WO2016071875A1 - Polymer packaging that delays the ripening and senescence process in fresh vegetable products - Google Patents

Polymer packaging that delays the ripening and senescence process in fresh vegetable products Download PDF

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Publication number
WO2016071875A1
WO2016071875A1 PCT/IB2015/058582 IB2015058582W WO2016071875A1 WO 2016071875 A1 WO2016071875 A1 WO 2016071875A1 IB 2015058582 W IB2015058582 W IB 2015058582W WO 2016071875 A1 WO2016071875 A1 WO 2016071875A1
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Prior art keywords
ethylene
capture
packaging
polymer composition
fruits
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PCT/IB2015/058582
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Spanish (es)
French (fr)
Inventor
Cesar Augusto SIERRA ÁVILA
Sugey Maryuri MARTÍNEZ GÓMEZ
Luis Alejandro GUTIERREZ CARRANZA
Ricaurte RODRÍGUEZ ANGULO
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Universidad Nacional De Colombia
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Publication of WO2016071875A1 publication Critical patent/WO2016071875A1/en

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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/144—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23B7/152—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere comprising other gases in addition to CO2, N2, O2 or H2O ; Elimination of such other gases
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3409—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23L3/3445—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere comprising other gases in addition to CO2, N2, O2 or H2O
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants

Definitions

  • the present invention relates to the sector of food chemistry, specifically to a package polymer made from polyolefins that incorporates in its composition at least one additive that allows to delay the maturation and senescence process in fruits, vegetables and foliage, thus offering the possibility of extending the life of these products perishable during transport, storage and marketing.
  • active packaging as one that can alter or preserve several aspects in the food to achieve extend their lifespan, which focus on the modification of physiological processes such as Breathing in fruits and vegetables.
  • active packaging can contain additives that perform specific functions inside the packaging as the modification of the process of breathing stated above.
  • the mechanisms of operation of an active package can be: a) compound release (eg breathing gases) required in the atmosphere surrounding the food, b) of adsorption-absorption of a compound of interest (Ex. Ethylene) or c) obstruction of compound activity determinant in maturation.
  • gases are found that affect their maturation process generating changes in color, taste and aroma, these are: oxygen (O 2 ), carbon dioxide ( CO 2 ) and ethylene (C 2 H 4 ).
  • O 2 oxygen
  • CO 2 carbon dioxide
  • C 2 H 4 ethylene
  • the control of the levels of the gases mentioned above is useful to delay the maturation process and thus extend the shelf life in fruits and vegetables.
  • O 2 inside the packaging are reduced and those of CO 2 are increased, it is possible to achieve that the ripening of fruits and vegetables can be delayed, since the speed of ethylene production is reduced and the speed of softening maturation itself manages to be delayed (Yahia, E. 2009).
  • the control of O 2 and CO 2 is carried out using the permeability of the film to said gases, or by means of adsorbent agents contained in a disposable hermetic bag known in English as sachet, (derived from the French word "sachet”);
  • sachet a disposable hermetic bag
  • sacks are additional envelopes that are not part of the packaging, but that travel inside the package together with the food and are made of a generally inorganic or polymeric material, with a specific pore size (US 4856650) that contains the active agent that It is responsible for the adsorption of gas.
  • this one It is generally carried out by methodologies complementary to the packaging itself, as they are, the use of adsorbent agents in “saches” (Ahvenainen, R. 2003) and direct treatments in the plant material that inhibits ethylene biosynthesis, in which the use of 1-MCP, AOA and AVG stand out (1-methylcyclopropane, aminooxyacetic acid and aminovinylglycine, respectively) in solution (Paliyath, et al ;, 2008).
  • the present invention relates to a polymeric package that prolongs the shelf life of fresh vegetable products, which can be used in the fruit, vegetable and foliage marketing chains.
  • This invention offers a product of easy production and agro-industrial implementation, capable of replacing existing technologies such as the use of specialized packaging materials in packaging systems with modified atmosphere, which only control the levels of O 2 and CO 2 , and that for Control ethylene use complementary attachments, such as the sacks already referred to, which are not part of the packaging entity.
  • This invention shows polymeric packages with "additives" within the film, which modify the transmission rate of O 2 and CO 2 (gas barrier property) and also the concentration of ethylene, without the need for additional elements.
  • the initial consideration for the design of the formulation was to find chemicals sufficiently active and compatible (with nature of the polymer used) to be part of the packaging film and at the same time exercise control over the internal atmosphere of the bag removing ethylene.
  • different substances of the family of fatty acid derived esters, terpenes and pyridine compounds taking into account a possible affinity with ethylene.
  • experimentally it they placed various chemical compounds from families mentioned in contact with fresh fruits of optimal quality, within appropriate containers for Study of the fruit ripening process.
  • additive defined substances, named in this invention as an "additive", with the best features to produce the film that desired, the percentages of additive that were determined should be added to achieve the optimal effect on the fruits or vegetables that could be stored. Be found that percentages below 5% addition of additive allow to reach the best conditions of packing. The useful time of the packaging was determined with a single fruit; gulupa, the family's climacteric fruit of the passionflower, whose respiration rate is high in relation to other fruits and vegetables normally Found in a supermarket.
  • Polyoxyethylene monooleate additives sorbitan oleate, glycerol ⁇ -monooleate and the mixture of monkey and triglycerides were chosen by their nature non-ionic surfactant that provide the properties required on the packaging, as considered non-toxic, and because of the thermal stability that allowed the processing of the packaging by means of extrusion. Further to a possible antifog activity, the structure chemistry of these aliphatic esters allows to wait for a interaction with ethylene produced by fruits and vegetables and thus have anti-ripening capacity.
  • Squalene is an olefinic substance capable of retaining within the polymeric film of the packaging to ethylene, the molecule responsible for maturation and over-ripening of fresh plant products. Squalene, due to its physicochemical properties, can become an integral part of the film of the polyolefin keeping unsaturations active present in its chemical structure, which favors the ethylene retention.
  • diludine 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate diethyl is a nitrogen heterocyclic compound that when incorporated, it provides a polymeric film slight yellow color.
  • the high reducing power of the diludine allows to eliminate ethylene from the environment internal packing, possibly turning it into ethane, which is not recognized by the receptors of ripening of the fresh vegetable product. While he is reaction takes place, in turn the color of the packaging it is modified until it becomes translucent, this being last one indicative of its functionality and the end of the conservation capacity provided by the packaging.
  • AOA aminooxyacetic acid
  • the additives introduced in the film retarding packaging of the ripening process and senescence in fruits, vegetables and foliage have a high capacity to extend product life of plant origin. According to the results, the products Fresh vegetables can maintain their properties organoleptic for times longer than 6 weeks.
  • the chemical characteristics and Biological additives, concentration used and affinity with the polymer chains of the film of packaging allow to ensure the safety of that type of active packaging, see the Material Safety Data Sheet, MSDS, for each additive according to registration number chemical: squalene: CAS # 111-02-4; diludine: CAS # 1149-23-1; AOA or aminooxyacetic acid: CAS # 645-88-5; polyoxyethylene monooleate: CAS # 9005-65-6; sorbitan oleate: CAS # 9015-08-1; Glycerol ⁇ -monooleate: CAS # 111-03-5; and the mixture of mono and triglycerides: CAS # 111-03-5 and 122-32-7, respectively.
  • Figure 6 shows the effect on production of ethylene, when using as an additive aliphatic esters to different concentrations (0.5%, 1.0% and 1.5% identified as AA1, AA2 and AA3, respectively) in a package of fruits, where it is appreciated that for times Less than 6 weeks of storage, production of ethylene does not exceed 160 microliters / kg / h, for None of the additive concentrations evaluated.
  • Figure 7 shows the effect on the ethylene production, using diludin as an additive at different concentrations (0.5%, 1.0% and 1.5% identified as AR1, AR2 and AR3, respectively) in a packing of fruits, where it is appreciated that the production of ethylene does not exceed 160 microliters / kg / h, for none of the additive concentrations evaluated and appreciate a variation of approximately 20 microliters / kg / h in ethylene production between the three concentrations.
