KR20180049411A - Conductive Coated Composition Comprising The Same, Antistatic Film And Display Device Using The Same - Google Patents

Abstract

A conductive coating liquid composition according to an embodiment of the present invention comprises, 10 to 100 parts by weight of a silane sol based on 100 parts by weight of a carbon nanotube dispersion composition, and 0.1 to 1 parts by weight of a silsesquioxane compound having a disulfide group linking a siloxane group based on 100 parts by weight of the conductive coating liquid composition. An object of the present invention is to provide the carbon nanotube dispersion composition having excellent dispersibility and composition stability of carbon nanotubes.

Description

Technical Field [0001] The present invention relates to a conductive coating liquid composition, an antistatic film using the same,

The present invention relates to a conductive coating liquid composition, an antistatic film using the same, and a display device.

Recently, as the information society has developed rapidly, there has been a need for a flat panel display having excellent characteristics such as thinness, light weight, and low power consumption. Among them, a liquid crystal display Color display, and picture quality, and is actively applied to a notebook or desktop monitor.

In general, a liquid crystal display device is a liquid crystal display device in which two substrates, each having electrodes formed on one surface thereof, are disposed so as to face the surface on which the electrodes are formed, a liquid crystal material is interposed between the two substrates, And moving the liquid crystal molecules by an electric field generated by applying the electric field to the liquid crystal molecules. At this time, a lot of static electricity is generated in the course of the unit process of manufacturing each substrate of the liquid crystal display device.

Therefore, in order to discharge such static electricity and to effectively discharge the charged electric charge in forming the finished product, indium-tin-oxide (ITO) or indium-zinc-oxide (IZO), which is a transparent conductive material, It is used as antistatic film. However, since indium-tin-oxide (ITO) or indium-zinc-oxide (IZO) is a very expensive transparent conductive metal material, it has become a factor for improving the manufacturing cost. In particular, Indium, which is the main material of indium-tin-oxide (ITO) or indium-zinc-oxide (IZO), is a rare metal and its price is rapidly increasing recently. This is a difficult situation.

In recent years, a touch sensor has been installed in a mobile phone, a PDA or a notebook which can be carried by a person, and a product having a function of touching the screen has been released. In recent years, various attempts have been made to provide a touch function even in a liquid crystal display device that has been used as a display device in various application products by taking advantage of such a tendency. Among these, the demand for an in-cell type liquid crystal display device in which a touch function is mounted is increasing. The liquid crystal display device of the in-cell touch method has advantages such as slimming of the product, cost structure improvement due to the reduction of the material cost, and lightness because the touch panel is formed inside the display panel without attaching a separate touch panel on the liquid crystal display device.

However, even if a touch sensor is provided in the form of an inshell in the display panel, it is impossible to detect a change in capacitance caused by the touch of a finger or the like due to the discharge by the above-mentioned antistatic layer, . In other words, since the antistatic film has a relatively large electrical conductivity compared to the capacitance generated by the finger touch, the antistatic film acts as a conductor to cause a discharge, and the touch sensor recognizes the touch of the operator's finger or the like I will not be able to do it. Therefore, if the antistatic film is removed to solve such a problem, the defective rate increases due to the generation of static electricity during the manufacturing process, which causes the manufacturing cost to rise again due to the increase in the failure cost, and the display quality is degraded.

In addition, scratches are generated in the antistatic film when cleaning the abrasive belt of the display panel after the antistatic film is formed on the display panel. The scratches generated in the antistatic film are visually recognized by the user and the display quality is deteriorated.

An object of the present invention is to provide a carbon nanotube dispersion composition having excellent dispersibility and composition stability of carbon nanotubes.

It is another object of the present invention to provide a conductive coating liquid composition comprising the carbon nanotube dispersion composition.

It is another object of the present invention to provide a display device having an antistatic film formed of the conductive coating liquid composition.

The present invention also provides an electrostatic discharge device which can easily discharge static electricity generated in the manufacturing process to the outside to suppress defects due to static electricity, prevent deterioration of touch sensitivity, improve sheet resistance uniformity, heat resistance and reliability, Prevention film and a display device.

It is still another object of the present invention to provide an antistatic film and a display device capable of improving film density, hardness and abrasion resistance.

In order to achieve the above object, the conductive coating liquid composition according to an embodiment of the present invention comprises 10 to 100 parts by weight of a silane sol per 100 parts by weight of a carbon nanotube dispersion composition, And 0.1 to 1 part by weight of a silsesquioxane compound having a disulfide group linking groups.

As an example, silsesquioxane compounds are bonded in random and cage types.

In one example, the conductive coating liquid composition further comprises nanoparticles made of metal, ceramic, metal oxide, or a mixture thereof.

For example, the carbon nanotube dispersion composition may contain 0.05 to 20% by weight of carbon nanotubes, 0.02 to 40% by weight of polyacrylic acid resin, 50 to 99.93 of linear alkanols having 2 to 5 carbon atoms per 100 parts by weight of the carbon nanotube dispersion composition By weight.

For example, the alkanol is at least one of ethanol, n-propanol, n-butanol and n-pentanol.

For example, it further includes an acrylic block copolymer dispersant.

For example, the acrylic block copolymer dispersant is substituted with at least one of an amine group and a carboxyl group.

For example, the acrylic block copolymer dispersant is included in an amount of 0.1 to 2% by weight based on the total weight of the composition.

For example, the silane sol includes an alkoxysilane compound, an acid catalyst, an alcohol-based solvent, and water.

For example, 20 to 60% by weight of an alkoxysilane compound, 0.01 to 10% by weight of an acid catalyst, 10 to 70% by weight of an alcoholic solvent and 5 to 60% by weight of water, based on the total weight of the silane sol.

In addition, the antistatic film according to an embodiment of the present invention is formed of the above-described conductive coating liquid composition.

Further, a display device according to an embodiment of the present invention includes an antistatic film formed of the conductive coating liquid composition described above.

Further, a display device according to an embodiment of the present invention includes a display panel, an upper polarizer, and an antistatic film. The display panel is positioned on the lower polarizer plate, and the upper polarizer plate is positioned on the display panel. The antistatic layer is disposed between the upper substrate and the upper polarizer of the display panel and includes a matrix material, a carbon nanotube dispersed in the matrix material, and a disulfide group connecting the siloxane group Silsesquioxane compounds.

The silsesquioxane compound is bonded in a random and cage type.

(여기서, R₂는 C1~C20의 알킬 그룹)에서 선택된다.The silsesquioxane compound is represented by the following formula, wherein R is independently an aromatic group or

(Wherein R < ₂ > is an alkyl group of C1-C20).

The antistatic film further comprises nanoparticles made of metal, ceramic, metal oxide, or a mixture thereof.

The antistatic film has a hardness of 8 to 9H.

The sheet resistance of the antistatic film is 10 ⁷ to 10 ⁹ Ω / □.

The anti-static film shows the number of times the steel wool is reciprocated from 113 to 483 times until a scratch is observed at a light quantity of 1.37 to 1500 mW / cm 2.

The display panel has a built-in touch electrode.

The carbon nanotube dispersion composition of the present invention is capable of effectively dispersing carbon nanotubes. By using an alcohol having a specific structure, the dispersion stability is also excellent.

The method for producing a carbon nanotube dispersion composition of the present invention can improve the dispersibility of carbon nanotubes and can significantly improve stability after dispersion.

The conductive coating liquid composition comprising the carbon nanotube dispersion composition of the present invention can form a uniform coating film, and the formed coating film has excellent chemical stability and electric conductivity.

The antistatic film produced by the conductive coating liquid composition according to the present invention exhibits excellent electrical conductivity and is excellent in mechanical strength and transparency and can be used as a coating film for anti-static use of a touch screen panel and an image display device.

The antistatic film made of the conductive coating liquid composition according to the present invention contains silsesquioxane having a disulfide group as a self-healing material, thereby improving the film density and thus improving hardness and abrasion resistance and improving scratch resistance have.

The antistatic film and the display device including the same according to the present invention can easily discharge the static electricity generated in the manufacturing process to the outside to suppress the defect caused by the static electricity, to prevent the deterioration of the touch sensitivity, to improve the uniformity of sheet resistance, And the manufacturing cost can be reduced.

1 is a sectional view showing a general display device;
2 and 3 are views schematically showing a display device of the present invention.
FIG. 4 is a waveform diagram showing a common voltage and a touch driving signal applied to the touch sensor shown in FIG. 2. FIG.
5 is a sectional view showing a display panel of the present invention.
6 is a cross-sectional view illustrating a display device according to an embodiment of the present invention.
FIG. 7 is a front view of the display device of FIG. 6; FIG.
8 is a plan view of an antistatic film according to an embodiment of the present invention.
9 to 11 are views schematically showing various display devices to which the antistatic film of the present invention is applied.
FIG. 12A is a table showing the sheet resistance and sheet resistance uniformity of the antistatic film for the sheet resistance of carbon nanotubes according to the embodiment, and FIG. 12B is a graph showing the sheet resistance uniformity of FIG. 12A.
13 is a graph showing a sheet resistance value of an antistatic film against the content of carbon nanotubes according to an embodiment.
14 is a table showing the light transmittance for the content of carbon nanotubes and the sheet resistance value according to the embodiment.
FIG. 15A is a graph showing changes in sheet resistance values of a general antistatic film over time, and FIG. 15B is a graph showing changes in sheet resistance values of the antistatic film according to the embodiment in a high temperature and high humidity environment.
16 is a graph comparing weight percentages of general antistatic films with temperature and weight percentages according to the temperature of the antistatic film according to the embodiment.
Fig. 17 is a schematic diagram of a curing process of a silsesquioxane compound. Fig.
18 is a schematic diagram showing a synthesis process of the silsesquioxane compound of the present invention.
19 is a Raman analysis graph of the silsesquioxane compound prepared in the present invention.
Figures 20 and 21 are FTIR analysis graphs of various silsesquioxane compounds.
22 is a diagrammatic illustration of the healing mechanism of self-healing materials;
23 and 24 are schematic diagrams of a healing mechanism of a silsesquioxane compound having a silane sol and a disulfide group.
25 is a graph showing the number of steel wool reciprocations in which scratches are observed according to the amount of UV light in the coating film prepared according to Example 14, Comparative Examples 6 and 7;
26 is a graph showing the sheet resistance and pencil hardness of the coating films prepared according to Example 15. Fig.

Hereinafter, some embodiments of the present invention will be described in detail with reference to exemplary drawings. It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference symbols as possible even if they are shown in different drawings. In the following description of the embodiments of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the invention, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected." In the same context, when an element is described as being formed on an "upper" or "lower" side of another element, the element may be formed either directly or indirectly through another element As will be understood by those skilled in the art.

1 is a cross-sectional view showing a general display device.

1, the display device 100 includes a lower substrate 120, an upper substrate 140 opposed to the lower substrate 120, and an antistatic film 150 positioned on the upper substrate 140 . A lower polarizer 110a is located on the outer side of the lower substrate 120 and a cell 130 is located between the lower substrate 120 and the upper substrate 130, And a touch electrode (not shown) may be disposed inside. On the other hand, the upper polarizer plate 110b is positioned on the upper substrate 140 and the antistatic film 150 is positioned on the upper polarizer plate 110b.

The display device 100 of FIG. 1 is an in-cell type display device 100 in which a touch electrode (not shown) is located inside a cell 130. However, this is for illustrative purposes only and is for convenience of explanation. The cell 130 may be, for example, a liquid crystal layer, and the display device 100 may be a liquid crystal display device.

The antistatic layer 150 may be formed of indium-tin-oxide (ITO) or indium-zinc-oxide (IZO) which is a transparent conductive material or may be formed of a conductive polymer such as PEDOT: PSS (polyethylenedioxythiphene: polystyrene sulfonic acid ). However, indium-tin-oxide (ITO) or indium-zinc-oxide (IZO) is a very expensive metal material, thus increasing manufacturing costs. In particular, Indium, which is the main material of indium-tin-oxide (ITO) or indium-zinc-oxide (IZO), is a rare metal and its price is rapidly increasing recently. This is a difficult situation. Since the sheet resistance value of indium-tin-oxide (ITO) or indium-zinc-oxide (IZO) is relatively low and electric conductivity is high, a voltage generated by a touch of a finger, 150, and thus the touch sensor can not recognize the touch. In addition, when the antistatic film 150 is made of a material such as PEDOT: PSS, reliability is lowered in a high temperature or high humidity (or high humidity) environment.

The antistatic layer 150 is connected to the edge of the lower substrate 120 through the first conductive member 170a, the conductive connection member 172, and the second conductive member 170b. A ground pad or the like made of a conductive material may be disposed on the edge of the lower substrate 120, though not shown. The static electricity generated in the display device 100 is transmitted to the outside due to the conductive material of the antistatic layer 150, the first conductive member 170a, the conductive connecting member 172, the second conductive member 170b, Is discharged.

The first conductive member 170a and the second conductive member 170b may be made of a metal such as silver or the like and the conductive connecting member 172 may be made of a metal material. However, since the first conductive member 170a, the conductive connecting member 172, and the second conductive member 170b must be formed, the number of processes increases and manufacturing cost increases. Further, there is a problem that the upper polarizer HPOL disposed on the antistatic film 250 shrinks and cracks occur in the first conductive member 170a.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an antistatic layer and a display device including the same according to embodiments of the present invention described below have a structure for solving the above-described problems. Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

≪ Embodiment 1 >

Hereinafter, an in-cell touch display device according to an embodiment of the present invention will be described.

2 and 3 are views schematically showing a display device of the present invention. 4 is a waveform diagram showing a common voltage Vcom and a touch driving signal Tdrv applied to the touch sensor Cs shown in FIG.

2 to 4, the display device of the present invention includes a touch sensing device. The touch sensing device senses a touch input by using the touch sensors Cs built in the display panel 300. Since the capacitance of the touch sensing device increases when a finger touches the self-capacitance type touch sensor Cs, the touch sensing device can sense the touch input based on the capacitance change of the touch sensor Cs.

In the display panel 300, a liquid crystal layer is formed between two substrates. The liquid crystal molecules are driven by an electric field generated by a potential difference between a data voltage applied to the pixel electrode 12 and a common voltage Vcom applied to the sensor electrode 13. [ The pixel array of the display panel 300 includes pixels defined by data lines (S, S1 to Sm, m is a positive integer) and gate lines (G, G1 to Gn, n are positive integers) And touch sensors Cs connected to the touch sensors Cs.

The touch sensor Cs includes a sensor electrode and a sensor wiring M3 connected to the sensor electrode. The sensor electrodes COM, C1 to C4 may be patterned by a conventional method of dividing the common electrode. Each of the sensor electrodes COM, C1 to C4 is overlapped with a plurality of pixels. The sensor electrodes COM and C1 to C4 receive the common voltage Vcom during the display driving period Td through the sensor wiring M3 and supply the touch driving signal Tdrv during the touch sensor driving period Tt Receive. The common voltage Vcom is commonly applied to the pixels through the sensor electrodes.

The sensor wirings M3 are disposed at the boundary between the subpixels avoiding the position of the spacers. The sensor wirings M3 may overlap with the data lines S1 to Sm with an insulating layer (not shown) therebetween so that there is no problem of aperture area reduction of the pixels.

Since the touch sensors are embedded in the pixel array of the display panel 300, the touch sensors Cs are connected to the pixels through the parasitic capacitance. In order to reduce the mutual influence due to coupling of the pixels and the touch sensors Cs, one frame period is called a display driving period (hereinafter, referred to as "display driving period" (Hereinafter referred to as "touch sensor driving period") for driving the display panel 300. One frame period may be divided into at least one display driving period Td and at least one touch sensor driving period Tt. During the display driving period Td, data of the input image is written to the pixels. During the touch sensor driving period (Tt), the touch sensors are driven and the touch input is sensed.

Each of the pixels includes a pixel thin film transistor (TFT) formed at the intersections of the data lines S1 to Sm and the gate lines G1 to Gn, a pixel electrode to receive the data voltage through the pixel TFT, A common electrode to which a voltage Vcom is applied, and a storage capacitor (Cst) connected to the pixel electrode to maintain the voltage of the liquid crystal cell.

A black matrix, a color filter, and the like may be formed on the upper substrate of the display panel 300. The lower substrate of the display panel 300 may be implemented as a COT (Color Filter On TFT) structure. In this case, the color filter may be formed on the lower substrate of the display panel 100. [ On the upper substrate and the lower substrate of the display panel 300, a polarizing plate is attached and an alignment film for forming a pre-tilt angle of liquid crystal on the inner surface in contact with the liquid crystal is formed. Spacers for maintaining the cell gap of the liquid crystal layer are formed between the upper substrate and the lower substrate of the display panel 300.

A backlight unit may be disposed under the rear surface of the display panel 300. [ The backlight unit is implemented as an edge type or direct type backlight unit to irradiate the display panel 300 with light. The display panel 300 may be implemented by any known liquid crystal mode such as TN (Twisted Nematic) mode, VA (Vertical Alignment) mode, IPS (In Plane Switching) mode, FFS (Fringe Field Switching) In a self-luminous display device such as an organic light emitting diode display device, a backlight unit is not required.

 The display apparatus of the present invention further includes a display driver 302, 304, 306 for writing data of an input image to pixels, and a touch sensor driver 310 for driving the touch sensors Cs. The display driver units 302, 304, and 306 and the touch sensor driver unit 310 are synchronized with each other in response to the synchronization signal Tsync.

The display driver 302, 304, and 306 write data to the pixels during the display driving period Td. The pixels hold the data voltage charged in the previous display driving period Td since the TFT is in the off state during the touch sensor driving period Tt. The display driving units 302, 304, and 306 apply the touch signals to the touch sensors Cs in order to minimize the parasitic capacitance between the touch sensors Cs and the signal lines connected to the pixels during the touch sensor driving period Tt. It is possible to supply an AC signal having the same phase as the touch driving signal Tdrv to the signal lines S1 to Sm and G1 to Gn. Here, the signal lines connected to the pixels are the data line lines S1 to Sm and the gate lines G1 to Gn.

The display drivers 302, 304, and 306 include a data driver 302, a gate driver 304, and a timing controller 306.

The data driver 302 converts the digital video data RGB and RGBW of the input image received from the timing controller 306 during the display driving period Td into an analog positive / negative gamma compensation voltage to output a data voltage . The data voltage output from the data driver 302 is supplied to the data lines S1 to Sm. The data driver 302 may apply an AC signal having the same phase as the touch driving signal Tdrv applied to the touch sensors during the touch sensor driving period Tt to the data lines S1 to Sm. This is because the voltage across both ends of the parasitic capacitance changes simultaneously and the smaller the voltage difference becomes, the smaller the amount of charge charged in the parasitic capacitance becomes.

The gate driver 304 sequentially applies a gate pulse (or a scan pulse) synchronized with the data voltage to the gate lines G1 to Gn during the display driving period Td to sequentially apply the data voltage to the display panel 300, ≪ / RTI > The gate pulse swings between the gate high voltage (VGH) and the gate low voltage (VGL). The gate pulse is applied to the gate of the pixel TFTs through the gate lines G1 to Gn. The gate high voltage VGL is set to a voltage higher than the threshold voltage of the pixel TFT to turn on the pixel TFT. The gate-low voltage VGL is lower than the threshold voltage of the pixel TFT. The gate driver 304 may apply an AC signal having the same phase as the touch driving signal Tdrv applied to the touch sensors during the touch sensor driving period Tt to the gate lines G1 to Gn.

The timing controller 306 receives a timing signal such as a vertical synchronizing signal, a horizontal synchronizing signal, a data enable signal, and a main clock inputted from the host system 308 and supplies the timing signal to the data driving unit 302, the gate driving unit 304, The operation timing of the driving unit 310 is synchronized. The scan timing control signal includes a gate start pulse (GSP), a gate shift clock, a gate output enable signal (GOE), and the like. The data timing control signal includes a source sampling clock (SSC), a polarity control signal (Polarity), a source output enable signal (SOE), and the like.

The timing controller 306 transfers input image data (RGB) from the host system 308 to the data driver 302. The timing controller 306 converts the RGB data into RGBW data using a known white gain calculation algorithm and transmits the RGBW data to the data driver 302.

The host system 308 may be implemented in any one of a television system, a set-top box, a navigation system, a DVD player, a Blu-ray player, a personal computer (PC), a home theater system, and a phone system. The host system 308 includes a system on chip (SoC) with a built-in scaler to convert the digital video data of the input image into a format suitable for the resolution of the display panel 300. The host system 308 transmits the timing signals to the timing controller 306 together with digital video data (RGB, RGBW) of the input image. In addition, the host system 308 executes an application program associated with the coordinate information XY of the touch input input from the touch sensor driver 310. [

The timing controller 306 or the host system 308 may generate a synchronization signal Tsync for synchronizing the display drivers 302, 304, and 306 with the touch sensor driver 310.

The touch sensor driving unit 310 generates the touch driving signal Tdrv during the touch sensor driving period Tt. The touch driving signal Tdrv is supplied to the sensor electrodes 13, C1 to C4 through the sensor wiring M3. The touch sensor driving unit 310 can sense the touch position and the touch area by measuring the capacitance change of the touch sensor Cs. The touch sensor driver 310 calculates coordinate information XY of the touch input and transmits it to the host system 308.

The data driving circuit 12 and the touch sensor driving unit 310 may be integrated in one integrated circuit (IC).

5 is a sectional view showing the sectional structure of the display panel 300. As shown in Fig.

Referring to Fig. 5, the lower plate of the display panel 300 includes a TFT array on the lower substrate SUBS1. The top plate of the display panel 300 includes a color filter array on the top substrate SUBS2. A liquid crystal layer LC is formed between the upper panel and the lower panel of the display panel 300.

A buffer insulating film BUF, a semiconductor pattern ACT, and a gate insulating film GI are formed on the lower substrate SUBS1. A first metal pattern is formed on the gate insulating film (GI). The gate metal pattern includes a gate (GE) of a TFT and gate lines (G1 to Gn) connected to the gate (GE). The interlayer insulating film INT covers the second metal pattern. A source-drain metal pattern is formed on the interlayer insulating film INT. The second metal pattern includes data lines S1 to Sm and a source SE and a drain DE of the TFT. The drain DE is connected to the data lines S1 to Sm. The source SE and the drain DE of the TFT are in contact with the semiconductor pattern ACT of the TFT through the contact hole penetrating the interlayer insulating film INT.

The first protective film PAS1 covers the second metal pattern. A second protective film PAS2 is formed on the first protective film PAS1. A contact hole exposing the source SE of the TFT is formed in the second protective film PAS2. The third protective film PAS2 is formed on the second protective film PAS2 and the third metal pattern is formed on the third protective film PAS3. The third metal pattern includes the sensor wiring M3. The fourth protective film PAS4 is formed on the third protective film PAS3 so as to cover the third metal pattern. And a fourth metal pattern is formed on the fourth protective film PAS4. The fourth metal pattern includes a sensor electrode 13 (COM) formed of a transparent electrode material such as indium-tin oxide (ITO). The fifth protective film PAS5 is formed on the fourth protective film PAS4 so as to cover the fourth metal pattern. The first, third, fourth and fifth protective films PAS1, PAS3, PAS4 and PAS5 may be formed of an inorganic insulating material such as SiOx or SiNx. The second protective film PAS2 may be formed of an organic insulating material such as photo-acryl.

The third, fourth and fifth protective films PAS1, PAS3, PAS4 and PAS5 are patterned to include a contact hole exposing the source SE of the TFT. A fifth metal pattern is formed on the fifth protective film PAS5. The fifth metal pattern includes a pixel electrode 12 (PXL) formed of a transparent electrode material such as ITO. The alignment film ALM is formed on the fifth protective film PAS5 so as to cover the fifth metal pattern.

A black matrix BM and a color filter CF are formed on the upper substrate SUBS2 and a planarizing film OC is formed thereon. The planarizing film OC may be formed of an organic insulating material. Although not shown, a spacer is formed between the upper substrate and the lower substrate to maintain a cell gap of the liquid crystal layer.

The antistatic film 250 of the present invention is formed on the upper substrate SUBS2. The antistatic layer 250 according to the present invention exhibits excellent electrical conductivity and is excellent in mechanical strength and transparency and can be used as a coating layer for antistatic use in touch screen panels and display devices. The method of forming the antistatic film 250 is not particularly limited, but it may be formed by applying the conductive coating liquid composition according to the present invention to a substrate and curing the substrate. The coating method is not particularly limited, and a coating method such as a slit coating method, a knife coating method, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, Known methods such as a coating method, a screen printing method, a gravure printing method, a flexo printing method, an offset printing method, an inkjet coating method, a dispenser printing method, a nozzle coating method and a capillary coating method can be used. After the application, the antistatic film 250 can be formed by curing the coating film through a drying process at a predetermined temperature.

A display device including the above-described antistatic film will be described in detail as follows.

6 is a cross-sectional view illustrating a display device according to an embodiment of the present invention, FIG. 7 is a front view of the display device of FIG. 6, and FIG. 8 is a plan view of an antistatic film according to an embodiment of the present invention.

6 to 8, the display device 200 includes a display panel 300 positioned on the lower polarizer LPOL, an upper polarizer HPOL located on the display panel 300, and a display panel 300 And an antistatic film 250 disposed between the upper substrate SUBS2 and the upper polarizer HPOL.

More specifically, the display panel 300 includes a lower substrate SUBS1, a cell 230, and an upper substrate SUBS2 which are sequentially stacked. Here, the lower substrate SUBS1 may be an array substrate SUBS1 having transistors for driving the cells 230 and various signal lines and electrodes, and the upper substrate SUBS2 may be a color filter (not shown) and a black The matrix (Black Matrix) (not shown) may be a color filter substrate. In this specification, the lower substrate SUBS1 may be used in the same sense as the array substrate, and the upper substrate SUBS2 may be used in the same meaning as the color filter substrate. The lower substrate SUBS1 and the upper substrate SUBS2 may be made of, for example, glass, but are not limited thereto.

The display panel 300 may be a liquid crystal display panel including a liquid crystal layer, and the display device 200 may be a liquid crystal display device. However, the present invention is not limited to the liquid crystal display device. For example, the cell 230 may be an organic layer of an organic light emitting display. When the display device 200 is a liquid crystal display device, the cell 230 may include liquid crystal. Accordingly, by moving the liquid crystal by the electric field generated by applying a voltage to the electrodes formed on the substrates SUBS1 and SUBS2, the image is expressed by the transmittance of light depending on the electric field.

A touch electrode may be formed on the cell 230. As described above, the display device 200 may be an in-cell type display device, and electrodes for the touch function, for example, Rx and Tx electrodes are built in the cell 230. [ Since the touch panel is formed inside the display panel 300 without attaching a separate touch panel on the liquid crystal display device, the in-cell touch type liquid crystal display device has advantages such as slimming of the product, cost structure improvement due to the reduction of the material cost, . For example, although not shown, the structure for the touch function may be an In-Plane Switching mode (IPS mode), but is not limited thereto.

The lower polarizing plate LPOL and the upper polarizing plate HPOL polarize the light and output the light to the outside of the liquid crystal display 200. [ However, when the lower polarizer LPOL and the upper polarizer HPOL are attached to the display panel 300, static electricity may be generated. Also, static electricity may be generated during driving for displaying an image.

The antistatic film 250 is disposed to remove the static electricity. 8, the antistatic layer 250 includes a matrix material 252 and carbon nanotubes (CNTs) 254 dispersed in the matrix material 252. The antistatic layer 250 includes a matrix material 252, The sheet resistance value of the sheet member 250 may be 10 ² Ω / □ to 10 ⁹ Ω / □, preferably 10 ⁷ Ω / □ to 10 ⁹ Ω / □. More specifically, the antistatic film 250 may be formed by curing a solution containing a matrix material 252, carbon nanotubes 254 dispersed in a matrix material, a solvent, a dispersion additive, and the like. By including the carbon nanotubes 254 dispersed in the matrix material 252, heat resistance and reliability are improved. A more detailed description of the structure of the antistatic film 250 will be described later.

The carbon nanotubes 254 dispersed over the entire surface of the antistatic layer 250 have a very high stiffness and strength due to the sp ² bond between carbon and carbon. In particular, the single wall carbon nanotube (SWCNT) Can achieve a Young's modulus of 5.5 TPa and tensile strength of up to 45 GPa, making it a high strength / lightweight composite material.

The sheet resistance value of the carbon nanotubes 254 may be 1000? /? To 20000? / ?. In the case where the display device 200 is an in-cell touch type liquid crystal display device, when the sheet resistance value of the antistatic film 250 is excessively small (less than 10 ⁷ ? / Square), a voltage generated by a touch of a finger, The barrier film 250 is discharged, which causes a problem that the touch sensor can not recognize the touch. Therefore, it is necessary to increase the sheet resistance value of the antistatic film 250, thereby increasing the sheet resistance value of the carbon nanotubes 254 themselves and realizing a sheet resistance value of 1000? /? To 20000? / ?.

When the sheet resistance value of the carbon nanotubes 254 is less than 1,000 OMEGA / & squ &, the sheet resistance value of the antistatic film 250 becomes small, thereby causing a problem of deterioration of touch sensitivity due to discharge. On the other hand, when the sheet resistance value of the carbon nanotubes 254 is larger than 20000? / ?, the sheet resistance value of the antistatic layer 250 becomes excessively large, thereby reducing the effect of the discharge.

The content of the carbon nanotubes 254 in the antistatic film 250 can be adjusted according to the design value for the light transmittance. As the content of the carbon nanotubes 254 increases, the light transmittance of the antistatic layer 250 decreases, so that the content can be controlled according to the light transmittance required for the product.

On the other hand, the sheet resistance value of the antistatic film 250 is uniformly formed over the entire surface. Specifically, the sheet resistance value is 10 ² Ω / □ to 10 ⁹ Ω / □, preferably, 10 ⁷ Ω / □ to 10 ⁹ Ω / □. In the case where the display device 200 is an in-cell touch type liquid crystal display device, when the sheet resistance value of the antistatic film 250 is excessively small (less than 10 ⁷ ? / Square), a voltage generated by a touch of a finger, The barrier film 250 is discharged, which causes a problem that the touch sensor can not recognize the touch. Therefore, an antistatic film 250 having a relatively high resistance value should be used. On the other hand, when the sheet resistance value of the antistatic layer 250 is excessively large (more than 10 ⁹ ? / □), the touch sensitivity is excellent, but the electrostatic discharge phenomenon is delayed.

Therefore, the sheet resistance value of the antistatic layer 250 of the display device 200 according to the embodiment of the present invention should be 10 ² Ω / □ to 10 ⁹ Ω / □, It can be easily discharged to the outside to suppress the failure due to the static electricity and at the same time to prevent deterioration of the touch sensitivity.

One end of the antistatic film 250 is connected to the edge of the lower substrate SUBS1 of the display panel 300 through the conductive member 270. [ Here, the conductive member 270 connects the antistatic layer 250 and the metal pad (or ground pad, not shown) of the lower substrate SUBS1 of the display panel 300. Specifically, the conductive member 270 covers the edge of the outer surface of the antistatic film 250 and contacts the metal pad (not shown) through the connection portion 270 'to serve as a passage for discharging the static electricity to the outside of the device. The conductive member 270 may be made of a metal material such as gold, silver or copper.

Comparing this conductive member 270 with the first conductive member 170a, the conductive connecting member 172 and the second conductive member 170b of the general display device 200 shown in Fig. 1, 270), it is possible to reduce the number of steps, shorten the process time, and reduce the manufacturing cost.

It should be noted that the shape and arrangement of the conductive member 270 of the display device 200 shown in Figs. 6 and 7 are shown by way of example, and the embodiments are not limited thereto.

9 to 11 are views schematically showing various display devices to which the antistatic film of the present invention is applied.

9, a display device according to an exemplary embodiment of the present invention includes a display panel 300 on which a lower substrate SUBS1 on which a thin film transistor array is formed and an upper substrate SUBS2 on which a color filter array is formed are adhered, And a cover window (COV) on the panel 300. The antistatic film 250 of the present invention may be attached to both sides of the display panel 300. [ That is, the antistatic film 250 may be disposed between the lower substrate SUBS1 and the lower polarizing plate LPOL, and the upper polarizing plate HPOL may be disposed between the upper substrate SUBS2 and the upper polarizing plate HPOL. In this case, the antistatic film 250 is used for the purpose of reducing touch noise, and the lower the sheet resistance, the better. In addition, when the touch element is an in-cell type, a sheet resistance of 10 ⁶ to 10 ⁹ ? /? Is required, and in the case of an add-on type, the sheet resistance is advantageously lower.

10 and 11, a display device according to an exemplary embodiment of the present invention includes a display panel 300 in which a color filter array is formed on a lower substrate SUBS3, a thin film transistor array is formed on an upper substrate SUBS4, And may include a cover window (COV) on the display panel 300. 10 and 11 have a structure in which the color filter array and the thin film transistor array are inverted, unlike in FIG. 9, though the light is taken out in the same manner as in FIG. 9 described above. In this case, as shown in FIG. 10, the antistatic film 250 may be disposed between the upper substrate SUBS4 on which the thin film transistor array is formed and the upper polarizer HPOL. 11, the antistatic layer 250 includes a lower substrate SUBS3 and a lower polarizing plate LPOL disposed between an upper substrate SUBS4 on which a thin film transistor array is formed and an upper polarizer HPOL and on which a color filter array is formed, As shown in FIG. However, the present invention is not limited thereto, and the antistatic film may be attached to any surface of various display devices.

