JPH1053657A - Treatment of whole surface of nonconductive porous material, apparatus for treating the whole surface and new modified nonconductive porous material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for treating the whole surface of a nonconductive porous material obtained by electric discharge, by which the nonconductive porous material can be treated not only on the surface of the exterior thereof but also on the surface of the cell in the interior thereof, hardly cause the treated material to be damaged by a sparking, etc., and capable of using every kind of gas and continuously treating the material. SOLUTION: The whole surface of a nonconductive porous material 11 is treated by arranging the porous material 11 between a pair of electrodes 21 and 22 with dielectric material layers 41 and 42 arranged at each mutually facing surface side of the electrode 21 and 22 so that the nonconductive porous material 11 may not be brought into contact with the electrodes 21 and 22 but brought into direct contact with the surfaces of the dielectric material layers 41 and 42, charging a low frequency alternating voltage having 0.1-100kHz frequency between the electrodes 21 and 22 and electrically discharging in the vacancies of the interior of the nonconductive porous material 11.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating the entire surface of a non-conductive porous body, an apparatus for treating the entire surface, and a novel non-conductive porous body. According to the present invention, for example, imparting hydrophilicity, hydrophobicity, or adhesion to the entire surface of the nonconductive porous body, improving hydrophilicity, hydrophobicity, or adhesion, or The entire surface of the porous body can be roughened.

[0002]

2. Description of the Related Art Conventionally, methods for surface treatment of non-conductive materials (whether porous or not) by electric discharge include, for example, a method utilizing AC corona discharge or DC corona discharge, and a low-pressure glow discharge. And a method utilizing atmospheric pressure glow discharge have been known. In the method using AC corona discharge, an object to be processed is brought into contact with a surface of a dielectric provided in surface contact with a surface of a counter electrode (induction electrode) such as a plate electrode, and a predetermined distance ( Usually about 1
mm to several mm), a discharge electrode such as a wire electrode or a needle electrode is disposed, and in air or a predetermined gas, an AC high voltage is applied between the discharge electrode and the counter electrode. This is a method of performing a surface treatment on the object to be processed by the action of a linear corona generated from a discharge electrode. In general, in order to stabilize the generated linear corona, a dielectric is inserted between the object to be processed and the counter electrode. The gas is appropriately selected according to the type of the functional group introduced to the surface of the object. The surface treatment of the object to be processed can also be performed by using a DC corona discharge generated by applying a DC high voltage instead of an AC high voltage.

In this method, in order to generate a corona discharge, it is necessary to apply a certain or more electric field strength between the discharge electrode and the counter electrode, that is, a high voltage higher than the corona starting voltage. If the voltage is too high, spark discharge may occur between the electrodes through a weak portion of the object to be processed, which may cause damage such as making a large hole in the object to be processed.
Further, in the case of processing a processing object having irregularities, the discharge cannot be performed uniformly, which may cause processing unevenness or damage such as a hole in the processing object. Furthermore, since the stability of the discharge greatly depends on the gas used, a stable discharge cannot be generated depending on the kind of the gas used, and the surface treatment may not be performed by this method.

[0004] In a method utilizing low-pressure glow discharge, a pair of electrodes facing each other are provided inside a discharge vessel which can be decompressed, an object to be processed is arranged between the electrodes, and the inside of the discharge vessel is depressurized by a decompression device. The pressure of air or a given gas is about 10
^-2 to about 10 Torr, an AC voltage of several KHz to several MHz is usually applied between the electrodes, and the surface treatment of the object is performed by the action of glow discharge generated between the electrodes. The way to do it. In this method, an AC voltage is applied to the object to be processed in a state where the object is arranged so as not to contact the electrode or in a state where the object is arranged so as to contact only one of the electrodes. In this method, according to Paschen's law, the discharge under low pressure is more likely to occur with a certain distance between the electrodes.Therefore, it is necessary to increase the distance between the electrodes as compared with the above-described method using AC corona discharge. Can be. In addition, at low pressure, ionized chemical species are hardly deactivated and spark discharge hardly occurs, so that there are many types of gases that can be used for discharge.

However, a pressure reducing device for reducing the pressure in the discharge vessel is required, which is not suitable for continuous machining.
Further, when the object to be treated contains a volatile substance, for example, water or a plasticizer, it is difficult to control the pressure. Furthermore, when processing a porous body using low-pressure glow discharge, depending on the pressure and the type of gas, small pores (for example,
No discharge is generated inside Paschen's law (with a pore diameter of less than 0.1 mm), so that the entire surface of such a porous body cannot be treated.

A method using an atmospheric pressure glow discharge [for example, described in Industrial Heating, Vol. 27, No. 1 (1990)]
Is provided with a pair of electrodes facing each other at a predetermined interval (usually several mm) inside a discharge vessel that can be sealed,
While a rare gas, particularly a mixed gas containing helium as a main component and simultaneously containing a predetermined reactive gas used for introducing a functional group, is supplied to the discharge vessel, usually several KH is applied between the electrodes.
This is a method in which an AC voltage of z to several tens of MHz is applied, and the surface of the object is treated by the action of glow discharge generated between the electrodes. In this method, in order to stabilize the generated glow discharge, a dielectric is generally provided in contact with the surface of one of the electrodes. An AC voltage is applied to the object to be processed in a state where it is arranged so as not to contact with any of the electrode and / or the dielectric, or in a state where it is arranged so as to contact only one of the dielectric and the electrode. .

In this method, an expensive rare gas is required as a gas capable of stably generating a discharge, and the discharge becomes unstable if the amount of a reactive gas used for introducing a functional group is increased. Therefore, the amount of gas is also limited. Generally, a reactive gas can be mixed only up to about 10%. In addition, since only the portion where the gas flows can be discharged, it is difficult to treat the surface of the void inside the object, in which the reactive gas is difficult to enter, when treating the porous body. It is difficult to uniformly treat the entire surface of the porous body.

As a method of utilizing the atmospheric pressure glow discharge,
Japanese Patent Application Laid-Open No. 4-74525 discloses a method using a dielectric-coated electrode in which a dielectric is provided on the surfaces of both electrodes facing each other. However, this method applies an AC voltage in a state where it is arranged so as not to contact with any of the electrodes and / or the dielectric, or in a state where it is arranged so as to contact only one of the dielectric and the electrode. This publication does not disclose a method of applying an AC voltage in a state where each of the dielectrics and the object to be processed are arranged so as to be in direct contact with each other. This method also cannot be processed in air, and requires an expensive rare gas as a gas capable of stably generating electric discharge. In the case where the porous body is treated, the surface of the void inside the porous body, in which the reactive gas is difficult to enter, is treated because the reactive gas flows in the part where the reactive gas flows in the atmospheric pressure glow discharge. It is difficult to uniformly treat the entire surface of the porous body.

As another method utilizing the atmospheric pressure glow discharge, a discharge treatment apparatus in which a pair of cylindrical electrodes covered with ceramics (thickness = 0.5 mm to 2 mm) are arranged in parallel is disclosed in Japanese Unexamined Patent Publication No. Hei. It is disclosed in JP-A-7-119021. This processing apparatus also requires an expensive rare gas (atmospheric gas containing a mixed gas of helium and argon as a main component), and from the viewpoint of obtaining a stable discharge, a gas capable of stably generating a discharge. The type is limited (the preferred oxygen concentration is less than 0.5%) and cannot be processed in air. In addition, even in this apparatus, since only the portion in contact with the reactive gas can be processed,
When treating a porous body, it is difficult to treat the surface of voids inside the object, into which the reactive gas is difficult to enter, and it is therefore difficult to uniformly treat the entire surface of the porous body.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to treat not only the outer surface of a porous body but also the surface of a void inside the porous body, and furthermore, the object to be processed by spark discharge or the like. An object of the present invention is to provide means for treating the entire surface of a non-conductive porous body by electric discharge, which is hardly damaged, can use any kind of gas, and can be continuously treated.

[0011]

SUMMARY OF THE INVENTION The object of the present invention is to provide a semiconductor device according to the present invention, in which a dielectric layer is provided on each of the opposing surfaces, and the pair of electrodes are disposed opposite each other. A non-conductive porous body is arranged so as not to be in direct contact with each of the derivative layers and the outer surface to be in direct contact, and a low-frequency AC voltage having a frequency of 0.1 kHz to 100 kHz is applied between the two electrodes. Then, a discharge can be generated in the internal space of the non-conductive porous body sandwiched between the two electrodes, and the method can be achieved by a method for treating the entire surface of the non-conductive porous body. The object of the present invention is to provide (1) a pair of electrodes arranged to face each other, (2) a dielectric layer arranged on each of the opposing surfaces of the electrodes, and (3) an electric connection to both electrodes. And a means for treating the total surface of the non-conductive porous body, characterized by including means capable of applying an AC voltage between both electrodes. The present invention also relates to a modified non-conductive porous body having a functional group introduced into at least a part of the total surface of the non-conductive porous body, wherein the functional group introduction efficiency on the inner surface where the functional group is introduced. Functional group introduction efficiency (A) with respect to (B) on the exposed surface where the functional group is introduced
, Wherein the introduction efficiency ratio (A / B) is less than 1.

In the present specification, the term “total surface” is a concept including both the outer surface of the non-conductive porous body to be treated and the inner surface of the non-conductive porous body. The “outer surface” refers to the surface of the non-conductive porous body in contact with a virtual solid having a smooth surface circumscribing the non-conductive porous body. The “inner surface” means the entire surface of all the internal voids included in the virtual solid of the non-conductive porous body. Therefore, the inner surface is the surface of each cell in the foam-type porous body, and the surface of the concave structure (for example, a hollow or a groove) or the surface of the through-hole in the film-type porous body, The surface of the internal porous body formed by the constituent fibers in the quality-type porous body, that is, the entire surface of each constituent fiber is included. The bubbles include open-cells and closed cells (c).
closed-cell). Further, in the present specification, the “exposed surface” means a surface which can be analyzed by X-ray photoelectron spectroscopy, out of the total surface of the object to be processed, and the “inner surface” means the surface of the object to be processed. Of the total surface,
Means a surface other than the exposed surface.

