WO2009122882A1

WO2009122882A1 - Method of manufacturing support for planographic printing plate

Info

Publication number: WO2009122882A1
Application number: PCT/JP2009/054916
Authority: WO
Inventors: 久堀田; 徹山崎
Original assignee: 富士フイルム株式会社
Priority date: 2008-03-31
Filing date: 2009-03-13
Publication date: 2009-10-08
Also published as: CN101983261B; JPWO2009122882A1; CN101983261A

Abstract

Provided is a method of manufacturing a support for a planographic printing plate, by which the variation in image quality can be reduced and an even tone of sand can be achieved stably. A metal web (MW) formed of aluminum or an aluminum alloy is transferred, being dipped in an electrolyte (EL) of a plurality of electrolyte baths (11) sequentially, and current is supplied between the metal web (MW) and a plurality of electrodes (13) opposite to the metal web (MW) in the electrolyte baths (11) to perform an electrochemical surface roughening treatment on the metal web (MW). During this treatment, the flow rate of the electrolyte (EL) in the electrolyte baths (11) are so set that an average flow rate in the electrolyte baths may be 500 to 4000 mm/sec. and a flow rate distribution of the electrolyte (EL) in the width direction perpendicular to the direction in which the metal web (MW) is transferred in the electrolyte baths (11) may be within +/- 50% of the average flow rate. Letting a region of the transfer path of the metal web which is opposite to a gap between each two adjacent electrodes be a treatment suspension zone between electrodes in the bath, the metal web (MW) is transferred at such a speed that the time (Tin) for the metal web (MW) to pass through one treatment suspension zone between electrodes in the bath may be 0.05 to 1 sec.

Description

Method for producing support for lithographic printing plate

The present invention sequentially immerses a metal web in an electrolytic solution of a plurality of electrolytic cells, supplies current between the metal web and a plurality of electrodes opposed to the metal web in the electrolytic cell, The present invention relates to a method for producing a lithographic printing plate support which is continuously subjected to electrochemical surface roughening.

Aluminum plates are used as printing plate supports, especially lithographic printing plate supports. From the diversification of users, aluminum plates are also close to pure aluminum, and have been diversified from those with increased strength by adding manganese. Yes. In order to use such an aluminum plate as a lithographic printing plate support, it is necessary that the surface of the support has appropriate adhesion and water retention with, for example, a photosensitive material which is an image recording layer. is there. For this purpose, the surface of the aluminum plate must be roughened so as to have a uniform and fine grain. This roughening treatment has a significant effect on printing performance such as the stain performance of the plate material when printing is actually performed. Therefore, the quality is an important factor in the production of the plate material.

There are mechanical graining methods, electrochemical graining methods, and the like as roughening methods for the aluminum support for printing plates, and surface roughening is performed in a timely combination. Examples of the mechanical graining method include ball grain, wire grain, brush grain, and liquid honing. As an electrochemical graining method, an AC electrolytic etching method is generally used, and as a current, a special alternating current such as a normal sine wave AC current or a rectangular wave is used. Further, as a pretreatment for this electrochemical graining, an etching process may be performed with caustic soda.

Among them, in the AC electrolytic etching method, since there is one liquid supply nozzle for supplying the electrolytic solution in both the radial type cell and the tank type cell, the electrolytic solution replenished from here is the aluminum plate and the electrode. Since it flows to the opposite side through a defined narrow space (for example, 10 mm) and exits to the electrolyte outlet, the electrolyte gradually becomes fatigued due to electrolysis in the flow path, and the electrolyte at the beginning and end of the electrode. However, due to fatigue, a difference in the components appeared and sufficient electrolysis efficiency could not be obtained, and the temperature difference between the liquid inlet and outlet became large and the desired graininess could not be obtained. In order to improve the above-described drawbacks, there is an electrolytic processing apparatus in which two or more liquid supply nozzles are provided between electrodes (Patent Document 1).

In addition, a plurality of liquid supply nozzles are provided from the electrode side to the both ends in the width direction of the aluminum plate, and the liquid supplied from the plurality of supply nozzles is curtained at both ends in the width direction of the aluminum plate. There is a method of forming a film and preventing the electrolyte in the center from flowing to both ends (Patent Document 2).

Also, in the AC electrolytic etching method, when the flow rate distribution of the electrolyte solution in the width direction of the aluminum plate is greatly deviated from the average flow rate, the graininess in the width direction changes greatly, resulting in a difference in printing performance. To do. In order to eliminate this, in order to regulate the flow velocity distribution in the width direction within an average flow velocity of ± 50%, guide vanes for increasing frictional resistance in the width direction of the aluminum plate in the liquid supply nozzle are appropriately spaced in the width direction. There is a way to insert differently. (Patent Document 3).

JP-A-2-015198 (Claim 1, FIG. 1) JP-A-5-195300 (Claim 1, paragraph 7) Japanese Patent Laid-Open No. 9-248977 (pages 5-7, FIG. 1) JP-A-9-39431 JP 2006-44263 A JP-A-10-869 JP 2002-283762 A Japanese Patent Laid-Open No. 5-4466

However, in the method described in the above-mentioned Patent Document 1, the electrolytic solution is fatigued and a difference in its components occurs, so that sufficient electrolytic efficiency cannot be obtained, and the temperature difference between the liquid inlet and the outlet becomes large. In order to prevent the desired graininess from being obtained, two or more electrolyte supply ports are provided between the counter electrodes. However, the improvement in image quality unevenness due to the electrolytic treatment cannot be said to be sufficient. It was desired.

Further, in the method described in Patent Document 2, a plurality of liquid supply nozzles are provided with respect to the plate width from the electrode side at both ends in the width direction of the aluminum plate, and supplied from the plurality of liquid supply nozzles. Although the liquid forms curtain films at both ends in the width direction of the aluminum plate to prevent the electrolyte at the center from flowing to both ends, the improvement in the uniformity of grain and unevenness in image quality is sufficient. Therefore, further improvement has been desired.

Further, the method described in Patent Document 3 has been proposed to improve the image quality unevenness and to obtain a stable texture of honeycomb-shaped pits. Strength and adhesion are reduced.

Further, in the method described in Patent Document 4, in the electrolytic treatment of the lithographic printing plate support, electrodes are respectively installed in three electrolytic baths, and a treatment pause time of 1 to 20 seconds is provided during the electrolytic treatment. Was set to 1 to 30 seconds, but the stain performance was insufficient and the stripe-like image quality unevenness was insufficient.

In addition, in the method described in Patent Document 5, in order to solve the problem that it is impossible to obtain a lithographic printing plate support rich in printing durability and stain resistance by AC electrolysis in an aqueous solution containing hydrochloric acid. In addition, an electrochemical roughening treatment using an alternating current in an aqueous solution containing hydrochloric acid and sulfuric acid on an aluminum plate, and an electrochemical roughening using an alternating current in an aqueous solution containing hydrochloric acid Although the treatments are performed in this order, the improvement of the uniformity of grain and the unevenness of image quality cannot be said to be sufficient, and further improvement has been desired.

At this time, by combining the treatment pause time of the method described in Patent Document 4 and the mixed electrolyte of the method described in Patent Document 5, the surface roughness after the roughening treatment shown in FIG. Even if it was attempted to eliminate the occurrence of a flat portion in the portion, a flat portion remained on the convex portion in the same manner as in Patent Document 3, and it was impossible to prevent a decrease in printing durability and adhesion. Further, the image quality unevenness is not sufficient, and further improvement has been desired.

Moreover, in the method described in the above-mentioned Patent Document 6, aluminum or its The alloy sheet web is continuously subjected to electrolytic treatment while being conveyed in acidic electrolysis. At that time, the electrolytic treatment is performed so that a portion where the progress of the electrolytic treatment is fast and a portion where the progress of the electrolytic treatment is slow or stops alternately exist multiple times in all the electrolytic processes. At that time, the amount of electricity in the electrolytic treatment in the partial process where the electrolytic treatment proceeds rapidly is reduced to 100 C / dm ² or less on average, and attention is paid to the division treatment for electrolytic surface roughening. However, closely related to the uniformity of grain is the rest time between each electrolytic treatment, and can be uniformed when the rest time is 0.6 seconds to 5 seconds or less, but uniform when 0.5 seconds or less. There was a problem that the effect of. In addition, streak-like processing unevenness and chatter marks are not sufficiently lost, and improvement in image quality unevenness has been desired.

In the method described in Patent Document 7, the average speed of the electrolytic solution is 500 to 4000 mm / s, and the flow velocity distribution in the width direction is within ± 50% of the average flow velocity. Unevenness improvement was not sufficient, and further improvement was desired.

Moreover, in the method described in the above-mentioned Patent Document 8, electrochemical roughening is carried out by applying an AC voltage in an acidic electrolyte containing sulfate ions and chloride ions, and the chloride ions are in the form of aluminum chloride. Although the application is performed by application, the stain performance is not satisfactory, and improvement has been desired. Further, streak-like processing unevenness and chatter marks are not sufficiently lost, and improvement in image quality unevenness has been desired.

That is, even if the methods described in the above patent documents are combined, as shown in FIG. 8, unevenness of the grain of aluminum 500 may remain, and a flat portion 503 may remain on the convex portion 501. Still, the above problems could not be solved. Further, streak-like processing unevenness and chatter marks are not sufficiently lost, and the problem of uneven image quality cannot be solved.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a lithographic printing plate support capable of improving image quality unevenness and stably obtaining uniform grain.

The above object of the present invention is achieved by the following configurations.
(1) A metal web made of aluminum or an aluminum alloy is conveyed while being sequentially immersed in an electrolytic solution of a plurality of electrolytic cells, and a plurality of electrodes disposed opposite to the metal web in the electrolytic cell and the metal web A method for producing a support for a lithographic printing plate in which an electric current is supplied during the electrochemical surface roughening treatment of the metal web,
The flow rate of the electrolytic solution in the electrolytic cell is an average flow rate of 500 to 4000 mm / second in each electrolytic cell, and the flow rate distribution of the electrolytic solution in the width direction perpendicular to the conveying direction of the metal web in the electrolytic cell is Within ± 50% of the average flow rate,
When the conveyance path section of the metal web facing the gap region between adjacent electrodes among the plurality of electrodes is defined as the inter-bath electrode processing pause section, the single inter-bath electrode treatment pause section is passed. A method for producing a support for a lithographic printing plate, comprising transporting the metal web at a speed of 0.05 to 1 second.

According to this method for producing a lithographic printing plate support, the flow rate of the electrolytic solution is set to an average flow rate of 500 to 4000 mm / second in the electrolytic cell, and the flow rate distribution in the width direction of the electrolytic solution in the electrolytic cell is ±± of the average flow rate. Within 50%, when the region between adjacent electrodes of the plurality of electrodes is defined as a treatment interval between the electrodes in the tank, the time required to pass through the treatment interval between the electrodes in the tank is 0.05 to By conveying the metal web at a speed of 1 second, the aluminum grain can be made uniform, the stain performance is good, the printing durability and the adhesion are improved, and the image quality unevenness can be improved.

(2) A method for producing a lithographic printing plate support according to (1),
A method for producing a support for a lithographic printing plate, wherein the electrolytic solution contains chlorine ions, sulfate ions, and aluminum ions.

According to this method for producing a lithographic printing plate support, the electrolyte contained in the electrolytic cell contains chlorine ions, sulfate ions, and aluminum ions, thereby making the aluminum grain more uniform. In addition to further improving the printing durability and adhesion, the image quality unevenness can be improved.

(3) A method for producing a lithographic printing plate support according to (1) or (2),
A method for producing a support for a lithographic printing plate, wherein the electrolytic solution is caused to flow in a direction opposite to a conveying direction of the metal web.

According to this method for producing a lithographic printing plate support, the electrolyte solution on the surface of the metal web can be stirred by causing the electrolyte solution to flow in the direction of conveyance of the metal web. Can be reliably updated.

(4) A method for producing a lithographic printing plate support according to any one of (1) to (3),
A method for producing a support for a lithographic printing plate, characterized in that at least three sections of the inter-bath electrode inter-process treatment are provided in one electrolytic bath.

According to this method for producing a lithographic printing plate support, it is possible to further improve the uniformity of the aluminum grain by providing at least three inter-battery electrode processing pause sections in the electrolytic cell.

(5) A method for producing a lithographic printing plate support according to any one of (1) to (4),
The metal web is taken out of the electrolytic solution in the electrolytic cell, and the outside of the metal web conveyance path section is suspended until the metal web is immersed in the electrolytic solution in another electrolytic cell arranged on the downstream side of the metal web conveyance path. The sum of both conveying path sections from both ends of the plurality of electrodes in the electrolytic cell in the direction of arrangement to the electrolyte gas-liquid interface of the electrolytic cell When the sum of the processing interval between the electrode ends outside the tank and the continuous processing interval is defined as the inter-vessel processing pause interval, the time required to pass through the inter-vessel processing pause interval is 1 to 5 seconds. A method for producing a support for a lithographic printing plate, comprising conveying a web.

According to this method for producing a lithographic printing plate support, the aluminum web is made uniform by conveying the metal web at a speed of 1 to 5 seconds passing through one inter-bath treatment pause section. Can be further improved.

(6) A method for producing a lithographic printing plate support according to (5),
A method for producing a lithographic printing plate support, comprising at least three inter-tank processing pause sections.

According to this method for producing a lithographic printing plate support, it is possible to further improve the uniformity of the aluminum grain by providing at least three inter-tank processing pause sections.

(7) A method for producing a lithographic printing plate support according to any one of (1) to (6),
A method for producing a support for a lithographic printing plate, wherein the electrolyte solution is sprayed and supplied from a plurality of electrolyte solution supply ports arranged between the metal web and the electrode in correspondence with the electrode.

According to this method for producing a lithographic printing plate support, an electrolyte solution is injected and supplied from a plurality of electrolyte solution supply ports arranged in correspondence with the electrode between the metal web and the electrode, whereby the flow of the electrolyte solution Can be made forcibly and the flow of the electrolyte can be made even more reliably.

According to the method for producing a lithographic printing plate support of the present invention, a metal web made of aluminum or an aluminum alloy is sequentially immersed in an electrolytic solution of a plurality of electrolytic cells, and is disposed opposite to the metal web in the electrolytic cell. In the method of manufacturing a lithographic printing plate support, in which an electric current is supplied between a plurality of electrodes and a metal web, and the metal web is continuously subjected to electrochemical surface roughening, the unevenness of image quality is improved, and the uniformity is stable. It is possible to provide a planographic printing plate that can obtain a fine grain and is excellent in dirt performance and printing durability.

It is a conceptual diagram of the lithographic printing plate support manufacturing apparatus applied to the lithographic printing plate support manufacturing method according to one embodiment of the present invention. It is a principal part enlarged view of the lithographic printing plate support manufacturing apparatus of FIG. It is an external appearance perspective view of the electrolyte solution supply part applied to the lithographic printing plate support manufacturing apparatus of FIG. It is a figure which shows an example of the control method of the electrolyte solution in the manufacturing method of the support body for lithographic printing plates of this invention. It is a graph which shows an example of the alternating waveform current waveform figure used for the electrochemical roughening process in the manufacturing method of the support body for lithographic printing plates of this invention. It is a side view which shows an example of the radial type cell in the electrochemical roughening process using alternating current in the manufacturing method of the support body for lithographic printing plates of this invention. It is a side view which shows another example of the radial type cell in the electrochemical roughening process using alternating current in the manufacturing method of the support body for lithographic printing plates of this invention. It is the schematic of the metal web manufactured using the manufacturing method of the conventional support body for lithographic printing plates.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Electrolysis tank 13 Electrode 29 Electrolyte supply port 100 Support body manufacturing apparatus for lithographic printing plates EL Electrolyte MW Metal web

Hereinafter, preferred embodiments of a method for producing a lithographic printing plate support according to the present invention will be described in detail with reference to the drawings.
FIG. 1 is a conceptual diagram of a lithographic printing plate support manufacturing apparatus applied to a lithographic printing plate support manufacturing method according to an embodiment of the present invention. FIG. 2 is a planographic printing plate support manufacturing apparatus of FIG. FIG. 3 is an external perspective view of an electrolyte solution supply unit applied to the planographic printing plate support manufacturing apparatus of FIG.
In addition, although description of the component requirements described below may be made | formed based on the typical embodiment of this invention, this invention is not limited to such an embodiment. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

As shown in FIGS. 1 and 2, there are a plurality of lithographic printing plate support manufacturing apparatuses 100 applied to the method for manufacturing a lithographic printing plate support according to an embodiment of the present invention. 4) electrolytic cells 11, a plurality of electrodes 13 installed in each of the electrolytic cells 11 (in this embodiment, five in each tank), and a conveyance path for the metal web MW below each electrode 13. And a plurality of (six as an example in the present embodiment, six in each tank) each of the electrolyte supply units 15. Each electrode 13 has an equal electrode area. Although not shown, each electrolytic cell 11 is provided with an electrolytic solution discharge port for discharging the electrolytic solution. The electrolytic solution is discharged from the discharge port and the electrolytic solution is supplied from the electrolytic

solution supply units

15 and 15A. By supplying, the electrolytic solution in the electrolytic cell 11 is circulated.

