US2757133A - Electrodeposition of nickel - Google Patents

Description

United States Patent 2,757,133 ELECTRODEPOSITION OF NICKEL Wilbur J. Shenk, Jr., Shaker Heights, Ohio, assignor to The Harshaw Chemical Company, Elyria, Ohio, a corporation of Ohio No Drawing. Application June 10, 1952,

Serial No. 292,725

'17 Claims. (Cl. 204-49)" This invention relates to electrodeposition of nickel, and more specifically to the use of certain addition agents which effectively enhance brightness and improve ductility.

It is recognized that prior to the present invention a great variety of organic addition agents have been used or proposed for use for the production of bright or semibright nickel deposits. Some of these have proved to be of commercial value, while others have failed because of their sensitivity to impurities or failure to continue pro ducing good deposits over sufliciently long periods of time. Some of the proposed addition agents have not been commercialized merely because other addition agents were found to be somewhat superior. Such considerations as the rate of consumption in the plating solution, the difiiculty of analyzing the solution or otherwise determining the concentration of brightener, and the build-up of the concentration of degradation products are important in the choice of brightening addition agents.

The present invention has to do with the use, either as the sole brightening addition agent or as a cooperating addition agent for use with other brighteners, of a class of compounds, one representative of which is a compound known as dibenzenesulfonamide or dibenzenesulfonyl amine and having the formula,

0 H o Q ti ti Other examples of the class are:

TABLE I 1) Trichlorodibenzenesulfonamides- Cl2CsHzSO2NHSO2CsH4C1 (2) Tetrachlorodibenzenesulfonamides- ClaCeHsSOzNHSOzCsHsClz (3 Di-B-naphthalenesulfonamide- CIOH'ISOZNHSO2C10H7 (4) 2,2,4,4,6,6'-HeXachlorodibenzenesulfonamide- ClsCsHzSOzNHSOzCsI-IzCls (5) Pentachlorodibenzenesulfonamides- ClaCsHzSOzNHSOzCsHaClz (6) Methyldichlorodibenzenesulfonamides- Cl2CsH3SO2NHSO2CsH4CH3 (7) 2,4,6-Trichl-orodibenzenesulfonarnide- ClaCsHzSOzNHSOzCeHs (8) 2,5 -Dichloro-3 -sulfamyldibenzenesulfonamide- C12C6H3S02NHSO2C6H4SO2NH2 9 Disulfonilamide-NHzCsH4SO2NI-ISO2CsH4NHz (10) N-phenylsulfonyl-fi-naphthalenesulfonamide- 2,757,133 Patented July 31, 1956 I CC 2 (1 l) Di-p-toluenesulfonamide- CH3C6H4SO2NHSO2C6H4CH3 l2) 4-Methyldibenzenesulfonamide- CeH5SO2NHSO2CsH4CI-Is l 3) N,N'-bis (phenylsulfonyl) -m-sulfamylbenzarnide- CsHsSOzNHSOzCsHrCONHSOzCsHs l4) Dicumenesulfonamide (CH3)2CHCsH4SO2NHSOzCsI-I4CH(CH3)2 l 5) 4-Ethyldibenzenesulfonamide- CBHSSOZNHSOZCGHCZHE 16) 4,4-Dicarboxyldibenzenesulfonamide- COOHCsH4SO2NHSO2CsH4COOH l7) 2,2,4,4'-Tetramethyldibenzenesulfonamide- CH3 zCsH's'SOzNHSOzCsHs (CH3 2 18 Dichlorodibenzenesulfonamidescncsrnsomnsozcsm (19) 4-Fluorodibenzenesulfonamides- FCsH4SO2NHSO2CsH5 (20) 4-Carboxyldibenzenesulfonamide- CsH5SO2NHSO2CsH4COOH (21) N,N' bis (phenylsulfonyl) 1,3 benzenedisulfonamide-CsH5SO2NHSO2CBH4SO2NHSO2C6H5 (22) N,N'-bi-s(dichlorophenylsulfonyl)-1,3-benzenedisulfonamidcs-ClzCGH3SO2NHSO2CGH4SOzNHSOaCaI-IzClz (23) N,N bis (phenylsulfonyl) 4,4 diphenyldisulfonamide-CsHsSOzNHSOaCsH4CeH4SO2NHSO2CsH5 (24) p,p-Oxy-bis(dibenzenesulfonamide)- (26) N,N-bis (2,4,6-trichlorophenylsulfonyl)-1,3-benzenedisulfonamide- (27) N,N'-bis (p-tolylsulfonyl) 4,4 diphenyldisulfonamide- CH3CsH4SO2'NHSO2CsH4CsH4SOzNHSOzCsHtCHa 28) N-ethylsulfonylbenzenesulfonamide- CsHsSOzNHSOzCHzCHs (29) N-vinylsulfonylbenzenesulfonamide- CsH5SOzNHSO2CH=CH2 (30) N-(n-butylsulfonyl)benzenesulfonamide- CsHsSO2NHSO2C4H9 (31 N- (n-laurylsulfonyl -benzenesulfonamide- CsH5SO2NHSO2C12H25 (32) Di-a-toluenesulfonamide- C6H5CH2SO2NHSO2CH2C6H5 3 3 N-benzylsulfonylbenzenesulfonamide- CsHsSOzNHSOzCHzCsHa (34) N-ethylsulfonyldichlorobenzenesulfonamides- ClzCsHsSOzNHSOzCzHs (35 N-methallylsulfonylbenzenesulfonamide- CeH5SO2NHSOzCH2C(CH3 =cn2 (3 6) N-methyl-sulfonylbenzenesulfonamide- CsHsSOzNI-ISOzCI-Is (37) Dimethanesulfonamide-CHsSOzNI-ISOzCI-Ia (Inoperative) (38) Didodecanesulfonamide (inoperative) (39) N,N'-bis(phenylsulfonyl)- 1,5 naphthalenedisulfonamide somnsmQ CrzHzsSOzNI-ISOzCrzI-Izs somnsoQ (40) N,N'-bis (phenylsulfonyl) 3,3'-benzophenonedisulfonamide-CsHsSOzNI-ISOzCsHsCOCsHaSOzNHSOzCsI-Ia PhSOzNHSOzPh has a pH of 1.3 in tenth normal solution whereas PhSOzNHz is only about as acidic as phenol. Again, they are very soluble in water. For example, PhSOzNHSOzPh is soluble in water at 20 C. to the extent of about 50 grams per liter, while PhSO2NH2 is soluble under the same conditions only to the extent of about 3 grams per liter. This solubility difference increases in importance as one considers nuclear substitution products of benzenesulfonamide which have less solubility. Thus 2,5-dichlorobenzenesulfonarnide, ClzCsHsSOaNI-Iz, appears to have promise as a scratchfilling carrier in certain bright baths, but its low solubility, 0.5 g./l. in Watts bath solution, severely limits its usefulness. On the other hand, 2,5-dichlorodibenzenesulfonamide, ClzCsHsSOaNHSOzCeHB, has a solubility of approximately 30 g./l. in the Watts bath, thus permitting its use over a wide range of concentrations, and it has been found to be an excellent scratch-filling carrier.

