JP2019093425A - Discoloration-resistant solder material, and discoloration-resistant solder joint - Google Patents
Discoloration-resistant solder material, and discoloration-resistant solder joint Download PDFInfo
- Publication number
- JP2019093425A JP2019093425A JP2017225677A JP2017225677A JP2019093425A JP 2019093425 A JP2019093425 A JP 2019093425A JP 2017225677 A JP2017225677 A JP 2017225677A JP 2017225677 A JP2017225677 A JP 2017225677A JP 2019093425 A JP2019093425 A JP 2019093425A
- Authority
- JP
- Japan
- Prior art keywords
- solder
- mass
- examples
- content
- wettability
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 182
- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000002845 discoloration Methods 0.000 title claims abstract description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 39
- 239000000956 alloy Substances 0.000 claims description 39
- 229910052718 tin Inorganic materials 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 238000004383 yellowing Methods 0.000 abstract description 18
- 229910001128 Sn alloy Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 65
- 239000010410 layer Substances 0.000 description 46
- 238000011156 evaluation Methods 0.000 description 33
- 230000001629 suppression Effects 0.000 description 30
- 238000004458 analytical method Methods 0.000 description 18
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 16
- 239000010949 copper Substances 0.000 description 16
- 229910004298 SiO 2 Inorganic materials 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 239000000523 sample Substances 0.000 description 10
- 229910017944 Ag—Cu Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000004544 sputter deposition Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 7
- 239000007769 metal material Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 229910017868 Cu—Ni—Co Inorganic materials 0.000 description 5
- 229910018956 Sn—In Inorganic materials 0.000 description 5
- 238000005476 soldering Methods 0.000 description 5
- 229910052785 arsenic Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910020836 Sn-Ag Inorganic materials 0.000 description 1
- 229910020830 Sn-Bi Inorganic materials 0.000 description 1
- 229910020888 Sn-Cu Inorganic materials 0.000 description 1
- 229910020935 Sn-Sb Inorganic materials 0.000 description 1
- 229910020988 Sn—Ag Inorganic materials 0.000 description 1
- 229910018728 Sn—Bi Inorganic materials 0.000 description 1
- 229910019204 Sn—Cu Inorganic materials 0.000 description 1
- 229910008757 Sn—Sb Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000000538 analytical sample Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 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 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Landscapes
- Electric Connection Of Electric Components To Printed Circuits (AREA)
Abstract
Description
本発明は、耐変色性はんだ材料、及び耐変色性はんだ継手に関する。 The present invention relates to a tarnish resistant solder material and tarnish resistant solder joints.
プリント基板への電子部品の実装といった、電子機器における電子部品の固定と電気的接続は、コスト面及び信頼性の面で最も有利なはんだ付けにより一般に行われている。
はんだ付けに用いるはんだのうち、Ｓｎ又はＳｎ系合金を含むはんだは、はんだの表面が酸化すると酸化膜であるＳｎＯ被膜を形成して黄色に変化する。このような酸化膜（ＳｎＯ被膜）の膜厚が厚くなるほど、はんだ表面の黄色度は高くなる。
Fixing and electrical connection of electronic components in electronic devices, such as mounting of electronic components on a printed circuit board, is generally performed by the most advantageous soldering in terms of cost and reliability.
Among the solders used for the soldering, when the solder surface is oxidized, the solder containing Sn or Sn-based alloy forms a SnO film which is an oxide film and turns yellow. As the thickness of such an oxide film (SnO film) increases, the yellowness of the solder surface increases.
Ｓｎ又はＳｎ系合金を含むはんだを用いてはんだ部品を搭載した場合やはんだ継手を形成した場合に、はんだ表面が黄色に変化していて金属光沢を失っていると、はんだの画像認識の自動処理の際に、はんだが検出されず、実際には存在しているはんだが認識されないという恐れがある。 When solder parts are mounted using solder containing Sn or Sn-based alloy, or when solder joints are formed, if the solder surface turns yellow and loses metallic gloss, automatic processing of image recognition of solder There is a risk that the solder will not be detected, and the solder actually present will not be recognized.
従来の表面の黄色変化を抑制したはんだとしては、例えば、Ｓｎの含有量が４０％以上の合金からなる金属材料またはＳｎの含有量が１００％である金属材料からなるはんだ層と、前記はんだ層の表面を被覆する被覆層を備えた直径が１〜１０００μmの球体であり、前記被覆層は、前記はんだ層の外側にＳｎＯ膜が形成され、前記ＳｎＯ膜の外側にＳｎＯ2膜が形成され、前記被覆層の厚さは、０ｎｍより大きく４．５ｎｍ以下であるはんだ材料が提案されている（特許文献１）。特許文献１のはんだにおいては、ＳｎＯ2膜を形成することにより、はんだ表面の黄色変化を抑制している。
しかし、特許文献１のはんだにおいては、ＳｎＯ2膜を形成するために、高エネルギー状態のプラズマ照射等が必要であり、製造工程が複雑となってしまう。
As a conventional solder in which the yellow color change on the surface is suppressed, for example, a solder layer made of a metal material consisting of an alloy having a content of 40% or more of Sn or a metal material having a content of Sn of 100% And a covering layer covering the surface of the ball, and the covering layer has a SnO film formed on the outside of the solder layer, and a SnO 2 film formed on the outside of the SnO film. The solder material whose thickness of the said coating layer is 4.5 nm or less larger than 0 nm is proposed (patent document 1). In the solder of Patent Document 1, the yellow change of the solder surface is suppressed by forming the SnO 2 film.
However, in the solder of Patent Document 1, plasma irradiation or the like in a high energy state is required to form the SnO 2 film, and the manufacturing process becomes complicated.
また、従来、Ｓｎ又はＳｎ系合金を含むはんだ表面の黄色変化を抑制するために、Ｐ、Ｇｅ、Ｇａなどの元素を添加することが行われている。これらの元素は、Ｓｎよりも酸化物生成自由エネルギーが小さく、非常に酸化されやすい。したがって、溶融はんだからはんだボールを形成する際に、ＳｎではなくＰ、Ｇｅ、Ｇａなどの元素が酸化されて表面に濃化し、はんだ表面の黄色変化を抑制することができる。しかし、一般的にはんだには、溶融した際に電子部品の金属上を広がっていく性質（濡れ性）が求められるところ、はんだ表面の黄色変化を抑制するためにこれらの元素の添加量を多くし濃化の度合いを高めると、はんだの濡れ性が低下してしまう。 Moreover, in order to suppress the yellow change of the solder surface containing Sn or Sn type alloy conventionally, adding elements, such as P, Ge, Ga, is performed. These elements have smaller oxide formation free energy than Sn and are very easily oxidized. Therefore, when forming a solder ball from molten solder, elements such as P, Ge, Ga, etc., instead of Sn, are oxidized and concentrated on the surface, and it is possible to suppress yellow change of the solder surface. However, in general, the solder is required to have the property (wettability) to spread on the metal of the electronic component when it is melted, but in order to suppress the yellow change of the solder surface, the addition amount of these elements is large When the degree of thickening is increased, the wettability of the solder is reduced.
以上のように、表面の黄色変化を抑制し、濡れ性に優れるはんだ材料が望まれている。 As mentioned above, the solder material which controls the yellow change of the surface and is excellent in wettability is desired.
本発明は、表面の黄色変化を抑制し、濡れ性に優れるはんだ材料又ははんだ継手を提供することを目的とする。 An object of the present invention is to provide a solder material or a solder joint which suppresses yellowing of the surface and is excellent in wettability.
本発明者らは、上記課題を解決するべく鋭意研究した結果、はんだ材料に特定量のＡｓ（砒素）を添加し、はんだ材料の表面にＡｓ濃化層を形成することで上記課題を解決できることを知見し、本発明を完成するに至った。本発明のはんだ材料においては、Ａｓの添加量が少量であるので、濡れ性を悪化させずに維持しながら、はんだ材料表面の黄色変化を抑制することができる。本発明の具体的態様は以下のとおりである。
なお、本明細書において、「〜」を用いて数値範囲を表す際は、その範囲は両端の数値を含むものとする。
As a result of intensive studies to solve the above problems, the present inventors can solve the above problems by adding a specific amount of As (arsenic) to the solder material and forming an As-concentrated layer on the surface of the solder material. The present invention has been completed. In the solder material of the present invention, since the amount of As added is small, it is possible to suppress the yellowing of the surface of the solder material while maintaining the wettability without deteriorating. Specific embodiments of the present invention are as follows.
In addition, in this specification, when expressing a numerical range using "-", the range shall include the numerical value of both ends.
[１]
Ｓｎ又はＳｎ系合金と、４０〜３２０質量ｐｐｍのＡｓとを含み、Ａｓ濃化層を有することを特徴とする耐変色性はんだ材料。
[２]
前記Ｓｎ又はＳｎ系合金が、０〜４質量％のＡｇ、０〜１質量％のＣｕ、０〜５２質量％のＩｎ、０〜０．１５質量％のＮｉ、及び０〜０．０１５質量％のＣｏを含み、残部がＳｎであることを特徴とする[１]に記載のはんだ材料。
[３]
粉末であることを特徴とする、[１]又は[２]に記載のはんだ材料。
[４]
前記粉末が、球径１〜１０００μｍの球状粉末であることを特徴とする[１]〜[３]のいずれかに記載のはんだ材料
[５]
Ｓｎ又はＳｎ系合金と、４０〜３２０質量ｐｐｍのＡｓとを含み、Ａｓ濃化層を有することを特徴とする耐変色性はんだ継手。
[1]
What is claimed is: 1. A color-resistant solder material comprising a Sn or Sn-based alloy and 40 to 320 mass ppm of As, and having an As-enriched layer.
[2]
The said Sn or Sn-type alloy is 0-4 mass% Ag, 0-1 mass% Cu, 0-52 mass% In, 0-0.15 mass% Ni, and 0-0.015 mass% The solder material according to [1], which contains Co and the balance is Sn.
[3]
The solder material according to [1] or [2], which is a powder.
[4]
The solder material according to any one of [1] to [3], wherein the powder is a spherical powder having a sphere diameter of 1 to 1000 μm.
[5]
A discoloration resistant solder joint comprising an Sn or Sn-based alloy and 40 to 320 mass ppm of As and having an As-enriched layer.
本発明のはんだ材料又ははんだ継手は、濡れ性を維持しながら、表面の黄色変化を抑制することができる。 The solder material or the solder joint of the present invention can suppress the yellowing of the surface while maintaining the wettability.
以下、本発明のはんだ材料及びはんだ継手について、説明する。 Hereinafter, the solder material and the solder joint of the present invention will be described.
本発明の耐変色性はんだ材料は、Ｓｎ又はＳｎ系合金と、４０〜３２０質量ｐｐｍのＡｓとを含み、Ａｓ濃化層を有する。 The color-resistant solder material of the present invention contains a Sn or Sn-based alloy and 40 to 320 mass ppm of As, and has an As-concentrated layer.
Ｓｎとしては、特に限定されず、純度が３Ｎ（９９．９％以上）、４Ｎ（９９．９９％以上）、５Ｎ（９９．９９９％以上）であるもの等の当業界で一般的なものを用いることができる。
Ｓｎ系合金としては、Ｓｎ−Ａｇ合金、Ｓｎ−Ｃｕ合金、Ｓｎ−Ａｇ−Ｃｕ合金、Ｓｎ−Ａｇ−Ｃｕ−Ｎｉ−Ｃｏ合金、Ｓｎ−Ｉｎ合金、Ｓｎ−Ｂｉ合金、Ｓｎ−Ｓｂ合金や前記合金組成にＡｇ、Ｃｕ、Ｉｎ、Ｎｉ、Ｃｏ、Ｓｂ、Ｂi、Ｇｅ、Ｐ、Ｆｅ、Ｚｎ、Ａｌ、Ｇａ等を更に添加した合金が挙げられる。
Ｓｎ又はＳｎ系合金は、不可避不純物を含んでいてもよい。
本発明の耐変色性はんだ材料に含まれるＳｎ又はＳｎ系合金は、０〜４質量％のＡｇ、０〜１質量％のＣｕ、０〜５２質量％のＩｎ、０〜０．１５質量％のＮｉ、及び０〜０．０１５質量％のＣｏを含み、残部がＳｎであることが好ましい。
はんだ材料全体の質量に対するＡｇの含有量は、０〜４質量％が好ましく、１〜４質量％がより好ましく、１〜３質量％が最も好ましい。
はんだ材料全体の質量に対するＣｕの含有量は、０〜１質量％が好ましく、０．３〜０．７５質量％がより好ましく、０．５〜０．７質量％が最も好ましい。
はんだ材料全体の質量に対するＩｎの含有量は、０〜５２質量％が好ましく、０〜１０質量％又は４０〜５２質量％がより好ましい。
上記の各元素の含有量の数値範囲について、各元素ごとに単独で用いても良く、又は、複数の元素の数値範囲を組み合わせて用いても良い。
The Sn is not particularly limited, and those generally used in the industry such as those having a purity of 3N (99.9% or more), 4N (99.99% or more), 5N (99.999% or more), etc. It can be used.
Examples of Sn-based alloys include Sn-Ag alloy, Sn-Cu alloy, Sn-Ag-Cu alloy, Sn-Ag-Cu-Ni-Co alloy, Sn-In alloy, Sn-Bi alloy, Sn-Sb alloy, and the like. The alloy which added Ag, Cu, In, Ni, Co, Sb, Bi, Ge, P, Fe, Zn, Al, Ga etc. to an alloy composition is mentioned.
The Sn or Sn-based alloy may contain unavoidable impurities.
The Sn or Sn-based alloy contained in the color-resistant solder material of the present invention contains 0 to 4% by mass of Ag, 0 to 1% by mass of Cu, 0 to 52% by mass of In, 0 to 0.15% by mass It is preferable that Ni and 0 to 0.015% by mass of Co be contained, with the balance being Sn.
0-4 mass% is preferable, as for content of Ag with respect to the mass of the whole solder material, 1-4 mass% is more preferable, and 1-3 mass% is the most preferable.
As for content of Cu with respect to the mass of the whole solder material, 0-1 mass% is preferable, 0.3-0.75 mass% is more preferable, 0.5-0.7 mass% is the most preferable.
0-52 mass% is preferable, and, as for content of In with respect to the mass of the whole solder material, 0-10 mass% or 40-52 mass% is more preferable.
About the numerical range of content of each above-mentioned element, you may use individually for every element, or may be used combining the numerical range of several elements.
はんだ材料全体の質量に対するＡｓの含有量は、４０〜３２０質量ｐｐｍ（０．００４０〜０．０３２０質量％）であり、７０〜３２０質量ｐｐｍが好ましく、７０〜２００質量ｐｐｍがより好ましい。Ａｓの含有量が上記範囲内であれば、黄色変化が抑制され、濡れ性に優れたはんだ材料が得られる。 Content of As with respect to the mass of the whole solder material is 40-320 mass ppm (0.0040-0.0320 mass%), 70-320 mass ppm is preferable, and 70-200 mass ppm is more preferable. When the content of As is within the above range, yellowing is suppressed, and a solder material having excellent wettability can be obtained.
本発明において、はんだ材料に含まれるＡｓ濃化層とは、はんだ材料の表面に形成されたＡｓの濃度がはんだ内部より高くなっている領域であり、以下の判定基準により存在を確認することができる。
（判定基準）
５．０ｍｍ×５．０ｍｍの大きさのサンプルにおいて、任意の７００μｍ×３００μｍのエリアを選定し、イオンスパッタリングを併用したＸＰＳ分析を行う。サンプル１個につき１つのエリアを選定し、３つのサンプルについてそれぞれ１回ずつ、合計３回の分析を行った。全３回の分析の全てにおいてＳ１≧Ｓ２となる場合、Ａｓ濃化層が形成されていると判断する。
ここで、
Ｓ１：ＸＰＳ分析のチャートにおいて、ＳｉＯ２換算の深さが０〜２×Ｄ１（ｎｍ）の領域におけるＡｓの検出強度の積分値
Ｓ２：ＸＰＳ分析のチャートにおいて、ＳｉＯ２換算の深さが２×Ｄ１〜４×Ｄ１（ｎｍ）の領域におけるＡｓの検出強度の積分値
Ｄ１：ＸＰＳ分析のチャートにおいて、Ｏ原子の検出強度が最大となったＳｉＯ２換算の深さ（Ｄｏ・ｍａｘ（ｎｍ））より深い部分において、Ｏ原子の検出強度が最大検出強度（Ｄｏ・ｍａｘにおける強度）の１／２の強度となる最初のＳｉＯ２換算の深さ（ｎｍ）。
上記のＡｓ濃化層の判定基準の詳細な条件は、後述の「（１）Ａｓ濃化層の有無の評価」の記載に従う。はんだ材料がＡｓ濃化層を有することにより、はんだの黄色変化を抑制することができる。
Ａｓ濃化層の厚み（ＳｉＯ２換算）は、０．５〜８．０ｎｍが好ましく、０．５〜４．０ｎｍがより好ましく、０．５〜２．０ｎｍが最も好ましい。Ａｓ濃化層の厚みが上記範囲内であれば、黄色変化が抑制され、濡れ性に優れたはんだ材料が得られる。
In the present invention, the As-enriched layer contained in the solder material is a region in which the concentration of As formed on the surface of the solder material is higher than that in the solder, and the existence thereof is confirmed by the following criteria. it can.
(Judgment criteria)
For a sample of 5.0 mm × 5.0 mm in size, an arbitrary 700 μm × 300 μm area is selected, and XPS analysis using ion sputtering in combination is performed. One area was selected for each sample, and three analyzes were performed once for each of three samples. If S1 ≧ S2 in all three analyzes, it is determined that an As-enriched layer is formed.
here,
S1: In the chart of XPS analysis, the integral value of the detection intensity of As in the region of SiO 2 converted
The detailed conditions of the judgment criteria of the above-described As-enriched layer follow the description of “(1) Evaluation of presence or absence of As-enriched layer” described later. When the solder material has an As-enriched layer, it is possible to suppress the yellow change of the solder.
The thickness of As concentrated layer (SiO 2 basis) is preferably 0.5～8.0Nm, more preferably 0.5~4.0nm, 0.5~2.0nm is most preferred. When the thickness of the As-enriched layer is within the above range, yellowing is suppressed, and a solder material having excellent wettability is obtained.
本発明において、はんだ材料の形態は特に限定されないが、粉末であることが好ましく、球状粉末であることが好ましい。はんだ材料が粉末であることにより微細な部品へのはんだ付けが可能となり、また、球状粉末であることによりはんだ材料の流動性が向上する。
また、はんだ材料が球状粉末である場合、球径は１〜１０００μｍが好ましく、１〜３００μｍがより好ましく、１〜１２０μｍが最も好ましい。球状粉末であるはんだ材料の球径が上記範囲内であれば、微細なはんだ付けが可能となる。
はんだ材料が球状粉末である場合、真球度は０．９０以上が好ましく、０．９５以上がより好ましく、０．９９以上が最も好ましい。
本発明において、球状粉末であるはんだ材料の球径及び真球度は、最小領域中心法（ＭＺＣ法）を用いるＣＮＣ画像測定システム（ミツトヨ社製のウルトラクイックビジョン ＵＬＴＲＡ ＱＶ３５０−ＰＲＯ測定装置）を使用して測定する。本願明細書において、真球度とは真球からのずれを表し、例えば５００個の各ボールの直径を長径で割った際に算出される算術平均値であり、値が上限である１．００に近いほど真球に近いことを表す。
In the present invention, the form of the solder material is not particularly limited, but a powder is preferable, and a spherical powder is preferable. The powder of the solder material enables soldering to fine parts, and the spherical powder improves the flowability of the solder material.
When the solder material is a spherical powder, the sphere diameter is preferably 1 to 1000 μm, more preferably 1 to 300 μm, and most preferably 1 to 120 μm. If the sphere diameter of the solder material which is spherical powder is within the above range, fine soldering becomes possible.
When the solder material is a spherical powder, the sphericity is preferably 0.90 or more, more preferably 0.95 or more, and most preferably 0.99 or more.
In the present invention, the spherical diameter and sphericity of the solder material which is a spherical powder use a CNC image measurement system (Ultra Quick Vision ULTRA QV350-PRO measurement device manufactured by Mitutoyo Corp.) using the minimum area center method (MZC method) Measure. In the specification of the present application, sphericity represents deviation from a true sphere, and is, for example, an arithmetic average value calculated when the diameter of each of 500 balls is divided by the major diameter, and the upper limit is 1.00. The closer to, the closer to a true sphere.
本発明において、はんだ材料のＬ＊ａ＊ｂ＊表色系における黄色度ｂ＊は、０〜１０．０が好ましく、３．０〜５．７がより好ましく、３．０〜５．０が最も好ましい。はんだ材料のＬ＊ａ＊ｂ＊表色系における黄色度ｂ＊が上記範囲内であれば、黄色度が低く、はんだが金属光沢を有するため、はんだの画像認識の自動処理の際に、はんだが的確に検出される。
後述の「（２）黄色変化の抑制の評価」において示すように、本発明において、黄色度ｂ＊は、ＣＭ−３５００ｄ２６００ｄ型分光測色計（コニカミノルタ社製）を使用して、Ｄ６５光源、１０度視野において、ＪＩＳ Ｚ ８７２２「色の測定方法−反射及び透過物体色」に準じて分光透過率を測定して、色彩値（Ｌ＊、ａ＊、ｂ＊）から求めることができる。
In the present invention, the yellowness b * of the solder material in the L * a * b * color system is preferably 0 to 10.0, more preferably 3.0 to 5.7, and 3.0 to 5.0. Most preferred. If the degree of yellowness b * in the L * a * b * color system of the solder material is within the above range, the degree of yellowness is low, and the solder has a metallic luster. Is accurately detected.
In the present invention, as shown in “(2) Evaluation of suppression of yellowing change” described later, in the present invention, the degree of yellowness b * is a D65 light source using a CM-3500d2600d type spectrophotometer (manufactured by Konica Minolta), The spectral transmittance can be measured from the color values (L * , a * , b * ) according to JIS Z 8722 "Measurement method of color-reflection and transmission object color" in a 10 ° visual field.
本発明の耐変色性はんだ継手は、Ｓｎ又はＳｎ系合金と、４０〜３２０質量ｐｐｍのＡｓとを含み、Ａｓ濃化層を有する。耐変色性はんだ継手は、上述の耐変色性はんだ材料から形成することができ、上述の耐変色性はんだ材料と同様の組成、物性を有することができる。 The color-resistant solder joint of the present invention contains a Sn or Sn-based alloy and 40 to 320 mass ppm of As, and has an As concentrated layer. The tarnish resistant solder joint can be formed from the tarnish resistant solder material described above, and can have the same composition and physical properties as the tarnish resistant solder material described above.
本発明のはんだ材料の使用形態は特に限定されず、はんだボールや、ロジン系樹脂、活性剤、溶剤等を含むフラックスと混合して製造するはんだペースト等として使用できるが、はんだボールとして使用することが好ましい。はんだボールとして使用する場合は、Ｓｎ又はＳｎ系合金とＡｓとを含む金属材料を、当業界で一般的な方法である滴下法を用いてはんだボールを製造することができる。また、はんだボールを、フラックスを塗布した１つの電極上にはんだボールを１つ搭載して接合するなど、当業界で一般的な方法で加工することによりはんだ継手を製造することができる。
このようにして製造された耐変色性はんだ継手は、濡れ性を維持しながら、表面の黄色変化を抑制することができる。
The use form of the solder material of the present invention is not particularly limited, and it can be used as a solder paste manufactured by mixing it with a solder ball, a flux containing a rosin resin, an activator, a solvent, etc. Is preferred. When used as a solder ball, a metal material containing a Sn or Sn-based alloy and As can be used to manufacture a solder ball using a dropping method which is a method common in the art. In addition, a solder joint can be manufactured by processing the solder ball by a method common to the industry, such as mounting and joining one solder ball on one flux-coated electrode.
The color-resistant solder joint manufactured in this manner can suppress the yellowing of the surface while maintaining the wettability.
このようにして調製されたはんだボールを用いて、電子機器などの部材を接合することができる。 A component such as an electronic device can be joined using the solder ball prepared in this manner.
以下、本発明について実施例により具体的に説明するが、本発明は実施例に記載の内容に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the contents described in the examples.
（評価）
実施例１〜４４及び比較例１〜４０それぞれのはんだボールについて、以下のとおり、（１）Ａｓ濃化層の有無の評価、（２）黄色変化の抑制の評価、及び（３）はんだ濡れ性の評価を行った。
(Evaluation)
About each solder ball of Examples 1 to 44 and Comparative Examples 1 to 40, (1) Evaluation of presence or absence of As-enriched layer, (2) Evaluation of suppression of yellow change, and (3) Solder wettability The evaluation of
（１）Ａｓ濃化層の有無の評価
Ａｓ濃化層の有無は、ＸＰＳ（Ｘ線光電分光法：X-ray Photoelectron Spectroscopy）による深さ方向分析を用いて以下の様に評価した。
（分析条件）
・分析装置：ＡＸＩＳ Ｎｏｖａ(クレイトス・アナリティカル社製)
・分析条件：Ｘ線源 ＡｌＫα線、Ｘ線銃電圧 １５ｋＶ、Ｘ線銃電流値 １０ｍＡ、分析エリア ７００μｍ×３００μｍ
・スパッタ条件：イオン種 Ａｒ＋、加速電圧 ２ｋＶ、スパッタリングレート ０．５ｎｍ／ｍｉｎ（ＳｉＯ２換算）
・カーボンテープを貼ったステージ上にはんだボールを隙間なく平坦に敷き詰めたものをサンプルとして分析を行った。サンプルの大きさは５．０ｍｍ×５．０ｍｍとした。
（評価手順）
５．０ｍｍ×５．０ｍｍの大きさのサンプルにおいて、任意の７００μｍ×３００μｍのエリアを選定し、イオンスパッタリングを行いながらＳｎ、Ｏ、Ａｓの各原子についてＸＰＳ分析を行い、ＸＰＳ分析のチャートを得た。サンプル１個につき１つのエリアを選定し、３つのサンプルについてそれぞれ１回ずつ、合計３回の分析を行った。得られたＸＰＳ分析のチャートにおいて、横軸は、スパッタ時間（ｍｉｎ）及びスパッタ時間からＳｉＯ２標準試料のスパッタエッチングレートを用いて算出したＳｉＯ２換算の深さ（ｎｍ）のいずれかから選択でき、縦軸は、検出強度（ｃｐｓ）である。以後の測定においては、ＸＰＳ分析のチャートにおける横軸を、スパッタ時間からＳｉＯ２標準試料のスパッタエッチングレートを用いて算出したＳｉＯ２換算の深さ（ｎｍ）とする。
図１〜３にＸＰＳ分析により得られるチャートの例を示す。図１〜３は、同一のサンプルについて縦軸の検出強度（ｃｐｓ）のスケールを変更したものであり、横軸はスパッタ時間から算出したＳｉＯ２換算の深さ（ｎｍ）である。
図２に示すように、各サンプルのＸＰＳ分析のチャートにおいて、Ｏ原子の検出強度が最大となったＳｉＯ２換算の深さをＤｏ・ｍａｘ（ｎｍ）とした。そして、Ｄｏ・ｍａｘより深い部分において、Ｏ原子の検出強度が、最大検出強度（Ｄｏ・ｍａｘにおける強度）の１／２の強度となる最初のＳｉＯ２換算の深さをＤ１（ｎｍ）とした。
図３に示すように、各サンプルのＸＰＳ分析のチャートにおいて、最表面から深さ２×Ｄ１までの領域（ＳｉＯ２換算の深さが０〜２×Ｄ１（ｎｍ）の領域）におけるＡｓの検出強度の積分値（Ｓ１）と、深さ２×Ｄ１からさらに２×Ｄ１だけ深い部分までの領域（ＳｉＯ２換算の深さが２×Ｄ１〜４×Ｄ１（ｎｍ）の領域）におけるＡｓの検出強度の積分値（Ｓ２）との比較を行った。そして、以下の基準に基づいて評価を行った。
・全３回の測定の全てにおいてＳ１≧Ｓ２となる
：Ａｓ濃化層が形成されている（○）
・全３回の測定のうちの２回以下の回数でＳ１≧Ｓ２となる
：Ａｓ濃化層が形成されていない（×）
(1) Evaluation of the presence or absence of the As-enriched layer The presence or absence of the As-enriched layer was evaluated as follows using depth direction analysis by XPS (X-ray photoelectron spectroscopy).
(Analysis conditions)
・ Analyzer: AXIS Nova (made by Kratos Analytical)
Analysis conditions: X-ray source AlK α ray, X-ray gun voltage 15 kV, X-ray gun current value 10 mA, analysis area 700 μm × 300 μm
Sputtering conditions: ion species Ar + , acceleration voltage 2 kV, sputtering rate 0.5 nm / min (SiO 2 equivalent)
・ Analytical samples were prepared by laying solder balls flat on a carbon tape-covered stage without gaps. The size of the sample was 5.0 mm × 5.0 mm.
(Evaluation procedure)
Arbitrary 700 μm × 300 μm area is selected for the sample of 5.0 mm × 5.0 mm size, XPS analysis is performed for each atom of Sn, O, As while performing ion sputtering, and a chart of XPS analysis is obtained The One area was selected for each sample, and three analyzes were performed once for each of three samples. In the chart of the obtained XPS analysis, the horizontal axis can be selected from any of the sputtering time (min) and the SiO 2 equivalent depth (nm) calculated using the sputtering etching rate of the SiO 2 standard sample from the sputtering time. The vertical axis is the detection intensity (cps). In the subsequent measurements, the horizontal axis in the chart of the XPS analysis is taken as the SiO 2 equivalent depth (nm) calculated using the sputter etching rate of the SiO 2 standard sample from the sputtering time.
The example of the chart obtained by XPS analysis in FIGS. 1-3 is shown. 1-3 is obtained by changing the scale of the detected intensities of the longitudinal axis (cps) for the same sample, the horizontal axis represents the depth in terms of SiO 2 calculated from the sputtering time (nm).
As shown in FIG. 2, in the chart of the XPS analysis of each sample, the SiO 2 converted depth at which the detected intensity of O atoms is maximized is taken as Do · max (nm). Then, in a portion deeper than Do · max, the first SiO 2 converted depth is defined as D1 (nm) at which the detected intensity of O atoms is half the maximum detected intensity (intensity at Do · max) .
As shown in FIG. 3, in the chart of the XPS analysis of each sample, detection of As in the region from the outermost surface to the
・ S1 ≧ S2 in all three measurements
: As enriched layer is formed (○)
・ S1 ≧ S2 in two or less of all three measurements
: As concentrated layer not formed (x)
（２）黄色変化の抑制の評価
空気雰囲気の恒温槽を２００℃に加熱し、各はんだボール（球径０．３ｍｍ）を恒温槽中で２時間加熱した。Ｌ＊ａ＊ｂ＊表色系における黄色度ｂ＊について、加熱前及び加熱後のはんだボールの測定を行い、加熱後のｂ＊から加熱前のｂ＊を引いた増加量（Δｂ＊）を算出した。ただし、実施例３８〜４４及び比較例３５〜４０のＳｎ−Ｉｎ系はんだについては、融点が２００℃以下であるため、１００℃に加熱した恒温槽中で２０日間加熱して同様の測定及び算出を行った。
黄色度ｂ＊は、ＣＭ−３５００ｄ２６００ｄ型分光測色計（コニカミノルタ社製）を使用して、Ｄ６５光源、１０度視野において、ＪＩＳ Ｚ ８７２２「色の測定方法−反射及び透過物体色」に準じて分光透過率を測定して、色彩値（Ｌ＊、ａ＊、ｂ＊）から求めた。なお、色彩値（Ｌ＊、ａ＊、ｂ＊）は、ＪＩＳ Ｚ ８７２９「色の表示方法―色彩値Ｌ＊ａ＊ｂ＊表色系及びＬ＊Ｕ＊Ｖ＊表色系」に規定されているとおりである。
各金属組成のはんだボールにおいて、Ａｓを添加しない比較例１、７、１３、１９、２５、２７、３３又は３５のはんだボールのΔｂ＊（Δｂ＊（基準））との比較を行い、以下の基準に基づいて評価を行った。
Δｂ＊の値がΔｂ＊（基準）の５０％以下である ：○○（非常に良好）
Δｂ＊の値がΔｂ＊（基準）の５０％を超え７０％以下である：○（良好）
Δｂ＊の値がΔｂ＊（基準）の７０％より大きい ：×（不可）
(2) Evaluation of suppression of yellowing A constant temperature bath in an air atmosphere was heated to 200 ° C., and each solder ball (ball diameter 0.3 mm) was heated in the constant temperature bath for 2 hours. L * a * b * for yellowness b * in the color system performs measurement of the solder ball after heating before and heated, increasing the amount of minus b * before heating the b * after heating ([Delta] b *) Calculated. However, since the melting point of the Sn-In solders of Examples 38 to 44 and Comparative Examples 35 to 40 is 200 ° C. or less, the same measurement and calculation are performed by heating for 20 days in a thermostat heated at 100 ° C. Did.
The degree of yellowness b * is in accordance with JIS Z 8722 “Measurement method of color-reflection and transmission object color” in a D65 light source and 10 ° visual field using a CM-3500d2600d type spectrocolorimeter (manufactured by Konica Minolta) Spectral transmittance was measured and determined from color values (L * , a * , b * ). The color values (L * , a * , b * ) are defined in JIS Z 8729 "Color display method-color values L * a * b * color system and L * U * V * color system". As it is.
The solder balls of each metal composition were compared with Δb * (Δb * (reference)) of the solder balls of Comparative Examples 1, 7, 13, 19, 25, 27, 33 or 35 in which As was not added. Evaluation was performed based on the criteria.
The value of [Delta] b * is less than 50% of [Delta] b * (reference): ○○ (very good)
The value of [Delta] b * is less than 70% more than 50% of [Delta] b * (reference): ○ (good)
The value of [Delta] b * is greater than 70% of [Delta] b * (reference): × (poor)
（３）はんだ濡れ性の評価
Ｂａｒｅ−Ｃｕ（裸銅）の電極パッド（基板に設けた電極の開口径（Solder Resist Opening）： ０．２４ｍｍ）に、フラックスＷＦ−６４００（千住金属工業社製）を厚みが０．１１５ｍｍとなるように印刷し、その上に各はんだボールをマウントした。はんだボールをマウントした電極パッドを、２５℃から昇温速度１℃/ｓｅｃにてＮ２雰囲気下で２６０℃まで昇温し、リフローした。ただし、実施例３８〜４４及び比較例３５〜４０のＳｎ−Ｉｎ系はんだについては、融点が２００℃以下であるため、温度範囲を２５℃〜１８０℃に設定し、それ以外の条件は同様にしてリフローした。リフロー後に、はんだボールをマウントした電極パッドを、蒸留水中に浸漬し、１分間超音波洗浄を行った。はんだ付けされずに洗浄工程でなくなってしまったバンプ数（ミッシングバンプ数）をカウントし、以下の基準に基づいて評価を行った。
１００バンプ中のミッシングバンプが０個 ：○○（非常に良好）
１００バンプ中のミッシングバンプが１〜５個 ：○（良好）
１００バンプ中のミッシングバンプが６個以上 ：×（不可）
(3) Evaluation of solder wettability The electrode pad of Bare-Cu (naked copper) (the opening diameter of the electrode provided on the substrate (Solder Resist Opening): 0.24 mm), the flux WF-6400 (manufactured by Senju Metal Industry Co., Ltd.) Were printed to a thickness of 0.115 mm, and each solder ball was mounted thereon. The electrode pad mounted with the solder ball was reflowed by raising the temperature to 25 ° C. to 260 ° C. in an N 2 atmosphere at a temperature rising rate of 1 ° C./sec. However, for the Sn-In solders of Examples 38 to 44 and Comparative Examples 35 to 40, since the melting point is 200 ° C. or less, the temperature range is set to 25 ° C. to 180 ° C., and the other conditions are the same. Reflowed. After reflow, the electrode pad mounted with the solder ball was immersed in distilled water and subjected to ultrasonic cleaning for 1 minute. The number of bumps not removed in the cleaning process without soldering (number of missing bumps) was counted and evaluated based on the following criteria.
0 pieces of missing bumps in 100 bumps: ○ ○ (very good)
1 to 5 missing bumps in 100 bumps: ○ (Good)
6 or more missing bumps in 100 bumps: x (not allowed)
（実施例１〜７、比較例１〜６）
以下の表１に示す組成で実施例１〜７及び比較例１〜６のはんだ用金属材料を調合した。調合した実施例１〜７及び比較例１〜６のはんだ用金属材料から滴下法によりはんだボール（球径０．３ｍｍ）を製造した。得られた実施例１〜７及び比較例１〜６のはんだボールを、空気中において乾燥装置を用いて３０分間乾燥させ、Ａｓをはんだボール表面側に濃化させた。
なお、以下の表１〜６中の各成分の数値は、はんだ用金属材料全体の質量に対する各成分の質量％を表し、Ｓｎ以外の元素については配合時に実際に計量した量であり、Ｓｎについては合計が１００質量％となるように残部として配合した量を意味する。また、以下の表１〜６において、各はんだ用金属材料に用いたＳｎは、３Ｎ材であり不可避不純物を含むものである。
(Examples 1 to 7, Comparative Examples 1 to 6)
The metal materials for solder of Examples 1 to 7 and Comparative Examples 1 to 6 were prepared with the compositions shown in Table 1 below. Solder balls (ball diameter: 0.3 mm) were manufactured from the prepared metal materials for solder of Examples 1 to 7 and Comparative Examples 1 to 6 by a dropping method. The obtained solder balls of Examples 1 to 7 and Comparative Examples 1 to 6 were dried in air using a drying device for 30 minutes to concentrate As on the solder ball surface side.
In addition, the numerical value of each component in the following Tables 1-6 represents the mass% of each component with respect to the mass of the whole metal material for solder, and it is the quantity actually measured at the time of mixing about elements other than Sn about Sn Means an amount blended as the balance so that the total is 100% by mass. Moreover, in Tables 1 to 6 below, Sn used for each solder metal material is a 3N material and contains unavoidable impurities.
そして、実施例１〜７及び比較例１〜６それぞれのはんだボールについて、上記のとおり、（１）Ａｓ濃化層の有無の評価、（２）黄色変化の抑制の評価、及び（３）はんだ濡れ性の評価を行った。評価結果を以下の表１に示す。 And about the solder ball of each of Examples 1 to 7 and Comparative Examples 1 to 6, as described above, (1) evaluation of presence or absence of As concentrated layer, (2) evaluation of suppression of yellow change, and (3) solder The wettability was evaluated. The evaluation results are shown in Table 1 below.
上記表１の結果より、Ｓｎを含むはんだに関して、Ａｓの含有量が４０〜３２０質量ｐｐｍ（０．００４０〜０．０３２０質量％）である実施例１〜７においては、Ａｓ濃化層が形成されており、黄色変化の抑制及びはんだ濡れ性のいずれにおいても非常に良好又は良好であった。特に、Ａｓの含有量が７０〜２００質量ｐｐｍ（０．００７０〜０．０２００質量％）である実施例２〜５においては、黄色変化の抑制及びはんだ濡れ性のいずれも非常に良好であった。 From the results in Table 1 above, in Examples 1 to 7 in which the content of As is 40 to 320 mass ppm (0.0040 to 0.0320 mass%) with respect to the solder containing Sn, an As-rich layer is formed. It was very good or good in both suppression of yellowing and solderability. In particular, in Examples 2 to 5 in which the content of As is 70 to 200 mass ppm (0.0070 to 0.0200 mass%), both suppression of yellow change and solder wettability were very good. .
一方、Ａｓを含まない比較例１においては、はんだ濡れ性は非常に良好であるものの、黄色変化を抑制することができなかった。また、Ａｓの含有量が４０質量ｐｐｍ（０．００４０質量％）未満である比較例２〜５においては、はんだ濡れ性は非常に良好であるものの、Ａｓ濃化層が形成されておらず、黄色変化を抑制することができなかった。さらに、Ａｓの含有量が３２０質量ｐｐｍ（０．０３２０質量％）を超える比較例６においては、Ａｓ濃化層が形成されており、黄色変化の抑制は良好であるものの、十分なはんだ濡れ性が得られなかった。 On the other hand, in Comparative Example 1 in which As was not contained, although the solder wettability was very good, the yellow change could not be suppressed. Moreover, in Comparative Examples 2 to 5 in which the content of As is less than 40 mass ppm (0.0040 mass%), although the solder wettability is very good, the As concentrated layer is not formed, It was not possible to suppress yellowing. Furthermore, in Comparative Example 6 in which the content of As exceeds 320 mass ppm (0.0320 mass%), an As-enriched layer is formed, and although suppression of yellow change is good, sufficient solder wettability is obtained. Was not obtained.
（実施例８〜１４、比較例７〜１２）
上記の表１に示す組成の代わりに、以下の表２に示す組成を用いた以外は実施例１〜７及び比較例１〜６と同様にして、実施例８〜１４及び比較例７〜１２のはんだボールを製造した。
(Examples 8-14, comparative examples 7-12)
Examples 8 to 14 and Comparative Examples 7 to 12 are the same as Examples 1 to 7 and Comparative Examples 1 to 6 except that the compositions shown in Table 2 below were used instead of the compositions shown in Table 1 above. Manufactured solder balls.
そして、実施例８〜１４及び比較例７〜１２それぞれのはんだボールについて、上記のとおり、（１）Ａｓ濃化層の有無の評価、（２）黄色変化の抑制の評価、及び（３）はんだ濡れ性の評価を行った。評価結果を以下の表２に示す。 And about each solder ball of Examples 8-14 and Comparative Examples 7-12, as mentioned above, evaluation of the existence of (1) As concentrated layer, (2) evaluation of suppression of yellow change, and (3) solder The wettability was evaluated. The evaluation results are shown in Table 2 below.
上記表２の結果より、Ｓｎ−Ａｇ−Ｃｕ合金（Ａｇの含有量：３質量％、Ｃｕの含有量：０．５質量％）を含むはんだに関しても、Ａｓの含有量が４０〜３２０質量ｐｐｍ（０．００４０〜０．０３２０質量％）である実施例８〜１４においては、実施例１〜７と同様に、Ａｓ濃化層が形成されており、黄色変化の抑制及びはんだ濡れ性のいずれにおいても非常に良好又は良好であった。特に、Ａｓの含有量が７０〜２００質量ｐｐｍ（０．００７０〜０．０２００質量％）である実施例９〜１２においては、黄色変化の抑制及びはんだ濡れ性のいずれも非常に良好であった。 From the results in Table 2 above, the content of As is also 40 to 320 mass ppm for solders containing Sn-Ag-Cu alloy (Ag content: 3 mass%, Cu content: 0.5 mass%) In Examples 8 to 14 in which the amount is (0.0040 to 0.0320 mass%), an As-enriched layer is formed as in Examples 1 to 7, and any of suppression of yellow change and solder wettability Were also very good or good. In particular, in Examples 9 to 12 in which the content of As is 70 to 200 mass ppm (0.0070 to 0.0200 mass%), both suppression of the yellow change and solder wettability were very good. .
一方、Ｓｎ−Ａｇ−Ｃｕ合金（Ａｇの含有量：３質量％、Ｃｕの含有量：０．５質量％）を含むはんだに関しても、Ａｓを含まない比較例７においては、比較例１と同様に、はんだ濡れ性は非常に良好であるものの、黄色変化を抑制することができなかった。また、Ａｓの含有量が４０質量ｐｐｍ（０．００４０質量％）未満である比較例８〜１１においては、比較例２〜５と同様に、はんだ濡れ性は非常に良好であるものの、Ａｓ濃化層が形成されておらず、黄色変化を抑制することができなかった。さらに、Ａｓの含有量が３２０質量ｐｐｍ（０．０３２０質量％）を超える比較例１２においては、Ａｓ濃化層が形成されており、黄色変化の抑制は非常に良好であるものの、十分なはんだ濡れ性が得られなかった。 On the other hand, the solder containing the Sn-Ag-Cu alloy (Ag content: 3% by mass, Cu content: 0.5% by mass) is also similar to Comparative Example 1 in Comparative Example 7 not containing As. Although the solder wettability was very good, it was not possible to suppress the yellow change. Further, in Comparative Examples 8 to 11 in which the content of As is less than 40 mass ppm (0.0040 mass%), as in Comparative Examples 2 to 5, although the solder wettability is very good, the As concentration is high. Layer was not formed, and the yellowing could not be suppressed. Furthermore, in Comparative Example 12 in which the content of As exceeds 320 mass ppm (0.0320 mass%), an As-enriched layer is formed, and although the suppression of yellow change is very good, sufficient solder Wettability was not obtained.
（実施例１５〜２１、比較例１３〜１８）
上記の表１に示す組成の代わりに、以下の表３に示す組成を用いた以外は実施例１〜７及び比較例１〜６と同様にして、実施例１５〜２１及び比較例１３〜１８のはんだボールを製造した。
(Examples 15-21, Comparative Examples 13-18)
Examples 15 to 21 and Comparative Examples 13 to 18 are the same as Examples 1 to 7 and Comparative Examples 1 to 6 except that the compositions shown in Table 3 below were used instead of the compositions shown in Table 1 above. Manufactured solder balls.
そして、実施例１５〜２１及び比較例１３〜１８それぞれのはんだボールについて、上記のとおり、（１）Ａｓ濃化層の有無の評価、（２）黄色変化の抑制の評価、及び（３）はんだ濡れ性の評価を行った。評価結果を以下の表３に示す。 And about each solder ball of Examples 15-21 and Comparative Examples 13-18, as mentioned above, evaluation of the existence of (1) As concentrated layer, (2) evaluation of suppression of yellow change, and (3) solder The wettability was evaluated. The evaluation results are shown in Table 3 below.
上記表３の結果より、Ｓｎ−Ａｇ−Ｃｕ合金（Ａｇの含有量：１質量％、Ｃｕの含有量：０．５質量％）を含むはんだに関しても、Ａｓの含有量が４０〜３２０質量ｐｐｍ（０．００４０〜０．０３２０質量％）である実施例１５〜２１においては、実施例１〜７と同様に、Ａｓ濃化層が形成されており、黄色変化の抑制及びはんだ濡れ性のいずれにおいても非常に良好又は良好であった。特に、Ａｓの含有量が７０〜２００質量ｐｐｍ（０．００７０〜０．０２００質量％）である実施例１６〜１９においては、黄色変化の抑制及びはんだ濡れ性のいずれも非常に良好であった。 From the results of Table 3 above, the content of As is 40 to 320 mass ppm also for the solder containing Sn-Ag-Cu alloy (Ag content: 1 mass%, Cu content: 0.5 mass%) In Examples 15 to 21 of (0.0040 to 0.0320 mass%), an As-enriched layer is formed as in Examples 1 to 7, and any of suppression of yellow change and solder wettability Were also very good or good. In particular, in Examples 16 to 19 in which the content of As is 70 to 200 mass ppm (0.0070 to 0.0200 mass%), both suppression of yellow change and solder wettability were very good. .
一方、Ｓｎ−Ａｇ−Ｃｕ合金（Ａｇの含有量：１質量％、Ｃｕの含有量：０．５質量％）を含むはんだに関しても、Ａｓを含まない比較例１３においては、比較例１と同様に、はんだ濡れ性は非常に良好であるものの、黄色変化を抑制することができなかった。また、Ａｓの含有量が４０質量ｐｐｍ（０．００４０質量％）未満である比較例１４〜１７においては、比較例２〜５と同様に、はんだ濡れ性は非常に良好であるものの、Ａｓ濃化層が形成されておらず、黄色変化を抑制することができなかった。さらに、Ａｓの含有量が３２０質量ｐｐｍ（０．０３２０質量％）を超える比較例１８においては、Ａｓ濃化層が形成されており、黄色変化の抑制は非常に良好であるものの、十分なはんだ濡れ性が得られなかった。 On the other hand, also with respect to the solder containing the Sn-Ag-Cu alloy (content of Ag: 1% by mass, content of Cu: 0.5% by mass), Comparative Example 13 containing no As is the same as Comparative Example 1 Although the solder wettability was very good, it was not possible to suppress the yellow change. Moreover, in Comparative Examples 14 to 17 in which the content of As is less than 40 mass ppm (0.0040 mass%), as in Comparative Examples 2 to 5, although the solder wettability is very good, the As concentration is high. Layer was not formed, and the yellowing could not be suppressed. Furthermore, in Comparative Example 18 in which the content of As exceeds 320 mass ppm (0.0320 mass%), an As concentrated layer is formed, and although the suppression of yellow change is very good, sufficient solder Wettability was not obtained.
（実施例２２〜２９、比較例１９〜２６）
上記の表１に示す組成の代わりに、以下の表４に示す組成を用いた以外は実施例１〜７及び比較例１〜６と同様にして、実施例２２〜２９及び比較例１９〜２６のはんだボールを製造した。
(Examples 22-29, comparative examples 19-26)
Examples 22 to 29 and Comparative Examples 19 to 26 are the same as Examples 1 to 7 and Comparative Examples 1 to 6 except that the compositions shown in Table 4 below were used instead of the compositions shown in Table 1 above. Manufactured solder balls.
そして、実施例２２〜２９及び比較例１９〜２６それぞれのはんだボールについて、上記のとおり、（１）Ａｓ濃化層の有無の評価、（２）黄色変化の抑制の評価、及び（３）はんだ濡れ性の評価を行った。評価結果を以下の表４に示す。 And about each solder ball of Examples 22-29 and comparative examples 19-26, as mentioned above, evaluation of the existence of (1) As concentrated layer, (2) evaluation of suppression of yellow change, and (3) solder The wettability was evaluated. The evaluation results are shown in Table 4 below.
上記表４の結果より、Ｓｎ−Ａｇ−Ｃｕ合金（Ａｇの含有量：４質量％、Ｃｕの含有量：０．５質量％）を含むはんだに関しても、Ａｓの含有量が４０〜３２０質量ｐｐｍ（０．００４０〜０．０３２０質量％）である実施例２２〜２８においては、実施例１〜７と同様に、Ａｓ濃化層が形成されており、黄色変化の抑制及びはんだ濡れ性のいずれにおいても非常に良好又は良好であった。特に、Ａｓの含有量が７０〜２００質量ｐｐｍ（０．００７０〜０．０２００質量％）である実施例２３〜２６においては、黄色変化の抑制及びはんだ濡れ性のいずれも非常に良好であった。 From the results of Table 4 above, the content of As is 40 to 320 mass ppm also for the solder containing Sn-Ag-Cu alloy (Ag content: 4 mass%, Cu content: 0.5 mass%) In Examples 22 to 28 in which the amount is (0.0040 to 0.0320 mass%), an As-enriched layer is formed as in Examples 1 to 7, and any of suppression of yellow change and solder wettability can be obtained. Were also very good or good. In particular, in Examples 23 to 26 in which the content of As is 70 to 200 mass ppm (0.0070 to 0.0200 mass%), both suppression of yellow change and solder wettability were very good. .
また、Ａｇの含有量を４質量％、Ｃｕの含有量を１質量％に変更したＳｎ−Ａｇ−Ｃｕ合金を含むはんだに関しても、Ａｓの含有量が４０〜３２０質量ｐｐｍ（０．００４０〜０．０３２０質量％）である実施例２９において、実施例２２〜２８と同様に良好な評価結果が得られた。実施例２９については、実施例２３〜２６と同様に、黄色変化の抑制及びはんだ濡れ性のいずれも非常に良好であった。 In addition, the content of As is 40 to 320 mass ppm (0.0040 to 0) also for a solder containing a Sn-Ag-Cu alloy in which the content of Ag is changed to 4% by mass and the content of Cu to 1% by mass. In Example 29 which is .0320% by mass), good evaluation results were obtained as in Examples 22 to 28. For Example 29, as in Examples 23 to 26, both suppression of yellowing and solderability were both very good.
一方、Ｓｎ−Ａｇ−Ｃｕ合金（Ａｇの含有量：４質量％、Ｃｕの含有量：０．５質量％）を含むはんだに関しても、Ａｓを含まない比較例１９においては、比較例１と同様に、はんだ濡れ性は非常に良好であるものの、黄色変化を抑制することができなかった。また、Ａｓの含有量が４０質量ｐｐｍ（０．００４０質量％）未満である比較例２０〜２３においては、比較例２〜５と同様に、はんだ濡れ性は非常に良好であるものの、Ａｓ濃化層が形成されておらず、黄色変化を抑制することができなかった。さらに、Ａｓの含有量が３２０質量ｐｐｍ（０．０３２０質量％）を超える比較例２４においては、Ａｓ濃化層が形成されており、黄色変化の抑制は非常に良好であるものの、十分なはんだ濡れ性が得られなかった。 On the other hand, also with respect to the solder containing the Sn-Ag-Cu alloy (content of Ag: 4% by mass, content of Cu: 0.5% by mass), similar to Comparative Example 1 in Comparative Example 19 not containing As. Although the solder wettability was very good, it was not possible to suppress the yellow change. In addition, in Comparative Examples 20 to 23 in which the content of As is less than 40 mass ppm (0.0040 mass%), as in Comparative Examples 2 to 5, although the solder wettability is very good, the As concentration is high. Layer was not formed, and the yellowing could not be suppressed. Furthermore, in Comparative Example 24 in which the content of As exceeds 320 mass ppm (0.0320 mass%), an As concentrated layer is formed, and although the suppression of yellow change is very good, sufficient solder Wettability was not obtained.
また、Ａｇの含有量を４質量％、Ｃｕの含有量を１質量％に変更したＳｎ−Ａｇ−Ｃｕ合金を含むはんだに関しても、Ａｓを含まない比較例２５においては比較例１９と同様に、Ａｓの含有量が３２０質量ｐｐｍ（０．０３２０質量％）を超える比較例２６においては比較例２３と同様に、不十分な評価結果となった。 Further, as to the solder containing a Sn-Ag-Cu alloy in which the content of Ag is changed to 4% by mass and the content of Cu to 1% by mass, Comparative Example 25 not containing As is similar to Comparative Example 19 In Comparative Example 26 in which the content of As exceeds 320 mass ppm (0.0320 mass%), the evaluation results are insufficient as in Comparative Example 23.
（実施例３０〜３７、比較例２７〜３４）
上記の表１に示す組成の代わりに、以下の表５に示す組成を用いた以外は実施例１〜７及び比較例１〜６と同様にして、実施例３０〜３７及び比較例２７〜３４のはんだボールを製造した。
(Examples 30 to 37, Comparative Examples 27 to 34)
Examples 30 to 37 and Comparative Examples 27 to 34 are the same as Examples 1 to 7 and Comparative Examples 1 to 6 except that the compositions shown in Table 5 below were used instead of the compositions shown in Table 1 above. Manufactured solder balls.
そして、実施例３０〜３７及び比較例２７〜３４それぞれのはんだボールについて、上記のとおり、（１）Ａｓ濃化層の有無の評価、（２）黄色変化の抑制の評価、及び（３）はんだ濡れ性の評価を行った。評価結果を以下の表５に示す。 And about the solder ball of each of Examples 30 to 37 and Comparative Examples 27 to 34, as described above, (1) evaluation of presence or absence of As concentrated layer, (2) evaluation of suppression of yellow change, and (3) solder The wettability was evaluated. The evaluation results are shown in Table 5 below.
上記表５の結果より、Ｓｎ−Ａｇ−Ｃｕ−Ｎｉ−Ｃｏ合金（Ａｇの含有量：３質量％、Ｃｕの含有量：０．５質量％、Ｎｉの含有量：０．０５質量％、Ｃｏの含有量：０．０１質量％）を含むはんだに関しても、Ａｓの含有量が４０〜３２０質量ｐｐｍ（０．００４０〜０．０３２０質量％）である実施例３０〜３６においては、実施例１〜７と同様に、Ａｓ濃化層が形成されており、黄色変化の抑制及びはんだ濡れ性のいずれにおいても非常に良好又は良好であった。特に、Ａｓの含有量が７０〜２００質量ｐｐｍ（０．００７０〜０．０２００質量％）である実施例３１〜３４においては、黄色変化の抑制及びはんだ濡れ性のいずれも非常に良好であった。 From the results in Table 5 above, Sn-Ag-Cu-Ni-Co alloy (Ag content: 3% by mass, Cu content: 0.5% by mass, Ni content: 0.05% by mass, Co In Examples 30 to 36 in which the content of As is 40 to 320 mass ppm (0.0040 to 0.0320 mass%), a solder containing 0.01 mass% of the content of As in the case of ̃7, an As-enriched layer was formed, and it was very good or good in both suppression of yellow change and solder wettability. In particular, in Examples 31 to 34 in which the content of As is 70 to 200 mass ppm (0.0070 to 0.0200 mass%), both suppression of yellow change and solder wettability were very good. .
また、Ｎｉの含有量を０．１５質量％、Ｃｏの含有量を０．０１５質量％に変更したＳｎ−Ａｇ−Ｃｕ−Ｎｉ−Ｃｏ合金を含むはんだに関しても、Ａｓの含有量が４０〜３２０質量ｐｐｍ（０．００４０〜０．０３２０質量％）である実施例３７において、実施例３０〜３６と同様に良好な評価結果が得られた。実施例３７については、実施例３１〜３４と同様に、黄色変化の抑制及びはんだ濡れ性のいずれも非常に良好であった。 In addition, the content of As is 40 to 320 also for a solder including a Sn-Ag-Cu-Ni-Co alloy in which the content of Ni is changed to 0.15% by mass and the content of Co to 0.015% by mass. In Example 37 which is mass ppm (0.0040-0.0320 mass%), the favorable evaluation result was obtained similarly to Examples 30-36. For Example 37, as in Examples 31 to 34, both suppression of yellowing and solderability were both very good.
一方、Ｓｎ−Ａｇ−Ｃｕ−Ｎｉ−Ｃｏ合金（Ａｇの含有量：３質量％、Ｃｕの含有量：０．５質量％、Ｎｉの含有量：０．０５質量％、Ｃｏの含有量：０．０１質量％）を含むはんだに関しても、Ａｓを含まない比較例２７においては、比較例１と同様に、はんだ濡れ性は非常に良好であるものの、黄色変化を抑制することができなかった。また、Ａｓの含有量が４０質量ｐｐｍ（０．００４０質量％）未満である比較例２８〜３１においては、比較例２〜５と同様に、はんだ濡れ性は非常に良好であるものの、Ａｓ濃化層が形成されておらず、黄色変化を抑制することができなかった。さらに、Ａｓの含有量が３２０質量ｐｐｍ（０．０３２０質量％）を超える比較例３２においては、Ａｓ濃化層が形成されており、黄色変化の抑制は非常に良好であるものの、十分なはんだ濡れ性が得られなかった。 Meanwhile, Sn-Ag-Cu-Ni-Co alloy (Ag content: 3% by mass, Cu content: 0.5% by mass, Ni content: 0.05% by mass, Co content: 0 As for the solder containing .01% by mass, in Comparative Example 27 not containing As, as in Comparative Example 1, although the solder wettability was very good, the yellow change could not be suppressed. Moreover, in Comparative Examples 28 to 31 in which the content of As is less than 40 mass ppm (0.0040 mass%), as in Comparative Examples 2 to 5, although the solder wettability is very good, the As concentration is high. Layer was not formed, and the yellowing could not be suppressed. Furthermore, in Comparative Example 32 in which the content of As exceeds 320 mass ppm (0.0320 mass%), an As-enriched layer is formed, and although the suppression of yellow change is very good, sufficient solder Wettability was not obtained.
また、Ｎｉの含有量を０．１５質量％、Ｃｏの含有量を０．０１５質量％に変更したＳｎ−Ａｇ−Ｃｕ−Ｎｉ−Ｃｏ合金を含むはんだに関しても、Ａｓを含まない比較例３３においては比較例２７と同様に、Ａｓの含有量が３２０質量ｐｐｍ（０．０３２０質量％）を超える比較例３４においては比較例３２と同様に、不十分な評価結果となった。 Further, in the case of a solder including a Sn-Ag-Cu-Ni-Co alloy in which the content of Ni is changed to 0.15% by mass and the content of Co to 0.015% by mass, Comparative Example 33 not containing As is In the same manner as in Comparative Example 27, in Comparative Example 34 in which the content of As exceeds 320 mass ppm (0.0320 mass%), the evaluation results are insufficient as in Comparative Example 32.
（実施例３８〜４４、比較例３５〜４０）
上記の表１に示す組成の代わりに、以下の表６に示す組成を用いた以外は実施例１〜７及び比較例１〜６と同様にして、実施例３８〜４４及び比較例３５〜４０のはんだボールを製造した。
(Examples 38 to 44, Comparative Examples 35 to 40)
Examples 38 to 44 and Comparative Examples 35 to 40 are the same as Examples 1 to 7 and Comparative Examples 1 to 6 except that the compositions shown in Table 6 below are used instead of the compositions shown in Table 1 above. Manufactured solder balls.
そして、実施例３８〜４４及び比較例３５〜４０それぞれのはんだボールについて、上記のとおり、（１）Ａｓ濃化層の有無の評価、（２）黄色変化の抑制の評価、及び（３）はんだ濡れ性の評価を行った。評価結果を以下の表６に示す。 And about each solder ball of Examples 38-44 and comparative examples 35-40, as mentioned above, evaluation of the existence of (1) As concentrated layer, (2) evaluation of suppression of yellow change, and (3) solder The wettability was evaluated. The evaluation results are shown in Table 6 below.
上記表６の結果より、Ｓｎ−Ｉｎ合金を含むはんだに関しても、Ａｓの含有量が４０〜３２０質量ｐｐｍ（０．００４０〜０．０３２０質量％）である実施例３８〜４４においては、実施例１〜７と同様に、Ａｓ濃化層が形成されており、黄色変化の抑制及びはんだ濡れ性のいずれにおいても非常に良好又は良好であった。特に、Ａｓの含有量が７０〜２００質量ｐｐｍ（０．００７０〜０．０２００質量％）である実施例３９〜４２においては、黄色変化の抑制及びはんだ濡れ性のいずれも非常に良好であった。 From the results of Table 6 above, Examples 38 to 44 in which the content of As is 40 to 320 mass ppm (0.0040 to 0.0320 mass%) also for the solder containing the Sn-In alloy, As in 1 to 7, an As-enriched layer was formed, and it was very good or good in both suppression of yellow change and solder wettability. In particular, in Examples 39 to 42 in which the content of As is 70 to 200 mass ppm (0.0070 to 0.0200 mass%), both suppression of yellow change and solder wettability are very good. .
一方、Ｓｎ−Ｉｎ合金を含むはんだに関しても、Ａｓを含まない比較例３５においては、比較例１と同様に、はんだ濡れ性は非常に良好であるものの、黄色変化を抑制することができなかった。また、Ａｓの含有量が４０質量ｐｐｍ（０．００４０質量％）未満である比較例３６〜３９においては、比較例２〜５と同様に、はんだ濡れ性は非常に良好であるものの、Ａｓ濃化層が形成されておらず、黄色変化を抑制することができなかった。さらに、Ａｓの含有量が３２０質量ｐｐｍ（０．０３２０質量％）を超える比較例４０においては、Ａｓ濃化層が形成されており、黄色変化の抑制は非常に良好であるものの、十分なはんだ濡れ性が得られなかった。 On the other hand, regarding the solder containing the Sn-In alloy, in Comparative Example 35 not containing As, as in Comparative Example 1, although the solder wettability is very good, the yellow change could not be suppressed. . Moreover, in Comparative Examples 36 to 39 in which the content of As is less than 40 mass ppm (0.0040 mass%), as in Comparative Examples 2 to 5, although the solder wettability is very good, the As concentration is high. Layer was not formed, and the yellowing could not be suppressed. Furthermore, in Comparative Example 40 in which the content of As exceeds 320 mass ppm (0.0320 mass%), an As-enriched layer is formed, and although the suppression of yellow change is very good, sufficient solder Wettability was not obtained.
また、実施例１〜４４のはんだボールを、当業界で一般的な方法で加工することによりはんだ継手を製造することができる。Ａｓの含有量が４０〜３２０質量ｐｐｍ（０．００４０〜０．０３２０質量％）であり、Ａｓ濃化層が形成されており、黄色変化の抑制及びはんだ濡れ性のいずれも優れた結果が得られている実施例１〜４４のはんだボールは、加熱しても変色しにくいため、このようなはんだボールから得られるはんだ継手もまた変色しにくい。 Moreover, a solder joint can be manufactured by processing the solder ball of Examples 1-44 by a general method in this field. The content of As is 40 to 320 mass ppm (0.0040 to 0.0320 mass%), an As-concentrated layer is formed, and excellent results are obtained in terms of both suppression of yellow change and solder wettability. Since the solder balls of Examples 1 to 44 which have been subjected to this method do not easily discolor even if heated, the solder joints obtained from such solder balls also do not easily discolor.
Claims (5)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017225677A JP6671013B2 (en) | 2017-11-24 | 2017-11-24 | Discoloration resistant solder alloy and discoloration resistant solder joint |
| US16/766,259 US11344976B2 (en) | 2017-11-24 | 2018-11-21 | Solder material, solder paste, and solder joint |
| PCT/JP2018/042943 WO2019103025A1 (en) | 2017-11-24 | 2018-11-21 | Solder material, solder paste, and solder joint |
| KR1020207018118A KR102600306B1 (en) | 2017-11-24 | 2018-11-21 | Solder materials, solder paste and solder joints |
| CN201880073066.XA CN111344106B (en) | 2017-11-24 | 2018-11-21 | Solder material, solder paste, and solder joint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017225677A JP6671013B2 (en) | 2017-11-24 | 2017-11-24 | Discoloration resistant solder alloy and discoloration resistant solder joint |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019070389A Division JP7013636B2 (en) | 2019-04-02 | 2019-04-02 | Discoloration resistant solder alloys and discoloration resistant solder joints |
| JP2020017740A Division JP2020097057A (en) | 2020-02-05 | 2020-02-05 | Discoloration-resistant solder material and discoloration-resistant solder joint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2019093425A true JP2019093425A (en) | 2019-06-20 |
| JP6671013B2 JP6671013B2 (en) | 2020-03-25 |
Family
ID=66972451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017225677A Active JP6671013B2 (en) | 2017-11-24 | 2017-11-24 | Discoloration resistant solder alloy and discoloration resistant solder joint |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6671013B2 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002224881A (en) * | 2001-02-05 | 2002-08-13 | Hitachi Metals Ltd | Solder ball |
| JP2005246480A (en) * | 2004-02-04 | 2005-09-15 | Senju Metal Ind Co Ltd | Solder alloy for preventing fe erosion and method for preventing fe erosion |
| JP2006181636A (en) * | 2004-12-03 | 2006-07-13 | Tamura Seisakusho Co Ltd | Tool for reducing erosion of solder bath, and soldering device having the same |
| JP2006289434A (en) * | 2005-04-11 | 2006-10-26 | Nihon Superior Co Ltd | Solder alloy |
| WO2014168027A1 (en) * | 2013-04-09 | 2014-10-16 | 千住金属工業株式会社 | Solder paste |
| JP2015098052A (en) * | 2013-10-16 | 2015-05-28 | 三井金属鉱業株式会社 | Solder alloy and solder powder |
-
2017
- 2017-11-24 JP JP2017225677A patent/JP6671013B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002224881A (en) * | 2001-02-05 | 2002-08-13 | Hitachi Metals Ltd | Solder ball |
| JP2005246480A (en) * | 2004-02-04 | 2005-09-15 | Senju Metal Ind Co Ltd | Solder alloy for preventing fe erosion and method for preventing fe erosion |
| JP2006181636A (en) * | 2004-12-03 | 2006-07-13 | Tamura Seisakusho Co Ltd | Tool for reducing erosion of solder bath, and soldering device having the same |
| JP2006289434A (en) * | 2005-04-11 | 2006-10-26 | Nihon Superior Co Ltd | Solder alloy |
| WO2014168027A1 (en) * | 2013-04-09 | 2014-10-16 | 千住金属工業株式会社 | Solder paste |
| JP2015098052A (en) * | 2013-10-16 | 2015-05-28 | 三井金属鉱業株式会社 | Solder alloy and solder powder |
Non-Patent Citations (2)
| Title |
|---|
| ＪＩＳ Ｈ ２１０８ すず地金, vol. 第１版, JPN6019033769, 19 January 2007 (2007-01-19), pages 401, ISSN: 0004106573 * |
| ＪＩＳ Ｚ ３２８２ はんだ−化学成分及び形状, JPN7019002798, 21 March 2017 (2017-03-21), pages 4 - 5, ISSN: 0004106572 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6671013B2 (en) | 2020-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102600306B1 (en) | Solder materials, solder paste and solder joints | |
| TWI383052B (en) | Low silver solder alloy and solder paste composition | |
| TWI629364B (en) | Solder alloy | |
| US10780530B2 (en) | Solder ball, solder joint, and joining method | |
| JP2014097532A (en) | Silver-free and lead-free solder composition | |
| JP6691305B2 (en) | Solder materials, solder pastes, and solder joints | |
| JP6548537B2 (en) | Solder alloy and solder composition | |
| JP2011235294A (en) | Solder alloy, and joined body using the same | |
| JP6678704B2 (en) | Solder materials, solder paste, and solder joints | |
| JP6671013B2 (en) | Discoloration resistant solder alloy and discoloration resistant solder joint | |
| JP7013636B2 (en) | Discoloration resistant solder alloys and discoloration resistant solder joints | |
| JP2020097057A (en) | Discoloration-resistant solder material and discoloration-resistant solder joint | |
| WO2020241319A1 (en) | Solder alloy, solder paste, solder ball, solder preform, and solder joint | |
| JP2021037548A (en) | Solder alloy, solder paste, solder ball, solder preform and solder joint | |
| JP6722378B2 (en) | Solder material, solder paste, and solder joint | |
| JP2020055038A (en) | Solder material, solder paste and solder joint | |
| CN115485098B (en) | Lead-free and antimony-free solder alloy, solder ball, ball grid array and solder joint | |
| KR20150127445A (en) | Silver-free and lead-free solder composition | |
| JP2020011301A (en) | Solder material, solder paste, and solder joint | |
| WO2020241316A1 (en) | Solder alloy, solder powder, solder paste, solder ball and solder preform | |
| JP2020110843A (en) | Solder material, solder paste, and solder joint | |
| JP2020099950A (en) | Solder material, solder paste and solder joint | |
| JP2013248664A (en) | Lead-free solder alloy and solder paste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180724 |
|
| A871 | Explanation of circumstances concerning accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A871 Effective date: 20180724 |
|
| A975 | Report on accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A971005 Effective date: 20180731 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20181122 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20181205 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20190111 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190402 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190516 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190605 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190902 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20191024 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20191204 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20200130 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20200212 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6671013 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |