GB2449876A - Active packaging materials incorporating micro-porous solids and essential oils - Google Patents

Active packaging materials incorporating micro-porous solids and essential oils Download PDF

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Publication number
GB2449876A
GB2449876A GB0710811A GB0710811A GB2449876A GB 2449876 A GB2449876 A GB 2449876A GB 0710811 A GB0710811 A GB 0710811A GB 0710811 A GB0710811 A GB 0710811A GB 2449876 A GB2449876 A GB 2449876A
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Prior art keywords
composition according
micro
porous solid
composition
essential oil
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GB0710811D0 (en
GB2449876B (en
Inventor
Adnan Sabehat
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POST HARVEST SOLUTIONS Ltd
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POST HARVEST SOLUTIONS Ltd
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Priority to GB0710811A priority Critical patent/GB2449876B/en
Publication of GB0710811D0 publication Critical patent/GB0710811D0/en
Priority to PCT/IB2008/001786 priority patent/WO2008149232A2/en
Priority to EP08776337A priority patent/EP2170043A2/en
Priority to AU2008259508A priority patent/AU2008259508A1/en
Publication of GB2449876A publication Critical patent/GB2449876A/en
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Publication of GB2449876B publication Critical patent/GB2449876B/en
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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/154—Organic compounds; Microorganisms; Enzymes
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/16—Coating with a protective layer; Compositions or apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/28—Applications of food preservatives, fungicides, pesticides or animal repellants

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • General Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Agronomy & Crop Science (AREA)
  • Microbiology (AREA)
  • Plant Pathology (AREA)
  • Toxicology (AREA)
  • Dentistry (AREA)
  • Environmental Sciences (AREA)
  • Nutrition Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)

Abstract

A composition contains essential oils absorbed within the pores of a micro-porous solid material. The composition may be incorporated into active packaging material developed to offer anti-microbial properties and extension of shelf life to packaged perishable foodstuffs. The active packaging material may be in the form of a polymeric or natural fibre substrate coated with the composition or in the form of granular beads produced from the composition and contained within a porous sachet. The micro-porous solid may be a large or medium pore zeolite or may be an ion-exchanged form of zeolite or clay. The composition may also be sprayed over growing crops or fresh cut fruits and vegetables.

Description

Active Packaging Materials incorporating Micro-porous solids and
Essential Oils This invention relates to active packagmg materials, in particular, but not exclusively, fur packaging perishable foodstuffs.
In this application, "perishable foodstuffs" is defined as any foodstuff that requires special treatment and handling conditions to prevent rapid quality loss through microbiological, physiological or chemical spoilage. The term fresh produce" is defined as harvested fruit, vegetables and flowers, including processed fresh fruit and vegetables. With the exception of flowers, fresh produce is a sub-division of perishable foodstuf. The term "active packaging" is defined as packaging WhCh has been specifically designed to change the atmosphere within packs of perishable foodstuffs including packed vegetables, fruits, flowers, or processed food in order to extend their shelf life, improve their safety or enhance their sensoiy properties.
Many fruits, vegetables and flowers are sensitive to ethylene which acts as a plant hormone that has various physiological effects on fresh produce. It accelerates respiration, leading to enhanced maturity and senescence, and also to softening and ripening of a wide variety of agricultural commodities. To prolong shelf life and maintain acceptable visual and organoleptic quality, accumulation of ethylene in packs of perishable foodstuffs should therefore be mitigated either by placing an ethylene removal agent inside the pack or by incorporating an ethylene removal agent as a component of the active packaging.
An effective ethylene absorber consists of a solid support impregnated with potassium permanganate solution (KMnO4) However, due to the chemical properties of potassium permanganate, precautions must be taken to prevent contamination of the contents of the pack by contact with the chemical. Disposal of the packagmg waste is a further disadvantage of the use of such a product as an ethylene absorber. Use of other materials with ethylene absorbing capability and with fewer disadvantages would therefore be desirable.
Another factor contributing to food spoilage derives from microbial contamination on the food surface. Packaging with antimicrobial properties provides an effective solution fur fbod surface contamination problems. One of the most promising applications of active packaging is
I
antimicrobial packaging film from which an active ingredient is released on to the fbod surface thereby inhibiting growth of micro-organisms.
The effectiveness of currently developed active packaging is limited as active materials have hitherto generally been incorporated within the mass of the packaging film and this in turn has interfered with extrusion, thus limiting active material content and hence efficacy.
