Description:
TECHNICAL FIELD OF THE INVENTION
The present invention relates to hard surface cleaning aqueous composition. More specifically, the present invention relates to synergistic composition offering transparent, clear, stable, antimicrobial and superior cleaning performance. Particularly, it relates to a cationic and an anionic mild surfactant, which are individually low on performance, but performing synergistically in terms of antimicrobial and cleaning property and additionally offering transparent, clear and stable formulation.

BACKGROUND AND PRIOR ART
Hard surface cleaning is one of the most important activities at various spaces like homes, offices, hotels, shopping malls and at various public places like train stations, bus stands and airports. In particular, hard surface cleaning includes cleaning hard surfaces like e.g. marble, stone, granite, tiles, glasses, pots, surfaces in a kitchen and surfaces in bathrooms by manually or by using machines like dishwash machines and washing machines. Normally, hard surfaces are cleaned by applying a hard surface cleaning composition in aqueous dilute form or neat concentrated form followed by cleaning the hard surface with a suitable means like e.g. scrub, sponge, paper, cloth, wipes and simply by using hands. These liquid compositions can be used in both the undiluted and diluted form.

Hard surfaces such as marble, stone, granite, tiles, glasses, pots, surfaces in a kitchen and surfaces in bathrooms, are usually contaminated by dust particles and also by various organic materials that contain or support the growth of various microorganisms, which require frequent cleaning and disinfection. As is known to those skilled in the art, a liquid cleanser when used on a hard surface forms films and/or streaks on the surfaces. Thus, after treatment, the formation of visible residues (streaks and/or films) can be observed. The addition of certain additives, such as antimicrobial agents, to the compositions have been also observed to increase the tendency to form films and streaks on the hard surface being treated. These films are known to reduce the shine that the surfaces normally exhibit (US7910532B2).

General purpose household cleaning compositions for hard surfaces such as metal, glass, ceramic, plastic and linoleum surfaces are commercially available in both solid powdered and liquid form. Solid powdered cleaning compositions consist mainly of builder or buffering salts such as phosphates, carbonates, and silicates and although such compositions may display good inorganic soil removal, they exhibit inferior cleaning performance on organic soils such as greasy/fatty/oily soils.

Liquid cleaning compositions, on the other hand, have the great advantage that they can be applied to hard surfaces in either diluted form or neat or concentrated form so that a relatively high level of surfactant material is delivered directly to the soil. Moreover, it is a rather more straightforward task to incorporate high concentrations of anionic or nonionic surfactant in a liquid rather than a granular composition. For both reasons, therefore, liquid cleaning compositions have the potential to provide superior removal of grease and oil from the surfaces, over powdered cleaning compositions.

There are cream/liquid products in the marketplace, such as Soft Scrub® or Comet®, which are claimed to be mild abrasive multipurpose bathroom and kitchen cleaner.

These cleaning compositions for use as hard surface cleansers are disclosed in U.S. patents/applications U.S. Nos. 20050043203, 2005043204, 20050106979, 20050148488, U.S. Pat. Nos. 6423677, 6635609, 6984269, 6936579, 6821937, and 6723692.

There is a known fact that anionic and cationic surfactants cannot be used in the same formula without loss of efficacy. On the other hand, cationic surfactants are one of the most important class of compounds used as strong antimicrobial agent. To overcome the issue, US5441541 discloses a complex formed by mixture of anionic and cationic surfactants, that is found to perform remarkably better than either the cationic or anionic surfactants from which they are formed. Similarly, US4264457A discloses a mixture of cationic-anionic surfactants having mole ratio being 0.8:1 to about 10:1. More specifically, the composition discloses C4-C10 alcohol sulfates and C12-C22 alcohol ethoxylated ether sulfates as anionic surfactants and have incorporated non-ionic surfactants to get desired properties.

US20040071653A1 discloses an antimicrobial blend of quaternary ammonium compound and an anionic surfactant. Moreover, antimicrobial blend further comprises bridging surfactants of the groups of amine oxides, ethoxamides, and betaines for attaining the desired properties. In the similar line WO2023062360A1 also discloses antimicrobial composition comprising mixture of quaternary ammonium compounds, non-ionic or amphoteric or anionic surfactants, and organosilanes. However, the composition is used for treating and/or preventing skin and/or wound infections and not specifically in hard surface cleaning.

Recently, US20240052277A1 demonstrated the use of Benzalkonium chloride (BKC) as a cationic surfactant in hard surface cleaning. According to US20240052277A1, if Benzalkonium chloride is mixed with anionic surfactants (e.g. alpha olefin sulphonate), the surfactants would come out of solution (i.e. precipitate), thus rendering them ineffective and reduction in stability and performance. So, to overcome the issue US20240052277A1 prepared hard surface cleaning composition of Benzalkonium chloride by excluding anionic surfactants.

Moreover, US5441541 mentioned that most of the anionic/cationic surfactant mixtures studied in the prior arts are insoluble or only slightly soluble. Therefore, their practical use is very limited in areas where high concentration of surfactants is needed.

Furthermore, WO2023180053A1 publication also discloses Benzalkonium chloride based hard surface cleaning composition, however the composition comprises sulphate based anionic surfactants and are solid in nature. So, composition requires an extra time for dissolution compared to liquid compositions which can be used directly.

WO2023213522A1 discloses use of amino acid surfactants for preparing hard surface cleaning composition. Similarly, US6667289B2 discloses aqueous hard cleaning and disinfecting spray formats based on quaternary ammonium surfactant, amino oxide, N-acyl amino acid surfactants (especially sarcosinate), alkylene glycol ether solvents and alkylating agents. However, they have not specifically demonstrated stability and cleansing efficacy performance. Moreover, composition utilized hazardous organic solvents in the composition.

It is always desired by the consumer that the cleaning products are formulated with mild cleansing systems which are not considered harsh i.e. are mild on skin and have acceptable sensory properties like having no unpleasant chlorine smell. The generation of foam is desired as an indicator to the user of the cleaning action of the composition and high levels of foam may be associated by the user with cleaning performance of the composition. Anionic surfactants (e.g. SLS) are more preferred to achieve best cleaning performances, while cationic surfactant (e.g. BKC) is necessary to achieve best antimicrobial property. When both anionic surfactants (e.g. SLS) and cationic surfactants (e.g. BKC) are mixed both specifically at equal ratios, they form unstable complexes which lead to precipitation and there is loss of efficiency of both surfactants. Moreover, use of overdose of surfactant systems for better performance and for stability of composition, increase the cost of formula and it is not preferred.

Considering all above-mentioned problems, there is a need to solve the solubility and instability issue in the composition with quaternary ammonium compounds and anionic surfactants to formulate a composition which can simultaneously provide milder, transparent, clear, stable, antimicrobial and superior cleaning performance and are based on optimum / synergistic concentrations of quaternary ammonium compounds and anionic surfactants preferably having 1:1 ratio on wt% active basis.

OBJECTIVES OF THE INVENTION

i. It is an objective of the present invention to provide an aqueous, transparent, clear, thermostable cleaning composition with 1:1 ratio of anionic & cationic surfactants together to achieve 99.99% germ kill with superior cleaning for home care products such as floor cleaner.

ii. It is another objective of the present invention to provide a stable, homogeneous aqueous composition with BKC as cationic surfactant which effectively delivers best germ kill property (> 99%)

iii. It is another objective of the present invention to provide floor cleaner formulations with the combination of anionic surfactants which are compatible with cationic surfactants.

iv. It is another objective of the present invention to provide a hard surface cleaner system which is stable transparent, and clear at 5 deg. C to 50 deg. C

v. It is another objective of the present invention to provide a hard surface / floor cleaning composition to offer superior results compared to high active formula.

vi. It is another objective of the present invention to provide effective cleaning without compromising cationic activity in presence of mild anionic surfactant in the formula.

SUMMARY OF THE INVENTION
It is an aspect of the present invention to provide a clear transparent and stable aqueous cleaning composition comprising: a) from 0.0075 wt % to 50 wt % of a quaternary ammonium compound; b) from 0.0075 wt % to 19 wt% of N-acyl amino acid surfactants; and c) from 0.001 wt % to 10 wt% fatty alcohol ethoxylates;
wherein the composition synergistically provides antimicrobial property and cleaning performance on applying to a hard surface; and wherein the active content weight ratio of the quaternary ammonium compound to N-acyl amino acid surfactant ranges from 1:2 to 2:1.

BRIEF DESCRIPTION OF THE FIGURES
The patent or application file contains following figures for demonstration of the invention. So that those having ordinary skill in the art will have a better understanding of how to make and use the disclosed process and methods:

Figure 1: Germ kill performance of formulations/ compositions containing 1: 1 of anionic and anionic surfactants (2 wt% active basis for both).

Figure 2: Germ kill performance of formulations/ compositions containing 1: 2 of anionic and anionic surfactants (2 wt% and 4 wt% on active basis for anionic and cationic respectively).

Figure 3: Germ kill performance of formulations/ compositions containing 2: 1 of anionic and anionic surfactants (4 wt% and 2 wt% on active basis for anionic and cationic respectively).

Figure 4 Cleaning performance on marble floor: A) Using 2 wt% SLS based Floor cleaner (15 ml) B) Using 2 wt% SLG based Floor cleaner (15 ml)

Figure 5 : Cleaning performance of floor cleaner on marble tile as per protocol (lower the strokes, better the performance)

DETAILED DESCRIPTION OF THE INVENTION
The present invention provides stable aqueous composition of anionic and cationic surfactant mixtures. The present invention relates to a composition comprising a quaternary ammonium compound and an anionic surfactant, and is a transparent, clear, aqueous, thermostable composition which provides 99.99% germ kill antimicrobial property and excellent cleaning performance during hard surface cleanings without separation of active, reduction of cationic activity, or precipitation, and having superior performance and mild to hard surface and to the skin of the consumer.

Generally, cationic surfactants induce germ-kill capacity while anionic surfactants are mostly involved in cleaning performance. The present invention is based on cationic and anionic surfactants, which generally interact with each other and reduces/neutralizes the individual properties of both types of surfactants. Consequently, there is a general notion that anionic and cationic surfactants cannot be used in the same formula without loss of efficacy.

This invention overcomes above mentioned drawbacks and offers clear, aqueous, thermostable composition which simultaneously delivers superior antimicrobial property and excellent cleansing performance by using a cationic surfactant such as most preferred benzalkonium chloride and a mild anionic surfactant such as most preferred sodium lauryl glycinate. The composition does not include any other cationic or anionic surfactant to support said performance, however, one can use any other cationic or anionic surfactant if further required.

The following detailed description of the invention is merely exemplary in nature and is not intended to limit the invention or the ingredient ranges or the formulations/compositions ranges and uses of the invention. Furthermore, there is no intention to be bound by any theory presented in the preceding background of the invention or the following detailed description of the invention.

DEFINITIONS
The term, ‘hard surface’, refers to materials that are partially resistance to penetration by objects and usually do not absorb liquids readily that are found in both households and industry. Examples are marble; stone; granite; tiles; glass; pots, both ceramic and metallic; sinks, both porcelain and metal; porcelain; kitchen appliances including glass cook tops.

Term ‘quaternary ammonium compound’ refers to quaternized nitrogenous compounds as follow: Benzalkonium chloride, didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium saccharinate, octyl decyl dimethyl ammonium chloride, alkyl dimethyl ethyl benzyl ammonium chloride, methyldodecylbenzyl ammonium chloride, methyldodecylxylene-bis-trimethyl ammonium chloride, methyl benzethonium chloride, cetyl pyrinidinium chloride, cetrimonium bromide

Term ‘amino acid surfactants’ refers to N-acylate amino acid-based compounds such as sodium cocoyl glycinate, sodium lauroyl glycinate, potassium cocoyl glycinate, potassium lauroyl glycinate, sodium cocoyl glutamate, sodium lauroyl glutamate, sodium lauroyl sarcosinate, sodium cocoyl taurate.

Term “w/w” means, weight of molecule, including water and other ingredients or impurities or content of respective molecule.

Term “wt %” is actual weight of respective molecule or actual activity of molecule or active content or active matter or activity or purity of the molecule.

The present invention provides a clear transparent and stable aqueous cleaning composition comprising:
a) from 0.0075 wt % to 50 wt % of a quaternary ammonium compound;
b) from 0.0075 wt % to 19 wt% of N-acyl amino acid surfactants; and
c) from 0.001 wt % to 10 wt% fatty alcohol ethoxylates;
wherein the composition synergistically provides antimicrobial property and cleaning performance on applying to a hard surface; and
wherein the active content weight ratio of the quaternary ammonium compound to N-acyl amino acid surfactant ranges from 1:2 to 2:1.

In a preferred embodiment, the active content weight ratio of the quaternary ammonium compound to the N-acyl amino acids is 1:1.

In a preferred embodiment, the quaternary ammonium compound is present in an amount from 1 to 5 wt% by weight of the composition.

In a preferred embodiment, the N-acyl amino acid surfactant is present in an amount of preferably from 1 to 5 wt% by weight of the composition.

In an embodiment, the quaternary ammonium compound is selected from a group of alkyl dimethyl benzyl ammonium chloride, diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, methyl benzethonium chloride, cetyl pyrinidinium chloride, cetrimonium bromide or mixtures thereof. In a preferred embodiment, the quaternary ammonium compound is benzalkonium chloride.

In an embodiment, the N-acyl amino acid surfactant is selected from a group of sodium cocoyl glycinate, sodium lauroyl glycinate, potassium cocoyl glycinate, potassium lauroyl glycinate, sodium cocoyl glutamate, sodium lauroyl glutamate, sodium lauroyl sarcosinate, sodium cocoyl taurate or mixtures thereof. In a preferred embodiment, the N-acyl amino acid surfactant is sodium lauroyl glycinate.

The cleaning composition as provided herein comprises a non-ionic surfactant such as fatty alcohol ethoxylates to act as an emulsifier and secondary surfactant in the formulation. The fatty alcohol ethoxylates is added to also avoid forming very high concentrated surfactant mixture of cationic-anionic mixture. The fatty alcohol ethoxylates does not contribute to the germ-killing but may add to the cleaning performance only when it uses at very high concentration. , so not effectively contributing to the desired properties as per the objective of the invention. Moreover, the non-ionic surfactants did not contribute to synergistic effect of simultaneous germ-killing and cleaning performance of the formulation.

The cleaning composition as described herein shows synergistic cleaning performance on applying to a hard surface. The hard surface is selected from the group consisting of marble, stone, granite, tiles, glasses, pots, kitchen platforms and bathroom surfaces.

In an embodiment, the cleaning composition is formulated in a home cleaning liquid formulation selected from the groups of floor cleaning liquid, glass cleaning liquid, and kitchen surface cleaning liquid.

The cleaning composition is stable from 5 deg. C to 50 deg. C.

The cleaning composition also exhibits antimicrobial property. The germ-killing capability is measured in accordance with EN 1276; such that the log reduction value of Staphylococcus aureus ATCC 6538, and/or Escherichia coli ATCC 8739 and/or Pseudomonas aeruginosa ATCC 15442 is at least 90% (1 log), more preferably at least 99% (2 log), most preferably at least 99.9% (3 log).

Table 2 to 4 demonstrated different formulation examples with varying ratios of cationic and anionic surfactants. These tables provide the systematic details of stability, viscosity, pH, %cationic activity, and germ-killing data of the respective formulations.

Specifically, table 2 to 4 shows data after 30 days at respective temperatures. It was observed that the recorded data at 1st day and at 30th day remained the same. More specifically, table 2 to 4 demonstrating formulations having BKC as a cationic active surfactant. Moreover, table 2 to 4 formulations examples consisting various anionic surfactants, as mentioned in table 1.

It was observed that among all the selected anionic surfactants, the formulations having SLS as anionic surfactant seems to be unstable resulting into separation and settling of precipitate. It was also observed that SLS based formulations either did not show any %cationic activity or showed very little %cationic activity during titration test. This strongly suggested that SLS forms unstable complex with BKC and hence there is no further availability of cationic surfactant in the formulation. This also leads to decrease in germ kill performance of formulation too. On the other hand, formulation containing amino acid based anionic surfactants showed better performance in terms of stability and germ-killing capacity. Higher the log reduction better the germ kill effect

ADVANTAGES OF THE INVENTION

1) It is an advantage of the present invention to provide aqueous cleaning composition/ formulation offering synergistic germ-killing efficiency at 1:1 ratio of anionic & cationic surfactants.
2) Another advantage of present invention is to provide transparent, clear, and thermostable cleaning composition/ formulation for home care products.
3) Another advantage of the present invention is usability of broad concentration range of ingredients (cationic and anionic surfactants) in composition/ formulation.
4) Another advantage of present invention is the applicability of the compositions/ formulations from concentrated to dilute form.

Examples

Materials and Method
Ingredients specification and their active ingredient/ wt % / activity is as follows :

Table 1: List of surfactants and their details
Trade name INCI name wt % or % active basis
Galaxy BKC Benzalkonium chloride 80
Galsoft SCG Sodium Cocoyl Glycinate 24
Galsoft SLG Sodium Lauroyl Glycinate 20
Galsoft KCG Potassium Cocoyl Glycinate 24
Galsoft KLG Potassium Lauroyl Glycinate 20
Galsoft NaLS Sodium Lauroyl Sarcosinate 30
Galsoft SCGL Sodium Cocoyl glutamate 30
Galsoft SLGL Sodium Lauroyl Glutamate 20
Galsoft SCT Sodium Cocoyl Taurate 32
GalEcocare 165 Decyl Glucoside 50
Galaxy SLS Sodium Lauryl Sulfate 29
Galaxy MW 259 9 mole laureth ethoxylate 100

Formulations were prepared by considering w/w of each ingredient, however different purity grades of the surfactants are available so, wt% of each ingredient was considered to make formulations with 1:1 in table 2, 1:2 in table 3, and 2:1 in table 4.

pH of formulation was measured by using pH electrode and formulation was tested (without dilution) accordingly.

Viscosity and appearance of each formulation were observed after 24 hrs and further with intervals of after every 7 days till 30 days.

EXAMPLE 1 Formulations/compositions with 1:1 (Anionic : Cationic surfactants, at ratio on active basis) and corresponding stability and germ kill capacity evaluations:

Formulations/ compositions with 1:1 ratio of anionic surfactants and cationic surfactants were prepared and evaluated their corresponding stability, viscosity, pH, %cationic activity, and germ-killing capacities. Table 2 provides data for the formulations containing anionic and cationic at 1:1 ratio (active basis). It was observed that among all the selected anionic surfactants, the formulations having SLS as anionic surfactant (Exp. 8) seems to be unstable resulted into separation and settling of precipitate. Similarly, it was also observed that SLS based formulations did not show any %cationic activity during titration test. This also lead to decrease in germ kill performance of formulation. On the other hand, formulation containing amino acid based anionic surfactants showed better stabilities and showed % cationic activity leading to better germ-killing capacity. Surprisingly it was observed that Galsoft SCG (Exp.1) and Galsoft SLG (Exp.2) based formulations showed significantly higher germ kill performance compared to others.

TABLE 2 Formulations with 1:1 of Anionic : Cationic ratio on active basis (2wt% : 2wt%)

Ingredient / w/w Exp.1 Exp.2 Exp.3 Exp.4 Exp.5 Exp.6 Exp.7 Exp.8
Galaxy BKC AT 2.49 2.49 2.49 2.49 2.49 2.49 2.49 2.49
Galsoft SCG 8.21 0 0 0 0 0 0 0
Galsoft SLG 0 9.66 0 0 0 0 0 0
Galsoft NaLS 0 0 6.63 0 0 0 0 0
Galsoft SCGL 0 0 0 6.57 0 0 0 0
Galsoft SLGL 0 0 0 0 9.92 0 0 0
Galsoft SCT 0 0 0 0 0 6.33 0 0
Ecocare 165 0 0 0 0 0 0 4 0
Galaxy SLS 0 0 0 0 0 0 0 6.85
Galaxy MW 259 1.30 1.30 1.30 1.30 1.30 1.30 1.30 1.30
D.M.water q.s. to 100 q.s. to 100 q.s. to 100 q.s. to 100 q.s. to 100 q.s. to 100 q.s. to 100 q.s. to 100
Tests
pH as is 9.2 10 7.9 10.3 9.9 9.3 10.6 10.5
Viscosity at 25 deg. C , Cp < 50 cps < 50 cps < 50 cps < 50 cps < 50 cps < 50 cps < 50 cps < 50 cps
% cationic activity 2.00 2.10 2.16 2.17 2.11 0 2.13 0
Germ kill @ 5 min./ Log reduction 99.99 99.99 99 90 99 99 99 <90
Appearance at 25 deg. C after 24 hrs Transparent clear solution Transparent clear solution Transparent clear solution Transparent clear solution Transparent clear solution Transparent clear solution Transparent clear solution ppt and separated solution
Stability data on 30th day
Stability at 5 deg. C Stable Stable Stable Stable Stable Stable Stable Not stable
Stability at 25 deg. C Stable Stable Stable Stable Stable Stable Stable Not stable
Stability at 40 deg. C Stable Stable Stable Stable Stable Stable Stable Not stable
Stability at 50 deg. C Stable Stable Stable Stable Stable Stable Stable Not stable

Note: Ingredients weights are in ‘gm’ and is calculated based on 2 wt% active basis for all the surfactants .

EXAMPLE 2 Formulations/compositions with 1:2 (Anionic : Cationic surfactants, at ratio on active basis) and corresponding stability and germ kill capacity evaluations:

Formulations/ compositions with 1:2 ratio of anionic surfactants and cationic surfactants were prepared and evaluated their corresponding stability, viscosity, pH, %cationic activity, and germ-killing capacities. Table 3 provides data for the formulations containing anionic and cationic at 1:2 ratio (active basis). Here formulations have higher cationic surfactant (e.g. BKC) concentration compared to anionic surfactants. It was expected that these formulations will perform better in terms of germ-killing capacity compared than Table 2 due more availability of unreacted cationic surfactants. It was observed that among all the selected anionic surfactants, the formulations having SLS as anionic surfactant (Exp. 16) seems to be unstable resulted into separation and settling of precipitate. Similarly, it was also observed that SLS based formulations showed low %cationic activity during titration test. This also led to lower germ kill capacity of the formulation. On the other hand, formulation containing amino acid based anionic surfactants showed better stabilities and showed better %cationic activity leading to better germ-killing capacity. Surprisingly, it was observed that Galsoft SCG (Exp.9), Galsoft SLG (Exp. 10), and Galsoft SCT (Exp.14) based formulations showed significantly higher germ kill performance compared to others.

TABLE 3 Formulations with 1:2 of Anionic : Cationic ratio on active basis (2wt% : 4wt%)

Ingredient / w/w Exp.9 Exp.10 Exp.11 Exp.12 Exp.13 Exp.14 Exp.15 Exp.16
Galaxy BKC AT 4.97 4.97 4.97 4.97 4.97 4.97 4.97 4.97
Galsoft SCG 8.21 0 0 0 0 0 0 0
Galsoft SLG 0 9.66 0 0 0 0 0 0
Galsoft NaLS 0 0 6.63 0 0 0 0 0
Galsoft SCGL 0 0 0 6.57 0 0 0 0
Galsoft SLGL 0 0 0 0 9.92 0 0 0
Galsoft SCT 0 0 0 0 0 6.33 0 0
Ecocare 165 0 0 0 0 0 0 4 0
Galaxy SLS 0 0 0 0 0 0 0 6.85
Galaxy MW 259 2 2 2 2 2 2 2 2
D.M.water q.s. to 100 q.s. to 100 q.s. to 100 q.s. to 100 q.s. to 100 q.s. to 100 q.s. to 100 q.s. to 100
Tests
pH as is 8.99 9.95 7.36 10.34 9.88 9.657 10.548 9.671
Viscosity at 25 deg. C , Cp < 50 cps < 50 cps < 50 cps < 50 cps < 50 cps < 50 cps < 50 cps < 50 cps
% cationic activity 4.33 4.33 4.3 4.34 4.3 2.14 4.11 1.76
Germ kill @ 5 min./ Log reduction 99.999 99.999 99.9 99.9 99.9 99.999 99.999 99
Appearance at 25 deg. C after 24 hrs Transparent clear solution Transparent clear solution Transparent clear solution Transparent clear solution Transparent clear solution Transparent clear solution Transparent clear solution ppt and separated solution
Stability data on 30th day
Stability at 5 deg. C Stable Stable Stable Stable Stable Stable Stable Not stable
Stability at 25 deg. C Stable Stable Stable Stable Stable Stable Stable Not stable
Stability at 40 deg. C Stable Stable Stable Stable Stable Stable Stable Not stable
Stability at 50 deg. C Stable Stable Stable Stable Stable Stable Stable Not stable

Note: Ingredients weights are in ‘gm’ and is calculated based on 2 wt% active basis for anionic/ non-ionic surfactants and 4 wt% active basis for cationic surfactant.

EXAMPLE 3 Formulations/compositions with 2:1 (Anionic : Cationic surfactants, at ratio on active basis) and corresponding stability and germ kill capacity evaluations:

Formulations/ compositions with 2:1 ratio of anionic surfactants and cationic surfactants were prepared and evaluated their corresponding stability, viscosity, pH, %cationic activity, and germ-killing capacities. Table 4 provides data for the formulations containing anionic and cationic at 2:1 ratio (active basis). Here formulations have lower cationic surfactant (e.g. BKC) concentration compared to anionic surfactants. It was expected that these formulations will show low germ-killing capacity compared than tables 2 and 3 due very low availability of unreacted cationic surfactants. It was observed that among all the selected anionic surfactants, the formulations having SLS as anionic surfactant (Exp. 24) seems to be unstable resulted into separation and settling of precipitate. Similarly, it was also observed that SLS based formulations did not show any %cationic activity during titration test. This also led to lower germ kill capacity of the formulation. On the other hand, formulation containing amino acid based anionic surfactants showed better stabilities and showed better %cationic activity leading to better germ-killing capacity. Surprisingly, it was observed that Galsoft SLG (Exp. 18) and Galsoft NaLS (Exp.19) based formulations showed significantly higher germ kill performance compared to others.

TABLE 4 Formulations with 2:1 of Anionic : Cationic ratio on active basis (4wt% : 2wt%)
Ingredient / w/w Exp.17 Exp.18 Exp.19 Exp.20 Exp.21 Exp.22 Exp.23 Exp.24
Galaxy BKC AT 2.49 2.49 2.49 2.49 2.49 2.49 2.49 2.49
Galsoft SCG 16.42 0 0 0 0 0 0 0
Galsoft SLG 0 19.32 0 0 0 0 0 0
Galsoft NaLS 0 0 13.27 0 0 0 0 0
Galsoft SCGL 0 0 0 13.14 0 0 0 0
Galsoft SLGL 0 0 0 0 19.83 0 0 0
Galsoft SCT 0 0 0 0 0 12.66 0 0
Ecocare 165 0 0 0 0 0 0 8.00 0
Galaxy SLS 0 0 0 0 0 0 0 13.7
Galaxy MW 259 2 2 2 2 2 2 2 2
D.M.water q.s. to 100 q.s. to 100 q.s. to 100 q.s. to 100 q.s. to 100 q.s. to 100 q.s. to 100 q.s. to 100
Tests
pH as is 9.5 10 8 10.6 9.9 10 11 11
Viscosity at 25 deg. C , Cp < 50 cps < 50 cps < 50 cps < 50 cps < 50 cps < 50 cps < 50 cps < 50 cps
% cationic activity 2.09 2.08 2.12 2.06 2.05 0 2.04 0
Germ kill @ 5 min./ Log reduction 90 99 99 90 90 90 <90 <90
Appearance at 25 deg. C after 24 hrs Transparent clear solution Transparent clear solution Transparent clear solution Transparent clear solution Transparent clear solution Transparent clear solution Transparent clear solution ppt and separated solution
Stability data on 30th day
Stability at 5 deg. C Stable Stable Stable Stable Stable Stable Stable Not stable
Stability at 25 deg. C Stable Stable Stable Stable Stable Stable Stable Not stable
Stability at 40 deg. C Stable Stable Stable Stable Stable Stable Stable Not stable
Stability at 50 deg. C Stable Stable Stable Stable Stable Stable Stable Not stable

Note: Ingredients weights are in ‘gm’ and is calculated based on 4 wt% active basis for anionic/ non-ionic surfactants and 2 wt% active basis for cationic surfactant.

From above examples 1-3 and corresponding experiments 1-24, it can be concluded that formulations/ compositions based on cationic surfactant (BKC) and anionic surfactants (N-acyl amino acid surfactants) showed better stability and germ-killing capacity than corresponding SLS based compositions/ formulations. More specifically, composition/ formulation based on Galsoft SLG showed synergistic effect which led to significantly better germ-kill efficiency and stability compared to other amino acid-based surfactants.

EXAMPLE 4 Germ kill evaluations of varying active concentrations at constant 1:1 (Anionic : Cationic surfactants) ratio.

Table 5: Formulations with varying concentrations of SLG:BKC at 1:1 wt%

Sr. No. Ingredients Exp. 25 Exp. 26 Exp. 27
gm % wt gm % wt gm % wt
1 Galsoft SLG 0.0375 0.0075 35.00 7.00 70.00 14.00
2 Galaxy BKC 0.0094 0.0075 8.75 7.00 17.50 14.00
3 Galaxy MW 259 0.0010 0.001 5.00 5.00 10.00 10.00
4 Water 99.953 - 51.25 2.50
Tests Appearance at 25 deg. C after 24 hrs Transparent clear solution Transparent clear solution Transparent clear solution
pH as is at 25 deg. 7 to 8 9 to 10 9 to 10
Viscosity at 25 deg. C , Cp < 50 cps < 100 cps < 200 cps
% Cationic activity 0.0075 7.00 14.00
Germ kill @ 5 min./ Log reduction 99.99 99.999 99.999

Table 5 demonstrated varying concentrations of both SLG and BKC by maintaining 1:1 on the basis of active wt% and as in weight basis which is w/w in gm.
Exp. 25 is ready to use spray format (can be used as glass cleaner) and Exp no. 26 and 27 are concentrated formulations for hard surface cleaner. These can be diluted as per recommended or standard dilutions and then shall apply on hard surface to achieve desired performance. All samples from exp. 25, 26 and 27 delivered desired cleaning performance on tile with recommended dilutions. Hence it is very much feasible to prepare lower and higher concentrate formulations as per requirement with 1:1 ratio of anionic: cationic.

EXAMPLE 5 Germ kill evaluations of varying active concentrations at varying ratios.

Table 6: Formulations with varying concentrations of SLG/KLG:BKC and SCG/KCG:BKC at different ratios

Sr. No. Ingredient Exp. 28 Exp. 29 Exp. 30 Exp. 31 Exp. 32 Exp. 33 Exp. 34
gm % wt gm % wt gm % wt gm % wt gm % wt gm % wt gm % wt
1 Galsoft SLG 32.50 6.5 90 18 80 16 0 0 0 0 0 0 0 0
2 Galsoft SCG 0 0 0 0 0 0 66.66 16 0.0315 0.0075 0 0 0 0
3 Galsoft KLG 0 0 0 0 0 0 0 0 0 0 0.0375 0.0075 0 0
4 Galsoft KCG 0 0 0 0 0 0 0 0 0 0 0 0 0.0315 0.0075
5 Galaxy BKC 62.50 50 5 4 20 16 20.00 16 0.0094 0.0075 0.0094 0.0075 0.0094 0.0075
6 Galaxy MW 259 5.00 5 5 5 0 0 0.001 0.001 0.001 0.001 0.001 0.001
7 Water 0.00 0.00 0.00 13.34 99.67 99.67 99.67
Tests Appearance at 25 deg. C after 24 hrs Transparent clear solution Transparent clear solution Transparent clear solution Transparent clear solution Transparent clear solution Transparent clear solution Transparent clear solution
pH as is at 25 deg. 10 10.2 10.13 10.13 7 to 8 7 to 8 7 to 8
Viscosity at 25 deg. C , Cp < 200 < 1000 < 150 < 150 < 100 < 100 < 100
% Cationic activity ~50 ~4 ~16 ~16 ~0.0075 ~0.0075 ~0.0075
Germ kill @ 5 min. % 99.999 < 90 99.999 99.99 99.9 99.9 99.9

Table 6 illustrates varying concentrations of both SLG and SCG with BKC on the basis of active wt%.

Formulation of exp. 28 is with comparatively high BKC (cationic) concentration, formulation of exp. 29 is with high concentration of SLG and formulation exp. 30 is with equal concentration of BKC and SLG. Both formulations of exp. 28 and exp. 30 showed significantly better germ-killing efficiency while formulation of exp. 29 showed low germ-killing efficiency. Significant variations in the viscosity were observed in exp 29 compared to exp. 28 and exp. 30, however cleaning performance was found to be acceptable range. Formulations of exp. 31 and exp. 32 are based on SCG and BKC at 1:1 ratio but have variations in the concentration ranges. Viscosity of both formulations were less than 200 cps at 25 deg. C while germ-killing efficiency of exp. 32 was found to be slightly less than exp. 31.

Exp. 33 and exp. 34 demonstrated the use of KLG and KCG in the formulations along with BKC. Both the formulations were found to be clear and transparent and having good germ-killing capacity. It can be suggested that even with potassium salt of N-acyl amino acid surfactants showed clear and stable formula.

GERM KILL EVALUATIONS: Antimicrobial effect by Time Kill Method
Test Protocol:
• Sample dilution: 15ml in 4 liters
• Method details: Time Kill study is used for assessment of antimicrobial activity of the test sample for its application as floor cleaner. In this study the sample is inoculated with the known concentration of test organism and reduction in count or organisms with respect time is studied.
Common methods of measuring germ kill include the following test protocols: EN1276, AOAC 955.14; 955.15; 964.02 Usage Dilution Test and ASTM 2274. So, aaccordingly germ killing capability is measured in accordance with EN 1276.

• Diluent and Media: Sterile TAT broth, Sterile Neutralizing Broth, Sterile Molten modified Lethean Agar and Distilled Water
• Test organism Used and Preparation of the Inoculum.
Mix Culture Inoculum level: Mix Culture 1 × 108 -1 ×109 cfu/ml
Initial inoculum 2.20 x 109
Sr. No. Culture Name Suitable medium Incubation temp. Incubation Time
1 Staphylococcus aureus ATCC 6538 TAT Broth 30-3 ⁰C 24 hrs.
2 Escherichia coli ATCC 8739 TAT Broth 30-3 ⁰C 24 hrs.
3 Pseudomonas aeruginosa ATCC 15442 TAT Broth 30-3 ⁰C 24 hrs.

• Acceptance Criteria: - 3 Log reduction in 05mins corresponds to 99.9% germ kill

Figure 1 demonstrating germ kill efficiency data of formulations containing anionic and cationic surfactants having active w/w concentration as1:1 based on active wt% of respective surfactants. Figure 1 clearly shows that SLG and SCG based formulations provide 99.999% germ kill efficacy. On the other hand, SLS and SCGL based formulations showed 99.9%. This may be due to loss of activity of due to formation of unstable complexes during interactions with BKC.

The figures 2 and 3 describe that the formulations/ compositions based on amino acid based surfactants showed better germ kill efficacy compared to Galaxy SLS. More specifically, formulations/ compositions based on Galsoft SLG showed synergism and provided significantly better germ kill capacity in all the proportions compared to other amino acid based surfactants. Also it was observed that non ionic surfactant, such as Ecocare 165 also did not show any synergism with BKC. Moreover, Galaxy SLS has shown poor performance due to formation of unstable complex with BKC. Hence, less active wt% of respective surfactants are available to show their performance of germ-killing capacity and cleaning performance.

It is reported that synergism in terms of critical micelle concentration, surface tension, and microemulsion behavior between anionic and anionic or nonionic and nonionic is less than anionic and nonionic or cationic and nonionic which in turn are much less than those of anionic and cationic mixtures (Rosen et al. in "Phenomena in Mixed Surfactant Systems" (Scamehorn, J. F., ed.), ACS Symposium Series 311, Washington, D.C. (1986), pp. 144-1621 and Zhao et al. in "Phenomena in Mixed Surfactant Systems" (Scamehorn, J. F., ed.) ACS Symposium Series 311, Washington, D.C. (1986) pp. 184-198). However, the synergism restricted to cleaning efficiency on fabrics only.

When BKC used greater than anionic surfactant content (Figure 2), it was expected to observe better germ kill capacity of > 99% and the observations are in-line as expected. However in case of SLS based formulation, the germ killing capacity is lower than expected. On the other hand, when BKC is used in lower ratio compared to anionic surfactants(Figure 3), it was expected to observe lower germ kill capacity of < 99%. However, better germ killing efficiency was observed in case of amino acid based formulations. Moreover, it surprisingly observed that at 1:1 ratio, SLG i.e. anionic surfactant did not show unstable interaction with BKC i.e. cationic surfactant, and hence performed best among all amino acid based surfactants (Figure 1). So, it can be concluded that at 1:1 of SLG and BKC, synergy was observed for germ killing capacity.

