WO2024071809A1 - Transparent heating element for eye protection goggles and eye protection goggles comprising same - Google Patents

Abstract

The present invention relates to: a transparent heating element for eye protection goggles such as snowmobile goggles, ski goggles, motorcycle goggles, etc., having an anti-fog function; and eye protection goggles comprising same. Provided in the present invention are a transparent heating element for eye protection goggles, and eye protection goggles comprising same, in which the transparent heating element that is a calcined body of conductive ink or paste and has a grid pattern of straight lines or curves having a fine line structure is formed on the surface of a transparent substrate constituting a lens for eye protection goggles.

Description

Transparent heating element for eye protection goggles, eye protection goggles containing the same

The present invention relates to a transparent heating element for eye protection goggles and eye protection goggles including the same.

When using snowmobile goggles, ski goggles, motorcycle goggles, etc. in winter, a transparent conductive film is used as a transparent heating element in the goggles to remove snow, prevent snowfall, or prevent fogging. The transparent heating conductive film is used as a transparent oxide conductor (ITO). Indium Tin Oxide (Indium Tin Oxide) films are mainly used, and nanowire film films or films with a fine wire structure using conductive ink are also used.

In order to prevent the goggles from fogging, an ITO transparent conductive film, which is an oxide transparent conductor, is installed, electrodes are attached to the upper and lower edges of the transparent conductive film, electrode protection plates are attached to the surfaces of these electrodes, and power supply lines are connected to the upper and lower electrodes, respectively. A method was used to supply power from a power source and energize the transparent conductive film to increase the temperature of the goggles and dry the moisture condensed on the inner surface of the goggles.

The temperature is relatively low in the central area of such ski or motorcycle goggles, and the temperature is relatively high in the areas on both sides of the goggles, resulting in a temperature difference in these areas. In order to ensure the vision of the helmet wearer, it is necessary to first increase the temperature to prevent fogging of the central part of the goggles. In patent document 1, “Anti-fog lens structure and eye protection (KR 10-1857804 B1),” when a current is passed to raise the temperature of the central area to the level necessary to prevent fogging, more current flows in the areas on both sides, resulting in power loss. The harmful effects of this unnecessary consumption are being revealed.

In terms of lightness and flexibility, transparent substrates such as PET (polyethylene terephthalate), which have low heat resistance, are used in goggles, so the maximum heating temperature in all areas of the goggles is preferably 80 ℃ or lower. However, when the temperature in the central area rises, the temperature on both sides increases. Since the maximum heating temperature of the area is not disclosed, the heating characteristics of conventional ITO goggles for snowmobiles were measured and confirmed as shown in Figures 1, 2, 3, and 4. In particular, the maximum heating temperature of the electrode areas on both sides was 82 ~ 82. It was as high as 114 ℃. And as a result of measuring the heating characteristics of the goggles made of nanowires in Figure 5, the maximum heating temperature was as high as 81 ~ 106 ℃. This can also be confirmed through Table 1 below.

	Company A ITO	Company B ITO	Company C ITO	Company D ITO	Company E nanowire
Voltage (V)	12.0	12.0	12.0	12.0	12.0
Current (A)	0.851	0.575	0.851	1.117	0.800
best fever temperature (℃)	82.5	114.0	87.1	81.6	105.5
goggles average temperature (℃)	49.4	38.7	50.0	58.2	51.2

Since the distance between the electrodes at the top and bottom of the goggles is different depending on the location, the center of the goggles covers the face avoiding the nose area, so the distance between the top and bottom electrodes is shortened and the resistance is reduced. As a result, a larger current flows through the center of the goggles, raising the temperature. It becomes higher. To maintain the lowest required surface temperature to prevent fogging and to maximize battery life, it is necessary to heat the goggles uniformly across the entire front. To this end, in Patent Document 2, “PWM Heating System for Protective Glasses (JP 2017-040930 A),” the upper and lower electrodes were subdivided and the amount of current flowing was changed according to the distance between the upper and lower electrodes to equalize the temperature of the heating surface.

Patent Document 2 above proposes a method of dividing the upper and lower electrodes, but in order to change the amount of current according to the distance between the upper and lower electrodes, it is necessary to introduce a new control element to control the power source, which makes the circuit complicated. This causes a problem in that the performance of required functions is degraded and manufacturing costs are high.

In addition, in the case of goggles with fine lines formed with a conductor with a volume resistivity of 9 μΩ·cm or less, they were manufactured in the same way as conventional ITO goggles for snowmobiles, and in measuring heating characteristics, the heating temperature was measured at a constant voltage of 12 V. As a result of the measurement (Figure 6), the average heating temperature of the goggles in the fine line area was 61.4 ℃ and the maximum heating temperature was quite high at 121.8 ℃. The reason is that the conductivity of the conductor forming the fine wire is good and the distance between the upper and lower electrodes is Because it changes.

Here, a simple way to adjust the average and maximum heating temperature of the goggles in the fine line area is to change the power supply used, that is, from a 12 V constant voltage to a lower voltage power supply, but for snowmobile use, it is limited to 12 V constant voltage.

So, by lowering the conductivity of the conductor forming the fine line, a shield was manufactured using a conductor with reduced conductivity. As a result of measuring the heat generation temperature at a constant voltage of 12 V in the case of a snowmobile, the average heat generation of the goggle in the fine line area was found to be The temperature was 48.6 ℃ and the highest heat generation temperature was confirmed to be 71.9 ℃, which means that as a result of lowering the conductivity, less current flows and heat generation is suppressed (Figure 7).

A simple way to lower the conductivity of ink is to add a large amount of organic polymers, such as dispersants or adhesion aids, as conductivity-inhibiting impurities. Adding conductivity-inhibiting impurities has a detrimental effect on the reproducibility, stability, and reliability of the ink's electrical characteristics, so it is good. There is a need for a conductive transparent heating material that can secure visibility and heat generation characteristics. Accordingly, the present inventors focused on the above technical requirements and developed a stable average heat generation temperature and maximum heat generation in the entire area of the goggles at a constant voltage of 12 V and by varying the voltage of the power source. A transparent heating element for eye protection goggles that achieves a temperature of 80°C or lower was developed and the present invention was completed.

The present invention was invented to solve the above problems, and provides a transparent heating element for eye protection goggles with a maximum heating temperature of 80 ℃ or less and an average heating temperature of 30 to 60 ℃, and eye protection goggles including the same. Make it a problem to solve.

In order to solve the above technical problems, the present invention includes: a rectangular transparent substrate; A grid pattern formed by applying a conductive water-based ink to the transparent substrate and forming a stack, and made of fine lines; and electrodes formed on both ends of the transparent substrate and connected to the grid pattern, wherein the conductive water-based ink includes metal nanoparticles with a size of 5 to 50 nm and a water-soluble solvent, and the metal The nanoparticles are protected with a dispersion stabilizer composed of branched polyalkyleneimine segments, polyoxyalkylene segments, and amine salts, so that the maximum heating temperature of the transparent substrate is 80 ° C. or less, and the average heating temperature of the fine lines is 30 ~ 30. Provided is a transparent heating element for eye protection goggles, characterized in that the temperature is 60°C.

In the present invention, the grid pattern is characterized by a line width of 0.5 to 10 ㎛ and a pitch of 0.05 to 1.0 mm.

In the present invention, the grid pattern is characterized in that the maximum value of volume resistivity is 9 μΩ·cm.

In the present invention, the grid pattern is formed by applying the conductive water-based ink using imprint printing, screen printing, gravure printing, gravure offset printing, gravure reverse printing, or inkjet printing, and then firing.

In the present invention, the transparent substrate is characterized in that the vertical and horizontal length ratio is 1:2 to 5.

In the present invention, the conductive water-based ink is characterized in that it further contains metal particles having a size of 100 to 900 nm.

In the present invention, the water-soluble solvent is characterized in that it is at least one selected from alkylene glycol and glycerin.

In order to solve the above other technical problems, the present invention provides eye protection goggles, characterized in that they include the transparent heating element.

According to the transparent heating element for eye protection goggles of the present invention as a means of solving the above problem, the average heating temperature satisfies a stable range of 30 to 60 ℃ in all areas of the goggles with a grid pattern made of fine lines, and the maximum heating temperature is 80 ℃ or less. By achieving good visibility and heat generation characteristics on a transparent substrate, it can be used as eye protection goggles such as snowmobile goggles, ski goggles, or motorcycle goggles with anti-fog function.

In particular, the conductive water-based nano silver ink, which enables the creation of a transparent heating element with good conductivity, has a good lattice pattern formation of fine lines and shows good conductivity with low-temperature firing, ensuring sufficient heat generation even under various operating voltages, such as low-voltage batteries. This has the effect of forming a grid pattern with excellent visibility.

Figure 1 is a thermal image measurement image of company A's ITO goggles.

Figure 2 is a thermal image measurement image of Company B's ITO goggles.

Figure 3 is a thermal image measurement image of Company C's ITO goggles.

Figure 4 is a thermal image measurement image of Company D's ITO goggles.

Figure 5 is a thermal imaging image of company E's nanowire goggles.

Figure 6 is a thermal image measurement image of goggles with fine lines formed with a good conductor.

Figure 7 is a thermal image measurement image of goggles in which fine lines are formed using a conductor with reduced conductivity.

Figure 8 shows the shape of goggles simplified to a rectangle or square.

Figure 9 is a TEM photo of silver nanoparticles.

Figure 10 is an optical micrograph of the lattice pattern after firing.

Figure 11 is a measurement point of the heating temperature of a transparent heating element using a thermal imaging camera.

Figure 12 is a photograph of the left and right vertical electrode plates of various goggle models.

Figure 13 is a photograph of the upper and lower horizontal electrode plates of various goggle models.

Figure 14 is a photograph of the heating temperature of the transparent heating element according to Example 1 measured using a thermal imaging camera.

Figure 15 is a photograph of the heating temperature of the transparent heating element according to Example 2 measured using a thermal imaging camera.

Figure 16 is a photograph of the heating temperature of the transparent heating element according to Example 3 measured using a thermal imaging camera.

Figure 17 is a photograph of the heating temperature of the transparent heating element according to Example 4 measured using a thermal imaging camera.

Figure 18 is a photograph of the heating temperature of the transparent heating element according to Example 5 measured using a thermal imaging camera.

Figure 19 is a photograph of the heating temperature of the transparent heating element according to Example 6 measured using a thermal imaging camera.

Figure 20 is a photograph of the heating temperature of the transparent heating element according to Example 7 measured using a thermal imaging camera.

Figure 21 is a photograph of the heating temperature of the transparent heating element according to Example 8 measured using a thermal imaging camera.

Figure 22 is a photograph of the heating temperature of the transparent heating element according to Example 9 measured using a thermal imaging camera.

Figure 23 is a photograph of the heating temperature of the transparent heating element according to Example 10 measured using a thermal imaging camera.

Figure 24 is a photograph of the heating temperature of the transparent heating element according to Comparative Example 1 measured using a thermal imaging camera.

Figure 25 is a photograph of the heating temperature of the transparent heating element according to Comparative Example 2 using a thermal imaging camera.

Figure 26 is a photograph of the heating temperature of the transparent heating element according to Comparative Example 3 measured using a thermal imaging camera.

Figure 27 is a photograph of the heating temperature of the transparent heating element according to Comparative Example 4 measured using a thermal imaging camera.

Before explaining the present invention, the present inventors used a metal nanoparticle dispersion stabilizer containing a metal nanoparticle protective polymer composed of branched polyalkyleneimine segments and polyoxyalkylene segments, and an amine salt composed of an amine and an inorganic acid. Using a highly conductive water-based ink configured to protect nanoparticles, all of the goggles equipped with fine wires were measured using a 12 V constant voltage and by varying the voltage of the power source, in the same way as measuring the heating characteristics of conventional ITO goggles for snowmobiles. In order to overcome the difficulty in achieving a stable average heating temperature of 30 ~ 60 ℃ and a maximum heating temperature of 80 ℃ or less in the region, the resistance between electrodes was reduced with the same effect of lowering the conductivity of the conductor by changing the position of the electrodes and the grid pattern. We studied a method of dropping, that is, a method of reducing the current flow between electrodes, a method of reducing the deviation of resistance or current between electrodes by reducing the deviation of the distance between electrodes, and a method of changing the applied voltage.

That is, the present invention provides a transparent heating element for eye protection goggles. The transparent heating element of the present invention is a rectangular transparent substrate with a vertical and horizontal length ratio of 1:2 to 5, and fine lines with a line width of 0.5 to 10 μm and a pitch of 0.05 to 1.0 mm have a volume resistivity of 9 μΩ·cm or less. It is formed of a conductor to form a grid pattern, and electrodes connected to the fine lines are formed at both left and right ends or both upper and lower ends of the rectangular transparent substrate, and the highest heating temperature within the rectangular transparent substrate including the electrode is 80° C. or less. The average heating temperature of the fine lines forming the grid pattern is 30 to 60 ℃ and the light transmittance is 95% or more.

In the rectangular transparent substrate of the present invention, the shape of eye protection goggles such as snowmobile goggles, ski goggles, or motorcycle goggles is made of a rectangular transparent substrate, and has visibility without obstructing the field of view of the user wearing the eye protection goggles. In order to secure and appropriately secure the length of the electrodes and the distance between the electrodes formed at both ends of the left and right sides or both ends of the upper and lower sides of the transparent substrate, the ratio of the length and width of the rectangular transparent substrate should be 1:2 to 5. It is preferable, and the range of 1:2.5 to 4.5 is most preferable.

In the rectangular transparent substrate of the present invention, fine lines using good conductors form a grid pattern, and by setting the wiring width of the fine lines to 0.5 to 10 μm, visibility is not deteriorated and it is comfortable for users wearing eye protection goggles. Does not block or obstruct vision. And by setting the line width to 0.5 to 10 μm and the wiring pitch to 0.05 to 1.0 mm, the actual light transmittance (light transmittance ignoring the transparent substrate) can be over 95%, and by changing the line width and pitch of the fine lines, the transparency of the transparent substrate can be improved. The surface resistance value can be controlled. The line width of the fine wire is 0.5 to 10 μm, which is a desirable range from the viewpoint of ensuring conductivity, and is more preferably 1.0 to 7 μm. The pitch of the fine wires is 0.05 to 1.0 mm, which is a preferable range from the viewpoint of light transmittance of the transparent heating element, and is more preferable if it is 0.1 to 0.7 mm.

By adjusting the line width of the fine lines and the pitch between the fine lines within the above range, sufficient heat generation can be secured under various voltage conditions, such as low-voltage power, and the surface resistance value of the net grid pattern film can be controlled. As a result, it is possible to uniformly control the sufficient heat generation amount of the grid pattern film consisting of a net structure.

In addition, since the grid pattern of very fine lines is strong against bending or curvature of the transparent substrate and is formed by a simple printing method, it is possible to reduce manufacturing costs by eliminating the need for waiting time for large vacuum equipment and vacuum processing such as ITO film forming. .

The grid pattern consisting of a net structure of fine lines according to the present invention has a line or mesh shape formed by a combination of a plurality of straight lines or curves and is intended to flexibly respond to changes such as heat shrinkage of the transparent substrate. For example, the mesh-shaped unit grid shape may be a triangle such as an equilateral triangle or scalene triangle, a square such as a square or rectangular rhombus, a polygon such as a hexagon or octagon, a circle, or a cone. Additionally, irregular polygonal or circular patterns can be applied to reduce moiré phenomenon. Fine lines in a grid pattern composed of a net structure made of a good conductor are opaque, but appear transparent as light passes through the gaps between the fine lines or empty spaces in the mesh, resulting in the formation of a transparent heating element.

The fine lines formed on the rectangular transparent substrate of the present invention are made of a good conductor whose maximum volume resistivity is in the range of 9 μΩ·cm or less, and the electrodes connected to the fine lines are formed on the rectangular transparent substrate according to the voltage of the applied power source. It is formed at both ends of the left and right sides or both ends of the upper and lower sides, and the maximum heating temperature within the rectangular transparent substrate including the electrode is 80 ℃ or less, and the average heating temperature of the fine line portion is 30 to 60 ℃. It is a transparent heating element for eye protection goggles. .

The highest heating temperature within the rectangular transparent substrate and the average heating temperature of the fine line portion depend on the amount of heat (Q). As shown in Equation 1 below, the amount of heat (Q) is proportional to the flow of current, and the flow of current forms the fine line. It is inversely proportional to the resistance of the conductor. And it can be seen that the amount of heat (Q) is proportional to the applied voltage (V).

[Equation 1]

Heat (Q) = I ² R = IV, V = IR, I = V/R

Here, I is current, V is voltage, and R is resistance.

Therefore, in order to obtain a maximum heating temperature of 80 ℃ or less and an average heating temperature of 30 to 60 ℃, when using a conductor with good fine wire resistivity, the current must be controlled by various methods such as adjusting the length of the electrodes and the spacing between electrodes and adjusting the applied voltage of the electrode power source. The target temperature can be achieved by controlling the flow.

As shown in Figures 1 to 7, the width:length ratio of the conventional snowmobile shield is approximately 3:1, so the width:length ratio is 3:1, 1:1, and 1:3 as shown in A, B, and C of Figure 8. It can be explained that the resistance value of the transparent substrate formed with fine lines between the electrodes is adjusted by adjusting the length of the electrodes formed on the left and right ends or the upper and lower ends of the rectangular transparent substrate and the spacing between the electrodes.

As shown in Equation 2 below, the unit of surface resistivity (ρs) between two electrodes is Ω/□, which is the resistance value per unit area. And the surface resistance value (Rs) is also called surface resistance and the unit is Ω.

[Equation 2]

ρs = (V/I) × (W/L) Ω/□

Rs = V/I

Rs = ρs × (L/W) Ω

Here, W is the length of the electrode and L is the distance between electrodes.

As shown in Equation 2, the surface resistance of the transparent substrate between electrodes is inversely proportional to the length of the electrode. As the electrode becomes longer, the surface resistance of the transparent substrate decreases, and as the electrode length becomes shorter, the surface resistance of the transparent substrate increases. In addition, in proportion to the distance between electrodes, it can be seen that as the distance between electrodes becomes longer, the surface resistance of the transparent substrate increases, and as the distance between electrodes becomes shorter, the surface resistance of the transparent substrate decreases. Therefore, by adjusting the length of the electrodes formed on the left and right ends or the upper and lower ends of the rectangular transparent substrate or the distance between the electrodes, the surface resistance of the transparent substrate on which the grid pattern of fine lines between electrodes is formed can be adjusted, thereby controlling the flow of current. Therefore, the maximum heating temperature within the rectangular transparent substrate can be adjusted to 80 ℃ or less and the average heating temperature of the fine line portion can be adjusted to 30 ~ 60 ℃.

Fine lines on a rectangular transparent substrate are formed using a highly conductive water-based ink (NIM-006) with a volume resistivity of 9 μΩ·cm or less. Using transparent electrode films of the same conductivity, the length of the electrodes or between the electrodes is as shown in A, B, and C. When the distance varies, the surface resistance of the transparent substrate between electrodes changes.

The surface resistance of the transparent substrate between electrodes can be expressed as Rs = ρs It is surface resistivity. Here, for A, the surface resistance of the transparent substrate between electrodes is RsA = ρs × (1/3) = 1/3 ρs, and for B, the surface resistance of the transparent substrate between electrodes is RsB = ρs × (1/1) = 1 ρs. , In the case of C, the surface resistance of the transparent substrate between electrodes is RsC = ρs × (3/1) = 3 ρs. In other words, compared to A, in case of C, the same high-conductivity water-based ink (NIM-006) was used, but as the length of the electrode and the distance between electrodes change due to changes in the position and pattern of the electrode, the surface resistance of the transparent substrate between electrodes increases by 9 times. Therefore, compared to A, in the case of C, the flow of current can be controlled while using highly conductive water-based ink, so excessive heat generation can be controlled. In addition, compared to the electrode A formed on the longer left and right ends of the rectangular transparent substrate, the electrode C formed on the shorter upper and lower ends has the advantage of reducing the variation in the distance between electrodes and thus reducing the variation in resistance or current between electrodes. It also has the advantage of ensuring visibility without blocking or obstructing the view of a user wearing eye protection goggles.

As mentioned above, as a result of measuring the heating characteristics of conventional ITO goggles for snowmobiles, the highest heating temperature in the electrode area on both sides was particularly high at 82 ~ 114 ℃, and the heating characteristics of goggles made of nanowires were also measured and confirmed to have the highest heating temperature. The temperature was high, ranging from 81 to 106 degrees Celsius. Currently, the surface resistance of ITO for eye protection goggles is approximately 30 Ω/□. To apply a short vertical electrode using ITO, a surface resistance of about 10 Ω/□ is required. To form a low surface resistance film with an ITO film, the film thickness must be increased. Because it must be deposited thicker than 0.5 μm, it is difficult to apply due to increased manufacturing costs and low visibility due to low light transmittance. In addition, in order to improve the surface resistance of nanowires, a higher concentration of nanowires must be used, which increases manufacturing costs and increases haze, making it difficult to apply due to low visibility.

Using the highly conductive water-based ink (NIM-006), the heat quantity (Q), which represents the highest heating temperature within the rectangular transparent substrate and the average heating temperature of the fine line portion, is proportional to the applied voltage as shown in Equation 1 above and also depends on the flow of current. It is proportional. Therefore, by adjusting the voltage of the power supply applied to the electrodes formed on the long left and right ends of the rectangular substrate or the short upper and lower ends, the maximum heating temperature in the rectangular transparent substrate is 80 ℃ or less and the fine line portion is maintained. The average heating temperature can be adjusted to 30 ~ 60 ℃.

At the highest heating temperature within the rectangular transparent substrate of the present invention, organic films that have low heat resistance on the transparent substrate and are easy to make thin, flexible, or lightweight include, for example, PET (polyethylene terephthalate), PEN (polyethylene naphthalate), and PC ( Since polycarbonate (polycarbonate) is mainly used, the maximum heating temperature within the transparent substrate is preferably 80 ℃ or lower, and even better is 70 ℃ or lower.

Since the eye protection goggles made of a transparent heating element of the present invention require snow removal, snow prevention, and fogging prevention, the average heating temperature of the fine line portion is preferably in the range of 30 to 60 ℃, and more preferably in the range of 35 to 55 ℃. there is.

In order to always secure the helmet wearer's field of vision, fogging occurs when a temperature difference occurs where the temperature relatively increases or decreases depending on the area, such as the center or both sides of goggles for snowmobiles, skis, or motorcycles. It is necessary to first increase the temperature in the area to prevent goggles from fogging. However, if the temperature of the low-temperature area is raised to prevent fogging and a large amount of current flows, more current than necessary will flow in the high-temperature area, which not only increases power consumption but also increases the maximum heating temperature within the transparent substrate and the average heating temperature of the fine line area. Increasing harm occurs. Therefore, the temperature deviation in the entire area of the fine line portion in the transparent substrate of the present invention is preferably ±10°C based on the average heating temperature of the fine line portion, and it is even better if it is ±5°C.

The conductor used in the transparent heating element for eye protection goggles of the present invention is a good conductor with a volume resistivity of 9 μΩ·cm or less, and protects metal nanoparticles composed of branched polyalkyleneimine segments and polyoxyalkylene segments. A metal colloid solution composed to protect silver nanoparticles, which are metal nanoparticles, is used as a metal nanoparticle dispersion stabilizer containing a polymer and an amine salt composed of an amine and an inorganic acid.

Volume resistivity is expressed in Equation 3 and represents the inherent value of the conductor as the surface resistivity, which is the resistance per unit area, multiplied by the thickness of the conductive film. The unit is Ωm or μΩ·cm, and the volume resistivity (ρv) and surface resistivity (ρs) are proportional. It's a relationship.

[Equation 3]

R = ρv × (L/S)

ρv × (L/t × W) = ρv/t × (L/W) = ρs × (L/W)

ρv/t = ρs, ρv = ρs × t

Here, S is the cross-sectional area of the conductive film, t is the thickness of the cross-sectional area, W is the width of the cross-sectional area, and L is the length of the conductive film.

The metal nanoparticle dispersion stabilizer of the present invention is composed of a metal nanoparticle protective polymer composed of branched polyalkyleneimine segments and polyoxyalkylene segments, and an amine salt composed of an amine and an inorganic acid. That is, the metal nanoparticle dispersion stabilizer of the present invention immobilizes the metal into nanoparticles by coordinating the nitrogen atom of the alkyleneimine of the polyalkyleneimine segment with the metal or metal ion, and forming a bond between the polyalkyleneimine and the amine salt. It is a metal nanoparticle dispersion stabilizer that improves dispersion stability by coordinating amines generated by amine salt exchange with metals or metal ions and immobilizing them on the surface of metal nanoparticles. Therefore, the metal colloidal solution in which the metal nanoparticle complex protected by the dispersion stabilizer of the present invention is dispersed exhibits high dispersion stability due to the dispersion stabilizer.

Amine salts, which are composed of amines and inorganic acids, contribute to improved dispersion stability and good conductive performance. Amine, which is a component of amine salts, has a boiling point of 180°C or less, and more preferably 50°C to 130°C. This is because when the metal colloid solution of the present invention or a conductive material prepared by adjusting the solution with a conductive water-based ink is applied by printing on a transparent substrate and then fired at low temperature, the amine generated by amine exchange between polyalkyleneimine and amine salt is This is because it is easily removed at low temperatures and contributes to improving conductive performance. Therefore, the metal colloidal solution in which the metal nanoparticle complex protected by the dispersion stabilizer of the present invention is dispersed exhibits good conductivity even when fired at low temperatures. Preferably, the amine is a low molecular weight amine that can be easily removed at low temperatures, such as methylamine, dimethylamine, methylethylamine, ethylamine, diethylamine, propylamine, isopropylamine, butylamine, and isobutyl. One or more of amines and pentylamines may be used. In addition, the low-molecular-weight amine salt containing the low-molecular-weight amine may include, for example, hydrochloric acid, nitric acid, or sulfuric acid as an inorganic acid.

In addition, the polyalkyleneimine segment in the protective polymer of the present invention is a segment that can immobilize a metal into nanoparticles because the nitrogen atom site of the alkyleneimine is capable of coordinating with a metal or metal ion. As a result, when the complex of metal nanoparticles protected with the protective polymer of the present invention is manufactured or preserved in a hydrophilic solvent, the polyalkyleneimine segment and the polyoxyalkylene segment have hydrophilicity, and the polyalkyleneimine segment coordinates with the metal. By bonding, it is immobilized on the surface of the metal nanoparticle, while the polyoxyalkylene segment moves freely and actively in the solvent, forming a repulsive force between the metal nanoparticles, and as a result, the obtained metal colloid solution exhibits excellent dispersion stability and storage stability.

In addition, in the metal colloid solution containing the metal nanoparticle complex protected by the dispersion stabilizer of the present invention, the particle size, stability, or conductivity of the metal nanoparticle complex are determined by the weight average molecular weight of the protective polymer used or the polyalkyleneimine segment. It is also affected by the number of alkylene imine units, the structure or composition ratio of the protective polymer, or the amount of metal nanoparticle dispersion stabilizer used. Therefore, the number of alkyleneimine units in the polyalkyleneimine segment is not particularly limited, but if the number of units is too small, the protective ability of the metal nanoparticle as a protective polymer tends to be insufficient, while if the number of units is too large, the metal nanoparticle and the protective polymer are likely to be insufficient. The particle size of the formed metal nanoparticle complex tends to become large, which affects the dispersion stability. Accordingly, considering the ability to immobilize metal nanoparticles or prevent the nanoparticle complex from enlarging, the number of alkyleneimine units in the polyalkyleneimine segment may be 10 to 5,000, and more preferably in the range of 100 to 2,000. It can be.

If the weight average molecular weight is too small, the dispersion stability will deteriorate due to a decrease in the ability to protect the metal nanoparticles as a protective polymer. On the other hand, if the weight average molecular weight is too large, the nanoparticles may agglomerate, etc., thereby affecting the particle size or stability of the metal nanoparticle composite in the colloidal solution. becomes an inhibitory factor. Therefore, the weight average molecular weight of the protective polymer composed of polyalkylene imine segments and polyoxyalkylene segments is preferably in the range of 500 to 150,000, and more preferably in the range of 1,000 to 100,000. In addition, as described above, when the number of alkyleneimine units of the polyalkyleneimine segment is in the range of 100 to 2,000, the usage ratio in the mixture of the protective polymer composed of the branched polyalkyleneimine segment and the polyoxyalkylene segment and the low molecular weight amine salt can improve good conductive performance and dispersion stability in low-temperature firing by adjusting the amine equivalent of the low-molecular-weight amine salt relative to the amine equivalent of the polyalkyleneimine segment. At this time, the amine equivalent of the low-molecular-weight amine salt may preferably be in the range of 0.1 to 1.0 equivalents, and more preferably in the range of 0.2 to 0.9 equivalents, based on 1 equivalent of the amine of the polyalkyleneimine segment.

In addition, the polyoxyalkylene segment constituting the protective polymer of the present invention is a segment that exhibits high affinity with the solvent and maintains the storage stability of the colloidal solution when a hydrophilic medium such as water is used as a metal colloid solution. Polyoxyalkylene segments can be used without particular limitation as long as they are generally commercially available or synthetic. However, when using a hydrophilic solvent, it is better to use a nonionic polymer in that a colloidal solution with excellent stability can be obtained. As the polyoxyalkylene segment, for example, polyoxyethylene segment or polyoxypropylene segment is good, and polyoxyethylene segment is more preferred because it is easy to obtain industrially. In addition, the metal nanoparticle protective polymer of the present invention, which consists of the polyalkylene imine segment and the polyoxyalkylene segment, cannot sufficiently protect the metal nanoparticles when used in too small an amount, so a good particulate metal colloid solution cannot be obtained. In addition, when a large amount is used, the extra dispersion stabilizer interferes with the separation and purification process of metal nanoparticles, thereby worsening the separability of the tablets. Therefore, the metal nanoparticle protective polymer of the present invention is preferably used in an amount of 2 to 15 wt%, more preferably 3 to 10 wt%, based on the total weight of the metal nanoparticles, to disperse the metal colloid solution synthesized and obtained. It can improve stability and storage stability and show tablet separability.

As described above, the metal nanoparticle dispersion stabilizer of the present invention is composed of a metal nanoparticle protective polymer consisting of a polyalkyleneimine segment and a polyoxyalkylene segment and a low molecular weight amine salt, and the nitrogen of the alkyleneimine of the polyalkyleneimine segment The atomic site coordinates with the metal or metal ion, and the amine produced by amine exchange between the polyalkylene imine and the amine salt coordinates with the metal or metal ion and is immobilized on the surface of the metal nanoparticle, showing dispersion stability. , the polyoxyalkylene segment shows good solvent affinity in hydrophilic solvents and high association power in hydrophobic solvents, contributing to the stabilization of metal nanoparticles or easy purification and separation. Accordingly, the metal colloidal solution in which metal nanoparticles protected by the dispersion stabilizer of the present invention are dispersed, or the conductive material prepared by adjusting the solution with conductive water-based ink, is capable of low-temperature firing and has excellent performance when applied by printing on a transparent substrate and then fired. It has challenging performance. In other words, the quaternary amine unit in the polyalkyleneimine produced by amine exchange between a branched polyalkyleneimine and a low-molecular amine in the metal nanoparticle protective polymer has a weak bonding force, so it is attached to the surface of the metal nanoparticle to which it is coordinating. It is possible to easily separate (decouple) at low temperatures, making low-temperature firing possible. In addition, since it can be easily and completely separated at low temperatures, the protective polymer does not impede conductivity during the fusion process of the separated metal nanoparticles, resulting in good conductivity.

In the present invention, the conductive water-based ink, which can implement a transparent heating element with good visibility and conductivity, has good fine line grid pattern formation and shows good conductivity with low-temperature firing. Such low-temperature firing performance and good conductive performance are due to the dispersion stabilizer of metal nanoparticles composed of a mixture of a polymer having polyalkyleneimine segments and polyoxyalkylene segments having side yarns and a low-molecular-weight amine salt, which facilitates the formation of metal nanoparticles at low temperatures. This is because it is separated from the surface and subsequently the activated metal nanoparticles are firmly fused.

In addition, unlike conventional oil-based inks, the conductive water-based ink of the present invention does not dissolve or swell general-purpose plastic substrates and has no odor or toxicity, so there is no deterioration of the working environment and no risk of fire or explosion. In addition, electrically conductive water-based ink is printed using imprint printing, screen printing, and gravure printing, and is fired at a lower temperature compared to the conventional one to show good conductive performance, ensuring sufficient heat generation even under various operating voltages, such as low-voltage batteries. It is possible to form a grid pattern that exhibits excellent visibility.

The conductive water-based ink for a conductive transparent heating element of the present invention is reduced by adding a small amount of metal ions to a polymer solvent, and after a certain period of time, the remaining amount of metal ions is added again for reduction to obtain metal nanoparticles, and then an appropriate poor solvent is added. Metal nanoparticles are produced by precipitating, purifying, and separating metal nanoparticles and adding low-molecular-weight amine salts to the concentrated liquid of the separated metal nanoparticles. The raw material of the metal ion may be a metal salt or a metal ion solution. The raw material of the metal ion may be a water-soluble metal compound. Salts of a metal cation and an acid radical anion or a metal contained in the acid radical anion can be used. Metal ions containing metal types such as transition metals can also be used, but among these metal ions, metal ions of silver, gold, and platinum are particularly good because they are spontaneously reduced at room temperature or under heating and converted into nonionic metal nanoparticles. Additionally, when using the obtained metal colloid solution as a conductive material, it is preferable to use silver ions from the viewpoint of the ability to develop conductivity and the anti-oxidation properties of the coating film obtained by printing and painting.

In the conductive water-based ink of the present invention, metal particles having a particle size of 100 to 900 nm may be used together with metal nanoparticles having a size of 5 to 50 nm. Metal particles are relatively large in particle size compared to metal nanoparticles, and like metal nanoparticles, they are metal particles in a stable state that do not need to be protected on the surface with protective stabilizers. As metal particles, any known dried powder can be used. For example, gold (Au), silver (Ag), and platinum (Pt) can be used. There is no need to worry about clogging during printing and grid patterns can be formed. Considering that this is possible and that it is possible to form fine lines with a low resistance value after firing and excellent surface smoothness, metal particles with a particle size of 100 to 900 nm, and among metal particles, silver particles in the form of thin film scales are preferable.

In the present invention, by using metal nanoparticles in combination with metal particles, it is easy to obtain a film having better volume resistance in thermal baking than when only metal nanoparticles are used. Metal nanoparticles can completely fill the space between metal particles used together to form a film in a completely filled state. When heated and fired in this state, the protective polymer is easily separated (decoupled) from the surface of the metal nanoparticles even at low temperatures, and fusion of the metal nanoparticles progresses. At this time, the metal nanoparticles in the fully filled state fill the space between the metal particles to be used together, maintain the fully filled state, and become a fully sintered body integrated in the form of metal nanoparticles connecting the metal particles, thereby providing better conductive performance. indicates. The ratio of metal nanoparticles to metal particles used is not particularly limited, but the mass ratio of metal nanoparticles: metal particles = 10:90 to 80:20 is good, and good volume resistance can be obtained even if the ratio of metal nanoparticles is small. Considering this, the mass ratio of metal nanoparticles: metal particles = 15:85 to 40:60 is more preferable.

In manufacturing conductive water-based ink, it is good to contain the total of metal nanoparticles and metal particles protected with a protective stabilizer to be 40 wt% or more, preferably 40 to 95 wt%, based on the mass of solid content. It is more desirable. In order to improve the printing characteristics by considering all the physical properties of fine lines, it is effective to control the solid content in the composition of the conductive water-based ink. To do so, a binder resin may be used separately. The binder resin added at that time is unnecessary for fine lines during firing. Since it remains as a resistance component and impairs conductive performance, it is desirable to control the combined use of binder resin as a third component to the minimum necessary amount.

In the present invention, at least one type of alkylene glycol or glycerin may be used as the water-soluble solvent. As alkylene glycols, for example, alkylene glycols that are liquid at room temperature, such as ethylene glycol monoalkyl ether, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol, are preferable, and among them, 150 Alkylene glycol, which begins to volatilize above ℃, is more preferable, and glycerin is also very good. Water-soluble solvents such as alkylene glycols and glycerin with high volatile points have low vapor pressure at room temperature and do not volatilize easily, so they are excellent for producing various types of conductive water-based inks for printing. It has good miscibility with an aqueous solution of metal nanoparticles protected by a protective stabilizer composed of a mixture, does not cause phase separation, does not dissolve or swell various thermoplastic plastics, enables firing at low temperatures, and has low odor or toxicity. It's even better because it doesn't worsen the working environment.

The water-soluble solvent is preferably in the range of 2 to 20 wt% based on the total weight of the metal nanoparticles and metal particles protected with the protective stabilizer, and considering that it can improve printing characteristics, 3 to 8 wt% is more preferable.

Conductive water-based ink is a water-soluble solvent and an aqueous solution of metal nanoparticles protected by a dispersion stabilizer consisting of a mixture of a polymer having the polyalkylene imine segment and polyoxyalkylene segment and a low-molecular-weight amine salt having the side yarns, or a water-soluble solvent. An aqueous solution of metal nanoparticles protected with a dispersion stabilizer consisting of a mixture of a polymer having polyalkylene imine segments and polyoxyalkylene segments and a low molecular weight amine salt is premixed with the metal particles and a water-soluble solvent, for example, as required. It can be manufactured by stirring and dispersing with a certain shear force.

In the metal nanoparticles prepared by the above method, a quaternary amine unit among polyalkyleneimines is generated through amine salt exchange between the added low molecular weight amine salt and the polyalkylene imine segment of the protective polymer. Among the produced polyalkylene imines, the quaternary amine unit has a weak binding force, so it is easily separated (decoupled) from the surface of the metal nanoparticle to which it is coordinating, even at low temperatures. Accordingly, low-temperature sintering is possible while being easily and completely separated, and the protective polymer does not impede conductivity during the fusion process of the separated metal nanoparticles, resulting in good conductive performance. In addition, low-molecular-weight amines produced by amine exchange between polyalkyleneimines and low-molecular-weight amines can also be immobilized on the surface of metal nanoparticles through coordination bonds with metals, contributing to improved dispersion stability.

The size of the metal nanoparticles included in the non-volatile content of the metal colloid solution obtained in the present invention is not particularly limited, but in order for the metal colloid solution to have better dispersion stability and conductivity, the size of the metal nanoparticles is 5 to 50 nm. It may be a fine particle in the range, preferably in the range of 10 to 40 nm. In general, metal nanoparticles in the tens of nanometer-sized region have characteristic optical absorption due to surface plasmons depending on the type of metal. Accordingly, by measuring the plasmon absorption of the metal colloid solution obtained in the present invention, it can be confirmed that the metal exists as nanometer-sized particles in the solution, and the average particle size and distribution of the solution can be confirmed by measuring the transmission electron microscope (TEM) photograph of the solution. You can check the width, etc. However, the average particle size in the present invention is the average value of metal nanoparticles measured by TEM using H-7500 manufactured by Hitachi Corporation, and then the sizes of about 100 particles are measured.

In the transparent substrate used in the transparent heating element for eye protection goggles of the present invention, there is no limitation to the type, but an organic film or a glass substrate can be used, and an organic film that has low heat resistance and is easy to make thin, flexible, or lightweight can be used. . As the organic film, for example, PET (polyethylene terephthalate), PEN (polyethylene naphthalate), or PC (polycarbonate) can be used.

The method of forming fine lines on the transparent substrate of the transparent heating element for eye protection goggles of the present invention is, for example, an imprint printing method. It can be formed by screen printing, gravure printing, gravure offset printing, gravure reversal printing, and inkjet printing, and can be appropriately selected in terms of ease of manufacturing, performance of the transparent substrate being manufactured, and manufacturing cost.

The transparent heating element for eye protection goggles of the present invention can be used as eye protection goggles such as snowmobile goggles, ski goggles, or motorcycle goggles, and can be applied to various goggles other than the above types as long as the goggles can protect the eyes. These eye protection goggles can be used regardless of the season, but they can be better applied in winter when snow removal, snow prevention, or fogging prevention are required. In addition, by forming fine lines using a good conductor with a volume resistivity of 9 μΩ·cm or less on a transparent substrate that has low heat resistance and is easy to make thin, flexible, and lightweight, a conductive transparent substrate is created that secures visibility and prevents fogging with appropriate heat generation performance. It is also possible to provide various transparent heat-generating devices for eye protection, including:

Hereinafter, embodiments of the present invention will be described in more detail as follows. However, the following examples are merely illustrative to aid understanding of the present invention and are not intended to limit the scope of the present invention.

Analytical instruments and measurement methods used

¹ H-NMR: Japan Electronics Co., Ltd. product, JNM ECP-400, 400 Hz

GPC measurements: ACQUITY APC Core System, a product of Waters Corporation

TEM measurement: Hitachi Co., Ltd. product, H-7500

SEM measurement: JSM-6490LV, manufactured by Japan Electronics Co., Ltd.

Volume resistivity measurement: PMX35-3A manufactured by Kikusui Co., Ltd. and U1252A manufactured by Argyrant Technology Co., Ltd.

Solid content measurement method: The content of non-volatile substances including metal nanoparticles contained in the silver nanoparticle centrifugal coagulation paste was measured. From the silver nanoparticle centrifugal coagulation paste prepared in the following examples, about 0.5 g of the agglomeration paste was dropped onto an aluminum dish, pre-dried at 60 degrees Celsius, and then dried at 180 degrees Celsius using a hot air dryer to remove the residual solvent. After drying for 30 minutes, the solid content was measured by calculating the difference in weight of the sample before and after drying.

Solid content (%) = (Weight of sample after drying / Weight of sample before drying) × 100

Method for measuring volume resistance of a conductive water-based ink film: After film formation and printing of a conductive water-based ink composition on a glass substrate was completed, the film was baked at 120°C for 30 minutes using a heat oven, and the volume resistance was measured using the fired film sample. The thickness of the obtained film sample was measured using an SEM (JSM-6490LV, manufactured by Japan Electronics Co., Ltd.), and the surface resistivity (Ω/□) was measured using a low resistor (U1252A, manufactured by Argyrant Technology Co., Ltd.) and a constant current constant voltage device (Kikusui Co., Ltd.). Product, PMX35-3A) was used to measure.

Volume resistivity (Ωㆍcm) = Surface resistivity (Ω / □) × Thickness (cm)

Preparation Example 1: Polymer synthesis of polyalkyleneimine segment and polyoxyalkylene segment

All of the following reactions were carried out under a nitrogen atmosphere. Weigh 60.0 g of monomethoxypolyethylene glycol (M _n = 2,000) and 420.0 ml of toluene and add them to the reactor. Heat the internal temperature of the reaction solution to about 60 degrees Celsius under a stirring speed of 200 rpm to confirm that it is dissolved, and then add the reaction solution to the reactor. The internal temperature was lowered to below 18 degrees Celsius. Thereafter, 20.0 ml of a toluene suspension of pulverized potassium hydroxide 4.0 was added to the reactor, and it was confirmed that the temperature of the reaction solution was maintained between 18 degrees Celsius and 25 degrees Celsius. Next, 17.2 g of p-toluenesulfonyl chloride was added in small amounts to the inside of the reaction vessel, and then 60.0 mL of a toluene suspension of pulverized potassium hydroxide 12.0 was slowly added. Each time the toluene suspension was added to the reaction vessel, the temperature of the reaction solution decreased by degrees Celsius. It was confirmed that the temperature was maintained between 18 degrees and 25 degrees Celsius. Again, 2.0 g of p-toluenesulfonyl chloride was added to the reaction vessel, and then 40.0 ml of a toluene suspension of pulverized potassium hydroxide 8.0 was added. Similarly, after confirming that the temperature of the reaction solution was maintained between 18 degrees Celsius and 25 degrees Celsius, the reaction solution was stirred for an additional 30 minutes.

In order to filter the reaction solution, filter paper (5 ㎛) and silica gel or anhydrous magnesium sulfate were placed on it in a Buchner funnel, prepared for filtration, connected to a pressure pump, and then subjected to reduced pressure filtration. Reduced-pressure filtration was repeated approximately three times until the filtered reaction mixture became a clear solution.

The solvent was distilled from the filtered reaction mixture using a rotary evaporator. At this time, the cooling water was maintained at about 5 degrees Celsius and the temperature of the rotary evaporator bath was maintained at 40 degrees Celsius to produce 50.4 g of tosylated polyethylene glycol monomethyl ether (yield 78 degrees Celsius). %) was prepared.

The 1H-NMR (400MHz) measurement results for the manufactured product are as follows.

¹ H-NMR (D ₂ O) measurement results:

δ(ppm) = 7.8(d, 2H), 7.2(d, 2H), 4.2(t, 2H), 3.7 to 3.8(m, PEGmethylene), 3.5(s, 3H)

Next, the target polymer was prepared by grafting polyethylene glycol onto the side yarn polyethyleneimine. All of the following reactions were carried out under a nitrogen atmosphere. 380 g of dimethylacetamide was added to the reactor and slowly heated at a stirring speed of 200 rpm, 73.0 g of side polyethyleneimine (M _n = 10,000) was added and dissolved, and 48.0 g of tosylated polyethylene glycol monomethyl ether prepared previously was added. It was dissolved and 100.0 g of dimethylacetamide was added again. The temperature of the reaction solution was maintained at 120 degrees Celsius and the reaction was stirred for about 6 hours.

After filtering the reaction solution, solvents such as dimethylacetamide were distilled off using a reduced pressure solvent remover.

Then, about 320.0 g of distilled water was added to the reaction vessel and dissolved well, and then the aqueous product solution was filtered using a Loca device. At this time, 437.0 g of the prepared polymer product was prepared and stored as a 25% aqueous solution.

¹ H-NMR (400 Hz) and GPC measurement results for the manufactured product are as follows.

¹ H-NMR (D ₂ O) measurement results:

δ (ppm) = 3.5 to 3.6 (m, PEGmethylene), 3.2 (s, 3H), 2.3 to 2.7 (m, bPEI ethylene)

GPC measurement results:

Rt = 23.586, Mw = 16,480

Preparation Example 2: Synthesis of silver nanoparticle centrifugation flocculation paste

All of the following reactions were carried out under a nitrogen atmosphere. 284 g of distilled water was added to the reactor, the stirring speed was operated at 100 rpm, 23.04 g of the polymer aqueous solution prepared in Preparation Example 1 and 181.2 g of dimethylethanolamine were added, and the reaction solution was heated to a temperature of 40 degrees Celsius. After confirming that the solution had been reached, the stirring speed was adjusted to 200 rpm. Afterwards, 192 g of distilled water was added to 115.2 g of silver nitrate, and the aqueous solution of silver nitrate, which had been stirred and dissolved in advance, began to be added dropwise over 30 minutes. An amount equivalent to about 2% of the prepared aqueous silver nitrate solution was added dropwise over 3 minutes, and then added dropwise for 3 minutes. After the reaction was stopped and sufficiently stirred, the remaining silver nitrate aqueous solution was added dropwise over 24 minutes. After completing the dropwise addition of the silver nitrate aqueous solution, the reaction solution was heated and the stirring reaction was maintained for about 3 hours from the time the temperature reached 50 degrees Celsius, and then cooled again to 30 degrees Celsius and the reaction was terminated after confirming that the temperature had been reached. did.

In order to purify and separate the silver nanoparticles synthesized in the reaction solution, 800 g of the above synthetic mixture was added to 3,200 g of acetone, stirred for about 5 minutes, and allowed to stand for a certain period of time to separate the silver nanoparticles by sedimentation. Next, the above sedimentation solution was added to 1,200 g of acetone, stirred for about 5 minutes, and allowed to stand for a certain period of time to sediment and separate the silver nanoparticles again. After confirming the separation layer, the transparent upper layer solution was separated and removed, and then 4.7 g of the previously prepared amine salt aqueous solution was added to the separated silver nanoparticle solution and stirred. To prepare the amine salt, 10.0 g of distilled water was added to 73.1 g of diethylamine (bp. 56°C) using an ice bath, and while stirring, 101.3 g of hydrochloric acid aqueous solution (36%) was slowly added and mixed to obtain a molar ratio of 1:1. An aqueous solution of amine salt was prepared as a mixed solution. Then, the silver nanoparticle solution to which the aqueous amine salt solution was added was centrifuged at 3,000 rpm for 10 minutes using a centrifuge to prepare 86.2 g of silver nanoparticle centrifugation aggregation paste with a silver solid content of 89.0%.

Figure 9 shows the TEM measurement results of silver nanoparticles, and it is confirmed that the average particle size of the silver nanoparticles is 23 nm and that they are monodisperse, good crystalline particles.

Preparation Example 3: Preparation of highly conductive water-based ink NIM-006 for fine line filling

83.0 g of centrifugal agglomeration paste of metal nanoparticles protected with a protective stabilizer consisting of a mixture of a polymer having side polyalkyleneimine segments and polyoxyalkylene segments and a low molecular weight amine salt obtained in Preparation Example 2 (non-volatile matter 89%) ), 5.2 g of glycerin, 6.2 g of distilled water, and 3.0 g of ethylene glycol monobutyl ether were placed in a container, stirred well, and premixed. The low-volatile point volatile solvent was removed under reduced pressure using a mixture of premixed nanoparticle agglomeration pastes. After premixing by stirring well again, 0.34 g of antifoaming agent (Antimussol UDF, manufactured by Archroma) was added and mixed and dispersed using a high-speed disperser. Then, 0.02 g of surfactant (SM-3310P, manufactured by KCC, Korea) was added and further dispersed. NIM-006, a water-based ink for highly conductive fine line filling, was manufactured. The volume resistance of the highly conductive water-based ink NIM-006 for filling fine lines prepared in this way was measured according to the volume resistance measurement method of the conductive water-based ink film described above and was 4.2 μΩcm.

Preparation Example 4: Preparation of screen water-based ink Sc-005 for electrode of rectangular transparent substrate

74.2 g of centrifugal agglomeration paste of metal nanoparticles protected with a protective stabilizer consisting of a mixture of a polymer having side polyalkyleneimine segments and polyoxyalkylene segments and a low molecular weight amine salt obtained in Preparation Example 2 (non-volatile matter 89%) ), 4.6 g of glycerin, 9.0 g of distilled water, 2.7 g of ethylene glycol monobutyl ether, and 7.0 g of epoxy binder resin were placed in a container and stirred well for premixing. The low-volatile point volatile solvent was removed under reduced pressure using a mixture of premixed nanoparticle agglomeration pastes. After stirring well again and premixing, 0.30 g of antifoamer (Antimussol UDF, manufactured by Archroma) and 0.04 g of thickener were added and mixed and dispersed using a high-speed disperser, followed by 0.02 g of surfactant (SM-3310P, manufactured by KCC, Korea). and further dispersed to prepare screen water-based ink Sc-005 for electrodes on transparent substrates. The volume resistance of the water-based electrode screen ink Sc-005 prepared in this way was 8.1 μΩcm as measured according to the volume resistance measurement method of the conductive water-based ink film described above.

Example 1

A transparent trench PET film substrate for imprint printing having a lattice pattern composed of fine lines with a line width of 2.0 ㎛ and a line spacing of 200 ㎛ was printed using the imprint printing method using the highly conductive water-based ink NIM-006 for filling fine lines prepared in Preparation Example 3. Lines were filled and printed. After filling printing is completed, pre-drying is performed at 60°C for 5 minutes using a drying oven, and baking is performed at 120°C for 30 minutes using a heat oven to form a grid pattern consisting of fine lines with a line width of 2.0 ㎛ and a spacing of 200 ㎛ on the PET film. A conductive transparent heating substrate was obtained laminated on the substrate.

Subsequently, a screen printing method was performed on the left and right ends of the rectangular transparent substrate on which the grid pattern was formed using the water-based screen ink Sc-005 for electrodes prepared in Preparation Example 4 and left and right vertical electrode engraving of goggle model #2001 (see FIG. 12). Left and right vertical electrodes were printed. After printing was completed, pre-drying was performed at 60°C for 5 minutes using a drying oven, and baking was performed at 120°C for 30 minutes using a heat oven to obtain a transparent heating substrate with formed electrodes.

The grid pattern after firing was confirmed by the optical microscope picture in Figure 10, and the transmittance was measured using Linshang's transmittance meter LS162, and the transmittance, ignoring the transparent trench PET film substrate, was 95.5%.

Then, a power source was connected to the transparent heating substrate on which the electrodes were formed, a 12 V voltage was applied to the fine wire, and the electrical and heating characteristics were measured. Heating temperature was measured at 30 points in total, including 24 points on the fine lines of the transparent heat-generating PET substrate and 6 points, 3 points on each electrode, using FLUKE's thermal imaging camera TI300Plus (see FIGS. 11 and 14).

Example 2

A transparent heating substrate with electrodes was produced in the same manner as in Example 1, except that the left and right vertical electrode plates of goggle model #2001 used in Example 1 were changed to the left and right vertical electrode plates of goggle model #2002 (see FIG. 12). After obtaining, a 12 V voltage was applied to the fine wire in the same manner as in Example 1, and the electrical characteristics and heat generation characteristics were measured (see FIG. 15).

Example 3

A transparent heating substrate with electrodes was prepared in the same manner as in Example 1, except that the left and right vertical electrode plates of goggle model #2001 used in Example 1 were changed to the left and right vertical electrode plates of goggle model #2003 (see FIG. 12). After obtaining, a 12 V voltage was applied to the fine wire in the same manner as in Example 1, and the electrical characteristics and heat generation characteristics were measured (see FIG. 16).

Example 4

The electrodes were made in the same manner as in Example 1, except that the left and right vertical electrode plates of the goggle model #2001 used in Example 1 were changed to the left and right vertical electrodes of the long rectangular square goggle model #1001 (see FIG. 12). After obtaining this transparent heating substrate, the electrical and heating characteristics were measured by applying a voltage of 17 V to the fine wire in the same manner as in Example 1 (see FIG. 17).

Example 5

After obtaining a transparent heating substrate with electrodes formed in the same manner as in Example 4, the electrical characteristics and heat generation were measured in the same manner as in Example 4, except that a voltage of 17 V was applied to the fine wire and a voltage of 18 V was applied to the fine wire. The properties were measured (see Figure 18).

Example 6

A transparent heating substrate with electrodes was prepared in the same manner as in Example 1, except that the left and right vertical electrode plates of goggle model #2001 used in Example 1 were changed to upper and lower horizontal electrode plates of goggle model #2001 (see FIG. 13). After obtaining, a 4 V voltage was applied to the fine wire in the same manner as in Example 1, and the electrical characteristics and heat generation characteristics were measured (see FIG. 19).

Example 7

A transparent heating substrate with electrodes was prepared in the same manner as in Example 1, except that the left and right vertical electrode plates of goggle model #2001 used in Example 1 were changed to upper and lower horizontal electrode plates of goggle model #2002 (see FIG. 13). After obtaining, a 4 V voltage was applied to the fine wire in the same manner as in Example 1, and the electrical characteristics and heat generation characteristics were measured (see FIG. 20).

Example 8

A transparent heating substrate with electrodes was prepared in the same manner as in Example 1, except that the left and right vertical electrode plates of goggle model #2001 used in Example 1 were changed to upper and lower horizontal electrode plates of goggle model #2003 (see FIG. 13). After obtaining, a 4 V voltage was applied to the fine wire in the same manner as in Example 1, and the electrical characteristics and heat generation characteristics were measured (see FIG. 21).

Example 9

The electrodes were made in the same manner as in Example 1, except that the left and right vertical electrode plates of the goggle model #2001 used in Example 1 were changed to the top and bottom horizontal electrodes of the long rectangular square goggle model #1001 (see FIG. 13). After obtaining this transparent heating substrate, the electrical and heating characteristics were measured by applying a 4 V voltage to the fine wire in the same manner as in Example 1 (see FIG. 22).

Example 10

After obtaining a transparent heating substrate with electrodes formed in the same manner as in Example 9, the electrical characteristics and heat generation were measured in the same manner as in Example 9, except that a 4 V voltage was applied to the fine wire and a 2 V voltage was applied to the fine wire. The properties were measured (see Figure 23).

Comparative example 1

A transparent heating substrate with electrodes was prepared in the same manner as in Example 1, except that the left and right vertical electrode plates of goggle model #2001 used in Example 1 were changed to upper and lower horizontal electrode plates of goggle model #2001 (see FIG. 13). After obtaining, a 12 V voltage was applied to the fine wire in the same manner as in Example 1, and the electrical characteristics and heat generation characteristics were measured (see FIG. 24).

Comparative Example 2

A transparent heating substrate with electrodes was prepared in the same manner as in Example 1, except that the left and right vertical electrode plates of goggle model #2001 used in Example 1 were changed to upper and lower horizontal electrode plates of goggle model #2002 (see FIG. 13). After obtaining, a 12 V voltage was applied to the fine wire in the same manner as in Example 1, and the electrical characteristics and heat generation characteristics were measured (see FIG. 25).

Comparative Example 3

A transparent heating substrate with electrodes was prepared in the same manner as in Example 1, except that the left and right vertical electrode plates of goggle model #2001 used in Example 1 were changed to upper and lower horizontal electrode plates of goggle model #2003 (see FIG. 13). After obtaining, a 12 V voltage was applied to the fine wire in the same manner as in Example 1, and the electrical characteristics and heat generation characteristics were measured (see FIG. 26).

Comparative Example 4

The electrodes were made in the same manner as in Example 1, except that the left and right vertical electrode plates of the goggle model #2001 used in Example 1 were changed to the top and bottom horizontal electrodes of the long rectangular square goggle model #1001 (see FIG. 13). After obtaining the formed fine wire transparent heat-generating substrate, a 6 V voltage was applied to the fine wire in the same manner as in Example 1, and the electrical and heat generation characteristics were measured (see FIG. 27).

Examples 1 to 10 and Comparative Examples 1 to 4 are summarized and shown in Tables 2 to 4 below.

	Example 1	Example 2	Example 3	Example 4	Example 5
goggle type		#2001	#2002	#2003	#1001	#1001
Electrode type	vertical electrode	vertical electrode	vertical electrode	vertical electrode	vertical electrode
electrode length (cm)	15.5	11.0	15.0	4.5	4.5
Distance between electrodes (cm)	31.8	29.4	33.2	24.0	24.0
applied voltage (V)	12.0	12.0	12.0	17.0	18.0
electric current (A)	0.32	0.33	0.34	0.34	0.36
Average fever temperature (℃)	40.1	41.9	42.3	52.9	58.1
highest fever temperature (℃)	48.7	56.8	55.9	61.3	66.2

	Example 6	Example 7	Example 8	Example 9	Example 10
goggle type		#2001	#2002	#2003	#1001	#1001
Electrode type	horizontal electrode	horizontal electrode	horizontal electrode	horizontal electrode	horizontal electrode
electrode length (cm)	29.7/25.0	25.0/28.9	24.5/25.8	25.0	25.0
Distance between electrodes (cm)	7.8	7.4	7.2	4.0	4.0
applied voltage (V)	4.0	4.0	4.0	4.0	2.0
electric current (A)	0.39	0.56	0.61	0.71	0.36
Average fever temperature (℃)	32.1	34.3	33.0	36.5	31.7
highest fever temperature (℃)	47.3	53.4	49.4	73.4	42.0

	Comparative Example 1	Comparative Example 2	Comparative Example 3	Comparative Example 4
goggle type		#2001	#2002	#2003	#1001
Electrode type	horizontal electrode	horizontal electrode	horizontal electrode	horizontal electrode
electrode length (cm)	29.7/25.0	25.0/28.9	24.5/25.8	25.0
Distance between electrodes (cm)	7.8	7.4	7.2	4.0
applied voltage (V)	12.0	12.0	12.0	6.0
electric current (A)	1.13	1.63	1.75	1.05
Average fever temperature (℃)	46.5	56.5	51.6	44.0
highest fever temperature (℃)	>110	>110	>110	>110

Referring to Table 2, the electrode length at both left and right ends of the transparent substrate is 4.0 to 20.0 cm, more precisely 4.5 to 15.5 cm, and the distance between electrodes is 20 to 35 cm, more precisely 24.0 to 33.2 cm, Example 1 ~ As a result of using the highly conductive water-based ink NIM-006 in various types of goggles as shown in 5 and using vertical electrodes on the left and right ends of the goggles with a short electrode length and a long inter-electrode distance, when applying the 12 V constant voltage used in snowmobiles or 18 For eye protection goggles that satisfy the range of 30 ~ 60 ℃ and a maximum heating temperature of 80 ℃ or less of the transparent heating substrate with a grid pattern made of fine lines by controlling the flow of current to a low level even when applying a high voltage of V. A transparent heating element was obtained.

Referring to Table 3, the electrode length at both upper and lower ends of the transparent substrate is 24.0 to 30.0 cm, more precisely 24.5 to 29.7 cm, and the distance between electrodes is 4 to 8 cm, more precisely 4.0 to 7.8 cm, Example 6 Highly conductive water-based ink NIM-006 is used in various types of goggles as shown in ~ 10, and the horizontal electrodes at the top and bottom of the goggles, which have a long electrode length and a short distance between electrodes, apply a voltage at a low voltage of 2 V to 4 V to prevent the flow of current. As a result of low adjustment, a transparent heating element for eye protection goggles was obtained that satisfies the range of the average heating temperature of 30 ~ 60 ℃ and the maximum heating temperature of 80 ℃ or less of the transparent heating substrate equipped with a grid pattern made of fine lines.

However, referring to Table 4, the electrode length at both upper and lower ends of the transparent substrate is 24.0 to 30.0 cm, more precisely 24.5 to 29.7 cm, and the distance between electrodes is 4 to 8 cm, more precisely 4.0 to 7.8 cm, Comparative Example Highly conductive water-based ink NIM-006 is used in various types of goggles as shown in 1 to 4, and the same voltage of 12 V as in Examples 1 to 4 shown in Table 2 is applied to the horizontal electrodes at the top and bottom of the goggles with long electrode length and short inter-electrode distance. In Comparative Example 4, when 6 V was applied, the flow of current between electrodes increased, and as a result, it was not possible to obtain a transparent heating element for eye protection goggles that satisfied the heating characteristics, especially with a maximum heating temperature of 110 ° C. or higher.

As a result of Examples 1 to 10 and Comparative Examples 1 to 4, while using the highly conductive water-based ink NIM-006 in various types of goggles, the length of the electrode, the distance between electrodes, adjustment of the voltage applied to the electrode, and the shape of the electrode were adjusted. By appropriately controlling the flow of current, it is possible to manufacture a transparent heating element for eye protection goggles that satisfies the average heating temperature of 30 ~ 60 ℃ and the maximum heating temperature of 80 ℃ or less of the transparent heating substrate.

In summary, the present invention provides a transparent heating element in which a sintered body of conductive water-based ink is present on a transparent substrate that can be formed to a required heating characteristic value while ensuring the visibility and heating characteristics of goggles. The surface of the transparent substrate is formed of a sintered body of conductive water-based ink so that a grid pattern with a line width of 0.5 to 10 μm and a pitch of 0.05 to 1.0 m is good, the volume resistivity of the conductor is in the range of 9 μΩ·cm or less, and the electrode is It is formed at both long horizontal ends or both short vertical ends of a rectangular transparent substrate, and the maximum heating temperature within the rectangular transparent substrate, including the electrodes, is 80 ℃ or less, and the average heating temperature of the fine lines forming the grid pattern is 35 to 55 ℃. It is characterized by a light transmittance of more than 95% in the area ignoring the transparent substrate.

The above description is merely an illustrative explanation of the technical idea of the present invention, and those skilled in the art will be able to make various modifications and variations without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention, but are for explanation, and the scope of the technical idea of the present invention is not limited by these examples. The scope of protection of the present invention should be interpreted in accordance with the scope of the patent claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of rights of the present invention.

Claims (8)

1. Rectangular transparent substrate;

   A grid pattern formed by applying a conductive water-based ink to the transparent substrate and forming a stack, and made of fine lines; and

   It includes electrodes formed on both ends of the transparent substrate and connected to the grid pattern,

   The conductive water-based ink includes metal nanoparticles with a size of 5 to 50 nm and a water-soluble solvent,

   The metal nanoparticles are protected with a dispersion stabilizer consisting of branched polyalkyleneimine segments, polyoxyalkylene segments and amine salts,

   A transparent heating element for eye protection goggles, characterized in that the maximum heating temperature of the transparent substrate is 80 ℃ or less, and the average heating temperature of the fine wire is 30 to 60 ℃.
2. According to claim 1,

   The grid pattern is a transparent heating element for eye protection goggles, characterized in that the line width is 0.5 to 10 ㎛ and the pitch is 0.05 to 1.0 mm.
3. According to claim 1,

   A transparent heating element for eye protection goggles, wherein the grid pattern has a maximum volume resistivity of 9 μΩ·cm.
4. According to claim 1,

   The grid pattern is formed by applying the conductive water-based ink using imprint printing, screen printing, gravure printing, gravure offset printing, gravure reverse printing, or inkjet printing, and then firing the transparent heating element for eye protection goggles. .
5. According to claim 1,

   The transparent substrate is a transparent heating element for eye protection goggles, characterized in that the length ratio of the vertical and horizontal is 1: 2 to 5.
6. According to claim 1,

   A transparent heating element for eye protection goggles, wherein the conductive water-based ink further includes metal particles having a size of 100 to 900 nm.
7. According to claim 1,

   A transparent heating element for eye protection goggles, wherein the water-soluble solvent is at least one selected from alkylene glycol and glycerin.
8. Eye protection goggles, characterized in that they comprise a transparent heating element according to any one of claims 1 to 7.

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