It has been established that 2,5-dichlorodibenzenesulfonamide is slowly converted principally to dibenzenesulfonamide by hydrogenolysis during the plating operation, and

it appears that the superior leveling properties of the bath containing this compound are in some way related to this reaction which is presumably taking place catalytically on the freshly deposited nickel surface.

If one tries to increase the degree of halogenation to say 2,2,5,5-tetrachlorodibenzenesulfonamide low solubility (in this case about 1 g./l.) again becomes a limiting factor but this can be overcome by using a compound containing two disulfonamide groups. Thus, N,N-bis- (2,S-dichlorophenylsulfonyl) 1,3 benzenedisulfonamide,

compounds for use in accordance with the invention:

TABLE II n and n each indicating an integer from 0 to 3 and the sum of 12 plus n not exceeding 3.

SOzNHSOa SOQNHSOZ n and n each indicating an integer from 0 to 3 and the sum of n plus n not exceeding 6.

n and n each indicating an integer from 0 to 3 and the sum of n plus 11' not exceeding 6.

n and n each indicating an integer from 0 to 3, and the sum of n plus 11 not exceeding 6.

n and 11 each indicating an integer from 0 to l. (7) C6H5SO2NHSO2C6H4COCsHtSOzNHSOzCeHs.

These compounds indicated in Tables 1 and II are examples of the class of disulfonamides which produce semibright to bright deposits when used in the acid nickel plating solution as the sole brightener, for example in a solution of the Watts type, which might, for example, contain 240 grams per liter of nickel sulfate hexahydrate, 40 grams per liter of nickel chloride hexahydrate, and 40 grams per liter of boric acid, remainder water. It is to be understood that such a nickel plating bath would normally contain an anti-pit agent of the wetting-agent type, such for example as sodium lauryl sulfate or other aliphatic sulfate having 8 to 18 carbon atoms or mixtures thereof, and that the same might be present within the limits of solubility but preferably about 0.1 to 0.5 grams per liter. The anti-pit agent is not always necessary, since the bath sometimes produces pit-free deposits without it, and sometimes the degree of pitting is such as can be tolerated even though some pits are present.

As above indicated, the novel class of compounds can be effectively used in combination with a wide variety of other brighteners, with the result that there is produced bright, ductile deposits having good throwing power and capable of being operated trouble-free for long periods of time. Examples of such cooperating brighteners are as follows:

TABLE III Ethylene cyanohydrin Vinyl pyridine Triaminotriphenylmethane N-Methylquinaldinium methyl sulfate Allyl alcohol Succinonitrile (7) Cyclohexanone oxime (8) Butyraldoxime (9) Benzaldehyde (10) N-Methylisoquinolinium methyl sulfate (11) N-methylpyridinium methyl sulfate (12) Pyruvic aldehyde (13) Barbituric acid The disulfonamides contemplated by the invention for use in nickel plating solutions are of the character indicated by the foregoing examples, that is, they are compounds of the type:

enema where (1) R and R both may be aromatic radicals, or (2) R may be an aromatic radical While R is an aliphatic radical, or (3) both R and R may be aliphatic or aryl substituted aliphatic radicals. The aromatic radicals should in all instances be limited to not more than nuclear carbons and may carry one or a plurality of substitucnts of the class chlorine, bromine, fluorine, methyl, ethyl, carboxyl, sulfamyl, R'SOzNHSOzR,

OR'SOzNI-ISOzR and SOzNHSOaR. The aliphatic radicals, when both R and R are aliphatic, must contain at least 2 but should not contain more than 18 carbon atoms, must have at least one unsaturated carbon to carbon bond, which, however, may be in an aryl substituent, and may carry one or a plurality of substituents of the class consisting" of chlorine, bromine fluorine, methyl, ethyl, carboxyl, R'SO2NHSO2'R, CHzRSOzNHSOaR, OR'SOzNHSOzR and SO2NHSO2R. When R is aromatic and R is aliphatic, R should be limited to not more than 10 carbon atoms and R may be saturated or unsaturated and may contain froml to 18 carbon atoms. Either R or R in that case may be substituted by chlorine, bromine, fluorine, carboxyl or sulfamyl, aryl having not more than 6 carbon atoms, R'SOaNHSOzR, CHzR'SOzNHSOz'R, OR'SOzNI-ISOzR or SOzNI-ISOzR. In other Words, R is an organic radical of the class consisting of aromatic radicals having not more than ten nuclear carbon atoms and aliphatic radicals having at least one unsaturated carbon to carbon bond, and R is selected from the class consisting of aromatic radicals having not more than ten nuclear carbon atoms, aliphatic radicals having from i to 18 carbon atoms, aryl substituted aliphatic radicals having from 7 to 11 carbon atoms, and radicals of the formula RSO2NHSO2R.

In general, the concentration of the disulfonamide should be from 0.2 to 6 grams per liter, preferably from 0.5 to 6.0 grams per liter when used as the sole brightening addition agent in a Watts type bath to produce a semi bright deposit. When used in conjunction with aryl sulfonic acids, sulfonates, sulfonamides or sulfirnides, which are themselves effective to produce semi-bright deposits and, in cooperation with auxiliary brighteners such as those listed above, to produce fully bright deposits, the concentration may vary from a very small amount, for example 0.1 gram per liter up to 6 grams per liter, and may be expected to perform its function to a degree in proportion to its concentration. The auxiliary brightening addition agents such as ethylene cyanohydrin and others listed above may be present in various concentrations, ordinarily quite small, and up to such concentration as tends to embrittle the deposit excessively. Suitable concentrations of various auxiliary brightening addition agents are as indicated in the specific examples hereinafter set forth.

The constituents of the bath according to the preferred practice of the invention are: 1) water; (2) nickel sulfate, nickel chloride, or nickel sulfate with nickel chloride; (3) a disulfonamide of the class above indicated or a plurality thereof; (4) a wetting agent such as sodium lauryl sulfate or a mixture of aliphatic sulfates having from 8 to 18 carbon atoms, the wetting agent being optional; and (5) an auxiliary brightening addition agent such as those listed above, the auxiliary brightening addition agent also being optional. An additional ingredientof the solution which is desirable is a buifering agent such as boric acid, formic acid, or the like.

It Will be noted that in respect to major constituents, the solutions are similar to the Well-known all sulfate, all chloride, and sulfate-chloride 01' Watts type acid nickel plating solutions. It will be noted also that the auxiliary brighteners such as ethylene cyanohydrin and others listed therewith above are, for the most part, con ventional auxiliary brighteners for use with aromatic sulfonic acids and sulfonamides. The essence of the 6 present invention is in the use of dibenzenesulfonamide and/ or other compounds listed above, it having been discovered that this class of compounds, either as. the sole brightening addition agent or as a cooperating brightening addition agent, imparts to the bath unexpected properties of bright throwing power, ductility and smoothness. A further important feature of the invention is the use of dibenzenesulfonamide and the other members of its group as above indicated, in solutions which already contain aromatic sulfonic acids, sulfonates or sulfonamides as a partial substitute for those compounds for the purpose of imparting the unexpected properties in dicatedabove. In other words, the dibenzenesulfonamide type of addition agent imparts superior bright throwingpower, ductility and smoothness to bright plating solutions of the type wherein principal reliance is placed on a combination of a mononuclear aromatic sulfonyl compound and an auxiliary brightening agent. In conventional solutions, the aromatic sulfonate, for example naphthalene sulfonate, is often referred to as a carrier, while an auxiliary brightener such as triaminotriphenylmethane is referred to as the brightener. In this terminology the disulfonamide is useful either as carrier or as a partial substitute for the usual type of carrier to impart enhanced bright throwing-power, ductility and smoothness. Again, Where the disulfonamide is used without the brightener, it produces semi-bright deposits having good semi-bright throwing power, excellent ductility and a good smoothing action.

The preferred basic solutions in connection with which the invention is realized are as follows:

All sulfate NiSO .7H20 s to 400 g., preferably 200 to 300 g. Boriq a'cid 0 to 60 g., preferably 10 to 40 g. Wetting agent (e. g., soiium lauryl sulfa 0' to 0.5 g'., preferably 0.05 to 0.2 g. H20 to make 1009 cc.

All chloride 50 to 250 g., preferably 100 to 200 g. 0 to 60 g., preferably 10 to 40 g.

NiCl2.6HeO r Boric acid Wetting agent (e. g.,

solium lauryl sula 0 to 0.5 g., preferably 0.05 to 0.2 g. H2O to make 1000 cc.

Wetting agent (e. g.,

sotdium lauryl sul- 13261;) 155128166356. 0 to 0.5 g., preferably 0.025 to 0.2 g.

To each of the foregoing basic solutions may be added a quantity of the disulfonamide and, if full brightness is desired, a quantity of a brightener and, optionally, a carrier of the aromatic sulfonate or aromatic sulfonamide type.

The following specific examples of plating solutions will serve to illustrate the invention, it being understood that the various examples listed above are interchange able in the following solutions with addition agents of the same class (carrier or auxiliary brightener) and give similar results although some of the compounds of Table I do give very superior results especially in some instances as herein elsewhere indicated.

H2O to make one liter.

EXAMPLE II (Semi-Bright) NiSO4.6I-Iz grams 240 NiCl2.6H2O do 40 H3BO3 do 40 Dibenzenesulfonarnide do- 6 pH 3.5 Temperature F 140 Cathode current density A. S. F 40 H2O to make one liter.

EXAMPLE III (All Chloride-Bright Semi-Bright) NiClz.6H2O grams 300 HsBOz do 50 Dibenzenesulfonamide do 2 pH 3.5 Temperature F 140 Cathode current density A. S. F 40 H2O to make one liter.

EXAMPLE IV (Bright) NiSO4.6H2O grams 240 NiCl2.6I-I2O do 40 1131303 do 40 Dibenzenesulfonamide do 0.5 Ethylene cyanohydrin do 0.24 pH 3.5 Temperature F 140 Cathode current density A. S. F 40 H2O to make one liter.

