CN101205306A - PE composite fresh-keeping packaging film for food modified atmosphere packaging as well as preparation and uses thereof - Google Patents

PE composite fresh-keeping packaging film for food modified atmosphere packaging as well as preparation and uses thereof Download PDF

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Publication number
CN101205306A
CN101205306A CNA2007101507954A CN200710150795A CN101205306A CN 101205306 A CN101205306 A CN 101205306A CN A2007101507954 A CNA2007101507954 A CN A2007101507954A CN 200710150795 A CN200710150795 A CN 200710150795A CN 101205306 A CN101205306 A CN 101205306A
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molecular sieve
packaging
composite fresh
air conditioned
keeping film
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CNA2007101507954A
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CN101205306B (en
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黄震
杨传民
苏峻峰
郭玉花
滕立军
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Tianjin University of Commerce
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Tianjin University of Commerce
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  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)

Abstract

The invention discloses a PE composite preservative packaging membrane for modified atmosphere packaging of foods and a preparation method, which aims at providing a packaging membrane capable of adjusting the gas compositions in the pack so as to further extend the shelf life of the fresh foods. The packaging membrane is prepared through the following raw materials according to a certain weight percentage: 75 per cent to 98 per cent of polymer substrates, 1.5 per cent to 20 per cent of molecular sieves and 0.5 per cent to 5 per cent of plasticizers. By utilizing the molecular sieves as active inorganic particles, the PE composite preservative packaging membrane of the invention ensures that the membrane has favorable permeability, moisture permeability and porosity and is capable of spontaneously adjusting the gas compositions in the pack so as to suppress the respiration of the fresh foods and extend the freshness period of the fresh foods. The invention also discloses a preparation method for PE composite preservative packaging membrane and the packaging membrane prepared through the method has the advantages of uniform membrane, adjustable thickness, tear resistance, impact resistance, high heat sealing strength, simple processing technique, and convenient realization of industrialized production, etc.

