CN116096528A - 助焊剂和焊膏 - Google Patents
助焊剂和焊膏 Download PDFInfo
- Publication number
- CN116096528A CN116096528A CN202180051885.6A CN202180051885A CN116096528A CN 116096528 A CN116096528 A CN 116096528A CN 202180051885 A CN202180051885 A CN 202180051885A CN 116096528 A CN116096528 A CN 116096528A
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- Prior art keywords
- acid
- content
- organic
- flux
- flux according
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- 239000013543 active substance Substances 0.000 claims abstract description 8
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- 125000001931 aliphatic group Chemical group 0.000 claims description 10
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- 239000005642 Oleic acid Substances 0.000 description 5
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- 125000002091 cationic group Chemical group 0.000 description 4
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- 238000000034 method Methods 0.000 description 4
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- 229940035437 1,3-propanediol Drugs 0.000 description 3
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- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/362—Selection of compositions of fluxes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3601—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with inorganic compounds as principal constituents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
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Abstract
一种助焊剂,其包含作为活性剂的2‑羟基异丁酸0.1wt%~20wt%、阳离子系表面活性剂10wt%~60wt%、非离子系表面活性剂5wt%~60wt%。一种焊膏,其包含该助焊剂和金属粉。
Description
技术领域
本发明涉及用于焊接的助焊剂和使用该助焊剂的焊膏。
背景技术
一般而言,在焊接中使用助焊剂。助焊剂将存在于焊料的表面的金属氧化物以及存在于焊接的对象物的金属表面的金属氧化物以化学方式去除。由此,能够在焊料与对象物的边界上进行金属元素的移动,两者被牢固地接合。
助焊剂被分类为树脂系助焊剂、水溶性助焊剂和无机助焊剂。树脂系助焊剂是在松香或合成树脂等树脂中添加了活性剂的助焊剂。水溶性助焊剂是在水或有机溶剂等溶剂中溶解了有机酸系的活性剂而成的助焊剂。在有机酸系的活性剂之外,有时还将聚乙二醇、水溶性基础剂等添加到水溶性助焊剂中。无机助焊剂是使用了盐酸、氯化锌等无机系的材料的助焊剂。
焊膏是将焊料合金的粉末与助焊剂混合而得的复合材料。使用了焊膏的焊接例如如下进行。首先,在基板的电极等焊接部印刷焊膏。接着,在焊接部搭载部件。然后,在被称为回流炉的加热炉中加热基板。由此,在焊接部接合了部件。以下,也将接合了部件的焊接部称为“焊料接合部”。
专利文献1公开了一种水溶性助焊剂,其包含碳原子数为20以下的酸酐、表面活性剂和基础树脂。在该以往的助焊剂中,酸酐通过吸收水而作为活性剂发挥功能。出于使水等低分子极性分子与助焊剂成分相容的目的而添加表面活性剂。作为表面活性剂,可例示阴离子性、阳离子性、两性以及非离子性的表面活性剂。专利文献1还公开了包含上述必要成分的助焊剂抑制了焊接部中的空洞的产生的实施例。
现有技术文献
专利文献
专利文献1:日本特开2016-179496号公报
发明内容
发明所要解决的课题
顺便提及,关于向助焊剂添加表面活性剂的目的,典型的是,改善焊接时的焊料的润湿性。然而,表面活性剂本身也是空洞的原因物质。因此,在使用含有表面活性剂作为必要成分的助焊剂的焊接中,抑制焊料接合部中的空洞的产生的技术的开发在研究专利文献1的助焊剂的替代品方面也是重要的。
本发明的一个目的在于,在使用含有表面活性剂作为必要成分的助焊剂的焊接中,抑制焊料接合部处的空洞的产生。本发明的另一目的在于提供使用了这样的助焊剂的焊膏。
用于解决课题的手段
本发明人等发现,在含有阳离子系和非离子系的表面活性剂的助焊剂中添加2-羟基异丁酸(以下,也称为“HBA”)时,与未添加HBA的助焊剂相比,能够抑制空洞的产生。因此,本发明人等进行了进一步的研究,结果发现若这些成分的含量分别处于适当的范围,则能够充分抑制空洞的产生,从而完成了本发明。
第1发明是具有如下特征的助焊剂。
上述助焊剂包含:
作为活性剂的2-羟基异丁酸0.1~20wt%、
阳离子系表面活性剂10~60wt%、
非离子系表面活性剂5~60wt%。
第2发明是在第1发明中还具有如下特征。
上述2-羟基异丁酸的含量为1~10wt%。
第3发明是在第1或第2发明中还具有如下特征。
上述阳离子系表面活性剂是脂肪族单胺或脂肪族二胺的环氧烷加成物。
第4发明是在第1~3发明中还具有如下特征。
上述非离子系表面活性剂为脂肪族一元醇或芳香族多元醇的环氧烷加成物、或山梨糖醇酐脂肪酸酯中的至少一者。
第5发明是在第1~4发明中还具有如下特征。
上述助焊剂还包含活性助剂。
上述活性助剂为上述2-羟基异丁酸以外的其他有机酸、胺、有机磷化合物、有机硫化合物、有机卤化物、胺氢卤酸盐中的至少一种。
第6发明是在第5发明中还具有如下特征。
上述其他有机酸的含量超过0wt%且为10wt%以下。
第7发明是在第5或第6发明中还具有如下特征。
