(1) 九、發明說明 【發明所屬之技術領域】 本發明係關於一種新的導電性糊料組成物及印刷電路 板。較理想地本發明係關於多層印刷電路板的層與層間連 接用的電極凸塊的形成所適用之導電性糊料組成物及使用 其之印刷電路板。 【先前技術】 傳統上，導電性糊料組成物在電子領域被使用於1C 電路用、導電性黏附劑、電磁波遮蔽等多種用途。特別是 最近，已有提案將在至少一側的面的既定位置設置以導電 性糊料所做的圓錐形導電凸塊之第一基板，以及在至少一 側的面設置配線圖形之第二基板，使設置上述導電凸塊的 面與設置上述配線圖形的面成爲內側地相對向，於上述第 一基板與上述第二基板間，配置絕緣體層而構成層合體， 使該層合體藉由層合擠壓而使上述凸塊貫穿絕緣體層的厚 度方向，形成導電配線部之印刷電路板的製造方法（曰本 公開專利特開平6-3 5025 8號公報）。 而且，已有提案印刷電路板層與層間連接用之導電性 糊料組成物（日本公開專利特開2002-270033號公報）， 係預浸體貫穿性良好且貫穿時及擠壓時不會產生損壞，又 可製成貫穿後的凸塊與配線圖形的黏附力大的凸塊，具有 貫穿型的導電配線部之印刷電路板的製造中，提供作爲良 率高、連接可靠性良好之導電性糊料之含有酚樹脂、三聚 -5- (2) (2)1342571 氰胺樹脂、環氧樹脂、導電粉末以及溶劑所構成的導電性 糊料，其中該環氧樹脂的軟化點爲80°C以上、130°C以下 〇 而且，爲了提供可形成高硬度、無破損、與配線圖形 無接觸不良的凸塊之印刷電路板層與層間連接用之導電性 糊料組成物，已有提案使用包含選自三聚氰胺樹脂、酚樹 脂以及環氧樹脂所成群的至少1種、導電性粉末、沸點 180 °C以上的2價醇以及（或）3價醇之印刷電路板層與層 間連接用之導電性糊料組成物（曰本公開專利特開2003 -7 7 3 3 7號公報）。 而且，根據日本專利第3588400號公報’已知作爲網 版印刷後可以用水清洗裝置、治具及容器之熱硬化性導電 性樹脂組成物之提供例’其特徵爲包含水溶性熱硬化性樹 脂、導電性粒子、2價醇之導電性樹脂組成物。 根據日本公開專利特開平9-286924號公報，與專利 第3 5 8 8400號公報同樣地，作爲印刷後可用水洗淨網版等 之導電性樹脂組成物，已知包含水溶性熱硬化性樹脂 '平 均粒徑0.05〜50μηι的導電性粒子、2價醇。 根據日本公開專利特開200 1 - 1】3 88號公報，已知包 含可用水洗淨印刷用的版之水溶性樹脂、二醇類之層合電 容器用電極糊料組成物。 根據日本公開專利特開2003 -3 3 1 64 8號公報以及特開 2004-265826號公報，已知作爲可低溫燒成的金屬糊料， 係包含週期表3族〜1 5族金屬之有機金屬化合物及醇化 -6- (3) (3)1342571 合物，較理想爲包含二醇類之金屬糊料。 〔專利文獻1〕日本公開專利特開平6-3 5 02 5 8號公 報 〔專利文獻2〕日本公開專利特開2002-270033號公 報 〔專利文獻3〕日本公開專利特開2003 -773 3 7號公 報 〔專利文獻4〕日本專利第3588400號公報 〔專利文獻5〕日本公開專利特開平9-286924號公 報 〔專利文獻6〕日本公開專利特開2 0 0 1 - 1 1 3 8 8號公 報 〔專利文獻7〕曰本公開專利特開2003-3 3 1 648號公 報 〔專利文獻8〕日本公開專利特開2004-265 8 26號公 報 【發明內容】 發明所欲解決之課題 以上述特開平6-3 5025 8號公報記載的方法形成電極 凸塊時，使用如特開2002-27003 3號公報以及特開2003 -773 3 7號公報所揭露之導電性糊料組成物的情況，由於以 1次的導電性糊料組成物的塗佈作業，無法得到可貫穿絕 緣層之凸塊的高度，所以導電性糊料組成物的塗佈作業進 (4) (4)1342571 行複數次，必須反覆塗佈。特別是爲了貫穿絕緣層時及擠 壓時不產生凸塊的彎折、缺陷，使用不讓凸塊過度尖銳之 糊料，無法得到凸塊的高度、易增加重複印刷的次數。 專利第3 5 88400號公報、特開平9-286924號公報以 及特開200 1 - 1 1 3 88號公報所記載的技術係使用水溶性樹 脂，而特開2003 -3 3 1 648號公報以及特開2004-265 826號 公報所記載的技術係使用燒成型的金屬糊料，如本發明的 非水溶性的非燒成型的導電性糊料組成物，係以1次塗佈 作業可得充分的塗佈厚度之糊料組成物，以本發明人等之 瞭解，由傳統習知的技術無法得到。 解決課題的手段 本發明主要藉由使用含有特定化合物的溶劑，解決上 述課題。 所以，根據本發明的導電性糊料組成物，係由酚樹脂 '三聚截胺樹脂、導電性粉末、溶劑以及具有酸鍵之2價 醇所構成。 如此的根據本發明之導電性糊料組成物，較理想的態 樣係上述具有醚鍵之2價醇，其分子結構具有伸乙基二氧 基（ethylenedioxy)部分。 如此的根據本發明之導電性糊料組成物，較理想的態 樣係上述具有醚鍵之2價醇，於其兩端具有羥基。 如此的根據本發明之導電性糊料組成物，較理想的態 樣係該具有醚鍵之2價醇係選自二乙二醇、三乙二醇、四 (5) 1342571 乙二醇、五乙二醇以及六乙二醇所成群的至少1種° 如此的根據本發明之導電性糊料組成物’較理想的態 ' 樣係上述溶劑與上述具有醚鍵之2價醇總共爲1 00質量％ - 的情況下，上述具有醚鍵之2價醇爲0.1〜50質量％ ° 如此的根據本發明之導電性糊料組成物’較理想的態 樣係上述溶劑係選自丁卡必醇醋酸酯（butyl carbitol acetate )、乙酸乙酯、乙酸丁酯、乙二醇乙醚（ethyl • cellosolve)、乙二醇丁 醒（butyl cellosolve)、乙卡必 醇（ethyl carbitol) 、丁 卡必醇（butyl carbitol)、異丙 醇、丁醇、松香醇（terpineol )、己醇、乙二醇丁醚乙酸 酯、異佛酮（isophorone)所成群的至少1種。 如此的根據本發明之導電性糊料組成物，較理想的態 樣係更包含顔料，較理想爲擴展劑顏料。 所以，根據本發明的印刷電路板，其特徵爲使用上述 的導電性糊料組成物。 〔發明的效果〕 根據本發明之導電性糊料組成物，可以1次的塗佈作 ' 業可形成充分厚度的塗佈膜。 - 所以，即使以比傳統少的塗佈次數，也可形成充分高 度的凸塊。 因此，可以減少導電性糊料組成物重複印的次數，可 提高生產性。而且，根據本發明之導電性糊料組成物，由 於不是燒成型，無需進行燒成作業。 -9 - (6) (6)1342571 【實施方式】 <導電性糊料組成物> 根據本發明之導電性糊料組成物，其特徵爲由酚樹脂 、三聚氰胺樹脂、導電性粉末、溶劑以及具有醚鍵之2價 醇所構成。此處，所謂「構成」係指不排除與上述必要成 分（即酚樹脂、三聚氰胺樹脂、導電性粉末、溶劑以及具 有醚鍵之2價醇）以外的其他成分共存之導電性糊料組成 物。亦即，根據本發明之導電性糊料組成物，包含只由上 述必要成分構成的導電性糊料組成物以及含有上述必要成 分與這些必要成分以外的其他成分所構成的導電性糊料組 成物兩者。而且，上述所謂「導電性」係指體積電阻値至 少爲1 X 1 (T3cm . Ω以下。 根據本發明之導電性糊料組成物，黏度爲200〜500 Pa.s，較理想爲 300〜400 Pa.s。此外，該黏度係以 Malcom公司製Spiral黏度計於lOrpm /分鐘、25°C下測定 而得者。 所以，根據本發明之導電性糊料組成物，其觸變指數 (Thixotropic index)爲 0.75 〜1.0，特別是 0.8 〜0.95 較 理想。而且，該觸變指數係由Malcom公司製Spira丨黏度 計於lOrpm/分鐘、5rpm/分鐘，25°C下測定之導電性糊料 組成物的黏度，以觸變指數計算式log ( 5 rpm時的黏度値 /lOrpm時的黏度値）/log[10(rpm)/5(rpm)]所算出。觸變 指數係靜置時視黏度上升而激烈混合時視黏度下降之顯示 -10- (7) 1342571 變得容易塗佈的性質之指標。 • ( 1 )酚樹脂 . 作爲本發明使用的酚樹脂，可利用酚醛樹脂型以及甲 階酚醛樹脂型的任一種，特別是於酚、甲酚、二甲酚、聚 對乙烯酚、對-烷基酚、氯酚、雙酚A、酚磺酸、間苯二 酚等的具有酚性羥基者附加、縮合甲醛、2-呋喃甲醛等的 B 醛類之樹脂等爲較理想的樹脂。其中，特別是聚對乙烯酚 較理想。 (2 )三聚氰胺樹脂 作爲本發明使用的三聚氰胺樹脂，較理想的例如羥甲 基三聚氰胺、烷基化三聚氰胺。 (3 )導電性粉末 # 作爲本發明使用的導電性粉末，可使用各種導電性微 粉末，例如銀粉、金粉、銅粉、鎳粉、鉑粉、鈀粉、銲粉 、上述金屬的合金粉末等的金屬粉末等。這些導電性粉末 ' 可以倂用2種以上。而且，也可使用金屬以外的導電性粉 - 末，例如碳粉。導電性粉末也可以爲進行表面處理過者。 導電性粉末的形態及大小，只要不違反本發明的目的 ’可以爲任意。於本發明，可使用例如樹枝狀、輪片狀、 球狀 '薄片狀的形態者，特別理想的可使用輪片狀與球狀 的混合物。平均粒徑爲 0.5〜ΙΟμιη，特別是 1.0〜5.0μπι -11 - (8) (8)1342571 者較理想。 (4 )具有醚鍵之2價醇以及溶劑 根據本發明之導電性糊料組成物係含有具有醚鍵之2 價醇。於本發明，具有醚鍵之2價醇中，其分子結構具有 伸乙基二氧基（ethylenedioxy)部分者較理想，特別是於 其兩端具有羥基之具有醚鍵之2價醇特別理想。作爲如此 較理想的化合物的具體例，例如二乙二醇、三乙二醇、四 乙二醇、五乙二醇以及六乙二醇。其中，特別是三乙二醇 較理想。於本發明，可由這些具有醚鍵之2價醇選擇1種 單獨使用，或2種以上合倂使用。 作爲本發明使用的溶劑，可使用例如可使上述酚樹脂 、三聚氰胺樹脂以及導電性粉末形成糊料組成物之各種有 機溶劑。作爲如此的有機溶劑較理想的具體例，例如丁卡 必醇醋酸醋（butyl carbitol acetate)、乙酸乙醋、乙酸 丁醋、乙二醇乙醚（ethyl cellosolve )、乙二醇丁醚（ butyl cellosolve)、乙卡必醇（ethyl carbitol) 、丁卡必 醇（butyl carbitol)、異丙醇、丁醇、松香醇（terpineol )、己醇、乙二醇丁醒乙酸醋、異佛酮（isophorone)的 單獨或這些的混合溶劑。 溶劑與具有醚鍵之2價醇總共爲1 00質量％的情況下 ，具有醚鍵之2價醇的含有比例爲0 . 1〜5 0質量％，較理 想爲0.5〜40質量％，更理想爲1〜30質量％。 -12- (10) (10)1342571 導電性粉末的量’對樹脂成分爲i 00質量部時，較理 想爲300〜1100質量部，更理想爲500〜900質量部。 顏料的量，對樹脂成分爲1〇〇質量部時，較理想爲1 〜30質量部’更理想爲5〜25質量部。 樹脂成分中’酚樹脂以及三聚氰胺樹脂的比例，以質 量比表示’（酚樹脂）/(三聚氰胺樹脂）較理想爲1 0/90 〜90/10，更理想爲30/70〜70/30，更加理想爲60/40〜 40/60的範圍。 (7 )導電性糊料組成物的利用 根據本發明之導電性糊料組成物係具有良好的導電性 ，例如藉由網版印刷法、金屬遮罩印刷法等習知的方法， 可印刷於基板上。所以，根據本發明之導電性糊料組成物 ，可用於與傳統相同的寬廣的領域。 所以，根據本發明之導電性糊料組成物，由於每1次 的印刷作業的塗膜厚度厚，可有效率地形成充分厚度的導 電性層。 因此，根據本發明之導電性糊料組成物，可以比傳統 少的塗佈次數，例如即使只塗佈1次，可形成充分高度的 凸塊，可期望提高生產性。 <印刷電路板> 根據本發明之印刷電路板，其特徵爲使用上述的導電 性糊料組成物。 -14 - (11) 1342571 如此的根據本發明之印刷電路板，較理想的態樣包含 藉由上述導電性糊料組成物所形成的凸塊電連接層與層間 所構成的印刷電路板。 〔實施例〕 <實施例1〜7 > 將酚樹脂' 三聚氰胺樹脂、銀粉、擴展劑顏料、溶劑 • 以及具有醚鍵之2價醇以表1記載的質量比例混合，以3 個滾筒充分混練，製造根據本發明之導電性糊料組成物。 該導電性糊料組成物的黏度以及觸變指數如表1所記載。 使用該導電性糊料，進行網版（孔版）印刷。具體地 ，使用具有0 220μπι的開孔之鋁製金屬遮罩版，使用硬度 80°的胺基甲酸乙酯樹脂製的橡皮輥（squeegee)，控制環 境使氣體環境溫度爲2 0°C、濕度爲50%，進行印刷，形 成凸塊。 # 評價所形成的凸塊的高度以及形狀。結果如表丨所言己 載。 -15- 1342571(1) Description of the Invention [Technical Field of the Invention] The present invention relates to a novel conductive paste composition and a printed circuit board. More preferably, the present invention relates to a conductive paste composition suitable for the formation of electrode bumps for layer-to-layer connection of a multilayer printed circuit board and a printed circuit board using the same. [Prior Art] Conventionally, conductive paste compositions have been used in various fields such as 1C circuits, conductive adhesives, and electromagnetic wave shielding in the field of electronics. In particular, recently, it has been proposed to provide a first substrate of a conical conductive bump made of a conductive paste at a predetermined position on at least one side of the surface, and a second substrate having a wiring pattern on at least one side of the surface. And a surface on which the conductive bump is provided and a surface on which the wiring pattern is provided are opposed to each other, and an insulator layer is disposed between the first substrate and the second substrate to form a laminate, and the laminate is laminated A method of manufacturing a printed circuit board in which a conductive wiring portion is formed by squeezing the bump in a thickness direction of the insulating layer (Japanese Laid-Open Patent Publication No. Hei 6-3 5025 8). Further, there has been proposed a conductive paste composition for connecting a printed circuit board layer and