CN115230271B

CN115230271B - High-barrier anti-adhesion composite film and preparation method and application thereof

Info

Publication number: CN115230271B
Application number: CN202110443333.1A
Authority: CN
Inventors: 胡晨曦; 王宇韬; 初立秋; 茹越; 张晓红; 乔金樑; 戚桂村; 董穆; 蔡传伦; 赖金梅; 蒋海斌; 李�杰; 高达利; 张师军
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2021-04-23
Filing date: 2021-04-23
Publication date: 2024-05-07
Anticipated expiration: 2041-04-23
Also published as: CN115230271A

Abstract

The invention relates to a high-barrier anti-adhesion composite film and a preparation method and application thereof, belonging to the technical field of high polymer materials. The high-barrier anti-adhesion composite film comprises an outer layer film and an inner layer film; the outer film comprises an anti-adhesion composition; the anti-blocking composition comprises a polyolefin resin, a multifunctional additive; the multifunctional additive is selected from at least one of zinc salt microsphere composition and guanidine salt microsphere composition; the inner film comprises a high barrier thermoplastic resin. The high-barrier anti-adhesion composite film has excellent barrier property and openness, higher added value of products, low cost of related raw materials, simple preparation process and easy industrialized popularization.

Description

High-barrier anti-adhesion composite film and preparation method and application thereof

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a high-barrier anti-adhesion composite film, a preparation method and application thereof.

Background

Compared with the traditional packaging materials (such as paper, aluminum foil, ceramic, glass and the like), the plastic package has the advantages of low price, light weight, easy molding and transportation and the like. With the rapid development of the plastic packaging industry and the improvement of living standard, the requirements of people on packaging materials are continuously improved, and the functional film gradually becomes one field with the most development prospect of packaging technology. Plastic packaging films with high barrier properties, easy opening properties and the like have become one of the hot spots for market development.

The food and the medicine generally need to isolate oxygen and water vapor in the transportation and preservation processes, and most of the existing plastic packaging materials use PVDC coatings, EVOH, PVA, nylon and the like as barrier layers, but PVDC environmental protection is poor, and materials such as EVOH, PVA and nylon are not waterproof. The above barrier materials which are generally not water resistant need to be used in combination with other materials, such as PP, PE, PET, which have good moisture barrier properties. The patent (publication number: CN 204506031U) takes a PE film as an outer layer and an EVOH film as a barrier layer, so that a tearing-resistant and high-barrier composite film is prepared; liang Xiaogong et al (study on mechanical, thermal and barrier properties of ethylene-vinyl alcohol copolymer composite film, plastic technology, 2015,43 (06), 21-24) for preparing multilayer composite film by using EVOH, PA6 and PE, study shows that under high humidity environment, the oxygen barrier property of EVOH is gradually increased, but the water vapor barrier property tends to be reduced, and the ductility of the film after the EVOH is compounded with PA6 and PE is improved, which shows that the three can be compounded to obtain the tough composite film.

Plastic film materials, due to their high surface coefficient of friction, adhere under heat and pressure (air pressure, extrusion, compression roller, rolling), and may also adhere during processing, use and storage of the film (especially PE, PP-type materials). To solve such problems, an opening agent is often added to the film to facilitate the subsequent use. Currently, common opening agents can be classified into organic and inorganic ones, and organic opening agents such as amide compounds and stearates can migrate to the surface of a film to act as a barrier to play a role in opening; the inorganic opening agent has low price and rich types, and comprises silicon dioxide, calcium carbonate, calcium hydrophosphate, diatomite, talcum powder, molecular sieve and the like.

The multifunctional plastic packaging film has wide development prospect, but the modification research of the current composite film is more complex. Therefore, the development of the high-performance composite film with integrated barrier property and opening property and the preparation method and application thereof have important market value and economic significance.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a high-barrier anti-adhesion composite film. In particular to a high-barrier anti-adhesion composite film and a preparation method and application thereof. The high-performance composite membrane has high barrier and anti-adhesion functions, the cost of the related raw materials is low, the preparation process is simple, and the industrial popularization is easy.

One of the purposes of the invention is to provide a high-barrier anti-adhesion composite film which can comprise an outer layer film and an inner layer film which are overlapped;

The outer film may comprise an anti-adhesion composition;

The anti-blocking composition may comprise a polyolefin resin, a multifunctional additive;

The multifunctional additive can be selected from at least one of zinc salt microsphere composition and guanidine salt microsphere composition;

the inner layer film may comprise a high barrier thermoplastic resin.

Preferably, the method comprises the steps of,

The total thickness of the high-barrier anti-adhesion composite film can be 10-250 mu m;

The thickness ratio of the outer layer film to the inner layer film can be (10-0.1): 1, preferably (10 to 0.5): 1.

Specifically, the anti-adhesion composition may comprise the following components in parts by weight:

The polyolefin resin is 100 parts by weight, and the multifunctional additive is 0.1 to 30 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.2 to 20 parts by weight.

The polyolefin resin may be at least one selected from various polypropylene resins and polyethylene resins which are already known in the art; wherein the polypropylene resin can be selected from at least one of homo-polypropylene and co-polypropylene; the polyethylene resin may be at least one selected from high-density polyethylene and low-density polyethylene, preferably linear low-density polyethylene.

The zinc salt microsphere composition comprises a mixture of zinc salt microspheres and a release agent; wherein, the weight ratio range of the zinc salt microsphere to the isolating agent can be 1: (0.1 to 1), preferably 1: (0.1 to 0.5);

The guanidinium microsphere composition comprises a mixture of guanidinium microspheres and a release agent; wherein, the weight ratio range of the guanidine salt microsphere to the isolating agent can be 1: (0.1 to 1), preferably 1: (0.1-0.5).

The zinc salt microsphere and/or guanidine salt microsphere can be maleic anhydride cross-linked alternating copolymer zinc salt and/or guanidine salt derivative.

The zinc salt microsphere and/or guanidine salt microsphere can be microsphere or spheroid, and the average particle size can be in the conventional particle size range of conventional polymer microsphere, for example, 150-3000 nm.

The zinc salt microsphere and/or guanidine salt microsphere are polymer microsphere with surface generating grafting or complexing reaction with zinc ion and/or guanidine salt polymer;

In the zinc salt microsphere, the weight fraction of zinc element can be 10% -70%, preferably 20% -60%. The content in the concrete use can be adjusted according to actual conditions.

The guanidine salt polymer can be at least one selected from polyhexamethylene (bis) guanidine inorganic salt, polyhexamethylene (bis) guanidine organic salt, polyoxyethylene guanidine inorganic salt and polyoxyethylene guanidine organic salt; the guanidine salt polymer is preferably at least one selected from the group consisting of polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine phosphate, polyhexamethylene (bis) guanidine sulfonate, polyhexamethylene (bis) guanidine acetate, polyhexamethylene (bis) guanidine propionate, polyhexamethylene (bis) guanidine stearate, polyhexamethylene (bis) guanidine laurate, polyhexamethylene (bis) guanidine benzoate, polyoxyethylene guanidine hydrochloride, polyoxyethylene guanidine phosphate, polyoxyethylene guanidine sulfonate, polyoxyethylene guanidine acetate, polyoxyethylene guanidine propionate, polyoxyethylene guanidine stearate, polyoxyethylene guanidine laurate, and polyoxyethylene guanidine benzoate; more preferably at least one of polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine propionate and polyoxyethylene guanidine hydrochloride.

