KR810000022B1 - Tin electro-plating solution - Google Patents

Abstract

Tin electro-plating solution contains sulfamic acid ion 30-300 g/l, divalent tin ion 15-300 g/l and aromatic nucleus OH group or the salt 5-100 g/l. Thus, the plating solution which contains divalent tin ion 70.2 g/l, sulfamic acid ion 2 10 g/l, polyethyleneglycol nonylphenylether 20 g/l and O-cresol sulfonic acid 40 g/l is coated on the copper plate at the temp. 30≰C with 25 A/dm2 current density for 50 seconds.

Description

Tourmaline plating solution

The present invention relates to a tourmaline plating solution of a novel composition.

Conventionally, sulfuric acid baths and boron fluoride baths are mainly used as stone plating solutions, but sulfuric acid baths have a current density of about 10 A / dm ² , and boron fluoride baths are difficult to remove fluorides and extinguishing products in the waste liquid treatment step. It also had the drawback of being highly corrosive.

MEANS TO SOLVE THE PROBLEM The present inventor has reached | attained this invention as a result of repeating research in order to obtain the stone solution which does not have the above faults. That is, the present invention comprises (1) a sulfamic acid ion, a divalent stone ion (a first stone ion), an aromatic nucleus-OH group or an aromatic sulfonic acid having a -OH group and a -CH ₃ group or a salt thereof. A stone plating solution characterized in that a nonionic or anionic surfactant is added to the plating solution and the plating solution of the above (1), or to a stone plating solution characterized by adding glue or gelatin to the plating solution of the above (1). .

The sulfamic acid ion source used in the present invention may be any one that generates sulfamic acid ions in an aqueous solution, but specific examples thereof include sulfamic acid, sodium sulfamate, potassium sulfamate, and ammonium sulfamate. The concentration of sulfamic acid ions is in the range of preferably 30 to 300 g / l, and less than 30 g / l can not sufficiently maintain the concentration of stones in the plating solution, resulting in poor electrical conductivity. If it exceeds 300g / ℓ, there is no special obstacle but it is unnecessary.

The divalent stone can be added in the form of a oxidizing agent, a first sulfate, a first chloride, or the like, and the divalent stone ion concentration is preferably in the range of 15-300 g / L, and less than 15 g / L. Although the smoothness of electrodeposition is not sufficient, the current density is not sufficiently large, and there is no particular obstacle even if it exceeds 300 g / L, but the loss of the stone due to the expenditure of liquid is severe, so it is usually within this range. Good to do.

Examples of the aromatic sulfonic acid include cresol sulfonic acid, phenolsulfonic acid, naphthasulfonic acid or salts thereof, and the concentration thereof is preferably in the range of 5-100 g / l. If the concentration is less than 5 g / l, the stabilization effect of the stone is insufficient and 100 g / l. There is no obstacle in particular, but it is unnecessary. Moreover, the salt, for example, sodium salt and potassium salt, also shows an effect in the same range. Moreover, their ortho, meta and para isomers all have the same effect, and in general they are synthesized as mixtures and can be suitably used alone or in mixtures in their use.

As for the surfactant, nonionic compounds include polyethylene glycol nonylphenyl ether, polyethylene glycol isooctyl ether, polyethylene glycol lauryl ether, and the like. bad. Anionic ones include sodium n-octyl sulfate. Surfactant concentration is usually 1g / l or more as a pure component, and the smoothing effect is large. Less than 1g / l has a smoothing effect, but it is not enough. Above 30g / l, in particular, the electrodeposited material has problems. None, but it is unnecessary because the bubble of the plating liquid is severe.

In addition, smooth electrodeposition can be obtained by using gelatin or glue without using a surfactant. The amount of glue or gelatin added is 1-10 g / L, and there is no particular problem other than this range, but sufficient smoothing action is expected within a predetermined range.

When plating using the calcification solution of the present invention, it is preferable to operate within a current density range of 1 A / dm ² -100 A / dm ² at a temperature range of 5-80 ° C., in which case a current density of ^{2 A} / dm ² or more. It is preferable to carry out stirring in the range.

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

Example 1

The electrodeposition liquid was deposited on a copper plate at a temperature of 30 ° C. at a current density of 25 A / dm ² for 50 seconds to obtain an electrodeposition having a good smooth surface.

The electrodeposition solution was electrodeposited at 25 ° C. for 25 seconds at 25 A / dm ² on a linkage line having a diameter of 1 mm at 25 ° C. to obtain an electrodeposition material having a plating thickness of 10 μm and a nonuniformity of plating thickness of μm or less. It has good corrosion resistance, and almost no discoloration is seen in the room left for one year, the solderability is safe, and there is no property to swell during soldering.

Example 2

10 g / L of any of polyethylene glycol isooctyl ether, polyethylene glycol lauryl ether, and sodium n-octyl sulfate was added in place of the polyethylene glycol nonyl phenol ether of Example 1, and the plating was carried out under the same conditions as in Example 1. Could get a good electrodeposition like 1.

Example 3

To 5A / dm ² for copper wire with a diameter of 1.2mm at 20 ℃ using the electrodeposition solution to the plating cell hayeoseo 4 minutes before the complex obtained is the case where there has a smooth exterior hayeoseo heated to melt the coating layer, the melted portion and The swelling phenomenon was not seen at the boundary of the unmelted portion, and no spark was generated even when melted. Thereby, it can be said that it is excellent compared with the conventional sulfuric acid bath and the borosilicate bath.

Example 4

The electrodeposited product obtained by electroplating at a current density of 20 A / dm ² on a copper plate at a temperature of 25 ° C. by using an electrodeposition liquid of the present invention exhibits a smooth appearance.

Example 5

The electrodeposited product obtained by plating for 2 minutes at 5 A / dm ² at a linkage wire of 1.2 mm in diameter at 20 ° C. using the electrodeposition liquid having the electrodeposited liquid had a semi-gloss of a plating thickness of 5 μ, and the solderability test also showed good results. The results of the solderability test of the sample prepared by the method of the present example showed that there was no solder loaming and no swelling phenomenon during soldering.

In addition, the electrodeposited product obtained by plating for 10 minutes at 10 / dm ² had a matte thickness of 10 µm but a smooth surface and a good solderability test result.

[Comparative Example]

The conventional plating method used the electrodeposition liquid of the following composition as an example.

Plating was performed for 2 minutes on the copper wire of diameter 0.6mm, stirring at liquid temperature of 25 degreeC, and current density of 10A / dm <^2> , and 10-micrometer plating layer was obtained. The appearance was good, but there was a lot of swelling when heated at 180 ° C. for 30 minutes.

Example 6

The electrolytic solution was plated with stirring at a current density of 1 A / dm ² -50 A / dm ² at a linkage line of 1.2 mm in diameter at 20 ° C., and an electrodeposited material having a good smooth surface was obtained.

As a result of the soldering test of the electrodeposited in this way with a current density of 10 A / dm ² for 2 minutes, solderability was safe and there was no swelling phenomenon at all.

In preparing the electrodeposition solution, first, the sulfamic acid and the cresol sulfonic acid are dissolved in a predetermined amount of water, followed by dissolution by adding a cuprous oxide to the solution, and then the solution is filtered, and the gelatin (5 g of gelatin) swollen with water in advance in the filtrate. A ratio of about 100 ml of water is appropriate, but this ratio does not have to be strictly adhered to).

Example 7

5 g / l glue was added instead of the gelatin of Example 6 and plated under the same condition as in Example 6, whereby good electrodeposition material was obtained as in Example 6.

Example 8

20 g / l of paraphenolsulfonic acid or 27 g / l of sodium paraphenol sulfonic acid was added instead of ortho phenol sulfonic acid of Example 3, and plating was carried out under the same conditions as in Example 3 to obtain a good electrodeposition product as in Example 3. Could.

Example 9

45 g / l of 1-naphthol-4-sulfonic acid sodium 45g / l or 1-naphthol-5-sulfonic acid sodium 45g / l was added instead of ortho cresol sulfonic acid of Example 1, and plating was performed under the same conditions as in Example 1. As described above, good electrodepositions were obtained.

Example 10

The electrodeposition liquid was deposited on a copper plate at a temperature of 30 ° C. for 3 minutes at a current density of 5 A / dm ² to obtain an electrodeposited material having a good smooth surface. In all cases of these examples, the material to be plated is first used as a pretreatment for plating.

In an alkali degreasing liquid having a composition of 1 min. With cathodic electrolytic degreasing at a liquid temperature of 60-80 ° C. and a current density of 5 A / dm ² , it is washed with water. Further, the solution was immersed in 20% aqueous sulfuric acid solution for 30 seconds, washed with water, and plated under the conditions of the respective examples. In addition, when a nonionic surfactant or anionic surfactant was used in each Example, these were previously added with water for 3-20 with respect to 1 use of a surfactant pure component, stirring, heating, and mixing, use.

In each example, all solderability tests were carried out in accordance with MIL-standard-202C.

Claims (1)

30-300 g / l of sulfamic acid ions, 15-300 g / l of divalent cation ion, containing 5-100 g / l of aromatic sulfonic acid or salt thereof having -OH group or -OH group and -CH ₃ group Stone stone amount to be.