CN119329156A - Functional packaging film capable of controlling the sustained release of chlorine dioxide antibacterial agent and its production process - Google Patents
Functional packaging film capable of controlling the sustained release of chlorine dioxide antibacterial agent and its production process Download PDFInfo
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- CN119329156A CN119329156A CN202411467953.9A CN202411467953A CN119329156A CN 119329156 A CN119329156 A CN 119329156A CN 202411467953 A CN202411467953 A CN 202411467953A CN 119329156 A CN119329156 A CN 119329156A
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- antibacterial agent
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- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 239000004155 Chlorine dioxide Substances 0.000 title claims abstract description 93
- 235000019398 chlorine dioxide Nutrition 0.000 title claims abstract description 93
- 239000012785 packaging film Substances 0.000 title claims abstract description 57
- 229920006280 packaging film Polymers 0.000 title claims abstract description 57
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 15
- 238000013268 sustained release Methods 0.000 title claims description 13
- 239000012730 sustained-release form Substances 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920000098 polyolefin Polymers 0.000 claims abstract description 18
- 229910001919 chlorite Inorganic materials 0.000 claims abstract description 17
- 229910052619 chlorite group Inorganic materials 0.000 claims abstract description 17
- 150000007524 organic acids Chemical class 0.000 claims abstract description 16
- 230000035699 permeability Effects 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 14
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 9
- 238000013329 compounding Methods 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 37
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 27
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 22
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 20
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 18
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 16
- 229960002218 sodium chlorite Drugs 0.000 claims description 16
- 229920001684 low density polyethylene Polymers 0.000 claims description 15
- 239000004702 low-density polyethylene Substances 0.000 claims description 15
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 11
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 11
- 239000004743 Polypropylene Substances 0.000 claims description 8
- -1 polypropylene Polymers 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- 239000011256 inorganic filler Substances 0.000 claims description 5
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 238000006136 alcoholysis reaction Methods 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 239000004334 sorbic acid Substances 0.000 claims description 3
- 235000010199 sorbic acid Nutrition 0.000 claims description 3
- 229940075582 sorbic acid Drugs 0.000 claims description 3
- WOHVONCNVLIHKY-UHFFFAOYSA-L [Ba+2].[O-]Cl=O.[O-]Cl=O Chemical compound [Ba+2].[O-]Cl=O.[O-]Cl=O WOHVONCNVLIHKY-UHFFFAOYSA-L 0.000 claims description 2
- QXIKMJLSPJFYOI-UHFFFAOYSA-L calcium;dichlorite Chemical compound [Ca+2].[O-]Cl=O.[O-]Cl=O QXIKMJLSPJFYOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000010451 perlite Substances 0.000 claims description 2
- 235000019362 perlite Nutrition 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims 2
- 238000010101 extrusion blow moulding Methods 0.000 claims 1
- 235000013305 food Nutrition 0.000 abstract description 17
- 238000004806 packaging method and process Methods 0.000 abstract description 5
- 230000005923 long-lasting effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 59
- 239000000203 mixture Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 17
- 230000008569 process Effects 0.000 description 14
- 241000167854 Bourreria succulenta Species 0.000 description 8
- 230000000844 anti-bacterial effect Effects 0.000 description 8
- 235000019693 cherries Nutrition 0.000 description 8
- 239000011229 interlayer Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 6
- 230000029058 respiratory gaseous exchange Effects 0.000 description 6
- 238000000071 blow moulding Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 235000012055 fruits and vegetables Nutrition 0.000 description 5
- 239000004626 polylactic acid Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003094 microcapsule Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 235000021485 packed food Nutrition 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 229920000747 poly(lactic acid) Polymers 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000010345 tape casting Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 208000019331 Foodborne disease Diseases 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 239000000839 emulsion Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009920 food preservation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
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- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010944 pre-mature reactiony Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
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- Wrappers (AREA)
Abstract
The invention discloses a functional packaging film of a controllable slow-release chlorine dioxide antibacterial agent and a production process thereof, wherein the functional packaging film is composed of an inner layer film, an intermediate layer film and an outer layer film from inside to outside, the functional packaging film is obtained by multilayer coextrusion compounding, the inner layer film is composed of inorganic porous filler and polyolefin with water vapor permeability, the mass of the functional packaging film is 20-30%, the intermediate layer film is composed of chlorite, organic acid and hydrophilic polymer, the mass of the functional packaging film is 20-30%, and the outer layer film is composed of polyolefin, the mass of the functional packaging film is 45-60%. The functional packaging film provided by the invention can realize controllable and long-lasting slow release of chlorine dioxide, has a slow release period of more than 40 days, is used for packaging food, can prolong the shelf life of the food, and is simple in production process and easy to industrialize.
