[go: up one dir, main page]

WO2002046492A1 - Procede de fabrication d'une solution de plaquage pour depot autocatalytique de platine, cette solution et procede de plaquage correspondant - Google Patents

Procede de fabrication d'une solution de plaquage pour depot autocatalytique de platine, cette solution et procede de plaquage correspondant Download PDF

Info

Publication number
WO2002046492A1
WO2002046492A1 PCT/JP2001/010608 JP0110608W WO0246492A1 WO 2002046492 A1 WO2002046492 A1 WO 2002046492A1 JP 0110608 W JP0110608 W JP 0110608W WO 0246492 A1 WO0246492 A1 WO 0246492A1
Authority
WO
WIPO (PCT)
Prior art keywords
plating
electroless platinum
complex
solution
platinum plating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2001/010608
Other languages
English (en)
Japanese (ja)
Inventor
Katsutsugu Kitada
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tanaka Kikinzoku Kogyo KK
Original Assignee
Tanaka Kikinzoku Kogyo KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tanaka Kikinzoku Kogyo KK filed Critical Tanaka Kikinzoku Kogyo KK
Publication of WO2002046492A1 publication Critical patent/WO2002046492A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents

Definitions

  • the present invention relates to an electroless plating solution having excellent stability and capable of producing a high-quality platinum thin film.
  • the present invention also relates to a method for plating platinum using the electroless platinum plating solution.
  • this electroless platinum plating solution has a certain effect due to its stabilizer
  • the plating solution containing such a stabilizer has the problem that decomposition occurs when the plating solution is replenished during the plating operation. There is. Therefore, the plating operation using this plating solution is based on a batch process, which is not suitable for a continuous plating operation, but this does not allow efficient plating.
  • electroless platinum plating described in JP-A-5-222543.
  • the plating solution is mainly composed of a tetravalent platinum amine salt represented by the general formula [Pt (NH 3 ) 6 X], and is used for continuous plating without a stabilizer. It is disclosed that platinum plating can be performed stably. According to this plating liquid, it is possible to produce a high-quality platinum thin film, and it is also applicable to the plating of decorative articles because of its good gloss.
  • the stability of the electroless platinum plating solution described in Japanese Patent Application Laid-Open No. 5-222543 is not always sufficient, and the present inventor conducted preliminary tests.
  • the present invention has been made in view of the above background, and has extremely high stability, enables continuous plating operation, and has an electroless platinum plating solution capable of producing a high-quality thin film.
  • the purpose is to provide. And it aims at providing the plating method using this plating solution. Disclosure of the invention
  • the present inventor evaluated the stability of the electroless platinum plating solution containing the above hexaminoplatinum complex ([Pt (NH 3 ) 6 X]) as a main component, After a detailed study to improve the stability, it was found that this plating solution contained the following impurities, although it contained a tetravalent hexaaminoplatinum complex as a main component. Equation 1
  • Such impurities are considered to be generated in the process of preparing the plating solution during the production of the hexaminoaminoplatinum complex salt used as the raw material, but are less stable than the hexaminoplatinum complex as the main component. It decomposes in the solution to produce platinum fine particles that easily adhere to the plating tank wall and the adherend. Then, the catalytic action of the platinum fine particles promotes the deposition of platinum on portions other than the plating tank wall surface and the plated portion of the adherend.
  • the present inventor has determined that in order to improve the stability of the plating solution, it is necessary to eliminate the above-mentioned impurities, and for that purpose, in the production process of the plating solution, a hexaminoplatinum complex was used. It was considered appropriate to purify in advance.
  • a hexaneaminoplatinum complex salt as a raw material is made into an aqueous solution, and carbon dioxide gas is blown into the aqueous solution. A technique for extracting platinum complexes was found.
