TWI620201B - Organic conductive composition, conductive film, it element and method for forming conductive film - Google Patents

Abstract

The present invention provides a problem of the conventional organic conductive composition which is difficult to maintain stable physical properties due to the fact that the conductive polymer is easily oxidized, and provides a specific binder and a primary and secondary antioxidant by mixing and mixing. The organic conductive composition containing the oxidative stability of the organic conductive composition of the conductive polymer is greatly improved. The organic conductive composition of the present invention comprises: (a) a conductive polymer, (b) a dopant, (c) a decane coupling agent, and (d) a group selected from the group consisting of phenol-based derivative compounds. One or more kinds of primary antioxidants, (e) one or more secondary antioxidants selected from the group consisting of phosphorus compounds or sulfur compounds, and (f) residual amounts of solvents.

Description

Organic conductive composition, conductive film, information technology component, and method for forming conductive film Technical field

The present invention relates to an organic conductive composition, and more particularly to a problem of a conventional organic conductive composition which is incapable of maintaining stable physical properties due to the property of being easily oxidized by a conductive polymer. By mixing and using a specific binder and primary and secondary antioxidants, the organic conductive composition containing the oxidative stability of the organic conductive composition of the conductive polymer is greatly improved.

Background technique

The organic conductive composition is widely used in various fields. In particular, as the IT field is leaps and bounds, when a functional layer is required in an IT element including various display elements, the organic conductive composition has the advantage of being able to easily form a thin film layer having physical properties required for conductivity and the like. It is even more noticeable.

The organic conductive composition generally used in the past contains a conductive polymer. However, the conductive polymer is oxidized by the mechanism shown in Fig. 1, whereby the stability of the composition is largely attenuated.

Moreover, as shown in FIG. 2, it is understood that the organic conductive composition is compared with It is supplied with a high-temperature, high-humidity (80 ° C, humidity 90%) environment with moisture, and it will deteriorate more rapidly in an environment where only hot hot plates (80 ° C) are added to the atmosphere. Moreover, in the vacuum oven environment, the degree of deterioration is the smallest, and it can be seen that the supply of oxygen is the biggest factor in the deterioration of oxygen supply.

About 20.9% of oxygen is present in the air, and most of the conductive high scores When it comes into contact with air, it will produce an oxidation reaction on the surface. In particular, the free radicals generated during the molding process will lose the original physical properties and deteriorate, and it is not easy to use.

In addition, recently, in order to increase the penetration rate of conductive materials, When the thin film layer is formed by thinly coating the organic conductive composition to form a thin film layer, there is an urgent need for a method for solving the deterioration of the performance of the organic conductive composition due to oxidation.

Summary of invention

In order to solve the problems as described above, an object of the present invention is to provide an organic conductive material which is excellent in oxidative stability and conductivity of an organic conductive composition which is not easily maintained by a property of being easily oxidized by a conductive polymer. Sexual composition.

Further, an object of the present invention is to provide a method for forming a conductive film using an organic conductive composition which remarkably improves the oxidation stability and conductivity, a conductive film formed by the above method, and a film comprising the same IT components.

To achieve the foregoing objects, the present invention provides a method comprising: (a) a conductive polymer, (b) a dopant, (c) a decane coupling agent, (d) one or more primary antioxidants selected from the group consisting of phenol-based derivative compounds, and (e) selected from the group consisting of An organic conductive composition of one or more secondary antioxidants of a group consisting of a phosphorus-based compound or a sulfur-based compound, and (f) a residual amount of a solvent.

Moreover, the present invention provides for coating the aforementioned organic material on a substrate. A method of forming a conductive film at a stage of a conductive composition, a conductive film formed by the above method, and an IT element including the conductive film.

The organic conductive composition of the present invention has a problem of not being able to maintain a stable physical property due to the fact that the conductive polymer is easily oxidized, and the specific binder is mixed and used once and twice. The antioxidant can greatly improve the oxidation stability of the organic conductive composition containing the conductive polymer.

Figure 1 is a schematic view showing the mechanism of peroxidation decomposition of polythiophene.

Fig. 2 is a view showing a change in sheet resistance of each storage environment using a conductive composition having PEDOT.

Fig. 3 is a view showing a change in sheet resistance of Example 1 and Comparative Examples 1 to 4 of the present invention.

Form for implementing the invention

The characteristic of the organic conductive composition of the present invention comprises: (a) a conductive polymer, (b) a dopant, (c) a decane coupling agent, (d) one or more primary antioxidants selected from the group consisting of phenol-based derivative compounds, and (e) selected from the group consisting of One or more secondary antioxidants and (f) a residual amount of a solvent composed of a phosphorus compound or a sulfur compound.

Hereinafter, each component will be described in detail.

(a) Conductive polymer

The conductive polymer used in the present invention has a basic function of making the organic conductive composition conductive. The conductive polymer which is generally used for the organic conductive composition is not particularly limited, and examples thereof include polyaniline, polypyrrole, polythiophene and its derivative or the like - a monomer thereof (aniline) For example, a polymer obtained by polymerizing a derivative of pyrrole or thiophene as a monomer, and more specifically, a poly(3,4-) polymerized by a derivative of thiophene 3,4-extended ethyldioxythiophene Ethyl dioxythiophene is exemplified.

In the present invention, the amount of the conductive polymer used is preferably 0.1 to 10% by weight based on the organic conductive composition. When the content of the conductive polymer is less than 0.1% by weight, the organic conductive composition is less likely to exhibit conductivity, and when it is more than 10% by weight, there is a problem that the dispersibility is deteriorated.

(b) dopant

The dopant used in the present invention is not particularly limited, and a conductive polymer generally used for an organic conductive composition can be used, and examples thereof include dodecylbenzenesulfonic acid, toluenesulfonic acid, camphorsulfonic acid, and benzenesulfonate. Acid, hydrochloric acid, styrenesulfonic acid, 2-propenylamine-2-methylpropanesulfonic acid and their respective chlorine compounds, 2-sulfosuccinate, sodium isophthalate-5-sulfonate, isophthalic acid Sodium dicarboxylate-5-sulfonate or sodium 5-sulfonate-bis(β-hydroxyethyl)isophthalate For example, the dopants may be used singly or in combination of two or more.

In the present invention, the amount of the dopant used is preferably from 0.1 to 40% by weight based on the organic conductive composition. In particular, since the dopant in the present invention is related to the content of the conductive polymer, the content of the dopant is 100 to 400 parts by weight based on 100 parts by weight of the conductive polymer. good.

(c) decane coupling agent

The organic conductive composition of the present invention contains a decane coupling agent. The decane coupling agent has an effect of improving the dispersibility and oxidation stability of the conductive polymer. As the decane coupling agent, for example, an alkyloxy decane compound, an amino decane compound, a vinyl decane compound, an epoxy decane compound, a methacryl decyloxy decane compound, an isocyanate decane compound or The fluorodecane-based compound may be used singly or in combination of two or more kinds thereof.

In the present invention, the amount of the decane coupling agent used is preferably from 3 to 90% by weight based on the organic conductive composition. When it is in the above range, the dispersibility and oxidation stability of the conductive polymer in the organic conductive composition can be simultaneously satisfied.

(d) and (e) antioxidants

The organic conductive composition of the present invention comprises (d) one or more primary antioxidants selected from the group consisting of phenol-based derivative compounds, and (e) selected from phosphorus-based compounds or sulfur-based compounds. One or more secondary antioxidants of the group.

The organic conductive composition of the present invention comprises the aforementioned 1 The secondary antioxidant and the secondary antioxidant can effectively prevent oxidation of the conductive polymer and achieve an effect of remarkably improving the oxidative stability of the organic conductive composition.

In the present invention, two or more kinds of (d) phenol-based derivative compounds, that is, primary antioxidants may be used, and simple phenolics, bisphenolics, and polyphenols may be used as the phenol-based derivatives. Polyphenolics, thiobisphenolics. More specifically, examples of the aforementioned phenol-based derivative include: 2,6-di-3-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and stearin Bismuth (3,5-di-3-butyl-4-hydroxyphenyl)propionate, distearyl bismuth (3,5-di-3-butyl-4-hydroxybenzyl) phosphate, Thiodiethylene glycol bis[(3,5-di-3-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene bis[(3,5-di-3) Grade-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylenebis[(3,5-di-3-butyl-4-hydroxyphenyl)propanamide], 4,4'-thiobis(6-3 grade-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-3 grade-butylphenol), 2, 2'-methylenebis(4-ethyl-6-3-butylphenol), bis[3,3-bis(4-hydroxy-3-3-butylphenyl)butyric acid] alcohol, 4,4'-butylene bis(6-3-butyl-m-cresol), 2,2'-ethylenebis(4,6-di-3-butylphenol), 2,2 '-Ethylene bis (4-2 grade - butyl-6-3 grade - butyl phenol), 1, 1,3-parade (2-methyl-4-hydroxy-5-3 grade - butylbenzene) Butane, bis[2-3 grade-butyl-4-methyl-6-(2-hydroxy-3-3-butyl-5-methylbenzyl)phenyl]terephthalic acid, 1,3,5-gin (2,6-dimethyl-3-hydroxy-4-3-butyl-butyl)isocyanate, 1,3,5-paran (3,5-di-3-butyl base 4-hydroxybenzyl)isocyanate, 1,3,5-gin (3,5-di-3-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5 - ginseng [(3,5-di-3-butyl-4-hydroxyphenyl)propenyloxyethyl]isocyanate, tetra[methylene-3-(3,5-di-3-butyl) 4-hydroxyphenyl)propionate]methane, 2-3 grade-butyl-4-methyl-6(2-propenyloxy-3-3 grade-butyl-5-methylbenzyl Phenol, 3,9-bis 1,1-dimethyl-2-[(3-3-butyl-5-methylbenzyl)propoxy]ethyl-2,4,8, 10-four Spiro[5,5]undecane, triethylene glycol bis[(3-3-butyl-4-hydroxy-5-methylphenyl)propionate], carbon number 1 to 5 Acid alkyl esters and the like.

The above-mentioned Bisphenolics/Polyphenolics have the low volatility and the relatively low Equivalent weight which are higher than the molecular weight of the simple phenolics, and are excellent in processability. It is preferably used in combination with simple phenolics. Further, polyphenolics antioxidants can be used as 8-Hydroxyquinoline or 8-Hydroxyquinoline sulfate. , 8-Hydroxyquinoline-5-sulfonic acid, tetrakis (methylene-3,5-di-t-butyl-4-hydroxysulphonic acid) methane (Tetrakis (methylene) -3,5-di-t-butyl-4-hydroxyhydrocinnamate)methane).

In the present invention, two or more kinds of secondary antioxidants selected from the group consisting of phosphorus compounds or sulfur compounds can be used alone or in combination, and secondary antioxidants can be prevented from being caused by hydrogen. The action of the diffusion of alkoxy groups and hydroxyl radicals caused by the decomposition of a hydroperoxide. Examples of the phosphorus-based antioxidant include: decyl (nonylphenyl) phosphite, ginseng (2,4-di-3 -butylphenyl) phosphite, and ginseng [2-3 grade-butyl -4-(3-3-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tridecyl phosphite, octyl diphenylphosphite Ester, bis(indenyl)monophenylphosphite, monodecyldiphenylphosphite, mono(didecylphenyl) Bis(nonylphenyl)phosphite, di(tridecyl)neopentanol diphosphite, distearyl neopentyl glycol diphosphite, bis(nonylphenyl)pentaerythritol Diphosphite, bis(2,4-di-3-butylphenyl)neopentitol diphosphite, bis(2,6-di-3-butyl-4-methylphenyl) Neopentyl alcohol diphosphite, tetrakis(tridecyl)isopropylidene-diphenyl diphosphite, tetra (C12-16 mixed alkyl)-4,4'-n-butylene bis ( 2-3 grade -butyl-5-methylphenol) diphosphite, hexakis(tridecyl) 1,1,3-parade (2-methyl-4-hydroxy-5-3 grade-butylbenzene Butane triphosphite, tetrakis(2,4-di-3-butylphenyl)-stranded diphenyl bisphosphite, 2,2'-methylene bis (2,4-di-3 -butylphenyl)octyl)phosphite, and the like.

Examples of the aforementioned sulfur-based antioxidant include: methyl thioimidazole (Methimazole), dialkyl dithiopropionate [dilauryl thiopropionate, dimyristyl thiopropionate or di-hard Lipid thiopropionate], β-alkylmercaptopropionate of polyol [tetrapentaerythritol tetra(β-dodecylthioethanol propionate)].

In the organic conductive composition of the present invention, the amount of the primary antioxidant and the secondary antioxidant used is independently 5 to 10,000 ppm (0.005 to 1% by weight). When the amount is less than 5 ppm, the oxidation stability is not sufficiently obtained, and when it is more than 10,000 ppm, the conductivity of the organic conductive composition may be lowered.

The organic conductive composition of the present invention contains (f) a solvent, and the content of the residual amount after removing the components (a) to (e) is not particularly limited, and a solvent generally used for the organic conductive composition can be used. , can be used alone or in combination, such as: water; alcohols and glycols, polyols, methanol, ethanol, isopropanol, ethylene glycol, butanediol, neopentyl glycol, 1,3-pentanediol, 1,4-cyclohexanedimethanol, diethylene glycol, polyethylene glycol, polybutanol, a monomer selected from dimethylolpropane and trimethylolpropane or a derivative thereof One or more alcohols of the group formed, those produced by esterification of a diol or a polyol; chloroform, dichloromethane, tetrachloromethane, trichloroethane, dibromoethane, Halogen such as dibromopropane; n-methylpyrrolidone, dimethyl hydrazine; triethylamine, tributylamine, trioctylamine; or cresol.

Further, the organic conductive composition of the present invention contains the aforementioned components. In addition, a surfactant and other additives which can be usually added to the organic conductive composition may be contained.

Moreover, the present invention provides for coating the aforementioned organic layer on a substrate. A method for forming a conductive film at a stage of a conductive composition, a conductive film formed by the above method, and an IT element including the conductive film, wherein the coating method can be applied to a substrate, usually by applying organic conductivity The spray coating method, the bar coating method, the doctor blade method, the roll coating method, the dipping method, and the like of the composition, and the formation of the conductive film other than the coating may include a well-known stage generally used. Specifically, the organic conductive composition having a thickness of 5 to 20 μm is applied onto the substrate by a spray coating method, a bar coating method, a doctor blade method, or a roll coating method, and softly baked at 110 ° C for 180 seconds to form a thickness. After the film layer of 100 to 300 nm is dried in an oven at 120 ° C for about 10 minutes, a conductive film can be formed on the substrate.

As described above, the organic conductive composition of the present invention is used When a conductive film is formed, a conductive film having stable physical properties can be formed with high reliability, and the formed film can be made into a film made using a conventional organic conductive composition, and electrical conductivity, durability, and oxidation stability can be produced. excellent Different and reliable IT components.

In the following, the embodiments of the present invention are disclosed, but the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited by the following examples.

[Comparative Example 1]

PEDOT: PSS (poly 3,4-extended ethyldioxythiophene: polystyrene sulfonate, weight ratio: 1:2.5, 1.6% by weight) aqueous dispersion 5 wt%, TEOS (tetraethoxydecane) 10% by weight, 1% by weight of acetic acid, 1000 ppm of surfactant, 30% by weight of ethylene glycol (Ethyleneglycol), and IPA (isopropyl alcohol) as a residual amount, and an organic conductive composition was produced.

[Comparative Example 2]

To the above Comparative Example 1, 0.02% by weight of methyl thiolate (Methylgallate) was added once to prepare an organic conductive composition.

[Comparative Example 3]

To the above Comparative Example 1, 0.02% by weight of methyl thioimidazole (Methimazole) of the oxidation stabilizer was added twice to prepare an organic conductive composition.

[Comparative Example 4]

To the above Comparative Example 1, 0.06 wt% of methyl thiolate of an oxidation stabilizer was added to prepare an organic conductive composition.

[Example 1]

To the composition of Comparative Example 1, 0.02% by weight of Methylgallate and 0.02% by weight of methyl thioimidazole (Methimazole) of a secondary oxidation stabilizer were added once to prepare an organic conductive composition. .

Organic conductivity produced in the above Example 1 and Comparative Examples 1 to 4 The change in the sheet resistance of the composition (measured by ST-4 of Simco) was shown in Fig. 3. As shown in FIG. 3, it can be seen that Comparative Examples 2 to 3 using an antioxidant alone showed a slight anti-oxidation effect compared with Comparative Example 1, and when the primary antioxidant content was increased to 3 times (Comparative Example 4), The improvement effect is still not large, and the effect of the first embodiment is as shown in Example 1 when the antioxidant is used together with the secondary antioxidant.

Claims (9)

An organic conductive composition comprising (a) a conductive polymer of 0.1 to 10% by weight, (b) a dopant of 0.1 to 40% by weight, (c) a decane coupling agent of 3 to 90% by weight, (d) One or more kinds of primary antioxidants selected from the group consisting of phenolic derivative compounds, and 5 to 10000 ppm, and (e) one or more selected from the group consisting of phosphorus compounds and sulfur compounds. 2 times the antioxidant 5~10000ppm, and (f) residual solvent. The organic conductive composition of claim 1, wherein the (a) conductive polymer comprises poly(3,4-extended ethyldioxythiophene). The organic conductive composition of claim 1, wherein the (b) dopant is contained in an amount of 100 to 400 parts by weight based on 100 parts by weight of the conductive polymer (a). The organic conductive composition of claim 1, wherein the aforementioned decane coupling agent is tetraethoxydecane. The organic conductive composition of claim 1, wherein the primary antioxidant of the (d) phenolic derivative compound is methyl gallate. The organic conductive composition of claim 1, wherein the (e) secondary antioxidant is methyl mercaptan imidazole. A method of forming a conductive film, comprising the step of coating the substrate with the organic conductive composition according to any one of claims 1 to 6. A conductive film formed by the method of claim 7. An information technology (IT) component comprising the conductive film of claim 8.