JPS6231076B2 - - Google Patents

Description

[Detailed description of the invention]

Many methods have been adopted in the nickel plating industry to preserve nickel and reduce costs. These methods include reducing the thickness of the nickel plating layer, replacing some or all of the nickel with cobalt when cobalt is cheap or readily available, and more recently, reducing the thickness of the nickel plating layer. Approximately 60% of the total cost is made of relatively inexpensive iron such as nickel-iron, cobalt-iron, or nickel-cobalt-iron alloy. However, as the thickness of the plating layer decreases, more effective or "stronger" nickel brighteners or higher concentrations of nickel are required to obtain the gloss and leveling levels customary in the nickel plating industry. It will be necessary to use brighteners. More “stronger” nickel brighteners or high concentration brighteners are
Although it is possible to obtain the desired gloss and leveling, it also causes unexpected side effects. If the plating layer peels off or if strong stress is applied,
It can become severely embrittled and less receptive to subsequent chrome plating, or it can also become hazy, have poor coverage at low current densities, and exhibit "throw" or striations and scratches. skip plate),
That is, there may be a portion where the plating layer is not obtained. To overcome such deleterious effects of "strong" brighteners or high concentration brighteners, the addition of various sulfuric acids or their salts has been proposed in U.S. Pat.
Recommended by Brown in No. 2654703;
For this purpose, the use of organic hydroxysulfonates has been described by Passal in US Pat. No. 3,697,391.
Recommended by Unfortunately, these compounds significantly reduce the leveling and bright range of the plating layer. Various further attempts have been made to improve the low current density properties when using "strong" brighteners or high concentrations of brighteners: (i) aromatic monoamines by Du Rose, U.S. Pat. No. 3,630,857; Use of aromatic polyamines, polyethylene polyamines without substituents. (ii) U.S. Patent No. 3,862,019, N by Rosenberg
- Use of (3-sulfopropyl)pyridinium inner salt. (iii) Use of N-disubstituted aminopropyl or its hydrochloride salt according to US Pat. No. 4,054,495, Law. Although these compounds do improve the low current density properties, they have not yet been able to provide low current density plated layers without darkness or fading of the finish. It is an object of the present invention to provide a method and composition for electrodepositing nickel electroplating that has greater tolerance for "heavy" brighteners or high concentration brighteners. It is also an object of the invention to achieve this tolerance without affecting the leveling of the plating layer. It is also an object of the present invention to achieve this tolerance while providing a low current area without darkening or fading of the gloss without affecting the gloss range. From this standpoint, the present invention relates to methods and compositions for making nickel electroplating. That is,
The present invention provides a method for producing a nickel electrodeposited layer, which comprises passing a current from an anode to a cathode in an acidic electroplating aqueous solution containing at least one nickel compound (i) an acetylenic amine or Substituted amines, aliphatic or aromatic acetylenic amines or substituted amines, and (ii) acetylenic sulfonic acids and their salts (provided that the acetylene bond and sulfonic acid group have 1 carbon number)
linked by ~6 carbon chains. ), for a sufficient period of time to form a metal electroplating on the cathode. The concentration of said compound is: (i) acetylenic amine or substituted acetylenic amine, aliphatic or aromatic;
………0.005-0.1g/ (ii) Acetylenic sulfonic acid and its salts
…0.005 to 0.25 g/, and the preferred range is (i) aliphatic or aromatic acetylenic amine or substituted amine …0.01 to 0.04 g/ (ii) acetylenic sulfonic acid and its salts
......0.01~0.10g/. Examples of the acetylenic amines and substituted acetylenic amines of the present invention include, but are not limited to, 4-diethylamino-2-butyn-1-ol 1,6-bis-(diethylamino)-2-hexyne 1-dimethylamino -2-propyne N-methylpropargylamine Propargylamine 1-diethylamino-2-propyne 5-dimethylamino-2-methyl-3-pentyn-2-ol 1-dimethylamino-2-pentyne 3-methylamino-1-butyne 1-dimethylamino-2-hexyne 1-dimethylamino-2-butyne 1-diethylamino-2-butyne 1-diethylamino-2-hexyne 4-diethylamino-1-butyne 4-diethylamino-2-pentyn-4-ol 1. 6-bis(morpholino)-2-hexyne There is 6-diethylamino-1-piperidino-2-hexyne. Examples of the acetylenic sulfonic acids of the present invention include, but are not limited to, 2-butyne-1,4-disulfonic acid 2-butynesulfonic acid propargyl sulfonic acid 1-butynesulfonic acid 1-pentinsulfonic acid The plating bath may contain an effective amount of at least one material selected from the group consisting of (a) class brighteners, (b) class brighteners, and (c) anti-pitting agents or wetting agents. The term “class brightener” as used herein is taken from Modern Electroplating, edited by F. Lowenheim.