The present invention has been made from a consideration of the foregoing problems and the disadvantages of known packaging materials and seeks to provide a solution to the undesirable effects of ethylene accumulation and microbial contamination on packaged fbodstuffs, in particular penshable foodstuf According to one aspect of the present invention, we provide a composition comprising a micro-porous solid and an essential oil in which the essential oil is included within the pores of the micro-porous solid.
The present invention addresses the limitations described above by combining micro-porous solids with essential oils in a bespoke process and then appropriately fonnulating the composition for impregnating within the mass ot or coating on to, a packaging film to provide active packaging materials which both adsorb unwelcome odours released by the packaged produce and emit essential oil vapour at a controlled rate, thereby providing anti-microbial protection of the packaged produce The rate of release of essential oil vapour from the active packaging may be varied by use of an appropriate micro-porous solid and of an appropriate process by which the essential oil is included within the pores of the micro-porous solid.
In at least one embodiment, the micro-porous solid is a zeolite. The micro-porous solid may selected from the group consisting of large-pore zeolites with channel free diameter from 12A to 5.9A or from the group consisting of medium-pore zeolites with channel free diameter from 5.9A to 5 oA. It will be noted that zeolites and essential oils are naturally occurring, non-toxic materials and friendly to humans and to the environment. The use of a combination of zeolites and essential oils according to this embodiment has been found to extend storage life of vegetables, fruits, flowers and other perishable produce.
In another embodiment, the micro-porous solid is selected from the group consisting of montmonulonjte KSF clay or montmorillonite Kl0 clay, and mixtures thereof.
Advantageously, the micro-porous solid is an ion-exchanged form of zeolite or clay, as the properties of the clay or the zeolite are affected by the nature of the exchangeable cation, for example, without being limited by the following examples, pore size (in the case of zeolite), interlaying spacing (in the case of clay), water absorption capacity, catalytic properties, adsorption affinity to organic compounds, tactoid size i.e. number of layers in the flock, antimicrobial activity (e.g Cu-clay), and acidity of the surface. For example, the micro-porous solid may be a cation-exchanged zeolite or clay with metals, such as K, Na, Li, Cs, Be2, Cr43, Ce43, Cu2, Ca2, Mg2, Fe2, Fe3, Ag, Ba2 or Zn2, and mixtures thereof In one preferred embodiment, the micro-porous solid is selected from the group consisting of hydrophobic organophilic pentasil zeolites with high Si:Al ratio.
In another preferred embodiment, the micro-porous solid is selected from the group of meso-porous solids such as silica gel Si02 and aluminum oxide Al203.
Preferably, the particle size of the micro-porous solid is from 1 micron (.z) to about 100 microns () The essential oil may be selected from the group consisting of thymol, carvacrol, eucaliptol, cinnamaldehyde, eugenol, menthol, cummal, anethole, estragole, citronnellal, carvone, menthone, limonene, isoeugenol, bisabolol, camphor, geraniol, citral, and mixtures thereof in mixtures with ethanol or other antimicrobial volatile matenal.
The essential oil is preferably natural in origin, typically oregano oil, thyme oil, or clove oil, although many other natural essential oils can be used in active packaging applications as defined herein. A source of these natural essential oils is Frutarom Industries Limited, a multi-national corporation traded on the Tel-Aviv and London stock exchanges, who offer Thyme Oil Red or Thyme Oil White, either or both of which is suitable in these active packaging applications. It is also possible to use synthetic essential oils such as thymol or carvacrol but natural essential oils are preferred, firstly because they are natural and hence environmentally attractive in fresh produce packaging, and secondly because they are often liquid at ambient temperatures whereas the synthetic equivalent may often be solid at ambient temperatures
S
The composition may further comprise one or more additional ingredients selected from the group consisting of protective colloids, adhesives, binding agents, chelating agents, thickening agents, thixotropic agents, penetrating agents, stabilizing agents, sequestering agents, anti-foam agents, antioxidants, natural or synthetic seasonings andlor flavours, dyes and/or colorants, vitamins, minerals, nutrients, enzymes, insecticides, deodorants, and mixtures thereof The composition may comprise a granular product in the form of a powder, pellets, beads, or granules that may be presented in a porous sachet.
Alternatively, the composition may comprise a suspension in a solvent such as water.
We have found that the composition according to the first aspect of the invention has many uses in applications where antimicrobial activity is beneficially released from the composition over a prolonged penod of time.
For example, the composition may be used: * for protecting fbod products from bacterial and fungal infection during storage by dusting with the composition prepared as a powder presentation. The food products may be fresh fruits and vegetables, fresh cut fruits, vegetables or flowers, semi-processed food or fully processed food.
* for antimicrobial protection of agncultural crops by such means as soil microbial sterilisatiori or over-spraying of the crops with the composition * for providing anti-microbial protection in medical hand lotions and cleaning or sanitizing agents for medical use * for providing anti-microbial protection in air filtration systems or scrubbers in which it is required to impart anti-microbial activity to the filtered air without damage to the health of those subsequently inhaling the filtered air or without damage to the environment.
* for masking of bad odours over an extended period of time which is beneficial to those working in or living close to the source of the bad odours such as livestock farms, abattoirs, and disposal sites for animal and human waste. It is also envisaged to incorporate the composition in powder ibm into animal feedstufl to reduce bad odours emanating from animal manure.
According to a second aspect of the present invention, we provide a packaging material impregnated with or coated with the composition according to the first aspect of the invention.
We have found that packaging material impregnated with or coated with the composition offers improved properties when used as packaging for perishable foodstuffs including properties such as ethylene removal, water permeability and antimicrobial activity, all of which are beneficial to the freshness and quality of packed penshable products.
We have found that the composition according to the second aspect of the present invention can also be used in the medical field as a packaging film where antimicrobial protection is required.
Our research programme has included (a) testing the antimicrobial activity of zeolitefessential oil combinations against a wide range of target micro-organisms, and (b) investigating the physico-mechanical properties of different presentations of zeolite/essentiaj oil combinations, and (c) studying the rate of release of essential oils from zeolite/essential oil combinations, and (d) assessing the feasibility of different uses of zeolite/essential oil combinations in food packaging applications, and (e) evaluating the efficacy of ethylene adsorbing and antimicrobial releasing formulations of zeolite/essentiai oil combinations to extend freshness and improve quality of fresh fruits, vegetables and cut flowers under laboratory and commercial conditions.
Active packaging materials using this invention have been developed fbr ethylene removal and for releasing antimicrobial essential oils allowing the original qualities of fruits, vegetables, flowers and processed food to be maintained during a longer period. Amongst other applications, this is of crucial importance in developing the export of fresh products to distant markets It will be obvious, but will be stated nevertheless, that in the case where the active packaging has been produced by coating the composition on to a packaging film, then following conversion of the active packaging material into a suitable packaging format such as, for example, bags, by whatever process and of whatever configuration, the coated side of the active packaging substrate is always located on the inside of the pack containing the perishable foodstuff Furthermore, it is not necessary tbr the active packaging material to be flood coated with the composition containing the micro-porous solid/essential oil combination. Preferably, the active packagmg material is strip coated or pattern coated in order to provide both economic and technical benefits as the strip or pattern coating can be applied in such a way that the coating does not interfere with heat sealing of the active packaging substrate According to another aspect of the present invention, the micro-porous solid and the essential oil are combined together in a bespoke process and the resulting slurry is dried by various means including movement of air at ambient or higher temperatures, fluid bed drying, spray drying, freeze drying, vacuum filtration, regular filtration, centnfuging, pan granulation, and extrusion granulation, in order to produce active packaging granules or beads of diameter between 1mm and 5mm, preferably around 3mm. It has been found that these active packaging granules or beads when packed in a porous sachet and placed within packs of fruits, vegetables or other perishable foodstufl, offer similar protection to the perishable foodstuff to that obtained by coating the composition on to a packaging film.
In this embodiment, the porous sachet is preferably made from materials based upon naturai fibres such as paper, or upon polymeric materials manu&ctured from petroleum, renewable, or sustainable sources, or upon combinations of natural fibres and polymeric matenals. By way of example only, appropriate materials are heatseal beverage filter paper as used to make tea bags, interwoven polymeric fibre materials such as those made from viscose, polyester, polypropylene, polyethylene (e.g. Tyvek ), which are sufficiently porous to permit the passage of essential oil vapour emanating from the granules located within the sachet into the pack of penshable foodstuff to provide an antimicrobial effect, and to permit the passage of ethylene and undesirable odours into the sachet to be adsorbed on the active packing granules or beads without allowing any part of the active packing granules or beads to escape through the pores of the sachet into the pack of perishable produce. It will be noted that the material from which the porous sachet is made should comply with food contact legislation, e.g. FDA 21 CFR 176.170 within the USA, or within the UK, implementation of European Commission Directives is enacted by Statutory Instrument No. 1376 "The Plastic Material and Articles in Contact with Food Regulations 1998" and its subsequent amendments.
