JPS58204168A - Electroless plating bath of rhodium or rhodium alloy - Google Patents

Abstract

PURPOSE:To provide a titled plating bath which has high stability, offers a high utilizing rate of metal, and is high in plating speed by using rhodium or the other metal as ammine complex salt together with rhodium and contg. hydroxyl amine salt and hydrazine therein. CONSTITUTION:Ammine complex salt of rhodium or a mixture thereof and the other ammine complex salt, hydroxyl amine salt as a stabilizer and hydrazine as a reducing agent are incorporated and the pH thereof is controlled to 10-13, whereby an electroless plating bath of rhodium or a rhodium alloy is obtained. Rhodium salt or hexaammine salt or the like obtd. by causing the mixture of said salt and the salt of the other metal such as platinum to react with ammonia is preferable as the ammine complex salt. Water-soluble hydrochloride or the like is preferable as the hydroxyl amine salt and hydrazine hydrate or the like which forms hydrazine in the state of an aq. soln. is preferably usable for the hydrazine.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a metal or non-metal surface with 0 dium or 0 . ;
The present invention relates to a hydrazishi-type raw temperature for electroless metallurgy of ram alloys, and in particular to a novel raw temperature for metallurgy that has excellent stability of the bath liquid, high utilization rate of 0 dium or rhodium alloys, and high metallization speed.

Generally, 0. ;Rum or 0. ; Lamb alloy chemists add hydra, sodium borohydride, or alkaline chloride as a reducing agent to a mixed solution of these metal salts and ethylene diamic acid (which forms a complex salt), asimonia, etc. A material with 5 grains added is used. However, if the above composition remains as it is, the stability of the atricide complex salt in the bath liquid is poor, and 0. ; Because the reduction of rhum or rhodium alloy progresses too much and precipitates in the bath (i.e. self-decomposes), it is normal to add a stabilizer to suppress the reaction; Even in these cases, a bath liquid with sufficient stability has not yet been obtained.

On the other hand, from a practical point of view, since O,; ram itself is expensive, it is desirable that the rate of precipitation from metal salts is high, in addition to low self-decomposition in the bath liquid.

In other words, it is ideal that the ram is almost completely utilized in each batch.

Furthermore, from the standpoint of operability, it is desirable that the precipitation time be fast.

The present inventors have met the above requirements: (1) Stability of bath liquid; (2) 0. When the known bathing method was retried taking into consideration the utilization rate of liquid and bathing speed, no satisfactory bath liquid could be found.

That is, despite the use of a stabilizer, a bath using a borohydride salt as a reducing agent has poor results (1) and (2), and a bath solution using alkyl amicide borax has poor results (2) and (2).

Hydra! ; As for the bath, ■ was unstable. However, in the former two, there is no room for improvement even when various bath liquid compositions are tried, whereas in the case of the hydrazide bath, it has been found that improvements in (1) can be expected by improving the bath liquid.

Both methods using hydra and hydra as reducing agents for 0,;ram's chemical method use a solution consisting of 0dium chloride or sulfate, ethyrecidiamic acid, and sodium hydroxide. salt alone or in combination with a borohydride salt, and potassium ferrodiazide (Chemical Abstracts Vol. 86, 94262) as a stabilizer.
n), dimethyl cryo-cow sim (Chemical Abstracts Vol. 86, 46520y, Vol. 87, 271547F), etc. are used.

However, when rhodium is actually grown on the surface of metals, plastics, sulfur exchange membranes, etc. using these known bath solutions and methane conditions, any of the above items (1), (2), and (2) are insufficient and are not satisfied. There was nothing to gain. In addition, ethylene diamine itself, which is present in the basic bath, cannot be used in the case of rhodium bonding for the purpose of bonding a catalyst electrode to an sulfur exchange membrane because it causes contamination of the membrane.

The present inventor has proposed the above-mentioned ■,
As a result of intensive investigation of reagents and coexisting stabilizers in order to obtain a Metsushi bath that was excellent in both (1) and (2), we found that 0. ；Using the metals of the alloy composition to be bonded or bonded as a tricythic complex salt solution, and human silica as a stabilizer:
The present invention was completed based on the discovery that the intended purpose could be achieved when J salt was used.

That is, the present invention is directed to a body) 0. ; Lamb's A, 7-misi complex salt or a mixture of this and other metal amici complex salts, (h) human 0
+ silua trisulfate, and (c) hydrazisyl, and the PH
It is characterized by being IO~13. ,;ram or 0.
;Relates to the electroless raw temperature of ram alloy.

As the 0, 1; lamb reed trisic complex salt in the present invention, for example, 0 dium salt is put into an autoclave together with asimonia and water, and the 0, 1; pressure, 120-1
He + Saashimishi salt [Rh(NH3)6]x3 (X is H0geshi,
Although it is preferable to use a solution obtained by boiling a rhodium salt with acetic acid water while adding acetic acid water until the solution becomes pale yellow, it is also possible to use a solution obtained by boiling the rhodium salt with acetic acid water and adding acetic acid water until the solution becomes pale yellow.

When combining 0dium alloy, 0dium and platinum,
Preferably, mixed salts with salts of ruthenium, iridium, nickel, cobalt, etc. are similarly treated with hot asimonia water under pressure and used as a stable mixed a,7 trisalt complex solution. At this time, the molar ratio of the metal added to rhodium is 0.1 to 1.07 mol to 1 mol of rhodium, and the molar ratio of metal added to 1 mol of rhodium is 0.1 to 1.07 mol. On the other hand, it is preferable that the total number of moles of added metals is 17 or less. To give an example of three elements, for example, 0
If platinum or iridium is used for 1 mole of dium, the ratio is 0.
．． In the case of ruthenium, nickel or cobalt, it is preferably 0.1-1 mol.

As the salt used in the present invention, water-soluble salts such as hydrochloride, sulfate, nitrate, etc. are preferable.

Hydrochlorides, sulfates, etc. can be suitably used.

The composition of the bath liquid of the present invention is 0.001-0.001 by using rhodium or a zero-dium alloy as the asimici complex salt. I N/t(0
o, t-tof/z) for dium) preferably 0.00
1 to 0.05 M/l (0.1 to 5 f/l for 0 dium
), human O+cilamici from 0.003 to 1.5 &/4 (
0.1-50 f/l) preferably 0.003-0.
15 M/l (0,1-52) and Hydra! ;Shi is 0
．． 003-1.5M/lc In the case of hydrazide hydrate 1
~5 Qt/l) preferably 0.003 to 0.3M
/l (1-10 t/l in case of hydrazide hydrate). In the present invention, the bath solution having the above composition is adjusted to have a pH in the range of 10 to 13, preferably 11 to 12, using aqueous acetate or an alkaline pH buffer.

When the pH is higher than 13, the reduction rate becomes faster and self-decomposition increases, and when the pH is lower than lO, the growth rate is low and the growth time becomes long. When the Human Oshiru Shiramishi reaches 5097 or more, growth is extremely suppressed and it becomes difficult for the Metsushi to progress.

The method of the present invention is that the A, 7-complex A, 3+ n [Rh (Horse) 6] in the bath liquid is RhC1 or Rh2 (
S04) 0 in aqueous or alkaline solution of 3
,; Umuioshi (R3+, (RhC16)3-1 [R
h (NH2C! 4 Lab L2) 3) 30, etc.) (same goes for rhodium alloys), and when human oxygen salt is added, an even more stable complex is formed, and self-decomposition is almost suppressed. It will be done.

Therefore, the medical treatment bath of the present invention has extremely excellent stability without self-decomposition over a long period of time when the body to be treated is not immersed.

When the body to be treated is immersed, the reduction reaction starts catalytically and the membrane selectively progresses, but if 0dium or 0% is present in the bath liquid,
It continues until it is consumed at a high rate of 95 or more as a dium alloy. The time required for treatment is not constant as it depends on the shape of the body to be treated, but to give an example of obtaining a middle layer of ↑ 3μ, it is a short time of 1.5 to 2 hours.

Table 1 shows a comparison of the stability between an example of the lukewarm meat of the present invention and a known hydrazine type meat meat bath.

Table 1 As is clear from Table 1, it can be seen that the present invention's medicinal fluid has extremely excellent stability of the bath solution and selectivity to the body to be treated.

Examples of objects to which the present invention can be applied include metals such as copper, nickel, iron, alloys thereof, titanium, tashital, etc., and industrial materials such as electronic parts and electrodes. Furthermore, it can be applied to materials that can be treated with ordinary electroless metallurgy, such as synthetic resins, glass, and ceramics. Furthermore, the present invention's metsu beef bath does not contain sulfur-active substances such as ethylesidium and dimethyl chloride, so the sulfuric acid exchange membrane contains rhodium or 0.5%. ; It is particularly excellent as a bath liquid for bonding ram alloys, and in recent years, it can be applied as a technique for creating bonded bodies in which electrodes are bonded to the membrane surface of solid polymer electrolytes (iodine exchange membranes) used in aqueous electrolysis.

In either case, it is preferable to perform activation processing on the body to be treated in advance.

In the case of metal, the surface is immersed in a salt solution such as palladium, platinum, or 0 dilam, and if necessary, subsequently immersed in an aqueous boron hydride salt solution for activation, and then immersed in the method of the present invention. .

In the case of polymers, glass, and ceramics, the surface is usually subjected to surface hydrophilic treatment, sensitization treatment, and activation treatment, which are used when applying copper, nickel, etc., to the surface. Soak in the invention Metsu beef bath.

In the case of an iodine exchange membrane, after the surface is roughened, a metal salt (preferably ammici complex salt) solution is adsorbed, and then reduced with a sodium borohydride solution to bond a 1 to 2μ first layer. The melon of the present invention is grown by immersing it in lukewarm temperature.

The temperature is in each case carried out at 50-90°C, preferably 60-75°C.

The thickness of the bath is determined by pre-existing the amount of 0 dium or 0 dium alloy required from the surface area of the body to be treated in the bath liquid. Rhodium in the bath liquid or 0. The utilization rate as a ram alloy is as high as 95% or more, and the small amount of O, ram remaining in the waste liquid can be recovered by adding boron hydride salt to precipitate it.

The middle layer of the present invention has electrical properties and mechanical strength equivalent to those of electroless mets+, and can be used for the complex-shaped metsu+ bodies that are characteristic of electroless mets, small electronic parts, and electrical contacts. , suitable for use with non-magnetic or magnetic zero-dium alloys.

Further, as an industrial material, it can be used as a method for producing sulfur exchange membrane-electrode assemblies for aqueous electrolysis or fuel cells.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example: 1' Add 28 NH4OH50d to RhCl35f,
In autoclay, 20Kp/ctl, 1 at 150℃
After treatment for 2 hours, the solution was taken out, filtered while hot, and the P solution was concentrated to crystallize the chloride of hexafluoride::'JO,;um(2). Using this, the present invention's Metsu Heizoku having the following composition was prepared.

[RA(MI5)6]Ct30. t2 yH20H-
HCl 0, 1 fN2 included/H
2O2puMζ0H (28chi) 10go water
Total amount: 100 dpH: 11.5゛ Bath temperature: 70 to 80°C Using the above bath solution, a copper plate was coated.

After degreasing sample copper plate (2x4crn) with alkali, hydrochloric acid (3
%)K for 10-20 seconds at room temperature, then 54Pd
It was activated by immersing it in a C12(7) 2N-HC1 solution at room temperature for 30 seconds. After washing with water, it was immersed in the above-mentioned methane bath solution for 2 hours to obtain a 0-dium oxide film with a thickness of about 2 μm.

No precipitation was observed in the bath liquid or on the vessel wall, and the residual amount of 0 dium in the bath liquid after treatment was less than IIIF, and the 0 dium utilization rate was 98.
It was more than 1.

Example 2 A bath solution having the following composition was prepared using a solution of the complex ion [Rh(NH3)6] obtained by boiling RnCl3 with NH4OH for 3 hours.

[Rh (#773)6) Solution 0 dium and Te 0
．． 04 tm20H-HCl
'O,'5 fN2H4・H2O2,51LA
'PH12 (D buffer 1
0m/(0,l MlZ NaOH10.1 MlZ
Nα2B20) Water total amount 10
0 mlP H12,0 Bath temperature 70~80℃ Using the above solution, apply 0 to ABS resin (3 x 3c!n specimen).
．． ;I performed Rammetsu 10.

For sample pretreatment, the following bath solution was used, as is usually done with plastic Metsu+.

Etch Schiff bath #, So4550ml Cr0 2
Q H2O (total amount) t
ooo vt etch: Jj was performed at 65° C. for 20 minutes and washed with water.

Medium setalist bath palladium chloride 0.32 stannous chloride
15f hydrochloric acid (35clb) 250
d Water (total amount) 1000 d Immersed in the above bath solution at 30° C. for 3 minutes.

Activation bath Sodium borohydride 0.51 water Total amount
It was treated in a 1000g activation bath for 2 minutes at room temperature.

Subsequently, it was immersed in a 0-dium metal bath for 30 minutes to obtain a glossy 0-dium metal with a diameter of about 0.5μ. The 0-dium metal bath was used three times using the same type of sample, and the same 0-dium metal was obtained for each sample. During this time, the bath liquid was stable and no decomposition occurred.

Example 3 Extreme fluorine -sulfosic acid -type IOshaden membrane [Duum was joined.

The membrane is pre-treated by first roughening it with Sacid Rust, and then
It was boiled with N-HCl to de-iosify and washed with water.

Then, it was immersed in a solution of 0 dium acyl tricyclocomplex [Rh(NH3)6]3+ prepared in the same manner as in Example 1 (room temperature, 5 hours).
After rinsing with water, acetic Na1311a 0.05
% solution at 40-60° C. to precipitate a 1-1.5 μm O-dium layer. A bath solution with a bottom fertilizer composition was used for the growth of this o;ram layer.

[Rh(A'#3)6) Solution o, ; As ram 0.31NH2°H''HC1O,5r N2H4-H,,03,OWLl Nlll, OH (28%)
IOmJ water total amount 150dp
g 11.5-11.8 bath temperature
75-80'℃ Metsushi treatment was performed for 2 hours, and the 0dium layer on the treated edge was approximately 5μ
It grew thick. No decomposition was observed in the bath liquid, and the rhodium utilization rate was 99q6.

Example 4 Rhct3hptct4 was Pi/Rh (Den ratio T O
, 5/'1.0 ratio, and put it in an autoclave with anhydrous water at 20Ky/di, 160℃,
After treatment for 10 hours, a mixture of Ashimishi complex salts was prepared and used.

Pi-Rh mixed Ashikoshi complex salt 0 as 0ium 0
．． 12m20H-HCl
2. OfN2H4°H20”
4go NH40H (2816>
20rttl water total amount
A 200g pH 11.6 nickel sample plate (5 x 5 cm) was degreased with alkali and activated using a solution of RhCl32f, HCtl 0ml and water gold amount 11. After washing with water, it was immersed in the above plating bath and heated at 70°C. , 2 hr medical treatment was performed.

A 0-dium-platinum alloy with a thickness of about 3 μm was obtained on the nickel surface, and 0. ; The utilization rate of rum and platinum was over 95%.

(That's all) 19- Procedural amendment (voluntary) 1. Indication of the case Patent Application No. 85535 of 1987 2. Name of the invention Electroless plating bath for rhodium or rhodium alloy 3. Person making the amendment Relationship to the case Patent Applicant Address: 1-3-1 Kasumigaseki, Chiyoda-ku, Tokyo Name
(114) Director of the Agency of Industrial Science and Technology Hirobe Yoda 4, Designated agent address: 1-8-31 Midorigaoka, Ikeda City, Osaka Prefecture Section 7 of “Detailed Description of the Invention” in the specification Contents of the amendments Contents of the amendments as attached in the attached sheet 1. Specification, page 5, lines 8 to 9 [120℃ to 160℃
Correct the text "Temperature of 110℃ to 160℃".

2. Specification page 5, lines 10-11 “Hexammine salt [Rh(NH3)a) X3 (X is halogen, No.
2nd grade)” is replaced with “hexaammine salt (Rh(NH3)
)6) X3v or pentaamine salt (Rh(N
H3)S X) Xe (X is halogen, No2, etc.)
” is corrected.

3. On page 7, line 7 of the specification, "1 to 50 g/Q, 1" is corrected to rO, 15 to 75 g/fil.

4. On page 7, line 8 of the specification, ``1~10g10'' should be corrected to ``10.15~15g/Q''.

5. Specification page 8, line 1 r (Rh(NHa)a)
)” is RhCl32. r (Rh(NHa
)63 a+, [Rh(NH3)5CΩ]2+.

(Rh(NHa)S H20)” etc. are RhCf13
Correct to J.

6. Specification page 15, line 4 r (Rh(NH3)6
) 3 “Solution” r (Rh(NH3)s C
Q) ”+ and (Rh(NH3)a)120)
” is corrected to mixed solution j.

7. Specification page 15, line 6 rRh(NH3) “solution”
Correct the statement to "rhodium ammine complex salt solution."

8. Specification page 17 line 16 r (Rh(NH3)a
) Correct the word "solution" to "rhodium ammine complex ion solution."

that's all 1-

Claims (1)

[Claims] ■ Rhodium containing (α) rhodium ashimishi complex salt or a mixture of this and other metal ashimishi complex salts, (h) human O-beef sylamishi salt, and (C) hydrazishi, and having a pH of 10 to 13. or 0. ;Electroless raw temperature of ram alloy.