WO2008035758A1 - Pâte de soudure sans plomb - Google Patents

Pâte de soudure sans plomb Download PDF

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Publication number
WO2008035758A1
WO2008035758A1 PCT/JP2007/068363 JP2007068363W WO2008035758A1 WO 2008035758 A1 WO2008035758 A1 WO 2008035758A1 JP 2007068363 W JP2007068363 W JP 2007068363W WO 2008035758 A1 WO2008035758 A1 WO 2008035758A1
Authority
WO
WIPO (PCT)
Prior art keywords
solder
lead
solder paste
flux
free solder
Prior art date
Application number
PCT/JP2007/068363
Other languages
English (en)
Japanese (ja)
Inventor
Kunihito Takaura
Kazuya Kitazawa
Original Assignee
Senju Metal Industry Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Senju Metal Industry Co., Ltd. filed Critical Senju Metal Industry Co., Ltd.
Priority to JP2008501086A priority Critical patent/JP4162707B2/ja
Publication of WO2008035758A1 publication Critical patent/WO2008035758A1/fr

Links

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
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • 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
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3457—Solder materials or compositions; Methods of application thereof
    • H05K3/3485—Applying solder paste, slurry or powder

Definitions

  • the present invention relates to a solder paste used for soldering electronic equipment, and more particularly to a Sn—Zn-based lead-free solder paste.
  • a method for soldering electronic components there are a brazing method, a flow method, a reflow method, and the like.
  • the brazing method is a method of soldering by applying a greased solder wire to a soldered part! /, And heating and melting the solder wire with a soldering iron.
  • This brazing method has a problem in productivity because soldering is performed for each soldered portion, and is not suitable for mass production.
  • the flow method is to perform soldering by bringing the soldering surface of the printed circuit board into contact with the molten solder, and is capable of soldering the entire printed circuit board in one operation. It is.
  • this flow method can form a bridge where solder adheres across electronic components with a narrow pitch, or molten solder directly onto electronic components that are vulnerable to heat. In some cases, the electronic components may be damaged due to heat, resulting in functional deterioration.
  • a connection component such as a connector is mounted on the soldering surface of the printed circuit board, there is a problem that the molten solder penetrates into the connector hole and cannot be used.
  • solder paste consisting of solder powder and flux is applied only to the necessary parts of the printed circuit board by a printing method or a discharge method, and an electronic component is mounted on the applied part, followed by heating like a reflow furnace.
  • This is a method in which solder paste is melted by an apparatus and the electronic component and the printed circuit board are soldered.
  • This reflow method not only enables soldering at many locations in a single operation, but also reduces the occurrence of bridging even for electronic components with narrow pitch, and also improves productivity and reliability that solder does not adhere to unnecessary locations. Excellent soldering is possible.
  • solder paste used in the conventional reflow method has solder powder of Pb-Sn compound. It was money.
  • This Pb-Sn alloy has an eutectic composition (Pb_63Sn) with a melting point of 183 ° C, and it has little heat effect even on electronic components that are vulnerable to heat or has excellent solderability. There are few occurrences of soldering defects such as dewetting! When an electronic device soldered with a solder paste using this Pb-Sn alloy becomes old or fails, it has been disposed of without being upgraded or repaired.
  • Lead-free solder is composed mainly of Sn, and currently used lead-free solder is Sn-3.5Ag (melting point: 221 ° C), Sn_0.7Cu (melting point: 227 ° C), Sn_9Zn (melting point: 199 ° C), Sn-58 Bi (melting point: 139 ° C) and other binary alloys, Ag, Cu, Zn, Al, Bi, In, Sb, Ni, etc.
  • a third element such as Cr, Co, Fe, Mn, P, Ge, or Ga is appropriately added.
  • the “system” in the present invention is an alloy itself or an alloy to which one or more third elements are added based on a binary alloy.
  • Sn-Ag-based lead-free solder, Sn-Cu-based lead-free solder, etc. have a melting point of 220 ° C or higher. Therefore, when solder paste is used in the reflow method, the peak temperature force during reflow is 3 ⁇ 450 ° C. As a result, there is a problem that electronic components and printed circuit boards are thermally damaged.
  • Sn-Bi eutectic lead-free solder has a melting point of around 139 ° C, and even when used as a solder paste in the reflow method, the peak temperature is 200 ° C or less. There is no thermal effect on the printed circuit board.
  • the lead-free solder containing a large amount of Bi has a problem in heat resistance because its melting point is too low. In other words, the case inside the electronic device When the heat generated by the power transistor etc. is high, the soldered portion of the printed circuit board soldered with the lead-free solder may be peeled off due to a decrease in bonding strength.
  • Pb-free solder containing a large amount of brittle Bi has a problem that it can be easily peeled off even if a slight impact is applied to the soldered part.