  • the reason for once reacting with the carbon dioxide gas is that the carbonate ions have excellent reactivity and selectivity with respect to the tetravalent hexaminoaminoplatinum complex to be purified.
  • This is based on the idea that the hexaminoaminoplatinum complex can be extracted with high purity. That is, the present invention provides a method for producing an electroless platinum plating solution containing a hexaminoplatinum complex using a salt of the hexaminoplatinum complex represented by the following general formula as a raw material, A method for producing an electroless platinum plating solution, which comprises a step of purifying a complex. Equation 2
  • a is, C n H 2 n + 1 NH 2 (n is an amino group represented by 0 to 1 0 integer).
  • a hexaminoplatinum complex salt is converted into an aqueous solution.
  • a hydroxide as the hexamino platinum complex salt. This is because coprecipitation of impurities is the least in the subsequent step of reacting with carbon dioxide to form carbonate.
  • the amount of the hexaaminoplatinum complex salt dissolved in the aqueous solution is preferably 1 g / L to 20 gZL in terms of platinum.
  • the amount is less than 1 gZL, a sufficient amount of carbonate cannot be purified, and the efficiency is low. Also, if it exceeds 20 gZL, the salt will not be dissolved. Then, carbon dioxide gas is blown into the aqueous solution to precipitate carbonates.
  • the amount of carbon dioxide gas passing here depends on the concentration of the hexaminoplatinum complex salt solution in the aqueous solution. As a guide, it is better to blow carbon dioxide gas until the solution becomes neutral.
  • the hexaminoaminoplatinum complex in the aqueous solution precipitates as a carbonate.
  • This carbonate is a high purity hexaaminoplatinum complex carbonate that does not contain the above-mentioned impurities.
  • the carbonate is dissolved with an acid in order to extract the hexaminoplatinum complex for platinum plating from the carbonate.
  • an acid for dissolving the carbonate a halogen acid such as hydrochloric acid can also dissolve the carbonate.
  • the halogen remains in the dissolution solution, and this is fixed.
  • the thin film is adsorbed on the thin film, thereby decreasing the deposition rate and darkening the appearance of the thin film.
  • sulfuric acid generates sulfate, and nitric acid has a problem that the appearance of the thin film is deteriorated.
  • an organic sulfonic acid such as methanesulfonic acid or ethanesulfonic acid
  • a low molecular weight organic carboxylic acid such as acetic acid or propionic acid.
  • These acids are added in the form of an aqueous solution.
  • carbonate ions remain in the solution after the addition of the acid, it is desirable to remove the carbonate ions when producing the plating solution.
  • co 2 a carbonate in which dissolve in an acid such as an organic sulfonic acid or organic carboxylic acids described above can be foamed easily carbonate by to Rukoto reduced pressure atmosphere solution upon dissolution The ions are removed.
  • the aqueous solution after these purification steps is a high-purity hexaaminoplatinum complex solution.
  • the hexaminoplatinum complex solution can be used as it is as an electroless platinum plating solution, but it may be appropriately diluted to bring the concentration of the platinum complex to a predetermined concentration. It can be a platinum plating liquid.
  • a reducing agent As this reducing agent, phosphinic acid, phosphonic acid, hydrazine, boron hydride, formalin, L-ascorbic acid, formic acid and the like are applicable.
  • concentration of these reducing agents is preferably 1 to 10 times the platinum ion concentration (molar concentration) in the plating solution.
  • the plating solution according to the present invention enables the production of a high-precision thin film.
  • a leveling agent may be applied to a general electroless plating solution other than platinum.
  • a cationic surfactant is applied.
  • the platinum thin film intended for the production of the present invention tends to adsorb the organic substances in these surfactants, so that the deposition rate is reduced and, in some cases, the deposition reaction is interrupted. When these surfactants are added, insoluble precipitates may be formed.
  • the leveling agent for the electroless plating solution of the present invention polyoxyethylene alkyl ether, polyalkylphenyl ether, polyoxyethylene polyoxypropyl alkyl ether, dalyserine ester, polyglycerin ester, sorbitan ester It is preferable to use a nonionic surfactant such as ester.
  • the concentration of these leveling agents is preferably 0.1 to 100 ppm.
  • the conditions for performing platinum plating using the electroless platinum plating solution according to the present invention are as follows: pH is set to 8 to 12, and the liquid temperature is set to 40 to 80 ° C. It is good. This is because, when the pH is less than pH 8, precipitation of platinum does not occur, and when the pH exceeds pH 12, the working environment deteriorates. In addition, when the liquid temperature is lower than 40 ° C, platinum does not precipitate, and when the liquid temperature is higher than 80 ° C, evaporation of amine in the plating liquid becomes remarkable.
  • pH of this plating solution add acid or aluminum to the plating solution.
  • adding the alkali it is necessary to apply an alkali having the same amino group as the amino group (a in Chemical formula 3) coordinated to platinum in the hexamino platinum complex. Is preferred.
  • First Embodiment 5 L of a “Pt (NH 3 ) 6 ] (OH) 4 solution having a platinum concentration of 10 gZL was prepared, and carbon dioxide gas was blown into the solution for 3 hours. The carbonate was weighed so that the amount of platinum contained was 30 g, and 45 mL of acetic acid was added thereto to dissolve the carbonate, and further water was added. Then, the solution after dissolution was reduced in pressure to remove carbonic acid.
  • Kisaamino platinum complex solution to the purified [P t (NH 3) 6] (CH 3 COO) 4 solution) was taken platinum amount 3 g portion of the solution (1 0 OML), reduced to this
  • glycerin ester (20 ppm) was further added as a leveling agent.
  • the electroless platinum plating solution produced as described above was heated to a temperature of 60 ° C., and an alumina plate treated with a catalyst was immersed in the solution to perform platinum plating. As a result, platinum with good gloss was deposited at a deposition rate of 1: 8 mZh.
  • the plating solution after the plating treatment was left for one week, but it was confirmed that the plating solution did not decompose.
  • Second Embodiment: [P t (NH 3) 6] in 1 0 GZL platinum concentration (OH) 4 was prepared, and carbon dioxide gas was blown into the solution for 3 hours. The precipitated carbonate was collected by filtration, washed, and dried. Next, 50 mL of maleic sulfonic acid was added to the carbonate to dissolve the carbonate, and water was further added to make the volume 1 L, and then the carbonic acid was removed from the solution.
  • a solution (100 mL) of 3 g of platinum was collected from the platinum complex solution, and 3 mL of hydrazine monohydrate was added as a reducing agent to adjust the solution pH to pH 10.5.
  • deionized water was added so as to have a liquid volume of 1 L, and polyoxyethylene dodecyl ether 20 ppm as a leveling agent was further added.
  • a platinum plating treatment was performed on an alumina plate at a liquid temperature of 60 ° C. As a result, platinum with good gloss was deposited at a deposition rate of 1.3 zm / h.
  • a carbonate is produced using an aqueous solution of [Pt (NH 3 ) 6 ] (OH) 4 as a raw material.
  • 6 OmL of ethanesulfonic acid was added to dissolve the carbonate, and a reducing agent was added to adjust the pH and the volume of the solution to produce a plating solution.
  • other conditions such as the concentration of [Pt (NH 3 ) 6 ] (OH) 4 are the same as in the second embodiment.
  • the plating rate was 2.0 m_ / h, which was not inferior to those of the first to fifth embodiments. Deposition speed was obtained, but when the plating solution after the plating treatment was allowed to stand, platinum was deposited on the bottom and wall of the plating tank one day later. Was confirmed. This is because, although the stabilizer was added in the comparative example, the raw material [Pt (NH 3 ) 6 ] (OH) 4 was not purified, and the impurities contained therein caused the purification. It is considered that the plating liquid was decomposed. Industrial applicability
  • the present invention aims to further improve the stability of a conventional electroless platinum plating solution containing a hexaminoaminoplatinum complex as a main component, and to improve the stability of an electroless platinum plating solution for purifying a hexaminoplatinum complex.
  • This is a method of producing an electroless platinum plating solution, which does not contain impurities and does not decompose the composition of the solution during the plating operation.
  • a high-quality platinum thin film can be produced from its stability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)

