WO2021205809A1 - Discharge electrode plate - Google Patents

Abstract

[Purpose] The present invention pertains to a discharge electrode plate forming an elongated discharge electrode for causing corona discharge. The purpose of the present invention is to smoothly supply electrons over a long period of time even when a conductive glass sintered film serving as a discharge electrode material is being made to perform corona discharge, and to extend the service life of the electrode by arranging a conductive metal sintered film in a substrate and thereby improving electrical conductivity and making corona discharge uniform. [Configuration] A discharge electrode plate provided with: a heat-resistant plate formed from a heat-resistant material; and a discharge electrode comprising two layers, namely, a conductive metal sintered film formed in an elongated shape on the heat-resistant plate and a conductive glass sintered film formed in an elongated shape on the conductive metal sintered film. Deterioration resulting from corona discharge is reduced and the service life is extended by forming the conductive glass sintered film constituting the discharge electrode from conductive glass having electron conductivity, and decreases in voltage resulting from electron flow or current flowing from the end to the center of the conductive glass sintered film are reduced and uniform corona discharge is generated by forming the conductive metal sintered film.

Description

Discharge electrode plate

The present invention relates to a discharge electrode plate that forms an elongated discharge electrode for corona discharge.

Conventionally, there is a method of modifying the surface of a polymer resin to make a smooth surface into a small unevenness or a thorny shape, and one method of passing it through an atmospheric corona discharge.

By passing the polymer resin through the corona discharge, the activated ions in the plasma appropriately make the surface of the resin uneven or jagged.

When the surface of the polymer resin has a small uneven shape, it changes from water repellent to hydrophilic. For example, as an applied product, it is convenient that the surface of the bamboo blind for drying seaweed has small irregularities. As a result, the seaweed pulled up from the seawater has a certain degree of adhesion, but when the surface of the polymer resin is in a slippery state, this adhesion cannot be obtained and the seaweed does not adhere to the bamboo blinds.

In this way, the surface modification treatment of the polymer resin is performed by causing a corona discharge in the atmosphere. Conventionally, metals (for example, stainless steel and tungsten) have been used as the material of the discharge electrode.

As shown in FIG. 10, when metals (stainless steel, tungsten) are used as the above-mentioned conventional discharge material for corona discharge, a large amount of ozone O3 is generated under the corona discharge plasma, so that the time is extremely short. There is a drawback that the surface is oxidized in (a fast one is about one week), electrons are not smoothly supplied from the surface of the discharge electrode (metal plate 22), and the discharge electrode (metal plate 22) cannot be used.

Further, there is a drawback that the surface of the discharge electrode (metal plate 22) is oxidized in a short time (about one week) and discharge cannot be performed, so that it is required to replace the discharge electrode.

In order to eliminate these drawbacks, as shown in FIG. 11, the discharge is performed by replacing the metal electrode (stainless steel, tungsten, etc.) with the electron conductive glass sintered film 22-1 that does not oxidize under corona discharge plasma. I was able to prevent the electrode from oxidizing.

However, when this is also actually used, as shown in FIG. 12, the discharge (corona discharge) is stable near the take-out part (power supply part) of the external wiring 24, and unstable at the center part, as shown in the figure. There was a problem that the corona discharge stopped in about one month.

Hereinafter, FIGS. 10 to 12 will be briefly described.

FIG. 10 shows a conventional technique (an electrode is a metal or a metal sintered film).

In FIG. 10, the ceramic plate 21 is a heat-resistant and insulating plate, and holds a metal plate 22 to which a high frequency voltage (for example, 7.5 KV, 30 KHz) is applied.

The metal plate 22 is a metal plate that discharges corona, and is an elongated plate such as stainless steel or W.

The external wiring 24 is a wiring (lead wire) for applying a high frequency voltage to the metal plate 22 from the outside.

The solder 25 is a solder that solders the external wiring 24 to the metal plate 22.

Under the above configuration, a high-frequency power source (for example, 7.5 KV, 30 KHz) is applied between the opposing metal plates 22 to generate a corona discharge in the atmosphere between the two metal plates 22. Then, for example, the above-mentioned polymer resin sheet is passed at a constant speed during the corona discharge, and minute irregularities are formed on the surface of the polymer resin sheet by the corona discharge.

FIG. 11 shows a conventional technique (the electrode is an electron conductive glass sintered film). Here, since the ceramic substrate 21, the external wiring 24, and the solder 25 are the same as those having the same number in FIG. 10, the description thereof will be omitted.

In FIG. 11, the electron conductive glass sintered film 22-1 is an electron conductive glass sintered film 22-1 that discharges corona discharge, and is a film obtained by sintering electron conductive glass.

Under the above configuration, a high frequency power source (for example, 6.5 KV, 30 KHz) is applied between the opposing electron conductive glass sintered films 22-1, and between the two electron conductive glass sintered films 22-1. Generates a corona discharge in the atmosphere. Then, for example, the above-mentioned polymer resin sheet is passed at a constant speed during the corona discharge, and minute irregularities are formed on the surface of the polymer resin sheet by the corona discharge.

FIG. 12 shows an example of the discharge state of the electrode of the conventional electron conductive glass sintered film.

In FIG. 12, the upper electrode 25 shows the upper electrode of the electron conductive glass sintered film 22-1 of FIG. 11, and the lower electrode 26 shows the lower electrode of the electron conductive glass sintered film 22-1 of FIG.

Under the above configuration, a high-frequency power source (for example, 6.5 KV, 30 KHz) is applied between the upper electrode 25, which is the opposite electron conductive glass sintered film 22-1, and the lower electrode 26. When a corona discharge is generated between the upper electrode 5 and the lower electrode 6 in the atmosphere, the discharge (corona discharge) is stable near the take-out part (power supply part) of the external wiring 24 as shown in the figure. , It became unstable in the central part. Therefore, after long-term use (for example, about January), corona discharge has occurred.

Therefore, it has been desired to solve the problem that the corona discharge of FIG. 12 becomes stable at the end and unstable at the center in the atmosphere, and further to extend the life of the discharge electrode (electroconductive glass sintered film). ..

The present inventors can smoothly supply electrons for a long period of time even if a conductive glass sintered film is corona-discharged as a discharge electrode material, and in addition, a conductive metal sintered film is arranged on a base to be electrically conductive. It was discovered in experiments that the properties can be improved, the corona discharge can be made uniform, and the life of the electrode can be extended.

And, in particular, it was confirmed by experiments that the corona discharge was made uniform even in the atmosphere and the life of the electrodes was extended.

Therefore, according to the present invention, in a discharge electrode plate for forming an elongated discharge electrode for corona discharge, a heat-resistant plate made of a heat-resistant material, a conductive metal sintered film formed elongated on the heat-resistant plate, and conductivity are provided. A discharge electrode composed of two layers of a conductive glass sintered film formed on a metal sintered film is provided, and a conductive glass sintered film constituting the discharge electrode is formed of electronically conductive conductive glass by corona discharge. Along with reducing deterioration and extending the service life, a conductive metal sintered film is formed to reduce the voltage drop due to the current or electron flow flowing from the edge to the center of the conductive glass sintered film to generate a uniform corona discharge. I have to.

At this time, the discharge electrode is placed in the atmosphere to discharge the corona.

In addition, the conductive glass is vanadate glass composed of vanadium, barium, and iron.

Also, the heat-resistant plate is made of heat-resistant glass or ceramic.

In addition, the size of the conductive glass sintered film formed on the conductive metal sintered film is made smaller than that of the conductive metal sintered film so as not to protrude.

In addition, when the discharge electrodes are arranged facing each other, the portion of the external wiring soldered to the end of the facing discharge electrode is shifted in the length direction so as not to enter the corona discharge region, and the soldered portion is damaged. I am trying to reduce.

In addition, the external wiring is connected by soldering to both the conductive metal sintered film and the conductive glass sintered film that make up the discharge electrode.

Also, the external wiring is soldered to the discharge electrode by ultrasonic soldering.

Further, in the formation of the discharge electrode by applying and firing the conductive glass, a paste containing the powder of the conductive glass is generated, and the produced paste is applied and fired to form the electronically conductive discharge electrode. ing.

In addition, the conductive glass sintered film is obtained by sintering a conductive metal sintered film and then applying, drying, and sintering on the conductive metal sintered film to prevent the metal particles and the conductive glass particles from thermally diffusing.

Further, a high frequency voltage in the range of 10 KHz to 5 MHz is applied between the other electrode facing the discharge electrode or the other electrode on the back surface of the discharge electrode to discharge the corona around the discharge electrode.
Further, when the conductive glass sintered film is formed of electronically conductive conductive glass, the conductive glass is obtained by heating the crushed conductive glass powder to a predetermined sintering temperature and sintering it to room temperature. After the first sintering heat treatment to be returned, the heating is performed to a predetermined annealing temperature lower than the sintering temperature to raise the temperature, and then the heating is stopped and the second annealing heat treatment for natural cooling is performed.
Further, the conductive glass sintered film after the first sintering heat treatment and the second annealing heat treatment has a resistance value of 10 squared to 3 or more as compared with the conductive glass before crushing. I try to reduce it small.

In the present invention, as described above, even if a conductive glass sintered film is corona discharged as a discharge electrode material, electrons can be smoothly supplied for a long period of time, and in addition, a conductive metal sintered film is arranged as a base. As a result, the electrical conductivity was improved, the corona discharge was made uniform, and the life of the electrode was extended.

In addition, by using an electrically conductive glass sintered film for the discharge electrode, it was possible to reduce the high-frequency voltage, enable longer-term use, and extend the service life.

In addition, the corona discharge was made uniform even in the atmosphere, and the life of the electrodes could be extended.

FIG. 1 shows a structural diagram of an embodiment of the present invention (two layers of electronically conductive glass and a metal sintered film). In the embodiment, the two ceramic substrates 1 are opposed to each other, and two layers of an aluminum sintered film 2 and an electronically conductive glass sintered film 3 are formed on the lower surface of the upper ceramic substrate 1 and the upper surface of the lower ceramic substrate 1. Although the discharge electrodes are formed respectively, the present invention is not limited to this, and two layers of discharge electrodes may be formed on the upper surface and the lower surface of one ceramic substrate 1, respectively, and corona discharge in the atmosphere may be performed between the two layers. Hereinafter, in the embodiment, an example in which two ceramic substrates 1 are opposed to each other will be described.

In FIG. 1, the ceramic substrate 1 holds a discharge electrode formed of an aluminum sintered film 2 and an electron conductive glass sintered film 3 in an insulated state, and has heat resistance that can withstand the high temperature caused by corona discharge. Moreover, it is a high-frequency voltage insulating plate. The ceramic substrate 1 may be a heat-resistant glass plate in addition to the ceramic plate, and may have heat resistance and high-frequency voltage insulation.

The aluminum sintered film 2 is an example of a conductive metal sintered film formed on the ceramic substrate 1. In addition to the aluminum sintered film, a metal sintered film such as copper or silver may be used. In the experiment, the width is about 1 mm to 30 mm, the length is 10 cm, and if it can be realized, it may be longer.

The electron conductive glass sintered film 3 is a sintered film of electron conductive glass, and is a sintered film of a semiconductor glass made of vanadium, barium, or iron (described later).

The external wiring 4 is for ultrasonically soldering the aluminum sintered film 2 and the electron conductive glass sintered film 3 with solder 5 and applying a high frequency voltage to each of them from the outside.

The solder 5 is a solder that ultrasonically solders the external wiring 4 to the aluminum sintered film 2 and the electron conductive glass sintered film 3.

Under the above configuration, when a high-frequency voltage of a high-frequency power source (for example, 6.5 KV, 30 KHz) is applied to the aluminum sintered film 2 and the electron conductive glass sintered film 3 via the external wiring 4, it is shown in the atmosphere. A corona discharge is generated between the upper side and the lower side of the electron conductive glass sintered film 3. When the resin sheet is passed during this corona discharge, minute irregularities are formed on the surface of the resin sheet.

