CN109776923A - A kind of transparent antibacterial film for marine product transport - Google Patents
A kind of transparent antibacterial film for marine product transport Download PDFInfo
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- CN109776923A CN109776923A CN201910116265.0A CN201910116265A CN109776923A CN 109776923 A CN109776923 A CN 109776923A CN 201910116265 A CN201910116265 A CN 201910116265A CN 109776923 A CN109776923 A CN 109776923A
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Abstract
The present invention relates to polymeric packaging material technical fields, more particularly to a kind of transparent antibacterial film for marine product transport, it is prepared from the following raw materials in parts by weight: 40-55 parts of polyethylene, 20-30 parts of polyvinylidene chloride, 15-20 parts of ethyl 2-methacrylate, 7-12 parts of acrylic resin, polyamide/25-35 parts of noble metal quantum dot composite material, 8-14 parts of Ag- chitosan anti-bacteria particle, 3-7 parts of acid fiber by polylactic, 7-11 parts of graphene oxide, 3-7 parts of organo montmorillonite, 2-5 parts of activated alumina, 3-6 parts of silica, 2-4 parts of surfactant.Transparent antibacterial film for marine product transport of the invention has good anti-bacterial effect, blocks gas permeability strong, and the antibacterial film has stronger tensile strength and impact strength, can meet marine product transportation demand.
Description
Technical field
The present invention relates to polymeric packaging material technical fields, and in particular to a kind of transparent antibacterial for marine product transport
Film.
Background technique
China's marine product is abundant, and as economy continues to develop, people's living standard is continuously improved, and resident is to marine product.
Demand it is increasing, but marine product transport just becomes the key link for wherein comparing, because consumption is wished
The marine product bought is fresher, is more able to maintain and goes back that product is genuine and high-quality, this just must be preferable in marine product transport
Fresh-keeping tool.
And traditional marine product transport is mostly fresh-keeping using common polybag progress, but the polybag cracky, causes
Fresh-keeping effect is not achieved by external environment destruction in marine product, and conventional plastic bag barrier property is poor, and shelf life of products is short,
Internal easy endophytic bacteria causes to go bad fast, not easy to maintain.
And based on the above issues, it is necessary to a kind of transparent antibacterial film for being exclusively used in marine product transport is developed, to solve to pass
Unite plastic barrier it is poor, shelf life of products is short, internal easy endophytic bacteria, it is not easy to maintain the problems such as.
Based on this, inventor retrieves the prior art, public in Chinese Patent Application No. 201711204908.4
Opened a kind of antimicrobial form transparent explosion-proof film, using polyethylene terephthalate as main material, in conjunction with by polyurethane resin,
PMMA particle, ethyl 2-methacrylate, polyimides and polyetheretherketonefiber fiber at high temperature with epoxy glue made of ethylene glycol
Liquid, using organo montmorillonite, active organosilicon, graphene, indium oxide, zinc oxide and stannic oxide as filler and poly terephthalic acid
Glycol ester glue and mixed glue solution mix after adding aldol condensation catalyst, and nanometer silver antimicrobial is sprayed after film forming
Liquid can be prepared by transparent membrane wear-resisting, that light transmittance is high, have the advantages that strong explosion-proof capabilities, good anti-bacterial effect and appearance are clear.
But this, which has the nanometer silver antimicrobial liquid of antibacterial action, is attached on film by spraying method, adhesive force is insufficient, makes for a long time
After being scraped with the rear or film, which can fall off, to influence the antibacterial effect of the film.
And a kind of super transparent EVA film of antibacterial and its preparation side are provided in Chinese Patent Application No. 201610807208.3
Method, including nano silica, the nano silica have the little particle of good light transmittance, film can be made to become
Densification helps to improve the transparency of plastic foil；It also added silver-based inorganic antibacterial agent in raw material, in the high transparency for guaranteeing film
Property while have broad spectrum antibacterial.The program be realize the anti-microbial property of film by the way that silver-based inorganic antibacterial agent is added, and
By the silver-based inorganic antibacterial agent with EVA is compound be blended by way of, solve in above-mentioned application number 201711204908.4
Nanometer silver antimicrobial layer falls off problem, but the silver-based inorganic antibacterial agent is largely filled in EVA, and only small part is exposed to film
Antibacterial is played the role of on surface, and antibacterial action is limited, meanwhile, the tensile strength of the EVA film, wear-resisting, impact strength and blocking are saturating
Gas is not all satisfied the requirement of the transparent antibacterial film of marine product transport.
Based on above-mentioned the deficiencies in the prior art, the present invention provides a kind of transparent antibacterial films for marine product transport, resist
Bacterium effect is good, blocks gas permeability strong, and the antibacterial film has stronger tensile strength, impact strength and wearability, can meet sea
Product transport is required with preservative film.
Summary of the invention
In order to solve the problems in the existing technology, the present invention provides a kind of transparent antibacterials for marine product transport
Film has good anti-bacterial effect, blocks gas permeability strong, and the antibacterial film has stronger tensile strength and impact strength, can meet
Marine product transportation demand.
It is of the existing technology in order to solve the problems, such as, it adopts the following technical scheme that
A kind of transparent antibacterial film for marine product transport, the transparent antibacterial film are prepared from the following raw materials in parts by weight:
40-55 parts of polyethylene, 15-20 parts of ethyl 2-methacrylate, 7-12 parts of acrylic resin, gathers 20-30 parts of polyvinylidene chloride
Amide/25-35 parts of noble metal quantum dot composite material, 8-14 parts of Ag- chitosan anti-bacteria particle, 3-7 parts of acid fiber by polylactic, oxidation
7-11 parts of graphene, 3-7 parts of organo montmorillonite, 2-5 parts of activated alumina, 3-6 parts of silica, 2-4 parts of surfactant.
