503147 A7 _ B7 _ 五、發明説明（1 ) 蝥領域 (請先閲讀背面之注意事項再填寫本頁) 本發明爲關於電子零件表面裝配中所用之焊膏’更詳 言之，爲關於保存安定性優良之焊膏，及，使用該焊膏之 塗附焊藥之方法，及粘合物。 發明之背景 焊膏爲被使甩於電子產業之電子零件的表面裝配。焊 膏爲因其印刷適性，粘合性故適於自動化，近年其使用量 增大。 於電子產業中，焊膏爲於印刷基板上，以絹網印刷或 以分散器予以塗佈，並且載放電子零件，其次進行逆流， 令電子零件被固定化。此處所謂逆流，係指將載放電子零 _件之基板予以預熱，其後將焊膏於熔解溫度以上加熱並進 行零件粘合的一連串操作。 7 經濟部智慧財產局員工消費合作社印製 另一方面，最近因爲電子製品小型化，故要求精細齒 距化，且精細齒距之零件例如爲使用0 . 3 m m齒距之 Q F P ( Quad Flat Package )類型之 LSI ，且多使用 C S P ( Chip Size Package )等。因此，對於焊膏要求符 合精細齒距之印刷性能。爲了符合此類產業界之要求，乃 將焊藥粒子之平均粒徑降低，但因反而令焊藥粒子全體之 比表面積增大，故促進焊藥粒子與助熔劑之反應，具有使 得焊膏之保存安定性更加惡化之問題點。 令焊膏保存安定性降低的最大原因爲，保存中之焊藥 粉末爲與助熔劑優先反應，進行焊藥粉末的氧化且消耗助 本紙張尺度適用中.國國家標準（CNS)A4規格（210x297公釐）' 503147 A7 B7 五、發明説明（2 ) (請先閲讀背面之注意事項再填寫本頁) 熔劑中的活性劑，令助熔劑之活性度降低，且同時因爲反 應產物而令焊膏之粘度增加。因此，在使用焊膏時，無法 維持適當的印刷特性，加上產生逆流時無法溶解之問題。 以往，爲了提.高焊膏之保存安定性，乃保護焊藥粒子 之表面，並且努力降低粒子金屬的反應性。 例如，揭示以甘油覆蓋焊藥粉末之方法（特公平 5 - 2 6 5 9 8號公報）、將焊藥粉末以對於焊膏溶劑爲 不溶性或難溶性之塗層劑予以塗層之方法（特開平 1 一 1 1 3 1 9 7號公報）。後者塗層劑之適當例可列舉 矽油、聚矽氧基底之高分子量化合物、氟化矽油、氟聚矽 氧樹脂及氟化烴類基底之高分子化合物等。 又，揭示將焊藥粉末，以常溫下與助熔劑不相溶’但 於塗附焊藥之溫度下相溶之以樹脂做爲主體之樹脂予以塗 層之方法（特開平3 - 1 8 4 6 9 8號公報、特7開平 4 — 25 169 1 號公報）。 經濟部智慧財產局員工消費合作社印製 前述方法若以較多量之塗層劑進行塗覆，則可有效抑 制焊藥粉末之氧化，但是多量的塗覆材料不適於焊膏的逆 流，且相反恐發生許多焊藥孔。又，此些塗覆爲僅以物理 性進行，附著爲非常弱，恐於製造焊膏時之混練或使用時 之移送，印刷等之操作中剝離。又，前述以樹脂做爲主體 之樹脂塗層劑本身含有許多反應性之有機酸，故難稱其可 保護粉末。 另外，提案添加酚系、亞磷酸酯系或硫系抗氧化劑做 爲塗附焊藥助熔劑之活性劑之方法（特公昭 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_ 5 _ 503147 Α7 Β7 五、發明説明（3 ) (請先閲讀背面之注意事項再填寫本頁) 59 — 22632號公報、特開平3 — 1 24092號公 報），將分子內容有一個或以上具有第三丁基之苯酚骨架 之抗氧化劑一種或以上添加1〜3 0重量％之方法（特開 平5 - 1 8 5 2 8 3號公報）、或使用特定之界面活性劑 (特開平2 — 1 4 7 1 9 4號公報）等。 又，最近因環境問題，乃推崇不含鉛的無鉛焊膏，並 且進行開發。其中亦以S η — 2 η系之焊膏爲於資源，費 用上爲有利的，且因爲可令逆流溫度降低至與S η - P b 系焊藥同等程度，故使得裝配零件長壽命化，又亦可符合 零件的多樣化，故特別受到注目。但是，S η — Ζ η系之 焊膏爲比通常之P b基底之焊膏的保存安定性更差，且經 由焊藥粉末中之Ζ η氧化之進行和Ζ η與助熔劑之反應， ，使得歷時的粘度上升。特別以Ζ η於常溫與助熔劑中之鹵 素化合物反應，且令焊膏之保存安定性惡化。女，助熔劑 中之鹵化合物、與焊藥粉末中之Ζ η反應並發生微量之氫 氣，且所發生之氫氣於零件接合後亦被內藏於焊藥平緣內 ，故對於信賴性造成重大之影響。 經濟部智慧財產局員工消費合作社印製 發明之摘要 本發明爲鑑於上述之問題點，以提供保存安定性優良 之焊膏，且再經由使用此焊膏，提供信賴性高之塗附焊藥 之方法，及接合物爲其目的。 發明者等人爲了解決上述課題而致力努力檢討，結果 達成本發明。即，本發明爲關於 Λ! t in ( CNS ) Α4ΜΛ ( 210 X 297^^-) — 503147 Α7 Β7 五、發明説明（4 ) (請先閲讀背面之注意事項再填寫本頁) 〔1〕一種焊膏，其特徵爲於含有鹵素化合物之焊膏 中’助熔劑每1克之鹵離子濃度以氯換算値爲3 0 0 0 P P m以下， 〔2〕如〔1〕記載之焊膏，其中鹵離子爲溴離子， 〔3〕如〔1〕或〔2〕記載之焊膏，其中焊膏爲含 有Ζ η做爲焊藥粉末， 〔4〕一種電路板之塗附择藥方法，其特徵爲包含將 〔1〕或〔2〕記載之焊膏，於電路板上塗佈之工程，及 將該焊膏予以逆流之工程， 〔5〕一種電路板之塗附焊藥方法，其特徵爲包含將 含有Ζ η做爲焊藥粉末之〔1〕或〔2〕記載之焊膏，於 電路板上塗佈之工程，及將該焊膏予以逆流之工程， 〔6·〕一種粘合物，其爲經由包含將〔1〕或〔2〕 記載之焊膏於電路板上塗佈之工程，及將該焊鲁予以逆流 之工程之電路板塗附焊藥方法所製造之粘合物， 經濟部智慧財產局員工消費合作社印製 〔7〕一種粘合物，其爲經由包含將含有Ζ η做爲焊 藥粉末之〔1〕或〔2〕記載之焊膏於電路板上塗佈之工 程，及將該焊膏予以逆流之工程之電路板塗附焊藥方法所 製造之粘合物。 發明之詳細記述 焊膏中所含的助熔劑爲配合松脂或合金樹脂系之樹脂 成分，做爲活性劑之鹵素化合物和/或有機酸成分、溶劑 、觸變劑等。此些成分中’逆流時除去焊藥金屬之表面氧 本紙張尺度適用中.國國家標準（CNS ) Α4規格（210Χ297公釐.） ^03147 A7 B7 五、發明説明（5 ) (請先閱讀背面之注意事項再填寫本頁) ft牧/並且取得良好結合之有效成份爲使用做爲活性劑之鹵 ^化合物和/或有機酸成分。此些活性劑可提高表面氧化 物之除去能去，但做爲焊膏時，或保存中，與焊藥粉末反 g且令焊膏惡化。特別以鹵素化合物做爲活性劑之效果高 ’但卻令焊膏惡化之影響變強。 本發明者對於焊膏中之焊藥粉末與活性劑之反應進行 檢討’結果發現令焊膏之助熔劑每1克中之鹵離子濃度以 氯換算値爲3〇0 0 p pm以下，較佳爲1 〇 〇 〇 p pm 以下，更佳爲5 0 0 p p m以下，最佳爲3 0 0 p p m以 下，則可抑制焊藥粉末與活性劑之反應，並防止焊膏之惡 化，且可能提高保存安定性。 鹵離子對於焊膏之保存安定性造成不良影響之理由雖 然未明，·但認爲係因在鹵離子存在下，令助熔劑中添加之 鹵素、匕合物的氧化力增強，並且促進與焊藥金屬7之反應。 經濟部智慧財產局員工消費合作社印製 鹵離子濃度之氯換算値爲秤量焊膏，將有機溶劑-水 系萃取時之水層中所含之鹵離子濃度，以離子層析予以定 量，再換算氯並且由換算成助熔劑每1克之値而求出。所 謂氯換算値爲指將含鹵離子換算成氯離子時之値。例如， 於活性劑使用溴化合物時，若將焊膏中之溴離子定量値（ vg/g)乘以35·453/79·904(氯原子量 /溴原子量）値即可。又，於活性劑使用碘化合物時，若 將該離子定量値（# g / g )乘以3 5 · 4 5 3 / 126.9045 (氯原子量/溴原子量）値即可。 此處，萃取中所用之有機溶劑若爲不與助熔劑反應， 本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐）-8 - 503147 A7 B7__ 五、發明説明（6 ) 於有機合成等所使用之先前習知之於水中不可溶之不含鹵 ' \ (請先閱讀背面之注意事項再填寫本頁) 離子之溶劑即可，.可列舉例如氯仿、二氯甲烷、甲苯、二 甲苯、苯、二乙醚、石油醚等。由助熔劑之溶解性、萃取 操作之容易度等而言，則以氯仿、甲苯、二甲苯、二乙醚 、石油醚爲適於使用。萃取中所使用之水若爲不含有鹵離 子即可，且例如以超純水爲最適使用。尙，以有機溶劑-水萃取測定鹵離子濃度，亦可於使用水溶性助熔劑、非水 溶性助熔劑任一種之焊膏中實施。 本發明爲令焊膏，於焊膏之助熔劑中之鹵離子濃度以 氯換算値爲.3 0 0 0 P P m以下。例如’適合使用做爲活 性劑之有機鹼鹵化氫酸鹽之異丙胺氫溴酸鹽、丁基胺氫氯 酸鹽、和環己胺氫溴酸鹽等之鹵化氫酸胺鹽、1 ，3 —二 .苯基胍氫溴酸鹽等之情況，則此些化合物中所含之鹵素爲 全量之鹵離子。因此，其添加量在不倂用其他齒素化合物 之情況中，則鹵離子之氯換算値爲3 0 0 0 p p m以下計 算添加即可。 經濟部智慧財產局員工消費合作社印製 鹵素化合物若爲通常使用做爲焊藥用助熔劑之鹵素化 合物即可，但爲了更加改良焊膏之焊藥塗附性、濕潤性， 則以焊膏保存中可以鹵素化合物型式安定存在，且逆流溫 度下，可分解發揮活性力之鹵素化合物，特別爲有機溴化 合物其鹵離子之氯換算値爲3 0 0.0 p pm以下爲較佳使 用。 若列舉具有此類性能之有機溴化合物之一例，則可舉 出具有碳數1 〇個以上烷基取代基之苯基溴化合物、或於 本紙張尺度適用中.國國家標準（CNS ) A4規格（210X29：7公釐）7〇7~ 一 503147 A7 B7 五、發明説明（7 ) 碳數1 0個以上之脂肪酸或脂環式化合物之一分子中含有 4個以上溴之多溴北合物，且其亦可混合使用。 (請先閲讀背面之注意事項再填寫本頁) 具有碳數1 0個以上烷基鏈之苄基溴化合物具體可列 舉例如4 -硬脂醯氧基苄基溴、4 -硬脂氧基苄基溴、4 -硬脂基苄基溴、4 -溴甲基苄基硬脂酸酯、4 -硬脂醯 胺基苄基溴、2，4 -雙溴甲基苄基硬脂酸酯等之化合物 。其他亦可列舉4-棕櫚醯氧墓苄基溴、4-肉豆蔻醯氧 基苄基溴、4 -月桂醯氧基苄基溴、4 -十一烷醯氧基苄 基溴等。 又，多溴化合物例如爲具有羧基、醯基、醇基、醚基 、酮基等，且結合4個以上之溴原子之化合物。 此些化合物之具體例可列舉9，1 0，1 2，1 3， .1 5 ，1 6 —六溴硬脂酸、9 ，1 〇，1 2 ，1 3 ，1 5 ，1 6 —六溴硬脂酸甲酯，同乙酮、9，1 0，71 2， 1 3 —四溴硬酯酸、同甲酯、同乙酯、9 ，1 0 ，1 2 ’ 1 3，1 5，1 6 —六溴硬脂醇、9，1 0，1 2，1 3 —四溴硬脂醇、1 ，2，5，6，9 ，1 0 —六溴環十二 經濟部智慧財產局員工消費合作社印製 烷等。特別以六溴硬脂酸、六溴環十二烷爲佳。 又，上述以外，若再例示有機溴化合物則可列舉1 一 溴—2 — 丁醇、1—溴—2 -丙醇、3 -溴—1 一丙醇、 .3 —溴—1，2 —丙二醇、1，4 一 二溴一 2 - 丁醇、1 ，3 —二溴一2 —丙醇、2 ，3 —二溴一1 —丙醇、1 ’ 4 —二溴、2，3 — 丁 二醇、2，3 —二溴—2 - 丁烯一 1 ，4 —二醇、1—溴一3 —甲基一1— 丁烯、1，4一 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐.） .>|〇 . 503147 ΑΊ B7 五、發明説明（8 ) (請先閲讀背面之注意事項再填寫本頁) 二溴丁烯、1 —溴一 1 一丙烯、2，3 —二溴丙烯、溴醋 酸乙酯、α -溴辛酸乙酯、α -溴丙酸乙酯、0 —溴丙酸 乙酯、α —溴—醋酸乙酯、2 ，3 —二溴琥珀酸、2 -溴 琥珀酸、2，2 —溴己二酸、2 ，4 —二溴乙醯苯、1 ， 1 —二溴四氯乙烷、1 ，2 —二溴—1 —苯基乙烷、1 ， 2 -二溴苯乙烯等之溴化物，但並非限定於此些例示。又 ，亦可使用含有氯、碘代替溴乏有機鹵素化合物。 此些鹵素化合物之添加量，爲令焊膏中之鹵離子爲助 熔劑每1克之氯換算値爲3 0 0 0 p p m以下。又，鹵素 化合物可添加一種或以上，且亦可倂用有機鹵素化合物和 有機鹼之鹵化氫酸鹽。 本發明中之有機酸成分可列舉先前習知的琥珀酸、酞 酸、硬脂酸、癸二酸等，且以到達逆流溫度時發生有機酸 之化合物有機酸衍生物爲適於使用。其例可列每各種脂族 羧酸酯、芳香族羧酸酯、脂族磺酸酯、芳香族磺酸酯等。 經濟部智慧財產局員工消費合作社印製 此些酯之醇殘基爲烷基、烯丙基，特別以酯分解性高 之第三丁基、異丙基、異丁基爲佳，又，此些化合物亦可 含有鹵原子。 具體例可列舉對甲苯磺酸正丙酯、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、溴醋酸第三丁酯等 本紙張尺度適用中周國家摞準（CNS ) A4規格（210X297公釐）-11 - 503147 A7 B7 五、發明説明（9 ) (請先閲讀背面之注意事項再填寫本頁} 。其中特別以對甲苯磺酸正丙酯、水楊酸異丁酯、溴醋酸 第三丁酯爲特佳。添加量相對於助熔劑全量使用0 · 0 1 〜20質量％，較佳爲〇·05〜5質量％之範圍。 上述之分解性有機酸酯因爲單獨於逆流溫度中之分解 性亦低，故爲了促進分解，其有效爲添加少量之酯分解觸 媒。酯分解觸媒若爲分解性之有機酸酯爲在逆流溫度下分 解，並且具有促進酸發生作用之觸媒即可，且其中特別以 有機鹼之鹵化氫酸鹽爲有效。 本發明之焊膏中所配合之樹脂成分，可使用先前助熔 劑中所配合.之習知樹脂，例如，天然松脂、不均化松脂、 聚合松脂、改質松脂等，且合成樹脂可使用聚酯、聚胺基 甲酸酯、丙烯酸系樹脂。 溶劑可利用與先前之助熔劑和焊膏同樣之醇類、醚類 、酯類、或芳香族系之溶劑，例如苄醇、丁醇I乙基溶纖 劑、可基溶纖劑、丁基卡必醇、二甘醇己醚、丙二醇單苯 醚、酞酸二辛酯、二甲苯等一種或混合使用。 經濟部智慧財產局員工消費合作社印製 又，爲了改善印刷性所添加之觸變劑可使用微細之矽 石粒子、高嶺土粒子等之無機系物質、或氫化篦麻油、醯 胺化合物等之有機系物質。 本發明之焊膏中，在倂用還原劑做爲安定劑下，可令 保存安定性更加提筒。 上述還原劑可使用通常樹脂等之抗氧化劑，可列舉可~ 於溶劑中溶解之苯酚系化合物、磷系化合物、硫系化合物 、生育酚及其衍生物、L 一抗壞血酸及其衍生物等。 本紙張尺度適用中.國國家標準（CNS ) A4規格（210x297公釐）-12 - A7 B7 五、發明説明（10 ) 具體而言，苯酚系化合物可列舉氫醌、兒茶酚、2， 6〜二〜第三丁基—對—甲酚、丁基羥基茴香醚、2， 2 >〜亞甲基雙（4 —甲基一 6 —第三丁基苯酚）等。 磷系化合物可列舉亞磷酸三苯酯、亞磷酸三（十八烷 酷）、亞磷酸十三烷酯等。 又，硫系化合物可列舉二月桂基一 3，3 / —硫基二 丙酸酯、二硬脂基—3，3 >二硫基二丙酸酯、二肉蔻基 〜3，3 '—硫基二丙酸酸等。. 生育酚及其衍生物，L -抗壞血酸及其衍生物若爲具 有還原性，且對於溶劑可溶之化合物，例如其酯類均可使 用。特別於倂用生育酚或其衍生物及L -抗壞血酸或其衍 生物二種時，可取得好結果。配合比爲重量〇 · 5 : 1〜 • 1 : 0 · 5，特佳爲約1對1爲佳。 L -抗壞血酸衍生物之具體例可列舉抗壞血酸- 2 -磷酸、.抗壞血酸一 2 -硫酸、抗壞血酸一 2 -糖苷、抗壞 '血酸一 2，6 —二丁酸酯、抗壞血酸—2，6 —二硬脂酸 酯、抗壞血酸—2，6 —二肉豆蔻酸酯、抗壞血酸—6 — 棕櫚酸酯、.