CN104385731B - Barrier film encapsulated for flexible electronic product and preparation method thereof - Google Patents
Barrier film encapsulated for flexible electronic product and preparation method thereof Download PDFInfo
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- CN104385731B CN104385731B CN201410564013.1A CN201410564013A CN104385731B CN 104385731 B CN104385731 B CN 104385731B CN 201410564013 A CN201410564013 A CN 201410564013A CN 104385731 B CN104385731 B CN 104385731B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
- B32B2255/102—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer synthetic resin or rubber layer being a foamed layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
- B32B2255/205—Metallic coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/28—Multiple coating on one surface
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- Electroluminescent Light Sources (AREA)
Abstract
The present invention provides a kind of barrier film encapsulated for flexible electronic product and preparation method thereof.The barrier film includes base material layer and forms the barrier composite bed at least one surface of base material layer；Wherein, on the direction away from base material layer, barrier composite bed includes at least first inorganic coating, flexible organic coating and the second inorganic coating successively；Flexible organic coating is solidify to form by the organic composite of the oligomer including acrylic ester compound, hydroxyl and amino, and its thickness control is 200 2000 nanometers；The material of first inorganic coating and the second inorganic coating is formed by silicon, aluminium, magnesium, zinc, tin, nickel, titanyl compound, nitride or carbide, and its thickness is controlled as 5 600 nanometers.The barrier film of the present invention not only has good barriering effect, and with excellent resistance to bend(ing) energy, may be used as flexible display element, the gas barrier property component of the various flexible electronic products of flexible organic solar batteries and flexible organic electro-luminescence element etc..
Description
Technical field
The present invention relates to a kind of barrier film and preparation method thereof；More particularly, it relates to which a kind of be used for flexibility
Barrier film of electronic product packaging and preparation method thereof.
Background technology
Barrier film is derived from packing film, the gas barrier property component as encapsulation electronic product.Packing film is used to obstruct
Oxygen, vapor enter food, in pharmaceuticals packaging, prevent from influenceing because of oxygen, the entrance of vapor food, the quality of pharmaceuticals and
Quality.With the development of electronic product, many electronic products use active metal, in order to avoid it is contacted with oxygen, vapor
And causing the performance degradation of electronic product, barrier film starts to be applied to electronic product, while the requirement to its barrier property
In lifting.For example, for liquid crystal display panel, EL display panels, Electronic Paper, the resistance of the encapsulation such as solar cell package material
Every film, it is desirable to which it has the barrier property higher than general barrier film.Especially for soft such as Flexible Displays product
Property electronic product, due to needing to be subjected to bending repeatedly, therefore also require that its used barrier film has good toughness, instead
Still there is outstanding barrier property after multiple bending.
Chinese patent application 201310319310.5 provides a kind of preparation method of sandwich construction high-isolation film, including
Following steps：A. one layer of inorganic coating is deposited with plasma enhanced chemical vapor deposition method over the transparent substrate；B. in 1-
Under 80Pa vacuum states, the inorganic coating of deposition is carved using the gas discharge formation plasma with etching performance
Erosion；C. one layer of inorganic coating is deposited in the above-mentioned inorganic coating surface plasma enhanced chemical vapor deposition method being etched；
Repeat the above steps, obtain multilayer high-barrier film.In the technical scheme, due to utilizing the gas discharge with etching performance
Plasma is formed to perform etching the inorganic coating of deposition, therefore coating can form interface with plating interlayer, cause film to bend
When coating be moved or be layered, the barriering effect of film declines, and is not suitable for being applied to flexible package.
Chinese patent application 200980117732.6 provides a kind of gas barrier laminated film for organic devices, and it has multi-disc
Gas barrier laminate, and the gas barrier laminated film is to clip bond layer between multi-disc gas barrier laminate to carry out lamination and shape
Into, gas barrier laminate is that have at least one face of matrix material film formed by least two layers inorganic thin film layer,
Wherein, at least two layers inorganic thin film layer includes more than two layers of the inorganic thin film layer to be formed that contacts with each other, and will treat the choke of lamination
Property laminated body matrix material film side face it is relative with the face of the inorganic thin film layer side of another gas barrier laminate with carry out
The lamination of gas barrier laminate, and bond layer is by with m-xylene diamine skeleton, p dimethylamine's skeleton and bisphenol backbone
At least one of skeleton epoxies bonding agent constitute.In the technical scheme, bond layer is two layers of gas barrier laminate
While bonding, also inorganic thin film layer is hardened, become fragile so that the resistance to bend(ing) after high-isolation film encapsulation can have a greatly reduced quality.
Chinese patent application 201080014715.2 discloses a kind of gas barrier film, and it has：Matrix material, it is successively set on
The layer and inorganic layer containing poly organo siloxane compound on an at least side surface for matrix material, wherein, inorganic matter
Layer is formed by dynamic ion beam mixing method.The gas barrier film is not easy to crack when having closely sealed interfloor height, bending
Advantage, but its moisture-vapor transmission is still higher, such as embodiment 1 into embodiment 7 obtained by gas barrier film vapor it is saturating
Rate is crossed for 0.01-0.10g/m2.day, the moisture-vapor transmission after bend test reaches 0.10-0.35g/m2.day。
It can be seen that, either above-mentioned barrier film warp resist bending poor-performing of the prior art, or vapor water barriers performance
Deficiency, when using it for liquid crystal display panel, EL display panels during the encapsulation of flexible electronic product such as Electronic Paper, are easily caused
Flexible electronic product fails because aoxidizing, being passivated.Accordingly, it is desirable to provide a kind of barrier suitable for flexible electronic product encapsulation is thin
Film and preparation method thereof.
The content of the invention
There is being used for for good resistance to bend(ing) energy again it is an object of the invention to provide a kind of existing preferable barrier property
Barrier film of flexible electronic product encapsulation and preparation method thereof.
On the one hand, in order to realize the purpose of the present invention, the invention provides a kind of resistance encapsulated for flexible electronic product
Every film, it includes base material layer and forms the barrier composite bed at least one surface of base material layer；Remote
On the direction of base material layer, it is inorganic that barrier composite bed includes at least first inorganic coating, flexible organic coating and second successively
Coating；Flexible organic coating is consolidated by the organic composite of the oligomer including acrylic ester compound, hydroxyl and amino
Change what is formed, its thickness control is 200-2000 nanometers；The material of first inorganic coating and the second inorganic coating be by silicon, aluminium,
What magnesium, zinc, tin, nickel, titanyl compound, nitride or carbide were formed, its thickness is controlled as 5-600 nanometers.
Selectively, barrier composite bed also includes being sequentially laminated on flexible organic coating on the second inorganic coating, the 3rd
Inorganic coating；Barrier composite bed can further include more flexible organic coatings and inorganic coating, and each flexibility is organic
Coating and inorganic coating arranged for interval, to reach more preferably barriering effect.Preferably, barrier composite bed includes 2-5 layers of inorganic plating
Layer.
There is a flexible organic coating, each flexibility in the barrier film of the present invention, between two layers adjacent of inorganic coating
Organic coating covers the projection and pit of its previous inorganic coating surface, and more smooth growth base is provided for latter inorganic coating
Face so that the surface roughness reduction of latter inorganic coating, so as to reduce the pinprick on its surface, the defect such as hole finally gives
The barrier film that surface roughness is low, defect is few, improves barrier property good.Meanwhile, each flexible organic coating increase water vapour with
Oxygen extends through the time by the passage of barrier film, and this also enhances barrier property.Further, since in inorganic coating
Fault location can produce stress concentration when barrier film is bent, therefore the defect reduced in inorganic coating can also improve barrier film
Resistance to bend(ing) energy.
In the barrier film of the present invention, flexible organic coating has good toughness, the flexible organic coating of high tenacity
Serve not only as the adhesive of adjacent inorganic coating, it is often more important that be combined with inorganic coating, can be with when barrier film is bent
Play a part of scattered stress, reinforcement and protect inorganic coating, reduce the probability that inorganic coating fractures with displacement.Therefore,
The barrier film of the present invention has excellent resistance to bend(ing) energy, even across multiple bending, remains in that good barrier property.
In the present invention, the thickness of flexible organic coating is 200-2000 nanometers.If flexible organic coating is excessively thin, it is to nothing
The strengthening action of machine coating is not abundant enough；It is uneconomical if its is blocked up, simultaneously because its molecular gap is larger, barrier can be caused
Hydraulic performance decline.
In the present invention, the thickness of each inorganic coating is respectively 5-600 nanometers.If less than 5 nanometers, the particle of inorganic coating is arranged
Cloth is not fine and close, easily leaves passage, while pinprick is a lot, barrier property reduction；If more than 600 nanometers, same material
Inorganic coating internal stress increase, and coating is more brittle, and bending radius is greatly increased, and coating easily ftractures, and barrier property declines.
In the present invention, the material of each inorganic coating is silicon, aluminium, magnesium, zinc, tin, nickel, titanyl compound, nitride or carbonization
Thing.Not only there is excellent barrier property by the inorganic coating obtained by these materials, and light transmission is good, is particularly suitable for
The encapsulation of flexible electronic product.
In the present invention, the material of each inorganic coating can be with identical, can also be different.Preferably, the material of each inorganic coating
It is different, further to improve the resistance to bend(ing) energy of barrier film.
According to the embodiment of the present invention, the thickness of each flexible organic coating is 400-1500 nanometers.Preferably,
Its thickness is 600-1200 nanometers.It is highly preferred that its thickness is 800-1000 nanometers.
In the present invention, each flexible organic coating can be solidify to form by following organic composite, and by weight, this has unit
Compound includes following components：The acrylic ester compound of A, 25%-85% 1-6 reactive functional group degree, B, 15%-75% 4-
The hydroxyl of 6 reactive functional group degree and the oligomer of amino, C, 1%-10% toughener, D, 1%-15% light trigger；Its
In, the percentage by weight of each component is on the basis of component A and component B weight summation.
Preferably, the percentage by weight of the acrylic ester compound of 1-6 reactive functional groups degree is 50- in organic composite
The percentage by weight of the hydroxyl of 85%, 4-6 reactive functional group degree and the oligomer of amino is 15-50%.
It is highly preferred that the percentage by weight of the acrylic ester compound of 1-6 reactive functional groups degree is 75- in organic composite
The percentage by weight of the hydroxyl of 85%, 4-6 reactive functional group degree and the oligomer of amino is 15-25%.
Preferably, formed in the organic composite of each flexible organic coating, acrylic ester compound is selected from diacrylate
Pentadiol ester analog derivative, the tetrol triacrylate analog derivative of trimethylolpropane penta, tetra-acrylate class are derived
Thing, 2,3-butanediol dimethylacrylate analog derivative, methacrylic acid -2- hydroxy methacrylates analog derivative, acrylic acid -1- hydroxyls
The group that base propyl ester analog derivative is constituted.More preferably organic composite includes at least two kinds of different esters of acrylic acids
Compound.
Preferably, formed in the organic composite of each flexible organic coating, the oligomer of hydroxyl and amino is selected from binary
The group that alcohol acrylic resin analog derivative, polyoxyalkylene acrylate analog derivative, the acrylate derivative of polyurethane six are constituted.
Preferably, formed in the organic composite of each flexible organic coating, toughener is end hydroxy butadiene.More preferably
Ground be selection molecular weight be 1000-3000Mn, the end hydroxy butadiene that viscosity is 0.5-5cP (25 DEG C).Because terminal hydroxy group is poly-
The molecular end of butadiene is hydroxyl, has certain compatibility with organic polymer chain, while the double bond on its strand has one
End hydroxy butadiene and mixed with resin are good before fixed activity, the initiation grafting cross-linking reaction in the presence of free radical, photocuring
It is good, thus end hydroxy butadiene, with part resin formation inierpeneirating network structure, enhances two groups in the presence of light trigger
The compatibility divided, improves light transmission rate；Cooperative effect is produced simultaneously, plays a part of " forcing containing ", so that increasing flexibility has
The toughness and stability of organic coating.
Preferably, formed in the organic composite of each flexible organic coating, light trigger is selected from 2- hydroxy-methyls phenyl third
Alkane -1- ketone, 2,4,6- trimethylbenzoy-diphenies phosphine oxide, 2,2- dimethoxy -2- phenyl acetophenones and 2- isopropyls
At least one of thioxanthone.
In the barrier film of the present invention, base material layer is used to support and keep to obstruct composite bed, its material and thickness
Can suitably it be selected according to the particular use of barrier film.For example, base material layer can be prepared from by plastics, this is not only easy
In manufacture, and be conducive to lighting and the softness of barrier film.
According to the embodiment of the present invention, base material layer is by PET (PET), PEN
(PEN), PE (polyethylene), PA (polyamide), PP (polypropylene), PI (polyimides), PCTFE (poly- three
Fluorine vinyl chloride), PC (makrolon), at least one of COC (cyclic olefine copolymer) and COP (cyclic olefin polymer) prepare shape
Into.Using these materials can obtain light transmission it is excellent transparent matrix material layer, be particularly suitable for use in translucency have compared with
The barrier film of high request.
According to another embodiment of the present invention, the thickness of base material layer is 12-200 microns.Preferably, it is thick
Spend for 30-150 microns.It is highly preferred that its thickness is 50-125 microns.The thickness control of base material layer in aforementioned range,
Not only preferably it can support and keep to obstruct composite bed, and with preferable pliability.
In the barrier film of the present invention, inorganic coating, which is played, prevents the gas permeation barrier film such as vapor and oxygen
Effect.
According to another embodiment of the present invention, the thickness of each inorganic coating is respectively 20-500 nanometers.Preferably,
The thickness of each inorganic coating is respectively 40-400 nanometers.It is highly preferred that the thickness of each inorganic coating is respectively 50-300 nanometers.
According to another embodiment of the present invention, the thickness of the second inorganic coating is more than the thickness of the first inorganic coating
Degree.When barrier film also includes the more inorganic coating such as the 3rd inorganic coating, the thickness of the 3rd inorganic coating is more than second
The thickness of inorganic coating, and the like, i.e., on the direction away from base material layer, the thickness of each inorganic coating increases successively
Plus.
Preferably, the thickness of the first inorganic coating is 5-200 nanometers, and the thickness of the second inorganic coating is 80-600 nanometers.
It is highly preferred that the thickness of the first inorganic coating is 20-100 nanometers, the thickness of the second inorganic coating is 100-500 nanometers.It is more excellent
Selection of land, the thickness of the first inorganic coating is 30-60 nanometers, and the thickness of the second inorganic coating is 100-300 nanometers.
In the barrier film of the present invention, the thinner thickness of the first inorganic coating, therefore, its surface roughness is smaller, table
Planar defect is also less, and resulting flexible organic coating layer surface is also just more smooth on this surface, and then is follow-up nothing
Machine coating provides more smooth growth basal plane so that the surface roughness reduction of follow-up inorganic coating, surface defect is reduced,
So as to once form thicker inorganic coating, the barrier property and preparation efficiency of barrier film are improved.
According to another embodiment of the present invention, the thickness of each inorganic coating is respectively less than the thickness of each flexible organic coating
Degree.The main function of flexible organic coating is dispersive stress, reinforcement and the inorganic plating of protection when barrier film is bent in the present invention
Layer, reduces the probability that inorganic coating fractures with displacement.Therefore, the thickness of inorganic coating is less than the thickness of flexible organic coating
Degree, makes relatively thin inorganic coating under the support and protection of thicker flexible organic coating, with more preferable resistance to bend(ing) energy.
Each inorganic coating in the present invention can be formed by various appropriate methods, for example, using plasma strengthens
Chemical vapour deposition technique, vacuum vapour deposition, sputtering method, ion plating method, e-beam evaporation, ion-beam evaporation, outside molecular beam
Prolong the inorganic coating of the formation such as method, ion beam mixing method, ion beam implantation.
According to another embodiment of the present invention, each inorganic coating is by plasma enhanced chemical vapor deposition
Method formation.
Plasma enhanced chemical vapor deposition (Plasma-enhancedChemical vapor deposition, letter
Claim PECVD) it is the excited gas in chemical vapor deposition, it is produced low temperature plasma, the chemistry of intensified response material is living
Property, so as to carry out a kind of method of extension.This method can form solid film at a lower temperature, its difference with conventional gas phase method
It is：Hot plasma is as heating source, and temperature is heated or the heating of chemical combustion flame far above conventional, electric-resistance, can synthesize one
It is difficult to the material synthesized under a little low temperature, and because temperature could possibly be higher than the gasification point of many materials, reaction raw materials are except using
Outside the gaseous compound or volatile metal compounds that conventional gas phase method is used, solid bulky grain material and liquid can also be used
Material, greatly expands the accommodation of vapor phase method, and product also more enriches.PECVD specific film build method is：In a reaction
Matrix material is placed on negative electrode by interior, is passed through reacting gas to compared with low pressure, matrix keeps certain temperature, produces aura and puts
Gas ionization near electricity, matrix surface, reacting gas is activated, while matrix surface produces cathodic sputtering, so as to improve
Surface-active.Common thermal chemical reaction is not only there is on matrix surface, the plasma chemistry that also there is complexity is anti-
Should, deposited plating layer is formed under both collective effects chemically reacted.Exciting the method for glow discharge mainly has：Penetrate
Frequency is excited, and high direct voltage is excited, pulse excitation and microwave-excitation.The characteristics of PECVD methods are different from other CVD methods is
Contain the electronics of a large amount of high-energy in gas ions, they can provide the activation energy needed for chemical vapor deposition processes.If by etc.
Gas ions method for generation is divided, and can be divided into the PECVD devices such as direct current glow discharge, radio frequency discharge, microwave discharge.
On the other hand, in order to realize the purpose of the present invention, prepared present invention also offers one kind above-mentioned for flexible electronic
The preparation method of the barrier film of product encapsulation, this method comprises the following steps:
A, offer base material layer；
B, using plasma enhanced chemical vapor deposition method base material layer at least one surface deposit the first nothing
Machine coating；
It is c, inorganic first using the organic composite of the oligomer including acrylic ester compound, hydroxyl and amino
Flexible organic coating is solidify to form on coating；
D, using plasma enhanced chemical vapor deposition method the second inorganic coating is deposited on flexible organic coating.
Selectively, preparation method of the invention also comprises the following steps：
It is e, inorganic second using the organic composite of the oligomer including acrylic ester compound, hydroxyl and amino
Flexible organic coating is solidify to form on coating；
F, using plasma enhanced chemical vapor deposition method the 3rd inorganic coating is deposited on flexible organic coating.
The preparation method of the present invention, which can further include, stacks gradually more flexible organic coatings and inorganic coating
The step of.
In the preparation method of the present invention, flexible organic coating can be prepared by following methods：By precision coating or
Organic composite is coated in corresponding inorganic coating surface by the method for spraying, and carries out UV or electronic beam curing to obtain high tenacity
Flexible organic coating.
According to the embodiment of the present invention, the organic composite in above-mentioned preparation method is to make as follows
For what is obtained：
1. by weight, following material is prepared：
The acrylic ester compound of A, 25%-85% 1-6 reactive functional group degree；
The hydroxyl and the oligomer of amino of B, 15%-75% 4-6 reactive functional group degree；
C, 1%-10% toughener；
D, 1%-15% light trigger；
Wherein, the percentage by weight of each component is on the basis of component A and component B weight summation；
2. in no ultraviolet light and solar radiation, relative air humidity is less than under conditions of 50%, respectively by acrylate
Class compound, the oligomer of hydroxyl and amino, toughener and light trigger are added sequentially in stainless steel, and at each group
It is sufficiently stirred for after dividing addition, to improve the compatibility of each component.
It should be noted that in the material that 1. step is prepared, acrylic ester compound potentially includes two or more
Different components, these different components step 2. in be also to be added sequentially in stainless steel, and each component addition
After be sufficiently stirred for.
Preferably, in addition to step 2. resulting mixture is filtered the step of, to remove impurity.
The barrier film of the present invention not only has good barriering effect, and with excellent resistance to bend(ing) energy, can be with
As flexible display element, flexible various flexible electronic products such as organic solar batteries and flexible organic electro-luminescence element
Gas barrier property component.
Embodiment
Embodiment 1
Barrier film in the present embodiment includes including PET matrix material layer 38 microns thick, the oxygen of 20 nanometer thickness successively
The flexible organic coating of high-ductility and the oxidation titanium coating of 600 nanometer thickness of SiClx coating, 800 nanometer thickness.Its preparation method is as follows：
A, in the one sides of 38 microns thick PET matrix material layers the silica of one layer of 20 nanometer thickness is deposited with PECVD, structure is
SiOx (x=l-2)；
B, the organic composite for being coated with suitable thickness with bar in silica coating surface, and with light-focusing type height are pressed with pole water
Silver-colored lamp (80W/cm) is with 600mJ/cm2Irradiation energy it is irradiated, obtain thickness be 800 nanometers high-ductility flexibility it is organic
Coating；
C, a layer thickness is deposited with PECVD in flexible organic coating layer surface is 600 nanometers of titanium oxide, obtains barrier film
Z-1#.Survey its performance.
Wherein, organic composite is prepared by the following method：
1. following material component is prepared：
2. in no ultraviolet light and solar radiation, relative air humidity is less than under conditions of 50%, by above-mentioned material component
It is added sequentially in stainless steel, and is sufficiently stirred for 20 minutes after the addition of each component；
3. to step, 2. resulting mixture is filtered, and is removed impurity, is obtained organic composite.
Comparative example 1：
Barrier film in this comparative example includes including PET matrix material layer 38 microns thick, the oxygen of 20 nanometer thickness successively
The oxidation titanium coating of SiClx coating and 600 nanometer thickness.Its preparation method is as follows：
A, in the one sides of 38 microns thick PET matrix material layers the silica of one layer of 20 nanometer thickness is deposited with PECVD, structure is
SiOx (x=l-2)；
B, the silica coating surface obtained by step a deposit the titanium oxide that a layer thickness is 600 nanometers with PECVD,
Obtain barrier film D-1#.Survey its performance.
Embodiment 2：
Barrier film in the present embodiment includes including PET matrix material layer 38 microns thick, the oxygen of 200 nanometer thickness successively
The flexible organic coating of high-ductility and the oxidation silicon cladding of 600 nanometer thickness of SiClx coating, 1000 nanometer thickness.Its preparation method is as follows：
A, the one side silica of PECVD one layer of 200 nanometer thickness of deposition in 38 microns thick PET matrix material layer, structure
For SiOx (x=l-2)；
B, the organic composite for being coated with suitable thickness with bar in silica coating surface, and with light-focusing type height are pressed with pole water
Silver-colored lamp (80W/cm) is with 600mJ/cm2Irradiation energy it is irradiated, it is that 1000 nanometers of high-ductility flexibility has to obtain thickness
Organic coating；
C, a layer thickness is deposited with PECVD in flexible organic coating layer surface is 600 nanometers of silica, obtains barrier film
Z-2#.Survey its performance.
Wherein, organic composite is prepared by the following method：
1. following material component is prepared：
2. in no ultraviolet light and solar radiation, relative air humidity is less than under conditions of 50%, by above-mentioned material component
It is added sequentially in stainless steel, and is sufficiently stirred for 20 minutes after the addition of each component；
3. to step, 2. resulting mixture is filtered, and is removed impurity, is obtained organic composite.
Comparative example 2：
Barrier film in this comparative example includes including successively PET matrix material layer 38 microns thick, the of 200 nanometer thickness
Second oxidation silicon cladding of silicon monoxide coating and 600 nanometer thickness.Its preparation method is as follows：
A, the one side silica of PECVD one layer of 200 nanometer thickness of deposition in 38 microns thick PET matrix material layer, structure
For SiOx (x=l-2)；
B, the silica coating surface obtained by step a deposit the silica that a layer thickness is 600 nanometers with PECVD,
Obtain barrier film D-2#.Survey its performance.
Embodiment 3：
Barrier film in the present embodiment includes including PET matrix material layer 125 microns thick, the nitrogen of 50 nanometer thickness successively
The flexible organic coating of high-ductility and the nitridation silicon cladding of 300 nanometer thickness of SiClx coating, 400 nanometer thickness.Its preparation method is as follows：
A, the one side silicon nitride of PECVD one layer of 50 nanometer thickness of deposition in 125 microns thick PET matrix material layer, structure
For Si3Nx (x=3-4)；
B, the organic composite for being coated with suitable thickness with bar in silicon nitride coating surface, and with light-focusing type height are pressed with pole water
Silver-colored lamp (80W/cm) is with 600mJ/cm2Irradiation energy it is irradiated, obtain thickness be 400 nanometers high-ductility flexibility it is organic
Coating；
C, a layer thickness is deposited with PECVD in flexible organic coating layer surface is 300 nanometers of silicon nitride, obtains barrier film
Z-3#.Survey its performance.
Wherein, organic composite is prepared by the following method：
1. following material component is prepared：
2. in no ultraviolet light and solar radiation, relative air humidity is less than under conditions of 50%, by above-mentioned material component
It is added sequentially in stainless steel, and is sufficiently stirred for 20 minutes after the addition of each component；
3. to step, 2. resulting mixture is filtered, and is removed impurity, is obtained organic composite.
Comparative example 3：
Barrier film in this comparative example includes including successively PET matrix material layer 125 microns thick, the of 50 nanometer thickness
Second nitridation silicon cladding of one nitridation silicon cladding and 300 nanometer thickness.Its preparation method is as follows：
A, the one side silicon nitride of PECVD one layer of 50 nanometer thickness of deposition in 125 microns thick PET matrix material layer, structure
For Si3Nx (x=3-4)；
B, the silicon nitride coating surface obtained by step a deposit the silicon nitride that a layer thickness is 300 nanometers with PECVD,
Obtain barrier film D-3#.Survey its performance.
