CN109705424A - A kind of Biaxially-oriented polyethylene antibacterial film and preparation method thereof - Google Patents
A kind of Biaxially-oriented polyethylene antibacterial film and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to Biaxial tension polyethylene film field, it is related to a kind of Biaxially-oriented polyethylene antibacterial film and preparation method thereof.The Biaxially-oriented polyethylene antibacterial film includes polyethylene core and the antimicrobial surface layer for being attached to a polyethylene core at least side surface, and the antimicrobial surface layer is the polyethylene layer for being dispersed with guanidine salt complex antimicrobials；The guanidine salt complex antimicrobials contain guanidine salt polymer, zinc salt and/or mantoquita, migration inhibitor, nanometer grade powder rubber and dispersing agent；In the guanidine salt complex antimicrobials, by the content of guanidine salt polymer be 100 parts by weight in terms of, the content of the zinc salt and/or mantoquita is 0.01~40 parts by weight, the content of the migration inhibitor is 0.1~10 parts by weight, the content of the nanometer grade powder rubber is 0.5~100 parts by weight, and the content of the dispersing agent is 0.1~10 parts by weight.Biaxial tension polyethylene film of the invention has both excellent anti-microbial property, optical property and mechanical strength.
Description
Technical field
The invention belongs to Biaxial tension polyethylene film fields, more particularly, to a kind of Biaxially-oriented polyethylene antibacterial
Film and preparation method thereof.
Background technique
Biaxial tension polyethylene film (BOPE film) uses the stretch processes machine-shaping of flat membrane method, stretching ratio
Greatly, high production efficiency, film have excellent mechanical strength, optical property, heat sealability, water resistance and the permeability that blocks water,
It is ideal packaging material, is widely used in the packaging of food, vegetables and fruits, infant article etc., occupies on the market critically important
Status.In recent years, with the improvement of living standards with the enhancing of health consciousness, people increasingly pay attention to healthy living environment
It pursues, therefore the demand of antibacterial BOPE film and its product is increasingly increased.Currently, generalling use to Biaxially-oriented polyethylene
The method of antibacterial agent is added in film to assign BOPE film preferable antibacterial and mouldproof.
Used antibacterial agent mainly includes inorganic and organic antibacterial agent two major classes.Wherein, guanidine salt polymer is a kind of point
There are the antibacterial polymer of guanidino group in minor structure, kind mainly includes polyhexamethylene (double) guanidine hydrochloride, poly- six Asia
Methyl (double) guanidine hydrochloride, polyhexamethylene (double) guanidine propionate, polyhexamethylene (double) guanidine stearate and poly- six methylene
Other inorganic salts or organic salt, polyoxyethylene groups guanidine of base (double) guanidine etc..Due to guanidine salt polymer have in water it is excellent
Dissolubility, therefore guanidine salt polymer is applied as an aqueous solution mostly, as patent JP05209195, US4891423,
Water process is used for as fungicide in CN101156586A.Compared with other organic antibacterial agents, guanidine salt polymer has good
Thermal stability, thermal decomposition temperature is higher, can reach 280 DEG C, therefore can be used as antibacterial additives applied to plastics, fiber,
In rubber product, antimicrobial product is obtained.But since the water solubility of most of guanidine salt polymer is stronger, it is difficult that powder-like is made
Product limit it in the application of plastics, rubber and fiber art.
Patent document CN101037503A discloses a kind of method for preparing powdered guanidine salt polymer product, passes through ion
Separation exchange membrane separates guanidine salt polymer from aqueous solution is made powder sample.Patent document CN1350022A,
CN1445270A, US7282538B2 disclose a kind of method for preparing polyamine and guanidine salt polymer, guanidine salt polymer molecule knot
Contain double bond, epoxy isoreactivity group in structure, for being melted with resinous polymer, solution and solid state shear pulrerizing, system
Standby antibiotic plastic product.Patent document CN102453315A, CN102453316A, CN102286176A using guanidine salt polymer with
Complex antimicrobials have been prepared in the method for the co-precipitation such as pyridinium sulfate, silicate, and are applied to polylactic acid, polypropylene
It is applied in equal film articles, foam plastic product.
As can be seen that preparing guanidine salt polymer powder in CN101037503A, CN1350022A in patent documents above
Condition is harsher, and process is more complicated；Need for guanidine salt polymer to be made antibacterial mother in CN1445270A, US7282538B2
Grain, complex steps, higher cost；Needed in CN102453315A, CN102453316A using pyrithione acid sodium, cost compared with
It is high；CN102453273A needs to be operated at a certain temperature in the process for preparing antibacterial agent, and energy consumption is larger, and dry, powder
Product pattern and size controlling are bad after broken.
As it can be seen that cannot prepare good anti-bacterial effect using existing antibacterial agent, optical property and stable mechanical property it is anti-
Bacterium BOPE film is unable to satisfy the application of film in practice.
Summary of the invention
The purpose of the present invention is overcoming, existing polyethylene film does not have anti-microbial property or anti-microbial property is bad and thin
The lower problem of film-strength provides a kind of Biaxially-oriented polyethylene antibacterial film and preparation method thereof, biaxial tension of the invention
Polyethylene film has both excellent anti-microbial property, optical property and mechanical strength.
First aspect present invention provides a kind of Biaxially-oriented polyethylene antibacterial film, and the Biaxially-oriented polyethylene antibacterial is thin
Film includes polyethylene core and the antimicrobial surface layer for being attached to a polyethylene core at least side surface, the antimicrobial surface layer
For the polyethylene layer for being dispersed with guanidine salt complex antimicrobials；Wherein, the guanidine salt complex antimicrobials contain guanidine salt polymer, zinc salt
And/or mantoquita, migration inhibitor, nanometer grade powder rubber and dispersing agent；In the guanidine salt complex antimicrobials, with guanidine salt polymer
Content be 100 parts by weight meters, the content of the zinc salt and/or mantoquita is 0.01~40 parts by weight, and the migration inhibitor contains
Amount is 0.1~10 parts by weight, and the content of the nanometer grade powder rubber is 0.5~100 parts by weight, and the content of the dispersing agent is
0.1~10 parts by weight；Preferably, the content of the zinc salt and/or mantoquita is 5~25 parts by weight, the content of the migration inhibitor
For 0.2~5 parts by weight, the content of the nanometer grade powder rubber is 4.5~50 parts by weight, and the content of the dispersing agent is 0.5
~5 parts by weight；It is further preferred that the content of the migration inhibitor is 0.3~2 parts by weight, the nanometer grade powder rubber
Content is 10~30 parts by weight.
The polyethylene is a kind of thermoplastic resin produced using ethylene as raw material, has good resistance to low temperature (most
It is low to use reachable -70 DEG C to -100 DEG C of temperature), chemical stability and corrosion resistance are widely used in packaging material.At this
Invent provide polyethylene film in, the polyethylene raw material can by Chinese patent CN105623057A,
Polyethylene structure described in CN105623056A, CN105623061A, CN105623055A and preparation method obtain.
Target product according to the present invention, polyethylene in the polyethylene core and antimicrobial surface layer 190 DEG C,
Melt index under 2.16kg load is 0.5g/10min-5g/10min, preferably 1g/10min-3.5g/10min；Further
Preferably, the melting temperature of the polyethylene core and the polyethylene in antimicrobial surface layer is 105-138 DEG C.
According to the present invention, the thickness of the thickness of the polyethylene core and antimicrobial surface layer can be thin according to the polyethylene
The use condition of film suitably selects, if the condition used requires the polyethylene film to have biggish mechanical strength,
Higher anti-microbial property, then the thickness of the thickness of the polyethylene core and antimicrobial surface layer can be thicker；It is used if described
Condition requires the polyethylene film to have preferable light transmission, then the thickness of the polyethylene core and antimicrobial surface layer
Thickness can be relatively thin.Under normal conditions, the thickness of the polyethylene core can be 5-100 microns, be attached to the polyethylene
The thickness of the antimicrobial surface layer of a sandwich layer at least side surface can be 0.1-10 microns, correspondingly, of the antibacterial agent
Grain diameter is 0.01-10 microns；It is described under preferable case for the comprehensive performance of the polyethylene film further increased
The thickness of polyethylene core can be 10-60 microns, and the thickness of the antimicrobial surface layer of the polyethylene core side can be 1-5
Micron, correspondingly, the particle diameter of the antibacterial agent are 0.1-5 microns.
The Biaxially-oriented polyethylene antibacterial film of the invention preferably have the feature that longitudinal tensile strength >=
80MPa, transverse tensile strength >=100MPa, antibiotic rate >=95%.
According to the present invention, the content of complex antimicrobials described in polyethylene surface layer can change in a wider range, this
Field technical staff should be understood that the content of the guanidine salt complex antimicrobials is bigger, and anti-microbial property is better, but Film Optics
Performance and mechanical property will be declined, therefore performance synthesis from every side considers, and tests through the present inventor
Obtain, under preferable case, by the polyvinyl resin of the antimicrobial surface layer be 100 parts by weight in terms of, guanidine salt complex antimicrobials are
0.05~2.0 parts by weight.
According to the preferred embodiment of the present invention, the antimicrobial surface layer can also include other components, for example, described anti-
Bacterium superficial layer it is optional include mould inhibitor and/or other auxiliary agents.
According to the present invention, the mould inhibitor can be selected from pyrithione class, isothiazolinone, 10, and 10 '-oxo diphenol are disliked
Piperazine (OBPA), 3-Iodo-2-propynyl butyl carbamate (IPBC), 2,4,4 '-three chloro- 2 '-dihydroxy diphenyl ethers (triclosan)
At least one of with 2- (thiazole-4-yl) benzimidazole (probenazole)；The pyrithione class is preferably zinc pyrithione, pyrrole
At least one of pyridine thioketones copper and Bispyrithione；The isothiazolinone is preferably 2- methyl-1-isothiazoline-3- ketone
(MIT), 5- chloro-2-methyl -1- isothiazoline -3- ketone (CMIT), Kathon (OIT), 4,5- bis-
Chloro- 2- n-octyl -3- isothiazolinone (DCOIT), 1,2- benzisothiazole-3-ketone (BIT), 4- methyl-1,2- benzisoxa
At least one of thiazoline -3- ketone (MBIT) and 4- normal-butyl -1,2- benzisothiazole-3-ketone (BBIT).It is described mould proof
The content of agent can refer to prior art conventional amount used and determine, for example, the content of the mould inhibitor can be 0~5.0 parts by weight, it is excellent
It is selected as 0.05~0.5 parts by weight.
In the present invention, " other auxiliary agents " refer in addition to clearly state containing auxiliary agent (such as antibacterial agent) other than other
Function additive.For example, other described auxiliary agents may include mould inhibitor, antioxidant, light when the antimicrobial surface layer is free of mould inhibitor
Stabilizer, fire retardant, glass fibre, toughener, compatilizer, pigment, inorganic filler.When the antimicrobial surface layer contains mould inhibitor
When, other described auxiliary agents may include that (such as phenolic antioxidant, phosphite ester antioxidant are made of compound antioxidant the two
Antioxidant), light stabilizer, fire retardant, glass fibre, toughener, compatilizer, pigment, inorganic filler (such as nanometer grade calcium carbonate).
The content of other auxiliary agents is determined see also prior art conventional amount used, for example, the content for stating other auxiliary agents can be with
For 0~100 parts by weight, it is preferable that the content of other auxiliary agents is 0.1~100 parts by weight.
According to the present invention, the guanidine salt polymer can be the various polyguanidine salt in antimicrobial technology field, it is preferable that the guanidine salt
Polymer is selected from least one of inorganic acid salt and/or acylate, polyoxyethylene groups guanidine of polyhexamethylene (double) guanidine；Into
One step is preferably selected from polyhexamethylene (double) guanidine hydrochloride, polyhexamethylene (double) guanidine phosphate, polyhexamethylene (double) guanidine second
Hydrochlorate, polyhexamethylene (double) guanidine propionate, polyhexamethylene (double) guanidine stearate, polyhexamethylene (double) guanidine lauric acid
At least one of salt, polyhexamethylene (double) guanidine benzoate and polyhexamethylene (double) guanidine sulfonate；Still further preferably
For polyhexamethylene (double) guanidine hydrochloride and/or polyhexamethylene (double) guanidine propionate.
According to the present invention, the zinc salt and/or mantoquita can be selected from various water-soluble zinc salts and/or mantoquita, for example, being selected from sulphur
At least one of sour zinc, zinc nitrate, zinc chloride, zinc acetate, copper sulphate, copper nitrate and copper chloride；Preferably inorganic zinc salt and/
Or inorganic mantoquita, such as selected from least one of zinc sulfate, zinc nitrate, zinc chloride, copper sulphate, copper nitrate and copper chloride；Into
One step is preferably zinc sulfate and/or copper sulphate.The addition of zinc salt and/or mantoquita so that guanidine salt complex antimicrobials of the present invention antibacterial
Performance significantly improves.
The addition of migration inhibitor can effectively improve water resistance of the guanidine salt polymer in product, even if guanidine salt is compound anti-
Microbial inoculum dosage is seldom, can also make to reach preferable antibacterial effect before and after boiling.It anti-is moved in accordance with the present invention it is preferred that described
Shifting agent is blocked polyisocyanate, is further preferably selected from the closed polyisocyanates of phenol, the closed polyisocyanate of caprolactam
At least one of cyanate and the closed polyisocyanates of diacetylmonoxime.In the present invention, the blocked polyisocyanate can lead to
Cross it is commercially available, such as Cohan wound2794 XP, Bayer BL5140.
Powdered rubber helps to reduce its water imbibition in storage in guanidine salt complex antimicrobials used in the present invention, improves
Its moisture resistance, can also improve the dispersibility of antibacterial agent, to increase the operability and use of antibacterial agent in practical applications
Timeliness.In the present invention, the nanometer grade powder rubber can be the various powdered rubber particles of nano-scale, preferably through spoke
Penetrate crosslinking full vulcanization butadiene-styrene rubber, entirely vulcanize carboxylic styrene-butadiene rubber, full-sulfurized nitrile rubber, entirely vulcanize carboxy nitrile rubber,
In full vulcanized acrylate rubber, full cured ethylene vinyl acetate rubber, full sulphurated siliastic and full vulcanization butadiene-styrene-vinyl pyridine rubber
At least one；Further preferably vulcanize butadiene-styrene rubber and/or full sulphurated siliastic entirely.
According to the present invention, the dispersing agent is used to improve the dispersibility of antibacterial agent, can be various points of this field routine
Powder, preferably nanometer-level inorganic powder are further preferably selected from nanoscale calcium carbonate, silica, montmorillonite, oxidation
In zinc, talcum powder, titanium dioxide, carbon nanotube, graphene, carbon fiber, boron nitride, zirconium dioxide, wollastonite and zeolite extremely
Few one kind；More preferably nanometer grade calcium carbonate and/or nano grade gas phase silicon dioxide.
According to the present invention, the guanidine salt complex antimicrobials are preferably made by method comprising the following steps:
A, guanidine salt polymer aqueous solution is contacted with the aqueous solution of zinc salt and/or mantoquita, forms transparent liquid mixture；
B, the resulting liquid mixture of step a is mixed with the latex solution after crosslinking by radiation, anti-migration is then added
Agent obtains mixture；
C, the resulting mixture of step b is spray-dried, obtains solid powder, then with dispersant, obtained
The guanidine salt complex antimicrobials.
In accordance with the present invention it is preferred that the mass concentration of the guanidine salt polymer aqueous solution is 10%~40%, preferably
15%~25%；The mass concentration of the aqueous solution of the zinc salt and/or mantoquita is 15%~30%, preferably 20%~25%；
The mass concentration of the latex solution is 30%~40%, is directly used after the latex solution crosslinking by radiation.
Show the aqueous solution and latex solution of guanidine salt polymer aqueous solution, zinc salt and/or mantoquita by many experiments
Concentration could preferably prepare guanidine salt complex antimicrobials in the range of the preparation method.Used guanidine in the method for the present invention
The concentration of salt aqueous solutions of polymers, the aqueous solution of zinc salt and/or mantoquita and latex emulsion is unsuitable excessively high, is otherwise unfavorable for stirring
Uniformly, it there is also coacervation, subsequent spray-drying operation can not be carried out；Concentration is also unsuitable too low, otherwise will cause life
Produce low efficiency, waste water resource and the energy.Preparation and hybrid manipulation due to solution carry out at room temperature, can be into after mixing
Row spray-drying operation, therefore the preparation method energy consumption of guanidine salt complex antimicrobials used in the present invention is low, the time is short, high-efficient, it can
Carry out continuous production.
In the above method, the spray drying can carry out in spray-dried instrument.The mixing of solid powder and dispersing agent can
It is carried out in high speed agitator, after high-speed stirred, dispersion, obtains guanidine salt complex antimicrobials of the invention.
In the above method, the guanidine salt polymer aqueous solution can by obtaining guanidine salt polymer solid is soluble in water,
It can be directly commercially available.
In the above method, it is preferable that guanidine salt polymer, the zinc salt and/or copper in the guanidine salt polymer aqueous solution
Zinc salt and/or mantoquita in the aqueous solution of salt, the soluble solids in the latex solution, the migration inhibitor and the dispersing agent
Weight ratio is 100:0.01~40:0.5~100:0.1~10:0.1~10；Preferably, in the guanidine salt polymer aqueous solution
Zinc salt and/or mantoquita in the aqueous solution of guanidine salt polymer, the zinc salt and/or mantoquita, the soluble solids in the latex solution,
The weight ratio of the migration inhibitor and the dispersing agent is 100:5~25:4.5~50:0.5~5:0.5~5.
In the above method, the latex can be determined according to the type of powdered rubber needed for final, it is preferable that the latex is
Styrene-butadiene latex, carboxylic styrene butadiene latex, NBR latex, carboxylic acrylonitrile butadiene rubber latex, acrylate latex, ethylene vinyl acetate latex,
At least one of silicone rubber latex and butadiene styrene vinyl pyridine latex；Preferably styrene-butadiene latex and/or silicone rubber latex.
According to the present invention, it is sprayed again after being uniformly dispersed in latex due to antimicrobial components such as guanidine salt polymer and zinc salts
It is dry, therefore the dispersion of antimicrobial component in the final product is more uniform, is also beneficial to powdered rubber and plays in process
Better peptizaiton improves antibacterial effect.
The second aspect of the present invention provides the preparation method of above-mentioned Biaxially-oriented polyethylene antibacterial film, this method include with
Lower step:
A, polyvinyl resin and guanidine salt complex antimicrobials and optional mould inhibitor and/or other auxiliary agents are uniformly mixed,
Uniformly mixed material melts are kneaded simultaneously extruding pelletization again, obtain antimicrobial surface layer raw material；
B, the antimicrobial surface layer raw material and polyethylene raw material are sent into the extrusion casting apparatus with multi-layer co-extruded structure
Middle extrusion curtain coating, obtain include polyethylene core at least side surface for being attached to the polyethylene core antimicrobial surface layer
Cast-sheet；
C, obtained cast-sheet is subjected to biaxial tension, obtains the Biaxial tension polyethylene film.The two-way drawing
It stretches and the progress of flat membrane method can be used.
According to the present invention, the more excellent polyethylene film of performance in order to obtain, under preferable case, this method further include
Before polyethylene and complex antimicrobials are mixed, and the antimicrobial surface layer raw material and polyvinyl resin are being sent into casting machine
Before, polyethylene and complex antimicrobials are dried.The method and condition of the drying can be public for those skilled in the art
The drying means and condition known, for example, can be vacuum drying, forced air drying etc., drying temperature can be 30-100 DEG C.It is dry
Equipment is usually the drying equipment for including heating, dry warm air blowoff or vacuum system, for example, can for continuous dryer,
Vacuum drying oven and hot-air oven etc..
Generally, the mode that the polyvinyl resin and complex antimicrobials are uniformly mixed can be for by the polyethylene and again
It is uniform that conjunction antibacterial agent is added to blended under agitation in existing various mixing apparatus.Wherein, the mixing apparatus for example can be to stir
Mix machine, kneader, open mill and mixer etc..The temperature and time of blended under agitation is known to those skilled in the art, for example,
The temperature of blended under agitation can be 25-65 DEG C, and the time of blended under agitation can be 1-30 minutes, and the revolving speed of blended under agitation can be
50-300 revs/min；Under preferable case, first stir 1-15 minutes under 50-100 revs/min of revolving speed, then again 100-200 turns/
It is stirred 1-15 minutes under the revolving speed divided.
According to the present invention, the mixture that polyethylene and complex antimicrobials are obtained after mixing carries out melting mixing
And extruding pelletization obtain antimicrobial surface layer raw material method, condition and extruder used it is known to those skilled in the art.
For example, using double screw extruder or can use single screw extrusion machine, screw speed is 150-360 revs/min, respectively
Zone temperatures are respectively 150-220 DEG C, 160-230 DEG C, 160-230 DEG C, 170-240 DEG C, 170-240 DEG C, 170-240 DEG C, respectively
The vacuum degree of section is extruding pelletization under conditions of 0.02 to 0.09 megapascal.Vacuum degree in the present invention refers to absolute pressure and big
The absolute value of the difference of atmospheric pressure.
It should be noted that squeezing out casting apparatus generally includes multiple extruders, it can be to different in multiple extruders
Material is heated, and the material after different extruder heating can be multiple by the same multilayer for including at least two layers
Mold head squeeze out curtain coating, thus obtain include multilayer cast-sheet；Wherein, the material in each extruder is from the multilayer
Wherein one layer of extrusion of compound die head.Therefore, those skilled in the art should be readily understood that, when needing to obtain polyethylene
When one side surface of sandwich layer is attached with the polyethylene film of antimicrobial surface layer, described it can will be resisted using two different extruders
Bacterium superficial layer raw material and polyethylene melting, and by molten product simultaneously pass through it is same include two layers die head squeeze out curtain coating, squeeze
The two membranes obtained after out are stacked together just to obtain cast-sheet, then polyethylene of the invention can be obtained after biaxial tension
Antibacterial film；It, can be with when the both side surface for needing to obtain polyethylene core is attached with the polyethylene film of antimicrobial surface layer
Raw material melting (wherein, is added polyethylene, is added in the extruder of surface layer anti-in main extruder using three different extruders
Bacterium superficial layer raw material), and molten product passed through simultaneously same includes that three layers of die head squeezes out curtain coating, three obtained after extrusion
Tunic is stacked together to obtain cast-sheet, then polyethylene antibiotic film of the invention can be obtained after biaxial tension.
According to the present invention, the condition for squeezing out curtain coating and extruder used are known to the skilled person.For example,
It can be using single screw extrusion machine, double screw extruder etc..The condition of extrusion generally includes extrusion temperature and curtain coating cooling temperature,
The extrusion temperature includes extruder temperature, draping area temperature and head temperature, and the extrusion temperature can be 150-250 DEG C；
The curtain coating cooling temperature refers generally to the temperature of casting roller, can be 10-95 DEG C.
According to the present invention, the biaxial tension can carry out in biaxial tension equipment, such as be purchased from Germany Br ü
Biaxial tension is carried out in the film biaxial orientation stretching machine of the model Karo IV of ckner company.The biaxial tension can be using same
Footwork stretches, i.e., carries out film longitudinal (MD) simultaneously and laterally (TD) is stretched；It can also be stretched, i.e., first carried out thin using the method for fractional steps
Film longitudinal (MD) stretches, and then carries out film and laterally (TD) stretches；It laterally (TD) stretches alternatively, first carrying out film, then carries out
Film longitudinal (MD) stretches.Specifically, the Synchronos method stretches are as follows: will squeeze out the cast-sheet for being cast and obtaining at 80-140 DEG C
After being fully warmed-up, the synchro-draw in the direction MD and TD is carried out；Wherein, MD stretching ratio can be 2-7 times, and TD stretching ratio can be with
It is 2-7 times, draft temperature can be 80-140 DEG C.The method of fractional steps stretches are as follows: will squeeze out the cast-sheet for being cast and obtaining in 80-
After being fully warmed-up at 140 DEG C, the stretching in the direction MD is first carried out, stretching ratio can be 2-7 times, and draft temperature can be 80-140
℃；Then the stretching in the direction TD is carried out after being fully warmed-up at 80-140 DEG C again, stretching ratio can be 2-7 times, draft temperature
It can be 80-140 DEG C.
According to the present invention, obtained film can also be made annealing treatment after the drawing and forming, with what is prevented
Film generates larger contraction；Or the film after stretching is directly subjected to cutting edge and polyethylene of the invention can be obtained after winding
Antibacterial film product.
Key of the invention is the provision of the group that Biaxially-oriented polyethylene antibacterial film is especially wherein antimicrobial surface layer
Point, it will be appreciated by those skilled in the art that this field can be used is normal by the preparation process of the Biaxially-oriented polyethylene antibacterial film
The various techniques of rule, as long as meeting the polyethylene antibiotic film that above structure and composition can be made.
In the present invention, on the one hand, added guanidine salt complex antimicrobials are spherical in shape, and mode of appearance is regular, partial size it is smaller and
Particle diameter distribution is uniform.After biaxial tension, antibacterial agent exists the polyethylene film prepared using the antibacterial agent and the method for the present invention
Film surface layer is uniformly dispersed, so that obtained polyethylene film has preferable antibacterial effect and water resistance；Further, it adopts
Polyethylene antibiotic film is prepared with method of the invention, migrates without waiting for antibacterial agent to the surface layer of the film, can be improved
The production and service efficiency of film.
In addition, guanidine salt complex antimicrobials good fluidity of the present invention, moisture absorption are low, in polyethylene antibiotic film system
During standby, guanidine salt polymer does not glue wall, and easy blanking, production operation is simple, controls without excessive working condition.It is prepared
Antibacterial film good anti-bacterial effect, water resistance is also improved.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Detailed description of the invention
Exemplary embodiment of the invention is described in more detail in conjunction with the accompanying drawings.
Fig. 1 shows the electron microscope of guanidine salt complex antimicrobials used in one embodiment of the present invention.
Specific embodiment
The preferred embodiment of the present invention is described in more detail below.
Hot-air oven used in embodiment and comparative example leads to instrument plant, model DF205 purchased from system in Beijing Jing；Extruding pelletization
Device therefor is double screw extruder, is purchased from WP company, Germany, model ZSK25；Biaxial orientation stretching machine is purchased from Germany Br ü ckner
Company, model Karo IV；It squeezes out casting apparatus and is purchased from Sweden Labtech company, model LCR400；The melting of polyethylene
Index is measured by the fusion index instrument of the model MP600 purchased from U.S. TO company.
Raw materials used and source is as follows in embodiment and comparative example:
Poly (hexamethylene) hydrochloride: Shanghai Hipoly Industry Co., Ltd.
Polyhexamethylene guanide propionate: Shanghai Hipoly Industry Co., Ltd.
Hexamethylene: the Industrial Co., Ltd. of upper seamount
Zinc sulfate: Xilong Chemical Co., Ltd
Zinc acetate: Xilong Chemical Co., Ltd
Zinc nitrate: Xilong Chemical Co., Ltd
Styrene-butadiene latex: middle petrochemical industry Beijing Chemical Research Institute
NBR latex: middle petrochemical industry Beijing Chemical Research Institute
Silicone rubber latex: middle petrochemical industry Beijing Chemical Research Institute
Migration inhibitor: Cohan wound2794 XP
Nanometer grade calcium carbonate: Jiangxi Huaming nanometer calcium carbonate Co., Ltd
Fumed silica: Shanghai Kai Yin Chemical Co., Ltd.
Zinc pyrithione: Mount Everest Fine Chemical Co., Ltd
MIT, DCOIT: Dalian Bio-Chem Co., Ltd.
Composite antioxidant: antioxidant 1010 and irgasfos 168 (weight ratio 1:1), BASF Aktiengesellschaft
Polyethylene: the trade mark BOPE-1, BOPE-2, BOPE-3, middle petrochemical industry Beijing Chemical Research Institute；
Antibacterial examination criteria and operating procedure are as follows:
1, antibacterial test standard: QB/T 2591-2003A " antibiotic plastic test method of antibacterial performance and antibacterial effect ", inspection
It surveys and uses bacterium: Escherichia coli (Escherichia coli) ATCC 25922, Staphylococcus aureus (Staphylococcus
aureus)ATCC 6538。
2, antibacterial test step is tested referring to antibiotic plastic examination criteria QB/T 2591-2003, and specific steps are such as
Under: sample to be tested is handled and dried with 75% ethanol disinfection, the bacteria suspension that strain is diluted to debita spissitudo with sterile water is standby
With.It takes the bacteria suspension of 0.2mL to drip in sample surfaces, is overlying on thereon, is made with the polyethylene film (4.0cm × 4.0cm) of 0.1mm thickness
Bacteria suspension forms uniform liquid film between sample and film.It is cultivated 18~24 hours in 37 DEG C of holding relative humidity 90%.With nothing
Bacterium water washes down bacterium solution, is diluted to concentration gradient appropriate, and 0.1mL is taken to be uniformly coated on the sterile agar culture prepared
On.It is cultivated 18~24 hours in 37 DEG C, observes result.Negative control is replaced with sterilized petri dishes, other operations are identical.
3, it fungus-proof test: is tested according to ASTM G21-96
The case where cultivating the growth mould of observation in 28 days:
0 grade: not growing, i.e., observation has no growth under microscope (50 times of amplification)；
1 grade: trace growth, i.e. naked eyes visible growth, but area coverage is grown less than 10%；
2 grades: growth area coverage is not less than 10%.
Bacterium is used in detection:
| Serial number | Title | Bacterium number |
| 1 | Aspergillus niger (Aspergillus niger) | AS 3.4463 |
| 2 | Aspergillus terreus (Aspergillus terreus) | AS 3.3935 |
| 3 | Aureobasidium pullulans (Aureobasium Pullulans) | AS 3.3984 |
| 4 | Paecilomyces varioti (Paecilomuces Varioti) | AS 3.4253 |
| 5 | Penicillium funiculosum (Penicillium funicolosum) | AS 3.3872 |
| 6 | Ball hair shell (Chaetoomium globsum) | AS 3.4254 |
Embodiment 1
The embodiment is used to illustrate the preparation of polyethylene antibiotic film provided by the invention.
In the embodiment, the polyethylene of polyethylene core and antimicrobial surface layer is formed as the production of middle petrochemical industry Beijing Chemical Research Institute
BOPE-1, the melt index under 190 DEG C, 2.16kg load is 1 gram/10 minutes, melting temperature is 128 DEG C.
(1) preparation of antimicrobial surface layer raw material:
Preparing for guanidine salt complex antimicrobials is as follows: a, being configured to poly (hexamethylene) hydrochloride 1000.0g is soluble in water
The aqueous solution of mass concentration 20%；50.0g zinc sulfate is configured to the aqueous solution that mass concentration is 25%.125.0g styrene-butadiene latex
It is directly used after solution crosslinking by radiation, concentration 40%.B, prepared guanidine salt polymer aqueous solution is added to filling and is contained
Zinc, aqueous copper solution container in, stir while adding, until be uniformly mixed, form transparent liquid mixture.C, by step
Liquid mixture in b is added into latex solution, stirs while adding, until being uniformly mixed.Then, it is added into mixture
5.0g migration inhibitor.D, the resulting mixture of step c is dried using spray-dried instrument, obtains solid powder, particle is straight
Diameter is 1-2 microns；Obtained solid powder is transferred in high speed agitator, addition 5.0g fumed silica as dispersing agent,
After mixed at high speed, dispersion, guanidine salt complex antimicrobials 1# of the invention is obtained.
Polyethylene is dried in hot-air oven, later by the polyvinyl resin after drying of 100 parts by weight
With the above-mentioned guanidine salt complex antimicrobials 1# of 1.2 parts by weight and the mould inhibitor zinc pyrithione of 0.2 parts by weight, it is added to stirring
Stirred evenly at 25 DEG C in machine, blender first with 100 revs/min mixed on low speed about 1 minute, then again with 200 revs/min of height
Speed mixing 1 minute；
The above-mentioned mixture stirred evenly is sent into double screw extruder.The revolving speed of adjustment screw to 350 revs/min,
Each zone temperatures control respectively: 190 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C and 210 DEG C；The vacuum degree of each section is kept
For 0.02 to 0.09 megapascal；Mixture is in the screw rod and cylinder of above-mentioned extruder, by melting, shearing, dispersion, compression, row
It gas, plasticizing, extrusion and then is squeezed out through 210 DEG C of die heads, after tie rod water cooling pelletizing, finally obtains antimicrobial surface layer raw material.
(2) preparation of cast-sheet:
The antimicrobial surface layer raw material that polyethylene and step (1) obtain is dried in hot-air oven respectively, wherein dry
Dry mode is continuously to be purged 8 hours with 80 DEG C of drying hot-air.Polyethylene after drying is added and squeezes out casting apparatus
In main extruder, the antimicrobial surface layer raw material that step (1) is obtained is added in the surface layer extruder for squeezing out casting apparatus, is melted
Melt extrusion, and through casting roller tape casting, obtaining skin depth is 35 microns, the raw material sheet material that core layer thickness is 350 microns.Its
In, the temperature setting of two extruders is consistent, and each zone temperatures of extruder are respectively 210 DEG C, 220 DEG C, 230 DEG C, 230 DEG C, 230
DEG C, draping area temperature is 240 DEG C, and head temperature is 235 DEG C, and curtain coating roll temperature is 25 DEG C.
(3) biaxial tension forms:
The raw material sheet material that step (2) obtains is subjected to biaxial tension with biaxial orientation stretching machine.Stretching mode used is first to carry out
MD carries out TD stretching after stretching, wherein the preheating temperature that MD is stretched is 110 DEG C, draft temperature is 100 DEG C, stretching ratio 5
Times；The preheating temperature that TD is stretched is 110 DEG C, draft temperature is 100 DEG C, stretching ratio is 7 times.Formed include polyethylene core and
It is attached to the polyethylene antibiotic film X1 of the antimicrobial surface layer of a side surface of the polyethylene core, wherein polyethylene core
With a thickness of 10 microns, antimicrobial surface layer with a thickness of 1 micron.
The test of film tensile strength is carried out after prepared polyethylene antibiotic film X1 is cut into standard batten, is obtained:
The longitudinal tensile strength of film is 85MPa, transverse tensile strength 103MPa.
Prepared polyethylene antibiotic film X1 is cut into the sample of 50mm × 50mm, carries out antibacterial and mouldproof test.Its
Middle sample segment is placed in 50 DEG C of hot water before antibacterial and mouldproof test and impregnates 16h.
Antibacterial and mouldproof result:
Before boiling: Staphylococcus aureus antibiotic rate: 99.9%；Escherichia coli antibiotic rate: 99.9%；Mould proof 0 grade.
After boiling: Staphylococcus aureus antibiotic rate: 99.9%；Escherichia coli antibiotic rate: 99.9%；Mould proof 0 grade.
Embodiment 2
The embodiment is used to illustrate the preparation of polyethylene film provided by the invention.
In the embodiment, the polyethylene of polyethylene core and antimicrobial surface layer is formed as the production of middle petrochemical industry Beijing Chemical Research Institute
BOPE-2, the melt index under 190 DEG C, 2.16kg load is 2 grams/10 minutes, melting temperature is 123 DEG C.
(1) preparation of antimicrobial surface layer raw material:
Preparing for guanidine salt complex antimicrobials is as follows: a, by hexamethylene 1000.0g preparation soluble in water
At the aqueous solution of mass concentration 10%；200.0g zinc nitrate is configured to the aqueous solution that mass concentration is 30%.125.0g silicon rubber
It is directly used after glue latex solution crosslinking by radiation, concentration 40%.B, by prepared guanidine salt polymer aqueous solution be added to
It fills in the container of the aqueous solution containing zinc, stirs while adding, until being uniformly mixed, form transparent liquid mixture.It c, will step
Liquid mixture in rapid b is added into latex solution, stirs while adding, until being uniformly mixed.Then, add into mixture
Enter 5.0g migration inhibitor.D, the resulting mixture of step c is dried using spray-dried instrument, obtains solid powder, particle
Diameter is 2-4 microns；Obtained solid powder is transferred in high speed agitator, addition 30.0g talcum powder is as dispersing agent, high speed
After mixing, dispersion, guanidine salt complex antimicrobials 2# of the invention is obtained.
Polyethylene is dried in hot-air oven, later by the polyvinyl resin after drying of 100 parts by weight
With the above-mentioned guanidine salt complex antimicrobials 2# of 0.8 parts by weight and mould inhibitor 2- methyl-1-isothiazoline-3- ketone of 0.5 parts by weight
(MIT) be added in blender and stirred evenly at 25 DEG C, blender first with 80 revs/min mixed on low speed about 2 minutes, then again
With 150 revs/min mixed at high speed 0.5 minute；
The above-mentioned mixture stirred evenly is sent into double screw extruder.The revolving speed of adjustment screw to 350 revs/min,
Each zone temperatures control respectively: 190 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C and 210 DEG C；The vacuum degree of each section is kept
For 0.02 to 0.09 megapascal；Mixture is in the screw rod and cylinder of above-mentioned extruder, by melting, shearing, dispersion, compression, row
It gas, plasticizing, extrusion and then is squeezed out through 210 DEG C of die heads, after tie rod water cooling pelletizing, finally obtains antimicrobial surface layer raw material.
(2) preparation of cast-sheet:
The antimicrobial surface layer raw material that polyethylene and step (1) obtain is dried in hot-air oven respectively, wherein dry
Dry mode is continuously to be purged 8 hours with 80 DEG C of drying hot-air.Polyethylene after drying is added and squeezes out casting apparatus
In main extruder, the antimicrobial surface layer raw material that step (1) is obtained is added in the surface layer extruder for squeezing out casting apparatus, is melted
Melt extrusion, and through casting roller tape casting, obtaining skin depth is 70 microns, the raw material sheet material that core layer thickness is 875 microns.Its
In, the temperature setting of two extruders is consistent, and each zone temperatures of extruder are respectively 210 DEG C, 220 DEG C, 230 DEG C, 230 DEG C, 230
DEG C, draping area temperature is 240 DEG C, and head temperature is 235 DEG C, and curtain coating roll temperature is 35 DEG C.
(3) biaxial tension forms:
The raw material sheet material that step (2) obtains is subjected to biaxial tension with biaxial orientation stretching machine.Stretching mode used be simultaneously into
Row film longitudinal (MD) and laterally (TD) stretching, wherein preheating temperature when stretching is 110 DEG C, draft temperature is 100 DEG C, MD
Stretching ratio is 5 times, and TD stretching ratio is 7 times.Formed includes polyethylene core and the side for being attached to the polyethylene core
The polyethylene film X2 of the antimicrobial surface layer on surface, wherein polyethylene core with a thickness of 25 microns, the thickness of antimicrobial surface layer
It is 2 microns.
The test of film tensile strength is carried out after prepared polyethylene antibiotic film X2 is cut into standard batten, is obtained:
The longitudinal tensile strength of film is 90MPa, transverse tensile strength 110MPa.
Prepared polyethylene antibiotic film X2 is cut into the sample of 50mm × 50mm, carries out antibacterial and mouldproof test.Its
Middle sample segment is placed in 50 DEG C of hot water before antibacterial and mouldproof test and impregnates 16h.
Antibacterial and mouldproof result:
Before boiling: Staphylococcus aureus antibiotic rate: 99.9%；Escherichia coli antibiotic rate: 99.9%；Mould proof 0 grade.
After boiling: Staphylococcus aureus antibiotic rate: 99.9%；Escherichia coli antibiotic rate: 99.9%；Mould proof 0 grade.
Embodiment 3
The embodiment is used to illustrate the preparation of polyethylene film provided by the invention.
In the embodiment, the polyethylene of polyethylene core and antimicrobial surface layer is formed as the production of middle petrochemical industry Beijing Chemical Research Institute
BOPE-3, the melt index under 190 DEG C, 2.16kg load is 3.5 grams/10 minutes, melting temperature is 118 DEG C.
(1) preparation of antimicrobial surface layer raw material:
Preparing for guanidine salt complex antimicrobials is as follows:
A, by the polyhexamethylene guanide propionate 1000.0g aqueous solution soluble in water for being configured to mass concentration 40%；It will
100.0g zinc acetate is configured to the aqueous solution that mass concentration is 15%.Directly make after 150.0g NBR latex solution crosslinking by radiation
With concentration 30%.B, prepared guanidine salt polymer aqueous solution is added into the container for filling the aqueous solution containing zinc, side is added
Side stirring forms transparent liquid mixture until being uniformly mixed.C, the liquid mixture in step b is added molten to latex
It in liquid, stirs while adding, until being uniformly mixed.Then, 5.0g migration inhibitor is added into mixture.It d, will be obtained by step c
Mixture be dried using spray-dried instrument, obtain solid powder；Obtained solid powder is transferred in high speed agitator,
15.0g nanometer calcium carbonate is added as dispersing agent, after mixed at high speed, dispersion, obtains guanidine salt complex antimicrobials 3# of the invention.
Polyethylene is dried in hot-air oven, later by the polyvinyl resin after drying of 100 parts by weight
With the above-mentioned guanidine salt complex antimicrobials 3# of 0.1 parts by weight, the mould inhibitor of 0.25 parts by weight of composite antioxidant and 1 parts by weight
DCOIT is added in blender to stir evenly at 25 DEG C, blender first with 80 revs/min mixed on low speed about 2 minutes, then again
With 150 revs/min mixed at high speed 0.5 minute；
The above-mentioned mixture stirred evenly is sent into double screw extruder.The revolving speed of adjustment screw to 350 revs/min,
Each zone temperatures control respectively: 190 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C and 210 DEG C；The vacuum degree of each section is kept
For 0.02 to 0.09 megapascal；Mixture is in the screw rod and cylinder of above-mentioned extruder, by melting, shearing, dispersion, compression, row
It gas, plasticizing, extrusion and then is squeezed out through 210 DEG C of die heads, after tie rod water cooling pelletizing, finally obtains antimicrobial surface layer raw material.
(2) preparation of cast-sheet:
The antimicrobial surface layer raw material that polyethylene and step (1) obtain is dried in hot-air oven respectively, wherein dry
Dry mode is continuously to be purged 8 hours with 80 DEG C of drying hot-air.Polyethylene after drying is added and squeezes out casting apparatus
In main extruder, the antimicrobial surface layer raw material that step (1) is obtained is added in the surface layer extruder for squeezing out casting apparatus, is melted
Melt extrusion, and through casting roller tape casting, obtaining skin depth is 70 microns, the raw material sheet material that core layer thickness is 875 microns.Its
In, the temperature setting of two extruders is consistent, and each zone temperatures of extruder are respectively 210 DEG C, 220 DEG C, 230 DEG C, 230 DEG C, 230
DEG C, draping area temperature is 240 DEG C, and head temperature is 235 DEG C, and curtain coating roll temperature is 35 DEG C.
(3) biaxial tension forms:
The raw material sheet material that step (2) obtains is subjected to biaxial tension with biaxial orientation stretching machine.Stretching mode used be simultaneously into
Row film longitudinal (MD) and laterally (TD) stretching, wherein preheating temperature when stretching is 110 DEG C, draft temperature is 100 DEG C, MD
Stretching ratio is 5 times, and TD stretching ratio is 7 times.Formed includes polyethylene core and the side for being attached to the polyethylene core
The polyethylene film X3 of the antimicrobial surface layer on surface, wherein polyethylene core with a thickness of 60 microns, the thickness of antimicrobial surface layer
It is 5 microns.
The test of film tensile strength is carried out after prepared polyethylene antibiotic film X3 is cut into standard batten, is obtained:
The longitudinal tensile strength of film is 90MPa, transverse tensile strength 120MPa.
Prepared polyethylene antibiotic film X3 is cut into the sample of 50mm × 50mm, carries out antibacterial and mouldproof test.Its
Middle sample segment is placed in 50 DEG C of hot water before antibacterial and mouldproof test and impregnates 16h.
Antibacterial and mouldproof result:
Before boiling: Staphylococcus aureus antibiotic rate: 99.9%；Escherichia coli antibiotic rate: 99.9%；Mould proof 0 grade.
After boiling: Staphylococcus aureus antibiotic rate: 99.9%；Escherichia coli antibiotic rate: 99.9%；Mould proof 0 grade.
Comparative example 1
The comparative example is used to illustrate the reference preparation of polyethylene film.
Polyethylene film is prepared in the way of embodiment 1, the difference is that by the guanidine salt composite antibacterial in embodiment 1
Agent 1#1.2 parts by weight replace with 1.2 parts by weight of poly (hexamethylene) hydrochloride, other steps cut system with embodiment 1, by film
At sample, and carry out antibacterial and mouldproof test.
The anti-bacterial result:
Before boiling: Staphylococcus aureus antibiotic rate: 93.5%；Escherichia coli antibiotic rate: 90.6%；Mould proof 1 grade.
After boiling: Staphylococcus aureus antibiotic rate: 45.5%；Escherichia coli antibiotic rate: 43.2%；Mould proof 2 grades.
Above-mentioned comparison result explanation, guanidine salt complex antimicrobials not only increase the antibacterial and mouldproof effect of film, also have compared with
Good water resistance, the antibacterial and mouldproof effect of antibacterial and mouldproof film is better than the effect of pure poly (hexamethylene) hydrochloride before and after boiling
Fruit.
Comparative example 2
The comparative example is used to illustrate the reference preparation of polyethylene film.
Polyethylene film is prepared according to the method for embodiment 2, the difference is that by 0.8 parts by weight in embodiment 2
The zinc pyrithione of guanidine salt complex antimicrobials 2# and 0.2 parts by weight replace with the cosmocil stearate acid of 1.0 parts by weight
Salt, film is cut and sample is made by other steps with embodiment 2, and carries out antibacterial and mouldproof test.
Antibacterial and mouldproof result:
Before boiling: Staphylococcus aureus antibiotic rate: 65.4%；Escherichia coli antibiotic rate: 59.6%；Mould proof 1 grade.
After boiling: Staphylococcus aureus antibiotic rate: 0；Escherichia coli antibiotic rate: 0；Mould proof 2 grades.
Above-mentioned comparison result explanation is thin after reducing the dosage of guanidine salt complex antimicrobials and being aided with mould inhibitor zinc pyrithione
Film still has preferable antibacterial and mouldproof effect, and the antibacterial and mouldproof effect of film is better than pure cosmocil stearate before and after boiling
The effect of hydrochlorate.
Comparative example 3
The comparative example is used to illustrate the reference preparation of polyethylene film.
Polyethylene film is prepared according to the method for embodiment 3, the difference is that by 0.1 parts by weight in embodiment 3
The mould inhibitor DCOIT of guanidine salt complex antimicrobials 3# and 1 parts by weight replace with the polyhexamethylene guanide propionate of 1.1 parts by weight,
Film is cut and sample is made step by he with embodiment 3, and carries out antibacterial and mouldproof test.
Antibacterial and mouldproof result:
Before boiling: Staphylococcus aureus antibiotic rate: 70%；Escherichia coli antibiotic rate: 55%；Mould proof 1 grade.
After boiling: Staphylococcus aureus antibiotic rate: 0；Escherichia coli antibiotic rate: 0；Mould proof 2 grades.
Above-mentioned comparison result explanation, even if the dosage of guanidine salt complex antimicrobials is very low, film still has preferable antibacterial anti-
Mould effect, the antibacterial and mouldproof effect of film is better than the effect of pure polyhexamethylene guanide propionate before and after boiling.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (12)
1. a kind of Biaxially-oriented polyethylene antibacterial film, which is characterized in that the Biaxially-oriented polyethylene antibacterial film includes poly-
Ethylene sandwich layer and the antimicrobial surface layer for being attached to a polyethylene core at least side surface, the antimicrobial surface layer are to be dispersed with
The polyethylene layer of guanidine salt complex antimicrobials；Wherein,
The guanidine salt complex antimicrobials contain guanidine salt polymer, zinc salt and/or mantoquita, migration inhibitor, nanometer grade powder rubber with
And dispersing agent；In the guanidine salt complex antimicrobials, by the content of guanidine salt polymer be 100 parts by weight in terms of, the zinc salt and/or copper
The content of salt is 0.01~40 parts by weight, and the content of the migration inhibitor is 0.1~10 parts by weight, the nanometer grade powder rubber
Content be 0.5~100 parts by weight, the content of the dispersing agent is 0.1~10 parts by weight；Preferably, the zinc salt and/or copper
The content of salt is 5~25 parts by weight, and the content of the migration inhibitor is 0.2~5 parts by weight, and the nanometer grade powder rubber contains
Amount is 4.5~50 parts by weight, and the content of the dispersing agent is 0.5~5 parts by weight.
2. Biaxially-oriented polyethylene antibacterial film according to claim 1, wherein the polyethylene core and antimicrobial surface
Melt index of the polyethylene under 190 DEG C, 2.16kg load in layer is 0.5g/10min-5g/10min, preferably 1g/
10min-3.5g/10min；The melting temperature of the polyethylene core and the polyethylene in antimicrobial surface layer is 105-138 DEG C.
3. Biaxially-oriented polyethylene antibacterial film according to claim 1, wherein the polyethylene core with a thickness of 5-
100 microns, be attached to the antimicrobial surface layer of a polyethylene core at least side surface with a thickness of 0.1-10 microns；Institute
The particle diameter for stating guanidine salt complex antimicrobials is 0.01-10 microns；Preferably, the polyethylene core is micro- with a thickness of 10-60
Rice, be attached to the antimicrobial surface layer of a polyethylene core at least side surface with a thickness of 1-5 microns；The guanidine salt is multiple
The particle diameter for closing antibacterial agent is 0.1-5 microns.
4. Biaxially-oriented polyethylene antibacterial film according to claim 1, wherein the Biaxially-oriented polyethylene antibacterial is thin
Longitudinal tensile strength >=80MPa of film, transverse tensile strength >=100MPa, antibiotic rate >=95%.
5. Biaxially-oriented polyethylene antibacterial film according to claim 1, wherein the antimicrobial surface layer includes poly- second
Alkene, guanidine salt complex antimicrobials and optional mould inhibitor and/or other auxiliary agents；Preferably, in terms of by polyethylene for 100 parts by weight,
The content of the guanidine salt complex antimicrobials is 0.05~2.0 parts by weight, and the content of the mould inhibitor is 0~5.0 parts by weight, described
The content of other auxiliary agents is 0~100 parts by weight.
6. Biaxially-oriented polyethylene antibacterial film described in any one of -5 according to claim 1, wherein the guanidine salt polymerization
Object is selected from least one of inorganic acid salt and/or acylate, polyoxyethylene groups guanidine of polyhexamethylene (double) guanidine；
It is preferably selected from polyhexamethylene (double) guanidine hydrochloride, polyhexamethylene (double) guanidine phosphate, polyhexamethylene (double) guanidine second
Hydrochlorate, polyhexamethylene (double) guanidine propionate, polyhexamethylene (double) guanidine stearate, polyhexamethylene (double) guanidine lauric acid
At least one of salt, polyhexamethylene (double) guanidine benzoate and polyhexamethylene (double) guanidine sulfonate；
Further preferably polyhexamethylene (double) guanidine hydrochloride and/or polyhexamethylene (double) guanidine propionate.
7. Biaxially-oriented polyethylene antibacterial film described in any one of -5 according to claim 1, wherein the zinc salt and/
Or mantoquita is inorganic zinc salt and/or inorganic mantoquita；It is preferably selected from zinc sulfate, zinc nitrate, zinc chloride, copper sulphate, copper nitrate and chlorine
Change at least one of copper；Further preferably zinc sulfate and/or copper sulphate.
8. Biaxially-oriented polyethylene antibacterial film described in any one of -5 according to claim 1, wherein the migration inhibitor
For blocked polyisocyanate, it is preferably selected from the closed polyisocyanates of phenol, the closed polyisocyanates of caprolactam and fourth
At least one of closed polyisocyanates of ketoxime.
9. Biaxially-oriented polyethylene antibacterial film described in any one of -5 according to claim 1, wherein the nanoscale powder
Last rubber is the full vulcanization butadiene-styrene rubber of crosslinking by radiation, vulcanizes carboxylic styrene-butadiene rubber entirely, full-sulfurized nitrile rubber, vulcanizes carboxylic entirely
Base nitrile rubber, full vulcanized acrylate rubber, full cured ethylene vinyl acetate rubber, full sulphurated siliastic and vulcanize fourth entirely
At least one of benzene pyrrole rubber；Preferably vulcanize butadiene-styrene rubber and/or full sulphurated siliastic entirely.
10. Biaxially-oriented polyethylene antibacterial film described in any one of -5 according to claim 1, wherein the dispersing agent
For nanometer-level inorganic powder, it is preferably selected from nanoscale calcium carbonate, silica, montmorillonite, zinc oxide, talcum powder, titanium dioxide
At least one of titanium, carbon nanotube, graphene, carbon fiber, boron nitride, zirconium dioxide, wollastonite and zeolite；Further preferably
For nanometer grade calcium carbonate and/or nano grade gas phase silicon dioxide.
11. Biaxially-oriented polyethylene antibacterial film described in any one of -5 according to claim 1, wherein the guanidine salt is multiple
Antibacterial agent is closed to be made by method comprising the following steps:
A, guanidine salt polymer aqueous solution is contacted with the aqueous solution of zinc salt and/or mantoquita, forms transparent liquid mixture；
B, the resulting liquid mixture of step a is mixed with the latex solution after crosslinking by radiation, migration inhibitor is then added, obtains
To mixture；
C, the resulting mixture of step b is spray-dried, obtains solid powder, then with dispersant, obtained described
Guanidine salt complex antimicrobials；
Preferably, the mass concentration of the guanidine salt polymer aqueous solution is 10%~40%, preferably 15%~25%；The zinc
The mass concentration of the aqueous solution of salt and/or mantoquita is 15%~30%, preferably 20%~25%；The quality of the latex solution
Concentration is 30%~40%.
12. the preparation method of Biaxially-oriented polyethylene antibacterial film described in any one of claim 1-11, feature exist
In, method includes the following steps:
A, polyvinyl resin and guanidine salt complex antimicrobials and optional mould inhibitor and/or other auxiliary agents are uniformly mixed, then will
Uniformly mixed material melts are kneaded and extruding pelletization, obtain antimicrobial surface layer raw material；
B, the antimicrobial surface layer raw material and polyethylene raw material are sent into the extrusion casting apparatus with multi-layer co-extruded structure and are squeezed
Be cast out, obtain include polyethylene core and be attached to the polyethylene core an at least side surface antimicrobial surface layer stream
Prolong sheet material；
C, obtained cast-sheet is subjected to biaxial tension, obtains the Biaxial tension polyethylene film.
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