TW538133B

TW538133B - Process for producing plating solution for electroless platinum plating, plating solution for electroless platinum plating, and method of electroless platinum plating

Info

Publication number: TW538133B
Application number: TW90128927A
Authority: TW
Inventors: Katsutsugu Kitada
Original assignee: Tanaka Kikinozoku Kogyo Kk
Priority date: 2000-12-05
Filing date: 2001-11-22
Publication date: 2003-06-21
Also published as: WO2002046492A1; JP4463972B2; JP2002173780A

Abstract

A process for producing from a hexaaminoplatinum complex salt a plating solution for electroless platinum plating which contains the hexaaminoplatinum complex, is characterized by including a process for hexaaminoplatinum complex purification which comprises (a) a step in which an aqueous solution of a hexaaminoplatinum complex salt as a starting material is prepared and carbon dioxide is passed through the aqueous solution to produce the carbonate of the hexaaminoplatinum complex and (b) a step in which the hexaaminoplatinum complex carbonate is dissolved with an acid.

Description

538133538133

技術彳、可能製造高品質的係有關於使用此無電本發明係有關於有良好的安定性白金薄膜之無電解白金電鍍液。且，解白金電鍍液之白金電鍍方法。習知此無電解白金電鍍液，雖因其安定劑承認，但含有如此般的安定劑之電鍍液，補充電鍵液’則有分解產生之問題。因此用的電鍍操作係以分批處理作為基本的，操作並不適合，如此不能進行高效的電鍍一方面’作為比上述無電解白金電鍍好的’有在特開平5-222543號公報中所記電鑛液。此電鍍液係以一般式[pt ( NJJ3 ) ] 白金氨鹽為主要成分的，即使無安定劑，作為無電解白金電鍍液的’但此些的大多數因有關的實用化的可能性。又，盡決策略，但公開了充分的解昭5 9 - 3 3 6 6 7號公報中公開著位化合物或硝氨配位化合物了沒氨基鹽作為安定劑的無金電鍍液中，雖然聯氨有優液體組成的安定性之不利點選擇並添加了羥氨基鹽作為，至今雖然有幾個係眾所週知於安定性的問題，而沒有足夠管對於此安定性問題提出了解決策略的還很少。例如，特公 ’作為白金離子，含有硝基配，以聯氨作為還原劑，且添加電解白金電鍍液。此無電解白良的還原作用，從著眼於降低，作為其安定性的改善策略，安定劑。的暫時效果而被若在電鍍操作中 ’此電鍍液所適對於連續的電鍍處理。液之安定性更良載的無電解白金所表示的、4價在連續的電錢處Technology: It is possible to produce high quality. This invention relates to the use of this electroless. The present invention relates to an electroless platinum plating solution that has good stability for platinum films. In addition, the platinum plating method of the platinum plating solution is solved. It is known that although this electroless platinum plating solution is recognized because of its stabilizer, a plating solution containing such a stabilizer and a supplementary keying fluid 'have problems caused by decomposition. Therefore, the plating operation used is based on batch processing, and the operation is not suitable. Therefore, efficient plating cannot be performed. On the one hand, it is better than the electroless platinum plating described above in Japanese Unexamined Patent Publication No. 5-222543. Mineral fluid. This plating solution is based on the general formula [pt (NJJ3)] platinum ammonia salt as the main component, and even if it does not have a stabilizer, it is used as an electroless platinum plating solution. However, most of these are due to the possibility of practical application. In addition, due to decisive strategies, a sufficient solution is disclosed in the publication No. 5 9-3 3 6 6 7 in which a chalcogenide compound or a nitramine complex is disclosed in a gold-free plating solution containing an amino salt as a stabilizer. The disadvantages of stability of ammonia with excellent liquid composition have been selected and added as hydroxyamino salts. Although there are several systems that are well-known for stability problems, there are not enough tubes to put forward solutions to this stability problem. . For example, as the platinum ion, nitrogen is contained, hydrazine is used as a reducing agent, and an electrolytic platinum plating solution is added. The reduction effect of this non-electrolytic white is focused on the reduction, as a stabilizer for improving its stability. The temporary effect of the electroplating solution is suitable for continuous electroplating treatment. The stability of the liquid is better, and the price of the electroless platinum is 4 yuan.

2l69-4495-PF(N) ;Chiumeow.ptd2l69-4495-PF (N); Chiumeow.ptd

8133 發明說明（2) 用此電鍍液，玎很良好，被認為載的無電解白金等預先進行了實分解，電鍍槽的。因此，此無電度控制之白金薄擴大，從至今的導體裝置的電容 3而且，為了用金薄膜，習知的安定的、優良的，以提供安定性品質薄膜之無電此電鍍液的電鍍理時，亦可進行安定的白金電鍍。又，利製造咼品質的白金薄膜，且由於其光澤亦也可適用於裝飾品的電鍍。然而’特開平5 - 2 2 2 5 4 3號公報中所記電鍍液，其安定性不一定足夠，本發明人驗，確認此習知的電鍍液不能完全地抑制壁面上有白金析出，使膜厚控制變得困難解白金電鍍液被認為，對於需要嚴密的厚膜製造係不合適的。近年，白金般的貴金屬的用途不段地裝飾品、催化劑、耐熱材料等用途，到半器-電極之尖端技術領域的利用被期待著無電解電鍍製造如此般的領域中使用的白無電解電鍍液無法照舊使用，期待開發更無電解白金電鍍液。一本發明係在卩上所述的f景下完成的極兩、可連續進行電鍍操作的、可製造高解白金電鍍液為目的。並，以提供利用方法為目的。發明概沭本發明者對上述以六氨基白金配位化合物（[pt (N扎） X])為主要成分的無電解白金電鍍液之安定性進行評價的同日守，更對需提高其安定性進行了詳細的研討。其結果，此電鍍液雖係以4價的六氨基白金配位化合物為主要成8133 Description of the invention (2) With this plating solution, 玎 is very good, and it is considered that the electroless platinum and the like contained in the plating solution have been decomposed in advance, and the plating bath is used. Therefore, the platinum thickness of this electroless control has been expanded from the capacitors of conductor devices until today. Moreover, in order to use gold thin films, the conventionally stable and excellent ones are used to provide stable quality thin films without electroplating. It can also perform stable platinum plating. In addition, it is suitable for the manufacture of high-quality platinum thin films, and is also suitable for plating of decorative articles due to its gloss. However, the stability of the plating solution described in JP-A No. 5-2 2 2 5 4 3 may not be sufficient, and the inventors have verified that the conventional plating solution cannot completely suppress the precipitation of platinum on the wall surface, so that It is difficult to control the thickness of the film, and it is considered that the solution for platinum plating is not suitable for a thick film manufacturing system that requires strictness. In recent years, the use of platinum-like precious metals has been inexhaustible in decorations, catalysts, and heat-resistant materials. The use of advanced technology in the half-electrode field is expected. Electroless plating is expected to produce white electroless plating used in such fields. The liquid cannot be used as usual, and the development of a more electroless platinum plating solution is expected. An object of the present invention is to complete the two poles described in the above-mentioned scene, which can be used for continuous plating operations, and to produce a high-resolution platinum plating solution. And, the purpose is to provide utilization methods. Summary of the Invention The present inventors evaluated the stability of the above-mentioned electroless platinum plating solution containing hexaamino platinum complex compound ([pt (Nz) X]) as the main component, and also required the stability to be improved. Conducted a detailed discussion. As a result, although this plating solution is mainly composed of a tetravalent hexaamino platinum complex compound,

2169-4495-PF(N) ； Chiumeow.ptd $ 5頁 538133 明(3) " ' 分’但被發現含有下述般的不純物。 ϋ [Pt Cl (a)5]3+ [Pt Cl2 (a)4F [pt Cl3 (a)3] + [Pt (a)4]2+ 如此般的，在不純物成為原料的六氨基白金配位化合、之製造步驟中，雖被認為係在電鍍液的調製過程中產生，丄因為與主要成分的六氨基白金配位化合物相比，缺乏 f定性，所以在溶液中分解，而產生白金微粒子（容易附者於電鍍槽的壁面或被電鍍物）。且，由於此白金微粒子 1催化作用，促進電鍍槽的壁面或被電鍍物之電鍍部分以外的地方有白金析出。、/至此’本發明人等為了提高此電鍍液的安定性，認為頁排除上述不純物，因此，在電鍍液的製造步驟中，適 §地預先精製六氨基白金配位化合物。而且，作為其具體、手法使原料的六氨基白金配位化合物成為水溶液，對此/谷液吹入二氧化碳氣體，一旦製造以精製為目的的六氨基白金配位化合物之碳酸鹽，然後抽取六氨基白金配位化口物。如此般地，使之一旦與二氧化碳氣體反應，碳酸離子對於精製目的的六氨基白金配位化合物之反應性及選擇性良好，藉此，可高純度地抽取六氨基白金配位化合物，此做法係基於以上的想法。即是’本發明係有關於無電解白金電鍍液之製造方法2169-4495-PF (N); Chiumeow.ptd $ 5 538133 Ming (3) "quot" but found to contain the following impurities. ϋ [Pt Cl (a) 5] 3+ [Pt Cl2 (a) 4F [pt Cl3 (a) 3] + [Pt (a) 4] 2+ In this way, the impurity becomes the raw material of the hexaamino platinum complex Although it is thought that it is generated during the preparation of the plating solution during the compounding and manufacturing steps, because of its lack of f qualitative properties compared to the main component of the hexaamino platinum complex, it decomposes in the solution to produce platinum fine particles ( Easy to attach to the wall surface of the plating tank or to be plated). In addition, due to the catalytic action of the platinum fine particles 1, platinum is precipitated out of the wall surface of the plating bath or outside the plated part of the plating object. To this end, in order to improve the stability of this plating solution, the present inventors believe that the above-mentioned impurities are excluded from the page. Therefore, in the manufacturing process of the plating solution, the hexaamino platinum complex compound is appropriately purified in advance. In addition, as a specific method, the hexaamino platinum complex compound as a raw material is made into an aqueous solution, and carbon dioxide gas is blown into the valley liquid, once the carbonate of the hexaamino platinum complex compound for the purpose of purification is manufactured, and then the hexaamino group is extracted. Platinum complexes. In this way, once it reacts with carbon dioxide gas, the carbonic acid ion has good reactivity and selectivity for the hexaamino platinum complex compound for purification purpose, and thus, the hexaamino platinum complex compound can be extracted with high purity. Based on the above ideas. That is, the present invention relates to a method for manufacturing an electroless platinum plating solution.

2i69-4495-PF(N) ； Chiumeow.ptd 第6頁 538133 五發明說明（4) 合ίΠί於在：下述一般式所表示的六氨基白金配位化白金電鍍液之製造方法中，纟有以下物之無電：六氨基白金配位化合物之精製過程。所顯不的 ^2 [Pt (a)6 ]4+ 氨基（=巾’ a係顯示C人+ιΝΗ2(η係〇〜1〇的整數）所表示的二氧(化m*?六氨基白金配位化合物作成水溶液，使舲Μ山人體通過上述水溶液，製造六氨基白全配位化入物的碳酸鹽之步驟。 4配位化口步驟用I /谷解上述六氨基白金配位化合物的碳酸鹽之以下，對作為本發明特徵之精製步驟進行說明。物作i t::精製步驟中，f先，將六氨基白金配位化合使用贵二:t。於此，作為六氨基白金配位化合物，最好體反i、=占山L此係因為氫氧化物，在其後與二氧化碳氣 :生成奴酸鹽的過程中，不純物的共沉澱最少。一方作成水溶液時，六氨基白金配位化合物的溶解，用=金換算lg/L〜20g/L。因為若不滿ig/L，則 ^^足夠里的碳酸鹽，此外，效率也不良。但是，若起過20g/L，則鹽不溶解。、欠洛液σ人入一氧化碳氣體，使碳酸鹽沉殿。關於一氧化碳氣體的吹入量，雖因水溶液中六2i69-4495-PF (N); Chiumeow.ptd Page 6 538133 Five invention descriptions (4) In the following: In the method for producing a hexaamino platinum complexed platinum plating solution represented by the following general formula, there is no The following are non-electrical: Refining process of hexaamino platinum complex. ^ 2 [Pt (a) 6] 4+ amino group (= 'a' shows a dioxin (chemical m *? Hexaamino platinum) represented by C-person + ιΝΗ2 (η is an integer from 0 to 10) The step of preparing the complex compound as an aqueous solution and passing the human body through the above aqueous solution to produce carbonate of the hexaamino white fully complexed compound. 4 The complexation step uses I / Valley to dissolve the hexaamino platinum complex The following is a description of the purification step which is a feature of the present invention with respect to carbonate. In the refining step, f: first, the hexaamino platinum is coordinated to use Gui 2: t. Here, as the hexaamino platinum coordination Compounds, preferably anti-i, = Zhanshan L. This is because the hydroxide, in the subsequent process with carbon dioxide gas: the formation of sulfanoate, the co-precipitation of impurities is the least. When one side is made into an aqueous solution, hexaamino platinum is coordinated. For the dissolution of the compound, lg / L ~ 20g / L is converted into gold. Because if it is less than ig / L, carbonate is sufficient, and the efficiency is also poor. However, if it exceeds 20g / L, the salt will not change. Dissolve. 欠 The Luo liquid σ enters the carbon monoxide gas, which makes the carbonate sink. The amount of gas blown, six was by an aqueous solution

538133 異，作為其標準，則一性為好。六氨基白金配位化合物的不含有不純物的高純〇用於白金電鍍的六氨基酸鹽溶解。此處，作為酸類，雖亦可使碳酸鹽液中_素會殘留，此鹵出速度，且使薄膜的外 ’則生成硫酸鹽，硝酸五、發明說明（5) 氨基白金配直吹入二氧藉以上作為碳酸鹽度六氨基白接著，白金配位化使碳酸鹽溶溶解，但使素將吸附於觀變黑。又亦有使薄膜因此，石黃酸等的有酸。且，此酸後的溶液最好先除去溶解於上述解時使溶液經過此配位化合物可原封不動化合物的濃為與本發明位化合物溶化碳氣體，的操作，使沉澱。此碳金配位化合必須從此碳合物之離子解的酸，鹽用此些酸的電鍍薄膜， ’同樣地，的外觀惡化作為本發明機續酸，或些酸係以水中’碳酸離碳酸離子。有機續酸或處於減壓氣些精製步驟溶液。而且 &作為無電度成所定的有關的無電液之濃度而至溶液呈中水溶液中的酸鹽係上述物之碳酸鹽酸鹽中抽取，用酸使碳酸等的鹵素場合，溶解不僅降低析若使用硫酸的問題。中適用的酸乙酸、丙酸溶液的狀態子仍殘留著做為此碳酸有機羧酸等氛中，可容後的水溶液，此六氨基解白金電鍍濃度，可適解白金電鍍 ’最好使用等的低分子添加。又，，所以製造的除去方法酸時，因產易地除去碳係高純度之白金配位化液使用，為當地稀釋，液0 曱磺酸、乙量的有機羧由於添加此電鍍液時，，將碳酸鹽生C 02，溶酸離子。六氨基白金合物溶液雖使白金配位藉此使之成 Η 2169-4495-PF(N) ； Chiumeow.ptd 第8頁538133 difference, as its standard, one is better. High purity of hexaamino platinum complex compound containing no impurities. ○ Hexaminate for platinum plating is dissolved. Here, as an acid, it is possible to make _ element remain in the carbonate solution, this halogenation rate, and the outside of the film will generate sulfate, nitric acid V. Description of the invention (5) Amino platinum with straight blowing into two Oxygen is used as the carbonate to the degree of hexaamino white. Then, the platinum is coordinated to dissolve the carbonate, but the element will be adsorbed on the surface and become black. There are also acids that make films, such as lutein. Moreover, the solution after the acid is preferably removed first, and the solution is allowed to pass through the complex compound when dissolved in the above solution. The concentration of the compound can be left intact, and the carbon gas is dissolved with the compound of the present invention to precipitate. This carbon-gold complex must be an acid that decomposes from the ions of this carbide. Salts are plated with these acids. 'Similarly, the appearance deteriorates as the organic acid of the present invention, or some acids are carbonated in water.' ion. Organic continuous acid or some refining solution under reduced pressure. In addition, & is extracted from the carbonate of the above-mentioned acid salt in the aqueous solution as the electroless liquid at a predetermined concentration of the electroless liquid, and the dissolution of the halogen such as carbonic acid with an acid will not only reduce the analysis if Problems using sulfuric acid. Applicable acidic acetic acid and propionic acid solution state remains as a solution that can be contained in the atmosphere of carbonic acid, organic carboxylic acid and the like. This hexaamino solution platinum plating concentration can be used to resolve platinum plating. Of low molecular weight. In addition, when the acid is removed by the manufacturing method, it is used to easily remove the carbon-based high-purity platinum complexing solution, which is locally diluted. When the plating solution is added with the amount of organic carboxylic acid of 0 sulfonic acid and B, , Carbonate will be C 02, dissolve acid ions. Hexaamino platinum solution Although platinum is coordinated to make it into Η 2169-4495-PF (N); Chiumeow.ptd page 8

538133 五、發明說明（6) 在此，對於與本發明有關的無電解白金電鍍液，最好適當地添加還原劑。作為此還原劑，次磷酸、磷酸、聯氨、氫化硼、甲醛水、L-抗壞血酸、甲酸等可適用。這些原劑的濃度最好係電鍍液中的白金離子濃度（莫耳濃度^之卜10倍。 X 、 /又又，與本發明有關的電鍍液雖可能製造高精度的薄臈，但為了製造形態良好的、無凹痕的白金薄添加鍍平劑。此處，由於鍍平劑亦可適用於一'般的、白金以外的無電解電鍍液，這種情形下，陽離子活劑較適用。然而，作為本發明的製造目的之白金薄膜，容易吸附此些介面活性劑中的有機物，使析出速度降低’ 在有些場合甚至使析出中斷。且’在添加此些介面活性時，會有不溶性的沉澱物產生。因此，作為本發明的I 解電，液之鑛平劑’最好使用聚環氧乙燒喊、聚烧基苯醚、聚壤氧乙烷-裱氧丙烷醚、甘油脂、聚甘油脂、山醇酐酯等的非離子系介面活性劑。$些鍍度最係0· ；1〜lOOppm。又取戈t 根據與本發明有關的無電解白金電鍍液，盔解產生的、可能進行安定的白金電鍍處理，具 ' = 梯覆蓋的同時，可製造高精度的白金薄膜。而且，用二本發明有關的無電解白金電鍍液進行白金電鍍了 pH 8〜12、液溫40〜8〇°C為條件。關於PH，若pH未滿8，子以因為白金無法析出，而pH超過丨2，則係因為操作产亞化。又，關於液溫，若未滿4〇它，係因為白金無法衣析兄w 第9頁 2169-4495-PF(N) > Chiumeow.ptd 538133 五、發明說明（7) 而超過8 0 °C，則係因為電鍍液中胺的蒸發變得顯著。而且’在調整此電鑛液的pH時，雖係向電鐘液中添加酸或驗’添加鹼時，最好適用含有與在六氨基白金配位化合物中、對白金配位著的氨基（化3的a)相同的氨基之鹼。實施發明的最佳^態以下’共同說明本發明適當的實施形態與比較例。皇1實施形H ••準備白金濃度為10g/L的[Pt(NHQ) 〇 ^ 叫（0H)4溶液5L，將二氧化碳氣體對著此溶液吹入3小時。且’將沉澱的碳酸鹽過濾提取後，將其洗淨、乾燥。接著，將此碳酸鹽秤量，使之含有白金3Og，對此添加乙酸 45mL，使碳酸鹽溶解，再加水使溶液量成il後，將溶解後的溶液減壓而除去碳酸。如此般地，從精製了的六氨基白金配位化合物溶液 ([Pt(NH3)6] (CHsCOO)4溶液）中，提取白金量3g分的溶液 (1 0 0 m L)’對此添加聯氨-水合物3 m L作為還原劑，並添加 2 8%的氨水70 mL，使溶液的pH成pH 11後，添加無離子水至溶液量成1 L。另外，添加20ppm的甘油脂作為鍍平劑。以上般地，使製造的無電解白金電鍍液保持液溫6 〇 ^ ，對此浸潰施行了催化附與處理的氧化鋁板，以進行白金電鍍處理。其結果，光澤良好的白金以1. 8 /zm/h的析出速度析出。又，雖將此電鍍處理後的電鍍液放置1週，確％無電鍍液分解的產生。 ~ 第2實施形態:準備白金濃度為10g/L的[Pt(NH3)] (OH)4溶液5L，將二氧化破氣對著此溶液吹入3小時。且，538133 V. Description of the invention (6) Here, it is preferable to appropriately add a reducing agent to the electroless platinum plating solution related to the present invention. As this reducing agent, hypophosphorous acid, phosphoric acid, hydrazine, boron hydride, formaldehyde water, L-ascorbic acid, formic acid, and the like are applicable. The concentration of these original agents is preferably the platinum ion concentration in the plating solution (10 times the molar concentration). X, and again, although the electroplating solution related to the present invention may produce high-precision thin slabs, A flat, thin, non-pitched platinum is added with a plating agent. Here, since the plating agent can also be applied to a general electroless plating solution other than platinum, in this case, a cationic activator is more suitable. However, the platinum thin film, which is the manufacturing purpose of the present invention, easily adsorbs organic substances in these interfacial active agents and reduces the precipitation rate. In some cases, the precipitation is even interrupted. And, when these interfacial activities are added, there will be insoluble Precipitates are produced. Therefore, as the solution of I in the present invention, the liquid leveling agent 'is best to use polyethylene oxide, polyphenylene oxide, polyoxyethylene-epoxypropane ether, glycerolipid, Non-glyceride surfactants such as polyglycerol esters and behenyl anhydride esters. The most suitable plating degree is 0 ·; 1 ~ 100ppm. Also take Get according to the electroless platinum plating solution related to the present invention. Stable Gold plating treatment, with '= ladder cover, can produce high-precision platinum thin film. Moreover, the electroless platinum plating solution according to the present invention is used for platinum plating with a pH of 8 to 12, and a liquid temperature of 40 to 80 ° C. For the pH, if the pH is less than 8, the platinum cannot be precipitated because of platinum, and the pH is higher than 2, it is because of sub-chemical operation. Moreover, if the liquid temperature is less than 40, it is because platinum cannot be used. Yi Yixiong w Page 9 2169-4495-PF (N) > Chiumeow.ptd 538133 V. Description of the invention (7) Above 80 ° C, it is because the evaporation of amine in the plating solution becomes significant. And ' When adjusting the pH of this electric mineral liquid, although adding acid or adding alkali to the electric clock liquid, it is best to apply an amino group (chemically complexed with platinum) that contains a hexaamino platinum complex compound. A) The base of the same amino group. The best embodiment for carrying out the invention The following descriptions together describe suitable embodiments and comparative examples of the invention. Example 1 H •• Prepare [Pt (NHQ) with a platinum concentration of 10 g / L 〇 ^ Called (0H) 4 solution 5L, blowing carbon dioxide gas against this solution for 3 hours. After the carbonate was filtered and extracted, it was washed and dried. Then, this carbonate was weighed to contain 30 g of platinum, 45 mL of acetic acid was added to dissolve the carbonate, and water was added to make the solution into il, and then dissolved. The subsequent solution was depressurized to remove carbonic acid. In this manner, a solution (1 0) of 3 g of platinum was extracted from the purified hexaamino platinum complex solution ([Pt (NH3) 6] (CHsCOO) 4 solution). 0 m L) 'To this was added 3 ml of hydrazine-hydrate as a reducing agent, and 70 mL of 28% ammonia water was added to make the pH of the solution to pH 11, and then deionized water was added to the solution to 1 L. In addition, 20 ppm of glycerol was added as a leveling agent. In the above manner, the manufactured electroless platinum plating solution was maintained at a liquid temperature of 60 ^, and the alumina plate subjected to catalytic adhesion treatment was immersed in the impregnation to perform platinum plating treatment. As a result, platinum having a good gloss was precipitated at a precipitation rate of 1.8 / zm / h. In addition, although the plating solution after this plating treatment was left for one week, it was confirmed that there was no occurrence of decomposition of the plating solution. ~ 2nd Embodiment: Prepare 5 L of a [Pt (NH3)] (OH) 4 solution with a platinum concentration of 10 g / L, and blow in the dioxide gas against this solution for 3 hours. And

