3,133,005 United States Patent ‘O?ice Patented May 12, 1964 1 2 3,133,005 atoms may be present in the molecule, at present the AQH) NICKEL PLATE‘J G BATH lower carbon chains are considered to be more desirable. Barnet D. Ostrow, 125 Redwood Drive, and Fred I. Nobel, Together with the substances of the invention, the struc 75 Fern Drive, both of Roslyn, N.Y. tural formulas of which are given above, other acetylenic No Drawing. Filed May 28, 1962, Ser. No. 197,860 compounds may be incorporated into the bath, thus em 6 Claims. (Cl. MAL-49) ploying a mixture of unsaturated compounds. The structural formulas given below are illustrative of The present invention relates to the electrolytic deposi the substances included in the invention. tion of nickel, and it is directed primarily to the produc (1) H ’ tion of bright, smooth and lustrous deposits. 10 HCEC—-CH2—N—CH2—OHECH2 Previously, acid nickel plating baths were modi?ed by Allyl propargyl amine the introduction therein of additives intended to produce brightness of nickel deposits. Among such additives were (2) CH2CH=CHg various types of substances in conjunction with aromatic . ' HCEC-CH2—N and aliphatic sulfonates, sulfonamids and sulfonimids. 15 OHgCH=CH2 These prior suggested substances included alkynes, al Diallyl propargyl amine kenes, amines, alkyne amines, and alkene amines. Such (3) CH2CH=CH2 substances had in the molecule an allylic or vinyl group only, an acetylenic group only, or an active amino group nozo-om_?-onzon=orn only. It has also been proposed to incorporate com 20 CHzCH=CHn pounds having in the same molecule an amino and an Triallyl 'propargyl amine allyl or vinyl group. The essence of the invention lies in the structures of the While some addition agents accomplished this purpose additives in which there are combined in a single molecule, in some degree, they did not contribute to superior level the amino, alkyne and alkene radicals. The deposits re ing coupled with the ease of control. Also, because of 25 sulting from baths containing these additives have high the high concentration of these compounds that were nec~ lustre and are smooth with excellent leveling. In addi essary to produce the desired brightness and leveling the tion, the deposits do not exhibit low current density grey ductility was impaired. In some cases as with the alkynols ness which often occurs when additives such as amines or the deposit has a marked tendency to “skip plate,” i.e. to polyamines are used in the bath. prevent deposition of nickel at the-low current densities. Compounds of the present invention may be used The present invention has among its objects to intro~ singly or in mixtures or in the absence of other types of duce additives, for the above purpose, into aqueous acid additives. They may be used in standard Watts baths, all nickel plating baths, which will result in excellent leveling chloride baths, or high chloride baths. Improved results of the deposit. are obtained where there is incorporated therewith in the It is also among the objects of the invention to provide 35 bath a sulfonic acid, sulfonarnid or sulfonimid. a bath for the purpose described which will reduce the Typical standard nickel baths which are employed in low current density skip plate in the deposited ?lm of the invention are as follows in grams per liter. _ nickel. In practicing the invention, there is provided the usual Watts bath: aqueous acid nickel plating bath and there is incorporated 40 NiSO4.7H2O ______100-400 therein an additive which consists of at least one com NiCl2.7H2O ______5-80 pound which contains in the same molecule. an amino, an Wetting agents ______0-1 alkyne, and an alkene group. Substances having these Boric acid ______5-60 three groups impart superior leveling characteristics to the All chloride bath: bath, with a substantial improvement in low current den 45 NiCl2.7H2O ______50-200 sity characteristics of the nickel deposit. Relatively small Boric acid ______0-50 amounts of these substances are very effective, and they do Wetting agent ______. not impair the ductility of the deposit. Among typical wetting agents are sodium lauryl sul— These substances have the following structural for fates, sodium‘Z-ethyl hexyl sulfate, and sodium octyl sul 50 fonic acid. The range of pH is from 2.5 to 4.5 in usual practice. The following are speci?c examples of baths according to the invention which are employed to obtain bright, level and ductile deposits; the amounts being in grams per 55 liter of aqueous solution:

H a w is; or

Nickel Sulfate_____ 60 Nickel Chloride___ Boric Acid. _ _ Saccharin ______Bromo BBHTQHB Sulfonate ______1,5-Benzene Dislllfonate ______Vinyl Ben-".ene Sulfonate ____ ._ Sodium Allyl Sulfonate ______65 Sodium Ben ialdehyde Sulfona Dibenzene sulfonamid ______. Allyl sulfonamid ______wherein R1 is an alkene group; R3 is an alkyne group; R2 B-Diallyl amino propyne-l ______and R4 are alkene, alkyne, H, CH3, C2H5, C3H7, phenyl 1-Al1yl3-aminoTriallyl propargyl dipropyne amine chloride- ____ and naphthyl and X is an acid group, such as halogen, l-Allyl amino 2-buty-ne. _ SO3H, or P04. Compounds (C) and (D) may be quater Allyl propargyl amine__ nized. 70 pH ______. . ____ _- 3. 6 4. 0 Temp, ° F ______135 140 140 135 155 While alkene and alkyne carbon chains up to 8 carbon 3,133,006 3 4 Examples of amino vinyl acetylenic compounds are as from the class consisting of alkene, alkyne, H, and lower alkyl, and R3 is alkyne. follows: 2. An aqueous acid nickel electroplating bath having Allyl propargyl amine incorporated therein an amine having as substituent groups Diallyl propargyl amine an alkene and an alkyne radical attached to nitrogen and Triallyl propargyl amine having the following structural formula: Vinyl propargyl amine Allyl dipropargyl amine Divinyl propargyl amine Triallyl propargyl amine hydrochloride Bis l,4-allyl amine Z-butyne 10 Bis 1,4-diallyl amine Z-butyne wherein R1 is alkene, R3 is alkyne, and R2 and R4 are Bis 1,4-triallyl amine Z-butyne taken from the class consisting of alkene, alkyne, H, and The following sulfonic acids may be incorporated in lower alkyl, and X is an acid group. the bath with the principal additive; they may be in the 15 3. An aqueous acid nickel electroplating bath having form of salts, such as of nickel, sodium, magnesium, etc. incorporated therein an amine having as substituent groups an alkene and an alkyne radical attached to nitro Benzene sulfonic acid gen and having the following structural formula: Di-benzene sulfonic acid Vinyl benzene sulfonic acid R Allyl benzene sulfonic acid 20 Bromo benzene sulfonic acid 1,5-naphthalene disulfonic acid R4 R3 1,3,6 naphthalene trisulfonic acid wherein R1 is alkene, R3 is alkyne, and R2 and R4 are Among the sulfonamids and sulfonimids which are 25 taken from the class consisting of alkene, alkyne, H, and suitable are the following: - lower alltyl. '~ Saccharin Na salt 4. An aqueous acid nickel electroplating bath having Benzene sulfonamid incorporated therein an amine having as substituent groups Dibenzene sulfonamid an alkene and an allcyne radical attached to nitrogen, and Allyl sulfonamid 30 having the following structural formula: The baths of the invention may be operated over a wide range of concentration, pH, and current densities. A pH range of 3.0 to 4.8 is typical. The concentration of the additive may vary from about .001 to .50 gram per 35 liter when used with cooperating sulfo oxygen type ma wherein R1 is alkene, R3 is alkyne, and R2 and R4 are terials. The concentration of the sulfo oxygen will gen taken from the class consisting of alkene, alkyne, H, and erally determine the concentration of the alkene-alkyne lower alkyl. , amine. When used alone, the concentration of the alkene 5. A nickel plating bath according to claim 3, charac alkyne amine generally ranges from about .001 to 1.0 40 terized in that said compounds are quaternized. gram per liter. 6. A nickel plating bath according to claim 4, charac These baths may be operated with or without mechani terized in that said compounds are quaternized. cal or air agitation. When air is used, a compatible low foaming or non-foaming type of wetting agent is em References Cited in the ?le of this patent ployed in the bath; The invention may be used in all 45 sulfate baths, that is baths substantially free from chlo , UNITED STATES PATENTS rides; and it is suitable for sulfamate baths also. 2,800,442 Brown ______July 23, 1957 We claim: a ‘ 2,978,391 Du Rose ______-- Apr. 4, 1961 1. An aqueous acid nickel electroplating bath having 3,006,822 Todt ______Oct. 31, 1961 ‘ incorporated therein an amine having as substituent 50 FOREIGN PATENTS groups an alkene and an alkyne radical attached to nitro gen and having the following structural formula: 858,718 Great Britain ______'__ Jan. 11, 1961 I'M B1—-N—-R3 55 wherein R1 is an alkene group and R4 is a radical taken UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3, 133,006 May 12' 1964

Barnet D. Ostr'ow et a1"- ’ that error appears in the above numbered pat It is hereby certified that. the said Letters Patent should read as ent requiring correction and corrected below. Column 2, lines 9 and 10, formula (1) should appear as shown below instead of as in the patent:

Signed and sealed this 29th day of December 1964‘,

(SEAL) Attest: EDWARD J. BRENNER AttestingERNEST OfficerW. SWIDER' Commissioner_ of Patents