抗壞血酸- 6 -硬脂酸酯、抗壞血酸一 6 -肉 豆蔻酸酯、抗壞血酸一 2，3，5，6 —四棕櫚酸酯、抗 壞血酸一 2，3，5，6 —四肉豆蔻酸酯、抗壞血酸一 2 ，3 ，5 ，6 —四硬脂酸醋、抗壞血酸一 2 —糖脊一 6 — 棕櫚酸酯、抗壞血酸- 2 -糖苷一 6 -肉豆蔻酸酯、抗壞 血酸一 2 -糖苷一 6 -硬脂酸酯、抗壞血酸—5，6 —亞 苄基、抗壞血酸一 5，6 -亞丙基、抗壞血酸一 2 —磷酸 、 _____ -本紙張尺度適用中.國國家標準（CNS ) A4規格(210 x297公釐.)~3 - ——,丨丨.—— (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 503147 A7 ____ _ B7 五、發明説明（11 ) —5 ’ 6 —亞苄基、抗壞血酸一 2 -磷酸—5，6 —亞丙 (請先閲讀背面之注意事項再填寫本頁) 基等’生育酚衍生物之具體例可列舉生育酚、醋酸生育酚 、磷酸生育酚、山梨酸生育酚、菸鹼酸生育酚酯等。 此些還原劑可單獨或混合使用。還原劑之添加量若爲 可充分確保焊膏保存安定性之份量即可，一般相對於助熔 劑全量爲〇 · 005質量％以上20質量％以下。添加量 若過少則安定化效果無，而即便添加2 0質量％以上亦未 察見配合高濃度添加所造成之效果提高，故爲不佳。 本發明之焊膏中所用之助熔劑，例如相對於助熔劑全 量，使用2.0〜26質量％之樹脂成分、0·04〜20 質量％之觸變劑、0.01〜20質量％之有機酸成分， 滿足上述鹵離子範圍之鹵素化合物，0 . 0 0 5〜2 0質 .量％之還原劑及做爲殘餘部分之溶劑。將此助熔劑，例如 相對於焊膏全量將1 4〜8質量％，與焊藥粉末τ8 6〜 9 2質量％混練作成本發明之焊膏。此時之鹵化物添加量 •必須令焊膏混練後之助熔劑中之鹵離子濃度以氯換算値爲 300ppm以下。 經濟部智慧財產局員工消費合作社印製 於配合物之調合，混練中’調節助熔劑等之水分’氛 圍氣之濕氣，令焊膏中之水分含量爲0 · 5質量％以下’ 更佳爲0 · 3質量％以下爲佳。焊膏中之水分若混入多於 0 · .5質量％ ’則促進鹵化物之解離’且此解離之鹵素爲 與焊藥合金粉末反應，故爲不佳。又’焊膏之p H値亦較 佳爲4〜9，更佳爲6〜8之範圍，可抑制焊藥粉與助熔 劑之反應爲佳。此時’ P H調整劑較佳使用院醇胺類'、脂 本紙張尺度適用中.國國家標準（CNS)A4規格（210x297公资]"14~~: 503147 A7 __ B7 五、發明説明（12 ) 族第一〜第三胺類、脂肪不飽和胺類、脂環式胺類、芳香 族胺類等之胺化合物。 此些胺化合物之具體化合物可列舉乙醇胺、丁胺、胺 基丙醇、聚氧乙烯油胺、聚氧乙烯月桂胺、聚氧乙烯硬脂 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、乙基乙氧基丙胺、雙 丙胺、異丙胺、二異丙胺等。' 胺化合物之使用量相對於焊膏之助熔劑全量，以 〇 · 〇 5〜2 0質量％爲佳。未滿〇 · 0 5質量％則做爲 P Η調節劑之效果不夠充分，若超過2 0質量％則一般令 Ρ Η超過9，移行至鹼側且令焊膏易吸濕。 更且，爲了令電路之銅防銹，可於助熔劑中添加吡咯 類，例如苯並三唑、苯並咪唑、甲苯基三唑等。防銹劑之 添加量相對於助熔劑全量以0 · 0 5〜2 0質量τ%爲佳。 本發明之焊膏中所使用之焊藥粉末可爲先前習知之金 屬組成物質，且以含有易氧化之Ζ η之焊藥粉末爲適於使 用。可列舉例如S η、Ζ η系、S η — A g — Ζ η系、 (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 B- n s A I n s B I n s 系 n z- b .系 η ζ i u c 系 n z I b s n503147 A7 _ B7 _ V. Description of the invention (1) 蝥 Field (please read the precautions on the back before filling out this page) The present invention is about solder paste used in the surface assembly of electronic parts. More specifically, it is about storage stability Excellent solder paste, method for applying flux using the solder paste, and adhesive. BACKGROUND OF THE INVENTION Solder paste is a surface mount of electronic parts that have been dumped in the electronics industry. Solder paste is suitable for automation because of its printability and adhesion, and its use has increased in recent years. In the electronics industry, solder paste is printed on a printed circuit board by silk screen printing or coated with a disperser, and the electronic parts are placed, followed by countercurrent, so that the electronic parts are fixed. The so-called backflow here refers to a series of operations in which the substrate on which the electronic parts are placed is preheated, and then the solder paste is heated above the melting temperature and the parts are bonded. 7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs On the other hand, recently, due to the miniaturization of electronic products, fine pitches are required, and parts with fine pitches are, for example, QFP (Quad Flat Package) with a pitch of 0.3 mm. ) Type LSI, and more often use CSP (Chip Size Package). Therefore, the solder paste is required to meet the printing performance of fine pitch. In order to meet the requirements of this industry, the average particle diameter of the flux particles is reduced, but the specific surface area of the entire flux particles is increased, so the reaction between the flux particles and the flux is promoted, which has the effect of making the solder paste Keep the problem of deteriorating stability. The biggest reason to reduce the stability of solder paste storage is that the flux powder during storage is preferentially reacted with the flux, which oxidizes the flux powder and consumes the paper. The national paper standard (CNS) A4 (210x297) (Mm) '503147 A7 B7 V. Description of the invention (2) (Please read the notes on the back before filling this page) The active agent in the flux reduces the activity of the flux, and at the same time, the solder paste is caused by the reaction product. The viscosity increases. Therefore, when the solder paste is used, proper printing characteristics cannot be maintained, and there is a problem that it cannot be dissolved when a counter current is generated. In the past, in order to improve the storage stability of the solder paste, the surface of the solder particles was protected, and efforts were made to reduce the reactivity of the particulate metal. For example, a method of coating a flux powder with glycerin (Japanese Unexamined Patent Publication No. 5-2 6 5 98) is disclosed, and a method of coating a flux powder with a coating agent that is insoluble or hardly soluble in a solder paste solvent (specially Kaiping 1-1 1 3 1 9 7). Suitable examples of the latter coating agent include silicone oils, high molecular weight compounds of polysiloxy base, fluorinated silicone oils, fluoropolysiloxane resins, and polymer compounds based on fluorinated hydrocarbons. Also disclosed is a method of coating a flux powder with a resin as the main body that is incompatible with the flux at normal temperature but is compatible with the temperature at which the flux is applied (Japanese Patent Application Laid-Open No. 3-1 8 4 No. 6 9 No. 8 and No. 7 Kaihei 4 — 25 169 No. 1). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs if the above method is applied with a larger amount of coating agent, it can effectively inhibit the oxidation of the solder powder, but a large amount of coating material is not suitable for the backflow of the solder paste, and the contrary may Many flux holes occur. In addition, these coatings are performed only physically, and the adhesion is very weak, so that they may be peeled during operations such as kneading during solder paste production, transfer during use, and printing. In addition, since the resin coating agent mainly composed of the resin itself contains many reactive organic acids, it is difficult to say that it can protect the powder. In addition, it is proposed to add phenol-based, phosphite-based or sulfur-based antioxidants as an active agent for coating flux (special paper size of this paper applies Chinese National Standard (CNS) A4 specification (210X297 mm) _ 5 _ 503147 Α7 Β7 V. Description of the invention (3) (Please read the precautions on the back before filling out this page) 59-22632, JP-A-H3-1 24092), one or more of the molecular contents have the first Tributyl phenol skeleton antioxidant One or more methods of adding 1 to 30% by weight (Japanese Patent Laid-Open No. 5-1 8 5 2 8 3), or using a specific surfactant (Japanese Patent Laid-open No. 2 — 1 4) 7 1 9 4) and so on. Recently, due to environmental problems, lead-free solder paste has been promoted and developed. Among them, S η-2 η-based solder paste is also a resource and cost-effective, and because the countercurrent temperature can be reduced to the same level as that of S η-P b -based solder, the assembly parts have a longer life. It can also meet the diversification of parts, so it attracts special attention. However, S η — Z η-based solder pastes are less stable than ordinary P b-based solder pastes, and undergo the oxidation of Z η in the flux powder and the reaction of Z η with the flux, Makes the viscosity increase over time. Especially, Z η reacts with the halogen compound in the flux at normal temperature, and deteriorates the storage stability of the solder paste. Female, the halogen compound in the flux reacts with Z η in the flux powder and generates a small amount of hydrogen, and the generated hydrogen is also built into the flat edge of the flux after the parts are joined, so it has a great impact on reliability. Influence. Abstract of the Invention Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The present invention is to provide a solder paste with excellent storage stability in view of the above-mentioned problems, and then use this solder paste to provide a highly reliable coated solder paste. Methods, and conjugates for this purpose. The inventors and others worked hard to solve the above-mentioned problems, and as a result, they achieved the invention. That is, the present invention is about Λ! T in (CNS) Α4ΜΛ (210 X 297 ^^-) — 503147 Α7 Β7 V. Description of the invention (4) (Please read the precautions on the back before filling this page) 〔1〕 One The solder paste is characterized in that the concentration of halogen ions per 1 gram of the flux in the solder paste containing halogen compounds is less than 3 0 0 PP m in terms of chlorine, and [2] The solder paste according to [1], wherein The ions are bromide ions. [3] The solder paste as described in [1] or [2], wherein the solder paste contains Z η as a flux powder, [4] a method for selecting and applying a circuit board, which is characterized by: Including the process of coating the solder paste described in [1] or [2] on a circuit board, and the process of counter-flowing the solder paste, [5] a method of applying solder flux to a circuit board, which is characterized by including [1] or [2], a process of applying solder paste described in [1] or [2] containing solder powder as a flux powder on a circuit board, and a process of counterflowing the solder paste, [6 ·] an adhesive, This is a process including applying the solder paste described in [1] or [2] on a circuit board, and countercurrently applying the solder paste. Adhesives produced by the method of applying soldering flux to printed circuit boards of the project are printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [7] A kind of adhesives, which are prepared by containing Zn as a flux powder [1] The process of applying the solder paste described in [] or [2] to a circuit board, and the adhesive produced by the method of applying a solder paste to a circuit board of a process in which the solder paste is reversed. Detailed description of the invention The flux contained in the solder paste is a halogen compound and / or an organic acid component, a solvent, a thixotropic agent, etc., which are blended with a resin component of rosin or an alloy resin type as an active agent. Among these ingredients, the surface oxygen of the flux metal is removed when countercurrent. The paper size is applicable. National Standard (CNS) A4 (210 × 297 mm.) ^ 03147 A7 B7 V. Description of the invention (5) (Please read the back first (Please note this page and fill in this page again). The effective ingredients for good combination are halogen compounds and / or organic acid ingredients used as active agents. These active agents can improve the removal ability of surface oxides, but when used as a solder paste, or during storage, they will react with the flux powder and worsen the solder paste. In particular, the effect of using a halogen compound as an active agent is high, but the effect of worsening the solder paste becomes stronger. The inventor reviewed the reaction between the flux powder and the active agent in the solder paste, and found that the halide ion concentration per gram of the flux of the solder paste is 3,000 or less in terms of chlorine, which is better. Below 1000 ppm, more preferably below 500 ppm, and most preferably below 300 ppm, the reaction between the flux powder and the active agent can be suppressed, the deterioration of the solder paste can be prevented, and the preservation can be improved. Stability. Although the reason why the halide ions adversely affect the storage stability of the solder paste is unknown, it is believed that the presence of the halide ions enhances the oxidizing power of the halogens and dagger compounds added to the flux, and promotes the flux Reaction of metal 7. The chloride conversion of the halide ion concentration printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is measured as a solder paste for weighing. The halide ion concentration in the water layer during organic solvent-water extraction is quantified by ion chromatography, and then converted into chlorine. And it is calculated | required by converting it into 1 g of flux per gram. The term "chlorine-converted plutonium" refers to plutonium when halogen-containing ions are converted into chloride ions. For example, when using a bromine compound as an active agent, multiply the quantitative bromine ion (vg / g) in the solder paste by 35 · 453/79 · 904 (chlorine atom weight / bromine atom weight) 値. When an iodine compound is used as the active agent, it is sufficient to multiply the ion quantitative osmium (# g / g) by 3 5 · 4 5 3 / 126.9045 (chlorine atom weight / bromine atom weight) 値. Here, if the organic solvent used in the extraction does not react with the flux, the paper size applies the Chinese national standard (CNS> A4 specification (210X297 mm) -8-503147 A7 B7__ V. Description of the invention (6) in organic synthesis The previously used halogen-insoluble in water, which is previously known, '(Please read the precautions on the back before filling in this page) Ionic solvents. For example, chloroform, dichloromethane, toluene, xylene , Benzene, diethyl ether, petroleum ether, etc. In terms of solubility of the flux, ease of extraction operation, etc., chloroform, toluene, xylene, diethyl ether, petroleum ether are suitable for use. Used in extraction