CN110527123A - A kind of food Package antibacterial barrier plastic foil and low cost preparation method - Google Patents
A kind of food Package antibacterial barrier plastic foil and low cost preparation method Download PDFInfo
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- CN110527123A CN110527123A CN201910849797.5A CN201910849797A CN110527123A CN 110527123 A CN110527123 A CN 110527123A CN 201910849797 A CN201910849797 A CN 201910849797A CN 110527123 A CN110527123 A CN 110527123A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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Abstract
The present invention proposes that a kind of food Package antibacterial obstructs plastic foil and low cost preparation method, the antibacterial barrier plastic foil is first silicon source to be added in the hydrolyzate of isopropyl alcohol and water mixed preparing, then it is coated on membrane surface and forms boehmite barrier layer, silver ammino solution and chitosan-acetic acid mixed solution are sprayed again, and are reacted by chitosan quaternary ammonium salting liquid and be made.Method provided by the invention; membrane surface by organic silicon source hydrolyze to form boehmite barrier layer and by nano silver reduction and chitosan film forming be fixed; impart the excellent barrier property of film; and there is good anti-microbial property; this invention simplifies the preparation processes of antibacterial barrier film simultaneously; without repeatedly coating or depositing organic inorganic layer, production cost is reduced, large-scale production is conducive to.
Description
Technical field
The present invention relates to plastics package technical field of membrane, more particularly to a kind of food Package antibacterial obstruct plastic foil and
Low cost preparation method.
Background technique
The storage of food drug and sealing up for safekeeping during electronical display need packaging material to have excellent oxygen-barrier property
Can, thus high resistant oxygen packaging material plays significant application value in people's daily life.Plastic barrier oxygen film conduct
The main material of marketing packing is gradually instead of packaging materials such as traditional glass, metal, stationeries.But various plastics packages
Film all has different degrees of gas-premeable, seriously restricts the packaging quality of plastic material.
Although the oxygen barrier property of the plastic package material of inorganic matter addition is widely studied by people always, and no matter
Experiment still theoretically all proves that inorganic lamellar material can effectively extend the diffusion path of oxygen molecule, however currently hinders oxygen
Packaging material manufacturing technique method such as steamed bun technique, corona treatment coating and sol-gel method craft technical requirements
Higher, process complex precise constrains the application extension of separated packaging material.
In addition, the inorganic lamellar material character of current most of synthesis is random and is easy to reunite, lead to composite oxygen barrier packet
The oxygen barrier property rising space for filling film is limited, this is a bottleneck to the barrier property for improving material.And it is current general
It is to be alternatively formed multilayer (generally higher than 5 layers) on plastic basis material to have the organic/inorganic layer of water oxygen barriers function can all over technique
Significantly to improve the water proof oxygen barrier property of plastic basis material, this method is current more feasible water oxygen Barrier Technology.However,
The way for repeatedly coating or depositing organic inorganic layer greatly increases the complexity of technique and production cost.Therefore, for high resistant
People are constantly subjected to every the research of the food package film of low cost to pay attention to.
Chinese invention patent application number 201310370729.3 discloses a kind of anti-bacterial packaging film, including nano-antibacterial layer,
The adhesive layer of barrier layer, extexine and the connection nano-antibacterial layer, barrier layer and extexine；Wherein nano-antibacterial layer is with weight
Component meter, including 70-150 parts of LDPE, it is 20-60 parts of LLDPE, 30-50 parts of silver ion antimicrobial agent, 4-8 parts of polyethylene wax, stearic
It is 3-7 parts sour；The preparation process of the invention is that antibacterial plastic concentrate, barrier layer, extexine, binder are respectively put into each hopper of extruder
In, coextrusion casting is compound to obtain co-extrusion anti-bacterial packaging film.Chinese invention patent application number 201510877704.1 discloses one kind
Antibacterial high-barrier food package film including paper substrate, the aluminium film that is compound in the paper substrate upper surface, is compound in paper substrate following table
The poly- second layer in face, poly- second layer surface are coated with antibiotic layer.
While in order to keep package plastics of food film water oxygen high barrier, antibiotic property, it is further simplified preparation process, is dropped
Low preparation cost, it is necessary to propose a kind of preparation method of novel foodstuff plastic foil, and then realize high-barrier food package film
Low cost preparation.
