CN107599575A - A kind of gas barrier film - Google Patents

A kind of gas barrier film Download PDF

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Publication number
CN107599575A
CN107599575A CN201710802199.3A CN201710802199A CN107599575A CN 107599575 A CN107599575 A CN 107599575A CN 201710802199 A CN201710802199 A CN 201710802199A CN 107599575 A CN107599575 A CN 107599575A
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layer
base material
nanomaterial
barrier film
gas barrier
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CN201710802199.3A
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于盟盟
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Abstract

The invention provides a kind of gas barrier film, including:Base material, the material of base material are chosen to the material with Electrostatic Absorption function, and base material has first surface and the second surface with first surface opposite direction, and first surface is attached on sample to be isolated;Polymeric layer, it forms the second surface in base material, and polymeric layer includes the siloxane reaction product of primary amino radical or tertiary amino functionalized silane with least three silane groups;Layer of nanomaterial, it is formed includes CNT and/or graphene in the surface of polymeric layer, the material that layer of nanomaterial is selected;Ultraviolet resistant layer, it is formed is handled in the surface of layer of nanomaterial, ultraviolet resistant layer by vacuum ultraviolet light.The gas barrier film of the present invention does not need more lamination, the only four layers barrier that higher vapor and oxygen can be achieved, and inventor passes through lot of experiment validation, and initiative choose the preferable material of above-mentioned bending resistance, it is therefore prevented that the crackle as caused by membrane stress.

Description

A kind of gas barrier film
Technical field
The present invention relates to needing the high food of barrier properties for gases, the packaging applicationss of pharmaceuticals, solar cell, electronics The gas barrier film used in paper (electronicpaper), organic EL etc. electronic unit purposes.
Background technology
On the surface of polymeric membrane base material, the inorganic matters such as aluminum oxide, silica, magnesia (including inorganic oxide is used Thing), utilize the physical vapor growth method (PVD method) or plasma chemistry of vacuum vapour deposition, sputtering method, ion plating method etc. Chemical gas phase growth methods (CVD) of vapor growth method, thermal chemical vapor growth method, photochemical vapor growth method etc. etc., formed The transparent gas barrier film that the evaporation film of the inorganic matter forms, it is used as needing to separate the various gases such as vapor and oxygen The electronic components of the packaging material and slim TV machines of food and medicine product etc., solar cell etc..
As barrier properties for gases technology is improved, for example, once having used following methods:By using containing organo-silicon compound Steam and oxygen gas, formed using plasma CVD method on base material by based on Si oxide and containing carbon, hydrogen, The layer that the compound of at least one kind of element in silicon and oxygen is formed, to improve barrier properties for gases when maintaining the transparency.Separately Outside, as the raising barrier properties for gases technology beyond film build method, once used:By being alternately laminated epoxidation on substrate Compound organic layer and crackle caused by membrane stress is prevented with the silicon systems oxide skin(coating) that plasma CVD method is formed and is lacked The gas barrier film of the multilayer laminate constructions of sunken generation.
However, in the method that using plasma CVD forms using Si oxide as the barrier properties for gases layer of principal component, The barrier properties for gases layer formed is very fine and close and high rigidity layer, therefore in order to obtain in organic EL and Electronic Paper purposes In required for moisture-vapor transmission 10-3g/(m2High gas-obstructing character 24hratm) below is, it is necessary to thick-film.
On the other hand, in the method for forming organic layer and the inorganic layer alternately barrier properties for gases layer of multilayer laminated composition In, in order to obtain moisture-vapor transmission 10-3g/(m2High gas-obstructing character 24hratm) below is, it is necessary to tens of layers more Layer stackup.
The content of the invention
In order to solve the above-mentioned technical problem, the invention provides a kind of gas barrier film, including:
Base material, the material of the base material are chosen to the material with Electrostatic Absorption function, and the base material has first surface With the second surface with the first surface opposite direction, the first surface is attached on sample to be isolated;
Polymeric layer, it forms the second surface in the base material, and the polymeric layer, which includes, has at least three The primary amino radical of silane group or the siloxane reaction product of tertiary amino functionalized silane;
Layer of nanomaterial, it is formed includes carbon in the surface of the polymeric layer, the material that the layer of nanomaterial is selected Nanotube and/or graphene;
Ultraviolet resistant layer, it is formed passes through vacuum-ultraviolet light in the surface of the layer of nanomaterial, the ultraviolet resistant layer According to processing.
Further, the base material selects the PVDC modified resins with high-barrier water oxygen performance.
Further, the thickness 50-100nm of the base material, the thickness of the polymeric layer is 100-200nm, described to receive The thickness of rice material layer is 10-50nm, and the thickness of the ultraviolet resistant layer is 100-200nm.
Further, the ratio between density of the base material, polymeric layer, layer of nanomaterial and ultraviolet resistant layer is 0.5-1:1- 2:0.5-0.8:1-1.2。
Further, the material that the layer of nanomaterial is selected also includes the component of following parts by weight:Vinyl ester resin 10-30 parts;Ethene acid monomers 40-60 parts;Light trigger 1-5 parts;Dispersant 0.2-0.5 parts;Coupling agent 0.2-0.5 parts.
Further, the polymeric layer and the layer of nanomaterial are prepared by coating process.
Further, the coefficient of thermal expansion of the base material is less than 500ppm/ DEG C, and more than 200ppm/ DEG C.
Further, the layer of nanomaterial be by PECVD fabricated in situ on the polymeric layer.
Further, the base material, polymeric layer, layer of nanomaterial and ultraviolet resistant layer are flexible.
Further, the Obstruct membrane is bent to radius of curvature be 10mm after water vapor permeance be less than 0.005g/m2·day。
The gas barrier film of the present invention does not need more lamination, the only four layers resistance that higher vapor and oxygen can be achieved Every, and inventor passes through lot of experiment validation, and it is initiative choose the preferable material of above-mentioned bending resistance, prevent The crackle as caused by membrane stress.In addition, it is flexible per Rotating fields, even if Obstruct membrane bending that is, of the invention can also maintain Higher water vapour and oxygen barrier performance.
According to the accompanying drawings will be brighter to the detailed description of the specific embodiment of the invention, those skilled in the art Above-mentioned and other purposes, the advantages and features of the present invention.
Brief description of the drawings
Some specific embodiments of the present invention are described in detail by way of example, and not by way of limitation with reference to the accompanying drawings hereinafter. Identical reference denotes same or similar part or part in accompanying drawing.It should be appreciated by those skilled in the art that these What accompanying drawing was not necessarily drawn to scale.In accompanying drawing:
