WO2011151169A1

WO2011151169A1 - Hard surface treatment composition

Info

Publication number: WO2011151169A1
Application number: PCT/EP2011/057930
Authority: WO
Inventors: Sameer Keshav Barne; Kalpana Kamalakar Nayak; Aravindakshan Perincheery; Maya Treesa Saji
Original assignee: Unilever Nv; Unilever Plc; Hindustan Unilever Limited
Priority date: 2010-05-31
Filing date: 2011-05-17
Publication date: 2011-12-08
Also published as: EP2576747B1; BR112012028719A2; ZA201208409B; CN102906237B; BR112012028719B1; EA201201618A1; CN102906237A; AR081502A1; EA020708B1; PL2576747T3; EP2576747A1

Abstract

The invention is in the field of hard surface cleaning, especially hard surface treatment for obtaining a lasting anti-microbial benefit. It remains to be desired to prepare hard surface cleaning compositions having a high anti-microbial effect, even after longer time, with a low dosage of anti-microbial essential oils. It is therefore an object of the invention to provide a hard surface treatment composition, having good anti-microbial properties, at low levels of essential oil. Surprisingly it has been found that composition comprising a low amount of essential oil and a polymer complex provides improved anti-microbial efficacy.

Description

HARD SURFACE TREATMENT COMPOSITION Field of the invention

The invention is in the field of hard surface cleaning, especially in the field of hard surface cleaning composition having anti-microbial effect.

Background of the invention

Hygiene is of high priority to present day consumers. Consumers all over the world use various kinds of disinfecting cleaning compositions for hard surfaces.

Many micro organisms found on household surfaces 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 gram-positive and gram-negative bacteria can be found on any household surface.

Therefore present day consumers appreciate hard surface cleaning products that have anti-microbial activity. The most commonly known disinfectant in house hold care is hypochlorite. However hypochlorite causes bad smell, bleaches clothes that come in contact with it and is unpleasant to skin mostly caused by its high alkalinity.

Various alternative 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.

EP-A-912678 discloses the use of essential oil compounds for anti microbial effect on hard surfaces. However, essential oils are relatively expensive ingredients. Additionally, essential oils are also known for their fragrances; using high amounts may cause a peculiar smell that is not always appreciated by the consumer.

WO1998/20735 (Procter and Gamble) describes a spray-able liquid disinfecting composition comprising a hydrogen peroxide, an antimicrobial essential oil, and a shear thinning polymeric thickener. The hydrogen peroxide in presence shear thinning polymeric thickener provides safe and effective disinfection on clean surfaces. The Application doesn't disclose a composition comprising a polymer complex and an antimicrobial composition.

US 2007/0238634 (Foland et.al) describes a treatment formulation comprising of an active material selected from the group consisting of a surfactant, a fragrance, a dye and a combination thereof, and an ionically cross linked polymer for incorporation into nonwoven substrates. The Application doesn't disclose a composition comprising a polymer complex and an antimicrobial composition.

It is further desired that the hygiene benefit is not only active shortly after deposition, but remains on the surface for a longer time. Accordingly it remains to be desired to prepare hard surface cleaning composition having a high anti-microbial effect, even with a low dosage of anti-microbial essential oils

It is therefore an object of the invention to provide a hard surface cleaning

composition, having good anti-microbial properties, at low levels of essential oil.

It is therefore another object of the invention to provide a hygiene benefit is not only active shortly after deposition, but remains on the surface for a longer time. It is a further object of the invention to provide a composition that is effective against common bacteria, including both gram-positive and gram-negative bacteria. Surprisingly it has been found that composition comprising a low amount of essential oil and quaternary ammonium biocide and a polymer complex provides improved hygiene efficacy.

5 Summary of the invention

Accordingly the present invention provides in a first aspect a hard surface treatment composition comprising 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

0 pyrrolidone; and/or the group of homopolymers and copolymers of vinyl alcohol,

saccharides, hydroxyalkyl cellulose; and an antimicrobial composition comprising essential oil and quaternary ammonium biocide.

In a second aspect the invention provides a method for providing an anti-microbial5 effect to a hard surface comprising the steps of applying a composition according to the first aspect to the surface, and waiting for at least 5 seconds.

In a third aspect the invention provides the use of a combination of a polymer complex comprising polymer A selected from the group of homopolymers and

o 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; and an antimicrobial composition comprising essential oil and a quaternary ammonium biocide, for providing a anti-microbial effect on hard surfaces.

5

By anti-microbial effect is meant being able to kill bacteria under the standard

European suspension test (EST) - EN 1276.

These and other aspects, features and advantages will become apparent to those of 0 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 and an antimicrobial composition.

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 polymers, 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 200μηη, preferably less than Ι ΟΟμηη, more preferably less than 50μηη still more preferably less than Ι Ομιτι, or even less than 5μηη.

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 from 10⁵ to 10⁹ D. 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 0.001 and 25% by weight, more preferably at least 0.002%, or even at least 0.005%, 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.

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 20Όμηη, more preferably less than Ι ΟΌμηη, even more preferably less than 50μηη still more preferably less than 10μηη, or even less than 5μηη.

Polymers and homopolymers of carboxylic acid and/or saccharides 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 semi- synthetic 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 homopolymers or copolymers of vinyl pyrrolidone or alkylene oxide.

The concentration of polymer B in the composition according to the invention is preferably between 0.001 and 20% by weight, more preferably at least 0.002%, or even at least 0.005%, 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.

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) Poly vinyl alcohol (PVA)

Sodium carboxymethyl cellulose (SCMC) Polyethylene Oxide (PEO)

Polyacrylic acid(PAA) Hydroxyethyl cellulose

Starch-graft-polymethacrylic acid Polyethylene Oxide

Starch-graft-polymethacrylic acid Polyvinyl pyrrolidone

Pluronic-g-Polyacrylic 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. Antimicrobial composition

The polymer complex according to the invention comprises an antimicrobial composition comprising essential oil and quaternary ammonium biocide.

Essential oil

Essential oils are typically concentrated, hydrophobic liquid containing volatile aroma compounds from plants. Essential oils are also known as volatile, ethereal oils or aetherolea. An oil is "essential" in the sense that it carries a distinctive scent, or essence, of the plant. Essential oils do not as, a group, need to have any specific chemical properties in common, beyond conveying characteristic fragrances.

Essential oils may also be obtained though synthetic or semi-synthetic routes.

Essential oils are generally extracted by distillation. Other processes include expression, or solvent extraction. They are used in perfumes, cosmetics, soap and other products, for flavoring food and drink, and for scenting incense and household cleaning products.

Examples of aromatic essential oils suitable for use in the present invention include amyl salicylate, carvacrol, cymene, e.g. p-cymene, dihydroeugenol, eugenol, hexyl eugenol, hexyl salicylate, isoeugenol, methyl eugenol, methyl isoeugenol, methyl salicylate, tert butyl cresol, thymol, and vanillin. Examples of non-aromatic essential oils of terpenoid compounds include cedrene, cineole, citral (including geranial and neral), citronellal, citronellol, eucalyptol (also known as 1 ,8 cineole)

paradihydrolinalool, dihydromyrcenol (DH myrcenol), farnesol, geraniol, hexyl cinnamaldehyde, hydroxycitronallol, hydroxycitronellal, isocitral, limonene, preferably d-limonene, linalool, longifolene, menthol, nerol, nerolidiol, pinene, e.g. a-pinene, phellendrene, terpinene, e.g. a-terpinene and γ-terpinene, terpineol, e.g. γ-terpineol and terpin-4-ol, and tetrahydromyrcenol (THM).

The most preferred essential oils in the context of the present invention are thymol, terpineol and eugenol.

The essential oil is preferably present in the composition in a concentration of between 0.001 and 10% by weight of the composition, but preferably at least 0.002%, or even at least 0.005% 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%, or even not more than 0.1 % by weight of the concentration.

It is preferred that the composition comprises a second essential oil, wherein the essential oils are even more preferably selected from any combination of a thymol, a terpineol and/or a eugenol.