  • Figure 8 shows the effect on production of ethylene, from AOA at different concentrations (0.5%, 1.0% and 1.5% identified as AI1, AI2 and AI3, respectively) as an additive in a fruit package, where it is appreciated that the maximum peak in the production of ethylene is between 250 and 350 microliters / kg / h at five weeks, this time being observe the biggest difference in ethylene production in the three concentrations.
  • the sensory shelf life of the fruit with the help of a panel trained cupping (made up of 8 panelists).
  • the methodology involved the storage of different lots of fruit (8 per package) under the same conditions (8 ° C,% H.R. 54.5 ⁇ 3) at different times, 7, 6, 5, 4, 3, 2 weeks Then a fruit of each period of time was arranged for sensory analysis by The panelists.
  • the analysis was performed on three Critical parameters in fruit quality, with which were previously trained; appearance and color of the shell, appearance and color of the pulp of the fruit and the aroma and flavor of the pulp of the fruit, by means of a descriptive test of scores.
  • the data resulting are compared with those obtained for a commercial polymeric packaging currently used by tropical fruit exporters from the same family Vegetable to the studied.
  • the aforementioned adsorbents, absorbents, reducers or inhibitors of ethylene that allow reducing or modifying the concentration of ethylene in the atmosphere surrounding the fruits, vegetables or foliage whose ripening and senescence process is sought to be delayed, will be identified as a single group of compounds called ethylene capture agents , regardless of the chemical mechanism of the interaction of said agent with ethylene.
  • the preferred methodology used in the manufacture of flexible anti-ripening packages for plant material consists in obtaining a plastic film by extrusion and blowing, using as a load a physical mixture between the additives (in the form of pellets; masterbatch ) and the polymer matrix in pellets .
  • the direct addition of the liquid or solid additives used in this invention to the extruder causes problems of processability and heterogeneity of the additive in the film, with a high detriment of the desired anti-aging properties. Therefore, the additive has to be pre-extruded with the polyolefin in order to obtain a " masterbatch " with high percentages of additive (between 10 and 20%) in the form of pellets.
  • the final presentation of the translucent polymeric packaging It has a thickness between 0.035 and 0.052 mm and no microperforations.
  • Fig. 1 the process of maturation over six (6) weeks for a set of gulupa fruits (Passiflora edulis Sims fo. edulis) stored under the same conditions environmental in different types of packaging, where “without pack ”represents fruit samples stored without use of packaging, "polyolefin film” represents a polyethylene or polypropylene packaging without additive some, and “polyolefin film with absorbent” represents a polyethylene or polypropylene gasket which through an extrusion process has been introduced 2% (w / w) squalene as an additive ethylene absorbent.
  • Figure 2 shows the process of maturation over six (6) weeks for a set of gulupa fruits (Passiflora edulis Sims fo. edulis) stored under the same conditions environmental in different types of packaging, where “without pack ”represents fruit samples stored without use of packaging, "polyolefin film” represents a polyethylene or polypropylene packaging without additive some, and “polyolefin film with reducer” represents a polyethylene or polypropylene gasket which through an extrusion process has been introduced 2% (w / w) diludine as an additive ethylene reducer
  • Figures 3, 4 and 5 show the gulupa sensory quality parameters in two different packages and at different periods of storage at a temperature of 8 ° C: a package commercial polymer (dark bars) and a gasket asset containing squalene as an absorbent additive of the present invention (light gray bars).
  • Figure 1 shows the process of maturation over six weeks for a set of gulupa fruits (Passiflora edulis Sims fo. edulis) stored under the same environmental conditions in Different types of packaging.
  • the fruit stored in the packing with the adsorbent additive in a concentration of 2% establishes an atmosphere in the packaging with a lower concentration of ethylene throughout all trial weeks, which makes a big difference with unpacked fruit and fruit in a package plastic without the adsorbent additive.
  • Remarkable is the decrease in the climatic peak (maximum production of ethylene in five weeks) where with the film with additive is presented 3 and 6 times less concentration of ethylene than with the polymer film without additive or with Fruit without packaging, respectively.
  • Figure 2 presents the results for the case in which the additive used in one of the packages it is an olefin reducing agent in a concentration less than 2% and its comparison with other types of packaging. Also in this case the gulupa fruits stored in The polyolefin bag with the additive is preserved in better way than the other two samples with which Compare the ripening process. Similar to previous example, in the climacteric peak the reduction of Ethylene production with the reducer packaging is appreciable.
  • a shaped cupping panel by 8 trained panelists evaluated the appearance-color of the shell, appearance-color of the pulp and aroma-flavor of the pulp. And it was compared to a package Commercial used currently.
  • the values obtained for the three attributes were averaged for all experiments and its value is reported as “Medium scores” in Figures 3, 4 and 5.
  • Figures 3, 4 and 5 show these results for each attribute, values close to the maximum they represent the best possible quality and close values to one they represent a totally undesirable quality.
  • the results for absorbent and reducing additives ethylene are very similar, therefore only Show the result with the absorbent.
  • Figure 3 and 5 show that the appearance and color of the shell and appearance and color of the pulp during the period of storage suffer small differences with respect to commercial packaging. But after 4 and until 7 week, there are no appreciable changes. Therefore the developed packaging behaves the same as packaging commercial in these attributes.
  • Figure 4 shows how Commercial packaging better preserves the aroma and flavor of the pulp of the fruit during the first 4 weeks of storage. But the packing with absorbent here developed presents better results in recent storage weeks (from week 4 to week 7). The above is very important, since the last weeks of storage, are precisely those that They use to display the fruit to the final buyer. Fits note that within the analyzed attributes, the aroma and taste of the pulp of the fruit is the most important For the final consumer.
  • additives "A” ethylene inhibitors "I” such as AOA or “R” ethylene reducers such as diludine a different concentrations ranging from 0.5: 1.0 and 1.5% (w / w).
  • the scope of this invention is defined to fruit products that in their post-harvest process They produce ethylene within their metabolic process. May be for cargo packaging in transport or for domestic storage

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Abstract

The present invention relates to a polymer composition for absorbing ethylene and other gaseous compounds, which comprises a polymer substrate that consists of polyolefin or a mixture of polyolefins and one or more ethylene capture agents in a concentration between 0.5% and 5%. The invention also relates to a packaging that delays the process of ripening and senescence in fruits, vegetables and foliage and which is characterised in that it contains the above-mentioned composition, and a method for extending the shelf life of said perishable products during transport, storage and sale thereof.

Description

EMPAQUE POLIMÉRICO QUE RETARDA EL PROCESO DE MADURACION Y SENESCENCIA DE PRODUCTOS VEGETALES FRESCOSPOLYMER PACKAGING THAT DELAYS THE PROCESS OF             MATURATION AND SENESCENCE OF FRESH VEGETABLE PRODUCTS
La presente invención se refiere al sector de la química de alimentos, específicamente a un empaque polimérico fabricado a partir de poliolefinas que incorpora en su composición al menos un aditivo que permite retardar el proceso de maduración y senescencia en frutas, vegetales y follaje, ofreciendo así la posibilidad de extender la vida útil de dichos productos perecederos durante su transporte, almacenamiento y comercialización.The present invention relates to the sector of                 food chemistry, specifically to a package                 polymer made from polyolefins that                 incorporates in its composition at least one additive that                 allows to delay the maturation and senescence process                 in fruits, vegetables and foliage, thus offering the                 possibility of extending the life of these products                 perishable during transport, storage and marketing.