Water is not required as long as it does not contain halide ions, and ultrapure water is the most suitable. For example, the concentration of halide ions can be determined by organic solvent-water extraction. It can also be used with any of water-soluble fluxes and non-water-soluble fluxes. The invention is implemented in soldering paste. The present invention is to make the soldering paste, and the halogen ion concentration in the flux of the soldering paste is less than .3 0 0 0 PP m in terms of chlorine. For example, 'suitable for use as an organic base hydrogen halide Salt difference In the case of amine hydrobromide, butylamine hydrochloride, cyclohexylamine hydrobromide, etc., amine hydrohalide amine salts, 1,3-di.phenylguanidine hydrobromide, etc. The halogen contained in the compound is the full amount of halogen ions. Therefore, if the addition amount is not in the case of using other dentin compounds, the chloride conversion of the halogen ions is less than 3 000 ppm and calculated and added. If the halogen compound printed by the Intellectual Property Bureau ’s consumer cooperative is a halogen compound commonly used as a soldering flux, it can be stored in solder paste in order to improve the solder paste applicability and wettability of the solder paste. Types of halogen compounds exist stably, and halogen compounds that can decompose and exert their activity at countercurrent temperature, especially organic bromine compounds, have a chlorine ion conversion of halogen ions of less than 3 0 0.0 p pm. It is preferred to use such properties. An example of an organic bromine compound is a phenyl bromide compound having a carbon number of 10 or more alkyl substituents, or in the application of this paper. National Standard (CNS) A4 specification (210X29: 7 mm) ) 7 7 ~ a 503147 A7 B7 V. Description of the invention (7) One of fatty acids or alicyclic compounds with more than 10 carbon atoms has a polybrominated northern compound containing more than 4 bromines in the molecule, and it can also be used in combination. (Please read the notes on the back before filling out this page.) Specific examples of benzyl bromide compounds with an alkyl chain of 10 or more carbons include 4-stearyloxybenzyl bromide and 4-stearyloxybenzyl. Bromine, 4-stearylbenzyl bromide, 4-bromomethylbenzyl stearate, 4-stearylamine benzyl bromide, 2,4-bisbromomethylbenzyl stearate, etc. Other compounds include 4-palmitoylbenzyl bromide, 4-myristyloxybenzyl bromide, 4-laurylpyroxybenzyl bromide, and 4-undecanepyroxybenzyl bromide. The polybromine compound is, for example, a compound having a carboxyl group, a fluorenyl group, an alcohol group, an ether group, a ketone group, and the like, and having four or more bromine atoms bonded thereto. Specific examples of these compounds include 9,10,1,2,1,3,1,5,16-hexabromostearic acid, 9,1,0,1,2,1,3,1,5,16--6 Methyl bromostearate, same as ethyl ketone, 9,1 0,71 2,1 3 -tetrabromostearic acid, same methyl ester, same ethyl ester, 9,1 0,1 2 '1 3,1 5, 1 6 —hexabromostearyl alcohol, 9,1 0,1 2,1 3 —tetrabromostearyl alcohol, 1,2,5,6,9,1 0 —hexabromocyclo twelve employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer cooperatives produce alkanes, etc. Particularly preferred are hexabromostearic acid and hexabromocyclododecane. In addition to the above, if the organic bromine compound is further exemplified, 1-bromo-2-butanol, 1-bromo-2-propanol, 3-bromo-1 monopropanol, .3-bromo-1, 2— Propylene glycol, 1,4-dibromo-2 -butanol, 1,3-dibromo-2 -propanol, 2,3-dibromo-1 -propanol, 1 '4-dibromo, 2,3-butane Diol, 2,3-dibromo-2-butene-1, 4-diol, 1-bromo-3-methyl-1-butene, 1, 4-This paper size applies Chinese National Standards (CNS) A4 specifications (210X297 mm.). ≫ | 〇. 503147 ΑΊ B7 V. Description of the invention (8) (Please read the precautions on the back before filling this page) Dibromobutene, 1-bromo-1, 1-propylene, 2,3-dibromopropene, ethyl bromoacetate, ethyl a-bromocaprylate, ethyl a-bromopropionate, ethyl 0-bromopropionate, α-bromo-ethyl acetate, 2,3-dibromo Succinic acid, 2-bromosuccinic acid, 2,2-bromoadipic acid, 2,4-dibromoacetophenone, 1,1-dibromotetrachloroethane, 1,2-dibromo-1-phenyl Bromides such as ethane, 1,2-dibromostyrene, but not limited to These exemplified. Alternatively, a bromine-depleted organic halogen compound containing chlorine and iodine may be used instead. The addition amount of these halogen compounds is to make the halogen ions in the solder paste into the flux, which is less than 3 0 0 p p m in terms of chlorine per 1 g of the flux. Further, one or more halogen compounds may be added, and an organic halogen compound and an organic base halide may be used. Examples of the organic acid component in the present invention include conventionally known succinic acid, phthalic acid, stearic acid, sebacic acid, and the like. Among them, an organic acid derivative which is a compound that generates an organic acid when reaching a countercurrent temperature is suitable for use. Examples thereof include each of various aliphatic carboxylic acid esters, aromatic carboxylic acid esters, aliphatic sulfonic acid esters, and aromatic sulfonic acid esters. The alcohol residues printed by the employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs of these esters are alkyl and allyl groups, especially tertiary butyl, isopropyl, and isobutyl groups with high ester decomposition properties are preferred. These compounds may also contain a halogen atom. Specific examples include n-propyl p-toluenesulfonate, isopropyl p-toluenesulfonate, isobutyl p-toluenesulfonate, n-butyl p-toluenesulfonate, n-propyl besylate, isopropyl benzenesulfonate, Isobutyl besylate, n-propyl salicylate, isopropyl salicylate, isobutyl salicylate, n-butyl salicylate, isopropyl 4-nitrobenzoate, 4-nitrobenzene Tertiary butyl formate, tertiary butyl methacrylate, tertiary butyl acrylate, tertiary butyl malonate, tertiary butyl bromoacetate, etc. This paper is applicable to the CNS A4 specification ( 210X297mm) -11-503147 A7 B7 V. Description of the invention (9) (Please read the notes on the back before filling out this page}. Among them, n-propyl p-toluenesulfonate, isobutyl salicylate, bromine Tertiary butyl acetate is particularly preferred. The added amount is in the range of 0 · 0 1 to 20% by mass, preferably 0.05 to 5% by mass relative to the total amount of the flux. The above-mentioned decomposable organic acid esters are used in countercurrent alone. Decomposition at temperature is also low, so in order to promote decomposition, it is effective to add a small amount of ester decomposition catalyst. If the ester decomposition catalyst is decomposed Organic acid esters are catalysts that decompose at the countercurrent temperature and have the function of promoting acid generation, and among them, a hydrohalide of an organic base is particularly effective. The resin component in the solder paste of the present invention, Conventional resins, such as natural turpentine, heterogeneous turpentine, polymerized turpentine, modified turpentine, etc., can be used, and synthetic resins can use polyester, polyurethane, and acrylic resins. The solvent can use the same alcohols, ethers, esters, or aromatic solvents as the previous fluxes and solder pastes, such as benzyl alcohol, butanol I ethyl cellosolve, base cellosolve, butadiene Kikabitol, diethylene glycol hexyl ether, propylene glycol monophenyl ether, dioctyl phthalate, xylene, etc., or a mixture of them. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and added to improve printability. As the modifying agent, inorganic substances such as fine silica particles and kaolin particles, or organic substances such as hydrogenated ramie oil and ammonium compounds may be used. In the solder paste of the present invention, when a reducing agent is used as a stabilizer, can Stability is improved even more. As the reducing agent, antioxidants such as ordinary resins can be used. Examples include phenol-based compounds, phosphorus-based compounds, sulfur-based compounds, tocopherols and their derivatives, and L-ascorbic acid that can be dissolved in solvents. And its derivatives, etc. This paper is applicable in China National Standard (CNS) A4 size (210x297 mm) -12-A7 B7 V. Description of the invention (10) Specifically, phenol compounds can be listed as hydroquinone, Tea phenol, 2, 6 to 2 to 3rd butyl-p-cresol, butyl hydroxyanisole, 2, 2 > to methylene bis (4-methyl-1, 6-third butylphenol), etc. Examples of the phosphorus-based compound include triphenyl phosphite, tris (octadecyl phosphite), and tridecyl phosphite. Examples of the sulfur-based compound include dilauryl-3,3 / -thiodipropyl. Acid ester, distearyl-3,3 > dithiodipropionate, dimyristoyl ~ 3,3'-thiodipropionate and the like. Tocopherol and its derivatives, L-ascorbic acid and its derivatives can be used if they are reducing and solvent-soluble compounds such as their esters. Especially when two kinds of tocopherol or its derivative and L-ascorbic acid or its derivative are used, good results can be obtained. The compounding ratio is weight 0 · 5: 1 to • 1: 0 · 5, particularly preferably about 1 to 1. Specific examples of the L-ascorbic acid derivative include ascorbic acid 2-phosphoric acid, .ascorbic acid 2-sulfuric acid, ascorbic acid 2-glucoside, ascorbic acid 2,6-dibutyrate, and ascorbic acid-2,6 — Distearate, ascorbic acid—2,6—dimyristate, ascorbic acid—6—palmitate, ascorbic acid—6-stearate, ascorbic acid—6-myristate, ascorbic acid—2, 3 , 5,6—tetrapalmitate, ascorbic acid-2,3,5,6—tetramyristate, ascorbic acid-2,3,5,6—tetrastearate, ascorbic acid-2—sugar spine-6 — Palmitate, ascorbic acid 2-glucoside-6-myristate, ascorbic acid 2-glucoside-6-stearate, ascorbic acid-5,6-benzylidene, ascorbic acid-5,6-propylene 、 Ascorbic acid 2—Phosphoric acid, _____-This paper size is applicable. National Standard (CNS) A4 (210 x 297 mm.) ~ 3-——, 丨 丨 .—— (Please read the precautions on the back first (Fill in this page) Order Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 503147 A7 ____ _ B7 V. Description of the invention (11) —5 '6 —benzylidene, ascorbic acid 2 -phosphate —5,6 — propylene (please read the notes on the back before filling this page) and other tocopherol derivatives Specific examples of the substance include tocopherol, tocopherol acetate, tocopheryl phosphate, tocopherol sorbate, and tocopheryl nicotinate. These reducing agents can be used alone or in combination. The addition amount of the reducing agent may be an amount sufficient to ensure the storage stability of the solder paste, and is generally 0.0005 to 20% by mass relative to the total amount of the flux. If the added amount is too small, the stabilization effect will not be obtained, and even if it is added at 20 mass% or more, the effect caused by the high concentration addition is not observed, which is not good. For the flux used in the solder paste of the present invention, for example, a resin component of 2.0 to 26% by mass, a thixotropic agent of 0.04 to 20% by mass, and an organic acid component of 0.01 to 20% by mass are used with respect to the total amount of the flux. A halogen compound that satisfies the above-mentioned range of halide ions, 0.05 to 20% by mass of a reducing agent and a residual solvent. This flux is kneaded with the flux powder τ8 6-9 2 mass% with respect to the total amount of the solder paste, for example, to form the solder paste of the present invention. The amount of halide added at this time • The halide ion concentration in the flux after kneading the solder paste must be 300 ppm or less in terms of chlorine. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed on the blending of the complexes. During the kneading, the “moisturizing flux and other moisture” atmosphere moisture, so that the moisture content in the solder paste is 0. 5 mass% or less. It is preferably 0. 3% by mass or less. If the moisture content in the solder paste is more than 0. .5% by mass, ′ promotes the dissociation of the halide, and the dissociated halogen reacts with the flux alloy powder, which is not preferable. The p H 焊 of the solder paste is also preferably in the range of 4 to 9, more preferably in the range of 6 to 8, and it is preferable to suppress the reaction between the flux powder and the flux. At this time, 'PH adjusting agent is better to use the alcohol amines', and the size of the paper is applicable. National National Standard (CNS) A4 specification (210x297 public funds) " 14 ~~: 503147 A7 __ B7 V. Description of the invention 12) amine compounds of the first to third amines of the family, aliphatic unsaturated amines, alicyclic amines, aromatic amines, etc. Specific examples of these amine compounds include ethanolamine, butylamine, and aminopropanol , Polyoxyethylene oleylamine, polyoxyethylene laurylamine, polyoxyethylene stearylamine, diethylamine, triethylamine, methoxypropylamine, dimethylaminopropylamine, dibutylaminopropylamine, ethylhexylamine, Ethoxypropylamine, ethylethoxypropylamine, dipropylamine, isopropylamine, diisopropylamine, etc. The amount of amine compound used is better than 0.05 to 20% by mass relative to the total amount of flux in the solder paste. If the content is less than 0.05% by mass, the effect as a P Η regulator is insufficient. If it exceeds 20% by mass, P Η will generally exceed 9 and migrate to the alkali side to make the solder paste easily hygroscopic. Moreover, In order to prevent the copper of the circuit from rust, you can add pyrrole to the flux, such as benzotriazole, benzimidazole, Phenyltriazole, etc. The added amount of the rust inhibitor is preferably from 0.5 to 20 mass τ% relative to the total amount of the flux. The flux powder used in the solder paste of the present invention may be a conventionally known metal composition Substances, and fluxes containing easily oxidizable Z η are suitable for use. Examples include S η, Zn η, S η — A g — Zn η, (Please read the precautions on the back before filling in this Page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs B- ns AI ns BI ns Department n z- b. Department η ζ iuc Department nz I bsn
