HK1210797B - Cyclodextrin compositions, articles, and methods - Google Patents

Description

Cyclodextrin compositions, articles, and methods

The application is a divisional application of Chinese patent application with the application number of 201110431674.3 and the invention name of cyclodextrin composition, article and method, which is filed on 20/12/2011.

This application was filed under the name of a united states company CELLRESIN techlologies, LLC (as applicant in all designated countries except the united states), and the inventors Willard e.wood, William j.kuduk, and Joseph s.keute (as the designated applicant for the united states only), and claimed priority to U.S. patent application serial No. 61/468,041 filed 3/27/2011.

Background

The shelf life of the produce or produce material (including whole plants and parts thereof, including fruits, vegetables, tubers, bulbs, cut flowers and other active respiring plants or plant materials) is typically determined at least in part by the amount of ethylene hormone produced by the respiring material. Ethylene is a known plant maturation or maturation hormone. At any substantial ethylene concentration within and around the plant material, maturation of the plant is initiated, maintained or accelerated depending on the concentration. Ethylene-sensitive and ethylene-insensitive horticultural commodities (agricultural products and ornamentals) are classified as either catastrogenic or non-catastrogenic based on the manner of ethylene production and responsiveness to added ethylene. Mutant crops respond to ethylene by inducing an increase in respiration at an early stage and accelerate ripening in a concentration-dependent manner. Non-climacteric crops are matured without ethylene and respiration mutations. However, certain non-saltating crops are sensitive to exogenous ethylene, which can significantly reduce the post-harvest shelf life. Non-climacteric agricultural products hide several active ethylene receptors. Thus, exposure of non-saltating agricultural products to exogenous ethylene can trigger physiological abnormalities, thereby reducing shelf life and quality. See Plant Physiol et al (1967) 42144-. Many attempts have been made to remove ethylene from the ambient packaging atmosphere surrounding the produce or from the storage environment in an attempt to improve shelf life. It is understood that reduced ethylene concentrations are achieved by a reduction in the stimulation of specific ethylene receptors within the plant. Many compounds other than ethylene interact with this receptor: some mimic this effect of ethylene; others prevent ethylene binding and thus counteract its effect.

Many compounds used as antagonists or inhibitors block the action of ethylene by binding to ethylene binding sites. These compounds can be used to counteract the effects of ethylene. Unfortunately, they typically diffuse away from the binding site over a period of several hours, resulting in a longer reduction in the inhibitory effect. See e.sisler and c.wood, plantargrowth reg.7,181-191 (1988). Thus, one problem associated with such compounds is that the exposure must be continuous if the effect is to last for more than a few hours. Cyclopentadiene has been shown to be an effective blocking agent for ethylene binding. See E.Sisler et al Plant Growth Reg.9,157-164 (1990). Methods of using dicyclopentadiene and its derivatives to combat ethylene responses in plants are disclosed in U.S. Pat. No. 5,100,462 to Sisler et al. U.S. Pat. No. 5,518,988 to Sisler et al describes the use of a catalyst having C_1-4The cyclopropene of the alkyl group serves to block the action of ethylene.

An appropriate olefinic antagonist or inhibitor of ethylene production in the recipient site or agricultural product is 1-methylcyclopentene, derivatives and analogues thereof have been tried as an antagonist or inhibitor of ethylene production from respiratory plant or agricultural product materials. 1-methyl-cyclopropene (1-MCP), 1-butene, and other olefins have been shown to have at least some measurable activity for inhibiting ethylene production and thus extending shelf life. There have been several proposals for methods of producing and releasing 1-MCP to inhibit ethylene release and thus slow down maturation and maintain the quality of plant material. Currently, 1-MCP is dispensed by the release of 1-MCP from a moisture activated powder or a packet of powder containing complexed 1-MCP. In these techniques, 1-MCP is released from a point source, which creates a concentration gradient in the storage chamber, thus leading to a change in ripening inhibition, where some produce has an extended lifetime and others exposed to smaller concentrations of 1-MCP tend to have less ethylene inhibition and have a reduced shelf life.

Despite these efforts, there remains a substantial need in the art for improved prevention of plant maturation and degradation. In particular, pressure from world urbanization, manufacturing, and population growth has necessitated the development of new technologies to improve the efficiency and yield of natural resources consumed for delivering food to the growing global population. For example, in the united states, profit losses between 8% and 16% in fresh produce are estimated to be due to spoilage and shrinkage, which is estimated to range from 80 to 280 billion pounds in a full system. This loss translates into significant wasted resources, such as the use of pesticides, fertilizers, and herbicides; land and water use; transportation, including the use of oil and natural gas; and resources associated with agricultural product storage. These and other resource losses are due to inefficiencies in production and shipping, such that fruits and vegetables spoil significantly before these critical produce can reach the consumer. The feasibility study of the Asia-Pacific agricultural engineering and machinery center of the United nations on the application of green technology to sustainable agricultural development states that:

"technology is a link that links sustainability with enhanced productivity, effectively maintaining productivity of natural resources by carefully planning the conservation and development of these resources, soil, water, plants, and animals. "

(feasibility study of the Asia-Pacific agriculture engineering and machinery center of United nations for applying green technology to sustainable agriculture development,pdf, at 20 th:// www.unapcaem.org/publication/GreenTechPage). As the world population grows and the amount of arable land shrinks, climate change is promoting the rigors of agricultural technology. More mouthpieces to feed, plus less farmable land and varying rainfall patterns, means that there is an increasing need to have farmers make more technology with less. The EU Committee recently announced an action to optimize food Packaging without compromising safety in order to reduce food waste (Harrington, R., "Packaging placing center stage in European food waste," http:// www.foodqualitynews.com/Public-centers/Packaging-placing-centerstage-in-European-food-waste-stream). This action is directed to recent findings: 179kg of food is wasted per person each year. This project focuses on the need for innovations, such as "active packaging" or "smart packaging," as one aspect of the solution.

Therefore, a technology that addresses the problem of fruit and vegetable spoilage is crucial as a "green" technology that reduces the waste of food and its associated resources by increasing the effective efficiency of the arable land.

Brief description of the invention

The present invention relates to a packaging material comprising a cyclodextrin composition. The cyclodextrin composition comprises an effective amount and a controlled release amount of an olefinic inhibitor of ethylene production in an agricultural product. The packaging material is coated on at least a portion of one surface thereof with the cyclodextrin composition. After coating, the cyclodextrin composition is subjected to electromagnetic radiation, such as Ultraviolet (UV) radiation, or electron beam (e-beam) radiation. The cyclodextrin composition reacts upon exposure to the radiation such that the composition becomes bound to the packaging material, or polymerizes to form a polymer layer or coating on the surface of the packaging material, or a combination of polymerization and binding. The coated and irradiated packaging material is then used to form a container, package, or packaging component or insert that produces a uniform amount of the olefinic inhibitor that inhibits ethylene such that the live agricultural products stored within the container have consistent quality and extended useful life. Extending the life of fresh produce can result in a significant reduction in food waste. In some cases, the packaging material is formed into a container, package, or packaging component, and then the container, package, or packaging component is coated with the cyclodextrin composition and irradiated. The irradiated cyclodextrin compositions form a coating or layer on at least a portion of the packaging material or container. The coating or layer comprises the cyclodextrin inclusion complex and the olefinic inhibitor compound in the cyclodextrin central pore, thereby acting as an effective source of the olefinic inhibitor.

The present invention contemplates a treated article that is a treated packaging material or container having disposed thereon an irradiated cyclodextrin composition. The cyclodextrin composition comprises an inclusion complex. Within the inclusion complex, the cyclodextrin molecule comprises an effective amount of the olefinic inhibitor of ethylene production in agricultural products. The treated packaging material or container is coated with the cyclodextrin composition and the coated packaging material or container is irradiated to form a treated packaging material or container. The treated packaging material is then formed into a flexible, rigid, or semi-rigid container. The treated container releases the olefinic inhibitor into an enclosed volume within a packaging structure such that the living plant material contained therein has an extended or longer useful life.

The present invention contemplates a cyclodextrin composition comprising one or more radiation polymerizable monomers and a cyclodextrin inclusion complex comprising cyclodextrin and an olefinic inhibitor. The invention also contemplates a cyclodextrin composition comprising a substituted cyclodextrin compound, wherein the substituted cyclodextrin compound is reactive to electromagnetic radiation, and wherein a portion of the substituted cyclodextrin compound comprises an inclusion complex. The present invention also contemplates a radiation-cured coating of a cyclodextrin composition such that a cyclodextrin compound or substituted cyclodextrin is bound to a polymer chain or backbone, wherein some portion of the bound cyclodextrin compound comprises an inclusion complex. The present invention also contemplates a radiation-cured coating of a cyclodextrin composition in which the cyclodextrin and/or cyclodextrin inclusion complex is not part of the radiation-polymerized polymer, but is entrapped or entangled within the polymerized coating. The present invention also contemplates a packaging material having surface functionalization on at least a portion of one major surface thereof, wherein the surface functionalization comprises a radiation-cured cyclodextrin composition.

The present invention also contemplates a method of forming an inclusion complex of an olefinic inhibitor and cyclodextrin to form a cyclodextrin composition, then coating the cyclodextrin composition onto at least a portion of a major surface of a packaging material or container, and irradiating at least the coated portion of the packaging material or container to form a treated sheet or film.

The present invention also contemplates that the treated packaging material or container may be manufactured by a method wherein the treated packaging material or container is formed under conditions having a reduced moisture content.

The invention also contemplates the use of the treated packaging material or container for packaging respiratory agricultural product materials. Enclosing the produce material within the packaging material or container and contacting the treated portion of the treated packaging material or container with an appropriate and active amount of water such that the cyclodextrin releases the olefinic inhibitor at a concentration sufficient to inhibit ripening or maturation of the produce. The olefinic inhibitor is also released from the treated packaging material or container by exposure to a controlled level of humidity. During dispensing and storage, when the storage temperature of the packaged produce material is low (e.g., between about 0 ℃ and about 14 ℃), the humidity within the enclosed volume around the produce will be high (e.g., between about 70% to about 100% relative humidity) due to normal moisture loss from the produce respiration into the enclosed packaging volume. In many cases, the amount of water vapour exceeds the amount corresponding to 100% relative humidity, and liquid water condenses inside the package. The water vapor and/or liquid water released by the produce within the enclosed volume of the package is sufficient to release the olefinic inhibitor. Alternatively, the internal humidity of the packaging material or container is adjusted by adding water to release the olefinic inhibitor prior to sealing the package or container. The relative humidity can be controlled by adding moisture (water mist, spray or steam) to the air by a humidifier during packaging.

The present invention further contemplates a container or package for agricultural products made from conventional packaging materials and containing a packaging insert comprising a section of the treated sheet or film of the present invention which can release the olefinic inhibitor by increasing or adding a controlled level of humidity.

Drawings

FIG. 1 is a plot of 1-butene headspace concentration versus time.

FIG. 2 is a graph of 1-MCP headspace concentration versus coating composition.

FIG. 3 is a graph of 1-MCP headspace concentration versus time and coated surface area.

FIG. 4 is a graph of 1-MCP headspace concentration versus time, coating composition.

FIG. 5 is a plot of 1-MCP headspace concentration versus time.

Detailed Description

1. Definition of

As used herein, the term "cyclodextrin composition" refers to a composition comprising a cyclodextrin inclusion complex that (1) is capable of coating a sheet, film, or container and reacting with UV or electron beam radiation to form a treated sheet, film, or container; or (2) coated on a sheet, film, or container; or (3) is a polymeric layer on at least a portion of a major surface of a sheet, film, or container; or (4) covalently bonded to at least a portion of a major surface of a sheet, film, or container; or (5) is a combination of (3) and (4).

As used herein, the term "cure" or "radiation cure" refers to exposing a cyclodextrin composition to electromagnetic radiation or electron beam radiation under conditions that cause the composition to undergo a reaction, such as polymerization, bonding or grafting to a polymer or surface, crosslinking, or a combination thereof. Electromagnetic radiation includes, but is not limited to, Ultraviolet (UV) radiation, microwave radiation, and gamma radiation. "radiation polymerizable" or "radiation curable" monomers and crosslinkers are compounds that are polymerized or crosslinked due to interaction with electromagnetic or electron beam radiation. In certain embodiments, the radiation polymerizable monomers and the crosslinking agent are also polymerizable by thermal means.

As used herein, the term "cyclodextrin" or "cyclodextrin compound" refers to a cyclic maltooligosaccharide having at least five glucopyranose units linked by α (1-4) linkages. Examples of useful cyclodextrins include alpha-, beta-, or gamma-cyclodextrins, wherein the alpha-cyclodextrin has six glucose residues; beta-cyclodextrin has seven glucose residues; whereas gamma-cyclodextrin has eight glucose residues. Cyclodextrin molecules are characterized by a rigid, truncated conical molecular structure having a hollow interior, or pore, of a specified volume. "Cyclodextrin" may also include a cyclodextrin derivative, as defined below, or a blend of one or more cyclodextrins. The following table lists the properties of alpha-, beta-, and gamma-cyclodextrins.

As used herein, the term "cyclodextrin inclusion complex" refers to a combination of an olefinic inhibitor compound and a cyclodextrin, wherein the olefinic inhibitor compound is substantially disposed within the pores of the cyclodextrin ring. The complexed olefinic inhibitor compound must meet this size criterion to at least partially fit into the cyclodextrin internal cavity or pore to form an inclusion complex. These cyclodextrin inclusion complexes include an amount of "uncomplexed" cyclodextrin that is inherent to the formation and presence of the inclusion complex because (1) in embodiments, the synthesis of the inclusion complex does not result in 100% formation of the inclusion complex; and (2) in embodiments, the inclusion complex is in equilibrium with uncomplexed cyclodextrin/uncomplexed olefinic inhibitor. Each combination of cyclodextrin and olefinic inhibitor has a characteristic balance associated with the cyclodextrin inclusion complex.

As used herein, the term "cyclodextrin derivative" or "functionalized cyclodextrin" refers to a cyclodextrin having a functional group bound to the hydroxyl groups of the cyclodextrin glucose moieties (moiety). An example is a group that makes the cyclodextrin derivative soluble in a radiation polymerizable monomer. Certain cyclodextrin derivatives are described, for example, in U.S. patent No. 6,709,746.

As used herein, the term "olefinic inhibitor", "olefinic inhibitor compound" or "olefinic inhibitor of ethylene production" refers to an olefinic compound that contains at least one olefinic double bond, has from about 3 to about 20 carbon atoms, and can be aliphatic or cyclic with at least minimal ethylene antagonist or inhibitory activity.

As used herein, the term "packaging material" refers to any packaging component that contains produce therein or is exposed to the enclosed volume within a produce bag or container. Packaging materials include, for example, sheets or films that can be made into packages for enclosing produce, or any package made into packages for enclosing produce, or any material used on or within a package. Packaging materials include, for example, thermoplastic packaging films and foils, and wraps or bags formed therefrom; coated or uncoated paper sheets and bags or cartons; a thermoformed flat basket; a wax or film coating applied directly to the produce or container; multilayer packaging constructions, printed coatings, embossed indicia, labels placed on or in the packaging or on the agricultural product, adhesives used to close or seal the packaging or to adhere labels and the like thereto; ink printed directly on the produce, directly on the packaging, or printed on a label (which is then adhered to the packaging); and the like. In various embodiments, one or more packaging materials employed in the package comprise a cyclodextrin composition of the invention.

As used herein, the term "treated packaging material" refers to a packaging material or container having disposed on at least a portion of a major surface thereof a cyclodextrin composition and wherein the cyclodextrin composition has been further cured.

As used herein, the term "treated package insert" refers to a piece or length of treated packaging material that is inserted into a produce package or into some other container that defines an enclosed volume.

As used herein, the term "treated laminate material" or "treated laminated packaging material" refers to a cyclodextrin composition or cured cyclodextrin composition that is bonded and disposed between a surface of a first packaging material and a surface of a second packaging material, wherein the first and second packaging materials are the same or different. In general, the treated packaging material comprises a treated laminated packaging material.

As used herein, the term "treated container" or "treated package" refers to a packaging material that has been (1) formed into a flexible, semi-rigid, or rigid container or package to seal produce, then coated with a cyclodextrin composition, and cured; or (2) a treated packaging material that has been formed into a flexible, semi-rigid, or rigid container or package. Treated containers include bags, boxes, cardboard, flat baskets, and other containers used to package produce material. In conjunction with its intended use and for a certain period of time, the treated container will comprise a closed volume. Thus, the treated container will be closed or sealed to contain an enclosed volume; or within an enclosed volume.

As used herein, the term "treated laminated container" refers to (1) a first packaging material that has been formed into a flexible, semi-rigid, or rigid container to seal produce, wherein a cured cyclodextrin composition is bonded and disposed between a surface of the first packaging material and a surface of a second packaging material, wherein the first and second packaging materials are the same or different; or (2) a first packaging material that has been formed into a flexible, semi-rigid, or rigid container to seal produce, wherein a cyclodextrin composition is incorporated and disposed between a surface of the container and a second layer of packaging material that is the same as or different from the first packaging material, and then the cyclodextrin composition is cured; or (3) a processed laminated packaging material that has been formed into a flexible, semi-rigid, or rigid container. In general, the treated container comprises a treated laminated container.

As used herein, the term "permeable" when applied to a packaging material, cured cyclodextrin composition, treated packaging material, treated container, treated laminated packaging material, or treated laminated container means that the material, container, or composition has a permeability to the olefinic inhibitor that is equal to or greater than 0.01 (cm) at Standard Temperature and Pressure (STP) and a relative humidity of 0% >³·mm/m²24hrs bar); or a permeability to water vapor of 0.1 (g.mm/m) or more at 38 ℃ and 90% relative humidity when measured according to ASTM D96²24 hr-bar); or to O when measured according to ASTM D3985₂Has a permeability of 0.1 (g.mm/m) or more at 23 ℃ and 0% relative humidity²24 hr-bar); or to CO when measured according to ASTM D1434₂Has a permeability of 0.1 (g.mm/m) or more at 23 ℃ and 0% relative humidity²24 hr-bar); or a combination thereof. As used herein, the term "impermeable" when applied to a packaging material, cured cyclodextrin composition, treated packaging material, treated container, treated laminated packaging material, or treated laminated container means that the material, container, or composition has a permeability to the olefinic inhibitor of less than 0.01 (cm) at STP and 0% relative humidity (cm) at which the material, container, or composition is coated with the olefinic inhibitor³·mm/m²24hrs bar); or a permeability to water vapor of less than 0.01 (g.mm/m) at 38 ℃ and 90% relative humidity when measured according to ASTM D96²24 hr-bar); or to O when measured according to ASTM D3985₂Has a permeability of less than 0.1 (g.mm/m) at 23 ℃ and 0% relative humidity²24 hr-bar); or to CO when measured according to ASTM D1434₂Has a permeability of less than 0.1 (g.mm/m) at 23 ℃ and 0% relative humidity²24 hr-bar); or a combination thereof.

The term "produce" or "produce material" includes any whole plant, plant part such as fruit, flower, cut flower, seed, bulb, cutting, root, leaf, flower, or other actively respiring material, and as part of its mature body, ethylene (catagen) or non-ethylene as the maturation hormone and a mutation of respiration, i.e., maturation (non-catagen).

2. Composition, article, and method of manufacture

We have found that one or more cyclodextrin compounds can be used to form cyclodextrin compositions using mild conditions. These cyclodextrin compositions can be used to form a coating on at least a portion of a major surface of one or more packaging materials or containers. After a cyclodextrin composition is coated onto at least a portion of a surface of a packaging material or container, the coated surface is irradiated with UV or electron beam radiation to form a treated sheet, film, or container. In certain embodiments, the treated packaging material is used to form a container. In other embodiments, a treated packaging insert is formed using the treated packaging material, wherein a section of the treated packaging material is attached to or simply inserted into an produce container. The produce is packaged using the treated container, or a container having a treated packaging insert disposed therein.

The use of the compositions, articles, and methods of the present invention enables the olefinic inhibitor compound to be employed in a safe, convenient, and scalable manner that avoids subjecting the cyclodextrin inclusion complex to harsh conditions that may result in the loss of olefinic inhibitor from the cyclodextrin inclusion complex. In addition, the treated packaging materials, containers, and package inserts of the present invention, when placed within an enclosed volume, impart low but constant levels of olefinic inhibitor release under conditions of water vapor, and thus provide long-term inhibition of ripening or ripening of produce placed inside the enclosed volume.

The cyclodextrin compositions of the present invention comprise at least one cyclodextrin inclusion complex and a monomer. In embodiments, the cyclodextrin inclusion complex is simply mixed with the monomer in a desired ratio to form the cyclodextrin composition.

The cyclodextrin used to form the cyclodextrin inclusion complex is selected based on the specific volume of the cyclodextrin pores. That is, the pore size of the cyclodextrin is selected to accommodate the molecular size of the olefinic inhibitor. The olefinic inhibitor is a compound having from 3 to about 20 carbon atoms, including at least one olefinic bond and including a cyclic, olefinic or diazodiene structure. Examples of compounds useful as olefinic inhibitors of ethylene production include 1-methylcyclopropene, 1-butene, 2-butene, and isobutene. Of these, 1-methylcyclopropene, or 1-MCP, has been found to be particularly useful. 1-MCP has been found to have a molecular size suitable for forming an inclusion complex when combined with alpha-cyclodextrin, or alpha-CD. In various embodiments, the inclusion complex comprises about 0.10 to 0.99 moles of olefinic inhibitor per mole of cyclodextrin, or about 0.20 to 0.95 moles of olefinic inhibitor per mole of cyclodextrin, or about 0.30 to 0.90 moles of olefinic inhibitor per mole of cyclodextrin, or about 0.50 to 0.80 moles of olefinic inhibitor per mole of cyclodextrin, or about 0.30 to 0.70 moles of olefinic inhibitor per mole of cyclodextrin.

Methods of forming cyclodextrin inclusion complexes are known and described, for example, in U.S. Pat. Nos. 6,017,849 and 6,548,448 and in Neoh, T.Z. et al J.Agric.food chem.2007,55,11020-11026. The cyclodextrin is typically mixed in a solution with the olefinic inhibitor for a period of time sufficient to form the inclusion complex. In the case of 1-MCP and alpha-cyclodextrin, the alpha-cyclodextrin is dissolved in water and the 1-MCP is bubbled into the solution at room temperature for a period of time. The inclusion complex precipitates out of the solution as it forms and is therefore easily isolated by simple filtration followed by vacuum drying. The dried cyclodextrin inclusion complex is then ready for use. It is sufficient to store in a dry container with minimal headspace.

In certain embodiments, the cyclodextrin inclusion complex is formed with a cyclodextrin derivative. Cyclodextrin derivatives are used in certain embodiments to form the inclusion complex to improve miscibility in cyclodextrin compositions. Cyclodextrin derivatives used to improve the miscibility of cyclodextrin compositions include any of those described in U.S. patent No. 6,709,746 or in Croft, a.p. and Bartsch, r.a., Tetrahedron vol.39, No.9, pp.1417-1474 (1983). In certain embodiments employing a cyclodextrin derivative to form the cyclodextrin inclusion complex, the olefinic inhibitor is introduced into a non-aqueous solvent, such as a hydrocarbon having 1 to 10 carbons, an alcohol having 1 to 10 carbons, a heterocyclic or aromatic solvent having 4 to 10 carbons. In some such embodiments, a blend of one or more solvents is used. In other embodiments, the inclusion complex is formed prior to functionalization of the cyclodextrin derivative. In such embodiments, the technique must be carefully used during the functionalization and the functional group chemistry chosen to avoid dislodging the olefinic inhibitor from the inclusion complex, for example by preferential inclusion of one of these compounds employed in the functionalization.

Monomers useful in forming the cyclodextrin composition include any of the known compounds having one or more unsaturated bonds that are polymerizable by free radical polymerization or plasma polymerization methods such as electron beam radiation polymerization. In various embodiments, useful vinyl monomers include acrylate, methacrylate, acrylamide, allylic monomers, alpha-olefins, butadiene, styrene and styrene derivatives, acrylonitrile, and the like. Some examples of useful monomers include acrylic acid, methacrylic acid, and alkyl esters of acrylic acid or methacrylic acid, where the ester groups have between 1 and 18 carbons, in certain embodiments between 1 and 8 carbons, and are linear, branched, or cyclic. In various embodiments, a blend of two or more monomers is employed in the cyclodextrin composition. In some such embodiments, one or more monomers are selected for improved wettability, adhesion, or both of the cyclodextrin composition to a target substrate. In some such embodiments, one or more monomers are selected to provide specific permeation characteristics. In certain embodiments, the monomers are selected to provide a targeted permeability of the cured cyclodextrin composition to water, or to the olefinic inhibitor, or to both. Careful control of the permeability is chosen to give the best controlled release of the olefinic inhibitor during use. Different additional components (as described below) are further selected to control the release profile of the olefinic inhibitor and other physical properties of the cured cyclodextrin composition of the invention. The monomer or blend of two or more monomers is included in the cyclodextrin composition of the invention at about 99.999% by weight to 70% by weight of the composition, or about 99% by weight to 75% by weight of the composition, or about 95% by weight to 75% by weight of the composition.

In certain embodiments, monomers having more than one unsaturated and polymerizable bond are used in the cyclodextrin composition, for example diacrylates such as ethylene glycol diacrylate, hexanediol diacrylate, and tripropylene glycol diacrylate; triacrylates, such as glycerol triacrylate and trimethylolpropane triacrylate; and tetraacrylates such as erythritol tetraacrylate and pentaerythritol tetraacrylate; divinylbenzene and derivatives thereof, and the like. Such monomers provide crosslinking to the cured cyclodextrin composition. Other compounds that are useful monomers when UV polymerization is employed include photoactive crosslinkers. Photoactive crosslinkers include, for example, benzaldehyde, acetaldehyde, anthraquinones, substituted anthraquinones, various benzophenone-type compounds, and certain chromophore-substituted vinyl halomethyl-s-triazines, such as 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine. In some such embodiments, a monomer having more than one unsaturated and polymerizable bond, or a photoactive crosslinker, is present at less than about 10% by weight of the cyclodextrin composition, such as about 0.1% to 5% by weight of the cyclodextrin composition. In embodiments, the monomer or monomer blend is liquid at the temperature at which the cyclodextrin composition is coated onto a thermoplastic sheet, film, or container. In certain embodiments, the cyclodextrin, cyclodextrin inclusion complex, or both are miscible in the monomer or monomer blend.

The cyclodextrin composition is a mixture of cyclodextrin inclusion complex and one or more monomers, and optionally one or more cross-linking agents, along with any additional components that are desired to be included in the cyclodextrin composition. In embodiments, the amount of cyclodextrin inclusion complex used in the cyclodextrin composition is about 0.001% to 25% by weight of the composition, or about 0.01% to 10% by weight of the composition, or about 0.05% to 5% by weight of the composition. The amount of cyclodextrin inclusion complex included in a particular formulation is selected based on the amount of olefinic inhibitor desired within the enclosed space of the treated container, in combination with variables such as the permeability of the coating to water and olefinic inhibitor. The indicators that provide this selection are described in more detail below.

In various embodiments, one or more additional components are added to the cyclodextrin composition. Examples of additional materials that may be added to the cyclodextrin compositions in certain embodiments are adhesion promoters,Anti-fouling agents, thermal or oxidative stability, colorants, adjuvants, plasticizers, and small amounts of solvents. In some embodiments, the cyclodextrin composition includes a polymerization initiator. In certain embodiments where curing is by UV radiation, it is desirable to include a photoinitiator that will absorb UV radiation and become activated, thereby initiating polymerization of the unsaturated polymerizable monomer(s) and any other components of the cyclodextrin composition that include a UV polymerizable moiety. In many embodiments, a photoinitiator is selected based on the wavelength of UV radiation to be employed. When a photoinitiator is employed, it is included in the cyclodextrin composition at about 0.01% by weight to 5% by weight based on the weight of the cyclodextrin composition, for example 0.5% by weight to 2% by weight based on the weight of the cyclodextrin composition. Examples of suitable photoinitiators include Ciba Specialty Chemicals Corp. by Tarrytown, NYThose sold under the market; trade name of Sun Chemical Company of Tokyo, JapanThose sold under the market; and sold by BASF Corporation of Charlotte, NCTPO。

In some embodiments, an additional component is a prepolymer. The prepolymer is formed in situ from the cyclodextrin composition by its prepolymerization, optionally followed by the addition of further monomers and photoinitiators, or is added to the cyclodextrin composition in order to increase the coating viscosity of the composition prior to curing. Prepolymerization is a bulk or continuous polymerization process in which a small amount of polymerization, for example 1% to 10% of the bulk coating composition, is carried out to achieve the target viscosity. The prepolymers have any suitable molecular weight and are soluble in the one or more monomers of the cyclodextrin composition. The prepolymer is formed in situ or added to the cyclodextrin composition in any amount useful for providing a target coating viscosity. In a typical prepolymerization, a cyclodextrin composition is subjected to UV radiation in bulk or continuous mode until the desired viscosity is reached, thereby forming a prepolymerized cyclodextrin composition. In certain embodiments, the target viscosity of the pre-polymerized cyclodextrin composition is from about 10cP to 2000cP, or about 100cP to 1000 cP. In various embodiments, one or more additional monomers, crosslinkers, initiators, or combinations thereof are then added to the pre-polymerized cyclodextrin composition. The prepolymerized cyclodextrin composition is then coated and cured, wherein the viscosity of the prepolymerized cyclodextrin composition allows for the application of a thicker layer than can be achieved using a cyclodextrin composition that is not prepolymerized. In various embodiments, pre-polymerized cyclodextrin composition coatings of 25 microns and greater, for example, between about 25 microns and 100 microns, are formed. Such coating thicknesses are useful, for example, when the cured cyclodextrin composition is a pressure sensitive adhesive. In certain embodiments, the cyclodextrin inclusion complex is added to the coating composition after pre-polymerization; in many embodiments, however, the cyclodextrin inclusion complex is added prior to prepolymerization because mixing of the components is more easily accomplished prior to forming a higher viscosity composition.

In some embodiments, an additional component is a water scavenger. A water scavenger is a compound that is soluble or dispersible in the coating composition to be cured and is available to preferentially react with water molecules, such that it is used to effectively scavenge moisture from the environment from airborne moisture under standard processing conditions. The amount of water scavenger added should be the minimum amount to react with ambient moisture during processing. This is because in packaging applications where the contemplated cyclodextrin composition is included in a produce container, water is required to assist in the release of the olefinic inhibitor into the container. Thus, the amount of water scavenger that should be provided in the cyclodextrin composition is quickly depleted upon encountering a substantial amount of water vapor. Examples of water scavengers suitable for use in the cyclodextrin compositions of the invention include different ortho esters as well as hexamethyldisilazane. In various embodiments, about 1 wt% or less of a water scavenger based on total cyclodextrin composition weight is added to the cyclodextrin composition, for example about 0.01 wt% to 1 wt% based on total cyclodextrin composition weight, or about 0.05 wt% to 0.5 wt% based on total cyclodextrin composition weight.

In some embodiments, an additional component is a desiccant. In the present invention, desiccants are used to remove water from within an enclosed volume in which a respiratory agricultural material is expected to produce water in excess of desired values. The effect of excess water is described in more detail below. In certain embodiments, the desiccant is also added to the interior of the treated container or treated laminate of the present invention directly, separately from the cyclodextrin composition itself; however, in certain embodiments, for convenience and/or efficiency, the drying agent is added directly to the cyclodextrin composition. Suitable desiccant materials include, for example, silica gel and molecular sieve type desiccants. The amount of desiccant incorporated into the cyclodextrin composition or the cured cyclodextrin composition is not particularly limited and is selected based on the particular end use, i.e., the type of packaging, the volume of the enclosed space, the type of agricultural product to be packaged, and the like. Generally, the amount of drying agent is selected to be about 0.001 wt% to 99 wt% based on the total weight of the cyclodextrin composition, or about 0.1 wt% to 50 wt% based on the total weight of the cyclodextrin composition, or about 1 wt% to 10 wt% based on the total weight of the cyclodextrin composition.

Packaging materials suitably coated on at least one portion thereof with a cyclodextrin composition include any packaging material suitable for surface coating followed by curing with UV or electron beam radiation. Suitable packaging materials include paper and paperboard and other natural and synthetic biomass-based packaging materials, as well as synthetic, petroleum-based thermoplastic polymer films, sheets, fibers, or woven or non-woven fabrics, and composites comprising one or more of the same, useful as packaging materials for agricultural products. Some examples of packaging materials often used to form containers, labels, laminates (i.e., treated laminated packaging materials) or packaging inserts include paper, paperboard, coated paper or paperboard, such as extrusion coated paper or paperboard, particle board, nonwoven or woven fabrics, wood/thermoplastic composites, polyvinyl halides such as polyvinyl chloride (plasticized and unplasticized) and copolymers thereof; polyvinylidene halides such as polyvinylidene chloride, and copolymers thereof; polyolefins such as polyethylene, polyphenylenes and morphological variants thereof including LLDPE, LDPE, HDPE, UHMWPE, metallocene polymerized polypropylene, and the like; polyesters, such as polyethylene terephthalate (PET) or polylactic acid (PLA) and plasticized variants thereof; polystyrene and its copolymers, including HIPS; polyvinyl alcohol and copolymers thereof; copolymers of ethylene with vinyl acetate; and the like. Their blends, alloys, cross-linked forms, and composites thereof are also useful in various embodiments. In certain embodiments there are two or more such layers of packaging material, as a multilayer film or carton construction.

In certain embodiments these packaging materials comprise one or more fillers, stabilizers, colorants, and the like. In certain embodiments these packaging materials have one or more surface coatings thereon. In certain embodiments the packaging material has a top coat thereon prior to coating the cyclodextrin composition. Surface coatings include protective coatings such as waxes, acrylic polymer coatings, and the like; a coating for making a surface printable; a coating for otherwise rendering the permeable packaging material impermeable; an adhesive coating; priming paint; a tie layer coating; a metallized or reflective coating; and the like. The type and function of the surface coating is not particularly limited within the scope of the invention; similarly, the manner in which the surface coating is applied is also not particularly limited. In various embodiments where a surface coating is exposed to the enclosed volume of the produce package, the surface coating is subsequently coated with the cyclodextrin composition.

In one such commercially important embodiment, commercial growers and distributors often use polyethylene extrudate coated recyclable paperboard or carton board packaging to ship produce. The polyethylene coating provides water resistance and water vapor protection in generally moist and humid environments that are typical for the shipping and storage conditions of fresh fruits and vegetables. Printed paperboard packaging can range from bulky cabinets to specialized display cartons. The printed indicia is in certain embodiments embossed indicia. The extrudate-coated surface provides the opportunity to include a cyclodextrin composition of the present invention.

In certain embodiments the packaging material is treated with a plasma or corona treatment prior to coating the cyclodextrin composition. Such surface treatments are known in the industry and are often used in the industry to modify the surface energy of packaging materials, for example to improve the wettability or adhesion of the coated or printed material to the surface of the packaging material. Such surface treatments may also be used in certain embodiments to improve the wetting and adhesion of the cyclodextrin composition to the packaging material.

In certain embodiments the packaging material is treated with a primer prior to coating the cyclodextrin composition. In some such embodiments, films and sheets of thermoplastics used as packaging materials are obtained that have been pre-coated with a primer; a wide variety of such films and sheets are available in the industry and are aimed at improving the adhesion of different types of coatings thereto. In certain embodiments, a flat film or sheet "in line" is coated with a primer designed to improve the adhesion of the radiation polymerizable coating prior to application of the cyclodextrin composition. Too many such coatings and techniques are available and the skilled person will understand that the primer coating is optimized for each coating formulation and each film or sheet type. Some examples of primer compositions that are suitably disposed between the surface of the packaging material and the cyclodextrin composition of the present invention include polyethyleneimine polymers, such as polyethyleneimine, alkyl-modified polyethyleneimine (wherein the alkyl group has 1 to 12 carbon atoms), poly (ethyleneimine urea), ethyleneimine adducts of polyamine polyamides, and epichlorohydrin adducts of polyamine polyamides, acrylate polymers such as acrylamide/acrylate copolymers, acrylamide/acrylate/methacrylate copolymers, polyacrylamide derivatives, oxazoline group-containing acrylate polymers, and poly (acrylates). In embodiments, the primer composition is an acrylic resin, a polyurethane resin, or mixtures thereof. In various embodiments the primer composition includes at least one radiation curable polymer, oligomer, macromer, monomer, or mixture of one or more thereof.

In certain embodiments the packaging material is a sheet or film formed into a container suitable for enclosing produce within an enclosed space. In other embodiments the packaging material is a sheet or film that is fashioned into coupons, strips, tabs, and the like for the purpose of insertion into the enclosed space defined by an untreated produce container. In certain embodiments the coupons, strips, tabs, and the like are labels that are adhesively applied to the produce of the container. In some such embodiments, the test pieces, strips, tabs, and the like are labels further printed with one or more indicia. In embodiments, the indicia are embossed indicia. The cyclodextrin composition is present in various embodiments on any surface that is directly or indirectly exposed to an enclosed space. In some embodiments, the packaging material is a treated laminate material. In certain embodiments, the treated laminate material is permeable to the olefinic inhibitor on a first side thereof and impermeable to the olefinic inhibitor on a second side thereof. In certain embodiments, the packaging material is a treated laminate material that is water permeable on at least a first side thereof.

Containers suitable for enclosing produce within an enclosed space include, for example, bags, boxes, cartons, trays, and flat baskets. In certain embodiments, the package is designed to contain a single produce item, such as a bag containing a banana or a head lettuce; in other embodiments, the package is a carton containing articles, such as a carton containing a bushel apple or several pints of berries; in still other embodiments, the package is designed to enclose a pallet of smaller produce boxes or flat baskets, such as large polyethylene bags for shipping that enclose a pallet of berries. In still other embodiments, the container is a truck, ship, or airplane, wherein a sealed and/or controlled environment is provided for transporting the produce.

In many embodiments, more than one packaging material is employed in forming the container; in such embodiments, the cyclodextrin composition is present on one or more packaging components. In one illustrative example, a semi-rigid polypropylene container is filled with produce and then sealed with a polyvinyl chloride film. The agricultural product includes a paper label attached to the agricultural product. Within the container is a polyester packet or cup containing sauce, spices, or other ingredients. The packet or cup has indicia printed thereon. In this example, the cyclodextrin composition is present on all or part of an inner surface of the container or film, an outer surface of the packet or cup or the paper label, and/or included in ink printed on the packet or cup. Alternatively, the cyclodextrin composition comprises a package insert or label added to the container separately prior to sealing the container with the film. In certain embodiments, the combination of more than one such surface comprises the cyclodextrin composition. In yet another illustrative example, a polyethylene extrudate coated carton is coated or printed with a cyclodextrin composition on one surface thereof, followed by curing. The carton is then filled with produce, stacked with other cartons on a pallet, and the pallet is enclosed in a polyethylene bag. In certain embodiments, all of the cartons comprise the cured cyclodextrin composition; in other embodiments, only one or a few percent of the carton comprises the cured cyclodextrin composition. In some examples of this technique, the bag further comprises a controlled atmosphere or a modified atmosphere, or is a selectively permeable film material. Variations of such atmospheres, as well as permeable membrane materials, are discussed in detail below. In certain embodiments, the pouch further comprises a desiccant in the packet or packet containing the pharmaceutical powder.

In yet another representative example, a plastic bag containing produce is a treated laminated container, i.e., the cured cyclodextrin composition does not directly contact the interior of the container. The cyclodextrin composition is cured directly on a first packaging material, wherein a second packaging material is applied on top of the cyclodextrin composition and cured after lamination to form a treated laminate material; the treated laminate material is then formed into a bag. The packaging material forming the exterior of the bag is impermeable to the olefinic inhibitor. The packaging material contacting the inside of the bag is at least permeable to the olefinic inhibitor. At least one of these packaging materials is water vapor permeable. In a related example, the treated laminate material is a film, such as a carton or other container for wrapping produce. In another related example, the cyclodextrin composition is cured directly on a first packaging material, wherein a second packaging material is applied on top of the cyclodextrin composition and cured after lamination to form a treated laminate material; the laminate is tentered (oriented, or stretched) either uniaxially or biaxially before or after the cyclodextrin composition is cured. After curing and tentering, the treated laminate material is formed into a bag or used as a wrap for an agricultural product container. In yet another related example, the cured cyclodextrin composition is a pressure sensitive adhesive disposed on a packaging material; the pressure sensitive adhesive is attached to a container to form a treated laminated container. The pressure sensitive adhesive is adhered to the interior or exterior side of the container to form a treated laminated container.

In certain embodiments, the packaging material is applied directly to the produce as a continuous or discontinuous coating, or as part of an adhesive, or as printed characters on printed or reverse printed produce labels, for two days. In such embodiments, all or a portion of the container or label comprises the cyclodextrin composition. In certain embodiments, an adhesive for adhering a label to produce or to packaging or for sealing a package comprises the cyclodextrin composition. Adhering the label to the inside or outside of the package; i.e. the surface that contacts the interior of the enclosed volume, or the surface that does not directly, but only indirectly (e.g. through the permeability of the packaging material to water and/or olefinic inhibitor) contact the interior of the enclosed volume. Such a construction is an embodiment of a treated laminated container. The treated laminated containers include those having a cured cyclodextrin composition disposed between a surface of the container and a second layer of a packaging material that is the same or different from the first packaging material forming the container. In such embodiments, the cyclodextrin composition is generally not in direct contact with the enclosed volume inside the container; i.e. it is arranged between two layers of packaging material. Thus, the surface of the packaging material that is in contact with the produce and also in contact with the cured cyclodextrin composition must be permeable to water and the olefinic inhibitor so that the olefinic inhibitor is released from the cyclodextrin inclusion complex and into the interior volume of the container. In some such embodiments, the laminate structure is permeable to the olefinic inhibitor on a first side thereof and impermeable to the olefinic inhibitor on a second side thereof; in certain embodiments, the container is a treated laminated container, wherein the laminated structure is water permeable on at least a first side thereof.

In some embodiments, the packaging material itself is permeable to the olefinic inhibitor. In some such embodiments, the cyclodextrin composition is coated on, or in contact with, the exterior of the package by lamination, and the olefinic inhibitor is released such that it diffuses through the package into the interior space in which the agricultural product is located. In some such embodiments, the packaging material is also water permeable and the release of the olefinic inhibitor is controlled by water vapor permeating through the packaging material from the interior of the enclosed volume; in other such embodiments, the packaging material is water impermeable and the release of the olefinic inhibitor is controlled by the ambient humidity present outside the enclosed volume. In some embodiments, the packaging material is not permeable to the olefinic inhibitor. In such embodiments, the packaging material is a barrier that prevents the olefinic inhibitor from escaping from the enclosed space defining the produce package. In still other embodiments, the packaging material itself is permeable to the olefinic inhibitor, but one or more surface treatments, coatings, or layers (e.g., in the case of multilayer films or cartons) provide a barrier function.

