CN101758337B - 一种助焊剂用非卤素活性剂 - Google Patents

一种助焊剂用非卤素活性剂 Download PDF

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CN101758337B
CN101758337B CN 200910227146 CN200910227146A CN101758337B CN 101758337 B CN101758337 B CN 101758337B CN 200910227146 CN200910227146 CN 200910227146 CN 200910227146 A CN200910227146 A CN 200910227146A CN 101758337 B CN101758337 B CN 101758337B
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acid
active agent
soldering flux
halogen
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CN101758337A (zh
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易宗明
刘艺
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HUNAN ASTAR BIO-CHEMICAL TECHNOLOGY Co Ltd
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Priority to PCT/CN2010/000285 priority patent/WO2011066706A1/zh
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01Sulfonic acids
    • C07C309/02Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/04Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing only one sulfo group
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36Selection 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36Selection 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
    • B23K35/362Selection of compositions of fluxes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01Sulfonic acids
    • C07C309/02Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/05Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing at least two sulfo groups bound to the carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01Sulfonic acids
    • C07C309/02Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/06Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing halogen atoms, or nitro or nitroso groups bound to the carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01Sulfonic acids
    • C07C309/02Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/07Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
    • C07C309/08Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing hydroxy groups bound to the carbon skeleton

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

一种助焊剂用非卤素活性剂,是用磺酸与有机碱作用形成的磺酸盐。上述磺酸可以是烷基磺酸、烷基二磺酸、羟基磺酸、卤代磺酸,如甲磺酸、乙磺酸、丙磺酸、甲二磺酸、乙二磺酸、丙二磺酸、羟基乙磺酸等。所述磺酸盐,如三乙胺甲二磺酸盐、二苯胍甲二磺酸盐等。所述有机碱,可以是有机胺类、胍类、咪唑类、磷类等。本发明的优越性:1、高活性,在活性状态下,属强酸性物质。其酸性强度与氢卤酸相近。2、低腐蚀,在非焊接条件下,对焊盘与焊料金属无腐蚀性,具有有机酸类活性剂低腐蚀的优点。3、应用范围广,可作为多类助焊剂中的活性成份。

