KR101081524B1 - Conductive Film and Sheet, and Method for preparing the same - Google Patents

Abstract

The present invention relates to a large-area conductive film and sheet having flexibility and transparency, and a manufacturing method thereof, comprising: a functional polymer substrate; A conductive metal layer coated on the functional polymer substrate; Conductive polymer layer coated on the conductive metal layer; and includes, the conductive metal layer is a lattice-shaped conductive film and sheet. The conductive metal powder forming the conductive metal layer includes silver (Ag), silver coated Cu, copper, aluminum, nickel, iron, tin, tin and zinc. The conductive metal powder selected from the group consisting of (Zn) can be mixed and used in an appropriate blending ratio according to the electrical properties. The metal layer forms a layer by a method of printing a metal powder by deposition or mixing with an organic binder to prepare a paste. The conductive polymer layer is made of polythiophene or its derivative poly (3,4-ethylenedioxythiophene), polyaniline, polypyrrole and its derivatives, or a conjugated structure It can be formed by the method of coating by thermal curing and UV curing using a polymer having a method of coating the monomer of the conductive polymer by the in-situ method. According to the present invention, it is possible to obtain a conductive thin film sheet and a film which not only reduce cost and have high reliability, but also have excellent resistance characteristics in flexibility, transparency, and large area. The present invention is antistatic, electromagnetic wave absorber, electromagnetic shielding material, photochemical cell, electrochromic device (ECD) film and sheet, cable shielding, light emitting diode device (LED) film and sheet and hole transport layer application, transparent Applications include conductive films and sheets, field effect transistors (FETs), and polymer dispersed liquid crystal (PDLC) displays.

Conductive films and sheets, flexibility, transparency, metal layers, conductive polymers

Description

Conductive Film and Sheet, and Method for Preparing the Same {Conductive Film and Sheet, and Method for preparing the same}

  1 is a plan view of a conductive film and a sheet according to an embodiment of the present invention.

 The recent development of scientific civilization has provided many conveniences to human life. In particular, the development of electrical, electronic and communication-related equipment is playing a part in making our lives more convenient and profitable. The scientific civilization, which provides convenience to humans, has both sides which may be good or bad depending on how and where it is used.

 One of the latest scientific literature that harms humans is electromagnetic waves. The production and transmission of electricity, radio and television, telephone and other communications, microwave ovens and ovens, airplanes and ships sailing, space exploration, everything is unimaginable. As technology develops, electronics will pour and electromagnetic waves will increase. Even now, electromagnetic waves wander around us as colorless and odorless, like the air we breathe. However, these electromagnetic waves, which are indispensable to humans, are also called electromagnetic interference (EMI), which disturbs other electromagnetic waves, causing malfunction of various machines, causing industrial accidents, and directly or indirectly affecting the human body. In addition, efficiency and shortening of lifespan of internal electronic products caused by high voltage generators of automobiles, mutual disturbance between electronic equipments, glaucoma that can be caused by long-term exposure to microwaves of human body, and reduction of fertility are mentioned. . The space inhabited by modern people is no longer a safe zone from electromagnetic waves, and as scientific civilization develops, its seriousness will increase. The human body has a microscopic electronic signaling system that enables mechanisms of emotion regulation, memory, and behavior. Pregnancy, childbirth, illness and stress in human history would be shocking if they were never related to electromagnetic waves, but that is true. Under these circumstances, advanced countries such as the United States, Japan, and the Soviet Union have established safety exposure standards for electromagnetic waves to strongly regulate external exposure, and continue to study the harmfulness of electromagnetic waves.

In particular, in order to maintain high-quality information and minimize the impact on the human body, which has been derived in proportion to the rapidly increasing information and communication in the 21st century's high information and communication era, advanced countries have already been in business for over 20 years. EMI has been regulated for a long time, and recently, it has been very active in protecting the electromagnetic environment by forcing the maintenance of EMI.

As life becomes rich, the development of the information society has accelerated, and the amount of information that humans can access is enormous, and the types of information are diversified. One of such media is an image information display apparatus, and multiple displays are currently used. ELD (Electroluminescence Device) applied to electric and electronic products such as PCS terminals, Pager, etc. and various display panels is an active solid state display device that emits energy by interaction between energetic electrons generated by high electric field and emission center. After OWDestriau discovered the EL phenomenon by inserting a crystalline powder of ZnS: Cu between two films and sheets in 1936 and applying alternating current electric field, the research on powder type EL was concentrated. In 1969, D. Kahng et al. ZnSahcp Multicolor EL luminescence was observed by adding transition element Mn and rare earth fluoride compound. In 1974, the research result of thin film type EL device by T. Inoguchi et al. The EL element is of interest as a new display device because of its advantages of being heavier in weight, very thin in thickness, and capable of achieving uniform light emission and large area compared to the CRT, which is mainly used as an information display element.

The general EL device is manufactured by screen printing method which is simple, thin film, large area, and can be produced in various patterns by using phosphor paste, dielectric paste and silver paste as basic materials.

As described above, a material used as a conductive electromagnetic shielding material or display electrode having flexibility and transparency was a material coated with ITO or a conductive polymer. However, conventional ITO coated film or sheet has a disadvantage in that it is difficult to industrialize because of the disadvantages of the large area and the price problem. In particular, large-area ITO coating has a large change in resistance, which not only reduces electromagnetic shielding efficiency but also reduces brightness and luminous efficiency when used as a display electrode. In addition, films and sheets coated with conductive polymers such as polythiophene, poly (3,4-ethylenedioxythiophene), polypyrrole, polyaniline, and derivatives thereof have a high surface resistance of 10E4 to 10E5 Ω / □. Therefore, the use of antistatic films and sheets is limited, so it is difficult to use as an electrode for electromagnetic shielding and display that require excellent surface resistance.

 An object of the present invention is to secure the shortcomings of the large area of ITO and the disadvantage of high surface resistance of the conductive polymer, which is a disadvantage of the prior art, and there is almost no change in resistance in the large area. To produce a conductive film and sheet having flexibility and transparency that can exhibit excellent shielding efficiency and brightness, luminous efficiency in use.

 BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a conductive film and sheet having a large area with flexibility and transparency, and a method for manufacturing the same and an application thereof, and particularly, to secure the disadvantage of the large area of ITO, which is a disadvantage of the above, and the high surface resistance of the conductive polymer. Thus, a conductive film and sheet having flexibility and transparency and excellent surface resistance in a large area are provided.

According to one embodiment of the invention, the invention is a functional polymer substrate; A conductive metal layer coated on the functional polymer substrate; And a conductive polymer layer coated on the conductive metal layer, and the conductive metal layer has a lattice shape.
According to another embodiment of the present invention, the present invention is a functional polymer substrate; A conductive polymer layer coated on the functional polymer substrate; And a conductive metal layer coated on the conductive polymer layer, wherein the conductive metal layer has a lattice shape.
According to one embodiment, as the functional polymer substrate, polyester having a transparency and opacity, polycarbonate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polyolefin and polyurethane may be used.
In example embodiments, the conductive metal layer may include silver (Ag), silver coated copper, copper, aluminum, nickel, iron, tin, and tin. It is formed using a powder of metal made of zinc (Zn). These electroconductive powders are mixed and used in an appropriate compounding ratio according to electrical characteristics. According to an embodiment, a layer may be formed by printing by adjusting the lattice spacing, width, and height of the metal paste by using a screen printing method, etc., after preparing a paste by mixing the metal with an organic binder or deposition. .
Examples of the conductive polymer forming the conductive polymer layer include a polythiophene or a derivative thereof such as poly (3,4-ethylenedioxythiophene), polyaniline, polypyrrole, and a derivative thereof. Or a polymer having a conjugated structure can be used.
The conductive polymer layer may be coated by thermal curing and UV curing using the polymer and a method of coating monomers of the conductive polymer by an in-situ method.
According to the present invention, there is an advantage in that it is possible to obtain a thin film sheet and a film, which not only reduce cost and have high reliability, but also have excellent resistance characteristics in flexibility, transparency, and large area. The conductive film and sheet according to the present invention are antistatic, electromagnetic wave absorber, electromagnetic wave shielding material, photochemical battery, electrochromic device (ECD) film and sheet, cable shielding, light emitting diode device (LED) film and sheet And hole transport layer applications, transparent conductive films and sheets, field effect transistors (FETs), and polymer dispersed liquid crystal (PDLC) displays.

The manufacturing method of the conductive film and sheet | seat with which a large area which has flexible transparency by this invention is as follows.

(Example 1)

In the present invention, a metal paste is printed on a polyester film, particularly a polyethylene terephthalate (PET) film substrate, which is a transparent insulator film, using a roll screen printing method. Detailed paste preparation method is as follows.

The metal paste composition of this invention consists of the ratio of 1.0-60.0% of conductive metal powder and 40.0-99.0% of an organic binder.

Silver powder, copper powder, and silver coated copper powder are used as the conductive metal powder. However, the metal powder of the Flake type is used to have excellent electrical characteristics. These metal powders are prepared by the conventional coprecipitation method which is well known in the art.

   In addition, the composition of the organic binder in the invention is very important because it determines the fluidity of the metal paste and the dryness of the coated metal film and the molded sheet and film, and determines the dispersibility of the metal powder, as well as the composition of the dried coating film, sheet and film. This is because the surface roughness characteristics, flexibility, tensile strength, and adhesion to the adherend are influenced. The organic binder of the present invention has the following composition in order to improve the fluidity and dryness of the slurry composition, the dryness of sheets and films, the dispersibility of metal powder, and the like. All% shown below is a weight%.

Acetic acid alkyl ester

(Acetic acid alkyl (methyl, ethyl, butyl) ester): 20.0-80.0%

Diethylene glycol monobutyl ether

(Diethylene glycol monobutyl ether): 5.0-20.0%

Isopropyl alcohol: 10.0-20.0%

Acetone: 10.0-20.0%

Dibutyl phthalate: 0.5-5.0%

Phosphate esther: 0.5-1.0%

Ethylcellulose: 1.0-20.0

   First, each component of the organic binder having the above composition is weighed and placed in an organic binder manufacturing tank maintained at 25 ° C. or lower by a water jacket, followed by stirring with a mixer made of a turbine type impeller. The organic binder is prepared by completely dissolving the components.

   Next, the organic binder 40.0-99.0% prepared as described above and the conductive metal powder (Ag, Cu, Ag coated Cu) prepared by the coprecipitation method were weighed at a composition ratio of 1.0-60.0% and maintained at 25 ° C or below by a water jacket. Into the slurry manufacturing tank to be mixed by the mixer (anchor type) of the impeller (Impeler) at a speed of 1-100rpm for 0.5-5 hours (Mixing) to disperse the metal powder evenly. After mixing, paint is filled in the paint storage container by automatic packing device and then sealed to manufacture the final product. The rolls of the printed metal paste are manufactured using roll screen printing. The thickness of the metal paste is 1 mm (mm) to 10 centimeters (cm), the height is 1 micrometer (um) to 10 mm (mm), and the width is 1 micrometer. (um) ~ 1 cm (cm) to form a thin film sheet and film of the desired spacing, height, thickness.

