TWI402381B - Method to electrodeposit metals using ionic liquids - Google Patents

Method to electrodeposit metals using ionic liquids Download PDF

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TWI402381B
TWI402381B TW96105493A TW96105493A TWI402381B TW I402381 B TWI402381 B TW I402381B TW 96105493 A TW96105493 A TW 96105493A TW 96105493 A TW96105493 A TW 96105493A TW I402381 B TWI402381 B TW I402381B
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ionic liquid
ammonium
metal
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TW200734491A (en
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Boris Kuzmanovic
Strien Cornelis Johannes Govardus Van
Colin Eric Bartel
Michael Zeitler
Johanna Christina Speelman
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Akzo Nobel Nv
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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
    • C25D3/66—Electroplating: Baths therefor from melts
    • C25D3/665—Electroplating: Baths therefor from melts from ionic liquids

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Description

使用離子液體電沈積金屬之方法Method for electrodepositing metal using ionic liquid

本發明係關於一種使用離子液體作為電解質在一基板上電沈積金屬之方法。The present invention relates to a method of electrodepositing a metal on a substrate using an ionic liquid as an electrolyte.

離子液體為具有低於100℃之熔點的非揮發性鹽。有許多種離子液體甚至在室溫時即為液體，其代表一類相對新型之溶劑。Ionic liquids are non-volatile salts having a melting point below 100 °C. There are many types of ionic liquids that are liquid even at room temperature, which represent a relatively new class of solvents.

吾人已知，一般而言離子液體可用於多種應用，例如反應溶劑、萃取溶劑、電池及電沈積中之電解質、催化劑、熱交換液，作為塗料中之添加劑。It is known that ionic liquids are generally used in a variety of applications, such as reaction solvents, extraction solvents, electrolytes in batteries and electrodeposition, catalysts, heat exchange fluids, as additives in coatings.

迄今為止，所有適於在電沈積中用作電解質之市售離子液體價格均相對較高，亦即大約為每公斤約50歐元至高達約1,000歐元。應將本申請案中之術語"電沈積"理解為包括電鍍及電解拋光兩者。To date, all commercially available ionic liquids suitable for use as electrolytes in electrodeposition are relatively expensive, i.e., from about 50 euros per kilogram to as high as about 1,000 euros per kilogram. The term "electrodeposition" as used in this application is to be understood to include both electroplating and electropolishing.

例如在Merck及Iolitec之網頁上揭示關於離子液體用途之若干實例：www.ionicliquids－merck.de及www.iolitec.com(日期為2006年2月3日)。Several examples of ionic liquid use are disclosed, for example, on the pages of Merck and Iolitec: www.ionicliquids-merck.de and www.iolitec.com (date: February 3, 2006).

據稱可用於電沈積方法之離子液體特定言之為三氟甲磺酸三辛基甲基銨、雙(三氟甲基磺醯基)醯亞胺N－甲基，N－三辛基銨、雙(三氟甲基磺醯基)醯亞胺三甲基－N－己基銨、雙(三氟甲基磺醯基)醯亞胺N－丁基，N－三甲基銨、雙(三氟甲基磺醯基)醯亞胺1－丁基－1－甲基－吡咯啶鎓、參(五氟乙基)三氟磷酸1－己基－3－甲基咪唑鎓、三氟乙酸1－丁基－3－甲基咪唑鎓，其均相當昂貴且具有形成極危險之HF(作為含氟離子液體之分解產物)的風險。The ionic liquids which are said to be useful in the electrodeposition process are specifically trioctylmethylammonium trifluoromethanesulfonate, bis(trifluoromethylsulfonyl) quinone imine N-methyl, N-trioctyl ammonium. , bis(trifluoromethylsulfonyl) quinone imine trimethyl-N-hexylammonium, bis(trifluoromethylsulfonyl) quinone imine N-butyl, N-trimethylammonium, bis ( Trifluoromethylsulfonyl) quinone imine 1-butyl-1-methyl-pyrrolidinium quinone, hexafluoroethyltrifluorophosphate 1-hexyl-3-methylimidazolium, trifluoroacetic acid 1 Butyl-3-methylimidazolium, which are both relatively expensive and have a risk of forming extremely dangerous HF (as a decomposition product of a fluorine-containing ionic liquid).

諸如氯化膽鹼/氯化鉻六水合物或氯化膽鹼/氯化鋅(亦報導為用於電沈積)之共熔混合物之價格同樣相當高。此外，作為該等離子液體之增效組分的金屬鹽在電沈積過程期間之消耗可能導致該等離子液體之分解。The price of a eutectic mixture such as choline chloride/chromium chloride hexahydrate or choline chloride/zinc chloride (also reported for electrodeposition) is also quite high. Furthermore, the consumption of the metal salt as a synergistic component of the plasma liquid during the electrodeposition process may result in decomposition of the plasma liquid.

WO 2002/026381揭示了氯化膽鹼及諸如氯化鉻(III)之(水合)金屬鹽的離子液體(共熔混合物)及其在電沈積及電解拋光中之用途。該等混合物由氯化膽鹼及(水合)金屬鹽按1：1與1：2.5之間的銨與金屬離子之比率組成，且特定言之，據稱其適用於在金屬基板上沈積鉻、鈷、鋅或銀。WO 2002/026381 discloses ionic liquids (eutectic mixtures) of choline chloride and (hydrated) metal salts such as chromium (III) chloride and their use in electrodeposition and electropolishing. The mixtures consist of choline chloride and (hydrated) metal salts in a ratio of ammonium to metal ions between 1:1 and 1:2.5, and in particular, are said to be suitable for depositing chromium on metal substrates, Cobalt, zinc or silver.

然而，存在對適用於電沈積製程之離子液體的需要，該離子液體對基板上之電沈積金屬賦予良好品質(亦即具有良好外觀或具有足夠硬度之電塗基板)同時在經濟上具有吸引力，或換言之，可獲得高品質低價位。在工業中亦需要適用於電沈積製程之電解質，其具有高能量效率，不基於使用有毒化學製品，且其可實現大規模電鍍。此外，需要一種在基板上沈積金屬之方法，該方法僅要求溶劑中之低金屬濃度，因為如此可得到就經濟性觀點而言之改良且使得該製程更具可控性。However, there is a need for an ionic liquid suitable for use in an electrodeposition process that imparts good quality to an electrodeposited metal on a substrate (i.e., an electrocoated substrate having a good appearance or sufficient hardness) while being economically attractive. Or, in other words, high quality and low price. There is also a need in the industry for electrolytes suitable for electrodeposition processes that are highly energy efficient, are not based on the use of toxic chemicals, and that enable large scale plating. In addition, there is a need for a method of depositing a metal on a substrate that requires only a low metal concentration in the solvent, as this provides an improvement in terms of economy and makes the process more controllable.

亦存在對在基板上電沈積金屬之方法的需要，在該方法中將離子液體用作電解質，其中該離子液體具有良好電導率，令人滿意之電化學穩定性範圍，且可溶解足量待令人滿意地沈積於該基板上之金屬鹽。There is also a need for a method of electrodepositing a metal on a substrate in which an ionic liquid is used as an electrolyte, wherein the ionic liquid has a good electrical conductivity, a satisfactory range of electrochemical stability, and is soluble enough. A metal salt that is satisfactorily deposited on the substrate.

最後，存在對使用電化學方法來沈積特定金屬之更合適途徑的需要，該等材料當前係使用此項技術中已知之方法沈積，該等方法有顯著之健康及環境風險。鋁及鈦為無法自水溶液沈積而可自非水性有機電解質沈積之金屬的實例。由於該等有機浴存在***及起火危險，因此該等金屬在更可接受之溶劑中的電沈積將為高度有益的。此外，當前之工業鉻沈積製程仍基於含有高度致癌性鉻(VI)之鉻酸(參看，例如，F.A.Lowenheim之Modern Electroplating ,1942或L.J.Durney之Electroplating Engineering Handbook ,1996)。此外，習知鉻電鍍浴需要使用具有顯著處理問題之強酸，而使用本發明之化合物可使得該等處理難度最小化或得以消除。Finally, there is a need for a more suitable route for the deposition of specific metals using electrochemical methods, which are currently deposited using methods known in the art, which have significant health and environmental risks. Aluminum and titanium are examples of metals that can be deposited from a non-aqueous organic electrolyte that cannot be deposited from aqueous solutions. Electrodeposition of such metals in more acceptable solvents will be highly beneficial due to the risk of explosion and fire in such organic baths. In addition, current industrial chromium deposition processes are still based on chromic acid containing highly carcinogenic chromium (VI) (see, for example, Modern Electroplating by FA Lowenheim, 1942 or Electroplating Engineering Handbook , LJ Durney, 1996). In addition, conventional chromium plating baths require the use of strong acids with significant processing problems, and the use of the compounds of the present invention minimizes or eliminates such processing difficulties.

本發明現提供一種在一基板上電鍍或電解拋光金屬之方法，其中將選自N＋ R1 R2 R3 R4 X－ 及N＋ R5 R6 R7 R8 Y－ 之群的離子液體用作電解質，且將添加至該離子液體之金屬鹽用作金屬源，或將一金屬陽極用作該金屬源，其中R1 至R8 中之任一者獨立地代表氫、烷基、環烷基、芳基或芳烷基，該等基團可經選自OH、Cl、Br、F、I、苯基、NH2 、CN、NO2 、COOR9 、CHO、COR9 或OR9 之基團取代，R5 至R8 中之至少一者為脂肪烷基鏈，且R5 至R8 中之一或多者可為(聚)氧基伸烷基，其中該伸烷基為C1 至C4 伸烷基且氧基伸烷基單元之總數可為1至50個氧基伸烷基單元，且R1 至R8 中之至少一者為C1 至C4 烷基鏈，R9 為烷基或環烷基，X－ 為具有N－醯基磺醯基醯亞胺陰離子(－CO－N－ －SO2 －)官能性之陰離子，Y－ 為與N＋ R5 R6 R7 R8 銨陽離子相容之陰離子，諸如鹵化物陰離子、羧酸鹽陰離子、硫酸根(有機及無機硫酸根兩者)、磺酸根、碳酸根、硝酸根、亞硝酸根、硫氰酸根、氫氧根或磺醯基醯亞胺陰離子；其較佳為Cl－ 、Br－ 或CH3 SO4 － 。The present invention now provides a method of electroplating or electrolytically polishing a metal on a substrate, wherein an ion selected from the group consisting of N + R 1 R 2 R 3 R 4 X - and N + R 5 R 6 R 7 R 8 Y - The liquid is used as an electrolyte, and a metal salt added to the ionic liquid is used as a metal source, or a metal anode is used as the metal source, wherein any one of R 1 to R 8 independently represents hydrogen, an alkyl group, a cycloalkyl, aryl or aralkyl group, which may be selected from OH, Cl, Br, F, I, phenyl, NH 2 , CN, NO 2 , COOR 9 , CHO, COR 9 or OR 9 Substituting a group, at least one of R 5 to R 8 is a fatty alkyl chain, and one or more of R 5 to R 8 may be a (poly)oxyalkylene group, wherein the alkylene group is C 1 to C 4 alkyl and the total number of oxyalkyl units may be 1 to 50 oxyalkyl units, and at least one of R 1 to R 8 is a C 1 to C 4 alkyl chain, R 9 Is an alkyl or cycloalkyl group, X - is an anion having an N-fluorenylsulfonyl quinone imine anion (-CO-N - -SO 2 -) functionality, and Y - is an N + R 5 R 6 R 7 R 8 ammonium cation compatible anion, such as halide anion, a carboxylate anion, a sulfate (both organic and inorganic sulfate), a sulfonate, a carbonate, a nitrate, a nitrite, a thiocyanate, a hydroxide or a sulfonyl imide anion; preferably Cl - , Br - or CH 3 SO 4 - .

在一實施例中，Y－ 係選自F－ 、Cl－ 、Br－ 、I－ 之群；R10 COO－ 陰離子之群，其中R10 可為氫、C1 －C22 烷基、烯基或芳族基；R11 SO4 － 陰離子之群，其中R11 可不存在(在該情況下陽離子為二價)、氫、C1 －C22 烷基、烯基或芳族基；R12 SO3 － 陰離子之群，其中R12 可不存在(在該情況下陽離子為二價)、氫、C1 －C22 烷基、烯基或芳族基；R13 CO3 － 陰離子之群，其中R13 可不存在(在該情況下陽離子為二價)、氫、C1 －C22 烷基、烯基或芳族基；及R14 －N－ －SO2 －R15 陰離子之群，其中R14 及/或R15 獨立地可為氫、C1 －C22 烷基、烯基或芳族基，且R14 可經由羰基連接至氮原子。In one embodiment, the Y - line is selected from the group consisting of F - , Cl - , Br - , I - ; a group of R 10 COO - anions, wherein R 10 can be hydrogen, C 1 -C 22 alkyl, alkenyl or an aromatic group; R 11 SO 4 - anion of the group, wherein R 11 may be absent (in this case the cation is divalent), hydrogen, C 1 -C 22 alkyl, alkenyl or aromatic group; R 12 SO 3 - the anionic group, wherein R 12 may be absent (in this case the cation is divalent), hydrogen, C 1 -C 22 alkyl, alkenyl or aromatic group; R 13 CO 3 - anions group, wherein R 13 may be absent (in this case the cation is divalent), hydrogen, C 1 -C 22 alkyl, alkenyl or aromatic; and a group of R 14 -N - -SO 2 -R 15 anions, wherein R 14 And/or R 15 may independently be hydrogen, C 1 -C 22 alkyl, alkenyl or aromatic, and R 14 may be attached to the nitrogen atom via a carbonyl group.

脂肪烷基鏈意謂包括飽和及/或不飽和鏈且含有8至22個碳原子；較佳地，其含有10至22個碳原子，最佳含有12至20個碳原子。The fatty alkyl chain is meant to include saturated and/or unsaturated chains and contain from 8 to 22 carbon atoms; preferably, it contains from 10 to 22 carbon atoms, and most preferably from 12 to 20 carbon atoms.

在一實施例中，N＋ R5 R6 R7 R8 Y－ 離子液體具有1 g I2 /100 gr離子液體以上、較佳2 g I2 /100 gr離子液體以上、更佳3 g I2 /100 gr離子液體以上且最佳5 g I2 /100 gr離子液體以上之碘價。該碘價通常為210 g I2 /100 gr離子液體以下。In one embodiment, the N + R 5 R 6 R 7 R 8 Y - ionic liquid has more than 1 g I 2 /100 gr ionic liquid, preferably 2 g I 2 /100 gr ionic liquid, more preferably 3 g I Iodine price above 2 / 100 gr ionic liquid and optimal 5 g I 2 /100 gr ionic liquid. The iodine value is usually below 210 g I 2 /100 gr ionic liquid.

在一較佳實施例中，X－ 係基於一種稱為甜味劑之化合物。在另一較佳實施例中，N＋ R1 R2 R3 R4 為胺，其中R1 至R4 之基團為氫或視情況經OH或Cl取代之烷基或環烷基；更佳地，其至少三者為烷基，更佳為C1 至C4 烷基。In a preferred embodiment, X - is based on a compound called sweeteners. In another preferred embodiment, N + R 1 R 2 R 3 R 4 is an amine wherein the group of R 1 to R 4 is hydrogen or an alkyl or cycloalkyl group optionally substituted by OH or Cl; Preferably, at least three of them are alkyl groups, more preferably C 1 to C 4 alkyl groups.

在一較佳實施例中，該離子液體係選自下列化合物中之任一者：糖酸膽鹼、乙醯胺基磺酸膽鹼、氯化十六基三甲基銨、氯化十八基三甲基銨、氯化可可三甲基銨、氣化動物脂三甲基銨、氯化氫化動物脂三甲基銨、氯化氫化棕櫚三甲基銨、氯化油基三甲基銨、氯化大豆三甲基銨、氯化可可苄基二甲基銨、氯化C12－16－烷基苄基二甲基銨、氯化氫化動物脂苄基二甲基銨、氯化二辛基二甲基銨、氯化二癸基二甲基銨、硝酸二可可二甲基銨、氯化二可可二甲基銨、氯化二(氫化動物脂)二甲基銨、氯化二(氫化動物脂)苄基甲基銨、氯化二動物脂二甲基銨、氯化二(十八基)二甲基銨、氯化氫化動物脂(2－乙基己基)二甲基銨、甲硫酸氫化動物脂(2－乙基己基)二甲基銨、氯化三(十六基)甲基銨、氯化十八基甲基雙(2－羥基乙基)銨、硝酸可可雙(2－羥基乙基)甲基銨、氯化可可雙(2－羥基乙基)甲基銨、氯化可可雙(2－羥基乙基)苄基銨、氯化油基雙(2－羥基乙基)甲基銨、氯化可可[聚氧伸乙基(15)]甲基銨、甲硫酸可可[聚氧伸乙基(15)]甲基銨、氯化可可[聚氧伸乙基(17)]甲基銨、氯化十八基[聚氧伸乙基(15)]甲基銨、氯化氫化動物脂[聚氧伸乙基(15)]甲基銨、乙酸參(2－羥基乙基)動物脂銨、二氯化動物脂－1,3－丙烷五甲基二銨。In a preferred embodiment, the ionic liquid system is selected from any of the following compounds: choline disaccharide, choline acetyl sulfonate, hexadecyl trimethyl ammonium chloride, chlorinated octa Trimethylammonium chloride, cocotrimethylammonium chloride, gasified tallow trimethylammonium, hydrogenated tallow trimethylammonium chloride, hydrogenated palmithomethylammonium chloride, chlorinated oil trimethylammonium, chlorine Soy trimethylammonium chloride, cocobenzyl dimethylammonium chloride, C12-16-alkylbenzyldimethylammonium chloride, hydrogenated tallow benzyldimethylammonium chloride, dioctyldimethyl chloride Base ammonium, dimercaptodimethylammonium chloride, dicocodyl ammonium dichloride, dicocodyl ammonium chloride, di(hydrogenated tallow) dimethyl ammonium chloride, chlorinated di (hydrogenated tallow) Benzylmethylammonium, diammonium chloride dimethylammonium chloride, di(octadecyl)dimethylammonium chloride, hydrogenated tallow (2-ethylhexyl)dimethylammonium, hydrogenated hydrogenated animal Lipid (2-ethylhexyl) dimethylammonium, tris(hexadecyl)methylammonium chloride, octadecylmethylbis(2-hydroxyethyl)ammonium chloride, cocoa nitric acid (2-hydroxyethyl) Methylammonium, chlorination Cocoa bis(2-hydroxyethyl)methylammonium, chlorinated cocobis(2-hydroxyethyl)benzylammonium chloride, chlorinated bis(2-hydroxyethyl)methylammonium chloride, chlorinated cocoa [polyoxygen] Ethyl (15)]methylammonium, cocoa-methylsulfate [polyoxyethyl (15)] methylammonium chloride, chlorinated cocoa [polyoxyethyl (17)] methyl ammonium, octadecyl chloride [Polyoxyethyl (15)] methylammonium, hydrogenated tallow [polyoxyethylene (15)] methylammonium, acetic acid ginseng (2-hydroxyethyl) tallow ammonium, dichlorinated tallow -1,3-propane pentamethyl diammonium.

