KR800001243B1 - Acid copper plating solution - Google Patents

Abstract

Acid copper plating soln. was prepd. by mixing dye derivs. (I; A is the dyestuff which is able to form the atomic arrangement structure of II; B is the dyestuff which is able to form the quaternary ammonium structure in the acid solution) with acid copper aq. solution which is comprising the copper sulfate and sulfuric acid. Thus, dye deriv. 0.015g/l was added to the acid copper plating soln., which is composed of copper sulfate 220g/l,sulfuric acid 60g/l and chloride 10mg/l, and air stirred at 25≰C to give the titled plating solution.

Description

Acid Copper Plating Solution

The present invention relates to an acidic copper plating solution characterized by containing a dye derivative represented by the general formula B-N = N-A-N = N-B in an acidic copper aqueous solution composed of copper sulfate and sulfuric acid.

의 원자배열구조를 가질 수 있는 염료 즉 메틴계 염료, 아조메틴계 및 티아졸계 염료 등이 있으며, 그 예로서는 아스트라 프록신 FF(Antna Phloxine FF), 아스트라존레드 6B(Astrazone Red 6B), 피나시아놀(Pinacyanol), 아스트리프록신 바이오렛(Astraphloxine Violet), 아스트라존 오렌지 R(Astrasone Orange R), 로졸 레드 6B(Rosol Red 6B), 티오플라빈 티(Thioflavine T), 씨트로플라빈 8G(Citroflavine 8G) 등이 있다.Herein, the dye derivative represented by the above general formula will be described in detail.

Dyes which may have an atomic arrangement of ie, methine dyes, azomethine and thiazole dyes, and the like. (Pinacyanol), Astraphloxine Violet, Astrasone Orange R, Rosol Red 6B, Thioflavine T, Citroflavine 8G ).

Meanwhile, B in the general formula includes dyes capable of forming a quaternary ammonium structure in an acidic solution, that is, thiazine-based, oxazine-based, azine-based, and atrizine-based dyes. Examples thereof include Lauth's Violet. ), Methylene Blue, Acriflavine, Acridine Yellow, Rhoduling Violet B, Toluylene Red, Toluidine Blue O) etc. can be mentioned.

In the conventional copper acid plating solution, the size of copper electrodeposited particles is uniform in a wide current density range, obtaining fine and flexible copper plating, and having high gloss and smoothness and high conductivity and excellent conductivity at extremely low stress for a long time. In terms of what you can get, there are many things that need to be improved.

The present inventors continued to improve the conventional defects in the acidic copper plating solution. When the acidic copper plating solution contains the dye derivative represented by the general formula of the present invention, the size of the electrodeposited copper particles is uniform. It has been confirmed by many experiments that fine copper can be obtained with smooth copper plating having low stress and high malleability.

Hereinafter, the present invention will be described in detail. First, the compound of the present invention is to validate the dye derivative represented by the general formula B-N = N-A-N = N-B of the present invention as described above.

The concentration of the dye derivative of the present invention contained in the acidic copper plating solution is determined by the required plating surface state in combination with the individual compounds used and other compounds, but when used at 0.0002 g / l or less, there is no practical effect. On the contrary, the case where 0.15 g / l or more is used also has no effect similarly to the case below. Sometimes they are not used because they are plated on tree branches. Therefore, the range of 0.0002 g / l to 0.15 g / l is usually suitable.

Next, the characteristics of the copper plating solution of the present invention will be described with reference to the acid copper plating solution of the prior art.

A solution containing 0.01 g / l of a dye derivative in which A is Astrazone Red 6B and B is Laus Violet in an acidic copper plating solution of 220 g / l of copper sulfate, 60 g / l of sulfuric acid, and liquid temperature of 25 ° C. With stirring, the current density is up to 8 A / dm 2, and if it is strongly stirred, if the electrodeposited particles are uniform in size up to the current density, that is, the allowable current density is fine, moreover, the semi-gloss smooth copper plating rich in low stress conductivity is produced. You can get

In addition, this liquid can be smoothly used as a primary coating for glossy nickel plating and other plating because of the above-mentioned smooth copper plating with good physical properties and semi-gloss. In addition, there is no boot-phase plating or tree-plated plating at a wide range of temperatures and current densities, and furthermore, semi-gloss smooth copper plating with good physical properties can be obtained. Therefore, printing rollers, printing rollers, and electric poles are used. It can be used for thick plating such as, and for continuous plating such as wire rod and post-member. However, in an acidic copper plating solution containing 0.01 g / L of a known dye, which is very similar to the dye derivative represented by the general formula of the present invention, for example, Janus Blue in US Patent No. 2,707,166, solution temperature 25 Current densities up to 6 A / dm 2 can be used with normal agitation at < RTI ID = 0.0 > C, < / RTI > but portions of current density below 1 A / dm 2 are coarse in size and coarse. On the contrary, at high current densities, it is likely to be boot-phase plating. On the other hand, if the liquid temperature is raised to 35 ° C, the booth-phase plating decreases, but the entire surface becomes coarse particles, and in particular, the current density portion of 6 A / dm 2 or less becomes rough plating. In addition, when the concentration is increased to 0.03 g / L, the coarse precipitate portion is partially increased, the plating is weakened, and the adhesion is reduced, so that satisfactory results can be obtained not only for the initial copper plating but also for thick plating. Janus buru therefore needs to be used in combination with other materials, such as dextrin 1.5 naphthalene disulfonate (sodium salt), to at least obtain satisfactory plating.

