JPH08180959A - Corona polarization treating method and corona polarization device - Google Patents

Abstract

PURPOSE: To uniformly electrify the surface of material to be polarized to treat corona polarization having no difference in polarity by heating the material to be heated, arranged on a lower side electrode, to a given temperature to perform corona electric discharge between plural needlelike electrodes. CONSTITUTION: A material 5 to be polarized such as a polyurea film is placed on the lower part electrode 2 of Al on the like, and voltage is applied by a power source 4 to needlelike electrodes 3, opposite to the material 5, of W or the like to generate corona electric discharge to electrify the surface of the material 5 to be polarized. Together with this, the temperature of the material 5 to be polarized is risen by a heater 6. This makes a dipole in the material 5 to be polarized rotatable by heating, and is oriented along an electric field gradient generated by this electrification. In this corona polarization treating method, the plural needlelike electrodes 3 are arranged, and a grid electrode is located between both the electrodes as required. Also, the corona electric discharge can be made with the needlelike electrodes or the grid electrode or the material 5 to be polarized moved in a horizontal direction to an electric field.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a corona polarization treatment method and a corona polarization device, and more particularly, to an electret such as a microphone and a condenser, an acceleration sensor, a fluid sensor, a piezoelectric sensor such as a pressure sensor,
The present invention relates to a corona polarization treatment method for subjecting an insulating material used for a pyroelectric sensor such as an infrared sensor to a polarization treatment, and a corona polarization device used for the same.

[0002]

2. Description of the Related Art Corona discharge occurs when a high electric field (for example, several KV / cm) is applied between a needle electrode made of stainless steel, tungsten, etc. and a plate electrode at a position apart from the needle electrode. In this case, polarity is generated. Can be either.

When an insulator is placed between the electrodes, ions moving from the vicinity of the needle electrode toward the plate electrode at the time of discharge enter the surface of the insulator and are charged. When charged, a strong electric field gradient occurs inside the insulator.

When a material having a dipole in an insulator is placed between electrodes and the dipole can rotate (for example, the temperature of the insulator is raised to allow the dipole to move), the dipole The child is oriented along the generated electric field. If the movement of the dipole is fixed (for example, the temperature of the insulator is lowered) while maintaining this alignment state, the alignment is maintained even if the electric field is subsequently removed.

The process of orienting the dipole in a certain direction in this way is called a polarization process. This polarization process is also called poling.

[0006] Conventionally, as a corona polarization device for performing so-called polarization treatment, in which a polarized material formed of, for example, a polyurea film on a substrate is subjected to corona discharge to orient the dipoles contained in the polarized material. Is for heating a lower electrode a made of aluminum, a needle electrode b made of tungsten arranged at a position opposite to the lower electrode a, and a polarized material arranged on the back surface side of the lower electrode a as shown in FIG. A corona polarization device is known in which a lower electrode a and a needle electrode b are connected via a power source d for generating a corona discharge.

Then, a polarized material e made of, for example, a polyurea film is placed on the lower electrode a, and the lower electrode a from the power source d is placed.
An electric field of, for example, 300 KV / m is applied between the needle-shaped electrode b and the needle-shaped electrode b to perform corona discharge f to charge the surface of the polarized material e, and at the same time raise the temperature of the polarized material e to 180 ° C. by the heater c. To orient the dipoles contained in the polarized material e.

However, when the material e to be polarized is polarized by corona discharge using the corona polarization device, it is polarized depending on the positional relationship between the needle-shaped electrode b and the material e to be polarized and the distance between the two. There is a difference in the degree of. That is, the portion closest to the needle-shaped electrode b is likely to be polarized, and the farther away it is, the less likely it is to polarize. That is, as shown in FIG. 10, a large polarization portion g is formed at the central portion of the polarized material e, and a small polarization portion h is formed at the end portion of the polarized material e.

Among the materials to be polarized that have been polarized,
The one in which the electric charge charged on the surface is preserved for a long time even if the electric field is removed is called an electret.In addition, the dipole is oriented and remanent polarization occurs inside, and the remanent polarization changes due to force or heat. The one through which an electric current flows to compensate is called a piezoelectric body for force and a pyroelectric body for heat.

Therefore, when polarization treatment is performed using the above-mentioned polarization device, a difference in charge amount (how much V is charged), piezoelectricity, or pyroelectricity occurs inside the polarized material. There is a problem.

In order to solve this problem, therefore, a grid electrode i made of metal such as stainless steel is arranged between the lower electrode a and the needle electrode b as shown in FIG. There is. In the figure, j indicates a power source arranged between the lower electrode a and the grid electrode i.

By arranging the grid electrode between the lower electrode and the needle electrode as in the polarization device shown in FIG. 11, the electric field between the material to be polarized, which is an insulator, and the grid electrode becomes uniform, and the material to be polarized becomes uniform. Is polarized.

[0013]

The grid electrode of the polarization device in which the grid electrode shown in FIG. 11 is arranged cannot prevent discharge from the needle electrode, and ions generated near the needle electrode are incident on the surface of the material to be polarized. For this purpose, a mesh-like metal material such as stainless steel is used.

The inventors of the present invention have diligently studied in order to apply a uniform polarization treatment to the polarized material, and as a result, the polarized material, which is considered to be uniformly polarized, is polarized as shown in FIG. It was found that there are a portion k in which the polarization is sufficiently performed and a portion m in which the polarization is insufficient.

That is, it was found that polarization was insufficient in the portion m of the mesh of the grid electrode as seen from the tip of the needle electrode.

The reason is that the incidence of ions on the material to be polarized is hindered by the mesh of the grid electrode, and as a result, the charge on the material to be polarized is distributed and the polarization of the material to be polarized is different.

At the present time, sensors and the like tend to be miniaturized, and as miniaturization is concerned, there is a concern that the difference in polarization due to the shadow of the mesh will cause variations in the sensitivity of each sensor.

Therefore, there is no difference in polarization between the shaded portion of the grid electrode (the portion with insufficient polarization: symbol m in FIG. 12) and the other portion (the portion with sufficient polarization: symbol k in FIG. 12). Is expected to emerge.

An object of the present invention is to provide a corona polarization treatment method having no difference in polarization and a corona polarization device used therefor.

[0020]

A corona polarization treatment method according to claim 1 utilizes corona discharge between a lower electrode and a needle electrode to charge a surface of a material to be polarized on the lower electrode, and at the same time polarizes the material to be polarized. In the corona polarization treatment method of raising the temperature of the material to orient the dipoles contained in the material to be polarized,
It is characterized in that corona discharge is performed from a plurality of needle electrodes.

According to a second aspect of the present invention, the corona polarization treatment method utilizes corona discharge between the lower electrode and the needle electrode via the grit electrode to charge the surface of the material to be polarized on the lower electrode,
At the same time, in the corona polarization treatment method in which the temperature of the polarized material is raised to orient the dipoles contained in the polarized material, the corona discharge is performed from a plurality of needle electrodes.

The corona polarization treatment method of claim 3 utilizes corona discharge between the lower electrode and the needle-shaped electrode via the grit electrode to charge the surface of the material to be polarized on the lower electrode,
At the same time, in the corona polarization treatment method in which the temperature of the polarized material is raised to orient the dipoles contained in the polarized material, the corona discharge is performed while moving the needle electrode horizontally with respect to the electric field. To do.

According to a fourth aspect of the present invention, the corona polarization treatment method utilizes corona discharge between the lower electrode and the needle-shaped electrode through the grit electrode to charge the surface of the polarized material on the lower electrode,
At the same time, in the corona polarization treatment method in which the temperature of the polarized material is raised to orient the dipoles contained in the polarized material, corona discharge is performed from the needle electrode while moving the grit electrode horizontally with respect to the electric field. Is characterized by.

The corona polarization treatment method of claim 5 utilizes corona discharge between the lower electrode and the needle-shaped electrode through the grit electrode to charge the surface of the material to be polarized on the lower electrode,
At the same time, in the corona polarization treatment method in which the temperature of the polarized material is raised to orient the dipoles contained in the polarized material, corona discharge is performed from the needle electrode while moving the polarized material horizontally with respect to the electric field. It is characterized by

The corona polarization treatment method of claim 6 is the same as that of claim 3.
The corona polarization treatment method according to any one of claims 1 to 5, wherein the needle electrode is a plurality of needle electrodes.

According to a seventh aspect of the present invention, there is provided a corona polarization device, which comprises a lower electrode and a needle-shaped electrode arranged at a position opposite to the lower electrode, and utilizes corona discharge between the lower electrode and the needle-shaped electrode. In the corona polarization device for orienting the dipoles contained in the material to be polarized, the needle-shaped electrode is composed of a plurality of needle-shaped electrodes.

The corona polarization device according to the present invention comprises a lower electrode, a needle-shaped electrode arranged at a position opposite to the lower electrode, and a grit electrode arranged between the lower electrode and the needle-shaped electrode. In the corona polarization device for orienting the dipoles contained in the material to be polarized on the lower electrode by utilizing the corona discharge between the lower electrode and the needle electrode via the needle electrode, the needle electrode is composed of a plurality of needle electrodes. It is characterized by

A corona polarization device according to a ninth aspect of the present invention comprises a lower electrode, a needle electrode disposed at a position opposite to the lower electrode, and a grit electrode disposed between the lower electrode and the needle electrode. In the corona polarization device that uses the corona discharge between the lower electrode and the needle electrode to orient the dipoles contained in the material to be polarized on the lower electrode, the needle electrode is moved horizontally to the electric field. It is characterized by being placed freely.

A corona polarization device according to a tenth aspect of the present invention comprises a lower electrode, a needle-shaped electrode arranged at a position opposite to the lower electrode, and a grit electrode arranged between the lower electrode and the needle-shaped electrode. In the corona polarization device that uses the corona discharge between the lower electrode and the needle electrode to orient the dipoles contained in the material to be polarized on the lower electrode, the grit electrode can be moved horizontally with respect to the electric field. It is characterized by being placed in.

The corona polarization device of claim 11 comprises a lower electrode, a needle-shaped electrode arranged at a position opposite to the lower electrode, and a grit electrode arranged between the lower electrode and the needle-shaped electrode. In a corona polarization device that uses a corona discharge between the lower electrode and the needle electrode to orient the dipoles contained in the polarized material on the lower electrode, the polarized material is moved horizontally with respect to the electric field. It is characterized by being placed freely.

The corona polarization device of claim 12 is the same as that of claim 9.
The corona polarization device according to any one of claims 1 to 11, wherein the needle-shaped electrode is a plurality of needle-shaped electrodes.

[0032]

[Function] In corona polarization treatment by corona discharge, by configuring the needle-shaped electrode with a plurality of needle-shaped electrodes, corona discharge can be uniformly performed on the surface of the material to be polarized having a large area, and the surface of the material to be polarized is uniform. As a result, it is possible to perform uniform polarization treatment.

In corona polarization treatment by corona discharge, a grid electrode is provided between the lower electrode and the needle electrode in order to make the polarization (magnitude of charge) uniform.
By moving either the grid electrode or the polarized material horizontally to the electric field, the grid electrode does not prevent the ions generated by the corona discharge from entering the polarized material, so the surface of the polarized material is uniform. As a result, it is possible to perform uniform polarization treatment.

[0034]

First, the basic idea of the present invention will be described.

1) Regarding the Number of Needle-Shaped Electrodes (1) There is no limitation on the number of needle-shaped electrodes per unit area when the needle-shaped electrodes are composed of a plurality of needle-shaped electrodes. The reason is that the polarization must be evenly distributed with respect to the material to be polarized, and therefore the number per unit area can be increased (overcrowded state), but it is simply a waste if productivity, cost, etc. are taken into consideration. It just becomes.

There are various methods for the poling process (for example, the distance between the substrate and the electrode such as the needle or the wire, and the electric field strength are different in the report of the experimental results). The current situation is that it is not subject to.

This is because the poling method itself is merely a means (tool), and the research subject is directed to the physical properties and characteristics of the polarized material after the poling treatment.

(2) For example, the size of the substrate is 1 m square (1000 mm
X 1000 mm), it is extremely difficult to uniformly polarize the material to be polarized with a single needle electrode, even if a grid electrode is placed between the lower electrode and the needle electrode. Have difficulty.

From the results of various experiments, the distance between the needle electrodes is about 5 to 10 cm. However, even in this case, since the parameters of the distance between the needle electrode and the substrate and the distance between the grid electrode and the substrate greatly change, the distance between the needle electrode and the substrate is, for example, X mm, or the distance between the grid electrode and the substrate, for example, When the distance is Hmm, the distance between the needle electrodes is only determined to some extent such as the range of Y to Zmm.

As an example, when the distance (distance) between the needle electrode and the substrate is 2 cm, the voltage is 10 kV, the distance (distance) between the grid electrode and the substrate is 1 cm, and the voltage is 2 kV (needle) It is preferable that the distance between the needle-shaped electrodes is 5 to 10 cm in the case of the negative electrodes and the grid electrodes being negative and the substrate being at the ground potential or vice versa.

(3) As shown in FIG. 12, ions generated between the needle-shaped electrode and the substrate (negative ions and electrons when the needle-shaped electrode is negative, positive ions and electrons when the needle-shaped electrode is positive) are generated. The electric field attracts the substrate, charges the surface of the material to be polarized, and causes polarization. At this time, the grid electrode interferes with the incidence of ions on the material to be polarized, and if the surface of the material to be polarized cannot be charged, the polarization becomes non-uniform.

Therefore, by moving any of the needle electrode, the grid electrode, and the material to be polarized (substrate) during poling (time is 30 to 40 minutes), it is possible to allow ions to enter the entire material to be polarized. Good.

2. Movement of Needle-Shaped Electrode, Grid Electrode, and Material to be Polarized (Substrate) (1) Ions and electrons generated between the needle-shaped electrode and the substrate are attracted to the substrate and uniformly incident on the substrate. As a result, since it is sufficient to make the charging on the surface uniform, any method (means) can be adopted as the moving means. However, the electric field strength changes during the movement as the distance between the electrode and the substrate changes, and it is generally difficult to control the electric field strength. Therefore, it is preferable to move the electric field in a horizontal direction with respect to the electric field.

(2) In the corona polarization treatment method, the movement when performing corona discharge while moving any of the needle electrode, the grid electrode, and the material to be polarized in the horizontal direction with respect to the electric field is, for example, the needle electrode. It is either a case of reciprocating within a predetermined range of the material to be polarized, for example, a case of rotating the needle electrode around a part of the material to be polarized.

(3) In the corona polarization device, when the needle electrode, the grid electrode, or the material to be polarized is arranged with respect to the electric field, the term "movable" means, for example, that the needle electrode is within a predetermined range of the material to be polarized. It is either a case of reciprocating the inside, for example, a case of rotating the needle electrode around a part of the material to be polarized.

(4) The movement speed is polling (time is 30-40
Minute) inside needle-shaped electrode, grid electrode, polarized material (substrate)
It is sufficient to allow ions to be incident on the entire material to be polarized by moving either of the above.

Specific examples of the corona polarization device of the present invention will be described below.

Example 1 FIG. 1 is an explanatory view of the device when the needle-shaped electrode is composed of a plurality of needle-shaped electrodes.

In the figure, reference numeral 1 denotes a corona polarization device. The corona polarization device 1 comprises a lower electrode 2 made of aluminum and a tungsten made above it having a diameter of 1-2 mm and a length of 50-.
The lower electrode 2 and the needle electrode 3 are connected via a power source 4, and the polarized material 5 is heated to a predetermined temperature during poling on the back side of the lower electrode 2 by a 100 mm needle electrode 3. The heater 6 for maintaining the temperature was placed.

A voltage of, for example, 10 kV is applied from the power source 4 between the lower electrode 2 and the needle electrode 3 to generate corona discharge between them, and the polarized material 5 is charged by the corona so that it is polarized. I chose

The plurality of needle-shaped electrodes 3 may be arranged at intervals of 1 to 2 cm.

The region directly below the needle-shaped electrode 3 is most polarized, but the plurality of needle-shaped electrodes 3 makes the surface of the material 5 to be polarized uniform, and the difference in the polarization imparted to the material 5 to be polarized can be reduced. To lose.

Example 2 FIG. 2 is an explanatory view in the case where the device is provided with a grid electrode and the needle electrode is composed of a plurality of needle electrodes.

In the apparatus shown in FIG. 2, a mesh grid electrode 7 made of stainless steel and having a diameter of 0.5 to 1 mm and a mesh opening interval of 1 to 2 mm is disposed between the lower electrode 2 and the needle electrode 3, and the lower electrode 2 and the grid electrode 3 are arranged. 3 has the same configuration as that of the apparatus shown in FIG. 1 except that 3 is connected via a power source 8. The same reference numerals as those of the apparatus shown in FIG. 1 are omitted.

In this case, the needle electrode 3 may be arranged so that the mesh of the grid electrode 7 is not shaded when viewed from the tip of the needle electrode 3.

Example 3 FIG. 3 is an explanatory view of a device including a grid electrode and configured to move the needle electrode during corona discharge.

In the figure, reference numeral 11 denotes a corona polarization device, which is a lower electrode 12 made of aluminum.
And a diameter of 1-2 mm made of tungsten placed above it,
A needle electrode 13 having a length of 50 to 100 mm and a stainless steel diameter of 0.5 to 1 mm arranged between the lower electrode 12 and the needle electrode 13;
It is composed of a mesh grid electrode 17 having a mesh opening interval of 1 to 2 mm. The lower electrode 12 and the needle electrode 13 are connected via a power supply 14, and the lower electrode 12 and the grid electrode 17 are connected via a power supply 18. did.

Further, a heater 16 for heating the polarized material 15 to a predetermined temperature during poling and maintaining the temperature on the back side of the lower electrode 12 was arranged.

Then, a voltage of, for example, 10 kV is applied from the power source 14 between the lower electrode 12 and the needle electrode 13, and a voltage of, for example, 2 kV is applied from the power source 18 between the lower electrode 12 and the grid electrode 17 to lower the lower electrode 12. A corona discharge was generated between the needle electrode 13 and the needle electrode 13, and the polarized material 15 was charged by the corona so that the material 15 was polarized.

During the corona discharge, the needle electrode 13 is moved horizontally from the solid line shown in FIG. 3 to a virtual line by a driving device (not shown) such as a linear motor in a horizontal direction with respect to the electric field. did. By moving the needle-shaped electrode 13 in the horizontal direction with respect to the electric field during the corona discharge in this manner, the shaded portion of the mesh of the grid electrode as viewed from the tip of the needle-shaped electrode cannot be formed.

Example 4 FIG. 4 is an explanatory view of a device including a grid electrode and configured so that the grid electrode is moved during corona discharge.

In the figure, reference numeral 21 denotes a corona polarization device, which is a lower electrode 22 made of aluminum.
And a diameter of 1-2 mm made of tungsten placed above it,
A needle electrode 23 having a length of 50 to 100 mm, and a stainless steel diameter of 0.5 to 1 mm arranged between the lower electrode 22 and the needle electrode 23,
It is composed of a mesh grid electrode 27 having a mesh opening interval of 1 to 2 mm. The lower electrode 22 and the needle electrode 23 are connected via a power supply 24, and the lower electrode 22 and the grid electrode 27 are connected via a power supply 28. did.

Further, a heater 26 for heating the polarized material 25 to a predetermined temperature during poling and maintaining the temperature on the back surface side of the lower electrode 22 is arranged.

Then, a voltage of, for example, 10 kV is applied from the power source 24 between the lower electrode 22 and the needle electrode 23, and a voltage of, for example, 2 kV is applied from the power source 28 between the lower electrode 22 and the grid electrode 27. A corona discharge was generated between the needle electrode 23 and the needle electrode 23, and the polarized material 25 was charged by the corona so that the material 25 was polarized.

Further, during the corona discharge, the grid electrode 27 is moved horizontally with respect to the electric field by a driving device (not shown) such as a linear motor.

Thus, during the corona discharge, the grid electrode 2
By moving 7 in the horizontal direction with respect to the electric field, the shaded portion of the mesh of the grid electrode cannot be seen when viewed from the tip of the needle electrode.

Example 5 FIG. 5 is an explanatory view of an apparatus having a grid electrode and configured to move a polarized material to be polarized during corona discharge.

In the figure, 31 indicates a corona polarization device, and the corona polarization device 31 is a lower electrode 32 made of aluminum.
And a diameter of 1-2 mm made of tungsten placed above it,
A needle electrode 33 having a length of 50 to 100 mm, and a stainless steel diameter of 0.5 to 1 mm arranged between the lower electrode 32 and the needle electrode 33,
It is composed of a mesh grid electrode 37 having a mesh opening interval of 1 to 2 mm. The lower electrode 32 and the needle electrode 33 are connected via a power source 34, and the lower electrode 32 and the grid electrode 37 are connected via a power source 38. did.

Further, a heater 36 for heating the polarized material 35 to a predetermined temperature during poling and maintaining the temperature on the back surface of the lower electrode 32 is arranged.

Then, a voltage of, for example, 10 kV is applied between the lower electrode 32 and the needle electrode 33 from the power source 34, and a voltage of, for example, 2 kV is applied between the lower electrode 32 and the grid electrode 37 from the power source 38, thereby lowering the lower electrode 32. A corona discharge was generated between the needle electrode 33 and the needle electrode 33, and the material 35 to be polarized was charged by the corona so that the material 35 was polarized.

Further, during the corona discharge, the polarized material 35 is moved in the horizontal direction with respect to the electric field from a solid line to a virtual line as shown in FIG. 5 by a driving device (not shown) such as a linear motor. I did it.

As described above, the polarized material 35 is generated during the corona discharge.
Is moved in the horizontal direction with respect to the electric field, the shadow of the mesh of the grid electrode cannot be formed when viewed from the tip of the needle electrode.

Specific examples of the corona polarization treatment method of the present invention will be described below together with comparative examples.

Example 6 This example is a polarization treatment method in which a single needle electrode is used and corona discharge is performed while moving the grid electrode to perform polarization treatment, and a polyurea film was used as the material to be polarized.

The polyurea film was prepared on the substrate by the present applicant in the method for forming an organic piezoelectric pyroelectric film proposed in Japanese Patent Application Laid-Open No. 2-284485 (Japanese Patent Application No. 1-104562). The polyurea film was formed according to the method for forming the film, and the polyurea film was formed on the substrate by using the apparatus shown in FIG. The production of the polyurea film will be described.

First, one of the evaporation containers 46, 46 is 4,4'-diaminophenyl ether, which is a raw material monomer a of polyurea, and the other is diisocyanate 4,4'-diisocyanic acid, a raw material monomer b of polyurea. The total pressure inside the vacuum processing chamber 41 was 1.3 × 1 with the vacuum distilling system 42 filled with methyldiphenyl and the shutter 49 closed.
Set to 0 ^-3 Pa (1 × 10 ^-5 Torr).

Next, while measuring the amount of evaporation of each of the raw material monomers a and b from the evaporation containers 46 and 46 by the evaporation monitors 47 and 47, the heaters 48 and 48 were used to heat the 4,4'-diaminophenyl ether to a temperature of 135 ±. The diisocyanate 4,4'-methyldiphenyl diisocyanate is heated to 2 DEG C. and to a temperature of 75. +-. 2.

Next, after the raw material monomers a and b have reached a predetermined temperature and a required amount of evaporation has been obtained, the shutter 49 is opened, and the substrate 43 (size 25 cm × 25 cm) held by the holder 44 in the vacuum processing chamber 41 is opened. Aluminum having a film thickness of 0.1 μm is vapor-deposited on the surface of the slide glass as a lower electrode), and the raw material monomers a and b are deposited at a deposition rate of 2Å / min to a thickness of 2000Å, and then the shutter 49 is closed. A polymerization reaction of polyurea (also referred to as polyurea) is caused on the substrate 43 to form a polyurea film on the substrate 43.

The raw material monomers a and b are adjusted to 1: by adjusting the evaporation amount so that a polyurea film is stoichiometrically formed.
Evaporation was carried out at a molar ratio of 1. The pressure in the vacuum processing chamber 41 during the evaporation of the raw material monomers a and b is 4 × 1.
It was set to 0 ⁻³ Pa (3 × 10 ⁻⁵ Torr). Further, reference numeral 50 in the figure denotes a partition plate provided between both evaporation containers 46.

The above-mentioned Japanese Patent Laid-Open No. 2-284485 (Japanese Patent Application No. 1-1045)
In the method of forming an organic piezoelectric pyroelectric film proposed in No. 62), poling (polarization treatment) is not a corona method, but a method of directly applying an electric field to upper and lower electrodes provided on both surfaces of a polyurea film is used. In the present invention, the upper and lower electrodes are not provided.

The substrate having the polyurea film thus formed is taken out from the vacuum processing chamber, and the polyurea film formed on the substrate is used as the material to be polarized. The material to be polarized is polarized by corona discharge by the following method. Treated.

The device shown in FIG. 7 was used for the polarization treatment.

In the figure, reference numeral 21 denotes a corona polarization device, which is a lower electrode 22 made of aluminum.
And a needle-shaped electrode 23 made of tungsten and having a diameter of 1 mm and a length of 100 mm, which is arranged above the lower electrode 22, and the needle-shaped electrode 2.
3 and a mesh grid electrode 27 made of stainless steel disposed between the lower electrode 22 and the needle electrode 23 via a power source 24, and the lower electrode 22 and the grid electrode 27 via a power source 28. Connected.

Further, a heater 26 for heating the material 25 to be polarized to a predetermined temperature during poling and maintaining the temperature on the back surface side of the lower electrode 22 is arranged. The configuration of the corona polarization device is the same as that of the device shown in FIG.

Further, the grid electrode 27 is made of stainless steel as shown in FIG. 8 and has a wire diameter of 0.85 mmφ and the mesh spacing is 5.55.
mm, aperture ratio 75%.

Then, the lower electrode 22 and the grid electrode 27
The space between them is 1 cm, and the needle electrode 23 and the grid electrode 27 are
The distance between the electrodes is 1 cm, the substrate is mounted on the lower electrode 22, and the lower electrode 22 is formed on the substrate (25 cm x 25 cm glass).
Connected to.

After heating the polarized material 25 from the room temperature to 200 ° C. at a temperature rising rate of 12 ° C./minute with the heater 26, the voltage of −10 kV is applied to the lower part from the power source 24 while maintaining the temperature for 10 minutes. While applying a voltage of -1.5 kV from the power supply 28 between the lower electrode 22 and the grid electrode 27 while applying the voltage between the electrode 22 and the needle electrode 23, a corona discharge is generated between the lower electrode 22 and the needle electrode 23. During the corona discharge, the grid electrode 27 is moved horizontally at a speed of 30 cm / min so as to reciprocate in the horizontal direction with a width of 3 cm, and the material to be polarized is subjected to corona discharge (10 minutes) to perform polarization treatment, Then, the temperature of the polarized material was gradually cooled (cooled) down to 100 ° C., and then taken out from the polarization device.

As shown in FIG. 9, the material to be polarized (polyurea film) on the substrate thus taken out was placed in a square of 7.5 mm in length and width with the center just below the tip of the needle electrode 22, as shown in FIG. 1 mm
After the upper electrode M made of aluminum having a size of 0.5 mm square at intervals is coated by a vacuum vapor deposition method to make a total of 25 pyroelectric elements L, the pyroelectric coefficient of each element 1 is measured, and The results are shown in Table 1.

The pyroelectric rate was measured as follows.

That is, the prepared pyroelectric element was placed in a heating oven, the upper and lower electrodes were connected to an ammeter, and heated at a constant temperature rising rate. The pyroelectric rate was calculated from the pyroelectric current flowing at that time by the following formula.

[0091]

[Equation 1]

Comparative Example 1 A total of 2 samples were prepared in the same manner as in Example 6 except that the grid electrode was not used and the distance between the lower electrode and the needle electrode was 3 cm.
After producing five pyroelectric elements, the pyroelectric rate of each element was measured, and the results are shown in Table 1.

Comparative Example 2 Twenty-five pyroelectric elements in total were produced by the same method as in Example 6 except that the grid electrode was fixed and corona discharge was performed. Measured and the results are shown in Table 1.
Shown in

[0094]

[Table 1]

As is clear from Table 1, in Example 6 of the present invention, the same pyroelectric rate was obtained in all the elements,
Both Comparative Example 1 in which the grid electrode was not arranged and Comparative Example 2 in which the grid electrode was in a fixed state had large differences in pyroelectric rates.

In Comparative Example 1, the element located farther from the element directly below the needle electrode tended to have a smaller pyroelectric coefficient. The pyroelectric coefficient of the element at a position 2 cm (20 mm) away from the position just below the tip of the needle electrode from the lower electrode was 0.

Example 7 Using the apparatus shown in FIG. 1 (without grid electrode), the needle electrode was 2 cm.
A total of 9 vertical / horizontal and 3 horizontal (total 5cm x 5cm of the material to be polarized) are arranged, no grid electrode is used, and the needle electrode is fixed. After producing 25 pyroelectric elements L in total by the same method as in Example 6, the pyroelectric rate of each element was measured and found to be 22 (μC / m ²
K), minimum 18 (μC / m ² K), average 19 (μC / m ² K).

Example 8 Using the apparatus shown in FIG. 2, nine needle electrodes were arranged vertically and horizontally at 2 cm intervals (with respect to the size of the material to be polarized of 5 cm × 5 cm), and the grid electrodes were fixed. In the same manner as in Example 6 except that the needle-shaped electrode was fixed, a total of 25 pyroelectric elements L were produced, and then the pyroelectric rates of the respective elements were measured.
Maximum 23 (μC / m ² K), Minimum 18 (μC / m ² K), Average 19 (μC / m ² K)
K).

Example 9 Using the apparatus shown in FIG. 3, the needle electrode (one needle electrode) was moved at a speed of 30 cm / min so as to reciprocate horizontally with a width of 3 cm with respect to the electric field during corona discharge. Except for the above, a total of 25 pyroelectric elements L were produced in the same manner as in Example 6, and the pyroelectric rates of the respective elements were measured. The maximum value was 21 (μC / m ² K) and the minimum value was 18
(μC / m ² K) and the average was 19 (μC / m ² K).

Example 10 Using the apparatus shown in FIG. 5, the material to be polarized (the size of the material to be polarized was 5 cm × 5 cm) was 3 cm in the horizontal direction with respect to the electric field during corona discharge.
After a total of 25 pyroelectric elements L were produced by the same method as in Example 6 except that the element was moved back and forth at a speed of 30 cm / min, the pyroelectric rate of each element was measured. 23 (μC
/ M ² K), minimum 18 (μC / m ² K), average 20 (μC / m ² K).

As is clear from the results of the above examples,
Even if there is no grid electrode, the polarized material can be subjected to polarization treatment, but by providing the grid electrode between the lower electrode and the needle-shaped electrode, the width of the sweep increases,
By providing a grid electrode, for example, the size is 500m
It can also be used for a wide area of polarized material (substrate) such as m x 500 mm.

In Example 6, the grid electrode was moved so as to reciprocate within a width of 3 cm during corona discharge. The grid electrode was moved above the material to be polarized in the horizontal direction to the electric field at a speed of 100 rotations / minute. In each case, the pyroelectric constant of each element was the same as that of Example 6.

In Example 7, the plurality of needle-shaped electrodes were fixed during the corona discharge, but the plurality of needle-shaped electrodes were simultaneously reciprocated in the horizontal direction with a width of 3 cm with respect to the electric field at a speed of 3 cm.
When moved at 0 cm / min, or when each needle-shaped electrode is simultaneously swung at a speed of 100 rotations / min so as to draw a circle in a horizontal direction with respect to the electric field above the material to be polarized, each element The pyroelectric constant of was the same as that of Example 7.

In Example 8, the plurality of needle-shaped electrodes were fixed during the corona discharge, but the speed was set so that the plurality of needle-shaped electrodes simultaneously reciprocated in the horizontal direction with respect to the electric field at a width of 3 cm.
When moved at 0 cm / min, or when each needle-shaped electrode is simultaneously swung at a speed of 100 rotations / min so as to draw a circle in a horizontal direction with respect to the electric field above the material to be polarized, each element The pyroelectric constant of was equal to that of Example 8.

In Example 9, the needle-shaped electrode was moved so as to reciprocate within the width of 3 cm during corona discharge. The needle-shaped electrode was rotated at a speed of 100 revolutions / in a circle above the material to be polarized /
In the case of turning in minutes, the pyroelectric constant of each element was the same as that of Example 9.

In Example 10, the material to be polarized was moved so as to reciprocate within the width of 3 cm during corona discharge. However, the material to be polarized was rotated below the needle electrode at a speed of 100 revolutions / minute. In all cases, the pyroelectric constant of each element was the same as that of Example 10.

Needless to say, the method of the present invention is not limited to the above-mentioned embodiment, and the method of moving the needle electrode and the method of moving the grid electrode are combined, the method of moving the needle electrode, and the substrate are moved. Various combinations such as a method in which the above methods are combined may be used.

Corona discharge was performed by setting the polarity between the needle electrode and the lower electrode to be positive (+) or negative (-), and the pyroelectric rate of each element was examined. The polarity of the material to be polarized did not change at all, whether the polarity was positive (+) or negative (-).

[0109]

According to the corona polarization treatment method of the first aspect of the present invention, since a plurality of needle electrodes are used, the surface of the material to be polarized is uniformly charged, and as a result, uniform polarization treatment can be performed. effective.

According to the corona polarization treatment method of the second aspect of the present invention, a grid electrode is provided between the lower electrode and the needle electrode in order to make the magnitude of polarization, that is, charging uniform, and the needle electrode Since a plurality of electrodes are arranged, the grid electrode does not prevent ions from the needle-shaped electrode from entering the material to be polarized, so that the surface of the material to be polarized is uniformly charged, and as a result, uniform polarization treatment can be performed. .

According to the corona polarization treatment method of the third to sixth aspects of the present invention, a grid electrode is provided between the lower electrode and the needle-shaped electrode in order to make the magnitude of polarization, that is, charging uniform. , A plurality of needle-shaped electrodes are arranged, or corona discharge is performed from the needle-shaped electrodes while moving any of the needle-shaped electrodes, the grid electrodes, and the material to be polarized. Does not hinder the incident on the polarized material, the surface of the polarized material is uniformly charged,
As a result, there is an effect that uniform polarization treatment can be performed.

According to the corona-polarizing device of the seventh aspect of the present invention, since a plurality of needle-shaped electrodes are arranged, the surface of the material to be polarized is uniformly charged, and the material to be polarized is uniformly polarized. The effect is to provide a device that can be used.

According to the corona-polarizing device of the eighth aspect of the present invention, a grid electrode is provided between the lower electrode and the needle electrode in order to make polarization, that is, the magnitude of charging uniform, and the needle electrode is provided. Since a plurality of materials are arranged, the surface of the material to be polarized is uniformly charged, and there is an effect of providing an apparatus capable of performing uniform polarization treatment on the material to be polarized.

According to the corona-polarizing device of the ninth to twelfth aspects of the present invention, a grid electrode is provided between the lower electrode and the needle electrode in order to make the magnitude of polarization, that is, charging uniform, A plurality of needle-shaped electrodes are arranged, or one of the needle-shaped electrodes, the grid electrode, and the material to be polarized is arranged so as to be movable during corona discharge. It is effective to provide a device that can perform uniform polarization treatment.

[Brief description of drawings]

FIG. 1 is an example of a corona polarization device of the present invention, and is an explanatory view of a device having a plurality of needle electrodes.

FIG. 2 is another example of a corona polarization device, which is an explanatory view of a device including a grid electrode and having a plurality of needle electrodes.

FIG. 3 is another example of the corona polarization device, which is an explanatory view of a device that includes a grid electrode and moves a needle electrode;

FIG. 4 is another example of the corona polarization device, which is an explanatory view of a device including a grid electrode and moving the grid electrode;

FIG. 5 is another example of the corona polarization device, which is an explanatory view of a device including a grid electrode and for moving a material to be polarized,

FIG. 6 is an explanatory view of an apparatus for forming polarized material in the corona polarization treatment method of the present invention,

FIG. 7 is an explanatory view of an example of a corona polarization device for carrying out the corona polarization treatment method of the present invention,

FIG. 8 is an enlarged view of a main part of a grid electrode used in the apparatus shown in FIG.

FIG. 9 is an explanatory view showing the position of each element for measuring the pyroelectric constant of the material to be polarized that has been polarized by using the apparatus shown in FIG.

FIG. 10 is an explanatory view of a conventional corona polarization device,

FIG. 11 is an explanatory view of a conventional corona polarization device in which grid electrodes are arranged,

FIG. 12 is an explanatory view of a polarization state of a polarized material by a corona polarization device in which a conventional grid electrode is arranged, and an explanatory view showing an ionic state of a needle electrode, a grid electrode, and a polarized material.

[Explanation of symbols]

1, 11, 21, 31 Corona polarization device, 2, 12, 2
2, 32 lower electrode, 3, 13, 23, 33 needle-shaped electrode, 4, 14, 24, 34 power source, 5, 15, 25,
35 polarized material, 7, 17, 27, 37 grid electrode, 8, 18, 28, 38 power supply, L element.

Claims (12)

[Claims] 1. Utilizing corona discharge between a lower electrode and a needle electrode to charge the surface of a material to be polarized on the lower electrode,
At the same time, in the corona polarization treatment method of raising the temperature of the material to be polarized to orient the dipoles contained in the material to be polarized, corona discharge treatment method is performed by corona discharge from a plurality of needle electrodes. 2. The surface of the material to be polarized on the lower electrode is charged by using corona discharge between the lower electrode and the needle-shaped electrode via the grid electrode, and at the same time, the temperature of the material to be polarized is increased to polarize the material to be polarized. A corona polarization treatment method for orienting dipoles contained in a material, characterized in that corona discharge is performed from a plurality of needle electrodes. 3. The surface of the material to be polarized on the lower electrode is charged by utilizing corona discharge between the lower electrode and the needle-shaped electrode via the grid electrode, and at the same time, the temperature of the material to be polarized is increased to be polarized. A corona polarization treatment method for orienting dipoles contained in a material, which comprises performing corona discharge while moving a needle electrode in a horizontal direction with respect to an electric field. 4. A corona discharge between a lower electrode and a needle-shaped electrode via a grit electrode is used to charge the surface of the material to be polarized on the lower electrode while at the same time increasing the temperature of the material to be polarized to be polarized. In a corona polarization treatment method for orienting dipoles contained in a material, corona discharge treatment is performed from a needle electrode while moving a grit electrode in a horizontal direction with respect to an electric field. 5. A corona discharge between a lower electrode and a needle-shaped electrode via a grit electrode is used to charge the surface of the material to be polarized on the lower electrode while at the same time increasing the temperature of the material to be polarized to be polarized. A corona polarization treatment method for orienting dipoles contained in a material, which comprises performing corona discharge from a needle electrode while moving a material to be polarized in a horizontal direction with respect to an electric field. 6. The needle-shaped electrode is a plurality of needle-shaped electrodes, according to any one of claims 3 to 5.
The method of corona polarization treatment according to item. 7. A lower electrode and a needle-shaped electrode arranged at a position opposite to the lower electrode, and contained in a material to be polarized on the lower electrode by utilizing corona discharge between the lower electrode and the needle-shaped electrode. A corona polarization device for orienting dipoles, wherein the needle electrode is composed of a plurality of needle electrodes. 8. A lower electrode, a needle-shaped electrode arranged at a position opposite to the lower electrode, and a grit electrode arranged between the lower electrode and the needle-shaped electrode. The lower electrode and the needle-shaped electrode via the grit electrode. A corona-polarizing device for orienting dipoles contained in a material to be polarized on a lower electrode by utilizing corona discharge between electrodes, characterized in that the needle-shaped electrode is composed of a plurality of needle-shaped electrodes. apparatus. 9. A lower electrode, a needle electrode arranged at a position opposite to the lower electrode, and a grit electrode arranged between the lower electrode and the needle electrode, wherein the lower electrode and the needle electrode are interposed via the grit electrode. In a corona polarization device that uses a corona discharge between electrodes to orient the dipoles contained in the polarized material on the lower electrode, the needle electrodes are arranged so that they can move horizontally with respect to the electric field. Corona polarization device. 10. A lower electrode, a needle electrode arranged at a position opposite to the lower electrode, and a grit electrode arranged between the lower electrode and the needle electrode, wherein the lower electrode and the needle electrode are interposed via the grit electrode. In a corona polarization device that uses a corona discharge between electrodes to orient the dipoles contained in the material to be polarized on the lower electrode, the grit electrode is arranged so as to be movable in the horizontal direction with respect to the electric field. Corona polarization device. 11. A lower electrode, a needle-shaped electrode arranged at a position opposite to the lower electrode, and a grit electrode arranged between the lower electrode and the needle-shaped electrode. The lower electrode and the needle-shaped electrode via the grit electrode. In the corona polarization device that uses the corona discharge between the electrodes to orient the dipoles contained in the material to be polarized on the lower electrode, the material to be polarized is arranged horizontally movable with respect to the electric field. Corona polarization device. 12. The corona polarization device according to claim 9, wherein the needle electrode is a plurality of needle electrodes.