JP2002293055A - Method for manufacturing substrate for lithographic printing plate, substrate for lithographic printing plate, and original plate for lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a substrate for a lithographic printing plate, the substrate for the lithographic printing plate and an original plate for the lithographic printing plate in which there exists no generation of severe contamination with an ink and which can be stably and inexpensively manufactured. SOLUTION: The method for manufacturing the substrate for the lithographic printing plate comprising a surface-roughening processing in which an aluminum alloy sheet is electrolytically surface-roughened by using AC in an acidic solution and an anodizing treatment process characterized by using an AC wave shape with a time of 1.5-6 msec from 0 to the peak in the electrolitically surface-roughening process is provided. In addition, the substrate for the lithographic printing plate characterized by being manufactured by the method for manufacturing the substrate for the lithographic printing plate is provided. In addition, the original plate for the lithographic printing is characterized by successively forming an undercoat layer with a dry weight of 0.001-1 g/m<2> , a positive type photo-sensitive layer or a negative type photo-sensitive layer with a dry weight of 1-3 g/m<2> and a mat layer with a dry weight of 0.001-1 g/m<2> in this order on the surface of the substrate for the lithographic printing plate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a lithographic printing plate support, a lithographic printing plate support, and a lithographic printing plate precursor.

[0002]

2. Description of the Related Art Conventionally, a lithographic printing plate support is produced by subjecting one or both surfaces of an aluminum alloy plate to a roughening treatment. Then, a photosensitive layer is applied to the surface of the lithographic printing plate support to produce a lithographic printing plate precursor. This lithographic printing plate precursor is subjected to exposure, development, and the like, so that an image is formed and the lithographic printing plate precursor is ready for printing, and a lithographic printing plate is manufactured.

[0003] In order to improve the abrasion resistance of a lithographic printing plate during printing, in the process of producing a lithographic printing plate support, the surface after roughening is often subjected to anodizing treatment. Further, in order to shorten the vacuum contact time during plate making, a fine projection called a mat layer may be provided on the surface of the photosensitive layer of the lithographic printing plate precursor. As described above, the lithographic printing plate precursor is subjected to plate making processes such as image exposure, development, and water washing to be a lithographic printing plate. The image exposure method includes a method in which a lithographic film on which an image is printed is brought into close contact with a light source to make a difference between an image part and a non-image part, or a method using a laser or a method of projecting an image to directly form an image part or a non-image part. A method of writing a non-image portion to make a difference between an image portion and a non-image portion is used. During the development process after image exposure, the undissolved photosensitive layer forms an image area as an ink receptor, and the portion where the photosensitive layer has been dissolved and removed exposes the surface of the aluminum plate or anodic oxide film below it. To form a non-image area as a water receptor. After development, if necessary, hydrophilic treatment,
A gumming process and, if necessary, a burning process may be performed.

The lithographic printing plate is mounted on a cylindrical plate cylinder of a printing press. By supplying ink and fountain solution to the plate cylinder, the ink adheres to the lipophilic image area, and the lipophilic non-hydrophilic printing plate becomes hydrophilic. Water adheres to the image area, transfers the ink in the image area to the blanket cylinder, and then prints the image on paper from the blanket cylinder.
However, in some cases, the ink adheres to the non-image portion in a dot-like or annular shape, and as a result, there is a problem that a dot-like or annular stain is generated on the paper surface (severe ink stain). .

[0005] Further, as a raw material, a material whose alloy component is not controlled, that is, a scrap material containing various impurities,
Alternatively, it is conceivable to use a secondary metal or a reclaimed metal which has a lower market price than a new metal and contains many impurity elements. However, almost no control of the alloy components has been made, so that it could not be used at all for raw materials requiring high quality surface treatment appearance and printing performance, such as lithographic printing plates. In particular, there has been a problem that it is difficult to perform uniform roughening due to impurities, resulting in a non-uniform surface, and a printing performance defect such as blanket contamination is likely to occur. Further, there is a problem in that the oxide film is defective due to the intermetallic compound, ink is easily applied to the defect, and dot-like stain (severe ink stain) occurs in a non-image portion of a printed matter.

Further, in recycling used aluminum with a small amount of energy consumption, it is essential to use a low-purity aluminum plate as a support for a lithographic printing plate in order to reduce energy consumption in the future. It was an issue.

[0007] Further, in the electrolytic surface roughening treatment in the manufacturing process of the lithographic printing plate support, an alternating current or a direct current is used. When the component fluctuates greatly and the component of the aluminum material fluctuates, there may be a problem that it is difficult to form a roughened shape within a certain range, and it is necessary to strictly control the current waveform.

[0008]

From the foregoing, it is an object of the present invention to provide a stable and low-cost method that does not cause severe ink stains even when an aluminum alloy plate whose alloy components are not controlled is used as a raw material. The present invention provides a method for producing a lithographic printing plate support, a lithographic printing plate support, and a lithographic printing plate precursor that can be produced by the method described above.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have arrived at the present invention. That is, the present invention relates to a method for producing a lithographic printing plate support, comprising: <1> a surface roughening treatment step of subjecting an aluminum alloy sheet to electrolytic surface roughening treatment using an alternating current in an acidic solution; and an anodizing treatment step. A method for producing a lithographic printing plate support, characterized in that in the electrolytic surface roughening treatment, an alternating current waveform having a time from 0 to a peak of 1.5 to 6 msec is used.

<2> The method for producing a lithographic printing plate support according to <1>, wherein the purity of the aluminum alloy plate is 95 to 99.4% by mass.

<3> The method for producing a lithographic printing plate support according to <1> or <2>, wherein the aluminum alloy plate contains at least five kinds of the following metals in the following ranges: . Fe: 0.3 to 1.0% by mass, S
i: 0.15 to 1.0% by mass, Cu: 0.1 to 1.0% by mass, Mg: 0.1 to 1.5% by mass, Mn: 0.1 to 1.0%
1.5% by mass, Zn: 0.1 to 0.5% by mass, Cr:
0.01 to 0.1% by mass, Ti: 0.03 to 0.5% by mass.

<4> Before the electrolytic surface roughening treatment and / or
Or <1> to after having the following steps
<3> The method for producing a lithographic printing plate support according to any of <3>. (1) In an alkaline aqueous solution, the aluminum alloy
5 g / m ² dissolving alkali etching treatment step,
(2) A desmutting step of desmutting the aluminum alloy plate having undergone the alkali etching step in an acidic solution.

<5> The desmut treatment in the desmut treatment step uses an acidic solution having an acid solution concentration of 250 to 500 g / l and an aluminum ion concentration of 1 to 15 g / l, and is treated at 60 to 90 ° C. for 1 to 180 seconds. The method for producing a lithographic printing plate support according to any one of <1> to <4>, wherein

<6> The method for producing a lithographic printing plate support according to <4> or <5>, wherein a mechanical surface roughening step is provided before the alkali etching step.

<7> The support for a lithographic printing plate as described in any one of <1> to <6>, wherein a sealing step and / or a hydrophilizing step are provided after the anodizing step. It is a method of manufacturing the body.

<8> Before the electrolytic roughening step,
The method for producing a lithographic printing plate support according to any one of <1> to <7>, further comprising an activation treatment step of performing an activation treatment on the surface of the aluminum alloy plate.

<9> A lithographic printing plate support produced by the method for producing a lithographic printing plate support according to any one of <1> to <8>.

[0018] <10> dry weight 0.001 to 1 g / m ² of the subbing layer on the surface of the lithographic printing plate support according to <9>, dry weight of 1 to 3 g / m ² positive photosensitive layer or negative A lithographic printing plate precursor comprising: a photosensitive layer; and a mat layer having a dry weight of 0.001 to 1 g / m ² .

<11> Average surface roughness (Ra) is 0.3
The lithographic printing plate precursor as described in <10>, wherein the lithographic printing plate precursor has an L * value of 50 to 95 and a delta Eab * of 2 or less.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS << Method of Manufacturing Lithographic Printing Plate Support >> The lithographic printing plate support of the present invention is prepared by preparing, for example, a web-like aluminum alloy plate made of aluminum or an aluminum alloy. At least by performing a surface roughening treatment and an anodic oxidation treatment. Specifically, the roughening treatment (roughening treatment step) includes at least (1) a degreasing step for removing rolling oil adhering to the aluminum alloy sheet, (2) a mechanical roughening treatment step, and Alkali etching treatment step, (3) electrolytic surface roughening treatment step,
(4) It is preferable to have a desmutting step.
After the surface roughening treatment, (5) anodizing treatment (anodizing treatment step) is performed to finally produce a lithographic printing plate support. Hereinafter, a method for producing a lithographic printing plate support will be described in detail.

<Raw Materials for Aluminum Alloy Sheet> As the raw materials for the aluminum alloy sheet used in the present invention, known materials described in the Aluminum Handbook, 4th edition (1990, Light Metal Association), for example, JIS1050 material, J
IS1100 material, JIS3003 material, JIS3103
Materials, JIS 3005 materials and the like can be used.
9.4 mass%, and iron (Fe), silicon (S
i) an aluminum alloy containing at least five or more of copper (Cu), magnesium (Mg), manganese (Mn), zinc (Zn), chromium (Cr), and titanium (Ti) in a range described later. It is preferable to use an aluminum alloy plate using a scrap aluminum material or a secondary metal.

In the present invention, the content of Al is 95-99.
It is preferable to use a 4 mass% aluminum alloy plate. If the content exceeds 99.4% by mass, the allowable amount of impurities is reduced, so that the cost reduction effect may be reduced. On the other hand, if the content is less than 95% by mass, impurities are contained in large amounts, and problems such as cracks may occur during rolling. A more preferable Al content is 95 to 99% by mass, and particularly preferably 95 to 99% by mass.
97% by mass.

The content of Fe is preferably 0.3 to 1.0% by mass. Fe is 0.1-0.
Among the elements contained at about 2% by mass, the amount of solid solution in Al is small, and most of them remain as intermetallic compounds. If the Fe content exceeds 1.0% by mass, cracks are likely to occur during rolling, and if it is less than 0.3% by mass, the cost reduction effect decreases, which is not preferable. A more preferable Fe content is 0.5 to 1.0% by mass.

The content of Si is preferably 0.15 to 1.0% by mass. Si is JIS2000, 4000
It is an element contained in a large amount of scrap of 6000 series materials. In addition, 0.03-0.1% by mass of new bullion
It is an element contained before and after, and exists as a solid solution in Al or as an intermetallic compound. When heated in the process of manufacturing the support, Si that has been dissolved may precipitate as elemental Si. It is known that elemental Si and FeSi-based intermetallic compounds adversely affect severe ink stain resistance. When the content of Si exceeds 1.0% by mass,
For example, treatment with sulfuric acid described below (desmut treatment step)
In some cases, this cannot be completely removed, and if it is less than 0.15% by mass, the cost reduction effect is reduced. A more preferred Si content is 0.3 to 1.0% by mass.

The Cu content is preferably 0.1 to 1.0% by mass. Cu is an element contained in a large amount of JIS2000-based and 4000-based scrap. Relatively A
Easy to dissolve in l. If the Cu content exceeds 1.0% by mass, it may not be possible to completely remove the Cu by, for example, a treatment with sulfuric acid described below. If the Cu content is less than 0.1% by mass, the cost reduction effect decreases. More preferred C
The content of u is 0.3 to 1.0% by mass.

The Mg content is preferably 0.1 to 1.5% by mass. Mg is JIS2000, 3000
-Based, 5000-based, and 7000-based materials. Particularly, since it is contained in a large amount in the can end material, one of the main impurity metals contained in the scrap material is
One. Mg is relatively easily dissolved in Al and forms an intermetallic compound with Si. Mg content of 1.5% by mass
If the amount exceeds 0.1%, it may not be possible to completely remove it by, for example, a treatment with sulfuric acid described below. If the amount is less than 0.1% by mass, the cost reduction effect is reduced. More preferred M
The content of g is 0.5 to 1.5% by mass, and more preferably 1.0 to 1.5% by mass.

The Mn content is preferably from 0.1 to 1.5% by mass. Mn is an element contained in a large amount of JIS 3000-based material scrap. Especially can body
It is one of the main impurity metals contained in the scrap material because it is contained in a large amount in the material. Mn is also relatively easily dissolved in Al and forms an intermetallic compound with AlFeSi. Mn
If the content exceeds 1.5% by mass, for example, it may not be possible to completely remove this by treatment with sulfuric acid described below,
If the amount is less than 0.1% by mass, the cost reduction effect is reduced. A more preferable Mn content is 0.5 to 1.5% by mass, and still more preferably 1.0 to 1.5% by mass.

The Zn content is preferably 0.1 to 0.5% by mass. Zn is an element particularly contained in JIS 7000 series scrap. It is relatively easy to form a solid solution in Al. If the Zn content exceeds 0.5% by mass, for example, it may not be possible to completely remove the Zn by treatment with sulfuric acid described below, and if it is less than 0.1% by mass, the cost reduction effect is reduced. A more preferred Zn content is 0.1.
3 to 0.5% by mass.

The Cr content is preferably 0.01 to 0.1% by mass. Cr is JIS 5000 series, 6000
Metal is an impurity metal contained in a small amount in scraps of 7000 series and 7000 series. If the content of Cr exceeds 0.1% by mass, for example, it may not be possible to completely remove the content by treatment with sulfuric acid described below, and if it is less than 0.01% by mass, the cost reduction effect is reduced. A more preferable Cr content is 0.05 to 0.1% by mass.

The content of Ti is preferably 0.03 to 0.5% by mass. Ti is usually used as a crystal refining material.
It is an element added in an amount of from 0.01 to 0.04% by mass. JIS5
000 series, 6000 series, and 7000 series scraps are relatively large as impurity metals. If the content of Ti exceeds 0.5% by mass, for example, it may not be possible to completely remove the Ti by treatment with sulfuric acid described below, and if it is less than 0.03% by mass, the cost reduction effect is reduced.
A more preferable content of Ti is 0.05 to 0.5% by mass.

The aluminum alloy plate used in the present invention is made of a material containing aluminum at the above-mentioned content (purity) and containing at least five of the eight impurity element groups. The aluminum alloy plate is subjected to a rolling process or a heat treatment as appropriate, using a casting method using the above-described raw materials, to a thickness of 0.1 to 0.7 mm, and to a flatness correction process as necessary. Manufactured. As a method for manufacturing the aluminum alloy plate, a DC casting method, a method in which a soaking treatment and / or an annealing treatment is omitted from the DC casting method, and a continuous casting method can be used.

<Electrolytic surface-roughening treatment step> The electrolytic surface-roughening treatment step is a step of electrochemically roughening the surface of the aluminum alloy plate by passing an alternating current in an acidic solution using the aluminum alloy plate as an electrode. This is different from the mechanical roughening process described later.

As the acidic solution used in the present invention, those used for electrochemical surface roughening treatment using ordinary direct current or alternating current can be used, and among them, an acidic solution mainly containing hydrochloric acid or nitric acid is used. Is preferred. Here, “mainly” as used in the present invention means that the main component is contained in the aqueous solution in an amount of 30% by mass or more, preferably 50% by mass or more based on the whole components. Hereinafter, the same applies to other components.

The acidic solution mainly composed of nitric acid includes:
As described above, it is possible to use those used for electrochemical surface roughening treatment using normal DC current or AC current, for example,
One or more of nitric acid compounds such as aluminum nitrate, sodium nitrate, and ammonium nitrate can be used by adding to nitric acid aqueous solution having a nitric acid concentration of 5 to 15 g / liter from 0.01 g / liter to saturation. Iron, copper, manganese,
Metals and the like contained in aluminum alloys such as nickel, titanium, magnesium, and silicon may be dissolved.
The acidic solution mainly composed of nitric acid contains nitric acid, an aluminum salt and a nitrate, and has an aluminum ion of 1 to 15 g / liter, preferably 1 to 10 g.
/ Liter, and ammonium ion is 10 to 300
It is preferable to use those obtained by adding aluminum nitrate and ammonium nitrate to a nitric acid aqueous solution having a nitric acid concentration of 5 to 15 g / liter so that the concentration becomes ppm. The aluminum ions and ammonium ions increase spontaneously during the electrochemical graining treatment. The liquid temperature at this time is 10
-95 ° C is preferred, and 40-80 ° C is more preferred.

As the acidic solution mainly composed of hydrochloric acid, as in the case of nitric acid, those used for electrochemical surface roughening treatment using a direct current or an alternating current can be used.
For example, 0.01 g of one or more hydrochloric acid compounds such as aluminum chloride, sodium chloride, and ammonium chloride are added.
Per liter / liter until saturation is reached
Per liter of hydrochloric acid aqueous solution. In the acidic solution mainly composed of hydrochloric acid, metals contained in aluminum alloys such as iron, copper, manganese, nickel, titanium, magnesium and silicon may be dissolved.

The alternating current waveform used in the electrochemical surface roughening treatment includes a time T from when the current reaches 0 to a peak.
An alternating current waveform with p of 1.5 to 6 msec is used. When the Tp is less than 1.5 msec, it is difficult to form uniformly shaped crater-shaped concave portions,
If it exceeds c, the shape of the roughened surface becomes unstable. A preferred Tp value is 2 to 5 msec, and a more preferred Tp value is 2.5 msec to 4.5 msec.
sec.

If the condition of the Tp value is satisfied, a sine wave (50 Hz or 60 Hz commercial alternating current), a rectangular wave, a trapezoidal wave, a triangular wave, or the like can be used. Above all, a sine wave or a trapezoidal wave is preferable. When a sine wave (commercial alternating current) is used, an arbitrary roughened shape can be obtained industrially advantageously by controlling the firing angle by a thyristor and adjusting the current waveform. The commercial AC may be a single-phase AC or a three-phase AC, and it is preferable to use a sine-wave AC whose phase angle is controlled. When a trapezoidal wave is used, any desired roughened shape can be obtained industrially advantageously by adjusting the rise time of the waveform.

The frequency is preferably 40 to 150 Hz, and 5
0 to 120 Hz is more preferable, and 50 to 60 Hz is still more preferable. 1 and 2 show examples of a sine wave and a trapezoidal wave preferably used in the present invention. By using a sine wave or trapezoidal wave, the rise time of the waveform can be lengthened, so that the voltage can be reduced in designing the power supply, which is particularly advantageous in terms of cost.

The alternating current aluminum alloy plate used for the electrochemical surface roughening treatment is an alternating current in which the ratio of the quantity of electricity QA as an anode to the quantity of electricity QC as a cathode, and QC / QA is 0.9 to 1.0. It is preferably used, and more preferably 0.95 to 0.99. The duty of AC is 0.25-0.5,
From the viewpoint of the production of the power supply device, it is preferably 0.33 to 0.5. The term "duty" as used in the present invention refers to ta / T when the time during which an aluminum alloy plate undergoes an anodic reaction is ta in an AC cycle T. In particular, in addition to the formation of a smut component consisting mainly of aluminum hydroxide on the surface of the aluminum alloy plate during the cathode reaction, dissolution and destruction of the oxide film occur, and the pitting reaction during the next anode reaction of the aluminum alloy plate , The selection of duty has a large effect on uniform roughening. However, it is particularly preferable to set the duty to 0.33 to 0.5 in manufacturing the power supply.

The current density is a peak value of a trapezoidal or rectangular wave, and is preferably 10 to 200 A / dm ² on both the anode cycle side Ia and the cathode cycle side Ic of the current. Ic /
Ia is preferably in the range of 0.9 to 1.5. The sum of the quantities of electricity involved in the anodic reaction of the aluminum alloy plate at the time when the electrochemical graining is completed is 50 to 80.
0 C / dm ² is preferred.

As the electrolytic cell used for electrochemical surface roughening using alternating current in the present invention, an electrolytic cell used for a known surface treatment such as a vertical type, a flat type, and a radial type can be used. As a power supply method to the aluminum alloy plate, a direct power supply method using a conductor roll or a liquid power supply method without using a conductor roll (indirect power supply method) can be used.

The electrolytic solution passing through the electrolytic cell may be parallel or counter to the progress of the aluminum web (aluminum alloy plate). One or more AC power supplies can be connected to one electrolytic cell. Further, two or more electrolytic cells can be used.

When the indirect power supply system is used,
It is preferable to adjust the ratio of the amount of electricity at the time of anode to the amount of electricity at the time of cathode applied to the aluminum alloy plate by a method using an auxiliary anode described in Japanese Patent No. 37716 and Japanese Patent Publication No. 5-42520. It is particularly preferable to control the current flowing through the auxiliary anode by using a rectifier such as a thyristor, a diode, or a GTO. When the method described in Japanese Patent Publication No. Hei 6-37716 is used, the amount of AC current at the anode and the amount of AC current at the surface of the aluminum alloy plate facing the carbon electrode of the main electrode where the electrochemical surface roughening reaction is performed are performed. Of electricity (current value) can be easily controlled. Further, the influence of the magnetic bias of the transformer is small in the production of the power supply device, which is very advantageous in terms of cost.

For controlling the current value when performing electrochemical surface roughening using a sine wave, a transformer, a variable induction voltage regulator, and the like are used in combination to change the current value used for electrolysis. This is done by feeding back to the induction voltage regulator. then,
In the method of controlling the current value, a method of controlling the phase with a thyristor can be used together as described in JP-A-55-25381.

In the electrochemical surface roughening treatment, if the distance between the aluminum alloy plate and the electrode and the liquid flow velocity are not constant, the current tends to be biased. What is not suitable as a support is produced. In order to solve the problem, a liquid supply nozzle provided with a liquid pool chamber therein and having a slit for discharging liquid of 1 to 5 mm in the width direction of the aluminum web can be used. In addition, it is particularly preferable to provide a plurality of liquid pool chambers, and provide a valve and a flow meter in a pipe connected to each liquid pool chamber to adjust the amount of liquid blown out from each slit.

The distance between the aluminum alloy plate and the electrode is 5 to
100 mm is preferable, and 8 to 15 mm is more preferable.
In order to keep this distance constant, there is a method described in Japanese Patent Publication No. 61-30036, in which a running aluminum alloy plate is run while pressing the web against a sliding surface by using static pressure on a surface on which the plate can slide. used. Or JP-A-8-3008
As described in JP-A-43-43, a method of using a roller having a large diameter to keep the distance between the electrode and the aluminum alloy plate constant can also be used.

When the direct power supply system is used, Japanese Patent Laid-Open No.
It is preferable to conduct a surface roughening treatment electrochemically using a conductor roll as described in JP-A-177441 and an apparatus described in JP-A-56-123400. Although the conductor roll can be provided on the upper surface or the lower surface of the aluminum alloy plate, it is particularly preferable that the conductor roll is provided on the upper surface of the aluminum alloy plate and pressed against the aluminum alloy plate by a nip device. The length of the aluminum alloy plate in contact with the conductor roll is preferably 1 mm to 300 mm with respect to the aluminum traveling direction. The pass roll facing the conductor roll with the aluminum alloy plate interposed therebetween is preferably a rubber roll. The pressing pressure and the hardness of the rubber roll are arbitrarily set under the condition that no arc spot is generated. By installing the conductor roll on the upper surface of the aluminum alloy plate, replacement work and inspection work of the conductor roll are simplified. It is preferable to use a method in which power is supplied to the end of the conductor roll while sliding the power supply brush against the rotating body.

The conductor roll pressed against the aluminum alloy plate should always be cooled with an electrolytic solution having the same composition and the same temperature as the electrolytic solution used for electrochemical surface roughening in order to prevent the generation of arc spots. preferable. If foreign matter enters the electrolyte, an arc spot is likely to be caused. Therefore, it is preferable to wind a filter cloth or the like around the spray used for cooling, or to put a filter with a fine mesh into the pipe on the upstream side of the spray pipe.

As the electrolysis apparatus used in the above-mentioned surface roughening treatment step, a known electrolysis apparatus such as a vertical type, a flat type and a radial type can be used. Electrolysis devices are particularly preferred. FIG. 3 is a schematic diagram of a radial electrolytic device used in the present invention. In FIG. 3, an aluminum alloy plate W is wound around a radial drum roller 12 arranged in a main electrolytic cell 10 and electrolyzed by main electrodes 13a and 13b connected to an AC power supply 11 in a conveying process. It is processed.
The acidic solution 15 is supplied from a solution supply port 14 through a slit 16 to a solution passage 17 between the radial drum roller 12 and the main poles 13a and 13b. Next, the aluminum alloy plate W treated in the main electrolytic cell 10 is subjected to electrolytic treatment in the auxiliary anode cell 20. An auxiliary anode 21 is disposed in the auxiliary anode tank 20 so as to face the aluminum alloy plate W, and the acidic solution 15 is supplied so as to flow between the auxiliary anode 21 and the aluminum alloy plate W. The auxiliary anode 21 can be selected from a known oxygen generation electrode such as ferrite, iridium oxide, platinum, or platinum clad or plated with a valve metal such as titanium, niobium, or zirconium. The main poles 13a and 13b are made of carbon,
It can be selected from platinum, titanium, niobium, zirconium, stainless steel and an electrode used for a cathode for a fuel cell, and carbon is particularly preferred. As the carbon, generally commercially available impervious graphite for chemical equipment,
Resin-core graphite or the like can be used.

The supply direction of the acidic solution passing through the main electrolytic cell 10 and the auxiliary anode cell 20 is the direction of the aluminum alloy plate W
May be parallel or counter to the progress of the game. The relative flow rate of the acidic solution to the aluminum alloy plate is 10 to 100
0 cm / sec is preferable. One or more AC power supplies can be connected to one electrolytic device. Further, two or more electrolysis devices may be used, and electrolysis conditions in each device may be the same or different. Further, after the electrolytic treatment is completed, it is preferable to perform liquid drainage by a nip roller and water washing by spraying so as not to carry out the treatment liquid to the next step.

Further, in the electrolytic surface roughening treatment,
Nitric acid and water, for example, (i) the conductivity of the acidic solution, (ii) the propagation speed of the ultrasonic wave, and (iii) the temperature Based on the nitric acid and aluminum ion concentrations determined from above, add the nitric acid and water while adjusting the amount of addition, and sequentially discharge the acidic solution of the same volume as the added volume of nitric acid and water from the electrolytic device. By doing so, it is preferable to keep the concentration of the acidic solution constant.

As a pretreatment for the electrolytic surface roughening treatment, Japanese Patent Laid-Open No.
It is preferable to perform a surface activation treatment by immersion in an aqueous solution of dimethylaminoborane described in 00-239852. In electrochemically roughening the aluminum alloy plate, if a copper component is segregated on the surface, it is difficult to electrochemically roughen only that portion, and the appearance is likely to be damaged. Therefore, when the aluminum surface is activated by immersion in an aqueous solution of dimethylaminoborane, a uniform surface suitable for a lithographic printing plate holder having no appearance failure can be obtained.

Dimethylaminoborane acts as a reducing agent for activating copper on the surface of the aluminum alloy plate, and its amount is preferably 1.0 to 10 g / liter. Each of the above-mentioned activator liquids may contain an aluminum salt, a surfactant and the like as other components. The preferable temperature of the activation treatment is 20 to 6
0 ° C. The processing time is 1 to 30 seconds in the dipping or spraying process.

<Mechanical surface roughening step, alkali etching step, desmutting step> Each of the mechanical surface roughening step, alkali etching step, and desmutting step is performed by electrolytic surface roughening. It is preferably provided in a stage (second processing step) before (the first processing step) and / or after the surface roughening processing step and before the anodic oxidation processing step described later. Further, an acid etching process step may be appropriately provided. However, each of these processing steps is an example, and the present invention is not limited to the contents of the following steps. The following processes including the above-described process are optionally performed.

(Mechanical surface roughening process) The mechanical surface roughening process in the mechanical surface roughening process is a process of mechanically roughening the surface of the aluminum alloy plate using a brush or the like. , Is preferably performed in the first processing step. As the mechanical surface roughening treatment, the bristle diameter is 0.07 to 0.3.
It is preferable to perform treatment with a 57 mm rotating nylon brush roll and an abrasive slurry liquid supplied to the surface of the aluminum alloy plate. Known abrasives can be used as the abrasive used in the mechanical roughening process,
JP-A-6-135175, JP-B-50-4004
It is preferable to use silica sand, quartz, aluminum hydroxide, or a mixture thereof described in JP-A-7.

The slurry has a specific gravity of 1.05.
Those in the range of ~ 1.3 are preferred. As a method for supplying the slurry liquid to the surface of the aluminum alloy plate,
A method of spraying the slurry liquid, a method of using a wire brush, and a method of transferring the surface shape of a roll provided with irregularities to an aluminum alloy plate are exemplified. Also, JP-A-55-074898 and JP-A-61-1
The method described in, for example, JP-A-62351 and JP-A-63-104889 may be used. further,
As described in JP-A-9-509108, a mixture of particles composed of alumina and quartz is mixed with 95:
A method of brush-polishing the surface of an aluminum alloy plate in an aqueous slurry containing a mass ratio of 5 to 5:95 can also be used. At this time, the volume average particle diameter of the mixture is preferably in the range of 1 to 40 μm, particularly 1 to 20 μm.

The nylon brush preferably has a low water absorption. For example, nylon bristle 200T (6,10-nylon, softening point: 180 ° C., manufactured by Toray Industries, Inc.)
Melting point: 212-214 ° C, specific gravity: 1.08-1.09,
Moisture percentage: 1.4 to 1. 1 at 20 ° C and 65% relative humidity.
8, 2.2 ° C at 20 ° C and 100% relative humidity.
8. Dry tensile strength: 4.5-6 g / d, dry tensile elongation: 20-35%, boiling water shrinkage: 1-4%, dry tensile resistance: 39-45 g / d, Young's modulus (dry) : 380
440 kg / mm ² ).

(Alkali Etching Treatment) The alkaline etching treatment in the alkaline etching treatment step is as follows.
A treatment for chemically etching the surface of an aluminum alloy plate in an alkaline aqueous solution, and is preferably performed in each of the first treatment step and the second treatment step. The concentration of the alkaline aqueous solution is preferably 1 to 30% by mass,
The alkaline aqueous solution may contain not only aluminum but also 0.5 to 10% by mass of an alloy component contained in the aluminum alloy plate. As the alkaline aqueous solution,
Particularly, an aqueous solution mainly containing sodium hydroxide (caustic soda) is preferable.

The alkali etching treatment performed before the electrochemical graining treatment or after the mechanical graining treatment is preferably carried out for 1 to 120 seconds at a liquid temperature of an alkaline aqueous solution of from room temperature to 95 ° C. Dissolution of the aluminum alloy plate (etching amount) is preferably set to 1 to 15 g / m ^2, and more preferably set to 3 to 10 g / m ^2.
When mixing a chemical etching liquid in an alkaline aqueous solution for the first time, it is preferable to prepare a treatment liquid using liquid sodium hydroxide (caustic soda) and sodium aluminate (sodium aluminate). After the completion of the alkali etching treatment, it is preferable to perform draining with a nip roller and washing with water by spraying so as not to carry out the treatment liquid to the next step.

(Acid Etching Step) The acidic etching step in the acid etching step refers to a step of chemically etching an aluminum alloy plate in an acidic solution, and is preferably performed in the second processing step. It is also preferable to apply after the alkali etching treatment. When the above-described acidic etching treatment is performed after the above-described alkali etching treatment is performed on the aluminum alloy plate, an intermetallic compound containing silica or simple Si can be removed from the surface of the aluminum alloy plate, and a subsequent anodic oxidation step The defect of the anodic oxide film generated in the above can be eliminated.

As the acid which can be used in the above-mentioned acidic etching treatment, phosphoric acid, nitric acid, sulfuric acid, chromic acid, hydrochloric acid, or a mixed acid containing two or more of these acids can be used, and an aqueous sulfuric acid solution is particularly preferable. The concentration of the acidic solution is 30
The acid solution is preferably 0 to 500 g / liter, and the acidic solution may contain not only aluminum but also alloy components contained in the aluminum alloy plate.

In the above-mentioned acidic etching treatment, the solution temperature is set to 60 to
The treatment is preferably performed at 90 ° C., preferably 70 to 80 ° C., for 1 to 10 seconds. At this time, the dissolution amount of the aluminum alloy plate is preferably 0.001 to 0.2 g / m ² . Also, acid concentration, for example, sulfuric acid concentration, aluminum concentration,
Is preferably selected from a range that does not crystallize at room temperature.
The preferred aluminum ion concentration is 0.1 to 15 g / liter, particularly preferably 5 to 15 g / liter. After the completion of the acidic etching treatment, it is preferable to perform draining with a nip roller and washing with water to prevent the treatment liquid from being taken to the next step.

(Desmut treatment process) When the chemical etching treatment is performed using an alkaline aqueous solution,
Generally, a smut is formed on the surface of an aluminum alloy plate, so-called desmut treatment (desmut treatment) in which the smut is dissolved in an acidic solution containing phosphoric acid, nitric acid, sulfuric acid, chromic acid, hydrochloric acid, or a mixed acid comprising two or more of these acids. Treatment step). The desmut treatment is preferably performed as appropriate in the first and second treatment steps, and is more preferably performed after the alkali etching treatment or the like. The concentration of the acidic solution (sulfuric acid concentration when sulfuric acid is used) is preferably from 250 to 500 g / liter. Further, aluminum is added to the acidic solution in an amount of 1-1.
Preferably, it contains 5 g / l. Further, 0.001 to 15 g / liter of an alloy component (excluding aluminum) contained in the aluminum alloy plate may be dissolved.

In the desmutting treatment, the temperature of the acidic solution is preferably from 60 to 90 ° C., more preferably from 60 to 70 ° C. Further, the processing time is preferably 1 to 180 seconds,
1 to 120 seconds are more preferable, and 2 to 60 seconds are still more preferable. After the end of the desmutting treatment, it is preferable to perform draining with a nip roller and washing with water by spraying so as not to carry the treatment liquid to the next step. Also,
As the desmut treatment liquid (acid solution), it is preferable to use the waste liquid of the acidic solution used in the surface roughening treatment step from the viewpoint of reducing the amount of the waste liquid.

As a first treatment step performed before the above-mentioned roughening treatment step in the present invention, the mechanical graining treatment on the aluminum alloy sheet and / or the dissolution amount of the aluminum alloy sheet is 1 to 10%. 15 g / m ² (more preferably, 3 to 10 g / m ²⁾ was subjected to alkali etching treatment so that is preferably subjected to a desmutting treatment in the acidic solution. Also, after the above-mentioned roughening treatment step,
As a second processing step performed before the anodic oxidation processing step described later, for example, 60-90
1 to 10 seconds in an aqueous sulfuric acid solution at 10 ° C. or an alkali etching process in which an aluminum alloy plate is dissolved in an aqueous alkaline solution by 0.01 to 5 g / m ² , and then in the above acidic solution. Or an acidic etching treatment in an aqueous sulfuric acid solution at 60 to 90 ° C. for 1 to 10 seconds. When the aluminum alloy plate is subjected to alkali etching,
Intermetallic compounds containing silica on the surface of the aluminum alloy plate,
Alternatively, in order to remove the elemental Si, it is preferable to perform the acidic etching treatment under the conditions of a liquid temperature of 60 to 90 ° C. and 1 to 10 seconds. As described above, the acidic etching treatment can eliminate defects in the anodized film generated in the subsequent anodizing treatment step, and as a result, a dot-like ink is formed on a non-image portion called a dust stain during printing. Can be improved.

After the aluminum alloy plate is treated in an aqueous acid or alkali solution or mechanically roughened using an abrasive, a cleaning step is provided for the purpose of removing the chemical solution or the abrasive from the surface of the aluminum alloy plate. Is preferred. The washing process in the washing step includes a washing process using water, a washing process using dry ice, and the like.

Washing is generally provided between treatment tanks having different types and compositions of chemicals, but the time required to enter the cleaning step from one treatment tank or the time required from cleaning to the next treatment tank is 10 seconds. The following is preferable, and 0.1 to 10 seconds is more preferable. If the time exceeds 10 seconds, chemical modification of the surface proceeds, and processing unevenness may easily occur.

The interval between the processing tanks with the cleaning step interposed between them is 15 seconds or less as the passage time of the aluminum web.
Particularly, it is preferably 5 seconds or less. If the time exceeds 15 seconds, chemical modification of the surface proceeds, making it difficult to perform a uniform roughening treatment in the next step.

In cleaning the aluminum alloy plate, the following method is preferably used, and a cleaning method using dry ice powder is particularly preferable for the purpose of reducing the amount of drainage.

(1) Washing treatment with water: As a method for washing an aluminum alloy plate for a lithographic printing plate, a method of washing the surface drained by a nip roller using water sprayed from a spray tip is used. General. Water flows 45-45 downstream in the direction of travel of the aluminum alloy plate.
It is preferable to inject at an angle of 90 degrees. The injection pressure of water is the pressure immediately before the injection nozzle and is usually 0.5 to 5 kg / c.
m ² and the liquid temperature are preferably from 10 to 80 ° C. The traveling speed of the traveling aluminum alloy plate is preferably 20 to 200 m / min. The amount of water sprayed on the aluminum alloy plate is 0.1 to 10 liter / in one washing step.
m ² is preferable. In one washing tank, washing water is sprayed from at least two spray tubes on the front surface and at least two spray tubes on the back surface of the aluminum alloy plate. One spray tube is provided with 5 to 30 spray tips at a pitch of 50 to 200 mm. The spray angle of the spray tip is preferably 10 to 150 °, and the distance between the aluminum alloy plate and the spray tip spraying surface is preferably 10 to 250 mm. The cross-sectional shape (spray pattern) of the spray of the spray tip includes an annular shape, a circular shape, an elliptical shape, a square shape, a rectangular shape and the like. The flow rate distribution (spray water distribution on the surface of the aluminum alloy plate) has an annular distribution, a uniform distribution, and a mountain-shaped distribution. A mountain distribution that facilitates distribution is preferred. The flow distribution changes depending on the spray pressure and the distance between the spray tip and the aluminum alloy plate. The particle size of the spray varies depending on the structure of the spray tip, the spray pressure, and the spray amount, but is preferably from 10 to 10,000 μm,
1000 μm is more preferred. The material of the spray nozzle preferably has abrasion resistance to a liquid flowing at a high speed. The material is preferably brass, stainless steel, ceramic or the like, and ceramic is particularly preferable.

The spray nozzle provided with the spray tip is 45 to 90 ° with respect to the traveling direction of the aluminum alloy plate.
However, it is preferable that the longer center line of the centers of the spray patterns be perpendicular to the direction of travel of the aluminum alloy plate. The washing time passing through the water washing step is industrially preferably 10 seconds or less, more preferably 0.5 to 5 seconds.

(2) Cleaning process using dry ice powder: A method of spraying dry ice powder on both surfaces of an aluminum alloy plate for cleaning is disclosed in Japanese Patent Application Laid-Open No. H10-6690.
A well-known shot blasting device as described in JP-A No. 5 can be used. Injection nozzle
A plurality of known injection nozzles as described in JP-A-28901 and JP-A-10-28902 can be arranged on both sides of an aluminum alloy plate. The spray nozzles may be arranged horizontally in a straight line, but are preferably installed obliquely so that the spray patterns on the surface of the aluminum alloy plate overlap in the width direction of the aluminum alloy plate. The distance between the injection nozzle and the aluminum alloy plate is preferably from 1 to 100 mm, particularly preferably from 10 to 50 mm.

As a method for producing powdery dry ice, a production apparatus as described in Japanese Utility Model Application Laid-Open No. 7-38104 can be used. As the gas for injection, N ₂ gas or air can be used. The volume average particle diameter of the powdery dry ice is preferably from 1 to 1000 μm, more preferably from 10 to 100 μm. CO ₂ supply per injection nozzle (solid weight) is 0.1 ~ 1
kg / min is preferable and the supply pressure is 1 to 20MPa.
a is preferred. Cleaning pressure on aluminum alloy plate is 1 ~
20 MPa is preferred.

<Anodic Oxidation Step> In the method for producing a support of the present invention, the surface roughening step or the second
After the treatment step, anodizing treatment is preferably performed to increase the wear resistance of the surface of the aluminum alloy plate (anodizing treatment step). The anodic oxidation treatment in the present invention refers to a process in which an aluminum alloy plate is immersed in an electrolytic solution as an anode, and an anodic oxide film is formed on the surface of the aluminum alloy plate by passing an electric current. The aluminum alloy plate that has undergone the anodic acid treatment step may be appropriately subjected to a hydrophilic treatment in the hydrophilic treatment step or a sealing treatment in the sealing treatment step.

As the electrolytic solution used for the anodic oxidation treatment of the aluminum alloy plate, any electrolytic solution capable of forming a porous oxide film can be used. Generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixture thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte. Since the conditions of the anodizing treatment vary depending on the electrolytic solution to be used, they cannot be specified unconditionally. 1 to 60 A / dm ² ,
It is appropriate that the voltage is in the range of 1 to 100 V and the electrolysis time is in the range of 10 to 300 seconds.

The sulfuric acid method using an aqueous solution of sulfuric acid as the electrolytic solution is a common method.
This is performed using normal DC current, but AC current may be used.
No. The amount of the anodic oxide film formed is 1 to 10 g.
/ M ^TwoEspecially 1.1 to 5 g / m^TwoIs preferable. the above
The amount formed is 1 g / m^TwoIf less than this, the printing durability becomes insufficient
The lithographic printing plate is easily scratched on the non-image area,
So-called scratch stains, where ink adheres to scratched parts
It will be easier. In addition, the formation amount of the anodic oxide film is 10 g / m
^TwoOver, the anodic oxide coating on the aluminum edge
Is easier to concentrate. Edge part of aluminum alloy plate
The difference in the amount of anodic oxide coating between the center and the central part is 1 g / m^TwoLess than
It is preferred that

In the above anodic oxidation treatment, it is preferable to use a sulfuric acid aqueous solution as an electrolytic solution.
No. 453 and JP-A-48-45303. The sulfuric acid aqueous solution preferably has a sulfuric acid concentration within a range of 10 to 300 g / l and an aluminum ion concentration within a range of 1 to 25 g / l.
Aluminum sulfate is added to an aqueous solution of sulfuric acid of 0 to 200 g / liter to adjust the aluminum ion concentration to 2 to 10 g / liter.
More preferably, it is liter. Liquid temperature is 30-60 ° C
Is preferred. When a direct current method using a direct current is used, the current density is preferably 1 to 60 A / dm ² ,
0 A / dm ² is more preferred.

When anodizing treatment is continuously performed on an aluminum alloy plate (aluminum sheet), the anode is initially treated at a low current density of 5 to 10 A / dm ^{2 in} order to prevent current concentration called burning of the aluminum alloy plate. Oxidation treatment, gradually increase the current density in the second half
It is preferable to set the current density until the current density reaches 50 A / dm ² or more. At this time, it is preferable that the current density is gradually increased in 5 to 15 steps. It is preferable that an independent power supply is provided for each step, and the current density is controlled by the current value of the power supply. As a power supply method, a liquid power supply method using no conductor roller is preferable. In general, iridium oxide or lead can be used for the anode, and aluminum is used for the cathode. An example of an apparatus used for the anodizing treatment is described in Japanese Patent Application No. 11-178624.

A trace component element contained in the aluminum alloy plate may be dissolved in the sulfuric acid aqueous solution. Also,
Since aluminum is eluted in the sulfuric acid aqueous solution during the anodizing treatment, it is necessary to control the sulfuric acid concentration and the aluminum ion concentration in order to control the process. If the aluminum ion concentration is set low, the aqueous sulfuric acid solution for anodic oxidation must be renewed frequently, and the amount of waste liquid increases, which is not economical and has environmental problems. On the other hand, when the aluminum ion concentration is set to be high, the electrolysis voltage is increased, the electric power cost is increased, and it is not economical. Preferred combinations of the sulfuric acid concentration, aluminum ion concentration, and liquid temperature for the anodic oxidation include (i) a sulfuric acid concentration of 100 to 20.
0 g / liter, more preferably 130-180 g /
Liter, aluminum ion concentration of 2 to 10 g / liter, more preferably 3 to 7 g / liter, and liquid temperature of 30
-40 ° C, more preferably 33-38 ° C, (ii) sulfuric acid concentration of 50-125 g / liter, more preferably 80
~ 120 g / l, aluminum ion concentration is 2 ~
10 g / liter, more preferably 3 to 7 g / liter, liquid temperature of 40 to 70 ° C, more preferably 50 to 60 ° C
It is.

There are two types of power supply to the aluminum alloy plate in the anodic oxidation treatment: a direct power supply system in which power is directly supplied to the aluminum alloy plate using a conductor roll, and a liquid power supply system in which power is supplied to the aluminum alloy plate through an electrolytic solution. The direct power supply method is often used in an anodizing apparatus having a relatively low speed and low current density of 30 m / min or less in line speed, and the indirect power supply method is often used in an anodizing apparatus having a high speed and high current density exceeding 30 m / min in line speed. .

As for the indirect power supply method, a Yamagoshi type or straight type tank layout can be used as shown on page 289 of the continuous surface treatment technology (General Technology Center, published on September 30, 1986). At high speeds and high current densities, there is a problem of spark generation between the conductor roll and the aluminum web, so the direct feed roll method is disadvantageous. To prevent sparking of the conductor roll and heat generation of the aluminum alloy plate, a spray of the same composition and the same temperature as the electrolyte used for the anodic oxidation treatment is applied to the part where the conductor roll and the aluminum alloy plate pass through the air by spraying. Preferably, it is sprayed. The conductor roll may be on the upper surface or the lower surface of the aluminum alloy plate.

When the anodizing tank is separated into two or more tanks and the direct power supply system for each electrolytic tank is used, the conductor roll is generally made of aluminum. In order to extend the life of the roll,
138 as described in, after casting with industrial pure aluminum, the use of which the Al-Fe-based crystallized products subjected to high temperature homogenization treatment improved the corrosion resistance as a single layer of Al ₃ Fe Particularly preferred.

In the anodic oxidation step, a large current flows, and a Lorentz force acts on the aluminum alloy plate by a magnetic field generated by the current flowing through the bus bar. As a result, a problem of meandering of the web occurs.
It is particularly preferable to use a method as described in 1290.

Since a large current flows through the aluminum alloy plate, a Lorentz force acts toward the center in the width direction of the aluminum alloy plate due to a magnetic field caused by the current flowing through the aluminum alloy plate itself. As a result, the aluminum alloy plate is liable to be broken. Therefore, a pass roller having a diameter of 100 to 200 mm is placed in the anodizing tank.
It is particularly preferable to adopt a method in which a plurality of fins are provided at a pitch of 3000 mm and wrapped at an angle of 1 to 15 ° to prevent breakage due to Lorentz force.

Further, the formation amount of the anodic oxide film differs in the width direction of the aluminum alloy plate. As a result, there arises a problem that the aluminum alloy plate cannot be successfully wound by the winding device.
This can be solved by stirring the liquid stream by the method described in JP-B-62-30275 or JP-B-55-21840. If that method is not sufficient, a method of winding the aluminum alloy sheet by oscillating in the width direction of the aluminum alloy sheet with an amplitude of 5 to 50 mm at a cycle of 0.1 to 10 Hz is used in combination. Is particularly preferred.

On the aluminum support for a lithographic printing plate, only one surface is subjected to a roughening treatment to form an undercoat layer.
There is a product coated with a mat layer (lithographic printing plate precursor), and a product coated with a primer layer, a photosensitive layer and a mat layer on both sides successively after roughening the both surfaces (lithographic printing plate precursor).

At this time, in order to use the anodizing tank effectively
Case where anodizing treatment is performed on only one side and both sides are performed simultaneously
Case occurs. In this case, in the anodizing tank
Use a U-shape for the electrode facing the aluminum alloy plate
So that the aluminum web passes through
preferable. At this time, the web with only one side as a product flows
The anodic oxide coating on the non-product side to prevent scratches.
0.1-1 g / m ^TwoIt only needs to be formed,
No upper anodic oxide coating is required. Effective use of energy
As a method to solve this problem,
No. 8233, when performing electrolysis on only one surface,
Place an electrical insulating material between the metal plate and the other side electrode,
When electrolytically treating both surfaces of the strip-shaped metal plate, the electric insulating material is used.
The material is moved from the previous location to
It is particularly preferred that the current flow to the side.

Further, in an anodizing treatment tank using a direct current in which only one side is a product, the opposing cathode is arranged on the upper surface of an aluminum web (aluminum alloy plate).
Aluminum web and 5 below the aluminum web
It is particularly preferable to arrange PVC insulating plates at intervals of up to 20 mm.

As described in JP-B-56-12518, an anodized aluminum alloy plate is formed by forming an anodized film and then etching the oxide film.
Steam or hot water, or an organic solvent, an amine compound,
A more excellent aluminum support for a lithographic printing plate can be obtained by treating with a hot aqueous solution containing at least one compound selected from organic acids, oxyacid salts of phosphoric acid, and boric acid. Of course, the etching treatment after the anodic oxidation treatment is not essential.

It is preferable that chemicals used for electrolytic surface roughening treatment, mechanical roughening treatment, desmutting treatment, chemical etching treatment (alkali etching treatment), anodic oxidation treatment, hydrophilic treatment, etc. are recycled as much as possible. . In an aqueous caustic soda solution in which aluminum ions are dissolved, aluminum and caustic soda can be separated by crystallization.
With an aqueous sulfuric acid solution, nitric acid solution or aqueous hydrochloric acid solution in which aluminum ions are dissolved, electrodialysis or recovery of sulfuric acid or nitric acid using an ion exchange resin can be performed.

The hydrochloric acid aqueous solution in which aluminum ions are dissolved can be recovered by evaporation as described in JP-A-2000-282272.

It is preferable that the surface characteristic value of the aluminum alloy sheet roughened in the present invention be within the following range, as measured by a contact type surface roughness meter. As a factor, the average surface roughness (Ra): the height of the peak from the straight line parallel to the average line and not crossing the cross-sectional curve to the maximum of the fifth in the longitudinal magnification direction in the portion extracted by the reference length from the cross-sectional curve 10-point average roughness (Rz), which is the sum of the average value of and the average value of the depths of the valleys from the deepest to the fifth, expressed in μm units; The maximum height (Rma) in which the peak and the deepest valley are sandwiched by two straight lines parallel to the parallel line, and the interval is measured in μm units
x): average depth (Rp) representing the distance between the maximum peak and the average line between the measured lengths of the cross-sectional curve; average of the portion obtained by taking a filtered undulation curve with a roughness meter and cutting out by the length of the measured length Across the line, the average value of the interval between the point going from the peak to the valley and the crossing point going from the next peak to the valley is the average value of the undulation average peak interval (Sm);
There is 2). A preferable range of these is that Ra is 0.3 to
0.6 μm, Rz 2-5 μm, Rmax 2-5 μm
m, Rp is 0.5 to 1.5 μm, Sm is 20 to 70 μm
It is. The non-porosity (%) according to the Abbot curve at a cutting depth Cv three times Ra is preferably 15 to 35. Further, Japanese Patent Application Laid-Open No. 62-15035
No. 3, the area per bearing (tpmi) at a cutting depth three times Ra is 10 to 50%.
Is preferred. Further, the whiteness measured by a Macbeth densitometer is preferably in the range of 0.15 to 0.45 after the anodizing treatment.

[0093] Well-known steel or the like whose surface is plated or lined, metal rolls, resin rolls used in continuous production lines of plating, electrolytic capacitors, lithographic printing plates, etc.
It can be used by selecting from a rubber roll and a nonwoven fabric roll.

The material of the rolls (pass rolls and the like) used in the apparatus for carrying out the method for producing a lithographic printing plate support of the present invention and the physical properties of the surfaces are determined by the corrosion resistance and the resistance to the chemicals and the state of the aluminum surface at that time. Select in consideration of wear resistance, heat resistance, chemical resistance, etc. Hard chrome plating rolls are generally used as metal rolls. Rubber rolls include natural rubber, isoprene rubber, styrene butadiene rubber, butadiene rubber, butyl rubber, chloroprene rubber, chlorosulfonated polyethylene, nitrile rubber, acrylic rubber,
Epichlorohydrin rubber, urethane rubber, polysulfide rubber,
As a matter of course, fluororubbers and the like to which a small amount of additives are added can be used. Rubber roll hardness is 60
~ 90 is preferred.

In the roughening process of the lithographic printing plate support, the coating process of the photosensitive layer described later, and the manufacturing process such as the drying process, a material containing silicon is used as an apparatus.
It is particularly preferable not to use it as a lubricating oil or to use it in work articles including clothes and measuring instruments. If these components adhere to the surface of the aluminum alloy plate, spots having a diameter of 0.1 to 5 mm that are not applied are generated in the application step, and the yield is extremely reduced. It is particularly preferable that cosmetics, hairdressings and printed materials do not use silicon.

(Hydrophilic treatment step) The aluminum alloy plate is preferably subjected to anodizing treatment in the anodizing treatment step, and then, if necessary, to the surface of the aluminum alloy plate in the hydrophilizing treatment step. . As the hydrophilic treatment, the alkali metal silicate (for example, sodium silicate aqueous solution) method disclosed in US Pat. Nos. 2,714,066, 3,181,461, 3,280,734 and 3,902,734 is used. It is preferably used. In this method, the support is immersed in an aqueous solution of sodium silicate or subjected to electrolytic treatment in the aqueous solution. Other preferable methods include potassium fluoride zirconate disclosed in JP-B-36-22063 and U.S. Pat. Nos. 3,276,868, 4,153,461 and 468.
For example, a method of treating with polyvinyl phosphonic acid disclosed in No. 9272 is used. Among these, it is preferable to perform the hydrophilization treatment using an aqueous solution of sodium silicate and polyvinyl phosphonic acid.

(Sealing Treatment Step) In the present invention, after the anodic oxidation treatment is performed in the anodic oxidation treatment step, the sealing treatment is performed to close a hole called a micropore formed in the anodic oxide film. preferable. Such a sealing treatment is performed by immersion in hot water and a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath or the like. Further, it is preferable to perform the above-mentioned hydrophilic treatment after the sealing treatment step. Examples of the inorganic salts include silicates, borates, phosphates, and nitrates, and examples of the organic salts include carboxylate.

<Production Apparatus That Can Be Used in the Production Method of the Present Invention>
Hereinafter, a manufacturing apparatus that can be used in the method for manufacturing an aluminum support for a lithographic printing plate of the present invention will be described. As the production process of the support of the present invention, (1) the rolled and coiled aluminum alloy plate is sent out from a feeder composed of a multi-axial turret, and (2) the above-mentioned processes (mechanical roughening) Treatment, alkali etching treatment, acid etching treatment, desmut treatment, electrochemical surface roughening treatment,
After the anodizing treatment, the sealing treatment, and the hydrophilic treatment), the aluminum alloy plate is dried, and (3) the aluminum alloy plate is wound into a coil by a winding device including the multiaxial turret, or Preferably, the flatness of the aluminum alloy plate is corrected, and thereafter, the aluminum alloy plate is cut into a predetermined length and integrated. Also, if necessary, a step of forming (undercoat layer, photosensitive layer, mat layer) in the above process and performing a drying treatment is provided, and the lithographic printing plate precursor is wound into a coil by the winding device. Is also good.

Further, in the manufacturing method of the present invention, the defect is continuously inspected by using an apparatus for inspecting a defect on the surface of the aluminum alloy plate, and a label of a mark is attached to an edge portion of the found defect. Is preferably provided in one or more steps. Furthermore, in the production method of the present invention, in the feeding step of the aluminum alloy plate, and the winding step,
When replacing the aluminum coil, it is preferable to provide a reservoir device that keeps the traveling speed of the aluminum alloy plate constant in each of the above steps even if the traveling of the aluminum alloy plate is stopped. After the step (b), it is preferable to provide a step of joining the aluminum alloy plate by ultrasonic or arc welding.

The manufacturing apparatus used in the manufacturing method of the present invention includes:
It is preferable to have one or more devices for detecting the traveling position of the aluminum alloy plate and correcting the traveling position. Further, it is preferable that the manufacturing apparatus has one or more driving devices for controlling the tension of the aluminum alloy plate and controlling the traveling speed, and one or more dancer roll devices for controlling the tension. Also, the tracking device records whether or not the state of each process is a desired condition, and before the aluminum coil is wound, a label is attached to the edge of the aluminum web, and the condition after the label is the desired condition. It is also preferable that the determination can be made later.

It is preferable that the aluminum alloy plates are charged together with the interleaving paper and adsorbed to each other, and then cut and / or slit to a predetermined length. Also, based on the information on the label affixed to the edge portion of the aluminum alloy plate, after cutting to a predetermined length or before cutting, to separate the non-defective part and the defective part using the label as a mark, It is preferable to accumulate only non-defective parts.

In each step including the above-mentioned feeding step and the like, the size (thickness and width) of the aluminum alloy plate, the aluminum material, or the traveling speed of the aluminum web depends on
It is important to set the optimal tension under each condition. Therefore, it is preferable to provide a plurality of tension control devices that feedback-control a signal from a tension sensing device by using a driving device for the purpose of tension reduction and traveling speed control and a dancer roll for the purpose of tension control. The driving device generally uses a control method combining a DC motor and a main driving roller. The main drive roller is made of a general rubber material, but in the step where the aluminum web is in a wet state, a roller made by laminating a nonwoven fabric can be used. In general, rubber or metal is used for each pass roller, but in places where slippage easily occurs with the aluminum web, in order to prevent this slip, a motor or reduction gear is connected to each pass roller, and the signal from the main drive unit is used. It is also possible to provide an auxiliary driving device such as controlling the rotation at a constant speed.

The support for a lithographic printing plate is described in JP-A-10-11 / 1999.
As described in Japanese Patent No. 4046, average surface roughness (R ¹ ) in the rolling direction as arithmetic average surface roughness (Ra)
(R ¹ −R ² ) between the average surface roughness (R ² ) in the direction perpendicular to the rolling direction is the average surface roughness (R ¹ ) in the rolling direction.
, And the average curvature in the rolling direction is 1.5 ×
It is within 10 ⁻³ mm ⁻¹ and the curvature distribution in the width direction is 1.
It is preferable that the curvature in the direction perpendicular to the rolling direction is 5 × 10 ⁻³ mm ^{−1 or} less and 1.0 × 10 ⁻³ mm ^{−1 or} less. The lithographic printing plate support manufactured by performing the above-mentioned surface roughening treatment has a roll diameter of 20 mm to 80 mm and a rubber hardness of 5 mm.
It is preferable to perform correction using a correction roll of 0 to 95 degrees. Thereby, even in the automatic transporting step of the lithographic printing press, it is possible to supply an aluminum coil-shaped plate having a flatness which does not cause exposure deviation of the lithographic printing plate precursor. JP-A-9-194093 describes a web curl measuring method and apparatus, a curl correcting method and apparatus, and a web cutting apparatus.

In the continuous production of a lithographic printing plate support, it is electrically monitored whether each process is operating under appropriate conditions, and a tracking device is used to check whether the state of each process is the desired condition. Before and after the aluminum coil is wound, a label is attached to the edge of the aluminum web, and it is possible to determine whether the condition after the label is the desired condition. At the time, the quality of the part can be determined at the time of integration.

In the apparatus for treating an aluminum alloy plate used in the above-described surface roughening treatment step, at least one of the temperature, specific gravity, electric conductivity, and ultrasonic wave propagation velocity of the liquid is measured to determine the composition of the liquid. It is preferable that the liquid concentration is controlled to be constant by feedback control and / or feedforward control. In the acidic solution in the processing apparatus, components contained in the aluminum alloy plate including aluminum ions are dissolved as the surface treatment of the aluminum alloy plate proceeds. Therefore, in order to keep the aluminum ion concentration and the acid or alkali concentration constant, it is preferable to keep the liquid composition constant by intermittently adding water and acid or water and alkali. The concentration of the acid or alkali added here is preferably from 10 to 98% by mass.

In order to control the concentration of the acid or alkali, for example, the following method is preferable. First, the conductivity, specific gravity, or ultrasonic wave propagation speed of each component liquid in the concentration range that is to be used in advance is measured for each temperature to create a data table. Then, the concentration is measured by referring to the data table of the non-measurement liquid in which the conductivity, the specific gravity or the propagation speed of the ultrasonic wave and the temperature data of the liquid to be measured are prepared in advance. A method for measuring the propagation time of ultrasonic waves with high accuracy and high stability is disclosed in
-235721. A concentration measuring system utilizing the propagation speed of the ultrasonic wave is disclosed in Japanese Patent Application Laid-Open No. 58-77665. Further, a method of preparing a data table showing a correlation between a plurality of physical quantity data for each liquid component and measuring the concentration of the multi-component liquid with reference to the data table is disclosed in Japanese Patent Laid-Open No. 1955/1992.
No. 9 discloses this.

When the above-described concentration measurement method using the ultrasonic wave propagation velocity is applied to the surface roughening step of the lithographic printing plate support by combining the conductivity and temperature values of the liquid to be measured, the process management is performed in real time. In this case, it is possible to manufacture products of a certain quality, which leads to an improvement in the yield. In addition to the combination of temperature and ultrasonic wave propagation speed and conductivity, data tables are created for each concentration and temperature with physical quantities such as temperature and specific gravity, temperature and conductivity, temperature and conductivity and specific gravity, etc. If the method of measuring the concentration of the multi-component liquid with reference to the data table is applied to the step of roughening the surface of the lithographic printing plate support, the same effect as described above can be obtained. Further, the specific gravity and the temperature are measured, and the slurry concentration of the object to be measured is determined with reference to a data table created in advance, so that the slurry concentration can be measured quickly and accurately.

Since the above ultrasonic wave propagation velocity measurement is easily affected by bubbles in the liquid, it is more preferable to measure the ultrasonic velocity in a pipe that is vertically arranged and has a flow velocity that goes upward from below. The above ultrasonic wave propagation velocity measurement is preferably performed within a pressure range of 1 to 10 kg / cm ² in the pipe, and the frequency of the ultrasonic wave is preferably 0.5 to 3 MHz.
In addition, since the measurement of the specific gravity, the conductivity, and the propagation speed of the ultrasonic wave are easily affected by the temperature, the measurement can be performed in a pipe in a heat-retaining state and in which the temperature fluctuation is controlled within ± 0.3 ° C. preferable. Furthermore, since the conductivity and specific gravity, or the conductivity and the ultrasonic wave propagation velocity are preferably measured at the same temperature, it is particularly preferable to measure the same in the same pipe or in the same pipe flow. Since the pressure fluctuation at the time of measurement leads to a temperature fluctuation, it is preferable to be as low as possible.
It is preferable that the flow velocity distribution in the pipe to be measured is as small as possible. Further, since the above measurement is easily affected by slurry, dust, and bubbles, it is preferable to measure the liquid that has passed through a filter, a deaerator, or the like.

<< Lithographic Printing Plate Support >><UndercoatLayer> The lithographic printing plate support produced by the production method of the present invention is provided with a photosensitive layer on the surface thereof to form a lithographic printing plate precursor. Before the coating, an (organic) undercoat layer may be provided as necessary.

Examples of the organic compound used in the organic undercoat layer include phosphonic acids having an amino group such as carboxymethylcellulose, dextrin, gum arabic and 2-aminoethylphosphonic acid, and phenyl which may have a substituent. Phosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, organic phosphonic acids such as methylenediphosphonic acid and ethylenediphosphonic acid, and phenylphosphoric acid which may have a substituent, naphthylphosphoric acid,
Organic phosphoric acids such as alkylphosphoric acid and glycerophosphoric acid, and organic phosphinic acids such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid which may have a substituent, glycine and β
-Selected from amino acids such as alanine, and hydrochlorides of amines having a hydroxyl group such as triethanolamine hydrochloride, and two or more of these may be used in combination.

The organic undercoat layer can be provided, for example, by the following method. (A) a method in which a solution obtained by dissolving the above organic compound in water or an organic solvent such as methanol, ethanol, or methyl ethyl ketone, or a mixed solvent thereof is coated on the support of the present invention and dried, b) Water, or an organic solvent such as methanol, ethanol, methyl ethyl ketone, or a solution obtained by dissolving the above organic compound in a mixed solvent thereof, by immersing the support of the present invention to adsorb the organic compound, The organic undercoat layer can be provided by a method of washing and drying with water or the like to provide an organic undercoat layer.

In the above method (a), 0.005 to 10
% By weight of the organic compound solution can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used. In the method (b), the concentration of the organic solvent solution is 0.01 to 20% by mass, preferably 0.05 to 5% by mass.
The immersion temperature is 20 to 90 ° C., preferably 25 to 5 ° C.
0 ° C., and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute. The solution used for this is ammonia,
Basic substances such as triethylamine and potassium hydroxide,
Adjust the pH with acidic substances such as hydrochloric acid, phosphoric acid, etc.
It can be used in the range of 1 to 12. Further, a yellow dye may be added to improve the tone reproducibility of the photosensitive lithographic printing plate. The coating amount of the organic undercoat layer after drying is suitably from ² to 200 mg / m ² , and preferably from 5 to 100 mg / m ² . The coating amount is 2m
If it is less than g / m ² , sufficient printing durability may not be obtained. Further, the same may occur even when the amount exceeds 200 mg / m ² .

<Backcoat layer> When the lithographic printing plate precursor is stacked on the back surface (the side on which the photosensitive layer is not provided) of the lithographic printing plate precursor using the support obtained by the production method of the present invention. A coating layer made of an organic polymer compound (hereinafter, sometimes referred to as a “backcoat layer”) may be provided as necessary so that the photosensitive layer is not damaged. The main component of the back coat layer has a glass transition point of 20
It is preferable to use at least one resin selected from the group consisting of a saturated copolymerized polyester resin, a phenoxy resin, a polyvinyl acetal resin and a vinylidene chloride copolymerized resin at a temperature of not lower than ° C.

The saturated copolymerized polyester resin comprises a dicarboxylic acid unit and a diol unit. As the dicarboxylic acid unit of the polyester used in the present invention, phthalic acid, terephthalic acid, isophthalic acid, tetrabromophthalic acid, aromatic dicarboxylic acids such as tetrachlorophthalic acid; adipic acid, azelaic acid, succinic acid, oxalic acid;
Examples include saturated aliphatic dicarboxylic acids such as suberic acid, sebacic acid, malonic acid, and 1,4-cyclohexanedicarboxylic acid.

The back coat layer further includes a dye or pigment for coloring, a silane coupling agent, a diazo resin composed of a diazonium salt, an organic phosphonic acid, an organic phosphonic acid for improving the adhesion to the support of the present invention. Phosphoric acid, a cationic polymer, and the like, as well as a wax generally used as a slipping agent, a higher fatty acid, a higher fatty acid amide, a silicone compound composed of dimethylsiloxane, a modified dimethylsiloxane, a polyethylene powder, and the like may be appropriately added. The thickness of the back coat layer is basically even without interleaving paper,
It is sufficient that the photosensitive layer has a thickness that does not easily damage the photosensitive layer described below.
The range of 01 to 8 μm is preferred. The thickness is 0.01 μm
If it is less than 10, it is difficult to prevent the photosensitive layer from being scratched when handling the lithographic printing plates in an overlapping manner. In addition, the thickness is 8 μm.
m, during printing, the back coat layer swells due to the chemicals used around the lithographic printing plate precursor and the thickness fluctuates,
The printing pressure may change to deteriorate the printing characteristics.

Various methods can be applied as a method for coating the back coat layer on the back surface of the support of the present invention. For example, the above-mentioned components for the back coat layer are dissolved in an appropriate solvent and applied as a solution, or an emulsified dispersion is applied and dried. The method of bonding to the support of the present invention, a method of forming a molten coating with a melt extruder and bonding the support to the support of the present invention, and the like. This is a method in which the back coat component is dissolved in an appropriate solvent, made into a solution, applied, and dried. The solvent used herein is described in JP-A-62-152739.
Organic solvents such as those described in JP-A No. 195/1992 can be used alone or as a mixture. Further, in the production of the lithographic printing plate precursor, either the back coat layer on the back surface or the photosensitive composition layer on the front surface may be coated on the support first,
Alternatively, both may be applied simultaneously.

<< Lithographic Printing Plate Precursor >> A lithographic printing plate precursor according to the invention can be prepared by providing a photosensitive layer described below on the support of the invention. The lithographic printing plate precursor is subjected to exposure, development, and the like, and an image is formed on the lithographic printing plate precursor so as to be ready for printing.

<[I] When a photosensitive layer containing a novolak resin of a mixture of o-naphthoquinonediazidosulfonic acid ester and phenol / cresol is provided> The support of the present invention comprises o-naphthoquinonediazidosulfonic acid ester and phenol / cresol. A photosensitive layer containing a mixed novolak resin can be provided. The o-quinonediazide compound is an o-naphthoquinonediazide compound. For example, U.S. Pat. Nos. 2,766,118, 2,767,092, and 2,772.
No. 2,972, No. 2,859,112, No. 3,102,809, No. 3,10
No. 6,465, 3,635,709, 3,647,443, and many other publications, and these are preferably used. it can. Further, among these, o-naphthoquinonediazidosulfonic acid ester or o-naphthoquinonediazidocarboxylic acid ester of an aromatic hydroxy compound, and o-naphthoquinonediazidosulfonic acid amide or o-naphthoquinonediazidecarboxylic acid amide of an aromatic amino compound are particularly preferred. Preferred, especially US Pat.
No. 5,0709, U.S. Pat. No. 4,028,5,709, which is obtained by subjecting a condensate of pyrogallol and acetone to an ester reaction with o-naphthoquinonediazidosulfonic acid.
No. 111, which is obtained by subjecting a polyester having a terminal hydroxy group to an ester reaction with o-naphthoquinonediazidesulfonic acid or o-naphthoquinonediazidocarboxylic acid, and British Patent 1,494,043.
O-naphthoquinonediazide sulfonic acid, a homopolymer of p-hydroxystyrene or a copolymer thereof with another copolymerizable monomer as described in
Or, an ester reaction of o-naphthoquinonediazidocarboxylic acid or a copolymer of p-aminostyrene and another copolymerizable monomer as described in U.S. Pat. No. 3,759,711. Those obtained by subjecting o-naphthoquinonediazidesulfonic acid or o-naphthoquinonediazidocarboxylic acid to an amide reaction are very excellent.

The above-mentioned o-quinonediazide compound can be used alone, but is preferably used in combination with an alkali-soluble resin. Suitable alkali-soluble resins include novolak-type phenol resins, and specifically include phenol formaldehyde resin, o-cresol formaldehyde resin, m-cresol formaldehyde resin, and the like. No. 4,028,1.
As described in the specification of Patent No. 11, when a condensate of phenol or cresol substituted with an alkyl group having 3 to 8 carbon atoms, such as t-butylphenol formaldehyde resin, and a condensate of formaldehyde are used together with the phenol resin. More preferred. Further, in order to form a visible image by exposure, for example, o-naphthoquinonediazide-
A compound such as an inorganic anion salt of 4-sulfonyl chloride, p-diazodiphenylamine, a trihalomethyloxadiazole compound, or a trihalomethyloxadiazole compound having a benzofuran ring is added.

On the other hand, an image coloring agent may be used in the photosensitive layer. Victoria Blue-
A triphenylmethane dye such as BOH, crystal violet or oil blue is used. In addition, Japanese Unexamined Patent Publication
The dyes described in JP-A-2-293247 are particularly preferred. Further, as a sensitizer, Japanese Patent Publication No. 57-2325
No. 3 phenol substituted with an alkyl group having 3 to 15 carbon atoms, such as t-butylphenol, n-octylphenol, a novolak resin obtained by condensing t-butylphenol with formaldehyde as described in JP-A-3
Alternatively, an o-naphthoquinonediazide-4- or -5-sulfonic acid ester of such a novolak resin (for example, described in JP-A-61-242446) can be contained.

Further, in order to improve the developability, a nonionic surfactant as described in JP-A-62-251740 can be further contained. The composition described above can be dissolved in a solvent that dissolves the above components and applied on the support of the present invention. As the solvent used here, ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate,
Methyl lactate, ethyl lactate, dimethylsulfoxide, dimethylacetamide, dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol,
Acetone, diacetone alcohol, methanol, ethanol, isopropanol, diethylene glycol dimethyl ether and the like can be mentioned, and it is preferable to use these solvents alone or as a mixture.

<[II] When a photosensitive layer containing a diazo resin and a water-insoluble and lipophilic polymer compound is provided> The support of the present invention comprises a photosensitive layer containing a diazo resin and a water-insoluble and lipophilic polymer compound. Layers can also be provided. Examples of the diazo resin include, for example, a diazo resin inorganic salt which is an organic solvent-soluble reaction product of p-diazodiphenylamine and formaldehyde, or a condensate of acetaldehyde, hexafluorophosphate, and tetrafluoroborate. Also, as described in U.S. Pat. No. 3,300,309, the above condensate and a sulfonic acid such as P-toluenesulfonic acid or a salt thereof, a phosphinic acid such as benzenephosphinic acid or a salt thereof, a hydroxyl group Contained compounds, for example, organic solvent-soluble diazo resin organic acid salts, which are reaction products with 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid or a salt thereof, and the like.
In the present invention, other diazo resins that can be suitably used include a carboxyl group, a sulfonic acid group, a sulfinic acid group, an aromatic compound having at least one organic group among oxygen groups and hydroxyl groups of phosphorus, and diazonium. It is a co-condensate containing a compound, preferably an aromatic diazonium compound, as a structural unit. The aromatic ring preferably includes a phenyl group and a naphthyl group. As the above-mentioned aromatic compound having at least one of a carboxyl group, a sulfonic acid group, a sulfinic acid group, an oxygen acid group of phosphorus, and a hydroxyl group, various compounds can be mentioned, but preferred is 4-methoxybenzoic acid. Acid, 3-chlorobenzoic acid, 2,4-dimethoxybenzoic acid, p-phenoxybenzoic acid, 4-anilinobenzoic acid, phenoxyacetic acid, phenylacetic acid, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, benzenesulfone Acids, p-toluenesulfinic acid, 1-naphthalenesulfonic acid, phenylphosphoric acid, and phenylphosphonic acid.

The aromatic diazonium compound constituting the constitutional unit of the above-mentioned co-condensation diazo resin includes, for example, JP-B-49-4
Although diazonium salts such as those described in JP-A-8001 can be used, diphenylamine-4 is particularly preferred.
-Diazonium salts are preferred. Diphenylamine-4
-Diazonium salts are derived from 4-amino-diphenylamines, such 4-amine-diphenylamines being 4-aminodiphenylamine,
-Amino-3-methoxydiphenylamine, 4-amino-2-methoxydiphenylamine, 4'-amino-2-
Methoxydiphenylamine, 4′-amino-4-methoxydiphenylamine, 4-amino-3-methyldiphenylamine, 4-amino-3-ethoxydiphenylamine, 4-amino-3-β-hydroxyethoxydiphenylamine, 4-amino-diphenylamine-2 -Sulfonic acid, 4-amino-diphenylamine-2-carboxylic acid, 4-amino-diphenylamine-2′-carboxylic acid and the like, and particularly preferably, 3-methoxy-4-amino-4-diphenylamine, 4-amino Diphenylamine.

The diazo resin other than the cocondensation diazo resin with an aromatic compound having an acid group is disclosed in
The diazo resin condensed with an aldehyde having an acid group or an acetal compound thereof described in JP-A-8559, JP-A-3-163551 and JP-A-3-253857 can also be preferably used. The counter anion of the diazo resin includes an anion which forms a salt with the diazo resin stably and makes the resin soluble in an organic solvent.

These include organic carboxylic acids such as decanoic acid and benzoic acid, and organic phosphoric acids and sulfonic acids such as phenylphosphoric acid. Alkanesulfonic acid, laurylsulfonic acid, dioctylsulfosuccinic acid, dicyclohexylsulfosuccinic acid, camphorsulfonic acid, tolyloxy-3-propanesulfonic acid, nonylphenoxy-3-propanesulfonic acid, nonylphenoxy-4-butanesulfonic acid, dibutylphenoxy-3 -Propanesulfonic acid, diamylphenoxy-
3-propanesulfonic acid, dinonylphenoxy-3-propanesulfonic acid, dibutylphenoxy-4-butanesulfonic acid, dinonylphenoxy-4-butanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, p-chlorobenzene Sulfonic acid, 2,
5-dichlorobenzenesulfonic acid, sulfosalcylic acid,
2,5-dimethylbenzenesulfonic acid, p-acetylbenzenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-chloro-5 -Nitrobenzenesulfonic acid, butylbenzenesulfonic acid,

Octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, butoxybenzenesulfonic acid, dodecyloxybenzenesulfonic acid, 2-hydroxy-4-methoxybenzophenone-
5-sulfonic acid, isopropyl naphthalene sulfonic acid, butyl naphthalene sulfonic acid, hexyl naphthalene sulfonic acid, octyl naphthalene sulfonic acid, butoxy naphthalene sulfonic acid, dodecyl oxy naphthalene sulfonic acid, dibutyl naphthalene sulfonic acid, dioctyl naphthalene sulfonic acid, triisopropyl naphthalene Sulfonic acid, tributylnaphthalenesulfonic acid, 1-naphthol-5-sulfonic acid, naphthalene-1-sulfonic acid,
Aliphatic and aromatic sulfonic acids such as naphthalene-2-sulfonic acid, 1,8-dinitro-naphthalene-3,6-disulfonic acid and dimethyl-5-sulfoisophthalate;
2,2 ′, 4,4′-tetrahydroxybenzophenone,
1,2,3-trihydrooxybenzophenone, 2,
Hydroxy group-containing aromatic compounds such as 2′4-trihydroxybenzophenone; halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid; and perhalogen acids such as HClO ₄ and HIO _4. It is not something that can be done. Among these, particularly preferred are butylnaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, hexafluorophosphoric acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and dodecylbenzenesulfonic acid.

The molecular weight of the diazo resin used in the present invention can be obtained as an arbitrary value by variously changing the molar ratio of each monomer and the condensation conditions.
In order to effectively serve the intended use of the present invention, those having a molecular weight of about 400 to 100,000, preferably about 8
Those having a size of from 00 to 8,000 are suitable. Examples of the water-insoluble and lipophilic high-molecular compound include copolymers having a molecular weight of usually from 100,000 to 200,000, having monomers represented by the following (1) to (17) as structural units.

(1) Acrylamides, methacrylamides, acrylates, methacrylates and hydroxystyrenes having an aromatic hydroxyl group, such as N- (4-hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) ) Methacrylamide, o-, m-, p-hydroxystyrene, o-, m
-, P-hydroxyphenyl-acrylate or methacrylate.

(2) Acrylic esters and methacrylic esters having an aliphatic hydroxyl group, for example, 2-
They are hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 4-hydroxybutyl methacrylate.

(3) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride and itaconic acid.

(4) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl Acrylate,
(Substituted) alkyl acrylates such as N-dimethylaminoethyl acrylate.

(5) (Substituted) alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, glycidyl methacrylate and N-dimethylaminoethyl methacrylate.

(6) Acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N Acrylamide or methacrylamides such as -nitrophenylacrylamide and N-ethyl-N-phenylacrylamide.

(7) Ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether,
Vinyl ethers such as octyl vinyl ether and phenyl vinyl ether.

(8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.

(9) Styrenes such as styrene, α-methylstyrene and chloromethylstyrene.

(10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone.

(11) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.

(12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like.

(13) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-aceketyl methacrylamide, N-propionyl methacrylamide, and N- (p-chlorobenzoyl) methacrylamide.

(14) N (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-amino) sulfonylphenylmethacrylamide, N- (1- (3-amino Sulfonyl) naphthyl) methacrylamide, N- (2
-Aminosulfonylethyl) methacrylamides such as methacrylamide, and acrylamides having the same substituents as described above, and o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, Unsaturated sulfonamides such as methacrylic esters such as 1- (3-aminosulfonylnaphthyl) methacrylate and acrylic esters having the same substituents as described above.

(15) Unsaturated monomers having a crosslinkable group in the side chain, such as N- (2- (methacryloyloxy) -ethyl) -2,3-dimethylmaleimide and vinyl cinnamate. Further, a monomer copolymerizable with the above monomer may be copolymerized.

(16) Phenol resins described in US Pat. No. 3,751,257 and polyvinyl acetal resins such as polyvinyl formal resin and polyvinyl butyral resin.

(17) JP-B-54-19773 in which polyurethane is solubilized with alkali, JP-A-57-904
No. 747, No. 60-182437, No. 62-
No. 58242, No. 62-123452, No. 6
It is a polymer compound described in JP-A-2-123453, JP-A-63-111450, and JP-A-2-14642.

If necessary, a polyvinyl butyral resin, a polyurethane resin, a polyamide resin, an epoxy resin, a novolak resin, a natural resin, or the like may be added to the above copolymer.

The photosensitive composition used in the photosensitive layer according to the invention may further contain a dye for the purpose of obtaining a visible image by exposure and a visible image after development. Examples of the dye include Victoria Pure-BOH
[Hodogaya Chemical Co., Ltd.], Oil Blue # 603 [Orient Chemical Co., Ltd.], Patent Pure Blue [Sumitomo Mikuni Chemical Co., Ltd.], Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Violet, Methyl Green, Erythrosin B, Basic Fuchsin ,
Malachite green, oil red, m-cresol purple, rhodamine B, auramine, 4-p-diethylaminophenyliminaphthoquinone, triphenylmethane series represented by cyano-p-diethylaminophenylacetanilide, diphenylmethane series, oxazine series,
Xanthen, iminonaphthoquinone, azomethine or anthraquinone dyes are mentioned as examples of color changing agents that change from colored to colorless or different colored tones.

On the other hand, examples of the color-changing agent that changes from colorless to colored include leuco dyes and, for example, triphenylamine,
Diphenylamine, o-chloroaniline, 1,2,3-
Triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p'-bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p,
p ', p "-tris-dimethylaminotriphenylmethane, p, p'-bis-dimethylaminodiphenylmethylimine, p, p', p" -triamino-o-methyltriphenylmethane, p, p'-bis -Dimethylaminodiphenyl-4-anilinonaphthylmethane, p, p ', p "
Primary or secondary arylamine dyes represented by -triaminotriphenylmethane. Particularly preferably, triphenylmethane-based and diphenylmethane-based dyes are effectively used, more preferably triphenylmethane-based dyes, and particularly, Victoria Pure Blue BO
H.

Various additives can be further added to the photosensitive composition used for the photosensitive layer in the present invention. For example, alkyl ethers (eg, ethyl cellulose, methyl cellulose) for improving coatability, fluorinated surfactants, nonionic surfactants (especially fluorinated surfactants are preferable), flexibility of the coating film, and resistance to Plasticizers for imparting abrasion properties (for example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate,
Oligomers and polymers of trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid, of which tricresyl phosphate is particularly preferred), and a sensitizing agent for improving the liposensitivity of the image area (for example, No. 55-527, a half-esterified product of a styrene-maleic anhydride copolymer with an alcohol, a novolak resin such as a pt-butylphenol-formaldehyde resin, and 50% of p-hydroxystyrene.
% Fatty acid ester), stabilizers {for example, phosphoric acid, phosphorous acid, organic acids (citric acid, oxalic acid, dipicolinic acid, benzenesulfonic acid, naphthalenesulfonic acid, sulfosalicylic acid, 4-methoxy-2-hydroxybenzophenone- 5-sulfonic acid, tartaric acid, etc.), development accelerators (eg, higher alcohols, acid anhydrides, etc.) and the like are preferably used.

In order to provide a photosensitive layer containing the above-mentioned photosensitive composition on the support of the present invention, a predetermined amount of a photosensitive diazo resin, a lipophilic polymer compound and, if necessary, various additives are appropriately added. Solvents (e.g., methyl cellosolve, ethyl cellosolve, dimethoxyethane, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethylformamide, dimethylacetamide,
Cyclohexanone, dioxane, tetrahydrofuran,
The composition may be dissolved in methyl lactate, ethyl lactate, ethylene dichloride, dimethyl sulfoxide, water or a mixture thereof to prepare a coating solution of the photosensitive composition, which may be coated on a support and dried. The solvent used may be a single solvent, but is more preferably a mixture of a high boiling solvent such as methyl cellosolve, 1-methoxy-2-propanol, methyl lactate and the like, and a low boiling solvent such as methanol and methyl ethyl ketone. When the photosensitive composition is coated on the lithographic printing plate support of the present invention, the solid concentration of the photosensitive composition is from 1 to 5
It is preferable to be within the range of 0% by mass.

<Negative Infrared Laser Recording Material> When the lithographic printing plate precursor of the present invention is to be a negative lithographic printing plate precursor that can be exposed to an infrared laser, the photosensitive layer can be formed by a useful negative photosensitive material for an infrared laser. Should be provided.
As the negative photosensitive material for infrared laser, (A) a compound which decomposes by light or heat to generate an acid, (B)
A crosslinking agent that is crosslinked by an acid, (C) an alkali-soluble resin, (D) an infrared absorber, (E) a general formula (R ¹ —X) _n —
Compound represented by Ar- (OH) _m ｛R ¹ : C 6-3
2, an alkyl group or an alkenyl group, X: a single bond, O,
S, COO, or CONH, Ar: an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a heterocyclic group, n = 1 to 3,
Compositions consisting of m = 1-3% are useful.

The negative type lithographic printing plate precursor has the disadvantage that fingerprints are easily formed after development and the strength of the image area is weak. However, such a disadvantage can be solved by forming a photosensitive layer with the above constituents. Hereinafter, the components of the negative type lithographic printing plate precursor will be described in detail.

Examples of the compound (A) which decomposes by light or heat to generate an acid include photo-decomposable compounds represented by iminosulfonate described in Japanese Patent Application No. 3-140109. Compounds that generate sulfonic acid include irradiation with a wavelength of 200 to 500 nm, or 100
Compounds that generate an acid when heated at a temperature of not less than ° C are exemplified. Suitable acid generators include a cationic photopolymerization initiator,
An initiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, and the like can be used. These acid generators are preferably added in an amount of 0.01 to 50% by mass based on the total solid content of the image recording material.

Examples of the crosslinking agent (B) for crosslinking with an acid include (i) an aromatic compound substituted with an alkoxymethyl group or a hydroxyl group, (ii) an N-hydroxymethyl group, an N-alkoxymethyl group, A compound having an acyloxymethyl group, and (iii) an epoxy compound.

As the alkali-soluble resin (C),
Novolak resins and polymers having a hydroxyaryl group in the side chain are exemplified.

Examples of the composition comprising the infrared absorbent (D) include commercially available dyes such as azo dyes, anthraquinone dyes and phthalocyanine dyes which effectively absorb infrared rays of 760 to 1200 nm, or black pigments described in Color Index. Red pigments, metal powder pigments, and phthalocyanine pigments are exemplified. Further, it is preferable to add an image colorant such as oil yellow or oil blue # 603 in order to improve the visibility of the image. Further, in order to improve the flexibility of the coating film, a plasticizer such as polyethylene glycol or phthalic ester can be added.

[Positive Infrared Laser Recording Material] When the lithographic printing plate precursor according to the invention is to be used as a positive lithographic printing plate precursor capable of being exposed to an infrared laser, the photosensitive layer is formed of a useful positive photosensitive material for an infrared laser. It is good to provide. Examples of the positive photosensitive material for an infrared laser include (A) an alkali-soluble polymer, (B) a compound that is compatible with the alkali-soluble polymer and reduces alkali solubility, and (C) a compound that absorbs an infrared laser. The positive photosensitive material for an infrared laser is useful. By using the above-mentioned positive type photosensitive material for infrared laser, it is possible to eliminate the lack of solubility in the alkali developing solution in the non-image area, and it is hard to be damaged, and has excellent alkali developing resistance in the image area, and the development stability. A good lithographic printing plate can be obtained.

Examples of the (A) alkali-soluble polymer include (i) a phenolic resin, a cresol resin, a novolak resin, and a pyrogallol resin, which are represented by a polymer compound having a phenolic hydroxyl group, and (ii) a polymer having a sulfonamide group. A compound obtained by copolymerizing a monomer alone or with another polymerizable monomer, (iii) N-
(P-toluenesulfonyl) methacrylamide or N-
Compounds having an active imide group typified by (p-toluenesulfonyl) acrylamide in the molecule are preferred. Examples of the component (B) include compounds that interact with the component (A), such as a sulfone compound, an ammonium salt, a sulfonium salt, and an amide compound. For example, when the component (A) is a novolak resin, a cyanine dye is suitable as the component (B).

The component (C) includes 750 to 120
A material that has an absorption region in the infrared region of 0 nm and has a light / heat conversion capability is preferable. Examples of those having such a function include squarylium dyes, pyrylium salt dyes, carbon black, insoluble azo dyes, and anthraquinone dyes. These pigments preferably have a size in the range of 0.01 μm to 10 μm, add a dye, dissolve them in methanol, methyl ethyl ketone or the like as an organic solvent,
The mass after drying on an aluminum alloy plate is 1 to 3 g / m ²
Is applied and dried so that

[Photopolymerizable Photopolymer Laser Recording Material] In the case of producing a negative type lithographic printing plate precursor that can be exposed to an infrared laser, a photopolymerizable photopolymer photosensitive material is used as a further useful material for a photosensitive layer capable of laser exposure. Materials. When the photopolymerizable photopolymer photosensitive material is used, prior to the application of the photosensitive layer, the support is coated on the support with the aim of improving the adhesion between the support and the photosensitive layer. No. 56177, JP-A-8-320
It is preferable to provide an adhesive layer containing a silicone compound having a reactive functional group described in JP-A-551-551. That is, a silane compound such as ethylene tetramethoxy silane or ethylene tetraethoxy silane is dissolved in a solvent such as methanol or ethanol at a ratio of 1 to 20% by mass, and is dissolved under an acid catalyst such as hydrochloric acid, nitric acid, phosphoric acid, and sulfonic acid. For hydrolysis. Then, a -Si-O-Si- bond is formed to form a sol, which can be provided as an adhesive layer on the support of the present invention. At this time, the viscosity is 0.2 mPa · s by dissolving the silane compound in a suitable solvent such as methanol.
(0.2 centipoise) to 2000 mPa · s (20 poise), and adjust the applied mass after drying to 1 to 10 mPa · s (20 poise).
It is preferably 0 mg / m ² . A photosensitive layer having a polymerizable compound having an addition-polymerizable unsaturated bond (compound having a terminal ethylenic photopolymerizable group), which is a photopolymerizable photopolymer photosensitive material, can be provided on the surface of the adhesive layer.
The photosensitive layer may contain a photopolymerization initiator, an organic polymer binder, a coloring agent, a plasticizer, a thermal polymerization inhibitor, and the like.

Examples of the compound having a terminal ethylenically unsaturated bond include esters of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound (eg, acrylates, methacrylates, itaconates, and maleates), and the like. An amide of a saturated carboxylic acid and an aliphatic polyamine compound (such as methylenebisacrylamide and xylylenebisacrylamide) is exemplified. As the photopolymerization initiator, a titanocene compound, a triazine-based, a benzophenone-based, or a benzimidazole-based sensitizer can be used. Further, a sensitizer such as a cyanine dye, a merocyanine dye, a xanthene dye, and a coumarin dye may be used. A negative type lithographic printing plate precursor capable of being exposed to infrared laser is provided by providing a photosensitive layer having a coating amount of 1 to 3 g / m ² after drying the photosensitive composition having such a composition on the surface of the support of the present invention. Can be produced.

[Photocrosslinking Photopolymer Type Laser Recording Material] A photocrosslinking photopolymer may be used as the material for the photosensitive layer. As the photocrosslinkable photopolymer,
For example, polyester compounds disclosed in JP-A-52-96696, British Patent No. 1,112,277
JP-A-62-278 having a maleimide group in a side chain is preferred.
No. 544 is more preferable.

[Sulfonate-type infrared laser recording material] Further, as the material for the photosensitive layer, a sulfonate-type infrared laser recording material may be used. As the above-mentioned sulfonate type infrared laser recording material, for example, sulfonate compounds disclosed in JP-A-270480, JP-A-2704872, and the like can be used. In addition, photosensitive materials that generate sulfonic acid by the heat generated by infrared laser irradiation and are solubilized in water, and photosensitive materials whose surface polarity changes by irradiating infrared laser with solidifying styrene sulfonic acid ester with sol-gel, Japanese Patent Application No. 9-89816, Japanese Patent Application No. 10-22406, Japanese Patent Application No. 10-027655.
It is possible to use a photosensitive material whose hydrophobic surface changes to hydrophilic by laser exposure described in the specification. In order to further improve the characteristics of the photosensitive layer made of a polymer compound capable of generating a sulfonic acid group by the above heat, it is preferable to use the following methods in combination. Examples of such a method include (1) a method using in combination with an acid or base generator described in Japanese Patent Application No. 10-7062, and (2) a specific method described in Japanese Patent Application No. 9-340358. Method of providing an intermediate layer, (3) Japanese Patent Application No. 9-248
No. 994, JP-A-10-43921, and (5) Japanese Patent Application No. 10-43921. 1
Examples thereof include a method used in the mode of modifying the surface of solid particles described in the specification of JP-A No. 15354.

Other examples of the composition for changing the hydrophilicity / hydrophobicity of the photosensitive layer by utilizing the heat generated by laser exposure include, for example, the W described in US Pat. No. 2,764,085.
a composition comprising an erner complex which changes to hydrophobic by heat, a specific saccharide described in JP-B-46-27219, a composition which changes to hydrophilic upon exposure to a melamine formaldehyde resin or the like; -63704
No. 4,081,572, which is dehydrated by heat, such as a phthalyl hydrazide polymer described in US Pat. No. 4,081,572.
A composition comprising a polymer to be hydrophobized;
JP-A-60-132760 which discloses a composition having a tetrazolium salt structure described in JP-A-100
JP-A-64-3543, a composition comprising an imide precursor polymer described in JP-A-64-3543, and a composition which becomes hydrophobic by exposure. JP-A-74706 discloses a composition comprising a fluorocarbon polymer, which is made hydrophilic by exposure to light.

Further, a composition comprising a hydrophobic crystalline polymer which is made hydrophilic by exposure described in JP-A-3-197190 and a side group insolubilized by heat described in JP-A-7-186562 are disclosed. Comprising a polymer which changes into hydrophilic and a photothermal conversion agent;
A composition comprising a three-dimensionally cross-linked hydrophilic binder containing microcapsules described in JP-A-1849 and hydrophobized by exposure, or valence isomerization or proton transfer isomerization described in JP-A-8-3463. JP-A-60-228 describes a composition, a composition that changes the phase structure (compatibilization) in a layer by heat described in JP-A-8-141819 and changes hydrophilicity / hydrophobicity, and JP-B-60-228. A composition in which the surface morphology and the hydrophilicity / hydrophobicity of the surface are changed by the heat of the above.

Another preferred example of the photosensitive layer material is a composition which changes the adhesiveness between the photosensitive layer and the support by so-called heat mode exposure utilizing heat generated by high power and high density laser light. You can give things. Specifically, a composition comprising a heat-fusible or heat-reactive substance described in JP-B-44-22957 can be used.

[Electrophotographic photosensitive resin-based laser recording material] As a photosensitive layer of the lithographic printing plate precursor according to the present invention, for example, a ZnO photosensitive layer disclosed in US Pat. No. 3,001,872 is provided. And JP-A-56-16
A photosensitive layer using an electrophotographic photosensitive resin described in JP-A No. 1550, JP-A-60-186847, JP-A-61-238063 or the like may be provided. The coating amount of the photosensitive layer provided on the support of the present invention may be about 0.1 to about 7 g / m ² in terms of dry mass after coating,
Preferably, it is 0.5 to 4 g / m ² .

The basic patent of the electrophotographic method is disclosed in Japanese Patent Publication No. 37-17162, and in addition, Japanese Patent Application Laid-Open No. 56-107246 and Japanese Patent Publication No. 59-36259.
The method disclosed in each gazette such as the gazette can be used. The electrophotographic photosensitive resin is mainly composed of a photoconductive compound and a binder. For the purpose of improving sensitivity and obtaining a desired photosensitive wavelength, known pigments, dyes, chemical sensitizers, and other necessary additives are used. Can be used.

The planographic printing plate precursor according to the invention includes
To increase the adhesion between the light-sensitive support and the photosensitive layer, or after development
To prevent the photosensitive layer from remaining on the
Provide an intermediate layer as necessary to prevent
You may. In order to improve the adhesion, generally
In the interlayer, a diazo resin or a phosphor adsorbing to aluminum, for example, is used.
Use acid compounds, amino compounds, carboxylic acid compounds, etc.
Is preferred. Also, make sure that the photosensitive layer does not remain after development.
To provide an intermediate layer using a highly soluble substance
Preferably, a polymer having good solubility or a water-soluble polymer
It is preferred to use a mer. Further prevention of halation
To do so, include a dye or UV absorber in the intermediate layer
Is preferred. The thickness of the intermediate layer is arbitrary,
Thickness that causes a uniform bond formation reaction with the upper photosensitive layer when
Must. Usually about 1-100m with dry solid
g / m ^TwoIs preferable, and 5 to 40 mg / m^TwoGasa
More preferred.

A mat layer composed of protrusions provided independently of each other may be provided on the applied photosensitive layer. The purpose of providing the mat layer is to improve the vacuum adhesion between the negative image film and the photosensitive lithographic printing plate in the contact exposure, thereby shortening the evacuation time and further crushing the fine halftone dots at the time of exposure due to poor adhesion. Is to prevent. As a method for coating the mat layer, see
Japanese Patent Application Laid-Open No. 58-1826 discloses a method for heat-sealing powdered solid powder described in JP-A-12974.
A method of spraying and drying polymer-containing water described in Japanese Patent Publication No. 36 can be selected as appropriate, but the matte layer itself is dissolved in an aqueous alkali developer containing substantially no organic solvent or removed by this. Possible ones are preferred.

The photosensitive layer provided as described above, excluding the electrophotographic photosensitive resin-based laser recording material, has a dry weight of 1 regardless of whether it is a positive photosensitive layer or a negative photosensitive layer.
３3 g / m ² , preferably 1.5-2.5 g
/ M ² is more preferable. It is preferable that a known mat layer having a dry weight of 0.001 to 1 g / m ² (more preferably 0.005 to 0.2 g / m ² ) is sequentially formed on the photosensitive layer. Further, the average surface roughness of the lithographic printing plate precursor (Ra: JIS B0601-19)
94) is preferably from 0.3 to 0.6 μm, more preferably from 0.35 to 0.55. The L * value is preferably from 50 to 95, and more preferably from 60 to 90. Delta Eab * is preferably 2 or less, more preferably 0 to 1. Here, the L * value and the delta Eab * are based on JIS Z8729-
L * value and delta Eab * defined in 1980
Say. In addition, the average surface roughness of the lithographic printing plate precursor (R
a), L * value and delta Eab * refer to values in a state of a lithographic printing plate support on which a photosensitive layer or the like is not formed.

<< Lithographic Printing Plate >> The lithographic printing plate precursor described above, in which the photosensitive layer is provided on the support of the present invention, is exposed by an infrared laser or the like, developed with an alkali developing solution or the like, and processed. Becomes The light source used for exposure is 700
An infrared laser of ~ 1200 nm can be used. In recent years, in the plate making / printing industry, automatic developing machines for printing plate materials have been widely used in order to rationalize and standardize plate making operations, and it is preferable to use the automatic developing machine also in the method of the present invention. In developing the exposed lithographic printing plate precursor of the present invention,
JP-A-54-62004 describes a developer mainly containing an alkali silicate such as sodium silicate and potassium silicate, and saccharose having no free aldehyde group or ketone group and showing no reducibility. The developer described in JP-A-8-305039 containing a non-reducing sugar such as trehalose as a main component can be used. Furthermore, an alkali agent such as potassium hydroxide, a development stabilizer such as a polyethylene glycol adduct of a sugar alcohol disclosed in JP-A-6-282079, a reducing agent such as hydroquinone, and a hard water such as ethylenediamine. Softener, nonionic,
Anionic or amphoteric surfactant, or Japanese Patent Publication 3
For example, a polyoxyethylene / polyoxypropylene block polymerization type surfactant disclosed in JP-A-54339 can be added. In the case of alkali silicate,
The molar ratio of SiO ₂ / M ₂ O (M represents an alkali metal)
Is preferably in the range of 0.3 to 3.0. By this development processing, Si can be attached to the surface. Further, it is also possible to measure the amount of Si element present on the surface by ESCA. Further, C, Al, O, S,
The amounts of Si and Ca were measured, and their element ratios (atom.%)
Is calculated as The Si amount is 1 to 25 atom.
%, Especially 5 to 20 atom. %.
If the Si content is in this range, it is effective in preventing halation at the time of irradiating infrared laser light.

On the other hand, in the case of the developer containing the above-mentioned non-reducing sugar as a main component, it is necessary to previously hydrophilize the surface of the aluminum support by silicate treatment or the like. Even in this case, the amount of Si adhering to the surface after development is 1 to 25 at.
om. % Is preferred. In the above, the development is preferably carried out using an automatic developing machine. By adding a replenisher having a higher alkali strength than the developer to the developer, the development can be stably performed for a long time. A surfactant such as an anionic surfactant can be added to the replenisher in order to disperse the developing residue and increase the ink affinity of the printed image area. Further, if necessary, an antifoaming agent and a water softener can be added.

The surface of the developed lithographic printing plate precursor is as follows:
It is preferable to carry out a post-treatment with a rinsing solution having a surfactant or a desensitizing solution containing arabic gum or a starch derivative. When using an aqueous solution containing 5 to 15% by mass of arabic gum or a starch derivative at a solid content concentration, the wet application amount is 1 to
The surface after development is protected to 10 ml / m ² .
Further, the coating amount after drying is preferably from 1 to 5 g / m ² . Furthermore, when higher printing durability is required,
It is preferable to perform a burning treatment described in JP-B-61-2518. Also, as the application method,
For example, the surface conditioning liquid disclosed in Japanese Patent Publication No. 55-28062 may be applied with a sponge or absorbent cotton, or may be applied with an automatic coater. When a surface conditioning liquid is used, generally, 0.3 to 0.8 g / m ² (dry mass) is appropriate.

As described above, the lithographic printing plate precursor according to the present invention is subjected to processing including development by an ordinary method after image exposure, and a resin image is formed to form a lithographic printing plate. For example, in the case of a photosensitive lithographic printing plate precursor having the photosensitive layer of the above [I], after image exposure, U.S. Pat. No. 4,259,434.
The exposed portion is removed by developing with an alkaline aqueous solution as described in the specification, a lithographic printing plate is obtained, and in the case of the lithographic printing plate precursor having the photosensitive layer of the above [II], After exposure, US Pat. No. 4,186,006
The photosensitive layer in the unexposed areas is removed by development with a developing solution as described in the specification, and a lithographic printing plate is obtained. Also, JP-A-59-84241 and JP-A-57-84241
192,952 and JP-A-62-24263.
An aqueous alkaline developer composition used for developing a positive-working lithographic printing plate precursor as described in each of the publications can also be used.

[0175]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 Using an aluminum alloy plate having the composition shown in Table 1, alkali etching, desmutting, electrolytic surface roughening,
An alkali etching treatment, a desmutting treatment, and an anodic oxidation treatment were sequentially performed to produce a lithographic printing plate support.

[0177]

[Table 1]

Alkali etching treatment: An alkaline aqueous solution (NaOH: 27% by mass, aluminum ion: 6.5% by mass) at 70 ° C. was sprayed from a spray tube to perform an alkali etching treatment on the aluminum alloy plate (alkali etching treatment step). . The dissolution amount of the aluminum alloy plate on the surface to be electrochemically roughened in a later step is 6 g /
m ² . The dissolution amount of the aluminum alloy plate on the back surface was 1 g / m ² . For the concentration of the alkaline aqueous solution, refer to a table created in advance from the relationship between the NaOH concentration, the aluminum ion concentration, the temperature, the specific gravity, and the conductivity of the liquid. And a 48% by mass NaOH solution were added to keep the concentration of the alkaline aqueous solution constant. Thereafter, a water washing treatment (water washing treatment) was performed with a water injection pressure of 2 kg / cm ² , a moving speed of the aluminum alloy plate of 30 m / min, and an amount of sprayed water of 5 L / m ² .

Desmutting treatment: Next, the aluminum alloy plate was subjected to desmutting treatment using an aqueous hydrochloric acid solution as an acidic solution (desmutting treatment step). As the hydrochloric acid aqueous solution used for the desmut treatment, a waste liquid of the hydrochloric acid used for the electrolytic surface roughening treatment in the next step was used. The liquid temperature (treatment temperature) was 45 ° C., and the concentration was 7.5 g / liter of hydrochloric acid (the concentration of aluminum contained therein was 5 g / liter). The acidic solution was sprayed with a spray to perform a desmutting treatment for 2 seconds. afterwards,
The same water washing treatment as above was performed.

Electrolytic surface-roughening treatment: AC current for generating a sine wave obtained by adjusting the current and voltage of a commercial alternating current of 60 Hz by an induction voltage regulator and a transformer (electrical quantity QA in which an aluminum alloy plate is an anode and cathode). Ratio to electric quantity QC: QC
The electrolytic surface roughening treatment was continuously performed using / QA = 1, AC duty: 1) (electrolytic surface roughening treatment step). The time from 0 to the peak was 4.15 msec.
The electrolytic cell shown in FIG. 3 was used, and the main electrode was a carbon electrode. QC / QA until passing through main electrolytic cell 10 in FIG.
Was 0.95. Liquid temperature 45 ° C, hydrochloric acid concentration 7.5 g
An aluminum chloride was added to a 1 / liter aqueous solution to adjust the aluminum ion concentration to 5 g / liter, and an electrolytic solution was used.

The current density was 50 at the time of the peak of AC and at the time of the anode reaction and the cathode reaction of the aluminum alloy plate.
A / dm ² . The amount of electricity applied to the aluminum alloy plate is the sum of the amount of electricity at the time of anode of the aluminum alloy plate, which is 4
It was 00 C / dm ² . Thereafter, the same water washing treatment as described above was performed.

The concentration of the hydrochloric acid aqueous solution was controlled by adding a 35% by mass hydrochloric acid stock solution and water in proportion to the amount of electricity supplied, and successively circulating an acidic electrolytic solution having the same volume as the added volume of hydrochloric acid and water. From the circulation tank system, and refer to the table created from the relationship between the hydrochloric acid concentration, the aluminum ion concentration, the temperature, the conductivity of the liquid, and the ultrasonic wave propagation speed of the liquid, and determine the temperature, conductivity, and The concentration of the aqueous hydrochloric acid solution was determined from the sound wave propagation speed, and the concentration was kept constant by performing control to sequentially adjust the addition amounts of the hydrochloric acid stock solution and water. The liquid was discharged out of the system from the circulation tank by overflow.

Alkali etching treatment: An alkaline aqueous solution (NaOH: 5% by mass, aluminum ion: 0.5% by mass) at 45 ° C. was sprayed from a spray tube to perform an alkali etching treatment on the aluminum alloy plate (alkali etching treatment step). . The dissolution amount of the aluminum alloy plate on the surface subjected to the electrolytic surface roughening treatment in the previous step is 0.1 g / m ^2.
Met. The dissolution amount of the aluminum alloy plate on the back surface was 0.1 g / m ² . For the concentration of the alkaline aqueous solution, refer to a table created in advance from the relationship between the NaOH concentration, the aluminum ion concentration, the temperature, the specific gravity, and the conductivity of the liquid,
The concentration of the aqueous alkali solution is determined from the temperature, specific gravity, and conductivity, and water and NaOH are 48 mass% by feedback control.
And the concentration of the aqueous alkaline solution was kept constant.
Thereafter, the same water washing treatment as described above was performed.

Desmutting treatment: Next, the aluminum alloy plate was subjected to desmutting treatment using sulfuric acid as an acidic solution (desmutting treatment step). The sulfuric acid concentration was 300 g / liter (containing 5 g / liter of aluminum ions), the liquid temperature was 70 ° C., and desmutting was performed by spraying with a spray for 2 seconds. For the concentration of the liquid, refer to a table created in advance from the relationship between the sulfuric acid concentration, the aluminum ion concentration, the temperature, the specific gravity, and the conductivity of the liquid. And the sulfuric acid was added to keep the solution concentration constant. Thereafter, the same water washing treatment as described above was performed.

Anodizing treatment: Next, a 50 ° C. sulfuric acid aqueous solution (sulfuric acid concentration: 100 g /
Liter, aluminum ion: 5 g / liter) As an electrolyte, using a DC voltage, the amount of anodized film was 2.4 g / liter.
Anodizing treatment was performed so as to obtain m ² (anodizing treatment step). The voltage was 20 V, the current density was 10 A / dm ² , and the electrolysis time (treatment time) was 30 seconds. For the concentration of the anodizing solution, refer to a table created in advance from the relationship between the sulfuric acid concentration, the aluminum ion concentration, the temperature, the specific gravity, and the conductivity of the solution. The solution concentration was kept constant by adding 50% by weight of sulfuric acid. Thereafter, the same water washing treatment as described above was performed.

Each of the above treatments was performed to produce a lithographic printing plate support. Observation at a magnification of 750 using a scanning electron microscope confirmed that the lithographic printing plate had a surface shape with uniform irregularities suitable for a lithographic printing plate.

(Example 2) The aluminum alloy plate was subjected to various treatments in the same manner as in Example 1 except that the AC current used in the electrolytic surface roughening treatment of Example 1 was changed to a power supply for generating a trapezoidal wave AC current. A lithographic printing plate support was produced. The frequency of the alternating current in the electrolytic surface-roughening treatment was 60 Hz, and the time Tp from the zero to the peak of the current was 2 msec. The current density was 50 A / d at the time of the peak of AC and at the time of the anodic reaction and the cathodic reaction of the aluminum alloy plate.
m ² . The amount of electricity added to the aluminum alloy plate is
400C in total of the quantity of electricity at the time of anode of aluminum alloy plate
/ Dm ² .

Observation with a scanning electron microscope at a magnification of 750 times confirmed that the lithographic printing plate had a surface with uniform unevenness suitable for a lithographic printing plate.

(Example 3) Before the alkali etching treatment in Example 1, mechanical surface roughening treatment was performed, and the total amount of electricity at the time of anode of an aluminum alloy plate subjected to electrolytic surface roughening treatment in an aqueous hydrochloric acid solution. A lithographic printing plate support was produced in the same manner as in Example 1 except that the value was changed to 50 C / dm ² .

For the mechanical surface roughening treatment, a roller-shaped nylon brush rotating while supplying a suspension of silica sand and water having a specific gravity of 1.12 as a polishing slurry to the surface of the aluminum alloy plate with a spray tube. Mechanically roughened. The nylon brush was made of nylon 6/10, and a No. 3 brush with a hair length of 50 mm was used. Nylon brushes were made by drilling holes in a stainless steel cylinder with a diameter of 300 mm and densely implanting the hairs. Three rotating brushes were used. The distance between the two support rollers (φ200mm) below the brush is 3
00 mm. The brush roller controls the load of the drive motor for rotating the brush against the load before pressing the brush roller against the aluminum alloy plate, and the average surface roughness (Ra) of the roughened aluminum alloy plate is 0.3. ~
It was pressed down to 0.4 μm (center value: 0.35 μm). The rotating direction of the brush was the same as the moving direction of the aluminum alloy plate. Then, it was washed with water. For the concentration of the abrasive, refer to the table created from the relationship between the abrasive concentration, temperature and specific gravity in advance, find the abrasive concentration by temperature and specific gravity, and add water and abrasive by feedback control to keep the abrasive concentration constant Kept. Since the abrasive was pulverized to reduce the particle size and the surface shape of the roughened aluminum alloy plate changed, the abrasive having a small particle size was sequentially discharged out of the system by the cyclone. The particle size of the abrasive was in the range of 1 to 15 μm, and its volume average particle size determined by a Horiba laser particle size distribution analyzer (LA910) was 8 μm.

Observation at a magnification of 750 using a scanning electron microscope confirmed that the lithographic printing plate had a surface shape having uniform unevenness suitable for a lithographic printing plate.

Example 4 A lithographic printing plate support was produced in the same manner as in Example 1 except that JIS1050H18 was used as the material for the aluminum alloy plate used in Example 1. Observation at a magnification of 750 using a scanning electron microscope confirmed that the lithographic printing plate had a surface shape with uniform irregularities suitable for a lithographic printing plate.

(Example 5) The current density in the electrolytic surface roughening treatment of Example 3 was set to 5 A / dm ² , and the electric quantity at the time of the anode of the aluminum alloy plate was set to 100 C / dm ² . The dissolution amount of aluminum in the alkali etching treatment (dissolution amount of the surface subjected to the electrolytic surface roughening treatment) was set to 0.3 g /
except that the m ² was making a lithographic printing plate support in the same manner as in Example 3. 750 magnification using a scanning electron microscope
Observation at × 2 confirmed that the lithographic printing plate had a surface shape having uniform unevenness suitable for a lithographic printing plate.

Example 6 Before the electrolytic surface roughening treatment of Example 1, an aluminum alloy plate was treated with an aqueous solution containing 2.0 g / liter of dimethylaminoborane at 40 ° C. for 5 seconds by using a spray. A lithographic printing plate support was produced in the same manner as in Example 1 except that an activation treatment for activating the surface was performed (activation treatment step), and then the same water washing treatment was performed. 750 magnification using a scanning electron microscope
Observation at × 2 confirmed that the lithographic printing plate had a surface shape having uniform unevenness suitable for a lithographic printing plate.

(Example 7) Before the electrolytic surface roughening treatment of Example 3, an aluminum alloy plate was treated with an aqueous solution containing 2.0 g / liter of dimethylaminoborane at 40 ° C for 5 seconds by using a spray. A lithographic printing plate support was produced in the same manner as in Example 3 except that an activation treatment for activating the surface was performed (activation treatment step), and then the same water washing treatment was performed as described above. Observation at a magnification of 750 using a scanning electron microscope confirmed that the lithographic printing plate had a surface shape with uniform irregularities suitable for a lithographic printing plate.

(Example 8) Each of the lithographic printing plate supports produced in Examples 1 to 7 was covered with JP-A-60-1494.
No. 91, the undercoat layer described in Example 1 (dry weight: 0,1).
01 g / m ² ), positive photosensitive layer (dry weight: 1.0 g / m ² )
m ² ) was applied and dried to produce a lithographic printing plate precursor, which was then exposed and developed in the same manner as in Example 1 of JP-A-60-149491 to produce a lithographic printing plate. When the printing evaluation was performed using each of the manufactured planographic printing plates, the printing plate was found to have good blanket stains and severe ink stains. In the printing evaluation, blanket stain was determined by the degree of adhesion of ink to a blanket cylinder after printing, and severe ink stain was determined by the degree of dot-like ink adhered to a non-image portion of a printed material. In all cases, those having a low degree of adhesion were judged to be good lithographic printing plate supports (the same applies hereinafter).

Example 9 An aqueous solution containing 2.5 mass% of No. 3 sodium silicate was immersed in each of the lithographic printing plate supports produced in Examples 1 to 7 at 70 ° C. for 10 seconds. A hydrophilization treatment was performed (hydrophilization treatment step). Thereafter, the undercoat layer described in Example 1 of JP-A-59-101651 (dry weight 0.05 g / m ^2), the negative photosensitive layer (dry weight 2.0 g / m ²⁾ was coated and dried, A lithographic printing plate precursor was manufactured, and Example 1 of JP-A-59-101651 was manufactured.
In the same manner, a lithographic printing plate was produced by performing exposure and development treatments. When the printing evaluation was performed using each of the manufactured lithographic printing plates, the printing plate was found to have good blanket stain, severe ink stain, and the like.

Example 10 An aqueous solution containing 1% by mass of No. 3 sodium silicate was immersed in each of the lithographic printing plate supports produced in Examples 1 to 7 at 30 ° C. for 10 seconds to obtain a hydrophilic surface. (Hydrophilization treatment step). Thereafter, an undercoat layer (dry weight: 0.01 g / m ² ) and a positive photosensitive layer capable of infrared laser exposure (dry weight: 1.8 g / m ² ) described in Example 1 of JP-A-2000-62333 were used. Coating ・
After drying, a lithographic printing plate precursor was manufactured.
Exposure and development were performed in the same manner as in Example 1 of JP-A No. 333 to produce a lithographic printing plate. When printing evaluation was performed using each of the manufactured lithographic printing plates, blanket stains,
Severe ink stains and the like were good printing plates.

(Example 11) Each of the lithographic printing plate supports produced in Examples 1 to 7
The undercoat layer (dry weight: 0.11 g / m ² ) described in Example 2 of JP-A-333 and a negative photosensitive layer (dry weight: 1.5 g / m ² ) capable of being exposed to an infrared laser are coated and dried, and then lithographic printing. A printing plate precursor was manufactured, and thereafter,
Exposure and development were carried out in the same manner as in Example 2 of JP-A No. 3 to produce a lithographic printing plate. When the printing evaluation was performed using each of the manufactured lithographic printing plates, the printing plate was found to be excellent in severe ink stains and the like.

(Example 12) Each of the lithographic printing plate supports produced in Examples 1 to 7 was covered with JP-A-2000-62.
No. 333, an undercoat layer (dry weight: 0.02 g / m ² ), a photopolymer type photosensitive layer capable of laser exposure (dry weight: 1.5 g / m ² ), and a protective layer (dry weight: 2 g / m ² ) m ² ) was applied and dried to produce a lithographic printing plate precursor, which was then exposed and developed in the same manner as in Example 3 of JP-A-2000-62333 to produce a lithographic printing plate. When the printing evaluation was performed using each of the manufactured lithographic printing plates, a favorable printing plate such as a blanket stain and severe ink stain was found.

Example 13 The lithographic printing plate supports manufactured in Examples 1 to 3 were measured for physical properties before forming a photosensitive layer by coating. , 0.5, 0.55, 0.35μ
m, L * values are 80, 85, 75, Delta Ea, respectively
b * was 0.5, 0.8, and 0.3, respectively, and it was a support having a surface shape suitable for a printing plate, and had a uniform appearance excellent in plate inspection properties.

The average surface roughness (Ra) was measured using a Surfcom 575A (probe diameter 2 μmR) manufactured by Tokyo Seimitsu Co., Ltd.
L * value and delta Eab * were measured according to IS B 0601-1982, respectively, according to JIS Z 87
The measurement was performed using SM-3-SCH manufactured by Suga Test Instruments Co., Ltd. according to 29-1980 and JIS Z8730-1980.

(Example 14) A lithographic printing plate support was produced in the same manner as in Example 1 except that the washing treatment with water in Example 1 was carried out using dry ice powder. The conditions for the cleaning treatment using dry ice powder were as follows: powder-type dry ice having a volume average particle diameter of 100 μm was used, and the supply amount of CO ₂ per injection nozzle (solid weight) was 0.24 kg / min. The supply pressure was 6 MPa. Observation at a magnification of 750 using a scanning electron microscope confirmed that the lithographic printing plate had a surface shape with uniform irregularities suitable for a lithographic printing plate. Further, the amount of waste liquid was significantly reduced as compared with the case of performing the water washing treatment, and the cost required for waste liquid treatment could be reduced.

Example 15 A lithographic printing plate support was produced in the same manner as in Example 2 except that the washing treatment with water in Example 2 was carried out using dry ice powder. The conditions for the cleaning treatment using dry ice powder were as follows: powder-like dry ice having a volume average particle diameter of 50 μm was used, and the supply amount of CO ₂ per injection nozzle (by solid weight) was 0.12 kg / min. The supply pressure was 3 MPa. Magnification of 75 using a scanning electron microscope
When observed at 0 magnification, it was confirmed that the lithographic printing plate had a surface shape having uniform unevenness suitable for a lithographic printing plate.
In addition, the amount of waste liquid is significantly reduced compared to performing a water washing process,
The cost required for waste liquid treatment could be reduced.

Example 16 A lithographic printing plate support was produced in the same manner as in Example 3, except that the washing treatment with water in Example 3 was carried out using dry ice powder. The conditions for the cleaning treatment using dry ice powder were as follows: powder-like dry ice having a volume average particle diameter of 80 μm was used, and the supply amount of CO ₂ per injection nozzle (by solid weight) was 0.18 kg / min. The supply pressure was 7 MPa. Magnification of 75 using a scanning electron microscope
When observed at 0 magnification, it was confirmed that the lithographic printing plate had a surface shape having uniform unevenness suitable for a lithographic printing plate.
In addition, the amount of waste liquid is significantly reduced compared to performing a water washing process,
The cost required for waste liquid treatment could be reduced.

(Comparative Example 1) In the electrolytic surface roughening treatment in Example 1, the ratio of the quantity of electricity QA of the aluminum alloy plate as the anode to the quantity of electricity QC as the cathode: QC / QA was set to 0.1.
85. A lithographic printing plate support was produced in the same manner as in Example 1, except that a trapezoidal wave alternating current having a duty of 0.25, the alternating current duty of 0, and a peak from 0 to 0.05 msec was used. Observation with a scanning electron microscope at a magnification of 750 times revealed that large deep recesses unsuitable as a lithographic printing plate support were unevenly formed.

[0207]

According to the present invention, even when an aluminum alloy plate whose alloy components are not controlled is used as a raw material,
A method for producing a lithographic printing plate support, a lithographic printing plate support, and a lithographic printing plate precursor that can be produced stably and at low cost without causing severe ink stains can be provided.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing an example of an alternating current waveform (sine wave) that can be used in the present invention.

FIG. 2 is an explanatory diagram showing an example of an alternating current waveform (trapezoidal wave) that can be used in the present invention.

FIG. 3 is a schematic view showing an example of an apparatus that can be used for electrolytic surface roughening treatment.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 ... Main electrolytic cell 11 ... AC power supply 12 ... Radial drum roller 13a, 13b ... Main electrode 14 ... Solution supply port 15 ... Aqueous aqueous solution 20 ... Auxiliary anode tank 21. ..Auxiliary anode W ... Aluminum alloy plate

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C25D 11/16 301 C25D 11/16 301 C25F 3/04 C25F 3/04 D G03F 7/00 503 G03F 7 / 00 503 7/09 501 7/09 501 (72) Inventor Hirokazu Sawada 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Inside Fujisha Shin Film Co., Ltd. (72) Akio Uesugi 4000 Kawajiri, Yoshida-machi, Yoshida-machi, Haibara-gun, Shizuoka Fuji Photo film F-term (reference) 2H025 AA12 AB03 AD01 AD03 DA02 DA18 DA20 DA36 2H096 AA06 BA01 BA09 CA03 CA05 CA20 2H114 BA01 BA10 DA04 DA64 EA09 GA05 GA06 GA08 GA09

Claims (11)

[Claims] 1. A method for producing a lithographic printing plate support, comprising: a surface roughening step of electrolytically roughening an aluminum alloy plate using an alternating current in an acidic solution; and an anodizing step. A method for producing a lithographic printing plate support, wherein an alternating current waveform having a time from 0 to a peak of 1.5 to 6 msec is used in the electrolytic surface roughening treatment. 2. The purity of said aluminum alloy plate is 95-95.
The method for producing a lithographic printing plate support according to claim 1, wherein the amount is 99.4% by mass. 3. The method for producing a lithographic printing plate support according to claim 1, wherein the aluminum alloy plate contains at least five kinds of the following metals in the following range. Fe: 0.3 to 1.0% by mass, Si: 0.15 to
1.0% by mass, Cu: 0.1 to 1.0% by mass, Mg:
0.1-1.5% by mass, Mn: 0.1-1.5% by mass,
Zn: 0.1 to 0.5% by mass, Cr: 0.01 to 0.1
% By mass, Ti: 0.03 to 0.5% by mass. 4. The method for producing a lithographic printing plate support according to claim 1, comprising the following steps before and / or after the electrolytic surface-roughening treatment. (1) In an alkaline aqueous solution, the aluminum alloy
5 g / m ² dissolving alkali etching treatment step,
(2) A desmutting step of desmutting the aluminum alloy plate having undergone the alkali etching step in an acidic solution. 5. The desmutting treatment in the desmutting treatment step is performed by using an acidic solution having an acid solution concentration of 250 to 500 g / l and an aluminum ion concentration of 1 to 15 g / l at 60 to 90 ° C. for 1 to 180 seconds. The method for producing a lithographic printing plate support according to any one of claims 1 to 4, characterized in that: 6. The method for producing a lithographic printing plate support according to claim 4, wherein a mechanical surface roughening treatment step is provided before the alkali etching treatment step. 7. The lithographic printing plate support according to claim 1, wherein a sealing treatment step and / or a hydrophilic treatment step are provided after the anodizing treatment step. Method. 8. The lithographic plate according to claim 1, further comprising an activation step of activating the surface of the aluminum alloy plate before the electrolytic roughening step. A method for producing a printing plate support. 9. A lithographic printing plate support produced by the method for producing a lithographic printing plate support according to claim 1. Description: 10. An undercoat layer having a dry weight of 0.001 to 1 g / m ^{2 on} the surface of the lithographic printing plate support according to claim 9,
Dry weight 1 to 3 g / positive photosensitive layer or a negative photosensitive layer of m ^2, the lithographic printing plate precursor mat layer having a dry weight of 0.001 to 1 g / m ^2, characterized in that the are sequentially formed. 11. An average surface roughness (Ra) of 0.3 to 0.1.
The lithographic printing plate precursor according to claim 10, wherein the L * value is 50 to 95, and the delta Eab * is 2 or less.