TW202333882A - 水溶性助焊劑及焊膏 - Google Patents
水溶性助焊劑及焊膏 Download PDFInfo
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- TW202333882A TW202333882A TW111139299A TW111139299A TW202333882A TW 202333882 A TW202333882 A TW 202333882A TW 111139299 A TW111139299 A TW 111139299A TW 111139299 A TW111139299 A TW 111139299A TW 202333882 A TW202333882 A TW 202333882A
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- Prior art keywords
- acid
- mass
- flux
- boiling point
- examples
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- 230000004907 flux Effects 0.000 title claims abstract description 103
- 229910000679 solder Inorganic materials 0.000 title claims description 61
- 238000009835 boiling Methods 0.000 claims abstract description 88
- 150000004715 keto acids Chemical class 0.000 claims abstract description 65
- 239000002904 solvent Substances 0.000 claims abstract description 53
- 238000002844 melting Methods 0.000 claims abstract description 35
- 230000008018 melting Effects 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims description 51
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- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 44
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 44
- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- 150000001412 amines Chemical class 0.000 claims description 31
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- 229910045601 alloy Inorganic materials 0.000 claims description 16
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- 229920001187 thermosetting polymer Polymers 0.000 claims description 5
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 claims description 3
- -1 monocyclic alkane Chemical class 0.000 description 44
- 150000002430 hydrocarbons Chemical group 0.000 description 33
- 239000000376 reactant Substances 0.000 description 27
- CFQZKFWQLAHGSL-FNTYJUCDSA-N (3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e)-octadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoic acid Chemical compound OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C CFQZKFWQLAHGSL-FNTYJUCDSA-N 0.000 description 20
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- 235000020661 alpha-linolenic acid Nutrition 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 13
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- 150000003505 terpenes Chemical class 0.000 description 10
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- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 9
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- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 8
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 8
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- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 5
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- 229910020816 Sn Pb Inorganic materials 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 2
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000007824 aliphatic compounds Chemical class 0.000 description 2
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Abstract
本發明之水溶性助焊劑可進一步抑制孔洞產生,其含有熔點40℃以下的酮酸與沸點240℃以下的溶劑。
Description
本發明係關於水溶性助焊劑及焊膏。
本案根據2021年11月10日在日本提出申請的日本特願2021-183673號主張優先權,並將其內容援用至此。
一般係藉由焊接來進行零件對基板的固定以及零件對基板的電連接。焊接中會使用助焊劑、焊料粉末以及將助焊劑及焊料粉末混合而成的焊膏。
助焊劑具有將存在於作為焊接對象之接合對象物的金屬表面及焊料上的金屬氧化物以化學方式去除並且可使金屬元素在兩者之邊界移動的功能。因此,藉由使用助焊劑進行焊接,兩者之間形成金屬間化合物,而可得到穩固的接合。
使用焊膏的焊接中,首先將焊膏印刷於基板上之後,將零件搭載於其上,在稱為回焊爐的加熱爐中,將搭載有零件的基板加熱。藉此,焊膏所包含的焊料粉末熔融而使零件於基板進行焊接。
一般而言,助焊劑包含樹脂成分、溶劑、活化劑、觸變劑等。為了提高焊料與接合對象物的接合可靠度,會藉由清洗來去除焊接後剩餘的助焊劑。即使進行了清洗仍殘留的助焊劑則被稱為助焊劑殘渣。
以往係使用電絕緣性、耐濕性等優良的松香作為助焊劑中的樹脂成分。包含松香的助焊劑在焊接後的清洗中需要有機溶劑,故可能在安全方面、環境方面等產生問題。因此要求一種可用水輕易地清洗焊接後之助焊劑的水溶性助焊劑。
對此,專利文獻1記載一種助焊劑,其包含有機酸聚甘油酯、觸變劑與具有特定SP值之溶劑。根據專利文獻1記載之助焊劑,焊接後以水進行清洗的性能進一步提高。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開2016-43398號公報
近年來逐漸使用四方無引線構裝(QFN,Quad Flat Non-Leaded Package)等小型化零件。QFN在封裝的周邊不具有引線,而是在封裝的背面具有引線框架的露出面及電極端子,因此在將QFN焊接時,係以焊膏將QFN的背面與基板的表面之間接合。
在將QFN等封裝背面之引線框架的露出面及電極端子相對於基板進行焊接時,封裝的背面容易殘留助焊劑殘渣。然後,殘留於封裝背面的助焊劑殘渣,成為孔洞產生的原因。對此,使用了專利文獻1記載之助焊劑的焊膏中,難以抑制孔洞的產生。
於是,本發明之目的在於提供一種可進一步抑制孔洞產生的助焊劑及焊膏。
為了解決上述課題,本發明採用以下的構成。
亦即,本發明的第1態樣係一種水溶性助焊劑,其含有熔點40℃以下的酮酸與沸點240℃以下的溶劑。
第1態樣之水溶性助焊劑中,前述酮酸較佳係沸點進一步為250℃以下。
第1態樣之水溶性助焊劑中,前述酮酸的含量相對於水溶性助焊劑的總質量(100質量%)較佳為10至25質量%。
第1態樣之水溶性助焊劑中,前述酮酸較佳係包含分子內具有1個羧基的有機酸。
第1態樣之水溶性助焊劑中,前述酮酸較佳係包含乙醯丙酸。
第1態樣之水溶性助焊劑中,前述酮酸與前述溶劑的比率,以溶劑/酮酸所示的質量比計,較佳為0.60至4.0。
第1態樣之水溶性助焊劑中,較佳係更含有非離子界面活性劑及胺。
第1態樣之水溶性助焊劑中,較佳係不含選自由松香及熱硬化性樹脂所成群組中的1種以上之樹脂成分。
又,本發明的第2態樣係一種焊膏,其含有焊料合金粉末與第1態樣之水溶性助焊劑。
根據本發明,可提供一種可抑制孔洞產生的助焊劑及焊膏。
圖1係顯示孔洞面積率之評價中的回焊溫度曲線(reflow profile)的圖。
(水溶性助焊劑)
本實施型態之水溶性助焊劑含有酮酸與溶劑。
本說明書中,所謂的水溶性助焊劑,係指以水清洗其助焊劑殘渣而可藉此將其去除的助焊劑。以下有時將水溶性助焊劑僅記載為助焊劑。
本說明書中,所謂的沸點係指對象液體的飽和蒸氣壓等於1大氣壓(亦即1013hPa)時,該液體的溫度。
又,本說明書中,所謂的熔點係指固體熔解成為液體時的溫度。本說明書中的化合物之熔點的值主要係記載於「化學手冊 基礎編 修訂5版(日本化學會,丸善出版社)」的值。
<酮酸>
≪特定酮酸≫
本實施型態之水溶性助焊劑的特定酮酸係含有熔點40℃以下的酮酸。所謂的酮酸,係含酮基及羧基的化合物。在本發明中,作為特定酮酸,可列舉例如下述通式(1)表示的化合物。
特定酮酸的熔點較佳為38℃以下。特定酮酸的熔點較佳為5℃以上,更佳為10℃以上,再佳為15℃以上,特佳為20℃以上,最佳為25℃以上。
藉由使特定酮酸的熔點在上述上限值以下,即使在較低溫中,亦容易提高助焊劑殘渣的流動性。藉此,更容易從助焊劑殘渣中排出孔洞。
[式中,R1為可具有取代基的烴基;R2為可具有取代基的烴基或單鍵]。
R1中的烴基可列舉例如:碳數1至20的鏈狀烴基、碳數3至20的脂環族烴基、芳香族烴基、-OR11等。
R1為鏈狀烴基時,前述鏈狀烴基可為直鏈狀,亦可為分支鏈狀。前述鏈狀烴基為飽和烴基或不飽和烴基,較佳為飽和烴基。
R1為脂環族烴基時,前述脂環族烴基可為多環式基,亦可為單環式基。作為單環式的脂環族烴基,較佳係從單環烷烴去除1個以上之氫原子而成的基。作為多環式的脂環族烴基,較佳係從多環烷烴去除1個以上之氫原子而成的基。
R1中的取代基可列舉:羰基、羧基、羥基、胺基、鹵素原子等。R1中的鹵素原子可列舉:氟原子、氯原子、溴原子、碘原子。
R1為芳香族烴基時,前述芳香族烴基為具有至少1個芳香環的烴基,可列舉例如:苯、萘、蒽、菲等芳香族烴環;構成芳香族烴環的碳原子之一部分經雜原子取代而成的芳香族雜環;芳香族烴環與芳香族雜環縮合而成的縮合環等。R1中的芳香族烴基具有取代基時,作為前述取代基,可列舉:碳數1至20的烴基、
羧基、羥基、胺基、鹵素原子等。前述取代基為烴基時,前述烴基可列舉例如與R1中的烴基相同者。
-OR11中的R11可列舉與上述R1中的烴基相同者。
R1較佳為鏈狀烴基。前述鏈狀烴基的碳數較佳為1至10,更佳為1至5,再佳為1至3,特佳為1。碳數1至5的烴基可列舉例如:甲基、乙基、丙基、異丙基、正丁基、異丁基、第三丁基、戊基、異戊基、新戊基等。
R2中的烴基可列舉例如:碳數1至20的鏈狀烴基、碳數3至20的脂環族烴基、芳香族烴基等。R2中的取代基可列舉在R1中所述者。
R2為鏈狀烴基時,前述鏈狀烴基可為直鏈狀,亦可為分支鏈狀。前述鏈狀烴基為飽和烴基或不飽和烴基,較佳為飽和烴基。
R2中的直鏈狀烴基較佳為直鏈狀的伸烷基,具體可列舉:亞甲基[-CH2-]、伸乙基[-(CH2)2-]、三亞甲基[-(CH2)3-]、四亞甲基[-(CH2)4-]、五亞甲基[-(CH2)5-]等。
R2中的分支鏈狀烴基較佳為分支鏈狀的伸烷基,具體可列舉:-CH(CH3)-、-CH(CH2CH3)-、-C(CH3)2-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3)-、-C(CH2CH3)2-等烷基亞甲基;-CH(CH3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-、-C(CH2CH3)2-CH2-等烷基伸乙基;-CH(CH3)CH2CH2-、-CH2CH(CH3)CH2-等烷基三亞甲基;-CH(CH3)CH2CH2CH2-、-CH2CH(CH3)CH2CH2-等烷基四亞甲基等烷基伸烷基等。
R2為脂環族烴基時,前述脂環族烴基係在R1中從上述脂環族烴基去除1個氫原子而成者。
R2為芳香族烴基時,前述芳香族烴基係在R1中從上述芳香族烴基去除1個氫原子而成者。
R2較佳為鏈狀烴基,更佳為直鏈狀烴基。
前述鏈狀烴基的碳數較佳為1至10,更佳為1至5,再佳為1至3。前述鏈狀烴基較佳為亞甲基、伸乙基或三亞甲基。
特定酮酸可列舉例如:丙酮酸(熔點:13.6℃,沸點:165℃)、乙醯丙酸(熔點:37.2℃,沸點:245℃)、3-側氧丁酸(熔點:36.5℃)、5-側氧己酸(熔點:13℃,沸點:274℃)、6-側氧庚酸(熔點:36℃,沸點:335℃)、7-側氧辛酸(熔點:28℃,沸點:370℃)、2-側氧丁酸(熔點:32℃,沸點:208℃)、2-側氧戊酸(熔點:7℃,沸點:230℃)等。
特定酮酸可單獨使用1種,亦可混合2種以上使用。
特定酮酸較佳係包含分子內具有1個羧基的有機酸。藉此更容易抑制孔洞產生。
特定酮酸較佳係包含選自由丙酮酸及乙醯丙酸所成群組中的1種以上,更佳係包含乙醯丙酸。
特定酮酸的沸點(Tk)較佳為150℃以上,更佳為200℃以上,特佳為220℃以上,最佳為230℃以上。藉由使Tk在前述下限值以上,在回焊時,容易抑制特定酮酸完全揮發。此外,相較於特定酮酸,特定溶劑容易先揮發。因此,回焊時,特定酮酸會與已開始揮發的溶劑一起揮發。藉此,在回焊時,溶劑及特定酮酸揮發而產生之氣泡(孔洞)互相融合而變大,孔洞容易從焊膏排出。亦即,回焊時更容易抑制孔洞產生。
Tk較佳為280℃以下,更佳為270℃以下,再佳為260℃以下,特佳為250℃以下。藉由使Tk在前述上限值以下,在回焊時,特定酮酸容易與溶劑一起揮
發。藉此,在回焊時溶劑及特定酮酸揮發而產生之孔洞互相融合變大,孔洞容易從焊膏排出。亦即,回焊時更容易抑制孔洞產生。
Tk較佳為150℃以上280℃以下,更佳為200℃以上270℃以下,再佳為220℃以上260℃以下,特佳為230℃以上250℃以下。
≪其他酮酸≫
本實施型態之水溶性助焊劑可含有熔點超過40℃的酮酸之其他酮酸。
其他酮酸可列舉例如:草乙酸(熔點:161℃)、α-酮戊二酸(熔點:113.5℃)、丙酮二羧酸(熔點:138℃)、α-酮己二酸(熔點:127℃)、β-酮己二酸(熔點:124-126℃)等。
其他酮酸可單獨使用1種,亦可混合2種以上使用。
前述助焊劑中,特定酮酸的含量相對於前述助焊劑的總量(100質量%)較佳為5質量%以上,更佳為10質量%以上,再佳為15質量%以上。又,前述含量較佳為30質量%以下,更佳為25質量%以下,再佳為20質量%以下。
例如,前述助焊劑中,特定酮酸的含量相對於前述助焊劑的總量(100質量%)可為10質量%以上25質量%以下,可為15質量%以上25質量%以下,亦可為15質量%以上20質量%以下。
前述助焊劑中,特定酮酸的含量相對於酮酸的總質量(100質量%),較佳為90質量%以上,更佳為100質量%。
藉由使特定酮酸的含量在前述下限值以上,更容易抑制孔洞產生。藉由使特定酮酸的含量在前述上限值以下,前述助焊劑保管時的經時穩定性容易提高。
<溶劑>
≪特定溶劑≫
本實施型態之水溶性助焊劑係含有沸點240℃以下的溶劑(S1)之特定溶劑。特定溶劑之沸點的下限值並無特別限定,例如可為150℃以上。
特定溶劑可列舉例如:水、沸點240℃以下的二醇醚系溶劑、沸點240℃以下的萜品醇類、沸點240℃以下的醇系溶劑、沸點240℃以下的酯系溶劑等。
沸點240℃以下的二醇醚系溶劑可列舉例如:苯基甘醇(沸點237℃:乙二醇單苯醚)、丁基卡必醇(沸點231℃:二乙二醇單丁醚)、己二醇(沸點197℃:2-甲基戊烷-2,4-二醇)等。
沸點240℃以下的萜品醇類可列舉例如:α-萜品醇(沸點217℃)。
沸點240℃以下的醇系溶劑可列舉例如:乙醇(沸點78℃)、1-丙醇(沸點97℃)、2-丙醇(沸點82℃)、1,2-丁二醇(沸點192℃)、2,2-二甲基-1,3-丙二醇(沸點210℃)、2,5-二甲基-2,5-己二醇(沸點215℃)、2,5-二甲基-3-己炔-2,5-二醇(沸點206℃)、2,3-二甲基-2,3-丁二醇(沸點174℃)、2-甲基戊烷-2,4-二醇(沸點197℃)、1-乙炔基-1-環己醇(沸點180℃)等。
特定溶劑可單獨使用1種,亦可混合2種以上使用。
特定溶劑較佳係包含選自由沸點240℃以下的二醇醚系溶劑、沸點240℃以下的萜品醇類、沸點240℃以下的醇系溶劑及沸點240℃以下的酯系溶劑所成群組中的1種以上,更佳係包含選自由沸點240℃以下的二醇醚系溶劑、及沸點240℃以下的萜品醇類所成群組中的1種以上。
特定溶劑較佳係包含選自由苯基甘醇、己二醇及α-萜品醇所成群組中的1種以上,再更佳為包含α-萜品醇。
特定溶劑的沸點(Ts)較佳為150℃以上,更佳為180℃以上,再佳為190℃以上,特佳為200℃以上,最佳為210℃以上。藉由使Ts在前述下限值以上,容易抑制孔洞產生。
Ts為240℃以下,較佳為235℃以下,更佳為230℃以下,再佳為225℃以下。藉由使Ts在前述上限值以下,更容易抑制孔洞產生。
Ts較佳為150℃以上240℃以下,更佳為180℃以上235℃以下,再佳為200℃以上230℃以下,特佳為210℃以上225℃以下。
Tk與Ts的溫度差△T的絕對值較佳為0℃以上,更佳為3℃以上,再佳為5℃以上。
藉由使△T在前述下限值以上,更容易抑制孔洞產生。
△T較佳為70℃以下,更佳為60℃以下,再佳為55℃以下。
藉由使△T在前述上限值以下,更容易抑制孔洞產生。
再者,Tk及Ts較佳係滿足Ts<Tk的關係。
Ts<Tk時,△T較佳為5℃以上50℃以下,更佳為10℃以上45℃以下,再佳為15℃以上40℃以下,特佳為20℃以上35℃以下。
藉由使△T在前述範圍內,更容易抑制孔洞產生。
≪其他溶劑≫
本實施型態之水溶性助焊劑係可含有其他溶劑(亦即特定溶劑以外的溶劑)。
其他溶劑可列舉例如:沸點超過240℃的二醇醚系溶劑、沸點超過240℃的醇系溶劑、沸點超過240℃的酯系溶劑等。
沸點超過240℃的二醇醚系溶劑可列舉例如:二乙二醇單己醚(沸點258℃)、二乙二醇單-2-乙基己醚(沸點272℃)、二乙二醇二丁醚(沸點256℃)、
三乙二醇單丁醚(沸點278℃)、三乙二醇丁基甲醚(沸點261℃)、四乙二醇二甲醚(沸點275℃)、三丙二醇單甲醚(沸點243℃)等。
沸點超過240℃的醇系溶劑可列舉例如:2,4-二乙基-1,5-戊二醇(沸點264℃)、2-乙基-2-羥基甲基-1,3-丙二醇(沸點292℃)、2,2’-氧基雙(亞甲基)雙(2-乙基-1,3-丙二醇)(沸點448℃)、1,2,6-三羥基己烷(沸點386℃)、1,4-環己二醇(沸點293℃)、1,4-環己烷二甲醇(沸點283℃)、2,4,7,9-四甲基-5-癸炔-4,7-二醇(沸點255℃)、2,2-雙(羥基甲基)-1,3-丙二醇(沸點437℃)、異莰基環己醇(沸點318℃)等。
沸點超過240℃的酯系溶劑可列舉例如:雙(2-乙基己基)癸二酸酯(沸點377℃)等。
其他溶劑可單獨使用1種,亦可混合2種以上使用。
前述助焊劑中,特定溶劑的含量相對於前述助焊劑的總量(100質量%)較佳為10質量%以上70質量%以下,更佳為15質量%以上60質量%以下,再佳為15質量%以上50質量%以下。
前述助焊劑中,特定溶劑的含量相對於溶劑的總質量(100質量%)較佳為90質量%以上,更佳為100質量%。
藉由使特定溶劑的含量在前述下限值以上,更容易抑制孔洞產生。
特定酮酸與特定溶劑的混合比,作為特定溶劑/特定酮酸表示的質量比、亦即特定溶劑之含量相對於特定酮酸之含量的比率,較佳為0.60至4.0,更佳為0.60至3.0,再佳為0.60至2.5。
若此混合比在前述較佳範圍內,則更容易抑制孔洞產生。
<其他成分>
本實施型態中的助焊劑,除了酮酸及溶劑以外,可因應需求含有其他成分。
其他成分可列舉:酮酸以外的有機酸、胺、鹵化物等其他活性劑、界面活性劑、金屬鈍化劑、矽烷偶合劑、抗氧化劑、著色劑等。
[酮酸以外的有機酸]
酮酸以外的有機酸可列舉例如:羧酸、有機磺酸等。
羧酸可列舉例如:脂肪族羧酸、芳香族羧酸等。
羧酸可列舉例如:乙二酸、丙二酸、丁二酸、戊二酸、己二酸、壬二酸、二十烷二酸、水楊酸、吡啶二甲酸、二丁基苯胺二乙醇酸、辛二酸、癸二酸、對苯二甲酸、十二烷二酸、對羥基苯基乙酸、吡啶甲酸、苯基丁二酸、鄰苯二甲酸、月桂酸、苯甲酸、酒石酸、異三聚氰酸參(2-羧基乙基)、1,3-環己烷二羧酸、2,2-雙(羥基甲基)丙酸、2,2-雙(羥基甲基)丁酸、2,3-二羥基苯甲酸、2,4-二乙基戊二酸、2-喹啉羧酸、3-羥基苯甲酸、對大茴香酸、硬脂酸、12-羥基硬脂酸、油酸、亞麻油酸(Linoleic Acid)、次亞麻油酸(Linolenic Acid)、肉豆蔻酸、棕櫚酸、庚二酸、己酸、庚酸、辛酸、壬酸、異壬酸、癸酸、癸烯酸(Caproleic acid)、十一烷酸、月桂酸、烏藥酸(Linderic Acid)、十三酸、肉豆蔻油酸(Myristoleic Acid)、十五酸、異棕櫚酸、棕櫚油酸(Palmitoleic Acid)、十六碳三烯酸、大風子油酸(Hydnocarpic Acid)、反式脂肪酸、異硬脂酸、反油酸(Elaidic Acid)、芹子酸(Petroselinic Acid)、4,8,12,15-十八碳四烯酸(Moroctic Acid)、油硬脂酸(Eleostearic Acid)、塔日酸(Tariric Acid)、牛油酸(Vaccenic Acid)、蓖麻油酸(Ricinoleic Acid)、斑鳩菊酸(Vernolic Acid)、蘋婆酸(Sterculic Acid)、十九烷酸、二十烷酸、二聚物酸、三聚物酸、於二聚物酸中添加氫而成氫化物的氫化二聚物酸、於三聚物酸中添加氫而成氫化物的氫化三聚物酸等。
二聚物酸、三聚物酸可列舉例如:屬於油酸與亞麻油酸之反應物的二聚物酸、屬於油酸與亞麻油酸之反應物的三聚物酸、屬於丙烯酸之反應物的二聚物酸、屬於丙烯酸之反應物的三聚物酸、屬於甲基丙烯酸之反應物的二聚物酸、屬於甲基丙烯酸之反應物的三聚物酸、屬於丙烯酸與甲基丙烯酸之反應物的二聚物酸、屬於丙烯酸與甲基丙烯酸之反應物的三聚物酸、屬於油酸之反應物的二聚物酸、屬於油酸之反應物的三聚物酸、屬於亞麻油酸之反應物的二聚物酸、屬於亞麻油酸之反應物的三聚物酸、屬於次亞麻油酸之反應物的二聚物酸、屬於次亞麻油酸之反應物的三聚物酸、屬於丙烯酸與油酸之反應物的二聚物酸、屬於丙烯酸與油酸之反應物的三聚物酸、屬於丙烯酸與亞麻油酸之反應物的二聚物酸、屬於丙烯酸與亞麻油酸之反應物的三聚物酸、屬於丙烯酸與次亞麻油酸之反應物的二聚物酸、屬於丙烯酸與次亞麻油酸之反應物的三聚物酸、屬於甲基丙烯酸與油酸之反應物的二聚物酸、屬於甲基丙烯酸與油酸之反應物的三聚物酸、屬於甲基丙烯酸與亞麻油酸之反應物的二聚物酸、屬於甲基丙烯酸與亞麻油酸之反應物的三聚物酸、屬於甲基丙烯酸與次亞麻油酸之反應物的二聚物酸、屬於甲基丙烯酸與次亞麻油酸之反應物的三聚物酸、屬於油酸與次亞麻油酸之反應物的二聚物酸、屬於油酸與次亞麻油酸之反應物的三聚物酸、屬於亞麻油酸與次亞麻油酸之反應物的二聚物酸、屬於亞麻油酸與次亞麻油酸之反應物的三聚物酸、屬於上述各二聚物酸之氫化物的氫化二聚物酸、屬於上述各三聚物酸之氫化物的氫化三聚物酸等。
例如,屬於油酸與亞麻油酸之反應物的二聚物酸為碳數36的二聚物。又,屬於油酸與亞麻油酸之反應物的三聚物酸為碳數54的三聚物。
有機磺酸可列舉例如:脂肪族磺酸、芳香族磺酸等。脂肪族磺酸可列舉例如:烷烴磺酸、烷醇磺酸等。
烷烴磺酸可列舉例如:甲烷磺酸、乙烷磺酸、1-丙烷磺酸、2-丙烷磺酸、1-丁烷磺酸、2-丁烷磺酸、戊烷磺酸、己烷磺酸、癸烷磺酸、十二烷磺酸等。
烷醇磺酸可列舉例如:2-羥基乙烷-1-磺酸、2-羥基丙烷-1-磺酸、2-羥基丁烷-1-磺酸、2-羥基戊烷-1-磺酸、1-羥基丙烷-2-磺酸、3-羥基丙烷-1-磺酸、4-羥基丁烷-1-磺酸、2-羥基己烷-1-磺酸、2-羥基癸烷-1-磺酸及2-羥基十二烷-1-磺酸等。
芳香族磺酸可列舉例如:1-萘磺酸、2-萘磺酸、對甲苯磺酸、二甲苯磺酸、對酚磺酸、甲酚磺酸、磺酸基水楊酸、硝基苯磺酸、磺酸基苯甲酸及二苯胺-4-磺酸等。
酮酸以外的有機酸可單獨使用1種,亦可混合2種以上使用。
酮酸以外的有機酸較佳係包含選自由羧酸及有機磺酸所成群組中的1種以上。羧酸較佳為包含脂肪族二羧酸,更佳為包含戊二酸。有機磺酸較佳為包含芳香族磺酸,更佳為包含對甲苯磺酸。
前述助焊劑中的酮酸以外的有機酸的含量相對於助焊劑的總質量(100質量%)較佳為1質量%以上10質量%以下,更佳為2質量%以上6質量%以下。
前述助焊劑中的特定酮酸的含量相對於有機酸的總質量(100質量%)較佳為75質量%以上,更佳為80質量%以上,再佳為85質量%以上。特定酮酸之前述含量的上限值並無特別限定,可為100質量%。
藉由使特定酮酸的含量在前述下限值以上,更容易抑制孔洞產生。
[胺]
胺可列舉例如:唑類、胍類、烷胺化合物、胺醇化合物、胺聚氧伸烷基加成物等。
唑類可列舉例如:2-甲基咪唑、2-乙基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-十一烷基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-十一烷基咪唑鎓偏苯三酸酯、1-氰基乙基-2-苯基咪唑鎓偏苯三酸酯、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三、2,4-二胺基-6-[2’-十一烷基咪唑基-(1’)]-乙基-s-三、2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2,3-二氫-1H-吡咯并[1,2-a]苯并咪唑、氯化1-十二烷基-2-甲基-3-苄基咪唑鎓、2-甲基咪唑啉、2-苯基咪唑啉、2,4-二胺基-6-乙烯基-s-三、2,4-二胺基-6-乙烯基-s-三異三聚氰酸加成物、2,4-二胺基-6-甲基丙烯醯氧基乙基-s-三、環氧基-咪唑加成物、2-甲基苯并咪唑、2-辛基苯并咪唑、2-戊基苯并咪唑、2-(1-乙基戊基)苯并咪唑、2-壬基苯并咪唑、2-(4-噻唑基)苯并咪唑、苯并咪唑、1,2,4-三唑、2-(2’-羥基-5’-甲基苯基)苯并三唑、2-(2’-羥基-3’-第三丁基-5’-甲基苯基)-5-氯苯并三唑、2-(2’-羥基-3’,5’-二-第三戊基苯基)苯并三唑、2-(2’-羥基-5’-第三辛基苯基)苯并三唑、2,2’-亞甲基雙[6-(2H-苯并三唑-2-基)-4-第三辛基酚]、6-(2-苯并三唑基)-4-第三辛基-6’-第三丁基-4’-甲基-2,2’-亞甲基雙酚、1,2,3-苯并三唑、1-[N,N-雙(2-乙基己基)胺基甲基]苯并三唑、羧基苯并三唑、1-[N,N-雙(2-乙基己基)胺基甲基]甲基苯并三唑、2,2’-[[(甲基-1H-苯并三唑-1-基)甲基]亞胺基]雙乙醇、1-
(1’,2’-二羧基乙基)苯并三唑、1-(2,3-二羧基丙基)苯并三唑、1-[(2-乙基己胺基)甲基]苯并三唑、2,6-雙[(1H-苯并三唑-1-基)甲基]-4-甲基酚、5-甲基苯并三唑、5-苯基四唑等。
胍類可列舉例如:1,3-二苯基胍、1,3-二鄰甲苯基胍、1-鄰甲苯基雙胍、1,3-二鄰異丙苯基胍、1,3-二鄰異丙苯基-2-丙醯基胍等。
烷胺化合物可列舉例如:乙胺、三乙胺、乙二胺、三乙四胺、環己胺、十六烷胺、硬脂胺等。
胺醇化合物可列舉例如:單異丙醇胺等。
胺聚氧伸烷基加成物、可列舉例如:末端二胺聚烷二醇、脂肪族胺聚氧伸烷基加成物、芳香族胺聚氧伸烷基加成物、多胺聚氧伸烷基加成物等。
源自胺聚氧伸烷基加成物的環氧烷(alkylene oxide)可列舉例如:環氧乙烷、環氧丙烷、環氧丁烷等。
末端二胺聚烷二醇係聚烷二醇的兩末端經胺基化而成的化合物。
末端二胺聚烷二醇可列舉例如:末端二胺聚乙二醇、末端二胺聚丙二醇、末端二胺聚乙二醇-聚丙二醇共聚物等。
末端二胺聚乙二醇-聚丙二醇共聚物可列舉例如:聚乙二醇-聚丙二醇共聚物雙(2-胺基丙基)醚、聚乙二醇-聚丙二醇共聚物雙(2-胺基乙基)醚。
脂肪族胺聚氧伸烷基加成物、芳香族胺聚氧伸烷基加成物及多胺聚氧伸烷基加成物,係胺的氮原子與聚氧伸烷基鍵結而成者。前述胺可列舉例如:乙二胺、1,3-丙二胺、1,4-丁二胺、六亞甲基二胺、月桂胺、硬脂胺、油胺、牛脂胺、硬化牛脂胺、牛脂丙二胺、間二甲苯二胺、二乙三胺、間二甲苯二胺、甲苯二胺、對二甲苯二胺、苯二胺、異佛爾酮二胺、1,10-癸二胺、1,12-十二烷二
胺、4,4-二胺基二環己基甲烷、4,4-二胺基二苯基甲烷、丁烷-1,1,4,4-四胺、嘧啶-2,4,5,6-四胺等。
作為脂肪族胺聚氧伸烷基加成物,可舉出聚氧伸烷基烷胺。聚氧伸烷基烷胺可列舉例如聚氧伸烷基乙二胺。聚氧伸烷基乙二胺,係乙二胺的任一氮原子與至少1個聚氧伸烷基鍵結而成者。聚氧伸烷基乙二胺可列舉:聚氧伸乙基乙二胺、聚氧伸丙基乙二胺、聚氧伸乙基聚氧伸丙基乙二胺。聚氧伸乙基乙二胺,係乙二胺的任一氮原子與1個以上的聚氧伸乙基鍵結而成者;聚氧伸丙基乙二胺係乙二胺的任一氮原子與1個以上之聚氧伸丙基鍵結而成者。聚氧伸乙基聚氧伸丙基乙二胺係乙二胺的任一氮原子與至少1個聚氧伸丙基或聚氧伸乙基鍵結而成者。
聚氧伸烷基乙二胺可列舉例如:N-聚氧伸丙基乙二胺、N-聚氧伸乙基乙二胺、N-聚氧伸乙基聚氧伸丙基乙二胺、N,N,N’,N’-肆(2-羥乙基)乙二胺、N,N,N’,N’-肆(2-羥基丙基)乙二胺等。
胺可單獨使用1種,亦可混合2種以上使用。
胺較佳係包含選自由唑類、烷胺化合物及胺聚氧伸烷基加成物所成群組中的1種以上。
唑類較佳係包含2-乙基咪唑。
烷胺化合物較佳係包含三乙四胺。
胺聚氧伸烷基加成物較佳係包含末端二胺聚烷二醇及/或脂肪族胺聚氧伸烷基加成物。
作為脂肪族胺聚氧伸烷基加成物,較佳係包含聚氧伸烷基乙二胺,更佳係包含N,N,N’,N’-肆(2-羥基丙基)乙二胺。
作為末端二胺聚烷二醇,較佳係包含末端二胺聚乙二醇-聚丙二醇共聚物。
唑類及烷胺化合物的總含量相對於助焊劑的總質量(100質量%)較佳為0.5質量%以上6質量%以下,更佳為1質量%以上4質量%以下。
脂肪族胺聚氧伸烷基加成物的含量相對於助焊劑的總質量(100質量%)較佳為10質量%以上40質量%以下,更佳為15質量%以上30質量%以下。
[鹵化物]
鹵化物可列舉例如:胺氫鹵酸鹽、胺氫鹵酸鹽以外的有機鹵化物等。
胺氫鹵酸鹽係使胺與鹵化氫反應而成的化合物。
此處的胺可列舉:脂肪族胺、唑類、胍類等。鹵化氫可列舉例如:氯、溴、碘的氫化物。
脂肪族胺可列舉例如:乙胺、二乙胺、三乙胺、乙二胺等。胍類及唑類可列舉在「胺」的段落中所述者。
更具體而言,胺氫鹵酸鹽可列舉例如:環己胺氫溴酸鹽、十六烷基胺氫溴酸鹽、硬脂醯胺氫溴酸鹽、乙胺氫溴酸鹽、二苯基胍氫溴酸鹽、乙胺鹽酸鹽、硬脂醯胺鹽酸鹽、二乙基苯胺鹽酸鹽、二乙醇胺鹽酸鹽、2-乙基己胺氫溴酸鹽、吡啶氫溴酸鹽、異丙胺氫溴酸鹽、二乙胺氫溴酸鹽、二甲胺氫溴酸鹽、二甲胺鹽酸鹽、松香胺氫溴酸鹽、2-乙基己胺鹽酸鹽、異丙胺鹽酸鹽、環己胺鹽酸鹽、2-甲基哌啶氫溴酸鹽、1,3-二苯基胍鹽酸鹽、二甲基苄胺鹽酸鹽、水合肼氫溴酸鹽、二甲基環己胺鹽酸鹽、三壬胺氫溴酸鹽、二乙基苯胺氫溴酸鹽、2-二乙胺基乙醇氫溴酸鹽、2-二乙胺基乙醇鹽酸鹽、氯化銨、二烯丙胺鹽酸鹽、二烯丙胺氫溴酸鹽、二乙胺鹽酸鹽、三乙胺氫溴酸鹽、三乙胺鹽酸鹽、肼一鹽酸鹽、肼二鹽酸鹽、肼一氫溴酸鹽、肼二氫溴酸鹽、吡啶鹽酸鹽、苯胺氫溴酸鹽、丁胺鹽
酸鹽、己基胺鹽酸鹽、正辛胺鹽酸鹽、十二烷胺鹽酸鹽、二甲基環己胺氫溴酸鹽、乙二胺二氫溴酸鹽、松香胺氫溴酸鹽、2-苯基咪唑氫溴酸鹽、4-苄基吡啶氫溴酸鹽、L-麩胺酸鹽酸鹽、N-甲基啉鹽酸鹽、甜菜鹼鹽酸鹽、2-甲基哌啶氫碘酸鹽、環己胺氫碘酸鹽、1,3-二苯胍氫氟酸鹽、二乙胺氫氟酸鹽、2-乙基己胺氫氟酸鹽、環己胺氫氟酸鹽、乙胺氫氟酸鹽、松香胺氫氟酸鹽、環己胺四氟硼酸鹽及二環己胺四氟硼酸鹽等。
又,作為鹵化物,例如亦可使用胺與四氟硼酸(HBF4)反應而成的鹽、胺與三氟化硼(BF3)反應而成的錯合物。
前述錯合物可列舉例如:三氟化硼哌啶等。
胺氫鹵酸鹽以外的有機鹵化物可列舉例如:鹵化脂肪族化合物。鹵化脂肪族烴基係指構成脂肪族烴基之氫原子的一部分或全部由鹵素原子取代而成者。
鹵化脂肪族化合物可列舉:鹵化脂肪族醇、鹵化雜環式化合物。
鹵化脂肪族醇可列舉例如:1-溴-2-丙醇、3-溴-1-丙醇、3-溴-1,2-丙二醇、1-溴-2-丁醇、1,3-二溴-2-丙醇、2,3-二溴-1-丙醇、1,4-二溴-2-丁醇、反式-2,3-二溴-2-丁烯-1,4-二醇等。
鹵化雜環式化合物可列舉例如:下述通式(2)表示的化合物。
R21-(R22)n (2)
[式中,R21表示n價的雜環式基;R22表示鹵化脂肪族烴基]。
作為R21中的n價雜環式基的雜環,可列舉:構成脂肪族烴或芳香族烴環的碳原子的一部分經雜原子取代而成的環結構。此雜環中的雜原子可
列舉氧原子、硫原子、氮原子等。此雜環較佳為3至10員環,更佳為5至7員環。此雜環可列舉例如:三聚異氰酸酯環等。
R22中的鹵化脂肪族烴基,較佳係碳數1至10,更佳係碳數2至6,再佳係碳數3至5。又,R22較佳為溴化脂肪族烴基、氯化脂肪族烴基,更佳為溴化脂肪族烴基,再佳為溴化飽和脂肪族烴基。
鹵化雜環式化合物可列舉例如:參-(2,3-二溴丙基)三聚異氰酸酯等。
又,胺氫鹵酸鹽以外的有機鹵化物可列舉例如:2-碘苯甲酸、3-碘苯甲酸、2-碘丙酸、5-碘水楊酸、5-碘鄰胺苯甲酸等碘化羧基化合物;2-氯苯甲酸、3-氯丙酸等氯化羧基化合物;2,3-二溴丙酸、2,3-二溴丁二酸、2-溴苯甲酸等溴化羧基化合物等鹵化羧基化合物。
鹵化物可單獨使用1種,亦可混合2種以上使用。
≪界面活性劑≫
界面活性劑可列舉例如:非離子界面活性劑等。
非離子界面活性劑可列舉:聚烷二醇類。
源自聚烷二醇類的環氧烷可列舉例如:環氧乙烷、環氧丙烷、環氧丁烷等。
聚烷二醇類可列舉例如:聚乙二醇、環氧乙烷-間苯二酚共聚物、聚氧伸烷基乙炔二醇類、聚氧伸烷基甘油醚、聚氧伸烷基烷醚、聚氧基伸烷酯、聚氧伸烷基烷醯胺等。
或是非離子界面活性劑可列舉:醇的聚氧伸烷基加成物。前述醇可列舉例如:脂肪族醇、芳香族醇、多元醇。
界面活性劑可單獨使用1種,亦可混合2種以上使用。
本實施型態之水溶性助焊劑較佳係含有界面活性劑。
界面活性劑較佳係包含非離子界面活性劑,更佳係包含選自由環氧乙烷-間苯二酚共聚物及脂肪族醇聚氧伸烷基加成物所成群組中的1種以上。
界面活性劑的含量相對於助焊劑的總質量(100質量%)較佳為5質量%以上75質量%以下,更佳為5質量%以上65質量%以下,再佳為5質量%以上30質量%以下。
≪金屬鈍化劑≫
金屬鈍化劑可列舉例如:受阻酚系化合物、氮化物等。
此處所述的「金屬鈍化劑」,係指具有防止金屬因與某種化合物的接觸而劣化之性能的化合物。
所謂的受阻酚系化合物,係指酚的鄰位的至少一邊具有大體積之取代基(例如第三丁基等分支狀或環狀烷基)的酚系化合物。
受阻酚系化合物並無特別限定,可列舉例如:雙[3-(3-第三丁基-4-羥基-5-甲基苯基)丙酸][伸乙基雙(氧基伸乙基)]、N,N’-六亞甲基雙[3-(3,5-二-第三丁基-4-羥基苯基)丙醯胺]、1,6-己二醇雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、2,2’-亞甲基雙[6-(1-甲基環己基)-對甲酚]、2,2’-亞甲基雙(6-第三丁基-對甲酚)、2,2’-亞甲基雙(6-第三丁基-4-乙基酚)、三乙二醇-雙[3-(3-第三丁基-5-甲基-4-羥基苯基)丙酸酯]、1,6-己二醇-雙-[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、2,4-雙-(正辛基硫基)-6-(4-羥基-3,5-二-第三丁基苯胺基)-1,3,5-三、新戊四醇肆[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、2,2-硫基-二伸乙基雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、十八烷基-3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯、N,N’-六亞甲基雙(3,5-二-第三丁基-4-羥基-氫桂皮醯胺)、3,5-二-第三丁基-4-羥基苄基膦酸二乙酯、
1,3,5-三甲基-2,4,6-參(3,5-二-第三丁基-4-羥基苄基)苯、N,N’-雙[2-[2-(3,5-二-第三丁基-4-羥基苯基)乙基羰氧基]乙基]草醯胺、下述通式(3)表示的化合物等。
(式中,Z為可經取代之伸烷基;R101及R102分別獨立地為可經取代的烷基、芳烷基、芳基、雜芳基、環烷基或雜環烷基;R103及R104分別獨立地為可經取代的烷基)。
金屬鈍化劑中的氮化合物可列舉例如:醯肼系氮化合物、醯胺系氮化合物、三唑系氮化合物、三聚氰胺系氮化合物等。
醯肼系氮化合物只要是具有醯肼骨架的氮化合物即可,可列舉:十二烷二酸雙[N2-(2羥基苯甲醯基)肼]、N,N’-雙[3-(3,5-二-第三丁基-4-羥基苯基)丙醯基]肼、癸二羧酸二柳醯肼、N-亞柳基-N’-柳基醯肼、間硝基苯并醯肼、3-胺基鄰苯二甲醯肼、鄰苯二甲二醯肼、己二醯肼、草醯基雙(2-羥基-5-辛基亞苄基醯肼)、N’-苯甲醯基吡咯啶酮羧醯肼、N,N’-雙(3-(3,5-二-第三丁基-4-羥基苯基)丙醯基)肼等。
醯胺系氮化合物只要是具有醯胺骨架的氮化合物即可,可列舉:N,N’-雙{2-[3-(3,5-二-第三丁基-4-羥基苯基)丙醯氧基]乙基}草醯胺等。
三唑系氮化合物只要是具有三唑骨架的氮化合物即可,可列舉:N-(2H-1,2,4-三唑-5-基)柳醯胺、3-胺基-1,2,4-三唑、3-(N-柳醯基)胺基-1,2,4-三唑等。
三聚氰胺系氮化合物只要是具有三聚氰胺骨架的氮化合物即可,可列舉:三聚氰胺、三聚氰胺衍生物等。更具體可列舉例如:參胺基三、烷基化參胺基三、烷氧基烷基化參胺基三、三聚氰胺、烷基化三聚氰胺、烷氧基烷基化三聚氰胺、N2-丁基三聚氰胺、N2,N2-二乙基三聚氰胺、N,N,N’,N’,N”,N”-陸(甲氧基甲基)三聚氰胺等。
金屬鈍化劑可單獨使用1種,亦可混合2種以上使用。
本實施型態之助焊劑較佳係不含樹脂成分。本說明書中,樹脂成分可列舉例如:松香、松香以外的樹脂等。
本說明書中所述之「松香」,係包含以松香酸作為主成分而含有松香酸與其異構物之混合物的天然樹脂、及將天然樹脂進行化學修飾而成者(有時亦稱為松香衍生物)。
天然樹脂中的松香酸含量,作為一例,係相對於天然樹脂為40質量%以上80質量%以下。
本說明書中所述的「主成分」,係指構成化合物的成分之中,其化合物中的含量為40質量%以上的成分。
作為代表性的松香酸之異構物,可列舉:新松香酸、長葉松酸(Palustric acid)、左旋海松酸(Levopimaric acid)等。松香酸的結構呈示如下。
前述「天然樹脂」可列舉例如:膠松香、木松香及妥爾油松香等。
本發明中所述的「對於天然樹脂進行化學修飾而成者(松香衍生物)」,係包含對前述「天然樹脂」實施選自由氫化、脫氫化、中和、環氧烷加成、醯胺化、二聚化及多聚化、酯化以及狄耳士-阿爾德(Diels-Alder)環化加成所成群組中的1種以上之處理而成者。
松香衍生物可列舉例如:精製松香、改性松香等。
改性松香可列舉例如:氫化松香、聚合松香、聚合氫化松香、岐化松香、酸改性松香、松香酯、酸改性氫化松香、無羥基改性氫化松香、酸改性岐化松香、酸酐改性岐化松香、酚改性松香及α,β不飽和羧酸改性物(丙烯酸改性松香、馬來酸改性松香、富馬酸改性松香等)、以及該聚合松香的精製物、氫化物及岐化物、以及該α,β不飽和羧酸改性物的精製物、氫化物及岐化物、松香醇、松香胺、氫化松香醇、松香酯、氫化松香酯、松香皂、氫化松香皂、酸改性松香皂等。
松香胺可列舉例如:脫氫松香基胺(dehydroabiethylamine)、二氫松香基胺(dihydroabiethylamine)等。松香胺係指岐化松香胺。脫氫松香基胺、二氫松香基胺的各結構呈示如下。
松香以外的樹脂可列舉例如:萜烯樹脂、改性萜烯樹脂、萜烯酚樹脂、改性萜烯酚樹脂、苯乙烯樹脂、改性苯乙烯樹脂、二甲苯樹脂、改性二甲苯樹脂、丙烯酸樹脂、聚乙烯樹脂、丙烯酸-聚乙烯共聚合樹脂、其他熱硬化性樹脂等。
改性萜烯樹脂可列舉:芳香族改性萜烯樹脂、氫化萜烯樹脂、氫化芳香族改性萜烯樹脂等。改性萜烯酚樹脂可列舉:氫化萜烯酚樹脂等。改性苯乙烯樹脂可列舉:苯乙烯丙烯酸樹脂、苯乙烯馬來酸樹脂等。改性二甲苯樹脂可列舉:酚改性二甲苯樹脂、烷基酚改性二甲苯樹脂、酚改性間苯二甲酚型二甲苯樹脂、多元醇改性二甲苯樹脂、聚氧伸乙基加成二甲苯樹脂等。
其他熱硬化性樹脂可列舉例如:環氧樹脂。
環氧樹脂可列舉例如:雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、環氧丙基胺型樹脂、脂環族環氧樹脂、胺基丙烷型環氧樹脂、聯苯型環氧樹脂、萘型環氧樹脂、蒽型環氧樹脂、三型環氧樹脂、二環戊二烯型環氧樹脂、三苯基甲烷型環氧樹脂、茀型環氧樹脂、酚芳烷基型環氧樹脂、酚醛清漆型環氧樹脂等。
本實施型態之助焊劑因為不含選自由松香及熱硬化性樹脂所成群組中的至少1種以上之樹脂成分,作為水溶性助焊劑更為理想。
以上說明的本實施型態之水溶性助焊劑,藉由含有熔點40℃以下的酮酸與沸點240℃以下的溶劑並將其組合,在回焊時(回焊溫度為例如180至300℃),可進一步抑制孔洞產生。可得到此效果的理由尚不明確,但推論如下。
廣泛作為活性劑使用的二羧酸等有機酸,通常熔點在100℃左右或100℃以上。相對於此,本實施型態之水溶性助焊劑中的特定酮酸熔點在40℃以下。本實施型態之水溶性助焊劑藉由含有特定酮酸,在回焊時,焊膏的流動性更高。又,本實施型態之水溶性助焊劑中的特定溶劑其沸點在240℃以下,因此在回焊時會揮發而容易產生氣泡(孔洞)。推測藉由此等的加乘效果,在焊膏中產生之孔洞互相融合而變大,孔洞容易從焊膏排出。
再者,特定酮酸的沸點在250℃以下的情況,特定酮酸會與溶劑一起揮發,因此推測孔洞更容易從焊膏排出。
(焊膏)
本實施型態的焊膏含有焊料合金粉末與上述助焊劑。
焊料合金粉末可由Sn單體的焊料粉體構成,或是亦可由Sn-Ag系、Sn-Cu系、Sn-Ag-Cu系、Sn-Bi系、Sn-In系等或是在此等合金中添加Sb、Bi、In、Cu、Zn、As、Ag、Cd、Fe、Ni、Co、Au、Ge、P等而成之焊料合金的粉體構成。
焊料合金粉末亦可由Sn-Pb系或是在Sn-Pb系中添加Sb、Bi、In、Cu、Zn、As、Ag、Cd、Fe、Ni、Co、Au、Ge、P等而成之焊料合金的粉體構成。
焊料合金粉末較佳為不含Pb的焊料。
焊料合金粉末例如可使用其熔融溫度為150至250℃者。
助焊劑的含量:
焊膏中,助焊劑的含量相對於焊膏的總質量為5至30質量%,更佳為5至15質量%。
本實施型態之焊膏因為含有包含熔點40℃以下的酮酸與沸點240℃以下之溶劑的助焊劑,故可進一步抑制孔洞產生。
如上所述,本實施型態之焊膏,推測係在回焊時因為特定酮酸及特定溶劑揮發而孔洞容易從焊膏排出。孔洞容易從焊膏排出之助焊劑的構成如下。
亦即,前述助焊劑係含有特定酮酸與特定溶劑者,特定酮酸的沸點(Tk)及特定溶劑的沸點(Ts)較佳係滿足以下的條件。
Tk較佳為150℃以上280℃以下,更佳為200℃以上270℃以下,再佳為220℃以上260℃以下,特佳為230℃以上250℃以下。
Ts較佳為150℃以上240℃以下,更佳為180℃以上235℃以下,再佳為200℃以上230℃以下,特佳為210℃以上225℃以下。
Tk與Ts的溫度差△T的絕對值較佳為0℃以上,更佳為3℃以上,再佳為5℃以上。
藉由使△T在前述下限值以上,更容易抑制孔洞產生。
△T較佳為70℃以下,更佳為60℃以下,再佳為55℃以下。
藉由使△T在前述上限值以下,更容易抑制孔洞產生。
前述助焊劑中,特定酮酸的含量相對於前述助焊劑的總量(100質量%)較佳為10質量%以上25質量%以下,可為15質量%以上25質量%以下,亦可為15質量%以上20質量%以下。
前述助焊劑中,特定溶劑的含量相對於前述助焊劑的總量(100質量%)較佳為10質量%以上70質量%以下,更佳為15質量%以上60質量%以下。
再者,Tk及Ts較佳係滿足Ts<Tk的關係。
滿足此關係的情況,回焊溫度到達焊料熔融溫度時,特定酮酸會與已開始揮發之特定溶劑一起揮發。藉此,孔洞容易從焊膏排出。
Ts<Tk時,△T較佳為5℃以上50℃以下,更佳為10℃以上45℃以下,再佳為15℃以上40℃以下,特佳為20℃以上35℃以下。
藉由使△T在前述範圍內,更容易抑制孔洞產生。
[實施例]
以下藉由實施例說明本發明,但本發明不限於以下的實施例。
<助焊劑的製備>
(實施例1至9、比較例1至4)
依照表1至表2所示的組成調製實施例及比較例的各助焊劑。
使用的原料如下所示。
實施例中使用之化合物的熔點值係記載於「化學手冊 基礎編 修訂5版(日本化學會,丸善出版社)」中所記載之值。實施例中使用之化合物的沸點值係對象液體之飽和蒸氣壓等於1大氣壓(亦即1013hPa)時所測定之該液體溫度而得的值。
特定酮酸:
乙醯丙酸(熔點:37.2℃,沸點:245℃)、丙酮酸(熔點:13.6℃,沸點:165℃);
其他酮酸:
丙酮二羧酸(熔點:138℃,沸點:408.4℃)
其他有機酸:
戊二酸、對甲苯磺酸
胺:
2-乙基咪唑、三乙四胺
N,N,N’,N’-肆(2-羥基丙基)乙二胺
末端二胺聚乙二醇-聚丙二醇共聚物(重量平均分子量600)
特定溶劑:
α-萜品醇(沸點:217℃)、乙二醇單苯醚(沸點:237℃)、己二醇(沸點:197℃)
其他溶劑:
二乙二醇單己醚(沸點:258℃)、二乙二醇單-2-乙基己醚(沸點:272℃)
界面活性劑:
聚氧伸乙基間苯二酚(重量平均分子量1136)
聚氧伸乙基二十二烷醚(環氧乙烷平均加成莫耳數:30mol)
<焊膏的製備>
將各例的助焊劑與下述焊料合金粉末分別混合以調製焊膏。調製之焊膏皆為助焊劑11質量%、焊料合金粉末89質量%。
焊膏中的焊料合金粉末係由3質量%的Ag、0.5質量%的Cu且殘餘部分為Sn的焊料合金構成之粉末。
此焊料合金的固相線溫度為217℃,液相線溫度為219℃。
焊料合金粉末,係在JIS Z 3284-1:2014中的粉末尺寸之分類(表2)中,滿足符號4的尺寸(粒度分布)。
<孔洞面積率的評價>
驗證方法:
使用金屬遮罩(開口部的尺寸與電極尺寸相同,遮罩厚度80μm),在經Ni/Au鍍覆處理的電極上印刷焊膏。接著,在印刷有焊膏之電極搭載QFN(1邊的長度為4mm,底面電極1邊的長度為1.7mm)。接著進行回焊而完成焊接。
圖1係呈示回焊溫度曲線的圖。回焊溫度曲線係從150℃至180℃保持70秒以進行預熱,在220℃以上保持60秒,峰值為245℃。
對已焊接之接合體,從基板的垂直方向照射X光,藉由分析穿透X光,測定孔洞面積。測定係使用XD7600NT Diamond X光檢查系統(Nordson DAGE公司製)。孔洞面積的測定中,X光再通過至少1個孔洞時,則作為存在孔洞者而進行測定。孔洞係檢測直徑0.1μm以上者。接著,算出孔洞總面積相對於底面電極總面積的比率,作為孔洞面積率(%)。
使用不含特定溶劑之比較例1至2的助焊劑時,無法充分抑制孔洞產生。
又,不含特定酮酸的比較例3至4之助焊劑,無法充分抑制孔洞產生。
使用含有特定酮酸及特定溶劑之實施例1至9的助焊劑時,相較於使用比較例之助焊劑的情況,可進一步抑制孔洞產生。
含有乙醯丙酸(沸點245℃)及α-萜品醇(沸點217℃)的實施例1之助焊劑,相較於含有丙酮酸(沸點165℃)及α-萜品醇(沸點217℃)的實施例4之助焊劑,可進一步抑制孔洞產生。
實施例1中,回焊溫度到達焊料熔融溫度時,乙醯丙酸(特定酮酸)與已開始揮發的α-萜品醇一起揮發。另一方面,實施例4中,回焊溫度到達焊料熔融溫度之前,丙酮酸(特定酮酸)已開始揮發,之後α-萜品醇揮發。因為此點不同而認為實施例1的助焊劑中,相較於實施例4的助焊劑,孔洞更容易從焊膏排出。
[產業上的可利用性]
根據本發明,可提供可進一步抑制孔洞產生的助焊劑及焊膏。此助焊劑及焊膏適合在封裝周邊不具有引線的QFN等的焊接。
Claims (9)
- 一種水溶性助焊劑,含有熔點40℃以下的酮酸與沸點240℃以下的溶劑。
- 如請求項1所述之水溶性助焊劑,其中前述酮酸的沸點進一步為250℃以下。
- 如請求項1所述之水溶性助焊劑,其中前述酮酸的含量相對於水溶性助焊劑的總質量為10至25質量%。
- 如請求項1所述之水溶性助焊劑,其中前述酮酸包含分子內具有1個羧基的有機酸。
- 如請求項1所述之水溶性助焊劑,其中前述酮酸包含乙醯丙酸。
- 如請求項1所述之水溶性助焊劑,其中前述酮酸與前述溶劑的比率,以溶劑/酮酸所示的質量比計為0.60至4.0。
- 如請求項1所述之水溶性助焊劑,其更含有非離子界面活性劑及胺。
- 如請求項1所述之水溶性助焊劑,其不含選自由松香及熱硬化性樹脂所成群組中的1種以上之樹脂成分。
- 一種焊膏,其含有焊料合金粉末與如請求項1至8中任一項所述之水溶性助焊劑。
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JP6398464B2 (ja) | 2014-08-26 | 2018-10-03 | 三菱マテリアル株式会社 | ハンダペースト用水溶性フラックス及びハンダペースト |
US20170173745A1 (en) * | 2015-12-22 | 2017-06-22 | International Business Machines Corporation | No clean flux composition and methods for use thereof |
JP6332525B1 (ja) * | 2017-05-25 | 2018-05-30 | 千住金属工業株式会社 | ソルダペースト |
JP2021065929A (ja) * | 2019-10-28 | 2021-04-30 | パナソニックIpマネジメント株式会社 | はんだペースト及び接合構造体 |
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2022
- 2022-10-04 CN CN202280072746.6A patent/CN118215555A/zh active Pending
- 2022-10-04 JP JP2023559473A patent/JPWO2023084949A1/ja active Pending
- 2022-10-04 WO PCT/JP2022/037136 patent/WO2023084949A1/ja active Application Filing
- 2022-10-04 KR KR1020247015202A patent/KR20240105383A/ko unknown
- 2022-10-17 TW TW111139299A patent/TW202333882A/zh unknown
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JPWO2023084949A1 (zh) | 2023-05-19 |
WO2023084949A1 (ja) | 2023-05-19 |
KR20240105383A (ko) | 2024-07-05 |
CN118215555A (zh) | 2024-06-18 |
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