KR101272959B1 - Preparing method of transparent heating generator forming a nano pattern using roll to roll gravure printing and transparent heating generator forming a nano pattern using thereof - Google Patents

Abstract

PURPOSE: A manufacturing method of a transparency heating element with a micro-pattern formed by using a roll-to-roll gravure printing method and a transparency heating element with a micro-pattern formed by using the same are provided to use conductive paste, thereby improving conductivity. CONSTITUTION: Conductive paste is coated. A roll-to-roll gravure printing method is applied for the coating. A micro-pattern is formed by the coating. The conductive paste includes a conductive polymer and carbon paste. The conductive paste includes conductive particles, nano silver gel, and binder resin.

Description

TECHNICAL FIELD OF THE INVENTION A method for manufacturing a transparent heating element having a fine pattern using a roll-to-roll gravure printing method and a transparent heating element having a fine pattern using the same USING THEREOF}

The present invention relates to a method for manufacturing a transparent heating element having a micropattern formed using a roll-to-roll gravure printing method, and more particularly to a transparent heating element having a micropattern formed using the same. A method of manufacturing a transparent heating element in which a micropattern is formed using a roll-to-roll gravure printing method capable of forming a transparent micropattern having a line width, a leading edge, and a line spacing, and realizing excellent heating characteristics at low power, and a transparent heating element having a micropattern formed thereon It is about.

In general, a vehicle side mirror defrosting device is a device that functions to remove water droplets or frost generated in the side mirrors during rainy weather and winter seasons to secure a driver's rear view and to drive safely. However, in the early days, the cost of the side mirror defroster was increased because it uses imported hot wire material, and even if the side mirror defroster is operated, it takes a long time to generate heat and it takes effect after a certain time. There was a problem that you have to drive or stop while receiving vision impairment.

In the case of a planar heating element using a conductive paste made of a conventional carbon material, the resistance value of the heating layer is not uniform, which has a disadvantage in that the heating temperature variation is large. there was. Since carbon materials such as carbon black and graphite powder, which are commonly used, are difficult to realize low resistance values, there is a limit to the application of a large area with a low voltage DC and a large distance between electrodes.

In addition, when the planar heating element is higher than the proper use temperature, the resistance value designed by external factors such as heat insulation, heat storage, and overvoltage changes, resulting in a change in the performance of the product, and easily deteriorated to reduce durability. . In order to solve this problem, a conductive material for a planar heating element in which a high-purity carbon material having high thermal conductivity is recently selected, a ceramic binder resin or a heat-resistant resin having high temperature stability, or a new material such as carbon nanofibers or carbon nanotubes is applied. Ink composition is introduced, but the price of the material is very expensive, it is difficult to apply practically.

Conventional transparent heating elements have been proposed by manufacturing electrodes by connecting electrodes after forming a heat generating layer through a sputtering process using a transparent conductive material such as ITO (Indium Tin Oxide) or Ag thin film on top of the glass. Due to the high sheet resistance of the transparent heating element, there is a problem that it is difficult to drive at a low voltage of 40V or less.

In addition, a method of patterning the heat generating layer by applying a conductive paste using screen printing has been used. However, the conventional screen printing method requires a high degree of proficiency, and when the screen printing is performed, the viscosity is low, so that the paste can flow down on the substrate, and it is difficult to obtain a large screen pattern with precision because the precision by the screen is reduced. In addition, the conventional screen printing method has a disadvantage that short-circuit or disconnection due to the screen during printing has been gradually reduced its use.

On the other hand, in recent years, a photolithography method using a photosensitive resin composition has been developed to form a high-precision pattern suitable for a large area. By forming a uniform thick film, exposing using a mask, and then implementing a required pattern using an alkaline developer, the photolithography method is difficult to apply to the production of transparent heating elements due to the complicated manufacturing process and high manufacturing cost. have.

Korean Patent Laid-Open Publication No. 10-2010-0040033 (Patent Document 1) discloses a high conductivity paste composition having a low resistance and a stable resistance coefficient and a method of manufacturing the same by including carbon nanotubes surface-treated with a heating element, but it is conductive By using carbon nanotubes surface-treated as an imparting material alone, the manufacturing cost increases, and there is a problem that it is difficult to form a uniform pattern because the coating film is formed by printing by screen printing.

Therefore, in order to solve the above problems, the present invention has been completed by developing a transparent heating element capable of uniformly and quickly forming a fine pattern using a gravure printing method widely used in the conventional printing industry.

Republic of Korea Patent Publication No. 10-2010-0040033

In order to solve the above problems, the present invention by applying a roll-to-roll gravure printing method of a conductive paste having a viscosity of 500 to 20,000 cP (25 ℃) a method for producing a transparent heating element formed a fine and uniform pattern quickly and accurately It aims to provide.

In addition, the present invention by using a conductive paste containing a conductive polymer, carbon paste, silver paste, conductive particles, silver nanogel and binder resin, to improve the electrical conductivity and to produce a transparent heating element that can obtain a high sinterability at low temperature firing It is an object to provide a method.

In addition, the present invention by using a conductive paste optimized for the roll-to-roll gravure printing method, it is possible to mass-produce a transparent heating element formed with a fine and uniform micro-pattern, and to provide a manufacturing method of a transparent heating element that can reduce the manufacturing cost It aims to do it.

In addition, an object of the present invention is to provide a transparent heating element having a fine pattern manufactured by the method of manufacturing a transparent heating element for forming a fine pattern.

The present invention for achieving the above object relates to a method for producing a transparent heating element to form a fine pattern satisfying the following formula 1 to formula 3 by applying a conductive paste in a roll-to-roll gravure printing method.

10 ≤ L _w ≤ 20 [Equation 1]

5 ≤ L _t ≤ 30 [Equation 2]

100 ≤ L _d ≤ 1000 [Equation 3]

(Equation 1, L _w is the line width of the fine pattern (μm), L _t is the leading edge of the fine pattern (μm) in Equation 2, and L _d is the line interval (μm) of the fine pattern in Equation 3. )

The conductive paste may include a conductive polymer, carbon paste, silver paste, conductive particles, silver nanogel, and a binder resin.

The conductive polymer is poly (3,4-ethylenedioxythiophene), polyaniline, polypyrrole, 2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene, polyphenylenevinylene And polythiophene selected from the group consisting of one or two or more selected from the group consisting of carbon nanotubes, graphene, copper, nickel, gold, silver, platinum, palladium, tin, and aluminum having an average particle size of 1 to 500 nm. , Indium oxide, zinc oxide and tin oxide may be selected.

The silver nanogel contains 0.1 to 0.5 parts by weight of hydrazine aqueous solution, 0.001 to 0.1 parts by weight of polymer binder, and 0.05 to 0.5 parts by weight of 2,2-azobis (diethanol) in 100 parts by weight of 0.1 to 0.5 M of silver ion aqueous solution. can do.

The fine pattern may be formed in a horizontal, vertical, curved, mesh, circular and oval, the gravure printing method is a printing speed of 5 to 40m / min, printing pressure is 20 to 40Kgf / ㎠, The film tension may be 5 to 10 kgf / cm 2, and the printing temperature may be 100 to 400 ° C.

In addition, the present invention is prepared by the above-described manufacturing method, and relates to a transparent heating element formed with a fine pattern satisfying the following formula 1 to formula 3.

10 ≤ L _w ≤ 20 [Equation 1]

5 ≤ L _t ≤ 30 [Equation 2]

100 ≤ L _d ≤ 1000 [Equation 3]

(Equation 1, L _w is the line width of the fine pattern (μm), L _t is the leading edge of the fine pattern (μm) in Equation 2, and L _d is the line interval (μm) of the fine pattern in Equation 3. )

It is preferable that the transmittance | permeability of the said transparent heating element is 70 to 90%, the time to reach 50 degreeC is 1 to 10 second, and sheet resistance is 0.5 to 100 mW / square.

The transparent heating element may be included in a vehicle side mirror heater, a steering wheel for a vehicle, a heating vest, a heating stroller, a self-wind power generating heating element, a heating insole, a building glass ultraviolet vehicle group, a heating film, a defrosting heating curtain, and a heating mat.

According to the method of manufacturing a transparent heating element having a fine pattern formed using the roll-to-roll gravure printing method of the present invention and the transparent heating element formed with the micropattern using the same, the conductive paste is applied by the roll-to-roll gravure printing method to quickly apply a fine and uniform pattern. And there is an advantage that can be formed accurately.

By using a conductive paste including conductive polymer, carbon paste, silver paste, conductive particles, silver nanogel and binder resin, there is an advantage that the electrical conductivity can be improved and high sinterability can be obtained at low temperature firing.

In addition, by controlling the optimized gravure printing speed, printing pressure, film tension and printing temperature, the conductive paste optimized for the roll-to-roll gravure printing method can form fine and uniform fine patterns, and can be driven at low power. It is possible to provide a transparent heating element which has significantly reduced the time to reach the ℃. ,

Such a transparent heating element can be mass-produced, and there is an advantage of reducing the manufacturing cost.

1 is a view showing a pattern for a car side mirror heater to which a transparent heating element of the mesh type according to an embodiment of the present invention is applied. .
2 is a view showing a pattern for a vehicle side mirror heater to which a transparent heating element of a mesh type according to an embodiment of the present invention is applied.
3 is a view showing a pattern for a vehicle side mirror heater to which a transparent heating element of a mesh and a line type according to an embodiment of the present invention are applied.
Figure 4 shows a 3D image of the transparent heating element formed by the roll-to-roll gravure printing method of the conductive paste according to an embodiment of the present invention.
Figure 5 shows a conventional automotive side mirror heater infrared thermal analysis photograph of the present invention.
Figure 6 shows a printed transparent heating element infrared thermal analysis photograph of the present invention.
7 shows an SEM image of a conductive paste according to an embodiment of the present invention.
Figure 8 shows an optical photograph of the gravure roll pattern line width and line spacing of the present invention.
9 is a schematic diagram of a two degree roll to roll gravure printing equipment.

Hereinafter, a preferred embodiment and a method for measuring physical properties of a method of manufacturing a transparent heating element having a fine pattern using the roll-to-roll gravure printing method of the present invention and a transparent heating element having the fine pattern will be described in detail. The present invention may be better understood by the following examples, which are for the purpose of illustrating the present invention and are not intended to limit the scope of protection defined by the appended claims.

The present invention for achieving the above object relates to a method for manufacturing a transparent heating element to form a fine pattern by applying a conductive paste in a roll-to-roll gravure printing method.

In roll-to-roll gravure printing method, the base film is applied between the rubber roll and the intaglio pattern roll and passes at a speed of 4 to 100 m per minute, the intaglio pattern is transferred to the base film, and the portions other than the intaglio pattern are simultaneously bladded. It is a printing method that can form a pattern. Such a roll-to-roll gravure printing method has superior characteristics of production speed and pattern uniformity compared to screen or offset printing methods, and has characteristics suitable for implementing a complex and fine pattern.

Therefore, the present invention can form a fine pattern that satisfies Equations 1 to 3 by manufacturing a transparent heating element using a conductive paste optimized for roll-to-roll gravure printing.

Conductive paste according to an embodiment of the present invention is composed of a conductive polymer, carbon paste, silver paste, conductive particles, silver nanogel and binder resin.

The conductive polymer may be used without limitation of the conductive polymer known in the art, for example, poly (3,4-ethylenedioxythiophene), polyaniline, polypyrrole, 2-methoxy-5- (2-ethyl It is preferable that 1 type, or 2 or more types are selected from hexyloxy) -1, 4-phenylene vinylene, polyphenylene vinylene, and polythiophene.

The carbon paste is to control the viscosity of the conductive paste and to improve conductivity, and can be used without limitation of the carbon paste surface known in the art. In particular, it is effective to reduce the change over time and improve the stability of the conductive paste of the present invention, for example, by mixing a certain ratio of carbon materials such as graphene, carbon nanotubes, carbon black, etc. in the polymer binder.

The silver paste is added with carbon paste to adjust the viscosity of the conductive paste and to improve conductivity, and any silver paste known in the art may be used without limitation. Particularly, for example, the use of a silver powder and a silver nanogel of the present invention to be described below in a proportion to the polymer binder is effective in order to reduce the change over time and improve the stability of the conductive paste of the present invention.

The conductive particles play a pivotal role in imparting conductivity in the conductive paste, so the conductivity is improved by the contact of the added conductive particles, and thus the contact area between the conductive particles must be increased. Accordingly, in the present invention, conductivity is greatly improved by adding various kinds of conductive particles having nano-sized particle sizes.

The conductive particles are preferably selected from carbon nanotubes, graphene, copper, nickel, gold, silver, platinum, palladium, tin, aluminum, indium oxide, zinc oxide and tin oxide, but are not limited thereto. It is not.

The carbon nanotubes have better electrical properties than metal materials having relatively high electrical conductivity or specific resistance, thereby reducing electrical resistance and improving thermal conductivity of the transparent heating element of the present invention. The carbon nanotubes may be selected from one or more selected from single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, and bundle-type carbon nanotubes, and carbon nanotubes surface-treated with acids / bases or organic groups. You may add a tube.

Among the conductive particles, metal oxides of indium oxide, zinc oxide and tin oxide are excellent transparent materials and are effective in forming a transparent heating element.

The conductive particles preferably have an average particle size of 1 to 500 nm, more preferably 20 to 500 nm. When the average particle size of the conductive particles is less than 1 nm, aggregation occurs in the conductive paste, and when the micropattern is formed, there is a problem in that short-circuit occurs in each part and the durability is remarkably reduced, and the ink production yield is significantly lowered. Problems may occur that make it difficult to form fine and uniform patterns.

In the conductive paste of the present invention, the silver nanogel is formed with an average particle size of 20 to 50 nm, and thus, may exhibit excellent conductive performance because it serves to reduce grain formation between particles during heat treatment of the pattern.

The silver nanogel preferably contains 0.01 to 1.0 parts by weight of a hydrazine aqueous solution, 0.001 to 0.1 parts by weight of a polymeric binder, and 0.05 to 0.5 parts by weight of 2,2-azobis (dieethanol) in 100 parts by weight of a 0.1 to 0.5 M silver ion aqueous solution. Do.

The silver nanogel is preferably prepared by mixing and reacting a silver ion aqueous solution, a hydrazine aqueous solution and a polymer binder, centrifuging, and then adding 2,2-azobis (diethanol), and the polymer binder included in the silver nanogel At least one may be selected from polypyrrolidone, polyurethane and polyamide.

The binder resin may be at least one selected from the group consisting of epoxy, cellulose, acrylic, vinyl chloride, vinyl acetate, polyvinyl alcohol, polyurethane, and polyester, which are well known in the art. You may use it.

As described above, the conductive paste of the present invention includes conductive polymers, carbon pastes, silver pastes, conductive particles, silver nanogels, and binder resins, thereby forming an electrical bridge between the respective materials to smooth the flow of electrons between the conductive particles. Can improve electrical conductivity.

The conductive paste of the present invention preferably has a viscosity of 100 to 20,000 cP to be suitable for a roll-to-roll gravure printing process. If the viscosity range is less than 100 cP, there may be a problem of bleeding and coffee stain effect of the printed matter, and if it exceeds 20,000 cP, ink may not be filled in the gravure dots and the ink may harden due to the bladder heat during high speed printing. Since the conductive paste may have a viscosity range, a uniform and fine pattern may be uniformly formed.

In addition, the optimum gravure printing conditions for forming a fine pattern as the core of the transparent heating element of the present invention is preferably a printing temperature of 100 to 400 ℃, more preferably 100 to 200 ℃. The printing temperature is preferably maintained in the above range as the temperature at the time of roll-to-roll gravure printing to maintain the appropriate viscosity of the conductive paste of the present invention to form a fine pattern.

In addition, the printing speed is 5 to 40m / min, the printing pressure is 20 to 40kgf / ㎠, the film tension is maintained at 5 to 10kgf / ㎠ is most suitable for forming a fine pattern.

The printing speed means the moving speed of the film according to the rotation of the roll during gravure printing, the printing pressure is the pressure between the pattern roll and the pressure roll of the gravure printing apparatus, the film tension is a force to pull the film from both sides it means.

When manufacturing a transparent heating element by printing roll-to-roll gravure printing using the conductive paste of the present invention in the range of the above range, each of the conditions are organically bonded to each other and uniform as shown in Figures 6 and 3 below. Since the line width, line spacing and leading thickness are formed, an ideal fine pattern of the transparent heating element can be formed.

The transparent heating element formed with a fine pattern manufactured according to the present invention is characterized by satisfying the following Equations 1 to 3.

10 ≤ L _w ≤ 20 [Equation 1]

5 ≤ L _t ≤ 30 [Equation 2]

100 ≤ L _d ≤ 1000 [Equation 3]

(Equation 1, L _w is the line width of the fine pattern (μm), L _t is the leading edge of the fine pattern (μm) in Equation 2, and L _d is the line interval (μm) of the fine pattern in Equation 3. )

The fine pattern is formed according to the structure of the roll pattern of the gravure printing roll, it may be formed in a horizontal, vertical, curved, mesh, circular and elliptical, as shown in Figure 1 to 3 transparent heating element It is possible to freely change the design according to the required property and usage. 1 and 2 is a view showing a pattern of the mesh type auto side mirror heater according to an embodiment of the present invention, Figure 3 is a mesh and a silver line type of the car side mirror heater according to an embodiment of the present invention The figure which shows a pattern.

The transparent heating element formed to satisfy the line width, head thickness, and line spacing of the fine pattern has transmittance of 70 to 90%, a time to reach 50 ° C. for 1 to 10 seconds, and a sheet resistance of 0.5 to 100 μs / □. It features. It was found that due to the conductive paste optimized for the roll-to-roll gravure printing method, the conductivity is remarkably improved, the transmittance is excellent, and the power can be driven at low power. Such a transparent heating element formed with a fine pattern of the present invention can be quickly and mass-produced by using a roll-to-roll gravure printing method, and can exhibit cost-effectiveness, a vehicle side mirror heater, a steering wheel for a vehicle, a heating vest, and a heating stroller. It can be applied to printed circuit boards such as various electronic devices, as well as self-winding power generating element, heating insole, building glass ultraviolet car group, heating film, and defrosting heating glass and heating mat.

Hereinafter, the transparent heating element in which the micropattern of the present invention is formed will be described in detail through Examples and Comparative Examples.

Property measurement

1. Initial resistance measurement

An automobile side mirror heater including a transparent heating element manufactured according to an embodiment of the present invention was left at room temperature (25 ± 5 ° C.) for 4 hours, and then resistance was measured using a digital multimeter.

2. Maximum current measurement at -40 ℃

An automobile side mirror heater including a transparent heating element manufactured according to an embodiment of the present invention was maintained at an ambient temperature of −40 ± 2 ° C., and current consumption was measured using a digital multimeter.

3. Thermal Performance Measurement

An automobile side mirror heater including a transparent heating element manufactured according to an embodiment of the present invention is assembled between the glass and the glass holder to assemble in a mirror subassembly state. The assembled mirror subassembly was left at -18 ° C for 2 hours, and then sprayed with water to form an ice layer until the ice thickness became 0.5 mm. The mirror subassembly shall be operated at 13.5 ± 0.3V when it is fixed at the same vertical position as the actual vehicle and then left at the test temperature for 4 hours and operated, and ice removal should be visually confirmed.

If it meets the following requirements, it is marked with ○, otherwise it is marked with X.

4. Evaluation of surface temperature control performance

When the ambient temperature of the vehicle side mirror heater including the transparent heating element manufactured according to an embodiment of the present invention is left at 100 ± 2 ℃ for 4 hours and then operated at 40 ℃, it operates at 13.5 ± 0.3V and the surface If the temperature does not exceed 65 ° C., it is indicated by o, otherwise it is indicated by X.

5. Heat durability evaluation

A: temperature exposure test

The temperature exposure test is carried out at 150 ° C, 20 ° C, 90 ° C, and -30 ° C for 24 hours, respectively.

B: Continuous Operation Test

Continuous operation tests are performed at 70 ° C, -10 ° C, 27 ° C and -30 ° C for 500 hours each.

C: Periodic Operational Test

Operate 1000 cycles at -5 ° C, 70 ° C and -30 ° C with 1 cycle of running the heater for 5 minutes and stopping for 10 minutes.

After each test, there should be no damage to the side mirror heater, and if the resistance is measured within 20% of the initial resistance range, it is marked with ○, otherwise it is marked with X.

6. Overvoltage test

After applying a voltage of 20 ± 0.3V to a mirror sub-assembly including a transparent heating element manufactured according to an embodiment of the present invention at room temperature (25 ± 5 ° C.) for 24 hours, if no breakdown or burn marks are indicated by ○ Otherwise, X is indicated.

7. Insulation Resistance Test

Measure the resistance between the outer conductor and the lead by applying 500V for 1 minute between the outer conductor (aluminum clad or chromed glass) and the side mirror heater lead, and if the insulation resistance measured at 500V is 1meg-ohm or more, And X otherwise.

8. Brine deposition test

The mirror subassembly including the transparent heating element manufactured according to an embodiment of the present invention was completely immersed in a 5 wt% sodium chloride aqueous solution in a vertical manner for 5 minutes as in a real vehicle, and then removed and operated at 13.5 ± 0.3V for 10 minutes. Perform 200 times with 1 cycle. At this time, there is no visible defect on the surface of the mirror subassembly, there is no connection connection of the terminal, and when the heater is operated, it is indicated by ○, otherwise it is indicated by X.

9. 50 ℃ reach time

An automobile side mirror heater including a transparent heating element manufactured according to an embodiment of the present invention was operated at room temperature (25 ± 5 ° C.) to measure the time (seconds) to reach 50 ° C.

10. Transmittance Measurement

The transmittance of the transparent heating element prepared according to one embodiment of the present invention was measured using HM-150 MURAKAMI HAZEMETER.

[Production Example 1]

Preparation of silver nanogel

To 10 ml of 0.2 M AgNO ₃ aqueous solution, 0.02 g of polypyrrolidone (Mn: 50,000) was added and stirred to disperse uniformly. 0.5 g of 10% aqueous hydrazine solution was slowly added dropwise to the dispersed solution and stirred at 25 ° C. for 3 hours to prepare a dark green solution. 20 ml of acetone was added to the obtained solution, followed by further stirring for 1 minute, and then 0.1 g of 2,2-azobis (diethanol) was added to the silver precipitate obtained by separating at 6000 rpm for 30 minutes using a centrifuge. 0.2 g was prepared.

[Production Example 2]

Preparation of Carbon Paste

100 g of phenol resin was mixed with 400 g of ethyl carbitol acetate, and stirred for 12 hours to prepare a uniform phase phenolic resin solution. Then, 30 g of carbon powder was added thereto and stirred while mixing uniformly for 3 hours using a homomixer and a three roll mill. Carbon paste was prepared.

[Production Example 3]

Manufacture of silver paste

1% by weight of the silver nanogel prepared in Preparation Example 1, 13% by weight of epoxy resin (Mw: 50,000), 84% by weight of silver particles, and 2% by weight of a curing agent (amine type) were added to the homomixer and three roll mill at 25 ° C. By using a uniform mixing for 3 hours to prepare a silver paste.

Example 1

Manufacture of Conductive Paste

30 g of conductive polymer (poly (3,4-ethylenedioxythiophene), Mw: 33000), 0.5 g of conductive particles (carbon nanotubes having an average particle diameter of 150 nm), 20 g of carbon paste (Preparation Example 2), silver paste (Preparation Example 3 ) 20 g, silver nanogel (manufacturing example 1) 5 g, binder resin (polyvinylpyrrolidone (Mw: 50,000) 10 g, epoxy resin (Mw: 50,000) 10 g, polyphenol (Mw: 50,000) 10 g) at room temperature After stirring for 2 hours at 3, using a three roll mill paste dispersion equipment to prepare a conductive paste to ensure the uniformity of the particles.

Preparation of Transparent Heating Element

Using the roll-to-roll gravure printing equipment shown in Figure 9 as shown in Table 1 as a pattern of Figure 1, printing pressure 20kgf / ㎠, printing speed 10m / min, film tension 1kgf / ㎠ and printing temperature 150 ℃ conditions By carrying out, to produce a transparent heating element formed a fine pattern of the mesh type. The physical properties of the prepared transparent heating element are measured and shown in Table 2.

[Example 2]

In the preparation of the transparent heating element, as shown in Table 1, except that the roll-to-roll gravure printing under the conditions of printing pressure 30kgf / ㎠, printing speed 20m / min, film tension 1kgf / ㎠ and printing temperature 150 ℃ In the same manner to prepare a transparent heating element with a fine pattern was formed. The physical properties of the prepared transparent heating element are measured and shown in Table 2.

[Example 3]

In the preparation of the transparent heating element, as shown in Table 1, except that the roll-to-roll gravure printing under the conditions of printing pressure 40kgf / ㎠, printing speed 30m / min, film tension 1kgf / ㎠ and printing temperature 150 ℃ In the same manner to prepare a transparent heating element with a fine pattern was formed. The physical properties of the prepared transparent heating element are measured and shown in Table 2.

Example 4

A transparent heating element was manufactured in the same manner as in Example 1 except that the fine pattern of the mesh type shown in FIG. 2 was formed. The physical properties of the prepared transparent heating element are measured and shown in Table 2.

[Example 5]

A transparent heating element was manufactured in the same manner as in Example 1 except that the fine pattern of the mesh type shown in FIG. 3 was formed. The physical properties of the prepared transparent heating element are measured and shown in Table 2.

Comparative Example 1

The physical properties of the transparent heating element of the commercially available prototype are measured and shown in Table 2 below.

[Table 1]

[Table 2]

As shown in Table 2, using the conductive paste of the present invention it was possible to derive the roll-to-roll gravure printing conditions suitable for fine pattern formation. The transparent heating element manufactured by the manufacturing method of the present invention was able to form a fine pattern of the desired line width, head thickness and line spacing, and it was found that physical properties such as sheet resistance, 50 ° C reaching time and transmittance were much better than those of the actual products. In addition, it was confirmed that the physical properties such as heat resistance, flame resistance.

Thus, the transparent heating element manufactured by the manufacturing method of the present invention is a vehicle side mirror heater, vehicle steering wheel, heating vest, heating baby carriage, self-wind power generating heating element, heating insole, building glass ultraviolet car group, heating film, bathroom glass defrosting heating It can also be applied to curtains and heating mats.

Although the preferred embodiment of the present invention has been described above, it is clear that the present invention can use various changes and equivalents, and can be applied in the same manner by appropriately modifying the above embodiment. Accordingly, the above description is not intended to limit the scope of the invention as defined by the following claims.

Claims (11)

A conductive paste is applied by a roll-to-roll gravure printing method, and a method of manufacturing a transparent heating element for forming a fine pattern satisfying the following formulas 1 to 3,
The roll-to-roll gravure printing method has a printing speed of 5 to 40m / min, a printing pressure of 20 to 40Kgf / ㎠, film tension of 5 to 10kgf / ㎠, printing temperature is 100 to 400 ℃,
The conductive paste includes a conductive polymer, carbon paste, silver paste, conductive particles, silver nanogel and binder resin,
The silver nanogel contains 0.1 to 0.5 parts by weight of hydrazine aqueous solution, 0.001 to 0.1 parts by weight of polymer binder, and 0.05 to 0.5 parts by weight of 2,2-azobis (diethanol) in 100 parts by weight of 0.1 to 0.5 M of silver ion aqueous solution. Method for producing a transparent heating element for forming a fine pattern, characterized in that.
10 ≤ L _w ≤ 20 [Equation 1]
5 ≤ L _t ≤ 30 [Equation 2]
100 ≤ L _d ≤ 1000 [Equation 3]
(Equation 1, L _w is the line width of the fine pattern (μm), L _t is the leading edge of the fine pattern (μm) in Equation 2, and L _d is the line interval (μm) of the fine pattern in Equation 3. )
delete The method of claim 1,
The conductive polymer is poly (3,4-ethylenedioxythiophene), polyaniline, polypyrrole, 2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene, polyphenylenevinylene And Method of producing a transparent heating element for forming a fine pattern of one or two or more selected from polythiophene.
The method of claim 1,
The conductive particles One or two or more fine patterns selected from carbon nanotubes, graphene, copper, nickel, gold, silver, platinum, palladium, tin, aluminum, indium oxide, zinc oxide and tin oxide having an average particle size of 1 to 500 nm. Method for producing a transparent heating element to form a.
delete The method of claim 1,
The fine pattern is a method of manufacturing a transparent heating element to form a fine pattern formed in a horizontal, vertical, curved, mesh, circular and elliptical.
delete delete delete delete The method of claim 1,
The method of manufacturing the transparent heating element includes a vehicle side mirror heater, a vehicle steering wheel, a heating vest, a heating stroller, a self-wind power generating heating element, a heating insole, a building glass UV car group, a heating film, a bathroom glass defrosting heating curtain and a heating mat. Method for producing a transparent heating element to form a fine pattern that is to produce a transparent heating element.

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