It is even more preferred that the composition comprises three essential oils, wherein the essential oils are still more preferably selected from a combination of a thymol, a terpineol and a eugenol.

When more than one essential oil is present in the composition, the above mentioned concentrations may be considered to be the concentrations of the combined essential oils, but preferably relate to each of the individual essential oils. Quaternary ammonium biocide

A quaternary ammonium biocide may be used to provide additional biocidal efficacy. 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-Decyl-2-methyl-imidazolium Chloride, 1 -Hexadecyl-3-methyl-imidazolium Chloride, Didecyl-dimethyl-ammonium Bromide, Didecyl-dimethyl-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%, or even not more than 0.1 % by weight of the concentration. The quaternary ammonium biocide provides more complete kill with longer lasting hygiene.

Compositions

The compositions according to the invention may be applied in various hard surface cleaning composition, such as concentrated and dilute liquid compositions.

Concentrated composition include amongst other floor cleaner composition that need to be diluted by the consumers upon use. For this kind of composition, the above mentioned concentrations are relating to the diluted concentrations as used by the consumer.

Dilute liquid compositions include but are not limited to ready-to-use compositions, such as liquid abrasive cleaners and toilet cleaning compositions, and spray compositions for glass, kitchen surfaces and bathroom surfaces It is preferred that the contact time of the product with the surface before rinsing is at least 5 seconds, more preferably at least 10 seconds, still more preferably at least 15 seconds, or even at least 20 seconds. Stay on compositions, may stay for a longer period of time, preferably at least 5 minute, more preferably at least 15 minutes, still more preferably at least 1 hour, still more preferably at least 2 hours, or even more than 5 hours, or even days.

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 6.

Method

Consequently there is provided a method for providing an anti-microbial effect to hard surfaces comprising the steps of applying a composition according to the invention to the surface, waiting for at least 5 seconds.

It is preferred that the composition is not wiped away or rinsed, but may be wiped of after the indicated time.

Examples

The invention will now be illustrated by means of the following non-limiting examples.

Example 1 : EST challenge This test is not a surface test. It is a suspension test The standard European suspension test (EST) protocol - EN 1276 for antiseptics was followed. The test organisms were Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aureus, and Enterococcus hirae. Under clean conditions the test was done with 0.03% BSA (bovine serum albumin), while in dirty condition 0.3% BSA was used (see table 2 below). The contact time was 5 min. A 5 log reduction was required to pass the test. The compositions as used are given in table 1 below.

Table 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 total amount as given in the table.

Table 2

The test results against the individual organisms are given below.

EST - E.coli (5 min contact time)

Avg.d Fu/ml Log Rec uction

Sample Clean Dirty Clean Dirty

E.coli 135000000 125000000 0.0 0.0

Comparative B 4700000 17500000 1 .4 0.8

Comparative A 130000000 128000000 0.0 0.0

Example 1 0.0 0.0 8.1 8.0 EST- S. aureus (5 min contact time)

Avg.d Fu/ml Log Rec uction

Sample Clean Dirty Clean Dirty

S. aureus 4000000 4000000 0.0 0.0

Comparative B 2700000 2800000 0.2 0.2

Example 1 4.0 0.0 6.0 6.6

The results above show that very high reduction of bacteria is achieved with the compositions according to the inventions, while the single components do not achieve even a remotely similar effect.

Example 2: Long Lasting hygiene challenge.

In this example a multi day test has been done. The following compositions were used (as is)

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 total amount as given in the table, or its individual components.

Day 1

• Clean ceramic tiles of 10 by 10 cm are washed with Isopropanol (IPA, 70%) and dried.

• 10 microliter of a 10⁸ cfu/ml E.coli (ATCC 10536) suspension was spread over the tile and dried.

• 1 ml of the fest formulations of the table above was spread over the tiles and left for 10 minutes and the tiles were dried afterwards.

• The tiles were left overnight under moist conditions Day 2

• The tiles were wiped with one wet wipe (DM water only) and one dry wipe.

• Rinsed with water and left to dry

• Left over night under moist conditions Day 3

• 10 microliter of a 10⁸ cfu/ml E.coli suspension was spread over the tile and dried.

• The tiles were wiped with one wet wipe (DM water only) and one dry wipe. « 10 microliter of a 10⁸ cfu/ml E.coli suspension was spread over the tile and dried for 10 min

• 0.5 ml of a neutraliser (D/E Neutraliser) was spread over the tile and left for 5 min

• Neutraliser was collected from the tiles

· Collected neutraliser liquid was serially diluted and plated on CY Agar plate from HiMedia.

Test results (n=3) are given below

The above results show that even after 2 days, the compositions according to the invention still provides anti-microbial activity to the surface, even though the single ingredients do not show the same effect.

Example 3: Long Lasting hygiene challenge.

In this example a multi day test has been done as in example 2, but using different compositions.

The following compositions were used (as is) Comp E Example 3 Example 4

(%w) (%w) (%w)

Thymol 0.025 0.025

Terpineol 0.05 0.05

Eugenol 0.005 0.005

Poly acrylic acid ^v 0.015 0.015 0.015

Poly ethylene oxide ^v 0.01 0.01 0.01

C12-E05 Nonionic 0.15 0.15

Benzalkonium 0.15

chloride

Citric acid 0.02 0.02

Water Up to 100% Up to 100% Up to 100%

The polymer complex comprised PAA (poly acrylic acid; w 100,000 D, ex

Sigma-Aldrich) and PEO (poly ethylene oxide; Mw 100,000 D, ex Sigma-Aldrich), in a total amount as given in the table, or its individual components. Test results (n=3) are given below

The above results show that even after 2 days, the compositions according to the invention still provides anti-microbial activity to the surface, even though the single ingredients do not show the same effect. The additional benefit of benzalkonium chloride is also demonstrated.

Claims

1 A hard surface treatment composition comprising:

a 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 polymer A and polymer B are not of the same class; and,

b an antimicrobial composition comprising:

i essential oil

ii quaternary ammonium biocide

2 A composition according to any one of claims 1 wherein polymer A is present in a concentration of between 0.001 and 25% by weight of the composition.

3 A composition according to any one of claim 1 to 2, wherein polymer B is

present in a concentration of between 0.001 and 20% by weight by weight of the composition.

4 A composition according to any one of claim 1 to 3, wherein the essential oil is present in a concentration of between 0.001 and 10% by weight of the composition.

5 A composition according to any one of the preceding claims, wherein the

composition further comprises a second essential oil, preferably a second and a third essential oil.

6 A composition according to any one of the preceding claims, wherein the

essential oil is selected from amyl salicylate, carvacrol, cymene, e.g. p-cymene, dihydroeugenol, eugenol, hexyl eugenol, hexyl salicylate, isoeugenol, methyl eugenol, methyl isoeugenol, methyl salicylate, tert butyl cresol, thymol, vanillin, cedrene, cineole, citral (including geranial and neral), citronellal, citronellol, eucalyptol (also known as 1 ,8 cineole) paradihydrolinalool, dihydromyrcenol (DH myrcenol), farnesol, geraniol, hexyl cinnamaldehyde, hydroxycitronallol, hydroxycitronellal, isocitral, limonene, preferably d-limonene, linalool,

longifolene, menthol, nerol, nerolidiol, pinene, e.g. a-pinene, phellendrene, terpinene, e.g. a-terpinene and γ-terpinene, terpineol, e.g. γ-terpineol and terpin- 4-ol, and tetrahydromyrcenol (THM). A composition according to any one of the preceding claims, wherein the pH of the composition is between 2 and 9. A method for providing an anti-microbial effect to a hard surface comprising the steps of:

a applying a composition according to any one of claim 1 to 7 to the surface, and

b waiting for at least 5 seconds. A method according to claim 8, wherein the composition is wiped of the surface or rinsed of the surface after step 'b'. Use of a combination of

a a polymer complex comprising

i polymer A selected from the group of homopolymers and copolymers of carboxylic acid and , 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; and an antimicrobial composition comprising i essential oil, and

ii quaternary ammonium biocide,

roviding an anti-microbial effect on hard surfaces.