JP2002363799A - Aluminum plate, method for producing supporting body for planographic printing plate, supporting body for planographic printing plate and planographic printing original plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aluminum plate which has little reduction in strength on burning treatment at a high temperature, and is suitable as the material for a supporting body for a planographic printing plate, a method for producing a supporting body for a planographic printing plate, a supporting body for a planographic printing plate, and a planographic printing original plate. SOLUTION: The aluminum plate has a composition containing, by weight, 0.05 to 0.5% Fe, 0.02 to 0.2% Si, 0.001 to 0.05% Cu, 0.003 to 0.04% Ti, 0.001 to 0.3% Mg, 0.001 to 0.05% Mn and 0.001 to 0.05% Zn, and in which the width of the crystal grains in the surface is 20 to 200 μm. In the method for producing a supporting body for a planographic printing plate, at least one side in the above aluminum plate is roughened by a preceding alkali etching stage where etching treatment is performed thereto with an alkali solution, and an electrolytic roughening stage where electrolytic roughening treatment is performed thereto in a hydrochloric acid aqueous solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aluminum plate,
A method for producing a lithographic printing plate support, a lithographic printing plate support,
And a lithographic printing plate precursor, in particular, a method for producing a lithographic printing plate support that becomes a support for a lithographic printing plate precursor having a reduced strength when subjected to a burning treatment at a high temperature, The present invention relates to a support and a lithographic printing plate precursor using the lithographic printing plate support as a support.

[0002]

2. Description of the Related Art A lithographic printing plate precursor, which is a lithographic printing plate precursor, is generally obtained by roughening the surface of an aluminum web, which is a strip of pure aluminum or an aluminum alloy, and then subjecting the surface to an anodizing treatment. A lithographic printing plate support is obtained by forming an anodic oxide film, and a photosensitive resin or a heat-sensitive resin is applied to the surface of the lithographic printing plate support on which the anodic oxide film is formed to form a photosensitive or heat-sensitive resin. It is produced by forming a plate making layer. These photosensitive resin layers and heat-sensitive resin layers including an undercoat layer and a protective film layer are disclosed in JP-A-2000-62333, JP-A-59-101651, and
This is known in Japanese Patent Application Laid-Open No. 0-149491.

A lithographic printing plate is manufactured by exposing and developing the lithographic printing original plate and printing a print image such as a character and a picture on a plate-making layer.

In recent years, in order to increase the printing durability of a lithographic printing plate so that a large number of printed materials can be obtained from one lithographic printing plate,
Heat treatment, that is, burning treatment, of a lithographic printing plate after exposure and development has been widely performed to strengthen a printed image on the lithographic printing plate. The higher the temperature of the burning process, the shorter the required time, the higher the work efficiency. Therefore, in recent years, 28
It has been studied to perform the burning treatment at a high temperature of 0 ° C. or higher.

[0005]

However, in a conventional lithographic printing plate, when a burning treatment is performed at a high temperature, a recrystallization phenomenon occurs in an aluminum web forming a support, and the strength is greatly reduced. There was a problem that the printing plate became rigid and handling became difficult. Further, when such a lithographic printing plate is fixed to a plate cylinder of an offset printing press, the lithographic printing plate may be cut at a grip portion fixed to the plate cylinder, or the portion may be stretched or deformed to cause printing misalignment. There were also problems such as the occurrence of obstacles.

According to the present invention, even when a burning treatment is performed at a high temperature, the strength does not decrease so much, the grip does not cut off when the plate is mounted on the plate cylinder, the handling is easy, and the expansion and deformation are caused. Aluminum plate suitable as a material for a lithographic printing plate support that becomes a lithographic printing plate support that does not cause problems such as printing misregistration, a manufacturing method for manufacturing a lithographic printing plate support from the aluminum plate, and the problem described above. It is an object of the present invention to provide a lithographic printing plate support capable of producing a lithographic printing plate without generation of lithographic printing plate, and a lithographic printing plate precursor using the lithographic printing plate support as a support.

[0007]

According to a first aspect of the present invention, there is provided a method for manufacturing a semiconductor device, comprising: Fe: 0.05 to 0.5% by weight;
0.2% by weight, Cu: 0.001 to 0.05% by weight, T
i: 0.003 to 0.04% by weight, Mg: 0.001 to
0.3% by weight, Mn: 0.001 to 0.05% by weight, Z
n: 0.001 to 0.05% by weight, 50 from the surface
At a depth within μm, the width of the crystal grains is 20 to 200 μm.
m with respect to the aluminum plate.

[0008] The aluminum plate is suitable as a material for a lithographic printing plate precursor having excellent burning resistance since the aluminum plate is hardly reduced in strength when exposed to high temperatures.

In addition, since the size of the crystal grains of the aluminum plate is appropriate, in the etching treatment with an alkaline solution and the electrolytic surface roughening treatment with an alternating waveform current, the reactivity of the etching reaction and the pitting reaction depending on the orientation of the crystal grains is increased. Does not appear remarkably. Therefore, by roughening the aluminum plate by the etching process and the electrolytic surface roughening process, so-called streak,
A lithographic printing plate support having no processing unevenness called surface quality unevenness can be obtained.

According to a second aspect of the present invention, at least one surface of the aluminum plate according to the first aspect is provided with:
(1) a pre-alkali etching step of etching by contacting with an alkaline solution; and (2) electrolytic roughening of the etched aluminum plate in a hydrochloric acid aqueous solution containing hydrochloric acid as a main acid component. The present invention relates to a method for producing a lithographic printing plate support, wherein the surface is roughened by a roughening step having a roughening step.

The lithographic printing plate support obtained by the method for producing a lithographic printing plate support is formed by forming a plate-making layer on a roughened surface which is a surface subjected to a surface roughening treatment.
A lithographic printing plate precursor having excellent burning resistance can be obtained.
The lithographic printing plate precursor has a small decrease in strength even when a burning treatment is performed at a high temperature after exposure and development, and is stiff and easy to handle.

According to a third aspect of the present invention, in the electrolytic surface roughening step, hydrochloric acid and aluminum ions are contained at concentrations of 5 to 15 g / liter and 1 to 15 g / liter, respectively, and the liquid temperature is 20 to 15 g / liter. The present invention relates to a method for producing a lithographic printing plate support that is subjected to electrolytic surface roughening treatment in a 50 ° C. aqueous hydrochloric acid solution.

According to the method for producing a lithographic printing plate support, honeycomb pits in which small holes are densely arranged in a honeycomb shape are particularly uniformly formed on the roughened surface of the aluminum plate.

According to a fourth aspect of the present invention, in the electrolytic roughening step, an alternating waveform current is applied to the aluminum plate so that the total amount of electricity when the aluminum plate is an anode is 10 to 1000 C / dm ^2. The present invention relates to a method for producing a lithographic printing plate support in which an electrolytic surface roughening treatment is performed by applying a voltage.

According to the method for producing a lithographic printing plate support, honeycomb pits having particularly high uniformity can be formed on the surface of the aluminum plate.

According to a fifth aspect of the present invention, the frequency of the alternating waveform current is 40 to 120 Hz, and the time from when the current reaches 0 to a positive or negative peak is 0.5 to 6 ms.
ec, wherein the current density at the positive or negative peak is a trapezoidal wave current of ²⁰ to 100 A / dm ² .

According to the method for producing a lithographic printing plate support,
Not only can a uniform electrolytic surface roughening process be performed,
The power supply device can be configured at low cost.

According to a sixth aspect of the present invention, there is provided a second-stage alkali etching step in which an alkali solution is brought into contact with the aluminum plate which has been subjected to the electrolytic surface roughening process in the electrolytic surface roughening step to perform an etching process; The present invention relates to a method for producing a lithographic printing plate support, which comprises one of a post-electrolysis desmutting step in which an acidic solution is brought into contact with the aluminum plate which has been subjected to electrolytic surface roughening treatment in the step and desmutting is performed.

In the electrolytic roughening step, a film of aluminum hydroxide is formed on the surface of the aluminum plate by a cathode reaction, and the film of aluminum hydroxide is dissolved and removed in the subsequent alkaline etching step. Is done. On the other hand, the concavities and convexities formed in the electrolytic surface roughening step can be appropriately left by appropriately selecting the composition, the liquid temperature, and the contact time of the alkaline solution in the subsequent alkaline etching step.

Therefore, when the anodic oxidation step is performed subsequent to the roughening step, a particularly uniform anodic oxide film can be formed on the surface of the aluminum plate.

The invention according to claim 7, wherein in the roughening step, a pre-stage desmutting step in which the aluminum plate etched in the pre-stage alkali etching step is brought into contact with an acidic solution to perform a desmutting process; The present invention relates to a method for producing a lithographic printing plate support, comprising at least one of a subsequent desmutting step in which the aluminum plate etched in the etching step is brought into contact with an acidic solution and desmutted.

When the aluminum plate is etched with an alkaline solution, Fe contained in the aluminum plate is removed.
May change to hydroxide and precipitate on the surface of the aluminum plate as a black smut.

However, in the method for producing a lithographic printing plate support, the aluminum plate etched in the first alkali etching step or the second alkali etching step is treated with an acidic solution in the first desmutting step or the second desmutting step. Thereby, the smut is dissolved and removed in the acidic solution.

According to the present invention, in the desmutting step after the electrolysis, the aluminum plate may have a sulfuric acid concentration of 100 to 500 g / liter and a liquid temperature of 60 g / l.
The present invention relates to a method for producing a lithographic printing plate support, which is brought into contact with a sulfuric acid aqueous solution at ~ 90 ° C for 1-180 seconds.

In the method for producing a support for a lithographic printing plate, the sulfuric acid solution is used in the desmutting step after the electrolysis, whereby the smut generated on the surface of the aluminum plate in the electrolytic surface roughening step is particularly effectively treated. Can be removed.

According to a ninth aspect of the present invention, in the desmutting treatment, the aluminum plate is treated with a sulfuric acid concentration of 2%.
50-500 g / liter, liquid temperature 60-90 ° C
A lithographic printing plate support that is brought into contact with an aqueous sulfuric acid solution for 1 to 180 seconds.

In the method for producing a lithographic printing plate support, by performing the desmut treatment under the above conditions, the smut generated on the surface of the aluminum plate in the first alkali etching step or the second alkali etching step can be particularly effectively reduced. Can be removed.

In the case where the anodic oxidation step is performed after the latter-stage desmutting step, if the sulfuric acid solution is used in the latter-stage desmutting step, the anodic oxidation processing can be immediately performed without washing the aluminum plate after the desmutting step. Can be. Therefore, there is no need to provide a cleaning line between the line for the surface roughening step and the line for the anodic oxidation step.

According to a tenth aspect of the present invention, in the roughening step, a mechanical surface roughening treatment is performed on a surface of the aluminum plate to be roughened before the etching treatment is performed in the pre-alkali etching step. The present invention relates to a method for producing a lithographic printing plate support having a mechanical roughening step.

In the method for producing a support for a lithographic printing plate, a uniform and non-directional grain can be formed on the surface of the aluminum plate by the mechanical roughening treatment.
The roughened surface formed in the roughening process is excellent in water retention. Therefore, the lithographic printing plate support obtained by the above production method becomes a lithographic printing plate support excellent in water-ink balance.

An invention according to claim 11, wherein the aluminum plate roughened in the roughening step is anodized to form an anodized film on the roughened surface of the aluminum plate. And a method for producing a lithographic printing plate support comprising:

According to the method of manufacturing a lithographic printing plate support, a high hardness and dense anodic oxide film is formed on the roughened surface of the aluminum plate. A lithographic printing plate using a printing plate support as a support is particularly excellent in the durability of the non-image area.

A twelfth aspect of the present invention relates to a method for producing a lithographic printing plate support, wherein in the anodizing step, a hydrophilic treatment for hydrophilizing an anodic oxide film formed on the surface of the aluminum plate is performed. .

The lithographic printing plate support obtained by the above-mentioned method for producing a lithographic printing plate support is particularly excellent in adhesion between the anodic oxide film and the plate-making layer.

According to a thirteenth aspect of the present invention, there is provided a lithographic printing plate support, wherein, in the anodizing step, a sealing treatment is performed to seal small holes in the anodized film formed on the surface of the aluminum plate. About the method.

A lithographic printing plate using the lithographic printing plate support produced by the method for producing a lithographic printing plate support has excellent image quality because a plate-making layer hardly remains in a non-image area after development. Printed matter is obtained.

According to a fourteenth aspect of the present invention, after at least one of the roughening step and the anodic oxidation step is completed, particulate dry ice is sprayed on the roughened surface of the aluminum plate. The present invention relates to a method for producing a lithographic printing plate support to be washed.

In the method of manufacturing a support for a lithographic printing plate, a treatment liquid such as an alkaline solution or an acidic solution adhered to the aluminum plate in each step is recovered by the dry ice washing without being diluted. So
It is extremely easy to reuse and treat the recovered alkaline solution and acidic solution.

According to the fifteenth aspect of the present invention,
4. A lithographic printing plate support produced by the production method according to any one of 4.

By forming a plate making layer on the roughened surface of the lithographic printing plate support, a lithographic printing plate precursor having excellent burning resistance can be obtained.

According to a sixteenth aspect of the present invention, there is provided a lithographic printing original plate characterized in that a plate making layer is formed on a roughened surface of the lithographic printing plate support of the fifteenth aspect.

Since the lithographic printing plate precursor has excellent burning resistance, the lithographic printing plate prepared from the lithographic printing plate precursor does not become weak even when subjected to burning at a high temperature. It has the feature that the grip part fixed to the plate cylinder at the time of mounting on the plate cylinder of the offset printing machine is not cut, and there is no trouble such as printing misalignment due to stretching or deformation during printing. .

[0043]

BEST MODE FOR CARRYING OUT THE INVENTION Aluminum plate As described above, the aluminum plate used in the present invention includes Fe, Si, Cu, Ti, Mg, Mn, and Z.
n is represented by the following ratios: Fe: 0.05 to 0.5% by weight, Si: 0.02 to 0.2% by weight, Cu: 0.00
1 to 0.05% by weight, Ti: 0.003 to 0.04% by weight, Mg: 0.001 to 0.3% by weight, Mn: 0.00
1 to 0.05% by weight, and Zn: 0.001 to 0.0
It is contained at a ratio of 5% by weight.

The remainder of the aluminum plate may be made only of aluminum or may contain unavoidable impurities. However, the content of aluminum is preferably 95% by weight or more, and particularly preferably 99% by weight or more.

The aluminum plate is also 5
At a depth of 0 μm or less, the width of the crystal grains is 20 to 200.
μm. Here, the width of the crystal grain is a dimension in the width direction of the crystal grain. Further, the crystal grains have a length of 40-5.
It is preferably 00 μm. Here, the length of the crystal grain is a dimension in the longitudinal direction of the crystal grain.

The length and width of the crystal grains are, for example,
Buffing to finish to the extent that scratches are not visually observed, etching the surface with aqueous hydrogen fluoride solution, washing with water
After drying, it can be measured by visual observation or photography with an optical microscope equipped with a polarizing filter.

The aluminum plate is, for example, appropriately subjected to a rolling treatment or a heat treatment on an ingot obtained by casting a base metal of an aluminum alloy having the above-described composition by a conventional method, to a thickness of 0.1 to 0.7.
mm and hot-rolled and cold-rolled, and if necessary, flattening treatment.

The method for producing the ingot is DC
In the casting method and the DC casting method, a method in which at least one of the soaking heat treatment and the annealing treatment is omitted, and a continuous casting method can be used.

The aluminum plate may be a continuous band-like sheet material or an aluminum web which is a plate material, or may be a sheet-like sheet cut to a size corresponding to a lithographic printing original plate to be shipped as a product. Good. The thickness of the aluminum web and the sheet-like sheet is usually about 0.05 to 1 mm, preferably in the range of 0.1 to 0.5 mm.

2. Roughening step The method for producing a lithographic printing plate support according to the present invention may have only a roughening step of roughening the surface of the aluminum plate, in addition to the roughening step, The method may include an anodizing step of anodizing the surface of the aluminum plate roughened in the roughening step.

Since various elements contained in the aluminum plate to be roughened are dissolved in the processing solution such as an alkaline solution and an acidic solution used in the surface roughening process, the processing solution is Of course, the element may be contained in advance. In addition, it is preferable to predict the concentrations of these elements in a steady state, and to add in advance an amount of the elements corresponding to the prediction result.

The surface roughening step includes at least (1) a preliminary alkali etching step and (2) an electrolytic surface roughening step.

The surface roughening step may comprise (1) a first-stage alkali etching step, (2) an electrolytic roughening step, and (3) a second-stage alkali etching step. Alternatively, a desmutting step after electrolysis may be provided.

The roughening step further comprises: (1) a pre-stage alkali etching step, (1a) a pre-stage desmutting step,
It may include (2) electrolytic surface roughening step, (3) post-stage alkali etching step, and (3a) post-stage desmutting step.

In addition, in the surface roughening step, (4) a mechanical surface roughening step may be provided before the first-stage alkali etching step (1).

The first-stage alkali etching step (1), the electrolytic roughening step (2), the second-stage alkali etching step (3), the first-stage desmutting step (1a), the second-stage desmutting step (3a), and the mechanical roughening step ( Each of 4) will be described in detail below.

(2-1) Pre-Alkali Etching Step (1) In the pre-alkali etching step, an etching treatment is performed by bringing the aluminum plate into contact with an alkali solution.

As a method of bringing the aluminum plate into contact with the alkaline solution, for example, a method of continuously passing through the tank containing the alkaline solution, a method of immersing it in the tank containing the alkaline solution, and a method of contacting the alkaline solution with the alkaline solution There is a method of spraying on the surface of the aluminum plate.

The etching amount is determined on the roughened surface, that is, the surface on the side to be electrolytically roughened in the next electrolytic roughening step.
The range of 1 to 15 g / m ² is preferable, and the range of 0.1 to 5 g / m ² (about 10 to 40% of the etching amount on the roughened surface) is preferable on the surface opposite to the surface. If the etching amount is within the above range, the oils and fats attached to the surface of the aluminum plate during the rolling are almost completely removed, so that the water retention in the non-image portion is high, and the ink adheres to the non-image portion. As a result, a lithographic printing plate precursor that does not cause appearance defects such as so-called blank stains can be obtained.

Examples of the alkali solution include solutions of caustic alkali and alkali metal salts. The concentration of caustic and alkali metal salts in the solution is
It can be determined based on the etching amount.
It is preferably from 50 to 50% by weight, particularly preferably from 10 to 35% by weight. When the alkaline solution contains aluminum ions, the concentration of the aluminum ions is set to 0.1.
The range is preferably from 01 to 10% by weight, particularly preferably from 3 to 8% by weight.

The temperature of the alkaline solution is preferably in the range of 20 to 90 ° C.

Examples of the caustic alkali include sodium hydroxide and potassium hydroxide.

Examples of the alkali metal salt include alkali metal silicates such as sodium metasilicate, sodium silicate, potassium metasilicate and potassium silicate, alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium aluminate and potassium aluminate. Such as alkali metal aluminates, alkali metal aldonates such as sodium gluconate and potassium gluconate, and sodium diphosphate, potassium diphosphate, tertiary sodium phosphate,
And alkali metal hydrogen phosphates such as potassium tertiary phosphate. As the alkali solution, a solution of caustic alkali and a solution of the caustic alkali and an alkali metal aluminate are particularly preferable in terms of high etching rate and low cost.

The etching treatment can be performed using an etching bath usually used for etching an aluminum plate. As the etching tank, any of a batch type and a continuous type can be used. Further, instead of the etching tank, a spray device for spraying the alkaline solution onto an aluminum plate may be used.

(2-2) Electrolytic Surface Roughening Step (2) In the electrolytic surface roughening step, the aluminum plate is subjected to electrolytic surface roughening treatment in an aqueous hydrochloric acid solution by alternating current or direct current.

The concentration of hydrochloric acid in the aqueous hydrochloric acid solution is 5 to 1
A range of 5 g / liter is preferable, and a range of 5 to 10 g / liter is particularly preferable. The concentration of aluminum ions is preferably in the range of 1 to 15 g / liter, and particularly preferably in the range of 1 to 7 g / liter. The concentration of the aluminum ion can be adjusted by adding aluminum chloride to the aqueous hydrochloric acid solution.

The aqueous hydrochloric acid solution may further contain at least one of sodium chloride and ammonium chloride, and may contain Fe, Si, Cu, Mg, Mn, Zn,
Cr and Ti ions may be contained.

The liquid temperature is preferably from 20 to 50 ° C.

In the electrolytic surface roughening step, a direct current may be applied to the aluminum plate, but it is preferable to apply an alternating waveform current. As the alternating waveform current,
Examples include a sine wave current, a rectangular wave current, a triangular wave current, and a trapezoidal wave current. Among them, a sine wave current and a trapezoidal wave current are preferable. The alternating waveform current is a single-phase, two-phase,
Alternatively, a three-phase current may be applied, and a current obtained by superimposing the alternating waveform current and a direct current may be applied.

The frequency of the alternating waveform current is preferably 40 to 120 Hz from the viewpoint of the cost of manufacturing the power supply device.

