CN111116960A

CN111116960A - Film and method for producing same

Info

Publication number: CN111116960A
Application number: CN201911292648.XA
Authority: CN
Inventors: 林小锋
Original assignee: Suzhou Puxi Environmental Protection Technology Co Ltd
Current assignee: Suzhou Puxi Environmental Protection Technology Co Ltd
Priority date: 2019-12-16
Filing date: 2019-12-16
Publication date: 2020-05-08

Abstract

Membranes and methods of making the same are disclosed. The film comprises: a base layer, wherein the base layer comprises one or more first barrier layers on at least one surface thereof; and the second barrier layer is arranged on the surface of the at least one barrier layer. Since the film comprises one or more first barrier layers on at least one surface of the substrate layer and further comprises a second barrier layer disposed on the surface of at least one first barrier layer, by the way that the first barrier layer overlaps the second barrier layer, even if pores, pinholes, cracks and the like occur in the first barrier layer, sealing can be performed by the second barrier layer, and the sealing performance can be improved compared with the prior art.

Description

Film and method for producing same

Technical Field

The application relates to the technical field of material processing, in particular to a membrane and a preparation method thereof.

Background

With the development of society, films such as plastic films and metal foils are generally used in sealing processes in food, beverage bottles, pharmaceuticals, optical and electronic industries, and the like. The existing film is limited by preparation materials, preparation processes and the like, and tiny pores, pinholes, cracks and the like are usually formed on the surface, so that the sealing performance of the film is influenced. Therefore, it is necessary to provide a film having more excellent sealing performance to solve the problems of the prior art.

Disclosure of Invention

The embodiment of the application provides a membrane and a preparation method thereof, which are used for solving the problem of poor membrane sealing performance in the prior art.

The embodiment of the application provides a preparation method of a membrane, which comprises the following steps:

providing a substrate layer, wherein at least one surface of the substrate layer comprises one or more first barrier layers;

and generating a second barrier layer on the surface of at least one first barrier layer of the substrate layer.

Preferably, the generating a second barrier layer on the surface of at least one first barrier layer of the substrate layer specifically includes:

and generating a second barrier layer on the surface of at least one first barrier layer of the substrate layer by using a metal material in a magnetron sputtering mode.

and generating a second barrier layer on the surface of at least one first barrier layer of the substrate layer by using a graphene material or a water-soluble high polymer material.

and fixing the second barrier layer on the first barrier layer through the chemical reaction of the first reactant on the surface of the first barrier layer and the second reactant on the surface of the second barrier layer.

and generating a second barrier layer on the surface of at least one first barrier layer of the substrate layer by a dip coating process for a water-soluble high polymer material.

Embodiments of the present application also provide a membrane, including: a base layer, wherein the base layer comprises one or more first barrier layers on at least one surface thereof; and the number of the first and second groups,

and the second barrier layer is arranged on the surface of the at least one barrier layer.

Preferably, the substrate layer is specifically a flexible organic substrate layer.

Preferably, the thickness of the base layer is greater than or equal to 5 micrometers and less than or equal to 250 micrometers.

Preferably, the thickness of the first barrier layer is greater than or equal to 30 microns and less than or equal to 150 microns.

Preferably, the thickness of the second barrier layer is greater than or equal to 1 nm and less than or equal to 500 nm.

The embodiment of the application adopts at least one technical scheme which can achieve the following beneficial effects:

with the film provided by the embodiment of the present application, since at least one surface of the substrate layer of the film includes one or more first barrier layers, and the film further includes a second barrier layer disposed on a surface of the at least one first barrier layer, even if a pore, a pinhole, a crack, or the like occurs in the first barrier layer, the film can be sealed by the second barrier layer by the way that the first barrier layer overlaps the second barrier layer, and the sealing performance can be improved compared with the prior art.

Drawings

The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:

FIG. 1 is a schematic cross-sectional view of a film according to an embodiment of the present disclosure;

FIG. 2 is a schematic cross-sectional detail view of another film provided in an embodiment of the present application;

fig. 3 is a schematic flow chart of a specific method for preparing a membrane according to an embodiment of the present disclosure.

Detailed Description

In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be described in detail and completely with reference to the following specific embodiments of the present application and the accompanying drawings. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

The technical solutions provided by the embodiments of the present application are described in detail below with reference to the accompanying drawings.

As described above, the existing membrane is limited by the preparation materials, preparation processes, etc., and tiny pores, pinholes, cracks, etc. are usually formed on the surface, so that the membrane can transmit oxygen, water vapor, carbon dioxide, hydrogen sulfide, sulfur oxide, nitrogen oxide, solvent, solute, etc., thereby affecting the sealing performance.

Based on this, the present application provides a film that can solve the problems in the prior art. A schematic cross-sectional view of the membrane 10 is shown in fig. 1. As can be seen in fig. 1, the film 10 comprises a substrate layer 11, wherein at least one surface of the substrate layer 11 comprises one or more first barrier layers 12, and the film 10 further comprises a second barrier layer 13 disposed on a surface of at least one of the first barrier layers 12.

Wherein the substrate layer 11 is used to provide mechanical support and/or fluid flow paths, depending on the particular application. For example, in membranes used for water filtration, the substrate layer needs to provide mechanical support and fluid flow channels.

Also, the material of the substrate layer 11 may be organic and/or inorganic materials and mixtures thereof, for example, the substrate layer 11 may be a single block or a structure comprising a plurality of adjacent different blocks of material. The material of the substrate layer 11 may be a thermoplastic. The material of the base layer 11 may also be an organic polymeric resin such as, but not limited to, polyethylene terephthalate (PET), polyacrylate, polynorbornene, Polycarbonate (PC), silicone, epoxy, silicone-functionalized epoxy, or polyethylene naphthalate (PEN). The material of the further substrate layer 11 may be an ultra-thin glass layer or a metal foil or a fused ceramic, which has pores, pinholes or cracks. Furthermore, the materials of the substrate layer 11 of different industry names may include Aclar, Vectran, Tefzel, Surlyn, PET ST504, PET mylar D, Armstrong A661, Tedlar, BRP-C, PVC Black, P0100, P0130, Kapton, PVC clear, Korad, EVA, PVB, TPU, DC Sy1guards, GE RTV 615. It should be noted that a combination of materials formed by a plurality of materials is also within the scope of the present application.

For example, the material of the substrate layer 11 may be a flexible organic material such as PET, so as to prepare a flexible organic substrate layer with flexibility; the material of the base layer 11 may also be a metal material such as gold, silver, copper, etc., so that the base layer 11 of the prepared metal foil is processed using these metal materials.

In addition, as for the thickness of the base layer 11, the thickness thereof may be greater than or equal to 5 micrometers and less than or equal to 250 micrometers. For example, the base layer 11 has a thickness of 5 microns, 10 microns, 15 microns, 20 microns, 30 microns, 50 microns, 80 microns, 100 microns, 110 microns, 135 microns, 150 microns, 170 microns, 195 microns, 200 microns, 220 microns, 230 microns, 250 microns, or other thickness values between 5 microns and 250 microns. In practical applications, the specific thickness of the substrate layer 11 can be determined according to specific application scenarios, the material of the substrate layer 11, and the like.

For both surfaces of the substrate layer 11, at least one surface thereof comprises one or more first barrier layers 12. For example, the substrate layer 11 includes a first barrier layer 12 on one surface and no first barrier layer 12 on the other surface; alternatively, the substrate layer 11 includes one first barrier layer 12 on one surface and one or more first barrier layers 12 on the other surface; alternatively, the base layer 11 includes a plurality of first barrier layers 12 on one surface, a plurality of first barrier layers 12 on the other surface, and the like.

For both surfaces of the substrate layer 11, specifically, one or both surfaces include the first barrier layer 12, which may be determined according to actual needs, for example, for the fields related to life and health, such as medicine, food, etc., in order to avoid pollution caused by direct contact of the substrate layer 11 with the medicine, food, etc., the first barrier layer 12 may be disposed on both surfaces of the substrate layer 11.

In addition, the specific number of the first barrier layers 12 on either surface of the base layer 11 may be generally 1. Of course, when high sealability is required, there may be a plurality of the first barrier layers 12, such as 2, 3, 4 or other numbers, and these first barrier layers 12 are stacked on the surface of the substrate layer 11.

Generally, the greater the number of first barrier layers 12, the greater the sealability of the film 10, but at a correspondingly higher cost, the number of first barrier layers 12 may be determined in conjunction with the actual sealing needs and cost considerations.

The thickness of any one of the first barrier layers 12 may be greater than or equal to 30 microns and less than or equal to 150 microns. For example, the first barrier layer 12 has a thickness of 30 microns, 35 microns, 45 microns, 60 microns, 80 microns, 90 microns, 100 microns, 110 microns, 135 microns, 150 microns, or other thickness values between 30 microns and 150 microns.

The first barrier layer 12 may be formed using a metallic or ceramic material and may be produced by dip coating, spray coating, physical vapor deposition, Chemical Vapor Deposition (CVD), Plasma Enhanced Chemical Vapor Deposition (PECVD), magnetron sputtering, and/or reactive sputtering, or other means.

The material of the first barrier layer 12 may be a nitride, such as silicon nitride. The material of the first barrier layer 12 may also be those of organic materials, inorganic materials, ceramic materials, and any combination thereof.

For example, in one example, the material of the first barrier layer 12 is a recombination product from a reactive plasma species and deposited onto the substrate layer 11. In another example, the material of the first barrier layer 12 is an organic barrier coating material, which may generally include carbon and hydrogen, optionally with other elements such as oxygen, nitrogen, silicon, sulfur, and the like.

The material of the first barrier layer 12 may also be an inorganic material, a ceramic material, typically including oxides, nitrides, borides, or any combination thereof of elements of groups IIA, IIIA, IVA, VA, VIA, VIIA, IB, or IIB; metals of group IIIB, IVB or VB or of rare earth elements. For example, the first barrier layer 12 comprising a silicon carbide material may be deposited onto the substrate layer 11 by recombination of plasmas generated from silane and an organic material such as methane or xylene. The first barrier layer 12 comprising a carbon-containing silicon oxide material may be deposited from a plasma generated from silane, methane and oxygen, or silane and propylene oxide, or from a plasma generated from an organosilicone precursor, such as tetraethoxyorthosilicate (TE0S), Hexamethyldisiloxane (HMDS), Hexamethyldisilazane (HMDZ), or octamethylcyclotetrasiloxane (D4). The first barrier layer 12 of silicon nitride-containing material may be deposited from a plasma generated from silane and ammonia. The first barrier layer 12 comprising the carbon-containing aluminum oxynitride material may be deposited from a plasma generated, for example, from a mixture of aluminum tartrate and ammonia.

In some embodiments, the first barrier layer 12 comprising an organic material can be deposited by known methods such as, but not limited to, spin coating, flow coating, doctor blading, extrusion, gravure or microgravure printing, dip coating, spray coating, vacuum deposition, Chemical Vapor Deposition (CVD), Plasma Enhanced Chemical Vapor Deposition (PECVD), or similar methods such as radio frequency plasma enhanced chemical vapor deposition (RF-PECVD), expanding thermal-plasma chemical vapor deposition, reactive sputtering, electron-cyclotron resonance plasma enhanced chemical vapor deposition (ecrpevd), Inductively Coupled Plasma Enhanced Chemical Vapor Deposition (ICPECVD), sputter deposition, evaporation, layer deposition, or combinations thereof.

The film 10 further comprises a second barrier layer 13 disposed on a surface of the at least one first barrier layer 12. For example, in fig. 1, the film 10 includes a second barrier layer 13 disposed on a surface of a first barrier layer 12; as shown in fig. 2, a plurality of second barrier layers 13 may be further included, and the second barrier layers are respectively disposed on the surfaces of the plurality of first barrier layers 12. Of course, for each first barrier layer 12, a corresponding second barrier layer 13 may be provided on the surface thereof. The greater the number of the second barrier layers 13, the better the sealing effect is, but the higher the corresponding manufacturing cost is, the number of the second barrier layers 13 can be determined by combining the requirements of sealing performance, cost and other factors.

The thickness of the second barrier layer 13 may be the same as or different from the thickness of the first barrier layer 12, and in general, the thickness of the second barrier layer 13 may be greater than or equal to 1 nm and less than or equal to 500 nm. For example, the thickness of the second barrier layer 13 is 1 nm, 3 nm, 7 nm, 10 nm, 16 nm, 30 nm, 50 nm, 70 nm, 100 nm, 140 nm, 170 nm, 200 nm, 230 nm, 270 nm, 300 nm, 350 nm, 390 nm, 400 nm, 420 nm, 450 nm, 480 nm, 500 nm or other thickness values between 1 nm and 500 nm.

As the material of the second barrier layer 13, a material having higher density or larger specific surface area than that of the first barrier layer 12 is generally used, so that the barrier or adsorption property of the second barrier layer 13 is larger than that of the first barrier layer 12. For example, a nano silver material, a carbon nanofiber material, a carbon nanotube material, graphene, and the like with a large specific surface area may be used as a material for preparing the second barrier layer 13, so that the second barrier layer 13 has a great adsorption performance.

Since the metal material has high denseness, a metal material such as gold, silver, or aluminum may be used as the material of the second barrier layer 13, and particularly, the second barrier layer 13 may be formed on the surface of the first barrier layer 12 by magnetron sputtering of the metal material. The magnetron sputtering method has low cost and simple operation, and can generally reduce the manufacturing cost of the second barrier layer 13.

In addition, it should be noted that the second barrier layer 13 is generated by using the surface of the first barrier layer 12 made of the dense metal material in a magnetron sputtering manner, and since the dense metal material does not chemically react with the first barrier layer 12 in the magnetron sputtering manner, the second barrier layer 13 may be peeled off from the outer surface of the first barrier layer 12 in physical manners such as scratching and reverse flushing if necessary, and then the second barrier layer 13 is generated again, so as to achieve the purpose of recycling, and contribute to environmental protection and cost reduction.

For example, when the second barrier layer 13 has a groove, a crack, or the like after a long time use, the second barrier layer 13 may be peeled off from the outer surface of the first barrier layer 12, and a new second barrier layer 13 may be regenerated, and the other parts may be recycled.

Of course, the second barrier layer 13 may be formed on the surface of the first barrier layer 12 by providing a first reactant on the surface of the first barrier layer 12 and providing a second reactant on the surface of the second barrier layer 13, and then connecting the second barrier layer 13 to the first barrier layer 12 by a chemical reaction between the first reactant and the second reactant. In this method, since the first barrier layer 12 and the second barrier layer 13 are connected by the functional group generated by the chemical reaction of the two reactants, the connection is tighter, but the reusability is poor, compared to the physical deposition method. Therefore, in determining the specific formation manner of the second barrier layer 13, the manner of using chemical reaction or physical deposition may be determined in accordance with specific needs.

It should be noted that in some special scenarios, such as scenarios involving drugs and life health, the substrate layer 11 may need to be in direct contact with drugs, blood, etc., in this case, by disposing the first reactant and the second reactant on the surfaces of the first barrier layer 12 and the second barrier layer 13, respectively, so as to finally form the second barrier layer 13 on the surface of the first barrier layer 12, the reactant is prevented from being disposed directly on the substrate layer 11, so as to avoid contamination of the drugs or blood due to the residue of the reactant.

With the film 10 provided in the embodiment of the present application, since at least one surface of the substrate layer 11 of the film 10 includes one or more first barrier layers 12, and the film 10 further includes a second barrier layer 13 disposed on a surface of at least one first barrier layer 12, by overlapping the first barrier layer 12 and the second barrier layer 13, even if pores, pinholes, cracks, and the like occur in the first barrier layer 12, sealing can be performed by the second barrier layer 13, and sealing performance can be improved compared with the prior art.

Based on the same concept as the film 10 provided in the embodiments of the present application, the embodiments of the present application also provide a method for producing the film 10, and for the production method, reference may be made to the embodiments of the structural portion of the film 10, if unclear. As shown in fig. 3, a specific flow diagram of the preparation method is shown, which comprises the following steps:

step S31: a substrate layer is provided, wherein at least one surface of the substrate layer includes one or more first barrier layers thereon.

Step S32: a second barrier layer is created on a surface of at least one barrier layer of the base layer.

For example, a metallic material may be magnetron sputtered onto the surface of the at least one barrier layer to form a metallic second barrier layer. The metal material has high compactness, so that the second barrier layer is formed by adopting the metal material, and the integral barrier property of the film can be improved.

In addition, the second barrier layer may be formed on the surface of at least one of the barrier layers of the base layer using a material having a large specific surface area, such as a nano silver material, a carbon nanofiber material, a carbon nanotube material, or graphene. Thereby utilizing the adsorbability of the materials with large specific surface area to improve the overall barrier performance of the membrane.

In addition, the second barrier layer 13 of a polymer may be formed on the first barrier layer 12 by a dip coating process using a water-soluble polymer material, and may be cleaned to remove residues after the dip coating process. For example, 5g of a 2000k molar mass polyvinyl amide (PEI) is selected to be sufficiently dissolved in 1000ml of an aqueous solution, the outer surface of the first barrier layer 12 is exposed to the PEI aqueous solution for 15 minutes, so that PEI is deposited under the noncovalent bond actions such as electrostatic adsorption, hydrogen bonding, charge transfer, coordination, specific molecule recognition and the like, and then redundant PEI molecules which are not effectively adsorbed are washed away by pure water, and finally the second barrier layer 13 of PEI is formed. The resulting second barrier layer 13 of PEI utilizes the hydrophilic properties of PEI materials in addition to blocking voids, thereby increasing the hydrophilic properties of the membrane surface for enhanced flux and anti-fouling properties.

It is to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in the process, method, article, or apparatus that comprises the element.

The above are merely examples of the present application and are not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.

Claims

1. A method of making a film, comprising:

2. The method according to claim 1, wherein forming a second barrier layer on a surface of at least one first barrier layer of the substrate layer comprises:

3. The method according to claim 1, wherein forming a second barrier layer on a surface of at least one first barrier layer of the substrate layer comprises:

and generating a second barrier layer on the surface of the at least one first barrier layer of the substrate layer by using the graphene material.

4. The method according to claim 1, wherein forming a second barrier layer on a surface of at least one first barrier layer of the substrate layer comprises:

5. The method according to claim 1, wherein forming a second barrier layer on a surface of at least one first barrier layer of the substrate layer comprises:

6. A film, comprising: a base layer, wherein the base layer comprises one or more first barrier layers on at least one surface thereof; and the number of the first and second groups,

7. The film according to claim 6, wherein the substrate layer is in particular a flexible organic substrate layer.

8. The film of claim 6, wherein the substrate layer has a thickness of greater than or equal to 5 microns and less than or equal to 250 microns.

9. The film of claim 6, wherein the first barrier layer has a thickness of greater than or equal to 30 microns and less than or equal to 150 microns.

10. The film of claim 6, wherein the second barrier layer has a thickness of greater than or equal to 1 nanometer and less than or equal to 500 nanometers.