JPS61147896A - Nickel and nickel alloy electroplating bath - Google Patents

Abstract

PURPOSE:To obtain an electrodeposited material which is uniform and is excellent in stress and ductility by adding a sulfonic acid compd., aliphat. unsatd. alcohol compd. and aliphat. unsatd. carboxylic acid compd. to an acidic nickel and nickel alloy plating bath. CONSTITUTION:The sulfonic acid compd. and aliphat. unsatd. alcohol compd. are added to the acidic nickel plating bath and acidic nickel cobalt alloy plating bath or acidic nickel-iron alloy plating bath and further the aliphat. unsatd. carboxylic acid compd. is incorporated therein. A vinyl sulfonic acid, benzene sulfonic acid, etc., are adequately used for the above-mentioned sulfonic acid compd., propargyl alcohol, 3-butine-1-ole, etc. for the aliphat. unsatd. alcohol compd. and maleic acid, aconitic acid, etc., for the aliphat. unsatd. carboxylic acid compd. The electrodeposited material obtd. in the above-mentioned manner has the brightness and smoothness, has no leveling effect and is uniform as said material has low internal stress and excellent ductility.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is applicable to nickel, nickel-cobalt, nickel-cobalt, and nickel-cobalt.
This relates to electrodeposition plating of metals such as iron.

<Prior Art> Conventionally, this type of technology has used additives in combination with a sulfonic acid compound and an aliphatic unsaturated alcohol compound.

<Problems to be solved by the invention> Conventional additives using a combination of a sulfonic acid compound and an aliphatic unsaturated alcohol compound have a smoothing effect as well as gloss, but may cause warping depending on the substrate. .

In addition, due to the lack of suitable additives for the demand for architectural hardware and parts of weak electrical products, it is necessary to dilute general acidic nickel electroplating brighteners or to use sulfonic acid compounds and aliphatic unsaturated alcohol compounds (e.g. saccharin). and 1,4-butynediol, etc.), but because they have gloss and leveling, there are significant differences depending on the usage conditions, and it is difficult to maintain the same performance. This method is extremely difficult and has the disadvantage of lacking uniformity. In addition, in conventional work, the gloss and leveling differed depending on the temperature difference inside the plating bath, resulting in a lack of overall uniformity, and even in the same rack, the current distribution was different between the top and bottom, causing gloss and leveling to vary between the top and bottom. It was often seen that this resulted in differences in leveling.

The electroplating bath of the present invention is intended to eliminate these conventional drawbacks and provide an electrodeposited product that is uniform and has excellent stress and ductility under all working conditions.

<Means for Solving the Problems> The present invention provides acidic nickel plating baths, acidic nickel-cobalt alloy plating baths, and acidic nickel plating baths using sulfonic acid compounds, aliphatic unsaturated alcohol compounds, and aliphatic unsaturated carboxylic oxides as additives. - It is added to the iron alloy plating bath and contains these three types of compounds together. Representative examples of the three types of compounds are as follows.

Typical examples of sulfonic compounds: vinylsulfonic acid, benzenesulfonic acid, allylsulfonic acid, toluenesulfonic acid, chlorbenzenesulfonic acid, brominebenzenesulfonic acid, dichlorobenzenesulfonic acid, benzenedisulfonic acid, benzenetrisulfonic acid, sulfobenzoic acid, Sulfosalcylic acid, aminobenzenesulfonic acid, naphthalene monosulfonic acid, naphthalene disulfonic acid, naphthalene trisulfonic acid, diphenyl disulfonic acid, diphenyl sulfone disulfonic acid, diphenyl ether disulfonic acid, thiophene sulfonic acid, benzene aldehyde sulfonic acid, benzene sulfonic acid Amide, benzenesulfimide, toluenesulfonic acid, dinaphthalenesulfamide, N-phenylsulfonylnaphthalenesulfamide, methylbenzenesulfamide, N-N'bis(dichlorophenylsulfonyl)benzenesulfonamide, P-P' Methylenebis(dibenzenesulfonamide), N-N'-(P-trusulfonyl)-4,4'-diphenyldisulfonamide, methylenebisnaphthalenesulfonic acid, methylenebisbenzenesulfonic acid, saccharin, N-acetylbenzenesulfimide , allylsulfonamide.

Typical examples of fatty unsaturated alcohol compounds Propargyl alcohol, 3-butyn-1-ol, 2-
Butyne-1,4-diol, 1-methyl-3-butyne-
2-ol, 3-methyl-1-pentyn-3-ol,
3-ethyl-1-pentyn-3-ol, 4-methoxy-2-butyn-1-ol, 3-hexyne-2,5-diol, 4-octyl-3,6-diol, 2,5-dimethyl- 3-hexyne-2,5-diol, 3-pentyn-1-ol, 2,4-hexazine-1,6-diol, 2-butene-1,4-diol, 2-methyl-2-
Buten-1-ol, vinyl alcohol, 2-propan-1-ol, 3-buten-1-ol, 4-penten-1-ol, 2-methyl-4-penten-2-ol.

Typical examples of aliphatic unsaturated carboxylic acid compounds Maleic acid, aconitic acid, fumaric acid, dihydromuconic acid, itaconic acid, muconic acid, mesaconic acid, acetylene dicarboxylic acid, glutaconic acid, acrylic acid, crotonic acid, citraconic acid,
Sorbic acid.

<Function> It is known that adding sulfonic acid compounds such as saccharin and unsaturated aliphatic alcohols to an acidic nickel bath can produce electrodeposit with leveling and gloss.
The plating bath in the present invention has leveling properties by adding not only nickel alone but also a sulfonic acid compound, aliphatic unsaturated alcohol, and aliphatic unsaturated carboxylic acid to a nickel-based electroplating bath containing cobalt and iron. It is possible to form a nickel-based plating film that gives luster.

<Example> The present invention will be specifically explained below using examples.

However, the plating data piece for each example is 10C111×6a1.
Puff polish a 1×0.03clI brass plate, and then scratch in the middle with #800 sandpaper.

Furthermore, each current density and plating time are varied using the same adjusted sample pieces, and the leveling property is tested using a roughness tester to determine the effect. (For the following examples, refer to roughness test data Figures 1 and 2) <Example 1> N15On・6 Hz 250 g/j
! NiC1t・6Hz 45g/J!
H3B03 40 gallp H
4.0 Add 1 part sodium naphthalene trisulfonate to the basic bath having the above composition.
~3g/j! , 3-hexyne-2,5-diol 0.1
~0.05 g/Il and 1-3 g/j of crotonic acid
! were added respectively, the bath temperature was 40-55℃, and the current density was 2-4^.
/dm", air agitation, and plating for 10 to 15 minutes. As shown in Figures 1 and 2, there is no leveling of the precipitate on the material piece, and it has a glossy, homogeneous appearance and low stress. , it is possible to obtain a material with excellent ductility.

<Example 2> Ni S04.6 Hzo 300 g/
lNiC1□・6Hz0 40g/j! H3B
03 40 g/lp H4,2 1 to 3 g of sodium benzenesulfonate to the basic bath with the above composition
/l, 2-butyne-1,4-diol 0.05-0.1
g/j! and 1 to 3 g/It of fumaric acid, respectively, at a bath temperature of 40 to 55°C and a current density of 1 to 4 A/da"%.
When plating was carried out for 10 to 15 minutes with air agitation, the deposits on the material pieces were shiny with no leveling.
It has a homogeneous appearance, low stress, and excellent ductility.

<Example 3> N i (NHzS 03) z ・4 Hz
450 g/lNiC1, 6Hz030g/I H3B 03 40 g/
7! pH 4.0 1-3 g/i of saccharin in the basic bath of the above composition! , propargyl alcohol 0.05-0.03 g/12 and fumaric acid 0.5-1.5 g/j! and bath temperature 4.
When plating is carried out for 10 to 15 minutes at 0 to 55°C, current density of 2 to 3 A/da'', and air agitation, the precipitate on the material piece has no leveling, is glossy, and has a homogeneous appearance. It is possible to obtain products with low stress and excellent ductility.

<Example 4> N15O, 6 Hz 270 g/l
NiC1,・6Hz0 30g/jICOS
Oa・7Hz015g/I H3B03 40g#! pH4,
2 Add 1 part of sodium naphthalene trisulfonate to the basic bath having the above composition.
~3g/12,3-pentyn-1-ol 0.1-0.
05gait and citraconic acid 0.5-2.0g/l
By adding each of these and performing plating under the same working conditions as in Example 1, it is possible to obtain a homogeneous electrodeposited product that is glossy and has no leveling and has excellent ductility.

<Example 5> Ni (NHzSOs)z・4 Hzo 60
0 g/βNiC1g・6Hz0 5
g/βH3B03 40 g
/j! pH 4.0 Using the same additives as in Example 4 in the basic bath with the above configuration,
When plating is performed under the same working conditions, it is possible to obtain a glossy electrodeposited plating with excellent ductility and no leveling.

<Example 6> 1 to 3 g/1 saccharin to the basic bath described in Example 1
2.3-hexyne-2,5-diol 0.01g/1
When plating is carried out by adding 1 to 3 g/l of sorbic acid and sorbic acid, a ductile, uniform, glossy precipitate without leveling can be obtained.

<Example 7> N i (NHzS 03) z ・4 Hz
450 g/ItFe (NHzSOs)
' 5 Hz 25 g/lNiC1□・6H
z0 5g/IH3B 03
40 g/βpH 3.0 1 1 sodium naphthalene trisulfonate in the basic bath with the above composition
~3g/12-butyne-1,4-diol 0.05~0
．． 1g/j! , itaconic acid 1-3 g/l were added, the bath temperature was 40-55°C, and the current density was 1-3^/dII+2.
When plating is carried out for 10 to 15 minutes without stirring, the precipitate on the sample piece has no leveling, has a glossy, homogeneous appearance, and has excellent stress and ductility.

<Effects of the Invention> As detailed above, the present invention uses a combination of three types, a sulfonic acid compound, an aliphatic unsaturated alcohol compound, and an aliphatic unsaturated carboxylic acid compound, to smoothen microscopically uneven surfaces. It is possible to completely maintain the original shape of the material surface along the unevenness of macroscopic surfaces and eliminate leveling. Furthermore, the electrodeposited film has low internal stress, excellent ductility, and is homogeneous, and can be applied to a wide range of materials such as architectural hardware and parts of light electrical appliances. It can also be widely applied to pins, sockets, terminals, etc. of electronic parts that require gloss and physical properties.

Claims (1)

[Claims] Characterized by adding a sulfonic acid compound and an aliphatic unsaturated alcohol compound to an acidic nickel plating bath, an acidic nickel-cobalt alloy plating bath, an acidic nickel-iron alloy plating bath, and further containing an aliphatic unsaturated carboxylic acid compound. Nickel and nickel-based alloy electroplating baths.