Description

一种助焊剂用非卤素活性剂
技术领域
本发明涉及电子工业焊接用的助焊剂,特指助焊剂中的活性成份,即一种助焊剂用非卤素活性剂。
技术背景
在钎焊过程中,助焊剂是不可或缺的材料,其作用极为重要。而助焊剂中活性成份是最为关键的部分。助焊剂中活性剂的作用主要是除去基材表面的氧化膜,使焊接时的表面张力减小,增加焊料和焊盘金属的润湿性,提高可焊性。
对理想的活性剂要求是:在通常情况下,它们是稳定的,即使跟基材接触,也不会与其发生任何作用。在使用过程中,活性物质被加热到一定温度时,开始融化并润湿焊料和焊盘;随着温度的进一步提高,活性物质开始逐渐释放活性能力;当达到最佳焊接温度时,活性能力全部被释放。焊接完成后,随着温度的降低,剩余的活性物质又重回原来的惰性状态。焊接过程中,与氧化膜作用产生的铜、锡等盐类物质,不影响电气性能;当然,更不能腐蚀基材。
目前的活性剂一般为有机物的无机酸盐、有机酸类物质,或是它们的混合物。无机酸盐类一般以卤酸盐类使用居多,如盐酸胺类、盐酸胍类、氢溴酸胺类、氢溴酸胍类等,它们的特点是:有很高的活性。然而,缺点也是致命的:腐蚀基材、严重影响电气性能。有机酸类活性剂是目前开发的热点,不断有专利出现。如Pat.US5507882,1996(Bristol Samuel V Low residue water-based soldering flux andprocess for soldering with same)、Pat.CN 1209374A,1999(李圣波.低固含量免清洗助焊剂)、Pat.CN 1398698A,2003(邓和升等.免清洗液体助焊剂)、Pat.CN1011564805A,2009(雷永平等,低银SnAgCu无铅焊膏用新型环保型助焊剂)。一般倾向选择有机羧酸,特别是二元羧酸如丁二酸、戊二酸、己二酸等。它们主要目的是解决卤素类活性剂中腐蚀问题及由此而产生的电器性能问题。的确,问题是解决了。遗憾的是,活性却大为降低,根本无法与卤素类相提并论。折中的方案是:有机酸与卤素联用,在腐蚀性与活性之间找一个平衡,如Pat.CN101543943A,2009(秦俊虎等,无铅松香芯低卤素免清洗助焊剂及其制备方法)、Pat.CN101569966A,2009(吴坚等,一种无铅锡膏及其助焊剂的制备方法)等。这种方案只能应用于性能要求较低的品种,不能用于对性能有高要求的品种。
发明内容
本发明的目的是提供这样的一种物质:它对金属基材、焊料均没有腐蚀作用,可是对其所形成的金属氧化物,却有很高的反应活性。采用它们作活性剂,既有卤素活性剂的高活性,又兼具有机酸低腐蚀性。
本发明是这样实现的:这种助焊剂用非卤素活性剂是用磺酸与有机碱作用形成的磺酸盐。在通常情况下,这种盐是非常稳定的,与焊料、基材及其所形成的金属氧化物不发生任何作用。焊接温度时,磺酸盐分解出游离的磺酸,释放活性。焊接完成后,随着温度的降低,余下的磺酸与有机碱又重新结合为惰性磺酸盐。
本发明所述磺酸盐中的磺酸具有如下通式:
其中,R为烷基、苯基或氢原子;X为卤原子、磺酸基、羟基、氢原子。
上述磺酸可以是烷基磺酸、烷基二磺酸、羟基磺酸、卤代磺酸、如甲磺酸、乙磺酸、丙磺酸、甲二磺酸、乙二磺酸、丙二磺酸、羟基乙磺酸、苯磺酸、对甲苯磺酸、氯代甲磺酸等。
上述磺酸优选烷基二磺酸,如甲二磺酸、乙二磺酸、丙二磺酸等。
在上述磺酸中,其中特别优选甲二磺酸,其结构示性式为:
HOSO2-CH2-SO2OH,CAS:503-40-2。
本发明所述磺酸盐,如三乙胺甲二磺酸盐、二苯胍甲二磺酸盐、二异丁胺甲二磺酸盐、二苯胺甲二磺酸盐、三乙醇胺甲二磺酸盐、N-甲基咪唑甲二磺酸盐、甲二磺酸吡啶、十二胺甲二磺酸盐、十八胺甲二磺酸盐、甲二磺酸钾、甲二磺酸钠、甲二磺酸铜、甲二磺酸亚锡等。
本发明所述磺酸盐,在助焊剂中作为活性剂既可独立使用,也可以和其它种类活性剂联合使用。
本发明所述磺酸盐,在助焊剂中是不可能存在的,除非有意添加。据此,我们提出:只要离子色谱法能检测到磺酸根,即可判定为使用本专利。
本发明所述有机碱,其范围很广。可以是有机胺类、胍类、咪唑类、磷类等,它们的作用是为了与上述磺酸成盐,在非焊接条件下不产生活性。
本发明的优越性:
1、高活性,本发明所述活性剂,在活性状态下,属强酸性物质。其酸性强度与氢卤酸相近,活性可与卤素活性剂媲美。
2、低腐蚀,本发明所述活性剂,在非焊接条件下,对焊盘与焊料金属无腐蚀性。具有有机酸类活性剂低腐蚀的优点。
3、应用范围广,本发明所述活性剂,既解决了传统卤素活性剂的强腐蚀性,又克服了目前有机酸类活性剂活性低的不足。可作为多类助焊剂中的活性成份,配制出各种高性能的无卤素助焊剂。如溶剂型免清洗助焊剂、水溶性型助焊剂、水溶性型免清洗助焊剂,以适用于不同要求的焊接工艺。既可用于有铅焊接,也可用于无铅焊接。
具体实施方式
为进一步描叙本发明,用以下实例说明。当然,不仅限于本发之实例。
实施例1:在免清洗液态助焊剂中的应用
重量配方比例如下:异丙醇95%、二乙二醇单甲醚3%、丁二酸1.5%、甲二磺酸二苯胍盐0.5%。搅拌溶解完全后得到无色透明液态助焊剂。在250℃情况下,能在锡99.3%、铜0.7%合金的金属液面上快速扩散,与液面锡铜氧化物反应迅速,具有良好的助焊效果。在室温状态下,助焊剂不会与铜、锡基材发生化学腐蚀。在波峰焊生产线上,电子产品焊锡后,PCB板面绝缘阻抗达到1×1013Ω以上,具有良好的电气性能。
实施例2:在锡线内含固态助焊剂中的应用
重量配方比例如下:松香95%、乙二醇单苯醚3%、甲二磺酸咪唑盐2%。加热焙融分散完全后得到透明淡黄色固体助焊剂。在锡线生产中,将该助焊剂挤压在锡线中的含量控制在2.8%至3.0%之间,锡线选用Sn99.3%、Cu0.7%的合金。制成的锡线在铜箔上润湿性良好、焊点光亮、残留物透明。在使用过程中,无臭味、无松香飞溅,助焊效果良好,锡线残留物的绝缘阻抗达到1×1013Ω以上。
实施例3:在助焊膏中的应用
重量配方比例如下:松香50%、二乙二醇单丁醚40%、硬脂酸酰胺5%、甲二磺酸胍盐5%。加热熔融分散完全后得到半透明淡黄色膏状助焊剂。选用金属成份Sn96.5%、Ag3.0%、Cu0.5%的锡粉,锡粉直径在25微米至45微米之间。将锡粉90%,助焊剂10%,相互搅拌混溶后,得到锡膏。该锡膏具有良好的印刷效果,在铜、锡、镍基材的焊盘上,可以加热得到饱满光亮的焊点。焊点残留物的绝缘阻抗达到1×1013Ω,室温状态下焊点在6个月后不会被腐蚀发黑。