US 4,849,438揭示了糖酸膽鹼、一種製備糖酸膽鹼之方法及糖酸膽鹼用於保護植物免受真菌及細菌侵害之用途。製備實例1之糖酸膽鹼反應產物首先為油狀物質，稍後由於存在0.3 mol H2 O/mol糖酸膽鹼而呈晶體形式。在製備實例3中，藉由使氯化膽鹼與糖酸鈉反應而製備糖酸膽鹼。並未確認糖酸膽鹼為離子液體，但在實例3中隱含地將其理解為離子液體。No. 4,849,438 discloses the use of choline glycolate, a process for the preparation of choline glycolate and the use of choline glycolate for the protection of plants from fungi and bacteria. The choline reaction product of Preparation Example 1 was first an oily substance which was later in the form of a crystal due to the presence of 0.3 mol H 2 O/mol of choline. In Preparation Example 3, choline saccharate was prepared by reacting choline chloride with sodium saccharate. Choline citrate was not confirmed to be an ionic liquid, but was implicitly understood in Example 3 as an ionic liquid.

E.B.Carter等人於Chemical Communications 2004,(6),630－631頁中揭示了糖酸鹽陰離子及乙醯胺基磺酸鹽陰離子與四級銨陽離子(諸如三乙基甲基銨或咪唑鎓陽離子)之離子液體。EB Carter et al., Chemical Communications 2004, (6), pages 630-631, discloses saccharide anions and acetoguanidine sulfonate anions with quaternary ammonium cations (such as triethylmethylammonium or imidazolium cations). Ionic liquid.

J.Tang等人於Polymer 46(2005),12460－12467頁中揭示了基於十二基三乙基銨之離子液體及其CO2 吸收作用。The ionic liquid based on dodecyltriethylammonium and its CO 2 absorption are disclosed by J. Tang et al., Polymer 46 (2005), pages 12460-12467.

然而，以上文獻均未揭示或提出用於在基板上電沈積金屬之方法的基於N－醯基磺醯基醯亞胺或基於脂肪烷基之離子液體的適用性。However, none of the above documents disclose or suggest the suitability of an N-mercaptosulfonyl quinone imine or a fatty alkyl-based ionic liquid for a method of electrodepositing a metal on a substrate.

如上文所示形成之離子液體係安全的(潛在食品級)，且可作為溶劑應用於電沈積或電解拋光方法中，此係因為其含有相對低濃度之金屬鹽。另一方面，該金屬鹽濃度範圍較廣，或換言之根據本發明用於在基板上電沈積金屬之方法係在相對低之金屬鹽濃度的廣泛範圍上可控。相較於使用其他離子液體作為電解質之現有技術的方法，由根據本發明之方法製得之電鍍基板具有改良外觀。此外，當在電沈積方法中使用現有技術中所揭示之某些離子液體作為電解質時，完全無法得到沈積於基板上之金屬層，尤其在按照本描述內容中所指定之較佳量來使用金屬時。The ionic liquid system formed as described above is safe (potential food grade) and can be used as a solvent in electrodeposition or electropolishing processes because it contains relatively low concentrations of metal salts. On the other hand, the metal salt has a wide concentration range, or in other words, the method for electrodepositing metal on a substrate according to the present invention is controllable over a wide range of relatively low metal salt concentrations. The plated substrate produced by the method according to the present invention has an improved appearance compared to prior art methods using other ionic liquids as the electrolyte. In addition, when certain ionic liquids disclosed in the prior art are used as the electrolyte in the electrodeposition method, it is impossible to obtain a metal layer deposited on the substrate at all, especially in a preferred amount as specified in the description. Time.

如上文所示用於根據本發明之方法的離子液體可藉由鹽之簡單反應而製備，例如藉由氯化膽鹼與糖酸鈉(乙醯胺基磺酸鈉)之複分解反應以形成糖酸膽鹼(乙醯胺基磺酸膽鹼)離子液體。The ionic liquids used in the process according to the invention as indicated above can be prepared by simple reaction of salts, for example by metathesis of choline chloride with sodium saccharate (sodium acetal sulfonate) to form sugars. Acid choline (acetylamine choline) ionic liquid.

又已發現根據市售化合物製造之用作界面活性劑及流變改質劑的離子液體(諸如氯化氫化動物脂甲基[聚氧伸乙基(15)]銨、氯化可可烷基甲基[聚氧伸乙基(15)]銨、甲硫酸可可烷基甲基[聚氧伸乙基(15)]銨、氯化十八基甲基[聚氧伸乙基(15)]銨及氯化二(氫化動物脂)二甲基銨)適用於根據本發明之方法。It has also been found that ionic liquids (such as hydrogenated tallow methyl [polyoxy-extended ethyl (15)] ammonium, chlorinated cocoalkyl methyl groups are used as surfactants and rheology modifiers based on commercially available compounds. [Polyoxy-extended ethyl (15)] ammonium, cocoamethylmethylsulfate methyl [polyoxyethyl (15)] ammonium, octadecylmethyl chloride [polyoxyethyl (15)] ammonium and Di(hydrogenated tallow) dimethylammonium chloride is suitable for use in the process according to the invention.

在一較佳實施例中，離子液體之銨陽離子與來自所溶解之鹽或來自金屬陽極之金屬鹽之金屬陽離子的莫耳比處於1,000：1與3：1之間。500：1與5：1之間的離子液體之銨陽離子與金屬鹽之金屬陽離子的莫耳比更佳，100：1與7：1之間的莫耳比最佳，該莫耳比提供高品質金屬層、金屬於離子液體中之極佳溶解及製程成本與電鍍基板產物外觀之間的良好平衡。In a preferred embodiment, the molar ratio of the ammonium cation of the ionic liquid to the metal cation from the dissolved salt or metal salt from the metal anode is between 1,000:1 and 3:1. The molar ratio of the ammonium cation of the ionic liquid between 500:1 and 5:1 to the metal cation of the metal salt is better, and the molar ratio between 100:1 and 7:1 is optimal, and the molar ratio is high. Excellent balance of quality metal layer, metal in ionic liquid and process cost and appearance of plated substrate product.

在根據本發明之另一較佳電沈積方法中沈積金屬鉻、鋁、鈦、鋅或銅中之一者；更佳為沈積鉻或鋁，最佳為沈積鉻。One of the metallic chromium, aluminum, titanium, zinc or copper is deposited in another preferred electrodeposition process according to the present invention; more preferably, chromium or aluminum is deposited, preferably deposited chromium.

電沈積較佳在90℃以下之溫度、更佳在室溫下於開放電沈積容器中進行，但電沈積不限於該等條件。在使用金屬陽極之實施例中，該陽極可為金屬條、金屬塊、金屬片形式或熟習此項技術者所已知的任何其他合適形式。The electrodeposition is preferably carried out at a temperature below 90 ° C, more preferably at room temperature in an open electrodeposition vessel, but electrodeposition is not limited to these conditions. In embodiments in which a metal anode is used, the anode can be in the form of a metal strip, a metal block, a sheet of metal, or any other suitable form known to those skilled in the art.

根據本發明之離子化合物亦可應用於電解拋光中。例如，可使用根據本發明之化合物將不銹鋼拋光。不銹鋼形成電解拋光之最大商業應用，而傳統上拋光浴含有基於濃硫酸及濃磷酸之混合物。該等混合物具有高度毒性及腐蝕性，且由於歸因於所用高電流密度之大量氣體逸出，因此在電解拋光期間傾向於形成毒性及腐蝕性"霧"。根據本發明之較佳電解拋光方法的主要優勢為該等方法相較於習知方法通常更加環保。所提供之其他優勢為該等方法可在室溫下進行且可以較低功率消耗進行操作，同時提供相較於傳統技術更有光澤之反射修飾面層。根據本發明之材料的另一優勢為當將該等材料用於電解浴(尤其為電鍍浴或電解拋光浴)時，析氫相較於習知使用之酸性浴顯著減少。此具有若干重要結論。首先，其導致極高之電流效率。在有利環境下可獲得高達90%或以上之電流效率。就安全觀點而言，減少之析氫亦為有利的，且減少之析氫顯著減少在電化學製程期間於基板材料中出現之氫脆量。其亦得到具有改良表面修整之電鍍材料，該材料相較於藉由習知方法所得之電鍍具有大為減少之微裂紋。此又可改良塗層之耐蝕性及/或允許使用更薄但仍提供與習知塗層相當耐蝕性之塗層，該塗層因此在製造上更為廉價、消耗原料更少且更環保。The ionic compound according to the invention can also be used in electrolytic polishing. For example, the stainless steel can be polished using the compound according to the invention. Stainless steel forms the largest commercial application for electrolytic polishing, whereas conventional polishing baths contain a mixture based on concentrated sulfuric acid and concentrated phosphoric acid. These mixtures are highly toxic and corrosive and tend to form toxic and corrosive "fogs" during electropolishing due to the large amount of gas escaping due to the high current density used. A major advantage of the preferred electropolishing process in accordance with the present invention is that such processes are generally more environmentally friendly than conventional methods. Other advantages provided are that the methods can be performed at room temperature and can be operated at lower power consumption while providing a more reflective reflective finish layer than conventional techniques. A further advantage of the material according to the invention is that when these materials are used in an electrolytic bath, in particular an electroplating bath or an electropolishing bath, the hydrogen evolution phase is significantly reduced compared to conventionally used acidic baths. This has several important conclusions. First, it results in extremely high current efficiency. Current efficiencies of up to 90% or more can be obtained in an advantageous environment. From a safety standpoint, reduced hydrogen evolution is also advantageous, and reduced hydrogen evolution significantly reduces the amount of hydrogen embrittlement that occurs in the substrate material during the electrochemical process. It also results in an electroplated material having an improved surface finish which has greatly reduced microcracks compared to electroplating obtained by conventional methods. This, in turn, improves the corrosion resistance of the coating and/or allows the use of thinner coatings that still provide comparable corrosion resistance to conventional coatings, which are therefore less expensive to manufacture, consume less raw materials and are more environmentally friendly.

實例Instance 製備實例A－製備半無水糖酸膽鹼離子液體Preparation Example A - Preparation of semi-anhydrous choline ionic liquid

使用61丙酮作為溶劑，將1,080g糖酸鈉水合物(99%，購自Acros)與732 g固體氣化膽鹼(99%，購自Acros)混合。攪動8小時後，考慮到將發生離子交換反應，過濾所形成之懸浮液。濾液在旋轉蒸發器中經受於約60℃之溫度及約40毫巴之最小壓力下的蒸發，直至不再觀測到溶劑蒸發。剩餘產物為液體，且經元素化學組份分析(氯化物、鈉及硫濃度)確認為糖酸膽鹼。1,080 g of sodium saccharate hydrate (99%, purchased from Acros) was mixed with 732 g of solid gasified choline (99%, purchased from Acros) using 61 acetone as a solvent. After stirring for 8 hours, it was considered that an ion exchange reaction would occur, and the resulting suspension was filtered. The filtrate was subjected to evaporation in a rotary evaporator at a temperature of about 60 ° C and a minimum pressure of about 40 mbar until solvent evaporation was no longer observed. The remaining product was a liquid and was confirmed to be choline disaccharide by elemental chemical composition analysis (chloride, sodium and sulfur concentrations).

製備實例B－製備無水糖酸膽鹼離子液體Preparation Example B - Preparation of an anhydrous choline ionic liquid

將糖酸鈉水合物(99%，購自Acros)於120℃之溫度下乾燥，直至不再觀測到質量減少，以移除所有存在之水分。之後使用丙酮作為溶劑，將該無水糖酸鈉與氣化膽鹼(99%，購自Acros)以1：1之莫耳比混合。攪動8小時後，考慮到將發生離子交換反應，過濾所形成之懸浮液。濾液在旋轉蒸發器中經受於約85℃之溫度及約40毫巴之最小壓力下的蒸發，直至不再觀測到溶劑蒸發。剩餘產物為液體，且經元素化學組份分析(氯化物、鈉及硫濃度亦及水濃度)確認為無水糖酸膽鹼。Sodium saccharate hydrate (99%, purchased from Acros) was dried at 120 ° C until no further reduction in mass was observed to remove all moisture present. The anhydrous sodium saccharate was then mixed with gasified choline (99%, purchased from Acros) at a molar ratio of 1:1 using acetone as the solvent. After stirring for 8 hours, it was considered that an ion exchange reaction would occur, and the resulting suspension was filtered. The filtrate was subjected to evaporation in a rotary evaporator at a temperature of about 85 ° C and a minimum pressure of about 40 mbar until solvent evaporation was no longer observed. The remaining product was a liquid and was confirmed to be anhydrous choline choline by elemental chemical composition analysis (chloride, sodium and sulfur concentrations as well as water concentration).

實例1－在半無水糖酸膽鹼中將銅電鍍於黃銅上Example 1 - Electroplating Copper on Brass in Semi-Anhydrous Choline

向所製備含有約2重量%水之糖酸膽鹼離子液體中裝入氯化銅(II)二水合物鹽，且攪拌該混合物直至固體鹽溶解。在所製備之溶液中，銅濃度為約11 g/kg，而胺鹽與銅水合鹽之莫耳比為21：1。To the prepared choline cation solution containing about 2% by weight of water, a copper(II) chloride dihydrate salt was charged, and the mixture was stirred until the solid salt was dissolved. In the prepared solution, the copper concentration was about 11 g/kg, and the molar ratio of the amine salt to the copper hydrated salt was 21:1.

將約250 ml該溶液倒入裝配有電加熱元件之哈氏槽(Hull cell)中，該哈氏槽具有陽極側上65 mm之長度及陰極側上102 mm之長度、48 mm之最短陽極－陰極距離、127 mm之最長陽極－陰極距離及65 mm之深度。將該槽加熱至70℃與80℃之間的溫度。使用中心定位頂伸式葉輪攪拌該液體。Approximately 250 ml of this solution was poured into a Hull cell equipped with an electric heating element having a length of 65 mm on the anode side and a length of 102 mm on the cathode side, the shortest anode of 48 mm - Cathode distance, longest anode-cathode distance of 127 mm and depth of 65 mm. The tank was heated to a temperature between 70 ° C and 80 ° C. The liquid is agitated using a centrally located overhead impeller.

將鍍鉑鈦板用作陽極，且將其連接至直流電源之正極端子；而將黃銅板用作陰極(基板)，且將其連接至負極端子。使用市售去污粉清潔該基板，依次在脫礦質水、丙酮中且之後在乙醇中且最終在4 M－HCl水溶液中洗滌，隨後將其導入該浴中。當將兩板均連接且導入該槽時，將電壓差設定為30 V。在串聯之儀錶上監視電流。A platinized titanium plate was used as the anode and connected to the positive terminal of the direct current power source; a brass plate was used as the cathode (substrate), and it was connected to the negative terminal. The substrate was cleaned using commercially available soil release powder, followed by demineralized water, acetone and then in ethanol and finally in 4 M-HCl aqueous solution, which was then introduced into the bath. When both boards are connected and introduced into the slot, the voltage difference is set to 30 V. Monitor the current on the meter in series.

在1.5小時之電鍍後，將陰極與電源之連接斷開，且自槽中取出。將該板在水及丙酮中洗滌，接著將其乾燥。在該板於電鍍期間浸沒於離子液體中之部分上觀測到橙色/棕色銅沈積層。由於在陰極之不同位置上電流密度的差異，該層之厚度自板一側至另一側而減少。After 1.5 hours of plating, the cathode was disconnected from the power source and removed from the tank. The plate was washed in water and acetone and then dried. An orange/brown copper deposit was observed on the portion of the plate that was immersed in the ionic liquid during electroplating. The thickness of the layer decreases from one side of the board to the other due to differences in current density at different locations of the cathode.

實例2－在含水糖酸膽鹼中將來自Cr(III)鹽之鉻電鍍至碳鋼上Example 2 - Electroplating chromium from Cr(III) salt onto carbon steel in aqueous choline choline

向所製備含有約7重量%水之糖酸膽鹼離子液體中裝入氯化鉻(III)六水合物鹽，且攪拌該混合物直至固體鹽溶解。為提高胺鹽與鉻鹽之比率且同時改良鉻鹽之溶解性，添加氯化膽鹼。在所製備之溶液中，鉻(III)之濃度為約20 g/kg，而胺鹽與鉻水合鹽之莫耳比為9：1。To the prepared choline chloride ionic liquid containing about 7% by weight of water, chromium (III) chloride hexahydrate salt was charged, and the mixture was stirred until the solid salt was dissolved. In order to increase the ratio of the amine salt to the chromium salt and at the same time to improve the solubility of the chromium salt, choline chloride is added. In the solution prepared, the concentration of chromium (III) was about 20 g/kg, and the molar ratio of amine salt to chromium hydrated salt was 9:1.

將約250 ml該溶液倒入如實例1中所述之哈氏槽中。將該槽加熱至70℃與80℃之間的溫度。使用中心定位頂伸式葉輪攪拌該液體。Approximately 250 ml of this solution was poured into a Hastelloy bath as described in Example 1. The tank was heated to a temperature between 70 ° C and 80 ° C. The liquid is agitated using a centrally located overhead impeller.

將鍍鉑鈦板用作陽極，且連接至直流電源之正極端子；而將碳鋼用作陰極(基板)，且連接至負極端子。使用市售去污粉清潔該基板，依次在脫礦質水、丙酮中且之後在乙醇中且最終在4 M－HCl水溶液中洗滌，隨後將其導入該浴中。當將兩板均連接且導入該槽中時，將電壓差設定為30 V。在串聯之儀錶上監視電流。A platinized titanium plate was used as the anode and connected to the positive terminal of the direct current power source; carbon steel was used as the cathode (substrate) and connected to the negative terminal. The substrate was cleaned using commercially available soil release powder, followed by demineralized water, acetone and then in ethanol and finally in 4 M-HCl aqueous solution, which was then introduced into the bath. When both boards are connected and introduced into the slot, the voltage difference is set to 30 V. Monitor the current on the meter in series.

在5小時之電鍍後，將陰極與電源之連接斷開，且自槽中取出。將該板在水及丙酮中洗滌，接著將其乾燥。在該板於電鍍期間浸沒於離子液體中之部分上觀測到淺灰色(金屬色)沈積層。由於在陰極之不同位置上電流密度的差異，該層之厚度自板一側至另一側而減少，在一側上無可見層。藉由掃描電子顯微鏡組合以X－射線散射(SEM/EDX)來分析該板之化學組份。After 5 hours of plating, the cathode was disconnected from the power source and removed from the tank. The plate was washed in water and acetone and then dried. A light gray (metal color) deposited layer was observed on the portion of the plate that was immersed in the ionic liquid during electroplating. Due to the difference in current density at different locations of the cathode, the thickness of the layer decreases from one side of the board to the other, with no visible layer on one side. The chemical composition of the plate was analyzed by X-ray scattering (SEM/EDX) by scanning electron microscope combination.

該分析確認在基板之浸沒部分上存在鉻(圖1a)，而在非浸沒表面上未發現鉻(圖1b)。This analysis confirmed the presence of chromium on the immersed portion of the substrate (Fig. 1a) and no chromium on the non-immersed surface (Fig. 1b).

實例3－在半無水糖酸膽鹼中將來自Cr(III)鹽之鉻電鍍至碳鋼上Example 3 - Electroplating chromium from Cr(III) salt onto carbon steel in semi-anhydrous choline choline

向所製備含有約2重量%水之糖酸膽鹼離子液體中裝入氯化鉻(III)六水合物鹽，且攪拌該混合物直至固體鹽溶解。在所製備之溶液中，鉻(III)之濃度為約12 g/kg，而胺鹽與鉻水合鹽之莫耳比為13：1。To the prepared choline chloride ionic liquid containing about 2% by weight of water, chromium (III) chloride hexahydrate salt was charged, and the mixture was stirred until the solid salt was dissolved. In the solution prepared, the concentration of chromium (III) was about 12 g/kg, and the molar ratio of amine salt to chromium hydrated salt was 13:1.

將約250 ml該溶液倒入如實例1中所述之哈氏槽中。將該槽加熱至70℃與80℃之間的溫度。使用中心定位頂伸式葉輪攪拌該液體。Approximately 250 ml of this solution was poured into a Hastelloy bath as described in Example 1. The tank was heated to a temperature between 70 ° C and 80 ° C. The liquid is agitated using a centrally located overhead impeller.

將鍍鉑鈦板用作陽極，且連接至直流電源之正極端子；而將碳鋼用作陰極(基板)，且連接至負極端子。使用市售去污粉清潔該基板，依次在脫礦質水、丙酮中且之後在乙醇中且最終在4 M－HCl水溶液中洗滌，隨後將其導入該浴中。當將兩板均連接且導入該槽中時，將電壓差設定為30 V。在串聯之儀錶上監視電流。A platinized titanium plate was used as the anode and connected to the positive terminal of the direct current power source; carbon steel was used as the cathode (substrate) and connected to the negative terminal. The substrate was cleaned using commercially available soil release powder, followed by demineralized water, acetone and then in ethanol and finally in 4 M-HCl aqueous solution, which was then introduced into the bath. When both boards are connected and introduced into the slot, the voltage difference is set to 30 V. Monitor the current on the meter in series.

在5小時之電鍍後，將陰極與電源之連接斷開，且自槽中取出。將該板在水及丙酮中洗滌，接著將其乾燥。藉由之掃描電子顯微鏡組合以X射線散射(SEM/EDX)的化學分析顯示存在極薄之沈積層。After 5 hours of plating, the cathode was disconnected from the power source and removed from the tank. The plate was washed in water and acetone and then dried. Chemical analysis by X-ray scattering (SEM/EDX) by scanning electron microscope combination revealed the presence of a very thin deposited layer.

比較實例4－在氯化鉻(III)六水合物與氯化膽鹼之2：1莫耳比共熔混合物中將來自Cr(III)鹽之鉻電鍍至碳鋼上Comparative Example 4 - Electroplating chromium from Cr(III) salt onto carbon steel in a 2:1 molar ratio eutectic mixture of chromium (III) hexahydrate and choline chloride

以2：1之莫耳比將氯化鉻(III)六水合物與氯化膽鹼混合。將該固體混合物在烘箱中於約120℃之溫度下加熱若干小時。不時地振動該混合物，直至不再觀測到固體。將深綠色液體產物冷卻至室溫。The chromium (III) chloride hexahydrate was mixed with choline chloride at a molar ratio of 2:1. The solid mixture was heated in an oven at a temperature of about 120 ° C for several hours. The mixture was shaken from time to time until no solids were observed. The dark green liquid product was cooled to room temperature.

重複實例2，但使用所得2：1莫耳比之氯化鉻(III)六水合物與氯化膽鹼之共熔混合物替代實例2中所用溶液。Example 2 was repeated except that the resulting solution of Example 2 was replaced with a eutectic mixture of 2:1 molar ratio chromium(III) chloride hexahydrate and choline chloride.

在圖2中，圖解說明實例2基板之外觀及比較實例4基板之外觀。可清楚的說明根據本發明之方法得到電鍍基板之改良視覺外觀(有光澤之金屬色而非暗淡無光澤沈積物)。In Fig. 2, the appearance of the substrate of Example 2 and the appearance of the substrate of Comparative Example 4 are illustrated. The improved visual appearance of the plated substrate (glossy metallic color rather than dull matte deposit) can be clearly illustrated in accordance with the method of the present invention.

實例5－在氯化可可烷基甲基[聚氧伸乙基(15)]銨中將來自CrClExample 5 - from CrCl in chlorinated cocoalkylmethyl [polyoxyethyl (15)] ammonium chloride 33 六水合物鹽之鉻電鍍至碳鋼上Chrome plating of hexahydrate salt onto carbon steel

將氯化鉻(III)六水合物鹽添加至含有0.2重量%水之氯化可可烷基甲基[聚氧伸乙基(15)]銨離子液體中，且將該混合物於約50℃之溫度下攪動，直至固體鹽溶解。在所製備之溶液中，氯化鉻(III)六水合物之濃度為75 g/kg。The chromium (III) chloride hexahydrate salt is added to a chlorinated cocoalkylmethyl [polyoxyethyl (15)] ammonium ionic liquid containing 0.2% by weight of water, and the mixture is at about 50 ° C. Stir at temperature until the solid salt dissolves. In the prepared solution, the concentration of chromium (III) chloride hexahydrate was 75 g/kg.

將約250 ml該溶液倒入如實例1中所述之哈氏槽中。將該槽加熱至70℃與80℃之間的溫度。Approximately 250 ml of this solution was poured into a Hastelloy bath as described in Example 1. The tank was heated to a temperature between 70 ° C and 80 ° C.

將鍍鉑鈦板用作陽極，且連接至直流電源之正極端子；而將碳鋼用作陰極(基板)，且連接至負極端子。使用市售去污粉清潔該基板，依次在脫礦質水、丙酮中且之後在乙醇中且最終在4 M－HCl水溶液中洗滌，隨後將其導入該浴中。當將兩板均連接且導入該槽中時，將電壓差設定為30 V。使用中心定位頂伸式葉輪攪拌該液體。在串聯之儀錶上監視電極之間的電流。A platinized titanium plate was used as the anode and connected to the positive terminal of the direct current power source; carbon steel was used as the cathode (substrate) and connected to the negative terminal. The substrate was cleaned using commercially available soil release powder, followed by demineralized water, acetone and then in ethanol and finally in 4 M-HCl aqueous solution, which was then introduced into the bath. When both boards are connected and introduced into the slot, the voltage difference is set to 30 V. The liquid is agitated using a centrally located overhead impeller. Monitor the current between the electrodes on a series connected meter.

在18小時之電鍍後，將陰極與電源之連接斷開，且自槽中取出。將該板在水及丙酮中洗滌，接著將其乾燥。藉由掃描電子顯微鏡組合以X－射線散射(SEM/EDX)對該基板進行化學分析。對於該板之浸沒部分及未浸沒部分均進行分析。在未浸沒部分上僅發現鐵、碳及氧，而浸沒部分含有鉻、鐵、碳及氧，從而確認鉻於基板上之沈積。除此之外，可目視觀測到該板浸沒部分上由金屬層覆蓋。After 18 hours of plating, the cathode was disconnected from the power source and removed from the tank. The plate was washed in water and acetone and then dried. The substrate was subjected to chemical analysis by X-ray scattering (SEM/EDX) by scanning electron microscope combination. The immersed and unimmersed portions of the panel were analyzed. Only iron, carbon and oxygen were found on the unimmersed portion, while the immersed portion contained chromium, iron, carbon and oxygen to confirm the deposition of chromium on the substrate. In addition to this, it was visually observed that the immersed portion of the plate was covered with a metal layer.

實例6－鉻源將鉻電鍍至碳鋼上Example 6 - Chromium source plating chromium onto carbon steel

將無水氯化鉻(II)添加至含有0.2重量%水之氯化可可烷基甲基[聚氧伸乙基(15)]銨離子液體中，且將該混合物於約50℃之溫度下攪動，直至可認為固體鹽已溶解。在所製備之溶液中，氯化鉻(II)之濃度為30 g/kg。Anhydrous chromium (II) chloride is added to a chlorinated cocoalkylmethyl [polyoxyethyl (15)] ammonium ionic liquid containing 0.2% by weight of water, and the mixture is agitated at a temperature of about 50 ° C. Until the solid salt is considered to have dissolved. In the prepared solution, the concentration of chromium (II) chloride was 30 g/kg.

將約250 ml該溶液倒入如實例1中所述之哈氏槽中。將該槽加熱至70℃與80℃之間的溫度。Approximately 250 ml of this solution was poured into a Hastelloy bath as described in Example 1. The tank was heated to a temperature between 70 ° C and 80 ° C.

將鍍鉑鈦板用作陽極，且連接至直流電源之正極端子；而將碳鋼用作陰極(基板)，且連接至負極端子。使用市售去污粉清潔該基板，依次在脫礦質水、丙酮中且之後在乙醇中且最終在4 M－HCl水溶液中洗滌，隨後將其導入該浴中。當將兩板均連接且導入該槽中時，將電壓差設定為30 V。使用中心定位頂伸式葉輪攪拌該液體。在串聯之儀錶上監視電極之間的電流。A platinized titanium plate was used as the anode and connected to the positive terminal of the direct current power source; carbon steel was used as the cathode (substrate) and connected to the negative terminal. The substrate was cleaned using commercially available soil release powder, followed by demineralized water, acetone and then in ethanol and finally in 4 M-HCl aqueous solution, which was then introduced into the bath. When both boards are connected and introduced into the slot, the voltage difference is set to 30 V. The liquid is agitated using a centrally located overhead impeller. Monitor the current between the electrodes on a series connected meter.

在18小時之電鍍後，將陰極與電源之連接斷開，且自槽中取出。將該板在水及丙酮中洗滌，接著將其乾燥。在該板於電鍍期間浸沒於離子液體中的部分上，觀測到淺藍灰色金屬沈積層覆蓋95%以上之區域。藉由掃描電子顯微鏡組合以X－射線散射(SEM/EDX)對該基板進行化學分析。對於該板之浸沒部分及未浸沒部分均進行分析。在未浸沒部分上發現鐵、碳及氧，而浸沒部分含有鉻、鐵及碳，從而確認鉻於基板上之沈積。After 18 hours of plating, the cathode was disconnected from the power source and removed from the tank. The plate was washed in water and acetone and then dried. On the portion of the plate that was immersed in the ionic liquid during electroplating, it was observed that the light blue-gray metal deposition layer covered more than 95% of the area. The substrate was subjected to chemical analysis by X-ray scattering (SEM/EDX) by scanning electron microscope combination. The immersed and unimmersed portions of the panel were analyzed. Iron, carbon and oxygen were found on the unimmersed portion, while the immersed portion contained chromium, iron and carbon to confirm the deposition of chromium on the substrate.

實例7－在含水甲硫酸可可烷基甲基[聚氧伸乙基(15)]銨中使用CrClExample 7 - Use of CrCl in aqueous cocoalkylmethylsulfate [polyoxyethyl (15)] ammonium 33 六水合物作為鉻源將鉻電鍍至碳鋼上Phosphate is electroplated onto carbon steel as a source of chromium

在添加鉻鹽之前將10重量%水導入甲硫酸可可烷基甲基[聚氧伸乙基(15)]銨離子液體中，隨後將氯化鉻(III)六水合物裝入該離子液體中。在約50℃之溫度下攪動該混合物，直至固體鹽溶解。在所製備之溶液中，氯化鉻(III)六水合物之濃度為74 g/kg。Introducing 10% by weight of water into a cocoamethylmethylsulfate methyl [polyoxyethylidene (15)] ammonium ionic liquid prior to the addition of the chromium salt, followed by charging the chromium (III) hexahydrate into the ionic liquid . The mixture was agitated at a temperature of about 50 ° C until the solid salt dissolved. In the prepared solution, the concentration of chromium (III) chloride hexahydrate was 74 g/kg.

將約250 ml該溶液倒入如實例1中所述之哈氏槽中。將該槽加熱至70℃與80℃之間的溫度。Approximately 250 ml of this solution was poured into a Hastelloy bath as described in Example 1. The tank was heated to a temperature between 70 ° C and 80 ° C.

將鍍鉑鈦板用作陽極，且連接至直流電源之正極端子；而將碳鋼用作陰極(基板)，且連接至負極端子。使用市售去污粉清潔該基板，依次在脫礦質水、丙酮中且之後在乙醇中且最終在4 M－HCl水溶液中洗滌，隨後將其導入該浴中。當將兩板均連接且導入該槽中時，將電壓差設定為30 V。使用中心定位頂伸式葉輪攪拌該液體。在串聯之儀錶上監視電極之間的電流。A platinized titanium plate was used as the anode and connected to the positive terminal of the direct current power source; carbon steel was used as the cathode (substrate) and connected to the negative terminal. The substrate was cleaned using commercially available soil release powder, followed by demineralized water, acetone and then in ethanol and finally in 4 M-HCl aqueous solution, which was then introduced into the bath. When both boards are connected and introduced into the slot, the voltage difference is set to 30 V. The liquid is agitated using a centrally located overhead impeller. Monitor the current between the electrodes on a series connected meter.

在5小時之電鍍後，將陰極與電源之連接斷開，且自槽中取出。將該板在水及丙酮中洗滌，接著將其乾燥。藉由掃描電子顯微鏡組合以X－射線散射(SEM/EDX)對該基板進行化學分析。對於該板之浸沒部分及未浸沒部分均進行分析。在未浸沒部分上發現鐵、碳及氧，而浸沒部分含有鉻、鐵、碳及氧，從而確認鉻於基板上之沈積。After 5 hours of plating, the cathode was disconnected from the power source and removed from the tank. The plate was washed in water and acetone and then dried. The substrate was subjected to chemical analysis by X-ray scattering (SEM/EDX) by scanning electron microscope combination. The immersed and unimmersed portions of the panel were analyzed. Iron, carbon and oxygen were found on the unimmersed portion, while the immersed portion contained chromium, iron, carbon and oxygen to confirm the deposition of chromium on the substrate.

實例8－在氯化可可烷基甲基[聚氧伸乙基(15)]銨中使用乙醯基丙酮酸鉻(III)作為鉻源將鉻電鍍至碳鋼上Example 8 - Electroplating of chromium onto carbon steel using chromium (III) acetoxypyruvate as chromium source in chlorinated cocoalkylmethyl [polyoxyethyl (15)] ammonium chloride

將乙醯基丙酮酸鉻(III)(97%，購自Acros)添加至含有0.2重量%水之氯化可可烷基甲基[聚氧伸乙基(15)]銨離子液體中，且將該混合物於約50℃之溫度下攪動，直至可認為固體鹽已溶解。在所製備之溶液中乙醯基丙酮酸鉻(III)之濃度為10 g/kg。Chromium (III) acetoxypyruvate (97%, purchased from Acros) was added to a chlorinated cocoalkylmethyl [polyoxyethyl (15)] ammonium ionic liquid containing 0.2% by weight of water, and The mixture is agitated at a temperature of about 50 ° C until the solid salt is considered to have dissolved. The concentration of chromium (III) acetyl phthalate in the prepared solution was 10 g/kg.

將約250 ml該溶液倒入如實例1中所述之哈氏槽中。將該槽加熱至70℃與80℃之間的溫度。Approximately 250 ml of this solution was poured into a Hastelloy bath as described in Example 1. The tank was heated to a temperature between 70 ° C and 80 ° C.

將鍍鉑鈦板用作陽極，且連接至直流電源之正極端子；而將碳鋼用作陰極(基板)，且連接至負極端子。使用市售去污粉清潔該基板，依次在脫礦質水、丙酮中且之後在乙醇中且最終在4 M－HCl水溶液中洗滌，隨後將其導入該浴中。當將兩板均連接且導入該槽中時，將電壓差設定為30 V。使用中心定位頂伸式葉輪攪拌該液體。在串聯之儀錶上監視電極之間的電流。A platinized titanium plate was used as the anode and connected to the positive terminal of the direct current power source; carbon steel was used as the cathode (substrate) and connected to the negative terminal. The substrate was cleaned using commercially available soil release powder, followed by demineralized water, acetone and then in ethanol and finally in 4 M-HCl aqueous solution, which was then introduced into the bath. When both boards are connected and introduced into the slot, the voltage difference is set to 30 V. The liquid is agitated using a centrally located overhead impeller. Monitor the current between the electrodes on a series connected meter.

在5小時之電鍍後，將陰極與電源之連接斷開，且自槽中取出。將該板在水及丙酮中洗滌，接著將其乾燥。藉由掃描電子顯微鏡組合以X－射線散射(SEM/EDX)對該基板進行化學分析。對於該板之浸沒部分及未浸沒部分均進行分析。在未浸沒部分上發現鐵、碳及氧，而浸沒部分含有鉻、鐵、碳及氧，從而確認鉻於基板上之沈積。After 5 hours of plating, the cathode was disconnected from the power source and removed from the tank. The plate was washed in water and acetone and then dried. The substrate was subjected to chemical analysis by X-ray scattering (SEM/EDX) by scanning electron microscope combination. The immersed and unimmersed portions of the panel were analyzed. Iron, carbon and oxygen were found on the unimmersed portion, while the immersed portion contained chromium, iron, carbon and oxygen to confirm the deposition of chromium on the substrate.

實例9－在氯化可可烷基甲基[聚氧伸乙基(15)]銨中使用鉻陽極(鉻金屬晶片)作為鉻源將鉻電鍍至碳鋼上Example 9 - Electroplating of chromium onto carbon steel using a chromium anode (chromium metal wafer) as a chromium source in chlorinated cocoalkylmethyl [polyoxyethyl (15)] ammonium chloride

將約250 ml含有0.2重量%水之氯化可可烷基甲基[聚氧伸乙基(15)]銨離子液體倒入如實例1中所述之哈氏槽中。將該槽加熱至70℃與80℃之間的溫度。About 250 ml of a chlorinated cocoalkylalkylmethyl [polyoxyethyl (15)] ammonium ionic liquid containing 0.2% by weight of water was poured into a Hastelloy bath as described in Example 1. The tank was heated to a temperature between 70 ° C and 80 ° C.

將2 mm厚之鉻金屬晶片裝入鈦筐中。將該筐用作陽極，且連接至直流電源之正極端子；而將碳鋼用作陰極(基板)，且連接至負極端子。使用市售去污粉清潔該基板，依次在脫礦質水、丙酮中且之後在乙醇中且最終在4 M－HCl水溶液中洗滌，隨後將其導入該浴中。當將兩板均連接且導入該槽中時，將電壓差設定為30 V。使用中心定位頂伸式葉輪攪拌該液體。在串聯之儀錶上監視電極之間的電流。A 2 mm thick chrome metal wafer was placed in a titanium basket. The basket was used as an anode and connected to the positive terminal of the direct current power source; carbon steel was used as the cathode (substrate) and connected to the negative terminal. The substrate was cleaned using commercially available soil release powder, followed by demineralized water, acetone and then in ethanol and finally in 4 M-HCl aqueous solution, which was then introduced into the bath. When both boards are connected and introduced into the slot, the voltage difference is set to 30 V. The liquid is agitated using a centrally located overhead impeller. Monitor the current between the electrodes on a series connected meter.

在5小時之電鍍後，將陰極與電源之連接斷開，且自槽中取出。將該板在水及丙酮中洗滌，接著將其乾燥。藉由掃描電子顯微鏡組合以X－射線散射(SEM/EDX)對該基板進行化學分析。對於該板之浸沒部分及未浸沒部分均進行分析。在未浸沒部分上發現鐵、碳及氧，而浸沒部分含有鉻、鐵、碳及氧，從而確認鉻於基板上之沈積。After 5 hours of plating, the cathode was disconnected from the power source and removed from the tank. The plate was washed in water and acetone and then dried. The substrate was subjected to chemical analysis by X-ray scattering (SEM/EDX) by scanning electron microscope combination. The immersed and unimmersed portions of the panel were analyzed. Iron, carbon and oxygen were found on the unimmersed portion, while the immersed portion contained chromium, iron, carbon and oxygen to confirm the deposition of chromium on the substrate.

比較實例10－在雙(三氟甲基磺醯基)醯亞胺N－甲基－N－三辛基銨中將來自CrClComparative Example 10 - from CrCl in bis(trifluoromethylsulfonyl) quinone imine N-methyl-N-trioctyl ammonium 33 六水合物鹽之鉻電鍍至碳鋼上Chrome plating of hexahydrate salt onto carbon steel

重複實例5，但使用雙(三氟甲基磺醯基)醯亞胺N－甲基－N－三辛基銨離子液體(98%，購自Solvent Innovation)替代實例5中所用之氯化可可烷基甲基[聚氧伸乙基(15)]銨離子液體。Example 5 was repeated, but using bis(trifluoromethylsulfonyl) quinone imine N-methyl-N-trioctyl ammonium ionic liquid (98%, available from Solvent Innovation) instead of the chlorinated cocoa used in Example 5. Alkylmethyl [polyoxyethyl (15)] ammonium ionic liquid.

在18小時之電鍍後，將陰極與電源之連接斷開，且自槽中取出。將該板在水及丙酮中洗滌，接著將其乾燥。藉由掃描電子顯微鏡組合以X－射線散射(SEM/EDX)對該基板進行化學分析。對於該板之浸沒部分及未浸沒部分均進行分析。在該板之任何部分上均未發現鉻。因此，未發生可偵測之鉻沈積。在相同條件下且應用相同鉻源(實例5)的情況下，當使用本發明所涵蓋之氯化可可烷基甲基[聚氧伸乙基(15)]銨離子液體時則形成鉻沈積，清楚地展示根據本發明之方法的優勢。After 18 hours of plating, the cathode was disconnected from the power source and removed from the tank. The plate was washed in water and acetone and then dried. The substrate was subjected to chemical analysis by X-ray scattering (SEM/EDX) by scanning electron microscope combination. The immersed and unimmersed portions of the panel were analyzed. No chromium was found on any part of the board. Therefore, no detectable chromium deposits occurred. Under the same conditions and with the same chromium source (Example 5), chromium deposits are formed when using the chlorinated cocoalkylmethyl [polyoxyethyl (15)] ammonium ionic liquid covered by the present invention, The advantages of the method according to the invention are clearly shown.

比較實例11－在雙(三氟甲基磺醯基)醯亞胺N－甲基－N－三辛基銨中將來自CrClComparative Example 11 - from CrCl in bis(trifluoromethylsulfonyl) quinone imine N-methyl-N-trioctyl ammonium 22 之鉻電鍍至碳鋼上Chrome plating onto carbon steel

重複實例6，但使用雙(三氟甲基磺醯基)醯亞胺N－甲基－N－三辛基銨離子液體(98%，購自Solvent Innovation)替代實例6中所用之氯化可可烷基甲基[聚氧伸乙基(15)]銨離子液體。Example 6 was repeated, but using bis(trifluoromethylsulfonyl) quinone imine N-methyl-N-trioctyl ammonium ionic liquid (98%, available from Solvent Innovation) instead of the chlorinated cocoa used in Example 6. Alkylmethyl [polyoxyethyl (15)] ammonium ionic liquid.

在5小時之電鍍後，將陰極與電源之連接斷開，且自槽中取出。將該板在水及丙酮中洗滌，接著將其乾燥。藉由掃描電子顯微鏡組合以X－射線散射(SEM/EDX)對該基板進行化學分析。對於該板之浸沒部分及未浸沒部分均進行分析。在該板之任何部分上均未發現鉻。因此，未發生可偵測之鉻沈積。在相同條件下且應用相同鉻源(實例6)的情況下，當使用本發明所涵蓋之氯化可可烷基甲基[聚氧伸乙基(15)]銨離子液體時則形成鉻沈積，清楚地展示根據本發明之方法的優勢。After 5 hours of plating, the cathode was disconnected from the power source and removed from the tank. The plate was washed in water and acetone and then dried. The substrate was subjected to chemical analysis by X-ray scattering (SEM/EDX) by scanning electron microscope combination. The immersed and unimmersed portions of the panel were analyzed. No chromium was found on any part of the board. Therefore, no detectable chromium deposits occurred. Under the same conditions and with the same chromium source (Example 6), chromium deposits are formed when using the chlorinated cocoalkylmethyl [polyoxyethyl (15)] ammonium ionic liquid covered by the present invention, The advantages of the method according to the invention are clearly shown.

圖1a及圖1b展示藉由掃描電子顯微鏡組合以X－射線散射(SEM/EDX)對自實例2所得板之化學組份分析。1a and 1b show chemical composition analysis of the panels obtained from Example 2 by X-ray scattering (SEM/EDX) by scanning electron microscope combination.

圖2圖解說明實例2基板及比較實例4基板之外觀。2 illustrates the appearance of the substrate of Example 2 and the substrate of Comparative Example 4.

Claims (8)

一種電沈積金屬至基板上之方法，其中該電沈積為電鍍或電解拋光，且其中將式N+ R5 R6 R7 R8 Y- 的離子液體用作電解質，且將添加至該離子液體之金屬鹽用作金屬源，或將一金屬陽極用作該金屬源，其中R5 至R8 中之任一者獨立地代表氫、烷基、環烷基、芳基或芳烷基，該等基團可經選自OH、Cl、Br、F、I、苯基、NH2 、CN、NO2 、COOR9 、CHO、COR9 或OR9 之基團取代，且R5 至R8 中之至少一者為具有8至22個碳原子之飽和或不飽和烷基鏈，且R5 至R8 中之一或多者為(聚)氧基伸烷基，其中該伸烷基為C1 至C4 伸烷基且氧基伸烷基單元之總數可為1至50個氧基伸烷基單元，且R5 至R8 中之至少一者為C1 至C4 烷基鏈，R9 為烷基或環烷基，Y- 為與N+ R5 R6 R7 R8 銨陽離子相容之陰離子，諸如鹵化物陰離子、羧酸鹽陰離子、有機或無機硫酸根、磺酸根、碳酸根、硝酸根、亞硝酸根、硫氰酸根、氫氧根或磺醯基醯亞胺陰離子。A method of electrodepositing a metal onto a substrate, wherein the electrodeposition is electroplating or electrolytic polishing, and wherein an ionic liquid of the formula N + R 5 R 6 R 7 R 8 Y - is used as an electrolyte, and is added to the ionic liquid The metal salt is used as a metal source, or a metal anode is used as the metal source, wherein any one of R 5 to R 8 independently represents hydrogen, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. The group may be substituted with a group selected from OH, Cl, Br, F, I, phenyl, NH 2 , CN, NO 2 , COOR 9 , CHO, COR 9 or OR 9 and R 5 to R 8 At least one of them is a saturated or unsaturated alkyl chain having 8 to 22 carbon atoms, and one or more of R 5 to R 8 is a (poly)oxyalkylene group, wherein the alkylene group is C 1 The total number of alkyl groups and alkyloxyalkyl units to C 4 may be from 1 to 50 alkyloxyalkyl units, and at least one of R 5 to R 8 is a C 1 to C 4 alkyl chain, and R 9 is An alkyl or cycloalkyl group, Y - is an anion compatible with the N + R 5 R 6 R 7 R 8 ammonium cation, such as a halide anion, a carboxylate anion, an organic or inorganic sulfate, a sulfonate, a carbonate, Nitrate, nitrous acid , Thiocyanate, hydroxide or sulfo acyl acyl imide anion. 如請求項1之方法，其中Y- 係選自F- 、Cl- 、Br- 、I- 之群；R10 COO- 陰離子之群，其中R10 可為氫、C1 -C22 烷基、烯基或芳族基；R11 SO4 - 陰離子之群，其中R11 可為空缺(在陽離子為二價之情況下)、氫、C1 -C22 烷基、烯基或芳族基；R12 SO3 - 陰離子之群，其中R12 可不存在(在該情況下陽離子為二價)、氫、C1 -C22 烷基、烯基或芳族基； R13 CO3 - 陰離子之群，其中R13 可不存在(在該情況下陽離子為二價)、氫、C1 -C22 烷基、烯基或芳族基；及R14 -N- -SO2 -R15 陰離子之群，其中R14 及/或R15 獨立地可為氫、C1 -C22 烷基、烯基或芳族基，且R14 可經由羰基連接至氮原子。The method of claim 1, wherein the Y - is selected from the group consisting of F - , Cl - , Br - , I - , and the group of R 10 COO - anions, wherein R 10 is hydrogen, C 1 -C 22 alkyl, alkenyl or aromatic group; R 11 SO 4 - anion of the group, wherein R 11 may be a gap (in the case of a divalent cation of), hydrogen, C 1 -C 22 alkyl, alkenyl or aromatic group; R 12 SO 3 - anion of the group, wherein R 12 may be absent (in this case the cation is divalent), hydrogen, C 1 -C 22 alkyl, alkenyl or aromatic group; R 13 CO 3 - anions group Wherein R 13 may be absent (in this case the cation is divalent), hydrogen, C 1 -C 22 alkyl, alkenyl or aromatic; and a group of R 14 -N - -SO 2 -R 15 anions, Wherein R 14 and/or R 15 may independently be hydrogen, C 1 -C 22 alkyl, alkenyl or aromatic, and R 14 may be attached to the nitrogen atom via a carbonyl group. 如請求項2之方法，其中Y- 為Cl- 、Br- 或CH3 SO4 - 。The method of claim 2, wherein Y - is Cl - , Br - or CH 3 SO 4 - . 如請求項1至3中任一項之方法，其中該式N+ R5 R6 R7 R8 Y- 之離子液體具有1 g I2 /100 g離子液體以上之碘價。The method of any one of claims 1 to 3, wherein the ionic liquid of the formula N + R 5 R 6 R 7 R 8 Y - has an iodine value of 1 g I 2 /100 g ionic liquid or more. 如請求項1至3中任一項之方法，其中該離子液體之銨陽離子與該金屬鹽之金屬陽離子或源自該金屬陽極之金屬陽離子的莫耳比處於1,000：1與3：1之間。 The method of any one of claims 1 to 3, wherein the molar ratio of the ammonium cation of the ionic liquid to the metal cation of the metal salt or the metal cation derived from the metal anode is between 1,000:1 and 3:1 . 如請求項5之方法，其中該莫耳比處於100：1與7：1之間。 The method of claim 5, wherein the molar ratio is between 100:1 and 7:1. 如請求項1至3中任一項之方法，其中金屬鉻、鋁或銅中之一者被沈積。 The method of any one of claims 1 to 3, wherein one of the metallic chromium, aluminum or copper is deposited. 如請求項1至3中任一項之方法，其中該離子液體係選自下列化合物之群：氯化十八基甲基雙(2-羥基乙基)銨、硝酸可可雙(2-羥基乙基)甲基銨、氯化可可雙(2-羥基乙基)甲基銨、氯化可可雙(2-羥基乙基)苄基銨、氯化油基雙(2-羥基乙基)甲基銨、氯化可可[聚氧伸乙基(15)]甲基銨、甲硫酸可可[聚氧伸乙基(15)]甲基銨、氯化可可[聚氧伸乙基(17)]甲基銨、氯化十八基[聚氧伸乙基(15)]甲基銨及氯化氫化動物脂[聚氧伸乙基(15)]甲基銨。The method of any one of claims 1 to 3, wherein the ionic liquid system is selected from the group consisting of octadecylmethylbis(2-hydroxyethyl)ammonium chloride, cocoa nitric acid (2-hydroxyethyl) Methyl ammonium, chlorinated cocoa bis(2-hydroxyethyl)methylammonium chloride, cocoa bis(2-hydroxyethyl)benzylammonium chloride, chlorinated bis(2-hydroxyethyl)methyl Ammonium, chlorinated cocoa [polyoxy-extended ethyl (15)] methyl ammonium, methyl sulfate, cocoa [polyoxyethyl (15)] methyl ammonium, chlorinated cocoa [polyoxyethyl (17)] Alkyl ammonium, octadecyl chloride [polyoxyethyl (15)] methyl ammonium and hydrogenated tallow [polyoxyethyl (15)] methyl ammonium.
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