1265838 經濟部智慧財產局員工消費合作社印製 A7 ____B7____ 五、發明説明（1 ) 發明所屬之技術領域 本發明係有關封裝電子元件等用之金屬焊藥’焊接用 助熔劑、焊料糊漿等。 發明之先前技術 金屬焊藥、焊接用助熔劑、焊料糊漿等係用於電子產 業中將電子零件加以表面封裝。又，焊料糊漿由於其印刷 適應性、黏著性適於自動化，近年來使用量增加。 於電子產業中，焊料糊漿係以網篩印刷法或分散器將 其塗佈於印刷基板上，然後將電子元件裝載於上，再回焊 使電子元件固定化。此處之回焊係指將裝載有電子元件之 基板預熱，然後加熱至焊料糊漿熔融之溫度以上並使元件 接合之系列操作。 另一方面，由於近來電子製品小型化而要求微間距化 ，微間距之元件例如0.3mm間距之線組扁平封裝（QFP， Quad Flat Package )型大型積體（LSI，Large scale integration )之使用以及廣泛使用於電路晶片尺寸構裝（ CSP ’ Chip Size Package)等。因此要求焊料糊漿在微間距 元件接合時須具高浸潤性及接合後須具優越之耐熱衝擊性 及元件裝載性。因應此種業界之強烈需求，渴求能獲得在 接合時具高浸潤性及接合後具優越耐熱衝擊性及元件裝載 性之金屬焊藥及焊料糊漿。 但是由於近來裝載元件之微間距化及大型化，以往之 焊藥合金或焊料糊漿不能獲得充分之浸潤性及耐熱衝擊性 (請先閱讀背面之注意事項再填寫本頁) 裝·1265838 Ministry of Economic Affairs, Intellectual Property Office, Employees' Cooperatives, Co., Ltd. A7 ____B7____ V. Technical Field of the Invention The present invention relates to a metal flux for soldering electronic components, such as a soldering flux, a solder paste, and the like. Prior Art of the Invention Metal solder, flux for soldering, solder paste, etc. are used in the electronics industry to surface encapsulate electronic components. Further, the solder paste is suitable for automation due to its printability and adhesion, and the amount of use has increased in recent years. In the electronics industry, a solder paste is applied to a printed substrate by a screen printing method or a disperser, and then electronic components are mounted thereon, and then re-welded to immobilize the electronic components. Reflow here refers to a series of operations in which a substrate on which electronic components are mounted is preheated and then heated to a temperature above which the solder paste is melted and the components are joined. On the other hand, due to the recent miniaturization of electronic products, micro-pitching is required, and the use of micro-pitch components such as a 0.3 mm pitch Quad Flat Package type LSI (Large Scale Integration) and Widely used in CSP 'Chip Size Packages' and so on. Therefore, the solder paste is required to have high wettability when the micro-pitch members are joined and to have excellent thermal shock resistance and component loadability after bonding. In response to the strong demand in the industry, it is eager to obtain metal solder and solder paste which have high wettability at the time of bonding and excellent thermal shock resistance and component loadability after bonding. However, due to the recent fine pitch and large size of the load components, conventional solder alloys or solder pastes have not been able to obtain sufficient wettability and thermal shock resistance (please read the back note before filling in this page).
、1T -線 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -5- 1265838 A7 B7 五、發明説明（2 ) ’而發生接合部可信度降低之情況。又最近因環境問題而 推崇不含鉛之無鉛焊藥，有鑑於此而加快無鉛焊藥之開發 〇 (請先閲讀背面之注意事項再填寫本頁) 無鉛金屬焊藥就融點或浸潤性、接合信賴性而言以Sn_ 系、Sn-Cu系、Sn-Bi系、Sn-Zn系最有希望。就融點而 r以Sn-Bi系爲佳但因脆弱易壞而不能貫用化。Sn-Cu系、 Sn-Ag系因融點過高元件之耐熱性成爲問題點。又sn-Ag 系除因含昂貴之銀，其價格高於以往之Sn-Pb系以外，亦 擔心資源枯竭化及銀溶出時就生命週期評估（LCA，Life Cycle Assessment )之觀點而言對生態系所產生之影響。 咸認融點與Sn-Pb共晶合金最接近之Sii-Zn系爲最有 希望之無鉛焊藥材料。Sn-Zn系焊藥材料爲進一步降低融點 及改良浸潤性可添加鉍。然而已確知添加鉍則接合物之耐 衝擊性降低。而Sn-9Zn共晶合金則即使以助熔劑等解決浸 潤性問題，但仍有元件裝載時之晶片翹起現象問題。 經濟部智慧財產局員工消費合作社印製 以往之Sn-Pb系焊藥因Sn、Pb電位非常接近而甚安定 ，無鉛金屬焊藥則因Sn與Ag、Cu、Zn產生電位差，金屬 焊藥易氧化，焊接性降低。特別是Sn-Zn系焊藥，因Zn之 電位較Pb更低，因此氧化非常激烈於大氣下之焊接欲實用 化甚爲困難。大氣下之焊接必須使用添加強力活性劑或增 多添加量作爲助熔劑，此種情況下，金屬焊藥與助熔劑易 起反應，經常會降低焊料糊漿之安定性。 發明欲解決之問題 -6 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1265838 經濟部智慧財產局員工消費合作社印製 A7 一― _ B7五、發明説明（3 ) 本發明人有鑑於上述問題點，其目的係提供Sn-Zn-Bi 系合金在鉍添加量少時或不含鉍之Sn-Zn系二元合金中， 浸潤性及接合物之耐衝擊性高之金屬組成或助熔劑成分。 解決問題之方法 本發明人爲解決上述問題銳意努力檢討之結果，發現 若將鉍添加量降至約1 %範圍則大幅改善耐衝擊性，且藉由 使用特定之助熔劑可大幅改善浸潤性，而可提供接合可信 度高之焊藥材料。 此外亦發現Sn-Zn系二元合金若將鋅之濃度降低至約 7%左右則可抑制氧化並改善浸潤性，同時可抑制晶片翹起 現象。藉由與特定助熔劑組合可提供浸潤性大幅改善且元 件裝載性亦優越之焊藥材料，藉由使用含有1個以上一級 、二級或三級C Η鍵之烴化合物與含鹵之氫供予體化合物作 爲活性劑，即使以往使用有困難之無鉛焊料於大氣下之焊 接，亦有良好之焊接性，於焉完成本發明。 亦即本發明係有關下列者。 (1 ) 鋅含量在8.8至5.0質量％範圍內，鉍含量在 〇.〇5質量％以下或爲〇，餘份爲錫或不可避免之雜質的金屬 焊藥。 (2) 鋅含量在9.0至5.0質量％範圍內，鉍含量在2.0 至0.05質量％範圍內，餘份爲錫或不可避免之雜質的金屬 焊藥。 (3) 鋅含量在8·5至6.5質量％範圍內，鉍含量在1.5 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） TjZ ' (請先閲讀背面之注意事項再填寫本頁) 1265838 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（4 ) 至0. 1質量％範圍內’餘份爲錫或不可避免之雜質的金屬焊 藥。 (4 )鋅含量在8· 3至7.5質量％範圍內，鉍含量在1.2 至〇. 5質量％範圍內，餘份爲錫或不可避免之雜質的金屬焊 藥。 (5 ) ( 1 )至（4 )項中任一項之金屬焊藥，其中，焊 藥粉末中所含20// m以下之焊藥粒子其個數分布爲3 〇%以 下者。 (6 ) —種焊接用助熔劑，其特徵爲含有1個以上一級 '二級或三級CH鍵之烴化合物與含鹵之氫供予體化合物。 (7 ) ( 6 )項之焊接用助熔劑，其中，含鹵之氫供予 體化合物爲有機鹵化合物者。 (8 ) ( 6 )或（7 )項之焊接用助熔劑，其中，含有1 個以上一級、二級或三級CH鍵之烴化合物爲選自四氫化萘 、四異丁烯、八氫化蒽、l-α-萘基-1-正丁基十六碳烯、9 ’ 10-二氫-9，10-二異丁基蒽、正十八烷基苯、y3-正十八 烷基四氫化萘、聚異丁烯所成組群之任一者。 (9 ) ( 6 )至（8 )項項中任一項之焊接用助熔劑，其 中，含鹵之氫供予體化合物之含量，對焊接用助熔劑全量 而言以氯計其量爲0.02質量％至20質量％範圍內。 (1〇) ( 6 )至（9 )項中任一項之焊接用助熔劑，其 中，含有1個以上一級、二級或三級CH鍵之烴化合物之含 量，對焊接用助熔劑全量而言爲0.01質量％至20質量％範 圍內。 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -8- 1265838 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（5 ) (11) 含有（1 )至（5 )項中任一項之金屬焊藥與（ 6)至（1 0 )項中任一項之焊接用助熔劑的焊料糊漿。 (12) ( 1 1 )項之焊料糊漿，其中，對焊料糊漿全量 而言金屬焊藥之比率爲8 6至92質量％範圍內，焊接用助熔 劑之比率爲1 4至8質量％範圍內。 (1 3 )將（1 1 )或（1 2 )項之焊料糊漿塗佈於電路基 板上，並將電子元件裝載於該塗佈部分上，然後將電路基 板加熱使電子元件接合在電路基板上而製造電路基板之方 法。 (14) 將（6 )至（10 )項中任一項之焊接用助熔劑 以溶劑稀釋而製作之焊用液狀助熔劑。 (1 5 ) 含有（1 )至（5 )項中任一項之金屬焊藥與（ 6)至（1 〇 )項中任一項之焊接用助熔劑的摻有樹脂之焊藥 線。 實施發明之方式 本發明之金屬焊藥爲： 鋅含量在8.8至5.0質量％範圍內，鉍含量在0.05質量 %以下或爲〇，餘份爲錫或不可避免之雜質的金屬焊藥、 鋅含量在9.0至5.0質量％範圍內，鉍含量在2.0至 0.05質量％範圍內，餘份爲錫或不可避免之雜質的金屬焊藥 鋅含量在8.5至6.5質量％範圍內，鉍含量在1.5至0.1 質量％範圍內，餘份爲錫或不可避免之雜質的金屬焊藥、 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210〆297公釐） -9- 1265838 A7 _____ B7 五、發明説明（6 ) (請先閲讀背面之注意事項再填寫本頁) 鋅含量在8.3至7·5質量％範圍內，鉍含量在1.2至0.5 質量％範圍內，餘份爲錫或不可避免之雜質的金屬焊藥。藉 由使用該組成範圍內的金屬焊藥，可獲得電子元件接合時 之高浸潤性以及接合元件之高度耐衝擊性及高焊接性。 不可避免之雜質係指於製造金屬焊藥時必然會混入之 元素。此外，即使係屬添加只要對金屬焊藥之特性無甚影 響之元素亦可定義爲不可避免之雜質。不可避免之雜質其 混入量一般爲各元素之1質量％以下，不可避免之雜質元素 可例示如非金屬元素、半金屬元素、碳元素、氧元素、氮 元素、過渡金屬元素等。特別以鉛、銀、銻、銅、鐵、’鋁 、砷、鎘等元素易混入金屬焊藥中，此等元素即使混入本 發明之金屬焊藥中對其特性亦無不良影響，可定義爲不可 避免之雜質。 經濟部智慧財產局員工消費合作社印製 將金屬焊藥之組成定於上述範圍之理由，係因Sn-Zn 系二元合金之情況下，若鋅含量高於8.8質量％則金屬焊藥 之氧化情況激烈，且浸潤性顯著低劣，裝載元件並回焊時 產生晶片翹起現象。而若鋅含量低於5.0質量％則融（液相 線溫度）超過2 1 5°C由於電子元件之耐熱性因而電子元件之 使用壽命顯著減低。又藉由使鉍含量在〇 . 0 5質量％以下或 爲0，可提高接合物之可信度及浸潤性。, 1T-line This paper scale applies to the Chinese National Standard (CNS) Α4 specification (210X297 mm) -5-1265838 A7 B7 V. Invention description (2) ‘There is a decrease in the reliability of the joint. Recently, due to environmental issues, lead-free solders that do not contain lead have been promoted. In view of this, the development of lead-free solders has been accelerated (please read the notes on the back and fill out this page). Lead-free metal solders melt or infiltrate. In terms of bonding reliability, the Sn_ system, the Sn-Cu system, the Sn-Bi system, and the Sn-Zn system are most promising. In terms of melting point, r is preferably Sn-Bi, but it is not easy to be used because it is fragile and fragile. The Sn-Cu system and the Sn-Ag system have problems due to the heat resistance of the element having a too high melting point. In addition to the high-grade silver, the price of the sn-Ag system is higher than that of the conventional Sn-Pb system. It is also worried about the depletion of resources and the dissolution of silver during the life cycle assessment (LCA). The impact of the system. The Sii-Zn system, which is the closest to the Sn-Pb eutectic alloy, is the most promising lead-free solder material. The Sn-Zn based flux material can be added to further reduce the melting point and improve the wettability. However, it has been confirmed that the impact resistance of the joint is lowered by the addition of niobium. On the other hand, the Sn-9Zn eutectic alloy solves the problem of the wetting property even with a flux or the like, but there is a problem that the wafer is lifted when the component is loaded. The Ministry of Economic Affairs, Intellectual Property Office, and the Consumers' Cooperatives printed the previous Sn-Pb fluxes because of the close proximity of Sn and Pb potentials. The lead-free metal fluxes have potential differences due to Sn and Ag, Cu, and Zn. Metallic fluxes are easily oxidized. , weldability is reduced. In particular, in the Sn-Zn type solder, since the potential of Zn is lower than that of Pb, the oxidation is very intense and it is difficult to apply it to the welding under the atmosphere. In the atmosphere, solder must be added with a strong active agent or an added amount as a flux. In this case, the metal solder reacts with the flux easily, which often reduces the stability of the solder paste. Problems to be Solved by the Invention -6 - The paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1265838 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed A7 I_B7 V. Invention Description (3) The present invention In view of the above problems, the object of the present invention is to provide a metal having a high impact resistance of a Sn-Zn-Bi alloy in a Sn-Zn-based binary alloy containing a small amount of niobium or a niobium-free binary alloy. Composition or flux composition. Means for Solving the Problems As a result of intensive efforts to solve the above problems, the