EXAMPLE V (Bright) NiSO4.6HzO grams 240 NiClz.6HzO do 40 HsBOa do 40 Dibenzenesulfonamide do 0.5 Naphthalene disulfonate do 4 Triaminotriphenyl methane do 0.005 pH 3.2 Temperature F 140 Cathode current density A. S. F 40 E20 to make one liter.

EXAMPLE VI (Bright) NiSO4.6H2O grams 240 NiCl2.6H2O d0.. 40 H3303 do 40 Dibenzenesulfonamide do 0.5 Benzaldehyde do 0.4 pH 3.5 Temperature F 140 Cathode current density A. S. F 40 H2O to make one liter.

EXAMPLE VII (Bright) NiSO4.6I-I2O grams 240 NiCl2.6I-I2O do 40 H3BO3 do 40 Naphthalene benzene disulfonamide (N-phenyl sulfonyl-Z-naphthalene sulfonarnide "grams" 0.3

Triaminotriphenyl methane do 0.005 pH 3.5 Temperature F 140 Cathode current density A. S. F 40 B20 to make one liter.

EXAMPLE VIII (Semi-Bright) NiSO4.6H2O "grams" 240 NiCl2.6H2O d0 40 I-I3BO3 do 40 ClzCsI-IsSOzNHSOzCsI-MCI d0.. 0.5 pH 3.5 Temperature F 140 Cathode current density A. S. F 40 H2O to make one liter.

Having thus described my invention, what I claim is:

1. An acid, nickel electroplating solution comprising a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride and mixtures thereof, together with an addition agent of the formula R-SO2NHSO2R, where R is an aromatic radical having not more than ten nuclear carbon atoms and R is selected from the class consisting of aromatic radicals having not more than ten nuclear carbon atoms, aliphatic radicals having from 1 to 18 carbon atoms, including at least one unsaturated carbon to carbon bond, aryl substituted aliphatic radicals having 7 to 11 carbon atoms, radicals of the formula R"SO2NHSO2 radicals of the formula RR"-SO2NHSOz-R"', radicals of the formula RORSO2NHSO2R and radicals of the formula RCH2R-SO2NHSO2-R", R, R" and R occurring in said last four radicals, indicating aromatic radicals having not more than ten nuclear carbon atoms, said addition agent being present to the extent of from 0.1 to 6 grams per liter.

2. The process of electroplating metallic surfaces by electrolytic deposition from nickel salt solution which comprises passing current to said metallic surface as a cathode through said solution containing as an additive a compound of the formula R-SO2NHSO2R, where R is an aromatic radical having not more than ten nuclear carbon atoms and R is selected from the class consisting of aromatic radicals having not more than ten nuclear carbon atoms, aliphatic radicals having from 1 to 18 carbon atoms including at least one unsaturated carbon to carbon bond, aryl substituted aliphatic radicals having 7 to 11 carbon atoms, radicals of the formula R--SO2NHSO2 radicals of the formula radicals of the formula RORSO2NHSO2R and radicals of the formula RCH2R"SO2NHSO2-R", R, R and R' occurring in said last four radicals indicating aromatic radicals having not more than ten nuclear carbon atoms, said addition agent being present to the extent of from 0.1 to 6 grams per liter.

3. An acid, nickel electroplating solution comprising a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride and mixtures thereof, together with an addition agent having the formula where R and R are aromatic radicals having not more than ten nuclear carbon atoms, said addition agent being present to the extent of from 0.1 to 6 grams per liter.

4. An acid, nickel electroplating solution comprising a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride and mixtures thereof, together with an addition agent having the formula where R is an aromatic radical having not more than ten nuclear carbon atoms and R is an aliphatic radical having from 1 to 18 carbon atoms and containing at least one unsaturated carbon to carbon bond, said addition agent being present to the extent of from 0.1 to 6 grams per liter.

5. An acid, nickel electroplating solution comprising a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride and mixtures thereof, together with an addition agent having the formula where R, R and R" are aromatic radicals having not more than ten nuclear carbon atoms, said addition agent being present to the extent of from 0.1 to 6 grams per liter.

6. An acid, nickel electroplating solution comprising a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride and mixtures thereof, together with an addition agent having the formula where R, R', R and R' are aromatic radicals having not more than ten nuclear carbon atoms, R and R" being connected through nuclear carbon, said addition agent being present to the extent of from 0.1 to 6 grams per liter.

