CN1845984B - 基于氟化烃和仲丁醇的用于使电子板去焊的组合物 - Google Patents
基于氟化烃和仲丁醇的用于使电子板去焊的组合物 Download PDFInfo
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Abstract
本发明涉及氟化烃领域且涉及含氟化烃、仲丁醇和任选的DMSO的新型组合物。这些新型组合物特别有利地用于使电子板去焊，特别是使含″非清洗″焊剂的电子板去焊。
Description
本发明涉及氟化烃领域，更具体地说涉及含氟化烃和仲丁醇的新型组合物，其可用于使电子板去焊(defluxing electronic board)，特别是用于使含″非清洗″焊剂的电子板去焊。
在电子板制造过程中，为了去除粘附到印刷电路的焊剂，有必要进行这样的操作，该操作由清洗用于改进焊料质量(称为焊剂)的残留物质组成。在该领域中，该去除操作称为去焊。在该领域中广泛使用氟化烃，且更具体地说1，1-二氯-1-氟代乙烷(称为HCFC 141b)。基于HCFC 141b和甲醇的共沸配方(在本领域称为FORANE
141b MGX)特别适用于在热条件下用于去焊机。
然而，由于其对臭氧层存在影响(非零(臭氧降解电位ODP＝0.11))，HCFC 141b受相当多法规限制，这些法规日益用于消除HCFC 141b的使用。因而，从2002年1月1日开始，在除航空和航天领域之外，有关对臭氧层有害物质的欧洲法规(no.2037/2000)已禁止使用HCFC(含氢氯氟烃)(hydrochloroflurocarbon)如HCFC 141b用于溶剂应用，从2009年开始，该禁令也将在欧洲的航空和航天领域生效。
在去焊应用中，已提出用于替代HCFC 141b的取代方案，特别是HFC(含氢氟烃)(hydrofluorocarbon)和/或HFE(氢氟醚)(hydrofluoro ether)的应用。HFC和HFE对臭氧层没有影响(ODP为零或相对于已生效的法规来说是可忽略不计的)。
在最广为人知且最普遍使用的HFC中，可提及，例如，1，1，1，3，3-五氟丁烷(365mfc)、1，1，1，2，3，4，4，5，5，5-十氟戊烷(4310mee)、1，1，1，2-四氟乙烷(134a)、五氟乙烷(125)、1，1，1-三氟乙烷(143a)、二氟甲烷(32)、1，1-二氟乙烷(152a)、1-氟代乙烷(161)、1，1，1，2，3，3，3-七氟丙烷(227ea)、1，1，1，3，3，五氟丙烷(245fa)、八氟丙烷(218)、(全氟丁基)乙烯(C4H9CH＝CH2)、1，1，2，2，3，4，5-七氟环戊烷(C5H3F7)、全氟己基乙烯(C6F13CHCH2)、十三氟己烷(C6F13H)和全氟(甲基吗啉)(PF 5052)以及它们的混合物，其可有助于改善某些性能，例如不燃性。
在最广为人知且最普遍使用的HFE中，可提及，例如，甲基七氟丙基醚(C3F7OCH3)、甲基九氟丁基醚(C4F9OCH3)、乙基九氟丁基醚(C4F9OC2H5)和全氟吡喃(C5F10O)、以及它们的混合物。
HFC和HFE展现出能与HCFC 141b相比的物理化学性质：良好的热和化学稳定性、低毒性、低沸点、低表面张力。然而，已经证实，在某些去焊应用中，特别是用于含有通常不希望被清洗的焊剂的电子板的去焊，它们是无效的。这些焊剂很难去除且在该领域称为″非清洗″焊剂。这些焊剂来自用于难以焊接的表面的非-洗焊膏。这些膏基于有机和无机化合物的复合混合物。在这些化合物中，可提及基于锡、银、铅等的具有小粒径的金属粉末、粘合剂例如松香、溶剂、表面活性剂树脂、触变剂或卤化活化剂。
出人意料地，发现使用含氟化烃和仲丁醇的组合物，可容易地去除″非清洗″焊剂，通过二甲基亚砜(在下文中称为DMSO)的存在，可增强该组合物的作用。
因此，本发明的主题是含氟化基物(fluorinated base)、仲丁醇和任选的DMSO的组合物，这些新型组合物特别适用于含″非清洗″焊剂的电子板的去焊。这些新型组合物还可适用于去除其它焊剂。
表达方式″可用于本发明组合物的氟化基物″是指在25℃下表面张力小于30mN/m(根据ISO 304标准测定)且对臭氧层的作用可忽略不计(零或可忽略不计的ODP)的一种或多种氟化物的混合物。该氟化物可选自氢氟烃(HFC)和/或氢氟醚(HFE)。
本发明的组合物包含1-40重量％的氟化基物、50-99重量％的仲丁醇和0-30重量％的DMSO，各成分的重量百分数之和等于100。优选，它们含有15-25重量％的氟化基物、50-70重量％的仲丁醇和15-25重量％的DMSO。
作为HFC的非限制性实例，可提及1，1，1，3，3-五氟丁烷(365mfc)、1，1，1，2，3，4，4，5，5，5-十氟戊烷(4310mee)、1，1，1，2-四氟乙烷(134a)、五氟乙烷(125)、1，1，1-三氟乙烷(143a)、二氟甲烷(32)、1，1-二氟乙烷(152a)、1-氟代乙烷(161)、1，1，1，2，3，3，3-七氟丙烷(227ea)、1，1，1，3，3，五氟丙烷(245fa)、八氟丙烷(218)、(全氟丁基)乙烯(C4H9CH＝CH2)、1，1，2，2，3，4，5-七氟环戊烷(C5H3F7)、全氟己基乙烯(C6F13CHCH2)、十三氟己烷(C6F13H)和全氟(甲基吗啉)(PF5052)。
作为HFE的非限制性实例，可提及甲基七氟丙基醚(C3F7OCH3)、甲基九氟丁基醚(C4F9OCH3)、乙基九氟丁基醚(C4F9OCH2H5)和全氟吡喃(C5F10O)。
这些化合物中的大部分是可市购的。
在可用于本发明组合物的氟化基物中，可提及，例如，HFC 4310mee，或二元或三元混合物HFC 365mfc/HFC 4310mee、HFC 365mfc/HFC 4310mee/HFC 227ea和HFC 227ea/HFE。
优选，HFC 365mfc和HFC 4310mee的混合物用作氟化基物。有利地，这些混合物包含1-99％的HFC 365mfc和1-99％的HC 4310mee。优选的混合物由4％的HFC 365mfc和96％的HFC 4310mee组成。这些混合物可任选地含有HFC 227ea。
该氟化基物还可包含反式-1，2-二氯乙烯，其沸点为47.8℃。
通过对这些成分进行简单混合，可制备本发明的组合物。
本发明的组合物展现出至少相当于广泛用于该应用的基于HCFC 141b和甲醇的共沸组合物FORANE
141b MGX的去焊性能水平。与单独使用HFC或HFE衍生物相比，它们具有相对经济的优点。本发明的组合物是不燃的，它们不具有闪点，它们展现出低毒性水平且对臭氧层不具有任何破坏作用。
下面描述在单个图中表示的用于运用、说明已知的用于去焊的实施方式的机器和方案。
该机械包括两个槽(清洗槽(2)和漂洗槽(8))、和盖子(13)。优选，槽(2)和(8)高且窄，以便于适当地捕集溶剂蒸汽。槽(2)和(8)可装配有超声系统。
最初，使用加热电阻(1)，使含有本发明去焊组合物的清洗槽(2)达到该组合物中所存在的氟化基物的表观沸点。70℃的最大表观沸点可防止各组分被清洗。由于DMSO(189℃)和仲丁醇(99.5℃)的沸点明显高于该氟化基物的沸点(通常小于55℃)，这些溶剂的混合物保持在清洗浴(2)的液相中，而不发生任何显著的蒸发。
漂洗槽(8)仅填充有氟化基物。
来自于槽(2)的沸腾的氟化基物的蒸汽(3)在漂洗槽(8)中经由冷却盘管4循环并在沟槽(5)中回收。测温探头(9)和(10)可控制液相和蒸汽相的温度。包含例如3A型分子筛的分离器(7)的作用是从溶剂中分离水，这些水来自于大气中蒸汽的冷凝。通过溢流系统，从槽(8)以相对清洁的循环的氟化基物供给清洗槽(2)，与清洗槽相比，污染百分数最大为10％。泵(11)可过滤溶剂，以特别保留固体颗粒。以与HCFC 141b的应用相似的方式，当清洗槽含有约30％的污染时，可更换清洗浴。
该机器的应用在于最初将待清洗的电子板浸入清洗槽(2)中。在″非清洗″焊剂中覆盖的区域发现在待处理表面上。
然后将已清洗的组分浸入漂洗浴(8)中。通过对组分表面的夹带作用，由纯的氟化基物组成的漂洗浴(8)可逐渐被焊剂污染。如果发生相当大的夹带，可使用第二漂洗浴。在该机器的冷却区域(6)中进行干燥之前，还可在包括蒸汽相的氟化基物的区域(3)中进行进一步的漂洗。
因此，本发明的另一个主题是用于使电子板去焊的方法，该方法包括第一清洗步骤和第二漂洗步骤，特征在于在清洗槽(2)中以本发明组合物进行该清洗步骤且在漂洗槽(8)中以纯的氟化基物进行该漂洗步骤，该氟化基物可不同于存在于该清洗槽(2)中的氟化基物。
根据本发明方法的优选的变体，存在于漂洗槽中的氟化基物与存在于清洗槽的氟化基物相同。使用该过程的方法可获得不含焊剂和痕量溶剂的清洁的干组分。在清洗困难的情况中，优选使用含有任选地具有DMSO的高含量(至少70％)仲丁醇的清洗组合物。如果漂洗浴含有的氟化基物不同于存在于清洗浴中的氟化基物，也不脱离本发明的范围。
相对于大部分待处理表面(无论它们是否由金属、塑料或玻璃制成)，本发明的组合物也是惰性的。因此，该组合物可用于与HCFC 141b相同的应用。具体地说，它们可用作用于清洗固体表面或使其脱脂的试剂或用作用于固体物体表面除水、用于织物干洗、用于制冷装置清洗的干燥剂，用作用于发泡聚氨脂泡沫的试剂，或用作气溶胶喷射剂、传热流体或硅氧烷沉积剂。
