NZ264819A - Aqueous disinfecting hard-surface cleaner containing quaternary disinfectant, nonionic surfactants and no anionic surfactants - Google Patents

Description

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..CAw..... w ONLV\V HO 01 No.: Date: NEW ZEALAND PATENTS ACT, 1953 COMPLETE SPECIFICATION ANTIMICROBIAL DISH WASHING LIQUID 3 1 nr.T 1994 We, EASTMAN KODAK COMPANY, a corporation created and existing under the laws of the State of New Jersey, and having a place of business at 343 State Street, Rochester, New York 14650, United States of America hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- (followed by page -1A-) €4819 Field of the Invention This invention relates to formulations for 5 manually washing dishes.

Background of the Invention Light-duty liquid detergent formulations for kitchen surfaces are well known. Kitchen surfaces 10 include counter tops, stove tops, dishes and any other hard surface commonly found in kitchen environments. The term "dishes" includes any utensils involved in food preparation or consumption. Kitchen surfaces, particularly dishes, must be washed free of food 15 residues, grease, proteins, starches, gums, dyes, oils and burnt organic residues.

Most of the consumer accepted formulations in use include anionic synthetic surfactants with or without a nonionic surfactant. Many of such 20 formulations contain a sulphonate-type anionic surfactant, for example, an alkylbenzene sulphonate or an alkane sulfonate, in conjunction with a sulphate or alkyl ether sulphate, or a nonionic surfactant, for example, an alcohol ethoxylate, an alkyl phenol 25 ethoxylate, a mono- or diethanolamide or an amine oxide. The sulphonate material generally predominates.

It is the anionic surfactant that provides the typical high foaming (suds) characteristics generally associated with dish washing formulations. 30 Foam (suds) is the cleaning efficacy signal relied on by consumers. Nonionic surfactants generally do not provide good foaming characteristics.

It is known from US Patent No. 2,746,928 that it is not possible to mix anionic surface-active agents 35 with quaternary ammonium germicides. The cationic quaternary ammonium germicide reacts with the anionic surface-active agent resulting in a reduction in germicidal and detergent activity. ' t- / [, .

* W s ^ Thus anionic surfactants are incompatible with cationic quaternary antimicrobial surfactants and nonionic surfactants do not normally provide significant foaming capability to liquid formulations.

Therefore current dish washing formulations can only mechanically eliminate bacteria from kitchen hard surfaces. They are not effective in killing or controlling the spread of germs throughout the kitchen environment. Thus dish washing liquids combining good 10 foaming and antimicrobial activities are not available to the consumer.

Summary of the Invention The present invention provides an aqueous 15 disinfecting liquid formulation for cleaning hard surfaces, particularly dishes, in a kitchen environment; wherein said formulation is free of anionic surfactants and consisting essentially of: a) 0.5 to 15 weight percent of a quaternary 20 disinfecting compound; b) 0.5 to 20, preferably 13 to 14, weight percent of a C22-C13 alcohol ethoxylate nonionic surfactant. * c) 0.0 to 20, preferably 3 .0 to 5, weight 25 percent of a c43- C45 alcohol ethoxylate nonionic surfactant; d) 0.5 to 20.0, preferably 2, weight percent of a nonionic surfactant selected from the group consisting of cocomonoethanolamide, cocodiethanolamide and combinations thereof; e) 0.5 to 12, preferably 3.0 to 9.0, weight percent cocoamidopropyl betaine nonionic surfactant; f) 0 to 2.0, preferably 1.0, weight percent of the sodium salts of EDTA.

This formulation of this invention will control the presence and spread of bacteria on hard surfaces in the kitchen environment, especially dishes. This invention contains a microbiologically active quaternary ingredient homogeneously incorporated into a ( / - \ C -<■ * O I nonionic aqueous surfactant system. Unexpectedly the formulation has good flash foaming and residual foaming capability although no anionic surfactants are included. Moreover, the formulation has excellent viscosity and color stability.

Details of the Invention Optional ingredients can include fragrances, dyes and stabilizers.