inventors have found that if the amount of niobium added is reduced to about 1%, the impact resistance is greatly improved, and the infiltration property can be greatly improved by using a specific flux. It can provide solder material with high reliability. Further, it has been found that the Sn-Zn binary alloy can suppress oxidation and improve wettability by reducing the concentration of zinc to about 7%, and at the same time suppress wafer lift-up. By combining with a specific flux, it can provide a flux material with greatly improved wettability and excellent component loadability, by using a hydrocarbon compound containing one or more primary, secondary or tertiary C Η bonds and hydrogen-containing hydrogen. As the active compound, the precursor compound has good weldability even if it is conventionally used in the welding of lead-free solder which is difficult to be used in the atmosphere, and the present invention has been completed. That is, the present invention relates to the following. (1) A metal flux in which the zinc content is in the range of 8.8 to 5.0% by mass, the cerium content is 5% by mass or less, or the remainder is tin or an unavoidable impurity. (2) A metal flux having a zinc content in the range of 9.0 to 5.0% by mass and a bismuth content in the range of 2.0 to 0.05% by mass, the remainder being tin or unavoidable impurities. (3) The zinc content is in the range of 8.5 to 6.5 mass%, and the cerium content is 1.5. The paper size is applicable to the Chinese National Standard (CNS) Α4 specification (210X297 mm) TjZ ' (please read the notes on the back and fill in the form) Page) 1265838 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printing V. Inventions (4) To 0.1% by mass of metal fluxes that are tin or inevitable impurities. (4) A metal solder having a zinc content in the range of 8.3 to 7.5% by mass and a bismuth content in the range of 1.2 to 5% by mass, the remainder being tin or an unavoidable impurity. (5) The metal flux according to any one of (1) to (4), wherein the number of the solder particles of 20/m or less contained in the solder powder is not less than 3 %. (6) A flux for soldering characterized by a hydrocarbon compound containing one or more primary or tertiary CH bonds and a halogen-containing hydrogen donor compound. (7) The fluxing agent for welding according to the item (6), wherein the halogen-containing hydrogen donor compound is an organic halogen compound. (8) The flux for welding according to the item (6) or (7), wherein the hydrocarbon compound containing one or more primary, secondary or tertiary CH bonds is selected from the group consisting of tetralin, tetraisobutylene, octahydroquinone, and l. -α-naphthyl-1-n-butylhexadecene, 9 ' 10-dihydro-9,10-diisobutylphosphonium, n-octadecylbenzene, y3-n-octadecyltetrahydronaphthalene Any one of the group of polyisobutylene. (9) The flux for welding according to any one of the items (6) to (8), wherein the content of the halogen-containing hydrogen donor compound is 0.02 in terms of chlorine for the entire flux of the welding flux. The mass is in the range of % to 20% by mass. (1) The flux for welding according to any one of (6) to (9), wherein the content of the hydrocarbon compound containing one or more primary, secondary or tertiary CH bonds is the total amount of the flux for welding. It is in the range of 0.01% by mass to 20% by mass. (Please read the note on the back and fill out this page.) This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) -8- 1265838 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention (5) (11) A solder paste containing the metal flux of any one of (1) to (5) and the flux for soldering according to any one of (6) to (10). (12) The solder paste of (1 1), wherein the ratio of the metal solder to the total amount of the solder paste is in the range of 86 to 92% by mass, and the ratio of the flux for soldering is 14 to 8 mass% Within the scope. (1 3) Applying a solder paste of (1 1 ) or (1 2 ) to a circuit substrate, and mounting an electronic component on the coated portion, and then heating the circuit substrate to bond the electronic component to the circuit substrate A method of manufacturing a circuit board. (14) A soldering flux for soldering prepared by diluting a flux for soldering according to any one of (6) to (10) with a solvent. (1) A resin-incorporated soldering wire comprising the metal flux of any one of (1) to (5) and the welding flux of any one of (6) to (1). MODE FOR CARRYING OUT THE INVENTION The metal flux of the present invention is: a metal flux having a zinc content of 8.8 to 5.0% by mass, a cerium content of 0.05% by mass or less or bismuth, and a remainder of tin or an unavoidable impurity, and a zinc content. In the range of 9.0 to 5.0% by mass, the cerium content is in the range of 2.0 to 0.05% by mass, and the metal flux of the remainder of tin or unavoidable impurities is in the range of 8.5 to 6.5% by mass, and the cerium content is in the range of 1.5 to 0.1% by mass. Within the range of mass %, the remainder is tin or inevitable impurities of metal solder, (please read the back note before refilling this page) This paper scale applies to China National Standard (CNS) A4 specification (210〆297 mm) -9- 1265838 A7 _____ B7 V. Description of invention (6) (Please read the note on the back and fill out this page) Zinc content is in the range of 8.3 to 7.5 mass%, and bismuth content is in the range of 1.2 to 0.5 mass%. Inside, the remainder is a metal flux that is tin or an inevitable impurity. By using the metal solder in the composition range, high wettability at the time of joining of the electronic component and high impact resistance and high solderability of the joint member can be obtained. Inevitable impurities refer to the elements that must be mixed in the manufacture of metal solder. Further, even if it is added, an element which does not affect the characteristics of the metal solder can be defined as an unavoidable impurity. The amount of the inevitable impurities is usually 1% by mass or less of each element, and the unavoidable impurity elements are exemplified by non-metal elements, semi-metal elements, carbon elements, oxygen elements, nitrogen elements, transition metal elements, and the like. In particular, elements such as lead, silver, antimony, copper, iron, and 'aluminum, arsenic, and cadmium are easily incorporated into the metal solder. These elements are not adversely affected by the characteristics of the metal solder of the present invention. Inevitable impurities. The reason why the composition of the metal solder is set in the above range is printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs. The oxidation of the metal solder is obtained if the zinc content is higher than 8.8% by mass in the case of the Sn-Zn binary alloy. The situation is fierce, and the wettability is remarkably inferior, and the wafer is lifted when the components are loaded and reflowed. On the other hand, if the zinc content is less than 5.0% by mass, the melting (liquidus temperature) exceeds 2 15 ° C, and the service life of the electronic component is remarkably reduced due to the heat resistance of the electronic component. Further, by setting the cerium content to 5% by mass or less or 0, the reliability and wettability of the conjugate can be improved.
Sn-Zn-Bi系三元合金之情況，若鋅含量高於9.0質量％ 則氧化情況激烈，且浸潤性顯著低劣。而若鋅含量低於5.0 質量％則融點超過2 1 5 °C由於裝載元件之耐熱性因而元件之 使用壽命顯著惡化。因此爲防止金屬焊藥之氧化並提高浸 本紙張尺度適用中國國家標準（CNS ) A4規格（210乂297公釐1 「10- 1265838 A7 ____B7 _ 五、發明説明（7 ) 潤性，鋅含量以在8· 5至6.5質量％範圍內爲佳，8.3至7.5 質量％範圍內更佳。鉍含量若超過2.0質量％則裝載有元件 之接合部其耐衝擊性顯著惡化。鉍含量若低於〇.〇5質量％ 則浸潤性顯著惡化。爲獲得耐衝擊性及高度浸潤性，鉍含 量以在1.50至0.1質量％範圍內爲佳，2至0.5質量％範 圍內更佳。 由金屬焊藥製造焊藥粉末之方法代表者爲例如霧化法 。具體而言碟型霧化器法或噴霧法均佳。進行霧化時爲防 止粉末氧化，以於氮氣或氬氣、氦氣等惰性氣體大氣下進 行爲佳。真空下進行之霧化法當然亦可。製造焊藥粉末後 ，通常以分級機過篩分開。粒度範圍因裝載物品之間距而 異。裝載〇.3mm間距或0603間距元件、〇.5mmCPS等微間 距元件時，係使用分級爲38至22// m，一般分級爲45至 22//m之粉末。分級機以震動過飾式、風力式爲佳，但爲 防止氧化以在氮氣等惰性氣流中進行分級爲佳。當然使用 溶劑之濕式分級亦可。 焊藥粉末之粒徑藉由過篩分開爲依據日本工業規格（ JIS，Japan Industrial Scale )爲 63 至 22// m、45 至 22// m 級3 8至22 μ m等規格。焊藥粉末之粒度測定一般係依據 JIS規定使用標準過篩與天平之方法。但是焊藥粉末之表面 大多會因靜電而附著微粒子焊藥粉末，以此方法不能徹底 分離附著於焊藥粉末上之微粒子，所測得焊藥微粒子之量 實際上小於焊藥粉末中所含微粒子之量。例如依據ns測定 粒度分布之過篩分離後之焊藥粉末以顯微鏡觀察時，可見 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 7γΓί " '~~ - (請先閱讀背面之注意事項再填寫本頁) -裝· 經濟部智慧財產局員工消費合作社印製In the case of the Sn-Zn-Bi ternary alloy, if the zinc content is more than 9.0% by mass, the oxidation is severe and the wettability is remarkably inferior. On the other hand, if the zinc content is less than 5.0% by mass, the melting point exceeds 2 15 ° C, and the service life of the element is remarkably deteriorated due to the heat resistance of the load member. Therefore, in order to prevent the oxidation of metal solder and improve the size of the immersion paper, the Chinese National Standard (CNS) A4 specification (210乂297 mm 1 “10-1265838 A7 ____B7 _ V, invention description (7)) It is preferably in the range of 8.5 to 6.5 mass%, more preferably in the range of 8.3 to 7.5 mass%, and if the cerium content exceeds 2.0% by mass, the impact resistance of the joint portion loaded with the element is remarkably deteriorated. 