Summary of the invention
For the food plastic packaging material currently with inorganic matter addition preparation there are preparation process complexity is cumbersome, cost
Higher problem, the present invention proposes that a kind of food Package antibacterial obstructs plastic foil and low cost preparation method, thus effectively real
The high barrier of package plastics of food film is showed, anti-microbial property is excellent, and prepares simple and at low cost.
To solve the above problems, the invention adopts the following technical scheme:
A kind of food Package obstructs the low cost preparation method of plastic foil with antibacterial, it is specific the preparation method is as follows:
(1) isopropyl alcohol and water is first hybridly prepared into hydrolyzate, silicon source is then added and is sufficiently stirred, then will obtain
Silicon source/hydrolyzate is coated on membrane surface, is placed in air dry oven and is dried, and is formed in membrane surface with a thickness of 5-20 μm
Boehmite barrier layer, obtain surface have barrier layer plastic foil；
(2) silver ammino solution is first configured, is then added in chitosan-acetic acid mixed solution and is sufficiently stirred；In microwave heating item
Under part, spray is added as reducing agent in chitosan quaternary ammonium salting liquid and is carried out instead in the plastic film with barrier layer
It answers, so that the nano silver antimicrobials that reduction obtains jointly fix boehmite barrier layer with the dry chitosan film being precipitated,
It is dry to obstruct plastic foil to get food Package antibacterial.
Preferably, source of aluminium is aluminium isopropoxide.
Preferably, the basement membrane is CPP film, LDPE film, HDPE film, BOPP film, PET film, BOPET film, BOPA film, PVDC
The composite membrane of one of film monofilm or two or more compositions, with a thickness of 40-250 μm.
Preferably, the concentration of the silver ammino solution is 0.05-0.1mol/L.
Preferably, in step (1), isopropanol, water, silicon source mass ratio be 100:40-80:10-40.
Preferably, 80 DEG C of temperature dry described in step (1), dry 12-13h.
Preferably, in step (2), acetic acid, chitosan, silver ammino solution mass ratio be 100:1-4:50-100.Shell is poly-
Sugared quaternary ammonium salt solution is as reducing agent, and wherein chitosan quaternary ammonium salt dosage is the 20% of silver liquid ammonia quality.
Preferably, the microwave power of microwave heating described in step (3) is 800-900W, and heating temperature is 60-70 DEG C.
Preferably, in spray described in step (3), the height of spray head is 30-50mm, and the spray flow of spray head is 50-
100mL/min, reaction time 30-40min.
It is raw material that the present invention, which selects organic silicon source aluminium isopropoxide, prepares boehmite using hydrolysis.Aluminium isopropoxide
It is a kind of typical aluminium-alcohol salt, compared with other alkoxide, relative boiling point is lower, more easy purification, and production cost is relatively low；Separately
Outside, it selects isopropanol as reaction dissolvent, there is apparent price and environment-friendly advantage, volatility is high, while studies have shown that passing through
The additive amount for controlling isopropanol, can effectively realize pattern control, and boehmite produced by the present invention has very thin gauffer piece
Layer structure, therefore can assign film excellent barrier property.
Further, silver ammino solution is added in chitosan-acetic acid mixed solution, chitosan quaternary ammonium salt is as a kind of by shell
Glycan carries out quaternised modified a kind of chitosan derivatives, and good film forming, flocculability, biology can be had by not only maintaining
Compatibility and biological degradability, and there is good bacteria resistance and moisture absorbability and moisture retentivity, at the same time as reducing agent, season
Ammonium, just by that can reduce metal ions to metal simple-substance, utilizes chitosan quaternary ammonium salting liquid will be silver-colored as reproducibility in the present invention
Silver in ammonia solution is reduced to extension nano silver, not only has excellent anti-microbial property, and can prevent its leakage, overflow, simultaneously
Boehmite barrier layer is fixed in reducing nano-silver and chitosan film forming, improves the barrier property of plastic foil.
The present invention also provides a kind of food Package that above-mentioned preparation method is prepared antibacterials to obstruct plastic foil.The food
Object antibacterial packing obstructs plastic foil, and the antibacterial barrier plastic foil is the water that silicon source is first added to isopropyl alcohol and water mixed preparing
It solves in liquid, is then coated on membrane surface and forms boehmite barrier layer, then spray silver ammino solution and chitosan-acetic acid mixing
The chitosan quaternary ammonium salting liquid that solution is prepared is reacted and is made.
The plastic package material of existing inorganic matter addition is there are preparation process complexity is cumbersome, the problem of higher cost, limit
Its application is made.In consideration of it, the present invention proposes that a kind of food Package antibacterial obstructs plastic foil and low cost preparation method, first take
The mixing of isopropyl alcohol and water, is configured to hydrolyzate, and silicon source aluminium isopropoxide is added and is sufficiently stirred, silicon source/hydrolyzate is coated on
Then membrane surface is dried at 80 DEG C, form boehmite barrier layer；Silver ammino solution is configured, chitosan-vinegar is added
In sour mixed solution, under microwave heating condition, chitosan quaternary ammonium salting liquid is added and is reacted as reducing agent spray, so that
It restores obtained nano silver antimicrobials and the dry chitosan film being precipitated is jointly fixed to get food by boehmite barrier layer
Antibacterial packing barrier film.Method provided by the invention hydrolyzes to form boehmite barrier layer simultaneously by organic silicon source
It is fixed by nano silver reduction and chitosan film forming, imparts the excellent barrier property of film, and had good anti-
Bacterium performance, while this invention simplifies the preparation processes of antibacterial barrier film, without repeatedly coating or depositing organic inorganic layer, drop
Low production cost is conducive to large-scale production.
The present invention proposes that a kind of food Package antibacterial obstructs plastic foil and low cost preparation method, with prior art phase
Than the feature and excellent effect protruded is:
1, the present invention forms boehmite barrier layer in plastic film, very using it by the hydrolysis of organic silicon source
Thin gauffer lamellar structure imparts the excellent barrier property of film.
2, the present invention is fixed boehmite barrier layer by nano silver reduction and chitosan film forming, not only has
Excellent anti-microbial property, and its leakage can be prevented, overflowed, further improve barrier property.
3, this invention simplifies the preparation processes of antibacterial barrier film drops without repeatedly coating or depositing organic inorganic layer
Low production cost is conducive to large-scale production.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
(1) isopropyl alcohol and water is first hybridly prepared into hydrolyzate, silicon source is then added and is sufficiently stirred, then will obtain
Silicon source/hydrolyzate is coated on membrane surface, is placed in air dry oven and is dried, and forming average thickness in membrane surface is 12
μm boehmite barrier layer, obtain surface have barrier layer plastic foil；Silicon source is aluminium isopropoxide；Basement membrane is BOPP film,
Average thickness is 100 μm；Wherein, isopropanol, water, silicon source mass ratio be 100:70:30；80 DEG C of dry temperature, it is dry
12.5h；
(2) silver ammino solution is first configured, is then added in chitosan-acetic acid mixed solution and is sufficiently stirred；Silver ammino solution it is dense
Degree is 0.07mol/L；Wherein, acetic acid, chitosan, silver ammino solution mass ratio be 100:3:70；Under microwave heating condition,
Spray is added as reducing agent in chitosan quaternary ammonium salting liquid to react in the plastic film with barrier layer, so that reduction
Obtained nano silver antimicrobials jointly fix boehmite barrier layer with the dry chitosan film being precipitated, dry to get food
Object antibacterial packing obstructs plastic foil；The microwave power of microwave heating is 860W, and heating temperature is 66 DEG C；In spray, spray head
Height be 38mm, the spray flow of spray head is 70mL/min, with a thickness of 20 microns, reaction time 34min.
Test method:
The plastic foil that the present embodiment is prepared carries out permeability test, has carried out oxygen respectively through test and water
Vapor permeability test, permeability test is referring to GB/T 1038-2000 standard, and water vapo(u)r transmission test is referring to GB/T
1037-1988, obtains that the results are shown in Table 1.
Embodiment 2
(1) isopropyl alcohol and water is first hybridly prepared into hydrolyzate, silicon source is then added and is sufficiently stirred, then will obtain
Silicon source/hydrolyzate is coated on membrane surface, is placed in air dry oven and is dried, and forming average thickness in membrane surface is 5 μ
The boehmite barrier layer of m obtains the plastic foil that surface has barrier layer；Silicon source is aluminium isopropoxide；Basement membrane is BOPP film, is put down
With a thickness of 100 μm；Wherein, isopropanol, water, silicon source mass ratio be 100:40:10；80 DEG C of dry temperature, it is dry
12h；
(2) first configure silver ammino solution, then be added chitosan-acetic acid mixed solution in be sufficiently stirred, silver ammino solution it is dense
Degree is 0.05mol/L；Wherein, acetic acid, chitosan, silver ammino solution mass ratio be 100:1:50；
(3) under microwave heating condition, spray is added in barrier layer using chitosan quaternary ammonium salting liquid as reducing agent
Plastic film reacted so that the obtained nano silver antimicrobials of reduction and the chitosan film of dry precipitation will intend jointly it is thin
Diaspore barrier layer is fixed, dry to obstruct plastic foil to get food Package antibacterial；The microwave power of microwave heating is 800W,
Heating temperature is 60 DEG C；In spray, the height of spray head is 30mm, and the spray flow of spray head is 50mL/min, micro- with a thickness of 20
Rice, reaction time 40min.
It is tested using the method for embodiment 1, test result is as shown in table 1.
Embodiment 3
(1) isopropyl alcohol and water is first hybridly prepared into hydrolyzate, silicon source is then added and is sufficiently stirred, then will obtain
Silicon source/hydrolyzate is coated on membrane surface, is placed in air dry oven and is dried, and forming average thickness in membrane surface is 20
μm boehmite barrier layer, obtain surface have barrier layer plastic foil；Silicon source is aluminium isopropoxide；Basement membrane is BOPP film,
Average thickness is 100 μm；Wherein, isopropanol, water, silicon source mass ratio be 100:80:40；80 DEG C of dry temperature, it is dry
13h；
(2) first configure silver ammino solution, then be added chitosan-acetic acid mixed solution in be sufficiently stirred, silver ammino solution it is dense
Degree is 0.1mol/L；Wherein, acetic acid, chitosan, silver ammino solution mass ratio be 100:4:100；Under microwave heating condition,
Spray is added as reducing agent in chitosan quaternary ammonium salting liquid to react in the plastic film with barrier layer, so that reduction
Obtained nano silver antimicrobials jointly fix boehmite barrier layer with the dry chitosan film being precipitated, dry to get food
Object antibacterial packing obstructs plastic foil；The microwave power of microwave heating is 900W, and heating temperature is 70 DEG C；In spray, spray head
Height be 50mm, the spray flow of spray head is 100mL/min, with a thickness of 20 microns, reaction time 30min.
It is tested using the method for embodiment 1, test result is as shown in table 1.
Embodiment 4
(1) isopropyl alcohol and water is first hybridly prepared into hydrolyzate, silicon source is then added and is sufficiently stirred, then will obtain
Silicon source/hydrolyzate is coated on membrane surface, is placed in air dry oven and is dried, and forming average thickness in membrane surface is 10
μm boehmite barrier layer, obtain surface have barrier layer plastic foil；Silicon source is aluminium isopropoxide；Basement membrane is BOPP film,
Average thickness is 100 μm；Wherein, isopropanol, water, silicon source mass ratio be 100:60:25；80 DEG C of dry temperature, it is dry
12.5h；
(2) first configure silver ammino solution, then be added chitosan-acetic acid mixed solution in be sufficiently stirred, silver ammino solution it is dense
Degree is 0.08mol/L；Wherein, acetic acid, chitosan, silver ammino solution mass ratio be 100:2:80；Under microwave heating condition,
It is added chitosan quaternary ammonium salting liquid as reducing agent, spray is reacted in the plastic film with barrier layer, so that also
The nano silver antimicrobials that original obtains and the dry chitosan film being precipitated jointly fix boehmite barrier layer, it is dry to get
Food Package obstructs plastic foil with antibacterial；The microwave power of microwave heating is 850W, and heating temperature is 65 DEG C；In spray, spray
The height of head is 40mm, and the spray flow of spray head is 80mL/min, with a thickness of 20 microns, reaction time 35min.
It is tested using the method for embodiment 1, test result is as shown in table 1.
Comparative example 1
Comparative example 1 compared with Example 1, is not added with silver ammino solution, and plastic foil obtained is carried out using the method for embodiment 1
Test, test result are as shown in table 1.
Comparative example 2
Compared with Example 1, not formed boehmite barrier layer, plastic foil obtained is using embodiment 1 for comparative example 2
Method is tested, and test result is as shown in table 1.
Table 1:
Claims (10)
1. the low cost preparation method that a kind of food Package obstructs plastic foil with antibacterial, which is characterized in that specific preparation method is such as
Under:
(1) isopropyl alcohol and water is first hybridly prepared into hydrolyzate, silicon source is then added and is sufficiently stirred, then the aluminium that will be obtained
Source/hydrolyzate is coated on membrane surface, is placed in air dry oven and is dried, and is formed in membrane surface with a thickness of 5-20 μm
Boehmite barrier layer obtains the plastic foil that surface has barrier layer；
(2) silver ammino solution is first configured, is then added in chitosan-acetic acid mixed solution and is sufficiently stirred；Under microwave heating condition,
Spray is added as reducing agent in chitosan quaternary ammonium salting liquid to react in the plastic film with barrier layer, so that
Obtained nano silver antimicrobials are restored jointly to fix boehmite barrier layer with the dry chitosan film being precipitated, it is dry, i.e.,
It obtains food Package and obstructs plastic foil with antibacterial.
2. a kind of food Package according to claim 1 obstructs the low cost preparation method of plastic foil, feature with antibacterial
It is, source of aluminium is aluminium isopropoxide.
3. a kind of food Package according to claim 1 obstructs the low cost preparation method of plastic foil, feature with antibacterial
Be, in step (1), isopropanol, water, silicon source mass ratio be 100:40-80:10-40.
4. a kind of food Package according to claim 1 obstructs the low cost preparation method of plastic foil, feature with antibacterial
It is, dry 80 DEG C of temperature described in step (1), dry 12-13h.
5. a kind of food Package according to claim 1 obstructs the low cost preparation method of plastic foil, feature with antibacterial
It is, the basement membrane is one of CPP film, LDPE film, HDPE film, BOPP film, PET film, BOPET film, BOPA film, PVDC film
The composite membrane of monofilm or two or more compositions, with a thickness of 40-250 μm.
6. a kind of food Package according to claim 1 obstructs the low cost preparation method of plastic foil, feature with antibacterial
It is, the concentration of the silver ammino solution is 0.05-0.1mol/L.
7. a kind of food Package according to claim 1 obstructs the low cost preparation method of plastic foil, feature with antibacterial
Be, in step (2), acetic acid, chitosan, silver ammino solution mass ratio be 100:1-4:50-100.
8. a kind of food Package according to claim 1 obstructs plastic foil and low cost preparation method, feature with antibacterial
It is, the microwave power of microwave heating described in step (3) is 800-900W, and heating temperature is 60-70 DEG C.
9. a kind of food Package according to claim 1 obstructs the low cost preparation method of plastic foil, feature with antibacterial
It is, in spray described in step (2), the height of spray head is 30-50mm, and the spray flow of spray head is 50-100mL/min,
Reaction time is 30-40min.
10. a kind of food Package antibacterial that the preparation method as described in claim 1-9 any claim is prepared obstructs plastics
Film.
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| CN111484660A (en) * | 2020-04-28 | 2020-08-04 | 海南华塑新型管业有限公司 | Nano antibacterial plastic and preparation method thereof |
| KR20220165123A (en) | 2021-06-07 | 2022-12-14 | 신수관 | Antibacterial, antiviral, antifungal cellulose resin composition and molded body of the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20220165123A (en) | 2021-06-07 | 2022-12-14 | 신수관 | Antibacterial, antiviral, antifungal cellulose resin composition and molded body of the same |
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| Publication number | Publication date |
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| CN110527123B (en) | 2022-05-06 |
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