TWI659130B - Barrel plating or high-speed rotary plating using a neutral tin plating solution - Google Patents

Barrel plating or high-speed rotary plating using a neutral tin plating solution Download PDF

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TWI659130B
TWI659130B TW106137168A TW106137168A TWI659130B TW I659130 B TWI659130 B TW I659130B TW 106137168 A TW106137168 A TW 106137168A TW 106137168 A TW106137168 A TW 106137168A TW I659130 B TWI659130 B TW I659130B
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plating
plating solution
barrel
acid
tin
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TW106137168A
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TW201817921A (en
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近藤誠
Makoto Kondo
水野陽子
Yoko Mizuno
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美商羅門哈斯電子材料有限公司
Rohm And Haas Electronic Materials Llc
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/16—Apparatus for electrolytic coating of small objects in bulk
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/16—Apparatus for electrolytic coating of small objects in bulk
    • C25D17/18—Apparatus for electrolytic coating of small objects in bulk having closed containers
    • C25D17/20—Horizontal barrels
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

一種對電子組件進行滾鍍或高速旋轉電鍍之方法，及其中使用之中性鍍錫液。使用包括（A）亞錫離子、（B）酸或鹽、（C）錯合劑及（D）具有聚氧伸烷基鏈之二胺且pH值在4與8之間的範圍內之電鍍液。使用此中性鍍錫液能夠防止電子組件在滾鍍期間耦接在一起，從而實現滾鍍可製造性之改善。A method for performing barrel plating or high-speed rotary plating on electronic components, and using a neutral tin plating solution in the method. Use a plating solution that includes (A) stannous ion, (B) acid or salt, (C) complexing agent, and (D) a diamine with a polyoxyalkylene chain and a pH value in the range of 4 and 8. . The use of this neutral tin plating solution can prevent electronic components from being coupled together during barrel plating, thereby improving the manufacturability of barrel plating.

Description

使用中性鍍錫液之滾鍍或高速旋轉電鍍Barrel plating or high speed spin plating using a neutral tin plating solution

本發明係關於一種使用中性鍍錫液對電子組件進行滾鍍或高速旋轉電鍍之方法，且關於其中使用之中性鍍錫液。更具體而言，其係關於一種滾鍍或高速旋轉電鍍方法，且關於其中使用之中性鍍錫液，該中性鍍錫液能夠提高電鍍在電子組件上之覆蓋率，同時防止電子組件在進行滾鍍或高速旋轉電鍍時彼此耦接。The invention relates to a method for performing barrel plating or high-speed rotary plating of electronic components by using a neutral tin plating solution, and to use a neutral tin plating solution therein. More specifically, it relates to a barrel plating or high-speed rotary plating method, and regarding the use of a neutral tin plating solution therein, the neutral tin plating solution can improve the coverage of electroplating on electronic components while preventing the electronic components from They are coupled to each other when barrel plating or high-speed spin plating is performed.

為提高電子組件之可焊性，廣泛地進行鍍錫。電子組件鍍錫之方法可選自各種不同之方法，諸如滾鍍、掛鍍及其類似方法，視電鍍位置之形狀、結構及其類似因素而定。滾鍍通常用作諸如片式電阻、片式電容器及其類似組件的小電子組件電鍍之方法。此外，近年來，已經藉由導流電鍍器及其類似物進行高速旋轉電鍍，作為小電子組件之電鍍方法。In order to improve the solderability of electronic components, tin plating is widely performed. The method of tinning electronic components can be selected from various methods, such as barrel plating, rack plating, and the like, depending on the shape, structure, and the like of the plating location. Barrel plating is commonly used as a method for plating small electronic components such as chip resistors, chip capacitors, and the like. In addition, in recent years, high-speed rotary electroplating has been performed by a flow guide electroplater and the like as a plating method for small electronic components.

通常，在進行滾鍍時，將待電鍍之電子組件及用於在電鍍期間提高導電性之導電金屬（虛設球）裝載至稱為滾筒之籠形容器中，且藉由在使滾筒以其浸沒於電鍍液中之狀態旋轉或振動時施加電流來電鍍電子組件。然而，近年來，隨著電子組件之尺寸愈來愈小，在滾鍍期間，電子組件往往會彼此耦接，或虛設球結塊在一起，或電子組件及虛設球黏在一起，從而產生在滾鍍時對電子組件之可製造性造成不良影響之問題。此外，視電鍍液之類型而定，溶液表面可能起泡，從而產生對電鍍操作造成不良影響之問題。在高速旋轉電鍍中，將作為電鍍對象之電子組件***至圓盤形單元中，且在使單元以高速旋轉之同時進行電鍍，且可能發生與滾鍍時相同之問題。Generally, when barrel plating is performed, an electronic component to be plated and a conductive metal (dummy ball) for improving conductivity during electroplating are loaded into a cage-shaped container called a drum, and by immersing the drum with it Apply electrical current to electroplating electronic components while rotating or vibrating in the plating solution. However, in recent years, with the size of electronic components becoming smaller and smaller, during barrel plating, electronic components are often coupled to each other, or dummy balls are agglomerated, or electronic components and dummy balls are stuck together, resulting in The problem of adversely affecting the manufacturability of electronic components during barrel plating. In addition, depending on the type of the plating solution, the surface of the solution may be foamed, thereby causing a problem that adversely affects the plating operation. In high-speed rotary electroplating, an electronic component to be plated is inserted into a disc-shaped unit, and electroplating is performed while the unit is rotated at a high speed, and the same problems as in barrel plating may occur.

日本未審查專利申請公開案2009-299123揭露一種pH值為1或更低之片式組件之錫電鍍液，包括亞錫離子、氧、二聚氧伸烷基烷基胺或氧化胺及結合抑制劑。然而，在***作為電鍍對象之電子組件陶瓷部件時，pH值為1或更低之電鍍液之使用損壞陶瓷部件，這並非較佳。Japanese Unexamined Patent Application Publication 2009-299123 discloses a tin plating solution for chip components having a pH value of 1 or lower, including stannous ion, oxygen, dioxyalkylene alkylamine or amine oxide, and binding inhibition Agent. However, when inserting a ceramic component of an electronic component as a plating target, the use of a plating solution having a pH of 1 or lower damages the ceramic component, which is not preferable.

日本未審查專利申請公開案2003-293186揭露一種中性鍍錫浴，包括可溶性亞錫鹽、酸或鹽、選自氧基羧酸或其類似物之錯合劑及四級胺聚合物。然而，在本發明人之研究中，使用四級胺聚合物之中性鍍錫液並不足夠有效地防止電鍍對象之間的耦接，且需要進一步改善。Japanese Unexamined Patent Application Publication 2003-293186 discloses a neutral tin plating bath including a soluble stannous salt, acid or salt, a complexing agent selected from an oxycarboxylic acid or the like, and a quaternary amine polymer. However, in the research of the present inventors, the use of a quaternary amine polymer neutral tin plating solution is not effective enough to prevent the coupling between the plating objects, and further improvement is needed.

因此，本發明之目的是即使在對近年來已經小型化之電子組件進行滾鍍或高速旋轉電鍍時亦能夠抑制電子組件之間的耦接，提供一種電子組件電鍍方法及其中使用之中性鍍錫液，其中在進行滾鍍或高速旋轉電鍍時電鍍液極少起泡。Therefore, the object of the present invention is to suppress the coupling between electronic components even when performing barrel plating or high-speed rotary plating on electronic components that have been miniaturized in recent years, and to provide an electronic component plating method and neutral plating used therein. Tin bath, in which the plating bath rarely foams during barrel plating or high-speed spin plating.

本發明人藉由以下發現實現本發明：藉由防止電鍍對象耦接在一起，以及藉由電鍍液中極少起泡，藉由將具有聚氧伸烷基鏈之二胺添加至中性鍍錫液，可提高滾鍍或高速旋轉電鍍之可製造性。The present inventors achieved the present invention by discovering that by preventing the plating objects from being coupled together, and by having few bubbles in the plating solution, by adding a diamine having a polyoxyalkylene chain to neutral tin plating It can improve the manufacturability of barrel plating or high-speed rotary plating.

亦即，本發明之一個態樣提供一種電子組件滾鍍或高速旋轉電鍍方法，該方法包括使用包括（A）亞錫離子、（B）酸或鹽、（C）錯合劑及（D）包括聚氧伸烷基鏈之二胺且pH值在4與8之間的範圍內之鍍錫液對電子組件進行滾鍍或高速旋轉電鍍之步驟。That is, one aspect of the present invention provides a method for barrel plating or high-speed rotary plating of electronic components, which method includes using (A) stannous ions, (B) acid or salt, (C) complexing agent, and (D) including A step of barrel plating or high-speed rotary plating of electronic components using a tin plating solution of polyoxyalkylene diamine and a pH value in a range between 4 and 8.

此外，本發明之一個態樣提供一種用於滾鍍或高速旋轉電鍍之中性鍍錫液，該中性鍍錫液包括（A）亞錫離子、（B）酸或鹽、（C）錯合劑及（D）包括聚氧伸烷基鏈之二胺，且其中pH值在4與8之間的範圍內。In addition, one aspect of the present invention provides a neutral tin plating solution for barrel plating or high-speed rotary plating. The neutral tin plating solution includes (A) stannous ion, (B) acid or salt, and (C) The mixture and (D) include a diamine having a polyoxyalkylene chain, and the pH value is in a range between 4 and 8.

除非另外定義，否則在整個說明書中所使用之縮寫具有以下含義：g=公克；mg=毫克；℃=攝氏度；min=分鐘；m=公尺；cm=公分；L=公升；mL=毫升；A=安培；以及dm2 =平方分米。所有數值均包括其邊界值，且可以任意排序組合。在整個本說明書中，術語「電鍍液」及「電鍍浴」具有相同含義，且可以互換使用。此外，除非特別規定，否則在整個說明書中，百分比（%）表示重量百分比。Unless otherwise defined, the abbreviations used throughout the specification have the following meanings: g = gram; mg = mg; ℃ = degree Celsius; min = minute; m = meter; cm = cm; L = liter; mL = ml; A = ampere; and dm 2 = square decimeter. All values include their boundary values and can be combined in any order. Throughout this specification, the terms "plating solution" and "plating bath" have the same meaning and are used interchangeably. In addition, unless otherwise specified, throughout the specification, percentage (%) means weight percentage.

根據本發明之對電子組件進行滾鍍或高速旋轉電鍍之方法具有一個顯著特徵，即使用包括（A）亞錫離子、（B）酸或鹽、（C）錯合劑及（D）包括聚氧伸烷基鏈之二胺且其中pH值在4與8之間的範圍內之電鍍液。此電鍍液將在下文依序解釋。 （A）亞錫離子The method for barrel plating or high-speed spin plating of electronic components according to the present invention has a significant feature, that is, the use of (A) stannous ions, (B) Electroplating solution of an alkylene diamine with a pH in the range between 4 and 8. This plating solution will be explained in order below. (A) stannous ion

在本發明中所使用之電鍍液中，包括亞錫離子作為一個必需之結構要求。亞錫離子係雙氧化錫離子。在電鍍液中，可使用任意化合物，只要其為能夠提供亞錫離子之化合物即可。一般而言，較佳為電鍍液中所使用之無機酸或有機酸之錫鹽。舉例而言，作為無機酸之錫鹽，存在硫酸及鹽酸之亞錫鹽，且作為有機酸之錫鹽，存在例如經取代或未經取代之烷磺酸及烷醇磺酸（例如甲烷磺酸、乙烷磺酸、丙烷磺酸、2-羥基乙烷-1-磺酸、2-羥基丙烷-1-磺酸及1-羥基丙烷-2-磺酸）之亞錫鹽。提供亞錫離子之特別較佳之來源對於無機酸鹽而言為磺酸亞錫，或對於有機酸鹽而言為甲烷磺酸亞錫。能夠提供此等離子之此等化合物可單獨或以其兩者或超過兩者之混合物形式使用。In the plating solution used in the present invention, stannous ions are included as a necessary structural requirement. The stannous ion is a tin oxide ion. In the plating solution, any compound can be used as long as it is a compound capable of providing stannous ions. In general, a tin salt of an inorganic acid or an organic acid used in a plating solution is preferred. For example, as the tin salts of inorganic acids, there are stannous salts of sulfuric acid and hydrochloric acid, and as the tin salts of organic acids, there are, for example, substituted or unsubstituted alkanesulfonic acids and alkanolsulfonic acids (such as methanesulfonic acid , Ethanesulfonic acid, propanesulfonic acid, 2-hydroxyethane-1-sulfonic acid, 2-hydroxypropane-1-sulfonic acid and 1-hydroxypropane-2-sulfonic acid). A particularly preferred source for providing stannous ions is stannous sulfonate for inorganic acid salts or stannous methanesulfonate for organic acid salts. These compounds capable of providing such ions can be used alone or as a mixture of two or more of them.

電鍍液內亞錫離子之包括比例可為以錫離子形式例如在5 g/L與30 g/L之間，或較佳在8 g/L與25 g/L之間，或更佳在10 g/L與20 g/L之間。 （B）酸或鹽The inclusion ratio of stannous ions in the plating solution may be in the form of tin ions, such as between 5 g / L and 30 g / L, or preferably between 8 g / L and 25 g / L, or more preferably 10 g / L and 20 g / L. (B) acid or salt

本發明中所使用之電鍍液可使用任意酸或鹽，只要此酸或鹽具有為電鍍液提供導電性之功能即可。可使用任何有機酸、無機酸或其鹽。作為有機酸，存在例如經取代或未經取代之烷磺酸或烷醇磺酸，例如甲烷磺酸、乙烷磺酸、丙烷磺酸、2-羥基乙烷-1-磺酸、2-羥基丙烷-1-磺酸及1-羥基丙烷-2磺酸。較佳為甲烷磺酸。對於無機酸而言，可使用例如硫酸或鹽酸，且較佳為硫酸。作為其鹽，可使用任意鹽，如鹼金屬鹽、鹼土金屬鹽、銨鹽、胺鹽等等。酸及鹽可單獨或以兩者或超過兩者之組合形式使用。雖然較佳使用如上所述，亞錫離子鹽所用之無機酸或有機酸或其鹽，但對其不存在限制。The plating solution used in the present invention can use any acid or salt, as long as the acid or salt has a function of providing conductivity to the plating solution. Any organic acid, inorganic acid or salt thereof can be used. As organic acids, there are, for example, substituted or unsubstituted alkanesulfonic acids or alkanolsulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, 2-hydroxyethane-1-sulfonic acid, 2-hydroxy Propane-1-sulfonic acid and 1-hydroxypropane-2sulfonic acid. Methanesulfonic acid is preferred. For the inorganic acid, for example, sulfuric acid or hydrochloric acid can be used, and sulfuric acid is preferable. As its salt, any salt such as an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an amine salt, and the like can be used. The acids and salts can be used alone or in a combination of two or more. Although it is preferable to use an inorganic acid or an organic acid or a salt thereof as described above for the stannous ion salt, there is no limitation thereon.

應注意，因此本發明中所使用之電鍍液將為中性電鍍液，在將如上所述之有機酸或無機酸用於導電物質時，可將各種鹼中之任一種作為pH調節劑添加至電鍍液以將pH值調節至4與8之間的範圍。It should be noted that, therefore, the plating solution used in the present invention will be a neutral plating solution. When an organic acid or an inorganic acid as described above is used for a conductive substance, any one of various bases may be added as a pH adjuster to The plating solution is used to adjust the pH to a range between 4 and 8.

電鍍液中酸或鹽之包括比例在例如30 g/L與300 g/L之間，且較佳在50 g/L與200 g/L之間，且更佳在80 g/L與150 g/L之間。 （C）錯合劑The inclusion ratio of the acid or salt in the plating solution is, for example, between 30 g / L and 300 g / L, preferably between 50 g / L and 200 g / L, and more preferably between 80 g / L and 150 g / L. (C) Blend

本發明中所使用之電鍍液包括錯合劑作為一個必需之結構條件。通常，鍍錫液中之雙電離錫離子在強酸中穩定，但接近中性時變得不穩定，且往往會呈錫金屬分離出來，因此電鍍液往往會分解。為使本發明之鍍錫液具有在4與8之間的範圍內之pH值，必須包括錯合劑。對錯合劑沒有特定限制，只要其具有穩定電鍍液之作用即可。錯合劑可為例如葡糖酸、檸檬酸、丙二酸、丁二酸、酒石酸或其鹽。在此等錯合劑中，較佳為葡糖酸或其鹽，且最佳為葡糖酸鈉。The plating solution used in the present invention includes a complexing agent as a necessary structural condition. Generally, the double ionized tin ions in the tin plating solution are stable in strong acids, but become unstable when they are close to neutral, and they tend to separate out as tin metal, so the plating solution tends to decompose. In order for the tin plating solution of the present invention to have a pH value in a range between 4 and 8, a complexing agent must be included. There is no particular limitation on the complexing agent as long as it has the effect of stabilizing the plating solution. The complexing agent may be, for example, gluconic acid, citric acid, malonic acid, succinic acid, tartaric acid, or a salt thereof. Among these complexing agents, gluconic acid or a salt thereof is preferred, and sodium gluconate is most preferred.

電鍍液中錯合劑之包括比例在例如80 g/L與250 g/L之間，且較佳在100 g/L與200 g/L之間，且更佳在125 g/L與175 g/L之間。 （D）具有聚氧伸烷基鏈之二胺The inclusion ratio of the complexing agent in the plating solution is, for example, between 80 g / L and 250 g / L, preferably between 100 g / L and 200 g / L, and more preferably between 125 g / L and 175 g / Between L. (D) Diamine with polyoxyalkylene chain

本發明中所使用之電鍍液包括具有聚氧伸烷基鏈之二胺作為一個必需之結構條件。包括此化合物防止電鍍對象耦接在一起，從而實現滾鍍可製造性之改善。較佳地，包括聚氧伸烷基伸烷基鏈之二胺為以下化學式所描述之化合物： The plating solution used in the present invention includes a diamine having a polyoxyalkylene chain as an essential structural condition. The inclusion of this compound prevents the plating objects from being coupled together, thereby improving the manufacturability of barrel plating. Preferably, the diamine including polyoxyalkylene and alkylene chain is a compound described by the following chemical formula:

此處在上式中，R1 為碳數在1與10之間的直鏈或分支鏈伸烷基，且較佳為碳數在1與6之間的直鏈或分支鏈伸烷基，且更佳為碳數在1與4之間的直鏈或分支鏈伸烷基。R2 至R5 各獨立地為碳數在1與10之間的直鏈或分支鏈伸烷基，且較佳為碳數在1與6之間的直鏈或分支鏈伸烷基，且更佳為碳數在1與4之間的直鏈或分支鏈伸烷基。n、m、o及p各為0與15之間的整數，其中n、m、o及p不均為0。較佳地，n、m、o及p各為1與12之間的整數，且更佳為1與8之間的整數。應注意，n、m、o及p之總數在1與60之間，且較佳在2與30之間，且更佳在4與25之間。Here in the above formula, R 1 is a straight or branched chain alkylene group having a carbon number of 1 to 10, and is preferably a straight or branched chain alkylene group having a carbon number of 1 to 6, And more preferably a straight or branched chain alkylene group having a carbon number of 1 to 4. R 2 to R 5 are each independently a straight or branched chain alkylene group having a carbon number of 1 to 10, and preferably a straight or branched chain alkylene group having a carbon number of 1 to 6, and More preferred are straight or branched chain alkylene groups having a carbon number between 1 and 4. n, m, o, and p are each an integer between 0 and 15, where n, m, o, and p are not all 0. Preferably, n, m, o, and p are each an integer between 1 and 12, and more preferably an integer between 1 and 8. It should be noted that the total number of n, m, o, and p is between 1 and 60, and preferably between 2 and 30, and more preferably between 4 and 25.

本發明人發現，包括上述化合物之電鍍液能夠在進行滾鍍或高速旋轉電鍍時減少電子組件之耦接，且能夠穩定地進行電鍍操作，極少產生在進行電鍍時將造成問題之氣泡。The inventors have found that a plating solution including the above compounds can reduce the coupling of electronic components when performing barrel plating or high-speed rotary plating, and can stably perform plating operations, and rarely generates bubbles that cause problems when performing plating.

具有聚氧伸烷基鏈之二胺之重均分子量較佳在200與1100之間，且更佳在300與600之間。此處，重均分子量係使用GPC方法所量測之值。The weight average molecular weight of the diamine having a polyoxyalkylene chain is preferably between 200 and 1100, and more preferably between 300 and 600. Here, the weight average molecular weight is a value measured using a GPC method.

具有聚氧伸烷基鏈之二胺可使用市售二胺，且例如可使用Adeka聚醚EDP-450、Adeka聚醚BM-54（Adeka Co., Ltd.製造）或類似物。As the diamine having a polyoxyalkylene chain, a commercially available diamine can be used, and for example, Adeka polyether EDP-450, Adeka polyether BM-54 (manufactured by Adeka Co., Ltd.), or the like can be used.

電鍍液中具有聚氧伸烷基鏈之二胺之包括比例在例如0.1 g/L與30 g/L之間，且較佳在0.5 g/L與20 g/L之間，且更佳在1 g/L與5 g/L之間。 （E）pH調節劑The inclusion ratio of the diamine having a polyoxyalkylene chain in the plating solution is, for example, between 0.1 g / L and 30 g / L, and preferably between 0.5 g / L and 20 g / L, and more preferably Between 1 g / L and 5 g / L. (E) pH adjuster

本發明中所使用之中性鍍錫液之pH值在4與8之間的範圍內，且較佳在5與7之間的範圍內。可將鹼或酸添加至電鍍液中以將pH值調節至此範圍。可使用之酸包括例如甲烷磺酸、乙烷磺酸、丙烷磺酸、鹽酸、硫酸及其類似物。作為可使用之鹼，存在例如氫氧化鈉、氫氧化鉀及氨水。The pH value of the neutral tin plating solution used in the present invention is in a range between 4 and 8, and preferably in a range between 5 and 7. An alkali or acid can be added to the plating solution to adjust the pH to this range. Acids that can be used include, for example, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, hydrochloric acid, sulfuric acid, and the like. Examples of usable bases include sodium hydroxide, potassium hydroxide, and ammonia.

本發明中所使用之中性鍍錫液可包括通常添加至電鍍溶液中之組份作為其他任意組份。舉例而言，可使用氧化抑制劑、光亮劑、光滑劑、導電鹽、陽極溶劑、腐蝕抑制劑、潤濕劑及其類似物。 （F）氧化抑制劑The neutral tin plating solution used in the present invention may include, as other arbitrary components, components usually added to the plating solution. For example, oxidation inhibitors, brighteners, smoothing agents, conductive salts, anode solvents, corrosion inhibitors, wetting agents, and the like can be used. (F) Oxidation inhibitor

在根據本發明之電鍍液中，可視需要使用氧化抑制劑。氧化抑制劑用於防止錫離子自2+氧化至4+，其中可使用例如對苯二酚、鄰苯二酚、間苯二酚、間苯三酚、鄰苯三酚、對苯二酚、磺酸、其鹽或其類似物。In the plating solution according to the present invention, an oxidation inhibitor may be used as necessary. Oxidation inhibitors are used to prevent the oxidation of tin ions from 2+ to 4+. Among them, hydroquinone, catechol, resorcinol, resorcinol, catechol, hydroquinone, Sulfonic acid, a salt thereof, or the like.

在電鍍浴中，氧化抑制劑適合以例如在100 mg/L與50 g/L之間，或較佳在200 mg/L與20 g/L之間，且更佳在0.5 g/L與5 g/L之間的濃度使用。In the plating bath, the oxidation inhibitor is suitably, for example, between 100 mg / L and 50 g / L, or preferably between 200 mg / L and 20 g / L, and more preferably between 0.5 g / L and 5 Use between g / L.

在最初構成電解電鍍浴時，對各種組份之添加順序不存在特定限制；然而，自安全性角度看，在添加水之後添加酸及鹽，隨後在充分混合之後添加錫鹽，然後在徹底溶解之後視需要添加其他化學物質。When the electrolytic plating bath was initially formed, there was no specific restriction on the order of addition of the various components; however, from a safety point of view, acid and salt were added after adding water, followed by tin salt after thorough mixing, and then completely dissolved Add other chemicals later as needed.

對本發明中作為電鍍對象之電子組件不存在特定限制，且其可為例如電阻、電容器、電感器（或電感變壓器）、熱敏電阻、壓敏電阻、可變電阻、可變電容器或其他無源組件；或晶體振盪器、LC濾波器、陶瓷濾波器、延遲線、SAW濾波器或其他功能組件；或開關、連接器、繼電器保險絲、光連接器或其他連接組件。具體而言，電容器、電感器、熱敏電阻及壓敏電阻在組件內具有陶瓷部分，意謂無法使用強酸電鍍溶液，因此使用本發明之中性電鍍浴之電鍍係較佳。 電鍍方法There are no specific restrictions on the electronic component as the object of plating in the present invention, and it may be, for example, a resistor, a capacitor, an inductor (or an inductor transformer), a thermistor, a varistor, a variable resistor, a variable capacitor, or other passive Components; or crystal oscillators, LC filters, ceramic filters, delay lines, SAW filters, or other functional components; or switches, connectors, relay fuses, optical connectors, or other connected components. Specifically, capacitors, inductors, thermistors, and varistors have ceramic parts in the module, which means that a strong acid plating solution cannot be used, so the plating system using the neutral plating bath of the present invention is preferred. Plating method

將解釋使用根據本發明之電鍍液進行滾鍍之方法。如上所述，通常，在進行滾鍍時，作為電鍍對象之電子組件與虛設球一起裝載，且以其浸沒於電鍍液中之狀態，在使滾筒旋轉時施加電流，但根據本發明之滾鍍方法包括僅將電鍍對象置於滾筒而不添加虛設球之情況。滾鍍方法可使用任意裝置，諸如水平或傾斜旋轉滾筒類型、樞轉滾筒類型、振動滾筒類型或其類似物。可在電鍍液之溫度在例如10℃與50℃之間且較佳在20℃與40℃之間時進行滾鍍。此外，陰極電流密度可視需要在例如0.01 A/dm2 與10 A/dm2 之間，且較佳在0.05 A/dm2 與5 A/dm2 之間，且更佳在0.1 A/dm2 與0.5 A/dm2 之間的範圍內選擇。可選擇一種方法，其中例如在電鍍過程期間不攪拌電鍍浴，或例如可使用攪拌器攪拌，或該方法可使用泵進行流體流動。A method for barrel plating using a plating solution according to the present invention will be explained. As described above, generally, when barrel plating is performed, an electronic component to be plated is loaded with a dummy ball, and an electric current is applied when the drum is rotated in a state in which it is immersed in a plating solution. The method includes a case where only a plated object is placed on the drum without adding a dummy ball. The barrel plating method may use any device, such as a horizontal or inclined rotating drum type, a pivoting drum type, a vibrating drum type, or the like. Barrel plating may be performed when the temperature of the plating solution is, for example, between 10 ° C and 50 ° C, and preferably between 20 ° C and 40 ° C. In addition, the cathode current density may be, for example, between 0.01 A / dm 2 and 10 A / dm 2 , and preferably between 0.05 A / dm 2 and 5 A / dm 2 , and more preferably 0.1 A / dm 2 Choose from a range between 0.5 A / dm 2 . A method may be selected in which, for example, the electroplating bath is not stirred during the electroplating process, or for example, agitator may be used for stirring, or the method may use a pump for fluid flow.

此外，在使用根據本發明之電鍍液進行高速旋轉電鍍時，可在陰極電流密度在0.01 A/dm2 與10 A/dm2 之間，在10℃與50℃之間的條件下，使用例如導流電鍍器或其類似物進行電鍍，其中在高速旋轉期間電鍍作為電鍍對象之小電子組件。 實施例1In addition, when performing high-speed rotary electroplating using the plating solution according to the present invention, under conditions where the cathode current density is between 0.01 A / dm 2 and 10 A / dm 2 and between 10 ° C and 50 ° C, for example, A deflector plater or the like performs electroplating, in which small electronic components as objects to be plated are plated during high-speed rotation. Example 1

製備具有以下組份之鍍錫液之電解浴： （A）甲烷磺酸亞錫：39 g/L（15 g/L作為錫離子） （B）甲烷磺酸鈉：100 g/L （C）葡糖酸鈉：145 g/L （D）Adeka聚醚EDP-450（分子量：450）：2 g/L （E）氫氧化鈉：足以使電鍍液之pH值達至6 （F）異抗壞血酸鈉：2 g/L （G）水：餘量An electrolytic bath for preparing a tin plating solution having the following components: (A) stannous methanesulfonate: 39 g / L (15 g / L as tin ion) (B) sodium methanesulfonate: 100 g / L (C) Sodium gluconate: 145 g / L (D) Adeka polyether EDP-450 (molecular weight: 450): 2 g / L (E) Sodium hydroxide: sufficient to bring the pH of the plating solution to 6 (F) erythorbic acid Sodium: 2 g / L (G) Water: balance

Adeka聚醚EDP-450之結構 Structure of Adeka Polyether EDP-450

使用兩升製備之電解浴之鍍錫液在以下條件下對已經鍍鎳之片式電阻進行滾筒鍍錫，且進行各種評估。結果呈現在表1中。 滾鍍條件1 滾筒：Yamamoto微型滾筒（容量：約140 mL） 經受電鍍之對象：片式電阻：5 g 虛設球：鋼球，直徑：0.71 mm至0.85 mm，60 g 電流密度：0.2 A/dm2 電鍍時間：50分鐘 電鍍液溫度：35℃ 旋轉速度：6 rpm （焊料可濕性測試）The tin-plated resistors having been plated with nickel were subjected to drum tin plating using the two-liter prepared tin bath of the electrolytic bath under the following conditions, and various evaluations were performed. The results are presented in Table 1. Barrel plating conditions 1 Roller: Yamamoto miniature roller (capacity: about 140 mL) Subject to plating: Chip resistance: 5 g Dummy ball: Steel ball, diameter: 0.71 mm to 0.85 mm, 60 g Current density: 0.2 A / dm 2 Plating time: 50 minutes Plating bath temperature: 35 ° C Rotation speed: 6 rpm (solder wettability test)

根據實施例及比較實例之電鍍溶液各製備兩升，且進行鍍錫，持續50分鐘。在35℃之浴溫下，以0.2 A/dm2 在片式電阻之外部電極上沈積5 µm鍍錫塗層。在所產生之各鍍錫塗層上進行濕熱測試程序（溫度為105℃，濕度為100%之PCT程序，持續四個小時），且使用由Tarutin製造之多可焊性測試儀SWET-2100評估濕熱測試前後電鍍塗層之焊料可濕性，以藉由焊膏平衡方法量測零交叉時間（「ZCT」）。量測條件如下： 零交叉時間量測條件 焊膏：Sn:Ag:Cu = 95.75:3.5:0.75 測試溫度：245℃ 浸沒深度：0.15 mm 測試速度：2 mm/s 保持時間：8 sTwo liters of each of the plating solutions according to the examples and comparative examples were prepared, and tin plating was performed for 50 minutes. At a bath temperature of 35 ° C, a 5 µm tin-plated coating was deposited on the external electrodes of the chip resistor at 0.2 A / dm 2 . A moist heat test program was performed on each of the resulting tin-plated coatings (PCT program with a temperature of 105 ° C and a humidity of 100% for four hours) and evaluated using a multi-solderability tester SWET-2100 manufactured by Tarutin The wettability of the solder of the electroplated coating before and after the moist heat test, the zero-cross time ("ZCT") was measured by the solder paste balance method. The measurement conditions are as follows: Zero-cross time measurement conditions Solder paste: Sn: Ag: Cu = 95.75: 3.5: 0.75 Test temperature: 245 ° C Immersion depth: 0.15 mm Test speed: 2 mm / s Hold time: 8 s

在PCT程序前後均量測焊料可濕性，且在表1中給出結果。The solder wettability was measured before and after the PCT procedure, and the results are shown in Table 1.

計算耦接比例（黏附芯片相對於總芯片重量之重量比例）及結塊比例（結塊在一起之虛設球相對於虛設球總重量之重量比例），且類似地在表1中給出。 電鍍外觀及電鍍粒度（Particle Size）（粒度（Grain Size））Calculate the coupling ratio (the weight ratio of the adhesive chip to the total chip weight) and the agglomeration ratio (the weight ratio of the dummy ball to the total weight of the dummy ball), and are similarly given in Table 1. Plating Appearance and Particle Size (Grain Size)

使用製備之電解浴之電鍍液進行霍爾槽（Hull cell）測試，且裸眼觀測製備之電鍍塗層之外觀，且使用SEM（在2000 x下）量測電鍍粒度。 比較實例1A Hull cell test was performed using the prepared electrolytic bath plating solution, and the appearance of the prepared plating coating was observed with naked eyes, and the particle size of the plating was measured using a SEM (at 2000 x). Comparative Example 1

使用與第一實施例中相同之組成製備鍍錫液之電解浴，不同之處在於使用2 g/L二甲胺基乙酸十二烷酯甜菜鹼（Amphitol 20BS，由Kao Corp.製造）而非第一實施例中之（D）Adeka聚醚EDP-450。電鍍液之發泡性較高，因此不適合用於滾鍍。 比較實例2至比較實例4An electrolytic bath was prepared using the same composition as in the first example, except that 2 g / L dimethylamino dodecyl betaine (Amphitol 20BS, manufactured by Kao Corp.) was used instead (D) Adeka polyether EDP-450 in the first embodiment. The foaming property of the plating solution is high, so it is not suitable for barrel plating. Comparative Example 2 to Comparative Example 4

使用與第一實施例中相同之組成製備鍍錫液之電解浴，不同之處在於分別使用2 g/L四級銨鹽聚合物（Papiogen P-113（比較實例2））、SenkaFix 401（比較實例3）及四級銨鹽（Eretat M-65（比較實例4））而非第一實施例中之（D）Adeka聚醚EDP-450。比較實例4中所產生之電鍍液具有高發泡性，因此不適合用於滾鍍。對於比較實例2及比較實例3中所產生之電鍍液而言，各進行與第一實施例中相同之程序。對於比較實例2中所產生之電鍍液而言，霍爾槽測試中所獲得之電鍍塗層之外觀為白色，結果極佳，但在滾鍍測試中，耦接率高，達81.3%。對於比較實例3中所獲得之電鍍液而言，霍爾槽測試中所產生之電鍍塗層之外觀為淺灰黑色，此不合需要。 表1 實施例2An electrolytic bath was prepared using the same composition as in the first example, except that 2 g / L quaternary ammonium polymer (Papiogen P-113 (Comparative Example 2)), SenkaFix 401 (Comparative Example 3) and quaternary ammonium salt (Eretat M-65 (Comparative Example 4)) instead of (D) Adeka polyether EDP-450 in the first example. The electroplating solution produced in Comparative Example 4 has high foaming properties and is therefore not suitable for barrel plating. For the electroplating solutions produced in Comparative Example 2 and Comparative Example 3, the same procedures as those in the first embodiment were each performed. For the electroplating solution produced in Comparative Example 2, the appearance of the electroplated coating obtained in the Hall groove test was white, and the results were excellent, but in the barrel plating test, the coupling rate was high, reaching 81.3%. For the electroplating solution obtained in Comparative Example 3, the appearance of the electroplated coating produced in the Hall groove test was light grayish black, which was not desirable. Table 1 Example 2

以與第一實施例中相同之方式進行測試，不同之處在於將滾鍍條件1改變成下文滾鍍條件2，且量測耦接率及結塊率。結果為，芯片耦接率為0.1%，且虛設球結塊率為0%。此外，電鍍液極少起泡。 滾鍍條件2 滾筒：Yamamoto微型滾筒（容量：約140 mL） 經受電鍍之對象：片式電阻：5 g 虛設球：鋼球，直徑：0.71 mm至0.85 mm，60 g 電流密度：0.2 A/dm2 電鍍時間：50分鐘 電鍍液溫度：35℃ 旋轉速度：12 rpmThe test was performed in the same manner as in the first embodiment, except that the barrel plating condition 1 was changed to the barrel plating condition 2 below, and the coupling ratio and the blocking ratio were measured. As a result, the chip coupling rate was 0.1%, and the dummy ball agglomeration rate was 0%. In addition, the plating solution rarely foams. Barrel plating conditions 2 Drum: Yamamoto miniature drum (capacity: approx. 140 mL) Subject to plating: Chip resistance: 5 g Dummy ball: Steel ball, diameter: 0.71 mm to 0.85 mm, 60 g Current density: 0.2 A / dm 2 Plating time: 50 minutes Plating bath temperature: 35 ° C Rotation speed: 12 rpm

無no

無no

Claims (5)

一種對電子組件進行滾鍍或高速旋轉電鍍之方法，包括使用鍍錫液對電子組件進行滾鍍或高速旋轉電鍍之步驟，該鍍錫液包括(A)5g/L至30g/L之亞錫離子、(B)30g/L至300g/L之酸或鹽、(C)80g/L至250g/L之錯合劑及(D)0.1g/L至30g/L之具有聚氧伸烷基鏈之二胺，且其中pH值在4與8之間的範圍內。A method for barrel plating or high-speed rotary plating of electronic components, comprising the steps of barrel plating or high-speed rotary plating of electronic components using a tin plating solution, the tin plating solution comprising (A) 5 g / L to 30 g / L of stannous tin Ion, (B) 30g / L to 300g / L acid or salt, (C) 80g / L to 250g / L complexing agent, and (D) 0.1g / L to 30g / L with polyoxyalkylene chain Diamine, and wherein the pH value is in the range between 4 and 8. 如申請專利範圍第1項所述之方法，其中滾鍍在電流密度在0.05A/dm2與0.5A/dm2之間下進行。The method according to item 1 of the scope of patent application, wherein barrel plating is performed at a current density between 0.05 A / dm 2 and 0.5 A / dm 2 . 如申請專利範圍第1項所述之方法，其中該電子組件選自電容器、電感器、熱敏電阻及壓敏電阻。The method of claim 1, wherein the electronic component is selected from a capacitor, an inductor, a thermistor, and a varistor. 一種用於滾鍍或高速旋轉電鍍之中性鍍錫液，包含：(A)5g/L至30g/L之亞錫離子；(B)30g/L至300g/L之酸或鹽；(C)80g/L至250g/L之錯合劑；及(D)0.1g/L至30g/L之具有聚氧伸烷基鏈之二胺，其中pH在4與8之間的範圍內。A neutral tin plating solution for barrel plating or high-speed rotary electroplating, comprising: (A) stannous ions of 5 g / L to 30 g / L; (B) acids or salts of 30 g / L to 300 g / L; (C) ) 80g / L to 250g / L complexing agent; and (D) 0.1g / L to 30g / L diamine having polyoxyalkylene chain, wherein the pH is in the range between 4 and 8. 如申請專利範圍第4項所述之用於滾鍍或高速旋轉電鍍之中性鍍錫液，其中該具有該聚氧伸烷基鏈之二胺具有在200與1100之間的分子量。The neutral tin plating solution for barrel plating or high-speed rotary electroplating as described in item 4 of the scope of patent application, wherein the diamine having the polyoxyalkylene chain has a molecular weight between 200 and 1100.
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