cyclodextrin compositions and method of manufacturing a treated packaging material

专利摘要:
Cyclodextrin methods, articles and compositions are cyclodextrin compositions which include one or more radiation polymerizable monomers and a cyclodextrin inclusion complex, wherein the cyclodextrin inclusion complex includes a cyclodextrin compound and a one-generation olefin inhibitor. ethylene in production, applied as a coating on packaging and cured materials. Treated containers and treated packaging leaflets have cured cyclodextrin compositions are useful in packaging breathing plant materials.
公开号:BR112013024750B1
申请号:R112013024750-9
申请日:2011-10-20
公开日:2019-02-05
发明作者:Willard E. Wood；William J. Kuduk；Joseph S. Keute
申请人:Cellresin Technologies, Llc；
IPC主号:

专利说明:

“CYCLODEXTRIN COMPOSITIONS AND METHOD OF MANUFACTURING A TREATED PACKAGING MATERIAL” [001] This application is filed as a PCT International Patent application on October 19, 2011, in the name of CELLRESIN TECHNOLOGIES, LLC, a company with national capital of the USA, claimant for designation of all countries except the US, and Inventors Willard E. Wood, a US Citizen, and William J. Kuduk, a US Citizen, claimants for the US designation only, and claims priority on Request US Patent No. 61 / 468,041, filed March 27, 2011.
BACKGROUND [002] The useful life of production or production materials, including whole plants and parts thereof including fruits, vegetables, tubers, bulbs, cut flowers and other active breathing plants or plant materials, is typically determined, at least in partly by the amount of an ethylene hormone generated by the respiration plant material. Ethylene is a known plant ripening or maturing hormone. At any substantial concentration of ethylene in and around plant material, plant maturation is initiated, maintained or accelerated, depending on the concentration. Agricultural goods sensitive and insensitive to ethylene (production and ornamental) are categorized as climacteric or non-climacteric on the basis of the ethylene production pattern and correspondence to externally added ethylene. Climacteric crops respond to ethylene by an early induction of an increase in respiration and accelerated ripening in a concentration-dependent manner. Non-climacteric crops mature without bursting of ethylene and breathing. However, some non-climatic crops are sensitive to exogenous ethylene, which can significantly reduce the useful life after harvest. Non-climatic production houses several ethylene receptors that are active. Therefore, the production exposure
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2/83 non-climacteric exogenous ethylene can trigger physiological disturbances that shorten its useful life and quality. See, Burg et al., Plant Physiol. (1967) 42 144 to 152 and generally Fritz et al. U.S. Patent No. 3,879,188. Many attempts have been made to remove ethylene from the packaging atmosphere of the environment surrounding the production or to remove ethylene from the storage environment in an attempt to increase the service life. The reduced ethylene concentration is understood to be achieved through a decrease in stimulation of a specific ethylene receptor in plants. Many compounds in addition to ethylene interact with this receptor: some imitate the action of ethylene; others prevent ethylene from making connections and, therefore, prevent its action.
[003] Many compounds that act as an antagonist or inhibitor block the action of ethylene by binding to the ethylene binding site. These compounds can be used to prevent the action of ethylene. Unfortunately, they often diffuse from the binding site over a period of several hours until a longer reduction in inhibition. See E. Sisler and C. Wood, Plant Growth Reg. 7, 181 to 191 (1988). Therefore, a problem 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 to 164 (1990). Methods for combating the ethylene response in plants with diazocyclopentadiene and derivatives thereof are disclosed in U.S. Patent No. 5,100,462 to Sisler et al. U.S. Patent No. 5,518,988 to Sisler et al. describes the use of cyclopropenes that have a C1-4 alkyl group to block the action of ethylene.
[004] An appropriate olefinic antagonist or inhibitor of receptor sites or ethylene generation in production is 1-methylcyclopropene, derivatives and analogs thereof have also been tried as an antagonist or inhibitor for the generation of
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3/83 ethylene from breathing plant or production material. 1-methyl-cyclopropene (1-MCP), 1-butene and other olefins have been shown to have at least some measurable activity to inhibit ethylene generation and thus extend service life. Several proposals have been made for the method of producing and releasing 1-MCP to inhibit the release of ethylene and, as a result, delay maturation and maintain the quality of plant materials. Currently, 1-MCP is dispensed by releasing 1-MCP from a powder activated by hydration or sachet that contains complexed 1-MCP. In these technologies, 1-MCP is released from a point source that causes a concentration gradient within the storage chamber, thus resulting in a variation in maturation inhibition in which some production had an extended life span when another production exposed to a lower concentration of 1-MCP tends to have less ethylene inhibition and has a shorter service life.
[005] Despite these efforts, there is still a substantial need in the technique for improved plant maturation and prevention of degradation. In particular, the pressure of urbanization, manufacturing, and world population growth requires the development of innovative technologies to increase the efficiency and yield of natural sources spent on providing food to the growing global population. In the United States, for example, it is estimated that between 8% and 16% of loss of profit from fresh production is due to deterioration and shrinkage, which is estimated at $ 8 billion - $ 28 billion across the system. This loss translates into a significant waste of resources, for example, use of pesticides, fertilizer, and herbicide; land and water use; transportation, including use of oil and gas; and resources associated with production storage. The loss of these and other resources is due to inefficiencies in production and delivery that allow significant deterioration of fruits and vegetables before these critical products can reach the consumer. The United Nations Center for Asia and Pacific Agricultural Machinery and Engineering Feasibility Study on the
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Green Technology Application for Sustainable Agriculture Development (United Nations Asian and Pacific Center for Agricultural Engineering and Machinery's Feasibility Study) states:
[006] "Technology is a link that connects sustainability with increased productivity, in which the productivity of natural resources is effectively maintained by careful planning for the conservation and exploitation of resources such as soil, water, plants, and animals".
[007] (Feasibility Study on the Application of Green Technology for Sustainable Agriculture Development, United Nations Asian and Center for Agricultural Engineering and Machinery, http://www.unapcaem.org/publication/GreenTech.pdf, p. 20.) climate change has increased the possibility of risks for agricultural technology as the world population grows and the amount of arable land decreases. More mouths to feed, and less arable land and changes in rainfall patterns, mean increasing demand for technology that allows farmers to do more with less. The European Commission recently announced an initiative to improve food packaging without compromising safety in order to reduce food waste (Harrington, R., “Packaging placed center stage in European food waste strategy”, http://www.foodqualitynews.com / PublicConcerns / Packaqinq-placed-center-staqe-in-European-food-waste-strateqy). The initiative is in response to recent findings that up to 179 kg of food per person is wasted each year. The plan reinforces the need for innovation, such as "active packaging" or "smart packaging" as an aspect of the solution.
[008] The technology that addresses the issue of fruit and vegetable spoilage is therefore of great importance as a "green" technology that reduces food waste and its associated resources by actually increasing efficiency
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5/83 arable land.
BRIEF DESCRIPTION OF THE INVENTION [009] The invention relates to a packaging material including a cyclodextrin composition. The cyclodextrin composition contains an effective amount and a controlled release amount of an olefinic ethylene generation inhibitor in production. The packaging material is coated on at least part of a surface thereof with the cyclodextrin composition. After coating, the cyclodextrin composition is subjected to electromagnetic radiation, such as ultraviolet (UV) radiation, or electron beam radiation (e-beam). The cyclodextrin composition reacts when exposed to radiation, so that the composition becomes bound to the packaging material, or polymerizes to form a polymeric coating or layer on the surface of the packaging material, or a combination of polymerization and bonding. The coated and irradiated packaging material is then used to form containers, packaging, or packaging components or leaflets that generate a uniform amount of ethylene inhibition from the olefinic inhibitor, so that the live production stored within the container has a consistent quality and extended service life. Extending the life span of fresh produce can result in a significant reduction in food waste. In some cases, packaging material is formed into a container, packaging, 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 contains the cyclodextrin inclusion complex with the compound olefinic inhibitor in the central pore of the cyclodextrin, therefore acting as an effective source of the olefinic inhibitor.
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6/83 [010] The invention contemplates a treated article that is a treated packaging material or container that has an irradiated cyclodextrin composition disposed therein. The cyclodextrin composition contains an inclusion complex. Within the inclusion complex, cyclodextrin molecules contain an effective amount of the olefinic ethylene generation inhibitor in production. 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 in a flexible, rigid or semi-rigid container. The treated container releases olefinic inhibitor in a confined volume within a packaging structure so that living plant material contained therein has an extended or more useful life span.
[011] The invention contemplates a cyclodextrin composition including one or more radiation polymerizable monomers and a cyclodextrin inclusion complex containing a cyclodextrin and an olefinic inhibitor. The invention also contemplates a cyclodextrin composition including a substituted cyclodextrin compound, in which the substituted cyclodextrin compound is reactive to electromagnetic irradiation, and in which some portion of the substituted cyclodextrin compound includes an inclusion complex. The invention also contemplates a radiation cured coating of a cyclodextrin composition so that a substituted cyclodextrin or cyclodextrin compound is attached to a polymer chain or backbone in which some portion of the bound cyclodextrin compound includes an inclusion complex. The invention also contemplates a radiation cured coating of a cyclodextrin composition in which cyclodextrin and / or cyclodextrin inclusion complexes are not part of the radiation polymerized polymer, but are instead retained or captured within the polymerized coating. The invention also contemplates a material of
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7/83 packaging which has surface functionalization on at least part of a main surface thereof, wherein the surface functionalization includes a radiation cured cyclodextrin composition.
[012] The invention also contemplates a method for forming an olefinic inhibitor inclusion complex with a cyclodextrin to form a cyclodextrin composition, followed by coating the cyclodextrin composition on at least part of a main surface of a packaging material or container, and irradiate at least the coated portion of the packaging material or container to form a treated slide or film.
[013] The invention also contemplates that the treated packaging material or container can be manufactured using a method according to which the treated packaging material or container is formed under conditions that have a reduced water content.
[014] The invention also contemplates the use of packaging material or treated container for packaging breathing material. The production material is confined within the packaging material or container and the treated portion of the treated packaging material or container is brought into contact with an appropriate amount and of water activation, so that the cyclodextrin releases the olefinic inhibiting material in sufficient concentration to inhibit ripening or maturation of production. The olefinic inhibitor is also released from the treated packaging material or container by exposure to a controlled level of humidity. During distribution and storage when the storage temperature of the packaged production material is low (for example, between about 0 ° C to about 14 ° C), the humidity in the confined volume around the production will be high (for example, between about 70% to about 100% relative humidity) due to the loss of normal water from the production breath in the confined packaging volume. In many cases, the amount of water vapor
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8/83 exceeds the amount that corresponds to 100% relative humidity, and liquid water condenses inside the package. The water vapor and / or liquid water released by the production within the confined volume of the package is sufficient for the release of the olefinic inhibitor. Alternatively, the internal humidity of the packaging material or container is adjusted by adding water before sealing the package or container to release the olefinic inhibitor. Relative humidity can be controlled by adding hydration (mist, spray or water vapor) to the air by humidifiers during packaging.
[015] The invention further contemplates a container or packaging for production that is produced from conventional packaging materials and contains a packaging leaflet comprising a section of a slide or film treated of the invention that can release the olefinic inhibitor by increasing or adding a controlled level of humidity.
DETAILED DESCRIPTION
Definitions [016] As used herein, the term “cyclodextrin composition” means a composition that contains a cyclodextrin inclusion complex that is (1) capable of coating a slide, film, or container and reacting with UV or UV radiation. electron beam to form a treated slide, film, or container; or (2) is coated on a slide, film, or container; or (3) is a polymerized layer on at least a portion of a main surface of a slide, film or container; or (4) is covalently attached to at least a portion of a main surface of a slide, film or container; or (5) a combination of (3) and (4).
[017] As used herein, the term “cure (do)” or “cure (do) with radiation” means to expose a cyclodextrin composition to electromagnetic radiation or electron beam radiation in conditions that cause
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9/83 the composition is subjected to the reaction as polymerization, bonding or grafting to a polymer or a surface, crosslinking, or a combination thereof. Electromagnetic radiation includes, but is not limited to, ultraviolet (UV) radiation, microwave radiation, and gamma radiation. Monomers and crosslinkers “radiation curable” or “radiation curable” are compounds that are polymerizable or crosslinked as a result of interaction with electromagnetic radiation or electron beam radiation. In some embodiments, radiation polymerizable monomers and crosslinkers are also polymerizable by thermal means.
[018] As used herein, the term "cyclodextrin" or "cyclodextrin compound" means a cyclomalto-oligosaccharide that has at least five units of glycopyranosis joined by an α (1-4) bond. Examples of useful cyclodextrins include α-, β-, or γ-cyclodextrin, with α-cyclodextrin having six glucose residues; β-cyclodextrin has seven glucose residues, and γcyclodextrin has eight glucose residues. Cyclodextrin molecules are characterized by a truncated and rigid conical molecular structure that has a hollow interior, or pore, of specific volume. "Cyclodextrin" may also include cyclodextrin derivatives, as defined below, or a mixture of one or more cyclodextrins. The following table lists properties of α-, β-, and γ-cyclodextrin.
TYPICAL CYCLODEXTRIN PROPERTIES
Α-CD β-CD γ-CD PROPERTIES
FROM CD
Degree ofpolymerization (n =)Molecular size (A °) 6 7 8 Internal diameter 5.7 7.8 9.5 External diameter 13.7 15.3 16.9 Height 7.0 7.0 7.0 Rotation +150.5 +162.5 +177.4 specific fa] ²⁵ D Complex color blue yellow Brown of iodine yellowish
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Solubility at 14.50 1.85 23.20 distilled water (g / 100 ml) at 25 ° C [019] As used herein, the term “cyclodextrin inclusion complex” means the combination of an olefinic inhibitor compound and a cyclodextrin in which the olefin inhibitor compound is disposed substantially within the pore of the cyclodextrin ring. The complexed olefinic inhibitor compound must meet the size criterion to fit at least partially into the internal pore or cavity of the cyclodextrin, to form an inclusion complex. Inclusion complexes of cyclodextrin include, inherently in the formation and existence of the inclusion complex, some amount of "non-complexed" cyclodextrin; this is due to the fact that (1) in modalities, the synthesis of the inclusion complex does not result in 100% formation of the inclusion complex; and (2) in modalities, the inclusion complex is in equilibrium with non-complexed cyclodextrin / non-complexed olefinic inhibitor. Each combination of cyclodextrin and olefin inhibitor has a characteristic balance associated with the cyclodextrin inclusion complex.
[020] As used herein, the term "cyclodextrin derivative" or "functionalized cyclodextrin" means a cyclodextrin that has a functional group attached to one of the hydroxyl groups of the chemical portion of the cyclodextrin glucose. An example is a group that makes the cyclodextrin derivative soluble in a radiation polymerizable monomer. Some cyclodextrin derivatives are described, for example, in U.S. Patent No. 6,709,746.
[021] As used herein, the term “olefinic inhibitor”, “olefinic inhibitor compound” or “olefinic inhibitor of ethylene generation” is intended to mean an olefinic compound that contains at least one olefinic double bond, has about from 3 to about 20 carbon atoms and can be aliphatic or cyclic, having at least minimal inhibiting activity or ethylene antagonist.
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11/83 [022] As used herein, the term “packaging material” means any packaging component in which production is contained or in which it is exposed to the volume confined within a production container or pouch. The packaging material includes, for example, sheets or films from which packaging for production confinement is made, or any packaging produced for production confinement, or any material used in or inside a package. The packaging material includes, for example, films and sheets of thermoplastic packaging, and wrapping or bags formed therefrom; coated or uncoated sheets and rolls of paper, as well as bags or cardboard boxes; thermoformed envelopes; wax or film coatings applied directly to production or in a container; multilayer packaging constructions; printed coatings, embossed signs, labels placed on or inside packaging or in production, adhesives used to close or seal packaging or adhere labels and the like; ink printed directly on the production, directly on the packaging, or on a label that is then adhered to the packaging; and the like. In embodiments, one or more packaging materials employed in a package include a cyclodextrin composition of the invention.
[023] As used herein, the term "treated packaging material" means a packaging material or container that has arranged on at least a portion of a main surface thereof a cyclodextrin composition and in which the cyclodextrin composition has been additionally cured.
[024] As used herein, the term “treated packaging leaflet” means a piece or section of treated packaging material that is inserted into production packaging or in
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12/83 some other container that defines a confined volume.
[025] As used herein, the term "treated laminate" or "treated laminate packaging material" means a cyclodextrin composition or cured cyclodextrin composition combined with and disposed between a surface of a first packaging material and a surface of a second packaging material, wherein the first and the second packaging materials are the same or different. In general, treated packaging materials include treated laminate packaging materials.
