EP2170043A2 - Matériaux actifs incorporant des matières solides microporeuses et des huiles essentielles - Google Patents
Matériaux actifs incorporant des matières solides microporeuses et des huiles essentiellesInfo
- Publication number
- EP2170043A2 EP2170043A2 EP08776337A EP08776337A EP2170043A2 EP 2170043 A2 EP2170043 A2 EP 2170043A2 EP 08776337 A EP08776337 A EP 08776337A EP 08776337 A EP08776337 A EP 08776337A EP 2170043 A2 EP2170043 A2 EP 2170043A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- micro
- composition
- composition according
- essential oil
- porous solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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- 238000000605 extraction Methods 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 239000010647 garlic oil Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 239000010648 geranium oil Substances 0.000 description 1
- 235000019717 geranium oil Nutrition 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- 239000010800 human waste Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000001469 lavandula hydrida abrial herb oil Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003750 molluscacide Substances 0.000 description 1
- 230000002013 molluscicidal effect Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000010661 oregano oil Substances 0.000 description 1
- 229940111617 oregano oil Drugs 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010816 packaging waste Substances 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 239000003375 plant hormone Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000611 regression analysis Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000011012 sanitization Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000009758 senescence Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 235000020994 smoked meat Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012438 synthetic essential oil Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229930007845 β-thujaplicin Natural products 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
- A23B7/00—Preservation of fruit or vegetables; Chemical ripening of fruit or vegetables
- A23B7/16—Coating with a protective layer; Compositions or apparatus therefor
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
- A23B2/00—Preservation of foods or foodstuffs, in general
- A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
- A23B2/725—Preservation of foods or foodstuffs, in general 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—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
- A23B7/00—Preservation of fruit or vegetables; Chemical ripening of fruit or vegetables
- A23B7/14—Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10
- A23B7/153—Preserving or ripening with chemicals not covered by group A23B7/08 or A23B7/10 in the form of liquids or solids
- A23B7/154—Organic compounds; Microorganisms; Enzymes
-
- 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
Definitions
- This invention relates to active materials, in particular, but not exclusively, for packaging perishable goods, particularly perishable foodstuffs.
- active materials in this application is defined as materials which release essential oil vapour in a controlled manner over time.
- One application of such active materials is in offering protection of perishable goods from quality loss during storage and display throughout the supply chain.
- perishable goods is defined as any good that requires special treatment and handling conditions to prevent or inhibit quality loss through microbiological, physiological or chemical spoilage.
- fresh produce is defined as harvested fruit, vegetables and cut flowers, uncooked meat and fish. Fresh produce is comprised within "perishable goods”.
- Processed foods including, but not limited to, processed fresh fruit and vegetables, juices, drinks, dairy produce, cheese, cooked or smoked meat and fish, and potted ornamental plants, are similarly comprised within "perishable goods".
- active packaging is defined as packaging which has been specifically designed to change the atmosphere within packs of perishable goods in order to extend their shelf life, improve their safety or enhance their sensory properties.
- ethylene acts as a plant hormone that has various physiological effects on fresh produce. It accelerates respiration, leading to enhanced maturity and senescence, and 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 (KMnO 4 ).
- potassium permanganate solution KMnO 4
- precautions must be taken to prevent contamination of the contents of the pack by contact with the chemical.
- Disposal of the packaging 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. This may arise from the foodstuff itself or from human contact with the foodstuff during harvesting or subsequent handling and processing.
- Packaging offering anti-microbial properties provides an effective solution for microbial contamination of the food surface from whatever source the contamination may have arisen.
- One of the most promising applications of active packaging is anti-microbial packaging film from which an active ingredient is released into the atmosphere surrounding the perishable goods or on to their surface thereby inhibiting growth of micro-organisms .
- 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 perishable goods, in particular foodstuffs.
- the efficacy of different active packaging materials in extending freshness and improving quality of fresh fruits, vegetables and cut flowers have been evaluated.
- 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 essential oil within the pores of the micro-porous solid.
- the solvent may be an alcohol, for example ethanol, or an alkane, for example pentane, hexane, heptane, octane, iso-octane or mixtures thereof. It is a feature of this invention that the solvent, preferably ethanol, when used in this way to increase adsorption of essential oil, also enhances the anti-microbial efficacy of the composition.
- the present invention addresses the limitations described above by combining micro-porous solids with essential oils in a bespoke process and then appropriately formulating the composition in such a way that it may be presented in different forms.
- the presentations can include:
- the composition will emit essential oil vapour at a controlled rate over an extended period of time which expression when used herein is defined as a longer period than has hitherto been described using natural materials.
- This characteristic of the composition may find uses in many different fields in addition to anti-microbial applications.
- the rate of release of essential oil vapour from the composition 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.
- a combination of benefits can be obtained.
- the composition can be formulated within active materials which provide both anti-microbial protection of the packaged goods and absorb unwelcome odours released by the packaged goods.
- a further example of a combination of benefits is where the solvent used to increase adsorption of the essential oil on the micro-porous solid is selected for its own anti- microbial properties, being released as a vapour along with the vapour of the essential oil, thereby enhancing the anti-microbial efficacy of the active material.
- 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 5.9 A or from the group consisting of medium-pore zeolites with channel free diameter from 5.9A to 5.0 A.
- 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.
- the micro-porous solid is a form of clay, preferably selected from the group consisting of montmorillonite KSF clay or montmorillonite KlO clay, and mixtures thereof.
- the micro-porous solid is a form of diatomite, preferably selected from the group consisting of diatomaceous earths which consist principally of amorphous silica.
- Diatomaceous earth deposits are usually categorised based upon their fresh water or salt water origin. After mining and drying at temperatures up to 650 0 C, both the chemical composition and the physical structure of diatomaceous earths make them of great commercial value for a wide spectrum of uses, including filter aids, functional fillers, carriers for active ingredients and diluents, and aggregates. In a few regions of the world, the diatomaceous earth deposits have been formed in sufficient thickness and purity to be mined for many uses beneficial to civilization, including practising this invention.
- the micro-porous solid is a form of cellulose fibre produced from natural materials including, but not limited to, the bark of trees, which may be selected, for example in the form of a micro-porous chip, granule, powder, or mat on to which the essential oil combined with a solvent may be adsorbed and then, where necessary, the resulting composition may be converted into granules, tablets, coatings or printing inks.
- 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 .
- pore size in the case of zeolite
- interlaying spacing in the case of clay
- water absorption capacity 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
- the micro-porous solid may be a cation-exchanged zeolite or clay with metals, such as K + , Na + , Li + , Cs + , Be +2 , Cr +3 , Ce +3 , Cu +2 , Ca +2 , Mg +2 , Fe +2 , Fe +3 , Ag + , Ba +2 or Zn +2 , and mixtures thereof.
- the micro-porous solid is selected from the group consisting of hydrophobic organophilic pentasil zeolites with Si:Al ratio higher than 10.
- the micro-porous solid is selected from the group of meso- porous solids such as silica gel SiO 2 and aluminum oxide Al 2 O 3 .
- the particle size of the micro-porous solid is generally less than 1000 microns ( ⁇ ) although larger particle sizes may be used in certain applications.
- presentation as a coating or within the mass of a substrate is preferably practised with particle sizes less than 25 microns whereas presentation as a tablet is preferably practised with particle sizes between 100 microns and 500 microns, and as a granule with particle sizes between 200 microns and 1000 microns, although these ranges of particle size are by no means limiting.
- essential oil is defined as any concentrated, hydrophobic liquid containing volatile aroma compounds either obtained directly from aromatic herbs or aromatic plants ("natural oils”), or synthesized (“nature-identical oils”) to be identical to those of natural origin. This invention has been practised with both natural oils and nature-identical oils with equally effective results.
- An oil is “essential” in the sense that it carries a distinctive scent, or essence, of the plant.
- the essential oil may be 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, although this list is by no means limiting.
- Active packaging materials using this invention have been developed for ethylene removal and for releasing anti-microbial essential oils allowing the original qualities of fruits, vegetables, flowers and processed food to be maintained during an extended period. Amongst other applications, this is often of crucial importance in developing the export of fresh products to distant markets.
- the essential oil is typically oregano oil, thyme oil, lavandin oil, clove oil or cinnamon oil, although many other essential oils can be used.
- a source of these essential oils is Frutarom Industries Limited, a multi-national corporation traded on the Tel-Aviv and London stock exchanges, who offer a large variety of essential oils suitable for use in applications described herein.
- synthetic essential oils such as thymol or carvacrol
- 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.
- 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, suspension aids, surfactants, penetrating agents, stabilizing agents, sequestering agents, anti-foam agents, antioxidants, natural or synthetic seasonings and/or flavours, dyes and/or colorants, vitamins, minerals, nutrients, enzymes, insecticides, deodorants, and mixtures thereof.
- additional ingredients selected from the group consisting of protective colloids, adhesives, binding agents, chelating agents, thickening agents, thixotropic agents, suspension aids, surfactants, penetrating agents, stabilizing agents, sequestering agents, anti-foam agents, antioxidants, natural or synthetic seasonings and/or 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.
- the granular product may then be compressed into a tablet.
- Smaller tablets may be presented in a porous sachet whereas larger tablets may be used without any packaging within circulating air systems where anti-microbial activity is advantageous, e.g. storage depots for fresh produce, air conditioning systems, including those used within aircraft, hotels, and hospitals.
- the granules are dried until they are substantially free of any surface liquid, then mixed with a powdered binding agent such as polyethylene glycols, preferably of molecular weight between 3000 and 6000, and then compressed causing the granules to adhere to each other for the lifetime of the tablet.
- a powdered binding agent such as polyethylene glycols, preferably of molecular weight between 3000 and 6000
- composition according to the first aspect of the invention has many uses in applications where anti-microbial activity is beneficially released from the composition over an extended period of time.
- the composition may be used:
- the food products may be fresh fruits and vegetables, fresh cut fruits, vegetables or flowers, semi-processed food or fully processed food.
- composition in powder form may also be incorporated into animal feedstuffs to prevent microbial development within the gastro-intestinal tract.
- repelling unwanted pests such as, but not limited to, slugs, snails and insects from agricultural crops, horticultural nursery stock, sports turf and garden plants.
- a packaging material impregnated with or coated or printed with the anti-microbial composition according to the first aspect of the invention.
- a suspension agent such as those provided within the Solsperse® range manufactured by Lubrizol Corporation has been beneficial in suspending the micro-porous solid, hi the embodiment where the packaging material is coated or printed with an anti-microbial composition, it can subsequently be converted into different packaging products including filmic bags, pouches and sachets including reclosable "zipped" versions or used as a face material in labelstock constructions suitable for subsequent conversion into self-adhesive labels.
- the anti-microbial coating or printing ink is located on the opposite side of the face material to the pressure sensitive adhesive.
- the self-adhesive label will be applied to the internal wall of the bag, pouch or sachet containing the perishable goods.
- the active packaging has been produced by coating or printing the composition on a packaging film, then following conversion of the active packaging material into a suitable packaging format such as, for example, filmic bags, pouches and sachets by whatever process and of whatever configuration, the coated or printed side of the active packaging substrate is always located on the inner surface of the pack containing the perishable foodstuff. Furthermore, it is not necessary for the active packaging material to be flood coated with the composition.
- the composition may be strip coated, pattern coated or printed in order to provide the economic and technical benefits of this invention. The strip or pattern coating or printing can be applied in such a way that the composition does not interfere with heat sealing of the active packaging substrate.
