US3539520A - Compositions comprising quaternary ammonium germicides and nonionic surfactants - Google Patents

Description

United States Patent 01 ice 3,539,520 Patented Nov. 10, 1970 3,539,520 COMPGSITIONS COMPRISING QUATER- NARY AMMONIUM GERMICIDES AND NONIONIC SURFACTANTS Abraham Cantor, Elkins Park, Pa., and Murray W. Winicov, Flushing, N.Y., assignors to West Laboratories, Inc., Long Island City, N.Y., a corporation of New York No Drawing. Filed July 12, 1967, Ser. No. 652,685 Int. Cl. (111d 3/48 U.S. Cl. 252106 11 Claims ABSTRACT OF THE DISCLOSURE Compositions comprising quaternary ammonium germicides and nonionic detergents wherein unique compatibility with respect to performance of the quaternary ammonium germicides is achieved in the presence of amounts of detergent which are at least twice the amount of germicide, by employing a nonionic detergent in which the major portion of the molecule is made up of block polymeric C to C alkylene oxides, with alkylene oxide blocks containing C to C alkylene oxides and -45 ethylene oxide providing a significant hydrophobic function, and alkylene oxide blocks containing ethylene oxides and 045% of C to C alkylene oxide providing a significant hydrophilic function.

Preferred compositions are detergent sanitizers con taining quaternary ammonium germicides in combination with 5 to times as much detergent. In such compositions enhanced and extended germicidal action can be provided by employing as the nonionic detergent component a detergent-iodine complex, or by adding a PVP- iodine complex.

BACKGROUND OF THE INVENTION With the commercial introduction of quaternary ammonium germicides (germicidal quats) about 25 years ago, the desirability of combining germicidal quates with detergents in the formulating of disinfecting and sanitizing products was immediately apparent. The then available anionic detergents were tried and found unsuitable in such combinations due to reaction with the quaternary ammonium compound. When nonionic detergents became commercially available, it was initially thought that detergent-sanitizer compositions could be prepared with quaternary ammonium germicides'and varying amounts of nonionic detergent.

The recognition that germicidal quats are adversely affected by hard water came only shortly after the introduction of these chemicals of phenomenally high phenol coefficient. Early literature on the subject of combinations of quats and nonionics was marked by conflicting reports from reputable laboratories in which similar ratios of nonionic to quat were shown to be effective or ineffective for apparently similar uses. The situation was complicated by the tendency to measure disinfecting properties under prolonged kill time or stasis conditions. Not only was water hardness frequently not considered as a factor, but the added effect of nonionic interference in the presence of hard water was not recognized. Some investigators, working with distilled water, found that nonionic detergents could increase germicidal performance of quats under certain conditions, especially where prolonged kill times were used.

More recently, quat manufacturers found that certain quats were more resistant to hard water than others. During this time ofiicial government agencies began to rec- OgniZe the need for fast killing detergent-quat performance in the presence of hard Water. The official performance test for detergent-sanitizers (e.g. nonionic-quat formulations) is given in the AOAC Tenth Edition, 1965, paragraphs 51023 to 5.032 inclusive. This test prescribes a 30 second performance end point under hard water test conditions.

Quat manufactures, who acutally participated in the development of this method through industry-regulatory agency cooperation, quickly put a ceiling on the amount (ratio) of nonionic which could be used with quats. This ceiling, universally adopted by the trade for the past ten years, places a limit of from 1.5 to 2.0 parts of nonionic to one part of quat in a detergent-sanitizer formulation. At the same time, a minimum of 200 p.p.m. quat was, and is now, generally accepted as being the least amount of quat which can be safely recommended in a detergentsanitizer use dilution based on a conventional nonionic and germicidal (even hard water) quat. This means, in effect, that use concentrations containing 200 p.p.m. quat limited to 400 p.p.m. of detergent are significantly below the generally recognized level of about 1000 p.p.m. (0.1%) of nonionic, which is necessary for light duty hard surface detergency. For many diflicult cleaning jobs, ten times this amount of detergent is indicated. At-the present time, therefore, quat-nonionic detergent-sanitizers are not used for this purpose in part because of the prohibitive cost of the concomitant quat germicide. For example, at todays prices, germicidal quats cost from 5 to 10 times as much as the widely used nonionic detergents.

THE INVENTION The present invention resides in the discovery that the expected interference of nonionic detergent with germicidal quats can be avoided, paving the way for the formulating of compositions containing both germicidal quats and nonionic detergents without the traditional limitation on the proportions of components, by selecting the detergent from a limited class of nonionic detergents in which the major portion of the molecule is made up of block polymeric C C' alkylene oxides, with alkylene oxide blocks containing C to C alkylene oxides and 0-45 ethylene oxide providing a significant hydrophobic function, and alkylene oxide blocks containing ethylene oxide and 0-45 of C to C alkylene oxide providing a significant hydrophilic function. Such detergents, while preferably built up from an alkylene oxide chain starting group, can have as a starting nucleus almost any active hydrogen containing group including, without limitation, amides, phenols, and secondary alcohols.

The reason for the unique compatibility of the type nonionic detergents above described with germicidal quats is not understood, but it appears to be in some way tied to the block polymer nature of the detergents and particularly to the presence of a C to C alkylene oxide block or a mixed ethylene oxide and C to C alkylene oxide block providing a significantly hydrophobic function in the detergent. Samples of various known detergents answering this description have consistently been found to perform satisfactorily in the new type compositions and to contrast sharply with more conventional nonionic detergents.

One group of detergents containing the characteristic block polymer of propylene oxide, and commercially available under the trademark Pluronic can be represented by the formula:

Formula A )X( )y( )X where E and PO represent ethylene oxide and propylene oxide respectively, equals at least 15, (EO equals 20 to 90% of the total weight of said compound, and the molecular weight is in the range of about 2000 to 15,000. Typical Pluronics which will hereinafter be referred to are:

Another group of detergents appropriate for use in the new compositions can be represented by the formula:

Formula B Alkoxy (EO,PO) (EO=,PO) H wherein the alkoxy group contains 1 to 20 carbon atoms, the weight percent of E0 is within the range of O to 45% in one of the blocks a, b, and within the range of 60 to 100% in the other of the blocks a, b, and the total number of moles of combined EO and PO is in the range of 6 to 125 moles, with 1 to 50 moles in the PO rich block and to 100 moles in the E0 rich block.

Typical detergents falling within Formula B above which may be employed in the new compositions include the following, identified in terms of the stated values for the difierent variables in the formula:

Moles Moles Carbon percent E0 plus plus in in a in P0 P0 alkoxy b in n in u Other examples of detergents of the general type embraced by Formula B include: Tergitol XD, Tergitol XH, and Tergitol X60 which are butoxy derivatives of propylene oxide, ethylene oxide block polymers having molecular weights within the range of about 2000-5000.

Other suitable detergents generally related to the above formulae, but containing polymeric butoxy (BO) groups can be represented as follows:

Formula C RO(BO),,(EO) H wherein R is an alkyl group containing 1 to 20 carbon atoms, n is about 15 and x is about 15; and

Formula D where (EO) and (P0) are ethoxy and propoxy respectively, the amount of (PO) is such as to provide a molecular weight prior to ethoxylation of about 300 to 7500, and the amount of (130),, is such as to provide about 20% to of the total weight of said compound.

The examples hereinafter appearing are directed essentially to comparisons between compositions in which conventional germicidal quats are associated with various nonionic detergents embraced by Formulas A to E, and with other common nonionic detergents which are in extensive commercial use. Such conventional germicidal quats, some of which will be referred to in the examples include the following, identified by trade name and chemical composition. Those identified with the asterisk are generally recognized as hard water quats.

Cationic germicide: Composition Hyamine 2389 Methyl dodecylbenzyl trimethyl ammonium chloride, and methyl dodecyl xylylene bis (trimethyl) ammonium chloride.

Beloran Lauryl benzyl diethanolammonium chloride.

*Tetrosan 3, 4 D Alkyl dimethyl 3, 4 dichlorobenzyl ammonium chloride.

*BTC 471 A1ky1** dimethyl ethylbenzyl ammonium chloride C 50%, C 30%, C 17%, C 3%.

*BTC 927 Alkyl** dimethyl dimethylbenzyl ammonium chloride C 50%, C 30%, C 17%, C 3%.

*BTC 1100 Alkyl** dimethyl l-naphthylmethyl ammonium chloride monohydrate C 98%, C 2%.

Emcol E607 N(lauroyl colaminoformylmethyl) pyridinium chloride.

*Hyamine 3500 N-alkyl (C12, C14, C dimethyl benzyl ammonium chloride.

Cetab Cetyltrimethylammonium bromide.

CPC Cetylpyridinium chloride.

LPC Laurylpyridinium chloride.

Hyamine 1622 Diisobutyl phenoxy ethoxy ethyl dimethylbenzyl ammonium chloride.

For comparison purposes the examples include data for compositions employing a number of common nonionic detergents which are outside the scope of the invention, having the trade designations and chemical identifications as follows:

Igepal CO-710 Nonyl phenol-ethylene oxide condensate with 10-11 moles of ethylene oxide.

Igepal CO-880 Nonyl phenol-ethylene oxide condensate with about 30 moles of ethylene oxide.

Igepal CO-990 Nonyl phenol-ethylene oxide condensate with about 100 moles of ethylene oxide.

Igepal AR660 Polyoxyethylene* fatty alkyl ether 60-65% ethylene oxide Cm-Cm (3V. C14) Octyl phenol-ethylene oxide condensate with about 10 moles of ethylene oxide.

Triton X100 from coco fatty acids x+y=5.

Ethomid HT60 As above from hydrogenated tallow x+y=50. Ethomid HTlS As above In the examples germicidal activity is measured by one of the following test procedures:

Procedure A.The test procedure described in Ofificial Methods of Analysis of the Association of Official Agricultural Chemists, Tenth Edition (1965) pp. 87-89 and page 80.

Procedure B.The following procedure, which involves slight modification of Procedure A:

The test solution is prepared by appropriate dilution of a sample in water of specific hardness (page 88). A sterile 250 ml. erlenmeyer flask containing 99 ml. of the test solution is placed in a 20 C. constant temperature water bath, and the solution is brought to temperature. A 24- hour culture of S. choleraesuis ATCC No. 10708 grown in AOAC broth (page 80) is used as the test culture. This culture meets the AOAC requirements for phenol resistance, i.e., it is killed by a 1:90 dilution of phenol in minutes, but not in .5 minutes, and it resists a 1:100 dilution of phenol for minutes.

One ml. of the test culture is added to 99 ml. of the test solution held at C. At the end of specified time intervals sec., 1 min., 2 min.), 1 ml. of the culture-solution mixture is removed and diluted in 9 ml. Letheen neutralizer blank (page 87). One ml. and 0.1 ml. amounts of this neutralizer dilution are plated in duplicate in Tryptone Glucose Extract Agar containing Letheen (page 87) as a neutralizer. The plates are incubated at 37 C. for 48 hours. At the end of this time, the resultant colonies are counted. The average counts per ml. when multiplied by the above dilution made prior to plating gives the number of surviving organisms per ml. of germicidal test solution.

The actual number of organisms (the challenge) originally subjected to the action of the test solution is determined at the same time as follows: One ml. of the test culture is added to 99 ml. of phosphate buflFer (pH 7.2) dilution water (page 87) held at 20 C. At the end of 30 seconds, 1 ml. of the culture-buffer mixture is transferred serially to 3 bottles containing 100 ml. each of phosphate buffer dilution water. The final dilution is plated in duplicute in 1 ml. and 0.1 ml. amounts in Tryptone Glucose Extract Agar, and the resultant colonies counted. The average counts per ml. when multiplied by the above dilution figure give the number of organisms (the challenge) actually subjected to the action of the test solution. A comparison of this challenge count with the number surviving in the test solution is the basis for calculating the percent reduction achieved by the test solution.

EXAMPLE I In standard 500 p.p.m. hard water germicidal detergent solutions were prepared containing '200 p.p.m. of Hyamine 3500 and amounts of different nonionic detergents. These were tested by Procedure B above described using 1 ml. S. clmlerasuis broth in 100 ml. of test solution (3,000,000 organisms per ml. of test solution) and plate counts determined at /2 min., 1 min., and 2 min. inter vals. The results obtained are as follows:

Rdatgd Plate count, minutes Detergent quat kg 1 2 o Plnronic P Essentially the same results are obtained when the amount of Pluronic P65 is increased to 10/1 or even to 1. Note in this connection that as optimum proportions for most practical detergent sanitizer compositions, the detergent/ quaternary ratio should be in the 5/1 to 10/1 range.

EXAMPLE II Following the same procedure as described in Example I using 500 p.p.m. hard water, solutions containing 200 p.p.m. of Beloran (which is not a hard water quat) and various detergents in the amounts indicated were prepared and tested with the following results:

Ratio Plate count, minutes det./ Detergent quat 1 2 one c 14, 000 1, 400 10 Igepal CO7l0 2/1 1,000, 000 50, 000 500 Do 5 1 1, 000,000 1, 000, 000 1, 000, 000 Pluronic L44 5/1 13, 000 1, 600 30 Pluronic P54. 5/1 12, 500 300 10 Pluronic P65. 5/1 12, 800 1,100 10 Pluronic L62. 5/1 26, 400 1, 400 20 Plnronie P85. 5/1 6, 000 400 10 Pluronie P 4/1 64, 000 7, 200 Tergitol XD 4/1 7, 300 3 10 Tergitol XH 4/1 26, 000 70 20 Ethomid C/15. 5/1 1, 000, 000 640, 000 320, 000 Ethomid HT60- 5/1 1, 000, 000 700, 000 28, 000 5/1 1, 000, 000 780, 000 180, 000 5/1 360, 13, 700 5/1 1, 000, 000 1, 000, 000 1, 000,000 5/1 1, 000, 000 1, 000, 000 1, 000, 000 3/1 660, 000 150, 000 8, 400 3/1 1, 000, 000 1, 000, 000 25,000 5/1 1, 000, 000 1, 000, 000 1, 000, 000

In the foregoing tabulation it should be pointed out that Igepal CO-990 which shows what might be considered borderline performance at the 5/1 detergent/ quaternary ratio should be disregarded because this material contains so much ethylene oxide that it is no longer useful as a detergent.

EXAMPLE III Following the same procedure as described in Example I, but preparing solutions in 300 p.p.m. hard water, solutions containing 200 p.p.m. of different cationic germicides and the indicated amounts of different nonionic de- 7 tergents were prepared and tested, giving the results shown in the following tabulations:

Plate counts, minutes Composition tested 1 2 Hyamine 3500 alone 10 10 10 Plus 2/1 Igepal (JO-710- 12, 300 170 50 Plus 5/1 Igepal (30-710 1, 000, 000 468, 000 103,000 Plus 5/1 Pluronic P65 10 10 Beloran alone..." 1, 550 25 10 Plus 2/1 Igepal C 84, 500 6, 000 240 Plus 5/1 Igepal (30-710- 820,000 470, 000 145, 000 Plus 5/1 Igepal AR660 1, 000, 000 880,000 510, 000 Plus 5/1 Pluronic P65... 570 10 10 Emcol E607 alo11e 62, 500 5, 200 1, 700 Plus 2/1 Igcpal (JO-710- 410, 099 195, 000 65, 000 Plus 5/1 Igepal OO710 1, 000, 000 1, 000, 000 1, 000, 000 Plus 5/1 Pluronic P65 71,000 3, 500 710 Hyamine 2389 alone 270, 000 108, 000 27, 000 Plus 5/1 Igepal OO710 1, 000, 000 1, 000, 000 900, 000 Plus 5/1 Pluronic P65 520, 000 35, 000 95, 000

The foregoing tabulation is of special interest in showing a substantial variation in activity of the germicide alone, from the very quick acting Hyamine 3500 to the much slower acting (but widely used commercially) Hy amine 2389. The advantage of Pluronic P65 over lgepal CO710 at the 5/1 detergent/quaternary level is quite apparent with each of the germicides, in spite of the differing activities of the germicides per se.

EXAMPLE IV Detergent-germicide solutions were prepared in 500 p.p.m. hard water using as germicide 200 p.p.m. of Tetrosan 3,4 D and varying amounts of different detergents as indicated. The resulting solutions were tested for germicidal activity by Procedure A above described using E. coli as the test organism. The comparative results, at 30 sec. and 1 min., expressed in plate count and percent, reduction in the number of organisms, for the germicide alone and the germicide plus detergent under the varied conditions are as follows:

8 ing organisms were equivalent to the quat alone; that is, there was no interference with quat kill under these conditions.

EXAMPLE VI A number of solutions were prepared in water of different hardness, as indicated, containing 200 p.p.m. of Hyamine 3500 and detergents in the proportions indicated; and these solutions were tested according to Procedure A above using E. coli as the test organism with the following results expressed in percent reduction in the number of organisms:

Ratio Hard Result det./ Water, Detergent quat p.p.m. 30 sec. 1 min.

e 500 Igepal C07l0.- 2/1 500 Do 2/1 300 99. 8 Do 2/1 209 99. 991 D0 2/1 100 99. 998 99. 999 D0- 2/1 DO 1/1 300 99.987 99. 999 D0- 1/1 100 99. 993 99. 999 D 1 2 300 Amine oxide A 2/1 200 Amine oxide B 2/1 200 D0 2/1 100 99. 724 99. 844 D0 2/1 50 99.758 99.996 D0 1/1 100 99.998 99. 999 D o 1/2 100 1 Passes. 2 Too numerous to count.

These results indicate clearly the effect of both water hardness and detergent/quat ratio on the germicidal activity in the presence of these conventional detergents. The results here are given for both the 30 second and 1 minute kill merely to enable better visualizing of these elfects. It should be noted, however, that to pass the test Procedure A there must be at least a 99.999% reduction in the number of organisms in 30 seconds; and

30 seconds 1 minute Ratio det./ Percent Percent D etergent quat Count reduction Count reduction EXAMPLE V A number of solutions were prepared in water of different hardness as indicated, containing Hyamine 3500 alone at the 200 p.p.m. level, and Hyamine 3500 plus 2/1, 5/1 and 10/1 ratios of difierent type detergents. These were tested by Procedure B above described for 1 minute kill, and the plate counts of surviving organisms are tabulated below.

in the following examples passing and failing results have reference only to the'3O sec. test.

EXAMPLE VII A number of solutions were prepared in 200 p.p.m. hard water containing 200 p.p.m. of Hyamine 3500 and 400 p.p.m. (2/1 detergent/quat ratio) of various conventional detergents and block polymer detergents, and

Plate count at water hardness indicated, one

Ratio minute kill det.

Detergent quat 500 p.p.m. 300 p.p.m. 100 p.p.m. 0 p.p.m

None 10 10 10 10 Igepal GO-710 2/1 3,000 170 10 10 Do 5/1 500, 000 470, 000 44, 000 10 Do. 10/1 1, 000, 000 1, 000, 000 1, 000,000 10 Pluronie P 2/1 10 10 10 10 Do 5/1 10 10 10 10 Do 10/1 10 10 10 10 these solutions were tested according to test Procedure A. The solutions containing the conventional detergents Igepal CO710, Myrj 78, Ethomid HT 15, Amine Oxide A and Amine Oxide B all failed to pass this test.

The solutions containing the block polymer detergents Pluronics P65, P85, P105, P108 and P123, Tergitol XH, and Tetronic 704 (a compisition according to Formula E in which the molecular weight prior to ethoxylation is 2500-3000, and the molecular weight of the ethylene oxide is 16002000) all passed the test. Also passing the test were solutions in which the block polymers are identified as follows:

Block polymer A.a compound of the formula HO(C H O) (C H O) (C H O) H having a molecular weight of approximately 4000 with equal parts by weight of ethylene oxide and propylene oxide.

Block polymer B.a compound similar to the Pluronics of Formula A in which the hydrophobe y contains about 90% PO and E0 and has a molecular weight of about 2500 and the hydrophile x+x contains about 90% E0 and 10% PO and has a molecular weight of about 1700.

Block polymer C.-a compound similar to Block polymer B in which both hydrophobe and hydrophile have molecular weights of about 2500.

EXAMPLE VIII A number of solutions were prepared in water of different hardness, as indicated, containing 200 p.p.m. of Tetrosan 3, 4 D and difierent detergents of the conventional type and the block polymer type in the proportions indicated. These solutions were tested according to Procedure A above using E. coli as the test organism with the following results:

EXAMPLE IX The procedure of Example VIII was repeated using a different quaternary ammonium compound, BTC 471, at the 200 p.p.m. level, and a number of conventional type detergents and block polymer detergents in the amounts indicated. Testing of the solutions according to Procedure A gave the following results:

Ratio Hard det./ water, quat p.p.m. Result Conventional deter ents:

f. 800 Passes. Igepal C0710, 400 p p m 2/1 300 Fails. Myrj 53, 400 p p m-. 2/1 300 Do. Bryj 78, 400 p.p.m-. 2/1 300 D0. Ethomid HI15, 00 2/1 500 Do. Amine oxide A 2/1 300 D0. Amine oxide B 2/1 300 Do. Triton X-100, 400 p.p.m 2/1 300 Do. Block Polymer detergents:

Pluronic P65, 400 p.p.m 2/1 300 Passes.

Do 2/1 800 Do. Pluronie P65, 4,000 p.p.m.. /1 500 Do. Block, Polymer D, 400 pp. 2/1 300 Do. Block Polymer E, 400 p.p.m. 2/1 300 Do.

In the foregoing tabulation Block Polymer D is a nonionic detergent identified by Formula B(a) and Block Polymer E is identified by Formula B(g).

EXAMPLE X The Procedure of Example VIII was repeated using as quaternary ammonium compounds:

A-BTC 927 at 200 p.p.m. B-BTC 1100 at 200 ppm.

and typical conventional type and block polymer type detergents in the amounts indicated. Testing of the solutions according to Procedure A gave the following results:

In the formulating of germicidal detergent sanitizer products using quaternary ammonium germicides it is frequently desirable to include added components such as builders, pH regulating additives, and/or organic sequestering agents. It has been found that such additives can be used in formulating products containing block polymer type detergents of the present invention. This is demonstrated in the following example:

EXAMPLE XI A solution containing 200 p.p.m. of Hyamine 3500 and 500 p.p.m. of Pluronic P65 (2.5/1 ratio of detergent/ quat) in 200 p.p.m. hard Water readily passes the Official AOAC germicidal and Detergent Sanitizer Test-Procedure A.

Similar solutions were prepared containing additive in the amounts indicated and these were tested according to Procedure A with the following results:

Additive Concentration, Solution, Type p.p.m. pH Result 400 11 Passes. 400 3 Do. 200 10.8 Do. 200 10.8 Do.

1 Ethylene diarnine tetraaeetic acid sodium salt. 2 Sodium tripolyphosphate.

The results when using the block polymeric material Pluronic P65 in the foregoing examples are characteristic of block polymer detergents generally as embraced by Formulas A to E above. While there may be some variation in organism kill obtained when switching from one block polymer to another as indicated in Example II or when switching from one cationic material to another as indicated in Example III, the use of block polymer detergents permits extensive variation of the detergent/ quat ratio and of the water hardness without the severe restriction in the functioning of the germicide which is characteristic of ordinary nonionic detergents.

The foregoing examples have clearly demonstrated the unusual freedom from interference with the germicidal quat by the special block polymeric nonionic detergents herein described when the detergent: quat ratio is equal to or greater than 2:1, and even as high as :1. There is special value in being able to provide a nonionic detergent: germicidal quat ratio in the range of about 5:1 to 10:1 since this permits a combination of optimum germicidal action and optimum hard surface detergency in a single composition. The term germicidal quat as here used is understood to embrace any quaternary ammonium compound recognized as having germicidal activity of practical significance. As a class such quaternary ammonium compounds are characterized as having at least one long chain alkyl or aryl group of 8 to 22 carbon atoms joined to the quaternary nitrogen. Furthermore, germicidal activity which is of practical significance requires that the quaternary ammonium compound have a phenol coeflicient of at least 50, and preferably at 11 least 100, with respect to S. aureus and S. typhosa at 20 C.

The preceding examples have demonstrated the superiority of block polymer nonionic detergents in situations where hard water is a factor. The present invention, however, extends into areas where distilled water is used as the testing medium. The most important ofiicial test method for testing disinfactants to determine the maximum dilution which is effective for practical disinfection is called the Use-Dilution Method. This method is described on pages 8284 of AOAC 1965) previously cited. Distilled water is used as the test medium.

By the way of background, it should be pointed out that the minimum amount of the most active quaternary ammonium compound accepted as passing this test is 400 p.p.m. When formulating end use products with detergents, builders, pH regulating additives, and/or organic sequestering agents for purposes of better cleaning, the quat level may actually have to be increased, so that as much as 500 p.p.m. of quat are necessary.

It has now been found that in contrast to such adverse performance in the presence of conventional detergent, germicidal quats become more effective when combined with the block polymer nonionic detergents of the present invention. This is clearly demonstrated in the following example:

EXAMPLE XII Amounts in parts per million, p.p.m.

Pluronic Hyam1ne Igepal 3500 P65 P123 C0710 STPP NazCOa EDTA Results 50 400 50 Do. 50 400 50 Passes. 50 400 50 Do.

In utilizing the present invention to formulate commercial products in the field of detergent-sanitizers, it is within the scope of the present invention not only to combine compatible acids and alkaline substances as normally employed in such products, but also to employ other compatible active components in such products.

By way of illustration, in the detergent sanitizer field it is frequently desired to have a single product both long sustained germicidal action and rapid kill of organisms. Some of the germicides which are most desirable for the sustained germicidal action are too slow acting for the desired rapid kill performance. This problem can be met by supplying the nonionic detergent as a detergent-iodine complex. The rapid kill germicidal activity of nonionic detergent-iodine complexes is well recognized in the art and some of the nonionics embraced by Formulas A to B have been employed in detergent iodine products as detergent-sanitizers and the like.

The block polymeric nature of the nonionic detergents embraced by Formulas A to E makes them inherently capable of complexing with iodine, and while not all of the detergents would be detergents of choice for straight detergent-iodine compositions, it is considered that any of the disclosed nonionic detergents supplied as an iodine complex would effectively supplent the activity of the germicidal quat.

In such a dual purpose detergent sanitizer the amount of iodine present is preferably about 1 to 2 times the amount of germicidal quat, with the optimum amount in each instance being dependent upon the relative activity 12 of the germicidal quat and the physical stability of the inherently complex formulation.

The following example illustrates a typical detergentsanitizer composition of the present invention containing both germicidal quat and iodine.

EXAMPLE XIII A detergent sanitizer is prepared by combining:

The HI-I is first mixed with the Pluronic. The other components are then added in the order listed and mixed until a uniform clear dark-brown colored solution is obtained, the entire mixing being effected at room temperature.

This composition is a multipurpose detergent-sanitizer currently being readied for commercial distribution.

At 1:50 dilution in waters of normally varying hardness it is an excellent heavy duty cleaner-sanitizer.

At 1:200 dilution the composition provides a good general purpose detergent-sanitizer, which passes the Use Dilution Confirmation Test AOAC. (1965 pages 82-84.

In this composition the major germicidal activity is the rapid activity which is provided by the iodine. The germicidal quat, however, fills an important role. It provides a continuing germicidal action on surfaces coated with the composition.

EXAMPLE XIV A detergent sanitizer is prepared containing:

Percent Component: by weight Pluronic P-123 10.0 HII (57% I 1.75 Tetrosan 3,4 D (60% act.) 1.8 PVP (polyvinylpyrrolidone) 5.0 Water 81.45

The order of mixing is not critical. The HII can be first mixed with the Pluronic and the other components added, or the HII can be mixed with the PVP aqueous solution and the other components added. Either procedure leads to a similar distribution of complexed iodine between the Pluronic and the PVP.

This is a stable product which readily dilutes to practical use solutions. At a 1:100 dilution it is an effective general purpose detergent sanitizer.

The various examples have shown block polymer nonionic detergents with as few as 2 or 3 and as many as 8 blocks per molecule. The number of blocks appears to be immaterial, and detergents with intermediate numbers of blocks or higher numbers, as well as a greater number of alternating blocks are within the scope of the invention provided these blocks provide the essential hydrophobic and hydrophilic functions previously described.

Various changes and modifications in the versatile compositions of block polymeric nonionic detergents and germicidal quats herein disclosed will occur to those skilled in the art, and to the extent that such changes and modi fications are embraced by the appended claims, it is to be understood that they constitute part of the present invention.

We claim:

1. A germicidal detergent composition consisting essentially of a germicidal quaternary ammonium compound and a nonionic detergent in which the major portion of the molecule is made up of block polymeric C to C alkylene oxides, with alkylene oxide blocks containing C to C alkylene oxides and -45 ethylene oxide providing a significant hydrophobic function, and alkylene oxide blocks consisting of ethylene oxide and 0-45 of C to C alkylene oxide providing a significant hydrophilic function, the nonionic detergent being a member selected from the group consisting of the following formulae:

wherein EO and PO represent ethylene oxide and proylene oxide, respectively, y equals at least 15, (E0) equals 20-90% of the total weight of said compound and the molecular weight is within the range of about 2,000 to 15,000;

wherein the alkoxy group contains 1-20 carbon atoms, EO and PO represent ethylene oxide and propylene oxide, respectively, the weight percent of E0 is within the range of 0 to 45% in one of the blocks a, b and within the range of 60 to 100% in the other of the blocks a, b, and the total number of moles of combined EO and PO is in the range of 6 to 125 moles, with 1 to 50 moles in the PO rich block and to 100 moles in the E0 rich block;

having a molecular weight of approximately 4000 with equal parts by weight of ethylene oxide and propylene oxide; and,

wherein EO and P0 are ethylene oxide and propylene oxide, respectively, the group (PO,EO) contains 90% PO and has a molecular weight of about 2500, and the groups (EO,PO) contain about 90% E0 and have a molecular weight of about 1700, the minimum ratio of nonionic detergent to quaternary ammonium compound in said composition being not less than 2:1, and in which composition said germicidal quaternary ammonium compound has a phenol coeflicient of at least 50 with respect to S. aureus and S. typhosa at 20 C., and is further characterized by having at least one 8-22 carbon atom containing substituent selected from the group consisting of alkyl and aryl radicals which substituent is joined to the quaternary nitrogen.

2. A germicidal detergent composition as defined in claim 1 wherein the nonionic detergent: quaternary ammonium compound ratio is in the range of about 5:1 to 10:1.

3. A germicidal detergent composition as defined in claim 1 wherein the nonionic detergent is a compound of Formula A.

4. A germicidal detergent composition as defined in claim 1 wherein the nonionic detergent is a compound of Formula B.

5. A germicidal detergent composition as defined in claim 1 wherein the nonionic detergent is a compound of Formula C.

6. A germicidal detergent composition as defined in claim 1 wherein the nonionic detergent is a compound of Formula D.

7. A germicidal detergent composition as defined in claim 1 wherein the nonionic detergent is a compound of Formula E.

8. A germicidal detergent composition as defined in claim 1 wherein the nonionic detergent is a compound of Formula F.

9. A germicidal detergent composition as defined in claim 1 wherein the nonionic detergent is a compound of Formula G.

10. A germicidal detergent composition as defined in claim 1 wherein the nonionic detergent component is a nonionic detergent-iodine complex, the amount of iodine in said complex being about one to two times the amount of said quaternary ammonium compound such as to provide additional germicidal activity.

11. A germicidal detergent composition as defined in claim 1, employing a complex of PVP-I, the amount of iodine in said complex being about one to two times the amount of said quaternary ammonium compound such as to provide additional germicidal activity.

References Cited UNITED STATES PATENTS 2,677,700 5/1954 Jackson et al. 252152 2,739,922 3/1956 Shelanski 252-106 3,028,301 3/1962 Winicov 252-106 X 3,223,643 12/1965 Law 252-106 3,337,463 8/1967 Schrnolka 25289 MAYER WEINBLATT, Primary Examiner P. E. WILLIS, Assistant Examiner US. Cl. X.R.