Patent Application
20110081530
The present application is concerned with anti-microbial polymeric film, particularly polyester film.
The preparation of polymeric films having anti-microbial properties is well-known. Such films are of use in the provision of anti-microbial surfaces, for example in medical and catering environments. The anti-microbial properties are imparted using an anti-microbial agent. The preparation of such films typically involves disposing the anti-microbial agent into the polymer matrix or on one or more surface(s) as a coating. Desirably, the anti-microbial agent should have a broad spectrum of activity over different microbes, and a low toxicity profile for higher organisms. Metal ions, particularly silver ions, have long been known to exhibit anti-fungal, anti-bacterial and anti-algal activity (hereinafter referred to as anti-microbial activity). Recently, it has been proposed to use an anti-microbial metal ion supported on zirconium phosphate, as disclosed in, for instance, U.S. Pat. No. 5,441,717, JP-A-3/83905 and U.S. Pat. No. 5,296,238. U.S. Pat. No. 5,556,699 discloses use of a zeolite antibacterial agent in a coextruded or laminated film comprising inter alia PVC, polyolefin, polyester and/or polyvinyl alcohol layers, which is useful for packaging foods and medical equipment. U.S. Pat. No. 5,639,466 discloses a packaging film comprising an anti-bacterial composition of (a) 5-40% lactide or lactic acid oligomer; (b) 0-20% organic plasticiser; and (c) 60-95% lactic acid polymer or copolymer, which is coated as a layer of at least 5 μm in thickness on a polymeric substrate. EP-A-0846418 discloses antibacterial films comprising an inorganic and/or organic antibacterial agent and a hydrophilic substance, which is suitable for use in food packaging.
WO-2004/063254-A discloses an anti-microbial polymeric film comprising a polymeric substrate layer and on a surface thereof a polymeric coating comprising an anti-microbial compound, wherein the polymeric coating also provides heat-sealability and/or barrier properties.
WO-2006/000755-A discloses an anti-microbial polymeric film comprising a polymeric substrate layer which contains 0.05 to 0.7 wt % of a silver-containing anti-microbial compound. The anti-microbial compound is preferably added to the substrate polymer after polymerisation and prior to film formation.
It is desired to provide an antimicrobial film having greater anti-microbial efficacy. In addition, anti-microbial agents are relatively expensive and the consumer must generally balance anti-microbial efficacy against cost. It would be desirable to provide more economical anti-microbial films for a given anti-microbial efficacy, or films having greater anti-microbial efficacy for a given cost. It is also desirable for an anti-microbial film to exhibit good optical properties, such as low haze and high gloss, comparable with a film without the anti-microbial agent.
In addition, it is desirable for an anti-microbial film to exhibit excellent durability in that the anti-microbial activity is retained over time. In the prior art anti-microbial films, the anti-microbial agent has a tendency to be lost or abraded from the surface of the film, and this is particularly a problem for those prior art films in which the anti-microbial agent is in particulate form. The inventors have nevertheless observed that it remains desirable for the anti-microbial agent to be present near the surface of the film in order to maximise anti-microbial activity. One of the particular objects of the present invention is to resolve this trade-off and provide a film which shows excellent initial anti-microbial activity as well as excellent retention of anti-microbial activity over time. It is a further object of this invention to provide an anti-microbial film containing a particulate anti-microbial agent which exhibits improved abrasion resistance of the particulate anti-microbial agent.
It is an object of this invention to provide an anti-microbial film which addresses one or more of the afore-mentioned problems.
According to the present invention, there is provided a method of manufacture of an anti-microbial polymeric film, said method comprising:
(a) coextruding a polymeric substrate layer comprising a first layer of a first polymeric material and a second layer of a second polymeric material wherein the crystalline melting temperature (TM2) of said second polymeric material is lower than the crystalline melting temperature (TM1) of the first polymeric material;
(b) stretching the coextruded substrate in a first direction
(c) optionally stretching the substrate layer in a second, orthogonal direction;
(d) disposing on the surface of the polymeric second layer a composition comprising a particulate antimicrobial compound and a liquid vehicle, and preferably also a surfactant; and
(e) heat-setting the stretched film at a temperature above the crystalline melting temperature (TM2) of the second polymeric material but below the crystalline melting temperature (TM1) of the first polymeric material;
wherein step (d) is prior to step (b), or between steps (b) and (c), or after step (c), and before step (e);
such that in the final film said second layer comprises said anti-microbial compound in an amount of from about 1 to about 80% by weight of said polymeric material of the second layer.
The inventors have found that the application of a particulate antimicrobial compound to a coextruded film during the process of film manufacture provides unexpectedly greater anti-microbial activity than incorporation of the antimicrobial compound into the polymeric material used to make the coextruded film. Further, the novel manufacturing process allows for the retention of the antimicrobial compound on the film surface.
According to a further aspect of the present invention, there is provided an anti-microbial polymeric film comprising a coextruded stretched and heat-set polymeric substrate layer comprising a first layer of a first polymeric material and a second layer of a second polymeric material, wherein:
(i) the crystalline melting temperature (TM2) of said second polymeric material is lower than the crystalline melting temperature (TM1) of the first polymeric material; and
(ii) said second layer comprises a particulate anti-microbial compound in an amount of from about 1 to about 80% by weight of said polymeric material of the second layer, wherein said anti-microbial compound is applied via a liquid vehicle to the exposed surface of the second layer prior to heat-setting the coextruded film.
