KR20170018158A - Conductive substrate and manufacturing method thereof - Google Patents

Conductive substrate and manufacturing method thereof Download PDF

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KR20170018158A
KR20170018158A KR1020150110825A KR20150110825A KR20170018158A KR 20170018158 A KR20170018158 A KR 20170018158A KR 1020150110825 A KR1020150110825 A KR 1020150110825A KR 20150110825 A KR20150110825 A KR 20150110825A KR 20170018158 A KR20170018158 A KR 20170018158A
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South Korea
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base substrate
poly
photosensitive
polymer electrolyte
photosensitive resin
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KR1020150110825A
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Korean (ko)
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신권우
최윤수
장덕진
길승범
우란
박수빈
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전자부품연구원
주식회사 상보
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Priority to KR1020150110825A priority Critical patent/KR20170018158A/en
Publication of KR20170018158A publication Critical patent/KR20170018158A/en

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    • 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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Abstract

The present invention relates to a conductive substrate using a photosensitive coating liquid containing a metal nanowire and a photosensitive resin and a method of manufacturing the same. A conductive substrate according to the present invention comprises a base substrate, an exposure region and a non-exposure region. The base substrate is surface-treated with an ionic polymer electrolyte having polarity, and a polar functional group is introduced to the surface. The exposure area and the non-exposure area are formed by applying a photosensitive coating liquid containing a photosensitive resin and metal nanowires having the same polarity as that of the ionic polymer electrolyte, and then exposing and cleaning. At this time, the photosensitive resin of the photosensitive coating solution contained in the non-exposed region is removed by using the polar functional group introduced into the base substrate and the repulsive force between the photosensitive resin of the photosensitive coating liquid and the non-exposed region to form a wiring pattern having electric conductivity .

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a conductive substrate,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive substrate and a method of manufacturing the same, and more particularly, to a conductive substrate having a conductive film formed of a coating liquid containing metal nanowires on a base substrate surface-treated with an ionic polymer electrolyte, and a method of manufacturing the same.

The conductive film including the metal nanowires can be formed by coating on the base substrate as a conductive film formed by successive contact of conductive nanomaterials in the form of wires, tubes, and nanoparticles. The conductive film including the metal nanowires can be formed as a conductive film having electrical conductivity by forming a dispersion by coating with various base substrates by a simple solution process. Conductive films containing such metal nanowires are used as transparent electrodes or circuit electrodes in touch panels and displays.

In order to use a conductive film including metal nanowires as a transparent electrode or a circuit electrode, it is necessary to control electric connection and non-connection (insulation) 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.

Here, the photolithography method includes a method of forming a photoresist pattern on a conductive film by applying a photoresist on a conductive film, exposing and developing ultraviolet rays, and then forming a wiring pattern by etching the conductive film in a specific pattern by a wet or dry method to be.

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 in the etched region and the non-etched region of the conductive film in which the wiring pattern is formed, light reflection, light transmittance, and haze difference may be formed, thereby causing a problem that the wiring pattern of the conductive film is visually recognized.

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.

In order to solve such a problem, a technique of forming a wiring pattern by a non-etching method using a photosensitive coating liquid has been introduced. That is, in the non-etching method, a photosensitive coating liquid containing metal nanowires is coated on a base substrate to form a photosensitive coating layer, a photosensitive material in an exposed region is exposed by exposing ultraviolet rays to a part of the photosensitive coating layer, Thereby forming a wiring pattern by forming a difference in conductivity between exposed and unexposed regions.

In the exposed and non-exposed regions formed by selective irradiation of ultraviolet rays, a difference in solubility of the photosensitive resin to the cleaning solvent is formed during the cleaning process, and thereby, a difference in electrical conductivity between exposed and unexposed regions occurs, The wiring pattern can be formed only by the exposure and cleaning processes.

In such a non-etching method, the exposed region corresponds to an insulating region or a region having a high resistance, and the non-exposed region has a high solubility of the photosensitive resin with respect to the solvent, so that more photosensitive resin is removed during the cleaning process, . This non-etching method is such that the metal nanowires are similarly distributed in the exposed and unexposed regions having different electrical conductivities, and are damaged or unetched in both regions.

A major factor in determining the characteristics of the patterned wiring pattern through such a non-etching method is that it must be able to form a clear boundary at the boundary of the exposed and non-exposed areas, the photosensitive resin is easily removed during the cleaning process, And uniform characteristics should be secured over the entire substrate.

However, in the case of the conventional non-etching method, depending on the type of the base substrate and the characteristics of the surface of the base substrate, the photosensitive resin in the non-exposed region may not be sufficiently or completely removed in the cleaning process. When the photosensitive resin is not sufficiently or completely removed in the non-exposed region as described above, the resistance of the non-exposed region becomes high, the resistance uniformity becomes poor, the haze increases when the non-exposed region is formed as a transparent electrode, There is a problem that the boundaries of the regions are unclear.

Korean Registered Patent No. 10-1447516 (September 29, 2014)

Accordingly, an object of the present invention is to provide a method of forming a conductive film by a non-etching method, in which a photosensitive resin in a non-exposed region is sufficiently removed in a cleaning process to lower the sheet resistance and haze of an unexposed region, to secure resistance uniformity, And a boundary between the exposed and unexposed areas can be clarified, and a method of manufacturing the same.

Another object of the present invention is to provide a conductive substrate capable of lowering the sheet resistance and haze of a conductive film formed on a base substrate through surface treatment of the base substrate and improving light transmittance, and a method of manufacturing the same.

In order to achieve the above object, the present invention provides a method for manufacturing a photosensitive substrate, comprising the steps of: applying a photosensitive coating liquid containing a metal nanowire and a photosensitive resin having polarity to a surface of a base substrate to be coated with an ionic polymer electrolyte having the same polarity as the polarity of the photosensitive resin of the photosensitive coating liquid And introducing the polar functional group to the surface of the base substrate; Forming a photosensitive coating layer by coating the photosensitive coating liquid on the surface-treated base substrate; And washing the base substrate coated with the photosensitive coating layer to produce a conductive substrate.

The present invention may further comprise a step of exposing the photosensitive coating layer of the base substrate, which is performed between the forming and the forming, to form an exposure area and a non-exposure area.

At this time, the photosensitive resin of the photosensitive coating solution contained in the non-exposed region is removed using the polar functional group introduced into the base substrate and the repulsive force between the photosensitive resin of the photosensitive coating liquid during cleaning, Can be formed into a wiring pattern having electrical conductivity.

The ionic polymer electrolyte may be a cationic polymer electrolyte such as poly (diallydimethylammonium chloride), poly (allyamine hydrochloride), polyaniline, poly (3,4-ethylenedioxythiophene) (PEDOT) (acrylamide-co-diallylmethylammonium chloride), cationic polythiophene, or polyaniline.

The photosensitive resin of the photosensitive coating solution may include polyvinyl alcohol (poly (vinyl alcohol)) having a photosensitive functional group such as N-methyl-4 (4'-formylstyryl) pyridinium methosulfate acetal.

The metal nanowires of the photosensitive coating solution may include silver nanowires having a diameter of 1 to 100 nm and a length of 1 to 300 μm, copper nanowires or gold nanowires.

The introducing may include: immersing the base substrate in an aqueous solution of a cationic polyelectrolyte, removing the base substrate, and washing the base substrate; And immersing the base substrate in an aqueous acid solution, removing the base substrate, and washing the base substrate.

In the method of manufacturing a conductive substrate according to the present invention, the ionic polymer electrolyte may further include an anionic polymer electrolyte. The anionic polyelectrolyte may be a salt of poly (acrylic acid), poly (acrylic acid), poly (styrene sulfonic acid), poly (styrene sulfonic acid), polyvinyl alcohole, polyarmic acid, poly (vinylsulfonic acid), poly (vinylsulfonic acid salt, poly (anetholesulfonic acid), poly (anetholesulfonic acid) salt, poly (4-styrenesulfonic acid-co-maleic acid), poly (4-styrenesulfonic acid-co-maleic acid ) Or a salt of Nafion.

At this time, the photosensitive resin of the photosensitive coating liquid may have a negative polarity.

The introducing may include: treating the surface of the base substrate with the cationic polymer electrolyte; And treating the surface of the base substrate surface-treated with the anionic polyelectrolyte by the anionic polyelectrolyte.

The step of treating the surface with the cationic polyelectrolyte may include: immersing the base substrate in an aqueous solution of a cationic polymer electrolyte, and then removing the base substrate; And immersing the base substrate in an aqueous acid solution, removing the base substrate, and washing the base substrate.

The step of treating the surface with the anionic polyelectrolyte may include: immersing the base substrate surface-treated with the cationic polymer electrolyte in an aqueous anionic polyelectrolyte solution, and then removing the base substrate; And immersing the base substrate in an aqueous base solution, removing the substrate base, and washing the base substrate.

The present invention also provides a base substrate comprising: a base substrate surface-treated with an ionic polymer electrolyte; And a conductive film formed by coating a surface-treated base substrate with a coating solution containing metal nanowires.

The present invention also provides a base substrate comprising a base substrate having a polar functional group surface-treated with an ionic polymer electrolyte having polarity, And a conductive film including an exposed region formed by applying a photosensitive coating liquid containing a photosensitive resin having the same polarity as the ionic polymer electrolyte and a metal nanowire and exposed and washed and a non-exposed region, to provide. In this case, the photosensitive resin of the photosensitive coating solution contained in the non-exposed region is removed using both the polar functional group introduced into the base substrate and the repulsive force between the photosensitive resin of the photosensitive coating liquid during cleaning, Pattern.

According to the present invention, surface treatment with an ionic polymer electrolyte on a base substrate can lower the sheet resistance and haze of a conductive film including metal nanowires formed on a surface-treated base substrate, and improve light transmittance.

The surface of the base substrate is treated with an ionic polymer electrolyte having the same polarity as the polarity of the photosensitive resin of the photosensitive coating liquid containing the metal nanowires coated on the base substrate, The bonding force can be weakened. That is, since the functional groups having the same polarity as the polarity of the photosensitive resin contained in the photosensitive coating liquid through the surface treatment of the base substrate are formed on the surface of the base substrate, the polarities of the same polarity repel each other. Can be weakened.

This makes it possible to easily remove the photosensitive resin in the non-exposed region in the cleaning process for the base substrate coated with the photosensitive coating liquid.

In forming the conductive film by the non-etching method as described above, since the photosensitive resin in the non-exposed region can be sufficiently removed in the cleaning process, the sheet resistance and haze of the non-exposed region can be lowered, resistance uniformity can be secured, . In addition, when the exposed and non-exposed regions are formed through exposure and cleaning on the base substrate coated with the photosensitive coating liquid, the boundaries between the exposed and unexposed regions can be clarified.

1 is a cross-sectional view showing a conductive substrate according to the present invention.
2 is a flowchart illustrating a method of manufacturing a conductive substrate according to the present invention.
FIGS. 3 to 6 are views showing respective steps according to the manufacturing method of FIG.

In the following description, only parts necessary for understanding embodiments of the present invention will be described, and descriptions of other parts will be omitted to the extent that they do not disturb 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 cross-sectional view showing a conductive substrate according to the present invention.

Referring to FIG. 1, a conductive substrate 100 according to the present invention includes a surface-treated base substrate 10 and a conductive film 30 formed on the base substrate 10.

The base substrate 10 is surface-treated with an ionic polymer electrolyte having polarity, and a polar functional group is introduced to the surface. The surface treatment layer 20 shows a portion where the polar functional group is introduced into the surface of the base substrate 10. The functional group of the polarity of the surface treatment layer 20 has one polarity in the anode and the cathode.

Various materials such as PET (polyethylene terephthalate), PC (polycarbonate), PI (polyimide), PP (polypropylene substrate), glass and quartz can be used as the base substrate 10, .

The conductive film 30 is formed by applying a photosensitive coating liquid containing a photosensitive resin and a metal nanowire having the same polarity as that of the ionic polymer electrolyte, and then exposing and cleaning the exposed region 35 and the non-exposed region 37 Respectively. The photosensitive resin of the photosensitive coating liquid contained in the non-exposed region 37 is removed by using the repulsive force between the polar functional group introduced into the base substrate 10 and the photosensitive resin of the photosensitive coating liquid during cleaning, And is formed of a wiring pattern 39 having conductivity.

As the photosensitive resin of the photosensitive coating liquid, for example, polyvinyl alcohol (N-methyl-4 (4'-formylstyryl) pyridinium methosulfate acetal functional group as a photosensitive functional group may be used. The polyvinyl alcohol having N-methyl-4 (4'-formylstyryl) pyridinium methosulfate acetal functionalities has a cationic polarity.

The metal nanowires of the photosensitive coating liquid include silver nanowires having a diameter of 1 to 100 nm and a length of 1 to 300 μm, copper nanowires or gold nanowires.

The reason for carrying out the surface treatment on the base substrate 10 in the present invention is as follows. That is, a photosensitive coating liquid containing metal nanowires is coated on the base substrate 10, and ultraviolet rays are exposed to and cleaned in a specific region of the coated base substrate 10 to remove the photosensitive resin for the cleaning solvent in the ultraviolet- And the resistance difference between the regions is formed. Such a non-etching method can be applied to a technique of forming a pattern of a transparent electrode.

At this time, as the photosensitive resin undergoes the chemical bond reaction by the ultraviolet rays in the exposure region 35, the solubility in the solvent is greatly reduced to become an insulating or high resistance region. On the contrary, the photosensitive resin in the non-exposed region 37 is removed during cleaning to improve the contact characteristics between the metal nanowires and to form a conductive region or a low resistance region.

 In forming the wiring pattern 39 through such a non-etching method, it is important to adjust the surface characteristics of the base substrate 10. The bonding force between the base substrate 10 and the photosensitive resin varies according to the type and surface characteristics of the base substrate 10. That is, when the mutual coupling force between the base substrate 10 and the photosensitive resin is strong, the photosensitive resin is not removed well during the cleaning of the non-exposed region 37. Therefore, the contact property between the metal nanowires becomes poor due to the residual photosensitive resin. And the residual photosensitive resin increases the surface roughness to cause optical haze and make the interface between the exposure area 35 and the non-exposure area 37 unclear.

 Therefore, in order to weaken mutual bonding force between the photosensitive resin and the base substrate 10, the surface treatment of the base substrate 10 is performed in the present invention. At this time, the surface treatment is performed by treating the surface of the base substrate 10 with an ionic polymer electrolyte having the same polarity as the polarity of the photosensitive resin of the photosensitive coating liquid containing the metal nanowires coated on the base substrate 10, It is possible to weaken the mutual bonding force between the photosensitive resin 10 and the photosensitive resin of the photosensitive coating liquid. That is, since the functional group having the same polarity as the polarity of the photosensitive resin contained in the photosensitive coating liquid is formed on the surface of the base substrate 10 through the surface treatment of the base substrate 10, It is possible to weaken the mutual bonding force between the photosensitive resin 10 and the photosensitive resin of the photosensitive coating liquid.

Accordingly, the photosensitive resin in the non-exposed region 37 can be easily removed during the cleaning process for the base substrate 10 coated with the photosensitive coating liquid.

Since the photosensitive resin in the non-exposed region 37 can be sufficiently removed in the cleaning process in forming the conductive film 30 by the non-etching method, the sheet resistance of the non-exposed region 37 can be lowered, And the haze can be lowered. The boundary between the exposure region 35 and the non-exposure region 37 is clearly defined when the exposure region 35 and the non-exposure region 37 are formed through exposure and cleaning on the base substrate 10 coated with the photosensitive coating liquid can do.

The surface treatment of the base substrate 10 according to the present invention can be carried out as follows according to the polarity of the photosensitive resin contained in the photosensitive coating liquid.

First, when the photosensitive resin is cationic, a cationic polymer electrolyte is adsorbed on the base substrate 10, a photosensitive coating liquid containing a cationic photosensitive resin and metal nanowires is coated thereon, (30) can be formed. A method of adsorbing the cationic polymer electrolyte on the base substrate 10 is as follows.

 The cationic polyelectrolyte material is dissolved in water to form an aqueous solution. Then, the base substrate 10 to be coated with the photosensitive coating liquid is immersed in a cationic polyelectrolyte aqueous solution. Then, the immersed base substrate 10 is taken out, washed with distilled water, immersed in an aqueous acid solution such as an aqueous hydrochloric acid solution, and then washed with distilled water to complete the surface treatment on the base substrate 10.

