HK1235627A1 - Liquid antimicrobial comprising polyvinylalcohol and two water-soluble antimicrobial agents - Google Patents

Description

This invention relates to a liquid antimicrobial composition comprising water, a water-soluble polymer and two water-soluble antimicrobials. The invention also relates to products incorporating or treated with the liquid antimicrobial composition.

Background

It is known to incorporate antimicrobials into consumer products in order to inhibit the growth of, for example, bacteria and/or fungi and/or viruses. For absorbent fabrics such as clothing, curtains/blinds and bedding, antimicrobials can be incorporated by applying a liquid containing the antimicrobial to the fabric, and then allowing the fabric to dry. US 5,421,898 describes a composition for use in disinfectant wipes which includes polyvinyl alcohol and benzalkonium chloride. WO 2007/100654 discloses an antimicrobial composition comprising polyvinyl alcohol and benzalkonium chloride for the treatment of beds and textiles used in a healthcare environment. WO 2014/060755 describes an antimicrobial composition comprising polyhexamethylene biguanide, benzalkonium chloride and didecyl dimethylammonium chloride for the treatment of textiles, wall papers or carpets.

A disadvantage of applying antimicrobials in this way is that once the fabric has dried it can have a different feel on the user's skin compared to how the fabric felt to the user before treatment. This is generally considered by users of such fabrics to be unpleasant and undesirable. Thus, this invention seeks to provide a liquid antimicrobial which, when applied to an absorbent fabric which is then dried, more closely retains the original feel of the fabric.

An additional problem with applying antimicrobials to absorbent fabrics as described above is that the antimicrobial will be washed out of the fabric as it is repeatedly laundered. This invention therefore also seeks to provide a liquid antimicrobial that has an increased retention time in absorbent fabrics after repeated laundry cycles.

Statement of invention

This invention relates to a liquid antimicrobial composition comprising:

1. (a) water,
2. (b) a water-soluble polymer, and
3. (c) two water-soluble antimicrobials,

wherein the water-soluble polymer is polyvinyl alcohol, and wherein the two water-soluble antimicrobials are benzalkonium chloride and didecyldimethylammonium chloride. In this way, a liquid antimicrobial is provided which can be applied to absorbent materials. It is believed that, compared to prior art compositions, the inclusion of the water-soluble polymer can provide (i) a reduced detrimental effect to the feel of the fabric, and (ii) an increased retention time in the fabric after repeated laundry cycles.

In relation to this invention, the term "antimicrobial" is used to refer to a substance that can kill microorganisms or inhibit their growth. Examples of antimicrobials include germicides, antibiotics, antibacterials, antivirals and antifungals. It is preferred that the antimicrobial provides up to a log 4 reduction in the number of cells of the microorganism in question. For example, a reduction in the number of cells from 10⁸ to 10⁴ would be a log 4 reduction (ie killing of 99.9% of the cells in question).

It is preferred that the liquid antimicrobial composition comprises:

1. (a) at least 30wt% water,
2. (b) 1-10wt% of the water soluble polymer, and
3. (c) 5-69wt% of the two water-soluble antimicrobials.

Preferably, the liquid antimicrobial composition comprises:

1. (a) 50-60wt% water,
2. (b) 3-7wt% of the water-soluble polymer, and
3. (c) 35-45wt% of the two water-soluble antimicrobials.

More preferably, the liquid antimicrobial composition comprises:

1. (a) 56.5wt% water,
2. (b) 5wt% of the water-soluble polymer, and
3. (c) 38.5wt% of the two water-soluble antimicrobials.

Preferably, the water-soluble polymer is a film forming agent, ie an agent that assists in allowing the composition to form a film (or coating) when it is applied to a substrate.

Water-soluble polymers include a water-soluble polyalkyl alcohol or a polyhexanide, preferably polyhexamethylene biguanide. The water-soluble polymer of the invention is polyvinyl alcohol. Preferably, the polyvinyl alcohol is at least partially hydrolysed, more preferably at least 60mole% hydrolysed. In a preferred embodiment, the polyvinyl alcohol is 85-93mole% hydrolysed. Preferably, the polyvinyl alcohol has a viscosity of 10-34 mPa·s as a 4wt% solution in water at 20°C. Water-soluble polymers, ie polyvinyl alcohol, are particularly preferred because they assist in retaining the water soluble antimicrobial in the fibres of the fabric to which the liquid antimicrobial composition is applied. Without wishing to be bound to any theory, it is believed that this is due to the water-soluble polymer swelling upon contact with water during laundering, helping to lock the antimicrobial into the fibres of the fabric.