In one embodiment of the present invention, there is provided an anti-microbial polymeric film comprising a coextruded polymeric substrate layer comprising a first layer of a first polymeric material and a second layer of a second polymeric material, wherein:
(i) the crystalline melting temperature (TM2) of said second polymeric material is lower than the crystalline melting temperature (TM1) of the first polymeric material;
(ii) said second layer comprises a particulate anti-microbial compound in an amount of from about 1 to about 80% by weight of said polymeric material of the second layer; and
(iii) the exposed surface of the second layer exhibits a Surface Area Index of at least 1.10 and/or an Average Surface Slope of at least 6°.
As used herein, the term “anti-microbial” means microbicidal activity or microbe growth inhibition in a microbe population, particularly Escherichia coli and/or methicillin-resistant Staphylococcus aureus (MRSA; also referred to as multiple-resistant Staphylococcus aureus). As used herein, the term “anti-microbial” means a greater than 3 log reduction, preferably a greater than 4 log reduction, and more preferably a greater than 5 log reduction in a population of microbes relative to a control, measured after 24 hours. In a preferred embodiment, the term “anti-microbial” means a greater than 3 log reduction, preferably a greater than 4 log reduction, and more preferably a greater than 5 log reduction in a population of microbes relative to a control, measured after 12 hours, preferably after 6 hours, more preferably after 3 hours. The films disclosed herein represent an improvement over currently commercially available anti-microbial films in that they exhibit a higher log reduction of a microbe population and/or higher kill rates. Antimicrobial activity is measured herein according to “the standard method” of JIS Z 2801:2000 as described hereinbelow, and preferably according to the more challenging conditions of “the scenario method” of JIS Z 2801:2000 as described hereinbelow.
The anti-microbial agent may be an inorganic or organic compound or a mixture thereof.
The term “inorganic anti-microbial agent” used herein is a general term for inorganic compounds which contain a metal or metal ions, such as silver, zinc, copper and the like which have anti-microbial properties. The metal-containing species may be supported on an inorganic substance such as silica or like metal oxides, zeolite, synthetic zeolite, zirconium phosphate, calcium phosphate, calcium zinc phosphate, ceramics, soluble glass powders, alumina silicone, titanium zeolite, apatite, calcium carbonate and the like. Other metal-containing anti-microbial compounds include mercury acetates and organozinc compounds.
Solid organic anti-microbial agents include 2-bromo-2-nitropropane-1,3-diol (for example, Canguard® 409 made by Angus Chemical Co., Buffalo Grove, Ill., USA); 3,5-dimethyltetrahydro-1,3,5-2H-thiazine-2-thione (for example, Nuosept® made by Creanova, Inc., Piscataway, N.J., USA or Troysan® 142 made by Troy Chemical Corp., West Hanover, N.J., USA); N-(trichloromethyl)-thiophthalimide (for example, Fungitrol® 11 made by Creanova, Inc.); butyl-p-hydroxy-benzoate (for example, Butyl Parabens® made by International Sourcing Inc., Upper Saddle River, N.J., USA); diiodomethyl-p-tolysulfone (for example, Amical® WP made by Angus Chemical Co.); and tetrachloroisophthalonitrile (for example, Nuocide® 960 by Creanova, Inc.).
With regard to metal-containing anti-microbial agents, silver-containing agents are particularly preferred. Sources of silver for anti-microbial use include metallic silver, silver salts and organic compounds that contain silver. Silver salts include silver carbonate, silver sulfate, silver nitrate, silver acetate, silver benzoate, silver chloride, silver fluoride, silver iodate, silver iodide, silver lactate, silver nitrate, silver oxide and silver phosphates. Organic compounds containing silver may include for example, silver acetylacetonate, silver neodecanoate and silver ethylenediaminetetraacetates. Silver containing zeolites (for example, AJ10D containing 2.5% silver as Ag(I), made by AgION™. Tech. L.L.C., Wakefield, Mass., USA) are of particular use. Zeolites are useful because when carried in a polymer matrix they may provide silver ions at a rate and concentration that is effective at killing and inhibiting micro-organisms without harming higher organisms.
In a preferred embodiment, the anti-microbial compound is selected from those disclosed in U.S. Pat. No. 5,441,717 or U.S. Pat. No. 5,296,238. Preferably, the anti-microbial compound has formula (I):
M1aHbAcM22(PO4)3.nH2O (I)
wherein
M1 is at least one metal ion selected from silver, copper, zinc, tin, mercury, lead, iron, cobalt, nickel, manganese, arsenic, antimony, bismuth, barium, cadmium and chromium;
A is at least one ion selected from an alkali or alkaline earth metal ion;
M2 is a tetravalent metal ion;
a and b are positive numbers and c is 0 or a positive number such that (ka+b+mc)=1;
k is the valence of metal M1;
m is the valence of metal A; and
0≦n≦6.
Preferably, M1 is silver and the anti-microbial compound has formula (II):
AgaHbAcM2(PO4)3.nH2O (II)
wherein
A is at least one ion selected from an alkali or alkaline earth metal ion;
M is a tetravalent metal ion;
a, b and c are positive numbers such that (a+b+mc)=1;
m is the valence of metal A; and
0≦n≦6.
The anti-microbial compounds of formula (I) may be prepared according to the methods described in U.S. Pat. No. 5,441,717 or U.S. Pat. No. 5,296,238. The anti-microbial silver ion is supported on the zirconium phosphate. The metal A is preferably selected from lithium, sodium, potassium, magnesium and calcium, and is preferably sodium. The metal M is preferably selected from zirconium, titanium and tin, preferably from zirconium and titanium, and is preferably zirconium.
The value of the parameter “a” is preferably at least 0.001, more preferably at least 0.01, and is preferably in the range of 0.01 to 0.5, more preferably 0.1 to 0.5, more preferably 0.10 to 0.30. In one embodiment, the value of the parameter “a” is in the range from 0.4 to 0.5 or in the range 0.15 to 0.25, preferably in the range 0.4 to 0.5.