7. An acid, nickel electroplating solution comprising a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride and mixtures thereof, together with an addition agent having the formula where R is an aromatic radical having not more than ten nuclear carbon atoms and R is an aryl substituted aliphatic radical having from 7 to 11 carbon atoms, said addition agent being present to the extent of from 0.1 to 6 grams per liter.

8. An acid, nickel electroplating solution comprising a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride and mixtures thereof, together with an addition agent having the formula:

21 and n each indicating an integer from to 3, and the sum of n plus n not exceeding 3, said addition agent being present to the extent of from 0.1 to 6 grams per liter.

9. An acid, nickel electroplating solution comprising a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride and mixtures thereof, together with an addition agent having the formula:

n and n each indicating an integer from 0 to 3, and the sum of n plus n not exceeding 6, said addition agent being present to the extent of from 0.1 to 6 grams per liter.

10. An acid, nickel electroplating solution comprising a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride and mixtures thereof, together with an addition agent having the formula:

@s OINHS O2S olNns 02G 01.

n and n each indicating an integer from 0 to 3, and the sum of n plus it not exceeding 6, said addition agent being present to the extent of from 0.1 to 6 grams per liter.

11. An acid, nickel electroplating solution comprising a nickel electrolyte of the class consisting of nickel sul- Gin fate, nickel chloride and mixtures thereof, together with an addition agent having the formula:

n and 11' each indicating an integer from O to 3, and the sum of 11 plus It not exceeding 6, said addition agent being present to the extent of from 0.1 to 6 grams per liter.

12. An acid, nickel electroplating solution comprising a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride and mixtures thereof, together with an addition agent having the formula:

said addition agent being present to the extent of from 0.1 to 6 grams per liter.

13. An acid, nickel electroplating solution comprising a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride and mixtures thereof, together with an addition agent having the formula:

@somnso,

Q}somnso= 16. The invention as defined in claim 1 wherein said addition agent is C6H5SO2NHSO2C6H4OCGH4SOZNHSOZCGH5 17. The process of electroplating metallic surfaces by electrolytic deposition from nickel salt solutions which comprises passing current to said metallic surface as a cathode through said solution containing as an additive SOQNHSO CH CH:

said additive being present in said solution to the extent of 0.1 gram per liter.

References Cited in the file of this patent UNITED STATES PATENTS 2,191,813 Brown Feb. 27, 1940 2,467,580 Brown Apr. 19, 1949 2,644,788 Shenk July 7, 1953 2,644,789 Shenk July 7, 1953

Claims (1)

1. AN ACID, NICKEL ELECTROPLATING SOLUTION COMPRISING A NICKEL ELECTROLYTE OF THE CLASS CONSISTING OF NICKEL SULFATE, NICKEL CHLORIDE AND MIXTURES THEREOF, TOGETHER WITH AN ADDITION AGENT OF THE FORMULA R-SO2NHSO2-R'', WHERE R IS AN AROMATIC RADICAL HAVING NOT MORE THAN TEN NUCLEAR CARBON ATOMS AND R'' IS SELECTED FROM THE CLASS CONSISTING OF AROMATIC RADICALS HAVING NOT MORE THAN TEN NUCLEAR CARBON ATOMS, ALIPHATIC RADICALS HAVING FROM 1 TO 18 CARBON ATOMS, INCLUDING AT LEAST ONE UNSATURATED CARBON TO CARBON BOND, ARYL SUBSTITUTED ALIPHATIC RADICALS HAVING 7 TO 11 CARBON ATOMS, RADICALS OF THE FORMULA R"-SO2NHSO2-R"'', RADICALS OF THE FORMULA RR"-SO2NHSO2-R"'', RADICALS OF THE FORMULA ROR"-SO2NHSO2-R'''''' AND RADICALS OF THE FORMULA RCH2"-SO2NHSO2-R'''''', R, R" AND R'''''' OCCURING IN SAID LAST FOUR RADICALS, INDICATING AROMATIC RADICALS HAVING NOT MORE THAN TEN NUCLEAR CARBON ATOMS, SAID ADDITION AGENT BEING PRESENT TO THE EXTENT OF FROM 0.1 TO 6 GRAMS PER LITER.