Description
Technical Field
The invention relates to the technical field of packaging material preparation, in particular to a functional packaging film of a controllable slow-release chlorine dioxide antibacterial agent and a production process thereof.
Background
With the enhancement of environmental awareness and the continuous improvement of the requirements on sanitation and safety, the development of novel food fresh-keeping technology is attracting attention. The antibacterial package can protect food during food preservation by preventing external contact and microorganisms from entering the food and regulating internal and external air, thereby ensuring food safety. Chlorine dioxide is a safe, efficient and powerful broad-spectrum bactericide, has no three substances (carcinogenic, teratogenic and mutagenic) in the use process, and has unique advantages in reducing food-borne diseases, reducing microbial spoilage, maintaining food freshness and maintaining food nutritional quality. Chlorine dioxide is recommended by world health organization as an A1-grade product in safe disinfection substances, and has been widely applied to the fields of fruit and vegetable fresh-keeping and the like. However, chlorine dioxide is very unstable, especially in the liquid state, which makes it difficult to store for a long period of time. Compared with liquid chlorine dioxide, the gaseous chlorine dioxide has stronger permeability and better antibacterial property. When gaseous chlorine dioxide is exposed to light, it is easily decomposed, which limits its use. Therefore, there is a need to develop a stable chlorine dioxide formulation that slowly releases chlorine dioxide gas over a period of time.
In order to achieve the above object, many researchers have conducted researches and have published a number of research papers. Li et al (Langmuir.2009, 25 (23): 13472-13480.) A microcapsule coating film with good antimicrobial activity was prepared from polyoxyethylene-polyoxypropylene as the shell material by water-in-oil-in-water (W/O/W) double emulsion for encapsulation of stable chlorine dioxide solutions. Ray (Journal Food science.2013,78 (2): 276-284.) a slow release film for chlorine dioxide was prepared by incorporating sodium chlorite and citric acid powder into a polylactic acid (PLA) shell by solution casting. However, since sodium chlorite (NaClO 2) and acid are directly mixed in the film, this results in premature release and further results in a short release cycle. Bai et al (Journal of Agricultural and Food chemistry 2016,64 (45): 8647-8652.) used acrylic pressure sensitive adhesive polymers impregnated with sodium chlorite and acid-containing polyvinyl alcohol compounds to prepare a binary composite film that was moisture activated to release chlorine dioxide gas, followed by a model of a slow release mechanism. The film is prepared by loading sodium chlorite and acid on different film materials to prepare two layers of films, and the problem of uneven release may exist. Jain et al (ACS APPLIED MATERIALS & interfaces.2017,9 (19): 16594-16603.) studied photochemical activation of films containing solid sodium chlorite by Ultraviolet (UV) irradiation and studied the generation of gaseous chlorine dioxide upon exposure to moisture. The film requires external Ultraviolet (UV) light and cannot self-generate chlorine dioxide gas according to the environment. Although researchers have tried many methods, the preservation and sustained release of solid chlorine dioxide products is extremely susceptible to temperature and humidity, resulting in low preservation rates and short release periods. Huang (Journal of Materials science.2018, 53:12704-12717.) prepared an antimicrobial polylactic acid (PLA) film that can release chlorine dioxide on a sustained basis using microcapsule technology. Namely, the chlorine dioxide microcapsule is prepared by encapsulating stable chlorine dioxide solution (taking sodium chlorite as a main component). The microcapsules and tartaric acid are then added to the polylactic acid to produce an antimicrobial film capable of sustained release of chlorine dioxide gas upon moisture activation. From published research papers, the sustained-release chlorine dioxide has short release duration, is uncontrollable, needs light or water to trigger, and in addition, the preparation process of the film or the capsule of the sustained-release chlorine dioxide is complicated and complex, so that industrialization is not easy to realize.