Hereinafter, effects of the embodiment of the present invention will be described with reference to the attached tables and graphs.

<First Experimental Example>

12A is a table showing the sheet resistance and sheet resistance uniformity of the antistatic film for the sheet resistance of carbon nanotubes according to the embodiment, and FIG. 12B is a graph showing the sheet resistance uniformity of FIG. 12A.

Referring to FIG. 12A, it can be seen that the sheet resistance uniformity of the antistatic layer is increased from 17.32% to 6.67% as the sheet resistance value of the carbon nanotubes itself is increased from 477? /? To 1800? / ?. In other words, the variation of the sheet resistance value in each area in the antistatic film is reduced.

In the case of the display device is a liquid crystal display of Insel system apparatus as described above, in order to maintain the touch sensitivity at the same time performing a function of the discharge, the 10 ⁷ Ω / range of the sheet resistance of the antistatic film □ to 10 ⁹ Ω / □.

However, for sample 1 (Sample 1), the sheet resistance value is 10 ^{7. 4} Ω / □ to 10 ¹⁰ are formed in a large range of variation of ⁵ Ω / □, even in the case of sample 2 (Sample 2), the sheet resistance The value is 10 ^7.7 ? /? To 10 ^{10. It} can be seen that the deviation of ¹ ? /? Is formed in a large range. Therefore, in Sample 1 and Sample 2, there arises a problem that the function of discharge is deteriorated in a region where the sheet resistance is large and the sheet resistance is excessively large.

On the other hand, as seen in sample 4 (Sample 4), forming a sheet resistance value itself of the carbon nanotube to 1800Ω / □, the sheet resistance value of 10 ^{7. 7} Ω / □ to 10 ⁸ are formed by ⁸ Ω / □, The discharge function can be performed while maintaining the touch sensitivity.

A graph relating to the sheet resistance uniformity of the antistatic film is shown in Fig. 5B. From the sample 1 (Sample 1) to the sample 4 (Sample 4), it can be seen that the self-resistance of the carbon nanotubes rises and thus the sheet resistance uniformity improves.

13 is a graph showing a sheet resistance value of an antistatic film with respect to the content of carbon nanotubes according to an embodiment.

Referring to FIG. 13, the first line L1 represents the sheet resistance value of the antistatic film of a general display device, and the second line L2 represents the sheet resistance value of the antistatic film of the display device according to the embodiment. The display device of Fig. 13 is an in-cell type liquid crystal display device.

When examining the area A in the first line (L1), it can be seen that the slope at around 10 ⁸ Ω / □, which is the sheet resistance value of the antistatic film capable of simultaneously performing the discharge function while maintaining the touch sensitivity, is very rapid. This means that the sheet resistance value of the antistatic film can be greatly changed even if the content of the carbon nanotubes is minute. In other words, the uniformity of the sheet resistance value is relatively low.

On the other hand, when examining the area B of the second line (L2), it can be seen that the slope when the sheet resistance value of the antistatic film is near 10 ⁸ Ω / □ is very gentle. This means that even when the content of carbon nanotubes is changed, the uniformity of the sheet resistance value is relatively high, so that the change of the sheet resistance value is minute. Therefore, the display device according to the embodiment has the effect that the touch sensitivity can be maintained and the anti-static function can be smoothly performed even when the content of the carbon nanotubes changes.

14 is a table showing the light transmittance with respect to the content of carbon nanotubes and the sheet resistance value according to one embodiment.

Referring to FIG. 14, the content and the sheet resistance value of the carbon nanotube according to the design value of the light transmittance can be seen. Specifically, in the case of a display device requiring a light transmittance of 100%, 0.13% of carbon nanotubes are included, and the sheet resistance value of carbon nanotubes is designed to 1800? / ?. Also, in the case of a display device requiring a light transmittance of 99% or more, the carbon nanotubes may contain 0.26%, and the sheet resistance value of the carbon nanotubes may be designed to 5000? / ?.

Here, as shown in FIG. 14, if the sheet resistance of the antistatic layer capable of smoothly performing the discharge function is maintained while the touch sensitivity is maintained, the content of the carbon nanotubes and the sheet resistance value are adjusted to adjust the light transmittance Can be seen.

15A is a graph showing a change in sheet resistance value of a general antistatic film over time, and FIG. 15B is a graph showing a change in sheet resistance value of an antistatic film in a high temperature and high humidity environment.

15A shows a change in the sheet resistance value of the antistatic film over time in an environment of 95 캜 in which the antistatic film is made of a conductive high molecular material of PEDOT: PSS. Referring to the graph, we can see that the sheet resistance value continues to increase over time. Specifically, when the initial sheet resistance value was set to about 8.5? / ?, the value increased to 9.7? /?, And when the initial sheet resistance value was set to about 8.0? /? have.

On the other hand, referring to FIG. 15B, in the case of the antistatic layer according to the embodiment, when the antistatic layer having the initial sheet resistance value of about 8? /? Is exposed to the antistatic layer at 105 占 폚 for 1500 hours, . This is also true when the antistatic film is exposed to a high humidity (or high humidity) environment.

Therefore, it can be seen that the antistatic film according to the embodiment is superior in heat resistance and reliability to a general antistatic film.

16 is a graph comparing the weight% of the general antistatic film with the temperature and the weight% of the antistatic film according to the embodiment.

Referring to FIG. 16, a general antistatic layer and an antistatic layer according to an embodiment can be analyzed by a thermogravimetric analyzer (TGA). The thermogravimetric analyzer measures the mass change of a sample as a function of temperature by applying heat to the sample.

In the case of the antistatic film of a general display device, it can be seen that the conductive polymer PEDOT: PSS contained in the antistatic film is completely lost by heat at a temperature of about 500 ° C. On the other hand, in the case of the antistatic film included in the display device according to the embodiment, it can be seen that the carbon nanotubes do not disappear to about 900 DEG C but remain.

Therefore, it can be seen that the antistatic film according to the embodiment has excellent heat resistance as compared with a general antistatic film.

In summary, when the display device is a liquid crystal display device including a touch function, by the antistatic film 250 having a sheet resistance value of 10 ⁷ Ω / □ to 10 ⁹ Ω / □ and having a uniform sheet resistance value over the entire surface , The display device can easily discharge the static electricity generated in the manufacturing process to the outside to suppress the defect caused by the static electricity, to prevent the deterioration of the touch sensitivity, to improve the sheet resistance uniformity, heat resistance and reliability, .

Hereinafter, a conductive coating liquid composition comprising the carbon nanotube dispersion composition for producing the antistatic film according to the first embodiment of the present invention will be described.

&Lt; Embodiment 2 >

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon nanotube dispersion composition and a conductive coating liquid composition comprising the carbon nanotube dispersion composition. More particularly, the present invention relates to a carbon nanotube dispersion composition, The acidity and stability after dispersion can be remarkably improved and it can be used in the conductive coating liquid composition together with the silane sol to form a coating film having excellent chemical stability and electric conductivity and to improve the uniformity of the formed coating film. Further, the carbon nanotube dispersion composition contains a silsesquioxane compound in combination with a silane sol, whereby an antistatic film having improved film density, hardness and abrasion resistance can be produced.

<Carbon Nanotube Dispersion Composition>

The carbon nanotube dispersion composition according to the present invention includes a carbon nanotube, a polyacrylic acid resin, and a straight chain alkanol having 2 to 5 carbon atoms.

Carbon nanotube

Carbon nanotubes are excellent conductive materials. When a coating film is formed, it can exhibit excellent electrical conductivity as well as mechanical strength and can be applied to a conductive layer, an antistatic film, and the like in electronic products such as display devices .

The carbon nanotubes (CNTs) may be manufactured by a conventional method such as an arc discharge method, a laser deposition method, a plasma chemical vapor deposition method, a gas phase synthesis method, a pyrolysis method, and the like, and then heat-treated. The carbon nanotubes synthesized by the above synthesis method include carbon impurities such as amorphous carbon or crystalline graphite particles and catalyst transition metal particles. For example, when manufactured by an arc discharge method, 15 to 30% by weight of carbon nanotubes, 45 to 70% by weight of carbon impurities and 5 to 25% by weight of catalyst transition metal particles are contained in 100% by weight of the product. When the impurity-containing carbon nanotubes are used without purification, the dispersibility and coating properties of the impregnation solution deteriorate, and unique physical properties inherent to the carbon nanotubes are hardly manifested. Therefore, in the present invention, carbon nanotubes in which impurities are removed as much as possible by heat treatment of a product produced by an arc discharge method are used.

Specifically, the product prepared by the above synthesis method is made into a sheet or a granular form having an average diameter of 2 to 5 mm, and then the granular product is fed into a rotatable reactor inclined at an angle of 1 to 5 degrees downward with respect to the traveling direction The oxidizing gas is supplied at a rate of 200 to 500 cc / min to 1 g of the charged product while heating the rotatable reactor at 350 to 500 ° C, followed by heat treatment for 60 to 150 minutes. At this time, the inclined rotatable reactor is rotated at a speed of 5 to 20 rpm to disperse the product, thereby maximizing the contact surface area and automatically moving in the traveling direction, maximizing the contact surface area with the oxidizing gas and preventing local oxidation Heat treated. According to this method, the weight of the charged product is reduced by 60 to 85%, and a high-purity carbon nanotube is obtained.

Carbon nanotubes contain carbon impurities in an amount of not more than 40% by weight, more preferably not more than 25% by weight, in 100% by weight of the total weight of the carbon nanotubes.

The carbon nanotubes may be single-walled carbon nanotubes, double-walled carbon nanotubes, or multi-walled carbon nanotubes. These carbon nanotubes may be used singly or in combination of two or more. In order to improve interaction with other components described below, Carbon nanotubes are more preferable.

The content of the carbon nanotubes according to the present invention is not particularly limited, but may be, for example, 0.05 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 10% by weight, 1% by weight. When it is included in the above content range, it can exhibit excellent dispersibility and it is easy to secure the electric conductivity, scratch resistance and permeability of the coating film when formed into a coating film.

Polyacrylic resin

The polyacrylic acid resin according to the present invention is a component that acts as a dispersant for effectively dispersing carbon nanotubes. The polyacrylic acid resin is well dissolved in a specific dispersion medium to be described later, and can be well bonded to a hydrophobic carbon nanotube. Also, the electrostatic repulsion between the carbon nanotube strands and the strands and the steric hindrance effect due to the intrinsic properties of the polymer chain can improve the dispersibility of carbon nanotubes and prevent re-aggregation.

The content of the polyacrylic acid resin according to the present invention is not particularly limited, but may be in the range of 0.02 to 40% by weight, preferably 0.05 to 10% by weight, more preferably 0.1 to 1% by weight, &Lt; / RTI &gt; When the carbon nanotubes are contained in the above-mentioned content range, their activity for dispersing the carbon nanotubes can be remarkably improved by being present in a dissolved state in an appropriate range in the composition.

The weight average molecular weight of the polyacrylic acid resin according to the present invention is not particularly limited, but may be, for example, from 2,000 to 3,000,000, and preferably from 8,000 to 12,000. When the weight average molecular weight is in the above range, it is easy to penetrate between the strands and the strands of the carbon nanotubes and can have a steric hindrance effect suitable for re-aggregation. In addition, it can be present in the dispersion composition in a well-dissolved state in the dispersion medium, so that the carbon nanotubes can be effectively dispersed.

The dispersion composition of the present invention may contain a trace amount of water. The polyacrylic acid resin may be included in the dispersion in a form dissolved or emulsified in water, but is not limited thereto.

A straight chain alkanol having 2 to 5 carbon atoms

The linear alkanol having 2 to 5 carbon atoms according to the present invention is a dispersion medium for effectively dispersing carbon nanotubes and also interacts with the polyacrylic acid resin described above as a hydrophilic alcohol solvent to remarkably improve the dispersion stability of carbon nanotubes . In the case of using a branched chain alkanol as a dispersion medium, the solubility and stability of the polyacrylic acid resin in the dispersion medium are remarkably lowered, and it is difficult to maintain the dispersion stability in an appropriate range.

Specific examples of the straight chain alkanol having 2 to 5 carbon atoms according to the present invention include ethanol, n-propanol, n-butanol and n-pentanol, and preferably ethanol, n-propanol, n- And n-pentanol, and more preferably n-propanol.

The content of the alkanol according to the present invention is not particularly limited and may be, for example, from 50 to 99.93% by weight, and preferably from 80 to 99% by weight, based on the total weight of the composition. When the content is within the above range, the viscosity of the dispersion can be kept low, the dispersion stability of the carbon nanotubes can be further improved, and it can be effectively mixed with the binder component when applied to a coating film.

Additional dispersant

The carbon nanotube dispersion composition according to the present invention may further include an additional dispersant if necessary. The type of the additional dispersant is not particularly limited. For example, the carbon nanotube dispersion composition may be an acrylic block copolymer dispersant.

In the present invention, the acrylic block copolymer refers to a copolymer formed by block copolymerization of different acrylic monomers and formed of AAAAAABBBBBB when the monomer units are A and B, respectively. The acrylic block copolymer dispersant can further improve dispersion stability by polarity separation of the carbonyl group in the copolymer. Preferably, the acrylic block copolymer may contain at least one functional group such as an amine group or a carboxyl group in each monomer unit. By controlling the content of the monomer unit containing the substituent, the hydrophilic and hydrophobic component ratios can be controlled, The dispersibility of the tube can be further improved. Specific examples of commercially available acrylic copolymer dispersants include polymer dispersants of DISPERBYK 2001 and DISPERBYK 2155 manufactured by BYK Corporation.

The content of the additional dispersing agent is not particularly limited, but may be in the range of 0.1 to 2% by weight, and preferably in the range of 0.5 to 1% by weight based on the total weight of the composition. When it is contained within the above range, the scratch resistance and the viscosity increase due to the use of the additional dispersing agent can be prevented, and the dispersion stability can be effectively maintained.

The carbon nanotube dispersion composition according to the present invention may further contain a trace amount of water if necessary. Water can be used for improving the solubility and dispersibility of the above-mentioned components and can be used, for example, as a solvent for improving the dispersing activity of the polyacrylic acid resin, but is not particularly limited thereto.

&Lt; Process for producing carbon nanotube dispersion composition >

A method for producing a carbon nanotube dispersion composition containing the above-described components will be described below.

First, a carbon nanotube, a polyacrylic acid resin, and a straight chain alkanol having 2 to 5 carbon atoms are mixed. The concentration of the aqueous solution is not particularly limited, but it is preferable that the solid content of the polyacrylic acid resin is 0.02 to 40% based on the total content of the carbon nanotube dispersion composition And more preferably from 20 to 30% by weight. The specific content of each component of the carbon nanotube dispersion composition is also as described above.

Next, the components of the carbon nanotube dispersion composition are mixed and then subjected to high-pressure dispersion at 1000 to 1800 bar. When the dispersion is carried out under a high pressure of 1000 to 1800 bar, the carbon nanotubes can be collided with an appropriate shear stress, whereby the strands of the carbon nanotubes can be effectively dispersed, and the aggregation of carbon nanotubes So that the interaction with the polyacrylic acid resin and the alkanol can be effectively carried out.

When the pressure is less than 1000 bar, the energy transferred to the carbon nanotubes is low, and the dispersing effect may be significantly deteriorated. If the pressure exceeds 1800 bar, the polyacrylic acid resin may break the polymer chains due to too high energy, There is a problem that dispersion stability is poor. The above-mentioned barometric pressure can more preferably be performed at 1200 to 1600 bar, and in this case, the above-mentioned effect can be further improved.

The dispersion may be performed by spraying the composition with the nozzle having the predetermined particle size in the above-described pressure range, wherein the diameter of the nozzle through which the composition is sprayed may be 50 to 400 탆, preferably 80 to 200 탆 . In addition, the dispersion may be performed simultaneously by connecting nozzles having different sizes in series or may be performed separately using each nozzle twice.

When the nozzle having the above range is used, the process can be easily performed at a high pressure of 1,000 bar to 1,800 bar as described above, so that the dispersion can be effectively performed.

The aperture of the nozzle and the flow rate may be selected in an appropriate range to suit the above pressure range.

Further, the stirring step may be further performed before the high-pressure dispersion step, in which case the efficiency of the high-pressure dispersion step can be further improved by optimizing the mixing of the composition.

&Lt; Conductive coating liquid composition >

A silsesquioxane compound having from 10 to 100 parts by weight of a silane sol and having a disulfide group linking a siloxane group to 100 parts by weight of the conductive coating liquid composition is mixed with a silsesquioxane compound of from 0.1 to 10 parts by weight per 100 parts by weight of the carbon nanotube dispersion composition, By weight based on the total weight of the conductive coating liquid composition.

<Carbon Nanotube Dispersion Composition>

The above-described carbon nanotube dispersion composition may be applied in the same manner as the above-mentioned components and contents, and as described above, those prepared by high-pressure dispersion may be used.

<Silane sol>

The silane sol according to the present invention serves as a binder in the coating liquid composition, and may include an alkoxysilane compound, an acid catalyst, an alcohol solvent, and water.

Alkoxysilane compound

The alkoxysilane compound according to the present invention is a binder resin, and its kind is not particularly limited, and examples thereof include tetraalkoxysilane compounds such as tetraethoxysilane, tetramethoxysilane and tetra-n-propoxysilane; Methyltrimethoxysilane, methyltriethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, methyltripropoxysilane, methyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltri Alkylalkoxysilane of a substituted or unsubstituted straight-chain or branched alkyl group such as methoxymethylsilane, diethoxysilane, diethoxysilane, diethoxysilane, diethoxysilane, diethoxysilane, diethoxysilane, diethoxysilane, diethoxysilane, diethoxysilane, diethoxysilane, Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxysilane; Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 2-aminoethyl-3-aminopropyltrimethoxysilane, N -? - (aminoethyl) N- (n-butyl) -3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane; Dimethyldimethoxysilane, diethyldiethoxysilane,? -Glycidyloxypropyltrimethoxysilane,? -Glycidyloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3- Capped propyl trimethoxysilane; Tridecafluoro-1,1,2,2-tetrahydrooctylpryethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriisopropoxysilane, etc. Fluoroalkylsilane, and the like. These may be used alone or in combination of two or more.

Of these, alkylalkoxysilane compounds having 1 to 20 carbon atoms in the alkyl group are most preferable, and tetraethoxysilane compounds can be more preferably used.

The content of the alkoxysilane compound according to the present invention is not particularly limited, but may be 20 to 60 wt%, preferably 30 to 50 wt%, based on the total weight of the silane sol. When the content is within the above range, a sol-gel reaction occurs well, the obtained silane sol has good physical properties and is excellent in adhesion so that it is easy to form a coating film, and is particularly suitable for coating on a glass substrate.

Acid catalyst

The acid catalyst according to the present invention promotes the hydrolysis of water and alkoxysilane and imparts a proper degree of crosslinking. The type is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, diluted fluorine And hydrofluoric acid. These may be used alone or in admixture of two or more, and the acid catalyst to be used may be contained in the form of an aqueous solution upon mixing.

The content of the acid catalyst according to the present invention is not particularly limited, but may be 0.01 to 10% by weight, preferably 0.05 to 5% by weight based on the total weight of the silane sol. When it is included in the above content range, a coating film can be formed with an appropriate degree of crosslinking.

Alcoholic solvent

The kind of the alcoholic solvent according to the present invention is not particularly limited, but it is preferable to use a hydrophilic alcoholic solvent in view of the compatibility with the carbon nanotube dispersion. Examples thereof include methanol, ethanol, n-propanol, isopropanol, n Butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, 1-ethyl-1-propanol, 2-methyl- -Hexanol or cyclohexanol, which may be used alone or in combination of two or more. Of these, ethanol, n-butanol, n-propanol, n-pentanol and the like are preferable from the viewpoint of improvement of stability with the carbon nanotube dispersion, and more preferred is n-propanol.

The content of the alcoholic solvent according to the present invention is not particularly limited, but may be 10 to 70% by weight, preferably 20 to 50% by weight, based on the total weight of the silane sol. When included in the above content range, the reactivity of the sol-gel reaction can be further improved.

water

The water according to the present invention is a component which undergoes a hydrolysis reaction with alkoxysilane and the content thereof is not particularly limited and may be 5 to 60% by weight, preferably 8 to 35% by weight, . When it is included in the above content range, sufficient hydrolysis can be carried out and excellent adhesion to the substrate can be obtained.

Polar solvent

The polar solvent according to the present invention includes a polar solvent having a polarity of 10 or more for improving conductivity and improving the dispersibility of carbon nanotubes in a conductive coating liquid composition.

The polar solvent of the present invention maximizes the dispersibility by increasing the repulsive force of the carboxyl group of the polyacrylic resin surrounding the carbon nanotubes in the conductive coating liquid composition, thereby improving the dispersion of the carbon nanotubes as the conductive filler in the coating film state, . For example, referring to FIG. 10, when a solvent having a low polarity is included in the conductive coating liquid composition, the dispersibility of the polyacrylic resin surrounding the carbon nanotubes is low due to the low repulsion of carboxyl groups. On the other hand, referring to FIG. 11, when a solvent having a high polarity is included in the conductive coating liquid composition, the repulsive force of the carboxyl group of the polyacrylic resin surrounding the carbon nanotubes is increased to improve the dispersibility.

In addition, the polar solvent of the present invention assists in securing an appropriate viscosity at the time of coating the conductive coating liquid composition, and allows a uniform coating film to be realized by controlling the drying speed in an appropriate range during coating.

The polar solvent of the present invention is a polar solvent having a polarity of 10 or more and may be selected from n-methyl pyrolidone (NMP), dimethyl sulphoxide (DMSO), or dimethyl formamide (DMF) . Particularly, n-methylpyrrolidone, dimethylsulfoxide, and dimethylformamide can further improve the conductivity with inherent permittivity, so that a coating film with low resistance can be realized.

The polar solvent of the present invention may be contained in an amount of 0.1 to 5% by weight based on 100% by weight of the conductive coating liquid composition. If the polar solvent is 0.1 wt% or more based on 100 wt% of the conductive coating liquid composition, the dispersibility of the carbon nanotubes in the conductive coating liquid composition can be improved to improve the uniformity of the surface resistance and facilitate the control of the surface resistance, If the amount is 5% by weight or less based on 100% by weight of the conductive coating liquid composition, it is possible to prevent the surface resistance of the antistatic layer made of the conductive coating liquid composition from becoming too low.

additive

The conductive coating liquid composition according to the present invention may further contain additives as required in addition to the carbon nanotube dispersion and the silane sol.

Examples of usable additives include, but are not limited to, a dispersing agent, a silane coupling agent, a leveling agent, a slip agent, a surfactant, a pH adjusting agent, a lubricant, and a viscosity adjusting agent. Can be used.

More specifically, the slip agent may further include a slip agent for improving the slipperiness of the coating film. The slip agent is not particularly limited, and examples thereof include BKY 333 manufactured by BYK Corporation, but are not limited thereto. Further, a dispersant of BYK 2001 described above may be further used.

The polar solvent such as ethylene glycol or dimethylformamide or 1-methyl-2-pyrrolidone maximizes the dispersibility by increasing the repulsive force of the carboxyl group of the polyacrylic resin surrounding the carbon nanotubes in the dispersion, Thereby improving the electric conductivity of the carbon nanotube. In addition, they are effective in securing an appropriate viscosity at the time of coating, and a uniform coating film can be realized by adjusting the drying speed in an appropriate range during coating. In addition, the conductivity can be further improved by the inherent permittivity of ethylene glycol, dimethylformamide and 1-methyl-2-pyrrolidone, which is more suitable for realizing a coating film of low resistance.

The additional additives may be used alone or in admixture of two or more. The content of the additional additives may be 0.01 to 10% by weight, preferably 0.1 to 5% by weight based on the total weight of the conductive coating composition, , The effect of the additive described above can be realized without deteriorating the effect of the present invention.

The silane sol according to the present invention can be prepared by reacting the above-described components under predetermined conditions. The reaction conditions are not particularly limited. For example, the silane sol may include heating and stirring at 30 to 90 占 폚, The time is not particularly limited, and can be, for example, 4 to 30 hours. In addition, the reactor in which the reaction takes place may include a reflux condenser. After the reaction, the product may be used after being concentrated by rotary evaporation and then diluted with a specific solvent. Accordingly, when the coating solution is applied to a glass substrate, the prepared silane sol is given strong adhesion and excellent strength characteristics can be ensured.

<Silsesquioxane compound>

FIG. 17 is a schematic view showing the curing process of the silsesquioxane compound, and FIG. 18 is a schematic view showing a process of synthesizing the silsesquioxane compound of the present invention.

The silsesquioxane compound of the present invention is a compound having a disulfide group linking a siloxane group.

17, the silsesquioxane compound of the present invention is introduced to improve the film density, abrasion resistance and hardness of the antistatic film. In order to realize a self-healing function for silsesquioxane A disulfide group (SS) was introduced as a functional group. In order to maximize the self-healing function, the silsesquioxane-disulfide-SSQ was clustered by curing.

(여기서, R₂는 C1~C20의 알킬 그룹)에서 선택된다. 그리고 촉매의 조절을 통해 랜덤 타입과 케이지 타입의 실세스퀴옥산 화합물의 비율을 조절할 수 있다.Referring to FIG. 18, the silsesquioxane compound of the present invention combines a random type and a cage type structure in order to increase the healing site and improve the reactivity with the silane sol . The R group plays a role in regulating the reactivity and the light absorption region. R is independently an aromatic group or

(Wherein R &lt; ₂ &gt; is an alkyl group of C1-C20). The ratio of random and cage silsesquioxane compounds can be controlled through the control of the catalyst.

The method of synthesizing the clustered silsesquioxane compound of the present invention is as follows.

0.5 to 10 mL hydrochloric acid, 10 to 100 mL methanol and 0.5 to 30 mL MPTS (3-mercaptopropyl trimethoxysilane) are stirred in a round bottom flask at 60-100 ° C for 12-60 hours. The reaction mixture is then washed several times with methanol to remove unreacted materials. The precipitate is dissolved in 0.1 to 10 mL of THF (tetrahydrofuran), and then slowly added dropwise to 1 to 300 mL of acetonitrile. Thereafter, the mixture is crystallized at 0 to -20 DEG C for at least 24 hours. The silsesquioxane compound (SSQ-SH) having the disulfide group thus synthesized is washed in acetone and then dried in a vacuum oven for at least 12 hours. The dried material is dispersed in a PGMEA solvent and heated at 20 to 100 DEG C for each hour to obtain a clustered silsesquioxane compound.

FIG. 19 is a Raman analysis graph of the silsesquioxane compound prepared in the present invention, and FIGS. 20 and 21 are FTIR analysis graphs of various silsesquioxane compounds. FIG.

Referring to FIG. 19, the silsesquioxane compound prepared in the present invention can be confirmed to have disulfide peaks by Raman analysis to confirm disulfide peaks.

20 and 21, # 1 and # 2 represent a silsesquioxane compound combined with a random type and a cage type prepared in the present invention, # 3 represents a known silsesquioxane compound, and # 4 represents a silsesquioxane compound of the cage type. As shown in FIG. 20, a silsesquioxane compound having a random type and a cage type bonded with # 2 among the silsesquioxane compounds of the present invention had peaks at which Si-O-Si bonds could be confirmed. As shown in FIG. 21, the known silsesquioxane compounds represented by # 3 can not confirm SH bonds, but the silsesquioxane compounds of the present invention represented by # 1, # 2 and # 4 can confirm SH bonds there was.

Figure 22 is a schematic representation of the healing mechanism of self-healing materials.

As shown in FIG. 22, a film containing a self-healing material has no defects in the polymer network, but a micro defect occurs when a certain stress is applied. When additional stress is applied to the film where the micro-defect is generated, a macro defect occurs and a crack occurs. Here, the micro-defect is a defect that is not visually recognized, and the macro-defect is a defect that is recognized. When the above-described defects occur, the specific binding of the self-healing material is broken. However, when light of 280 nm or more is irradiated, the specific binding of the self-healing material is recombined again to heal the defects.

The healing mechanism when the silsesquioxane compound having the disulfide group of the present invention is introduced into the antistatic film will be described as follows.

23 and 24 are diagrams illustrating the healing mechanism of the silsesquioxane compound having a silane sol and a disulfide group.

Referring to FIG. 23, TEOS silanol, which is a tetraethoxysilane compound, is hydrolyzed to produce a TEOS silanol and mixed with a silsesquioxane compound having a disulfide group. Then, a hydrochloric acid catalyst is added to the mixture, followed by coating and heat treatment to produce a film in which a silsesquioxane compound having TEOS and a disulfide group is condensed. The silanol generated by the hydrolysis of the TEOS sol reacts with OH of the silsesquioxane compound to promote cross-linking, thereby improving the density and hardness of the film.

Referring to FIG. 24, when external stress is applied to a manufactured film, disulfide bonds having relatively low bonding enthalpy are dissociated. When irradiated with light, the dissociated portion again generates disulfide bonds and heals the defects due to stress.

As described above, the present invention improves the film density, abrasion resistance and hardness of the antistatic film by incorporating a silsesquioxane compound having a disulfide group as a self-healing material. A more detailed effect will be demonstrated in the experiments described below.

Meanwhile, the conductive coating liquid composition of the present invention may further include nanoparticles to improve the hardness of the antistatic film. The nanoparticles may be made of metal, ceramic, metal oxide, or a mixture thereof, and examples thereof include silica (SiO ₂ ) or aluminum oxide (Al ₂ O ₃ ).

&Lt; Preparation of conductive coating liquid composition >

The conductive coating liquid composition according to the present invention can be prepared by preparing a carbon nanotube dispersion and a silane sol, respectively, and then mixing a carbon nanotube dispersion, a silane sol, a silsesquioxane compound having a disulfide group, a polar solvent, have. The conductive coating liquid composition of the present invention is prepared by mixing 10 to 100 parts by weight of a silane sol with respect to 100 parts by weight of a carbon nanotube dispersion composition and adding 0.1 to 1 weight of a silsesquioxane compound having disulfide groups per 100 parts by weight of the total conductive coating liquid composition By weight.

When the content of the silane sol is less than 10 parts by weight at the time of mixing, it is difficult to secure the adhesion of the coating layer. If the content of the silane sol is more than 100 parts by weight, the coatability of the coating layer may be lowered. Also, the mixing ratio may be 25 to 60 parts by weight of the silane sol, or 10 to 20 parts by weight of the silane sol, based on 100 parts by weight of the carbon nanotube dispersion composition. When the silane sol is mixed at 25 to 60 parts by weight, it is suitable for realizing a coating film having a high resistance. When the silane sol is mixed at 10 to 20 parts by weight, it is suitable for realizing a low resistance coating film.

If the content of the silsesquioxane compound having a disulfide group is less than 0.1 part by weight, the film density, hardness and abrasion resistance of the coating layer can be improved, and when the content of the silsesquioxane compound having disulfide groups exceeds 1 part by weight The surface resistance of the undercoat layer is increased and it can not be used as an antistatic film.

The mixing method is not particularly limited, but may be performed using an ultrasonic dispersing machine, a high pressure dispersing machine, a homogenizer, a mill, or the like. Preferably, when the same high pressure dispersion process as in producing a carbon nanotube dispersion is applied, Acidity and stability can be ensured.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

&Lt; Second Experimental Example &

An experimental example of forming an antistatic film using the carbon nanotube dispersion and a conductive coating liquid composition containing the carbon nanotube dispersion is described below.

Experiment 1: Conductive coating liquid composition and its Of the coating film (antistatic film)  Characterization

Example  One

&Lt; Production of Carbon Nanotube Dispersion >

A carbon nanotube (SA100, Nano Solutions, Inc.) synthesized by an arc discharge method was rotated at a rotation speed of 5-20 rpm, a temperature of 420 캜, an oxidizing gas of 250 cc / min using a rotary kiln rotary reactor having an inclination angle of 3 Treated at a feed rate for 100 minutes to use carbon nanotubes A having a carbon impurity content of 15%.

Thereafter, 0.15 part by weight of carbon nanotube A, 0.24 part by weight of a polyacrylic acid resin solution (solid content 25% / polyacrylic acid resin Mw = (250,000)) 0.24 part by weight, acrylic block copolymer (trade name: DISPERBYK2001 acid value 19 mg KOH / g, amine value 29 mg KOH / ) And 99.61 parts by weight of n-propanol were mixed and dispersed at a pressure of 1500 bar using an injector having a nozzle diameter of 100 탆 to prepare a carbon nanotube dispersion.

&Lt; Preparation of silane sol &

21.7 parts by weight of n-propanol and 62.6 parts by weight of TEOS were charged into a reactor equipped with a reflux tube and stirred for 30 minutes at 300 rpm at room temperature (25 ° C) using a stirrer. 15.2 parts by weight of water was added thereto and stirred at 500 rpm. By weight was slowly added dropwise.

&Lt; Conductive coating liquid composition >

33 parts by weight of a binder, 0.95 parts by weight of BYK2001 and 0.05 parts by weight of BYK333 as a surface slip agent were added to 66 parts by weight of the carbon nanotube dispersion thus prepared, and the mixture was passed through a nozzle having a diameter of 100 mu m under a pressure of 1500 at a pressure of 1,500, And a cooling device was used to prevent the temperature of the solution from rising.

Example 2 (when the kind of dispersion medium is different)

A conductive coating liquid composition was prepared in the same manner as in Example 1, except that ethanol was used as a dispersion medium in the preparation of the carbon nanotube dispersion.

Example 3 (when the kind of the dispersion medium is different)

A conductive coating liquid composition was prepared in the same manner as in Example 1, except that butanol was used as a dispersion medium in the preparation of the carbon nanotube dispersion.

Example 4 (when the type of dispersion medium is different)

A conductive coating liquid composition was prepared in the same manner as in Example 1, except that pentanols were used as a dispersion medium in the preparation of the carbon nanotube dispersion.

Example 5 (when the weight average molecular weight of PAA is different)

A conductive coating liquid composition was prepared in the same manner as in Example 1 except that, in the preparation of the carbon nanotube dispersion, the polyacrylic acid resin having a weight average molecular weight of 1,250,000 was used.

Example 6 (when BYK 2155 was used)

A conductive coating liquid composition was prepared in the same manner as in Example 1, except that DISPERBYK 2155 was used instead of DISPERBYK 2001 in the preparation of the carbon nanotube dispersion.

Example 7 (when injection pressure is different)

A conductive coating liquid composition was prepared in the same manner as in Example 1, except that the carbon nanotube dispersion was sprayed at a pressure of 1000 bar.

Example 8 (when injection pressure is different)

A conductive coating liquid composition was prepared in the same manner as in Example 1, except that the carbon nanotube dispersion liquid was sprayed at a pressure of 1,800 bar.

Example 9 (when jet nozzle diameters were different)

A conductive coating liquid composition was prepared in the same manner as in Example 1, except that the carbon nanotube dispersion liquid was sprayed using a nozzle having a diameter of 500 mu m.

Example 10 (when jet nozzle diameters were different)

A conductive coating liquid composition was prepared in the same manner as in Example 1, except that the carbon nanotube dispersion liquid was sprayed using a nozzle having a diameter of 300 mu m.

Example 11

14 parts by weight of a binder, 0.95 parts by weight of BYK 2001, 5 parts by weight of ethylene glycol, and 0.05 parts by weight of BYK 333 as a surface slip agent were put in 80 parts by weight of the carbon nanotube dispersion thus prepared and passed through a nozzle Was performed five times to prepare a coating solution. At this time, a cooling device was used to prevent the temperature of the solution from rising.

Comparative Example 1 (when the kind of the dispersion medium is out of the range of the present invention)

A conductive coating liquid composition was prepared in the same manner as in Example 1, except that isopropanol was used as a dispersion medium in the preparation of the carbon nanotube dispersion.

Comparative Example 2 (when sodium dodecylsulfonate was used instead of PAA as a dispersant)

A conductive coating liquid composition was prepared in the same manner as in Example 1, except that a sodium dodecylsulfonate aqueous solution was used instead of the polyacrylic acid aqueous solution in the preparation of the carbon nanotube dispersion.

Comparative Example  3 (when isopropanol is used and the injection pressure is out of the range of the present invention)

A conductive coating liquid composition was prepared in the same manner as in Comparative Example 1, except that the carbon nanotube dispersion was sprayed at a pressure of 900 bar.

Comparative Example  4 (if isopropanol is used and the injection pressure is outside the scope of the present invention)

A conductive coating liquid composition was prepared in the same manner as in Comparative Example 1, except that the carbon nanotube dispersion liquid was sprayed at a pressure of 2000 bar.

Test Methods

(1) Evaluation of dispersibility

The zeta potential was measured to evaluate the carbon nanotube dispersion composition prepared according to Examples and Comparative Examples and evaluated according to the following evaluation criteria.

<Evaluation Criteria>

○: When the absolute value exceeds 25 mV

?: When the absolute value is in the range of 10 to 25 mV

Ⅹ: When the absolute value is less than 10mV

(2) Evaluation of dispersion stability

The carbon nanotube dispersion composition prepared according to Examples and Comparative Examples was put into a glass bottle and evaluated for agglomeration at room temperature for 30 days according to the following evaluation criteria.

<Evaluation Criteria>

○: Coagulation occurred after 14 days

?: Coagulation occurred after 7 days

X: Coagulation occurred within 2 days

(3) Evaluation of Coating Property

The conductive coating liquid compositions prepared according to Examples and Comparative Examples were applied on a glass substrate at 400 rpm for 15 seconds using a spin coater and then dried at 140 ° C. for 10 minutes using a hot plate, And further dried for 30 minutes to form a conductive coating film. The uniformity of the formed coating film was visually observed and evaluated according to the following evaluation criteria.

<Evaluation Criteria>

○: When there is no pin hole

?: Less than 2 pinholes

X: Two or more pinholes

(4) Surface resistivity evaluation

The conductive coating liquid compositions prepared according to Examples and Comparative Examples were applied on a glass substrate at 400 rpm for 15 seconds using a spin coater and then dried at 140 ° C. for 10 minutes using a hot plate, And further dried for 30 minutes to form a conductive coating film. The surface resistivity of the formed coating film was measured by using a surface resistance analyzer. At this time, the surface resistivity was measured by a 4-point probe method, and the coating film was divided into third portions in the longitudinal direction and measured at the center portion thereof.

(5) Transmission

The conductive coating liquid compositions prepared according to Examples and Comparative Examples were applied on a glass substrate at 400 rpm for 15 seconds using a spin coater and then dried at 140 ° C. for 10 minutes using a hot plate, And further dried for 30 minutes to form a conductive coating film. The formed coating film was measured for transmittance at 550 nm using a spectrophotometer, and the transmittance of 90.5% of the glass substrate on which the coating film was not formed was evaluated according to the following evaluation criteria.

<Evaluation Criteria>

?: 89.5?? Transmittance (%)

?: 87.5? Transmittance (%) <89.5

X: Permeability (%) <87.5

(6) Scratch resistance

The conductive coating liquid compositions prepared according to Examples and Comparative Examples were applied on a glass substrate at 400 rpm for 15 seconds using a spin coater and then dried at 140 ° C. for 10 minutes using a hot plate, And further dried for 30 minutes to form a conductive coating film. The surface of the formed coating film was measured using a pencil hardness tester (221-D, Yoshimitsu).

<Evaluation Criteria>

?: 8 to 9 H

?: 6 to 7 H

X: ~ 5 H

The dispersion characteristics, coating properties, surface resistivity, permeability and scratch resistance of the coating films prepared according to the above-described Examples and Comparative Examples were measured and shown in Table 1 below. In Table 1, &quot; Good &quot; indicates good, &quot; Good &quot; indicates good, and &quot; Good &quot; indicates poor.

Dispersion characteristic Coating property Surface resistivity (Ω / □) Permeability (%)
of mine
Scratchiness Dispersibility Dispersion stability Example 1 ○ ○ ○ 10 ^8.0 ○ ○ Example 2 ○ ○ ○ 10 ^8.0 ○ ○ Example 3 ○ ○ ○ 10 ^8.2 ○ ○ Example 4 ○ △ ○ 10 ^8.7 ○ ○ Example 5 ○ ○ ○ 10 ^8.2 ○ ○ Example 6 ○ ○ ○ 10 ^8.1 ○ ○ Example 7 ○ ○ ○ 10 ^8.1 ○ ○ Example 8 ○ △ ○ 10 ^8.3 ○ ○ Example 9 ○ △ ○ 10 ^8.1 ○ ○ Example 10 ○ △ ○ 10 ^8.3 ○ ○ Example 11 ○ ○ ○ 10 ^5.0 ○ ○ Comparative Example 1 △ X △ 10 ^8.2 ○ ○ Comparative Example 2 X X X 10 ^9.4 X △ Comparative Example 3 △ X △ 10 ^8.3 ○ △ Comparative Example 4 △ X △ 10 ^8.5 ○ ○

With reference to Table 1, Examples 1 to 3 using propanol, ethanol and butanol as solvents in the preparation of the carbon nanotube dispersion showed excellent dispersibility, dispersion stability, coating property, permeability and scratch resistance, The specific resistances were 10 ^8.0 , 10 ^8.0 and 10 ^8.2 (Ω / □), respectively. Example 4 exhibited excellent dispersibility, coatability, permeability and scratch resistance, good dispersion stability, and a surface resistivity of 10 ^8.7 .

In Example 5 using a polyacrylic acid resin having a weight average molecular weight of 1,250,000 and in Example 6 using DISPERBYK 2155 in producing a carbon nanotube dispersion liquid, the dispersibility, dispersion stability, coatability, permeability and scratch resistance were excellent And surface resistivities were 10 ^8.2 and 10 ^8.1 (Ω / □), respectively.

Also, Example 7 in which carbon nanotube dispersion was sprayed at 1000 bar pressure showed excellent dispersibility, dispersion stability, coating property, permeability and scratch resistance, and surface resistivity was 10 ^8.1 (? /?) . In Example 8, which was sprayed at a pressure of 1800 bar, the dispersibility, coatability, permeability and scratch resistance were excellent, and the surface resistivity was 10 ^8.3 (Ω / □), except that the dispersion stability was good .

Further, in Examples 9 and 10 in which the diameter of the carbon nanotube dispersion was sprayed using nozzles of 500 μm and 300 μm, respectively, the surface resistivities were 10 ^8.1 and 10 ^8.3 (Ω / □), respectively. Coating properties, transparency and scratch resistance, except for the good appearance.

Also, Example 11, which was prepared with 14 parts by weight of the binder, 0.95 part by weight of BYK 2001 and 5 parts by weight of ethylene glycol, showed a surface resistivity of 10 ^5.0 (? /?) In 80 parts by weight of the carbon nanotube dispersion, Dispersion stability, coating property, permeability and scratch resistance.

On the other hand, Comparative Example 1 using isopropanol as a dispersion medium in the preparation of the carbon nanotube dispersion showed a surface resistivity of 10 ^8.2 (Ω / □), excellent permeability and scratch resistance, and good dispersion and coating properties But the dispersion stability was poor.

Comparative Example 2 using a sodium dodecylsulfonate aqueous solution instead of a polyacrylic acid aqueous solution showed a surface resistivity of 10 ^9.4 (Ω / □) and a good scratch resistance, but the dispersibility and dispersion Stability, coating properties and permeability were poor.

Also, in Comparative Examples 3 and 4, in which isopropanol was used in the preparation of the carbon nanotube dispersion liquid at a pressure of 900 bar and 2000 bar, the surface resistivities were 10 ^8.3 and 10 ^8.5 (Ω / □), respectively, and the permeability was excellent The dispersibility and coating properties were good, and the dispersion stability was poor. The scratch resistance of Comparative Example 3 was good and the scratch resistance of Comparative Example 4 was excellent.

From these results, it can be confirmed that the coating film prepared according to the production process of the carbon nanotube dispersion of the present invention is excellent in dispersibility, dispersion stability, coating property, surface resistivity, permeability and scratch resistance.

Experiment 2: Measurement of the characteristics of the conductive coating liquid composition and the antistatic film made therefrom

Example 12

Methylpyrrolidone (NMP) as a polar solvent was added to a conductive coating solution composition containing 83.3% by weight of a carbon nanotube dispersion, 16.65% by weight of a TEOS sol binder and 0.05% by weight of an additive, The process of passing a nozzle of 100 mu m under atmospheric pressure was performed five times to prepare a conductive coating liquid composition.

Example  13

A conductive coating liquid composition was prepared under the same conditions as in Example 12 except that dimethylformamide (DMF) was added as a polar solvent.

Comparative Example 5

Under the same conditions as in Example 12, except that a polar solvent was not added, a conductive coating liquid composition was prepared.

In Examples 12 and 13, the conductive coating liquid composition was prepared by varying the polar solvent by 1, 2, 3, 4, and 5 wt%, spin-coated on the substrate, and then cured at 140 ° C for 10 minutes The surface resistance of the back coat was measured and shown in Table 2 below. In Table 2, the surface resistance represents an X index at 10 ^X ? / ?. (Here, the surface resistance was measured using a surface resistance meter model name ST-4 (manufactured by SYMCO JAPAN, INC.))

Polar solvent (wt%)
Surface resistance
(10 ^X ? /?)
NMP DMF Comparative Example 5 0 0 8.8

Example 12

#One One 0 7 #2 2 0 6.4 # 3 3 0 5.5 #4 4 0 4.9 # 5 5 0 4.5

Example 13

#One 0 One 8.2 #2 0 2 7.5 # 3 0 3 6.3 #4 0 4 5.6 # 5 0 5 5.1

Referring to Table 2, the antistatic layer made of the conductive coating liquid composition containing no polar solvent showed a surface resistance of 10 ^{8 8} ? / ?. On the other hand, the antistatic layer made of the conductive coating liquid composition of Example 12 containing n-methylpyrrolidone as a polar solvent had a surface resistivity of 10 ⁷ Ω / □ as the polar solvent content increased from 1 to 5 ^{. 5} Ω / □. In addition, embodiments of antistatic film 13 made of a conductive coating composition containing dimethylformamide as a polar solvent increases to 5, the content of the polar solvent 1, the surface resistance 10 ^{8. 2} Ω / □ at 10 ^5.1 Ω / □.

From these results, it can be seen that the antistatic layer made of the conductive coating liquid composition containing the polar solvent can have a lower surface resistance than the antistatic layer made of the conductive coating liquid composition containing no polar solvent. Also, it can be seen that it is possible to control the surface resistance of the antistatic film to be lowered or increased to a desired level by controlling the content of the polar solvent.

Accordingly, the conductive coating liquid composition of the present invention includes a polar solvent having a polarity of 10 or more, so that the surface resistance of the antistatic film can be lowered and the surface resistance can be controlled.

Experiment 3: Disulfide  With a group Silsesquioxane Self Healing  Characterization

Example  14

The acrylic hard coating composition was prepared by mixing silsesquioxane having a disulfide group, coating the mixture, soft baking and UV curing the coating film.

Comparative Example  6

Under the same conditions as in Example 14, a coating film was prepared by mixing TCE, which is a self-healing material, instead of silsesquioxane having a disulfide group.

< TCE >

<TCE>

Comparative Example  7

A coating film was prepared without mixing silsesquioxane having disulfide groups under the same conditions as in Example 14 described above.

The number of steel wool reciprocations in which scratches were observed according to the amount of UV light was measured on the coating film prepared according to Example 14, Comparative Examples 6 and 7, and is shown in FIG. For example, 73 points in FIG. 25 indicate that when the steel wool was rubbed against the coating film without irradiating UV light, the number of reciprocations of the steel wool was observed at 73 times. 25, the light amount of 1.5 mW / cm 2 represents the indoor environment, the light amount of 10 mW / cm 2 represents the backlight unit environment, the light amount of 200 mW / cm 2 represents the shade environment of clear day and the light amount of 1500 mW / It represents the sunlight environment at noon.

Referring to FIG. 25, in Comparative Example 6 including TCE, which is a known self-healing material, and Comparative Example 7, which does not include the self-healing material, the number of times the steel wool reciprocates is only about 107 times even if the light amount is increased to 1500 mW / , Example 14 including silsesquioxane having the disulfide group of the present invention shows that the number of reciprocations is increased up to about 483 times.

From these results, it can be seen that the silsesquioxane having the disulfide group of the present invention has an excellent self-healing effect and can improve abrasion resistance and hardness when it is included in a coating film.

Experiment 4: Disulfide  With a group Silsesquioxane  Determination of the characteristics of the antistatic film included

Example  15

(D-SSQ) having a disulfide group as a self-healing material was added to a conductive coating solution composition containing 83.3% by weight of a carbon nanotube dispersion, 16.65% by weight of a TEOS sol binder, and 0.05% by weight of an additive. The conductive coating liquid compositions were prepared by varying the content of silsesquioxane having disulfide groups to 0, 0.1, 0.3, 0.5, 0.7, and 1.0 wt%, respectively, and then passed through a nozzle having a thickness of 100 μm at 1500 atm using a high pressure disperser Was performed five times to prepare conductive coating liquid compositions. Coated on a substrate with a slit coater, and then thermally cured at 140 ° C for 20 minutes to prepare coating films having a thickness of about 100 nm.

The sheet resistance and pencil hardness of the coating films prepared according to Example 15 were measured and are shown in the following Table 3 and shown in the graph of FIG.

The content of silsesquioxane (wt%) 0 0.1 0.3 0.5 0.7 1.0 Sheet resistance (Ω / □) 10 ^7.9 10 ^8.0 10 ^8.2 10 ^8.3 10 ^8.5 10 ^8.9 Hardness (H) 8 8 8 ~ 9 8 ~ 9 9 8 ~ 9

Referring to Table 3 and FIG. 26, as the content of silsesquioxane having disulfide groups is increased from 0 to 1.0 wt%, the sheet resistance is continuously increased and the content of silsesquioxane having disulfide groups is increased from 0 to 0.7 wt% %, Indicating a hardness of 9H, and a little lowering at 1.0 wt%.

As a result, it was found that when the content of silsesquioxane having a disulfide group was 0.1 to 1.0 wt%, the hardness of the coating film was improved to 8 to 9H and the role of the antistatic film .

As described above, the carbon nanotube dispersion composition of the present invention can effectively disperse carbon nanotubes by using a polyacrylic acid resin as a dispersant, and by using an alcohol having a specific structure, dispersion stability is also excellent.

The method for producing a carbon nanotube dispersion composition of the present invention is a method for producing a carbon nanotube dispersion composition by performing high pressure dispersion in a specific pressure range to significantly increase the dispersing activity of the polyacrylic acid resin to improve the dispersibility of carbon nanotubes, .

The conductive coating liquid composition comprising the carbon nanotube dispersion composition of the present invention can form a uniform coating film, and the formed coating film has excellent chemical stability and electric conductivity.

The antistatic film produced by the conductive coating liquid composition according to the present invention exhibits excellent electrical conductivity and is excellent in mechanical strength and transparency and can be used as a coating film for anti-static use of a touch screen panel and an image display device.

The antistatic film made of the conductive coating liquid composition according to the present invention contains silsesquioxane having a disulfide group as a self-healing material, thereby improving the film density and thus improving hardness and abrasion resistance and improving scratch resistance have.

The antistatic film and the display device including the same according to the present invention can easily discharge the static electricity generated in the manufacturing process to the outside to suppress the defect caused by the static electricity, to prevent the deterioration of the touch sensitivity, to improve the uniformity of sheet resistance, And the manufacturing cost can be reduced.

The foregoing description is merely illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.

LPOL: lower polarizer plate HPOL: upper polarizer plate
SUBS1: Lower substrate 230: Cell
SUBS2: upper substrate 250: antistatic film

Claims (20)

0.1 to 1 part by weight of a silsesquioxane compound having 10 to 100 parts by weight of a silane sol based on 100 parts by weight of a carbon nanotube dispersion composition and having a disulfide group linking a siloxane group to 100 parts by weight of a conductive coating liquid composition Conductive coating liquid composition. The method according to claim 1,
The silsesquioxane compound is bonded to a random and cage type conductive composition. The method according to claim 1,
Wherein the conductive coating liquid composition further comprises nanoparticles composed of a metal, a ceramic, a metal oxide, or a mixture thereof. The method according to claim 1,
The carbon nanotube dispersion composition contains 0.05 to 20% by weight of carbon nanotubes, 0.02 to 40% by weight of a polyacrylic acid resin, 50 to 99.93% by weight of a straight chain alkanol having 2 to 5 carbon atoms per 100 parts by weight of the carbon nanotube dispersion composition &Lt; / RTI &gt; The method according to claim 1,
Wherein the alkanol is at least one of ethanol, n-propanol, n-butanol and n-pentanol. The method according to claim 1,
Acrylic block copolymer dispersing agent. The method according to claim 6,
Wherein the acrylic block copolymer dispersant is substituted with at least one of an amine group and a carboxyl group. The method according to claim 6,
Wherein the acrylic block copolymer dispersant is contained in an amount of 0.1 to 2% by weight based on the total weight of the composition. The method according to claim 1,
Wherein the silane sol comprises an alkoxysilane compound, an acid catalyst, an alcohol-based solvent, and water. 10. The method of claim 9,
Wherein the composition comprises 20 to 60% by weight of an alkoxysilane compound, 0.01 to 10% by weight of an acid catalyst, 10 to 70% by weight of an alcoholic solvent and 5 to 60% by weight of water based on the total weight of the silane sol. An antistatic film formed from the conductive coating liquid composition according to any one of claims 1 to 10. A display device comprising an antistatic film formed from the conductive coating liquid composition according to any one of claims 1 to 10. A display panel positioned on the lower polarizer plate;
An upper polarizer disposed on the display panel; And
And an antistatic layer disposed between the upper substrate and the upper polarizer of the display panel,
The anti-
A display device comprising a matrix material, a carbon nanotube dispersed in the matrix material, and a silsesquioxane compound having a disulfide group linking the siloxane group. 14. The method of claim 13,
Wherein the silsesquioxane compound is bonded with the following random and cage type. 14. The method of claim 13,
Wherein the silsesquioxane compound is represented by the following formula, R is independently an aromatic group or

(Wherein R2 is a C1 to C20 alkyl group).

14. The method of claim 13,
Wherein the antistatic film further comprises nanoparticles formed of a metal, a ceramic, a metal oxide, or a mixture thereof. 14. The method of claim 13,
Wherein the antistatic film has a hardness of 8 to 9H. 14. The method of claim 13,
Wherein the sheet resistance of the antistatic film is 10 ⁷ to 10 ⁹ Ω / square. 14. The method of claim 13,
Wherein the antistatic film exhibits a number of oscillations of the steel wool from 113 to 483 times until a scratch is observed at a light quantity of 1.37 to 1500 mW / cm &lt; 2 &gt;. 14. The method of claim 13,
And a touch electrode is built in the display panel.

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