A predetermined amount of electrolytic solution EL is stored in the electrolytic bath 11, and a plurality of electrodes 13 are disposed in the electrolytic solution EL in the electrolytic solution EL, and an electrolytic solution supply unit 15 is disposed below each electrode 13. ing.

The electrolytic solution EL accommodated in the electrolytic cell 11 contains chlorine ions, sulfate ions, and aluminum ions. Containing chlorine ions, sulfate ions, and aluminum ions makes it relatively difficult for charge concentration to occur, improves the uniformity of the aluminum grain, and improves printing durability and adhesion, resulting in uneven image quality. Is obtained.

The electrolytic cell 11 is arranged outside the electrolytic cell 11 from the upstream side to the downstream side in the transport direction A of the metal web MW made of aluminum or aluminum alloy and is not immersed in the electrolytic solution EL. The roller group which has the

internal rollers

19 and 21 arrange | positioned in electrolyte solution EL inside, and the electric power feeding roller 23 arrange | positioned out of the electrolytic vessel 11 and connected to AC power supply BL is provided.

Here, the conveyance path section of the metal web MW where the metal web MW faces the electrode 13 in the electrolytic cell 11 is defined as a processing section, and a plurality of electrodes are conveyed when being conveyed between the pair of

internal rollers

19 and 21 in the electrolytic cell 11. 13, a region between a pair of adjacent electrodes 13 and 13 (a region that does not face the electrode 13), that is, a conveyance path section of the metal web MW that faces a gap region between adjacent electrodes among the plurality of electrodes 13. It is set as a process pause interval between inner electrodes. The section in which the treatment is suspended in the electrolytic cell 11 includes not only the section facing the gap area between the electrodes but also the electrode 13 that is closest to the gas-liquid interface between the inner roller 19 and the outer roller 17. The interval between the conveying path area facing and the area between the gas-liquid interface between the inner roller 21 and the outer roller 23 and the conveying path area facing the last electrode 13 is the same as the process pause period. However, in this case, it is referred to as the in-vessel electrode end outer processing pause section in distinction from the in-vessel electrode processing pause section. In other words, the conveyance path section from the end in the arrangement direction of the plurality of electrodes 13 in the electrolytic cell 11 to the electrolyte gas-liquid interface of the electrolytic cell 11 is defined as an in-battery electrode end outer processing pause period.

In addition, the region transported between the pair of

external rollers

23 and 17 outside the electrolytic cell 11, that is, the metal web MW is taken out from the electrolytic solution in the electrolytic cell 11, and disposed on the downstream side of the transport path of the metal web MW. Let the conveyance path area of the metal web MW until it is immersed in the electrolyte solution of the other electrolytic tank 11 be a tank outside process stop area. That is, the section between the gas-liquid interface between the inner roller 21 and the outer roller 23 and the gas-liquid interface between the adjacent outer roller 17 and the inner roller 19 is defined as the outside processing section. Further, the sum of the outside processing section and the in-tank electrode outer side processing suspension section that follows this is defined as the inter-tank processing suspension section. In the inter-bath processing pause section, the metal web MW is immersed in the first electrolytic cell on the transport path and faces the first electrode, and is out of the position facing the last electrode of the last electrolytic tank on the transport path. After that, it shall not be included in this inter-bath processing suspension section.

And, the time required for the metal web MW (any one point of the metal web MW) to pass through the length of a single inter-bath electrode inter-process treatment interval expressed between the pair of electrodes 13 is Tin, and the out-of-bath treatment pause interval The time required for the metal web MW (any one point of the metal web MW) to pass is defined as Tout. Also, Ts_in_a is the time required for the both-end treatment pause section on the electrolytic cell outlet side which is the electrode electrode outer side treatment pause section, and it is required for the both-end treatment pause section on the electrolytic cell inlet side which is also the inner electrode edge outer treatment pause section. Let time be Ts_in_b.
Here, if the time required for the inter-tank processing suspension period is Tab, Tab is represented by Ts_in_a + Tout + Ts_in_b.

As shown in FIG. 2, each electrode 13 is connected to an AC power supply BL, and the power supply roller 23 connected to the AC power supply BL is in contact with the metal web MW. Applies a predetermined alternating current to the metal web MW through the electrolytic solution EL.

As shown in the configuration example of the electrolytic solution supply unit 15 in FIG. 3, the electrolytic solution supply unit 15 in the electrolytic cell 11 is paired with both ends in the width direction perpendicular to the conveying direction of the metal web MW in the electrolytic cell 11. A guide portion 25 is provided, and a cylindrical injection portion 27 is provided between the guide portions 25. A slit-shaped electrolyte supply port 29 is formed in the width direction of the injection unit 27.

The pair of guide portions 25 are connected to an electrolyte solution tank (not shown) and constantly supply the electrolyte solution to the injection portion 27. The electrolyte EL supplied to the injection unit 27 is injected over the entire width of the electrolytic cell 11 through the electrolyte supply port 29 in a direction opposite to the conveyance direction A of the metal web MW, that is, in a direction opposite to the conveyance direction A. . As described above, the electrolyte solution supply unit 15 transfers the electrolyte solution EL in the transport direction A of the metal web MW from the plurality of electrolyte solution supply ports 29 arranged in correspondence with the electrode 13 between the metal web MW and the electrode 13. On the other hand, the electrolyte EL in the vicinity of the electrode 13 is forced to flow by spraying in the opposite direction. Thereby, the surface of the metal web MW always comes into contact with the fresh electrolyte EL. Further, since the electrolytic solution EL is discharged from a discharge port (not shown), the electrolytic solution EL circulates in the electrolytic cell 11 together with the electrolytic solution EL supplied from the electrolytic solution supply unit 15.

In the electrolytic solution supply unit 15A arranged on the most upstream side in the conveying direction of the metal web MW in the electrolytic cell 11, the injection unit 27 is rotated by a rotation mechanism (not shown) built in the guide unit 25. As a result, the electrolytic solution supply port 29 changes the injection direction of the electrolytic solution EL while spraying the electrolytic solution EL toward the metal web MW, so that the electrolytic solution EL is sufficiently stirred in the electrolytic bath 11 and locally. So that no itch is generated. The electrolytic solution supply unit 15A capable of changing the injection direction of the electrolytic solution supply port 29 is the same for all other electrolytic solution supply units 15 in addition to the one on the most upstream side in the conveyance direction of the metal web MW. It is good also as a structure of.

In the lithographic printing plate support manufacturing apparatus 100 having the above-described configuration, the metal web MW is sequentially immersed in the electrolytic solution EL of the electrolytic cell 11, and the electrode 13 and the metal web disposed to face the metal web MW in the electrolytic cell 11. The metal web MW is continuously subjected to an electrochemical surface roughening treatment by energizing with the MW. At that time, the flow rate of the electrolytic solution EL is set such that the average flow rate in the electrolytic cell 11 is 500 to 4000 mm / second, and the flow rate distribution of the electrolytic solution EL with respect to the width direction perpendicular to the conveying direction of the metal web MW in the electrolytic cell 11. Within ± 50% of the average flow rate. Then, the relationship between the passage time Tin of the inter-bath electrode processing pause section and the passage time Tab of the inter-bath treatment pause section for the processing section in which the metal web MW faces the electrode 13 in the electrolytic bath 11 is once. The metal web MW is transported at a speed such that the time Tin passing through the inter-battery treatment pause interval is 0.05 to 1 second, and the time Tab passing through one bath treatment pause interval is 1 to 5 seconds. To do. By carrying out the method for producing a lithographic printing plate support under the above-mentioned conditions, it is possible to improve the unevenness of the image quality of the aluminum surface of the metal web MW and make the grain uniform, and to improve the stain performance and the printing durability. be able to.

The planographic printing plate support manufacturing apparatus 100 according to the present embodiment provides 16 inter-battery electrode processing pause sections (Tin) in the electrolytic bath 11 and an inter-bath processing pause zone (Tab) including the outside of the electrolytic bath 11. There are 3 sections.
In this way, by providing a prescribed number of inter-battery electrode processing pause intervals (Tin) and inter-vessel treatment pause intervals (Tab), it is possible to improve the uniformity of the aluminum grain. It is desirable to provide at least three sections for the inter-bath electrode processing suspension section and the inter-tank processing suspension section. The larger the number of sections, the higher the effect of uniformizing the properties of the plate surface of the metal web MW. In addition, it has been confirmed by experiments that the properties of the printing plate are deteriorated when the inter-battery electrode processing pause section and the inter-tank processing pause section are two sections or less.

In addition, since the size of the electrolytic cell 11 is increased when the number of in-battery inter-electrode processing pauses is increased, for example, it is practical to set the number of in-battery inter-electrode treatment pauses to 3 to 50, for example. Is preferred. Further, if the number of inter-tank processing pause sections is increased, a large installation space is required for the entire apparatus. For example, it is practically preferable to set 10 sections to the maximum and the inter-tank processing pause section to 3 to 10 sections. However, the number of sections is the case where the dimension of the metal web MW is, for example, about 0.1 to 0.5 mm in thickness and about 500 to 2000 mm in width. The number varies.

Then, the lithographic printing plate support manufacturing apparatus 100 includes a lithographic printing plate support while injecting the electrolytic solution EL from the electrolytic solution supply port 29 of the electrolytic solution supply unit 15 in a direction opposite to the conveying direction of the metal web MW. Manufacture.

Next, a method for producing a lithographic printing plate support will be described in detail.
[Method for producing support for lithographic printing plate]
<Aluminum plate (rolled aluminum)>
A known aluminum plate can be used in the method for producing a lithographic printing plate support of the present invention. The aluminum plate used in the present invention is a metal whose main component is dimensionally stable aluminum, and is made of aluminum or an aluminum alloy. In addition to a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements can also be used.

In this specification, various substrates made of the above-described aluminum or aluminum alloy are collectively referred to as an aluminum plate. The foreign elements that may be contained in the aluminum alloy include silicon, iron, copper, manganese, magnesium, chromium, zinc, bismuth, nickel, titanium, etc., and the content of the foreign elements in the alloy is 10% by mass or less. It is.

Thus, the composition of the aluminum plate used in the present invention is not specified. For example, a conventionally known material described in the fourth edition of the Aluminum Handbook (1990, published by the Light Metal Association), for example, JIS Al-Mn based aluminum plates such as A1050, JIS A1100, JIS A1070, JIS A3004 containing Mn, and internationally registered alloy 3103A can be used as appropriate. For the purpose of increasing the tensile strength, an Al—Mg alloy or an Al—Mn—Mg alloy (JIS A3005) in which 0.1% by mass or more of magnesium is added to these aluminum alloys can also be used. Furthermore, an Al—Zr alloy or an Al—Si alloy containing Zr or Si can also be used. Furthermore, an Al—Mg—Si based alloy can also be used.
Moreover, the aluminum plate obtained by rolling the UBC (Used Beverage Can) ingot which melt | dissolved the used aluminum beverage can can also be used.
In this aluminum plate, the Cu content is preferably 0.00% by mass or more, more preferably 0.01% by mass or more, and more preferably 0.02% by mass or more, and 0.15% by mass. % Or less, preferably 0.11% by mass or less, more preferably 0.03% by mass or less. Particularly preferred are Si: 0.07 to 0.09 mass%, Fe: 0.20 to 0.29 mass%, Cu: 0.03 mass% or less, Mn: 0.01 mass% or less, Mg: 0 0.01% by mass or less, Cr: 0.01% by mass or less, Zn: 0.01% by mass or less, Ti: 0.02% by mass or less, and Al: 99.5% by mass or more.

Regarding the JIS 1050 material, the techniques proposed by the applicant of the present application are disclosed in Japanese Patent Application Laid-Open Nos. 59-153861, 61-51395, 62-146694, 60-215725, and 60-215725. JP-A-60-215726, JP-A-60-215727, JP-A-60-216728, JP-A-61-272367, JP-A-58-11759, JP-A-58-42493, JP-A-58- 221254, JP-A-62-148295, JP-A-4-254545, JP-A-4-165541, JP-B-3-68939, JP-A-3-234594, JP-B-1-47545, and JP-A-62. It is described in each publication of -140894. In addition, techniques described in Japanese Patent Publication No. 1-35910 and Japanese Patent Publication No. 55-28874 are also known.

Regarding the JIS 1070 material, the techniques proposed by the applicant of the present application are disclosed in JP-A-7-81264, JP-A-7-305133, JP-A-8-49034, JP-A-8-73974, JP-A-8-108659 and It is described in JP-A-8-92679.

Regarding the Al-Mg alloy, the techniques proposed by the applicant of the present application are disclosed in Japanese Patent Publication Nos. 62-5080, 63-60823, 3-61753, JP-A-60-20396, JP-A-60-203497, JP-B-3-11635, JP-A-61-274993, JP-A-62-23794, JP-A-63-47347, JP-A-63-47348, JP-A-63-47349 JP-A 64-1293, JP-A 63-135294, JP-A 63-87288, JP-B 4-73392, JP-B 7-1000084, JP-A 62-149856, JP-B JP-A-4-73394, JP-A-62-181191, JP-B-5-76530, JP-A-63-30294, and JP-B-6-37116. Also described in JP-A-2-215599, JP-A-61-201747, and the like.

Regarding the Al—Mn alloy, the techniques proposed by the applicant of the present application are described in JP-A-60-230951, JP-A-1-306288, and JP-A-2-293189. JP-B-54-42284, JP-B-4-19290, JP-B-4-19291, JP-B-4-19292, JP-A-61-35995, JP-A-64-51992, JP-A-4-1952 No. 226394, US Pat. No. 5,009,722, US Pat. No. 5,028,276 and the like.

Regarding the Al—Mn—Mg alloy, the techniques proposed by the applicant of the present application are described in Japanese Patent Application Laid-Open Nos. Sho 62-86143 and Hei 3-2222796. JP-B 63-60824, JP-A 60-63346, JP-A 60-63347, JP-A-1-293350, European Patent No. 223,737, US Patent No. 4,818, No. 300, British Patent No. 1,222,777, etc.

Regarding the Al—Zr alloy, the technique proposed by the applicant of the present application is described in Japanese Patent Publication No. 63-15978 and Japanese Patent Application Laid-Open No. 61-51395. Also described in JP-A-63-143234 and JP-A-63-143235.

The Al—Mg—Si alloy is described in British Patent No. 1,421,710.

In order to use an aluminum alloy as a plate material, for example, the following method can be employed. First, a molten aluminum alloy adjusted to a predetermined alloy component content is subjected to a cleaning process and cast according to a conventional method. In the cleaning process, in order to remove unnecessary gas such as hydrogen in the molten metal, flux treatment, degassing process using argon gas, chlorine gas, etc., so-called rigid media filter such as ceramic tube filter, ceramic foam filter, A filtering process using a filter that uses alumina flakes, alumina balls or the like as a filter medium, a glass cloth filter, or a combination of a degassing process and a filtering process is performed.