Embodiment 4
Barrier film in the present embodiment includes including PET matrix material layer 200 microns thick, the carbon of 60 nanometer thickness successively
The flexible organic coating of high-ductility and the oxidation silicon cladding of 80 nanometer thickness of SiClx coating, 900 nanometer thickness.Its preparation method is as follows：
A, the one side carborundum of PECVD one layer of 60 nanometer thickness of deposition in 200 microns thick PET matrix material layer, structure
For SiCx (x=1-2)；
B, the organic composite for being coated with suitable thickness with bar in carborundum coating surface, and with light-focusing type height are pressed with pole water
Silver-colored lamp (80W/cm) is with 600mJ/cm2Irradiation energy it is irradiated, obtain thickness be 900 nanometers high-ductility flexibility it is organic
Coating；
C, a layer thickness is deposited with PECVD in flexible organic coating layer surface is 80 nanometers of silica, obtains barrier film
Z-4#.Survey its performance.
Wherein, organic composite is prepared by the following method：
1. following material component is prepared：
2. in no ultraviolet light and solar radiation, relative air humidity is less than under conditions of 50%, by above-mentioned material component
It is added sequentially in stainless steel, and is sufficiently stirred for 20 minutes after the addition of each component；
3. to step, 2. resulting mixture is filtered, and is removed impurity, is obtained organic composite.
Comparative example 4：
Barrier film in this comparative example includes including successively PET matrix material layer 200 microns thick, the of 60 nanometer thickness
Second carbonization silicon cladding of one carbonization silicon cladding and 80 nanometer thickness.Its preparation method is as follows：
A, the one side carborundum of PECVD one layer of 60 nanometer thickness of deposition in 200 microns thick PET matrix material layer, structure
For SiCx (x=l-2)；
B, the carborundum coating surface obtained by step a deposit the silica that a layer thickness is 80 nanometers with PECVD, obtain
To barrier film D-4#.Survey its performance.
Embodiment 5
Barrier film in the present embodiment includes including PEN base material layers 125 microns thick, the oxygen of 30 nanometer thickness successively
The flexible organic coating of high-ductility and the oxidation silicon cladding of 100 nanometer thickness of SiClx coating, 1000 nanometer thickness.Its preparation method is as follows：
A, the one side silica of PECVD one layer of 30 nanometer thickness of deposition in 125 microns of thickness PEN base material layers, structure
For SiOx (x=1-2)；
B, the organic composite for being coated with suitable thickness with bar in silica coating surface, and with light-focusing type height are pressed with pole water
Silver-colored lamp (80W/cm) is with 600mJ/cm2Irradiation energy it is irradiated, it is that 1000 nanometers of high-ductility flexibility has to obtain thickness
Organic coating；
C, a layer thickness is deposited with PECVD in flexible organic coating layer surface is 100 nanometers of silica, obtains barrier film
Z-5#.Survey its performance.
Wherein, organic composite is prepared by the following method：
1. following material component is prepared：
2. in no ultraviolet light and solar radiation, relative air humidity is less than under conditions of 50%, by above-mentioned material component
It is added sequentially in stainless steel, and is sufficiently stirred for 20 minutes after the addition of each component；
3. to step, 2. resulting mixture is filtered, and is removed impurity, is obtained organic composite.
Comparative example 5：
Barrier film in this comparative example includes including successively PEN base material layers 125 microns thick, the of 30 nanometer thickness
Second oxidation silicon cladding of silicon monoxide coating and 100 nanometer thickness.Its preparation method is as follows：
A, the one side silica of PECVD one layer of 30 nanometer thickness of deposition in 125 microns of thickness PEN base material layers, structure
For SiOx (x=l-2)；
B, the silica coating surface obtained by step a deposit the silica that a layer thickness is 100 nanometers with PECVD,
Obtain barrier film D-5#.Survey its performance.
Embodiment 6
Barrier film in the present embodiment includes including PEN base material layers 50 microns thick, the oxidation of 5 nanometer thickness successively
The flexible organic coating of high-ductility and the oxidation silicon cladding of 100 nanometer thickness of silicon cladding, 800 nanometer thickness.Its preparation method is as follows：
A, in the one sides of 50 microns of thickness PEN base material layers the silica of one layer of 5 nanometer thickness is deposited with PECVD, structure is
SiOx (x=1-2)；
B, the organic composite for being coated with suitable thickness with bar in silica coating surface, and with light-focusing type height are pressed with pole water
Silver-colored lamp (80W/cm) is with 600mJ/cm2Irradiation energy it is irradiated, obtain thickness be 800 nanometers high-ductility flexibility it is organic
Coating；
C, a layer thickness is deposited with PECVD in flexible organic coating layer surface is 100 nanometers of silica, obtains barrier film
Z-6#.Survey its performance.
Wherein, organic composite is prepared by the following method：
1. following material component is prepared：
2. in no ultraviolet light and solar radiation, relative air humidity is less than under conditions of 50%, by above-mentioned material component
It is added sequentially in stainless steel, and is sufficiently stirred for 20 minutes after the addition of each component；
3. to step, 2. resulting mixture is filtered, and is removed impurity, is obtained organic composite.
Comparative example 6：
Barrier film in this comparative example includes including PEN base material layers 50 microns thick, the first of 5 nanometer thickness successively
Aoxidize silicon cladding and the second oxidation silicon cladding of 100 nanometer thickness.Its preparation method is as follows：
A, in the one sides of 50 microns of thickness PEN base material layers the silica of one layer of 5 nanometer thickness is deposited with PECVD, structure is
SiOx (x=l-2)；
B, the silica coating surface obtained by step a deposit the silica that a layer thickness is 100 nanometers with PECVD,
Obtain barrier film D-6#.Survey its performance.
Embodiment 7
Barrier film in the present embodiment includes including PEN base material layers 50 microns thick, the oxygen of 30 nanometer thickness successively
SiClx coating, the flexible organic coating of high-ductility of 800 nanometer thickness, the oxidation silicon cladding of 100 nanometer thickness, 800 nanometer thickness high-ductility it is soft
The oxidation silicon cladding of property organic coating and 300 nanometer thickness.Its preparation method is as follows：
A, in the one sides of 50 microns of thickness PEN base material layers the silica of one layer of 30 nanometer thickness is deposited with PECVD, structure is
SiOx (x=1-2)；
B, the organic composite for being coated with suitable thickness with bar in silica coating surface, and with light-focusing type height are pressed with pole water
Silver-colored lamp (80W/cm) is with 600mJ/cm2Irradiation energy it is irradiated, obtain thickness be 800 nanometers high-ductility flexibility it is organic
Coating；
C, a layer thickness is deposited with PECVD in flexible organic coating layer surface is 100 nanometers of silica；
D, the organic composite for being coated with suitable thickness with bar in silica coating surface, and with light-focusing type height are pressed with pole water
Silver-colored lamp (80W/cm) is with 600mJ/cm2Irradiation energy it is irradiated, obtain thickness be 800 nanometers high-ductility flexibility it is organic
Coating；
E, a layer thickness is deposited with PECVD in flexible organic coating layer surface is 300 nanometers of silica, obtains barrier film
Z-7#.Survey its performance.
Wherein, organic composite is prepared by the following method：
1. following material component is prepared：
2. in no ultraviolet light and solar radiation, relative air humidity is less than under conditions of 50%, by above-mentioned material component
It is added sequentially in stainless steel, and is sufficiently stirred for 20 minutes after the addition of each component；
3. to step, 2. resulting mixture is filtered, and is removed impurity, is obtained organic composite.
Comparative example 7：
Barrier film in this comparative example includes including successively PEN base material layers 50 microns thick, the of 30 nanometer thickness
3rd oxidation silicon cladding of silicon monoxide coating, the second oxidation silicon cladding of 100 nanometer thickness and 300 nanometer thickness.Its preparation method
It is as follows：
A, in the one sides of 50 microns of thickness PEN base material layers the silica of one layer of 30 nanometer thickness is deposited with PECVD, structure is
SiOx (x=1-2)；
B, the silica coating surface obtained by step a deposit the silica that a layer thickness is 100 nanometers with PECVD；
C, the silica coating surface obtained by step b deposit the silica that a layer thickness is 300 nanometers with PECVD,
Obtain barrier film D-7#.Survey its performance.
Barrier property test knot of the barrier film of each embodiment and comparative example before alternating bending is shown in table 1 below
Really, show that the barrier film of each embodiment and comparative example is tested through the barrier property after alternating bending 1000 times in table 2 below to tie
Really.Wherein, barrier film is bent by national standard GB/T 6742-2007, from 32mm diameter shaft.
Can be seen that the present invention by the related data in Tables 1 and 2 includes the barrier film of flexible organic coating not only
With good, stable barrier property, and with excellent resistance to bend(ing) energy, after alternating bending 1000 times, still keep high
Barrier.
Table 1：Barrier property test result of each barrier film before alternating bending
Table 2：Each barrier film is through the barrier property test result after alternating bending 1000 times
In table, the method for testing of properties is as follows：
1. barrier composite bed (is made up of) thickness measure each inorganic coating and flexible organic coating
Obtained barrier film is embedded in resin, ultra-thin section is made along its cross-wise direction, and utilize Hitachi
S4800 Electronic Speculum is observed.
2. moisture-vapor transmission
Rice is tested with the type moisture-inhibiting instrument of Aquatran Model 2 of M0C0N companies of the U.S..
3. OTR oxygen transmission rate
Tested using the type oxygen flow instrument of Ox-Tran Model 2/21 of M0C0N companies of the U.S..
Although the present invention is disclosed above with preferred embodiment, the scope that the present invention is implemented is not limited to.This area
Those of ordinary skill, in the invention scope for not departing from the present invention, according to the equal improvement made of the present invention, should be the present invention
Invention scope covered.
Claims (11)
1. a kind of barrier film encapsulated for flexible electronic product, it includes base material layer and formed in described matrix material
Barrier composite bed at least one surface of layer；Wherein, on the direction away from described matrix material layer, the barrier is compound
Layer includes at least first inorganic coating, flexible organic coating and the second inorganic coating successively；
Described flexible organic coating is by the oligomer including acrylic ester compound, hydroxyl or amino, toughener, light
What the organic composite of initiator was solidify to form, its thickness control is 200-2000 nanometers；Wherein, described esters of acrylic acid
Compound is selected from such as next group of material：Diacrylate is to pentadiol ester analog derivative, the acrylic acid of penta tetrol of trimethylolpropane three
Ester derivative, tetra-acrylate analog derivative, 2,3-butanediol dimethylacrylate analog derivative, metering system
Acid -2- hydroxy methacrylates analog derivative and acrylic acid -1- hydroxy propyl ester analog derivatives；Described hydroxyl or the oligomer of amino
Selected from such as next group material：Dihydric alcohol acrylic resin analog derivative, polyoxyalkylene acrylate analog derivative and the propylene of polyurethane six
Acid derivative；Described toughener is end hydroxy butadiene；
The first described inorganic coating and the material of the second inorganic coating be by silicon, aluminium, magnesium, zinc, tin, nickel, titanium oxidation
What thing, nitride or carbide were formed；Wherein, on the direction away from base material layer, the thickness of each inorganic coating increases successively
Plus, the thickness of the second inorganic coating is more than the thickness of the described first inorganic coating, and the thickness of the first inorganic coating is
5-200 nanometers, the thickness of the second inorganic coating is 80-600 nanometers.