EXAMPLE 6 Cleaning performance of formulations/compositions:

Study : CLEANING PERFORMANACE OF FORMULATION
Test Protocol:
• Instrument: Wet abrasion tester
• Tile: 10 x 10 cm2 Marble tile, Porcelain tile
• Scrub/ Sponge: Cellulose Sponge / Brush provided with Instrument
• Soil g/tile: 2 gm.
• Sample Qty: 5ml and 15 ml
• Stroke: 5 to 10
• RPM: 25
• Temperature: 25 deg. C
• Soil component: Calcium stearate, Turpentine, Lanolin, Grease, Carbon black.
• Procedure: Take 5 ml or 15 ml of the floor cleaner samples and directly add on the soiled tile. Set the wet abrasion tester for 25 rpm, 5 STROKEs and continue to 10 strokes if required further.

Figure 4 shows comparative cleaning efficiency of floor cleaning composition using 15 mL solution based on 2 wt% SLS and 2wt% SLG (active contents each). It was observed that SLG based composition provided better cleaning performance and with a smaller number of strokes too.

Figure 5 demonstrates comparative cleaning performance on marble tiles. Compositions used for this study were selected form table 2, where cationic:anionic is present at 1:1 ratio and having 2 wt% each (based on active content). The performance was measured using concentrations of 5 mL and 15 mL. As expected, it was observed that 5mL concentrated solution required higher number of strokes to clean the marble tiles compared to 15 mL concentrated solution in most of the compositions. However, formulations based on SLG:BKC and NaLS:BKC showed cleaning efficiency at only 1 stroke. These results clearly indicate that SLG based formulation performs better even at lower concentration. Moreover, 100% cleaning was observed without dragging and only after 1 stroke as showed in Table 7. Comparative visual observations for 5 mL and 15 mL formulations is provided in Table 7.

Table 7: Comparative visual observation of cleaning performance of formulations on tiles

Sr. No. Aqueous Floor cleaner 5 ml neat sample run on tile 15 ml neat sample run on tile
2:2 wt% 5 ml 15 ml
1 SCG:BKC 100% cleaning after 2 strokes without dragging 100% cleaning after 1 stroke without dragging
2 SLG:BKC 100% cleaning after 1 stroke without dragging 100% cleaning at 2 strokes without dragging
3 NaLS:BKC 100% cleaning after 1 stroke without dragging 100% cleaning after 1 stroke without dragging
4 SCGL:BKC Not clean properly at the up to 5 strokes without dragging Not properly Clean at 3 strokes without dragging
5 SLGL:BKC Not clean Properly Not clean Properly
6 SCT:BKC 100% cleaning after 1 stroke without dragging 100% Cleaning at 1 stroke without drag
7 APG:BKC 100% Cleaning after 3 strokes without drag 100% Cleaning after 1 stroke without drag
8 SLS:BKC Clean after 10 strokes and slightly drag Not Properly Clean after 5 strokes and slightly drag

, Claims:
1. A clear transparent and stable aqueous cleaning composition comprising:
a) from 0.0075 wt % to 50 wt % of a quaternary ammonium compound;
b) from 0.0075 wt % to 19 wt% of N-acyl amino acid surfactants; and
c) from 0.001 wt % to 10 wt% fatty alcohol ethoxylates;
wherein the composition synergistically provides antimicrobial property and cleaning performance on applying to a hard surface; and
wherein the active content weight ratio of the quaternary ammonium compound to N-acyl amino acid surfactant ranges from 1:2 to 2:1.

2. The composition according to claim 1, wherein the active content weight ratio of the quaternary ammonium compound to the N-acyl amino acids is most preferably at 1:1.

3. The composition according to claim 1, wherein the quaternary ammonium compound is selected from a group of alkyl dimethyl benzyl ammonium chloride, diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, methyl benzethonium chloride, cetyl pyrinidinium chloride, cetrimonium bromide or mixtures thereof, preferably benzalkonium chloride.

4. The composition according to claim 1, wherein the N-acyl amino acid surfactants is selected from a group of sodium cocoyl glycinate, sodium lauroyl glycinate, potassium cocoyl glycinate, potassium lauroyl glycinate, sodium cocoyl glutamate, sodium lauroyl glutamate, sodium lauroyl sarcosinate, sodium cocoyl taurate or mixtures thereof, preferably sodium lauroyl glycinate.

5. The composition according to claim 1, wherein the quaternary ammonium compound is present in an amount of preferably from 1 to 5 wt% by weight of the composition.

6. The composition according to claim 1, wherein the N-acyl amino acid surfactant is present in an amount of preferably from 1 to 5 wt% by weight of the composition.

7. The composition according to according to claim 1, wherein the hard surface is selected from the group consisting of marble, stone, granite, tiles, glasses, pots, kitchen platforms and bathroom surfaces.

8. The composition according to claim 1, wherein the composition is stable from 5 deg. C to 50 deg. C.

9. The composition according to claim 1, wherein germ-killing capability is measured in accordance with EN 1276 such that the log reduction value of Staphylococcus aureus ATCC 6538, and/or Escherichia coli ATCC 8739 and/or Pseudomonas aeruginosa ATCC 15442 is at least 90% (1 log), more preferably at least 99% (2 log), most preferably at least 99.9% (3 log).

10. The composition according to claim 1, wherein the composition is formulated in a home cleaning liquid formulation selected from the groups of floor cleaning liquid, glass cleaning liquid, and kitchen surface cleaning liquid.