KR20090087530A - Transparence conductive coating composition - Google Patents

Abstract

A polymer coating composition is provided to ensure high thin film permeability and high conductivity and to be useful as a coating agent for shielding electromagnetic waves and preventing static electricity of various display screens. A polymer coating composition comprises a conductive polymer, an oxidant, a dopant, solvent, and additive. The conductive polymer solution composition is thinned by a wet coating method and the thin film is hardened at 80 ‹C. The conductivity of the hardened thin film is 10^3 Ф/□ or less and transparency is 85% or more. The conductive polymer is obtained from at least monomer selected from group consisting of aniline and aniline derivative, pyrrole and pyrrole derivative, or 3,4-ethylenedioxythiophene and its derivative.

Description

Transparent conductive coating composition

The conductive polymer coating composition has been applied as a transparent electrode, an electromagnetic shielding material, a flexible display, an antistatic material by applying the electrical properties of the conductive polymer. The transparent electrode material can ultimately be used not only as a common electrode, but also as a patterned pixel electrode and even as a printable thin film transistor electrode.

Conventionally, as known in US Pat. No. 6,322,860 as a thin film having conductivity and transmittance, indium tin oxide (ITO) sputtered on a substrate has been studied a lot. However, the ITO thin film requires an expensive vacuum process, and it is difficult to use the substrate as a plastic when heat-treated at a high temperature in order to lower the resistance. Other methods of manufacturing thin films with conductivity and transparency include chemical vapor deposition using a variety of metal oxides and reactive evaporation deposition, but there are limitations that require expensive processing costs in order to coat metal oxides on substrates such as sputtering. Coating is difficult. On the other hand, in the case of thin film manufacturing using conductive polymers such as polyaniline, polypyrrol, polythiophene, and the like, dip coating, spray coating, spin coating, bar coating, etc. Various polymer coating methods can be used over a large area, thereby reducing the process cost and facilitating workability. There are potential applications of transparent electrodes, electromagnetic shielding materials, flexible displays, and antistatic materials by applying the electrical properties of these conductive polymers, but they have problems in commercialization due to insoluble in various solvents and difficult processing and poor thermal stability. Meanwhile, as described in US Pat. Nos. 5,035,926 and 5,391,472, polyethylene dioxythiophene (Poly (3,4-ethylenedioxythiophene): PEDOT) is introduced, and the material has excellent electrical conductivity, transparency and processability. Many possibilities are recognized. In recent years, Ormecon of Germany has been commercialized by producing a conductive nanoparticles doped with polyaniline.

In general, conductive polymer conductivity increases in proportion to the thickness of the coating film, but when used in a display, it is difficult to use it with low permeability as the thickness of the coating film increases, and in case of thin coating, it does not satisfy the requirement of high surface resistance. There is a disadvantage. In the case of using a commercially available conductive polymer, it is difficult to obtain a sheet resistance of 10 ³ Ω / sq or less. In view of this, there is a need for a conductive polymer solution that exhibits excellent transmittance and low sheet resistance of 10 ³ Ω / sq or less.

The present invention relates to a polymer coating composition having a permeability and conductivity and a method of manufacturing the same. More specifically, by mixing a conductive polymer compound and an additive well dispersed in a solvent to lower the permeability of the conventional conductive polymer solution to more than 85%, the sheet resistance to 10 ³ Ω / sq or less.

The film manufacturing method, which required conductivity and transparency through a transparent conductive coating or printing process using a metal oxide that has been used in the past, requires a high process cost, and thus the present invention has a large area of a flexible conductive transparent film. The use of a simple wet manufacturing process is expected to increase economics.

Hereinafter, the present invention will be described in detail.

According to the present invention, a thin film obtained by curing a conductive polymer solution composition consisting of a conductive polymer, an oxidizing agent, a dopant, a solvent, and an additive by a wet coating method and then curing at 80 degrees has a sheet resistance of 10 ³ Ω / □ or less, and a transmittance. It is characterized in that the polymer coating composition having a transparency and conductivity of at least 85%.

The conductive polymer used in the present invention is a polymer compound having transparency and conductivity obtained from aniline and at least one monomer selected from the group consisting of aniline derivatives, pyrrole, pyrrole derivatives, or thiophene and derivatives thereof, and polyaniline and polypyrrole , Polythiophene, polydioxyethylenethiophene.

As the oxidizing agent used in the present invention, at least one compound selected from the group consisting of iron chloride, ferric toluenesulfonate, ferricdodecylbenzene sulfonate, and ferric anthraquinonesulfonate has a monomer and molar ratio of 1: 1 to 1: Can be used in the range of 10.

As the dopant of the conductive polymers used in the present invention, organic compounds substituted with sulfonic acid groups are preferable, and examples thereof include para-toluene sulfonic acid, dodecyl benzene sulfonic acid, anthraquinone sulfonic acid, 4-hydroxy benzene sulfonic acid, methyl sulfonic acid and nitrobenzene. At least one compound selected from the group consisting of sulfonic acid, polystyrenesulfonate, poly (styrene-co-styrenesulfonic acid), poly (2-acrylamido-2-methyl-1-propanesulfonic acid-co-acrylonitrile) The monomer and molar ratio of the conductive polymer may be used in the range of 1: 1 to 1:10.

The solvent in the present invention is water or alcohol having 1 to 6 carbon atoms or formamide, such as methanol, ethanol, propanol, isopropanol, normal butanol, normal pentanol, normal hexanol, N-methylformamide, N, N-dimethylform At least one solvent or a mixed solvent selected from the group consisting of amide solvents such as amides or sulfoxide solvents such as methyl sulfoxide and dimethyl sulfoxide may be used in a range of 1:50 to 1: 500 based on the conductive polymer monomer (weight ratio). Can be used in a range.

Additives in the present invention are imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, dimethylacetamide, 2-undecylimidazole, pyridine, pyrimidine At least one selected from the group consisting of, etc. can be used in the polymer monomer reference molar ratio 1: 0.1 ~ 1:10.

In addition, the conductive polymer composition solution is characterized in that the surfactant is further mixed in an amount of 0.01 to 1 parts by weight based on the total solution weight during the preparation step. In this case, as the surfactant, one or more compounds of polyethylene oxide, polyvinyl alcohol, sodium dodecylbenzenesulfonate, polyvinylpyrrole, and triton exback (X-100) may be used.

In addition, the method for preparing a conductive polymer solution includes mixing and stirring an oxidizing agent and a dopant in a solvent in a ratio of 10 to 90% by weight, adding an additive in an amount of 0.001 to 1% by weight of the total content, and conducting polymer monomer in the mixed solution. Adding in an amount of 0.001 to 1% by weight, adding the surfactant in an amount of 0.001 to 1% by weight of the total content.

The method for coating the conductive polymer solution mixture obtained in the present invention is a well-known process such as dip coating, spray coating, spin coating, bar coating to form a thin film having a thickness of 0.01 ~ 5 micrometers on a transparent substrate, 100 After the curing process in the range of 1 to 30 minutes at a temperature of less than the degree, the thin film is washed with distilled water to remove the remaining oxidant and dopant to obtain a final thin film.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited thereto.

Example 1. Preparation and coating of PEDOT-based conductive polymer solution

1.26 mmol (0.854 g) of ferrictoluenesulfonate was added to a round 100 ml reactor, n-butanol 0.023 mol (1.725 g) and 1.2 mmol (0.086 g) of imidazole were stirred for 30 minutes, and then 3.4-ethylenedioxe, a conductive polymer monomer, was added. 0.422 mmol (0.06 g) of citofene and 0.15 g (5 wt%) of surfactant Triton X-100 were added, and the mixed solution was coated on a polyethylene terephthalate substrate at 500 rpm using a spin coater and dried at 80 ° C. After curing and washing with distilled water to obtain a transparent coating thin film.

Example 2. Preparation of PEDOT-Based Conductive Polymer Solution

1.24 mmol (0.84 g) of ferrictoluenesulfonate was added to a round 100 ml reactor, 0.023 mol (1.722 g) of n-butanol and 1.24 mmol (0.102 g) of 2-methyl-imidazole were stirred for 30 minutes, and then a conductive polymer monomer was added. 0.415 mmol (0.059 g) of 3.4-ethylenedioxythiophene and 0.14 g (5 wt%) of surfactant Triton X-100 were added and the mixed solution was coated on a polyethylene terephthalate substrate at 500 rpm using a spin coater. After drying and curing at 80 degrees and washing with distilled water, a transparent coating thin film is obtained.

Example 3. Preparation of PEDOT-Based Conductive Polymer Solution

1.21 mmol (0.825 g) of ferrictoluenesulfonate was added to a round 100 ml reactor, 0.023 mol (1.717 g) of n-butanol and 1.21 mmol (0.117 g) of 2-ethyl-imidazole were stirred for 30 minutes, and then a conductive polymer monomer was added. 0.408 mmol (0.058 g) of 3.4-ethylenedioxythiophene and 0.14 g (5 wt%) of the surfactant Triton X-100 were added, and the mixed solution was coated on a polyethylene terephthalate substrate at 500 rpm using a spin coater. After drying and curing in the figure and washed with distilled water to obtain a transparent coating thin film.

Example 4. Preparation of PEDOT-Based Conductive Polymer Solution

1.19 mmol (0.811 g) of ferrictoluenesulfonate was added to a round 100 ml reactor, 0.023 mol (1.714 g) of n-butanol and 1.19 mmol (0.132 g) of 2-ethyl-4-methyl-imidazole were added thereto, followed by stirring for 30 minutes. 0.4 mmol (0.057 g) of the conductive polymer monomer (0.457 g) and 0.14 g (5 wt%) of the surfactant Triton X-100 were added and the mixed solution was spun at 500 rpm on a polyethylene terephthalate substrate using a spin coater. After coating, drying and curing at 80 degrees, washed with distilled water to obtain a transparent coating thin film.

Example 5. Preparation of PEDOT-Based Conductive Polymer Solution

1.05 mmol (0.715 g) of ferrictoluenesulfonate was added to a round 100 mL reactor, 0.023 mol (1.714 g) of n-butanol and 1.05 mmol (0.235 g) of 2-undecyl-imidazole were added and stirred for 30 minutes. 0.35 mmol (0.05 g) of phosphorus 3.4-ethylenedioxythiophene and 0.14 g (5 wt%) of surfactant Triton X-100 were added, and the mixed solution was coated on a polyethylene terephthalate substrate at 500 rpm using a spin coater. After drying and curing at 80 degrees and washing with distilled water, a transparent coating thin film is obtained.

Example 6. Preparation of PEDOT-Based Conductive Polymer Solution

1.24 mmol (0.843 g) of ferrictoluenesulfonate was added to a round 100 ml reactor, 0.02 mol (1.5 g) of n-butanol and 1.23 mmol (0.098 g) of pyridine were stirred for 30 minutes, and 3.4-ethylenedioxyti, a conductive polymer monomer, was stirred. 0.415 mmol (0.059 g) of fen and 0.12 g (5 wt%) of surfactant Triton X-100 were added, and the mixed solution was coated on a polyethylene terephthalate substrate at 500 rpm using a spin coater, dried and cured at 80 ° C. After washing with distilled water to obtain a transparent coating thin film.

Example 7. Preparation of PEDOT-based Conductive Polymer Solution

1.24 mmol (0.843 g) of ferrictoluenesulfonate was added to a round 100 ml reactor, n-butanol 0.02 mol (1.5 g) and pyrimidine 1.22 mmol (0.098 g) were stirred for 30 minutes, and then 3.4-ethylenedioxe, a conductive polymer monomer, was added. 0.415 mmol (0.059 g) of citofene and 0.12 g (5% by weight) of surfactant Triton X-100 were added, and the mixed solution was coated on a polyethylene terephthalate substrate at 500 rpm using a spin coater and dried at 80 ° C. After curing and washing with distilled water to obtain a transparent coating thin film.

Example 8. Preparation of PEDOT-Based Conductive Polymer Solution

1.23 mmol (0.83 g) of ferrictoluenesulfonate was added to a round 100 ml reactor, 0.02 mol (1.5 g) of n-butanol and 1.23 mmol (0.107 g) of dimethylacetamide were stirred for 30 minutes, followed by 3.4- of conductive polymer monomer. 0.411 mmol (0.058 g) of ethylenedioxythiophene and 0.13 g (5 wt%) of surfactant Triton X-100 were added, and the mixed solution was coated on a polyethylene terephthalate substrate at 500 rpm using a spin coater at 80 ° C. After drying and curing and washing with distilled water, a transparent coating thin film is obtained.

Example 9. Preparation of PEDOT-Based Conductive Polymer Solution

The same process as in Example 1 was carried out except that the surfactant was polyethylene oxide.

Example 10 Preparation of PEDOT-Based Conductive Polymer Solution

The same process as in Example 1 was carried out except for using polyvinyl alcohol as the surfactant.

Example 11. Preparation of PEDOT-Based Conductive Polymer Solution

The same process as in Example 1 was conducted except that the surfactant was sodium dodecylbenzenesulfonate.

Example 12 Preparation of PEDOT-Based Conductive Polymer Solution

The same process as in Example 1 was carried out except that the surfactant was polyvinylpyrrole.

Comparative Example 1. PEDOT Coating

The PEDOT-based conductive polymer was coated without using an additive, and the experiment was conducted under the same conditions as in Example 1.

Comparative Example 2. PEDOT Coating

PEDOT-based conductive polymers were coated without using a surfactant, and the experiment was conducted under the same conditions as in Example 1.

Comparative Example 2. PEDOT Coating

The PEDOT-based conductive polymer was coated without using an additive and a surfactant, and the experiment was conducted under the same conditions as in Example 1.

Basic properties Surface Resistance ⁽¹⁾ (Ω / sq) Permeability ⁽²⁾ (%) Example 1 668 91 Example 2 402 85 Example 3 337 87 Example 4 283 87 Example 5 1412 81 Example 6 612 90 Example 7 548 90 Example 8 897 89 Example 9 780 88 Example 10 976 87 Example 11 1203 84 Example 12 1100 80 Comparative Example 1 1186 68 Comparative Example 2 1020 67 Comparative Example 3 3184 44

⁽¹⁾ Surface resistance: (Changmin 4-point probe), ⁽²⁾ Permeability: UV-Vis spectrometer (UV-VIS, US / 8453, Hewlett packard) using 550 nm transmittance for PET film Relative permeability

As can be seen from Table 1, when the additive was added to the conductive polymer solution (Example), most of the surface resistance was 10 ³ Ω / □ or less, the transmittance could satisfy 85% or more.

Claims (7)

The present invention is 10 ³ Ω / □ or less conductive polymer, an oxidant and dopant, and the solvent, after the conductive polymer solution composition consisting of additives thinned by a wet coating method, the conductivity of the film obtained by curing at 80 °, the transparency 85 Polymer coating compositions having a transmittance and conductivity of at least% The conductive polymer of claim 1 is a polymer compound having transparency and conductivity obtained from aniline and at least one monomer selected from the group consisting of aniline derivatives, pyrrole, pyrrole derivatives, or 3,4-ethylenedioxythiophene and derivatives thereof. , Polyaniline, polypyrrole, conductive polymer compound characterized by being polydioxyethylene thiophene The at least one compound selected from the group consisting of iron chloride, ferric toluenesulfonate, ferricdodecylbenzene sulfonate, and ferric anthraquinonesulfonate as claimed in claim 1 is 1: 1 to 1:10. Conductive polymer, characterized in that the range of The dopants of the conductive polymers according to claim 1 are para toluene sulfonic acid, dodecyl benzene sulfonic acid, anthraquinone sulfonic acid, 4-hydroxy benzene sulfonic acid, methyl sulfonic acid, nitrobenzene sulfonic acid, polystyrene sulfonic acid, poly (styrene-co-styrene sulfonic acid ), At least one compound selected from the group consisting of poly (2-acrylamido-2-methyl-1-propanesulfonic acid-co-acrylonitrile) has a monomer and molar ratio of 1: 1 to 1:10 Conductive polymer coating composition, characterized in that used in The solvent in claim 1 is water or alcohol having 1 to 6 carbon atoms or formamide, such as methanol, ethanol, propanol, isopropanol, normal butanol, normal pentanol, normal hexanol, N-methylformamide, N, N-dimethylform At least one solvent or a mixed solvent selected from the group consisting of amide solvents such as amides or sulfoxide solvents such as methyl sulfoxide and dimethyl sulfoxide may be used in a range of 1:50 to 1: 500 based on the conductive polymer monomer (weight ratio). Conductive polymer coating composition, characterized in that used in the range The additive in claim 1 is an imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, dimethylacetamide, 2-undecylimidazole, pyridine, pyrimidine Conductive polymer coating composition, characterized in that it is used in one or more selected from the group consisting of polymer monomers in a molar ratio of 1: 0.1 to 1:10. The surfactant of claim 1, wherein the surfactant is at least one compound of polyethylene oxide, polyvinyl alcohol, sodium dodecylbenzenesulfonate, polyvinylpyrrole, and triton exback (X-100), which is further contained in an amount of 0.01 to 1 parts by weight based on the total content. Conductive coating composition characterized by mixing