JP2000319427A - Apparatus for surface treatment of plastic support, method for surface treatment of plastic support and method for surface treatment of aluminum support for lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus and a method for a surface treatment enabling a uniform discharging plasma treatment in a gas of a plastic support, a surface-treated electrode for a discharging plasma treatment in a gas which can be made cheaply and easily, a method for a surface treatment which causes no defect in coating on the plastic support after the discharging plasma treatment in a gas, a method for a surface treatment by a discharging plasma treatment in a gas to impart a plastic support with excellent adhesive properties and resistance to blocking, and further a method for a surface treatment enabling not only reduction of hydrophilization processes, space and cost but also impartation of excellent printing durability in manufacturing an aluminum support for a lithographic printing plate. SOLUTION: In the title apparatus for a surface treatment of a plastic support, a plastic support 5 continuously traveling between a pair of electrodes is subjected to a discharging plasma treatment in a gas in a mixed gas atmosphere comprising at least 50 pressure %, relative to inert gases introduced, of argon gas under atmospheric pressure or a pressure near the same. In this case, at least one of the pair of the electrodes 6, 7 is transformed so as to give different impedance in a lengthwise direction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus and a method for treating a plastic support used for a silver halide photographic light-sensitive material, and a method for treating a surface of an aluminum support used for a lithographic printing plate. More specifically, under the atmospheric pressure or a pressure near the atmospheric pressure, 50% by weight or more of the inert gas to be introduced is used as an argon gas, and the surface of the plastic support which is continuously transported is subjected to a discharge plasma treatment in a gas. The present invention relates to an apparatus and a surface treatment method, and to a surface treatment method for an aluminum support for a lithographic printing plate, which is subjected to a hydrophilic treatment by a flame treatment.

[0002]

2. Description of the Related Art In recent years, corona discharge treatment, vacuum glow discharge treatment and the like have been proposed as techniques capable of promoting the adhesion of a constituent layer of a silver halide photographic material to a support.
Although the corona discharge treatment is easy to use in that it can be treated in air, it has many discharge irregularities and often causes a concentrated discharge on the support, which is difficult to control.
Further, the processing strength is weak, and the surface modification of the plastic support is not sufficient. On the other hand, the vacuum glow discharge treatment is naturally not limited in terms of productivity and cost because the capacity of the treatment equipment itself is limited by applying a vacuum to the treatment equipment itself.

On the other hand, recently, a method of discharging and treating by using helium gas at or near atmospheric pressure is disclosed in Japanese Patent Application Laid-Open Nos. 3-143930 and 4-74525.
And Japanese Patent Publication Nos. 2-48626, 6-72308, and 7-48480.

However, in the surface treatment method described in the above publication, the helium gas supplied between the electrodes to be treated is very expensive, so that it is difficult to be suitable for industrial production. Therefore, processing can be performed while continuously transporting the support,
There has been a demand for a processing method which can promote the adhesion of a non-adhesive substance such as a constituent layer of a silver halide photographic light-sensitive material to a support, is low in cost, and is excellent in productivity.

[0005] In order to solve these problems, when the gap between the pair of electrodes is set to 10 mm or less under the atmospheric pressure or a pressure close thereto, at least 50% by pressure of the inert gas is continuously transferred as argon gas. A method and apparatus for subjecting a body to a discharge plasma treatment in a gas is disclosed in Japanese Patent Application No. 10-9.
No. 4468, No. 10-97426, and No. 10-24
No. 5151 has been proposed by the present applicant. With this method, the problems of each of the above methods were solved.

On the other hand, regarding the surface treatment of aluminum supports for lithographic printing plates, aluminum plates have been used as lithographic printing plate supports for many years by degreasing, polishing, anodizing and making hydrophilic aluminum plates. This surface treatment process is very long,
Huge equipment was needed. If at least one of these steps can be shortened, space saving of equipment, equipment cost or manufacturing cost can be reduced, and improvement has been required.

[0007]

In the process of performing the surface treatment of the plastic support, it has been found that there is a problem that needs improvement in small parts. During the gas discharge plasma treatment, it is difficult for the discharge from the high-voltage side electrode to the ground side electrode to be uniform at the end where the support is lost, and the discharge is concentrated directly on the ground side electrode avoiding the end of the support. The end was not treated, or the electrode was damaged at the point of concentration, and the electrode had to be replaced frequently. In addition, when the concentrated discharge occurs, the current efficiency is reduced and not only leads to energy loss, but also the processing efficiency is reduced.

[0008] Various electrodes have been proposed for a discharge processing apparatus under a near atmospheric pressure. For example, an electrode obtained by compression-molding ultrafine fibers of stainless steel into a web and then sintering the electrode (JP-A-7-111195), or an electrode obtained by coating an electrically conductive cylinder with an insulator such as ceramics (see Japanese Unexamined Patent Publication Nos. Hei 5-00914 and No. 7-119021) and an electrode in which a conductive liquid is introduced into a glass tube (Japanese Unexamined Patent Publication No. 7-220895). Thus, the cost is too high for the processing device. Therefore, there has been a demand for an electrode which is easy to manufacture and inexpensive.

As another problem, during processing, the plastic support is charged and dust easily adheres, and when coating a silver halide emulsion layer or the like after processing, coating unevenness or coating defects may occur. There are a number of issues that need to be solved, such as blocking when the treated surfaces overlap after being wound up.

A first object of the present invention is to provide a surface treatment apparatus and a treatment method for uniformly performing a gas discharge plasma treatment on a plastic support. A second object is to provide a surface-treated electrode for in-gas discharge plasma treatment that can be easily manufactured at low cost. The third purpose is
An object of the present invention is to provide a surface treatment method that does not cause coating defects on a plastic support after gas discharge plasma treatment. A fourth object of the present invention is to provide a surface treatment method using a gas discharge plasma treatment, which has good adhesion of a plastic support and is resistant to blocking. A fifth object is to provide a surface treatment method capable of shortening the step of hydrophilizing an aluminum support for a lithographic printing plate, saving space and cost, and having excellent printing durability.

[0011]

The present invention comprises the following constitutions.

(1) At atmospheric pressure or a pressure close thereto,
Under a mixed gas atmosphere having a composition in which 50% by pressure or more of the inert gas to be introduced is argon gas, a plastic support continuously transferred between a pair of electrodes is treated by a plasma discharge gas. A surface treatment device for a plastic support, wherein at least one of the pair of electrodes has a different impedance in a length direction.

(2) At atmospheric pressure or a pressure close to atmospheric pressure,
Under a mixed gas atmosphere having a composition in which 50% by pressure or more of the inert gas to be introduced is argon gas, a plastic support continuously transferred between a pair of electrodes is treated by a plasma discharge gas. A surface treatment device for a plastic support, wherein at least one of the pair of electrodes has a different permittivity in a length direction.

(3) At atmospheric pressure or a pressure close to atmospheric pressure,
Under a mixed gas atmosphere having a composition in which 50% by pressure or more of the inert gas to be introduced is argon gas, a plastic support continuously transferred between a pair of electrodes is treated by a plasma discharge gas. A surface treatment apparatus for a plastic support, wherein at least one of the pair of electrodes is in a pipe shape, and a metal pipe is provided in a dielectric pipe of the electrode.

(4) The surface treatment apparatus for a plastic support according to (3), wherein the electrode has an insulating cooling medium inside.

(5) A method for treating a surface of a plastic support, wherein the method is carried out by the apparatus according to any one of (1) to (4).

(6) At atmospheric pressure or a pressure close to atmospheric pressure,
When a plastic support continuously transferred between a pair of electrodes is subjected to discharge plasma treatment in a gas under a mixed gas atmosphere having a composition in which 50% by pressure or more of an inert gas to be introduced is argon gas, the support is used. Wherein the effective gas in the gas composition near both ends is reduced.

(7) At atmospheric pressure or a pressure close thereto,
Under a mixed gas atmosphere having a composition in which 50% by pressure or more of the inert gas to be introduced is argon gas, a plastic support continuously transferred between a pair of electrodes is treated by a plasma discharge gas. In the surface treatment apparatus, at least one selected from the upstream side and the downstream side in the support transfer direction of the apparatus has at least one selected from a static elimination unit and a dust removal unit of the support, wherein the plastic support is provided. Surface treatment equipment.

(8) A static eliminator in which the static elimination means has a plurality of static elimination electrodes for generating positive and negative ions and ion attraction electrodes opposed to each other so as to sandwich the support. The surface treatment apparatus for a plastic support according to claim 7, wherein the apparatus is a high-density static elimination system having a static eliminator and an AC type static eliminator further downstream thereof.

(9) The surface treatment apparatus for a plastic support according to (7) or (8), wherein the dust removing means is a non-contact type jet wind decompression type dust removal apparatus.

(10) A method for surface treatment of a plastic support, wherein the method is performed by the apparatus according to any one of (7) to (9).

(11) The gas is continuously transferred between a pair of electrodes under a pressure of the atmospheric pressure or a pressure close to the atmospheric pressure and in a mixed gas atmosphere having a composition in which 50% by pressure or more of the inert gas to be introduced is argon gas. In the surface treatment method for a plastic support in which the plastic support is subjected to a discharge plasma treatment in a gas, an average roughness (Ra) of the surface of the support is 0.1.
A surface treatment method for a plastic support, which is not less than μm.

(12) Continuous transfer between a pair of electrodes under an atmosphere pressure or a pressure near the same and in a mixed gas atmosphere having a composition in which 50% by weight or more of an inert gas to be introduced is argon gas. A surface treatment method for a plastic support, wherein the plastic support has a roughened portion at both ends, wherein the plastic support is subjected to a discharge plasma treatment in a gas.

(13) The support is 5 to 30 mm from the edge
The surface treatment method for a plastic support according to (12), wherein the plastic support has a roughened portion.

(14) A method of treating the surface of an aluminum support for a lithographic printing plate by a degreasing treatment, a polishing treatment, an anodic oxidation treatment, a sealing treatment and a hydrophilic treatment, wherein the hydrophilic treatment is carried out by a flame treatment. Surface treatment method for an aluminum support for a lithographic printing plate.

The present invention will be described in detail.

First, the plasma discharge treatment in gas of the present invention will be described.

According to the present invention, the basic matters, the processing apparatus, the processing conditions, the processing method, etc. of the discharge plasma processing in gas are described in Japanese Patent Application Nos. 10-97426, 10-94468 and 10-245151. Matters, especially Japanese Patent Application Hei 10-
245151.

Here, the in-gas discharge plasma treatment will be briefly described with reference to FIG.

FIG. 1 shows a first embodiment of an in-gas discharge plasma processing apparatus.
In the schematic view showing the example, the electrodes are shown as a pair of flat types, but the shape of the electrodes is not limited to this.

The gas discharge plasma processing apparatus 1 will be described. A process formed by mixing an inert gas containing 50% or more of the inert gas with argon gas and another reactive gas or an inert gas in the processing chamber 2 at or near atmospheric pressure. Gas is introduced from the inlet. Processing room 2
The space between the pair of electrodes 6 and 7 is also filled with a processing gas. The high-frequency power source 10 is connected to one electrode 6 of the pair of electrodes 6 and 7, and the other electrode 7 is grounded by a ground 10E. The in-gas discharge plasma discharge occurs in the gap between the pair of electrodes 6 and 7 and processes the continuously transported (transported) plastic support. In front of the processing chamber 2, a preparatory chamber 3 a is provided in order to shut off air entrained by the plastic support 5.
Is provided. The pair of electrodes 6 and 7 are connected to a metal portion (6
A, 7A) and the dielectric portion covering them (6B, 7A).
B). The metal portions 6A and 7A are made of conductive metal such as stainless steel, aluminum and copper, and the dielectric portions 6B and 7B are made of dielectric material such as rubber, glass, ceramic, Kapton, Teflon (registered trademark) and mica. It consists of a body. This dielectric coating may cover all or part of the metal part. As for the shape of the electrode, a flat electrode is used like a pair of electrodes 6 and 7 in FIG. 1, but in addition, one or both electrodes may be square, cylindrical (pipe, roll, drum). , Deformation thereof), etc. may be used. Reference numeral 3b denotes a spare room on the exit side. 8 is a guide roll
Reference numeral 9 denotes partition means for shutting off entrained air.

Next, the processing gas used in the present invention will be described.

In the present invention, "50% by pressure of inert gas"
The expression "as argon" means 50% by pressure of the inert gas in the total processing gas including the inert gas and the active gas, and is not related to the pressure% of the active gas. Therefore, for example, 100% pressure of argon gas
And the amount of active gas (eg, nitrogen gas) is not affected by the amount of argon gas and can be any percentage.

According to the present invention, of the processing gas introduced into the processing chamber 2, at least 50% by pressure of the inert gas is replaced with argon (Ar).
In-gas discharge plasma treatment is performed as a gas. Other inert gases include neon (Ne) gas, helium (He) gas, krypton (Kr) gas, xenon (X
e) There are gases and the like, and these inert gases can also be used at less than 50% by pressure of the inert gas. It is preferable to use argon (Ar) gas as a main component of the processing gas of the present invention, and to use argon gas at 60% by pressure or more in order to obtain an efficient reforming effect.

The processing effect of the argon gas in the in-gas discharge plasma processing may not be seen with the helium gas. Because argon has a larger atomic weight than helium and a larger size as a monoatomic gas, during processing, etching that occurs when argon is blown on the surface of the plastic support is likely to occur, and it is easy to generate irregularities on the surface . As described above, a remarkable reforming effect can be obtained, and argon gas is superior to other inert gases, so that argon gas has an advantage. Other inert gases, such as krypton gas and xenon gas, are required to generate plasma using them.
High power and high frequency are required and the surface treatment is too strong, damaging the plastic support.

In the present invention, it is preferable to mix the above-mentioned inert gas and the following reactive gas to obtain a processing gas.
In the in-gas discharge plasma treatment of the present invention, examples of the active gas used as the treatment gas include a nitrogen (N ₂ ) gas, a hydrogen (H ₂ ) gas, an ammonia (NH ₃ ) gas, and water vapor. By gas discharge plasma treatment,
The separated (free) reactive molecules react on the support surface,
-NH ₂ group, chemically active groups such as -OH group, -COOH group is expressed and can be chemically modified plastic support surface, contributes to enhancement of adhesion to quality goods. The ratio of the reactive gas to the total pressure% of the inert gas (100% by pressure) is preferably 0 to 0.30% by pressure, and more preferably 0.01 to 0.2% by pressure.

The discharge state of the gas discharge plasma treatment of the present invention is a discharge state similar to a glow discharge occurring in a vacuum, but by cutting off the air accompanying the support, the discharge state of the present invention is improved. The discharge state of the in-gas discharge plasma treatment becomes more suitable for the surface treatment.

The discharge intensity of the in-gas discharge plasma treatment of the present invention is 50 W · min / m ² or more and 500 W · min / m ^{2 in order} to perform stable and effective treatment without causing arc discharge.
Less than m ² is preferable because excellent adhesiveness can be obtained.

FIG. 2 is a schematic view showing another example of a similar in-gas discharge plasma processing apparatus in which a large number of pairs of square electrodes 16 and 17 are used as electrodes. The square electrode is composed of metal parts 16A and 17A and dielectric parts 16B and 17B.

FIG. 3 is a schematic cross-sectional view of an example of a plasma discharge processing apparatus in gas, viewed from the front. The width of the pair of electrodes 26 and 27 is longer than the width of the support 5. 21
Is an in-gas discharge plasma processing apparatus, 22 is a processing chamber, 26A
And 27A are the metal parts of the electrodes, 26B and 27B are the dielectric parts,
20 is a high frequency power supply, and 20E is a ground.

In the process of studying using the above-mentioned gas discharge plasma processing apparatus, in the processing chamber 2 or 22, different discharges are generated between the widthwise end portion and the middle portion of the plastic support 5. The situation was often observed, and it was found that the end portions were difficult to be subjected to the plasma discharge treatment in gas. Furthermore, concentrated discharge is likely to occur near the portion corresponding to the widthwise end of the plastic support 5 of the ground electrode, and the electrode is damaged.
It was found that the frequency of electrode replacement also increased.

FIG. 4 (a) is a diagram schematically showing a state of discharge of a plasma in a gas discharge. In FIG. 4 (a), a mark 38 indicates a location where concentrated discharge is likely to occur, and a symbol 39 indicates a location where concentrated discharge occurs. Are shown schematically. FIG.
It is the figure which expanded the edge part of (a), and was the figure which showed typically the state of discharge of the discharge plasma in gas. 31 is a gas discharge plasma processing apparatus, 32 is a processing chamber, 33 is a schematic discharge state visually drawn, and the discharge state is indicated by a line, and 33 'is an end of the plastic support visually. The typical state of avoiding and discharging is indicated by a line, 36 and 37 are electrodes, 36A and 37A are metal parts of electrodes, 36B
Reference numerals 37B and 37B denote dielectric portions, 38 denotes a portion where concentrated discharge is likely to occur by a circle, and 39 denotes a portion where concentrated discharge is received. At the end of the plastic support 5, 33 '
It is considered that the discharge escapes to the lower electrode 37 by bypassing the end of the plastic support 5 without processing the end as schematically shown in FIG. Then, the discharge concentrates at the location 39 to damage the electrode 37. Normal discharge is plastic support 5
It is thought that the discharge falls vertically toward the surface, but at the end, unlike the part inside, discharge flows outside the finite object to be processed.

As a result of diligent studies on this phenomenon, the present inventor has first found that a concentrated discharge does not occur and that the discharge does not bypass.

In the configuration (1) of the present invention, the electrode is prevented from being damaged by the concentrated discharge near the end of the plastic support in the processing chamber. In order to prevent the concentrated discharge, the portion through which the plastic support does not pass is used. This is an apparatus in which the electrode itself or the vicinity of the electrode is improved so as to change the impedance generated between the electrodes at the electrode ends (in the width direction).

One of them is to deform at least one of the pair of electrodes so as to warp, gradually increasing the distance between the electrodes, and changing the impedance.

FIG. 5 is an enlarged schematic diagram showing a portion where the distance between the electrodes near the end of the electrode of the apparatus for plasma-in-gas plasma treatment of the configuration (1) is changed. By increasing the distance (gap) between the electrodes by warping the ends of the electrodes 46 and 47, the discharge at the warped portion is weakened and the concentration of the discharge does not occur.
The degree of the increase in the gap is preferably at least 2 mm, more preferably at least 5 mm, than the middle portion of the plastic support. However, depending on how to bend, discharge concentration may occur at the bent part,
It is better to avoid such shapes.

FIG. 6 is an enlarged schematic view showing a portion where the thickness of the electrode dielectric at the end of the electrode changes, and the thickness of the dielectric portions 56B and 57B at the ends of the electrodes 56 and 57 is changed as shown in FIG. By changing the impedance, the impedance between the electrodes is changed. This corresponds to configurations (1) and (2). The shape in which the thickness is changed may be thicker toward the end of the electrode, or may have a rounded shape,
It is not limited to the form shown in FIG. In this case, an increase in the impedance decreases the dielectric constant, but it is preferable to decrease the impedance by the resistance of the plastic support. In the drawing, reference numeral 51 denotes an in-gas discharge plasma processing apparatus, and reference numeral 52 denotes a processing chamber.

Another configuration for changing the dielectric constant is to provide an insulator between the two electrodes (gap) from a portion of the processing chamber through which the support does not pass to a position slightly inside the end of the support. It does not induce concentrated discharge by insertion (FIG. 7). FIG. 7 is an enlarged schematic view showing a portion where an insulator is inserted between the electrodes at the ends of the electrodes. The plastic support is sandwiched between the electrodes 66 and 67 so as to sandwich the insulator 63 near the end of the plastic support 5. 5 is a diagram installed on both sides of FIG. The insulator 63 can be used without limitation as long as it can be insulated and is not destroyed by electric discharge. In the figure, 61 is an in-gas discharge plasma processing apparatus, 62 is a processing chamber, 66A and 67A are metal parts (of electrodes), 66B and 6
7B is a dielectric portion.

The structure (3) of the present invention is a gas discharge plasma processing apparatus having at least one of a pair of electrodes having a metal pipe inside a dielectric pipe, and having a metal pipe electrode. FIG. 8A is a schematic cross-sectional view from the front showing another example of the in-gas discharge plasma processing apparatus in which pipe-shaped electrodes are arranged. FIG. 8B
FIG. 9 is a partial cross-sectional view (one side) of the pipe electrode of FIG.

FIG. 8B shows an example of an electrode having a metal pipe in a dielectric pipe. The pipe-shaped electrode 73 includes a metal pipe 74, a dielectric pipe 75, an insulator pipe joint 76, and an insulator pipe 77. And a metal block (hollow cylindrical shape) 78. The metal pipe 74 is fixed in contact with the hollow portion of the metal block 78, and an insulator pipe 77 is joined to the outer half of the block 78, and the other half is joined to an insulator pipe joint 7 to which a dielectric pipe 75 is joined.
6 are joined. Outside of the metal block 78, the joint between the insulator pipe 77 and the insulator pipe joint 76 is slightly vacant, and a lead wire 70 for connecting to a high-frequency power source or ground is provided there. Insulator pipe 77
The material of the joint 76 and the insulator pipe may be a plastic pipe such as that usually used for plastic piping, such as vinyl chloride, and any pipe having an insulator can be used without any limitation.

The metal pipe 74 and the insulator pipe 77 provided inside the dielectric pipe 75 are formed by a metal block 78.
The liquid is tightly joined through the through hole so that the liquid to be inserted therein does not leak. The liquid is cooled by flowing through the insulating cooling medium 79, whereby the conditions can be leveled and the processing effect can be made uniform.
Can achieve a stable surface treatment effect, particularly an adhesive effect (configuration (4)). Further, the electrodes do not have heat and the dielectric pipe is hardly damaged. The material of the dielectric pipe is the same as that of the dielectric, but a pipe processed is used. For example, glass pipes and the like are easy to procure, have good performance, and have a low cost, which is preferable. The insulating cooling medium is, for example, a liquid hydrocarbon compound which is usually liquid, and preferably has a viscosity as low as possible and a high heat conduction efficiency. Depending on the purpose of use, a conductive cooling liquid such as an aqueous solution containing an inorganic salt or an organic salt may be used.

