JP2014065943A - Reduction type electroless tin plating bath - Google Patents
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本発明は、還元型無電解スズめっき浴に関し、詳しくは銅又は銅合金等の基材上に所望の膜厚のスズめっき皮膜を緻密かつ迅速に形成できる還元型無電解スズめっき浴に関する。 The present invention relates to a reduced electroless tin plating bath, and more particularly, to a reduced electroless tin plating bath capable of forming a tin plating film having a desired film thickness on a substrate such as copper or a copper alloy densely and rapidly.
スズめっき皮膜は、電子部品等に良好なハンダ付け性を付与することから、回路部品を構成したり、配線基板の電極表面に形成されている。 Since the tin plating film imparts good solderability to an electronic component or the like, it forms a circuit component or is formed on the electrode surface of a wiring board.
このスズめっき皮膜の形成は、電気めっきや無電解めっき等により形成される。無電解めっきは、均一の膜厚が得られるため、電子部品や回路の小型化に伴い、微小、微細な部品や独立回路へのめっきに適している。 The tin plating film is formed by electroplating or electroless plating. Since electroless plating provides a uniform film thickness, it is suitable for plating on minute and fine components and independent circuits as electronic components and circuits become smaller.
この無電解スズめっきは、強酸性浴である置換反応型無電解スズめっき浴を用いた置換析出反応により、スズめっき皮膜を形成する方法が主流となっていたが、この無電解スズめっき浴を用いた場合にはスズめっき皮膜の厚膜化が困難である。また、強アルカリ浴である不均化反応型無電解スズめっき浴を用いた不均化反応により、スズめっき皮膜を形成する方法が提案されているが、スズ皮膜の厚膜化は可能であるが、４価のスズ（ＳｎＯ３ ２−）の生成が問題となり、浴安定性やスズ析出速度において問題がある。 In this electroless tin plating, a method of forming a tin plating film by a substitution deposition reaction using a substitution reaction type electroless tin plating bath which is a strong acid bath has become the mainstream. When used, it is difficult to increase the thickness of the tin plating film. A method of forming a tin plating film by a disproportionation reaction using a disproportionation-type electroless tin plating bath, which is a strong alkaline bath, has been proposed, but it is possible to increase the thickness of the tin film. However, the production of tetravalent tin (SnO 3 2− ) becomes a problem, and there are problems in bath stability and tin deposition rate.
これに対して、自己触媒型（還元型）無電解スズめっき浴は中性から弱アルカリ性のめっき浴であり、スズ皮膜の厚膜化は可能であるが、自己触媒性を必要とする。この自己触媒型無電解スズめっき浴は、２価のスズ塩と還元剤と錯化剤を基本組成とするめっき浴である。還元剤としては３価のチタンが一般的に用いられている。 On the other hand, the autocatalytic (reduction) electroless tin plating bath is a neutral to weakly alkaline plating bath, and it is possible to increase the thickness of the tin film, but it requires autocatalytic properties. This self-catalyzed electroless tin plating bath is a plating bath having a basic composition of a divalent tin salt, a reducing agent, and a complexing agent. As the reducing agent, trivalent titanium is generally used.
しかし、このような還元型無電解スズめっき浴を用いた場合でも、スズ上では反応が起こりにくい、還元剤の自然劣化が早い等の理由によって、厚膜化が阻害され、密着不良、ハンダ付け性の低下を招くという問題がある。また、形成されたスズ皮膜自身に良好な緻密性が得られなかったり、浴安定性に劣る、基材によってはスズめっき皮膜の形成が困難である等の問題も生ずる。 However, even when such a reduced electroless tin plating bath is used, it is difficult to cause a reaction on tin, and the natural degradation of the reducing agent is accelerated, so that thickening is hindered, resulting in poor adhesion and soldering. There is a problem of causing a decline in sex. In addition, there are problems that the formed tin film itself does not have good denseness, has poor bath stability, and depending on the substrate, it is difficult to form a tin plating film.
このような還元型無電解スズめっき浴の問題を解決する試みが種々提案されている。特許文献１（特開昭５８−１８５７９号公報）には、２価のスズ塩と還元剤として用いられる３価のチタン塩を含有するめっき液に特定の有機スルホン酸を含有させることが提案されている。この無電解スズめっき浴によれば、難溶性化合物の形成が防止され、密着性やハンダ付け性の不良が回避されるとされている。 Various attempts to solve the problem of such a reduced electroless tin plating bath have been proposed. Patent Document 1 (Japanese Patent Laid-Open No. 58-18579) proposes that a specific organic sulfonic acid is contained in a plating solution containing a divalent tin salt and a trivalent titanium salt used as a reducing agent. ing. According to this electroless tin plating bath, it is said that formation of a hardly soluble compound is prevented, and poor adhesion and solderability are avoided.
また、特許文献２（特開平８−６０３７６号公報）には、２価のスズイオンもしくは２価のスズイオンと鉛イオン、錯化剤、還元剤及びｐＨ調整剤とを含む無電解めっき浴に、酸化防止剤を添加し、不活性ガスを通気する無電解めっき方法が記載されている。この無電解めっき方法により、めっき浴の劣化を防止することができるとされている。 Patent Document 2 (JP-A-8-60376) discloses that an electroless plating bath containing divalent tin ions or divalent tin ions and lead ions, a complexing agent, a reducing agent, and a pH adjusting agent is oxidized. An electroless plating method in which an inhibitor is added and an inert gas is passed is described. It is said that this electroless plating method can prevent the deterioration of the plating bath.
特許文献３（再公表ＷＯ２００９／１５７３３４号公報）には、水溶性スズ化合物、水溶性チタン化合物、有機錯化剤、並びに、メルカプタン類及びスルフィド類からなる群より選ばれる有機イオウ化合物を構成成分とする無電解スズめっき液が記載されている。この有機イオウ化合物を構成成分とする無電解スズめっき液によれば、母材銅又は母材銅合金への置換反応を抑制し、めっき液中に銅の溶出が抑制され、高速で安定なスズの析出を可能とし、めっき液が安定である等、実用に耐え得る還元型無電解スズめっき液を提供できると記載されている。 Patent Document 3 (Republished WO2009 / 157334) includes a water-soluble tin compound, a water-soluble titanium compound, an organic complexing agent, and an organic sulfur compound selected from the group consisting of mercaptans and sulfides as constituent components. An electroless tin plating solution is described. According to the electroless tin plating solution containing the organic sulfur compound as a constituent component, the substitution reaction to the base material copper or the base material copper alloy is suppressed, and the elution of copper is suppressed in the plating solution, and the tin is stable at high speed. It is described that it is possible to provide a reduced electroless tin plating solution that can withstand practical use, such as being capable of being deposited and being stable.
さらに、特許文献４（特開２０１０−２０２８９５号公報）には、銅又は銅合金に、３価のチタン化合物を還元剤とする無電解スズめっき浴を用いて複数回スズめっき皮膜を形成するスズめっき皮膜の形成方法が記載されている。 Furthermore, Patent Document 4 (Japanese Patent Laid-Open No. 2010-202895) discloses that tin is formed on a copper or copper alloy a plurality of times by using an electroless tin plating bath having a trivalent titanium compound as a reducing agent. A method for forming a plating film is described.
しかし、これら特許文献１〜４で提案された還元型無電解スズめっき浴又は還元型無電解スズめっき方法等においても、良好な緻密性を有し、しかも厚膜化されたスズめっき皮膜を迅速に、工業性をもって形成できる還元型無電解スズめっき浴は得られていない。 However, even in the reduced electroless tin plating bath or the reduced electroless tin plating method proposed in Patent Documents 1 to 4, a tin plating film having good denseness and having a thick film can be quickly formed. In addition, a reduced electroless tin plating bath that can be formed with industrial properties has not been obtained.
従って、本発明の目的は、良好な緻密性を有し、しかも厚膜化されたスズめっき皮膜を迅速に形成できる還元型無電解スズめっき浴を提供することにある。 Accordingly, an object of the present invention is to provide a reducing electroless tin plating bath that has a good denseness and can rapidly form a thickened tin plating film.
本発明者らは、上記のような課題を解決すべく鋭意検討した結果、還元型無電解スズめっき浴に、析出反応促進剤、すなわち膜厚促進剤を含有させることによって、上記課題が解決することを知見し、本発明に至った。 As a result of intensive studies to solve the above-described problems, the present inventors have solved the above-mentioned problems by adding a precipitation reaction accelerator, that is, a film thickness accelerator, to the reduced electroless tin plating bath. As a result, the present invention has been achieved.
すなわち、本発明は、水溶性スズ塩、錯化剤、及び３価の水溶性チタン塩からなる還元剤を含有する還元型無電解スズめっき浴に、膜厚促進剤を含有させたこと特徴とする還元型無電解スズめっき浴を提供するものである。 That is, the present invention is characterized by including a film thickness accelerator in a reduced electroless tin plating bath containing a water-soluble tin salt, a complexing agent, and a reducing agent comprising a trivalent water-soluble titanium salt. A reduced electroless tin plating bath is provided.
本発明に係る前記還元型無電解スズめっき浴において、前記膜厚促進剤として二酸化ゲルマニウムが好ましく用いられる。 In the reduced electroless tin plating bath according to the present invention, germanium dioxide is preferably used as the film thickness accelerator.
本発明に係る前記還元型無電解スズめっき浴において、前記膜厚促進剤としてニッケル、カルシウム、マンガン及びコバルトから選択される少なくとも１種の塩化物が好ましく用いられる。 In the reduced electroless tin plating bath according to the present invention, at least one chloride selected from nickel, calcium, manganese and cobalt is preferably used as the film thickness accelerator.
本発明に係る前記還元型無電解スズめっき浴において、前記水溶性スズ塩が第２スズ塩（ＩＶ）であることが望ましい。 In the reduced electroless tin plating bath according to the present invention, the water-soluble tin salt is preferably a stannic salt (IV).
本発明に係る前記還元型無電解スズめっき浴において、前記膜厚促進剤の濃度は０．５〜１５ｍｍｏｌ／Ｌであることが望ましい。 In the reduced electroless tin plating bath according to the present invention, the concentration of the film thickness promoter is preferably 0.5 to 15 mmol / L.
本発明に係る還元型無電解スズめっき浴は、良好な緻密性を有し、しかも厚膜化されたスズめっき皮膜を迅速に形成できる。特に、４価の水溶性スズ塩を用いることによって、優れた浴安定性を有する。 The reduced electroless tin plating bath according to the present invention has a good denseness and can rapidly form a thickened tin plating film. In particular, by using a tetravalent water-soluble tin salt, it has excellent bath stability.
以下、本発明を実施するための形態について説明する。
＜本発明に係る還元型無電解スズめっき浴＞
Hereinafter, modes for carrying out the present invention will be described.
<Reduced electroless tin plating bath according to the present invention>
本発明に係る還元型無電解スズめっき浴は、水溶性スズ塩、錯化剤、及び３価の水溶性チタンからなる還元剤を含有する。 The reduced electroless tin plating bath according to the present invention contains a reducing agent comprising a water-soluble tin salt, a complexing agent, and trivalent water-soluble titanium.
本発明に係る還元型無電解スズめっき浴に用いられる水溶性スズ塩としては、２価の第１スズ塩及び４価の第２スズ塩のいずれも使用可能であるが、浴安定性が高く、かつ低温でもめっき可能であるという点から４価の第２スズ塩が好ましく用いられる。 As the water-soluble tin salt used in the reduced electroless tin plating bath according to the present invention, either a divalent stannous salt or a tetravalent stannic tin salt can be used, but the bath stability is high. In addition, tetravalent stannic salts are preferably used because they can be plated even at low temperatures.
具体的な水溶性スズ塩としては、塩化第１スズ、塩化第２スズ、硫酸第１スズ、硫酸第２スズ、水酸化第１スズ、水酸化第２スズ等が例示されるが、水溶性であれば特に制限されない。これらの中でも、塩化第１スズ、塩化第２スズ、硫酸第１スズ、硫酸第２スズが、得られるめっき皮膜性能、経済性、取扱い性から好ましく、塩化第２スズ及び硫酸第２スズが浴安定性から特に好ましい。 Specific examples of water-soluble tin salts include stannous chloride, stannic chloride, stannous sulfate, stannic sulfate, stannous hydroxide, stannic hydroxide, and the like. If it is, it will not be restrict | limited in particular. Among these, stannous chloride, stannic chloride, stannous sulfate, and stannic sulfate are preferable from the viewpoint of the obtained plating film performance, economy, and handleability, and stannic chloride and stannic sulfate are baths. Particularly preferred from the standpoint of stability.
本発明に係る還元型無電解スズめっき浴中の水溶性スズ塩の濃度は、０．０５〜０．５ｍｏｌ／Ｌが好ましく、さらに好ましくは０．１〜０．２ｍｏｌ／Ｌである。水溶性スズ塩の濃度が０．０５ｍｏｌ／Ｌ未満では、スズ皮膜の析出速度が遅く、所望の膜厚のスズ皮膜が得られず、０．５ｍｏｌ／Ｌを超えると、溶解しないスズ塩が浴中に残存し、スズ皮膜の形成を阻害する恐れがあり、また経済的にも不利である。 The concentration of the water-soluble tin salt in the reduced electroless tin plating bath according to the present invention is preferably 0.05 to 0.5 mol / L, more preferably 0.1 to 0.2 mol / L. When the concentration of the water-soluble tin salt is less than 0.05 mol / L, the deposition rate of the tin film is slow, and a tin film having a desired film thickness cannot be obtained. There is a risk that it will remain in the film, obstructing the formation of the tin film, and is also disadvantageous economically.
本発明に係る還元型無電解スズめっき浴に用いられる錯化剤は、スズイオン及び後述する３価のチタンイオンの錯化剤として用いられる。 The complexing agent used in the reduced electroless tin plating bath according to the present invention is used as a complexing agent for tin ions and trivalent titanium ions described later.
ここに用いられる錯化剤としては、特に制限はないが、カルボン酸類、例えばクエン酸、グルタル酸、コハク酸、リンゴ酸、酒石酸、乳酸、グルコン酸及びこれらの塩；リン酸類、例えばトリポリリン酸、ヒドロキシエタンジホスホン酸及びこれらの塩；糖類、例えばソルビートル、マンニトール及びこれらの塩；アミノ酸類、例えばフェニルアラニン、グルタミン酸、アスパラギン酸、アラニン、グリシン及びこれらの塩；ＥＤＴＡ系、例えばＨＥＤＴＡ、ＥＤＴＡ、クアドールがそれぞれ挙げられる。これらの錯化剤は適宜組み合わせて用いられる。具体的な組み合わせとしては、例えば無水クエン酸、ニトリロ三酢酸ナトリウム及びピロリン酸カリウムの組み合わせやクエン酸ナトリウム、ニトリロ三酢酸ナトリウム及びＥＤＴＡ−Ｎａの組み合わせが挙げられる。 The complexing agent used here is not particularly limited, but carboxylic acids such as citric acid, glutaric acid, succinic acid, malic acid, tartaric acid, lactic acid, gluconic acid and salts thereof; phosphoric acids such as tripolyphosphoric acid, Hydroxyethane diphosphonic acid and salts thereof; sugars such as sorbitol, mannitol and salts thereof; amino acids such as phenylalanine, glutamic acid, aspartic acid, alanine, glycine and salts thereof; EDTA systems such as HEDTA, EDTA, quadrole Respectively. These complexing agents are used in appropriate combination. Specific examples include a combination of anhydrous citric acid, sodium nitrilotriacetate and potassium pyrophosphate, and a combination of sodium citrate, sodium nitrilotriacetate and EDTA-Na.
本発明に係る還元型無電解スズめっき浴中の錯化剤の濃度は、０．０５〜１．０ｍｏｌ／Ｌが好ましく、さらに好ましくは０．１〜０．５ｍｏｌ／Ｌである。錯化剤の濃度が０．０５ｍｏｌ／Ｌ未満では、めっき浴中にスズが析出され、浴安定性に劣り、１．０ｍｏｌ／Ｌを超えると、錯体形成が過剰に進み、スズの析出速度が低下し、所望の膜厚のスズ皮膜が得られない。 The concentration of the complexing agent in the reduced electroless tin plating bath according to the present invention is preferably 0.05 to 1.0 mol / L, more preferably 0.1 to 0.5 mol / L. If the concentration of the complexing agent is less than 0.05 mol / L, tin is precipitated in the plating bath, resulting in poor bath stability. If it exceeds 1.0 mol / L, complex formation proceeds excessively, and the deposition rate of tin is increased. A tin film having a desired film thickness cannot be obtained.
本発明に係る還元型無電解スズめっき浴に用いられる還元剤としての３価の水溶性チタン塩としては、具体的には三塩化チタン、三臭化チタン、三ヨウ化チタン等のハロゲン化チタンや硫酸チタンが用いられる。得られるめっき皮膜性能、経済性、取扱い性から三塩化チタンが好ましく用いられる。 Specific examples of the trivalent water-soluble titanium salt as a reducing agent used in the reducing electroless tin plating bath according to the present invention include titanium halides such as titanium trichloride, titanium tribromide, and titanium triiodide. Or titanium sulfate is used. Titanium trichloride is preferably used from the viewpoint of the obtained plated film performance, economy, and handleability.
本発明に係る還元型無電解スズめっき浴中の還元剤としての３価の水溶性チタン塩の濃度は、０．０１〜０．２ｍｏｌ／Ｌが好ましく、さらに好ましくは０．０２〜０．１ｍｏｌ／Ｌである。３価の水溶性チタン塩の濃度が０．０１ｍｏｌ／Ｌ未満では、スズ皮膜の析出速度が遅く、所望の膜厚のスズ皮膜が得られず、０．２ｍｏｌ／Ｌを超えると、還元的な反応が急速に進行し、めっき浴中のスズ塩が異常析出してしまい、浴安定性に劣り、また経済的にも不利である。 The concentration of the trivalent water-soluble titanium salt as the reducing agent in the reduced electroless tin plating bath according to the present invention is preferably 0.01 to 0.2 mol / L, more preferably 0.02 to 0.1 mol. / L. When the concentration of the trivalent water-soluble titanium salt is less than 0.01 mol / L, the deposition rate of the tin film is slow, and a tin film having a desired film thickness cannot be obtained. The reaction proceeds rapidly, the tin salt in the plating bath is abnormally precipitated, the bath stability is poor, and it is economically disadvantageous.
本発明に係る還元型無電解スズめっき浴には、前記水溶性スズ塩、錯化剤、及び３価の水溶性チタン塩からなる還元剤に加えて、膜厚促進剤（析出反応促進剤）を含有させる。ここに用いられる膜厚促進剤としては、酸化ゲルマニウムやニッケル、カルシウム、マンガン及びコバルトから選択される少なくとも１種の塩化物が挙げられる。緻密で膜厚のスズ皮膜を得るためには、特に二酸化ゲルマニウム、塩化コバルトが好ましく用いられる。 In the reduced electroless tin plating bath according to the present invention, in addition to the reducing agent comprising the water-soluble tin salt, complexing agent, and trivalent water-soluble titanium salt, a film thickness accelerator (precipitation reaction accelerator) Containing. Examples of the film thickness accelerator used here include at least one chloride selected from germanium oxide, nickel, calcium, manganese, and cobalt. In order to obtain a dense and thick tin film, germanium dioxide and cobalt chloride are particularly preferably used.
本発明に係る還元型無電解スズめっき浴中の膜厚促進剤の含有量は０．５〜１５ｍｍｏｌ／Ｌがスズ皮膜の厚膜化の観点から好ましく、１．０〜１０ｍｍｏｌ／Ｌがさらに好ましい。膜厚促進剤の含有量が０．５ｍｍｏｌ未満では、膜厚促進剤の含有効果が得られず、スズ皮膜の厚膜化が図れない。また、膜厚促進剤の含有量が１５ｍｍｏｌを超えると、それ以上の厚膜化が図れず、経済的に不利である。 The content of the film thickness accelerator in the reduced electroless tin plating bath according to the present invention is preferably 0.5 to 15 mmol / L from the viewpoint of thickening the tin film, and more preferably 1.0 to 10 mmol / L. . When the content of the film thickness promoter is less than 0.5 mmol, the effect of including the film thickness accelerator cannot be obtained, and the tin film cannot be thickened. On the other hand, if the content of the film thickness accelerator exceeds 15 mmol, the film thickness cannot be increased further, which is economically disadvantageous.
本発明に係る還元型無電解スズめっき浴中には、前記必須成分に加えて、ｐＨ調整剤、酸化防止剤、界面活性剤、光沢剤等の添加剤を含有することができる。 The reduced electroless tin plating bath according to the present invention may contain additives such as a pH adjuster, an antioxidant, a surfactant, and a brightener in addition to the essential components.
ｐＨ調整剤としては炭酸ナトリウム水溶液、アンモニア水、塩酸等が用いられ、還元型無電解スズめっき浴を中性又は弱アルカリ性に維持する。また、酸化防止剤、界面活性剤、光沢剤等の添加剤としては公知のものが使用可能である。 As the pH adjuster, an aqueous sodium carbonate solution, aqueous ammonia, hydrochloric acid or the like is used, and the reduced electroless tin plating bath is maintained neutral or weakly alkaline. Moreover, well-known things can be used as additives, such as antioxidant, surfactant, and a brightener.
本発明に係る還元型無電解スズめっき浴を用いたスズめっき条件は特に限定されないが、液温３０〜９０℃が好ましく、液温４０〜８０℃が特に好ましい。めっき時間も特に限定されないが、１分〜５時間が好ましく、１０分〜２時間が特に好ましい。 The tin plating conditions using the reduced electroless tin plating bath according to the present invention are not particularly limited, but a liquid temperature of 30 to 90 ° C is preferable, and a liquid temperature of 40 to 80 ° C is particularly preferable. The plating time is not particularly limited, but 1 minute to 5 hours is preferable, and 10 minutes to 2 hours is particularly preferable.
本発明に係る還元型無電解スズめっき浴を用いたスズめっきの対象となる基材は、銅又は銅合金が一般的であるが、他の種々の基材にも適用可能である。 The base material to be subjected to tin plating using the reduced electroless tin plating bath according to the present invention is generally copper or a copper alloy, but can be applied to other various base materials.
以下、実施例等に基づき本発明を具体的に説明する。なお、実施例の効果の認識が容易となるように、実施例の冒頭に比較例１に関して述べる。 Hereinafter, the present invention will be specifically described based on examples and the like. Note that Comparative Example 1 will be described at the beginning of the example so that the effect of the example can be easily recognized.
［比較例１］
下記浴組成の無電解スズめっき浴を調製した。また、めっき条件（ｐＨ、浴温）は下記の通りとした。
塩化スズ（ＩＶ） ０．０２ｍｏｌ／Ｌ
無水クエン酸 ０．１０ｍｏｌ／Ｌ
ニトリロ三酢酸ナトリウム ０．０６ｍｏｌ／Ｌ
ピロリン酸カリウム ０．０２４ｍｏｌ／Ｌ
塩化チタン（塩酸溶液） ０．０４ｍｏｌ／Ｌ
ｐＨ（アンモニア水で調整） ９．０
浴温 ５０℃
[Comparative Example 1]
An electroless tin plating bath having the following bath composition was prepared. The plating conditions (pH, bath temperature) were as follows.
Tin (IV) chloride 0.02 mol / L
Citric anhydride 0.10 mol / L
Sodium nitrilotriacetate 0.06mol / L
Potassium pyrophosphate 0.024 mol / L
Titanium chloride (hydrochloric acid solution) 0.04 mol / L
pH (adjusted with ammonia water) 9.0
Bath temperature 50 ° C
この浴組成の無電解スズめっき浴を用い、前記めっき条件で銅板上にスズめっき皮膜を形成した。得られたスズめっき皮膜のめっき時間とめっき膜厚との関係を図１に示す。また、得られた皮膜の電子顕微鏡写真を図２（×３０００）に示す。 Using an electroless tin plating bath having this bath composition, a tin plating film was formed on a copper plate under the above plating conditions. The relationship between the plating time and the plating film thickness of the obtained tin plating film is shown in FIG. Moreover, the electron micrograph of the obtained film | membrane is shown in FIG. 2 (* 3000).
［実施例１］
比較例１の無電解スズめっき組成に、二酸化ゲルマニウムを２ｍｍｏｌ／Ｌ含有させ無電解スズめっき浴とした。
[Example 1]
The electroless tin plating composition of Comparative Example 1 contained 2 mmol / L of germanium dioxide to form an electroless tin plating bath.
この浴組成の無電解スズめっき浴を用い、比較例１と同様のめっき条件で銅板上にスズめっき皮膜を形成した。得られたスズめっき皮膜のめっき時間とめっき膜厚との関係を図１に示す。また、得られた皮膜の電子顕微鏡写真を図３（×３０００）に示す。 Using an electroless tin plating bath having this bath composition, a tin plating film was formed on a copper plate under the same plating conditions as in Comparative Example 1. The relationship between the plating time and the plating film thickness of the obtained tin plating film is shown in FIG. Moreover, the electron micrograph of the obtained film | membrane is shown in FIG. 3 (* 3000).
図１の結果から明らかなように、第２スズ塩を用い、膜厚促進剤（二酸化ゲルマニウム）を含有させた実施例１の無電解スズめっき浴は、膜厚促進剤を含有させない比較例１に比べて、高いレベルで厚膜化が可能である。めっき２時間後のめっき厚を比較するに、比較例１が０．２２μｍであるのに対し、実施例１は０．９８μｍであった。また、図２及び図３に示されるように、比較例１で形成されたスズ皮膜は隙間が見られるのに対し、実施例１で形成されたスズ皮膜は緻密に形成されていた。 As is clear from the results of FIG. 1, the electroless tin plating bath of Example 1 using a second tin salt and containing a film thickness accelerator (germanium dioxide) is Comparative Example 1 in which no film thickness accelerator is contained. Compared to the above, the film thickness can be increased at a high level. When comparing the plating thickness after 2 hours of plating, Comparative Example 1 was 0.22 μm, while Example 1 was 0.98 μm. Moreover, as FIG.2 and FIG.3 shows, while the tin film formed in the comparative example 1 showed the clearance gap, the tin film formed in Example 1 was formed densely.
［実施例２〜５］
比較例１の無電解スズめっき組成に、表１に示す膜厚促進剤として塩化ニッケル（実施例２）、塩化カルシウム（実施例３）、塩化マンガン（実施例４）及び塩化コバルトをそれぞれ７．５ｍｍｏｌ／Ｌ含有させ無電解スズめっき浴とした。
[Examples 2 to 5]
In the electroless tin plating composition of Comparative Example 1, nickel chloride (Example 2), calcium chloride (Example 3), manganese chloride (Example 4) and cobalt chloride are used as film thickness accelerators shown in Table 1, respectively. An electroless tin plating bath was prepared by containing 5 mmol / L.
この浴組成の無電解スズめっき浴をそれぞれ用い、比較例１と同様のめっき条件で銅板上にスズめっき皮膜を形成した。得られたスズめっき皮膜のめっき時間とめっき膜厚との関係を比較例１の結果と共に表１に示す。 Each of the electroless tin plating baths having this bath composition was used to form a tin plating film on the copper plate under the same plating conditions as in Comparative Example 1. Table 1 shows the relationship between the plating time and the plating film thickness of the obtained tin plating film together with the results of Comparative Example 1.
表１の結果から明らかなように、実施例２〜５は、比較例１に比較して、４０分、６０分及び１２０分での析出膜厚が増加する。特に、膜厚促進剤として塩化コバルトを用いた実施例５は１２０分での析出膜厚が大幅に増加する。また、実施例２〜４の１２０分での析出膜厚はほぼ同様であるが、６０分での析出膜厚は、実施例４＞実施例２＞実施例３の順となる。 As is clear from the results in Table 1, in Examples 2 to 5, the deposited film thickness increases at 40 minutes, 60 minutes, and 120 minutes as compared with Comparative Example 1. In particular, in Example 5 using cobalt chloride as the film thickness accelerator, the deposited film thickness in 120 minutes is significantly increased. Moreover, although the deposit film thickness in 120 minutes of Examples 2-4 is substantially the same, the deposit film thickness in 60 minutes is in the order of Example 4> Example 2> Example 3.
［比較例２］
下記浴組成の無電解スズめっき浴を調製した。また、めっき条件（ｐＨ、浴温）は下記の通りとした。
塩化スズ（ＩＩ） ０．０８ｍｏｌ／Ｌ
クエン酸ナトリウム ０．３４ｍｏｌ／Ｌ
ニトリロ三酢酸ナトリウム ０．２０ｍｏｌ／Ｌ
ＥＤＴＡ−Ｎａ ０．０２４ｍｏｌ／Ｌ
塩化チタン（塩酸溶液） ０．０４ｍｏｌ／Ｌ
ｐＨ（アンモニア水で調整） ９．０
浴温 ８０℃
[Comparative Example 2]
An electroless tin plating bath having the following bath composition was prepared. The plating conditions (pH, bath temperature) were as follows.
Tin (II) chloride 0.08mol / L
Sodium citrate 0.34 mol / L
Sodium nitrilotriacetate 0.20 mol / L
EDTA-Na 0.024 mol / L
Titanium chloride (hydrochloric acid solution) 0.04 mol / L
pH (adjusted with ammonia water) 9.0
Bath temperature 80 ° C
この浴組成の無電解スズめっき浴を用い、前記めっき条件で銅板上にスズめっき皮膜を形成した。得られたスズめっき皮膜のめっき時間とめっき膜厚との関係を図４に示す。 Using an electroless tin plating bath having this bath composition, a tin plating film was formed on a copper plate under the above plating conditions. FIG. 4 shows the relationship between the plating time and the plating film thickness of the obtained tin plating film.
［実施例６］
比較例２の無電解スズめっき組成に、二酸化ゲルマニウムを４ｍｍｏｌ／Ｌ含有させ無電解スズめっき浴とした。
[Example 6]
The electroless tin plating composition of Comparative Example 2 contained 4 mmol / L of germanium dioxide to form an electroless tin plating bath.
この浴組成の無電解スズめっき浴を用い、比較例２と同様のめっき条件で銅板上にスズめっき皮膜を形成した。得られたスズめっき皮膜のめっき時間とめっき膜厚との関係を図４に示す。 Using an electroless tin plating bath having this bath composition, a tin plating film was formed on a copper plate under the same plating conditions as in Comparative Example 2. FIG. 4 shows the relationship between the plating time and the plating film thickness of the obtained tin plating film.
図４の結果から明らかなように、第１スズ塩を用い、膜厚促進剤（二酸化ゲルマニウム）を含有させた実施例６の無電解スズめっき浴は、膜厚促進剤を含有させない比較例２に比べて、高いレベルで厚膜化が可能である。めっき２時間後のめっき厚を比較するに、比較例２が０．４６μｍであるのに対し、実施例６は１．４０μｍであった。なお、第１スズ塩を用いた実施例６は、第２スズ塩を用いた実施例１に比較して、析出膜厚は大きいものの、浴温度を上げないと析出が有効に行うことができず、浴安定性が乏しい傾向にあった。 As is clear from the results of FIG. 4, the electroless tin plating bath of Example 6 using a stannous salt and containing a film thickness accelerator (germanium dioxide) is Comparative Example 2 that does not contain a film thickness accelerator. Compared to the above, the film thickness can be increased at a high level. When comparing the plating thickness after 2 hours of plating, Comparative Example 2 was 0.46 μm, while Example 6 was 1.40 μm. In addition, although Example 6 using the stannous salt had a larger deposition film thickness than that of Example 1 using the second tin salt, the precipitation could be effectively performed without increasing the bath temperature. The bath stability tended to be poor.
本発明に係る還元型無電解スズめっき浴は、良好な緻密性を有し、しかも厚膜化されたスズめっき皮膜を迅速に形成することができる。特に４価の水溶性第２スズ塩を用いることによって、比較的低温でスズめっき皮膜の形成が可能なので、浴安定性が良好である。 The reduced electroless tin plating bath according to the present invention has good denseness and can rapidly form a thick tin plating film. In particular, by using a tetravalent water-soluble stannic salt, a tin plating film can be formed at a relatively low temperature, so that the bath stability is good.
従って、本発明は、銅又は銅合金を始めとして種々の基材上に所望の膜厚のスズめっきを形成するための還元型無電解スズめっき浴として好適に用いられる。 Therefore, the present invention is suitably used as a reducing electroless tin plating bath for forming tin plating having a desired film thickness on various substrates such as copper or copper alloys.
Claims (5)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170129312A1 (en) * | 2014-07-14 | 2017-05-11 | Denso Corporation | Air blowing device |
| TWI728217B (en) * | 2016-12-28 | 2021-05-21 | 德商德國艾托特克公司 | Tin plating bath and a method for depositing tin or tin alloy onto a surface of a substrate |
| CN114561633A (en) * | 2022-02-23 | 2022-05-31 | 吉安宏达秋科技有限公司 | Tin plating solution, preparation method thereof and tin plating method for printed circuit board |
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2012
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170129312A1 (en) * | 2014-07-14 | 2017-05-11 | Denso Corporation | Air blowing device |
| TWI728217B (en) * | 2016-12-28 | 2021-05-21 | 德商德國艾托特克公司 | Tin plating bath and a method for depositing tin or tin alloy onto a surface of a substrate |
| CN114561633A (en) * | 2022-02-23 | 2022-05-31 | 吉安宏达秋科技有限公司 | Tin plating solution, preparation method thereof and tin plating method for printed circuit board |
| CN114561633B (en) * | 2022-02-23 | 2023-11-14 | 吉安宏达秋科技有限公司 | Tinning liquid, preparation method thereof and tinning method for printed circuit board |
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