WO2012177102A2

WO2012177102A2 - Method for preparing carbon nanotube film

Info

Publication number: WO2012177102A2
Application number: PCT/KR2012/005000
Authority: WO
Inventors: 정다정; 방윤영; 김승렬
Original assignee: (주)탑나노시스
Priority date: 2011-06-23
Filing date: 2012-06-25
Publication date: 2012-12-27
Also published as: KR101285414B1; KR20130000487A; CN103635422A; WO2012177102A3

Abstract

The present invention provides a method for preparing a carbon nanotube film which can be wet-etched. The method for preparing a carbon nanotube film, according to the present invention, comprises the steps of: forming a base binder layer including a material which can be wet-etched, on a substrate; forming a CNT coating layer including carbon nanotube, on the upper surface of the base binder layer; forming a top binder layer including a material which can be wet-etched, on the upper surface of the CNT coating layer; and removing the regions to be etched of the CNT coating layer, the top binder layer, and the base binder layer through wet-etching.

Description

Carbon Nanotube Film Manufacturing Method

The present invention relates to a carbon nanotube film manufacturing method, and more specifically, to form a carbon nanotube pattern in a desired shape on a substrate, carbon nanotubes that can be applied to various fields such as charging, display, optical It relates to a film production method.

In general, transparent conductive films have high conductivity (for example, sheet resistance of ¹ × 10 ³ Ω / sq or less) and high transmittance (80% or more) in the visible region. Accordingly, the transparent conductive film may include a plasma display panel (PDP), a liquid crystal display (LCD) device, a light emitting diode (LED), an organic light emitting diode (OLED), and an organic light emitting diode (OLED). ), As an electrode of various light-receiving elements and light-emitting elements in touch panels or solar cells, as well as transparent electromagnetic wave shielding agents such as antistatic films and electromagnetic wave shielding films used in automobile window glass or building window glass, and transparent heating elements such as heat ray reflecting films and refrigerated showcases. It is used.

Recently, research has been made on using carbon nanotubes as electrodes coated on a substrate.

The carbon nanotubes are evaluated as an ideal material capable of realizing conductivity while maintaining optical properties due to the theoretical percolation concentration of only 0.04%, and when light is coated on a specific substrate in nanometer units, light transmits in the visible region. It can be used as a transparent electrode because it shows transparency and maintains electrical property, which is a unique characteristic of carbon nanotubes. In addition, carbon nanotubes can be printed and used in a paste state in addition to the direct growth method, so that the large area is easy.

Carbon nanotubes are chemically very stable and resistant to wet etching. Accordingly, dry etching is used to form the carbon nanotube pattern.

Conventionally, lasers have been used as one of the dry etching methods for forming carbon nanotube patterns. However, since the laser has a small beam size, there is a problem in that a work time for forming a large area pattern is long and a pattern defect rate is high.

In addition, in order to form a carbon nanotube pattern on the carbon nanotube film, there is a problem that a separate dry equipment other than the conventional wet etching equipment used to be manufactured and applied.

It is an object of the present invention to provide a method for producing a carbon nanotube film which can produce a large area and a fine carbon nanotube pattern simply and quickly.

Therefore, the carbon nanotube film manufacturing method according to a preferred embodiment of the present invention, the step of forming a base binder layer comprising a wet etchable material on the substrate, and the carbon nanotube on the upper surface of the base binder layer Forming a CNT coating layer, forming a top binder layer including a wet etchable material on an upper surface of the CNT coating layer, and wet etching the CNT coating layer, the top binder layer, and a target binder layer to be etched. Removal is performed through etching.

Carbon nanotube film manufacturing method according to another embodiment of the present invention, the step of forming a CNT coating layer comprising a carbon nanotube on the upper surface of the substrate, and forming a wet etchable top binder layer on the upper surface of the CNT coating layer And removing the etching target region of the top coating layer through wet etching, and plasma etching the exposed portion of the CNT coating layer to the outside.

Carbon nanotube film production method according to another preferred embodiment of the present invention, forming a CNT coating layer comprising an additive containing a carbon nanotube and a wet etchable material on the substrate, and a wet surface on the CNT coating layer Forming an etchable top binder layer, and removing the CNT coating layer and the etching target region of the top binder layer through wet etching.

According to still another preferred embodiment of the present invention, a method of manufacturing a carbon nanotube film includes forming a wet etchable base binder layer on a substrate, and forming carbon nanotubes and wet etchable nanoparticles on an upper surface of the base binder layer. Forming a CNT coating layer including particles, forming a wet etchable top binder layer on the upper surface of the CNT coating layer, wet etching the CNT coating layer, the top binder layer, and a region to be etched of the base binder layer. It includes removing through.

According to the present invention, a pattern may be formed by wet etching carbon nanotubes. Accordingly, it is possible to form a fine carbon nanotube pattern, it is possible to quickly form a carbon nanotube pattern even in the case of a large area carbon nanotube film.

In addition, by applying a conventional wet etching equipment to form a carbon nanotube pattern, the manufacturing cost is reduced.

1 is a flowchart of a carbon nanotube film manufacturing method according to a first embodiment of the present invention.

2 to 6 are cross-sectional views showing each step of the carbon nanotube film manufacturing method according to the first embodiment of the present invention.

7 is a flow chart of a carbon nanotube film manufacturing method according to a second embodiment of the present invention.

8 to 12 are cross-sectional views showing each step of the carbon nanotube film manufacturing method according to a second embodiment of the present invention.

13 is a flow chart of a carbon nanotube film manufacturing method according to a third embodiment of the present invention.

14 to 17 are cross-sectional views showing respective steps of the carbon nanotube film manufacturing method according to the third preferred embodiment of the present invention.

18 is a flowchart illustrating a carbon nanotube film manufacturing method according to a fourth preferred embodiment of the present invention.

19 to 21 are cross-sectional views showing each step before etching in the carbon nanotube film manufacturing method according to the fourth embodiment of the present invention.

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

1 is a flow chart showing each step of the method for producing a carbon nanotube film (S100) according to an embodiment of the present invention.

As shown in FIG. 1, the carbon nanotube film manufacturing method (S100) according to the first embodiment of the present invention includes forming a base binder layer including a wet etchable material on a substrate (S110). Forming a CNT coating layer including carbon nanotubes on the upper surface of the base binder layer (S120), and forming a top binder layer including a wet etchable material on the upper surface of the CNT coating layer (S130); The wet etching is performed to remove the CNT coating layer, the top binder layer and the etching target region of the base binder layer (S140).

2 to 6 are cross-sectional views showing each step of the carbon nanotube film production method of the present invention. 2 to 6, each step of the carbon nanotube film manufacturing method according to the first embodiment of the present invention will be described in more detail. First, as shown in FIG. 2, a base binder layer 120 including a wet etchable material is formed on the substrate 110.

The substrate 110 may be glass or a material such as a polymer such as PET, PC, PI, PEN, COC, or the like. In this case, the substrate 110 is coated with a CNT coating layer on the upper surface, it can be applied as a display panel, a touch screen, a lighting means. To this end, the substrate 110 is preferably made of a transparent material.

In addition, the substrate 110 may be used as a member requiring flexibility such as electronic paper. In this case, it is preferable that the base material is made of a transparent inorganic substrate or a transparent polymer substrate to have flexibility.

The base binder layer 120 is made of a binder material including a wet etchable material. The wet etchable material may be a ceramic-based and metal oxide, and may be, for example, a material such as TiO 2, SiO 2, ZnO, SnO, SiNx, SiON, SiN _x , ITO, ATO, or the like.

The base binder layer 120 functions to bond the substrate 110 and the carbon nanotube coating layer 130 (see FIG. 3) to be described later. In addition, as will be described in detail later, the base binder layer 120 is wet-etched together with the top binder layer 140 (see FIG. 4), which will be described later, and the CNT coating layer 130 between the base binder layer 120 and the top binder layer. 4) is wet etched.

Thereafter, as shown in FIG. 3, the CNT coating layer 130 is formed on the base binder layer 120. The CNT coating layer 130 includes carbon nanotubes (c). Carbon Nanotubes (CNTs) form a tube where one carbon is bonded to another carbon atom in a hexagonal honeycomb pattern to form a tube. The diameter of the tube is extremely small, at the nanometer level, and exhibits unique electrochemical properties. When the nanotubes are formed of a thin conductive film on a plastic or glass substrate, they can be used as transparent electrodes because they exhibit high transmittance and conductivity in the visible light region.

The coating method of the CNT coating layer 120 may use a general wet coating method such as spray coating, gravure coating, slot die coating, dip coating, bar coating, roll to roll coating.

In this case, a part of the carbon nanotubes (C) constituting the CNT coating layer 130 may be inserted into the base binder layer 120 to be bonded.

Thereafter, as shown in FIG. 4, a top binder layer 140 including a wet etchable material is coated on the CNT coating layer 130. The top binder layer 140 is made of a binder material. The top binder layer 140 may be a binder including a ceramic-based and metal oxide, and may include, for example, materials such as TiO 2, SiO 2, ZnO, SnO, SiNx, SiON, SiN _x , ITO, ATO, and the like. .

The binder material serves to bond between the carbon nanotube strands. Therefore, at least a portion of the top binder layer 140 is coupled to the carbon nanotube strands of the CNT coating layer 130. Accordingly, the CNT coating layer 130 is coupled to the bottom by the binder material of the base binder layer 120, and is coupled to the binder material of the top binder layer 140 to the upper side.

Thereafter, the etching target region E of the base binder layer 120, the CNT coating layer 130, and the top binder layer 140 is removed by wet etching.

For example, as shown in FIG. 5, the etching paste 150 is pattern-coated on the etching target region E of the top binder layer 140. The surface on which the etching paste 150 is applied is etched by the wet etching equipment. The etching paste has a viscosity of about thousands to tens of thousands of Cps and is patterned on the top binder layer.

As a method of pattern-forming the said etching paste 150, the screen printing method can be used. The screen printing method may be performed by disposing a screen mask on the top binder layer 140 and printing an etching paste on the top binder layer through the hollow portion of the screen mask with a squeeze.

Thereafter, although not shown, the coating layer may be subjected to a heat treatment step of heating to an appropriate temperature to react with the etching paste. The etching rate can be increased by introducing heat into the etching paste through the above process.

Thereafter, as illustrated in FIG. 6, the etching paste 150, the top binder layer 140, the CNT coating layer 130, and the base binder layer 120 to which the etching paste is applied are removed by washing. Go through the steps. In the washing step, when the etching paste 150 is rinsed in di-water, the top binder layer 140 coated with the etching paste 150 and the etching paste, the CNT coating layer 130, and the base The binder layer 120 is etched and removed to complete the patterned carbon nanotube film 100.

Originally, carbon nanotubes (C) are not removed by wet etching. On the other hand, the top binder layer 140 and the base binder layer 120 is made of a material that can be removed by wet etching.

According to the present invention, the CNT coating layer 130 is bound to the top binder layer 140 on the upper side and bound to the base binder layer 120 on the lower side, so that the top binder layer 140 and the base binder layer 120 are bound. ) Is etched along the etching paste 150, thereby allowing the CNT coating layer 130 bound thereto to be etched.

On the other hand, it is obvious that the wet etching method is not limited to the wet etching method using the above-described etching paste. That is, the wet etching that can be applied to the present invention can apply a photoresist method. That is, a photoresist, which is a photosensitive resin, is coated, and a photoresist is selectively transmitted by transmitting light having a wavelength in a specific region using a mask serving as a patterned disc, and then a photoresist is selectively developed. The etching target region E, which is a portion selectively exposed by the developing process, can be removed by a chemical method such as an etching solution or a reactive gas.

The present invention is not limited to the etching paste coating method or the photoresist method, and the top binder layer 140, the CNT coating layer 130, and the base binder layer (in the etching target region E) using a chemical solution ( If 120 can be melted, all of the present invention.

According to the present invention, the CNT coating layer 130 is patterned by wet etching. Accordingly, there is an advantage that the conventional wet etching equipment for forming a pattern of an electrode such as ITO can be applied as it is. In addition, there is an advantage that can be quickly etched, and have a fine pattern width.

