KR101468496B1 - Coating solution having conductive nano material and coated conductive film - Google Patents

Coating solution having conductive nano material and coated conductive film Download PDF

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Publication number
KR101468496B1
KR101468496B1 KR1020130087791A KR20130087791A KR101468496B1 KR 101468496 B1 KR101468496 B1 KR 101468496B1 KR 1020130087791 A KR1020130087791 A KR 1020130087791A KR 20130087791 A KR20130087791 A KR 20130087791A KR 101468496 B1 KR101468496 B1 KR 101468496B1
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South Korea
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conductive
conductive film
region
photosensitive
exposed region
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KR1020130087791A
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Korean (ko)
Inventor
신권우
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전자부품연구원
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Priority to KR1020130087791A priority Critical patent/KR101468496B1/en
Priority to CN201480009151.1A priority patent/CN105073912B/en
Priority to US14/760,089 priority patent/US9977327B2/en
Priority to PCT/KR2014/002057 priority patent/WO2014157856A1/en
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Publication of KR101468496B1 publication Critical patent/KR101468496B1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors

Abstract

The present invention relates to a photosensitive coating composition including conductive nanomaterials and a coated conductive film using the same. The present invention is to allow electricity to flow in a specific pattern shape by forming difference in electrical conductivity in a local region of a conductive film by using a simple exposure method without directly etching the conductive film including conductive nanomaterials. The present invention provides the photosensitive coating composition for manufacturing the coated conductive film comprising 0.01-5 wt% of conductive nanomaterials, 0.01-3 wt% of photosensitive materials, and 1 wt% or less of binders. The present invention provides the coated conductive film formed on a substrate by using the photosensitive coating composition. The coated conductive film comprises the conductive nanomaterials, ultraviolet sensitive materials, and binders and includes an exposed region and a non-exposed region by exposing and washing. The non-exposed region has electrical conductivity more than two times than the exposed region.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive coating liquid composition including a conductive nanomaterial and a coating film using the conductive nanomaterial and a conductive film,

More particularly, the present invention relates to a photosensitive coating liquid composition containing a conductive nanomaterial such as a metal nanowire or nano carbon, and a coated conductive film using the same.

The conductive thin film including metal nanowires or nanocarbon can be formed by coating on a substrate as a conductive film formed by successive contact of conductive nanomaterials in the form of wires, tubes, and nanoparticles. The conductive film including metal nanowires or nanocarbon can be formed as a conductive film having electrical conductivity by forming a dispersion by coating with various substrates by a simple solution process and thus can be used as a transparent electrode and a circuit electrode in a touch panel, have.

In order to use a conductive film composed of a metal nanowire or nano carbon as a transparent electrode or a circuit electrode, it is necessary to control electric connection and non-connection in a local region of the conductive film to conduct electricity in a specific pattern form.

Photolithography and a laser etching process were mainly applied to form a wiring pattern on a conductive substrate having a conductive film formed thereon. In the photolithography process, a photoresist is coated on a conductive film, a photoresist pattern is formed on the conductive film by exposing and developing ultraviolet rays, and then a wiring pattern is formed by etching the conductive film in a specific pattern by a wet or dry method. The laser etching method is a method of forming a wiring pattern by etching a conductive film in a specific pattern using a laser.

This method can form a fine pattern of the conductive film using existing known processes. However, due to the difference in the distribution of the metal nanowires or nano-carbon in the etched region and the unetched region in the conductive film having the wiring pattern, the wiring pattern of the conductive film is visually recognized due to the formation of the light reflectance, light transmittance and haze difference .

In addition, in the case of the photolithography process, a separate process is required to form a wiring pattern of the conductive film, which requires a further additional processing cost and low productivity.

U.S. Patent No. 8,018,568 (September 23, 2011)

It is therefore an object of the present invention to provide a photosensitive coating solution containing a conductive nanomaterial capable of electric conduction in a specific pattern form by forming a difference in electric conductivity in a local region of the conductive film by using a simple exposure method without direct etching of the conductive film containing the conductive nanomaterial And a coated conductive film using the same.

Another object of the present invention is to provide a method of forming a conductive film having a different electrical conductivity in a localized region, but a conductive nanomaterial corresponding to a conductive filler of the conductive film is uniformly distributed over the entire conductive film, The present invention also provides a photosensitive coating composition comprising the conductive nanomaterial and a coated conductive film using the same.

Still another object of the present invention is to provide a photosensitive coating liquid composition comprising a conductive nanomaterial that is not chemically / physically etched in a specific region of the conductive film, is oxidized by a chemical method or does not form a sulfide, and the conductive nanomaterial is hardly damaged, And to provide a coated conductive film using the same.

In order to achieve the above object, the present invention provides a photosensitive coating solution composition for the production of a coated conductive film, which comprises 0.01 to 5% by weight of a conductive nanomaterial, 0.01 to 3% by weight of a photosensitive material, and 1% by weight or less of a binder.

In the photosensitive coating liquid composition according to the present invention, the conductive nanomaterial is a metal nanowire or nanocarbon. The photosensitive material is a polyvinyl alcohol having a photosensitive functional group. And the binder is a water-dispersible polyurethane or a cationic polymer electrolyte.

In the photosensitive coating liquid composition according to the present invention, the cationic electrolyte is selected from the group consisting of poly (diallydimethylammonium chloride), poly (allyamine hydrochloride), poly (3,4-ethylenedioxythiophene) (PEDOT) , poly (acrylamide-co-diallylmethylammonium chloride), cationic polythiophene, polyaniline, poly (vinylalcohol), or derivatives thereof.

The present invention also relates to a coated conductive film formed on a substrate, comprising a conductive nanomaterial, an ultraviolet sensitive material and a binder, wherein the exposed and unexposed areas are formed by exposure and cleaning, To provide a coated conductive film having an electrical conductivity of at least two times the exposed area.

In the coated conductive film according to the present invention, the conductive nanomaterial is metal nanowire or nanocarbon. The photosensitive material is a polyvinyl alcohol having a photosensitive functional group. And the binder is a water-dispersible polyurethane or a cationic polymer electrolyte.

In the coated conductive film according to the present invention, the non-exposed region may include a polymeric substance including a photosensitive polymeric substance which is removed in the cleaning process more than ultraviolet light-sensitive material and finally remains in the coated conductive film Is lower.

In the coated conductive film according to the present invention, the conductive nanomaterials are similarly distributed to the non-exposed region and the exposed region, and there is no difference in degree of damage of the nanomaterial.

In the coated conductive film according to the present invention, the exposed region has a structure in which the conductive nanomaterial is impregnated with the polymer substance more than the non-exposed region.

According to the present invention, after forming a photosensitive thin film including a photosensitive material and a binder together with a conductive nanomaterial on a substrate, the photosensitive thin film is exposed and washed according to the shape of a wiring pattern to be formed, A wiring pattern having a conductivity difference can be formed.

That is, the photosensitive coating composition for forming a photosensitive thin film contains a photosensitive material, a binder, and other compositions in addition to the conductive nanomaterial. When the photosensitive thin film is exposed to ultraviolet rays, physical or chemical bonds between the photosensitive material and the photosensitive material and other compositions are formed or broken to form a difference in solubility with respect to a specific solvent such as water. The area where the photosensitive material and other compositions are removed much when exposed to the solvent exhibits high electrical conductivity and the area where the photosensitive material and other compositions are less removed shows a low electrical conductivity. For example, when the photosensitive thin film is exposed and then washed with a solvent, relatively large portions of the photosensitive material and other compositions are removed from the unexposed portion as compared with the exposed portion, so that the exposed portion and the unexposed portion form a pattern of electric current flow The difference in the electrical conductivity is enough to be able to do.

As described above, the present invention forms a wiring pattern capable of flowing electricity in a specific pattern form by forming a difference in electrical conductivity in a local region of a coated conductive film by using a simple exposure method without direct etching on a coated conductive film including a conductive nanomaterial can do.

The coated conductive film according to the present invention forms a wiring pattern by a post-exposure cleaning process to form a difference in electric conductivity in the local region. However, the conductive nanomaterial corresponding to the conductive filler of the coated conductive film is distributed in different regions having different electric conductivity And have a similar distribution structure, similar distribution density.

The present invention can also provide a coated conductive film comprising a conductive nanomaterial that is not chemically and physically etched in a particular region of the coated conductive film, is not oxidized or formed by chemical methods, and is not physically damaged by the conductive nanomaterial have. This makes it possible to control the electrical flow characteristics of the conductive nanomaterials without directly etching the coated conductive film and solve the problem of pattern visibility due to the difference in the distribution of the conductive nano-density, Can be simplified.

1 is a perspective view showing a conductive substrate on which a coated conductive film including a conductive nanomaterial according to the present invention is formed.
2 is an enlarged view of a portion "A" in Fig.
3 is a flow chart according to the method of manufacturing the coated conductive film of FIG.
FIGS. 4 to 7 are views showing respective steps according to the manufacturing method of FIG.
8 is a view showing a structure of an insulation test pattern according to a line width of a wiring pattern of a coated conductive film manufactured according to the first embodiment of the present invention.
9 to 11 are photographs showing a coated conductive film manufactured according to the first embodiment of the present invention.
12 and 13 are photographs showing a coated conductive film manufactured according to the second embodiment of the present invention.

In the following description, only parts necessary for understanding the embodiments of the present invention will be described, and the description of other parts will be omitted so as not to obscure the gist of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and the inventor is not limited to the meaning of the terms in order to describe his invention in the best way. It should be interpreted as meaning and concept consistent with the technical idea of the present invention. Therefore, the embodiments described in the present specification and the configurations shown in the drawings are merely preferred embodiments of the present invention, and are not intended to represent all of the technical ideas of the present invention, so that various equivalents And variations are possible.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a perspective view showing a conductive substrate on which a coated conductive film including a conductive nanomaterial according to the present invention is formed. 2 is an enlarged view of a portion "A" in Fig.

1 and 2, a conductive substrate 100 according to the present invention includes a substrate 10, a conductive nanomaterial 21 formed on the substrate 10, a photosensitive material and a binder, And a coating conductive film 20 on which a wiring pattern 29 is formed.

Here, the substrate 10 may be made of a transparent material having light transmittance. For example, as the material of the substrate 10, any one of glass, quartz, transparent plastic substrate, and transparent polymer film may be used. As the material of the transparent polymer film, PET, PC, PEN, PES, PMMA, PI, PEEK and the like can be used, but the present invention is not limited thereto. The substrate 10 of the transparent polymeric film material may have a thickness of 1 to 10,000 mu m.

The photosensitive coating composition for forming the coating conductive layer 20 may include a conductive nanomaterial 21, a photosensitive material and a binder, and may include other dispersing agents, additives, and the like. For example, the photosensitive coating liquid composition contains 0.01 to 5% by weight of a conductive nanomaterial, 0.01 to 3% by weight of a photosensitive material, 1% by weight or less of a binder, and the other is water. And the photosensitive coating liquid composition may further include not more than 5 wt% of the additive.

Conductive nanomaterial 21 includes metal nanowires or nanocarbons. The metal nanowire may be silver nano wire, copper nanowire, gold nanowire, or the like, but is not limited thereto. As the metal nanowires, metal nanowires having a diameter of 300 nm or less and a length of 1 mu m or more may be used. Metal nanowires include metal nanotubes. As the nano carbon, carbon nanotubes, graphenes, carbon nano plates, carbon black, and the like can be used, but the present invention is not limited thereto.

At this time, the higher the composition ratio of the conductive nanomaterials contained in the photosensitive coating solution, the more the electric conductivity increases and the resistance of the coated conductive film 20 can be lowered. However, when the concentration is too high, that is, when it is more than 5% by weight, it is difficult to disperse the conductive nanomaterial in solution. Therefore, the conductive nanomaterial is preferably used in an amount of 0.1 to 0.5% by weight.

The photosensitive material is preferably a material which is exposed to one or more energy irradiation such as light (infrared light, visible light, ultraviolet light), heat, laser, etc., and the energy source is not limited thereto.

For example, as the photosensitive material, an aqueous photosensitive material having photosensitivity to ultraviolet rays may be used. As the water-soluble photosensitive material, a polyvinyl alcohol material having a photosensitive functional group and polyvinyl alcohol having N-methyl-4 (4'-formylstyryl) pyridinium methosulfate acetal functional group may be used, but the present invention is not limited thereto.

The photosensitive material may have a different concentration depending on the target resistance difference between the exposed region 25 and the unexposed region 27. [ For example, 0.1 to 1% by weight is suitable for forming the pattern of the transparent electrode. However, if the photosensitive material is added too much, the photosensitive material of the non-exposed region 27 may be removed while the conductive nanomaterial 21 is also removed in the post-exposure cleaning process, thereby damaging the transparent electrode or increasing the resistance.

As the binder, a water-dispersible polyurethane or a cationic polyelectrolyte may be used. Examples of cationic electrolytes include poly (diallydimethylammonium chloride), poly (allyamine hydrochloride), poly (3,4-ethylenedioxythiophene) (PEDOT), poly (2-vinylpyridine), poly (ethylenenimine), acrylamide-co-diallylmethylammonium chloride ), cationic polythiophene, polyaniline, poly (vinylalcohol), or derivatives thereof.

The reason for using such a binder is that the polyvinyl alcohol used as the photosensitive material forms a positive charge in the aqueous solution and therefore when the water dispersible polyurethane or the cationic polymer electrolyte is used as the binder, This is because the photosensitive polyvinyl alcohol material in the non-exposed region 27 does not form an electrical or chemical bonding force with the binder during the cleaning process, and thus the photosensitive polyvinyl alcohol material is easily removed by washing.

In addition, the binder functions to fix the conductive nanomaterial 21 corresponding to the conductive filler so that the conductive nanomaterial 21 does not fall off the coated conductive film 20 from which the conductive nanomaterial 21 corresponding to the conductive filler is manufactured during the solvent cleaning process for manufacturing the coated conductive film 20. That is, if the binder is not included in the photosensitive coating solution, the conductive nanomaterial 21 is removed as a photosensitive material or the coating conductive film is not formed or the uniformity of the resistance is greatly reduced during the solvent washing process of the coated conductive film.

The reason for not using an anionic polymer electrolyte as a binder is that when an anionic polymer electrolyte is used as a binder, precipitation occurs in the photosensitive coating liquid and the photosensitive material in the non-exposed region is not removed when the conductive film is washed after the exposure, A problem that the electric conductivity of the electrode is lowered occurs.

As described above, the binder is added to the photosensitive coating solution at 1 weight% or less to prevent the conductive nanomaterial 21 from falling off the substrate 10 during the post-exposure cleaning. At this time, if the content of the binder is high, the adhesion of the conductive nanomaterial 21 to the substrate 10 is improved, but the resistance of the coated conductive film 20 may increase. If the binder is absent or is too small, the conductive nanomaterial 21 may be detached from the substrate 10 during cleaning, and the characteristics of the coated conductive film 20 may deteriorate. On the other hand, when the content of the photosensitive material is as low as 0.1% by weight or less, the adhesion of the conductive nanomaterial 21 to the substrate 10 is maintained without the binder, and thus the production of the coated conductive film 20 according to the present invention is performed You may.

The dispersing agent may be classified into a dispersing agent for metal nanowires and a dispersant for nanocarbon according to the conductive nanomaterial (21) to be used. For example, hydroxypropyl methyl cellulose (HPMC), carboxymethyl cellulose (CMC), and 2-hydroxy ethyl cellulose (HC) may be used as the dispersing agent of the silver nano wire. Examples of dispersants for carbon nanotubes include sodium dodecyl sulfate (SDS), lithium dodecyl sulfate (LDS), sodium dodecylbenzenesulfonate (SDBS), sodium dodecylsulfonate (DTBS), dodecyltrimethylammonium bromide (DTAB), cetyltrimethylammonium bromide (CTAB) , Triton X-series, and poly (vinylpyrrolidone).

The additives can be selectively used for the purpose of improving the coating property of the photosensitive coating liquid, improving dispersibility, preventing metal nano wire corrosion, and improving the durability of the coated conductive film 20. [ For example, the additive can promote the stability of the photosensitive coating fluid (e.g., an oil treatment agent), help wettability and coating properties (e.g., surfactant, solvent additive, etc.), form secondary particles And may assist in the formation of a phase separation structure in the formation of the coating conductive film 20, and may assist in promoting drying.

The coated conductive film 20 according to the present invention includes a conductive nanomaterial 21 uniformly formed on a substrate 10. The coated conductive film 20 may include an exposed area 25 and an unexposed area 27 and the unexposed area 27 may form a wiring pattern 29. [ The electrical conductivity of the exposed region 25 and the non-exposed region 27 may have a difference of two times or more.

The coated conductive film 20 may be formed of one layer including the conductive nanomaterial 21, the photosensitive material and the binder, or may have a structure in which a layer of the photosensitive material is formed on the conductive nanomaterial layer.

As described above, in the coated conductive film 20 according to the present invention, the difference in electrical conductivity between the exposed region 25 and the unexposed region 27 is as follows. The photosensitive thin film including the conductive nanomaterial 21, the photosensitive material and the binder before being formed into the coating conductive film 20, that is, before the ultraviolet light exposure and cleaning, has a very low electric conductivity by the photosensitive material and the binder.

However, when the photosensitive thin film is exposed to ultraviolet rays, physical or chemical bonds between the photosensitive materials or between the photosensitive material and other compositions are formed or broken to form a difference in solubility with respect to a specific solvent. On the other hand, there is little change in the chemical or physical properties of the conductive nanomaterial 21 during the exposure process. Where a particular solvent can be a solvent with high solubility selectively for the photosensitive material. For example, when a water-soluble photosensitive material is used as a photosensitive material, a difference in solubility with respect to water is formed.

That is, the photosensitive material has a high solubility characteristic with respect to a specific solvent before being exposed, but may have a property of being insoluble in the solvent because it is cured upon exposure. Accordingly, the present invention forms the wiring pattern 29 using the difference in solubility of the photosensitive material with respect to a specific solvent.

Therefore, in the photosensitive thin film, the exposed region 25 and the unexposed region 27 form a solubility difference with respect to a specific solvent. Particularly, when the photosensitive thin film contains a large amount of other composition, a difference in electric conductivity between the two regions is greatly formed, and a difference in electric conductivity is large enough to form a pattern of a transparent electrode and a circuit electrode. A region in which a photosensitive material and other compositions are largely removed when exposed to a solvent usually exhibits a high electrical conductivity and a region in which a photosensitive material and other compositions are less removed exhibits a low electrical conductivity.

For example, if the unexposed area 27 is more soluble in solvent than the exposed area 25, the unexposed area 27 is formed in the wiring pattern 29.

In the present invention, the non-exposed region 27 has a higher solubility than the exposed region 25, but may exhibit opposite characteristics depending on the type of the photosensitive substance. That is, when the exposed region 25 has a higher solubility than the unexposed region 27, the exposed region 25 can be formed as a wiring pattern.

The widths of the exposed region 25 and the non-exposed region 27 forming the coated conductive film 20 are 1 탆 or more and the shape of the wiring pattern 29 is determined by exposure. The shape of the wiring pattern 29 is usually determined according to the shape of the mask used for exposure.

The method of manufacturing the coated conductive film 20 according to the present invention will now be described with reference to FIGS. 1 to 7. FIG. Here, FIG. 3 is a flow chart according to the method of manufacturing the coating conductive film 20 of FIG. And FIGS. 4 to 7 are views showing respective steps according to the manufacturing method of FIG.

First, as shown in FIG. 4, a substrate 10 on which a coated conductive film is to be formed is prepared.

Next, as shown in FIG. 5, a photosensitive thin film 23 including a conductive nanomaterial, a photosensitive material, and a binder is formed on the substrate 10 in step S51. That is, the photosensitive coating composition according to the present invention is applied to form a photosensitive thin film 23. The photosensitive coating composition may include a conductive nanomaterial, a photosensitive material, a binder, and water, and may further include other compositions. For example, 0.01 to 5% by weight of a conductive nanomaterial, 0.01 to 3% by weight of a photosensitive material, 1% by weight or less of a binder, and 5% by weight or less of other composition.

Meanwhile, the photosensitive thin film 23 may be formed of one layer including a conductive nanomaterial, a photosensitive material and a binder, or may have a structure in which a photosensitive material layer is formed on a conductive nanomaterial layer. When the photosensitive thin film 23 is formed as a single layer such as an electron, other compositions such as a dispersing agent, an additive, etc. may be included together. In the case of the latter photosensitive film 23, other compositions such as a binder, a dispersant, and an additive are included in the conductive nanomaterial layer.

Subsequently, as shown in FIG. 6, in step S53, a part of the photosensitive thin film 23 is exposed. That is, the photosensitive thin film 23 is exposed to ultraviolet rays by using a mask 30 having a pattern hole 31 corresponding to an area to be exposed.

The ultraviolet exposure time in the exposure process is generally within a few minutes, preferably within a few seconds). There is little change in the chemical and physical properties of conductive nanomaterials during the exposure process.

7, the conductive thin film, which has been exposed in step S55, is washed with a solvent and dried to produce the conductive substrate 100 having the coating conductive film 20 having the wiring pattern 29 formed thereon. The removal of the photosensitive material and other composition in the unexposed area 27 is more likely because the unexposed area 27 is relatively more soluble in solvent than the exposed area 25.

The conductive substrate 100 manufactured by the manufacturing method of the present invention is free from direct etching of the coating conductive film 20 and can be formed in the conductive nano- It is possible to form the coated conductive film 20 having the wiring pattern 29 capable of regulating the electric conductivity in a specific region to form an electric current without damage and chemical conversion of the material.

The photosensitive thin film according to the present invention includes a conductive nanomaterial, a photosensitive material and a binder, and may include other composition materials such as a dispersant and an additive.

As described above, the conductive substrate 100 according to the present invention is formed by forming a photosensitive thin film containing a photosensitive material together with the conductive nanomaterial on the substrate 10, exposing the photosensitive thin film to the shape of the wiring pattern 29 to be formed, , The coated conductive film 20 having the wiring pattern 29 having the electrical conductivity difference between the exposed region 25 and the unexposed region 27 can be formed.

That is, the photosensitive thin film includes other compositions such as a dispersing agent and an additive in addition to the conductive nanomaterial. When the photosensitive thin film is exposed to light, physical or chemical bonds between the photosensitive materials or between the photosensitive material and the other composition are formed or broken to form a difference in solubility with respect to a specific solvent such as water. The area where the photosensitive material and other compositions are removed much when exposed to the solvent exhibits high electrical conductivity and the area where the photosensitive material and other compositions are less removed shows a low electrical conductivity. For example, washing with a post-exposure solvent for the photosensitive film results in a relatively high removal of photosensitive materials and other compositions in the unexposed areas 27 relative to the exposed areas 25, The region 27 has a difference in electric conductivity so as to form a pattern of electric current.

Thus, the present invention provides a method of forming an electrical conductivity difference in a localized region of a coated conductive film 20 using a simple exposure method without direct etching of the coated conductive film 20 comprising the conductive nanomaterial, It is possible to form the wiring pattern 29 which can flow.

In addition, the conductive substrate 100 according to the present invention forms a coating conductive film 20 having a different electrical conductivity in the local region by forming the wiring pattern 29 in the post-exposure cleaning process, The conductive nanomaterials corresponding to the conductive filler of the conductive film 20 are all distributed even in regions having different electric conductivity and can be uniformly distributed over the entire coated conductive film 20. [

The present invention also relates to a conductive substrate 20 comprising a conductive nanomaterial that is not chemically and physically etched in a particular region of the coated conductive film 20, is not oxidized or sulfide formed by a chemical method, and is not physically damaged by the conductive nanomaterial (100).

In addition, the coated conductive film 20 according to the present invention has a problem that a pattern visibility problem occurs due to the presence of the conductive nanomaterials in the exposed region 25 and the unexposed region 27 similarly even when the exposure and cleaning are performed .

The characteristics of the coated conductive film will be described below with reference to the conductive substrate according to the present invention.

First Embodiment

The conductive substrate according to the first embodiment of the present invention uses a PET film as a substrate and a silver nano wire as a conductive nano material.

That is, in the first embodiment, a silver nano wire coating liquid containing a silver nanowire, a photosensitive polyvinyl alcohol as a water-soluble photosensitive material, and a water-dispersible polyurethane binder is coated on a substrate and exposed and washed to form a high conductivity region and a low conductivity region To form a pattern. The silver wire was 20 to 40 nm in diameter and 10 to 30 탆 in length. At this time, silver nano wire (0.15 wt%), photosensitive polyvinyl alcohol (0.6 wt%) as a water-soluble photosensitive material, dispersant HPMC (0.2 wt%) and water dispersible polyurethane binder (0.01 wt%) were contained in the silver nano wire coating solution.

The silver nano wire aqueous dispersion was coated on the substrate by a bar coating method, and the coated substrate was dried at a temperature of 130 ° C for 1 minute. The sheet resistance value of the dried photosensitive thin film was high (not less than 10 MΩ / sq) so as not to be measured by the sheet resistance meter. The photosensitive thin film was irradiated with ultraviolet rays for 1 second in a specific pattern form using a chromium photomask and post baking at 130 캜 for 5 minutes. Then, the coated conductive film according to the first embodiment formed on the substrate can be obtained by washing with water as a solvent and drying.

The ultraviolet ray exposure area of the coated conductive film according to the first example was formed by a straight line having various line widths as shown in Fig. 8, and the insulating property according to the exposure line width was examined. 8 is a view showing a structure of an insulation test pattern according to a line width of a wiring pattern of a coated conductive film manufactured according to the first embodiment of the present invention.

Referring to FIG. 8, the ultraviolet exposure line is formed of a transparent conductive film that is visible with a slight translucent line, but the translucent line of the exposure line is not visible when another polymeric material is overcoated or adhered to another film thereon.

The exposure line has a linear shape with different line widths, and the resistance is measured with each exposure line as a boundary. The first exposure line 41 formed between the A region and the B region has a line width of 150 mu m. And the second exposure line 42 formed between the B region and the C region has a line width of 100 mu m. The third exposure line 43 formed between the C region and the D region has a line width of 60 mu m. The fourth exposure line 44 formed between the D region and the E region has a line width of 40 mu m. The fifth exposure line 45 formed between the E region and the F region has a line width of 30 mu m. And the sixth exposure line 46 formed between the F region and the G region has a line width of 20 mu m. The first to sixth exposure lines were formed to have a length of 80 mm.

The resistance values of the first to fourth exposure lines 41, 42, 43 and 44 were all 10 MΩ / sq or more, and the insulation of the exposure line was high enough that the resistance measurement by the resistance measuring device was impossible. The resistance value of the fifth exposure line 45 was 20 to 30 kΩ, and the resistance value of the sixth exposure line 46 was measured to be 2 kΩ.

The areas A, B C, D, E, F, and G are areas having high electrical conductivity to the areas where the photosensitive material has been removed by washing into the respective non-exposure areas. In this region, the sheet resistance value was 120 ~ 150? / Sq, the light transmittance was 90%, and the haze was 1.5.

In order to examine the surface morphology of the portion irradiated with the ultraviolet ray and the portion irradiated with the ultraviolet ray, the ultraviolet ray exposure line and the non-exposed region were observed with an electron microscope, as shown in Figs. 9 to 11 are photographs showing the coated conductive film manufactured according to the first embodiment of the present invention.

As a result of analysis, it was found that all of the silver nanowires are uniformly distributed in the ultraviolet exposure line regions (a) and (b) and the ultraviolet light non-exposure regions (c) and (d) .

However, in the enlarged electron microscopic images (b) and (d), in the ultraviolet exposure line area (b), the silver nano-irid is covered by the photosensitive material and the binder and impregnated more than the ultraviolet non- The contact characteristics between the wires are not good and the resistance is increased. In (b) and (d), the binder polyurethane prevents silver nano wire from falling off during the cleaning process by bonding the silver nano wire to the substrate.

A, B, C, D, E, and E are formed on the conductive substrate according to the first embodiment after exposing again 5 seconds to the ultraviolet rays of the same output, in order to confirm the damage of the silver nano wire itself by the ultraviolet ray exposure, F, and G, respectively. The sheet resistances of the A, B, C, D, E, F, and G regions before UV exposure were 120-150? / Sq and the light transmittance was 90%. The sheet resistance of the A, B, C, D, E, F, and G areas was 120 ~ 150 Ω / sq and the light transmittance was 90% after 5 seconds of ultraviolet exposure. Able to know.

Second Embodiment

As a second embodiment, a pattern composed of a region having a high conductivity and a region having a low conductivity was formed using a carbon nanotube / silver nano wire photosensitive coating solution.

The carbon nanotube / silver wire sensitizing coating solution includes single-wall carbon nanotubes, silver nanowires of 20 to 40 nm in diameter, 10 to 30 μm in length, and polyethylene imine binders. At this time, the carbon nanotube / silver nano wire aqueous dispersion solution contained 0.1 wt% of carbon nanotubes, 0.1 wt% of silver nanowires, 0.1 wt% of HPMC, 0.1 wt% of CTAB, 0.6 wt% of photosensitive polyvinyl alcohol as a water- % Is included.

The carbon nanotube / silver nanowire water dispersion was coated on a PET film by a bar coating method, and the coated substrate was dried at a temperature of 130 ° C for 1 minute. The sheet resistance value of the dried photosensitive thin film was high (not less than 10 MΩ / sq) so as not to be measured by the sheet resistance meter. The photosensitive thin film was irradiated with ultraviolet ray for 1 second in a specific pattern form using a chromium photomask and subjected to subsequent heat treatment at 130 캜 for 5 minutes. Then, the coated conductive film according to the first embodiment formed on the substrate can be obtained by washing with water as a solvent and drying.

The ultraviolet ray exposure area of the coated conductive film according to the second example was formed by a straight line having various line widths as shown in Fig. 8, and the insulating property according to the exposure line width was examined.

As a result, the ultraviolet exposure line is formed of a transparent conductive film that is visible with a slight translucent line, but the translucent line of the exposure line is not visible when over polymerizing another polymeric material thereon or joining another film.

The resistance values of the first to fourth exposure lines 41, 42, 43 and 44 were all 10 MΩ / sq or more, and the insulation of the exposure line was high enough that the resistance measurement by the resistance measuring device was impossible. The resistance value of the fifth exposure line 45 was 30 to 50 kΩ, and the resistance value of the sixth exposure line 46 was measured to be 3 kΩ.

The areas A, B C, D, E, F, and G are areas having high electrical conductivity to the areas where the photosensitive material has been removed by washing into the respective non-exposure areas. In this region, the sheet resistance value was 110 ~ 140? / Sq, the light transmittance was 89%, and the haze was 1.3.

In order to examine the surface morphology of the portion irradiated with ultraviolet rays and the portion irradiated with ultraviolet rays, an ultraviolet ray exposure region and a non-exposed region were observed with an electron microscope, as shown in Figs.

As a result of the analysis, there was almost no difference in the distribution of silver nano wires in the ultraviolet exposure line regions (a), (b), and ultraviolet non-exposure regions (c) and (d) there was.

However, in the enlarged electron microscope images (b) and (d), in the ultraviolet exposure line region (b), the silver nanoaire is covered with the photosensitive material and the binder as compared with the ultraviolet non-exposure region (d) The resistance is increased and the resistance is increased. (B) and (d), which are not well visible in the SEM image due to the very small particle size of the carbon nanotubes. (b), carbon nanotubes can be identified in some areas although they are not clearly seen due to photosensitive materials and other compositions.

B, C, D, and E after exposing again to the ultraviolet rays of the same condition for the conductive substrate according to the second embodiment in order to confirm that there is no damage to the silver nano wire itself due to ultraviolet exposure. , F, and G, respectively. The sheet resistances of the regions A, B, C, D, E, F, and G before UV exposure were measured to be 110-140? / Sq, with a light transmittance of 89% and a haze of 1.3. The sheet resistivity of the regions A, B, C, D, E, F and G after UV 5 sec exposure was 110 ~ 135? / Sq, the light transmittance was 89% and the haze was 1.3. It can be confirmed that there is almost no deterioration.

It should be noted that the embodiments disclosed in the present specification and drawings are only illustrative of specific examples for the purpose of understanding, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that other modifications based on the technical idea of the present invention are possible in addition to the embodiments disclosed herein.

10: substrate
21: Conductive nanomaterials
23: Photosensitive thin film
25: exposed area
27: unexposed area
29: wiring pattern
20: Coated conductive film
30: Mask
31: pattern hole
100: conductive substrate

Claims (8)

0.01 to 5 wt% of a conductive nanomaterial, 0.01 to 3 wt% of an ultraviolet sensitive material, and 1 wt% or less of a binder,
The conductive nanomaterial is a metal nanowire or nanocarbon,
The ultraviolet sensitive material is a photosensitive functional group, polyvinyl alcohol having N-methyl-4 (4'-formylstyryl) pyridinium methosulfate acetal functional group,
Wherein the binder is a water-dispersible polyurethane or a cationic polymer electrolyte. delete The positive electrode according to claim 1,
poly (2-vinylpyridine), poly (ethylenenimine), poly (acrylamide-co-diallylmethylammonium chloride), cationic polythiophene, polyaniline , poly (vinylalcohol), or a derivative thereof. A coated conductive film formed on a substrate,
Wherein the non-exposed region comprises a conductive nanomaterial, an ultraviolet sensitive material and a binder, wherein the exposed and unexposed regions are formed by ultraviolet exposure and cleaning, the unexposed region has an electrical conductivity twice or more than the exposed region, Wherein the conductive nanomaterial is uniformly distributed in the exposed region and the non-exposed region. 5. The method of claim 4,
Wherein the conductive nanomaterial is a metal nanowire or nanocarbon and the ultraviolet sensitive material is a polyvinyl alcohol having a photosensitive functional group such as N-methyl-4 (4'-formylstyryl) pyridinium methosulfate acetal functional group, and the binder is a water dispersible polyurethane Or a cationic polymer electrolyte. 5. The method of claim 4,
Wherein the unexposed area is more removed in the cleaning process than the exposed area to have a lower residue content. The method according to claim 6,
Wherein the conductive nanomaterials are distributed in the unexposed region and the exposed region and form a similar distribution structure and a similar distribution density in the two regions. 5. The method of claim 4,
Wherein the non-exposed region and the exposed region of the exposed region have a structure wherein the conductive nanomaterial is more impregnated with the ultraviolet sensitive material than the unexposed region.
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US14/760,089 US9977327B2 (en) 2013-03-25 2014-03-12 Photosensitive coating composition, coating conductive film using photosensitive coating composition, and method for forming coating conductive film
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KR20170087851A (en) * 2017-07-21 2017-07-31 전자부품연구원 Conductive substrate and manufacturing method thereof
KR20190009923A (en) * 2017-07-20 2019-01-30 포항공과대학교 산학협력단 Method for positioning microparticles on large substrate and polymer composite comprising the microparticles positioned by the same

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KR20160095295A (en) 2015-02-02 2016-08-11 전자부품연구원 Conductive film with a protective coating layer and method for manufacturing of the same
KR20190009923A (en) * 2017-07-20 2019-01-30 포항공과대학교 산학협력단 Method for positioning microparticles on large substrate and polymer composite comprising the microparticles positioned by the same
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