Abstract

Cette invention concerne un procédé d'obtention, à partir d'un sel complexe d'hexa-aminoplatine, d'une solution pour dépôt autocatalytique de platine renfermant un complexe hexa-aminoplatine, caractérisé par l'inclusion d'un processus de purification de l'hexa-aminoplatine. Ce procédé consiste à : (a) préparer comme matériau de départ une solution aqueuse d'un sel complexe d'hexa-aminoplatine, au travers de laquelle on fait passer du dioxyde de carbone pour obtenir le carbonate du complexe hexa-aminoplatine ; et (b) dissoudre le carbonate du complexe hexa-aminoplatine avec un acide.
PCT/JP2001/010608 2000-12-05 2001-12-05 Procede de fabrication d'une solution de plaquage pour depot autocatalytique de platine, cette solution et procede de plaquage correspondant Ceased WO2002046492A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000-369528 2000-12-05
JP2000369528A JP4463972B2 (ja) 2000-12-05 2000-12-05 無電解白金めっき液の製造方法及び無電解白金めっき液並びに無電解白金めっき方法

Publications (1)

Publication Number Publication Date
WO2002046492A1 true WO2002046492A1 (fr) 2002-06-13

Family

ID=18839548

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2001/010608 Ceased WO2002046492A1 (fr) 2000-12-05 2001-12-05 Procede de fabrication d'une solution de plaquage pour depot autocatalytique de platine, cette solution et procede de plaquage correspondant

Country Status (3)

Country Link
JP (1) JP4463972B2 (fr)
TW (1) TW538133B (fr)
WO (1) WO2002046492A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5931397B2 (ja) * 2011-10-20 2016-06-08 日本碍子株式会社 貴金属被膜およびその製造方法
KR102541103B1 (ko) 2017-05-18 2023-06-08 니혼 고쥰도가가쿠 가부시키가이샤 무전해 백금 도금액 및 그것을 사용하여 얻어진 백금 피막

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05222543A (ja) * 1992-02-14 1993-08-31 Electroplating Eng Of Japan Co 白金無電解めっき浴及びそれを用いた白金めっき品の製造方法
EP1024211A2 (fr) * 1999-01-19 2000-08-02 Shipley Company LLC Bain de placage d'un alliage d'argent et méthode pour obtenir un film en alliage d'argent l'utilisant

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05222543A (ja) * 1992-02-14 1993-08-31 Electroplating Eng Of Japan Co 白金無電解めっき浴及びそれを用いた白金めっき品の製造方法
EP1024211A2 (fr) * 1999-01-19 2000-08-02 Shipley Company LLC Bain de placage d'un alliage d'argent et méthode pour obtenir un film en alliage d'argent l'utilisant

Also Published As

Publication number Publication date
TW538133B (en) 2003-06-21
JP4463972B2 (ja) 2010-05-19
JP2002173780A (ja) 2002-06-21

Similar Documents

Publication Publication Date Title
WO2008019582A1 (fr) Catalyseur pd/c supporté et son procédé de préparation
TWI259175B (en) Process for the preparation of amino carboxylic acid salts
RU2007122483A (ru) Высокоактивный и высокостабильный катализатор дегидрирования на основе оксида железа с низкой концентрацией титана и его получение и применение
KR101311626B1 (ko) 하이드록실 암모늄의 연속 제조 방법
WO2002046492A1 (fr) Procede de fabrication d'une solution de plaquage pour depot autocatalytique de platine, cette solution et procede de plaquage correspondant
KR102241757B1 (ko) 백금 화합물 촉매의 제조 방법
JPH01275419A (ja) ヒドロキシルアンモニウム塩の製法
JPS62198641A (ja) カルボン酸塩の製造法
JP2007308796A (ja) 無電解金めっき液及び無電解金めっき方法
JP2011093748A (ja) 亜硝酸ロジウム錯イオン溶液の精製方法と、そのアンモニウム塩の製造方法。
JP4178398B2 (ja) ロッド状銀粒子の製造方法
JP3545658B2 (ja) 硝酸イリジウム溶液の製造方法
EP4209477A1 (fr) Procédé de production de méthanol
JP2011038158A (ja) 金属微粒子およびその製造方法
JPS61195935A (ja) 滅菌用浄化剤の製造方法
JP4554193B2 (ja) ヒドロキシルアミン安定剤の製造方法及び精製方法
JP4370023B2 (ja) ２，４−ペンタンジオナトジカルボニルロジウム（ｉ）の製造方法
KR20030055505A (ko) 수산화세륨으로부터의 탄산세륨 제조방법
JP2007022956A (ja) 高純度アミノメチレンホスホン酸の製造方法
JP2002020367A (ja) ホモシスチンの精製方法
JPH04228419A (ja) 硫酸アンモニウム溶液の精製方法
JPS6148506A (ja) 気相法微粒子の精製方法
CN118547377A (zh) 一种硫酸四氨合铜晶体的生产工艺
JP2006117460A (ja) 酸化タンタルゾル及びその製造方法
EP1977995B1 (fr) Procédé de fabrication d'hydroxylamine

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): KR SG US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase