WO2014014262A2

WO2014014262A2 - Organic conductive composition

Info

Publication number: WO2014014262A2
Application number: PCT/KR2013/006379
Authority: WO
Inventors: 이정훈; 김선영; 김병욱; 최경희
Original assignee: 주식회사 동진쎄미켐
Priority date: 2012-07-20
Filing date: 2013-07-17
Publication date: 2014-01-23
Also published as: TW201411653A; WO2014014262A3; KR20140012509A; CN104380390A; TWI620201B; KR102026446B1

Abstract

The present invention relates to an organic conductive composition, and more specifically, to an organic conductive composition comprising (a) a conductive polymer, (b) a dopant, (c) a silane coupling agent; (d) one or more first antioxidants selected from the group consisting of phenol-based derivative compounds, (e) one or more second antioxidants selected from the group consisting of phosphorus-based compounds and sulfur-based compounds; and (f) a solvent. It is difficult to maintain stable physical properties by using a conventional organic conductive composition due to the vulnerability of a conductive polymer to oxidation, but the organic conductive composition of the present invention can greatly improve oxidation stability of an organic conductive composition containing a conductive polymer by mixing a specific binder and first and second antioxidants.

Description

Organic conductive composition

The present invention relates to an organic conductive composition, and more particularly to the problem of the conventional organic conductive composition is difficult to maintain stable physical properties due to the oxidizable properties of the conductive polymer is a mixture of a specific binder and the primary and secondary antioxidants It relates to an organic conductive composition that greatly improved the oxidation stability of the organic conductive composition comprising a conductive polymer through.

Organic conductive compositions are widely used in various fields. In particular, when the functional layer is required for the IT device including various display devices with the rapid growth of the IT field, the organic conductive composition is attracting more attention because of the advantage of easily forming a thin film layer having required physical properties such as conductivity.

Conventionally commonly used organic conductive compositions include conductive polymers. However, the conductive polymer is oxidized through the mechanism as shown in FIG. 1, and thus the composition has a problem in that the stability is largely weak.

In addition, as shown in FIG. 2, the organic conductive composition is deteriorated faster in an environment of a hot plate (80 ° C.) that only heats in the atmosphere than an environment of high temperature and high humidity (80 ° C. and 90% humidity) supplied with moisture. have. In addition, the smallest deterioration in the vacuum oven environment indicates that the supply of oxygen is the most important factor of deterioration.

About 20.9% of oxygen is present in the air, and most conductive polymers undergo oxidation reactions on the surface when they are in contact with air. In particular, during the molding process, the generated radicals lose their original properties and deteriorate, making it difficult to use.

Furthermore, in recent years, when the organic conductive composition is thinly applied to form a thin film layer to increase the permeability of the conductive material, the possibility of air penetration is increased, and thus a solution for deterioration of the organic conductive composition due to oxidation is urgently required. It is becoming.

In order to solve the above problems, an object of the present invention is to provide an organic conductive composition that significantly improves the oxidation stability and conductivity of the organic conductive composition is difficult to maintain stable physical properties due to the oxidizable properties of the conductive polymer.

In addition, an object of the present invention is to provide a method for forming a conductive thin film using an organic conductive composition that significantly improves the oxidation stability and conductivity, the conductive thin film formed by the method, and an IT device including the thin film.

The present invention to achieve the above object,

(a) conductive polymers;

(b) dopants;

(c) silane coupling agents;

(d) a primary antioxidant selected from the group consisting of phenol derivative compounds;

(e) a secondary antioxidant selected from the group consisting of phosphorus compounds or sulfur compounds; And

(f) residual solvent

It provides an organic conductive composition comprising a.

In another aspect, the present invention provides a method for forming a conductive thin film comprising the step of applying the organic conductive composition on a substrate, a conductive thin film formed by the method, and an IT device comprising the conductive thin film.

The organic conductive composition of the present invention includes a conductive polymer through a mixed use of a specific binder and a primary and a secondary antioxidant, which is difficult to maintain stable physical properties due to the oxidizable property of the conductive polymer. Oxidation stability of the organic conductive composition can be greatly improved.

1 is a schematic diagram showing the peroxidation mechanism of polythiophene (Polythiophene),

Figure 2 shows the change in sheet resistance according to the storage environment of the conductive composition using PEDOT,

3 shows changes in sheet resistance of Example 1 and Comparative Examples 1-4 of the present invention.

The organic conductive composition of the present invention is a primary antioxidant selected from the group consisting of (a) conductive polymers, (b) dopants, (c) silane coupling agents, and (d) phenol derivative compounds, (e) It is characterized by including a secondary antioxidant selected from the group consisting of phosphorus compounds or sulfur compounds and (f) a residual amount of solvent.

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 is not particularly limited as long as it is a conductive polymer that can be generally used in an organic conductive composition, and examples thereof include polyaniline, polypyrrole, polythiophene and derivatives or analogs thereof of the monomers (aniline, pyrrole and thiophene). The polymer which the derivative superposed | polymerized by the monomer is mentioned, More specifically, the poly (3, 4- ethylene dioxythiophene) superposed | polymerized by the 3, 4- ethylene dioxythiophene which is a derivative of thiophene is mentioned.

The amount of the conductive polymer used in the present invention is preferably 0.1-10% by weight of the organic conductive composition. When the content of the conductive polymer is less than 0.1% by weight, it is difficult for the organic conductive composition to exhibit conductivity, and when the content of the conductive polymer is greater than 10% by weight, dispersibility becomes poor, which makes processing difficult.

(b) dopant

The dopant used in the present invention may be used without particular limitation as long as it is a conductive polymer that can be used in an organic conductive composition. Acrylamido-2-methylpropanesulfonic acid and its respective salt compounds, 2-sulfosuccinic acid ester salts, sodium 5-sulfoisophthalic acid, dimethyl-5-sodium sulfoisophthalate or 5-sodiumsulfo-bis (β- Hydroxyethyl) isophthalate is mentioned, The said dopant can be used individually or in mixture of 2 or more types.

The amount of the dopant used in the present invention is preferably 0.1-40% by weight of the organic conductive composition. In particular, since the dopant is linked to the content of the conductive polymer in the present invention, the content of the dopant is more preferably 100 to 400 parts by weight based on 100 parts by weight of the conductive polymer in terms of conductivity.

(c) silane coupling agent

The organic conductive composition of the present invention contains a silane coupling agent. The silane coupling agent functions to improve dispersibility and oxidative stability of the conductive polymer. As the silane coupling agent, for example, an alkyloxy silane compound, an amino silane compound, a vinyl silane compound, an epoxy silane compound, a methacryloxy silane compound, an isocyanate silage compound or a fluorine silane compound may be used. The said silane coupling agent can be used individually or in mixture of 2 or more types.

The amount of the silane coupling agent used in the present invention is preferably 3-90% by weight of the organic conductive composition. When in the above range can be satisfied at the same time the dispersibility and oxidation stability of the conductive polymer in the organic conductive composition.

(d) and (e) antioxidants

The organic conductive composition of the present invention comprises (d) at least one primary antioxidant selected from the group consisting of phenol derivative compounds and (e) at least one secondary antioxidant selected from the group consisting of phosphorus compounds or sulfur compounds. Include.

The organic conductive composition of the present invention is a primary antioxidant and a secondary antioxidant

At the same time, it effectively prevents the oxidation of the conductive polymer to significantly improve the oxidation stability of the organic conductive composition.

In the present invention, (d) the primary antioxidant, which is a phenol derivative compound, may be used alone or in mixture of two or more kinds. As the phenol derivative, simple phenolics, bisphenolics, polyphenolics, thiobisphenolics may be used. More specifically, examples of the phenol derivatives include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert) -Butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphate, thiodiethylene glycol bis [(3,5-di-3 Tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6- Hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2 ' Methylene bis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy -3-tert-butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis (6-tert-butyl-m-cresol), 2,2'-ethylidenebis (4,6-di -Tert-butylphenol), 2,2'-ethylidene bis (4-tert-butyl-6-tert-butylphenol), 1,1,3 Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-) 5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris ( 3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2, 4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2-3-butyl-4-methyl-6 (2-acryloyloxy-3-tert-butyl -5-methylbenzyl) phenol, 3,9-bis 1,1-dimethyl-2-[(3-tert-butyl-5-methylbenzyl) propionyloxy] ethyl-2,4,8,10-tetra Oxaspiro [5,5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], carbon number 1 And the like alkyl go Kate of five.

The Bisphenolics / Polyphenolics is preferably used in combination with simple phenolics in order to obtain optimum processability due to low volatility and relatively low equivalent weight due to high molecular weight compared to simple phenolics, and 8-Hydroxyquinoline, 8 as polyphenolics antioxidant -Hydroxyquinoline sulfate, 8-Hydroxyquinoline-5-sulfonic acid, Tetrakis (methylene-3.5-di-t-butyl-4-hydroxyhydrocinnamate) methane can be used.

In the present invention, (e) at least one secondary antioxidant selected from the group consisting of phosphorus compounds or sulfur compounds may be used alone or in combination of two or more thereof, and the secondary antioxidant may be used for the decomposition of hydroperoxide. Acts to prevent diffusion of alkoxy and hydroxy radicals. Examples of the phosphorus antioxidant include tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl) -4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecylphosphite, octyldiphenylphosphite, di (decyl) monophenylphosphite, monodecyldiphenylphosphite, mono (dinonyl Phenyl) bis (nonylphenyl) phosphite, di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-3 Tert-butylphenyl) pentaerythritoldiphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritoldiphosphite, tetra (tridecyl) isopropylidene-diphenyldiphosphite, tetra ( C12-16 mixed alkyl) -4,4'-n-butylidene bis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) 1,1,3-tris (2-methyl 4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylene diphosphite, 2,2'-methylenebis (2, 4-di-tert-butylphenyl) octyl) phosphite and the like.

Examples of the sulfur-based antioxidant include Methimazole (mesimiazole), dialkyldithiopropionate [dilaurylthiopropionate, dimyristylthiopropionate or distearylthiopropionate], β-al of polyol Chelmercaptopropionic acid esters (tetra (β-dodecylmercaptopropionate) of pentaerythritol).

The amount of the primary antioxidant and the secondary antioxidant in the organic conductive composition of the present invention is 5-10000 ppm (0.005-1 wt%) each independently. If less than 5 ppm oxidative stability does not exhibit the effect as desired, if more than 10000 ppm may lower the conductivity of the organic conductive composition.

The organic conductive composition of the present invention includes a solvent (f), and is included in the remaining amount except for the components of (a) to (e) described above, and is not particularly limited as long as it is a solvent usually used in the organic conductive composition. No water; Alcohols and diols, polyol methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, butanediol, neopentyl glycol, 1,3-pentanediol, 1,4-cyclohexanedimethanol, diethylene glycol, polyethylene glycol, polybutylene Prepared by esterification of one or more alcohols, diols or polyols selected from the group consisting of monomers or derivatives thereof consisting of glycol, dimethylolpropane and trimethylolpropane; Halogens such as chloroform, dichloromethane, tetrachloroethylene, trichloroethylene, dibromoethane and dibromopropane; Normal methylpyrrolidone, dimethyl sulfoxide; Triethylamine, tributylamine, trioctylamine; Or cresol etc. can be used individually or in mixture.

In addition, the organic conductive composition of the present invention may further include a surfactant and other additives that may be added to the organic conductive composition, in addition to the above components.

In another aspect, the present invention provides a method for forming a conductive thin film comprising the step of applying the organic conductive composition on a substrate, a conductive thin film formed by the method, and an IT device comprising the conductive thin film, the method of applying in the above Silver may be generally applied to the spray method, bar coating method, doctor blade method, roll coating method, dipping method and the like to apply the organic conductive composition on a substrate, and known steps that are generally applied to the formation of a conductive thin film Of course it can include. As a specific example, the organic conductive composition is coated on the substrate to a thickness of 5-20 μm using a spray method, a bar coating method, a doctor blade method, or a roll coating method, and soft baked for 180 seconds on a 110 ° C. hot plate. After forming a film layer of 100-300 nm and dried for 10 minutes in an oven at 120 ℃ to form a conductive thin film on the substrate.

When the conductive thin film is formed using the organic conductive composition of the present invention as described above, the conductive thin film can be formed with high reliability so as to have stable physical properties, and the formed thin film is also more conductive and durable than the thin film manufactured by using the conventional organic conductive composition. And it is useful in manufacturing a reliable IT device with excellent oxidation stability.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Comparative Example 1

PEDOT: PSS (poly 3,4-ethylenedioxythiophene: polystyrenesulfonate, weight ratio: 1: 2.5, Concentration of 1.6% by weight) 5% by weight of aqueous dispersion, 10% by weight of TEOS (tetraethyloxysilane), 1% by weight of acetic acid, 1000 ppm of surfactant, 30% by weight of Ethyleneglycol, and the remainder of IPA (isopropyl alcohol). ), An organic conductive composition was prepared.

Comparative Example 2

An organic conductive composition was prepared by adding 0.02% by weight of Methylgallate (methylgallate), which is a primary oxidative stabilizer, to Comparative Example 1.

Comparative Example 3

An organic conductive composition was prepared by adding 0.02% by weight of a second oxidation stabilizer, Methimazole (mesimiazole), to Comparative Example 1.

[Comparative Example 4]

An organic conductive composition was prepared by adding 0.06% by weight of Methylgallate (methylgallate) as a primary oxidation stabilizer to Comparative Example 1.

Example 1

In Comparative Example 1, an organic conductive composition was prepared by adding 0.02% by weight of a primary oxidative stabilizer, Methyl gallate (methyl gallate) and 0.02% by weight of a secondary oxidative stabilizer, Methimazole (mesimiazole).

The change in sheet resistance of the organic conductive compositions prepared in Example 1 and Comparative Examples 1-4 was measured (measured by Simco's ST-4) and is shown in FIG. 3. As shown in FIG. 3, Comparative Example 2-3 using antioxidant alone compared to Comparative Example 1 showed some antioxidant effect, even when the primary antioxidant content was increased three times (Comparative Example 4). Although the improvement effect is not large, when the primary antioxidant and the secondary antioxidant are used together as in Example 1, it can be seen that the effect is dramatically improved.

Claims

(a) conductive polymers;

(b) dopants;

(c) silane coupling agents;

(d) a primary antioxidant selected from the group consisting of phenol derivative compounds;

(e) a secondary antioxidant selected from the group consisting of phosphorus compounds or sulfur compounds; And

(f) residual solvent

Organic conductive composition comprising a.
The method of claim 1,

(a) 0.1 to 10 wt% of conductive polymer;

(b) 0.1 to 40 weight percent of the dopant;

(c) 3 to 90 weight percent of silane coupling agent;

(d) 5-10000 ppm of a primary antioxidant selected from the group consisting of phenol derivative compounds;

(e) 5-10000 ppm of a secondary antioxidant selected from the group consisting of phosphorus compounds or sulfur compounds; And

(f) residual solvent

Organic conductive composition comprising a.
The method of claim 1,

The (a) conductive polymer is an organic conductive composition, characterized in that it comprises a poly (3,4-ethylenedioxythiophene).
The method of claim 1,

The (b) dopant is an organic conductive composition, characterized in that it comprises 100 to 400 parts by weight based on 100 parts by weight of the conductive polymer of (a).
The method of claim 1,

The said silane coupling agent is tetraethyloxysilane, The organic conductive composition characterized by the above-mentioned.
The method of claim 1,

The organic antioxidant composition, wherein the primary antioxidant (d) is a phenol derivative compound is methyl gallate.
The method of claim 1,

(E) The secondary antioxidant is an organic conductive composition, characterized in that the mesimizol.
A method for forming a conductive thin film comprising applying the organic conductive composition of any one of claims 1 to 7 on a substrate.
A conductive thin film formed by the method of claim 8.
An IT device comprising the conductive thin film of claim 9.