a layer (Japanese Laid-Open Patent Publication No. 2002-270033), which has a good penetration property of the prepreg and does not occur during penetration and extrusion. In addition, it is possible to produce a bump having a large adhesion force between the bump and the wiring pattern after the penetration, and to provide a conductive layer having high yield and good connection reliability in the manufacture of a printed circuit board having a through-type conductive wiring portion. The paste contains a conductive paste composed of a phenol resin, a trimeric-5-(2) (2) 1,342,571 cyanamide resin, an epoxy resin, a conductive powder, and a solvent, wherein the epoxy resin has a softening point of 80°. In order to provide a conductive paste composition for connecting a printed circuit board layer and a layer which can form a bump having high hardness, no damage, and no contact failure with a wiring pattern, it has been proposed to use a conductive paste composition of C or more and 130 ° C or less. A printed circuit board layer comprising at least one selected from the group consisting of a melamine resin, a phenol resin, and an epoxy resin, a conductive powder, a divalent alcohol having a boiling point of 180 ° C or higher, and/or a trivalent alcohol, and an interlayer connection layer guide Paste composition (Laid-Open Patent Publication said present 2003-7733 Publication 7). Further, according to Japanese Patent No. 3588400, the provision of a thermosetting conductive resin composition which is known as a water-cleaning device, a jig and a container after screen printing is characterized in that it contains a water-soluble thermosetting resin. A conductive resin composition of conductive particles or a divalent alcohol. In the same manner as in the case of the conductive resin composition such as a screen which can be washed with water after printing, it is known to contain a water-soluble thermosetting resin, as disclosed in Japanese Patent Laid-Open No. Hei 9-286924. 'Electrical particles having an average particle diameter of 0.05 to 50 μm, and a divalent alcohol. An electrode paste composition for a laminated capacitor comprising a water-soluble resin which can be used for water-washing printing and a glycol is disclosed in Japanese Laid-Open Patent Publication No. 2001- 1-3. It is known that the metal paste which can be fired at a low temperature is an organic metal containing a metal of Group 3 to Group 15 of the periodic table, as disclosed in Japanese Laid-Open Patent Publication No. 2003-3 3 1 64 8 and JP-A-2004-265826. The compound and the alcoholated-6-(3) (3)1342571 compound are preferably a metal paste containing a glycol. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. 2002-270033 (Patent Document 3) Japanese Laid-Open Patent Publication No. 2002-270033 (Patent Document 3) Japanese Laid-Open Patent Publication No. 2003-773 No. Japanese Patent Laid-Open No. Hei 9-286924 (Patent Document 6) Japanese Laid-Open Patent Publication No. Hei 2 0 0 1 - 1 1 3 8 8 [Patent Document 7] Japanese Laid-Open Patent Publication No. 2003-3 3 648 (Patent Document 8) Japanese Laid-Open Patent Publication No. 2004-265 No. 8-26. SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION In the case of the method of the present invention, the conductive paste composition disclosed in Japanese Laid-Open Patent Publication No. 2002-27003 No. 2003-773, and