The ratio Qc / Qa of the quantity of electricity when the aluminum plate becomes an anode, ie, the quantity of electricity Qa at the time of anode, and the quantity of electricity when it becomes a cathode, ie, quantity of electricity Qc at the time of cathode, is 0.9.
It is preferable to be within the range of 1 to 1 because uniform honeycomb pits can be generated on the surface of the aluminum plate.
In particular, it is preferable that the Qc / Qa is in the range of 0.95 to 0.99. When the electrolytic surface roughening treatment is performed in an AC electrolytic cell having an auxiliary electrode for shunting the anode current of the main electrode, Japanese Patent Application Laid-Open Nos.
As described in JP-A-52098, the ratio Qc / Qa can be controlled by controlling the current value of the anode current shunted to the auxiliary electrode.

The duty of the alternating waveform current is most preferably 0.5 from the viewpoint of uniformly roughening the surface of the aluminum plate and the convenience in manufacturing the power supply device. The duty in the present invention is defined as the time during which an aluminum plate undergoes an anodic reaction (anode reaction time) in a cycle T of an alternating waveform current.
It means ta / T when a is used.

At the time of the cathode reaction, an oxide film mainly composed of aluminum hydroxide is formed on the surface of the aluminum plate, and further, the oxide film may be dissolved or broken. When the oxide film dissolves or breaks, the portion where the dissolution or break occurs becomes a starting point of the pitting reaction at the time of the next anodic reaction of the aluminum plate. Therefore, the selection of the duty of the alternating waveform current is particularly important from the viewpoint of performing a uniform electrolytic surface roughening treatment.

The time tp required for the current value of the alternating waveform current to reach a positive or negative peak from 0 is 0.5 to 0.5 when the alternating waveform current is a trapezoidal current.
The range of 6 msec is preferable, and in particular, 1.5 to 5 msec.
Is preferable. When the time tp is within the above range, more uniform crater-shaped concave portions (pits) are formed on the surface of the aluminum plate.

The amount of electricity from the start to the end of the electrolytic graining treatment is preferably in the range of 10 to 1000 C / dm ^{2 in} total when the aluminum plate is the anode.
Particularly, a range of 40 to 500 C / dm ² is preferable.

In the alternating waveform current, the peak current Iap on the anode cycle side and the peak current Icp on the cathode cycle side are both 20 to 100 A.
/ Dm ² is preferred. Also, Icp / Iap is 0.9
~ 1.5, preferably 0.9 ~ 1.
A range of 0 is particularly preferred.

In the electrolytic surface roughening treatment, an electrolytic surface roughening apparatus having various types of AC electrolytic cells such as a vertical type, a flat type, and a radial type can be used. As the electrolytic surface roughening apparatus, an apparatus having a flat type or radial type AC electrolytic cell is most preferable.

An electrolytic surface roughening apparatus in which a plurality of the AC electrolytic cells are arranged in series is also preferable.

In the case where an electrolytic surface roughening device having one AC electrolytic cell is used in the electrolytic surface roughening treatment, the aluminum plate passes between the electrodes of the AC electrolytic cell to form an alternating waveform. It is preferable that at least one pause period in which no current flows is provided and the length of the pause period is set to 0.001 seconds to 0.6 seconds or less, since honeycomb pits are uniformly formed on the entire surface of the aluminum plate.

In the case of using an electrolytic surface roughening apparatus having a plurality of AC electrolytic cells arranged in series, a time period during which no current is supplied to the aluminum plate between one AC electrolytic cell and another AC electrolytic cell is 10 minutes. It is preferable to arrange each AC electrolytic cell and set the transport speed of the aluminum plate so that the time is not more than seconds, particularly preferably not more than 5 seconds.

FIG. 1 shows an example of an electrolytic surface roughening apparatus having a flat type AC electrolytic cell.

As shown in FIG. 1, the electrolytic surface roughening apparatus 100 conveys the aluminum web W in a substantially horizontal direction while alternating a three-phase alternating current (hereinafter referred to as a "three-phase alternating current").
This is an electrolytic surface roughening device for applying an electric field to make the surface rough.

The electrolytic surface roughening apparatus 100 includes a shallow box-shaped AC electrolytic cell 2 extending in the transport direction a of the aluminum web W and having an open upper surface. Three plate-shaped main poles 4A, 4B, and 4C arranged in parallel with the transfer surface T, which is a transfer path of the aluminum web W, along the transfer direction a, and the transfer direction inside the AC electrolytic cell 2. The aluminum web W is disposed near the upstream (hereinafter, referred to as “upstream”) and downstream (hereinafter, referred to as “downstream”) ends, and conveys the aluminum web W inside the AC electrolytic cell 2. Transport rollers 6A and 6B
And an introduction roller 8A that is located on the upstream side above the AC electrolytic cell 2 and introduces the aluminum web W into the inside of the AC electrolytic cell 2, and that is located on the downstream side above the AC electrolytic cell 2, A lead roller 8B is provided to lead the aluminum web W passing through the inside to the outside of the AC electrolytic cell 2.

The main poles 4A, 4B, and 4C are respectively connected to a U terminal, a V terminal of a three-phase power supply for generating a three-phase alternating waveform current.
Terminal and the W terminal. Therefore, the alternating waveform currents applied to main poles 4A, 4B, and 4C are out of phase by 120 °.

The operation of the electrolytic surface roughening apparatus 100 will be described below.

[0086] The aluminum web W is introduced into the introduction roller 8A.
Is introduced into the AC electrolytic cell 2 by the transport roller 6
A and 6B convey at a constant speed along the conveying direction a.

Inside the AC electrolytic cell 2, the aluminum web W moves parallel to the main poles 4A, 4B, and 4C, and receives an alternating waveform current from the main poles 4A, 4B, and 4C. Thereby, in the aluminum web W, an anodic reaction and a cathodic reaction occur alternately. When an anodic reaction occurs, a honeycomb pit mainly occurs, and when a cathodic reaction occurs, a film of aluminum hydroxide mainly forms. Are generated and the surface is roughened.

In the electrolytic surface roughening apparatus, the main electrode 4
Since the alternating waveform currents applied to A, 4B and 4C are out of phase by 120 ° as described above,
In B, the anodic reaction and the cathodic reaction are repeated at a phase delayed by 120 ° from the main electrode 4A, and the anodic reaction and the cathodic reaction are repeated at the main electrode 4C at a phase delayed by 120 ° from the main electrode 4B. It is.

Therefore, as a whole, the anodic reaction and the cathodic reaction are repeated three times as frequently as the case where a single-phase alternating waveform current having the same frequency is applied to the entire aluminum web W. Even when the electrolytic surface roughening treatment is performed at a current density, chatter marks, which are stripes in the width direction, hardly occur.

FIG. 2 shows another example of an electrolytic surface roughening apparatus having a flat type AC electrolytic cell. 2, the same reference numerals as those in FIG. 1 indicate the same elements as those shown in FIG.

As shown in FIG. 2, the electrolytic graining device 102 is an electrolytic graining device in which an auxiliary electrolytic cell 10 is disposed at a stage subsequent to the AC electrolytic cell 2 provided in the electrolytic graining device 100.

The auxiliary electrolytic cell 10 has a box shape with an open upper surface, and has a transport surface T of the aluminum web W near the bottom surface.
A plate-shaped auxiliary electrode 12 is provided in parallel to the auxiliary electrode 12.

The transport rollers 14 A and 14 B for transporting the aluminum web W above the auxiliary electrode 12 are located near the upstream side wall and the downstream side wall of the auxiliary electrolytic cell 10.
Are arranged. On the upstream side above the auxiliary electrolytic cell 10, an aluminum web W is
Is provided on the downstream side above the auxiliary electrolytic cell 10, and a lead-out roller 16B is provided on the downstream side above the auxiliary electrolytic cell 10 to discharge the aluminum web W having passed through the inside of the auxiliary electrolytic cell 10.

The U-phase, V-phase and V-phase of the power supply Tac are connected to the auxiliary electrode 12, respectively, and are connected to the U-phase, V-phase and V-phase.
A thyristor Th is provided between the phase and the auxiliary electrode 12.
1, Th2 and Th3 are interposed. The thyristors Th1, Th2, and Th3 are all connected so that current flows from the power supply Tac toward the auxiliary electrode 12 at the time of ignition. Therefore, the thyristors Th1, T
Regardless of which of h2 and Th3 is fired, the anode current flows through the auxiliary electrode 12, so that the thyristors Th1 and Th1
2. By controlling the phase of Th3, the current value of the anode current flowing through the auxiliary electrode 12 can be controlled.
Qc / Qa can also be controlled.

FIG. 3 shows an example of an electrolytic surface roughening apparatus having a radial type AC electrolytic cell.

As shown in FIG. 3, the electrolytic surface roughening device 104 includes an AC electrolytic cell 20 having an AC electrolytic cell main body 22 for storing an aqueous hydrochloric acid solution, and an AC electrolytic cell main body 22 housed inside the AC electrolytic cell main body 22 and extending in a horizontal direction. A feed roller 24 is disposed rotatably about the extending axis and feeds the aluminum web W in the direction of arrow a, that is, from left to right in FIG.

The inner wall surface of the AC electrolytic cell main body 22 is formed in a substantially cylindrical shape so as to surround the feed roller 24. On the inner wall surface, semi-cylindrical main poles 26A and 26B are sandwiched by the feed roller 24. Is provided. Main poles 26A and 26B
Is divided into a plurality of small electrodes, and an insulating spacer is interposed between each of the small electrodes. The small electrode can be formed by using, for example, graphite or metal, and the spacer can be formed by, for example, a vinyl chloride resin. The thickness of the spacer is 1 to 10 mm
Is preferred. Although not shown in FIG.
In each of 6A and 26B, each of the electrodes divided by the spacer is connected to an AC power supply AC.

An opening 22 A for introducing and leading the aluminum web W into and out of the AC electrolytic cell main body 22 is formed in the upper part of the AC electrolytic cell 20. In the vicinity of the opening 22A in the AC electrolytic cell main body 22, a liquid supply nozzle 28A for replenishing the AC electrolytic cell main body 22 with an aqueous hydrochloric acid solution is provided. On the other hand, between the main electrode 26A and the main electrode 26B of the AC electrolytic cell main body 22, a liquid supply nozzle 28B for replenishing the AC electrolytic cell main body 22 with the hydrochloric acid aqueous solution is similarly provided.

Opening 22 above AC electrolytic cell 20
In the vicinity of A, the aluminum web W is placed in the AC
2, an upstream guide roller 30A for guiding the inside and a group of downstream guide rollers 30B for guiding the aluminum plate W electrolyzed in the AC electrolytic cell main body 22 to the outside are provided.

In the AC electrolytic cell 20, an overflow tank 32 is provided adjacent to the downstream side of the AC electrolytic cell main body 22. The overflow tank 32 has a function of temporarily storing the hydrochloric acid aqueous solution overflowing from the AC electrolytic cell main body 22 and maintaining the level of the hydrochloric acid aqueous solution in the AC electrolytic tank main body 22 at a constant level.

An auxiliary electrolytic cell 34 is provided downstream of the overflow tank 32.
Is provided. The auxiliary electrolytic cell 34 is shallower than the AC electrolytic cell main body 22 and has a flat bottom surface 34A. An auxiliary liquid supply nozzle 38 for supplying an aqueous hydrochloric acid solution to the auxiliary electrolytic cell 34 is provided near the upstream side wall surface of the auxiliary electrolytic cell 34, and an aqueous hydrochloric acid solution supplied from the auxiliary liquid supply nozzle 38 is provided near the upstream side wall surface. An overflow weir 34B that overflows and holds the level of the aqueous hydrochloric acid solution in the auxiliary electrolytic tank 34 at a constant height is provided. A plurality of columnar auxiliary electrodes 36 are provided on the bottom surface 34A.

The auxiliary electrode 36 is preferably formed of a highly corrosion-resistant metal such as platinum or ferrite, or may be plate-shaped.

The auxiliary electrode 36 is connected in parallel with the main pole 26B on the side to which the main pole 26B of the AC power supply AC is connected. In the middle, the thyristor Th4 is connected to the AC power supply AC during ignition. The connection is made such that a current flows from the side to the auxiliary electrode 36.

The side of the AC power supply AC to which the main electrode 26A is connected is also connected to the auxiliary electrode 3 via the thyristor Th5.
6 is connected. The thyristor Th5 is also connected so that a current flows from the side of the AC power supply AC to which the main electrode 26A is connected to the auxiliary electrode 36 at the time of ignition.

When the thyristors Th4 and Th5 are fired, an anode current flows through the auxiliary electrode. Therefore, by controlling the phase of the thyristors Th4 and Th5, the current value of the anode current flowing through the auxiliary electrode 36 can be controlled, and therefore, Qc / Qa can also be controlled.

The function of the electrolytic surface roughening device 104 will be described below.

The aluminum plate W guided to the AC electrolytic cell 20 from the left in FIG. 3 is first guided to the electrolytic cell main body 22 by the upstream guide roller 30A. Then, the paper is fed from the left side to the right side in FIG. 3 by the feed roller 24, and is guided into the auxiliary electrolytic cell 34 by the downstream side guide roller 30B.

AC electrolytic cell main body 22 and auxiliary electrolytic cell 34
Inside, the surface of the aluminum plate W facing the main electrodes 6A and 6B is roughened by the alternating current applied to the main electrodes 26A and 26B and the anode current applied to the auxiliary electrode 36, Almost uniform honeycomb pits are formed.

(2-3) Second-stage alkali etching step (3) In the second-stage alkali etching step, an alkali solution such as a solution of caustic alkali and an alkali metal salt is sprayed onto the aluminum plate, as in the first-stage alkali etching step. Alternatively, it can be carried out by immersing in the alkaline solution or passing through the alkaline solution.

The concentration of the caustic alkali and alkali metal salt in the alkaline solution is preferably 0.01 to 30% by weight, and the temperature is preferably in the range of 20 to 90 ° C.

The amount of etching is preferably in the range of 0.01 to 1 g / m ² .

The etching treatment can be performed using the same etching bath or spray device as described in the preceding alkaline etching step.

(2-4) First Desmutting Step (1a) and Second Desmutting Step (3a) It is preferable to perform desmutting processing after the first and second alkali etching steps (1) and (3).

The desmutting treatment can be performed by immersing the aluminum plate in the acidic solution or passing the aluminum plate through the acidic solution. The acidic solution may be sprayed on the aluminum plate.

In the former desmutting step (1a), it is preferable to use a waste solution of the hydrochloric acid solution discharged in the electrolytic graining step (2) as the acidic solution, and in the latter desmutting step (3a), As the solution, it is preferable to use a sulfuric acid solution discharged in a subsequent anodizing treatment step.

In the subsequent desmutting step (3a), instead of using the waste liquid of the sulfuric acid solution, the concentration of sulfuric acid is 100 to 600 g / l, aluminum ions are contained at 1 to 10 g / l, and The desmutting treatment may be performed using a sulfuric acid solution having a temperature of 60 to 90 ° C.

In the case where a post-electrolysis desmutting step is performed instead of the latter-stage alkaline etching step,
Also in the post-electrolysis desmutting step, the same desmutting treatment as in the former-stage desmutting step (1a) and the latter-stage desmutting step (3a) can be performed.

(2-5) Mechanical Surface Roughening Step (4) In the mechanical surface roughening step, the surface of the cylindrical body is coated with a synthetic resin such as nylon (trade name), propylene, or vinyl chloride resin. It is common to apply a mechanical surface roughening treatment to mechanically roughen one or both surfaces of the aluminum plate by using a roller-like brush in which a large number of brush hairs such as synthetic resin hairs are implanted. is there. Further, in the mechanical surface roughening treatment, the aluminum plate may be roughened using a polishing roller, which is a roller having a polishing layer on the surface, instead of the roller brush. When a roller-shaped brush is used, a mechanical roughening process can be performed while spraying an abrasive slurry liquid described later on the rotating roller-shaped brush.

The length of the bristles in the roller brush can be appropriately determined according to the outer diameter of the roller brush and the diameter of the body.
The range is 0 mm.

As abrasives, silica sand and pumice stone are used. Silica sand is harder than pumice stone and hard to break, so that it is preferable because the surface of the aluminum plate can be sharpened very efficiently.

The average particle size of the abrasive is from 3 to 4 from the viewpoint that the roughening efficiency is high and the graining pitch can be narrowed.
A range of 0 μm is preferred, and a range of 6 to 30 μm is particularly preferred.

The abrasive can be used, for example, as a polishing slurry liquid suspended in water. The polishing slurry liquid may further contain a thickener, a dispersant such as a surfactant, a preservative, and the like.

(3) Anodizing Step In the present invention, it is preferable to subject the aluminum plate to a roughening treatment and then to perform an anodizing treatment.

In the anodizing step, the aluminum plate subjected to the surface roughening treatment is anodized according to a conventional method.

In the anodic oxidation treatment, for example, in an acidic electrolyte containing at least one of sulfuric acid, phosphoric acid, oxalic acid, chromic acid and amidosulfonic acid as an acid component,
DC, pulsating or alternating current is applied to the aluminum plate.

The conditions of the anodizing treatment vary depending on the composition of the acidic electrolytic solution to be used, and thus cannot be specified unconditionally. The temperature is preferably in the range of 5 to 70 ° C. The current density is preferably in the range of 1 to 60 A / dm ² , and the voltage is preferably in the range of 1 to 100 V. The electrolysis time is 10
A range of 300 seconds is appropriate.

As the acidic electrolyte, JP-A-54-1
As described in No. 2853 and JP-A-48-45303, those containing sulfuric acid as an acid component are preferred.

The concentration of sulfuric acid in the acidic electrolyte is 10 to
The concentration is preferably 300 g / liter (1 to 30% by weight), and the concentration of aluminum ion is preferably 1 to 25 g / liter (0.1 to 2.5% by weight), and particularly preferably 2 to 10 g.
/ Liter (0.2-1% by weight) is preferred. Such an acidic electrolyte has a sulfuric acid concentration of 50 to 2 for example.
It can be prepared by adding aluminum to 00 g / liter diluted sulfuric acid.

When performing the anodic oxidation treatment in the acidic electrolytic solution containing sulfuric acid, a direct current or an alternating current may be applied to the aluminum plate.

[0130] When applying a DC to the aluminum plate, the current density is preferably in the range of 1 to 60 A / dm ^2, in particular in the range of 5 to 40 A / dm ² is preferred.

In the case where the anodic oxidation treatment is performed continuously,
So-called "burn" when current is partially concentrated on the aluminum plate
In the beginning of the anodizing treatment, 5
Applying a current at a low current density of 10 A / dm ^2, as the anodizing treatment proceeds, it is preferable to increase the current density 30~50A / dm ² or more, the.

In the above case, it is preferable that the aluminum plate is subjected to anodizing treatment by a liquid supply system for supplying power through the acidic electrolytic solution. Further, as the electrode for supplying power to the aluminum plate, an electrode formed of lead, iridium oxide, platinum, ferrite, or the like can be used. Among the electrodes, an electrode mainly formed of iridium oxide and an electrode in which the surface of a substrate is coated with iridium oxide are preferable. As a substrate coated with iridium oxide, a so-called valve metal such as titanium, tantalum, niobium, and zirconium is preferable, and titanium and niobium are particularly preferable. Since the valve metal has relatively high electric resistance, the base material may be formed by cladding the valve metal on a surface of a core material made of copper. In the case of cladding the valve metal on the surface of a core material made of copper, a base material having a too complicated shape is difficult to manufacture,
The base material may be assembled by cladding the valve metal on a core material in a form in which the base material is divided for each component, and then combining the components.

In the anodic oxidation treatment, the amount of the anodic oxide film is 1 to 5
g / m ² is preferred from the viewpoint of the printing durability of the lithographic printing plate. Further, it is preferable to perform the process so that the difference in the amount of the anodic oxide film between the center and the vicinity of the edge of the aluminum plate is 1 g / m ² or less.

In the anodizing treatment, the aluminum plate on which the anodized film has been formed is immersed in an aqueous solution of an alkali metal silicate such as sodium silicate and potassium silicate, or subjected to a hydrophilic treatment. It is preferable to form a hydrophilic undercoat layer by applying a vinyl polymer or a hydrophilic compound.

The hydrophilization treatment with an aqueous solution of an alkali metal silicate such as sodium silicate and potassium silicate is described in US Pat. No. 2,714,066 and US Pat.
181 461, and the formation of the hydrophilic undercoat layer can be performed according to the method and procedure described in the specification of US Pat.
JP-A-59-101651 and JP-A-60-1
It can be carried out in accordance with the conditions and procedures described in US Pat. Examples of the hydrophilic vinyl polymer include polyvinyl sulfonic acid, a vinyl polymerizable compound having a sulfonic acid group such as p-styrenesulfonic acid having a sulfonic acid group, and a normal vinyl polymerizable compound such as an alkyl (meth) acrylate. And a copolymer of
Examples of the hydrophilic compound include a compound having at least one of an NH ₂ group, a —COOH group, and a sulfone group.

Further, the aluminum plate having the anodic oxide film formed thereon may be subjected to a sealing treatment for closing small holes in the anodic oxide film by bringing the aluminum plate into contact with boiling water, hot water or steam.

[0137] 3. Lithographic printing plate precursor A laser beam such as a visible light exposure type plate-making layer or an infrared laser beam for exposing the surface of the lithographic printing plate support prepared by the above-described method on the surface subjected to the surface roughening treatment to ordinary visible light. A lithographic printing original plate can be produced by forming a laser exposure type plate-making layer to be exposed by the above method.

(3-1) Visible light exposure type plate making layer The visible light exposure type plate making layer can be formed of a composition containing a photosensitive resin and, if necessary, a coloring agent.

Examples of the photosensitive resin include a positive photosensitive resin which becomes soluble in a developing solution when exposed to light, and a negative photosensitive resin which becomes insoluble in a developing solution when exposed to light.

Examples of the positive photosensitive resin include a combination of a diazide compound such as a quinonediazide compound and a naphthoquinonediazide compound with a phenol resin such as a phenol novolak resin and a cresol novolak resin.

On the other hand, examples of the negative photosensitive resin include diazo resins such as condensates of aromatic diazonium salts and aldehydes such as formaldehyde, inorganic acid salts of the diazo resins, and the like.
And a diazo compound such as an organic acid salt of the diazo resin,
Combination with a binder such as (meth) acrylate resin, polyamide resin and polyurethane, and (meth)
Examples include a combination of a vinyl polymer such as an acrylate resin and a polystyrene resin, a vinyl polymerizable compound such as a (meth) acrylate ester and styrene, and a photopolymerization initiator such as a benzoin derivative, a benzophenone derivative, and a thioxanthone derivative.

Examples of the coloring agent include ordinary dyes,
Exposure coloring dyes that develop color upon exposure, and exposure decoloring dyes that become almost or completely colorless upon exposure can be used. Examples of the exposure coloring dye include a leuco dye. On the other hand, examples of the exposure decoloring dye include triphenylmethane dyes, diphenylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.

The visible light exposure type plate-making layer can be formed by applying a photosensitive resin solution in which the photosensitive resin and the coloring agent are mixed in a solvent and drying.

Examples of the solvent used in the photosensitive resin solution include a solvent which dissolves the photosensitive resin and has a certain degree of volatility at room temperature. Solvent, ester solvent, ether solvent, glycol ether solvent, amide solvent, carbonate ester solvent and the like.

As the alcohol solvent, ethanol,
And propanol and butanol. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, and diethyl ketone. Examples of the ester solvent include ethyl acetate, propyl acetate, methyl formate, ethyl formate and the like. Examples of ether solvents include tetrahydrofuran and dioxane, and examples of glycol ether solvents include ethyl cellosolve, methyl cellosolve, and butyl cellosolve.
Examples of the amide-based solvent include dimethylformamide and dimethylacetamide. Examples of the carbonate-based solvent include ethylene carbonate, propylene carbonate, diethyl carbonate, and dibutyl carbonate.

As a method for applying the photosensitive resin solution,
Conventionally known methods such as a spin coating method, a wire bar method, a dip coating method, an air knife coating method, a roll coating method, and a blade coating method are exemplified.

(3-2) Laser exposure type plate making layer As the laser exposure type plate making layer, a negative type laser plate making layer in which a portion irradiated with a laser beam remains, and a positive type laser plate making in which a portion irradiated with a laser beam is removed. The main layer includes a layer and a photopolymerization type laser plate making layer which photopolymerizes when irradiated with a laser beam.

The negative type laser plate making layer is composed of (A) an acid precursor which decomposes by heat or light to generate an acid, and (B) an acid which is crosslinked by an acid generated by decomposing the acid precursor (A). It can be formed from a negative type laser plate making layer forming solution in which a crosslinkable compound, (C) an alkali-soluble resin, (D) an infrared absorber, and (E) a phenolic hydroxyl group-containing compound are dissolved or suspended in an appropriate solvent.

Examples of the acid precursor (A) include compounds which decompose by ultraviolet light, visible light or heat to generate sulfonic acid, such as iminophosphate compounds. In addition, a compound generally used as a photocationic polymerization initiator, a photoradical polymerization initiator, or a photochromic agent can also be used as the acid precursor (A).

Examples of the acid-crosslinkable compound (B) include an aromatic compound having at least one of an alkoxymethyl group and a hydroxyl group, a compound having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group, And epoxy compounds.

Examples of the alkali-soluble resin (C) include novolak resins and polymers having a hydroxyaryl group in the side chain such as poly (hydroxystyrene).

As the infrared absorbing agent (D), 760 nm
Dyes and pigments that absorb infrared rays of up to 1200 nm, specifically, black pigments, red pigments, metal pigments, phthalocyanine-based pigments, and azo dyes, anthraquinone dyes, phthalocyanine dyes that absorb infrared rays of the above-mentioned wavelengths, And cyanine dyes.

As the phenolic hydroxyl group-containing compound (E), compounds represented by the general formula (R ₁ -X) _n -Ar- (OH) _m (R ₁ is
X is an alkyl group or alkenyl group having 6 to 32 carbon atoms, X is an end bond, O, S, COO, or CONH; Ar is an aromatic hydrocarbon group, an alicyclic hydrocarbon group,
Or, it is a heterocyclic group, and n and m are each a natural number of 1 to 3. )). Specific examples of the compound include alkylphenols such as nonylphenol.

A plasticizer and the like can be further added to the negative type laser plate making layer forming liquid.

The positive type laser plate making layer is prepared by dissolving or suspending (F) an alkali-soluble polymer, (G) an alkali dissolution inhibitor, and (H) an infrared absorber in an appropriate solvent. It can be formed with a forming liquid.

Examples of the alkali-soluble polymer (F) include a phenolic polymer having a phenolic hydroxyl group such as a phenolic resin, a cresol resin, a novolak resin, a pyrogallol resin, and poly (hydroxystyrene), and at least a part of monomer units. Sulfonamide group-containing polymer which is a polymer having a sulfonamide group, active imide group-containing polymer obtained by homopolymerization or copolymerization of a monomer having an active imide group such as N- (p-toluenesulfonyl) (meth) acrylamide group, etc. Can be used.

Examples of the alkali dissolution inhibitor (G) include compounds which react with the alkali-soluble polymer (F) by heating or the like to decrease the alkali-solubility of the alkali-soluble polymer (F). Examples include a sulfone compound, an ammonium salt, a sulfonium salt, and an amide compound. For example, alkali-soluble polymer (F)
When the above-mentioned novolak resin is used, a cyanine dye which is a kind of a sulfone compound is preferable as the alkali dissolution inhibitor (G).

Examples of the infrared absorbing agent (H) include squarylium dyes, pyrylium dyes, carbon black, insoluble azo dyes, anthraquinone dyes and the like.
Dyes, dyes, and pigments that have an absorption region in the infrared region of 0 nm and have a light / heat conversion ability are included.

The photopolymerization type laser plate making layer can be formed by (I) a photopolymerization type laser plate making layer forming solution containing a vinyl polymerizable compound having an ethylenically unsaturated bond at a molecular terminal. The photopolymerization type laser plate making layer forming liquid may contain (J) a photopolymerization initiator and (K) a sensitizer, if necessary.

Examples of the vinyl polymerizable compound (I) include ethylenically unsaturated carboxylic acids which are esters of ethylenically unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid and maleic acid with aliphatic polyhydric alcohols. Ester,
Examples include ethylenically unsaturated carboxylic acid polyamides such as methylenebis (meth) acrylamide and xylylene (meth) acrylamide comprising the above-mentioned ethylenically unsaturated carboxylic acid and polyamine.

Examples of the vinyl polymerizable compound (I) include aromatic vinyl compounds such as styrene and α-methylstyrene, and ethylenically unsaturated carboxylic acids such as methyl (meth) acrylate and ethyl (meth) acrylate. Acid monoesters can also be used.

As the photopolymerization initiator (J), a photopolymerization initiator usually used for photopolymerization of a vinyl monomer can be used.

Examples of the sensitizer (K) include titanocene compounds, triazine compounds, benzophenone compounds, benzimidazole compounds, cyanine dyes, merocyanine dyes, xanthene dyes, and coumarin dyes.

Solvents used in the negative type laser plate making layer forming liquid, the positive type laser plate making layer forming liquid, or the photopolymerization type laser plate making layer forming liquid, and the negative type laser plate making layer forming liquid, the positive type laser plate making layer The method of applying the forming liquid or the photopolymerization type laser plate making layer forming liquid is the same as the solvent and the coating method described in “(3-1) Visible light exposure type plate making layer”.

When forming the photopolymerizable laser plate making layer, a silicone compound having a reactive functional group such as a partially decomposed silane compound obtained by partially decomposing a silane compound with water, alcohol or carboxylic acid is used. If the roughened surface of the lithographic printing plate support is treated in advance, the adhesion between the lithographic printing plate support and the photopolymerizable laser plate-making layer is preferably improved.

(3-3) Plate Making The lithographic printing original plate is cut into an appropriate size as required, exposed and developed to make a plate.

In the case of a lithographic printing original plate having a photosensitive plate-making layer, a plate can be made by overlaying a transparent film on which a printed image is formed, exposing the film with ordinary visible light, and then performing development.

In the case of a lithographic printing original plate having a laser-exposed type plate-making layer, the plate can be made by irradiating various laser beams to directly write the printed image, exposing it, and then developing it.

[0169]

The present invention will be described in more detail with reference to the following examples.

Example 1 << Preparation of Support for Lithographic Printing Plate >> A molten aluminum ingot having the composition shown in Table 1 was degassed, filtered, and then cast by an ordinary method to obtain an ingot. Obtained.

[0171]

[Table 1]

Both sides of the obtained ingot were chamfered to a thickness of 500
mm, width 1000 mm, and length 3500 mm, a soaking treatment was performed, and an aluminum alloy plate having a thickness of 1.5 mm was obtained by hot rolling and cold rolling.

The above aluminum alloy plate was heated at 360 ° C. for 1 hour.
Intermediate annealing treatment was performed for a period of time, finish cold rolling was performed at a rolling reduction of 80%, and finish annealing treatment was performed to obtain an aluminum web having a thickness of 0.3 mm.

The aluminum web was buffed to such an extent that no scratches were visually observed, and then 10% room temperature.
Etching was performed with an HF aqueous solution for 45 seconds. Using an optical microscope, the surface of this aluminum web was observed at a magnification of 15 times through a polarizing filter.
The following aluminum crystal grains were found on the entire surface.

1. Roughening The aluminum web was subjected to a roughening treatment comprising the following steps.

(1) First-stage alkali etching step (1a) First-stage desmutting step (2) Electrolytic surface-roughening step (3) Second-stage alkali etching step (3a) Second-stage desmutting step Each time each of the above steps is completed, treatment is performed with a nip roller. The solution was drained and washed with water. The rinsing was performed by using a rinsing nozzle provided with a spray tip for drawing a fan-shaped spray pattern on a tube at an interval of 100 mm, and spraying water from both sides of the aluminum web from the rinsing nozzle. The washing nozzle has a distance of 100 from a discharge port of the spray tip to a conveying surface of the aluminum web.
mm. Further, after the water washing treatment, water droplets adhering to the surface of the aluminum web were cut by a nip roller.

In the first-stage alkali etching step (1), the first-stage desmutting step (1a), the second-stage alkali etching step (3), and the second-stage desmutting step (3a), a treatment liquid was sprayed on both surfaces of the aluminum web. In these steps, a treatment liquid spray nozzle having an injection hole having a diameter of 4 mm was formed in a tube at intervals of 50 mm to spray the treatment liquid onto the aluminum web. The processing liquid spray nozzle has a distance of 50 m from the injection hole to the conveying surface of the aluminum web.
m.

The steps from the first alkali etching step (1) to the second desmutting step (3a) will be described in detail below.

(1) Pre-Alkali Etching Step In the pre-alkali etching step, an alkali solution containing sodium hydroxide and aluminum ions at 27% by weight and 6.5% by weight, respectively, and having a liquid temperature of 70 ° C. was used as a processing liquid. Was. The treatment liquid spray nozzle is used so that the dissolution amount of the roughened surface of the aluminum web is 6 g / m ² and the dissolution amount of the surface opposite to the roughened surface is 1 g / m ^2. The alkaline solution was sprayed on both surfaces of the aluminum web to perform an etching process.

Regarding the concentration of sodium hydroxide and aluminum ions in the alkaline solution, the relationship between the temperature, specific gravity, and conductivity of the alkaline solution and the concentration of sodium hydroxide and aluminum ions was determined in advance, The temperature, specific gravity, and conductivity of the aqueous solution are measured to determine the concentrations of sodium hydroxide and aluminum ions based on the measurement results. Water and 48 wt. Controlled by replenishment with a sodium hydroxide solution.

(1a) First-stage desmutting step The waste liquid of the hydrochloric acid solution used in the electrolytic surface roughening step to be performed next is sprayed onto both surfaces of the etched aluminum web by the treatment liquid spray nozzle at a liquid temperature of 45 ° C.
For 2 seconds to perform desmut treatment.

(2) Electrolytic surface roughening step Using an electrolytic surface roughening apparatus in which three AC electrolytic cells 2 in FIG. 1 were arranged in tandem, the concentration of hydrochloric acid was 7.5 g / liter, and the concentration of aluminum ions was The aluminum web was subjected to electrolytic surface roughening treatment in an aqueous solution of hydrochloric acid at a liquid temperature of 45 ° C. prepared by adding aluminum chloride to hydrochloric acid so that the solution became 5 g / liter.

A sine wave current generated by adjusting the current and voltage of a commercial alternating current having a frequency of 60 Hz using an induction voltage regulator and a transformer was applied to the aluminum web as an alternating waveform current. The total amount of electricity when the aluminum web was an anode was 400 C / dm ² , and the current density was 50 A / d at both the anode reaction and the cathode reaction of the aluminum web.
dm ² .

With respect to the concentrations of hydrochloric acid and aluminum ions in the aqueous hydrochloric acid solution, the relationship between the temperature, conductivity, and ultrasonic wave propagation speed and the concentrations of hydrochloric acid and aluminum ions was determined. 35% by weight of concentrated hydrochloric acid and water are added to the inside of the electrolytic cell main body from the liquid supply nozzle so that the temperature, conductivity, and ultrasonic wave propagation velocity of the aqueous hydrochloric acid solution become predetermined values. Was kept constant by overflowing.

(3) Subsequent Alkali Etching Step An alkali solution containing 5% by weight and 0.5% by weight of sodium hydroxide and aluminum ions, respectively, and having a liquid temperature of 45 ° C. was used as a treatment liquid. The etching treatment was performed so that the dissolution amount was 0.1 g / m ² on both the planarized surface and the opposite surface.

The concentrations of sodium hydroxide and aluminum ions in the alkaline solution were also controlled in the same manner as in the preceding alkaline etching step (1).

(3a) Post-stage desmutting process A sulfuric acid aqueous solution containing 300 g / l and 5 g / l of sulfuric acid and aluminum ions at a liquid temperature of 70 ° C, respectively, is sprayed on both surfaces of the aluminum web subjected to the etching treatment in the latter-stage alkali etching process. For 2 seconds.

With respect to the concentrations of sulfuric acid and aluminum ions in the aqueous sulfuric acid solution, the relationship between the temperature, specific gravity, and electrical conductivity and the sulfuric acid and aluminum ion concentrations was determined, and the temperature, specific gravity, and electrical conductivity of the aqueous sulfuric acid solution were determined. Sulfuric acid and water having a concentration of 50% by weight were replenished to keep the concentrations of sulfuric acid and aluminum ions constant so as to obtain predetermined values.

[0189] 2. Anodizing process Sulfuric acid and aluminum ions were each added at 100 g /
Liter and 5 g / liter in a sulfuric acid aqueous solution at a liquid temperature of 50 ° C., the amount of the anodic oxide film is 2.4 g / m 2.
^A direct current was applied to the aluminum web so as to be ² .

The concentration of sulfuric acid and aluminum ions in the aqueous sulfuric acid solution was controlled in the same manner as in the latter desmutting step.

Observation of the surface of the lithographic printing plate support at a magnification of 750 times with a scanning electron microscope revealed that uniform irregularities suitable for lithographic printing plates had been formed.

The lithographic printing plate support was dried to form an undercoat layer on the roughened surface, and a positive photosensitive layer having a dry film thickness of 2.0 g / m ² was formed on the undercoat layer. On the back side of the roughened surface, a saturated copolymerized polyester resin (trade name:
A surfactant (trade name: Rapisol B-80, Nippon Oil & Fats Co., Ltd.) was added to a solution prepared by dissolving 1.0 part by weight of Chemit K-1294 (manufactured by Toray Industries, Inc.) in 100 parts by weight of methyl ethyl ketone.
Co., Ltd.) and a back coat layer forming solution to which 0.05 part by weight was added was applied and dried to form a 0.2 μm thick back coat layer.

The resulting lithographic printing plate precursor was exposed and developed according to a conventional method to prepare a lithographic printing plate.

When the planographic printing plate was subjected to a burning treatment by heating at 300 ° C. for 8 minutes in a burning processor, the tensile strength after the burning treatment was 13 kg / mm.
It was ² and the elongation was 9%. It was found that the workability was as good as the planographic printing plate not subjected to the burning treatment.

The surface quality of the non-image portion of this lithographic printing plate was uniform and excellent in plate inspection. Then, when used for offset printing, no ink was found to adhere to the non-image areas of the printed matter, and it was found that the printed matter was very excellent in terms of image quality and the number of printed sheets.

(Example 2) Using the same aluminum web as in Example 1, an electrolytic surface roughening device having a flat type AC electrolytic cell and an auxiliary electrolytic cell as shown in FIG.
A roughening treatment was carried out in the same manner as in Example 1 except that an electrolytic roughening treatment was performed by applying a trapezoidal wave current as an alternating waveform current to the AC electrolyzer using the ones arranged in series. Then, an anodizing treatment was carried out to prepare a lithographic printing plate support.

The frequency of the trapezoidal wave current is 60 Hz.
From the point when the current value reaches 0 to the positive or negative peak.
The rise time tp is determined by the aluminum web anode
2 msec for both reaction and cathode reaction
c, and the current density at the peak
And 50 A / dm at the time of cathode reaction^TwoIn
Was. The amount of electricity at the time of the anode is
Is 400C / dm ^TwoMet.

When the roughened surface of the lithographic printing plate support was observed at a magnification of 750 with a scanning electron microscope, it was found that uniform irregularities suitable for the lithographic printing plate were formed.

A lithographic printing original plate was obtained by forming a positive photosensitive layer and a back coat layer on the lithographic printing plate support in the same manner as in Example 1.

When the obtained lithographic printing plate precursor was subjected to a burning treatment under the same conditions as in Example 1, the tensile strength after the burning treatment was 13 kg / mm ² , the elongation was 9%, and the burning treatment was not carried out. Workability was as good as the lithographic printing plate.

The surface quality of the non-image portion of this lithographic printing plate was uniform and excellent in plate inspection. Then, when used for offset printing, no ink was found to adhere to the non-image areas of the printed matter, and it was found that the printed matter was very excellent in terms of image quality and the number of printed sheets.

Example 3 A mechanical surface roughening treatment was performed before the pre-alkali etching step, and in the electrolytic surface roughening step, the total amount of electricity when the aluminum web was an anode was 5%.
The surface roughening treatment and the anodic oxidation treatment were performed in the same manner as in Example 1 except that the electrolytic surface roughening treatment was performed so as to be 0 C / dm ² .

The mechanical roughening treatment was performed as follows.

As an abrasive slurry, a suspension prepared by suspending silica sand having a specific gravity of 1.12 in water was used. The suspension was placed along a conveying direction of the aluminum web above a conveying surface which was a conveying path of the aluminum web. Mechanical roughening treatment was performed by a mechanical roughening device provided with three roller-like brushes.

The roller-shaped brush used was a No. 3 nylon brush having a bristle length of 50 mm, which was planted so as to be dense on the surface of a stainless steel roller having a diameter of 300 mm.

In the mechanical roughening device, two stainless steel support rollers each having a diameter of 200 mm are provided for each roller brush on the opposite side of the roller brush with respect to the transport surface. Established. The support rollers were disposed such that the distance between the centers was 300 mm.

The roller-like brush has an average surface roughness of 0.3 to 0.35 of the aluminum web after the mechanical roughening treatment.
The aluminum web was pressed against the aluminum web with a pressure of μm, and rotated so that the direction of rotation on the roughened surface was the same as the direction of conveyance of the aluminum web. The pressure for pressing the roller-shaped brush against the aluminum web was controlled based on the load of a drive motor for rotating the roller-shaped brush.

The concentration of silica sand in the abrasive slurry was continuously determined from the temperature and specific gravity of the abrasive slurry, and the mechanical roughness was replenished with water and silica sand so that the concentration became constant. Surface treatment was performed. The silica sand pulverized and refined in the mechanical surface roughening treatment was continuously removed by a cyclone so that the particle size distribution of the silica sand in the abrasive slurry was substantially constant. The particle size of the silica sand during the mechanical surface-roughening treatment was in the range of 1 to 15 μm, and the average particle size was 8 μm as measured by a laser particle size distribution analyzer (LA910, manufactured by Horiba, Ltd.). .

When the roughened surface of the obtained lithographic printing plate support was observed with a scanning electron microscope at a magnification of 750, uniform unevenness suitable for lithographic printing plates was formed on the entire surface. It was recognized that.

When the obtained lithographic printing plate precursor was subjected to a burning treatment under the same conditions as in Example 1, the tensile strength after the burning treatment was 13 kg / mm ² and the elongation was 9%, and the burning treatment was not carried out. Workability was as good as the lithographic printing plate.

The surface quality of the non-image portion of this lithographic printing plate was uniform and the plate printing was excellent. Then, when used for offset printing, no ink was found to adhere to the non-image areas of the printed matter, and it was found that the printed matter was very excellent in terms of image quality and the number of printed sheets.

(Example 4) A liquid temperature of 40 ° C and a concentration of 2.0 g /
1 liter of dimethylaminoborane aqueous solution was sprayed onto the surface of the aluminum web for 5 seconds using the processing liquid spray nozzle described in Example 1, the surface was activated, and then the electrolytic surface roughening treatment was performed. Surface roughening treatment and anodic oxidation treatment were performed in the same procedure as in Example 1 or Example 3 to obtain a lithographic printing plate support.

When the roughened surface of the resulting lithographic printing plate support was observed with a scanning electron microscope at a magnification of 750, uniform unevenness suitable for use in a lithographic printing plate was formed on the entire surface. It was recognized that.

Example 5 An undercoat solution having the following composition was applied to the roughened surface of the lithographic printing plate support obtained in Examples 1 to 4, and dried at 80 ° C. for 30 seconds to obtain an undercoat layer. Was formed. The amount of the undercoat layer after drying was 10 mg / m ² .

[Undercoat liquid composition] Dihydroxyethylglycine: 0.05 parts by weight Methanol: 94.95 parts by weight Water: 5.00 parts by weight A photosensitive resin solution having the following composition was applied on the undercoat layer. And dried at 100 ° C. for 2 minutes to form a positive type visible light exposure type plate-making layer, thereby preparing a positive type lithographic printing original plate. The weight of the plate making layer after drying was 2.5 g / m ² .

[Composition of Photosensitive Resin Solution] a. Ester compound of naphthoquinone-1,2-diazide-5-sulfonyl chloride and pyrogallol-acetone resin... 0.73 g b. Cresol novolak resin ... 2.00 g c. Oil Blue # 603 (manufactured by Orient Chemical Co., Ltd.) 0.04 g d. Ethylene dichloride 16g e. 2-methoxyethyl acetate ... 12 g The obtained lithographic printing original plate was exposed and developed according to the following procedure, and a printing test was performed.

The lithographic printing plate precursor was exposed through a transparent positive film through a transparent positive film for 50 seconds using a 3 kW metal halide lamp in a vacuum printing frame. Thereafter, the resultant was developed with a 5.26% aqueous solution of sodium silicate (pH = 12.7) having a molar ratio of SiO ₂ to Na ₂ O of 1.74, and gummed to prepare a lithographic printing plate.

As a printing machine, a Harris printing machine manufactured by Aurelia Co., Ltd. was used. As a dampening solution, EU-3 (1: 100) manufactured by Fuji Photo Film Co., Ltd. with 10% isopropanol added was used. did. Graph G (S) red manufactured by Dainippon Ink and Chemicals, Inc. was used as the ink.

As a result of visually evaluating the degree of adhesion of the ink to the blanket of the printing machine after printing 1,000 sheets, it was found that there was almost no adhesion of the ink to the blanket and good printing characteristics were exhibited.

Example 6 The lithographic printing plate support obtained in Examples 1 to 4 was treated at a liquid temperature of 30 ° C. and a concentration of 1% by weight as described in JP-A-59-101651. 3
No. 10 sodium silicate solution for 10 seconds to make it hydrophilic.

As described in Example 1 of the above-mentioned patent publication, methyl methacrylate / ethyl acrylate /
Sodium 2-acrylamide-2-methylpropanesulfonate copolymer (molar ratio of monomer units: 50: 3)
0:20, an average molecular weight of about 60,000), and an undercoat layer having a coating amount of 0.05 g / m ² was formed. The undercoat layer was dried at 100 ° C. for 30 seconds.

On the undercoat layer, a photosensitive resin solution having the following composition was applied and dried at 120 ° C. for 40 seconds to form a negative visible light exposure type plate-making layer. Was prepared.

[Composition of Photosensitive Resin Solution] a. 2-hydroxyethyl methacrylate copolymer (described in Example 1 of U.S. Pat. No. 4,123,276) 0.87 g b. 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonate of a condensate of p-diazodiphenylamine and paraformaldehyde 0.1 g c. Oil blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.) 0.03 g d. Methanol 6 g e. 2-methoxyethanol 4 g The amount of the coating after drying was 2.0 g / m ² .

The resulting lithographic printing plate precursor was exposed and developed according to the following procedures, and a printing test was performed.

The lithographic printing plate precursor was placed in a vacuum furnace at a distance of 0.7 m and 3 kW through a transparent negative film.
Was exposed for 50 seconds using a metal halide lamp. Thereafter, the following composition is used:-450 g of benzyl alcohol-150 g of triethanolamine-10 g of monoethanolamine-150 g of sodium t-butylnaphthalenesulfonate-30 g of sodium sulfite-8420 g of ion-exchanged water, gumming and lithography A printing plate was prepared.

The evaluation of the printing characteristics was performed in the same manner as in Example 5. It was found that good printing characteristics were exhibited.

Example 7 The lithographic printing plate support obtained in Examples 1 to 4 was treated with a liquid temperature of 30 ° C. and a concentration of 1% by weight as described in JP-A-2000-62333. 3
No. 10 sodium silicate solution for 10 seconds to make it hydrophilic.

An undercoat solution having the following composition was applied on the roughened surface of the lithographic printing plate support having been hydrophilized as described in Example 1 of the above-mentioned patent publication, and the solution was coated at 80 ° C. for 30 seconds. After drying, an undercoat layer having a coating amount of 10 mg / m ² was formed.

[Undercoat liquid composition] a. β-alanine 0.5 g b. Methanol 95g c. Water: 5 g Next, a positive laser plate making layer forming solution having the following composition was applied onto the undercoat layer using a wire bar so that the applied amount after drying was 1.8 g / m ² , and 120
After drying at a temperature of 2 ° C. for 2 minutes, a positive laser plate making layer was formed.

[Composition of Positive Laser Plate Making Layer Solution] a. Alkali-soluble polymer A: 0.7 g b. 2,6-dimethylene- (4,5-naphthalene-1,2,3-trimethylpyrrole) -4-monochloro-5.6-propane-heptene-methylbenzenesulfonate [cyanine dye (alkali dissolution inhibitor)] 0.1 g c. Tetrahydrophthalic anhydride 0.05 g d. Dye in which the counter anion of Victoria Pure Blue BOH is changed to 1-naphthalenesulfonic acid anion ... 0.02 g e. Fluorine-based surfactant (MegaFac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) 0.05 g f. γ-butyrolactone 8 g g. Methyl ethyl ketone 8 g h. 1-methoxy-2-propanol 4 g The alkali-soluble polymer A was synthesized according to the following procedure.

In a 500 ml three-necked flask equipped with a stirrer, a condenser, and a dropping funnel, 31.0 g of methacrylic acid was added.
(0.36 mol), 39.1 g of ethyl chloroformate (0.
The mixture was stirred while cooling in an ice-water bath, and 36.4 g (0.36 mol) of triethyleneamine was added over about 1 hour using the dropping funnel.

After the addition of triethyleneamine, 30 minutes at room temperature.
After stirring for 51 minutes, p-aminobenzenesulfonamide 51.
7 g (0.30 mol) was added, and the mixture was stirred for 1 hour while being heated to 70 ° C. in an oil bath.

After stirring for 1 hour, the contents of the three-necked flask were emptied into water to form a slurry.
A white solid of (p-aminosulfenyl) methacrylamide was obtained.

The above N- (p-aminosulfenyl) methacrylamide (5.04 g, 0.021 mol), ethyl methacrylate 2.05 g (0.018 mol), acrylonitrile 1.11 g (0.021 mol) and N , 20 g of N-dimethylacetamide and heated to 65 ° C.
0.15 g of V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was charged and stirred for 2 hours under a nitrogen stream.

The reaction product thus produced was further added with the above-mentioned N- (p-
5.04 g of aminosulfenyl) methacrylamide
(0.021 mol) and 2.05 g of ethyl methacrylate
(0.018 mol) and 1.11 g of acrylonitrile
(0.021 mol) and N, N-dimethylacetamide 2
A mixture of 0 g and 0.15 g of V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 2 hours to carry out a polymerization reaction.

After the completion of the reaction, 40 g of methanol was added to the obtained reaction solution, and after mixing for 30 minutes, the precipitate was collected by filtration and dried to obtain 15 g of a white alkali-soluble polymer A.
The molecular weight of the alkali-soluble polymer A is 53,000.
Met.

The obtained lithographic printing original plate was output at 500 m
W, a print image was directly written at a main scanning speed of 5 m / sec using a semiconductor laser device having a wavelength of 830 nm and a beam diameter of 17 μm, and developed for 30 seconds with an alkali developer 1 or an alkali developer 2 having the following composition to perform lithography. A printing plate was prepared.

[Composition of Alkaline Developer 1] a. Sodium hydroxide 2.8% by weight b. Silica ... 2.0% by weight c. Nonionic surfactant (Pluronic PE-3100, manufactured by BASF) 0.5% by weight d. Water: 94.7% by weight [Composition of alkaline developer 2] a. Potassium hydroxide 2.8% by weight b. D-Sorbit 2.5% by weight c. Diethylenetriaminepenta (methylenesulfonic acid) 5Na salt 0.1% by weight d. Nonionic surfactant (Pluronic P-85, manufactured by Asahi Denka Kogyo KK) 0.5% by weight e. Water: 94.5% by weight When printing was performed using the lithographic printing plate, it was found that the lithographic printing plate had good printing performance.

(Example 8) As described in Example 2 of JP-A-2000-62333, an undercoat solution having the following composition was applied to the lithographic printing plate support obtained in Examples 1 to 4. The coating was performed so that the coating amount after drying was 11 mg / m ^2, and dried at 80 ° C. for 30 seconds to form an undercoat layer.

[Undercoat liquid composition] a. β-alanine 0.1 g b. Phenylsulfonic acid 0.05 g c. Methanol ... 40 g d. Water: 60 g Next, a negative type laser plate making layer forming solution having the following composition was applied onto the undercoat layer using a wire bar so that the coating amount after drying was 1.5 g / m ² , and then 120
It dried at 2 degreeC for 2 minutes, and formed the negative type laser plate making layer.

[Composition of Negative Laser Plate Making Layer Forming Solution] a. Nonylphenol (acid-crosslinkable compound) ... 0.05 g b. 2,4,6-trimethoxydiazonium-2,6, -dimethylbenzenesulfonate (acid precursor) 0.3 g c. Crosslinking agent A (acid crosslinkable compound) ... 0.5 g d. Poly (p-hydroxystyrene) (alkali-soluble resin) 1.5 g e. 2,6-dimethylene- (4,5-naphthalene-1,2,3-trimethylpyrrole) -4-monochloro-5.6-propane-heptene-methylbenzenesulfonate (cyanine dye, infrared absorbing agent) ... 0. 07 g f. Aizen Spiron Blue C-RH (manufactured by Hodogaya Chemical Co., Ltd.) 0.035 g g. Megafac F-177 (manufactured by Dainippon Ink and Chemicals, Inc., fluorine-based surfactant) 0.01 g h. Methyl ethyl ketone 12 g i. Methyl alcohol ... 10 g j. 1-methoxy-2-propanol 8 g The cross-linking agent A was synthesized by the following procedure.

1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis (4-hydroxyphenyl) ethyl] benzene was reacted with formalin in an aqueous potassium hydroxide solution. .

The obtained reaction solution was acidified with sulfuric acid and crystallized to obtain a crosslinking agent A having a purity of 92%.

The lithographic printing original plate on which the negative type laser plate making layer is formed is exposed using a semiconductor laser device, and a developing solution P
D-4 (manufactured by Fuji Photo Film Co., Ltd., 1: 8 water dilution)
And developed.

When printing was performed using the lithographic printing plate, it was found that the lithographic printing plate had good printing performance.

(Embodiment 9) JP-A-2000-62333
As described in Example 3 of the report, methylene ethoxy
50 g of silane, 1.1 g of acetic acid, 7.7 g of distilled water, and
And 100 g of ethanol at room temperature.
The sol was prepared by heating. The obtained sol was prepared in Examples 1 to
The amount of the coated lithographic printing plate support after drying was 2
0mg / m ^TwoApply at 170 ° C for 10 minutes
It was dried to form an undercoat layer.

Next, a photopolymerizable laser plate making layer having the following composition was applied so that the coating amount after drying was 1.5 g / m ² , and dried to form a photopolymerizable laser plate making layer. did.

[Composition of Photopolymerization Type Laser Plate Making Layer Forming Solution] a. Pentaerythritol tetraacrylate (vinyl polymerizable compound) 1.5 g b. Allyl methacrylate / methacrylic acid copolymer (copolymerization ratio 80/20) 2.0 g c. 1,2- (p-styrylphenyl) -4,6-bis (trichloromethyl) -S-triazine (sensitizer) 0.2 g d. Propylene glycol monomethyl ester 20 g e. Methyl ethyl ketone 20 g f. Megafac F-177 (manufactured by Dainippon Ink and Chemicals, Ltd., fluorine-based surfactant) 0.03 g g. Oil-soluble dye (Victoria Pure Blue BOH) 0.02 g The lithographic printing plate precursor on which the photopolymerization type laser plate making layer is formed is
Exposure was performed using a YAG laser at an exposure amount of 0.0132 mW / cm ^{2, and} the film was immersed in the alkaline developer 1 described in Example 7 and developed.

When printing was performed using the lithographic printing plate, it was found that the lithographic printing plate had good printing performance.

Example 10 A lithographic printing plate support was prepared according to the same procedure as in Examples 1 to 4, except that washing was performed by spraying dry ice powder instead of washing with water after each step. .

Since the amount of waste liquid discharged in the cleaning step was significantly reduced, the cost required for waste liquid treatment was also significantly reduced.

(Comparative Example 1) A lithographic printing plate precursor was prepared in the same manner as in Example 1 except that an aluminum base metal having the composition shown in Table 2 was used.

[0253]

[Table 2]

The resulting lithographic printing plate precursor was exposed and developed according to the same procedure as in Example 1 and subjected to burning treatment. The lithographic printing plate after the burning treatment had no rigidity and was very poor in workability.

[0255]

According to the present invention, a method for producing a lithographic printing plate support capable of forming uniform honeycomb pits with a smaller amount of electricity even when an aluminum plate produced from recycled aluminum base metal is used, A lithographic printing plate support and a lithographic printing original plate are provided.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing an example of an electrolytic surface roughening apparatus having a flat type AC electrolytic tank, which is used in a method of manufacturing a lithographic printing plate support according to the present invention.

FIG. 2 is a cross-sectional view showing another example of an electrolytic surface roughening apparatus including a flat AC electrolytic cell.

FIG. 3 is a cut-away view showing an example of an electrolytic surface roughening apparatus used in the method of manufacturing a lithographic printing plate support according to the present invention, the apparatus including a radial type AC electrolytic cell.

[Explanation of symbols]

 2 AC electrolytic tank 4A Main pole 4B Main pole 4C Main pole 6A Transport roller 6B Transport roller 8A Introducing roller 8B Outgoing roller 10 Auxiliary electrolytic tank 12 Auxiliary electrode 14A Transport roller 14B Transport roller 16A Introducing roller 16B Outgoing roller Th1 Thyristor Th2 Thyristor Th Th4 thyristor 20 AC electrolyzer 22 AC electrolyzer main body 24 Feed roller 26A Main pole 26B Main pole 28A Liquid supply nozzle 28B Liquid supply nozzle 30A Upstream guide roller 30B Downstream guide roller 32 Overflow tank 34 Auxiliary electrolytic tank 36 Auxiliary electrode

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C22C 21/00 C22C 21/00 M C23C 28/00 C23C 28/00 Z C23F 1/00 104 C23F 1/00 104 1/36 1/36 C23G 5/00 C23G 5/00 C25D 11/04 C25D 11/04 E 11/18 301 11/18 301A 313 313 (72) Inventor Hirokazu Sawada 4000, Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Fujisha Shin Film Co., Ltd. (72) Inventor Akio Uesugi 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture F-term inside Fujisha Shin Film Co., Ltd. GA08 GA09 GA38 4K044 AA06 AB02 BA13 BA21 BB03 BB14 BC02 CA04 CA16 CA17 CA53 4K053 PA10 PA12 QA06 RA01 RA02 RA12 SA04 TA10 4K057 WA05 WB0 5 WB11 WD05 WE21 WE22 WK01

Claims (16)

[Claims] 1. Fe: 0.05 to 0.5% by weight, Si: 0.02 to 0.2% by weight, Cu: 0.001 to 0.05% by weight, Ti: 0.003 to 0.04% % By weight, Mg: 0.001 to 0.3% by weight, Mn: 0.001 to 0.05% by weight, Zn: 0.001 to 0.05% by weight, and at a depth within 50 μm from the surface, An aluminum plate having a crystal grain width of 20 to 200 μm. 2. The aluminum plate according to claim 1, wherein at least one surface of the aluminum plate is subjected to (1) a preliminary alkali etching step of etching by contacting with an alkali solution, and (2) the etched aluminum plate. A method for producing a support for a lithographic printing plate, wherein the surface is roughened by an electrolytic surface roughening step of performing an electrolytic surface roughening treatment in an aqueous hydrochloric acid solution containing hydrochloric acid as a main acid component. . 3. In the electrolytic surface roughening step, hydrochloric acid and aluminum ions are contained at a concentration of 5 to 15 g / l and 1 to 15 g / l, respectively, and a hydrochloric acid aqueous solution having a liquid temperature of 20 to 50 ° C. The method for producing a lithographic printing plate support according to claim 2, wherein the surface is subjected to electrolytic surface roughening treatment. 4. In the electrolytic surface roughening step, the total amount of electricity when the aluminum plate is an anode is 10 to 100.
4. The method for manufacturing a lithographic printing plate support according to claim 2, wherein an alternating waveform current is applied to the aluminum plate so as to be 0 C / dm ² to perform electrolytic surface roughening treatment. 5. The alternating current having a frequency of 40 to 40.
120 Hz, the time for the current to reach a positive or negative peak from 0 is 0.5 to 6 msec, and the current density at the time of the positive or negative peak is 20 to 100 A
5. The method for producing a lithographic printing plate support according to claim 4, wherein the trapezoidal current is / dm ² . 6. A second-stage alkali etching step in which an alkali solution is brought into contact with the aluminum plate that has been subjected to the electrolytic surface-roughening treatment in the electrolytic surface-roughening step to perform etching, and an electrolytic surface-roughening treatment in the electrolytic surface-roughening step. 6. The production of a lithographic printing plate support according to any one of claims 2 to 5, further comprising one of a post-electrolysis desmutting step in which an acidic solution is brought into contact with the prepared aluminum plate and desmutted. Method. 7. A pre-stage desmutting step in which the aluminum plate etched in the pre-stage alkali etching step is brought into contact with an acidic solution to perform desmutting, and the aluminum plate etched in the post-stage alkali etching step is converted into an acidic solution. The method for producing a lithographic printing plate support according to any one of claims 2 to 6, further comprising at least one of a subsequent desmutting step of contacting and desmutting. 8. In the post-electrolysis desmutting step, the aluminum plate is subjected to a sulfuric acid concentration of 100 to 50.
The method for producing a lithographic printing plate support according to claim 6, wherein the substrate is brought into contact with an aqueous solution of sulfuric acid at 0 g / liter and a liquid temperature of 60 to 90 ° C for 1 to 180 seconds. 9. In the desmutting treatment, the aluminum plate is placed in an aqueous sulfuric acid solution having a sulfuric acid concentration of 100 to 500 g / liter and a liquid temperature of 60 to 90 ° C.
The method for producing a lithographic printing plate support according to claim 7, wherein the support is contacted for 180 seconds. 10. The roughening step includes a mechanical roughening step of performing a mechanical roughening process on a surface of the aluminum plate to be roughened before the etching process in the pre-alkali etching process. Claims 2 to 9 having
The method for producing a lithographic printing plate support according to any one of the above. 11. An anodizing step of forming an anodized film on the roughened surface of the aluminum plate by anodizing the aluminum plate roughened in the roughening step. The method for producing a lithographic printing plate support according to any one of 2 to 10. 12. The method for producing a lithographic printing plate support according to claim 11, wherein in the anodic oxidation treatment step, a hydrophilization treatment for hydrophilizing an anodic oxide film formed on the surface of the aluminum plate is performed. 13. The anodic oxidation treatment step, wherein a sealing treatment for closing small holes in the anodic oxide film formed on the surface of the aluminum plate is performed.
3. The method for producing a lithographic printing plate support according to item 1. 14. After the at least one of the surface roughening step and the anodizing step is completed, the roughened surface of the aluminum plate is washed by spraying particulate dry ice thereon. The method for producing a lithographic printing plate support according to any one of the above. 15. A lithographic printing plate support produced by the production method according to claim 2. Description: 16. A lithographic printing original plate, wherein a plate-making layer is formed on the roughened surface of the lithographic printing plate support according to claim 15.