上述胺的含量超过0wt%且为5wt%以下。
第8发明是在第5~7发明的任一项中还具有如下特征。
上述有机磷化合物的含量超过0wt%且为3wt%以下。
第9发明是在第5~8发明的任一项中还具有如下特征。
上述有机硫化合物的含量超过0wt%且为3wt%以下。
第10发明是在第5~9发明的任一项中还具有如下特征。
上述有机卤化物的含量超过0wt%且为5wt%以下。
第11发明是在第5~10发明的任一项中还具有如下特征。
上述胺氢卤酸盐的含量超过0wt%且为2wt%以下。
第12发明是在第1~11发明的任一项中还具有如下特征。
上述助焊剂还包含超过0wt%且为0.5wt%以下的树脂组合物。
第13发明是在第1~12发明的任一项中还具有如下特征。
上述助焊剂还包含超过0wt%且为76wt%以下的溶剂。
第14发明是具有如下特征的焊膏。
上述焊膏包含第1~13发明的任一项中的助焊剂、和金属粉。
具体实施方式
以下对本发明的实施方式进行详细说明。需要说明的是,在本申请中,“wt%”是指“质量%”。另外,构成助焊剂的成分的wt%以助焊剂整体的质量为基准。另外,在使用“~”表示数值范围的情况下,其范围包含两端的数值。
1.助焊剂
实施方式的助焊剂含有作为活性剂的HBA、阳离子系以及非离子系的表面活性剂作为必要成分。以下,对这些成分和各成分的含量(含有比例)进行详细说明。
1-1.HBA
HBA是具有在具有甲基和羟基的碳原子上键合了羧基的结构的有机酸。HBA的含量为0.1~20wt%。若HBA的含量少于0.1wt%,则HBA对氧化物的还原作用变弱,焊接时的焊料的润湿性降低。若HBA的含量多于20wt%,则HBA容易腐蚀焊接的对象物的金属表面。HBA的含量优选为1~10wt%,更优选为1~5wt%。如果HBA的含量在该范围内,则能够在抑制HBA所导致的金属表面的腐蚀的同时,去除氧化物。
1-2.阳离子系和非离子系表面活性剂
1-2-1.阳离子系表面活性剂
作为阳离子系表面活性剂,可例示有机胺环氧烷(AO)型的阳离子系表面活性剂和聚氧化烯胺型的阳离子系表面活性剂。
有机胺AO型的表面活性剂具有在脂肪族胺(脂肪族单胺及多胺(脂肪族二胺及脂肪族三胺))或芳香族胺(芳香族单胺及多胺(芳香族二胺及芳香族三胺))等有机胺中加成了选自环氧乙烷(EO)、环氧丙烷(PO)和环氧丁烷(BO)中的至少一种AO的结构。作为有机胺AO型的表面活性剂,优选使用脂肪族单胺和脂肪族二胺的AO加成物,更优选使用脂肪族单胺的EO加成物和脂肪族二胺的PO加成物。
聚氧化烯胺型的表面活性剂具有在分子内具有氧化乙烯嵌段、氧化丙烯嵌段等氧化烯嵌段的重复单元、且在末端的碳原子上键合有氨基的结构。根据末端氨基的总数,分类为单胺型、二胺型和三胺型。作为聚氧化烯胺型的表面活性剂,优选使用聚氧二胺型的表面活性剂,更优选使用分子内具有氧化乙烯嵌段、氧化丙烯嵌段的重复单元并且在两末端的碳原子键合有氨基的聚氧化烯胺型的表面活性剂。
阳离子系表面活性剂的含量(在使用2种以上的阳离子系表面活性剂的情况下,它们的总含量)为10~60wt%。若阳离子系表面活性剂的含量少于10wt%,则焊接时的焊料的润湿性降低。若阳离子系表面活性剂的含量多于60wt%,则容易产生空洞。从兼顾润湿性的提高和抑制空洞的产生的观点出发,阳离子系表面活性剂的含量优选为20~46wt%,更优选为30~46wt%。
1-2-2.非离子系表面活性剂
作为非离子系表面活性剂,可例示醇醚型的非离子系表面活性剂和羧酸酯型的非离子系表面活性剂。