the Japanese Patent Publication No. 2003-77337, In the coating operation of the secondary conductive paste composition, the height of the bump that can penetrate the insulating layer cannot be obtained. Therefore, the application of the conductive paste composition is carried out in (4) (4) 1344571, and must be repeated. Coating. In particular, in order to penetrate the insulating layer and to bend and form defects without bumps during extrusion, a paste which does not make the bumps excessively sharp is used, and the height of the bumps cannot be obtained, and the number of times of repeated printing is easily increased. In the technique described in the Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The technique described in Japanese Laid-Open Patent Publication No. 2004-265 826 uses a baked metal paste, such as the water-insoluble non-fired conductive paste composition of the present invention, which is obtained by one coating operation. A sufficient coating thickness of the paste composition, which is known to the inventors of the present invention, cannot be obtained by conventional techniques. Means for Solving the Problems The present invention mainly solves the above problems by using a solvent containing a specific compound. Therefore, the conductive paste composition according to the present invention is composed of a phenol resin 'trimeric amine resin, a conductive powder, a solvent, and a divalent alcohol having an acid bond. Such a conductive paste composition according to the present invention is preferably a divalent alcohol having an ether bond as described above, and having a molecular structure having an ethylenedioxy moiety. Such a conductive paste composition according to the present invention is preferably a divalent alcohol having an ether bond as described above and having a hydroxyl group at both ends thereof. Such a conductive paste composition according to the present invention is preferably a divalent alcohol having an ether bond selected from the group consisting of diethylene glycol, triethylene glycol, tetrakis(5) 1342571 ethylene glycol, and five. At least one of a group of ethylene glycol and hexaethylene glycol. The conductive paste composition according to the present invention is in a 'preferred state'. The solvent and the above-mentioned divalent alcohol having an ether bond are 1 in total. In the case of 00% by mass -, the above-mentioned divalent alcohol having an ether bond is 0.1 to 50% by mass. The preferred embodiment of the conductive paste composition according to the present invention is that the solvent is selected from the group consisting of Butyl carbitol acetate, ethyl acetate, butyl acetate, ethyl ether (cellosolve), butyl cellosolve, ethyl carbitol, butyl carbitol At least one of a group of (butyl carbitol), isopropyl alcohol, butanol, terpineol, hexanol, ethylene glycol butyl ether acetate, and isophorone. Such a conductive paste composition according to the present invention contains a pigment more preferably, more preferably an extender pigment. Therefore, the printed circuit board according to the present invention is characterized by using the above-described conductive paste composition. [Effects of the Invention] According to the conductive paste composition of the present invention, a coating film having a sufficient thickness can be formed by one application. - Therefore, a