2169-4495-PF(N) ； Chiumeow.ptd 第10頁 538133 五、發明說明（8) 將沉殿的碳酸鹽過濾、提取後’將其洗淨、乾燥。接著，對此碳酸鹽添加甲績酸5 0 m L，使碳酸鹽溶解，再加水使溶液量成1 L後，從溶液中除去碳酸。如此般地，從白金配位化合物溶液中，提取白金量3 g 分的溶液（1 00mL)，對此添加聯氨-水合物3 mL作為還原劑，並添加28%的氨水70 mL，使溶液的pH成pHl 0.5後，添加無離子水至溶液量成1 L。另外，添加2 〇 p p m的聚環氧乙燒基-十二烷基醚作為鍍平劑。與第1實施形態同樣地，使液溫保持6 〇 °C，對氧化紹板進行白金電鍍處理。其結果，光澤良好的白金以丨.3 # m/h的析出速度析出。又，雖將此電鍍處理後的電鍍液放置1週，確認無電鍍液分解的產生。第3實施形態:在本實施形態中，與第2實施形態同樣地’以[?七(^113)6](〇11)4水溶液為原料製造碳酸鹽，對此取代弟2實施形悲的甲績酸，添加乙績酸6 〇 m l，使碳酸鹽溶解，添加還原劑、進行pH調整、溶液量調整，以製造電鍍液。此處的[Pt(NH3)6](〇H)4濃度等的其他條件係與第2實又施形態同樣的。 ' 並且，使液溫保持60 t：，對氧化鋁板進行白金電鍍處理的結果，光澤良好的白金以丨· j 的析出速度析出。又，雖將此電鍍處理後的電鍍液放置1週，確認無鍍液分解的產生。 ^ ^ :在本實施形態中’取代第2實施形態的 [Pt(NH3)6](OH)4，用白金濃度 l〇g/L· 的[Pt(CH3NH2)6](〇H\2169-4495-PF (N); Chiumeow.ptd Page 10 538133 V. Description of the invention (8) After filtering and extracting the carbonate of Shendian ’, it is washed and dried. Next, 50 ml of formic acid was added to this carbonate to dissolve the carbonate, and water was added to make the amount of the solution 1 L, and then carbonic acid was removed from the solution. In this manner, a solution (100 mL) of 3 g of platinum was extracted from the platinum complex solution, 3 mL of hydrazine-hydrate was added as a reducing agent, and 70 mL of 28% ammonia water was added to the solution. After the pH was adjusted to pH 1 and 0.5, deionized water was added until the solution volume became 1 L. In addition, a polyethylene oxide-dodecyl ether of 2 p p m was added as a leveling agent. In the same manner as in the first embodiment, the liquid temperature was maintained at 60 ° C, and the platinum plate was subjected to a platinum plating treatment. As a result, platinum having a good gloss was precipitated at a precipitation rate of 3 # m / h. The plating solution after this plating treatment was left for one week, and it was confirmed that no decomposition of the plating solution occurred. Third embodiment: In this embodiment, the same as in the second embodiment, the carbonate is produced by using [? VII (^ 113) 6] (〇11) 4 aqueous solution as a raw material. Formic acid was added with 600 ml of acetic acid to dissolve carbonate, and a reducing agent was added, pH adjustment and solution amount adjustment were performed to produce a plating solution. Other conditions such as the [Pt (NH3) 6] (OH) 4 concentration here are the same as those in the second embodiment. 'Furthermore, the liquid temperature was maintained at 60 t: As a result of platinum electroplating treatment on the alumina plate, platinum with good gloss was precipitated at a deposition rate of 丨 · j. The plating solution after this plating treatment was left for one week, and it was confirmed that no decomposition of the plating solution occurred. ^ ^: In this embodiment, 'Pt (NH3) 6] (OH) 4 is used instead of [Pt (NH3) 6] (OH) 4 in the second embodiment, and [Pt (CH3NH2) 6] (〇H \ with a platinum concentration of 10 g / L ·

538133 五、發明說明（9) ---*------ 溶液5 L作為/、氨基白金配位化合物的。而且，用與第2 實施形，同樣的條件吹入二氧化碳氣體，肖提取的碳酸鹽二力乙尹、酉夂使之，谷解。然後，提取1 〇〇 m L·此溶液，添加 ^原劑，進行pH調整、溶液量調整，以製造電鍍液。且，還原劑的量等條件係與第2實施形態同樣的。並且，使液溫保持60乞，對氧化鋁板進行白金電鍍處理的結I，光澤良好的白金以i · 〇 # m/h的析出速度析出。又’雖將此電鍍處理後的電鍍液放置1週，確認無電鍍液分解的產生。星實&形態:在本實施形態中，對第4實施形態中精製的六氨基白金配位化合物溶液1 0 0mL，添加次磷酸2 〇g作為還原劑後，使溶液的pH成pH8地進行pH調整，並添加去離子水至使〉谷液I成1 L。而且，添加2 〇 p p m的聚環氧乙烧基-十二烧基_作為鑛平劑。並且’用此電鍍液使液溫保持80 t；，對氧化鋁板進行白金電鐘處理的結果，光澤良好的白金以〇·95 vuj/h的析出速度析出。又，雖將此電鍍處理後的電鍍液放置丨週，確認無電鍍液分解的產生。也較例:作為與實施形態相對的比較例，作為原料，使用與第1實施形態同樣的[Pt(NH3)6](OH)4，並不經過/精製步驟，而直接製造電鍍液，對其安定性進行研討。在此比較例中，用白金濃度1(^/1的[?1：(關3)6](〇1〇4溶液11，添加聯氨-水合物3mL及乙氨酸0.2g作為還原劑，並加入〇 2mg —氧化鉛作為安定化劑。且，調整溶液量，將其調製， 538133 五、發明說明（ίο) 成pH為pH12的電鍍液。並且，使此電鍍液的液溫保持60 r，對氧化鋁板進行白金電鍍處理的結果，析出速度係2 0/zm/h，與第ι第5 實施形態相比’雖得到並不差的析出速度，但將電鍍處理後的電鍍液放置1日後，電鍍槽的底面及壁面上，確認有白金析出。此係因為，雖然在比較例中添加了安定叫庐未對原料的[PUNHs^KOH)4進行精製，此被認為係二於原料中所含有的不純物而使電錢液分解。產業上利用的可能性538133 V. Description of the invention (9) --- * ------ 5 L of solution is used as the amino platinum complex compound. Further, carbon dioxide gas was blown in under the same conditions as in the second embodiment, and the carbonates extracted by Shao Erli Yin and Yan Li were used to make the solution. Then, 1000 ml of this solution was extracted, and an original agent was added, and pH adjustment and solution amount adjustment were performed to produce a plating solution. The conditions such as the amount of the reducing agent are the same as those in the second embodiment. In addition, while maintaining the liquid temperature at 60 ° C, the alumina plate was subjected to platinum plating treatment, and platinum having a good gloss was precipitated at a deposition rate of i · 〇 # m / h. Furthermore, the plating solution after this plating treatment was left for one week, and it was confirmed that no decomposition of the plating solution occurred. Star Fruit & Form: In this embodiment, 100 mL of the hexaamino platinum complex solution purified in the fourth embodiment is added, and 20 g of hypophosphorous acid is added as a reducing agent, and the pH of the solution is adjusted to pH 8 The pH was adjusted and deionized water was added to make> Valley I to 1 L. Further, polyethylene oxide-dodecyl- 2 pm was added as a leveling agent. Further, 'the liquid temperature was maintained at 80 t with this plating solution, and as a result of platinum clocking the alumina plate, platinum with a good gloss was precipitated at a deposition rate of 0.95 vuj / h. In addition, it was confirmed that the plating solution after the electroplating treatment was left undisturbed for generation of decomposition of the plating solution. Also a comparative example: As a comparative example opposite to the embodiment, as the raw material, [Pt (NH3) 6] (OH) 4 similar to the first embodiment is used, and the plating solution is directly produced without going through / refining steps. Research on its stability. In this comparative example, a platinum concentration of 1 (^ / 1 of [? 1: (Guan3) 6] (〇104) solution 11, 3mL of hydrazine-hydrate and 0.2g of acetic acid were used as reducing agents. 〇2mg—lead oxide was added as a stabilizing agent. The solution amount was adjusted to prepare it. 538133 V. Description of the Invention (ίο) A plating solution having a pH of pH 12. The liquid temperature of the plating solution was maintained at 60 r. As a result of the platinum plating treatment on the alumina plate, the deposition rate was 20 / zm / h. Compared with the fifth embodiment, although the deposition rate was not bad, the plating solution after the plating treatment was left at 1 In the future, platinum deposits were confirmed on the bottom surface and wall surface of the plating tank. This is because, although a comparative example was added, the stability of the raw material [PUNHs ^ KOH) 4 was not refined. The impure substance contained in it causes the electricity liquid to decompose.

如以上所說明的，本發明係為提高習知的、以六氨基白金配位化合物為主要成分的無電解白金電鍍液之安定性 ’對六氨基白金配位化合物進行精製的無電解白金電鍵液之製造方法。藉此’使之不含不純物，可取得電鍍操作中無液組成分解的、極其安定的無電解白金電鍍液。且，利用與本發明有關的無電解白金電鍍液，從其安定性出發，可製造高品質的白金薄膜。、 X 參As described above, the present invention is to improve the stability of a conventional electroless platinum plating solution containing a hexaamino platinum complex compound as a main component. Of manufacturing method. Thereby, it is made free of impurities, and an extremely stable electroless platinum plating solution can be obtained in which no liquid composition is decomposed during the plating operation. In addition, by using the electroless platinum plating solution according to the present invention, a high-quality platinum thin film can be produced from its stability. , X parameters

2169-4495-PF(N) ； Chiumeow.ptd 第13頁 538133 圖式簡單說明 2169-4495-PF(N) » Chiumeow.ptd 第14頁2169-4495-PF (N); Chiumeow.ptd page 13 538133 Schematic illustration 2169-4495-PF (N) »Chiumeow.ptd page 14

Claims

，.一—--—----- 538哽先,. One ---------- 538

種無電解白金電鍍液之製造方法’用下述一般式表示的六氨基白金配位化合物之鹽為原料下34般 Μ 所 [Pt(a)J4+(式中，a係顯示CnH2n+1NH2(n 氨基；係0〜1 0的整數）所表示的配位化合物之精製=徵係下述步驟所示包含六氨基白金二負料的六氨基白金配位化合物作成水溶液，使H ^體通過上述水溶液，製造m金配位化合物的奴酸鹽之步驟；以及 (b)錢溶解上述六氨基白金配位化合物的碳酸鹽之步驟。 2 ·如申明專利範圍第1項所述的無電解白金電鐘液之製造方法’其中作為（a)步驟的六氨基白金配位化合物係採用氫氧化物。 3 ·如申請專利範圍第1項所述的無電解白金電鍵液之製造方法，其中作為（b)步驟的酸係採用有機磺酸或分子量3 0 〇以下的有機羧酸。 4 ·如申請專利範圍第2項所述的無電解白金電鍍液之製造方法，其中作為（b)步驟的酸係採用有機磺酸或分子量300以下的有機羧酸。 5 · —種無電解白金電鍍液，其係以申請專利範圍第1 項所述的方法製造。Kind of method for producing electroless platinum electroplating solution '34 using hexaamino platinum complex salt represented by the following general formula as raw material [Pt (a) J4 + (where a shows CnH2n + 1NH2 (n Amino group: an integer from 0 to 10) Purification of the coordination compound represented by the formula = = The hexaamino platinum complex compound containing the hexaamino platinum di-negative material shown in the following steps is used as an aqueous solution to pass the H ^ body through the aqueous solution Steps of manufacturing m-gold complex compounds; and (b) steps of dissolving carbonates of the above-mentioned hexaamino platinum complex compounds. 2. The electroless platinum electric clock as described in the first patent claim The method for producing a liquid 'wherein the hexaamino platinum complex compound as the step (a) is a hydroxide. 3 · The method for producing an electroless platinum bond liquid as described in item 1 of the patent application scope, wherein (b) The acid in the step is an organic sulfonic acid or an organic carboxylic acid having a molecular weight of 300 or less. 4 · The method for producing an electroless platinum plating solution as described in item 2 of the patent application scope, wherein the acid in step (b) is adopted Have An organic sulfonic acid or an organic carboxylic acid having a molecular weight of 300 or less. 5-An electroless platinum plating solution manufactured by the method described in item 1 of the scope of patent application.

2169-4495-PF(N) ; Chiumeow.ptd2169-4495-PF (N); Chiumeow.ptd

種無電解白金電鍍液項所述的方法製造。六、申請專利範圍 7 · —種無電解白金電鍍液，其係以申請專利範圍第3 項所述的方法製造。 8 ·如申請專利範圍第5項所述的無電解白金電鍍液，其中作為還原劑使用至少包括次磷酸、磷酸、聯氨、氫化爛、曱酸、L -抗壞金酸、甲酸中的任何一種。 9 ·如申請專利範圍第6項所述的無電解白金電鑛液，其中作為還原劑使用至少包括次磷酸、磷酸、聯氨、氮化爛曱®^、L -抗壞血酸、甲酸中的任何一^種。如申請專利範圍第7項所述的無電解白金電鍍液，八中作為還原劑使用至少包括次磷酸、磷酸、硼、甲醛、L-抗壞血酸、甲酸中的任何—種。戈里全雷\請專利範圍第5〜10項任一項所述的益電解白、電鍍液，其中含有非離子活性 12. -種無電解白金電鑛方法？為鍍千劑。利範圍第5〜1 〇項任一項所、+、^ — ，、匕括·使如申請專物相接觸，其中上述無電解白液與被電鍍 a-種無電m妒；被電鍍物相接觸。利範圍第1 1項所述的無 1方法，其包括··使如申請專，其中上述無電解白金電白金電鍍液與被電鍍物相接觸 40〜80 °C的條件下，盥、二夜係在PH值為pH8〜12、液溫為、罨鍍物相接觸。 2169-4495-PF(N) ； Chiumeow.ptd 第16頁A method of electroless platinum plating solution. 6. Scope of patent application 7 · An electroless platinum plating solution is manufactured by the method described in item 3 of the scope of patent application. 8. The electroless platinum plating solution according to item 5 of the scope of the patent application, wherein as the reducing agent, any one of at least hypophosphorous acid, phosphoric acid, hydrazine, hydrogenated rot, osmic acid, L-ascorbic acid, and formic acid is used. One. 9 · The electroless platinum power ore liquid as described in item 6 of the scope of the patent application, wherein at least one of hypophosphorous acid, phosphoric acid, hydrazine, nitrocarburic acid, L-ascorbic acid, and formic acid is used as a reducing agent. ^ Species. As the electroless platinum electroplating solution described in item 7 of the scope of patent application, Bazhong uses at least any one of hypophosphorous acid, phosphoric acid, boron, formaldehyde, L-ascorbic acid, and formic acid as a reducing agent. Gorry Quan Lei \ Please use the beneficial electrolytic whitening and electroplating solution described in any of the items 5 to 10 of the patent scope, which contains non-ionic activity 12.-A non-electrolytic platinum electro-mineral method? For a thousand agents. The scope of any of the items 5 to 10 of the scope of benefit, +, ^ — ,, and daggers. Make contact with the application subject matter, wherein the above-mentioned electroless white liquor is electroplated with a-type electroless m; contact. The non-one method according to item 11 of the scope of benefit, which includes: applying the above-mentioned electroless platinum electroplating electroplating solution to the object to be electroplated at a temperature of 40 ~ 80 ° C for two nights as described in the application. It is in the pH value of 8 ~ 12, the liquid temperature is in contact with the hafnium plating. 2169-4495-PF (N); Chiumeow.ptd page 16