The polymer microspheres are maleic anhydride alternating copolymer microspheres, preferably maleic anhydride cross-linked alternating copolymer microspheres.

Specifically, the polymer microspheres in the zinc salt microspheres and/or the guanidine salt microspheres can be maleic anhydride crosslinked alternating copolymers obtained by jointly obtaining a structural unit A provided by maleic anhydride, a structural unit B provided by a monomer M and a structural unit C provided by a crosslinking agent. Wherein the monomer M can be selected from monomers containing isolated carbon-carbon double bonds; the crosslinking agent may be selected from vinyl-containing monomers having more than two functionalities capable of free radical polymerization.

The zinc salt microsphere and/or guanidine salt microsphere is characterized in that: the maleic anhydride in the microsphere and the zinc ion and/or guanidine salt polymer generate grafting or complexing reaction, and one zinc ion and/or guanidine salt polymer can be connected with one or more maleic anhydride cross-linked alternating copolymer molecular chains.

Wherein the monomer M can be selected from monomers containing isolated carbon-carbon double bonds; preferably at least one of the olefins selected from the group consisting of vinyl acetate, styrene, alpha-methylstyrene, carbon 4, carbon 5, carbon 8, and carbon 9; preferably at least one of vinyl acetate, styrene, alpha-methylstyrene, carbon 4, carbon 5 mixed olefins; wherein the carbon 4, carbon 5 mixed olefins are selected from the group consisting of carbon four and/or carbon five fractions of the oil refining or ethylene industry, preferably from the petrochemical industry ethylene cracking.

The crosslinking agent may be a vinyl-containing monomer capable of undergoing radical polymerization with various common difunctional or higher. Preferably, the crosslinking agent may be divinylbenzene and/or an acrylic crosslinking agent containing at least two acrylic groups; the structural formula of the acrylic ester group can be as follows: -O-C (O) -C (R ') =ch ₂, R' is H or C1-C4 alkyl (e.g. methyl); more preferably, the crosslinking agent may be selected from at least one of divinylbenzene, propylene glycol-based bis (meth) acrylate, ethylene glycol-based bis (meth) acrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tetraacrylate, trimethylolpropane tetramethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethylene glycol phthalate diacrylate, pentaerythritol tetraacrylate, pentaerythritol pentaacrylate, pentaerythritol hexaacrylate, and ethoxylated multifunctional acrylate;

The propylene glycol type di (meth) acrylate is preferably at least one selected from 1, 3-propylene glycol dimethacrylate, 1, 2-propylene glycol dimethacrylate, 1, 3-propylene glycol diacrylate, 1, 2-propylene glycol diacrylate and the like; the ethylene glycol di (meth) acrylate is preferably at least one selected from ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and the like.

In particular embodiments, the anti-adhesion composition may further comprise other adjuvants;

The amount of the other auxiliary agent is 0.1 to 5 parts by weight based on 100 parts by weight of the polyolefin resin. The other auxiliary agent may be at least one of antioxidants (such as hindered phenols, phosphite antioxidants, etc.), antistatic agents (such as quaternary ammonium salts, sulfonic acid type, carboxylate type antistatic agents, etc.), lubricants (such as erucamide, stearic acid type, ethylene bis stearamide, etc.), ultraviolet absorbers (such as salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, triazines, etc.), plasticizers, etc., which are commonly used in the art, and the kind and addition amount of these auxiliary agents are well known to those skilled in the art.

In the high-barrier anti-adhesion composite film of the present invention, the high-barrier thermoplastic resin forming the inner film may be selected from the commonly used high-barrier thermoplastic resin types, preferably at least one of ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyethylene naphthalate (PEN), nitrile resin, polyamide, and the like.

The second purpose of the invention is to provide a preparation method of the high-barrier anti-adhesion composite film, which comprises the following steps:

and (3) carrying out multilayer coextrusion on the components comprising the anti-adhesion composition and the high-barrier thermoplastic resin to obtain the high-barrier anti-adhesion composite film.

Specifically, the preparation method of the high-barrier anti-adhesion composite film can comprise the following steps:

(1) Fully mixing the components including the polyolefin resin and the multifunctional additive, and carrying out melt granulation by an extruder to obtain an anti-adhesion composition;

(2) And (3) carrying out multilayer coextrusion casting film making on the material obtained in the step (1) and the high-barrier thermoplastic resin, wherein the multilayer coextrusion casting film comprises the procedures of coextrusion die casting, cooling, thickness measurement, traction, coiling, slitting and the like, and the high-barrier anti-adhesion composite film with different thickness and width specifications is obtained.

Preferably, in the steps (1) and (2), the temperature of the extruder depends on the resin used, and specifically, the temperature of the coextrusion die in the step (2) may be 190 to 250 ℃. The cooling temperature of the delay of the co-extrusion die flow in the step (2) is 30-65 ℃.

In the step (1), the multifunctional additive is at least one of zinc salt microsphere composition and guanidine salt microsphere composition. The mixing method can be a mixing method and mixing equipment which are commonly used for resin in the prior art, and high-speed stirrer equipment is preferably adopted; the addition amount of the other auxiliary agents is the conventional dosage or is properly adjusted according to the actual situation.

Specifically, the polymer microsphere may be a maleic anhydride crosslinked alternating copolymer obtained by combining a structural unit A provided by maleic anhydride, a structural unit B provided by a monomer M and a structural unit C provided by a crosslinking agent.

The guanidine salt microsphere or the polymer microsphere in the zinc salt microsphere can be prepared by adopting a self-stabilization precipitation polymerization method. Specifically, the microspheres can be prepared from raw materials including maleic anhydride, a monomer M, a cross-linking agent, an initiator and an organic solvent by a self-stabilizing precipitation polymerization method conventional in the field.

Wherein the ratio of the amount of maleic anhydride to the amount of the monomer M may be conventionally selected, for example, in a specific embodiment, the amount of the monomer M may be 50 to 150mol, more preferably 75 to 100mol, with respect to 100mol of the maleic anhydride; the amount of crosslinking agent may be 1% to 20% by weight of the polymerized monomer (sum of the amounts of maleic anhydride and monomer M). In specific implementation, the dosage can be adjusted according to actual conditions.

The polymerization of the polymeric microspheres can be self-made by methods known in the art, for example according to literature: polymer composites with high haze and high Transmitance. Polymer. Chem.,2015,6,6632-6636; liu Zhenjie research on preparing monodisperse copolymer microsphere by self-stabilizing precipitation polymerization [ D ]. Beijing university of chemical industry, 2008; and the microsphere preparation method proposed in patent CN101338008A, CN109705269B, CN111793167A, CN111944155A, CN111944156A, CN111944232A, CN111944233A and the like.