In this case, for example, in dextrin, the stability of the copper plating solution is deteriorated due to the harmful substances by decomposition. On the other hand, since the sulfonic acid compound is stably present in the liquid, it results in an unbalanced behavior in the vicinity of the negative electrode of both compounds, and is likely to be partially coarse plating and dendritic plating, making it difficult to use industrially.

As described above, the Janus buru has drawbacks. On the contrary, a good result can be obtained with the dye derivative of the present invention, that is, although the two compounds have a very similar structure in part, the effect is remarkably different. Presumably due to the same reason.

의 원자한 85중량%의 클라블란산이 함유되어 있는 것을 나타낸다.In these two compounds, when the basic structure acting as an important factor in the precipitation of copper in the liquid, the dye derivatives represented by the general formula of the present invention are about 2.5 times larger in molecular weight than Janus buru. Absolutely has a large number of conjugated double bonds containing a number capable of forming a quaternary ammonium structure and a diazo group (-N = N-). Structure in which a diazo group is adjacent to both sides of a molecule having an ammonium structure, that is,

To 85% by weight of clavlanic acid.

It is assumed to be in an array structure.

Therefore, since dyes having a structure such as Janus buru are very easy in charge transfer of ions, they appear to have an effective function, but they are easy to decompose in a liquid, but are disadvantageous in booth phase plating or tree branch plating. There is this.

On the other hand, in the salt derivatives represented by the general formula of the present invention, the easy charge transfer of all the ions of the compound is similar to that of Janus bru, but since the molecules are large, they have a tautomatic structure having various and complicated behaviors. It becomes stable in a liquid. In fact, the dye derivative of the present invention does not show a single color in the liquid, but shows a complex color in various ways depending on the conditions of the liquid. Therefore, even in the liquid, the behavior around the cathode is complicated, and as a result, it is estimated to have an extremely similar effect.

This is because in the general formula of the present invention, when there is one diazo group (-N = N-), that is, a dye derivative having an structure of AN = NB ', for example, A is Astrazone Red 6B, B' is Raus Biolet. Although it is more effective than phosphorus dye derivatives than Janus bluru, it can be estimated from the fact that only the result which was inferior in effect compared with the dye derivative represented by the said general formula of this invention was obtained.

As a suitable composition of the acidic copper plating solution of the present invention, a dye derivative represented by the above general formula of 0.0002 to a acidic plating solution of copper sulfate 40 to 260 g / l, sulfuric acid 20 to 200 g / l and chlorine ion 5 to 120 g / l 0.15 g / l.

In addition, the operating conditions of the acid copper plating solution of the present invention is in the range of a liquid temperature of 10 to 40 ℃, preferably 20 to 30 ℃, moreover, to increase the allowable current density of the copper plating solution and to stir the liquid in order to promote the gloss and smoothness of the plating It is advantageous. This agitation is carried out by air agitation, cathodic movement, or both methods in combination.

Hereinafter, the present invention will be described in detail by way of examples.

Example 1

220 g / L of copper sulfate, 60 g / L of sulfuric acid, 10 mg / L of chlorine, and acidic copper plating solution contain 0.015 g / L of a dye derivative in which A is Astrazone Pink FG and B is Violet B with rhodium B in the above formula. Air stirring is performed at 25 ° C. The bronze plate was plated for 15 minutes using a 5 × 10 × 0.03 cm sample polished with 280 # emery polishing cloth. As a result, a semi-gloss smooth copper plating having a uniform and fine size and excellent malleability was obtained at a current density of 0.5 A / dm 2 to 8 A / dm 2.

Example 2

In the acidic copper plating solution as in Example 1, 0.01 g / L of a dye derivative in which A is astraproxin violet and B is rhodium violet B in the general formula of the present invention is contained, and the liquid temperature is 25 ° C. to 35 ° C. As a result of performing a plating with a thickness of 20 microns using the same sample as in Example 1, the size of the coin particles was uniform, fine and more malleable in the current density range of 0.3 A / dm 2 -10 A / dm 2. A smooth copper plating with good gloss was obtained.

Claims (1)

A plating solution characterized by containing a dye derivative represented by the general formula B-N = N-A-N = N-B in an acidic copper aqueous solution of copper sulfate and sulfuric acid. In which A is

Denotes a dye capable of forming an atomic arrangement of and B denotes a dye capable of forming a quaternary ammonium structure in an acidic solution.