The transparent antibacterial film is prepared from the following raw materials in parts by weight in one of the embodiments: 48 parts of polyethylene gathers
25 parts of vinylidene chloride, 18 parts of ethyl 2-methacrylate, 9.5 parts of acrylic resin, polyamide/noble metal quantum dot composite wood
30 parts of material, 11 parts of Ag- chitosan anti-bacteria particle, 5 parts of acid fiber by polylactic, 9 parts of graphene oxide, 5.5 parts of organo montmorillonite, activity
3.5 parts of aluminium oxide, 4.5 parts of silica, 3 parts of surfactant.
In one of the embodiments, the polyamide/noble metal quantum dot composite material the preparation method comprises the following steps:
(1) polyaniline is placed in aqueous formic acid, carries out ultrasonic agitation stirring, temperature is then risen to 80-90 DEG C again
High-speed stirred to polyaniline is carried out to be completely dissolved；
(2) silane coupling agent is added in Xiang Shangshu solution, the 120-140 DEG C of heating water bath 10-15min under ultrasound, then
Vacuum distillation removes formic acid removal and water, then is washed to neutrality with distillation, in an oven under the conditions of 60 DEG C it is dry for 24 hours, obtain modified gather
Amide；
(3) modified polyamide is sent into mixer, vacuumizes guarantee and atm difference >=0.07MPa, smelting temperature is
150-170 DEG C, after mixing 12-16min, the noble metal quantum dot that will account for modified polyamide gross mass 1/10 is added in mixer,
Mixing 6-10min together, discharge；
(4) the mixture cooled to room temperature that upper step is discharged, and be sent in electron beam irradiation, in 0.7-
20-30min is reacted under the irradiation energy of 0.9MeV to get polyamide/noble metal quantum dot composite material.
The noble metal quantum dot is Pt noble metal quantum dot, Au noble metal quantum in one of the embodiments,
Point, Pd noble metal quantum dot or Ag noble metal quantum dot.
In one of the embodiments, the Ag- chitosan anti-bacteria particle the preparation method comprises the following steps:
(1) chitosan is placed in acetic acid aqueous solution, carries out ultrasonic agitation stirring, it is poly- to shell then to carry out high-speed stirred again
Sugar is completely dissolved；
(2) under ultrasonic agitation, silver nitrate aqueous solution is added dropwise in the chitosan solution that obtains to step (1), is added dropwise
It stirs evenly, then vacuum distillation removes acetic acid and water；
(3) step (2) products therefrom is sent into pelletizer and is granulated to get Ag- chitosan anti-bacteria particle.
The surfactant is dodecyl sodium sulfate, lauryl sodium sulfate or spits in one of the embodiments,
Temperature 80.
The present invention also provides the preparations of the above-mentioned transparent antibacterial film for marine product transport in one of the embodiments,
Method, comprising the following steps:
(1) polyamide/noble metal quantum dot composite material is taken to be added in drying machine, and by the air of dryer inner into
The dry 3-4h of row, so that air themperature is 120 DEG C, air humidity 0.03%, then by the polyamide after drying process/your gold
Belong to quantum dot composite material to be transferred in reaction kettle, and the temperature of reaction kettle is adjusted to 185-205 DEG C, and surface-active is added
Agent, so that polyamide/noble metal quantum dot composite material, which melts, is made polyamide/noble metal quantum dot composite glue solution, it is spare；
(2) it takes graphene oxide, organo montmorillonite, activated alumina, silica to be added in ball mill, passes through ball milling
The mixing of 200 mesh is made so that above-mentioned material is uniformly mixed in mechanical milling process in the ball milling processing that machine persistently carries out 30-50min
Then mixed-powder obtained is added in step (1) reaction kettle by powder, starting blender is stirred with the revolving speed of 100rpm
It mixes, so that mixed-powder and polyamide/noble metal quantum dot composite glue solution are uniformly mixed, rubber cement is made, it is spare；
(3) it takes polyethylene, polyvinylidene chloride, ethyl 2-methacrylate, acrylic resin to be added to another to be used for
In the reaction kettle of melt-processed, and temperature is adjusted to 135-155 DEG C, and starts blender simultaneously and stirred with the revolving speed of 50rpmm
Then 20-30min adds acid fiber by polylactic, stir 5-10min, and mixed glue solution is made, spare；
(4) rubber cement is made in step (2) to be added in the mixed glue solution in step (3), starts blender with the revolving speed of 80rpm
30-50min is stirred, mixed mortar is made；
(5) Ag- chitosan anti-bacteria particle is distributed on glass panel, then by step (4) mixed mortar in glass panel
It is upper to be slowly cast, mixed mortar is evenly laid out on glass panels, meanwhile, it is poly- that Ag- shell is evenly distributed on mixed mortar surface
Then sugared antibacterial granule suppresses mixed mortar using pressing plate, then stand cooling to get the transparent antibacterial film.
The revolving speed of the ball mill in the step (2) is 300-400rpm in one of the embodiments,.
Compared with prior art, the present invention it has the advantages that
Transparent antibacterial film for marine product transport of the invention, has good anti-bacterial effect, blocks gas permeability strong, and this is anti-
Mycoderm has stronger tensile strength and impact strength, specifically: the polyamide of addition/noble metal quantum dot composite material has
Tridimensional network, and open tridimensional network by adding surfactant, and graphene oxide, organic illiteracy are taken off
The fillers such as soil, activated alumina, silica fill the tridimensional network, realize to the cladding of filler, make to tie between filler
That closes is even closer, thus improve transparent antibacterial film tensile strength of the invention, impact strength and block permeability, in addition,
By melting polyethylene, polyvinylidene chloride, ethyl 2-methacrylate, acrylic resin for glue, improve it is above-mentioned at
/ binding force, and acid fiber by polylactic is added in the glue, by being mutually intertwined and connected between acid fiber by polylactic, improves
The impact strength of glue, meanwhile, glass panel is distributed in using Ag- chitosan anti-bacteria particle, and by mixed mortar in glass surface
It is slowly cast on plate, realizes that Ag- chitosan anti-bacteria particle is embedded on the transparent antibacterial film, also, by resisting Ag- chitosan
Bacterium particle is distributed in mixed mortar surface, which is embedded under the effect of gravity and is bonded in transparent antibacterial
On film, which is bonded in transparent antibacterial film surface, can preferably bond with transparent antibacterial film, and the Ag-
Chitosan anti-bacteria particle is predominantly located in transparent antibacterial film surface, can play preferable antibacterial effect, to solve the prior art
In when antibacterial agent bonding surface is easy to fall off and antibacterial agent compound blending, small part is exposed to film surface, and antibacterial action is limited
Problem.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Clear, complete description.Obviously, the described embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.