A n z I u c 爲 η s 以 舉 列 可 I 例 η 體 Ζ 具 I 之 η 述 S 上 系 Β 系 % 量 質 爲 n z 藥 焊 晶 共 之 % 量 、5 質心 4 η η s 1—I 9 以 下 以 中 爲 x\ly 示 表 η ΖA nz I uc is η s. To give an example I. η body Z with I η said S above B system% mass and mass are the total amount of nz flux-welded crystals, 5 centroids 4 η η s 1—I 9 In the following, x \ ly is used to indicate η ZZ
A Β S 3 η ζ 1 η / ζ η τ—Is \ 4 τ—I 5 Β η 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）_ 15 - 503147 A7 B7 五、發明説明（13 ) (請先閱讀背面之注意事項再填寫本頁) 5Sb/lzn、88.2Sn/l〇Bi/〇.8Cu /lZn、88Sn/4Ag/7Sb/lZn、 97Sn/lAg/lSb/lZn. 91 . 2Sn/ 2Ag/〇 · 8Cu/6Zn、8 9Sn/8Zn/ 3Bi、86Sn/8Zn/6Bi、89.1Sn/ 2Ag/〇·9Cu/8Zn等。又，本發明之焊藥粉末 亦可混合二種以上不同組成之焯藥組成。 本發明之焊膏爲適合使用於將基板，例如印刷電路板 與電子零件粘合製造粘合物。本發明焊膏之使用方法、及 電子零件粘合物之製造方法，可列舉例如在欲塗附焊藥之 部分，以印刷法等塗佈焊膏，並載放電子零件，其後加熱 令焊藥粒子熔融並凝固，則可於基板上粘合電子零件。 經濟部智慧財產局員工消費合作社印製 基板與電子零件之粘合方法（裝配方法）可列舉例如 表面裝配技術（S Μ T )。此裝配方法首先爲7以印刷法， 於基板，例如電路板上之所欲處塗附焊膏。其次，將晶片 零件和Q F Ρ等之電子零件載放於焊膏上，並以逆流熱源 一倂塗附焊藥。於逆流熱源可使用熱風爐、紅外線爐、蒸 氣冷凝塗附焊藥裝置、光束1塗附焊藥裝置等。 本發明之逆流過程爲依焊藥合金組成而異，、於 91Sn/9Zn、89Sn/8Zn/3Bi、 8 6 S η / 8 Ζ η / 6 B i等之S η — Ζ η系之情況，以 預加熱和逆流之二段工程進行爲佳，且各條件爲預加熱溫 度爲1 3 0〜1 8 0 °C，較佳爲1 3 0〜1 5 0 °C，預加 熱時間爲6 0〜1 2 0秒，較佳爲6 0〜9 0秒’逆流溫 本紙張尺度適用中.國國家標準（CNS ) A4規格(210X297公釐） :16 - 503147 A7 B7 五、發明説明（14 ) 度爲2 1 0〜2 3 0 °C，較佳爲2 1 0〜2 2 0 °C，逆流 時間爲3 0〜6 0秒’較佳爲3 0〜4 0秒。尙，其他合 (請先閲讀背面之注意事項再填寫本頁) 金系中之逆流溫度相封於合金溶點+ 2 0〜+ 5 0 °C，較 佳相對於合金熔點+ 2 0〜+ 3 〇 °C，其他之預加熱溫度 、預加熱時間、逆流時間可與上述同樣之範圍。 本發明之焊膏可在氮氣中或大氣中進行上述之逆流過 程。氮逆流之情況爲令氧濃度爲5體積％以下，較佳爲 0 · 5體積％以下’可比大氣逆流之情況令焊藥對於電路 板等基板之浸潤性更加提高，且焊藥孔之發生亦變少，故 可安定處理。 其後，將基板冷却且令表面裝配完畢。根據此裝配方 法製造電子零件粘合物之方法中，亦可在印刷電路板等之 基板（被粘合板）兩面進行粘合。尙，可使用本發明焊膏 之電子零件可列舉例如L S I、電阻器、電容-、晶體管 、電感器、濾波器、發振子-振動子等，但並非限定於此 〇 經濟部智慧財產局員工消費合作社印製 又，本發明爲預先於基板之指定表面，例如印刷基板 之電路金屬之指定表面，經由化學反應形成粘合性被膜， 並使其附著焊藥粉末後塗佈助熔劑，並加熱至焊藥之熔融 溫度令其逆流，形成焊藥緩衝層之電路基板（特開平 7 — .7 2 4 4公報），使用本發明之焊膏並以S Μ T (表 面裝配技術）裝配時，具有更優良之焊藥塗附性。 經由本發明之焊膏，可使用環境污染少且不含P b之 焊藥合金，粘合電子零件造成精細齒距化，例如可符合裝 本紙張尺度適用中.國國家標準（CNS ) A4規格（210X 297公釐） -- 503147 A7 . B7 _ 五、發明説明（15 ) 配電路板之精細齒距化，零件之多樣化，且因而可提供零 件壽命優良之電路板。 (請先閱讀背面之注意事項再填寫本頁) 用以實施發明之最佳形態 以下根據實施例更加具體說明本發明之內容，但本發 明並不被其所限定。 〔試驗法〕 ①鹵離子濃度測定 於焊膏1克中加入氯仿5毫升並攪拌，將助熔劑部分 溶解後，加入超純水1 0毫升並將鹵離子萃取至水中，且 以離子層·析測定水層。 使用之裝置：YOKOGAWA ICM00 ‘ 分離柱：SAM 3—125 充塡劑：親水性低交換容量強離子交換樹脂 粒徑：1 0 μ m 經濟部智慧財產局員工消費合作社印製 交換容量：60//eq/U ' 溶離液和流量：4 m Μ N a 2 C〇3 / 4 m Μ NaHC〇3、2m£ /分鐘 除去液和流量：0 · 0 5 M 正十二烷基苯磺酸、2 /分鐘 溫度：4 0 °C 樣品量：1 0 0微升 -18- 本紙張尺度適用中周國家標準（CNS ) A4規格（210X297公釐） 503147 A7 B7 五、發明説明（16 ) ② 粘度測定 將製造時及2 5 °C、7日後之焊膏於1 〇 r P m中之 粘度，使用MARCOM公司製PCU— 205型SPIRAL粘度 計予以測定。 ③ 空隙之觀察（粘合之信賴性） 對6 0mm平方之銅板使用厚度1 5 0微米之金屬遮 蔽物，印刷6 m m X 6個圖型後，於大氣氛圔氣下逆流’ 其次以小刀將焊藥與銅板切斷後，以顯微鏡觀察該胃_部 分，並且觀察空隙的發生狀況。對於6個圖型計測大小爲 1 0 //m以上之空隙，並且以每1個圖型之平均個數爲2 個以上之情況視爲不合格。 (實施例1〜9、比較例1〜3 ) <助熔劑及焊膏之製造> 加入做爲樹脂成分之聚合松脂1 7 · 5質量％、不均 化松脂2 7 . 5質量％、做爲觸變劑之氫化箆麻油7質量 %、做爲有機鹼鹵化氫酸鹽之二苯基胍氫溴酸鹽、環乙胺 氫溴酸鹽、做爲鹵素化合物之六溴環十二烷、2，3 —二 溴—.2 -丁烯—1，4 —二醇、4 —硬脂醯氧基苄基溴、 做爲有機酸成分之水楊酸異丁酯、對-甲苯磺酸正丙酯分 別以表1所示之份量、及做爲P Η調整劑之三乙醇胺2質 量％、做爲還原劑之氫醌〇 · 3質量％、做爲防銹劑之苯 本紙張尺度適用中國國家標準（CNS ) Α4規格（2i0X 297公釐）_ 1 g嶋 I丨·"--,---1^1 — (請先閱讀背面之注意事項再填寫本頁) 、11 經濟部智慧財產局員工消費合作社印製 503147 A7 B7 _____ 五、發明説明（17 ) 並咪唑1質量％，並加入做爲溶劑之一甘醇單2 —乙基己 醚作爲1 0 0質量％，調製助熔劑。 於此助熔劑1 1質量％中添加8 9 S η / 8 Ζ η / 3 Β 1之無P b焊藥粉末8 9質量％ ’並以行星式磨予以 混練，製造3公斤之焊膏。製造條件示於表1。 (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 本紙張尺度適用中.國國家標準（CNS ) A4規格（210X297公釐） -20 - 503147A Β S 3 η ζ 1 η / ζ η τ—Is \ 4 τ—I 5 Β η This paper size applies to the Chinese National Standard (CNS) Α4 specification (210X297 mm) _ 15-503147 A7 B7 V. Description of the invention ( 13) (Please read the precautions on the back before filling out this page) 5Sb / lzn, 88.2Sn / l0Bi / 〇.8Cu / lZn, 88Sn / 4Ag / 7Sb / lZn, 97Sn / lAg / lSb / lZn. 91. 2Sn / 2Ag / 〇.8Cu / 6Zn, 89Sn / 8Zn / 3Bi, 86Sn / 8Zn / 6Bi, 89.1Sn / 2Ag / 〇9Cu / 8Zn, etc. In addition, the flux powder of the present invention may be mixed with two or more different peony compositions. The solder paste of the present invention is suitable for use in bonding substrates, such as printed circuit boards, and electronic parts to produce adhesives. The method for using the solder paste of the present invention and the method for manufacturing an adhesive for electronic parts include, for example, applying solder paste to a portion to be coated with a solder paste by a printing method, and placing the electronic part, followed by heating and soldering. When the drug particles melt and solidify, electronic components can be bonded to the substrate. For example, the method of bonding substrates and electronic parts (assembly method) printed by employees' cooperatives in the Intellectual Property Bureau of the Ministry of Economic Affairs may include, for example, surface mounting technology (SMT). This assembling method is 7 firstly, applying a solder paste to a substrate, such as a circuit board, by printing. Next, the wafer parts and electronic components such as Q F P are placed on the solder paste, and the flux is applied with a countercurrent heat source. For the countercurrent heat source, a hot blast stove, an infrared furnace, a vapor condensation coating flux device, a beam 1 coating flux device, and the like can be used. The countercurrent process of the present invention is different depending on the composition of the flux alloy. For the cases of S η — Zn η system such as 91Sn / 9Zn, 89Sn / 8Zn / 3Bi, 8 6 S η / 8 Zn η / 6 Bi, etc., The pre-heating and counter-current two-stage project is better, and each condition is that the pre-heating temperature is 130 to 180 ° C, preferably 130 to 150 ° C, and the pre-heating time is 60 to 60 120 seconds, preferably 60 ~ 90 seconds. The counter current temperature is applicable to this paper. National Standard (CNS) A4 (210X297 mm): 16-503147 A7 B7 5. Description of the invention (14) The temperature is 2 1 0 to 2 3 0 ° C, preferably 2 1 0 to 2 2 0 ° C, and the backflow time is 30 to 60 seconds, preferably 30 to 40 seconds.