KR102025194B1

KR102025194B1 - A high molecule copolymer-complex with a excellent water-resisting, chemical-resisting, and weather-resisting property, and the fabrciation method of the same.

Info

Publication number: KR102025194B1
Application number: KR1020130009618A
Authority: KR
Inventors: 김중현; 이선종; 이승환; 박홍관; 김인영; 조원석; 유도혁; 이정준
Original assignee: 주식회사 한국엔티켐
Priority date: 2013-01-29
Filing date: 2013-01-29
Publication date: 2019-09-25
Also published as: KR20140096707A

Abstract

The present invention has been made in order to remove a hydrophilic group of a conductive emulsifier having a hydrophilic group, and to form a hydrophobic group through reaction with another alcoholic polymer. In addition, by inducing a chemical bond by copolymerization without physical bonding by a non-conductive binder, it has excellent water resistance and maintains the intrinsic electrical properties of the conductive emulsifier or conductive material. Therefore, a dehydration condensation reaction between the conductive emulsifier and the alcoholic polymer is produced to produce a graft copolymer having an electrical conductivity that can be applied as a conductive material, and the film is impregnated with a polar solvent or left in the air for a long time. The present invention provides a graft copolymer between a conductive emulsifier and an alcoholic polymer having a property of intrinsic physical properties such as electrical conductivity and a method of manufacturing the same.

Description

A composite comprising a polymer copolymer having excellent water resistance, chemical resistance, and weather resistance, and a method for preparing the same. (A HIGH MOLECULE COPOLYMER-COMPLEX WITH A EXCELLENT WATER-RESISTING, CHEMICAL-RESISTING, AND WEATHER-RESISTING PROPERTY, AND THE FABRCIATION METHOD OF THE SAME.}

The present invention relates to a conductor having water resistance, chemical resistance, and weather resistance to moisture or the surrounding environment, wherein an alcoholic polymer is added to the conductive material and the polymer of the conductive emulsifier, mixed with the same, and then heated to induce a dehydration condensation reaction. The present invention relates to a technology capable of producing a composite including a graft copolymer having water resistance, chemical resistance, and weather resistance.

Conductive emulsifiers have unique properties that allow electricity to pass through the inherent properties of the emulsifier, which dissolves or disperses components that are insoluble in solvents, and can maintain conductivity while dispersing conductive polymers or nanowires. It has been active.

Particularly in the fields of electricity and electronics, it is applied to electrolytic capacitors, electric double layer capacitors, switching elements, nonlinear elements, field effect transistors, optical recording materials, display elements, and anisotropic conductor sensors, and continues to be applied to new fields. Research is ongoing.

However, despite the advantages of the conductive emulsifiers, most of the conductive polymers or nanowires to which the conductive emulsifiers are to be dispersed are sensitive to moisture or polar solvents in the air, and most conductive emulsifiers also contain hydrophilic groups. When exposed to the atmosphere, the original intrinsic properties are lost, and the reliability as a unit functional film of an electric component or an integrated circuit is very weak. As such, the conductive emulsifier is vulnerable to moisture and polar solvents, and thus, it is difficult to safely maintain the target material to be dispersed in the air, and thus is limited to applications such as electric and electronic components requiring long-term reliability.

In order to solve this problem, there is a method of adding an additive such as an additional binder or an adhesive to the conductive emulsifier, but this can generate physical bonds between the conductive materials to protect it from moisture, but most of the additives such as binders use a certain amount or more as a nonconductor. In this case, there is a problem of inhibiting the inherent electrical properties of the inherently conductive emulsifier or dispersed conductive material. Therefore, there is a need for the development of a conductive emulsifier that can maintain the intrinsic electrical properties while having water resistance or chemical resistance. It is becoming.

Patent No. 10-0725151 relates to a method for preparing conductive polyaniline and mixtures thereof for use in electrode materials for secondary batteries, various display device materials, electromagnetic shielding antistatic coatings, and the like, and includes aniline, polymer acids, emulsifiers, water, and nonpolar substances. Disclosed is a polyaniline production method characterized in that a polyaniline polymer is prepared by subjecting an emulsion composed of an organic solvent to polymerization in the presence of a polymerization initiator, and a polyaniline mixed composition in which the polyaniline is mixed with a polymer binder in the presence of a compatibilizer. Compared to the conventional method, it is possible to provide polyaniline and its mixed composition, which are easier to manufacture and purify and exhibit excellent electrical and physical properties.

The present invention has been made in order to remove a hydrophilic group of a conductive emulsifier having a hydrophilic group, and to form a hydrophobic group through reaction with another alcoholic polymer. In addition, by inducing chemical bonding by copolymerization without physical bonding by a non-conductive binder, it is possible to maintain the inherent electrical properties of the conductive emulsifier or conductive material while having excellent water resistance. Accordingly, the present invention causes a dehydration and condensation reaction between the conductive emulsifier and the alcoholic polymer to produce a composite including a graft copolymer having an electrical conductivity capable of being applied as a conductive material, and impregnating it with a polar solvent. The present invention also provides a graft copolymer between a conductive emulsifier and an alcoholic polymer, a composite made of a conductive material, and a method of manufacturing the same, having a property of intrinsic physical properties such as electrical conductivity even after being left in the air for a long time. Shall be.

In order to solve the above problems, the present invention is to first convert the hydrophilic group of the conductive emulsifier to a hydrophobic group in order to prevent the reaction of the conductive emulsifier with water and the polar solvent. More specifically, a graft copolymerization reaction in which a hydrophilic group of a conductive emulsifier and a hydrophilic group of an alcoholic polymer are removed through a dehydration condensation reaction by mixing a conductive material, a polymer of a conductive emulsifier and an alcoholic polymer, and heat-treating them at a range of temperatures. copolymerization). The graft copolymer (graft copolymer) between the conductive emulsifier and the alcoholic polymer produced by the copolymerization reaction, the composite consisting of a conductive material does not have a hydrophilic group, do not react with moisture or a polar solvent, it has excellent water resistance and chemical resistance, Therefore, even when it is left in the air, excellent weather resistance does not change in physical properties.

Secondly, in particular, by not using a binder added for the physical bonding between the conductive emulsifier and the material to be dispersed, it is possible to prevent the decrease in the electrical conductivity due to the use of the binder as a nonconductor. Therefore, the present invention can be applied as an emulsifier having water resistance, chemical resistance, and weather resistance while maintaining the electrical properties of the conductive material. In addition, by maintaining such a relatively high electrical conductivity, it has an antistatic property, and application as an antistatic functional film is also possible.
The graft copolymer between the conductive emulsifier and the alcoholic polymer according to the present invention, a composite made of a conductive material is a conductive emulsifier having a hydrophilic group and a conductive material made of any one or a combination of conductive polymers, carbon materials or metal materials Has a physically bonded polymer and two end groups, the first end group is a hydrophilic group, and the second end group is formed by dehydrating a hydrophobic alcoholic polymer, wherein the conductive material is (i) a conductive polymer. Poly (3,4-ethylenedioxythiophene), Polythiophene, Polypyrrole, Polyaniline, Thiophene derivatives Poly (3-methyl thiophene), Poly (3-hexyl thiophene), Poly octylthiophene, Polyfullerene, Polyacetylene, Polyfuran, Polyphenylene sulfide, poly (phenylenevinylene ), poly (thienylene-vinylene), Poly sulfur nitride, (ii) Carbon nanotubes, Graphene, Ac tivate carbon, (iii) a metal material consisting of any one or a combination of two or more of gold pariticle, silver nanowire, silver nanoparticle, the conductive emulsifier is 4-toluenesulfonic acid (p-Toluenesulfonic acid), 1-naphthalene sulfonic acid Any one or more of (1-Naphthalenesulfonic acid), dodecyl benezene sulfonic acid, poly (vinyl sulfonic acid), polystyrene sulfonic acid (poly (4-styrene sulfonic acid)) Combination material or any one or two or more combinations selected from poly (acrylic acid), polymethacrylic acid (poly (methacrylic acid)), the alcoholic polymer is the first terminal group And a second terminal group is a polyethylene-based reactant which is an alkyl group.