The purpose of the quaternary ammonium disinfectants is to kill on contact gram positive and gram negative organisms the organisms encountered in kitchen environments. Useful disinfectants include BTC 8358 which is N- Alkyl (50% C14, 40% C]_2, and 10% C^g) dimethyl benzyl ammonium chloride. Other quaternary ammonium salt may be any of the well-known class of quaternary ammonium germicides characterized by the formula: r, \ / N / \ R, wherein at least one of the radicals , R2, r3 and r4 is a hydrophobic, aliphatic, aryl aliphatic, or aliphatic aryl radical of from 6 to 26 carbon atoms and the entire cation portion of the molecule has a molecular weight of at least 165. The hydrophobic radicals may be long-chain alkyl, long-chain alkoxy aryl, long-chain alkyl aryl, halogen-substituted long-chain alkyl aryl, long-chain alkyl phenoxy alkyl, aryl alkyl, etc., in nature. The remaining radicals on the nitrogen atom other than the hydrophobic radicals are substituents of hydrocarbon structure usually containing a total of no more than 12 carbon atoms. The radical x in the above formula is any salt-forming anionic radical.

Suitable quaternary ammonium salts within the above description include the alkyl ammonium halides such as cetyl trimethyl ammonium bromide, alkyl aryl ammonium halides such as octadecyl dimethyl benzyl 5 ammonium bromide, N-alkyl pyridinium halides such as N-cetyl pyridinium bromide, and the like. Other suitable types of quaternary ammonium salts include those in which the molecule contains either, amide or ester linkages such as octyl phenoxy ethoxy ethyl dimethyl 10 benzyl ammonium chloride, N- (laurylcocoaminoformylmethyl) - pyridinium chloride, etc. Other very effective types of quaternary ammonium germicides are those in which the hydrophobic radical is characterized by a substituted aromatic nucleus as 15 in the case of lauryloxyphenyltrimethyl ammonium chloride, cetylaminophenyltrimethyl ammonium methosulfate, dodecylphenyltrimethyl ammonium methosulfate, dodecylbenzyltrimethyl ammonium chloride, chlorinated dodecylbenzyltrimethyl ammonium chloride, 20 and the like.

Preferred quaternary ammonium germicides of the above general types are the long-chain alkyl dimethylbenzyl quaternary ammonium salts, the alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary 25 ammonium salts, the N-(acylcocoaminoformylmethyl)-pyridinium halides, the long-chain alkyl trimethyl ammonium halides, the long-chain alkyl benzyl dimethyl benzyl ammonium halides, and the long-chain alkyl benzyl diethyl ethanol ammonium halides in which the 30 alkyl radical contains from 8-18 carbon atoms.

The mechanism of this nonionic system for cleaning standard food and kitchen soils is through emulsification of the soils. Current anionic light duty liquids solubilize most food soils. When soil is 35 emulsified within a system, it will affect the type, density and amount of foam that can be generated. In general, emulsified fatty soils will reduce the amount of foam that can be generated as further cleaning takes place. Since anionic systems solubilize soils, the 4 3 effect on the foam is not as great as with nonionic systems. Therefore, foam generated from anionic systems is of greater volume and more stable throughout the cleaning process, In general, anionic surfactant systems such as those found in the current light duty liquids are classified as high foamers. Conversely, nonionic surfactant systems are classified as low foamers.

The challenge was to achieve disinfection 10 activity while producing consumer acceptable foam using a nonionic and cationic surfactant combination. By careful selection and great experimentation, we have identified a surfactant mixture, expressed in Example 1, Table 1, that produce consumer acceptable foam 15 comparable to commercial dish washing liquids using anionic detergents. The useful nonionic surfactants have various chain lengths and degrees of ethoxylation that allow the dish washing liquid to be effective on a wide range of food soils while providing good flash 20 foam volume as well as moderate foam stability. This system provides the consumer with effective cleaning on, but not limited to, greasy food soils, fatty food soils, and oily food soils while maintaining disinfection.

Example 1-3 The unexpected foaming properties of the formulations of the invention are illustrated in these examples. The foaming properties are due to the 30 carefully balanced mix of nonionic surfactants. The formulations of examples 1-3 are presented in Table 1. -6-Table I 6 -/t' Content in the Weight Perc-pnf INGREDIENTS Water, D.I Di sodium EDTA neodol 25-12 Neodol 23-6.5 Mackam DZ (30%) Mackamide c MONAMID CMA BTC 8358 (80%) Fragrance 24 HR. *Viscosity 6 Weeks Room Temp. * Viscosity Example 1 62.95% 1.00% 14.00% 16.70% 3.00% 2.00% 0.35% 610 CPs 618 CPs Exemple 2 64.05% 1.00% 4.00% 13.00% 13.60% 2.00% 2.00% 0.35% 712 CPs 728 CPs ExamnlP 61.95% 1.00% 3.00% 13.00% 16.70% 2.00% 2.00% 0.35% 766 CPs 734 CPs *Brookfield Model LVT, spindle 3 at 60 rpm The formulations were prepared by adding the ingredients to ambient temperature water in the order described and mixed until dissolved. Alternatively, if Monamid CMA is used (examples 2 & 3 above), the mixture is warmed to about 38 °C before the addition of 10 Monamid CMA to aid dissolution. Other known methods may be used know to those skilled in the art. The batch can then be cooled down to add any volatile components.

The chemical name and function of each 15 ingredient in Table I is presented below in Table II. / f /' C * r ' 1 t I i Table II TRADENAME D.I. WATER MACKAMIDE C MONAMID CMA NEODOL 25-12 NEODOL 23-6.5 MACKAM DZ (30-35%) DISODIUM EDTA BTC 8358 (80%) CHEMICAL NAME DEIONIZED WATER COCOAMIDE DEA (cocodiethanol amide) COCOAMIDE MEA (cocomonoethanol amide) C13-C15 ALCOHOL ETHOXYLATE C12-C13 ALCOHOL ETHOXYLATE COCOAMIDOPROPYL BETAINE DISODIUM EDTA N-ALKYL DIMETHYL BENZYL AMMONIUM CHLORIDE FUNCTION DILUENT NONIONIC SURFACTANT NONIONIC SURFACTANT NONIONIC SURFACTANT NONIONIC SURFACTANT NONIONIC SURFACTANT CHELATOR GERMICIDE The good foaming capability is established by measuring 5 foam height according to the Standard Test method for Foaming Properties of Surface-Active Agents, astm D1173-53 (Reapproved 1986). The method was modified by using a 500 mL cylinder as the foam receiver. Foam heights in the foam receiver were taken initially after 10 the dropping of the solution and at various time intervals thereafter. Foam height was determined in both unloaded and loaded systems. A loaded system refers to water in which oil has been added to simulate oils encountered during dish washing. An unloaded 15 system refers to water to which no oil has been added.

A second method for measuring foam heights was also utilized. This method, designed by the Shell Development Co., is entitled Soil Titration Test for Determination of Foam Performance of Dish washing 20 Detergents. It was published January 1987 as SC:967-87. The method is a procedure to evaluate the foam performance of detergent formulations in the presence of dish washing soils. Foam heights are measured as a percent of a standard formulation.

Table III FOAM HEIGHT STABILITY IN USE Method Eyaluatipn Modified ASTM D1173-53 Foam Height (1:256.CM) Unloaded (cm) Loaded (cm) Example 1 Minutes 0 5 Example 2 Minutes 0 5 10 15 14.5 14.5 14 15 14.5 14 14 14.5 14 13.5 15 15 Example 1 Minutes 0 5 14 13.5 15.5 15 16 15.5 15 13 14.5 14 Soil Titration Test Foam Performance 51 49 58 Hating, % The formulations of this invention were 10 compared to commercial anionic based dish washing liquids using the modified ASTM D1173-53 method. In an unloaded soil system, foam heights ranged from 16 - 19 cm. In a loaded soil system, foam heights ranged from 13.5 - 15.5 cm. Our invention of a non-15 ionic compared quite favorably.

Examples 4-6 The formulation of example 3 was tested using various levels of active BTC 8358 for antimicrobial 20 activity against Staphvloccus aureus (ATTC 6538) and Kleb pneumoniae (ATTC 4352) by a quantitative suspension test. The test was carried out at dilution of one part formulation to 256 parts of deionized water at room temperature for a 30 second contact time. The 25 test protocol was as follows. 1. Sample Inoculation A. Inoculate 1.0 ml of the test culture into each sample tube. Repeat for organism.

I V - b I 0 - 9 - * ^ B. Subculture 1.0 ml of the sample after 1-minute and 1.0 ml after 5 minute contact time.

C. Subculture the sample into 9.0 ml of DIFCO AOAC Letheen Broth. This the 10"^ sample dilution. 2 . Samnle Dilutions and Plating A. Plate the 10"1, 10~3( and 10~5 dilutions for each sample/organism/contact time combination. 1. From the 10~1 dilution: a. Plate 1.0 ml = 10"^- plate. b. Pipet and transfer 0.1 ml into 9.9 ml of Letheen Broth = 10"^ sample dilution. 2. From the 10~3 sample dilution: a. Plate 1.0 ml = 10"3 plate. b. Pipet and transfer 0.1 ml into 9.9 ml of Letheen Broth = 10"5 sample dilution.

B. Pour each plate with Tryptic Soy Agar containing polysorbate 80 and lecithin (either DIFCO or BBL) .

C. Incubate the plates for 48hr at 35C. 3. Control Counts: Dilutions and Plating A. Inoculate 1.0 ml of culture into 9.0 ml Letheen Broth.

B. Subculture 1.0 ml of that Letheen tube into 9.0 ml Letheen Broth at 1 minute and 5 minutes exposure. These are the 10"1 dilution tubes for the 1-minute and 5-minute contact time controls.

C. Plate the 10"^ and 10"^ dilutions for each 3 0 contact time. 1. Pipet 0.1 ml of the 10"1 dilution into 9.9 ml Letheen Broth = 10~3. 2. Plate 0.1 ml of the 10"^ dilution = 10"^ plate. 3. Pipet 0.1 ml of the 10"^ dilution into 9.9 ml of Letheen Broth = 10"^ dilution. 4. Plate 1.0 ml of the 10~5 dilution = 10"^ plate.

Claims (7)

-10- D. Pour the plates with Tryptic Soy Agar containing polysorbate 80 and lecithin. E. Incubate at 35°C for 48hr. 5 4. Log Reduction Calculations A. Determine the number of bacteria survivors at each contact time for both the controls and test samples. 1. Count the number of colonies on the 10 petri dish. The plate is acceptable for counting with a colony count between 2 5 and 250. 2. Multiply the number of colonies by the plate dilution factor = the number of surviving bacteria. 15 B. Determine the Log Reduction in bacteria for each sample/organism/contact time combination. Log^o Control Count - Log^o Survivor Count = # Logs of bacteria reduced by the sample. The results obtained are presented in Table IV. 20 TABLE IV PERCENT OF BACTERIAL REDUCTION AT 3 0 SECOND CONTACT TIME Percent Percent Reduction % BTC 83 58 IN Reduction of MICROBIOLOGY FORMULA £f Kleb. TEST NUMBER (ACTTVE) DILUTION S, Ayr^y? Pneumoniae (Control) 0.00 1:256 83.1818 47.6623 1 0.50 1:256 85.4545 77.9220 2 1. 00 1:256 87.2727 76.6233 3 1.50 1:256 95.0909 88.9610 4 2.00 1:256 94.1818 94.1558 5 2 . 50 1:256 97.6818 97.3766 7 3 . 00 1:256 99.4363 98.9090 8 3 . 50 1:256 99.8772 99.7441 9 4.00 1:256 99.992 99.8481 25 -11- WHATWE CLAIM IS 264819

1. An aqueous disinfecting liquid formulation for cleaning hard surfaces in a kitchen environment; 5 wherein said formulation is free of anionic surfactants and consisting essentially of: a) substantially 0.5 to 15 weight percent of a quaternary disinfecting compound; b) 0.5 to 20 weight percent of a Ci2-Cl3 10 alcohol ethoxylate nonionic surfactant. c) 0.0 to 20 weight percent of a C13- C15 alcohol ethoxylate nonionic surfactant; d) 0.5 to 20.0 weight percent of a nonionic surfactant selected from the group consisting of 15 cocomonoethanolamide, cocodiethanolamide and combinations thereof; e) 0.5 to 12 weight percent cocoamidopropyl betaine nonionic surfactant; f) 0 to 2.0 weight percent of the sodium 20 salts of EDTA.

2. The formulation of claim 1 consisting essentially of a) 2 weight percent of a quaternary disinfecting compound; 25 b) 13 to 14 weight percent of a C12-C13 alcohol ethoxylate nonionic surfactant. c) 3.0 to 5 weight percent of a C13- C15 alcohol ethoxylate nonionic surfactant; d) 2 weight percent of a nonionic 30 surfactant selected from the group consisting of cocomonoethanolamide, cocodiethanolamide and combinations thereof; e) 3.0 to 9.0 weight percent cocoamidopropyl betaine nonionic surfactant; 35 f) 1.0 weight percent of the sodium salts of EDTA. 2648 -12-

3. The formulation of claim 1 or 2 wherein the quaternary disinfecting compound is alkyl (50% C^, 40% C^2 an<3 ^0% Cig) dimethyl benzyl ammonium chloride.

4. The formulation of claim 1 or 2 having a 5 viscosity of 250 to 1000 cPs.

5. The formulation of claims 1 or 2 having a viscosity of 250 to 80C cPs. .

A method of manually washing hard surfaces in a kitchen environment, comprising the steps 10 of: a) providing a disinfecting liquid according to any one of claims 1, 2 and 3; b) diluting the liquid with water; and c) contacting the surfaces with the diluted 15 formulation.

7. An aqueous disinfecting liquid formulation for cleaning hard surfaces in a kitchen environment substantially as herein described with reference to the examples. fk£k<rQ(\ toh.L-f 1./ the authorised agents A J PARK & SON