其他, other combinations (please read the precautions on the back before filling this page) The countercurrent temperature in the gold system is sealed at the melting point of the alloy + 2 0 ~ + 5 0 ° C, preferably relative to the melting point of the alloy + 2 0 ~ + 30 ° C, other pre-heating temperature, pre-heating time and counter current time can be in the same range as above. The solder paste of the present invention can be subjected to the above-mentioned reverse flow process in nitrogen or the atmosphere. In the case of nitrogen backflow, the oxygen concentration is 5 vol% or less, preferably 0.5 vol% or less. 'Compared to the case of air backflow, the wettability of the solder to substrates such as circuit boards is improved, and the occurrence of solder holes also occurs. Reduced, so stable processing. After that, the substrate is cooled and the surface is assembled. In the method for manufacturing an adhesive for electronic parts according to this assembly method, it is also possible to adhere both sides of a substrate (adhered board) such as a printed circuit board. Alas, the electronic parts that can use the solder paste of the present invention include, for example, LSI, resistor, capacitor-, transistor, inductor, filter, oscillator-vibrator, etc., but it is not limited to this. Employees ’Intellectual Property Bureau of the Ministry of Economic Affairs employee consumption Cooperative society printing, the present invention is a predetermined surface of a substrate, for example, a specified surface of a circuit metal of a printed substrate, to form an adhesive film through a chemical reaction, and apply flux to the flux powder after it is adhered to the surface, and heat it to The melting temperature of the flux causes it to flow backward to form a circuit substrate of the flux buffer layer (Japanese Unexamined Patent Publication No. Hei 7-.7 2 4 4). When the solder paste of the present invention is used and assembled by SMT (surface mounting technology), it has Better soldering ability. Through the solder paste of the present invention, a solder alloy with less environmental pollution and no P b can be used, and the electronic components can be bonded to cause fine tooth pitch. For example, it can meet the specifications of the paper in which it is installed. National Standard (CNS) A4 (210X 297 mm)-503147 A7. B7 _ V. Description of the invention (15) Fine pitch of the circuit board, diversification of parts, and thus can provide circuit boards with excellent part life. (Please read the precautions on the back before filling out this page.) Best Modes for Implementing the Invention The content of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. [Test method] ① Determination of halide ion concentration Add 5 ml of chloroform to 1 g of solder paste and stir. After partially dissolving the flux, add 10 ml of ultrapure water and extract halide ions into the water. The water layer was measured. Device used: YOKOGAWA ICM00 'Separation column: SAM 3—125 Filler: Hydrophilic, low exchange capacity, strong ion exchange resin Particle size: 10 μm Printed exchange capacity by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs: 60 // eq / U 'Eluent and flow rate: 4 m Μ N a 2 C〇3 / 4 m Μ NaHC〇3, 2m £ / min removal solution and flow rate: 0 · 0 5 M n-dodecylbenzenesulfonic acid, 2 Temperature per minute: 40 ° C Sample volume: 100 microliters -18- This paper size applies the National Standard (CNS) A4 specification (210X297 mm) 503147 A7 B7 V. Description of the invention (16) ② Viscosity measurement The viscosity of the solder paste at 10 r P m at the time of manufacture and at 25 ° C and 7 days later was measured using a PCU-205 SPIRAL viscometer manufactured by MARCOM. ③ Observation of voids (reliability of bonding) Use a metal shield with a thickness of 150 micrometers for a copper plate of 60 mm square, print 6 mm X 6 patterns, and countercurrently flow under a large atmosphere of radon. After the solder was cut from the copper plate, the stomach portion was observed with a microscope, and the occurrence of voids was observed. If the size of the six patterns is more than 1 0 // m, and the average number of each pattern is 2 or more, it is considered unacceptable. (Examples 1 to 9, Comparative Examples 1 to 3) < Production of Flux and Solder Paste > Adding polymer rosin 17.5% by mass as a resin component, unequal turpentine 27.5% by mass, 7% by mass of hydrogenated ramie oil as a thixotropic agent, diphenylguanidine hydrobromide as an organic base halide, cycloethylamine hydrobromide, and hexabromocyclododecane as a halogen compound , 2,3-dibromo-.2-butene-1,4-diol, 4-stearyloxybenzyl bromide, isobutyl salicylate as organic acid component, p-toluenesulfonic acid The normal propyl esters are used in the amounts shown in Table 1, and 2% by mass of triethanolamine as a P Η modifier, 0.3% by mass of hydroquinone as a reducing agent, and benzene paper as a rust inhibitor. China National Standard (CNS) Α4 specification (2i0X 297 mm) _ 1 g 嶋 I 丨 · "-, --- 1 ^ 1 — (Please read the notes on the back before filling this page), 11 Ministry of Economic Affairs Printed by the Intellectual Property Bureau's Consumer Cooperatives 503147 A7 B7 _____ V. Description of the invention (17) 1% by mass of benzimidazole, and added as a solvent, glycol 2-ethylhexyl ether as 1 0 0 quality % Flux modulation. To this flux 11 mass% was added 8 9 S η / 8 Z η / 3 Β 1 Pb-free flux powder 8 9 mass% ′ and kneaded with a planetary mill to produce a 3 kg solder paste. The manufacturing conditions are shown in Table 1. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is applicable in China. National Standard (CNS) A4 Specification (210X297 mm) -20-503147
