Detergent Properties of Ether Sulfonates D
4
F. J. VAN ANTWERPEN 60 East 42nd Street, New York,N. Y.
flocculation. The dispersion of soil is important in detergent action, for in this manner large particles are broken up. Equally important, however, is the necessity of keeping the dispersed soil in suspension, for this greatly facilitates rinsing. The superior detersives have, as a common characteristic, great deflocculating power; although it would not be a direct or total measurement of detergency, a comparison of deflocculating power would indicate the relative soil-removing efficiency of various types of cleansing agents. Tests of this nature were made by shaking finely divided carbon black in a dilute solution of the detergent and allowing the mixture to stand 24 hours. The solution was then examined with a photoelectric turbidimeter and the carbon number, expressed as milligrams of suspended carbon per 100 ml. of solution, was determined. The results shown in Figure 1 indicate that the deflocculating power of the sulfonated ether is superior to that of the other detergents tested.
ETERGENTS generally available may be broadly classified as saponified vegetable oils or soaps, sulfonated esters, and sulfated alcohols. All three have limitations; those of soap in hard water or acid solutions are well known. The sulfonated esters and sulfated alcohols (organic synthetics) have greater adaptability than soaps in regard to the physical conditions under which they can be used effectively as detergents. Up to a certain point synthetic compounds are efficient in hard water, but in water above 5 grains hardness it is necessary to keep the solution a t about 120140" F. to prevent the precipitation of the mineral salts.
8 o d 5ooc
?/SULFONATED
7 0.1
__
np
/
A
ESTER
SULFATED ALCOHOL
04 0 .6 . CONCENTRATION (100%BASIS), %
__
OB ,
Adsorption
If a scouring agent is highly adsorbed by textiles or shows strong preferential adsorption, trouble is experienced because excessive quantities of detergent are removed from the bath and continuous operation becomes difficult to control. Adsorption becomes doubly serious in laundry operations, for in a rinsing bath the molecules of a material showing such properties will cling to the rinsed goods. In order to remove the cleansing agent, additional washings would be necessary, A comparison of adsorption rates is a fairly accurate estimation of the comparative costs to be expected in the use of various synthetic organic soaps. Those showing the highest adsorption would exhaust from a scouring bath in the short-
I 1.0
FIGURE 1. DISPERSION OF CARBON Sulfated alcohols and sulfonated esters have the unwanted property of decomposing under certain conditions of moisture and acidity to form sulfuric acid. On textiles which have absorbed such compounds, this may prove to be inconvenient. There are other limitations; the sulfonated esters cannot be used successfully in strongly alkaline baths, while sulfated alcohols are not effective in strongly acid baths. Obviously there is room for improvement in the field of synthetic detergents, and a recently introduced sulfonated aliphatic ether may now be used under conditions which heretofore have limited the efficiency of the other compounds. As would be expected of an ether compound, the outstanding characteristic of this new substance is its stability under diverse chemical conditions, It does not decompose in boiling acid or alkali, and in a commercial textile application it retains detergent properties after 18 hours in a boiling 1 per cent solution of potassium permanganate. It is adaptable for use in hard water. A mixture containing 1 per cent calcium chloride, l per cent sulfonated ether, and 98 per cent water is quite clear even in the cold; other detergents are precipitated by water of 10 grains hardness. Though stability is the most important feature, tests and practical trials have indicated superior detergent and deflocculating properties. The cleansing action of soaps is due largely to the fact that particles of dirtare dispersed and subsequently held in suspension, and these simultaneous actions may be described as de-
CONCENTRATION OF SOLUTION, %
FIGURE
2.
ADSORPTION CURwS
est time. Such empirical comparisons were obtained by mixing a weighed amount of carbon with increasing amounts of detergent and noting the quantity required to produce a permanent froth. Figure 2 shows the results obtained with a sulfated alcohol, a sulfonated ester, and the sulfonated ether. 64
JANUARY, 1939
INDUSTRIAL AND ED;IGINEERING CHEMISTRY
The resu1t.s obtained by the adsorption test which show a lesser adsorption of the ether are borne out also by Figure 3 which illustrates the breaking strength of cloth after repeated washings in the three synthetic detergents. Figure 3 does not indicate that the sulfonated ether actually increased the tensile strength of the fibers. The results must be interpreted as showing that the pieces of cloth washed with the ether compound retained the normal gain in tensile strength usually present in a washed piece of goods. This increase of strength, due to the alignment of fibers and the attendant distribution of strain, is lost in the samples washed with soap, sulfonated est.crs, and sulfated alcohols; for continued s o r p tion~.of detergent and precipitates of hard water soap have +lo
65
Scouring Properties The scouring properties of this new detergent are illustrated by Figure 4 which shows skeins of wool which were scoured in various baths of detergents and dyed with an oilsoluble dye. Each skein was given three baths in the treatment noted, consisting of an immersion of 3 minutes a t 135"F. and two 1-minute immersions a t 120°F. The depth of shade prduced by the oil-soluble dye is an inverse measurement of the amount of oil left in the fiber by the various treatments; tlie darker the shade, the less efficient the detergent. This trial was checked by a further experiment in which 10-gmm skeins of wool were subjected to the threebath scouring process, and the oil remaining in the skein was removed by etber extraction. The tabulated results follow:
z
SULFONATEO ETHER
Sample NO.
0.5% Soda Ash Plus Following
1
2
0.25 soep 0.25eulfonsted ether
3
0.08eulfonated ether
4
0.25 sulfated doohol
Detergent %
G?~sseRem~ini.na in l0-Gram Skein earn
0.039 0.027
paste
0.040
paste
ti7
-I5[
-.i;j
SMWU
OLEATE 1SOAPI
-20 NUMBER OF LAUNEERINOS
FrowuE 3. BREAKING STRENGTH OF CLOTHABTER b P E A T E D WASRINQS IN SYNTBETIC DETERGENTS
1.
0.5 per cent soda as11
2.
+
0.6 p e r cent aods aah 0.25 pei Cent aulfated alcohol
As Figure 4 and the table show, the ether is about three times as effective on a pound-for-pound basis &s is soap, and these figures have been c o n h n e d by actual practice in woolen mills. The salts of the sulfated alcohol and sulfonated esters formed by the reaction with the calcium and magnesium compounds in moderately hard water are not soluble in cold solutions, and they are not as soluble in hot solutions as the corresponding salts of the sulfonated ethers. If present in low concentrations, the salts of hard water act as a builder for
CouiLeay, Rdhm & H m Company
+
3. 0.5 Der Cent Bods sah 0.25 per cent sulfonated eater
FIGURE4. SCOURING EFFICI~ ENCY caused overlubrication and slippage of fibers. From Figure 3 it is apparent that as the washings increase, more and more of the alcohol, ester, and soap detergents are taken up by the fiber. I n tbe case of the ether, repeated washings remove as much detergent as is regained by the fabric; therefore, a maximum saturation of t.extile is reached which limits lubrication and slippage. This is interesting from the standpoint of health and comfort, because sulfated alcohols and sulfonated esters can hydrolyze to sulfuric acid under conditions which a perspiring human would afford, and material left in a washed piece of goods could cause irritation. The sulfonated ether does not decompose in this manner and therefore may be a safer product to use for laundry operations. The tests were carried out according to the methods developed by Pauline Beery Mack, of Pennsylvania State College, and allowance for shrinkage was made by subjecting the same number of threads to the pull of the strength test machine.
0.075
OF
4.
+
0.5 per aent soda ash 0.25 pel oent sulfonated ether
SYNTHETIC DETERCENTS 5
SULFONATED EWER
4
Y
..---.+ 5
5 20 WRDNESS , ORAIIWS
10
25
FIGWEE 5. PROPERTIES OF SYNTKETIC DETERGENTS IN TBE PRESENCE OF HnRn WATERAT ROOMTEMPERATURE
INDUSTRIAL AND ENGINEERING CHEMISTRY
66
any detergent. As the hardness of the water increases, a point is usually reached a t which precipitation begins; this, in a sense, is equivalent to titrating the detergent against the hard water salts. The insoluble curds formed inactivate the detergent and, through removal of calcium and magnesium salts by precipitation of insoluble soaps, soften the water. Figure 5, obtained by plotting interfacial tension against grains of hardness, illustrates the properties of the common synthetic detergents in the presence of hard water a t room temperature. The change in interfacial tension is directly proportional to the increase in activity of the detergent; the more the change, the greater the increase. In common concentrations the interfacial tension is almost independent of the concentration of detergent. For this reason the loss in activity due to the formation of insoluble soaps is not immediately reflected in the interfacial tension. The sulfonated ether is not affected by strong acid solutions, and it may be used as a scouring and leveling agent in electroplating work. It has found application in the washing of
VOL. 31. NO. 1
fruit; and the chemical stability of this compound has given it unique possibilities in the cosmetic industry, for small amounts left in the pores of the skin should not decompose to form irritating substances. It may, for instance, have value as an acid soap for individuals who are sensitive to alkaline compounds. Skin normally has a pH of 5.5, and dermatitis is sometimes caused by the inability of the skin to regain this condition after the use of an alkaline soap. The sulfonated ether may be used in a slightly acid bath, and the small amounts retained by the skin should cause no ill effects. The possible applications of this newly developed compound are numerous, and it has already proved helpful in overcoming many industrial problems in detergency.
