US3223644A - Liquid detergent-sanitizer - Google Patents

Description

United States Patent 3,223,644 LIQUID DETERGENT-SANITIZER Andrew B. Law, Levittown, 1221., assignor to Rohm 8: Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Filed Nov. 12, 1964, Ser. No. 410,720 9 Claims. (Cl. 252106) This application is a continuation-in-part of my application Serial No. 146,016 which was filed on October 18, 1961, and which has since been abandoned.

This invention relates to a liquid detergent-sanitizer of high hard water tolerance. It has particular reference to a composition containing a quaternary ammonium composition as the sanitizer and a nonionic as the detergent.

One of the principal components of the present invention is an outstanding commercially available sanitizer which consists of an aqueous solution of a mixture of alkyl dimethyl benzyl ammonium chlorides. The mixture consists of alkyl dimethyl benzyl ammonium chlorides whose alkyl groups can range from C to C although its most elfective germicidal components are those whose alkyl groups are C (lauryl or dodecyl), C (myristyl or tetradecyl), and C (cetyl or hexadecyl). The proportions of the C -C components can vary, depending upon the manufacturer and the particular batch of the product. However, for the purposes of the present invention the proportions are not critical, the sanitizer being effective in its various proportions, some to a greater and others to a lesser degree, in the invention as described hereinbelow.

One of the most outstanding features of this conventional quaternary sanitizing composition is its exceptional effectiveness in hard water. The sanitizing dilution for quaternaries which is considered standard in the United States and in most foreign countries is 200 p.p.m., and in many states and local governments this requirement is specified by law. At this dilution the hard water ceiling for the quaternary mixture described above is 550 p.p.m. hard water. This means that the mixture is capable of killing 99.999 percent of specified test organisms, in 30 seconds, in water containing up to 550 p.p.m. (32 grains per gallon) hardness calculated at CaCO when tested by the method of Chambers (1. Milk & Food Tech, vol. 19, No. 7 (1956), pp. 183-187). This method is also known as the Association of Official Agricultural Chemists, Official Method of Evaluation of Germicidal and Detergent Sanitizers (cf. Methods of A.O.A.C., 9th ed., 1960, Washington, DC, pp. 70-72). In accordance with this procedure an inoculum containing a known number of bacteria is added to hard water solutions of the aciddetergentsanitizer formulations. Aliquots of the solu- 3,223,644 Patented Dec. 14, 1965 tions are then removed at timed intervals and the quaternary inactivated by diluting 1:10 with a lecithin-Tween 80 solution known commercially as Letheen. Tween is a fatty acid ester of anhydrosorbitols which have been solubilized by etherifying the free hydroxyl groups with ethylene oxide. Agar pour plates are prepared from the Letheen solutions, incubated at 37 C. for 48 hours and counted for surviving bacteria. It should be understood that, for some applications, this stringent kill/ time requirement need not be met. For example, a killing power of 99.999 percent in seconds for water of the same hardness may be acceptable under appropriate circumstances.

With the development of this quaternary it was believed that the need for a liquid detergent-sanitizer of high hard water tolerance, particularly for use in the dairy and restaurant fields, could easily be met. However, when the quaternary was combined with any one of a number of well-known nonionic surfactants that are commonly used in detergent-sanitizer formulations, it was discovered that the hard water tolerance of the quaternary was greatly reduced. The detergent efficiency of the nonionics generally being so high, it became desirable to devise a detergent-sanitizer which would have the detersive advantages of the nonionics without appreciably sacrificing the hard water tolerance of the quaternary.

The present invention exceptionally satisfies the need just described. It consists of a detergent-sanitizer formulation of which the sanitizer is the mixture of alkyl dimethyl benzyl ammonium chlorides defined above, and the detergent is a mixture of an ethoxylated 11-14 carbon amine having the general structural formula in which 11:1 to 80. The carbon values for this amine, it should be understood, are average values. Thus, a C amine is a mixture and may have as its constituents some compositions that are below as well as some that are above a value of C but the average will be about C The same applies to each of the other amines in the indicated range.