On the other hand, the prior art is disclosed in
JP-A-6718 discloses an electrode in which the outer wall of a metal pipe is covered with a dielectric such as ceramic, and JP-A-7-220895 describes an electrode in which a glass pipe is silver-plated. However, these are difficult to coat so that there is no thickness or unevenness of the coat, and require fairly precise techniques, and are expensive and impractical. The configurations (3) and (4) of the present invention provide a low-cost and efficient pipe electrode.

The constitution (5) of the present invention is a method for performing a discharge plasma treatment in a gas on a plastic support using the apparatus described in the constitutions (1) and (4). As described above, various constituent layers of the silver halide photographic material, such as an undercoat layer, an antihalation layer,
A crossover light cut layer, a silver halide emulsion layer, an antistatic layer and the like can be firmly adhered.

The structure (6) of the present invention is the same as the structure (5), except that the plastic support continuously transported in the processing chamber in the gas discharge plasma processing apparatus is subjected to the atmospheric pressure or a pressure close to the atmospheric pressure. When 50% or more of the inert gas to be introduced is treated as an argon gas, the treatment is performed such that the effective gas at the end of the support is smaller than the middle in the width direction. The gas atmosphere at the end of the plastic support is locally reduced, the effective gas in the composition of the processing gas is reduced, or the gas concentration is reduced. This reduces the processing capacity of the end portion and suppresses the concentrated discharge. Means for locally changing the atmosphere are implemented by providing a partition with an insulator or extending the opening of the gas inlet near the support separately from the middle of the plastic support. I can do it. The effective gas concentration in the composition is preferably such that the argon gas is reduced to 10 to 20% by pressure. Further, the whole gas concentration may be diluted with a gas other than oxygen or air, for example, a nitrogen gas, and may occupy 30 to 40% of the whole gas.

The constitutions (7) to (9) of the present invention relate to an apparatus for removing dust which is liable to be adhered in a gas discharge plasma treatment.

FIG. 9 is a schematic diagram showing a static eliminator, a gas discharge plasma treatment apparatus with a cleaner, and a coating and drying process. The plastic support 105 pulled out from the plastic support roll 100 is first processed by the gas discharge plasma processing apparatus 101, and
2, each is processed by the static eliminator 103 and then by the dust remover 104, and the coating device 1 is placed on the back roll 107.
In step 06, a coating liquid is applied, dried in the drying device 108, and finally wound up as a coated roll 109.

First, the configuration (8) will be described. When a plastic support is transported in a roll, it contacts or separates from a roll (for example, a guide roll of 102) and is charged or peeled off, and attracts and adheres a small amount of dust floating in the air. There are many. When a coating liquid of a constituent layer such as an undercoat layer, an antistatic layer, an antihalation layer, a crossover light cut layer, a silver halide emulsion layer, or the like is later applied to the plastic support to which dust is attached by such charging. In addition, coating defects such as repelling and tailing may be generated at places of dust, and adhesiveness may be partially deteriorated. As a result, the quality of the product as a product is impaired.
The charge of such a plastic support is a mixture of positive and negative polarities, and may be as high as 20 kV or more. In particular, the plastic support that has been subjected to the discharge plasma treatment in gas is easily charged by the discharge treatment, and is liable to be contaminated by dust and the like.

Countermeasures against charging and contamination before and after the gas discharge plasma treatment can be performed by subjecting the plastic support to a static elimination treatment and a dust removal treatment as described below before and after the treatment. For the charging as described above, an effect can be found only by a normal blower type or a contact type, but the present inventors have proposed a plurality of positive / negative ion generating static elimination electrodes and an ion attraction electrode so as to sandwich the support. , A high-density static elimination system having a positive / negative DC type static eliminator, and an AC type static eliminator behind the static eliminator (for example, JP-A-7-263173).
It is found that the static elimination effect is remarkable by providing (hereinafter described in Japanese Patent Application Laid-Open No. H10-203) before or after the discharge plasma treatment in gas. These charge removal treatments may be performed before or after the in-gas discharge plasma treatment, but it is preferable to perform the treatment before, after, and before and after the in-gas discharge plasma treatment. The latter is more preferable in terms of equipment costs.

As the high-density static elimination system, an apparatus and a method described in JP-A-7-26173 are preferable. In this system, when the positive and negative ion generating electrodes generate positive and negative ions alternately or simultaneously, a positive and negative high voltage is alternately applied to the ion attraction electrode. The generated positive and negative ions are attracted by the ion attracting electrode. In other words, the plastic film (charged film) being charged and transferred has a coupling capacity C with the ion attraction electrode, or directly when there is no coupling capacity,
Since positive and negative potentials are induced alternately, positive and negative ions from the positive / negative ion generating neutralizing electrode are forcibly attracted toward the charged film surface. As a result, a myriad of small positive and negative charged parts are randomly mixed to form a complicated charged pattern,
Even if the surface of the charged film is microscopically neutralized, in addition to the above-mentioned potential being induced in the charged film, negative ions are applied to the positively charged portion and negatively charged portions are provided. Positively reacts positively to positively and negatively charge each of the positively and negatively charged portions separately. In this case, since the ion attracting electrode has a surface extending in the direction perpendicular to the running direction of the charged film and in the direction perpendicular thereto, there is no spatial unevenness in the ion attracting force, and positive and negative ions can be equally attracted. There is little uneven static elimination. The polarity of the voltage applied to the positive and negative ion generating electrode and the ion attracting electrode changes, and the charged film moves with respect to these electrodes. And the place where the charge removal by the negative ions is strong alternates.
Therefore, a plurality of positive / negative ion generating static elimination electrodes are arranged in parallel in the traveling direction of the charged film, and the positive and negative ions due to these are forcibly irradiated on the charged film in different places,
Not only can the static elimination efficiency be increased, but also the positive and negative static elimination actions can be averaged in the running direction of the charged film to reduce such static elimination unevenness. In addition, the elimination of such macroscopically appearing static elimination unevenness is achieved by gradually weakening the static elimination action by a plurality of positive / negative ion generating static elimination electrodes in the traveling direction of the charged film, and by using a DC neutralizer as a next auxiliary process. The combined use of a weak DC neutralization and a weak AC neutralization by an AC neutralizer can further improve the performance.

Next, the dust removing device 104 having the configuration (9) will be described. In order to remove dust and the like adhering to the plastic support, it is effective to provide and use a non-contact type jet wind decompression type dust removing device such as the device described in JP-A-7-60211. This non-contact type jet wind decompression type dust remover has an ultrasonic generator inside an air jet nozzle, and sprays the jetted ultrasonic air (also called ultrasonic pressure) from two directions onto the surface of a plastic support. They are merged to generate a turbulent flow, give buoyancy to the dust, peel off the dust, and suck the dust by a suction nozzle.

A favorable effect can be obtained by installing and using the dust removing device in combination with the above-described static removing device. In the configuration (7), by providing the static eliminator and the dust eliminator before and / or after the in-gas discharge plasma processing apparatus, it is possible to effectively obtain a treated plastic support free of dust. If a further effect is desired, it is preferable to install it behind the gas discharge plasma processing apparatus. In the present invention, the static eliminator and the dust eliminator are not limited to the above.

The structure (10) of the present invention comprises the structures (7) to (7).
(9) The method of performing static elimination processing and dust elimination processing using the device of (9),
This is a method of treating a plastic support subjected to discharge plasma treatment in a gas without contamination. As a result, the coating property of the adhered object of the plastic support subjected to the discharge plasma treatment in gas is improved, and a product having no defect in coating quality can be manufactured.

The constitution (11) of the present invention is a method for further improving the adhesion of the plastic support by physically roughening the surface of the plastic support and performing discharge plasma treatment in gas. The non-adhered material cannot be adhered simply by roughening, but the present inventors have found that the treatment with a discharge plasma in a gas significantly improves the adhesiveness of a plastic support that is not roughened. Was found. In particular, the surface roughness is defined as Ra at the center line average roughness of 0.1.
This effect is remarkable by setting it to μm or more. Examples of such a roughening method include sandblasting and addition of a filler in plastic, but are not particularly limited. In addition, the present inventors have found that since the treated surface of a plastic support subjected to discharge plasma treatment in gas is easily blocked when wound in a roll, blocking can be suppressed by roughening the surface in advance.

According to the constitutions (12) and (13) of the present invention, for a plastic support whose surface used as a product cannot be roughened, only the both ends of the support are roughened to perform a discharge plasma treatment in gas. This is a method for treating a plastic support that is difficult to block even when wound into a roll. The roughened portion is preferably 5 to 30 mm from both edges. Also, when the constituent layers of the silver halide photographic light-sensitive material are coated on the plastic support, the constituent layer coating solution is applied to the far end, so that even in the case of the present constitutions (12) and (13), The coating material is applied to both end portions of the surface, but the coating material in that portion does not block even if it is wound into a roll after drying. Further, the adhesiveness of the portion is good, and the portion does not peel off during drying.

The constitution (14) of the present invention relates to a method for surface treatment of an aluminum support for a lithographic printing plate.

Conventionally, the treatment of an aluminum support for a lithographic printing plate is performed entirely by a wet method. First, the aluminum plate is degreased, and then complicated processes such as washing, polishing (also called graining), washing, anodizing, washing, sealing, hydrophilizing, washing, and drying are performed. It is done individually. However, the process up to anodization is a process necessary for imparting the specificity of the lithographic printing plate aluminum support (including the subsequent hydrophilization), and cannot be omitted at present. Nevertheless, if simplification can be achieved only by sealing treatment or hydrophilization treatment after anodic oxidation, it greatly contributes to the reduction of manufacturing time and cost of the lithographic printing plate aluminum support, space saving in the treatment step, and the like.

The aluminum plate used in the present invention can be used as long as it is grained. The graining method is such that after the surface of the aluminum plate is degreased, the graining is performed by a brush polishing method, a ball polishing method, a chemical polishing method, an electrolytic etching method, etc., preferably, a deep and uniform grain is obtained. Grained by electrolytic etching. Anodizing treatment is, for example, an inorganic salt such as phosphoric acid, chromic acid, boric acid, or an organic acid such as oxalic acid alone, or in an aqueous solution of a mixture of two or more of these acids, preferably in an aqueous sulfuric acid solution. This is performed by passing a current through an aluminum plate as an anode. Anodized film amount is 5-60
mg / dm ² is preferred, and more preferably 5 to 30 mg.
/ Dm ² . Thereafter, a sealing treatment and a hydrophilic treatment are performed. The sealing treatment and the hydrophilization treatment are performed by immersing in a 0.1 to 3% aqueous solution of sodium silicate at a temperature of 80 ° C. to 95 ° C. for 10 seconds to 2 minutes. Then 40-95
It is common to immerse in water at 10 ° C. for 10 seconds to 2 minutes for treatment.

Also, for example, a method of graining the surface of an aluminum plate and treating it with a silicate (US Pat. No. 2,714,066) or a method of treating it with an organic acid salt (US Pat. No. 2,714) , 066), a method of treating with phosphonic acid and derivatives thereof (US Pat. No. 3,220,8).
No. 32), a method of treating with potassium hexafluorozirconate (US Pat. No. 2,946,683), a method of anodizing, and a method of treating with an aqueous solution of an alkali metal silicate after the anodizing (US Pat. 181 461)
Etc.

In the constitution (14) of the present invention, the above-mentioned hydrophilic treatment (including the sealing treatment) is performed by a flame treatment, which is cheaper in terms of equipment than ordinary sealing treatment and hydrophilic treatment, and low in cost. Not only can the aluminum lithographic printing plate support of the present invention be obtained, but also the printing durability can be greatly improved.

Generally, the flame emitted from the burner includes an outer flame and an inner flame, and the outer flame portion is a portion of the inner flame portion, which is usually light blue in which unreacted (cannot burn) gas is heated. The so-called blue gas flame is a part where the temperature is high, and the non-blue flame part is a part where the internal flame is relatively low and the oxygen supply is low. In the present invention, it is preferable to use the tip portion of the internal flame portion. It is common practice to mix an active gas, such as air or oxygen, in the combustion gas as a gas mixture before forming a flame in order to increase the combustion temperature. In addition, when entrained air is entrained in the support to be transferred, the flame fluctuates and becomes unstable, so it is preferable to shut off the entrained air. The shutoff of the entrained air can be performed by a method as described in Japanese Patent Application No. 10-45361.

The combustion gas used in the present invention is a paraffinic gas such as city gas, natural gas, methane gas, ethane gas, propane gas, butane gas, and the olefinic gas is ethylene gas, propylene gas, or acetylene gas. It is useful, and only one kind or two or more kinds may be mixed.

The treatment with the flame of the present invention is carried out by introducing at least one kind of each of an inert gas and a reactive gas (also referred to as an active gas) from the outside so as to surround the flame of the flame part. This is a method of eliminating the fluctuation of the treatment and efficiently activating the surface of the support.
The combustion gas and the oxidizing gas may be mixed and used to such an extent that the surface treatment of the present invention is not hindered. The mixing ratio varies depending on the type of combustion gas. For example, in the case of propane gas and air, a preferable mixing ratio of propane gas to air is 1:15 to 1:22, preferably 1:16 to 1:22 by volume ratio. 19, and in the case of natural gas and air, 1: 6 to 1:10, more preferably 1: 7 to 1: 9.
It is preferred that The ratio of the size of the internal flame to the size of the external flame differs depending on the type of combustion gas, the type of oxidizing gas, their mixture ratio, the gas supply speed, and the like.

At least one of the reactive gas and the inert gas used in the present invention may be, for example, nitrogen gas or argon gas alone, or may be a mixture of nitrogen gas and argon gas. Any number of types may be mixed regardless of a reactive gas and an inert gas.

The reactive gas used in the hydrophilization treatment (flame treatment) of the present invention is preferably a nitrogen gas, an oxygen gas, a carbon dioxide gas, a hydrogen gas, a water vapor gas, or an ammonia gas. Although it can be used, nitrogen gas, oxygen gas, carbon dioxide gas and steam gas are particularly preferable.

Examples of the inert gas used in the present invention include helium gas, neon gas, argon gas, krypton gas, and xenon gas. The inert gas is used to reduce fluctuations in processing on a photographic support. Helium gas, neon gas and argon gas are preferable, and argon gas is particularly preferable in view of cost.

The present invention preferably treats the support with a restricted flame at a distance within 30 mm from the tip of the inner flame. A large amount of plasma is generated in the flame within 30 mm from the tip of the inner flame, and the processing of the support can be performed most effectively.

In the present invention, the time for applying a flame to the aluminum plate, that is, the time for the aluminum plate to pass through an effective flame portion is preferably 0.001 second or more and 2 seconds or less.
More preferably, the time is 0.01 second or more and 1 second or less. If it is longer than 2 seconds, the surface of the aluminum plate is eroded and loses its adhesive ability. If the time is less than 0.001 second, the oxidation reaction hardly occurs and it is hard to contribute to the adhesion. The processing speed of the aluminum plate in the present invention is 1 to 50 m / min, preferably 3 to 30 m / mi.
n. If the treatment energy is 100 W / min / m ² or more, the hydrophilicity-imparting effect is sufficient and the printing durability is improved as compared with the conventional hydrophilization treatment, but preferably 150 to 700.
W / min / m ² .

The burner for surface treatment used in the present invention is not limited as long as it can uniformly apply a flame to the surface of the aluminum plate. A horizontal slit box burner having a width equal to or larger than the width of the aluminum plate may be used, and may be one which maintains uniformity in the direction. Further, a plurality of such horizontally slit box-type burners may be arranged in the traveling direction of the aluminum plate.

The shielding plate may be flat or curved. The curved shielding plate may be curved along the back roll or may be curved to the opposite side. In addition, the plate-shaped shielding plate may be a single plate, a finned shape, or a hollow shape through which cooling water can pass, and the shape is not limited. A form that can be cooled is preferable for the purpose of protecting the web from unnecessary heat and for facilitating control. In each case of the horizontally slit box burner, the effective processing holes are opened as long narrow slits. The effective processing hole may be covered with a mesh.

The flame treatment of the present invention may be carried out with a back roll, or without a roll between two rolls.

In general, the diameter of the back roll is preferably increased when the burner output is large. However, the diameter of the back roll is not so affected by the burner output, and may be appropriately selected.

The direction in which the flame is applied may be from the upper side of the back roll, from the side, or from below.

The material of the back roll used in the flame treatment of the present invention is not particularly limited as long as it is a heat-resistant material.
Iron, iron chrome plating, SUS304, 316, 42
Rolls such as 0 can be used. Also alumina,
Ceramic rolls such as zirconia and silica are also preferably used. Further, in order to obtain the surface stability of the back roll, it is particularly preferable to use a cooling back roll capable of maintaining a constant temperature, and in this manner, a rubber back roll can also be used. In the present invention, a rubber roll is elastic, and is particularly preferable because of its compatibility with the nip roll. Cooling roll is 0 ° C ~ 95
It is better to control between ° C. Especially 25 ° C to 80
C is preferred. Metal or ceramic is preferred from the viewpoint of heat resistance.

In the present invention, the position where the nip roll for shutting off the entrained air is pressed against the back roll is located between the position where the conveyed aluminum plate is in contact with the back roll and the position for flame treatment, and the position for flame treatment. It is better to be 10 to 30 cm in front.

As the material of the nip roll of the present invention, any of rubber, resin, metal and ceramic can be used. These materials can be substantially the same as the back roll. Rubber is preferable in terms of elasticity and ceramic is preferable in terms of heat resistance, but it is preferable not to use the same material as the material of the back roll. In the case of rubber, its hardness is 5-9.
If it is 0 (JIS), it can be used, and preferably about 20.

The force by which the nip roll of the present invention presses the aluminum plate toward the back roll is 1 to 500 kg.
/ Cm, preferably in the range of 30 to 100 kg / cm. Almost all entrained air can be cut off in the former range, but entrained air can be cut off completely in the latter range.

When shutting off the air entrained by the aluminum plate being transported according to the present invention, a decompression box may be provided at the same location to suck the shut off air.

Hereinafter, the present invention will be described with reference to Examples, but it should not be construed that the invention is limited thereto.

[0089]

EXAMPLES (Evaluation of Adhesion Test 1) Gelatin coating solution (3
(A coating solution containing a small amount of a surfactant in a 1% by weight aqueous gelatin solution) was applied to a treated plastic support with a wire bar so as to have a dry film thickness of 0.1 μm, and dried. Cut the razor blade in parallel at an angle of 45 ° to the film surface at an interval of about 2 cm so that the gelatin surface reaches the plastic support surface.
Put a book. A commercially available cellophane tape having a width of 2.54 cm is attached to the gelatin surface by rubbing it tightly with a round tip. Hold the end of the tape with your finger and pull the tape from the gelatin surface by pulling it in the direction opposite to the 45 ° cut. The presence of a film is evaluated according to the following evaluation criteria (% of the peeled area with respect to the area of the attached cellophane tape).

A: No peeling at all (0%) B: Very little peeling at the blade (2% or less) C: 3 to 10% D: 11 to 50% E: 51 to 100% F: 101 %that's all.

(Evaluation of Adhesion Test 2) The above gelatin coating solution was applied to a plastic support subjected to discharge plasma treatment in gas with a wire bar so as to have a dry film thickness of 0.1 μm. Cut to length. Next, two samples were placed on each other with the gelatin surfaces facing each other at 50 mm on one end.
Were adhered to each other so that the remaining portions were overlapped with each other, and a heavy weight was put on an atmosphere of 35 ° C. and 80% RH for 2 days and left to adhere. These samples were kept at 20 ° C,
After being left for 1 day in an atmosphere of 40% RH, the non-adhered end of the sample was fixed to upper and lower clips by a Tensilon (manufactured by Toyo Seiki) tensile tester, and a T-shaped 10 cm / mi was formed.
Pulled with n. Maximum tensile strength during tension (gfm)
Was the peel strength.

(Evaluation of coatability) As described above, a gelatin coating solution was coated on a plastic support subjected to discharge plasma treatment in a gas, dried, and spots of coating abnormalities (for example, cissing, crater, tailing, etc.) per 10 m ² were obtained. Was evaluated.

(Evaluation of blocking) A roll of a plastic support or a roll coated with a gelatin coating solution was wound up, and then left for 48 hours in an atmosphere of 30 ° C. and 55% RH.
Unravel and see how it sticks.

A: Not at all disentangled (rattles loose) B: Not distorted, but not loosen as A E: The support breaks due to cracking.

Embodiment 1 The electrodes of the gas discharge plasma processing apparatus having the structure as shown in FIG. 2 were obtained by straightening the both ends of the electrode as shown in FIG. 3 (a), by warping it as shown in FIG. 5 (b), As shown in FIG. 6, a thicker dielectric (c) and an insulator as shown in FIG. 7 (d) were prepared. The upper and lower electrodes are made of a metal of aluminum and a dielectric of ceramic.
(A) is a comparative example.

Operating conditions Under the following conditions, the processing chamber was purged for 10 minutes after the gas introduction was started, and the plastic support was transported to start the processing.
The processed product 2 minutes after the stabilization was sampled.

Plastic support: 400 mm width, 1
Polyethylene-2,6-naphthalate film of 00 μm Processing gas: Introduced inert gas 100% pressure argon gas, ratio of inert gas to reactive gas: Ar: N ₂ =
50: 1 Frequency: 10 kHz Gap between electrodes (in the case of an electrode whose both ends are changed, at the center): 5 mm Electrode length: 600 mm Position changed at both ends of the electrode: 5 mm in from both ends of the plastic support width To the electrode both ends Transport speed: 150 m / min Transport time: 60 minutes Processing time: 0.5 sec Output: 22 kW / m ² After processing under the above conditions, the result of confirming the concentrated discharge trace of the electrode and the above gelatin on the processed plastic support The coating solution was applied and the results of adhesion are shown in Table 1.

[0098]

[Table 1]

(Results) It was found that the straight electrode of the comparative example had two concentrated discharges during the experiment. In contrast, concentrated discharge did not occur in the electrode of the present invention in which the impedance was changed or the dielectric constant was changed. In the comparative example, the adhesiveness of the end portion where the concentrated discharge easily occurs was not satisfactory because the plasma discharge treatment in gas was not sufficient. On the other hand, the electrode of the present invention had considerably good adhesiveness.

Example 2 A straight electrode was used.
The procedure was performed in the same manner as in Example 1 except that the atmosphere near both ends of the 6-naphthalate film was as described below.

Process gas: Inert gas to be introduced is 100% by pressure argon gas, and the ratio of inert gas to reactive gas is
Ar: N ₂ = 50: 1 Process gas near both ends: 85% by pressure argon gas, 15
The pressure ratio of helium gas, inert gas and reactive gas was set to (Ar + He): N ₂ = 70: 1. Table 2 shows the results of confirmation of the trace of concentrated discharge of the electrode and the results of adhesion obtained by applying the gelatin coating solution to the treated plastic support.

[0102]

[Table 2]

(Results) In the comparative example treated with a uniform gas composition, concentrated discharge occurred and the adhesion at the end portions was poor. Showed sex.

Example 3 A process was performed in the same manner as in Example 1 except that the pipe electrodes shown in FIGS. 8A and 8B were used as the electrodes. A comparative example using a normal straight electrode was used.

Electrode: glass pipe electrode, hydrocarbon containing octane as a main component as insulating cooling medium (3 ° C., flow rate 1)
0 l / min), electrode using a ceramic pipe as a dielectric. After treatment under the above conditions, the above gelatin coating solution was applied to the treated plastic support, and the adhesion was shown in Table 3. In addition, a pipe electrode similar to that described in JP-A-6-96718 was manufactured, and the cost of the pipe-shaped electrode of the present invention when the manufacturing cost was set to 1.0 was compared.
It was shown to.

[0106]

[Table 3]

(Results) It was found that when the electrode of the present invention was used, the adhesiveness at the end portion was good and it was more advantageous than the ordinary electrode. The production cost of the pipe electrode of the present invention is:
The production cost of the pipe electrode of the present invention can be reduced by 30% when the cost of producing the same electrode as the pipe-shaped electrode described in JP-A-6-96718 is 1.0.

Example 4 A treatment was performed in a test room using a series of devices shown in FIG. 9, and the above gelatin coating solution was applied, dried and wound up.

Gas discharge plasma processing apparatus: same as in FIG. 1 Static eliminator: Use of high-density static elimination processing system manufactured by Kasuga Electric Co., Ltd. Dust remover: Use of jet wind decompression type dust remover Coating apparatus: Extruder type coater, dryer Clean test room Degree: Class 100, Class 1000,
The coatability of the sample on which the class 10000 gelatin layer had been coated was evaluated, and the results are shown in Table 4.

[0110]

[Table 4]

(Results) From the viewpoint of applicability, a processing apparatus having neither a static eliminator nor a dust remover had poor applicability and was worse as the cleanliness decreased. It has been found that, in a processing apparatus having either a static eliminator or a dust eliminator, by having these, the applicability is greatly improved. Further, in the processing equipment provided with both the static eliminator and the dust remover, there was no problem in applicability.

Example 5 A polyethylene-2,6-naphthalate film, which had been roughened with a carborundum, washed with water and dried, was subjected to an in-gas discharge plasma treatment in the same apparatus as in FIG. 1 to apply the above gelatin coating solution. Then, it was subjected to adhesiveness evaluation. Table 5 shows the roughness and the results. Those having a surface roughness Ra of less than 0.1 were used as comparative examples.

[0113]

[Table 5]

(Results) In the present invention in which the surface of the plastic support was roughened, the adhesiveness was improved, and blocking hardly occurred. On the other hand, the plastic support having a very small roughness (Ra <0.1) of the comparative example was susceptible to blocking.

Example 6 The same procedure as in Example 5 was carried out except that a polyethylene-2,6-naphthalate film whose both surfaces were roughened only at 30 mm in the same manner as described above was used. Those which were not roughened were used as comparative examples. Table 6 shows the results.

[0116]

[Table 6]

(Results) The comparative example in which both end portions were not roughened had strong blocking and slightly poor adhesion, whereas the roughened end portion of the present invention had good adhesion, and No blocking occurred.

Example 7 [Preparation of flame-treated lithographic printing aluminum support 1] An aluminum plate having a thickness of 0.3 mm (material 1050, temper H
16) was immersed in a 10% by weight aqueous solution of sodium hydroxide kept at 85 ° C., degreased for 1 minute, and then washed with water. The degreased aluminum plate was immersed in a 10% by weight aqueous sulfuric acid solution kept at 25 ° C. for 1 minute, subjected to desmut treatment, and washed with water. Next, this aluminum plate was placed in a 2.0% by weight aqueous hydrochloric acid solution at a temperature of 30%.
The surface was roughened for 30 seconds at a temperature of 80 ° C. and a current density of 80 A / dm ² . Thereafter, the substrate was immersed in a 1% by weight aqueous sodium hydroxide solution maintained at 70 ° C. for 10 seconds, and then washed with water. Next, the film was immersed in a 10% aqueous sulfuric acid solution maintained at 25 ° C. for 10 seconds, and then washed with water. Then, in a 30% sulfuric acid aqueous solution,
Anodizing treatment was performed for 2 minutes at a temperature of 45 ° C. and a current density of 3 A / dm ² , followed by washing with water. Thereafter, flame treatment was performed under the following conditions to obtain an aluminum support for lithographic printing.

[Preparation of hydrophilically treated lithographic printing aluminum support 2] Comparative Example The same treatment was carried out until the anodic oxidation of the flame-treated lithographic printing aluminum support, and then the temperature was maintained at 80 ° C.
Sealed by immersing in 0% ammonium acetate aqueous solution for 1 minute,
The substrate was subjected to a hydrophilic treatment, washed with water, and dried at 80 ° C. for 5 minutes to obtain an aluminum support for lithographic printing.

Flame treatment conditions Aluminum plate width: 65 mm Burner: 1 slit box type burner Combustion gas: propane gas: air = 1: 18 (volume ratio), mixed and burned, and the aluminum plate was further burned by internal flame Combustion energy, processing speed, processing time: described in Table 7 Gap: 30 mm Photosensitive layer: novolak resin (molar ratio of phenol / m-cresol / p-cresol is 10/54/36, weight 6.70 g Pyrogallol acetone resin (weight average molecular weight 3000) and o-naphthoquinone diazide-5-sulfonyl chloride condensate esterification rate 30%) 1.50 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.08 g 2,4- Bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15 g fluorinated surfactant FC-430 (manufactured by Sumitomo 3M) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0 .02 g ethylene glycol monomethyl ether 100 ml The photosensitive layer coating solution was applied to the aluminum support with a wire bar so that the dry film thickness was 2.0 g / m ² .
After drying at 80 ° C. for 2 minutes, a lithographic printing plate was obtained and exposed to a 4 kW metal halide lamp from a distance of 1 m for 30 seconds. The exposed plate was immersed in a 6-fold diluted solution of SDR-1 developer manufactured by Konica Corporation at 25 ° C. for 30 seconds, washed with water and developed. The exposed lithographic printing plate was printed using a Heidel GTO printing machine, and the printing durability was examined. We also estimated the rate of cost reduction by flame treatment. Table 7 shows the results of the applied processing energy, printing durability, and cost reduction rate.

[0121]

[Table 7]

(Results) The planographic printing plate made hydrophilic by the flame treatment was excellent in printing durability, and in particular, the sample 32 to which a large amount of processing energy was applied had extremely high printing durability. On the other hand, the printing durability of the comparative example was small. In addition, it was found that the cost reduction rate could be reduced by 8 to 10% by using the flame treatment.

[0123]

According to the present invention, it is possible to provide an excellent surface treatment apparatus and method for a plastic support by an in-gas discharge plasma treatment, and a surface treatment apparatus and a treatment method for a plastic support having inexpensive electrodes.

Separately, it is possible to provide an aluminum support for a lithographic printing plate which can be reduced in cost by flame treatment and has excellent printing durability.

[Brief description of the drawings]

FIG. 1 is a schematic view showing one example of an in-gas discharge plasma processing apparatus.

FIG. 2 is a schematic view showing another example of the in-gas discharge plasma processing apparatus.

FIG. 3 is a schematic cross-sectional view as viewed from the front, showing an example of an in-gas discharge plasma processing apparatus.

FIG. 4 is a diagram schematically showing a state of discharge of discharge plasma in gas.

FIG. 5 is an enlarged schematic view showing a portion where an inter-electrode distance at an electrode end changes.

FIG. 6 is an enlarged schematic view showing a portion where the thickness of an electrode dielectric at an electrode end changes.

FIG. 7 is an enlarged schematic view showing a portion where an insulator is inserted between electrodes at an electrode end.

FIG. 8 shows still another example of the in-gas discharge plasma processing apparatus.
It is the cross section which was seen from the front which shows the example which arranged the pipe-shaped electrode.

FIG. 9 is a schematic diagram showing a static eliminator, a gas discharge plasma treatment apparatus with a cleaner, and a coating and drying process.

[Explanation of symbols]

1,21,31 Discharge plasma processing apparatus in gas 2,22,32 Processing chamber 3a, 3b Preparatory chamber 5 Plastic support 6,7,16,17,26,27,36,37 Electrodes 6A, 7A, 16A, 17A , 26A, 27A, 36
A, 37A Metal parts 6B, 7B, 16B, 17B, 26B, 27B, 36
B, 37B Dielectric part 8 Guide roll 10, 20, 30, 70 High frequency power supply 70 Lead wire 73 Pipe-shaped electrode 74 Metal pipe 75 Dielectric pipe 76 Insulator pipe joint 77 Insulator pipe 78 Metal block 79 Insulating cooling medium 100 Plastic support roll 101 Gas discharge plasma treatment apparatus in gas 102 Guide roll 103 Static eliminator 104 Dust remover 105 Plastic support 106 Coating device 107 Back roll 108 Drying device 109 Coated roll

Claims (14)

[Claims] 1. A plastic that is continuously transferred between a pair of electrodes under an atmospheric pressure or a pressure in the vicinity thereof, under a mixed gas atmosphere having a composition in which 50% by weight or more of an inert gas to be introduced is an argon gas. What is claimed is: 1. A surface treatment apparatus for a plastic support, wherein said support is treated by discharge plasma in a gas, wherein at least one of said pair of electrodes has a different impedance in a longitudinal direction. apparatus. 2. A plastic that is continuously transferred between a pair of electrodes under an atmospheric pressure or a pressure close to the atmospheric pressure, and in a mixed gas atmosphere having a composition in which 50% by weight or more of an inert gas to be introduced is an argon gas. A surface treatment apparatus for a plastic support for treating a support by discharge plasma in a gas, wherein at least one of the pair of electrodes has a different dielectric constant in a length direction. Processing equipment. 3. A plastic that is continuously transferred between a pair of electrodes under a pressure of the atmospheric pressure or a pressure close to the atmospheric pressure, and in a mixed gas atmosphere having a composition in which 50% by weight or more of an inert gas to be introduced is an argon gas. What is claimed is: 1. A plastic surface treating apparatus for treating a support by discharge plasma in a gas, wherein at least one of the pair of electrodes has a pipe shape, and a metal pipe is provided in a dielectric pipe of the electrode. Support surface treatment equipment. 4. The apparatus according to claim 3, wherein the electrode has an insulating cooling medium therein. 5. A method for treating a surface of a plastic support, wherein the method is carried out by the apparatus according to claim 1. Description: 6. A plastic that is continuously transferred between a pair of electrodes under an atmospheric pressure or a pressure close to the atmospheric pressure, and in a mixed gas atmosphere having a composition in which 50% by weight or more of an inert gas to be introduced is an argon gas. A surface treatment method for a plastic support, characterized in that when the support is subjected to discharge plasma treatment in a gas, the effective gas in the gas composition near both ends of the support is reduced. 7. A plastic that is continuously transferred between a pair of electrodes under an atmosphere pressure or a pressure close to the atmospheric pressure, and in a mixed gas atmosphere having a composition in which 50% by weight or more of an inert gas to be introduced is an argon gas. In the surface treatment apparatus for a plastic support for treating the support by discharge plasma in gas, at least one selected from the upstream side and the downstream side in the support transfer direction of the apparatus is selected from a neutralization unit and a dust removal unit of the support. A surface treatment device for a plastic support, comprising at least one of the following: 8. A static eliminator in which said static eliminator has a plurality of positive / negative ion generating neutral electrodes and an ion attraction electrode opposed to sandwich said support, and a positive / negative DC neutralizer on the downstream side in the support transfer direction. The surface treatment apparatus for a plastic support according to claim 7, wherein the apparatus is a high-density static elimination system having an apparatus and an AC type static eliminator further downstream thereof. 9. The surface treatment apparatus for a plastic support according to claim 7, wherein said dust removing means is a non-contact type jet wind decompression type dust removal apparatus. 10. A surface treatment method for a plastic support, wherein the method is performed by the apparatus according to claim 7. Description: 11. A plastic which is continuously transferred between a pair of electrodes under an atmosphere pressure or a pressure close to the atmospheric pressure, under a mixed gas atmosphere having a composition in which 50% by weight or more of an inert gas to be introduced is an argon gas. A surface treatment method for a plastic support, which comprises subjecting the support to discharge plasma treatment in a gas, wherein the average roughness (Ra) of the surface of the support is 0.1 μm or more. 12. A plastic that is continuously transferred between a pair of electrodes under an atmosphere pressure or a pressure close to the atmospheric pressure, and in a mixed gas atmosphere having a composition in which 50% by weight or more of an inert gas to be introduced is an argon gas. A surface treatment method for a plastic support, wherein the support has a roughened portion at both ends, wherein the support has a roughened portion at both ends. 13. The method according to claim 12, wherein the support has a roughened portion 5 to 30 mm from an edge. 14. A degreasing treatment, a polishing treatment, an anodizing treatment,
A method for treating the surface of an aluminum support for a lithographic printing plate, wherein the surface treatment of the aluminum support for a lithographic printing plate is performed by flame treatment.