KR20140074748A

KR20140074748A - Composition of transparent electro-conductive film, Transparent electro-conductive film containing of the same and Preparing method of the same

Info

Publication number: KR20140074748A
Application number: KR1020120143048A
Authority: KR
Inventors: 김동환; 이정환; 김효석
Original assignee: 도레이케미칼 주식회사
Priority date: 2012-12-10
Filing date: 2012-12-10
Publication date: 2014-06-18

Abstract

The present invention relates to a transparent electroconductive film composition, a transparent electroconductive film, and a method for producing the same. More specifically, the present invention relates to an electroconductive film having peelability and excellent physical properties by introducing polypodamine and efficiently producing the electroconductive film in a short time Lt; / RTI >

Description

TECHNICAL FIELD The present invention relates to a transparent electroconductive film composition, a transparent electroconductive film containing the same, and a method of manufacturing the same.

The present invention relates to a transparent electroconductive film composition having excellent electrical and mechanical properties without using a dispersant, a transparent electroconductive film produced using the same, and a method for efficiently producing the same.

At present, vacuum deposited metal oxides such as indium tin oxide (ITO) provide optical transparency and electrical conductivity to dielectric surfaces such as glass and polymeric films. It is an industry standard material. However, the metal oxide film is weak and prone to damage by warping or other physical stresses. In addition, they require high deposition temperatures and / or high annealing temperatures to achieve high conductivity levels. Adhesion of the rapid oxide film to substrates that are susceptible to moisture, such as plastic and organic substrates, such as polycarbonate, may also be a problem. Therefore, application of a metal oxide film on a flexible substrate is very limited. In addition, vacuum deposition is a costly process and requires specialized equipment. Moreover, vacuum deposition processes are not helpful in forming patterns and circuits, which typically results in costly patterning processes such as photolithography.

Conventional electroconductive films have low conductivity values and high light absorptivity and lack chemical and long term stability. Therefore, there is a need for research to produce an electrically conductive film that can be manufactured in a low cost, high throughput process and has suitable electrical, optical, mechanical properties, and the like.

The mussel, a type of shellfish, can be seen to adhere well to various surfaces of oil and inorganic materials, as well as to wet surfaces and generally glazed surfaces. Analysis of the protein on the surface of the mussels shows that 3,4-dihydroxy-L-phenylalanine (DOPA) and lysine amino acids are contained in large amounts have. It is known that DOPA has strong covalent or noncovalent interactions with substrates. This characteristic of DOPA comes from the catechol group of DOPA, and the characteristics of lysine amino acids that enhance these properties come from the amine group. Thus, dopamine, which has both the catechol group of DOPA and the amine group of the lysine amino acid, mimics the adhesive material made in the mussel, and can act like an adhesive of the mussel. Recently, it has been reported that dopamine can function as a coating material that can be coated on various surfaces. Recently, it has been known that the functional group of polypodamine can have a high interface bonding force while interacting with a functional group of a specific adhesive substance have.

The present inventors have made efforts to produce an electrically conductive film excellent in electrical conductivity and mechanical properties while being capable of being peeled off. As a result, it has been found that the introduction of polydodamine can greatly improve the compatibility of the electrically conductive material and the polymer resin, .

In order to provide an electrically conductive film suitable for recent trends such as miniaturization and exfoliation of electronic products, the present invention provides a transparent electroconductive film composed of one layer not constituted of separate layers of an electrically conductive material by introducing polydopamine I want to.

In order to solve the above problems, the present invention relates to a transparent electroconductive film composition comprising a polymer selected from the group consisting of polyethylene oxide (PEO), a fluorinated polymer, a sulfonated polysulfone, a sulfonated polyimide, a sulfonated polyether sulfone, a sulfonated polyether ether ketone, A polymer resin containing at least one selected from the group consisting of phosphate complex polybenzimidazole, polyvinylidene fluoride and polyacrylonitrile; Electrically conductive material; And a polypodamine resin.

In one preferred embodiment of the present invention, the transparent electroconductive film composition of the present invention comprises 60 to 90% by weight of the polymer resin, 0.5 to 5% by weight of the electroconductive material and 2 to 20 mg / ml of the polydopamine resin .

In one preferred embodiment of the present invention, the electroconductive film composition of the present invention may further include at least one selected from carbon nanotubes, carbon nanowires, silver nanoparticles, and silver nanowires.

As another preferred embodiment of the present invention, in the transparent electroconductive film composition of the present invention, the electroconductive material is selected from the group consisting of PEDOT: PSS (poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate) Poly (phenylacetylene), poly (vinylidene fluoride), polyaniline, polydiphenyl, acetylene, poly (t- butyl) diphenylacetylene, poly (trifluoromethyl) diphenylacetylene, Cu- t-butyldiphenyl) acetylene, poly (trimethylsilyl) diphenylacetylene, poly (carbazole) diphenylacetylene, polydiacetylene, polyphenylacetylene, polypyridine acetylene, polymethoxyphenylacetylene, polymethylphenylacetylene, poly (trifluoromethyl) phenylacetylene, and poly (trimethylsilyl) phenylacetylene, which is preferably selected from the group consisting of t-butyl have.

In another preferred embodiment of the present invention, the polypodamine resin comprises a polypodamine polymer containing at least one selected from the group consisting of polydopamine represented by the following formula (1) and polydopamine represented by the following formula (2) To 2 mg / ml, based on the total weight of the composition.

[Chemical Formula 1]

(2)

In the above formulas (1) and (2), n is a rational number satisfying a weight average molecular weight of 10 to 200.

In another preferred embodiment of the present invention, the polydopamine resin is one selected from the group consisting of sodium periodate, dimethyl dioxirane, potassium permanganate, hydrogen peroxide, trifluoroperacetic acid, N-methylmorpholine N-oxide and oxone Or more of the oxidizing agent.

Another aspect of the present invention relates to a transparent electroconductive film, which can be characterized in that it comprises the electroconductive film composition described above, and the electroconductive film of the present invention has a surface resistance of 450 to 800 Ω / square and a transparency of 80% or more when measured by the ASTM D1003 method. It is also characterized by a single layer structure having an average thickness of 10 to 200 탆.

Another aspect of the present invention relates to a method for producing a transparent electrically conductive film, wherein the electrically conductive film composition of any one of claims 1 to 6 is subjected to electrospinning to produce an electrically conductive film And the electrospinning is carried out at 20 ° C to 80 ° C, at a voltage of 5 to 15 kV, and at a radiation distance of 10 to 20 cm.

The electroconductive film of the present invention can produce a transparent electrically conductive film having excellent electrical conductivity, optical and mechanical properties without using a conventional dispersant by introducing polydodamine as a crosslinking agent and dispersibility enhancer between a polymer resin and an electroconductive substance And a film which can be produced as a single layer unlike the conventional multilayer electroconductive film.

Hereinafter, the present invention will be described in detail.

The transparent electroconductive film of the present invention is a polydopamine resin which is introduced as an electroconductive substance and a polymer resin crosslinking agent and as a dispersing agent for improving the dispersibility of an electroconductive substance, and the composition of the electroconductive film of the present invention will be described.

The transparent electroconductive film composition of the present invention may include 60 to 95% by weight of a polymer resin, 4 to 35% by weight of an electrically conductive material and 1 to 10% by weight of a polypopamine resin, and the carbon nanotube, carbon nanowire, Particles and silver nanowires may be further included.

In the composition of the present invention, the polymer resin may be at least one selected from the group consisting of polyethylene oxide (PEO), fluoropolymer, sulfonated polysulfone, sulfonated polyimide, sulfonated polyether sulfone, sulfonated polyether ether ketone and phosphate complexed polybenzimidazole, Polyvinylidene fluoride, polyvinylidene fluoride, polyvinylidene fluoride, polyvinylidene fluoride, polyvinylidene fluoride, polyvinylidene fluoride, polyvinylidene fluoride, polyvinylidene fluoride and polyacrylonitrile, preferably polyethylene oxide and polyimide. The amount of the polymer resin to be used is preferably 60 to 95% by weight, preferably 70 to 95% by weight, more preferably 75 to 95% by weight, based on the total weight of the composition. %, The nano-web can not be formed, and the electrospinning itself may not be attained. If the amount of the polypodamine resin is more than 95% by weight, the amount of the polypodamine resin to be used may be relatively small.

In the composition of the present invention, the electrically conductive material is selected from the group consisting of PEDOT: PSS (poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate)), polyaniline, polydiphenyl, acetylene, poly (T-butyldiphenyl) acetylene, poly (trimethylsilyl) di (triphenylmethyl) diphenylacetylene, poly (Meth) acrylates, such as phenylacetylene, poly (acetylenes), phenylacetylene, poly (carbazole) diphenylacetylene, polydiacetylene, polyphenylacetylene, polypyridine acetylene, polymethoxyphenylacetylene, polymethylphenylacetylene, At least one member selected from the group consisting of PEDOT: PSS, polyaniline, polynitrophenylacetylene, poly (trifluoromethyl) phenylacetylene, Cetylenes, and poly (trimethylsilyl) phenylacetylenes. The amount of the electrically conductive material to be used is preferably 4 to 35% by weight, more preferably 10 to 35% by weight, and more preferably 15 to 35% by weight based on the total weight of the composition. The electrical conductivity may not be good, and even if it is used in an amount exceeding 35% by weight, it is not economical since there is no longer an effect of increasing the electric conductivity due to the increase in the use amount.

In the composition of the present invention, the polydopamine resin includes a polydopamine polymer, and the polydopamine polymer is a polymer in which a catechol functional group of polypodamine is introduced between a polymer resin and an electrically conductive substance to improve mutual adhesion and dispersibility will be. Such a polydopamine resin may comprise a polydopamine polymer, a buffer and a solvent, and may further comprise an oxidizing agent.

The polydopamine polymer may include at least one polymer selected from the group consisting of polydopamine represented by the following formula (1) and polydopamine represented by the following formula (2).

[Chemical Formula 1]

(2)

In the above formulas (1) and (2), n is a rational number satisfying a weight average molecular weight of 10 to 200, and preferably n is a rational number satisfying a weight average molecular weight of 100 to 200.

The concentration of the polydopamine polymer is preferably 2 to 20 mg / ml, preferably 2 to 10 mg / ml, based on the total amount of the polydopamine resin. If the concentration is less than 2 mg / ml, the interfacial adhesion between the electroconductive substance and the polymer resin There may be a problem that the improvement effect is deteriorated. When the amount exceeds 20 mg / ml, the viscosity of the polypodamine resin is too high, so that there is a problem that the electroconductive resin is not mixed well with other compositions.

Examples of the buffer solution include Triz base, sodium phosphate, TBE (Tris / Borate / EDTA), TBS (sodium phosphate), and the like. Tris-buffered saline, and PBS (phosphate buffered saline).

Also, the solvent commonly used in the art can be used, and for example, distilled water or the like can be used.

The oxidizing agent is an important factor for increasing the reaction rate, and the higher the oxidizing power, the faster the reaction rate. The oxidizing agent may be selected from the group consisting of sodium perioate, dimethyldioxirane, potassium permanganate, hydrogen peroxide, trifluoroperacetic acid, N-methylmorpholine N-oxide (N-methylmorpholine N-oxide) and oxone.

In the present invention, the polypodamine resin preferably has a pH of 8 to 9, preferably a pH of 8.2 to 8.8, and if the pH is less than 8, the effect of improving the interfacial adhesion between the electroconductive substance and the polymer resin is deteriorated And when the pH exceeds 9, the effect of dispersing the electroconductive substance may be reduced. Therefore, it is necessary to adjust the pH by using the amount of the buffer and the acid.

In the transparent electroconductive film composition of the present invention, the amount of the polypodamine resin is preferably 1 to 10% by weight, preferably 2 to 10% by weight, and more preferably 3 to 8% by weight.

The transparent electroconductive film of the present invention can be produced by conducting electrospinning of the above-described various types of transparent electroconductive film compositions.

The electrospinning is preferably carried out at 20 캜 to 80 캜, preferably at 40 캜 to 80 캜. When electrospinning is carried out under a voltage of less than 5 kV, the amount of polymer introduced into the jet is small, and electrospinning is suppressed. If the voltage exceeds 15 kV, a larger amount of the polymer solution may be introduced into the jet, resulting in a thick fiber, which may make it difficult to control the thickness of the web. . In addition, the spinning distance is preferably 10 to 20 cm, preferably 12 to 18 cm, and when the spinning is performed at a distance of less than 10 cm, the electrically conductive film composition may not be uniformly spinned uniformly, If radiation is performed at a distance, it may be difficult to trap the nano-web on the current collecting plate after radiation.

It is preferable that the electrospinning is performed for 2 to 4 hours under the above conditions.

The transparent electroconductive film of the present invention produced by such a method has a surface resistance of 450 to 800 Ω / square, preferably 480 to 700 Ω / square when measured by the ASTM D257 method, and transparency when measured by the ASTM D1003 method 80% or more.

The transparent electrically conductive film of the present invention has a single layer structure having an average thickness of 10 to 200 占 퐉, preferably 100 to 150 占 퐉, whereby the film can be peeled off.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by the following examples.

[ Example ]

Example One

(One) Polydopamine Manufacture of resin

The solution was added to 100 ml of a Trizma base buffer solution adjusted to pH 8.5 with hydrochloric acid to a concentration of 10 mg / ml of a polydopamine polymer represented by the following formula (1-1), followed by adding 1 equivalent of sodium periodate to dissolve To prepare a polypodamine resin (hereinafter referred to as DOPA resin).

[Formula 1-1]

In Formula 1-1, n is a rational number satisfying a weight average molecular weight of 100 to 110 of the polymer.

(2) Preparation of transparent electrically conductive resin

80% by weight of polyethylene oxide resin (manufactured by Aldrich, hereinafter referred to as PEO), 4% by weight of the above polydopamine resin and 16% by weight of PEDOT: PSS (manufactured by Korea Biochem Co., Ltd.) were mixed and stirred to prepare a transparent electroconductive resin .

(3) Preparation of transparent electrically conductive film

The transparent electrically conductive resin was subjected to electrospinning using an electrospinning machine (manufactured by Woongjin Chemical) at 27 DEG C under a voltage of 15 kv and a radiation distance of 15 cm for 4 hours to prepare a transparent electrically conductive film having a thickness of 150 mu m.

Example 2 ~ Example 7

A transparent electrically conductive film was prepared in the same manner as in Example 1, except that the composition and electrospinning conditions shown in Table 1 were used.

Example 8

A transparent electroconductive film was prepared in the same manner as in Example 1 except that a polyelectrolyte prepared by using a polydopamine resin prepared at a concentration of 1 mg / .

Example 9

A transparent electroconductive film was prepared in the same manner as in Example 1 except that a polyelectrolyte film having a composition of polydopamine of 23 mg / .

Comparative Example One

A transparent electroconductive resin was prepared in the same manner as in Example 1, and then a casting method was used instead of electrospinning. The casting method was a method in which a transparent paper sheet of Sol- The conductive resin was coated and then laminated to produce a transparent electrically conductive film .

Comparative Example 2 ~ Comparative Example 5

division Composition (% by weight) Electrospinning conditions PEO DOPA resin PEDOT: PSS Voltage Room distance Example 1 80 wt% 4 wt% 16 wt% 13 kV 15 cm Example 2 76 wt% 8 wt% 16 wt% 13 kV 15 cm Example 3 70 wt% 5 wt% 25 wt% 13 kV 15 cm Example 4 66 wt% 4 wt% 30 wt% 13 kV 15 cm Example 5 80 wt% 4 wt% 16 wt% 10 kV 15 cm Example 6 80 wt% 4 wt% 16 wt% 15 kV 15 cm Example 7 80 wt% 4 wt% 16 wt% 13 kV 13 cm Example 8 80 wt% 4 wt% 16 wt% 13 kV 15 cm Example 9 80 wt% 4 wt% 16 wt% 13 kV 15 cm Comparative Example 1 80 wt% 4 wt% 16 wt% Casting method, not electrospinning Comparative Example 2 58 wt% 4 wt% 38 wt% 13 kV 15 cm Comparative Example 3 90 wt% 9.5 wt% 0.5 wt% 13 kV 15 cm Comparative Example 4 80 wt% 4 wt% 16 wt% 3 kV 15 cm Comparative Example 5 80 wt% 4 wt% 16 wt% 13 kV 22 cm

Experimental Example : Measurement of physical properties of film

In order to confirm the electrical characteristics of the electroconductive films prepared in Examples and Comparative Examples, the surface resistance was measured by the ASTM D257 method, and the transmittance was measured by the ASTM D1003 method to confirm the transmission characteristics. The results are shown in Table 2 below .

(1) Transmittance (haze,%)

Measured according to ASTM D1003 and expressed as a percentage. The haze and light transmittance of the film were measured in the visible light region using a haze meter (TOYOSEIKI, Japan).

(2) Surface resistivity (Ω / sq)

The surface resistivity (? / Sq) was measured according to ASTM D257 under the conditions of 23 占 폚 and 60% RH.

division Permeability (%) Surface resistivity (Ω / sq) Example 1 91 655 Example 2 90 631 Example 3 87 553 Example 4 88 532 Example 5 88 644 Example 6 87 648 Example 7 85 661 Example 8 89 758 Example 9 89 583 Comparative Example 1 86 1,100 Comparative Example 2 74 547 Comparative Example 3 88 Not measurable Comparative Example 4 89 Not measurable Comparative Example 5 90 Not measurable

From the results of the experiment shown in Table 1, it can be seen that Examples 1 to 9 of the present invention show a high transmittance of 80% or more and a low surface resistance of 800 Ω / sq or less. However, Comparative Example 1 produced by the casting method showed a very high surface resistivity, and Comparative Example 2 using too much electroconductive material showed good surface resistivity, but the transparency was too low. In Comparative Example 3 in which the amount of the electrically conductive material was too small, the transparency was excellent, but the surface resistivity could not be measured. In addition, in the case of Comparative Example 4 and Comparative Example 5, in which the voltage and the radiation distance in the case of the electrospinning of the present invention were out of range, the surface resistivity could not be measured either because failure of formation of the nanobubbles by the spinning conditions, This is probably due to a problem that can not be done.

Through the Examples and Experimental Examples, it was confirmed that the transparent electroconductive film of the present invention has excellent transparency (or transparency) and excellent electrical properties. The transparent electrically conductive film of the present invention is expected to be widely used in various display parts and various fields such as a touch screen, a functional inner and outer window, a flexible display electrode, a transparent electrode, an OLED electrode, and a solar cell.

Claims

A polymer selected from the group consisting of polyethylene oxide, fluoropolymer, sulfonated polysulfone, sulfonated polyimide, sulfonated polyether sulfone, sulfonated polyether ether ketone and phosphate complex polybenzimidazole, polyvinylidene fluoride and polyacrylonitrile A polymeric resin comprising at least one of the above;
Electrically conductive material; And
Polydopamine resins;
Wherein the transparent electroconductive film composition is a transparent electroconductive film.

The electroconductive film composition according to claim 1, which comprises 60 to 95% by weight of the polymer resin, 4 to 35% by weight of the electroconductive material, and 1 to 10% by weight of the polypopamine resin.

The transparent electroconductive film composition according to claim 1, further comprising at least one selected from carbon nanotubes, carbon nanowires, silver nanoparticles, and silver nanowires.

2. The method of claim 1 wherein the electrically conductive material is selected from the group consisting of PEDOT: PSS (poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate)), polyaniline, polydiphenyl, acetylene, poly (T-butyldiphenyl) acetylene, poly (trimethylsilyl) diphenyl (triphenylmethyl) diphenylacetylene, poly (Meth) acrylates such as acetylene, poly (carbazole) diphenylacetylene, polydiacetylene, polyphenylacetylene, polypyridine acetylene, polymethoxyphenylacetylene, polymethylphenylacetylene, (Fluoromethyl) phenylacetylene, and poly (trimethylsilyl) phenylacetylene. The transparent electroconductive film composition of claim 1,

The method of claim 1, wherein the polydopamine resin comprises
Characterized in that it contains 2 to 20 mg / ml of a polypopamine polymer containing at least one selected from the group consisting of polypopamine represented by the following general formula (1) and polydodamine represented by the following general formula (2) Conductive film composition.
[Chemical Formula 1]

(2)

The method of claim 5, wherein the polydopamine resin comprises
Further comprising at least one oxidizing agent selected from the group consisting of sodium iodate, dimethyl dioxylan, potassium permanganate, hydrogen peroxide, trifluoroperacetic acid, N-methylmorpholine N-oxide and oxone.

A transparent electroconductive film comprising the electroconductive film composition of any one of claims 1 to 6.

The transparent electrically conductive film according to claim 7, having a surface resistance of 450 to 800? / Square as measured by the ASTM D257 method and a transparency of 80% or more as measured by the ASTM D1003 method.

The transparent electrically conductive film according to claim 7, wherein the transparent electroconductive film has an average thickness of 10 to 200 占 퐉.

A method for producing a transparent electroconductive film by conducting electrospinning an electroconductive film composition of any one of claims 1 to 6.

11. The method of claim 10,
Wherein the electrospinning is carried out at a temperature of 20 ° C to 80 ° C, a voltage of 5 to 15 kV and a radiation distance of 10 to 20 cm.