CN108265276A - A kind of magnetron sputtering preparation process of fold resistant high-barrier composite packing film - Google Patents
A kind of magnetron sputtering preparation process of fold resistant high-barrier composite packing film Download PDFInfo
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- CN108265276A CN108265276A CN201810069708.0A CN201810069708A CN108265276A CN 108265276 A CN108265276 A CN 108265276A CN 201810069708 A CN201810069708 A CN 201810069708A CN 108265276 A CN108265276 A CN 108265276A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/12—Organic material
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Abstract
The invention discloses a kind of magnetron sputtering preparation process of fold resistant high-barrier composite packing film, it is characterised in that：It comprises the following steps：(1) preparation of base material；(2) base material is sent into pre-sputtering vacuum tank and carries out pre-sputter cleaning, pre-sputtering gas is 99.95% 99.99% argon gas, and pre-sputtering power increase rate is 0.1 6W hour/square centimeter, and sputtering time is 30 500 seconds；(3) radio-frequency power supply is opened, on pre-sputtering matrix carries out more targets and deposit simultaneously to prepare compound high resistance film, wherein, the base material by pre-sputtering is wrapped in cylinder surface and fixes, and the vacuum degree control of vacuum chamber is 0.1 10 × 10‑5Pa, working gas is argon gas or argon oxygen gas mixture, purity of argon is 99.95% 99.99%, throughput is 10 450sccm, and oxygen purity is 99.95% 99.999%, and throughput is 0.5 100sccm, operating air pressure control is 0.2 2Pa, target-substrate distance is 4 16cm, and drum rotation speed control is 0.5 10m/ points, and sputtering time is 5 300 minutes.
Description
Technical field
The present invention relates to the technical field of barrier package, more particularly to a kind of life of fold resistant magnetron sputtering high-resistant diaphragm
Production. art.
Background technology
The development of barrier package be derived from the oxidizable denaturation of the packing materials such as food, drug, microelectronic product it is rotten and to packet
Fill the barrier demand that film proposes.It is typically that the very strong material of barrier properties for gases and heat suture property, moisture barrier is very strong
Polyolefin, which is carried out at the same time, to be squeezed out, and is the film of multilayered structure.Magnetron sputtering technique since the advent of the world, due to its deposition rate
Soon, the advantages that underlayer temperature is low, sputter cathode size can be scaled up.It has been applied to from microelectronic component to several square metres
The numerous areas of coating film on glass, and the main stream approach for large area high speed deposition is developing progressively, and applied to barrier package material
The production of material.There is metallized film at first in nineteen fifty-nine, the gas barrier packaging material of vacuum deposition class, real in 1970 or so
Now industrialize, and in decades thereafter researcher to the pass of the preparation method of aluminizer, Al film thicknesses and barrier property
Combination interface of system, the structure feature of Al, metal and PET base material etc. is studied.Various height had been produced in succession later
Barrier film includes：ZnO, SiOx, SiNyOx, ITO and DLC etc..
At present, the method for depositing barrier film mainly includes physical vapour deposition (PVD) (PVD), plasma enhanced chemical vapor sinks
Product (PECVD) etc..However, due to the coefficient of thermal expansion difference of growth stresses of thin film and film material and base material, PVD methods are utilized
There are a large amount of blind crack and nano cracks for such material prepared, strongly limit the application of such material.It is although domestic
The crack problem that outer researcher prepares film for PVD method gives careful research, but still lack effective solution route.
General barrier packaging material is mostly high molecule plastic, is entwined by macromolecule mostly, plastics
The barrier property of itself does not reach requirement.Therefore, the barrier property technology for improving plastics package base material is come into being.At present, material is improved
The barrier property of material is generally using technologies such as multiple elements design, MULTILAYER COMPOSITE, blending, vacuum evaporation, plasma vapor depositions.In fact, work as
The technology of the high plastics barrier property of premise is to be combined the material for having more high barrier with plastics nothing more than.And combined method can return
Become two kinds：Plastics are regenerated first, barrier material is mixed into base material masterbatch；Second is that in existing plastic sheet surface system
Standby high barrier material.The former forms multicomponent material after blending, often also needs to multi-layer co-extruded formation high-barrier plastic bag
Package material, technology of preparing does not meet the main trend of Packaging Reduce, and is usually had in preparation process using volatile
Solvent.The latter is using the plastics that market is widely present as base material, has a wide application prospect, but existing conventional PVD
There are the defects of a large amount of crackles, pin hole and easy embrittlement in use for barrier film prepared by method.
The top periodical Packaging Technology and Science chief editor David Shires of International Packaging circle are first
Life once sayed that effectively (2012 International Packagings were big with important researching value and bright prospects for the relevant technologies of solution PVD method crackle
Meeting plenary lecture, ningbo of china).According to statistics, whole world damage of agricultural product and food caused by lacking Trend of High Obstructive Materials Ordnance Engineering College
It fails to keep an appointment and accounts for total output 20% or so；The 20% of the annual fruit and vegetable total output in China is also because shipping storage process packaging material obstructs
Property not enough and caused by loss up to 400,000,000,000 yuan.On the other hand, Trend of High Obstructive Materials Ordnance Engineering College is widely used in precision machinery zero and matches
The encapsulation of part, electronic component and solar components improves its service life, for packagings such as food, drug and medical instruments and equipments
Prevent harmful substance from migrating.Therefore, the research of high-barrier packaging material is of great significance.
Patent 2015104585235, which is mentioned, is introduced macromolecule soft segment in sedimentary, but not using sputtering method
It puts into practice, does not also explicitly introduce the specific method and technique of macromolecule soft segment.In addition, the patent is by mixing altogether
The method of extrusion introduces macromolecule soft segment in the substrate, and the raising of the overall flexibility of composite membrane is mostly derived from base material flexibility
Raising, the micro-crack of substrate surface deposited barrier layers and tough sex chromosome mosaicism are there is no improving, after folding, ceramic barrier it is crisp
Property and easy fracture problem can not be solved thoroughly.
Invention content
The technical problem to be solved by the present invention is to：Film class gas barrier film is prepared for PVD method (sputtering method) easily to go out
Show crackle and be improved in the problems such as not folding during such materials'use, used using high molecular polymer as target,
It is subjected to magnetic control co-sputtering vacuum plasma deposition technique system in frosting simultaneously with inorganic or inorganic oxide target
It is prepared by standby flexible, fold resistant compound high-isolation film, the magnetron sputtering for developing a kind of compound high-isolation film of fold resistant
Technique.
The technical scheme is that：A kind of magnetron sputtering preparation process of fold resistant high-barrier composite packing film, packet
Containing following steps：(1) preparation of base material；(2) base material is sent into pre-sputtering vacuum tank and carries out pre-sputter cleaning, pre-sputtering gas is
99.95%-99.99% argon gas, pre-sputtering power increase rate be 0.1-6W hours/square centimeter, sputtering time 30-500
Second；(3) radio-frequency power supply is opened, on pre-sputtering matrix carries out more targets and deposit simultaneously to prepare compound high resistance film, wherein, by pre-
The base material of sputtering is wrapped in cylinder surface and fixes, and the vacuum degree control of vacuum chamber is in 0.1-10 × 10-5Pa, working gas are argon gas
Or argon oxygen gas mixture, purity of argon 99.95%-99.99%, throughput 10-450sccm, oxygen purity are
99.95%-99.999%, throughput 0.5-100sccm, operating air pressure control are 0.2-2Pa, target-substrate distance 3-16cm, are rolled
Cylinder rotary speed control is 0.5-10m/ points, and sputtering time is 5-300 minutes；More target cosputterings are with polyphosphazene polymer
Conjunction object is target, it either is formed double targets or three targets two kinds with any one in inorganic target, inorganic oxide target
Material sputters simultaneously.
The base material for use by polyethylene terephthalate, PP, EVOA and PA one-component or one kind with
Upper component multilayer plastic alloy.
The macromolecule target using PI, PTFE, polyethylene LLDPE, polyisoprene and epoxy resin it is single or
The high molecular polymer of more than one blendings.
The inorganic material is Si, Al, one or more than one kinds of in Ti, graphite；Inorganic oxide for SiOx,
ZnO、Al2O3、SiNyOx、TiO2, it is one or more than one kinds of in ITO and DLC etc..
The Sputtering power density of the macromolecule target be 0.1-10W/ square centimeters, preferably 0.3-5W/ square centimeters,
The inorganic Sputtering power density with inorganic oxide target is 0.1-15W/ square centimeters, preferably 0.5-6W/ square centimeters, is adjusted
The power density ratio of macromolecule target and ceramic target is between 0.1-10, between preferably 0.5-2.5.
The vacuum degree control of the vacuum chamber is in 2-5 × 10-5Pa, working gas are that working gas is argon gas or argon oxygen
Gaseous mixture, purity of argon 99.95%-99.99%, throughput 40-150sccm, oxygen purity 99.95%-
99.999%, throughput 5-45sccm, operating air pressure control are 0.55-0.9Pa, and target-substrate distance 4-10cm, roller rotates fast
Degree control is 1-3m/ points, and sputtering power control is 0.5-6W/ square centimeters, and sputtering time is 15-90 minutes.
The base material single side or double-sided deposition flexible barrier layers.
The composite target material raw material is polymer and inorganic material, then working gas is argon oxygen gas mixture, wherein, argon gas
The ratio of flow and oxygen flow is 100:1-100:Between 90, preferably 15:1-2:Between 1；The composite target material raw material is
Polymer and inorganic oxide, then working gas be argon gas or argon oxygen gas mixture, preferably simple argon gas.
Beneficial effects of the present invention：Macromolecule soft segment is introduced laminated film by the laminated film prepared by the present invention
Inorganic barrier layer, it is strong to water vapour, oxygen, obstructing capacity, reduce the permeability of water, oxygen, extend pack content
Mould tide and rotten time, improve the food shelf time.In addition, the packaging material prepared by the preparation process also is able to effectively
Extend the fragrance remaining time of food, reduce the permeability and cost of toxic gas in transportational process.Folding high resistant of the present invention
There is high economic value every the magnetron sputtering preparation process of film.
Advantage of the invention is that：
By pre-sputtering step, the adsorbed gas of substrate surface, pollutant, oxide are removed, also by poor adhesion
Particle removes so that surface increases activity, and the adhesive force of base material is enhanced.
Using macromolecule as target, it is broken that organic polymer flexible chain is introduced in film layer is obstructed using RF magnetron co-sputtering method
Piece improves the folding resistance of film.
By high molecular polymer be target, magnetic control co-sputtering technology deposition laminated film after material overall performance will
To raising.
(1) deposition laminated film post-tensioning performance will have large change, and whole tensile property improves, and laminated film is resistance to
Folding is had excellent performance, and polymer segment introduces film and forms composite construction, can significantly improve its toughness, even across repeatedly repeatedly
It folds, deposited barrier layers are also not in be completely severed crackle, still maintain higher obstructing capacity.
(2) deposit laminated film after, after the introducing of macromolecule soft segment, alleviate inorganic nanoparticles deposition when due to
The crackle and defect problem that island is mended effect and generated improve the compactness of deposition Obstruct membrane and to H2The resistance of O steam, oxygen
Every ability.
(3) will have to migration of the organic polymer to pack content in inhibition heavy metal and plastics after depositing laminated film
Apparent effect, SiO2、Al2O3、ZrO2It waits inorganic particulates that can reduce polymer segment movement degree, reduces free volume, reduce
The channel and probability of migration.
(4) by the film of three layers of duplex spread-blade, the compound high-resistant diaphragm of fold resistant also significantly proposes the reservation of food flavor
Height while meeting the extension food shelf time, maintains the original fragrance of food.
Description of the drawings
Fig. 1 is the magnetron sputtering deposition process schematic representation of the macromolecule of the present invention, inorganic compounding target；M1 is macromolecule target
Material, M2 are inorganic target；
Fig. 2 is the embodiment of the present invention 1 and its SEM being folded after 100 times figures；
Fig. 3 is that the embodiment of the present invention 2 is schemed with comparative example 2 and the SEM being separately folded after 100 times；
Fig. 4 is the XRD diagram of the embodiment of the present invention 3 and comparative example 3；
Fig. 5 is that the embodiment of the present invention 3 and the SEM of comparative example 3 scheme；
Fig. 6 is that the embodiment of the present invention 3 is folded 100 times SEM figures and its enlarged drawing after folding with comparative example 3.
Specific embodiment
The present invention is further described with reference to specific embodiment, but does not limit the invention to these tools
Body embodiment.One skilled in the art would recognize that present invention encompasses may include in Claims scope
All alternatives, improvement project and equivalent scheme.
A kind of macromolecule, inorganic material composite target material sputtering vacuum plasma deposition technique prepare fold resistant high-barrier answer
The preparation process of packing film is closed, is as follows：
Embodiment 1
(1) preparations such as cleaning, drying of base material；Using PA as base material, it is cleaned by ultrasonic respectively with acetone, alcohol, deionized water
15 minutes, it is then fed into the drying of wind turbine portion.
(2) ready base material is sent into pre-sputtering vacuum tank and carries out pre-sputter cleaning, pre-sputtering gas is 999.99%
Argon gas, it is 2W hours/square centimeter that sputtering power, which increases rate, and sputtering time is 150 seconds；
(3) respectively with PI, SiO2For target, radio-frequency power supply is opened, carries out being co-deposited preparation C-SiO on pre-sputtering matrix2
Compound high resistance film, the vacuum degree control of vacuum chamber is 4 × 10-5Pa, working gas are 999.99% argon gas, and argon stream amount is
50sccm, operating air pressure control are 0.4Pa, and target-substrate distance 10cm, drum rotation speed control is 1.5m/ points, PI, SiO2Splash
It is 1.4W/ square centimeters to penetrate power and control, and sputtering time is 40 minutes, is prepared for PI/SiO2/ PA composite membranes；Finally, divide
It cuts, after product inspection qualification, winding, packaging and storage.Compare for convenience, comparative example 1 is identical with 1 base material of embodiment, with SiO2For
Sputtering target material, under the conditions of identical sputtering technology, deposition is prepared for SiO2/ PA composite membranes.Example 3 and water, the oxygen of comparative example 3 obstruct
Ability is listed in table 1.
Embodiment 2
(1) preparations such as cleaning, drying of base material；Using PET as base material, it is cleaned by ultrasonic respectively with acetone, alcohol, deionized water
30 minutes, it is then fed into the drying of wind turbine portion.
(2) ready base material is sent into pre-sputtering vacuum tank and carries out pre-sputter cleaning, pre-sputtering gas is 999.99%
Argon gas, it is 2W hours/square centimeter that sputtering power, which increases rate, and sputtering time is 100 seconds；
(3) respectively using PI, ZnO as target, radio-frequency power supply is opened, co-deposition preparation F-Si is carried out on pre-sputtering matrix and is answered
High resistance film is closed, the vacuum degree control of vacuum chamber is in 3 × 10-5Pa, and working gas is 999.99% argon gas, and argon stream amount is
60sccm, operating air pressure control are 0.2Pa, and target-substrate distance 6cm, drum rotation speed control is 2m/ points, the sputtering work(of PI, ZnO
It is 1W/ square centimeters that rate, which controls, and sputtering time is 40 minutes, is prepared for PI/ZnO/PET composite membranes；Finally, it cuts, finished product
After the assay was approved, it winds, packaging and storage.Comparing for convenience, 2 base material of comparative example is same as Example 2, using ZnO as sputtering target material,
Under the conditions of identical sputtering technology, deposition is prepared for ZnO/PET composite membranes.Example 2 and water, the oxygen obstructing capacity of comparative example 2 are listed in
Table 1.
Embodiment 3：
(1) preparations such as cleaning, drying of base material；With 90 parts by weight of polyethylene terephthalate (PET), polyethylene
6.5 parts by weight of LLDPE flexible molecules, butanediol auxiliary agent 0.5-15 parts by weight；Using twin-screw by poly terephthalic acid second two
The mixture extrusion of alcohol ester above-mentioned raw materials prepares compound PET, and basal temperature control is 190-195 DEG C；And using compound PET as base
Material is cleaned by ultrasonic 30 minutes respectively with acetone, alcohol, deionized water, is then fed into the drying of wind turbine portion.
(2) ready compound PET base material is sent into pre-sputtering vacuum tank and carries out pre-sputter cleaning, pre-sputtering gas is
999.99% argon gas, it is 1.5W hours/square centimeter that sputtering power, which increases rate, and sputtering time is 120 seconds；
(3) respectively using PTFE, ZnO as target, radio-frequency power supply is opened, carries out being co-deposited preparation CF- on pre-sputtering matrix
The compound high resistance films of ZnO, vacuum degree control is 2 × 10-5Pa, working gas are 99.99% argon gas, and argon stream amount is
60sccm, operating air pressure control are 0.3Pa, and target-substrate distance 8cm, drum rotation speed control is 2m/ points, the sputtering of PTFE, ZnO
It is 0.5W/ square centimeters that power, which controls, and sputtering time is 30 minutes, is prepared for the compound PET of composite barrier film PTFE/ZnO/；
Finally, it cuts, after product inspection qualification, winding, packaging and storage.Comparing for convenience, comparative example 3 is identical with 3 base material of embodiment, with
ZnO is sputtering target material, and under the conditions of identical sputtering technology, deposition is prepared for the compound PET of composite barrier film ZnO/.Example 1 and comparison
Water, the oxygen obstructing capacity of example 1 are listed in table 1.
Embodiment 4
(1) preparations such as cleaning, drying of base material；Using PA as base material, it is cleaned by ultrasonic respectively with acetone, alcohol, deionized water
15 minutes, it is then fed into the drying of wind turbine portion.
(2) ready base material is sent into pre-sputtering vacuum tank and carries out pre-sputter cleaning, pre-sputtering gas is 999.99%
Argon gas, it is 1.5W hours/square centimeter that sputtering power, which increases rate, and sputtering time is 100 seconds；
(3) respectively with PTFE, SiO2For target, radio-frequency power supply is opened, carries out being co-deposited preparation C- on pre-sputtering matrix
The compound high resistance films of Zr, the vacuum degree control of vacuum chamber is in 3 × 10-5Pa, and working gas is 999.99% argon gas, argon stream
It measures as 60sccm, operating air pressure control is 0.3Pa, and target-substrate distance 8cm, drum rotation speed control is 2m/ points, PTFE, SiO2
Sputtering power be controlled as 2.29W/ square centimeters and 3.42W/ square centimeters, sputtering time is 30 minutes, PTFE/
SiO2/ PA compares for convenience, and comparative example 4 is identical with 4 base material of embodiment, with SiO2For sputtering target material, identical sputtering technology condition
Under, deposition is prepared for SiO2/ PET composite membranes.Example 4 and water, the oxygen obstructing capacity of comparative example 4 are listed in table 1.
Embodiment 5
(1) preparations such as cleaning, drying of base material；Using PET as base material, it is cleaned by ultrasonic respectively with acetone, alcohol, deionized water
15 minutes, it is then fed into the drying of wind turbine portion；
(2) ready base material is sent into pre-sputtering vacuum tank and carries out pre-sputter cleaning, pre-sputtering gas is 999.99%
Argon gas, it is 1.5W hours/square centimeter that sputtering power, which increases rate, and sputtering time is 100 seconds；
(3) respectively with PP, Al2O3For target, radio-frequency power supply is opened, carries out being co-deposited preparation C-Al on pre-sputtering matrix
Compound high resistance film, the vacuum degree control of vacuum chamber is in 3 × 10-5Pa, and working gas is 999.99% argon gas, argon stream amount
For 60sccm, operating air pressure control is 0.3Pa, and target-substrate distance 8cm, drum rotation speed control is 2m/ points, PP, Al2O3Splash
It penetrates power and is controlled as 0.39W/ square centimeters and 1.42W/ square centimeters, sputtering time 60min prepares composite barrier film
PP/Al2O3/PET.Compare for convenience, comparative example 5 is identical with 5 base material of embodiment, with Al2O3For sputtering target material, identical sputtering work
Under the conditions of skill, deposition is prepared for Al2O3/ PET composite membranes.Example 5 and water, the oxygen obstructing capacity of comparative example 5 are listed in table 1.
Advantage of the invention is that：
By pre-sputtering step, the adsorbed gas of substrate surface, pollutant, oxide are removed, also by poor adhesion
Particle removes so that surface increases activity, and the adhesive force of base material is enhanced.
Using macromolecule as target, it is broken that organic polymer flexible chain is introduced in film layer is obstructed using RF magnetron co-sputtering method
Piece improves the folding resistance of film.
By high molecular polymer be target, magnetic control co-sputtering technology deposition laminated film after material overall performance will
To raising.
(1) deposition laminated film post-tensioning performance will have large change, and whole tensile property improves, and laminated film is resistance to
Folding is had excellent performance, and polymer segment introduces film and forms composite construction, can significantly improve its toughness, even across repeatedly repeatedly
It folds, deposited barrier layers are also not in be completely severed crackle, still maintain higher obstructing capacity.
(2) deposit laminated film after, after the introducing of macromolecule soft segment, alleviate inorganic nanoparticles deposition when due to
The crackle and defect problem that island is mended effect and generated improve the compactness of deposition Obstruct membrane and to H2The resistance of O steam, oxygen
Every ability.
(3) will have to migration of the organic polymer to pack content in inhibition heavy metal and plastics after depositing laminated film
Apparent effect, SiO2、Al2O3、ZrO2It waits inorganic particulates that can reduce polymer segment movement degree, reduces free volume, reduce
The channel and probability of migration.
(4) by the film of three layers of duplex spread-blade, the compound high-resistant diaphragm of fold resistant also significantly proposes the reservation of food flavor
Height while meeting the extension food shelf time, maintains the original fragrance of food.
Table 1
Table 1 is embodiment 1-5 and water, the oxygen permeability of corresponding comparative example, is compared by numerical value as can be seen that with macromolecule
Polymer is target, flexible composite film prepared by itself and inorganic material cosputtering deposition, barrier to water, oxygen and anti-
Rotten, moisture-proof, the fragrant ability of guarantor is above inorganic, inorganic oxide as target, and (inorganic oxide deposition is thin for prepared laminated film
Film) and former film.
The SEM figures of (B) after Fig. 2 is the embodiment of the present invention 1 (A) and folds 100 times.The A and B of Fig. 2 shows radio frequency magnetron
Sputtering method prepare PI SiO2Compound barrier film surface uniformly, it is fine and close, and after 100 times fold, PI SiO2Barrier film surface
The slight crack of appearance is slight, does not extend to bottom, remains to the higher water of holding, oxygen obstructing capacity, i.e. macromolecule PI soft segments
Introducing, effectively increase the toughness of composite membrane, improve its resistant to collapsing ability and service life.
Fig. 3 is the embodiment of the present invention 2 (A) and comparative example 2 (B) and the SEM figures being separately folded after 100 times (C and D).Fig. 3
A and B show radio-frequency magnetron sputter method prepare barrier film PI ZnO compound PET and ZnO compound pet sheet face uniformly,
Densification can play preferable iris action to water, oxygen.Fig. 3 C and 3D show 100 times after folding that ZnO barrier films surface goes out
Now fold fracture, and extend to base material bottom, although and PI ZnO barrier films surface it can be seen that slight crack, slight crack are light
It is micro-, and do not extend to bottom, remain to the higher water of holding, oxygen obstructing capacity.Fig. 3 A-D show macromolecule PI soft segments
It introduces, while improving compactness, the barrier property of film, also adds the toughness of composite membrane, improve its resistant to collapsing ability with making
Use the service life.
Fig. 4 is the XRD diagram of embodiment 3 and comparative example 3, from Fig. 4, the XRD curves of comparative example 3 it is found that 2 θ be 34.3 °,
Occur the diffraction maximum of apparent zinc oxide at 47.2 °, 62.5 °, 67.8 °, corresponded to zinc oxide hexagonal crystal system respectively
(002), (102), (103), (112), compared to embodiment 3, barrier layer XRD curves at 31.3 °, 35.6 ° also in 2 θ to occur
The diffraction maximum of PTFE, has corresponded to (111) of PTFE hexagonal crystal systems, (200) crystal face respectively, and the introducing of macromolecule PTFE for
The diffraction maximum position of zinc oxide hexagonal crystal system and intensity effect are little, when showing double target cosputterings, macromolecule soft segment
Introduce that there is no the crystalline structures for changing zinc oxide, uniform distribution is among zincite crystal, increasing oxygen in the form of crystallization
Change zinc barrier layer is flexible simultaneously, has filled up the crackle generated due to " island benefit effect " during zinc oxide sputtering, can be further
The compactness for improving composite membrane and the obstructing capacity to small molecules such as water oxygens.
Fig. 5 is that the embodiment of the present invention 3 (A) and the SEM of comparative example 3 (B) scheme.The A and B of Fig. 5 shows radio-frequency magnetron sputter method
The barrier film PTFE of preparation ZnO compound PET and ZnO compound pet sheet face uniformly, it is fine and close, water, oxygen can be played compared with
Good iris action.
Fig. 6 is that the SEM after the embodiment of the present invention 3 (A) folds 100 times with comparative example 3 (B) schemes and it amplifies SEM and schemes (C
And D).The A-D of Fig. 6 shows 100 times after folding that ZnO barrier films surface occurs folding fracture, and extend to base material bottom,
And PTFE ZnO barrier films surface be only capable of seeing slight crack, but slight crack is slight.Observe enlarged drawing 6C understand PTFE ZnO barriers it is thin
The slight crack of film surface does not extend to bottom, remains to the higher water of holding, oxygen obstructing capacity.Fig. 5 A, 5B and Fig. 6 A-D association lists
Bright, the introducing of macromolecule PTFE soft segments while improving compactness, the barrier property of film, also adds the toughness of composite membrane,
Improve its resistant to collapsing ability and service life.
Fig. 6 B and D are also shown that only introduces macromolecule soft segment in the substrate, though the flexibility of base material PET can be improved,
The micro-crack of barrier layer, toughness and folding resistance are not relieved, also illustrate patent 2015104585235 for
The raising of composite membrane folding resistance is nothing like method and technique that this patent is reported.
Claims (8)
1. a kind of magnetron sputtering preparation process of fold resistant high-barrier composite packing film, it is characterised in that：It comprises the following steps：
(1) preparation of base material；(2) base material is sent into pre-sputtering vacuum tank and carries out pre-sputter cleaning, pre-sputtering gas is 99.95%-
99.99% argon gas, pre-sputtering power increase rate are 0.1-6W hours/square centimeter, and sputtering time is 30-500 seconds；(3) it opens
Radio-frequency power supply is opened, more targets are carried out on pre-sputtering matrix deposits simultaneously to prepare compound high resistance film, wherein, by the base of pre-sputtering
Material is wrapped in cylinder surface and fixes, and the vacuum degree control of vacuum chamber is in 0.1-10 × 10-5Pa, working gas are argon gas or argon oxygen
Gaseous mixture, purity of argon 99.95%-99.99%, throughput 10-450sccm, oxygen purity 99.95%-
99.999%, throughput 0.5-100sccm, operating air pressure control are 0.2-2Pa, and target-substrate distance 4-16cm, roller rotates fast
Degree control is 0.5-10m/ points, and sputtering time is 5-300 minutes；More target cosputterings are using high molecular polymer as target
Material sputters its target double with composition one or two kinds of in inorganic target, inorganic oxide target or three targets simultaneously.
2. a kind of magnetron sputtering preparation process of fold resistant high-barrier composite packing film according to claim 1, special
Sign is：The base material be using by polyethylene terephthalate, PP, EVOA and PA one-component or more than one
Component multilayer plastic alloy.
3. a kind of magnetron sputtering preparation process of fold resistant high-barrier composite packing film according to claim 1, special
Sign is：The macromolecule target is single or one using PI, PTFE, polyethylene LLDPE, polyisoprene and epoxy resin
Kind or more blending high molecular polymer.
4. a kind of preparation process for sputtering fold resistant high-barrier composite film according to claim 1, it is characterised in that：Institute
The inorganic material stated is Si, Al, one or more than one kinds of in Ti, graphite；Inorganic oxide is SiOx, ZnO, Al2O3、
SiNyOx、TiO2, it is one or more than one kinds of in ITO and DLC etc..
5. a kind of magnetron sputtering preparation process of fold resistant high-barrier composite packing film according to claim 1, special
Sign is：The Sputtering power density of the macromolecule target is 0.1-10W/ square centimeters, inorganic and inorganic oxide target
Sputtering power density for 0.1-15W/ square centimeter, the power density ratio for adjusting macromolecule target and ceramic target is 0.1-10
Between.
6. a kind of magnetron sputtering preparation process of fold resistant high-barrier composite packing film according to claim 1, special
Sign is：The vacuum degree control of the vacuum chamber is in 2-5 × 10-5Pa, working gas are that working gas is argon gas or argon oxygen
Gaseous mixture, purity of argon 99.95%-99.99%, throughput 40-150sccm, oxygen purity 99.95%-
99.999%, throughput 5-45sccm, operating air pressure control are 0.55-0.9Pa, and target-substrate distance 4-10cm, roller rotates fast
Degree control is 1-3m/ points, and sputtering power control is 0.5-6W/ square centimeters, and sputtering time is 15-90 minutes.
7. a kind of preparation process for sputtering fold resistant high-barrier composite film according to claim 5, it is characterised in that：Institute
The base material single side or double-sided deposition flexible barrier layers stated.
8. a kind of preparation process for sputtering fold resistant high-barrier composite film according to claim 6, it is characterised in that：Institute
The co-deposition target stated is respectively polymer and inorganic material, then working gas is argon oxygen gas mixture, wherein, argon flow amount and oxygen
The ratio of throughput is 100:1-100:Between 90；The co-deposition target is respectively polymer and inorganic oxide, then work
Make gas as argon gas or argon oxygen gas mixture.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109468603A (en) * | 2018-12-24 | 2019-03-15 | 昆山英利悦电子有限公司 | A kind of vacuum coating method suitable for mobile phone Kato |
| CN109795793A (en) * | 2019-03-25 | 2019-05-24 | 成都新柯力化工科技有限公司 | A kind of heavy packaging high-barrier plastic packaging film and preparation method |
| CN114388372A (en) * | 2021-05-19 | 2022-04-22 | 上海音特电子有限公司 | Technological method for power semiconductor PN junction protection |
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| CN101359723A (en) * | 2003-03-07 | 2009-02-04 | 友达光电股份有限公司 | Preparation of organic light emitting display |
| CN102877036A (en) * | 2012-10-26 | 2013-01-16 | 哈尔滨商业大学 | Crack-free multilayer high-barrier packaging film prepared by adopting rotary radio frequency magnetron sputtering method |
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| CN101359723A (en) * | 2003-03-07 | 2009-02-04 | 友达光电股份有限公司 | Preparation of organic light emitting display |
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| CN109468603A (en) * | 2018-12-24 | 2019-03-15 | 昆山英利悦电子有限公司 | A kind of vacuum coating method suitable for mobile phone Kato |
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Application publication date: 20180710 |