FORM - 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See Section 10 and Rule 13)
LAUNDRY TREATMENT COMPOSITION
HINDUSTAN UNILEVER LIMITED, a company incorporated under
the Indian Companies Act, 1913 and having its registered office
at 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India
The following specification particularly describes the invention and the manner in which it is to be performed.

Field of the invention
The present invention relates to a method for treatment of a fabric with anti-microbial material. It further relates to compositions for depositing such anti-microbial material onto a fabric.
Background of the invention
Hygiene is of high priority to present day consumers.
Human skin generally contains several different micro-organisms in concentrations exceeding millions or even billions of colony forming units (cfu's) per square centimetre (cm2). Many of these micro organisms are harmless, but there are also various pathogenic types or sub-species present, such as Escherichia coli, also referred to a E. coli, and Staphylococcus aureus, also referred to as S. aureus. Several other bacteria can be found in the skin flora, such as Staphylococcus epidermidis, also referred to as S. epidermidis, which is generally non-pathogenic, but is thought to be causing unpleasant body odour.
When an anti microbial agent could be deposited onto a garment, the bad smell created by the growth of skin bacteria in sweat could be reduced.
Therefore present day consumers appreciate laundry treatment products that have anti-microbial activity.
Various other hygiene materials have been proposed in the art. In recent years a number of publications have been made on the use of essential oils for anti-bacterial action.
WO 00/34423 (Hindustan Lever Limited, 2000) discloses a synergistic detergent composition for cleaning fabric or hard surfaces. The detergent composition comprises of an anionic surfactant, cationic disinfectant component and an anionic polymer. The invention describes that incorporation of the anionic polymer in a anionic surfactant based detergent formulation enables the cationic surfactant to be active.

This provides the detergent composition to provide superior soil removal and hygienic benefits to the substrate. This Application does not disclose a polymer complex.
EP 1111034 A1 (The Procter & Gamble Company, 2001) discloses a laundry and/or cleaning and/or fabric treatment composition comprising a benefit agent and a carrier. The benefit agent may be selected from a flavour ingredient, a pharmaceutical ingredient, a bio control ingredient, a perfume composition, a refreshing cooling ingredient and a mixture thereof. The carrier agent is a polymer. The combination of the benefit agent with the carrier provides the benefit agent sufficient protection against oxidation and further effective deposition on the fabric. This Application doesn't disclose a polymer complex providing improved and fasting hygiene efficacy.
However, a laundry product having anti-microbial effect remains to be desired, preferably at low dosage of the anti-microbial agent for safety reasons.
It is therefore an object of the invention to provide a laundry treatment composition, having good anti-microbial properties, at low levels of anti microbial agent.
It is a further object of the invention to provide a composition that is effective against common skin bacteria, including both gram-positive and gram-negative bacteria.
Surprisingly it has been found that composition comprising a low amount of quaternary ammonium biocide and a polymer complex provides improved and lasting hygiene efficacy.

