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Publication numberUS2666010 A
Publication typeGrant
Publication dateJan 12, 1954
Filing dateSep 5, 1950
Priority dateSep 5, 1950
Publication numberUS 2666010 A, US 2666010A, US-A-2666010, US2666010 A, US2666010A
InventorsRichard D Stayner
Original AssigneeCalifornia Research Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Quaternary ammonium germicidal compositions
US 2666010 A
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Description  (OCR text may contain errors)

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Patented Jan. 12, 1954 Y* UNITED STATES PATENT `OFFICE QUATERNARY AMMONIUM GERM-'ICIDAL GOMPOSITION S Richard D. SrtaynenvAlbany, Calif., assignor to 'California Research Corporation, San Fran-,- cisco, Calif., acorporation of Delaware Application September 5, 1950 Serial No. 183,277


This invention relates to new and improved compositions for the control of micro-organisms, such as bacteria, fungi, algae, protozoa and the like. More particularly, the invention relates to compositions which comprise a quaternary ammonium germicide and a promoter` Prior to my invention Quaternary ammonium compounds per se have been used as g'ermicides'. The activity of these compounds varies widely with different types of organic cation radicals contained therein. As a consequence, a great amount of experimental eiort and expense has been necessary to develop more eiiicient types oi quaternary ammonium germcide materials. Such Quaternary ammonium compounds are usually costly and in many cases are characterized lby their poor efficiency in the control of micro-organisms, ,particularly spore-forming bacteria, fungi, molds and the like.

It is an object of my invention to provide novel Quaternary ammonium compositions which are economical to produce and more eiiicient than the Quaternary ammonium compounds themselves as germicideaparticularly toward sporeforming bacteria, fungi, molds, and the like,v

Other objects and advantages of my invention will be apparent Yfrom the disclosure which hereina'fter appears.

I have found that quaternary. ammonium germicides and ,promoters of the 'type hereinafter described may be combined in su'ch proportions as to produce strongly germicidal compositions having germicidal activity even exceeding that. of the quaternary ammonium compounds them` selves. This resultant improvement in eiiiciency` is highly unexpected, since the promoters as hereinafter described are, of themselves, rela# tively poor germicides, particularly toward sporeforming bacteria, fungi, etc., against which even the quaternary ammoniumlcompounds` are relatively ineffective.

The production of these novel and more highly effective germicidal compositions according to my invention requires only the simplest of procedures. It involves none of the complicated experimentation 'that is necessary when improvement of the germicidal efficiency of a quaternary ammonium compound is attempted through' modication of the hydrophobic cationic .portion of the molecule.

The extraordinary effect of my discovery is illustrated graphically by the curve shown in" Figure 1 of the accompanying drawing. Uponv reference to this curve it will be seen 'that when certain substantial amounts of Quaternary ammonium compound are combined With promoters of the type hereinafter described, the resultant composition possesses germicidal activity against a representative fungus far in excess of the quaternary alone.

n generic term. These compounds Vare generally characterized by the formula wherein at least one of the radicals, Ri, Rz, Rs and R4, attached to the nitrogen atom is a hydrophobic aliphatic, unsaturated aliphatic, cycloaliphatic, aryl, araliphatic or aliphaticaryl radical of from 6 to 26 carbon atoms. The hydrophobic radicals may be long-chain alkyl, longchain alkenyl, cycloalkyl, long-chain alkoxyaryl, long-chain alkylaryl, halogen-substituted longchain alkylaryl, long-chain alkylphenoxyalkyl, arylalkyl, etc., in nature. The remaining radicals cn the nitrogen atom yother than the hydrophobic radicals may be substituents of hydrocarbon structure ordinarily containing a total of no more than about 12 carbo-n atoms. Various -compounds of these types are more fully illustrated in the disclosure which follows. Mixtures of quater--v naries may be used as' Well as the single compounds. r