In the present specification, "treatment of the entire surface" means that at least a part of the entire surface of the non-conductive porous material to be treated is chemically or physically treated. Chemical treatment means chemically modifying the entire surface of the non-conductive porous body, for example, a treatment for introducing a desired functional group into a compound constituting the non-conductive porous body. To impart hydrophilicity, hydrophobicity, or adhesiveness to the entire surface of the non-conductive porous body, or improve hydrophilicity, hydrophobicity, or adhesiveness. In the presence of a surface treatment gas capable of introducing a desired functional group, a discharge is generated in an internal void included in the virtual solid of the non-conductive porous body, whereby the desired functional group is formed. An introduced chemical treatment can be performed. For example, hydrophilicity is achieved by introducing a functional group containing an oxygen atom from air, oxygen gas, carbon dioxide gas, or carbon monoxide gas, and hydrophobicity is achieved by introducing a fluorine atom from tetrafluoromethane or the like. By introducing a functional group containing, it can be imparted or improved, respectively.

[0014] The physical treatment means physically modifying the entire surface of the non-conductive porous body, and examples thereof include roughening by plasma treatment. Rough surface processing can be performed by generating electric discharge in a surface treatment gas such as air. Note that the chemical treatment and the physical treatment can be performed simultaneously. For example,
When air is used as the surface treatment gas, the hydrophilicity of the non-conductive porous body can be improved and rough surface processing can be performed. In general, when performing a physical treatment, a chemical treatment also occurs at the same time, but when it is necessary to selectively perform a chemical treatment, treatment conditions, such as an applied voltage, an applied time, and The chemical treatment can be mainly performed by appropriately selecting the type of the surface treatment gas and the like according to the purpose of the treatment of the entire surface.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the accompanying drawings. FIG. 1 shows the basic principle of the present invention. As shown in FIG. 1, a pair of electrodes 21 and
2 are arranged to face each other. The electrode 21 carries a dielectric layer 41 that is in surface contact with the facing surface side, and the electrode 22 also
A dielectric layer 42 that is in surface contact with the facing surface side is carried.
Furthermore, a non-contact between the dielectric layer 41 and the dielectric layer 42 is made so that the outer surface does not come into contact with either of the electrodes 21 and 22 but each of the dielectric layer 41 and the dielectric layer 42 comes into direct contact. The conductive porous body 11 is disposed. At this time, by pressing the electrode 21 and the electrode 22 with an appropriate pressure, the electrode 21 and the dielectric layer 41, the dielectric layer 41 and the non-conductive porous body 11, the non-conductive porous body 11, Dielectric layer 42,
In addition, surface contact is made between each of the dielectric layer 42 and the electrode 22 so that substantially no space is formed. The size of the electrode 21 and the electrode 22 is adjusted by the
In addition, it is preferable that the size be smaller than the size of the dielectric layer 42 because no spark is generated between the ends of the electrodes 21 and 22. Also, the size of the electrode 21 or the electrode 22 is
When the size of the dielectric layer 41 or the dielectric layer 42 is in contact with each other, a covering material (for example, vinyl tape) made of a dielectric material is provided around the electrodes, so that the two electrodes 21 and 22 are formed. Sparks between the ends can be prevented. The electrode 21 is connected to an AC power supply 51,
Ground.

When an AC high voltage is applied from an AC power supply 51, a discharge occurs in the internal space of the non-conductive porous body 11, and plasma is generated. The plasma generated in the internal voids of the non-conductive porous body 11 acts on the inner surface of the non-conductive porous body 11, thereby modifying the inner surface of the non-conductive porous body 11. At this time, the non-conductive porous body 1
1 is in contact with the dielectric layer 41 or the dielectric layer 42, the plasma generated in the internal voids of the non-conductive porous body 11 theoretically has the outer surface of the non-conductive porous body 11. Does not act on the point of contact with the derivative layer. However, in practice, the point of contact is a very small area compared to the area of the outer surface, so it can be said that substantially all of the outer surface has been treated. In addition, since the non-conductive porous body is treated not only by plasma but also by radicals generated by the plasma, when the porous body and the dielectric layer are separated from each other, the contact point is generated by radicals remaining without being deactivated. Is also processed. In the present invention, since a discharge is generated in the internal space of the non-conductive porous body, damage to the object to be processed due to spark discharge or the like hardly occurs.

In the present invention, the lower limit of the AC voltage applied to generate a discharge by the AC power source is not particularly limited because it depends on the distance between the electrodes including the dielectric layer and the type of gas. But preferably 0.25 KVp
And more preferably 0.5 KVp or more (KVp
Indicates a voltage difference from the maximum value peak of the AC voltage to 0). This is because when the voltage is less than 0.25 KVp, substantially no discharge occurs. The upper limit of the AC voltage is not particularly limited as long as the voltage does not cause damage to the non-conductive porous body.

The upper limit of the frequency of the AC voltage is not particularly limited, but is preferably 100 KHz, more preferably 50 KHz. If the frequency exceeds 100 KHz, the dielectric conductive heating may cause the nonconductive porous body to be overheated and be broken. Further, when the frequency is 50 KHz or less, it is more preferable that the dielectric and the electrode are hardly heated, so that the treatment can be stably performed for a long time. The lower limit of the frequency is preferably 0.1 KHz, more preferably 0.5 KHz,
More preferably, it is 1 KHz. Frequency is 0.1KHz
If it is less than the above, the processing efficiency due to the discharge may decrease. It is more preferable that the frequency be 1 KHz or more, since the processing efficiency is high and the processing time is short.

The output of the AC is not particularly limited since it depends on the shape of each electrode or the material or thickness of the dielectric layer or the object to be used. When the porous body is treated by sandwiching it in a certain area (for example, see FIG. 1 or FIG. 4 described later), 0.5
It is preferably from 5 to 5 W / cm ² . Further, in the case where the pair of electrodes is processed by sandwiching the non-conductive porous body in a linear manner (for example, see FIG. 2, FIG. 3, FIG. 5, or FIG. 6 described later), the output of the AC is: It is preferably 0.1 to 9 W / cm, and more preferably 0.1 to 6 W / cm. In the case where the non-conductive porous body is treated by sandwiching the same in a linear manner and a plurality of electrodes are used (for example,
In FIG. 3, FIG. 5, or FIG. 6 described later), the range of the AC output means a value per electrode.

In the present invention, when the AC output is lower than the above range (that is, when the non-conductive porous body is sandwiched between certain regions and processed), it is less than 0.5 W / cm ² , In the case where the conductive porous body is linearly sandwiched and processed, the discharge is mainly generated at a place where the nonconductive porous body is likely to discharge. It may not be possible to process uniformly. Further, when the AC output is higher than the above range (that is, when the non-conductive porous body is sandwiched between certain regions and the processing is performed, it exceeds 5 W / cm ² , or the non-conductive porous body has a linear shape). In the case where the treatment exceeds 9 W / cm, the non-conductive porous body may have holes due to arc discharge.

The waveform of the applied voltage is not particularly limited, and may be, for example, a sine wave, a triangular wave, a rectangular wave, or the like. (A pulse wave shown in FIG. 10). In the pulse wave, the rise time of the voltage wave (for example, time t in FIG. 10) is 1
The time is preferably not more than microsecond, more preferably not more than 0.5 microsecond. Further, the voltage pulse width (half width) (for example, the width w in FIG. 10) is preferably 10 μs or less, more preferably 2 μs or less. The preferred range of the frequency when using the pulse wave (for example, the frequency when one cycle of the wavelength λ in FIG. 10) is not limited, but the upper limit is preferably set for the same reason as described above. Is 100 KHz, more preferably 50 KHz, and the lower limit thereof is preferably 0.1 KHz, more preferably 0.5 KHz, and still more preferably 1 KHz. By using such a pulse wave, the entire surface treatment can be performed without making a hole even in a non-conductive porous material (for example, a melt-blown nonwoven fabric) in which holes are easily formed by spark discharge. Note that these values relating to the alternating current applied to generate a discharge largely deviate from the above-mentioned range because they greatly depend on the shape of each electrode, the material of the non-conductive porous body, the discharge voltage waveform, and the processing time. Sometimes used.

FIG. 1 shows an embodiment in which an AC power supply 51 is connected to the electrode 21 and the electrode 22 is grounded. However, in the present invention, the AC power supply 51 is connected to the electrode 22 and May be grounded.

[0023] As the material of the electrode which can be used in the present invention, the specific resistance is preferably 10 ³ Ω · cm or less, and more preferably can be used the following conductor 10 ⁰ Ω · cm, for example, metal (For example, stainless steel,
Aluminum, tungsten, or the like), conductive metal oxide, carbon, or conductive rubber obtained by combining a conductor (for example, metal powder or carbon powder) with rubber can be used. Also, as the shape of the electrode,
For example, a sheet electrode, a plate electrode, or a columnar electrode can be used. As in the embodiments shown in FIGS. 2 to 6 described below, when the non-conductive porous body and the electrode relatively move, so that it is difficult to damage the surface of the non-conductive porous body, A columnar electrode that is capable of rotating itself around the central axis of the column in synchronization with the parallel movement of the nonconductive porous body is preferable.

In the present invention, the lower limit of the pressure applied between both electrodes ensures surface contact between the electrodes and the dielectric layer, and between the dielectric layer and the non-conductive porous body, and substantially ensures the surface contact. This pressure does not create a space. The upper limit is a pressure that does not destroy the shape of the non-conductive porous body that is the object to be processed.

The dielectric layer that can be used in the present invention is:
It can be entirely non-porous, or it can include a porous portion in part. If a dielectric layer composed entirely of a porous portion is used as the dielectric layer, a spark discharge may be generated inside the object to be processed and the porous portion of the dielectric. Therefore, in the present invention, it is not preferable to use such a dielectric layer. For the same reason, it is not preferable to use a dielectric layer including a porous portion continuous in the thickness direction as the dielectric layer. When a dielectric layer having a porous portion is used on the contact surface with the object to be processed, the contact surface between the dielectric layer and the object to be processed is smaller than when a dielectric layer made entirely of non-porous material is used. Because of the reduction, the outer surface of the object can be more efficiently treated.

As the material of the dielectric layer that can be used in the present invention, for example, glass, ceramic (for example, alumina, etc.), rubber (for example, synthetic rubber, for example, silicone rubber, chloroprene rubber, or butadiene rubber, or Natural rubber) or a thermoplastic resin (eg, polytetrafluoroethylene or polyester). The dielectric layer in contact with the non-conductive porous body that is the object to be processed, especially the contact surface, it is preferable to use rubber or thermoplastic resin in terms of excellent elasticity, it is excellent in elasticity, It is more preferable to use rubber from the viewpoint of excellent adhesion to the object. In particular, it is preferable to use rubber that does not easily damage the surface of the object to be processed or polytetrafluoroethylene that is resistant to dielectric breakdown. The thickness of the dielectric layer is not particularly limited, but is preferably about 0.05 to 5 mm.
When the thickness is more than 5 mm, a very high voltage is required for discharging, and when the thickness is less than 0.05 mm, the mechanical strength decreases,
This is because dielectric breakdown easily occurs.

As the non-conductive porous body whose entire surface can be treated according to the present invention, a porous body made of any non-conductive organic or inorganic material can be used. As the organic material, various organic polymer compounds, for example, polyolefin such as polyethylene and polypropylene, polyester, polycarbonate, polyvinyl chloride, fluorinated ethylene propylene copolymer (FEP),
Examples thereof include polyvinylidene fluoride (PVDF) and a vinylidene fluoride-trifluoroethylene copolymer. As the inorganic material, various ceramics (for example, alumina, silica, or silica-alumina),
Alternatively, glass (eg, soda glass or silica glass) can be given.

As the porous body made of the various materials,
For example, a fibrous porous body, a film porous body, or a foam porous body can be used. The fibrous porous body is made of, for example, a woven fabric, a knitted fabric, a fibrous porous film, or a nonwoven fabric. Examples of the nonwoven fabric include a dry nonwoven fabric (a hydroentangled nonwoven fabric, a needle-punched nonwoven fabric, a binder-bonded nonwoven fabric, or a heat-sealed nonwoven fabric), a spunbonded nonwoven fabric, a meltblown nonwoven fabric, and a wet nonwoven fabric. Examples of the foam include an open-cell foam and a closed-cell foam made of a resin such as polyolefin, polyester, or polyurethane. Examples of the film-type porous body include a film having an uneven structure and a perforated film.

The present invention is particularly applicable to the treatment of a fibrous porous body made of a non-conductive organic material. For example, the present invention can be applied to a non-woven sheet, particularly a non-woven sheet which can be used as a separator for an alkaline battery. Can be applied. Non-woven fabrics that can be used as the alkaline battery separator include, but are not limited to, for example, polyolefin fibers, i.e., polyethylene, ethylene copolymer, polypropylene, propylene copolymer, polybutene, A fiber comprising one or more butene-based copolymers, polymethylpentene, or a pentene-based copolymer as a resin component, for example, formed by hydroentanglement, heat fusion, or meltblowing, or a combination thereof. Non-woven fabrics can be used.

The shape of the non-conductive porous body whose entire surface can be treated by the present invention is such that when the outer surface of the non-conductive porous body comes into contact with the dielectric layer, a void is formed inside the porous body. The shape is not particularly limited as long as it has. The porosity (porosity in the state at the time of treatment) of the non-conductive porous body whose entire surface can be treated by the present invention is higher than 0% and less than 99%. In particular, the inner surface of the non-conductive porous body having a porosity of 95% or less is difficult to treat by the conventional glow discharge, but can be treated by the present invention.

The upper limit of the size of the internal void is not particularly limited, but preferably the average void diameter of the void is 1 mm or less. In particular, the inner surface of the non-conductive porous body having an average pore diameter of 0.1 mm or less, particularly 30 μm or less, was difficult to be treated by the conventional glow discharge. Can be. The average pore diameter of the fibrous porous body can be measured, for example, with a Coulter Porometer II (manufactured by Coulter).
If the average pore diameter exceeds 1 mm, arc discharge may occur and damage the porous body. However, even if the average pore diameter exceeds 1 mm, any material can be used as long as it can be compressed during processing to reduce the average pore diameter to 1 mm or less. When the average pore diameter is 0.1 mm or less, sparks are unlikely to occur. The lower limit of the size of the internal void is not particularly limited as long as a discharge can be generated in the internal void of the non-conductive porous body.

The preferred thickness of the non-conductive porous body (thickness between both dielectric layers) also varies depending on the thickness of the dielectric layer, the type of the porous body, and the like. Although not particularly limited, it is preferably 10 mm or less, more preferably 1 mm or less. 10mm
This is because, when the temperature exceeds the limit, arc discharge easily occurs, and a high discharge voltage is required. When the thickness is 1 mm or less, sparks are less likely to occur, and processing is possible even with materials that are weak to heat. In addition, even if the thickness of the non-conductive porous body exceeds 10 mm, it is compressed during processing to reduce the thickness to 1 mm.
What is necessary is just to be able to be 0 mm or less. Further, the inner surface of the non-conductive porous body having a thickness of 0.1 mm or more has been difficult to treat by the conventional glow discharge, but can be treated by using the present invention. The air permeability of the non-conductive porous body is not particularly limited. Air permeability of 0.5 to 200 ml / cm ²
Seconds, in particular, the inner surface of the non-conductive porous body of 1 to 150 ml / cm ² · sec has been difficult to treat by the conventional glow discharge, but is treated by using the present invention. be able to.

Non-conductive porous material having a porosity of 95% or less, non-conductive porous material having an average internal pore diameter of 0.1 mm or less, and non-conductive porous material having a thickness of 0.1 to 10 mm The inner surface of a body (including a body that is compressed to fall within this range) or a non-conductive porous body having an air permeability of 0.5 to 200 ml / cm ² · sec may be treated by glow discharge. On the other hand, when the present invention is used, each of the above-mentioned non-conductive porous bodies (particularly, a non-conductive porous body that satisfies all the conditions, ie, porosity, The entire surface of the nonconductive porous body having an average pore diameter, thickness, and air permeability within the above ranges can be treated.

The present invention can be carried out in an open system, ie, at atmospheric pressure, generally in the presence of air, but need not be carried out in a closed system, eg, an airtight vessel, Discharge can also be generated while supplying a surface treatment gas other than air to the internal space of the non-conductive porous body. In addition, the present invention does not require an inert gas (for example, a rare gas) that is necessary for stably generating a discharge in a conventional atmospheric pressure glow discharge. As means for supplying a surface treatment gas to the internal voids of the non-conductive porous body,
For example, a method of forcibly sending a surface treatment gas into the inside of a non-conductive porous body, a method of spraying a surface treatment gas to the non-conductive porous body and its vicinity, or Examples of the method include a method of forming an atmosphere of a surface treatment gas, and these methods can be performed in an open system or a closed system.

For example, when a discharge is generated by applying an AC high voltage while supplying a surface treatment gas to the internal space of the non-conductive porous body using a gas supply pipe or the like, the non-conductive porous Due to the action of the plasma generated in the internal voids of the porous body, the inner surface of the non-conductive porous body reacts with the surface treatment gas to modify the inner surface of the non-conductive porous body, for example, a desired functional property. Groups can be introduced.

When a surface treatment gas other than air is supplied to the voids inside the non-conductive porous body, the non-conductive porous body and its vicinity are filled with a specific gas and mixed with air. It is preferable that contact does not occur and an unintended reaction does not occur. Further, when the surroundings of the non-conductive porous body is set to the atmosphere of the surface treatment gas, for example,
The non-conductive porous body, the electrode, and the dielectric layer may be disposed in an airtight container, and the discharge treatment may be performed in a state in which the surface treatment gas is sealed therein. In this case, the processing region can be filled with a specific gas, and no contact with air occurs, which is preferable.

The "surface treatment gas" that can be used in the present invention is not particularly limited, and can be appropriately selected from known surface treatment gases according to the desired surface treatment. When imparting hydrophilicity to the non-conductive porous body or performing a surface treatment for improving the hydrophilicity, for example, air or oxygen gas can be used to impart hydrophobicity to the non-conductive porous body. In the case of applying or performing a surface treatment for improving hydrophobicity, for example, tetrafluoromethane (C
F ₄ ) can be used. Also, the concentration of the surface treatment gas is not particularly limited, and can be appropriately selected according to the desired total surface treatment. Furthermore, the total surface treatment of the non-conductive porous body can be performed under constant conditions or with time without changing the type and / or concentration of the surface treatment gas.

Physical treatment on the entire surface of the non-conductive porous body,
For example, in the case of performing rough surface processing, it is preferable to apply a higher AC voltage than in the case of performing only a chemical treatment in which a discharge treatment is performed while supplying a surface treatment gas. Preferably, the time is lengthened. In particular, when performing rough surface processing while maintaining the water repellency of the nonconductive porous body, the treatment is performed while supplying a gas (for example, tetrafluoromethane) that imparts water repellency as a surface treatment gas. Is preferred.

Further, according to the present invention, since the nonconductive porous body is substantially treated only on the entire surface of the portion sandwiched between the pair of electrodes, it is possible to adjust the shape of at least one of the electrodes. Thereby, the shape of the region to be processed can be arbitrarily adjusted. For example, one of the electrodes is a plate-like electrode, the other electrode of a desired shape, such as a reticulated electrode or a linear electrode, by the same pattern as the desired shape, for example, a reticulated pattern or a linear pattern The non-conductive porous body can be selectively treated.

In a porous modified body whose surface has been modified by a conventional surface treatment method utilizing glow discharge, a sufficient amount of gaseous active chemical species is present in the voids further inside the surface layer region of the object to be treated. The degree of surface treatment drops sharply from the outer surface to the inner surface, since the inner surface cannot be treated to the same extent as the outer surface, and the inner surface is hardly treated . On the other hand, in the present invention, a discharge is generated in the internal void and the surface is treated by the discharge, so that the entire surface can be treated uniformly. However, the degree of surface treatment on the exposed surface may be lower than the degree of surface treatment on other total surfaces (that is, the inner surface).
Because a part of the exposed surface of the object is in contact with the dielectric layer when generating a discharge in the internal void, the plasma generated in the internal void does not work in theory, and the contact surface This is because, when the dielectric layer and the object to be processed are separated from each other, the processing is mainly performed by the residual plasma itself existing in the vicinity of the contact surface or radicals generated by the plasma.

The non-conductive porous modified body of the present invention is obtained by, for example, chemically treating at least a part of the entire surface of the non-conductive porous body by using the method of the present invention to obtain desired properties. It can be prepared by introducing a functional group that can be imparted or improved to the surface to be treated. As the non-conductive porous body, various non-conductive porous bodies which can be treated on the entire surface according to the present invention as described above can be used. In particular, a non-conductive porous body that is difficult to process by a conventional glow discharge, for example, a porosity of 95%
The following non-conductive porous body, a non-conductive porous body having an average pore diameter of 0.1 mm or less, a thickness of 0.1 to
10 mm non-conductive porous material (including one that is compressed to fall within this range), or air permeability of 0.5 to 200 ml / c
Non-conductive porous material that is m ² · second, particularly a non-conductive porous material that satisfies all the conditions, that is, the porosity, the average pore diameter of the internal voids, the thickness, and the air permeability are in the above range The inner surface of the non-conductive porous body can be treated according to the present invention.

In the non-conductive porous modified article of the present invention, the efficiency of introducing a functional group on the exposed surface to which the functional group is introduced [hereinafter referred to as the exposed surface introducing efficiency (A)], The introduction efficiency ratio (A), which is the ratio of the exposed surface introduction efficiency (A) to the internal surface introduction efficiency (B), in relation to the functional group introduction efficiency on the internal surface (hereinafter referred to as the internal surface introduction efficiency (B)). / B) is less than 1 (A
/ B <1), preferably 0.3 or more and 0.95
(0.3 ≦ A / B ≦ 0.95), more preferably 0.4 or more and 0.85 or less (0.4 ≦ A / B ≦
0.85). When a dielectric layer including a porous dielectric portion on at least a part of the opposing surface side surface is used as the dielectric layer, the introduction efficiency ratio can be made closer to 1. In this case, the ratio of the contact surface between the outer surface of the object to be processed and the dielectric layer (theoretically, the surface on which plasma generated by discharge cannot act) is determined by the ratio of the non-porous dielectric layer. This is because the number is reduced as compared with the case of using. When the surface treatment is performed by using the conventional glow discharge, the internal surface is hardly treated, so that the introduction efficiency ratio is larger than 1.

The functional group introduction efficiency on each surface-treated surface, ie, each surface on which a functional group is introduced, is expressed as a value by which the degree of functional group introduction on each surface can be objectively compared. The index is not particularly limited as long as it can be used, and the degree of introduction can be compared by appropriately selecting an appropriate atomic group or atom according to the functional group to be introduced. For example, when the non-conductive porous body to be processed is made of an organic material, the efficiency of functional group introduction is defined as the ratio of the number of introduced functional groups to the number of carbon atoms on the surface where the functional groups are introduced. Or "the ratio of the number of specific atoms contained in the introduced functional group to the carbon atoms on the surface into which the functional group has been introduced".

When the ratio of the number of specific atoms contained in the introduced functional group to the number of carbon atoms on the surface where the functional group is introduced is used as the introduction efficiency, for example,
Using X-ray photoelectron spectroscopy, the peak area of the carbon atom on the target surface and the peak area of the specific atom contained in the introduced functional group on the target surface are measured, and the photoionization cross-sectional area is corrected. Thereby, the introduction efficiency on the target surface can be obtained. The introduction efficiency on the exposed surface can be determined by directly measuring the modified product as it is using X-ray photoelectron spectroscopy. The introduction efficiency on the internal surface can be determined by a process for exposing the internal surface, for example, Part of the interior of the body (for example,
Fiber or the like or after slicing the modified product, and then using X-ray photoelectron spectroscopy.

For example, when a non-conductive porous material is treated in the air using the present invention for imparting hydrophilicity or improving hydrophilicity, a non-conductive porous material having oxygen atoms introduced into the surface to be treated is used. The porous modified body of the invention can be obtained. In this case, for example, by using X-ray photoelectron spectroscopy, the peak areas of carbon atoms and oxygen atoms on the exposed surface and the internal surface are respectively measured, and the exposed surface and the internal surface are corrected by adding a photoionization cross-sectional area correction. Can be determined (that is, the ratio of the number of introduced oxygen atoms to carbon atoms), and further, the introduction efficiency ratio can be determined.

The non-conductive porous modified material according to the present invention can be identified by detecting the modification (treatment) and detecting the difference in physical properties between the exposed surface and the internal surface. For example,
The case where the wetting index is used to detect the modification and the difference in the physical properties will be described below.

(1) A certain porous body sample is analyzed using a means such as an infrared spectrometer to determine a constituent material of a portion not belonging to the total surface. As the portion not belonging to the total surface, when the sample is a film-type porous body or a foam-type porous body, for example, a solid portion can be mentioned. In the case of the body, for example, the inner part of the constituent fiber can be mentioned. Determine the wetting index of the porous body made of the determined constituent material,
Determined in accordance with "Method of Wetting Test for Polyethylene and Polypropylene Films" (JIS K ^6768-1977 ). In the case of a plurality of components, the wetting index of the component having the smaller wetting index is determined. An indicator is selected that can wet and color the material having this wetting index.

(2) After immersing the sample in a liquid of an indicator (containing a coloring agent) having a wetting index determined in the step (1),
When pulled up, depending on the state of the surface of the sample, the coloring state of the surface of the sample corresponds to one of the following states (a) to (c): (a) colored part (non-processed area) and not colored The part appears. It can be seen that the uncolored portion has been subjected to a hydrophobic treatment. In this case, subsequently, a step (4) described later is performed. (B) The entire sample is not colored. It can be seen that the entire sample has been subjected to the hydrophobic treatment. In this case, subsequently, a step (4) described later is performed. (C) The entire sample is colored. It is conceivable that a part or the whole of the sample has been subjected to a hydrophilization treatment, or that the surface treatment has not been performed. In this case, the next step (3) is subsequently performed.

(3) The sample is immersed in a liquid of an indicator having a higher wettability index than the indicator used in the step (2), and then pulled up. In addition, as the indicator, it is preferable to use an indicator having a slightly higher wetting index than the indicator used in the step (2), and to use an indicator having a higher wetting index sequentially, and repeat the above operation. The condition of the surface of the sample corresponds to any of the following conditions (d) to (f): (d) When an indicator having a slightly higher wetting index than the indicator used in the step (2) is used, The whole sample is not colored. It can be seen that this sample was not subjected to any surface treatment. (E) When an indicator having a wetting index slightly higher than the indicator used in the step (2) is used, an uncolored portion (non-processed region) and a colored portion appear. It can be seen that the colored portion has been subjected to a hydrophilic treatment. In this case, subsequently, a step (4) described later is performed. (F) When an indicator having a wetting index higher than the indicator used in the step (2) is sequentially used, the entire sample is colored up to a certain wetting index, and the wetting index is slightly higher than the wetting index. When the indicator is used, the whole sample is not colored. It can be seen that the entire sample has been hydrophilized. In this case, the next step (4) is subsequently performed. Through the above steps (1) to (3), the presence or absence of reforming (processing) can be detected. When the modification is performed, subsequently, a difference in physical properties between the exposed surface and the inner surface is detected.

(4) The ratio of the number of each introduced functional group to the number of carbon atoms on the exposed surface and the inner surface of the processing region is determined by, for example, X-ray photoelectron spectroscopy. When the surface treatment is a hydrophilic treatment [when the sample surface is in the state (e) or the state (f)], a specific atom of the functional group, for example, an oxygen atom can be selected, When the surface treatment is a hydrophobic treatment [when the sample surface is in the state (a) or the state (b)], a specific atom of a functional group, for example, a fluorine atom can be selected. If the introduction efficiency ratio, that is, the ratio (A / B) of the ratio (A) of the number on the exposed surface to the ratio (B) of the number on the inner surface is smaller than 1, the sample is a porous material of the present invention. It is a modified body.

The present invention is not limited to the embodiment shown in FIG. 1 in which electric discharge is generated in a state where the non-conductive porous body is stationary, and the non-conductive porous body is continuously moved while the non-conductive porous body is moved. Surface treatment of the porous body can also be performed. Another embodiment of the present invention is shown in FIG.

In this embodiment, the columnar electrode 21 and the columnar electrode 22 are arranged to face each other. The surfaces of the electrodes 21 and 22 are the dielectric layers 41 and 42.
Each is covered. The electrode 21 and the electrode 22 may be capable of rotating themselves with the column central axis as a rotation axis, or may be fixed without rotating. When the non-conductive porous body moves, it is an electrode that can rotate itself around the center axis of the cylinder in that the surface of the non-conductive porous body is not easily scratched. preferable.

The electrode 21 is connected to an AC power supply 51 and the electrode 2
Ground 2 The non-conductive porous body 11 is provided with two electrodes 2
The electrode 21 and the electrode 22 are moved by a transfer means (for example, a pair of delivery rollers: not shown) provided upstream of the electrodes 21 and 22.
Are continuously supplied at a predetermined speed in the direction shown by arrow A between the dielectric layer 41 and the dielectric layer 42 carried on the surfaces of the two dielectric layers 41 and 42, respectively.
Pass between. The non-conductive porous body 11 having passed between the two dielectric layers 41 and 42 is moved at a predetermined speed by a transfer means (for example, a pair of delivery rollers: not shown) provided downstream of the two electrodes 21 and 22. Transferred continuously. A driving means (for example, a motor) for supplying a driving force for transporting the non-conductive porous body 11 can be connected to the above-mentioned delivery roller and / or a rotatable electrode.

The supply speed and the transfer speed of the nonconductive porous body 11 are not particularly limited, and may be a constant speed or a speed that changes periodically or irregularly.
These speeds are preferably constant so that the surface treatment time of the non-conductive porous body becomes 0.1 seconds or more. If the speed is higher than this, a sufficient total surface treatment effect may not be obtained.

The nonconductive porous body 11 is
When an AC high voltage is applied from an AC power supply 51 when the AC power supply passes through the space between
In addition, a discharge is generated in an internal space of the non-conductive porous body 11 sandwiched between the contact surface between each of the dielectric layers 42 and the non-conductive porous body 11, and plasma is generated. By the action of the plasma generated in the internal space of the non-conductive porous body 11,
The inner surface of the non-conductive porous body 11 is modified.
At this time, the plasma generated in the internal gap of the non-conductive porous body 11 does not act on the contact surface between each of the dielectric layers 41 and 42 and the non-conductive porous body 11. However, since the non-conductive porous body 11 is continuously transferred at a predetermined speed, the outer surface of the non-conductive porous body 11, which was the contact surface, is separated from the dielectric layer 41 and the dielectric layer 42. The outer surface of the non-conductive porous body 11 is reformed by the action of the plasma generated in the internal space in the vicinity immediately after separation.

Since the non-conductive porous body 11 is continuously transferred at a predetermined speed, the untreated non-conductive porous body 11
Is continuously supplied between the two dielectric layers 41 and 42, while the non-conductive porous body 11 whose entire surface is modified is continuously supplied between the two dielectric layers 41 and 42. Thus, the total surface treatment of the non-conductive porous body 11 can be performed continuously.

In the embodiment shown in FIG. 2, the AC voltage applied to generate the discharge by the AC power supply is not particularly limited, but for the same reason as described in the embodiment shown in FIG. It is preferable that they are in the same range as the AC voltage and the frequency. In the embodiment shown in FIG. 2, the AC power supply 51 is connected to the electrode 21 and the electrode 22 is grounded. On the contrary, the AC power supply 51 may be connected to the electrode 22 and the electrode 21 may be grounded. . The embodiment shown in FIG. 2 can be carried out in an open system, that is, under atmospheric pressure and generally in the presence of air, but uses a surface treatment gas other than air depending on the desired total surface treatment. When necessary, a discharge can be generated while supplying the surface treatment gas to the treatment region.

In the embodiment shown in FIG. 2, only one columnar electrode 21 carrying a dielectric layer 41 is provided on the surface thereof, but the number of electrodes 21 is not particularly limited, and one electrode 21 is provided. Or a plurality can be provided. A plurality of electrodes carrying a dielectric layer may be provided so that any one point on the outer surface of the non-conductive porous body can make multiple contact with the dielectric layer carried on the surface of the electrode. This is preferable in that the processing effect can be enhanced and the processing speed can be increased.

Five small-diameter cylindrical electrodes carrying a dielectric layer on its surface are arranged in parallel at predetermined intervals along the surface of the dielectric layer carried on the large-diameter cylindrical electrode surface. Yet another embodiment of the present invention, located at FIG. The five columnar electrodes 21 (sometimes referred to as 21a, 21b, 21c, 21d, and 21e from the upstream side in the flow direction of the non-conductive porous body) are formed into cylindrical columns having a diameter larger than those electrodes. Are arranged in parallel at predetermined intervals along the surface of the dielectric layer 42 carried on the surface of the electrode 22, and the five electrodes 21a to 21e and the electrode 22 are arranged so as to face each other. The five electrodes 21a to 21e are respectively connected to dielectric layers 41a to 41e (hereinafter, collectively referred to as dielectric layers 41a to 41e).
).

The electrode 21 and the electrode 22 may be such that they can rotate themselves with the column central axis as a rotation axis, or may be fixed without rotating, and may be non-conductive. When the porous body 11 and the electrode 21 and the electrode 22 move relatively, the surface of the non-conductive porous body is hardly damaged, so that the cylinder itself rotates about the center axis of the cylinder. It is preferable that the electrode be capable of being used.

The five electrodes 21a to 21e are connected to one common AC power supply 51, and the electrode 22 is grounded. In addition,
When the electrodes 21a to 21e are connected to the same AC power supply, each electrode can be arranged so that a certain electrode is in contact with an adjacent electrode. In the mode shown in FIG. 3, the five electrodes 21a to 21e are connected to one common AC power supply 51, and the same AC high voltage is applied to all of the five electrodes 21a to 21e. Different AC high voltages may be applied to the electrodes by connecting different electrodes to different AC power supplies. However, when different electrodes are connected to different AC power supplies, they need to be sufficiently separated so that the electrodes do not contact each other.

The non-conductive porous body 11 is transported by the transfer means (for example, a pair of delivery rollers 81a and 81b) provided upstream of the electrodes 21 and 22 to form the electrodes 21 and 2
2 is continuously supplied at a predetermined speed in the direction indicated by arrow A between the dielectric layer 41 and the dielectric layer 42 respectively carried on the surface of the electrode 2, and one surface of the dielectric layer is carried on the surface of the electrode 22. It comes into continuous contact with the body layer 42, and at the same time, the opposite surface is covered with five dielectric layers 41a, 41b, 41c, 41
It passes between the dielectric layer 41e and the dielectric layer 42 while sequentially contacting d and 41e. Dielectric layer 41 and dielectric layer 4
The non-conductive porous body 11 that has passed between the
And, by a transfer means (for example, a pair of delivery rollers 82a, 82b) provided downstream of the electrode 22, the transfer is continuously performed at a predetermined speed. A driving means (for example, a motor) for supplying a driving force for transporting the non-conductive porous body 11 can be connected to the above-mentioned delivery roller and / or a rotatable electrode.

The supply speed and the transfer speed of the non-conductive porous body 11 are not particularly limited, and may be a constant speed or a speed that changes periodically or irregularly.
In the embodiment shown in FIG. 3, it is preferable that the speed is constant and the speed is such that the total surface treatment time of the non-conductive porous body is 0.1 second or more. If the speed is higher than this, a sufficient total surface treatment effect cannot be obtained.

Also in the embodiment shown in FIG. 3, when the nonconductive porous body 11 passes between the dielectric layer 41 and the dielectric layer 42 while being in contact with them, the AC power supply 51 supplies the AC high voltage. Is applied, a discharge is generated in the internal space of the non-conductive porous body 11 sandwiched between the contact surface between each of the dielectric layers 41 and 42 and the non-conductive porous body 11,
Plasma is generated. As described in the embodiment shown in FIG. 2, the inner surface and the outer surface of the non-conductive porous body 11 are modified by the action of the plasma generated in the voids inside the non-conductive porous body 11.

In the embodiment shown in FIG. 3, the non-conductive porous body 1
Five electrodes 21a to 21e are provided so that any one point on the outer surface of one can contact the dielectric layer carried on the surface of the electrode a plurality of times. Five electrodes 21a-
21e, the surface of each of the dielectric layers 41a-41
e. Therefore, the non-conductive porous body 11 whose entire surface has been modified by the dielectric layer 41a carried on the surface of the electrode 21a and the dielectric layer 42 is transported in the direction shown by the arrow A, and The dielectric layer 41b is supplied between the dielectric layer 41b carried on the surface of the dielectric layer 21b and the dielectric layer 42, and the entire surface is reformed again by the dielectric layer 41b and the dielectric layer 42. 41c, the dielectric layer 41d, and the dielectric layer 41e are sequentially supplied, the entire surface is modified, and supplied from between the dielectric layer 41e and the dielectric layer 42.

Since the non-conductive porous body 11 is continuously transferred at a predetermined speed, the untreated non-conductive porous body 11
Is continuously supplied between the dielectric layer 41a and the dielectric layer 42, and the non-conductive porous body 11 whose surface has been modified is placed between the dielectric layer 41e and the dielectric layer 42. , And the total surface treatment of the non-conductive porous body 11 can be continuously performed.

The embodiment shown in FIG. 3 can be implemented in an open system or a closed system as in the embodiment shown in FIG. In the case where a gas supply pipe capable of supplying a surface treatment gas is provided, the number of gas supply pipes is not particularly limited as long as the gas can be sufficiently supplied to the processing region. One electrode and one dielectric layer may be provided, or one electrode and one dielectric layer may be provided. Further, the total surface treatment can be performed by changing the type and / or concentration of the surface treatment gas supplied to each gas supply pipe. Further, the total surface treatment may be performed by changing the type and / or concentration of the gas over time.
By changing the type and / or concentration of the surface treatment gas,
State of total surface treatment (eg, hydrophilic or hydrophobic state)
And its degree can be controlled.

Instead of the five pairs of electrodes 21a to 21e and the dielectric layers 41a to 41e shown in FIG. Still another embodiment is shown in FIG. Four fixed rollers 91a, 91b, 91c, 91
d is arranged so that the axial directions are parallel to each other, and the four fixed rollers are positioned at each vertex of the rectangle when viewed from the axial direction. The fixed roller 91a is provided near the dielectric layer 42, and the fixed roller 91b is provided downstream of the fixed roller 91a and close to the dielectric layer 42. The two fixed rollers 91c and 91d are arranged apart from the dielectric layer 42.

The endless belt-shaped aluminum vapor-deposited film 31 in which the aluminum layer 23 was formed by vapor-depositing aluminum on one surface of the polyester dielectric film layer 43 was fixed to the four fixed rollers 9.
It arrange | positions so that it may pass outside 1a, 91b, 91c, 91d. At this time, the aluminum layer 23 of the aluminum vapor-deposited film 31 is placed inside (that is, so as to be able to contact the four fixing rollers 91a, 91b, 91c, 91d), and the polyester dielectric film layer 43 is placed outside. (That is, the fixed roller 91
a and the polyester dielectric film layer 4 of the aluminum vapor-deposited film 31 passing between the fixed roller 91b and the fixed roller 91b
3 and a dielectric layer 4 carried on the surface of the cylindrical electrode 22
2 so as to face each other).

On the other hand, the electrode 22 having the dielectric layer 42 on its surface is fixed from the fixed roller 91a to the fixed roller 91a.
The endless belt-shaped aluminum vapor-deposited film 31 and the dielectric layer 42 are arranged so as to be in continuous surface contact in the entire region up to b. In this embodiment, it is not always necessary to make surface contact in the entire area between the fixed roller 91a and the fixed roller 91b, and by adjusting the distance between the endless belt-shaped aluminum vapor-deposited film 31 and the electrode 22, the fixed roller It is sufficient that at least a part of the region between the fixing roller 91b and the fixing roller 91b is in contact with the dielectric layer 42.

The electrode 22 itself can rotate around the central axis of the cylinder as a rotation axis. Also, the four fixed rollers 91a, 91b, 91c, 91d can also rotate themselves around the column central axis as a rotation axis.
1 can move in one direction (for example, the direction indicated by arrow B). The aluminum layer 23 of the aluminum deposition film 31 is connected to an AC power supply 51, and the electrode 22 is grounded. The embodiment shown in FIG. 4 connects an AC power supply 51 to the aluminum layer 23 and grounds the electrode 22.
Conversely, an AC power supply 51 may be connected to the electrode 22 and the aluminum vapor-deposited film 31 may be grounded.

The non-conductive porous body 11 is
1a and a transfer unit (for example, a pair of delivery rollers 81a and 81b) provided upstream of the electrode 22.
Layer 42 and fixed roller 91 carried on the surface of
a is continuously supplied at a predetermined speed in the direction indicated by arrow A, and one surface of the dielectric layer 4 is supported by the electrode 22.
2 and continuously passes between the dielectric layer 42 and the fixed roller 91b, while continuously contacting the opposite surface with the polyester dielectric film layer 43 at the same time. The non-conductive porous body 11 that has passed between the dielectric layer 42 and the fixed roller 91b is fixed by a transfer means (for example, a pair of sending rollers 82a and 82b) provided downstream of the fixed roller 91b and the electrode 22. Conveyed continuously at speed. A driving means (for example, a motor) for supplying a driving force for transferring the non-conductive porous body 11 can be connected to the fixed roller, the sending roller, and / or the rotatable electrode.

In the embodiment shown in FIG. 4, the total surface treatment of non-conductive porous body 11 can be continuously performed in the same manner as the embodiment shown in FIG. The embodiment shown in FIG. 4 has a larger discharge area than the embodiment shown in FIG. 3, so that the processing effect can be enhanced and the processing speed can be increased. Also, in the embodiment shown in FIG. 4, similarly to the embodiment shown in FIG. 3, it can be implemented in an open system or a closed system. In addition, as a belt-shaped laminate of an electrode layer and a dielectric layer that can be used in the embodiment shown in FIG. 4, in addition to the belt-shaped aluminum vapor-deposited film, the electrode of the belt-shaped laminate is, for example, a metal foil. , A metal sheet, or a conductive resin sheet containing a conductive substance, and the like. Examples of the dielectric material of the belt-shaped laminate include a resin film, a resin sheet, and a rubber sheet. They can be appropriately laminated and used. Naturally, a metal vapor deposition film other than aluminum can also be used.

FIG. 5 shows still another embodiment of the present invention in which a flat electrode 22 and a dielectric carrier 44a are used as one set of electrodes and a dielectric layer. Dielectric transport made of a dielectric material capable of transporting the nonconductive porous body 11 in a fixed direction (the direction indicated by arrow A) by a pair of transport drive rollers 92a and 92b arranged at a predetermined interval. Body 44a
And five columnar electrodes 21 (21a, 21a from the upstream side in the flow direction of the non-conductive porous body 11) which are arranged in parallel at predetermined intervals along the surface of the dielectric carrier 44a.
b, 21c, 21d, and 21e)
And are arranged so as to face each other. Five electrodes 21a-2
1e is covered with dielectric layers 41a to 41e (hereinafter, may be collectively referred to as dielectric layer 41).

The electrode 21 may be capable of rotating itself with its cylindrical central axis as a rotation axis, or may be fixed without rotating, and may be a non-conductive porous material. When the electrode and the electrode move relative to each other, the surface of the non-conductive porous body is hardly damaged, so that the electrode itself can rotate around the center axis of the cylinder. preferable. For the dielectric carrier 44a,
An electrode 22 made of a plate-like electrode or the like is arranged on the opposite side of the electrode 21 so as to face the electrode 21.

The five electrodes 21a to 21e are connected to one common AC power supply 51, and the electrode 22 is grounded. The mode shown in FIG. 5 connects five electrodes 21a to 21e to one common AC power supply 51 and applies the same AC high voltage to all five electrodes 21a to 21e. By connecting different electrodes to different AC power supplies, different AC high voltages can also be applied to each electrode. Also,
In the embodiment shown in FIG. 5, a common AC power supply 51 is connected to the five electrodes 21a to 21e and the electrode 22 is grounded. Conversely, an AC power supply is connected to the electrode 22 and the five electrodes 21a to 21e are connected to the ground. 21a to 21e may be grounded.

The non-conductive porous body 11 is transferred onto the dielectric transfer body 44a by transfer means (for example, a pair of delivery rollers 81a, 81b) provided upstream of the electrodes 21 and 22, and the dielectric transfer is performed. The electrode 21a by the body 44a
Is continuously supplied at a predetermined speed in the direction indicated by the arrow A between the electrode and the electrode 22, one surface of which is always in contact with the dielectric carrier 44a, and at the same time, the surface opposite to the dielectric carrier 44a is made of five dielectric materials 41a.
a, 41b, 41c, 41d, and 41e, and passes between the electrode 21e and the electrode 22 while sequentially contacting the electrodes. Electrode 21
non-conductive porous body 11 that has passed between electrode e and electrode 22
Is transported on the dielectric carrier 44a, and is continuously transported at a predetermined speed by transport means (for example, a pair of delivery rollers 82a and 82b) provided downstream of the electrodes 21 and 22. A driving means (for example, a motor) for supplying a driving force for transferring the non-conductive porous body 11 can be connected to the carrier driving roller, the delivery roller, and / or the rotatable electrode.

In the embodiment shown in FIG. 5, the total surface treatment of the non-conductive porous body 11 can be continuously performed in the same manner as in the embodiment shown in FIG. In this embodiment, by using the dielectric carrier, a normal flat electrode can be used as the inducing electrode. The embodiment shown in FIG.
In the same manner as in the embodiment shown in FIG. In the embodiment shown in FIG. 5, as a combination of an electrode and a dielectric layer, a combination of a plate-shaped electrode 22 and a dielectric carrier 44a, five sets of electrodes 21a to 21e and a dielectric layer 41a
Although the combination of No. to 41e is used, a belt-like laminate of an electrode layer and a dielectric layer shown in FIG. 4 can be used instead of one or both of them.

FIG. 6 shows an embodiment in which a belt-like laminate of an electrode layer and a dielectric layer is used instead of the combination of the flat electrode 22 and the dielectric carrier 44a shown in FIG. In the embodiment shown in FIG. 6, a three-layer laminate including a polyester dielectric film layer 44, an aluminum layer 23, and a carrier 43 is used. The three-layer laminate can be prepared by laminating an aluminum vapor-deposited film composed of the aluminum layer 23 and the polyester dielectric film layer 44 and the carrier 43. This polyester dielectric film layer 44 is brought into contact with the aluminum layer 23 on one side and simultaneously with the non-conductive porous body 11. In this embodiment, a two-layer laminate composed of the aluminum layer 23 and the polyester dielectric film layer 44 can be used, but the carrier 43 can improve the durability of the aluminum layer 23 as an electrode layer. .

As the dielectric layer, the entire surface of the dielectric layer facing the object to be processed is a dielectric layer composed of a porous dielectric layer, that is, a porous dielectric layer on the side facing the object to be processed; FIG. 7 shows another embodiment of the present invention using a dielectric layer composed of a non-porous dielectric layer on the electrode side. As shown in FIG. 7, a pair of electrodes 21 and 22 composed of a plate-like electrode or the like are arranged to face each other. The electrode 21, which is the first electrode, carries a dielectric layer 45 on the opposite surface side, and the dielectric layer 45
A non-porous dielectric layer 46 on one side and a porous dielectric layer 47 on the opposite surface side. The electrode 22, which is the second electrode,
The non-porous dielectric layer 42 is carried on the opposing surface side.

The porous dielectric layer 47 and the non-porous dielectric layer 47 are not in contact with either of the electrodes 21 and 22, but are in contact with the porous dielectric layer 47 and the non-porous dielectric layer 42 such that the outer surfaces thereof are in direct contact with each other. The non-conductive porous body 11 is disposed between the non-conductive porous body 11 and the porous dielectric layer 42. At this time, by pressing the electrode 21 and the electrode 22 with an appropriate pressure, the gap between the porous dielectric layer 47 and the non-conductive porous body 11 and between the non-conductive porous body 11 and the non-porous The surface dielectric layer 42 is brought into surface contact with the dielectric layer 42 so that substantially no space (gap) is formed. When a space is formed between the dielectric layer and the object, discharge does not occur uniformly, and a hole may be formed in the object. One electrode, for example, the electrode 21 is connected to an AC power supply 51,
The other electrode, for example, electrode 22 is grounded. Electrode 22
May be connected to an AC power supply 51 and the other electrode 21 may be grounded.

When an AC high voltage is applied from the AC power supply 51, discharge occurs not only in the internal voids of the non-conductive porous body 11 to be processed, but also in the internal voids of the porous dielectric layer 47, and plasma is generated. Is done. The plasma generated in the internal space of the non-conductive porous body 11 acts on the inner surface and the outer surface of the object to be processed, and the plasma generated in the internal space of the porous dielectric layer 47 also has Acting on the surface and the outer surface, the entire surface of the non-conductive porous body 11 is modified. At this time, a portion of the outer surface of the non-conductive porous body 11 which is in contact with the porous dielectric layer 47 is theoretically formed by plasma generated in the internal void of the porous dielectric layer 47. , Not modified. However, in practice, the point of contact is a very small area compared to the area of the outer surface, so it can be said that substantially all of the outer surface has been treated.

In the present invention, both of the dielectric layers can be replaced with a dielectric layer including a porous dielectric portion on at least a part of the surface on the facing surface side. Also, in the embodiments shown in FIGS. 2 to 6, one or both of the dielectric layers
It can be replaced with a dielectric layer including a porous dielectric portion on at least a part of the opposing surface side surface.

[0084]

EXAMPLES The present invention will be described below in more detail with reference to examples, but these examples do not limit the scope of the present invention. Example 1 As an object to be treated, a nonwoven fabric prepared by wet-making a polypropylene / polyethylene split fiber and then splitting and entangled the split fiber by a hydroentanglement treatment (thickness =
0.3 mm, porosity = 80%, average pore diameter = 9 μm, air permeability = 15.3 ml / cm ² · sec). An apparatus similar to the apparatus shown in FIG. 1 was used as the total surface treatment apparatus.
That is, the dielectric layers 41 and 42 made of a polyester film were carried on the electrodes 21 and 22 made of aluminum. The size of each electrode was 100 mm x 150 mm, and the size of the nonwoven fabric was the same. The nonwoven fabric sheet 11 was sandwiched between dielectric layers 41 and 42 made of a polyester film, and an AC power supply 51 applied a voltage of 4 KVp, a current of 25 mA, and a frequency of 3 KHz to the electrodes 21 and 22 to generate discharge. . Processing is 30 in air
Seconds. The nonwoven fabric before the treatment was very hard to get wet with water, but the nonwoven fabric after the treatment was instantly wetted to the inside when immersed in water.

Example 2 The same nonwoven fabric as in Example 1 was used as the object to be treated. An apparatus similar to the apparatus shown in FIG. 6 was used as the total surface treatment apparatus. That is, an endless sheet manufactured by laminating a polyester film 44 carrying an aluminum vapor-deposited layer 23 on one side to a chloroprene rubber sheet (dielectric carrier) 43 having a thickness of 2 mm so that the aluminum vapor-deposited surface is on the inner side, A pair of rollers 92 arranged at a distance from each other
a, 92b. On the other hand, a rotatable cylindrical metal rod 21a having a diameter of 12 mm covered with a polytetrafluoroethylene layer 41a is arranged, and further, a downstream side in the flow direction of the object to be processed is covered with a polytetrafluoroethylene layer having a similar structure. Seven cylindrical metal rods were arranged. In the apparatus shown in FIG. 6, five columnar electrodes 21a to 21e each carrying a dielectric layer 41a to 41e are arranged, but in the present embodiment, each of the circular electrodes covered with a polytetrafluoroethylene layer is used. Eight columnar metal rods were arranged. Between the eight cylindrical metal rods 21 each covered with the polytetrafluoroethylene layer 41 and the polyester film 44,
While being in contact with the polytetrafluoroethylene coating layer 41 and the polyester film 44, a feed rate of 0.1 m /
The treatment was performed in the air through a nonwoven fabric sheet 11 (width = 18 cm). The AC power supply 51 supplies a voltage of 4K.
Discharge was generated by applying an alternating current of Vp, a current of 25 mA, and a frequency of 3 KHz to perform processing. The nonwoven fabric before the treatment was very hard to get wet with water, but the nonwoven fabric after the treatment was instantly wetted to the inside when immersed in water.

Example 3 The same nonwoven fabric as in Example 1 was used as the object to be treated. As a total surface treatment device, an aluminum vapor deposition layer 23
The same apparatus as in Example 2 was used except that the polyester film 44 having the aluminum layer 23 adhered to one side in a mesh shape was used in place of the polyester film 44 carrying. Between the eight cylindrical metal rods 21 respectively coated with the polytetrafluoroethylene layer 41 and the polyester film 44, while being in contact with the polytetrafluoroethylene coating layer 41 and the polyester film 44, the feed rate is 0.1 m / In a nonwoven sheet 11 (width = 1
8 cm) in air. It should be noted that the AC power supply 51 applied an alternating current having a voltage of 4 KVp, a current of 25 mA, and a frequency of 3 KHz to generate a discharge for processing. The non-woven fabric before the treatment was very hard to get wet with water, but when the non-woven fabric after the treatment was immersed in water, only the mesh portion corresponding to the shape of the electrode made of aluminum adhered in a mesh shape was instantaneously wetted.

Example 4 A non-woven fabric (thickness = 2) was prepared by wet-making polypropylene / polyethylene split fibers and then splitting and entangled the split fibers by a hydroentanglement treatment.
(3 μm, porosity = 70%, average pore size = 7 μm) (air permeability = 5.56 ml / cm ² · sec)
Was used. An apparatus similar to the apparatus shown in FIG. 1 was used as the total surface treatment apparatus. As each of the electrodes 21 and 22, a flat stainless steel electrode (size = 150 mm × 300)
mm), and a polytetrafluoroethylene (PTFE) film (thickness = 0.2 m) is used as each of the dielectric layers 41 and 42.
m) was used. The nonwoven fabric laminate 11 is sandwiched between the two PTEF films 41 and 42, and a voltage of 6
An alternating current of KVp, a frequency of 13 KHz and an output of 800 W was applied to the electrodes to generate a discharge. The treatment was performed in the atmosphere for one minute.

The treated non-woven fabric laminate is divided into the original three non-woven fabric sheets, and the surface of the non-woven fabric sheet located outside at the time of lamination (the surface which was in contact with the PTFE film at the time of the discharge treatment) and the inside surface at the time of lamination (O / C ratio) between the number of oxygen atoms and the number of carbon atoms on the surface of the nonwoven sheet located at
Was determined by an X-ray photoelectron spectrometer (manufactured by ULVAC-PHI, model 558UP; excitation source = Mg-Kα, output = 300 W, voltage = 15 KV, extraction angle = 60 °), and the nonwoven sheet positioned outside was determined. The O / C ratio (A ₄ ) is 0.113, the O / C ratio (B ₄ ) of the non-woven sheet located inside is 0.266, and the introduction efficiency ratio (A ₄ / B ₄ ) is 0.13. 42. The measurement by the X-ray photoelectron spectrometer was performed after argon sputtering.

Example 5 Instead of using a flat stainless steel electrode (size = 150 mm × 300 mm) as the electrodes 21 and 22, convex portions (length = 2 mm, width = 2 mm) were spaced by 2 mm in the vertical and horizontal directions. Stainless steel plate (length = 1)
The procedure of Example 4 was repeated, except that 50 mm, width = 300 mm) was used. The treated nonwoven sheet
Only the region sandwiched between the convex portions of the stainless steel electrode was treated, and the other regions were not treated. The treated nonwoven fabric laminate was divided into the original three nonwoven fabric sheets, and the surface of the nonwoven fabric sheet located outside during lamination (the surface that was in contact with the PTFE film during the discharge treatment) and the inside located during lamination The O / C ratio of the treated region and the non-treated region on the surface of the nonwoven fabric sheet was determined by an X-ray photoelectron spectrometer in the same manner as in Example 4. Regarding the treated area, the O / C ratio (A ₅ ) of the nonwoven fabric located on the outside was 0.120, and the O / C ratio (B ₅ ) of the nonwoven fabric located on the inside was 0.2.
The introduction efficiency ratio (A ₅ / B ₅ ) was 0.47. In the non-treated area, the O / C ratio of the nonwoven fabric located on the outside and the O / C ratio of the nonwoven fabric located on the inside were also 0.
Met.

Example 6 As the object to be treated, the object to be treated used in Example 4, that is, a laminate in which three nonwoven fabric sheets were laminated was used. An apparatus similar to the apparatus shown in FIG. 3 was used as the total surface treatment apparatus. As a columnar electrode 22 having a large diameter carrying a dielectric layer 42, an aluminum oxide layer (thickness = 5)
00 μm), and a columnar stainless steel 22 (diameter = 217 mm, length = 500 mm) further covered with a silicone rubber layer (thickness = 2 mm) was arranged thereon. That is, in the device shown in FIG. 3, the electrode 22 carries one dielectric layer 42, but in the device used in this embodiment, the electrode 22 carries two dielectric layers 42. As a columnar electrode 21a having a small diameter carrying the dielectric layer 41a, an aluminum oxide layer 41a is formed on the surface thereof.
A cylindrical stainless steel electrode 21a (diameter = 20 mm, length = 520 mm) provided with (thickness = 200 μm) is provided, and further, an aluminum oxide layer having the same structure is supported downstream in the flow direction of the object to be processed. Nine cylindrical stainless steel electrodes were arranged. In the apparatus shown in FIG. 3, five columnar electrodes 21a to 21e carrying dielectric layers 41a to 41e are arranged. In this embodiment, an aluminum oxide layer (thickness = 200 μm) is carried. Ten cylindrical stainless steel electrodes were placed. Electrode 2
While supplying the nonwoven fabric laminated body 11 at a speed of 0.5 m / min between 1 and 22, a voltage of 6 KV
An alternating current of p, frequency 20 KHz, and output 1 KW was applied to the electrode to generate a discharge. Processing was performed in air.

The treated non-woven fabric laminate is divided into the original three non-woven fabric sheets, and the surface of the non-woven fabric sheet located outside at the time of lamination (the surface which was in contact with the silicone rubber during the discharge treatment) and the inside surface at the time of lamination (O / C ratio) between the number of oxygen atoms and the number of carbon atoms on the surface of the nonwoven sheet located at
Was determined by an X-ray photoelectron spectrometer in the same manner as in Example 4, and the O / C ratio (A
₆ ) is 0.203, and the O /
The C ratio (B ₆ ) is 0.250, and the introduction efficiency ratio (A ₆ /
B ₆ ) was 0.81.

Example 7 As the object to be processed, the object to be processed used in Example 4, that is, a laminate in which three nonwoven fabric sheets were laminated was used. As the total surface treatment apparatus, the same apparatus as the apparatus shown in FIG. 7 was used. That is, a polytetrafluoroethylene sheet (width = 200 mm, length = 250 mm, thickness = 0.1 m)
m), and a glass nonwoven sheet (width =
A stainless steel electrode (width = 160 mm, length = 210 mm) carrying 200 mm, length = 250 mm, thickness = 0.2 mm, gap height in the thickness direction ≦ 100 μm) was arranged. Polytetrafluoroethylene sheet (width = 2
A stainless steel electrode (width = 160 mm, length = 210 mm) carrying 00 mm, length = 250 mm, thickness = 0.1 mm) was arranged. The nonwoven fabric laminate 11 is sandwiched between the electrodes 21 and 22, and a voltage 6
An alternating current of KVp, a frequency of 13 KHz and an output of 800 W was applied to the electrodes to generate a discharge. The treatment was performed in the atmosphere for one minute.

The treated non-woven fabric laminate is divided into the original three non-woven fabric sheets, and the surface of the non-woven fabric sheet located outside at the time of lamination (the surface which was in contact with the glass non-woven fabric sheet at the time of electric discharge treatment) and at the time of lamination The ratio of the number of oxygen atoms / carbon atoms on the surface of the nonwoven fabric sheet located inside (O / C ratio)
Was determined by an X-ray photoelectron spectrometer in the same manner as in Example 4, and the O / C ratio (A
₇ ) is 0.138, and the O /
The C ratio (B ₇ ) is 0.255, and the introduction efficiency ratio (A ₇ /
B ₇ ) was 0.54.

Example 8 As the object to be processed, a melt-blown nonwoven fabric made of polypropylene (area density = 78 g / m ² , thickness = 0.85 m)
m, average fiber diameter = 1.8 μm, size = 100 mm × 1
50 mm, porosity 90%, average pore diameter of internal voids 7 μm,
(Air permeability = 7 ml / cm ² · sec) was used. An apparatus similar to the apparatus shown in FIG. 1 was used as the total surface treatment apparatus. A flat aluminum electrode (size = 100 mm × 150 mm) is used as each of the electrodes 21 and 22, a glass plate (thickness = 1 mm) is used as the dielectric layer 41, and a polyester film (thickness = 50 μm) is used as the dielectric layer 42. Each was used. The nonwoven fabric sheet 11 is interposed between the dielectric layers 41 and 42.
From the pulse power supply 51 [voltage pulse width (half width) = 1 microsecond, rise time = approximately 0.4 microsecond, frequency 15 kHz, voltage peak value 8 KVp, output 4
00W] was applied to the electrode to generate a discharge. The treatment was performed in the atmosphere for 30 seconds. The hydrophilic treatment could be performed without making a hole in the object.

Example 9 The same nonwoven fabric as in Example 1 was used as the object to be treated. The discharge treatment was performed using an apparatus similar to the apparatus shown in FIG. As the electrodes 21 and 22, flat stainless steel electrodes (width = 150 mm, length = 300 mm) were used.
As the dielectric layers 41 and 42, a polytetrafluoroethylene sheet (width 180 mm, length = 350 mm, thickness =
0.1 mm). Impulse power supply 51 (frequency =
(13 KHz), an alternating current of 800 W was applied for 1 minute to perform a discharge treatment in the air, and then the nonwoven fabric sheet was washed with water and dried. Cylindrical paste-paste sealed nickel-metal hydride battery (battery capacity = 1700 mAh) using the obtained nonwoven fabric sheet as a separator for an alkaline battery
Was prepared. A positive electrode filled with nickel hydroxide in a foamed nickel support, a negative electrode filled with a hydrogen storage alloy (mesh metal MmNi ₅ type) in a foamed nickel support, and 7.2 N potassium hydroxide /
5 g of a 1.0 N lithium hydroxide aqueous solution was used. The nonwoven fabric used as a separator had good electrolyte absorbability and was excellent in workability in battery production.

In a thermostat at 20 ° C., the battery was
Charge for 4 hours with mAh (0.3C, 1 for theoretical capacity)
20%), and a charge / discharge operation consisting of discharging at 510 mAh until the final voltage reached 1 V was defined as one cycle, and five cycles of charge / discharge for battery activation were performed. Using a battery that was subjected to 5 cycles of charge / discharge for battery activation, the battery was charged at 1700 mAh for 1.5 hours (1.0 C, 150% of the theoretical capacity) in a thermostat at 20 ° C. A life test was performed in which a charge / discharge operation consisting of discharging at 1700 mAh was performed as one cycle. FIG. 8 shows the battery discharge capacity after each cycle, and FIG. 9 shows the average charge voltage in each cycle. As is clear from FIG. 8, no decrease in the discharge capacity was observed even after 450 cycles of the charge / discharge operation. Further, as is apparent from FIG. 9, since the rise in the charging voltage was small, the rise in the internal resistance was small (that is, it is considered that the liquid drainage of the separator was small. The nonwoven fabric treated by the method of the present invention was used as the separator. Thereby, a battery having a long cycle life can be manufactured.

[0097]

According to the present invention, not only the outer surface of the porous material but also the surface of the void inside the porous material can be treated, and the object to be treated due to spark discharge or the like is hardly damaged. Can be used, and it is possible to continuously perform the total surface treatment of the non-conductive porous body. Further, according to the present invention, it is not necessary to use a rare gas or the like, and an object to be processed can be processed in the atmosphere of 1 atm. Further, according to the present invention, since the nonconductive porous body is substantially treated only on the entire surface of the portion sandwiched between the pair of electrodes, one of the electrodes is a plate-like electrode and the other electrode is Is formed into an electrode having a desired shape, for example, a reticulated electrode or a linear electrode, whereby the surface of the non-conductive porous body can be selectively treated in the same pattern as the desired shape. INDUSTRIAL APPLICABILITY The present invention can be applied to the treatment of a fibrous porous body made of a non-conductive organic material, and particularly to the treatment of a nonwoven fabric sheet that can be used as a separator for an alkaline battery.

[Brief description of the drawings]

FIG. 1 is a sectional view schematically showing a basic principle of the present invention.

FIG. 2 is a perspective view schematically illustrating one embodiment of the present invention.

FIG. 3 is a cross-sectional view schematically illustrating another embodiment of the present invention.

FIG. 4 is a cross-sectional view schematically showing still another embodiment of the present invention.

FIG. 5 is a cross-sectional view schematically showing still another embodiment of the present invention.

FIG. 6 is a cross-sectional view schematically showing still another embodiment of the present invention.

FIG. 7 is a sectional view schematically showing still another embodiment of the present invention.

FIG. 8 is a graph showing a cycle change of a battery discharge capacity in a life test of a nickel-metal hydride battery using an alkaline battery separator manufactured according to the present invention.

FIG. 9 is a graph showing a cycle change of an average charging voltage in a life test of a nickel-metal hydride battery using an alkaline battery separator manufactured according to the present invention.

FIG. 10 is an explanatory diagram showing a shape of a pulse wave that can be used in the present invention.

[Explanation of symbols]

11. non-conductive porous body; 21, 22, electrodes 23
..Aluminum layer; 31.aluminum vapor-deposited film; 41,42..non-porous dielectric layer; 43..carrier; 44..polyester dielectric film layer; 44a
..Dielectric carrier; 45. Dielectric layer; 46. Non-porous dielectric layer; 47. Porous dielectric layer; 51 .. AC power supply; 81a, 81b, 82a, 82b. 91a, 91b, 91c, 91d fixed roller; 92a, 92b roller

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazuya Sato 7-chome, Kitatone, Sowa-cho, Sarushima-gun, Ibaraki Prefecture Within Japan Vilene Co., Ltd.

Claims (3)

[Claims] 1. A dielectric layer is provided on each opposing surface side, and between a pair of electrodes arranged opposite to each other, the pair of electrodes do not directly contact each other, but each of the derivative layers and the outer surface A non-conductive porous body is disposed so that the non-conductive body is in direct contact with the non-conductive porous body, and a low-frequency AC voltage having a frequency of 0.1 KHz to 100 KHz is applied between the two electrodes. A method for treating the entire surface of a non-conductive porous body, characterized in that a discharge is generated in internal voids of the conductive porous body. 2. A pair of electrodes arranged opposite to each other,
(2) a dielectric layer disposed on each of the opposing surfaces of the electrodes; and (3) means electrically connected to the two electrodes so as to apply an AC voltage between the two electrodes. An apparatus for treating the entire surface of a non-conductive porous body. 3. A modified non-conductive porous body in which a functional group is introduced into at least a part of the total surface of the non-conductive porous body, wherein the functional group introduction efficiency on the inner surface where the functional group is introduced ( The introduction efficiency ratio (A /
B) is less than 1, wherein the nonconductive porous modified material is characterized in that: