CN109795793A - A kind of heavy packaging high-barrier plastic packaging film and preparation method - Google Patents
A kind of heavy packaging high-barrier plastic packaging film and preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of heavy packaging high-barrier plastic packaging film and preparation methods, belong to the modified field of PET film.The preparation method of high-barrier plastic packaging film, step are packed again are as follows: a, using plasma enhance chemical vapor deposition unit, and PET is placed in vacuum chamber, then being evacuated to background vacuum is 1~5 × 10‑3Pa；Then argon gas is passed through, opens radio-frequency power supply, is activated 5~10 minutes under the pressure of 14~18Pa；After the completion of processing, closes radio-frequency power supply and stop being passed through for Ar；B, graphene is put into vacuum chamber again, is passed through oxygen and argon gas, gas pressure in vacuum is made to keep 25~35Pa, the air pressure ratio of argon gas and oxygen is 1~2:1, is then turned on radio-frequency power supply, handles 4~8 minutes, packed high-barrier plastic packaging film again.This method using plasma enhancing chemical vapor deposition method makes graphene oxide be deposited directly to PET film surface, promotes the barrier property of film.
Description
Technical field
The present invention relates to a kind of heavy packaging high-barrier plastic packaging film and preparation methods, belong to the modified field of PET film.
Background technique
Many barrier film materials, such as polyethylene terephthalate (PET), polyvinylidene chloride (PVDC), second
Alkene-ethenol copolymer (EVOH) etc. has carried out large-scale application in each field of group.But weight packaging field, due to by
Pressure is big, to airtight barrier property require it is higher, many experiments show polyester film be most practical application value inner liner it is thin
Membrane material.
Polyethylene terephthalate since commercialization, cheap raw material and obtained film and container it is light,
It is transparent, be easy to reseal, it is increasing using field and dosage, become the fastest-rising resin of dosage in plastics package.Mesh
Before, often it is only PET bottle in the world and consumes 3,000,000 tons of resin or more, is used mostly as non-returnable container, by American science work
Industry is evaluated as the maximum achievement of 2nd century packing business.In recent years, with the increasingly raising of people's living standard and the level of consumption,
Requirement to plastics packed high-performance, multifunctionality and environment friendly is higher and higher.Wherein, high barrier is as PET packet
The major function of package material, is increasingly subject to the concern of people, and is rapidly developed.So-called high barrier is typically referred to gas
Liquid penetrant has the material of high-barrier effect, that is, prevents and treats the intrusion of oxygen in order to avoid commodity oxidation deterioration；Prevent water or vapor
Infiltration mildew in order to avoid commodity make moist；Prevent fragrance, fragrance and carbon dioxide from escaping, in case commodity are spoiled and rotten etc..
Since the barrier property of base resin PET is poor, polyester sealant film commonly used at present is DuPont Corporation S
Type Mylar polyester film.The some researchers in China by aluminizing in PET film, silicon or its oxide, can also be improved film
Air-tightness.In addition, PVDC and EVOH also have excellent barrier property, but PVDC can become fragile under photooxidation, impact resistance
And cold resistance is bad；EVOH poor heat resistance is influenced big by temperature and humidity.
Application No. is 201610441375.0 Chinese patents to disclose a kind of vertical food of leakproof pressure resistance high temperature resistant high-barrier
Product oil bag and preparation method thereof.The present invention relates to a kind of vertical food oil bag of leakproof pressure resistance high temperature resistant high-barrier and its preparation sides
Method is formed by the way that high-barrier packaging material composite membrane is sent into cutting machine cutting, the composite membrane after cutting is carried out to heat-sealing bag making,
The high-barrier packaging material composite membrane includes A, B, C, D, E, F, G layers, and wherein A is damage resistant polyethylene film layer, and B is adhesive
Layer, C are vacuum polyester aluminium plating membrane (VMPET), and D is adhesive phase, and E is compound high-barrier plastic film layer, and F is adhesive phase, G
For biaxially oriented polypropylene film (BOPP) layer.The vertical food oil bag of leakproof pressure resistance high temperature resistant high-barrier of the invention is poly- with vacuum
Ester aluminium plating membrane and compound high-barrier plastic film layer can obtain high-barrier air-tightness, oil resistant, humidity, guarantee the quality, protect gas
Taste, adhesive of the invention have anti-ultraviolet function, the opacity and barrier property of packaging bag are improved, so that the guarantor of food oil
The matter phase is longer.
Application No. is the novel VMPET that 201521097265.4 Chinese patent discloses a kind of high barrier aluminize it is thin
Film.The utility model discloses a kind of novel VMPET metallized film of high barrier, including the outer layer, barrier layer, line successively stacked
Type low density polyethylene films layer and protective layer, barrier layer use polyethylene terephthalate (PET) film layer, thermoplastic propene
Acid resin and the compound realization of aluminium coated multipass, the thickness range of aluminium coated are 450-520A.
A kind of barrier film is disclosed application No. is 201310009546.9 Chinese patent and using the barrier film
Vacuum heat-insulating plate.The present invention provides a kind of barrier film and the vacuum heat-insulating plate being combined using the barrier film,
The barrier film is made of surface layer, gas barrier layer and hot sealing layer bonding；Gas barrier layer is made of at least one layer of aluminum plated PET film layer；Plating
The preparation process of aluminium PET film are as follows: (1) PET base film is placed on to indoor carry out of aluminizing vacuum aluminum-coated, in the table of PET base film
Face forms aluminium coated；(2) after aluminizing, it is filled with nitrogen to the interior of aluminizing stage by stage, is filled with nitrogen for the first time to the nitrogen
Atmospheric pressure is 800-1200Pa, is maintained 8~12 hours；Being filled with nitrogen to the nitrogen pressure again is 1300-1500Pa, and
At least 12 hours are maintained to get aluminum plated PET film is arrived.Due to the aluminizer that the aluminizer is prepared compared with the prior art,
The barrier property of barrier film entirety can be effectively improved, so that it is in the same energy of occasion to barrier harshness
Enough meet the requirements.
Above-mentioned material is to be aluminized on a pet film to improve the air-tightness of material, and the present invention wants to provide another system
Preparation Method, to further increase the barrier property of PET film.
Summary of the invention
The disadvantages of poor for current PET film material barrier, provides a kind of system of heavy packaging high-barrier plastic packaging film
Preparation Method.
A kind of preparation method of heavy packaging high-barrier plastic packaging film, sequentially includes the following steps:
A, be activated to substrate: using plasma enhances chemical vapor deposition unit, will using PET film as substrate
Substrate is placed in the electric pole plate surface of PECVD vacuum chamber, then by vacuum chamber to background vacuum is 1 × 10-3~5 ×
10-3Pa；Then argon gas is passed through PECVD plasma generation chamber, opens radio-frequency power supply, Ar is utilized under the pressure of 14~18Pa
Plasma is activated substrate, and the processing time is 5~10 minutes；After the completion of processing, closes radio-frequency power supply and stop
Ar's is passed through；
B, it precipitates graphene oxide: graphene being put into PECVD vacuum chamber again, is passed through oxygen and argon gas, protects gas pressure in vacuum
25~35Pa is held, the air pressure ratio of argon gas and oxygen is 1~2:1, is then turned on radio-frequency power supply, handles 4~8 minutes, packed again
High-barrier plastic packaging film.
PECVD, that is, plasma enhanced chemical vapor phase deposition method: being to make to form original containing film by microwave or radio frequency etc.
The gas ionization of son, is being partially formed plasma, and plasma chemistry activity is very strong, it is easy to react, in substrate
On deposit desired film.In order to carry out chemical reaction can at a lower temperature, the activity of plasma is utilized
Promote to react, thus this CVD is known as plasma enhanced chemical vapor deposition (PECVD) experiment mechanism: it is by micro-
Wave or radio frequency etc. make the gas containing film composed atom, are being partially formed plasma, and plasma chemistry activity is very strong,
It is easy to react, goes out desired film in deposition on substrate.Plasma enhanced chemical vapor phase deposition method advantage: basic
Temperature is low；Deposition rate is fast；Quality of forming film is good, and pin hole is less, is not easily cracked.
PET is used primarily in the packaging field to food, beverage etc. as non fiber use PET, to prevent oxygen, steam, two
The infiltration of carbonoxide.But the barrier property of PET film is poor, easily makes content due to the spilling of the entrance of oxygen or carbon dioxide
It rots.
Using plasma of the present invention enhances chemical meteorology deposition method, and deposited oxide graphene, makes by changing on a pet film
PET film barrier property after property greatly enhances.
The technology of the present invention point is using plasma enhancing chemical vapor deposition unit, and using PET film as substrate, argon gas is
Diluent gas pre-processes base film, then using oxygen and graphene respectively as oxidant and monomer, in PET film
Upper precipitating graphene oxide, obtains graphene oxide/PET film.
The present invention uses gas of the argon gas as plasma, and reason has: first, argon gas is easier to obtain, and second, argon
Gas is inert gas, is not reacted with other elements, and protective gas can be often done, and the electron collision reaction of third, argon gas is fewer.Institute
To generate plasma using argon gas discharging.
Further, in order to improve the barrier property of PET film: in step a, being by vacuum chamber to background vacuum
2×10-3~3 × 10-3Pa。
Further, in order to improve the barrier property of PET film: in step a, Ar plasma is utilized under the pressure of 15Pa
Substrate is activated.
Further, in order to improve the barrier property of PET film: in step a, being activated the time is 5 minutes.
Further, in order to improve the barrier property of PET film: in step b, the air pressure ratio of argon gas and oxygen is 1.5~2:
1。
Further, in step b, when the air pressure ratio of argon gas and oxygen is 2:1, barrier of the PET film to oxygen and water
Property is best.
Further, in order to improve the barrier property of PET film: in step b, gas pressure in vacuum keeps 30Pa.
Further, in order to improve the barrier property of PET film: in step b, handling the time 6 minutes.
The invention solves second technical problem be to provide a kind of heavy packaging high-barrier plastic packaging film.
A kind of heavy packaging high-barrier plastic packaging film, using the above-mentioned preparation method for packing high-barrier plastic packaging film again
It is prepared.
A kind of heavy packaging high-barrier plastic packaging film of the invention and preparation method, it is compared with prior art, outstanding
Feature and excellent effect are:
1, graphene is existed due to its unique two-dimensional characteristics, big specific surface area, excellent electric conductivity, thermal conductivity and high intensity
It is huge to may make that the performance of material has by a small amount of graphene is added in favor, especially modified material for the fields such as new material
It is promoted.
2, this method using plasma enhancing chemical vapor deposition method makes graphene oxide be deposited directly to PET film
Surface can reduce the surface defect of PET film by plasma treatment, promote basement membrane flatness, and the defect of basement membrane will lead to resistance
Cracked inside interlayer, the infiltration for gas molecule is provided convenience, so as to cause barrier property decline；When its surface is coated with
When graphene oxide, the defect of substrate surface is repaired, and the infiltration lane of gas molecule is separated, thus to gas molecule is hindered
Infiltration, promotes the barrier property of film.
3, the plasma surface treatment technology that the present invention uses has easy to operate, cleaning, efficient, safety non-pollution
The advantages that, it is able to satisfy the requirement of environmental protection, while making material interface physical property significantly improve, material body will not be by
To influence.
4, the present invention improves the barrier property of PET film using graphene, at low cost, there is wide market application prospect.
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
A, be activated to substrate: using plasma enhances chemical vapor deposition unit, will using PET film as substrate
Substrate is placed in the electric pole plate surface of PECVD vacuum chamber, then by vacuum chamber to background vacuum is 3 × 10-3Pa；So
Argon gas is passed through PECVD plasma generation chamber afterwards, opens radio-frequency power supply, using Ar plasma to base under the pressure of 15Pa
Material is activated, and the processing time is 5 minutes；After the completion of processing, closes radio-frequency power supply and stop being passed through for Ar；
B, it precipitates graphene oxide: graphene being put into PECVD vacuum chamber again, is passed through oxygen and argon gas, protects gas pressure in vacuum
30Pa is held, the air pressure ratio of argon gas and oxygen is 2:1, is then turned on radio-frequency power supply, handles 6 minutes, packed high-barrier plastics again
Packaging film.
Embodiment 2
A, be activated to substrate: using plasma enhances chemical vapor deposition unit, will using PET film as substrate
Substrate is placed in the electric pole plate surface of PECVD vacuum chamber, then by vacuum chamber to background vacuum is 1 × 10-3Pa；So
Argon gas is passed through PECVD plasma generation chamber afterwards, opens radio-frequency power supply, using Ar plasma to base under the pressure of 14Pa
Material is activated, and the processing time is 5 minutes；After the completion of processing, closes radio-frequency power supply and stop being passed through for Ar；
B, it precipitates graphene oxide: graphene being put into PECVD vacuum chamber again, is passed through oxygen and argon gas, protects gas pressure in vacuum
25Pa is held, the air pressure ratio of argon gas and oxygen is 1:1, is then turned on radio-frequency power supply, handles 4 minutes, packed high-barrier plastics again
Packaging film.
Embodiment 3
A, be activated to substrate: using plasma enhances chemical vapor deposition unit, will using PET film as substrate
Substrate is placed in the electric pole plate surface of PECVD vacuum chamber, then by vacuum chamber to background vacuum is 5 × 10-3Pa；So
Argon gas is passed through PECVD plasma generation chamber afterwards, opens radio-frequency power supply, using Ar plasma to base under the pressure of 18Pa
Material is activated, and the processing time is 10 minutes；After the completion of processing, closes radio-frequency power supply and stop being passed through for Ar；
B, it precipitates graphene oxide: graphene being put into PECVD vacuum chamber again, is passed through oxygen and argon gas, protects gas pressure in vacuum
35Pa is held, the air pressure ratio of argon gas and oxygen is 2:1, is then turned on radio-frequency power supply, handles 8 minutes, packed high-barrier plastics again
Packaging film.
Embodiment 4
A, be activated to substrate: using plasma enhances chemical vapor deposition unit, will using PET film as substrate
Substrate is placed in the electric pole plate surface of PECVD vacuum chamber, then by vacuum chamber to background vacuum is 2 × 10-3Pa；So
Argon gas is passed through PECVD plasma generation chamber afterwards, opens radio-frequency power supply, using Ar plasma to base under the pressure of 15Pa
Material is activated, and the processing time is 5~10 minutes；After the completion of processing, closes radio-frequency power supply and stop being passed through for Ar；
B, it precipitates graphene oxide: graphene being put into PECVD vacuum chamber again, is passed through oxygen and argon gas, protects gas pressure in vacuum
26Pa is held, the air pressure ratio of argon gas and oxygen is 1.1:1, is then turned on radio-frequency power supply, handles 5 minutes, is packed high-barrier modeling again
Expect packaging film.
Embodiment 5
A, be activated to substrate: using plasma enhances chemical vapor deposition unit, will using PET film as substrate
Substrate is placed in the electric pole plate surface of PECVD vacuum chamber, then by vacuum chamber to background vacuum is 3 × 10-3Pa；So
Argon gas is passed through PECVD plasma generation chamber afterwards, opens radio-frequency power supply, using Ar plasma to base under the pressure of 16Pa
Material is activated, and the processing time is 6 minutes；After the completion of processing, closes radio-frequency power supply and stop being passed through for Ar；
B, it precipitates graphene oxide: graphene being put into PECVD vacuum chamber again, is passed through oxygen and argon gas, protects gas pressure in vacuum
28Pa is held, the air pressure ratio of argon gas and oxygen is 1.4:1, is then turned on radio-frequency power supply, handles 4.5 minutes, packed high-barrier again
Plastic packaging film.
Embodiment 6
A, be activated to substrate: using plasma enhances chemical vapor deposition unit, will using PET film as substrate
Substrate is placed in the electric pole plate surface of PECVD vacuum chamber, then by vacuum chamber to background vacuum is 4 × 10-3Pa；So
Argon gas is passed through PECVD plasma generation chamber afterwards, opens radio-frequency power supply, using Ar plasma to base under the pressure of 17Pa
Material is activated, and the processing time is 7 minutes；After the completion of processing, closes radio-frequency power supply and stop being passed through for Ar；
B, it precipitates graphene oxide: graphene being put into PECVD vacuum chamber again, is passed through oxygen and argon gas, protects gas pressure in vacuum
27Pa is held, the air pressure ratio of argon gas and oxygen is 1.7:1, is then turned on radio-frequency power supply, handles 7 minutes, is packed high-barrier modeling again
Expect packaging film.
Embodiment 7
A, be activated to substrate: using plasma enhances chemical vapor deposition unit, will using PET film as substrate
Substrate is placed in the electric pole plate surface of PECVD vacuum chamber, then by vacuum chamber to background vacuum is 1 × 10-3Pa；So
Argon gas is passed through PECVD plasma generation chamber afterwards, opens radio-frequency power supply, using Ar plasma to base under the pressure of 18Pa
Material is activated, and the processing time is 5 minutes；After the completion of processing, closes radio-frequency power supply and stop being passed through for Ar；
B, it precipitates graphene oxide: graphene being put into PECVD vacuum chamber again, is passed through oxygen and argon gas, protects gas pressure in vacuum
35Pa is held, the air pressure ratio of argon gas and oxygen is 1:1, is then turned on radio-frequency power supply, handles 8 minutes, packed high-barrier plastics again
Packaging film.
Embodiment 8
A, be activated to substrate: using plasma enhances chemical vapor deposition unit, will using PET film as substrate
Substrate is placed in the electric pole plate surface of PECVD vacuum chamber, then by vacuum chamber to background vacuum is 1.5 × 10-3Pa；
Then argon gas is passed through PECVD plasma generation chamber, opens radio-frequency power supply, Ar plasma is utilized under the pressure of 16.5Pa
Substrate is activated, the processing time is 7.6 minutes；After the completion of processing, closes radio-frequency power supply and stop being passed through for Ar；
B, it precipitates graphene oxide: graphene being put into PECVD vacuum chamber again, is passed through oxygen and argon gas, protects gas pressure in vacuum
32Pa is held, the air pressure ratio of argon gas and oxygen is 1.6:1, is then turned on radio-frequency power supply, handles 6 minutes, is packed high-barrier modeling again
Expect packaging film.
Comparative example 1
Prepare PET film
Using plasma enhances chemical vapor deposition unit and substrate is placed in PECVD vacuum chamber using PET film as substrate
Electric pole plate surface, then by vacuum chamber to background vacuum be 3 × 10-3Pa；Then by argon gas be passed through PECVD etc. from
Daughter generating chamber is opened radio-frequency power supply, is activated using Ar plasma to substrate under the pressure of 15Pa, when processing
Between be 5 minutes；After the completion of processing, closes radio-frequency power supply and stop being passed through for Ar, obtain plastic packaging film.
Test example
In order to prove that the technical effect of preparation process obtains in the present invention high-isolation film, the present invention test Examples 1 to 8
With the OTR oxygen transmission rate and water vapour permeability of the film of comparative example 1:
1, OTR oxygen transmission rate (ASTM D-3985)
Specific testing procedure are as follows: the sample pre-processed is placed between test chamber up and down, is clamped, first to low pressure chamber
(cavity of resorption) is vacuum-treated, and is then vacuumized to whole system, after reaching defined vacuum degree, closes test cavity of resorption, to
High pressure chest (epicoele) is filled with the oxygen of certain pressure, and guarantees to form a constant pressure difference (adjustable) in sample two sides, in this way
Gas can be permeated under the action of differential pressure gradients by high side to low side, be handled by the monitoring to pressure in low-pressure side, from
And obtain every barrier property parameter of institute's test specimens.
2, moisture-vapor transmission (ASTM F-1249-90) is measured using electrolytic sensors method (GB/T21529-2008)
Instrument: U.S. ILLINOIS moisture-vapor transmission analyzer；
Specific testing procedure are as follows: the sample pre-processed is clamped between test chamber, there is the nitrogen for stablizing relative humidity
It is flowed in the side of film, drying nitrogen is flowed in the other side of film, and due to the presence of moist gradient, vapor can be from high humidity
Side passes through film diffusion to low humidity side, and in low humidity side, the drying nitrogen that the vapor of transmission is flowed is carried to sensor, enters
Electric signal in proportion can be generated when sensor, by the analytical calculation to sensor electric signal, to show that the water of sample steams
The parameters such as vapor permeability.The index of two kinds of standards is as shown in the table:
| Project | Testing standard | Test condition |
| OTR oxygen transmission rate | ASTM D-3985 | 23℃ 50%RH |
| Moisture-vapor transmission | ASTM F-1249-90) | 38℃ 100%RH |
After tested, the OTR oxygen transmission rate of the film of the Examples 1 to 8 and comparative example 1 and moisture-vapor transmission are respectively as follows:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 1 | |
| OTR oxygen transmission rate (cc/m2Day) | 0.0068 | 0.0076 | 0.0066 | 0.0081 | 0.007 | 0.0075 | 0.0076 | 0.0070 | 8 |
| Moisture-vapor transmission (g/m2Day) | 0.0045 | 0.005 | 0.0037 | 0.0064 | 0.0052 | 0.005 | 0.0051 | 0.0048 | 21 |
Claims (9)
1. a kind of preparation method of heavy packaging high-barrier plastic packaging film, which is characterized in that sequentially include the following steps:
A, be activated to substrate: using plasma enhances chemical vapor deposition unit, will using PET film as substrate
Substrate is placed in the electric pole plate surface of PECVD vacuum chamber, then by vacuum chamber to background vacuum is 1 × 10-3~5 ×
10-3Pa；Then argon gas is passed through PECVD plasma generation chamber, opens radio-frequency power supply, Ar is utilized under the pressure of 14~18Pa
Plasma is activated substrate, and the processing time is 5~10 minutes；After the completion of processing, closes radio-frequency power supply and stop
Ar's is passed through；
B, it precipitates graphene oxide: graphene being put into PECVD vacuum chamber again, is passed through oxygen and argon gas, protects gas pressure in vacuum
25~35Pa is held, the air pressure ratio of argon gas and oxygen is 1~2:1, is then turned on radio-frequency power supply, handles 4~8 minutes, packed again
High-barrier plastic packaging film.
2. a kind of preparation method of heavy packaging high-barrier plastic packaging film according to claim 1, it is characterised in that: step
It is 2 × 10 by vacuum chamber to background vacuum in a-3~3 × 10-3Pa。
3. a kind of preparation method of heavy packaging high-barrier plastic packaging film according to claim 1 or 2, it is characterised in that:
In step a, substrate is activated using Ar plasma under the pressure of 15Pa.
4. a kind of preparation method of heavy packaging high-barrier plastic packaging film according to claim 1 or 2, it is characterised in that:
In step a, being activated the time is 5 minutes.
5. a kind of preparation method of heavy packaging high-barrier plastic packaging film according to claim 1 or 2, it is characterised in that:
In step b, the air pressure ratio of argon gas and oxygen is 1.5~2:1.
6. a kind of preparation method of heavy packaging high-barrier plastic packaging film according to claim 5, it is characterised in that: step
In b, the air pressure ratio of argon gas and oxygen is 2:1.
7. a kind of preparation method of heavy packaging high-barrier plastic packaging film according to claim 1 or 2, it is characterised in that:
In step b, gas pressure in vacuum keeps 30Pa.
8. a kind of preparation method of heavy packaging high-barrier plastic packaging film according to claim 1 or 2, it is characterised in that:
In step b, handle the time 6 minutes.
9. a kind of heavy packaging high-barrier plastic packaging film, which is characterized in that using the packaging high resistant again described in claim 1~8
It is prepared every the preparation method of plastic packaging film.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111647872A (en) * | 2020-04-01 | 2020-09-11 | 湖南二零八先进科技有限公司 | Method for preventing gas leakage of laser gyroscope based on surface CVD growth graphene |
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| AU8993798A (en) * | 1997-10-09 | 1999-05-03 | Tetra Laval Holdings & Finance Sa | Packaging laminate with gas and aroma barrier properties |
| CN103298608A (en) * | 2011-01-10 | 2013-09-11 | 栗村化学株式会社 | Laminated film having carbon layer |
| CN104962875A (en) * | 2015-07-01 | 2015-10-07 | 中国乐凯集团有限公司 | Preparation method of high-barrier film |
| CN106349462A (en) * | 2016-08-22 | 2017-01-25 | 广东纳路纳米科技有限公司 | Preparation of high-barrier nano modified PET composite material for packaging products |
| CN108265276A (en) * | 2018-01-24 | 2018-07-10 | 贵州民族大学 | A kind of magnetron sputtering preparation process of fold resistant high-barrier composite packing film |
| CN109468607A (en) * | 2018-11-27 | 2019-03-15 | 河北大学 | A kind of preparation method of gas barrier film |
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2019
- 2019-03-25 CN CN201910226310.8A patent/CN109795793A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU8993798A (en) * | 1997-10-09 | 1999-05-03 | Tetra Laval Holdings & Finance Sa | Packaging laminate with gas and aroma barrier properties |
| CN103298608A (en) * | 2011-01-10 | 2013-09-11 | 栗村化学株式会社 | Laminated film having carbon layer |
| CN104962875A (en) * | 2015-07-01 | 2015-10-07 | 中国乐凯集团有限公司 | Preparation method of high-barrier film |
| CN106349462A (en) * | 2016-08-22 | 2017-01-25 | 广东纳路纳米科技有限公司 | Preparation of high-barrier nano modified PET composite material for packaging products |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111647872A (en) * | 2020-04-01 | 2020-09-11 | 湖南二零八先进科技有限公司 | Method for preventing gas leakage of laser gyroscope based on surface CVD growth graphene |
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| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190524 |
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| WW01 | Invention patent application withdrawn after publication |