  • the lead-free solder of Sn-9Zn eutectic has a melting point of 199 ° C, which is close to the melting point of conventional Pb_Sn eutectic solder.
  • the power is less than 3 ⁇ 430 ° C and there is little thermal effect on electronic components and printed circuit boards.
  • Sn_9Zn eutectic solder paste has poor solderability to the soldered part of copper and does not adhere to solder! /! “Unsoldered” or wet! / In some cases, soldering defects such as “dewetting” that would cause repellency! Such poor soldering deteriorates the strength and strength of the joint when the joint strength is weakened.
  • solder paste of Sn_9Zn eutectic has been discolored from the interface of the copper foil and copper land after many years have passed since the solder paste of the copper land printed circuit board and the copper lead has been soldered. There was something to do. The peeling of the soldered portion causes a failure in the electronic device. Furthermore, the Sn_9Zn eutectic solder paste also had a chip standing that caused a small chip component to rise during soldering. When a chip stands on a printed circuit board, the electronic device incorporating it cannot function at all.
  • solder paste that has improved solderability includes Sn-8Zn_3Bi lead-free solder paste in which Bi is added to an alloy near Sn-Zn eutectic, and this solder paste is currently widely used.
  • present applicants have proposed lead-free solder in which Ag is added to an alloy near Sn_9Zn eutectic to improve corrosion resistance.
  • Sn-Zn-based lead-free solder has a melting point close to that of conventional Sn_Pb solder and uses Zn, which is an essential component for humans. Therefore, it is more harmful to the human body than other lead-free solders. Not that, Zn has excellent properties compared to other lead-free solders, such as In, Ag, Bi, etc. For this reason, Sn-Ag lead-free solder is used as solder paste solder, despite its poor solderability. One solder does not have heat resistance of the part! /, So it cannot be used! /
  • Patent Document 2 there has been proposed a method for improving the soldering strength with Cu at high temperature by adding a small amount of A1 to Sn-Zn lead-free solder.
  • A1 is a metal that easily oxidizes, it is oxidized prior to other components during the production of solder powder, and the components of 0.002% to 0.008% by mass disclosed in this document must be maintained in mass production. Is Have difficulty.
  • a small amount of A1 added to Sn-Zn lead-free solder is effective for improving the soldering strength at high temperatures. It has no effect on moisture resistance. High temperatures such as 85 ° C and 85% RH, high It cannot withstand humidity.
  • Sn-Zn lead-free solder powder (Patent Document 4) that adsorbs amine on the surface of Sn-Zn lead-free solder powder and prevents oxidation of the solder powder due to preheating during reflow is disclosed.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2002-224880
  • Patent Document 2 US Pat. No. 6,361,626
  • Patent Document 3 Japanese Patent Laid-Open No. 2005-21958
  • Patent Document 4 Japanese Patent Laid-Open No. 2001-212692
  • Sn-Zn lead-free solder solder paste with liquid paraffin and paraffin wax added to the flux of solder paste has an excellent effect on strength at high temperatures S, flow added to the flux Paraffin or paraffin wax remains almost in the flux residue after soldering, and if a large amount of liquid paraffin or paraffin wax is added in order to expect a moisture-proof effect, There was a problem that the paste residue increased and the appearance was uncomfortable. In addition, when soldering with Sn-Zn lead-free solder paste, the ceramic capacitor soldered when placed under high temperature and high humidity causes the insulation resistance to deteriorate.
  • the present inventors have found that the soldered portion is damaged in a high-temperature and high-humidity environment. Degradation causal force of capacitor insulation resistance S, due to corrosion of Zn, and by making the flux residue after soldering neutral and basic, the Zn-H20 series in the measured corrosion area diagram of Zn The present inventors have found that it is possible to control to the passivated region and completed the present invention.
  • the cause of the decrease in strength of Sn-Zn lead-free solder is the ionization of Zn.
  • a passive film is formed on Zn by adding a material that adjusts the pH of the flux residue after soldering to neutral and basic so that Zn + ions are not generated.
  • the strength of the soldered part is prevented from decreasing.
  • the strength of the soldering part is prevented from decreasing by forming a passivating film of Zn (OH) 2. Yes.
  • the passivity of Zn-H20 system is not formed unless the flux residual force is in the neutral or basic region.
  • the formation of Zn—H20 passivity in the flux residue is effective for the deterioration of the insulation of the chip capacitor as well as the reduction in the strength of the Sn—Zn lead free solder.
  • a guanidine derivative has been found as a material for adjusting the pH of the flux residue after soldering in order to solve this conflicting problem.
  • the guanidine derivative has a high heat resistance, with H of the amino group substituted by an aromatic hydrocarbon, a melting point of around 150 ° C.
  • This guanidine derivative has the property that it remains reliably in the flux residue because it is hard to be decomposed by heat, which is strongly basic as an amine.
  • Guanidine derivatives have the same solderability as organic acids. For this reason, the flux residue after soldering can be adjusted to a pH value of 7 to 11, and solderability is also good.
  • the present invention uses 1,3 diphenyldanidine, 1,3 di-0-tolylguanidine, and 1-0-tolylbiguanide, more preferably the same effect as long as it is a guanidine derivative. And good. These guanidine derivatives may be used alone or in combination of two or more. These guanidine derivatives are also excellent in solderability with solder paste that only adjusts the pH of the flux residue. In general, the addition of amines in the flux biases the flux to be basic, thus hindering the action of the activator. Only However, the guanidine derivatives of the present invention do not inhibit the action of the active agent.
  • the present invention is a solder paste in which a Sn-Zn-based lead-free solder alloy powder and a flux are kneaded, wherein a guanidine derivative is added to the flux.
  • the Sn—Zn alloy powder in the present invention includes Sn—Zn binary alloy powder and ternary or higher alloy powder obtained by adding other elements to the binary alloy powder.
  • solder paste of the present invention it is possible to prevent a decrease in bonding strength that occurs in a Sn-Zn-based lead-free solder alloy even in an environment of high temperature and high humidity, and a general lead-free solder alloy
  • the Sn-Ag-Cu solder alloy used as a high temperature can not be used at a high temperature! /, And the heat resistance is low, and electronic parts can be used with high reliability.
  • the guanidine derivative used in the present invention adjusts the pH of the flux unlike Patent Document 4 and the like, so it is always used together with the flux.
  • the amount of amine used to coat the solder powder of Patent Document 4 is not sufficient to adjust the pH of the flux residue, and it is not possible to use it by coating the powder!
  • the total amount of guanidine derivatives used in the present invention is preferably 10 to 30% by mass. Even more preferably, the amount of guanidine derivatives is 15 to 20% by mass in total.
  • an amine that reacts at a relatively low temperature can be added to the solder paste flux as an amine.
  • diamine, tripropylamine, dihexylamine, trihexyloleamine, decylamine, didecylamine, undecylamine, didecylamine, dodecylamine, didodecylamine, hexadecylamine, octadecylamine , Siku Examples include oral hexylamine, dicyclohexylamine, polyoxyethylene dicyclohexylamine, dimethylaniline, diphenylamine, and triphenylamine.
  • the guanidine derivative used in the present invention can prevent a decrease in solder joint strength at higher temperatures and higher humidity by coexisting with liquid paraffin or paraffin wax.
  • Liquid paraffin or paraffin wax itself is neutral and, when added to the solder paste flux, hardly changes the pH of the flux residue.
  • a layer that does not allow moisture to pass through is formed on the surface of the flux residue, and the solder alloy is prevented from being ionized by separating it from moisture and the solder alloy. Furthermore, it prevents the solder joint strength from decreasing at high temperature and high humidity.
  • Caro liquid paraffin or paraffin wax to the present invention is preferably 5 to 20 mass 0/0 during the solder paste flux. Liquid paraffin or paraffin wax added to the present invention may be added alone or in combination.
  • the Sn-Zn lead-free solder has poor wettability, and in the present invention, the pH of the flux residue must be 7.0 to 11;
  • the amine hydrohalide generally used as a flux activator is used in the solder paste of the present invention, the ⁇ ⁇ of the flux residue increases (acidic region).
  • Suitable as the activator of the present invention is that the pH in the flux is not biased to the acidic range! /
  • Organic halogen compounds are suitable! /.
  • the organic halogen compounds include hexasuboxycyclodidecane, trans ns-2,3 dib-mouth mode 2 butene 1,4-diol, 2,3 dib-mouth mode 1,4 as aliphatic organic halogen compounds.
  • Tris (2,3 dibromopropyl) isocyanurate is also suitable, although it is not an aliphatic organic halogen compound.
  • Example 1 As the Sn-Zn lead-free solder composition, the general Sn-3Bi_8Zn and Sn_9Zn compositions were used. Table 1 shows the flux composition.
  • test substrate Preheat the test substrate to 150 ⁇ ; 170. C, 90 seconds, peak temperature 220. C, 200. Reflow soldering under the reflow conditions of C and 30 seconds, oxygen concentration 3000ppm.
  • test substrate After allowing the test substrate to cool, measure the shear strength using a shear strength tester under conditions of test speed SOO ⁇ m / sec and test height 15 ⁇ .
  • test substrate Preheat the test substrate to 150 ⁇ ; 170. C, 90 seconds, peak temperature 220. C, 200. Reflow soldering under the reflow conditions of C and 30 seconds, oxygen concentration 3000ppm.
  • Judgment criteria of insulation deterioration test were determined to be 1 X 107 ⁇ or less as a failure.
  • the solder paste of the present invention had a strength that hardly deteriorated the insulation resistance and hardly deteriorated even in an environment of 85 ° C and 85% RH.
  • the solder paste of the comparative example showed a decrease in strength and an insulation resistance in an environment of 85 ° C. and 85% RH.
  • solder paste of the present invention can also be used for general lead-free solder alloys other than Sn-Zn-based lead-free solder pastes.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