[026] As used herein, the term “treated container” or “treated packaging” means (1) packaging material that has been formed into a flexible, semi-rigid or rigid container or packaging to confine production, then coated with a composition cyclodextrin and cured; or (2) a treated packaging material that has been formed in a flexible, semi-rigid or rigid container or packaging. Treated containers include bags, boxes, packages, wrappers, and other such containers used to pack production material. Along with its intended use and for some period of time, the treated container will include a contained volume. Thus, the treated container will be closed or sealed to contain a confined volume; or it will be included within a confined volume.
[027] As used herein, the term “treated laminated container” means (1) a first packaging material that has been formed in a flexible, semi-rigid or rigid container to confine production, in which a cured cyclodextrin composition is combined with and arranged 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; or (2) a first packaging material that was formed in a flexible, semi-rigid or rigid container for
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13/83 confine production, wherein a cyclodextrin composition is combined with and disposed between a container surface and a second layer of a packaging material that is the same or different from the first packaging material, and then the cyclodextrin composition is cured; or (3) a treated laminate packaging material that has been formed in a flexible, semi-rigid or rigid container. In general, treated containers include treated laminated containers.
[028] As used herein, the term “permeable” as applied to a packaging material, a cured cyclodextrin composition, a treated packaging material, a treated container, a treated laminate packaging material, or a container treated laminate means that the material, container, or composition has an olefinic inhibitor permeability equal to or greater than 0.01 (cm ³ • mm / m ² • 24 hours • kPa (bar)) at standard temperature and pressure (STP ) and 0% relative humidity; or water vapor permeability equal to or greater than 0.1 (g • mm / m ² • 24 hours) at 38 ° C and 90% relative humidity, when measured according to ASTM D96; or O2 permeability equal to or greater than 0.1 (cm ³ · mm / m ² · 24 hours · kPa (bar)) at 23 ° C and 0% relative humidity, when measured according to ASTM D3985; or CO2 permeability equal to or greater than 0.1 (cm ³ · mm / m ² · 24 hours · kPa (bar)) at 23 ° C and 0% relative humidity, when measured according to ASTM D1434; or a combination of them. As used herein, the term “impermeable”, as applied to a packaging material, a cured cyclodextrin composition, a treated packaging material, a treated container, a treated laminated packaging material, or a treated laminated container means that the material, container, or composition has an olefinic inhibitor permeability of less than 0.01 (cm ³ · mm / m ² · 24 hours · kPa (bar)) in STP and 0% relative humidity;
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14/83 or water vapor permeability of less than 0.1 (g · mm / m ² · 24 hours) at 38 ° C and 90% relative humidity, when measured according to ASTM D96; or O2 permeability of less than 0.1 (cm ³ • mm / m ² • 24 hours • kPa (bar)) at 23 ° C and 0% relative humidity, when measured according to ASTM D3985; or CO2 permeability of less than 0.1 (cm ³ · mm / m ² · 24 hours · kPa (bar)) at 23 ° C and 0% relative humidity, when measured according to ASTM D1434; or a combination of them.
[029] The term “production” or “production material” includes any whole plant, part of a plant, such as a fruit, flower, cut flower, seed, bulb, seedling, root, leaf, flower, or other material that is breathing actively and, as a part of its maturation, generates ethylene as a maturation hormone (climacteric) or matures without breaks in ethylene and respiration (non-climacteric).
Compositions, Articles and Manufacturing Methods [030] It has been found that one or more cyclodextrin compounds are useful to form a cyclodextrin composition with the use of moderate conditions. Cyclodextrin compositions are useful for forming a coating on at least a portion of a main surface of one or more packaging materials or containers. After coating a cyclodextrin composition on at least a portion of a packaging material or container surface, the coated surface is irradiated with UV or electron beam radiation to form a treated slide, film, or container. In some embodiments, the treated packaging material is used to form a container. In other embodiments, the treated packaging material is used to form a treated packaging leaflet, in which a section of the treated packaging material is attached to or simply inserted into a production container. The treated container, or a container that has a treated packaging leaflet disposed inside, is used to package the production.
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[031] The use of the compositions, articles, and methods of the invention allows olefinic inhibitor compounds to be employed in a safe, convenient and gradual manner that avoids subjecting the cyclodextrin inclusion complex to stringent conditions that can cause loss of olefinic inhibitor of the cyclodextrin inclusion complex. In addition, the treated packaging material, containers, and packaging leaflets of the invention provide low, but constant, levels of olefinic inhibitor release from them when disposed within a confined volume in the presence of water vapor and thus provide long-term inhibition of ripening or maturation of production while arranged within the confined volume.
[032] The cyclodextrin compositions of the invention include at least one cyclodextrin inclusion complex and a monomer. In embodiments, the cyclodextrin inclusion complex is simply mixed with addition with the monomer in the desired ratio to form the cyclodextrin composition.
[033] The cyclodextrin used to form the cyclodextrin inclusion complex is selected for the specific volume of the cyclodextrin pore. That is, the pore size of cyclodextrin is selected to fit the molecule size of the olefinic inhibitor. The olefinic inhibitor is a compound having from 3 to about 20 carbon atoms, which comprises at least one olefinic bond and which comprises a cyclic, olefinic or diazo-diene structure. Examples of compounds useful as the olefinic ethylene generation inhibitor include 1-methyl cyclopropene, 1-butene, 2-butene, and isobutylene. Of these, 1-methyl cyclopropene, or 1MCP has been found to be particularly useful. It was found that 1-MCP has a molecular size that is suitable for the formation of an inclusion complex when combined with α-cyclodextrin, or α-CD. In embodiments, the inclusion complex contains about 0.10 to 0.99 mol of the olefinic inhibitor per mol of cyclodextrin, or about 0.20 to 0.95 mol of the olefinic inhibitor per mol of
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cyclodextrin, or fence in 0.30 The 0.90 mol of inhibitor olefinic per mol in cyclodextrin, or fence in 0.50 The 0.90 mol of inhibitor olefinic per mol in cyclodextrin, or fence in 0.50 The 0.80 mol of inhibitor olefinic per mol in cyclodextrin, or fence in 0.30 The 0.70 mol of inhibitor olefinic per mol in
cyclodextrin.
[034] Methods for forming cyclodextrin inclusion complexes are known and are described, for example, in U.S. Patent Nos. 6,017,849 and 6,548,448 as well as in Neoh, T. Z. et al., J. Agric. Food Chem. 2007, 55, 11020 to 11026. Typically, the cyclodextrin and the olefinic inhibitor are mixed together in a solution for a period of time sufficient to form the inclusion complex. In the case of 1-MCP and α-cyclodextrin, α-cyclodextrin is dissolved in water and 1-MCP is bubbled into the solution for a period of time at room temperature. The inclusion complex precipitates out of solution as it is formed and is thus easily isolated by simple filtration followed by vacuum drying. The dry cyclodextrin inclusion complex is then ready for use. Storage in a dry container with minimal empty space is sufficient.
[035] In some embodiments, the cyclodextrin inclusion complex is formed with a cyclodextrin derivative. Cyclodextrin derivatives are used to form the inclusion complex in some modalities to improve miscibility in the composition of cyclodextrin. Derivatives of cyclodextrin employed to enhance the miscibility of the cyclodextrin composition include any of the cyclodextrin derivatives described in US Patent No. 6,709,746 or in Croft, AP and Bartsch, R, Tetrahedron Vol. 39, No. 9, pages 1417 to 1474 (1983). In some embodiments in which a cyclodextrin derivative is used to form the cyclodextrin inclusion complex, the olefinic inhibitor is introduced in a non-water solvent, for example, a hydrocarbon that has 1 to 10 carbons, an alcohol that has 1 to 10 carbons, a heterocyclic solvent or
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17/83 aromatic that has 4 to 10 carbons. In some such embodiments, mixtures of one or more solvents are employed. In other embodiments, the inclusion complex is formed prior to the functionalization of the cyclodextrin derivative. In such modalities, care must be taken during functionalization to employ techniques and select functional chemistries from the group that avoid displacing the olefinic inhibitor from the inclusion complex, for example, by preferential inclusion of one of the compounds used in functionalization.
[036] Monomers useful in forming cyclodextrin compositions include any of the known compounds that have one or more unsaturated bonds that are polymerizable by free radical polymerization methods or plasma polymerization methods such as electron beam radiation polymerization. In embodiments, useful vinyl monomers include acrylates, methacrylates, acrylamides, allyl monomers, α-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 or methacrylic acid in which the ester groups are between 1 and 18 carbons, in some embodiments between 1 and 8 carbons, and are linear, branched, or cyclic . In modalities, mixtures of two or more monomers are used in the cyclodextrin compositions. In some such modalities, one or more monomers are selected for humidification, adhesion, or both enhanced of the cyclodextrin composition to the target substrate. In some such embodiments, one or more monomers are selected to provide specific permeability properties. In some embodiments, monomers are selected to provide targeted permeability of the cyclodextrin composition cured in water, or in the olefinic inhibitor, or both. Careful control of permeability is selected for optimal controlled release of the olefinic inhibitor during use. Several additional components, as described below, are still
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18/83 selected to control olefin inhibitor release properties and other physical properties of the cured cyclodextrin compositions of the invention.
[037] In some embodiments, monomers that have more than one unsaturated and polymerizable bond are used in cyclodextrin compositions, 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; divinyl benzene and derivatives thereof, and the like. Such monomers provide crosslinking to the cured cyclodextrin composition. Other compounds that are useful monomers in which UV polymerization is employed include photoactive crosslinking agents. Photoactive cross-linking agents include, for example, benzaldehyde, acetaldehyde, anthraquinone, substituted anthraquinones, various benzophenone-type compounds and certain chromophore-substituted vinyl-methyl-s-triazines, such as 2,4-bis (trichloromethyl) -6-p-methoxystyryl- s-triazine. In some such embodiments, a monomer that has more than one unsaturated and polymerizable bond, or a photoactive crosslinker, is present in less than about 10% by weight of the cyclodextrin composition, for example, in about 0.1% at 5% by weight of the cyclodextrin composition. In embodiments, the monomer or mixture of monomers is a liquid at the temperature in which the cyclodextrin composition is coated on a slide, film, or thermoplastic container. In some embodiments, cyclodextrin, the cyclodextrin inclusion complex, or both are miscible in the monomer or monomer blend.
[038] The cyclodextrin composition is a mixture with addition of the cyclodextrin inclusion complex and one or more monomers, and optionally one or more crosslinking agents, along with any additional components desirably included in the cyclodextrin composition. In modalities, the amount of cyclodextrin inclusion complex used in the composition of
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19/83 cyclodextrin is about 0.001% by weight to 25% by weight of the composition, or about 0.01% by weight to 10% by weight of the composition, or about 0.05% by weight to 5% by weight composition. The amount of cyclodextrin inclusion complex included in a particular formulation is selected based on the amount of desired olefinic inhibitor in the confined space within the treated container, along with variables such as water-coating permeability and the olefinic inhibitor. Criteria that inform about this selection are described in more detail below.
[039] In embodiments, one or more additional components are added to the cyclodextrin composition. Adhesion promoters, anti-fouling agents, thermal or oxidizing stabilizers, dyes, adjuvants, plasticizers, and small amounts of solvents are examples of additional materials that are added to cyclodextrin compositions in some embodiments. In some embodiments, the cyclodextrin composition includes a polymerization initiator. In some modalities in which the cure is carried out by UV radiation, it is desirable to include a photoinitiator that will absorb UV radiation and become activated, therefore initiating the polymerization of the unsaturated polymerizable monomer (s) and any other components of the cyclodextrin composition that contain UV polymerizable chemical moieties. 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 compositions at about 0.01% by weight to 5% by weight based on the weight of the cyclodextrin composition, for example, 0.5% by weight at 2% by weight. weight based on the weight of the cyclodextrin composition. Examples of suitable photoinitiators include those marketed under the trade name IRGACURE® by Ciba Specialty Chemicals Corp. from Tarrytown, NY, those marketed under the trade name CHEMCURE® by Sun Chemical Company of Tokyo, Japan; and
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20/83
LUCIRIN® TPO marketed by BASF Corporation of Charlotte, NC.
[040] In some embodiments, an additional component is a prepolymer. Prepolymers are formed in situ from the cyclodextrin composition by prepolymerizing them, optionally followed by the addition of more monomer and photoinitiator, or are added to the cyclodextrin composition in order to increase the coating viscosity of the composition before curing . Prepolymerization is a method of bulk or continuous polymerization, in which a smaller amount of polymerization, for example, 1% to 10%, of the bulk coating composition is carried out to achieve a target viscosity. Prepolymers are of any suitable molecular weight and are soluble in the monomer or monomers of the cyclodextrin composition. Prepolymers are formed in situ or added to the cyclodextrin composition in any amount that is useful to provide the 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, forming a prepolymerized cyclodextrin composition. In some embodiments, targeted viscosities for prepolymerized cyclodextrin compositions are about 0.01 Pa.s (10 cP) to 2Pa.s (2,000 cP), or about 0.1 Pa.s (100 cP) at 1 Pa.s (1,000 cP). In embodiments, one or more additional monomers, crosslinkers, initiators, or a combination thereof are then added to the prepolymerized cyclodextrin composition. The prepolymerized cyclodextrin composition is then coated and cured, wherein the viscosity of the prepolymerized cyclodextrin composition allows a thicker layer to be coated than would be practicable with the use of the cyclodextrin composition without prepolymerization. In embodiments, 25 micron and thicker coatings of prepolymerized cyclodextrin composition are formed, for example, between about 25 microns and 100 microns. Such coating thicknesses are useful, for example, when the composition of
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21/83 cured cyclodextrin is a pressure sensitive adhesive. In some embodiments, the cyclodextrin inclusion complex is added to the coating composition after prepolymerization; however, in many embodiments, the cyclodextrin inclusion complex is added prior to prepolymerization due to the fact that the mixing of the components is more easily performed before forming a higher viscosity composition.
[041] In some modalities, 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 preferably react with water molecules, so that it effectively acts to sequester the environment's moisture from the humidity of the air during standard processing conditions. The amount of water scavenger added must be a minimum amount to react with the hydration of the environment during processing. This is due to the fact that, in the intended packaging applications in which the cyclodextrin compositions are included in a production container, water is required to facilitate the release of the olefinic inhibitor in the container. Thus, a quantity of water scavenger must be provided in the cyclodextrin composition which is rapidly depleted once a substantial amount of water vapor is encountered. Examples of water scavengers suitably employed in the cyclodextrin compositions of the invention include various orthoesters and hexamethyldisilazane. In embodiments, about 1% by weight or less based on the total weight of the cyclodextrin composition of the water scavenger is added to the cyclodextrin compositions, for example, about 0.01% by weight to 1% by weight based on the total weight of cyclodextrin composition or about 0.05% by weight to 0.5% by weight based on the total weight of cyclodextrin composition.
[042] In some embodiments, an additional component is a desiccant.
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22/83
In the present invention, desiccants are employed to sequester water from the interior of a confined volume in which a respiration material is expected to generate an excess of the desired amount of water. The effects of excess water are described in more detail below. Desiccants are also added, in some embodiments, directly into a treated container or treated laminated container of the invention separately from the cyclodextrin composition itself; however, in some embodiments, the desiccant is added directly to the cyclodextrin composition for convenience and / or effectiveness. Suitable desiccant materials include, for example, silica gel and molecular sieve-type desiccants. The amount of desiccant incorporated within a cyclodextrin composition or cured cyclodextrin composition is not particularly limited and is selected based on the particular end use, that is, the type of packaging, volume of confined space, type of production to be packed and similar. In general, the amount of desiccant is selected to be about 0.001% by weight to 99% by weight based on the total weight of the cyclodextrin composition, or about 0.1% by weight to 50% by weight based on weight. total cyclodextrin composition, or about 1% by weight to 10% by weight based on the total weight of the cyclodextrin composition.
[043] Packaging materials that are suitably coated with a cyclodextrin composition in at least a portion thereof include any packaging material that is suitable for surface coating followed by UV or electron beam curing. Suitable packaging materials include paper and cardboard and other packaging materials based on natural and synthetic biomass, as well as synthetic petroleum-based thermoplastic woven or non-woven films, foils, fibers, or cloths that are useful as packaging materials. production, and composite materials including one or more of them. Some
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23/83 examples of packaging materials usefully used to form containers, labels, laminates (i.e., treated laminate packaging materials) or packaging leaflets include paper, cardboard, coated paper or cardboard, such as extruded coated paper or cardboard, recycled cardboard, woven or non-woven cloths, wood / thermoplastic composites, polyvinyl halides such as poly (vinyl chloride) (plasticized and non-plasticized) and copolymers thereof; polyvinylidene halides such as polyvinylidene chloride and copolymers thereof; polyolefins such as polyethylene, polypropylene, and copolymers and morphological variations thereof, including LLDPE, LDPE, HDPE, UHMWPE, metallocene polymerizable polypropylene, and the like; polyesters, such as polyethylene terephthalate (PET) or polylactic acid (PLA) and plasticized variations thereof; polystyrene and copolymers thereof, including HIPS; polyvinyl alcohol and copolymers thereof; copolymers of ethylene and vinyl acetate; and the like. Mixtures, alloys, reticulated versions of them, and composites of the same are also useful in several modalities. Two or more layers of such packaging materials are present in some embodiments such as multilayer films or cardboard constructions.
[044] The packaging materials contain, in some modalities, one or more fillers, stabilizers, colorants and the like. In some embodiments, packaging materials have one or more surface coatings on them. In some embodiments, the packaging material has a surface coating on it before coating the cyclodextrin composition. Surface coatings include protective coatings such as wax, acrylic polymer coatings and the like; coatings to make surfaces printable; coatings to make packaging materials otherwise permeable and impermeable; adhesive coating; initiators; adhesive layer coating; reflective or metallized coatings and
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24/83 similar. The type and function of surface coatings are not limited, in particular, within the scope of the invention; likewise, the way in which surface coatings are applied is not particularly limited. In various embodiments in which a surface coating will be exposed to the confined volume within a product package, the surface coating is subsequently coated with the cyclodextrin composition.
[045] In a commercially important modality, traders and distributors commonly use recyclable cardboard coated by extrusion of polyethylene or a cardboard box packaging to transport product. The polyethylene coating provides water resistance and water vapor protection in environments, usually hydrated and humid, which are typical of shipping and storage conditions for fresh fruits and vegetables. The printed cardboard packaging can vary from volume compartments to specialized showcase cardboard boxes. Printed marking areas are, in some modalities, highlighted marking areas. The extrusion-coated surface provides an opportunity to include a cyclodextrin composition of the invention.
[046] In some embodiments, the packaging material is treated with a corona or plasma treatment before coating the cyclodextrin composition. Such surface treatments are well known in the industry and are often used in industry to modify the surface energy of packaging materials, for example, to improve the wetting or adhesion of coatings or printed materials to the surface of a packaging material. packing. Such surface treatments are also useful in some embodiments to improve wetting and adhesion of cyclodextrin compositions to the packaging material.
[047] In some embodiments, the packaging material is treated with a primer before coating the cyclodextrin composition. In some such
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25/83 modalities, films and sheets of thermoplastics, used as packaging materials, are obtained pre-coated with an initiator; a wide variety of such films and foils are available in the industry and are aimed at improving the adhesion of various types of coatings to them. In some embodiments, a flat film, or foil, is coated "in line" with an initiator designed to improve adhesion of polymerizable radiation coatings before coating the cyclodextrin composition. A variety of such coatings and technologies are available and a person skilled in the art will understand that initiator coatings are optimized for each coating formulation and each type of film or foil. Some examples of starter compositions suitably arranged between the packaging material surface and the cyclodextrin compositions of the invention include polyethyleneimine polymers such as polyethyleneimine, alkyl modified polyethyleneimines in which the alkyl has 1 to 12 carbon atoms, poly (ethyleneimine urea), ethyleneimine polyamine adducts and polyamine epichlorohydrin adducts, acrylic ester polymers such as acrylic ester / acrylamide copolymers, methacrylic ester / acrylic ester / acrylamide copolymers, polyacrylamide derivatives, polyacrylamide derivatives containing oxazoline groups, and poly (acrylic esters). In the embodiments, the initiator composition is an acrylic resin, a polyurethane resin or a mixture thereof. In embodiments, the initiator composition includes at least one radiation curable polymer, oligomer, macromonomer, monomer, or a mixture of one or more of them.
[048] In some embodiments, the packaging material is a blade, or film, that is formed in a suitable container to confine a product in a confined space. In other embodiments, the packaging material is a foil, or film, which is converted into coupons, strips, plates and the like for the purpose
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26/83 insertion into the confined space defined by an otherwise untreated product container. In some modalities, coupons, strips, plates and the like are labels that are applied, adhesively, to the product or the container. In some such modalities, coupons, strips, plates and the like are labels that are additionally printed with one or more marking areas. In the modalities, the marking areas are highlighted. The cyclodextrin composition is present, in various modalities, on any surface that is exposed, directly or indirectly, to the confined space. In some embodiments, the packaging material is treated laminate. In some embodiments, the treated laminate is permeable to the olefinic inhibitor on one side of it and is impermeable to the olefinic inhibitor on the second side of it. In some embodiments, the packaging material is a treated laminate that is permeable to water on at least one first side of it.
[049] Suitable containers for enclosing the product within a confined space include, for example, bags, boxes, cardboard boxes, pallets and baskets. In some embodiments, the package is designed to contain a single item of product, such as a bag to hold a banana or a head of lettuce; in other modalities, the package is a cardboard box to hold multiple items, such as a cardboard box to hold a bushel of apples or several pints of wild fruit; in still other modalities, the container is designed to enclose a pallet of smaller product boxes or baskets, such as larger polyethylene bags that enclose a pallet of wild fruits for transportation. In still other modalities, the container is a truck, boat or airplane in which a controlled and / or sealed environment is provided for product transportation.
[050] In many embodiments, more than one packaging material is used to form a container; in such embodiments, the cyclodextrin composition is present in one or more packaging components. On a
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27/83 illustrative example, a semi-rigid polypropylene container is filled with product and then sealed with a polyvinyl chloride film. The product includes a paper tag attached to the product. Inside the container is a polyester pouch or cup that contains a spicy sauce, sauce or other condiment. The bag or body has marking areas printed on it. In this example, the cyclodextrin composition is present in all or a portion of an inner surface of the container or film, an outer surface of the cup or bag or paper and / or included in the ink that is printed on the cup or on the handbag. Alternatively, the cyclodextrin composition is included in a package leaflet or on a label that is added separately to the container before sealing with the film. In some embodiments, a combination of more than one such surface includes the cyclodextrin composition. In yet another illustrative example, a cardboard box coated by extrusion of polyethylene is coated or printed on its surface with a cyclodextrin composition, followed by curing. The cardboard box is then filled with product, stacked on a pallet with a plurality of other cardboard boxes and the pallet is confined to a polyethylene bag. In some embodiments, all cardboard boxes include the cured cyclodextrin composition; in other embodiments, only one, or a percentage of the cardboard boxes, includes the cured cyclodextrin composition. In some examples of this technology, the bag additionally contains a controlled atmosphere or a modified atmosphere or is selectively in a permeable membrane material. Such variations in atmosphere and permeable membrane materials are discussed in detail below. In some embodiments, the bag additionally contains a desiccant in a bag or sachet.
[051] In yet another representative example, a plastic bag containing a product is a treated laminated container, that is, the composition of
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28/83 cured cyclodextrin does not come into direct contact with the inside of the container. The cyclodextrin composition is directly cured in a first packaging material with a second packaging material applied on top of the cyclodextrin composition and is cured after lamination to form a treated laminate; the treated laminate is then transformed into a bag. The packaging material that forms the outside of the bag is impermeable to the olefinic inhibitor. The packaging material that comes into contact with the inside of the bag is at least permeable to the olefinic inhibitor. At least one of the packaging materials is permeable to water vapor. In a related example, the treated laminate is a packaging film, for example, a cardboard box or other container for production material. In another related example, the cyclodextrin composition is directly cured to a first packaging material with a second packaging material applied on top of the cyclodextrin composition and is cured after lamination to form a treated laminate; the laminate is tensioned (oriented or stretched) monoaxially or biaxially before or after the cyclodextrin composition is cured. After curing and tensioning, the laminate is treated into a bag or used as a packaging for a 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 affixed to a container to form a treated laminated container. The pressure sensitive adhesive is adhered to the inside or outside of the container to form a treated laminated container.
[052] In some embodiments, the packaging material is applied directly to the product, for example, as a continuous or discontinuous coating or as part of an adhesive or in characters printed on a printed or printed product label. reverse. In such modalities,
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29/83 all or a portion of the coating, or label, contains the cyclodextrin composition. In some embodiments, an adhesive used to adhere a label to a product or package, or to seal a package, includes the cyclodextrin composition. The label is attached to the inside or outside of the package; that is, the contact surface with the interior of the confined volume, or the surface that does not come into contact with the interior of the confined volume, directly, but only indirectly, for example, through a permeability of the material of packaging to water and / or the olefinic inhibitor. Such constructions are modalities of treated laminate containers. Treated laminate containers include those that have a cured cyclodextrin composition that is disposed between a surface of the container and a second layer of a packaging material that is the same or different from the packaging material that is the packaging material of which the container It is formed. In such embodiments, the cyclodextrin composition, in general, is not in direct contact with the inner confined volume of the container; that is, it is arranged between two layers of the packaging material. Therefore, the packaging material surface, in contact with the product and also in contact with the cured cyclodextrin composition, must be permeable to water and the olefinic inhibitor, in order for the olefinic inhibitor to be released from the cyclodextrin inclusion complex. and for the inner volume of the container. In some embodiments, the laminate structure is permeable to the olefinic inhibitor on the first side of it and is impermeable to the olefinic inhibitor on the second side of it; in some embodiments the container is a treated laminate container in which the laminate structure is water permeable on at least one side of it.
[053] In some embodiments, the packaging material itself is permeable to the olefinic inhibitor. In some such embodiments, the cyclodextrin composition is coated in, or placed in contact with, the outside of the package by
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30/83 lamination medium and the olefinic inhibitor is released so that it diffuses through the package in the interior space where the product is located. In some such modalities, the packaging material is also permeable to water and the release of the olefinic inhibitor is controlled by water vapor that permeates the packaging material inside the confined volume; in other such modalities, the packaging material is impermeable to water and the release of the olefinic inhibitor is controlled by the humidity of the environment that leaves the outside for the confined 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 escape of the olefinic inhibitor from the confined space that defines the product package. In still other modalities, the packaging material itself is permeable to the olefinic inhibitor, however, only one or more surface treatments, coatings or layers (in the case of a multilayer film or a cardboard box, for example) provide a barrier function .
[054] In treated laminate containers, two different packaging materials are employed in some modalities such as the first and the second packaging materials between which the cyclodextrin composition is placed; as such, the packaging materials can be of differentiable permeability. Therefore, for example, the side facing the inside of the laminate is permeable to the olefinic inhibitor, however, in some modalities, it is impermeable to water, while the side facing the outside of the laminate is impermeable to the olefinic inhibitor and, in some modalities , is permeable to water. In some such embodiments, a controlled humidity atmosphere provided outside the container - such as in a storage facility - is used to control the release rate of the olefinic inhibitor, rather than the interior atmosphere within the container itself.
[055] Cyclodextrin compositions are coated on the surface of a packaging material, or directly on the product, and cured. The coating is
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31/83 made using any of the known coating technologies available in industries where mixtures of curable monomers are coated prior to curing. In some embodiments, the coating is done without applying high temperatures, that is, through the use of ambient temperatures in a processing facility. In other embodiments, the temperature during coating and curing is between approximately 5 ° C and 75 ° C or between approximately 0 ° C and 25 ° C. Useful coating techniques employed to coat the cyclodextrin compositions include, for example, matrix coating, curtain coating, soak coating, opening coating, chamfer coating, coiled wire extraction coating, dip coating, coating brush, spray coating, standard coating, such as rotogravure coating, and printing coating that employs printing technologies such as flexographic printing, inkjet printing, lithographic printing techniques, letter printing and screen printing. The viscosity profile of the cyclodextrin composition that includes properties, such as shear thinning, the shape and composition of the packaging material or product, and the desire to coat all or a portion of a surface, which of the known coating technologies are useful for coating cyclodextrin compositions. For example, matrix coating, notch bar coating and the like are usefully used to coat an entire substantially flat blanket of packaging material, since, in the modalities where only a portion of a surface is to be coated, or coating in formed container or product, it is desirable, one or more spray coating, dipping or printing technologies are desirably employed. When only a specific portion of a packaging material is to be coated, coating by printing, or in some embodiments,
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32/83 rotogravure coating is desirable. In some of these embodiments, the print coating is a prominent marking area.
[056] Radiation-curable inks, such as UV-curable inkjet and flexographic inks, are known in the industry and such devices for applying and curing such inks are easily obtained. In addition, radiation curable ink formulations are easily modified to include the amount of the cyclodextrin inclusion complex necessary to deliver the required amount of the complexed olefinic inhibitor to a surface of one or more packaging materials. Therefore, in an embodiment of the invention, a UV-curable inkjet ink is modified to include an amount of a cyclodextrin inclusion complex, for example, by mixing by adding the cyclodextrin inclusion complex to the ink; the modified inkjet ink is delivered in a target area to the packaging material and cured to provide a treated packaging material. Other printing techniques, for example, flexographic printing, are also useful in delivering an accurate and reproducible amount of the cyclodextrin inclusion complex to a packaging material by similarly incorporating the cyclodextrin inclusion complex that contains olefinic inhibitors. Large-scale production of packaging will, in some modalities, provide greater efficiency with flexographic printing instead of inkjet printing.
[057] The desired thickness of the coated cyclodextrin composition layer is dictated by the amount of the cyclodextrin inclusion complex in the cyclodextrin composition, the inherent equilibrium ratio of the cyclodextrin inclusion complex with non-complexed olefinic inhibitor, the permeability of the composition of cyclodextrin cured to the olefinic inhibitor, viscosity or coating thickness requirements of the technique employed to coat the cyclodextrin composition, the size of the portion of the surface area that
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33/83 contains the cured cyclodextrin composition, the type of product to be packaged and the volume of the confined space around the product. In short, the coating thickness is selected to provide a complex amount of inclusion of cyclodextrin that is effective in providing an adequate atmospheric (gaseous) concentration of the olefinic inhibitor to the confined space so that the product's life is extended. In some embodiments, an effective amount of the olefinic inhibitor in the atmosphere within the confined space of the product container is between approximately 2.5 parts per billion (ppb) and approximately 10 parts per million (ppm), or between approximately 25 ppb and 1 ppm . In various embodiments, the coating thickness is between approximately 0.001 micrometer (pm) and 10 millimeter (mm) thick, or between approximately 0.01 pm and 1 mm thick, or between approximately 0.1 pm and 0.5 mm thick, or between approximately 1 pm and 0.25 mm thick, or between approximately 2 pm and 0.1 mm thick.
[058] Since the cyclodextrin composition is coated on a packaging material, it is cured in situ to form a treated packaging material. In situ curing is done without the need to employ high temperatures; however, in some modalities, elevated temperatures are employed, in an appropriate manner; the curing process is not limited, in particular, to the temperatures employed. For example, in the embodiments, the temperature employed during curing the cyclodextrin composition is approximately 0 ° C to 135 ° C, or approximately 30 ° C to 120 ° C, or between approximately 50 ° C to 110 ° C. Maintenance of both the coating and curing temperatures at or below approximately 100 ° C is easily accomplished. In modalities where the cyclodextrin inclusion complex is 1MCP complexed with α-cyclodextrin, elevated temperatures do not cause a noticeable release of the olefinic inhibitor from the cyclodextrin inclusion complex.
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34/83 [059] In some modalities, in situ curing is performed using UV radiation. UV radiation is electromagnetic radiation that has a wavelength between 10 nm and 400 nm. In embodiments, wavelengths between about 100 nm and 400 nm are useful; in other embodiments, wavelengths between about 200 nm and 380 nm are useful. Wavelength, as well as radiation intensity and exposure time, is selected based on processing parameters such as the absorption characteristics of the photoinitiator employed, polymerization kinetics of the selected monomer (s), and thickness of the cyclodextrin composition coating. Suitable photoinitiators and amounts employed in the cyclodextrin compositions are described above. Useful methodologies and criteria to consider in UV curing are described, for example, in U.S. Patent No. US 4,181,752.
[060] In modalities, the cure is carried out in an environment that is substantially free of atmospheric hydration, air or both. Such an environment is achieved, in some modalities, by purging the area coated with an inert gas such as carbon dioxide or nitrogen during curing. In other embodiments, more conveniently where the coated packaging material is a flat sheet or film, water and air are properly excluded during curing by applying a UV-transparent water-impermeable liner on top of the coated uncured cyclodextrin composition. The coated cyclodextrin composition is cured by radiating through the lining; then the liner is removed, for example, to facilitate wrapping of the treated packaging film or foil, where the layers of film or foil provide an adequate 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 package leaflet, at which point the liner is removed. The lining material is not
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35/83 particularly limited in composition or thickness and is selected for UV transparency at the desired wavelength. In embodiments, the liner is selected to have a sufficiently low adhesion level for the cured cyclodextrin composition that the liner can be removed after curing without appreciable damage to the cured cyclodextrin composition. In some embodiments, the liner is added after curing to facilitate storage of the treated packaging material or treated container; in such cases, the ceiling does not need to be transparent to radiation, but instead, it is selected primarily to exclude water.
[061] In some embodiments, curing of the coated cyclodextrin composition is performed using electron beam radiation, or e-beam. In other embodiments, prepolymerization of the cyclodextrin composition is followed by coating on a packaging material, and subjecting to e-beam radiation in order to crosslink the cyclodextrin composition. In some such embodiments, additional monomers, which include monomers with more than one polymerizable chemical moiety, are added to the polymerized cyclodextrin composition before coating and subjecting to e-beam radiation. E-beam methods used to polymerize the cyclodextrin composition are described, for example, in the Web article by Weiss et al., “Pulsed Electron Beam Polímerization”. posted on January 1, 2006 (http://www.adhesivesmaq.com/Articles/Feature Article / 47965fdd41 bc801 OVqnVCM 1 Q0000f932a8c0). Numerous methods of pelimerization and / or crosslinking facilitated by e-beam are described in both patent and non-patent literature. Some examples of useful methods to polymerize and / or crosslink the cyclodextrin compositions of the invention include, for example, U.S. Patent ^Nos. US 3,940,667; 3,943,103; 6,232,365; 6,271,127; 6,358,670; 7,569,160; 7,799,885, and the like.
[062] The e-beam is a high energy ionization radiation that creates
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36/83 free radicals and is able to penetrate materials that are opaque to UV radiation. As such, the use of polymerization or cross-linking by e-beam presents the possibility of grafting components of the cyclodextrin composition into the packaging material directly. Many of the packaging materials listed above, for example, polyolefin, polyvinyl chloride, and polystyrene, are susceptible to e-beam radiation; that is, one or more free radicals are formed along the main polymer chain in some cases by e-beam irradiation. Free radical formation along the polymer backbone, in turn, presents an opportunity for the polymer backbone to bind to one or more components of the cyclodextrin composition. In embodiments, one or more inclusion complexes of cyclodextrin or monomers are attached, or grafted, to the packaging material using e-beam-mediated polymerization or e-beam-mediated crosslinking. The delivered radiation dose is carefully adjusted in each case to avoid domination by the concurrent chain splitting process.
[063] In the manufacture of the cyclodextrin compositions of the invention wherein the cyclodextrin composition comprises the cyclodextrin inclusion complex formed from 1-MCP and α-cyclodextrin (1-MCP / c / a-CD), it has been found that Careful control of water content during coating, curing, and subsequent storage before use is useful to maintain the stability of the 1-MCP / c / aCD complex. As water is reduced, 1-MCP is more controllably maintained within the central pore of α-cyclodextrin. Storage of treated packaging materials containing 1-MCP / c / a-CD is advantageously carried out or by covering the treated portion of the treated packaging material with a liner that is impermeable to water vapor; or in the case of treated films or sheets formed from water vapor impermeable thermoplastics, roll the films or sheets into rolls, or store sheets or containers in piles; or otherwise contain
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37/83 the packaging materials treated in a low humidity environment. In some embodiments, bulky quantities of treated packaging materials, such as rolls of treated packaging film or nested stacks of treated containers, are wrapped in water-impermeable plastic or foil packages or confined in water-impermeable bags for storage and / or send.
[064] In some embodiments, where a liner is applied over the cured cyclodextrin compositions, the liner includes one or more desiccants. In some such modalities, desiccants are integrated or adhered to the liner. The desiccant is used together with the liner itself to exclude water during storage and / or shipping. Examples of desiccants that are suitably employed include silica gel, charcoal, calcium sulfate, calcium chloride, montmorillonite clay, and molecular sieves. The desiccant is attached to the liner in such a way that it remains substantially attached to the liner when the liner is removed from the treated packaging material or treated container.
[065] In some embodiments, a treated packaging material or treated laminate is stretched before or after curing the cyclodextrin composition. Monoaxial or biaxial stretching, or stripping by stripping, of materials forming thermoplastic film and laminates formed from such materials is carried out as an efficient and economical way to form thin films with intensified strength. Where the cyclodextrin composition is applied to a thermoplastic film before stripping, a relatively thick coating and / or a high concentration of the cyclodextrin inclusion complex is employed, as the layer containing the cyclodextrin inclusion complex is predictably made thinner at the prescribed stretch ratio.
3. Uses of Compositions, Methods and Articles [066] Treated packaging materials and treated containers are
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38/83 usefully employed in the production of feedlots. The treated package leaflets are usefully included within the confined volume of package production. In embodiments, the treated packaging material, treated container, or treated package leaflet is arranged in such a way that the cured cyclodextrin composition comes into contact with the interior atmosphere of the confined volume that surrounds one or more items of production, the confined volume is provided by the container. The type and shape of the production container are not particularly limited; any bag, box, packaging, bathtub, glass, pellet bag, transport interior (e.g. truck interior), etc. defining a confined space usefully employs the treated packaging materials, containers, and / or package leaflets of the invention.
[067] The surface area and thickness of the cured cyclodextrin composition exposed to the interior of a production vessel is selected to provide an appropriate atmospheric (gaseous) concentration of the olefinic inhibitor to the confined space in such a way that the production life is optimized . In many embodiments, optimum production life means extended for the maximum amount of time possible. The optimal atmospheric concentration of the olefinic inhibitor is dictated by the type of production to be packaged and the expected storage temperature of the production as well as the partial pressure of the olefinic inhibitor at the target temperature. Factors affecting the provision of the optimal atmospheric concentration of olefin inhibitor include the amount of cyclodextrin inclusion complex in the cyclodextrin composition, the inherent equilibrium ratio of the cyclodextrin inclusion complex with non-complexed olefin inhibitor, the permeability of the cyclodextrin composition cured to the olefinic inhibitor, the permeability of the packaging material to the olefinic inhibitor - that is, the expected loss rate of the olefinic inhibitor to the outside of the package or container - to requirements for coating thickness or viscosity of the technique employed to coat the composition
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39/83 of cyclodextrin, the volume of the confined space surrounding the production, and the amount of water expected within the container as a result of the initial added / confined amount and expected transposition of the plant material. If the container is not completely sealed to the outside atmosphere, for example, if there are gaps or the packaging material itself has pores or holes, then any expected loss of released olefinic inhibitor (gaseous) also needs to be taken into account when calculating the amount of cyclodextrin composition to be disposed inside the production container.
[068] In modalities, the amount of olefinic inhibitor in the atmosphere that is required for a particular packaging application is estimated based on which production is to be packed and the known effective level of that inhibitor in relation to the specific production material; then the coating thickness and coated area (i.e., the total coating volume) are varied based on the confined volume, and concentration of the cyclodextrin inclusion complex included in the cured cyclodextrin composition. Other factors affecting release of olefinic inhibitor from the cyclodextrin inclusion complex within a cured cyclodextrin composition of the invention include the presence and amount of humectants or desiccants within the package, water permeation / adsorption / absorption capacity and 1-MCP of the composition of cured cyclodextrin, permeation / adsorption / water absorption capacity and 1-MCP of the packaging material, any controlled or modified atmosphere present within the package, and respiration rate of the targeted production material. Additionally, the amount of water supplied within the confined space, that is, the amount of water vapor vs. liquid water in the confined space at the target temperature also needs to be considered.
[069] In such calculations, the delivery value of a quantity of coating targeted to the targeted confined volume is realized. Certain
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The embodiments described above are particularly advantageous in delivering a precisely measured amount of olefinic inhibitor to a confined volume, as well as allowing an easily varying amount of cyclodextrin composition to a target container. For example, inkjet printing is well known for delivering accurate and easily varied volumes of material to substrates over an easily varied volume. In addition, UV-curable inkjet inks are known in the industry and such devices for applying and curing such inks are easily obtained. It has been found that UV-curable inkjet formulations are easily modified to include the small amount of the cyclodextrin inclusion complex necessary to achieve delivery of the required amount of olefinic inhibitor to a surface of one or more packaging materials. Thus, in an embodiment of the invention, a UV-curable inkjet ink is modified to include an amount of a cyclodextrin inclusion complex, for example, by adding the cyclodextrin inclusion complex to the ink by mixing; in some such embodiments, the ink is dried with a desiccant to remove water before adding the cyclodextrin inclusion complex. The modified inkjet ink thus obtained is delivered over a target area to the packaging material and cured to provide a treated packaging material. Other printing techniques, for example, flexographic printing, are also useful in delivering an accurate and reproducible amount of cyclodextrin inclusion complex to a packaging material.
[070] Another advantage of using printing techniques to deliver the cyclodextrin compositions of the invention is that printing is easily incorporated into a production assembly line configuration. In addition, ink is easily kept dry while in a tank awaiting printing on a production line. In that way, problems of
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41/83 long-term storage found in some applications, that is, the need to keep the cyclodextrin composition cured dry, is avoided. Yet another advantage of using printing techniques to apply cyclodextrin compositions is the ability to employ reverse print labeling. In reverse print labeling, a transparent identification label is printed with signs on the side of the label that will come in contact with the package, typically by virtue of an adhesive. Alphanumeric characters are thus printed on the reverse, that is, as mirror images of them. When the label is applied to the package, the identification label protects the printed signs of wear and shear. In current use, the cyclodextrin composition printed in reverse labeling mode is then arranged against the package or production. Reverse print labeling is also useful for printing on what will become the inside of a transparent package, such that the printed signs are directly exposed to the inside of the package.
[071] In some embodiments, delivery of a targeted amount of coating to the targeted confined volume is accomplished by coating and curing a cyclodextrin composition on a flat mat, then cutting the mat in portions as treated package leaflets. In some such embodiments, treated package leaflets of varying sizes are cut to provide different amounts of cyclodextrin inclusion complexes to address different production requirements or different confined volumes. In other embodiments, uniform sections are cut and one, two, or more sections are included as package leaflets treated in multiple packages depending on the type of production and volume confined in each application. For example, in modalities where the treated package leaflet is a label, a label is applied to each production item and several production items are included in a single confined space. Containers of varying size that carry a varying number of items of
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42/83 production are easily addressed in this way.
[072] Still in a different set of modalities, the adhesive coated on a label is used on the outside of a package to provide a packaging material that is a laminated packaging material.
[073] In some embodiments, the packaging material used to make the treated packaging materials of the invention and the treated packages and containers of the invention employ additional means to control the amount of water (vapor and / or liquid) contained within the treated package. while in the presence of the production material. While the amount of water in a confined space of the package is of concern from the point of view of releasing the olefinic inhibitor from the cured cyclodextrin compositions of the invention, it is well known that very high levels of hydration in a package containing production material it is also separately harmful for certain hydration-sensitive production (berries, citrus, lettuce, mushrooms, onions, and peppers, for example). Excessive hydration triggers various physiological disturbances in some post-harvest vegetables and fruits, which shortens shelf life and quality. In particular, liquid water in the form of condensation on production material surfaces accelerates deterioration and considerably shortens storage life. In some embodiments, internal moisture controllers (humectants and desiccants) are incorporated in porous sachets, within the packaging material of the invention, or even within the cyclodextrin compositions themselves in conjunction with the treated packaging material of the invention. In modalities, humidity controllers help to maintain relative humidity in an optimal package (about 85% to 95% for cut fruits and vegetables), reduce loss of hydration from the production material itself, and / or prevent accumulation of hydration in excess in empty space and interstices where microorganisms can proliferate. The amount of 1-MCP incorporated within the
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43/83 packaging structure will be different in packages that have excess water as contrasted by low moisture packaging of low-transpiration post-harvest products. Therefore, in order to operate the technology, a number of factors (chemical and biological) will be considered to manufacture optimal packaging structure and bulky shipping containers for different groups of post-harvest products.
[074] The treated packaging materials of the invention are also useful in embodiments in which modified atmosphere packaging (MAP), equilibrium modified atmosphere packaging (EMAP), or controlled atmosphere packaging (CAP) is employed. The objective in MAP is to provide a desired atmosphere around production by providing a sealed container that has controlled permeability for oxygen and carbon dioxide, which results in an improvement in production quality when compared to air storage. Typically, the permeability of the container changes with temperature and partial pressures of each gas outside the container. The objective in CAP is to move part or all of the atmospheric air composition (78% in N2, 21% in O2) into the container with, for example, carbon dioxide or nitrogen or a mixture of two or more gases in a desired proportion . A number of patents have established several MAP and CAP resources. Patent No. US 7,601,374 discusses both approaches and also references a substantial list of other patents issued for various MAP and CAP technologies. It will be appreciated that the cured cyclodextrin compositions of the invention find additional utility in conjunction with MAP, CAP, or technologies that combine resources from both approaches.
[075] MAP is a useful approach for maintaining enhanced flavored fruits and vegetables while minimizing the development of undesirable aromas due to fermentative metabolism or odor transfer from fungi or other sources. MAP
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44/83 is recognized for improving resistance to post-harvest stresses, decay and other plant disorders. An 'active package' that has a modified atmosphere integrated with the controlled release of an olefinic inhibitor, as delivered by the cyclodextrin compositions of the invention, will improve the quality of fresh cut fruits and vegetables for consumers that includes unique service, ready-to-eat packaging and containers for vending machines. In an exemplary embodiment of the invention, MAP or CAP is used in conjunction with the treated packaging materials of the invention for larger polyethylene bags used to package box pellets, in which the boxes contain fresh produce. Such pellet-sized bags are widely used for shipping production pellets, supported in boxes; bags are used for the purpose of confining production to a modified or controlled atmosphere during shipment. In some such embodiments, bags, cardboard boxes (for example, polyethylene-coated cardboard), labels on boxes or bags, a treated leaflet, or a combination of two or more of them include treated packaging material of the invention.
[076] EMAP is a method to help extend the shelf life of fresh produce by optimizing the equilibrium atmosphere in the package. This is achieved by modifying the permeability of the packaging film. Microperforation of film is a way to regulate equilibrium concentrations of O2 and CO2. Microperforated films are films with openings or, otherwise, made porous, by puncture or by stretching a film made of a mixture of a thermoplastic material and particulate charge. These films allow transfer only by diffusion of molecular gas / vapor and block the transfer of liquid. Examples of microperforated or microporous films include FRESHHOLD ^® film, available from River Ranch Technology, Inc. of Salinas, CA; P-PLUS® film, available from Sidlaw Packaging of Bristol, Great
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Britain and described in U.S. Patent ^Nos. US 6,296,923 and 5,832,699; and film Clopay Plastic Products Co. of Mason, OH described in U.S. Patent ^Nos. US 7,629,042 and 6,092,761.
