POLYMERIC FILMS

Abstract

A polymeric film includes a substrate at least partially coated with hydrophobic particles, the hydrophobic particles include: a metal oxide core; and a hydrocarbon chain having from 2 to 40 carbon atoms, wherein the hydrocarbon chain is chemically bound to the metal oxide core

Claims

1. A polymeric film comprising a substrate at least partially coated with hydrophobic particles, the hydrophobic particles comprising: an aluminium oxide core; and a hydrocarbon chain having from 2 to 40 carbon atoms, wherein the hydrocarbon chain is chemically bound to the aluminium oxide core, the hydrophobic particles and the substrate are secured to one another by an adhesive and wherein the mass ratio of the hydrophobic particles and the adhesive is from approximately 1.0:1.0 to approximately 2.0:1.0.

2. A polymeric film according to claim 1, wherein the average diameter of the hydrophobic particles is less than or equal to approximately 200 nm.

3. A polymeric film according to claim 2, wherein the average diameter of the hydrophobic particles is less than or equal to approximately 50 nm.

4. A polymeric film according to claim 3, wherein the average diameter of the hydrophobic particles is from approximately 8 nm to approximately 20 nm.

5. (canceled)

6. A polymeric film according to claim 1, wherein the hydrocarbon chain is aliphatic.

7. A polymeric film according to claim 1, wherein the hydrocarbon chain is straight or branched.

8. A polymeric film according to claim 1, wherein the hydrocarbon chain has from 6 to 32 carbons; or wherein the hydrocarbon chain has from 6 to 24 carbons.

9. (canceled)

10. A polymeric film according to claim 1, wherein the hydrocarbon chain is covalently bound to the metal aluminium oxide core via a functional group.

11. A polymeric film according to claim 10, wherein the functional group comprises any one or a combination of hydroxide, carboxylate, phosphonate, phosphinate, thiolate and thiocarboxylate.

12. A polymeric film according to claim 1, wherein the hydrophobic particles are free from fluorine.

13. A polymeric film according to claim 1, wherein the substrate comprises a thermoplastic film.

14. A polymeric film according to claim 13, wherein the thermoplastic film comprises polyolefin, vinyl polymer or polyacetal film.

15. A polymeric film according to claim 1, wherein the substrate comprises a co-extruded bilayer or multilayer film.

16.-18. (canceled)

19. Use of a polymeric film according to claim 1 as a food packaging film.

20. A food or liquid container comprising a surface, wherein a polymeric film according to claim 1 is laminated to the surface.

21. A food or liquid container according to claim 20, wherein the surface comprises metal, alloy, plastics, cardboard and/or glass.

22. A glass sheet having a polymeric film according to claim 1 laminated thereto.

23. A plastics sheet having a polymeric film according to claim 1 laminated thereto.

24. A fabric sheet having a polymeric film according to claim 1 laminated thereto.

25. An article of clothing or footwear having a polymeric film according to claim 1 laminated thereto.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0047] Embodiments of the invention will now be described by way of example only with reference to the accompanying drawings, in which:

[0048] FIG. 1 is a representation of a hydrophobic particle;

[0049] FIG. 2 shows a polymeric film according to an embodiment of the invention comprising a substrate having hydrophobic particles at least partially embedded therein; and

[0050] FIG. 3 shows a polymeric film according to an embodiment of the invention comprising a substrate and hydrophobic particles bonded thereto by an adhesive.

DESCRIPTION OF EMBODIMENTS

[0051] Referring to FIG. 1 there is shown a hydrophobic particle, represented generally at 1. The hydrophobic particle 1 comprises a metal oxide core 10 and six hydrocarbon chains 12. It is to be appreciated that in other embodiments the hydrophobic particle 1 may have greater than or less than six hydrocarbon chains 12. Each hydrocarbon chain 12 has from 2 to 40 carbon atoms. The hydrocarbon chains 12 are branched, although they could be straight.