- the coating or printing is suitably pigmented or coloured, and the bag, sachet or pouch is made from a transparent filmic substrate
- the coating or printing can be reverse printed or otherwise used to carry a marketing message providing, amongst other uses, information to the consumer.
- packaging material impregnated with, coated with, or printed with the antimicrobial composition offers improved properties when used as packaging for perishable foodstuffs including properties such as ethylene removal, water permeability and anti-microbial activity, all of which are beneficial to the freshness and quality of packed perishable products.
- composition according to the second aspect of the present invention can also be used in the medical or veterinary fields as a packaging film where anti-microbial protection is required.
- the micro-porous solid, the essential oil and solvent are combined together in a bespoke process resulting in a slurry.
- the slurry may be dried by various means including 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, in order to produce active packaging granules or beads.
- the granules or beads are of diameter between lmm and 5mm, more preferably around 3mm.
- the porous sachet is preferably made from materials based upon natural fibres such as paper, or upon polymeric materials manufactured from petroleum, renewable, or sustainable sources, or upon combinations of natural fibres and polymeric materials.
- natural fibres such as paper, or upon polymeric materials manufactured from petroleum, renewable, or sustainable sources, or upon combinations of natural fibres and polymeric materials.
- appropriate materials are heat sealable 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 perishable goods to provide an anti-microbial 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 goods.
- 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.
- the quantity of essential oil adsorbed into the micro-pores of the zeolite may be up to 35% by weight, preferably 10 to 35% by weight, more preferably 10 to 30% by weight, still more preferably 10 to 25% by weight, even more preferably 15-25% by weight. This can be seen from the experimental results shown in Figures 6, 7 and 8.
- micro-porous solid selected from the group consisting of large-pore zeolites with channel free diameter from 5.9A to 12A, such as
- 5.9A such as ZSM-5, Silicalite, Ferrierite types, Linde-T, Merlinoite types, or Linde W, and mixtures thereof.
- a suitable solvent for example an alcohol such as 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, whether subsequently presented as a coating or as a granule or tablet.
- a suitable solvent for example an alcohol such as ethanol or an alkane such as pentane, hexane, heptane, octane, iso-octane or a mixture thereof.
- the present invention has been found to offer controlled release of essential oils from micro- porous solids during longer periods than has hitherto been described using natural materials. This has enabled the invention, in addition to the preservation of perishable goods, to find further application for use as a mollusc repellent and as an insect repellent.
- the invention provides an insect or mollusc repellent impregnated or coated with the composition according to the invention. These applications are of particular interest in the ornamental nursery market and the home and garden markets in those countries where the use of molluscicides and insecticides is declining in favour of natural alternative remedies such as those described here. Different types of essential oil may be required for each field of application. Mollusc repellent activity has been confirmed using pine oil, cedarwood oil and garlic oil. Insect repellent activity has been confirmed using aniseed oil, lemon eucalyptus oil, cedarwood oil, geranium oil and lemongrass oil.
- 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 purity are essential. However, we have found naturally occurring zeolites to be entirely suitable for the practice of this invention.
- 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 crystals with dimensions of a comparable size to their natural counterparts. Typically, naturally occurring zeolites present lower Si:Al ratios than synthetic ones.
- 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 de-alumination of polar zeolites. This is done by treating the zeolite with steam at elevated temperatures, greater than 500 0 C. This high temperature heat treatment breaks the aluminium-oxygen bonds and the aluminium atom is expelled from the zeolite framework.
- zeolites may differ in the following important respects:
- 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)
- particle sizes varying up to lOOO ⁇ m where smaller particle sizes are preferred for coating and printing ink formulations and larger particle sizes may be used in granular and tablet 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
- adsorption e.g. taint removal, O 2 scavenging, ethylene scavenging and water removal
- absorption e.g. condensation control and drip collection
- hydrolysis e.g., SO 2 release
- desorption e.g. ethanol, hinokitiol and water release
- Polymeric and natural fibre substrates of many types with different physico-chemical properties have been used by the inventor for the production of active packaging materials according to this invention e.g., polyethylene, polypropylene, polyester, polyamide and other polymeric substrates of petroleum and of plant "bio-polymer” origins, and mixtures and laminations thereof with each other or with natural fibre materials such as paper.
- micro-porous materials with various anti-microbial active essential oils have been investigated. Furthermore, the effect of water content, calcination temperature, particle size, solid content and physical form, on the activity of the composition as ethylene adsorber and as anti-microbial releasing agent, have been studied using different micro-porous materials, e.g. large-pore zeolites; medium-pore zeolites; small-pore zeolites; micro-porous clays; diatomaceous earths, ion-exchanged zeolites; active micro-porous solids and hydrophobic pentasil zeolites.
- large-pore zeolites e.g. large-pore zeolites; medium-pore zeolites; small-pore zeolites; micro-porous clays; diatomaceous earths, 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 complex within the active packaging, have been determined by us under various humidity conditions.
- a solution of an essential oil in a solvent is added a micro-porous solid.
- the slurry composition is preferably stirred.
- a suspension agent may be added when the slurry composition is subsequently to be incorporated in a coating or printing ink.
- the mixture may be cooled to room temperature.
- different presentations of the composition may be prepared. If it is required to present the composition as a coating or a printing ink, the slurry composition may be added directly to a binding agent which has been dissolved in an organic solvent.
- the binding agent and solvent must be compatible with the components within the slurry.
- a suitable binding agent is DSM NeoResins product NeoCryl B-723 dissolved in ethyl acetate.
- the slurry is vacuum filtered and the precipitated solid is washed by a small quantity of cold solvent and then dried at room temperature, for example vacuum dried.
- FIGS 1 to 4 show the rate of loss of an essential oil (thymol) from different micro porous solids
- Figure 5 shows the results of a comparative trial of five different products offering antimicrobial properties including the composition according to the invention
- Figures 6 to 8 show the rate of loss of an essential oil (thymol) from different types of zeolite using different adsorbed amounts of essential oil-ethanol.
- Figures 9 and 10 show the rate of loss of an essential oil (thymol) from different types of zeolite using two different solvents to assist adsorption of the essential oil.
- the slurry is formulated with binding agents commonly used in the formulation of solvent-based inks and coatings such as that produced and marketed by DSM NeoResins.as NeoCryl B-723
- 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 bespoke 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 is measured by extraction of the residual thymol from the micro-porous solid at regular time intervals and then subjecting the extract to gas chromatography - mass spectrometry (GC- MS) analysis.
- GC- MS gas chromatography - mass spectrometry
- Ethanol adsorbed on to a silica gel (EtOH-SG) 2. Ethanol adsorbed on to a zeolite (EtOH-Zeo)
- composition according to the invention comprising an essential oil adsorbed on a zeolite using an ethanol solvent has produced an outstanding result hi which none of the grapes showed any microbial damage.
- This composition was produced by the bespoke process according to the invention.
- the zeolite is a natural zeolite of particle size between 100 and 200 microns.
- the relative proportions of the components are as follows: 1.0 gram of thymol in 2.0 mis of ethanol adsorbed on to 3.0 grams of zeolite Air dried zeolite Reference S
- the zeolite is a natural zeolite of particle size between 200 and 300 microns.
- the relative proportions of the components are the same as in figure 6.
- the zeolite is the synthetic zeolite SylosivAlO® of particle size between 3 and 5 microns taken from hermetically sealed bags supplied by Grace Davison.
- the relative proportions of the components are as follows: 1.0 gram thymol in 2 ml ethanol added to 3.0 grams of zeolite Reference AL 1.5 grams thymol in 3 ml ethanol added to 3.0 grams of zeolite Reference AH 2.0 grams thymol in 4 ml ethanol added to 3.0 grams of zeolite Reference AHH
- the zeolite is a natural zeolite of particle size between 100 and 200 microns.
- the relative proportions of the components are as follows:
- the zeolite is the synthetic zeolite Sylosiv A10® of particle size between 3 and 5 microns taken from hermetically sealed bags supplied by Grace Davison.
- the relative proportions of the components are as follows: 1.5 grams thymol in 2 ml ethanol added to 3.0 grams of zeolite Reference AE
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Food Science & Technology (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pest Control & Pesticides (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- Microbiology (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Toxicology (AREA)
- Dentistry (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
Abstract
Des matériaux actifs employant une composition contenant des huiles essentielles adsorbées en combinaison avec un solvant à l'intérieur d'une matière solide microporeuse ont été développés. La libération contrôlée ultérieure d'une vapeur d'huile essentielle fournit de nombreuses applications comprenant des propriétés antimicrobiennes et une prolongation de la durée de conservation à des marchandises périssables conditionnées. Le matériau actif peut se présenter sous la forme d'un substrat polymère ou de fibres naturelles, revêtu ou imprimé par la composition ou sous la forme de granulés ou de comprimés facultativement contenus à l'intérieur d'un sachet poreux.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0710811A GB2449876B (en) | 2007-06-06 | 2007-06-06 | Active packaging materials incorporating micro-porous solids and essential oils |
| PCT/IB2008/001786 WO2008149232A2 (fr) | 2007-06-06 | 2008-06-06 | Matériaux actifs incorporant des matières solides microporeuses et des huiles essentielles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2170043A2 true EP2170043A2 (fr) | 2010-04-07 |
Family
ID=38318787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP08776337A Withdrawn EP2170043A2 (fr) | 2007-06-06 | 2008-06-06 | Matériaux actifs incorporant des matières solides microporeuses et des huiles essentielles |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2170043A2 (fr) |
| AU (1) | AU2008259508A1 (fr) |
| GB (1) | GB2449876B (fr) |
| WO (1) | WO2008149232A2 (fr) |
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| EP2442643A4 (fr) * | 2009-06-17 | 2014-08-06 | Isp Investments Inc | Procédé de préparation de substances actives biocides stables, microencapsulées et à libération lente et composition apparentée |
| WO2012010185A1 (fr) * | 2010-07-22 | 2012-01-26 | Desert-Tree Bvba | Procédé de fabrication d'une pièce en argile servant à l'hydratation du tabac, pièce en argile servant à l'hydratation du tabac, procédé de production d'un tabac aromatisé et tabac aromatisé |
| CL2010001342A1 (es) * | 2010-12-03 | 2014-08-01 | Univ Santiago Chile | Proceso de obtencion de un film que comprende la incorporacion de agentes antimicrobianos de origen natural en una estructura polimerica, para el desarrollo de envases destinados a incrementar la vida util de carne refrigerada, preferentemente de salmon fresco refrigerado. |
| US8445032B2 (en) | 2010-12-07 | 2013-05-21 | Kimberly-Clark Worldwide, Inc. | Melt-blended protein composition |
