JP5954558B2 - Method for producing polymer membrane and electropolymerization apparatus for polymer membrane production - Google Patents

Description

  The present invention relates to a method for producing a polymer film, a conductive substrate with a polymer film having a polymer film produced by the production method, and an electropolymerization apparatus for producing a polymer film used in the production method.

Conventionally, an electrolytic polymerization method is known as a method for producing a polymer film (particularly a conductive polymer film) on a substrate (Patent Document 1). The electrolytic polymerization method is a method in which a monomer is electrochemically electrolytically oxidized or electrolytically reduced on the electrode surface to cause a polymerization reaction. For example, in order to form a polypyrrole film by an electrolytic polymerization method, a pair of plate-like anode and cathode electrodes are inserted into an electrolytic polymerization tank containing an electrolytic solution containing a pyrrole monomer and a supporting electrolyte, By applying a voltage to the polymer, polymerization proceeds by coupling of radical cation species generated by anodic oxidation, and a film-like polypyrrole is deposited on the anode.
The electrolytic polymerization method is useful as a method for producing members of various functional devices such as solar cells because the procedure is simple and a polymer having high conductivity can be synthesized.

  In the conventional method, an electrolytic polymerization apparatus 300 for producing a polymer film as shown in FIG. 7 has been used when performing electrolytic polymerization. In the apparatus 300, a flat cathode 306 and an anode 308 are inserted into an electropolymerization tank 304 containing an electrolytic solution 302. The cathode 306 and the anode 308 are connected to a power source 310 via an external supply terminal (not shown). doing.

JP-A-60-137923

  In the conventional method, for example, when a polymer film (for example, polypyrrole, polythiophene) is produced on the surface of a large number of plate-like anodes 308, the anode substrate with the polymer film is externally fed after completion of one electrolytic polymerization. It was necessary to remove the terminal and connect the external power feeding terminal to another new flat plate-like anode 308 again. In other words, every time an anode substrate with a polymer film is completed, it is necessary to reconnect the external supply terminal to the plate-like anode 308, and the work is complicated. It was not always a satisfactory method.

In recent years, with the demand for improving the performance of functional devices, there is a demand for miniaturization of functional devices having conductive polymer films. Therefore, it is necessary to manufacture a polymer film (especially a conductive polymer film) on a substrate having a smaller area.
On the other hand, in the conventional electropolymerization method described above, since it is difficult to connect the external power supply terminal and the substrate having a small area in the first place, it is necessary to manufacture a special external power supply terminal, which lacks versatility.

Furthermore, in order to improve the performance of the functional device, it is necessary to further improve the flatness of the surface of the polymer film (particularly, the conductive polymer film).
The flatness of the polymer film obtained by the above-described conventional electrolytic polymerization method does not necessarily satisfy the level required recently, and further improvement has been required.

In view of the above circumstances, the present invention can produce a polymer film having excellent flatness on a substrate by an electrolytic polymerization method without being connected to an external power supply terminal. It aims at providing the manufacturing method of a film | membrane.
Another object of the present invention is to provide an electropolymerization apparatus for producing a polymer film used in the production method.

As a result of intensive studies, the present inventors have found that the above problem can be solved by utilizing the bipolar phenomenon.
Specifically, the present inventors have found that the above object can be achieved by the following means.

(1) A conductive substrate is immersed in the solution so that the cathode or the anode and the main surface face each other between a cathode and an anode immersed in a solution containing an electropolymerizable monomer and a supporting electrolyte. A polymer film is produced by applying a voltage between the cathode and the anode and utilizing a bipolar phenomenon to produce a polymer film by electrolytic polymerization of the electropolymerizable monomer on the surface of the conductive substrate. Method.

(2) Before applying the voltage, an insulating partition having an opening through which the solution flows is disposed between the conductive substrate and the cathode or between the conductive substrate and the anode. The manufacturing method of the polymer film as described in (1).

(3) The method for producing a polymer film according to (1) or (2), wherein the insulating partition has an opening at a position facing the central portion of the conductive substrate.

(4) The method for producing a polymer membrane according to any one of (1) to (3), wherein the concentration of the supporting electrolyte in the solution is 1000 mM or less.

(5) Any of (1) to (4), wherein the electropolymerizable monomer includes at least one selected from the group consisting of benzene, pyrrole, aniline, phenol, phthalocyanine, thiophene, furan, azulene and derivatives thereof. A method for producing the polymer film according to claim 1.

(6) A polymer having a conductive substrate and a polymer film obtained by the method for producing a polymer film according to any one of (1) to (5) disposed on the surface of the conductive substrate. Conductive substrate with film.

