機溶劑’宜調整成適於平版印刷之膠漿 黏度、例如50〜1 000 dPa· s»黏度未達50 dPa· s時，所印 -13- 201220325 刷之圖型的膜厚變薄，所得到之導電圖型的表面阻 高。另外，若黏度超過1〇〇〇 dPa· s’於凹版印刷時 之膠漿很難刮取，易引起地污染（膠漿於非畫線部 )、或滲浸等之印刷不良。更佳之黏度爲1〇〇~750 〇 又，在本發明之膠漿的黏度係使用錐板式黏度 切速度以10s·1、25 °C的條件所測定的値。 又，在本實施形態之平版印刷用導電性膠漿中 成3次元網目鏈構造，爲提昇所形成之圖型的耐溶 密著性，宜進一步含有交聯劑。 交聯劑係只要不使印刷適性劣化，可與有機黏 脂反應，交聯即可。如此之交聯劑係只要爲藉加熱 樹脂即可，無特別限定。但可舉例如環氧樹脂、酚 三聚氰胺樹脂、醇酸樹脂、聚胺基甲酸酯樹脂、聚 '丙烯酸樹脂、聚醯亞胺樹脂、及其等之改性樹脂 此等單獨或組合2種以上而使用。其他，可舉例如 中至少具有2個氧雜環丁烷基之氧雜環丁烷化合物。 如此之交聯劑中，宜至少含有於1分子中含有 油基2個以上的環氧樹脂。如此之環氧樹脂，可舉 酚A型、氫化雙酚a型、雙酚F型、雙酚S型、酚酚 型、甲酌酚醛清漆型、雙酚A之酚醛清漆型、聯酚 二甲酸型、三酚甲烷型、N_縮水甘油基型、N_縮水 型之環氧樹脂、脂環式環氧樹脂等公知之環氧樹脂 限定於特定者’又，可使此等單獨或組合2種以上 抗易變 刮刀板 之附著 d P a · s 計，剪 ，宜形 劑性、 合劑樹 硬化之 樹脂、 酯樹脂 ，可使 於分子 縮水甘 例如雙 醛清漆 型、聯 甘油基 ，但不 而使用 -14- 201220325 此等環氧樹脂之調配率係有機黏合劑樹脂每100質量 份，適宜爲1~1〇〇質量份，宜爲5〜40質量份。 又，上述成分以外，亦可調配用以促進有機黏合劑樹 脂與交聯劑之反應的硬化觸媒例如胺化合物、咪唑衍生物 等。 又，爲著色本實施形態之平版印刷用導電性膠漿，可 含有著色劑。著色劑之種類或形狀等無特別限定，可使用 公知者。著色劑之顏色例如作爲顯示器用途時，爲用以抑 制外光反射造成充分的亮度降低宜爲適宜之顏色。較佳係 可舉例如藍、黑、3色混合所產生之黑色等。 尤其黑色爲適宜，可使用碳黑、溶劑黑、油墨等，但 ，從取得容易性等，適宜爲色材用碳黑。可舉例如碳黑係 通道黑、爐黑、或燈黑等之色材用碳黑、及導電性碳黑、 乙決黑等。 如此之著色劑的調配量係可得到良好的印刷適性，只 要爲可著色於目的之亮度即可。就印刷適性之觀點，相對 於有機黏合劑樹脂100質量份，宜爲100質量份以下。若超 過100質量份，產生明顯黏度之上昇或搖變性太高等之問 題。更佳係80質量份以下。 又，下限係例如作爲顯示器用途時，相對於有機黏合 劑樹脂1 〇〇質量份，宜爲5質量份以上。著色劑之調配量未 達5質量份時係膠漿之亮度變高，顯示器之辨視性惡化 更佳係10質量份以上。 -15- 201220325 如此之著色劑係可以粉體或分散液添加。 在本實施形態之平版印刷用導電性膠漿中，爲得到更 優異之印刷適性與導電性，有機黏合劑樹脂、導電粉末、 著色劑（所含有的情形）之調配量在質量基準中，宜（導 電粉末之調配量+著色劑之調配量）/有機黏合劑樹脂之調 配量：滿足A爲12SAS26 之關係。 若A値未達12，因相對地導電粉之比率減少，導電性 降低，且膠漿中之粉體成分的比率變少，故很難形成適於 印刷之搖變性，若超過26，膠漿中之粉體的比率太多，成 爲搖變性高的膠漿，無法達成適於印刷之流變性。更佳係 1 3 S A $ 22。 其他，在無損印刷適性之範圍，亦可調配金屬分散劑 、搖變賦予劑、消泡劑、流平劑、表面張力降低劑、稀釋 劑、可塑劑、抗氧化劑、金屬惰性化劑、偶合劑或塡充劑 等之添加劑。 在本實施形態之平版印刷用導電性膠漿中，爲產生良 好的印刷適性，宜爲使膠漿之沾黏値爲5〜35 »若沾黏値未 達5，印刷時膠漿之轉移性差，使印刷品質惡化，印刷後 之膜厚變薄，有表面電阻變高之傾向。另外，若沾黏値超 過3 5，印刷時易引起被印刷物之拾取（被印刷物之破壞） 或堵塞（被印刷物堵塞於印刷機）。更宜爲1 〇〜30 » 又，沾黏値係使用旋轉沾黏計（一般名：Incometer) ，爲以30°C、400旋轉的條件所測定之値。 -16- 201220325 如此所構成之本實施形態的平版印刷用導電性膠漿， 可於印刷電路板、玻璃基板、或所謂P E T薄膜等之樹脂薄 膜的基材上，藉平版印刷形成導電性膠漿。 首先，於凹版（Gravure)等之凹版或凸版等的版上 ，供給導電性膠漿，形成所希望之圖型。此時，使用於如 凹版平版印刷之凹版印刷之版，係對銅、42合金、玻璃等 所構成之筒體或平版表面，實施照相製版或雷射雕刻等而 製版。依需要而實施鍍鉻處理或DLC (類鑽石碳）處理， 提昇凹版之耐久性。 如此做法，使所形成之圖型1次轉印於由例如聚矽氧 橡膠等所構成之膠印滾筒表面。使經1次轉印之圖型進一 步2次轉印至平台上所載置之基材上，俾於基材上形成塗 膜圖型。 然後，使所得到之塗膜圖型藉由例如熱風循環式乾燥 爐等，以80〜200°C乾燥或硬化。如此做法，於基材上可形 成導電圖型。在所得到之導電圖型中，可得到具有良好形 狀且高精細的導電圖型。 又，藉由於透明基材上形成網目狀之導電圖型，可形 成使用來作爲顯示器前面板（遮蔽材）之透光性導電薄膜 〇 此時，透明基材係可使用樹脂薄膜，可舉例如聚酯樹 脂、丙烯酸樹脂、聚碳酸酯樹脂、聚醚颯樹脂、聚丙烯樹 脂、三乙醯基纖維素樹脂、二環戊二烯樹脂、降冰片烯樹 脂、胺基甲酸酯樹脂等所構成之樹脂薄膜。薄膜之表面係 -17- 201220325 依需要亦可設有硬塗層、易接著層、離型處理層、導電性 聚合物層、油墨接受層等，又，亦可實施電漿處理等。薄 膜之厚度一般爲20~800μηι ^ 又，所謂網目狀之導電圖型係可爲三角形、四角形、 五角形、其他之Ν角形（Ν爲6以上之整數）等之格子狀， 亦可爲圓形、葉型等之圖型，亦可爲不定形。 又，此圖型之線寬宜爲10〜8 Ομηι，線間隔爲 10 0~5〇0μιη。若使線寬或線間隔太增大，所得到之導電性 圖型易顯目，有畫面之辨視性降低之傾向。又，若線間隔 太小，所得到之導電圖型變細（每單位面積之線的條數變 多）、可見光線之透過率降低，有畫面變暗之傾向。另外 ，若線寬、線間隔小，有很難形成均一圖型的傾向。更佳 係線寬爲1 〇〜4 0 μ m，線間隔爲1 2 5〜5 0 0 μ m。 又，此時，藉由於膠漿中添加著色劑，不需要黑化處 理。 進一步，亦可依需要而對所得到之透光性導電薄膜， 實施抗反射處理、用以色補正的著色處理、近紅外線吸收 處理等之後處理。又，進一步，亦可層合用以貼黏於顯示 器的黏著劑。 在如此做法所形成之透光性導電薄膜中，可不實施電 鍍處理，賦予充分的導電性，得到優異之電磁波遮蔽性能 【實施方式】 -18- 201220325 〔實施例〕 以下，表示實施例及比較例而更具體地說明本實施形 態，但本發明係不限定於此等實施例。又，在以下中，所 謂「份」係只要無特別聲明，全部表示「質量份」。 (含有羧酸之樹脂的合成例1) 於具備溫度計、攪拌機、滴入漏斗、及回流冷卻器之 燒瓶中，以0.80: 0.20之莫耳比饋入甲基丙烯酸甲醋與丙 烯酸’置入作爲溶劑之三乙二醇單丁基醚（沸點27丨°C ) 、作爲觸媒之偶氮雙異丁腈，氮環境下，以80艺攪拌6小 時，得到不揮發成分爲40質量％之含有羧酸的樹脂溶液。 