A lo largo de la historia se han desarrollado técnicas y procesos encaminados hacia el desafío de preservar los alimentos en las mejores condiciones tanto sensoriales como fitosanitarias. El diseño y creación de empaques para alimentos es una pieza muy importante dentro de las técnicas dirigidas al mantenimiento y aseguramiento de la calidad alimenticia, puesto que el empaque se encuentra directamente relacionado con dos funciones básicas que son: el proceso de conservación y la protección de los alimentos. Así, el desempeño que cumple un empaque, además de tener un rol activo en la extensión de la vida útil del alimento, es cuidar el alimento de las condiciones ambientales como luz, oxígeno, humedad, microorganismos, daños mecánicos y contaminantes (Ahvenainen, R. 2003).Throughout history they have developed                 techniques and processes aimed at the challenge of                 preserve food in the best conditions both                 sensory as phytosanitary. The design and creation of                 food packaging is a very important piece                 within the techniques aimed at maintenance and                 food quality assurance, since the                 packaging is directly related to two                 basic functions that are: the conservation process and                 Food protection. So, the performance that                 fulfills a package, in addition to having an active role in the                 extension of the shelf life of food, is to take care of the                 nourishment of environmental conditions such as light,                 oxygen, moisture, microorganisms, mechanical damage and                 pollutants (Ahvenainen, R. 2003).
De esta manera surge una definición de “empaque activo” como aquel que puede alterar o conservar varios aspectos en el alimento para así lograr extender su vida útil, los cuales se centran en la modificación de procesos fisiológicos como es el caso de la respiración en frutas y vegetales. Para cumplir con el proceso de conservación, los empaques activos pueden contener aditivos que desempeñan funciones específicas dentro del empaque como la modificación del proceso de respiración anteriormente enunciado. Los mecanismos de operación de un empaque activo pueden ser de: a) liberación de compuestos (Ej. gases de respiración) requeridos en la atmósfera que rodea al alimento, b) de adsorción-absorción de un compuesto de interés (Ej. Etileno) o c) obstrucción de la actividad del compuesto determinante en la maduración.In this way a definition of                 "Active packaging" as one that can alter or                 preserve several aspects in the food to achieve                 extend their lifespan, which focus on the                 modification of physiological processes such as                 Breathing in fruits and vegetables. To accomplish with                 the conservation process, active packaging can                 contain additives that perform specific functions                 inside the packaging as the modification of the process of                 breathing stated above. The mechanisms of                 operation of an active package can be: a)                 compound release (eg breathing gases)                 required in the atmosphere surrounding the food, b) of                 adsorption-absorption of a compound of interest (Ex.                 Ethylene) or c) obstruction of compound activity                 determinant in maturation.
En la atmósfera circundante de los alimentos de origen vegetal (frutas y verduras, entre otros), se encuentran gases que afectan su proceso de maduración generando cambios de color, sabor y aroma, éstos son: oxígeno (O2), dióxido de carbono (CO2) y etileno (C2H4). En los procesos de manejo poscosecha y conservación de alimentos perecederos, el control de los niveles de los gases antes mencionados, es útil para lograr retrasar el proceso de maduración y de esta forma extender la vida útil en frutas y vegetales. Cuando los niveles de O2 en el interior del empaque se reducen y los de CO2 se incrementan, es posible lograr que la maduración de frutas y vegetales pueda ser retrasada, ya que la velocidad de producción de etileno es reducida y la velocidad de ablandamiento propio de la maduración logra ser retrasada (Yahia, E. 2009).In the surrounding atmosphere of plant-based foods (fruits and vegetables, among others), gases are found that affect their maturation process generating changes in color, taste and aroma, these are: oxygen (O 2 ), carbon dioxide ( CO 2 ) and ethylene (C 2 H 4 ). In the processes of post-harvest management and preservation of perishable foods, the control of the levels of the gases mentioned above is useful to delay the maturation process and thus extend the shelf life in fruits and vegetables. When the levels of O 2 inside the packaging are reduced and those of CO 2 are increased, it is possible to achieve that the ripening of fruits and vegetables can be delayed, since the speed of ethylene production is reduced and the speed of softening maturation itself manages to be delayed (Yahia, E. 2009).
Al usar películas como empaques, el control de O2 y CO2 se realiza haciendo uso de la permeabilidad propia de la película a dichos gases, o por medio de agentes adsorbentes contenidos en una bolsa hermética desechable conocida en inglés como sachet, (derivada de la palabra francesa “sachet”); estos sacos son sobres adicionales que no hacen parte del empaque, pero que viajan al interior del mismo junto con el alimento y se fabrican de un material inorgánico o polimérico generalmente, con un tamaño de poro específico (US 4856650) que contiene el agente activo que se encarga de la adsorción del gas. Cuando se requiere atrapar oxígeno empleando los referidos sacos, se han encontrado buenos resultados utilizando sales de cobre y de hierro como agentes adsorbentes (US 7147799); otra posibilidad es usar el agente absorbente de oxígeno directamente en el material de empaque y para estas aplicaciones generalmente se han incorporado sales de metales de transición (US 5700554), o aluminosilicatos porosos con alto poder de retención de gases (US 5221571).When using films as packaging, the control of O 2 and CO 2 is carried out using the permeability of the film to said gases, or by means of adsorbent agents contained in a disposable hermetic bag known in English as sachet, (derived from the French word "sachet"); These sacks are additional envelopes that are not part of the packaging, but that travel inside the package together with the food and are made of a generally inorganic or polymeric material, with a specific pore size (US 4856650) that contains the active agent that It is responsible for the adsorption of gas. When oxygen trapping is required using the said sacks, good results have been found using copper and iron salts as adsorbents (US 7147799); Another possibility is to use the oxygen absorbing agent directly in the packing material and for these applications, transition metal salts (US 5700554), or porous aluminosilicates with high gas retention power (US 5221571) have generally been incorporated.
Con respecto al manejo de los niveles de etileno en el interior de empaques para alimentos, éste generalmente es llevado a cabo mediante metodologías complementarias al empaque en sí, como lo son, la utilización de agentes adsorbentes en “sachés” (Ahvenainen, R. 2003) y los tratamientos directos en el material vegetal que inhiben la biosíntesis del etileno, en los que sobresalen el uso del 1-MCP, AOA y AVG (1-metilciclopropano, ácido aminooxiacético y aminovinilglicina, respectivamente) en solución (Paliyath, et al;, 2008).With regard to the management of the levels of                 ethylene inside food packaging, this one                 It is generally carried out by methodologies                 complementary to the packaging itself, as they are, the                 use of adsorbent agents in “saches”                 (Ahvenainen, R. 2003) and direct treatments in the                 plant material that inhibits ethylene biosynthesis,                 in which the use of 1-MCP, AOA and AVG stand out                 (1-methylcyclopropane, aminooxyacetic acid and                 aminovinylglycine, respectively) in solution                 (Paliyath, et al ;, 2008).
Aplicaciones donde el empaque polimérico directamente, debido a un sinergismo de sus propiedades barrera y/o a la presencia de aditivos en la película, produzca una disminución de la concentración de etileno en la atmósfera interna del empacado no son muy comunes, siendo el más cercano a este tipo de mecanismo, el trabajo desarrollado por Holland Robert (US 5334623), el cual se basa en el uso de dienos electro deficientes incorporados en empaques poliméricos de polietileno o policarbonatos. El aditivo empleado consiste en un diesteroctílico de tetrazina que induce coloración roja, y cuando el etileno es absorbido dentro de la película su coloración desaparece, sirviendo por tanto como indicador de la funcionalidad, por periodos de tiempo de entre las 40 horas hasta los varios días (p.ej. cuatro días) a 20ºC.Applications where polymeric packaging                 directly, due to a synergism of its properties                 barrier and / or the presence of additives in the film,                 produce a decrease in ethylene concentration                 in the internal atmosphere of the packing they are not very common,                 being the closest to this type of mechanism, the                 work developed by Holland Robert (US 5334623), the                 which is based on the use of electro-deficient dienes                 incorporated in polymeric polyethylene packages or                 polycarbonates The additive used consists of a                 tetrazine diesteroctyl that induces red coloration,                 and when ethylene is absorbed into the film                 its coloration disappears, serving as much as                 Functionality indicator, for periods of time                 between 40 hours and several days (eg four                 days) at 20 ° C.
La presente invención relaciona un empaque polimérico que prolonga la vida útil de productos vegetales frescos, el cual puede ser usado en las cadenas comercializadoras de frutas, vegetales y follajes. Esta invención ofrece un producto de fácil producción e implementación agroindustrial, capaz de reemplazar tecnologías existentes tales como el uso de materiales de empaque especializado en los sistemas de empaque con atmósfera modificada, que solo controlan los niveles de O2 y CO2, y que para controlar el etileno usan aditamentos complementarios, como los sachés ya referidos, que no hacen parte de la entidad del empaque. Esta invención muestra empaques poliméricos con “aditivos” dentro de la película, que modifican la velocidad de transmisión de O2 y CO2 (propiedad barrera de gases) y además la concentración del etileno, sin necesidad de elementos adicionales.The present invention relates to a polymeric package that prolongs the shelf life of fresh vegetable products, which can be used in the fruit, vegetable and foliage marketing chains. This invention offers a product of easy production and agro-industrial implementation, capable of replacing existing technologies such as the use of specialized packaging materials in packaging systems with modified atmosphere, which only control the levels of O 2 and CO 2 , and that for Control ethylene use complementary attachments, such as the sacks already referred to, which are not part of the packaging entity. This invention shows polymeric packages with "additives" within the film, which modify the transmission rate of O 2 and CO 2 (gas barrier property) and also the concentration of ethylene, without the need for additional elements.
La consideración inicial para el diseño de la formulación, fue el encontrar sustancias químicas suficientemente activas y compatibles (con la naturaleza del polímero utilizado) como para formar parte de la película del empaque y a la vez ejercer control sobre la atmósfera interna de la bolsa retirando el etileno. Para ese propósito se estudiaron diferentes sustancias de la familia de los ésteres derivados de ácidos grasos, terpenos y compuestos piridínicos teniendo en cuenta una posible afinidad con el etileno. Experimentalmente se colocaron diversos compuestos químicos de las familias mencionadas en contacto con frutas frescas de óptima calidad, dentro de recipientes apropiados para el estudio del proceso de maduración de frutas. Y de acuerdo a los resultados preliminares sobre la incidencia del compuesto químico en las propiedades organolépticas externas del fruto (color, textura y olor) se redujo su número a siete: monooleato de polioxietileno, oleato de sorbitan, α-monooleato de glicerol, mezcla de mono y trigliceridos, escualeno, diludina y AOA (ácido aminooxiacético).The initial consideration for the design of the                 formulation was to find chemicals                 sufficiently active and compatible (with nature                 of the polymer used) to be part of the                 packaging film and at the same time exercise control over the                 internal atmosphere of the bag removing ethylene. For                 that purpose different substances of the                 family of fatty acid derived esters,                 terpenes and pyridine compounds taking into account a                 possible affinity with ethylene. Experimentally it                 they placed various chemical compounds from families                 mentioned in contact with fresh fruits of optimal                 quality, within appropriate containers for                 Study of the fruit ripening process. And of                 according to the preliminary results on the                 incidence of the chemical compound in the properties                 external organoleptic of the fruit (color, texture and                 smell) its number was reduced to seven: monooleate                 polyoxyethylene, sorbitan oleate, α-monooleate                 glycerol, mixture of mono and triglycerides, squalene,                 diludine and AOA (aminooxyacetic acid).
Definidas las sustancias, denominadas en esta invención como “aditivo”, con las mejores características para producir la película que se deseaba, se determinaron los porcentajes de aditivo que debían agregarse para alcanzar el efecto óptimo sobre las frutas o vegetales que se pudiesen almacenar. Se encontró que porcentajes inferiores al 5% de adición de aditivo permiten alcanzar las mejores condiciones de empaque. El tiempo útil del empaque se determinó con una sola fruta; gulupa, fruta climatérica de la familia de las pasifloráceas, cuya tasa de respiración es alta en relación con las demás frutas y vegetales normalmente encontradas en un supermercado.Defined substances, named in this                 invention as an "additive", with the best                 features to produce the film that                 desired, the percentages of additive that were determined                 should be added to achieve the optimal effect on                 the fruits or vegetables that could be stored. Be                 found that percentages below 5% addition of                 additive allow to reach the best conditions of                 packing. The useful time of the packaging was determined with                 a single fruit; gulupa, the family's climacteric fruit                 of the passionflower, whose respiration rate is high                 in relation to other fruits and vegetables normally                 Found in a supermarket.
Varias son las frutas que presentan una crisis climatérica y por ende la modificación de la producción de etileno puede permitir retrasar la senescencia de este tipo de frutos y extender su vida útil (Hernández et al. 2010).There are several fruits that present a crisis                 climacteric and therefore the production modification                 of ethylene can allow to delay the senescence of                 this type of fruit and extend its useful life (Hernández                 et al. 2010).
“De acuerdo con el patrón respiratorio y la síntesis de etileno en una etapa temprana de la madurez, los frutos han sido clasificados en dos categorías: climatéricos o no climatéricos (Kuntz et al. 1998, Seymour et al. 1993).“According to the respiratory pattern and the                 ethylene synthesis at an early stage of maturity,                 The fruits have been classified into two categories:                 climacteric or non-climacteric (Kuntz et al. 1998,                 Seymour et al. 1993).
Rhodes (1980), citado por Herrero y Guardia (1992), define la crisis climatérica como un período de evolución de ciertos frutos en el que se sucede una serie de cambios bioquímicos que se inician con la producción autocatalítica del etileno, marcando el paso del crecimiento hacia la senescencia, presentando un aumento de la respiración, que conducen a la maduración. En los frutos tropicales como guayaba (Psidium guajava), arazá (Eugenia stipitata), copoazú (Theobroma grandiflorum), gulupa o cholupa (Passiflora edulis) se encuentra que hay crisis climatérica al inicio de la maduración; sin embargo, en otros casos como el camucamu (Myrciaria dubia), la coconá (Solanum sessiliflorum) y algunas variedades de ají (Capsicum spp), la maduración no se encuentra acompañada de crisis climatérica (Bardales et ál. 2008; Hernández et ál. 2007; Barrera et ál. 2008; Jiménez et ál. 2008)”.Rhodes (1980), cited by Blacksmith and Guard                 (1992), defines the climate crisis as a period of                 evolution of certain fruits in which a                 series of biochemical changes that begin with the                 autocatalytic production of ethylene, marking the step                 of growth towards senescence, presenting a                 increased breathing, which lead to maturation.                 In tropical fruits like guava (Psidium guajava),                 arazá (Eugenia stipitata), copoazú (Theobroma                 grandiflorum), gulupa or cholupa (Passiflora edulis) se                 find that there is a climate crisis at the beginning of the                 maturation; however, in other cases such as camucamu                 (Myrciaria dubia), coconá (Solanum sessiliflorum) and                 some varieties of chili pepper (Capsicum spp), ripening                 It is not accompanied by weather crisis                 (Bardales et al. 2008; Hernández et al. 2007; Barrera et                 to the. 2008; Jiménez et al. 2008) ”.
Los aditivos monooleato de polioxietileno, oleato de sorbitan, α-monooleato de glicerol y la mezcla de mono y trigliceridos se escogieron por su naturaleza surfactante no iónica que proporcionan las propiedades requeridas en el empaque, por considerarse no tóxicos, y por la estabilidad térmica que permitió el procesamiento de los empaques por medio de extrusión. Adicionalmente a una posible actividad antiempañante, la estructura química de estos esteres alifáticos permite esperar una interacción con el etileno producido por las frutas y verduras y así tener capacidad antimaduración.Polyoxyethylene monooleate additives,                 sorbitan oleate, glycerol α-monooleate and the mixture                 of monkey and triglycerides were chosen by their nature                 non-ionic surfactant that provide the properties                 required on the packaging, as considered non-toxic, and                 because of the thermal stability that allowed the processing                 of the packaging by means of extrusion. further                 to a possible antifog activity, the structure                 chemistry of these aliphatic esters allows to wait for a                 interaction with ethylene produced by fruits and                 vegetables and thus have anti-ripening capacity.
El escualeno es una sustancia olefínica capaz de retener dentro de la película polimérica del empaque al etileno, molécula responsable de la maduración y sobremaduración de productos de origen vegetal frescos. El escualeno, por sus propiedades fisicoquímicas, puede entrar a formar parte integral de la película de la poliolefina manteniendo activas las insaturaciones presentes en su estructura química, lo cual favorece la retención del etileno.Squalene is an olefinic substance capable                 of retaining within the polymeric film of the packaging                 to ethylene, the molecule responsible for maturation and                 over-ripening of fresh plant products.                 Squalene, due to its physicochemical properties, can                 become an integral part of the film of the                 polyolefin keeping unsaturations active                 present in its chemical structure, which favors the                 ethylene retention.
Por su parte, la diludina (2,6-dimetil-1,4-dihidropiridina-3,5-dicarboxilato de dietilo) es un compuesto heterocíclico nitrogenado que al incorporarse proporciona en la película polimérica un ligero color amarillo. El alto poder reductor de la diludina permite eliminar el etileno del ambiente interno del empaque, convirtiéndolo posiblemente en etano, el cual no es reconocido por los receptores de maduración del producto vegetal fresco. Mientras esta reacción tiene lugar, a su vez la coloración del empaque se va modificando hasta hacerse traslúcido, siendo esto último un indicativo de su funcionalidad y del final de la capacidad de conservación brindada por el empaque.On the other hand, diludine                 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate                 diethyl) is a nitrogen heterocyclic compound that                 when incorporated, it provides a polymeric film                 slight yellow color. The high reducing power of the                 diludine allows to eliminate ethylene from the environment                 internal packing, possibly turning it into                 ethane, which is not recognized by the receptors of                 ripening of the fresh vegetable product. While he is                 reaction takes place, in turn the color of the packaging                 it is modified until it becomes translucent, this being                 last one indicative of its functionality and the end of                 the conservation capacity provided by the packaging.
El efecto del escualeno y la diludina, como aditivos absorbente y reductor, en la retención o remoción del etileno a una temperatura de 8ºC pueden verse en las Figuras 1 y 2, respectivamente. La producción de etileno se determinó como la cantidad de etileno presente en la atmósfera circundante al conjunto de frutos con respecto al peso en kg de fruta dentro del empaque, el cual en el momento inicial es cero y su aumento es debido a la producción de etileno por los frutos con el paso de los días. Para el empaque con aditivo se observa una reducción en la cantidad de etileno (producido por la fruta) presente en la atmósfera al interior del empaque en comparación con la fruta sin empacar y la película sin aditivo. Esta reducción se hace más evidente en el pico climatérico (tiempo de mayor producción de etileno por una fruta climatérica), el cual ocurre a las 5 semanas de almacenamiento, donde la producción de etileno es superior a 600 microlitros /kg /h en el caso de las frutas sin empacar y se reduce a aproximadamente 100 microlitros /kg /h con la “película poliolefínica con absorbente” o la “película poliolefínica con reductor” de la presente invención.The effect of squalene and diludin, as                 absorbent and reducing additives, in retention or                 ethylene removal at a temperature of 8 ° C can                 see in Figures 1 and 2, respectively. The                 Ethylene production was determined as the amount of                 ethylene present in the atmosphere surrounding the whole                 of fruits with respect to the weight in kg of fruit within the                 packing, which at the initial moment is zero and its                 increase is due to ethylene production by                 Fruits with the passing of days. For packing with                 additive a reduction in the amount of                 ethylene (produced by the fruit) present in the                 atmosphere inside the package compared to the                 Unpacked fruit and film without additive. This                 reduction becomes more evident in the climacteric peak                 (time of increased production of ethylene for one fruit                 climacteric), which occurs 5 weeks after                 storage, where ethylene production is                 greater than 600 microliters / kg / h in the case of                 unpacked fruits and reduced to approximately 100                 microliters / kg / h with the "polyolefin film with                 absorbent ”or“ polyolefin film with reducer ”                 of the present invention.
En cuanto al del ácido aminooxiacético (AOA), ha sido ampliamente estudiada su función como alternativa para controlar la sobremaduración en frutos climatéricos. Es conocido que el AOA interviene en la biosíntesis de la hormona que afecta la función de la enzima ACC (acido-1-aminocyclopropil-1-carboxilico, por sus siglas en ingles), la cual participa en la producción de etileno.As for aminooxyacetic acid (AOA),                 its function has been widely studied as                 alternative to control over-ripening in fruits                 weather. It is known that the AOA intervenes in the                 hormone biosynthesis that affects the function of the                 ACC enzyme (acid-1-aminocyclopropyl-1-carboxylic acid, by                 its acronym in English), which participates in the                 ethylene production
Los aditivos introducidos en la película de los empaques retardantes del proceso de maduración y senescencia en frutos, verduras y follaje, presentan una alta capacidad para extender la vida útil de productos de origen vegetal. Según los resultados, los productos vegetales frescos pueden mantener sus propiedades organolépticas por tiempos superiores a las 6 semanas. Adicionalmente, las características químicas y biológicas de los aditivos, la concentración usada y la afinidad con las cadenas poliméricas de la película del empaque permiten asegurar la inocuidad de ese tipo de empaques activos, ver el Material safety Data Sheet, MSDS, para cada aditivo según número de registro químico: escualeno: CAS#111-02-4; diludina: CAS#1149-23-1; AOA ó ácido aminooxiacético: CAS#645-88-5; monooleato de polioxietileno: CAS#9005-65-6; oleato de sorbitan: CAS#9015-08-1; α-monooleato de glicerol: CAS#111-03-5; y la mezcla de mono y trigliceridos: CAS#111-03-5 y 122-32-7, respectivamente.The additives introduced in the film                 retarding packaging of the ripening process and                 senescence in fruits, vegetables and foliage, have a                 high capacity to extend product life                 of plant origin. According to the results, the products                 Fresh vegetables can maintain their properties                 organoleptic for times longer than 6 weeks.                 Additionally, the chemical characteristics and                 Biological additives, concentration used and                 affinity with the polymer chains of the film of                 packaging allow to ensure the safety of that type of                 active packaging, see the Material Safety Data Sheet,                 MSDS, for each additive according to registration number                 chemical: squalene: CAS # 111-02-4; diludine:                 CAS # 1149-23-1; AOA or aminooxyacetic acid:                 CAS # 645-88-5; polyoxyethylene monooleate:                 CAS # 9005-65-6; sorbitan oleate: CAS # 9015-08-1;                 Glycerol α-monooleate: CAS # 111-03-5; and the mixture of                 mono and triglycerides: CAS # 111-03-5 and 122-32-7, respectively.
La Figura 6 muestra el efecto en la producción de etileno, al usar como aditivo ésteres alifáticos a diferentes concentraciones (0.5%, 1.0% y 1,5% identificados como AA1, AA2 y AA3, respectivamente) en un empaque de frutos, donde se aprecia que para tiempos inferiores a 6 semanas de almacenamiento, la producción de etileno no supera los 160 microlitros /kg /h, para ninguna de las concentraciones de aditivo evaluadas.Figure 6 shows the effect on production                 of ethylene, when using as an additive aliphatic esters to                 different concentrations (0.5%, 1.0% and 1.5%                 identified as AA1, AA2 and AA3, respectively) in                 a package of fruits, where it is appreciated that for times                 Less than 6 weeks of storage, production                 of ethylene does not exceed 160 microliters / kg / h, for                 None of the additive concentrations evaluated.
La Figura 7 muestra el efecto sobre la producción de etileno, al usar como aditivo la diludina a diferentes concentraciones (0.5%, 1.0% y 1,5% identificados como AR1, AR2 y AR3, respectivamente) en un empaque de frutos, donde se aprecia que la producción de etileno no supera los 160 microlitros /kg /h, para ninguna de las concentraciones de aditivo evaluadas y se aprecia una variación de aproximadamente 20 microlitros /kg /h en la producción de etileno entre las tres concentraciones.Figure 7 shows the effect on the                 ethylene production, using diludin as an additive                 at different concentrations (0.5%, 1.0% and 1.5%                 identified as AR1, AR2 and AR3, respectively) in                 a packing of fruits, where it is appreciated that the production                 of ethylene does not exceed 160 microliters / kg / h, for                 none of the additive concentrations evaluated and                 appreciate a variation of approximately 20 microliters                 / kg / h in ethylene production between the three concentrations.
La Figura 8 muestra el efecto en la producción de etileno, del AOA a diferentes concentraciones (0.5%, 1.0% y 1,5% identificados como AI1, AI2 y AI3, respectivamente) como aditivo en un empaque de frutos, donde se aprecia que el pico máximo en la producción de etileno se encuentra entre los 250 y 350 microlitros /kg /h a las cinco semanas, siendo este tiempo en el cual se observa la mayor diferencia en la producción de etileno en las tres concentraciones.Figure 8 shows the effect on production                 of ethylene, from AOA at different concentrations (0.5%,                 1.0% and 1.5% identified as AI1, AI2 and AI3,                 respectively) as an additive in a fruit package,                 where it is appreciated that the maximum peak in the production of                 ethylene is between 250 and 350 microliters / kg                 / h at five weeks, this time being                 observe the biggest difference in ethylene production                 in the three concentrations.
Es muy importante anotar que los aditivos mencionados pueden agregarse a cualquier poliolefina que espere usarse en la fabricación de empaques para el manejo y transporte de frutas, vegetales y follajes. Los resultados entre uno y otro tipo de poliolefina difieren muy poco, aunque los ensayos hechos para esta invención se centraron en el uso de polietileno y polipropileno.It is very important to note that the additives                 mentioned can be added to any polyolefin that                 Expect to be used in the manufacture of packaging for                 handling and transport of fruits, vegetables and foliage. The                 results between one type of polyolefin differ                 very little, although the tests done for this invention                 They focused on the use of polyethylene and polypropylene.
Con el ánimo de asegurar que el empaque polimérico con los aditivos además de retardar el proceso de maduración de la gulupa mantiene inalteradas las propiedades organolépticas de la fruta, se evaluó la vida útil sensorial del fruto con ayuda de un panel de catación entrenado (conformado por 8 panelistas). La metodología involucró el almacenamiento de diferentes lotes de fruta (8 por empaque) en iguales condiciones (8°C, % H.R. 54,5±3) en diferentes tiempos, 7, 6, 5, 4, 3, 2 semanas. Luego una fruta de cada periodo de tiempo fue dispuesta para el análisis sensorial por parte de los panelistas. El análisis se realizó sobre tres parámetros críticos en la calidad de la fruta, con los cuales fueron previamente entrenados; apariencia y color de la cáscara, apariencia y color de la pulpa de la fruta y el aroma y sabor de la pulpa de la fruta, por medio de una prueba descriptiva de puntajes. Los datos resultantes son comparados con los obtenidos para un empaque polimérico comercial usado actualmente por los exportadores de frutas tropicales de la misma familia vegetal al estudiado.In order to ensure that the packaging                 polymeric with additives in addition to retarding the                 gulupa maturation process remains unchanged                 the organoleptic properties of the fruit, the                 sensory shelf life of the fruit with the help of a panel                 trained cupping (made up of 8 panelists). The                 methodology involved the storage of different                 lots of fruit (8 per package) under the same conditions                 (8 ° C,% H.R. 54.5 ± 3) at different times, 7, 6, 5, 4,                 3, 2 weeks Then a fruit of each period of time                 was arranged for sensory analysis by                 The panelists. The analysis was performed on three                 Critical parameters in fruit quality, with                 which were previously trained; appearance and color                 of the shell, appearance and color of the pulp of the                 fruit and the aroma and flavor of the pulp of the fruit, by                 means of a descriptive test of scores. The data                 resulting are compared with those obtained for a                 commercial polymeric packaging currently used by                 tropical fruit exporters from the same family                 Vegetable to the studied.
Para la presente invención, los agentes adsorbentes, absorbentes, reductores o inhibidores de etileno mencionados que permiten reducir o modificar la concentración de etileno en la atmósfera circundante a los frutos, vegetales o follaje cuyo proceso de maduración y senescencia se busca retardar, se identificaran como un solo grupo de compuestos denominados agentes de captura de etileno, independientemente del mecanismo químico propio de la interacción de dicho agente con el etileno.For the present invention, the aforementioned adsorbents, absorbents, reducers or inhibitors of ethylene that allow reducing or modifying the concentration of ethylene in the atmosphere surrounding the fruits, vegetables or foliage whose ripening and senescence process is sought to be delayed, will be identified as a single group of compounds called ethylene capture agents , regardless of the chemical mechanism of the interaction of said agent with ethylene.
La metodología preferida utilizada en la fabricación de los empaques flexibles antimaduración para material vegetal, consiste en la obtención de una película plástica mediante extrusión y soplado, usando como carga una mezcla física entre los aditivos (en forma de pellets; “masterbatch”) y la matriz polimérica en “pellets”. La adición directa de los aditivos líquidos o sólidos usados en esta invención a la extrusora, ocasiona problemas de procesabilidad y heterogeneidad del aditivo en la película, con un alto detrimento de las propiedades antimaduración deseadas. Por lo tanto, el aditivo tiene que ser pre-extruido con la poliolefina para así obtener un “masterbatch” con altos porcentajes de aditivo (entre 10 y 20%) en forma de pellets.The preferred methodology used in the manufacture of flexible anti-ripening packages for plant material consists in obtaining a plastic film by extrusion and blowing, using as a load a physical mixture between the additives (in the form of pellets; masterbatch ) and the polymer matrix in pellets . The direct addition of the liquid or solid additives used in this invention to the extruder causes problems of processability and heterogeneity of the additive in the film, with a high detriment of the desired anti-aging properties. Therefore, the additive has to be pre-extruded with the polyolefin in order to obtain a " masterbatch " with high percentages of additive (between 10 and 20%) in the form of pellets.
Se recomienda hacer el proceso de extrusión manteniendo una temperatura de tornillo entre 180 y 210°C, una relación de halado 50/100 rpm o menos y una proporción entre poliolefina y “masterbatch” que resulte en una concentración de aditivo entre 0.5 y 5% en peso. La presentación final del empaque polimérico translucido tiene un espesor entre 0,035 y 0,052 mm y ausencia de microperforaciones.It is recommended to do the extrusion process                 maintaining a screw temperature between 180 and                 210 ° C, a pull ratio 50/100 rpm or less and a                 proportion between polyolefin and “masterbatch” that results                 in an additive concentration between 0.5 and 5% by weight.                 The final presentation of the translucent polymeric packaging                 It has a thickness between 0.035 and 0.052 mm and no microperforations.
En la Fig. 1 se presenta el proceso de maduración a lo largo de seis (6) semanas para un conjunto de frutos de gulupa (Passiflora edulis Sims fo. edulis) almacenados bajo las mismas condiciones ambientales en diferentes tipos de empaque, donde “sin empacar” representa muestras de fruta almacenadas sin uso de empaque, “película poliolefínica” representa un empaque de polietileno o polipropileno sin aditivo alguno, y “película poliolefínica con absorbente” representa un empaque de polietileno o polipropileno al cual mediante un proceso de extrusión se le ha introducido un 2% (p/p) de escualeno como aditivo absorbente de etileno.In Fig. 1 the process of                 maturation over six (6) weeks for a                 set of gulupa fruits (Passiflora edulis Sims fo.                 edulis) stored under the same conditions                 environmental in different types of packaging, where “without                 pack ”represents fruit samples stored without                 use of packaging, "polyolefin film" represents a                 polyethylene or polypropylene packaging without additive                 some, and "polyolefin film with absorbent"                 represents a polyethylene or polypropylene gasket                 which through an extrusion process has been                 introduced 2% (w / w) squalene as an additive                 ethylene absorbent.
En la Figura 2 se presenta el proceso de maduración a lo largo de seis (6) semanas para un conjunto de frutos de gulupa (Passiflora edulis Sims fo. edulis) almacenados bajo las mismas condiciones ambientales en diferentes tipos de empaque, donde “sin empacar” representa muestras de fruta almacenadas sin uso de empaque, “película poliolefínica” representa un empaque de polietileno o polipropileno sin aditivo alguno, y “película poliolefínica con reductor” representa un empaque de polietileno o polipropileno al cual mediante un proceso de extrusión se le ha introducido un 2% (p/p) de diludina como aditivo reductor de etileno.Figure 2 shows the process of                 maturation over six (6) weeks for a                 set of gulupa fruits (Passiflora edulis Sims fo.                 edulis) stored under the same conditions                 environmental in different types of packaging, where “without                 pack ”represents fruit samples stored without                 use of packaging, "polyolefin film" represents a                 polyethylene or polypropylene packaging without additive                 some, and "polyolefin film with reducer"                 represents a polyethylene or polypropylene gasket                 which through an extrusion process has been                 introduced 2% (w / w) diludine as an additive                 ethylene reducer
En las Figuras 3, 4 y 5 se muestran los parámetros de calidad sensorial de la gulupa en dos empaques diferentes y a diferentes periodos de almacenamiento a una temperatura de 8ºC: un empaque polimérico comercial (barras oscuras) y un empaque activo que contiene escualeno como aditivo absorbente de la presente invención (barras gris claro).Figures 3, 4 and 5 show the                 gulupa sensory quality parameters in two                 different packages and at different periods of                 storage at a temperature of 8 ° C: a package                 commercial polymer (dark bars) and a gasket                 asset containing squalene as an absorbent additive of                 the present invention (light gray bars).
En las Figuras 6, 7 y 8 se muestra el efecto de otros agentes absorbentes como esteres alifáticos (CAS#111-03-5 y CAS#122-32-7 identificados como “AA”, Figura 6), agentes reductores como la diludina (identificado como AR, Figura 7) y agentes inhibidores de etileno como el AOA (identificado como AI, Figura 8).The effect is shown in Figures 6, 7 and 8                 of other absorbent agents such as aliphatic esters                 (CAS # 111-03-5 and CAS # 122-32-7 identified as “AA”,                 Figure 6), reducing agents such as diludine                 (identified as AR, Figure 7) and inhibitory agents                 of ethylene as the AOA (identified as AI, Figure 8).
Maneras de realizar la invenciónWays to realize the invention EjemplosExamples
EJEMPLO 1EXAMPLE 1
En la Figura 1 se presenta el proceso de maduración a lo largo de seis semanas para un conjunto de frutos de gulupa (Passiflora edulis Sims fo. edulis) almacenados bajo las mismas condiciones ambientales en diferentes tipos de empaque. La fruta almacenada en el empaque con el aditivo adsorbente en una concentración del 2%, establece una atmósfera en el empaque con una menor concentración de etileno a lo largo de todas las semanas del ensayo, lo que marca una gran diferencia con la fruta sin empacar y con la fruta en un empaque plástico sin el aditivo adsorbente. Destacable es la disminución en el pico climatérico (máxima de producción de etileno en cinco semanas) donde con la película con aditivo se presenta 3 y 6 veces menos concentración de etileno que con la película polimérica sin aditivo o con la fruta sin empaque, respectivamente.Figure 1 shows the process of                 maturation over six weeks for a set                 of gulupa fruits (Passiflora edulis Sims fo. edulis)                 stored under the same environmental conditions in                 Different types of packaging. The fruit stored in the                 packing with the adsorbent additive in a concentration                 of 2%, establishes an atmosphere in the packaging with a                 lower concentration of ethylene throughout all                 trial weeks, which makes a big difference with                 unpacked fruit and fruit in a package                 plastic without the adsorbent additive. Remarkable is the                 decrease in the climatic peak (maximum production                 of ethylene in five weeks) where with the film with                 additive is presented 3 and 6 times less concentration of                 ethylene than with the polymer film without additive or with                 Fruit without packaging, respectively.
EJEMPLO 2EXAMPLE 2
La Figura 2 presenta los resultados para el caso en que el aditivo empleado en uno de los empaques es un agente reductor de olefinas en una concentración menor del 2% y su comparación con otro tipo de empaques. También en este caso las frutas de gulupa almacenadas en la bolsa de poliolefina con el aditivo se conservan en mejor forma que las otras dos muestras con las que se compara el proceso de maduración. De manera similar al ejemplo anterior, en el pico climatérico la reducción de la producción de etileno con el empaque con reductor es apreciable.Figure 2 presents the results for the                 case in which the additive used in one of the packages                 it is an olefin reducing agent in a concentration                 less than 2% and its comparison with other types of packaging.                 Also in this case the gulupa fruits stored in                 The polyolefin bag with the additive is preserved in                 better way than the other two samples with which                 Compare the ripening process. Similar to                 previous example, in the climacteric peak the reduction of                 Ethylene production with the reducer packaging is appreciable.
EJEMPLO 3EXAMPLE 3
Para medir la senescencia de los frutos en los empaques con aditivos, un panel de catación conformado por 8 panelistas entrenados evaluó la apariencia-color de la cáscara, apariencia-color de la pulpa y aroma-sabor de la pulpa. Y se comparó a un empaque comercial usado actualmente. Cada atributo con una escala de puntaje diferente teniendo en cuenta la importancia del atributo en el consumidor final, así la apariencia-color de la cascara tiene un puntaje máximo de 7 (este es el primer aspecto que impacta al consumidor), el aroma-sabor de la pulpa un puntaje máximo de 5 y la apariencia-color de la pulpa un máximo de 3 (menor impacto sobre el consumidor). Los valores obtenidos para los tres atributos fueron promediados para todos los experimentos y su valor es reportado como “medianas de puntaje” en las Figuras 3, 4 y 5.To measure the senescence of the fruits in the                 packaging with additives, a shaped cupping panel                 by 8 trained panelists evaluated the appearance-color                 of the shell, appearance-color of the pulp and                 aroma-flavor of the pulp. And it was compared to a package                 Commercial used currently. Each attribute with a                 different score scale considering the                 importance of the attribute in the final consumer, thus the                 appearance-color of the shell has a maximum score                 of 7 (this is the first aspect that impacts the                 consumer), the aroma-flavor of the pulp a score                 maximum of 5 and the appearance-color of the pulp a maximum                 of 3 (less impact on the consumer). The values                 obtained for the three attributes were averaged                 for all experiments and its value is reported as                 “Medium scores” in Figures 3, 4 and 5.
Las Figuras 3, 4 y 5 muestran estos resultados para cada atributo, valores cercanos al máximo representan la mejor calidad posible y valores cercanos a uno representan una calidad totalmente indeseable. Los resultados para los aditivos absorbente y reductor de etileno son muy similares, por lo tanto solo se muestra el resultado con el absorbente. La Figura 3 y 5 muestran que la apariencia y color de la cáscara y apariencia y color de la pulpa durante el periodo de almacenamiento sufren pequeñas diferencias con respecto al empaque comercial. Pero después de 4 y hasta la 7 semana, no hay cambios apreciables. Por lo tanto el empaque desarrollado se comporta igual al empaque comercial en estos atributos. La Figura 4 muestra como el empaque comercial conserva mejor el aroma y sabor de la pulpa de la fruta durante las primeras 4 semanas de almacenamiento. Pero el empaque con absorbente aquí desarrollado presenta mejores resultados en las últimas semanas de almacenamiento (de la semana 4 a la semana 7). Lo anterior es muy importante, ya que las últimas semanas de almacenamiento, son precisamente las que se usan para exhibir el fruto al comprador final. Cabe anotar que dentro de los atributos analizados, el aroma y sabor de la pulpa de la fruta es el más importante para el consumidor final.Figures 3, 4 and 5 show these results                 for each attribute, values close to the maximum                 they represent the best possible quality and close values                 to one they represent a totally undesirable quality.                 The results for absorbent and reducing additives                 ethylene are very similar, therefore only                 Show the result with the absorbent. Figure 3 and 5                 show that the appearance and color of the shell and                 appearance and color of the pulp during the period of                 storage suffer small differences with respect                 to commercial packaging. But after 4 and until 7                 week, there are no appreciable changes. Therefore the                 developed packaging behaves the same as packaging                 commercial in these attributes. Figure 4 shows how                 Commercial packaging better preserves the aroma and flavor of                 the pulp of the fruit during the first 4 weeks of                 storage. But the packing with absorbent here                 developed presents better results in recent                 storage weeks (from week 4 to week                 7). The above is very important, since the last                 weeks of storage, are precisely those that                 They use to display the fruit to the final buyer. Fits                 note that within the analyzed attributes, the aroma                 and taste of the pulp of the fruit is the most important                 For the final consumer.
EJEMPLO 4EXAMPLE 4
Variaciones en la concentración o la naturaleza del aditivo a una temperatura de almacenamiento de 8ºC pueden llevar a inhibir la capacidad antimaduración de los empaques como lo muestra la Figura 6. Cuando se usa un aditivo absorbente “AA” de etileno como los esteres alifáticos (CAS#111-03-5 y 122-32-7) en concentraciones de 0,5: 1,0 ó 1,5% (p/p), representado como AA1, AA2 y AA3 respectivamente, se aprecia que la producción de etileno en la frutas no se afecta drásticamente, obteniéndose menores producciones de etileno pero aun mostrando un aumento progresivo hasta llegar a un pico climatérico a un tiempo igual al obtenido por la fruta sin empacar.Variations in concentration or                 nature of the additive at a temperature of                 8 ° C storage can lead to inhibit                 anti-aging capacity of the packaging as shown                 Figure 6. When an absorbent additive "AA" of                 ethylene as aliphatic esters (CAS # 111-03-5 and                 122-32-7) in concentrations of 0.5: 1.0 or 1.5% (w / w),                 represented as AA1, AA2 and AA3 respectively, it                 appreciate that the production of ethylene in fruits is not                 drastically affects, obtaining lower productions                 of ethylene but still showing a progressive increase                 until reaching a climacteric peak at a time equal to                 obtained by the unpacked fruit.
Similares resultados se encuentran cuando se usan aditivos “A” inhibidores de etileno “I” como el AOA o reductores de etileno “R” como la diludina a diferentes concentraciones que van desde 0,5: 1,0 y 1,5%(p/p).Similar results are found when                 use additives "A" ethylene inhibitors "I" such as AOA                 or "R" ethylene reducers such as diludine a                 different concentrations ranging from 0.5: 1.0 and 1.5% (w / w).
El alcance de esta invención se define para productos frutales que en su proceso postcosecha producen etileno dentro de su proceso metabólico. Puede ser para empaques de carga en transporte o para almacenamiento doméstico.The scope of this invention is defined to                 fruit products that in their post-harvest process                 They produce ethylene within their metabolic process. May                 be for cargo packaging in transport or for                 domestic storage
Aunque la presente invención ha quedado descrita con las realizaciones preferentes mostradas, queda entendido que las modificaciones y variaciones que conserven el espíritu y el alcance de esta invención se entienden dentro del alcance de las reivindicaciones adjuntas.Although the present invention has remained                 described with the preferred embodiments shown,                 it is understood that the modifications and variations that                 keep the spirit and scope of this invention be                 understood within the scope of the appended claims.
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Claims (10)

  1. Una composición polimérica para capturar etileno que comprende:
    a) un sustrato polimérico que consiste en una poliolefina o una mezcla de poliolefinas, y
    b) uno o más de los agentes de captura de etileno, en concentraciones entre 0.5% y 5% en relación peso a peso, seleccionado del grupo compuesto por: escualeno, diludina (2,6-dimetil-1,4-dihidropiridina-3,5-dicarboxilato de dietilo), ácido aminooxiacético, monooleato de polioxietileno, oleato de sorbitan, α-monooleato de glicerol y la mezcla de mono y triglicéridos (CAS#111-03-5 y CAS#122-32-7).    A polymeric composition for capturing ethylene comprising:
    a) a polymeric substrate consisting of a polyolefin or a mixture of polyolefins, and
    b) one or more of the ethylene capture agents, in concentrations between 0.5% and 5% in weight to weight ratio, selected from the group consisting of: squalene, diludin (2,6-dimethyl-1,4-dihydropyridine-3 , Diethyl 5-dicarboxylate), aminooxyacetic acid, polyoxyethylene monooleate, sorbitan oleate, glycerol α-monooleate and the mixture of mono and triglycerides (CAS # 111-03-5 and CAS # 122-32-7).
  2. La composición polimérica para capturar etileno según la reivindicación 1 caracterizada porque la poliolefina del sustrato polimérico es polietileno o polipropileno.The polymer composition to capture ethylene                 according to claim 1 characterized in that the                 Polyolefin of the polymeric substrate is polyethylene or polypropylene.
  3. La composición polimérica para capturar etileno según la reivindicación 1 donde el agente de captura de etileno es diludina.The polymer composition to capture ethylene                 according to claim 1 wherein the capture agent of                 Ethylene is diludine.
  4. La composición polimérica para capturar etileno según la reivindicación 1 donde el agente de captura de etileno es escualeno.The polymer composition to capture ethylene                 according to claim 1 wherein the capture agent of                 Ethylene is squalene.
  5. La composición polimérica para capturar etileno según la reivindicación 1 donde el agente de captura de etileno es ácido aminooxiacético.The polymer composition to capture ethylene                 according to claim 1 wherein the capture agent of                 Ethylene is aminooxyacetic acid.
  6. La composición polimérica para capturar etileno según la reivindicación 1 donde el agente de captura de etileno es monooleato de polioxietileno.The polymer composition to capture ethylene                 according to claim 1 wherein the capture agent of                 Ethylene is polyoxyethylene monooleate.
  7. La composición polimérica para capturar etileno según la reivindicación 1 donde el agente de captura de etileno es oleato de sorbitan.The polymer composition to capture ethylene                 according to claim 1 wherein the capture agent of                 Ethylene is sorbitan oleate.
  8. La composición polimérica para capturar etileno según la reivindicación 1 donde el agente de captura de etileno es α-monooleato de glicerol.The polymer composition to capture ethylene                 according to claim 1 wherein the capture agent of                 Ethylene is glycerol α-monooleate.
  9. La composición polimérica para capturar etileno según la reivindicación 1 donde el agente de captura de etileno es la mezcla de mono y triglicéridos: CAS#111-03-5 y 122-32-7, en partes iguales peso a peso.The polymer composition to capture ethylene                 according to claim 1 wherein the capture agent of                 Ethylene is the mixture of mono and triglycerides:                 CAS # 111-03-5 and 122-32-7, in equal parts weight to weight.
  10. Películas y empaques poliméricos que extienden la vida útil de frutas o vegetales frescos por más de 4 semanas a una temperatura inferior a 10 ºC que comprenden: a) un sustrato polimérico que consiste en polietileno, polipropileno o la mezcla de los mismos entre 95% a 98%; b) uno o más agentes de captura de etileno seleccionado del grupo compuesto por: escualeno; diludina (2,6-dimetil-1,4-dihidropiridina-3,5-dicarboxilato de dietilo); ácido aminooxiacético; monooleato de polioxietileno; oleato de sorbitan; α-monooleato de glicerol; y, la mezcla de dichos mono y triglicéridos entre 2% a 5%.Polymeric films and packaging that extend                 the shelf life of fresh fruits or vegetables for more than 4                 weeks at a temperature below 10 ° C which                 they comprise: a) a polymeric substrate consisting of                 polyethylene, polypropylene or the mixture thereof                 between 95% to 98%; b) one or more capture agents of                 ethylene selected from the group consisting of: squalene;                 diludine                 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate                 diethyl); aminooxyacetic acid; monooleate                 polyoxyethylene; sorbitan oleate; α-monooleate                 glycerol; and, the mixture of said mono and triglycerides                 between 2% to 5%.
PCT/IB2015/058582 2014-11-06 2015-11-06 Polymer packaging that delays the ripening and senescence process in fresh vegetable products WO2016071875A1 (en)

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ES2148157T3 (en) * 1991-04-02 2000-10-16 Cryovac Inc COMPOSITIONS, ARTICLES AND METHODS FOR ELIMINATING OXYGEN.
US7345008B1 (en) * 1998-07-29 2008-03-18 Kao Corporation Freshness-keeping agents for plants
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