sufficiently high bump can be formed even with a smaller number of coatings than conventional ones. Therefore, the number of times the conductive paste composition is repeatedly printed can be reduced, and productivity can be improved. Further, according to the conductive paste composition of the present invention, since it is not baked, it is not necessary to perform a firing operation. -9 - (6) (6) 1342571 [Embodiment] <Conductive paste composition> The conductive paste composition according to the present invention is characterized by a phenol resin, a melamine resin, a conductive powder, and a solvent. And a divalent alcohol having an ether bond. Here, the term "constitution" means a conductive paste composition which does not exclude other components other than the above-mentioned essential components (i.e., a phenol resin, a melamine resin, a conductive powder, a solvent, and a divalent alcohol having an ether bond). In other words, the conductive paste composition of the present invention comprises a conductive paste composition composed only of the above-mentioned essential components, and a conductive paste composition comprising the above-mentioned essential components and other components other than these essential components. Both. Further, the above-mentioned "conductivity" means that the volume resistance 値 is at least 1 X 1 (T3 cm Ω or less. The conductive paste composition according to the present invention has a viscosity of 200 to 500 Pa.s, preferably 300 to 400. In addition, the viscosity was measured by a Spiral viscometer manufactured by Malcom Co., Ltd. at 10 rpm/min and 25 ° C. Therefore, the conductive paste composition according to the present invention has a thixotropic index (Thixotropic index). It is preferably 0.75 to 1.0, particularly 0.8 to 0.95. Further, the thixotropic index is a conductive paste composition measured by a Mala company Spira(R) viscometer at 10 rpm/min, 5 rpm/min, 25 °C. The viscosity is calculated by the thixotropy index formula (viscosity at 5 rpm / viscosity at 10 rpm /) / log [10 (rpm) / 5 (rpm)]. The thixotropic index is increased when the temperature is allowed to stand. In the case of intense mixing, the apparent viscosity is decreased. -10- (7) 1342571 An indicator of the properties that become easy to apply. (1) Phenolic resin. As the phenol resin used in the present invention, a phenol resin type and a resol type can be used. Any of the resin types, especially phenol, cresol, xylenol, poly a resin having a phenolic hydroxyl group such as a vinyl phenol, a p-alkylphenol, a chlorophenol, a bisphenol A, a phenolsulfonic acid or a resorcin, and a B aldehyde such as a formaldehyde or a 2-furaldehyde. More preferred resins, among which poly(p-vinylphenol) is preferred. (2) Melamine resin As the melamine resin used in the present invention, it is preferably, for example, methylol melamine or alkylated melamine. (3) Conductive powder# As the conductive powder used in the present invention, various conductive fine powders such as silver powder, gold powder, copper powder, nickel powder, platinum powder, palladium powder, solder powder, metal powder such as alloy powder of the above metal, and the like can be used. The powder may be used in combination of two or more kinds. Further, a conductive powder other than metal may be used, for example, carbon powder. The conductive powder may be subjected to surface treatment. The form and size of the conductive powder are not The object of the present invention may be any. In the present invention, for example, a dendritic, a wheel-like, or a spherical "flaky shape" may be used, and a particularly desirable combination of a wheel-shaped and a spherical shape may be used. The average particle diameter is 0.5 to ΙΟμιη, particularly 1.0 to 5.0 μπι -11 - (8) (8) 1344571. (4) Divalent alcohol having an ether bond and solvent. The conductive paste according to the present invention. The composition of the material contains a divalent alcohol having an ether bond. In the present invention, it is preferred that the divalent alcohol having an ether bond has a molecular structure having an ethylenedioxy moiety, particularly at both ends thereof. A divalent alcohol having an ether bond having a hydroxyl group is particularly preferable. Specific examples of such a preferred compound include diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, and hexaethylene glycol. Among them, especially triethylene glycol is preferred. In the present invention, one of these divalent alcohols having an ether bond may be used alone or in combination of two or more. As the solvent to be used in the present invention, for example, various organic solvents which can form the paste composition by the above phenol resin, melamine resin and conductive powder can be used. Preferred examples of such an organic solvent include, for example, butyl carbitol acetate, ethyl acetate, butyl acetate, ethyl cellosolve, and butyl cellosolve. , ethyl carbitol, butyl carbitol, isopropanol, butanol, terpineol, hexanol, ethylene glycol acetonide acetate, isophorone Separate or a mixed solvent of these. When the solvent and the divalent alcohol having an ether bond are a total of 100% by mass, the content ratio of the divalent alcohol having an ether bond is 0.1 to 50% by mass, preferably 0.5 to 40% by mass, more preferably It is 1 to 30% by mass. -12- (10) (10) 1344571 The amount of the conductive powder is preferably 300 to 1100 parts by mass, more preferably 500 to 900 parts by mass, in the case where the resin component is i 00 parts by mass. When the amount of the pigment is 1 part by mass, the amount of the pigment is preferably 1 to 30 parts by mass, more preferably 5 to 25 parts by mass. The ratio of the 'phenol resin and the melamine resin in the resin component is preferably expressed by mass ratio '(phenol resin) / (melamine resin) is preferably 10/90 to 90/10, more preferably 30/70 to 70/30, more preferably Ideally in the range of 60/40 to 40/60. (7) Use of Conductive Paste Composition The conductive paste composition according to the present invention has good conductivity, and can be printed on, for example, by a conventional method such as screen printing or metal mask printing. On the substrate. Therefore, the conductive paste composition according to the present invention can be used in the same broad field as the conventional one. Therefore, according to the conductive paste composition of the present invention, since the coating film thickness per one printing operation is thick, a conductive layer having a sufficient thickness can be efficiently formed. Therefore, according to the conductive paste composition of the present invention, the number of coatings can be made less than conventionally, for example, even