所得到之樹脂係數目平均分子量爲1 5000、重量平均 分子量爲約40000，酸價爲約97mgK〇H/g。又，重量平均 分子量係藉由三根串聯之高速液體色層分析測定島津製作 所公司製泵浦LC-6AD.與昭和電工公司製管柱shodex (註 冊商標）KF-804、KF-803、KF-802。以下，稱此含有殘酸 的樹脂溶液爲清漆-1。 (含有羧酸的樹脂之合成例2) 將溶劑改變爲三丙二醇單甲基醚（沸點=2 4 3 t )，以 與合成例1同樣的合成方法、同樣之饋入比，得到不揮發 成分40質量％之含有羧酸的樹脂。數目平均分子量、重量 平均分子量及酸價係與清漆-1同樣的値。以下，稱此含有 羧酸的樹脂爲清漆-2° -19- 201220325 (實施例1〜5、及比較例1、2 ) 以表1所示之調配比率調配各成分，以3根輥輪進行混 練而得到導電性膠漿。又，膠漿之黏度係調整於約1 5〇d Pa· s 〇 【表1】 調配成分 實施例 比較例 1 2 3 4 5 1 2 清漆一 1 250 250 250 — — | - 250 清漆一 2 — — — 250 — | 250 — 苯氧樹脂※1 — 一 — — 100 — 導電粉末※2 1880 1880 1880 1880 1880 1880 1880 有機溶劑※3 37.5 110 160 37.5 125 125 0 有機溶劑※4 77 0 0 80 225 0 125 硬化觸媒※5 1 1 1 1 1 1 1 交聯劑※6 20 20 20 20 20 20 20 微粉二氧化矽※7 0 0 2 0 0 0 0 * 1 : Inchem公司製PKHB(Mn=9500) *2 :平均粒徑1·5μπι之球狀銀粉末 *3 :二乙二醇單乙基醚乙酸醋(沸點=217°C、甘醇酯系溶劑） *4 :三乙二醇單丁基醚(沸點=271°C、高沸點溶劑） *5 : 2,4-二胺基-6-[2’-甲基咪唑基-(1)]-乙基·s-三嗪三聚異氰酸加成物 *6 :雙酣A型環氧樹脂(三菱化學公司製jER-828) *7:日本Aerosil公司製Aerosil#200 將實施例1〜4及比較例1、2之有機溶劑中的高沸點溶 劑之比例表示於表2中。 -20- 201220325 【表2】 溶劑比率[質量％] 實施例 比較例 1 2 3 4 5 1 2 髙沸點溶劑 86% 58% 48% 30¾ 64¾ 0% 100% 其他溶劑 14¾ 42% 52% 70% 36¾ 100¾ 0% 對於如此做法所得到之各導電性膠漿，如以下般進行 評估。 (簡易凹版印刷之印刷適性的評估） (試料之製作） 使所得到之各導電性膠漿，於形成線/距=70/30μιη、 版深：ΙΟμιη的條紋圖型之玻璃凹版的凹部，使用不銹鋼刮 刀而塡充。 然後，使此玻璃凹版抵住由橡膠硬度30°之聚矽氧橡 膠所構成的膠印滾筒，使塡充於凹部之導電性膠漿轉印至 膠印滾筒表面（off步驟）。進一步，於厚1.8mm之鈉玻璃 表面轉印膠印滾筒表面之導電性膠漿的圖型（Set步驟） 〇 對於所得到之試料，如以下般進行評估。 (印刷適性1 :轉印性評估）, tetraethylene glycol alcohol (boiling point 2 5 5~2 5 9 t : , diethylene glycol monoacetate (boiling point 25〇t), triethyl), triethylene glycol monoethyl ether (boiling point 256 t), alkyl ether (boiling point 2 7 1 °C), tetraethylene glycol (she is 1 9 7 3 -12- 201220325 monobutyl ether (boiling point 304 ° C), tripropylene glycol (boiling point 26 7 t:), 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (boiling point: 253 t), etc. Further, petroleum-based hydrocarbons include, for example, AF Solvent No. 4 manufactured by New Nihon Petroleum Co., Ltd. (boiling point 240) ~265 °C), No. 5 (boiling point = 275~306°C) 'No. 6 (boiling point 296~317°C), No. 7 (boiling point 259~282°C), and No. 0 Solvent Η (boiling point 245~265) (C), etc. These may be used singly or in combination of two or more kinds thereof. Among them, a triethylene glycol derivative or a tripropylene glycol derivative can be suitably used from the viewpoint of solubility of the organic binder resin and the like. The boiling point boiling agent contains 30 to 90% by mass in the organic solvent. If it is less than 30% by mass, the drying speed of the dope is too fast, and it is difficult to obtain good transferability such as transferability. %, the glue is difficult to dry, The printing property is deteriorated on the offset cylinder, and is preferably 30 to 60% by mass. Further, the organic solvent other than the high-boiling solvent may be any one that can dissolve the organic binder resin, and a known one can be used. Such as toluene, xylene, ethyl acetate, butyl acetate, methanol, ethanol, isopropanol, isobutanol, 1-butanol, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Monoethyl ether, propylene glycol monomethyl ether