JP2000301711A - Surface treatment method, production of ink jet recording medium and ink jet recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the image receiving capacity of an ink image receiving layer to a large extent and to also eliminate the generation of contamination and positional shift by applying plasma treatment to a support provided with a surface layer so as to have a gap structure. SOLUTION: A long support 1 is continuously fed to the treatment part 2 formed between a pair of electrodes 3, 4 constituted of metal electrodes 3A, 4A and solid dielectrics 3B, 4B to be brought to an atmosphere open state. The metal electrodes 3A, 4A are generally composed of a conductive material such as silver, gold, copper, stainless steel or aluminum to be bonded to the solid dielectrics 3B, 4B. As the solid dielectrics 3B, 4B, sintered ceramics high in heat resistance may be also used. A high frequency power supply 5 is connected to one electrode 3 while the other electrode 4 is grounded by an earth 6 and an electric field is pulsated to be applied across a pair of the opposed electrodes 3, 4 to generate discharge plasma which is, in turn, used in surface treatment to develop sufficient surface treatment function even in air.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate having a void structure and a technique for manufacturing the same, and more particularly, to a recording medium effective for forming a high-quality image using an ink jet recording method, and a technique for manufacturing the same. Things. More specifically, the present invention relates to a technique for improving the ink receiving performance by subjecting a substrate having a support such as paper or a plastic film to a discharge plasma treatment at or near atmospheric pressure.

[0002]

2. Description of the Related Art The ink jet system in a broad sense includes, for example, a bubble jet system, a piezo electrode system, and the like. It is widely sold for consumer use and is under active development.

As is well known, the ink jet method is a technique in which an image is formed by ejecting ink from fine holes and colliding with a recording medium. In the present specification, “collision”, “arrival”, or “landing” is used to express the behavior when an ink droplet reaches an image receiving surface of a recording medium to form an image.
Is used synonymously. Further, when forming an image by an ink jet method, particularly when forming image data instead of character data, the recording medium causes ink ejected from an ink droplet ejecting device (also called a printer head) to land on a correct position, It is required to absorb light quickly and sufficiently so that there is no blur in the surface direction of the image receiving surface.

[0004] Plain paper is often used as such an ink jet recording medium. However, the development of ink has made it possible to print on cloth and the like. In addition, along with finer and multi-colored ink, or higher image quality by precise position control of the print head,
Inkjet systems have also begun to be introduced for printing small numbers of copies.

[0005] Recently, ink jet printers capable of printing at a high resolution of 1200 dpi or more have been sold. Such models not only perform fine printing but also have a high-speed printing function.

[0006] That is, the ink jet printer is required to have high image quality and high speed. The research has been conducted not only on the printer but also on the software for driving the printer, and also on the ink and the recording medium. For example, as of January 1999, some of the current consumer products employ particles as small as 6 pl (6 liters per trillion).

At the same time, special printing paper for contributing to higher image quality of the recording medium itself has been proposed, and the demand for the special recording paper has been increasing.

As described above, the ink jet system is a system in which ink is ejected onto a recording medium and collides with the recording medium. Therefore, when the recording medium is liable to bleed the ink, the sharpness of an image is reduced. Has low affinity,
If the ink is repelled, image formation becomes impossible.

[0009] Special recording papers proposed or sold so far include organic or inorganic (silica) materials such as gelatin and PVA on the surface of paper or plastic film (PET, PE, PP, PEN, etc.) as a base material. ) Is formed by applying a functional layer containing (i.e., the same) as a main component, thereby improving the image receiving performance of the ink.

[0010]

However, it is extremely difficult to control surface properties such as "wetting" inside the voids only by a coating method. In addition, since there is a difference in the type, quality, and performance of each ink from each manufacturer and product, it is difficult to determine the prescription of a universal coating layer, taking into account the compatibility with the ink. It is not easy to control the ink receiving performance by changing it appropriately.

There is also a problem of adhesion and transfer after printing.
This is a phenomenon where the printed ink works just like an adhesive. Specifically, when the printed matter is closely adhered and overlapped, the image receiving surface sticks to other paper surface etc.If this is forcibly peeled, the printed image will be transferred or severely peeled or torn. is there.

[0012] Further, the ink ejection pitch (time interval) is shortened due to the improvement of the printing speed.
An outbreak problem is emerging. This is because, when the speed at which the ink droplets landed on the image receiving surface penetrates into the surface from the image receiving surface is low, as shown in FIG. Is attracted and deviates from the originally intended position. As a result, there is a place where there should be no ink where it should be (ink drops do not land at a target position), and the chromaticity is significantly deteriorated.

[0013] Further, an adverse effect is also brought about by improving the image receiving performance. The first is the problem of "dirt". For example, when the image receiving surface is touched with a finger, dirt and fingerprints are attached, and the image receiving layer swells due to moisture absorption, and the image is disturbed. The second is an increase in “lateral bleeding”.
This is a problem in that the ink that has landed on the image receiving surface spreads in the surface direction, mixes with the ink that has landed adjacently, and causes unnecessary color mixing.

Although this is a problem that becomes more apparent as the image receiving performance is improved, no effective solution has been found at present, and each company is developing a recording medium by groping. For example, in the case of the technology described in Japanese Patent Application Laid-Open No. Hei 10-193783, a technique of forming an image receiving layer having a dense structure and making the surface hydrophilic has been proposed. It only promotes the spread in the direction, and conversely reduces the quality.

Therefore, the inventors of the present application have studied and found that the ejected ink easily permeates the image receiving surface, in other words, the water absorbing capacity (capacity, speed) in the thickness direction (also referred to as the depth direction) of the recording medium. ) Is an important element, specifically, hydrophilizing the inside of the void structure,
It has been found that by improving the water absorption efficiency and the water absorption speed of the image receiving surface, interference between ink droplets (also referred to as dots) that land adjacently can be suppressed, and the recording performance of the ink jet system can be improved.

Further, it has been found that, contrary to the hydrophilicity, by making the outermost surface water-repellent, it is effective as a measure against stains on the paper surface.

It has been found that an ink jet recording medium that is very effective has a high image receiving ability when the surface layer is made hydrophilic and only the surface is made water-repellent.

However, as described above, no effective means has been found for changing the film physical properties of the coating layer to improve image receiving performance, which is inexpensive, easy to switch in accordance with the performance of the ink, and effective. "Dirt" associated with improved image receiving performance
And the increase of “horizontal bleeding” are also issues that conflict with the image receiving performance, and no solution has been proposed that can achieve both.

Various techniques have been proposed for modifying the surface properties of the support. For example, when performing coating, surface treatments for improving adhesion (with a film) include corona discharge treatment, vacuum glow discharge treatment, flame treatment, and recently proposed atmospheric pressure plasma surface treatment technology. Particularly, the last atmospheric pressure plasma treatment is described in JP-A-3-143930 and JP-A-4-745.
No. 25, No. 2-48626, No. 6-7230
No. 8, Japanese Patent Publication No. 7-48480, and the like.
Discharge is performed in an atmosphere containing argon gas or helium gas as a main component to generate plasma, and the plasma is used to perform a surface treatment on the support.

The inventors of the present invention have confirmed that such a surface modification technique can significantly improve the image receiving performance of the ink image receiving layer, and can also solve the problem of "dirt" and the occurrence of "position shift". Thus, the present invention has been accomplished.

However, the plasma processing has problems that the conditions for generating plasma are severe and that the control thereof is difficult.

Further, in the plasma treatment, the moisture in the reaction gas contributes to the addition of the functional group. However, when the proportion of the water is increased to improve the efficiency of the application, the output of the power supply is reduced and the discharge becomes unstable. there were.

On the other hand, as a result of the study, it was found out that conditions for controlling the plasma in the plasma treatment were very effective in improving the ink receiving layer.