[0052] The hydrocarbon chains 12 are chemically bound to the metal oxide core 10. In some embodiments, the hydrocarbon chains 12 may be covalently bound to the metal oxide core 10 via a functional group 14. Suitable metal oxide cores 10 include aluminium oxide, iron oxide, zinc oxide, and silicon oxide.

[0053] The term “oxide” as used herein is intended to include oxide-hydroxides, hydroxides and also oxides having multiple metal oxidation states. For example, iron oxide may include Fe.sub.3O.sub.4 or Fe.sub.2O.sub.3 or a combination thereof.

[0054] In some embodiments, the hydrophobic particle 1 comprises a metal oxide core 10 having a hydrocarbon chain 12 covalently bound thereto by a carboxylate functional group 14. In other embodiments, alternative functional groups may be employed as long as a stable covalent interaction is formed between the metal oxide core 10 and the hydrocarbon chain 12. Alternative functional groups 14 may comprise any one or a combination of hydroxide, phosphonate, phosphinate, thiolate and thiocarboxylate.

[0055] In some embodiments, the hydrocarbon chain 12 may be aliphatic. In particular, the hydrocarbon chain 12 may be chosen from any suitable alkyl organic group as defined by the formula C.sub.xH.sub.y, where x and y are whole numbers and x is from 2 to 40. In some embodiments, the hydrocarbon chain 12 may have from 6 to 32 carbons, such as from 6 to 24 carbons.

[0056] In some embodiments, the hydrocarbon chain 12 may be straight. For instance, the hydrophobic particle 1 may be created by reaction of octanoic acid (CH.sub.3(CH.sub.2).sub.6CO.sub.2H) with the metal oxide core 10.

[0057] In some embodiments, the hydrocarbon chain 12 may be branched. For instance, the hydrophobic particle 1 may be created by reaction of any one of isostearic acid (CH.sub.3(CH.sub.2).sub.16COOH) and 2-hexyldecanoic acid (CH.sub.3(CH.sub.2).sub.7CH[(CH.sub.2).sub.5CH.sub.3]CO.sub.2H) with the metal oxide core 10.

[0058] Creation of the hydrocarbon chains 12 as described herein can provide the advantage that the resultant hydrophobic particles 1 are free from fluorine. This means that the hydrophobic particles 1 of the invention have environmental benefits in that they are less toxic when compared to prior art materials.

[0059] Referring now to FIG. 2, there is shown a polymeric film, indicated generally at 2. The polymeric film 2 comprises a substrate 3 having the hydrophobic particles 1 at least partially embedded therein.

[0060] In some embodiments, the polymeric film 2 is prepared by depositing, e.g. spraying, the hydrophobic particles 1 onto a heated substrate 3. The hydrophobic particles 1 may be dissolved or suspended in a solvent. The exposed surface of the substrate 3 may be heated until it is softened, followed by deposition of the solution or suspension onto the softened surface. After allowing the solvent to evaporate and the substrate 3 to cool the hydrophobic particles 1 become at least partially embedded in the substrate 3. The result is a polymeric film 2 having a stable, textured and hydrophobic surface. In some embodiments, the substrate 3 may be heated by radiation (for example, by infra-red lamps) or by conduction (for example, by placing the substrate 3 on a hot plate or by exposing to heated air). It is to be understood that any method that provides sufficient heating to soften the substrate 3 without compromising its integrity may be employed.

[0061] The choice of solvent is limited only by the need for the solvent to evaporate from the surface of the substrate 3. Suitable solvents include, but are not limited to, isopropanol, toluene and ethanol.

[0062] Referring now to FIG. 3, there is shown a polymeric film, indicated generally at 20. The polymeric film 20 comprises a substrate 30. The hydrophobic particles 1 are secured to the substrate 30 by an adhesive 40.