Optionally, there can be incorporated in the formulation one or more alkaline builders or sequestering agents. Examples of suitable additives are sodium hydroxide, sodium tripolyphosphate, tetrasodium pyrophosphate, trisodium phosphate, sodium metasilicate, and the sodium and potassium salts of ethylenediamine tetraacetic acid.

By way of comparison, Table I shows the results of Chambers tests of the compatibility of a number of excellent nonionic detergents with the hard water tolerance of the quaternary mixture. It will be seen that all the combinations thus tested failed to show the required bactericidal effect even in water hardness of only 500 p.p.m.

TABLE I [Chambers tests comparing compatibility of several nonionic detergents with the hard water tolerance of a (Is-C18 alkyl dimethyl benzyl ammonium chloride sanitizer using an AOAC synthetic hard water.]

See footnotes at end of table.

TA-BLE I Continucd Exposure Time in Seconds etergent Non l henox ethanol 9.5 ethox rou s T.S./ml TNC TN 0 TNC y p y y g p i 408 000 1 e 8 0 t l he 0 tha 01 30 ethox rou s T.S.m

c y p n xye n y g p Percent Kill-.. 99T5IZI0i Oct 1 henox ethanol cthox rou s T.S.m1

yp y yg p) Perc/ent Kill... e g 99. 99. 9935 Oct 1 bone ethanol 16 ethox rou s T.S. ml

yp Xy yg p) Percent Kill... 99 99 99. 9917 Nonylphenoxyethanol (9-10 cthoxy groups) I.S./ml TN 0 TN 0 TN 0 Percent Kill... 99

NOTE.NO. organisms/ml. at O time=109,000,000.

1 Total Survival/m1.

2 TN C=Organisins too numerous to count.

20 TABLE II--'Continued NOTES:

- Exposure Time in Seconds (1) The final concentration of active quaternary was Concentration of sodium 200 p.p.m. Tripolyphosphate (2) The final concentration of active detergent was 15 60 200 p.p.m.

(3) The water hardness was 500 p.p.m. g f gfliii g Even the addition of an alkaline builder or sequester- 00p p m Kinm 99 99 ing agent which helps to raise the hard water ceiling of 1 -9 gg -g g g some compositions failed to provide the required bac- 800 ppm TNC 161,000 60 tericidal effect except when abnormally large, impractical 1 000 m gag g; Kill... 147 33 .8323 90. 9993 amounts were added. This is shown in Table II which 'f 'f 993469 100 100 follows.

TABLE II Norm-No. organisms/m1. at 0 time=96,000,000.

, 1 Total Survival/m1. [Chambers tests in which various amounts of sodium tripolyphosphate 35 2 TN O=Organisms too numerous to count were added to attempt to raise hard water tolerance of a (la-(31 alkyl dimethyl benzyl ammonium chloride sanitizer and octylphenoxy- NOTES: ethanol (9-10 ethoxy groups)] (1) The final concentration of active quaternary was Exposure Time in Seconds 200 P-P- aq f i fig ggg 40 (2) The final concentration of active detergent was rpo yp p 15 30 60 200 p.p.m. in (A) the first four tests and 400 p.p.m.

in (B) the last five tests. A None T.S./ml. ZTNC TNC 470,000 (3) The water hardness was 500 p.p.m.

' Percent Kill-.. 99 99 99.5104 200 p.p.m T.s./m1-. TNC TNO 300, 000 The use of several combinations of alkaline builders moppm E?? S fggg and/or sequestering agents likewise failed to raise to Percent K111--. 99 99 99. 9921 satisfactory levels the bactericidal elfect and hard water 800 ppm ggfiggg 332 8 tolerance of another nonionic detergent-sanitizer combination as shown in Table III which follows.

TAB LE III [Chambers tests in which various alkaline builders and sequestering agents were added to attempt to ra se the hard water tolerance of a 03-018 alkyl dimethyl benzyl ammonium chloride sanitizer and octylphenoxyethanol (1243 ethoxy groups)] Norm-No. organisms/nil. at 0 time=1l3,000,000.

1 Total Survival/ml.

2 TNC =Orgam'sms too numerous to count. 8 Versenc=Sodium salt of ethylenediaminetetraacetic acid.

. 6 NOTES: A comparison of the results in the foregoing tables (1) The first test was run Without any detergent with those in Table V clearly illustrates the unique and (2) The final concentration of active quaternary was remarkable effectiveness of the present invention in which a particular type of ethoxylated t-carbinamide is em- 200 p.p.m. 1 d th d t t h (3) The final concentration of active detergent was 5 i amme 1st 6 mlxture 200 ppm. resen e y e ormu a (4) The water hardness was 600 p.p.m. t-C H NH(CH CH O) H Another series of well known, commercially available, where n is 1 to 80. As shown in Table V, these surand highly efiicient surfactants were employed as the defactants are quite compatible with the C C alkyl ditergents in combination with a C -C alkyl dimethyl 10 methyl benzyl ammonium chloride sanitizers.

TABLE V [Chambers tests in which various ethoxylated t-carbinamines (t-Cn-14H2:-z0NHz) were screened for compatibility with (J -C18 alkyl dimethyl benzyl ammonium chloride snni tizers regarding the hard water tolerance of the mixture] Exposure Time in Seconds Detergent None t-Cn-uHza-wNH(CHzCH2O)H T S t-Cn-uHzg-znNH(CHzCHzO)3H r T S /I11l t-C11-14Hz3-20NH(CH2CH20)5H T S t-Cn-uHza-nNH(CHzCHqO); 5H T S /1Tl1 t-C 1-1 H23-a0NH(CHaCHnOhH T S /!1 1 t'Cl1-l4 23-59NH(C 2C 2 )10H T S t-Cn-nHza-WNH(CHzCHzO)11,511 T S lIIll t-Cn-uHn-zsNH(CH2CHr0)irH T S t-Cu-n n-nNH(CH2CH2O)17.aH T S t-C1 4H23-20NH(CHzCHaOhoH T S/ 1 t- 11-14 2s-20NH(CH2C zO)zz,uH T S t-Cn-uHza-ztNH(CH2CH2O)a H T 5 [I111 t-Cn-uHza-zoNH(CH2CH2O)40H .c T S lml t-Cu-nHz uNH(CHaCHzOmH T.S./ml 176, 000 2, s00 30 Percent Killru 99. 8257 99.9972 99.9999

Note-N0. organisms at 0 tlme=101,000,000. 1 Total Survival/m1. TNC=0rganisms too numerous to count.

benzyl ammonium chloride sanitizer. These were the NoTEs: surfactants represented by the formula 49 (1) The final concentration of active quaternary was (2) The final concentration of active detergent was 200 p.p.m.

(3) The water hardness was 600 p.p.m.

where n is an average of 5, 15 or 25. As shown in Table IV, this combination had a lower hard water tolerance than the quaternary alone, and certainly is an unsatisfactory detergent-sanitizer composition.

TABLE IV [Chambers tests in which various ethoxylated t-carbinamines (t-C1g 24H37 4gN I2) were screened for compatibility with a 0 -01 alkyldimethyl benzyl ammonium chloride sanitizer regarding the hard water tolerance of the mixture] Exposure Time in Seconds Detergent None I.S./ml. 146, 000 400 0 Percent Kill 99, 8719 999996 100 t-C1s-24H3740NH(CH2CH20)5H T.S./rn1 2 TNC TNC 470, 000 Percent Kill. 99 99 99.5877 t-C -zrHy-q NH(CHzCHzO)15H T.S./m1 TNC TNC 66,300 Percent Kill 99 99 99. 9418 1;-C gz-1H3740NH(CH2CH2O)25H T.S./IT11 TNC TNC 117, 000 Percent Kill 99 99 99. 8974 No'rE,No. organisms/ml, at 0 time=l14,000,000. 1 Total Survival/ml. 2 TNC=Organisms too numerous to count.

Names:

(1) The final concentration of active quaternary was As indicated above, the basic compositions of the pres- 200 p.p.m. ent invention can be modified by the addition of various (2) The final concentration of active detergent was alkaline builders and/or sequestering agents. In no case 200 p.p.m. is the hard water tolerance lessened, and in most cases it (3) The water hardness was 600 p.p.m. is increased. To illustrate, in Table VI there are listed several formulations of the compositions of this invention. Table VII indicates the hard Water ceilings of some of those formulations.

Table VIII discloses the effect of various sequestering agents on one of those formulations.

TABLE VI.FORMULATIONS MADE IN ACCORDANCE WITH PRESENT t-C11-14H2a-2QNH(CH2CH2O) 'mT-T Distilled water Trisodium phosphate-. Sodium metasilicate- Versene* Sodium $65555;

Sodium salt of ethylenediamine tetraacetic acid.

TABLE VII A. Hard Water Ceilings of Composition No. 1 From Table VI Exposure Time in Seconds Final Concentratin Water Hardness of Active Quaternary 200 p.p.m 500 p.p.m T.S.lml. 105,300 510 0 Percent Kill--- 99. 9007 99. 9995 100 200 p.p.m 550 p.p.m T.S. ml 176,000 1,740 0 Percent Kill-.. 99.8340 99.9984 100 200p.p.n1 600 p.p.m T.S.lml 530,000 8,200 200 Percent Kill--- 99.5000 99.9923 99.9998

N0. organisms/ml. at O time=106,000,000

B. Hard Water Ceilings of Composition No. 2 From Table VI 200 p.p.m 500 p.p.m T.S.lml 53,000 260 0 Percent Kill--- 99. 9500 99. 9998 100 200 p.p.m 550 p.p.m T.S.Iml 240,000 820 Percent Kill--- 99.7736 99.9992 99.9999 200 p.p.m 600 p.p.m T.S.Iml 700,000 4,900 150 Percent Kill.-- 99.3396 99.9954 99.9999

N0. organisms/ml. at 0 time=106,000,000

0. Hard Water Ceilings of Composition N0. 3 From Table VI 200 p.p.m 500 p.p.m T.S.lml 41,000 50 0 Percent Kill--- 99.9620 99.9999 100 200 p.p.m 550 p.p.m T.S.lml 293,000 460 0 Percent Kill-.. 99. 7287 99. 9996 100 200 p.p.m 600 p.p.m T.S./ml 760,000 1,830 0 Percent Kill... 99.2963 99.9983 100 200 p.p.m 650 p.p.m TS. in TNC 5,200 100 Percent Kill-.- 99 99. 9952 99.9999

No. or organisms/ml at 0 time=108,000,000

D. Hard Water Ceilings of Composition No. 4 From Table VI 200 p.p.m 550 p.p.m T.S.lml ,00 0 Percent Kill--. 99.9352 99.9999 100 200 p.p.m 600 p.p.m.---. T.S. m 130,000 43 0 Percent Kill... 99.8796 99.9996 100 200 p.p.m 650 p.p.m T.S./m1 TN 2,340 0 Percent Kill-.. .9978 100 200 p.p.m 700 p.p.m T.S.Iml TNC 6,600 40 Percent Kill-.. 99. 9939 99.9999

No. organisms/m1. at 0 time=108,000,000

E. Hard Water Ceilings of Composition No. 5 from Table VI 200 p.p.m 500 p.p.m T.S.lml 5 0 0 Percent Kill..- 99.9995 100 100 200 p.p.m 550 p.p.m T.S.lml 2,800 0 0 Percent Kill... 99.9972 100 100 200 p.p.m 600 p.p.m T.S.lml 17,200 30 0 Percent Kill-.. 99.9828 99.9999 100 200 p.p.m 650 p.p.m T.S.lml 38,000 570 0 Percent Kill-.. 99.9620 99.9994 100 200 p.p.m 700 p.p.m T.S.lml 96, 000 1,880 0 Percent Kill... 99.9040 99. 9981 100 200 p.p.m 750 p.p.m T.S.lml 250, 000 5, 100 0 Percent Kill--- 99.7500 99.9949 100 No. organisms/ml. at 0 t1me=100,000,000