Summary of the invention
Accordingly the present invention provides a method for providing an anti-microbial effect to laundry comprising the steps of depositing a polymer complex comprising polymer A selected from the group of homopolymers and copolymers of carboxylic acid, and a polymer B selected from the group of homopolymers and copolymers of alkylene oxides, vinyl pyrrolidone; and/or the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose; wherein the polymer A and polymer B are not of the same class and an quaternary ammonium biocide to a fabric article, and leaving the fabric article to dry; and, wherein the fabric is not rinsed between steps of depositing and drying.
In a second aspect the invention provides the use of a combination of a polymer complex or mixture comprising polymer A selected from the group of homopolymers and copolymers of carboxylic acid and , and a polymer B selected from the group of homopolymers and copolymers of alkylene oxides, vinyl pyrrolidone and/or their; and/or the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose ; and an quaternary ammonium biocide, for providing a antimicrobial effect on fabric articles.
By anti-microbial effect is meant being able to kill bacteria under standard test conditions (e.g. AATCC 100-1999) for antibacterial finishes on textile material.
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". 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.
Detailed description of the invention
The composition according to the invention thus comprises a polymer complex or mixture and a quaternary ammonium biocide.
Polymer complex
The polymer complex according to the invention comprises a polymer A selected from the group of homopolymers and copolymers of carboxylic acid , and a polymer B selected from the group of homopolymers and copolymers of alkylene oxides, vinyl pyrrolidone ; and/or the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose
The composition according to the Invention comprises a polymer A and a polymer B. Polymers A and B are typically selected such that they form a complex due to the formation of hydrogen bonds.
The polymers may be homo polymers or co polymere wherein by copolymer of monomer X is meant any polymer that contains the monomer x and at least one further monomer.
Polymers A and B are preferably present in the composition in a ratio of between 1:5 and 5:1, more preferably between 1:2 and 2:1
Polymer A
According to the present invention, polymer A is a polymer selected from the group of
homopolymers and copolymers of carboxylic acid . Polymer A has a plurality of

carboxyl groups. The polymer A has a molecular mass preferably from 300 to 109 D (Dalton, also referred to as atomic mass units, amu). The polymer A is selected from the class consisting of homopolymers or copolymers of carboxylic polymers, including natural synthetic and semi-synthetic polymers in this class.
Some non-limiting examples of polymer A according to the present invention include:
(a) homopolymers of a carboxylic acid, including but not limited to polycarboxylic acid such as polyacrylic acid, polymaleic acid or copolymers of acrylic and maleic acid.
(b) polysaccharides comprising carboxyl groups. Such polysaccharides may include (but are not limited to) starch, cellulose, sodium alginate, natural gums, and their modified materials such as sodium carboxymethyl cellulose, hydroxyethyl cellulose.
Homopolymers or copolymers of carboxylic acid have a molecular mass of preferably from 2x103 to 107 D more preferably from 5x104 to 106 D and most preferably from 9x104 to 5x105 D.
If the polymers are in particulate form, the particle size is preferably less than 200µm, preferably less than 100µm, more preferably less than 50µm still more preferably less than 10um, or even less than 5µm.
The homopolymers or copolymers of polysaccharide have a molecular mass of preferably from 103 to 109 D, more preferably from 104 to 109 D and most preferably from105to109D.
Polymer A is preferably at least partially neutralised in the Sodium (Na+) form, preferably at least 10%w of polymer A is neutralised, more preferably at least 20%, still more preferably at least 50%.
Polymer A may be synthetic, semi-synthetic or natural. However, synthetic or semisynthetic polymers are preferred.
Polymer A is preferably water soluble or water dispersible, most preferably polymer A is water soluble.

It is preferred that the polymer A is selected from a class consisting of homopolymers or copolymers of carboxylic acid.
The homopolymers or copolymers of carboxylic acid are preferably a polyacrylic acid or a copolymer thereof. Examples include SOKALAN® PA (BASF) and CARBOPOL® (Lubrizol).
The concentration of polymer A in the composition according to the invention is preferably between 0.005 and 25% by weight, more preferably at least 0.01%, or even at least 0.05%, but preferably not more than 15%, more preferably less than 5%, still more preferably less than 1%, even more preferably less than 0.5%, even less than 0.1%, or even less than 0.05% by weight of the composition.
The amount of polymer A relative to the fabric surface area is preferably from 0.5 to 200 ug/cm2 of fabric surface area, more preferably from 1 to 100 ug/cm2, and most preferably from 2 to 50 ug/cm2 of fabric surface area. The term "fabric surface area" as used herein refers to surface area of one side of the fabric.
Polymer B
According to the present invention, polymer B has a monomeric unit comprising a
group that can form hydrogen bonds with the carboxyl groups of polymer A..
Accordingly, polymer B is selected from the group of homopolymers and copolymers of alkylene oxides, vinyl pyrrolidone ; and/or the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose.
The group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose, is generally not water soluble. In order to obtain the benefit of this group of polymers the particle size is set such that the particles are easily dispersible in water or and aqueous solution (i.e. a wash or rinse liquor). If the polymers are in particulate form, the particle size is preferably less than 200µm, more

preferably less than 100µm, even more preferably less than 50µm still more preferably less than 10µm, or even less than 5µm.
Polymers and homo polymers of carboxylic acid and/or sacchharides and/or polyalkylene glycol/ether qualify to be selected both as polymer A or polymer B, as they comprise hydroxyl or carboxyl group and either a carbonyl or an ether group. However, according to an essential aspect, polymer A and polymer B are not of the same class. It is particularly preferred that the polymers A and B are selected from different classes of polymers. Without wishing to be limited by theory, it is believed that the two polymers A and B, when dissolved in water, form a complex with a solubility lower than each of the polymers A and B, which helps in enhanced deposition and other benefits.
Polymer B preferably has a molecular mass from 103 to 109 D.
Homopolymers or copolymers of vinyl pyrrolidone or vinyl alcohol preferably have a molecular mass of between 103 and 107 D, more preferably from 104 to 106 D and most preferably from 30,000 to 500,000 D. Commercially available polyvinyl pyrrolidone can be used, one example of which is LUVISKOL® (BASF).
Homopolymers or copolymers of poly alkylene oxide preferably have a molecular mass greater than 2x104 D. The molecular mass is preferably from 2x104 to 106 D, more preferably from 3x104 to 5x105 D and most preferably from 5x104 to 2x105 D.
Homopolymers or copolymers of saccharide preferably have a molecular mass of preferably from 103 to 109 D, more preferably from 104 to 109 D and most preferably from 105 to 109 D. Any commercially available poly alkylene oxide, for example POLYOX® (Dow Chemical Co) can be used according to the present invention. Polymer B may be synthetic, semi-synthetic or natural. However, synthetic or semisynthetic polymers are preferred.
According to a preferred embodiment, the polymer B is water soluble.

It is particularly preferred that the polymer B is selected from a class consisting of homopoiymers or copolymers of vinyl pyrrolidone or alkylene oxide. The concentration of polymer B in the composition according to the invention is preferably between 0.005 and 20% by weight, more preferably at least 0.01%, or even at least 0.05%, but preferably not more than 10%, more preferably less than 5%, still more preferably less than 1%, even more preferably less than 0.5%, even less than 0.1%, or even less than 0.05% by weight of the composition.
The amount of polymer B relative to the fabric surface area is preferably from 0.5 to 200 ug/cm2 of fabric surface area, more preferably from 1 to 100 ug/cm2, and most preferably from 2 to 50 ug/cm2 of fabric surface area. The term "fabric surface area" as used herein refers to surface area of one side of the fabric.
Some examples of combinations of polymer A and polymer B, which are particularly preferred, are given below.
Table 1: Preferred combination of the polymers

Polymer A Polymer B
Polyacrylic acid (PAA) Poly vinyl pyrrolidone (PVP)
Polyacrylic acid (PAA) Polyethylene Oxide(PEO)
Polyacrylic acid (PAA) Polyethylene Glycol (PEG)
Polyacrylic acid (PAA) Po/y vinyl alcohol (PVA)
Sodium carboxymethyl cellulose (SCMC) Polyethylene Oxide (PEO)
Polyacrylic acid(PAA) Hydroxyethyl cellulose
Starch-graft-polymethacrylic acid Polyethylene Oxide
Starch-graft-polymethacryfic acid Polyvinyl pyrrolidone
Pluronic-g-PoIyacrylic acid Polyethylene Oxide
Pluronic-g-Polyacrylic acid Polyvinyl pyrrolidone
Sodium carboxymethyl cellulose Hydroxyethyl cellulose
Sodium carboxymethyl cellulose Polyvinyl alcohol

The most preferred combinations of the polymers are PAA-PVP, PAA-PEO, PAA-PEG, Starch-graft-polymethacrylic acid-Polyethylene Oxide.
Quaternary ammonium biocide
The quaternary ammonium biocide is preferably selected from Cetyl-trimethyl-ammonium Chloride, Cetyl-trimethyl-ammonium Bromide, Tetradecyl-trimethyl-ammonium Chloride, Dodecyl-trimethyl-ammonium Chloride, Stearyl-trimethyl-ammonium Chloride, Octadecyl-trimethyl-ammonium Chloride, Dodecylpyridinium Chloride, Cetylpyridinium Chloride, Benzalkonium Chloride, Tetrabutyl-ammonium. Chloride, Tetraheptyl-ammonium. Chloride, 1,3-Decy|-2-methyl-imidazolium Chloride, 1-Hexadecyl-3-methyl-imidazolium Chloride, Didecyl-dimethyl-ammonium. Bromide, Didecyl-dirrtethyl-ammonium. Chloride.
Bromides are typically not preferred due to their toxicity.
The most preferred quaternary ammonium biocide is benzalkonium chloride and cetylpyridinium chloride.
The quaternary ammonium biocide is preferably present in the composition in a concentration of between 0.01 and 10% by weight of the composition, but preferably at least 0.02%, or even at least 0.05% by weight of the composition, while preferably not more than 5%, more preferably not more than 1%, still more preferably not more than 0.5%, further preferably not more than 0.4%, further preferably not more than 0.3%, still further preferably not more than 0.2% or even not more than 0.1% by weight of the concentration.
It is preferred that the composition comprises a second quaternary ammonium biocide.
When more than one quaternary ammonium biocide is present in the composition, the above mentioned concentrations may be considered to be the concentrations of the

combined quaternary ammonium biocides, but preferably relate to each of the individual quaternary ammonium biocides.
Without wishing to be bound by theory, it is believed that the biocide is incorporated into the polymer complex formed from Polymer A and Polymer B during the dissolution of polymer. The polymer complex, having solubility lower than each of the polymers A and B, helps in enhanced deposition of the biocide onto the fabric. Thus, providing enhanced biocidal properties to the fabric.
Compositions
The compositions according to the invention may be applied in various laundry treatment compositions, but the use of the invention in fabric conditioner compositions is the most preferred.
The pH of the compositions is preferably neutral or mildly acidic, more preferably between pH 2 and 9, still more preferably at least pH 3, while more preferably less than pH 8, still more preferably less than pH 7, or even less than pH 5.
Method
In another aspect there is provided a method for treatment of a fabric, by depositing a composition according to the invention to a fabric in the rinse step for providing an antimicrobial effect comprising the steps of applying a composition to a rinse liquor, and leaving the fabric to dry. The fabric is left to dry after treatment, in order to reduce loss of the deposited material.
Preferably the rinse liquor to cloth (fabric) ratio is between 20:1 and 1:1.
Examples
The invention will now be illustrated by means of the following non-limiting examples.
Example 1: Anti-bacterial tests

In this example the antibacterial efficacy of a fabric treatment composition according to the invention is demonstrated using a standard method, AATCC 100-1999 for antibacterial finishes on textile materials.
Replicate samples of fabric were inoculated with working culture of individual bacterial species (eg S.epidermidis and E.coli) suspended in a common nutrient medium (TSB). The samples were incubated under humid conditions at 37oC for a specified contact time of 4 hours. After incubation, the cells were recovered in a neutralizer (D/E Neutralizer) using a Griffin® shaker. The viable count is determined by CY agar (supplied by HiMedia) pour plating Activity is assessed by comparing the size of the population of untreated with that of treated specimen
The following formulations were tested. Table 1a: Examples

Blank (%w) Example 1 (%w) Example 2 (%w) Example 3 (%w) Example 4 (%w)
S. epidermidis
(start,
cfu/cm2) 24x106 24x106 24x106 24x106 24x106

PAA1) 0.015 0.015 0.015 0.015
PEO1) 0.01 0.01 0.01 0.01
Benzalkonium chloride 0.05 0.02 0.01 0.005
Saline Solution 2) balance Balance balance balance Balance

Kill (cfu/cm2 remaining) 24x106 2 520 0.172x106 0.84x106
Kill (log reduction) 0.0 7.1 4.7 2.2 1.5

Table 1b: Comparative examples

Comp A
(%w) Comp B (%w) Comp C
(%w) Comp D (%w) CompE
(%w)
S. epidermidis
(start,
cfu/cm2) 24x106 24x106 24x106 24x106 24x106

PAA1) 0.015
PE01) 0.01
Benzalkonium chloride 0.05 0.02 0.01 0.005
Saline Solution 2) Balance balance balance Balance Balance

Kill (cfu/cm2 remaining) 19.4x106 0.004x106 0.014x106 0.48x106 1.08x106
Kill (log reduction) 0.1 3.8 3.3 1.7 1.4
1) The polymer complex comprised PAA (poly acrylic acid; Mw 100,000 D, ex Sigma-Aldrich) and PEO (poly ethylene oxide; Mw 100,000 D, ex Sigma-Aldrich), in a ratio of 1.5:1 in amounts as given in the table.
2) The saline solution comprised 0.1% NaCI and Citric acid to a pH of 3.6.
The results above show the unexpected improvement in bacterial kill of the polymer complex together with the quaternary ammonium biocide, while the separate components show substantially less kill of bacteria.
Example 2: Comparison with a commercially available fabric conditioners. The same protocol was followed as in example 1, but now also compared to a commercially available fabric conditioner (Comfort, ex Unilever India), which comprises

a quaternary ammonium surfactant, and a different quaternary ammonium compound, CPC (cetylpyridinium chloride).
The compositions and results for example 2 are given below.
Table 2: Comparative examples

Blank
(%w) Comp A
(%w) Comp F (%w) Comp G
(%w) Example 5
(%w)
S. epidermidis (start, cfu/cm2) 28x106 28x106 28x106 28x106 28x106

PAA1) 0.015 0.015
PEO1) 0.01 0.01
CPC 0.1 0.1
Comfort ® 1
Saline Solution 2) Balance balance balance Balance Balance

Kill (cfu/cm2 remaining) 28x106 27x106 1200 10x106 0
Kill (log reduction) 0.0 0.0 4.3 0.4 7.4
1) The polymer complex comprised PAA (poly acrylic acid; Mw 100,000 D, ex Sigma-Aldrich) and PEO (poly ethylene oxide; Mw 100,000 D, ex Sigma-Aldrich), in a ratio of 1.5:1 in amounts as given in the table.
2) The saline solution comprised 0.1% NaCI and Citric acid to a pH of 3.6.
The table above shows a surprising antibacterial effect of the combination of a polymer complex and a quaternary ammonium biocide.

Example 3: effect of polymer concentration
The same protocol was followed as in example 1, but now comparing different polymer
concentrations.
The following formulations were tested.
Table 3a: Examples

Example 6 Example 7 Example 8 Example 9
(%w) (%w) (%w) (%w)
S. epidermidis 24x106 24x106 24x106 24x106
(start, cfu/cm2)

PAA1) 0,003 0.006 0.015 0.06
PEO1) 0.002 0.004 0.01 0.04
Benzalkonium 0.02 0.02 0.02 0.02
chloride
Saline Balance Balance Balance Balance
Solution 2)

Kill (cfu/cm2 13000 580 520 500
remaining)
Kill (log 3.3 4.6 4.7 4.7
reduction)

Table 3b: Comparative examples

Blank Comparative H Comparative I
(%w) (%w) (%w)
S. epidermidis 24x106 24x106 24x106
(start, cfu/cm2)

PAA1) 0.015
PEO1) 0.01
Benzalkonium 0.02
chloride
Saline Balance Balance Balance
Solution 2)

Kill (cfu/cm2 24x106 20x106 0.014x106
remaining)
Kill (log 0.0 0.1 3.3
reduction)
1) The polymer complex comprised PAA (poly acrylic acid; Mw 100,000 D, ex Sigma-Aldrich) and PEO (poly ethylene oxide; Mw 100,000 D, ex Sigma-Aldrich), in a ratio of 1.5:1 in amounts as given in the table.
2) The saline solution comprised 0.1% NaCI and Citric acid to a pH of 3.6.
The results above show the unexpected improvement in bacterial kill of the polymer complex together with the quaternary ammonium biocide, while the separate components show substantially less kill of bacteria.
Example 4: lasting hygiene effect
The same protocol was followed as in example 1, but now comparing testing anti
bacterial efficacy after 4 hrs, 15 hrs and 24 hrs.
The following formulations were tested.

Table 4: Examples

Blank
(%w) Comp A (%w) Comp C
(%w) Ex 2
(%w)
S. epidermidis (start, cfu/cm2) 24x106 24x106 24x106 24x106

PAA1) 0,015 0.015
PEO1) 0.01 0.01
Benzalkonium chloride 0.02 0.02
Saline solution 2) Balance balance Balance Balance

Kill (cfu/cm2 remaining after 4hrs) 24x106 19.4x106 14000 520
Kill (log reduction after 4 hrs) 0.0 0.1 3.3 4.7
Kill (cfu/cm2 remaining after 15hrs) 18.6x106 11.6x106 2840 208
Kill (log reduction after 15 hrs) 0.1 0.3 3.9 5.1
Kill (cfu/cm2 remaining after 24hrs) 15.2x106 8.4x106 680 30
Kill (log reduction after 24 hrs) 0.2 0.5 4.6 5.9
1) The polymer complex comprised PAA (poly acrylic acid; Mw 100,000 D, ex Sigma-Aldrich) and PEO (poly ethylene oxide; Mw 100,000 D, ex Sigma-Aldrich), in a ratio of 1.5:1 in amounts as given in the table.
2) The saline solution comprised 0.1% NaCI and Citric acid to a pH of 3.6.
The results above show the unexpected improvement in bacterial kill of the polymer complex together with the quaternary ammonium biocide, even after 24 hrs.

Claims
1 A method of providing an anti-microbial effect to laundry comprising the steps of:
a depositing a polymer complex comprising
i polymer A selected from the group of homopolymers and copolymers
of carboxylic acid, and ii a polymer B selected from the group of homopolymers and copolymers of alkylene oxides, vinyl pyrrolidone; and/or the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose; wherein the polymer A and polymer B are not of the same class and
iii a quaternary ammonium biocide to a fabric article, and b leaving the fabric article to dry; and, wherein the fabric is not rinsed between steps a and b.
2 A method of providing an anti-microbial effect to laundry according to claim 1, wherein polymer A is present in a concentration of between 0.005 and 25% by weight of the composition.
3 A method of providing an anti-microbial effect to laundry according to any one of claim 1 or 2, wherein polymer B is present in a concentration of between 0.005 and 20% by weight by weight of the composition.
4 A method of providing an anti-microbial effect to laundry according to any one of claim 1 to 3, wherein the quaternary ammonium biocide is present in a concentration of between 0.01 and 10% by weight of the composition.
5 A method of providing an anti-microbial effect to laundry according to any one of the preceding claims, wherein the pH of the composition is between 2 and 9.
6 Use of a combination of a polymer complex comprising

a polymer A selected from the group of homopolymers and copolymers of carboxylic acid, and
b a polymer B selected from the group of homopolymers and copolymers of alkylene oxides, vinyl pyrrolidone; and/or the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose; and
c an quaternary ammonium biocide,
for providing a anti-microbial effect on fabric articles.