Claims (5)

1.一种非卤素活性剂在助焊剂中的应用,在助焊剂中含有非卤素活性剂,其特征在于,非卤素活性剂为甲二磺酸与有机碱作用形成的甲二磺酸盐。
2.根据权利要求1所述的一种非卤素活性剂在助焊剂中的应用,其特征在于,上述有机碱是胍类或咪唑类。
3.根据权利要求2所述的一种非卤素活性剂在助焊剂中的应用,其特征在于,在免清洗液态助焊剂中的应用,重量配方比例如下:异丙醇95%、二乙二醇单甲醚3%、丁二酸1.5%、甲二磺酸二苯胍盐0.5%,搅拌溶解完全后得到无色透明液态助焊剂。
4.根据权利要求2所述的一种非卤素活性剂在助焊剂中的应用,其特征在于,在锡线内含固态助焊剂中的应用,重量配方比例如下:松香95%、乙二醇单苯醚3%、甲二磺酸咪唑盐2%;加热焙融分散完全后得到透明淡黄色固体助焊剂,在锡线生产中,将该助焊剂挤压在锡线中的含量控制在2.8%至3.0%之间,锡线选用Sn99.3%、Cu0.7%的合金。
5.根据权利要求2所述的一种非卤素活性剂在助焊剂中的应用,其特征在于,在助焊膏中的应用,重量配方比例如下:松香50%、二乙二醇单丁醚40%、硬脂酸酰胺5%、甲二磺酸胍盐5%;加热熔融分散完全后得到半透明淡黄色膏状助焊剂,选用金属成份Sn96.5%、Ag3.0%、Cu0.5%的锡粉,锡粉直径在25微米至45微米之间,将锡粉90%,助焊剂10%,相互搅拌混溶后,得到锡膏。
CN 200910227146 2009-12-03 2009-12-03 一种助焊剂用非卤素活性剂 Expired - Fee Related CN101758337B (zh)

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CN102069315B (zh) * 2011-02-21 2012-11-21 四川大学 一种高润湿性的无铅无卤焊膏
US8430293B2 (en) * 2011-09-30 2013-04-30 Rohm And Haas Electronic Materials Llc Curable amine, carboxylic acid flux composition and method of soldering
JP6390989B1 (ja) * 2017-11-24 2018-09-19 千住金属工業株式会社 フラックス及びソルダペースト
CN110328467B (zh) * 2019-07-06 2021-10-29 浙江强力控股有限公司 一种助焊剂及其制备方法
CN114096376B (zh) * 2019-07-25 2023-10-31 斯泰潘公司 非水性焊剂组合物

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