CN105925175B - A kind of antibacterial environment protection film and preparation method thereof - Google Patents

A kind of antibacterial environment protection film and preparation method thereof Download PDF

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Publication number
CN105925175B
CN105925175B CN201610264755.1A CN201610264755A CN105925175B CN 105925175 B CN105925175 B CN 105925175B CN 201610264755 A CN201610264755 A CN 201610264755A CN 105925175 B CN105925175 B CN 105925175B
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parts
protection film
environment protection
coating
weight
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CN105925175A (en
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伍广科
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Guangdong baotexin New Material Technology Co.,Ltd.
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Foshan City Shunde District Letter Plastic Adhesive Products Co
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Priority to CN201710969085.8A priority Critical patent/CN107652884A/en
Priority to CN201610264755.1A priority patent/CN105925175B/en
Priority to CN201710969070.1A priority patent/CN107746673A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
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    • B32B27/00Layered products comprising a layer of synthetic resin
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    • B32LAYERED PRODUCTS
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    • C09D151/00Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/40Additives
    • C09D7/65Additives macromolecular
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/24All layers being polymeric
    • B32B2250/246All polymers belonging to those covered by groups B32B27/32 and B32B27/30
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/10Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/26Polymeric coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/714Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145Rot proof, resistant to bacteria, mildew, mould, fungi
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    • B32LAYERED PRODUCTS
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    • B32B2323/00Polyalkenes
    • B32B2323/04Polyethylene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00Polyesters, e.g. PET, i.e. polyethylene terephthalate
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    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
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Abstract

The invention discloses a kind of antibacterial environment protection film and preparation method thereof, the antibacterial environment protection film is pet layer successively from inside to outside, antibiotic layer, PE layers, sterilize coating, wherein, the antibiotic layer is by PLA, hydroxypropyl acrylate, acryloyl chloride, trifluoropropylmethyldichlorosilane, vinyl silane triisopropoxide, hydroxypropyl methyl cellulose, chitosan, eugenol, polyvinyl alcohol, emulsifying agent, what initiator and deionized water were formulated, the sterilization coating is by ethanol, polyethylene glycol, deionized water, cinnamic acid, beta cyclodextrin, titanate coupling agent, nano titanium oxide, organic siliconresin, what dispersant and defoamer were prepared.Antibacterial environment protection film prepared by the present invention has preferably sterilization antivirus effect, and durability is good, service life length, it is environmentally safe the advantages that.

Description

A kind of antibacterial environment protection film and preparation method thereof
Technical field
The invention belongs to thin film technique field, more particularly to a kind of antibacterial environment protection film and preparation method thereof.
Background technology
As scientific and technological progress and the fast development of modern industry, environmental problem are on the rise.With people focus more on it is strong Health and environmental consciousness is gradually stepped up, antibacterial to architectural glass film, the demand for purifying air are increasingly urgent.It is existing inorganic Although metal antibacterial coating has anti-microbial property, such as using Nano Silver as sterilization component, antibacterial time is short, easily occur oxidation and Lose, and be easy to contaminate dust, hygroscopic rotten, hardness is low to be easily damaged, and is easy to come off, and environmental-protecting performance is poor.Conventional antimicrobial Generally there is noxious material in agent, this carcinogen of formaldehyde can be produced after coating.
The content of the invention
In order to overcome the deficiencies in the prior art, the invention discloses a kind of antibacterial environment protection film and its preparation side Method, it is desirable to provide it is a kind of can antibacterial environmentally safe thin-film material again.
The present invention is realized by following technology:
A kind of antibacterial environment protection film, the antibacterial environment protection film are pet layer, antibiotic layer, PE layers, sterilization painting successively from inside to outside Layer.
As a further refinement of the present invention, thickness sum of the thickness of the antibiotic layer not less than pet layer and PE layers, The thickness of the sterilization coating is not less than the thickness of antibiotic layer, by pet layer, antibiotic layer, PE layers, sterilization coating superimposition order And the design of each layer thickness relationship, it is further ensured that the anti-microbial property of antibacterial environment protection film.
As a kind of preferred embodiment, the coating used in the antibiotic layer is formulated by the raw material of following parts by weight 's:
It is preferred that the emulsifying agent is preferably three phenethyl phenol polyethenoxy ethers, the initiator is preferably potassium sulfate.
Described PLA has good engineering properties and physical property.It is various that PLA is applied to blowing, thermoplastic etc. Processing method, application is quite varied, also possesses good glossiness and transparency, polylactic acid film have good gas permeability, Oxygen permeability and saturating carbon dioxide, it also has the characteristic of isolation smell.Virus and mould are easily attached to biological degradable membrane Surface, therefore have the doubt of safety and health, however, PLA is that uniquely have excellent antibacterial and anti-mildew characteristic biodegradable Film.
Described chitosan comes from chitin, and it is a kind of phytoalexin, has natural antibacterial, can suppress a variety of Fungi, the bacterium of food surface.
Described acryloyl chloride, the heat resistance of antibiotic layer is not only increased, while acryloyl chloride can be carried out with chitosan Crosslinked action, strengthen the bactericidal action of chitosan.
Described acetic acid can be very good dissolving chitosan and chitosan is dissolved into polymer, and preferred concentration is 0.1mol/L。
Described eugenol is the main component of caryophyllus oil, and primary efficacy is exactly antibacterial sterilization.
Described polyvinyl alcohol can improve the grafting efficiency of chitosan and methyl eugenol in PLA, pass through first The synergy of base eugenol and chitosan, improve the effect of antibacterial sterilization.
Described trifluoropropylmethyldichlorosilane improves the heat resistance of antibiotic layer.
As a further refinement of the present invention, the coating used in the antibacterial oxidant layer is to be prepared via a method which to form 's:
(1) prepared by pre-emulsion
By the PLA of corresponding parts by weight, hydroxypropyl acrylate, emulsifying agent, initiator, trifluoropropylmethyldichlorosilane, Vinyl silane triisopropoxide, polyvinyl alcohol mix with the deionized water of 1/2-3/4 parts by weight, and pre-emulsification obtains pre-emulsion;
(2) emulsion polymerization
By the hydroxypropyl methyl cellulose of corresponding parts by weight, chitosan, acetic acid (0.1M), eugenol and remaining deionization Water is added in reactor, and the material in reactor is stirred under the conditions of 300-400r/min and is warming up to 75-85 DEG C, then will be upper Pre-emulsion made from stating step (1) is added drop-wise in the reactor, and 1-2h is dripped off, and keeping temperature reacts 1-2h after dripping off, so After be warming up to 85-90 DEG C, continue insulation reaction 1h, be down to room temperature, discharging, filtering, obtain antibacterial coating.
As a kind of preferred embodiment, it is described sterilization coating used in coating be by following parts by weight raw material prepare and Into:
It is preferred that the dispersant is sodium citrate, the defoamer is organosilicon high effective antifoaming agent, is gathered by a variety of modifications Dimethyl siloxane and other refined high effective and modified organosilicon high effective antifoaming agents formed of efficiently defoaming component, from the rich defoaming of moral Agent factory.
Described cinnamyl alcohol also known as 3- phenylacroleins, cinnamic acid is nontoxic to human body or less toxic as antimildew agent for food, and Stronger inhibitory action can be played to the growth and breeding of microorganism, to aspergillus flavus, aspergillus niger, Penicillium citrinum, fusarium moniliforme, Bai Di Mould, yeast etc. has strong fungistatic effect.
Described nano titanium oxide has catalytic action to light, the microorganism for the part that can degrade.
Coating used in the sterilization coating is prepared via a method which to form:
(1) ethanol, polyethylene glycol, sodium citrate of corresponding parts by weight are added in deionized water, add corresponding weight The cinnamic acid, nano titanium oxide, beta-schardinger dextrin of part are measured, 10-30min is disperseed under the conditions of 300-500rpm, is then dripped dropwise Add titanate coupling agent, continue after reacting 30min under the conditions of the 300-500rpm, then with ball mill grinding 20-30min, be made Slurry;
(2) into the slurry obtained by above-mentioned steps (1) plus corresponding parts by weight organic siliconresin, under the conditions of 800rpm after After continuous scattered 20-30min, defoamer is added, the coating used in antimicrobial coating is obtained after continuing scattered 20-30min.
Compared with prior art, the film that prepared by the present invention has preferably sterilization antivirus effect, and environmentally safe, More carefully, service life is longer for durability.
Embodiment
In order that those skilled in the art more fully understands technical scheme, and make the present invention features described above, Purpose and advantage become apparent from understandable, are further explained explanation to the present invention in conjunction with embodiment, it is noted that herein All embodiments listed are merely illustrative, are not meant to be defined the scope of the invention.
Embodiment 1
A kind of antibacterial environment protection film, the antibacterial environment protection film are pet layer, antibiotic layer, PE layers, sterilization painting successively from inside to outside Layer, wherein, the thickness of pet layer and PE layers is 25 μm, and the thickness for sterilizing coating and antibiotic layer is 50 μm.
Coating used in the antibiotic layer is formulated by the raw material of following parts by weight:
Coating used in the antibacterial oxidant layer is prepared via a method which to form:
(1) prepared by pre-emulsion
By the PLA of corresponding parts by weight, hydroxypropyl acrylate, emulsifying agent, initiator, trifluoropropylmethyldichlorosilane, Vinyl silane triisopropoxide, polyvinyl alcohol mix with the deionized water of 1/2 parts by weight, and pre-emulsification obtains pre-emulsion;
(2) emulsion polymerization
By the hydroxypropyl methyl cellulose of corresponding parts by weight, chitosan, acetic acid (0.1M), eugenol and remaining deionization Water is added in reactor, and the material in reactor is stirred under the conditions of 300r/min and is warming up to 75 DEG C, then by above-mentioned steps (1) pre-emulsion made from is added drop-wise in the reactor, and 1h is dripped off, and keeping temperature reacts 2h after dripping off, and then heats to 85 DEG C, continue insulation reaction 1h, be down to room temperature, discharging, filtering, obtain antibacterial coating.
Coating used in the sterilization coating is prepared by the raw material of following parts by weight:
Coating used in the sterilization coating is prepared via a method which to form:
(1) ethanol, polyethylene glycol, sodium citrate of corresponding parts by weight are added in deionized water, add corresponding weight The cinnamic acid, nano titanium oxide, beta-schardinger dextrin of part are measured, 10min is disperseed under the conditions of 500rpm, titanate esters are then added dropwise dropwise Coupling agent, continue after reacting 30min under the conditions of the 500rpm, then with ball mill grinding 20min, slurry is made;
(2) into the slurry obtained by above-mentioned steps (1) plus corresponding parts by weight organic siliconresin, under the conditions of 800rpm after After continuous scattered 20min, defoamer is added, the coating used in antimicrobial coating is obtained after continuing scattered 30min.
Embodiment 2
A kind of antibacterial environment protection film, the antibacterial environment protection film are pet layer, antibiotic layer, PE layers, sterilization painting successively from inside to outside Layer, wherein, the thickness of pet layer is 22 μm, and antibiotic layer thickness is 50 μm, and PE thickness degree is 25 μm, sterilization coating layer thickness is 53 μm.
Coating used in the antibiotic layer is formulated by the raw material of following parts by weight:
Coating used in the antibacterial oxidant layer is prepared via a method which to form:
(1) prepared by pre-emulsion
By the PLA of corresponding parts by weight, hydroxypropyl acrylate, emulsifying agent, initiator, trifluoropropylmethyldichlorosilane, Vinyl silane triisopropoxide, polyvinyl alcohol mix with the deionized water of 3/4 parts by weight, and pre-emulsification obtains pre-emulsion;
(2) emulsion polymerization
By the hydroxypropyl methyl cellulose of corresponding parts by weight, chitosan, acetic acid (0.1M), eugenol and remaining deionization Water is added in reactor, and the material in reactor is stirred under the conditions of 400r/min and is warming up to 85 DEG C, then by above-mentioned steps (1) pre-emulsion made from is added drop-wise in the reactor, and 2h is dripped off, and keeping temperature reacts 1h after dripping off, and then heats to 90 DEG C, continue insulation reaction 1h, be down to room temperature, discharging, filtering, obtain antibacterial coating.
Coating used in the sterilization coating is prepared by the raw material of following parts by weight:
Coating used in the sterilization coating is prepared via a method which to form:
(1) ethanol, polyethylene glycol, sodium citrate of corresponding parts by weight are added in deionized water, add corresponding weight The cinnamic acid, nano titanium oxide, beta-schardinger dextrin of part are measured, 30min is disperseed under the conditions of 300rpm, titanate esters are then added dropwise dropwise Coupling agent, continue after reacting 30min under the conditions of the 300rpm, then with ball mill grinding 30min, slurry is made;
(2) into the slurry obtained by above-mentioned steps (1) plus corresponding parts by weight organic siliconresin, under the conditions of 800rpm after After continuous scattered 30min, defoamer is added, the coating used in antimicrobial coating is obtained after continuing scattered 20min.
Embodiment 3
A kind of antibacterial environment protection film, the antibacterial environment protection film are pet layer, antibiotic layer, PE layers, sterilization painting successively from inside to outside Layer, wherein, the thickness of pet layer is 30 μm, and antibiotic layer thickness is 55 μm, and PE thickness degree is 24 μm, sterilization coating layer thickness is 60 μ m。。
Coating used in the antibiotic layer is formulated by the raw material of following parts by weight:
Coating used in the antibacterial oxidant layer is prepared via a method which to form:
(1) prepared by pre-emulsion
By the PLA of corresponding parts by weight, hydroxypropyl acrylate, emulsifying agent, initiator, trifluoropropylmethyldichlorosilane, Vinyl silane triisopropoxide, polyvinyl alcohol mix with the deionized water of 3/5 parts by weight, and pre-emulsification obtains pre-emulsion;
(2) emulsion polymerization
By the hydroxypropyl methyl cellulose of corresponding parts by weight, chitosan, acetic acid (0.1M), eugenol and remaining deionization Water is added in reactor, and the material in reactor is stirred under the conditions of 350r/min and is warming up to 80 DEG C, then by above-mentioned steps (1) pre-emulsion made from is added drop-wise in the reactor, and 1.5h is dripped off, and keeping temperature reacts 1.5h after dripping off, and then heats up To 87 DEG C, continue insulation reaction 1h, be down to room temperature, discharging, filtering, obtain antibacterial coating.
Coating used in the sterilization coating is prepared by the raw material of following parts by weight:
Coating used in the sterilization coating is prepared via a method which to form:
(1) ethanol, polyethylene glycol, sodium citrate of corresponding parts by weight are added in deionized water, add corresponding weight The cinnamic acid, nano titanium oxide, beta-schardinger dextrin of part are measured, 20min is disperseed under the conditions of 400rpm, titanate esters are then added dropwise dropwise Coupling agent, continue after reacting 30min under the conditions of the 400rpm, then with ball mill grinding 25min, slurry is made;
(2) into the slurry obtained by above-mentioned steps (1) plus corresponding parts by weight organic siliconresin, under the conditions of 800rpm after After continuous scattered 23min, defoamer is added, the coating used in antimicrobial coating is obtained after continuing scattered 26min.
The sample obtained is according to JIS Z2801:2000 standards carry out antibacterial detection, its staphylococcus aureus antibiotic rate For 99.9%.

Claims (7)

  1. A kind of 1. antibacterial environment protection film, it is characterised in that:The antibacterial environment protection film is pet layer, antibiotic layer, PE successively from inside to outside Layer, sterilization Tu layer;The thickness of the antibiotic layer is not less than the thickness sum of pet layer and PE layers, and the thickness of the sterilization coating is not Less than the thickness of antibiotic layer;
    Wherein, the coating used in the antibiotic layer is formulated by the raw material of following parts by weight:
    PLA 10-15 parts,
    Hydroxypropyl acrylate 20-40 parts,
    Trifluoropropylmethyldichlorosilane 2-10 parts,
    Vinyl silane triisopropoxide 4-10 parts,
    Hydroxypropyl methyl cellulose 3-6 parts,
    Chitosan 4-6 parts,
    Acetic acid 1-3 parts,
    Eugenol 1-2 parts,
    Polyvinyl alcohol 2-4 parts,
    Emulsifying agent 3-6 parts,
    Initiator 1-2 parts,
    Deionized water 200-400 parts,
    Wherein, the concentration of acetic acid used is 0.1mol/L.
  2. 2. antibacterial environment protection film as claimed in claim 1, it is characterised in that:The emulsifying agent is three phenethyl phenol polyoxyethylene Ether.
  3. 3. antibacterial environment protection film as claimed in claim 1, it is characterised in that:The initiator is potassium sulfate.
  4. 4. antibacterial environment protection film as claimed in claim 1, it is characterised in that:Coating used in the antibacterial oxidant layer is by as follows What method was prepared:
    (1)It is prepared by pre-emulsion
    By the PLA of corresponding parts by weight, hydroxypropyl acrylate, emulsifying agent, initiator, trifluoropropylmethyldichlorosilane, ethene The isopropoxy silane of base three, polyvinyl alcohol mix with the deionized water of 1/2-3/4 parts by weight, and pre-emulsification obtains pre-emulsion;
    (2)Emulsion polymerization
    By the hydroxypropyl methyl cellulose of corresponding parts by weight, chitosan, 0.1mol/L acetic acid, eugenol and remaining deionization Water is added in reactor, and the material in reactor is stirred under the conditions of 300-400r/min and is warming up to 75-85 DEG C, then will be upper State step(1)Obtained pre-emulsion is added drop-wise in the reactor, and 1-2h is dripped off, and keeping temperature reacts 1-2h after dripping off, so After be warming up to 85-90 DEG C, continue insulation reaction 1h, be down to room temperature, discharging, filtering, obtain antibacterial coating.
  5. 5. antibacterial environment protection film as claimed in claim 1, it is characterised in that:Coating used in the sterilization coating is by weighing as follows What the raw material of amount part was prepared:
    Ethanol 30-50 parts,
    Polyethylene glycol 3-8 parts,
    Deionized water 30-50 parts,
    Cinnamic acid 4-6 parts,
    Beta-schardinger dextrin 3-5 parts,
    Titanate coupling agent 8-10 parts,
    Nano titanium oxide 3-5 parts,
    Organic siliconresin 20-30 parts,
    Dispersant 2-4 parts,
    Defoamer 2-3 parts;
    Wherein, the dispersant is sodium citrate.
  6. 6. antibacterial environment protection film as claimed in claim 5, it is characterised in that:The defoamer is organosilicon high effective antifoaming agent.
  7. 7. antibacterial environment protection film as claimed in claim 5, it is characterised in that:Coating used in the sterilization coating is by as follows What method was prepared:
    (1)The ethanol, polyethylene glycol, sodium citrate of corresponding parts by weight are added in deionized water, add corresponding parts by weight Cinnamic acid, nano titanium oxide, beta-schardinger dextrin, under the conditions of 300-500rpm disperse 10-30min, titanium is then added dropwise dropwise Acid esters coupling agent, continue after reacting 30min under the conditions of the 300-500rpm, then with ball mill grinding 20-30min, slurry is made;
    (2)To above-mentioned steps(1)Add the organic siliconresin of corresponding parts by weight in the slurry of gained, continue under the conditions of 800rpm After scattered 20-30min, defoamer is added, obtains sterilizing the coating used in coating after continuing scattered 20-30min.
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