Le problème à résoudre dans le cadre de cette invention concerne les pâtes de soudure classiques sans plomb en alliage de Sn-Zn qui présentent l'inconvénient d'une chute de résistance de joint lorsqu'elles sont placées dans un environnement à haut niveau d'humidité. Bien qu'on ait mis au point des alliages plus résistants par ajout d'une petite quantité d'un élément du groupe métallique 1B ou Al à la soudure, ces alliages possèdent une mauvaise propriété de mouillage et présentent, certes, des inconvénients et des avantages. Le problème est résolu en mettant à disposition une pâte de soudure sans plomb en alliage de Sn-Zn qui présentent d'excellentes propriétés quant à sa capacité d'empêcher une diminution de la résistance de joint et une détérioration de la résistance d'isolement (par exemple, empêchement de la détérioration de la résistance d'isolement du condensateur à puce soudée). La pâte de soudure sans plomb en alliage de Sn-Zn est une pâte de soudure en poudre d'alliage mélangée avec un flux, auquel de 10 à 30% d'un dérivé de guanidine est ajouté. Conformément, la valeur du pH du résidu de flux après soudage est ajustée sur neutralité ou basicité afin de supprimer la génération de ion Zn+. En outre, l'hydroxyle d'amine et Zn dans la pâte sont mis en réaction l'un avec l'autre de sorte à former un état passif Zn-H2O, en empêchant ainsi une diminution de la résistance de la partie soudée. Par conséquent, la résistance de joint peut être maintenue même dans un environnement à haut niveau d'humidité.
PCT/JP2007/068363 2006-09-22 2007-09-21 Pâte de soudure sans plomb WO2008035758A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008501086A JP4162707B2 (ja) 2006-09-22 2007-09-21 鉛フリーソルダペースト