[0063] In some embodiments, the adhesive 40 may be an epoxy resin. The adhesive 40 may be applied to the substrate 30, followed by deposition of the solution or suspension containing the hydrophobic particles 1, or vice versa. The adhesive 40 is allowed to cure, at which point the hydrophobic particles 1 become bonded to the substrate 30 by virtue of being at least partially embedded in the adhesive 40.

[0064] In some embodiments, the hydrophobic particles 1 and the adhesive 40 may be mixed and the resultant mixture may be deposited, e.g. sprayed, onto the substrate 30.

[0065] Spraying may be effected by dissolving or suspending the mixture in a solvent and utilising a propellant or a compressor as is well known in the industry.

Materials

[0066] The substrate may comprise a thermoplastic film, e.g. a polyethylene copolymer. The substrate used for all of the subsequent experiments was an EVA/EVA/PVDC/EVA/EVA five layer co-extrusion having a thickness of 75 micron.

[0067] Aluminium oxide (Al.sub.2O.sub.3) particles having an average diameter of 13 nm were purchased from Sigma-Aldrich.

[0068] Iron oxide (Fe.sub.3O.sub.4) particles having an average diameter of from 15-20 nm were purchased from Sigma-Aldrich.

[0069] Isostearic acid was purchased from Nissan Chemical Industries and was used without further purification.

[0070] Toluene and isopropanol were supplied by VWR Chemicals.

[0071] SP106 Multi-Purpose Epoxy Resin System 1 kg Slow Hardener was purchased from MB Fibreglass.

[0072] Spraycraft Universal Airbrush Propellant was used for the spray coating and was purchased from Axminster Tools and Machinery.

Water Contact Angle (WCA) Measurements

[0073] WCA measurements were used to study the wettability of the polymeric films. WCA measurements were obtained by depositing 4 μL droplets of H.sub.2O onto the polymeric films. The values of the WCAs that are reported herein are the average of three measurements, recorded at different positions on the surfaces. Standard deviations are used to represent the uncertainties that are associated with these values.

Comparative Example 1

[0074] The WCA of the uncoated substrate (i.e. the clean EVA/EVA/PVDC/EVA/EVA five layer co-extruded film) was 88.3°±1.7°.

Comparative Example 2

[0075] The substrate was coated with unfunctionalised Al.sub.2O.sub.3 particles. Deposition of the unfunctionalised Al.sub.2O.sub.3 particles onto the substrate was achieved through spray coating from 2% wt isopropanolic suspensions at ambient temperature. Three sprays were used to try to achieve maximum coverage of the substrate by the unfunctionalised Al.sub.2O.sub.3 particles.

[0076] Coating the substrate with the unfunctionalised Al.sub.2O.sub.3 particles at ambient temperature resulted in the surface of the polymeric film becoming superhydrophilic. Accordingly, it was not possible to accurately measure the WCA of the resultant polymeric film.

Comparative Example 3

[0077] The substrate was coated with unfunctionalised Fe.sub.3O.sub.4 particles. Deposition of the unfunctionalised Fe.sub.3O.sub.4 particles onto the substrate was achieved through spray coating from 2% wt isopropanolic suspensions at ambient temperature. Three sprays were used to try to achieve maximum coverage of the substrate by the unfunctionalised Fe.sub.3O.sub.4 particles.

[0078] The WCA of the resultant polymeric film was 107.2°±3.4°.

Example 1

[0079] Functionalised aluminium oxide (Al.sub.2O.sub.3) particles were synthesised as follows. Aluminium oxide (Al.sub.2O.sub.3) particles (d=13 nm, 10.0 g, 98.0 mmol, 1.0 equiv.) were refluxed with isostearic acid (39.1 g, 137.3 mmol, 1.4 equiv.) in toluene (250 mL) for 24 hours. Once the reaction time had elapsed, the reaction mixture was collected and centrifuged at 5000 rpm for one hour. The solid was then recovered and centrifuged at 5000 rpm in isopropanol for one hour. Following this, the solid was centrifuged in ethanol at 5000 rpm for one hour three further times, and then dried at 80° C. for six hours.