7 is a flow chart showing the steps of the carbon nanotube film manufacturing method according to a second embodiment of the present invention. As shown in FIG. 7, the carbon nanotube film manufacturing method S200 includes forming a CNT coating layer including carbon nanotubes on an upper surface of the substrate (S210), and a wet-etchable tower on the upper surface of the CNT coating layer. Forming a binder layer (S220), removing the etching target region of the top coating layer through wet etching (S230), and plasma etching the exposed portion of the CNT coating layer (S240). Include.

8 to 12 are cross-sectional views showing each step of the method for manufacturing a carbon nanotube film according to the second embodiment of the present invention.

First, as shown in FIG. 8, the CNT coating layer 230 including the carbon nanotubes (c) is formed on the substrate 210. The substrate 210 may be glass as described above, or may be a material such as a polymer such as PET, PC, PI, PEN, COC, or the like. In this case, the substrate is coated with a CNT coating layer, it can be applied to a display panel or a touch screen. For this purpose, the substrate is preferably made of a transparent material. In addition, the substrate may be used as a member requiring flexibility such as electronic paper. In this case, it is preferable that the base material is made of a transparent inorganic substrate or a transparent polymer substrate to have flexibility.

The CNT coating layer 230 includes carbon nanotubes (c). The coating method of the CNT coating layer 120 may use a general wet coating method such as spray coating, gravure coating, slot die coating, dip coating, bar coating, roll to roll coating.

Next, as shown in FIG. 9, the top binder layer 240 made of a wet etchable material is formed on the upper surface of the CNT coating layer 230. The top binder layer 240 may be a binder including a ceramic-based and a metal oxide, and may include, for example, materials such as TiO 2, SiO 2, ZnO, SnO, SiNx, SiON, SiN _x , ITO, ATO, and the like. .

Thereafter, the etching target region of the top binder layer 240 is removed by wet etching.

As one of the wet etching methods, as illustrated in FIGS. 10 and 11, an etching paste 250 is formed on the etching target region E of the top binder layer 240, and then washed to form the etching paste 250. Step 250 and the top binder layer 240 covered with the etching paste 250 may be removed.

As another wet etching method, a photoresist, which is a photosensitive resin, is coated on the top binder layer, and light is selectively reacted with the photoresist by transmitting light having a wavelength in a specific region using a mask serving as a pattern disc. After developing, develop the reaction part. The top binder layer can be selectively removed by chemically etching the portions selectively exposed by the developing process.

Thereafter, as shown in FIG. 12, the top binder layer 240 is removed from the CNT coating layer 230, and the exposed portion of the CNT coating layer 230 is exposed to the outside. By chemical dry etching is meant an etching in which the reactive species generated in the plasma are supplied to the surface of the material to be etched where a chemical reaction occurs between the reactive species and the surface atoms, resulting in the generation of volatile gases.

As one of the chemical dry etching methods, the CNT coating layer 230 may be subjected to oxygen plasma etching. Then, the carbon of the CNT coating layer 230 is chemically combined with oxygen during plasma etching to remove carbon dioxide (CO 2) to form a patterned carbon nanotube film 200. Chemical dry etching methods include reactive ion etching, reactive sputter etching, reactive ion beam milling, and the like, in addition to the plasma etching.

By using the plasma etching equipment 290, there is an advantage that the etching time is shortened compared to the laser etching method commonly used for the CNT coating layer pattern of the conventional carbon nanotube film.

In this case, during the oxygen plasma etching operation, the degree of plasma etching may be adjusted so that the carbon nanotubes (c) constituting the CNT coating layer may not be completely removed, but may remain so that electricity does not flow. The remaining carbon nanotubes (c) function to prevent visual differences from the CNT coating layer 230 other than the region to be removed. Accordingly, the user can see the surface having a homogeneous color instead of the mottled shape with the naked eye.

FIG. 13 is a flowchart illustrating a carbon nanotube film manufacturing method S300 according to a third embodiment of the present invention. As shown in FIG. 13, the carbon nanotube film manufacturing method (S300) according to the third exemplary embodiment of the present invention forms a CNT coating layer including an additive containing carbon nanotubes and a wet etchable material on a substrate. Step S310, forming a wet etchable top binder layer on the upper surface of the CNT coating layer (S320), and removing the etching target regions of the CNT coating layer and the top binder layer through wet etching (S330). Rough

14 to 17 are cross-sectional views showing each step of the carbon nanotube film manufacturing method according to the third embodiment of the present invention.

