CN116714333A - Polypropylene heat-sealing film with cold and hot antifogging effect for food packaging and preparation method thereof - Google Patents
Polypropylene heat-sealing film with cold and hot antifogging effect for food packaging and preparation method thereof Download PDFInfo
- Publication number
- CN116714333A CN116714333A CN202310992227.8A CN202310992227A CN116714333A CN 116714333 A CN116714333 A CN 116714333A CN 202310992227 A CN202310992227 A CN 202310992227A CN 116714333 A CN116714333 A CN 116714333A
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- heat
- layer
- modified
- cold
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 Polypropylene Polymers 0.000 title claims abstract description 159
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 89
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 89
- 235000013305 food Nutrition 0.000 title claims abstract description 44
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 41
- 230000000694 effects Effects 0.000 title claims abstract description 40
- 238000007789 sealing Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000010410 layer Substances 0.000 claims abstract description 73
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000004698 Polyethylene Substances 0.000 claims abstract description 44
- 229920000573 polyethylene Polymers 0.000 claims abstract description 44
- 239000012792 core layer Substances 0.000 claims abstract description 40
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 32
- 239000012793 heat-sealing layer Substances 0.000 claims abstract description 31
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 25
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 25
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims description 74
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 32
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 32
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 claims description 28
- 239000004593 Epoxy Substances 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 19
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 16
- 239000000155 melt Substances 0.000 claims description 15
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- 239000000600 sorbitol Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 9
- 239000005639 Lauric acid Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 3
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 abstract description 5
- 239000004033 plastic Substances 0.000 abstract description 4
- 239000012785 packaging film Substances 0.000 abstract description 3
- 229920006280 packaging film Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000889 atomisation Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000003405 preventing effect Effects 0.000 abstract 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 19
- 235000019441 ethanol Nutrition 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 235000013311 vegetables Nutrition 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 2
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- FRPAVHFNOFSNDR-UHFFFAOYSA-N 3-(2,4-dioxo-1,3-thiazolidin-3-yl)propanoic acid Chemical compound OC(=O)CCN1C(=O)CSC1=O FRPAVHFNOFSNDR-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 102220040412 rs587778307 Human genes 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
Classifications
-
- 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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/242—All polymers belonging to those covered by group B32B27/32
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
-
- 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
- B32B2553/00—Packaging equipment or accessories not otherwise provided for
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Wrappers (AREA)
Abstract
The invention relates to the technical field of packaging films, and particularly discloses a polypropylene heat-sealing film with a cold and hot antifogging effect for food packaging and a preparation method thereof. The heat sealing film is prepared by three layers of coextrusion, and sequentially comprises a heat sealing layer, a core layer and an antibacterial layer, wherein the heat sealing layer is composed of polypropylene, modified polyethylene and a compatilizer, meanwhile, the heat sealing layer has cold fog and hot fog preventing properties, water is easy to wet the surface of plastic, condensed small water drops can be rapidly diffused to form a water film, the atomization of water fog on the surface of the film is effectively avoided, the core layer is composed of polypropylene and metallocene polyethylene, the antibacterial layer is composed of polypropylene, low-density polyethylene and a modified antibacterial agent, the modified antibacterial agent added into the antibacterial layer has excellent antibacterial property, and meanwhile, the modified antibacterial agent with a long carbon chain is more entangled with resin, so that the migration rate of anti-fog components can be effectively slowed down, the anti-fog effective period of the film is prolonged, and the heat and cold fog preventing effect is excellent.
Description
Technical Field
The invention relates to the technical field of packaging films, in particular to a polypropylene heat-sealing film with a cold and hot antifogging effect for food packaging and a preparation method thereof.
Background
The prefabricated vegetables are finished products or semi-finished products which are obtained through preprocessing, are various in variety and low in price, and greatly facilitate the life of people. Along with the wider and wider application of the prefabricated vegetables in the market, the prefabricated vegetables are greatly changed in the modes of food production, circulation, storage, consumption and the like, wherein the packaging material is an important defense line in the circulation link of the prefabricated vegetables, and can directly influence the storage and transportation of the prefabricated vegetables, the cost control, sales and the food safety. Because the water content in the prefabricated vegetable is large, the temperature is greatly changed in the storage, transportation and sales processes, an opaque water mist layer can be generated in the inner layer of the packaging bag, so that a user cannot see the commodity condition in the packaging bag, the attractive force of the product is reduced, and meanwhile, the water mist can cause the reproduction of bacteria to influence the antibacterial effect of the film. The use of an anti-fog film with antibacterial effect is particularly important in order to allow a user or consumer to clearly see whether food is fresh or not and to inhibit bacterial growth.
The anti-fog film is a food packaging film which prevents water vapor from forming fog on the surface of the film to affect transparency, and can not form fog on the surface of the film due to condensation of the water vapor caused by temperature change, and is generally classified into a cold anti-fog film and a hot anti-fog film. Cold anti-fog means that the inner and outer layers of the film do not fog at low temperature, and hot anti-fog means that the inner and outer layers of the film do not fog at heating or high temperature. The commonly used antifogging film is a polyolefin antifogging film, which has the advantages of high transparency, good thickness uniformity, low cost and the like. Chinese patent CN103707603B discloses a double-sided heat-sealed double-sided antifogging BOPP film and a preparation method thereof, which is formed by co-extruding an inner surface layer, a core layer and an outer surface layer and then biaxially stretching, wherein the inner surface layer and the outer surface layer are made of polypropylene and an anti-sticking agent, the core layer is made of polypropylene, an antifogging agent and a slipping agent, the BOPP antifogging film has excellent antifogging performance, but the antibacterial performance of the antifogging film is poor, and the dispersibility of raw materials in the layers is general, so that the comprehensive performance of the antifogging film is affected to a certain extent.