In the treated laminated container, two different packaging materials are employed in certain embodiments as the first and second packaging materials sandwiching the cyclodextrin composition; in this way, these packaging materials may have distinguishable permeability. Thus, for example, the inner facing side of the laminate is permeable to the olefinic inhibitor, but in some embodiments is water impermeable, while the outer facing side of the laminate is impermeable to the olefinic inhibitor, but in some embodiments is water permeable. In some such embodiments, a controlled humidity atmosphere provided outside the container (e.g., in a storage facility) is used to control the release rate of the olefinic inhibitor, rather than with the internal atmosphere within the container itself.

The cyclodextrin compositions are coated onto the surface of a packaging material, or directly onto agricultural produce, and cured. Coating is carried out using any known coating technique available in the industry, wherein a mixture of curable monomers is applied prior to curing. In certain embodiments, the coating is performed without using elevated temperatures, i.e., by using the ambient temperature of a processing apparatus. In other embodiments, the temperature during coating and curing is between about 5 ℃ and 75 ℃, or between about 0 ℃ and 25 ℃. Useful coating techniques for coating cyclodextrin compositions include, for example: die coating, curtain coating, flood coating, gap coating, notch bar coating, wound wire bar stretch coating, dip coating, brush coating, spray coating, pattern coating such as gravure coating, and print coating using printing techniques such as flexography, inkjet printing, lithography, letterpress, and screen printing. The viscosity profile of the cyclodextrin composition, including characteristics such as shear thinning, the nature and composition of the packaging material or produce, and the need to coat an integral comparative portion of a surface, indicates which known coating techniques are useful for coating cyclodextrin compositions. For example, die coating, notch bar coating, and the like are effectively used to coat the entirety of a substantially planar sheet of packaging material, while in embodiments where only a portion of a surface is to be coated, or where it is desired to coat a formed container or to coat agricultural produce, it is desirable to employ one or more spray, dip, or print coating techniques. When only one specific portion of the packaging material is to be coated, it is desirable to use a print coating or, in embodiments, a gravure coating. In some such embodiments, the print coating is an embossed indicia.

Radiation curable inks, such as UV curable inkjet and flexographic inks, are known in the industry and such equipment for applying and curing such inks is readily available. Further, the radiation-curable ink formulation is readily modified to include the amount of cyclodextrin inclusion complex necessary to accomplish the transfer of the desired amount of complexed olefinic inhibitor onto the surface of the one or more packaging materials. Thus, in one embodiment of the present invention, a UV-curable inkjet ink is modified to include an amount of a cyclodextrin inclusion complex, for example, by mixing the cyclodextrin inclusion complex into the ink; the modified inkjet ink is delivered to a target area of the packaging material and cured to provide a treated packaging material. Other printing techniques, such as flexographic printing, also have utility in transferring precise and repeatable amounts of cyclodextrin inclusion complex onto a packaging material by simply incorporating the inclusion complex containing the olefinic inhibitor. Mass production of packaging using flexographic printing instead of inkjet printing will achieve greater efficiency in certain embodiments.

The desired thickness of the coated layer of cyclodextrin composition is determined by the amount of cyclodextrin inclusion complex in the cyclodextrin composition, the inherent equilibrium ratio between the cyclodextrin inclusion complex and uncomplexed olefinic inhibitor, the permeability of the cured cyclodextrin composition to the olefinic inhibitor, the viscosity or coating thickness requirements of the technique used to coat the cyclodextrin composition, the size of the portion of the surface area containing the cured cyclodextrin composition, the type of agricultural product to be packaged, and the volume of the enclosed space surrounding the agricultural product. In summary, the coating thickness is selected to provide an amount of cyclodextrin inclusion complex that is effective to provide an appropriate atmospheric (gaseous) concentration of the olefinic inhibitor to the enclosed space such that the useful life of the agricultural product is extended. In certain embodiments, the effective amount of the olefinic inhibitor in the atmosphere within the enclosed space of the produce container is between about 2.5 parts per billion (ppb) to about 10 parts per million (ppm), or between about 25ppb and 1 ppm. In various embodiments, the coating thickness is between about 0.001 micrometers (μm) and 10 millimeters (mm) thick, or between about 0.01 μm and 1mm thick, or between about 0.1 μm and 0.5mm thick, or between about 1 μm and 0.25mm thick, or between about 2 μm and 0.1mm thick.

Once the cyclodextrin composition is coated onto a packaging material, it is cured in situ to form a treated packaging material. In-situ curing can be performed without the use of elevated temperatures; in certain embodiments, however, elevated temperatures are suitably employed; the curing process is not particularly limited by the temperature employed. For example, in various embodiments, the temperature employed during curing of the cyclodextrin composition is from about 0 ℃ to 135 ℃, or from about 30 ℃ to 120 ℃, or between about 50 ℃ to 110 ℃. Maintaining the temperature of both the coating and curing at about 100 ℃ or less is readily accomplished. In embodiments where the cyclodextrin inclusion complex is 1-MCP complexed with alpha-cyclodextrin, the elevated temperature does not result in appreciable release of the olefinic inhibitor from the cyclodextrin inclusion complex.

In certain embodiments, in situ curing is accomplished using UV radiation. The UV radiation is electromagnetic radiation having a wavelength between 10nm and 400 nm. In various embodiments, wavelengths between about 100nm and 400nm are useful; in other embodiments wavelengths between about 200nm and 380nm are useful. The wavelength, along with the radiation intensity and exposure time, are selected based on processing parameters such as the absorption characteristics of the photoinitiator employed, the polymerization kinetics of the selected monomer or monomers, and the thickness of the coating of the cyclodextrin composition. Suitable photoinitiators and amounts thereof for use in the cyclodextrin compositions are described above. Useful methodologies and indices considered in UV curing are described, for example, in U.S. patent No. 4,181,752.

In embodiments, curing is carried out in an environment substantially free of atmospheric moisture, air, or both. Such an environment is achieved in some embodiments by purging the coated area with an inert gas, such as carbon dioxide or nitrogen, during the curing process. In other embodiments, more conveniently when the coated packaging material is a flat sheet or film, water and air are suitably excluded during the curing process by applying a UV transparent, water impermeable liner on top of the coated, uncured cyclodextrin composition. Curing the coated cyclodextrin composition by irradiating through the liner; the liner is then removed, for example to assist in terminating the treated packaging film or sheet, wherein the film or sheet layers provide a suitable water barrier. In other embodiments, the liner is left on top of the treated packaging material until it is used as a treated container or treated packaging insert, at which point the liner is removed. The liner material is not particularly limited in composition or thickness, and is selected for UV transparency at the desired wavelength. In various embodiments, the liner is selected to have a sufficiently low level of adhesion to the cured cyclodextrin composition such that the liner can be removed after curing without causing appreciable damage to the cured cyclodextrin composition. In certain embodiments, the liner is added after curing to aid in storage of the treated packaging material or treated container; in such cases, the liner need not be radiation transparent but is selected primarily to exclude water.

In certain embodiments, curing of the coated cyclodextrin composition is performed using electron beam, or e-beam radiation. In other embodiments the cyclodextrin composition is applied to a packaging material after pre-polymerization thereof and subjected to e-beam radiation to crosslink the cyclodextrin composition. In some such embodiments, additional monomers (including monomers having more than one polymerizable moiety) are added to the pre-polymerized cyclodextrin composition prior to coating and subjecting to e-beam radiation. Electron beam methods for polymerizing cyclodextrin compositions are described, for example, in Weiss et alPulsed Electron Beam Polymerization", post January 1,2006(http:// www.adhesivesmag.com/Articles/Feature _ Article/47965fdd41bc8010VgnVCM100000f932a8c0 ____). Electron beam assisted bulk polymerization and/or crosslinking processes are described in both the patent and non-patent literature. Some examples of methods useful for polymerizing and/or crosslinking the cyclodextrin compositions of the present invention include, for example, U.S. patent nos. 3,940,667; 3,943,103, respectively; 6,232,365, respectively; 6,271,127, respectively; 6,358,670, respectively; 7,569,160, respectively; 7,799,885, etc.

An electron beam is a high-energy ionizing radiation that generates free radicals and is transparent to materials that are opaque to UV radiation. Thus, the use of electron beam polymerization or crosslinking offers the possibility of grafting the components of the cyclodextrin composition directly onto the packaging material. Many of the packaging materials listed above, such as polyolefins, polyvinyl chloride, and polystyrene, are sensitive to electron beam radiation; that is, in some cases one or more free radicals are formed along the polymer backbone by electron beam irradiation. Free radical formation along the polymer backbone provides an opportunity for the polymer backbone to bind to one or more components of the cyclodextrin composition. In various embodiments, one or more monomers or cyclodextrin inclusion complexes are bound, or grafted, to the packaging material by employing electron beam mediated (cured) polymerization or electron beam mediated crosslinking. The dose of radiation delivered is carefully adjusted in each case to avoid antagonistic processes of chain scission.

In the manufacture of the cyclodextrin compositions of the present invention, wherein the cyclodextrin composition comprises a cyclodextrin inclusion complex formed from 1-MCP and alpha-cyclodextrin (1-MCP/c/alpha-CD), we have found that careful control of the water content during coating, curing, and subsequent storage prior to use is useful for maintaining the stability of the 1-MCP/c/alpha-CD complex. Because the water is reduced, the 1-MCP is more controllably maintained in the central pore of the a-cyclodextrin. Storage of the treated packaging material comprising 1-MCP/c/α -CD is advantageously accomplished by covering the treated portion of the treated packaging material with a water vapor impermeable liner; or in the case of treated films or sheets formed from water vapour impermeable thermoplastics, winding these into rolls, or storing the sheets or containers in stacks; or otherwise containing the treated packaging material in a low humidity environment. In certain embodiments, a bulk quantity of treated packaging material, such as rolls of treated packaging film or a set of stacked treated containers, is wrapped in a water-impermeable plastic or foil wrap or enclosed in a water-impermeable bag for storage and/or transport.

In certain embodiments in which a liner is applied to the cured cyclodextrin composition, the liner includes one or more desiccants. In some such embodiments, the desiccants are embedded in, or adhered to, the liner. The desiccant is used with the liner itself to remove water during storage and/or transportation. Examples of desiccants suitable for use include silica gel, activated carbon, calcium sulfate, calcium chloride, montmorillonite clay, and molecular sieves. The desiccant is attached to the liner in a manner such that the desiccant remains substantially attached to the liner when the liner is removed from the treated packaging material or treated container.

In certain embodiments, a treated packaging material or treated laminate is stretched before or after curing the cyclodextrin composition. Uniaxial or biaxial stretching or tentering of thermoplastic film-forming materials and laminates formed from such materials is performed in an efficient and economical manner to form films having enhanced strength. When applying the cyclodextrin composition to a thermoplastic film prior to tentering, a thicker coating and/or high concentration of the cyclodextrin inclusion complex is employed because the layer comprising the cyclodextrin inclusion complex can be expected to be made thinner at a specified draw ratio.

3. Use of compositions, methods and articles

These treated packaging materials and treated containers are useful for enclosing produce. These treated package inserts are usefully included within the enclosed volume of the packaged agricultural produce. In embodiments, the treated packaging material, treated container, or treated packaging insert is arranged such that the cured cyclodextrin composition contacts the internal atmosphere of an enclosed volume surrounding one or more items of produce, wherein the enclosed volume is provided by the container. The type and configuration of the produce container is not particularly limited; any bag, box, pannier, bucket, cup, pallet bag, vehicle interior (e.g., truck interior), etc., that defines an enclosed space, usefully employs the treated packaging material, container, and/or packaging insert of the present invention.

The surface area and thickness of the cured cyclodextrin composition exposed to the interior of a produce container is selected to provide the appropriate atmospheric (gaseous) concentration of olefinic inhibitor to the enclosed space so that the useful life of the produce is optimized. In many embodiments, the optimal useful life of the agricultural product refers to the time that is extended by the maximum amount possible. The optimum atmospheric concentration of the olefinic inhibitor is determined by the type of agricultural product to be packaged, and the expected storage temperature of the agricultural product, along with the partial pressure of the olefinic inhibitor at the target temperature. Factors that influence the optimum atmospheric concentration of the olefinic inhibitor include: the amount of cyclodextrin inclusion complex in the cyclodextrin composition, the inherent equilibrium ratio of cyclodextrin inclusion complex to uncomplexed olefinic inhibitor, the permeability of the cured cyclodextrin composition to olefinic inhibitor, the permeability of the packaging material to olefinic inhibitor (i.e., the expected loss ratio of olefinic inhibitor to the exterior of the package or container), the viscosity and coating thickness requirements of the technique used to coat the cyclodextrin composition, the volume of the enclosed space surrounding the agricultural product, and the expected amount of water in the container due to the initial add/close amount and the expected transpiration of the plant material. If the container is not completely sealed from the external atmosphere, for example if there are voids or the packaging material itself has holes or cavities, any expected loss of released (gaseous) olefinic inhibitor must also be taken into account when calculating the amount of cyclodextrin composition to be disposed inside the produce container.

In embodiments, the amount of olefinic inhibitor in the atmosphere required for a particular packaging application is estimated based on what agricultural product is to be packaged and the known effective level of the inhibitor relative to the particular agricultural product material; the coating thickness and coated area (i.e., total coated volume) are then varied depending on the enclosed volume, and the concentration of cyclodextrin inclusion complex contained in the cured cyclodextrin composition. Other factors that affect the release of olefinic inhibitors from the cyclodextrin inclusion complex in the cured cyclodextrin composition of the invention include: the presence and amount of humectant or desiccant within the package, the permeability/adsorbability/absorbency of the cured cyclodextrin composition to water and 1-MCP, the permeability/adsorbability/absorbency of the packaging material to water and 1-MCP, and any controlled or modified atmosphere present within the package, and the respiration rate of the target produce material. Further, the amount of water provided in the enclosed space, i.e., the amount of water vapor versus liquid water in the enclosed space at the target temperature, must also be considered.

In such calculations, the value of delivering the target coating volume into the target enclosed volume is realized. Certain embodiments described above are particularly advantageous for delivering accurately measured quantities of olefinic inhibitor to a closed volume, and allowing easily variable quantities of cyclodextrin composition to be delivered to a target container. For example, it is generally understood that inkjet printing delivers precise and easily changeable volumes of material to a substrate on an easily changeable volume. Further, UV curable inkjet inks are known in the industry and such equipment for applying and curing such inks is readily available. We have found that it is easy to modify the formulation of a UV-curable ink formulation to include a small amount of cyclodextrin inclusion complex necessary to accomplish the desired amount of transfer of the olefinic inhibitor onto the surface of one or more packaging materials. Thus, in one embodiment of the present invention, a UV-curable inkjet ink is modified to include an amount of a cyclodextrin inclusion complex, for example, by mixing the cyclodextrin inclusion complex into the ink; in some such embodiments, the ink is dried with a drying agent to remove water prior to adding the cyclodextrin inclusion complex. The modified inkjet ink so obtained is transferred onto a target area of the packaging material and cured to provide a treated packaging material. Other printing techniques, such as flexographic printing, also have utility in transferring precise and repeatable amounts of cyclodextrin inclusion complex onto a packaging material.