[077] Additionally, in some embodiments of the invention, the gas permeability of non-perforated and non-porous films is modified simply by making films with different thicknesses or by using the selectivity of hydrophilic films produced from segmented block copolymers, and using these materials as packaging materials in conjunction with the cured cyclodextrin compositions. Segmented block copolymers or multiblock copolymers consist of alternating soft flexible segments and rigid crystallizable segments. The properties of segmented block copolymers are varied by changing the block lengths of the flexible (soft) and rigid segments. Rigid and flexible segments are thermodynamically immiscible and, therefore, phase separation occurs. The rigid segments crystallize and form lamellae in the continuous soft phase. Rigid segments may contain groups of starch, urethane or ester, while the flexible segments are usually polyesters or polyethers - poly (ethylene oxide) (PEO) and / or poly (tetramethylene oxide) more hydrophobic (PTMO). In breathable film, the gas vapor is transported mainly through the soft phase; Selective gas permeability depends on the density of the hydrophilic groups in the polymer, the relative humidity, and the temperature.
[078] The treated packaging materials of the invention are also useful in embodiments in which specialized and selectively permeable packaging materials are employed. An example of a selectively permeable packaging material is BreatheWay® packaging, currently used in conjunction with fresh cut production provided by Apio, Inc. of Guadalupe, CA (www.breatheway.com; see also www.apioinc.com).
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BreatheWay® films are selectively permeable membranes that control inward flow of oxygen and outward flow of carbon dioxide in order to provide adjusted O2 / CO2 ratios to extend shelf life. The membranes are also responsive to temperature. While such packaging provides improved O2 / CO2 ratios to extend the shelf life of breathing productions, it does not otherwise inhibit ripening of production. Examples of other suitable hydrophilic breathable films include PEBAX®, a thermoplastic polyamide manufactured by Total Petrochemicals USA, Inc. of Houston, TX; SYMPATEX ^® , a block copolymer made of breathable hydrophilic polyether ester by SympaTex Technologies GmbH from Unterfohring, Germany; HYTREL®, a thermoplastic polyester elastomer manufactured by DuPont deNemours and Co. of Wilmington, DE; and segmented polyurethanes such as ELASTOLLAN® (ELASTOGRAN®) and PELLETHANE®, supplied by Dow Chemicals of Midland, MI. These polymers have a large and selective gas permeability range. The cured cyclodextrin compositions of the invention, in conjunction with such a permeable membrane technology, represent a complete solution for extending the shelf life of respiratory products.
[079] It will be appreciated that the end-use articles and applications of the invention benefit in a number of ways from the advantages offered by the compositions and methods described in this document. Inclusion complexes of cyclodextrin are easily formed and isolated with the use of moderate conditions and high yields of formation of inclusion complexes are performed. The cyclodextrin inclusion complexes are easily stored until they are added to a cyclodextrin composition. The cyclodextrin compositions are easily formed, coated, and cured using moderate conditions with generally small amounts of the cyclodextrin inclusion complex added to a sprayable or coatable composition and
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47/83 curable with easily varied viscosity. Cured cyclodextrin compositions are easily stored or can be formed and used on a production line. A variable and precise amount of cyclodextrin inclusion complex is easily and reproducibly added to production packages. A variety of easily deployed methods for delivering cured cyclodextrin compositions to production packages and packaging materials is possible.
4. 1-Methylcyclopropene (1-MCP) as the olefinic inhibitor [080] In modalities where 1-MCP is the olefinic inhibitor, the target concentration for many production items is between about 2.5 ppb to about 10 ppm , or between about 25 ppb and 1 ppm. In embodiments, the cyclodextrin inclusion complex of 1-MCP is formed with α-cyclodextrin; that is, 1-MCP / c / a-CD. One factor in addition to these factors mentioned above that affect the release of 1-MCP from 1-MCP / w / a-CD is the amount of water contained in the confined space. This requires consideration of the amount of water supplied within the confined space, the amount of water released by respirator production material, and the amount of water retained within the package, as that amount changes with plant respiration.
[081] In embodiments of the invention in which the cyclodextrin inclusion complex 1-MCP / c / a-CD is employed in cyclodextrin compositions, cured cyclodextrin compositions, treated packaging materials, and / or treated containers of the invention, production it is packaged in the contained volume defined by the container, and the treated packaging material is exposed to the interior atmosphere within the contained volume. Such exposure is, in various modalities, either direct exposure of a cured coating within the interior atmosphere, or indirect exposure of such a coating applied to the outside of a package, where the package is water-permeable, 1-MCP, or both. The volume
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48/83 confined includes an appropriate and activating amount of water in such a way that the 1-MCP / c / a-CD releases the 1-MCP in the inner package in sufficient concentration to inhibit ripening or maturation of production. 1-MCP is also released from the packaging material by exposing the packaging material to a controlled level of water vapor and / or liquid water. The release of 1-MCP from the cyclodextrin inclusion complex 1-MCP / c / a-CD facilitated by water vapor is explored and described in detail by Neoh, TZ et al., Carbohydrate Research 345 (2010), 2085 to 2089. In embodiments, the cured cyclodextrin composition is both permeable to the olefinic inhibitor and water vapor to a degree sufficient to maintain an amount of olefinic inhibitor that inhibits ripening or maturation within the confined volume and in the presence of water vapor.
[082] The researchers from Neoh, TZ et al., Carbohydrate Research 345 (2010), 2085 to 2089 studied dissociation of dynamic complex of 1-MCP / c / aCD and observed that increasing moisture generally triggered dissociation of 1-MCP complex . However, dissociation was highly delayed in relative humidity by 80%, presumably because of the collapse of the crystalline structure; then, abrupt dissociation that corresponds to complex dissolution was observed at 90% relative humidity. However, the researchers found, like the inventors in this present invention, that even at 100% relative humidity, less than 20% of the complexed 1-MCP is released. In fact, an average of less than a fifth (~ 17.6%) of the amount of total complexed 1-MCP was dissociated at the end of the experiments while 1-MCP at ~ 83.4% remained complexed.
[083] In some modalities, during distribution and storage of packaged production, when storage temperature is between about 0 ° C and 20 ° C, the relative humidity in the confined volume around the production will be between about 50% and 100 % due to normal water loss from breathing
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49/83 production within the confined package volume. The increase in humidity within the confined volume of the package is sufficient, in modalities, to release a portion of the 1-MCP from the 1-MCP / w / a-CD. In other embodiments, the internal humidity of the treated container is adjusted by adding water to the container before sealing to form the confined volume. In some such modalities, relative humidity within the confined volume is provided by adding hydration (mist, spray or water vapor) to the air by humidifiers during packaging or by controlling the ambient humidity at the packaging location, inside the package itself. , or both.
[084] Unexpectedly, the cured cyclodextrin compositions of the invention continue to release high concentrations of olefin inhibitor with increasing amounts of water, even when the amount of water in a confined space reaches, and exceeds, the amount necessary to result in relative humidity in 100% given the volume of space and the temperature. Thus, for example, in some embodiments, a package is formed from treated packaging material; live plant material is added, and the package is sealed. Initially, the package contains less than 100% relative humidity; as the plant material breathes into the package, 100% relative humidity is achieved. As the humidity increases, the amount of olefinic inhibitor present in the atmosphere inside the package also increases. In some embodiments, the amount of water released by the plant material exceeds the amount that constitutes 100% relative humidity, such that liquid water is formed. In such embodiments, it has been found that the amount of olefinic inhibitor released within the package continues to increase even though the amount of water in the vapor phase cannot be increased and only liquid water is released into the sealed package atmosphere. In the experiment, it was found that the levels of olefinic inhibitor released by the cyclodextrin compositions cured within a confined space
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50/83 continues to increase in a predictable manner with increasing amounts of water added, regardless of whether the water is in the form of vapor or liquid.
[085] The relationship between the amount of water in a confined space and the release of 1-MCP from 1-MCP / c / a-CD complex was very surprising when 1-MCP dissociation (release) was measured as a function of adding water to the complex. Α-CD water solubility is 14.5 grams / 100 mL, or 14.5% by weight, at typical ambient temperatures. As reported in Control Example A in the Experimental section below, a significant excess of water in addition to the amount required to completely dissolve α-CD was required to dissociate 100% of the 1-MCP from the complex. The relationship between the amount of water present and dissociation of 1-MCP from 1-MCP / c / a-CD was demonstrated in a complex supplied alone, as well as in the cured cyclodextrin compositions of the invention. Importing the relationship between water and 1-MCP dissociation is of great importance in employing the technology, because:
1) the amount of 1-MCP is regulated in the atmosphere surrounding fruits and vegetables on a country-by-country basis; and
2) the benefit (ie, shelf life extension) derived from 1-MCP differs with exposure concentrations for various types of production material (see, for example Blankenship, SM and Dole, JM, Postharvest Biology and Technology 28 ( 2003), 1 to 25); in addition, adverse effects to some production materials are possible with excessive 1-MCP treatment concentrations.
[086] In two examples of country-by-country regulations at the time of this writing, the United States Environmental Protection Agency (EPA) currently limits 1-MCP to a maximum of 1 ppm in air by the authority of Section 408 of the Federal Law of Food, Drugs, and Cosmetics (FFDCA); and the European Commission on Health and Consumer Protection Guidelines and Member States of the
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European Food Safety Authority similarly regulates 1-MCP over its various guidelines, which limits levels of 1-MCP to amounts ranging from 2.5 ppb v / v to 1 ppm v / v.
[087] Thus, in modalities, 1-MCP decoupling needs to be carefully managed within the empty package space by both controlling the amount of total 1-MCP incorporated within the packaging structure and the 1-MCP release from the inclusion. In addition, in embodiments, the amount of residual water inherently capable of adsorption or absorption by the cured cyclodextrin compositions of the invention further affects 1-MCP dissociation. In embodiments, the hydrophilic nature of the cyclodextrin itself increases the compatibility of water with a cured cyclodextrin composition in which a cyclodextrin inclusion complex is incorporated.
[088] In embodiments of the invention in which the cyclodextrin inclusion complex employed in the treated packaging materials of the invention is 1MCP / c / a-CD, the amount of 1-MCP in the atmosphere that is required for a particular packaging application it is calculated based on several factors; then the coating thickness and coated area (that is, the total coating volume) is varied based on the confined volume, concentration of 1MCP / w / a-CD included in the cured cyclodextrin composition, and approximate fraction of 1-MCP / c / a-CD that is complexed (vs. non-complexed a-CD) to reach in the targeted atmosphere. Factors that need to be considered in such a calculation include any humectants or desiccants within the package, permeation / adsorption / water absorption capacity and 1-MCP of the cured cyclodextrin complex, water permeation / adsorption / absorption capacity and 1-MCP of the packaging material, any controlled or modified atmosphere present within the package, and respiration rate of the targeted production material. For example, if
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52/83 an atmosphere containing 1 ppm of 1-MCP is required and the targeted confined volume is 1 liter, so assume 100% complexation and a general density of the cured cyclodextrin composition of 1 g / cm ³ , a composition of cured cyclodextrin containing α-cyclodextrin coated in 1.71% by weight with 12.7 pm thickness in an area totaling 2 cm ^{2 would} provide 1 ppm targeted 1-MCP to the confined volume in the presence of water vapor with the use of conversion of Ideal Gas Law. In modalities, the target weight range of 1-MCP / c / a-CD is 25 micrograms to 1 milligram per 1 liter of confined volume. In such calculations, the value of delivering a targeted coating quantity to the targeted confined volume is realized. Certain embodiments described above are particularly advantageous in delivering a precisely measured amount of 1-MCP to a confined volume, as well as allowing an easily varied amount of cyclodextrin composition to a target container. For example, in some embodiments, inkjet printing is well understood for delivering accurate and easily varied volumes of material to substrates over an easily varied volume. In other embodiments, adding the inclusion complex to an adhesive formulation on a label, followed by cutting a label of precise size to apply to a packaging material, results in delivering an accurate amount of 1-MCP / c / a-CD treated packaging material.
EXPERIMENTAL SECTION
Example 1 [089] A cyclodextrin inclusion complex is formed of α-cyclodextrin and 1-methyl cyclopropene (1-MCP) using the technique described by Neoh, T. L. et al., J. Agric. Food Chem. 2007, 55, 11020 to 11026 “Kinetics of Molecular Encapsulation of 1-Methylcyclopropene into α-Cyclodextrin.” The inclusion complex is called “1-MCP / w / a-CD.” A 500 ml bottle is loaded with 97 , 0 g of isobornyl acrylate, 1.0 g of hexanediol diacrylate, 1.0 g of 1-MCP / w / a-CD and 1.0 g of 1
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53/83 hydroxycyclohexyl benzophenone (IRGACURE® 184, obtained from Ciba Specialty Chemicals Corp. of Tarrytown, NY). The bottle is tightly capped and the components are mixed by shaking the bottle briefly by hand.
[090] About 2 ml of the mixture is removed with a measured dropper and dispensed on a 21.59 cm (8.5 inch) by 27.94 cm (11 inch) PET film and brought down with the use of a measuring rod (Mayer rod) that has a delivered coating thickness of 25 microns. The coated PET film is then placed on a flat surface approximately 5 cm below a medium pressure mercury arc lamp operating at 79 watts per cm (200 watts per inch). After 30 seconds under the lamp, the film is removed. A silicone-coated PET slide (about 50 microns thick) is placed over the cured coating and left to rest on a laboratory bench overnight.
[091] A mold cutter is used to cut a 1 cm by 1 cm square from the coated portion of the blade. The liner is removed from the coated square and the coated square is placed in a 250 ml bottle of serum. The flask is then sealed with a silicone divider with a TEFLON® face. The empty space concentrations of 1-MCP are measured after 1 hour after introducing the coated square into a flask. The empty space concentration of 1-MCP is quantified using gas chromatography by removing 1 ml of gas from the sample flask using a gas sampling valve aimed directly at a GC column that has a detector of FID. No measurable 1-MCP concentration is detected because of the lack of moisture in the empty space of the jar.
[092] Then 50 pl of deionized water is injected into the jar. Care is taken that liquid water does not come into direct contact with the coated square. The sealed jar is left to stand on the laboratory bench for
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54/83 one hour after the water injection, then a second sample of empty space is analyzed. A final sample of empty space is analyzed 24 hours after the water injection. In 1 hour after a water injection, 0.5 ppm of 1-MCP is measured in the void. After 24 hours, 0.5 ppm of 1-MCP is measured in the void.
Example 2 [093] An inclusion complex of 1-butene and α-cyclodextrin was formed using the technique described by Neoh, T. L. et al., J. Agric. Food Chem. 2007, 55, 11020 to 11026 “Kinetics of Molecular Encapsulation of 1-Methylcyclopropene into αCyclodextrin” except that 1-butene (99.0% pure, Scott Specialty Gases, Plumsteadville, PA) was bubbled through a saturated solution of αcyclodextrin instead of 1-MCP. A precipitate was formed during the process, which was collected by filtering through a 10 micron porous filter and dried at room temperature in 0.01 kPa (0.1 mm Hg) for about 24 hours. The inclusion complex was called “1-butene / w / a-CD.” [094] 1-butene / w / a-CD was analyzed by adding 100 mg of the collected precipitate and dried in a 250 ml glass vial. ml equipped with a divider cap, taking care to ensure that no dust adheres to the walls of the bottle. After about 1 hour, 250 pl of empty space gas was removed from the flask using a six-port two-position gas sampling valve (Valco # EC6W) aimed directly at a gas chromatograph (GC; Hewlett Packard 5890) using a GC RTx-5 column, internal diameter 30 mx 0.25 mm, a 0.25 pm film (obtained from Restek, Inc., Bellefonte, PA) and equipped with an ionization detector of flame (FID). No measurable 1-butene concentration was detected because of the lack of moisture (water vapor) in the empty space of the bottle. Then 3 ml of water was injected into the bottle through the partition and the bottle is placed on a mechanical stirrer and mixed vigorously for about 1 hour. After stirring, 250 pl of the empty space gas is removed and added in
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55/83 an empty 250 ml flask equipped with a divider cap, in which the inside of the flask was purged with nitrogen gas. The empty space concentration of 1butene was quantified in the second flask using gas chromatography by removing 250 μΙ of gas from the 250 ml flask using a six-port two-position gas sampling valve (Valco # EC6W) aimed directly at a GC column that has a FID detector previously calibrated with a 6-point calibration curve of 1-butene (99.0% pure, Scott Specialty Gases, Plumsteadville, PA). When using this method, the yield of complexed 1butene / c / a-CD was found to be 72.5%.
[095] A 20 ml bottle was loaded with 9.8 g of UV coating VP 10169/60 MF-2NE (obtained from Verga GmbH of Aschau am Inn, Germany) and 0.2 g of 1-butene / c / a -CD. The bottle was tightly capped and the components were mixed by shaking the bottle by hand until they were evenly dispersed.
[096] About 3 ml of the mixture was removed with a dropper and dispensed in a glass tray. A roll of rubber paint was used to spread the mixture across the glass and the roll. Then, the roller was used to coat the mixture on the coated side of a 20 cm by 20 cm section of polyethylene extruded coated paper (REYNOLDS® Freezer Paper, 90 microns in total thickness). The roll delivered a nominal coating thickness of 0.3 microns. A razor blade was used to cut a 5 cm by 10 cm rectangle from the coated blade. Then the coated cut rectangle was passed manually about 10 cm below a medium pressure mercury arc lamp operating at 79 watts per cm (200 watts per inch). After 1.5 seconds of exposure to the lamp, the cured rectangle was removed. The cured rectangle was left to stand on a laboratory bench overnight with the coating facing down.
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56/83 [097] Six replicated coated rectangles were made this way. Each rectangle was placed in a bottle with 250 ml of serum. Then the six vials were sealed with a silicone partition with a TEFLON® face. The empty space concentration of 1-butene was quantified using gas chromatography by removing 250 pl of gas from the sample flask using a six position two-port gas sampling valve facing the column directly. GC that has an FID detector. No measurable 1-butene concentration was detected in the vial void.
