# Patent

## Title
Liquid personal wash composition

## Abstract

The invention relates to a liquid personal cleaning composition. The present inventors have found that inclusion selected di or tricarboxylic acid or a salt thereof, when combined with thymol or terpineol provide synergistic antimicrobial action in a rapid fashion and such efficacy is very low concentrations of thymol and/or terpineol.

## Background
TECHNICAL FIELD
The invention relates to a liquid personal cleaning composition. The invention more particularly relates to a personal cleaning composition that provides synergistic antimicrobial efficacy.
BACKGROUND OF THE INVENTION
Liquid compositions for personal washing applications have been known. Such compositions include hand washing liquids usually dispensed from bottles provided with a hand pump which is actuated by pressing with the hand. Such kind of hand washing liquids are also dispensed in public places like bathrooms in airports, hotels, restaurants and offices. Other personal cleaning liquids include facewash liquids, bodywash liquids, shampoos and hair conditioners.
Such compositions are used not only to clean the surface of the body to give the consumer of feeling of being clean of dust, sebum, and sweat but also give the consumer a satisfaction of having disinfected the surface to be free of disease causing germs. Liquid forms of such compositions are known for personal care. Such compositions include antimicrobial actives that specifically target microorganisms like bacteria and virus to either kill or inactive them.
Sanitizing and disinfecting soap compositions comprising chlorine-based antimicrobial agent such as triclosan are known. Such compositions require rather long contact time to provide efficacious antimicrobial action. In practice, users, in particular children, do not spend long time in cleaning and as a result, cleaning with such compositions does not provide adequate prevention from surface or topical infection or adequate protection against diseases. The user, in spite of cleaning hands, is likely to have skin with relatively inadequate bacterial removal and may cause contamination of further animate and/or inanimate surfaces that may lead to spreading of pathogens and consequent diseases. Users in general and children in particular who wash contaminated hands before meals with slow-acting antimicrobial compositions for relatively short time are at risk of contacting diseases. These short time scales of cleaning action are ineffective in providing the desired benefit since most known antimicrobials commonly used in such products take several hours to provide the desired kill of microbes.
Therefore, the present applicant realized the need for providing a composition that gives relatively more efficacious antimicrobial action when cleaning period is relatively small, typically about 5 minutes or less, preferably lesser than 2 minutes and in many cases less than one minute or sometimes as low as 15 seconds or lesser. They have, in a prior patent application published as WO2010046238 disclosed a novel combination of thymol and terpineol that interact synergistically to enable fast antimicrobial action in less than about 15 seconds. The present inventors have found that inclusion of selected di or tricarboxylic acid or a salt thereof, when combined with thymol or terpineol provide similar synergistic antimicrobial action in a rapid fashion and such efficacy is obtained at much lower concentrations of thymol and/or terpineol. This invention has the advantage that essential oil actives like terpineol and thymol have a strong medicinal odour which is not liked by some consumers and it is advantageous to include thymol and terpineol at lower concentrations while ensuring the same efficient anti-microbial action. Further, it has been found by way of the present invention that inclusion of select anionic surfactants aids in further enhanced antimicrobial efficacy.
Liquid personal cleaning compositions are known. US2008045491 (Fitchmun) discloses a non-toxic antimicrobial surface sanitizer composition comprising a water-miscible alcohol, water, a weak acid and a multivalent cation (e.g. metal ion or metal compound). The composition may also include one or more of an emollient, oxidative agent, humectant, lubricant, plant-derived alkene, antimicrobial component or plant-derived essential oil can be formulated as solutions for sanitizing hard surfaces such as countertops and floors, or as solutions/gels for application to animal skin.
The above publication utilizes the well known antimicrobial efficacy of alcohol which is much stronger than most other known antimicrobial actives. Many consumers do not prefer to use products that utilize alcohol as they consider it as harsh on the skin and so it is desirable to develop new combination of actives that provide similar or better anti-microbial efficacy in much rapid time frame while utilizing actives that are considered mild on skin.
US2006093570 (Reckitt Benckiser) describes a surface treatment composition, preferably for personal use, comprising at least one surfactant and at least two different organic acids and/or salts or organic acids, and wherein the total concentration of the organic acids and/or salts in the composition is at least 0.5 percent (w/v). The invention further extends to a method of treating a surface, preferably hair or skin, to remove dirt and to remove or inhibit microbial growth.
The patent publication cited above does not address the problem of slow-acting antimicrobial composition, nor disclose the synergistic combination of actives disclosed and claimed in the present invention for the fast acting antimicrobial action in cleaning and disinfecting skin and/or other keratinous substrates of humans and/or animals.
It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative.
Another object of the present invention is to provide a liquid personal care cleaning and disinfecting composition that has relatively fast antimicrobial action.
SUMMARY OF THE INVENTION
According to the first aspect of the present invention there is provided a liquid personal cleaning composition with a pH in the range of 4.5 to 7.5 comprising less than 1% C1 to C3 alcohol comprising

    
    
        (a) 0.25 to 2.5% by weight of di or tri carboxylic acid or a salt thereof;
        (b) 0.01 to 2% by weight thymol;
        (c) 0.01 to 2% by weight terpineol; and
        (d) 70 to 90% by weight water.
    
    


According to another aspect of the present invention there is provided a method of disinfecting the external surface of an animal or human body comprising the steps of contacting the surface with a composition as claimed in any one of the preceding claims followed by the step of rinsing the surface with water or wiping the surface to be substantially free of the composition.


DETAILED DESCRIPTION OF THE INVENTION
These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims.
For the avoidance of doubt, any feature of one aspect of the present invention may be utilised in any other aspect of the invention. The word “comprising” is intended to mean “including” but not necessarily “consisting of” or “composed of”. In other words, the listed steps or options need not be exhaustive. It is noted that the examples given in the description below are intended to clarify the invention and are not intended to limit the invention to those examples per se. Similarly, all percentages are weight/weight percentages unless otherwise indicated.
Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word “about”. Unless specified otherwise, numerical ranges expressed in the format “from x to y” are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format “from x to y”, it is understood that all ranges combining the different endpoints are also contemplated.
By a personal cleaning composition as used herein, is meant to include a composition for cleaning and disinfecting topical areas e.g. skin and/or hair of mammals, especially humans. Such a composition may be generally classified as leave-on or rinse off, and includes any product applied to a human body for also improving appearance, cleansing, odor control or general aesthetics. It is more preferably a rinse off product. The composition of the present invention in the form of a liquid but may be modified to include a lotion, cream, foam or gel, or toner, or applied with an implement or via a face mask, pad or patch. “Skin” as used herein is meant to include skin on the face and body (e.g., neck, chest, back, arms, underarms, hands, legs, buttocks and scalp). The composition of the invention is also of relevance to applications on any other keratinous substrates of the human body other than skin e.g. hair where products may be formulated with specific aim of providing disinfection and cleaning.
The first aspect of the invention provides for a liquid personal cleaning composition with a pH in the range of 4.5 to 7.5 comprising less than 1% C1 to C3 alcohol comprising di or tri carboxylic acid or a salt thereof, thymol, terpineol and water.
The composition has a pH in the range of 4.5 to 7.5. The composition provides antimicrobial efficacy even without any contribution in such efficacy from low molecular weight alcohols viz. C1 to C2 alcohols e.g. methanol, ethanol, proponol or isopropyl alcohol which are usually water miscible.
If present, they may be less than 1% by weight of the composition, preferably less than 0.5%, more preferably less than 0.1% and optimally absent from the composition. The composition comprises 0.25 to 2.5%, preferably 0.5 to 2%, more preferably 0.75 to 1.25% by weight of the composition di or tri carboxylic acid or a salt thereof.
The di or tri carboxylic acid is preferably chosen from an oxalic, fumaric, phthalic, maleic, malic, malonic or citric acid. The di or tricarboxylic acid is most preferably a malic, malonic, or citric acid. It is possible that the part of the di or tricarboxylic acid that is added to prepare the composition of the invention is present as salt of the di or tricarboxylic acid depending on the pH at which the composition is formulated. In such cases, the salt is preferably alkali metal or alkaline earth metal salts, more preferably alkali metal salts of which sodium salt is most preferred. Structure of salts of some of the carboxylic acids are given below:




It is observed that inclusion of di or tri carboxylic acid in the composition of the invention provides for the desired antimicrobial efficacy while mono carboxylic acids do not demonstrate as good an efficacy.

The composition comprises a combination of essential oil antimicrobial actives thymol and terpineol at 0.01 to 2% by weight of the composition of each active.
Thymol is preferably present in 0.02 to 0.5%, more preferably up to 0.3% by weight, further more preferably up to 0.2% by weight of the composition. Thymol may be added to the antimicrobial composition in purified form. Alternatively, thyme oil or thyme extract comprising thymol may be added to the antimicrobial composition, while ensuring that thymol is present in the desired concentration in the composition of the present invention. Thyme oil or thyme extract is obtained from the thyme plant. Thyme plant refers to a plant belonging be genus Thymus and includes but is not limited to the following species: Thymus vulgaris, Thymus zygis, Thymus satureoides, Thymus mastichina, Thymus broussonetti, Thymus maroccanus, Thymus pallidus, Thymus algeriensis, Thymus serpyllum, Thymus pulegoide, and Thymus citriodorus. 
The structures of thymol and its isomer carvacrol are given below:




Preferred antimicrobial compositions of the present invention have terpineol in 0.05 to 1% more preferably up to 0.5% by weight of the composition. The terpineol is preferably selected from alpha-terpineol, beta-terpineol, gamma-terpineol or mixtures thereof. It is particularly preferred that the terpineol is alpha-terpineol. Terpineol may be added to the antimicrobial composition in purified form. Alternatively pine oil comprising terpineol may be added to the antimicrobial composition.

The structure of a terpineol compound is given below:




The composition of the invention comprises water as a preferred carrier. Water is present in 70 to 90%, preferably 85 to 90% by weight of the composition.

The composition of the invention optionally comprises a surfactant. Preferred surfactant is an anionic surfactant. Anionic surfactant is preferably present in 0.5 to 15%, more preferably 1 to 5% by weight of the composition. Particularly preferred anionic surfactants are glycinates, alkyl sulphates or ethoxylated alkyl sulphates.
The composition may further comprise various additional ingredients known to a person skilled in the art. Such additional ingredients include but are not limited to: perfumes, pigments, preservatives, emollients, sunscreens, emulsifiers, gelling agents, or thickening agents.
The antimicrobial composition may be in form of a liquid but the liquid composition may be further thickened to a gel or a paste. The antimicrobial composition of the present invention can be used for cleansing and care of human skin and hair.
According to another aspect of the present invention there is provided a method of cleaning and disinfecting a keratinous substrate of human and/or animals comprising applying to said surface a composition of the invention followed by a step of rinsing or wiping the surface to be substantially free of the composition. The composition is preferably diluted with water in a weight ratio of 1:10 to 1:40, preferably in a ratio of 1:20 to 1:30, before or during the step of applying the composition on the surface.
The method preferably comprises a step of rinsing the surface with a suitable solvent preferably water or the surface may be wiped with a suitable wipe.
The inventors have determined that the composition of the invention provides an antimicrobial action where the contact time of the antimicrobial actives with the surface is low, i.e. of the order of less than 5 minutes, preferably less than 2 minutes, further more preferably less than a minute and in many cases less than 15 seconds.
The invention will now be demonstrated by way of the following non-limiting examples.
EXAMPLES
Example 1 to 9
Compositions as shown in Table-1 were prepared and tested for antibacterial efficacy using the following test protocol.
Protocol: Contact kill Assay (15 second contact kill) The test bacteria E.coli ATCC 10536 was grown overnight in TSB broth (Difco-30 gpl) at 37° C. for 16 hours. 2 ml of this was sub-cultured in 40 ml of fresh TSB broth and kept to grow for 4 hours at 37° C. Then the culture was processed by spinning at 2057 g for 5 minutes, washing twice and collecting the cells.
The cell density was adjusted at 620 nm to get the final count of 108 cfu/ml (0.8 OD). The compositions as shown in Table-1 were prepared and kept for 3 hours for maturation.
9 ml of the compositions was taken in a sample container and 1 ml of processed culture was added to it. After a 15 second contact time, 1 ml of the above mixture was immediately neutralized in D/E broth (Difco-39 gpl). Serial dilution was done in D/E broth and plated on TSA (Difco-40 gpl) in duplicates. In case of the control, 1 ml of test culture was added to 9 ml of saline and was serially diluted and plated on TSA. After solidification, the plates were incubated at 37° C. for 48 hrs. The residual colonies were counted after 48hrs of incubation and the efficacy was determined by comparing with control. The data is summarized in Table-1 below.













TABLE 1









Di/tri

Log





Di/tri
carboxylic

re-



Thymol
Terpineol
Carboxylic
acid

duc-


Examples
(wt %)
wt %
Acid
(wt %)
pH
tion





















Example 1
0.2
0.5
—
—
6.9
7.2


Example 2
0.025
0.0625
—
—
6.9
0


Example 3
0.025
0.0625
Malic acid
1.0
5.0
7.2


Example 4
0.025
0.0625
Malic acid
1.0
7.3
6.1


Example 5
0.025
0.0625
Malonic
1.0
5.0
7.2





acid


Example 6
0.025
0.0625
Malonic
1.0
7.3
6.3





acid


Example 7
0.025
0.0625
Citric acid
1.0
5.0
7.2


Example 8
0.025
0.0625
Citric acid
1.0
7.2
6.5


Example 9
—
—
Malonic
1.0
5.0
0





acid


Example 10
—
—
Citric acid
1.0
5.0
0









The data in Table-1 indicates that when di or tri carboxylic acid are combined with low concentrations of essential oil actives (thymol and terpineol) they provide synergistic anti-bacterial efficacy (Examples 3 to 8) as compared to compositions outside the invention (Example 2, 9 and 10).

## Claims

1. A liquid personal cleaning composition with a pH in the range of 4.5 to 7.5 comprising less than 1% C1 to C3 alcohol consisting essentially of
(a) 0.25 to 2.5% by weight di or tri carboxylic acid or a salt thereof;
(b) 0.02 to 0.2% by weight thymol;
(c) 0.05 to 0.5% by weight terpineol; and
(d) 70 to 90% by weight water.

2. A composition as claimed in claim 1 wherein said di or tri carboxylic acid is chosen from an oxalic, fumaric, phthalic, maleic, malic, malonic or citric acid.

3. A composition as claimed in claim 2 wherein said di or tricarboxylic acid is chosen from a malic, or citric acid.

4. A composition as claimed in claim 1 comprising an anionic surfactant.

5. ) A composition as claimed in claim 4 wherein said anionic surfactant is present in an amount of 0.5 to 15% by weight of the composition.

6. A composition as claimed in claim 4 wherein said anionic surfactant is chosen from a glycinate, alkyl sulphate or ethoxylated alkyl sulphate.

7. A method of disinfecting the external surface of an animal or human body comprising the steps of contacting the surface with a composition as claimed in any one of the preceding claims followed by the step of rinsing the surface with water or wiping the surface to be substantially free of the composition.