Based on the embodiments of the present invention, those of ordinary skill in the art obtained institute without making creative work
There are other embodiments, belongs to the range that the present invention is protected.
Transparent antibacterial film in the prior art has the problem that the nanometer silver antimicrobial liquid of antibacterial action in the prior art
It is to be attached on film by spraying method, adhesive force is insufficient, and after long-time use or after the film scraped, the nano silver is anti-
Bacterium layer can fall off, thus influence the film antibacterial effect and silver-based inorganic antibacterial agent with high-molecular organic material is compound is blended
When, only small part is exposed to film surface, plays the role of antibacterial, and antibacterial action is limited, and the drawing of existing transparent antibacterial film
Stretch the requirement of intensity, wear-resisting, impact strength and the transparent antibacterial film for blocking gas permeability not to be all satisfied marine product transport.
Main idea is that: the present invention is had three-dimensional netted using polyamide/noble metal quantum dot composite material
The fillers such as graphene oxide, organo montmorillonite, activated alumina, silica are filled the tridimensional network by structure, are realized
To the cladding of filler, make to combine between filler it is even closer, thus improve transparent antibacterial film tensile strength of the invention, impact
Intensity and blocking permeability, meanwhile, glass panel is distributed in using Ag- chitosan anti-bacteria particle, and by mixed mortar in glass
It is slowly cast on glass panel, realizes that Ag- chitosan anti-bacteria particle is embedded on the transparent antibacterial film, also, by gathering Ag- shell
Sugared antibacterial granule is distributed in mixed mortar surface, which is embedded under the effect of gravity and is bonded in transparent
On antibacterial film, which is bonded in transparent antibacterial film surface, can preferably bond with transparent antibacterial film, and
The Ag- chitosan anti-bacteria particle is predominantly located in transparent antibacterial film surface, can play preferable antibacterial effect.
The advantages of this programme is as follows: the transparent antibacterial film for marine product transport of the invention has good anti-bacterial effect, resistance
Disconnected gas permeability is strong, and the antibacterial film has stronger tensile strength, impact strength and wearability, can meet marine product transport need
It asks.
The transparent antibacterial film for marine product transport of the invention is described further below with reference to embodiment 1-5.
Embodiment 1
The present embodiment for marine product transport transparent antibacterial film, the transparent antibacterial film by following weight proportion raw material
It is made: 40 parts of polyethylene, 20 parts of polyvinylidene chloride, 15 parts of ethyl 2-methacrylate, 7 parts of acrylic resin, polyamide/expensive
It is 25 parts of metal quantum point composite material, 8 parts of Ag- chitosan anti-bacteria particle, 3 parts of acid fiber by polylactic, 7 parts of graphene oxide, organic
3 parts of montmorillonite, 2 parts of activated alumina, 3 parts of silica, 2 parts of surfactant.
Wherein, the polyamide/noble metal quantum dot composite material the preparation method comprises the following steps:
(1) polyaniline is placed in aqueous formic acid, carries out ultrasonic agitation stirring, temperature is then risen to 80 DEG C and is carried out again
High-speed stirred to polyaniline is completely dissolved；
(2) silane coupling agent is added in Xiang Shangshu solution, 120 DEG C of heating water bath 10min, are then evaporated under reduced pressure under ultrasound
Be washed to neutrality except formic acid removal and water, then with distillation, in an oven under the conditions of 60 DEG C it is dry for 24 hours, obtain modified polyamide；
(3) modified polyamide is sent into mixer, vacuumizes guarantee and atm difference >=0.07MPa, smelting temperature is
150 DEG C, after mixing 12min, the noble metal quantum dot that will account for modified polyamide gross mass 1/10 is added in mixer, mixing together
6min, discharge；
(4) the mixture cooled to room temperature that upper step is discharged, and be sent in electron beam irradiation, in 0.7MeV
Irradiation energy under react 20min to get polyamide/noble metal quantum dot composite material.
Wherein, the noble metal quantum dot is Pt noble metal quantum dot.
Wherein, the Ag- chitosan anti-bacteria particle the preparation method comprises the following steps:
(1) chitosan is placed in acetic acid aqueous solution, carries out ultrasonic agitation stirring, it is poly- to shell then to carry out high-speed stirred again
Sugar is completely dissolved；
(2) under ultrasonic agitation, silver nitrate aqueous solution is added dropwise in the chitosan solution that obtains to step (1), is added dropwise
It stirs evenly, then vacuum distillation removes acetic acid and water；
(3) step (2) products therefrom is sent into pelletizer and is granulated to get Ag- chitosan anti-bacteria particle.
Wherein, the surfactant is dodecyl sodium sulfate.
