JPH08157574A - Conductive material - Google Patents

Abstract

PURPOSE: To obtain a conductive material which is sol. in various solvents and is excellent in processibility and electrical and mechanical characteristics by doping. a specific sol. conductive polymer with a specific dopant. CONSTITUTION: This conductive material is prepd. by doping a sol. polymer having structural units represented by formula I [wherein R<1> is (substd.) alkyl, (substd.) alkoxy, halogen, or (substd.) phenyl; and R<2> is (substd.) alkyl or (substd.) phenyl] and a wt. average mol.wt. of 500-1.000,000 with a dopant represented by formula II. The electrical conductivity of the material. pref. 1×10<-7> S/cm or higher, can be adjusted by adjusting conditions such as the mixing ratio of the polymer to the dopant, usually the molar ratio of the monomer unit represented by formula I to the dopant being (30:1)-(1:2). The doping is carried out by dissolving the polymer in a solvent, homogeneously mixing the resulting soln. with the dopant (soln.), and evaporating the solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive polymer material molding having excellent processability, a method for producing the same, and a homogeneous solution used for the same.

[0002]

2. Description of the Related Art Organic polymer materials having electronic conductivity are
In recent years, antistatic materials, electromagnetic wave shielding materials, secondary batteries,
A wide range of applications such as capacitors and electrochromic display devices are under consideration. As electron conductive polymer,
Polyacetylene, polyaniline, polyphenylene vinylene, polypyrrole, polythiophene, etc. are known. Among them, N-methyl-2 is a material soluble in a solvent.
-Polyaniline soluble in pyrrolidone (M. Abe et.
al. J .; Chm. Soc. Chem. Comm
un. , 1989, 1736), polypyrrole having a substituent such as an alkyl group introduced therein, and polythiophene (M.-.
A. Sato, S .; Tanaka, K .; Kaeriya
ma: Synth. Met. (1987, 18, 229)
There is. It is known that a polymer such as polyphenylene vinylene is soluble in its precursor polymer.
Since these polymers can be formed into films by casting, application of various polymer films to antistatic materials and the like is being studied. However, in order to impart conductivity to the conductive polymer, it is necessary to treat it with an electron-accepting or electron-accepting compound (hereinafter referred to as doping) after molding, soak it in an acidic solution, expose it to a dopant vapor, etc. However, this was a problem in terms of processing. As a means for solving the problems of these conductive polymers, a conductive polymer having a self-doping property in which a counter ion serving as a dopant is covalently bonded to a polymer (AO Patil et al. J. Am. Che.
m. Soc. 1987, 109, 1858-1859).
However, since this type of conductive polymer has a sulfonic acid group in the polymer chain, it is used in applications in which the polymer itself is strongly acidic and is in contact with materials that are corroded or decomposed by acid. Could not be used for. Furthermore, a method for producing a conductive polymer film using a uniform solution of an organic electron acceptor and a polypyrrole derivative (JP-A-3-329854) has been proposed, but in a high-concentration polymer solution, the mixed solution becomes a gel state. There was a problem that it was easy.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a conductive substance that is soluble in various solvents, has excellent processability, and has excellent electrical and mechanical properties, a molded product, a manufacturing method, and a uniform solution used for the same. The purpose is.

[0004]

The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, depending on the combination of the soluble conductive polymer and the dopant, a stable and uniform solution can be obtained even in a high-concentration solution. It was found that a mixed solution was obtained, and the present invention was completed.

That is, the present invention is based on the formula [I] (1)

[Chemical 7] (In the formula, R ¹ represents substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, halogen, substituted or unsubstituted phenyl, and R ² represents substituted or unsubstituted alkyl, substituted or unsubstituted phenyl.) To a soluble polymer having a weight average molecular weight of 500 to 1,000,000 having a structural unit represented by the formula [II]

Embedded image A conductive material doped with a dopant represented by
(2) A polymer compound molded body containing the conductive substance according to (1) above, (3) formula [I].

[Chemical 9] (Wherein R ¹ and R ² have the same meanings as described above), and a soluble polymer solution having a weight average molecular weight of 500 to 1,000,000 and a structural formula [II]

[Chemical 10] The method for producing a conductive substance according to (1) above, which comprises mixing the dopant represented by the formula (1) or a solution thereof and drying the mixture, (4) Formula [I]

[Chemical 11] (Wherein R ¹ and R ² have the same meanings as described above), and a soluble polymer having a weight average molecular weight of 500 to 1,000,000 and a formula [II]

[Chemical 12] It is a homogeneous solution containing the dopant represented by the following formula: mole number of monomer unit: mole number of dopant: 30: 1 to 1: 2.

A preferred specific example of the soluble polymer belonging to the formula [I] is that R ¹ is a linear alkyl group, more preferably a methyl group, and R ² is a linear alkyl group, more preferably a C 2-18 group. It is an alkyl group. The polymer used in the present invention is a copolymer of the monomer units represented by the formula [I] and a monomer unit other than the monomer units represented by the formula [I], for example, pyrrole, N-methylpyrrole, 3-methylpyrrole, thiophene. Copolymers including, 3-methylthiophene, and the like are also contemplated. A typical molecular weight is 10,000 to 200,000 in terms of weight average molecular weight.
In order to obtain high solubility, it is preferably 200,000 or less, and in order to obtain high conductivity and toughness, it is preferably 20,000 or more.

The electric conductivity of the electroconductive substance of the present invention can be adjusted by conditions such as the mixing ratio of the compound represented by the formula [I] and the compound represented by the formula [II]. The dopant mole number is 30: 1 to 1: 2,
It is preferably 20: 1 to 1: 1 and at least 1 × 1.
Those having a conductivity of 0 ⁻⁷ (S / cm) or more are preferable.

Examples of the polymer compound containing a conductive substance of the present invention include (soft, semi-rigid, and rigid) PVC; polyethylene; polypropylene; polyvinyl alcohol; polymethyl acrylate; polymethyl methacrylate; polyvinylidene chloride; polyacrylonitrile; Polybutadiene; polystyrene; ethylene-vinyl acetate copolymer; vinyl chloride-vinyl acetate copolymer; polyvinyl butyral; polyvinyl formal; PET; polyesters such as PBT; polyarylate; polycarbonate; polyester carbonate; phenoxy resin; nylon 6, nylon 6 / 6, nylon 11, nylon 12, MXD6
Polyamide such as nylon; polydimethylsiloxane;
Polytrimethylsilylpropyl; polyurethane; ionomers; cellophane; polyethylene cellophane; cellulose acetate; cellulose propionate; ethyl cellulose; nitrocellulose; and other soft and hard resins.

In the present invention, the molded product is, for example, a plate, a film, a fiber, a fiber, a powder, a fine particle or the like. The method for producing the molded body is not particularly limited, and the melting characteristics of the resin, extrusion molding depending on the solvent solubility, inflation molding,
A varnish produced by calender molding, injection molding, transfer molding, or the like, in which a polymer compound containing a conductive substance of the present invention is dissolved, is coated on glass, plastic plate, reflector film, or impregnated into woven cloth, non-woven cloth, paper, etc. It can be manufactured by

Since the molded product meets various conditions in use, it may be used in a kind and in an amount that does not impair the object of the present invention, such as an ultraviolet absorber, an antioxidant, a hindered amine light stabilizer, a lubricant, an antifogging agent and a drip agent. Additives can be added.

The polymer represented by the formula [I] has, for example, the formula [III]

[Chemical 13] (Wherein R ¹ and R ² have the same meanings as described above), the compound (one or more) is chemically polymerized in the presence of an oxidizable transition metal halide, and neutralized and washed. It can be manufactured by a method such as post-treatment (JP-A-3-122115). Further, a copolymer containing other monomer units can be produced in the same manner.

The compound represented by the formula [II] can be produced by appropriately selecting a known reaction or a similar reaction. For example, (Hiroshi Mitsuhashi et al., Seikei University Engineering Report 1978, No. 26, 1867-18.
It can be manufactured by the method of 68).

The conductive substance described in (1) above is prepared by dissolving the polymer of the formula [I] in a suitable solvent, and further adding the dopant of the formula [II] or the solution of the dopant of the formula [II] to the above mixing ratio. It can be produced by volatilizing the solvent after adding a homogeneous solution, and by the means at that time, powder,
It can be a film, block, etc. Suitable solvents for preparing a stable mixed solution include tetrahydrofuran, dioxane, tetrahydrofurfuryl acetate, tetrahydrofurfuryl alcohol, ethers such as tetrahydrofurfuryl methacrylate, dimethylformamide, dimethylacetamide, N-methyl-2. Amides such as pyrrolidone, cyclic ketones such as cyclohexanone and cyclopentanone, halogenated hydrocarbons such as chloroform, dimethyl sulfoxide, cyclic amines such as 1-methylpyrrolidine, hexamethylphosphoric Various solvents can be used, provided that they are used as an inert solvent such as phosphoric acid amides such as triamide, or a mixed solvent thereof, and further mixed with the above solvent.

[0014]

EXAMPLES Next, the present invention will be described in more detail by way of examples. Reference Example 1 48.6 g of anhydrous ferric chloride was dissolved in 400 ml of a mixed solvent of butyl acetate and chloroform 1: 1 (v / v), and insoluble matter was removed by filtration. A solution prepared by dissolving 18.1 g of butyl 4-methyl-3-pyrrolecarboxylate in 100 ml of the same mixed solvent was added to this solution at room temperature (20 to 25
(° C.) and added dropwise over 2 hours. Then, at the same temperature, add 10
4 more while blowing at a speed of 0 to 150 ml / min
Reacted for hours. After completion of the reaction, 300 ml of methanol was added and filtered, and the precipitate was thoroughly washed with methanol. Then 80
% Wash with 100 ml of hydrazine hydrate, wash well with water, wash with methanol and dry to give the desired poly (butyl 4-methyl-3-pyrrolecarboxylate) 1
Obtained 6.2 g. Yield 90.5% Weight average molecular weight 128,000 (VS. polystyrene) Elemental analysis value Calculated value Actual value C 67.0 66.5 H 7.3 7.1 N 7.8 7.7

Example 1 THF was added to 1 g of the polymer obtained in Reference Example 1 and a polymer prepared by the same method except that the monomer unit was changed to prepare a 2% polymer solution. [II]
The compound shown in Table 1 was added in the amounts shown in Table 1 to obtain a uniform mixed solution. The mixed solution was poured on a glass plate and dried to prepare a conductor film. Table 1 shows a representative example of the present invention including the results of measuring the conductivity of the obtained film by the DC 4-terminal method.

[Table 1]

Example 2 Tetracyanoethylene was doped in the same manner as in Example 1 and the conductivity was measured. Table 2 shows the results.

[Table 2]

Example 3 Using the polymer obtained in Reference Example 1, a uniform solution was prepared by controlling the polymer concentration, the kind of dopant and the amount of dopant. A typical example is shown in Table 3 including the results of the stability investigation. The stability was compared by the period until the liquid became a gel state and the fluidity disappeared.

[Table 3]

[0018]

The conductive material of the present invention is prepared from a homogeneous mixed solution having excellent stability. The homogeneous mixed solution can be stored for a longer period of time, and it is possible to prepare a solution having a higher concentration. The conductive substance of the present invention is soluble in various solutions, has excellent workability, and has excellent electrical and mechanical properties. The present invention is very useful because it can be applied to a wide range of applications such as antistatic materials, liquid crystal base films and transparent electrodes.

Claims (5)

[Claims] 1. A formula [1] (In the formula, R ¹ represents substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, halogen, substituted or unsubstituted phenyl, and R ² represents substituted or unsubstituted alkyl, substituted or unsubstituted phenyl.) A soluble polymer having a weight average molecular weight of 500 to 1,000,000 having a structural unit represented by the formula [II] A conductive substance doped with a dopant represented by. 2. The dopant according to claim 1, wherein the number of moles of monomer unit of the dopant: the number of moles of dopant is 30: 1 to 1: 1.
Conductive material doped to 2. 3. A polymer compound molded body containing the conductive substance according to claim 1 or 2. 4. The formula [I]: (Wherein R ¹ and R ² have the same meanings as described above), and a soluble polymer solution having a weight average molecular weight of 500 to 1,000,000 and a structural unit represented by the formula [II] ] The method for producing a conductive substance according to claim 1 or 2, wherein the dopant represented by or a solution thereof is mixed and dried. 5. The formula [I]: (Wherein R ¹ and R ² have the same meanings as described above), and a soluble polymer having a weight average molecular weight of 500 to 1,000,000 and a structural formula [II] A homogeneous solution containing the dopant represented by the following formula: monomer unit mole number: dopant mole number 30: 1 to 1: 2.