As a brief description. of the promoters` in. the compositions according to my invention any nonanionic organic materials having a Asolubility in Water of .less `than aboutf5% and generally characterized by a high molecular weight hydropho-T-' bic'group attached to a weakly hydrophilic radical may be used. The high molecular Weight hydrophobic group is desrably aliphatic, unsat-v urated aliphatic, cycloaliphatic, aryl,7 aral'iphatic, or aliphaticaryl in nature, and contains from about 8 to .18. carbon atoms. Examples of such hydrophobic groups are the long-chain alkyl. long-chain alkenyl, cycloalkyl, phenyl, phenylalkyl, alkylphenyl, alkylphenoxyalkyl, alkylphenoxyalkoxyalkyl, etc. groups. Among the hydrophilic radicals which are characteristic of the more desirable promoters are radicals such as the hydroxyl and amino radicals.

'I'he proportions of the Quaternary ammonium germicide and the promoter are critical. to the compositions according to my invention. How-v ever, these critical proportions may vary over a Wide range from a minimum amount of promoter just sufficient to promote the germicidal activity of the quaternary ammonium compound up to a maximum amount of about per cent by weight y of the composition. Avery marked ,improvement is obtained with proportions of promoter ranging from about 10 to about 60 per cent, While compositions containing the. promoter in proportions of about 30 to about 50-per cent exhibit the .greatest increase in germicidal activity.

The improved quaternary ammonium germicide compositions of my invention are suitably prepared by adding the promoter to the Quaternary ammonium compounds in suitable proportions and mixing them'together. Various means for mixing and handling the materials will be obvious to persons skilled in the art from this' disclosure, and as such are contemplated by my invention.

As more specic examples of the various Quaternary ammonium compounds used in my novel compositions alkyl ammonium halides such as cetyl trimethyl ammonium bromide, octadecyl dimethyl ethyl ammonium bromide, octadecenyl dimethyl ethyl ammonium bromide, dioctadecyl dimethyl ammonium chloride, etc. are contemplated.` Other relatedl Quaternary ammonium salts which also may be used are thealkylaryl ammonium halides such as the long-chain alkyl dimethyl benzyl ammonium chlorides in general, including octadecyl dimethyl benzyl ammonium bromide, alkyl dimethyl dichlorbenzyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, and the like. N-alkylmorpholinium and N-alkylpyridinium Quaternary ammonium salts as illustrated by N-cetylpyridinium bromide, N- myristylpicolinium chloride, N-dodecyl-N-methylmorpholinium methosulfate, etc. are also suitable. Another type of Quaternary ammonium salt which is contemplated is that wherein the molecule contains an ether linkage as exemplied by compounds such as para-tertiaryoctylphenoxyethoxyethyl dimethyl benzyl ammonium chloride and the like. Quaternary ammonium salts having oxygen in the form of amide or ester linkages, such as N-(laurylcolaminoformylmethyl) -pyridinium chloride and the like. Still other satisfactory types of Quaternary ammonium compounds are those containing a sulfonamide group such as 2-phenyl-3-p-sulfamidophenyl--undecyltetrazolium chloride, etc. Another type of very effective Quaternary ammonium germicide is that characterized by a substituted aromatic nucleus as in the case of lauryloxyphenyl trimethyl ammonium chloride, cetylaminophenyl trimethyl ammonium methosulfate, dodecylphenyl trimethyl ammonium methosulfate, dodecylbenzyl trimethyl ammonium chloride,-chlorinated dodecylbenzyl trimethyl ammonium chloride, lauryl dimethyl chlorobenzyl ammonium chloride, cetyl dimethyl nitrobenzyl ammonium chloride, and the like.

Although any of the above types of Quaternary ammonium germicides are ordinarily satisfactory in the compositions according to my invention, thosewhich are particularly effective are the long-chain alkyl dimethyl benzyl Quaternary ammonium salts, the alkylphenoxyalkoxyalkyl dimethyl benzyl Quaternary ammonium salts, the N-(acylcolaminoformylmethyl) -pyridinium halides, the long-chain alkyl trimethyl ammonium halides, as Well as the long-chain alkylarylmethyl Quaternary ammonium compounds.

Long-chain alkylarylmethyl Quaternary ammonium germicides which are particularly adapted to the novel compositions of my invention belong to the class of Quaternary ammonium salts illustrated by the type formula where R1 is an alkyl group of 8 to 18 carbon atoms, Ar is an aryl hydrocarbon nucleus, R is hydrogen or a methyl radical, m is from l to 4, Y is hydrogen or a halogen, n is from 1 to 8, R2,

R3 and R4 are substituents of hydrocarbon structure containing a total of no more than 12 carbon atoms, and X is a salt-forming anionic radical which may be the same as Y.

In the above long-chain alkylarylmethyl quaternary ammonium germicide the long-chain alkyl radical R1 can be any alkyl group of from 8 to 18 carbon atoms. When the acyclic alkyl radicals are of a straight chain nature those containing as few as 8 to 10 carbon atoms are found to be very satisfactory. However, when branched-chain structures predominate in the acyclic radical, the most satisfactory groups are those containing from 10 to 18 carbon atoms. Suitable alkyl radicals can be obtained from various sources such as the long-chain olens of 8 to 18 carbon atoms derived from cracked olenic petroleum fractions or from Fischer- Tropsch synthesis. A preferred source of longchain alkyl radicals is the class of acyclic propylene polymers having from 9 to l5 carbon atoms per molecule with from l2 to 15 carbon atoms being still more preferred.

The aryl nuclei of the long-chain alkylaryl Quaternary ammonium germicides represented by the above formula can be benzene, toluene, Xylene, naphthalene, anthracene, etc., with benzene and toluene being preferred. The N-substituted alkyl radicals in the formula preferably contain from 3 to 10 carbon atoms and may be separate alkyl radicals attached to the nitrogen atom or they may be combined alkyl and cycloaliphatic or aromatic hydrocarbon substituents as in the case of N-ethylpiperidine and pyridine.

Since the cationic portion of the abovev quaternary ammonium germicides is the active component, the salt-forming radicals are not generally regarded as being critical in nature. Any anionic radicals capable of yielding Water-soluble salts can be used, such as the halides, sulfates. phosphates, carbonates, nitrites, alkylsulfates, alkylphosphates, formate, acetate, tartrate, and the like. Halide radicals such as chloride and bromide are preferred, and short-chain alkylsulfates such as methosulfate, ethylsulfate, and the like, are among the more satisfactory alkyl sulfates contemplated as anionic radicals.

The above long-chain alkylarylmethyl Quaternary ammonium compounds can be appropriately prepared by chloromethylation of a long-chain alkylaryl compound to produce the corresponding l alkylarylmethyl chloride which may then be condensed With any suitable tertiary amine to get the desired product. The halogenated longchain alkylarylmethyl Quaternary ammonium compounds, on the other hand, are conveniently prepared by direct halogenation of a long-chain alkylaryl compound having from 1 to 4 methyl radicals attached to the aryl nucleus. When the halogenation is carried out in the absence of any halogenation catalysts which might promote substitution of the aryl nucleus a product is derived containing halogen in the long-chain alkyl radical as Well as in one of the methyl radicals substituted on the aryl nucleus. This compound which may be denominated a halogenated alkylarylmethyl chloride can then be condensed with any suitable tertiary amine as in the preceding example to give the desired halogenated longchain alkylarylmethyl Quaternary ammonium compound.

Promoters according to my invention which come within the scope of the above brief description are, for example, long-chain aliphatic amines, long-chain aliphatic alcohols, cycloaliphatic alcohols; alkyl; alkylcyclohexanols, andY alkylphenylglycolf etlrersgl alkylphenylpolyglycol: ethers, andaroylglycol others, having; at least lucarbonatomss andthe: like. Esters, such as the class ot aliphatic estersfillnstratedby ethylacetate,v etc., may also be, used. Morespeciiic ex.- amples of thepreceding types of promoterswhich are; veryl eftective arelauryl` alcohol cetyl amine, dodeeylaniline, terpineolf,`4 tetradecyl phenol, tertiary -bu-tylphenylmonoethylene glycol-` other,l do.- decylcycl'ohexanol, pine oil, tetradecylphenyl.- monoethyleneglycol ether, octylphenylmonoethyl enlegl-ycolV ether, and' octyl'phenyldiethyleneglycol ether.. Although, some of these compounds are mildly germicidal. of themselves;J their primary functiorrin the Quaternaryeompositionsis as activation agents to enhance the microbicidal effect of the Quaternary ammonium germicides. Of the foregoing illustrative promoters, pine oil, octylphenylethyleneglycol. ether and'. octylphenyldiethyleneglycol ether are the moresatisfactory ones.

Vari-ous mixtures of representative quaternary ammonium germicidesand promoters were prepared for-testing-to illustrate the present invention. Such` mixtures were prepared by placing thevquaternary-ammonium germicide in a Vessel and adding thepromoter", following which the ingredients were: intimately mixed'. to produce the new and. greatly improved germicidal compositions of this invention. The eiiicacy of the different Quaternary" ammonium ger-micides and promoter compositions containing varying proportions ofthaquaternary andpromoter is illustrated by' the results of thev tests which are set' out in the following table.

germz'ctde and promoter compositions towwrd Trichophyton rosaceum Proportions Maxlniium uaternary ame .ec' Qmonium com- Promoter tested (lltyer' mg'r klliu s pound tested pep pep uw cent by cent by tion in weight weight water Dodecylbenzyl trimethyl ammonium chloride. 100 1:30

Do 28. 6 71. 4 1:1000 33.3 66. 7 1: 1330 40. 0 60. 0 1:1600 52. 2 47. 8 1:2630 59. 3 40. 7 1:2960 63. 5 36. 5 1:3080 68. 6 31. 4 1:3463 73. 5 26. 5 1 :3340 89.8 10. 2 1:1800 Do 100 0 1:1500 Lauryl dimethyl benzyl ammonium chloride. do 50 50 1:1500 Dodecylbenzyl trit-Octylphenyl monmethyl ammooethylene-g l y c ol nium chloride... ether 50 50 1:3000 Do Lauryl amine 50 50 1:2500 Chlorinated do decylbenzyl trlmethyl ammonium chloride (approx. 5 chlorine The values for germicidal activity set out in the above table were obtained by determining the maximum effective killing dilutions of the different compositions prepared according'to this invention as Well as of the pure quaternary amcophyifon rosaceum and was; ohtainedby the test-v ingimethod setfoutin Navy Departrr-ient.y Specica.- tion 51D6. The` higher the eiectives dilution, the greater the germicidal power of the composition tested.

From` the above table of results and reference tothev curve in Figure 1 of the accompanying drawing which was obtained by plotting the max-v imum effective. killing dilution against various proportions of Quaternaryv and promoter, the unexpectedly high germicidal activity of compositions according: to my inventionis readily apparent. It can be seen that my germicidal compositions containing'substantial proportions of quaternary ammonium. germicides and less than about '70v per cent by weight of promoterare de.- cidedly superior toV the quaternary ammonium compound in germicid-al efficiency. Any lowering of germicidal activity, which would ordinarily be expected when a strongly germicidal material such asthe quaternaryis diluted with a material having little or no germicidal action as in the. case of the promoters of the present invention, is surprisingly absent when proportions according to the teaching of my-invention. are utilized.

Because of their higher germicidal activity, my novel compositions are more efficacious than either auaternary ammonium germicide or promoter alone. Their'greater -elicacy renders them extraordinarily useful in the control ofy micro.- organisms suchE as spore-forming bacteriaungi, and. the like.l Such; uses4l` include, the disinfection of utensilsVA andA equipment .usedin drin-king, ,eating and the preparation of foods,` etc.. Wearing aps parel, bedding, upholstery, and the like, can also be effectively sterilized by the use of my germi-l cidal compositions. Floors and walls as Well as various equipment such as lavatories and toilets in the areas where it is desirable to promote germfree surroundings can be conveniently disinfected with these germicidal compositions because of their greater germicidal activity. Other applications, such as their use as antiseptic ingredients in germicidal detergents, ointments, cosmetics, etc., are also indicated.

The germicidal compositions according to my invention may contain various dyes or coloring agents which are compatible with the quaternary ammonium germicides and the promoters in order to improve the general appearance of the compositions. The use of various perfumes and odor masking agents is also contemplated.

In some instances the germicidal compositions of this invention may contain water, as for example, when a composition is prepared by adding the promoter to a 50 per cent aqueous solution of the quaternary ammonium germicide. In the presence of certain amounts of Water, as for example amounts exceeding about 30 per cent and less than about per cent of the aqueous quater-nary ammonium germicide solution, a separation of the promoter and aqueous Quaternary ammonium germicide mixture may occur. Although such separation has no effect on the germicidal activity of my compositions, it will be preferred to maintain the Water in amounts of ,less than about 30 per cent or more than about 90 per cent by weight whenever clear and completely miscible or homogeneous mixtures are desired for the sake of appearances.

The foregoing description and examples of the where R1 is an alkyl group of 8 to 18 carbon atoms, R. is a member of the group consisting of hydrogen and a methyl radical, m is from 1 to 4, and R2, R3 and R4 are substituents of hydrocarbon structure containing a total Aof no more than 12 carbon atoms, said Quaternary being admixed with a member of the group consisting of octylphenylmonoethyleneglycol ether and octylphenyldiethyleneglycol ether as a promoter, the promoter being present in amounts sufficient to improve the germicidal activity oi the quaternary ammonium compound but not to exceed 70 per cent by weight of the composition.

2. A germicidal composition which comprises from 10 to 70 per cent by weight of octylphenylmonoethyleneglycol ether and from 30 to 90 per cent by Weight of an alkylarylquaternary ammonium compound as dened in claim 1. wherein R1 is an alkyl radical of polypropylene structure containing from 12 to 15 carbon atoms.

i 3. A 'germicidal composition which comprises from 10 to 70 per cent' by weight'of octylphenyldiethyleneglycol ether and from 30 to 90 per cent by weightoi an alkylaryl quaternary ammonium compound as dened in claim 1, wherein R1 is an alkyl radical of polypropylene structure containing from 12 to 15 carbon atoms.

4. A germicidal composition which comprises from 10 to 70 per cent by weight of octylphenylmonoethyleneglycol ether and from 30 to 90 per cent by weight of dodecylbenzyl trimethyl ammonium chloride. Y- A 5. A'germicidal composition whichv comprises from 10 to '70 per cent by weight of octylphenyldiethyleneglycol ether and-from 30 to 90 per cent by weight of dodecylbenzyl trimethyl ammonium chloride. l


References Cited in the file of this patent UNITED STATES PATENTS Number y Name Date 2,054,257 Hueter Sept. 15, 1936l 2,158,957 Coleman et al May 16, 1939 2,264,150 Hueter Nov. 25, 1941 2,309,592 Hueter Jan. 26, 1943 2,544,732 Scheichmeister Mar. 13, 1951 OTHER REFERENCES Lawrence et al.: Journal American Pharmaceutical Association, November 194'?, volume 36, pages 353 to 358.

Rawlins et al.: Journal American Pharmaceutical Association (1943) volume 32, pages 11 to 16.

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U.S. Classification514/642, 514/643, 514/718
International ClassificationA01N33/12
Cooperative ClassificationA01N33/12
European ClassificationA01N33/12