1 Total Survival/ml.

2 TNC=Organisms too numerous to count.

TABLE VIII [Chambers tests demonstrating effect of various sequestrants on the hard water tolerance of composition No. 1 from Table VI] Exposure Time in Seconds Alkali or Sequestrant 'I.S./ml. 410, 000 0 Percent Kill. 99. 6095 99.9991 100 None T.S./1nl 2 TNC 6, 50 90 Percent Kill. 90 99. 9938 90. 9999 Sodium tripolyphosphate. T.S./ml TNC 5, 2 50 Percent Kill 99 99.9950 99.9999 Tetrasodium pyrophos- T.S./ml 880,000 2, 210 0 phate. Percent Kill. 99. 1619 99.9979 100 Trisodium phosphate T.S./ml 350, 000 1, 300 0 Percent Kill. 90. 6667 99.9988 100 Versene 'I.S./ml 640, 000 1, 580 0 Percent Kill 99. 3905 99. 9985 100 Sodium metasilicate T.S./ml 176,000 1, 170 0 Percent Kill. 99. 8324 99.9989 100 Norr;.No. of organisms/mlat 0 time=105,000,000. 1 Total Survival/ml. 2 TNC: Organisms too numerous to count. 3 Verseue=Sodium salt of ethylenediamine tctraacetic acid.

NOTES:

(1) The final concentration of active quaternary was 200 ppm.

(2) The final concentration of active alkali or sequestrant was 150 ppm.

(3) The water hardness was 600 ppm.

From the foregoing examples and comparisons it will be apparent that I have provided a new and highly useful liquid detergent-sanitizer; that the combination of a C C alkyl dimethyl benzyl ammonium chloride sanitizer and a mixture of ethoxylated amines having the formula tC H NH(CH CH ),,H 71:1 to 80 surprisingly results in highly compatible detergentsanitizers with hard water tolerances substantially as high as that of the quaternary alone; and that the novel detergent sanitizers are also highly compatible with and benefited by alkali builders or sequestering agents.

It will also be clear that, although the particular types of sanitizer and the particular class of detergents are critical to the successful performance of the novel compositions, it is possible to vary the combinations thereof quite widely. The disclosed specific combinations thereof, with or without addition of alkali or sequestrants, should therefore be understood to be merely illustrative and the invention is not limited thereto. If higher detergency is desired, a relative drop in the quantity of the sanitizer in the composition is necessary as more detergent is added. This would slow down the speed of reaction, i.e., the rate of bactericidal action. In turn, this would call for more sequestering agent in order to offset the drop in rate of reaction. Thus, although the nature of the amine detergents that are combined with the samtizers is critical, the relative ratios of the two is not. Preferably, as shown by the data in Table VI above, a ratio of from 2.5 to percent of the detergent to 10 percent of the sanitizer (both on a volume basis), is employed in a solution, the balance of which essentially is water. This range is extended so that there may, in some cases, be more detergent than the sanitizer present in a proportion of up to 30% of the former to 10% of the latter. Although the preferred ranges of the detergent to sanitizer thus are from 1:4 to 1:1, it should be understood that ranges of from 1:6 to 321 may prove acceptable in some applications. Selecting a use ratio of a given combination of components thus will depend upon ones own satisfaction level and can be determined quite simply by those skilled in the art.

I claim:

1. A liquid detergent-sanitizer solution whose principal active ingredients are present in a total amount ranging from about 12.5% to about by volume, the ratios of said ingredients ranging from 1 part detergentz6 parts sanitizer to 1 part sanitizerz3 parts detergent, the remainder of the solution consisting of to 87.5% water, the detergent consisting of an ethoxylated amine having the general formula t'C 1 H23 2gNH(CH CH O) H in which 11:1 to 80, the carbon values for the amine representing quantities which are averages coming within the indicated range, and the sanitizer consisting of a C -C alkyl dimethyl benzyl ammonium chloride.