醇醚型的表面活性剂具有在脂肪族醇(包括一元醇和多元醇)或芳香族醇(包括一元醇和多元醇)上加成有选自环氧乙烷(EO)、环氧丙烷(PO)和环氧丁烷(BO)中的至少一种AO的结构。作为脂肪族一元醇,可例示甲醇、乙醇、丁醇等低级醇与鲸蜡醇、硬脂醇、山萮醇、油醇等高级醇。作为芳香族一元醇,可例示苯酚和苯甲醇。作为芳香族多元醇,可例示间苯二酚。
作为醇醚型的表面活性剂,优选使用脂肪族一元醇或芳香族多元醇的AO加成物,更优选使用聚乙二醇(PEG)、聚丙二醇(PPG)、PEG与PPG的共聚物、以及间苯二酚的EO加成物。
羧酸酯型的表面活性剂是脂肪族羧酸(包括单羧酸和多元羧酸)或芳香族羧酸(包括单羧酸和多元羧酸)与脂肪族醇(包括一元醇和多元醇)或芳香族醇(包括一元醇和多元醇)的酯。作为羧酸酯型的表面活性剂,优选使用山梨糖醇酐脂肪酸酯(脂肪族羧酸与山梨糖醇酐的酯),更优选使用山梨糖醇酐单月桂酸酯和山梨糖醇酐单硬脂酸酯。
非离子系表面活性剂的含量(在使用2种以上的非离子系表面活性剂的情况下,它们的总含量)为5~60wt%。若非离子系表面活性剂的含量少于5wt%,则焊接时的焊料的润湿性降低。若非离子系表面活性剂的含量多于60wt%,则在焊接时助焊剂难以气化。从该观点出发,非离子系表面活性剂的含量的上限优选低。具体而言,上限优选为50wt%,更优选为45wt%。
1-3.活性助剂
实施方式的助焊剂可以含有活性助剂。即,实施方式的助焊剂含有活性助剂作为任选成分。活性助剂是辅助HBA对氧化物的还原的添加剂。作为活性助剂,可例示HBA以外的其他有机酸、胺、有机磷化合物、有机硫化合物、有机卤化物和胺氢卤酸盐。这些活性助剂可以同时使用2种以上。
1-3-1.其他有机酸
作为其他有机酸,可例示戊二酸、己二酸、壬二酸、二十烷二酸、柠檬酸、乙醇酸、乳酸、琥珀酸、水杨酸、二甘醇酸、吡啶二羧酸(ジピコリン酸)、二丁基苯胺二甘醇酸、辛二酸、癸二酸、巯基乙酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、十二烷二酸、对羟基苯基乙酸、吡啶甲酸、苯基琥珀酸、富马酸、马来酸、丙二酸、月桂酸、苯甲酸、酒石酸、异氰脲酸三(2-羧基乙基)酯、甘氨酸、1,3-环己烷二羧酸、2,2-双(羟基甲基)丙酸、2,2-双(羟基甲基)丁酸、4-叔丁基苯甲酸、2,3-二羟基苯甲酸、2,4-二乙基戊二酸、2-喹啉羧酸、3-羟基苯甲酸、苹果酸、对茴香酸、棕榈酸、硬脂酸、12-羟基硬脂酸、油酸、亚油酸和亚麻酸。作为其他有机酸,另外可例示作为油酸与亚油酸的反应物的二聚酸、对该二聚酸加氢而得的氢化二聚酸、作为油酸与亚油酸的反应物的三聚酸、以及对该三聚酸加氢而得的氢化三聚酸。作为其他有机酸,还可例示出油酸与亚油酸的反应物以外的二聚酸、对该二聚酸加氢而得的氢化二聚酸、油酸与亚油酸的反应物以外的三聚酸、以及对该三聚酸加氢而得的氢化三聚酸。这些其他有机酸可以同时使用2种以上。
其他有机酸的含量(在使用2种以上的其他有机酸的情况下,它们的总含量)为0~10wt%。其他有机酸的含量的优选上限根据助焊剂的用途、目的而适当变更。例如,在重视助焊剂的还原作用的情况下,该上限为2.0wt%。若抑制助焊剂的经时变化,则该上限为0.5wt%。其他有机酸的含量优选为HBA的含量以下。即,其他有机酸相对于包含HBA和其他有机酸的全部有机酸的含有率优选为50%以下。如果其他有机酸的含有率为50%以下,则能够在辅助HBA对氧化物的还原的同时抑制由其他有机酸引起的金属表面的腐蚀。其他有机酸的含有率优选为40%以下。
1-3-2.胺