That is, a first object of the present invention is to improve the image receiving performance of a recording medium used in an ink jet system by using a surface modification method.

A second object of the present invention is to provide a recording medium used in an ink jet system using a surface modification method.
The problem is to reduce and eliminate the problem.

A third object of the present invention is to reduce or eliminate the occurrence of "horizontal bleeding" of a recording medium used in an ink jet system by using a surface modification method.

A fourth object of the present invention is to make suitable conditions for generating plasma used in the surface modification method.

[0028]

Means for Solving the Problems (1) A method for treating the surface of a support, wherein a plasma treatment is performed on the support having a surface layer having a void structure. (2) The surface treatment method according to (1), wherein a functional group is provided to the support by the plasma treatment. (3) The surface treatment method according to (1), wherein the gap is roughened by the plasma treatment. (4) The surface treatment method according to (1), wherein the plasma treatment is generated in an atmosphere mainly containing an inert gas. (5) The surface treatment method according to (1), wherein the surface layer having voids is a surface layer of the support. (6) The surface treatment method according to (1), wherein the surface layer having the voids is a coating layer provided on the support. (7) The inside of the gap and / or
Alternatively, the surface treatment method according to (1), wherein the surface layer is made hydrophilic. (8) The surface treatment method according to (1), wherein the water repellency of at least a surface layer of the gap is improved by the plasma treatment. (9) The surface treatment method according to (7), wherein the plasma treatment is performed by corona discharge. (10) The surface treatment method according to (7), wherein the plasma treatment is performed by a flame. (11) The surface treatment method according to (7) or (8), wherein the plasma treatment is performed by glow discharge under vacuum or under atmospheric pressure or a pressure near atmospheric pressure. (12) The atmosphere in which the plasma processing is performed is absolute humidity,
(1) The treatment method according to (1), wherein the amount is not less than 0.005 [kg-steam / kg-dry gas]. (13) The surface treatment method according to (1), wherein a water-repellent treatment is performed after the hydrophilic treatment is performed by the plasma treatment. (14) The surface treatment method according to (1), wherein the support is present in a gas atmosphere for performing a plasma treatment, and the plasma treatment is performed after the gap structure is filled with the gas. . (15) The surface treatment method according to (1), wherein the support is an ink jet recording medium. (16) An ink jet recording medium manufactured by using the surface treatment method of (1) to (14). (17) A method for treating a surface of a support, comprising performing plasma treatment on a support having a surface layer having a void structure using plasma generated in a pulsed electric field. (18) The absolute humidity of the atmosphere in which the plasma is generated is
(17) The surface treatment method according to (17), wherein the amount is not less than 0.005 [kg-steam / kg-dry gas]. (19) The surface treatment method according to (17), wherein a functional group is imparted to the support by the plasma treatment. (20) The surface treatment method according to (17), wherein the gap is roughened by the plasma treatment. (21) The surface treatment method according to (17), wherein the surface layer having voids is a surface layer of the support. (22) The surface treatment method according to (17), wherein the surface layer having voids is a coating layer provided on the support. (23) The surface treatment method according to (17), wherein the inside and / or the surface layer of the void is made hydrophilic by the surface modification. (24) The surface treatment method according to (17), wherein at least a surface layer of the void is made water-repellent by the surface modification. (25) The surface treatment method according to (17), wherein the plasma treatment is performed by glow discharge. (26) The surface treatment method according to (17), wherein the plasma treatment is performed under an atmospheric pressure or a pressure near the atmospheric pressure. (27) The surface treatment method according to (17), wherein the plasma treatment is performed in the atmosphere. (28) The plasma processing is performed in an atmosphere containing 30% by volume or more of a reaction gas.
7) The surface treatment method. (29) The atmosphere for performing the plasma processing is an absolute humidity,
(17) The treatment method according to (17), wherein the amount is not less than 0.005 [kg-steam / kg-dry gas]. (30) The surface treatment method according to (17), wherein after performing the hydrophilic treatment by the plasma treatment, a water-repellent treatment is performed. (31) The surface treatment method according to (17), wherein the support is an ink jet recording medium. (32) An inkjet recording medium manufactured by using the surface treatment method according to any one of (17) to (30). (33) Pretreating the continuously transported support,
A method for producing an ink jet recording medium, comprising: applying a coating liquid to the support, drying the coating to form a functional layer, and performing post-processing on the functional layer in a continuous process. (34) The method for manufacturing an ink jet recording medium according to (33), wherein the pretreatment is a plasma treatment. (35) The method for producing an ink jet recording medium according to (33), wherein the pretreatment is a corona discharge treatment. (36) The method for producing an ink jet recording medium according to (33), wherein the post-treatment is a plasma treatment. (37) The plasma processing is performed by using plasma generated in a pulsed electric field (3).
3) The method for producing an ink jet recording medium. (38) The absolute humidity of the atmosphere in which the plasma is generated is
(33) The surface treatment method according to (33), wherein the amount is not less than 0.005 [kg-steam / kg-dry gas].

In other words, the present invention can be described by expressing the following expressions. (1) A method for modifying a base material provided with a void layer having a void structure on a support, wherein the substrate is subjected to a plasma treatment. (2) The surface treatment method according to (1), wherein a functional group is provided to the substrate by the plasma treatment. (3) The method for modifying a base material according to (1), wherein the gap is roughened by the plasma treatment. (4) The void layer contains particles, and the particles are roughened by the plasma treatment. (5) The plasma treatment is generated in an atmosphere mainly composed of an inert gas. (6) The gap layer is provided at a position farthest from the support. (7) The gap layer is a layer provided by coating on the support. (8) By the plasma treatment, at least one of the inside of the gap layer and the surface layer of the gap layer is hydrophilized. (9) The surface of the void layer is made water-repellent by the plasma treatment. (10) The plasma processing is performed by corona discharge. (11) The plasma processing is performed by glow discharge under vacuum or under or near atmospheric pressure. (12) After performing the hydrophilic treatment by the plasma treatment, a water-repellent treatment is performed. (13) Before the step of performing the plasma treatment, the base material is present in a gas atmosphere, and the gas is introduced into the void structure. (14) The base material is an inkjet paper. (15) The plasma treatment is performed using plasma generated in a pulsed electric field. (16) The step of performing the plasma treatment includes a step of bringing a gas into a plasma state and a step of introducing the gas in a plasma state into the void structure. (17) before the step of performing the plasma processing, the method includes a step of introducing a gas into the void structure, wherein the plasma processing discharges the base material into which the gas has been introduced into the void structure. It is performed by. (18) In the method for producing an ink jet paper having a gap layer having a gap structure on a support, the gap layer is subjected to a plasma treatment. (19) In the method of (18), a void layer is formed on the support before performing the plasma treatment.

[0030]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.

FIG. 15 is a cross-sectional view of the substrate before the plasma processing according to the present embodiment. An undercoat layer such as a gelatin layer is provided on a support, and an image receiving layer (functional layer) having voids is provided thereon.

In the present specification, the uppermost part of the image receiving layer is referred to as “surface layer”, and the surface of the particles inside the void layer is referred to as “surface”.

As the support of the substrate having a void structure used in the present invention, a film and paper selected from polyethylene terephthalate, polyethylene naphthalate, polyethylene and polypropylene are used.

In particular, when an ink jet recording medium is manufactured, for example, a thin gelatin film is coated on a support having a PP layer formed on both sides of a pulp base paper, and silica and PVA are mainly coated thereon. The recording medium in which the image receiving layer (functional layer) is formed by applying the dispersed aqueous coating liquid in a single layer or a multi-layer, and drying, and performing plasma treatment on the image receiving layer, thereby improving the image receiving performance. With respect to the layer constitution, a coating liquid having the same components may be applied in a multi-layer coating, or the composition, film thickness and number of layers of the coating liquid can be selected as necessary. The image receiving layer is preferably formed by coating, but may be formed by another method.

With respect to coating for forming an image receiving layer, techniques have been proposed for application to the production of photosensitive materials and the like, and these techniques can be applied. For example, a suitable method such as a fountain type, an extrusion type, a wire bar type, a blade type, a slide hopper type, and a curtain type can be appropriately selected. Especially when applying a multilayer thin film on a wide support at high speed,
It is preferable to use a slide hopper type or curtain type technology.

The image receiving layer is composed of silica and PVA. Specifically, a PVA film is formed on silica particles, and a large number of these particles are aggregated in a state having voids. Then, when the ink droplets of the ink jet reach the image receiving layer, the ink penetrates into the gap to form an image.

When the image receiving layer is subjected to a plasma treatment so as to impart hydrophilicity, the PVA coating on the silica surface has a large number of polar functional groups (amino groups, carboxyl groups, hydroxyl groups, carbonyl groups, etc.). As a result, the water absorption efficiency and water absorption speed of the ink are improved. Furthermore, the surface of the PVA coating on the silica surface inside the image receiving layer is finely roughened by etching (anchor effect), so that the surface area of voids formed between the particles increases, which is also a factor in water absorption efficiency and water absorption rate. Contribute to improvement. Furthermore, contrary to hydrophilization,
By subjecting the outermost surface (surface layer) of the image receiving layer to a water-repellent treatment,
Spreading of ink droplets in the surface direction of the image receiving surface (also referred to as the lateral direction) can be suppressed, and “lateral bleeding” can be prevented as shown in FIG.

As described above, regarding the properties to be imparted and the degree thereof (degree of contribution of plasma processing), electric field strength, plasma processing gas conditions (reaction gas concentration, gas enclosing conditions, atmospheric pressure, etc.), discharge conditions, and humidity conditions to be described later It can be controlled as appropriate by changing the parameters. That is, the degree of imparting hydrophilicity and water repellency can be freely changed as needed. More specifically, the depth and thickness of the image receiving layer having improved hydrophilicity and water repellency, the degree of improvement in hydrophilicity and water repellency, and the like can be freely controlled in the thickness range of Å to sub μm. For this reason, it can respond to a variety of market demands and is suitable for variety switching and multi-product small-lot production.

The specific description of the hydrophilic treatment is as follows.
In the case where the processing is performed on the voids inside the image receiving layer as a target, it is effective to sufficiently fill the voids with the reaction gas necessary for discharge, and therefore it is preferable to lengthen the time for purging (filling) the gas. This may be a method of retaining the support in the gas chamber (also referred to as off-line purging) or a method of performing a gas purging step online. In a method other than the gas purge, it is preferable to employ a gas of a small molecule as a reaction gas. When a gas having a small molecular size is used, the reaction gas easily enters the void in a short time, and it is particularly preferable to use He or the like. The reaction gas sealed in the gap does not easily go out and is consumed in the plasma treatment, so that the effect of modifying the surface of the gap, that is, the effect of modifying the surface of the particles is enhanced.

The water-repellent treatment will be described specifically.
By using a fluorine-containing compound gas as the processing gas, a fluorine-containing group can be formed on the substrate surface (surface layer) to lower the surface energy and obtain a water-repellent surface. Examples of the fluorine element-containing compound include fluorine-carbon compounds such as carbon tetrafluoride, carbon hexafluoride, propylene hexafluoride, and cyclobutane octafluoride; halogen-carbon compounds such as carbon trifluoride and carbon trifluoride; And fluorine-sulfur compounds such as sulfur. From the viewpoint of safety, it is preferable to use carbon tetrafluoride, carbon hexafluoride, propylene hexafluoride and cyclobutane octafluoride, which do not generate hydrogen fluoride which is a harmful gas.

Next, a process using plasma generated by a pulsed electric field will be described. Plasma processing is
Plasma is generated mainly by generating an electric field in the reaction gas. By converting this electric field into a pulse-type electric field, the plasma intensity is particularly strong and uniform, so the reforming effect on the processed material Is big.

A discharge plasma is generated by applying a pulsed electric field to the electrodes arranged in the processing chamber. The pulse waveform is, for example, an example shown in FIG. 2, but is not limited thereto. The pulse waveforms shown in FIGS. 1A to 1D of Japanese Unexamined Patent Publication No. 10-130851 may be used. In FIG. 2, the vertical axis represents the pulse voltage, and the horizontal axis represents time.

When the discharge plasma generated by applying such a pulsed electric field is used for surface treatment, it has a sufficient surface treatment function even in air.

The frequency of the pulse electric field is 5 to 100 kHz.
The range of z is preferred.

The time for applying one pulse electric field is 1 μm.
It is preferably s to 1000 μs. The time during which one pulse electric field is applied is the time during which a pulse having one pulse waveform in FIG. 2 is applied.

The magnitude of the voltage applied to the counter electrode is not particularly limited, but the electric field strength when applied to the electrode is 1 to 1
It is preferable to set the range to be 00 kV / cm.

Next, a technique for controlling the humidity of the atmosphere to change the degree of plasma generation and the processing intensity will be described.

As described above, in the plasma treatment, the moisture (H ₂ O) in the air contributes as a reaction gas, but if this ratio is large, the output of the conventional power supply decreases or the discharge becomes unstable (the plasma treatment becomes unstable). (Uniformity).

On the other hand, by generating a plasma using a pulsed electric field, discharge (uniform plasma generation) in an atmosphere rich in H ₂ O becomes possible.
The above problems can be solved.

In particular, H ₂ O is very effective because it produces less ozone, which is a by-product of plasma generation, and has a surface modification effect, as compared with O 2 and CO ₂ .

The moisture content in the atmosphere is preferably at least 0.005 [kg-steam / kg-dry gas] in absolute humidity, more preferably 0.009 [kg-steam / kg-dry gas]. Above, more preferably 0.012
It is more than [kg-steam / kg-dry gas].

The absolute humidity can be determined with reference to a constant temperature / humidity chart (also called a wetness chart).

Further, "0.005 [kg-steam / kg-dry gas] or more" means, for example, (1) at a temperature of 20 ° C.
(2) When the temperature is 25 ° C., the relative humidity is 25% or more; (3) When the temperature is 30 ° C., the relative humidity is 19
% Or more.

Next, a technique for performing continuous processing will be described.

The base material to be subjected to the surface modification treatment is formed by coating the image receiving layer. However, by performing the pre-treatment, and then continuously performing the coating and the post-treatment, it is possible to eliminate waste in an integrated process. An inkjet recording medium that has been subjected to a surface treatment can be obtained.

More specifically, as shown in FIG. 12, the pre-treatment is performed while first passing the continuously transported support through the pre-treatment step.

The pretreatment step is a step for facilitating the transfer of the coating solution to the support. Specifically, it is preferable to use a plasma treatment, a corona discharge treatment or the like. Alternatively, gelatin or the like may be applied to form a gelatin layer.

After the pretreatment step, the support is transported to the coating step. In the coating step, a coating solution for the image receiving layer prepared in advance is applied to the support. As a coating method, a suitable method such as a curtain method and a slide hopper method can be applied.

In this coating step, the surface of the support is modified in the preceding pretreatment step, so that the liquid-adhering property (also referred to as film-adhering property) is improved, and high-speed and thin-film coating becomes possible. ing.

The next transported support enters a drying step.
In this step, the conditions of the dryer (temperature of hot air, blowout amount, shape, size, position of blowout port, etc.) are set so that the applied coating solution can be rapidly dried.

The support (namely, the substrate) on which the ink image receiving layer has been formed through the drying step is transported to the post-processing step.
In this post-processing step, the above-described surface modification of the voids (that is, the surface modification of the particles forming the voids of the image receiving layer) is performed, and the ink image receiving performance is improved. In this post-processing step, as described above, the atmosphere, humidity conditions, reaction gas, and the like for generating plasma can be appropriately selected and applied.

In the post-processing step, a plurality of plasma processing steps may be provided. For example, a hydrophilic treatment is first performed to increase the water absorbing capacity of the image receiving layer, and then a water repellent treatment is mainly performed on the surface layer of the image receiving layer to prevent surface contamination and to prevent lateral (plane) direction.
You can also take measures to prevent bleeding.

As described above, the ink jet recording medium can be manufactured efficiently by the continuous and continuous processing.

Although not shown in this figure, a setting step may be provided before the coating step and the drying step. When the coating liquid applied in the coating step is water-based and contains a binder, when directly entering the drying step after coating, the coating film is disturbed by the drying air,
The coating is once hardened by cold air and then dried.

Hereinafter, a specific processing apparatus will be described.

FIG. 1 is a schematic configuration diagram for explaining the first method and apparatus.

In FIG. 1, reference numeral 1 denotes a long support which is continuously conveyed, reference numeral 2 denotes a processing unit which continuously performs plasma processing under atmospheric pressure or a pressure close thereto, and reference numerals 3 and 4 denote a pair of processing units. Electrodes.

The processing section 2 is open to the atmosphere in order to carry out the first method, does not constitute a processing chamber, and a gap formed between the pair of electrodes 3 and 4 serves as a processing section. Constitute.

The processing section 2 only needs to have air that exists naturally under the atmospheric pressure or a pressure close to the atmospheric pressure. However, a shield plate for adding or regulating the flow of air, or for rectifying the flow of air is used. A nip roll can be added.
Further, a disposal duct for discharging and discarding generated by-products (for example, gas) can be provided.

When the surface treatment is carried out in the treatment section 2, the coating property on the support surface and the coating property of the coating film are improved, the functional group imparting property is improved, and optical, electrical, mechanical, etc. From the viewpoint of improving the applicability, a surface having the above function is formed, and it is preferable to apply immediately after the surface treatment in order to prevent the treated surface from deteriorating with time.

In the illustrated example, the pair of electrodes 3 and 4 are composed of metal electrodes 3A and 4A and solid dielectrics 3B and 4B, and the metal electrodes 3A and 4A are energized by silver, gold, copper, stainless steel, aluminum, or the like. Generally, a possible material is attached to the solid dielectrics 3B and 4B, but the solid dielectrics 3B and 4B can be attached by plating, vapor deposition, coating, thermal spraying, or the like.

As the solid dielectrics 3B and 4B, it is preferable to use a sintered ceramic obtained by sintering a highly airtight and high heat resistant ceramic. As the material of the sintered ceramics, for example, alumina, zirconia, silicon nitride,
It is a silicon carbide ceramic. The thickness of the alumina ceramic is preferably about 1 mm. The volume resistivity is preferably 10 ⁸ Ω · cm or more.

When an alumina-based sintered ceramic is used as the sintered ceramic, it is preferable to use an alumina-based sintered ceramic having a purity of 99.6% or more from the viewpoint of increasing the durability of the electrode. Regarding the alumina-based sintered ceramics having a purity of 99.6% or more, the invention (Japanese Patent Application No. 9-369413) previously proposed by the present applicant can be referred to.

In the method of manufacturing an electrode using this sintered ceramic, a sintered ceramic having high heat resistance is sintered to produce a sintered ceramic, and the sintered ceramic is plated, vapor-deposited, sprayed or coated to form a metal. Attach electrodes.

As the solid dielectrics 3B and 4B, a low-temperature glass lining described in Japanese Patent Application No. 10-300984 can be used.

The metal electrodes 3A and 4A may be entirely covered with the solid dielectrics 3B and 4B, or may be only partially covered.

The gap between the electrodes is equal to that of the opposing solid dielectric 3B.
And the distance between the surfaces of 4B is preferably in the range of 0.3 to 10 mm, more preferably in the range of 1 to 10 mm, and still more preferably 3 mm. In FIG. 1, a pair of electrodes 3,
Although a flat plate electrode is used as shown in FIG. 4, one or both of the electrodes may be a cylindrical electrode or a roll electrode, or a gas flow type curved electrode may be used. Details of such an electrode will be described in the description of the second method and apparatus.

One electrode 3 of the pair of electrodes 3 and 4
Is connected to a high-frequency power supply 5 and the other electrode 4 is grounded by an earth 6, so that a pulsed electric field can be applied between the pair of electrodes 3 and 4.

In the first method, it is preferable that before the surface treatment, the substrate surface (surface layer) is subjected to a static elimination treatment in advance and dust is further removed because the uniformity of the surface treatment is further improved. As the static elimination means, in addition to a normal blower type and a contact type, a static eliminator in which a plurality of positive and negative ion generating static elimination electrodes and an ion suction electrode are opposed to sandwich the base material, and then a positive and negative DC type static elimination device are provided. It is also preferable to use a high-density static elimination system (JP-A-7-263173). At this time, the charge amount of the support is preferably ± 500 V or less. As the dust removing means after the static elimination process, a non-contact type jet-type decompression type dust removing device (JP-A-7-60211)
No.) is preferred, but is not limited thereto.

In the first method and apparatus according to the present invention, the pressure under the atmospheric pressure means a pressure of 100 to 800 Torr, preferably 700 to 780 Torr.

In this method, a discharge plasma is generated by applying a pulsed electric field between the opposing electrodes. The pulse waveform is, for example, an example shown in FIG. 2, but is not limited thereto. JP-A-10-13085
The pulse waveforms shown in FIGS. 1A to 1D of Japanese Patent Publication No. 1 may be used. In FIG. 2, the vertical axis represents the pulse voltage, and the horizontal axis represents time.

When the discharge plasma generated by applying such a pulsed electric field is used for surface treatment, it has a sufficient surface treatment function even in air.

The frequency of the pulse electric field is 5 to 100 kHz.
The range of z is preferred.

The time for applying one pulse electric field is 1 μm.
It is preferably s to 1000 μs. The time during which one pulse electric field is applied is the time during which a pulse having one pulse waveform in FIG. 2 is applied.

The magnitude of the voltage applied to the counter electrode is not particularly limited, but the electric field strength when applied to the electrode is 1 to 1
It is preferable to set the range to be 00 kV / cm.

The output of the power supply applied to the counter electrode is 3 to 4
0 kW / m ² is preferable, and about 10 kW / m ² is more preferable.

The time for performing the plasma treatment on the support can be adjusted by controlling the transfer speed of the support according to the length of the processing chamber.
(Sec) is more preferable, and about 3 sec is more preferable.

Next, a second method and apparatus will be described.

FIG. 3 is a schematic configuration diagram showing one embodiment of the second method and apparatus.

As shown in the figure, a processing unit 2 for continuously plasma-treating a continuously transported long support 1 under atmospheric pressure or a pressure close to the atmospheric pressure is provided by an inlet 2B of the support 1. And a partitioned processing chamber having an outlet 2B. Hereinafter, the processing unit will be described as a processing chamber.

The processing chamber 2 is provided with opposed flat plate electrodes 3 and 4. The configuration of the plate electrode may be the same as that used in the first method and apparatus.

In the illustrated example, a preliminary chamber 10 is provided adjacent to the processing chamber 2 on the inlet side of the base material, and a preliminary chamber 11 is provided adjacent to the preliminary chamber 10. A preliminary chamber 12 is also provided adjacent to the processing chamber 2 on the outlet side of the support.

In the case of providing a spare chamber, as shown in the drawing, an embodiment in which two are provided on the inlet side of the base material 1 and one is provided on the outlet side may be used. One side may be provided, two sides may be provided on the inlet side, and no side may be provided on the outlet side, or two or more sides may be provided on the inlet side and two or more sides may be provided on the outlet side.

In any of the embodiments, the pressure in the processing chamber needs to be higher than the pressure in the preliminary chamber adjacent to the processing chamber, and is preferably 0.03 mmAq or more. By providing a pressure difference between the processing chamber and the spare chamber in this way, mixing of external air is prevented, the reactive gas can be used effectively, and the surface treatment effect is further improved.

Further, two or more at the entrance side adjacent to the processing chamber,
When two or more preparatory chambers are provided on the outlet side, the pressure between the preparatory chamber and the adjacent preparatory chamber is preferably set to be higher than that of the preparatory chamber close to the processing chamber, and is preferably 0.03 mmA.
It is preferable to be set higher than q. By providing a pressure difference between the plurality of spare chambers as described above, the mixing of external air is more effectively prevented, the reactive gas can be used more effectively, and the surface treatment effect is further improved.

It is preferable that the spare chamber contains at least one component of the processing gas from the viewpoint of efficient use of the reaction gas and improvement of the surface treatment effect.

Further, in order to provide a plurality of spare chambers and provide a pressure difference, it is preferable to provide a pressure reducing means 15. Examples of the pressure reducing means include a suction fan and a vacuum pump.

It is necessary that the processing chamber and the preparatory chamber and the room between the preparatory chambers be partitioned, and the partitioning means includes a nip roll 7 at the entrance side as shown in the figure.
7. An embodiment in which nip rolls 8 and 8 are provided on the outlet side is also preferable.

Although such a nip roll has a function of closing or partitioning while being in contact with the base material, since the rooms cannot be completely partitioned, the means for providing a pressure difference as in the present invention effectively functions. .

Further, the partition means may be a mode in which a predetermined gap is maintained with respect to the base material and the partition is not in contact with the base material. As such an embodiment, an air curtain system (not shown) or the like can be employed. It is also preferable to use the apparatus shown in FIGS. 10 and 11 described below. In the case where no spare chamber is provided, a partition may be provided between the processing chamber and the outside.

In FIG. 3, the portions denoted by the same reference numerals as those in FIG. 1 have the same configuration, and the description thereof will be omitted. In order to process using the apparatus shown in FIG.
Enters the processing chamber 2, and a pulsed electric field is applied in the processing chamber 2. With this application, the surface of the base material is subjected to plasma treatment, and the surface is treated.

In the second method, at the time of such surface treatment, the ratio of the reaction gas in the processing gas sealed in the processing chamber 2 is 30% or more, and the pressure in the processing chamber 2 is higher than the external pressure. Is preferred.

Since the gas from the outside does not enter the processing chamber 2 by setting the pressure in the processing chamber 2 higher than the external pressure, a specific element to be processed (to be introduced into the base material) is provided as necessary. Only gas can be sealed in the processing chamber with high purity, and more efficient processing can be performed. Further, when the ratio of the reaction gas in the processing gas is 30% or more, the amount of the inert gas can be reduced, and efficient processing can be performed at low cost.

In the present invention, the maximum effect can be obtained with a further minimum airtightness by the mode in which the pressure in the processing chamber 2 is higher than the external pressure by 0.03 mmAq or more.

Further, before the surface treatment, the surface of the base material is preferably subjected to a static elimination treatment and dust is further removed, so that the uniformity of the surface treatment is further improved. As the charge removing unit and the dust removing unit after the charge removing process, the same unit as the unit described in the first method can be employed.

The proportion of the reaction gas in the processing gas sealed in the processing chamber 2 is not less than 30%. Examples of the reaction gas include nitrogen (N ₂ ) gas, hydrogen (H ₂ ) gas, and ammonia (NH ₃ ). There are gas, fluorine gas, water vapor and the like, and any gas which can provide a polar functional group such as an amino group, a carboxyl group, a hydroxyl group, a carbonyl group or a chemically active group may be used. In particular, when performing a hydrophilization treatment, it is more preferable to insert an OH group, so that alcohol, H ₂ O, O
2, it is preferable to mainly use CO2 and the like. When performing the water-repellent treatment, it is preferable to use a fluorine-containing compound (such as fluorine and an organic fluoro compound). As the reaction gas, a compound containing an oxygen element (oxygen, ozone, water,
In addition to carbon monoxide and carbon dioxide, alcohols such as methanol, ketones such as acetone, aldehydes, etc., nitrogen-containing compounds (nitrogen-containing inorganic substances such as nitrogen, ammonia, nitric oxide, nitrogen dioxide, amine compounds, etc.) Nitrogen-containing organic substances) can also be used.

As a gas other than the reaction gas in the processing gas,
An inert gas can be used. Examples of the inert gas include argon (Ar) gas, neon (Ne) gas, helium (He) gas, krypton (Kr) gas, and xenon (Xe) gas.

In the present invention, prior to the introduction into the processing chamber 2, it is preferable to use a processing gas in which an inert gas and a reactive gas are mixed in advance. It is sufficient that the atmosphere between the electrodes 3 and 4 in the processing chamber 2 has the above-described ratio of the reaction gas.

Although the electrodes used in the embodiments described above are flat electrodes, it is also preferable to use cylindrical electrodes, roll electrodes, or gas flow type curved electrodes instead.

First, an example using a cylindrical electrode will be described.

FIG. 4 is a schematic configuration diagram showing another preferred embodiment of the second apparatus. The embodiment shown in FIG. 4 uses a cylindrical electrode in place of the plate electrode used in the embodiment shown in FIG. This is an example.

Note that, of the reference numerals shown in FIG. 4, the same components as those shown in FIG. 3 have the same configuration, and therefore, description thereof will be omitted.

In this embodiment, a plurality of cylindrical electrodes 3 are provided on both sides of the substrate 1. As shown in the drawing, the juxtaposition method may be such that the juxtaposition is made, but the juxtaposition method may be adopted. The inter-electrode gap L is represented by the distance between the lowermost end of the upper electrode of the substrate 1 and the uppermost end of the lower electrode. The spacing between the electrodes may or may not be uniform.

The cylindrical electrode has a conductive metal disposed inside,
It has a double-tube structure in which a dielectric is disposed outside, and the configuration of the conductive metal and the dielectric can adopt the above-described configuration.
A metal tube or rod can be inserted into the ceramic pipe.

Reference numerals 20, 21, and 22 denote transport rolls.

By using such a cylindrical electrode, the gas can be easily introduced between the electrodes, so that the contact efficiency between the reaction gas and the electrode is increased, and as a result, the surface treatment effect is also improved. In addition, the structure is simple, the compatibility is excellent, and the processing can be performed at low cost. Also, excellent effects are exhibited in high-speed transport of the substrate.

Next, an example using a roll type electrode will be described.

FIGS. 5 to 8 are schematic structural views showing another preferred embodiment of the second device. The embodiment shown in FIG. 5 is different from the plate electrode used in the embodiment shown in FIG. Note that among the reference numerals shown in FIGS. 5 to 8, FIG.
Since the same parts as those indicated by reference numerals have the same configuration, description thereof will be omitted.

In the form shown in FIGS. 5A and 5B, one electrode 3 is a cylindrical roll-type electrode, which rotates by itself, and is transported while the substrate 1 is in contact with the surface thereof. This electrode is provided with a dielectric on the surface of a roll-shaped conductive metal.

On the other hand, the electrode 4 is a curved electrode having a curved surface parallel to the curved surface of the roll type electrode.

The electrodes 3 and 4 are arranged as shown in the figure, and a gas supplied from a supply port (not shown) is blown out from a plurality of holes (not shown) from the curved electrode 4 side as shown by arrows.
The gas ejection direction may be the radial direction of the roll as shown in FIG. 5A, or may be the tangential direction of the roll as shown in FIG. 5B. The gas ejection hole may be a round hole or a slit.

When gas is ejected from the plurality of holes, the gas sufficiently spreads over the surface of the base material 1 being carried by the gas, thereby enabling stable discharge. Further, since the base material is in contact with and supported by one of the roll electrodes, the curved electrode can be brought closer to the base material, the surface treatment is stabilized, and the treatment effect is improved. Further, since the roll electrode is rotating, no damage is caused when the substrate is transported. There is also an effect that the number of nip rolls can be reduced as compared with the embodiment shown in FIG. Also, this form
Excellent effects are exhibited even in high-speed transport of substrates.

The embodiment shown in FIG. 6 is an example in which a processing chamber is formed by a combination of a plurality of roll electrodes and curved electrodes, and provides a practical apparatus. In addition, this mode exhibits an excellent effect even in high-speed transport of a substrate.

The embodiment shown in FIG. 7 is an example in which a roll-type electrode and a plurality of cylindrical electrodes are combined, and the example shown in FIG. 8 is provided with a plurality of devices in the form shown in FIG. It is an example. It should be noted that among the reference numerals shown in FIGS.
Since the same parts as those indicated by reference numerals have the same configuration, description thereof will be omitted. These forms also exhibit excellent effects in high-speed transport of a substrate.

Next, an example using a gas flow type curved electrode will be described.

FIG. 9 is a schematic configuration diagram showing another preferred embodiment of the second apparatus. The embodiment shown in FIG. 9 is an example in which a curved electrode is used in place of the flat plate electrode used in the embodiment shown in FIG. It is.

[0127] Of the reference numerals shown in FIG. 9, the same parts as those shown in FIG. 3 have the same configuration, and therefore description thereof will be omitted.

The electrodes 3 and 4 of the present embodiment are parallel to the surface of the substrate 1, and when viewed from a direction perpendicular to the direction of transport of the substrate 1, the cross-sectional shape of the facing surface is a curved surface. Curved electrode.

A plurality of electrodes 3 and 4 (in FIG. 9,
3) By arranging them in the transport direction, the substrate 1 being transported is configured to meander. Therefore, gas supplied from a supply port (not shown) is ejected from a plurality of holes (not shown) as indicated by arrows. Preferably, the jets are evenly distributed. The gas ejection holes may be round holes or slits.

When gas is ejected from the plurality of holes, the gap of the base material 1 carried by the gas is about 10 m.
m and is transported in a non-contact manner to a pair of electrodes 3 and 4 set to be equal to or less than m. In such an embodiment, the gas is directly ejected between the pair of electrodes, so that the diffusion of the gas is promoted and a stable discharge is enabled.
In addition, both surfaces of the substrate 1 can be processed simultaneously, and the processing efficiency is excellent.

In this embodiment, the substrate 1 is conveyed in a meandering manner, so that the substrate can be transported more stably as compared with the linear transport (transportation shown in FIG. 3). Also increase. In addition, this mode exhibits an excellent effect even in high-speed transport of a substrate.

In the illustrated embodiment, the sheet is conveyed in a meandering manner. However, various other modified forms can be adopted as long as non-contact conveyance is possible.

In the apparatus described above, in order to further improve the effect of blocking the air entrained by the substrate, FIG.
It is also preferable to use the apparatus shown in FIG.

FIG. 10 is an enlarged view of the gas flow blade device. The gas flow blade device can finely adjust the gap d between the surface of the base material 1 being conveyed on the conveyance roll 30 and the slit portion 31 and can be adjusted from the inside (the right side in the figure) of the gas flow blade device. The release gas 32 is released from the slit 31 to the surface of the base material in a pressurized state with the release angle taken in a direction opposite to the transport direction of the base material 1, and the angle is preferably 60 to 90 °. The gas may be released only from the slit, but the more effective treatment can be achieved by reducing the pressure of the released gas in a direction opposite to the direction of transport of the substrate 1 to form a gas flow 33. The smaller the width of the slit 31, the better
2.0 mm or less is preferable. This embodiment can also be applied to the device of FIG. It can be applied to the partition between the processing room and the spare room, and between the spare room and other spare rooms.

FIG. 11 is an enlarged view of a part of an apparatus provided with a film-like blade for increasing the security. Touching the confidentiality of gaps other than the gaps through which the base material 1 passes by rubbing the film-shaped blade 43 against a location where a roll is used as a partition, for example, the back side of the transport roll 41 and the free roll 42. Enhanced by. The nip rolls 41 and 42 may be paired, or if there is no roll above the substrate 1, the transport roll 41 alone may be used.

Next, a third method and apparatus will be described.

In FIG. 16, the substrate 1 is conveyed outside the dielectric, instead of being conveyed between two facing dielectrics. The two opposing dielectric surfaces are orthogonal to the substrate surface. Gas is introduced between the two facing dielectrics. The gas may be air. Then, an electric field is applied to the gas introduced between the two facing dielectrics to generate a discharge plasma, and the discharge plasma is introduced into the base material. With such a configuration, damage to the base material due to direct application of an electric field to the base material can be reduced. Furthermore, according to this configuration, since the base material does not intervene between the two facing dielectrics for generating plasma, an electric field can be easily generated, and the ratio of gas to be converted into plasma can be increased. Efficient and more excellent surface modification effects can be obtained.

Similarly, as shown in FIG. 17, the direction of the generated electric field may be changed from that in FIG.

FIG. 18 shows an embodiment of the configuration of FIG.

A discharge plasma is generated in a room that is cut off from the outside air, and the substrate is continuously transported into the room by a transport roller as transport means, so that the discharge plasma is generated on the substrate. Will be introduced. The nip roll pair also plays a role in reducing the introduction of outside air into the room and the discharge of discharge plasma out of the room at the entrance of the room (the opening through which the substrate enters the room). In addition, the exit of the room (the mouth for the substrate to exit the room)
Also, a nip roll pair is provided which plays a role of reducing the introduction of outside air into the room and the discharge of discharge plasma to the outside as in the case of the inlet.

Further, the present apparatus is provided with a circulation pipe for circulating discharge plasma and a fresh gas introduction pipe for introducing non-plasmaized gas. The circulation pipe is a pipe for circulating the discharge plasma so that the discharge plasma sucked from the gas suction port provided in the room can be discharged from the gas discharge port provided on the inlet side between the pair of solid dielectrics. is there. The discharge plasma discharged from the gas discharge port is turned into plasma again between the solid dielectric pairs and introduced into the base material. In addition, the fresh gas introduction pipe is a pipe for introducing a gas so that the non-plasmaized gas contained in the gas cylinder can be discharged from the gas discharge port provided on the inlet side between the solid dielectric pair. is there. The non-plasmaized gas discharged from the gas discharge port is converted into plasma between the solid dielectric pairs and introduced into the base material.

As described above, the discharge plasma is circulated and reused, and the non-plasmaized gas is introduced into the discharge plasma to be used. Thus, the waste of the gas can be reduced, and more efficiently and more efficiently. An excellent surface modification effect can be obtained.

Next, a fourth method and apparatus will be described.

FIG. 19 shows a plasma processing apparatus provided in a closed room.

An electric field is applied to a continuously transported base material by an electric field generated between a grounded roller and an electrode. Further, a gas injection unit having a nozzle having a slit for injecting gas is provided on the transport path of the base material immediately before the electric field (immediately before the electrode).

[0146] In the above-described structure, the gas which is injected from the slit of the gas injection means is introduced into the continuously transported substrate. Immediately thereafter, the gas introduced into the inside of the base material is turned into plasma by an electric field generated between the electrode and the roller, so that plasma processing is performed.

As described above, by performing the plasma treatment immediately after the injected gas is introduced into the base material, the gas can be more easily introduced into the base material. The surface modification effect can be obtained.

The nozzle shape is preferably a slit type or a porous type. Further, it is preferable that the pressure inside the nozzle at the time of injecting the gas is 15 mmAq or more in order to improve the efficiency of gas introduction into the base material. The distance between the nozzle tip and the substrate is preferably 5 mm or less, and the gas wind velocity at the nozzle tip is preferably 15 m / sec or more in order to improve the efficiency of gas introduction into the substrate.

Next, the surface-treated substrate of the present invention includes a substrate treated by any of the above methods and apparatuses.

The generation of plasma during the surface treatment of the present invention is based on the Optical Emission Spectr.
oscopy method (OES for short) or Photo
Electron Spectroscopy (Photoelectron Spectroscopy) (PES) can be used for measurement.

The active groups appearing on the substrate surface by the discharge plasma treatment of the present invention were determined by photoelectron spectroscopy (ESCA).
You can know by. For example, VG ESCALA
B-200R can be used.

Hereinafter, a substrate to which the present invention can be applied will be described.

In the present invention, it is preferable to use a substrate obtained by applying a coating solution in which silica is dispersed in PVA on a film or paper selected from polyethylene terephthalate, polyethylene naphthalate, polyethylene and polypropylene.

[0154]

EXAMPLES A substrate was subjected to plasma treatment using an apparatus under the following conditions. (1) Power supply condition (1) High frequency power supply SPG50-2 manufactured by Shinko Electric Co., Ltd.
5000 Conditions (2) Impulse high-frequency high-voltage power supply PHF-6K manufactured by Heiden Laboratories (2) Processing chamber Equipment equipped with a processing chamber of the type shown in Fig. 3 (Unless the gas purge is used, use without closing the processing chamber. ) Processing chamber volume 2000cm ³ Electrode area 250mm × 50
0 mm Dielectric Alumina ceramics 1 mm thickness Gap between electrodes 3 mm (3) Discharge conditions Frequency 50 kHz Output 10 kW / m ² Processing time 3 sec (4) Processing gas conditions Conditions (1) Gas purge Ar 80%, O ₂ 20% Conditions (2) Gas purge Ar 40 %, O ₂ 60% Condition (3) Gas purge Ar 50%, CF ₄ 50% Condition (4) Gas purge O ₂ 100% Condition (5) Gas purge N ₂ 100% Condition (6) Atmospheric discharge (no gas purge) (5) Substrate to be used A gelatin layer was applied as a subbing layer on Konica RC paper in which polypropylene was applied on both sides of a pulp base paper by 5 μm each, and a coating solution in which silica was dispersed in PVA was applied and dried over four layers. Was used as a substrate (hereinafter, Konica inkjet paper, Konica QP, or simply Also referred to as click-jet paper). (Example 1) Ink jet paper (QP made by Konica) was placed in a processing apparatus and discharged under the above conditions. FIBRO (Sweden) for treated inkjet paper
A fixed amount of liquid droplets (PMIC1C manufactured by EPSON, dark magenta color,
2 μL) was dropped, and the time required for the remaining liquid volume remaining on the surface of the surface layer to reach 0.5 μL was measured. The results are shown below.

[0155]

[Table 1]

When the amount of ink remaining on the surface of the surface layer is 0.5 μL
In this case, the horizontal bleeding phenomenon of dots that land adjacently is alleviated, and the horizontal bleeding is substantially eliminated. However, if it is left unprocessed, it takes 4 seconds or more to clear this value.

On the other hand, it can be seen that all the samples subjected to the plasma treatment have a shorter time, and the absorption rate is improved.

In particular, as shown by the present inventions 2 and 3, the longer the purge time, the better the reforming effect.

Further, when a pulse type power supply is used, a large surface modification effect can be obtained without performing gas purging.

In general, ink jet paper, for which it was impossible to substantially avoid interference between dots that land adjacent to each other, is significantly improved in ink absorption speed by plasma processing, thereby improving image forming ability. You can see that it was done. (Example 2) Corona power supply AGI manufactured by Kasuga Electric Co., Ltd.
The plasma processing was performed under the same conditions as in the above-mentioned application 1 except that the power supply was changed to -020 type power supply.
It was confirmed that the image forming ability was improved as compared with the untreated one. (Example 3) Ink jet paper (QP made by Konica) was placed in a processing apparatus, and after a gas purge for 5 minutes under the gas condition (3), discharge was performed under the same conditions as in the first application of Example 1. Using a contact angle measuring device DAT1100MkII manufactured by FIBRO (Sweden), a predetermined amount of droplets (PMIC1C manufactured by EPSON, dark magenta color, 2 μL) was dropped onto the treated inkjet paper, and the degree of spread of the landing diameter of the ink was observed.

[0161]

[Table 2]

From this, it can be confirmed that the spread (horizontal bleeding) after ink landing is improved by performing the plasma treatment. (Example 4) Ink jet paper subjected to the plasma treatment (treated under the conditions of the present application 5) under the gas condition (4) in the first embodiment, and further, the gas condition is Ar 90%, CF ₄ 1
As a result of the plasma treatment at 0%, good results were obtained in both the water absorption rate and the bleeding resistance.

[0163]

[Table 3]

(Embodiment 5) In a purge chamber capable of reducing pressure, 4
00mm width, 300m roll inkjet paper
(QP made by Konica) was installed, and gas was sealed under the gas condition (4) while maintaining the internal pressure at 20 Torr. After 5 minutes, the inkjet paper was taken out of the purge chamber, taken out of the processing line for about 10 minutes, and discharged under the above conditions while being transported and passed through the processing chamber. Using a contact angle measuring device DAT1100MkII manufactured by FIBRO (Sweden), apply a fixed amount of droplets (PMIC1C manufactured by EPSON, dark magenta color, 2 μm) to the treated inkjet paper.
L) As a result of dropping, almost the same results as in Example 1 Application 7 were obtained. (Example 6) Ink jet paper (QP made by Konica) was placed in a processing apparatus, and after one hour of gas charging, discharge was performed under the above conditions. Further, the plasma processing was performed while changing the humidity condition of the processing gas. A contact angle measuring instrument DAT1100Mk manufactured by FIBRO (Sweden) is applied to the treated inkjet paper.
A fixed amount of droplets using the II (PMIC1 manufactured by EPSON)
C, dark magenta color, 2 μL) was dropped, and the time until the volume of the liquid remaining on the surface became 0.5 μL was measured.
The results are shown below.

[0165]

[Table 4]

From this, it is understood that the image receiving performance is further improved by changing the humidity condition. (Example 7) The device (electrode, dielectric) in Example 1 was replaced with
Arranged as shown in FIG. 18 so as to be almost perpendicular to the base material, a constant flow of a mixed gas is introduced between the electrodes to discharge between the electrodes,
The activated gas was blown against the substrate. Processing room, power supply,
The discharge conditions, the processing gas conditions, and the conditions relating to the base material used are the same as in Example 1. Note that the distance d from the dielectric to the substrate (the distance from the position of the dielectric closest to the substrate to the substrate) is 2 mm, and the internal pressure inside the processing chamber is 3 mmAq. Then, in the same manner as in Example 1, a fixed amount of droplets (EPSON PMIC1C, dark magenta color, 2 μm) were applied to the treated inkjet paper using a contact angle measuring device DAT1100MkII manufactured by FIBRO.
L) Dropping was performed, and the time required for the remaining liquid volume remaining on the surface to reach 0.5 μL was measured. Table 5 shows the results.

[0167]

[Table 5]

As described above, in this embodiment, an excellent surface modification effect can be obtained while reducing damage to the substrate.

Further, the gap of the gas discharge port A (the port of the slit formed by the two dielectrics through which the plasma gas is discharged) is set to 0.3 mm, and the internal pressure inside the processing chamber is set to 30 mm.
Table 7 shows the results of experiments performed under the same conditions as in the new example (new example in Table 5) except that the gas that was jetted was blown onto the base material by setting it to Aq.

[0170]

[Table 6]

As described above, by spraying the gas that has been jetted onto the base material, it is possible to obtain an efficient and excellent surface modification effect up to the inside of the void. (Example 9) Table 6 shows the results of processing using the apparatus of FIG. The power source used is condition (1), the gas condition is (1), and the multiple conditions are the same as in the first embodiment. And
As in Example 1, F was applied to the treated inkjet paper.
Using a contact angle measuring device DAT1100MkII manufactured by IBRO, a fixed amount of droplets (PMIC1C manufactured by EPSON, dark magenta, 2 μL) was dropped.
The time until the volume of the remaining liquid remaining on the surface became 0.5 μL was measured.

[0172]

[Table 7]

As described above, in the present embodiment, by blowing the gas jet, the purging time is not required, and the gas can be efficiently sealed in the gap. The surface modification effect can be obtained.

[0174]

According to the present invention, it is possible to provide a method and apparatus for treating a surface of a substrate which is inexpensive and excellent in productivity, and to provide a substrate which has been subjected to a surface treatment. The effect of modifying the material surface can be obtained.

In particular, it is possible to dramatically improve the image receiving performance of an ink jet recording medium and to record a high-definition image.

Also, by using a pulse type power supply,
Plasma treatment can be performed even in the atmosphere, and treatment efficiency can be improved.

Further, by controlling the humidity in the processing gas, the processing efficiency, the degree of imparting hydrophilicity and hydrophobicity can be adjusted, and an ink jet recording medium having various performances can be manufactured.

By performing the production of the ink jet recording medium in a continuous and continuous process, the surface modification can be performed at high speed and with high efficiency.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing one embodiment of a first method and apparatus of the present invention.

FIG. 2 is a diagram showing one form of a pulse wave.

FIG. 3 is a schematic configuration diagram showing one embodiment of the first method and apparatus of the present invention.

FIG. 4 is a schematic configuration diagram showing an embodiment using a cylindrical electrode.

FIG. 5 is a schematic configuration diagram showing an embodiment using a roll-type electrode.

FIG. 6 is a schematic configuration diagram showing an embodiment using a roll-type electrode.

FIG. 7 is a schematic configuration diagram showing an embodiment using a roll-type electrode.

FIG. 8 is a schematic configuration diagram showing a mode using a roll-type electrode.

FIG. 9 is a schematic configuration diagram showing an embodiment using a gas flow type curved electrode.

FIG. 10 is a schematic diagram showing an example of an apparatus for improving airtightness.

FIG. 11 is a schematic configuration diagram showing another example of an apparatus for improving airtightness.

FIG. 12 is a process chart showing a continuous processing step of the present invention.

FIG. 13 is a view showing a landing state in which lateral bleeding has occurred;

FIG. 14 is a view showing a landing state in which lateral bleeding does not occur.

FIG. 15 is a diagram showing a cross section of a base material.

FIG. 16 is a diagram showing a state in which gas is blown onto a base material.

FIG. 17 is a diagram showing a state in which gas is blown onto a base material.

FIG. 18 is a view showing a mode of circulating gas.

FIG. 19 is a view showing a gas nozzle arranged near a roll.

FIG. 20 is a view showing a shape of a gas nozzle.

[Explanation of symbols]

 1: substrate 2: processing section to processing chamber 3, 4: electrode 5: power supply 6: ground 7, 8: nip roll 15: decompression means 12: preliminary chamber

Claims (38)

[Claims] 1. A method for treating a surface of a support, comprising performing a plasma treatment on a support having a surface layer having a void structure. 2. The surface treatment method according to claim 1, wherein a functional group is imparted to the support by the plasma treatment. 3. The surface treatment method according to claim 1, wherein said voids are roughened by said plasma treatment. 4. The method according to claim 1, wherein the plasma processing is performed in an atmosphere mainly composed of an inert gas.
Surface treatment method. 5. The surface treatment method according to claim 1, wherein the surface layer having voids is a surface layer of the support. 6. The surface layer having voids is a coating layer provided on the support.
Surface treatment method. 7. The surface treatment method according to claim 1, wherein at least one of the inside of the gap layer and the surface layer of the gap layer is made hydrophilic by the plasma treatment. 8. The surface treatment method according to claim 1, wherein the water repellency of at least a surface layer of the void is improved by the plasma treatment. 9. The surface treatment method according to claim 7, wherein the plasma treatment is performed by corona discharge. 10. The surface treatment method according to claim 7, wherein the plasma treatment is performed by a flame. 11. The surface treatment method according to claim 7, wherein the plasma treatment is performed by glow discharge under vacuum, atmospheric pressure, or a pressure near atmospheric pressure. 12. The processing method according to claim 1, wherein the atmosphere in which the plasma processing is performed has an absolute humidity of 0.005 [kg-steam / kg-dry gas] or more. 13. The surface treatment method according to claim 1, wherein a water-repellent treatment is performed after the hydrophilic treatment is performed by the plasma treatment. 14. The surface according to claim 1, wherein the support is present in a gas atmosphere for performing a plasma treatment, and the plasma treatment is performed after the gap structure is filled with the gas. Processing method. 15. The surface treatment method according to claim 1, wherein the support is an ink jet recording medium. 16. An ink jet recording medium manufactured by using the surface treatment method according to claim 1. Description: 17. A method for treating a surface of a support, comprising performing plasma treatment on a support having a surface layer having a void structure using plasma generated in a pulsed electric field. 18. The surface treatment method according to claim 17, wherein the absolute humidity of the atmosphere in which the plasma is generated is 0.005 [kg-steam / kg-dry gas] or more. 19. The surface treatment method according to claim 17, wherein a functional group is imparted to the support by the plasma treatment. 20. The surface treatment method according to claim 17, wherein the gap is roughened by the plasma treatment. 21. The surface treatment method according to claim 17, wherein the surface layer having voids is a surface layer of the support. 22. The surface treatment method according to claim 17, wherein the surface layer having voids is a coating layer provided on the support. 23. The surface treatment method according to claim 17, wherein the inside and / or the surface layer of the void is made hydrophilic by the surface modification. 24. The method according to claim 17, wherein at least a surface layer of the void is made water-repellent by the surface modification.
Surface treatment method. 25. The surface treatment method according to claim 17, wherein the plasma treatment is performed by glow discharge. 26. The surface treatment method according to claim 17, wherein the plasma treatment is performed under an atmospheric pressure or a pressure near the atmospheric pressure. 27. The surface treatment method according to claim 17, wherein the plasma treatment is performed in the atmosphere. 28. The surface treatment method according to claim 17, wherein the plasma treatment is performed in an atmosphere containing a reaction gas of 30% by volume or more. 29. The processing method according to claim 17, wherein the atmosphere in which the plasma processing is performed has an absolute humidity of 0.005 [kg-steam / kg-dry gas] or more. 30. The surface treatment method according to claim 17, wherein a water-repellent treatment is performed after the hydrophilic treatment is performed by the plasma treatment. 31. The surface treatment method according to claim 17, wherein the support is an ink jet recording medium. 32. An ink jet recording medium manufactured by using the surface treatment method according to claim 17. 33. A pre-treatment is performed on a continuously transported support, and then a coating solution is applied to the support, dried to form a functional layer, and post-processed on the functional layer. Is carried out continuously and in a continuous process. 34. The method according to claim 33, wherein the pre-processing is a plasma processing. 35. The method according to claim 33, wherein the pretreatment is a corona discharge treatment. 36. The method according to claim 33, wherein the post-processing is a plasma processing. 37. The method according to claim 33, wherein the plasma processing is performed using plasma generated in a pulsed electric field. 38. The surface treatment method according to claim 33, wherein the absolute humidity of the atmosphere in which the plasma is generated is 0.005 [kg-steam / kg-dry gas] or more.