Description

Food air conditioned packaging PE composite fresh-keeping film and preparation method and application
Technical field
The present invention relates to food fresh keeping wrapping material field, in particular, relate to a kind of PE composite fresh-keeping film that is applicable to fresh and alive food product pack and its production and application.
Background technology
The outlet of China's agricultural byproducts participates in competition in the international market, becomes to improve a kind of important channel that farmers' income is made the life better and built a Harmonious Society.The outlet of agricultural byproducts relates to the strong guarantee of the fresh-keeping of product and related packaging technology inevitably.The exploitation of the functional Perserving materials and the preservation technique of being correlated with becomes the increment in postpartum of agricultural-food and the key subject that solution is badly in need of in the agricultural-food field gradually with breakthrough.At present general plastics Perserving materials mainly adds all kinds of chemical preservatives in plastic substrate or plastic wrapping, the volatility that causes preservation agent is easily polluted and is reduced the safety performance of food greatly, may cause the complicated problem of material processing technique and antistaling process simultaneously.
Summary of the invention
The present invention is in order to overcome weak point of the prior art, a kind of gaseous constituent that can regulate package interior to be provided, and then prolongs the food air conditioned packaging PE composite fresh-keeping mould material of fresh and alive food shelf-life.
Another object of the present invention provides that a kind of complete processing is simple, and film is even, is convenient to realize the preparation method of the food air conditioned packaging PE composite fresh-keeping film of suitability for industrialized production
The present invention is achieved through the following technical solutions:
A kind of food air conditioned packaging PE composite fresh-keeping film is characterized in that made by following raw material by weight percentage: polymeric substrate is 75-98%, and the molecular sieve after the coupling agent treatment is 1.5-20%, and softening agent is 0.5-5%; Described polymeric substrate is mixed by LDPE, LLDPE and EVA, in the mixture base material by weight percentage LDPE be 30-100%, LLDPE is 0-50%, EVA is 0-20%; The amount of coupling agent is the 3-10% of molecular sieve by weight percentage.Described molecular sieve is any in zeolite molecular sieve, mesopore molecular sieve and the carbonaceous molecular sieve; Described softening agent be polyoxyethylene glycol, ethylene glycol, Sorbitol Powder, glycerine and stearic any; Described coupling agent is a silane compound.
The preparation method of the above-mentioned food air conditioned packaging PE composite fresh-keeping film of the present invention comprises the steps:
(1) LDPE, LLDPE and EVA are mixed, make polymeric substrate; In the mixture base material by weight percentage LDPE be 30-100%, LLDPE is 0-50%, EVA is 0-20%.
(2) with molecular sieve baking removing moisture, and the adding coupling agent carries out surface treatment; Filter washing, drying then.The storing temperature of molecular sieve is preferably 250 ℃.The surface treatment of coupling agent adopts ordinary method to carry out.The amount of coupling agent is the 3-10% of molecular sieve by weight percentage.
(3) molecular sieve after the above-mentioned processing is joined in the polymeric substrate behind the mixing, add softening agent again, mixing, extruding pelletization; Wherein, polymeric substrate is 75-98% by weight percentage, and the molecular sieve after the processing is 1.5-20%, and softening agent is 0.5-5%; The extruding pelletization temperature is preferably 170-200 ℃.
(4) the said mixture particle is obtained PE composite fresh-keeping film through extruding blowing mould.Extrude the blown film temperature and be preferably 165-200 ℃.
Described molecular sieve is any in zeolite molecular sieve, mesopore molecular sieve and the carbonaceous molecular sieve.Described softening agent be polyoxyethylene glycol, ethylene glycol, Sorbitol Powder, glycerine and stearic any.Described coupling agent is a silane compound, as vinyltriethoxysilane, vinyltrimethoxy silane, γ-(methacryloxy) propyl trimethoxy silicane, γ-glycidyl ether propyl trimethoxy silicane, β-(3,4 oxirane ring hexene methyl) ethyl trimethoxy silane etc.
Above-mentioned food air conditioned packaging PE composite fresh-keeping film of the present invention can be widely used in the Freshkeeping Packaging of vegetable and fruit Freshkeeping Packaging and meat fresh provisions.
The present invention has following technique effect:
PE composite fresh-keeping film of the present invention utilizes molecular sieve as active inorganic particulate, make film have air permeability and good, water vapour permeability, void content, gaseous constituent that can spontaneous adjusting package interior to suppress the respiration of fresh and alive food, prolongs the freshness date of fresh and alive food.
The packing film of the preparation method of PE composite fresh-keeping film of the present invention preparation has that film is even, thickness is adjustable, anti tear, shock-resistant, heat seal strength is high, complete processing is simple, be convenient to realize advantage such as suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment to the detailed description of the invention.
Embodiment 1
After 250 ℃ of bakings of zeolite molecular sieve beta are removed moisture, take by weighing 25 grams rapidly, put into 500 milliliters of toluene, and add 0.75 gram γ-(methacryloxy) propyl trimethoxy silicane room temperature reaction under nitrogen protection and carried out surface treatment in 24 hours.Filter then, and wash successively with 500 milliliters of toluene, 250 ml methanol, the gained molecular sieve was 110 ℃ of vacuum-dryings 1 hour.Weigh up that molecular sieve 5 grams that above-mentioned processing obtains join 60 gram LDPE, 30 gram LLDPE restrain in the mixture of EVA with 4, stirring and evenly mixing, adding 5 gram stearic acid then is fully mixed to evenly, carry out granulation with twin screw extruder, four sections extruding pelletization temperature are 170,200,200 and 170 ℃, screw speed is 30-70rpm.The said mixture particle put into extrude blow molding machine and be blow molded into film, extrude four sections temperature of inflation film manufacturing machine and be respectively 170,195,195 and 170 ℃, pulling speed is 4.5rpm.The thickness of film is 15 μ m, film longitudinal tensile strength 24Mpa, and transverse tensile strength 20Mpa, heat seal strength 7Mpa, tearing toughness are 3KN/m, and visible light transmittance rate is 90%, and rate of perviousness is 16g/m 2Day, CO 2Rate of permeation is 4100ml/m 2Day.
Above-mentioned film is used for the Freshkeeping Packaging that strawberry, spinach, rape and the cherry tomato of fresh harvesting seal, every packing 40 grams of strawberry wherein, every packing 100 grams of spinach and rape, every packing 200 grams of cherry tomato.In 20 ℃ of room temperatures and relative humidity is 40% time, freshness-retained 5 days of strawberry, and spinach and rape reach 6 days, cherry tomato 20 days; In 6 ℃ of storages of refrigerator, strawberry, spinach, rape and cherry tomato are all freshness-retained to be reached more than 20 days.
Embodiment 2
Mesopore molecular sieve MCM-41 after moisture is removed in 250 ℃ of bakings, is taken by weighing 25 grams rapidly, put into 500 milliliters of toluene, and add 2.5 gram vinyltriethoxysilanes room temperature reactions under nitrogen protection and carried out surface treatment in 24 hours.Filter then, and wash successively with 500 milliliters of toluene, 250 ml methanol, the gained molecular sieve was 110 ℃ of vacuum-dryings 1 hour.Take by weighing out molecular sieve 1.5 grams that above-mentioned processing obtains, join among the 98 gram LDPE stirring and evenly mixing, add 0.5 Keshan pears sugar alcohol then and be fully mixed to evenly, carry out granulation with twin screw extruder, four sections extruding pelletization temperature are 170,200,200 and 170 ℃, screw speed is 30-70rpm; The said mixture particle put into extrude blow molding machine and be blow molded into film, extrude four sections temperature of inflation film manufacturing machine and be respectively 170,195,195 and 170 ℃, pulling speed is 4.5rpm.The thickness of film is 25 μ m, film longitudinal tensile strength 7Mpa, and transverse tensile strength 15Mpa, heat seal strength 3Mpa, tearing toughness are 1KN/m, and visible light transmittance rate is 88%, and rate of perviousness is 15g/m 2Day, CO 2Rate of permeation is 34000ml/m 2Day.
Above-mentioned film is used for the Freshkeeping Packaging that strawberry, spinach, rape and the cherry tomato of fresh harvesting seal, every packing 40 grams of strawberry wherein, every packing 100 grams of spinach and rape, every packing 200 grams of cherry tomato.In 20 ℃ of room temperatures and relative humidity is 40% time, freshness-retained 4 days of strawberry, and spinach and rape reach 5 days, and the cherry tomato is more than 15 days; In 6 ℃ of storages of refrigerator, strawberry, spinach, rape and cherry tomato are all freshness-retained to be reached more than 15 days.
Embodiment 3
After 250 ℃ of bakings of carbonaceous molecular sieve are removed moisture, take by weighing 25 grams rapidly, put into 500 milliliters of toluene, and add 1.5 gram γ-glycidyl ether propyl trimethoxy silicanes room temperature reaction under nitrogen protection and carried out surface treatment in 24 hours.Filter then, and wash successively with 500 milliliters of toluene, 250 ml methanol, the gained molecular sieve was 110 ℃ of vacuum-dryings 1 hour.Weigh up molecular sieve 20 grams that above-mentioned processing obtains, join in the mixture of 22.5 gram LDPE, 37.5 gram LLDPE and 15 gram EVA, stirring and evenly mixing, adding 5 gram glycerine then is fully mixed to evenly, carry out granulation with twin screw extruder, the extruding pelletization temperature is 170-200 ℃, and screw speed is 30-70rpm.The said mixture particle put into extrude blow molding machine and be blow molded into film, extrude four sections temperature of inflation film manufacturing machine and be respectively 170,195,195 and 170 ℃, pulling speed is 4.5rpm.The thickness of film is 30 μ m film longitudinal tensile strength 15Mpa, transverse tensile strength 16Mpa, and heat seal strength 5Mpa, tearing toughness are 2KN/m, and visible light transmittance rate is 91%, and rate of perviousness is 18g/m 2Day, CO 2Rate of permeation is 8000ml/m 2Day.
Above-mentioned film is used for the Freshkeeping Packaging that strawberry, spinach, rape and the cherry tomato of fresh harvesting seal, every packing 40 grams of strawberry wherein, every packing 100 grams of spinach and rape, every packing 200 grams of cherry tomato.In 20 ℃ of room temperatures and relative humidity is 40% time, freshness-retained 6 days of strawberry, and spinach and rape reach 8 days, cherry tomato 25 days; In 6 ℃ of storages of refrigerator, strawberry, spinach, rape and cherry tomato are all freshness-retained to be reached more than 25 days.
Embodiment 4
After 250 ℃ of bakings of zeolite molecular sieve A are removed moisture, take by weighing 25 grams rapidly, put into 500 milliliters of toluene, and add 1.25 gram vinyltrimethoxy silanes room temperature reaction under nitrogen protection and carried out surface treatment in 24 hours.Filter then, and wash successively with 500 milliliters of toluene, 250 ml methanol, the gained molecular sieve was 110 ℃ of vacuum-dryings 1 hour.Weigh up molecular sieve 12 grams that above-mentioned processing obtains, join in the mixture of 60 gram LDPE, 25 gram LLDPE stirring and evenly mixing, adding 3 gram ethylene glycol then is fully mixed to evenly, carry out granulation with twin screw extruder, the extruding pelletization temperature is 170-200 ℃, and screw speed is 30-70rpm.The said mixture particle put into extrude blow molding machine and be blow molded into film, extrude four sections temperature of inflation film manufacturing machine and be respectively 170,195,195 and 170 ℃, pulling speed is 4.5rpm.The thickness of film is 20 μ m film longitudinal tensile strength 14Mpa, transverse tensile strength 15Mpa, and heat seal strength 4Mpa, tearing toughness are 1.5KN/m, and visible light transmittance rate is 90%, and rate of perviousness is 20g/m 2Day, CO 2Rate of permeation is 7000ml/m 2Day.
Above-mentioned film is used for the Freshkeeping Packaging that strawberry, spinach, rape and the cherry tomato of fresh harvesting seal, every packing 40 grams of strawberry wherein, every packing 100 grams of spinach and rape, every packing 200 grams of cherry tomato.In 20 ℃ of room temperatures and relative humidity is 40% time, freshness-retained 6 days of strawberry, and spinach and rape reach 7 days, cherry tomato 21 days; In 6 ℃ of storages of refrigerator, strawberry, spinach, rape and cherry tomato are all freshness-retained to be reached more than 25 days.
Embodiment 5
After a zeolite molecular sieve SBA-15250 ℃ baking removed moisture, take by weighing 25 grams rapidly, put into 500 milliliters of toluene, and add 2 gram β-(3,4 oxirane ring hexene methyl) ethyl trimethoxy silane room temperature reactions under nitrogen protection and carried out surface treatment in 24 hours.Filter then, and wash successively with 500 milliliters of toluene, 250 ml methanol, the gained molecular sieve was 110 ℃ of vacuum-dryings 1 hour.Weigh up molecular sieve 8 grams that above-mentioned processing obtains, join in the mixture of 45 gram LDPE, 36 gram LLDPE and 9 gram EVA, stirring and evenly mixing, adding 2 gram polyoxyethylene glycol then is fully mixed to evenly, carry out granulation with twin screw extruder, the extruding pelletization temperature is 170-200 ℃, and screw speed is 30-70rpm.The said mixture particle put into extrude blow molding machine and be blow molded into film, extrude four sections temperature of inflation film manufacturing machine and be respectively 170,195,195 and 170 ℃, pulling speed is 4.5rpm.The thickness of film is 25 μ m film longitudinal tensile strength 21Mpa, transverse tensile strength 20Mpa, and heat seal strength 6Mpa, tearing toughness are 2.5KN/m, and visible light transmittance rate is 91%, and rate of perviousness is 16g/m 2Day, CO 2Rate of permeation is 9000ml/m 2Day.
Above-mentioned film is used for the Freshkeeping Packaging that strawberry, spinach, rape and the cherry tomato of fresh harvesting seal, every packing 40 grams of strawberry wherein, every packing 100 grams of spinach and rape, every packing 200 grams of cherry tomato.In 20 ℃ of room temperatures and relative humidity is 40% time, freshness-retained 5 days of strawberry, and spinach and rape reach 6 days, cherry tomato 20 days; In 6 ℃ of storages of refrigerator, strawberry, spinach, rape and cherry tomato are all freshness-retained to be reached more than 20 days.

Claims (10)

1. a food air conditioned packaging PE composite fresh-keeping film is characterized in that made by following raw material by weight percentage: polymeric substrate is 75-98%, and the molecular sieve after the coupling agent treatment is 1.5-20%, and softening agent is 0.5-5%; Described polymeric substrate is mixed by LDPE, LLDPE and EVA, in the mixture base material by weight percentage LDPE be 30-100%, LLDPE is 0-50%, EVA is 0-20%; The amount of coupling agent is the 3-10% of molecular sieve by weight percentage.
2. food air conditioned packaging PE composite fresh-keeping film according to claim 1 is characterized in that described molecular sieve is any in zeolite molecular sieve, mesopore molecular sieve and the carbonaceous molecular sieve; Described softening agent be polyoxyethylene glycol, ethylene glycol, Sorbitol Powder, glycerine and stearic any; Described coupling agent is a silane compound.
3. the preparation method of the described food air conditioned packaging PE composite fresh-keeping film of claim 1 is characterized in that, comprises the steps:
(1) LDPE, LLDPE and EVA are mixed, make polymeric substrate;
(2) with molecular sieve baking removing moisture, and the adding coupling agent carries out surface treatment; Filtration washing then, drying; The amount of coupling agent is the 3-10% of molecular sieve by weight percentage;
(3) molecular sieve after the above-mentioned processing is joined in the polymeric substrate behind the mixing, add softening agent again, mixing, extruding pelletization; Wherein, polymeric substrate is 75-98% by weight percentage, and the molecular sieve after the processing is 1.5-20%, and softening agent is 0.5-5%;
(4) the said mixture particle is obtained PE composite fresh-keeping film through extruding blowing mould.
4. food air conditioned packaging PE composite fresh-keeping film according to claim 3 is characterized in that, in the mixture base material by weight percentage LDPE be 30-100%, LLDPE is 0-50%, EVA is 0-20%.
5. food air conditioned packaging PE composite fresh-keeping film according to claim 3 is characterized in that described molecular sieve is any in zeolite molecular sieve, mesopore molecular sieve and the carbonaceous molecular sieve.
6. food air conditioned packaging PE composite fresh-keeping film according to claim 3 is characterized in that, described softening agent be polyoxyethylene glycol, ethylene glycol, Sorbitol Powder, glycerine and stearic any.
7. food air conditioned packaging PE composite fresh-keeping film according to claim 3 is characterized in that described coupling agent is a silane compound.
8. food air conditioned packaging PE composite fresh-keeping film according to claim 3 is characterized in that the extruding pelletization temperature is 170-200 ℃; Extruding the blown film temperature is 165-200 ℃.
9. food air conditioned packaging PE composite fresh-keeping film according to claim 3 is characterized in that the storing temperature of molecular sieve is 250 ℃.
10. the application of the described food air conditioned packaging PE composite fresh-keeping film of claim 1 is characterized in that, is used for the Freshkeeping Packaging of vegetable and fruit Freshkeeping Packaging and meat fresh provisions.
CN2007101507954A 2007-12-07 2007-12-07 PE composite fresh-keeping packaging film for food modified atmosphere packaging as well as preparation and uses thereof Expired - Fee Related CN101205306B (en)

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ITMI20082064A1 (en) * 2008-11-20 2010-05-21 Consiglio Naz Delle Ricerche 16 67 METHOD FOR THE PRODUCTION OF A THERMOPLASTIC FILM CONTAINING A SUBSTANCE WITH ANTI-MICROBIAL ACTIVITY AND USE OF SUCH A FILM IN THE PRODUCTION OF FOOD PACKAGES
CN101967245A (en) * 2010-10-22 2011-02-09 北京印刷学院 Fruit-preserving green packing material with ethylene adsorption function and preparation method thereof
CN102174255A (en) * 2011-03-18 2011-09-07 国家农产品保鲜工程技术研究中心(天津) Spontaneous air-adjusting preservation method for cherries
CN101731321B (en) * 2009-12-10 2012-03-14 四川大学 Pear naked fresh-keeping method
CN102863685A (en) * 2012-09-26 2013-01-09 北京印刷学院 Fresh-keeping packaging material for tomatoes
WO2014101670A1 (en) * 2012-12-28 2014-07-03 广东美联新材料股份有限公司 Air-permeable masterbatch and method for producing air-permeable film therefrom
CN106275837A (en) * 2015-05-25 2017-01-04 姚本海 A kind of logistic turnover box based on food fresh keeping transport
CN106583205A (en) * 2016-10-31 2017-04-26 江南大学 Manufacturing method of food packaging film
CN107177072A (en) * 2017-05-25 2017-09-19 句容市兴武包装有限公司 A kind of preparation method of food oxydating resistance packaging film
CN107857919A (en) * 2017-10-11 2018-03-30 南京财经大学 A kind of food antibacterial fresh-keeping packaging material with sustained release performance and preparation method thereof
CN110549714A (en) * 2019-08-28 2019-12-10 浙江金石包装有限公司 Straw cup seals complex film
WO2024016017A1 (en) * 2022-07-15 2024-01-18 Csp Technologies, Inc. Blown films with active agent and methods of making the same

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ITMI20082064A1 (en) * 2008-11-20 2010-05-21 Consiglio Naz Delle Ricerche 16 67 METHOD FOR THE PRODUCTION OF A THERMOPLASTIC FILM CONTAINING A SUBSTANCE WITH ANTI-MICROBIAL ACTIVITY AND USE OF SUCH A FILM IN THE PRODUCTION OF FOOD PACKAGES
WO2010057658A2 (en) * 2008-11-20 2010-05-27 Università Degli Studi Di Foggia Method for producing a film of thermoplastic material containing a substance with antimicrobial activity and use of this film in the production of packaging for food
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CN101731321B (en) * 2009-12-10 2012-03-14 四川大学 Pear naked fresh-keeping method
CN101967245A (en) * 2010-10-22 2011-02-09 北京印刷学院 Fruit-preserving green packing material with ethylene adsorption function and preparation method thereof
CN101967245B (en) * 2010-10-22 2012-08-15 北京印刷学院 Fruit-preserving green packing material with ethylene adsorption function and preparation method thereof
CN102174255A (en) * 2011-03-18 2011-09-07 国家农产品保鲜工程技术研究中心(天津) Spontaneous air-adjusting preservation method for cherries
CN102863685A (en) * 2012-09-26 2013-01-09 北京印刷学院 Fresh-keeping packaging material for tomatoes
WO2014101670A1 (en) * 2012-12-28 2014-07-03 广东美联新材料股份有限公司 Air-permeable masterbatch and method for producing air-permeable film therefrom
RU2593590C2 (en) * 2012-12-28 2016-08-10 Мэлион Нью Матириалз Ко., Лтд. Concentrate for production of moisture-impermeable air-permeable film and method for production of air-permeable film using said method
CN106275837A (en) * 2015-05-25 2017-01-04 姚本海 A kind of logistic turnover box based on food fresh keeping transport
CN106583205A (en) * 2016-10-31 2017-04-26 江南大学 Manufacturing method of food packaging film
CN107177072A (en) * 2017-05-25 2017-09-19 句容市兴武包装有限公司 A kind of preparation method of food oxydating resistance packaging film
CN107857919A (en) * 2017-10-11 2018-03-30 南京财经大学 A kind of food antibacterial fresh-keeping packaging material with sustained release performance and preparation method thereof
CN110549714A (en) * 2019-08-28 2019-12-10 浙江金石包装有限公司 Straw cup seals complex film
CN110549714B (en) * 2019-08-28 2021-11-09 浙江金石包装有限公司 Straw cup seals complex film
WO2024016017A1 (en) * 2022-07-15 2024-01-18 Csp Technologies, Inc. Blown films with active agent and methods of making the same

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