JP2015140264A - Functional film, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a functional film which has high water repellency and is made inexpensive, and to provide a method for producing the functional film.SOLUTION: The method for producing the functional film comprises the steps of: preparing the functional film in which graphene nanoribbons are assembled, and a polycyclic aromatic compound in which a halogen is bonded to at least two carbons; subjecting the polycyclic aromatic compound to a radical polymerization reaction to produce a polymer; and subjecting aromatic rings in the produced polymer to a dehydrogenation-condensation-cyclization reaction to grow the polymer anisotropically so that the functional film, in which graphene nanoribbons are assembled, can be formed.

Description

  The present invention relates to a functional film and a manufacturing method thereof. In particular, the present invention relates to a functional film formed by gathering graphene nanoribbons and a method for producing the same.

  In recent years, a film or film containing a carbon material such as graphite, graphene, carbon black, or carbon nanotube as a constituent component has attracted attention as having various functions such as durability and conductivity.

  For example, Patent Document 1 below discloses a surface protective film containing a carbon nanotube and a polyurethane resin. The surface protective film is said to be excellent in transparency and antistatic properties.

JP 2007-137052 A

  However, although the film of Patent Document 1 is excellent in transparency and antistatic properties, it has insufficient water repellency because it contains polyurethane. Further, since expensive carbon nanotubes are contained, there is a problem that the cost is high.

  An object of the present invention is to provide a functional film having high water repellency and a low cost, and a method for producing the same.

  The functional film according to the present invention is formed by aggregating graphene nanoribbons.

  In a specific aspect of the functional film according to the present invention, a part of the graphene nanoribbon extends in a protruding shape in the thickness direction of the functional film.

  In another specific aspect of the functional film according to the present invention, the principal surfaces of the graphene nanoribbons are assembled so as to overlap each other.

The functional film according to the present invention preferably has a BET specific surface area of 10 cm ² / g or more.

  In the functional film according to the present invention, preferably, the graphene nanoribbon has a length of 5 to 200 nm and a width of 0.4 to 10 nm.

  The functional film according to the present invention is preferably a water-repellent film.

  The functional film according to the present invention is preferably an oil repellent film.

  In another broad aspect of the present invention, a method for producing a functional membrane constructed in accordance with the present invention is provided. The production method of the present invention includes a step of preparing a polycyclic aromatic compound in which halogen is bonded to at least two carbons, a step of producing a polymer by polymerizing the polycyclic aromatic compound, And forming a functional film in which graphene nanoribbons are assembled by anisotropically growing the polymer by dehydrogenating and condensing an aromatic ring in the polymer.

  In a specific aspect of the production method of the present invention, the step of producing a polymer by polymerizing the polycyclic aromatic compound, the polymer is produced, and the aromatic ring in the polymer is dehydrogenated and condensed. Thus, a step of forming the functional film formed by anisotropically growing the polymer and collecting graphene nanoribbons is performed by a CVD method. The polymerization is preferably radical polymerization.

  The functional film according to the present invention is formed by aggregating graphene nanoribbons. Therefore, according to the present invention, a functional film having high water repellency and low cost can be provided.

  According to the method for producing a functional film of the present invention, it is possible to produce a functional film having high water repellency and low cost.

It is an example of the reaction scheme for manufacturing the functional film | membrane which concerns on this invention. (A)-(c) is a schematic diagram for demonstrating that a graphene nanoribbon grows in a projection shape. It is a schematic diagram for demonstrating gathering so that the main surfaces of a graphene nanoribbon may overlap.

  Details of the present invention will be described below.

  The functional film according to the present invention is formed by aggregating graphene nanoribbons. In the present invention, the graphene nanoribbon refers to an elongated strip-like graphene that is anisotropically grown.

  Note that graphene refers to one layer constituting graphite, which is a layered compound. Therefore, graphene can be manufactured by exfoliating graphite. In addition, it is possible to manufacture by various methods such as a method of heat-treating silicon carbide and a method of synthesizing on a substrate by a CVD method without using peeling.

  The length of the graphene nanoribbon is not particularly limited, but the length is preferably 5 to 200 nm. In the case where the length of the graphene nanoribbon is limited to the above range, it is preferable because a projection structure described later can be easily formed. The width of the graphene nanoribbon is not particularly limited, but is preferably 0.4 to 10 nm. In that case, a denser film is formed, which is preferable.

  Hereafter, the detail of the manufacturing method of the said functional film concerning this invention is demonstrated previously, and the said functional film of this invention is demonstrated next.

(Method for producing functional film)
FIG. 1 is an example of a reaction scheme for producing a functional film according to the present invention. In the method for producing a functional film according to the present invention, a polycyclic aromatic compound in which halogen is bonded to at least two carbon atoms is used as a monomer.

  The polycyclic aromatic monomer in which halogen is bonded to the at least two carbon atoms is not particularly limited, but azulene, naphthalene, anthracene, fluorene, phenalene, phenanthrene, benz [a] anthracene, benzo [a] fluorene. , Benzo [c] phenanthrene, chrysene, fluoranthene, pyrene, tetracene, triphenylene, benzo [a] fluoranthene, benzo [b] fluoranthene, benzo [l] fluoranthene, benzo [k] fluoranthene, dibenz [a, h] anthracene, dibenz [A, l] anthracene, pentacene, perylene, picene, tetraphenylene, anthanthrene, 1,12-benzopyrene, circulene, corannulene, coronene, dicolonylene, diindenoperylene, helicene, f Possible recommendation, hexacene, kekulene, ovalene, zethrene, binaphthalene, it is used halide such bianthryl. More specifically, 5,6-dibromoazulene, 1,3-dibromoazulene, 4,7-dibromoazulene, 2,6-dibromonaphthalene, 1,7-dibromonaphthalene, 1,5-dibromonaphthalene, 1, 4-dibromonaphthalene, 1,2-dibromonaphthalene, 2,3-dibromonaphthalene, 1,6-dibromonaphthalene, 1,3-dibromonaphthalene, 2,7-dibromonaphthalene, 9,10-dibromoanthracene, 1,5 -Dibromoanthracene, 2,7-dibromoanthracene, 2,6-dibromoanthracene, 1,8-dibromoanthracene, 2,3-dibromoanthracene, 3,9-dibromoanthracene, 2,7-dibromofluorene, 9,10- Dibromophenanthrene, 1,8-dibromophenanthrene, 3,9-dibro Phenanthrene, 2,7-dibromophenanthrene, 1,6-dibromophenanthrene, 3,6-dibromophenanthrene, 2,8-dibromochrysene, 3,8-dibromofluoranthene, 1,6-dibromopyrene, 1,8- Dibromopyrene, 1,3-dibromopyrene, 2,7-dibromopyrene, 2,8-dibromopentacene, 2,9-dibromopentacene, 2,3-dibromopentacene, 2,10-dibromopentacene, 3,9-dibromo Perylene, 3,10-dibromoperylene, 1,7-dibromoperylene, 5,8-dibromopicene, 2,2′-dibromo-1,1′-binaphthalene, 10,10′-dibromo-9,9′-bianthryl and the like Is mentioned.

  The number of halogenated carbons is not particularly limited as long as it is 2 or more, but 2 is preferable. Moreover, it is more preferable that the two bonded halogens are line symmetric like 9,10-dibromoanthracene which is a monomer in the reaction scheme of FIG. This is because when two halogens are combined so as to be line symmetric, they can easily grow into a strip shape. However, as will be described later, as long as graphene grows anisotropically, line symmetry is not necessary.

  As shown in FIG. 1, the bond between carbon and halogen X of the polycyclic aromatic monomer in which halogen X is bonded to at least two carbon atoms is dissociated by heat, and the halogen of the polycyclic aromatic monomer is A radical is generated at the portion where X was bonded. Starting from this radical, a polymer is produced by radical polymerization of the polycyclic aromatic monomer. In this reaction scheme, the polymer was synthesized by radical polymerization, but the polymer can be synthesized by any other suitable polymerization method.

  In the present invention, the polymer grows anisotropically by dehydrogenating and condensing the aromatic ring in the polymer together with the production of the polymer. As a result, a functional film formed by gathering graphene nanoribbons is formed.

  The functional film of the present invention has high water repellency because the graphene nanoribbons having polycyclic aromatic groups are aggregated as described above. In addition, the functional film of the present invention can be manufactured at low cost because a polycyclic aromatic compound in which halogen is bonded to at least two carbon atoms is used as a raw material.

  Specifically, the series of manufacturing steps of the functional film can be performed by a CVD method (chemical vapor deposition method) or a sputtering method. It is preferable to manufacture by the CVD method.

  In the CVD method, for example, a polycyclic aromatic compound in which halogen is bonded to at least two carbon atoms is sublimated by heating under reduced pressure and then sprayed onto a preheated substrate. The above reaction is not limited to a reduced pressure, and can be performed in the presence of hydrogen gas as long as air is not present. And it is preferable that the heating under the said pressure reduction is performed for 20 minutes at 300 to 480 degreeC. Moreover, as a board | substrate, it is desirable to use a glass plate and to heat at 330 to 450 degreeC.

  In the CVD method, a polymer is generated by radical polymerization of the polycyclic aromatic monomer on a substrate. And with the production | generation of the said polymer, the said polymer grows anisotropically on a glass plate because the aromatic ring in the said polymer carries out dehydrogenation condensation reaction. In this way, in the CVD method, a functional film formed by aggregating graphene nanoribbons is formed on the substrate.

  In the CVD method, as shown in FIGS. 2A to 2C, the graphene nanoribbon 1 grows anisotropically on a substrate (not shown). Therefore, as shown in FIG. 2B, the growing graphene nanoribbons 1 may collide with each other. As a result, as shown in FIG. 2C, a part of the graphene nanoribbon 1 may grow in a protruding shape in the thickness direction of the functional film. Further, in the CVD method, as shown in FIG. 3, the main surfaces of the graphene nanoribbons 1 may be gathered so as to overlap each other.

  Thus, when a functional film is produced by the CVD method, a part of the graphene nanoribbons extends in a protruding shape in the thickness direction of the functional film, or the main surfaces of the graphene nanoribbons are gathered so as to overlap Sometimes. Therefore, the surface of the functional film produced by the CVD method has many irregularities. Therefore, the functional film produced by the CVD method is excellent not only in water repellency but also in oil repellency.

(Functional membrane)
The functional film according to the present invention is formed by aggregating graphene nanoribbons. Here, since the thickness of the graphene nanoribbon is at a monoatomic level, the functional film does not absorb in the visible light region and has transparency. Therefore, the said functional film does not inhibit the decorating property of a base material.

  Moreover, since the graphene nanoribbon is anisotropically grown graphene, it has a polycyclic aromatic group. Therefore, the functional film of the present invention in which the graphennan ribbon is assembled is excellent in water repellency.

  As described above, the functional film of the present invention uses, as a raw material, an inexpensive polycyclic aromatic compound in which halogen is bonded to at least two carbon atoms. Moreover, it can manufacture simply by heating in anaerobic gas. Therefore, the functional film of the present invention can be manufactured at low cost.

  In the functional film of the present invention, it is preferable that a part of the graphene nanoribbon extends in a protruding shape in the thickness direction of the functional film. In this case, since the irregularities are formed on the surface of the functional film, the functional film is excellent not only in water repellency but also in oil repellency. Thus, since the functional film can repel both water and oil, it has excellent antifouling properties. Therefore, when used as a surface material of a display such as a touch panel, fingerprints can be prevented from being attached.

  In addition, the same effect is acquired even when an unevenness | corrugation is formed in the surface of a functional film by gathering so that the main surfaces of a graphene nanoribbon may overlap. Therefore, in the present invention, it is desirable that the main surfaces of the graphene nanoribbons are gathered so as to overlap each other.

When the surface irregularities are large as described above, the functional film is excellent not only in water repellency but also in oil repellency. Therefore, it is desirable that the BET specific surface area of the functional film of the present invention is high. . More preferably, the BET specific surface area is 10 cm ² / g or more.

  Furthermore, the graphene nanoribbon constituting the functional film of the present invention has a polycyclic aromatic group, and therefore has high adhesion to a substrate and excellent durability. Therefore, the functional film of the present invention can reduce fluid friction. Since the functional film can reduce fluid friction in this way, for example, when used on the inner wall of a pipeline used for transporting oil, even if the flow rate of oil is increased, explosion due to static electricity hardly occurs. . It can also be used as an outer wall of ships, airplanes and the like.

  Next, specific examples and comparative examples will be described. The present invention is not limited to the following examples and comparative examples.

Example 1
10,10′-Dibromo-9,9′-bianthryl was used as a raw material, and was deposited on a glass plate as a substrate by a CVD method. Film formation by the CVD method was performed by heating at a temperature of 430 ° C. for 20 minutes in the presence of argon / hydrogen (hydrogen gas ratio 3%) gas. The glass plate was heated to 430 ° C. and used.

(Example 2)
A film was formed on a glass plate as a substrate in the same manner as in Example 1 except that 1,6-dibromopyrene was used as a raw material.

(Example 3)
A film was formed on a glass plate as a substrate in the same manner as in Example 1 except that 2,6-dibromonaphthalene was used as a raw material.

(Comparative Example 1)
Benzene was used as a raw material, and was deposited on a copper plate as a substrate by a CVD method. The copper plate was heated by heating to 650 ° C. Other points were the same as in Example 1, and a film was formed on the copper plate.

(Comparative Example 2)
Ethanol was used as a raw material, and was deposited on a copper plate as a substrate by a CVD method. The copper plate was heated by heating to 850 ° C. Other points were the same as in Example 1, and a film was formed on the copper plate.

(Evaluation method)
(1) Contact angle:
The contact angle was measured by the static method in JIS 3257. That is, 1 μL of distilled water or olive oil (trade name: BOSCO extra virgin olive oil) was dropped on the plane of the test piece kept horizontal with respect to the vertical direction, and the angle formed at the horizontal plane and the solid-liquid interface was measured as the contact angle. did.

(2) BET specific surface area:
The BET specific surface areas of the films obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were measured with a specific surface area measuring device ASAP-2000 manufactured by Shimadzu Corporation using nitrogen gas.

  The results are shown in Table 1 below.

  As is apparent from Table 1, the films formed in Examples 1 to 3 using polycyclic aromatic compounds in which halogen is bonded to at least two carbon atoms as raw materials are the same as those in Comparative Examples 1 and 2. It was confirmed that the contact angle and the BET specific surface area were effectively increased as compared with the membrane. Moreover, it has confirmed that the film | membrane with an unevenness | corrugation on the surface was formed in Examples 1-3 by this.

1. Graphene nanoribbon

Claims (10)

  A functional film made up of graphene nanoribbons.   The functional film according to claim 1, wherein a part of the graphene nanoribbon extends in a protruding shape in the thickness direction of the functional film.   The functional film according to claim 1, wherein main surfaces of the graphene nanoribbons are gathered so as to overlap each other. The functional film as described in any one of Claims 1-3 whose BET specific surface area is 10 cm < ² > / g or more.   The functional film according to claim 1, wherein the graphene nanoribbon has a length of 5 to 200 nm and a width of 0.4 to 10 nm.   The functional film according to claim 1, wherein the functional film is a water-repellent film.   The functional film according to any one of claims 1 to 6, wherein the functional film is an oil-repellent film. A method for producing a functional film according to any one of claims 1 to 7,
Providing a polycyclic aromatic compound in which a halogen is bonded to at least two carbons;
Producing a polymer by polymerizing the polycyclic aromatic compound;
A step of forming the polymer and forming a functional film in which graphene nanoribbons are assembled by anisotropically growing the polymer by dehydrocondensation reaction of an aromatic ring in the polymer. For producing a conductive film.   A step of producing a polymer by polymerizing the polycyclic aromatic compound; and producing the polymer and dehydrogenating and condensing an aromatic ring in the polymer to grow the polymer anisotropically, The method for producing a functional film according to claim 8, wherein the step of forming a functional film formed by aggregating nanoribbons is performed by a CVD method. The method for producing a functional film according to claim 8 or 9, wherein the polymerization is radical polymerization.

Images