if it is applied only once, a bump having a sufficient height can be formed, and productivity can be expected to be improved. <Printed Circuit Board> The printed circuit board according to the present invention is characterized in that the above-described conductive paste composition is used. Further, in a preferred embodiment of the printed circuit board according to the present invention, a printed circuit board formed by a bump electrical connection layer and a layer formed by the conductive paste composition is used. [Examples] <Examples 1 to 7 > A phenol resin, a melamine resin, a silver powder, an extender pigment, a solvent, and a divalent alcohol having an ether bond were mixed at a mass ratio shown in Table 1, and were sufficiently filled with three rolls. The conductive paste composition according to the present invention was produced by kneading. The viscosity and the thixotropic index of the conductive paste composition are as shown in Table 1. Screen printing was performed using this conductive paste. Specifically, a metal glazing plate having an opening of 0 220 μm is used, and a squeegee made of a urethane resin having a hardness of 80° is used to control the environment so that the gas ambient temperature is 20 ° C, humidity. For 50%, printing is performed to form bumps. # Evaluate the height and shape of the bumps formed. The results are as stated in the table. -15- 1342571
12)一 谳 實施例7 〇 ! 700 〇 1 1 1 1 卜· 213 0.75 in 良好 實施例6 〇 〇 卜 〇 1 1 1 cn 1 226 0.81 VO 良好 實施例5 Ο yri 〇 700 〇 1 1 1 1 229 0.80 S 良好 丨實施例4 ο 〇 700 〇 in 1 12.5 1 1 1 〇 ΓΛ 0.90 VO 良好 實施例3 〇 700 〇 1 I 1 1 〇 m 0.85 〇〇 良好 實施例2 700 〇 1 1 1 1 310 ' 0.85 ' 00 良好 實施例1 700 〇 —Η yri 卜·· 1 1 1 1 250 0.88 良好 酚樹脂 三聚氰胺樹脂 銀粉 擴展劑顏料 丁卡必醇醋酸酯 二乙二醇 三乙二醇 四乙二醇 五乙二醇 六乙二醇 黏度（Pa· s/25°C) 觸變指數 凸塊高度（μηι) 凸塊形狀 -16 - •(13) •(13)134257112) Example 7 〇! 700 〇1 1 1 1 卜·213 0.75 in Good Example 6 〇〇 〇 1 1 1 cn 1 226 0.81 VO Good Example 5 Ο yri 〇700 〇1 1 1 1 229 0.80 S Good 丨 Example 4 ο 〇 700 〇 in 1 12.5 1 1 1 〇ΓΛ 0.90 VO Good Example 3 〇 700 〇 1 I 1 1 〇 m 0.85 〇〇 Good Example 2 700 〇 1 1 1 1 310 ' 0.85 ' 00 Good Example 1 700 〇-Η yri Bu·· 1 1 1 1 250 0.88 Good phenolic resin melamine resin silver powder extender pigment butyl carbitol acetate diethylene glycol triethylene glycol tetraethylene glycol five ethylene two Alcohol hexaethylene glycol viscosity (Pa·s/25°C) Thixotropic index bump height (μηι) Bump shape-16 - •(13) •(13)1342571
<比較例1〜丨3 > 使用如表2以及表3記載的比例之溶劑，再除去具有 醒鍵之2價醇以外，與實施例1同樣地，製造導電性糊料 組成物（比較例），與實施例1同樣地進行網版印刷’評 價所形成的凸塊的高度以及形狀。結果如表2所記載。 -17- 1342571 比較例7 〇 〇 tr. Ο 卜 〇 f—^ ! ! ! ! ! W-) 1 1 ! ! 1 1 (N vo ON VD 〇 VO 良好 比較例6 〇 〇 〇 Ψ 1 1 1 1 卜^ 1 1 1 1 1 1 1 c^i <Τ) 〇 卜 比較例5 〇 〇 卜 〇 f * 1 1 1 to 1 1 1 1 1 1 1 1 (Ν s o 比較例4 〇 卜 〇 $ 1 1 1 1 1 1 1 1 1 1 1 m (Ν <N (N ON o m & 比較例3 Ο 〇 ^Τ) 〇 〇 ο V-N »〇 1 w-ϊ 1 1 1 I 1 1 1 1 1 1 C\ \〇 d 比較例2 〇 〇 〇 ο iT) 卜'· 1 1 1 1 1 1 1 1 1 1 1 (N 00 o 比較例1 〇 〇 〇 ο 1 1 1 1 1 1 1 1 1 1 1 1 o (N 沄 o 00 酚樹脂 三聚氰胺樹脂 銀粉 擴展劑顏料 丁卡必醇醋酸酯 | 2-丁烯 1-4 二醇 1-3 丁二醇 1-3丙二醇 1-5戊二醇 2-3 丁二醇 丙二醇 1-2-6己三醇 1-4 丁二醇 1-2 丁二醇 3甲基1-5戊二醇 2甲基2-4戊二醇 二乙二醇單甲醚 黏度（Pa*s/25°C) 觸變指數 凸塊高度（μπ〇 凸塊形狀 1 -18- 1342571 ε嗽 比較例13 〇 〇 〇 卜 〇 w Η 1 1 1 1 1 1 1 1 1 1 1 ΚΤί 5 <N Ό Ο 比較例12 〇 〇 卜 〇 1 _ 1 1 1 1 1 1 1 1 1 1 1 (Ν yn ΓΛ ο 卜 L比較例11 〇 卜 〇 1 1 1 1 1 1 1 1 1 卜* 1 1 00 ο 比較例10 〇 〇 ο 1 1 1 1 1 1 1 1 1 1 1 % ο 画 比較例9 〇 〇 〇 卜 ο 1' _ JTi 1 1 1 1 1 1 1 1 [ 1 I 00 ο 卜 -0¾ 比較例8 〇 〇 in 〇 卜 ο 1 1 1 1 1 1 1 1 1 1 1 〇 (Ν 卜 ο (Ν 酚樹脂 三聚氰胺樹脂 銀粉 擴展劑顏料 f 丁卡必醇醋酸酯 2-丁烯 1-4 二醇 1-3 丁二醇 1-3丙二醇 1-5戊二醇 2-3 丁二醇 丙二醇 1-2-6己三醇 1-4 丁二醇 _1 1-2 丁二醇 3甲基1-5戊二醇 2甲基2-4戊二醇！ 二乙二醇單甲醚 $m (Pa*s/25〇C) 1 觸變指數 凸塊高度（μπι) 凸塊形狀 -19- (16)1342571 <評價> 由上述表1、表2以及表3得知，含有既 鍵之2價醇之實施例1〜7，可形成凸塊的高β 8 6μηι (凸塊直徑：220μπι )之凸塊，與不使用 2價醇之比較例1(凸塊高度：58μιη;凸塊道 )比較，得知凸塊高度可急遽地提高4 8%。而 形狀亦爲圓錐狀，形狀良好。 使用1價、2價或3價醇取代實施例1〜 具有醚鍵之2價醇之比較例2〜13,凸塊的形 現凸塊高度變低。而且，即使變高者最大1 8.6 %的程度。 定的具有醚 【爲7 5 μ m〜 具有醚鍵之 徑：220μιη 且。凸塊的 7所使用的 狀變圓，發 &只有提高 -20 -<Comparative Example 1 to 丨3 > A conductive paste composition was produced in the same manner as in Example 1 except that the solvent having the ratio shown in Tables 2 and 3 was used, and the divalent alcohol having a ring-opening amount was removed. Example) The height and shape of the bump formed by the screen printing 'evaluation were performed in the same manner as in the first embodiment. The results are shown in Table 2. -17- 1342571 Comparative Example 7 〇〇tr. 〇 Bu 〇 f—^ ! ! ! ! ! W-) 1 1 ! ! 1 1 (N vo ON VD 〇VO Good Comparative Example 6 〇〇〇Ψ 1 1 1 1卜^ 1 1 1 1 1 1 1 c^i <Τ) 比较卜Comparative Example 5 〇〇卜〇f * 1 1 1 to 1 1 1 1 1 1 1 1 (Ν so Comparative Example 4 〇卜〇 $ 1 1 1 1 1 1 1 1 1 1 1 m (Ν <N (N ON om & Comparative Example 3 Ο 〇^Τ) 〇〇ο VN »〇1 w-ϊ 1 1 1 I 1 1 1 1 1 1 C\ \〇d Comparative Example 2 〇〇〇ο iT) 卜'· 1 1 1 1 1 1 1 1 1 1 1 (N 00 o Comparative Example 1 〇〇〇ο 1 1 1 1 1 1 1 1 1 1 1 1 o (N 沄o 00 phenol resin melamine resin silver powder extender pigment butyl carbitol acetate | 2-butene 1-4 diol 1-3 butanediol 1-3 propylene glycol 1-5 pentanediol 2-3 Butanediol propylene glycol 1-2-6 hexanetriol 1-4 butanediol 1-2 butanediol 3 methyl 1-5 pentanediol 2 methyl 2-4 pentanediol diethylene glycol monomethyl ether viscosity (Pa*s/25°C) Thix exponential bump height (μπ〇bump shape 1 -18- 1342571 ε嗽Comparative example 13 〇〇〇卜〇w Η 1 1 1 1 1 1 1 1 1 1 1 ΚΤί 5 <N Ό Ο Comparative Example 12 〇〇卜〇1 _ 1 1 1 1 1 1 1 1 1 1 1 (Ν yn ΓΛ ο 卜 L Comparative Example 11 〇 〇 1 1 1 1 1 1 1 1 1 卜 * 1 1 00 ο Comparative Example 10 〇〇ο 1 1 1 1 1 1 1 1 1 1 1 % ο Drawing Comparative Example 9 〇〇〇卜 ο 1' _ JTi 1 1 1 1 1 1 1 1 [ 1 I 00 ο 卜 -03⁄4 Comparative Example 8 〇 〇in 〇布ο 1 1 1 1 1 1 1 1 1 1 1 〇(Ν 卜ο (Ν phenol resin melamine resin silver powder extender pigment f butyl carbitol acetate 2-butene 1-4 diol 1-3 Butanediol 1-3 Propylene glycol 1-5 pentanediol 2-3 Butanediol Propylene glycol 1-2-6 hexanetriol 1-4 Butanediol_1 1-2 Butanediol 3 methyl 1-5 pentylene Alcohol 2 methyl 2-4 pentanediol! Diethylene glycol monomethyl ether $m (Pa*s/25〇C) 1 Thixotropic index bump height (μπι) Bump shape-19- (16)1342571 <Evaluation> From Table 1, Table 2 above And Table 3 shows that Examples 1 to 7 containing a divalent alcohol having a bond can form a bump of a high β 8 6 μη (bump diameter: 220 μm) bump, and Comparative Example 1 in which a divalent alcohol is not used. (Bump height: 58 μιη; bump track) comparison, it is known that the bump height can be sharply increased by 48%. The shape is also conical and the shape is good. In Comparative Examples 2 to 13 in which the monovalent, divalent or trivalent alcohol was used in place of the divalent alcohol having an ether bond, the height of the bump was lowered. Moreover, even if it is higher, the maximum is 18.6%. It has an ether [is 7 5 μ m~ with an ether bond diameter: 220 μιη and. The shape of the bump used by the 7 is rounded, and the hair & only improves -20 -