acetate, terpene alcohol, methyl ethyl ketone, carbitol, carbitol acetate, butyl carbitol, etc. These may be used alone or in combination of two or more. The conductive paste for lithographic printing of the present embodiment is preferably adjusted to a viscosity suitable for lithographic paste by an organic solvent containing such a high boiling point solvent, for example, a viscosity of 50 to 1 000 dPa·s» is less than 50. When dPa·s, the film thickness of the pattern of the printed-13-201220325 brush is thin, and the surface resistance of the obtained conductive pattern is high. In addition, if the viscosity exceeds 1〇〇〇dPa·s' in gravure printing The glue is difficult to scrape, which is easy to cause pollution (the glue is not painted) Printing), or impregnation, etc. The better viscosity is 1〇〇~750 〇, and the viscosity of the glue of the present invention is determined by the cone-plate viscosity cutting speed at 10s·1 and 25°C. Further, in the conductive paste for lithographic printing of the present embodiment, a three-dimensional mesh chain structure is formed, and in order to enhance the solvent resistance of the formed pattern, it is preferable to further contain a crosslinking agent. It can react with organic lipids and crosslink without deteriorating printability. The crosslinking agent is not particularly limited as long as it is a heating resin. However, for example, an epoxy resin, a phenol melamine resin, an alkyd resin, a polyurethane resin, a poly 'acrylic resin, a polyimide resin, and the like, and the like may be used alone or in combination of two or more. And use. Other examples include an oxetane compound having at least two oxetanyl groups. Among such a crosslinking agent, it is preferred to contain at least two or more epoxy resins containing one or more oil groups. Such an epoxy resin may be a phenol type A, a hydrogenated bisphenol a type, a bisphenol F type, a bisphenol S type, a phenol type, a novolac type, a novolac type phenol varnish type, a biphenol dicarboxylic acid type. A known epoxy resin such as a trisphenol methane type, an N-glycidyl type, an N_shrinkable type epoxy resin, an alicyclic epoxy resin, or the like is limited to a specific one's, and these may be individually or in combination 2 The above-mentioned anti-variable scraper plate adhesion d P a · s meter, shear, suitable shape, mixture of tree hardening resin, ester resin, can be condensed in the molecule such as dialdehyde varnish type, glycerol, but not The use ratio of the epoxy resin of the use of the epoxy resin is preferably from 1 to 1 part by mass, preferably from 5 to 40 parts by mass, per 100 parts by mass of the organic binder resin. Further, in addition to the above components, a curing catalyst such as an amine compound or an imidazole derivative for promoting the reaction between the organic binder resin and the crosslinking agent may be blended. Further, in order to color the conductive paste for lithographic printing of the embodiment, a coloring agent may be contained. The type, shape, and the like of the