Fig. 1 is the schematic diagram of the gas barrier film of one embodiment of the invention.
Embodiment
Fig. 1 shows the schematic diagram of the gas barrier film of one embodiment of the invention.It is as shown in figure 1, of the invention A kind of gas barrier film is provided, including:Base material 1, the material of the base material 1 are chosen to the material with Electrostatic Absorption function, The base material 1 has first surface and the second surface with the first surface opposite direction, and the first surface, which is attached to, to be treated Isolate on sample;Polymeric layer 2, it forms the second surface in the base material 1, and the polymeric layer 2, which includes, to be had extremely The primary amino radical of few three silane groups or the siloxane reaction product of tertiary amino functionalized silane;Layer of nanomaterial 3, it is formed The surface of the polymeric layer 2, the material that the layer of nanomaterial 3 is selected include CNT and/or graphene;Antiultraviolet Layer 4, it is formed is handled in the surface of the layer of nanomaterial 3, the ultraviolet resistant layer 4 by vacuum ultraviolet light.
The base material 1 is from the PVDC modified resins with high-barrier water oxygen performance.
The thickness 50-100nm of the base material 1, the thickness of the polymeric layer 2 are 100-200nm, the layer of nanomaterial 3 thickness is 10-50nm, and the thickness of the ultraviolet resistant layer 4 is 100-200nm.The base material 1, polymeric layer 2, nanometer material The ratio between density of the bed of material 3 and ultraviolet resistant layer 4 is 0.5-1:1-2:0.5-0.8:1-1.2.
In one embodiment, the thickness of the base material is 50nm, and the thickness of the polymeric layer 2 is 100nm, described to receive The thickness of rice material layer 3 is 10nm, and the thickness of the ultraviolet resistant layer 4 is 100nm.The base material 1, polymeric layer 2, nanometer material The ratio between density of the bed of material 3 and ultraviolet resistant layer 4 is 0.5:1:0.5:1.In another embodiment, the thickness of the base material 1 100nm, the thickness of the polymeric layer 2 are 200nm, and the thickness of the layer of nanomaterial 3 is 50nm, the ultraviolet resistant layer 4 Thickness be 200nm.The base material 1, polymeric layer 2, the ratio between the density of layer of nanomaterial 3 and ultraviolet resistant layer 4 are 1:2: 0.8:1.2.In another embodiment, the thickness 70nm of the base material 1, the thickness of the polymeric layer 2 is 150nm, described to receive The thickness of rice material layer 3 is 30nm, and the thickness of the ultraviolet resistant layer 4 is 150nm.The base material 1, polymeric layer 2, nanometer material The ratio between density of the bed of material 3 and ultraviolet resistant layer 4 is 0.6:1.6:0.6:1.1.
In one embodiment, the polymeric layer 2 and the layer of nanomaterial 3 are prepared by coating process. In another embodiment, the layer of nanomaterial 3 be by PECVD fabricated in situ on the polymeric layer 2.
The material that the layer of nanomaterial 3 is selected also includes the component of following parts by weight:Vinyl ester resin 10-30 parts; Ethene acid monomers 40-60 parts;Light trigger 1-5 parts;Dispersant 0.2-0.5 parts;Coupling agent 0.2-0.5 parts.The heat of the base material 1 Expansion rate is less than 500ppm/ DEG C, and more than 200ppm/ DEG C.
In one embodiment, the material that the layer of nanomaterial 3 is selected also includes the component of following parts by weight:Vinyl 10 parts of ester resin;40 parts of ethene acid monomers;1 part of light trigger;0.2 part of dispersant;0.2 part of coupling agent.The base material 1 it is hot swollen Swollen rate is 300ppm/ DEG C.In another embodiment, the material that the layer of nanomaterial 3 is selected also includes the group of following parts by weight Point:30 parts of vinyl ester resin;60 parts of ethene acid monomers;5 parts of light trigger;0.5 part of dispersant;0.5 part of coupling agent.The base The coefficient of thermal expansion of material 1 is 250ppm/ DEG C.In another embodiment, the material that the layer of nanomaterial 3 is selected also includes following weight Measure the component of part:20 parts of vinyl ester resin;50 parts of ethene acid monomers;3 parts of light trigger;0.4 part of dispersant;Coupling agent 0.3 Part.The coefficient of thermal expansion of the base material 1 is 400ppm/ DEG C.
The base material 1, polymeric layer 2, layer of nanomaterial 3 and ultraviolet resistant layer 4 are flexible.By the barrier Film is bent to radius of curvature is less than 0.005g/m for the water vapor permeance after 10mm2·day.In one embodiment, inciting somebody to action The water vapor permeance that the Obstruct membrane bends after being 10mm to radius of curvature is 0.001g/m2·day.In another embodiment In, it is 0.0005g/m the Obstruct membrane to be bent to the water vapor permeance after being 10mm to radius of curvature2·day。
The gas barrier film of the present invention does not need more lamination, the only four layers resistance that higher vapor and oxygen can be achieved Every, and inventor passes through lot of experiment validation, and it is initiative choose the preferable material of above-mentioned bending resistance, prevent The crackle as caused by membrane stress.In addition, it is flexible per Rotating fields, even if Obstruct membrane bending that is, of the invention can also maintain Higher water vapour and oxygen barrier performance.
So far, although those skilled in the art will appreciate that detailed herein have shown and described multiple showing for the present invention Example property embodiment, still, still can be direct according to present disclosure without departing from the spirit and scope of the present invention It is determined that or derive many other variations or modifications for meeting the principle of the invention.Therefore, the scope of the present invention is understood that and recognized It is set to and covers other all these variations or modifications.

Claims (10)

  1. A kind of 1. gas barrier film, it is characterised in that including:
    Base material, the material of the base material are chosen to the material with Electrostatic Absorption function, the base material have first surface and with The second surface of the first surface opposite direction, the first surface are attached on sample to be isolated;
    Polymeric layer, it forms the second surface in the base material, and the polymeric layer, which includes, has at least three silane The primary amino radical of group or the siloxane reaction product of tertiary amino functionalized silane;
    Layer of nanomaterial, it is formed includes carbon nanometer in the surface of the polymeric layer, the material that the layer of nanomaterial is selected Pipe and/or graphene;
    Ultraviolet resistant layer, it is formed on the surface of the layer of nanomaterial, and the ultraviolet resistant layer is by vacuum ultraviolet light Reason.
  2. 2. gas barrier film according to claim 1, it is characterised in that the base material, which is selected, has high-barrier water oxygen performance PVDC modified resins.
  3. 3. gas barrier film according to claim 2, it is characterised in that the thickness 50-100nm of the base material, it is described poly- The thickness of compound layer is 100-200nm, and the thickness of the layer of nanomaterial is 10-50nm, and the thickness of the ultraviolet resistant layer is 100-200nm。
  4. 4. gas barrier film according to claim 3, it is characterised in that the base material, polymeric layer, layer of nanomaterial and The ratio between density of ultraviolet resistant layer is 0.5-1:1-2:0.5-0.8:1-1.2.
  5. 5. according to the gas barrier film any one of claim 1-4, it is characterised in that what the layer of nanomaterial was selected Material also includes the component of following parts by weight:Vinyl ester resin 10-30 parts;Ethene acid monomers 40-60 parts;Light trigger 1-5 Part;Dispersant 0.2-0.5 parts;Coupling agent 0.2-0.5 parts.
  6. 6. gas barrier film according to claim 5, it is characterised in that the polymeric layer and the layer of nanomaterial are equal It is prepared by coating process.
  7. 7. gas barrier film according to claim 6, it is characterised in that the coefficient of thermal expansion of the base material is less than 500ppm/ DEG C, and more than 200ppm/ DEG C.
  8. 8. gas barrier film according to claim 5, it is characterised in that the layer of nanomaterial is former by PECVD Position synthesis is on the polymeric layer.
  9. 9. according to the gas barrier film any one of claim 1-4, it is characterised in that the base material, polymeric layer, receive Rice material layer and ultraviolet resistant layer are flexible.
  10. 10. gas barrier film according to claim 9, it is characterised in that bent by the Obstruct membrane to radius of curvature It is less than 0.005g/m for the water vapor permeance after 10mm2·day。
CN201710802199.3A 2017-09-07 2017-09-07 A kind of gas barrier film Pending CN107599575A (en)

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Application Number Priority Date Filing Date Title
CN201710802199.3A CN107599575A (en) 2017-09-07 2017-09-07 A kind of gas barrier film

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Publication Number Publication Date
CN107599575A true CN107599575A (en) 2018-01-19

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130059155A1 (en) * 2011-09-01 2013-03-07 Industry-University Cooperation Foundation Hanyang University Gas barrier thin film, electronic device including the same, and method of preparing gas barrier thin film
JP2014504236A (en) * 2010-11-02 2014-02-20 ザ プロクター アンド ギャンブル カンパニー Degradable sachets for market development
CN104768758A (en) * 2012-08-08 2015-07-08 3M创新有限公司 Barrier film, method of making the barrier film, and articles including the barrier film
CN105102215A (en) * 2013-02-07 2015-11-25 东洋制罐集团控股株式会社 Gas barrier laminate having excellent moisture barrier properties
CN105189103A (en) * 2012-10-18 2015-12-23 泰拉屏障膜公司 Encapsulation barrier stack

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014504236A (en) * 2010-11-02 2014-02-20 ザ プロクター アンド ギャンブル カンパニー Degradable sachets for market development
US20130059155A1 (en) * 2011-09-01 2013-03-07 Industry-University Cooperation Foundation Hanyang University Gas barrier thin film, electronic device including the same, and method of preparing gas barrier thin film
CN104768758A (en) * 2012-08-08 2015-07-08 3M创新有限公司 Barrier film, method of making the barrier film, and articles including the barrier film
CN105189103A (en) * 2012-10-18 2015-12-23 泰拉屏障膜公司 Encapsulation barrier stack
CN105102215A (en) * 2013-02-07 2015-11-25 东洋制罐集团控股株式会社 Gas barrier laminate having excellent moisture barrier properties

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