(7) An electropolymerization apparatus for producing a polymer film for producing a polymer film on the surface of a conductive substrate,
An electropolymerization tank in which a solution containing an electropolymerizable monomer and a supporting electrolyte is accommodated;
A cathode and an anode disposed in the electrolytic polymerization tank;
In the electrolytic polymerization tank, a conductive substrate disposed between the cathode and the anode so that the cathode or the anode and the main surface face each other,
In the electrolytic polymerization tank, having an insulating partition having an opening through which the solution flows, disposed between the conductive substrate and the cathode or between the conductive substrate and the anode,
Electrolysis for polymer film production in which a voltage is applied between the cathode and the anode, and a polymer film is produced on the surface of the conductive substrate by electropolymerization of the electropolymerizable monomer using a bipolar phenomenon. Polymerization equipment.

(8) The electropolymerization apparatus for producing a polymer film according to (7), wherein the insulating partition has an opening at a position facing the central portion of the conductive substrate.

According to the present invention, a polymer film excellent in flatness can be manufactured on a substrate by an electropolymerization method without being connected to an external power supply terminal, and a method for manufacturing a polymer film excellent in industrial productivity Moreover, according to the present invention, it is possible to provide an electrolytic polymerization apparatus for producing a polymer film used in the production method.

It is a schematic block diagram of 1st Embodiment of the electropolymerization apparatus for polymer film manufacture of this invention. It is a schematic block diagram which shows the modification of 1st Embodiment of the electropolymerization apparatus for polymer film manufacture of this invention. It is a schematic block diagram of 2nd Embodiment of the electropolymerization apparatus for polymer film manufacture of this invention. It is typical sectional drawing of 3rd Embodiment of the electropolymerization apparatus for polymer film manufacture of this invention. It is a figure which shows the transmittance | permeability of the board | substrate with a polymer film obtained in Example 2 and Comparative Example 1. FIG. (A) It is a figure which shows the cyclic voltammogram at the time of using a platinum electrode. (B) It is a figure which shows the cyclic voltammogram at the time of using the board | substrate with a polymer film obtained in Example 2. FIG. It is a schematic block diagram of the electropolymerization apparatus for polymer film manufacture used with the conventional method.

Below, the manufacturing method of the polymer film of this invention, the electroconductive board | substrate with a polymer film, and the electropolymerization apparatus for polymer film manufacture are demonstrated with reference to drawings.
First, the feature point compared with the prior art of this invention is explained in full detail.
A feature of the present invention is that a (wireless) conductive substrate that is not connected to an external power supply terminal is disposed between the cathode and the anode, and a polymer film is manufactured on the conductive substrate using the bipolar phenomenon. Can be mentioned. Specifically, when a voltage is applied with a conductive substrate sandwiched between a cathode and an anode, the cathode side surface of the conductive substrate behaves as an anode and the anode side surface of the conductive substrate behaves as a cathode. That is, the surface of the conductive substrate is polarized by the bipolar phenomenon, and becomes an electrode (bipolar electrode) that can be used for electrolytic polymerization. Therefore, polymerization of the electropolymerizable monomer proceeds on the surface of the conductive substrate, and a polymer film is formed. After the electropolymerization, if a new conductive substrate is placed instead, a polymer film can be obtained in the same manner, and it is not necessary to connect the conductive substrate itself to the external power supply terminal. Excellent.

Further, in this method, even when the area of the conductive substrate is small, the polymer film can be efficiently formed, and the demand for downsizing of the functional device can be met.
Moreover, the polymer film obtained by this method is more excellent in flatness.
Furthermore, as will be described later, since a plurality of (two or more) conductive substrates are disposed between the cathode and the anode, a polymer film can be simultaneously formed on the surface thereof. Compared with, it is excellent in productivity.

  In the following, first, an electropolymerization apparatus for producing a polymer film used in the method for producing a polymer film of the present invention will be described in detail, and then a method for producing the polymer film will be described in detail.

<Electropolymerization apparatus for polymer film production (first embodiment)>
First, a first embodiment of an electropolymerization apparatus for producing a polymer film used in the method for producing a polymer film of the present invention will be described below with reference to the drawings.
FIG. 1 is a schematic configuration diagram of an electropolymerization apparatus 10 for producing a polymer film of the present invention.
The electropolymerization apparatus 10 for producing a polymer film is used for producing a polymer film on the surface of a conductive substrate, and includes an electropolymerization tank 12, a cathode 14, an anode 16, a conductive substrate 18, and a power source 20. With.

The electrolytic polymerization tank 12 is a long tank for storing (reserving) a solution W containing an electrolytic polymerizable monomer and a supporting electrolyte, and has an upper surface opened. Electropolymerization of the electropolymerizable monomer proceeds in the tank 12.
The shape and size of the electrolytic polymerization tank 12 are not particularly limited to the form shown in FIG. 1, and a sexual shape and size can be appropriately selected according to the purpose of use. Moreover, the upper surface does not need to be opened.

The cathode 14 and the anode 16 are disposed in the electrolytic polymerization tank 12 so as to face each other, and are immersed in the solution W. Moreover, the cathode 14 and the anode 16 are connected to a power source 20 described later via an external power supply terminal (not shown), and a voltage is applied between the cathode 14 and the anode 16 when performing electropolymerization.
The material constituting the cathode 14 and the anode 16 is not particularly limited, and is a metal such as gold, platinum, copper, silver, stainless steel, thallium, aluminum, tungsten, niobium, titanium, zinc, nickel, or a metal such as tin, indium, or titanium. It is formed of a metal oxide containing at least one element or a conductor such as carbon. In the case of a metal oxide, a plurality of metals may be included (for example, indium tin oxide).

The shape of the cathode 14 and the anode 16 is a flat plate shape. In addition, the shape of the cathode 14 and the anode 16 is not limited to the form of FIG. 1, A shape (bar shape etc.) other than flat form may be sufficient.
In addition, as shown in FIG. 1, when the cathode 14 and the anode 16 are flat each other, it is preferable that both are arranged substantially in parallel from the viewpoint that the variation in film thickness of the obtained polymer film becomes smaller. .

The electroconductive substrate 18 is disposed in the electrolytic polymerization tank 12 between the cathode 14 and the anode 16 such that its main surface faces the cathode 14 or the anode 16, and is immersed in the solution W. The conductive substrate 18 is preferably arranged so as to be substantially parallel to the cathode 14 or the anode 16 as shown in FIG. 1 from the viewpoint that the variation in film thickness of the obtained polymer film becomes smaller. .
The conductive substrate 18 is flat and has a first main surface and a second main surface, and the main surfaces (the first main surface and the second main surface) are the anode 14 or the anode 16. It arrange | positions so that it may oppose.

The material which comprises the electroconductive board | substrate 18 will not be restrict | limited especially if it is a material which shows electroconductivity. For example, metal such as gold, platinum, copper, silver, stainless steel, thallium, aluminum, tungsten, niobium, titanium, zinc, nickel, metal oxide containing at least one metal element such as tin, indium, titanium, or carbon These conductors are mentioned. In the case of a metal oxide, a plurality of metals may be included (for example, indium tin oxide).
The configuration of the conductive substrate 18 is not limited as long as the surface exhibits conductivity. For example, the conductive substrate 18 has a configuration in which the surface of an insulating substrate (for example, a glass substrate) is covered with a conductive material (for example, ITO). May be.

In FIG. 1, the shape of the conductive substrate 18 is a flat plate shape.
The shape of the conductive substrate 18 is not limited to the shape shown in FIG. 1, and may be a shape other than a flat plate shape or a substrate having a curved surface.
The size of the conductive substrate 18 is preferably the same size as the cathode 14 and the anode 16 as shown in FIG. If it is this form, since the coverage of the polymer film on the electroconductive board | substrate 18 improves more, it is preferable.

  Although only one conductive substrate 18 is disposed between the cathode 14 and the anode 16 in FIG. 1, two or more conductive substrates 18 may be disposed. For example, as shown in FIG. 2, when two conductive substrates 18a and 18b are arranged, the surface on the cathode 14 side of the conductive substrates 18a and 18b serves as the anode, and the anode 16 side of the conductive substrates 18a and 18b. The surface of the substrate acts as a cathode, and both act as bipolar electrodes. Therefore, when the electropolymerization described later is performed, a polymer film can be simultaneously formed on the surfaces of both the conductive substrates 18a and 18b.

The power source 20 is connected to the above-described cathode 14 and anode 16 via wiring and an external power supply terminal (not shown).
In FIG. 1, the cathode 14, the anode 16, and a part of the conductive substrate 18 are immersed in the solution W, but each of them may be immersed in the solution W.

<Method for Producing Polymer Film (First Embodiment)>
Next, a method for producing a polymer film using the electrolytic polymerization apparatus 10 for producing the polymer film will be described in detail.
As a method for producing the polymer film, first, the conductive substrate 18 is placed in the solution W between the cathode 14 and the anode 16 immersed in the solution W so that the cathode 14 or the anode 16 faces the main surface. Immerse. Next, a voltage is applied between the cathode 14 and the anode 16 to produce a polymer film on the surface of the conductive substrate 18 by electrolytic polymerization of an electropolymerizable monomer using a bipolar phenomenon.
Below, the material (for example, an electropolymerizable monomer, a supporting electrolyte etc.) used with the said manufacturing method is explained in full detail first, and the detailed procedure of this method is explained in full detail after that.

(Electropolymerizable monomer)
The type of the electropolymerizable monomer to be used is not particularly limited as long as it is a monomer that can be electropolymerized by applying a voltage.
For example, as a monomer used in cathodic reduction polymerization, for example, vinyl monomers such as vinyl pyridine, acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, acrylonitrile, styrene, crotonic acid, acetonitrile, or derivatives thereof Or a compound in which two halogen atoms are bonded to an aromatic ring (eg, benzene, thiophene, pyrrole) (dihaloaromatic compound), or a dihalogen compound such as benzyl bromide.
Examples of the monomer used in the anodic oxidation polymerization include benzene, pyrrole, aniline, phenol, phthalocyanine, thiophene, furan, azulene, and derivatives thereof. More specifically, aniline, alkylanilines, alkoxyanilines, haloanilines, o-phenylenediamines, 2,6-dialkylanilines, 2,5-dialkoxyanilines, 4,4′-diaminodiphenyl ether, etc. Aniline and aniline derivatives of pyrrole; pyrrole and pyrrole derivatives such as pyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-propylpyrrole; thiophene, 3-methylthiophene, 3-ethylthiophene, 3,4-ethylenedioxythiophene, etc. And thiophene and thiophene derivatives thereof.

  The content of the electropolymerizable monomer in the solution W is not particularly limited, but is preferably 0.1 to 1000 mM from the viewpoint that the film formation of the polymer film proceeds more efficiently and the flatness thereof is more excellent. 100 mM is more preferable.

(Supporting electrolyte)
The solution W contains a supporting electrolyte. By including the supporting electrolyte, the film formation of the polymer film proceeds efficiently.
As the supporting electrolyte, a supporting electrolyte which is a substance capable of ionization, dissolves well in a solvent and dissociates into a cation and an anion, imparts ionic conductivity, hardly undergoes oxidation / reduction, and is stable in a wide potential range is desirable.
As the supporting electrolyte, a known supporting electrolyte can be used. For example, a compound represented by the general formula MX, R ₄ NX (where M = alkali metal ion, alkaline earth metal ion, transition metal ion, pyridinium ion) , Imidazolium ion, quaternary phosphonium ion, etc., X = A ⁻ (A is halogen), N (CF ₃ SO ₂ ) ²⁻ , BF ⁴⁻ , PF ⁶⁻ , CF ₃ SO ₃ ⁻ , CF ₃ CO ₂ ⁻ , NO ₃ ⁻ , SCN ⁻ , ClO ₄ ⁻ , carbonate ion, benzoate anion, alkylnaphthalene sulfonate ion, or picrate anion, R ₄ N: tetraalkylammonium salt (R; CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H _{9 and the} like)).
More specifically, butyl naphthalene sulfonate sodium etc. are mentioned.

  The content of the supporting electrolyte in the solution W is not particularly limited, but is preferably 1000 mM or less, more preferably 0.1 to 100 mM from the viewpoint that the film formation of the polymer film proceeds more efficiently and the flatness thereof is more excellent. Preferably, 1-50 mM is more preferable.

(Other ingredients)
The solution W may contain a solvent, and the kind thereof is not particularly limited, and examples thereof include water or an organic solvent (for example, acetonitrile, nitrobenzene, hexane, toluene, diethyl ether, benzene, etc.).

(Conditions for electrolytic polymerization)
As the electrolytic polymerization carried out in the present invention, either anodic oxidation polymerization or cathodic reduction polymerization can be carried out, and an optimum method is appropriately selected according to the electrolytic polymerizable monomer to be used.

  For the electropolymerization, a known electropolymerization method can be used, and any of a constant current method, a constant voltage method, and a potential scanning method may be used. The constant current method is preferable because the film thickness of the polymer film (particularly the conductive polymer film) deposited on the conductive substrate 18 can be controlled by the energization time.

The electropolymerization conditions are not particularly limited. For example, when the constant current method is used, the current density is preferably in the range of 0.01 to 50 mA / cm ² in that the obtained polymer film has more excellent flatness. The range of 1-10 mA / cm < ² > is more preferable.
In the potential scanning method, the potential range needs to be within a range in which the medium and the electrolyte are not decomposed. Therefore, the potential range is set according to the type of the medium and the supporting electrolyte. Usually, the potential range is -2 to 2 Vvs. Polymerization is possible in the range of saturated calomel electrode (SCE), -0.5 to 1.2 Vvs. The range of saturated calomel electrode (SCE) is more preferred.

  The time for electrolytic polymerization (electrolytic time) and the temperature of the solution W at the time of electrolytic polymerization are not particularly limited, and are appropriately selected so that a polymer film having a desired thickness can be obtained.

  If necessary, the electrolytic polymerization may be performed while discharging the solution W from the electrolytic polymerization tank 12 and supplying a new solution W. During the electropolymerization, reaction by-products are generated and may float in the solution W. Therefore, when performing electrolytic polymerization continuously, the properties of the polymer film produced by these byproducts are affected, and flatness and the like may be impaired. Accordingly, by continuously supplying new solution W to the electrolytic polymerization tank 12 and continuously replacing the solution W, it is possible to suppress deterioration of the properties of the polymer film.

The method for supplying the solution W is not particularly limited, and the solution W may be supplied to the electrolytic polymerization tank 12 via an injection pipe (not shown). In addition, when performing anodic oxidation polymerization, it is preferable to supply the solution W so that the solution W in the electrolytic polymerization tank 12 flows from the cathode 14 toward the conductive substrate 18. If it is this form, the new solution W will be continuously supplied on the surface where superposition | polymerization of the electroconductive board | substrate 18 advances, and a polymer film will be formed more efficiently as a result.
The method for discharging the solution W from the electrolytic polymerization tank 12 is not particularly limited, and the solution W may be discharged from a discharge port arranged at the bottom of the electrolytic polymerization tank 12 (not shown). 12 may be discharged after overflowing.

(Polymer film)
A polymer film excellent in flatness is obtained on the conductive substrate 18 by the above-described procedure.
The film thickness of the polymer film is appropriately adjusted by changing the conditions for electrolytic polymerization, but is preferably 10 nm to 100 μm and more preferably 10 nm to 500 nm in terms of more excellent flatness.

  In addition, by using benzene, pyrrole, aniline, phenol, phthalocyanine, thiophene, furan, azulene, or a derivative thereof as an electropolymerizable monomer, a polymer film (conductive polymer film) having excellent conductivity is obtained. be able to.

  The conductive substrate 18 having the polymer film (particularly a conductive polymer film) can be used for various applications. For example, it can be used as a member of a dye-sensitized solar cell.

<Electropolymerization apparatus for polymer film production (second embodiment)>
Below, 2nd Embodiment of the electropolymerization apparatus for polymer film manufacture of this invention is described with reference to drawings.
FIG. 3 is a schematic configuration diagram of an electropolymerization apparatus 100 for producing a polymer film of the present invention.
The polymer film production electrolytic polymerization apparatus 100 includes an electrolytic polymerization tank 12, a cathode 14, an anode 16, a conductive substrate 18, a power source 20, and an insulating partition wall 22.
An electropolymerization apparatus 100 for producing a polymer film shown in FIG. 3 is an electropolymerization apparatus used for anodizing polymerization, and the polymer film production shown in FIG. Therefore, the same constituent elements are denoted by the same reference numerals, the description thereof is omitted, and the insulating partition 22 will be mainly described.

The insulating partition wall 22 is disposed between the conductive substrate 18 and the anode 16 and has an opening 24 through which the solution W flows in the center. The insulating partition wall 22 is disposed in the electrolytic polymerization tank 12 so as to partition the cathode 14 and the anode 16.
When there is no insulating partition wall 22 (in the case of the electropolymerization apparatus 10 for producing a polymer film), a polymer film is formed on the surface of the conductive substrate 18 on the cathode 14 side when electrolytic polymerization is performed. In the peripheral region (edge region) of the surface on the cathode 14 side of 18, a region not covered with the polymer film may occur. This is because the current flowing in the solution existing around the conductive substrate 18 is not regulated, so that the anodic polarization of the entire surface of the conductive substrate 18 on the cathode 14 side is insufficient, and the surface of the conductive substrate 18 on the cathode 14 side is insufficient. This is because sufficient radical cations are not generated in the peripheral region and the polymerization reaction does not proceed sufficiently.
On the other hand, by providing the insulating partition wall 22, the current flow around the conductive substrate 18 can be regulated, and a sufficient amount of radical cations can be obtained in the peripheral region on the cathode 14 side surface of the conductive substrate 18. As a result, the coverage of the polymer film on the conductive substrate 18 is improved, and variations in the film thickness of the polymer film are further suppressed.