The conductive polymer layer is coated on the film or sheet on which the conductive metal is printed. Formation of the conductive polymer layer is as follows. 10 to 70% of poly (3,4-ethylenedioxythiophene) aqueous solution (PEDOT) which is a conductive polymer, preferably 30 to 40%, and 5 to 40% of polymer binder such as acrylic, urethane or urethane acrylic, preferably 10 To 20%, organic solvents such as dimethyl sulfoxide (DMSO) and enmethylpyrrolidinone (NMP), 1 to 30%, preferably 15 to 20%, alcohol solvent 20 to 60%, preferably isopropyl alcohol 30 to 50%, 1 to 5% of additives such as slip and wetting, 20 to 60% of dilute solvent, etc. are mixed. The mixed conductive polymer binder is coated on a conductive metal-printed film or sheet with a thickness of 0.1 micrometer (um) to 100 mm (mm) and surface resistance of 10E1 to 10E7 by coating methods such as gravure, laminating, and roll methods. Fabrication of Flexible Films and Sheets with Flexibility, Transparency, and Large Area Resistance The resistivity of the large-area conductive films and sheets produced with flexibility and transparency ranged from 0.05 to 10E2Ω / □.

(Example 2)

In the production of films and sheets capable of flexibility, transparency, and large area under the same conditions as in Example 1, the functional polymer substrate having transparent and opacity as the functional polymer substrate is selected from the group consisting of polyester, polycarbonate, polystyrene, A large area conductive film and sheet having flexibility and transparency was prepared using a sheet or film obtained from a material selected from the group of polyvinyl chloride, polyethylene terephthalate, polyolefin and polyurethane, and the resistance of the film and sheet was 0.05 to 10E2Ω / □ is shown.

(Example 3)

In manufacturing films and sheets capable of flexibility, transparency, and large area under the same conditions as those of Example 1, the conductive polymers were made of 50% water-soluble polypyrrole (or water-soluble polyaniline), 10% polymer binders such as acrylic, urethane or urethane acrylic, and dimethyl. 10% organic solvents such as sulfoxide (DMSO) and enmethylpyrrolidinone (NMP), 25% isopropyl alcohol as an alcohol solvent, 5% additives such as slip and wetting . Using to form a conductive polymer layer, the resistance of the prepared film and sheet showed 0.1 ~ 10E2Ω / □.

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(Example 4)

Conductive polymer layer is formed in the same manner as in Example 1 to prepare films and sheets capable of flexibility, transparency and large area as follows. As an oxidizing agent, iron trichloride (or iron chloride, iron sulfate, iron perchlorate, toluene sulfate, iron ammonium sulfate, etc.) was dissolved in an alcoholic solvent 2-5%, spin-coated with PET, the substrate film, and then 3 Dry for 4 minutes. At 20 ° C., the monomer 3,4-ethylenedioxy thiophene (or pyrrole, aniline) is reacted on an oxidant coated PET film. The unreacted material was washed with an alcohol solvent to produce conductive films and sheets capable of flexibility, transparency and large area. The resistance of the produced film and sheet was 0.05 ~ 10E2Ω / □.

(Example 5)

35% poly (3,4-ethylenedioxythiophene) aqueous solution (PEDOT) as a conductive polymer, 15% polymer binder such as acryl, urethane or urethane acryl, dimethyl sulfoxide (DMSO), enmethylpyrrolidinone (NMP) 10% of an organic solvent, 35% of isopropyl alcohol, which is an alcohol solvent, and 5% of an additive such as a slip and a wetting agent are mixed. The mixed conductive polymer solution was coated on a polyester (PET) film as an insulator and dried at 80 ° C. for 5 minutes to prepare a conductive film having a surface resistance of 10E5 Ω / □. The silver binder prepared in Example 1 was coated on the prepared conductive film at intervals of 0.2 micrometer (um) in height, horizontally and vertically 15 mm by screen roll printing to prepare a film having flexibility, transparency and large area. It was. The resistance of the large-area conductive film having flexibility and transparency produced was 0.05? / Sq.