Wherein, including following the present invention also provides the preparation method of the above-mentioned transparent antibacterial film for marine product transport
Step:
(1) polyamide/noble metal quantum dot composite material is taken to be added in drying machine, and by the air of dryer inner into
The dry 3h of row, so that air themperature is 120 DEG C, air humidity 0.03%, then by polyamide/noble metal after drying process
Quantum dot composite material is transferred in reaction kettle, and the temperature of reaction kettle is adjusted to 185 DEG C, and surfactant is added, and is made
It obtains polyamide/noble metal quantum dot composite material and melts obtained polyamide/noble metal quantum dot composite glue solution, it is spare；
(2) it takes graphene oxide, organo montmorillonite, activated alumina, silica to be added in ball mill, passes through ball milling
The mixed powder of 200 mesh is made so that above-mentioned material is uniformly mixed in mechanical milling process in the ball milling processing that machine persistently carries out 30min
Then mixed-powder obtained is added in step (1) reaction kettle by end, starting blender is stirred with the revolving speed of 100rpm
It mixes, so that mixed-powder and polyamide/noble metal quantum dot composite glue solution are uniformly mixed, rubber cement is made, it is spare；
(3) it takes polyethylene, polyvinylidene chloride, ethyl 2-methacrylate, acrylic resin to be added to another to be used for
In the reaction kettle of melt-processed, and temperature is adjusted to 135 DEG C, and starts blender simultaneously and stirred with the revolving speed of 50rpmm
Then 20min adds acid fiber by polylactic, stir 5min, and mixed glue solution is made, spare；
(4) rubber cement is made in step (2) to be added in the mixed glue solution in step (3), starts blender with the revolving speed of 80rpm
30min is stirred, mixed mortar is made；
(5) Ag- chitosan anti-bacteria particle is distributed on glass panel, then by step (4) mixed mortar in glass panel
It is upper to be slowly cast, mixed mortar is evenly laid out on glass panels, meanwhile, it is poly- that Ag- shell is evenly distributed on mixed mortar surface
Then sugared antibacterial granule suppresses mixed mortar using pressing plate, then stand cooling to get the transparent antibacterial film.
Wherein, the revolving speed of the ball mill in the step (2) is 300rpm.
Embodiment 2
The present embodiment for marine product transport transparent antibacterial film, the transparent antibacterial film by following weight proportion raw material
It is made: 55 parts of polyethylene, 30 parts of polyvinylidene chloride, 20 parts of ethyl 2-methacrylate, 12 parts of acrylic resin, polyamide/
35 parts of noble metal quantum dot composite material, 14 parts of Ag- chitosan anti-bacteria particle, 7 parts of acid fiber by polylactic, 11 parts of graphene oxide,
7 parts of organo montmorillonite, 5 parts of activated alumina, 6 parts of silica, 4 parts of surfactant.
Wherein, the polyamide/noble metal quantum dot composite material the preparation method comprises the following steps:
(1) polyaniline is placed in aqueous formic acid, carries out ultrasonic agitation stirring, temperature is then risen to 90 DEG C and is carried out again
High-speed stirred to polyaniline is completely dissolved；
(2) silane coupling agent is added in Xiang Shangshu solution, 140 DEG C of heating water bath 15min, are then evaporated under reduced pressure under ultrasound
Be washed to neutrality except formic acid removal and water, then with distillation, in an oven under the conditions of 60 DEG C it is dry for 24 hours, obtain modified polyamide；
(3) modified polyamide is sent into mixer, vacuumizes guarantee and atm difference >=0.07MPa, smelting temperature is
170 DEG C, after mixing 16min, the noble metal quantum dot that will account for modified polyamide gross mass 1/10 is added in mixer, mixing together
10min, discharge；
(4) the mixture cooled to room temperature that upper step is discharged, and be sent in electron beam irradiation, in 0.9MeV
Irradiation energy under react 30min to get polyamide/noble metal quantum dot composite material.
Wherein, the noble metal quantum dot is Ag noble metal quantum dot.
Wherein, the Ag- chitosan anti-bacteria particle the preparation method comprises the following steps:
(1) chitosan is placed in acetic acid aqueous solution, carries out ultrasonic agitation stirring, it is poly- to shell then to carry out high-speed stirred again
Sugar is completely dissolved；
(2) under ultrasonic agitation, silver nitrate aqueous solution is added dropwise in the chitosan solution that obtains to step (1), is added dropwise
It stirs evenly, then vacuum distillation removes acetic acid and water；
(3) step (2) products therefrom is sent into pelletizer and is granulated to get Ag- chitosan anti-bacteria particle.
Wherein, the surfactant is lauryl sodium sulfate.
Wherein, including following the present invention also provides the preparation method of the above-mentioned transparent antibacterial film for marine product transport
Step:
(1) polyamide/noble metal quantum dot composite material is taken to be added in drying machine, and by the air of dryer inner into
The dry 4h of row, so that air themperature is 120 DEG C, air humidity 0.03%, then by polyamide/noble metal after drying process
Quantum dot composite material is transferred in reaction kettle, and the temperature of reaction kettle is adjusted to 185-205 DEG C, and surface-active is added
Agent, so that polyamide/noble metal quantum dot composite material, which melts, is made polyamide/noble metal quantum dot composite glue solution, it is spare；
(2) it takes graphene oxide, organo montmorillonite, activated alumina, silica to be added in ball mill, passes through ball milling
The mixed powder of 200 mesh is made so that above-mentioned material is uniformly mixed in mechanical milling process in the ball milling processing that machine persistently carries out 50min
Then mixed-powder obtained is added in step (1) reaction kettle by end, starting blender is stirred with the revolving speed of 100rpm
It mixes, so that mixed-powder and polyamide/noble metal quantum dot composite glue solution are uniformly mixed, rubber cement is made, it is spare；
(3) it takes polyethylene, polyvinylidene chloride, ethyl 2-methacrylate, acrylic resin to be added to another to be used for
In the reaction kettle of melt-processed, and temperature is adjusted to 155 DEG C, and starts blender simultaneously and stirred with the revolving speed of 50rpmm
Then 30min adds acid fiber by polylactic, stir 10min, and mixed glue solution is made, spare；
(4) rubber cement is made in step (2) to be added in the mixed glue solution in step (3), starts blender with the revolving speed of 80rpm
50min is stirred, mixed mortar is made；
(5) Ag- chitosan anti-bacteria particle is distributed on glass panel, then by step (4) mixed mortar in glass panel
It is upper to be slowly cast, mixed mortar is evenly laid out on glass panels, meanwhile, it is poly- that Ag- shell is evenly distributed on mixed mortar surface
Then sugared antibacterial granule suppresses mixed mortar using pressing plate, then stand cooling to get the transparent antibacterial film.