  The insulating partition wall 22 has an opening 24 through which the solution W flows at a position facing the central portion of the conductive substrate 18. More specifically, in FIG. 3, an opening 24 is provided at the center of the insulating partition wall 22. By having the opening 24 at this position, the influence of the anode 16 on the peripheral region of the surface on the cathode 14 side of the conductive substrate 18 can be further suppressed, and as a result, the polymer film on the conductive substrate 18 is obtained. The coverage of can be further improved.

Note that the position of the opening 24 may be a position other than the position facing the center of the conductive substrate 18.
Further, the size of the opening 24 is not particularly limited, and an optimal size is appropriately selected according to the size of the conductive substrate 18 to be used. From the viewpoint of more efficiently forming the polymer film, the ratio (A / B) of the area A of the opening 24 to the area B of the insulating partition wall 22 is preferably 0.005 to 1. 01-0.1 is more preferable.
Further, the shape of the opening 24 is long in FIG. 3, but the shape is not particularly limited, and may be circular, elliptical, or amorphous.
Furthermore, although the number of the openings 24 is one in FIG. 3, the number is not particularly limited, and a plurality of openings 24 may be provided.

  The material which comprises the insulating partition 22 is not restrict | limited in particular, If it is the material which shows insulation, it will not restrict | limit in particular. For example, polymer (for example, polyethylene, polypropylene), glass, etc. are mentioned.

The conditions for the electropolymerization using the electropolymerization apparatus 100 for polymer film production are the same as the conditions for the electropolymerization using the electropolymerization apparatus 10 for polymer film production described above. In addition, before applying a voltage between the cathode 14 and the anode 16, the insulating partition 22 mentioned above is arrange | positioned.
The polymer film obtained by this form is more excellent in the coverage on the surface of the conductive substrate 18, and the variation in film thickness is smaller. More specifically, the coverage of the polymer film on the surface of the conductive substrate 18 is preferably 90% or more, and more preferably 95% or more. Most preferably, it is 100%.

  In addition, in FIG. 3, the electropolymerization apparatus 100 for polymer film manufacture was illustrated as a form used in the case of anodic oxidation polymerization. On the other hand, in the case of cathodic electropolymerization, it is preferable that the insulating partition wall 22 is disposed not between the anode 16 and the conductive substrate 18 but between the cathode 14 and the conductive substrate 18. If it is this form, the polymer film which shows a high coverage on the surface by the side of the anode 16 of the electroconductive board | substrate 18 can be formed efficiently.

<Electropolymerization apparatus for polymer film production (third embodiment)>
Below, 3rd Embodiment of the electropolymerization apparatus for polymer film manufacture of this invention is described with reference to drawings.
FIG. 4 is a schematic cross-sectional view of an electropolymerization apparatus 200 for producing a polymer film of the present invention.
The polymer film production electrolytic polymerization apparatus 200 includes an electrolytic polymerization tank 12, a cathode 14, an anode 16, a strip-like conductive substrate 26, and a roller 28. The cathode 14 and the anode 16 are connected to a power source (not shown) through an external power supply terminal and wiring.
An electropolymerization apparatus 200 for producing a polymer film shown in FIG. 4 is an electropolymerization apparatus used for electrolytic polymerization of the strip-shaped conductive substrate 26 except that the strip-shaped conductive substrate 26 and a roller 28 are provided. 1 has the same configuration as that of the electropolymerization apparatus 10 for producing a polymer film shown in FIG. 1, and therefore, the same components are denoted by the same reference numerals and the description thereof is omitted.

  The polymer film production electrolytic polymerization apparatus 200 is an apparatus that continuously performs electrolytic polymerization on the strip-shaped conductive substrate 26. Specifically, the strip-shaped conductive substrate 26 continuously supplied from a conductive substrate supply unit (not shown) is immersed in the solution W in the electrolytic polymerization tank 12 and is continuously connected to the cathode 14 and the anode via the roller 28. 16 is supplied. While passing between the cathode 14 and the anode 16, a polymer film is formed on the surface of the strip-like conductive substrate 26. If it is this form, a polymer film can be manufactured continuously and it is more excellent in industrial productivity.

  In the electrolytic apparatus 200 for polymer film production, the solution W described above is provided between the anode 14 and the strip-shaped conductive substrate 26 or between the anode 16 and the strip-shaped conductive substrate 26 as necessary. You may arrange | position the insulating partition which has the opening part which distribute | circulates. By disposing the insulating partition, the coverage of the polymer film on the strip-like conductive substrate 26 is further improved.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

Example 1
(Electrolyzer for polymer membrane production)
First, an electrolytic apparatus 10 for producing a polymer film shown in FIG. 1 was produced. As the cathode 14 and the anode 16, a stainless steel substrate (length: 10 mm, width: 10 mm) was used. As the conductive substrate 18, a glass substrate (vertical: 10 mm, horizontal: 10 mm) whose surface was coated with ITO was used.
In addition, the width | variety of the electrolytic polymerization tank 12 was 20 mm, and length was 35 mm. Further, the distance between the cathode 14 and the conductive substrate 18 was 16 mm. The distance between the anode 16 and the conductive substrate 18 was 16 mm.
Further, as shown in FIG. 1, the cathode 14, the anode 16, and the conductive substrate 18 were arranged so as to be substantially parallel to each other.

(Electrolytic polymerization)
As solution W, an aqueous solution containing sodium butylnaphthalenesulfonate (10 mM) and 3,4-ethylenedioxythiophene (EDOT) (20 mM) was prepared.
Next, the solution W is supplied into the electrolytic polymerization tank 12 to perform 4 mA / cm ² constant current electrolytic polymerization (electrolysis time 20 seconds), and a high thickness of 30 nm is formed on the surface of the conductive substrate 18 on the cathode 14 side. A molecular film (poly (3,4-ethylenedioxythiophene) (PEDOT) film) was produced.

(Various evaluations)
When the root mean square roughness (RMS) of the obtained polymer film was measured using a nanoscale hybrid microscope (Keyence VN-8000), the same numerical value as in Example 2 described later was obtained.
Moreover, when the coverage of the polymer film on the surface (one side) of the conductive substrate 18 was measured, it was 87%. The coverage was calculated from the area of one side of the portion of the conductive substrate 18 immersed in the solution W by observing the surface of the conductive substrate 18 with a microscope.

(Example 2)
(Electrolyzer for polymer membrane production)
First, an electrolytic device 100 for producing a polymer film shown in FIG. 3 was produced. As the cathode 14 and the anode 16, a stainless steel substrate (length: 10 mm, width: 10 mm) was used. As the conductive substrate 18, a glass substrate (vertical: 10 mm, horizontal: 10 mm) whose surface was coated with ITO was used. Further, a polypropylene substrate was used as the insulating partition wall 22. A rectangular opening 24 having a width of 2 mm is provided at the center of the insulating partition wall 22.
In addition, the width | variety of the electrolytic polymerization tank 12 was 20 mm, and length was 35 mm. The distance between the cathode 14 and the conductive substrate 18 was 15 mm, and the distance between the cathode 14 and the insulating partition wall 22 was 16 mm. Moreover, the distance between the anode 16 and the insulating partition 22 was 16 mm.
Further, as shown in FIG. 1, the cathode 14, the anode 16, the conductive substrate 18, and the insulating partition wall 22 were arranged so as to be substantially parallel to each other.

(Electrolytic polymerization)
Using the same solution W as in Example 1, a polymer film (poly (3,4-ethylenedioxythiophene) (PEDOT) film) with a film thickness of 30 nm was produced under the same conditions.

(Surface roughness evaluation)
It was 7.1 nm when the root mean square roughness (RMS) of the obtained polymer film was measured using the nanoscale hybrid microscope (Keyence VN-8000).
Moreover, when the coverage of the polymer film on the surface (one side) of the conductive substrate 18 was measured, it was 100%. The coverage was calculated from the area of one side of the portion immersed in the solution W of the conductive substrate 18 by observing the surface of the obtained conductive substrate with a microscope.
From the results, it was confirmed that the coating rate of the polymer film was improved by providing the insulating partition 22.

(Comparative Example 1)
An electrolytic apparatus 300 for polymer film production shown in FIG. 7 was produced. As the cathode 306, a stainless steel substrate (length: 10 mm, width: 10 mm) was used. As the anode 308, a glass substrate (length: 10 mm, width: 10 mm) whose surface was coated with ITO was used. The distance between the cathode 306 and the anode 308 was 16 mm.
Moreover, as the electrolytic solution 302, an aqueous solution containing sodium butylnaphthalenesulfonate (10 mM) and 3,4-ethylenedioxythiophene (EDOT) (20 mM) was prepared.
Next, 0.1 mA / cm ² constant current electropolymerization (electrolysis time 60 seconds) is performed, and a polymer film (poly (3,4-ethylenedioxythiophene) (PEDOT) film) having a film thickness of 30 nm is formed on the surface of the anode 308. Manufactured.
When the root mean square roughness (RMS) of the obtained polymer film was measured, it was 8.0 nm, which was inferior to the forms of Example 1 and Example 2.

(Other evaluation)
(Optical evaluation)
The transmittance | permeability was measured with respect to the board | substrate with a polymer film obtained in Example 2 and Comparative Example 1 using ultraviolet visible near-infrared spectrophotometer UV-3600. The results are shown in FIG. In FIG. 5, the form of Example 2 is “ITO / PEDOT (bipolar)”, the form of Comparative Example 1 is “ITO / PEDOT (normal)”, and the conductive substrate 18 having no polymer film is “pure ITO”. Display as.
As shown in FIG. 5, the polymer film obtained in Example 2 exhibits high transmittance and excellent transparency, similar to the polymer film produced by the conventional method (Comparative Example 1). Was confirmed.

(Electrochemical evaluation)
Platinum is mainly used as the counter electrode material of the dye-sensitized solar cell, but a conductive polymer such as PEDOT can also be used. In particular, if a conductive polymer transparent material such as PEDOT is used, cost reduction and total transparency can be expected.
Therefore, the reduction reaction of the iodine compound was measured by cyclic voltammetry (Hokuto Denko HZ-3000) using the substrate with the polymer film prepared in Example 2, and the electrode catalytic ability of the polymer film (PEDOT film) was examined. did. More specifically, cyclic voltammetry measurement in the case of using a platinum electrode and a substrate with a polymer film prepared in Examples in acetonitrile containing I ₂ (1 mM), LiI (10 mM), and LiBF ₄ (1M). Performed (FIG. 6). When the substrate with the polymer film obtained in Example 2 is used (FIG. 6B), the behavior is the same as that of the platinum electrode (FIG. 6A) and can be used instead of the platinum electrode. Was confirmed.

10, 100, 200, 300 Electropolymerization apparatus for polymer film production 12,304 Polymerization tank 14,306 Cathode 16,308 Anode 18, 18a, 18b Conductive substrate 20,310 Power source 22 Insulating partition 24 Opening 26 Band-like conductivity Substrate 28 Roller 302 Electrolytic solution W Solution containing electropolymerizable monomer and supporting electrolyte

Claims (6)

  An electroconductive substrate is immersed in the solution so that the cathode or the anode and the main surface face each other between a cathode and an anode immersed in a solution containing an electropolymerizable monomer and a supporting electrolyte, and the cathode A method of producing a polymer film, wherein a voltage is applied between the anode and the anode, and a polymer film is produced on the surface of the conductive substrate by electrolytic polymerization of the electropolymerizable monomer using a bipolar phenomenon. An insulating partition having an opening through which the solution flows is disposed between the conductive substrate and the cathode or between the conductive substrate and the anode before applying the voltage; A method for producing a molecular film.   The method for producing a polymer film according to claim 1, wherein the insulating partition has an opening at a position facing a central portion of the conductive substrate.   The method for producing a polymer membrane according to claim 1 or 2, wherein the concentration of the supporting electrolyte in the solution is 1000 mM or less.   The high in any one of Claims 1-3 in which the said electropolymerizable monomer contains at least 1 chosen from the group which consists of benzene, pyrrole, aniline, phenol, phthalocyanine, thiophene, furan, azulene, and these derivatives. A method for producing a molecular film. An electropolymerization apparatus for producing a polymer film for producing a polymer film on the surface of a conductive substrate,
An electropolymerization tank in which a solution containing an electropolymerizable monomer and a supporting electrolyte is accommodated;
A cathode and an anode disposed in the electrolytic polymerization tank;
In the electrolytic polymerization tank, a conductive substrate disposed between the cathode and the anode so that the cathode or the anode and the main surface face each other,
In the electrolytic polymerization tank, having an insulating partition having an opening through which the solution flows, disposed between the conductive substrate and the cathode or between the conductive substrate and the anode,
Electrolysis for polymer film production in which a voltage is applied between the cathode and the anode, and a polymer film is produced on the surface of the conductive substrate by electropolymerization of the electropolymerizable monomer using a bipolar phenomenon. Polymerization equipment. The electropolymerization apparatus for producing a polymer film according to claim 5 , wherein the insulating partition has an opening at a position facing the central portion of the conductive substrate.

Images