These cleaning treatments are preferably carried out in order to prevent defects caused by foreign substances such as non-metallic inclusions and oxides in the molten metal and defects caused by gas dissolved in the molten metal. Regarding filtering of the molten metal, JP-A-6-57432, JP-A-3-162530, JP-A-5-140659, JP-A-4-231425, JP-A-4-276031, JP-A-5-311261, and JP-A-5-311261 are disclosed. It is described in each publication of JP-A-6-136466. Further, the degassing of the molten metal is described in JP-A-5-51659, JP-A-5-49148, and the like. The applicant of the present application has also proposed a technique relating to degassing of molten metal in Japanese Patent Application Laid-Open No. 7-40017.

Next, casting is performed using the molten metal that has been subjected to the cleaning treatment as described above. As for the casting method, there are a method using a solid mold typified by a DC casting method and a method using a driving mold typified by a continuous casting method.
In DC casting, solidification occurs at a cooling rate of 0.5 to 30 ° C./second. When the temperature is less than 1 ° C., many coarse intermetallic compounds may be formed. When DC casting is performed, an ingot having a thickness of 300 to 800 mm can be produced. The ingot is chamfered as necessary according to a conventional method, and usually 1 to 30 mm, preferably 1 to 10 mm, of the surface layer is cut. Before and after that, soaking treatment is performed as necessary. When soaking treatment is performed, heat treatment is performed at 450 to 620 ° C. for 1 to 48 hours so that the intermetallic compound does not become coarse. If the heat treatment is shorter than 1 hour, the effect of soaking may be insufficient. In addition, when soaking is not performed, there is an advantage that the cost can be reduced.

Then, hot rolling and cold rolling are performed to obtain a rolled aluminum plate. A suitable starting temperature for hot rolling is 350 to 500 ° C. An intermediate annealing treatment may be performed before or after hot rolling or in the middle thereof. The conditions for the intermediate annealing treatment are heating at 280 to 600 ° C. for 2 to 20 hours, preferably 350 to 500 ° C. for 2 to 10 hours using a batch annealing furnace, or 400 to 600 ° C. using a continuous annealing furnace. Heating is performed for 6 minutes or less, preferably 450 to 550 ° C. for 2 minutes or less. The crystal structure can be made finer by heating at a heating rate of 10 to 200 ° C./second using a continuous annealing furnace.

The flatness of the aluminum plate finished to a predetermined thickness, for example, 0.1 to 0.5 mm by the above steps may be further improved by a correction device such as a roller leveler or a tension leveler. The flatness may be improved after the aluminum plate is cut into a sheet shape, but in order to improve the productivity, it is preferably performed in a continuous coil state. Further, a slitter line may be used for processing into a predetermined plate width. Moreover, in order to prevent generation | occurrence | production of the damage | wound by friction between aluminum plates, you may provide a thin oil film on the surface of an aluminum plate. As the oil film, a volatile or non-volatile film is appropriately used as necessary.

On the other hand, as the continuous casting method, a twin roll method (hunter method), a method using a cooling roll typified by the 3C method, a double belt method (Hazley method), a cooling belt or a cooling block typified by Al-Swiss Caster II type The method using is industrially performed. When the continuous casting method is used, it solidifies at a cooling rate of 100 to 1000 ° C./second. Since the continuous casting method generally has a higher cooling rate than the DC casting method, it has a feature that the solid solubility of the alloy component in the aluminum matrix can be increased. Regarding the continuous casting method, the techniques proposed by the applicant of the present application are disclosed in JP-A-3-79798, JP-A-5-201166, JP-A-5-156414, JP-A-6-262203, and JP-A-6-122949. JP-A-6-210406, JP-A-6-26308, and the like.

When continuous casting is performed, for example, if a method using a cooling roll such as the Hunter method is used, a cast plate having a thickness of 1 to 10 mm can be directly continuously cast, and the hot rolling step is omitted. The advantage of being able to In addition, when a method using a cooling belt such as the Husley method is used, a cast plate having a thickness of 10 to 50 mm can be cast. Generally, a hot rolling roll is arranged immediately after casting and continuously rolled. Thus, a continuous cast and rolled plate having a thickness of 1 to 10 mm can be obtained.

These continuous cast and rolled sheets are subjected to processes such as cold rolling, intermediate annealing, improvement of flatness, slits, and the like in the same manner as described for DC casting, and a predetermined thickness, for example, 0.1 to 0.00. Finished to a thickness of 5 mm. As for the intermediate annealing conditions and the cold rolling conditions when using the continuous casting method, the techniques proposed by the applicant of the present application are disclosed in JP-A-6-220593, JP-A-6-210308, JP-A-7-54111, It is described in JP-A-8-92709.

The aluminum plate used in the present invention is preferably subjected to H18 tempering as defined in JIS.

Various characteristics described below are desired for the aluminum plate thus manufactured.
The strength of the aluminum plate is preferably such that the 0.2% proof stress is 120 MPa or more in order to obtain the stiffness required for a lithographic printing plate support. Further, in order to obtain a certain level of waist strength even when performing the burning treatment, the 0.2% proof stress after heat treatment at 270 ° C. for 3 to 10 minutes is preferably 80 MPa or more, and 100 MPa or more. It is more preferable that In particular, when the waist strength is required for an aluminum plate, an aluminum material added with Mg or Mn can be used, but if the waist is strengthened, the ease of fitting to the plate cylinder of a printing press becomes inferior. Depending on the application, the material and the amount of trace components added are appropriately selected. With regard to these, techniques proposed by the applicant of the present application are described in Japanese Patent Application Laid-Open Nos. 7-126820 and 62-140894.
The aluminum plate preferably has a tensile strength of 160 ± 15 N / mm ² , a 0.2% proof stress of 140 ± 15 MPa, and an elongation defined by JIS Z2241 and Z2201 of 1 to 10%.

The crystal structure of the aluminum plate may cause poor surface quality when the surface of the aluminum plate is subjected to chemical or electrochemical surface roughening. It is preferably not too coarse. The crystal structure on the surface of the aluminum plate preferably has a width of 200 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, and the length of the crystal structure is 5000 μm or less. Is preferably 1000 μm or less, and more preferably 500 μm or less. With regard to these, techniques proposed by the applicant of the present application are described in Japanese Patent Laid-Open Nos. 6-218495, 7-39906, and 7-124609.

The alloy component distribution of the aluminum plate, when chemical surface roughening treatment or electrochemical surface roughening treatment is performed, poor surface quality occurs due to non-uniform distribution of the alloy component on the surface of the aluminum plate. Therefore, it is preferable that the surface is not very uneven. With respect to these, techniques proposed by the applicant of the present application are described in Japanese Patent Laid-Open Nos. 6-48058, 5-301478, and 7-132689.

In the intermetallic compound of the aluminum plate, the size and density of the intermetallic compound may affect the chemical roughening treatment or the electrochemical roughening treatment. With respect to these, techniques proposed by the applicant of the present application are described in Japanese Patent Laid-Open Nos. 7-138687 and 4-254545.

In the present invention, an aluminum plate as shown above can be used by forming irregularities by press rolling, transfer or the like in the final rolling step or the like.

Above all, along with cold rolling to adjust the final plate thickness, or finish cold rolling to finish the surface shape after final plate thickness adjustment, the uneven surface is transferred to the surface of the aluminum plate by pressing the uneven surface to the aluminum plate. A method of forming an uneven pattern is preferred. Specifically, the method described in JP-A-6-262203 can be suitably used.
By using an aluminum plate having a concavo-convex pattern on the surface, it is possible to obtain a concavo-convex pattern having a uniform average pitch and depth than the concavo-convex pattern formed by the brush and the abrasive, thereby improving the stain resistance. In addition, the amount of dampening water on the printing press can be easily adjusted while reducing energy consumed in the subsequent alkali etching treatment and surface roughening treatment. For example, in the first etching process described later, the etching amount can be reduced to about 3 g / m ² or less. In addition, when an aluminum plate having a concavo-convex pattern is used, the surface area of the obtained lithographic printing plate support is increased, so that the printing durability is more excellent.

The transfer is particularly preferably performed in the final cold rolling step of a normal aluminum plate. Rolling for transfer is preferably performed in 1 to 3 passes, and the rolling reduction of each is preferably 3 to 8%.
Moreover, it is more preferable that the unevenness | corrugation provided by transcription | transfer is provided on both surfaces of an aluminum plate. Thereby, since the elongation rate of the aluminum plate of the surface and a back surface can be adjusted to the same grade, an aluminum plate with sufficient flatness can be obtained.

Examples of a method for obtaining a rolling roll having irregularities on the surface used for irregularity transfer include a blast method, an electrolytic method, a laser method, an electric discharge machining method, and a method combining these. Among these, a method in which the blast method and the electrolytic method are combined is preferable. Among the blast methods, the air blast method is preferable.
The air pressure in the air blast method is preferably 1 to 10 kgf / cm ² (9.81 × 10 ⁴ to 9.81 × 10 ⁵ Pa), preferably 2 to 5 kgf / cm ² (1.96 × 10 ⁵ to More preferably 4.90 × 10 ⁵ Pa).
The grid used in the air blast method is not particularly limited as long as it is alumina particles having a predetermined particle size. If alumina particles having hard and sharp corners are used for the grid, it is easy to form deep and uniform irregularities on the surface of the transfer roll.
The average particle diameter of the alumina particles is 50 to 150 μm, preferably 60 to 130 μm, and more preferably 70 to 90 μm. If it is within the above range, a surface roughness having a sufficient size as a transfer roll can be obtained, so that the surface roughness of an aluminum plate provided with irregularities using this transfer roll is sufficiently increased. Also, the number of pits can be increased sufficiently.

In the air blast method, the injection is preferably performed 2 to 5 times, and more preferably 2 times. When the injection is performed twice, the uneven surface of the unevenness formed by the first injection can be scraped off by the second injection, so the surface of the aluminum plate provided with the unevenness using the obtained rolling roll, Locally deep recesses are less likely to be formed. As a result, the developability (sensitivity) of the lithographic printing plate is excellent.
The spray angle in the air blast method is preferably 60 to 120 °, more preferably 80 to 100 ° with respect to the spray surface (roll surface).

Polishing is preferably performed until the average surface roughness (R _a ) is reduced by 10 to 40% from the value after air blasting after the air blasting method and before the plating treatment described later. For polishing, it is preferable to use sandpaper, a grindstone, or a buff. By polishing, the height of the convex portions on the surface of the transfer roll can be made uniform. As a result, locally deep portions are not formed on the surface of the aluminum plate provided with irregularities using the transfer roll. As a result, the developability (sensitivity) of the lithographic printing plate is particularly excellent.

The average surface roughness (R _a ) of the transfer roll surface is preferably 0.4 to 1.0 μm, more preferably 0.6 to 0.9 μm. The number of peaks on the surface of the transfer roll is preferably 1000 to 40000 / mm ² , and more preferably 2000 to 10000 / mm ² . If the number of peaks is too small, the water retention of the lithographic printing plate support and the adhesion to the image recording layer will be poor. If the water retention is inferior, the halftone dot portion tends to become dirty when a planographic printing plate is used.

The material of the transfer roll is not particularly limited, and for example, a known material for a rolling roll can be used.
In the present invention, it is preferable to use a steel roll. Among these, a roll made by forging is preferable. Examples of preferred roll material compositions are: C: 0.07 to 6 mass%, Si: 0.2 to 1 mass%, Mn: 0.15 to 1 mass%, P: 0.03 mass% or less, S: 0.03% by mass or less, Cr: 2.5 to 12% by mass, Mo: 0.05 to 1.1% by mass, Cu: 0.5% by mass or less, V: 0.5% by mass or less, balance: iron And inevitable impurities.
Further, tool steel (SKD), high-speed steel (SKH), high carbon chromium bearing steel (SUJ), and forged steel containing carbon, chromium, molybdenum and vanadium as alloy elements, which are generally used as rolling rolls, are mentioned. It is done. In order to obtain a long roll life, high chromium alloy cast iron containing about 10 to 20% by mass of chromium can also be used.
Among these, it is preferable to use a roll manufactured by a forging method. In this case, the hardness after quenching and tempering is preferably 80 to 100 in terms of Hs. The tempering is preferably performed at a low temperature.
The diameter of the roll is preferably 200 to 1000 mm. The roll surface length is preferably 1000 to 4000 mm.

It is preferable that the transfer roll formed with irregularities by an air blast method or the like is subjected to hardening treatment such as quenching and hard chrome plating after washing. This improves wear resistance and prolongs life.
As the hardening treatment, hard chrome plating is particularly preferable. Hard chromium plating can be performed by electroplating using a conventionally known CrO ₃ —SO ₄ bath, CrO ₃ —SO ₄ —fluoride bath or the like as an industrial chromium plating method.
The thickness of the hard chrome plating film is preferably 3 to 15 μm, and more preferably 5 to 10 μm. If it is in the above range, the plating peeling is difficult to peel off from the boundary between the roll surface substrate and the plating film, and the effect of improving the wear resistance is sufficient. The thickness of the hard chrome plating film can be adjusted by adjusting the plating treatment time.
Before the hard chrome plating, it is preferable to perform electrolytic treatment with a quantity of electricity of 5,000 to 50,000 C / dm ² by using a roll as an anode and a direct current in a plating solution used for hard chrome plating. . Thereby, the unevenness | corrugation of the surface of a roll can be equalize | homogenized.

The aluminum plate used in the present invention is a continuous belt-like sheet material or plate material. That is, it may be an aluminum web, or a sheet-like sheet cut to a size corresponding to a planographic printing plate precursor shipped as a product.
Since scratches on the surface of the aluminum plate may become defects when processed into a lithographic printing plate support, it is possible to generate scratches at the stage prior to the surface treatment process for making a lithographic printing plate support It is necessary to suppress as much as possible. For that purpose, it is preferable that the package has a stable form and is hardly damaged during transportation.
In the case of an aluminum web, for example, the packing form of aluminum is, for example, laying a hardboard and felt on an iron pallet, applying cardboard donut plates to both ends of the product, wrapping the whole with a polytube, and inserting a wooden donut into the inner diameter of the coil Then, a felt is applied to the outer periphery of the coil, the band is squeezed with a band, and the display is performed on the outer periphery. Moreover, a polyethylene film can be used as the packaging material, and needle felt and hard board can be used as the cushioning material. There are various other forms, but the present invention is not limited to this method as long as it is stable and can be transported without being damaged.

The thickness of the aluminum plate used in the present invention is about 0.1 to 0.6 mm, preferably 0.15 to 0.4 mm, and more preferably 0.2 to 0.3 mm. This thickness can be appropriately changed according to the size of the printing press, the size of the printing plate, the user's desires, and the like.

<Surface treatment>
In the method for producing a lithographic printing plate support of the present invention, the aluminum plate described above is subjected to an electrochemical surface roughening treatment using alternating current in an electrolytic solution to obtain a lithographic printing plate support.
In the method for producing a lithographic printing plate support of the present invention, various steps other than those described above may be included.

Specifically, for example, an etching process in an alkaline aqueous solution (first etching process), a desmut process in an acidic aqueous solution, an electrochemical roughening process, an etching process in an alkaline aqueous solution (second etching process). A preferred example is a method in which a desmut treatment in an acidic aqueous solution and an anodizing treatment are performed in this order.
Further, before the anodizing treatment in the above treatment, an electrochemical surface roughening treatment, an etching treatment in an alkaline aqueous solution, and a desmut treatment in an acidic aqueous solution may be performed. Further, after the anodizing treatment, a sealing treatment, a hydrophilization treatment, or a sealing treatment and a subsequent hydrophilization treatment are also preferable.