Another advantage of using printing techniques to deliver the cyclodextrin compositions of the present invention is that the printing is easily incorporated into agricultural product assembly line equipment. Further, the ink is easily kept dry while in a tank waiting for printing on the production line. In this way, the long-term storage problems encountered in certain applications, i.e., the need to keep the cured cyclodextrin composition dry, are circumvented. Yet another advantage of using printing techniques to apply the cyclodextrin composition is the ability to use reverse printed labels. In reverse printed labels, a transparent label paper is printed with indicia, typically by means of an adhesive, on the side of the label that will contact the package. The alphanumeric characters are therefore reversed, i.e., as a mirror image thereof. The label paper protects the printed indicia from abrasion and tearing when the label is applied to the packaging. In current use, the printed cyclodextrin composition in reverse labeling mode is then disposed onto the package or agricultural product. The reverse printed label is also useful for printing onto what will become the interior of the transparent package so that the printed indicia is directly exposed to the interior of the package.

In certain embodiments, the delivery of the target coating amount to the target enclosed volume is achieved by coating a cyclodextrin composition onto a flat sheet and curing, followed by cutting the sheet into portions that are treated package inserts. In some such embodiments, different sizes of treated package inserts are cut to provide different amounts of cyclodextrin inclusion complex to address different produce requirements or different enclosed volumes. In other embodiments, uniform sections are cut and one, two or more sections are included as treated package inserts in different packages, depending on the type of agricultural product and the enclosed volume in each application. For example, in embodiments where the treated package insert is a label, applying a label to each produce item includes several produce items within a single enclosed volume. In this way, containers of different sizes containing variable quantities of produce items are easily solved.

In yet another set of different embodiments, the adhesive coated on the label is used on the outside of the package to provide a packaging material that is a laminated packaging material.

In certain embodiments, the packaging materials used to make the treated packaging materials of the present invention, as well as the treated packages and containers of the present invention, further employ means for controlling the amount of water (vapor and/or liquid) enclosed within the treated package in the presence of the produce material. While the amount of water within the enclosed space of the package is of concern from the standpoint of the release of the olefinic inhibitor from the cured cyclodextrin composition, it is well known that the moisture of very high waters in packages containing agricultural product materials is also detrimental to certain moisture sensitive agricultural products alone (e.g., berries, citrus, lettuce, mushrooms, onions, and peppers). Excessive moisture triggers different physiological changes in certain post-harvest fruits and vegetables, thereby shortening shelf life and quality. In particular, liquid water in condensed form on the surface of the agricultural product material accelerates spoilage and significantly shortens shelf life. In certain embodiments, internal humidity control agents (humectants and desiccants) are incorporated into the porous pill pouches in the packaging materials of the present invention, or even into the cyclodextrin compositions themselves, as well as the treated packaging materials of the present invention. In various embodiments, the humidity control agent helps maintain an optimal relative humidity within the package (about 85% to 95% for cut fruits and vegetables), reduces moisture loss from the produce material itself, and/or prevents excess moisture from accumulating in the headspace and interstices where microorganisms may grow. The amount of 1-MCP incorporated into the packaging structure is not the same in packages with excess water as the lower moisture packaging of low respiration post harvest products. Therefore, to operate the technology, a number of factors (chemical and biological) will be considered to produce optimal packaging configurations for different groups of post-harvest products, as well as bulky shipping containers.

The treated packaging material of the present invention employs Modified Atmospheric Packaging (MAP),Balanced modified atmosphere packages (EMAPs), or Controlled Atmosphere Packages (CAPs) embodiments are also useful. The goal in MAP is to provide the desired atmosphere surrounding the produce by providing a sealed container with controlled permeability to oxygen and carbon dioxide, resulting in an improvement in the quality of the produce compared to air storage. Typically, the permeability of the vessel varies with the temperature and partial pressure of each gas outside the vessel. The goal in CAP is to make up some or all of the atmospheric air (78% N) in the container₂，21％O₂) Replacement is made with, for example, carbon dioxide or nitrogen or a blend of two or more gases in the desired ratio. Many patents list different characteristics of MAP and CAP. U.S. patent No. 7,601,374 discloses both approaches and also mentions a substantial list of other patents issued for different MAP and CAP technologies. It will be appreciated that the cured cyclodextrin compositions of the invention are further useful in combination with MAP, CAP, or other techniques that combine the features of both pathways.

MAP is a useful way to maintain improved flavor fruits and vegetables by minimizing the development of odors caused by fermentative metabolism or odor transfer from fungi or other sources. MAP has been recognized to improve tolerance to post-harvest stress, spoilage, and other plant variations. An 'active package' (incorporating the controlled release of olefinic inhibitor delivered by the cyclodextrin composition of the invention) with a modified atmosphere will improve the quality of fresh cut fruits and vegetables supplied to consumers, including single-serve, ready-to-eat packages and containers for vending machines. In an exemplary embodiment of the invention, MAP or CAP is used in conjunction with the treated packaging material of the invention for large polyethylene bags used to package cartons of multiple pallets, where the cartons contain fresh produce. Such pallet sized bags are widely used for shipment of produce pallets loaded in cartons; the bags are used for the purpose of enclosing the produce in a modified or controlled atmosphere during transport. In some such embodiments, the bags, paperboard (e.g., polyethylene extrudate coated paperboard) boxes, labels on cartons or bags, treated inserts, or combinations of two or more thereof, comprise a treated packaging material of the present invention.

EMAP is a method that helps to extend the shelf life of fresh produce by optimizing the equilibrium atmosphere within the package. This is achieved by modifying the permeability of the packaging film. The micro-perforation of the film is to adjust₂And CO₂Is used to balance the concentration. The microperforated film is a perforated film or is otherwise rendered porous by needling or stretching a film made from a mixture of thermoplastic material and particulate filler. These films allow for transport by molecular gas/vapor diffusion and block liquid transport. Examples of microporous or microperforated films include those available from River Ranchtech technology of Salinas, CAA film; available from Sidlaw Packaging of Bristol, Great Britain and described in U.S. Pat. Nos. 6,296,923 and 5,832,699A film; and films from Clopay Plastic Products Co, Mason, OH, described in U.S. Pat. Nos. 7,629,042 and 6,092,761.

Additionally, in certain embodiments of the present invention, the gas permeability of non-perforated and non-porous films is modified by simply fabricating films of different thicknesses or using the selectivity of hydrophilic films produced from block copolymers and using these materials in combination with these cured cyclodextrin compositions as packaging materials. The block copolymer or multi-block copolymer is composed of alternating flexible soft segments and crystallizable rigid segments. The properties of the block copolymer are changed by changing the block length of these flexible (soft) and rigid segments. Rigid and flexible sections are thermodynamically immiscible and therefore phase separate. These rigid segments crystallize in a continuous soft phase and form a thin layer. The rigid segments may comprise ester, urethane or amide groups, while the flexible segments are often polyesters or polyethers (poly (ethylene oxide) (PEO) and/or more hydrophobic poly (tetrahydrofuran) (PTMO)). In breathable films, gas vapor is transported primarily through the soft phase; the selective gas permeability depends on the density of hydrophilic groups in the polymer, the relative humidity, and the temperature.

The treated packaging material of the present invention is also useful in embodiments employing specialized and selectively permeable packaging materials. An example of a selectively permeable packaging material isPackaging, currently with Guadalupe, CA: (A)www.breatheway.com(ii) a See alsowww.apioinc.com) The freshly cut agricultural products marketed are used in combination.The membranes are selectively permeable membranes that control the inflow of oxygen and the outflow of carbon dioxide to provide regulated O₂/CO₂To extend shelf life. These films are also temperature responsive. Although such packaging provides improved O₂/CO₂To extend the shelf life of respiratory produce, but it does not otherwise inhibit ripening of the produce. Examples of other suitable breathable hydrophilic films include:a thermoplastic polyamide manufactured by TotalPetrochemicals USA, inc. of Houston, TX;byA breathable hydrophilic polyester block copolymer manufactured by SympaTex Technologies GmbH of Germany;a thermoplastic polyester elastomer manufactured by DuPont DE nemours and co, Wilmington, DE; and block polyurethanes, such as those supplied by Dow Chemicals of Midland, MIAndthese polymers have a large selective gas permeability range. The cured cyclodextrin compositions of the present invention, in combination with such permeable film technology, represent a complete solution to extend the shelf life of respiratory agricultural products.

It will be appreciated that the articles and applications that are the end uses of the present invention can benefit in a variety of ways from the advantages provided by the compositions and methods described herein. These cyclodextrin inclusion complexes are easily formed and isolated using mild conditions and achieve high yield formation of the inclusion complex. These cyclodextrin inclusion complexes are readily stored until added to a cyclodextrin composition. Cyclodextrin inclusion complexes are readily formed, coated, and cured using mild conditions when a small amount of the cyclodextrin inclusion complex is added to a curable, coatable or sprayable composition having a readily changeable viscosity as a whole. These cured cyclodextrin compositions are easily stored or can be formed and used on a manufacturing line. Cyclodextrin inclusion complexes of variable and precise magnitude are easily and reproducibly incorporated into produce packaging. A variety of easily implemented methods of delivering the cured cyclodextrin composition to produce packaging and packaging materials are possible.

1-methylcyclopropene (1-MCP) as an olefinic inhibitor

In embodiments where 1-MCP is an olefinic inhibitor, the target concentration for many produce items is between about 2.5ppb and about 10ppm, or between about 25ppb and 1 ppm. In various embodiments, the 1-MCP cyclodextrin inclusion complex is formed with an alpha-cyclodextrin; i.e., 1-MCP/c/alpha-CD. One factor other than those mentioned above that affects the release of 1-MCP from 1-MCP/c/alpha-CD is the amount of water contained within the enclosed space. This requires consideration of the amount of water provided within the enclosed space, the amount of water released by the respiratory agricultural material, and the amount of water that remains within the package as this amount changes with the respiration of the plant.

In embodiments of the present invention that utilize the cyclodextrin inclusion complex 1-MCP/c/α -CD in the cyclodextrin compositions, cured cyclodextrin compositions, treated packaging materials, and/or treated containers of the present invention, the produce is enclosed within an enclosed volume defined by the container, and the treated packaging material is exposed to the internal atmosphere within the enclosed volume. Such exposure is in various embodiments either direct exposure of a cured coating in the internal atmosphere or indirect exposure of such a coating applied to the exterior of the package, wherein the package is permeable to water, 1-MCP, or both. The enclosed volume includes a suitable and active amount of water such that the 1-MCP/c/α -CD releases the 1-MCP into the package interior at a concentration sufficient to inhibit ripening or ripening of the produce. The 1-MCP also provides for the packaging material to be released from the packaging material by exposure to controlled levels of water vapor and/or liquid water. Water vapor-assisted release of 1-MCP from the cyclodextrin inclusion complex 1-MCP/c/alpha-CD was explored and described in detail in Carbohydrate Research 345(2010),2085-2089 to Neoh, T.Z et al. In embodiments, the cured cyclodextrin composition is permeable to both olefinic inhibitor and water vapor to an extent sufficient to maintain an amount of olefinic inhibitor that inhibits maturation or ripening within the enclosed volume and in the presence of water vapor.

Carbohydrate Research 345(2010) by researchers such as Neoh, T.Z, 2085-2089 studied the dynamic complex dissociation of 1-MCP/c/α -CD and observed that increased humidity triggers the dissociation of the 1-MCP complex as a whole. However, this dissociation is greatly slowed at 80% relative humidity, presumably due to the collapse of the crystalline structure; a sudden dissociation corresponding to the dissolution of the complex was then observed at a relative humidity of 90%. However, these investigators noted that, as the inventors did, less than 20% of the complexed 1-MCP was released even at 100% relative humidity. In fact, on average less than one fifth of the total amount (about 17.6%) of the complexed 1-MCP was dissociated at the end of the experiment, while about 83.4% of the 1-MCP remained complexed.

In certain embodiments, during dispensing and storage of the packaged produce, when the storage temperature is between about 0 ℃ and about 20 ℃, the relative humidity within the enclosed volume around the produce will be between about 50% and about 100% due to normal moisture loss from respiration of the produce within the enclosed packaging volume. The increase in humidity within the enclosed volume of the package is, in various embodiments, sufficient to release a portion of the 1-MCP from the 1-MCP/c/alpha-CD. Other embodiments adjust the internal humidity of the treated container by adding water prior to sealing to form the enclosed volume. In some such embodiments, the relative humidity within the enclosed volume is provided by adding moisture (water mist, spray or steam) to the air by a humidifier during packaging, or by controlling the humidity of the environment in the packaging location within the package itself, or both.

Unexpectedly, the cured cyclodextrin compositions of the invention continue to release higher concentrations of olefinic inhibitor when the amount of water is increased, even when the amount of water within the enclosed space reaches and exceeds the amount necessary to produce 100% relative humidity at a given volume of space and temperature. Thus, for example, in certain embodiments, a package is formed from the treated packaging material; live plant material is added and the package is sealed. Initially, the package contains a relative humidity of less than 100%; as the plant material respires within the package, a relative humidity of 100% is reached. As the humidity increases, the amount of olefinic inhibitor present in the atmosphere within the package also increases. In certain embodiments, the amount of water released by the plant material exceeds that amount which constitutes 100% relative humidity, such that liquid water is formed. In such embodiments, we have found that the amount of olefinic inhibitor released in the package continues to increase even though the amount of water in the vapour phase cannot be increased and only liquid water is released into the sealed package atmosphere. In our experiments, we found that the level of olefinic inhibitor released from the cured cyclodextrin compositions in an enclosed space continues to increase in a predictable manner with increasing amounts of water added, regardless of whether the water is in vapor or liquid form.