[0080] The substrate was coated with the functionalised Al.sub.2O.sub.3 particles. Deposition of the functionalised Al.sub.2O.sub.3 particles onto the substrate was achieved through spray coating from 2% wt isopropanolic suspensions at ambient temperature. Three sprays were used to try to achieve maximum coverage of the substrate by the functionalised Al.sub.2O.sub.3 particles.

[0081] The WCA of the resultant polymeric film was 151.1°±1.0°.

Example 2

[0082] Functionalised iron oxide (Fe.sub.3O.sub.4) particles were synthesised as follows. Iron oxide (Fe.sub.3O.sub.4) particles (d=15-20 nm, 5.0 g, 21.6 mmol, 1.0 equiv.) were refluxed in toluene (100 mL) with isostearic acid (18.4 g, 64.7 mmol, 3.0 equiv.) for approximately twenty-four hours, under mechanical stirring. Once the reaction time had elapsed, the mixture was centrifuged at 5000 rpm for one hour. Following this, the solid was recovered and dried at 80° C. for six hours.

[0083] The substrate was coated with the functionalised Fe.sub.3O.sub.4 particles. Deposition of the functionalised Fe.sub.3O.sub.4 particles onto the substrate was achieved through spray coating from 2% wt isopropanolic suspensions at ambient temperature. Three sprays were used to try to achieve maximum coverage of the substrate by the functionalised Fe.sub.3O.sub.4 particles.

[0084] The WCA of the resultant polymeric film was 151.9°±2.1°.

Example 3

[0085] The substrate was heated and coated with the functionalised Al.sub.2O.sub.3 particles described in Example 1. The functionalised Al.sub.2O.sub.3 particles were spray coated onto the substrate once it had been softened as a result of heating. Heating of the substrate was accomplished as follows. First, the substrate was physically attached at its edges to the surface of a glass petri dish. The purpose of this was to secure the substrate in order to limit the extent to which it changed shape during the heating process. Heat was then applied to the petri dish until physical deformation of the substrate was observed. Once physical deformation of the substrate was observed, deposition of the functionalised Al.sub.2O.sub.3 particles onto the substrate was achieved through spray coating. The functionalised Al.sub.2O.sub.3 particles were spray coated from a 2.0% wt suspension. Five sprays were used to try to achieve maximum coverage of the substrate by the functionalised Al.sub.2O.sub.3 particles. Following each spray, the substrate was continually heated in order to accelerate the removal of the isopropanol. Further spray coating was performed on the substrate when no liquid was observed its surface. The temperature of the substrate was not measured prior to spray coating. However, it was observed that the substrate would start to deform plastically when heated to between 80-90° C.

[0086] The WCA of the resultant polymeric film was 142.0°±3.9°.

[0087] Although this value is slightly lower than when the functionalised Al.sub.2O.sub.3 particles were deposited onto the substrate at ambient temperature (Example 1), it is noteworthy that water droplets would readily roll off the polymeric film. Accordingly, this suggests that heating of the substrate during application of the hydrophobic particles does not overly detriment the desired hydrophobic nature of the resultant polymeric film.

[0088] In order to determine how well the functionalised Al.sub.2O.sub.3 hydrophobic particles bonded to the substrate the polymeric film was sonicated in isopropanol for approximately ten minutes and the WCA was retested.

[0089] Following sonication, the WCA of the polymeric film was 137.7°±7.9°. It is evident that the WCA did not change significantly following sonication which indicates a strong thermal embedding of the functionalised Al.sub.2O.sub.3 hydrophobic particles within the substrate.

Example 4

[0090] The substrate was heated and coated with the functionalised Fe.sub.3O.sub.4 particles described in Example 2 according to the method described in Example 3.

[0091] The WCA of the resultant polymeric film was 151.9°±2.7°.

[0092] In order to determine how well the functionalised Fe.sub.3O.sub.4 hydrophobic particles bonded to the substrate the polymeric film was sonicated in isopropanol for approximately ten minutes and the WCA was retested.

[0093] Following sonication, the WCA of the polymeric film was 90.3°±0.5°. This represents a WCA close to that of the uncoated substrate. This indicates that most of the functionalised Fe.sub.3O.sub.4 hydrophobic particles were removed by the sonication. Without being bound to any particular theory, it is understood that functionalised Fe.sub.3O.sub.4 hydrophobic particles form relatively large agglomerates on the substrate that are less strongly embedded than, say, functionalised Al.sub.2O.sub.3 hydrophobic particles. Accordingly, the functionalised Fe.sub.3O.sub.4 hydrophobic particles or more easily removed than the functionalised Al.sub.2O.sub.3 hydrophobic particles. However, that is not to say that embodiments incorporating functionalised Fe.sub.3O.sub.4 hydrophobic particles are not commercially viable. The sonication test merely seeks to replicate a highly destructive environment to determine the degree of bonding between the hydrophobic particles and the substrate. Hydrophobic films are unlikely to experience such a highly destructive environment in normal use.

Examples 5 to 9

[0094] Bonding of the functionalised Al.sub.2O.sub.3 particles and the substrate by an epoxy resin was studied in examples 5 to 9.

[0095] In example 5, 0.08 g of epoxy resin was added to 0.66 g of the functionalised Al.sub.2O.sub.3 particles described in Example 1 and suspended in 40 mL of isopropanol, such that the mass ratio of functionalised Al.sub.2O.sub.3 particles:epoxy resin was approximately 8.6:1.0. Deposition of the mixture onto the substrate was performed through spray coating at ambient temperature, as described previously. Spray coating this suspension onto the substrate resulted in a polymeric film having a WCA of 144.3°±4.3°.

[0096] In examples 6 to 9, the ratio of the functionalised Al.sub.2O.sub.3 particles and epoxy resin was adjusted.

[0097] The functionalised Al.sub.2O.sub.3 particle and epoxy resin ratios and the corresponding WCAs for the polymeric films of examples 5 to 9 are summarised in Table 1. Table 1 also shows the WCAs for the polymeric films after they have been sonicated in isopropanol for approximately ten minutes.

TABLE-US-00001 TABLE 1 Water contact angle (°) before and after sonication as a function of the ratio of functionalised Al.sub.2O.sub.3 particles and epoxy resin. Functionalised Al.sub.2O.sub.3 Water contact particles:epoxy Water contact angle (°) after Example resin angle (°) sonication 5 8.6:1.0 144.3 ± 4.3° 132.2 ± 7.4° 6 2.0:1.0 149.9 ± 1.1° 137.1 ± 1.0° 7 1.5:1.0 150.7 ± 1.2° 135.9 ± 7.5° 8 1.0:1.0 149.0 ± 7.8° 141.1 ± 1.6° 9 1.0:1.4 138.1 ± 10.4° 142.0 ± 0.6°

[0098] Whilst all of examples 5 to 9 achieved high WCAs, it is clear that polymeric films with the best hydrophobicity were created when the ratio of the functionalised Al.sub.2O.sub.3 particles and epoxy resin was from approximately 1.0:1.0 (i.e. 149.0±7.8°) to approximately 2.0:1.0 (i.e. 149.9±1.1°), e.g. 1.5:1.0 (i.e. 150.7±1.2°).

[0099] Moreover, as with Example 3, it is evident that the WCAs of Examples 5 to 9 did not change significantly following sonication. This appears to indicate a strong embedding of the functionalised Al.sub.2O.sub.3 hydrophobic particles within the epoxy resin.

