JPS59219802A - Method of producing conductive polymer composition film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION FIELD OF INDUSTRIAL APPLICATION The present invention relates to a method for producing conductive polymer composition films used in the field of electronic devices.

Conventional structure and its problems Conventionally, for example, Keiji Kanazawa
et,al,.

J, Chem, Soc, Chem, Comm+,
854 (1979) and others, a method of producing a polymer composition by electrolytically oxidizing virol in the presence of a supporting electrolyte such as tetraethylammonium borofluoride is mentioned. These compositions have high electrical conductivity and are useful as electrical conductors. However, these compositions are generally porous and brittle, and not only do I/i7 have difficulties in practical use, but also mechanical properties and other properties deteriorate further when electrolytically oxidized repeatedly using the same electrolyte solution. do.

Purpose of the Invention The present invention provides a manufacturing method for efficiently supplying a conductive polymer composition film that is dense, has sufficient mechanical strength for practical use, and has uniform properties such as electrical conductivity. The purpose is to

Structure of the Invention The production method of the present invention is characterized by repeatedly performing electrolytic oxidation in an electrolyte solution containing an electrolytically oxidized substance (a substance that is electrolytically oxidized to give a polymer composition) in a non-uniformly dispersed state.

By the method of the present invention, a conductive polymer composition film having sufficient mechanical strength and uniform properties for practical use can be repeatedly and efficiently supplied in large quantities.

Description of examples The invention will be explained in more detail below with reference to the drawings.

Heterogeneously dispersed states include various states such as emulsions, suspensions or colloids. The colloidal state will be explained below as an example.

The figure shows colloidal particles 1 made of an electrolytically oxidized substance dispersed in an electrolyte solution 2. The effect of the present invention can be interpreted as follows. That is, it is considered that the boundary line 4 between the anode 3 and the colloidal particles 1' attached to the anode 3 becomes an active site for electrolytic oxidation, and the site where polymerization occurs is limited to a narrow range of this boundary line 4. Therefore, the growth reaction of each polymer is not hindered, the degree of polymerization is increased, and large mechanical strength is imparted to the electropolymer composition. These phenomena are well known in ordinary emulsion polymerization.

Further, as the electrolytic reaction progresses, by-products of the electrolytic reaction, such as a solvent or a supporting electrolyte, are generated in the cage electrolyte solution.

However, since the electrolytically oxidized substance is protected within colloidal particles 1,1', as long as colloidal particles 1,1' exist stably, electrolytic oxidation is thought to proceed stably regardless of these byproducts. . As a result, a large amount of film with stable properties can be repeatedly and efficiently supplied.

The electrolytic oxidizing substance used in the present invention is selected from the following compound group.

(2L) Benzene or a derivative thereof (b) A five-membered heterocyclic compound containing one oxygen group element or nitrogen group element (C) A benzene ring and one oxygen group element or nitrogen group element
Multiple rings 1fiW tangent 1 selected from five-membered complex rings containing
frlr1. Ethers, sulfides, selenides.

Compounds bonded via any telluride bond However, the benzene ring or five-membered hetero ring of each compound may contain a halogen group, a hydroxyl group, an amine group, or a hydrocarbon group having 8 or less carbon atoms. It is assumed that at most two groups of and a hydrogen group are bonded.

Specific examples include the following compounds.

Phenol, thiophenol, virol, furan, thiophene, selenophene, benzene, tellurophene, biphenyl, p-terphenyl, 0-terphenyl, p-quarterphenyl, 2-hydroxybiphenyl, diphenyl ether, diphenyl sulfite, diphenylselenide, diphenyl Telluride, 2-(α-thenyl)thiophene, 2-(α-thenyl)furan, 2-(2-pyrrolyl)virol, 2-(2-pyrrolyl)thiophene, 2-
Phenylthiophene, 3-phenylthiophene, α-chenyl-phenyl-ether, β-furyl-α-chenyl selenide, 2-(2-pyrrolyl)selenophene, 2
-(2-selenienyl)tellophene, 3-methylthiophene, 3-hydroxythiophene, 3-aminothiophene.

The electrolyte solution contains various compounds such as organic quaternary ammonium salts, inorganic salts, protic acids, TCNQ salts, such as tetraethylammonium borofluoride, tetra-n-butylammonium perchlorate, tetramethylammonium bromide, lithium perchlorate. , sulfuric acid, benzenesulfonic acid fc 41
Solutions such as acetonitrile, benzonitrile, nitrobenzene, dimethyl sulfate or diethyl sulfate containing tetraethylammonium TCNQ or the like as a supporting electrolyte are effectively used.

A colloidal state can be easily achieved by adding an appropriate surfactant. In particular, since virol or its derivatives easily and stably produce colloidal particles in sulfate esters such as dimethyl sulfate and diethyl sulfate, the present invention can be carried out effectively.

In addition, when electrolysis is repeated many times, electrolysis can be continued by appropriately supplementing an electrolytic oxidizing substance and a supporting electrolyte in the electrolyte solution. Good results are obtained when the number of repetitions is within about 1000 times. In particular, the best results are obtained when the number of times is 100 times or less.

Example 1 Regarding the eight combinations of supporting electrolytes and solvents shown in the following table,
Virol 52, supporting electrolyte. , 57 was dissolved in 200 mJ of solvent and stirred for 10 minutes to obtain an emulsion.

(Unit: 87 cm) A pair of indium oxide-tin glass electrode anode and platinum cathode was inserted into each of these, and electrolysis was repeated 20 times for 20 minutes at a current density of 2 mA/cm2, resulting in approximately 10
A dense and strong film with a thickness of μm was obtained. The average value of the electrical conductivity of these films at 25°C by the four-terminal method is shown in the table. The numbers in parentheses are the difference between the maximum and minimum conductivity of 20 films, respectively. 0.6 g of a surfactant was mixed with 200 ml of acetonitrile and subjected to ultrasonic dispersion for 30 minutes to obtain a suspension. This was repeated under the same conditions as in Example 1, and electrolysis was carried out 10 times, resulting in a thickness of approximately 10 μm and a conductivity of 1.2×10″6±0.4×
A 10′ S/Cm (7)7 ilm was obtained.

Example 3 Using the combination of tetraethylammonium tetrafluoroborate and dimethyl sulfate of Example 1, 1o and o@J electrolysis was repeated under the same conditions. However, at the end of the 60th electrolysis, 1 g of pyrrole and tetraethyla/monium tetrafluoroborate were added. , 11 were added and dissolved in the electrolyte solution, stirred for 10 minutes, and subsequent electrolysis was performed. As a result, strong films each having a thickness of 10 μm were obtained. The average value of the conductivity was 32 s/cm, and the maximum and minimum values were 60 and 19 S/cm, respectively.

As can be seen from these examples, the present invention provides conductive polymer composition films that are strong and have substantially uniform conductivity.

Effects of the Invention As described above, the production method of the present invention efficiently supplies a conductive polymer composition film that is dense, has sufficient mechanical strength, and has uniform properties.

[Brief explanation of the drawing]

The figure is a schematic diagram showing the principle of electrolytic oxidation according to the present invention. 1.1'... Colloidal particles, 2... Electrolyte solution, 4... Boundary line between colloidal particles and anode.

Claims (2)

[Claims] (1) A method for producing a conductive polymer composition film, which comprises repeated electrolytic oxidation in an electrolyte solution containing an electrolytically oxidized substance in a non-uniformly dispersed state. (2) The method for producing a conductive polymer composition film according to claim 1, wherein the number of repetitions is in the range of 2 to 1000 times.