TW202132219A - Cyanide-free liquid composition for immersion gold plating - Google Patents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
Description
本發明是關於一種金析出促進劑，其使用於在印刷線路基板等的電子工業零件上形成鍍金皮膜時；一種無電解鍍金液，其包含該金析出促進劑；以及一種使用該無電解鍍金液的鍍覆方法及金析出促進方法等。The present invention relates to a gold precipitation accelerator used when forming a gold-plated film on electronic industrial parts such as printed circuit boards; an electroless gold plating solution containing the gold precipitation accelerator; and an electroless gold plating solution using the electroless gold plating solution The plating method and the gold precipitation promotion method.
印刷基板，其在基板上及/或基板內部具有金屬線路圖案。在該線路上使用銅等的電性阻抗低的金屬，並且設置有防止線路的氧化、腐蝕用及/或防止與金的遷移用的障壁金屬層。作為障壁金屬層而被使用的金屬，除了鎳或鎳合金之外，還能夠使用鈀、鉑、銀、鈷及此等的合金。又，也有基於防止因熱處理而導致鎳的擴散之目的，而在鎳層之上形成鈀層的技術。雖然在這些基底金屬層的形成後，會進一步以金皮膜覆蓋而完成線路，但因為通常金皮膜是利用來防止線路的腐蝕及/或作為接點，所以孔隙度高的皮膜並不佳，而要求是空隙少的表面。The printed substrate has a metal circuit pattern on the substrate and/or inside the substrate. A metal with low electrical resistance such as copper is used for this line, and a barrier metal layer for preventing oxidation and corrosion of the line and/or preventing migration with gold is provided. As the metal used as the barrier metal layer, in addition to nickel or nickel alloys, palladium, platinum, silver, cobalt, and alloys thereof can also be used. There is also a technique of forming a palladium layer on the nickel layer for the purpose of preventing the diffusion of nickel due to heat treatment. Although these base metal layers will be further covered with a gold film to complete the circuit after the formation of these base metal layers, the gold film is usually used to prevent corrosion of the circuit and/or as a contact, so a film with high porosity is not good. The requirement is a surface with few voids.
作為鍍金方法，已知有電解鍍金、自催化型無電解鍍金、基底觸媒（表面觸媒）鍍金、以及置換鍍金等。自催化型電解鍍金是藉由將金作為觸媒的還原劑來進行金析出。基底觸媒（表面觸媒）鍍金是藉由將基底金屬作為觸媒的還原劑來進行金析出。置換鍍金，是藉由受鍍面的基底金屬與金離子及/或金離子錯合物的電性置換反應來進行金析出。這些鍍覆方法也有組合二種以上來使用的情況。As the gold plating method, electrolytic gold plating, autocatalytic type electroless gold plating, base catalyst (surface catalyst) gold plating, and displacement gold plating are known. Autocatalytic electrolytic gold plating uses gold as a reducing agent as a catalyst for gold precipitation. Base catalyst (surface catalyst) gold plating uses base metal as a reducing agent for the catalyst to perform gold precipitation. Displacement gold plating is to carry out gold precipitation by an electrical displacement reaction between the base metal of the plated surface and gold ions and/or gold ion complexes. These plating methods may also be used in combination of two or more types.
作為無電解鍍金液，雖然多數報告是以含氰化物之鍍覆液作為金源，但是除了保管及管理的問題和各種處理時的安全性問題，再加上還有廢液處理費用上漲的問題。因此，一直期望著開發出不含有氰化物的無電解鍍金液。專利文獻1中，記載著一種無電解電鍍液（鍍覆液），其是使用亞硫酸金鈉等的水溶性金鹽來取代氰化物而成的包含二種還原劑的無電解電鍍液，並探討著將一般作為錯合劑使用的乙二胺四乙酸（EDTA）和酒石酸等的氧代羧酸類作為反應促進劑來使用。專利文獻2中，記載著一種無電解電鍍液，其同樣使用亞硫酸金鈉作為金源，專利文獻2中探討著為了提升金析出速度而使用亞硫酸鉀，但其中亦記載著，由於若亞硫酸鉀的濃度過大，則鍍覆液變得不穩定而引起自體分解，因此將亞硫酸鉀的濃度限制在500mg/L以下。在專利文獻3，探討著以釋放鹵素離子的化合物來作為無電解鍍金液的金析出促進劑，該鹵素離子促進陽極反應作用強。在專利文獻4，將鉈鹽等的重金屬作為金析出促進劑來使用。 [先前技術文獻] (專利文獻)As an electroless gold plating solution, although most reports use cyanide-containing plating solution as the source of gold, in addition to storage and management issues and safety issues during various treatments, there is also the issue of increased waste treatment costs. . Therefore, it has been desired to develop an electroless gold plating solution that does not contain cyanide. Patent Document 1 describes an electroless plating solution (plating solution), which is an electroless plating solution containing two reducing agents that uses water-soluble gold salts such as gold sodium sulfite instead of cyanide. The use of oxocarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and tartaric acid, which are generally used as complexing agents, as reaction accelerators is under discussion. Patent Document 2 describes an electroless plating solution that also uses sodium gold sulfite as a gold source. Patent Document 2 discusses the use of potassium sulfite in order to increase the rate of gold precipitation. If the concentration of potassium sulfate is too large, the plating solution will become unstable and cause self-decomposition. Therefore, the concentration of potassium sulfite is limited to 500 mg/L or less. In Patent Document 3, the use of a halogen ion-releasing compound as a gold precipitation accelerator of an electroless gold plating solution is considered, and the halogen ion has a strong effect of promoting the anode reaction. In Patent Document 4, heavy metals such as thallium salts are used as gold precipitation accelerators. [Prior Technical Literature] (Patent Document)