In a specific implementation, the preparation method of the zinc salt microsphere composition can comprise the following steps:

adding the polymer microspheres into an alkali metal hydroxide aqueous solution for full reaction, and then adding a zinc salt aqueous solution for full reaction; or adding an alkali metal hydroxide aqueous solution into a polymerization system of the polymer microsphere, and then adding a zinc salt aqueous solution for full reaction; then separating, drying, and mixing the obtained zinc salt microsphere with a release agent in a high-speed stirrer to obtain the zinc salt microsphere composition;

Preferably, the preparation method of the zinc salt microsphere composition can comprise the following steps:

a. dissolving alkali metal hydroxide in water to obtain alkali metal hydroxide water solution; preferably, the weight ratio of the alkali metal hydroxide to water is in the range of (0.1-100): 100, more preferably (0.5 to 50): 100;

b. Adding the polymer microspheres into the alkali metal hydroxide aqueous solution prepared in the step a, and fully mixing and reacting; or adding the alkali metal hydroxide aqueous solution prepared in the step a into a polymerization system of the polymer microsphere (after the polymerization of the polymer microsphere is completed), and fully mixing and reacting; wherein the weight ratio of the polymer microspheres to the alkali metal hydroxide is preferably in the range of (0.1 to 20): 1, more preferably (0.1 to 10): 1, a step of; the reaction is an acid-base neutralization reaction of carboxylic acid groups of the microspheres and alkali metal hydroxide;

c. C, adding zinc salt solid into water to dissolve to obtain zinc salt aqueous solution, adding the zinc salt aqueous solution into the mixed solution obtained by the reaction in the step b, fully mixing and reacting, separating suspended matters, and drying to obtain the zinc salt microspheres; ion replacement occurs in the reaction process in the step c, and alkali metal ions on the reaction product of the alkali metal hydroxide and the microspheres obtained in the step b are replaced by high-valence zinc ions; preferably, the weight ratio of the zinc salt (solid) to the microspheres ranges from (0.1 to 20): 1, more preferably (0.1 to 10): 1, a step of;

The concentration of the zinc salt aqueous solution is not required as long as the content of the zinc salt in water is within the solubility range of the zinc salt.

D. C, mixing the zinc salt microsphere obtained in the step c with a release agent in a high-speed stirrer to obtain a zinc salt microsphere composition;

Wherein, preferably, the weight ratio of the zinc salt microsphere to the isolating agent is in the range of 1: (0.1 to 1), more preferably 1: (0.1 to 0.5); the isolating agent is selected from particles with the particle size of 150-5000 nm, preferably at least one of silicon dioxide, calcium carbonate, talcum powder, diatomite, kaolin, calcium hydrophosphate and silicone resin.

Wherein,

In the step a, the alkali metal hydroxide can be at least one selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide, preferably at least one selected from lithium hydroxide, sodium hydroxide and potassium hydroxide; and/or the number of the groups of groups,

In the step c, the zinc salt can be selected from various zinc salts in the prior art, preferably at least one of water-soluble zinc salts, more preferably at least one of zinc acetate, zinc lactate, zinc chloride, zinc bromide, zinc nitrate, zinc sulfate, zinc gluconate and the like;

In a specific implementation, the preparation method of the guanidine salt microsphere composition in the multifunctional additive can include the following steps:

Adding the polymer microsphere into a guanidine salt polymer aqueous solution for grafting reaction, or adding the guanidine salt polymer or the guanidine salt polymer aqueous solution into a polymerization system of the polymer microsphere (after the polymerization of the polymer microsphere is completed), and rapidly stirring for grafting reaction; further separating, and mixing the separated guanidine salt microsphere solid with a separating agent in a high-speed stirrer to obtain the guanidine salt microsphere composition.

Preferably, the method comprises the steps of,

The amount of the guanidine salt polymer or the aqueous guanidine salt polymer solution may be conventionally selected, for example, the amount of the aqueous guanidine salt polymer solution may be 500 to 10000g, preferably 1000 to 8000g, more preferably 1000 to 5000g, based on 1000g of the amount of maleic anhydride in the structural unit of the polymer microsphere (i.e., the amount of the raw material maleic anhydride used for preparing the polymer microsphere); the concentration of the aqueous guanidine salt polymer solution is 0.5 to 50wt%, preferably 1 to 30wt%, more preferably 1 to 20wt%;

And/or, the grafting reaction may be carried out under conventional conditions, for example, the grafting reaction conditions include: the temperature is 0 to 100 ℃, preferably 2.5 to 90 ℃, more preferably 5 to 80 ℃; the reaction time is 0.5 to 10 hours, preferably 0.5 to 8 hours, more preferably 0.5 to 6 hours; the stirring speed is 50 to 1000rpm, preferably 50 to 500rpm, more preferably 100 to 500rpm.

The isolating agent can be selected from particles with the particle size of 150-5000 nm, preferably at least one of silicon dioxide, calcium carbonate, talcum powder, diatomite, kaolin, calcium hydrophosphate, silicone resin and the like; the weight ratio of the guanidine salt microsphere to the release agent can be in the range of 1: (0.1 to 1), preferably 1: (0.1-0.5).

The guanidine salt microsphere obtained through the grafting reaction is subjected to further separation treatment to obtain a guanidine salt microsphere solid product, for example, the separation treatment can be performed in the following manner: centrifuging, washing with water, washing with organic solvent (such as at least one of n-hexane, isohexane, cyclohexane, n-heptane, n-octane, isooctane, methanol, ethanol, propanol, isopropanol, diethyl ether, isopropyl ether and methyl tert-butyl ether), centrifuging, and drying (such as vacuum drying).

In the process of preparing the high-barrier anti-adhesion composite film, the zinc salt and/or guanidine salt microsphere composition used by the outer layer component can form an uneven structure on the surface of the film after being blended with the polyolefin resin to form the film, so that the distance between the polyolefin films is increased, and the problem of poor opening property of the film is solved. After modification of zinc salt and/or guanidine salt, the microspheres are easy to adhere, because the introduced zinc or guanidine group can react with one or more molecular chains of the maleic anhydride copolymer, and the microspheres are easy to aggregate through interactions of ionic bonds, hydrogen bonds, coordination bonds and the like, and the aggregation can influence the dispersion effect of the microspheres in the polyolefin resin. The aggregation of the microspheres can be greatly reduced due to the introduction of the isolating agent in the microspheres, and the microspheres can be more uniformly dispersed in the resin due to the synergistic effect of the isolating agent and the resin, so that the openness of the film is further improved. In addition, as the microsphere matrix is maleic anhydride copolymer and the microsphere contains a large amount of polar groups, the microsphere in the outer layer polyolefin resin can be interacted with the inner layer high-barrier thermoplastic resin to be bonded when the high-barrier anti-bonding composite film is subjected to multilayer coextrusion, so that the use of a binder can be omitted, the production process is simplified, and the production cost is reduced.

The invention also aims to provide the application of the high-barrier anti-adhesion composite film or the composite film prepared by the preparation method of the second aim, in particular to the application in food and medicine packaging.

The applicant of the invention discovers in the research that a single-component and multifunctional product can be obtained after the microsphere is modified, the product is blended with polyolefin resin in the form of an additive and then is subjected to multi-layer compounding with high-barrier thermoplastic resin, so that a composite film with high barrier property and anti-adhesion property can be obtained, and the composite film can be used in the fields of food, medicine packaging and the like with high requirements on safety. The invention has the main advantages that:

① The high-performance composite film has excellent barrier property and openness and higher added value of products;

② The microsphere composition used in the outer layer of the high-performance composite film has a multifunctional effect, can be used as a mouth gag and a compatilizer for the inner and outer layer films, has mature industrial production flow of the microsphere, is easy to obtain raw materials, adopts cheap conventional materials as materials in the preparation process, and adopts common equipment in industrial production;

③ The inner and outer resins used by the high-performance composite film are commercial products, and the equipment involved in the film preparation is common equipment in industrial production.

Drawings

Fig. 1 is an element energy spectrum diagram of zinc salt microsphere 1# prepared in example 1, wherein the ordinate is intensity, the abscissa is energy value of the element, and the corresponding element can be found in the handbook according to the energy value.