Wherein, the revolving speed of the ball mill in the step (2) is 400rpm.
Embodiment 3
The present embodiment for marine product transport transparent antibacterial film, the transparent antibacterial film by following weight proportion raw material
It is made: 48 parts of polyethylene, 25 parts of polyvinylidene chloride, 18 parts of ethyl 2-methacrylate, 9.5 parts of acrylic resin, polyamide/
30 parts of noble metal quantum dot composite material, 5 parts of acid fiber by polylactic, 9 parts of graphene oxide, has 11 parts of Ag- chitosan anti-bacteria particle
5.5 parts of machine montmorillonite, 3.5 parts of activated alumina, 4.5 parts of silica, 3 parts of surfactant.
Wherein, the polyamide/noble metal quantum dot composite material the preparation method comprises the following steps:
(1) polyaniline is placed in aqueous formic acid, carries out ultrasonic agitation stirring, temperature is then risen to 85 DEG C and is carried out again
High-speed stirred to polyaniline is completely dissolved；
(2) silane coupling agent is added in Xiang Shangshu solution, 130 DEG C of heating water bath 13min, are then evaporated under reduced pressure under ultrasound
Be washed to neutrality except formic acid removal and water, then with distillation, in an oven under the conditions of 60 DEG C it is dry for 24 hours, obtain modified polyamide；
(3) modified polyamide is sent into mixer, vacuumizes guarantee and atm difference >=0.07MPa, smelting temperature is
160 DEG C, after mixing 14min, the noble metal quantum dot that will account for modified polyamide gross mass 1/10 is added in mixer, mixing together
8min, discharge；
(4) the mixture cooled to room temperature that upper step is discharged, and be sent in electron beam irradiation, in 0.8MeV
Irradiation energy under react 25min to get polyamide/noble metal quantum dot composite material.
Wherein, the noble metal quantum dot is Au noble metal quantum dot.
Wherein, the Ag- chitosan anti-bacteria particle the preparation method comprises the following steps:
(1) chitosan is placed in acetic acid aqueous solution, carries out ultrasonic agitation stirring, it is poly- to shell then to carry out high-speed stirred again
Sugar is completely dissolved；
(2) under ultrasonic agitation, silver nitrate aqueous solution is added dropwise in the chitosan solution that obtains to step (1), is added dropwise
It stirs evenly, then vacuum distillation removes acetic acid and water；
(3) step (2) products therefrom is sent into pelletizer and is granulated to get Ag- chitosan anti-bacteria particle.
Wherein, the surfactant is Tween 80.
Wherein, including following the present invention also provides the preparation method of the above-mentioned transparent antibacterial film for marine product transport
Step:
(1) polyamide/noble metal quantum dot composite material is taken to be added in drying machine, and by the air of dryer inner into
The dry 3.5h of row, so that air themperature is 120 DEG C, air humidity 0.03%, then by the polyamide after drying process/your gold
Belong to quantum dot composite material to be transferred in reaction kettle, and the temperature of reaction kettle be adjusted to 195 DEG C, and surfactant is added,
So that polyamide/noble metal quantum dot composite material, which melts, is made polyamide/noble metal quantum dot composite glue solution, it is spare；
(2) it takes graphene oxide, organo montmorillonite, activated alumina, silica to be added in ball mill, passes through ball milling
The mixed powder of 200 mesh is made so that above-mentioned material is uniformly mixed in mechanical milling process in the ball milling processing that machine persistently carries out 40min
Then mixed-powder obtained is added in step (1) reaction kettle by end, starting blender is stirred with the revolving speed of 100rpm
It mixes, so that mixed-powder and polyamide/noble metal quantum dot composite glue solution are uniformly mixed, rubber cement is made, it is spare；
(3) it takes polyethylene, polyvinylidene chloride, ethyl 2-methacrylate, acrylic resin to be added to another to be used for
In the reaction kettle of melt-processed, and temperature is adjusted to 145 DEG C, and starts blender simultaneously and stirred with the revolving speed of 50rpmm
Then 25min adds acid fiber by polylactic, stir 7.5min, and mixed glue solution is made, spare；
(4) rubber cement is made in step (2) to be added in the mixed glue solution in step (3), starts blender with the revolving speed of 80rpm
40min is stirred, mixed mortar is made；
(5) Ag- chitosan anti-bacteria particle is distributed on glass panel, then by step (4) mixed mortar in glass panel
It is upper to be slowly cast, mixed mortar is evenly laid out on glass panels, meanwhile, it is poly- that Ag- shell is evenly distributed on mixed mortar surface
Then sugared antibacterial granule suppresses mixed mortar using pressing plate, then stand cooling to get the transparent antibacterial film.
Wherein, the revolving speed of the ball mill in the step (2) is 350rpm.
Embodiment 4
The present embodiment for marine product transport transparent antibacterial film, the transparent antibacterial film by following weight proportion raw material
It is made: 44 parts of polyethylene, 23 parts of polyvinylidene chloride, 16 parts of ethyl 2-methacrylate, 8 parts of acrylic resin, polyamide/expensive
It is 28 parts of metal quantum point composite material, 9 parts of Ag- chitosan anti-bacteria particle, 4 parts of acid fiber by polylactic, 8 parts of graphene oxide, organic
4 parts of montmorillonite, 3 parts of activated alumina, 4 parts of silica, 2.5 parts of surfactant.
Wherein, the polyamide/noble metal quantum dot composite material the preparation method comprises the following steps:
(1) polyaniline is placed in aqueous formic acid, carries out ultrasonic agitation stirring, temperature is then risen to 80-90 DEG C again
High-speed stirred to polyaniline is carried out to be completely dissolved；
(2) silane coupling agent is added in Xiang Shangshu solution, 125 DEG C of heating water bath 11min, are then evaporated under reduced pressure under ultrasound
Be washed to neutrality except formic acid removal and water, then with distillation, in an oven under the conditions of 60 DEG C it is dry for 24 hours, obtain modified polyamide；
(3) modified polyamide is sent into mixer, vacuumizes guarantee and atm difference >=0.07MPa, smelting temperature is
155 DEG C, after mixing 13min, the noble metal quantum dot that will account for modified polyamide gross mass 1/10 is added in mixer, mixing together
7min, discharge；
(4) the mixture cooled to room temperature that upper step is discharged, and be sent in electron beam irradiation, in 0.8MeV
Irradiation energy under react 222min to get polyamide/noble metal quantum dot composite material.
Wherein, the noble metal quantum dot is Pd noble metal quantum dot.
Wherein, the Ag- chitosan anti-bacteria particle the preparation method comprises the following steps:
(1) chitosan is placed in acetic acid aqueous solution, carries out ultrasonic agitation stirring, it is poly- to shell then to carry out high-speed stirred again
Sugar is completely dissolved；
(2) under ultrasonic agitation, silver nitrate aqueous solution is added dropwise in the chitosan solution that obtains to step (1), is added dropwise
It stirs evenly, then vacuum distillation removes acetic acid and water；
(3) step (2) products therefrom is sent into pelletizer and is granulated to get Ag- chitosan anti-bacteria particle.
Wherein, the surfactant is dodecyl sodium sulfate.
Wherein, including following the present invention also provides the preparation method of the above-mentioned transparent antibacterial film for marine product transport
Step:
(1) polyamide/noble metal quantum dot composite material is taken to be added in drying machine, and by the air of dryer inner into
The dry 3.3h of row, so that air themperature is 120 DEG C, air humidity 0.03%, then by the polyamide after drying process/your gold
Belong to quantum dot composite material to be transferred in reaction kettle, and the temperature of reaction kettle be adjusted to 190 DEG C, and surfactant is added,
So that polyamide/noble metal quantum dot composite material, which melts, is made polyamide/noble metal quantum dot composite glue solution, it is spare；
(2) it takes graphene oxide, organo montmorillonite, activated alumina, silica to be added in ball mill, passes through ball milling
The mixed powder of 200 mesh is made so that above-mentioned material is uniformly mixed in mechanical milling process in the ball milling processing that machine persistently carries out 35min
Then mixed-powder obtained is added in step (1) reaction kettle by end, starting blender is stirred with the revolving speed of 100rpm
It mixes, so that mixed-powder and polyamide/noble metal quantum dot composite glue solution are uniformly mixed, rubber cement is made, it is spare；
(3) it takes polyethylene, polyvinylidene chloride, ethyl 2-methacrylate, acrylic resin to be added to another to be used for
In the reaction kettle of melt-processed, and temperature is adjusted to 140 DEG C, and starts blender simultaneously and stirred with the revolving speed of 50rpmm
Then 22min adds acid fiber by polylactic, stir 6min, and mixed glue solution is made, spare；
(4) rubber cement is made in step (2) to be added in the mixed glue solution in step (3), starts blender with the revolving speed of 80rpm
35min is stirred, mixed mortar is made；
(5) Ag- chitosan anti-bacteria particle is distributed on glass panel, then by step (4) mixed mortar in glass panel
It is upper to be slowly cast, mixed mortar is evenly laid out on glass panels, meanwhile, it is poly- that Ag- shell is evenly distributed on mixed mortar surface
Then sugared antibacterial granule suppresses mixed mortar using pressing plate, then stand cooling to get the transparent antibacterial film.
Wherein, the revolving speed of the ball mill in the step (2) is 330rpm.
Embodiment 5
The present embodiment for marine product transport transparent antibacterial film, the transparent antibacterial film by following weight proportion raw material
It is made: 52 parts of polyethylene, 28 parts of polyvinylidene chloride, 19 parts of ethyl 2-methacrylate, 11 parts of acrylic resin, polyamide/
32 parts of noble metal quantum dot composite material, 12 parts of Ag- chitosan anti-bacteria particle, 6 parts of acid fiber by polylactic, 10 parts of graphene oxide,
6 parts of organo montmorillonite, 4 parts of activated alumina, 5 parts of silica, 3.5 parts of surfactant.
Wherein, the polyamide/noble metal quantum dot composite material the preparation method comprises the following steps:
(1) polyaniline is placed in aqueous formic acid, carries out ultrasonic agitation stirring, temperature is then risen to 88 DEG C and is carried out again
High-speed stirred to polyaniline is completely dissolved；
(2) silane coupling agent is added in Xiang Shangshu solution, 135 DEG C of heating water bath 14min, are then evaporated under reduced pressure under ultrasound
Be washed to neutrality except formic acid removal and water, then with distillation, in an oven under the conditions of 60 DEG C it is dry for 24 hours, obtain modified polyamide；
(3) modified polyamide is sent into mixer, vacuumizes guarantee and atm difference >=0.07MPa, smelting temperature is
165 DEG C, after mixing 15min, the noble metal quantum dot that will account for modified polyamide gross mass 1/10 is added in mixer, mixing together
9min, discharge；
(4) the mixture cooled to room temperature that upper step is discharged, and be sent in electron beam irradiation, in 0.9MeV
Irradiation energy under react 28min to get polyamide/noble metal quantum dot composite material.
Wherein, the noble metal quantum dot is Ag noble metal quantum dot.
Wherein, the Ag- chitosan anti-bacteria particle the preparation method comprises the following steps:
(1) chitosan is placed in acetic acid aqueous solution, carries out ultrasonic agitation stirring, it is poly- to shell then to carry out high-speed stirred again
Sugar is completely dissolved；
(2) under ultrasonic agitation, silver nitrate aqueous solution is added dropwise in the chitosan solution that obtains to step (1), is added dropwise
It stirs evenly, then vacuum distillation removes acetic acid and water；
(3) step (2) products therefrom is sent into pelletizer and is granulated to get Ag- chitosan anti-bacteria particle.
Wherein, the surfactant is lauryl sodium sulfate.
Wherein, including following the present invention also provides the preparation method of the above-mentioned transparent antibacterial film for marine product transport
Step:
(1) polyamide/noble metal quantum dot composite material is taken to be added in drying machine, and by the air of dryer inner into
The dry 3.8h of row, so that air themperature is 120 DEG C, air humidity 0.03%, then by the polyamide after drying process/your gold
Belong to quantum dot composite material to be transferred in reaction kettle, and the temperature of reaction kettle be adjusted to 200 DEG C, and surfactant is added,
So that polyamide/noble metal quantum dot composite material, which melts, is made polyamide/noble metal quantum dot composite glue solution, it is spare；
(2) it takes graphene oxide, organo montmorillonite, activated alumina, silica to be added in ball mill, passes through ball milling
The mixed powder of 200 mesh is made so that above-mentioned material is uniformly mixed in mechanical milling process in the ball milling processing that machine persistently carries out 45min
Then mixed-powder obtained is added in step (1) reaction kettle by end, starting blender is stirred with the revolving speed of 100rpm
It mixes, so that mixed-powder and polyamide/noble metal quantum dot composite glue solution are uniformly mixed, rubber cement is made, it is spare；
(3) it takes polyethylene, polyvinylidene chloride, ethyl 2-methacrylate, acrylic resin to be added to another to be used for
In the reaction kettle of melt-processed, and temperature is adjusted to 150 DEG C, and starts blender simultaneously and stirred with the revolving speed of 50rpmm
Then 28min adds acid fiber by polylactic, stir 9min, and mixed glue solution is made, spare；
(4) rubber cement is made in step (2) to be added in the mixed glue solution in step (3), starts blender with the revolving speed of 80rpm
45min is stirred, mixed mortar is made；
(5) Ag- chitosan anti-bacteria particle is distributed on glass panel, then by step (4) mixed mortar in glass panel
It is upper to be slowly cast, mixed mortar is evenly laid out on glass panels, meanwhile, it is poly- that Ag- shell is evenly distributed on mixed mortar surface
Then sugared antibacterial granule suppresses mixed mortar using pressing plate, then stand cooling to get the transparent antibacterial film.
Wherein, the revolving speed of the ball mill in the step (2) is 380rpm.
Comparative example 1
Using antimicrobial form transparent explosion-proof film made from the method in Chinese patent (application number: CN201711204908.4).
Comparative example 2
Using the super transparent EVA film of antibacterial made from the method in Chinese patent (application number: CN201610807208.3).
Comparative example 3
In addition to changing polyamide/noble metal quantum dot composite material into polyamide, other material contents and preparation step are same
Embodiment 1 is consistent.
Comparative example 4
In addition to Ag- chitosan anti-bacteria particle is changed to mixed mortar blending method, other material contents and preparation step
It is consistent with embodiment 1.
Test example 1
Transparent antibacterial film made from transparent antibacterial film made from 1-5 of the embodiment of the present invention and comparative example 1-4 is subjected to resistance to punching
Hit intensity, OTR oxygen transmission rate, tensile strength and light transmittance test, specific test are shown in Table 1.
Table 1
As it can be seen from table 1 the impact resistant strength of transparent antibacterial film made from 1-5 of the embodiment of the present invention, OTR oxygen transmission rate,
Tensile strength and light transmittance are better than the prior art, and from comparative example 3 and comparative example 4 it is found that by adding into transparent antibacterial film
Entering polyamide/noble metal quantum dot composite material can be improved impact resistant strength, OTR oxygen transmission rate and tensile strength, and Ag- shell is poly-
Sugared antibacterial granule acts on the impact resistant strength of transparent antibacterial film, OTR oxygen transmission rate, tensile strength and light transmittance raising little.
Test example 2
Verify the transparent antibacterial film bactericidal effect of 1-5 of the embodiment of the present invention and comparative example 1-4 product.Its experimental condition are as follows:
2ml concentration is instilled in culture dish for the staphylococcus aureus of 1.0 × 107cfu/ml and Escherichia coli mixed bacteria liquid, then is fallen
Enter a certain amount of culture medium to be uniformly mixed, until place 1-5's of the embodiment of the present invention and comparative example 1-4 after cooling on culture medium
Culture medium, is then placed in insulating box and cultivates 24-48h by transparent antibacterial film, takes out and surveys its antibiotic rate, and concrete outcome is shown in Table 2.
Table 2
| Test item | Staphylococcus aureus (%) | Escherichia coli (%) |
| Embodiment 1 | 99.4 | 99.2 |
| Embodiment 2 | 99.6 | 99.4 |
| Embodiment 3 | 99.8 | 99.7 |
| Embodiment 4 | 99.6 | 99.5 |
| Embodiment 5 | 99.7 | 99.3 |
| Comparative example 1 | 96.5 | 95.8 |
| Comparative example 2 | 95.4 | 94.8 |
| Comparative example 3 | 99.2 | 99.1 |
| Comparative example 4 | 97.6 | 96.9 |
As shown in Table 2, transparent antibacterial film anti-microbial property made from 1-5 of the embodiment of the present invention be better than the prior art, also, by
Comparative example 4 reduces the anti-of the transparent antibacterial film of the present invention it is found that Ag- chitosan anti-bacteria particle is changed to mixed mortar blending method
Bacterium performance.
To sum up, the transparent antibacterial film for marine product transport of the invention has good anti-bacterial effect, blocks gas permeability strong, and
The antibacterial film has stronger tensile strength and impact strength, can meet marine product transportation demand.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (8)
1. a kind of transparent antibacterial film for marine product transport, which is characterized in that the transparent antibacterial film is by following weight proportion
Raw material is made: 40-55 parts of polyethylene, 20-30 parts of polyvinylidene chloride, 15-20 parts of ethyl 2-methacrylate, acrylic resin
7-12 parts, polyamide/25-35 parts of noble metal quantum dot composite material, 8-14 parts of Ag- chitosan anti-bacteria particle, acid fiber by polylactic
3-7 parts, 7-11 parts of graphene oxide, 3-7 parts of organo montmorillonite, 2-5 parts of activated alumina, 3-6 parts of silica, surface-active
2-4 parts of agent.
2. it is according to claim 1 for marine product transport transparent antibacterial film, which is characterized in that the transparent antibacterial film by
The raw material of following weight proportion is made: 48 parts of polyethylene, 25 parts of polyvinylidene chloride, 18 parts of ethyl 2-methacrylate, propylene
9.5 parts of acid resin, polyamide/30 parts of noble metal quantum dot composite material, 11 parts of Ag- chitosan anti-bacteria particle, acid fiber by polylactic 5
Part, 9 parts of graphene oxide, 5.5 parts of organo montmorillonite, 3.5 parts of activated alumina, 4.5 parts of silica, 3 parts of surfactant.
3. the transparent antibacterial film according to claim 1 for marine product transport, which is characterized in that the polyamide/expensive
Metal quantum point composite material the preparation method comprises the following steps:
(1) polyaniline is placed in aqueous formic acid, carries out ultrasonic agitation stirring, temperature is then risen to 80-90 DEG C and is carried out again
High-speed stirred to polyaniline is completely dissolved；
(2) silane coupling agent is added in Xiang Shangshu solution, 120-140 DEG C of heating water bath 10-15min, is then depressurized under ultrasound
Be distilled off formic acid and water, then be washed to neutrality with distillation, in an oven under the conditions of 60 DEG C it is dry for 24 hours, obtain modified polyamide；
(3) modified polyamide is sent into mixer, vacuumizes guarantee and atm difference >=0.07MPa, smelting temperature 150-
170 DEG C, after mixing 12-16min, the noble metal quantum dot that will account for modified polyamide gross mass 1/10 is added in mixer, together
Mixing 6-10min, discharge；
(4) the mixture cooled to room temperature that upper step is discharged, and be sent in electron beam irradiation, in 0.7-0.9MeV
Irradiation energy under react 20-30min to get polyamide/noble metal quantum dot composite material.
4. the transparent antibacterial film according to claim 3 for marine product transport, which is characterized in that the noble metal
Quantum dot is Pt noble metal quantum dot, Au noble metal quantum dot, Pd noble metal quantum dot or Ag noble metal quantum dot.
5. the transparent antibacterial film according to claim 1 for marine product transport, which is characterized in that the Ag- chitosan
Antibacterial granule the preparation method comprises the following steps:
(1) chitosan is placed in acetic acid aqueous solution, carries out ultrasonic agitation stirring, it is complete to chitosan then to carry out high-speed stirred again
Fully dissolved；
(2) under ultrasonic agitation, silver nitrate aqueous solution is added dropwise in the chitosan solution that obtains to step (1), stirring is added dropwise
Uniformly, then vacuum distillation removes acetic acid and water；
(3) step (2) products therefrom is sent into pelletizer and is granulated to get Ag- chitosan anti-bacteria particle.
6. the transparent antibacterial film according to claim 1 for marine product transport, which is characterized in that the surfactant
For dodecyl sodium sulfate, lauryl sodium sulfate or Tween 80.
7. the preparation method of the transparent antibacterial film according to claim 1-6 for marine product transport, feature
It is, comprising the following steps:
(1) it takes polyamide/noble metal quantum dot composite material to be added in drying machine, and the air of dryer inner is done
Dry 3-4h, so that air themperature is 120 DEG C, air humidity 0.03%, then by polyamide/noble metal amount after drying process
Son point composite material is transferred in reaction kettle, and the temperature of reaction kettle is adjusted to 185-205 DEG C, and surfactant is added,
So that polyamide/noble metal quantum dot composite material, which melts, is made polyamide/noble metal quantum dot composite glue solution, it is spare；
(2) it takes graphene oxide, organo montmorillonite, activated alumina, silica to be added in ball mill, is held by ball mill
The mixed powder of 200 mesh is made so that above-mentioned material is uniformly mixed in mechanical milling process in the continuous ball milling processing for carrying out 30-50min
Then mixed-powder obtained is added in step (1) reaction kettle by end, starting blender is stirred with the revolving speed of 100rpm
It mixes, so that mixed-powder and polyamide/noble metal quantum dot composite glue solution are uniformly mixed, rubber cement is made, it is spare；
(3) polyethylene, polyvinylidene chloride, ethyl 2-methacrylate, acrylic resin is taken to be added to another for melting
In the reaction kettle of processing, and temperature is adjusted to 135-155 DEG C, and starts blender simultaneously and 20- is stirred with the revolving speed of 50rpmm
Then 30min adds acid fiber by polylactic, stir 5-10min, and mixed glue solution is made, spare；
(4) rubber cement is made in step (2) to be added in the mixed glue solution in step (3), starts blender and is stirred with the revolving speed of 80rpm
Mixed mortar is made in 30-50min；
(5) Ag- chitosan anti-bacteria particle is distributed on glass panel, then by step (4) mixed mortar on glass panels into
Row is slowly cast, and mixed mortar is evenly laid out on glass panels, meanwhile, it is anti-that Ag- chitosan is evenly distributed on mixed mortar surface
Then bacterium particle suppresses mixed mortar using pressing plate, then stand cooling to get the transparent antibacterial film.
8. the preparation method of the transparent antibacterial film according to claim 7 for marine product transport, which is characterized in that described
The revolving speed of ball mill in step (2) is 300-400rpm.
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