| US9648874B2 (en) | 2010-12-07 | 2017-05-16 | Kimberly-Clark Worldwide, Inc. | Natural, multiple use and re-use, user saturated wipes |
| US10821085B2 (en) | 2010-12-07 | 2020-11-03 | Kimberly-Clark Worldwide, Inc. | Wipe coated with a botanical composition having antimicrobial properties |
| US9149045B2 (en) | 2010-12-07 | 2015-10-06 | Kimberly-Clark Worldwide, Inc. | Wipe coated with a botanical emulsion having antimicrobial properties |
| US9832993B2 (en) | 2010-12-07 | 2017-12-05 | Kimberly-Clark Worldwide, Inc. | Melt processed antimicrobial composition |
| US8524264B2 (en) | 2010-12-07 | 2013-09-03 | Kimberly-Clark Worldwide, Inc. | Protein stabilized antimicrobial composition formed by melt processing |
| FR2968893B1 (fr) * | 2010-12-20 | 2013-11-29 | Centre Nat Rech Scient | Composition phytosanitaire a base de zeolithe |
| US8691042B2 (en) * | 2011-09-22 | 2014-04-08 | Wei-Yin Chang | Eco anti-mold fresh-keeping chip |
| ITRM20110656A1 (it) | 2011-12-09 | 2013-06-10 | Esseoquattro Spa | Imballaggio per alimenti freschi di origine animale che inibisce lo sviluppo delle ammine biogene |
| US8574628B2 (en) | 2011-12-19 | 2013-11-05 | Kimberly-Clark Worldwide, Inc. | Natural, multiple release and re-use compositions |
| CZ2012167A3 (cs) * | 2012-03-09 | 2013-04-03 | Univerzita Tomáse Bati ve Zlíne | Antimikrobiální komponenta a její pouzití |
| CN113842362A (zh) | 2012-11-14 | 2021-12-28 | 格雷斯公司 | 含有生物活性材料与无序无机氧化物的组合物 |
| MA35295B1 (fr) * | 2012-12-31 | 2014-08-01 | Advanced Scient Developments | Complexe moleculaire detoxifiant et antimicrobien |
| IL225825A (en) * | 2013-04-18 | 2014-06-30 | Nobactra Israel Ltd | Kit and methods for the treatment or prevention of plant pathogenic infection and several isolated antagonistic missiles |
| ITBO20130607A1 (it) * | 2013-11-05 | 2015-05-06 | Chemia S P A | Formulato biostimolante, corroborante e concimante a base di zeolite ed estratti naturali vegetali |
| ITBO20130606A1 (it) * | 2013-11-05 | 2015-05-06 | Chemia S P A | Fungicida a base di estratti naturali |
| ES2525407B1 (es) * | 2014-08-08 | 2015-06-16 | Frutas El Dulze, S.L. | Procedimiento de preparación de un compuesto para aromatización de hortalizas, instalación para la aplicación de dicho compuesto aromático y soporte empleado |
| WO2016049015A1 (fr) * | 2014-09-22 | 2016-03-31 | Rutgers, The State University Of New Jersey | Huile essentielle à base de plantes pour la préservation des biomatériaux |
| ES2574332B1 (es) * | 2014-12-16 | 2017-03-27 | Ercros, S.A. | Comprimidos para el tratamiento y desinfección de aguas |
| GB2542340B (en) * | 2015-09-11 | 2019-05-01 | Agricultural Res Council Arc | Membrane and method for preservation of produce |
| IL292558A (en) * | 2016-02-19 | 2022-06-01 | Hazel Tech Inc | Preparations for the controlled release of active ingredients and methods for their preparation |
| ES2588261B1 (es) * | 2016-04-15 | 2017-05-10 | Universidad Politécnica De Cartagena | Envase de cartón para envasado activo de frutas y hortalizas frescas, y procedimiento de fabricación del mismo |
| KR102005027B1 (ko) * | 2017-06-21 | 2019-07-31 | 주식회사 매스컨 | 장기 발향 지속성을 갖는 발향 재료 및 그 제조 방법 |
