JP5695879B2 - Method for producing tin-plated copper powder - Google Patents
Method for producing tin-plated copper powder Download PDFInfo
- Publication number
- JP5695879B2 JP5695879B2 JP2010239100A JP2010239100A JP5695879B2 JP 5695879 B2 JP5695879 B2 JP 5695879B2 JP 2010239100 A JP2010239100 A JP 2010239100A JP 2010239100 A JP2010239100 A JP 2010239100A JP 5695879 B2 JP5695879 B2 JP 5695879B2
- Authority
- JP
- Japan
- Prior art keywords
- copper powder
- tin
- dispersion
- acid
- salt
- 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.)
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 279
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 183
- 239000006185 dispersion Substances 0.000 claims description 137
- 239000007788 liquid Substances 0.000 claims description 107
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 88
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 53
- 239000002253 acid Substances 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 43
- 229910052802 copper Inorganic materials 0.000 claims description 36
- 239000010949 copper Substances 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 36
- 150000003585 thioureas Chemical class 0.000 claims description 35
- 150000003839 salts Chemical class 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 28
- 150000007524 organic acids Chemical class 0.000 claims description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 26
- 239000004094 surface-active agent Substances 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 20
- 238000006467 substitution reaction Methods 0.000 claims description 17
- 230000002378 acidificating effect Effects 0.000 claims description 16
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 4
- 238000007747 plating Methods 0.000 description 45
- 239000000243 solution Substances 0.000 description 40
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000843 powder Substances 0.000 description 21
- -1 salts Chemical class 0.000 description 21
- 238000000034 method Methods 0.000 description 17
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000002776 aggregation Effects 0.000 description 11
- 238000004220 aggregation Methods 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- JALQQBGHJJURDQ-UHFFFAOYSA-L bis(methylsulfonyloxy)tin Chemical compound [Sn+2].CS([O-])(=O)=O.CS([O-])(=O)=O JALQQBGHJJURDQ-UHFFFAOYSA-L 0.000 description 6
- 229920002114 octoxynol-9 Polymers 0.000 description 6
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- 150000003460 sulfonic acids Chemical class 0.000 description 4
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- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
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- HNDXKIMMSFCCFW-UHFFFAOYSA-N propane-2-sulphonic acid Chemical compound CC(C)S(O)(=O)=O HNDXKIMMSFCCFW-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- AECLSPNOPRYXFI-UHFFFAOYSA-J tin(4+);tetrasulfamate Chemical compound [Sn+4].NS([O-])(=O)=O.NS([O-])(=O)=O.NS([O-])(=O)=O.NS([O-])(=O)=O AECLSPNOPRYXFI-UHFFFAOYSA-J 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
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Images
Description
本発明はスズめっき銅粉の製造方法に関して、個々の銅粉の全面にスズめっき皮膜を均一に被覆できるものを提供する。 The present invention provides a method for producing a tin-plated copper powder that can uniformly coat a tin-plated film on the entire surface of each copper powder.
近年、スズめっき銅粉やスズめっき銀粉は、電子工業分野において導電性ペーストや電磁波シールド用の導電性塗料などに導電性付与のフィラーとして活用されている。
例えば、銅粉や銀粉は導電性が良好であるため、そのままフィラーとして用いることも考えられる。しかし、銅粉は安価であるが、酸化され易く電気特性が不安定であり、他方の銀粉は酸化され難く安定であるが、高価であるうえ、ハンダ付け性に劣るという欠点を夫々持っている。
そこで、これらの長所を活かしつつ欠点を克服する方策として、銅粉の表面を銀めっき皮膜で形成した導電性材料が開発されているが、その一方で、スズは銀より安価であるため、銀めっき銅粉に比べても前述のスズめっき銅粉は導電性フィラーとしての有望性が高いのである。
In recent years, tin-plated copper powder and tin-plated silver powder have been used as conductive fillers in conductive pastes and conductive coatings for electromagnetic wave shielding in the electronic industry.
For example, since copper powder and silver powder have good conductivity, it can be considered to be used as a filler as it is. However, copper powder is inexpensive, but is easily oxidized and unstable in electrical characteristics, while the other silver powder is difficult to oxidize and is stable, but has the disadvantages of being expensive and inferior in solderability. .
Therefore, as a measure for overcoming the drawbacks while taking advantage of these advantages, conductive materials in which the surface of the copper powder is formed of a silver plating film have been developed. On the other hand, since tin is cheaper than silver, Compared to the plated copper powder, the above tin-plated copper powder has high potential as a conductive filler.
スズめっき銅粉を製造する従来技術は次の通りである。
(1)特許文献１
銅粉をコア材としてその表層に均一にスズ被覆膜を形成する目的で（段落１０）、銅粉に水を入れて撹拌した銅粉スラリーと、置換析出スズ溶液とを所定の割合で混合し、撹拌し、洗浄、ろ過、乾燥してスズコート銅粉を製造する方法が開示される（請求項３）。
この製造方法は無電解メッキ方式であるため、電気メッキ方式では不可能なレベルにスズコート銅粉の凝集を抑制できること（段落１７）、銅粉の粉粒表面を予め硫酸や塩酸で洗浄すると、余分な酸化皮膜が除去されて、均一で密着性の良いスズ被覆層を形成できる下地づくりに有効であることが記載される（段落３２）。
尚、得られたスズコート銅粉の用途としてはプリント配線板への導電性ペーストなどが挙げられる（請求項１、段落１）。
The prior art for producing tin-plated copper powder is as follows.
(1) Patent Document 1
For the purpose of uniformly forming a tin coating film on the surface layer of copper powder as a core material (paragraph 10), the copper powder slurry in which water is added to the copper powder and stirred and the substituted precipitation tin solution are mixed at a predetermined ratio. And a method for producing a tin-coated copper powder by stirring, washing, filtering and drying (claim 3).
Since this manufacturing method is an electroless plating method, it is possible to suppress the aggregation of the tin-coated copper powder to a level impossible with the electroplating method (paragraph 17). It is described that it is effective for making an undercoat that can form a tin coating layer having a uniform and good adhesion by removing a thin oxide film (paragraph 32).
In addition, as an application of the obtained tin coat copper powder, the electrically conductive paste etc. to a printed wiring board are mentioned (Claim 1, Paragraph 1).
(2)特許文献２
特許文献１の技術に基づいて、スズコート銅粉のさらに外層に銀コートを施した二層コート銅粉が記載される。
Based on the technique of patent document 1, the two-layer coat copper powder which gave the silver coat to the further outer layer of the tin coat copper powder is described.
上記特許文献１のように、銅粉を水に添加した銅粉分散液を置換析出用のスズ溶液（つまり、無電解スズめっき液）に混合して撹拌した場合、実際には、銅粉が凝集し易く、銅粉の全周面でスズの置換反応が起こるわけではないため、個々の銅粉の全面を均一にスズ皮膜で被覆できないという問題がある。
また、銅粉分散液と無電解スズめっき液とを混合する場合、例えば、撹拌しながら銅粉分散液を無電解スズめっき液に滴下しようとすると、銅粉が円滑に分散したままの状態で液全体をスズめっき液に混合することは容易でなく、先に液相の部分が供給され易く、比重の大きい銅粉はどうしても凝集した塊状になって残り易いため、後からスズめっき液に供給されてしまう。その結果、凝集した銅粉にスズ塩が作用して置換反応が起きるため、個々の銅粉の全面に均一なスズめっきを施すことができないという問題がある。
When the copper powder dispersion obtained by adding copper powder to water is mixed with the tin solution for displacement deposition (that is, the electroless tin plating solution) and stirred as in Patent Document 1, the copper powder is actually Since it is easy to aggregate and the tin substitution reaction does not occur on the entire circumferential surface of the copper powder, there is a problem that the entire surface of each copper powder cannot be uniformly coated with the tin film.
In addition, when mixing the copper powder dispersion and the electroless tin plating solution, for example, if the copper powder dispersion is dropped into the electroless tin plating solution while stirring, the copper powder remains in a smoothly dispersed state. It is not easy to mix the entire solution into the tin plating solution. The liquid phase part is easy to be supplied first, and the copper powder with a large specific gravity tends to remain in an agglomerated mass. Will be. As a result, a tin salt acts on the agglomerated copper powder to cause a substitution reaction, so that there is a problem that uniform tin plating cannot be applied to the entire surface of each copper powder.
本発明は、個々の銅粉の全面に均一にスズめっき皮膜を形成したスズめっき銅粉を製造することを技術的課題とする。 This invention makes it a technical subject to manufacture the tin plating copper powder which formed the tin plating film uniformly on the whole surface of each copper powder.
本発明者らは、銅粉分散液と無電解スズめっき液との混合方式を鋭意研究した結果、銅粉を酸に分散させた酸性分散液を銅粉分散液とすること、この酸性分散液と無電解スズめっき液の混合に際してはスズめっき液を酸性分散液に対して供給し、その逆ではないこと、混合液は強く撹拌させた状態を保持すること、混合液中ではスズと銅の重量比率を所定範囲に適正化することなどにより、個々の銅粉の全面にスズめっき皮膜を均一に被覆できることを見い出して、本発明を完成した。 As a result of diligent research on the mixing method of the copper powder dispersion and the electroless tin plating solution, the present inventors made an acidic dispersion obtained by dispersing copper powder in an acid into a copper powder dispersion, and this acidic dispersion When mixing the electroless tin plating solution and the electroless tin plating solution, supply the tin plating solution to the acidic dispersion, and not the other way around; keep the mixture in a state of strong stirring; The present invention was completed by finding that a tin plating film can be uniformly coated on the entire surface of each copper powder by optimizing the weight ratio within a predetermined range.