First, a graft copolymer is finally formed by mixing a conductive material, a polymer of a conductive emulsifier, and an alcoholic polymer and heat-treating it to remove the hydrophilic group of the conductive emulsifier and the hydrophilic group of an alcoholic polymer through a dehydration condensation reaction. The composite including) may have excellent water resistance by preventing the reaction with moisture in the air.

Second, the graft copolymer between the conductive emulsifier and the alcoholic polymer has only a hydrophobic group, and thus has strong chemical resistance to polar solvents such as methanol and ethanol.

Third, the graft copolymer between the conductive emulsifier and the alcoholic polymer does not react with moisture in the air, and when used in the air, the graft copolymer has weather resistance without change in physical properties with time.

Fourth, physical bonding is generally used to remove the binder used to improve weather resistance, and instead, a small amount of alcoholic polymer is added to induce chemical bonding by copolymerization, thereby reducing the electrical conductivity caused by the non-conductive binder. You can stop it. That is, the intrinsic electrical properties of the conductive material can be maintained.

1 relates to a graft copolymer between a conductive emulsifier and an alcoholic polymer, a method of manufacturing a composite made of a conductive material.
Figure 2 relates to a graft copolymer (graft copolymer) between the conductive emulsifier and the alcoholic polymer, a method for producing a film comprising a composite consisting of a conductive polymer.
Figure 3 relates to a method for producing a film comprising a composite made of a graft copolymer, a carbon material between the conductive emulsifier and the alcoholic polymer.
FIG. 4 relates to a graft copolymer between a conductive emulsifier and an alcoholic polymer, and a method of manufacturing a film including a composite made of a metal material.

1 is a graft copolymer between a conductive emulsifier and an alcoholic polymer, and a method for manufacturing a composite made of a conductive material. First, a conductive material including any one or a combination of two or more of a conductive polymer, a carbon material, or a metal material A conductive solution comprising a polymer having a physically bonded conductive emulsifier having a hydrophilic group and a hydrophilic group is prepared, and an alcoholic polymer having two end groups, a first end group is a hydrophilic group, and a second end group is a hydrophobic group is prepared. The alcoholic polymer is added to the conductive solution and dissolved in the prepared conductive solution to prepare a mixed solution. The hydrophilic group of the conductive emulsifier and the first terminal group of the alcoholic polymer are dehydrated and condensed through a heat treatment process to form a graft copolymer having only a hydrophobic group.

In the conductive solution manufacturing step, the conductive material is a poly (3,4-ethylenedioxythiophene), a polythiophene, a polypyrrole, a polyaniline, a carbonaceous carbon nanotube, a graphene, a silver nanowire of a metallic material, a conductive polymer having a molecular weight of 50 to 100,000 It is preferable to select any one or a combination of two or more materials, but is not limited thereto.

The conductive polymer is preferably selected to have a structural formula of any one of formulas (1), (2), (3) and (4). .

In the case where the conductive material is the conductive polymer, the monomer, the conductive emulsifier, the initiator and the deionized water of the conductive polymer are stirred at room temperature to form a conductive polymer and a polymer of the conductive emulsifier and the conductive emulsifier remaining. Solutions can be prepared.

The prepared polymer of the conductive polymer and the conductive emulsifier may be formed in a form in which the conductive emulsifier surrounds the conductive polymer.

The initiator is sodium persulfate (SPS) as the first oxidant, ammonium persulfate (APS), 30% by weight aqueous hydrogen peroxide (Hydrogen peroxide), iron (III) chloride, Iron (2) as the second oxidant. III) may be selected to include at least one of sulfate and Iron (III) tosylate, but is not limited thereto.

In addition, when the conductive solution is prepared, when the conductive material is a carbon material or a metal material, the conductive material may be prepared by mixing the carbon material or the metal material, the conductive emulsifier and deionized water at room temperature and stabilizing in an aqueous phase.

The mixed solution is preferably prepared by stirring and dissolving at a temperature of 10 ° C or more and 150 ° C or less for 5 minutes or more and 120 minutes or less. In particular, the heat treatment process for the dehydration condensation reaction is preferably carried out at a temperature of 50 ° C or more and 300 ° C or less, for a time of 5 minutes to 60 minutes.

The conductive emulsifier has any one of sulfonic acid, paratoluenesulfonic acid and carboxylic acid as a functional group as an organic acid, and it is preferable to select one having the structural formula of any one of the following Chemical Formulas 5 and 6.

Formula 5 is 4-toluene sulfonic acid (p-Toluenesulfonic acid), 1-naphthalene sulfonic acid (1-Naphthalenesulfonic acid), dodecyl benezene sulfonic acid (Dodecyl benezene sulfonic acid), polyvinyl sulfonic acid (poly (vinyl sulfonic acid) )] And polystyrene sulfonic acid (poly (4-styrene sulfonic acid)) of any one or a combination of two or more.

In addition, Formula 6 is a material consisting of any one or a combination of two or more selected from poly (acrylic acid) and polymethacrylic acid (poly (methacrylic acid)).

delete

The alcoholic polymer includes a graft copolymer and a conductive material between the conductive emulsifier and the alcoholic polymer, wherein the first terminal is a hydroxy group and the second terminal is an alkyl group. Method for preparing a composite.

The alcoholic polymer is preferably selected to have a structural formula of the following chemical formula 7.

R4 of Formula 7 includes an ether, Formula 7 is a polymer material having a molecular weight of 100 to 1,000,000,

R5 has 1 or more and 100 or less carbon atoms, and formula (7) is polyethylene glycol methyl ether [poly (ethylene glycol) methyl ether], polypropylene propylene glycol acrylate [poly (propylene glycol) acrylate], polypropylene glycol methacrylate [Poly] (propylene) methacrylate], polypropylene glycol monobutyl ether [Poly (propylene glycol) monobutyl ether], polypropylene glycol monooctyl ether [Poly (propylene glycol) monooctyl ether] A material consisting of any one or a combination of two or more.

In addition, the alcoholic polymer is to convert the hydrophilic group of the conductive polymer emulsifier to a hydrophobic group by forming a chemical bond by the hydrophilic group of the polymer emulsifier by the dehydration polymerization polymerization, for this purpose, the first end group of the alcoholic polymer is a hydrophilic group, The two terminal groups must be alcoholic polymers consisting of hydrophobic groups.

If the content of alcoholic polymer is less than 10% by weight, the conversion to dehydration condensation polymerization is low. Excess hydrophilic groups which are not converted into hydrophobic groups exist in the reaction product, resulting in lower water resistance. Although the conversion to the reaction is high, it is not preferable because the intrinsic properties of the conductive emulsifier can be changed by the influence of the remaining alcoholic polymer. In addition, considering the mass production, there is a disadvantage that is not economical due to the increase in material costs. Therefore, the amount of alcoholic polymer is used based on the weight of the conductive material and the conductive emulsifier. Preference is given to using 10 to 50% by weight.

Specifically describing the copolymerization reaction by heat treatment, the dehydration condensation reaction between the hydrophilic group of the conductive emulsifier and the hydrophilic group of the alcoholic polymer during the heat treatment process may be described by the formulas (8) and (9) below. However, this is only a representative example for explaining the present invention, and it is clear that both of the conductive emulsifier and the alcoholic polymer having a hydrophilic group are capable of such a dehydration condensation reaction.

Formula 8 is a case where the conductive emulsifier is a polymer containing sulfonic acid, has a hydrophilic -OH group, alcoholic polymer has a hydrophilic group only at one end. When the mixture is mixed and heat-treated, when the hydrophilic group of the conductive emulsifier reacts with the hydrophilic group of the alcoholic polymer, a graft copolymer having only H20 molecules and hydrophobic groups is formed through a dehydration condensation reaction.

Formula 9 is a case where the conductive emulsifier is a polymer containing a carboxylic acid, has a hydrophilic -OH group, alcoholic polymer has a hydrophilic group only at one end. When the mixture is mixed and heat treated, as in Formula 8, when the hydrophilic group of the conductive emulsifier reacts with the hydrophilic group of the alcoholic polymer, a graft copolymer having only H ₂ 0 molecules and a hydrophobic group is formed through a dehydration condensation reaction.

R1 of Chemical Formulas 8 and 9 is a conductive material of any of poly (3,4-ethylenedioxythiophene), polythiophene, polypyrrole, polyaniline, carbon nanotube, graphene, and silver nanowire, which are conductive polymers having a molecular weight of 50 to 100,000. It may be selected from materials consisting of one or two or more combinations.

Of course, R1, R2, R3, R4, and R5 are polymers of the same kind as described in the conductive emulsifier and the alcoholic polymer.

In addition, the composite finally obtained by the manufacturing process as described above has only a hydrophobic group at the end, the graft copolymer between the conductive emulsifier and the alcoholic polymer other than water in the reaction products of Formulas 8 and 9 (graft copolymer) ), A composite made of a conductive material. It is also evident that, depending on the choice of conductive material and conductive emulsifier, various composites can be obtained as a result.

A graft copolymer between the conductive emulsifier and the alcoholic polymer, a film including a composite made of a conductive material may be prepared. As shown in FIGS. 2, 3 and 4, a substrate is prepared, and a polymer in which a conductive material made of any one or two or more of a conductive polymer, a carbon material, or a metal material and a conductive emulsifier having a hydrophilic group is physically bound to the polymer. To prepare a conductive solution comprising a, and having two end groups, the first end group is a hydrophilic group, the second end group is prepared an alcoholic polymer is a hydrophobic group. The alcoholic polymer is added to the prepared conductive solution and dissolved to prepare a mixed solution. The prepared mixed solution is coated on the substrate and coated, and the coated mixed solution is heat-treated to dehydrate and condense the hydrophilic group of the conductive emulsifier and the first terminal group of the alcoholic polymer to obtain a graft copolymer having only a hydrophobic group ( It can form a film including a composite consisting of a graft copolymer) and a conductive material.

Coating the mixed solution onto the substrate is a wet coating including at least one of spin coating, spray coating, roll to roll, or bar coating. The conductive material may be made of poly (3,4-ethylenedioxythiophene), a polythiophene, a polypyrrole, a polyaniline, a carbon material carbon nanotube, graphene, and a metal material as described above. It may be made of any one or a combination of two or more of the silver nanowires.

In addition, the conductive emulsifier may be represented in the same manner as in Formula 5, 6, as described above, alcoholic polymer may also be represented in the same manner as in Formula 7.

When the hydrophilic group of the conductive emulsifier reacts with the hydrophilic group of the alcoholic polymer, the copolymerization reaction on the film forms a complex composed of a graft copolymer having only H ₂ 0 molecules and a hydrophobic group and a conductive material through a dehydration condensation reaction. This may be the same as represented by the formula (8), 9 and the same as when not in the film form described above.

This is a data that summarizes the results of experiments on water resistance, weather resistance, and chemical resistance according to the immersion time of a film made only of a polymer of a conductive material and a conductive emulsifier.

Water resistance, weather resistance, and weather resistance according to the immersion time of the film prepared by using a composite made of a conductive material and a graft copolymer between the conductive emulsifier and the alcoholic polymer, and a conductive material The data summarizes the results of experiments on chemical properties.

In particular, in order to see only the conductive properties of the conductive emulsifier, a glass substrate, which is an insulating substrate, was selected.

1) Water resistance when the conductive material is a conductive polymer

Water temperature (℃) conductivity
Polymer Conductive Polymer / Conductive Emulsifier: Immersion Time (hour) 0 hours 3 hours 6 hours 12 hours 24 hours 36 hours 48 hours 10 PT 10 ^7.3 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ PEDOT 10 ^4.0 Ω / □ > 10 ¹³ Ω / □ 10 ^8.5 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ PPY 10 ^4.5 Ω / □ > 10 ¹³ Ω / □ 10 ^9.5 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ PAN 10 ^7,1 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □

Water temperature
(℃) conductivity
Polymer Conductive Polymer / Conductive Emulsifier-g-Alcohol Polymer: Immersion Time (hour) 0 hours 3 hours 6 hours 12 hours 24 hours 36 hours 48 hours 10 PT 10 ^7.3 Ω / □ 10 ^7.4 Ω / □ 10 ^7.5 Ω / □ 10 ^7.5 Ω / □ 10 ^7.6 Ω / □ 10 ^7.6 Ω / □ 10 ^7.6 Ω / □ PEDOT 10 ^4.0 Ω / □ 10 ^4.1 Ω / □ 10 ^4.1 Ω / □ 10 ^4.1 Ω / □ 10 ^4.2 Ω / □ 10 ^4.2 Ω / □ 10 ^4.2 Ω / □ PPY 10 ^4.5 Ω / □ 10 ^4.5 Ω / □ 10 ^4.5 Ω / □ 10 ^4.5 Ω / □ 10 ^4.6 Ω / □ 10 ^4.6 Ω / □ 10 ^4.7 Ω / □ PANI 10 ^7,1 Ω / □ 10 ^7.2 Ω / □ 10 ^7.2 Ω / □ 10 ^7.2 Ω / □ 10 ^7.2 Ω / □ 10 ^7.3 Ω / □ 10 ^7.4 Ω / □ 30 PT 10 ^7.3 Ω / □ 10 ^7.5 Ω / □ 10 ^7.6 Ω / □ 10 ^7.6 Ω / □ 10 ^7.7 Ω / □ 10 ^7.7 Ω / □ 10 ^7.7 Ω / □ PEDOT 10 ^4.0 Ω / □ 10 ^4.1 Ω / □ 10 ^4.2 Ω / □ 10 ^4.2 Ω / □ 10 ^4.3 Ω / □ 10 ^4.3 Ω / □ 10 ^4.3 Ω / □ PPY 10 ^4.5 Ω / □ 10 ^4.6 Ω / □ 10 ^4.6 Ω / □ 10 ^4.6 Ω / □ 10 ^4.7 Ω / □ 10 ^4.7 Ω / □ 10 ^4.7 Ω / □ PANI 10 ^7,1 Ω / □ 10 ^7.3 Ω / □ 10 ^7.3 Ω / □ 10 ^7.3 Ω / □ 10 ^7.3 Ω / □ 10 ^7.3 Ω / □ 10 ^7.3 Ω / □ 50 PT 10 ^7.3 Ω / □ 10 ^7.5 Ω / □ 10 ^7.7 Ω / □ 10 ^7.7 Ω / □ 10 ^7.8 Ω / □ 10 ^7.8 Ω / □ 10 ^7.8 Ω / □ PEDOT 10 ^4.0 Ω / □ 10 ^4.2 Ω / □ 10 ^4.3 Ω / □ 10 ^4.4 Ω / □ 10 ^4.4 Ω / □ 10 ^4.5 Ω / □ 10 ^4.5 Ω / □ PPY 10 ^4.5 Ω / □ 10 ^4.8 Ω / □ 10 ^4.8 Ω / □ 10 ^4.8 Ω / □ 10 ^4.9 Ω / □ 10 ^4.9 Ω / □ 10 ^4.9 Ω / □ PANI 10 ^7,1 Ω / □ 10 ^7.4 Ω / □ 10 ^7.5 Ω / □ 10 ^7.5 Ω / □ 10 ^7.6 Ω / □ 10 ^7.6 Ω / □ 10 ^7.6 Ω / □

Table 1 summarizes the results of the experiments on the water resistance according to the immersion time of the film made of only the conductive material and the conductive emulsifier polymer when the conductive material is a conductive polymer.

The PT is a conductive polymer is a polythiophene, PEDOT is a conductive polymer is Poly (3,4-ethylenedioxythiophene), PPY is a conductive polymer is a polypyrrole, PANI is a conductive polymer is a polyaniline.

In this case, the initial sheet resistance was from 10 ^4.0 Ω / □ to 10 ^7.3 Ω / □, but during the first 3 hours of immersion time, the sheet resistance increased significantly, and after a certain time, the conductive emulsifier was dissolved to measure the properties of the conductive emulsifier. It means no. Therefore, it has insulation characteristics exceeding 10 ¹³ Ω / □ which is the sheet resistance measurement limit of the 4-point probe.

Table 2 shows a film prepared using a composite made of a graft copolymer and a conductive material between a conductive emulsifier and an alcoholic polymer prepared by adding an alcoholic polymer to a polymer of the conductive material and the conductive emulsifier when the conductive material is a conductive polymer. This data summarizes the results of the experiment on water resistance according to the immersion time of.

The change in sheet resistance was weakly maintained by keeping constant from 10 ^4.2 Ω / □ to 10 ^7.8 Ω / □ for 48 hours regardless of the water temperature. The results show that the graft copolymer between the conductive emulsifier and the alcoholic polymer and the conductive material are very stable to moisture, compared to a film composed only of a polymer of the conductive material and the conductive emulsifier, which is very vulnerable to moisture.

2) Weather resistance when the conductive material is a conductive polymer

Temperature
(℃) conductivity
Polymer Conductive Polymer / Conductive Emulsifier: Standby Time (hour) 0 hours 12 hours 24 hours 48 hours 96 hours 168 hours 30 PT 10 ^7.3 Ω / □ 10 ^7.8 Ω / □ 10 ^8.5 Ω / □ 10 ^8.7 Ω / □ 10 ^9.2 Ω / □ 10 ^9.9 Ω / □ PEDOT 10 ^4.0 Ω / □ 10 ^4.8 Ω / □ 10 ^5.2 Ω / □ 10 ^5.5 Ω / □ 10 ^5.5 Ω / □ 10 ^7.6 Ω / □ PPY 10 ^4.5 Ω / □ 10 ^4.7 Ω / □ 10 ^5.2 Ω / □ 10 ^5.7 Ω / □ 10 ^6.2 Ω / □ 10 ^8.5 Ω / □ PAN 10 ^7.1 Ω / □ 10 ^7.4 Ω / □ 10 ^7.7 Ω / □ 10 ^8.3 Ω / □ 10 ^8.9 Ω / □ 10 ^9.7 Ω / □

Temperature
(℃) conductivity
Polymer Conductive polymer / conductive emulsifier-g-alcohol polymer: stand time (hour) 0 hours 12 hours 24 hours 48 hours 96 hours 168 hours 30 PT 10 ^7.3 Ω / □ 10 ^7.3 Ω / □ 10 ^7.3 Ω / □ 10 ^7.4 Ω / □ 10 ^7.4 Ω / □ 10 ^7.6 Ω / □ PEDOT 10 ^4.0 Ω / □ 10 ^4.0 Ω / □ 10 ^4.0 Ω / □ 10 ^4.0 Ω / □ 10 ^4.1 Ω / □ 10 ^4.1 Ω / □ PPY 10 ^4.5 Ω / □ 10 ^4.5 Ω / □ 10 ^4.5 Ω / □ 10 ^4.6 Ω / □ 10 ^4.6 Ω / □ 10 ^4.6 Ω / □ PANI 10 ^7.1 Ω / □ 10 ^7.1 Ω / □ 10 ^7.1 Ω / □ 10 ^7.2 Ω / □ 10 ^7.2 Ω / □ 10 ^7.3 Ω / □ 80 PT 10 ^7.3 Ω / □ 10 ^7.4 Ω / □ 10 ^7.5 Ω / □ 10 ^7.5 Ω / □ 10 ^7.6 Ω / □ 10 ^7.8 Ω / □ PEDOT 10 ^4.0 Ω / □ 10 ^4.2 Ω / □ 10 ^4.2 Ω / □ 10 ^4.2 Ω / □ 10 ^4.4 Ω / □ 10 ^4.4 Ω / □ PPY 10 ^4.5 Ω / □ 10 ^4.5 Ω / □ 10 ^4.5 Ω / □ 10 ^4.6 Ω / □ 10 ^4.6 Ω / □ 10 ^5.0 Ω / □ PANI 10 ^7.1 Ω / □ 10 ^7.2 Ω / □ 10 ^7.2 Ω / □ 10 ^7.4 Ω / □ 10 ^7.5 Ω / □ 10 ^7.7 Ω / □ High temperature
Humidity
(80 ℃ /
Relative resolution
85%) PT 10 ^7.3 Ω / □ 10 ^7.5 Ω / □ 10 ^7.6 Ω / □ 10 ^7.6 Ω / □ 10 ^7.8 Ω / □ 10 ^7.9 Ω / □ PEDOT 10 ^4.0 Ω / □ 10 ^4.2 Ω / □ 10 ^4.3 Ω / □ 10 ^4.3 Ω / □ 10 ^4.4 Ω / □ 10 ^4.5 Ω / □ PPY 10 ^4.5 Ω / □ 10 ^4.6 Ω / □ 10 ^4.6 Ω / □ 10 ^4.7 Ω / □ 10 ^4.8 Ω / □ 10 ^5.1 Ω / □ PANI 10 ^7.1 Ω / □ 10 ^7.3 Ω / □ 10 ^7.5 Ω / □ 10 ^7.6 Ω / □ 10 ^7.8 Ω / □ 10 ^7.9 Ω / □

Table 3 summarizes the results of experiments on weather resistance according to the immersion time of a film made only of the polymer of the conductive material and the conductive emulsifier when the conductive material is a conductive polymer.

In this case, the initial sheet resistance was from 10 ^4.0 Ω / □ to 10 ^7.3 Ω / □, but the sheet resistance value began to increase during the first 3 hours of immersion, and after 168 hours, the conductive emulsifier was dissolved to measure the properties of the conductive emulsifier and the conductive polymer. It means you can't.

Table 4 shows a film prepared using a composite made of a graft copolymer and a conductive material between a conductive emulsifier and an alcoholic polymer prepared by adding an alcoholic polymer to a polymer of the conductive material and the conductive emulsifier when the conductive material is a conductive polymer. This data summarizes the results of the experiment on weatherability according to the time left to the outside.

The change in sheet resistance was weakly maintained at a constant of 10 ^4.1 Ω / □ to 10 ^7.9 Ω / □ for up to 168 hours regardless of the external temperature. The results show that the weather resistance of the graft copolymer between the conductive emulsifier and the alcoholic polymer and the conductive material is very excellent compared to the film composed of the polymer of the conductive material and the conductive emulsifier, which is very vulnerable to moisture.

3) Chemical resistance when the conductive material is a conductive polymer

Sedimentation
time
(hour) conductivity
Polymer Conductive Polymer / Conductive Emulsifier: Solvent Treatment 0 hours Acetone Methanol DMF THF 12 PT 10 ^7.3 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ PEDOT 10 ^4.0 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ PPY 10 ⁴⁵ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ PAN 10 ^7.1 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □

Sedimentation
time
(hour) conductivity
Polymer Conductive Polymer / Conductive Emulsifier-g-Alcohol Polymer: Solvent Treatment 0 hours Acetone Methanol DMF THF 12 PT 10 ^7.3 Ω / □ 10 ^7.4 Ω / □ 10 ^7.4 Ω / □ 10 ^7.3 Ω / □ 10 ^7.3 Ω / □ PEDOT 10 ^4.0 Ω / □ 10 ^4.1 Ω / □ 10 ^4.1 Ω / □ 10 ^4.2 Ω / □ 10 ^4.3 Ω / □ PPY 10 ^4.5 Ω / □ 10 ^4.6 Ω / □ 10 ^4.7 Ω / □ 10 ^4.6 Ω / □ 10 ^4.7 Ω / □ PAN 10 ^7.1 Ω / □ 10 ^7.2 Ω / □ 10 ^7.3 Ω / □ 10 ^7.2 Ω / □ 10 ^7.3 Ω / □ 24 PT 10 ^7.3 Ω / □ 10 ^7.5 Ω / □ 10 ^7.5 Ω / □ 10 ^7.4 Ω / □ 10 ^7.4 Ω / □ PEDOT 10 ^4.0 Ω / □ 10 ^4.2 Ω / □ 10 ^4.2 Ω / □ 10 ^4.3 Ω / □ 10 ^4.4 Ω / □ PPY 10 ^4.5 Ω / □ 10 ^4.7 Ω / □ 10 ^4.8 Ω / □ 10 ^4.7 Ω / □ 10 ^4.8 Ω / □ PAN 10 ^7.1 Ω / □ 10 ^7.3 Ω / □ 10 ^7.4 Ω / □ 10 ^7.3 Ω / □ 10 ^7.4 Ω / □ 48 PT 10 ^7.3 Ω / □ 10 ^7.7 Ω / □ 10 ^7.7 Ω / □ 10 ^7.8 Ω / □ 10 ^7.7 Ω / □ PEDOT 10 ^4.0 Ω / □ 10 ^4.5 Ω / □ 10 ^4.4 Ω / □ 10 ^4.6 Ω / □ 10 ^4.4 Ω / □ PPY 10 ^4.5 Ω / □ 10 ^4.8 Ω / □ 10 ^4.9 Ω / □ 10 ^4.8 Ω / □ 10 ^4.9 Ω / □ PAN 10 ^7.1 Ω / □ 10 ^7.5 Ω / □ 10 ^7.5 Ω / □ 10 ^7.6 Ω / □ 10 ^7.6 Ω / □

Table 5 shows acetone, methanol, methanol, dimethylformamide (DMF), and tetrahydrofuran (THF) for the chemical resistance test of a film made of a polymer of a conductive material and a conductive emulsifier when the conductive material is a conductive polymer. It is the data which measured the change of sheet resistance with time by depositing the said film in each solvent.

Table 6 shows a film prepared using a composite made of a graft copolymer and a conductive material between a conductive emulsifier and an alcoholic polymer prepared by adding an alcoholic polymer to a polymer of the conductive material and the conductive emulsifier when the conductive material is a conductive polymer. Acetone, methanol, dimethylformamide (DMF), and tetrahydrofuran (THF) were selected for the chemical resistance test, and the film was precipitated in each solvent to measure the change in sheet resistance over time.

The change in sheet resistance was found to be weakly maintained at a constant of 10 ^4.4 Ω / □ to 10 ^7.8 Ω / □ for 48 hours regardless of the water temperature. The results show that the graft copolymer between the conductive emulsifier and the alcoholic polymer and the conductive material are very stable to the chemical material, compared to the film composed of the polymer of the conductive material and the conductive emulsifier, which is very vulnerable to the chemical material.

4) Water resistance when the conductive material is carbon material

Water temperature (℃) Carbon
matter Carbon material / conductive emulsifier: Immersion time (hour) 0 hours 3 hours 6 hours 12 hours 24 hours 36 hours 48 hours 10 Graphene 10 ^6.2
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ CNT 10 ^5.7
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ 30 Graphene 10 ^6.2
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ CNT 10 ^5.7
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ 50 Graphene 10 ^6.2
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ CNT 10 ^5.7
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □

Water temperature
(℃) Carbon
matter Carbon material / conductive emulsifier-g-alcohol polymer: Immersion time (hour) 0 hours 3 hours 6 hours 12 hours 24 hours 36 hours 48 hours 10 Graphene 10 ^6.2 Ω / □ 10 ^6.2 Ω / □ 10 ^6.3 Ω / □ 10 ^6.3 Ω / □ 10 ^6.3 Ω / □ 10 ^6.3 Ω / □ 10 ^6.3 Ω / □ CNT 10 ^5.7 Ω / □ 10 ^5.7 Ω / □ 10 ^5.8 Ω / □ 10 ^5.8 Ω / □ 10 ^5.8 Ω / □ 10 ^5.8 Ω / □ 10 ^5.8 Ω / □ 30 Graphene 10 ^6.2 Ω / □ 10 ^6.3 Ω / □ 10 ^6.3 Ω / □ 10 ^6.3 Ω / □ 10 ^6.4 Ω / □ 10 ^6.4 Ω / □ 10 ^6.4 Ω / □ CNT 10 ^5.7 Ω / □ 10 ^5.8 Ω / □ 10 ^5.8 Ω / □ 10 ^5.9 Ω / □ 10 ^5.9 Ω / □ 10 ^5.9 Ω / □ 10 ^5.9 Ω / □ 50 Graphene 10 ^6.2 Ω / □ 10 ^6.3 Ω / □ 10 ^6.4 Ω / □ 10 ^6.5 Ω / □ 10 ^6.5 Ω / □ 10 ^6.6 Ω / □ 10 ^6.6 Ω / □ CNT 10 ^5.7 Ω / □ 10 ^5.8 Ω / □ 10 ^5.9 Ω / □ 10 ^5.9 Ω / □ 10 ^5.9 Ω / □ 10 ^5.9 Ω / □ 10 ^6.0 Ω / □

Table 7 summarizes the results of the experiment on the water resistance according to the immersion time of the film made of the polymer of the conductive material and the conductive emulsifier when the conductive material is a carbon material.

In this case, the initial sheet resistance was from 10 ^5.7 Ω / □ to 10 ^6.2 Ω / □, but during the first 3 hours of immersion time, the sheet resistance increased significantly, and after a certain time, the conductive emulsifier was dissolved to measure the characteristics of the conductive emulsifier. It means no. Therefore, it has insulation characteristics exceeding 10 ¹³ Ω / □ which is the sheet resistance measurement limit of the 4-point probe.

Table 8 shows a film prepared using a composite made of a graft copolymer and a conductive material between a conductive emulsifier and an alcoholic polymer prepared by adding an alcoholic polymer to a polymer of the conductive material and the conductive emulsifier when the conductive material is a carbon material. This data summarizes the results of the experiment on water resistance according to the immersion time of.

The change in sheet resistance was weakly maintained by keeping constant at 10 ^5.8 Ω / □ to 10 ^6.6 Ω / □ for 48 hours regardless of the water temperature. The results show that the graft copolymer between the conductive emulsifier and the alcoholic polymer and the conductive material are very stable to moisture, compared to a film composed only of a polymer of the conductive material and the conductive emulsifier, which is very vulnerable to moisture.

5) Weather resistance when the conductive material is carbon material

Temperature
Condition Carbon
matter Carbon material / conductive emulsifier: stand time (hour) 0 hours 12 hours 24 hours 48 hours 96 hours 168 hours Room temperature Graphene 10 ^6.2 Ω / □ 10 ^6.5 Ω / □ 10 ^6.7 Ω / □ 10 ^7.7 Ω / □ 10 ^8.4 Ω / □ 10 ^9.0 Ω / □ CNT 10 ^5.7 Ω / □ 10 ^6.0 Ω / □ 10 ^6.4 Ω / □ 10 ^7.2 Ω / □ 10 ^7.8 Ω / □ 10 ^8.5 Ω / □ 80 degrees Graphene 10 ^6.2 Ω / □ 10 ^6.8 Ω / □ 10 ^6.9 Ω / □ 10 ^7.9 Ω / □ 10 ^8.7 Ω / □ 10 ^9.3 Ω / □ CNT 10 ^5.7 Ω / □ 10 ^6.2 Ω / □ 10 ^6.7 Ω / □ 10 ^7.5 Ω / □ 10 ^8.1 Ω / □ 10 ^9.2 Ω / □ High temperature
Humidity
(80 ℃ /
Relative Resolution 85%) Graphene 10 ^6.2 Ω / □ 10 ^9.8 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ CNT 10 ^5.7 Ω / □ 10 ^9.7 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □

Temperature
Condition Carbon
matter Carbon material / conducting emulsifier-g-alcohol polymer: stand time (hour) 0 hours 12 hours 24 hours 48 hours 96 hours 168 hours Room temperature Graphene 10 ^6.2 Ω / □ 10 ^6.3 Ω / □ 10 ^6.3 Ω / □ 10 ^6.3 Ω / □ 10 ^6.3 Ω / □ 10 ^6.3 Ω / □ CNT 10 ^5.7 Ω / □ 10 ^5.8 Ω / □ 10 ^5.8 Ω / □ 10 ^5.8 Ω / □ 10 ^5.8 Ω / □ 10 ^5.8 Ω / □ 80 degrees Graphene 10 ^6.2 Ω / □ 10 ^6.3 Ω / □ 10 ^6.4 Ω / □ 10 ^6.4 Ω / □ 10 ^6.5 Ω / □ 10 ^6.5 Ω / □ CNT 10 ^5.7 Ω / □ 10 ^5.8 Ω / □ 10 ^5.8 Ω / □ 10 ^5.9 Ω / □ 10 ^5.9 Ω / □ 10 ^5.9 Ω / □ High temperature
Humidity
(80 ℃ /
Relative Resolution 85%) Graphene 10 ^6.2 Ω / □ 10 ^6.3 Ω / □ 10 ^6.5 Ω / □ 10 ^6.5 Ω / □ 10 ^6.6 Ω / □ 10 ^6.7 Ω / □ CNT 10 ^5.7 Ω / □ 10 ^5.8 Ω / □ 10 ^5.9 Ω / □ 10 ^6.0 Ω / □ 10 ^6.2 Ω / □ 10 ^6.3 Ω / □

Table 9 summarizes the results of the experiment on the weather resistance according to the time left to the outside of the film made only of the polymer of the conductive material and the conductive emulsifier when the conductive material is a carbon material.

In this case, the initial sheet resistance was 10 ^5.7 Ω / □ to 10 ^6.2 Ω / □, but the sheet resistance value began to increase during the first 3 hours immersion time, and after 168 hours, the conductive emulsifier was dissolved so that the characteristics of the conductive emulsifier could not be measured. It means.

Table 10 shows a film prepared using a composite made of a graft copolymer and a conductive material between a conductive emulsifier and an alcoholic polymer prepared by adding an alcoholic polymer to a polymer of the conductive material and the conductive emulsifier when the conductive material is a carbon material. This data summarizes the results of the experiment on weatherability according to the time left to the outside.

The change in sheet resistance was weakly maintained at a constant of 10 ^5.8 Ω / □ to 10 ^6.7 Ω / □ for up to 168 hours regardless of the external temperature. The results show that the weather resistance of the graft copolymer between the conductive emulsifier and the alcoholic polymer and the conductive material is very excellent compared to the film composed of the polymer of the conductive material and the conductive emulsifier, which is very vulnerable to moisture.

6) Chemical resistance when conductive material is carbon material

Sedimentation
time
(hour) Carbon
matter Carbon material / conductive emulsifier: solvent treatment 0 hours Acetone Methanol DMF THF 12 Graphene 10 ^6.2 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ CNT 10 ^5.7 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ 24 Graphene 10 ^6.2 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ CNT 10 ^5.7 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ 48 Graphene 10 ^6.2 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ CNT 10 ^5.7 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □

Sedimentation
time
(hour) Carbon
matter Carbon material / conductive emulsifier-g-alcoholic polymer: solvent treatment 0 hours Acetone Methanol DMF THF 12 Graphene 10 ^6.2 Ω / □ 10 ^6.3 Ω / □ 10 ^6.3 Ω / □ 10 ^6.2 Ω / □ 10 ^6.3 Ω / □ CNT 10 ^5.7 Ω / □ 10 ^5.8 Ω / □ 10 ^5.8 Ω / □ 10 ^5.7 Ω / □ 10 ^5.8 Ω / □ 24 Graphene 10 ^6.2 Ω / □ 10 ^6.4 Ω / □ 10 ^6.5 Ω / □ 10 ^6.4 Ω / □ 10 ^6.3 Ω / □ CNT 10 ^5.7 Ω / □ 10 ^5.9 Ω / □ 10 ^6.0 Ω / □ 10 ^5.9 Ω / □ 10 ^5.9 Ω / □ 48 Graphene 10 ^6.2 Ω / □ 10 ^6.6 Ω / □ 10 ^6.7 Ω / □ 10 ^6.8 Ω / □ 10 ^6.8 Ω / □ CNT 10 ^5.7 Ω / □ 10 ^6.2 Ω / □ 10 ^6.4 Ω / □ 10 ^6.3 Ω / □ 10 ^6.1 Ω / □

Table 11 shows acetone, methanol, methanol, dimethylformamide (DMF), and tetrahydrofuran (THF) for chemical resistance tests of films made of polymers of conductive material and conductive emulsifier when the conductive material is carbon. It is the data which measured the change of sheet resistance with time by depositing the said film in each solvent.

Table 12 shows a graft copolymer between a conductive emulsifier and an alcoholic polymer prepared by adding an alcoholic polymer to a polymer of a conductive material and a conductive emulsifier when the conductive material is a conductive polymer, and a film made of a composite made of a conductive material. Acetone, methanol, dimethylformamide (DMF), and tetrahydrofuran (THF) were selected for the chemical resistance test, and the film was precipitated in each solvent to measure the change in sheet resistance over time.

The change in sheet resistance was weakly maintained by keeping constant at 10 ^5.8 Ω / □ to 10 ^6.8 Ω / □ for 48 hours regardless of the water temperature. The results show that the graft copolymer between the conductive emulsifier and the alcoholic polymer and the conductive material are very stable to the chemical material, compared to the film composed of the polymer of the conductive material and the conductive emulsifier, which is very vulnerable to the chemical material.

7) Water resistance when conductive material is metal

Water temperature
(℃) metal
matter Silver Nanowire / Conductive Emulsifier: Immersion Time (hour) 0 hours 3 hours 6 hours 12 hours 24 hours 36 hours 48 hours 10 Silver nanowire 50
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ 30 Silver nanowire 50
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ 50 Silver nanowire 50
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □ > 10 ¹³
Ω / □

Water temperature
(℃) metal
matter Silver Nanowire / Conductive Emulsifier-g-Alcohol Polymer: Immersion Time (hour) 0 hours 3 hours 6 hours 12 hours 24 hours 36 hours 48 hours 10 Silver nanowire 50 Ω / □ 50 Ω / □ 52 Ω / □ 53 Ω / □ 55 Ω / □ 55 Ω / □ 55 Ω / □ 30 Silver nanowire 50 Ω / □ 50 Ω / □ 50 Ω / □ 52 Ω / □ 54 Ω / □ 55 Ω / □ 55 Ω / □ 50 Silver nanowire 50 Ω / □ 55 Ω / □ 55 Ω / □ 57 Ω / □ 58 Ω / □ 58 Ω / □ 60 Ω / □

Table 13 summarizes the results of the experiments on the water resistance according to the immersion time of a film made only of the polymer of the conductive material and the conductive emulsifier when the conductive material is a metal material.

When the initial sheet resistance was 50 Ω / □, the sheet resistance value is greatly increased during the first 3 hours immersion time, which means that after a certain time the conductive emulsifier is dissolved and the characteristics of the conductive emulsifier cannot be measured. Therefore, it has insulation characteristics exceeding 10 ¹³ Ω / □ which is the sheet resistance measurement limit of the 4-point probe.

Table 14 shows a graft copolymer between a conductive emulsifier and an alcoholic polymer prepared by adding an alcoholic polymer to a polymer of the conductive material and the conductive emulsifier when the conductive material is a metal material, and a film made of a composite made of a conductive material. This data summarizes the results of the experiment on water resistance according to the immersion time of.

The change in sheet resistance was found to be weakly maintained at a constant of 55 Ω / □ to 60 Ω / □ for 48 hours regardless of the water temperature. The results show that the graft copolymer between the conductive emulsifier and the alcoholic polymer and the conductive material are very stable to moisture, compared to a film composed only of a polymer of the conductive material and the conductive emulsifier, which is very vulnerable to moisture.

8) Weather resistance when the conductive material is metal

Temperature
Condition metal
matter Silver Nanowire / Conductive Emulsifier: Standby Time (hour) 0 hours 12 hours 24 hours 48 hours 96 hours 168 hours Room temperature Silver nanowire 50 Ω / □ 120 Ω / □ 320 Ω / □ 520 Ω / □ 700 Ω / □ 1050 Ω / □ 80 degrees Silver nanowire 50 Ω / □ 220 Ω / □ 520 Ω / □ 920 Ω / □ 1200 Ω / □ 2200 Ω / □ High temperature
Humidity
(80 ℃ /
Relative resolution
85%) Silver nanowire 50 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □

Temperature
Condition metal
matter Silver Nanowire / conductive emulsifier-g-alcohol polymer: stand time (hour) 0 hours 12 hours 24 hours 48 hours 96 hours 168 hours Room temperature Silver nanowire 50 Ω / □ 50 Ω / □ 50 Ω / □ 50 Ω / □ 50 Ω / □ 50 Ω / □ 80 degrees Silver nanowire 50 Ω / □ 50 Ω / □ 53 Ω / □ 53 Ω / □ 55 Ω / □ 56 Ω / □ High temperature
Humidity
(80 ℃ /
Relative resolution
85%) Silver nanowire 50 Ω / □ 50 Ω / □ 54 Ω / □ 54 Ω / □ 56 Ω / □ 57 Ω / □

Table 15 summarizes the results of the experiment on the weather resistance according to the time left to the outside of the film made only of the polymer of the conductive material and the conductive emulsifier when the conductive material is a metal material.

In this case, the initial sheet resistance was 50 Ω / □, but the sheet resistance value began to increase during the first 3 hours immersion time, and after 168 hours, the conductive emulsifier was dissolved, which means that the characteristics of the conductive emulsifier could not be measured.

Table 16 shows a graft copolymer between a conductive emulsifier and an alcoholic polymer prepared by adding an alcoholic polymer to a polymer of the conductive material and the conductive emulsifier when the conductive material is a metal material, and a film made of a composite made of a conductive material. This data summarizes the results of the experiment on weatherability according to the time left to the outside.

The change in sheet resistance was found to be weakly maintained constant at 50 Ω / □ to 57 Ω / □ for up to 168 hours regardless of the external temperature. The results show that the weather resistance of the graft copolymer between the conductive emulsifier and the alcoholic polymer and the conductive material is very excellent compared to the film composed of the polymer of the conductive material and the conductive emulsifier, which is very vulnerable to moisture.

9) Chemical resistance when conductive material is metal

Sedimentation
time
(hour) metal
matter Silver Nanowire / Conductive Emulsifier: Solvent Treatment 0 hours Acetone Methanol DMF THF 12 Silver nanowire 50 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ 24 Silver nanowire 50 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ 48 Silver nanowire 50 Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □ > 10 ¹³ Ω / □

Sedimentation
time
(hour) Carbon
matter Silver Nanowire / Conductive Emulsifier-g-Alcohol Polymer: Solvent Treatment 0 hours Acetone Methanol DMF THF 12 Silver nanowire 50 Ω / □ 53 Ω / □ 54 Ω / □ 55 Ω / □ 55 Ω / □ 24 Silver nanowire 50 Ω / □ 55 Ω / □ 58 Ω / □ 55 Ω / □ 61 Ω / □ 48 Silver nanowire 50 Ω / □ 59 Ω / □ 60 Ω / □ 62 Ω / □ 62 Ω / □

Table 17 shows acetone, methanol, dimethylformamide (DMF) and tetrahydrofuran (THF) for chemical resistance testing of films made of polymers of conductive material and conductive emulsifier when the conductive material is a metal material. It is the data which measured the change of sheet resistance with time by depositing the said film in each solvent.

Table 18 shows a film prepared using a composite made of a graft copolymer and a conductive material between a conductive emulsifier and an alcoholic polymer prepared by adding an alcoholic polymer to a polymer of the conductive material and the conductive emulsifier when the conductive material is a metal material. Acetone, methanol, dimethylformamide (DMF), and tetrahydrofuran (THF) were selected for the chemical resistance test, and the film was precipitated in each solvent to measure the change in sheet resistance over time.

The change in sheet resistance was found to be weakly maintained constant at 55 Ω / □ to 62 Ω / □ for 48 hours regardless of the water temperature. The results show that the graft copolymer between the conductive emulsifier and the alcoholic polymer and the conductive material are very stable to the chemical material, compared to the film composed of the polymer of the conductive material and the conductive emulsifier, which is very vulnerable to the chemical material.

Although the present invention has been described with reference to the accompanying drawings, it is merely one example of various embodiments including the gist of the present invention, which can be easily implemented by those skilled in the art. It is clear that the present invention is not limited to the above-described embodiment only. Therefore, the protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the scope equivalent to the change, substitution, substitution, etc. within the scope not departing from the gist of the present invention shall be the right of the present invention. It will be included in the scope. In addition, some of the components of the drawings are intended to more clearly describe the configuration, and it is clear that the exaggerated or reduced size is provided.

Claims

A conductive material composed of any one or two or more of a conductive polymer, a carbon material, or a metal material, and a conductive emulsifier having a hydrophilic group have a polymer and two terminal groups physically bonded, and the first terminal group is a hydrophilic group, and the second terminal group Is characterized in that formed by the dehydration condensation reaction of the alcoholic polymer is a hydrophobic group,
The conductive material includes (i) Poly (3,4-ethylenedioxythiophene), Polythiophene, Polypyrrole, Polyaniline, and Poly (3-methyl thiophene), Poly (3-hexyl thiophene), Poly (3-hexyl thiophene), Poly octylthiophene, Polyfullerene, and Polyacetylene, which are conductive polymers. , Polyfuran, Polyphenylene sulfide, poly (phenylenevinylene), poly (thienylene-vinylene), Poly sulfur nitride, (ii) Carbon nanotube, Graphene, Activate carbon, (iii) Gold pariticle, Silver nanowire, Silver nanoparticle Any one or a combination of two or more of them,
The conductive emulsifier is 4-toluenesulfonic acid (p-Toluenesulfonic acid), 1-naphthalenesulfonic acid (1-Naphthalenesulfonic acid), dodecyl benezene sulfonic acid (dodecyl benezene sulfonic acid), polyvinyl sulfonic acid (poly (vinyl sulfonic acid) )], Any one selected from poly (4-styrene sulfonic acid) or a combination of two or more selected from poly (acrylic acid) and polymethacrylic acid (poly (methacrylic acid)] One or a combination of two or more,
The alcoholic polymer includes a graft copolymer and a conductive material between the conductive emulsifier and the alcoholic polymer, wherein the first terminal is a hydroxy group and the second terminal is an alkyl group. Complex.

In the manufacturing method of a composite consisting of a graft copolymer, a conductive material between the conductive emulsifier and the alcoholic polymer,
(i) preparing a conductive solution comprising a polymer in which a conductive material made of any one or two or more of a conductive polymer, a carbon material, or a metal material and a conductive emulsifier having a hydrophilic group are physically bonded;
(ii) preparing an alcoholic polymer having two end groups, wherein the first end group is a hydrophilic group and the second end group is a hydrophobic group;
(iii) adding the alcoholic polymer to the conductive solution and dissolving it to prepare a mixed solution;
(iv) heat treating the mixed solution to dehydrocondensate the hydrophilic group of the conductive emulsifier and the first terminal group of the alcoholic polymer to form a graft copolymer having only a hydrophobic group;
Graft copolymer between the conductive emulsifier and the alcoholic polymer (graft copolymer), characterized in that it comprises a method for producing a composite made of a conductive material.

The method according to claim 2,
Step (iii) is a graft copolymer between the conductive emulsifier and the alcoholic polymer (graft copolymer), characterized in that the dissolved at a temperature of more than 10 ℃ 150 ℃ dissolution method of producing a composite made of a conductive material.

The method according to claim 2,
The heat treatment of step (iv) is a graft copolymer between the conductive emulsifier and the alcoholic polymer (graft copolymer), characterized in that at a temperature of 50 ℃ to 300 ℃ or less, a method for producing a composite made of a conductive material.

The method according to claim 2,
The conductive material includes (i) Poly (3,4-ethylenedioxythiophene), Polythiophene, Polypyrrole, Polyaniline, and Poly (3-methyl thiophene), Poly (3-hexyl thiophene), Poly (3-hexyl thiophene), Poly octylthiophene, Polyfullerene, and Polyacetylene, which are conductive polymers. , Polyfuran, Polyphenylene sulfide, poly (phenylenevinylene), poly (thienylene-vinylene), Poly sulfur nitride, (ii) Carbon nanotube, Graphene, Activate carbon, (iii) Gold pariticle, Silver nanowire, Silver nanoparticle Graft copolymer between the conductive emulsifier and the alcoholic polymer, characterized in that consisting of any one or a combination of two or more of the method of producing a composite made of a conductive material.

The method according to claim 2,
The conductive emulsifier is 4-toluenesulfonic acid (p-Toluenesulfonic acid), 1-naphthalenesulfonic acid (1-Naphthalenesulfonic acid), dodecyl benezene sulfonic acid (dodecyl benezene sulfonic acid), polyvinyl sulfonic acid (poly (vinyl sulfonic acid) )], Any one selected from poly (4-styrene sulfonic acid) or a combination of two or more selected from poly (acrylic acid) and polymethacrylic acid (poly (methacrylic acid)] A graft copolymer between a conductive emulsifier and an alcoholic polymer, characterized in that the material is made of one or two or more combinations.

The method according to claim 2,
The alcoholic polymer includes a graft copolymer and a conductive material between the conductive emulsifier and the alcoholic polymer, wherein the first terminal is a hydroxy group and the second terminal is an alkyl group. Method for preparing a composite.

The method according to claim 2,
The alcoholic polymer is polyethylene glycol methyl ether [Poly (ethylene glycol) methyl ether], polypropylene propylene glycol acrylate [Poly (propylene glycol) acrylate], polypropylene glycol methacrylate [Poly (propylene) methacrylate], polypropylene glycol Graphene between a conductive emulsifier and an alcoholic polymer, characterized in that the material is made of any one or a combination of two or more of mono (butyl glycol) monobutyl ether, poly (propylene glycol) monoooctyl ether Graft copolymer, a method for producing a composite consisting of a conductive material.

delete

In the method of manufacturing a film comprising a composite made of a graft copolymer, a conductive material between the conductive emulsifier and the alcoholic polymer,
(i) preparing a substrate;
(ii) preparing a conductive solution comprising a polymer in which a conductive material made of any one or two or more of a conductive polymer, a carbon material, or a metal material and a conductive emulsifier having a hydrophilic group are physically bonded;
(iii) preparing an alcoholic polymer having two end groups, wherein the first end group is a hydrophilic group and the second end group is a hydrophobic group;
(iv) adding the alcoholic polymer to the conductive solution and dissolving it to prepare a mixed solution;
(v) applying the mixed solution onto the substrate and coating the same;
(vi) heat-treating the coated mixed solution to dehydrocondensate the hydrophilic group of the conductive emulsifier and the first terminal group of the alcoholic polymer to include a composite made of a graft copolymer having only a hydrophobic group and a conductive material Forming a film to form;
Graft copolymer between the conductive emulsifier and the alcoholic polymer, characterized in that it comprises a method for producing a film comprising a composite made of a conductive material.

The method according to claim 11,
The coating of the mixed solution of the step (v) on the substrate may include at least one of spin coating, spray coating, roll to roll, or bar coating. Graft copolymer between the conductive emulsifier and the alcoholic polymer, characterized in that the wet coating (wet coating) comprising a method of producing a film comprising a composite consisting of a conductive material.

The method according to claim 11,
The conductive material is
(i) Poly (3,4-ethylenedioxythiophene), Polythiophene, Polypyrrole, Polyaniline, Thiophene derivatives, Poly (3-methyl thiophene), Poly (3-hexyl thiophene), Poly octylthiophene, Polyfullerene, Polyacetylene, Polyfuran, Polyphenylene sulfide, poly (phenylenevinylene), poly (thienylene-vinylene), poly sulfur nitride, (ii) carbon material carbon nanotube, graphene, Activate carbon, (iii) metal material gold pariticle, silver nanowire, silver nanoparticle or A graft copolymer between a conductive emulsifier and an alcoholic polymer, comprising a combination of two or more, a method of manufacturing a film comprising a composite made of a conductive material.

The method according to claim 11,
The conductive emulsifier is 4-toluenesulfonic acid (p-Toluenesulfonic acid), 1-naphthalenesulfonic acid (1-Naphthalenesulfonic acid), dodecyl benezene sulfonic acid (dodecyl benezene sulfonic acid), polyvinyl sulfonic acid (poly (vinyl sulfonic acid) )], Any one selected from poly (4-styrene sulfonic acid) or a combination of two or more selected from poly (acrylic acid) and polymethacrylic acid (poly (methacrylic acid)] A graft copolymer between a conductive emulsifier and an alcoholic polymer, characterized in that the material is made of one or two or more combinations, a method of manufacturing a film comprising a composite made of a conductive material.

The method according to claim 11,
The alcoholic polymer is polyethylene glycol methyl ether [Poly (ethylene glycol) methyl ether], polypropylene propylene glycol acrylate [Poly (propylene glycol) acrylate], polypropylene glycol methacrylate [Poly (propylene) methacrylate], polypropylene glycol Graphene between a conductive emulsifier and an alcoholic polymer, characterized in that the material is made of any one or a combination of two or more of mono (butyl glycol) monobutyl ether, poly (propylene glycol) monoooctyl ether Graft copolymer (graft copolymer), a method for producing a film comprising a composite consisting of a conductive material.

delete

The method according to claim 11,
The heat treatment in the step (vi) is a graft copolymer (graft copolymer) between the conductive emulsifier and the alcoholic polymer, characterized in that at a temperature of 50 ℃ to 300 ℃ or less, a method for producing a film comprising a composite consisting of a conductive material.

In the film comprising a composite made of a graft copolymer, a conductive material between the conductive emulsifier and the alcoholic polymer prepared by the method of claim 11,
A conductive emulsifier having a sheet resistance value of 10 ^1.0 to 10 ^13.0 Ω / □ and an increase in sheet resistance value of 20% or less based on the initial sheet resistance value even when impregnated with polar solvent for 48 hours or in the air for 168 hours. And a graft copolymer between the alcoholic polymer and a film comprising a composite made of a conductive material.