The two water-soluble antimicrobials according to the invention are benzalkonium chloride and didecyldimethylammonium chloride. It is preferred that benzalkonium chloride is present in an amount of 5-50wt%. In some embodiments, the amount of benzalkonium chloride is 10-25wt%, preferably 15-20wt%, more preferably 17.5wt%. It is preferred that didecyldimethylammonium chloride is present in an amount of 10-50wt%. In some embodiments, the amount of didecyldimethylammonium chloride is 14-28wt%, preferably 19-23wt%, more preferably 21wt%.

The inclusion of two antimicrobials can provide a broader spectrum of antimicrobial activity. The two water-soluble antimicrobials are benzalkonium chloride and didecyldimethylammonium chloride. It is preferred that the liquid antimicrobial composition comprises 15-20wt% benzalkonium chloride and 19-23wt% didecyldimethylammonium chloride, more preferably 17.5wt% benzalkonium chloride and 21wt% didecyldimethylammonium chloride.

Disclosed are also alternative antimicrobials that include 2-bromo-2-nitropropane-1,3-diol; polyhexanides, preferably polyhexamethylene biguanide; and/or chlorophenols, preferably 4-chloro-3,5-dimethylphenol, 2-chloro-3-methyl-phenol, 2,4-dichloro-3,5-dimethylphenol, 2,4-dichloro-5-methylphenol, 4-chloro-3-methylphenol and/or 2,4,6-trichlorophenol.

In some embodiments, the remainder of the liquid antimicrobial composition comprises incidental impurities.

A preferred liquid antimicrobial composition as described above comprises water, 85-93% hydrolysed polyvinyl alcohol, benzalkonium chloride, and didecyldimethylammonium chloride. A particularly preferred composition comprises:

1. (a) 50-60wt% water, preferably 56.5wt% water,
2. (b) 3-7wt% of 85-93% hydrolysed polyvinyl alcohol, preferably 5wt% of 85-93% hydrolysed polyvinyl alcohol,
3. (c) 15-20wt% benzalkonium chloride, preferably 17.5wt% benzalkonium chloride, and
4. (d) 19-23wt% didecyldimethylammonium chloride, preferably 21wt% didecyldimethylammonium chloride.

Also described is a method of preparing a liquid antimicrobial composition as described above, comprising the step of mixing water, a water-soluble polymer, and at least one aqueous solution of a water-soluble antimicrobial. Preferably, the method comprises the step of mixing 25-35wt% water, 3-7wt% of the water-soluble polymer, and 60-70wt% of the at least one aqueous solution of a water-soluble antimicrobial. More preferably, the method comprises the step of mixing 30wt% water, 5wt% of the water-soluble polymer, and 65wt% of the at least one aqueous solution of a water-soluble antimicrobial. In a preferred embodiment, the method comprises the step of mixing 30wt% water, 5wt% of the water-soluble polymer, 35wt% of a 50wt% aqueous solution of benzalkonium chloride, and 30wt% of a 70wt% aqueous solution of didecyldimethylammonium chloride.

This invention also relates to a method of applying a liquid antimicrobial composition as described above to an absorbent material, comprising the step of contacting the absorbent fabric with the liquid antimicrobial composition. The absorbent material may be an absorbent fabric. Preferably, the method comprises the step of drying the material after the contacting step. In some embodiments, the amount of liquid antimicrobial composition applied to the absorbent material is 20-100g/m², preferably 25-30g/m², more preferably about 27g/m².

In relation to this invention, the term "absorbent material" is used to mean any material which is capable of absorbing the liquid antimicrobial composition. In relation to this invention, the term "absorbent fabric" (for example a woven fabric such as cotton or a blend of polyester and cotton, or nonwoven fabric such as polypropylene or viscose) is used to mean a fabric or cloth which is capable of absorbing the liquid antimicrobial composition. The absorbent material may be an item of clothing, a curtain, a blind, an item of bedding, wallpaper or laundry product. Examples of items of clothing include t-shirts and socks. Examples of items of bedding include pillows and duvets.

This invention also relates to an item of clothing, a curtain, a blind, an item of bedding, wallpaper or laundry product comprising a water-soluble polymer and two water-soluble antimicrobials as described above. Examples of items of clothing include t-shirts and socks. Examples of items of bedding include pillows and duvets. The composition of the invention can be particularly useful in inhibiting the growth of fungi on the dead skin that accumulates in bedding. Bedbugs are known to feed on these fungi, so inhibiting its growth reduces the viability of the bedbugs. Examples of laundry products include a liquid formulation for use during or after a laundry cycle.

