Acetylenic compositions and nickel plating baths containing same

Claim 2

3-(2-propynoxy)-2-propenoic acid.

Claim 5

The method of claim 2 wherein the alkaline solution is a solution of alkali or alkaline earth metal base in water.

Claim 6

An acetylenic composition prepared by a process comprising the steps of (a) reacting propargyl alcohol with an alkali metal permanganate in an aqueous alkaline solution, (b) filtering the reaction mixture, and (c) acidifying the filtrate with acid.

Claim 7

An acetylenic composition prepared by a process comprising the steps of (a) reacting propargyl alcohol with an alkali metal permanganate in an aqueous alkaline solution, (b) filtering the reaction mixture, and (c) acidifying the filtrate with acid.

Claim 8

The composition of claim 4 wherein the permanganate is potassium permanganate.

Claim 9

The composition of claim 4 wherein the aqueous alkaline solution comprises a solution of sodium or potassium hydroxide in water.

Claim 10

The composition of claim 4 wherein the filtrate is acidified with sulfuric acid to a pH of less than about 2.

Claim 11

An acetylenic composition prepared by the process comprising the steps of (a) reacting about 1.5 parts of propargyl alcohol with about 0.1 to about 1.0 part of potassium permanganate in an aqueous alkaline solution at a pH of from about 9 to 11, (b) filtering the reaction mixture, and (c) acidifying the filtrate with acid to a pH less than about 2.

Claim 12

An acetylenic composition prepared by the process comprising the steps of (a) reacting about 1.5 parts of propargyl alcohol with about 0.1 to about 1.0 part of potassium permanganate in an aqueous alkaline solution at a pH of from about 9 to 11, (b) filtering the reaction mixture, and (c) acidifying the filtrate with acid to a pH less than about 2.

Claim 13

An aqueous acidic plating bath for the electrodeposition of nickel or a nickel-iron alloy on a substrate which bath comprises nickel ions, or a mixture of nickel ions and iron ions, and as a brightening and leveling agent, an effective amount of 3-(2-propynoxy)-2-propenoic acid.

Claim 14

An aqueous acidic plating bath for the electrodeposition of nickel or a nickel-iron alloy on a substrate which bath comprises nickel ions, or a mixture of nickel ions and iron ions, and as a brightening and leveling agent, an effective amount of 3-(2-propynoxy)-2-propenoic acid.

Claim 15

The bath of claim 9 also including a secondary brightener of the formula R.sub.1 C.tbd.CCH.sub.2 OR.sub.2 I wherein R 1 is selected from H, CH 2 OH, CH 2 OR 2 ; R 2 is selected from H, (CH 2 CH 2 O) n H, (CH 2 CH(OH)CH 2 ) n H, (CH 2 ) m SO 3 M, (CH 2 CH(OH)CH 2 ) n -SO 3 M, (CH 2 CH 2 O) n (CH 2 CH(OH)CH 2 )SO 3 M, and (CH 2 CH 2 O) n (CH 2 ) m SO 3 M, where n is an integer from 1 to 10; m is an integer from 1 to 4; and M is selected from hydrogen, ammonium, alkali metal, nickel and cobalt.

Claim 16

The bath of claim 10 wherein R 1 is hydrogen or hydroxymethyl.

Claim 17

The bath of claim 10 also containing at least one surfactant or wetting agent.

Claim 18

The bath of claim 10 also containing at least one heterocyclic leveling compound having the general formula RN.sup.+ --R'--SO.sub.3.sup.- II wherein RN is an aromatic heterocyclic nitrogen-containing group and R' is an alkylene or hydroxy alkylene group.

Claim 19

The plating bath of claim 13 wherein the heterocyclic leveling compound is at least one sulfo-betaine having the general formula ##STR12## wherein R 1 is hydrogen, benzo(b), one or more lower alkyl, halide, hydroxy, lower alkenyl or lower alkoxy groups or benzo(b) groups substituted with one or more lower alkyl, halide, hydroxy, lower alkenyl or lower alkoxy groups, R 2 is an alkylene or hydroxy alkylene group containing three or four carbon atoms in a straight chain, R 3 is an alkylene or hydroxy alkylene group containing two or three carbon atoms in a straight chain, and R 4 is hydrogen or a hydroxyl group.

Claim 20

The plating bath of claim 9 wherein the 3-(2-propynoxy)-2-propenoic acid is present in an amount of from about 0.001 to 0.05 gram per liter.

Claim 21

An aqueous acidic plating bath for the electrodeposition of nickel or a nickel-iron alloy on a substrate which bath comprises nickel ions or a mixture of nickel ions and iron ions, and as a brightening and leveling agent, an effective amount of an acetylenic composition of any one of claims 4-8.

Claim 22

The bath of claim 16 also including at least one surfactant or wetting agent.

Claim 23

The plating bath of claim 16 wherein the bath contains a mixture of nickel ions and iron ions and at least one bath-soluble complexing agent for iron which is an aliphatic carboxylic acid containing from 1 to 3 carboxyl groups and from about 1 to 6 hydroxyl groups.

Claim 24

The plating bath of claim 16 wherein the bath also contains at least one heterocyclic leveling compound having the general formula RN.sup.+ --R'--SO.sub.3.sup.- II wherein RN is an aromatic heterocyclic nitrogen-containing group and R' is an alkylene or hydroxy alkylene group.

Claim 25

The plating bath of claim 19 wherein the heterocyclic leveling compound is at least one sulfo-betaine having the general formula ##STR13## wherein R 1 is hydrogen, benzo(b), one or more lower alkyl, halide, hydroxy, lower alkenyl or lower alkoxy groups or benzo(b) groups substituted with one or more lower alkyl, halide, hydroxy, lower alkenyl or lower alkoxy groups, R 2 is an alkylene or hydroxy alkylene group containing three or four carbon atoms in a straight chain, R 3 is an alkylene or hydroxy alkylene group containing two or three carbon atoms in a straight chain, and R 4 is hydrogen or a hydroxyl group.

Claim 26

The plating bath of claim 20 wherein the sulfo-betaine compound is represented by Formula III and R 1 is hydrogen.

Claim 27

The plating bath of claim 20 wherein the sulfo-betaine is present in an amount of from about 0.1 to about 10 grams per liter of bath.

Claim 28

The plating bath of claim 16 wherein the acetylenic composition is present in the plating bath in an amount of from about 0.001 to about 1.0 gram per liter.

Claim 29

The plating bath of claim 16 wherein the bath also contains from about 0.5 to about 25 grams per liter of at least one brightener selected from the group consisting of an aliphatic or aromatic sulfonamide, sulfonimide, sulfonic acid or the bath-soluble salts thereof.

Claim 30

The method of electrodepositing a nickel or nickel-iron alloy on a substrate which comprises electroplating said substrate in an aqueous acidic bath of claim 16.

Claim 31

An aqueous acidic plating bath for electrodepositing nickel on a substrate, which bath comprises (a) from about 5 to about 350 grams per liter of nickel ions, (b) from about 0.01 to about 1.0 gram of the acetylenic composition of any one of claims 1-8, (c) at least one sulfo-betaine having the general formula ##STR14## wherein R 1 is hydrogen, benzo(b), one or more lower alkyl, halide, hydroxy, lower alkenyl or lower alkoxy groups or benzo(b) groups substituted with one or more lower alkyl, halide, hydroxy, lower alkenyl or lower alkoxy groups, R 2 is an alkylene or hydroxy alkylene group containing three or four carbon atoms in a straight chain, R 3 is an alkylene or hydroxy alkylene group containing two or three carbon atoms is a straight chain, and R 4 is hydrogen or a hydroxyl group, and (d) from about 0.5 to about 25 grams per liter of a brightener selected from the group consisting of an aliphatic or aromatic sulfonamide, sulfonimide, sulfonic acid or bath-soluble salts thereof.

Claim 32

The plating bath of claim 26 wherein R 1 in Formulas III, IV and V is a hydrogen atom.

Claim 33

A method of electrodepositing nickel on a substrate which comprises electroplating said substrate with the aqueous acidic plating bath of claim 25.

Claim 34

An additive composition for plating baths useful for electrodepositing of nickel or a nickel-iron alloy on a substrate comprising a mixture of (a) the acetylenic composition of any one of claims 1-8, (b) at least one sulfo-betaine having the general formula ##STR15## wherein R 1 is hydrogen, benzo(b), one or more lower alkyl, halide, hydroxy, lower alkenyl or lower alkoxy groups or benzo(b) groups substituted with one or more lower alkyl, halide, hydroxy, lower alkenyl or lower alkoxy groups, R 2 is an alkylene or hydroxy alkylene group containing three or four carbon atoms in a straight chain, R 3 is an alkylene or hydroxy alkylene group containing two or three carbon atoms in a straight chain, and R 4 is hydrogen or a hydroxyl group.

Claim 35

The additive composition of claim 29 also containing at least one aliphatic or aromatic sulfonamide, sulfonimide, sulfonic acid or bath-soluble salt thereof.

Claim 36

The additive composition of claim 29 also containing at least one bath-soluble complexing agent which is an aliphatic carboxylic acid containing from about 1 to 3 carboxyl groups and from about 1 to about 7 hydroxyl groups.

Claim 37

The additive composition of claim 29 wherein the acetylenic composition is 3-(2-propynoxy)-2-propenoic acid and the bath also contains propargyl alcohol or butynediol.