colorant are not particularly limited, and those known to use can be used. When the color of the coloring agent is used as a display, for example, it is preferable to use a color suitable for suppressing reflection of external light to have a sufficient brightness reduction. Preferably, for example, black, which is produced by mixing blue, black, or three colors, or the like can be given. In particular, black is suitable, and carbon black, solvent black, ink, or the like can be used. However, it is suitable for carbon black for color materials from the viewpoint of ease of availability. For example, carbon black for color materials such as carbon black channel black, furnace black, or lamp black, and conductive carbon black, black black, and the like can be given. Such a coloring agent can be formulated to have good printability, as long as it can be colored for the purpose. The viewpoint of the printability is preferably 100 parts by mass or less based on 100 parts by mass of the organic binder resin. If it exceeds 100 parts by mass, there is a problem that the apparent viscosity is increased or the shake is too high. More preferably, it is 80 parts by mass or less. In addition, the lower limit is preferably 5 parts by mass or more based on 1 part by mass of the organic binder resin. When the amount of the coloring agent is less than 5 parts by mass, the brightness of the dope becomes high, and the visibility of the display deteriorates more preferably 10 parts by mass or more. -15- 201220325 Such a coloring agent can be added in powder or dispersion. In the conductive paste for lithographic printing of the present embodiment, in order to obtain more excellent printability and conductivity, the amount of the organic binder resin, the conductive powder, and the colorant (in the case of inclusion) is preferably in the mass basis. (Adjustment amount of conductive powder + blending amount of colorant) / Formulation amount of organic binder resin: Satisfy the relationship of A to 12SAS26. If A値 is less than 12, the ratio of the relatively conductive powder is reduced, the conductivity is lowered, and the ratio of the powder component in the dope is reduced, so it is difficult to form a shakeability suitable for printing, and if it exceeds 26, the glue The ratio of the powder in the powder is too large, and it becomes a high-density glue, and it is impossible to achieve rheology suitable for printing. Better system 1 3 S A $ 22. Others, in the range of non-destructive printing suitability, metal dispersant, shake imparting agent, antifoaming agent, leveling agent, surface tension reducing agent, diluent, plasticizer, antioxidant, metal inerting agent, coupling agent may also be formulated. Or an additive such as a sputum. In the conductive paste for lithographic printing of the present embodiment, in order to produce good printability, it is preferable to make the glue adhere to 5 to 35. If the adhesive is less than 5, the transfer property of the paste is poor. The printing quality is deteriorated, the film thickness after printing is reduced, and the surface resistance tends to be high. In addition, if the adhesive is more than 3 5, it may cause picking up of the printed matter (destruction of the printed matter) or clogging (the printed matter is clogged in the printing machine). More preferably, it is 1 〇 to 30 » Further, the viscous sputum is measured by a rotary viscous meter (general name: Incometer) under the conditions of 30 ° C and 400 rotation. -16-201220325 The conductive paste for lithographic printing of the present embodiment thus constituted can form a conductive paste by lithographic printing on a substrate of a resin film such as a printed circuit board, a glass substrate or a so-called PET film. . First, a conductive paste is supplied onto a plate such as a gravure or a relief such as Gravure to form a desired pattern. In this case, a plate for gravure printing such as gravure printing is used to perform plate making or laser engraving on a cylinder or a lithographic surface composed of copper, 42 alloy, glass or the like. Chrome plating or DLC (Diamond-like Carbon) treatment is applied as needed to improve the durability of the intaglio. In this manner, the formed pattern is transferred once to the surface of the blanket cylinder composed of, for example, polyoxyethylene rubber or the like. The pattern of the primary transfer is transferred to the substrate placed on the stage by a second transfer, and a coating pattern is formed on the substrate. Then, the obtained coating film pattern is dried or hardened at 80 to 200 ° C by, for example, a hot air circulation type drying oven. In this way, a conductive pattern can be formed on the substrate. In the resulting conductive pattern, a conductive pattern having a good shape and high definition can be obtained. Further, by forming a mesh-like conductive pattern on the transparent substrate, a light-transmitting conductive film which is used as a front panel (masking material) of the display can be formed. In this case, a resin film can be used as the transparent substrate, for example, Polyester resin, acrylic resin, polycarbonate resin, polyether oxime resin, polypropylene resin, triethylene sulfonated cellulose resin, dicyclopentadiene resin, norbornene resin, urethane resin, etc. Resin film. Surface of the film -17- 201220325 A hard coat layer, an easy-adhesion layer, a release coating layer, a conductive polymer layer, an ink receiving layer, or the like may be provided as needed, or a plasma treatment may be performed. The thickness of the film is generally 20 to 800 μm ^ ^, and the so-called mesh-like conductive pattern may be a triangle, a quadrangle, a pentagon, or other corners (Ν is an integer of 6 or more), or may be a circle, The pattern of the leaf type, etc., may also be amorphous. Moreover, the line width of this pattern should be 10~8 Ομηι, and the line spacing is 10 0~5〇0μιη. If the line width or the line interval is too large, the obtained conductivity pattern is easy to be noticed, and there is a tendency that the visibility of the screen is lowered. Further, if the line