When the dissociation (release) of 1-MCP is measured as a function of water added to the complex, the relationship between the amount of water in an enclosed space and the release of 1-MCP from the 1-MCP/c/alpha-CD complex is very surprising. The water solubility of alpha-CD is 14.5 grams/100 mL or 14.5 wt-% at typical ambient temperatures. As reported in control example a in the experimental section below, a significant excess of water beyond the amount required to completely dissolve the a-CD was required to dissociate 100% of the 1-MCP from the complex. The relationship between the amount of water present and the dissociation of 1-MCP from 1-MCP/c/alpha-CD has been demonstrated in separately supplied complexes and in the cured cyclodextrin compositions of the present invention. The importance of the relationship between water and 1-MCP dissociation is most important for using this technique, because:

1) the amount of 1-MCP in the atmosphere surrounding fruits and vegetables is specified on a country to country basis; and is

2) The benefits (i.e., shelf life extension) obtained from 1-MCP vary from exposure concentration to different types of agricultural produce material (see, e.g., S.M and Postharvest Biology and Technology28(2003),1-25, by Dole, J.M); further, deleterious effects on certain agricultural product materials are possible when excess 1-MCP treatment concentrations are used.

In writing this article, the U.S. Environmental Protection Agency (EPA) currently limits 1-MCP to a maximum of 1ppm in the air by the legal authorities in section 408 of the federal food, drug and cosmetic act, in two instances of state to state regulation; and the European Union health and Consumer protection council, like the European food safety agency member states, prescribes 1-MCP under different directives, limiting 1-MCP to amounts ranging from 2.5ppb v/v to 1ppm v/v.

Thus, in various embodiments, the dissociation of 1-MCP within the headspace of the package must be carefully managed by controlling both the total amount of 1-MCP incorporated into the package structure and the release of 1-MCP from the inclusion complex. In addition, in various embodiments, the amount of residual water that may be inherently adsorbed or absorbed by the cured cyclodextrin compositions of the invention further affects the dissociation of the 1-MCP. In embodiments, the hydrophilic nature of the cyclodextrin itself increases the compatibility of water with a cured cyclodextrin composition into which a cyclodextrin inclusion complex is to be incorporated.

In embodiments of the present invention where the cyclodextrin inclusion complex used in the treated packaging material of the present invention is 1-MCP/c/α -CD, the amount of 1-MCP in the atmosphere required for a particular packaging application is calculated based on several factors, followed by a change in coating thickness and coated area (i.e., total coated volume) based on the enclosed volume, the concentration of 1-MCP/c/α -CD contained in the cured cyclodextrin composition, and the approximate fraction of complexed 1-MCP/c/α -CD (versus uncomplexed α -CD) at the time the target atmosphere is achieved, factors that must be considered in such calculations include any humectants or desiccants within the package, the permeability/adsorbability/absorbency/absorption of the cured cyclodextrin complex to water and 1-MCP, the permeability/adsorbability/absorption of the packaging material to water and 1-MCP, any controlled or modified atmosphere of dimensions within the package, and the respiration rate of the target material, e.g., if a sealed atmosphere containing 1-MCP/adsorbability/8638-CD is required and the total volume of the cured cyclodextrin complex is 100 g/1-MCP and the target volume is assumed to be 100 ppm of the cured cyclodextrin composition³Using ideal gas law transformation, containing in total 2cm²A cured cyclodextrin composition coated with 12.7 μm thick 1.71 wt% α cyclodextrin in the area will provide the targeted 1ppm1-MCP to the enclosed volume in the presence of water vapor in embodiments, the targeted weight range of 1-MCP/c/α -CD is 25 micrograms to 1 microgram per liter of enclosed volume in such calculations, the value of delivering the targeted coating amount to the targeted enclosed volume is achieved.

Experimental part

Example 1

A cyclodextrin inclusion complex was formed from α -cyclodextrin and 1-Methylcyclopropene (1-MCP) using the technique described in Neoh, T.L et al J.Agric.Food chem.2007,55,11020-184). The bottle was tightly capped and the components were mixed by simply shaking the bottle by hand.

Approximately 2mL of the mixture was removed with a metering dropper and dispersed onto an 8.5 inch by 11 inch PET film and stretched using a metering rod (meyer rod) with a 25 micron delivery thickness. The coated PET film was then placed on a flat surface approximately 5cm below a medium pressure mercury arc lamp operating at 200 watts per inch (79 watts/cm). After 30 seconds under the lamp, the film was removed. A silicone coated PET sheet (about 50 microns thick) was placed over the cured coating and allowed to stand overnight on a laboratory bench.

A die cutter was used to cut a 1cm by 1cm square of the coated portion of the sheet. The liner was removed from the coated square and the coated square was placed in a 250mL serum bottle. Then use one toThe bottle was sealed with a silicone septum that was a face. The headspace concentration of 1-MCP was measured 1 hour after the coated squares were introduced into the bottles. The headspace concentration of 1-MCP was quantified using gas chromatography by removing 1mL of gas from the sample vial with one gas sampling valve directly interfaced to the GC column with the FID detector. No detectable concentration of 1-MCP was detected due to the lack of humidity in the headspace of this tank.

Then 50 μ L of deionized water was injected into this tank. Care was taken so that liquid water did not directly contact the coated squares. This sealed can was allowed to sit for one hour on a laboratory bench after the water was injected and a second headspace sample was then analyzed. A final headspace sample was analyzed 24 hours after water injection. After 1 hour of water injection, 0.5ppm of 1-MCP was measured in the headspace. After 24 hours, 0.5ppm of 1-MCP was measured in the headspace.

Example 2

An inclusion complex of 1-butene with α -Cyclodextrin was formed using the technique described in Neoh, T.L et al, J.Agric.food chem.2007,55, 11020-. During this process a precipitate formed which was collected by filtration through a 10 micron frit filter and dried at ambient temperature and 0.1mm Hg for about 24 hours. This inclusion complex is referred to as "1-butene/c/α -CD. "

Analysis of 1-butene/c/α -CD was performed by adding 100mg of the collected and dried precipitate to a 250mL glass bottle equipped with a diaphragm lid, careful to ensure that no powder stuck to the bottle wall. After about 1 hour, about 250 μ L of headspace gas was removed from the vial using a six-way, two-position gas sampling valve (Valco # EC6W) interfaced directly to a gas chromatograph (GC; Hewlett Packard 5890) using a RTx-5GC column, 30m x 0.25mm I.D., 0.25 μm membrane (available from Restek, Inc. of Bellefonte, Pa.) and equipped with a Flame Ionization Detector (FID). No measurable concentration of 1-butene was detected due to the lack of humidity (water vapor) in the headspace of the bottle. Then 3mL of water was injected into the bottle through the diaphragm and the bottle was placed on a mechanical shaker and mixed vigorously for approximately 1 hour. After shaking, 250 μ L of headspace gas was removed and added to a 250mL empty bottle fitted with a diaphragm lid, wherein the interior of the bottle was purged with nitrogen. The headspace concentration of 1-butene was quantified using gas chromatography by removing 250 μ L of gas from the 250mL bottle with a six-way, two-position gas sampling bottle (Valco # EC6W) interfaced directly to a GC column with a FID detector previously calibrated with a 6-point 1-butene (99.0% pure, scott specialty Gases, Plumsteadville, PA) calibration curve. Using this procedure, a yield of complexed 1-butene/c/α -CD of 72.5% was found.

Into a 20mL bottleUV Coating VP 10169/60MF-2NE (obtained from Vegra GmbHof Ashhau am Inn, Germany; it is used in 4mm DIN cupsA form of VegraUV coating VP 10169MF-2 with a viscosity of 70sec at 20 ℃) and 0.2g of 1-butene/c/α -CD.

About 3mL of the mixture was removed with a dropper and dispersed on a glass plate. A rubber ink roller was used to spread the mixture over the glass and roller. Next, the mixture was coated using the roller on the coated side of a 20cm by 20cm polyethylene extrudate coated paper section(s) ((s))Freezer Paper, total thickness of 90 microns). The roller delivered a nominal thickness of the coating of 0.3 microns. A razor blade was used to cut a 5cm by 10cm rectangle from the coated sheet. The coated cut rectangle was then passed by hand approximately 10cm below a medium pressure mercury arc lamp operating at 200 watts per inch (79 watts/cm). After exposure to the lamp for 1.5 seconds, the cured rectangle was removed. The cured rectangle was allowed to sit overnight on a laboratory bench with the coated side down.

Six repeated rectangles were made in this manner. Each rectangle was placed in a 250mL serum bottle. Then use one toThese six bottles were sealed with a faced silicone septum. Gas chromatography was used to quantify 1-typical headspace concentration by removing 250 μ Ι _ of gas from the sample vial with a six-way, six-position gas sampling valve that directly interfaced to a GC column with a FID detector. No measurable concentration of 1-butene was detected in the headspace of the bottle.

50 μ L of deionized water was then injected into each vial. Care was taken so that the liquid water did not directly contact the coated rectangles. The headspace of each of the six sealed vials was analyzed 0.5, 1,2, 4, 8, 24, and 96 hours after the water was injected, with approximately 3mL of the headspace volume of the 250mL vial removed for each analysis. The amount of 1-butene released from the UV coated rectangles was quantified by gas chromatography against a six-point 1-butene calibration curve (with a correlation coefficient of 0.998) in each sample. Table 1 and figure 1 show the mean values and standard deviations for six replicate 1-butene headspace concentration samples.

TABLE 1. headspace concentration of 1-butene according to the procedure of example 2.

Example 3

A20 mL bottle was filled with 9.6g ofUV coating VP 10169/60MF-2NE (obtained from Vegra GmbHof Ashhaum am Inn, Germany; which is a form of VegraUV coating VP 10169MF-2 with a viscosity of 70sec at 20 ℃ in a 4mm DIN cup.) then 0.4g of 1-MCP/α -cyclodextrin complex (4.7% 1-MCP, obtained from Spring House, AgroFreeh of PA), known as "1-MCP/c/α -CD", is added to the bottle, this bottle is then tightly covered and the bottle is shaken by hand until the blends appear to be uniformly dispersed, yielding a 4.0 wt-% 1-MCP/c/α -CD blend three further blends are prepared in the same way, comprising 2.0 wt-%, 1.0 wt-% and 0.5 wt-% 1-MCP/c/α -CD%.

A thin (nominally 0.3 μm) coating was transferred using a rubber ink roll using the technique of example 2 to a 20cm by 20cm polyethylene extrudate coated paper sheet.

Using a razor blade, 2.5cm × 10cm rectangles were cut from the coated portion of each sheet, then the coated rectangular sheets were cured using the procedure of example 2The headspace of 1-MCP was analyzed using the technique used in example 2 and using the six point 1-butene calibration curve described in example 2 24 hours after water injection, Table 2 and FIG. 2 give the average 1-MCP headspace concentration and standard deviation for 24 hours for each of the coated and cured rectangular sheets, these data demonstrate that 1-MCP is released into the headspace in a linear fashion (correlation coefficient of 0.99) as the wt-% of 1-MCP/c/α -CD in the coating increases when exposed to water vapor (humidity).

TABLE 2Headspace concentration of 1-MCP according to the procedure of example 3

Example 4

A4.0 wt-% 1-MCP/c/alpha-CD blend was prepared according to the technique of example 3. A coating having a nominal thickness of 0.3 μm was transferred using a rubber ink roll to a 20cm by 20cm polyethylene extrudate coated paper sheet using the technique of example 2. The coated sheet was cured according to the procedure of example 2.

26cm cut from the coated portion of the sheet using a razor blade²、52cm²And 78cm²And (3) sampling. Each sample was placed in a 250mL serum bottle. Then use one toThese bottles were sealed with a faced silicone septum. Then 20 μ L of deionized water was injected into each bottle. Care was taken so that liquid water did not directly contact the test sample. According to the technique of example 3, the water is injected for 0.17 hours, 0.5 hours, 1 hour,The headspace analysis of the vials was performed after 2 hours, 4 hours, and 24 hours.1-MCP headspace concentrations as a function of area and time for the test samples are provided in table 3 and fig. 3. these data demonstrate that 1-MCP is released in a predictable manner over time as the surface area of the coating with 4.0 wt-% 1-MCP/c/α -CD increases when exposed to water vapor (humidity).

TABLE 3Headspace concentration of 1-MCP according to the procedure of example 4

Example 5

5cm × 10cm rectangles were cut using razor blades from coated sections of 20cm by 20cm sheets prepared as in example 3 and having 1.0 wt-%, 2.0 wt-% and 4.0 wt-% 1-MCP/c/α -CD, and the coated rectangles were cured according to the technique of example 2The results are provided in Table 4 and FIG. 4 and give the mean headspace concentration and standard deviation over time for different wt-% 1-MCP/c/α -CD coatings, these data demonstrate that 1-MCP is released into the headspace over time in a predictable manner as the wt-% of the 1-MCP/c/α -CD in the coating increases when exposed to water vapor (humidity).

TABLE 4Headspace concentration of 1-MCP according to the procedure of example 5

Example 6

A100 mL quartz beaker was charged with 54g of 2-isooctyl acrylate, 6g of acrylic acid, and 0.60g of 1-hydroxycyclohexyl phenyl ketone (g: (R))184, cirba Specialty chemicals Corp. of Tarrytown, NY.) the beaker was equipped with a mechanical stirrer and the contents were mixed for about 5 minutes while bubbling dry helium gas then the beaker was irradiated with a medium pressure mercury arc lamp operating at 79 watts/cm located about 15cm from one side of the beaker, this lamp was turned off when the contents of the flask had a honey-like consistency, and the beaker was further charged with 3.23g of 1-MCP/c/α -CD, 0.89g of 1-MCP/c/α -CD, at about 1.5 minutes184. 5.8g of isooctyl acrylate, and 0.72g of acrylic acid. The contents of the beaker were mixed until uniformly dispersed for about 5 minutes.

Approximately 4mL of the mixture in the bottle was removed with a metering dropper and dispersed onto a 30.5cm by 30.5cm white paper label paper and stretched using a metering rod (meyer rod #30) with a delivered coating thickness of 25 microns. A 21.5cm by 28cm sheet of silicone-coated Polyester (PET) film (120 μ M thick, available from 3M Company of st. paul, MN) was then placed on the coated label paper taking care not to entrain air bubbles. The coated and covered label paper was cut into a plurality of rectangles of 10cm by 20cm using a cutter. The cut samples were passed by hand approximately 15cm below a medium pressure mercury arc lamp at 79 watts/cm; the adhesive is cured using multiple manual passes under the UV lamp, or about 30 seconds under the lamp. These cured coated label paper sheets were allowed to stand overnight on a laboratory bench with the PET side up.

Use of oneThe guillotine was used to cut six repeated squares of 2.5cm by 2.5cm from these sheets. Because the UV-cured coating composition is a pressure sensitive adhesive or PSA, these 2.5cm by 2.5cm squares are referred to as "PSA labels". Each PSA label (with the silicone coated PET still in place) was placed in a 250mL serum bottle. By one toEach bottle was sealed with a faced silicone septum. After 1 hour of introducing the PSA label into one bottle, the headspace concentration of 1-MCP was measured using the technique of example 3, except that 250 μ Ι _ of gas was removed from the sample bottle for analysis. The quantitative limit of 1-MCP is below 0.01 ppm.