Examples 10 to 14

[0100] Bonding of the functionalised Fe.sub.3O.sub.4 particles and the substrate by an epoxy resin was studied in examples 10 to 14. The substrate was coated with a mixture of the epoxy resin and the functionalised Fe.sub.3O.sub.4 particles described in Example 2. In these examples, epoxy resin was added to the functionalised Fe.sub.3O.sub.4 particle suspension. Deposition of the mixture onto the substrate was performed through spray coating at ambient temperature, as described previously.

[0101] The functionalised Fe.sub.3O.sub.4 particle and epoxy resin ratios and the corresponding WCAs for the polymeric films of examples 10 to 14 are summarised in Table 2. Table 2 also shows the WCAs for the polymeric films after they have been sonicated in isopropanol for approximately ten minutes.

TABLE-US-00002 TABLE 2 Water contact angle (°) before and after sonication as a function of the ratio of functionalised Fe.sub.3O.sub.4 particles and epoxy resin. Water contact Isostearate functionalised Water contact angle (°) after Example Fe.sub.3O.sub.4 particles:epoxy resin angle (°) sonication 10 11.8:1.0 124.3 ± 10.6° 92.7 ± 8.3° 11  6.5:1.0 102.1 ± 4.3° 85.3 ± 14.5° 12  2.0:1.0  89.9 ± 4.7° 84.4 ± 5.9° 13  1.0:1.0  75.4 ± 2.2° 81.4 ± 3.0° 14  1.0:1.5  80.7 ± 10.8° 81.8 ± 2.5°

[0102] When compared with Examples 5 to 9, the WCAs of Examples 10 to 14 are not as high. However, there is a clear trend that the WCA increases when increasing the ratio functionalised Fe.sub.3O.sub.4 particles to epoxy resin. Therefore, it is plausible that the WCA could exceed 140° in embodiments where the functionalised Fe.sub.3O.sub.4 particle to epoxy resin ratio exceeds 15:1.

[0103] In summary, the present invention relates to polymeric films that have improved self-cleaning properties by virtue of attaching hydrophobic particles comprising a metal oxide core having hydrocarbon chains with from 2 to 40 carbon atoms to a substrate, such as a thermoplastic film. It has been found that the surface energy of these polymeric films is very low and non-toxic. Accordingly, the polymeric films can be used in a wide range of applications, including food and liquid packaging. It is also envisaged that the polymeric films can be laminated to a glass, plastics or fabric sheet for improving the hydrophobicity thereof.

[0104] It may be useful to tune the WCA at different regions of the polymeric film. In some embodiments, polymeric films may have a first region having an associated WCA measurement and a second region having an associated WCA measurement, whereby the WCA measurements at the first and second regions are different. One way in which this can be achieved is by varying the concentration of hydrophobic particles that are deposited at the first and second regions. For instance, a solution of 4 wt % of Al.sub.2O.sub.3 hydrophobic particles may be deposited at the first region and a solution of 2 wt % Al.sub.2O.sub.3 hydrophobic particles may be deposited at the second region. Accordingly, the first region will have a high WCA than the second region due to the high concentration of Al.sub.2O.sub.3 hydrophobic particles.

[0105] As used herein, the term “hydrocarbon chain” is intended to have its usual meaning, i.e. a molecule that consists entirely of hydrogen and carbon.

[0106] Representative features are set out in the following clauses, which stand alone or may be combined, in any combination, with one or more features disclosed in the text and/or drawings of the specification.

[0107] When used in this specification and claims, the terms “comprises” and “comprising” and variations thereof mean that the specified features, steps or integers are comprised. The terms are not to be interpreted to exclude the presence of other features, steps or components.

[0108] The features disclosed in the foregoing description, or the following claims, or the accompanying drawings, expressed in their specific forms or in terms of a means for performing the disclosed function, or a method or process for attaining the disclosed result, as appropriate, may, separately, or in any combination of such features, be utilised for realising the invention in diverse forms thereof.

[0109] Although certain example embodiments of the invention have been described, the scope of the appended claims is not intended to be limited solely to these embodiments. The claims are to be construed literally, purposively, and/or to encompass equivalents.