〇5 mass%, the wettability is remarkably deteriorated. In order to obtain impact resistance and high wettability, the cerium content is preferably in the range of 1.50 to 0.1% by mass, more preferably in the range of 2 to 0.5% by mass. The method of the flux powder is represented by, for example, an atomization method. Specifically, the dish atomizer method or the spray method is good. In order to prevent oxidation of the powder during atomization, an inert gas atmosphere such as nitrogen or argon gas or helium gas is used. It is preferred to carry out the lowering method. The atomization method carried out under vacuum is of course also possible. After the solder powder is produced, it is usually sieved by a classifier. The particle size range varies depending on the distance between the loaded articles. The loading is 3 mm pitch or 0603 pitch components, 〇.5mmCPS and other micro For the component, a powder with a grade of 38 to 22 // m and a general classification of 45 to 22 / / m is used. The classifier is preferably a vibrating type or a wind type, but is used to prevent oxidation in an inert gas stream such as nitrogen. It is preferred to carry out the classification in the middle. Of course, the wet classification of the solvent can be used. The particle size of the flux powder is separated by sieving according to Japanese Industrial Standards (JIS, Japan Industrial Scale) of 63 to 22 // m, 45 to 22 // m grade 3 8 to 22 μ m, etc. The particle size measurement of the flux powder is generally based on the standard sieving and balance method according to JIS regulations, but the surface of the flux powder is mostly attached to the microparticle flux powder due to static electricity. In this way, the fine particles attached to the solder powder cannot be completely separated, and the amount of the solder particles is actually smaller than the amount of the fine particles contained in the solder powder. For example, the flux after the sieve separation according to the ns is determined. When the powder is observed under a microscope, it can be seen that the paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). 7γΓί " '~~ - (Please read the notes on the back and fill out this page) - Installation · Ministry of Economic Affairs Hui Property Bureau employee consumption cooperative printed
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IJL 1265838 A7 ____ B7 五、發明説明（8 ) (請先閲讀背面之注意事項再填寫本頁) 到大焊藥粒子之表面附著有多數焊藥微粒子，焊藥粉末中 若此種微粒子之存在量增加則焊藥粉末越趨向易氧化，焊 料糊漿之保存安定性、回焊特性降低。 本發明人等發現對焊藥粉末之粒度分布測定，藉由依 據Π S規定之方法’以及採用焊藥粉末中所含微粒子成分之 個數分布，可獲得特性優越之焊藥粉末。 焊藥粉末中微粒子含量之測定可藉由顯微鏡之晝像解 析、電位區段（electrozone )法或庫爾特計數器（coulter counter )進行。有關庫爾特計數器於「粉體工學便覽」（ 粉體工學會編，第2版第19至20頁）中說明其原理，係 使分散有粉體之溶液通過隔壁上打開之細孔，藉測定該細 孔兩側之電阻變化可測定粉體之粒度，因此所測定之粉體 個數比率之再顯性良好。使用該方法測定焊藥粉末之粒度 分布時，將焊藥粉末分散於溶液之際，附著於焊藥粉末之 微粒子成分易於分離，因而藉以往過篩分離法之質量分布 或體積分布測定無法檢出者，以本方法可將附著於焊藥粉 末之微粒子定量化。 經濟部智慧財產局員工涓費合作社印製 藉由顯微鏡之畫像解析或庫爾特計數器之方法可測定 之微粒子下限界爲l//m左右。因l//m以下之微粒子之混 入量以任何方法均難以測定，以通常之霧化方法製作之焊 藥粉末，幾乎不含1 // m以下之微粒子，依據上述之焊藥微 粒子之個數分布測定以限於1 // m以上之粉體爲宜。 本發明之個數分布之管理條件以焊藥粉末中所含20 // πι以下之焊藥粒子係個數分布控制於3〇%以下較佳，20% -12- 本紙張尺度適用中.國國家標準（CNS ) A4規格（210 X 297公釐） 1265838 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（9 ) & T更佳。20 // m以下之焊藥粒子之個數分布若超過上述 @ ’則因每單位質量之表面積變大而易於氧化，因此在 製作焊料糊漿之回焊時，對焊藥粉末之融熔性有不良影響 。又因容易與助熔劑反應，焊料糊漿之保存期限縮短且黏 著力亦降低。 爲降低焊藥粉末中微粒子之混入量，將焊藥粉末分級 時之分級點設定爲較目標粒度更大者，同時反覆進行焊藥 粉末之風篩或過篩分離使焊藥粉末中微粒子之混入量成爲 目標水準以下’並延緩粉體供應速度則微粒子易被去除， 亦可採用使用水以外之溶劑的濕式分級方法。 本發明所使用之焊藥粉末，係以經過篩分離之焊藥粒 徑之上限在規定篩網網目以下粒度之粉末，其質量分布 90°/。以上，較好95%以上爲佳。 又’本發明所使用之焊藥粉末中氧原子含量亦以低者 爲佳，藉使成爲500ppm以下，更好300ppm以下可提昇焊 料糊漿之保存安定性及回焊特性。爲降低焊藥粉末中氧原 子含量，使製作焊藥粉末之霧化步驟於焊藥粉末不易氧化 之氣體中進行，而使製作之焊藥粉末在不易氧化之環境下 操作爲有效之方法。具體而言上述步驟以在氮氣、氬氣、 氨氣等惰性氣體存在之環境下或真空中進行爲佳。 焊接用助熔劑、焊料糊漿、焊藥線、焊用液狀助熔劑 中亦可配合活性劑、合成樹脂或松香所成之樹脂成分、溶 劑、觸變劑，視需要之pH調整劑、防鏽劑、抗氧化劑、有 機酸成分等。 本紙張尺度適用中.國國家標準（CNS ) A4規格（210X297公釐） -13- (請先閱讀背面之注意事 項再填· :寫本頁) 1265838 A7 B7 五、發明説明（10 ) (請先閲讀背面之注意事項再填寫本頁} 本發明之焊接用助熔劑，其特徵爲含有1個以上一級 、二級或三級CH鍵之烴化合物與含鹵之氫供予體化合物作 爲活性劑。 含鹵之氫供予體化合物係指含鹵之化合物，於焊接用 助熔劑中具有還原作用之化合物，特別以於焊接用助熔劑 之使用溫度下會熱分解而產生鹵素之化合物爲佳。 此類化合物可例舉於焊接用助熔劑之使用溫度下會熱 分解而產生鹵化氫之有機鹵化合物。 以往活性劑大多使用離子性物。但是離子性活性劑因 在室溫下亦具有活性，特別是對易發生氧化之無鉛焊藥之 保存安定性有不良影響。因此對無鉛焊藥而言以在回焊時 分解而表現活性之有機溴化物爲佳。於焊接用助熔劑中添 加有機鹵化合物一事揭示於例如日本特公昭5 6 - 3· 2 0 7 9號公 報、特開平3-100594號公報、特公平4-5 9079號公報、特 開平8- 1 5 5676號公報等。 經濟部智慧財產局員工消費合作社印製 本發明中所使用之較佳有機鹵化合物，可例示如1 _溴_ 2 - 丁醇、1 -溴-2 -丙醇、3 -溴-1 -丙醇、3 -溴-1，2 -丙二醇、1 ’ 4 -二溴-2 - 丁醇、1，3 -二溴-2 -丙醇、2，3 -二溴-1 -丙醇、 1，4·二溴-2，3-丁 二醇、2，3-二溴-2-丁烯-1，4-二醇、1-溴甲基-1-丁烯、1，二溴丁烯、；!·溴-^丙烯、2，3_二 溴丙烯、溴乙酸乙酯、α -溴辛酸乙酯、^ -溴丙酸乙酯、 冷-溴丙酸乙酯、α -溴乙酸乙酯、2，3-二溴琥珀酸、2-溴 琥珀酸、2，2-二溴己二酸、2，4-二溴乙醯苯、ii-二溴 四氯乙烷、1，2-二溴-1·苯基乙烷、1，2-二溴苯乙烯、4- -14 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1265838 A7 B7 五、發明説明（11 ) 硬脂醯氧基苯甲基、4-硬脂基氧基苯甲基溴、4-硬脂基苯甲 基溴、4-溴甲基苯甲基硬脂酸酯、4-硬脂醯胺基苯曱基溴、 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 2 ’ 4、雙溴甲基苯甲基硬脂酸酯、4-棕櫚醯氧基苯甲基溴、 4·肉荽蔻醯氧基苯甲基溴、4-月桂醯氧基苯甲基溴、4-十一 碳醯氧基苯甲基溴、9，10，12，13，15，16-六溴硬脂酸 ' 9，10，12，13，1 5，1 6-六溴硬脂酸甲酯、相同物之乙 酯、9，1 0，12，1 3 -四溴硬脂酸、相同物之甲酯、相同物 之乙酯、9，1 0，1 2，1 3，1 5，1 6-六溴硬脂醇、9，1 0，1 2 ’ 13-四溴硬脂醇、1，2，5，6，9，10 -六溴環十二院、雙 (2，3_二溴丙基）琥珀酸酯、雙（2，3-二溴丙基）鄰-苯 二甲酸酯、雙（2，3-二溴丙基）對-苯二甲酸酯、雙（2， 3-二溴丙基）.鄰、苯二甲醯胺、雙（2，3_二溴丙基）對-苯 二甲醯胺、三（2，3-二溴丙基）偏苯三酸酯、三（2，3-二 溴丙基）偏苯三醯胺、四（2，3-二溴丙基）均苯四甲酸酯 、三（2，3-二溴丙基）均苯四甲醯胺、四（2，3-二溴丙基 )均苯四甲醯胺、雙（2，3_二溴丙基）甘油、三羥甲基丙 烷雙（2，3_二溴丙基）醚、雙（2，3-二溴丙基）酒石醯胺 、N，Ν’-雙（2，3-二溴丙基）琥珀醯胺、N，N，N，，N’-四（2，3-二溴丙基）琥珀醯胺、Ν，Ν’-雙（2，3-二溴丙基 )脲、Ν，Ν，Ν、Ν·-四（2，3-二溴丙基）脲、2，2-雙[4-(2，3-二溴丙基）-3，5-二溴苯基]丙烷、α，α，α-三 溴甲基硕、α，yS-二溴乙基苯、（2, 3-二溴丙基）三聚異 氰酸酯等。其中特別以使用有機鹵化合物9，1 0，1 2，1 3， 1 5，1 6 -六溴硬脂酸、9，1 0，1 2，1 3，1 5，1 6 -六溴硬脂酸 -15- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1265838 A7 B7 五、發明説明（12 ) (請先閲讀背面之注意事項再填寫本頁) 甲酯、同化合物之乙酯、三（2，3 -二溴丙基）三聚異氰酸 酯爲佳。焊接用助熔劑以使用上述有機鹵化合物爲佳，其 理由並不淸楚，咸認係因熱分解產生鹵素之溫度接近於預 熱之溫度而適宜。 又，亦可使用含氯、碘替代溴之有機鹵化合物。此等 有機鹵化合物可單獨使用亦可2種以上合倂使用。 有機鹵化合物之添加量對焊接用助熔劑全量而言，以 氯計爲0.02質量％至20質量％範圍內，較好爲〇. 1質量％ 至10質量％範圍內。有機鹵化合物之添加量若小於〇.〇2質 量％，則回焊時不能獲得充分之焊接性，若多於20質量％ 則不僅不經濟，且其他助熔劑成分減少而不能充分達成助 熔劑要求之其他機能。 以氯計係指使用將有機溴化合物之溴換算成氯之分子 量所表示之換算量。 含離子性溴之活性劑爲價廉且少量添加即可產生活性 ，因此可使用無損於焊料糊漿安定性範圍之量。此外，爲 達減低昂貴有機鹵化合物之添加量，合倂使用亦有效。 經濟部智慧財產局8工消費合作社印製 其他適宜添加之離子性活性劑可例舉如異丙胺氫溴酸 鹽、丁基胺鹽酸鹽、環己胺氫溴酸鹽等氫鹵酸胺鹽，1，3 -二苯基胍氫溴酸鹽等。 亦可使用氯、碘之鹵化氫鹽替代溴。此等鹵化氫鹽可 單獨使用亦可2種以上合倂使用，其配合量對助熔劑全量 而言爲0.0 00 5質量％至2質量％範圍內，較好爲0.01質量 %至1質量％範圍內。添加量若低於0.0005質量％，則幾無 -16- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1265838 經濟部智慧財產局員工消費合作社印製 A7 __ B7 _五、發明説明（13 ) 活性效果，添加量若超過2質量％則與助熔劑內所含之活性 劑反應而損及焊料糊漿之安定性。 本發明以添加含有1個以上一級、二級或三級CH鍵之 烴化合物者爲佳，而較宜使用於約1 〇 〇至15 〇 °c下容易與氧 反應而氧化之化合物。此類化合物可列示如四氫化萘、四 異丁烯、八氫化蔥、l-α-萘基-1-正丁基十六碳烯、9，10-二氫-9，10-二異丁基蔥、正十八烷基苯、正十八烷基四 氫化萘、聚異丁烯、α-苯基-2-四氫化萘基丁烷、9，10-二 異丁基全氫蒽、5 -異丁基萘嵌戊烷等。其添加量對助熔劑 全量而言爲〇.〇1質量％至20質量％，較好爲〇.5質量％至5 質量％範圍內。 其作用並不明確，咸認添加至焊接用胁熔劑中之含有1 個以上一級、二級或三級CH鍵之烴化合物，在預熱溫度， 一般約100至150°C下容易與氧反應而氧化，而含鹵之氫供 予體化合物對該氧化反應具有觸媒之促進作用。 以往之焊藥糊漿於約1 50°C預熱階段焊藥粉末即顯著氧 化。本發明之焊藥糊漿則因含有含1個以上一級、二級或 三級CH鍵之烴化合物，在預熱溫度下本發明之烴化合物與 氧反應吸收氧氣，而抑制預熱溫度下焊藥粉末之氧化。此 外亦認爲因鹵化氫將焊藥經氧化之表面還原而提高焊接性 〇 本發明之焊接用助熔劑中除溶劑、樹脂成分、觸變劑 外，視需要亦可添加防鏽劑、抗氧化劑、pH調整劑。 本發明之焊接用助熔劑中配合之溶劑，與以往之助熔 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X；297公釐） -17- 1265838 A7 _______ 五、發明説明（14 ) (請先閲讀背面之注意事項再填寫本頁) 劑及焊藥糊漿相同，可使用醇類、醚類、酯類、二醇之中 級或闻級醇、芳族溶劑之一種或一種以上混合使用。例如 可使用苯甲醇'丁醇、乙基溶纖素、丁基溶纖素、丁基卡 必醇、丙撐二乙二醇單丁基醚、二乙二醇單苯基醚、二乙 一醇己基酸、丙二醇單苯基醚、二乙二醇單己基醚、二乙 一醇單2 -乙基己基醚、二辛基苯二甲酸酯、二甲苯、2_甲 基-1，3-己二醇、2-乙基-1，3-己二醇或此等之混合溶劑。 本發明之焊接用助熔劑中所配合之樹脂成分可使用以 往焊接用助熔劑中配合之習知樹脂，例如天然松香、不勻 化松香、聚合松香、加氫松香、改質松香、松香酯等松香 衍生物，合成樹脂可使用聚酯、聚胺基甲酸酯、丙烯酸系 樹脂等。 爲改善本發明之印刷性而添加之觸變劑可使用微細之 氧化矽粒子、高嶺土粒子等無機系物，或加氫蓖麻油、醯 胺化合物等有機系物。 經濟部智慧財產局P貝工消費合作社印製 本發明之焊接用助熔劑中所使用之pH調整劑可例示如 烷醇胺類、脂族第1至第3級胺類、脂族不飽和胺類 '環 脂族胺類、芳族胺類等胺化合物。此等化合物可單獨使用 亦可2種以上合倂使用。 本發明之焊接用助熔劑之pH値以調至4至9範圍內爲 佳，更好爲6至8之範圍，因可抑制焊藥粉末與助熔劑之反 應而佳。本發明pH調整劑之添加量對焊接用助熔劑全量而 言，以0.0 5質量％至2 0質量％範圍內爲佳。添加量若小於 〇.〇5質量％，貝[]pH調整劑之效果不足，添加量若超過20 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -18 - 1265838 A7 B7 五、發明説明（15 ) 質量％則焊藥糊漿易吸濕而不佳。 (請先閲讀背面之注意事項再填寫本頁) 此等胺化合物之具體化合物可例舉如乙醇胺、丁基胺 、胺基丙醇、聚氧化乙烯油基胺、聚氧化乙烯月桂基胺、 二乙胺、三乙胺、甲氧基丙胺、二甲胺基丙胺、二丁胺基 丙胺、乙基己胺、乙氧基丙胺、乙基己氧基丙胺、雙丙胺 、異丙胺、二異丙胺、六氫吡啶、2，6-二甲基六氫吡啶等 〇 本發明之焊接用助熔劑，於助熔劑中亦可添加作爲防 鏽劑之唑類，例如苯并三唑、苯并咪唑、甲苯三唑等。防 鏽劑之添加量對助熔劑全量而言，以0.0 5質量％至.2 0質量 %範圍內爲佳。 本發明之焊接用助熔劑以添加抗氧化劑爲佳。抗氧化 劑可使用一般合成樹脂等還原劑，可例舉如可溶解於溶劑 之酚系化合物、磷酸系化合物、硫系化合物、生育酚及其 衍生物或抗壞血酸及其衍生物。此等還原劑可單獨使用亦 可混合使用。其配合量對助熔劑全量而言爲0.0005質量％ 至20質量％範圍內，較好爲0.01質量％至10質量％範圍內 〇 經濟部智慧財產局員工消費合作社印製 添加抗氧化劑之作用機制並不十分淸楚，咸認可能是 此等抗氧化劑對焊藥糊漿中溶存之氧或空氣中之氧有效， 而可抑制金屬焊藥之氧化。咸認此等抗氧化劑可作爲自含 鹵成分游離之鹵素的接受體，而具有防止游離之鹵與金屬 焊藥反應之效果。 有機酸成分可例舉如以往習知之琥珀酸、苯二甲酸、 -19- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1265838 A7 _B7 ____ 五、發明説明（16 ) (請先閲讀背面之注意事項再填寫本頁) 硬脂酸、癸二酸等，可使用達到回焊溫度時會產生有機酸 之化合物之有機酸衍生物。分解性之有機酸酯，因單獨使 用時在回焊溫度時之分解性低，爲促進分解添加少量之酯 分解觸媒亦有效。酯分解觸媒爲具有可促進分解性有機酸 酯在回焊溫度分解產生酸之作用者即可，其中特別以有機 鹼與氫鹵酸鹽爲有效。 有機酸酯可例舉如各種脂族羧酸酯、芳族羧酸酯、脂 族磺酸酯、芳族磺酸酯等。具體例可舉如對甲苯磺酸-正-丙 酯、對甲苯磺酸異丙酯、對甲苯磺酸異丁酯、對甲苯磺酸_ 正-丁酯、苯磺酸-正-丙酯、苯磺酸異丙酯、苯磺酸異丁酯 、水楊酸-正-丙酯' 水楊酸異丙酯、水楊酸異丁酯、水楊酸 正丁酯、4_硝基苯甲酸異丙酯、4-硝基苯甲酸第三丁酯、甲 基丙烯酸第三丁酯、丙烯酸第三丁酯、丙二酸第三丁酯、 溴乙酸第三丁酯等。其添加量對助熔劑全量而言以使用 0.01質量％至20質量％範圍內爲佳，更好爲0.05質量％至 5質量％範圍內。 經濟部智慧財產局員工消費合作社印製 本發明係以將使用上述金屬焊藥之焊藥粉末與助熔劑 混練作爲焊藥糊漿使用爲佳。