This invention will be further described by reference to the following Figure in which: Figure 1 shows a photograph of testing of the antibacterial activity of the composition of the invention after various number of washing cycles.

Example

A liquid antimicrobial composition was prepared by mixing (a) about 30wt% water, (b) about 5wt% of 85-93% hydrolysed polyvinyl alcohol, (c) about 35wt% of a 50wt% aqueous solution of benzalkonium chloride, and (d) about 30wt% of a 70wt% aqueous solution of didecyldimethylammonium chloride. This composition was then applied to a polycotton blend t-shirt by spraying, in an amount of around 28g/m².

A portion of the treated t-shirt was removed i.e. after 0 washes. The treated t-shirt was then washed 10 times in a 1% solution of a biological laundry detergent at 40°C after which a sample was removed i.e. 10 washes. This procedure was repeated to give samples after 20, 30, 40 and 50 washes.

The unwashed and washed t-shirt samples were then sterilised at 121°C for 5 minutes and then tested for antibacterial activity as detailed below.

Evaluation of antimicrobial protection Test species: Staphylococcus aureus (ATCC 6538)

Testing was carried out according to EN ISO 20645:2004 - Determination of antibacterial activity - agar diffusion plate test.

A lower layer, 10 ml of culture media (trypticase soy agar, TSA), was poured into sterile Petri dishes and allowed to set. Culture media (TSA), pre-cooled to approximately 45°C, was inoculated with the test bacteria and poured over the lower layer to form an upper layer and allowed to set.

Swatches 25 x 25 mm of the t-shirt samples were aseptically transferred onto the two-layer agar plates and incubated at 35°C for 24 hours.

The level of antibacterial activity was assessed by examining the extent of the bacterial growth in the contact zone between the agar and the test swatch. Inhibition zones were calculated using the following formula: Where H is the inhibition zone in mm

• D is the total diameter of the swatch and the inhibition zone
• d is the diameter of the swatch in mm

The results of this testing are shown in Table 1 below. Table 1

0 wash	42 mm	No growth	≥ 1 mm no growth	Effective
10 washes	42 mm	No growth	≥ 1 mm no growth	Effective
20 washes	39 mm	No growth	≥ 1 mm no growth	Effective
30 washes	40 mm	No growth	≥ 1 mm no growth	Effective
40 washes	40 mm	No growth	≥ 1 mm no growth	Effective
50 washes	40 mm	No growth	≥ 1 mm no growth	Effective

According to the EN ISO 20645, standard inhibition zones ≥ 1 mm and no growth under the specimen are accepted as effective. 0 mm inhibition and slight growth are evaluated as limited effect.

A photograph of the Petri dishes used in this testing is shown in Figure 1. The samples are labelled as follows:

1. (i) 0 washes
2. (ii) 10 washes
3. (iii) 20 washes
4. (iv) 30 washes
5. (v) 40 washes, and
6. (vi) 50 washes.

Test results indicate that even after 50 washes the treated t-shirt swatches demonstrated effective antibacterial protection.

Claims (8)

1. A liquid antimicrobial composition comprising:

   (a) water,

   (b) a water-soluble polymer, and

   (c) two water-soluble antimicrobials

   wherein the water-soluble polymer is polyvinyl alcohol, and wherein the two water-soluble antimicrobials are benzalkonium chloride and didecyldimethylammonium chloride.
2. A liquid antimicrobial composition as claimed in claim 1, comprising:

   (a) 50-60wt% water,

   (b) 3-7wt% of the water-soluble polymer, and

   (c) 35-45wt% of the two water-soluble antimicrobials.
3. A liquid antimicrobial composition as claimed in either claim 1 or claim 2, wherein the polyvinyl alcohol is at least partially hydrolysed.
4. A liquid antimicrobial composition as claimed in claim 3, wherein the polyvinyl alcohol is 85-93% hydrolysed.
5. A liquid antimicrobial composition as claimed in any one of the preceding claims, comprising 15-20wt% benzalkonium chloride and 19-23wt% didecyldimethylammonium chloride.
6. A method of preparing a liquid antimicrobial composition as claimed in any preceding claim, comprising the step of mixing water, polyvinyl alcohol, an aqueous solution of benzalkonium chloride and an aqueous solution of didecyldimethylammonium chloride.
7. A method of applying a liquid antimicrobial composition as claimed in any one of claims 1-5 to an absorbent material, comprising the step of contacting the absorbent fabric with the liquid antimicrobial composition.
8. An item of clothing, a curtain, a blind, an item of bedding, wallpaper or laundry product comprising a water-soluble polymer as claimed in any one of claims 1-5 and two water-soluble antimicrobials as claimed in in any one of claims 1-5.