Patent document CN104097849a discloses a fresh-keeping packaging material of slow-release chlorine dioxide bactericide and a preparation method thereof. The fresh-keeping packaging material is a composite film prepared by dry-method compounding of a high-air-permeability cast polyethylene outer film and an EVA modified high-air-permeability cast polyethylene inner film through an adhesive containing chlorine dioxide release agent powder. Patent document CN106476380a discloses a preparation process of a slow-release chlorine dioxide antibacterial film. The reactive chlorine dioxide antibacterial film is prepared by compounding a film A and a film B by adopting wet compounding, wherein the film A adopts polyvinyl alcohol as a film forming substrate, a polyvinyl alcohol gel water solution is prepared by using a stable chlorine dioxide water solution, then the film is dried and formed by a tape casting process, the hygroscopicity of the film is increased by adding glycerol and carboxymethyl cellulose, and the release of chlorine dioxide is promoted, the film B adopts polylactic acid as a film forming substrate, the polylactic acid is dissolved by using methylene dichloride, and one of activating agents citric acid or tartaric acid is added into the film. Adding plasticizer and antioxidant, and casting to form the film. The preparation of the slow-release chlorine dioxide film disclosed by the patent technology mainly has the problem of complex preparation process.
Therefore, the present invention is particularly desired.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide the functional packaging film with controllable slow-release chlorine dioxide antibacterial agent and the production process thereof, and the obtained functional packaging film can realize the slow-release and controllable chlorine dioxide with long duration, and has simple production process and easy industrialization.
In order to achieve the above object, the present invention provides the following technical solutions:
In a first aspect, the invention provides a functional packaging film of a controllable slow-release chlorine dioxide antibacterial agent, wherein the functional packaging film consists of an inner layer film, an intermediate layer film and an outer layer film from inside to outside, and is obtained by multilayer coextrusion compounding;
the inner layer film consists of inorganic porous filler and polyolefin with water vapor permeability, and accounts for 20-30% of the mass of the functional packaging film;
the middle layer film consists of chlorite, organic acid and a polymer with hydrophilicity, and accounts for 20-30% of the mass of the functional packaging film;
The outer layer film is composed of polyolefin and accounts for 45-60% of the mass of the functional packaging film.
The technical scheme is that the applicant innovates the structure and the process improvement of the preparation of the slow-release chlorine dioxide film on the basis of the previous work, realizes controllable release of chlorine dioxide, and the duration time can reach more than 40 days. The invention innovatively applies the multilayer coextrusion process to the production of the functional packaging film, and the process is simple and easy to implement. The slow-release chlorine dioxide film prepared by the method can be applied to food packages such as fruits and vegetables, and the sterilization and fresh-keeping effects of the slow-release chlorine dioxide film are realized, so that the quality of the food is ensured, and the shelf life of the food is prolonged.
In the technical scheme, the functional packaging film is formed by compounding three layers of films of an outer layer, an intermediate layer and an inner layer by adopting a multilayer coextrusion blow molding or tape casting process. The film is characterized in that the outer layer is composed of polyolefin, can provide good protection and mechanical properties for the film, can be printed through corona treatment, the middle layer is composed of chlorite generating chlorine dioxide, organic acid and hydrophilic polymer, after the middle layer absorbs water, the chlorite reacts with the organic acid to generate chlorine dioxide, the chemical reaction formula is 2NaClO 2+C6H8O7→2ClO2↑+NaCl+3CO2↑+4H2 O, the inner layer is composed of porous inorganic filler and polyolefin with good water vapor permeability, on one hand, the inner layer can ensure compatibility and safety with package contents, and on the other hand, the inner layer can enable water vapor and chlorine dioxide gas to easily permeate, so that the film is one of key factors of the controllable slow-release chlorine dioxide of the functional package film.