下列实施例仅用于说明本发明且不应被解释为对本发明进行限制。在实施例中用以表示组成含量的百分数为重量百分数。
实施例1
为了评价去焊效率，使用表面积为8cm2的小不锈钢板。以FORANE141b脱脂级(141b DGX)，对每个小板进行预先脱脂，然后称重。
在每个小板上沉积约2g来自HERAEUS公司的F380 Ag3.5-90.OL25型焊膏。
在热板上，将引入玻璃结晶器内的每个小板在250℃下加热约1-2分钟。在加热期间，焊膏中所含的金属形成在小板上滑动的球，从而从残留在小板上的焊剂分离。在环境温度下，将含有焊剂的小板干燥约16小时，然后称重。
然后，在20-25℃的环境温度下，将每个小板在含60ml测试组合物的烧杯中浸渍30分钟。
接着，从该烧杯移出小板，以由HFC 365mfc和HFC 4310mee的混合物组成的FORANE
365 HX型溶剂进行漂洗，然后称重。从而，由该差值得到被去除的焊剂的量。
以由20％的氟化基物(19.2％的HFC 4310mee和0.8％的HFC 365mfc)、60％的仲丁醇和20％的DMSO组成的组合物，去除93％的焊剂。
实施例2
使用与实施例1所述相同的过程。基于25％的HFC 4310mee和75％的仲丁醇的组合物可去除86％的焊剂。
实施例3
对于该实施例，参考该单一附图，使用该清洗机器。
清洗槽(2)充满实施例1的组合物。清洗浴升温至69℃。
漂洗槽(8)充满FORANE 365 HX溶剂。漂洗槽(8)的温度为44℃。
该机器测试所使用的操作条件为：在槽(2)中，待清洗的板的浸渍时间为4分钟，且在槽(8)中，使用超声的漂洗时间为2分钟。在冷却区域(6)进行干燥3分钟。
在这些条件下，与通常使用FORANE
141b MGX所获得的焊剂去除率相比，焊剂去除率更高，且未观察到该清洗材料的可见的侵蚀。
Claims (9)
1.一种用于使电子板去焊的组合物，含有1-40重量％的氟化基物、50-99重量％的仲丁醇和0-30重量％的二甲基亚砜，各成分的重量百分数之和等于100％，其特征在于该氟化基物包括一种或多种在25℃下表面张力小于30mN/m并具有零臭氧降解潜势的氟化物。
2.权利要求1的组合物，含有15-25重量％的氟化基物、50-70重量％的仲丁醇和15-25重量％的二甲基亚砜。
3.权利要求1或2的组合物，特征在于其中氟化物选自氢氟烃和/或氢氟醚。
4.权利要求3的组合物，特征在于该氢氟烃选自1，1，1，3，3-五氟丁烷、1，1，1，2，3，4，4，5，5，5-十氟戊烷、1，1，1，2-四氟乙烷、五氟乙烷、1，1，1-三氟乙烷、二氟甲烷、1，1-二氟乙烷、1-氟代乙烷、1，1，1，2，3，3，3-七氟丙烷、1，1，1，3，3，五氟丙烷、八氟丙烷、全氟丁基乙烯、1，1，2，2，3，4，5-七氟环戊烷、全氟己基乙烯、十三氟己烷和全氟甲基吗啉。
5.权利要求3的组合物，该氢氟烃包括1，1，1，3，3-五氟丁烷和1，1，1，2，3，4，4，5，5，5-十氟戊烷以及任选的1，1，1，2，3，3，3-七氟丙烷的混合物。
6.权利要求3的组合物，特征在于该氢氟醚选自甲基七氟丙基醚、甲基九氟丁基醚、乙基九氟丁基醚和全氟吡喃。
7.权利要求1-6中任一项的组合物在使电子板去焊中的应用。
8.权利要求1-6中任一项的组合物在使含″非清洗″焊剂的电子板去焊中的应用。
9.用于使电子板去焊的方法，包括第一清洗步骤和第二漂洗步骤，特征在于在清洗槽(2)中以权利要求1-6中任一项的组合物进行该清洗步骤且在漂洗槽(8)中以纯的氟化基物进行该漂洗步骤，该氟化基物不同于存在于该清洗槽(2)中的氟化基物。
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| FR0310833A FR2859731B1 (fr) | 2003-09-16 | 2003-09-16 | Compositions a base d'hydrocarbures fluores et de butanol secondaire pour le defluxage de cartes electroniques |
| FR0310833 | 2003-09-16 | ||
| PCT/EP2004/007302 WO2005026310A1 (en) | 2003-09-16 | 2004-07-02 | Compositions based on fluorinated hydrocarbons and secondary butanol for defluxing electronic boards |