即ち、本発明１は、スズ塩含有液と撹拌状態下の銅粉分散液とを混合し、当該混合液中で銅とスズの間で置換反応を行った後、ろ過、洗浄、乾燥して、銅粉の表面上にスズめっき皮膜を形成するスズめっき銅粉の製造方法において、
上記銅粉分散液が銅粉と酸を含有した酸性分散液であるか、銅粉と酸に加えてチオ尿素とチオ尿素誘導体から選ばれたチオ尿素類と界面活性剤の少なくとも一方を含有した酸性分散液であり、
スズ塩含有液が可溶性第一スズ塩と有機酸とチオ尿素類を含有した液であるか、可溶性第一スズ塩と有機酸とチオ尿素類に加えて界面活性剤と還元剤の少なくとも一方を含有した液であり、
銅粉分散液の酸は有機スルホン酸であるとともに、銅粉分散液の酸濃度は０.１〜８モル／Ｌであり、
銅粉分散液に対してスズ塩含有液を供給することで両者を混合し、
混合液を撹拌しながら置換反応させ、
混合液中のスズと銅の混合重量比がスズ／銅＝０.０５〜１.００であり、
混合液の加温域の上限が７０℃であることを特徴とするスズめっき銅粉の製造方法である。
That is, the present invention 1 comprises mixing a tin salt-containing liquid and a stirred copper powder dispersion, performing a substitution reaction between copper and tin in the mixed liquid , and then filtering, washing, and drying. In the method for producing a tin-plated copper powder that forms a tin-plated film on the surface of the copper powder,
The copper powder dispersion is an acid dispersion containing copper powder and acid, or contains at least one of thioureas selected from thiourea and thiourea derivatives and a surfactant in addition to copper powder and acid . An acidic dispersion,
The tin salt-containing liquid is a liquid containing a soluble stannous salt, an organic acid, and a thiourea, or at least one of a surfactant and a reducing agent in addition to the soluble stannous salt, the organic acid, and the thiourea. Containing liquid,
The acid of the copper powder dispersion is organic sulfonic acid, and the acid concentration of the copper powder dispersion is 0.1 to 8 mol / L,
Both are mixed by supplying the tin salt-containing liquid to the copper powder dispersion,
While stirring the mixed solution,
The mixing weight ratio of tin and copper in the mixture is tin / copper = 0.05 to 1.00 ,
The upper limit of the heating region of the mixed solution is 70 ° C.
本発明２は、スズ塩含有液と撹拌状態下の銅粉分散液とを混合し、当該混合液中で銅とスズの間で置換反応を行った後、ろ過、洗浄、乾燥して、銅粉の表面上にスズめっき皮膜を形成するスズめっき銅粉の製造方法において、
スズ塩含有液を銅粉分散液に供給して混合する代わりに、チオ尿素とチオ尿素誘導体から選ばれたチオ尿素類を複合分散液に供給して両者を混合し、
上記複合分散液が、銅粉と有機酸と可溶性第一スズ塩を含有する酸性分散液であるか、銅粉と有機酸と可溶性第一スズ塩に加えて界面活性剤と還元剤の少なくとも一方を含有する酸性分散液であり、
複合分散液の有機酸は有機スルホン酸であるとともに、複合分散液の酸濃度は０.１〜８モル／Ｌであり、
複合分散液に対してチオ尿素類を供給することで両者を混合し、
混合液を撹拌しながら置換反応させ、
混合液中のスズと銅の混合重量比がスズ／銅＝０.０５〜１.００であり、
混合液の加温域の上限が７０℃であることを特徴とするスズめっき銅粉の製造方法である。
Invention 2 mixes a tin salt-containing solution and a copper powder dispersion under stirring, and after performing a substitution reaction between copper and tin in the mixture, is filtered, washed and dried, In the method for producing a tin-plated copper powder that forms a tin-plated film on the surface of the powder,
Instead of supplying and mixing the tin salt-containing liquid to the copper powder dispersion, the thioureas selected from thiourea and thiourea derivatives are supplied to the composite dispersion and mixed together.
The composite dispersion is an acidic dispersion containing copper powder, organic acid and soluble stannous salt, or at least one of surfactant and reducing agent in addition to copper powder, organic acid and soluble stannous salt An acidic dispersion containing
The organic acid of the composite dispersion is organic sulfonic acid, and the acid concentration of the composite dispersion is 0.1 to 8 mol / L.
Both are mixed by supplying thioureas to the composite dispersion,
While stirring the mixed solution,
The mixing weight ratio of tin and copper in the mixture is tin / copper = 0.5-1.00,
The upper limit of the heating region of the mixed solution is 70 ° C.
本発明３は、上記本発明１又は２において、混合液の撹拌において、混合液の収容手段が円筒又は球状の容器であり、円筒又は球状の容器の中心軸にプロペラ型撹拌手段の回転軸を沿わせて構成し、
当該円筒又は球状の容器の直径に対するプロペラ径の割合が５／１０〜９.５／１０であり、
プロペラの回転速度が１２０〜１２００回転／分であることを特徴とするスズめっき銅粉の製造方法である。
The present invention 3 is the above-described present invention 1 or 2, wherein in mixing the mixed liquid, the mixed solution storage means is a cylindrical or spherical container, and the rotation axis of the propeller-type stirring means is provided on the central axis of the cylindrical or spherical container. Configured alongside,
The ratio of the propeller diameter to the diameter of the cylindrical or spherical container is 5/10 to 9.5 / 10,
It is a manufacturing method of the tin plating copper powder characterized by the rotation speed of a propeller being 120-1200 rotation / min.
本発明４は、上記本発明１〜３のいずれかにおいて、混合液を経時的に温度勾配を持たせて加温することを特徴とするスズめっき銅粉の製造方法である。 The present invention 4 is the method for producing tin-plated copper powder according to any one of the present inventions 1 to 3 , wherein the mixed solution is heated with a temperature gradient over time.
本発明５は、上記本発明４において、１０℃／１０分の昇温速度により温度勾配を持たせて加温することを特徴とするスズめっき銅粉の製造方法である。 The present invention 5 is the method of producing tin-plated copper powder according to the present invention 4, wherein heating is performed with a temperature gradient at a rate of temperature increase of 10 ° C./10 minutes.
本発明では、先ず、銅粉分散液として銅粉を酸に分散させた酸性分散液を用いるため、銅粉を水に添加した場合に比べて、銅粉の凝集を防止できるうえ、脱脂や酸洗浄も併せて行える。また、この酸性分散液とスズ塩含有液の混合では、スズ塩含有液を酸性分散液に対して供給して混合し、その逆ではないため、混合に際しては銅粉が液中に均一に分散され、銅粉分散液とスズ塩含有液との混合液を撹拌状態にすることと相俟って、銅粉の全周面においてスズ塩との間で置換反応を円滑に促進できる。
さらに、これらの処理要件に加えて、混合液中ではスズと銅の重量比率を所定範囲に適正化するので、その総合的な結果として、混合液中の置換反応においては、凝集のない状態で、且つ、個々の銅粉の全面にスズめっき皮膜を均一に被覆できる（図５参照）。
In the present invention, since an acidic dispersion in which copper powder is dispersed in an acid is used as the copper powder dispersion, the copper powder can be prevented from agglomerating as compared with the case where the copper powder is added to water. It can also be washed. In addition, in the mixing of the acidic dispersion and the tin salt-containing liquid, the tin salt-containing liquid is supplied to the acidic dispersion and mixed, and vice versa, so the copper powder is uniformly dispersed in the liquid during mixing. In addition, in combination with bringing the mixed liquid of the copper powder dispersion and the tin salt-containing liquid into a stirring state, the substitution reaction can be smoothly promoted between the copper powder and the tin salt on the entire circumferential surface.
Furthermore, in addition to these processing requirements, the weight ratio of tin and copper is optimized within a predetermined range in the mixed solution, so that the overall result is that the substitution reaction in the mixed solution has no aggregation. And the tin plating film can be uniformly coated on the entire surface of each copper powder (see FIG. 5).
本発明は、銅粉を酸に分散させた銅粉分散液に対してスズ塩含有液を供給することで両者を混合させ、この混合液を撹拌しながら加温し、或は加温しないで、銅とスズの間で置換反応を行った後、ろ過、洗浄、乾燥して、銅粉の表面上にスズめっき皮膜を形成するスズめっき銅粉の製造方法である。 The present invention mixes both by supplying a tin salt-containing liquid to a copper powder dispersion in which copper powder is dispersed in an acid, and heats the mixed liquid with stirring or without heating. Then, after performing a substitution reaction between copper and tin, it is filtered, washed, and dried to form a tin plating film on the surface of the copper powder.
本発明１〜２はスズ塩含有液を銅粉分散液に対して供給することを特徴とし、特に本発明１では、スズ塩含有液は基本的に無電解スズめっき液に相当する。
この供給する側（スズ塩含有液）の成分と供給される側（銅粉分散液）の成分については、スズ塩含有液と銅粉分散液の全成分のうち、供給する側には無電解スズめっき液の含有成分の全てを含んでも良いし（本発明１参照）、チオ尿素類のみを含んでも良く（本発明２参照）、また、供給される側には銅粉と酸を最少含有成分として、本発明２では、無電解スズめっき液のチオ尿素類を除く成分の全て、或はいずれかを含んでも良い。
Inventions 1 and 2 are characterized in that a tin salt-containing liquid is supplied to a copper powder dispersion. In particular, in Invention 1, the tin salt-containing liquid basically corresponds to an electroless tin plating solution.
About the component of this supply side (tin salt containing liquid) and the component of the supplied side (copper powder dispersion), it is electroless in the supply side among all the components of a tin salt containing liquid and a copper powder dispersion. It may contain all of the components of the tin plating solution (see the present invention 1) or may contain only thioureas (see the present invention 2), and the supply side contains a minimum of copper powder and acid. In the present invention 2, all or any of the components except the thioureas of the electroless tin plating solution may be included as components.
本発明の銅粉分散液は銅粉に酸を添加した酸性分散液であり、銅粉と酸を必須成分とし、或はさらに界面活性剤や還元剤などの無電解スズめっき液に添加する成分を含有しても良い。
そこで、銅粉分散液の組成の代表例を示すと次の通りである。
(1)銅粉と酸
(2)銅粉と酸とチオ尿素類
(3)銅粉と酸と界面活性剤
(4)銅粉と酸とチオ尿素類と界面活性剤
(5)銅粉と酸とチオ尿素類と界面活性剤と還元剤
銅粉分散液に含有する酸には、有機スルホン酸、カルボン酸などの有機酸、塩酸、硫酸、硝酸などの無機酸が挙げられるが、本発明のスズ塩含有液には有機酸を使用するため、銅粉分散液の酸についてはこれと共通の有機スルホン酸が選択される。
酸を添加することで、銅粉を脱脂、洗浄し、或は銅粉の凝集を防止する機能を果し、銅粉を水に添加する場合に比べて、銅粉を水相で均一分散化でき（図１参照）、銅粉の全面へのスズめっき皮膜の被覆度合が促進される。尚、銅粉分散液に界面活性剤を添加すると、銅粉の分散性の向上に寄与することが期待できる。
The copper powder dispersion of the present invention is an acid dispersion obtained by adding an acid to copper powder, and contains copper powder and acid as essential components, or further added to an electroless tin plating solution such as a surfactant and a reducing agent. May be contained.