As described in the 3rd edition, aromatic sulfonates, sulfonamides, sulfonimides, etc., as well as aliphatic or aromatic-aliphatic olefin unsaturated sulfonates, sulfonamides, sulfonimides, etc. Examples of such plating additives are: (1) Sodium o-sulfobenzimide (2) Disodium 1,5-naphthalene trisulfonic acid (3) 1,3,6-naphthalene trisulfonic acid・
3-sodium (4) Sodium benzene monosulfonic acid (5) Dibenzene sulfonimide (6) 3-chloro-2-butene-1-sulfonic acid
Sodium (7) Sodium β-styrene sulfonate (8) Monoallyl sulfamide (9) Diallyl sulfamide (10) Allyl sulfonamide. Such plating additive compounds may be used alone or in suitable combinations, and may be used in amounts ranging from about 0.5 to 10
It is preferred to use amounts in the range of g/g, with the advantages described in the above literature and which are well known to those skilled in the art of nickel electroplating. As used herein, the term "class brightener" refers to diethoxylated 2-butyne-1,4-diol or dipropoxylated 2-butyne-1,4-diol, as described in Modern Electroplating, 3rd edition, edited by F. Lowenheim. Reaction products of epoxy compounds such as diols with alpha hydroxy acetylenic alcohols, other acetylenic compounds, N-
This means that it includes plating additive compounds such as heterocyclic compounds and pigments. Examples of such plating additives include: (1) 1,4-di-(β-hydroxyethoxy)-2
-butyne(2) 1,4-di-(β-hydroxyethoxy-γ
-chloropropoxy)-2-butyne (3) 1,4-di(β-,γ-epoxypropoxy)-2-butyne(4) 1,4-di-(β-hydroxy-γ-butenoxy)-2- Butyne (5) 1,4-di-(2'-hydroxy-4'-oxa-6'-heptenoxy)-2-butyne (6) N-(2,3-dichloro-2-propenyl)-
Pyridinium chloride (7) 2,4,6-trimethyl-N-propargyl-pyridinium bromide (8) N-allylquinaldinium bromide (9) 2-butyne-1,4-diol (10) Propargyl alcohol ( 11) 2-Methyl-3-butyn-2-ol (12) Quinaldyl-N-propanesulfonic acid betaine (13) Quinaldine dimethyl sulfate (14) N-allylpyridinium bromide (15) Isoquinaldyl-N-propanesulfone Acid betaine (16) Isoquinaldine dimethyl sulfate (17) N-allylisoquinaldine bromide (18) 1,4-di-(β-sulfoethoxy)-2-
Butyne (19) 3-(β-hydroxyethoxy)-propyne (20) 3-(β-hydroxypropoxy)-propyne (21) 3-(β-sulfoethoxy)-propyne (22) Phenosafranin (23) Fuchsin There is. When these classes of brighteners are used alone or in combination, preferably in amounts ranging from about 5 to 1000 mg/l, the electrodeposited layer exhibits no visible effect or a semi-gloss, semi-gloss, Generates a finely plated layer. However, the optimum plating gloss, gloss speed,
Best results are obtained when the class brighteners are used in conjunction with one or more class brighteners to provide leveling, bright plating current density ranges, low current density coatings, and the like. The term "anti-pitting agent or wetting agent" as used herein is meant to include materials that function to prevent or minimize gas pitting. Anti-pitting agents alone or in combination,
When used preferably in an amount in the range of about 0.05 to 1 g/g, the emulsifying, dispersing, dissolving action on contaminants such as oils, greases, etc. improves the compatibility of the contaminants with the bath; This promotes the formation of a more reliable plating layer. Preferred anti-pitting agents include sodium lauryl sulfate, sodium lauryl ether-sulfate and sodium dialkyl sulfosuccinate. Nickel compounds used for electrodeposited nickel are typically added as sulfate, chloride, sulfamate, or fluoborate salts. The sulfate, chloride, sulfamate and fluoborate salts of nickel are present in the electroplating solution of the present invention at a concentration of about 10 to 150
g/concentration of nickel. The nickel electroplating bath of the present invention further has a pH adjusted (e.g., about 3.5 to 4.5, preferably 4.0);
Boric acid or other buffering agent, about 30-60g/, to prevent high current density burning
Preferably it can contain about 45g/. To prevent "burning" of high current density areas and to control the temperature of the solution more uniformly, the solution is stirred. Stirring of the solution is sufficient using any of air agitation, mechanical agitation, pumps, cathode rods, and other solution agitation means. The solution can also be operated without stirring. The operating temperature of the electroplating bath of the present invention is from about 40°C to
The temperature is about 70°C, preferably about 50°C to 62°C. The average cathode current density is approximately 0.5-12 A/ ^dm2 , with an optimum range of 3-6 A/ ^dm2 . Representative nickel-containing electroplating aqueous solutions (which can be used in combination with effective amounts of co-additives) are as follows, with all concentrations in grams/grams unless otherwise specified.

[Table] During bath operation, the pH usually tends to increase, so adjust it with acids such as hydrochloric acid and sulfuric acid. The anode used in the bath is a bar, strip or small chunk of electrolyte or sulfur-containing nickel placed in a titanium basket. All anodes are typically covered with a cloth or plastic bag having the desired porosity to minimize the introduction of metal particles, anode slime, etc. into the bath. This is because metal particles, anode slime, and the like may mechanically or electrophoretically move to the cathode and roughen the plating layer of the cathode. Supports which can be coated with the nickel electrodeposited layer of the invention are metals or metal alloys commonly electrodeposited and used in the electroplating field, such as nickel, cobalt, nickel-cobalt, copper, tin, brass. etc. Other typical support base metals from which plated products are manufactured include iron, steel,
Alloys include steel, copper, tin and ferrous metals such as their alloys with lead, copper alloys such as brass, bronze etc., zinc, especially in the form of zinc-based die castings; It may also be covered with other metal plates such as. The base metal support has a variety of surface finishes, depending on the desired final appearance, and these vary depending on factors such as the luster, gloss, leveling, thickness, etc. of the nickel electroplating to be coated on the support. do. Nickel electrodeposited layers are obtained using the various parameters mentioned above, but the gloss, leveling, ductility and covering power are not sufficient or satisfactory for certain applications. In addition, the plated layer may become cloudy, exhibit wrinkles, step plates, peeling,
It may show areas of low gloss or low chromium receptivity. These conditions are particularly likely to occur after supplementation of excessive amounts of class brighteners or with the use of particularly strong class brighteners. (i) aliphatic or aromatic acetylenic amines or substituted acetylenic amines; and (ii) acetylenic sulfonic acid compounds and salts thereof;
(However, the acetylene bond and the sulfonic acid group are bonded by a carbon chain having 1 to 6 carbon atoms.) The above drawbacks can be corrected by adding or containing a certain amount to the acidic nickel electroplating aqueous bath. . Additionally, the combination of these types of compounds allows class brighteners to be used at higher than normal concentrations, thereby providing faster gloss and leveling than would normally be expected under these conditions. This is possible without vertical wrinkles, fading, areas with weak gloss, etc. The two classes of compounds of the present invention are characterized by the following features: That is, they act synergistically to reduce dark colors, creasing, fading, etc. in the presence of "strong" or high concentrations of class brighteners without affecting the leveling or gloss distribution of the electrodeposited layer. Forms a reliable low current density plating layer without any problems. If these compounds are used independently of each other and a "strong" or high concentration of class brighteners is present, the electrodeposited layer formed will still be affected by one or more of the following effects: Low current density shows dark color, vertical wrinkles, fading, and low gloss distribution. The concentrations of the compounds of the invention are: (i) acetylenic amines or substituted acetylenic amines, aliphatic or aromatic, acetylenic amines or substituted acetylenic amines;
………0.005-0.1g/ (ii) Acetylene series sulfonic acid compound and its salt (However, the acetylene bond and the sulfonic acid group are connected by a carbon chain having 1 to 6 carbon atoms)
…0.005 to 0.25 g/, and the preferred concentration is: (i) aliphatic or aromatic acetylenic amine or substituted acetylenic amine
………0.01 to 0.04 g/ (ii) Acetylene series sulfonic acid compounds and their salts (however, the acetylene bond and the sulfonic acid group are connected by a carbon chain having 1 to 6 carbon atoms)
......0.01~0.10g/. The following examples are provided to provide those skilled in the art of electroplating with a better understanding of various embodiments and embodiments of the present invention. It goes without saying that these examples do not limit the scope of the present invention in any way.

[Table] The conditions for plating panels from the above aqueous nickel electroplating composition were as follows. Zinc-coated steel panels were stripped in 50% hydrochloric acid, rinsed, and then scored with a horizontal single pass of 4/0 grit emery sand paper and 2 grit emery sand paper. The cleaned panels were then plugged with the above composition in a 267 ml Hull Cell for 10 minutes with cathodic rocker agitation at 2 amps of cell current. Observations: Panel #1 exhibits a ductile plating layer with considerable gloss and leveling, low current density dark color, fading, and haze at 2-4 asf, and thin plating areas at 0-1 1/2 asf. Panel #2...Shows a glossy, well-leveled, ductile plated layer and uniform gloss distribution without defects at low current density. Panel #3: Good gloss and leveling, excellent gloss distribution, exhibiting low current density dark color and unblemished ductile plated layer. Panel #4: Good gloss and leveling, good gloss distribution, exhibits low current density dark color and unblemished ductile plated layer. Panel #5... exhibits a low current density defect-free ductile plated layer with good gloss and leveling, uniform gloss distribution. Although the invention has been illustrated with reference to examples,
It goes without saying that those skilled in the art can easily make improvements and changes within the scope of the present invention.

Claims (1)

[Scope of Claims] 1. A composition for producing a nickel electrodeposited layer comprising an acidic electroplating aqueous solution containing at least one nickel compound, comprising: (i) an aliphatic or aromatic acetylenic amine or substituted amine, 0.005; g/~0.1 g/; and (ii) acetylenic sulfonic acids and their salts, 0.005
g/~0.25 g/ (however, the acetylene bond and the sulfonic acid group are bonded by a carbon chain having 1 to 6 carbon atoms) for a sufficient period of time to form metal electroplating on the cathode. A composition for producing a nickel electrodeposition layer, characterized by: 2. The composition according to claim 1, wherein the acetylenic amine is 4-diethylamino-2-butyn-1-ol. 3 The acetylenic amine is 1,6-bis-
The composition according to claim 1, which is (diethylamino)-2-hexyne. 4. The composition according to claim 1, wherein the acetylenic amine is 1-dimethylamino-2-propyne. 5. The composition according to claim 1, wherein the acetylenic amine is N-methylpropargylamine. 6. The composition according to claim 1, wherein the acetylenic amine is propargylamine. 7. The composition according to claim 1, wherein the acetylenic amine is 1-diethylamino-2-propyne. 8. The composition according to claim 1, wherein the acetylenic amine is 5-dimethylamino-2-methyl-3-pentyn-2-ol. 9. The composition according to claim 1, wherein the acetylenic amine is 1-dimethylamino-2-pentyne. 10. The composition according to claim 1, wherein the acetylenic amine is 3-methylamino-1-butyne. 11. The composition according to claim 1, wherein the acetylenic amine is 1-dimethylamino-2-hexyne. 12. The composition according to claim 1, wherein the acetylenic amine is 1-dimethylamino-2-butyne. 13. The composition according to claim 1, wherein the acetylenic amine is 1-diethylamino-2-butyne. 14. The composition according to claim 1, wherein the acetylenic amine is 1-diethylamino-2-hexyne. 15. The composition according to claim 1, wherein the acetylenic amine is 4-diethylamino-1-butyne. 16. The composition according to claim 1, wherein the acetylenic amine is 4-diethylamino-2-pentyn-4-ol. 17. The composition according to claim 1, wherein the acetylenic amine is 1,6-bis(morpholino)-2-hexyne. 18. The composition according to claim 1, wherein the acetylenic amine is 6-diethylamino-1-piperidino-2-hexyne. 19. The composition according to claim 1, wherein the acetylenic sulfonic acid is 2-butyne-1,4-disulfonic acid. 20. The composition according to claim 1, wherein the acetylenic sulfonic acid is 2-butinsulfonic acid. 21. The composition according to claim 1, wherein the acetylenic sulfonic acid is propargyl sulfonic acid. 22. The composition according to claim 1, wherein the acetylenic sulfonic acid is 1-butinsulfonic acid. 23. The composition according to claim 1, wherein the acetylenic sulfonic acid is 1-pentinesulfonic acid.