| CN110178893A (zh) * | 2019-07-08 | 2019-08-30 | 四川绿品源贸易有限公司 | 一种天然果蔬防霉抑菌组合熏蒸颗粒 |
| WO2021133301A1 (fr) * | 2019-12-25 | 2021-07-01 | Orta Dogu Teknik Universitesi | Matériaux zéolitiques antimicrobiens à résistance thermique accrue, ayant une structure hiérarchique, comprenant des huiles essentielles |
| JP2023529837A (ja) * | 2020-06-05 | 2023-07-12 | ヘイゼル テクノロジーズ, インコーポレイテッド | 有効成分を放出および送達するためのデバイスおよび方法 |
| CN111765699A (zh) * | 2020-07-09 | 2020-10-13 | 长虹美菱股份有限公司 | 一种食品保鲜冰箱及其方法 |
| FR3113560A1 (fr) * | 2020-09-02 | 2022-03-04 | Xeda International S.A. | Procédé de protection de produits végétaux pendant le transport, dispositif de traitement correspondant |
| CN112126187A (zh) * | 2020-10-10 | 2020-12-25 | 浙江锦晔科技有限公司 | 一种防蚊热塑性弹性体及其制备方法 |
| CN113040218B (zh) * | 2021-03-09 | 2023-05-16 | 广东省农业科学院蚕业与农产品加工研究所 | 一种基于等离子杀菌的气调包装用精油施用装置 |
| US20240156134A1 (en) * | 2021-04-16 | 2024-05-16 | Ryp Labs, Inc. | Controlled-release delivery compositions for extending the life of perishable goods and methods of production and use thereof |
| WO2023235158A1 (fr) * | 2022-05-31 | 2023-12-07 | Corning Research & Development Corporation | Récipient optique de composant optique formé à partir de composition polymère avec additif aversif |
| WO2025248522A1 (fr) * | 2024-05-31 | 2025-12-04 | Nemaguard Technologies Ltd | Composition nématocide à libération contrôlée à base d'huile essentielle et ses utilisations |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5863348A (ja) * | 1981-10-12 | 1983-04-15 | Toppan Printing Co Ltd | 青果物の保存方法 |
| JPS59132876A (ja) * | 1983-01-20 | 1984-07-31 | Toppan Printing Co Ltd | 食品の保存方法 |
| JPS60146803A (ja) * | 1984-01-06 | 1985-08-02 | Kiyoshi Saotome | 植物病原性細菌の発芽増殖阻害剤 |
| JPS60146804A (ja) * | 1984-01-06 | 1985-08-02 | Kiyoshi Saotome | 土壌病害菌の発芽増殖阻害剤 |
| JPS6187602A (ja) * | 1984-10-05 | 1986-05-06 | Daiwa Kagaku Kogyo Kk | 揮発性防カビ剤 |
| JPH01301607A (ja) * | 1988-05-31 | 1989-12-05 | Masaru Morita | ゲットウ精油防虫体 |
| JPH03262529A (ja) * | 1990-03-14 | 1991-11-22 | Yamada Koji | 脱臭材 |
| JPH11335218A (ja) * | 1998-05-21 | 1999-12-07 | Sekisui Chem Co Ltd | 殺ダニ剤 |
| JP4350230B2 (ja) * | 1999-10-04 | 2009-10-21 | 株式会社日本衛生センター | シロアリ殺虫剤及びシロアリ殺虫性材料 |
| US6543385B2 (en) * | 2000-12-07 | 2003-04-08 | Nestec, Ltd. | Animal litter composition containing silica gel and methods therefor |
| US20050214337A1 (en) * | 2002-02-26 | 2005-09-29 | Mcgee Thomas | Pesticidal compositions |
| TW200525015A (en) * | 2003-09-11 | 2005-08-01 | Taiyo Kagaku Kk | Porous silica having substance carried thereon |
-
2007
- 2007-06-06 GB GB0710811A patent/GB2449876B/en not_active Expired - Fee Related
-
2008
- 2008-06-06 WO PCT/IB2008/001786 patent/WO2008149232A2/fr not_active Ceased
- 2008-06-06 EP EP08776337A patent/EP2170043A2/fr not_active Withdrawn
- 2008-06-06 AU AU2008259508A patent/AU2008259508A1/en not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2008149232A3 * |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2008259508A1 (en) | 2008-12-11 |
| GB2449876B (en) | 2009-05-06 |
| WO2008149232A3 (fr) | 2009-01-29 |
| GB0710811D0 (en) | 2007-07-18 |
| WO2008149232A2 (fr) | 2008-12-11 |
| GB2449876A (en) | 2008-12-10 |
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