First, as shown in FIG. 14, a CNT coating layer 330 including a carbon nanotube (c) and an additive 336 containing a wet etchable material is formed on the substrate 310. The additive 336 containing the wet etchable material is a material that can be removed by wet etching, and the carbon nanotubes (c) must be firmly bonded to each other, and the carbon nanotubes bonded thereto by wet etching are also removed. It should be made of material The additive containing the wet etchable material may be an additive including a ceramic series and a metal oxide, and may include, for example, a material such as TiO 2, SiO 2, ZnO, SnO, SiNx, SiON, SiN _x , ITO, ATO, or the like. have.

In this case, the concentration of the additive 336 preferably accounts for 0.001 to 30% by weight relative to the total weight of the solution forming the CNT coating layer. This is because the etching effect is lowered when it is lower than 0.001wt%, and when it is higher than 30wt%, there is a problem that the conductivity is deteriorated due to the increase of the amount of the additive.

Next, a wet etchable top binder layer 340 is formed on the CNT coating layer 330. The top binder layer 340 is the same as the material and function of the

top binder layers

140 and 240 of the first and second embodiments of the present invention, so a detailed description thereof will be omitted.

Thereafter, the etching target region E of the top binder layer 340 and the CNT coating layer 330 is removed by wet etching.

An example of a wet etching method is a method of using an etching paste as shown in FIGS. 16 and 17.

That is, as shown in FIG. 16, the etching paste 350 is coated on the etching target region E of the top binder layer 340. After that, as shown in FIG. 17, the etching paste 350 and the CNT coating layer 330 covered by the etching paste are removed through the cleaning, thereby completing the patterned carbon nanotube film 300. .

Carbon nanotubes are not originally etched by wet etching methods. According to the present invention, the CNT coating layer 330 includes a wet etchable additive, and the top binder layer 350 is made of a wet etchable material, so that the carbon nanotubes are wetted with the top binder layer and the additive during wet etching. Can be removed together.

In addition, it is clear that the wet etching method of this invention is not limited only to the method by the said etching paste as mentioned above.

18 is a flowchart illustrating a method of manufacturing a carbon nanotube film according to a fourth preferred embodiment of the present invention, and FIGS. 19 to 21 illustrate each step before etching in a method of manufacturing a carbon nanotube film according to a fourth preferred embodiment of the present invention. It is sectional drawing which shows.

As shown in FIG. 18, the carbon nanotube film manufacturing method (S400) according to the fourth embodiment of the present invention includes forming a wet-etchable base binder layer on a substrate (S410) and the base binder layer. Forming a CNT coating layer including carbon nanotubes and wet etchable nanoparticles on the upper surface (S420), forming a wet etchable top binder layer on the upper surface of the CNT coating layer (S430), and wet etching Removing the CNT coating layer, the top binder layer, and the etching target region of the base binder layer through (S440).

Hereinafter, a carbon nanotube film manufacturing method according to a fourth embodiment of the present invention will be described with reference to FIGS. 19 to 21. In this case, removing the etching target region of the CNT coating layer, the top binder layer, and the base binder layer by wet etching may include removing the etching target region of the first embodiment of the present invention (S140); Since the steps are substantially the same, a description thereof will be omitted. In addition, the base material 410, the binder 421 of the base binder layer 420, the binder 443 of the top binder layer 440, and the carbon nanotube (C) also according to the first embodiment of the present invention Functions of the base material 110, the binder 121 of the base binder layer 120, the binder 143 of the top binder layer 140, and the carbon nanotube C in the description of the carbon nanotube film manufacturing method And since the material is substantially the same, it will be mainly described for the difference.

First, as shown in FIG. 19, a wet etchable base binder layer 420 is formed on the substrate 410.

The binder 421 used for the base binder layer 420 is applied according to the material of the substrate. Therefore, the binder used for the base binder layer 420 may not be wet etched.

The base binder layer 420 may be wet etched by further including wet-etchable nanoparticles 423 regardless of whether the binder is wet etchable. In this case, the nanoparticles 423 may be ceramic nanoparticles or metal oxide nanoparticles. In this case, the nanoparticles are TiO ₂ , SiO ₂ , SiON, SiN _x , SiN _x , ZnO, SnO, Al ₂ O ₃ , ZrO ₂ , Y ₂ O ₃ , WO ₃ , V ₂ O ₅ , NiO, Mn _{At least one selected from 3} O ₄ , MgO, La ₂ O ₃ , Fe ₂ O ₃ , Cr ₂ O ₃ , Co ₃ O ₄ , CuO, CeO ₂ , ITO, ATO, AZO, FTO, GZO, Sb ₂ O ₃ Can be.

In this case, as the solvent, alcohols, amines, distilled water and general organic solvents can be selected, and the solvent preferably has a boiling point of 150 ° C. or lower so that it can be easily removed later.

The base binder layer 420 may be formed by mixing the binder 421 and the nanoparticles 423 in a solvent to form a base binder solution, and then coating the substrate on the substrate.

In this case, the size of the nanoparticles 423 may be 1nm to 1㎛. When the size of the nanoparticles is less than 1 nm, even if the nanoparticles are wet-etched, there is a problem in that the etching is not performed together with the binder because the influence on the base binder layer is insignificant. This is because there is a problem that the coating surface is not uniformly dispersed within the sink, or the coating surface is formed unevenly after coating.

In addition, in the base binder solution constituting the base binder layer 420, the nanoparticles 423 preferably has a content of 1 to 500 relative to 100 parts by weight of the base binder, which is wet etching when less than 1 part by weight. This is because the problem is that if the content is more than 500 parts by weight, the physical properties of the base binder layer are changed, and the particles after the coating scatter light to increase haze.

Thereafter, as shown in FIG. 20, the CNT coating layer 430 is formed on the base binder layer 420. The CNT coating layer 430 includes a wet etchable nanoparticle 433. The nanoparticles 433 are bound to a binder together with the carbon nanotubes (C), thereby adhering to the carbon nanotubes (C). Accordingly, during the wet etching, the nanoparticles 433 are etched and the carbon nanotubes C are also etched.

The nanoparticles 433 may be ceramic nanoparticles or metal oxide nanoparticles. In this case, the nanoparticles are TiO ₂ , SiO ₂ , SiON, SiN _x , SiN _x , ZnO, SnO, Al ₂ O ₃ , ZrO ₂ , Y ₂ O ₃ , WO ₃ , V ₂ O ₅ , NiO, Mn _{At least one selected from 3} O ₄ , MgO, La ₂ O ₃ , Fe ₂ O ₃ , Cr ₂ O ₃ , Co ₃ O ₄ , CuO, CeO ₂ , ITO, ATO, AZO, FTO, GZO, Sb ₂ O ₃ Can be.

The CNT coating layer 430 may be formed by coating a CNT coating solution on the upper surface of the base binder layer 420. In this case, the CNT coating solution may be prepared by mixing a binder, a nanoparticle 433 and a carbon nanotube (C) in a solvent.

As one method of preparing the CNT coating solution, first, carbon nanotubes (C) are dispersed.

One example of the carbon nanotube dispersion method is to disperse the carbon nanotubes in an organic solvent such as amide-based DMF (NN-dimethylformamide) or NMP (1,2-dichlorobenzene, N-methylpyrrolidone).

Another example of the carbon nanotube dispersion method may be a water-soluble dispersant. Examples of the water-soluble dispersant include sodium dodecyl sulfate (SDS), triton x-100 (tx-100), sodium dodecylbenzene sulfonate (NaDDBS), and gum arabic.

Thereafter, a binder and nanoparticles are added to a solvent in which carbon nanotubes are dispersed. The binder can be applied to any conventional binder for binding between the carbon nanotubes.

In this case, in this case, the size of the nanoparticles may be 1nm to 1㎛.

Meanwhile, the forming of the CNT coating layer may be performed by coating a CNT coating solution in which a nanoparticle and carbon nanotubes are mixed in a solvent, and the nanoparticles may have a content of 1 to 500 with respect to 100 parts by weight of CNT. .

In this case, the size of the nanoparticles 433 is preferably 1nm to 1㎛. When the size of the nanoparticles is less than 1 nm, even if the nanoparticles are wet etched, the effect on the CNT coating layer is insignificant, and the etching solution penetrates into the base binder layer, thereby preventing the CNT coating layer and the base binder layer from being etched together. This is because when the size of the nanoparticles exceeds 1 μm, the nanoparticles do not uniformly disperse in the coating solution and sink or decrease the dispersibility of CNTs.

In addition, in the CNT coating solution, the nanoparticles 433 preferably have a content of 1 to 500 with respect to 100 parts by weight of the carbon nanotubes, which is less than 1 part by weight of the wet etching is not properly, 500 weight If the addition exceeds, the dispersibility of the CNT coating solution is lowered, the physical properties of the CNT coating layer after the coating is changed, and the nanoparticles scatter light to increase the haze.

Examples of the nanoparticles 433 include Titanium IV 2-propanolato, trisisooctadecanoato-O, Titanium IV bis 2-methyl-2-propenoato-O, isooctadecanoato-O 2-propanolato, Titanium IV 2-propanolato, and tris (dodecyl). ) benzenesulfanato-O, Titanium IV 2-propanolato, tris (dioctyl) phosphato-O, Zirconium IV 2. 2-dimethyl 1,3propanediolato, bis (dioctyl) pyrophosphato-O, (adduct) 2 moles N, N-dimethylamino -alkyl propenoamide, Zirconium IV (2-ethyl, 2-propenolatomethyl) 1,3-propanediolato, cyclobis 2-dimethylamino pyrophosphato-O, adduct with 2 moles of methanesulfonic acid, and Zirconium IV tetrakis 2,2 (bis-2 propenolatomethyl butanolato, adduct with 2 moles of di-tridecyl, hydrogen phosphite, Zirconium IV 2-ethyl, 2-propenolatomethyl 1, 3-propanediolato, cyclo di 2, 2- (bis 2-propenolatomethyl) butanolatopyrophosphato-O, O Can be.

Thereafter, as shown in FIG. 21, a wet etchable top binder layer 440 is coated on the CNT coating layer 430.

The top binder layer 440 may be formed by mixing wet etchable nanoparticles 443 with a binder 441. The binder can be selected according to the function of the top binder layer, and in this case, a binder which cannot be wet etched can be used as the main material of the top binder layer.

In this case, when the nanoparticles 443 are added to the binder 441, the entire top binder layer may be wet-etched as the nanoparticles are wet etched.

The nanoparticles may have a size of 1 nm to 1 μm. When the size of the nanoparticles is less than 1 nm, even if the nanoparticles are wet etched, the effects on the binder layer are insignificant, so that the nanoparticles may not be etched together with the binder. This is because there is a problem that the coating surface is not uniformly dispersed, or the coating surface is unevenly formed after coating.

In addition, in the top binder solution constituting the top binder layer, the nanoparticles preferably have a content of 1 to 500 with respect to 100 parts by weight of the top binder, which is less than 1 part by weight of the wet etching is not properly, 500 This is because when the weight part is exceeded, the physical properties of the base binder layer are changed, and the particles after coating have a problem in that haze is increased by scattering light.

Thereafter, although not shown in the drawings, the etching target regions of the base binder layer 420, the CNT coating layer 430, and the top binder layer 440 may be removed by wet etching.

According to the present invention, the CNT coating layer 430 is bound to the top binder layer 440 on the upper side and the base binder layer 420 on the lower side, and nanoparticles are added to the CNT coating layer. The layer 440 and base binder layer 420 are etched along the etching paste, allowing the CNT coating layer 430 bound thereto to be easily etched.

That is, the etchant etches the nanoparticles exposed to the outside of the top binder layer 440 and the CNT coating layer. The etchant then etches the base binder layer 420 through the etched portion of the CNT coating layer. Thereafter, upon washing, the remaining CNT coating layers are etched together.

As described above, although described with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and changed within the scope without departing from the spirit and scope of the invention described in the claims below I can understand that you can.

The present invention can be applied to the field in which the charging film is applied in the display industry, the semiconductor industry, the optical field, the lighting field, and the like.

Claims

Forming a base binder layer on the substrate, the base binder layer comprising a wet etchable material;

Forming a CNT coating layer including carbon nanotubes on an upper surface of the base binder layer;

Forming a top binder layer on the CNT coating layer, the top binder layer comprising a wet etchable material; And

Removing the CNT coating layer, the top binder layer, and the etching target region of the base binder layer by wet etching;

Carbon nanotube film manufacturing method comprising a.
The method according to claim 1,

The wet etching step includes:

Applying an etching paste on an upper surface of the etching target region of the top binder layer; And removing the etching paste, the top binder layer coated with the etching paste, the CNT coating layer, and the base binder layer by washing.

Carbon nanotube film manufacturing method comprising a.
The method according to claim 1,

The wet etching step includes:

Forming a mask using a photoresist in accordance with an etching target region of the top binder layer; And

Chemically etching the etching target region by supplying an etching solution or a reactive gas on the mask;

Carbon nanotube film manufacturing method comprising a.
The method according to claim 2 or 3,

The base binder layer and the top binder layer, the carbon nanotube film manufacturing method characterized in that it comprises a ceramic-based and metal oxide material.
Forming a CNT coating layer including a carbon nanotube on an upper surface of the substrate;

Forming a wet etchable top binder layer on the CNT coating layer;

Removing the etching target region of the top coating layer through wet etching; And

Plasma surface etching the exposed portion of the CNT coating layer to the outside;

Carbon nanotube film manufacturing method comprising a.
The method according to claim 5,

The top binder layer is a carbon nanotube film manufacturing method comprising a ceramic-based and a metal oxide material.
The method according to claim 5,

Plasma etching the portion exposed to the outside of the CNT coating layer, carbon nanotube film manufacturing method characterized in that the oxygen plasma etching treatment.
The method according to claim 5,

In the wet etching, the top binder layer is removed, wherein the top binder layer is removed by the etching paste coating method or the photoresist method.
Forming a CNT coating layer comprising an additive containing carbon nanotubes and a wet etchable material on the substrate;

Forming a wet etchable top binder layer on the CNT coating layer; And

Removing the etching target regions of the CNT coating layer and the top binder layer by wet etching;

Carbon nanotube film manufacturing method comprising a.
The method according to claim 9,

The concentration of the additive is a carbon nanotube film production method characterized in that occupies 0.001 to 30wt% content per weight of the solution forming the CNT coating layer.
The method according to claim 9,

Removing the CNT coating layer through wet etching, using the etching paste coating method or photoresist method, the carbon nanotube film manufacturing method, characterized in that for removing the CNT coating layer.
Forming a wet etchable base binder layer on the substrate;

Forming a CNT coating layer on the base binder layer, the CNT coating layer including carbon nanotubes and wet-etchable nanoparticles;

Forming a wet etchable top binder layer on the CNT coating layer; And

Removing the CNT coating layer, the top binder layer, and the etching target region of the base binder layer by wet etching;

Carbon nanotube film manufacturing method comprising a.
The method according to claim 12,

The nanoparticles are ceramic nanoparticles or metal oxide nanoparticles, characterized in that the carbon nanotube film production method.
The method according to claim 13,

The nanoparticles, the nanoparticles are TiO 2 , SiO 2 , SiON, SiN x system, SiN x system, ZnO, SnO, Al 2 O 3 , ZrO 2 , Y 2 O 3 , WO 3 , V 2 O 5 , NiO Selected from Mn 3 O 4 , MgO, La 2 O 3 , Fe 2 O 3 , Cr 2 O 3 , Co 3 O 4 , CuO, CeO 2 , ITO, ATO, AZO, FTO, GZO, and Sb 2 O 3 Carbon nanotube film production method characterized in that at least one.
The method according to claim 13 or 14,

Carbon nanotube film manufacturing method, characterized in that the size of the nanoparticles are 1 nm to 1 μm.
The method according to claim 12,

Forming the CNT coating layer is made by coating a CNT coating solution in which nanoparticles and carbon nanotubes are mixed in a solvent,

The nanoparticles carbon nanotube film manufacturing method characterized in that it has a content of 1 to 500 parts by weight relative to 100 parts by weight of the carbon nanotubes.
The method according to claim 12,

At least one of the base binder layer and the top binder layer, the carbon nanotube film manufacturing method characterized in that it comprises a ceramic-based or metal oxide-based nanoparticles.