2. A liquid detergent-sanitizer solution whose principal active ingredients, by volume, consist of from 2.5 to 30 percent of an ethoxylated amine detergent having the general formula t'C11 14H23 29NH(CHZCH O) H in which 11:1 to 80, the carbon value for the amine representing quantities which are averages coming within the indicated range, 10 percent of a C C alkyl dimethyl benzyl ammonium chloride sanitizer, and the remainder of the solution consisting of about 60.0% to about 87.5 water. i

3. The composition of claim 1 in which the sanitizer is a mixture principally consisting of a C C and C dimethyl benzyl ammonium chlorides.

4. The composition of claim 1 in which 0.5% to 7.75% of the water is replaced by an alkaline builder from the class consisting of sodium hydroxide, phosphate, silicate, and the sodium and potassium salts of ethylenediamine tetraacetic acid.

5. The composition of claim 4 in which the detergent, sanitizer and at least one of the alkaline builders are in the following proportions, all figures being represented as percent by volume: 10 percent of the sanitizer, 2.5 to 20 percent of the detergent, and 0.5 to 7.5 percent of the builder.

6. A liquid-detergent-sanitizer composition containing, in percent by volume, about 10 of a C C alkyl dimethyl benzyl ammonium chloride sanitizer, about 10 of an ethoxylated amine detergent having the general formula and about of distilled water.

7. A liquid-detergent-sanitizer composition containing, in percent by volume, about 10 of a C -C alkyl dimethyl benzyl ammonium chloride sanitizer, about 10 of an ethoxylated amine detergent having the general formula t'C11 H23 29NH(CHzCHzO)15H, about 0f water, about 7.50 trisodium phosphate, and about 0.25 of an alkaline sequestering agent consisting of a sodium salt of ethylenediaminetetraacetic acid.

8. A liquid-detergent-sanitizer composition containing, in percent by volume, about 10 of a C C alkyl dimethyl benzyl ammonium chloride sanitizer, about 10 of an ethoxylated amine detergent having the general formula about 72.25 of distilled water, about 7.50 of sodium metasilicate, and about 0.25 of an alkaline sequestering agent consisting of a sodium salt of ethylenediaminetetraacetic acid.

9. A liquid-detergent-sanitizer composition containing, in percent by volume, about 10 of a mixture of alkyl dimethyl benzyl ammonium chloride sanitizer, about 10 of an ethoxylated amine detergent having the general formula about 75.25 of distilled water, about 0.5 of an alkaline sequestering agent consisting of a sodium salt of ethylene- 11 12 diaminetetraacetic acid, and about 4.0 of sodium hy- OTHER REFERENCES droxlde- Lesser, Soap and Sanitary Chemicals, Detergent Sanitizers, August 1951, pp. 37-39, 67, 69, and 98. References Cited by the Examiner Sequestrene, publ. of Geigy Industrial Chemicals, 1952,

UNITED STATES PATENTS 5 25: and 1, 2 31 2 li l 2 -1 2 XR JULIUS GREENWALD, Primary Examiner. 2,87 ,2 6 9 9 iey 2 2 O XR 2,950,253 8/1960 Kling et a1 252 1s2 ALBERT MEYERS Emmmer- 2,950,255 8/1960 Goff 252152 10

Claims (1)

1. A LIQUID DETERGENT-SANITIZER SOLUTION WHOSE PRINCIPAL ACTIVE INGREDIENTS ARE PRESENT IN A TOTAL AMOUNT RANGING FROM ABOUT 12.5% TO ABOUT 40%, BY VOLUME, THE RATIOS OF SAID INGREDIENTS RANGING FROM 1 PART DETERGENT:6 PARTS SANITIZER TO 1 PART SANITIZER:3 PARTS DETERGENT, THE REMAINDER OF THE SOLUTION CONSISTING OF 60% TO 87.5% WATER THE DETERGENT CONSISTING OF AN ETHOXYLATED AMINE HAVING THE GENERAL FORMULA T-C11-14H23-29NH(CH2CH2O)NH IN WHICH N=1 TO 80, THE CARBON VALUES FOR THE AMINES REPRESENTING QUANTITIES WHICH ARE AVERAGES COMING WITHIN THE INDICATED RANGE, AND THE SANITIZER CONSISTING OF A C8-C18 ALKYL DIMETHYL BENZYL AMMONIUM CHLORIDE.