spacing is too small, the obtained conductive pattern becomes fine (the number of lines per unit area increases), and the transmittance of visible light decreases, and the screen tends to become dark. In addition, if the line width and the line interval are small, there is a tendency that it is difficult to form a uniform pattern. More preferably, the line width is 1 〇 to 4 0 μ m, and the line spacing is 1 2 5 to 5 0 0 μ m. Further, at this time, since the coloring agent is added to the dope, no blackening treatment is required. Further, the obtained light-transmitting conductive film may be subjected to an anti-reflection treatment, a coloring treatment for color correction, a near-infrared absorption treatment, or the like after the treatment. Further, it is also possible to laminate an adhesive for adhering to the display. In the light-transmitting conductive film formed by the above-described method, it is possible to provide sufficient conductivity without giving a plating treatment, and to obtain excellent electromagnetic wave shielding performance. [Embodiment] -18-201220325 [Embodiment] Hereinafter, examples and comparative examples are shown. The present embodiment will be more specifically described, but the present invention is not limited to the embodiments. In addition, in the following, "parts" are all "mass parts" unless otherwise stated. (Synthesis Example 1 of a carboxylic acid-containing resin) In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, a methyl ketone methacrylate and acrylic acid were fed at a molar ratio of 0.80: 0.20. Solvent triethylene glycol monobutyl ether (boiling point: 27 丨 ° C), azobisisobutyronitrile as a catalyst, and stirred at 80 ° for 6 hours in a nitrogen atmosphere to obtain a nonvolatile content of 40% by mass. A resin solution of a carboxylic acid. The obtained resin had a number average molecular weight of 15,000, a weight average molecular weight of about 40,000, and an acid value of about 97 mgK〇H/g. In addition, the weight average molecular weight was measured by three high-speed liquid chromatography layers in series, and the pumping LC-6AD manufactured by Shimadzu Corporation was used. The column shodex (registered trademark) KF-804, KF-803, and KF-802 manufactured by Showa Denko Co., Ltd. . Hereinafter, the resin solution containing the residual acid is referred to as varnish-1. (Synthesis Example 2 of a carboxylic acid-containing resin) The solvent was changed to tripropylene glycol monomethyl ether (boiling point = 2 4 3 t), and a non-volatile component was obtained by the same synthesis method as in Synthesis Example 1 and the same feed ratio. 40% by mass of a carboxylic acid-containing resin. The number average molecular weight, weight average molecular weight, and acid value are the same as those of varnish-1. Hereinafter, the carboxylic acid-containing resin is referred to as varnish-2° -19-201220325 (Examples 1 to 5, and Comparative Examples 1 and 2). The components are blended at the mixing ratio shown in Table 1, and are carried out by 3 rolls. The conductive paste is obtained by kneading. Moreover, the viscosity of the glue is adjusted to about 15 〇d Pa·s 〇 [Table 1] Formulation Composition Example Comparative Example 1 2 3 4 5 1 2 Varnish 1 250 250 250 — — | - 250 Varnish 1 - — — 250 — | 250 — phenoxy resin ※1 — one — — 100 — Conductive powder*2 1880 1880 1880 1880 1880 1880 1880 Organic solvent*3 37.5 110 160 37.5 125 125 0 Organic solvent*4 77 0 0 80 225 0 125 Hardening catalyst ※5 1 1 1 1 1 1 1 Crosslinking agent ※6 20 20 20 20 20 20 20 Micronized cerium oxide ※7 0 0 2 0 0 0 0 * 1 : PKHB made by Inchem Co., Ltd. (Mn=9500) *2 : Spherical silver powder with an average particle diameter of 1·5 μm *3: Diethylene glycol monoethyl ether acetate (boiling point = 217 ° C, glycol ester solvent) *4 : Triethylene glycol monobutyl Ether (boiling point = 271 ° C, high boiling point solvent) *5 : 2,4-diamino-6-[2'-methylimidazolyl-(1)]-ethyl·s-triazine trimeric isocyanide Acid addition product *6: biguanide type A epoxy resin (jER-828 manufactured by Mitsubishi Chemical Corporation) *7: Aerosil #200 manufactured by Japan Aerosil Co., Ltd. in the organic solvents of Examples 1 to 4 and Comparative Examples 1 and 2. The ratio of the high boiling point solvent is shown in Table 2. -20- 201220325 [Table 2] Solvent ratio [% by mass] Example Comparative Example 1 2 3 4 5 1 2 髙 Boiling point solvent 86% 58% 48% 303⁄4 643⁄4 0% 100% Other solvent 142⁄4 42% 52% 70% 363⁄4 1003⁄4 0% For each of the conductive pastes obtained in this way, evaluation was carried out as follows. (Evaluation of printability of simple gravure printing) (Production of sample) The obtained conductive paste was used in a concave portion of a glass intaglio pattern of a stripe pattern having a line/space = 70/30 μm and a plate depth: ΙΟμιη. Stainless steel scraper and charge. Then, the glass intaglio plate was pressed against a blanket cylinder composed of a polycarbonate rubber having a rubber hardness of 30, and the conductive paste filled in the concave portion was transferred to the surface of the blanket cylinder (off step). Further, the pattern of the conductive paste on the surface of the offset cylinder on the surface of the 1.8 mm thick soda glass (Set step) 〇 The obtained sample was evaluated as follows. (Printability 1 : Transferability evaluation)
Off步驟後’於10秒後進行Set步驟，以目視評估是否 於膠印滾筒表面殘存導電性膠漿，評估基準係如以下。 〇：於膠印滾筒表面無導電性膠漿的殘存（轉印1 〇〇% -21 - 201220325 △:於膠印滾筒表面之一部份’殘存導電性膠獎。 X :於膠印滾筒全面殘存導電性膠漿。 (印刷適性2 :於膠印滾筒上放置3 0秒後之轉印性評估） off步驟後，於30秒後進行Set步驟’以目視評估是否 於膠印滾筒表面殘存導電性膠漿’評估基準係如以下。 〇：於膠印滾筒表面無導電性膠漿的殘存（轉印1 0 0 % )° △:於膠印滾筒表面之一部份，殘存導電性膠漿。 X:於膠印滾筒全面殘存導電性膠漿。 (印刷適性3 :所形成之圖型的形狀） 以光學顯微鏡觀察轉印有導電性膠漿之圖型的玻璃基 板，評估所印刷之圖型的直進行、鬚缺陷之有無》評估基 準係如以下般。 〇：具有直進性、及/或完全看不出鬚缺陷。 △:略欠缺直進行、及/或僅產生鬚缺陷。 'X :有圖型之皺紋或斷線、及/或明顯地產生許多鬚缺 陷。 (比阻抗値的測定） 印刷線寬lmm、長40cm之測試圖型，使用熱風循環式 乾燥爐，以120 °C進行加熱處理30分鐘。使所得到之圖型 的阻抗値使用測試器（Hioki製Milliohm HiTester 3540) -22- 201220325 而測定，從圖型之膜厚算出比阻抗値。 將此等之評估結果表示於表2中。 【表3】 評價項目 實施例 比較例 1 2 3 4 5 1 2 印刷適性1 〇 〇 〇 〇 〇 △ Δ 印刷適性2 Δ Δ Δ 〇 △ X Δ 印刷適性3 〇 〇 〇 〇 △ Δ Δ 比阻抗値Ρΐ(Γ5Ω·απ] 9.4 5.9 8.3 4.9 13 23 25 從表2可知，在實施例1〜5中，任一者均印刷適性優異 ，即使off步驟至Set步驟之時間增長’膠漿保持轉移性。 另外，不含有高沸點溶劑之比較例1中係以長時間之 放置膠印滾筒表面的膠漿會乾燥，損及轉印性。又，在比 較例2中係轉移性雖可保持，但所形成之圖型係缺乏直進 性，印刷適性劣化。 又，嘗試使用聚酯樹脂（東洋紡社製Vylon 245 )作 爲黏合劑樹脂，但未溶解於三乙二醇單丁基醚，故中斷硏 究。 -23-After the Off step, the Set step was performed after 10 seconds to visually evaluate whether or not the conductive paste remained on the surface of the blanket cylinder, and the evaluation criteria were as follows. 〇: There is no residual conductive paste on the surface of the offset cylinder (transfer 1 〇〇% -21 - 201220325 △: one part of the surface of the offset cylinder 'remaining conductive glue. X: complete residual conductivity in the blanket cylinder Glue. (Printability 2: Transferability evaluation after placing on the blanket cylinder for 30 seconds) After the off step, the set step is performed after 30 seconds to visually evaluate whether or not the conductive paste remains on the surface of the blanket cylinder. The reference system is as follows. 〇: No residual of conductive paste on the surface of the offset cylinder (transfer 100%) ° △: Remaining conductive paste on one part of the surface of the blanket cylinder. X: Fully in the blanket cylinder Remaining conductive paste. (Printability 3: Shape of the formed pattern) The glass substrate on which the pattern of the conductive paste was transferred was observed with an optical microscope, and the pattern of the printed pattern was evaluated for straight progress and defects. The evaluation criteria are as follows: 〇: Straightness, and/or no need to be defective at all. △: Slightly lacking straightness, and/or only producing defects. 'X: Pattern wrinkles or broken Line, and/or obviously produce many shortcomings (Measurement of specific impedance 値) The test pattern with a printing line width of 1 mm and a length of 40 cm was heat-treated at 120 ° C for 30 minutes using a hot air circulating drying oven. The impedance of the obtained pattern was measured using a tester ( It was measured by Milloohm HiTester 3540) manufactured by Hioki -22-201220325, and the specific impedance was calculated from the film thickness of the pattern. The evaluation results of these were shown in Table 2. [Table 3] Evaluation item Example Comparative Example 1 2 3 4 5 1 2 Printing suitability 1 〇〇〇〇〇 △ Δ Printing suitability 2 Δ Δ Δ 〇 △ X Δ Printability 3 〇〇〇〇 △ Δ Δ Specific impedance 値Ρΐ (Γ5Ω·απ] 9.4 5.9 8.3 4.9 13 23 25 From As is clear from Table 2, in any of Examples 1 to 5, the printing suitability was excellent, and even if the time from the off step to the set step was increased, the "glue remained transferability. In addition, in Comparative Example 1 containing no high boiling point solvent, The glue placed on the surface of the blanket cylinder for a long time was dried to impair the transferability. Further, in Comparative Example 2, the transferability was maintained, but the pattern formed was lacking in straightness and the printability was deteriorated. Try using polyester resin ( Vylon 245 manufactured by Toyobo Co., Ltd. as a binder resin, but not dissolved in triethylene glycol monobutyl ether, was interrupted. -23-