By way of example only, it has been found that approximately 3 grams of zeolite after conversion into active packaging granules or beads and placed within a porous sachet according to this invention offers extended protection to packs containing 7 kilograms of grapes. However, if the combination of zeolite and essential oil, after appropriate formulation, is coated on to a packaging film according to this invention, the quantity of zeolite required for similar extended protection of such packs will be reduced due to the greater surface area exposed to the grapes per gram of zeolite. After drying, the quantity of essential oil adsorbed into the micro-pores of the zeolite may be up to 35% by weight, preferably 10-20%. Higher quantities of essential oil will be adsorbed into a micro-porous solid selected from the group consisting of large- pore zeolites with channel free diameter from 5.9A to 12A, such as Clinoptilolite, Beta, Linde X, Linde Y, Linde L, or Mordenite, and mixtures thereof; preferably NaX, NaY Lower quantities of essential oil will be adsorbed into a micro-porous solid selected from the group consisting of medium-pore zeolites with channel free diameter from 5.OA to 5.9A, such as ZSM-5, Silicalite, Ferriente types, Linde-T, Merlinoite types, or Linde W, and mixtures thereof It has been found that the addition of a suitable solvent, for example an alcohol such as denatured ethanol or an alkane such as pentane, hexane, heptane, octane, iso-octane or a mixture thereof, mixed with the essential oil assists in the adsorption of the essential oil into the pores of the zeolite.
Zeolites are naturally occurring or synthetically produced hydrated aluminium silicates which form a regular crystal lattice and release water at high temperature.
* Naturally occurring zeolites are rarely pure and are contaminated to varying degrees by other minerals, metals, quartz or other zeolites. For this reason, naturally occurring zeolites are excluded from many commercial applications where uniformity and punty are essential.
* Synthetic zeolites can be manufactured in a uniform, phase-pure state and in structures offering desirable properties which do not appear in nature. Since the principal raw materials used to manufacture zeolites are silica and alumina, which are among the most abundant mineral components on earth, the potential to supply zeolites is virtually unlimited Disadvantages include the inability to create csystals with dimensions of a comparable size to their natural counteiparts.
Zeolites are polar in nature and certain cations (sodium, potassium, lithium or calcium or any combination thereof) are implanted by ion exchange. The dehydrated crystals are interlaced with regular spaced channels of molecular dimension usually ranging from 2A to 9A Non polar zeolites are synthesized by dealummation of polar zeolites. This is done by treating the zeolite with steam at elevated temperatures, greater than 500 C. This high temperature heat treatment breaks the aluminium-oxygen bonds and the aluminium atom is expelled from the zeolite framework.
In addition to being naturally occurring or synthetically manufactured, zeolites may differ in the following important respects: * TypeXvsTypey.
X and Y zeolites have the same structure but X zeolites have a lower Si:AL ratio (1.0-1.5) than Y zeolites (1.6-3.0) * Hydrophilic vs hydrophobic * Pore size * Particle size Hydrophihc zeolite-based products as used for ethylene removal and as antimicrobial releasing agents, aie very limited under high humidity conditions prevailing within most packs containing perishable produce since the free pores are preferentially filled with water molecules. The hydrocarbon molecules, whether ethylene or essential oils, being hydrophobic, are typically left unabsorbed in the atmosphere created within the pack. We have found, however, that other zeolites, such as hydrophobic zeolites, have adsorption affinities that are much greater than those for water vapour alone, thereby offenng enhanced attractiveness as a component of active packaging.
We have found that this invention can be practised using zeolites of many different types and characteristics, i.e * naturally oCcurnng * synthetically manufctureJ -it is possible to manufacture desirable zeolite structures which do not occur in nature e g. Zeolite A * type X allowing comparatively higher quantity of active essential oil to be adsorbed * type Y allowing comparatively lower quantity of active essential oil to be adsorbed * hydrophilic for quicker release (typically up to 60 days) of active essential oil vapour * hydrophobic for slower release (typically up to a year or more) of active essential oil vapour due to the oil being more strongly bound in the zeolite structure * pore sizes of diameters varying from A3 to A12 * particle sizes varying from I jim to lOOj.un where smaller particle sizes are preferred for coating formulations and larger particle sizes may be used in granular preparations.
The efficacy of active packaging is based upon a number of different parameters including * porosity control (e.g. gas pressure release and gas composition balance), * polymer permeability control (e.g. gas composition balance and temperature compensation); * melting of waxes (e.g. temperature compensation), * inorganic or organic oxidation (e.g. 02 scavenging, 02 permeation barrier, 02 indicator, CO2 generation and ethylene scavenging); * enzyme catalysis (e.g. oxygen scavenging); * acid and base reaction (e g. CO2 absorption, CO2 generation and odour absoiption); * adsorption (e g. taint removal, 02 scavenging, ethylene scavenging and water removal); * absorption (e.g. condensation control and drip collection); hydrolysis (e.g., SO2 release); * desorption (e.g. ethanol, hinokitiol and water release); and * organic reactions (e.g. ethylene removal and 02 barner) Polyethylene is the most commonly used polymenc packaging film with its advantages of being relatively inert, permeable to some gases and having a low water vapour transmission rate.
However, due to the large variety and differing characteristics of penshable fbodstuff requinng packaging, no single packaging materia] has been found to be ideal for use with all perishable foodstufl. In order to achieve improved performance with many perishable foodstuff -packaging film combinations, highly permeable porous patches were introduced. Among these, a commercial product FH film containing natural zeolites embedded into the mass of the polyethylene, was reported to offer extended shelf life of various fruits and vegetables.
Polymeric materials of many types with different physico-cheniicaj properties have been used by the inventor for the production of active packaging materials e.g., polyethylene, polypropylene, polyester, polyamide and other polymeric substrates of petroleum and of renewable or sustainable origins, and lammations thereof with each other or with natural fibre materials such as paper.
The adsorbing properties of micro-porous materials with various antimicrobial active essential oils (such as thymol, carvacrol, eugenol and many others) have been investigated. Furthermore, the effect of water content, calcmation temperature, particle size, solid content and physical fbrm, on the activity of the composition as ethylene adsorber and as antimicrobial releasing agent, have been studied using different micro-porous materials, e.g. large-pore zeolites, medium-pore zeolites; small-pore zeolites; micro-porous clays, ion-exchanged zeolites; active micro-porous solids and hydrophobic pentasil zeolites.
Essential oil/zeolite adducts have been prepared by gas-solid reaction, The crystal structure, host:guest ratio, and the release rate of the active ingredient from the zeolite comple,c within the active packaging, have been determined by ourselves under various humidity conditions.
The efficacy of different active packaging materials in extending freshness and improving quality of fresh fruits, vegetables and cut flowers have been evaluated under laboratory and commercial conditions.
A process for preparmg the slurry composition compnsmg of essential oils, solvents, micro-porous solids has been developed. To a solution of an essential oil in a hydrophobic solvent is added a micro-porous solid. The suspension was stirred at certain temperature for a certain period of time The mixture was cooled to room temperature and vacuum filtered. The precipitated solid was washed by a small quantity of cold solvent and then vacuum dned at room temperature.
EXAMPLE
Dissolve 35kg of synthetic thymol in 30 litres of ethanol (typically denatured in such a way as to allow subsequent fbod contact use) and add the solution to 35kgs ofhydrophilic type X zeolite as supplied by Grace Davison under their trade name SYLOSIV AlO (pore openings of approximately 10k particle size approximately 4im). After evaporation of the ethanol, the process will differ whether the composition of zeolite and essential oil is required as a granule or as a coaling fbr packaging films.
In the case of the presentation of the active packaging as a granule or bead, 17 kg of calcium alginate or alternatively pectin are added to the slurry as coating agents, and finally 900 litres of water are added and mixed until homogeneity. The resulting mixture is then dried by any means which does not involve exposure to temperatures of greater than 40 C, and granulated.
In the case of the presentation of the active packaging as a film coating, the sluriy is formulated with binding agents commonly used in the formulation of water-based or solvent-based inks and coatings.
When crude natural thymol is used, due to its lower melting point compared to synthetic thyniol, the quantity of ethanol required can be significantly reduced, thereby enhancing the attractiveness of the process By way of example, figures 1 -5 illustrate some of the experimental results that have been obtained.
In figures 1 -4, the rate of loss of an essential oil (in these figures, thymol) from different micro-porous solids is measured. The thymol is first adsorbed on a micro-porous solid in accordance with the process described in the current invention. The micro-porous solid containing the adsorbed thymol is then exposed to air under ambient conditions and the rate of loss of thymol us measured by extraction from the micro-porous solid at regular time intervals and then subjecting the extract to gas chromatography -mass spectrometry (GC-MS) analysis. By this means, for different micro-porous solids, a relationship can be drawn over time of the quantity of residual thymol adsorbed within the micro-porous solid expressed as milligrams of thymol per gram of micro-porous solid. The line of best fit can then be determined by regression analysis.
It will be seen from figures 1 -4 that the rate of loss of thymol from different micro-porous solids vanes according to the characteristics of the micro-porous solid that has been selected for each experiment. The line of best fit and the experimentally determined results at each time interval can be clearly identified. In this way, the composition most appropnate to the application in hand can be identified.
In figure 5, the results of a comparative trial are shown in which three different compositions according to the current invention are compared with a standard ethanol based commercial treatment (ANTIMOLD ) and a control. Three different compositions according to the current invention and the commercial ANTIMOLD product have been placed in bags containing table grapes and the bags stored for 35 days at 0 C and then 3 days at 20 C. It will be immediately evident from figure 5 that the composition comprising an essential oil adsorbed on a zeolite using an ethanol solvent by a process according to the current invention has produced an outstanding result in which none of the berries showed any microbial damage

Claims (32)

  1. I. A composition compnsmg a micro-porous solid and an essential oil in which the essential oil is included within the pores of the micro-porous solid
  2. 2. A composition according to claim I in which the micro-porous solid is a zeolite.
  3. 3. A composition according to claim 2 wherein the micro-porous solid is selected from the group consisting of large-pore zeolites with channel free diameter from I 2A to 5 9A.
  4. 4. A composition according to claim 2 wherein the micro-porous solid is selected from the group consisting of medium-pore zeolites with channel free diameter from
  5. 5.9A to 5.OA.
    A composition according to claim 1 wherein the micro-porous solid is selected from the group consisting of montmorillonjte KSF clay or rnontmorillonjte K10 clay, and mixtures thereof
  6. 6. A composition according to any of claims 2 to 5 wherein the micro-porous solid is an ionexchanged form ofzeolite or clay
  7. 7 A composition according to claim 6 wherein the micro-porous solid is a cation-exchanged zeolite or clay with metals, such as K, Na, Lii, Cs, Be2, Cr3, Ce3, Cu2, Ca2, Mg2, +2 +3 + +2 +2 Fe, Fe, Ag, Ba or Zn, and mixtures thereof
  8. 8. A composition according to claim 1 wherein the micro-porous solid is selected from the group consisting of hydrophobic organophilic pentasil zeolites with high Si.AI ratio.
  9. 9 A composition according to claim I wherein the micro-porous solid is selected from the group of meso-porous solids such as silica gel Si02 and aluminum oxide A1203.
  10. 10. A composition according to any preceding claim wherein the essential oil is selected from the group consisting of thymol, carvacrol, eucaliptol, cmnamaldehyde, eugenol, menthol, cuminal, anethole, estragole, citronnellaj, carvone, menthone, limonene, isoeugenol, bisabolol, camphor, geraniol, citral, and mixtures thereof in mixtures with ethanol or other antimicrobial volatile matenal.
  11. 11. A composition according to any preceding claim wherein particle size of the micro-porous solid is from 1 micron (ii) to about 100 microns (ft).
  12. 12. A composition according to any preceding claim wherein the said composition further comprises one or more additional ingredients selected from the group consisting of protective colloids, adhesives, binding agents, chelating agents, thickening agents, thixotropic agents, penetrating agents, stabilizrng agents, sequestering agents, anti-fbarn agents, antioxidants, natural or synthetic seasonings and/or flavors, dyes andlor colorants, vitamins, minerals, nutrients, enzymes, insecticides, deodorants, and mixtures thereof
  13. 13. A composition according to any preceding claim comprising a granular product in the form of a powder, pellets, beads, or granules.
  14. 14. A composition according to claim 13 packed in a porous sachet
  15. 15. A composition according to any of claims I to 12 comprising a suspension m a solvent
  16. 16 A composition according to claim 15 where the solvent is water
  17. 17 A packaging material impregnated with the composition of any preceding claim.
  18. 18 A packaging material coated with the composition of any of claims Ito 16
  19. 19. A method for protecting food products from bacterial and fungal infection by treatmg a fruit or vegetable with the composition according to any of claims I to 16.
  20. 20. A method accordnig to claim 19 wherein the food products are fresh fruits and vegetables, fresh cut fruits and vegetables, semi-processed food or fully processed food.
    21 A method for antimicrobial protection of agricultural crops by such means as soil microbial sterilisation or over-spraying of the crops using the composition according to any of claims 1 to 16.
    22 A process for preparing the composition according to any of claims I to 16 wherein the inclusion of the essential oil within the pores of the micro-porous solid is assisted by mixing the essential oil with a solvent.
    23 A process according to claim 22 wherein the solvent is selected from alcohols such as ethanol.
    24. A process according to claim 22 wherein the solvent is selected from alkanes such as pentane, hexane, heptane, octane, iso- octane or a mixture thereof.
    25 A process according to claim 23 or claim 24 wherein any method of movement of air at ambient or higher temperatures, fluid bed drying, spray drying, freeze drying, vacuum filtration, regular filtration, centrifuging, pan granulation, and extrusion granulation may be used to convert the slurry into a material suitable for subsequent granulation.
    Amendments to the claims have been filed as follows:-
    CLAIMS S
    1. An anti-microbial composition comprising a micro-porous solid and an essential oil in which the essential oil is combined with a solvent in order to increase adsorption of the essential oil within the pores of the micro-porous solid.
    2. A composition according to claim I in which the micro-porous solid is a zeolite.
    3. A composition according to claim 2 wherein the micro-porous solid is selected from the group consisting of large-pore zeolites with channel free diameter from 12A to 5.9A.
    4. A composition according to claim 2 wherein the micro-porous solid is selected from the group consisting of medium-pore zeolites with channel free diameter from 5.9A tos.OA.
    5. A composition according to claim 2 wherein the micro-porous solid is an ion-exchanged form of zeolite.
    6. A composition according to claim 5 wherein the micro-porous solid is a cation-exchanged zeolite or clay with metals, such as K, Nat, Lit, Cs, Be2, Cr3, Ce3, Cu2, Ca2, Mg2, Fe2, Fe3, Ag, Ba2 or Zn42, and mixtures thereof.
    7. A composition according to claim 1 wherein the micro-porous solid is selected from the group consisting of hydrophobic organophilic pentasil zeolites with high Si:Al ratio.
    8. A composition according to claim I wherein the quantity of essential oil adsorbed into the micro-pores of the zeolite is up to 35% by weight 9. A composition according to claim 1 wherein the micro-porous solid is selected from the group of meso-porous solids such as silica gel Si02 and aluminum oxide Al203.
    10. A composition according to claim I wherein the micro-porous solid is a form of clay.
    11. A composition according to claim 10 wherein the micro-porous solid is selected from the group consisting of montmorillonite KSF clay or montmorillomte K 10 clay, and e.
    mixtures thereof S..
    12. A composition according to claim 10 wherein the micro-porous solid is an ion-exchanged form of clay.
    S 0SSS
    S S S... S..
    S *5*5*
    S S
    13 A composition according to any preceding claim wherein the essential oil is selected from the group Consisting of thymol, carvacrol, eucaliptol, cinnamaldehyde, eugenol, menthol, cuminal, anethole, estragole, citronnellal, carvone, menthone, limonene, isoeugenol, bisabolol, camphor, geraniol, citral, and mixtures thereof in mixtures with ethanol or other antimicrobial volatile material.
    14. A composition according to any preceding claim wherein particle size of the micro-porous solid is from 1 micron (ii) to about 1000 microns (ii).
    15. A composition according to claims I to 14 wherein the solvent is selected from alcohols such as ethanol.
    16. A composition according to claims I to 14 wherein the solvent is selected from alkanes such as pentane, hexane, heptane, octane, iso-octane or mixtures thereof.
    17. A composition according to any preceding claim wherein the said composition further comprises one or more additional ingredients selected from the group consisting of protective colloids, adhesives, binding agents, chelating agents, thickening agents, thixotropic agents, penetrating agents, stabilizing agents, sequestering agents, anti-foam agents, antioxidants, natural or synthetic seasonings and/or flavors, dyes and/or colorants, vitamins, minerals, nutrients, enzymes, insecticides, deodorants, and mixtures thereof.
    18. A composition according to any of claims I to 17 comprising a suspension in a fluid medium.
    19. A composition according to claim 18 where the fluid medium is water 20. A composition according to any preceding claim comprising a granular product in the form of a powder, pellets, beads, or granules.
  21. 21. A composition according to claim 20 packed in a porous sachet.
  22. 22. A packaging material impregnated with the composition of any preceding claim.
  23. 23. A packaging material coated with the composition of any of claims I to 19.
  24. 24. A method for protecting food products from bacterial and flingal infection by treating * ..* a fruit or vegetable with the composition according to any of claims I to 19 *.
  25. 25. A method according to claim 24 wherein the food products are fresh fruits and : vegetables, fresh cut fruits and vegetables, semi-processed food or fully processed food.
    S PS.. *
    p.....
    S S
  26. 26. A method for antimicrobial protection of agricultural crops by such means as soil microbial sterilisatjon or over-spraying of the crops using the composition according to any of claims I to 20.
  27. 27. A process for preparing the composition according to any of claims I to 20 wherein the adsorption of the essential oil within the pores of the micro-porous solid is increased by mixing the essential oil with a solvent.
  28. 28 A process according to claim 27 wherein the solvent is selected from alcohols such as ethanol.
  29. 29. A process according to claim 27 wherein the solvent is selected from alkanes such as pentane, hexane, heptane, octane, iso- octane or mixtures thereof
  30. 30. A process for preparing the packaging material according to claim 22.
  31. 31. A process for preparing the packaging material according to claim 23.
  32. 32. A process according to claims 27 to 31 wherein any method of movement of air at ambient or higher temperatures, fluid bed drying, spray drying, freeze drying, vacuum filtration, regular filtration, centrifuging, pan granulation, and extrusion granulation may be used to convert the combination of micro-porous solid, essential oil and solvent into a material suitable for subsequent granulation. *0*$
    S *SS,S a.
    S a a a...
    S "a..
GB0710811A 2007-06-06 2007-06-06 Active packaging materials incorporating micro-porous solids and essential oils Expired - Fee Related GB2449876B (en)

Priority Applications (4)

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GB0710811A GB2449876B (en) 2007-06-06 2007-06-06 Active packaging materials incorporating micro-porous solids and essential oils
PCT/IB2008/001786 WO2008149232A2 (en) 2007-06-06 2008-06-06 Active materials incorporating micro-porous solids and essential oils
EP08776337A EP2170043A2 (en) 2007-06-06 2008-06-06 Active materials incorporating micro-porous solids and essential oils
AU2008259508A AU2008259508A1 (en) 2007-06-06 2008-06-06 Active materials incorporating micro-porous solids and essential oils

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WO2012010185A1 (en) * 2010-07-22 2012-01-26 Desert-Tree Bvba Method for producing a piece of clay for hydrating tobacco, piece of clay for hydrating tobacco, method for producing flavoured tobacco and flavoured tobacco
WO2013084175A1 (en) 2011-12-09 2013-06-13 Esseoquattro Spa Material for packaging fresh food of animal origin inhibiting the development of biogenic amines
WO2014170893A1 (en) * 2013-04-18 2014-10-23 Nobactra Israel Ltd. Oil carrying particulate matter and uses thereof
ES2525407A1 (en) * 2014-08-08 2014-12-22 Frutas El Dulze, S.L. Procedure for the preparation of a compound for vegetable aromatization, installation for the application of such aromatic composite and support employee (Machine-translation by Google Translate, not legally binding)
ITBO20130607A1 (en) * 2013-11-05 2015-05-06 Chemia S P A FORMULA BIOSTIMULANTE, CORROBORANTE AND CONCANTANTE BASED ON ZEOLITE AND NATURAL VEGETABLE EXTRACTS
ITBO20130606A1 (en) * 2013-11-05 2015-05-06 Chemia S P A FUNGICIDE BASED ON NATURAL EXTRACTS
WO2021133301A1 (en) * 2019-12-25 2021-07-01 Orta Dogu Teknik Universitesi Antimicrobial zeolitic materials with increased thermal resistance, having a hierarchical structure, comprising essential oils
WO2021247958A1 (en) * 2020-06-05 2021-12-09 Hazel Technologies, Inc. Devices and methods for release and delivery of active ingredients
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WO2012010185A1 (en) * 2010-07-22 2012-01-26 Desert-Tree Bvba Method for producing a piece of clay for hydrating tobacco, piece of clay for hydrating tobacco, method for producing flavoured tobacco and flavoured tobacco
WO2013084175A1 (en) 2011-12-09 2013-06-13 Esseoquattro Spa Material for packaging fresh food of animal origin inhibiting the development of biogenic amines
US10285405B2 (en) 2013-04-18 2019-05-14 Nobactra Israel Ltd. Oil carrying particulate matter and uses thereof
WO2014170893A1 (en) * 2013-04-18 2014-10-23 Nobactra Israel Ltd. Oil carrying particulate matter and uses thereof
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US11278023B2 (en) 2016-02-19 2022-03-22 Hazel Technologies, Inc. Compositions for controlled release of active ingredients and methods of making same
WO2021133301A1 (en) * 2019-12-25 2021-07-01 Orta Dogu Teknik Universitesi Antimicrobial zeolitic materials with increased thermal resistance, having a hierarchical structure, comprising essential oils
WO2021247958A1 (en) * 2020-06-05 2021-12-09 Hazel Technologies, Inc. Devices and methods for release and delivery of active ingredients

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AU2008259508A1 (en) 2008-12-11
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WO2008149232A2 (en) 2008-12-11
GB2449876B (en) 2009-05-06

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