(Example 6)

35% polypyrrole aqueous solution as conductive polymer, 15% polymer binder such as acryl, urethane or urethane acryl, 10% organic solvents such as dimethyl sulfoxide (DMSO) and enmethylpyrrolidinone (NMP), isopropyl alcohol 35 as alcohol solvent %, 5% of additives such as slip and wetting, etc. are mixed. The mixed conductive polymer solution was coated on a polyester (PET) film as an insulator and dried at 80 ° C. for 5 minutes to prepare a conductive film having a surface resistance of 10E5.6 Ω / □. The silver binder prepared in Example 1 was coated on the prepared conductive film at intervals of 0.2 micrometer (um) in height, horizontally and vertically 15 mm by screen roll printing to prepare a film having flexibility, transparency and large area. The resistance of the large-area conductive film having flexibility and transparency produced was 0.1 Ω / square.

(Example 7)

35% polyaniline aqueous solution as conductive polymer, 15% polymer binder such as acryl, urethane or urethane acryl, 10% organic solvent such as dimethyl sulfoxide (DMSO), enmethylpyrrolidinone (NMP), isopropyl alcohol 35 as alcohol solvent %, 5% of additives such as slip and wetting, etc. are mixed. The mixed conductive polymer solution was coated on a polyester (PET) film as an insulator and dried at 80 ° C. for 5 minutes to prepare a conductive film having a surface resistance of 10E6 Ω / □. The silver binder prepared in Example 1 was coated on the prepared conductive film at intervals of 0.2 micrometer (um) in height, horizontally and vertically 15 mm by screen roll printing to prepare a film having flexibility, transparency and large area. The resistance of the large-area conductive film having flexibility and transparency produced was 0.12Ω / □.
Physical properties of the films and sheets prepared in Examples 5 to 7 are shown in Table 1 below.
Table 1 Measurement results of the surface resistance of the film and sheet prepared in Example
Conductive polymer Silver Paste (0.2um in height, 1mm in width) 15 mm thickness 30 mm thickness 50 mm thickness PEDOT 0.05Ω / □ 0.08Ω / □ 0.12Ω / □ Polypyrrole 0.1Ω / □ 0.14Ω / □ 0.19Ω / □ Polyaniline 0.12Ω / □ 0.17Ω / □ 0.21Ω / □

(Example 8)

As an oxidizing agent, iron trichloride (or iron chloride, iron sulfate, iron perchlorate, toluene sulfate, iron ammonium sulfate, etc.) was dissolved in an alcohol solvent by 3%, spin-coated with PET, a substrate film, and then 3 to 4 at 60 to 70 ° C. Dry for minutes. At 20 ° C., the monomer 3,4-ethylenedioxy thiophene (or pyrrole, aniline) is reacted on an oxidant coated PET film. After the unreacted product was washed with an alcohol solvent, a conductive film was prepared which was flexible, transparent and large in area. The resistance of the film produced showed 10E2Ω / □. The silver binder prepared in Example 1 was coated on the prepared conductive film at intervals of 0.2 micrometer (um) in height, horizontally and vertically 15 mm by screen roll printing to prepare a film having flexibility, transparency and large area. It was. The resistivity of the large-area conductive film having flexibility and transparency produced was 0.05? / Sq.

(Example 9)

In order to examine the applicability of the films prepared in Examples 1, 2, and 3 as electromagnetic wave shielding materials according to the present invention, electromagnetic wave shielding characteristics were measured. For the electromagnetic shielding performance test, the flanged coaxial transmission line measuring tool used as the far field shielding effect measuring tool was used. This tool was measured according to the standard of ASTM: D 4935-89. This measuring jig consists of an inner conductor (3.2 cm outer diameter) and an outer flange (13.3 cm outer diameter and 7.6 cm inner diameter). The shape of the test specimen is disc-shaped. The reference specimen has two pieces so that both coaxial transmission lines can be capacitively coupled through the specimen, and the inner and outer coaxial contact surfaces are empty. Measurement results of the electromagnetic shielding efficiency in the far field of the frequency band between 10MHz ~ 1GHz of the film prepared in Examples 1, 2, 3 according to the present invention showed an electromagnetic shielding efficiency of 65 ~ 70 dB.

As described above, the present invention relates to a conductive film and sheet having a large area with flexibility and transparency, and to a manufacturing and application thereof, and particularly preferred for replacing ITO, which is used as an existing conductive film and sheet. In addition to saving and high reliability, there is an advantage in that a thin film sheet and a film having excellent resistance characteristics in flexibility, transparency, and large area can be obtained. Sheets and films according to the present invention include antistatic, electromagnetic wave absorbers, electromagnetic wave shielding materials, photochemical cells, electrochromic device (ECD) electrodes, cable shielding, light emitting diode device (LED) electrodes and hole transport layer applications, Applications include transparent conductive electrodes, field effect transistors (FETs), and polymer dispersed liquid crystal (PDLC) displays.

Claims (10)

Functional polymer substrates; A conductive metal layer coated on the functional polymer substrate; And And a conductive polymer layer coated on the conductive metal layer. A conductive film and sheet, wherein the conductive metal layer has a lattice shape. Functional polymer substrates; A conductive polymer layer coated on the functional polymer substrate; And And a conductive metal layer coated on the conductive polymer layer. A conductive film and sheet, wherein the conductive metal layer has a lattice shape. The method according to claim 1 or 2, A conductive film characterized in that the functional polymer substrate is a sheet or film obtained from a material selected from the group consisting of polyesters, polycarbonates, polystyrenes, polyvinyl chlorides, polyethylene terephthalates, polyolefins and polyurethanes having transparency and opacity; Sheet. The method according to claim 1 or 2, The conductive metal layer is made of silver (Ag), silver coated Cu, copper, aluminum, nickel, nickel, iron, tin, and zinc. A conductive film and sheet, which is a powder of at least one metal selected from the group. The method of claim 1 In the lattice shape of the conductive metal layer, the spacing between the lattice forming the lattice shape is 1 mm ~ 10 cm, the height of the lattice is 1㎛ ~ 10mm, the width of the lattice is 1㎛ ~ 1cm Conductive film and sheet. The method according to claim 1 or 2 The conductive polymer is a polythiophene or a derivative thereof, poly (3,4-ethylenedioxythiophene) [poly (3,4-ethylenedioxythiophene)], polyaniline, polypyrrole and derivatives thereof. A conductive film and sheet, characterized in that the formed polymer, or a polymer having a conjugated structure. The method according to claim 1 or 2 The conductive film and sheet are metallization, antistatic, electromagnetic wave absorber, electromagnetic wave shielding material, storage battery, IR absorber, photochemical cell, electrochromic device (ECD) electrode, resistive heating , Cable shielding, microwave absorber, temperature, shock, chemical sensor, light emitting diode (LED) electrode, transparent conductive electrode, field effect transistor (FET), polymer dispersed liquid crystal (PDLC) display A conductive film and sheet, characterized in that used in. Coating a metal powder on the functional polymer substrate to form a conductive metal layer; And And forming a conductive polymer layer by coating a conductive polymer on the conductive metal layer. The forming of the conductive metal layer may include depositing the metal powder in a lattice shape; Or mixing the metal powder with an organic binder to prepare a paste, and then printing the grid in a lattice shape. The method of claim 8, Forming the conductive polymer layer is polythiophene (polythiophene) or a derivative thereof poly (3,4-ethylenedioxythiophene) [poly (3,4-ethylenedioxythiophene)], polyaniline (polyaniline), polypyrrole ( a polymer formed of polypyrrole) and derivatives thereof, or a polymer having a conjugated structure, is mixed with an organic binder, an organic solvent and an additive to prepare a conductive resin, and then coated by thermal curing and UV curing. Method of Making Films and Sheets. The method of claim 8 The step of forming the conductive polymer layer is a monomer formed of a thiophene (polythiophene) or a derivative thereof 3,4-ethylenedioxythiophene, aniline (aniline), pyrrole and derivatives thereof Or forming a conductive polymer layer by an in-situ method using a monomer having a conjugated structure by using an oxidizing agent, an additive, or the like.

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