作为胺,可例示单乙醇胺、二苯基胍、二甲苯基胍、乙胺、三乙胺、环己胺、乙二胺、三亚乙基四胺、咪唑、2-甲基咪唑、2-乙基咪唑、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盐、1-氰基乙基-2-苯基咪唑鎓偏苯三酸盐、2,4-二氨基-6-[2'-甲基咪唑基-(1')]-乙基-均三嗪、2,4-二氨基-6-[2'-十一烷基咪唑基-(1')]-乙基-均三嗪、2,4-二氨基-6-[2'-乙基-4'-甲基咪唑基-(1')]-乙基-均三嗪、2,4-二氨基-6-[2'-甲基咪唑基-(1')]-乙基-均三嗪异氰脲酸加成物、2-苯基咪唑异氰脲酸加成物、2-苯基-4,5-二羟基甲基咪唑、2-苯基-4-甲基-5-羟基甲基咪唑、2,3-二氢-1H-吡咯并[1,2-a]苯并咪唑、1-十二烷基-2-甲基-3-苄基咪唑鎓氯化物、2-甲基咪唑啉、2-苯基咪唑啉、2,4-二氨基-6-乙烯基-均三嗪、2,4-二氨基-6-乙烯基-均三嗪异氰脲酸加成物、2,4-二氨基-6-甲基丙烯酰氧基乙基-均三嗪、环氧-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、2-(2'-羟基-5'-甲基苯基)苯并三唑、2-(2'-羟基-3'-叔丁基-5'-甲基苯基)-5-氯苯并三唑、2-(2'-羟基-3',5'-二-叔戊基苯基)苯并三唑、2-(2'-羟基-5'-叔辛基苯基)苯并三唑、2,2'-亚甲基双[6-(2H-苯并三唑-2-基)-4-叔辛基苯酚]、6-(2-苯并三唑基)-4-叔辛基-6'-叔丁基-4'-甲基-2,2'-亚甲基双酚、1,2,3-苯并三唑、1-[N,N-双(2-乙基己基)氨基甲基]苯并三唑、羧基苯并三唑、1-[N,N-双(2-乙基己基)氨基甲基]甲基苯并三唑、2,2'-[[(甲基-1H-苯并三唑-1-基)甲基]亚氨基]双乙醇、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-乙基己基氨基)甲基]苯并三唑、2,6-双[(1H-苯并三唑-1-基)甲基]-4-甲基苯酚、5-甲基苯并三唑和5-苯基四唑。这些胺可以同时使用2种以上。
胺的含量(在使用2种以上的胺的情况下,它们的总含量)为0~5wt%。与其他有机酸的优选上限同样地,胺的含量上限根据助焊剂的用途、目的而适当变更。例如,在重视助焊剂的还原作用的情况下,该上限为2.5wt%。若抑制助焊剂的经时变化,则该上限为1.0wt%。
1-3-3.有机磷化合物
作为有机磷化合物,可例示甲基酸性磷酸酯、乙基酸性磷酸酯、异丙基酸性磷酸酯、单丁基酸性磷酸酯、丁基酸性磷酸酯、二丁基酸性磷酸酯、丁氧基乙基酸性磷酸酯、2-乙基己基酸性磷酸酯、双(2-乙基己基)磷酸酯、单异癸基酸性磷酸酯、异癸基酸性磷酸酯、月桂基酸性磷酸酯、异十三烷基酸性磷酸酯、硬脂基酸性磷酸酯、油基酸性磷酸酯、牛脂磷酸酯、椰子油磷酸酯、异硬脂基酸性磷酸酯、烷基酸性磷酸酯、二十四烷基酸性磷酸酯、乙二醇酸性磷酸酯、甲基丙烯酸-2-羟乙酯酸性磷酸酯、焦磷酸二丁酯酸性磷酸酯、2-乙基己基膦酸单-2-乙基己酯、和烷基(烷基)膦酸酯。这些有机磷化合物可以同时使用2种以上。
有机磷化合物的含量(在使用2种以上的有机磷化合物的情况下,它们的总含量)为0~3wt%。该含量的上限也可以为1wt%。
1-3-4.有机硫化合物
作为有机硫化合物,可例示烷烃磺酸、烷醇磺酸、芳香族磺酸等有机磺酸。有机磺酸可以包含在上述其他有机酸中。作为烷烃磺酸,可例示甲磺酸、乙磺酸、1-丙磺酸、2-丙磺酸、1-丁磺酸、2-丁磺酸、戊磺酸、己磺酸、癸磺酸和十二烷磺酸。作为烷醇磺酸,可例示2-羟基乙烷-1-磺酸、2-羟基丙烷-1-磺酸、2-羟基丁烷-1-磺酸、2-羟基戊烷-1-磺酸、1-羟基丙烷-2-磺酸、3-羟基丙烷-1-磺酸、4-羟基丁烷-1-磺酸、2-羟基己烷-1-磺酸、2-羟基癸烷-1-磺酸和2-羟基十二烷-1-磺酸。作为芳香族磺酸,可例示1-萘磺酸、2-萘磺酸、甲苯磺酸、二甲苯磺酸、对苯酚磺酸、甲酚磺酸、磺基水杨酸、硝基苯磺酸、磺基苯甲酸和二苯胺-4-磺酸。