A B 經濟部智慧財產局員工消費合作社印製 五、發明説明（18 ) 表1 實施例 有機鹵素化合物 有機鹽基鹵素化酸鹽 有機酸成分 1 姐 j \ \\ 環己胺氫溴酸鹽 1.2質量％ 水楊酸異丁酯 0.5質量％ 2 2,3-二溴-2-丁烯-1，4-二醇 3.5質量％ 環己胺氫溴酸鹽 0.3質量％ 對甲苯磺酸正丙酯 0.5質量％ 3 2,3-二溴-2-丁烯-1，4-二醇 3.5質量％ 姐 j \ \\ 對甲苯磺酸正丙酯 0.5質量％ 4 4-硬脂醯氧基苄基溴 3.5質量％ 二苯塞胍氫溴酸鹽 0.3質量％ . 水楊酸異丁酯 0.5質量％ 5 4-硬脂醯氧基苄基溴 3.5質量％ Μ . j \ \\ 水楊酸異丁酯 0·5質量％ 6 六溴環十二烷 3.5質量％ 二苯基胍氫溴酸鹽 0.1質量％ 水楊酸異丁酯 0.5質量％ 7 六溴環十二烷 3.5質量％ 姐 J \ \\ 水楊酸異丁酯 0.5質量％ 8 四溴硬脂酸2.0質量％ 六溴環十二烷 1.5質量％ 二苯基胍氫溴酸鹽 0.1質量％ 對甲苯磺酸正丙酯 0.5質量％ 9 四溴硬脂酸2.0重量％ 六溴環十二烷 1.5質量％ Μ J\\\ 對甲苯磺酸正丙酯 0.5質量％ 比較例 1 Μ η 環己胺氫溴酸鹽 5.0質量％ 水楊酸異丁酯 0.5質量％ 2 2,3-二溴-2-丁烯-1，4-二醇 3.5質量％ 二苯基胍氫溴酸鹽 3.0質量％ 水楊酸異丁酯 0.5 Mm% 3 4-硬脂醯氧基苄基溴 3.5質量％ 環己胺氫溴酸鹽 2.0質量％ 水楊酸異丁酯 0.5質量％ (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（21 OX 297公釐） -21 - 503147 A7 —B7 五、發明説明（19 ) <電子零件粘合物之製造> 使用S Μ T做爲裝配方法。將實施例1〜9、比較例 1〜3組成之焊膏分別於1枚之電路板上印刷，並將 L s I、晶片電阻、晶片電容器於焊膏上載放後，以逆流 熱源加熱塗附焊藥。逆流熱源爲使用熱風爐。 逆流條件爲預加熱溫度爲1 3 0 °C、預加熱時間爲 8 〇秒、逆流之波峰溫度爲2 2 0 °C，且2 0 0 °C以上之 逆流時間爲5 0秒鐘。 對於所製作之印刷電路板及所用之焊膏’根據前述之 測定方法比較特性。測定結果示於表2。尙，表2中之鹵 離子濃度爲表示氯換算値。 (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 本紙張尺度適用中.國國家標準（CNS ) A4規格（210X297公釐）-22 - 503147 A7 B7 五、發明説明（2〇 ) 經濟部智慧財產局員工消費合作社印製 表2 實施例 鹵離子濃度（ppm) 空隙發生 粘度（Pa · S) 初期値 7曰後 初期値 7曰後 1 2400 2450 〇 215 240 2 650 850 〇 201 220 3 180 200 〇 210 211 4 400 500 189 206 5 150 230 〇 205 210 6 150 250 〇 199 213 7 150 200 〇 195 208 8 150 200 〇 198 208 9 150 200 〇 195 206 比較例 ί · 1 9900 9950 X 不能測定 不能測定 2 4500 6150 X 372 不能測定 3 4000 7950 X 329 不能測定 〇：合格 X :不合格 (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（210X297公釐） _ 23 - 503147 A7 —_ B7 五、發明説明（21 ) 更且，同樣使用91Sn/9Zn、 86Sn/ (請先閲讀背面之注意事項再填寫本頁) 8 Z n/6 B i之無Pb焊藥粉末進行同樣之實驗，並且 取得完全同樣之結果。 又，比較實施例1〜9之逆流後之焊藥合金組織與先 前之S n — Pb系焊膏之焊藥合金組織時，S η — Pb系 之情況爲於高溫環境下之結晶粗大化顯著，相對地’本發 •明之S η - Ζ η系合金則爲粗矢化之傾向小，因此提高焊 藥之機械物性，並且確認使用其可提高裝配電路板的壽命 特性。 產業上之可利用性 根據本發明之焊膏，可大幅抑制焊藥合金與助熔劑之 反應，並且可取得極優良之保存安定性。特別’本發明在 先前保存安定性差之S η - Ζ η系焊膏中’亦可令保存安 定性格外提高，並且確認其有效性。 又，經由本發明焊膏之開發，則可提供裝配電路板之 精細齒距化，配合零件多樣化之信賴性高之電路板的塗附 焊藥方法，塗附焊藥粘合物。 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 ) Α4規格（210χ297公釐）-24 ·Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (18) Table 1 Examples of organic halogen compounds, organic salt-based halogenated acid salts, organic acid components, 1 j \ \\ cyclohexylamine hydrobromide 1.2 mass % Isobutyl salicylate 0.5% by mass 2 2,3-dibromo-2-butene-1,4-diol 3.5% by mass cyclohexylamine hydrobromide 0.3% by mass n-propyl p-toluenesulfonate 0.5 Mass% 3 2,3-dibromo-2-butene-1,4-diol 3.5% by mass Sister j \ \\ n-propyl p-toluenesulfonate 0.5% by mass 4 4-stearyloxybenzyl bromide 3.5% by mass diphenylthioguanidine hydrobromide 0.3% by mass. Isobutyl salicylate 0.5% by mass 5 4-stearyloxybenzyl bromide 3.5% by mass Μ. J \ \\ Isobutyl salicylate 0.5% by mass 6 hexabromocyclododecane 3.5% by mass diphenylguanidine hydrobromide 0.1% by mass isobutyl salicylate 0.5% by mass 7 hexabromocyclododecane 3.5% by mass Sister J \ \\ Isobutyl salicylate 0.5 mass% 8 tetrabromostearic acid 2.0 mass% hexabromocyclododecane 1.5 mass% diphenylguanidine hydrobromide 0.1 mass% n-propyl p-toluenesulfonate 0.5 mass% 9 tetra bromine 2.0% by weight of stearic acid 1.5% by weight of hexabromocyclododecane Μ J \\\ n-propyl p-toluenesulfonate 0.5% by weight Comparative Example 1 η cyclohexylamine hydrobromide 5.0% by weight isobutyl salicylate Esters 0.5% by mass 2 2,3-Dibromo-2-butene-1,4-diol 3.5% by mass Diphenylguanidine hydrobromide 3.0% by mass Isobutyl salicylate 0.5 Mm% 3 4-Hard Fatty alcohol benzyl bromide 3.5% by mass Cyclohexylamine hydrobromide 2.0% by mass Isobutyl salicylate 0.5% by mass (Please read the precautions on the back before filling this page) The paper dimensions apply to Chinese national standards ( CNS) A4 specification (21 OX 297 mm) -21-503147 A7 —B7 V. Description of the invention (19) < Manufacture of electronic component adhesives > SMT was used as the assembly method. The solder pastes composed of Examples 1 to 9 and Comparative Examples 1 to 3 were printed on one circuit board, and L s I, chip resistors, and chip capacitors were placed on the solder paste, and then heated and applied with a countercurrent heat source. Welding flux. The countercurrent heat source is the use of a hot blast stove. The counter current conditions are a pre-heating temperature of 130 ° C, a pre-heating time of 80 seconds, a peak temperature of the counter current of 220 ° C, and a counter current time of more than 200 ° C is 50 seconds. The characteristics of the produced printed circuit board and the solder paste 'were compared according to the aforementioned measurement methods. The measurement results are shown in Table 2.尙, the halide ion concentration in Table 2 is expressed in terms of chlorine, 値. (Please read the notes on the back before filling out this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is in use. China National Standard (CNS) A4 Specification (210X297 mm) -22-503147 A7 B7 V. Description of the invention (2〇) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Example 2 Halide ion concentration (ppm) Void generation viscosity (Pa · S) Early stage 7 Early stage 7 Early stage 1 2400 2450 〇215 240 2 650 850 〇201 220 3 180 200 〇210 211 4 400 500 189 206 5 150 230 〇205 210 6 150 250 〇199 213 7 150 200 〇195 208 8 150 200 〇198 208 9 150 200 〇195 206 Comparative example · 1 9900 9950 X can not be measured cannot be measured 2 4500 6150 X 372 cannot be measured 3 4000 7950 X 329 cannot be measured 〇: Pass X: Unqualified (please read the precautions on the back before filling this page) This paper size applies Chinese national standards (CNS) A4 specification (210X297 mm) _ 23-503147 A7 —_ B7 V. Description of the invention (21) In addition, 91Sn / 9Zn, 86Sn / are also used (Please read the precautions on the back before filling (Write this page) The same experiment was performed on Pb-free solder powder of 8 Z n / 6 B i and the exact same results were obtained. In addition, when comparing the flux alloy structure after the counterflow in Examples 1 to 9 with the previous solder alloy structure of the Sn—Pb-based solder paste, the situation of the Sη—Pb-based system is that the crystal coarsening in the high temperature environment is significant. In contrast, the S η-Zn η-based alloy of the present invention has a low tendency to roughen. Therefore, the mechanical properties of the solder are improved, and it is confirmed that the use of it can improve the life characteristics of the assembled circuit board. Industrial Applicability According to the solder paste of the present invention, the reaction between the flux alloy and the flux can be significantly suppressed, and excellent storage stability can be obtained. In particular, the present invention can improve storage stability and confirm its effectiveness in S η-Z η-based solder pastes with poor storage stability. In addition, through the development of the solder paste of the present invention, it is possible to provide a method for applying a solder paste to a circuit board with a fine tooth pitch and a highly reliable circuit board that is compatible with a variety of parts and to apply solder paste. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is in accordance with the Chinese National Standard (CNS) A4 specification (210 x 297 mm)-24 ·