[098] Then 50 pl of deionized water was injected into each vial. Care was taken that liquid water did not come into direct contact with the coated rectangles. The empty space of each one of the six sealed vials was analyzed 0.5, 1, 2, 4, 8, 24 and 96 hours after the water injection in which about 3 ml of the volume of empty space of the 250 ml vial has been removed for each analysis. In each sample, the amount of 1-butene released from the UV-coated rectangles was quantified by gas chromatography against a 6-point calibration curve of 1-butene which has a correlation coefficient of 0.998. Table 1 and Figure 1 illustrate the average of six replicated samples of 1-butene void concentration and standard deviation.
Hours 1 -butene Mean standard ppm deviation (v / v) (ppm)
0.5 0.460,24
1.50.55
3.00.61
4,90.78
6.00.35
7.61.6
7.81.7
Table 1. Concentration of 1-butene void according to the procedure of Example 2.
Example 3
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57/83 [099] A 20 ml bottle was loaded with 9.6 g of UV coating VP 10169/60 MF-2NE (obtained from Verga GmbH of Aschau am Inn, Germany). Then 0.4 g of 1-MCP / a-cyclodextrin complex (4.7% 1-MCP obtained from AgroFresh of Spring House, PA) called “1-MCP / w / a-CD” was added to the flask . The flask was then tightly capped and shaken by hand until the blends appear evenly dispersed, resulting in a blending of 4.0% by weight of 1MCP / w / a-CD. Three additional blends containing 2.0% by weight, 1.0% by weight and 0.5% by weight of 1-MCP / c / a-CD were prepared in the same manner.
[0100] A rubber paint roller was used to deliver a thin coating (nominally 0.3 pm) to a 20 cm by 20 cm polyethylene extrusion coated paper sheet using the technique of Example 2.
[0101] Using a razor blade, 2.5 cm x 10 cm rectangles were cut from the coated portion of each of the blades. Then the coated rectangular slides were cured using the procedure of Example 2. Each cured coated rectangle was placed in a vial with 250 ml of serum. The flask was then sealed with a silicone divider with a TEFLON® face. Then 20 pl of deionized water was injected into each vial. Care was taken that liquid water did not come into direct contact with the coated rectangles. The empty space was analyzed by 1-MCP 24 hours after water injection using the technique used in Example 2 and using the 6-point calibration curve of 1-butene as described in Example 2. Table 2 and Figure 2 generates an average of 24 hours of empty space concentration and standard deviation of 1-MCP for each of the cured and coated rectangular sheets. These data illustrate that 1-MCP was released into the empty space in a linear manner (correlation coefficient of 0.99) with an increase in weight of 1-MCP / c / a-CD in the coating when exposed to water vapor ( moisture).
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58/83% by weight mean Ppm Deviation 1-MCP / c / α- from 1-MCP standard
CD (v / v) (ppm)
0.5 0.090.03
0,200.02
0.560.13
1.10.22
Table 2. Concentration of 1-MCP empty space according to the procedure of Example 3.
Example 4 [0102] A mixture of 4.0% by weight of 1-MCP / c / a-CD was made according to the technique of Example 3. A rubber paint roller was used to deliver a coating that has a nominal thickness of 0.3 pm for a 20 cm by 20 cm polyethylene coated sheet of paper using the technique of Example 2. The coated sheet was cured according to the procedure of Example 2.
[0103] Using a razor blade, samples of 26 cm ² , 52 cm ² and 78 cm ² were cut from the coated portion of the blade. Each sample was placed in a vial with 250 ml of serum. The flasks were sealed with a silicone partition with a TEFLON® face. Then 20 pl of deionized water was injected into each vial. Care was taken that liquid water did not come into direct contact with the test sample. A vial empty space analysis was conducted according to the technique of Example 3 0.17 hour, 0.5 hour, 1 hour, 2 hours, 4 hours and 24 hours after water injection. The empty space concentrations of 1-MCP as a function of time and test sample area are provided in Table 3 and Figure 3. These data illustrate that 1-MCP was released into the empty space in a predictable manner over time with a increasing coated surface area that has 4.0% by weight of 1-MCP / c / a-CD when the coating is exposed to water vapor (moisture).
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TimeH 26 cm ² of 1-MCP (ppm — v / v) 52 cm2 of 1-MCP (ppm - v / v) 78 cm2 of 1-MCP (ppm - v / v) 0.17 0.25 0.66 1.7 0.5 1.5 2.2 3.4 1 2.4 4.2 5.2 2 3.7 7.0 7.9 4 5.8 9.9 12.4 24 9.6 16.1 20.0
Table 3. Concentration of 1-MCP empty space according to the procedure of Example 4.
Example 5 [0104] Using a razor blade, six rectangles of 5 cm x 10 cm were cut from the blades of coated portions of 20 cm by 20 cm prepared according to Example 3 and which have 1.0% by weight, 2.0% by weight and 4.0% by weight of 1-MCP / w / a-CD and the coated rectangles were cured according to the technique of Example 2. The rectangles were individually placed in 250 ml serum bottles . The flasks were sealed with a silicone partition with a TEFLON® face. Then 20 pl of deionized water was injected into each vial. Care was taken that liquid water did not come into direct contact with the test sample. The empty space of the bottle was analyzed 4, 8, 24 and 48 hours after the water injection using the technique of Example 3. The results are provided in table 4 and in Figure 4 and generate the concentration of empty space and the deviation standard averages for the different% by weight of 1MCP / w / a-CD coatings as a function of time. These data illustrate that 1-MCP was released into the void in a predictable manner over time with an increase in weight of 1-MCP / c / a-CD in the coating when exposed to water vapor (moisture).
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% in 1-MCPweight of (ppm - v / v)1-MCP / w / ina-CD, Space Detour coated Empty hours pattern
1 4 0.96 0.15 1 8 2.0 0.44 1 24 3.6 0.98 1 48 4.0 1.2 2 4 3.5 1.2 2 8 7.8 2.6 2 24 17.8 5.9 2 48 21.2 7.5 4 4 7.5 0.08 4 8 13.5 1.3 4 24 24.0 1.8 4 48 28.0 0.05
Table 4. Concentration of 1-MCP empty space according to the procedure of Example 5.
Example 6 [0105] A 100 ml quartz beaker was loaded with 54 g of 2-isooctyl acrylate, 6 g of acrylic acid and 0.60 g of 1-hydroxycyclohexyl phenyl ketone (IRGACURE ^® 184, Ciba Specialty Chemicals Corp. de Tarrytown, NY). The beaker was equipped with a mechanical stirrer and the contents were mixed for about 5 minutes while spraying with dry helium. Then the beaker was irradiated with a medium pressure mercury arc lamp operating at 79 watts per cm located about 15 cm from the side of the beaker. The light was turned off when the contents of the jar had a honey-like consistency, about 1.5 minutes. The beaker was additionally loaded with 3.23 g of 1-MCP / w / a-CD, 0.89 g of IRGACURE ^® 184, 5.8 g of isooctyl acrylate and 0.72 g of acrylic acid. The beaker contents were mixed until uniformly dispersed, in about 5 minutes.
[0106] About 4 ml of the mixture in the flask was removed with a measured dropper and dispensed on a white paper identification tag
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61/83 30.5 cm by 30.5 cm and brought down using a measuring rod (Meyer coating rod # 30) which has a delivered coating thickness of 25 microns. Then a 21.5 cm by 28 cm (120 pm thick silicone coated polyester film (PET) film (obtained from the 3M Company in St. Paul, MN) was placed over the coated identification tag, taking care to do not drag air bubbles. The covered and coated identification tag was cut into 10 cm by 20 cm rectangles using a paper cutter. The cut samples were passed manually about 15 cm below a mercury arc lamp medium pressure operating at 79 watts per cm; multiple manual passes under UV light or about 30 seconds under the lamp was used to cure the adhesive.The cured coated ID tag blades were left to rest with the PET side face up on a laboratory bench overnight.
[0107] A paper cutter was used to cut six replicas of 2.5 cm by 2.5 cm squares from the blades. Because the UV-cured coating composition is a pressure sensitive adhesive, or PSA, the 2.5 cm by 2.5 cm squares are called “PSA labels”. Each PSA label, with the silicone coated PET still in place, was placed in a 250 ml bottle of serum. Each flask was sealed with a silicone divider with a TEFLON® face. The empty space concentration of 1-MCP was measured 1 hour after the introduction of the PSA label in a flask, using the technique of Example 3 with the exception that 250 pl of gas was removed from the sample flask for analyze. 1-MCP was below the limit of quantification of 0.01 ppm.
[0108] Then 50 pl of deionized water was injected into each bottle. Care was taken that liquid water did not come in direct contact with the labels. The sealed space of the sealed bottle was analyzed in 10 minutes, 30 minutes and 60 minutes using the technique of Example 3. A final sample of
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62/83 empty space was analyzed 16 hours after water injection. These data are shown in table 5. The data illustrates that 1-MCP was released from a PSA tag in the empty space when exposed to water vapor (moisture) and that its concentration increases with time.
Average ppm (v / v) of 1- Deviation
Standard MCP hours
0.17 0.010.01
0.5 1.30.84
3.60.75
29.78.0
Table 5. Concentration of 1-MCP empty space according to the procedure of Example 6.
Example 7 [0109] This method is designed to measure the permeability of 1MCP through a polyethylene film in a confined space with a fixed volume after a release of a PSA label adhered to the surface of the film that defines the fixed volume. The methodology simulates the empty space of a flexible film package that initially has a low relative humidity, in which a PSA label containing 1-MCP is adhered to the outside of the package. As the humidity rises inside the package through breathing fresh agricultural products, the water vapor increases in concentration and it diffuses through the package film to the external environment but also in the PSA. Thus, as the water vapor diffuses through the film to the 1MCP adhesive label attached to the outside of the package film; the 1-MCP released from the label sticker into the fixed volume (empty space) was measured.
[0110] A coated cured ID tag blade made according to the procedure of Example 6 was cut manually in an 11 cm diameter circle. Afterwards, the PET liner was removed from the label and the
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63/83 the label was adhered by means of PSA to a polyethylene (PE) film 13.5 cm in diameter and 25 μπι (1 mil) thick (obtained from the Pliant Corporation of Schaumburg, IL). The paper side of this structure was then covered with aluminum foil. The structure placed in layers of sheet / paper / PSA / PE was mounted on the open end of a 1,000 ml glass reaction kettle bottom (6947-1LBO, from Corning Glass from Corning, NY) and sealed to the glass flange the kettle with the use of aluminum sealing rings. The layered structure was oriented over the 11 cm opening with the PE film facing inwards and the aluminum facing outwards. The glass reaction kettle has been modified with a silicone divider port to allow sampling of the 1,000 ml void space. The empty space analysis was conducted by removing 250 μl of the empty space volume from the 1,000 ml glass kettle and analyzing it according to the technique of Example 3.
[0111] Two hours after the film and the label are sealed to the reaction kettle bottom flange and without any water added within the volume of 1,000 ml; an initial empty space analysis was conducted and revealed no detectable level of 1-MCP (<0.01 ppm). Then 200 μl of water was added through the partition door into the glass kettle. The empty space was analyzed by 1-MCP 17, 25 and 90 hours after the water injection using the technique employed in Example 3. 17 hours, 25 hours and 90 hours after an injection of water, the concentration of empty space of 1-MCP was 3.6 ppm, 7.0 ppm and 8.0 ppm of 1-MCP, respectively. These results demonstrate a PSA-coated label that contains 1-MCP and adhered to a vapor permeable film surface can release 1-MCP into the empty space of the package after introducing water vapor into the empty space of the package.
Control example A [0112] An α-CD water solubility is 14.5 grams / 100 ml or
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14.5% by weight at normal ambient temperatures (Szejtli, J. (1988), Cyclodextrin Technology, Kluwer Academic Publishers, page 12). A 1MCP / c / a-CD powder sample was obtained (AgroFresh from Spring House, PA). According to the supplier specification table, the 1-MCP complex was 4.7% by weight of α-CD or 88.7% by weight of 1-MCP based on a theoretical molar ratio of 1: 1 from 1-MCP to α-CD; this corresponds to a resulting empty space concentration of 8,600 ppm. A series of tests was conducted to measure the dissociation of 1-MCP from the 1-MCP / c / a-CD provided as an added water function. First, 0.1 g aliquots of the supplied 1-MCP / c / a-CD powder were added to each of the 5 250 ml vials, which were then capped with a TEFLON®-faced partition. Variant amounts of water were added to the vials by syringe and then the vials were mechanically stirred for one hour, followed by an empty space measurement for 1-MCP according to the procedure in Example 3. The quantities of water added by 0.1 g of the supplied 1-MCP / c / a-CD complex and the resulting empty space measurements after 1 hour at about 20 ° C are shown in Table 6.
[0113] The test results showed 5.8% by weight of 1-MCP or 111% by weight of 1-MCP / c / a-CD complex (greater than a 1: 1 complex) resulting in a concentration empty space of 10,610 ppm. In 1.0 grams of water per 0.10 grams of 1-MCP / w / a-CD, a water solubility of α-CD was exceeded even though 1-MCP is only 66% dissociated. A polynomial regression was used to calculate the dissociation at 100% RH in the empty space for the five samples in table 6 (ie 4.3 milligrams of water per 250 ml volume, see Example 8 for the source and calculation information). The calculated amount of 1-MCP dissociated at 100% RH was 18% by weight.
[0114] These results were surprising since a significant excess of water beyond the amount required to completely dissolve the a
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CD (14.5 grams / 100 ml, as reported above) was required to dissociate 100% from the complexed 1-MCP.
1-MCP, ppm
H2O, g (v / v)
0.253.050
0.54,750
1,06,850
2,09,850
3.0 10,610
Table 6. Concentration of 1-MCP empty space according to the procedure of control example A.
Example 8 [0115] A 4.0% by weight coating blend of 1-MCP / w / aCD was made according to the technique of Example 3. A 20 cm by 20 cm polyethylene coated sheet of paper was coated with the mixture using the technique of Example 2. A paper cutter was used to cut nine 5 cm by 10 cm rectangles from the blade. The coated coated rectangles were passed manually about 10 cm below a medium pressure mercury arc lamp operating at 79 watts per cm. After 1.5 seconds of exposure to the lamp, the sample was removed. The cured sample was left to stand on a laboratory bench overnight with the coating facing down.
[0116] Each cured sample was placed in a 250 ml bottle of serum. Each flask was sealed with a silicone divider with a TEFLON® face. The amount of liquid water that can, in the form of steam, correspond to 100% relative humidity (RH) at 20 ^Q C (provided at http://hyperphvsics.phyastr.qsu.edu/hbase/kinetic/vappre.html# c) is 17.3 g / ^m3 and 17.3 g per 1.000 I. of water density at 20 ^Q C is 0.9982 g / ml. Thus, at 20 ^Q C, 4.3 μΙ of water
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66/83 liquid added in a confined volume of 250 ml and containing no other water will vaporize to generate 100% RH. The temperature of the laboratory facility was 20 ° C ± 5 ° C.
[0117] Three of the vials were injected with 10 pl of deionized water, three with 20 pl of deionized water and three with 50 pl of deionized water. Care was taken that liquid water did not come into direct contact with the coated square. The empty space of each flask was analyzed by 1-MCP 2 hours, 4 hours, 8 hours, 24 hours and 48 hours after the water injection, in which the empty space analysis was conducted using any analytical technique used in the Example 3. The results of mean empty space concentration and standard deviation are given in Table 7 and Figure 5.
1-MCP, ppm
Time, Mean Deviation
H2O, pl h (v / v) standard
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 Table 7. Concentration of empty space 1-MCP according to the
procedure of Example 8.
Example 9 [0118] UV curable ink designed for thermal inkjet cartridges and industrial printing was formulated with 1-MCP / c / a-CD and printed on
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67/83 film to demonstrate how UV ink can be incorporated into a flexible packaging structure to release 1-MCP. ImTech UVBLK Series 912 cartridges were obtained from ImTech Inc. of Corvallis, OR. About 40 g of black ink was removed from the cartridge in which the ink was supplied. The paint was dried overnight in a closed container with 3A molecular sieves to remove residual water contained in the paint. Then 17.5 g of the dried ink was transferred to a 70 ml roller mill jar filled with 50 g of 3 mm glass microspheres to which 0.875 g of 1-MCP / c / a-CD was added to the ink. of UV. The jar was sealed and spun in a roller mill at 140 rpm for four hours. At the end of the four hours of rolling to disperse the 1-MCP / w / a-CD, an additional 4.375 g of dry UV ink was added producing a ring containing 4% by weight of 1-MCP / w / a-CD. Then the paint was decanted from the glass microspheres.
[0119] A rubber ink roller was used to coat a thin, discontinuous UV coating (nominally 3 pm), but uniform in a 10 cm by 20 cm section of PET film (120 microns thick, obtained with 3M Company of St. Paul, MN) as described in Example 2. The UV-coated rectangles were manually passed about 10 cm below a medium pressure mercury arc lamp operating at 79 watts per cm for a 1.5 second exposure to the lamp. The cured sample was allowed to rest on a laboratory bench overnight with the paint side down.
[0120] A guillotine was used to cut two samples, 20 cm ² and 81 cm ² , from the PET film sheet coated with cured paint. The samples were placed individually in 250 ml serum bottles. The flasks were then sealed with a silicone partition with a TEFLON® face. Then 200 pl of deionized water was injected into the flask. Care was taken that liquid water did not come into direct contact with the PET film coated with paint.
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After the injection of water into the vial, 1-MCP was measured in the empty space using the analytical technique employed in Example 3. The test results are tabulated in Table 8; the results demonstrate a release of 1-MCP from the UV ink. The results further demonstrate that 1-MCP is released slowly, increasing the empty space concentration of the vial with increasing time.
cm ² of 81 cm ² of
1-MCP ppm 1-MCP ppm
Hours (v / v) (v / v)
0.17 ND ND 0.5 <0.01 <0.01 1 <0.01 0.05 2 0.01 0.18 4 0.04 - 8 0.05 - 21 - 0.51 27 0.09 - 48 - 0.60 170 0.76 -
Table 8. The empty space concentration of 1-MCP according to the procedure of Example 9.
Example 10 [0121] The ink containing 4% by weight of 1-MCP / c / a-CD from Example 9 was loaded back into the previously deflated cartridge. After refilling the cartridge, it was installed on an HP Inkjet 1600C printer (obtained from the Hewlett-Packard Company of Palo Alto, CA) and the calibration or head cleaning function was performed. A black hatch pattern of medium density obtained from the Microsoft EXCEL 2003 software program (obtained from Microsoft Corporation of Redman, WA) was used to form the entire printable page. The EXCEL standard image was printed on 3M Transparency Film, CG3460 (120 micron thick polyester film for HP Inkjet printers; obtained from 3M Company of St. Paul, MN) using the
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69/83 dry and ground ink containing 4% by weight of 1-MCP / w / a-CD of Example 9. Immediately after printing, the printed side of the transparency film was overlaid with a 25 mm polyethylene film pm and then manually passed about 10 cm below a medium pressure mercury arc lamp operating at 79 watts per cm for 3 seconds exposure to the lamp, with the polyethylene side facing the lamp. The methodology simulates a flexible multilayered packaging on which the inner surface of a transparent and outer layer of the flexible multilayered material has been printed (referred to as reverse printing). The printed surface was then laminated to other layers. The outer layer itself serves to protect the paint from misuse.
[0122] The following technique was designed to measure the permeability of 1-MCP, which was released from the 3M Transparency Film printed by reverse inkjet, through the PE film as the “inner layer” of a product packaging multilayered. In a multi-layer product package, as moisture grows inside the package through the breath of fresh agricultural products, the water vapor reaches a concentration that allows it to diffuse outside the package. In this example, water also diffuses through the ink layer that contains 1-MCP / w / a-CD. The printed ink inverted on the PET film releases 1-MCP which diffuses through the PE film into the package (empty space) under a low gradient of concentration of 1-MCP within the empty space of the bottle and concentration of 1- High MCP within the multilayer structure.
[0123] Using a guillotine, a 5.5 cm by 16 cm (88 cm ² ) rectangle was cut from the multilayer structure of the cured ink and printed on the PET sheet superimposed with PE. The rectangle was placed in a bottle with 250 ml of serum. The flask was then sealed with a silicone divider with a TEFLON® face. Then 100 pl of deionized water was injected into the flask. Careful was
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70/83 taken so that liquid water does not come into direct contact with the test sample. The empty flask space was analyzed at 0.17, 0.5, 1, 2, 4 and 24 hours after the water injection using the technique used in Example 3. The results in Table 8 illustrate the concentration of 1- Empty space MCP as a function of time for the “multilayer” film.
[0124] A second part of PET transparency film was printed as in Example 9 except that the transparency film was not covered with PE film; the printed ImTech UVBLK Series 912 ink was cured on the surface of PET film using a medium pressure mercury arc lamp that operates at 79 watts per cm in the same way as in Example 9. So, using a guillotine, a 1.2 cm by 16 cm (19 cm ² ) rectangle was cut from the blade. The rectangle was placed in a 250 ml serum bottle. The flask was then sealed with a silicone divider with a TEFLON® face. Then 100 pl of deionized water was injected into the flask. Care was taken that liquid water did not come in direct contact with the test sample. The vial empty space was analyzed at 0.17, 0.5, 1, 2, 4 and 24 hours after the water injection using the technique employed in Example 3. An empty space concentration of 1MCP as a function of time is also reported in Table 9 for the “single layer” film.
Hours 88 cm ² multiple layers 1-MCP ppm (v / v) Single 19 cm ² bed 1-MCP(v / v) ppm 0.17 0.25 0.500.5 0.46 0.521 1.1 0.502 1.5 0.514 3.2 0.5224 8.3 0.49
Table 9. The empty space concentration of 1-MCP according to the procedure of Example 10.
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Example 11 [0125] Cardboard coated by extrusion of polyethylene is one of the most frequently used fresh product packaging materials. Typically, cardboard is recyclable and has a thin layer (usually 30 pm or less) of polyethylene on one side or both sides. The extruded coated surface can be coated or printed with a UV curable coating that contains 1-MCP.
[0126] A 20 ml bottle was loaded with 9.6 g of UV-curable coating formulation (VP 10169/60 MF-2NE, obtained from Verga GmbH in Aschau am Inn, Germany). Then 0.4 g of 1-MCP / w / a-CD (4.7% 1-MCP, obtained from AgroFresh at School House, PA) was added to the flask. The bottle was tightly capped and the components mixed by shaking the bottle by hand until the contents appeared to be evenly dispersed, providing a UV-curable mixture.
[0127] A polyethylene-coated cardboard was prepared by hot laminating a 30 pm polyethylene film onto a 20 cm x 20 cm section of 600 pm thick solid bleached sulphate (SBS) cardboard (obtained from Graphic International Packaging of _) with the use of a heated vacuum press. A roll of rubber paint was used to deliver a thin coating (nominally 0.3 pm) of the UV curable mixture to the laboratory-coated polyethylene cardboard using the technique of Example 2. A guillotine was used to cut a 20 cm by 10 cm rectangle of the coated portion of the cardboard. The coated rectangle was manually passed about 10 cm below a medium pressure mercury arc lamp that operates at 79 watts per cm. After 1.5 seconds of exposure to the lamp, the sample was removed. The cured sample was allowed to rest on a laboratory bench overnight with the coating side down.
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72/83 [0128] After curing, the 5 cm by 5 cm sections were cut from the 20 cm by 10 cm rectangles. Each section was placed individually inside a 250 ml jar (clear and large WM SEPTA-JAR ™, Fisher Scientific P / N 05-719-452; obtained from Fisher Scientific of Waltham, MA) equipped with a partition with a face TEFLON ™ (Fisher Scientific P / N 14-965-84). Each jar was injected with 200 pl of deionized water. Care was taken that liquid water did not come into direct contact with the coated square. The jar empty space was analyzed for 1-MCP in five time periods (0.17, 0.5, 1, 2, 4 and 7 hours) after the water injection, using the analytical technique used in the Example 3. The average empty space concentration of 1-MCP and standard deviation are tabulated in Table 10. The results exemplify that larger amounts of 1MCP were released inside the empty space of the UV-coated substrate with increasing time.
1-MCP ppm Deviation
Standard hours (v / v)
0.17 0.160.09
0.5 0.630,40
1.60.67
3.61.5
7.32.5
12.52.8
Table 10. Concentration of 1-MCP empty space according to the procedure of Example 11.
Representative modalities [0129] At the moment, certain representative modalities of the invention are reported. The invention is not limited to these modalities and other modalities described above are also modalities of the invention or are modalities of the invention when combined with any combination of the modalities described below.
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Mode 1.
[0130] Mode 1 is suitably an embodiment of the invention alone or when combined in addition with any limitation or additional element as described above or in the following list. Mode 1 can be combined with a combination of two or more limitations or additional elements described above or in the following list. The following list contains limitations or elements that are intended to be combined in any way with modality 1 as additional aspects of the invention, including in combination with any one or more other limitations or elements described above.
[0131] Mode 1 of the invention is a cyclodextrin composition comprising one or more polymerizable monomers and a cyclodextrin inclusion complex, the cyclodextrin inclusion complex comprising a cyclodextrin compound and an olefinic inhibitor of an ethylene generation in production, and the olefinic inhibitor comprises a compound that has the structure:
[0132] where each of R ¹ , R ² are independently hydrogen or a C1-16 hydrocarbyl group and R ³ and R ⁴ are independently hydrogen or a C1-16 hydrocarbyl group under the condition that at least one of R ¹ or R ² is methyl.
[0133] The list of limitations or additional elements includes, without limitation, the following:
The. the one or more radiation polymerizable monomers comprise acrylic acid, methacrylic acid, an acrylate ester, a methacrylate ester, a
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74/83 acrylamide, a diacrylate, a triacrylate, a tetraacrylate or a mixture thereof;
B. the acrylate or methacrylate ester is an ester of an alcohol that has between 1 and 18 carbons and is a cyclic, branched or linear ester;
ç. the composition further comprises a photoinitiator;
d. the composition further comprises one or more prepolymers;
and. cyclodextrin comprises a cyclodextrin derivative;
f. the cyclodextrin inclusion complex contains about 0.1 to 0.99 mole of olefin inhibitor per mole of cyclodextrin;
g. the olefinic inhibitor comprises 1-methyl cyclopropene;
H. cyclodextrin comprises α-cyclodextrin;
i. the cyclodextrin inclusion complex contains about 0.80 to 0.99 mole of 1-methyl cyclopropene per mole of α-cyclodextrin;
j. the composition comprises between 0.01% by weight and 10% by weight of the cyclodextrin inclusion complex based on the weight of the composition;
k. the composition can be coated;
l. the composition is printable;
m. the composition is an ink;
n. the composition is a UV curable ink;
O. the composition additionally comprises one or more colorants;
P. the composition further comprises one or more adhesion promoters, antifouling agents, thermal stabilizers, oxidative stabilizers, water scavengers, adjuvants, plasticizers or a combination of two or more thereof;
q. the composition further comprises one or more desiccants;
r. the composition further comprises one or more desiccants comprising silica gel, molecular sieves or a combination thereof.
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Mode 2.
[0134] Mode 2 is suitably a mode of the invention alone or when combined in addition to any limitation or additional element as described above or in the following list. Mode 2 can be combined with a combination of two or more limitations or additional elements described above or in the following list. The following list contains limitations or elements that are intended to be combined in any way with modality 2 as additional aspects of the invention, including in combination with any one or more other limitations or elements described above.
[0135] 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, the cyclodextrin inclusion complex comprising cyclodextrin and an olefinic inhibitor of an ethylene generation in production, the olefinic inhibitor comprising a compound that has the structure:
[0136] where each of R ¹ , R ² are independently hydrogen or a C1-16 hydrocarbyl group and R ³ and R ⁴ are independently hydrogen or a C1-16 hydrocarbyl group under the condition that at least one of R ¹ or R ² is methyl.
[0137] The list of limitations or elements includes, without limitation, the
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The. the treated packaging material comprises a film, a blade, a sheet, a bag, a packaging, a plate, a glass, a cover, a label, cardboard, a cardboard box or a treated packaging leaflet;
B. the packaging material comprises a polyolefin or a polyester;
ç. the surface comprises a plasma treated surface;
d. the treated packaging material further comprises an initiator disposed between the packaging material and the cured cyclodextrin composition
and. the cured cyclodextrin composition is permeable to water and the olefinic inhibitor;
f. the cured cyclodextrin composition has different water permeability and the olefinic inhibitor;
g. the treated packaging material comprises a film, a blade, a treated packaging leaflet or a label and further comprises a liner arranged on top of the cured cyclodextrin composition;
H. the lining is transparent to UV light;
i. the lining is a leaf;
j. the liner additionally comprises one or more desiccants;
k. the liner is preferably removable at the interface of the liner and the cured cyclodextrin composition;
l. the lining is impermeable to water;
m. the packaging material is impermeable to water;
n. the packaging material is impermeable to the olefinic inhibitor;
O. the packaging material is water permeable, permeable to the olefinic inhibitor or permeable to both water and the olefinic inhibitor
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77/83
P. the packaging material is a selectively membrane permeable; q. the composition of cured cyclodextrin comprises an adhesive pressure sensitive;r. the composition of cured cyclodextrin 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 evidence;
u. the cured cyclodextrin composition is bonded to the packaging material;
v. the packaging material comprises a treated laminate;
w. the packaging material comprises a treated laminate which is permeable to the olefinic inhibitor on one first side of it and is impermeable to the olefinic inhibitor on a second side thereof;
x. the packaging material comprises a treated laminate which is permeable to water on at least one first side thereof;
y. the treated packaging material is dried under tension.
Mode 3.
[0138] Mode 3 is suitably a mode of the invention alone or when combined in addition to any limitation or additional element as described above or in the following list. Mode 3 can be combined with a combination of two or more limitations or additional elements described above or in the following list. The following list contains limitations or elements that are intended to be combined in any way with modality 3 as additional aspects of the invention, including in combination with any one or more other limitations or elements described above.
[0139] Modality 3 of the invention is a container comprising
Petition 870180057378, of 07/03/2018, p. 135/145
78/83 a treated packaging material, the container comprising a confined volume, the treated packaging material comprising a cured cyclodextrin composition disposed on at least a portion of a packaging material surface, the composition being The cured cyclodextrin compound comprises a polymer derived from one or more radiation polymerizable monomers and a cyclodextrin inclusion complex, the cyclodextrin inclusion complex comprising an olefinic inhibitor of a generation of ethylene in production, the olefinic inhibitor comprising a compound that has the structure:
wherein each of R ¹ , R ² are independently hydrogen or a C1-16 hydrocarbyl group and R ³ and R ⁴ are independently hydrogen or a C1-16 hydrocarbyl group on condition that at least least one of R ¹ or R ² is methyl.
[0140] The list of limitations or additional elements includes, without limitation, the following:
The. the container is a bag, packaging, plate, glass, or cardboard box;
B. the cured cyclodextrin composition is present as a coating on at least a portion of an inner surface of the container;
ç. the cured cyclodextrin composition is present as a coating on at least a portion of an outer surface of the container;
d. the cured cyclodextrin composition is present as a coating on a packaging leaflet;
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79/83
and. the container is a treated laminated container;
f. the container is a treated laminated container in which the laminated structure is permeable to the olefinic inhibitor on one first side of it and is impermeable to the olefinic inhibitor on a second side thereof;
g. the container is a treated laminated container in which the laminated structure is permeable to water on at least one first side thereof;
H. the container further comprises a desiccant;
i. the container additionally comprises a production item;
j. the confined volume comprises between 50% relative humidity and 100% relative humidity at a temperature between about 0 ° C and 20 ° C;
k. the confined volume comprises 100% relative humidity at a temperature between about 0 ° C and 20 ° C and additionally comprises liquid water;
l. the container comprises a modified atmosphere packaging;
m. the container comprises a controlled atmosphere packaging
n. the container comprises a selectively permeable membrane;
O. the olefinic inhibitor is present in the confined volume at a concentration of about 2.5 parts per billion to 10 parts per million;
P. the olefinic inhibitor is present in the confined volume at a concentration of about 25 parts per billion to 1 part per million.
Mode 4.
[0141] Mode 4 is suitably a mode of the invention alone or when combined in addition to any limitation or additional element as described above or in the following list. Mode 4 can be combined with a combination of two or more limitations or additional elements described above or in the following list. The following list contains limitations or elements that are intended to be combined in any way with modality 4 as additional aspects of the invention, including in combination with
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80/83 any one or more other limitations or elements described above.
[0142] Modality 4 of the invention is a method of manufacturing a treated packaging material, the method comprising:
form a cyclodextrin composition comprising one or more radiation polymerizable monomers of about 0.05% by weight to 10% by weight of a cyclodextrin inclusion complex based on the weight of the cyclodextrin composition, the cyclodextrin inclusion complex comprises cyclodextrin and an olefinic inhibitor of a generation of ethylene in production, the olefinic inhibitor comprising a compound having the structure:
wherein each of R ¹ , R ² are independently hydrogen or a C1-16 hydrocarbyl group and R ³ and R ⁴ are independently hydrogen or a C1-16 hydrocarbyl group on condition that at least minus one of R ¹ or R ² is methyl;
arranging the cyclodextrin composition on at least a portion of a packaging material surface in a thickness of about 0.01 micron to 1 millimeter to form a coating; and exposing the coating to a radiation source to form a cured cyclodextrin composition.
[0143] The list of limitations or elements includes, without limitation, the following:
The. the cyclodextrin composition additionally comprises about 0.1% by weight to 5% by weight of one or more photoinitiators based on the weight of the
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81/83 composition, in which irradiation is carried out with UV radiation;
B. the cyclodextrin composition additionally comprises about 0.1% by weight to 5% by weight of one or more photoinitiators based on the weight of the composition; and further comprises further exposing the cyclodextrin composition to a radiation source before coating, wherein the radiation source is ultraviolet radiation;
ç. one or more additional monomers, an additional photoinitiator, or a combination thereof is added to the cyclodextrin composition after additional exposure and before disposal;
d. the source of radiation is electron beam radiation;
and. the source of radiation is ultraviolet radiation;
f. the coating is arranged over the entire main surface of the packaging material;
g. the coating is disposed on a portion of a major main surface of the packaging material;
H. the arrangement is made through printing;
i. printing is gravure printing, flexo printing or inkjet printing;
j. the cured cyclodextrin composition comprises a pressure sensitive adhesive;
k. a liner is disposed on the cyclodextrin composition;
l. the ceiling is laid before irradiation;
m. the lining is disposed after irradiation;
n. the liner comprises a desiccant;
O. the treated packaging material is a treated container;
P. the method further comprises forming a treated container from the treated packaging material;
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q. the method further comprises forming a treated packaging leaflet from the treated packaging material;
r. the method further comprises forming a treated label from the treated packaging material;
s. the method further comprises forming a treated laminate;
t. the method further comprises forming a treated laminated container;
u. the method further comprises arranging the cured cyclodextrin composition within a container having a contained volume, wherein the cured cyclodextrin composition comes into contact with the contained volume;
v. the method further comprises arranging the cured cyclodextrin composition on the outside of a container having a confined volume, wherein the cured cyclodextrin composition is not in direct contact with the confined volume;
w. the method further comprises enclosing a production item within the container.
[0144] The foregoing reveals embodiments of the invention. In the description and claims, the expression about which modifies, for example, the amount of an ingredient in a composition, concentration, volume, process temperature, process time, yield, flow rate, pressure and similar values and ranges thereof , used in the description of the disclosure modalities, refers to the variation in the numerical quantity that can occur, for example, through typical handling and measurement procedures used to produce compounds, compositions, concentrates or formulations for use; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of starting materials or ingredients used to carry out similar methods and similar considerations. The term about also encompasses quantities
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83/83 that differ due to the aging of a formulation with a particular initial concentration or mixture, and quantities that differ due to mixing or processing a formulation with a particular initial concentration or mixture. When modified by the term, the claims attached thereto include equivalents to those quantities. "Optional" or "optionally" means that the event described subsequently or the circumstance may or may not occur, and that the description includes cases in which the event or circumstance occurs and cases where it does not. The present invention may comprise, consist of, or essentially consist of, suitably any of the elements recited or revealed. Therefore, the invention shown illustratively in this document can be practiced properly in the absence of any element that is not specifically disclosed in this document. The use of the singular typically includes and at least does not exclude the plural.
[0145] The specification, figures, examples and data provide a detailed explanation of the invention as it has been developed to date. The invention, however, can take the form of other modalities without departing from the spirit or the intended scope of the invention. The invention, therefore, resides in the appended claims.

权利要求:
Claims (15)
[1]
1. Cyclodextrin composition, CHARACTERIZED by the fact that it comprises one or more polymerizable radiation monomers comprising acrylic acid, methacrylic acid, an acrylate ester, a methacrylate ester, an acrylamide, a diacrylate, a triacrylate, a tetracrylate, or mixture thereof, and 0.001% to 25% by weight of a cyclodextrin inclusion complex based on the weight of the composition, the cyclodextrin inclusion complex comprising αcyclodextrin and 1-methylcyclopropene.
[2]
2. Composition according to claim 1, CHARACTERIZED by the fact that one or more radiation polymerizable monomers comprises acrylic acid, methacrylic acid, an acrylate ester, a methacrylate ester, an acrylamide, a diacrylate, a triacrylate, a tetraacrylate or a mixture thereof.
[3]
3. Composition, according to claim 1, CHARACTERIZED by the fact that it additionally comprises a photoinitiator, one or more prepolymers or both.
[4]
4. Composition according to claim 1, CHARACTERIZED by the fact that the olefinic inhibitor comprises 1-methyl cyclopropene and the cyclodextrin compound comprises α-cyclodextrin.
[5]
5. Composition of cured cyclodextrin, CHARACTERIZED by the fact that it comprises:
a polymer derived from a cyclodextrin composition as defined in any one of claims 1 to 4;
a cyclodextrin inclusion complex, the cyclodextrin inclusion complex comprising cyclodextrin and 1-methyl cyclopropene; and optionally one or more water scavengers, desiccants, adhesion promoters, anti-dirt agents, thermal stabilizers, oxidizing stabilizers,
Petition 870180159894, of 12/07/2018, p. 9/11
2/3 colorants, adjuvants, plasticizers or mixtures thereof;
where the cured cyclodextrin composition is derived from the electromagnetic irradiation of a cyclodextrin composition comprising one or more radiation polymerizable monomers and the cyclodextrin inclusion complex.
[6]
6. Cured cyclodextrin composition according to claim 5, CHARACTERIZED by the fact that it is present as a coating on at least a portion of a packaging material surface.
[7]
7. Cured cyclodextrin composition according to claim 5, CHARACTERIZED by the fact that the packaging material comprises a film, a blade, a bag, a package, a plate, a glass, a cover, a label, cardboard or a packaging leaflet.
[8]
8. Cured cyclodextrin composition according to claim 5, CHARACTERIZED by the fact that it comprises a pressure sensitive adhesive, a printed sign or a printed sign.
[9]
9. Cured cyclodextrin composition according to claim 5, CHARACTERIZED by the fact that the composition is arranged between a surface of a first packaging material and a surface of a second packaging material.
[10]
10. Cured cyclodextrin composition according to claim 5, CHARACTERIZED by the fact that the packaging material is included as part of a container.
[11]
11. Cured cyclodextrin composition according to claim 10, CHARACTERIZED by the fact that the packaging material is included as an addition within the container.
[12]
12. Cured cyclodextrin composition according to claim 10, CHARACTERIZED by the fact that the container additionally comprises a production item.
Petition 870180159894, of 12/07/2018, p. 11/10
3/3
[13]
13. Method of manufacturing a treated packaging material, CHARACTERIZED by the fact that it comprises:
The. form a cyclodextrin composition comprising one or more radiation polymerizable monomers and from 0.05% by weight to 10% by weight of a cyclodextrin inclusion complex based on the weight of the cyclodextrin composition, the cyclodextrin inclusion complex comprises α-cyclodextrin and 1-methylcyclopropene;
B. arranging the cyclodextrin composition on at least a portion of a packaging material surface at a thickness of 0.01 micron to 1 millimeter to form a coating; and
ç. exposing the coating to a radiation source to form a cured cyclodextrin composition.
[14]
14. Method according to claim 13, CHARACTERIZED by the fact that the cyclodextrin composition further comprises from 0.1% by weight to 5% by weight of one or more photoinitiators based on the weight of the composition, wherein the source of radiation is ultraviolet radiation.
[15]
15. Method according to claim 13, CHARACTERIZED by the fact that the cyclodextrin composition further comprises from 0.1% by weight to 5% by weight of one or more photoinitiators based on the weight of the composition; and further comprises exposing the cyclodextrin composition to ultraviolet radiation prior to disposal.

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法律状态:
2015-09-29| B27A| Filing of a green patent (patente verde) [chapter 27.1 patent gazette]|

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2016-03-01| B27C| Request for a green patent denied [chapter 27.3 patent gazette]|Free format text: O PEDIDO NAO ESTA APTO A PARTICIPAR DO PROGRAMA DE PATENTES VERDES.DESTA DATA CORRE PRAZO DE 60(SESSENTA) DIA PARA EVENTUAL RECURSO DO INTERESSADO |

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2016-10-11| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-04-03| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2018-08-07| B15K| Others concerning applications: alteration of classification|Ipc: A01N 25/10 (2006.01), A01N 25/22 (2006.01), A01N 2 |

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2018-09-11| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2019-01-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2019-02-05| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/10/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/10/2011, OBSERVADAS AS CONDICOES LEGAIS |

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2021-07-20| B25D| Requested change of name of applicant approved|Owner name: VERDANT TECHNOLOGIES, LLC (US) |

优先权:

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申请号 | 申请日 | 专利标题

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US201161468041P| true| 2011-03-27|2011-03-27|

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US61/468,041|2011-03-27|

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PCT/US2011/057017|WO2012134539A1|2011-03-27|2011-10-20|Cyclodextrin compositions, articles, and methods|

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