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-258074 2006-09-22
JP2006258074 2006-09-22

Publications (1)

Publication Number Publication Date
WO2008035758A1 true WO2008035758A1 (fr) 2008-03-27

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102642101A (zh) * 2010-12-02 2012-08-22 罗门哈斯电子材料有限公司 胺类助焊剂组合物和焊接方法
CN104476017A (zh) * 2014-11-13 2015-04-01 无锡伊佩克科技有限公司 一种无铅焊料用助焊剂及其制备方法
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

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107378313A (zh) * 2017-08-01 2017-11-24 东莞市盟纬电子有限公司 一种低固含量无松香无卤助焊剂及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09327789A (ja) * 1996-06-10 1997-12-22 Senju Metal Ind Co Ltd ソルダペースト
JPH10175092A (ja) * 1996-12-16 1998-06-30 Senju Metal Ind Co Ltd ソルダペースト
JP2000271781A (ja) * 1999-03-23 2000-10-03 Matsushita Electric Ind Co Ltd ソルダーペースト
JP2002103085A (ja) * 2000-10-03 2002-04-09 Fujifilm Arch Co Ltd 還元型フラックス組成物
JP2002114754A (ja) * 2000-10-03 2002-04-16 Fujifilm Arch Co Ltd ビグアニド化合物
JP2005021958A (ja) * 2003-07-01 2005-01-27 Senju Metal Ind Co Ltd 鉛フリーソルダペースト
WO2006126564A1 (fr) * 2005-05-25 2006-11-30 Senju Metal Industry Co., Ltd Pate de soudure sans plomb

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09327789A (ja) * 1996-06-10 1997-12-22 Senju Metal Ind Co Ltd ソルダペースト
JPH10175092A (ja) * 1996-12-16 1998-06-30 Senju Metal Ind Co Ltd ソルダペースト
JP2000271781A (ja) * 1999-03-23 2000-10-03 Matsushita Electric Ind Co Ltd ソルダーペースト
JP2002103085A (ja) * 2000-10-03 2002-04-09 Fujifilm Arch Co Ltd 還元型フラックス組成物
JP2002114754A (ja) * 2000-10-03 2002-04-16 Fujifilm Arch Co Ltd ビグアニド化合物
JP2005021958A (ja) * 2003-07-01 2005-01-27 Senju Metal Ind Co Ltd 鉛フリーソルダペースト
WO2006126564A1 (fr) * 2005-05-25 2006-11-30 Senju Metal Industry Co., Ltd Pate de soudure sans plomb

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102642101A (zh) * 2010-12-02 2012-08-22 罗门哈斯电子材料有限公司 胺类助焊剂组合物和焊接方法
CN104476017A (zh) * 2014-11-13 2015-04-01 无锡伊佩克科技有限公司 一种无铅焊料用助焊剂及其制备方法
CN104476017B (zh) * 2014-11-13 2016-09-21 兑元工业科技（惠州）有限公司 一种无铅焊料用助焊剂及其制备方法
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
WO2019102671A1 (fr) 2017-11-24 2019-05-31 千住金属工業株式会社 Flux et pâte à braser
KR20190069426A (ko) 2017-11-24 2019-06-19 센주긴조쿠고교 가부시키가이샤 플럭스 및 솔더 페이스트
JP2019093426A (ja) * 2017-11-24 2019-06-20 千住金属工業株式会社 フラックス及びソルダペースト
CN109996646A (zh) * 2017-11-24 2019-07-09 千住金属工业株式会社 助焊剂和焊膏
KR102026848B1 (ko) 2017-11-24 2019-09-30 센주긴조쿠고교 가부시키가이샤 플럭스 및 솔더 페이스트
US10843298B2 (en) 2017-11-24 2020-11-24 Senju Metal Industry Co., Ltd. Flux and solder paste
EP3683005A4 (fr) * 2017-11-24 2021-01-06 Senju Metal Industry Co., Ltd Flux et pâte à braser

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JP4162707B2 (ja) 2008-10-08
JPWO2008035758A1 (ja) 2010-01-28

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