有机硫化合物的含量(使用2种以上的有机磷化合物的情况下,它们的总含量)为0~3wt%。该含量的上限也可以为1.5wt%。
1-3-5.有机卤化物
作为有机卤化物,可例示反式-2,3-二溴-1,4-丁烯二醇、异氰脲酸三烯丙酯六溴化物、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、2,3-二溴-1,4-丁二醇、2,3-二溴-2-丁烯-1,4-二醇、反式-2,3-二溴-2-丁烯-1,4-二醇、顺式-2,3-二溴-2-丁烯-1,4-二醇、四溴邻苯二甲酸、溴代琥珀酸、2,2,2-三溴乙醇等有机溴化合物。作为有机卤化物,另外可例示氯代烷烃、氯化脂肪酸酯、氯菌酸、氯菌酸酐等有机氯化物。作为有机卤化物,还可例示氟表面活性剂、具有全氟烷基的表面活性剂、聚四氟乙烯等有机氟化物。这些有机卤化物可以同时使用2种以上。
有机卤化物(使用2种以上的有机卤化物的情况下,它们的总含量)为0~5wt%。该含量的上限也可以为1wt%。
1-3-6.胺氢卤酸盐
胺氢卤酸盐是使胺与卤化氢反应而得到的化合物。作为胺氢卤酸盐,可例示硬脂胺盐酸盐、二乙基苯胺盐酸盐、二乙醇胺盐酸盐、2-乙基己胺氢溴酸盐、吡啶氢溴酸盐、异丙胺氢溴酸盐、环己胺氢溴酸盐、二乙胺氢溴酸盐、单乙胺氢溴酸盐、1,3-二苯胍氢溴酸盐、二甲胺氢溴酸盐、二甲胺盐酸盐、松香胺氢溴酸盐、2-乙基己胺盐酸盐、异丙胺盐酸盐、环己胺盐酸盐、2-甲基哌啶氢溴酸盐、1,3-二苯胍盐酸盐、二甲基苄基胺盐酸盐、氢溴酸肼水合物、二甲基环己胺盐酸盐、三壬基胺氢溴酸盐、二乙基苯胺氢溴酸盐、2-二乙氨基乙醇氢溴酸盐、2-二乙氨基乙醇盐酸盐、氯化铵、二烯丙基胺盐酸盐、二烯丙基胺氢溴酸盐、单乙胺盐酸盐、二乙胺盐酸盐、三乙胺氢溴酸盐、三乙胺盐酸盐、肼一盐酸盐、肼二盐酸盐、肼一氢溴酸盐、肼二氢溴酸盐、吡啶盐酸盐、苯胺氢溴酸盐、丁胺盐酸盐、己胺盐酸盐、正辛胺盐酸盐、十二烷基胺盐酸盐、二甲基环己基胺氢溴酸盐、乙二胺二氢溴酸盐、松香胺氢溴酸盐、2-苯基咪唑氢溴酸盐、4-苄基吡啶氢溴酸盐、L-谷氨酸盐酸盐、N-甲基吗啉盐酸盐、甜菜碱盐酸盐、2-甲基哌啶氢碘酸盐、环己胺氢碘酸盐、1,3-二苯基胍氢氟酸盐、二乙胺氢氟酸盐、2-乙基己胺氢氟酸盐、环己胺氟氢酸盐、乙胺氢氟酸盐、松香胺氟氢酸盐、环己胺四氟硼酸盐、二环己胺四氟硼酸盐。
胺氢卤酸盐(使用2种以上的胺氢卤酸盐的情况下,它们的总含量)为0~2wt%。该含量的上限也可以为0.5wt%。
1-4.树脂组合物
实施方式的助焊剂可以含有树脂组合物。即,实施方式的助焊剂含有树脂组合物作为任选成分。作为树脂组合物,可例示脂松香、木松香、妥尔油松香等天然松香、以及由该天然松香得到的衍生物。作为松香衍生物,可例示精制松香、聚合松香、氢化松香、歧化松香、氢化歧化松香、酸改性松香、苯酚改性松香、α,β不饱和羧酸改性物(例如,丙烯酸化松香、马来化松香、富马酸松香)。作为松香衍生物,还可例示上述的聚合松香或α,β不饱和羧酸改性物的精制物、氢化物、歧化物、酯化物等。这些树脂组合物可以同时使用2种以上。
树脂组合物的含量(使用2种以上的树脂组合物的情况下,它们的总含量)为0~5wt%。该含量的上限可以为1wt%。
1-5.溶剂
实施方式的助焊剂可以含有溶剂。即,实施方式的助焊剂含有溶剂作为任选成分。为了有效地发挥活性剂和活性助剂的还原作用,溶剂优选在低于70℃时不挥发。如果溶剂挥发,则助焊剂干固,助焊剂难以浸润扩散到焊接部。因此,溶剂的沸点优选为200℃以上。但是,要求溶剂在加热时挥发。因此,溶剂的沸点优选为280℃以下。