The value of the parameter “b” is preferably at least 0.2, more preferably in the range of 0.2 to 0.7, more preferably in the range of 0.2 to 0.60. In one embodiment, the value of the parameter “b” is on the range 0.2 to 0.3.
In one embodiment, the antimicrobial compound is selected from Ag0.18Na0.57H0.25Zr2(PO4)3 and Ag0.46Na0.29H0.25Zr2(PO4)3.
Other specific examples of inorganic antibacterial agents are Novaron (product of Toagosei Co., Ltd.), Bactekiller (Kanebo Kasei Co., Ltd.), fine particles of antibacterial spherical ceramics S1, S2, S5 (Adomatex Co., Ltd.), Horonkiller (Nikko Co., Ltd.), Zeomic (Sinagawa Fuel Co., Ltd.), Amenitop (Matsushita Electric Industrial Co., Ltd.), Ionpure (Ishizuka Glass Co. Ltd.) and like silver-based antibacterial agents, Z-Nouve (Mitsui Mining & Smelting Co., Ltd.) and like zinc-based antibacterial agents, P-25 (Nippon Aerosil Co., Ltd.), ST-135 (Ishihara Sangyo Co., Ltd.).
In one embodiment, the particle size of the anti-microbial compound is such that the volume distributed mean particle diameter is in the range of from about 0.1 to about 10 μm, in a further embodiment from about 0.2 to about 2.0 μm, and in a further embodiment from about 0.5 to about 1.5 μm. The antimicrobial particles may, and typically do, become aggregated in the final film and for the avoidance of doubt the particle diameters quoted herein refer to those of the primary, non-aggregated particles.
The anti-microbial compound is present in the second layer in an amount from about 1 to about 80% by weight, in one embodiment from about 15 to about 80% by weight of the polymeric material of the second layer, and typically at least about 20%, more typically at least about 25%, more typically at least about 30%, more typically at least about 35%, more typically at least about 40%, more typically at least about 45%, and more typically at least about 50% by weight of the polymeric material of the second layer. In one embodiment, the anti-microbial compound is present in the second layer in an amount of no more than about 75% by weight of the polymeric material of the second layer, in a further embodiment no more than about 70%, and in a further embodiment no more than about 65% by weight. Thus, the present invention provides a method of disposing very high concentrations of antimicrobial agent into a polymeric film, and such high concentrations are simply not accessible using conventional manufacturing processes which incorporate the antimicrobial additive into the film-forming polymeric material prior to film formation.
In one embodiment, the anti-microbial compound is present in the second layer in an amount from about 1 to about 15% by weight of the total polymeric material of the second layer, and in a further embodiment in the range from about 1 to about 10% by weight of the total polymeric material of the second layer, and in a further embodiment in the range from about 5 to about 10% of the total polymeric material of the second layer.
In a further embodiment, the anti-microbial compound is present at no more than about 2.0% by weight of the total polymeric material of the substrate, and in a further embodiment in the range of from about 0.05% to about 0.7% by weight of the total polymeric material of the substrate.
The particulate anti-microbial compound is disposed in the second layer such that at least some of the anti-microbial particles are exposed in the final film, i.e. partially encapsulated by the polymeric material of the second layer so that the particles are held in place by, but not submerged within, the polymeric matrix. In one embodiment, at least 50%, preferably at least 70%, preferably at least 90%, of the anti-microbial particles are disposed in this way. The film of the present invention is thus characterised in having a very high surface concentration of anti-microbial agent.
The surfaces of the films disclosed herein can suitably be characterised using conventional non-contact interferometry techniques, and in particular on the basis of one or more of the parameters of Average Surface Roughness (Ra), Root Mean Square Average Surface Roughness (Rq), Surface Area Index and/or Average Surface Slope, as defined hereinbelow. In one embodiment, the films of the present invention exhibit a Surface Area Index of at least 1.10, preferably at least 1.15%, preferably at least 1.20, preferably at least 1.25 and preferably at least 1.30; and/or an Average Surface Slope of at least 6°, preferably at least 10°, more preferably at least 15°.
The coextruded polymeric substrate layer is a self-supporting film or sheet by which is meant a film or sheet capable of independent existence in the absence of a supporting base. The substrate comprises two or more discrete layers of the film-forming materials referred to hereinbelow. For instance, the substrate may comprise two, three, four or five or more layers and typical multi-layer structures may be of the AB, ABA, ABC, ABAB, ABABA or ABCBA type. In a preferred embodiment, the substrate comprises only two layers.
The substrate may be formed from any suitable film-forming polymer, including polyolefin (such as polyethylene and polypropylene), polyamide (including nylon), PVC and polyester. In a preferred embodiment, the substrate is polyester, and particularly synthetic linear polyester. The preferred synthetic linear polyesters of the substrate may be obtained by condensing one or more dicarboxylic acids or their lower alkyl (up to 6 carbon atoms) diesters, eg terephthalic acid, isophthalic acid, phthalic acid, 2,5-, 2,6- or 2,7-naphthalenedicarboxylic acid, succinic acid, sebacic acid, adipic acid, azelaic acid, 4,4′-diphenyldicarboxylic acid, hexahydro-terephthalic acid or 1,2-bis-p-carboxyphenoxyethane (optionally with a monocarboxylic acid, such as pivalic acid) with one or more glycols, particularly an aliphatic or cycloaliphatic glycol, e.g. ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol and 1,4-cyclohexanedimethanol. An aromatic dicarboxylic acid is preferred. An aliphatic glycol is preferred. Polyesters or copolyesters containing units derived from hydroxycarboxylic acid monomers, such as co-hydroxyalkanoic acids (typically C3-C12) such as hydroxypropionic acid, hydroxybutyric acid, p-hydroxybenzoic acid, m-hydroxybenzoic acid, or 2-hydroxynaphthalene-6-carboxylic acid, may also be used.
In a preferred embodiment, the polyesters used for the substrate layers are selected from polyethylene terephthalate and polyethylene naphthalate, or copolymers based thereon. Polyethylene terephthalate (PET) homopolymers and copolymers are particularly preferred. As used herein the term PET (or PEN) copolymer refers to a copolyester comprising monomeric units derived from ethylene glycol and terephthalic acid (or naphthalene dicarboxylic acid), together with one or more additional glycol(s) and/or one or more additional dicarboxylic acid units.
In a preferred embodiment, the polyester of the first layer is PET.
In a preferred embodiment, the polyester of the second layer is a copolyester comprising monomeric units derived from ethylene glycol and terephthalic acid, together with one or more additional glycol(s) and/or one or more additional dicarboxylic acid(s), particularly those noted above. In a preferred embodiment, the copolyester of the second layer comprises monomeric units derived from terephthalic acid (TA) and isophthalic acid (IPA), with one or more diols (preferably one diol) selected from the group consisting of aliphatic and cycloaliphatic diols, preferably ethylene glycol. Preferably, the molar ratios of the isophthalate polyester units to the terephthalate polyester units are from 1 to 40 mol % isophthalate and from 99 to 60 mol % terephthalate, preferably from 15 to 20 mol % isophthalate and from 85 to 80 mol % terephthalate. In a preferred specific embodiment, the copolyester comprises about 18 mol % ethylene isophthalate and about 82 mol % ethylene terephthalate.
The crystalline melting temperature (TM2) of the polymeric material of the second layer should be lower than the crystalline melting temperature (TM1) of the polymeric material of the first layer, and preferably (TM1-TM2) is at least 5° C., preferably at least 10° C., preferably at least 20° C., and preferably no more than about 70° C., preferably no more than 60° C. and preferably no more than about 50° C. In one embodiment, (TM2) is in the range of from about 200 to about 220° C.
Formation of the substrate is effected by coextrusion, a technique which is well-known in the art, and in accordance with the procedure described below. In general terms the process comprises the steps of extruding a layer of molten polymer, quenching the extrudate and orienting the quenched extrudate in at least one direction.
The substrate may be uniaxially-oriented, but is preferably biaxially-oriented. Orientation may be effected by any process known in the art for producing an oriented film, for example a tubular or flat film process. Biaxial orientation is effected by drawing in two mutually perpendicular directions in the plane of the film to achieve a satisfactory combination of mechanical and physical properties.
In a tubular process, simultaneous biaxial orientation may be effected by extruding a thermoplastics polymer tube which is subsequently quenched, reheated and then expanded by internal gas pressure to induce transverse orientation, and withdrawn at a rate which will induce longitudinal orientation.
In the preferred flat film process, the substrate-forming polymer is extruded through a slot die and rapidly quenched upon a chilled casting drum to ensure that the polymer is quenched to the amorphous state. Orientation is then effected by stretching the quenched extrudate in at least one direction at a temperature above the glass transition temperature of the polyester. Sequential orientation may be effected by stretching a flat, quenched extrudate firstly in one direction, usually the longitudinal direction, i.e. the forward direction through the film stretching machine, and then in the transverse direction. Forward stretching of the extrudate is conveniently effected over a set of rotating rolls or between two pairs of nip rolls, transverse stretching then being effected in a stenter apparatus. Alternatively, the cast film may be stretched simultaneously in both the forward and transverse directions in a biaxial stenter. Stretching is effected to an extent determined by the nature of the polymer, for example polyethylene terephthalate is usually stretched so that the dimension of the oriented film is from 2 to 5, more preferably 2.5 to 4.5 times its original dimension in the or each direction of stretching. Typically, stretching is effected at temperatures higher than the Tg of the polyester, preferably about 15° C. higher than the Tg. Greater draw ratios (for example, up to about 8 times) may be used if orientation in only one direction is required. It is not necessary to stretch equally in the machine and transverse directions although this is preferred if balanced properties are desired.
The stretched film is dimensionally stabilised by heat-setting under dimensional restraint. The heat-setting step is normally conducted at a temperature above the glass transition temperature of the polyester but below the melting temperature thereof, to induce crystallisation of the polyester. In the present invention, the temperature of the heat-setting step is below the melting temperature of the first layer but above the melting temperature of the second layer, and should normally also be selected so that it is sufficient to evaporate the liquid vehicle of the anti-microbial coating composition. In the present invention, the first layer typically exhibits relatively high crystallinity and the second layer typically exhibits relatively low crystallinity in the final film, which is a result of the combination of the compositional and process features described herein. In one embodiment, the heat-setting conditions should be sufficient to evaporate substantially all of said liquid vehicle (i.e. at least 80%, preferably at least 85%, preferably at least 90%, preferably at least 95%, preferably at least 99%). The actual heat-set temperature and duration will therefore vary depending on the composition of the film and coating composition, but should not be selected so as to substantially degrade the mechanical properties of the film. Within these constraints, a heat-set temperature of about 180° to 245° C. is generally desirable. The duration of the heat-setting step varies with the speed of the film-web through the heat-setting zone(s), but typical durations are in the range of from about 30 seconds to about 180 seconds, typically from about 100 to about 160 seconds. During the heat-setting, a small amount of dimensional relaxation may be performed in the transverse direction, TD by a procedure known as “toe-in”. Toe-in can involve dimensional shrinkage of the order 2 to 8% but an analogous dimensional relaxation in the machine direction (MD) is difficult to achieve since low line tensions are required and film control and winding becomes problematic.
Coextrusion of the multilayer substrate may be effected either by simultaneous coextrusion of the respective film-forming layers through independent orifices of a multi-orifice die, and thereafter uniting the still molten layers, or, preferably, by single-channel coextrusion in which molten streams of the respective polymers are first united within a channel leading to a die manifold, and thereafter extruded together from the die orifice under conditions of streamline flow without intermixing thereby to produce a multi-layer polymeric film, which may be oriented and heat-set as hereinbefore described.
In one embodiment, the substrate is heat-shrinkable. The shrinkage characteristics of a film are determined by the stretch ratios and heat-setting conditions employed during its manufacture, as is well-known to the skilled person. In general, the shrinkage behaviour of a film which has not been heat-set corresponds to the degree to which the film has been stretched during its manufacture. In the absence of heat-setting, a film which has been stretched to a high degree will exhibit a high degree of shrinkage when subsequently exposed to heat; a film which has only been stretched by a small amount will only exhibit a small amount of shrinkage. Heat-setting has the effect of providing dimensional stability to a stretched film, and “locking” the film in its stretched state. Thus, the shrinkage behaviour of a film under the action of heat depends on whether, and to what extent, the film was heat-set after the stretching operation(s) effected during its manufacture. In general, a film which has experienced a temperature T1 during the heat-setting operation will exhibit substantially no shrinkage below temperature T1 when subsequently exposed to heat after manufacture. Accordingly, in order to impart shrinkage characteristics, the substrate is not heat-set or partially heat-set at a relatively low temperature and/or using a relatively short duration after stretching has been effected. A shrinkable substrate may exhibit shrinkage in one or both directions of the film. The degree of shrinkage in one dimension may be the same as, or different to, the degree of shrinkage in the orthogonal direction. In one embodiment, the shrinkage is in the range of from about 0 to about 80% when placed in a water bath at 100° C. for 30 seconds, in a further embodiment from about 5 to about 80%, and in a further embodiment from about 10 to 60%.
The substrate is suitably of a thickness between about 5 and 350 μm, particularly from 12 to about 250 μm, particularly from about 12 to about 125 μm, and particularly from about 12 to about 50 μm. In one embodiment, the thickness of the second layer is from about 0.1 to about 30% of the thickness of the total substrate, in a further embodiment from about 0.1 to about 20%, in a further embodiment from about 0.1 to about 10%, in a further embodiment from about 0.2 to about 5%, and in a further embodiment from about 0.5 to about 2%, of the thickness of the total substrate. In a further embodiment, the thickness of the second layer is in the range of from about 0.1 to about 10 μm, in a further embodiment in the range of from about 0.2 to about 5 μm, and in a further embodiment in the range of from about 0.5 to about 2 μm. In a further embodiment, the thickness of the second layer is controlled as a function of the particle size of a particulate antimicrobial agent. Thus, in one embodiment, the thickness T (in μm) of the second layer is such that the T/D ratio, where D is the volume distributed mean particle diameter (in μm) of the anti-microbial particles is in the range of 0.3 to 10; in a further embodiment in the range of 0.3 to 5; in a further embodiment 0.4 to 4.0; in a further embodiment 0.5 to 3.5; in a further embodiment 0.5 to 2.5; and in a further embodiment 0.6 to 2.0.
The polymeric substrate may conveniently contain any of the additives conventionally employed in the manufacture of polymeric films. Thus, agents such as dyes, pigments, voiding agents, lubricants, anti-oxidants, radical scavengers, UV absorbers, fire retardants, thermal stabilisers, anti-blocking agents, surface active agents, slip aids, optical brighteners, gloss improvers, prodegradents, viscosity modifiers and dispersion stabilisers may be incorporated in the substrate as appropriate. In particular, the substrate may comprise one or more particulate filler(s), such as a particulate inorganic filler or an incompatible resin filler. Particulate inorganic fillers include metal or metalloid oxides, such as alumina, silica and titania, calcined china clay and alkaline metal salts, such as the carbonates and sulphates of calcium and barium. Filler particles, such as Aerosil™ OX50 or Seahostar™ KEP30 or KEP50, may be present in an amount of from about 0 to about 5%, and more preferably 0.1 to 2.5% by weight relative to the weight of the polymeric material of the layer. The components of the composition of a layer may be mixed together in a conventional manner. For example, by mixing with the monomeric reactants from which the layer polymer is derived, or the components may be mixed with the polymer by tumble or dry blending or by compounding in an extruder, followed by cooling and, usually, comminution into granules or chips. Masterbatching technology may also be employed.
The film preferably has a % of scattered visible light (haze) of <50%, preferably <30%, preferably <15%, preferably <12%, preferably <9%, preferably <6%, more preferably <3.5% and particularly <2%, measured according to the standard ASTM D 1003. In this embodiment, the substrate is unfilled or filler is typically present in only small amounts, generally not exceeding 0.5% and preferably less than 0.2% by weight of the substrate polymer.
The antimicrobial agent is applied to the substrate in a liquid coating vehicle, which may be an aqueous or organic solution, dispersion or emulsion, but is typically a dispersion, particularly an aqueous dispersion. The coating composition may be manufactured in accordance with conventional procedures. For instance, the anti-microbial agent can be added directly to the coating vehicle under adequate agitation. Alternatively, it can be pre-dispersed or pre-mixed in an appropriate liquid medium, and the pre-dispersed/pre-mixed anti-microbial agent then added to the main coating composition under adequate agitation to ensure uniform distribution. In an aqueous coating composition, surface emulsifiers may be used to help the dispersion of the anti-microbial agent.
A suitable liquid vehicle is water, although non-aqueous organic solvents can also be used, as well as mixtures of water with organic solvents. The liquid vehicle should be sufficiently volatile to be removed during the heat-setting step. In one embodiment, the liquid vehicle is sufficiently volatile that substantially all of said liquid vehicle (i.e. at least 90%, preferably at least 95%, preferably at least 99%) is evaporated during the heat-setting step.
In a preferred embodiment, the coating composition contains a surfactant to assist in the wetting of the substrate surface. Any conventional surfactant may be used, and suitable surfactants include ethoxylated non-ionic, alcohol ethoxylate and alcohol alkoxylate surfactants, such as the alkyl phenol ethoxylates and ethoxylated sorbitan fatty acid derivative surfactants, such as polyoxyethylene sorbitan monolaurate.
The coating is applied to the substrate “in-line”, i.e. during the process of film manufacture. The coating may be applied before the stretching operations are conducted or to a stretched substrate. However, application of the coating composition is preferably effected during the stretching operation(s). Thus, the coating is preferably applied to the film substrate between the two stages (longitudinal and transverse) of a biaxial stretching operation, i.e. it is applied as an “inter-draw” coating. Thus, the film substrate may be stretched firstly in the longitudinal direction over a series of rotating rollers, coated with the coating composition, and then stretched transversely in a stenter oven, prior to heat-setting. The coating composition may be applied to the polymer film by any suitable conventional coating technique such a gravure roll coating, reverse roll coating, dip coating, bead coating, slot coating, electrostatic spray coating, extrusion coating or melt coating. Prior to deposition of the coating composition onto the substrate, the exposed surface thereof may, if desired, be subjected to a chemical or physical surface-modifying treatment, as are well-known in the art, in order to improve the bond between that surface and the subsequently applied coating. Physical surface-modifying treatments include flame treatment, ion bombardment, electron beam treatment, ultra-violet light treatment and corona discharge.
The coating composition is applied to the substrate at a wet coat-weight in the range of from about 0.5 to about 50 μm.
The coating vehicle of the coating composition is normally substantially removed in the heat-setting step of the film-manufacturing process described hereinabove.
The combination of process conditions and compositional features used in the present invention allows the anti-microbial agent to become at least partially encapsulated in the molten polymeric material of the second layer of the substrate during the heat-setting step of the manufacturing process. The wetting/bonding interaction which takes place during the heat-setting step results in a film in which the particulate antimicrobial agent is held very firmly in place by the polymer matrix. Analysis of the film surface by scanning electron microscopy (SEM) demonstrates that the anti-microbial agent is held on or just below the surface of the polymer matrix in the final film, and presents a markedly different surface profile compared to a film which has been manufactured using a similar amount of antimicrobial agent incorporated into the polymer prior to film manufacture.
If desired, slight pressure may be applied over the layer of the particulate additive to impress the particles into the second layer, and such pressure may typically be applied in the stenter, and typically just prior to the transverse stretching stage. Excess particulate additive which has not bonded or penetrated into the second layer may be removed from the surface thereof, e.g. by inverting the coated substrate, by dispersing the particles with a blast of air, or by brushing or washing the particles away. The coated substrate may be allowed to cool in air or may be quenched to complete the bonding of the particles to the second layer and the cooling or quenching operation may be effected either before or after any excess particles have been removed from the surface of the film.
In one embodiment, the anti-microbial film comprises a coating layer disposed on the surface of the first layer which is remote from the co-extruded second layer, and this coating layer is a barrier coating layer which is sufficient to provide a barrier to water vapour and/or oxygen. In one embodiment, the coating is sufficient to provide a water vapour transmission rate in the range of 0.01 to 10 g/100 inches2/day, preferably 0.01 to 0.1 g/100 inches2/day, and in one embodiment 0.1 to 1.0 g/100 inches2/day, and/or an oxygen transmission rate in the range of 0.01 to 10 cm3/100 inches2/day/atm, preferably 0.01 to 1 cm3/100 inches2/day/atm, and in one embodiment 0.1 to 1 cm3/100 inches2/day/atm. Suitable coat weights are in the range of 0.01 to 14 g/m2, preferably 0.02 to 1.5 g/m2. Conventional barrier coatings include PVDC, PCTFE, PE, PP, EVOH and PVOH. PVDC layers are particularly suitable for providing a barrier to both gas and water vapour; EVOH and PVOH layers are particularly suitable for providing a barrier to gas; while PCTFE, PE and PP layers are particularly suitable for providing a barrier to water vapour. Suitable layers are known in the art and are disclosed, for instance, in U.S. Pat. No. 5,328,724 (EVOH), U.S. Pat. No. 5,151,331 (PVDC), U.S. Pat. No. 3,959,526 (PVDC), U.S. Pat. No. 6,004,660 (PVDC and PVOH). Suitable PVDC polymeric layers are copolymers of 65 to 96% by weight of vinylidene chloride and 4 to 35% of one or more comonomers such as vinyl chloride, acrylonitrile, methacrylonitrile, methyl methacrylate, or methyl acrylate, and are generally referred to as saran. A suitable grade contains about 7 weight percent methacrylonitrile, 3 weight percent methyl methacrylate, and 0.3 weight percent itaconic acid comonomers.
In a further embodiment, the anti-microbial film comprises a coating layer disposed on the surface of the first layer which is remote from the co-extruded second layer, and this coating layer is a sealant coating layer sufficient to provide a heat-seal strength of from 100 g/in to 2500 g/in when heat-sealed to itself according to the test method described herein. Preferably the, heat-seal strength is at least about 300 g/in, preferably at least 500 g/in, preferably at least 750 g/in. Suitable coat weights are in the range of 0.5 to 14 g/m2, preferably 1.0 to 10 g/m2. Suitable heat-sealable or sealant coatings include ethylene vinyl acetate (EVA), amorphous polyesters (APET), olefinic polymers such as polyethylene (PE), caprolactone, acid copolymers such as ethylene methacrylic acid (EMAA), ionomers such as Surlyn, and styrenic copolymers such as styrene isoprene styrene (SIS). Suitable layers are well-known in the art. U.S. Pat. No. 4,375,494 and U.S. Pat. No. 6,004,660 describe amorphous copolyester sealant layers. Suitable copolyesters may comprise an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid. Suitable aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, or 2,5-, 2,6- or 2,7-naphthalenedicarboxylic acid, and suitable aliphatic dicarboxylic acids include succinic acid, sebacic acid, adipic acid, azelaic acid, suberic acid or pimelic acid. A preferred aromatic dicarboxylic acid is terephthalic acid. Preferred aliphatic dicarboxylic acids are selected from sebacic acid, adipic acid and azelaic acid. A particularly preferred aliphatic diacid is sebacic acid. The concentration of the aromatic dicarboxylic acid present in the copolyester is preferably in the range from 40 to 80, more preferably 45 to 65, and particularly 50 to 60 mole % based on the dicarboxylic acid components of the copolyester. The glycol component of the copolyester of the coating layer preferably contains from 2 to 8, more preferably 2 to 4 carbon atoms. Suitable glycols include ethylene glycol, 1,3-propanediol, 1,3-butane diol, 1,4-butanediol, 1,5-pentane diol, neopentyl glycol, 2,2-dimethyl-1,3-propanediol, diethylene glycol, triethylene glycol and 1,4-cyclohexanedimethanol. An aliphatic glycol, particularly ethylene glycol or 1,4-butanediol, is preferred. In a particularly preferred embodiment, the aliphatic glycol is 1,4-butanediol. Such copolyesters preferably have a glass transition point of less than 10° C., more preferably less than 0° C., particularly in the range from −50° C. to 0° C., and especially −50° C. to −10° C., and a melting point in the range from 90° C. to 250° C., more preferably 110° C. to 175° C., and particularly 110° C. to 155° C. Particularly preferred examples of such copolyesters are (i) copolyesters of azeleic acid and terephthalic acid with an aliphatic glycol, preferably ethylene glycol; (ii) copolyesters of adipic acid and terephthalic acid with an aliphatic glycol, preferably ethylene glycol; and (iii) copolyesters of sebacic acid and terephthalic acid with an aliphatic glycol, preferably butylene glycol. Preferred polymers include a copolyester of sebacic acid/terephthalic acid/butylene glycol (preferably having the components in the relative molar ratios of 45-55/55-45/100, more preferably 50/50/100) having a glass transition point (Tg) of −40° C. and a melting point (Tm) of 117° C.), and a copolyester of azeleic acid/terephthalic acid/ethylene glycol (preferably having the components in the relative molar ratios of 40-50/60-50/100, more preferably 45/55/100) having a Tg of −15° C. and a Tm of 150° C. Suitable EVA polymers may be obtained from DuPont as Elvax™ resins. Typically, these resins have a vinyl acetate content in the range of 9% to 40%, and typically 15% to 30%.
In a further embodiment, the anti-microbial film comprises a coating layer disposed on the surface of the first layer which is remote from the co-extruded second layer, and this coating layer provides both barrier and heat-seal properties, and PVDC coatings are suitable in this regard
The barrier and/or sealant coating layer may be applied to the first layer of the substrate which is remote from the co-extruded second layer either in-line (e.g. by a conventional two-sided in-line coating process) or off-line. The coating may be applied to an already-oriented substrate. However, application of a coating composition is preferably effected before or during the stretching operation(s), as described hereinabove. The coating composition may be applied to the polymer film substrate in aqueous or organic solution, in a dispersion or in an emulsion, suitably in neat form, by any suitable conventional coating technique, such as those described hereinabove. Prior to deposition of a coating composition onto the substrate, the exposed surface thereof may be subjected to a surface-modifying treatment as those described hereinabove. The barrier and/or sealant coating layer typically has a thickness in the range of about 0.01 to 14.0 μm. In one embodiment, the coating thickness is no more than about 5 μm, preferably no more than about 4 μm, preferably no more than about 2 μm, and preferably no more than about 1 μm. Preferably, the coating layer is in the range of about 0.02 to about 1.5 μm, preferably 0.02 to about 1.0 μm. In one embodiment, the coating layer thickness is 0.5 microns or greater.
The films described herein may be used to provide an anti-microbial surface in a variety of applications, such as in medical and catering environments and equipment, and in food packaging. Other applications include restrooms, garbage disposals, animal feed troughs, schools, swimming pool areas, automobile fixtures, public access fixtures, public seating, public transportation fixtures, toys, and other industrial, agricultural, commercial or consumer products.
The following test methods may be used to determine certain properties of the polymeric film:
Antibacterial activity can also be assessed using a modified version of JIS Z 2801: 2000 in which the impact of a treated system on a microbial population delivered as a splash of a contaminated liquid (or as a residue of a contaminated liquid) can be studied, and this is referred to herein as “the scenario method”. Both the exposure conditions (temperature & humidity) and the liquid employed were varied, relative to the standard method. Thus, an aliquot (100 μl) of a log phase cell suspension of either MRSA (6.2×106 cells/ml) or E coli (4.6×106 cells/ml) suspended in either sterile 1.5% BSA (bovine serum albumin), sterile distilled water or sterile artificial urine solution (19.4 g urea, 8.0 g sodium chloride, 0.6 g calcium chloride, 1.0 g magnesium sulphate and 971.0 g sterile distilled water) were inoculated onto replicate samples and left uncovered for up to 24 hours at 20° C. and 65% relative humidity. The size of the surviving population on replicate (3) samples selected at random from those inoculated as above was determined at intervals of 3, 6, 12 and 24 hours using the method described in JIS Z 2801. The remainder of the test method proceeds in accordance with the description given above for the standard method.
In addition, simple adhesion tests and rub-resistance tests involving visual inspection can also usefully be used to assess durability. The methods used are described in Table 1 below.
The invention is further illustrated by the following examples. It will be appreciated that the examples are for illustrative purposes only and are not intended to limit the invention as described above. Modification of detail may be made without departing from the scope of the invention.
A coating composition was prepared as an aqueous dispersion (17% total solids) of the anti-microbial agent Alphasan™ RC2000 (Milliken (UK); particle size of 1.0 μm; contains silver at 10 wt %) by mixing the following ingredients:
(i) 825 grams of Alphasan™ RC2000
(ii) 250 grams of a 10% aqueous solution of 25 g Caflon™ NP10 surfactant (Univar, UK);
(iii) demineralised water to make the composition up to 5000 g.
The surfactant is placed in a suitably sized beaker and the water is added with sufficient stirring from a magnetic stirrer to generate a vortex, followed by slow addition of the Alphasan. The mixture is further mixed at high shear rates using an Ultra-Turrax machine at a speed of 357 rpm for 30 minutes.
A polymer composition comprising PET (which makes up the “first layer” as defined herein) was co-extruded with a copolyester comprising terephthalic acid/isophthalic acid/ethylene glycol (82/18/100) (which makes up the “second layer” as defined herein), cast onto a cooled rotating drum, pre-heated to a temperature of 80 to 81° C. and stretched in the direction of extrusion to approximately 3.4 times its original dimensions. The anti-microbial coating composition was then applied by offset-gravure coating at a line-speed of 90% (i.e. the tangential velocity of the gravure roller was 90% of the film-web speed) to a wet coat-weight of about 15.9 μm. The film was heated to a temperature of about 95° C., passed into a stenter oven at a temperature of 110° C. where the film was stretched in the sideways direction to approximately 3.6 times its original dimensions. The biaxially-stretched film was heat-set by successive heating in three zones of defined temperature (225, 220 and 200° C.) by conventional means at a film-web speed of 11.9 m/min; approximate residence time in each of the three zones was 40 seconds The total thickness of the final film was 100 μm, and the copolyester second layer was approximately 0.8 μm thick.
The amount of particulate antimicrobial agent in the final film was 4340 ppm by weight of the total polymeric material of the substrate, giving a silver content of 434 ppm by weight of the total polymeric material of the substrate. The amount of particulate antimicrobial agent in the second layer of the final film was 54% by weight of the total polymeric material of the second layer. An SEM analysis showed the antimicrobial particles to be protruding from the second layer with significant amounts of agglomeration and with high surface concentration.
The procedure of Example 1 was repeated except that (i) the thickness of the copolyester layer was varied; and (ii) the three heat-setting zones were at temperatures of 205, 220 and 220° C., respectively, and about 6-7% relaxation was applied during heat-setting. Wyko and SEM analyses showed that the antimicrobial particles were protruding from the second layer with significant amounts of agglomeration and with high surface concentration. The Examples are characterised in Table 2 below:
The procedure of Example 1 was repeated using a line-speed of 70%.
A coextruded two-layer film was prepared substantially in accordance with Example 1 except that (i) both layers of the film were PET; (ii) the pre-heater and sideways draw temperatures were 85° C. and 100° C. respectively; (iii) the three heat-setting zones were at temperatures of 195, 210 and 195° C., respectively; (iv) the thickness of the second layer was 4 μm; and (v) the antimicrobial agent was instead introduced into the second layer by addition to the molten polymer prior to film manufacture at levels of 20,000 ppm (2%; comparative example 1) and 80,000 ppm (8%; comparative example 2). These films showed poor antimicrobial activity. Surface analyses indicated that the antimicrobial agent was not proximate to the surface.
A coextruded two-layer film was prepared substantially in accordance with Example 1 except that (i) the thickness of the second layer was 1 μm; and (ii) the antimicrobial agent was instead introduced into the second layer by addition to the molten polymer prior to film manufacture at levels of 50,000 ppm (5%). The antimicrobial activity observed was poor. Wyko and SEM analyses showed the antimicrobial particles to be well submerged in the second layer polymer matrix with little agglomeration, and much lower surface concentration when compared to Example 1.
A coextruded two-layer film coated with an antimicrobial composition was prepared in the manner of Example 1 except that (i) both layers of the substrate were PET homopolymer; (ii) the thickness of the second layer was 1; and (iii) the line-speed was 80% to give a wet coat-weight of about 13.3 μm. The antimicrobial activity observed was poor. The antimicrobial particles were not well-bound and the film was very friable.
The antimicrobial activity of the above films was measured and the results are shown in Tables 3 and 4 below. The data in Table 3 were collected using a test based on JIS Z 2801: 2000. The data in Table 4 were collected using the “scenario method” described herein (a modified version of JIS Z 2801: 2000). The films according to the invention all show excellent antimicrobial efficacy, and superior to the films of the comparative examples.
The durability of Examples 1, 3 and 4 were tested against Comparative Example 4 using the tests described herein, and the results are shown in Table 5 below. The films according to the present invention exhibit superior durability.
The surface roughness characteristics of the above films were measured using the tests described herein, and the results are shown in Table 6 below, and in
E-Coli/Urine
E-Coli/Water
E-Coli/BSA
E-Coli
MRSA
E-Coli
| Number | Date | Country | Kind |
|---|---|---|---|
| 0810719.5 | Jun 2008 | GB | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/GB09/01459 | 6/10/2009 | WO | 00 | 12/10/2010 |