The high-frequency power supply used was a power supply of 30 KHz in the experiment, but the power supply is not limited to this, and can be used from 10 KH to about 5 MHz for corona discharge in the atmosphere. The higher the frequency, the more likely it is that corona discharge will occur in atmospheric pressure, but the power supply will be more expensive.

At this time, a current flows from the end (one end or both ends) of the external wiring 4 into the discharge electrode composed of two layers of the aluminum sintered film 2 and the electronically conductive glass sintered film (for example, the resistance is about 200 to 400 Ωcm) 3. However, since the aluminum sintered film 2 which is a metal conductive sintered film is in the lower layer, the voltage drop in the electron conductive glass sintered film 2 due to the current is reduced, and a substantially uniform high-frequency voltage is applied to the entire surface of the electron conductive glass sintered film 3. It was applied over a period of time, and a substantially uniform corona current was generated between the electron conductive glass sintered films 3 in the atmosphere, and the discharge electrode could be used continuously for a long period of time, and the life of the discharge electrode could be extended (Fig.). 4).

FIG. 2 shows a structural diagram of an embodiment of the present invention (No. 2) (external wiring connection of two layers of an electron conductive glass and a metal sintered film).

(A) of FIG. 2 shows a side view, and (b) of FIG. 2 shows a main part. Since the ceramic substrate 1, the aluminum sintered film 2, the electron conductive glass sintered film 3, and the external wiring 4 are the same as those having the same number in FIG. 1, the description thereof will be omitted.

In FIG. 2, the solder 5 is attached to both sides (layers) as shown in the main part (b) of FIG. In the figure, both the aluminum sintered film 2 sintered on the ceramic substrate 1 and the electronically conductive glass sintered film 3 sintered on the aluminum sintered film 2 (both layers), and the external wiring 4 are soldered with solder 5. It is to be soldered. As a result, a high voltage and high voltage is applied to both the aluminum sintered film 2 and the electron conductive glass sintered film 3 via the external wiring 4, and in atmospheric pressure between the upper and lower electron conductive glass sintered films 3. It was possible to generate a uniform corona discharge and extend the life of the discharge electrode composed of the aluminum sintered film 2 and the electron conductive gas sintered film 3 (extending the life of one month or more).

More specifically, when a high-frequency voltage is applied from one end (or both ends) of the aluminum sintered film 2 and the electronically conductive glass sintered film 3 from the external wiring 4, the current or the current associated with the conventional corona discharge of only the electronically conductive glass sintered film 3 or A voltage drop was generated by the electron flow, and the high-frequency voltage was high at the edges and low by the voltage drop at the center. The voltage at the opening of the opposing electron conductive glass sintered film 3 was low, and the corona discharge was unstable. In order to solve this, in the present invention, an aluminum sintered film 2 is formed on the base, which is a metal sintered film and has a small resistance value, and the voltage drop of the current or electron flow flowing from the edge to the center is very small. Since the high frequency voltage is supplied to the electron conductive glass sintered film 3 in a reduced manner, as a result, the high frequency voltage applied between the upper side and the lower side of the electron conductive glass sintered film 3 becomes substantially uniform at the ends and the center. It was possible to generate a uniform corona discharge over a long period of time, and it was confirmed in experiments that the life of the discharge electrode was extended (for example, one month or more).

FIG. 3 shows an example of forming the electron conductive glass sintered film of the present invention.

FIG. 3A shows the discharge surface on the upper surface, and FIG. 3B shows the discharge surface on the lower surface. Here, the aluminum sintered film 2 described in FIGS. 1 and 2 is formed between the ceramic substrate 1 under the electron conductive glass sintered film 3 shown in the drawing, but is omitted in the drawing.

In FIG. 3, as described on the lower side, the positions of the external wiring 4 on the upper surface and the lower surface of FIG. 3 are approximately 1 cm, shifted as shown in the drawing, removed from the discharge region, and the wiring is protected.

This is because when the upper surface and the lower surface of the external wiring 4 are at the same position, a corona discharge occurs between the electron conductive glass sintered film 3 between the upper surface and the lower surface facing each other, and the external wiring 4 is burnt with the electronic conductive glass. As shown in the figure, the portion of the condensate 3 that was ultrasonically soldered was also irradiated with ions and gradually disappeared, resulting in poor conductivity over a long period of time. For example, the electronically conductive glass sintered film 3 on the upper surface is shifted to the left side, and the electronically conductive glass sintered film 3 on the lower surface is shifted to the right side so that ion irradiation due to corona discharge does not occur in both soldered parts, and the soldered parts are damaged. Avoid (damage due to ion irradiation).

FIG. 4 shows an example of the discharge state of the two-layer electrode of the electron conductive glass and the metal sintered film of the present invention. FIG. 4 is a lateral photograph of the state of corona discharge in the atmosphere when a high frequency voltage (for example, 6.8 KV, 30 KHz) is applied to the upper surface and the lower surface of the electron conductive glass sintered film 3 of FIG. 1 described above. This is an example of a photo taken.

Here, it can be seen that the corona discharge is uniformly discharged over almost the entire area between the upper surface and the lower surface in the atmosphere.

FIG. 5 shows an example of forming the electron conductive glass sintered film of the present invention (No. 2).

FIG. 5A shows a bottom view / top view of the upper side (earth), and FIG. 5B shows a top view of the lower side (discharge electrode). Here, since the upper side (earth) of FIG. 5A may be formed on either the upper surface or the lower surface of the ceramic substrate 1, the upper side (a) of FIG. 5 is taken as a bottom view or a top view. be. Further, although the aluminum sintered film 2 described in FIGS. 1 and 2 is formed between the ceramic substrate 1 under the electron conductive glass sintered film 3 of FIG. 5 (b), the aluminum sintered film 2 described in FIGS. 1 and 2 is omitted in the drawing.

In FIG. 5A, the aluminum electrode (earth) 7 is an earth electrode when corona discharging is performed, and is used for corona discharging with the electron conductive glass sintered film 3 of FIG. 5B. It is a thing.

The ground side wiring 6 is an external wiring (external terminal) for giving a ground potential to the aluminum electrode 7.

In FIG. 5B, the electron conductive glass sintered film 3 is an electron conductive glass sintered film formed by forming an aluminum sintered film 2 on a ceramic substrate 1 and further forming the aluminum sintered film 2 on the ceramic substrate 1, and is an electron conductive glass sintered film of FIG. It is an electrode for corona discharge with the aluminum electrode (earth) of (a).

The external wiring 4 is an external wiring 4 soldered to the electron conductive glass sintered film 3 and the underlying aluminum sintered film 2 and is a wiring (external terminal) for applying a high frequency voltage. The external wiring 4 is a region outside the discharge portion where the corona discharge is performed, and here, the external wiring 4 is arranged outside so as not to come into contact with the surface modifier (wire) 8 and not interfere with it.

Under the above configuration, a high-frequency voltage is applied between the electron-conductive glass sintered film 3 and the aluminum electrode 7 in the atmosphere to generate a corona discharge on the electron-conductive glass sintered film 3, and this corona discharge is generated. The surface modifier (wire) 8 is passed through the discharge to modify the surface (for example, to form minute irregularities).

Next, a method of manufacturing a two-layer discharge electrode of electron conductive glass will be described in detail according to the order of the flowchart of FIG.

FIG. 6 shows a flow chart for manufacturing a two-layer discharge electrode of the metal and the electron conductive glass of the present invention.

In FIG. 6, S1 prepares an alumina substrate, an aluminum paste, and an electron conductive glass paste. this is,
-Alumina substrate 1 is prepared here as the ceramic substrate 1 of FIG.

・ Prepare an aluminum paste for forming the aluminum sintered film 2 shown in FIG.

-Prepare an electron conductive glass paste for forming the electron conductive glass sintered film 3 of FIG.

S2 prints the pattern of the aluminum layer on the alumina substrate with aluminum paste. This is the aluminum paste prepared in S1, and the pattern of the aluminum sintered film 2 of FIG. 1 is screen-printed on the alumina substrate 1 prepared in S1.

S3 dries and sinters the aluminum pattern film (800 ° C x 10 minutes). This involves drying the aluminum pattern film printed on the alumina substrate 1 in S2 with hot air, and then sintering (800 ° C. × 10 minutes).

S4 prints, dries, and fires (550 ° C. x 15 minutes) an electronically conductive glass paste that is one size smaller (2 mm or more) than the aluminum pattern. This involves printing an electroconductive glass paste 2 mm or more smaller than the pattern of the aluminum sintered film 2 on the aluminum sintered film 2 sintered in S3, drying with hot air, and firing (550 ° C. × 15 minutes). )I do.

In S5, firing (500 ° C. × 1H) (glass reheating treatment” is performed. This involves re-baking (for example, 500 ° C. × 1H), that is, annealing the electron conductive glass sintered film fired in S4 to obtain electrons. Make the resistance value of the conductive glass very small (for example, reduce it to about 10 minus 4 Ωcm).

S6 is soldered (ultrasonic wave, etc., aluminum film, electron conductive glass film). In this method, as shown in FIG. 2 described above, the external wiring 4, the aluminum sintered film 2, and the electron conductive glass sintered film 3 are ultrasonically soldered.

As described above, as shown in FIGS. 1 and 2, an aluminum sintered film 2 is formed on the ceramic substrate 1, an electron conductive glass sintered film 3 is further formed on the aluminum sintered film 2, and these aluminum sintered films 2 and electrons are formed. The external wiring 4 is ultrasonically soldered to the conductive glass sintered film 3, and the structures shown in FIGS. 1 and 2 are manufactured.

Here, the conductive glass sintered film is obtained by sintering a conductive metal sintered film and then applying, drying, and sintering on the conductive metal sintered film to prevent the metal particles and the conductive glass particles from thermally diffusing. As a result, heat diffusion was eliminated, and two layers (two layers of the aluminum sintered film 2 and the electron conductive glass sintered film 3) could be successfully manufactured. When the simultaneous firing was performed, the metal particles and the conductive glass particles were thermally diffused, and the two layers could not be formed well.

FIG. 7 shows a flow chart for manufacturing the electronically conductive glass paste of the present invention.

In FIG. 7, in S11, a glass raw material is mixed and melted (900 to 1200 ° C.) (placed in a place where the electric furnace temperature has risen and held for 1 hour). This is a glass raw material prepared when the glass raw material is mixed (see FIG. 8 described later) and the electric furnace temperature rises to a melting temperature (for example, the optimum temperature obtained in an experiment of 900 to 1200 ° C.). Is put in a platinum crucible and put in, and the mixture is well stirred and held for, for example, 1 hour.

S12 creates 3-5 mm pieces of glass (crushes the molten glass while pouring it through a chilled roller). In this method, the molten glass prepared in S11 is crushed while being poured between water-cooled rollers to prepare glass fragments of about 3-5 mm.

S13 is coarsely crushed glass, powder 2-3 mm, powder ~ 50 μm. This grinds the glass shards 3-5 mm prepared in S12 into a powder of 2-3 mm and a powder of -50 μm.

S14 is finely pulverized (2-3 μm, jet mill device). For this, the powder to 50 μm prepared in S13 is further finely pulverized to about 2-3 μm with a jet mill device.

S15 stirs the organic material, organic solvent, and resin together with the above-mentioned finely pulverized glass.

S16 completes the electron conductive glass paste.

According to the above procedure, the raw materials (vanadium, barium, iron, see FIG. 8) are melted and stirred, rapidly cooled and crushed, and the crushed fine powder and the organic material, organic solvent, and resin are well stirred to generate electrons. It becomes possible to produce a conductive glass paste.

FIG. 8 shows an example of the electron conductive glass of the present invention. The electron conductive glass raw material of FIG. 7 is composed of the following materials shown in the figure.

V2O5; 50-75 wt%
Bao; 10-25 wt%
-Fe2O3; 8.0-15 wt%
For the range of each of the above materials, it is necessary to prepare the electron conductive glass sintered film 3 of FIGS. 1 and 2 by experiment and select the optimum value suitable for good corona discharge and long life. Furthermore, it is necessary to determine the optimum values for the temperature and time of firing and glass reheating treatment (annealing) described in FIG. 6 by experiments.

FIG. 9 shows a flow chart for manufacturing the aluminum paste of the present invention.

In FIG. 9, S21 prepares aluminum fragments of 3-5 mm. For this, aluminum fragments of 3 to 5 mm are prepared as the aluminum material.

S22 is finely pulverized aluminum (2-3 μm, jet mill device). This is done by crushing 3-5 mm of aluminum fragments prepared in S21 to about 2-3 μm with a jet mill device.

S23 stirs the organic material, organic solvent, and resin together with the above-mentioned fine pulverization of aluminum.

S24 completes the aluminum paste.

By the above procedure, it is possible to produce an aluminum paste by well stirring the fine powder obtained by crushing the raw material (aluminum fragment) with the organic material, the organic solvent, and the resin.

FIG. 13 shows an explanatory diagram of the other electrodes and insulating layer of the present invention and their corona discharge. In FIG. 13, a thin insulating layer (30 to 300 μm, preferably 70 to 100 μm) is formed between the electrodes for corona discharge, and a low voltage (80 to 150 V commercial AC voltage (50 / 60 Hz)) corona discharge is shown. An example of an experiment that realized the above is shown. Hereinafter, the details will be sequentially described with reference to FIGS. 13 to 17.

FIG. 13 (a) shows a corona discharge (top view of a main part), FIG. 13 (a-1) shows a schematic top view, and FIG. 13 (a-2) is a side view of the schematic view. Is shown.

First, the three-layer structure of the conductive layer 12, the insulating layer 13, and the conductive layer 11 used in the experiment will be described, and then the phenomenon of low-voltage corona discharge will be described.

(1) As shown in (a-1) and (a-2) of FIG. 13, a disk-shaped conductive layer 12 is applied, dried, and sintered on a substrate (not shown), and then formed. , A disk-shaped insulating layer 13 is applied, dried, and sintered on the top, and a ring-shaped conductive layer 11 is further applied, dried, and sintered on the top.

(2) When a low voltage is applied between the conductive layer 11 formed in (1) and the conductive layer 12, a corona discharge occurs between the conductive layer 11 and the conductive layer 12 as shown in FIG. 13 (a). Occurred stably.

(3) The reason why stable corona discharge occurred at low voltage seems to be as follows.

(4) The ring-shaped corona discharge of FIG. 13A forms a thin insulating layer 13 between the ring-shaped conductive layer 11 and the conductive layer 12, and between the conductive layer 11 and the conductive layer 12. The state of the corona discharge generated when a low voltage (30 to 300 VAC) is applied is shown. When a low voltage is applied between the conductive layer 11 and the conductive layer 12, the surface of the conductive glass paste sintered film used in the experiment in which the conductive layers 11 and 12 are formed has irregularities of about 30 to 50 μm at the maximum. When the electric field is concentrated in this part and the discharge starts and an excessive current (electrons) flows, the conductive glass paste sintered film becomes hot and the resistance becomes low, and the current to the part increases and becomes hot, and the conductive glass becomes hot. It is expected that the paste sintered film will partially melt, the arc discharge like lightning will cease, and a stable corona discharge will occur and continue as shown in Fig. 13 (a). It is also considered that the conductive glass paste sintered films (conductive layers 11 and 12) are conductive and semiconductor (electron conductive), so that corona discharge is likely to occur at a low voltage. increase.

FIG. 13B shows a top view of the entire corona discharge. This shows the whole experimental apparatus including the main part of FIG. 13 (a).

FIG. 13 (c) shows the experimental conditions. Here, it is as shown below.

-Applied voltage: 80 to 150 V (AC)
・ Current: 0.9mA (AC)
-Electrode spacing: 30 to 300 μm (preferably 70 to 100 μm)
Here, the applied voltage is a voltage applied between the conductive layer 11 and the conductive layer 12 in FIGS. 13 (a-1) and 13 (a-2), and is a commercial frequency of 80 to 150 V. The current is the current that was passed at that time. The electrode spacing is the thickness of the insulating layer 13 of FIGS. 13 (a-1) and (a-2), and is the spacing between the conductive layer 11 and the conductive layer 12. The thickness of the insulating layer 13 is the interval at which corona discharge is performed when 80 to 150 V is applied in the atmosphere (in the air), and if it is smaller than this, arc discharge is performed, and the thickness is equal to or greater than the maximum interval. This is the interval at which the corona discharge does not start. Although the power supply (AC) was tested using a commercial frequency (50 / 60 Hz), a high frequency power supply may also be used.

FIG. 14 shows an explanatory view of the other electrodes and the insulating layer of the present invention.

FIG. 14 (a) shows an example of the structure of the present invention, and FIG. 14 (a-1) shows an example of experimental conditions.

In FIG. 14A, a feature of the structural example of the present invention is that a thin insulating paste sintered body 16 is formed between the conductive layers 15 for corona discharge, and stable corona discharge is realized by applying a low voltage. It is in. The experimental conditions of the present invention are as shown below.-Applied voltage: 80 to 150 V (AC)
-Current: 0.6 to 0.09 mA (AC)
-Electrode spacing: 30 to 300 μm (preferably 70 to 100 μm)
FIG. 14 (b) shows a conventional structural example, and FIG. 14 (b-1) shows an example of experimental conditions.

In (b) of FIG. 14, the feature of the conventional structural example is that a thick ceramic plate 18 is inserted between the conductive layers 15 for corona discharge, and stable corona discharge is realized by applying a large voltage. The conventional experimental conditions are as shown below.

-Applied voltage: 1,8 KV (AC)
・ Current: 0.9mA (AC)
・ Electrode spacing: 1 mm
As described above, in the conventional structural example of FIG. 14B, a 1 mm thick ceramic plate 18 is inserted between the conductive layers 15 and a large voltage (1.8 KVAC) is applied to generate a corona discharge. On the other hand, in the structural example of the present invention shown in FIG. 14A, a thin insulating paste sintered body 16 having a thickness of 30 to 300 μm is formed between the conductive layers 15 to apply a low voltage (80 to 150 VAC). It differs in that it is applied to generate a stable corona discharge. In other words, the present invention is characterized in that the distance between the electrodes is narrow and stable corona discharge is generated at a low voltage.

FIG. 15 shows an explanatory view (No. 2) of the other electrode and the insulating layer of the present invention.

FIG. 15 (a) shows a feature example, and FIG. 15 (b) shows a structural example (No. 2) of the present invention.

In FIG. 15A, the structure of the present invention is the structure of FIG. 14A described above.

The conventional structure is the structure (b) of FIG. 14 described above.

Comparing the structure of the present invention with the conventional structure, there are the following features shown in the figure.

Insulator thin film processing 3D shape of insulation layer Features Structure of the present invention 30 μm to 300 μm Easy low voltage compatible Conventional structure 300 μm or more Difficult Low voltage compatible
Here, in the present invention, a thin film of 30 to 300 μm can be easily and inexpensively produced by using an insulating glass described later in the present invention. However, the ceramic plate having a conventional structure is difficult to process and expensive. The same applies to the 3D shape of the insulating layer. Further, the present invention is capable of dealing with low voltage and generates a stable corona discharge at 80 to 150 VAC. With the structure of the prior art, the voltage is as high as 1.6 KV, and it is impossible to reduce the voltage.

(B) of FIG. 15 shows a structural example (No. 2) of the present invention.

In FIG. 15B, the illustrated structure is formed as follows.

(1) The conductive layer 15 is formed by applying, drying, and sintering a conductive glass paste, for example, on the substrate 14.

(2) An insulating glass paste is applied, dried, and sintered as an insulating paste sintered body 16 (see (a) in FIG. 14) on the insulating paste sintered body 16. As shown in the figure, the formed insulating paste sintered body 16 covers the entire lower conductive layer 15, but this is only at both ends, and the portion that generates the central corona discharge is. , The lower conductive layer 15 is exposed, and is formed so as to cause a corona discharge between the lower conductive layer 15 and the upper conductive layer 15.

(3) Further, a conductive glass paste is applied, dried, and sintered as a conductive layer 15 on the conductive layer 15 to form a three-layer structure (lower conductive layer 15, insulating paste sintered body 16, upper conductive layer) as shown in the figure. A three-layer structure of layer 15) is formed.

A low voltage is applied between the conductive layers 15 of the structural example (No. 2) of the present invention formed as described above, and a corona discharge is stably generated between the conductive layers 15.

Next, a method for forming the insulating paste sintered body 16 will be described in detail with reference to FIGS. 16 and 17.

FIG. 16 shows another flow chart for applying the insulating glass of the present invention.

In FIG. 16, S31 screen-prints the insulating glass paste. In this method, for example, a pattern is screen-printed on the portion of FIG. 14 (a) on which the insulating paste sintered body 16 is formed, using the insulating glass paste. At this time, the concentration of the paste is adjusted so that the thickness after sintering becomes a predetermined thickness (30 to 300 μm).

S32 is dried. This is the drying of the sintered glass paste after screen printing in S31, which is left in the air (may be omitted), for example, left for 1 hour to dry.

S33 dries. This is performed by hot air drying at 40 to 100 ° C. for 15 to 100 minutes in an electric furnace in order to remove the solvent.

S34 is cooled. This is left in the air for, for example, 2 to 24 hours (may be omitted) to cool.

S35 is fired. This is fired in an electric furnace at 340 to 900 ° C. for 10 to 100 minutes to form the insulating paste sintered body 16.

As described above, as the insulating paste sintered body 16 of FIG. 14 (a) described above, a uniform insulating layer having a thickness of 30 to 300 μm can be manufactured inexpensively, with high accuracy, and in an arbitrary shape.

FIG. 17 shows an example of the insulating glass paste composition of the present invention. This shows a composition example of the insulating glass paste used in S31 of FIG. 16 described above. Here, it has the following components, applicable ranges, and remarks shown in FIG.

Component Concentration application Remarks Soda glass (window glass) 75-80% Main material (powder 2-3 μm, maximum 30 μm)
Diethylene glycol 10-15% Bonding of main particle
Monobutyl acetate
Tabineol 5-10% Concentration adjustment
Cellulose-based resin 1-5% adjuster Here, as an insulating glass paste, soda glass granules, binders, concentration adjusters, etc., which are often used for general window glass, are used in the above range. Other glasses can be used in the same way.

FIG. 18 shows a test example of the resistivity of the ABL glass sintered film of the present invention.

FIG. 18A shows an example of an ABL glass sintered film sample. The resistivity was measured by measuring the resistance value between a and b as shown in the figure.

In FIG. 18A, the substrate 21 is an alumina substrate having a thickness of 1 mm as shown in the figure.

The ABL glass sintered film 22 is formed by screen-printing a pattern having a width of 5 mm and a length of 40 mm with a conductive glass paste, drying, sintering, and annealing (described later with reference to FIG. 19).

The resistance value is measured by measuring the resistance value between a and b in FIG. 18 (a) (described later with reference to FIG. 20).

FIG. 19 shows a flowchart of the ABL glass sintering process of the present invention. This is a flowchart for forming the ABL glass sintered film 22 of FIG. 18 described above.

In FIG. 19, S41 prints the ABL glass paste on the substrate. This involves screen-printing the illustrated pattern (5 mm × 40 mm) on the substrate 21 of FIG. 18 described above using ABL glass paste.

S42 is dried in an electric furnace at 100 ° C. for 10 minutes.

S43 is taken out at room temperature. Leave at room temperature for about 20 minutes. In these S42 and S43, the substrate 21 screen-printed on the substrate 21 in S41 is placed in an electric furnace heated to 100 ° C. and left for 10 minutes to dry the printed ABL glass paste. The drying is not limited to this, and hot air of about 100 ° C. may be blown for about 10 minutes to dry.

S44 is sintered in an electric furnace at 550 ° C. for 5 minutes.

S45 is taken out at room temperature. Leave at room temperature for 5 minutes. In these S44 and S45, the substrate 21 on which the pattern of the dried ABL glass paste is formed is placed in an electric furnace at 550 ° C. for 5 minutes, sintered, taken out to room temperature, and cooled. By this sintering, the glass sintered film 22 having the rectangular pattern shown in FIG. 18 described above is formed, and at the same time, it is strongly adhered to the substrate 21.

S46 is placed in an electric furnace at 500 ° C. for 60 minutes for annealing.

For S47, turn off the electric furnace and let it cool naturally until it reaches room temperature. After being left at a temperature lower than the annealing treatments of S46 and S47, that is, the sintering treatment of S44 and S45 (here, the optimum value is obtained by an experiment at 500 ° C.) for 60 minutes (the optimum leaving time is obtained by an experiment). By performing an annealing heat treatment in which the power of the ionizing furnace is turned off and naturally cooled (slowly cooled) as it is, an ABL glass sintered film having a low resistance value can be obtained.

It is considered that the production of the ABL glass sintered film having a low resistance value by the procedure of the above flowchart was formed as follows.

(1) The ABL glass itself (electron conductive semiconductor) used for sintering usually has a resistance value of about 10 Ωcm to 150 Ω cm because the particles are connected to each other and the hands that carry electrons are limited. It is a thing.

(2) On the other hand, the first sintering heat treatment (S44, S45) and the second annealing heat treatment (S46, S47) are performed by printing the ABL glass paste (electroconductive semiconductor) obtained by crushing (1) into fine particles. The ABL glass boiled film after the heat treatment has more hands to carry electrons between the connections between the sintered particles of the fine powder (fine particles), and the surface area of the particles is increased, resulting in usually 10 particles. It was confirmed by experiments that the resistance value was as small as 2 to 3 or more (see FIG. 20 described later).

Here, regarding the firing temperature: At this firing temperature, some of the ABL glass powder particles melt and the particles begin to bond with each other. It functions in the range of 550 ° C ± 70 ° C. After the lower limit, the glass particles do not melt and the particles do not bond sufficiently. When the upper limit is exceeded, the bonds between the particles extend over a large region, and glass plate-like particles are formed inside. When this becomes large, the resistivity (resistance value) increases.

Annealing: Annealing heat treatment is performed at a temperature lower than the sintering temperature of 550 ° C by about 50 to 70 ° C, and then naturally cooled (not taken out to the outside and rapidly cooled). As a result, the components inside the glass are matched and the resistivity (resistance value) is lowered.

The resistance value of the conjunctiva is determined by the sum of the current flowing inside the glass and the current flowing on the surface of the glass particles. At an appropriate firing temperature (for example, 550 ° C.), it is considered that the bonding of glass particles becomes appropriate and the current flowing on the glass surface plays a leading role, and the resistivity (resistance value) can be reduced. The resistance value of the glass solid of the conductive glass (electromagnetic conductive glass (semiconductor)) before burning is mainly the current flowing inside the glass.

FIG. 20 shows an example of the resistivity measurement value of the ABL glass sintered film of the present invention.

In FIG. 20, as a result of performing the above-mentioned first sintering heat treatment and second annealing heat treatment at a sintering temperature of 520 ° C., 550 ° C., and 580 ° C., the following measured values shown in the figure were obtained. The resistivity (resistance value) of the solid ABL glass (ABL glass before sintering) used here is 140 Ωcm.

The following measured values were obtained at a sintering temperature of 520 ° C. ,
520-1: Film thickness 15 μm, resistance value 5.7 KΩ, resistivity 1.068 Ω cm,
520-2: Film thickness 16 μm, resistance value 6.1 KΩ, resistivity 1.143 Ωcm,
520-3: Film thickness 20 μm, resistance value 7.0 KΩ, resistivity 1.75 Ω cm,
The following measured values were obtained at a sintering temperature of 550 ° C. ,
550-1: Film thickness 14 μm, resistance value 3.5 KΩ, resistivity 0.612 Ω cm,
550-2: Film thickness 17 μm, resistance value 2.4 KΩ, resistivity 0.510 Ω cm,
550-3: Film thickness 20 μm, resistance value 5.7 KΩ, resistivity 0.51 Ω cm,
The following measured values were obtained at a sintering temperature of 580 ° C.
580-1: Film thickness 11 μm, resistance value 4.5 KΩ, resistivity 0.618 Ω cm,
580-2: Film thickness 17 μm, resistance value 7.4 KΩ, resistivity 1.573 Ω cm,
580-3: Film thickness 23 μm, resistance value 5.7 KΩ, resistivity 1.638 Ω cm,
From the above measurement results, as a result of performing the first sintering heat treatment and the second annealing heat treatment, the illustrated measured values having a resistance value (resistivity) as small as about 10 squared to 3rd power or more were obtained. Here, since the resistivity (resistance value) fluctuates depending on the film thickness and the sintering temperature, it is necessary to obtain and determine the optimum value by an experiment. In the example of FIG. 20, the smallest resistance value is obtained at a sintering temperature of 550 ° C. and a film thickness of about 15 to 20 μm (here, the film thickness by screen printing). It became 0.51 Ωcm (it became smaller by about 4 × (10 3) Ωcm).

It is a structural drawing of 1 Example of this invention (two layers of an electron conductive glass and a metal sintered film). FIG. 2 is a structural diagram (No. 2) of 1 Example of the present invention (external wiring connection of two layers of electron conductive glass and a metal sintered film). This is an example of forming the electron conductive glass sintered film of the present invention. This is an example of the discharge state of the two-layer electrode of the electron conductive glass and the metal sintered film of the present invention. This is an example of forming the electron conductive glass sintered film of the present invention (No. 2). It is a manufacturing flowchart of the two-layer discharge electrode of the metal and the electron conductive glass of this invention. It is a manufacturing flowchart of the electron conductive glass paste of this invention. This is an example of the electron conductive glass of the present invention. It is a manufacturing flow chart of the aluminum paste of this invention. It is a prior art example (the electrode is a metal or a metal sintered film). It is a conventional technique (the electrode is an electron conductive glass sintered film). This is an example of the discharge state of the electrode of the conventional electron conductive glass sintered film. It is explanatory drawing of the other electrode and the insulating layer of this invention and the corona discharge thereof. It is explanatory drawing of the other electrode and the insulating layer of this invention. It is explanatory drawing (the 2) of the other electrode and the insulating layer of this invention. It is a flowchart of application of another insulating glass of this invention. This is an example of the insulating glass paste composition of the present invention. This is a test example of the resistivity of the ABL glass sintered film of the present invention. It is a flowchart of the ABL glass sintering process of this invention. This is an example of the resistivity measurement value of the ABL glass sintered film of the present invention.

1: Ceramic substrate 2: Aluminum sintered film 3: Electronically conductive glass sintered film 4: External wiring 5: Solder 6: Ground side wiring 7: Aluminum electrode 8: Surface modifier 11, 12, 15: Conductive layer 13: Insulating layer 14: Substrate 16: Insulating paste sintered body 17: Corona discharge portion 21; Substrate 22: ABL glass-brushed film

Claims (16)

1. In the discharge electrode plate that forms the discharge electrode that discharges the corona
   A heat-resistant board made of heat-resistant material and
   A discharge electrode composed of two layers of a conductive metal sintered film formed on the heat-resistant plate and a conductive glass sintered film formed on the conductive metal sintered film is provided.
   A current or electron flow that flows from the edge to the center of the conductive glass sintered film by forming the conductive metal sintered film while preforming the discharge electrode to reduce deterioration due to corona discharge and extending the life. A discharge electrode plate characterized in that a uniform corona discharge is generated by reducing the voltage drop due to the discharge.
2. In the discharge electrode plate that forms the discharge electrode that discharges the corona
   A thin insulator with a thickness of 30 to 300 μm made of an insulating and heat resistant material,
   A discharge electrode composed of a conductive layer formed on the front surface and the back surface of the thin insulator is provided.
   A discharge electrode plate characterized in that the conductive layers constituting the discharge electrode are each formed of conductive glass to satisfactorily start and continue low-voltage corona discharge, reduce deterioration, and extend the life.
3. The discharge electrode plate according to any one of claims 1 to 2, wherein the discharge electrode is arranged in the atmosphere to discharge a corona.
4. The discharge electrode plate according to any one of claims 1 to 3, wherein the conductive glass is vanadate glass composed of vanadium, barium, and iron.
5. The discharge electrode plate according to any one of claims 1, 3 to 5, wherein the heat-resistant plate is made of heat-resistant glass or ceramic.
6. The first aspect of the present invention is that the size of the conductive glass sintered film formed on the conductive metal sintered film is smaller than that of the conductive metal sintered film so as not to protrude. The discharge electrode according to any one of items 3 to 5.
7. When the discharge electrodes are arranged facing each other, the portion of the external wiring soldered to the end of the facing discharge electrode is shifted in the length direction so as not to enter the corona discharge region, and the soldered portion is damaged. The discharge electrode according to any one of claims 1 and 3 to 6, characterized in that
8. The method according to any one of claims 1 and 3 to 7, wherein the external wiring is connected by soldering to both the conductive metal sintered film and the conductive glass sintered film constituting the discharge electrode. The discharge electrode plate described.
9. The discharge electrode plate according to claim 1, wherein the external wiring is soldered to the discharge electrode by ultrasonic soldering.
10. The formation of the discharge electrode by applying and firing the conductive glass is characterized in that a paste containing the powder of the conductive glass is generated, and the produced paste is applied and fired to form the electronically conductive discharge electrode. The discharge electrode plate according to any one of claims 1 and 3 to 9.
11. The conductive glass sintered film is characterized in that after the conductive metal sintered film is sintered, it is coated, dried, and sintered on the conductive metal sintered film to prevent the metal particles and the conductive glass particles from thermally diffusing. The discharge electrode according to any one of claims 1 and 3 to 10.
12. A feature is that a high-frequency voltage in the range of 10 KHz to 5 MHz is applied between the other electrode facing the discharge electrode or the other electrode on the back surface, and corona discharge is performed around the discharge electrode. The discharge electrode according to any one of claims 1 and 3 to 11.
13. The discharge electrode according to any one of claims 2 to 4, wherein the thin insulator is an insulating paste sintered body obtained by sintering an insulating glass paste.
14. Any of claims 2 to 4, wherein an AC voltage of 80 V to 150 V is applied between the conductive layer formed on the front surface and the back surface of the discharge electrode to start and continue the corona discharge in the atmosphere. The discharge electrode described in.
15. When the conductive glass sintered film is formed of electronically conductive conductive glass, the conductive glass is obtained by heating crushed conductive glass powder to a predetermined sintering temperature and sintering it to room temperature. After the first sintering heat treatment for returning, the second annealing heat treatment is performed by heating to a predetermined annealing temperature lower than the sintering temperature to raise the temperature, and then stopping the heating and naturally cooling. The discharge electrode according to any one of items 1 to 14.
16. The conductive glass sintered film after the first sintering heat treatment and the second annealing heat treatment has a resistance value of 10 squared to 3 or more as compared with the conductive glass before crushing. The discharge electrode according to claim 15, wherein the discharge electrode is reduced to a small size.

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