Further, a mechanical surface roughening process can be performed before the first etching process. Thereby, the amount of electricity used for the electrochemical surface roughening treatment can be reduced.
Examples of the mechanical surface roughening treatment include, for example, a wire brush grain method in which the aluminum surface is scratched with a metal wire, a ball grain method in which the aluminum surface is grained with a polishing ball and an abrasive, JP-A-6-135175, and Japanese Patent Publication No. 50. The brush grain method of graining the surface with a nylon brush and an abrasive described in Japanese Patent No. 40047 can be used.
Moreover, the transfer method (transfer roll method) which press-contacts an uneven surface to an aluminum plate can also be used. That is, in addition to the methods described in JP-A-55-74898, JP-A-60-36195, and JP-A-60-20396, transfer is performed several times. The method described in Japanese Patent Laid-Open No. 55871 and Japanese Patent Laid-Open No. 6-24168 characterized in that the surface is elastic is also applicable.
Among these, the transfer roll method is preferable because it can easily cope with the speedup of the manufacturing process of the support for a lithographic printing plate. As described above, the transfer roll method preferably performs the transfer in the cold rolling for adjusting to the final plate thickness or the finish cold rolling for finishing the surface shape after the final plate thickness adjustment.

Hereinafter, each step of the surface treatment will be described in detail.

<First etching process>
The alkali etching treatment is a treatment for dissolving the surface layer by bringing the above-described aluminum plate into contact with an alkali solution.

Prior to the electrochemical surface roughening treatment, it is preferable to perform the first etching treatment. The first etching treatment is performed for the purpose of forming uniform concave portions by electrochemical surface roughening treatment and removing rolling oil, dirt, natural oxide film, etc. on the surface of the aluminum plate (rolled aluminum). Is called.
In the first etching treatment, the etching amount of the surface to be subjected to the electrochemical roughening treatment later is preferably 0.5 g / m ² or more, more preferably 1 g / m ² or more. but preferably not more 10 g / m ² or less, more preferably 5 g / m ² or less. When the etching amount is 0.5 g / m ² or more, uniform pits can be generated in the electrochemical surface roughening treatment. When the etching amount is 10 g / m ² or less, the amount of the alkaline aqueous solution used is reduced, which is economically advantageous.

The etching amount of the back surface of the surface subjected to the electrochemical roughening treatment is preferably 5% or more of the etching amount of the surface subjected to the electrochemical roughening treatment, preferably 10% or more. Is more preferably 50% by mass or less, and more preferably 30% by mass or less. It is excellent in the balance with the removal effect of the rolling oil of the back surface of an aluminum plate, and economical efficiency as it is the said range.
The same applies to a second etching process and a third etching process described later.

Examples of the alkali used in the alkaline solution include caustic alkali and alkali metal salts. Specifically, examples of caustic alkali include caustic soda and caustic potash. Examples of the alkali metal salt include alkali metal silicates such as sodium metasilicate, sodium silicate, potassium metasilicate, and potassium silicate; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium aluminate and alumina. Alkali metal aluminates such as potassium acid; alkali metal aldones such as sodium gluconate and potassium gluconate; dibasic sodium phosphate, dibasic potassium phosphate, primary sodium phosphate, primary potassium phosphate, etc. An alkali metal hydrogen phosphate is mentioned. Among these, a caustic alkali solution and a solution containing both a caustic alkali and an alkali metal aluminate are preferable from the viewpoint of high etching rate and low cost. In particular, an aqueous solution of caustic soda is preferable.

In the first etching treatment, the concentration of the alkaline solution is preferably 1% by mass or more, more preferably 20% by mass or more, and preferably 35% by mass or less, and 30% by mass or less. It is more preferable that
The alkaline solution preferably contains aluminum ions. The aluminum ion concentration is preferably 0.5% by mass or more, more preferably 4% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less. . Such an alkaline solution can be prepared using, for example, water, a 48 mass% sodium hydroxide aqueous solution, and sodium aluminate.

In the first etching treatment, the temperature of the alkaline solution is preferably 25 ° C. or higher, more preferably 40 ° C. or higher, preferably 95 ° C. or lower, and 80 ° C. or lower. More preferred.
In the first etching treatment, the treatment time is preferably 1 second or longer, more preferably 2 seconds or longer, more preferably 30 seconds or shorter, and more preferably 15 seconds or shorter. .

When the aluminum plate is continuously etched, the aluminum ion concentration in the alkaline solution increases and the etching amount of the aluminum plate varies. Therefore, the composition management of the etching solution is preferably performed as follows.
That is, a matrix of conductivity, specific gravity, and temperature, or a matrix of conductivity, ultrasonic propagation velocity, and temperature corresponding to the matrix of caustic soda concentration and aluminum ion concentration is prepared in advance, and the conductivity and specific gravity are prepared. The liquid composition is measured according to the temperature and temperature, or the electrical conductivity, the ultrasonic wave propagation speed, and the temperature, and caustic soda and water are added so that the control target value of the liquid composition is reached. Then, the amount of the etching solution increased by adding caustic soda and water is overflowed from the circulation tank, thereby keeping the amount of the solution constant. As the caustic soda to be added, 40 to 60% by mass for industrial use can be used.
As the conductivity meter and the specific gravity meter, it is preferable to use those that are temperature-compensated. As the hydrometer, it is preferable to use a differential pressure type.

Examples of the method of bringing the aluminum plate into contact with the alkaline solution include, for example, a method in which the aluminum plate is passed through a tank containing the alkaline solution, a method in which the aluminum plate is immersed in a tank containing the alkaline solution, The method of spraying on the surface of a board is mentioned.

Of these, a method of spraying an alkaline solution onto the surface of an aluminum plate is preferable. Specifically, a method of spraying an etching solution in an amount of 10 to 100 L / min per spray tube from a spray tube having holes of φ2 to 5 mm at a pitch of 10 to 50 mm is preferable. It is preferable to provide a plurality of spray tubes.

After the alkali etching treatment is completed, it is preferable to drain the liquid with a nip roller, and further perform the water washing treatment for 1 to 10 seconds and then drain the liquid with a nip roller.
The water washing treatment is preferably carried out using an apparatus for washing with a free-falling curtain-like liquid film, and further using a spray tube.

Further, as the spray tube used for the water washing treatment, for example, a spray tube having a plurality of spray tips spreading in the fan shape in the width direction of the aluminum plate can be used. The interval between spray tips is preferably 20 to 100 mm, and the amount of liquid per spray tip is preferably 0.5 to 20 L / min. It is preferable to use a plurality of spray tubes.

<First desmut treatment>
After the first etching process, it is preferable to perform pickling (first desmut process) in order to remove dirt (smut) remaining on the surface. The desmut treatment is performed by bringing an aluminum plate into contact with an acidic solution.

Examples of the acid used include nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, chromic acid, hydrofluoric acid, and borohydrofluoric acid. Of these, nitric acid and sulfuric acid are preferable. Specifically, for example, a waste solution of an aqueous sulfuric acid solution used in an anodic oxidation process described later can be suitably used.

In the composition management of the desmut treatment liquid, a method of managing by conductivity and temperature, a method of managing by conductivity, specific gravity and temperature, and a conductivity and superconductivity corresponding to a matrix of acidic solution concentration and aluminum ion concentration. Either of the methods managed by the propagation speed of sound waves and temperature can be selected and used.

In the first desmutting treatment, it is preferable to use an acidic solution containing 0.5 to 30% by mass of acid and 0.5 to 10% by mass of aluminum ions.

The temperature of the acidic solution is preferably 25 ° C. or higher, and preferably 95 ° C. or lower.

In the first desmutting treatment, the treatment time is preferably 1 second or more, more preferably 2 seconds or more, and preferably 30 seconds or less, more preferably 10 seconds or less. .

Examples of the method of bringing the aluminum plate into contact with the acidic solution include, for example, a method of passing the aluminum plate through a bath containing the acidic solution, a method of immersing the aluminum plate in a bath containing the acidic solution, and an acidic solution containing aluminum. The method of spraying on the surface of a board is mentioned.
Among these, a method in which an acidic solution is sprayed on the surface of an aluminum plate is preferable. Specifically, it is preferable to spray a desmating solution at a rate of 10 to 100 L / min per spray tube from a spray tube having φ2 to 5 mm holes at a pitch of 10 to 50 mm. It is preferable to provide a plurality of spray tubes.

After the desmutting process is completed, it is preferable to drain the liquid with a nip roller, and further perform the water washing process for 1 to 10 seconds and then drain the liquid with a nip roller.
The water washing treatment is the same as the water washing treatment after the alkali etching treatment. However, the amount of liquid per spray tip is preferably 1 to 20 L / min.

<Electrochemical roughening treatment>
As the electrochemical surface roughening treatment, it is desirable to perform an electrochemical surface roughening treatment using alternating current in a mixed aqueous solution containing chlorine ions and sulfate ions. By this electrochemical surface roughening treatment, the surface shape has a plateau portion (flat portion), a uniform concave portion having an average diameter of preferably 2 to 20 μm, and preferably an average surface roughness of 0.3 to 0.8 μm. Is obtained. As described above, in the present invention, since the plateau portion is small on the surface after the electrochemical surface roughening treatment, the printing durability when the planographic printing plate is obtained is excellent, and the pits are uniform. Therefore, the stain resistance when the planographic printing plate is obtained is excellent.
On the other hand, when an aqueous solution containing hydrochloric acid and not containing sulfuric acid is used as the electrolytic solution, the pits become shallow or overlap and become non-uniform. In addition, the plateau part increases.

The hydrochloric acid concentration in the mixed aqueous solution used as the electrolytic solution is preferably 3 to 30 g / L, more preferably 4 to 20 g / L, and still more preferably 10 to 18 g / L. Within the above range, the uniformity of the pits becomes high.

The sulfuric acid concentration in the mixed aqueous solution is preferably 0.01 to 10 g / L, more preferably 0.1 to 5 g / L, and still more preferably 1 to 4 g / L. Sulfuric acid forms an oxide film by an anodic reaction. Thereby, it is considered that a uniform uneven surface can be obtained.
Further, in the present invention, since sulfuric acid is added to the mixed aqueous solution, the average roughness _Ra is sufficient even when electrochemical roughening is performed using a plurality of electrolytic cells as described later. It can be.

The mixed aqueous solution can be used by adding a hydrochloric acid compound or a nitric acid compound having a nitrate ion such as aluminum nitrate, sodium nitrate or ammonium nitrate, or a hydrochloric acid ion such as aluminum chloride, sodium chloride or ammonium chloride. Also, a compound that forms a complex with copper can be added at a rate of 1 to 200 g / L. In the mixed aqueous solution, a metal contained in an aluminum alloy such as iron, copper, manganese, nickel, titanium, magnesium, or silicon may be dissolved. Hypochlorous acid or hydrogen peroxide may be added at 1 to 100 g / L.

The aluminum ion concentration in the mixed aqueous solution is preferably 3 to 30 g / L, more preferably 3 to 20 g / L, and still more preferably 8 to 18 g / L. Within the above range, the uniformity of the pits becomes high. Moreover, the replenishment amount of the mixed aqueous solution does not increase too much.

The concentration control of each component of the electrolytic solution is preferably performed using a combination of a multi-component concentration measurement method such as a concentration measurement method, feedforward control and feedback control. Thereby, accurate concentration management of the electrolytic solution becomes possible.
The multi-component concentration measurement method is, for example, a method of measuring the concentration using the propagation speed of ultrasonic waves in the liquid and the electric conductivity (conductivity) of the liquid, neutralization titration method, capillary electrophoresis analysis method, isotacophoresis (Isochophoresis, capillary tube isotachophoresis) Analytical method and ion chromatograph method are mentioned.
The ion chromatograph method is classified into an absorbance detection ion chromatograph, a non-suppressor type electric conductivity detection ion chromatograph, a suppressor type ion chromatograph, and the like depending on the type of detector. Among these, a suppressor type ion chromatograph is preferable from the viewpoint of ensuring measurement stability.

Specifically, it is preferable to control the concentration of each component of the electrolytic solution by the method described below.
When electrochemical surface roughening is performed, in the electrolytic solution, the hydrogen ion concentration decreases in proportion to the amount of energization, and the aluminum ion concentration increases. Therefore, by performing feedforward control based on the energization amount, the hydrogen ion concentration and the aluminum ion concentration can be kept constant.
That is, in order to increase the hydrogen ion concentration, the amount of electricity supplied, that is, the amount of acid proportional to the current value generated by the AC power supply is replenished to the electrolyte, and in order to reduce the aluminum ion concentration, the amount of electricity is proportional to the amount of electricity supplied. Since the amount of water is replenished to the electrolyte and the concentration of the acid is reduced by adding water, the amount of acid proportional to the amount of added water is replenished to the electrolyte, so that the hydrogen ion concentration and aluminum The ion concentration can be kept constant. In the following description, the water supplied to the electrolyte is also referred to as makeup water.

Furthermore, a concentration measurement system for measuring the concentration of the electrolyte is provided, and the concentration of each component of the electrolyte is controlled by using feedback control for controlling the supply of acid and makeup water based on the measured concentration of the electrolyte. It is preferable. By using feedback control in combination, the concentration of the electrolyte can be controlled with good control even when the electrolyte is taken out or brought in by an aluminum plate, the electrolyte is evaporated, or the like.
The concentration measurement method includes the multi-component concentration measurement method described above, and the correspondence between the electric conductivity of the electrolyte solution corresponding to the liquid composition of each component and the ultrasonic wave propagation velocity is taken, and the electric conductivity and the ultrasonic wave propagation velocity are determined. A method of measuring the concentration based on the value is particularly preferable.

Supplied water and acid are preferably supplied to the circulation tank. The circulation tank stores an electrolytic solution, supplies the stored electrolytic solution to the electrolytic bath, and stores the electrolytic solution discharged from the electrolytic bath. The electrolyte exceeding the capacity of the circulation tank is discharged due to overflow. The discharged electrolytic solution is detoxified and then discharged into a river or the like as a waste solution.

In the present invention, concentration control of three components such as sulfuric acid, hydrochloric acid, and aluminum ions is performed, but it is difficult to measure the concentration of the three components in real time. Therefore, it is preferable to control the concentration by previously adding sulfuric acid having the same concentration as the sulfuric acid concentration in the electrolytic solution to the replenishing water, and replenishing the replenishing water to which sulfuric acid has been added and hydrochloric acid.
In this method, it is preferable to control the sulfuric acid concentration in the makeup water. As a method for controlling the sulfuric acid concentration of the make-up water, there is a method of measuring the sulfuric acid concentration of the make-up water and adding sulfuric acid or water based on the measured result. Methods for measuring the sulfuric acid concentration of make-up water include measurement based on the conductivity, pH, specific gravity, or ultrasonic wave propagation speed of make-up water, neutralization titration method, capillary electrophoresis analysis, isotacophoresis analysis Method, ion chromatograph method and the like, and a method of measuring using the conductivity of makeup water is preferable.

FIG. 4 is a diagram showing an example of a system (hereinafter, also referred to as “concentration control system”) 200 for controlling the concentration of the electrolyte in the present invention.
In FIG. 4, by supplying the current output from the AC power source 201 to the electrode 202, an electrochemical roughening process is performed on the aluminum plate 204 that passes through the electrolytic solution 220 stored in the electrolytic bath 203. Therefore, the concentration control system 200 controls the concentration of the component contained in the electrolytic solution 220 in the electrolytic cell 203.

The concentration control system 200 includes a circulation tank 210, a first concentration measurement system 211 that measures the concentration of hydrochloric acid and aluminum ions contained in the electrolytic solution 220 in the circulation tank 210, a hydrochloric acid storage unit 212 that stores hydrochloric acid 221, Based on the data supplied from the AC power supply 201 and the first concentration measurement system 211, the hydrochloric acid 221 and / or the makeup water 222 to the circulation tank 210 based on the makeup water storage section 213 that stores the makeup water 222 containing water and sulfuric acid. And a second concentration measurement system 215 that measures the concentration of sulfuric acid contained in the makeup water 222. In FIG. 4, P indicates a pump. In FIG. 4, the solid line indicates the movement of the liquid, and the broken line indicates the signal flow.
In the concentration control system 200, the first concentration measurement system 211 measures the concentration of hydrochloric acid and aluminum ions in the electrolytic solution 220 in the circulation tank 210, and the controller 214 measures the concentration measured by the first concentration measurement system 211. And supply of hydrochloric acid from the hydrochloric acid reservoir 212 to the circulation tank 210 and supply of makeup water from the makeup water reservoir 213 to the circulation tank 210 based on the current generated by the AC power supply 201. The concentration is controlled. The electrolytic solution 220 stored in the circulation tank 210 is supplied to the electrolytic tank 203, and the electrolytic solution 220 in the electrolytic tank 203 is discharged to the circulation tank 210.
In the concentration control system 200, the sulfuric acid concentration in the makeup water 222 stored in the makeup water storage section 213 is measured by the second concentration measurement system 215, and water and / or sulfuric acid is replenished according to the measurement result. It controls by supplying to the water storage part 213.

As hydrochloric acid to be replenished to the electrolyte, it is preferable to use 10 to 35% by mass.
The sulfuric acid concentration in the makeup water is the same as the sulfuric acid concentration in the electrolytic solution. That is, for example, when the sulfuric acid concentration of the electrolytic solution is 3 g / L, the sulfuric acid concentration of makeup water is also 3 g / L. By making the sulfuric acid concentration of the makeup water equal to the sulfuric acid concentration of the electrolytic solution, the sulfuric acid concentration of the electrolytic solution can be kept constant without measuring the sulfuric acid concentration of the electrolytic solution.

Quantity of electricity in electrochemical graining treatment, an aluminum plate is amount of electricity when the anode sum is preferably from 150 ~ 800C / dm ^2, more preferably from 200 ~ 700C / dm ^2, 200 More preferably, it is ˜500 C / dm ² . When it is 150 C / dm ² or more, the surface roughness becomes sufficient, and the printing durability and the ease of adjusting the amount of water during printing become more excellent. When it is 800 C / dm ² or less, the stain resistance is more excellent.
In addition, when an aluminum plate having a concavo-convex pattern formed thereon by transfer is used, it is particularly preferably 200 to 400 C / dm ² .

The current density in the electrochemical surface roughening treatment is preferably 30 to 300 A / dm ² at the peak of the current value, more preferably 50 to 200 A / dm ² , and 75 to 125 A / dm ² . More preferably. When it is 30 A / dm ² or more, the productivity is further improved. When it is 300 A / dm ² or less, the voltage is not high and the power source capacity does not become too large, so that the power source cost can be reduced.
The current density is preferably set so as to increase gradually from the beginning to the end of the electrolytic treatment. This makes it easy to generate uniform pits. Specifically, the power supply and electrodes are divided and set so that the value of (final current density of electrolysis / initial current density of electrolysis) gradually increases to 1.1 to 2.0. It is preferable to do this.

The electrochemical surface roughening treatment can follow, for example, the electrochemical grain method (electrolytic grain method) described in Japanese Patent Publication No. 48-28123 and British Patent No. 896,563.

Various electrolyzers and power sources have been proposed. US Pat. No. 4,203,637, JP-A-56-123400, JP-A-57-59770, JP-A-53-12738, JP 53-32821, JP 53-32222, JP 53-32823, JP 55-122896, JP 55-13284, JP 62-127500, JP Those described in JP-A-1-52100, JP-A-1-52098, JP-A-60-67700, JP-A-1-230800, JP-A-3-257199, and the like can be used.
Further, JP-A-52-58602, JP-A-52-152302, JP-A-53-12738, JP-A-53-12739, JP-A-53-32821, JP-A-53-32222, JP 53-32833, JP 53-32824, JP 53-32825, JP 54-85802, JP 55-122896, JP 55-13284, JP 48-28123, JP-B-51-7081, JP-A-52-13338, JP-A-52-133840, JP-A-52-133844, JP-A-52-133845, JP-A-53-149135 And those described in JP-A No. 54-146234 and the like can also be used.

Furthermore, by adding and using a compound capable of forming a complex with Cu, uniform graining is possible even for an aluminum plate containing a large amount of Cu. Examples of the compound capable of forming a complex with Cu include ammonia; hydrogen atom of ammonia such as methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, cyclohexylamine, triethanolamine, triisopropanolamine, EDTA (ethylenediaminetetraacetic acid), etc. And amines obtained by substituting with a hydrocarbon group (aliphatic, aromatic, etc.); metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate and the like. In addition, ammonium salts such as ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium phosphate, and ammonium carbonate are also included.

The temperature of the mixed aqueous solution is preferably 20 ° C. or higher, more preferably 25 ° C. or higher, still more preferably 30 ° C. or higher, and preferably 60 ° C. or lower, preferably 50 ° C. or lower. More preferably, it is 40 ° C. or lower. When the temperature is 20 ° C. or higher, the refrigerator operating cost for cooling does not increase, and the amount of groundwater used for cooling can be suppressed. It is easy to ensure the corrosion resistance of equipment as it is 60 ° C. or lower.

The AC power supply wave used for the electrochemical surface roughening treatment is not particularly limited, and a sine wave, a rectangular wave, a trapezoidal wave, a triangular wave, or the like is used. A trapezoidal wave or a sine wave is preferable, and a sine wave is more preferable. A trapezoidal wave means what was shown in FIG. In the trapezoidal wave, the time until the current reaches a peak from zero (current rise time, TP) is preferably 0.5 to 3.5 msec, and more preferably 0.8 to 2.5 msec. If it is 0.5 msec or more, the production cost of the power supply is lowered. If it is 3.5 msec or less, the uniformity of the pits becomes more excellent. In the triangular wave, the current rise time can be arbitrarily selected.

Moreover, when using a sine wave, what is used substantially as a sine wave, such as commercial alternating current, can be used without particular limitation.

The duty of alternating current (time during which the aluminum plate in one cycle is an anode / time of one cycle) is preferably 0.33 to 0.66, more preferably 0.45 to 0.55. preferable.
The AC frequency is preferably 10 to 200 Hz, more preferably 20 to 150 Hz, and still more preferably 30 to 120 Hz. When the frequency is 10 Hz or more, large faceted (pitched square shape) pits are not easily formed, and the stain resistance is more excellent. If it is 200 Hz or less, it is difficult to be affected by the inductance component of the circuit through which the electrolytic current flows, and it becomes easy to manufacture a large-capacity power supply.

As the power supply device, for example, a commercial AC power supply, an inverter control power supply, or the like can be used. In particular, an inverter control power source using an IGBT (Insulated Gate Bipolar Transistor) element varies the voltage with respect to the width and thickness of the aluminum plate, the concentration of each component in the electrolytic solution, etc. When the current density of the plate) is controlled to be constant, this is preferable in terms of excellent followability.

One or more AC power supplies can be connected to the electrolytic cell. As shown in FIG. 6, the current ratio between the AC anode and cathode applied to the aluminum plate facing the main electrode is controlled to achieve uniform graining and to dissolve the carbon of the main electrode. In addition, it is preferable to install an auxiliary anode and divert part of the alternating current. In FIG. 6, 311 is an aluminum plate, 312 is a radial drum roller, 313a and 313b are main poles, 314 is an electrolytic treatment solution, 315 is an electrolyte supply port, and 316 is a slit. 317 is an electrolyte passage, 318 is an auxiliary anode, 319a and 319b are thyristors, 320 is an AC power source, 340 is a main electrolytic cell, and 350 is an auxiliary anode cell. An anodic reaction that acts on the aluminum plate facing the main electrode by diverting a part of the current value as a direct current to an auxiliary anode provided in a tank separate from the two main electrodes via a rectifier or switching element It is possible to control the ratio between the current value for the current and the current value for the cathode reaction. The current ratio (ratio of the total amount of electricity when the aluminum plate is the anode and the total amount of electricity when the aluminum plate is the cathode) is preferably 0.9 to 3, and preferably 0.95 to 2. More preferred.

In addition to the flat type described above, an electrolytic cell used for a known surface treatment such as a vertical type can be used as the electrolytic cell, but the radial type as described in JP-A-5-195300 can be used. The electrolytic cell is preferable from the viewpoint of preventing the back of the pit generated by the electrochemical surface roughening treatment.
When a flat electrolytic cell is used, an insulating plate is provided on the non-processed surface of the aluminum plate to prevent the back of the pit generated by the electrochemical surface roughening treatment, and current flows to the non-processed surface. It is preferable to take a method of preventing the above.
The electrolyte passing through the electrolytic cell may be parallel or counter to the traveling direction of the aluminum web, but a counter is more desirable.

By the way, when the aluminum plate is electrochemically roughened, it is preferable to increase the moving speed of the aluminum plate in order to improve the production amount. In order to increase the moving speed of the aluminum plate, it is necessary to increase the length of the electrochemical roughening treatment, that is, the treatment length.
As a method for increasing the treatment length, there is a method using a large electrolytic cell. However, since it is difficult to manufacture a large electrolytic cell, it is preferable to use a plurality of electrolytic cells. It is.

If the number of electrolytic cells to be used is increased, it becomes difficult to make the average roughness Ra of the aluminum plate surface _a sufficient value, but if the electrolytic solution contains sulfuric acid, it can be made a sufficient value. Therefore, the present invention makes it possible to make the average roughness Ra of the aluminum plate surface _a sufficient value even when the electrochemical surface roughening treatment is performed using a plurality of electrolytic cells. Can be improved.
The number of electrolytic cells is preferably 3 to 10. If the number is 3 to 7, the average roughness Ra can be _a sufficient value, and the productivity can be improved.

Here, also in the case of using the above radial type electrolytic cell, the flow rate of the electrolytic solution in the electrolytic cell is an average flow rate of 500 to 4000 mm / second in the same manner as described above, and the width orthogonal to the conveying direction of the metal web in the electrolytic cell. The flow rate distribution of the electrolyte with respect to the direction is within ± 50% of the average flow rate. Then, the metal web is conveyed at a speed of 0.05 to 1 second to pass through one inter-tank inter-electrode processing pause interval. In this case as well, a plurality of electrolyte solution supply ports are arranged between the metal web 311 and the

electrodes

313a and 313b corresponding to the

electrodes

313a and 313b. The electrolytic solution is sprayed and supplied from each electrolytic solution supply port.

In addition, after the electrochemical surface roughening treatment is completed, it is preferable to drain the liquid with a nip roller, further perform the water washing treatment for 1 to 10 seconds, and then drain the liquid with a nip roller.
The washing treatment is preferably carried out using a spray tube. As the spray tube used for the water washing treatment, for example, a spray tube having a plurality of spray tips in the width direction of the aluminum plate in which fan water spreads in a fan shape can be used. The interval between spray tips is preferably 20 to 100 mm, and the amount of liquid per spray tip is preferably 1 to 20 L / min. It is preferable to use a plurality of spray tubes.

Measurement of the average opening diameter of the recesses generated by the electrochemical surface roughening treatment is performed, for example, by photographing the surface of the support from directly above at a magnification of 2000 times or 50000 times using an electron microscope, and the obtained electron micrograph In FIG. 4, at least 50 pits each having a ring shape around each pit are extracted, and the diameter is read to obtain the opening diameter, and the average opening diameter is calculated.
In addition, in order to suppress variation in measurement, it is possible to perform equivalent circle diameter measurement using commercially available image analysis software. In this case, the electron micrograph is captured by a scanner, digitized, and binarized by software, and then an equivalent circular diameter is obtained.
As a result of measurement by the present inventor, the result of visual measurement and the result of digital processing showed almost the same value.

<Second etching process>
The second etching process is performed for the purpose of dissolving the smut generated by the electrochemical roughening process and dissolving the edge portion of the pit formed by the electrochemical roughening process. As a result, the edge portion of the large pit formed by the electrochemical surface roughening treatment is melted and the surface becomes smooth, and the ink is less likely to be caught on the edge portion, so that a lithographic printing plate precursor having excellent stain resistance is obtained. be able to.
The second etching treatment is basically the same as the first etching treatment, the etching amount is preferably at 0.01 g / m ² or more, more preferably 0.05 g / m ² or more, further preferably at 0.1 g / m ² or more, but preferably not more 10 g / m ² or less, more preferably at 5 g / m ² or less, more preferably at 3 g / m ² or less .

<Second desmut treatment>
After the second etching process, it is preferable to perform pickling (second desmut process) in order to remove dirt (smut) remaining on the surface. The second desmut process can be performed in the same manner as the first desmut process.

<Anodizing treatment>
The aluminum plate treated as described above may be further anodized. The anodizing treatment can be performed by a method conventionally used in this field. In this case, for example, in a solution having a sulfuric acid concentration of 50 to 300 g / L and an aluminum concentration of 5% by mass or less, an aluminum plate can be energized to form an anodic oxide film. As a solution used for the anodizing treatment, sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, amidosulfonic acid and the like can be used alone or in combination of two or more.

At this time, at least a component normally contained in an aluminum plate, an electrode, tap water, groundwater, or the like may be contained in the electrolytic solution. Furthermore, the second and third components may be added. Examples of the second and third components herein include metal ions such as Na, K, Mg, Li, Ca, Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn; Cation such as ammonium ion; anion such as nitrate ion, carbonate ion, chloride ion, phosphate ion, fluoride ion, sulfite ion, titanate ion, silicate ion, borate ion, etc., 0 to 10,000 ppm It may be contained at a concentration of about.

The conditions of the anodizing treatment cannot be determined unconditionally because they vary depending on the electrolyte used, but generally the electrolyte concentration is 1 to 80% by mass, the solution temperature is 5 to 70 ° C., and the current density is 0.5. It is appropriate that ˜60 A / dm ² , voltage 1˜100 V, electrolysis time 15 seconds˜50 minutes, and the anodic oxide film amount is adjusted to a desired amount.

Further, JP-A-54-81133, JP-A-57-47894, JP-A-57-51289, JP-A-57-51290, JP-A-57-54300, JP-A-57-136596, JP-A-58-107498, JP-A-60-200366, JP-A-62-136596, JP-A-63-176494, JP-A-4-17697, JP-A-4-280997, JP-A-6- The methods described in JP-A-207299, JP-A-5-24377, JP-A-5-32083, JP-A-5-125597, JP-A-5-195291 and the like can also be used.

Among these, as described in JP-A-54-12853 and JP-A-48-45303, it is preferable to use a sulfuric acid solution as the electrolytic solution. The sulfuric acid concentration in the electrolytic solution is preferably 10 to 300 g / L (1 to 30% by mass), more preferably 50 to 200 g / L (5 to 20% by mass), and the aluminum ion concentration Is preferably 1 to 25 g / L (0.1 to 2.5% by mass), more preferably 2 to 10 g / L (0.2 to 1% by mass). Such an electrolytic solution can be prepared, for example, by adding aluminum sulfate or the like to dilute sulfuric acid having a sulfuric acid concentration of 50 to 200 g / L.

The composition management of the electrolytic solution is conducted using the same method as in the case of hydrochloric acid electrolysis described above, and the conductivity, specific gravity and temperature, or conductivity and ultrasonic wave propagation corresponding to the matrix of sulfuric acid concentration and aluminum ion concentration. It is preferable to control by speed and temperature.

The liquid temperature of the electrolytic solution is preferably 25 to 55 ° C, more preferably 30 to 50 ° C.

When anodizing is performed in an electrolytic solution containing sulfuric acid, direct current may be applied between the aluminum plate and the counter electrode, or alternating current may be applied.
When a direct current is applied to the aluminum plate, the current density is preferably 1 to 60 A / dm ² , more preferably 5 to 40 A / dm ² .
In the case of continuous anodizing treatment, at the beginning of the anodizing treatment, so that current is concentrated on a part of the aluminum plate and so-called “burning” (part where the film becomes thicker than the surroundings) does not occur. It is preferable to increase the current density to 30 to 50 A / dm ² or more as the anodic oxidation process proceeds by passing a current at a low current density of 5 to 10 A / m ² .
Specifically, it is preferable that the current distribution of the DC power supply is set so that the current of the downstream DC power supply is equal to or greater than the current of the upstream DC power supply. By using such current distribution, so-called burning is less likely to occur, and as a result, high-speed anodization can be performed.

When the anodizing treatment is continuously performed, it is preferable that the anodizing process is performed by a liquid power feeding method in which power is supplied to the aluminum plate through an electrolytic solution.
By performing anodizing treatment under such conditions, a porous film having a large number of pores called micropores can be obtained. Usually, the average pore diameter is about 5 to 50 nm, and the average pore density is 300. It is about 800 / μm ² .

The amount of the anodized film is preferably 1 to 5 g / m ² . When it is 1 g / m ² or more, the plate is hardly damaged. If it is 5 g / m ² or less, a large amount of electric power is not required for production, which is economically advantageous. The amount of the anodized film is more preferably 1.5 to 4 g / m ² . Moreover, it is preferable to carry out so that the difference in the amount of the anodized film between the center portion of the aluminum plate and the vicinity of the edge portion is 1 g / m ² or less.
The amount of the anodized film on the back surface of the surface subjected to the electrochemical surface roughening treatment is preferably 0.1 to 1 g / m ² . When it is 0.1 g / m ² or more, the back surface is less likely to be damaged, and the image recording layer that comes into contact with the back surface is less likely to be damaged when stacked as a lithographic printing plate precursor. When it is 1 g / m ² or less, it is economically advantageous.

Examples of the electrolysis apparatus used for the anodizing treatment are those described in JP-A-48-26638, JP-A-47-18739, JP-B-58-24517, JP-A-2001-11698, and the like. Can be used.
Among these, the apparatus shown in FIG. 7 is preferably used. FIG. 7 is a schematic view showing an example of an apparatus for anodizing the surface of an aluminum plate.

In the anodizing apparatus 410 shown in FIG. 7, in order to energize the aluminum plate 416 via the electrolytic solution, a feeding tank 412 is provided on the upstream side in the traveling direction of the aluminum plate 416, and an anodizing tank 414 is provided on the downstream side. It is installed. The aluminum plate 416 is conveyed by the

pass rollers

422 and 428 as indicated by arrows in FIG. In the feed tank 412 into which the aluminum plate 416 is first introduced, an anode 420 connected to the positive electrode of the DC power supply 434 is installed, and the aluminum plate 416 serves as a cathode. Therefore, a cathode reaction occurs in the aluminum plate 416.

In the anodizing tank 414 into which the aluminum plate 416 is continuously introduced, a cathode 430 connected to the negative electrode of the DC power source 434 is installed, and the aluminum plate 416 serves as an anode. Therefore, an anodic reaction occurs on the aluminum plate 416, and an anodic oxide film is formed on the surface of the aluminum plate 416.
The distance between the aluminum plate 416 and the cathode 430 is preferably 50 to 200 mm. Aluminum is used as the cathode 430. The cathode 430 is preferably an electrode divided into a plurality of pieces in the traveling direction of the aluminum plate 416 in order to make it easy for hydrogen gas generated by the anode reaction to escape from the system. .

As shown in FIG. 7, it is preferable to provide a tank called an intermediate tank 413 in which an electrolytic solution does not accumulate between the power supply tank 412 and the anodizing treatment tank 414. By providing the intermediate tank 413, current can be prevented from bypassing from the anode 420 to the cathode 430 without passing through the aluminum plate 416. It is preferable to reduce the bypass current as much as possible by installing a nip roller 424 in the intermediate tank 413 to drain the liquid. The electrolyte discharged by draining is discharged out of the anodizing apparatus 410 from the drain port 442.

The electrolyte solution 418 stored in the power supply tank 412 has a higher temperature and / or higher concentration than the electrolyte solution 426 stored in the anodizing tank 414 in order to reduce voltage loss. In addition, the composition, temperature, and the like of the

electrolytic solutions

418 and 426 are determined from the formation efficiency of the anodized film, the micropore shape of the anodized film, the hardness of the anodized film, the voltage, the cost of the electrolytic solution, and the like.

The electrolytic solution is ejected from the

liquid supply nozzles

436 and 438 and supplied to the power supply tank 412 and the anodizing treatment tank 414. For the purpose of keeping the distribution of the electrolyte constant and preventing local current concentration of the aluminum plate 416 in the anodizing tank 414, the

liquid supply nozzles

436 and 438 are provided with slits, and the liquid flow to be ejected in the width direction. It has a constant structure.

In the anodizing tank 414, a shielding plate 440 is provided on the opposite side of the aluminum plate 416 from the cathode 430, and current flows to the opposite side of the surface of the aluminum plate 416 where the anodized film is to be formed. Deter. The distance between the aluminum plate 416 and the shielding shielding plate 440 is preferably 5 to 30 mm. It is preferable to use a plurality of DC power supplies 434 and connect the positive electrode sides in common. Thereby, the current distribution in the anodizing bath 414 can be controlled.

<Sealing treatment>
In this invention, you may perform the sealing process which seals the micropore which exists in an anodic oxide film as needed. By performing the sealing treatment, the developability (sensitivity) of the lithographic printing plate precursor can be improved.
It is well known that the anodized film is a porous film having pores called pores in a direction substantially perpendicular to the film surface. In the present invention, it is preferable to subject the anodizing treatment to a sealing treatment with a high sealing ratio. The sealing rate is preferably 50% or more, more preferably 70% or more, and still more preferably 90% or more. Here, the “sealing rate” is defined by the following formula.

Sealing rate = (surface area before sealing−surface area after sealing) / surface area before sealing × 100%

The surface area can be measured using, for example, a simple BET surface area measuring apparatus (for example, QUANTASORB (manufactured by Kantha Sorb), manufactured by Yuasa Ionics).

The sealing treatment is not particularly limited, and a conventionally known method can be used. For example, hydrothermal treatment, boiling water treatment, steam treatment, dichromate treatment, nitrite treatment, ammonium acetate salt treatment, electrodeposition sealing treatment, and the like described in JP-B 36-22063. Zirconate treatment, treatment with an aqueous solution containing a phosphate and an inorganic fluorine compound described in JP-A-9-244227, treatment with an aqueous solution containing a sugar described in JP-A-9-134002 , Treatment with an aqueous solution containing titanium and fluorine described in JP-A-2000-81704 and JP-A-2000-89466, alkali metal silica described in US Pat. No. 3,181,461, etc. Examples include acid salt treatment.

An example of a suitable sealing treatment is an alkali metal silicate treatment. The alkali metal silicate treatment uses an alkali metal silicate aqueous solution having a pH of 10 to 13 at 25 ° C. without causing gelation of the liquid and dissolution of the anodized film, and the alkali metal silicate concentration and treatment temperature. The processing conditions such as the processing time can be selected as appropriate. Suitable alkali metal silicates include, for example, sodium silicate, potassium silicate, and lithium silicate. Moreover, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. can be mix | blended in order to adjust pH of alkali metal silicate aqueous solution high.

Furthermore, you may mix | blend an alkaline-earth metal salt and / or a group 4 (Group IVA) metal salt with alkali metal silicate aqueous solution as needed. Examples of the alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate and barium nitrate; sulfates, hydrochlorides, phosphates, acetates, oxalates and boric acids of alkaline earth metals Examples thereof include water-soluble salts such as salts. Examples of Group 4 (Group IVA) metal salts include titanium tetrachloride, titanium trichloride, potassium fluoride titanium, titanium oxalate potassium, titanium sulfate, titanium tetraiodide, zirconium chloride oxide, zirconium dioxide, zirconium tetrachloride. And so on. Alkaline earth metal salts and Group 4 (Group IVA) metal salts can be used alone or in combination of two or more.
The concentration of the aqueous alkali metal silicate solution is preferably 0.01 to 10% by mass, and more preferably 0.05 to 5.0% by mass.

Another example of a suitable sealing treatment is a fluorinated zirconate treatment. The fluorinated zirconate treatment is performed using a fluorinated zirconate salt such as sodium fluorinated zirconate or potassium fluorinated zirconate. Among these, it is preferable to use sodium fluorinated zirconate. Thereby, the developability (sensitivity) of the lithographic printing plate precursor becomes excellent. The concentration of the fluorinated zirconate solution used for the fluorinated zirconate treatment is preferably 0.01 to 2% by mass, more preferably 0.1 to 0.3% by mass.
The fluorinated zirconate solution preferably contains sodium dihydrogen phosphate. The concentration of sodium dihydrogen phosphate is preferably 0.01 to 3% by mass, and more preferably 0.1 to 0.3% by mass.
The fluorinated zirconate solution may contain aluminum ions. In that case, the aluminum ion concentration of the fluorinated zirconate solution is preferably 1 to 500 mg / L.

The temperature for the sealing treatment is preferably 20 to 90 ° C., more preferably 50 to 80 ° C.
The sealing treatment time (immersion time in the solution) is preferably 1 to 20 seconds, and more preferably 5 to 15 seconds.

Further, after performing sealing treatment as necessary, a polymer or copolymer having the above-mentioned alkali metal silicate treatment, polyvinylphosphonic acid, polyacrylic acid, sulfo group or the like in the side chain, Japanese Patent Application Laid-Open No. 11-231509 A surface treatment such as a treatment of immersing or coating in a solution containing an organic compound having an amino group and a group selected from the group consisting of a phosphine group, a phosphone group, and a phosphoric acid group or a salt thereof described in the publication be able to.

It is preferable to perform a hydrophilization treatment described later after the sealing treatment.

<Hydrophilic treatment>
A hydrophilization treatment may be performed after the anodizing treatment or the sealing treatment. Examples of the hydrophilization treatment include treatment with potassium fluorozirconate described in US Pat. No. 2,946,638 and phosphomolybdate described in US Pat. No. 3,201,247. Treatment, alkyl titanate treatment described in British Patent 1,108,559, polyacrylic acid treatment described in German Patent 1,091,433, German Patent 1,134, No. 093 and British Patent No. 1,230,447, polyvinyl phosphonic acid treatment, Japanese Patent Publication No. 44-6409, phosphonic acid treatment, US Pat. No. 3,307,951 Phytic acid treatment described in the specification of JP, No. 58-16893 and JP-A No. 58-18291 Treatment with a salt of a molecular compound and a divalent metal, as described in US Pat. No. 3,860,426, hydrophilic cellulose (eg, zinc acetate) containing a water-soluble metal salt (eg, zinc acetate) And a treatment for providing a water-soluble polymer having a sulfo group described in JP-A-59-101651.

Further, phosphates described in JP-A-62-019494, water-soluble epoxy compounds described in JP-A-62-033692, and JP-A-62-097892 Phosphate-modified starch, diamine compounds described in JP-A-63-056498, amino acid inorganic or organic acids described in JP-A-63-130391, JP-A-63-145092 Organic phosphonic acids containing a carboxy group or a hydroxy group, compounds having an amino group and a phosphonic acid group described in JP-A-63-165183, and JP-A-2-316290 Specific carboxylic acid derivatives, phosphate esters described in JP-A-3-215095, JP-A-3-261592 Compounds having one amino group and one oxygen acid group of phosphorus described in the publication, phosphate esters described in JP-A-3-215095, and JP-A-5-246171 Aliphatic or aromatic phosphonic acids such as phenylphosphonic acid, compounds containing S atoms such as thiosalicylic acid described in JP-A-1-307745, and phosphorus described in JP-A-4-282737 Examples of the treatment include undercoating using a compound having a group of oxygen acids.
Further, coloring with an acid dye described in JP-A-60-64352 can also be performed.

In addition, hydrophilization treatment is performed by a method of immersing in an aqueous solution of an alkali metal silicate such as sodium silicate or potassium silicate, or a method of forming a hydrophilic component by applying a hydrophilic vinyl polymer or a hydrophilic compound. It is preferred to do so.

Hydrophilization treatment with an aqueous solution of an alkali metal silicate such as sodium silicate and potassium silicate is described in US Pat. No. 2,714,066 and US Pat. No. 3,181,461. It can be performed according to methods and procedures.
Examples of the alkali metal silicate include sodium silicate, potassium silicate, and lithium silicate. The aqueous solution of alkali metal silicate may contain an appropriate amount of sodium hydroxide, potassium hydroxide, lithium hydroxide or the like.
The aqueous solution of alkali metal silicate may contain an alkaline earth metal salt or a Group 4 (Group IVA) metal salt. Examples of the alkaline earth metal salt include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, and barium nitrate; sulfates; hydrochlorides; phosphates; acetates; oxalates; Examples of Group 4 (Group IVA) metal salts include titanium tetrachloride, titanium trichloride, potassium fluoride titanium, potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium tetrachloride. Is mentioned. These alkaline earth metal salts and Group 4 (Group IVA) metal salts are used alone or in combination of two or more.

The amount of Si adsorbed by the alkali metal silicate treatment can be measured with a fluorescent X-ray analyzer, and the amount of adsorption is preferably about 1.0 to 15.0 mg / m ² .
By this alkali metal silicate treatment, the effect of improving the dissolution resistance to the alkaline developer on the surface of the lithographic printing plate support is obtained, the dissolution of the aluminum component into the developer is suppressed, and the developer fatigue It is possible to reduce the occurrence of development residue due to the above.

Further, the adsorption amount of Si is more preferably 1.0 to 10.0 mg / m ² . When the amount of adsorbed Si is in the above range, the stain resistance of the halftone dot non-image portion is improved.
Specifically, in the shadow portion (halftone dot portion) of the printed matter, the area ratio of the halftone dot is high (70 to 90%), and in the area corresponding to that of the planographic printing plate, the image portion (image recording layer) The area is large, and the area of the non-image part (exposed part of the support) is relatively small. In such a case, at the time of printing, the inks placed on the adjacent image portions come into contact with each other (that is, entangled), the ink adheres to the non-image portions therebetween, and the non-image portions of the printed material are crushed ( In other words, the phenomenon of contamination) is likely to occur.
However, the hydrophilicity of the non-image area is improved by carrying out a hydrophilic treatment so that the amount of Si adhering to the surface of the lithographic printing plate support is within the above range, so that the obtained lithographic printing plate support is obtained. When a lithographic printing plate is prepared using and is printed, the stain resistance of the halftone dot non-image area can be improved.
In order to make the amount of Si within the above range, for example, an aqueous solution having a sodium silicate concentration of 1 to 5% by mass is used to perform a hydrophilic treatment. As sodium silicate, it is particularly preferable to use No. 1 sodium silicate.

The hydrophilization treatment by forming a hydrophilic component can also be performed according to the conditions and procedures described in JP-A Nos. 59-101651 and 60-149491.
Examples of the hydrophilic vinyl polymer used in this method include polyvinyl sulfonic acid, a sulfo group-containing vinyl polymerizable compound such as p-styrene sulfonic acid having a sulfo group, and ordinary vinyl polymerization such as (meth) acrylic acid alkyl ester. And a copolymer with a functional compound. Examples of the hydrophilic compound used in this method include compounds having at least one selected from the group consisting of —NH ₂ group, —COOH group and sulfo group.

<Dry>
After obtaining the lithographic printing plate support as described above, it is preferable to dry the surface of the lithographic printing plate support before providing the image recording layer. Drying is preferably performed after the final treatment of the surface treatment, after washing with water and draining with a nip roller.
The drying temperature is preferably 70 ° C or higher, more preferably 80 ° C or higher, preferably 110 ° C or lower, more preferably 100 ° C or lower.
The drying time is preferably 1 second or longer, more preferably 2 seconds or longer, more preferably 20 seconds or shorter, and even more preferably 15 seconds or shorter.

[Lithographic printing plate precursor]
The lithographic printing plate support obtained by the present invention can be provided with an image recording layer to form the lithographic printing plate precursor of the present invention. A photosensitive composition is used for the image recording layer.
Examples of the photosensitive composition suitably used in the present invention include a thermal positive photosensitive composition containing an alkali-soluble polymer compound and a photothermal conversion substance (hereinafter, this composition and an image recording layer using the same). ), A thermal negative photosensitive composition containing a curable compound and a photothermal conversion substance (hereinafter also referred to as “thermal negative type”), a photopolymerizable photosensitive composition (hereinafter referred to as “thermal positive type”). , Also referred to as “photopolymer type”), a negative photosensitive composition containing a diazo resin or a photocrosslinking resin (hereinafter also referred to as “conventional negative type”), and a positive photosensitive composition containing a quinonediazide compound. Product (hereinafter also referred to as "conventional positive type"), photosensitive composition that does not require a special development step (hereinafter referred to as Referred to as "non-treatment type".) It can be mentioned as, in particular, thermal positive type, thermal negative type, non-treatment type is preferred. Hereinafter, these suitable photosensitive compositions will be described.

<Thermal positive type>
<Photosensitive layer>
The thermal positive type photosensitive composition contains an alkali-soluble polymer compound and a photothermal conversion substance. In the thermal positive type image recording layer, the photothermal conversion substance converts the energy of light such as infrared lasers into heat, which effectively eliminates the interaction that reduces the alkali solubility of alkali-soluble polymer compounds. To do.

Examples of the alkali-soluble polymer compound include a resin containing an acidic group in the molecule and a mixture of two or more thereof. In particular, a phenolic hydroxy group, sulfonamide group (in -SO ₂ NH-R (wherein, R represents a hydrocarbon group.)), Active imino group _{_{(-SO 2 NHCOR, -SO 2 NHSO}} 2 R, -CONHSO A resin having an acidic group such as ₂ R (wherein R has the same meaning as described above) is preferable in terms of solubility in an alkali developer.
In particular, a resin having a phenolic hydroxy group is preferable from the viewpoint of excellent image-forming properties when exposed to light such as an infrared laser, such as phenol-formaldehyde resin, m-cresol-formaldehyde resin, p-cresol-formaldehyde resin, Novolac resins such as m- / p-mixed cresol-formaldehyde resin, phenol / cresol (any of m-, p- and m- / p-mixed) mixed-formaldehyde resin (phenol-cresol-formaldehyde co-condensation resin) Are preferable.
Further, the polymer compound described in JP-A No. 2001-305722 (particularly [0023] to [0042]), and the repetition represented by the general formula (1) described in JP-A No. 2001-215893 Preferred examples also include polymer compounds containing units, and polymer compounds described in JP-A No. 2002-311570 (particularly [0107]).

As the photothermal conversion substance, a pigment or a dye having a light absorption region in the infrared region having a wavelength of 700 to 1200 nm is preferably mentioned from the viewpoint of recording sensitivity. Examples of the dye include azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes (for example, , Nickel thiolate complex). Of these, cyanine dyes are preferable, and cyanine dyes represented by general formula (I) described in JP-A No. 2001-305722 are particularly preferable.

The thermal positive type photosensitive composition may contain a dissolution inhibitor. Preferable examples of the dissolution inhibitor include dissolution inhibitors described in JP-A-2001-305722, [0053] to [0055].
In addition, in the thermal positive type photosensitive composition, as a additive, a sensitivity modifier, a printing agent for obtaining a visible image immediately after heating by exposure, a compound such as a dye as an image colorant, a coating property In addition, it is preferable to include a surfactant for improving the processing stability. For these, compounds as described in JP-A-2001-305722, [0056] to [0060] are preferable.
In addition to the above points, the photosensitive composition described in detail in JP-A No. 2001-305722 is preferably used.

Further, the thermal positive type image recording layer is not limited to a single layer but may have a two-layer structure.
As an image recording layer having a two-layer structure (multilayer image recording layer), a lower layer (hereinafter referred to as “A layer”) having excellent printing durability and solvent resistance is provided on the side close to the support, and a positive layer is provided thereon. A type provided with a layer having excellent image formability (hereinafter referred to as “B layer”) is preferable. This type has high sensitivity and can realize a wide development latitude. The B layer generally contains a photothermal conversion substance. Preferred examples of the photothermal conversion substance include the dyes described above.
As the resin used for the A layer, a polymer having a monomer having a sulfonamide group, an active imino group, a phenolic hydroxy group or the like as a copolymerization component is preferably used because it has excellent printing durability and solvent resistance. . As the resin used for the B layer, an alkaline aqueous solution-soluble resin having a phenolic hydroxy group is preferably exemplified.
In addition to the resin, the composition used for the A layer and the B layer can contain various additives as necessary. Specifically, various additives as described in JP-A-2002-3233769, [0062] to [0085] are preferably used. Further, the additives described in [0053] to [0060] of the above-mentioned JP-A No. 2001-305722 are also preferably used.
About each component which comprises A layer and B layer, and its content, it is preferable to make it describe in Unexamined-Japanese-Patent No. 11-218914.
When the image recording layer having the two-layer structure described above is formed on a lithographic printing plate support having a surface Si adsorption amount of 1.0 to 10.0 mg / m ² by hydrophilization, the resulting lithographic printing plate is obtained as follows. , Ink inking property is improved, and stain resistance of a halftone dot non-image portion is improved.

<Intermediate layer>
An intermediate layer is preferably provided between the thermal positive type image recording layer and the support. Preferred examples of the component contained in the intermediate layer include various organic compounds described in JP-A-2001-305722, [0068].

<Others>
As a method for producing a thermal positive type image recording layer and a plate making method, methods described in detail in JP-A No. 2001-305722 can be used.

<Thermal negative type>
The thermal negative photosensitive composition contains a curable compound and a photothermal conversion substance. The thermal negative type image recording layer is a negative photosensitive layer in which a portion irradiated with light such as an infrared laser is cured to form an image portion.
<Polymerized layer>
As one of the thermal negative type image recording layers, a polymerization type image recording layer (polymerization layer) is preferably exemplified. Heavy / BR> ≡W contains a photothermal conversion substance, a radical generator, a radical polymerizable compound that is a curable compound, and a binder polymer. In the polymerization layer, infrared light absorbed by the light-to-heat conversion substance is converted into heat, the radical generator is decomposed by this heat to generate radicals, and the radical polymerizable compound is polymerized in a chain by the generated radicals and cured. .

As a photothermal conversion substance, the photothermal conversion substance used for the thermal positive type mentioned above is mentioned, for example. Specific examples of particularly preferred cyanine dyes include those described in JP-A-2001-133969, [0017] to [0019].
Preferred examples of the radical generator include onium salts. In particular, onium salts described in JP-A-2001-133969, [0030] to [0033] are preferable.
Examples of the radically polymerizable compound include compounds having at least one terminal ethylenically unsaturated bond, preferably two or more.
As the binder polymer, a linear organic polymer is preferably exemplified. Preferable examples include linear organic polymers that are soluble or swellable in water or weak alkaline water. Among them, a (meth) acrylic resin having an unsaturated group such as an allyl group or an acryloyl group or a benzyl group and a carboxy group in the side chain is preferable in that it has an excellent balance of film strength, sensitivity, and developability. .
As the radical polymerizable compound and the binder polymer, those described in detail in [0036] to [0060] of JP-A No. 2001-133969 can be used.

The thermal negative photosensitive composition contains an additive described in JP-A-2001-133969, [0061] to [0068] (for example, a surfactant for improving coatability). Is preferred.

As the method for producing the polymerization layer and the plate making method, methods described in detail in JP-A No. 2001-133969 can be used.

<Acid cross-linked layer>
Further, as one of the thermal negative type image recording layers, an acid cross-linked image recording layer (acid cross-linked layer) is also preferably exemplified. The acid crosslinking layer comprises a photothermal conversion substance, a thermal acid generator, a compound (crosslinking agent) that crosslinks with an acid that is a curable compound, and an alkali-soluble polymer compound that can react with the crosslinking agent in the presence of an acid. contains. In the acid cross-linking layer, infrared light absorbed by the photothermal conversion substance is converted into heat, the heat acid generator is decomposed by this heat to generate an acid, and the generated acid reacts with the cross-linking agent and the alkali-soluble polymer compound. And harden.

Examples of the photothermal conversion substance include the same substances as those used for the polymerization layer.
Examples of the thermal acid generator include thermal decomposition compounds such as photoinitiators for photopolymerization, photochromic agents for dyes, and acid generators used in microresists.
Examples of the crosslinking agent include an aromatic compound substituted with a hydroxymethyl group or an alkoxymethyl group; a compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group; and an epoxy compound.
Examples of the alkali-soluble polymer compound include a novolak resin and a polymer having a hydroxyaryl group in the side chain.

<Photopolymer type>
The photopolymerization type photosensitive composition contains an addition polymerizable compound, a photopolymerization initiator, and a polymer binder.
As the addition polymerizable compound, an ethylenically unsaturated bond-containing compound capable of addition polymerization is preferably exemplified. The ethylenically unsaturated bond-containing compound is a compound having a terminal ethylenically unsaturated bond. Specifically, for example, it has a chemical form such as a monomer, a prepolymer, and a mixture thereof. Examples of monomers include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, maleic acid) and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds. Is mentioned.
Moreover, as an addition polymerizable compound, a urethane type addition polymerizable compound is also preferably exemplified.

As the photopolymerization initiator, various photopolymerization initiators or a combination system (photoinitiation system) of two or more kinds of photopolymerization initiators can be appropriately selected depending on the wavelength of the light source to be used. For example, the initiation systems described in JP-A-2001-22079, [0021] to [0023] are preferable.
The polymer binder not only functions as a film-forming agent for the photopolymerization type photosensitive composition, but is soluble or swellable in alkaline water because it is necessary to dissolve the image recording layer in an alkaline developer. An organic high molecular polymer is used. As such an organic polymer, those described in JP-A-2001-22079, [0036] to [0063] are preferably exemplified.

In the photopolymer type photopolymerization type photosensitive composition, additives described in JP-A-2001-22079, [0079] to [0088] (for example, a surfactant for improving coatability) , Colorants, plasticizers, thermal polymerization inhibitors).

Further, it is preferable to provide an oxygen-blocking protective layer on the photopolymer type image recording layer in order to prevent the action of inhibiting the polymerization of oxygen. Examples of the polymer contained in the oxygen barrier protective layer include polyvinyl alcohol and copolymers thereof.
Furthermore, it is also preferable to provide an intermediate layer or an adhesive layer as described in [0124] to [0165] of JP-A-2001-228608.

<Conventional negative type>
The conventional negative photosensitive composition contains a diazo resin or a photocrosslinking resin. Among them, preferred is a photosensitive composition containing a diazo resin and an alkali-soluble or swellable polymer compound (binder).
Examples of the diazo resin include condensates of aromatic diazonium salts and compounds containing active carbonyl groups such as formaldehyde; condensates of p-diazophenylamines and formaldehyde with hexafluorophosphate or tetrafluoroborate. An organic solvent-soluble diazo resin inorganic salt which is a reaction product of In particular, a high molecular weight diazo compound containing 20 mol% or more of a hexamer described in JP-A-59-78340 is preferable.
Examples of the binder include a copolymer containing acrylic acid, methacrylic acid, crotonic acid, or maleic acid as an essential component. Specifically, a multi-component copolymer of monomers such as 2-hydroxyethyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylic acid as described in JP-A-50-118802, Examples thereof include multi-component copolymers composed of alkyl acrylate, (meth) acrylonitrile and unsaturated carboxylic acid as described in JP-A-56-4144.

The conventional negative type photosensitive composition has, as additives, the bake-out agent, dye, and flexibility and abrasion resistance described in JP-A-7-281425, [0014] to [0015]. It is preferable to contain a plasticizer for imparting, a compound such as a development accelerator, and a surfactant for improving coating properties.

Under the conventional negative type photosensitive layer, an intermediate layer containing a polymer compound having a component having an acid group and a component having an onium group as described in JP-A-2000-105462 is provided. Is preferred.

<Conventional positive type>
The conventional positive type photosensitive composition contains a quinonediazide compound. Among them, preferred is a photosensitive composition containing an o-quinonediazide compound and an alkali-soluble polymer compound.
Examples of o-quinonediazide compounds include esters of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and phenol-formaldehyde resin or cresol-formaldehyde resin, described in US Pat. No. 3,635,709. And esters of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and pyrogallol-acetone resin.
Examples of the alkali-soluble polymer compound include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde co-condensation resin, polyhydroxystyrene, N- (4-hydroxyphenyl) methacrylamide copolymer, Carboxy group-containing polymers described in JP-A-7-36184, acrylic resins containing phenolic hydroxy groups as described in JP-A-51-34711, and JP-A-2-866 Examples thereof include acrylic resins having a sulfonamide group and urethane resins.

Conventional positive type photosensitive compositions include compounds such as sensitivity modifiers, printing agents, dyes and the like described in JP-A-7-92660, [0024] to [0027] as additives. It is preferable to contain a surfactant for improving the coating property as described in [0031] of Kaihei 7-92660.

Under the conventional positive type photosensitive layer, it is preferable to provide an intermediate layer similar to the intermediate layer suitably used for the above-described conventional negative type.

<Non-treatment type>
Examples of the non-processing type photosensitive composition include a thermoplastic fine particle polymer type, a microcapsule type, and a sulfonic acid-generating polymer-containing type. These are all heat-sensitive types containing a photothermal conversion substance. The photothermal conversion substance is preferably the same dye as that used in the above-described thermal positive type.

The thermoplastic fine particle polymer type photosensitive composition is obtained by dispersing a hydrophobic and heat-meltable fine particle polymer in a hydrophilic polymer matrix. In the image recording layer of the thermoplastic fine particle polymer type, the hydrophobic fine particle polymer is melted by heat generated by exposure and is fused to form a hydrophobic region, that is, an image portion.
As the fine particle polymer, those in which fine particles melt and coalesce with heat are preferable, and those having a hydrophilic surface and capable of being dispersed in a hydrophilic component such as dampening water are more preferable. Specifically, Research Disclosure No. 33303 (January 1992), JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, and JP-A-9-171250, and European Patent Application Publication No. 931,647. Preferred examples thereof include thermoplastic fine particle polymers. Of these, polystyrene and polymethyl methacrylate are preferred. Examples of the fine particle polymer having a hydrophilic surface include those in which the polymer itself is hydrophilic; those in which a hydrophilic compound such as polyvinyl alcohol and polyethylene glycol is adsorbed on the surface of the fine particle polymer to make the surface hydrophilic.
The fine particle polymer preferably has a reactive functional group.

Examples of the microcapsule-type photosensitive composition include those described in JP-A No. 2000-118160 and compounds having a heat-reactive functional group as described in JP-A No. 2001-277740. A microcapsule type is preferable.

Examples of the sulfonic acid-generating polymer used in the sulfonic acid-generating polymer-containing photosensitive composition include sulfonic acid ester groups, disulfone groups, or sec- or tert-sulfonamides described in JP-A-10-282672. Examples thereof include polymers having a group in the side chain.

By including a hydrophilic resin in an unprocessed photosensitive composition, not only on-press developability is improved, but also the film strength of the photosensitive layer itself is improved. Examples of the hydrophilic resin include those having a hydrophilic group such as hydroxy group, carboxy group, hydroxyethyl group, hydroxypropyl group, amino group, aminoethyl group, aminopropyl group, carboxymethyl group, and hydrophilic sol-gel conversion system A binder resin is preferred.

The unprocessed image recording layer can be developed on a printing press without requiring a special development process. As a method for producing an unprocessed type image recording layer and a plate-making printing method, methods described in detail in JP-A No. 2002-178655 can be used.

<Back coat>
In this way, the backside of the lithographic printing plate precursor of the present invention obtained by providing various image recording layers on the lithographic printing plate support obtained by the present invention, if necessary, is an image in the case of overlapping. In order to prevent the recording layer from being damaged, a coating layer made of an organic polymer compound can be provided.

[Plate making method (lithographic printing plate production method)]
The lithographic printing plate precursor using the lithographic printing plate support obtained by the present invention is made into a lithographic printing plate by various treatment methods according to the image recording layer.
Examples of the active light source used for image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, and a chemical lamp. Examples of the laser beam include a helium-neon laser (He—Ne laser), an argon laser, a krypton laser, a helium-cadmium laser, a KrF excimer laser, a semiconductor laser, a YAG laser, and a YAG-SHG laser.

After the above exposure, if the image recording layer is any of thermal positive type, thermal negative type, conventional negative type, conventional positive type, and photopolymer type, after exposure, it is developed using a developer to obtain a lithographic printing plate. It is preferable to obtain.
The developer is preferably an alkaline developer, and more preferably an alkaline aqueous solution that does not substantially contain an organic solvent.
A developer substantially free of alkali metal silicate is also preferred. As a method for developing using a developer substantially not containing an alkali metal silicate, a method described in detail in JP-A-11-109637 can be used.
A developer containing an alkali metal silicate can also be used.

1. Production of aluminum plate Each component (mass%) shown in Table 1 is contained, and the balance is prepared by using an aluminum alloy composed of Al and inevitable impurities. An ingot having a width of 500 mm and a width of 1200 mm was produced by a DC casting method. After the surface was shaved with a chamfering machine with an average thickness of 10 mm, the temperature was kept constant at 550 ° C. for about 5 hours, and when the temperature dropped to 400 ° C., rolling with a thickness of 2.7 mm using a hot rolling mill A board was used. Furthermore, after performing heat processing using a continuous annealing machine at 500 degreeC, it cold-rolled and finished to 0.3 mm in thickness and 1060 mm in width, and the aluminum plate 1 was obtained.

2. Preparation of lithographic printing plate support (Examples 1 to 24 and Comparative Examples 1 to 9)
The aluminum plate obtained above was subjected to the following surface treatment to obtain each lithographic printing plate support shown in Table 2.

<Surface treatment>
As the surface treatment, the following various treatments (a) to (g) were continuously performed.

(A) Etching treatment in alkaline aqueous solution (first etching treatment)
Etching was performed by spraying an aqueous solution of caustic soda concentration of 370 g / L, aluminum ion concentration of 1 g / L, and a temperature of 60 ° C. onto the aluminum plate from a spray tube. The etching amount of the surface subjected to the electrochemical roughening treatment after the aluminum plate was 3 g / m ² .
Then, the liquid was drained with a nip roller, and further washed with water for 5 seconds using a spray tube having a spray tip in which spray water spread in a fan shape, and further drained with a nip roller.

(B) Desmutting treatment in an acidic aqueous solution An aluminum plate was sprayed with an aqueous solution having a sulfuric acid concentration of 170 g / L, an aluminum ion concentration of 5 g / L, and a temperature of 50 ° C. from a spray tube to perform desmutting treatment for 5 seconds. As a sulfuric acid aqueous solution, the waste liquid of the (i) anodizing process mentioned later was used. Then, the liquid was drained with a nip roller, and further washed with water for 5 seconds using a spray tube having a spray tip in which spray water spread in a fan shape, and further drained with a nip roller.

(C) Electrochemical roughening treatment using alternating current in an acidic aqueous solution As an electrolytic solution, an aqueous solution (temperature 35 ° C.) having a hydrochloric acid concentration, an aluminum ion concentration and a sulfuric acid concentration shown in Table 2 is used. The current was controlled by inverter control using a gate bipolar transistor) element, and an electrochemical roughening process was performed using a power source capable of generating an alternating current of arbitrary waveform. The AC current waveform, current rise time (in cases other than a sine wave), duty ratio, and frequency were as shown in Table 2, respectively.
A power source was installed for each electrolytic cell so that the current density gradually increased. The value of (final current density of electrolysis / initial current density of electrolysis) was 1.8. The current density during the anode reaction of the aluminum plate at the alternating current peak was 45 A / dm ² at the beginning of electrolysis.
The amount of electricity was the total amount of electricity when the aluminum plate was an anode, as shown in Table 2. Moreover, the current ratio (ratio of the total amount of electricity when the aluminum plate was the anode and the total amount of electricity when the aluminum plate was the cathode) was as shown in Table 2.
The concentration control of the electrolytic solution was performed by adding make-up water preliminarily added with an amount of hydrochloric acid proportional to the amount of energization and sulfuric acid of a desired concentration according to a data table obtained in advance. In addition, a data table is created by measuring the relationship between the electric conductivity of the liquid and the ultrasonic wave propagation speed corresponding to each composition, and added from the measurement results of the electric conductivity of the liquid and the ultrasonic wave propagation speed. The amount of hydrochloric acid and the amount of makeup water were feedback controlled.
Then, the liquid was drained with a nip roller, and further washed with water for 5 seconds using a spray tube having a spray tip in which spray water spread in a fan shape, and further drained with a nip roller.

(D) Etching process in alkaline aqueous solution (second etching process)
Etching was performed by spraying an aqueous solution of caustic soda concentration of 370 g / L, aluminum ion concentration of 1 g / L, and a temperature of 35 ° C. onto the aluminum plate from a spray tube. The etching amount of the aluminum plate subjected to the electrochemical surface roughening treatment was 0.2 g / m ² .
Then, the liquid was drained with a nip roller, and further washed with water for 5 seconds using a spray tube having a spray tip in which spray water spread in a fan shape, and further drained with a nip roller.

(E) Desmutting treatment in an acidic aqueous solution An aluminum plate was sprayed with an aqueous solution having a sulfuric acid concentration of 170 g / L, an aluminum ion concentration of 5 g / L, and a temperature of 50 ° C. from a spray tube to perform desmutting treatment for 5 seconds. As a sulfuric acid aqueous solution, the waste liquid of the (i) anodizing process mentioned later was used.
Then, the liquid was drained with a nip roller, and further washed with water for 5 seconds using a spray tube having a spray tip in which spray water spread in a fan shape, and further drained with a nip roller.

(F) Anodizing treatment As an electrolytic solution, an electrolytic solution (temperature 50 ° C.) in which aluminum sulfate was dissolved in a 170 g / L sulfuric acid aqueous solution to make an aluminum ion concentration 5 g / L was used. The anodizing treatment was performed so that the average current density during the anodic reaction of the aluminum plate was 15 A / dm ² , and the final oxide film amount was 2.7 g / m ² .
Then, the liquid was drained with a nip roller, and further washed with water for 5 seconds using a spray tube having a spray tip in which spray water spread in a fan shape, and further drained with a nip roller.

(G) Hydrophilization treatment 1
The aluminum plate was immersed in a 1.0 mass% aqueous solution of sodium silicate (temperature 20 ° C.) for 10 seconds. The amount of Si on the surface of the aluminum plate measured with a fluorescent X-ray analyzer was 3.5 mg / m ² .
Then, the liquid was drained with a nip roller, and further washed with water for 5 seconds using a spray tube having a spray tip in which spray water spread in a fan shape, and further drained with a nip roller. Furthermore, 90 degreeC wind was sprayed for 10 seconds, it was made to dry, and the support body for lithographic printing plates was obtained.

3. Observation of the surface of the lithographic printing plate support The surface shape of the lithographic printing plate support obtained in Examples 1 to 24 was measured using a scanning electron microscope (JSM-5500, manufactured by JEOL Ltd., the same shall apply hereinafter). When observed at a magnification of 50000 times, fine irregularities with a diameter of 0.1 to 0.2 μm were uniformly and densely formed on the surface. Further, when observed with a scanning electron microscope at a magnification of 2000, irregularities having a diameter of 1 to 20 μm were formed on the surface of these lithographic printing plate supports. Fine irregularities having a diameter of 0.1 to 0.2 μm were generated by being superimposed on the irregularities having a diameter of 1 to 20 μm.
On the other hand, when the surface shape of the lithographic printing plate support obtained in Comparative Examples 1 to 9 was observed in the same manner, fine irregularities with a diameter of 0.1 to 0.2 μm and a diameter of 1 to Although unevenness of 20 μm was generated, unevenness of 1 to 20 μm in diameter had a nonuniform distribution of depth and pit diameter as compared with the example. Moreover, many plateau parts existed on the surface.

4). Preparation of lithographic printing plate precursor A lithographic printing plate precursor was obtained by providing a thermal positive type image recording layer on the lithographic printing plate support obtained above as follows. Before providing the image recording layer, an intermediate layer was provided as described later.

(Examples 1 to 24, Comparative Examples 1 to 9)
An undercoat liquid A having the following composition was applied onto a lithographic printing plate support and dried at 80 ° C. for 15 seconds to form a component coating film (intermediate layer). The coating amount of the coating film after drying was 15 mg / m ² .

<Undercoat liquid A composition>
・ The following polymer compound 0.3g
・ Methanol 100g
・ Water 1g

Next, an image recording layer coating solution B1 having the following composition was coated on the components with a wire bar so as to be 0.85 g / m ² after drying, and dried at 140 ° C. for 50 seconds.
After that, the image recording layer coating liquid B2 having the following composition was applied with a wire bar so as to be 0.25 g / m ² after drying, and dried at 140 ° C. for 1 minute to form a multilayer thermal positive type image recording layer. And a lithographic printing plate precursor was obtained.

<Composition of coating liquid B1 for image recording layer>
N- (4-aminosulfonylphenyl) methacrylamide / acrylonitrile / methyl methacrylate copolymer (molar ratio 36/34/30, weight average molecular weight 50,000) 1.920 g
-M, p-cresol novolak (m-cresol novolak / p-cresol novolak ratio 6/4, weight average molecular weight 4000) 0.213 g
-0.032 g of cyanine dye B represented by the following formula
・ P-Toluenesulfonic acid 0.008g
・ Tetrahydrophthalic anhydride 0.19g
・ Bis-p-hydroxyphenylsulfone 0.126g
・ 2-methoxy-4- (N-phenylamino) benzenediazonium ・ hexafluorophosphate 0.032g
・ 0.078 g of dye having 1-naphthalenesulfonic acid anion as the counter anion of Victoria Pure Blue BOH
-Fluorosurfactant (Megafac F-780, manufactured by Dainippon Ink & Chemicals, Inc.) 0.020g
・ Γ-Butyrolactone 13.18g
・ Methyl ethyl ketone 25.41g
・ 1-methoxy-2-propanol 12.97g

<Composition of coating liquid B2 for image recording layer>
・ Phenol / m, p-cresol novolak (phenol / m-cresol novolak / p-cresol novolak = 5/3/2, weight average molecular weight 4000) 0.274 g
-0.029 g of cyanine dye B represented by the above formula
-Structural polymer C / methyl ethyl ketone 30% solution represented by the following formula (Structural polymer B / methyl ethyl ketone 30% solution) 0.14 g
-Quaternary ammonium salt D shown by the following formula 0.004 g
・ Sulphonium salt E represented by the following formula: 0.065 g
・ Fluorosurfactant (Megafac F-780, manufactured by Dainippon Ink & Chemicals, Inc.) 0.004g
・ Fluorosurfactant (Megafac F-782, manufactured by Dainippon Ink & Chemicals, Inc.) 0.020g
・ Methyl ethyl ketone 10.39g
・ 1-methoxy-2-propanol 20.98g

5). Evaluation of planographic printing plate precursor The evaluation of image quality, printing durability and stain resistance of the planographic printing plate were evaluated by the following methods.

(1) Evaluation of image quality Visual evaluation was performed on the unevenness of image quality regarding streaks and chatter marks on the coated surface of the planographic printing plate obtained as described above.
(A) Streaks ○: No streaks occur ○ △: Streaks occur from ○ but no streaks occur from △: Streaks occur from ○ △, but from × Little streaks X: Remarkably streaks (b) Chatter marks ○: No chatter marks occur ○ △: Chatter marks are generated compared to ○, but less than Δ
△: Chatter marks are generated more than △, but less than × ×: Remarkably chatter marks are generated (2) Printing durability The obtained lithographic printing plate precursor was used with a TrendSetter manufactured by Creo Then, an image was drawn at a drum rotation speed of 150 rpm and a beam intensity of 10 W.
Thereafter, using a PS processor 940H manufactured by FUJIFILM Corporation with an alkaline developer having the following composition, the solution was maintained at 30 ° C. and developed for 20 seconds to obtain a lithographic printing plate. All the lithographic printing plate precursors had good sensitivity.

<Alkali developer composition>
・ D-sorbite 2.5% by mass
-Sodium hydroxide 0.85 mass%
・ Polyethylene glycol lauryl ether (weight average molecular weight 10) 0.5 mass%
・ Water 96.15% by mass

The resulting lithographic printing plate was printed with a Lithrone printing machine manufactured by Komori Corporation using DIC-GEOS (N) black ink manufactured by Dainippon Ink and Chemicals. At the time of printing, a multi-cleaner manufactured by Fuji Film Co., Ltd. was attached to the surface of the image recording layer for 1 minute every 5,000 sheets and then wiped with water. The printing durability was evaluated based on the number of printed sheets when it was visually recognized that the density of the solid image started to decrease.
The results are shown in Tables 3 and 4. The meanings of symbols in Tables 3 and 4 are as follows.
○: 30,000 or more ○ △: 20,000 or more and less than 30,000 △: 10,000 or more and less than 20,000 × ×: less than 10,000

(3) Stain resistance Using a lithographic printing plate obtained in the same manner as in the evaluation of printing durability, a DIC-GEOS (s) red ink was applied using a Mitsubishi diamond F2 printer (manufactured by Mitsubishi Heavy Industries). The blanket was visually evaluated after the printing was performed and 10,000 sheets were printed.
The results are shown in Tables 3 and 4. The meanings of symbols in Tables 3 and 4 are as follows.
○: The blanket is hardly dirty ○ △: The blanket is slightly dirty, but the printed matter is not dirty △: The blanket is dirty and the printed matter is slightly dirty ×: The blanket is dirty and the printed matter is clear It is dirty

As is apparent from Tables 3 and 4, the lithographic printing plate using the lithographic printing plate support obtained by the method for producing a lithographic printing plate support of the present invention (Examples 1 to 24) is either Excellent printing durability and stain resistance. Further, the image surface unevenness with respect to the streaks and chatter marks on the coated surface was also excellent.
In contrast, in Comparative Examples 1 to 9, the obtained lithographic printing plates using the lithographic printing plate support were inferior in printing durability and stain resistance.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application No. 2008-94245 filed on Mar. 31, 2008, the contents of which are incorporated herein by reference.

Claims

A metal web made of aluminum or an aluminum alloy is conveyed while being sequentially immersed in an electrolytic solution of a plurality of electrolytic cells, and between the plurality of electrodes disposed opposite to the metal web in the electrolytic cell and the metal web A method for producing a support for a lithographic printing plate in which an electric current is supplied and the metal web is subjected to an electrochemical surface roughening treatment,
The flow rate of the electrolytic solution in the electrolytic cell is an average flow rate of 500 to 4000 mm / second in each electrolytic cell, and the flow rate distribution of the electrolytic solution in the width direction perpendicular to the conveying direction of the metal web in the electrolytic cell is Within ± 50% of the average flow rate,
When the conveyance path section of the metal web facing the gap region between adjacent electrodes among the plurality of electrodes is defined as the inter-bath electrode processing pause section, the single inter-bath electrode treatment pause section is passed. A method for producing a support for a lithographic printing plate, comprising transporting the metal web at a speed of 0.05 to 1 second.
The method for producing a lithographic printing plate support according to claim 1, wherein the electrolytic solution contains chlorine ions, sulfate ions, and aluminum ions.
3. The method for producing a lithographic printing plate support according to claim 1, wherein the electrolytic solution is caused to flow in a direction opposite to a conveying direction of the metal web.
The method for producing a support for a lithographic printing plate according to any one of claims 1 to 3, wherein at least three sections of the inter-battery electrode processing pause are provided in one electrolytic cell.
The metal web transport path section until the metal web is taken out of the electrolytic solution of the electrolytic tank and immersed in the electrolytic solution of another electrolytic tank disposed on the downstream side of the metal web transport path is stopped outside the tank. The sum of both conveying path sections from both ends of the plurality of electrodes in the electrolytic cell in the direction of arrangement to the electrolyte gas / liquid interface of the electrolytic cell When the sum of the electrode electrode outer side processing pause interval that is continuous to the inter-vessel treatment pause interval is taken as the sum of the time period for passing through the inter-vessel treatment pause interval 1 to 5 seconds, 5. The method for producing a lithographic printing plate support according to claim 1, wherein the web is conveyed.
6. The method for producing a lithographic printing plate support according to claim 5, wherein the inter-tank processing suspension section is provided with at least three sections.
The electrolyte solution according to any one of claims 1 to 6, wherein the electrolyte solution is jetted and supplied from a plurality of electrolyte solution supply ports arranged between the metal web and the electrode in correspondence with the electrode. A method for producing a lithographic printing plate support according to Item.