Therefore, there is a need for developing a polypropylene film for food packaging having a good cold and hot antifogging effect and an antibacterial effect.
Disclosure of Invention
In order to solve the technical problems, the invention provides a polypropylene heat-sealing film with a cold and hot antifogging effect for food packaging and a preparation method thereof, and solves the problems of poor cold and hot antifogging effect and poor antibacterial effect of the polypropylene heat-sealing film.
In order to achieve the aim, the invention discloses a polypropylene heat-sealing film with a cold and hot antifogging effect for food packaging, which is prepared by three layers of coextrusion and sequentially comprises a heat-sealing layer, a core layer and an antibacterial layer; the raw materials of the heat sealing layer comprise polypropylene, modified polyethylene and a compatilizer, wherein the mass ratio of the polypropylene to the modified polyethylene to the compatilizer is 100: (18-35): (0.5-1); the core layer raw material comprises polypropylene and metallocene polyethylene, wherein the mass ratio of the polypropylene to the metallocene polyethylene is 100: (5-10); the antibacterial layer comprises polypropylene, low-density polyethylene and a modified antibacterial agent, wherein the mass ratio of the polypropylene to the low-density polyethylene to the modified antibacterial agent is 100: (8-14): (2-5).
Preferably, the mass ratio of the heat sealing layer, the core layer and the antibacterial layer in unit area is 100: (78-90): (35-64).
Preferably, the compatilizer comprises one of polyoxyethylene monolaurate and polyoxyethylene lauryl ether.
Preferably, the modified polyethylene is prepared by the following steps:
step one, the mass ratio is 100: adding the low-density polyethylene and the maleic anhydride in the step (3-8) into a mixing roll for melt blending, wherein the melt blending temperature is 140-150 ℃, the melt blending time is 4min, the stirring speed in the blending process is 15-35r/min, and cooling is carried out after uniform mixing to obtain the maleic anhydride modified polyethylene;
step two, the mass ratio is (6000-7500): 100: (7-15): and (5) uniformly mixing the acetone, the maleic anhydride modified polyethylene, the sorbitol and the p-toluenesulfonic acid in the steps of (75-120), reacting, filtering after the reaction, washing with the acetone, and drying at 60 ℃ for 12 hours to obtain the modified polyethylene.
Further, the temperature of the reaction in the second step is 60-70 ℃, and the reaction time is 5-7h.
Preferably, the modified antibacterial agent is prepared by the following steps:
s1, dispersing nano titanium dioxide into absolute ethyl alcohol, and adding gamma-glycidoxypropyl trimethoxy silane after uniformly dispersing, wherein the mass ratio of the nano titanium dioxide to the absolute ethyl alcohol to the gamma-glycidoxypropyl trimethoxy silane is 100: (1500-1800): (75-125), in a nitrogen atmosphere, reacting, filtering, washing by using deionized water, and vacuum drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain epoxy modified titanium dioxide;
s2, dispersing epoxy modified titanium dioxide into deionized water by ultrasonic, adding 12-aminododecanoic acid and sodium carbonate after uniform dispersion, stirring and mixing to react, filtering after reaction, washing by using deionized water and ethanol in sequence, and vacuum drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain dodecanoic acid modified titanium dioxide;
s3, mixing lauric acid, triethanolamine, dodecanoic acid modified titanium dioxide and p-toluenesulfonic acid in a nitrogen atmosphere, reacting, taking water in a reaction product out of the mixture by the introduced nitrogen, filtering after the reaction, washing the mixture by deionized water and ethanol in sequence, and vacuum drying the mixture in a vacuum drying oven at 60 ℃ for 12 hours to obtain the modified antibacterial agent.
Further, the reaction temperature in the step S1 is 65-75 ℃, and the reaction time is 18-24h.
Further, the mass ratio of the epoxy modified titanium dioxide, the deionized water, the 12-aminododecanoic acid and the sodium carbonate in the S2 is 100: (900-1200): (50-80): (3-7).
Further, the reaction temperature in the step S2 is 55-60 ℃, and the reaction time is 18-24 hours.
Further, in the S3, the mass ratio of lauric acid, triethanolamine, dodecanoic acid modified titanium dioxide and p-toluenesulfonic acid is (40-70): 100: (55-75): (1-2).
Further, the reaction temperature in the step S3 is 150-160 ℃, and the reaction time is 1-2h.
Preferably, the preparation method of the polypropylene heat-sealing film with the cold and hot antifogging effect for food packaging comprises the following steps:
melt blending the heat-sealing layer raw material polypropylene, modified polyethylene and a compatilizer to obtain a heat-sealing layer melt; melt blending core layer raw material polypropylene and metallocene polyethylene to obtain a core layer melt; and (3) melting and blending antibacterial layer raw material polypropylene, low-density polyethylene and a modified antibacterial agent to obtain an antibacterial layer melt, and extruding and molding the heat-seal layer melt, the core layer melt and the antibacterial layer melt in a three-layer co-extrusion extruder to obtain the polypropylene heat-seal film with a cold and hot antifogging effect for food packaging.
Preferably, the heat seal layer raw material melt blending temperature is 170-180 ℃.
Preferably, the core raw material is melt blended at a temperature of 175-185 ℃.
Preferably, the temperature of the melt blending of the antibacterial layer raw materials is 155-165 ℃.
Preferably, the die temperature of the three-layer coextrusion extruder is 185-195 ℃.
In the invention, the modified polyethylene in the raw material of the heat sealing layer is prepared by modifying low-density polyethylene by maleic anhydride, obtaining maleic anhydride modified polyethylene after melt blending, and carrying out esterification reaction on anhydride groups on the maleic anhydride modified polyethylene and sorbitol under the action of p-toluenesulfonic acid; the modified antibacterial agent in the antibacterial layer raw material is prepared by modifying nano titanium dioxide by using gamma-glycidol ether oxypropyl trimethoxy silane, introducing epoxy groups on the surface of the nano titanium dioxide to obtain epoxy modified titanium dioxide, performing epoxy ring opening reaction on the epoxy groups on the epoxy modified titanium dioxide and amino groups on 12-amino dodecanoic acid to obtain dodecanoic acid modified titanium dioxide, introducing carboxyl on the surface of the titanium dioxide, and finally performing esterification reaction with hydroxyl on triethanolamine to obtain the modified antibacterial agent. The three-layer structure has higher oxygen barrier property and good fresh-keeping property.
Compared with the prior art, the invention has the beneficial effects that: the low-density polyethylene used in the invention has the characteristics of high impact strength, cold resistance, low temperature resistance and higher temperature resistance, the moisture resistance is better, the metallocene polyethylene has the characteristic of high heat resistance, and the polypropylene is colorless, odorless and odorless resin, and has excellent chemical resistance, heat resistance and mechanical strength.
The sorbitol introduced into the heat sealing layer contains a large amount of hydroxyl groups, has good hydrophilic activity, generates ester after reacting with maleic anhydride modified polyethylene, has long-term antifogging property, has cold fog resistance and hot fog resistance, ensures that water is easy to wet the surface of plastic, and can be rapidly diffused to form a water film, so that the atomization of water mist on the surface of the film is effectively avoided, the food condition of the inner package of the heat sealing film is conveniently checked, and the sorbitol is grafted onto the low-density polyethylene by a chemical grafting method, and is mixed with polypropylene and a compatilizer, so that the precipitation of micromolecular sorbitol is effectively avoided, and the micromolecular sorbitol can be uniformly distributed in a matrix. The polypropylene and the metallocene polyethylene in the core layer have excellent mechanical properties after being mixed. The nano titanium dioxide of the modified antibacterial agent has an empty conduction band and valence band structure, electrons are excited from valence band to conduction band in a water and air system under the illumination condition, corresponding holes are generated in the valence band to generate electron-hole pairs, the electrons and the holes are separated under the action of an electric field and migrate to the surface of the titanium dioxide, and the formed superoxide radicals react with organic matters in bacteria to kill the bacteria, so that the bacteria are decomposed, and the agglomeration of the nano titanium dioxide is effectively avoided after the modification, the nano titanium dioxide is uniformly dispersed in a matrix, and a better antibacterial effect is achieved. The alkyl long chain further improves the binding effect of the molecule to bacteria, thereby correspondingly enhancing the antibacterial ability. The triethanolamine laurate introduced on the nano titanium dioxide has excellent surface activity and good biodegradability, and is added into a matrix, so that the contact angle of a film and water drops is effectively reduced, the water drops can spread on the surface of the film, and the anti-fog purpose is further achieved. Meanwhile, the modified antibacterial agent with the long carbon chain has a larger molecular structure, is more entangled with resin, can effectively slow down the migration rate of the antifogging component, prolongs the antifogging effective period of the film, and has excellent cold and hot antifogging effect.
Drawings
FIG. 1 is a flowchart of the process for preparing a polypropylene heat-seal film for food packaging having a cold and hot antifogging effect according to the present invention;
FIG. 2 is a flow chart of the preparation of a modified antimicrobial agent in accordance with the present invention;
FIG. 3 is a graph showing the tensile strength in the machine direction and the elongation at break in the machine direction of examples 1 to 4 and comparative examples 1 to 2 in the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Example 1
The embodiment discloses a preparation method of a polypropylene heat-sealing film with a cold and hot antifogging effect for food packaging, which comprises the following steps:
(1) The mass ratio is 100:18:0.5 polypropylene, modified polyethylene and compatilizer polyoxyethylene monolaurate are melt-blended at 170 ℃ to obtain a heat-seal layer melt;
(2) The mass ratio is 100:5, melting and blending the polypropylene and the metallocene polyethylene at 175 ℃ to obtain a core layer melt;
(3) The mass ratio is 100:8:2, melting and blending the polypropylene, the low-density polyethylene and the modified antibacterial agent at 155 ℃ to obtain an antibacterial layer melt;
(4) Extruding and molding the heat-sealing layer melt, the core layer melt and the antibacterial layer melt in a three-layer co-extrusion extruder, wherein the die head temperature of the three-layer co-extrusion extruder is 185 ℃, and obtaining the polypropylene heat-sealing film with a cold and hot anti-fog effect for food packaging; the polypropylene heat-sealing film with the cold and hot antifogging effect for food packaging sequentially comprises a heat-sealing layer, a core layer and an antibacterial layer; the mass ratio of the heat sealing layer to the core layer to the antibacterial layer in unit area is 100:78:35;
wherein the modified polyethylene is prepared by the following steps:
step one, the mass ratio is 100:3, adding the low-density polyethylene and the maleic anhydride into a mixing roll for melt blending, wherein the melt blending temperature is 140 ℃, the melt blending time is 4min, the stirring speed in the blending process is 15r/min, and cooling is carried out after uniform mixing to obtain the maleic anhydride modified polyethylene;
step two, the mass ratio is 6000:100:7:75 acetone, maleic anhydride modified polyethylene, sorbitol and p-toluenesulfonic acid are uniformly mixed, reacted at 60 ℃ for 7 hours, filtered, washed by acetone and dried at 60 ℃ for 12 hours to obtain the modified polyethylene.
Wherein the modified antibacterial agent is prepared by the following steps:
s1, dispersing nano titanium dioxide into absolute ethyl alcohol, and adding gamma-glycidoxypropyl trimethoxy silane after uniformly dispersing, wherein the mass ratio of the nano titanium dioxide to the absolute ethyl alcohol to the gamma-glycidoxypropyl trimethoxy silane is 100:1500:75, reacting at 65 ℃ in a nitrogen atmosphere for 24 hours, filtering after the reaction, washing with deionized water, and vacuum drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain epoxy modified titanium dioxide;
s2, ultrasonically dispersing the epoxy modified titanium dioxide into deionized water, and adding 12-aminododecanoic acid and sodium carbonate after uniformly dispersing, wherein the mass ratio of the epoxy modified titanium dioxide to the deionized water to the 12-aminododecanoic acid to the sodium carbonate is 100:900:50:3, stirring and mixing, reacting for 24 hours at 55 ℃, filtering after the reaction, washing by using deionized water and ethanol in sequence, and vacuum drying for 12 hours in a vacuum drying oven at 60 ℃ to obtain the dodecanoic acid modified titanium dioxide;
s3, in a nitrogen atmosphere, the mass ratio is 40:100:55:1, lauric acid, triethanolamine, dodecanoic acid modified titanium dioxide and p-toluenesulfonic acid are mixed, reacted for 2 hours at 150 ℃, filtered, washed by deionized water and ethanol in sequence, and dried in vacuum in a vacuum drying oven at 60 ℃ for 12 hours, thus obtaining the modified antibacterial agent.
Example 2
The embodiment discloses a preparation method of a polypropylene heat-sealing film with a cold and hot antifogging effect for food packaging, which comprises the following steps:
(1) The mass ratio is 100:24:0.7, melting and blending polypropylene, modified polyethylene and a compatilizer polyoxyethylene monolaurate at 175 ℃ to obtain a heat-sealing layer melt;
(2) The mass ratio is 100:7, melting and blending the polypropylene and the metallocene polyethylene at 180 ℃ to obtain a core layer melt;
(3) The mass ratio is 100:10:3, melting and blending the polypropylene, the low-density polyethylene and the modified antibacterial agent at 160 ℃ to obtain an antibacterial layer melt;
(4) Extruding and molding the heat-sealing layer melt, the core layer melt and the antibacterial layer melt in a three-layer co-extrusion extruder, wherein the die head temperature of the three-layer co-extrusion extruder is 190 ℃, so as to obtain the polypropylene heat-sealing film with the cold and hot antifogging effect for food packaging; the polypropylene heat-sealing film with the cold and hot antifogging effect for food packaging sequentially comprises a heat-sealing layer, a core layer and an antibacterial layer; the mass ratio of the heat sealing layer to the core layer to the antibacterial layer in unit area is 100:82:45;
wherein the modified polyethylene is prepared by the following steps:
step one, the mass ratio is 100:6, adding the low-density polyethylene and the maleic anhydride into a mixing mill for melt blending, wherein the melt blending temperature is 145 ℃, the melt blending time is 4min, the stirring speed in the blending process is 30r/min, and cooling is performed after uniform mixing to obtain the maleic anhydride modified polyethylene;
step two, the mass ratio is 7000:100:12:105 acetone, maleic anhydride modified polyethylene, sorbitol and p-toluenesulfonic acid are uniformly mixed, reacted for 6 hours at 65 ℃, filtered, washed by acetone and dried for 12 hours at 60 ℃ to obtain the modified polyethylene.
Wherein the modified antibacterial agent is prepared by the following steps:
s1, dispersing nano titanium dioxide into absolute ethyl alcohol, and adding gamma-glycidoxypropyl trimethoxy silane after uniformly dispersing, wherein the mass ratio of the nano titanium dioxide to the absolute ethyl alcohol to the gamma-glycidoxypropyl trimethoxy silane is 100:1700:105, reacting at 70 ℃ in nitrogen atmosphere for 22 hours, filtering after the reaction, washing with deionized water, and vacuum drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain epoxy modified titanium dioxide;
s2, ultrasonically dispersing the epoxy modified titanium dioxide into deionized water, and adding 12-aminododecanoic acid and sodium carbonate after uniformly dispersing, wherein the mass ratio of the epoxy modified titanium dioxide to the deionized water to the 12-aminododecanoic acid to the sodium carbonate is 100:1050:70:5, stirring and mixing, reacting for 22 hours at 58 ℃, filtering after the reaction, washing by using deionized water and ethanol in sequence, and vacuum drying for 12 hours in a vacuum drying oven at 60 ℃ to obtain the dodecanoic acid modified titanium dioxide;
s3, in a nitrogen atmosphere, the mass ratio is 55:100:65:1.8 lauric acid, triethanolamine, dodecanoic acid modified titanium dioxide and p-toluenesulfonic acid are mixed, reacted for 1.5 hours at 155 ℃, filtered, washed by deionized water and ethanol in sequence, and dried in vacuum in a vacuum drying oven at 60 ℃ for 12 hours to obtain the modified antibacterial agent.
Example 3
The embodiment discloses a preparation method of a polypropylene heat-sealing film with a cold and hot antifogging effect for food packaging, which comprises the following steps:
(1) The mass ratio is 100:30:0.9 polypropylene, modified polyethylene and compatilizer polyoxyethylene monolaurate are melt blended at 175 ℃ to obtain a heat seal layer melt;
(2) The mass ratio is 100:9, melting and blending the polypropylene and the metallocene polyethylene at 180 ℃ to obtain a core layer melt;
(3) The mass ratio is 100:12:4, melting and blending the polypropylene, the low-density polyethylene and the modified antibacterial agent at 160 ℃ to obtain an antibacterial layer melt;
(4) Extruding and molding the heat-sealing layer melt, the core layer melt and the antibacterial layer melt in a three-layer co-extrusion extruder, wherein the die head temperature of the three-layer co-extrusion extruder is 190 ℃, so as to obtain the polypropylene heat-sealing film with the cold and hot antifogging effect for food packaging; the polypropylene heat-sealing film with the cold and hot antifogging effect for food packaging sequentially comprises a heat-sealing layer, a core layer and an antibacterial layer; the mass ratio of the heat sealing layer to the core layer to the antibacterial layer in unit area is 100:6:55;
wherein the modified polyethylene is prepared by the following steps:
step one, the mass ratio is 100:6, adding the low-density polyethylene and the maleic anhydride into a mixing mill for melt blending, wherein the melt blending temperature is 145 ℃, the melt blending time is 4min, the stirring speed in the blending process is 30r/min, and cooling is performed after uniform mixing to obtain the maleic anhydride modified polyethylene;
step two, the mass ratio is 7000:100:12:105 acetone, maleic anhydride modified polyethylene, sorbitol and p-toluenesulfonic acid are uniformly mixed, reacted for 6 hours at 65 ℃, filtered, washed by acetone and dried for 12 hours at 60 ℃ to obtain the modified polyethylene.
Wherein the modified antibacterial agent is prepared by the following steps:
s1, dispersing nano titanium dioxide into absolute ethyl alcohol, and adding gamma-glycidoxypropyl trimethoxy silane after uniformly dispersing, wherein the mass ratio of the nano titanium dioxide to the absolute ethyl alcohol to the gamma-glycidoxypropyl trimethoxy silane is 100:1700:105, reacting at 70 ℃ in nitrogen atmosphere for 22 hours, filtering after the reaction, washing with deionized water, and vacuum drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain epoxy modified titanium dioxide;
s2, ultrasonically dispersing the epoxy modified titanium dioxide into deionized water, and adding 12-aminododecanoic acid and sodium carbonate after uniformly dispersing, wherein the mass ratio of the epoxy modified titanium dioxide to the deionized water to the 12-aminododecanoic acid to the sodium carbonate is 100:1050:70:5, stirring and mixing, reacting for 22 hours at 58 ℃, filtering after the reaction, washing by using deionized water and ethanol in sequence, and vacuum drying for 12 hours in a vacuum drying oven at 60 ℃ to obtain the dodecanoic acid modified titanium dioxide;
s3, in a nitrogen atmosphere, the mass ratio is 55:100:65:1.8 lauric acid, triethanolamine, dodecanoic acid modified titanium dioxide and p-toluenesulfonic acid are mixed, reacted for 1.5 hours at 155 ℃, filtered, washed by deionized water and ethanol in sequence, and dried in vacuum in a vacuum drying oven at 60 ℃ for 12 hours to obtain the modified antibacterial agent.
Example 4
The embodiment discloses a preparation method of a polypropylene heat-sealing film with a cold and hot antifogging effect for food packaging, which comprises the following steps:
(1) The mass ratio is 100:35:1, polypropylene, modified polyethylene and a compatilizer polyoxyethylene monolaurate are melt-blended at 180 ℃ to obtain a heat-seal layer melt;
(2) The mass ratio is 100:10 and metallocene polyethylene are melt blended at 185 ℃ to obtain a core layer melt;
(3) The mass ratio is 100:14:5, melting and blending the polypropylene, the low-density polyethylene and the modified antibacterial agent at 165 ℃ to obtain an antibacterial layer melt;
(4) Extruding and molding the heat-sealing layer melt, the core layer melt and the antibacterial layer melt in a three-layer co-extrusion extruder, wherein the die head temperature of the three-layer co-extrusion extruder is 195 ℃, and obtaining the polypropylene heat-sealing film with cold and hot antifogging effect for food packaging; the polypropylene heat-sealing film with the cold and hot antifogging effect for food packaging sequentially comprises a heat-sealing layer, a core layer and an antibacterial layer; the mass ratio of the heat sealing layer to the core layer to the antibacterial layer in unit area is 100:90:64;
wherein the modified polyethylene is prepared by the following steps:
step one, the mass ratio is 100:8, adding the low-density polyethylene and the maleic anhydride into a mixing mill for melt blending, wherein the melt blending temperature is 150 ℃, the melt blending time is 4min, the stirring speed in the blending process is 35r/min, and cooling is performed after uniform mixing to obtain the maleic anhydride modified polyethylene;
step two, the mass ratio is 7500:100:15:120, maleic anhydride modified polyethylene, sorbitol and p-toluenesulfonic acid are uniformly mixed, reacted for 5 hours at 70 ℃, filtered, washed by acetone and dried for 12 hours at 60 ℃ to obtain the modified polyethylene.
Wherein the modified antibacterial agent is prepared by the following steps:
s1, dispersing nano titanium dioxide into absolute ethyl alcohol, and adding gamma-glycidoxypropyl trimethoxy silane after uniformly dispersing, wherein the mass ratio of the nano titanium dioxide to the absolute ethyl alcohol to the gamma-glycidoxypropyl trimethoxy silane is 100:1800:125, in a nitrogen atmosphere, reacting at 75 ℃ for 18 hours, filtering after the reaction, washing with deionized water, and vacuum drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain epoxy modified titanium dioxide;
s2, ultrasonically dispersing the epoxy modified titanium dioxide into deionized water, and adding 12-aminododecanoic acid and sodium carbonate after uniformly dispersing, wherein the mass ratio of the epoxy modified titanium dioxide to the deionized water to the 12-aminododecanoic acid to the sodium carbonate is 100:1200:80:7, stirring and mixing, reacting for 18 hours at 60 ℃, filtering after the reaction, washing by using deionized water and ethanol in sequence, and vacuum drying for 12 hours in a vacuum drying oven at 60 ℃ to obtain the dodecanoic acid modified titanium dioxide;
s3, in a nitrogen atmosphere, the mass ratio is 70:100:75:2, mixing lauric acid, triethanolamine, dodecanoic acid modified titanium dioxide and p-toluenesulfonic acid, reacting for 1h at 160 ℃, filtering after the reaction, washing by using deionized water and ethanol in sequence, and vacuum drying for 12h in a vacuum drying oven at 60 ℃ to obtain the modified antibacterial agent.
Comparative example 1
A preparation method of a polypropylene heat-sealing film for food packaging comprises the following steps:
(1) The mass ratio is 100:30:0.9 polypropylene, modified polyethylene and compatilizer polyoxyethylene monolaurate are melt blended at 175 ℃ to obtain a heat seal layer melt;
(2) The mass ratio is 100:9, melting and blending the polypropylene and the metallocene polyethylene at 180 ℃ to obtain a core layer melt;
(3) The mass ratio is 100:12:4, melting and blending the polypropylene, the low-density polyethylene and the epoxy modified titanium dioxide at 160 ℃ to obtain an antibacterial layer melt;
(4) Extruding and molding the heat-sealing layer melt, the core layer melt and the antibacterial layer melt in a three-layer co-extrusion extruder at the extrusion temperature of 190 ℃ to obtain a polypropylene heat-sealing film for food packaging; the polypropylene heat-sealing film with the cold and hot antifogging effect for food packaging sequentially comprises a heat-sealing layer, a core layer and an antibacterial layer; the mass ratio of the heat sealing layer to the core layer to the antibacterial layer in unit area is 100:6:55;
wherein the modified polyethylene is prepared by the following steps:
step one, the mass ratio is 100:6, adding the low-density polyethylene and the maleic anhydride into a mixing mill for melt blending, wherein the melt blending temperature is 145 ℃, the melt blending time is 4min, the stirring speed in the blending process is 30r/min, and cooling is performed after uniform mixing to obtain the maleic anhydride modified polyethylene;
step two, the mass ratio is 7000:100:12:105 acetone, maleic anhydride modified polyethylene, sorbitol and p-toluenesulfonic acid are uniformly mixed, reacted for 6 hours at 65 ℃, filtered, washed by acetone and dried for 12 hours at 60 ℃ to obtain the modified polyethylene.
Wherein the epoxy modified titanium dioxide is prepared by the following steps:
dispersing nano titanium dioxide into absolute ethyl alcohol, and adding gamma-glycidoxypropyl trimethoxy silane after uniform dispersion, wherein the mass ratio of the nano titanium dioxide to the absolute ethyl alcohol to the gamma-glycidoxypropyl trimethoxy silane is 100:1700:105, in a nitrogen atmosphere, reacting at 70 ℃ for 22 hours, filtering after the reaction, washing with deionized water, and vacuum drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain the epoxy modified titanium dioxide.
Comparative example 2
A preparation method of a polypropylene heat-sealing film for food packaging comprises the following steps:
(1) The mass ratio is 100:26.8:3.2:0.9 polypropylene, low density polyethylene, sorbitol and compatilizer polyoxyethylene monolaurate are melt blended at 175 ℃ to obtain a heat seal layer melt;
(2) The mass ratio is 100:9, melting and blending the polypropylene and the metallocene polyethylene at 180 ℃ to obtain a core layer melt;
(3) The mass ratio is 100:12:4, melting and blending the polypropylene, the low-density polyethylene and the modified antibacterial agent at 160 ℃ to obtain an antibacterial layer melt;
(4) The mass ratio is 100:6:55, the core layer melt, the antibacterial layer melt are extruded and molded in a three-layer co-extrusion extruder, and the die head temperature of the three-layer co-extrusion extruder is 190 ℃, so that the polypropylene heat-sealing film for food packaging is obtained.
Wherein the modified antibacterial agent is prepared by the following steps:
s1, dispersing nano titanium dioxide into absolute ethyl alcohol, and adding gamma-glycidoxypropyl trimethoxy silane after uniformly dispersing, wherein the mass ratio of the nano titanium dioxide to the absolute ethyl alcohol to the gamma-glycidoxypropyl trimethoxy silane is 100:1700:105, reacting at 70 ℃ in nitrogen atmosphere for 22 hours, filtering after the reaction, washing with deionized water, and vacuum drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain epoxy modified titanium dioxide;
s2, ultrasonically dispersing the epoxy modified titanium dioxide into deionized water, and adding 12-aminododecanoic acid and sodium carbonate after uniformly dispersing, wherein the mass ratio of the epoxy modified titanium dioxide to the deionized water to the 12-aminododecanoic acid to the sodium carbonate is 100:1050:70:5, stirring and mixing, reacting for 22 hours at 58 ℃, filtering after the reaction, washing by using deionized water and ethanol in sequence, and vacuum drying for 12 hours in a vacuum drying oven at 60 ℃ to obtain the dodecanoic acid modified titanium dioxide;
s3, in a nitrogen atmosphere, the mass ratio is 55:100:65:1.8 lauric acid, triethanolamine, dodecanoic acid modified titanium dioxide and p-toluenesulfonic acid are mixed, reacted for 1.5 hours at 155 ℃, filtered, washed by deionized water and ethanol in sequence, and dried in vacuum in a vacuum drying oven at 60 ℃ for 12 hours to obtain the modified antibacterial agent.
The low-density polyethylene used in the examples and comparative examples of the present invention was LDPE2426H, purchased from China petrochemical group, name of petrochemical Co., ltd; polypropylene is purchased from China petroleum Daqing petrochemical company, and the model is T30S; metallocene polyethylene was purchased from Dongguan Ming Yuan Plastic Co., ltd., brand: ceramic, trade name NG5401B; the nano titanium dioxide is purchased from Xuancheng Jinrui New material Co., ltd, the model is JR05, and the average grain diameter is 5nm.
The polypropylene heat-seal films prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to the relevant performance test as samples, and the specific test is as follows:
(1) Haze test: the anti-fog performance of the polypropylene heat-sealing film is evaluated by adopting a cold fog method in GB/T31726-2015, and the evaluation standard is as follows: 1) Completely transparent, free of water drops; 2) The transparency is good, a small amount of uneven large water drops exist, and the cleaning degree of the visual acuity chart with the area of more than 50% is completely consistent with that before the experiment; 3) Is basically transparent and has more water drops; 4) Semitransparent, has many tiny water drops; 5) Completely opaque, record anti-fog rating;
(2) Mechanical strength test: determination of tensile Properties of Plastic third section according to national Standard GB/T1040.3-2006: experimental conditions for films and sheets the longitudinal tensile strength (MPa) and the longitudinal elongation at break of polypropylene heat-seal films were tested;
(3) Antibacterial test: the antibacterial rate of the polypropylene heat-sealing film on escherichia coli and staphylococcus aureus is tested according to QB/T2591-2003 antibacterial plastic-antibacterial performance test method and antibacterial effect (film-sticking method);
(4) Heat seal strength test: the heat-seal strength (N/15 mm) of the polypropylene heat-seal film was tested according to standard QB/T2358-1998 Heat-seal Strength test method for Plastic packaging, and the sample used a 300mm/min draw rate; the test results are shown in table 1:
as can be seen from the test results of Table 1, the polypropylene heat-sealing films in examples 1 to 4 provided by the invention have excellent antifogging ability, high antibacterial rate, excellent mechanical properties and good heat-sealing strength. The excellent antibacterial effect and the antifogging capability can ensure the long-term fresh-keeping of the prepared vegetables, inhibit decay, effectively prolong the shelf life, and simultaneously, the antifogging effect is good and the food condition of the internal package of the heat sealing film is conveniently checked.
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 hereto without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The polypropylene heat-sealing film with the cold and hot antifogging effect for food packaging is characterized by being prepared by three layers of coextrusion and sequentially comprising a heat-sealing layer, a core layer and an antibacterial layer; the raw materials of the heat sealing layer comprise polypropylene, modified polyethylene and a compatilizer, wherein the mass ratio of the polypropylene to the modified polyethylene to the compatilizer is 100: (18-35): (0.5-1); the core layer raw material comprises polypropylene and metallocene polyethylene, wherein the mass ratio of the polypropylene to the metallocene polyethylene is 100: (5-10); the antibacterial layer comprises polypropylene, low-density polyethylene and a modified antibacterial agent, wherein the mass ratio of the polypropylene to the low-density polyethylene to the modified antibacterial agent is 100: (8-14): (2-5).
2. The polypropylene heat-sealing film for food packaging with cold and hot antifogging effect according to claim 1, wherein the mass ratio of the heat-sealing layer, the core layer and the antibacterial layer in unit area is 100: (78-90): (35-64).
3. A polypropylene heat-seal film for food packaging having a cold and hot antifogging effect according to claim 1, wherein said compatibilizer comprises one of polyoxyethylene monolaurate and polyoxyethylene lauryl ether.
4. The polypropylene heat-sealing film for food packaging with cold and hot antifogging effect according to claim 1, wherein the modified polyethylene is prepared by the following steps:
step one, the mass ratio is 100: adding the low-density polyethylene and the maleic anhydride in the step (3-8) into a mixing roll for melt blending, wherein the temperature of the melt blending is 140-150 ℃, the time of the melt blending is 4min, and cooling after uniform mixing to obtain the maleic anhydride modified polyethylene;
step two, the mass ratio is (6000-7500): 100: (7-15): and (75-120) uniformly mixing acetone, maleic anhydride modified polyethylene, sorbitol and p-toluenesulfonic acid, reacting, filtering, washing and drying to obtain the modified polyethylene.
5. The polypropylene heat-sealing film for food packaging with cold and hot antifogging effect according to claim 1, wherein the modified antibacterial agent comprises the following steps:
s1, dispersing nano titanium dioxide into absolute ethyl alcohol, and adding gamma-glycidoxypropyl trimethoxy silane after uniformly dispersing, wherein the mass ratio of the nano titanium dioxide to the absolute ethyl alcohol to the gamma-glycidoxypropyl trimethoxy silane is 100: (1500-1800): (75-125), in the nitrogen atmosphere, reacting, filtering, washing and drying to obtain the epoxy modified titanium dioxide;
s2, dispersing epoxy modified titanium dioxide into deionized water by ultrasonic, adding 12-aminododecanoic acid and sodium carbonate after uniform dispersion, stirring and mixing, reacting, filtering, washing and drying to obtain dodecanoic acid modified titanium dioxide;
s3, mixing lauric acid, triethanolamine, dodecanoic acid modified titanium dioxide and p-toluenesulfonic acid in a nitrogen atmosphere, reacting, filtering, washing and drying to obtain the modified antibacterial agent.
6. A method for producing a polypropylene heat-sealing film for food packaging having a cold and hot antifogging effect as claimed in any one of claims 1 to 5, comprising the steps of:
melt blending the heat-sealing layer raw material polypropylene, modified polyethylene and a compatilizer to obtain a heat-sealing layer melt; melt blending core layer raw material polypropylene and metallocene polyethylene to obtain a core layer melt; and (3) melting and blending antibacterial layer raw material polypropylene, low-density polyethylene and a modified antibacterial agent to obtain an antibacterial layer melt, and extruding and molding the heat-seal layer melt, the core layer melt and the antibacterial layer melt in a three-layer co-extrusion extruder to obtain the polypropylene heat-seal film with a cold and hot antifogging effect for food packaging.
7. The method for producing a polypropylene heat-seal film for food packaging having a cold and hot antifogging effect according to claim 6, wherein the heat-seal layer raw material is melt-blended at a temperature of 170 to 180 ℃.
8. The method for producing a polypropylene heat-sealing film for food packaging having a cold and hot antifogging effect according to claim 6, wherein the core layer raw material is melt-blended at a temperature of 175-185 ℃.
9. The method for producing a polypropylene heat-sealing film for food packaging having a cold and hot antifogging effect according to claim 6, wherein the raw material of said antibacterial layer is melt-blended at a temperature of 155 to 165 ℃.
10. The method for producing a polypropylene heat-sealing film for food packaging having a cold and hot antifogging effect according to claim 6, wherein the die temperature of the three-layer coextrusion extruder is 185 to 195 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310992227.8A CN116714333B (en) | 2023-08-08 | 2023-08-08 | Polypropylene heat-sealing film with cold and hot antifogging effect for food packaging and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310992227.8A CN116714333B (en) | 2023-08-08 | 2023-08-08 | Polypropylene heat-sealing film with cold and hot antifogging effect for food packaging and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116714333A true CN116714333A (en) | 2023-09-08 |
| CN116714333B CN116714333B (en) | 2023-10-13 |
Family
ID=87866413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310992227.8A Active CN116714333B (en) | 2023-08-08 | 2023-08-08 | Polypropylene heat-sealing film with cold and hot antifogging effect for food packaging and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116714333B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007230022A (en) * | 2006-02-28 | 2007-09-13 | Nippon Polyethylene Kk | Laminate excellent in antifungal and antibacterial properties and packaging bag |
| CN104098791A (en) * | 2014-06-30 | 2014-10-15 | 安徽巢湖南方膜业有限责任公司 | Biodegradable thermoplastic starch-polyethylene film |
| CN109049918A (en) * | 2018-06-07 | 2018-12-21 | 江阴通利光电科技有限公司 | A kind of antifog toughening antibacterial cast polypropylene food package film and preparation method thereof |
-
2023
- 2023-08-08 CN CN202310992227.8A patent/CN116714333B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007230022A (en) * | 2006-02-28 | 2007-09-13 | Nippon Polyethylene Kk | Laminate excellent in antifungal and antibacterial properties and packaging bag |
| CN104098791A (en) * | 2014-06-30 | 2014-10-15 | 安徽巢湖南方膜业有限责任公司 | Biodegradable thermoplastic starch-polyethylene film |
| CN109049918A (en) * | 2018-06-07 | 2018-12-21 | 江阴通利光电科技有限公司 | A kind of antifog toughening antibacterial cast polypropylene food package film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116714333B (en) | 2023-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2267756C (en) | Resin composition, production thereof, and laminate comprising a layer composed of said resin composition | |
| AU627589B2 (en) | Starch films based on high amylose starch | |
| CN110861381B (en) | Antibacterial, shockproof and moisture-absorbing degradable food fresh-keeping pad and preparation method thereof | |
| CN113234307B (en) | Full-degradable antibacterial food packaging film and preparation method thereof | |
| CN109054145B (en) | Antibacterial polyethylene food packaging film and preparation method thereof | |
| CN111333888A (en) | Degradable polylactic acid antibacterial film and preparation method thereof | |
| CN103707603A (en) | Double-face heat-sealed and anti-fogging type BOPP (biaxially-oriented polypropylene) film and preparation method thereof | |
| CN113667168A (en) | Water-blocking enhanced degradable antibacterial film and preparation method and application thereof | |
| CN110982158A (en) | Film and method for producing same | |
| JP2000136281A (en) | Resin composition and use thereof | |
| CN116714333B (en) | Polypropylene heat-sealing film with cold and hot antifogging effect for food packaging and preparation method thereof | |
| JP3871437B2 (en) | Method for drying saponified pellets of ethylene-vinyl acetate copolymer | |
| CN111763365B (en) | Antibacterial fresh-keeping material containing nano-silver and preparation method thereof | |
| JPH04164941A (en) | Polyolefin resin composition and use thereof | |
| JP2000044756A (en) | Manufacture of composition of saponified ethylene- vinylacetate copolymer | |
| JP2000128996A (en) | Saponified product pellet of ethylene-vinyl acetate copolymer | |
| CN115584043A (en) | High-barrier biodegradable film and preparation method and application thereof | |
| JP3895011B2 (en) | Resin composition and laminate thereof | |
| JP5004375B2 (en) | Saponified ethylene-vinyl acetate copolymer and laminate thereof | |
| JP3841943B2 (en) | Production method of resin composition | |
| JP4125417B2 (en) | Manufacturing method of resin composition | |
| JP3841941B2 (en) | Production method of resin composition | |
| CN110239181A (en) | A kind of polyvinyl alcohol biodegrade high-barrier plastic film material and preparation method thereof | |
| CN111015996A (en) | Granulation method based on PVA/starch, master batch prepared by granulation method and application of master batch | |
| JPH11293077A (en) | Preparation of resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |