AU672930B2

AU672930B2 - Antimicrobial dish washing liquid

Info

Publication number: AU672930B2
Application number: AU77561/94A
Authority: AU
Inventors: James William Cavanagh; Beth T.G. Graubart
Original assignee: Reckitt and Colman Inc
Current assignee: Reckitt Benckiser LLC
Priority date: 1993-11-01
Filing date: 1994-10-31
Publication date: 1996-10-17
Anticipated expiration: 2014-10-31
Also published as: EP0651049A3; AU7756194A; EP0651049A2; JPH07188697A; CA2132811A1; BR9404250A; NZ264819A

Description

-Y L--l

AUSTRALIA

Patents Act A2 0U COMPLETE SPECIFICATION

(ORIGINAL)

Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: I I Priority Related Art: 00 0 Name of Applicant: -CIli.tmnn Tn-Tnr~~nl*nmr\nnnv Jak] Tr k (01L lvldr JA16 Actual Inventor(s): /S C Beth T. G. Graubart 113 James William Cavanagh Address for Service: PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Invention Title: ANTIMICROBIAL DISH WASHING LIQUID Our Ref 384709 POF Code: 4703/4703 The following statement is a full description of this invention, including the best method of performing it known to applicant(s):

S--

u-T I I 1111111 A11111111111111511111111111111111111111111111 (12) PATENT ABRIDGMENT (11) Document No. AU-B-77561/94 (19) AUSTRALIAN PATENT OFFICE (10) Acceptance No. 672930 (54) Title ANTIMICROBIAL DISH WASHING LIQUID International Patent Classification(s) (51) 6 C11D 003/48 A61L 002/18 C11D 001/94 (21) Application No. 77561/94 (22) Application Date :31.10.94 Priority Data (31) Number (32) Date (33) Country 146542 01.11.93 US UNITED STATES OF AMERICA (43) Publication Date 18.05.95 (44) Publication Date of Accepted Application 17.10.96 (71) Applicant(s) RECKITT COLMAN INC.

(72) Inventor(s) BETH T.G. GRAUBART; JAMES WILLIAM CAVANAGH (74) Attorney or Agent PHILLIPS ORMONDE FITZPATRICK 367 Collins Street, MELBOURNE VIC 3000 (56) Prior Art Documents US H269 US 4540505 US 3983079 (57) Claim 1. An aqueous disinfecting liquid formulation for cleaning hard surfaces in a kitchen environment; wherein said formulation is free of anionic surfactants and consisting essentially of: a) about 0.5 to 15 weight percent of a quaternary disinfecting compound; b) 0.5 to 20 weight percent of a C12-C13 alcohol ethoxylate nonionic surfactant.

c) 0.0 to 20 weight percent of a C 13

C

1 alcohol ethoxylate nonionic surfactant; d) 0.5 to 20.0 weight percent of a nonionic surfactant selected from the group consisting of cocomonoethanolamide, cocodiethanolamide and combinations thereof; e) 0.5 to 12 weight percent cocoamidopropyl betaine nonionic surfactant; o-r~d f) 0 to 2.0 weight percent of the sodium salts of EDTA.

6. A method of manually washing hard surfaces in a kitchen environment, comprising the steps of: /2 ~p~al~ISpL~pll r (11) AU-B-77561/94 -2- 672930 a) providing a disinfecting liquid according to any one of claims 1, 2 or 3; b) diluting the liquid with water; and c) contacting the surfaces with the diluted formulation.

-1i- ANTIMICROBIAL DISH WASHING LIQUID Field of the Invention This invention relates to formulations for manually washing dishes.

Background of the Invention Light-duty liquid detergent rormulations for kitchen surfaces are well known. Kitchen surfaces 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 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.

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 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.

~F~P~P 9 -2- 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 foaming and antimicrobial activities are not available to the consumer.

Summary of the Invention The present invention provides an aqueous 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 C 12

-C

13 alcohol ethoxylate nonionic surfactant; c) 0.0 to 20, preferably 3 .0 to 5, weight percent of a C 13

C

15 alcohol ethoxylate nonionic i 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 psrce.nt 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 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 colour stability.

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

Preferably, the formulation according to the present invention has a viscosity of 250 to 1000 CPS, more preferably 250 to 800 CPS.

*0 0 °oco *8 o*o o°° *o °go o o *oo oo* -3nonionic aqueous surfactant system. Unexpectedly the formulation has good flash foaming and residual oaming capability although no anionic surfactants re included. Moreover, the formulatio as excellent viscosity and color stability.

Details of the In ion 0 -onal ingredients can include fragrances, dyes -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 ETC 8358 which is N- Alkyl (50% C 14 40% C 12 and 10% C 1 6 dimethyl benzyl ammonium chloride. Other quaternary ammonium salt may be any of the well-known class of quaternary ammonium germicides characterized by the formula: o a RI R,

N

R

4

R

2 R4 20 wherein at least one of the radicals R 1

R

2

R

3 and R 4 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 longchain 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 Y anionic radical.

'ji~ r i :r 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 ammonium bromide, N-alkyl pyridinium halides such as Ncetyl 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 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 in the case of lauryloxyphenyltrimethyl ammonium chloride, cetylaminophenyltrimethyl ammonium methosulfate, dodecylphenyltrimethyl ammonium methos.rlfate, 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 S.benzyl ammonium halides, and the long-chain alkyl benzyl diethyl ethanol ammonium halides in which the 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 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 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 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 i, Table i, that produce consumer acceptable foam 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 00 on, but not limited to, greasy food soils, fatty food soils, and oily food soils while maintaining disinfection.

Throughout the description and claims of this specification, the word "comprise" and variations of the o* word, such as "comprising" and "comprises", is not intended to exclude other additives, components, integers or steps.

Example 1-3 30 The unexpected foaming properties of the formulations of the invention are illustrated ii these examples. The foaming properties are due to the carefully balanced mix of nonionic surfactants. The formulations of examples 1-3 are presented in Table i.

-6- Table I

INGREDIENTS

WATER, D.I DISODIUM 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

Content in the Weight Percent Example 1 Example 2 Example 3 62.95% 64.05% 61.95% 1.00% 1.00% 1.00% 4.00% 3.00% 14.00% 13.00% 13.00% 16.70% 13.60% 16.70% 3.00% 2.00% 0.35% 610 CPS 618 CPS 2.00% 2.00% 0.35% 712 CPS 728 CPS 2.00% 2.00% 0.35% 766 CPS 734 CPS r o

D

*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 100 OF before the addition of 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 ingredient in Table I is presented below in Table II.

r o o r o Table II

TRADENAME

D.I. WATER MACKAMIDE C MONAMID CMA NEODOL 25-12 NEODOL 23-6.5 MACKAM DZ (30- DISODIUM EDTA BTC 8358 (80%) CHEMICAL NAME DEIONIZED WATER COCOAMIDE DEA (cocodiethanol amide) COCOAMIDE MEA (cocomonoethanol amide)

C

13

-C

15

ALCOHOL

ETHOXYLATE

C1 2

-C

13

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

o r The good foaming capability is established by measuring foam height according to the Standard Test method for Foaming Properties of Surface-Active Aqents, 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 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 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 Example 1 Example 2 Example 3 Evaluation Minutes Minutes Minutes Modified 0 5 10 15 0 5 5 10 ASTM D1173-53 Foam Height (1:256.CM) Unloaded (cm) 15 14.5 14.5 14 15 14.5 14 14 16 15.5 15 13 Loaded (cm) 15 14.5 14 13.5 15 15 14 13 .5 15.5 15 14.5 14 Soil Titration Test Foam Performance 51 49 58 Rating, 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 nonionic compared quite favorably.

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 nDeumoniae (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 test protocol was as follows.

1. Sample Inoculation A. Inoculate 1.0 ml of the test culture into each sample tube. Repeat for organism.

B. Subculture 1.0 ml of the sample after 1minute and 1.0 ml after 5 minute contact time.

C. Subculture the sample into 9.0 ml of DIFCO AOAC Letheen Broth. This the 10-1 sample dilution.

2. Sample 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 10-1 plate.

b. Pipet and transfer 0.1 ml into 9.9 ml of Letheen Broth 10 3 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).

S 20 C. Incubate the plates for 48hr at 3. Control Counts: Dilutions and Plating A. Inoculate 1.0 ml of culture into 9.0 ml Letheen Broth.

25 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 1minute and 5-minute contact time controls.

SC. Plate the 10- 4 and 10-5 dilutions for each 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- 3 dilution 10- 4 plate.

3. Pipet 0.1 ml of the 10-3 dilution into 9.9 ml of Letheen Broth 10- 5 dilution.

4. Plate 1.0 ml of the 10-5 dilution 10-5 plate.

D. Pour the plates with Tryptic Soy Agar containing polysorbate 80 and lecithin.

E. Incubate at 35 0 C for 48hr.

4. LoO 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 petri dish. The plate is acceptable for counting with a colony count between 25 and 250.

2. Multiply the number of colonies by the plate dilution factor the number of surviving bacteria.

B. Determine the Log Reduction in bacteria for each sample/organism/contact time combination. Logl0 Control Count Logl0 Survivor Count Logs of bacteria reduced by the sample.

The results obtained are presented in Table IV.

TABLE IV PERCENT OF BACTERIAL REDUCTION AT 30 SECOND CONTACT TIME o ro e r s o s o a

MICROBIOLOGY

TEST NUMBER (Control) 1 2 3 4 7 8 9 BTC 8358 IN

FORMULA

(ACTIVE)

0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 Percent Reduction of DILUTION S. Aureus 1:256 1:256 1:256 1:256 1:256 1:256 1:256 1:256 1:256 83.1818 85.4545 87.2727 95.0909 94.1818 97.6818 99.4363 99.8772 99.992 Percent Reduction of Kleb, Pneumoniae 47.6623 77.9220 76.6233 88.9610 94.1558 97.3766 98.9090 99.7441 99.8481

Claims

1. An aqueous disinfecting liquid formulation for cleaning hard surfaces in a kitchen environment; wherein said formulation is free of anionic surfactants and consisting essentially of: a) att 0.5 to 15 weight percent of a quaternary disinfecting compound; b) 0.5 to 20 weight percent of a C12-C13 alcohol ethoxylate nonionic surfactant. c) 0.0 to 20 weight percent of a C13- alcohol ethoxylate nonionic surfactant; d) 0.5 to 20.0 weight percent of a nonionic surfactant selected from the group consisting of cocomonoethanolamide, cocodiethanolamide and combinations thereof; ee) 0.5 to 12 weight percent cocoamidopropyl betaine nonionic surfactant; o-aC 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; b) 13 to 14 weight percent of a C12-C13 .alcohol ethoxylate nonionic surfactant. c) 3.0 to 5 weight percent of a C13- alcohol ethoxylate nonionic surfactant; d) 2 weight percent of a nonionic surfactant selected from the group consisting of cocomonoethanolamide, cocodiethanolamide and combinations thereof; e) 3.0 to 9.0 weight percent cocoamidopropyl betaine nonionic surfactant; ocr f) 1.0 weight percent of the sodium salts of EDTA. I

3. The formulation of claim 1 or. 2wherein the quaternary disinfecting compound is i E 5 0% Cin, C 1 2 and 10% C 1 6 dimethyl benzyl ammonium chloride.

4. The formulation of claims 1 or 2 having a viscosity of 250 to 1000 CPS. The formulation of claims 1 or 2 having a viscosity of 250 to 800 CPS.

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

7. A formulation as claimed in claim 1 substantially as hereinbefore described with reference to any one of the examples. DATED: 10 January 1996 PHILLIPS ORMONDE FITZPATRICK Attorneys for: RECKITT colman, inc. *o 6