Thus, a representative example of the composition of the copper powder dispersion is as follows.
(1) Copper powder and acid
(2) Copper powder, acid and thiourea
(3) Copper powder, acid and surfactant
(4) Copper powder, acid, thioureas and surfactant
(5) Copper powder, acid, thioureas, surfactant and reducing agent The acids contained in the copper powder dispersion include organic acids such as organic sulfonic acid and carboxylic acid, and inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid. can be mentioned, the tin salt containing liquid of the present invention to use the organic acid, acid for this a common organic acid copper powder dispersion is selected.
Adds acid to degrease and wash copper powder, or to prevent copper powder from agglomerating. Compared to adding copper powder to water, copper powder is uniformly dispersed in the aqueous phase. (See FIG. 1), and the covering degree of the tin plating film on the entire surface of the copper powder is promoted. In addition, when a surfactant is added to the copper powder dispersion, it can be expected to contribute to an improvement in the dispersibility of the copper powder.
銅粉分散液における銅粉と酸の混合割合は、銅／酸＝０.０２５〜８３０ｇ／Ｌが好ましい。例えば、酸３００〜２０００ｍＬに対して銅粉を５０〜２５０ｇ程度の割合で添加することになる。
銅／酸の比率が適正範囲より少ないと（銅が少なく酸が多いと）、スズめっきの対象となるコア材不足になるため、スズめっき銅粉ではなく、スズのみの析出物が生成され易い。逆に、この比率が適正範囲を越えると（銅が多く酸が少ないと）、銅が過剰となり、銅粉が凝集し易くなる。
この場合、銅粉分散液の酸濃度は０.１〜８モル／Ｌが好ましい。
また、銅粉分散液中の銅粉は比重が大きく、コロイド粒子でなければ沈降し易いため、スズ塩含有液と混合する前には撹拌状態を保持することが重要である。
銅粉の形状は、球状、偏平状、鱗片状、顆粒状、針状などの任意の形状をとり得る。銅粉は純銅をコア材とする粉末に限らず、樹脂表面に銅皮膜を被覆したものでも良い。
The mixing ratio of copper powder and acid in the copper powder dispersion is preferably copper / acid = 0.025 to 830 g / L. For example, copper powder is added at a ratio of about 50 to 250 g with respect to 300 to 2000 mL of acid.
If the copper / acid ratio is less than the appropriate range (if there is less copper and more acid), the core material that becomes the target of tin plating will be insufficient, so that only tin deposits are likely to be produced, not tin-plated copper powder. . On the contrary, when this ratio exceeds the appropriate range (when there is a large amount of copper and a small amount of acid), copper becomes excessive and the copper powder tends to aggregate.
In this case, the acid concentration of the copper powder dispersion is preferably 0.1 to 8 mol / L.
In addition, since the copper powder in the copper powder dispersion has a large specific gravity and tends to settle unless it is colloidal particles, it is important to maintain a stirring state before mixing with the tin salt-containing liquid.
The shape of the copper powder can be any shape such as a spherical shape, a flat shape, a scale shape, a granule shape, and a needle shape. The copper powder is not limited to a powder having pure copper as a core material, but may be a resin surface coated with a copper film.
前述した通り、本発明１のスズ塩含有液は基本的には無電解スズめっき液に相当し、可溶性第一スズ塩と有機酸とチオ尿素類を必須成分とし、界面活性剤、還元剤、或はその他の添加剤を含有しても良い。そこで、スズ塩含有液の組成の代表例を示すと次の通りである。
(ａ)可溶性第一スズ塩と有機酸とチオ尿素類
(ｂ)可溶性第一スズ塩と有機酸とチオ尿素類と界面活性剤
(ｃ)可溶性第一スズ塩と有機酸とチオ尿素類と還元剤
(ｄ)可溶性第一スズ塩と有機酸とチオ尿素類と界面活性剤と還元剤
従って、銅粉分散液とスズ塩含有液を混合する場合、銅粉分散液(1)〜(4)のいずれかと、スズ塩含有液(ａ)〜(ｄ)のいずれかを混合する組み合わせが代表例である。
前述したように、スズ塩含有液は原則として可溶性第一スズ塩と有機酸とチオ尿素類を必須成分とするが、例外として、銅粉分散液にチオ尿素類を含む場合（例えば、銅粉分散液(2)、(4)〜(5)）には、スズ塩含有液は可溶性第一スズ塩と有機酸だけを必須成分とし、チオ尿素類は必須成分ではなくて任意成分となる。従って、銅粉分散液にチオ尿素類を含む場合（銅粉分散液(2)、(4)〜(5)）には、スズ塩含有液にチオ尿素類を含んでも良いが（スズ塩含有液(ａ)〜(ｄ)）、含まなくても良い。
As described above, the tin salt-containing solution of the present invention 1 basically corresponds to an electroless tin plating solution, and includes a soluble stannous salt, an organic acid, and thioureas as essential components, a surfactant, a reducing agent, Or you may contain another additive. Therefore, a representative example of the composition of the tin salt-containing liquid is as follows.
(a) Soluble stannous salt, organic acid and thioureas
(b) Soluble stannous salt, organic acid, thioureas and surfactant
(c) Soluble stannous salt, organic acid, thioureas and reducing agent
(d) Soluble stannous salt, organic acid, thiourea, surfactant and reducing agent Therefore, when mixing a copper powder dispersion and a tin salt-containing liquid, the copper powder dispersions (1) to (4) A combination of any one of the tin salt-containing liquids (a) to (d) is a representative example.
As described above, the tin salt-containing liquid is essentially composed of a soluble stannous salt, an organic acid, and thioureas, except that when the copper powder dispersion contains thioureas (for example, copper powder) In the dispersions (2) and (4) to (5)), the tin salt-containing liquid contains only soluble stannous salt and an organic acid as essential components, and thioureas are not essential components but optional components. Therefore, when the copper powder dispersion contains thioureas (copper powder dispersion (2), (4) to (5)), the tin salt-containing liquid may contain thioureas (tin salt Liquids (a) to (d)) may not be included.
本発明の銅粉分散液とスズ塩含有液の混合については、スズ塩含有液を供給側とし、銅粉分散液を供給される側とするが、供給側（スズ塩含有液）にはチオ尿素類のみを含むことができる。
即ち、供給側（スズ塩含有液）がチオ尿素類を最大含有成分とする場合には、供給される側（銅粉分散液）には、銅粉と酸を最少含有成分として、無電解スズめっき液のチオ尿素類を除く成分のいずれか（つまり、他の含有可能な全ての成分、或はその一部の成分）を含んでも良い。
本発明２はこの方式を示したもので、本発明１のスズ塩含有液のうち、チオ尿素類を除く成分を銅粉分散液の成分に加えたものを複合分散液とし、この複合分散液に対してチオ尿素類を供給して、両者を混合することに特徴がある。
供給される側の上記複合分散液の成分を具体的に説明すれば、銅粉と有機酸と可溶性第一スズ塩、或はさらに界面活性剤、還元剤などを含有する酸性分散液を意味する。
Regarding the mixing of the copper powder dispersion and tin salt-containing liquid of the present invention, the tin salt-containing liquid is the supply side and the copper powder dispersion is supplied, but the supply side (tin salt-containing liquid) is thiol. Only ureas can be included.
That is, when the supply side (tin salt-containing liquid) has thioureas as the maximum component, the supplied side (copper powder dispersion) has electroless tin as the minimum component with copper powder and acid. Any of the components excluding thioureas in the plating solution (that is, all other components that can be contained, or a part of the components) may be included.
The present invention 2 shows this system. Among the tin salt-containing liquids of the present invention 1, a composition obtained by adding components excluding thioureas to the components of the copper powder dispersion is used as a composite dispersion. It is characterized by supplying thioureas to the mixture and mixing them.
Specifically describing the components of the above composite dispersion on the supply side, it means an acidic dispersion containing copper powder, an organic acid and a soluble stannous salt, or a surfactant, a reducing agent, etc. .
本発明は、銅粉分散液とスズ塩含有液を混合する際の供給手順に特徴があり、銅粉分散液にスズ塩含有液を供給することが必要で、逆に、銅粉分散液をスズ塩含有液に供給する方式は排除される。
銅粉分散液にスズ塩含有液を（或は、複合分散液にチオ尿素類を）供給する場合、基本はスズ塩含有液を銅粉分散液に滴下する方式であるが、例えば、銅粉分散液の中に供給路の出口を臨ませて、当該供給路を介してスズ塩含有液を少量づつ銅粉分散液中に送給する方式をとることなどにより、供給しても良い。
スズ塩含有液を銅粉分散液に滴下する方式にあっては、例えば、銅粉分散液の容量がスズ塩含有液の容量より多い条件下で、３００〜２０００ｍＬの銅粉分散液に１５０〜１０００ｍＬのスズ塩含有液を滴下し、その滴下速度は１０ｍＬ／分〜１０００ｍＬ／分であることが好ましい。
この場合、銅粉分散液／スズ塩含有液（容量割合）は２以上が好ましい。
The present invention is characterized in the supply procedure when mixing the copper powder dispersion and the tin salt-containing liquid, and it is necessary to supply the tin salt-containing liquid to the copper powder dispersion. The method of supplying the tin salt-containing liquid is excluded.
When supplying a tin salt-containing liquid to a copper powder dispersion (or supplying thioureas to a composite dispersion), the basic method is to drop the tin salt-containing liquid into the copper powder dispersion. You may supply by making the exit of a supply path face in a dispersion liquid, and taking the system which sends a tin salt containing liquid little by little in a copper powder dispersion liquid through the said supply path.
In the method of dropping the tin salt-containing liquid into the copper powder dispersion, for example, under a condition in which the volume of the copper powder dispersion is larger than the capacity of the tin salt-containing liquid, 150 to 300 to 2000 mL of the copper powder dispersion. It is preferable that 1000 mL of tin salt containing liquid is dripped and the dripping speed | rate is 10 mL / min-1000 mL / min.
In this case, the copper powder dispersion / tin salt-containing liquid (volume ratio) is preferably 2 or more.
銅粉分散液とスズ塩含有液（複合分散液とチオ尿素類）を混合した場合、混合液中のスズ／銅の混合重量比はスズ／銅＝０.０５〜１.００である。
当該重量比が適正範囲の下限より少ないとスズ皮膜が銅粉の全面を均一に被覆できない。逆に、重量比が適正範囲を越えても特に問題はないが、スズの割合が多ければメッキし易くなる一方、凝集し易くなり、また、スズ塩が多くなるとコストの無駄でもあるため、スズ／銅＝０.０５〜１.００の割合である。
また、銅粉の沈降を防止して、液中に浮遊状態に保持した銅粉に可溶性第一スズ塩、有機酸、チオ尿素類が任意の方位から接触可能になるように、混合液は撹拌状態にする必要がある。
混合液の撹拌強度については、本発明４に示すように、混合液の収容手段が円筒又は球状の容器である場合、円筒又は球状の容器の中心軸にプロペラ型撹拌手段の回転軸を沿わせて構成し、当該円筒又は球状の容器の直径に対するプロペラ径の割合は５／１０〜９.５／１０であり、プロペラの回転速度は１２０〜１２００回転／分であるように設定することが好ましい。
When the copper powder dispersion and the tin salt-containing liquid (composite dispersion and thioureas) are mixed, the mixing weight ratio of tin / copper in the mixture is tin / copper = 0.05 to 1.00.
If the weight ratio is less than the lower limit of the appropriate range, the tin film cannot uniformly cover the entire surface of the copper powder. Conversely, there is no particular problem even beyond the proper range by weight, while easily plating the more the proportion of tin, aggregation easily, and since there is also a waste of cost when the tin salt increases, tin /Copper=0.05 to 1.00.
In addition, the mixture is stirred so that soluble stannous salts, organic acids, and thioureas can come into contact with the copper powder held in a suspended state in the liquid to prevent copper powder from settling. It needs to be in a state.
As for the stirring strength of the mixed solution, as shown in the present invention 4, when the mixed solution storage means is a cylindrical or spherical container, the rotation axis of the propeller type stirring means is aligned with the central axis of the cylindrical or spherical container. The ratio of the propeller diameter to the diameter of the cylindrical or spherical container is preferably 5/10 to 9.5 / 10, and the rotation speed of the propeller is preferably set to 120 to 1200 rotations / minute. .
また、銅粉分散液とスズ塩含有液（或は、複合分散液とチオ尿素類）の混合液は加温しても、加温しなくても良いが、加温する場合には、一定温度で加温することもできるが、本発明５に示す通り、混合液を経時的に温度勾配を持たせて加温（つまり、スライド加温）することが好ましい。
例えば、一定の高温下で加熱すると、置換反応の速度が速いために、膜厚を一定に調整することが難しく、スズめっき銅粉はダマ状になり易いが、スライド加温させると、スズ皮膜の膜厚が一定になり易い。
スライド加温する場合、１０℃／１０分の昇温速度により温度勾配を持たせるのが好ましい（本発明６参照）。
In addition, the mixture of the copper powder dispersion and the tin salt-containing liquid (or the composite dispersion and thioureas) may or may not be heated. Although it can be heated at a temperature, as shown in the present invention 5, it is preferable to heat the mixed solution with a temperature gradient with time (that is, to warm the slide).
For example, when heated at a constant high temperature, the speed of the substitution reaction is fast, so it is difficult to adjust the film thickness to a constant level, and tin-plated copper powder tends to be lumpy. The film thickness tends to be constant.
When the slide is heated, it is preferable to provide a temperature gradient at a rate of temperature increase of 10 ° C./10 minutes (see Invention 6).
そこで、本発明の銅粉分散液及びスズ塩含有液に含まれる成分について具体的に説明する。
先ず、銅粉分散液の酸は、前述したように有機酸が好ましいが、無機酸を排除するものではない。無機酸としては、硫酸、塩酸、ホウフッ化水素酸、ケイフッ化水素酸、スルファミン酸などが挙げられる。
有機酸は、有機スルホン酸や脂肪族カルボン酸であり、その詳細はスズ塩含有液に含まれる有機酸と同じであり、後述する。
Then, the component contained in the copper powder dispersion liquid and tin salt containing liquid of this invention is demonstrated concretely.
First, the acid of the copper powder dispersion is preferably an organic acid as described above, but does not exclude inorganic acids. Examples of inorganic acids include sulfuric acid, hydrochloric acid, borohydrofluoric acid, silicohydrofluoric acid, sulfamic acid and the like.
The organic acid is an organic sulfonic acid or an aliphatic carboxylic acid, the details of which are the same as the organic acid contained in the tin salt-containing liquid, which will be described later.
本発明のスズ塩含有液に含まれる可溶性第一スズ塩としては、ホウフッ化第一スズ、硫酸第一スズ、酸化第一スズ、塩化第一スズ、ピロリン酸スズ、スルファミン酸スズ、亜スズ酸塩などの無機系の可溶性塩、アルカンスルホン酸第一スズ、アルカノールスルホン酸第一スズ、芳香族オキシスルホン酸第一スズ塩、スルホコハク酸第一スズ、脂肪族カルボン酸第一スズなどの有機系の可溶性塩などが挙げられる。
スズ塩含有液では有機酸が用いられるため、有機酸の第一スズ塩が好ましい。
Soluble stannous salts contained in the tin salt-containing liquid of the present invention include stannous borofluoride, stannous sulfate, stannous oxide, stannous chloride, tin pyrophosphate, tin sulfamate, stannic acid Organic salts such as inorganic soluble salts such as salts, stannous alkane sulfonate, stannous alkanol sulfonate, stannous aromatic oxysulfonic acid, stannous sulfosuccinate, stannous aliphatic carboxylate And soluble salts thereof.
Since an organic acid is used in the tin salt-containing liquid, a stannous salt of an organic acid is preferable.
次いで、スズ塩含有液に用いられる有機酸としては、有機スルホン酸、脂肪族カルボン酸が挙げられ、有機スルホン酸が好ましい（本発明７参照）。
有機スルホン酸には、アルカンスルホン酸、アルカノールスルホン酸、芳香族スルホン酸が挙げられる。
上記アルカンスルホン酸は、化学式ＣnＨ2n+1ＳＯ3Ｈ(例えば、ｎ=１〜１１)で示されるものであり、具体的には、メタンスルホン酸、エタンスルホン酸、１―プロパンスルホン酸、２―プロパンスルホン酸、１―ブタンスルホン酸、２―ブタンスルホン酸、ペンタンスルホン酸などが挙げられる。
上記アルカノールスルホン酸は、化学式
ＣmＨ2m+1-ＣＨ(ＯＨ)-ＣpＨ2p-ＳＯ3Ｈ(例えば、ｍ=０〜６、ｐ=１〜５)
で示されるものであり、具体的には、２―ヒドロキシエタン―１―スルホン酸、２―ヒドロキシプロパン―１―スルホン酸、２―ヒドロキシブタン―１―スルホン酸、２―ヒドロキシペンタン―１―スルホン酸、１―ヒドロキシプロパン―２―スルホン酸、３―ヒドロキシプロパン―１―スルホン酸、４―ヒドロキシブタン―１―スルホン酸、２―ヒドロキシヘキサン―１―スルホン酸などが挙げられる。
上記芳香族スルホン酸は、フェノールスルホン酸、クレゾールスルホン酸、ナフトールスルホン酸、スルホサリチル酸、１−ナフタレンスルホン酸、２−ナフタレンスルホン酸、トルエンスルホン酸、キシレンスルホン酸、ニトロベンゼンスルホン酸、スルホ安息香酸、ジフェニルアミン−４−スルホン酸などである。
Next, examples of the organic acid used in the tin salt-containing liquid include organic sulfonic acids and aliphatic carboxylic acids, and organic sulfonic acids are preferable (see the present invention 7).
Organic sulfonic acids include alkane sulfonic acids, alkanol sulfonic acids, and aromatic sulfonic acids.
The alkane sulfonic acid is represented by the chemical formula C n H 2n + 1 SO 3 H (eg, n = 1 to 11), and specifically includes methane sulfonic acid, ethane sulfonic acid, and 1-propane sulfonic acid. Examples thereof include 2-propanesulfonic acid, 1-butanesulfonic acid, 2-butanesulfonic acid, pentanesulfonic acid and the like.
The alkanol sulfonic acid has the formula C m H 2m + 1 -CH ( OH) -C p H 2p -SO 3 H ( e.g., m = 0~6, p = 1~5 )
Specifically, 2-hydroxyethane-1-sulfonic acid, 2-hydroxypropane-1-sulfonic acid, 2-hydroxybutane-1-sulfonic acid, 2-hydroxypentane-1-sulfone Acid, 1-hydroxypropane-2-sulfonic acid, 3-hydroxypropane-1-sulfonic acid, 4-hydroxybutane-1-sulfonic acid, 2-hydroxyhexane-1-sulfonic acid, and the like.
The aromatic sulfonic acid is phenol sulfonic acid, cresol sulfonic acid, naphthol sulfonic acid, sulfosalicylic acid, 1-naphthalene sulfonic acid, 2-naphthalene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, nitrobenzene sulfonic acid, sulfobenzoic acid, And diphenylamine-4-sulfonic acid.
スズ塩含有液に含まれる脂肪族カルボン酸は、乳酸、クエン酸、グルコン酸、リンゴ酸などが挙げられる。 Examples of the aliphatic carboxylic acid contained in the tin salt-containing liquid include lactic acid, citric acid, gluconic acid, and malic acid.
スズ塩含有液に含まれるチオ尿素類は、銅粉に配位して錯イオンを形成し、銅の電極電位を卑の方向に変移させ、スズとの化学置換反応を促進する作用をする。
チオ尿素類はチオ尿素及びチオ尿素誘導体からなる。チオ尿素誘導体としては、１,３―ジメチルチオ尿素、トリメチルチオ尿素、ジエチルチオ尿素(例えば、１,３―ジエチル―２―チオ尿素)、Ｎ,Ｎ′―ジイソプロピルチオ尿素、アリルチオ尿素、アセチルチオ尿素、エチレンチオ尿素、１,３―ジフェニルチオ尿素、二酸化チオ尿素、チオセミカルバジドなどが挙げられる。
Thioureas contained in the tin salt-containing liquid coordinate to copper powder to form complex ions, shift the electrode potential of copper in the base direction, and promote the chemical substitution reaction with tin.
Thioureas consist of thiourea and thiourea derivatives. Examples of thiourea derivatives include 1,3-dimethylthiourea, trimethylthiourea, diethylthiourea (eg, 1,3-diethyl-2-thiourea), N, N′-diisopropylthiourea, allylthiourea, acetylthiourea, ethylenethio Examples include urea, 1,3-diphenylthiourea, thiourea dioxide, and thiosemicarbazide.
スズ塩含有液には界面活性剤、還元剤、ｐＨ調整剤などの各種添加剤を含有できることはいうまでもない。また、これらの添加剤は前述したように、本発明１の銅粉分散液、或は、本発明２の複合分散剤に含有しても良い。
上記界面活性剤には通常のノニオン系、アニオン系、両性、或はカチオン系などの各種界面活性剤が挙げられ、スズ皮膜の外観、緻密性、平滑性、密着性などの改善、銅粉分散液での分散性などに寄与する。
上記アニオン系界面活性剤としては、アルキル硫酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩などが挙げられる。カチオン系界面活性剤としては、モノ〜トリアルキルアミン塩、ジメチルジアルキルアンモニウム塩、トリメチルアルキルアンモニウム塩などが挙げられる。ノニオン系界面活性剤としては、Ｃ1〜Ｃ20アルカノール、フェノール、ナフトール、ビスフェノール類、Ｃ1〜Ｃ25アルキルフェノール、アリールアルキルフェノール、Ｃ1〜Ｃ25アルキルナフトール、Ｃ1〜Ｃ25アルコキシルリン酸(塩)、ソルビタンエステル、ポリアルキレングリコール、Ｃ1〜Ｃ22脂肪族アミドなどにエチレンオキシド(ＥＯ)及び／又はプロピレンオキシド(ＰＯ)を２〜３００モル付加縮合させたものなどが挙げられる。両性界面活性剤としては、カルボキシベタイン、イミダゾリンベタイン、スルホベタイン、アミノカルボン酸などが挙げられる。
It goes without saying that the tin salt-containing liquid can contain various additives such as a surfactant, a reducing agent, and a pH adjuster. Further, as described above, these additives may be contained in the copper powder dispersion of the present invention 1 or the composite dispersant of the present invention 2.
Examples of the surfactant include various surfactants such as ordinary nonionic, anionic, amphoteric, and cationic surfactants. Improvement of tin film appearance, denseness, smoothness, adhesion, etc., copper powder dispersion Contributes to dispersibility in liquids.
Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl benzene sulfonates, and alkyl naphthalene sulfonates. Examples of the cationic surfactant include mono-trialkylamine salts, dimethyldialkylammonium salts, and trimethylalkylammonium salts. Examples of the nonionic surfactant, C 1 -C 20 alkanols, phenol, naphthol, bisphenol, C 1 -C 25 alkyl phenols, aryl phenols, C 1 -C 25 alkyl naphthol, C 1 -C 25 alkoxyl phosphoric acid (salt ), Sorbitan ester, polyalkylene glycol, C 1 -C 22 aliphatic amide and the like, and 2-300 mol addition-condensation of ethylene oxide (EO) and / or propylene oxide (PO). Examples of amphoteric surfactants include carboxybetaine, imidazoline betaine, sulfobetaine, and aminocarboxylic acid.
上記酸化防止剤は、スズ塩含有液中のＳｎ2+の酸化防止を目的としたもので、次亜リン酸又はその塩、アスコルビン酸又はその塩、ハイドロキノン、カテコール、レゾルシン、フロログルシン、クレゾールスルホン酸又はその塩、フェノールスルホン酸又はその塩、カテコールスルホン酸又はその塩、ハイドロキノンスルホン酸又はその塩、ヒドラジンなどが挙げられる。 The antioxidant is for the purpose of preventing the oxidation of Sn 2+ in the tin salt-containing liquid. Hypophosphorous acid or a salt thereof, ascorbic acid or a salt thereof, hydroquinone, catechol, resorcin, phloroglucin, cresolsulfonic acid Or the salt, phenolsulfonic acid or its salt, catecholsulfonic acid or its salt, hydroquinonesulfonic acid or its salt, hydrazine, etc. are mentioned.
上記ｐＨ調整剤としては、塩酸、硫酸等の各種の酸、アンモニア水、水酸化カリウム、水酸化ナトリウム等の各種の塩基などが挙げられるが、ギ酸、酢酸、プロピオン酸などのモノカルボン酸類、ホウ酸類、リン酸類、シュウ酸、コハク酸などのジカルボン酸類、乳酸、酒石酸などのオキシカルボン酸類などが有効である。 Examples of the pH adjuster include various acids such as hydrochloric acid and sulfuric acid, various bases such as aqueous ammonia, potassium hydroxide and sodium hydroxide, monocarboxylic acids such as formic acid, acetic acid and propionic acid, and boron. Dicarboxylic acids such as acids, phosphoric acids, oxalic acid and succinic acid, and oxycarboxylic acids such as lactic acid and tartaric acid are effective.
本発明では、混合工程において銅とスズの間で置換反応を行った後、ろ過し、ろ過液のｐＨが６〜７の中性域になるまで洗浄し、乾燥して、銅粉の表面上にスズめっき皮膜が形成されたスズめっき銅粉を得る。 In the present invention, after performing a substitution reaction between copper and tin in the mixing step, the mixture is filtered, washed until the pH of the filtrate reaches a neutral range of 6 to 7, dried, and then on the surface of the copper powder. A tin-plated copper powder having a tin-plated film formed thereon is obtained.
以下、本発明のスズめっき銅粉の製造実施例、当該実施例で得られたスズめっき銅粉の外観試験例を順次述べる。
尚、本発明は下記の実施例、試験例に拘束されるものではなく、本発明の技術的思想の範囲内で任意の変形をなし得ることは勿論である。
Hereinafter, the manufacture example of the tin plating copper powder of this invention and the external appearance test example of the tin plating copper powder obtained by the said Example are described one by one.
The present invention is not limited to the following examples and test examples, and it is needless to say that arbitrary modifications can be made within the scope of the technical idea of the present invention.
《スズめっき銅粉の製造実施例》
実施例１〜５のうち、実施例１〜４の全ては銅粉分散液をスズ塩含有液に滴下した本発明１に相当する例、実施例５はチオ尿素のみを複合分散液に滴下した本発明２の例である。
実施例１では、銅粉分散液が銅粉を有機スルホン酸に分散した酸性分散液であり、スズ塩含有液が可溶性第一スズ塩と有機スルホン酸とチオ尿素と還元剤と界面活性剤を含有する無電解スズめっき液である。実施例２は実施例１のスズ塩含有液の界面活性剤を、いわば銅粉分散液に移行した例である。実施例４は実施例１の銅粉分散液にさらにチオ尿素を加えた例である。実施例３は混合した後にスライド加温した例、他の実施例は常温で混合した例である。
一方、比較例１〜４のうち、比較例１は冒述の特許文献１の準拠例であり、銅粉を水に添加したものを銅粉分散液とした例である。比較例２は混合液中のスズ／銅の混合重量比を本発明の適正範囲の下限より少なくした例である。比較例３は混合液を撹拌せずに置換反応させた例である。比較例４は本発明の混合手順とは逆に、スズ塩含有液に銅粉分散液を滴下した例である。
<< Examples of production of tin-plated copper powder >>
Of Examples 1-5, all of Examples 1-4 are examples corresponding to the present invention 1 in which a copper powder dispersion was dropped onto a tin salt-containing liquid, and Example 5 was dropped only on thiourea into a composite dispersion. It is an example of the present invention 2.
In Example 1, the copper powder dispersion is an acidic dispersion in which copper powder is dispersed in organic sulfonic acid, and the tin salt-containing liquid contains soluble stannous salt, organic sulfonic acid, thiourea, reducing agent, and surfactant. This is an electroless tin plating solution. Example 2 is an example in which the surfactant of the tin salt-containing liquid of Example 1 was transferred to a so-called copper powder dispersion. Example 4 is an example in which thiourea was further added to the copper powder dispersion of Example 1. Example 3 is an example in which the slide is heated after mixing, and the other examples are examples of mixing at room temperature.
On the other hand, among Comparative Examples 1 to 4, Comparative Example 1 is a conforming example of Patent Document 1 described above, and is an example in which copper powder is added to water to make a copper powder dispersion. Comparative Example 2 is an example in which the mixing weight ratio of tin / copper in the mixed solution is less than the lower limit of the proper range of the present invention. Comparative Example 3 is an example in which the mixed solution was subjected to a substitution reaction without stirring. In contrast to the mixing procedure of the present invention, Comparative Example 4 is an example in which a copper powder dispersion was dropped into a tin salt-containing liquid.
(イ)実施例１
スズめっき銅粉の処理条件、銅粉分散液並びにスズ塩含有液の組成、両方の液を混合する際の条件を順次述べるととともに、スズめっき銅粉の製造工程を具体的に説明する。
(1)処理条件
銅粉分散液量：１Ｌ
スズ塩含有液量：５００ｍＬ（＝０.５Ｌ） スズ塩含有液のスズ濃度：３０ｇ／Ｌ
滴下速度＝５００ｍＬ／１０分＝５０ｍＬ／分
混合液の撹拌速度：３００回転／分
３Ｌビーカーの直径：１００ｍｍ 撹拌プロペラの径：８５ｍｍ
銅粉分散液／スズ塩含有液＝１Ｌ／０.５Ｌ＝２
混合液中でのスズと銅粉の混合割合：スズ／銅＝１５ｇ／１００ｇ＝０.１５
(A) Example 1
The processing conditions for the tin-plated copper powder, the composition of the copper powder dispersion and the tin salt-containing liquid, and the conditions for mixing both liquids will be sequentially described, and the production process of the tin-plated copper powder will be specifically described.
(1) Treatment conditions Copper powder dispersion volume: 1L
Tin salt-containing liquid amount: 500 mL (= 0.5 L) Tin concentration of tin salt-containing liquid: 30 g / L
Dropping speed = 500 mL / 10 min = 50 mL / min Stirring speed of the mixed solution: 300 revolutions / min 3L beaker diameter: 100 mm Stirring propeller diameter: 85 mm
Copper powder dispersion / tin salt-containing solution = 1L / 0.5L = 2
Mixing ratio of tin and copper powder in the mixed solution: tin / copper = 15 g / 100 g = 0.15
(2)銅粉分散液の組成
銅粉 １００ｇ／Ｌ
メタンスルホン酸 ０.３５モル／Ｌ
(3)スズ塩含有液（＝無電解スズめっき液）の組成
メタンスルホン酸第一スズ(Ｓｎ2+として） ３０ｇ／Ｌ
メタンスルホン酸 ２.０モル／Ｌ
次亜リン酸 ０.５モル／Ｌ
チオ尿素 ２.５０モル／Ｌ
ポリオキシエチレンオクチルフェニルエーテル(EO15モル) １０.０ｇ／Ｌ
(4)混合条件
温度浴温；２５℃ めっき時間；２０分
温度勾配を持たせず、常温反応させた。
(2) Composition of copper powder dispersion copper powder 100g / L
Methanesulfonic acid 0.35 mol / L
(3) Composition of tin salt-containing solution (= electroless tin plating solution) Stannous methanesulfonate (as Sn 2+ ) 30g / L
Methanesulfonic acid 2.0 mol / L
Hypophosphorous acid 0.5 mol / L
Thiourea 2.50 mol / L
Polyoxyethylene octyl phenyl ether (EO15 mol) 10.0 g / L
(4) Mixing conditions Temperature bath temperature: 25 ° C. Plating time: 20 minutes A normal temperature reaction was performed without a temperature gradient.
(5)スズめっき銅粉の製造工程
(ａ)メタンスルホン酸溶液（３５ｇ／Ｌ）の１Ｌを収容したビーカーに、銅粉１００ｇを投入して上記(2)の銅粉分散液を調製し、約１０分激しく撹拌した。
(ｂ)(ａ)の銅粉分散液に、ゆっくりと上記(3)の無電解スズめっき液５００ｍＬを滴下して、両者を混合した。この場合、無電解スズめっき液のスズ濃度は３０ｇ／Ｌであるが、滴下容量は５００ｍＬなので、混合液中のスズの供給量は１５ｇである。
(ｃ)(ｂ)の混合液を室温（約２５℃）で２０分撹拌して置換反応を行った。
(ｄ)置換反応後、工程(c)において、スズ被覆粉がビーカーの底に沈殿した時点で、上澄みを捨てた。
(ｅ)(ｄ)のスズ被覆粉の生成したビーカーに約１.５Ｌのイオン交換水を加えて再度撹拌した。
(ｆ)(ｅ)をろ過し、再度スズ被覆粉に約１.５Ｌのイオン交換水を加えて再度撹拌した。
(ｇ)(ｅ)〜(ｆ)に示す通り、イオン交換水によるろ過及び洗浄工程を、ろ液のｐＨが中性になるまで繰り返し、最後にろ過後、得られたスズめっき銅粉を乾燥した。
尚、ろ過及び洗浄工程では、洗浄に必要なイオン交換水量は、作業液（銅粉分散液１Ｌ＋スズ塩含有液０.５Ｌ＝１.５Ｌ）の１０倍が目安となる。
(5) Manufacturing process of tin-plated copper powder
(a) In a beaker containing 1 L of a methanesulfonic acid solution (35 g / L), 100 g of copper powder was added to prepare a copper powder dispersion of the above (2) and stirred vigorously for about 10 minutes.
(b) To the copper powder dispersion of (a), 500 mL of the electroless tin plating solution of (3) was slowly dropped and mixed. In this case, the tin concentration of the electroless tin plating solution is 30 g / L, but since the dropping capacity is 500 mL, the supply amount of tin in the mixed solution is 15 g.
(c) The mixture of (b) was stirred at room temperature (about 25 ° C.) for 20 minutes to carry out a substitution reaction.
(d) After the substitution reaction, in step (c), when the tin-coated powder settled on the bottom of the beaker, the supernatant was discarded.
(e) About 1.5 L of ion-exchanged water was added to the beaker in which the tin-coated powder of (d) was produced and stirred again.
(f) (e) was filtered, and about 1.5 L of ion-exchanged water was added to the tin-coated powder again and stirred again.
(g) As shown in (e) to (f), filtration and washing steps with ion-exchanged water are repeated until the pH of the filtrate becomes neutral. Finally, after filtration, the resulting tin-plated copper powder is dried. did.
In the filtration and washing process, the amount of ion-exchanged water necessary for washing is 10 times the working liquid (copper powder dispersion 1L + tin salt-containing liquid 0.5L = 1.5 L).
(ロ)実施例２
銅粉分散液にメタンスルホン酸と界面活性剤を含有したことを特徴とする。
(1)処理条件は上記実施例１と同じである。
(2)銅粉分散液の組成
銅粉 １００ｇ／Ｌ
メタンスルホン酸 ０.３５モル／Ｌ
ポリオキシエチレンオクチルフェニルエーテル(EO15モル) １０.０ｇ／Ｌ
(3)スズ塩含有液（＝無電解スズめっき液）の組成
メタンスルホン酸第一スズ（Ｓｎ2+として） ３０ｇ／Ｌ
メタンスルホン酸 １.５モル／Ｌ
次亜リン酸 ０.５モル／Ｌ
チオ尿素 ２.００モル／Ｌ
(4)混合条件は上記実施例１と同じである。
(5)スズめっき銅粉の製造工程は実施例１と同じである。
(B) Example 2
The copper powder dispersion contains methanesulfonic acid and a surfactant.
(1) The processing conditions are the same as in the first embodiment.
(2) Composition of copper powder dispersion copper powder 100g / L
Methanesulfonic acid 0.35 mol / L
Polyoxyethylene octyl phenyl ether (EO15 mol) 10.0 g / L
(3) Composition of tin salt-containing solution (= electroless tin plating solution) Stannous methanesulfonate (as Sn 2+ ) 30 g / L
Methanesulfonic acid 1.5 mol / L
Hypophosphorous acid 0.5 mol / L
Thiourea 2.00 mol / L
(4) The mixing conditions are the same as in Example 1 above.
(5) The manufacturing process of the tin-plated copper powder is the same as in Example 1.
(ハ)実施例３
温度勾配を持たせてスライド加温操作を行った。
(1)処理条件は実施例１と同じである。
(2)銅粉分散液の組成は実施例１と同じである。
(3)スズ塩含有液の組成は実施例１と同じである。
(4)混合条件は実施例１と同じである。
(5)スズめっき銅粉の製造工程は、工程(ｃ)を除いて実施例１と基本的に同じである。
工程(ｃ)では、めっき温度は２５℃でスタートし、１０分後に３５℃、さらに１０分後４５℃に昇温し、その後４５℃で一定にして、さらに１０分撹拌、置換反応を行った。
めっき時間の合計は３０分に設定した。
(C) Example 3
The slide heating operation was performed with a temperature gradient.
(1) The processing conditions are the same as in the first embodiment.
(2) The composition of the copper powder dispersion is the same as in Example 1.
(3) The composition of the tin salt-containing liquid is the same as in Example 1.
(4) The mixing conditions are the same as in Example 1.
(5) The production process of tin-plated copper powder is basically the same as that of Example 1 except for the step (c).
In the step (c), the plating temperature was started at 25 ° C., 10 minutes later, 35 ° C., and further 10 minutes later, the temperature was raised to 45 ° C., then kept constant at 45 ° C., and further stirred for 10 minutes to perform a substitution reaction. .
The total plating time was set to 30 minutes.
(ニ)実施例４
銅粉分散液にメタンスルホン酸と錯化剤を含有したことを特徴とする。
(1)処理条件は実施例１と同じである。
(2)銅粉分散液の組成
銅粉 １００ｇ／Ｌ
メタンスルホン酸 ０.３５モル／Ｌ
チオ尿素 ２.５０モル／Ｌ
(3)スズ塩含有液の組成
メタンスルホン酸第一スズ（Ｓｎ2+として） ３０ｇ／Ｌ
メタンスルホン酸 ２.０モル／Ｌ
次亜リン酸 ０.５モル／Ｌ
ポリオキシエチレンオクチルフェニルエーテル(EO15モル) １０.０ｇ／Ｌ
(4)混合条件は実施例と同じである。
(5)スズめっき銅粉の製造工程は実施例１と同じである。
(D) Example 4
The copper powder dispersion contains methanesulfonic acid and a complexing agent.
(1) The processing conditions are the same as in the first embodiment.
(2) Composition of copper powder dispersion copper powder 100g / L
Methanesulfonic acid 0.35 mol / L
Thiourea 2.50 mol / L
(3) Composition of tin salt-containing liquid Stannous methanesulfonate (as Sn 2+ ) 30 g / L
Methanesulfonic acid 2.0 mol / L
Hypophosphorous acid 0.5 mol / L
Polyoxyethylene octyl phenyl ether (EO15 mol) 10.0 g / L
(4) The mixing conditions are the same as in the examples.
(5) The manufacturing process of the tin-plated copper powder is the same as in Example 1.
(ホ)実施例５
チオ尿素（錯化剤）のみを複合分散液に滴下したことを特徴とする。
(1)処理条件は実施例１と同じである。
(2)複合分散液の組成
銅粉 １００ｇ／Ｌ
メタンスルホン酸第一スズ（Ｓｎ2+として） １５ｇ／Ｌ
メタンスルホン酸 ２.０モル／Ｌ
次亜リン酸 ０.５モル／Ｌ
ポリオキシエチレンオクチルフェニルエーテル(EO15モル) １０.０ｇ／Ｌ
(3)滴下するチオ尿素液の組成
チオ尿素 ２.５０モル／Ｌ
(4)混合条件は実施例と同じである。
(5)スズめっき銅粉の製造工程は実施例１と同じである。
(E) Example 5
Only thiourea (complexing agent) is dropped into the composite dispersion.
(1) The processing conditions are the same as in the first embodiment.
(2) Composition of composite dispersion Copper powder 100g / L
Stannous methanesulfonate (as Sn 2+ ) 15g / L
Methanesulfonic acid 2.0 mol / L
Hypophosphorous acid 0.5 mol / L
Polyoxyethylene octyl phenyl ether (EO15 mol) 10.0 g / L
(3) Composition of the thiourea solution to be dropped Thiourea 2.50 mol / L
(4) The mixing conditions are the same as in the examples.
(5) The manufacturing process of the tin-plated copper powder is the same as in Example 1.
(ヘ)比較例１
銅粉を水に添加したものを銅粉分散液とした。
(1)処理条件は実施例１と同じである。
(2)銅粉分散液の組成
銅粉 １００ｇ／Ｌ
イオン交換水 １Ｌ
(3)スズ塩含有液（＝無電解スズめっき液）の組成
メタンスルホン酸第一スズ（Ｓｎ2+として） ３０ｇ／Ｌ
メタンスルホン酸 ２.０モル／Ｌ
次亜リン酸 ０.５モル／Ｌ
チオ尿素 ２.５０モル／Ｌ
ポリオキシエチレンオクチルフェニルエーテル(EO15モル) １０.０ｇ／Ｌ
(4)混合条件は実施例と同じである。
(5)スズめっき銅粉の製造工程は実施例１と同じである。
(F) Comparative Example 1
A copper powder dispersion was prepared by adding copper powder to water.
(1) The processing conditions are the same as in the first embodiment.
(2) Composition of copper powder dispersion copper powder 100g / L
Ion exchange water 1L
(3) Composition of tin salt-containing solution (= electroless tin plating solution) Stannous methanesulfonate (as Sn 2+ ) 30 g / L
Methanesulfonic acid 2.0 mol / L
Hypophosphorous acid 0.5 mol / L
Thiourea 2.50 mol / L
Polyoxyethylene octyl phenyl ether (EO15 mol) 10.0 g / L
(4) The mixing conditions are the same as in the examples.
(5) The manufacturing process of the tin-plated copper powder is the same as in Example 1.
(ト)比較例２
混合液中のスズと銅の混合重量比が、本発明の適正範囲より少ない例である。
(1)処理条件
銅粉分散液量：１Ｌ
スズ塩含有液量：１００ｍＬ（＝０.１Ｌ） スズ塩含有液のスズ濃度：３０ｇ／Ｌ
滴下速度＝５００ｍＬ／２０分＝２５ｍＬ／分
混合液の撹拌速度：３００回転／分
３Ｌビーカーの直径：１００ｍｍ 撹拌プロペラの径：８５ｍｍ
銅粉分散液／スズ塩含有液＝１Ｌ／０.５Ｌ＝２
混合液中でのスズと銅粉の混合割合：スズ／銅＝３ｇ／１５０ｇ＝０.０２
この場合、スズ塩含有液のスズ濃度３０ｇ／Ｌであるが１００ｍｌ中であるので液中には３ｇ／Ｌ。
(G) Comparative Example 2
This is an example in which the mixing weight ratio of tin and copper in the mixed solution is less than the appropriate range of the present invention.
(1) Treatment conditions Copper powder dispersion volume: 1L
Tin salt-containing liquid amount: 100 mL (= 0.1 L) Tin concentration of tin salt-containing liquid: 30 g / L
Dropping speed = 500 mL / 20 minutes = 25 mL / min Mixing liquid stirring speed: 300 revolutions / min 3L beaker diameter: 100 mm Stirring propeller diameter: 85 mm
Copper powder dispersion / tin salt-containing solution = 1L / 0.5L = 2
Mixing ratio of tin and copper powder in the mixed solution: tin / copper = 3 g / 150 g = 0.02
In this case, the tin concentration of the tin salt-containing liquid is 30 g / L, but in 100 ml, the liquid is 3 g / L.
(2)銅粉分散液の組成
銅粉 １００ｇ／Ｌ
メタンスルホン酸 ０.３５モル／Ｌ
(3)スズ塩含有液（＝無電解スズめっき液）の組成
メタンスルホン酸第一スズ(Ｓｎ2+として） ３０ｇ／Ｌ
メタンスルホン酸 ２.０モル／Ｌ
次亜リン酸 ０.５モル／Ｌ
チオ尿素 ２.５０モル／Ｌ
ポリオキシエチレンオクチルフェニルエーテル(EO15モル) １０.０ｇ／Ｌ
(4)混合条件は実施例と同じである。
尚、スズ塩含有液のスズ濃度は３０ｇ／Ｌであるが、当該含有液の滴下量は１００ｍＬであり、混合液中のスズ濃度は３ｇ／Ｌであるので、上述の通り、混合液中でのスズと銅粉の混合割合（スズ／銅）は３ｇ／１５０ｇ＝０.０２である。
(5)スズめっき銅粉の製造工程は実施例１と同じである。
(2) Composition of copper powder dispersion copper powder 100g / L
Methanesulfonic acid 0.35 mol / L
(3) Composition of tin salt-containing solution (= electroless tin plating solution) Stannous methanesulfonate (as Sn 2+ ) 30g / L
Methanesulfonic acid 2.0 mol / L
Hypophosphorous acid 0.5 mol / L
Thiourea 2.50 mol / L
Polyoxyethylene octyl phenyl ether (EO15 mol) 10.0 g / L
(4) The mixing conditions are the same as in the examples.
In addition, although the tin concentration of the tin salt-containing liquid is 30 g / L, the dropping amount of the containing liquid is 100 mL, and the tin concentration in the mixed liquid is 3 g / L. The mixing ratio of tin and copper powder (tin / copper) is 3 g / 150 g = 0.02.
(5) The manufacturing process of the tin-plated copper powder is the same as in Example 1.
(チ)比較例３
混合液を撹拌せずに置換反応させた例である。
処理条件(1)、スズめっき銅粉の製造工程(5)のうちの撹拌態様を撹拌しない処理に変更した以外は、実施例１と同じである。
(2)銅粉分散液の組成、(3)スズ塩含有液（＝無電解スズめっき液）の組成、(4)混合条件は夫々実施例１と同じである。
(H) Comparative Example 3
In this example, the mixed solution is subjected to a substitution reaction without stirring.
It is the same as Example 1 except having changed into the process which does not stir the stirring aspect in the process conditions (1) and the manufacturing process (5) of tin plating copper powder.
(2) The composition of the copper powder dispersion, (3) the composition of the tin salt-containing solution (= electroless tin plating solution), and (4) the mixing conditions are the same as in Example 1.
(リ)比較例４
上記実施例１とは混合方式を逆にして、スズ塩含有液（＝無電解スズめっき液）に銅粉分散液を滴下する方法である。
処理条件(1)、スズめっき銅粉の製造工程(5)のうちのスズ塩含有液を銅粉分散液に滴下する混合態様を、銅粉分散液をスズ塩含有液に滴下する逆の手順に変更した以外は、実施例１と同じである。
(2)銅粉分散液の組成、(3)スズ塩含有液（＝無電解スズめっき液）の組成、(4)混合条件は夫々実施例１と同じである。
(R) Comparative Example 4
Example 1 is a method in which the mixing method is reversed and the copper powder dispersion is dropped into a tin salt-containing liquid (= electroless tin plating liquid).
Processing conditions (1), the mixed procedure of dropping tin salt-containing liquid into copper powder dispersion liquid in the manufacturing process (5) of tin-plated copper powder, reverse procedure of dropping copper powder dispersion liquid into tin salt-containing liquid Example 1 is the same as Example 1 except that the change is made.
(2) The composition of the copper powder dispersion, (3) the composition of the tin salt-containing solution (= electroless tin plating solution), and (4) the mixing conditions are the same as in Example 1.
《スズめっき銅粉におけるスズ皮膜の外観試験例》
実施例１〜５及び比較例１〜４で得られた各スズめっき銅粉について、銅粉表面へのスズめっきの被覆度合を目視観察により調べた。
評価基準は下記の通りである。
○：凝集のない均一な灰色の粉体であった。
×：赤茶色の不均一な（部分的に灰色や赤色が混在した状態の）粉体であった。
<< Example of tin film appearance test in tin-plated copper powder >>
About each tin plating copper powder obtained in Examples 1-5 and Comparative Examples 1-4, the coating degree of the tin plating to the copper powder surface was investigated by visual observation.
The evaluation criteria are as follows.
A: A uniform gray powder without aggregation.
X: Red-brown non-uniform powder (in a state where gray and red were partially mixed).
下表はその試験結果である。
被覆度合 被覆度合
実施例１ ○ 比較例１ ×
実施例２ ○ 比較例２ ×
実施例３ ○ 比較例３ ×
実施例４ ○ 比較例４ ×
実施例５ ○
The table below shows the test results.
Covering degree Covering example 1 ○ Comparative example 1 ×
Example 2 ○ Comparative Example 2 ×
Example 3 ○ Comparative Example 3 ×
Example 4 ○ Comparative Example 4 ×
Example 5 ○
そこで、上表の試験結果を説明する。
先ず、実施例１で得られたスズめっき銅粉は、凝集のない状態にあり、個々の銅粉の全面に亘りスズ皮膜が形成されていたため、銅の赤茶色或いは赤紫色が皮膜から露呈することがなく、均一な灰色の粉体であった。
同じく、銅粉分散液にメタンスルホン酸と界面活性剤を含有した実施例２、或は銅粉分散液にメタンスルホン酸と界面活性剤とチオ尿素を含有した実施例４も、凝集のない状態にあり、均一な灰色の粉体が得られた。
混合液をスライド加温した実施例３でも、同様に、凝集のない均一な灰色の粉体が得られた。
さらに、実施例５に示す通り、銅粉、可溶性スズ塩、界面活性剤などが含まれる複合分散液にチオ尿素のみを滴下しても、凝集のない均一な灰色の粉体が得られた。
この実施例の銅粉分散液、或は、得られた結果物の状態を説明すると、例えば、実施例１では、先ず、銅粉をメタンスルホン酸に添加した銅粉分散液の段階では、図１に示す通り、銅粉は水相中で良好に均一分散化していた。銅粉分散液をスズ塩含有液に滴下した後の撹拌状態にある混合液の段階でも、図２に示す通り、凝集（塊状物）のない均一な分散液を保持していた。そして、得られたスズめっき銅粉は、図３に示す通り、凝集のない滑らかな均一性を具備した灰色粉体であった。尚、本発明方法で製造すると、均一にスズめっきされているため、仮りに凝集部分が一部で発生したとしても、その部分に圧力をかけて凝集を潰すと、中の粒子は灰色を保持することができる。
Therefore, the test results in the above table will be described.
First, the tin-plated copper powder obtained in Example 1 is in an agglomeration-free state, and since a tin film was formed over the entire surface of each copper powder, copper reddish brown or reddish purple was exposed from the film. There was no uniform gray powder.
Similarly, Example 2 in which copper powder dispersion contains methanesulfonic acid and surfactant, or Example 4 in which copper powder dispersion contains methanesulfonic acid, surfactant and thiourea is also in a state without aggregation. A uniform gray powder was obtained.
Similarly, in Example 3 where the mixed solution was slide-heated, a uniform gray powder without aggregation was obtained.
Furthermore, as shown in Example 5, even when only thiourea was dropped into the composite dispersion containing copper powder, soluble tin salt, surfactant and the like, a uniform gray powder without aggregation was obtained.
The state of the copper powder dispersion of this example or the resulting product will be described. For example, in Example 1, first, at the stage of the copper powder dispersion obtained by adding copper powder to methanesulfonic acid, FIG. As shown in FIG. 1, the copper powder was uniformly dispersed in the aqueous phase. Even at the stage of the mixed solution in a stirring state after the copper powder dispersion was dropped into the tin salt-containing solution, a uniform dispersion without aggregation (lumps) was retained as shown in FIG. The obtained tin-plated copper powder was a gray powder having smooth uniformity without aggregation as shown in FIG. In addition, since it is tin-plated uniformly when manufactured by the method of the present invention, even if an agglomerated part is partially generated, if the agglomeration is crushed by applying pressure to that part, the particles inside will remain gray can do.
これに対して、実施例１〜５のような酸性の銅粉分散液ではなく、銅粉を水に添加しただけの分散液を使用した比較例１では、図４に示す通り、分散液の段階で既に不均一なうえ、一部はダマ状となって液表面に浮遊する状態になるため、たとえ、スズ塩含有液をこの分散液に滴下しても、銅粉の表面にスズ皮膜が均一に被覆した灰色の粉体は得られず、図５に示す通り、凝集して赤茶色或いは赤紫色の不均一な粉体しか生成しなかった。
この不均一な粉体は、スズ皮膜に覆われた灰色に銅の赤色が部分的に露出して混在した外観を呈し、粉体に圧力をかけて軽く粉体を潰すと、凝集が潰れてめっきされていない赤い粒子（コアの銅粉）が現れた。
混合液中のスズと銅の重量比が本発明の適正範囲より少ない比較例２では、やはり被覆するべきスズ量が不足して、赤茶色の不均一な粉体が生成し、スズ皮膜の灰色とコアの銅の赤色が混在して露呈した。
同様に、混合液を撹拌せずに処理した比較例３でも、赤茶色の不均一な（部分的に灰色や赤色（銅）が混在した状態の）粉体が生成された。
また、銅粉分散液を供給側としてスズ塩含有液に滴下した比較例４では、やはり、図５と同様に、赤茶色の不均一な（部分的に灰色や赤色（銅）がある状態の）粉体しか得られなかった。これは、ビーカーに収容した銅粉分散液を上から滴下すると、ビーカーの底に銅粉がたまり易く、上澄み液だけが先に添加された後、銅粉が塊となってめっき液（スズ塩含有液）に供給されるためであり、図６に示す通り、銅粉分散液がめっき液に供給された混合液中では、凝集した不均一な粉体（大小の塊状物）が認められた。
On the other hand, in the comparative example 1 which used the dispersion liquid which added only copper powder to water instead of acidic copper powder dispersion like Examples 1-5, as shown in FIG. Even if the tin salt-containing liquid is dropped into this dispersion, a tin film is not formed on the surface of the copper powder because it is already non-uniform at the stage and partly becomes lumpy and floats on the liquid surface. A uniformly coated gray powder could not be obtained, and as shown in FIG. 5, only a non-uniform powder of reddish brown or reddish purple was formed.
This non-uniform powder has a mixed appearance in which the copper red color is partially exposed in the gray covered with the tin film, and when the powder is lightly crushed by applying pressure to the powder, the agglomeration is crushed. Unplated red particles (core copper powder) appeared.
In Comparative Example 2 in which the weight ratio of tin and copper in the mixed solution is less than the appropriate range of the present invention, the amount of tin to be coated is still insufficient, and a reddish brown non-uniform powder is formed, and the tin coating is gray. And the copper core red were exposed.
Similarly, even in Comparative Example 3 where the mixed solution was processed without stirring, reddish brown non-uniform (partially mixed gray and red (copper)) powder was generated.
Further, in Comparative Example 4 in which the copper powder dispersion liquid was dropped onto the tin salt-containing liquid as the supply side, as in FIG. 5, red-brown unevenness (partially gray or red (copper) was present. ) Only powder was obtained. This is because when the copper powder dispersion contained in the beaker is dropped from above, the copper powder tends to accumulate at the bottom of the beaker, and after only the supernatant liquid is added first, the copper powder becomes a lump and the plating solution (tin salt) In the mixed solution in which the copper powder dispersion was supplied to the plating solution, agglomerated uneven powder (large and small lump) was observed as shown in FIG. .
Claims (5)
上記銅粉分散液が銅粉と酸を含有した酸性分散液であるか、銅粉と酸に加えてチオ尿素とチオ尿素誘導体から選ばれたチオ尿素類と界面活性剤の少なくとも一方を含有した酸性分散液であり、
スズ塩含有液が可溶性第一スズ塩と有機酸とチオ尿素類を含有した液であるか、可溶性第一スズ塩と有機酸とチオ尿素類に加えて界面活性剤と還元剤の少なくとも一方を含有した液であり、
銅粉分散液の酸は有機スルホン酸であるとともに、銅粉分散液の酸濃度は０.１〜８モル／Ｌであり、
銅粉分散液に対してスズ塩含有液を供給することで両者を混合し、
混合液を撹拌しながら置換反応させ、
混合液中のスズと銅の混合重量比がスズ／銅＝０.０５〜１.００であり、
混合液の加温域の上限が７０℃であることを特徴とするスズめっき銅粉の製造方法。 After mixing the tin salt-containing liquid and the copper powder dispersion under stirring, and performing a substitution reaction between copper and tin in the liquid mixture , filtering, washing and drying are performed on the surface of the copper powder. In the method for producing a tin-plated copper powder that forms a tin-plated film,
The copper powder dispersion is an acid dispersion containing copper powder and acid, or contains at least one of thioureas selected from thiourea and thiourea derivatives and a surfactant in addition to copper powder and acid . An acidic dispersion,
The tin salt-containing liquid is a liquid containing a soluble stannous salt, an organic acid, and a thiourea, or at least one of a surfactant and a reducing agent in addition to the soluble stannous salt, the organic acid, and the thiourea. Containing liquid,
The acid of the copper powder dispersion is organic sulfonic acid, and the acid concentration of the copper powder dispersion is 0.1 to 8 mol / L,
Both are mixed by supplying the tin salt-containing liquid to the copper powder dispersion,
While stirring the mixed solution,
The mixing weight ratio of tin and copper in the mixture is tin / copper = 0.05 to 1.00 ,
A method for producing a tin-plated copper powder, wherein the upper limit of the heating range of the mixed liquid is 70 ° C.
スズ塩含有液を銅粉分散液に供給して混合する代わりに、チオ尿素とチオ尿素誘導体から選ばれたチオ尿素類を複合分散液に供給して両者を混合し、
上記複合分散液が、銅粉と有機酸と可溶性第一スズ塩を含有する酸性分散液であるか、銅粉と有機酸と可溶性第一スズ塩に加えて界面活性剤と還元剤の少なくとも一方を含有する酸性分散液であり、
複合分散液の有機酸は有機スルホン酸であるとともに、複合分散液の酸濃度は０.１〜８モル／Ｌであり、
複合分散液に対してチオ尿素類を供給することで両者を混合し、
混合液を撹拌しながら置換反応させ、
混合液中のスズと銅の混合重量比がスズ／銅＝０.０５〜１.００であり、
混合液の加温域の上限が７０℃であることを特徴とするスズめっき銅粉の製造方法。 After mixing the tin salt-containing liquid and the copper powder dispersion under stirring, and performing a substitution reaction between copper and tin in the liquid mixture, filtering, washing and drying are performed on the surface of the copper powder. In the method for producing a tin-plated copper powder that forms a tin-plated film,
Instead of supplying and mixing the tin salt-containing liquid to the copper powder dispersion, the thioureas selected from thiourea and thiourea derivatives are supplied to the composite dispersion and mixed together.
The composite dispersion is an acidic dispersion containing copper powder, organic acid and soluble stannous salt, or at least one of surfactant and reducing agent in addition to copper powder, organic acid and soluble stannous salt An acidic dispersion containing
The organic acid of the composite dispersion is organic sulfonic acid, and the acid concentration of the composite dispersion is 0.1 to 8 mol / L.
Both are mixed by supplying thioureas to the composite dispersion,
While stirring the mixed solution,
The mixing weight ratio of tin and copper in the mixture is tin / copper = 0.5-1.00,
A method for producing a tin-plated copper powder, wherein the upper limit of the heating range of the mixed liquid is 70 ° C.
当該円筒又は球状の容器の直径に対するプロペラ径の割合が５／１０〜９.５／１０であり、
プロペラの回転速度が１２０〜１２００回転／分であることを特徴とする請求項１又は２に記載のスズめっき銅粉の製造方法。 In the stirring of the mixed liquid, the means for containing the mixed liquid is a cylindrical or spherical container, and the rotation axis of the propeller type stirring means is arranged along the central axis of the cylindrical or spherical container,
The ratio of the propeller diameter to the diameter of the cylindrical or spherical container is 5/10 to 9.5 / 10,
The method for producing a tin-plated copper powder according to claim 1 or 2 , wherein the rotation speed of the propeller is 120 to 1200 revolutions / minute.
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