此種情況對焊藥糊漿全量而 言焊藥粉末之比率以86至92質量％範圍內，助熔劑之比率 以I4至8質量％範圍內爲佳。 本發明之焊藥糊漿適宜於製造基板例如印刷電路板與 電子元件接合之接合物之際使用。本發明之助熔劑及焊藥 糊漿之使用方法以及電子元件接合物之製造方法，例如以 印刷法等將焊藥糊漿塗佈於欲焊接之部位，裝載電子元件 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -20 - 1265838 A7 B7 五、發明説明（17 ) ’然後加熱使焊藥粒子融熔後再凝固，即可將電子元件接 合在基板上。 (請先閲讀背面之注意事項再填寫本頁} 基板與電子元件之接合方法（封裝方法）可例舉如表 面封裝技術（SMT )。該封裝方法首先係以印刷法將焊藥 糊漿塗佈於基板，例如印刷電路板上欲焊接之部位，然後 將晶片元件或QFP等電子元件裝載於焊藥糊漿上，藉回焊 熱源整體焊接。回焊熱源可使用熱風爐、紅外線爐、蒸氣 凝聚焊接裝置、光束焊接裝置等。 本發明之回焊條件以進行預熱及回焊之2段步驟爲佳 ’其條件分別爲預熱溫度爲130至180°C，較好爲130至 150 °C，預熱時間爲60至120秒，較好爲60至90秒，回 焊溫度爲2 1 0至2 3 0 °C，較好爲2 1 0至2 2 0 °C，回焊時間爲 3 0至6 0秒，較好爲3 0至4 0秒。 本發明之焊藥糊漿可於氮氣中亦可於大氣中實施上述 之回焊步驟。氮氣回焊時氧濃度爲5體積％以下，較好爲 〇 · 5體積％以下，可較於大氣回焊下更提昇電路板等基板之 焊藥浸潤性，亦較少發生焊珠而爲安定之處理。 經濟部智慧財產局員工消費合作社印製 然後，將基板冷卻即完成表面封裝。以該封裝方法製 造電子元件接合物時，亦可進行印刷電路板等基板（被接 合板）兩面之接合。又，可使用本發明焊藥糊漿之電子元 件可例舉如LSI、電阻器、電容器、電晶體、電感、濾波器 、震盪器、震動器等，但並非限定於此等。 本發明係預先於基板預定之表面，例如僅於印刷基板 之電路金屬之預定表面藉由化學反應而形成黏著性黏膜， 本紙張尺度適用中國國家標準（CNsTa4規格（210X297公釐) -21: "" ——' 1265838 A7 B7 五、發明説明（18 ) 於其上附著焊藥粉末後塗佈助熔劑，加熱至焊藥融熔溫度 進行回焊，在焊藥所形成之電路基板（日本特開平7-7244 公報）上，使用本發明之焊藥糊漿以SMT (表面封裝技術 ，Sulface Mounted Technique)進行封裝時，具有更優越之 焊接性。 本發明之金屬焊藥、焊藥糊漿由於與習知者相較，具 有優越之回焊特性、焊接性、與欲接合金屬之浸潤性或者 印刷性等特性，且回焊時產生之焊珠亦減少。特別是對接 合之電子元件或電路基板之浸潤性顯著提昇，而接合物之 耐衝撃性亦顯著提昇。此外，依據本發明以廢棄物對環境 污染少之無鉛焊藥合金使電子元件之接合微間距化，例如 對應於封裝電路板之微間距化、元件之多樣化或藉此而可 提供元件壽命優越之電路板。 [實施例] 以下列實施例更進一部說明本發明之內容，但本發明 並非限定於此等者。 [試驗法] (1 )焊藥粉末之微粒子個數分布 使用克魯塔（Coalta)(股）製克魯塔計數器（多重分 級器II型），將lg焊藥粉末分散於l〇〇ml之1%氯化鈉電 解質溶液中並置於檢出器中，檢出管之細孔徑設定爲400 A m，測定1 // m以上粉體之粒度分布。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -22 - (請先閲讀背面之注意事項再填寫本頁) •裝. 訂 經濟部智慧財產局員工消費合作社印製 1265838 A7 __________^_B7_ 五、發明説明（19 ) (2 )氧氣濃度 以雷扣（Reko )公司之氧氣分析計（紅外線分析法） 測定。 (請先閲讀背面之注意事項再填寫本頁) (3 )水分 將焊藥糊漿置於水分汽化裝置（京都電子工業（股） 製：ADP-Wi)中，於iscrc加熱使汽化，以氮氣爲攜帶氣體 ’導入卡爾-費歇水分計（京都電子工業（股）製：MKC-210 )中，測定氣體中之水分。 (4 ) pH 値 於50ml甲苯、49.5ml異丙醇、〇 5ml水組成之混合溶 液中，溶解4g助熔劑並以pH計測定之。若爲焊藥糊漿時 大約取相當於4g助熔劑之焊藥糊漿同樣測定之。 (5 )焊珠試驗① 經濟部智慧財產局員工消費合作社印製 依據JIS Z-3 284進行測定。使用金屬罩於氧化鋁試驗 板上印刷焊藥糊漿，形成4個直徑6.5mm、厚度0.2mm之 圓型圖案。將該試驗板於1 5 0 °C乾燥1分鐘後，加熱至23 5 °C使焊藥融熔，融熔後於5秒內水平取出基板。水平放置 至基板上之焊藥固化，然後以20倍之放大鏡檢視焊藥外觀 ，並以50倍之放大鏡檢視焊藥粒子之發生情況。焊珠之發 生情況爲JIS之判定基準3以下者，當作不合格（表1以X 表示之）。判定基準高於3者，其發生狀況視爲良好而以 ◎、〇、△三階段評估之。 (6 )浸潤性 依據JIS Z-3 284進行測定。使用金屬罩於銅與黃銅之 -23- 本紙張尺度適用中.國國家標準（CNS ) A4規格（210X297公釐） 1265838 A7 B7 五、發明説明（20 ) (請先閲讀背面之注意事項再填寫本頁) 試驗板上印刷焊藥糊漿，形成4個直徑6.5mm、厚度 0.2mm之圓型圖案。將該試驗板於15〇°C乾燥1分鐘後，加 熱至23 5 °C使焊藥融熔，融熔後於5秒內水平取出基板。水 平放置至基板上之焊藥固化，然後檢視浸潤性之程度。浸 潤性爲JIS之判定基準3以下者，當作不合格（表1以X 表示之）。判定基準高於3者，其浸潤性狀況視爲良好而 以◎、〇、△三階段評估之。 (7 )耐衝擊性試驗 經濟部智慧財產局員工消費合作社印製 耐衝擊試驗（熱衝擊試驗）係使用1.6 m m X 1 0 0 m m x 100mm之試驗基板。裝載元件係使用銅線上電鍍Sn-lOPb 之1〇〇孔之之L-QFP。試驗基板係使用將銅圖案以軟性蝕 刻液（滅庫（股）滅庫布來特CB-801 )進行1至2微米蝕 刻處理後進行耐熱預助熔劑（滅庫預助熔劑R-4Ό3 0 )處理 之基板。使用1 5 0微米之金屬罩於該試驗基板上印刷焊藥 糊漿。印刷後於基板上裝載電鍍Sn-Pb之L_QFP。回焊條 件爲預熱溫度1 6 0 °C，9 0秒，高峰溫度爲2 2 0 °C，2 0 0 °C以 上爲3 〇秒。回焊處理係設想兩面回焊進行2次後，作爲熱 衝擊試驗用試驗片。此外於試驗片單面（未裝載元件之面 )之中心部位設置1.5mm之引線，兩端以耐熱性卡普頓膠 帶固定使成爲強制歪斜附重之狀態，以此狀態投至熱衝撃 試驗機內。熱衝擊試驗之條件以-40°Cx30分鐘，+125°Cx30 分鐘一循環爲初期，測定100循環、3〇〇循環、5〇〇循環時 之接合強度。接合強度之測定法係以45。剝離強度法測定 各20孔。測定剝離強度時之速度爲2〇mm/分鐘，以4〇倍 -24- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1265838 A7 _ B7 五、發明説明（21 ) 實體顯微鏡觀察強度及剝離面。觀察結果以銅與焊藥界面 發生1孔剝離亦視爲不合格（表1以X表示不合格，以〇 表示合格）。 (請先閱讀背面之注意事項再填寫本頁) (8 )晶片翹起試驗 晶片翅起S式驗係使用厚度1.6mm、100mm X 100mm之 試驗基板。裝載元件（晶片元件）係使用1 608 ( 1.6mm X O.Smm )之Sn-10Pb電鍍品。試驗基板係使用將銅圖案以軟 性蝕刻液（滅庫（股）滅庫布來特CB-8 01 )進行1至2微 米蝕刻處理後進行耐熱預助熔劑（滅庫（股）滅庫預助熔 劑R-4〇30)處理之基板。使用150微米之金屬罩於該試驗 基板上印刷焊藥糊漿。印刷後於基板上裝載電鍍Sn-Pb之 晶片元件1 〇個。回焊條件爲預熱溫度1 60°C，.90秒，高峰 溫度爲220°C，200°C以上爲30秒。完全無晶片翹起時評估 爲〇，有1個翹起時爲Λ，2個以上翹起爲X。 (9 )焊珠試驗② 經濟部智慧財產局員工消費合作社印製 使用具有5個厚度0.2 m m，直徑6.5 m m孔洞之印刷罩 ，將焊藥糊漿印刷至氧化鋁基板上。製作9個此等樣品。 將其中8個置於30°C 90%之恆溫恆濕槽內，每3小時各取 出8個。 將此等樣品展開於預先設定爲23 5 °C之熱板上，於焊藥 融熔後5秒取出，放置至焊藥冷卻。 以1〇倍放大鏡觀察凝固之焊藥外觀全貌’依據JISZ-3 2 8 4 (附冊：i〗）表1及第1圖規定之焊藥粒子凝集狀態評 估之。 -25- 本紙張尺度適用中.國國家標準（CNS ) A4規格（210X297公釐） 1265838 A7 ___B7_____ 五、發明説明（22 ) (請先閲讀背面之注意事項再填寫本頁) 亦即，焊藥粉末融熔而焊藥形成1個大球，周圍無焊 珠時評估爲1，焊藥粉末融熔而焊藥形成1個大球，周圍有 直徑75 // m以下之焊珠3個以上時評估爲2，焊藥粉末融 熔而焊藥形成1個大球，周圍有直徑75 // m以下之焊珠3 個以上且不爲半連續之環狀排列時評估爲3，焊藥粉末融熔 而焊藥形成1個大球，周圍有多數細珠呈半連續之環狀排 列時評估爲4，上述以外之情況評估爲5。 (1 〇 )空隙觀察 於60mm平方之銅板上使用150微米之金屬罩印刷直 徑6mm之6個焊藥後，於大氣下回焊，繼之以切割器將焊 藥連銅板一起切斷後，以顯微鏡觀察該焊藥部分以觀察空 隙發生之情況。計測6個焊藥上大於1 0 // m以上之空隙， 每1個焊藥之空隙平均個數爲2個以上時爲不合格。 (實施例1至1 1、比較例1至8 ) 經濟部智慧財產局員工消費合作社印製 本發明之實施例、比較例如下示。又，本發明之實施 方法並非限定於實施例1至1 1及例示之電子元件接合物之 製造方法者。 <助熔劑及焊料糊漿之製造> 添加作爲樹脂成分之聚合松香1 7.5質量％、不勻化松 香27.5質量％、作爲觸變劑之加氫蓖麻油6質量％、作爲有 機酯之對甲苯磺酸正丙酯〇·5質量％、作爲酯分散觸媒之環 己胺氫溴酸鹽0.08質量％、添加作爲有機鹵化合物之六溴 -26- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 1265838 A7 B7 五、發明説明（23 ) (請先閱讀背面之注意事項再填寫本頁) 硬脂酸3 . 5質量％或不添加、添加作爲還原劑之生育酚與l-抗壞血酸基-2 ’ 6 -二棕櫚酸1 :質量比之混合物1. 〇質 量％、以及添加作爲pH調整劑之三乙胺2質量％、作爲防 鏽劑之甲苯三唑1質量％、作爲溶劑之丙二醇單苯基醚至成 爲1 0 0質量％而調製助熔劑。 於該助熔劑1 1質量％中添加8 9質量。/。表1所示之金屬 火干藥組成之焊藥粉末，該焊藥粉末（粒徑2 0 // m以下粒子 之含量25個數％ )係帶有20至45//m粒度分布之個數分 布之金屬焊藥組成，以週轉式硏磨機混練而製得3 kg焊藥 糊漿。配合成分示於表1，所用焊藥粉末之組成，助熔劑之 pH測定値亦示於表1。又，焊藥粉末之氧濃度爲300ppm， 焊藥糊漿中之水分含量爲0.3質量。/〇。 <電子元件接合物之製造> 經濟部智慧財產局員工消費合作社印製 使用本發明焊藥糊漿之電子元件接合物之製造係使用 SMT。將實施例4之組成之焊藥糊漿印刷在電路板上，將 LSI、晶片阻、晶片電容器載置於焊藥糊漿上，然後以回焊 熱源加熱焊接，回焊熱源係使用熱風爐。 回焊條件爲預熱溫度1 3 0 °C，預熱時間8 0秒，回焊波 峰溫度爲22〇°C，20(TC以上之回焊時間爲50秒。 以前述測定方法比較製作之印刷電路板及使用之焊藥 糊漿之特性，焊珠試驗係使用①，測定結果示於表1。比較 例1、2、3、8之焊珠評估觀察到多量未溶解之焊藥粉末。 -27- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1265838 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（24 ) (實施例1 2至1 7、比較例9 ) <助熔劑及焊料糊漿之製造> 添加作爲觸變劑之加氫蓖麻油、作爲樹脂成分之勻化 松香、聚合松香、作爲離子性活性劑之環己胺氫溴酸鹽或1 ’ 3 -二苯基胍氫溴酸鹽、作爲防鏽劑之苯并三唑、作爲溶 劑之丙二醇單丁基醚、作爲有機鹵化合物之9，1 0，1 2，1 3 ，1 5，1 6 -六溴硬脂酸或9，1 0，1 2，1 3，1 5，1 6 -六溴硬脂 酸甲酯或三（2，3-二溴丙基）三聚異氰酸酯、作爲胺成分 之三丙胺、作爲有機成分之對甲苯磺酸正丙酯。 於該10質量％焊接用助熔劑中，添加91Sn/8Zn/lBi之 焊藥粉末90質量％，以週轉式硏磨機混練，製造焊料糊漿 〇 其配合情況示於表2，評估結果示於表3。又，焊珠試 驗係使用②。 於使用含鹵之氫供予體化合物與含有1個以上一級、 二級或三級CH鍵之烴化合物作爲活性劑之實施例1 2至1 7 中，焊珠試驗、空隙觀察中均具有較比較例9更顯著良好 之焊接性。 發明之效果 藉由使用本發明之金屬焊藥與助熔劑之焊料糊漿，可 獲得對電子元件之高浸潤性與高耐熱衝擊性，並減少晶片 翹起之情況，且大幅抑制焊藥粉末與與助熔劑之反應，而 獲得極佳之焊接性。 (請先閲讀背面之注意事項再填寫本頁) -裝·• L—... IJL 1265838 A7 ____ B7 V. INSTRUCTIONS (8) (Please read the precautions on the back and fill out this page). Most of the solder particles are attached to the surface of the large solder particles. When the amount of such fine particles is increased in the powder, the flux powder tends to be easily oxidized, and the storage stability and the reflow characteristics of the solder paste are lowered. The present inventors have found that the measurement of the particle size distribution of the flux powder can be achieved by the method according to Π S and the distribution of the number of fine particles contained in the flux powder. The measurement of the content of fine particles in the flux powder can be carried out by means of an image analysis by a microscope, an electrozone method or a coulter counter. The principle of the Coulter Counter is described in the "Powder Engineering Handbook" (Edited by the Society of Powder Engineering, 2nd edition, pp. 19-20). The solution in which the powder is dispersed is passed through the pores opened in the partition wall. The particle size of the powder can be measured by measuring the change in electrical resistance on both sides of the pores, so that the ratio of the number of powders measured is reproducible. When the particle size distribution of the flux powder is measured by the method, when the flux powder is dispersed in the solution, the fine particle component attached to the flux powder is easily separated, and thus the mass distribution or volume distribution measurement by the conventional sieve separation method cannot be detected. The microparticles attached to the flux powder can be quantified by this method. Printed by the Intellectual Property Office of the Ministry of Economic Affairs. The lower limit of the particle size measured by the image analysis of the microscope or the Coulter counter method is about l//m. The amount of fine particles of 1/m or less is difficult to measure by any method, and the flux powder produced by the usual atomization method contains almost no particles of 1 // m or less, according to the number of the above-mentioned solder particles. The distribution measurement is preferably limited to a powder of 1 // m or more. The management condition of the number distribution of the present invention is controlled to be less than 3% by mass of the number of solder particles of 20 // π or less contained in the flux powder, preferably 20% -12 - the paper size is applicable to the country. National Standard (CNS) A4 Specification (210 X 297 mm) 1265838 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed V. Invention Description (9) & T is better. If the number distribution of the solder particles of 20 // m or less exceeds the above @', the surface area per unit mass becomes large and it is easy to be oxidized. Therefore, when the solder paste is reflowed, the flux of the solder powder is melted. Have an adverse effect. Further, since it is easy to react with the flux, the storage period of the solder paste is shortened and the adhesion is also lowered. In order to reduce the amount of fine particles mixed in the flux powder, the classification point of the flux powder is set to be larger than the target particle size, and at the same time, the air sieving or sieving separation of the flux powder is repeated to mix the fine particles in the flux powder. When the amount becomes below the target level and the powder supply speed is delayed, the fine particles are easily removed, and a wet classification method using a solvent other than water can also be used. The flux powder used in the present invention is a powder having a particle size below the upper limit of the mesh size of the mesh which is sieved and separated, and has a mass distribution of 90 ° /. Above, preferably 95% or more is preferred. Further, the flux powder used in the present invention preferably has a lower oxygen atom content, and if it is 500 ppm or less, more preferably 300 ppm or less, the storage stability and reflow characteristics of the solder paste can be improved. In order to reduce the oxygen atom content in the solder powder, the atomization step of preparing the solder powder is carried out in a gas in which the solder powder is not easily oxidized, and the produced solder powder is operated in an environment which is not easily oxidized. Specifically, the above steps are preferably carried out in an atmosphere in which an inert gas such as nitrogen, argon or ammonia is present or in a vacuum. Welding flux, solder paste, solder wire, soldering liquid flux may also be blended with an active agent, a synthetic resin or a rosin resin component, a solvent, a thixotropic agent, a pH adjuster as needed, and an anti-oxidation agent. Rust, antioxidant, organic acid components, etc. This paper size applies to the national standard (CNS) A4 specification (210X297 mm) -13- (please read the notes on the back and fill in the following: write this page) 1265838 A7 B7 V. Inventions (10) (Please Read the back of the precautions and fill out this page. The flux for welding according to the present invention is characterized in that a hydrocarbon compound containing one or more primary, secondary or tertiary CH bonds and a halogen-containing hydrogen donor compound as an active agent are used. The halogen-containing hydrogen donor compound is a compound containing a halogen, and has a reducing action in a flux for soldering, and is particularly preferably a compound which thermally decomposes at a use temperature of a soldering flux to produce a halogen. Such a compound may, for example, be an organic halogen compound which is thermally decomposed to generate hydrogen halide at the use temperature of the flux for soldering. Conventionally, an ionic substance is often used as an active agent, but an ionic active agent is also active at room temperature. In particular, it has an adverse effect on the storage stability of the lead-free solder which is prone to oxidation. Therefore, it is preferable for the lead-free solder to be decomposed and active during reflow to be active. The addition of an organic halogen compound to a flux is disclosed in, for example, Japanese Patent Publication No. Sho. 5-6-3, 2007, Japanese Patent Publication No. Hei 3-100594, Japanese Patent Publication No. Hei 4-5 9079, and JP-A-8-5 5676 No. Bulletin, etc. The preferred organic halogen compound used in the present invention is printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs, and examples thereof include 1-bromo-2-butanol, 1-bromo-2-propanol, and 3-bromo. -1 -propanol, 3-bromo-1,2-propanediol, 1 '4-dibromo-2-butanol, 1,3 -dibromo-2-propanol, 2,3 -dibromo-1-propenyl Alcohol, 1,4·dibromo-2,3-butanediol, 2,3-dibromo-2-butene-1,4-diol, 1-bromomethyl-1-butene, 1, two Bromobutene, bromo-propene, 2,3-dibromopropene, ethyl bromoacetate, ethyl α-bromooctanoate, ethyl 2-bromopropionate, ethyl cold-bromopropionate, α- Ethyl bromoacetate, 2,3-dibromosuccinic acid, 2-bromosuccinic acid, 2,2-dibromoadipate, 2,4-dibromoethane benzene, ii-dibromotetrachloroethane, 1 , 2-dibromo-1·phenylethane, 1,2-dibromostyrene, 4- 14 - This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 126 5838 A7 B7 V. INSTRUCTIONS (11) Stearoxybenzyloxy, 4-stearyloxybenzyl bromide, 4-stearylbenzyl bromide, 4-bromomethylbenzyl hard Fatty acid ester, 4-stearyl phenylamino phenyl bromo, (please read the back of the note before you fill out this page) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 2 ' 4, bisbromomethyl benzyl Stearate, 4-palmitomethoxybenzyl bromide, 4·gumoxybenzyl bromide, 4-lauryloxybenzyl bromide, 4-undecyloxybenzophenone Base bromine, 9,10,12,13,15,16-hexabromostearic acid '9,10,12,13,1 5,1 6-hexabromo stearate, ethyl ester of the same, 9 , 10,12,1 3 -tetrabromostearic acid, methyl ester of the same substance, ethyl ester of the same substance, 9,10,1 2,1 3,1 5,1 6-hexabromostearyl alcohol, 9,1 0,1 2 '13-tetrabromostearyl alcohol, 1,2,5,6,9,10-hexabromocyclohexadol, bis(2,3-dibromopropyl) succinate, Bis(2,3-dibromopropyl)ophthalate, bis(2,3-dibromopropyl)-p-phthalate, bis(2,3-dibromopropyl). O-phthalate , bis(2,3-dibromopropyl)-p-dimethylguanamine, tris(2,3-dibromopropyl)trimellitic acid ester, tris(2,3-dibromopropyl)-p-phenylene Tridecylamine, tetrakis(2,3-dibromopropyl)-p-benzoic acid ester, tris(2,3-dibromopropyl)-p-tetradecylamine, tetrakis(2,3-dibromopropyl) Benzyltetramethyleneamine, bis(2,3-dibromopropyl)glycerol, trimethylolpropane bis(2,3-dibromopropyl)ether, bis(2,3-dibromopropyl) Tartaramine, N, Ν'-bis(2,3-dibromopropyl) succinylamine, N,N,N,,N'-tetrakis(2,3-dibromopropyl) succinylamine, Ν,Ν'-bis(2,3-dibromopropyl)urea, hydrazine, hydrazine, hydrazine, hydrazine--tetrakis(2,3-dibromopropyl)urea, 2,2-bis[4-(2 ,3-dibromopropyl)-3,5-dibromophenyl]propane, α,α,α-tribromomethyl, α,yS-dibromoethylbenzene, (2,3-dibromopropyl Base) trimeric isocyanate and the like. Among them, the organic halogen compound 9,10,1 2,1 3,15,16-hexabromostearic acid, 9,10,1 2,1 3,1 5,16-hexabromo-hard is especially used.酸酸-15- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1265838 A7 B7 V. Invention description (12) (Please read the note on the back and fill out this page) Methyl ester, same compound Ethyl ester and tris(2,3-dibromopropyl)trimeric isocyanate are preferred. It is preferable that the above-mentioned organic halogen compound is used for the flux for soldering, and it is not preferable that the temperature of the halogen generated by thermal decomposition is close to the temperature of the preheating. Further, an organic halogen compound containing chlorine or iodine instead of bromine may also be used. These organic halogen compounds may be used singly or in combination of two or more kinds. The amount of the organic halogen compound to be added is in the range of 0.02% by mass to 20% by mass based on the total amount of the fluxing flux for the welding, and is preferably in the range of 0.1% by mass to 10% by mass. If the amount of the organic halogen compound added is less than 〇.〇2% by mass, sufficient weldability cannot be obtained at the time of reflow, and if it is more than 20% by mass, it is not uneconomical, and other flux components are reduced to sufficiently satisfy the flux requirement. Other functions. The chlorine meter is a conversion amount expressed by the molecular weight of the bromine of the organic bromine compound converted to chlorine. The ionic bromine-containing active agent is active at a low cost and in a small amount, so that it can be used in an amount which does not impair the stability of the solder paste. In addition, in order to reduce the amount of the expensive organic halogen compound added, the combined use is also effective. The ionic active agent suitable for the addition of other suitable ionic active agents to be printed by the Intellectual Property Office of the Ministry of Economic Affairs may be exemplified by hydrohalic acid amine salts such as isopropylamine hydrobromide, butylamine hydrochloride and cyclohexylamine hydrobromide. 1,1,3-diphenylhydrazine hydrobromide, and the like. Chloride and iodine hydrogen halide salts can also be used instead of bromine. These hydrogen halide salts may be used singly or in combination of two or more kinds, and the compounding amount thereof is in the range of 0.000 to 2 mass%, preferably 0.01% by mass to 1 mass%, based on the total amount of the flux. Inside. If the amount of addition is less than 0.0005 mass%, then there is no -16 - the paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1265838 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 __ B7 _ five, invention (13) The effect of the activity, if the amount is more than 2% by mass, reacts with the active agent contained in the flux to impair the stability of the solder paste. The present invention is preferably a hydrocarbon compound containing one or more primary, secondary or tertiary CH bonds, and is preferably used in a compound which is easily oxidized by reacting with oxygen at about 1 Torr to 15 Torr. Such compounds may be listed, for example, tetrahydronaphthalene, tetraisobutylene, octahydro onion, l-α-naphthyl-1-n-butylhexadecene, 9,10-dihydro-9,10-diisobutyl. Onion, n-octadecylbenzene, n-octadecyltetrahydronaphthalene, polyisobutylene, α-phenyl-2-tetrahydronaphthylbutane, 9,10-diisobutyl perhydroanthracene, 5-iso Butyl naphthalene and the like. The amount of addition is from 质量1% by mass to 20% by mass, preferably from 5% by mass to 5% by mass, based on the total amount of the flux. The effect is not clear, and the hydrocarbon compound containing more than one primary, secondary or tertiary CH bond added to the flux for welding is easily reacted with oxygen at a preheating temperature of about 100 to 150 ° C. While oxidizing, the halogen-containing hydrogen donor compound has a catalyst-promoting effect on the oxidation reaction. In the past, the solder paste was significantly oxidized at a preheating stage of about 150 °C. The solder paste of the present invention contains a hydrocarbon compound containing one or more primary, secondary or tertiary CH bonds, and the hydrocarbon compound of the present invention reacts with oxygen to absorb oxygen at a preheating temperature, and suppresses welding at a preheating temperature. Oxidation of the drug powder. In addition, it is considered that hydrogen halide reduces the surface of the flux by oxidation to improve the solderability. In addition to the solvent, the resin component, and the thixotropic agent, the flux for soldering of the present invention may be added with a rust inhibitor or an antioxidant as needed. , pH adjuster. The solvent to be used in the flux for soldering of the present invention is compatible with the conventional fluxing (please read the following on the back of the page). The paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇X; 297 mm). -17- 1265838 A7 _______ V. Description of invention (14) (Please read the note on the back and fill out this page.) The agent and the solder paste are the same. Alcohols, ethers, esters, and diols can be used. Or a mixture of one or more of an alcohol or an aromatic solvent. For example, benzyl alcohol 'butanol, ethyl cellosolve, butyl cellosolve, butyl carbitol, propylene diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, diethylene glycol hexanoic acid can be used. , propylene glycol monophenyl ether, diethylene glycol monohexyl ether, diethyl alcohol mono-2-ethylhexyl ether, dioctyl phthalate, xylene, 2-methyl-1,3-hexanediol , 2-ethyl-1,3-hexanediol or a mixed solvent of these. The resin component to be blended in the flux for welding of the present invention may be a conventional resin blended with a conventional flux for welding, such as natural rosin, uneven rosin, polymerized rosin, hydrogenated rosin, modified rosin, rosin ester, etc. As the rosin derivative, a synthetic resin, a polyester, a polyurethane, an acrylic resin or the like can be used. The thixotropic agent to be added to improve the printability of the present invention may be an inorganic compound such as fine cerium oxide particles or kaolin particles, or an organic compound such as hydrogenated castor oil or a guanamine compound. The pH adjuster used in the flux for welding of the present invention printed by the Intellectual Property Office of the Ministry of Economic Affairs, P., can be exemplified by alkanolamines, aliphatic first to third amines, aliphatic unsaturated amines. Amine compounds such as cycloaliphatic amines and aromatic amines. These compounds may be used singly or in combination of two or more kinds. The pH of the flux for welding of the present invention is preferably adjusted to a range of 4 to 9, more preferably 6 to 8, because the reaction between the flux powder and the flux can be suppressed. The addition amount of the pH adjuster of the present invention is preferably in the range of 0.05 mass% to 20 mass%, based on the total amount of the flux for soldering. If the addition amount is less than 〇.〇5 mass%, the effect of shell [] pH adjuster is insufficient, and if the addition amount exceeds 20, the paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) -18 - 1265838 A7 B7 , invention description (15) mass%, the solder paste is not easy to absorb moisture. (Please read the precautions on the back and fill out this page.) Specific compounds of such amine compounds may, for example, be ethanolamine, butylamine, aminopropanol, polyoxyethylene oleylamine, polyoxyethylene laurylamine, and Ethylamine, triethylamine, methoxypropylamine, dimethylaminopropylamine, dibutylaminopropylamine, ethylhexylamine, ethoxypropylamine, ethylhexyloxypropylamine, dipropylamine, isopropylamine, diisopropylamine , hexahydropyridine, 2,6-dimethylhexahydropyridine, etc., the flux for welding of the present invention, and an azole as a rust preventive agent, such as benzotriazole or benzimidazole, may be added to the flux. Toluene triazole and the like. The amount of the rust inhibitor added is preferably in the range of 0.05 mass% to .20 mass% with respect to the total amount of the flux. The flux for soldering of the present invention is preferably added with an antioxidant. As the antioxidant, a reducing agent such as a general synthetic resin can be used, and examples thereof include a phenol compound, a phosphate compound, a sulfur compound, a tocopherol, and a derivative thereof, or ascorbic acid and a derivative thereof which are soluble in a solvent. These reducing agents may be used singly or in combination. The compounding amount is in the range of 0.0005 mass% to 20 mass%, preferably 0.01 mass% to 10 mass%, in the total amount of the flux, and the action mechanism of the antioxidants printed by the Ministry of Economic Affairs Intellectual Property Office employees consumption cooperatives It is not very uncomfortable, it may be that these antioxidants are effective for oxygen dissolved in the solder paste or oxygen in the air, and can inhibit oxidation of the metal solder. It is believed that these antioxidants can act as acceptors for halogens which are free from the halogen-containing component, and have the effect of preventing the reaction of the free halogen with the metal flux. The organic acid component can be exemplified by conventionally known succinic acid, phthalic acid, -19-. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1265838 A7 _B7 ____ V. Invention Description (16) (Please Read the precautions on the back and fill out this page. Stearic acid, sebacic acid, etc., can be used as an organic acid derivative which produces a compound of an organic acid at the reflow temperature. The decomposable organic acid ester is low in decomposability at the reflow temperature when used alone, and is also effective in promoting the decomposition by adding a small amount of ester decomposition catalyst. The ester-decomposing catalyst may have a function of promoting the decomposition of the decomposable organic acid ester to produce an acid at the reflow temperature, and particularly, an organic base and a hydrohalide are effective. The organic acid ester may, for example, be various aliphatic carboxylic acid esters, aromatic carboxylic acid esters, aliphatic sulfonic acid esters, aromatic sulfonic acid esters and the like. Specific examples thereof include p-toluenesulfonic acid-n-propyl ester, isopropyl p-toluenesulfonate, isobutyl p-toluenesulfonate, n-butyl p-toluenesulfonate, and n-propyl benzenesulfonate. Isopropylbenzenesulfonate, isobutyl benzenesulfonate, n-propyl salicylate isopropyl salicylate, isobutyl salicylate, n-butyl salicylate, 4-nitrobenzoic acid Isopropyl ester, tert-butyl 4-nitrobenzoate, tert-butyl methacrylate, tributyl acrylate, tert-butyl malonate, tert-butyl bromoacetate, and the like. The amount thereof to be added is preferably from 0.01% by mass to 20% by mass, more preferably from 0.05% by mass to 5% by mass, based on the total amount of the flux. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the consumer consortium of the present invention. The present invention is preferably used as a solder paste by kneading a flux powder and a flux using the above metal solder. In this case, the ratio of the total amount of the flux paste to the flux powder is in the range of 86 to 92% by mass, and the ratio of the flux is preferably in the range of I4 to 8 mass%. The flux paste of the present invention is suitably used for the production of a substrate such as a bonded joint of a printed circuit board and an electronic component. The method for using the flux and the solder paste of the present invention and the method for producing the electronic component joint, for example, applying a solder paste to a portion to be welded by a printing method or the like, and loading the electronic component. (CNS) A4 size (210X297 mm) -20 - 1265838 A7 B7 V. Inventive Note (17) 'Then, the solder particles are melted and solidified, and the electronic components can be bonded to the substrate. (Please read the precautions on the back and fill out this page.) The method of bonding the substrate to the electronic component (packaging method) can be exemplified by surface mount technology (SMT). The package method first coats the solder paste with a printing method. On the substrate, for example, the portion to be soldered on the printed circuit board, and then the electronic components such as the chip component or the QFP are mounted on the solder paste, and the solder heat source is integrally soldered. The heat source for the solder reflow can be a hot air oven, an infrared furnace, or a vapor condensation. Welding device, beam welding device, etc. The reflowing condition of the present invention is preferably carried out in two steps of preheating and reflowing, and the conditions are preheating temperature of 130 to 180 ° C, preferably 130 to 150 ° C, respectively. , preheating time is 60 to 120 seconds, preferably 60 to 90 seconds, reflow temperature is 2 1 0 to 2 30 ° C, preferably 2 1 0 to 2 2 0 ° C, reflow time is 3 0 to 60 seconds, preferably 30 to 40 seconds. The solder paste of the present invention can be subjected to the above-mentioned reflow step in the atmosphere in nitrogen gas. The oxygen concentration during nitrogen reflow is 5% by volume or less. , preferably 〇·5 vol% or less, which can improve the base of the circuit board and the like compared with the atmospheric reflow. The infiltration of the flux is less likely to occur in the case of solder beads. The Ministry of Economic Affairs, the Intellectual Property Office of the Ministry of Economic Affairs, prints and then cools the substrate to complete the surface encapsulation. When manufacturing the electronic component joints by this packaging method, The bonding of the substrate (the bonded board) such as a printed circuit board can be performed. Further, the electronic component of the solder paste of the present invention can be exemplified by an LSI, a resistor, a capacitor, a transistor, an inductor, a filter, and an oscillator. The present invention is formed by adhering to a predetermined surface of the substrate, for example, only by chemical reaction on a predetermined surface of the circuit metal of the printed substrate, and the paper scale is applicable to the Chinese national standard. (CNsTa4 specification (210X297 mm) -21: "" ——' 1265838 A7 B7 V. INSTRUCTIONS (18) After the flux powder is attached thereto, the flux is applied and heated to the flux melting temperature. Welding, in the circuit board formed by the flux (Japanese Unexamined Patent Publication No. Hei 7-7244), the solder paste of the present invention is used for SMT (Surface Mount Technology, Sulface Mounte) d Technique) It has superior solderability when it is packaged. The metal solder and solder paste of the present invention have superior reflow characteristics, weldability, and wettability with the metal to be joined as compared with the conventional one. Or characteristics such as printability, and the number of solder beads generated during reflow is also reduced. In particular, the wettability of the bonded electronic component or circuit substrate is remarkably improved, and the impact resistance of the bonded material is also remarkably improved. Further, according to the present invention, The lead-free solder alloy in which the waste is less polluting to the environment causes the pitch of the electronic components to be finely pitched, for example, corresponding to the micro-pitch of the package circuit board, the diversification of components, or the circuit board which provides superior component life. [Examples] The contents of the present invention will be further described in the following examples, but the present invention is not limited thereto. [Test method] (1) Distribution of the number of fine particles of the flux powder Using a Cruta counter (multiple classifier type II) made of a Colta (share), the lg solder powder was dispersed in l〇〇ml The 1% sodium chloride electrolyte solution was placed in the detector, and the pore diameter of the detection tube was set to 400 A m, and the particle size distribution of the powder of 1 // m or more was measured. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -22 - (Please read the note on the back and fill out this page) • Install. Customs Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1265838 A7 __________ ^_B7_ V. INSTRUCTIONS (19) (2) The oxygen concentration was measured by an oxygen analyzer (infrared analysis method) of Reko Corporation. (Please read the precautions on the back and fill out this page.) (3) Moisture The solder paste is placed in a water vaporization unit (Kyoto Electronics Industry Co., Ltd.: ADP-Wi), heated in iscrc to vaporize, with nitrogen The carrier gas was introduced into a Karl Fischer moisture meter (manufactured by Kyoto Electronics Industry Co., Ltd.: MKC-210) to measure the moisture in the gas. (4) pH 値 In a mixed solution of 50 ml of toluene, 49.5 ml of isopropyl alcohol, and 5 ml of water, 4 g of the flux was dissolved and measured by a pH meter. In the case of a solder paste, the solder paste corresponding to 4 g of flux is approximately measured. (5) Bead test 1 Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, and measured according to JIS Z-3 284. The solder paste was printed on a alumina test plate using a metal cover to form four circular patterns having a diameter of 6.5 mm and a thickness of 0.2 mm. After the test plate was dried at 150 ° C for 1 minute, it was heated to 23 5 ° C to melt the flux, and after melting, the substrate was taken out horizontally within 5 seconds. The flux placed on the substrate was cured horizontally, and then the appearance of the solder was examined with a magnifying glass of 20 times, and the occurrence of the solder particles was examined with a magnifying glass of 50 times. When the occurrence of the bead is less than or equal to the JIS judgment standard of 3, it is considered as a failure (Table 1 is indicated by X). If the judgment criterion is higher than 3, the occurrence status is regarded as good and it is evaluated in three stages of ◎, 〇, and △. (6) Wetting property Measured in accordance with JIS Z-3 284. Use metal cover for copper and brass -23- This paper size is applicable. National Standard (CNS) A4 Specification (210X297 mm) 1265838 A7 B7 V. Invention Description (20) (Please read the notes on the back first. Fill in this page) Print the solder paste on the test board to form four circular patterns with a diameter of 6.5 mm and a thickness of 0.2 mm. After the test plate was dried at 15 ° C for 1 minute, it was heated to 23 5 ° C to melt the flux, and after melting, the substrate was taken out horizontally within 5 seconds. The flux placed on the substrate is cured and the degree of wettability is examined. If the wettability is JIS below the criterion of 3, it is considered as a failure (Table 1 is indicated by X). If the criterion is higher than 3, the invasive condition is considered to be good and evaluated in three stages of ◎, 〇, and △. (7) Impact resistance test Printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs. The impact test (thermal shock test) uses a test substrate of 1.6 m m X 1 0 0 m m x 100 mm. The loading element is an L-QFP that is plated with a 1 hole of Sn-lOPb on a copper wire. The test substrate was subjected to a 1 to 2 micron etching treatment using a copper etching pattern as a soft etching solution (Chen-Chen-Chop-CB-801), followed by a heat-resistant preflux (pre-flux pre-flux R-4Ό3 0). The substrate to be processed. A solder paste was printed on the test substrate using a 150 micron metal cover. After printing, the L_QFP of the plated Sn-Pb is loaded on the substrate. The reflow condition is preheating temperature of 1 60 °C, 90 seconds, peak temperature of 2 2 0 °C, and above 200 °C for 3 〇 seconds. The reflow treatment is assumed to be a test piece for a thermal shock test after two-sided reflow is performed twice. In addition, a 1.5 mm lead wire was placed on the center of the test piece on one side (the surface of the unloaded component), and both ends were fixed by heat-resistant Kapton tape to be forcedly skewed, and the state was thrown into the thermal punching test machine. Inside. The conditions of the thermal shock test were measured at -40 ° C x 30 minutes, +125 ° C x 30 minutes, and the joint strength at 100 cycles, 3 cycles, and 5 cycles was measured. The bonding strength was measured at 45. Each of the 20 wells was measured by the peel strength method. The speed at which the peel strength is measured is 2〇mm/min, which is 4〇-24-. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1265838 A7 _ B7 V. Invention Description (21) Solid microscope Observe the strength and the peeling surface. Observed results, one-hole peeling at the interface between copper and flux was also considered unacceptable (Table 1 indicates X is unacceptable and 〇 indicates qualified). (Please read the precautions on the back and fill out this page.) (8) Wafer lifting test The wafer-winged S-type inspection system uses a test substrate with a thickness of 1.6 mm and a thickness of 100 mm X 100 mm. The loading element (wafer element) was a 1 608 (1.6 mm X O.Smm) Sn-10Pb plating product. The test substrate is subjected to a 1 to 2 micron etching treatment using a copper etching pattern as a soft etching solution (Chen-8), and then subjected to a heat-resistant pre-flux (killing) Flux R-4〇30) substrate treated. A solder paste was printed on the test substrate using a 150 micron metal cover. After printing, one wafer element of the Sn-Pb plated was placed on the substrate. The reflow conditions were a preheating temperature of 1 60 ° C, .90 seconds, a peak temperature of 220 ° C, and a temperature of 200 ° C or more of 30 seconds. When it is completely wafer-free, it is evaluated as 〇, when there is one cocking, it is Λ, and two or more cocking is X. (9) Bead test 2 Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperative of the Ministry of Economics, using a printing cover with five holes of 0.2 m m and a diameter of 6.5 m, the solder paste is printed onto the alumina substrate. Make 9 of these samples. Eight of them were placed in a 90% constant temperature and humidity chamber at 30 ° C, and 8 were taken every 3 hours. These samples were developed on a hot plate set at 23 5 ° C, taken out 5 seconds after the flux was melted, and placed until the flux was cooled. The appearance of the solidified flux was observed with a magnifying glass of 1 ’. According to JISZ-3 2 8 4 (attachment: i), the agglutination state of the flux particles specified in Table 1 and Figure 1 was evaluated. -25- This paper size is applicable to the national standard (CNS) A4 specification (210X297 mm) 1265838 A7 ___B7_____ V. Invention description (22) (Please read the note on the back and fill in this page) When the powder is melted and the flux forms a large ball, it is evaluated as 1 when there is no welding bead, the flux powder is melted and the flux forms a large ball, and there are more than 3 beads with a diameter of 75 // m or less. The evaluation is 2, the flux powder is melted and the flux forms a large ball. When there are more than 3 beads with a diameter of 75 // m or less and are not semi-continuous, the ring is evaluated as 3, and the flux powder is melted. The flux was formed into a large ball, and the number of fine beads surrounded by a semi-continuous ring was evaluated as 4, and the case other than the above was evaluated as 5. (1 〇) void observation on a 60mm square copper plate using a 150 micron metal cover to print 6 solders of 6mm diameter, and then reflowed under the atmosphere, followed by a cutter to cut the solder together with the copper plate, then use a microscope Observe the flux portion to observe the occurrence of voids. When the gap of more than 10 // m or more on the six solders is measured, the average number of voids per one flux is two or more, which is unacceptable. (Examples 1 to 1 and Comparative Examples 1 to 8) Printed by the Ministry of Economic Affairs, the Intellectual Property Office, and the Consumers' Cooperatives. The examples and comparisons of the present invention are as follows. Further, the embodiment of the present invention is not limited to the examples 1 to 11 and the method of manufacturing the electronic component conjugate described. <Production of Flux and Solder Paste> Addition of 7.5% by mass of polymerized rosin as a resin component, 27.5% by mass of uneven rosin, and 6% by mass of hydrogenated castor oil as a thixotropic agent, as a pair of organic esters 5% by mass of n-propyl tosylate, 0.08% by mass of cyclohexylamine hydrobromide as an ester dispersion catalyst, and hexabromo-26 as an organic halogen compound. This paper scale applies to the Chinese National Standard (CNS). Α4 size (210X297 mm) 1265838 A7 B7 V. Invention description (23) (Please read the note on the back and fill out this page) Stearic acid 3.5% by mass or not added, add tocopherol as reducing agent l-Ascorbyl-2'6-dipalmitic acid 1: mass ratio mixture 1. 〇% by mass, 2% by mass of triethylamine as a pH adjuster, 1% by mass of tolutriazole as a rust preventive agent, The flux was prepared by using propylene glycol monophenyl ether as a solvent to become 100% by mass. To the flux 11% by mass, 89 mass was added. /. The flux powder composed of the metal fire dry drug shown in Table 1, the flux powder (25% by particle content of particle size 2 0 // m or less) has a particle size distribution of 20 to 45 / / m The distribution of the metal flux consists of a 3 kg solder paste obtained by mixing with a revolving honing machine. The compounding ingredients are shown in Table 1. The composition of the flux powder used and the pH of the flux were also shown in Table 1. Further, the flux concentration of the flux powder was 300 ppm, and the moisture content in the flux paste was 0.3 mass. /〇. <Manufacturing of Electronic Component Joints> Printing by the Ministry of Economic Affairs, Intellectual Property Office, and Staff Consumer Cooperatives The use of the electronic component joint using the solder paste of the present invention uses SMT. The solder paste of the composition of the fourth embodiment was printed on a circuit board, and the LSI, the chip resistor, and the wafer capacitor were placed on the solder paste, and then heated by a reflow heat source. The heat source was reheated using a hot air furnace. The reflow condition is preheating temperature 130 °C, preheating time is 80 seconds, reflow peak temperature is 22〇°C, and 20 (reflow time above TC is 50 seconds. Printing by comparison with the above measurement method) The characteristics of the board and the solder paste used, the bead test was used, and the results are shown in Table 1. The weld beads of Comparative Examples 1, 2, 3, and 8 were evaluated for a large amount of undissolved flux powder. 27- This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1265838 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (24) (Example 1 2 to 17 7, comparative example 9) <Production of flux and solder paste> Hydrogenated castor oil as a thixotropic agent, homogenized rosin as a resin component, polymerized rosin, cyclohexylamine hydrobromide as an ionic active agent or 1 ' 3 -diphenylhydrazine hydrobromide, benzotriazole as a rust inhibitor, propylene glycol monobutyl ether as a solvent, 9,10,1 2,1 3 ,1 5 as an organic halogen compound ,1 6 -hexabromostearic acid or 9,1 0,1 2,1 3,1 5,16-hexabromostearic acid methyl ester or tris(2) , 3-dibromopropyl)trimeric isocyanate, tripropylamine as an amine component, and n-propyl p-toluenesulfonate as an organic component. In the 10% by mass welding flux, 91Sn/8Zn/lBi is added. 90% by mass of the drug powder was mixed with a revolving honing machine to produce a solder paste. The mixing conditions are shown in Table 2. The evaluation results are shown in Table 3. In addition, the bead test system was used. 2. The use of halogen-containing hydrogen was used. In the examples 1 2 to 17 in which the host compound and the hydrocarbon compound containing one or more primary, secondary or tertiary CH bonds were used as the active agent, both the bead test and the void observation were more remarkable than Comparative Example 9. Solderability. Effect of the Invention By using the solder paste of the metal flux and the flux of the present invention, high wettability and high thermal shock resistance to electronic components can be obtained, and wafer lift-up can be reduced, and soldering can be greatly suppressed. The powder is reacted with the flux to obtain excellent solderability. (Please read the notes on the back and fill out this page)
、1T ▼線 本紙張尺度適用中國國家標準（CNS ) Α4規格（21〇X297公釐） -28- 1265838 A7 _ B7 五、發明説明（25 ) 藉由使用含鹵之氫供予體化合物與含有1個以上一級 、二級或三級CH鍵之烴化合物作爲本發明無鉛焊藥之活性 劑，可提昇焊接性。特別是可減少回焊後產生焊珠並減低 焊藥中之空隙。 藉由開發本發明之焊料糊漿而可提供對應於封裝電路 板微間距化、元件多樣化之電路板之焊接方法、焊接之電 路板、電子元件之接合方法及接合物。 I-----r--------訂-----線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X297公釐） -29 -, 1T ▼ line paper size applicable to China National Standard (CNS) Α 4 specifications (21〇X297 mm) -28- 1265838 A7 _ B7 V. Description of invention (25) by using halogen-containing hydrogen donor compounds and containing A hydrocarbon compound having one or more primary, secondary or tertiary CH bonds can be used as an active agent for the lead-free solder of the present invention to improve weldability. In particular, it reduces the number of weld beads after reflow and reduces the gap in the flux. By developing the solder paste of the present invention, it is possible to provide a soldering method for a board having a fine pitch of a packaged circuit board, a circuit board, a soldering circuit board, a bonding method of an electronic component, and a bonding material. I-----r--------Book-----Line (please read the notes on the back and fill out this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Print this paper scale for China National Standard (CNS) A4 Specification (21〇X297 mm) -29 -