Acknowledgment The author wishes to acknowledge the cooperation of R. C. Whitman and L. P. Hall, of the Rohm & Haas Company, where this ether was developed, in obtaining and permitting the use of the data presented. RECEIVED December 7, 1938.
SURFACE ACTIVE AGENTS' Manufactured in America and Commercially Available NAME
TYPE
Aditex LU-1 Aerosol OS
Soluble terpene oils Alkyl aryl sulfonate
Kier boiling Wetting & detergent
Aerosol OT, MA, AY
Sulfonated esters of dicarboxylic acid Oil ester sulfate Sodium alkyl naphthalene sulfonate Sodium tetrahydronaphthalene sulfate Complex methyl esters of high-molecular-weight alcohols, acids & lactones
Wetting
Aliphatic ester sulfate Alkanol B, HG, SA Alkanol S Alox 350, 152, 800, 600, 700 Amalgol 2-Amino-2-ethyl1,3-propsnediol 2-Amino-3-hexanol 3-Amino4heptanol 2-Amino-2-isopropyl1,3-propanediol 2-Amino-2-methylI-butanol 3-Amino-3-methyl2-butanol 3-Amino-%methyl4-heptanol 3-Amino-3-methyl4-heptanol 2-Amino-2-methyl3-hexanol 3-Amino-3-methylZ-pentanol 2-Amino-2-methyl1,3-propanediol 2-Amino-2-methylI-propanol 5-Amino-4-octanol 2-Amino-1-pentanol 2-Amino-2-propyl1,3-propanediol Areskap
.....
IXDUSTRY
USE
Wetting Wetting Dispersing
Textile Electroplating, pigment, paper All uses
MANUFACTURER Hart Products Corp. ilmerican Cyanamid &Chemical Corp. Same
Textile Onyx Oil & Chemical Co. Textile, paper, leather, E. I. du Pont de Nemours & pigment Co., Ino. Metal processing Same
Wetting agents for metals Lubricating
Alox Corp.
Detergent
John Campbell & Co., Inc.
Fatty acid salts of
General wetting & emulsifying detergent
Monobutyl phenyl phenol sodium monosulfonate
Penetrant in textiles
Textile
Commercial Solvents Corp.
Fruit washing, embalming penetrant
Monsanto Chemical Co. (Continued on page 67)
1
Compiled by F. J. Van Antwerpen, Associate Editor,
INDIJSTRIAL AND ENGINEERING CHEMISTRY. /
JANUARY, 1939
INDUSTRIAL AND ENGINEERING CHEMISTRY
67
SURFACE-ACTIVE AGENTS (Continued from page 6 6 )
NAME Aresket Aresklene Arylene Bensapol Betasol OT-A Bozetol Cominol Daconol Daintex Darvan Daxad Deceresol OT
TYPE Monobutyl diphenyl sodium monosulfonate Dibutyl phenyl phenol sodium disulfonate Sulfonated aromatic compound Sulfonated oils & solvent Sulfonated ester of dicarboxylic acid Sulfonated derix-ative of castor oil Derivative higher sulfonated alcohol Alkyl aryl sodium sulfonate Miscible terpene alcohols & hydrocarbons Polymerized organic salts of sulfonic acids of alkyl aryl type Same Sulfonated ester of dicarboxylic acid
INDUSTRY
USE
Insecticides
Emulsifying oils, fats Wetting
Mold lubricant & pene- Same trant, latex conditioner Textile Hart Products Corp.
Wetting, detergent Wetting
Textile Leather
Wetting
Textile
Wetting, detergent
Textile
Antipitting agent Wetting, penetrant
Sickel plating Laundry
Commonwealth Color Chemical Co. S. A. Day Mfg. Co., Inc. Hercules Powder Co.
Dispersing
Color, textile, paint
R. T . Vanderbilt Co., Inc.
Same Wetting
Flotation, emulsification Textile
Dewey & Almy Chemical Co. American Cyanamid &Chemical Corp. Hart Products Corp. Commonwealth Color & Chemical Co. Stanco, Inc.
Detergent Textile Textile Derivative of higher sulfo- Wetting, detergent nated alcohol Textile, rubber mold, luWater-sol. sulfonated min- Wetting, lubricant Dipex bricant eral oil Washing of fine fabrics, Laundry Fatty alcohol sulfate Dreft woolens Fatty alcohol sulfate Shampoo purposes Drene Duponol L-144 WD, LS, Long-chain alcohol sulfates JT e t t i n g, emulsifying, Leather, textile, paper, softening, detergent felt cleaning ME, OS, WA, T , WS, 80 Wetting, detergent Cleaning Elemite Sulfonated oils & solvents Textile Evener 1, 25-2 Compound with sulfonated Wetting oil base Textile Sulfated compound with Detergent Extol solvents Condensation product of Wetting Paint, lubrication Floex higher fatty alcohol Gardinol LS, WA Fatty alcohol sulfate Wetting, emulsifier, dis- Textile persing, finishing agent Garclinol LS, special WA Long-chain alcohol sulfate Same Textile
Hartolein K-122 Hartopene Hornkem 1 Hornkem 3 Hymolit Hytergen Igepon AP Extra Igepon
'r
Intramine Invadine B, C, N Kliersol Lanaclarin LM Lightning Penetrator X Loupene Loupole W-950 Mapro Degum & Scourer Maprofix Mapromin Mapromol
Sulfated oils & solvents Sol. chlorinated solvents Glycol soaps containing buffered alkalies Pine oil soap containing buffered alkalies Pine oil gel Sulfonated natural materials Sulfonated natural materials
Monsanto Chemical Co
Wetting, spreading
Degumtex MK-105 Detanol
Hartex Oil K-40 Hartex Oil K-101 Hartex Oil L-33
MANUFACTURER
Jacques Wolf & Co. American Cyanamid &Chemical Corp. Hart Products Corp.
Procter & Gamble Co. Same E. I. du Pont de Nemours & Co., Inc. Jacques Wolf & Co. Hercules Powder Co. Hart Products Corp.
Ross and Rowe, Inc. Procter & Gamble Co.
E. I. du Pont de Nemours 8 Co.. Inc.
Detergent Detergent Detergent
Textile Textile Textile
Hart Products Corp. Same Same
Detergent
Textile
Same
Textile Dispersing agent for hy- Pigments drophobic particles Dispersing & wetting of Dry pigment, dry color hydrophobic particles ..... Detergent Textile ..... Detergent Textile Oleic acid ester of an ali- Detergent Textile phatic compound C I T H ~ ~ C O N H C ~ H ~ Detergent, O ~ N ~ wetting, emul- Textile sifying Sodium salt of sulfonated Detergent, wetting, emul- Textile, cosmetic lauryl and myristyl colsifying lamide Sodium alkyl phenylene sul- Wetting Bleaching, carbonizing, fonate neutral or acid baths Phosphate salt Regenerating lime soaps ..... Long-chain alcohol sulfate Wetting agent detergent, Textile dyeing assistant Sulfonated higher fatty al- Wetting, penetrant Textile cohol Sulfonated oils & solvents Wetting, detergent Textile Same Same Textile Sulfated fatty alcohol and Detergent Textile auxiliaries Sulfated fatty alcohol Wetting, detergent Textile Same Wetting Textile Same Same Textile (Continued o n page 6 8 )
&
Same A. C. Horn Co. Same Hart Products Corp. Same General Dyestuff Corp.
,
Same Synthetic Chemicals, Inc. Ciba Co., Inc. Hart Products Corp. E. I. du Pont de Nemours & Co., Inc. Commonwea1t.h Color & Chemical Co. Jacques Wolf & Co. Same Onyx Oil & Chemical Co. Same Same Same
INDUSTRIAL AND ENGINEERING CHEMISTRY
68
VOL. 31, NO. 1
SURFACE-ACTIVE AGENTS (Continued from page 6 7 )
TYPE
,\jAME
Wetting Sodium alkyl naphthalene Wetting, dyeing assistant sulfonate product Long-chain alcohol sulfate Detergent, wetting, dyeing assistant Sodium metasilicate penta- Detergent hydrate Metasilicate compn. Detergent Alkaline silicate Detergent Sodium sesquisilicate hy- Detergent drate Long-chain alcohol sulfate Wetting, detergent, dyeing assistant Fatty alcohol sulfate Wetting, detergent, emulsifier, finishing, dispersing, lubricating Highly sulfonated castor oil Wetting Alkyl naphthalene sulfonic Wetting acid ester Modified alkyl aryl sulfo- Detergent nate Sodium alkyl aryl sulfonate Detergent Same Antipi tting,agent Detergent,wetting,scourSame ing, dyeing assistant Same Detergent Same Detergent of high water soly. Sodium alkyl naphthalene Wetting sulfonate Same Wetting Wetting Naphthalene sulfonic acid
Merpol B, C Metso granular Metso 22 Metso 66 Metso 99 Modinal T Modinal T Monosulph N. S. A. E. Naccolene F Nacconol E Nacconol EP Nacconol NR Nacconol NRL Nacconol NRSF Naccosol A Nekal A, BX Neomerpin N Neomerpin VD
Sodium alkyl naphthalene Wetting sulfonate & solvents Sodium abietene sulfonate Wetting, dispersing
Neopen SS
Sol. pine oil Sulfonated oil, vegetable type Sulfonated alkyl hydrocarNopco 1967 bon Modified sodium alkyl Novonacco naphthalene sulfonate Modified alkyl naphthalene Novonacco N N sulfonic acid Oil ester sulfate Oleo Glyceryl Sulfate C Same Oleo Glyceryl Sulfate 0 Same Onyxol 66 Orthosil, regular and spe- Concd. alkaline cleaning compounds cial Fatty alcohol sulfate Orvus WA Nopco 1440 Nopco 1935
Para Oil Pemeko Penatrol 60, 65 Penetrex Pennsalt cleaners Pentaaicon T Pentogen Phosphosol Phosphotex Radiactine Rayon Scour A Resolin N F Rinfors L Royox Sandocarnit
INDUBTRY
USD
. ...
Mercer01 Merpentine
.
Wetting
Textile Textile
MANUFACTURER
Textile
Sandoz Chemical Works, Inc. E. I. du Pont de Nemours & Co., Inc. Same
General cleaning
Philadelphia Quartz Co.
Same Metal cleaning General cleaning
Same Same Same
Textile Textile
E. I. du Pont de Nemours & Co., Inc. Procter & Gamble Co.
Textile Textile
National Oil Products Co. Onyx Oil & Chemical Co.
Dry cleaning
National Aniline & Chemical Co., Inc. Same Same Same
Fruit washing Nickel plating Rug cleaning Laundry
Same Same
Textile
Same
Textile Electroplating
General Dyestuff Corp. E. I. du Pont de Nemours & Co., Inc. Same
. . ...
Textile, leather
Electroplating, textile, Same pickling baths Textile National Oil Products Co. Sanforizing process Same
Wetting
Textile
Same
Wetting
Textile
National Aniline & Chemical co. Same
Wetting, carbonizing Textile agent Wetting Textile Wetting Textile Wetting Textile Metal cleaning
Onyx Oil & Chemical Co. Same Same Pennsylvania Salt Mfg. Co.
Wetting, detergent, Textile, electroplating, Procter & Gamble Co. emulsifying, finishing, rubber dispersing, lubricating Wetting, detergent Textile Jacques Wolf & Co. Saponified oils Wetting Textile John Campbell & Co., Inc. Wetting, penetrant Paper, textile, leather, Beacon Co. metal cleaning Textile Hercules Powder Co. Compound with sulfonated Wetting, detergent oil base Pennsylvania Salt Mfg. Co. Concd. alkaline cleaning Metal cleaning compounds Textile Merck & Co., Inc. Sulfonated products of vege- Leveling, penetrant table oils, fats, hydrocarbons Hart Products Corp. Textile Sulfated compound contain- Detergent ing solvents Monsanto Chemical Co. Tetrapotassium pyrophos- Wetting, detergent, pene- All uses trant phate Same Tetrasodium pyrophos- Wetting, detergent, pene- All uses trant phate Sandoz Chemical Works, Inc. Leveling agent Textile Algin soap compound Detergent Textile Same Same Wetting agent Textile Same Same Same ..... Detergent Textile Royce Chemical Co. Detergent Laundry Pine oii with soap Sandoz Chemical Works, Ino. Wetting Textile .....
.....
.....
(Continued on page 69)
JANUARY, 1939
INDUSTRIAL AND ENGINEERING CHEMISTRY
69
SURFACE-ACTIVE AGENTS (Continued from page 68)
NAME Sandopan A Sandozol N Santomerse Sapamine A Scourtex H-73 Silvatol I, I1 Soapotol Solhex Solvadine NC Sulfatate Surfax W O Tar Remover “P” Tensol Tergitol Penetrant 4, 7 Tergitol Penetrant 08 Tramolin Trimethylol aminomethane Triton M-25 Triton W-30 Triton S-18 Triton 720, 812 Turkey red oil Tytrovon RZB Ultravon K, W Ultrawet Ultroil Wetanol Wetsit Wolfco Scour W-932B Wolfco Solvent Xynomids Yarmor 302 Yelkin T
USE
TYPE
INDUSTRY
.....
MANUFACTURER
Detergent Textile Wetting agent Textile Alkylated aryl sulfonate Wetting, detergent, pene- All uses trant Diethyl aminoethyl oleyl Leveling agent Textile amide acetate Sulfated oils and solvents Detergent Textile Pine oil compound Detergent Dry cleaning Derivative of higher sulfo- Wetting, detergent Textile nated alcohol Compound with sulfonated Wetting Textile oil base Alkylated aryl sulfonate Wetting Textile Sulfonated hydrocarbon Wetting Textile, paper, cosmetic, leather ..... Wetting, detergent Textile Compound with sulfonated Detergent Textile oil base Sulfonated ether Dispersing, emulsifying Textile, cosmetic Higher secondary alcohol W e t t i n g, dispersing, Textile, agricultural, rubsulfate penetrant ber, latex Synthetic primary alcohol Wetting, penetrant Coned. soln. of alkalies, sulfate acids, salts Sulfonated vegetable oil Wetting Textile Fatty acid salt of General wetting, detergency, emulsification
Sandoz Chemical Works, Inc. Same Monsanto Chemical Co.
Sodium salt of an organic ether acid Sulfonated aromatic ether alcohol Quaternary ammonium salt Sulfonated ether Sulfonated vegetable oil S a 1 t o f high-molecularweight sulfoacid Sulfonate of complex stearyl alkyl compound Aromatic monosodium sulfonate Sulfonated vegetable oil Modified sulfated fatty acid ester Alkylated aromatic sulfonate Emulsion of chlorinated solvents Saponified vegetable fats with solvents Sulfonated fatty acid condensates Terpene alcohol, terpene hydrocarbon, p i n e o i 1 fraction Oil-sol. organic phosphatide, chiefly lecithin
Rtihm & Haas Co.
.....
Wetting, penetrant
Textile
Ciba Co., Inc. Hart Products Corp. Ciba Co., Inc. Commonwealth Color Chemical Co. Hercules Powder Co. Ciba Co., Inc. Glyco Products Co., Inc.
E. F. Houghton & Co. Hercules Powder Co. Synthetic Chemicals Inc. Carbide & Carbon Chemicals Corp. Same Hercules Powder Co. Commercial Solvents Corp.
Wetting, penetrant, dis- Textile, cosmetic persing Wetting, emulsifying Lubricating Detergent Textile, cosmetic Wetting Textile Detergent Textile
Same
Detergent
Textile
Ciba Co., Inc.
Wetting, detergent
Wetting
Textile, laundry, agricul- Atlantic Refining Co. tural spray, paint Textile Hercules Powder Co. Textile, cosmetic, paper, Glyco Products Co., Inc. leather Textile, paper Jacques Wolf & Co.
Detergent
Textile
Same
Detergent
Textile, laundry
Same
Wetting, detergent
Textile
Onyx Oil & Chemical Co.
Wetting
Textile, laundry
Hercules Powder Co.
Wetting agent for oils
Textile, paint, leather
Ross & Rowe, Inc.
Wetting Wetting
&
Same Same Hercules Powder Co. Merck & Co., Inc.