50 μ L of deionized water was then injected into each vial. Care was taken so that liquid water did not directly contact the labels. The headspace of the sealed vial was analyzed at 10 minutes, 30 minutes, and 60 minutes using the technique of example 3. A final headspace sample was analyzed 16 hours after the water injection. These data are shown in table 5. These data demonstrate that 1-MCP is released from PSA labels into the headspace when exposed to water vapor (humidity) and its concentration increases over time.

TABLE 5Headspace concentration of 1-MCP according to the procedure of example 6

Hour(s)	Mean value of 1-MCP ppm (v/v)	Standard deviation of
			0.17	0.01	0.01

0.5	1.3	0.84
			1	3.6	0.75
16	29.7	8.0

Example 7

This method is designed to measure the permeability of 1-MCP through a defined, fixed volume of polyethylene film into the headspace of this defined, fixed volume after release from the film from a PSA label adhered to the surface of the film. The methodology simulates a headspace of flexible film initially having low relative humidity, with a 1-MCP containing PSA label adhered to the outside of the package. As the humidity within the package increases due to respiration of fresh produce, the water vapor concentration increases and it diffuses through the packaging film to the external environment, but also into the PSA. Thus, as water vapor diffuses through the film into the 1-MCP adhesive sticker adhered to the exterior of the packaging film; the release of 1-MCP from the label adhesive into the fixed volume (headspace) was measured.

A coated, cured label paper sheet made according to the procedure of example 6 was cut by hand into 11cm diameter circles. The PET liner was then removed from the label and the label was adhered by PSA to a 13.5cm diameter, 1 mil (25 μm) thick Polyethylene (PE) film (available from Pliant Corporation of Schaumburg, IL). The paper side of this structure was then covered with aluminum foil. The foil/paper/PSA/PE layered structure was mounted on the open end of a 1,000mL Glass autoclave bottom (6947-1LBO, Corning Glass from Corning, NY) and sealed to the Glass flange of the autoclave using aluminum sealing rings. The layered structure was oriented over the 11cm opening with the PE film facing inward and the aluminum facing outward. The glass reaction kettle was modified with an organosilicon diaphragm port to allow sampling of the 1,000mL headspace. The headspace analysis was performed by removing a 250 μ L headspace volume from the 1,000mL glass kettle and analyzing according to the technique of example 3.

Two hours after sealing the film and label to the flange on the top of the reaction kettle and without adding any water in this 1,000mL volume; an initial headspace analysis was performed and this analysis revealed no detectable 1-MCP levels (<0.01 ppm). 200 μ L of water was then added to the interior of the glass kettle through the diaphragm port. Headspace analysis was performed on 1-MCP after 17, 25 and 90 hours of water injection using the technique used in example 3. After 17 hours, 25 hours, and 90 hours of water injection, the 1-MCP headspace concentrations were 3.6ppm, 7.0ppm, and 8.0ppm of 1-MCP, respectively. These results demonstrate that a PSA-coated label containing 1-MCP and adhered to the surface of a vapor-permeable film can release 1-MCP into the package headspace after the injection of water vapor inside the package headspace.

Comparative example A

α -CD has a water solubility of 14.5 g/100 mL or 14.5 wt-% (Szejtli, J. (1988), Cyclodextrin Technology, Kluwer Academic Publishers, page 12) at typical ambient temperatures A sample of 1-MCP/c/α -CD powder was obtained (Spring House, AgroFreeh from PA.) 1-MCP was 4.7 wt% according to the supplier's specification sheetα -CD of (1-MCP) or a 88.7 wt% complex of 1-MCP based on a 1:1 theoretical molar ratio of 1-MCP to α -CD, which corresponds to a resulting headspace concentration of 8,600ppm A series of tests were conducted to measure the dissociation of 1-MCP from supplied 1-MCP/c/α -CD as a function of added water first, multiple 0.1 aliquots of supplied 1-MCP/c/α -CD powder were added to each of 5, 250mL bottles, then withThe bottles were capped for the facial diaphragm various amounts of water were added to the bottles by syringe and then the bottles were mechanically shaken for one hour, after which headspace measurements were taken for 1-MCP according to the procedure of example 3 the amount of water added for each 0.1g of 1-MCP/C/α -CD complex supplied, and the headspace measurements obtained at about 20C after 1 hour are shown in Table 6.

Our test results show that 5.8 wt% 1-MCP or 111 wt% 1-MCP/c/alpha-CD complex (greater than 1:1 complex) produces a headspace concentration of 10,610 ppm. At a concentration of 1.0 gram of water per 0.10 gram of 1-MCP/c/alpha-CD, the water solubility of alpha-CD is exceeded even if only 66% of the 1-MCP is dissociated. Polynomial regression was used to calculate the dissociation at 100% RH in the headspace for the five samples in table 6 (i.e., 4.3 mg water per 250mL volume, see example 8 for source and calculation of this information). The calculated value of 1-MCP dissociated at 100% RH was 18 wt-%.

These results were unexpected because the limited amount of filtered water required to dissociate 100% of the complexed 1-MCP was higher than that required to completely dissolve the a-CD (14.5 g/100 mL, as reported above).

TABLE 6Headspace concentration of 1-MCP according to the procedure of comparative example A

Example 8

A4.0 wt-% 1-MCP/c/alpha-CD coating blend was prepared according to the technique of example 3. A 20cm by 20cm polyethylene extrudate coated paper sheet was coated with the mixture using the technique of example 2. A guillotine cutter was used to cut nine rectangles of 5cm by 10cm from the sheet. The cut coated rectangles were passed by hand approximately 10cm below a medium pressure mercury arc lamp operating at 79 watts/cm. After exposure to the lamp for 1.5 seconds, the sample was removed. The cured sample was allowed to stand overnight on a laboratory bench with the coated side facing down.

Each cured sample was placed in a 250mL serum bottle. By one toEach bottle was sealed with a faced silicone septum. The amount of liquid water (at 20 ℃ C.) corresponding to 100% Relative Humidity (RH) in the form of a vapourhttp://hyperphysics.phy-astr.gsu.edu/hbase/kinetic/vappre.html#cProvided) is 3g/m³Or 17.3g per 1000L. The density of water at 20 ℃ was 0.9982 g/mL. Thus, at 20 ℃, 4.3 μ L of liquid water is added to a 250mL closed volume and no other water will evaporate to give 100% RH. The temperature of our laboratory equipment was 20 ℃. + -. 5 ℃.

Three of these vials were injected with 10 μ L of deionized water, three were injected with 20 μ L of deionized water, and three were injected with 50 μ L of deionized water. Care was taken so that liquid water did not directly contact the coated squares. Headspace analysis of individual vials was performed on 1-MCP after 2 hours, 4 hours, 8 hours, 24 hours, and 48 hours of water injection, using the technique used in example 3. The mean headspace concentration results and standard deviations are provided in table 7 and figure 5.

TABLE 7Headspace concentration of 1-MCP according to the procedure of example 8

H2O,μL	Time,hr	Average value of 1-MCP, ppm (v/v)	Standard deviation of
				10	2	1.3	0.77
10	4	2.5	0.81
				10	8	3.8	0.94
10	24	7.1	1.5
				10	48	10.0	2.0
20	2	2.6	1.1
				20	4	5.8	1.3
20	8	9.2	1.7
				20	24	15.7	1.9
20	48	20.5	2.0
				50	2	8.7	4.1
50	4	18.6	3.6
				50	8	30.8	0.42
50	24	55.3	10.7
				50	48	63.0	17.0

Example 9

UV curable inks for thermal inkjet cartridges as well as industrial printing were formulated with 1-MCP/c/α -CD and printed onto films to demonstrate how UV inks can be incorporated into flexible packaging structures to release 1-MCP. The ImTech UVBLK Series912 cassette is available from ImTech inc. Approximately 40 grams of black ink was removed from the cartridge that supplied the ink. The ink was dried overnight in a closed container with 3A molecular sieves to remove residual water contained in the ink. 17.5g of the dried ink was then transferred to a 70mL roller mill tank filled with 50g of 3mm glass beads, to which was added 0.875g of 1-MCP/c/α -CD to the UV ink. The jar was sealed and spun on a roller mill at 140rpm for four hours. At the end of the four hour roll to disperse the 1-MCP/c/α -CD, an additional 4.375g of dry UV ink was added to make up an ink containing 4 wt-% 1-MCP/c/α -CD. The ink was then poured out of the glass beads.

A discontinuous thin (nominally 3 μ M) but uniform UV ink coating was applied to a 10cm by 20cm section of PET film (120 μ M thick, available from 3M Company of st. paul, MN) using a rubber ink roller in the manner described in example 2. The UV ink coated rectangle was passed by hand approximately 10cm below a medium pressure mercury arc lamp operating at 79 watts/cm and exposed to the lamp for 1.5 seconds. The cured sample was allowed to sit overnight on a laboratory bench with the ink side facing down.

Two samples were cut from the cured ink coated PET film sheet using a guillotine cutter: 20cm²And 81cm². These samples were individually placed in a 250mL serum bottle. Then use one toThese bottles were sealed with a faced silicone septum. Then 200 μ L of deionized water was injected into the bottle. Care was taken so that liquid water did not directly contact the ink coated PET film. After water was injected into the bottle, the analytical technique employed in example 3 was used to measure 1-MCP in the headspace. The test results are tabulated in Table 8; these results confirm the release of 1-MCP from the UV ink. These results further demonstrate that 1-MCP is slowly released, increasing the headspace concentration of the vial with time.

TABLE 8Headspace concentration of 1-MCP according to the procedure of example 9

Example 10

The ink containing 4 wt-% 1-MCP/c/alpha-CD from example 9 was loaded back into the previously emptied cartridge. After refilling the cartridge, it was mounted on an HP Inkjet 1600C printer (available from Hewlett-Packard Company of Palo Alto, Calif.) and the calibration or head cleaning functions were run. The entire printable page is formatted using a medium density, black mesh grid (cross-hatch pattern) available from Microsoft EXCEL software program 2003 (available from Microsoft Corporation of Redman, WA). An image of the EXCEL pattern was printed onto a 3M, CG3460Transparency Film (120 micron thick polyester for HP ink jet printers; available from 3M Company of St. Paul, MN) using the milled ink containing 4 wt-% 1-MCP/c/α -CD of example 9. Immediately after printing, the printed side of the transparent film was covered with a 25 μm polyethylene film and then passed by hand approximately 10cm under a medium pressure mercury arc lamp operating at 79 watts/cm, exposed to the lamp with the polyethylene side facing the lamp, for 3 seconds. The methodology simulates a multilayer flexible package in which the inner surface of an outer transparent layer of the multilayer flexible material is printed (known as reverse printing). The printed surface is then laminated to other layers. The outer layer itself serves to protect the ink from abuse.

The following technique was designed to measure the permeability of 1-MCP released from the reverse inkjet printed 3M Transparency Film through PE Film (as an "inner layer" of a multilayer produce package). In a multi-layer produce package, as the humidity inside the package increases due to respiration of fresh produce, water vapor reaches a concentration that allows it to diffuse to the outside of the package. In this example, water also diffused through the 1-MCP/c/alpha-CD containing ink layer. The reverse printed ink on the PET film released 1-MCP that diffused through the PE film into the package (headspace) interior at a gradient of low 1-MCP concentration inside the bottle headspace and high 1-MCP concentration inside the multilayer structure.

A5.5 cm by 16cm rectangle (88 cm) was cut from this multilayer structure with printed cured ink on a PE-coated PET sheet using a guillotine²). The rectangle was placed in a 250mL serum bottle. Then use one toThe bottle was sealed with a faced silicone septum. Then 100 μ L of deionized water was poured into the bottle. Care was taken so that liquid water did not directly contact the test sample. The headspace of the bottle was analyzed using the technique used in example 3 after 0.17, 0.5, 1,2, 4 and 24 hours of water injection. The results in Table 8 show the 1-MCP headspace concentration of the "multilayer" film as a function of time.

A second sheet of PET clear film was printed as in example 9, except that the clear film was not covered by PE film; the printed ImTech UVBLK Series912 was cured onto the PET film using a medium pressure mercury arc lamp operating at 79 watts/cm in the same manner as example 9. A guillotine cutter was then used to cut a 1.2cm by 16cm rectangle (19 cm) from the sheet²). The rectangle was placed in a 250mL serum bottle. Then use one toThe bottle was sealed with a faced silicone septum. Then 100 μ L of deionized water was poured into the bottle. Care was taken so that liquid water did not directly contact the test sample. The headspace of the bottle was analyzed using the technique used in example 3 after 0.17, 0.5, 1,2, 4 and 24 hours of water injection. The 1-MCP headspace concentration of this "single layer" film as a function of time is also reported in Table 9.

TABLE 9Headspace concentration of 1-MCP according to the procedure of example 10

Example 11

Polyethylene extrudate coated paperboard is one of the most commonly used materials for packaging fresh produce. Typically, the paperboard is recyclable and has a thin layer of polyethylene (typically 30 μm or less) on one or both sides. The extrudate coated surface may be coated or printed with a UV curable coating containing 1-MCP.

A20 mL bottle was charged with 9.6g of the UV curable coating formulation (VP 10169/60MF-2NE, obtained from Vegra GmbH of Aschau am Inn, Germany). Then 0.4g of 1-MCP/alpha-CD (4.7% 1-MCP, obtained from School House, AgroFreesh, Pa.) was added to the flask. The bottle was tightly covered and the components were mixed by shaking the bottle by hand until the contents appeared to be well dispersed, providing a UV curable mixture.

A polyethylene coated paperboard was prepared as follows: a 30 μm thick polyethylene film heating layer was laminated to a 20cm x 20cm section of 600 μm thick Solid Bleached Sulfate (SBS) paperboard (available from Graphic packaging international of). A thin (nominally 0.3 μm) coating of the UV curable ink was transferred to the laboratory prepared polyethylene coated paperboard using a rubber ink roll using the technique of example 2. A guillotine was used to cut a 20cm by 10cm rectangle of the coated portion of the sheet. The coated rectangle was passed by hand approximately 10cm below a medium pressure mercury arc lamp operating at 79 watts/cm. After exposure to the lamp for 1.5 seconds, the sample was removed. The cured sample was allowed to stand overnight on a laboratory bench with the coated side facing down.

After curing, 5cm by 5cm sections were cut from these 20cm by 10cm rectangles. Each section was individually placed into a 250mL tank (high clean WM SEPTA-JAR)^TMFisher Scientific P/N05-719-452; obtained from Fisher Scientific, Waltham, MA), the tank is fitted with a TEFLON^TMIs the facial diaphragm (Fisher Scientific P/N14-965-84). 200 μ L of deionized water was injected into each tank. Care was taken so that the liquid water did not directly contact the coated rectangles. Headspace analysis of the tanks was performed on 1-MCP after five periods of water injection (0.17, 0.5, 1,2, 4 and 7 hours) using the technique used in example 3. The mean headspace concentrations and standard deviations for 1-MCP are tabulated in Table 10. These results illustrate that over time, greater amounts of 1-MCP are released from the UV coated substrate into the headspace.

Watch 10Headspace concentration of 1-MCP according to the procedure of example 11

Representative embodiments

We now list certain representative embodiments of the invention. The present invention is not limited to these embodiments and the other embodiments described above are also embodiments of the present invention or, when combined with any combination of the embodiments described below, embodiments of the present invention.

Embodiment 1.

Embodiment 1 is an embodiment of the present invention, either alone or in further combination with any of the additional limitations or elements described above or in the list below, as appropriate. Embodiment 1 may be combined with one combination of two or more additional limitations or elements described above or in the list below. The following list contains a number of limitations or elements which are intended to be combined with embodiment 1 in any way as further aspects of the invention, including in combination with one or more of the other limitations or elements described above.

Embodiment 1 of the invention is a cyclodextrin composition comprising one or more radiation polymerizable monomers and a cyclodextrin inclusion complex comprising a cyclodextrin compound and an olefinic inhibitor of ethylene production in production comprising a compound having the structure

Wherein each R¹、R²Independently is hydrogen or a C_1-16A hydrocarbon radical, and R³And R⁴Independently is hydrogen or a C_1-16A hydrocarbyl radical with the proviso that R¹Or R²At least one of which is methyl.

This list of additional limitations or elements includes, but is not limited to, the following:

a. the one or more radiation polymerizable monomers comprising acrylic acid, methacrylic acid, an acrylate, a methacrylate, acrylamide, a diacrylate, a triacrylate, a tetraacrylate, or mixtures thereof;

b. the acrylate or methacrylate is an ester of an alcohol having 1 to 18 carbons and is a linear, branched, or cyclic ester;

c. the composition further comprises a photoinitiator;

d. the composition further comprises one or more prepolymers;

e. the cyclodextrin comprises a cyclodextrin derivative;

f. the cyclodextrin inclusion complex comprises about 0.1 to 0.99 moles of the olefinic inhibitor per mole of cyclodextrin;

g. the olefinic inhibitor includes 1-methylcyclopropene;

h. the cyclodextrin includes alpha-cyclodextrin;

i. the cyclodextrin inclusion complex comprises about 0.80 to 0.99 moles of 1-methylcyclopropene per mole of alpha-cyclodextrin;

j. the composition comprises 0.01 wt% to 10 wt% of the cyclodextrin inclusion complex, based on the weight of the composition;

k. the composition is coatable;

the composition is printable;

m. the composition is an ink;

n. the composition is a UV curable ink;

the composition further comprises one or more colorants;

p. the composition further comprises one or more adhesion promoters, stain repellents, heat stabilizers, oxidation stabilizers, water scavengers, adjuvants, plasticizers, or combinations of two or more thereof;

the composition further comprises one or more desiccants;

the composition further comprises one or more desiccants comprising silica gel, molecular sieves, or a combination thereof.

Embodiment 2.

Embodiment 2 is an embodiment of the present invention, either alone or in further combination with any of the additional limitations or elements described above or in the list below, as appropriate. Embodiment 2 may be combined with one combination of two or more additional limitations or elements described above or in the list below. The following list contains a number of limitations or elements which are intended to be combined with embodiment 2 in any way as further aspects of the invention, including in combination with one or more of the other limitations or elements described above.

Embodiment 2 of the invention is a treated packaging material comprising a packaging material and a cured cyclodextrin composition disposed on at least a portion of a surface of the packaging material, the cured cyclodextrin composition comprising a polymer derived from one or more radiation polymerizable monomers and a cyclodextrin inclusion complex comprising cyclodextrin and an olefinic inhibitor produced to ethylene in production, the olefinic inhibitor comprising a compound having the structure

Wherein each R¹、R²Independently is hydrogen or a C_1-16A hydrocarbon radical, and R³And R⁴Independently is hydrogen or a C_1-16A hydrocarbyl radical with the proviso that R¹Or R²At least one of which is methyl.

This list of additional limitations or elements includes, but is not limited to, the following:

a. the treated packaging material comprises a film, sheet, foil, bag, basket, tray, cup, lid, label, paperboard, carton, or treated packaging insert;

b. the packaging material comprises a polyolefin or polyester;

c. the surface comprises a plasma treated surface;

d. the treated packaging material further comprises a primer disposed between the packaging material and the cured cyclodextrin composition;

e. the cured cyclodextrin composition is permeable to water and olefinic inhibitor;

f. the cured cyclodextrin composition has different permeabilities to water and to the olefinic inhibitor;

g. the treated packaging material comprises a film, sheet, treated packaging insert, or a label and further comprises a liner disposed on top of the cured cyclodextrin composition;

h. the liner is transparent to UV light;

i. the liner is a foil;

j. the liner further comprises one or more desiccants;

k. the liner is preferably removable at the interface of the liner and the cured cyclodextrin composition;

the liner is impermeable to water;

the packaging material is impermeable to water;

n. the packaging material is impermeable to the olefinic inhibitor;

the packaging material is permeable to water, permeable to the olefinic inhibitor, or permeable to both water and olefinic inhibitor;

p. the packaging material is a selectively permeable film;

the cured cyclodextrin composition comprises a pressure sensitive adhesive;

the cured cyclodextrin composition is present as a coating on the packaging material;

s. the coating is about 0.01 micron to 1 millimeter thick;

t. the coating comprises printed indicia;

the cured cyclodextrin composition is bonded to the packaging material;

v. the packaging material comprises a treated laminate material;

w. the packaging material comprises a treated laminate material which is permeable to the olefinic inhibitor on a first side thereof and impermeable to the olefinic inhibitor on a second side thereof;

the packaging material comprises a treated laminate material which is water permeable at least on a first side thereof;

y. the treated packaging material is tentered.

Embodiment 3.

Embodiment 3 is an embodiment of the present invention, either alone or in further combination with any of the additional limitations or elements described above or in the list below, as appropriate. Embodiment 3 may be combined with one combination of two or more additional limitations or elements described above or in the list below. The following list contains a number of limitations or elements which are intended to be combined with embodiment 3 in any way as a further aspect of the invention, including in combination with one or more of the other limitations or elements described above.

Embodiment 3 of the present invention is a container comprising a treated packaging material, wherein the container comprises an enclosed volume, the treated packaging material comprising a cured cyclodextrin composition disposed on at least a portion of a surface of a packaging material, the cured cyclodextrin composition comprising a polymer derived from one or more radiation polymerizable monomers and a cyclodextrin inclusion complex comprising an olefinic inhibitor produced in production for ethylene, the olefinic inhibitor comprising a compound having the structure

Wherein each R¹、R²Independently is hydrogen or a C_1-16A hydrocarbon radical, and R³And R⁴Independently is hydrogen or a C_1-16A hydrocarbyl radical with the proviso that R¹Or R²At least one of which is methyl.

This list of additional limitations or elements includes, but is not limited to, the following:

a. the container is a bag, basket, tray, cup, or carton;

b. the cured cyclodextrin composition is present as a coating on at least a portion of an interior surface of the container;

c. the cured cyclodextrin composition is present as a coating on at least a portion of an exterior surface of the container;

d. the cured cyclodextrin composition is presented as a coating on a package insert;

e. the container is a processed laminated container;

f. the container is a treated laminated container, wherein the laminated material structure is permeable to the olefinic inhibitor on a first side thereof and impermeable to the olefinic inhibitor on a second side thereof;

g. the container is a treated laminated container, wherein the laminated material structure is water permeable on at least a first side thereof;

h. the container further comprises a desiccant;

i. the container further comprises an item of agricultural produce;

j. the enclosed volume comprises between 50% and 100% relative humidity at a temperature between about 0 ℃ and 20 ℃;

k. the enclosed volume comprises a relative humidity of 100% at a temperature between about 0 ℃ and 20 ℃ and further comprises liquid water;

the container comprises a modified atmosphere package;

the container comprises a controlled atmosphere package;

the container comprises a selectively permeable membrane;

the olefinic inhibitor is present in the enclosed volume at a concentration of about 2.5 parts per billion to 10 parts per million;

p. the olefinic inhibitor is present in the enclosed volume at a concentration of about 25 parts per billion to 1 part per million.

Embodiment 4.

Embodiment 4 is an embodiment of the present invention, either alone or in further combination with any of the additional limitations or elements described above or in the list below, as appropriate. Embodiment 4 may be combined with one combination of two or more additional limitations or elements described above or in the list below. The following list contains a number of limitations or elements which are intended to be combined with embodiment 4 in any way as a further aspect of the invention, including in combination with one or more of the other limitations or elements described above.

Embodiment 4 of the present invention is a method for manufacturing a treated packaging material, the method comprising

Forming a cyclodextrin composition comprising one or more radiation polymerizable monomers and about 0.05 wt% to 10 wt%, based on the weight of the cyclodextrin composition, of a cyclodextrin inclusion complex comprising cyclodextrin and an olefinic inhibitor produced to ethylene in production, the olefinic inhibitor comprising a compound having the structure

Wherein each R¹、R²Independently is hydrogen or a C_1-16A hydrocarbon radical, and R³And R⁴Independently is hydrogen or a C_1-16A hydrocarbyl radical with the proviso that R¹Or R²At least one of which is methyl;

disposing the cyclodextrin composition on at least a portion of a surface of a packaging material at a thickness of about 0.01 microns to 1 millimeter to form a coating; and is

Exposing the coating to a radiation source to form a cured cyclodextrin composition.

This list of additional limitations or elements includes, but is not limited to, the following:

a. the cyclodextrin composition further comprises about 0.1 wt% to 5 wt%, based on the weight of the composition, of one or more photoinitiators, wherein the irradiating is with ultraviolet radiation;

b. the cyclodextrin composition further comprises about 0.1 wt% to 5 wt% of one or more photoinitiators, based on the weight of the composition, and further comprises additionally exposing the cyclodextrin composition to a radiation source prior to the coating, wherein the radiation source is ultraviolet radiation;

c. adding one or more additional monomers, an additional photoinitiator, or a combination thereof to the cyclodextrin composition after the additional exposure and prior to disposing;

d. the radiation source is electron beam radiation;

e. the radiation source is ultraviolet radiation;

f. the coating is disposed on the entirety of one major surface of the packaging material;

g. the coating is disposed on a portion of one major surface of the packaging material;

h. the arrangement is done by printing;

i. the printing is gravure printing, flexographic printing, or inkjet printing;

j. the cured cyclodextrin composition includes a pressure sensitive adhesive;

k. disposing a liner on the cyclodextrin composition;

the liner is disposed prior to irradiation;

the liner is disposed after the irradiation;

the liner comprises a desiccant;

the treated packaging material is a treated container;

p. the method further comprises forming a treated container from the treated packaging material;

q. the method further comprises forming a treated packaging insert from the treated packaging material;

the method further comprises forming a treated label from the treated packaging material;

s. the method further comprises forming a processed laminate material;

t. the method further comprises forming a container of a treated stack;

the method further comprises disposing the cured cyclodextrin composition inside a container having an enclosed volume, wherein the cured cyclodextrin composition contacts the enclosed volume;

v. the method further comprises disposing the cured cyclodextrin composition outside of a container having an enclosed volume, wherein the cured cyclodextrin composition does not directly contact the enclosed volume;

w. the method further comprises enclosing an item of produce inside the container.

The foregoing discloses embodiments of the present invention. In the present specification and claims, the word "about" used in describing embodiments of the present disclosure, for example, the amounts, concentrations, volumes, processing temperatures, processing times, yields, flow rates, pressures, and the like, of ingredients in a composition, and ranges thereof, refers to changes in the numerical values, such as by typical measurement and handling procedures used to make compounds, compositions, concentrates, or use formulations; by inadvertent error in these procedures; as may occur through differences in the manufacture, source, or quality of the starting materials or ingredients used to carry out the methods, and similar approximation considerations. The word "about" also encompasses amounts that vary due to aging of a formulation having a particular initial concentration or mixture, as well as amounts that vary due to mixing or treating a formulation with a particular initial concentration or mixture. When the word "about" is used to modify, the appended claims include equivalents to these amounts. "optional" or "optionally" means that the subsequently described event or circumstance may, but need not, occur, and that the description includes instances where the event or circumstance occurs and instances where it does not. The invention may suitably comprise, consist of, or consist essentially of the elements disclosed or exemplified. Thus, the invention illustratively disclosed herein suitably may be practiced in the absence of any element which is not specifically disclosed herein. The use of the singular typically includes, and at least does not exclude, the plural.

The specification, drawings, examples and data provide a detailed explanation of the invention as it has been developed thus far. The invention may take the form of other embodiments without departing from the spirit or intended scope of the invention. The invention resides in the claims hereinafter appended.

Claims (7)

1. A cyclodextrin composition comprising one or more radiation polymerizable monomers and a cyclodextrin inclusion complex comprising a cyclodextrin compound and an olefinic inhibitor of ethylene production in an agricultural product, the olefinic inhibitor comprising a compound having the structure

Wherein each R¹、R²Independently is hydrogen or a C_1-16A hydrocarbon radical, and R³And R⁴Independently is hydrogen or a C_1-16A hydrocarbyl radical with the proviso that R¹Or R²At least one of which is methyl.

2. The composition of claim 1, wherein the one or more radiation polymerizable monomers comprise acrylic acid, methacrylic acid, an acrylate, methacrylate, acrylamide, diacrylate, triacrylate, tetraacrylate, or mixtures thereof.

3. The composition of claim 1, wherein the composition further comprises a photoinitiator.

4. The composition of claim 1, wherein the composition further comprises one or more prepolymers.

5. The composition of claim 1, wherein the olefinic inhibitor comprises 1-methylcyclopropene.

6. The composition of claim 5, wherein the cyclodextrin compound comprises alpha-cyclodextrin.

7. The composition of claim 1, wherein the composition comprises 0.01 wt% to 10 wt% of the cyclodextrin inclusion complex, based on the weight of the composition.