In the above technical solution, the outer layer of the functional packaging film is composed of at least one polyolefin selected from Linear Low Density Polyethylene (LLDPE), low Density Polyethylene (LDPE), ethylene-vinyl acetate copolymer (EVA) and polypropylene (PP), and the outer layer film provides mechanical strength and barrier property to chlorine dioxide gas to the packaging film and is printable. The polyolefin used for the outer film may be selected according to the specific requirements of the functional packaging film for the outer film, and in general, the packaging film should have good puncture resistance. LLDPE has good puncture resistance and processability, and LDPE has good comprehensive properties. The outer layer polyolefin is preferably a blend of LLDPE and LDPE. As the optimization of the technical scheme of the invention, LLDPE accounts for 70-90% of the total mass of the outer layer film, and LDPE accounts for 10-30% of the total mass of the outer layer film. Because LLDPE and LDPE are nonpolar polymer materials, printing ink is not easy to fall off from the film, and the outer film can be subjected to corona treatment on line to increase the polarity of polyolefin, so that the adhesion of the printing ink on the outer film is increased.
In the technical scheme, the middle layer of the functional packaging film consists of chlorite, organic acid and hydrophilic polymer. The chlorite accounts for 1.5-6% of the total mass of the intermediate layer, the organic acid accounts for 3-10% of the total mass of the intermediate layer, and the polymer accounts for 80-95% of the total mass of the intermediate layer. The intermediate layer slowly releases chlorine dioxide gas, which is generated by the reaction of chlorite and organic acid. Chlorites include sodium chlorite, calcium chlorite and barium chlorite, with sodium chlorite being preferred. The organic acid includes any one of citric acid, tartaric acid, sorbic acid and malic acid. Among these four organic acids, citric acid is the most acidic, and citric acid is preferred. The hydrophilic polymer is one or two of EVA and PVA. The VA content in EVA can influence the hydrophilicity, and the VA content is high and the hydrophilicity is better. The molecular weight and alcoholysis degree of PVA can influence the hydrophilicity, and the molecular weight is low and alcoholysis degree is high, has better hydrophilicity, and in order to make PVA have better hydrophilicity, PVA does not melt when EVA melts, but is in solid powder form. The chlorite, organic acid and hydrophilic polymer should be sufficiently dry to prevent premature reaction of the chlorite and organic acid under the induction of water prior to the preparation of the functional packaging film.
Further, the inner layer of the functional packaging film is composed of porous inorganic filler and polyolefin with better water permeability. Chlorite has strong oxidizing property, and if the chlorite is directly contacted with packaged food, on one hand, the chlorite can oxidize and deteriorate the food, and on the other hand, the steam generated by respiration of the packaged food and residual water possibly attached to the food can induce the reaction of the chlorite and organic acid, which can lead to the reaction to be quick and slow before the reaction, and is unfavorable for the controllable slow release of chlorine dioxide. The inner film is composed of porous inorganic filler and polyolefin with better water vapor permeability, so that water generated by the package can permeate the inner film and enter the middle film, but the speed of water permeating the inner film is controlled due to the smaller pore diameter of the inner film, and the problems of high reaction speed, low reaction speed, and high reaction speed are avoided. The porous filler includes one or two of zeolite, diatomaceous earth, expanded perlite and porous ceramic, preferably zeolite. The mass of the porous filler accounts for 5-15% of the total mass of the inner layer film. The water-permeable polymer of the inner layer comprises one or two of LDPE, LLDPE, EVA and PP, and the mass of the polymer accounts for 85-95% of the total mass of the inner layer film.
Further, the inner layer of the functional packaging film has a porous structure, and can absorb part of ethylene gas released by packaged foods and chlorine dioxide can oxidize ethylene gas, so that the functional packaging film has the effect of preventing packaged fruits and vegetables from being premature.
Preferably, the organic acid is at least one selected from citric acid, tartaric acid, sorbic acid and malic acid.
As a preferable mode of the technical scheme, the polymer with hydrophilicity is at least one selected from polyvinyl alcohol and ethylene-vinyl acetate copolymer, wherein the molecular weight of the polyvinyl alcohol is 2.5 multiplied by 10 4～6.5×104, and the alcoholysis degree is less than 85 percent.
As a preferable mode of the technical scheme of the invention, the polyolefin in the inner layer film is at least one selected from low-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer and polypropylene, wherein the water vapor permeability of the low-density polyethylene is 10-30 mL/m 2 -day atm, the water vapor permeability of the linear low-density polyethylene is 5-20 mL/m 2 -day atm, the water vapor permeability of the ethylene-vinyl acetate copolymer is 10-30 mL/m 2 -day atm, and the water vapor permeability of the polypropylene is 5-20 mL/m 2 -day atm.
As the preferable technical scheme of the invention, the thickness of the functional packaging film is 25-35 mu m.
As the optimization of the technical scheme of the invention, when the concentration of the chlorine dioxide is 2.0-5.0 ppm, the chlorine dioxide has good sterilization effect. The concentration of the slow-release chlorine dioxide of the functional packaging film is 5.0-25.0 ppm, and the release period is more than 40 days.
In a second aspect, the present invention also provides a method for preparing the functional packaging film, which includes the following steps:
Firstly, accurately weighing raw materials of an inner layer film, an intermediate layer film and an outer layer film respectively, and uniformly mixing the raw materials to obtain respective mixtures;
And then, respectively putting the obtained mixtures into a multilayer coextrusion device, and adopting multilayer coextrusion blow molding or tape casting molding to obtain the functional packaging film. If the requirement for film thickness uniformity is not very high, multilayer coextrusion blow molding is preferred.
As the optimization of the technical scheme of the invention, the processing temperature of the outer layer is 170-200 ℃, the processing temperature of the middle layer is 125-145 ℃, and the processing temperature of the inner layer is 170-200 ℃. In the intermediate layer, the decomposition temperature of sodium chlorite is the lowest and is 175.0 ℃, and chlorite decomposition is prevented during processing.
Compared with the prior art, the invention has the following beneficial effects:
the functional packaging film provided by the invention has good antibacterial property, can effectively inhibit the growth of microorganisms such as bacteria, mould and the like, and prolongs the shelf life of fruits and vegetables in the package. The design of the functional packaging film adopts a controllable slow release technology, so that the chlorine dioxide antibacterial agent can be slowly released, and the duration time of the antibacterial effect is prolonged (more than 40 days).
Meanwhile, the key innovation of the invention is to adopt a multilayer coextrusion blow molding or casting process to produce the functional packaging film, the process is simple, continuous and efficient, the combination among layers is tight, the performance is stable, and the problem of interlayer separation is effectively avoided. And the industrialization and mass production are easy to realize.
Drawings
Figure 1 is a schematic diagram of the main structure of a functional packaging film.
Fig. 2 is a schematic diagram of the principle of function of the freshness protection package made of the functional packaging film.
Detailed Description
The following detailed description of embodiments of the invention is provided to emphasize that all embodiments are shown for the purpose of explaining the invention and are not to be construed as limiting the invention.
The test method adopted by the performance of the invention is as follows:
chlorine dioxide concentration (ppm) is detected by chlorine dioxide detector.
Example 1
Uniformly mixing 85.0 parts by weight of LLDPE (brand DFDA-7042, density of 0.918g/cm 3, melt index of 2.0g/10 min) and 15.0 parts by weight of LDPE (brand 18D, density of 0.917-0.923g/cm 3, melt index of 0.2-0.4g/10 min) of China petrochemical company, guangzhou corporation, into a multilayer coextrusion extruder hopper, wherein the temperatures of an extruder barrel and a machine head are 170 ℃ (zone 1), 175 ℃ (zone 2), 180 ℃ (zone 3), 180 ℃ (zone 4), 185 ℃ (zone 5) and 200 ℃ (machine head); after 2.0 parts by mass of sodium chlorite (Yunnan Jin Chu chemical Co., ltd., solid powder, decomposition temperature 175.0 ℃) and 4.0 parts by mass of citric acid (Jiangsu Raymond chemical Co., ltd., solid powder), 80.0 parts by mass of EVA (table plastic group, trade mark 7350M, VA content 18.0%, density 0.929g/cm 3, melt index 2.5g/10 min) and 20.0 parts by mass of PVA (Shanxi three-dimensional group Co., ltd., trade mark PVA 088-2017-88, density 1.27g/cm 3) were mixed uniformly, fed into a multilayer coextrusion extruder hopper, the extruder barrel and head temperatures were 125 ℃ (zone 1), 130 ℃ (zone 2), 135 ℃ (zone 3), 135 ℃ (zone 4), 135 ℃ (zone 5) and 140 ℃ (head), 5.0 parts by mass of zeolite (Han wire, ji Ye liter chemical Co., ltd.), 4A,200 mesh), 5.0 parts by mass of diatomaceous earth (Lingshou county far mica works, 300 mesh), 60.0 parts by mass of LDPE and 40 parts by mass of EVA were mixed uniformly and fed into an extruder hopper for multilayer coextrusion, the extruder barrel and the head having temperatures of 160℃C (zone 1), 170℃C (zone 2), 175℃C (zone 3), 175℃C (zone 4), 175℃C (zone 5) and 180℃C (head). The functional packaging film is prepared by adopting multilayer coextrusion blow molding, and the blow-up ratio is 2.5-3.5. The film produced by coextrusion can be directly added to a packaging bag as shown in fig. 1 and 2. The raw material composition of example 1 is shown in table 1.
The film prepared in example 1 was processed into a package having dimensions of 100.0mm by 100.0mm, a set of 10. Using cherries as test samples for packaging food, 100.0g of cherries were individually packed in 10 packaging bags, and sealed with heat seal. The chlorine dioxide concentration in the package was then measured over time as shown in table 2.
Example 2
The composition of example 2 is shown in table 1. The preparation procedure, process and chlorine dioxide concentration detection of example 2 were the same as in example 1. The films and bags produced are shown in figures 1 and 2. The chlorine dioxide concentration is shown in table 2 as a function of time.
Example 3
The composition of example 3 is shown in table 1. The preparation procedure, process and chlorine dioxide concentration detection of example 3 were the same as in example 1. The films and bags produced are shown in figures 1 and 2. The chlorine dioxide concentration is shown in table 2 as a function of time.
Example 4
The composition of example 4 is shown in table 1. The preparation procedure, process and chlorine dioxide concentration detection of example 4 were the same as in example 1. The films and bags produced are shown in figures 1 and 2. The chlorine dioxide concentration is shown in table 2 as a function of time.
Example 5
The composition of example 5 is shown in table 1. The preparation procedure, process and chlorine dioxide concentration detection of example 5 were the same as in example 1. The films and bags produced are shown in figures 1 and 2. The chlorine dioxide concentration is shown in table 2 as a function of time.
Example 6
The composition of example 6 is shown in table 1. The preparation procedure, process and chlorine dioxide concentration detection of example 6 were the same as in example 1. The films and bags produced are shown in figures 1 and 2. The chlorine dioxide concentration is shown in table 2 as a function of time.
It can be seen from examples 1 to 6 (as shown in Table 2) that the concentration of chlorine dioxide gradually increases with time, and increases faster and then slows down. This means that chlorine dioxide is continuously generated in the intermediate layer except for a part of the consumption of sterilization, and the amount of generated chlorine dioxide is more than the amount consumed.
Specifically, example 2 and example 1 differ in the amount of sodium chlorite and citric acid in the interlayer composition (as in table 1), and the mass of sodium chlorite and citric acid in example 2 is twice that of example 1. Over time, example 2 released chlorine dioxide faster than example 1, and thus at a higher concentration, especially during the first 14 days (as in table 2). Example 3 differs from example 1 in the amount of EVA and PVA in the inner layer composition (as in table 1), with the PVA content being higher in example 3. PVA is more hydrophilic than EVA, steam generated by cherry respiration in the packaging bag is easier to penetrate into the middle layer, and the middle layer with high PVA content can generate chlorine dioxide more quickly, but the speed of generating chlorine dioxide by the middle layer with high PVA content is slowed down along with the time (as shown in Table 2). Example 4 differs from example 1 in the amounts of EVA and PVA, and sodium chlorite and citric acid in the inner and middle layer compositions (as in Table 1), with higher amounts of PVA, sodium chlorite and citric acid in example 4. The middle layer with high PVA content produced chlorine dioxide faster and the sodium chlorite and citric acid content was high to produce more chlorine dioxide (as in table 2). Example 5 differs from example 1 in the amount of porous filler in the composition of the inner layer (as in table 1), and in example 5 the amount of porous filler is twice that of example 1, and since the porous filler plays an important role in the penetration of water vapor generated by the respiration of the packaged cherries into the intermediate layer, the rate of chlorine dioxide generated in example 5, which is high in the amount of porous filler, is faster and the concentration is higher (as in table 2). Example 6 differs from example 1 in the amount of PVA and porous filler in the middle and inner layer composition (as in table 1), and in example 6, the amount of PVA and porous filler is higher, and the steam generated by respiration of the packaged cherries more easily permeates into the middle layer, so that the generation rate of chlorine dioxide is faster and the concentration is higher (as in table 2).
Comparative example 1
Comparative example 1 differs from example 1 in that in the composition of the film interlayer, PVA was not present in the interlayer composition of comparative example 1. The preparation steps, process and chlorine dioxide concentration measurements of comparative example 1 and example 1 were the same as in example 1. The films and bags produced are shown in figures 1 and 2. The chlorine dioxide concentration is shown in table 2 as a function of time.
Comparative example 2
Comparative example 2 differs from example 1 in that in the composition of the inner layer of the film, the inner layer composition of comparative example 2 is free of a porous inorganic filler. The preparation steps, process and chlorine dioxide concentration measurements of comparative example 2 and example 1 were the same as in example 1. The films and bags produced are shown in figures 1 and 2. The chlorine dioxide concentration is shown in table 2 as a function of time.
Comparative example 1 differs from example 1 in that there is no PVA in the interlayer composition (as in table 1), which is a hydrophilic polymer, and has a certain acceleration effect on penetration of water vapor generated by cherry respiration in the package into the interlayer, and since comparative example 1 has no PVA in the interlayer, chlorine dioxide generated in comparative example 1 is slow and low in concentration as in table 2, compared with PVA in the interlayer of example 1. Comparative example 2 differs from example 1 in that the inner layer composition does not have a porous filler (as in table 1) which facilitates penetration of water vapor generated by cherry respiration in the package into the intermediate layer, and since comparative example 2 does not have a porous filler in the inner layer composition, the rate of chlorine dioxide generation in comparative example 2 is extremely slow and the concentration is low when the time is not long, but the concentration of chlorine dioxide increases only when the time is prolonged, water vapor may penetrate into the intermediate layer through the inner layer LDPE/EVA. As in table 2.
Table 1 raw material compositions of examples and comparative examples
Table 2 results of chlorine dioxide concentration variation in examples and comparative examples
The results of the examples and the comparative examples show that the composition of the raw materials for preparing the functional packaging film is reasonably designed, and the slow release speed of chlorine dioxide can be controlled, thereby controlling the concentration of the chlorine dioxide. Although the invention uses cherry to verify the application of the slow-release chlorine dioxide functional packaging film, the functional packaging film is also suitable for the preservation of other fruit and vegetable foods according to the same principle.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
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