專利文獻1：日本特開2003-221674號公報 專利文獻2：日本專利第4758470號公報 專利文獻3：日本特開2010-209415號公報 專利文獻4：日本特開2007-308796號公報Patent Document 1: Japanese Patent Application Publication No. 2003-221674 Patent Document 2: Japanese Patent No. 4758470 Patent Document 3: Japanese Patent Application Laid-Open No. 2010-209415 Patent Document 4: Japanese Patent Application Publication No. 2007-308796
[發明所欲解決之問題] 習知的將氧代羧酸類和亞硫酸鉀等的錯合劑作為反應促進劑使用的方法，是期待其藉由錯離子配位到金屬離子的界面錯合物的形成(interface complexation)來促進金的析出之作用，但由於錯合劑會依據其添加量而使對基底的侵蝕成為問題，或因錯合劑自體的分解使鍍覆液不穩定，而誘發鍍覆液的自體分解，故必須控制添加量，再者當包含還原劑或穩定劑時，不能不考慮到該等成分的相互作用，僅依錯合劑要得到期望的金析出速度是有困難的。另一方面，使用鉈等重金屬的金析出促進劑，其對環境的影響會成為問題。 因此，本發明提供一種金析出促進劑，其使無電解鍍金液的金析出速度輕易地提升，並能夠形成均勻的金皮膜；又，提供一種無電解鍍金液，其包含該金析出促進劑；並且，提供一種使用該無電解鍍金液之鍍金方法、及金的析出促進方法等。 [解決問題之技術手段][The problem to be solved by the invention] The conventional method of using complexing agents such as oxocarboxylic acids and potassium sulfite as reaction accelerators is expected to promote gold through the formation of interface complexes in which complex ions coordinate to metal ions. The effect of precipitation, but because the complex agent will cause corrosion to the substrate depending on its added amount, or the self-decomposition of the complex agent makes the plating solution unstable and induces the self-decomposition of the plating solution, it must be Control the amount of addition, and when a reducing agent or a stabilizer is included, the interaction of these components cannot be ignored. It is difficult to obtain the desired gold precipitation rate based on the complex agent alone. On the other hand, the use of heavy metals such as thallium and other gold precipitation accelerators, its impact on the environment may become a problem. Therefore, the present invention provides a gold precipitation accelerator, which can easily increase the gold precipitation speed of the electroless gold plating solution and can form a uniform gold film; and also provides an electroless gold plating solution, which contains the gold precipitation accelerator; In addition, a gold plating method using the electroless gold plating solution, a gold precipitation promotion method, and the like are provided. [Technical means to solve the problem]
本案發明人，在探討不依賴錯合劑而促進金的析出的方法中，發現鹼金屬離子會對金析出速度帶來影響，進一步深入研究，終於完成本發明。The inventor of the present case explored a method for promoting the precipitation of gold without relying on a complexing agent, and found that alkali metal ions would affect the precipitation rate of gold, further in-depth research, and finally completed the present invention.
亦即，本發明是關於下述所列舉者： ［1］ 一種金析出促進劑，其用於無電解鍍金，並包含1種或2種以上的鹼金屬化合物，前述鹼金屬化合物不是僅含作為鹼金屬的鈉之化合物，且前述鹼金屬化合物不是僅為鹼金屬的鹵化物、僅為亞硫酸鉀或僅為酒石酸鉀鈉。 ［2］ 一種無電解鍍金液，其包含如前述［1］所述之金析出促進劑、水溶性金源及錯合劑。 ［3］ 如前述［2］所述之無電解鍍金液，其中，以鈉以外的鹼金屬離子來換算時，鹼金屬化合物的濃度為0.001～5M。 ［4］ 一種金析出促進劑，其包含銣化合物及/或銫化合物。 ［5］ 一種無電解鍍金液，其包含如前述［4］所述之金析出促進劑、水溶性金源及錯合劑。That is, the present invention relates to those listed below: [1] A gold precipitation accelerator used for electroless gold plating and containing one or more kinds of alkali metal compounds, the alkali metal compound is not a compound containing only sodium as an alkali metal, and the alkali metal compound is not Only alkali metal halides, only potassium sulfite, or only potassium sodium tartrate. [2] An electroless gold plating solution comprising the gold precipitation accelerator, a water-soluble gold source and a complexing agent as described in [1]. [3] The electroless gold plating solution described in [2] above, wherein the concentration of the alkali metal compound is 0.001 to 5M when calculated in terms of alkali metal ions other than sodium. [4] A gold precipitation accelerator comprising a rubidium compound and/or a cesium compound. [5] An electroless gold plating solution comprising the gold precipitation accelerator described in [4] above, a water-soluble gold source and a complexing agent.
［6］ 如［2］、［3］或［5］之中的任一項所述之無電解鍍金液，其中，進一步包含鈉化合物。 ［7］ 如［2］、［3］、［5］或［6］之中的任一項所述之無電解鍍金液，其中，不包含氰化物。 ［8］ 如［2］、［3］、［5］、［6］或［7］之中的任一項所述之無電解鍍金液，其中，包含酸或鹼作為pH調整劑。[6] The electroless gold plating solution according to any one of [2], [3], or [5], which further contains a sodium compound. [7] The electroless gold plating solution as described in any one of [2], [3], [5] or [6], which does not contain cyanide. [8] The electroless gold plating solution according to any one of [2], [3], [5], [6], or [7], which contains an acid or an alkali as a pH adjuster.
［9］ 一種形成鍍金皮膜的方法，其包含將如［2］、［3］、［5］、［6］、［7］或［8］之中的任一項所述之無電解鍍金液應用在電子工業零件的表面的步驟。 ［10］ 一種促進無電解鍍金中的金析出的方法，其包含將1種或2種以上的鹼金屬化合物添加到無電解鍍金液中的步驟，前述鹼金屬化合物不是僅含作為鹼金屬的鈉之化合物，且前述鹼金屬化合物不是僅為鹼金屬的鹵化物、僅為亞硫酸鉀或僅為酒石酸鉀鈉。 ［11］ 如［10］所述之方法，其中，以鈉以外的鹼金屬離子來換算時，鹼金屬化合物的濃度為0.001～5M ［12］ 一種促進無電解鍍金中的金析出的方法，其是藉由添加銣化合物及/或銫化合物來促進無電解鍍金中的金的析出。 ［13］ 如［12］所述之方法，其中，以銣離子及/或銫離子來換算時，銣化合物及/或銫化合物的濃度為0.001M～5M。 [發明之功效][9] A method for forming a gold-plated film, which comprises adding the electroless gold plating solution as described in any one of [2], [3], [5], [6], [7] or [8] Steps applied to the surface of parts in the electronics industry. [10] A method for promoting the precipitation of gold in electroless gold plating, which includes the step of adding one or two or more kinds of alkali metal compounds to the electroless gold plating solution. The aforementioned alkali metal compounds do not only contain sodium as an alkali metal The aforementioned alkali metal compound is not only an alkali metal halide, only potassium sulfite, or only potassium sodium tartrate. [11] The method described in [10], wherein the concentration of the alkali metal compound is 0.001 to 5M when converted to alkali metal ions other than sodium [12] A method for promoting the precipitation of gold in electroless gold plating by adding rubidium compounds and/or cesium compounds to promote the precipitation of gold in electroless gold plating. [13] The method described in [12], wherein the concentration of the rubidium compound and/or cesium compound is 0.001M to 5M when converted to rubidium ions and/or cesium ions. [Effects of Invention]
根據本發明，由於能夠輕易地提升無電解鍍金液的金析出速度，故即使在不將氰化物作為金源且析出速度慢的無電解鍍金液中，仍能夠實現充分的金析出速度。又，由於藉由僅調整鈉以外的鹼金屬離子的濃度，就能夠調整金析出速度，故與僅依賴錯合劑來促進金的析出的情況相比，本發明可進行採用多成分的調整，能夠提供更穩定的無電解鍍金液。並且，由於本發明無須使金濃度增量，就能夠使析出速度提升，故能夠提供價廉的鍍覆液。According to the present invention, since the gold precipitation rate of the electroless gold plating solution can be easily increased, a sufficient gold precipitation rate can be achieved even in an electroless gold plating solution that does not use cyanide as a gold source and has a slow precipitation rate. In addition, since the gold precipitation rate can be adjusted only by adjusting the concentration of alkali metal ions other than sodium, the present invention can be adjusted with multiple components compared to the case where only a complex agent is used to promote gold precipitation. Provide a more stable electroless gold plating solution. In addition, since the present invention can increase the precipitation rate without increasing the gold concentration, it is possible to provide an inexpensive plating solution.
本發明之金析出促進劑，包含鹼金屬化合物。 本發明之金析出促進劑的金析出促進作用，是依據鹼金屬離子而來，本發明之金析出促進劑中所包含的鹼金屬化合物，只要是會解離生成鹼金屬離子者即可。令人驚訝地，即使同樣是鹼金屬離子但鈉離子不會促進金析出反應。因此，本發明之金析出促進劑中所包含的鹼金屬化合物，不是僅含作為鹼金屬的鈉之化合物，但只要存在著鈉以外的鹼金屬，則亦可包含鈉。作為這樣的化合物，例如可舉出酒石酸鉀鈉。The gold precipitation accelerator of the present invention includes an alkali metal compound. The gold precipitation promoting effect of the gold precipitation accelerator of the present invention is based on alkali metal ions. The alkali metal compound contained in the gold precipitation accelerator of the present invention may dissociate to form alkali metal ions. Surprisingly, even though it is also an alkali metal ion, sodium ion does not promote the gold precipitation reaction. Therefore, the alkali metal compound contained in the gold precipitation accelerator of the present invention is not a compound containing only sodium as an alkali metal, but may contain sodium as long as an alkali metal other than sodium is present. Examples of such compounds include potassium sodium tartrate.
本發明之金析出促進劑中所包含的鹼金屬化合物，較佳為選自由鉀化合物、銣化合物及銫化合物所組成之群組中的1種或2種以上，從析出促進性的觀點而言，進而較佳為銣化合物及/或銫化合物。從成本的觀點而言，鉀化合物亦佳。The alkali metal compound contained in the gold precipitation accelerator of the present invention is preferably one or two or more selected from the group consisting of potassium compounds, rubidium compounds, and cesium compounds, from the standpoint of precipitation promotion , More preferably a rubidium compound and/or a cesium compound. From the viewpoint of cost, potassium compounds are also preferable.
本發明之金析出促進劑中所包含的鹼金屬化合物，可舉出在以下記載的化合物，但並不限定於此。例如可舉出：碳酸鉀、碳酸銣、碳酸銫等的碳酸鹽；硝酸銫、硝酸銣、硝酸銫等的硝酸鹽；硫酸鉀、硫酸銣、硫酸銫等的硫酸鹽；鹵化物，作為鹵化物可舉出：氟化鉀、氟化銣、氟化銫等的氟化物；氯化鉀、氯化銣、氯化銫等的氯化物；溴化鉀、溴化銣、溴化銫等的溴化物；碘化鉀、碘化銣、碘化銫等的碘化物等。這些化合物亦可單獨使用亦可併用2種以上。The alkali metal compound contained in the gold precipitation accelerator of the present invention includes the compounds described below, but is not limited thereto. For example, carbonates such as potassium carbonate, rubidium carbonate, and cesium carbonate; nitrates such as cesium nitrate, rubidium nitrate, and cesium nitrate; sulfates such as potassium sulfate, rubidium sulfate, and cesium sulfate; halides, as halides Examples include fluorides such as potassium fluoride, rubidium fluoride, and cesium fluoride; chlorides such as potassium chloride, rubidium chloride, and cesium chloride; bromine such as potassium bromide, rubidium bromide, and cesium bromide Compounds; potassium iodide, rubidium iodide, cesium iodide and other iodides. These compounds can also be used individually or in combination of 2 or more types.
相對於該化合物中的鹼金屬離子的相對離子並沒有特別限制。作為該相對離子，例如可舉出：碳酸離子、硝酸離子、硫酸離子、亞硫酸離子、磷酸離子、硼酸離子、鹵化物離子、甲酸離子、乙酸離子、丙酸離子、丁酸離子、戊酸離子、己酸離子、庚酸離子、辛酸離子等的羧酸離子；乙醇酸離子、乳酸離子、蘋果酸離子、檸檬酸離子、酒石酸離子、異檸檬酸離子、柳酸離子等的羥酸離子；苯甲酸離子、苯二甲酸離子等的芳香族羧酸離子；乙二酸離子、丙二酸離子、丁二酸離子、戊二酸離子、己二酸離子、富馬酸離子、馬來酸離子等的二羧酸離子等。這些化合物可單獨使用亦可併用2種以上。The relative ion relative to the alkali metal ion in the compound is not particularly limited. Examples of the counter ion include: carbonate ion, nitrate ion, sulfate ion, sulfite ion, phosphate ion, borate ion, halide ion, formate ion, acetate ion, propionate ion, butyrate ion, and valerate ion. Carboxylic acid ion such as hexanoic acid ion, heptanoic acid ion and caprylic acid ion; hydroxyl acid ion such as glycolic acid ion, lactate ion, malate ion, citrate ion, tartrate ion, isocitrate ion, salicylic acid ion, etc.; benzene Aromatic carboxylic acid ions such as formic acid ion, phthalic acid ion, etc.; oxalic acid ion, malonic acid ion, succinate ion, glutaric acid ion, adipic acid ion, fumaric acid ion, maleic acid ion, etc. The dicarboxylic acid ion and so on. These compounds may be used alone or in combination of two or more kinds.
作為具有上述相對離子的化合物以外的鹼金屬化合物，可舉出在以下記載的化合物，但並不限定於此。例如可舉出：鹼金屬的氧化物、過氧化物、氫氧化物、鉻酸化合物、鎢酸化合物、硒酸化合物、鉬酸化合物、正鉬酸化合物、鈮酸化合物、過錳酸化合物、疊氮化合物、醯胺化合物、甲苯磺酸化合物、氫化物、苦味酸化合物、四氫硼酸化合物、六氟矽酸化合物、過錸酸化合物、過碘酸化合物、碘酸化合物、亞硝酸化合物、次膦酸化合物、硝苯磺酸化合物、苯磺酸化合物、烷氧化合物、碳酸氫鹽化合物、甲基丙烯酸化合物等。這些化合物可單獨使用亦可併用2種以上。As an alkali metal compound other than the compound which has the said counter ion, the compound described below can be mentioned, but it is not limited to this. Examples include: alkali metal oxides, peroxides, hydroxides, chromic acid compounds, tungstic acid compounds, selenate compounds, molybdate compounds, orthomolybdate compounds, niobic acid compounds, permanganic acid compounds, stacks Nitrogen compounds, amide compounds, toluene sulfonic acid compounds, hydrides, picric acid compounds, tetrahydroborate compounds, hexafluorosilicic acid compounds, perrhenic acid compounds, periodic acid compounds, iodic acid compounds, nitrous acid compounds, phosphine Acid compounds, nitrobenzene sulfonic acid compounds, benzene sulfonic acid compounds, alkoxy compounds, bicarbonate compounds, methacrylic acid compounds, etc. These compounds may be used alone or in combination of two or more kinds.
如此一來，本案發明之金析出促進劑，可以是鹼金屬化合物本身，或亦可以是含該化合物的組成物。組成物可能是由2種以上的鹼金屬化合物所構成的混合物。又，組成物亦可以是除了1種或2種以上的鹼金屬之外，再加上包含水、有機溶劑等的溶劑。In this way, the gold precipitation accelerator of the present invention may be the alkali metal compound itself, or may also be a composition containing the compound. The composition may be a mixture of two or more alkali metal compounds. In addition, the composition may be a solvent containing water, an organic solvent, etc., in addition to one or two or more kinds of alkali metals.
本發明之金析出促進劑中，金析出促進劑中所包含的鹼金屬化合物，不是僅為鹼金屬的鹵化物、僅為亞硫酸鉀或僅為酒石酸鉀鈉。 本發明之金析出促進劑的一個態樣中，金析出促進劑中所包含的鹼金屬化合物不是僅為亞硫酸鹽。 本發明之金析出促進劑的一個態樣中，金析出促進劑中所包含的鹼金屬化合物不是僅為酒石酸鹽。 本發明之金析出促進劑的一個態樣中，金析出促進劑在僅包含鉀化合物作為鹼金屬化合物的情況中，包含選自鹵化鉀、亞硫酸鉀及酒石酸鉀鈉的鉀化合物以外之鉀化合物。In the gold precipitation accelerator of the present invention, the alkali metal compound contained in the gold precipitation accelerator is not only an alkali metal halide, only potassium sulfite, or only potassium sodium tartrate. In one aspect of the gold precipitation accelerator of the present invention, the alkali metal compound contained in the gold precipitation accelerator is not only a sulfite. In one aspect of the gold precipitation accelerator of the present invention, the alkali metal compound contained in the gold precipitation accelerator is not only tartrate. In one aspect of the gold precipitation accelerator of the present invention, the gold precipitation accelerator includes potassium compounds other than potassium compounds selected from potassium halides, potassium sulfite, and potassium sodium tartrate when only a potassium compound is included as an alkali metal compound .
本發明之金析出促進劑，在包含該金析出促進劑的鍍覆液中，包含鈉以外的鹼金屬之鹼金屬化合物，能夠以下述方式調整來使用：以鈉以外的鹼金屬離子換算之濃度成為0.001M以上，較佳是成為0.01M以上，進而較佳是成為0.02M以上。從析出促進性的觀點而言，該濃度能調整如下：成為0.001M～5M，進而較佳是成為0.01M～2M，特佳是成為0.02M～0.5M。由於在金析出速度中亦可看到濃度依賴性，故藉由調整濃度，亦能夠調整期望的金析出速度。The gold precipitation accelerator of the present invention contains an alkali metal compound of an alkali metal other than sodium in a plating solution containing the gold precipitation accelerator, and can be used by adjusting the concentration in terms of alkali metal ions other than sodium It is 0.001M or more, preferably 0.01M or more, and more preferably 0.02M or more. From the standpoint of precipitation promotion, the concentration can be adjusted as follows: 0.001M to 5M, more preferably 0.01M to 2M, and particularly preferably 0.02M to 0.5M. Since concentration dependence can also be seen in the gold precipitation rate, it is also possible to adjust the desired gold precipitation rate by adjusting the concentration.
本發明的一個態樣中，本發明之金析出促進劑不含酒石酸鉀鈉。 本發明的一個態樣中，當本發明之金析出促進劑包含酒石酸鉀鈉或酒石酸鹽時，較佳是以下述方式調整來使用：鍍覆液中的酒石酸鉀鈉的濃度成為0.11M以上，較佳為大於0.11M，進而較佳是成為0.2M以上。從析出促進性的觀點而言，該濃度較佳為0.11M～5M，進而較佳為0.11M～2M，特佳為0.11M～0.5M。In one aspect of the present invention, the gold precipitation accelerator of the present invention does not contain potassium sodium tartrate. In one aspect of the present invention, when the gold precipitation accelerator of the present invention contains potassium sodium tartrate or tartrate, it is preferably adjusted and used in the following manner: the concentration of potassium sodium tartrate in the plating solution becomes 0.11M or more, It is preferably more than 0.11M, and more preferably 0.2M or more. From the standpoint of precipitation acceleration, the concentration is preferably 0.11M to 5M, more preferably 0.11M to 2M, and particularly preferably 0.11M to 0.5M.
本發明的一個態樣中，本發明之金析出促進劑不含亞硫酸鉀。 本發明的一個態樣中，當本發明之金析出促進劑包含亞硫酸鉀或亞硫酸鹽時，較佳是以鍍覆液中的亞硫酸鉀的濃度成為0.004M以上的方式調整來使用。從析出促進性的觀點而言，該濃度較佳為0.004M～5M，進而較佳為0.01M～2M，特佳為0.02M～0.5M。In one aspect of the present invention, the gold precipitation accelerator of the present invention does not contain potassium sulfite. In one aspect of the present invention, when the gold precipitation accelerator of the present invention contains potassium sulfite or sulfite, it is preferably adjusted and used so that the concentration of potassium sulfite in the plating solution becomes 0.004M or more. From the standpoint of precipitation acceleration, the concentration is preferably 0.004M to 5M, more preferably 0.01M to 2M, and particularly preferably 0.02M to 0.5M.
本發明又關於一種無電解鍍金液，其包含上述的本發明之金析出促進劑、水溶性金源及錯合劑。 包含本發明之金析出促進劑的無電解鍍金液中，鹼金屬化合物的濃度，以鈉以外的鹼金屬離子來換算時，較佳為0.001M以上，進而較佳為0.01M以上，特佳為0.02M以上。從析出促進性的觀點而言，該濃度較佳為0.001M～5M，進而較佳為0.01M～2M，特佳為0.02M～0.5M。金析出速度中亦可看到一定程度的濃度依賴性，故藉由調整濃度，能夠調整期望的金析出速度。The present invention also relates to an electroless gold plating solution, which comprises the above-mentioned gold precipitation promoter of the present invention, a water-soluble gold source and a complexing agent. In the electroless gold plating solution containing the gold precipitation accelerator of the present invention, the concentration of the alkali metal compound is preferably 0.001M or more, more preferably 0.01M or more, particularly preferably Above 0.02M. From the standpoint of precipitation promotion, the concentration is preferably 0.001M to 5M, more preferably 0.01M to 2M, and particularly preferably 0.02M to 0.5M. A certain degree of concentration dependence can also be seen in the gold precipitation rate, so by adjusting the concentration, the desired gold precipitation rate can be adjusted.
作為用於本發明中的金源，具體而言，能夠使用亞硫酸金鹽或氯化金酸鹽等的水溶性金鹽。從安全性以及廢液處理的問題的觀點而言，較佳為使用不含氰的金源。金源的濃度較佳為0.1～10g/L，更佳為0.5～5g/L。例如在使用亞硫酸金鈉的情況中，若考慮到析出皮膜的物性，則亞硫酸金鈉的濃度範圍以金濃度來換算時，較佳為0.1～10g/L，更佳為0.5～5g/L。本發明的一個態樣中，金源不含鈉以外的鹼金屬。又，本發明的一個態樣中，本發明之金析出促進劑包含不含金的鹼金屬化合物。As the gold source used in the present invention, specifically, water-soluble gold salts such as gold sulfite and gold chloride can be used. From the viewpoint of safety and waste liquid disposal, it is preferable to use a cyanide-free gold source. The concentration of the gold source is preferably 0.1-10 g/L, more preferably 0.5-5 g/L. For example, in the case of using sodium gold sulfite, considering the physical properties of the deposited film, the concentration range of sodium gold sulfite is preferably 0.1-10 g/L, more preferably 0.5-5 g/L when converted to gold concentration. L. In one aspect of the present invention, the gold source does not contain alkali metals other than sodium. Furthermore, in one aspect of the present invention, the gold precipitation accelerator of the present invention includes an alkali metal compound that does not contain gold.
本發明的一個態樣中，當金源包含鈉以外的鹼金屬時，本發明之無電解鍍金液，進一步包含不含金的鹼金屬化合物，此時，無電解鍍金液中的鈉以外的鹼金屬離子的濃度，較佳為0.001M以上，進而較佳為0.01M以上，特佳為0.02M以上。從析出促進性的觀點而言，該濃度較佳為0.001M～5M，進而較佳為0.01M～2M，特佳為0.02M～0.5M。該鹼金屬離子的濃度，是將源自金源的鹼金屬離子以及源自前述不含金的鹼金屬化合物的鹼金屬離子加總而得的濃度（不含鈉離子）。In one aspect of the present invention, when the gold source contains an alkali metal other than sodium, the electroless gold plating solution of the present invention further includes an alkali metal compound that does not contain gold. In this case, the alkali metal other than sodium in the electroless gold plating solution The concentration of metal ions is preferably 0.001M or more, more preferably 0.01M or more, and particularly preferably 0.02M or more. From the standpoint of precipitation promotion, the concentration is preferably 0.001M to 5M, more preferably 0.01M to 2M, and particularly preferably 0.02M to 0.5M. The concentration of the alkali metal ions is the sum of the alkali metal ions derived from the gold source and the alkali metal ions derived from the aforementioned alkali metal compound not containing gold (not containing sodium ions).
作為用於本發明中的錯合劑，並沒有特別限定，具體而言例如可舉出：亞硫酸鹽、硫代硫酸鹽等的能與一價或三價金離子形成錯合物的化合物等。錯合劑的濃度較佳為0.001M～5M，更佳為0.01M～0.5M，作為錯合劑，例如當使用亞硫酸鈉時，其濃度範圍，較佳為0.001～5M，更佳為0.01～0.5M。The complexing agent used in the present invention is not particularly limited, and specific examples include compounds capable of forming complexes with monovalent or trivalent gold ions such as sulfites and thiosulfates. The concentration of the complexing agent is preferably 0.001M-5M, more preferably 0.01M-0.5M. As the complexing agent, for example, when sodium sulfite is used, the concentration range is preferably 0.001-5M, more preferably 0.01-0.5M.
作為pH調整劑，例如，能夠使用：硫酸、鹽酸、磷酸等的各種酸；氫氧化鈉、氫氧化鉀等的氫氧化物塩；及，附有限制下使用的NR4 OH（R：氫或烷基）等的胺類等。作為pH調整劑，例如當使用磷酸緩衝液時，較佳為藉由磷酸與氫氧化鈉或者氫氧化鉀來進行。 pH值是配合組成而定，較佳為5～11的範圍，更佳為6～10。As the pH adjuster, for example, various acids such as sulfuric acid, hydrochloric acid, and phosphoric acid can be used; hydroxides such as sodium hydroxide and potassium hydroxide; and NR 4 OH (R: hydrogen or Alkyl) and other amines. As the pH adjuster, when a phosphate buffer is used, for example, it is preferably performed with phosphoric acid and sodium hydroxide or potassium hydroxide. The pH value depends on the compounding composition, and is preferably in the range of 5-11, more preferably 6-10.
本發明之金析出促進劑可以添加到用於無電解鍍金的鍍覆液中，但該鍍覆液亦能夠使用在自催化型無電解鍍金、基底觸媒（表面觸媒）鍍金、置換鍍金及組合這些鍍金方法的任何方法。尤其，從析出促進性的觀點而言，較佳為使用在置換鍍金。The gold precipitation accelerator of the present invention can be added to the plating solution for electroless gold plating, but the plating solution can also be used in autocatalytic electroless gold plating, substrate catalyst (surface catalyst) gold plating, replacement gold plating, and Any method that combines these gold plating methods. In particular, from the standpoint of precipitation promotion, it is preferably used for displacement gold plating.
本發明之鍍覆液可包含還原劑，亦可不含還原劑。作為還原劑，可舉出：抗壞血酸鈉等的抗壞血酸鹽；羥胺或羥胺鹽酸鹽、羥胺硫酸鹽等的羥胺的鹽類；羥胺-O-磺酸等的羥胺衍生物；肼、二甲基胺硼烷等的胺硼烷化合物；硼氫化鈉等的硼氫化物；葡萄糖等的糖類；次磷酸鹽（hypophosphite）類等。這些還原劑可單獨使用，亦可併用2種以上。其他，只要藉由能斯特的公式（Nernst equation），判斷出是能由金離子或金錯合物中將金還原析出的化合物，則使用哪一種皆可，但要考慮到對於其他鍍浴構成成分的反應性、鍍浴的穩定性等來使用。The plating solution of the present invention may or may not contain a reducing agent. Examples of the reducing agent include: ascorbates such as sodium ascorbate; salts of hydroxylamine such as hydroxylamine or hydroxylamine hydrochloride and hydroxylamine sulfate; hydroxylamine derivatives such as hydroxylamine-O-sulfonic acid; hydrazine and dimethylamine Amine borane compounds such as borane; borohydrides such as sodium borohydride; sugars such as glucose; hypophosphites, etc. These reducing agents may be used alone or in combination of two or more kinds. Others, as long as the Nernst equation is used to determine the compound that can be reduced and precipitated from gold ions or gold complexes, either one can be used, but it should be considered for other plating baths. The reactivity of the constituent components, the stability of the plating bath, etc. are used.
本發明之鍍覆液，能夠在適當的濃度範圍內使用結晶粒形調整劑、光澤劑等其他的添加劑。其他的添加劑並沒有特別限制，例如能夠使用從以往就在使用的添加劑。具體而言，可舉出聚乙二醇等的結晶粒形調整劑；鉈、銅、銻、鉛等的光澤劑。在這些添加劑以外，只要是滿足上述條件的添加劑就能夠使用。In the plating solution of the present invention, other additives such as crystal grain shape regulators and gloss agents can be used within an appropriate concentration range. Other additives are not particularly limited, and for example, additives that have been used in the past can be used. Specifically, crystal grain shape regulators such as polyethylene glycol; gloss agents such as thallium, copper, antimony, and lead can be cited. In addition to these additives, any additives that satisfy the above-mentioned conditions can be used.
本發明的一個態樣中，本發明之無電解鍍金液不含酒石酸鉀鈉。 本發明的一個態樣中，當本發明之無電解鍍金液包含酒石酸鉀鈉或酒石酸鹽時，鍍覆液中的酒石酸鉀鈉或酒石酸鹽的濃度，較佳是以下述方式調整來使用：以鈉以外的鹼金屬離子換算時，成為0.11M以上，較佳為大於0.11M，更佳為0.2M以上的濃度。從析出促進性的觀點而言，該濃度較佳為0.01M～5M，進而較佳為0.01M～2M，特佳為0.01M～0.5M。In one aspect of the present invention, the electroless gold plating solution of the present invention does not contain potassium sodium tartrate. In one aspect of the present invention, when the electroless gold plating solution of the present invention contains potassium sodium tartrate or tartrate, the concentration of potassium sodium tartrate or tartrate in the plating solution is preferably adjusted in the following manner: In terms of alkali metal ions other than sodium, the concentration is 0.11M or more, preferably more than 0.11M, and more preferably 0.2M or more. From the standpoint of precipitation acceleration, the concentration is preferably 0.01M to 5M, more preferably 0.01M to 2M, and particularly preferably 0.01M to 0.5M.
本發明的一個態樣中，本發明之無電解鍍金液不含亞硫酸鉀。 本發明的一個態樣中，當本發明之無電解鍍金液包含亞硫酸鉀時，較佳是以鍍覆液中的亞硫酸鉀的濃度成為0.004M以上的方式調整來使用。從析出促進性的觀點而言，該濃度為0.004M～5M，進而較佳為0.01M～2M，特佳為0.02M～0.5M。 本發明之無電解鍍金液的一個態樣中，無電解鍍金液在僅包含鉀化合物作為鹼金屬化合物的情況中，包含選自鹵化鉀、亞硫酸鉀及酒石酸鉀鈉的鉀化合物以外之鉀化合物。In one aspect of the present invention, the electroless gold plating solution of the present invention does not contain potassium sulfite. In one aspect of the present invention, when the electroless gold plating solution of the present invention contains potassium sulfite, it is preferable to adjust and use it so that the concentration of potassium sulfite in the plating solution becomes 0.004M or more. From the standpoint of precipitation promotion, the concentration is 0.004M to 5M, more preferably 0.01M to 2M, and particularly preferably 0.02M to 0.5M. In one aspect of the electroless gold plating solution of the present invention, the electroless gold plating solution contains potassium compounds other than potassium compounds selected from potassium halides, potassium sulfite, and potassium sodium tartrate when only a potassium compound is included as an alkali metal compound .
本發明又關於一種金析出促進劑，其包含銣化合物及/或銫化合物。銣離子及銫離子會促進金的析出。銣離子的濃度較佳為0.001～5M，進而較佳為0.01～2M，特佳為0.02～0.5M。銫離子的濃度較佳為0.001～5M，進而較佳為0.01～2M，特佳為0.02～0.5M。作為銣化合物及/或銫化合物的例子，可舉出：與作為上述的鹼金屬化合物的例子而舉出的化合物相同者。The present invention also relates to a gold precipitation accelerator, which comprises a rubidium compound and/or a cesium compound. Rubidium ions and cesium ions will promote the precipitation of gold. The concentration of rubidium ions is preferably 0.001 to 5M, more preferably 0.01 to 2M, and particularly preferably 0.02 to 0.5M. The concentration of cesium ions is preferably 0.001 to 5M, more preferably 0.01 to 2M, and particularly preferably 0.02 to 0.5M. As an example of a rubidium compound and/or a cesium compound, the same compound as the compound mentioned as an example of the said alkali metal compound can be mentioned.
包含本發明之金析出促進劑的無電解鍍金液的金析出速度，於pH7、浴溫80℃、4cm2 的Ni基板上，可為0.003μm/分鐘以上，較佳為0.004μm/分鐘以上，進而較佳為0.005μm/分鐘以上。The gold precipitation rate of the electroless gold plating solution containing the gold precipitation accelerator of the present invention can be 0.003 μm/min or more, preferably 0.004 μm/min or more, on a Ni substrate with a pH of 7, bath temperature of 80°C, and 4 cm 2. More preferably, it is 0.005 μm/min or more.
本發明又關於一種形成鍍金皮膜的方法，其包含將本發明之無電解鍍金液應用在電子工業零件的表面的步驟。前述步驟中的無電解鍍金液的使用溫度，從析出速度的觀點而言，較佳為20～90℃，更佳為40～70℃。從液體的穩定性與析出速度的觀點而言，pH值較佳為5～11，進而較佳為6～10。電子工業零件雖然沒有特別限定，典型上而言，可舉出電極、電線等。The present invention also relates to a method for forming a gold-plated film, which includes the step of applying the electroless gold plating solution of the present invention to the surface of electronic industrial parts. The use temperature of the electroless gold plating solution in the foregoing step is preferably 20 to 90°C, more preferably 40 to 70°C from the viewpoint of the precipitation rate. From the viewpoint of the stability of the liquid and the precipitation rate, the pH is preferably 5-11, and more preferably 6-10. The electronic industry parts are not particularly limited, but typically include electrodes, wires, and the like.
本發明又關於一種促進無電解鍍金中的金析出的方法，其包含將1種或2種以上的鹼金屬化合物添加到無電解鍍金液中的步驟，前述鹼金屬化合物不是僅含作為鹼金屬的鈉之化合物，且前述鹼金屬化合物不是僅為鹼金屬的鹵化物、僅為亞硫酸鉀或僅為酒石酸鉀鈉。The present invention also relates to a method for promoting the precipitation of gold in electroless gold plating, which includes the step of adding one or more kinds of alkali metal compounds to the electroless gold plating solution. Sodium compounds, and the aforementioned alkali metal compounds are not only alkali metal halides, only potassium sulfite, or only potassium sodium tartrate.
本發明之促進金析出的方法中，前述鹼金屬化合物的濃度，以鈉以外的鹼金屬離子換算時，可為0.001～5M，較佳為0.01～2M，進而較佳為0.02～0.5M。In the method for promoting gold precipitation of the present invention, the concentration of the alkali metal compound may be 0.001 to 5M, preferably 0.01 to 2M, and more preferably 0.02 to 0.5M when converted to alkali metal ions other than sodium.
本發明的一個態樣中，本發明之促進金析出的方法不包含添加酒石酸鉀鈉的步驟。 本發明的一個態樣中，當本發明之促進金析出的方法包含添加酒石酸鉀鈉的步驟時，較佳是以下述方式調整來添加：將鍍覆液中的酒石酸鉀鈉的濃度以鉀離子換算時，成為0.11M以上，較佳為大於0.11M，進而較佳為0.2M以上。從析出促進性的觀點而言，該濃度較佳為0.11M～5M，進而較佳為0.11M～2M，特佳為0.11M～0.5M。In one aspect of the present invention, the method for promoting gold precipitation of the present invention does not include the step of adding potassium sodium tartrate. In one aspect of the present invention, when the method for promoting gold precipitation of the present invention includes the step of adding potassium and sodium tartrate, it is preferably added in the following manner: the concentration of potassium and sodium tartrate in the plating solution is adjusted to potassium ion When converted, it becomes 0.11M or more, preferably more than 0.11M, and more preferably 0.2M or more. From the standpoint of precipitation acceleration, the concentration is preferably 0.11M to 5M, more preferably 0.11M to 2M, and particularly preferably 0.11M to 0.5M.
本發明的一個態樣中，本發明之促進金析出的方法不包含添加亞硫酸鉀的步驟。 本發明的一個態樣中，當本發明之促進金析出的方法包含添加亞硫酸鉀的步驟時，較佳是以鍍覆液中的亞硫酸鉀的濃度成為0.004M以上的方式調整來添加。從析出促進性的觀點而言，該濃度較佳為0.004M～5M，進而較佳為0.01M～2M，特佳為0.02M～0.5M。In one aspect of the present invention, the method for promoting gold precipitation of the present invention does not include the step of adding potassium sulfite. In one aspect of the present invention, when the method for promoting gold precipitation of the present invention includes the step of adding potassium sulfite, it is preferable to adjust and add it so that the concentration of potassium sulfite in the plating solution becomes 0.004M or more. From the standpoint of precipitation acceleration, the concentration is preferably 0.004M to 5M, more preferably 0.01M to 2M, and particularly preferably 0.02M to 0.5M.
本發明又關於一種方法，其是藉由添加銣化合物及/或銫化合物來促進無電解鍍金中的金的析出。較佳的是，銣化合物及/或銫化合物的濃度總和，以銣離子及/或銫離子換算時，較佳為0.001M～5M，進而較佳為0.01M～1M。當僅添加銣化合物時，該較佳濃度以銣離子換算時為0.001M～5M，進而較佳為0.01M～1M。當僅添加銫化合物時，較佳濃度以銫離子換算時為0.001M～5M，進而較佳為0.001M～1M。The present invention also relates to a method that promotes the precipitation of gold in electroless gold plating by adding a rubidium compound and/or a cesium compound. Preferably, the sum of the concentrations of the rubidium compound and/or cesium compound, when converted to rubidium ion and/or cesium ion, is preferably 0.001M to 5M, and more preferably 0.01M to 1M. When only the rubidium compound is added, the preferred concentration is 0.001M-5M in terms of rubidium ion, and more preferably 0.01M-1M. When only the cesium compound is added, the preferred concentration is 0.001M to 5M in terms of cesium ion, and more preferably 0.001M to 1M.
本發明又關於一種方法，是在其他的一個態樣中，促進無電解鍍金中的金的析出的方法，其是調整無電解鍍金液中的鹼金屬離子的濃度，來調整金析出速度。 無電解鍍金液中，全部的鹼金屬離子的濃度，是以下述方式來調整：成為0.001M～5M，較佳為0.01M～2M，進而較佳為0.02M～0.5M。 [實施例]The present invention also relates to a method, in another aspect, a method of promoting the precipitation of gold in electroless gold plating, which is to adjust the concentration of alkali metal ions in the electroless gold plating solution to adjust the gold precipitation rate. In the electroless gold plating solution, the concentration of all alkali metal ions is adjusted in the following manner: 0.001M to 5M, preferably 0.01M to 2M, and more preferably 0.02M to 0.5M. [Example]
以下，針對本發明之無電解鍍金液，藉由實施例及比較例更詳細地說明，但這些實施例及比較例並沒有將本發明做任何限定。鍍覆試片是使用銅板，且照以下的順序於此進行鍍Ni合金，並用於試驗上。Hereinafter, the electroless gold plating solution of the present invention will be described in more detail with examples and comparative examples, but these examples and comparative examples do not limit the present invention in any way. A copper plate was used for the plating test piece, and Ni alloy was plated here according to the following procedure and used for the test.
［比較例1～3］ 將表1所記載的金源、錯合劑以表1所記載的濃度進行混合來製備鍍金液，使用磷酸作為pH調整劑將鍍金液的pH值調整成pH7.0。使用4cm2 的Ni壓延板，於80℃進行10分鐘鍍覆，測定膜厚，算出析出速度。[Comparative Examples 1 to 3] The gold source and the complexing agent described in Table 1 were mixed at the concentration described in Table 1 to prepare a gold plating solution, and the pH of the gold plating solution was adjusted to pH 7.0 using phosphoric acid as a pH adjuster. A 4 cm 2 Ni rolled plate was used for plating at 80° C. for 10 minutes, the film thickness was measured, and the precipitation rate was calculated.
［實施例1～6］ 將表1所記載的金源、錯合劑、析出促進劑以表1所記載的濃度進行混合來製備鍍金液，使用磷酸作為pH調整劑將鍍金液的pH調整成pH7.0。使用4cm2 的Ni壓延板，於80℃進行10分鐘鍍覆，測定膜厚，算出析出速度。鍍金膜厚，是使用了日立製造的螢光X光膜厚測量儀「FT-9500X」。[Examples 1 to 6] The gold source, complexing agent, and precipitation promoter described in Table 1 were mixed at the concentration described in Table 1 to prepare a gold plating solution, and the pH of the gold plating solution was adjusted to pH 7 using phosphoric acid as a pH adjuster .0. A 4 cm 2 Ni rolled plate was used for plating at 80° C. for 10 minutes, the film thickness was measured, and the precipitation rate was calculated. For the thickness of the gold plating, a fluorescent X-ray film thickness measuring instrument "FT-9500X" manufactured by Hitachi is used.
〔表1〕
表1. 鍍覆液的組成及鍍覆條件
第1圖是基於表1的比較例1、實施例1～3的結果，比較變更了鹼金屬離子時的析出速度而成者。可看出，藉由添加鹼金屬離子，金析出速度會提升。又，從實施例1、實施例2及實施例3全部儘管包含同濃度的碳酸離子，但是金析出速度並不相同的方面而言，可看出金析出速度取決於鹼金屬離子。Figure 1 is based on the results of Comparative Example 1 in Table 1 and Examples 1 to 3, comparing the precipitation rate when alkali metal ions are changed. It can be seen that by adding alkali metal ions, the gold precipitation rate will increase. In addition, from the aspect that the gold precipitation rate is not the same even though all of Example 1, Example 2 and Example 3 contain the same concentration of carbonate ions, it can be seen that the gold precipitation rate depends on alkali metal ions.
結果可看出，含有金析出促進劑的無電解鍍金液，該金析出促進劑包含鈉離子以外的至少1種以上的鹼金屬離子，即使是變更銫鹽、金源及錯合劑的種類，相較於不含金析出促進劑的無電解鍍金液，金析出速度仍較快。 [產業利用性]The results show that the electroless gold plating solution containing a gold precipitation accelerator contains at least one alkali metal ion other than sodium ions, even if the types of cesium salt, gold source and complexing agent are changed, Compared with the electroless gold plating solution without the gold precipitation accelerator, the gold precipitation rate is still faster. [Industrial Utilization]
根據本發明，即使在使用了不將氰化物作為金源且析出速度慢的無電解鍍金液的無電解電鍍中，仍能夠實現充分的金析出速度。According to the present invention, even in electroless plating using an electroless gold plating solution that does not use cyanide as a gold source and has a slow precipitation rate, a sufficient gold precipitation rate can be achieved.
無without
第1圖是變更了鹼金屬離子時的金析出速度比較圖。Figure 1 is a comparison diagram of gold precipitation rate when alkali metal ions are changed.
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