CN105313433A - Method for improving barrier property of graphene complex gas barrier film - Google Patents
Method for improving barrier property of graphene complex gas barrier film Download PDFInfo
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- CN105313433A CN105313433A CN201510628933.XA CN201510628933A CN105313433A CN 105313433 A CN105313433 A CN 105313433A CN 201510628933 A CN201510628933 A CN 201510628933A CN 105313433 A CN105313433 A CN 105313433A
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- film
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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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0036—Heat treatment
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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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/16—Drying; Softening; Cleaning
- B32B38/162—Cleaning
Abstract
The invention discloses a method for improving a barrier property of a graphene complex gas barrier film. The graphene complex gas barrier film sequentially comprises a base film, a gas barrier functional layer, a bonding layer and a protective film; the base film and the protective film each adopts a polymer film; the gas barrier functional layer is one or two or multiple graphene films or overlapped graphene film and nanoscale metal film; before the gas barrier functional layer is compounded with the base film or the protective film containing the bonding layer, the base film or the protective film is put into an oven for heating; the heating temperature and the heating time meet the requirements that the heating temperature is larger than or equal to the debonding temperature of heat release tape or the bonding layer and is smaller than or equal to the deformation temperature of the base film or the protective film, and the heating time is larger than or equal to the debonding time of the heat release tape or the bonding layer. After baking is conducted, a polymeric membrane is shrunk and aged, a subsequent heating process can not cause influence of the size in the horizontal direction on the polymeric membrane, and therefore the graphene can not be damaged due to heat shrinkage.
Description
Technical field
The present invention relates to a kind of method improving Graphene composite gas Obstruct membrane barrier property.
Background technology
Early stage barrier material is all single macromolecular material (as PETG (PET), polyamide (PA), polyvinylidene chloride (PVDC) etc.), polymeric membrane owing to forming silica, aluminium oxide, magnesia etc. on surface as a kind of gas barrier film, effectively can stop oxygen, steam etc., therefore be widely used in the rotten packaging preventing food, industrial goods and pharmaceuticals etc.In addition, also can gas etc. owing to can effectively stop, also can be used for the electronic devices such as sealed solar energy battery, liquid crystal display cells, organic EL element.But there is grain boundary defects between oxide particle, along with the increase of time, some gas or liquid can be revealed, do not have the effect of strict sealing, because there is a lot of hole in macromolecular material, molecule can pass from hole.The defects such as and single macromolecular material also exists the limitation in serviceability, such as mechanical strength is low, printing difference.The employing of metal sealing film can improve sealing effectiveness, but sealing effectiveness is still undesirable.People select to arrange aluminium foil on basement membrane, can obtain stable oxygen, water vapor barrier property, but poor for the barrier of the less hydrogen of molecular weight gas, helium, and pliability is poor, cost is high, and opaque.What people developed in recent years has the Obstruct membrane formed by polyvinylidene chloride (PVDC) or ethylene-vinyl alcohol copolymer (EVOH), also effectively oxygen can be stopped, but the former contains chlorine, have pollution to environment, the barrier of the latter is larger with ambient influnence.The heat conductivility of common polymeric membrane is very poor, and the macromolecule heat conduction material on general industry is all boron nitride by conductive force, aluminium oxide powder is composited as filler, and complex manufacturing process, thermal conductivity is relatively low.
Along with flexible, the demand of transparent superelevation Obstruct membrane on value segment get more and more, as organic thin film solar cell, flexible Organic Light Emitting Diode, Electronic Paper and light vacuum heat-insulating shield.By compound, macromolecule and organic material compound, macromolecule Hana rice Material cladding between macromolecular material, its barrier property and other performances are improved, become the study hotspot of Impermeable Polymer Materials gradually.
Graphene, the bi-dimensional cellular shape crystal tightly packed by monolayer carbon atom, theory calculate shows that the pore-size that complete original graphite alkene film exists is 0.064nm, be less than the diameter (being respectively 0.28nm and 0.314nm) of less molecule hydrogen and helium, so the graphene film of theoretical ideal is impermeable, any gas can be stopped.Over most year, Graphene powder mixes in macromolecular material and makes barrier material by many researchers, and the improvement of barriering effect is comparatively large, but the dispersion of Graphene in macromolecular material also exists problem, because Graphene is easily reunited, to such an extent as to the amount being mixed into Graphene is less.
But, when preparing Graphene Obstruct membrane (graphene film here specially refers to be grown by CVD obtain), because graphene film will be transferred to polymeric membrane substrate from growing substrate, and the Thermal release adhesive tape that transfer process uses or polymethyl methacrylate (PMMA) need the pyroprocess through more than 100 degree.On the one hand, polymer-based counterdie can produce contraction more or less under the high temperature of degree more than 100, and this will cause bad impact to the integrality of the superincumbent graphene film of transfer, and small breakage or fold may occur Graphene; On the other hand, can leave cull on the surface of Graphene after Thermal release adhesive tape or polymethyl methacrylate transfer Graphene, make between graphene film and polymeric membrane, graphene film and graphene film by space increase.Above-mentioned two impacts of aspect on Graphene Obstruct membrane are exactly that final barrier property is deteriorated.
Summary of the invention
The destruction that the thermal contraction that the object of the invention is to solve polymeric membrane causes graphene film, provides a kind of method improving Graphene composite gas Obstruct membrane barrier property.
The technical scheme realizing the object of the invention is a kind of method improving Graphene composite gas Obstruct membrane barrier property, and Graphene composite gas Obstruct membrane is followed successively by basement membrane, gas barrier functional layer, bonding coat and diaphragm; Described basement membrane and diaphragm are polymer film; Described gas barrier functional layer is one deck or two-layer or multi-layer graphene film or graphene film and the superposing of nano level metal film; Thermal release adhesive tape is used to transfer to basement membrane by n (natural number, n >=1) layer graphene film from growing substrate; Or use n (natural number the diaphragm containing bonding coat, n >=1) layer graphene film transfers to diaphragm from growing substrate, before gas barrier functional layer and basement membrane or the diaphragm compound containing bonding coat, basement membrane or diaphragm are put into baking oven and heats; Described heating-up temperature and heat time meet: the deformation temperature of come unstuck temperature≤heating-up temperature≤basement membrane or the diaphragm of Thermal release adhesive tape or bonding coat; Heat time >=usually time of Thermal release adhesive tape or bonding coat.
At use Thermal release adhesive tape by n (natural number; n >=1) layer graphene film to transfer to basement membrane from growing substrate or uses n (natural number the diaphragm containing bonding coat; n >=1) layer graphene film transfers in the process diaphragm from growing substrate; often shift after on one deck graphene film to basement membrane or diaphragm, all the basement membrane of graphene-containing or diaphragm are positioned in organic solvent and soak.
During described often transfer one deck graphene film, the basement membrane of graphene-containing or diaphragm are positioned over the number of times soaked in organic solvent and are at least three times.
Describedly the basement membrane of graphene-containing or diaphragm are positioned over when soaking in organic solution, soak time successively shortens.
Described organic solvent is methylbenzene or dimethylbenzene or ethyl acetate or butanone or aforesaid mixed organic solvents.
After immersion completes, the cleaning of employing pure water, then puts into oven for drying, then shifts next layer graphene film.
Before next layer graphene film of transfer, last layer graphene is protected.
Described basement membrane and diaphragm are PET film or PE film.
Have employed technique scheme, the present invention has following beneficial effect: (1) the present invention is before carrying out graphene film transfer, first heat basement membrane or diaphragm, heating-up temperature and heat time meet: the deformation temperature of come unstuck temperature≤heating-up temperature≤basement membrane or the diaphragm of Thermal release adhesive tape or bonding coat; Heat time >=usually time of Thermal release adhesive tape or bonding coat, the temperature that this temperature is come unstuck higher than Thermal release adhesive tape, the time is also longer than the time that Thermal release adhesive tape comes unstuck far away.After overbaking, polymeric membrane there occurs shrink and aging, follow-up heating process just can not produce the size impact of horizontal direction to polymeric membrane, thus can not because of thermal contraction to Graphene produce destruction.
(2) the present invention is after often shifting one deck graphene film, all carry out immersion and remove cull, the Distance Shortened of graphene layer and interlayer, greatly reduce molecule from horizontal proliferation between graphene layer through probability, improve the barrier property of Obstruct membrane.