2. barrier film as claimed in claim 1, wherein, the thickness of the flexible organic coating is 400-1500 nanometers.
3. barrier film as claimed in claim 1, wherein, described matrix material layer be by PET, PEN, PE, PA, PP, PI,
At least one of PCTFE, PC and COP prepare what is formed.
4. barrier film as claimed in claim 1, wherein, described matrix material layer is prepared by COC to be formed.
5. barrier film as claimed in claim 1, wherein, the thickness of described matrix material layer is 12-200 microns.
6. barrier film as claimed in claim 1, wherein, the thickness of the first inorganic coating is 20-100 nanometers, described
The thickness of second inorganic coating is 100-500 nanometers.
7. barrier film as claimed in claim 6, wherein, the thickness of the first inorganic coating is 30-60 nanometers, described the
The thickness of two inorganic coating is 100-300 nanometers.
8. barrier film as claimed in claim 1, wherein, the thickness of the first inorganic coating and the second inorganic coating
The thickness of respectively less than described flexible organic coating.
9. barrier film as claimed in claim 1, wherein, the first inorganic coating and the second inorganic coating are to pass through
Plasma enhanced chemical vapor deposition method formation.
10. barrier film as claimed in claim 1, wherein, the barrier composite bed is also inorganic including being sequentially laminated on second
Flexible organic coating and the 3rd inorganic coating on coating.
11. a kind of method for preparing the barrier film as described in one of claim 1-10, this method comprises the following steps：
A, offer described matrix material layer；
B, using plasma enhanced chemical vapor deposition method described matrix material layer at least one surface deposition described the
One inorganic coating；
It is c, inorganic described first using the organic composite of the oligomer including acrylic ester compound, hydroxyl or amino
The flexible organic coating is solidify to form on coating；
D, using plasma enhanced chemical vapor deposition method the described second inorganic coating is deposited on the flexible organic coating；
Wherein, on the direction away from base material layer, the thickness of each inorganic coating increases successively, the second inorganic coating
Thickness is more than the thickness of the described first inorganic coating.
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| JPWO2016190284A1 (en) * | 2015-05-22 | 2018-03-08 | コニカミノルタ株式会社 | Gas barrier film and method for producing the same |
| CN105372725B (en) * | 2015-12-04 | 2018-06-05 | 江苏日久光电股份有限公司 | High transmission type optics barrier film |
| CN106206467A (en) * | 2016-08-31 | 2016-12-07 | 惠州市摩码菱丽光电材料有限公司 | A kind of water oxygen Obstruct membrane and preparation method thereof |
| CN206685388U (en) * | 2017-03-14 | 2017-11-28 | 京东方科技集团股份有限公司 | A kind of encapsulating structure, display panel and display device |
| KR102582784B1 (en) * | 2017-03-30 | 2023-09-25 | 린텍 가부시키가이샤 | Functional films and devices |
| CN107238973A (en) * | 2017-07-19 | 2017-10-10 | 苏州星烁纳米科技有限公司 | Quantum dot film and preparation method thereof |
| CN107329319A (en) * | 2017-07-21 | 2017-11-07 | 苏州星烁纳米科技有限公司 | Quantum dot diaphragm and preparation method thereof, backlight module |
| JP7298154B6 (en) * | 2017-08-10 | 2023-11-20 | 東洋紡株式会社 | Manufacturing method of gas barrier film |
| CN108084474A (en) * | 2017-12-18 | 2018-05-29 | 厦门菲尔牡真空技术有限公司 | A kind of nanometer barrier film and preparation method thereof |
| CN108395561A (en) * | 2018-03-28 | 2018-08-14 | 广东轩朗实业有限公司 | Packaging protection film and preparation method thereof |
| CN111116960A (en) * | 2019-12-16 | 2020-05-08 | 苏州普希环保科技有限公司 | Film and method for producing same |
| CN111073016A (en) * | 2019-12-23 | 2020-04-28 | 南京福仕保新材料有限公司 | Degradable film with enhanced water-oxygen barrier performance by chemical vapor deposition |
| CN112724444A (en) * | 2020-12-14 | 2021-04-30 | 兰州空间技术物理研究所 | Ultrahigh barrier film for industrial packaging and preparation method thereof |
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| JP2003071968A (en) * | 2001-09-03 | 2003-03-12 | Toyo Metallizing Co Ltd | Gas barrier film |
| JP4224969B2 (en) * | 2002-02-07 | 2009-02-18 | 凸版印刷株式会社 | Barrier film and conductive barrier film |
| JP4534658B2 (en) * | 2004-08-16 | 2010-09-01 | 凸版印刷株式会社 | Gas barrier film laminate |
| JP5213522B2 (en) * | 2008-05-16 | 2013-06-19 | 三菱樹脂株式会社 | Gas barrier laminated film for organic devices |
| CN103382549B (en) * | 2013-07-27 | 2016-01-27 | 中国乐凯集团有限公司 | A kind of preparation method of multilayered structure high-isolation film |
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