F IP 85 G5 XR 2 8; 3. G 3, 7 2,183,037 December 12,UNITED 1939 STATES PATENT OFFICE 2,183,037 GERMCDAL DETERGENT Milward Bayliss, Hurlock, Md., and John L. Wilson, St. Paul, and Erling J. Ordal, Minne apolis, Minn., assignors- to Economics Labo ratory Inc., St. Paul, Minn., a corporation of Delaware No Drawing. Application May 10, 1935, Serial No. 20,766 3 Claims. (Cl 16-14) This invention relates to improvements in higher alcohols are obtainable by catalytic reduc germicidal detergent compositions and includes tion, under proper conditions, from the fatty such compositions in a concentrated or dry state, acids of natural fats and their esters. When su Such as a dry powder, as well as germicidal Solu fonated With Concentrated Sulfuric acid under tions of such compositions. proper conditions they yield products known in The neW compositions are valuable for use in the trade as fatty alcohol sulfates or aalf sul homes, hotels, restaurants, hospitals and insti furic acid esters of the fatty alcohols. While tutions, as Well as in the beverage and dairy in referred to as Sulfonated fatty alcohols, they dustries, Where a germicidal action as well as a are more properly referred to as alkyl esters of detergent action is desired. Sulfuric acid having for example the general O The new germicidal detergent compositions are formula, R.O.SO2.ONa, where R is a straight chain in general admixtures of alkalies or buffer salts aliphatic radical containing 8 or 10 carbon and wetting agents of the character hereafter atoms or more. A Simpler formula for these st referred to, in such proportions that when, for fonated fatty alcohols is R.SO4Na, representing 5 example, a Solution is made of the composition the sodium salts of the alkyl sulfates, where R. 5 containing from A3% to 3% of the composition is a long chain aliphatic radical. Among these the Solution Will have a high pH value, in excess sulfonated fatty alcohols may be mentioned so of about 11.5. dium lauryl sulfate, sodium octadecyl sulfate, and The buffer salts which are used in the new sodium oley sulfate. The technical grade of sul composition are alkaline salts or alkalies, such fonated laury alcohol is known as sulfohated 20-..... as carbonates, phosphates or silicates, etc., used Loro and the technical grade of sulfotiated oleic in such amounts and proportions as will give or oley alcohol is known as stifonated Oceno. to the final solution the desired pH value. Where the alcohol -sulfonated is an unsaturated. Among Such buffer salts may be mentioned so alcohol the sulfuric acid may react by addition dium carbonate, mono-sodium-phosphate, di at the double bond to form sulfonic or sulfate Sodium phosphate, tri-sodium phosphate, sodium derivatives as well as by reaction with the hy 25 Silicates, etc. droxyl group to form the ester. The products In using these buffer salts, in making the new may be in part true sulfonic acids or may con composition, the proper pH is obtained by a se tain true Sulfonic acids as well as sulfates or su lection of the buffer salts employed which may, furic acid esters. When chloro-sulfonic acid is 30 in Some cases, be a single salt or salts of the same used for Sulfonating the unsaturated alcohols true. 30 acid, Cr salts of different acids, etc. For ex Sulfonic acids are produced and where the al anple, the proper pH may be obtained by the use coholic hydroxyl is converted into a sulfate the of a mixture of various phosphates and carbo Sulfonated alcohol may contain both a sulfonic nates, or various phosphates and silicates, or and a Sulfate group. The sulfonated higher al 35 carbonates and silicates, or by mixtures of phos cohols are marketed under various trade names, 35 phates, carbonates and silicates as well as by Such as Gardinols, Brilliant Avirols, Orvus, Dreft, mixtures of various phosphates alone, or carbo etc. The sodium oleyl sulfate, for example, is nates alone, or silicates alone. Similarly, other marketed under the trade name Gardinol CA and Salts besides phosphates, carbonates and silicates the lauryl Sodium sulfonate is marketed under may be used to obtain the proper pH. the trade name Gardinol WA. The higher fatty 40 The Wetting agents which are used, together alcohol sulfonates derived from steary and cety With the alkaline salts, in making the new com alcohols are marketed under the trade names positions, are in general wetting agents of a char Brilliant Avirols L142, L144 and L168. These acter which are superior to and distinguished various sulfonated alcohol products are used in 45 from ordinary soap. Among the important wet the form of their sodium salts. ting agents which are employed in accordance The sulfonated higher alcohols, although pro with the present invention, are sulfonated prod duced by the sulfonating of the alcohols, are in lucts such as Sulfonated hydrocarbons or sulfo their nature sulfonated hydrocarbons or hydro 50 nated higher alcohols and sulfonated oils which carbon Sulfates and may be referred to as alkyl 50 are free from a carboxyl (free or neutralized) Sulfates. group or which have a carboxyl group blanked or Other sulfonated hydrocarbon wetting agents made ineffective. Certain phenolic or alcoholic can also be used in the new composition of the Wetting agents are also included. present invention Such as the alkyl naphthalene The sulfonated higher fatty alcohols have re sulfonic acids sold in the trade as Nekals, Permi 55 cently been introduced in commerce as wetting nais, Merpentine and Akanol B. Substituted agents and these are well adapted for use in the naphthalene sulfonic acids are also Sold under new composition of the present invention. The the trade name Oranit. Isopropyl naphthalene 2 2,188,087 sulfonic acid is sold under the trade names Neo ients. Such a dry mixture of the ingredients merpin, Erkalin and Alkanol SA. The alkylated can be readily produced, handled, shipped and naphthalene sulfonic or sulfuric acid products are Stored and a definite amount measured or used in the form of their sodium salts, for ex weighed out for use in producing germicidal de ample, the sodium isopropylnaphthalene sulfo tergent Solutions. nate. Other sulfonated hydrocarbons are repre The particular alkali salt or salts used in the sented by sulfonated abietenes, or sulfonated composition for giving it the desired high pH abietanes, for example, sodium abietene sulfo value can be varied and are best defined by the nate; or the sodium salt of sulfonated abietanes pH value of the resulting solution rather than 0. 10 (hydrogenated abietenes). The naphthalene sul by attempting to give the various combinations fonic acid compound may be combined with one of chemicals which will provide the desired high of the fatty sulfonic acid compounds, as in Oranit pH value. BN Extra. The sodium salts of naphthalene sul In testing the Solutions of the new composi fonic acid derivatives are also marketed under the tion, We have used the following test: The dry 5 trade name Alkanol. Sodium tetralin sulfonate mixture, containing the ingredients of the com 15 is also marketed under the trade name Alkanol S. position, is made into a solution of from 2% to Sodium tetrahydro naphthalene sulfonate is the 3% strength. To 5 cc. of this solution is added A cc. of a 24 hour culture of the standard test active wetting agent in Alkanol PF. organism, Staphylococcus aureus (Insecticide Certain sulfonated wetting agents are made 20 20 Board strain). Before the culture is added to from oleic acid and isethionic acid. The prod the test solution, it is brought to the required uct having the formula - temperature; the temperature We have used has CH3(CH2) CH:CHCCH) COOCHCHSONa been 37° C. or in some cases a higher tempera is sold under the trade name Igepon A. A some ture. After the culture has been in the test solu 25 25 tion for five minutes, a 4 mm. loopful is removed What different product having the formula and added to a tube of molten agar at a tem perature of 45° C. and the mixture is poured into chich ch:Chch) conchschisonCs a Petri plate. The plates are incubated for 48 hours, at the end of which time a count is made is sold under the trade name Igepon T. Igepon T of the colonies appearing on the plate. The num 30 30 in a solvent is sold under the trade name Laven ber of organisms originally added to the test tine KB. The sodium salt of the oleic acid ester solution is in the neighborhood of five hundred of isethionic acid is sold under the trade name millions (500,000,000). If no organisms are of Igepon AP. killed, the loopful removed will contain an ex Wetting agents derived from ricinoleic acid by cess of 10,000 organisms, and therefore the num -35 35 Sulfonation and with the hydrogen of the car ber of colonies appearing on the plates will be boxyl group blanked to render it ineffective are in excess of 10,000. If some of the organisms represented by the sodium salt of. the sulfuric are killed, the number of colonies appearing on ester of butyl ricinoleic ester. the plates will be less than 10,000. In the data reported in the following examples, the numbers 40 C17H32(SO4Na).COOCH indicate the colonies appearing on the test plate Sold in the trade as Avirol AH Extra. Sulfonated after 48 hours of incubation. Similar tests were fatty oils are sold under the trade names Nopco made using Eberthella typhi (Hopkins strain). Castor and Intrasol. As illustrating the action of water alone, Sodi The sodium salt of the sulfuric ester of oleic um lauryl sulfate alone, in various amounts, 45 s amide is sold under the trade name Humec sodium carbonate, trisodium phosphate, Sodium O. C. meta-silicate and sodium sesqui-silicate, the foll The various wetting agents are used in the lowing table gives the results of tests made as new composition in the form of their sodium above described, with these various Substances, Salts together with the buffer or alkaline salts the tests being carried out with StaphylococcuS 50 in such proportions that there will be present in aureus (F. D. A. strain) at a temperature of 37 the solution made of the composition only a C. and with a plate count after 5 minutes and Small percentage of the wetting agent together 10 minutes respectively. The organism employed With such amount of the buffer salt as will give and the temperature and time of the test are in to the solution, a high pH value of around 11.5 5 or higher. While the wetting agents themselves accordance with the standards adopted by the are relatively ineffective as germicides, the com Federal Food and Drug Administration (F. positions in which they are used together with D. A.) : the alkaline salts are highly effective, such that solutions from the new compositions are excellent Plate counts 60 detergents and exhibit sufficient germicidal prop Solution tested erties So that they can also be used as germicides. 5 min. 10 min. In general the solutions made from the new com Water alone...... ------...-- 10,000-- 10,000 positions will contain from around 4% to 3% 0.01% sodium laurylsulfate - 10,000-- 10,000 of the composition, although the amount can be 0.1% sodium laury sulfate - 10,000-- 10.000-- 65 .0% sodium laurylsulfate. 0, 000-- 10,000 Somewhat varied. 2.0% sodium lauryl sulfate. ------10,000-- 10,000 The new compositions are advantageously com 1% sodium carbonate (Na2CO3) (pH = 11.4). 10,000-- i0,000-- 2% sodiun carbonate (Na2CO3) (pH = 11.5). 10.000-- 0, 000-- pounded and marketed in the form of a dry pow 1%. T. S. P. (trisodium phosphate) der containing the Wetting agent, where avail (NaapO.12H2O) (pH 12.0).------10,000-- 10,000 2%. T. S.P. (trisodium phosphate) 70 able in a dry powdered form, together with the (Na3PO.12H2O) (p=12.2).------3,000- 3,000 70 pulverulent alkaline salt, in the form of an inti 2%. Metso (sodium metasilicate) (Na2SiO3.5H2O) (pH = 12.6)------1,800 900 mate and substantially homogeneous mixture, 1% Metso (sodiur metasilicate) Such that a definite weight of the powdered con (Na2SiO3.5H2O) (pH = 12.3).------...- - 10,000-- 8,000 position can be used to give a solution of definite 1% Metso 99 (sodium sesquisilicate (pH = 12.6). 2,000 800 strength and proportions of the different ingred

w 4- V4 u ViVi i Us U V o . . . . S- '-' i \l V . . . . 353 2,188,087 3 From this table it will be seen that the various above referred to, the last three solutions rep alkaline salts alone are ineffective at this tem resenting phenol solutions used as control: perature and in these concentrations as germi cides and that the Sodium lauryl sulfate is like Plate counts 5 wise ineffective. However, when sodium lauryl Solution tested 5 Sulfate or other effective wetting agents, such OO eSte 5 min. 10 mi as those above referred to are used in combina- Illn. II. tion with the alkaline Salts, a pronounced germi- --- cidal action as well as detergent action is ob- 'S3SESSEE2%, Met ilicat - 3,000 700 10 tained The germrmicidal cidal actionacti of sodium laury 2%5%. Metso--.2%Meis2%inetol Erkalin------C O0. 0.0. 0 sulfate in various amounts used together with 3:23; ER.I. - - O 0. trisodium phosphate and sodium meta-silicate 5: MEEE?: EEAP. - 8 8 (Metso) are illustrated by the following table, the 5% ME32EnexB. O ... 0- - - organism used, the temperature, etc., being those 2% MetS0.2% Nopco Castor- m 0. O f to: 2% Metso--.2%, Orwusu- O () 15 above referred to: 60 phenol used as control.-- 0 6 lis 1io phenol used as control- 2 0 fas phenol used as control.-- 25 0 . Plate counts Solution tested From the above examples it will be noted that 20 the solution tested contained only a small frac- 20 tion of a percent of the wetting agent and only 3.T. S. EEEP.--.01% sodium laurylity sulfate------Ste. 2001g 20 around 1 or 2% of the total composition, but 5%. T.S.E.5%iniayat. S. P.--.02% sodium laurylsulfate 0. 80. the solution was nevertheless effective as a 3: E. S. E; sodium EY life. - 6 germicide in addition to its detergent properties. 25 25 2%1% T.Metso S. P.--.5% bi; sodium lauryllaurylsulfate------sulfate------. 0 (O The wetting agentS used in the comp Osition % MS 8.83% E. E. SA:------8 g impart improved penetrating properties to the i?; Metsetso 88:sodium sodiura laury laurylsulfate sulfate-- - 125 15 composition, making the composition effectiveo i % NE 8:EN t ife - 4g 19 its detergent as well as its germicidal properties. : 3% Metso;%dinallyetS0--0. ium laurylsulfate. sulfate...I. - 0 In general the amounts of wetting agents will be 30 3.NEE 88: E.E.------around 0.002% or higher, the amount to be used. 3 e.So Sodium lauryl Sulfate...---- 4. 5%. Meisiifinalisat...I. 7 3 inOn practicethe pH ofdepending the solution, on the on wettingthe temperature agent used, of the Solution, and on the length of time of con tact with and the kind of organisms to be killed. . These results are to be compared with the ac In general the amount of the Wetting agent will 35 35 tion of phenol solutions used as control where form only a small proportion of the dry mix the following results were obtained: ture, where the composition is prepared and marketed in dry form, the greater part of the Plate counts composition being made up of the alkaline or 40 Solution tested buffer salts of such nature and amount as will 40 5 min. 10 min. impart to the solution of the composition the ---360 phenol------0 desiredThe new high compositions pH value. are useful for wmany pur 45 EII.I.I.I.I.I.I.I.I. 38 posesmicidal as detergentsin hospitals are or important, institutions, as wherewell as ger in 45 hotels and restaurants for dish-washing and The results of tests made as above described other purposes, and in various industries such with compositions made with various wetting as the beverage and dairy industries, where it is agents and with sodium meta-silicate or sodium important, for example, to sterilize the bottles 50 carbonate, in accordance with the tests above re- and containers as well as to wash them. 50 ferred to are given in the following table: ralityIn some or mixture cases it ofis advantageousactive wetting to agents, use a plu in stead of only one active wetting agent, in the Plate counts new composition. The active wetting agents 55 Solution tested differ somewhat in their detergent or Sudsing 55 5 min. 10 min. properties, and it is sometimes advantageous to ------add a wetting agent which is less ineffective in Asiadiiminatasilicate)-%.53S3 sayse ------... 10,000+10,000-- 10,000+sooo the germicidalcomposition properties together whichwith anotherit imparts active to 60 }%NE.2% E; 1, i wetting agent which is more effective, thereby 60 3.NE; is 200 3 obtaining a balance in antiseptic and detergent 3: M33.3% FEE.I. properties by the use of two or more active 1%% EE:Metso.2%Orvus SE (sodium Fairginia. laurylsulfate). 205 9 wettingother in agentstheir properties, which differ or onesomewhat of which, So, though each 65 3.E. - - 28 8 more effective, is more expensive, and it. 65 1%MeSQQ2%ISYentire R --- - - 2. advantageously used in smaller amounts togeth % ME233; Elsulfate- : er with one or more other active wetting agents. It will be understood that, where a mixture or plurality of active wetting agents is used, the al 70 Another series of tests made with composi- kali salt, or mixture of alkali salts used to give 70 tions containing sodium meta-silicate and a frac- to the solution the high pH value, can be varied, tion of a percent of various wetting agents is and a single salt, or a mixture of salts, used, in indicated by the following table, the tempera- such proportions as will insure in the resulting ture maintained in these tests being 45 C. and solution the desired high pH value. is the same organism being used as in the tests By the term “wetting agents" we mean those 4. 2,188,087 wetting agents which are sulfonated products 2. A germicidal detergent composition com such as sulfonated hydrocarbons or sulfonated prising sodium lauryl sulfate and alkaline Salts higher alcohols, and which are free from car in Such proportion that an aqueous solution con boxyl groups, whether free or neutralized, or taining from A to 3% of the composition will which have carboxyl groups blanked or made in contain a small fraction of 1% of the sodium effective in a suitable manner, as by substituting lauryl sulfate and will have a pH value in excess of about 11.5. for the hydrogen of the carboxyl group an alkyl 3. A germicidal detergent composition con group, or an amido group, or other suitable taining a major proportion of buffer salts and group and which do not form objectionable pre containing a relatively small proportion of a O cipitates with calcium and magnesium ions mixture of active sulfonated wetting agents, in found in hard water, as distinguished from ordi cluding a sulfonated alcohol wetting agent, said nary soaps, which are neutralized carboxylic composition being adapted when dissolved in acids and which form objectionable precipitates water in amounts ranging from 4 to 3% to with calcium and magnesium ions present in form a germicidal detergent solution containing 5 hard water. a small frticipn of 1% of the wetting agents We1. A claim:germicidal detergent composition 3. com with a sufficient amount of the alkaline salts to prising a sulfonated alcohol wetting agent and give a pH value in excess of about 11.5. alkaline salts in such proportions that an acque 20 ous Solution containing from A to 3% of the MLWARD BAYSS. 20 composition will have a pH value in excess of JOHN J. WSON. about 11.5 and will contain a small fraction of ERLING J. ORDAL. 1% of the Sulfonated alcohol.