作为溶剂,可例示水、醇系溶剂、二醇醚系溶剂、萜品醇类。作为醇系溶剂,可例示异丙醇、1,2-丁二醇、异冰片基环己醇、2,4-二乙基-1,5-戊二醇、2,2-二甲基-1,3-丙二醇、2,5-二甲基-2,5-己二醇、2,5-二甲基-3-己炔-2,5-二醇、2,3-二甲基-2,3-丁二醇、1,1,1-三(羟基甲基)乙烷、2-乙基-2-羟基甲基-1,3-丙二醇、2,2′-氧代双(亚甲基)双(2-乙基-1,3-丙二醇)、2,2-双(羟基甲基)-1,3-丙二醇、1,2,6-三羟基己烷、双[2,2,2-三(羟基甲基)乙基]醚、1-乙炔基-1-环己醇、1,4-环己二醇、1,4-环己烷二甲醇、赤藓醇、苏糖醇、愈创木酚甘油醚、3,6-二甲基-4-辛炔-3,6-二醇和2,4,7,9-四甲基-5-癸炔-4,7-二醇。作为二醇醚系溶剂,可例示己基二甘醇、二乙二醇单-2-乙基己基醚、乙二醇单苯基醚、2-甲基戊烷-2,4-二醇、二乙二醇单己基醚、二乙二醇二丁基醚和三乙二醇单丁基醚。溶剂中可以使用上述溶剂中的1种,也可以同时使用2种以上。
溶剂的含量(在使用2种以上的溶剂的情况下,它们的总含量)为0~76wt%。该含量的上限可以为65wt%,可以为30wt%,可以为20.5wt%,可以为15.5wt%,也可以为12wt%。
1-6.其他添加剂
实施方式的助焊剂可以含有抗氧化剂、消泡剂和着色剂作为其他添加剂。作为抗氧化剂,可例示受阻酚系抗氧化剂。作为消泡剂,可例示丙烯酸聚合物、乙烯基醚聚合物、丁二烯聚合物和硅酮。其他添加剂可以使用上述添加剂中的1种,也可以同时使用2种以上。其他添加剂的含量(在使用2种以上的情况下,它们的总含量)为0~5wt%。
2.焊膏
实施方式的焊膏包含上述助焊剂和焊料粉末。
焊膏中使用的焊料粉末的组成没有特别限定,焊料粉末可以使用Sn单质和各种焊料合金。作为各种焊料合金,可例示二元系合金和三元系以上的多元系合金。作为二元系合金,可例示Sn-Sb系合金、Sn-Pb系合金、Sn-Cu系合金、Sn-Ag系合金、Sn-Bi系合金及Sn-In系合金。作为多元系合金,可例示在上述的二元系合金中添加了选自由Sb、Bi、In、Cu、Zn、As、Ag、Cd、Fe、Ni、Co、Au、Ge、P组成的组中的1种以上的金属的合金。
焊料粉末和助焊剂相对于焊膏的整体质量的含量没有限定。例如焊料粉末的含量为5~95质量%、助焊剂的含量为5~95质量%。
焊膏的制造方法没有限定,可以通过将原料同时或依次用任意的方法混合来制造。在制造焊膏时,最终将助焊剂的全部成分和焊料粉末混合即可。即,可以在预先制备的助焊剂的全部成分中混合焊料粉末,也可以在助焊剂的成分的一部分与焊料粉末混合后,进一步混合助焊剂的剩余成分。此外,也可以同时混合焊膏的全部成分。
3.实施例
以下,基于实施例对实施方式的助焊剂进行详细说明。
按以下表1~5所示的混配比例配制实施例和比较例的助焊剂。接着,将这些助焊剂与具有Sn-3.0Ag-0.5Cu(SAC305)的组成的焊料粉末以助焊剂:焊料粉末=11:89的质量比混合来配制焊膏。焊料粉末使用JIS Z 3284-1:2014的表2(粉末尺寸的分类)中分类为记号“6”的物质。接着,使用金属掩模,在Cu-OSP电极上(N=6)之上以80μm高度印刷焊膏。
之后,载置QFN(Quad Flat Non-Lead Package:四边无引线扁平封装),进行了回流。作为QFN,使用一边的长度为4mm的正方形、且下表面电极为一边的长度为1.7mm的正方形的部件。回流在N2气氛下实施,程序(プロファイル)在140~170℃下保持71秒,然后升温至244℃,在220℃以上进行58秒的主加热。