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| WO2007100886A2 (en) | 2006-02-28 | 2007-09-07 | E. I. Du Pont De Nemours And Company | Azeotropic compositions comprising fluorinated compounds for cleaning applications |
| US7540973B2 (en) * | 2006-12-12 | 2009-06-02 | E. I. Du Pont De Nemours And Company | Azeotrope-like mixtures comprising heptafluorocyclopentane |
| US20110215273A1 (en) * | 2008-11-13 | 2011-09-08 | Solvay Fluor Gmbh | Hydrofluoroolefins, manufacture of hydrofluoroolefins and methods of using hydrofluoroolefins |
| JP6122333B2 (ja) * | 2013-04-12 | 2017-04-26 | コーデックケミカル株式会社 | 洗浄剤組成物及び該組成物を含有する洗浄剤並びにそれらを用いた洗浄方法 |
| EP3303538B1 (en) | 2015-05-29 | 2020-09-30 | Zynon Technologies, LLC | Cleaning solvent compositions and their use |
| CN106190606A (zh) * | 2016-07-29 | 2016-12-07 | 广东工业大学 | 一种水性印刷电路板清洗剂及其制备方法 |
| WO2018102507A1 (en) | 2016-11-30 | 2018-06-07 | Zynon Technologies, Llc | Cleaning solvent compositions exhibiting azeotrope-like behavior and their use |
| US20210356461A1 (en) | 2018-10-10 | 2021-11-18 | Korea Research Institute Of Bioscience And Biotechnology | Carbene compound, carbene-metal nanoparticle complex and preparation method thereof |
| CN111304007A (zh) * | 2020-04-26 | 2020-06-19 | 苏州佩托斯光学材料有限公司 | 一种全氟聚醚类高分子稀释剂化合物 |
| US11713434B2 (en) | 2020-08-18 | 2023-08-01 | Zynon Technologies, Llc | Cleaning solvent compositions exhibiting azeotrope-like behavior and their use |
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| US7595289B2 (en) | 2009-09-29 |
| EP1678288B1 (en) | 2012-08-22 |
| ES2390876T3 (es) | 2012-11-19 |
| CN1845984A (zh) | 2006-10-11 |
| CA2536440C (en) | 2012-03-27 |
| JP4755987B2 (ja) | 2011-08-24 |
| EP1678288A1 (en) | 2006-07-12 |
| KR20060100365A (ko) | 2006-09-20 |
| JP2007505956A (ja) | 2007-03-15 |
| US20060217277A1 (en) | 2006-09-28 |
| FR2859731B1 (fr) | 2008-03-07 |
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