Detailed Description

The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.

The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.

1. The raw materials used in the examples and comparative examples and the instrumentation used include:

linear Low Density Polyethylene (LLDPE): zhongtianhe wound, EGF-34;

EVOH: japanese colali, F171B;

Polypropylene (PP): offshore petrochemical, F800E;

maleic anhydride grafted polyethylene: triple well ADMER, NF529;

PVA: sichuan vitamin chemical industry, SM-A2;

Nitrile resin: barex, uk oil company;

Calcium carbonate: enoKai with a particle size of 0.5 μm;

silicone resin: the grain diameter of the ternary chemical industry is MicrobeadT and is 2.5 mu m;

silica: enoKai with a particle size of 1.5 μm;

antioxidant 168: germany basf, irgafos168;

antioxidant 1010: german steam, irganox1010;

polyhexamethylene guanidine hydrochloride: shanghai high Polymer industries Co.Ltd

Polyhexamethylene guanidine propionate: shanghai high Polymer industries Co.Ltd

Polyhexamethylene biguanide hydrochloride: shanghai mountain Co.Ltd

Maleic anhydride, alpha-methylstyrene, styrene, divinylbenzene, isoamyl acetate, azobisisobutyronitrile, lithium hydroxide, sodium hydroxide, potassium hydroxide, zinc nitrate were all purchased from enoKai, analytically pure; mixed carbon 4 was from Zhenhai refines.

Other raw materials are all commercially available.

2. Raw materials of examples and comparative examples:

The maleic anhydride- α -methylstyrene crosslinked alternating copolymer Microspheres (MASC) used in example 1 were prepared as described in publication Polymercomposites with high haze AND HIGH TRANSMITTANCE (DOI: 10.1039/c5py01072 a), with reference to the main preparation conditions and parameters: the molar ratio of the reaction monomer maleic anhydride to the alpha-methylstyrene is 1:1, the crosslinking agent is divinylbenzene, the amount of divinylbenzene is 13.8 percent of the weight of the monomer (the sum of the weight of maleic anhydride and the weight of the alpha-methylstyrene), the medium is isoamyl acetate, the initiator is azodiisobutyronitrile, and the particle size of the prepared polymer microsphere is 2.5 mu m after the reaction is carried out for 6 hours at 70 ℃.

The maleic anhydride-styrene cross-linked alternating copolymer Microspheres (MSC) used in example 2 were prepared by reference to the preparation method described in publication No. CN101338008A, the main preparation conditions and parameters: the molar ratio of the reaction monomer maleic anhydride to the styrene is 1:1, the crosslinking agent is divinylbenzene, the dosage of the divinylbenzene is 1.9 percent of the weight of the monomer (the sum of the weight of maleic anhydride and the weight of the styrene), the medium is isoamyl acetate, the initiator is azodiisobutyronitrile, and the particle size of the prepared polymer microsphere is 600nm after the reaction is carried out for 6 hours at 70 ℃.

The maleic anhydride-carbon four-crosslinked alternating copolymer microsphere (MC 4C) used in example 3 refers to the preparation methods described in steps (1) to (2) in example 1 of Chinese patent publication No. CN109705269B, and the main preparation conditions and parameters are as follows: the reaction monomers are maleic anhydride (100 g) and mixed C-IV A (the molar ratio of the maleic anhydride to the effective component (terminal olefin) in the mixed olefin is 1:1), the medium is isoamyl acetate (800 mL), the initiator is azobisisobutyronitrile (6 g), divinylbenzene (25 g) and the reaction is carried out for 6 hours at 70 ℃ and 0.5MPa, wherein the mixed C-IV A comprises the following components in percentage by weight: trans-2-butene, 40.83%; cis 2-butene, 18.18%; n-butane, 24.29%; n-butene, 9.52%; isobutene, 2.78%; other, 4.4%. The particle size of the polymer microsphere obtained was 1.5. Mu.m.

3. Experimental data for examples and comparative examples were determined using the following method:

(1) Antibacterial test criteria: GB/T31402-2015 test method for antibacterial Property of Plastic surface; bacteria for detection: coli (ATCC 8739), staphylococcus aureus (ATCC 6538P).

An antibacterial test step, namely, referring to GB/T31402-2015 standard for testing, specifically comprising the following steps: the composite film to be tested was cut into 50X 50mm samples and the bacterial suspension was diluted with 1/500 nutrient broth for use. 0.4mL of inoculation liquid is dripped on the surface of a sample, a film with the thickness of 40 multiplied by 40mm is covered, then a culture dish cover is covered, the culture is carried out for 24 hours under the conditions of the temperature of 35 ℃ and the humidity of 90%, and finally the antibacterial rate is calculated by counting viable bacteria on the sample.

(2) Oxygen permeability test standard: GB/T19789-2005 Coulomb Meter assay for packaging Plastic films and sheets oxygen permeability test.

The oxygen permeability test step is carried out by referring to GB/T19789-2005 standard, and the specific steps are as follows: cutting the dried composite film into a proper size, placing the proper size on grease, fastening and sealing a cover of a ventilation chamber, blowing the ventilation chamber with nitrogen, setting the flow rate to be 5-15 mL/min for 30 minutes, then, introducing the nitrogen into a coulombmeter, measuring zero voltage E ₀, then, turning off the nitrogen, introducing oxygen, and measuring a stable test voltage Ee.

Oxygen permeability= (Ee-E ₀) Q/(a·r), where a is the composite membrane area, Q is the instrument test constant, and R is the load resistance value.

(3) Opening force and peel force test:

Collecting and cutting the composite film in two layers (the outer layers are contacted with each other), and then testing the direct opening force of the outer layers of the two layers of the composite film according to GB/T8808-1988 soft composite plastic material peeling test method;

the peeling force was measured by referring to GB/T8808-1988 method for peeling test of Soft composite Plastic Material, and the composite film was made into an outer layer/inner layer/outer layer structure, and the peeling force of the outer layer and the inner layer was measured.

Microsphere composition preparation:

Example 1:

5g of sodium hydroxide is dissolved in 100g of water, 15g of MASC microspheres are added into a sodium hydroxide aqueous solution, after stirring for 1 hour, a zinc nitrate solution (15 g of zinc nitrate is dissolved in 100g of water) is added, after stirring for 30 minutes, a suspension is separated and dried to obtain zinc salt microspheres 1#, the energy spectrum data is shown in figure 1, the 2.15eV position is gold element sprayed on the surface of a sample, zinc element exists in the product, the weight part of the zinc element is 39%, and no sodium element exists, so that the sodium element is completely replaced by zinc. 10g of zinc salt microsphere No.1 and 1g of silicon resin microsphere are taken and mixed in a high-speed mixer for 1 minute to obtain the zinc salt microsphere composition A.

Example 2:

1g of potassium hydroxide is dissolved in 200g of water, 10g of MSC microspheres are added into a potassium hydroxide aqueous solution, after stirring for 1 hour, a zinc nitrate solution (1 g of zinc nitrate is dissolved in 100g of water) is added, after stirring for 30 minutes, a suspension is separated and dried to obtain zinc salt microspheres No. 2, and the weight fraction of zinc element is 20% as measured by element energy spectrum analysis. 10g of zinc salt microsphere No. 2 and 2g of calcium carbonate are taken and mixed in a high-speed mixer for 1 minute to obtain the zinc salt microsphere composition B.

Example 3:

50g of lithium hydroxide is dissolved in 100g of water, 5g of MC4C microspheres are added into lithium hydroxide aqueous solution, after stirring for 1 hour, zinc nitrate solution (50 g of zinc nitrate is dissolved in 150g of water) is added, after stirring for 30 minutes, suspended matters are separated and dried, and zinc salt microspheres 3# are obtained, and the weight fraction of zinc element is 60% as measured by element energy spectrum analysis. 10g of zinc salt microsphere No. 3 and 5g of silicon dioxide are taken and mixed in a high-speed mixer for 1 minute to obtain the zinc salt microsphere composition C.

Example 4:

According to the preparation method disclosed in publication Polymer composites with high haze AND HIGH TRANSMITTANCE, maleic anhydride, alpha-methylstyrene, azobisisobutyronitrile and divinylbenzene were added in amounts of 100g, 120.52g, 1.97g, 15.20g, respectively, and reacted at 70℃for 6 hours. Then 200g (20 wt%) of polyhexamethylene biguanide hydrochloride aqueous solution was added thereto and reacted at 80℃for 3 hours. Standing and layering the reacted system, centrifugally separating a heavy phase for 20 minutes under the condition of 5000rad/min by a centrifugal machine, adding 2L of water into the solid, stirring and washing, centrifugally separating for 20 minutes under the condition of 5000rad/min by the centrifugal machine, and drying the solid in vacuum to obtain the guanidine salt microsphere 4# of the surface grafted guanidine salt polymer. 10g of guanidine salt microsphere No. 4 and 1g of silicone microsphere are taken and mixed in a high-speed mixer for 1 minute to obtain the guanidine salt microsphere composition D.

Example 5:

The solid polymerized MASC polymer microspheres of example 4 were isolated and then added to 100g (10 wt%) of polyhexamethylene guanidine hydrochloride aqueous solution and reacted at 80℃for 3 hours. Standing and layering the reacted system, centrifugally separating a heavy phase for 20 minutes under the condition of 5000rad/min by a centrifugal machine, adding 2L of water into the solid, stirring and washing, centrifugally separating for 20 minutes under the condition of 5000rad/min by the centrifugal machine, and drying the solid in vacuum to obtain the guanidine salt microsphere 6# of the surface grafted guanidine salt polymer. 10g of guanidine salt microsphere No. 6 and 2g of calcium carbonate are taken and mixed in a high-speed mixer for 1 minute to obtain the guanidine salt microsphere composition E.

Example 6:

The maleic anhydride-carbon four-crosslinked alternating copolymer (MC 4C) is prepared by referring to the preparation methods of steps (1) - (2) described in the Chinese patent publication No. CN109705269B, and the main preparation conditions and parameters are as follows: the reaction monomers are maleic anhydride (100 g) and mixed C-IV A (the molar ratio of the maleic anhydride to the effective component (terminal olefin) in the mixed olefin is 1:1), the medium is isoamyl acetate (800 mL), the initiator is azobisisobutyronitrile (6 g), divinylbenzene (25 g), wherein the composition (weight percent) of the mixed C-IV A is: trans-2-butene, 40.83%; cis 2-butene, 18.18%; n-butane, 24.29%; n-butene, 9.52%; isobutene, 2.78%; other, 4.4%. After the reaction was carried out at 70℃and 0.5MPa for 6 hours, 500g (1 wt%) of an aqueous solution of polyhexamethylene guanidine propionate was added thereto, and the reaction was carried out at 80℃for 3 hours. Standing and layering the reacted system, centrifugally separating a heavy phase for 20 minutes under the condition of 5000rad/min by a centrifugal machine, adding 1L of water into the solid, stirring and washing, centrifugally separating for 20 minutes under the condition of 5000rad/min by the centrifugal machine, and drying the solid in vacuum to obtain the guanidine salt microsphere 7# of the surface grafted guanidine salt polymer. 10g of guanidine salt microsphere No. 7 and 1g of silicon dioxide are taken and mixed in a high-speed mixer for 1 minute to obtain the guanidine salt microsphere composition F.

Preparation of high-performance composite film:

example 7:

The preparation of the high-performance composite film provided by the invention is illustrated in the example, wherein the mass of each 100 parts of materials in the example is 2kg;

The formula of the outer layer comprises the following steps: 100 parts of LLDPE resin (EGF-34, zhongtian, hereinafter the same), 1 part of zinc salt microsphere composition A,0.1 part of antioxidant 168;

Extrusion molding process: (a) raw material drying: weighing raw materials according to a formula, and drying LLDPE and EVOH resins (F171B, japanese colali and the same below) until the moisture content is 0.3%; (b) raw material mixing: and adopting a high-speed mixer to respectively carry out a high-rotation-speed and low-rotation-speed two-stage mixing process on the outer layer materials. The temperature of the materials in the high-speed mixing section is 50 ℃, the rotating speed of the main shaft is 1500rpm, and the mixing time is 2min; low-speed mixing section: the temperature of the materials is 35 ℃, the rotating speed of the main shaft is 80rpm, and the mixing time is 1min; (c) melting and plasticizing materials: the screw processing temperature of the outer layer LLDPE composition is as follows in sequence: 150. 190, 205 ℃, screw speed 60rpm; the screw processing temperature of the inner EVOH layer is 180, 200, 220 and 220 ℃ in sequence, and the screw rotating speed is 55rpm; (d) die temperature: the temperature of the coextrusion die head is 220 ℃; (e) The high-performance composite film-1 is obtained after the processes of cooling (the temperature is 30 ℃), traction, crimping and slitting. The thickness of the composite film-1 is 50 mu m, and the thickness ratio of the outer layer to the inner layer is 2:1.

Comparative example 1:

the zinc salt microsphere composition A in example 7 was removed from the outer layer formulation, and the other formulations and processing techniques were unchanged to produce composite film-2. The thickness of the composite film-2 is 50 mu m, and the thickness ratio of the outer layer to the inner layer is 2:1.

Comparative example 2:

the zinc salt microsphere composition A of the outer layer formula in example 7 is changed into zinc salt microsphere No.1, and other formulas and processing technologies are unchanged, so that the composite membrane-3 is prepared. The thickness of the composite film-3 is 50 mu m, and the thickness ratio of the outer layer to the inner layer is 2:1.

Comparative example 3:

The zinc salt microsphere composition A of the outer layer formulation in example 7 was changed to silicone microspheres, and other formulations and processing techniques were unchanged, to prepare composite membrane-4. The thickness of the composite film-4 is 50 mu m, and the thickness ratio of the outer layer to the inner layer is 2:1.

Comparative example 4:

In example 7, the zinc salt microsphere composition A of the outer layer formulation was changed to maleic anhydride grafted polyethylene, and other formulations and processing techniques were unchanged, to prepare composite film-5. The thickness of the composite film-5 is 50 mu m, and the thickness ratio of the outer layer to the inner layer is 2:1.

Comparative example 5:

The zinc salt microsphere composition A of the outer layer formulation in example 7 was changed to MASC microspheres, and other formulations and processing techniques were unchanged, to prepare composite membrane-6. The thickness of the composite film-6 is 50 mu m, and the thickness ratio of the outer layer to the inner layer is 2:1.

Example 8:

The formula of the outer layer comprises the following steps: 100 parts of PP resin (F800E, shanghai petrochemical industry), 0.2 part of zinc salt microsphere composition B,0.5 part of antioxidant 168,0.5 parts of lubricant PEG;

Extrusion molding process: (a) raw material drying: weighing raw materials according to a formula, and drying PP and EVOH resins until the water content is 0.3%; (b) raw material mixing: and adopting a high-speed mixer to respectively carry out a high-rotation-speed and low-rotation-speed two-stage mixing process on the outer layer materials. The temperature of the materials in the high-speed mixing section is 50 ℃, the rotating speed of the main shaft is 1500rpm, and the mixing time is 2min; low-speed mixing section: the temperature of the materials is 35 ℃, the rotating speed of the main shaft is 80rpm, and the mixing time is 1min; (c) melting and plasticizing materials: the screw processing temperature of the outer layer PP composition is as follows in sequence: 150. 190, 205 ℃, screw speed 60rpm; the screw processing temperature of the inner EVOH layer is 180, 200, 220 and 220 ℃ in sequence, and the screw rotating speed is 55rpm; (d) die temperature: the temperature of the coextrusion die head is 200 ℃; (e) The high-performance composite film-7 is obtained after the processes of cooling (temperature of 45 ℃), traction, crimping and slitting. The thickness of the composite film-7 is 100 mu m, and the thickness ratio of the outer layer to the inner layer is 10:1.

Example 9:

The formula of the outer layer comprises the following steps: 100 parts of PP resin (F800E, shanghai petrochemical industry), 20 parts of zinc salt microsphere composition C,2.5 parts of antioxidant 168,2.5 parts of plasticizer tributyl citrate;

Extrusion molding process: (a) raw material drying: weighing raw materials according to a formula, and drying PP and PVA resins (SM-A2, sichuan chemical industry) until the water content is 0.3%; (b) raw material mixing: and adopting a high-speed mixer to respectively carry out a high-rotation-speed and low-rotation-speed two-stage mixing process on the outer layer materials. The temperature of the materials in the high-speed mixing section is 50 ℃, the rotating speed of the main shaft is 1500rpm, and the mixing time is 2min; low-speed mixing section: the temperature of the materials is 35 ℃, the rotating speed of the main shaft is 80rpm, and the mixing time is 1min; (c) melting and plasticizing materials: the screw processing temperature of the outer layer PP composition is as follows in sequence: 150. 190, 205 ℃, screw speed 60rpm; the processing temperature of the screw of the PVA of the inner layer is 180, 200, 220 and 220 ℃ in sequence, and the rotating speed of the screw is 55rpm; (d) die temperature: the temperature of the coextrusion die head is 190 ℃; (e) The high-performance composite film-8 is obtained after the processes of cooling (temperature of 55 ℃), traction, crimping and slitting. The thickness of the composite film-8 is 10 mu m, and the thickness ratio of the outer layer to the inner layer is 1:1.

Example 10:

the formula of the outer layer comprises the following steps: 100 parts of LLDPE resin, 5 parts of guanidine salt microsphere composition D,1 part of antioxidant 168;

Extrusion molding process: (a) raw material drying: weighing raw materials according to a formula, and drying LLDPE and nitrile resin (Barex, british petroleum company) until the water content is 0.3%; (b) raw material mixing: and adopting a high-speed mixer to respectively carry out a high-rotation-speed and low-rotation-speed two-stage mixing process on the outer layer materials. The temperature of the materials in the high-speed mixing section is 50 ℃, the rotating speed of the main shaft is 1500rpm, and the mixing time is 2min; low-speed mixing section: the temperature of the materials is 35 ℃, the rotating speed of the main shaft is 80rpm, and the mixing time is 1min; (c) melting and plasticizing materials: the screw processing temperature of the outer layer LLDPE composition is as follows in sequence: 150. 190, 205 ℃, screw speed 60rpm; the screw processing temperature of the inner EVOH layer is 180, 200, 220, 240 and 240 ℃ in sequence, and the screw rotating speed is 55rpm; (d) die temperature: the temperature of the coextrusion die head is 230 ℃; (e) The high-performance composite film-9 is obtained after the processes of cooling (the temperature is 65 ℃), traction, crimping and slitting. The thickness of the composite film-9 is 200 mu m, and the thickness ratio of the outer layer to the inner layer is 0.5:1.

Example 11:

The formula of the outer layer comprises the following steps: 100 parts of LLDPE resin, 0.5 part of guanidine salt microsphere composition E,0.2 part of antioxidant 168;

extrusion molding process: (a) raw material drying: weighing raw materials according to a formula, and drying LLDPE and EVOH resins until the moisture content is 0.3%; (b) raw material mixing: and adopting a high-speed mixer to respectively carry out a high-rotation-speed and low-rotation-speed two-stage mixing process on the outer layer materials. The temperature of the materials in the high-speed mixing section is 50 ℃, the rotating speed of the main shaft is 1500rpm, and the mixing time is 2min; low-speed mixing section: the temperature of the materials is 35 ℃, the rotating speed of the main shaft is 80rpm, and the mixing time is 1min; (c) melting and plasticizing materials: the screw processing temperature of the outer layer LLDPE composition is as follows in sequence: 150. 190, 205 ℃, screw speed 60rpm; the screw processing temperature of the inner EVOH layer is 180, 200, 220 and 220 ℃ in sequence, and the screw rotating speed is 55rpm; (d) die temperature: the temperature of the coextrusion die head is 200 ℃; (e) The high-performance composite film-10 is obtained after the processes of cooling (the temperature is 30 ℃), traction, crimping and slitting. The thickness of the composite film-10 is 50 mu m, and the thickness ratio of the outer layer to the inner layer is 2:1.

Example 12:

the formula of the outer layer comprises the following steps: 100 parts of LLDPE resin, 0.3 part of guanidine salt microsphere composition F,0.2 part of antioxidant 168;

Extrusion molding process: (a) raw material drying: weighing raw materials according to a formula, and drying LLDPE and EVOH resins until the moisture content is 0.3%; (b) raw material mixing: and adopting a high-speed mixer to respectively carry out a high-rotation-speed and low-rotation-speed two-stage mixing process on the outer layer materials. The temperature of the materials in the high-speed mixing section is 50 ℃, the rotating speed of the main shaft is 1500rpm, and the mixing time is 2min; low-speed mixing section: the temperature of the materials is 35 ℃, the rotating speed of the main shaft is 80rpm, and the mixing time is 1min; (c) melting and plasticizing materials: the screw processing temperature of the outer layer LLDPE composition is as follows in sequence: 150. 190, 205 ℃, screw speed 60rpm; the screw processing temperature of the inner EVOH layer is 180, 200, 230, 250 and 250 ℃ in sequence, and the screw rotating speed is 55rpm; (d) die temperature: the temperature of the coextrusion die head is 250 ℃; (e) The high-performance composite film-11 is obtained after the processes of cooling (the temperature is 30 ℃), traction, crimping and slitting. The thickness of the composite film-11 is 250 mu m, and the thickness ratio of the outer layer to the inner layer is 5:1.

Data for composite films of examples and comparative examples

As can be seen from the above table, compared with the composite film 2, the zinc salt microsphere (composite film 3), the microsphere composition (composite film 1) or the silicone microsphere (composite film 4) has an opening effect on the outer layer of the composite film, wherein the opening effect of the zinc salt microsphere is equivalent to that of the commercially available silicone microsphere, the opening force of the original resin can be reduced by one order of magnitude, and the opening force of the microsphere composition can be reduced continuously by about 42%; the reduced opening force after modification with zinc salts and/or guanidine salts compared to unmodified microspheres (composite film 6) demonstrates that the microsphere composition of the present invention has more excellent openness. In addition, the comparison of the composite films 2 and 4 shows that after the silicone resin microsphere is added into the resin, the bonding effect of the outer layer and the inner layer of the composite film is reduced, and after the modified microsphere is added, the stripping force can be improved by about 78%, the reason is attributable to the fact that the modified microsphere is provided with a large number of polar groups, and the high-barrier material of the inner layer is also provided with a large number of polar groups, so that the microsphere and the inner layer directly have hydrogen bonds and other interactions, and the bonding effect is improved; the outer layer of the composite film belongs to nonpolar polyolefin, and the acting force of the microsphere and the microsphere is far lower than that of the microsphere and the inner layer material. The peel force of the modified microsphere composition is not significantly changed compared with that of the modified microsphere. The above examples and comparative examples demonstrate that the microsphere compositions used in the present invention have both an opening and a bonding effect, and the inner layer material provides excellent barrier properties to the composite film, ultimately providing high performance such as opening, barrier, etc.

Claims

1. A high-barrier anti-adhesion composite film comprises an outer layer film and an inner layer film;

the outer film comprises an anti-adhesion composition;

the anti-blocking composition comprises a polyolefin resin, a multifunctional additive;

The multifunctional additive is selected from at least one of zinc salt microsphere composition and guanidine salt microsphere composition;

The zinc salt microsphere composition comprises a mixture of zinc salt microspheres and a release agent; the weight ratio range of the zinc salt microsphere to the isolating agent is 1: (0.1-1);

The guanidinium microsphere composition comprises a mixture of guanidinium microspheres and a release agent; the weight ratio of the guanidine salt microsphere to the isolating agent is 1: (0.1-1);

the inner layer film comprises a high barrier thermoplastic resin;

The zinc salt microsphere and/or guanidine salt microsphere are polymer microsphere with surface generating grafting or complexing reaction with zinc ion and/or guanidine salt polymer; the polymer microsphere is a maleic anhydride alternating copolymer microsphere;

The isolating agent is selected from particles with the particle size of 150-5000 nm, and the isolating agent is at least one selected from silicon dioxide, calcium carbonate, talcum powder, diatomite, kaolin, calcium hydrophosphate and silicone resin.

2. The high barrier anti-adhesion composite film of claim 1, wherein:

The thickness ratio of the outer layer film to the inner layer film is (10-0.1): 1.

3. The high barrier anti-adhesion composite film of claim 1, wherein:

the thickness ratio of the outer layer film to the inner layer film is (10-0.5): 1.

4. The high barrier anti-adhesion composite film of claim 1, wherein:

the total thickness of the high-barrier anti-adhesion composite film is 10-250 mu m.

5. The high barrier anti-adhesion composite film of claim 1, wherein:

The anti-adhesion composition comprises the following components in parts by weight:

100 parts by weight of a polyolefin resin,

0.1-30 Parts by weight of a multifunctional additive.

6. The high barrier anti-adhesion composite film of claim 1, wherein:

100 parts of polyolefin resin and 0.1-20 parts of multifunctional additive.

7. The high barrier anti-adhesion composite film of claim 1, wherein:

The polyolefin resin is at least one selected from polypropylene resin and polyethylene resin;

Wherein the polypropylene resin is at least one selected from homo-polypropylene and co-polypropylene;

The polyethylene resin is at least one selected from high-density polyethylene and low-density polyethylene.

8. The high barrier anti-adhesion composite film of claim 7, wherein:

the polyethylene resin is selected from linear low density polyethylene.

9. The high barrier anti-adhesion composite film of claim 1, wherein:

The weight ratio range of the zinc salt microsphere to the isolating agent is 1: (0.1 to 0.5); and/or the number of the groups of groups,

The weight ratio of the guanidine salt microsphere to the isolating agent is 1: (0.1 to 0.5).

10. The high barrier anti-adhesion composite film of claim 1, wherein:

the polymer microsphere is a maleic anhydride cross-linked alternating copolymer microsphere.

11. The high barrier anti-adhesion composite film of claim 1, wherein:

The polymer microsphere is prepared by adopting a self-stabilizing precipitation polymerization method.

12. The high barrier anti-adhesion composite film of claim 1, wherein:

In the zinc salt microsphere, the weight fraction of zinc element is 10% -70%.

13. The high barrier, anti-adhesion composite film of claim 12, wherein:

In the zinc salt microsphere, the weight fraction of zinc element is 20% -60%.

14. The high barrier anti-adhesion composite film of claim 1, wherein:

The guanidine salt polymer is at least one selected from polyhexamethylene (bis) guanidine inorganic salt, polyhexamethylene (bis) guanidine organic salt, polyoxyethylene guanidine inorganic salt and polyoxyethylene guanidine organic salt.

15. The high barrier, anti-adhesion composite film of claim 14, wherein:

the guanidine salt polymer is at least one selected from polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine phosphate, polyhexamethylene (bis) guanidine sulfonate, polyhexamethylene (bis) guanidine acetate, polyhexamethylene (bis) guanidine propionate, polyhexamethylene (bis) guanidine stearate, polyhexamethylene (bis) guanidine laurate, polyhexamethylene (bis) guanidine benzoate, polyoxyethylene guanidine hydrochloride, polyoxyethylene guanidine phosphate, polyoxyethylene guanidine sulfonate, polyoxyethylene guanidine acetate, polyoxyethylene guanidine propionate, polyoxyethylene guanidine stearate, polyoxyethylene guanidine laurate, and polyoxyethylene guanidine benzoate.

16. The high barrier, anti-adhesion composite film of claim 15, wherein:

the guanidine salt polymer is at least one selected from polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine propionate and polyoxyethylene guanidine hydrochloride.

17. The high barrier anti-adhesion composite film of claim 1, wherein:

The polymer microspheres in the zinc salt microspheres and/or the guanidine salt microspheres are maleic anhydride crosslinked alternating copolymers obtained by jointly obtaining a structural unit A provided by maleic anhydride, a structural unit B provided by a monomer M and a structural unit C provided by a crosslinking agent; wherein the monomer M is selected from monomers containing isolated carbon-carbon double bonds; the cross-linking agent is selected from vinyl-containing monomers with more than two functionalities and capable of undergoing free radical polymerization.

18. The high barrier, anti-adhesion composite film of claim 17, wherein:

the monomer M is selected from monomers containing isolated carbon-carbon double bonds;

The cross-linking agent is divinylbenzene and/or acrylic ester cross-linking agent containing at least two acrylic ester groups; the structural formula of the acrylic ester group is as follows: -O-C (O) -C (R ') =ch ₂, R' is H or C1-C4 alkyl.

19. The high barrier, anti-adhesion composite film of claim 18, wherein:

the monomer M is at least one selected from vinyl acetate, styrene, alpha-methyl styrene and mixed olefin;

The mixed olefins are selected from the group consisting of carbon 4, carbon 5, carbon 8, and carbon 9 mixed olefins.

20. The high barrier, anti-adhesion composite film of claim 19, wherein:

The mixed olefins are selected from mixed olefins of carbon 4 and carbon 5.

21. The high barrier, anti-adhesion composite film of claim 18, wherein:

The cross-linking agent is at least one selected from divinylbenzene, propylene glycol bis (meth) acrylate, ethylene glycol bis (meth) acrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tetraacrylate, trimethylolpropane tetramethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethylene glycol diacrylate, pentaerythritol tetraacrylate, pentaerythritol pentaacrylate, pentaerythritol hexaacrylate and ethoxylated multifunctional acrylate.

22. The high barrier, anti-adhesion composite film of claim 21, wherein:

The propylene glycol type di (methyl) acrylic ester is at least one selected from 1, 3-propylene glycol dimethacrylate, 1, 2-propylene glycol dimethacrylate, 1, 3-propylene glycol diacrylate and 1, 2-propylene glycol diacrylate.

23. The high barrier, anti-adhesion composite film of claim 21, wherein:

the ethylene glycol di (methyl) acrylate is at least one selected from ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate and tetraethylene glycol diacrylate.

24. The high barrier anti-adhesion composite film of claim 1, wherein:

the anti-blocking composition comprises other adjuvants;

Based on 100 parts by weight of the polyolefin resin, the other auxiliary agents are 0.1-5 parts by weight;

the other auxiliary agent is at least one selected from antioxidant, antistatic agent, lubricant, ultraviolet absorbent and plasticizer.

25. The high barrier anti-adhesion composite film of claim 1, wherein:

The high-barrier thermoplastic resin is at least one selected from ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyethylene naphthalate (PEN), nitrile resin and polyamide.

26. The method for producing a high barrier anti-adhesion composite film according to any one of claims 1 to 25, characterized by comprising the steps of:

27. The method for preparing the high-barrier anti-adhesion composite film according to claim 26, comprising the following steps:

(1) Fully mixing the components comprising the polyolefin resin and the multifunctional additive, extruding, melting and granulating to obtain an anti-adhesion composition;

(2) And (3) carrying out multilayer coextrusion casting on the anti-adhesion composition obtained in the step (1) and the high-barrier thermoplastic resin to prepare a film, thereby obtaining the high-barrier anti-adhesion composite film.

28. The method for preparing the high-barrier anti-adhesion composite film according to claim 27, wherein:

And (3) cooling the coextrusion die casting in the step (2) at 30-65 ℃.

29. The method for preparing the high-barrier anti-adhesion composite film according to claim 27, wherein:

The preparation method of the zinc salt microsphere composition in the multifunctional additive comprises the following steps:

Adding the polymer microspheres into an alkali metal hydroxide aqueous solution for full reaction, and then adding a zinc salt aqueous solution for full reaction; or adding an alkali metal hydroxide aqueous solution into a polymerization system of the polymer microsphere, and then adding a zinc salt aqueous solution for full reaction; and then separating, drying, and mixing the obtained zinc salt microsphere with a release agent to obtain the zinc salt microsphere composition.

30. The method for preparing the high-barrier anti-adhesion composite film according to claim 29, wherein the method comprises the following steps:

the preparation method of the zinc salt microsphere composition comprises the following steps:

a. Dissolving alkali metal hydroxide in water to obtain alkali metal hydroxide water solution;

b. Adding the polymer microspheres into the alkali metal hydroxide aqueous solution prepared in the step a, and fully mixing and reacting; or adding the alkali metal hydroxide aqueous solution prepared in the step a into a polymerization system of polymer microspheres, and fully mixing and reacting;

c. B, adding zinc salt into water to dissolve to obtain zinc salt aqueous solution, adding the zinc salt aqueous solution into the mixed solution obtained by the reaction in the step b, fully mixing and reacting, separating suspended matters, and drying to obtain zinc salt microspheres;

d. and c, mixing the zinc salt microsphere obtained in the step c with a release agent to obtain the zinc salt microsphere composition.

31. The method for preparing the high-barrier anti-adhesion composite film according to claim 30, wherein the method comprises the following steps:

In the step a of the process,

The weight ratio of the alkali metal hydroxide to the water is (0.1-100): 100.

32. The method for preparing the high-barrier anti-adhesion composite film according to claim 31, wherein the method comprises the following steps:

In the step a of the process,

The weight ratio of the alkali metal hydroxide to the water is (0.5-50): 100.

33. The method for preparing the high-barrier anti-adhesion composite film according to claim 30, wherein the method comprises the following steps:

in the step b of the process,

The weight ratio of the polymer microsphere to the alkali metal hydroxide ranges from (0.1 to 20): 1.

34. The method for preparing the high-barrier anti-adhesion composite film according to claim 33, wherein:

in the step b of the process,

The weight ratio of the polymer microsphere to the alkali metal hydroxide ranges from (0.1 to 10): 1.

35. The method for preparing the high-barrier anti-adhesion composite film according to claim 30, wherein the method comprises the following steps:

in the step c, the weight ratio of the zinc salt to the polymer microsphere is (0.1-20): 1.

36. The method for preparing the high-barrier anti-adhesion composite film according to claim 35, wherein the method comprises the following steps:

in the step c, the weight ratio of the zinc salt to the polymer microsphere is (0.1-10): 1.

37. The method for preparing the high-barrier anti-adhesion composite film according to claim 30, wherein the method comprises the following steps:

the weight ratio range of the zinc salt microsphere to the isolating agent is 1: (0.1 to 0.5).

38. The method for preparing the high-barrier anti-adhesion composite film according to claim 30, wherein the method comprises the following steps:

in the step a, the alkali metal hydroxide is at least one selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide; and/or the number of the groups of groups,

In the step c, the zinc salt is selected from at least one of water-soluble zinc salts.

39. The method for preparing the high-barrier anti-adhesion composite film according to claim 38, wherein the method comprises the following steps:

the alkali metal hydroxide is at least one selected from lithium hydroxide, sodium hydroxide and potassium hydroxide.

40. The method for preparing the high-barrier anti-adhesion composite film according to claim 38, wherein the method comprises the following steps:

The zinc salt is at least one selected from zinc acetate, zinc lactate, zinc chloride, zinc bromide, zinc nitrate, zinc sulfate and zinc gluconate.

41. The method for preparing the high-barrier anti-adhesion composite film according to claim 27, wherein:

the preparation method of the guanidine salt microsphere composition in the multifunctional additive comprises the following steps:

Adding the polymer microsphere into a guanidine salt polymer aqueous solution for grafting reaction, or adding the guanidine salt polymer aqueous solution into a polymerization system of the polymer microsphere for grafting reaction; and then separating, drying, and mixing the obtained guanidine salt microsphere with a release agent to obtain the guanidine salt microsphere composition.

42. The method for preparing the high-barrier anti-adhesion composite film according to claim 41, wherein the method comprises the following steps:

In an amount of 1000g of maleic anhydride providing the structural units of the polymeric microspheres,

The dosage of the guanidine salt polymer aqueous solution is 500-10000 g; the concentration of the guanidine salt polymer aqueous solution is 0.5-50wt%; and/or the number of the groups of groups,

The grafting reaction conditions include: the temperature is 0-100 ℃; the reaction time is 0.5-10 h.

43. The method for preparing the high-barrier anti-adhesion composite film according to claim 42, wherein:

The dosage of the guanidine salt polymer aqueous solution is 1000-8000 g; the concentration of the guanidine salt polymer aqueous solution is 1-30wt%; and/or the number of the groups of groups,

The grafting reaction conditions include: the temperature is 2.5-90 ℃.

44. The method for preparing the high-barrier anti-adhesion composite film according to claim 41, wherein the method comprises the following steps:

45. Use of a high barrier anti-adhesion composite film according to any one of claims 1 to 25 or a composite film prepared according to the method of any one of claims 26 to 44.

46. The method of claim 45, wherein the method is used in packaging of foods and medicines.