At this time, various acidic aqueous solutions such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and phosphoric acid can be used as the acid aqueous solution, and it is preferable to control the concentration of the acid within a range that does not damage the base substrate 10.

Namely, by performing the surface treatment with the cationic polymer electrolyte on the base substrate, the amine functional group can be introduced into the surface of the base substrate. After introduction of the amine functional group, a positive charge can be introduced into the amine functional group through subsequent acid treatment.

On the other hand, the step of immersing in an aqueous acid solution may be omitted. In this case, the surface treatment process is completed by washing the water after immersing the cationic polymer electrolyte.

Examples of the cationic polymer electrolyte include poly (diallydimethylammonium chloride), poly (allyamine hydrochloride), polyaniline, poly (3,4-ethylenedioxythiophene) (PEDOT), poly (2-vinylpyridine) poly (ethylenenimine), poly (acrylamide-co-diallylmethylammonium chloride, cationic polythiophene, or polyaniline may be used, but the present invention is not limited thereto.

 Next, when the photosensitive resin is anion, an anionic polyelectrolyte is adsorbed on the base substrate 10 using an anionic polymer electrolyte, a photosensitive coating liquid containing an anionic photosensitive resin and metal nanowires is coated thereon, The conductive film 30 can be formed through exposure and cleaning.

 A method for adsorbing an anionic polyelectrolyte is as follows. Generally, since the anionic polymer electrolyte is not well adsorbed on the base substrate 10, a method of adsorbing the cationic polymer electrolyte on the base substrate 10 and then adsorbing the anionic polymer electrolyte can be used. After the cationic polymer electrolyte is adsorbed on the base substrate 10 in the above manner, the anionic polymer electrolyte is adsorbed by the following method.

 An anionic polyelectrolyte material is dissolved in water to form an aqueous solution. Then, the base substrate 10 to be coated with the photosensitive coating liquid is immersed in an aqueous solution of anionic polyelectrolyte. Then, the immersed base substrate 10 is taken out, washed with distilled water, immersed in an aqueous base solution, and then washed with distilled water to complete the surface treatment on the base substrate 10.

At this time, an aqueous solution of sodium hydroxide, potassium hydroxide, ammonia water or the like can be used as an aqueous base solution, and the base immersion step may be omitted in some cases.

The anionic polymer electrolytes include poly (acrylic acid), poly (acrylic acid) salt, poly (styrene sulfonic acid), poly (styrene sulfonic acid) salt, polyvinyl alcohole, polyarmic acid, polyarmic acid salt, poly (vinylsulfonic acid), poly (vinylsulfonic acid salt, poly (anetholesulfonic acid), poly (anetholesulfonic acid) salt, poly (4-styrenesulfonic acid-co-maleic acid), poly (4-styrenesulfonic acid-co-maleic acid ) Or Nafion may be used, but it is not limited thereto.

The reason why the base substrate 10 is immersed in the ionic polymer electrolyte solution in the ionic polymer electrolyte adsorption method and then treated with the acid or base aqueous solution is that the adsorbed ionic polymer electrolyte is more ionized and more positively or negatively charged So as to be able to form a lot. Depending on the type of the base substrate 10 and the ionic polymer electrolyte, the acid or base treatment process can be omitted because surface charge can be formed without an acid or base treatment.

A method of manufacturing the conductive substrate 100 according to the present invention will now be described with reference to FIGS. 1 to 6. FIG. 2 is a flowchart illustrating a method of manufacturing the conductive substrate 100 according to the present invention. FIGS. 3 to 6 are views showing respective steps according to the manufacturing method of FIG.

First, as shown in Fig. 3, a base substrate 10 on which a conductive film 30 is to be formed is prepared.

Next, as shown in FIG. 4, in step S51, the surface of the base substrate 10 is treated with an ionic polymer electrolyte having polarity. For example, when the photosensitive resin of the photosensitive coating liquid is cationic, a process of surface-treating the base substrate 10 with a cationic polymer electrolyte proceeds. That is, the base substrate 10 is immersed in a cationic polyelectrolyte aqueous solution and then taken out to be cleaned. Thereafter, the base substrate 10 is immersed in an aqueous acid solution, have.

Or if the photosensitive resin of the photosensitive coating liquid has an anionic property, a process of surface-treating the base substrate 10 with a cationic and an anionic polymer electrolyte may be performed. That is, the surface of the base substrate 10 is treated with the cationic polymer electrolyte described above. Then, the surface of the base substrate 10 surface-treated with the cationic polymer electrolyte is treated with an anionic polyelectrolyte. In this case, in the process of treating the surface with the anionic polyelectrolyte, the base substrate 10 surface-treated with the cationic polymer electrolyte is immersed in an aqueous anionic polyelectrolyte solution, and is taken out to be cleaned. Then, the base substrate 10 is immersed in an aqueous base solution The surface treatment for the base substrate 10 can be completed.

Next, as shown in FIG. 5, in step S53, the photosensitive coating solution containing the metal nanowire and the photosensitive resin 33 having the same polarity as the polarity of the ionic polymer electrolyte is coated on the surface-treated base substrate 10 A photosensitive coating layer 31 is formed. That is, the photosensitive coating liquid is applied to the base substrate 10 and then dried to form a photosensitive coating layer 31. The metal nanowires and the photosensitive resin 33 are uniformly distributed in the photosensitive coating layer 31. [

Here, the photosensitive coating liquid includes metal nanowires and photosensitive resin 33, and may include other binders, water, and other compositions. For example, the photosensitive coating liquid may contain 0.01 to 5% by weight of metal nanowires, 0.01 to 3% by weight of the photosensitive resin 33, 1% by weight or less of the binder, and 5% by weight or less of the other composition.

Subsequently, as shown in FIGS. 6 and 7, the base substrate 10 coated with the photosensitive coating layer 31 is washed in a step S55 to prepare the conductive substrate 100 having the conductive film 30. Next, as shown in FIG.

The conductive film 30 according to the step S55 can be formed as follows. That is, a part of the photosensitive coating layer 31 is exposed. That is, the photosensitive coating layer 31 is exposed to ultraviolet rays by using a mask 40 having pattern holes 41 corresponding to the areas 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 metal nanowires during the exposure process.

The conductive substrate 100 on which the conductive film 30 having the wiring pattern 39 is formed can be manufactured by washing and drying the exposed photosensitive coating layer 31 with a solvent. The photosensitive resin 33a is removed from the non-exposed region 37 and is formed as the wiring pattern 39 because the non-exposed region 37 has a relatively high solubility with respect to the solvent as compared with the exposed region 35. [ On the other hand, the photosensitive resin 33b of the exposure area 35 remains in the exposure area 35 due to the material cured by the exposure, though the photosensitive resin 33b of the exposure area 35 is partially removed.

At this time, by forming a functional group having the same polarity as the polarity of the photosensitive resin 33 included in the photosensitive coating layer 31 on the surface of the base substrate 10 through the surface treatment of the base substrate 10, The mutual bonding force between the base substrate 10 and the photosensitive resin 33 of the photosensitive coating layer 31 can be weakened. Accordingly, the photosensitive resin 33a of the non-exposed region 37 can be easily removed during the cleaning process of the base substrate 10 on which the photosensitive coating layer 31 is formed.

The properties of the conductive film 30 will be described below with reference to the conductive substrate 100 according to the present invention.

[Example 1]

In Example 1, a touch panel sensor was formed through exposure and cleaning processes using a photosensitive coating solution containing silver nanowires. A PET substrate was used as the base substrate. An indium tin oxide electrode is formed on a PET substrate, an indium tin oxide pattern is formed by an etching method, and an insulating layer polymer is formed thereon to form an insulating substrate. At this time, the indium tin oxide electrode forms a sensing electrode in one axial direction of the touch panel sensor. After coating the photosensitive coating liquid containing the silver nano wire on the insulating layer polymer, another sensing electrode is formed by the exposure and cleaning method. At this time, the insulating layer polymer serves to prevent the two directional sensing electrodes from being in electrical contact with each other.

The photosensitive coating liquid contains a photosensitive resin. As the photosensitive resin, a poly (vinyl alcohol), N-methyl-4 (4'-formylstyryl) pyridinium methosulfate acetal Were used.

An aqueous solution of 2 wt% poly (ethylenimine) was prepared for the surface treatment of the insulating substrate, and the insulating substrate was immersed in this solution for 3 minutes and then washed with distilled water. Then, the substrate was immersed in a 0.01 M hydrochloric acid solution for 1 minute, again washed with distilled water, and the insulating substrate was dried. Then, a photosensitive coating solution containing silver nano wire was coated and dried at 120 ° C for 5 minutes. The photosensitive coating solution containing silver nano wire contains 0.15 wt% of silver nanowire, 0.6 wt% of poly (vinyl alcohol), 4-formylstyryl (N-methyl-4) pyridinium methosulfate acetal and 0.1 wt% of hydroxy propyl methyl cellulose.

The insulating substrate on which the photosensitive coating layer was formed was irradiated with ultraviolet rays in specific regions and washed again with distilled water to form a transparent electrode pattern. As a result, the sheet resistance in the non-exposed region corresponding to the conductive region was 74 Ω / sq, the haze was 1.7%, and the transmittance was 90.2%. The exposed area showed insulation of 20 MΩ / sq or more in sheet resistance.

[Comparative Example 1]

As Comparative Example 1, a photosensitive coating liquid was coated on an insulating substrate not subjected to a surface treatment in the same manner, and then a transparent electrode pattern was formed through exposure and cleaning. In the case of the non-surface-treated insulating substrate, the sheet resistance in the non-exposed region corresponding to the conductive region was 420 Ω / sq, the haze was 3.4%, and the transparency was 89%. (4'-formylstyryl) pyridinium methosulfate acetal, which is a photosensitive resin in the non-exposed region, can not be completely removed and thus the resistance of the conductive region is increased, The increase in haze.

In the present invention, a photosensitive coating liquid is formed on a surface-treated substrate, and then an electroconductive film is formed through exposure and washing. However, the present invention is not limited thereto. For example, the surface treatment method according to the present invention can be used as a pretreatment method of a base substrate when coating a coating liquid containing metal nanowires on a base substrate.

That is, when the ionic polymer electrolyte is adsorbed on the base substrate and the coating solution containing the metal nanowires is coated on the base substrate, the transparent electrode having a constant characteristic can be formed regardless of the type of the base substrate or the surface state. This is because the surface properties of the original base substrate are offset by the adsorbed polymeric functional groups or charges and provide uniform surface properties.

[Example 2]

 The conductive substrate according to Example 2 was prepared by coating a coating liquid containing silver nano wires on a PET substrate surface-treated with a cationic polymer electrolyte as in Example 1. [ The properties of the conductive film coated on the conductive substrate of Example 2, that is, the transparent electrode film, were evaluated. The coating liquid contains 0.15 wt% silver nano wire and 0.18 wt% hydroxy propyl methyl cellulose. The sheet resistance of the transparent electrode film of Example 2 was 62 Ω / sq, the haze was 0.9%, and the transmittance was 91.0%.

[Comparative Example 2]

As Comparative Example 2, a coating solution containing silver nano wire was coated on a non-surface treated PET substrate, and the properties of the coated transparent electrode film were evaluated. As a result, the sheet resistance was 265? / Sq, the haze was 1.9%, the transmittance was 90.0%, and the characteristics of the transparent electrode film were inferior to those of the transparent electrode film subjected to the surface treatment according to Example 2.

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: base substrate
20: Surface treatment layer
30: Conductive membrane
31: Photosensitizer coating layer
33, 33a, 33b: photosensitive resin
35: Exposure area
37: Non-exposure area
39: wiring pattern
40: mask
41: pattern hole
100: conductive substrate

Claims (8)

The surface of the base substrate to be coated with the photosensitive coating liquid containing the metal nanowire and the photosensitive resin having polarity is treated with an ionic polymer electrolyte having the same polarity as the polarity of the photosensitive resin of the photosensitive coating liquid, Onto a surface of a substrate;
Forming a photosensitive coating layer by coating the photosensitive coating liquid on the surface-treated base substrate; And
Cleaning the base substrate coated with the photosensitive coating layer to produce a conductive substrate;
Wherein the conductive substrate comprises a conductive material. 2. The method of claim 1, further comprising:
Exposing the photosensitive coating layer of the base substrate to form an exposure region and a non-exposure region,
In the producing step,
Removing the photosensitive resin of the photosensitive coating liquid contained in the non-exposed region by using a polar functional group introduced into the base substrate and a repulsive force between the photosensitive resin of the photosensitive coating liquid and the non-exposed region, And forming a conductive layer on the conductive substrate. The method according to claim 1,
The ionic polymer electrolyte may be a cationic polymer electrolyte such as poly (diallydimethylammonium chloride), poly (allyamine hydrochloride), polyaniline, poly (3,4-ethylenedioxythiophene) (PEDOT) (acrylamide-co-diallylmethylammonium chloride), cationic polythiophene or polyaniline,
The photosensitive resin of the photosensitive coating solution contains polyvinyl alcohol having a photosensitive functional group, N-methyl-4 (4'-formylstyryl) pyridinium methosulfate acetal functional group,
Wherein the metal nanowire of the photosensitive coating solution comprises silver nano wire having a diameter of 1 to 100 nm and a length of 1 to 300 m, copper nanowire or gold nanowire. 4. The method of claim 3,
Immersing the base substrate in an aqueous solution of a cationic polyelectrolyte, removing the base substrate, and washing the base substrate; And
Immersing the base substrate in an aqueous acid solution, removing the base substrate, and washing the base substrate;
Wherein the conductive substrate comprises a conductive material. The method according to claim 1,
Wherein the ionic polymer electrolyte comprises a cationic polymer electrolyte and an anionic polymer electrolyte,
The cationic polyelectrolyte may be selected from the group consisting of poly (diallydimethylammonium chloride), poly (allyamine hydrochloride), polyaniline, poly (3,4-ethylenedioxythiophene) (PEDOT), poly chloride, cationic polythiophene or polyaniline,
The anionic polyelectrolyte may be a salt of poly (acrylic acid), poly (acrylic acid), poly (styrene sulfonic acid), poly (styrene sulfonic acid), polyvinyl alcohole, polyarmic acid, poly (vinylsulfonic acid), poly (vinylsulfonic acid salt, poly (anetholesulfonic acid), poly (anetholesulfonic acid) salt, poly (4-styrenesulfonic acid-co-maleic acid), poly (4-styrenesulfonic acid-co-maleic acid ) Or a salt of Nafion,
The photosensitive resin of the photosensitive coating liquid has a negative polarity,
Wherein the metal nanowire of the photosensitive coating solution comprises silver nano wire having a diameter of 1 to 100 nm and a length of 1 to 300 m, copper nanowire or gold nanowire. 6. The method of claim 5,
Treating the surface of the base substrate with the cationic polyelectrolyte; And
Treating the surface of the base substrate surface-treated with the cationic polymer electrolyte with the anionic polyelectrolyte,
The step of treating the surface with the cationic polymer electrolyte comprises:
Immersing the base substrate in an aqueous solution of a cationic polyelectrolyte, removing the base substrate, and washing the base substrate; And
Immersing the base substrate in an aqueous acid solution, removing the base substrate, and washing the base substrate,
The step of treating the surface with the anionic polyelectrolyte,
Immersing the base substrate surface-treated with the cationic polymer electrolyte in an aqueous anionic polyelectrolyte solution, removing the base substrate, and washing the base substrate; And
Immersing the base substrate in an aqueous base solution, removing the base substrate, and washing the base substrate;
Wherein the conductive substrate comprises a conductive material. A base substrate surface-treated with an ionic polymer electrolyte; And
A conductive film formed by coating a surface-treated base substrate with a coating solution containing metal nanowires;
And a conductive layer formed on the conductive substrate. A base substrate having a polar functional group surface-treated with an ionic polymer electrolyte having polarity and having the polar functional group introduced on a surface thereof; And
And a conductive film having an exposed region and an unexposed region formed by applying a photosensitive coating liquid containing a photosensitive resin having the same polarity as that of the ionic polymer electrolyte and metal nanowires,
Removing the photosensitive resin of the photosensitive coating liquid contained in the non-exposed region by using a polar functional group introduced into the base substrate and a repulsive force between the photosensitive resin of the photosensitive coating liquid and the non-exposed region, Wherein the conductive substrate is formed of a conductive material.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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