(3) the present invention to every layer graphene film soak remove cull time, soak number of times The more the better, soak time successively shortens, obtain as far as possible perfectly Obstruct membrane performance time, also ensure that production efficiency.
(4) the present invention first protects last layer graphene film before next layer graphene film of transfer, and the performance of Obstruct membrane can be made better.
Detailed description of the invention
(embodiment 1)
The method of the improvement Graphene composite gas Obstruct membrane barrier property of the present embodiment, Graphene composite gas Obstruct membrane is followed successively by basement membrane, gas barrier functional layer, bonding coat and diaphragm; Basement membrane and diaphragm are polymer film; Gas barrier functional layer is one deck or two-layer or multi-layer graphene film or graphene film and the superposing of nano level metal film.Basement membrane and diaphragm are PET film or PE film.
The preparation of gas barrier functional layer can be use Thermal release adhesive tape to transfer to basement membrane by n (natural number, n >=1) layer graphene film from growing substrate; Or use and n (natural number, n >=1) layer graphene film is transferred to diaphragm from growing substrate by the diaphragm containing bonding coat.
The emphasis of the present embodiment is following processing method:
(1) before by gas barrier functional layer and basement membrane or the diaphragm compound containing bonding coat, basement membrane or diaphragm are put into baking oven and heats; Heating-up temperature and heat time meet: the deformation temperature of come unstuck temperature≤heating-up temperature≤basement membrane or the diaphragm of Thermal release adhesive tape or bonding coat; Heat time >=usually time of Thermal release adhesive tape or bonding coat.When such as adopting Thermal release adhesive tape, by basement membrane under 130 DEG C of conditions, heat 30 minutes, the temperature that this temperature is come unstuck higher than Thermal release adhesive tape, the time is also longer than the time that Thermal release adhesive tape comes unstuck far away.After overbaking, polymeric membrane there occurs shrink and aging, follow-up heating process just can not produce the size impact of horizontal direction to polymeric membrane, thus can not because of thermal contraction to Graphene produce destruction.
(2) using Thermal release adhesive tape by n (natural number; n >=1) layer graphene film to transfer to basement membrane from growing substrate or uses n (natural number the diaphragm containing bonding coat; n >=1) layer graphene film transfers in the process diaphragm from growing substrate; often shift after on one deck graphene film to basement membrane or diaphragm, all the basement membrane of graphene-containing or diaphragm are positioned in organic solvent and soak.When often shifting one deck graphene film, the basement membrane of graphene-containing or diaphragm are positioned over the number of times soaked in organic solvent and are at least three times, number of times is more, and cull is removed more thorough.The basement membrane of graphene-containing or diaphragm are positioned over when soaking in organic solution, soak time successively shortens, and such as soaks three times, 30 minutes first times, second time 15 minutes, 10 minutes third times.Organic solvent is methylbenzene or dimethylbenzene or ethyl acetate or butanone or aforesaid mixed organic solvents.After above-mentioned process, the cull on each layer graphene surface eliminates, the Distance Shortened of graphene layer and interlayer, greatly reduce molecule from horizontal proliferation between graphene layer through probability, improve the barrier property of Obstruct membrane.
(3) soaked the cleaning of rear employing pure water, then put into oven for drying, after graphene film is protected, shift next layer graphene film again.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. improve a method for Graphene composite gas Obstruct membrane performance, Graphene composite gas Obstruct membrane is followed successively by basement membrane, gas barrier functional layer, diaphragm; Described basement membrane and diaphragm are polymer film; Described gas barrier functional layer is one deck or two-layer or multi-layer graphene film or graphene film and the superposing of nano level metal film; Thermal release adhesive tape is used to transfer to basement membrane by n (natural number, n >=1) layer graphene film from growing substrate; Or use n (natural number the diaphragm containing bonding coat, n >=1) layer graphene film transfers to diaphragm from growing substrate, it is characterized in that: before gas barrier functional layer and basement membrane or the diaphragm compound containing bonding coat, basement membrane or diaphragm are put into baking oven and heats; Described heating-up temperature and heat time meet: the deformation temperature of come unstuck temperature≤heating-up temperature≤basement membrane or the diaphragm of Thermal release adhesive tape or bonding coat; Heat time >=usually time of Thermal release adhesive tape or bonding coat.
2. a kind of method improving Graphene composite gas Obstruct membrane performance according to claim 1; it is characterized in that: at use Thermal release adhesive tape by n (natural number; n >=1) layer graphene film to transfer to basement membrane from growing substrate or uses n (natural number the diaphragm containing bonding coat; n >=1) layer graphene film transfers in the process diaphragm from growing substrate; often shift after on one deck graphene film to basement membrane or diaphragm, all the basement membrane of graphene-containing or diaphragm are positioned in organic solvent and soak.
3. a kind of method improving Graphene composite gas Obstruct membrane performance according to claim 2; it is characterized in that: during described often transfer one deck graphene film, the basement membrane of graphene-containing or diaphragm are positioned over the number of times soaked in organic solvent and are at least three times.
4. a kind of method improving Graphene composite gas Obstruct membrane performance according to claim 3, is characterized in that: describedly the basement membrane of graphene-containing or diaphragm are positioned over when soaking in organic solution, and soak time successively shortens.
5. a kind of method improving Graphene composite gas Obstruct membrane performance according to claim 4, is characterized in that: described organic solvent is methylbenzene or dimethylbenzene or ethyl acetate or butanone or aforesaid mixed organic solvents.
6. a kind of method improving Graphene composite gas Obstruct membrane performance according to Claims 2 or 3 or 4 or 5, is characterized in that: soaked the cleaning of rear employing pure water, then put into oven for drying, then shift next layer graphene film.
7. a kind of method improving Graphene composite gas Obstruct membrane performance according to claim 6, is characterized in that: described basement membrane and diaphragm are PET film or PE film.
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| CN201510628933.XA CN105313433A (en) | 2015-09-28 | 2015-09-28 | Method for improving barrier property of graphene complex gas barrier film |
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| CN201510628933.XA CN105313433A (en) | 2015-09-28 | 2015-09-28 | Method for improving barrier property of graphene complex gas barrier film |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589847A (en) * | 2016-12-08 | 2017-04-26 | 贵州省材料产业技术研究院 | High-barrier antistatic graphene/polymer nanocomposite sheet/film and preparation method thereof |
| CN112721384A (en) * | 2020-12-26 | 2021-04-30 | 北京普凡防护科技有限公司 | Bulletproof and gas-proof integrated protective lining and manufacturing method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62149415A (en) * | 1985-12-24 | 1987-07-03 | Diafoil Co Ltd | Manufacture of low shrinkable polyester film |
| CN101378891A (en) * | 2006-02-09 | 2009-03-04 | 杜邦帝人薄膜美国有限公司 | Manufacturing process for polyester film exhibiting low thermal shrinkage |
| US20120282419A1 (en) * | 2010-01-15 | 2012-11-08 | Jonghyun Ahn | Graphene protective film serving as a gas and moisture barrier, method for forming same, and use thereof |
| CN104553115A (en) * | 2014-12-26 | 2015-04-29 | 常州二维碳素科技有限公司 | Composite gas barrier film and preparation method thereof |
-
2015
- 2015-09-28 CN CN201510628933.XA patent/CN105313433A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62149415A (en) * | 1985-12-24 | 1987-07-03 | Diafoil Co Ltd | Manufacture of low shrinkable polyester film |
| CN101378891A (en) * | 2006-02-09 | 2009-03-04 | 杜邦帝人薄膜美国有限公司 | Manufacturing process for polyester film exhibiting low thermal shrinkage |
| US20120282419A1 (en) * | 2010-01-15 | 2012-11-08 | Jonghyun Ahn | Graphene protective film serving as a gas and moisture barrier, method for forming same, and use thereof |
| CN104553115A (en) * | 2014-12-26 | 2015-04-29 | 常州二维碳素科技有限公司 | Composite gas barrier film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 大石不二夫: "《高分子材料实用技术》", 31 October 1985 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589847A (en) * | 2016-12-08 | 2017-04-26 | 贵州省材料产业技术研究院 | High-barrier antistatic graphene/polymer nanocomposite sheet/film and preparation method thereof |
| CN112721384A (en) * | 2020-12-26 | 2021-04-30 | 北京普凡防护科技有限公司 | Bulletproof and gas-proof integrated protective lining and manufacturing method thereof |
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Application publication date: 20160210 |
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