在实施回流后,使用X射线透视装置(UNi-HiTE SYSTEM公司制造的Microfocus X-ray System XVR-160)观察焊料接合部的透射图像,求出空洞产生率。具体而言,从焊料接合部的上部朝向下部进行透射观察,得到焊料接合部的透射图像。然后,通过基于透射图像的色调的对比度来识别金属填充部和空洞部(金属非填充部)的自动解析来计算空洞面积率,将其作为空洞产生率。空洞的产生的抑制性的评价基准如下所述。
〇:6个焊料接合部中的空洞产生率的平均值为15%以下
×:6个焊料接合部中的空洞产生率的平均值大于15%[表1]
[表2]
[表3]
[表4]
[表5]
由表1~5可知,实施例1~78的助焊剂显示了充分抑制焊料接合部中的空洞的产生的结果。虽然获得优异的结果的理由的详细情况不明确,但本发明人等推测如下。即,HBA的挥发温度处于回流温度区域附近,因此助焊剂中的HBA在回流的过程中发挥活性并且挥发。因此,在回流后的焊料接合部不残留HBA,因此抑制了源自该HBA的空洞的产生。另外,通过在助焊剂中添加HBA,阳离子系和非离子系的表面活性剂在助焊剂整体中所占的含量相对地降低,因此抑制了源自这些表面活性剂的空洞的产生。
另一方面,可知在比较例1~2的助焊剂中,无法避免焊料接合部中的空洞的产生。该结果证实了与上述表面活性剂的含量相关的推测。
Claims (14)
1.一种助焊剂,其特征在于,其包含:
作为活性剂的2-羟基异丁酸0.1wt%~20wt%、
阳离子系表面活性剂10wt%~60wt%、和
非离子系表面活性剂5wt%~60wt%。
2.根据权利要求1所述的助焊剂,其特征在于,所述2-羟基异丁酸的含量为1wt%~10wt%。
3.根据权利要求1或2所述的助焊剂,其特征在于,所述阳离子系表面活性剂是脂肪族单胺或脂肪族二胺的环氧烷加成物。
4.根据权利要求1~3中任一项所述的助焊剂,其特征在于,所述非离子系表面活性剂为脂肪族一元醇或芳香族多元醇的环氧烷加成物、或山梨糖醇酐脂肪族酯中的至少一者。
5.根据权利要求1~4中任一项所述的助焊剂,其特征在于,其还包含活性助剂,所述活性助剂为所述2-羟基异丁酸以外的其他有机酸、胺、有机磷化合物、有机硫化合物、有机卤化物、胺氢卤酸盐中的至少一种。
6.根据权利要求5所述的助焊剂,其特征在于,所述其他有机酸的含量超过0wt%且为10wt%以下。
7.根据权利要求5或6所述的助焊剂,其特征在于,所述胺的含量超过0wt%且为5wt%以下。
8.根据权利要求5~7中任一项所述的助焊剂,其特征在于,所述有机磷化合物的含量超过0wt%且为3wt%以下。
9.根据权利要求5~8中任一项所述的助焊剂,其特征在于,所述有机硫化合物的含量超过0wt%且为3wt%以下。
10.根据权利要求5~9中任一项所述的助焊剂,其特征在于,所述有机卤化物的含量超过0wt%且为5wt%以下。
11.根据权利要求5~10中任一项所述的助焊剂,其特征在于,所述胺氢卤酸盐的含量超过0wt%且为2wt%以下。
12.根据权利要求1~11中任一项所述的助焊剂,其特征在于,其还包含超过0wt%且为5wt%以下的树脂组合物。
13.根据权利要求1~12中任一项所述的助焊剂,其特征在于,其还包含超过0wt%且为76wt%以下的溶剂。
14.一种焊膏,其特征在于,其包含权利要求1~13中任一项所述的助焊剂、和金属粉。
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