JP2003246160A - Manufacturing method for aluminum substrate for lithographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for an aluminum substrate for a lithographic printing plate which makes it possible to use an aluminum rolled sheet (an aluminum sheet containing lots of alloy constituents or an aluminum sheet of which the alloy constituents are not regulated) and which brings about no nonuniformity in treatment due to surface roughening treatment and can make compatible plate wear and printing performance (scumming performance) when it is made into the plate. <P>SOLUTION: In this manufacturing method, the aluminum sheet is subjected sequentially to (1) electrochemical surface roughening treatment in a nitric acid water solution in the condition that the ratio Qc/Qa between the quantity Qa of electricity of an alternating current on the occasion of the aluminum sheet being an anode and the quantity Qc of electricity of the current on the occasion of the sheet being a cathode is 0.9-1.0, (2) electrochemical surface roughening treatment in a hydrochloric acid water solution wherein the concentration of aluminum ions is made 1-8 g/L by adding an aluminum chloride hexahydrate in the rate of 10-70 g/L to a water solution containing a hydrochloric acid of 1-10 g/L, in the condition that the ratio of Qc/Qa is 0.9-1.0, and (3) anodizing treatment. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
In particular, the low purity aluminum
Minium rolled plate (aluminum plate containing many alloy components)
Or an aluminum plate with no alloy components prepared)
And there is no processing unevenness due to the roughening process.
Aluminum for planographic printing plates obtained by the production method of the present invention
Printing durability and marking when a lithographic printing plate is used as the support.
Aluminum for lithographic printing plates that can achieve both printing performance (dirt performance)
The present invention relates to a method for manufacturing a um support. [0002] 2. Description of the Related Art Aluminum supports for lithographic printing plates
Mechanical roughening, chemical etching in acid or alkaline solution
Ching, desmut treatment in acidic aqueous solution, acidic aqueous solution
Among anodizing treatment, hydrophilization treatment, sealing treatment, etc.
It is common to roughen the surface by combining one or more.
The In particular, electrochemical surface roughening makes it easy to obtain uniform irregularities.
How to roughen the aluminum support for lithographic printing plates
It has been commonly used as a law. Especially hydrochloric acid or nitric acid
Mainly used for electrochemical surface roughening in aqueous solution
It is common. Conventionally, it has been used to obtain uniform irregularities.
Electrolytic surface roughening using aqueous solution mainly composed of nitric acid
In the method, adjustment of the alloy components of the aluminum alloy plate
It must be done strictly. And the composition of alloy components fluctuated
As a result, the roughened shape changes significantly, so
If the condition is constant,
Aluminum alloy plate, especially high content of impurity elements
Uniform uneven surface roughened shape for aluminum alloy plate
There is a problem that it cannot be formed. On the other hand, in recent years, aluminum supports for planographic printing plates have been developed.
As a holder, a simplified aluminum plate rolling process
Luminium rolled plate, general-purpose aluminum plate, beverage can, etc.
Use bullion that has not been adjusted from alloy components recycled from
Using an inexpensive aluminum sheet that has been rolled
It is desired from the viewpoint of energy and effective use of resources. Shi
However, an aluminum plate that simplified the aluminum plate rolling process.
Um plate, aluminum plate with many alloy components, alloy components
For lithographic printing plates using unprepared aluminum plates
When an aluminum support is manufactured, the aluminum crystal orientation occurs.
Therefore, processing unevenness called streak tends to occur.
In addition, in the electrochemical roughening treatment, uniform roughening is performed.
First, the appearance failure (processing unevenness) or printing performance (
(Soil performance) is inferior. Further, an infrared laser for direct plate making
Having an image forming layer formed of a photosensitive image forming material
Number of printed sheets as an aluminum support for lithographic printing plates
Lithographic printing with both printing durability and dirt performance
An aluminum support for printing plates has been desired. But Al
If the alloy composition of the minium alloy plate is not adjusted,
Electrochemical roughening treatment is not performed uniformly, and printing durability
Aluminium for lithographic printing plates with compatible dirt performance
It is difficult to manufacture a um support. [0006] The present invention relates to a lithographic printing plate.
Low purity not used for aluminum support
Aluminum rolled plate (aluminum containing many alloy components)
Or aluminum plate with no alloy components prepared)
And uneven processing due to the roughening treatment
In addition, for lithographic printing plates obtained by the production method of the present invention
When the aluminum support is a lithographic printing plate (hereinafter simply
In some cases, "when lithographic printing is used". ) Excellent
A lithographic plate that achieves both printing durability and printing performance (dirt performance)
To provide a method for producing an aluminum support for a printing plate
With the goal. [0007] [Means for Solving the Problems] The present inventors have conducted extensive research.
As a result, used for electrochemical surface roughening in hydrochloric acid aqueous solution
Use an aqueous hydrochloric acid solution with a specific composition.
And in aqueous nitric acid and aqueous hydrochloric acid
AC aluminum plate for electrochemical roughening treatment
The ratio of the quantity of electricity Qa at the time of anode to the quantity of electricity Qc at the time of cathode, Qc
/ Qa is set to 0.9 to 1.0, so that a lithographic printing plate
Aluminum used for aluminum support
Even if the latitude of the amount of the plate alloy component is wide, the roughening treatment
The processing unevenness caused by
It is possible to achieve both printing durability and printing performance (dirt performance).
As a result, the present invention has been completed. That is, (1) the present invention is aluminum
In order, 1) In an aqueous nitric acid solution, when an alternating current aluminum plate is used as an anode
Ratio of electricity quantity Qa and electricity quantity Qc at the time of cathode, Qc / Qa is
Electrochemically roughening treatment under conditions of 0.9 to 1.0, 2) In an aqueous solution containing 1-10 g / L hydrochloric acid,
Add Minium Hexahydrate at a rate of 10-70 g / L
Hydrochloric acid aqueous solution having a ruminium ion concentration of 1 to 8 g / L
Inside, the amount of electricity Qa and the shade of the aluminum plate of AC
Ratio of electrical quantity Qc at the extreme, Qc / Qa is 0.9 to 1.0
Electrochemical roughening treatment under conditions, 3) An anodizing treatment for a lithographic printing plate
A method for producing a ruminium support is provided. (2) The present invention provides an aluminum plate.
In turn, 1) Mechanically roughening treatment, 2) In the nitric acid aqueous solution, the anode of the aluminum plate of alternating current
Ratio of electricity quantity Qa and electricity quantity Qc at the time of cathode, Qc / Qa is
Electrochemically roughening treatment under conditions of 0.9 to 1.0, 3) To an aqueous solution containing 1 to 10 g / L of hydrochloric acid,
Add Minium Hexahydrate at a rate of 10-70 g / L
Hydrochloric acid aqueous solution having a ruminium ion concentration of 1 to 8 g / L
Inside, the amount of electricity Qa and the shade of the aluminum plate of AC
Ratio of electrical quantity Qc at the extreme, Qc / Qa is 0.9 to 1.0
Electrochemical roughening treatment under conditions, 4) An anodizing treatment for a lithographic printing plate
A method for producing a ruminium support is provided. Here, the aqueous hydrochloric acid solution contains 1 to 1 hydrochloric acid.
It is preferable to contain 0 g / L, and 2 to 6 g / L is contained.
Is particularly preferred. Aluminum chloride hexahydrate to be added
Is preferably 10 to 70 g / L, and 20 to 50
More preferably, it is g / L, and it is 35-45 g / L.
It is particularly preferred. Added aluminum chloride hexahydrate
The concentration of aluminum ions in the aqueous hydrochloric acid solution is 1-8 g
/ L is preferable, and 2 to 6 g / L is more preferable.
4 to 5 g / L is particularly preferable. [0011] (3) The present invention provides the above nitric acid aqueous solution.
And / or electrochemical rough surface in the aqueous hydrochloric acid solution
In alkaline aqueous solution before and / or after crystallization treatment
Etching process and desmatter in acidic aqueous solution
(1) or (2)
A method for manufacturing aluminum supports for lithographic printing plates
To do. Here, the aluminum plates are in order, 1) Etching treatment in alkaline aqueous solution (1st Al
Potash etching process) 2) Desmut treatment in acidic aqueous solution
Processing) 3) Electrochemical roughening treatment in an aqueous solution mainly composed of nitric acid.
(First electrochemical roughening treatment) 4) Etching in alkaline aqueous solution (second al
Potash etching process) 5) Desmut treatment in acidic aqueous solution
Processing) 6) Electrochemical roughening treatment in an aqueous solution mainly composed of hydrochloric acid.
(2nd electrochemical roughening treatment) 7) Etching treatment in alkaline aqueous solution (3rd Al
Potash etching process) 8) Desmut treatment in acidic aqueous solution.
Processing) 9) Anodizing is particularly preferable. (4) The present invention provides the anodizing treatment.
After the sealing treatment or hydrophilization treatment or sealing treatment
(1) to characterized by performing treatment and hydrophilization treatment
(3) The aluminum support for lithographic printing plates according to any one of
A method for manufacturing a holding body is provided. (5) The present invention also provides the desmut treatment.
In reason, the aqueous nitric acid solution and / or the aqueous hydrochloric acid solution
Electrochemical surface roughening treatment or the anodic acid
It is characterized by using the waste liquid of the electrolyte used in the chemical treatment
The lithographic printing plate aluminum according to any one of (1) to (4)
Provided is a method for manufacturing a nium support. (6) The present invention provides the above aluminum.
Aluminum plate having the composition shown in Table 1 below
(AL1 to AL4)
Production of an aluminum support for a lithographic printing plate as described in (5)
Provide a method. [0016] [Table 1] (7) The present invention provides (1) to (6)
Production of an aluminum support for a lithographic printing plate according to any one of
Aluminum support for lithographic printing plate produced by the manufacturing method
I will provide a. [0018] (8) The present invention provides a flat plate according to (7).
Directly laser-printed on an aluminum support for printing plates
The alkaline developer by heat generated by photothermal conversion
It has a positive-type image-forming layer that changes its solubility in
A lithographic printing plate precursor characterized by: (9) The present invention directly draws with a laser.
However, the heat generated by the photothermal conversion makes the alkaline developer
The photosensitive layer whose solubility is changed is the following A layer and B layer in order.
Next layered, B layer contains compound that generates heat by absorbing light
The lithographic printing plate precursor as described in (8)
provide. Layer A: Small amount of monomers (a-1) to (a-3)
Copolymer containing at least 10 mol% as a copolymerization component
Layer B layer containing 50% by mass or more of polymer: phenolic
50% by mass of an aqueous alkali-soluble resin having a hydroxyl group
Layer containing [0020] (10) The present invention provides the method described in (7).
Direct laser with an aluminum support for lithographic printing plates
Drawing and alkali development by heat generated by photothermal conversion
It has a negative type image forming layer whose solubility in liquid changes
A lithographic printing plate precursor is provided. (11) The present invention is also directed to (7).
Radical addition on an aluminum support for lithographic printing plates
Image forming layer that can be drawn directly by laser using polymerization reaction
A lithographic printing plate precursor is provided. (12) Further, the present invention provides the method according to (7).
Positive photosensitive on an aluminum support for lithographic printing plates
Providing a lithographic printing plate characterized by having an image forming layer
To do. [0023] (13) The present invention provides the method described in (7).
Negative photosensitive on an aluminum support for lithographic printing plates
A lithographic printing plate precursor having an image forming layer
provide. (14) In the present invention, the development processing solution comprises:
It is characterized by developing with an alkaline aqueous solution containing silicic acid.
The lithographic printing plate precursor according to any one of (8) to (13)
A method for developing a plate is provided. (15) In the present invention, the developing solution may be
Develop with alkaline aqueous solution without silicate and saccharides
Any one of (8) to (13)
A lithographic printing plate precursor development method is provided. [0026] DETAILED DESCRIPTION OF THE INVENTION <Aluminum alloy sheet (rolled aluminum)
Mi)> The aluminum plate used in the present invention is pure aluminum
A small amount of foreign elements mainly composed of a aluminum plate and aluminum
Including alloy plate or aluminum laminate or
Selected from vapor-deposited plastic films. A
Trace amounts of foreign elements contained in the luminium plate
One or more selected from those listed,
Its content is 0.001 wt% to 1.5 wt%. The
Typical examples of foreign elements contained in aluminum alloys include
Elemental, iron, nickel, manganese, copper, magnesium, black
, Zinc, bismuth, titanium and vanadium.
Usually Aluminum Handbook 4th Edition (1990, light
Of materials known in the art as described in (Metal Society)
JIS A 1050 materials, JIS A 3103 materials,
JIS A 3005, JIS A 1100, J
For the purpose of increasing IS A 3004 material or tensile strength
Alloys with 5 wt% or less of magnesium added to these
Can be used. The aluminum plate used in the present invention is
Contains a lot of impurities recovered by scrapping beverage cans, etc.
It is also possible to use aluminum plates obtained by rolling
it can. For example, aluminum having the composition shown in Table 1 above
A nickel plate is mentioned. Aluminum for planographic printing plates of the present invention
In the manufacturing method of the um support, the trace element is contained in a large amount.
Even with electrochemical roughening in acidic aqueous solution
Honeycomb pits are generated. Also contains a lot of Si component
Even if it is rare, after anodizing after roughening
In this case, there is no defect of the anodized film, and the paper becomes dirty during printing.
It will never happen. Furthermore, even if a lot of Cu component is contained,
The area where the honeycomb pits are not formed is small and the appearance is
There is no obstacle. Aluminum support for lithographic printing plate of the present invention
The aluminum plate used in the manufacturing method is from the DC casting method.
Intermediate annealing treatment or soaking treatment, or intermediate annealing treatment
And aluminum plate manufactured by omitting soaking,
Or manufactured by omitting the intermediate annealing process from the continuous casting method
An aluminum plate may be used. The thickness of the aluminum plate used in the present invention is
0.05-0.8mm, preferably 0.1mm-0.6
mm. The aluminum support for lithographic printing plates of the present invention
In the manufacturing method of
Electrochemical surface roughening treatment in specific aqueous solution
Aluminum support for lithographic printing plates with surface treatment including finishing
This surface treatment includes various treatments.
It may be. Various processes used in the present invention
Used in the processing solution used in the process.
Because the alloy components of the aluminum alloy plate are eluted
The liquid may contain the alloy components of the aluminum alloy plate.
In particular, add the alloy components before treatment
Is preferably used in a steady state. In the present invention, each electrochemical roughening treatment is performed.
Before processing, alkali etching treatment or desmut
It is preferable to perform treatment, and alkali etching treatment
It is also preferable to perform treatment and desmut treatment in this order. Ma
After each electrochemical surface roughening treatment, alkaline etching
It is preferable to apply
Alkaline etching and desmutting
It is also preferable to apply in order. In addition, each electrochemical roughening treatment
Subsequent alkaline etching treatment can be omitted.
The In the present invention, the mechanical rough surface before these treatments.
It is also preferable to apply a crystallization treatment. In addition, each electrochemical roughening
You may perform a process twice or more. Also after these, Yang
It is also preferable to perform extreme oxidation treatment, sealing treatment, hydrophilic treatment, etc.
That's right. In particular, the surface treatment is an alkali etching treatment.
, Desmutting, electrochemical roughening in aqueous nitric acid
Surface treatment, alkali etching treatment and / or death
Matting treatment, electrochemical surface roughening treatment in hydrochloric acid aqueous solution
, Alkaline etching and / or desmut
It is preferable for the present invention to include the treatment and the anodizing treatment in this order.
This is one of the new embodiments. In this case, the surface treatment is anodic acid
After the hydrophilization treatment, sealing treatment and / or hydrophilization treatment are included.
This is one of the preferred embodiments of the present invention. Also this
In the case of the surface treatment, the first alkaline etching treatment
It is preferred that the present invention includes a mechanical surface roughening process before
This is one of the embodiments. Hereinafter, the mechanical surface roughening treatment, the first alkaline solution
Etching, first desmut treatment, first electrochemical roughing
Surface treatment, second alkali etching treatment, second desma
Treatment, second electrochemical surface roughening treatment, third alkali etch
Ching treatment, third desmut treatment, anodizing treatment, sealing
Each of treatment and hydrophilization treatment is explained in detail
To do. In the present specification, in an aqueous nitric acid solution
Electrochemical surface roughening treatment at the first electrochemical surface roughening treatment
The second electrochemical roughening treatment in hydrochloric acid solution
It may be called electrochemical roughening treatment. Also (machine
Before the first electrochemical surface roughening)
The first alkali etching is the alkali etching process
This is called treatment, and after the first electrochemical roughening treatment, the second electricity
Alkaline etching before chemical roughening
This is called the second alkaline etching treatment, and the second electrochemical roughing
Alkaline etch after surface treatment and before anodizing
In some cases, the etching process is called a third alkali etching process.
The Similarly, the desmut process is performed in the order described above.
The second desmut process, the second desmut process,
There is a case. Note that the desmut treatment is performed with alkaline alkali.
This is done after the etching process. <Mechanical surface roughening> In the present invention
The mechanical roughening treatment should be performed before the electrochemical roughening treatment.
It is preferable. Aluminum by mechanical surface roughening
The surface area of the plate is increased. First, brush the aluminum plate
Prior to graining, if desired, surface rolling oil
Degreasing treatment to remove water, such as surfactants, organic solvents
Degreasing treatment with an agent or alkaline aqueous solution
The However, degreasing treatment is omitted when there is little adhesion of rolling oil.
Can. Subsequently, one type or different hair diameter
Polishing slurry using at least two types of brushes
While supplying to the aluminum plate surface
Perform. Regarding mechanical surface roughening, Japanese Patent Laid-Open No. Hei 6
-135175, JP-B-50-40047
Are described in detail. The brush graining smell
The first brush used is called the first brush, and the last used
This brush is called the second brush. In FIG.
Luminium alloy plates 52 and 54 are roller brushes, 53
Is polishing slurry and 55, 56, 57, 58 are supported
Laura. At the grain time, as shown in FIG.
Roller-shaped brushes 52 and 54 sandwiching the minium plate 51
And two support rollers 55, 56 and 57, respectively.
58 is arranged. Two support rollers 55, 56 and 5
7 and 58, the shortest distance between the outer surfaces is the roller-shaped brush 52.
Are arranged so as to be smaller than the outer diameters of
Luminium plate 51 is formed by roller brushes 52 and 54.
Two supporting rollers 55, 56 and 57,
58 with the aluminum plate pushed in between
It is transported at a constant speed and polishing slurry liquid 53 is aluminized.
Rotating the roller-shaped brush by feeding it on the steel plate
It is preferable to polish the surface more. The brush used in the present invention has a roller shape.
Nylon, polypropylene, animal hair on the base, or
Uniform hair length and flocking of brush material such as steel wire
What is planted with distribution, brush with a small hole in the base
Hair transplanted, channel roller type
Etc. are preferably used. Of these, preferred materials are
It is nylon, and the preferred hair length after planting is 10 to 200.
mm. In addition, the flocking density when planting in the brush roller
Is 1cm²30-1000 per piece are preferred, and more preferred
The number is preferably 50 to 300. Preferred hair of the brush
The diameter is 0.24 to 0.83 mm, more preferably
0.295 to 0.72 mm. The cross-sectional shape of the hair is a circle
preferable. If the hair diameter is smaller than 0.24mm, shadow
The dirt performance at the part deteriorates and is larger than 0.83 mm
And the dirt performance on the blanket may deteriorate. hair
Material is preferably nylon, nylon 6, nylon 6
・ 6, nylon 6, 10 etc. are used, but pull
Strength, abrasion resistance, dimensional stability due to water absorption, bending strength, resistance
Nylon 6 · 10 is most preferable in terms of heat resistance and recoverability. The number of brushes is preferably 1 or more and 10
Or less, more preferably 1 or more and 6 or less.
The The brush roller is described in JP-A-6-135175.
Even if you combine brush rollers with different bristle diameters as listed
Good. Next, the rotation of the brush roller is preferably 100 rp.
m is arbitrarily selected from 500 rpm. Support roller is
Use a metal or metal surface that is kept straight.
I can. The direction of rotation of the brush roller is as shown in FIG.
It is preferable to perform forward rotation in the conveyance direction of the aluminum plate
However, if there are many brush rollers, some brush rollers
May be reversed. The pushing amount of the brush
It is preferable to manage with the load of the rotary drive motor.
The power consumption of the rolling drive motor is 1.0-15 kW, and 2
It is preferable to manage so that it may become 10 kw. In the present invention, the rough brush is used to roughen the surface.
After treatment with a thin brush, hydrophilicity and
A support that has both aqueous and adhesive properties is obtained.
preferable. In that case, shadow area when dampening water is low
Since there is no crushing of the water, the water width is wide and soiling is difficult to occur.
Furthermore, there is no deterioration in adhesion with the photosensitive layer. Main departure
The polishing slurry used for light is silica sand, hydroxide hydroxide
Minium, alumina powder, volcanic ash, pumice, carboranda
Average particle diameter of 1 to 50 μm (preferably
20-45 μm) abrasives with a specific gravity of 1.05-1.3
What is dispersed in water within such a range is preferable. average
The particle size is the volume of all abrasives contained in the slurry.
On the other hand, when the cumulative frequency of the proportion of particles of each diameter was taken
The particle size at which the cumulative ratio is 50%. The machine
The center line average roughness (Ra) after roughening is 0.3 to 1.
It is preferable to process so that it may become 0 micrometer. of course
A method of spraying slurry liquid, using a wire brush
The surface shape of the rolling roll with irregularities
For example, a method of transferring to a film plate may be used. Other methods
Are disclosed in JP-A-55-074898 and JP-A-6.
No. 1-162351, JP-A 63-104889
It is described in gazettes. Thus, the aluminum plate is brush gray
Then, the surface of the aluminum plate is chemically treated
It is preferable to perform etching. This chemical essence
Chinching is performed with brush grained aluminum.
Abrasives, aluminum scraps, etc.
Has the effect of removing the electrochemical
It is possible to achieve roughening more uniformly and effectively.
it can. <Chemical etching in aqueous alkali solution>
Treatment (first alkali etching treatment)> first alkali
Etching treatment is performed using the above aluminum alloy plate
Etching is performed by contacting the solution. First
Alkaline etching treatment is mechanical roughening treatment.
If not, the aluminum alloy plate (rolled aluminum)
Remove the rolling oil, dirt and natural oxide film on the surface of
And for the purpose of mechanical roughing
Has uneven edges generated by mechanical surface roughening
Dissolve the part and get a surface with smooth swell
It is done for the purpose. Aluminum alloy plate with alkali
As a method of contacting the solution, for example, aluminum
Passing the alloy plate through a tank containing an alkaline solution
Method, aluminum alloy plate in a tank containing alkaline solution
Soaking in aluminum, alkaline solution with aluminum alloy
The method of spraying on the surface of a board is mentioned. Details of the chemical etching method are described in US
It is described in Japanese Patent No. 3,834,398.
The More specifically, it can dissolve aluminum.
To be immersed in an aqueous solution, more specifically, an alkaline aqueous solution
Is the law. Examples of the alkali include sodium hydroxide
, Potassium hydroxide, tribasic sodium phosphate, tertiary phosphorus
Potassium acid, sodium aluminate, sodium metasilicate
Um and sodium carbonate. An aqueous base solution
When used, the etching rate is fast. Chemical etching of these alkalis
0.05 ° C. to 40% by mass (wt%) aqueous solution, 40 ° C.
It is preferable to treat for 5 to 300 seconds at a liquid temperature of -100 ° C.
Good. The concentration of alkaline aqueous solution is 1-30 wt%
Of course, aluminum is included in the aluminum alloy.
The alloy component may contain 0 to 10 wt%. Arca
An aqueous solution mainly composed of caustic soda
Is preferred. The liquid temperature is from room temperature to 95 ° C, and is treated for 1 to 120 seconds
It is preferable to manage. After the etching process is completed, the processing liquid
In order not to bring it into the next process
It is preferable to perform cutting and water washing by spraying. Al
The amount of chemical etching of the minium plate is
The dissolution amount of the minium plate is 0.001 to 30 g / m.²Preferred
More preferably 1-15 g / m²And especially
Preferably, 3-12 g / m²It is. <Acid etching process> Acid etching process
The chemical etching of the aluminum plate in an acidic aqueous solution
After the electrochemical roughening treatment.
It is preferred to do so. In addition, the electrochemical surface roughening treatment
Perform the alkali etching process before and / or after
If so, acid etch after alkali etching
It is also preferable to perform the processing. The above aluminum plate
After the potash etching treatment, the above acidic etching
When treated, a metal containing silica on the aluminum plate surface
Intercalation compound or simple substance Si can be removed, and then
Defects in the anodized film formed in the anodizing treatment of
Can be eliminated. As a result, when printing,
Trouble that dot ink adheres to the non-image area called
Can be prevented. Acidic water used for acid etching treatment
Liquids include phosphoric acid, nitric acid, sulfuric acid, chromic acid, hydrochloric acid,
Or an aqueous solution containing two or more of these mixed acids.
It is. Of these, a sulfuric acid aqueous solution is preferable. Concentration of acidic aqueous solution
The degree is preferably 50 to 500 g / L. Acid water
Solution is not only aluminum but also aluminum plate
The alloy component to be contained may be contained. In the acid etching treatment, the liquid temperature is set to 60 to 90.
℃, preferably 70-80 ℃, treated for 1-10 seconds
It is preferable to do so. Aluminium at this time
The dissolution amount of the steel plate is 0.001 to 0.2 g / m²Is
preferable. Also, acid concentration, such as sulfuric acid concentration and aluminum
Select the ion concentration from the range that does not crystallize at room temperature.
It is preferable. The preferred aluminum ion concentration is
0.1 to 50 g / L, particularly preferably 5 to 15 g
/ L. Also, after the acid etching process is finished
In order not to take the processing liquid to the next process,
It is preferable to perform draining with water and washing with spray.
That's right. <Desmutting treatment in acidic aqueous solution (first
Desmut treatment)> Chemical etching with alkaline water
In general, the surface of aluminum
In this case, phosphoric acid, nitric acid,
Contains acid, chromic acid, hydrochloric acid, or two or more of these acids
Desmut with mixed acid. The concentration of the acidic aqueous solution is 0.5
~ 60 wt% is preferred. In addition, aluminum in acidic aqueous solution
Alloy compositions contained in aluminum alloys as well as
Minutes of 0 to 5 wt% may be dissolved. Desma
Generated by electrochemical surface roughening treatment
Use of waste liquid and waste liquid generated by anodizing
preferable. The liquid temperature is from room temperature to 95 ° C.
70 ° C. is particularly preferred. Processing time is preferably 1 to 120 seconds
In particular, 1 to 5 seconds is preferable. Desmut processing is complete
In order to prevent the processing solution from being brought into the next process after
Perform draining with a prowler and washing with spray.
And are preferred. Liquid draining and spraying with nip rollers
Washing with water, desmut treatment liquid used in the next step
When using the same type of liquid or liquid with the same composition
Can be omitted. Electrochemical roughening treatment
This device is used to prevent dissolution of the electrode and control the roughened shape.
When using an auxiliary anode tank for rolls, the auxiliary anode tank
Electrochemical roughening treatment by alternating current flowing through the aluminum plate
If you bring it in front of the tank, electrochemical roughening
Omit desmutting step in acidic aqueous solution before treatment
You can also <Electrochemical roughening treatment> In the present invention
Electrochemical roughening treatment is an aqueous solution mainly composed of nitric acid.
Electrochemical surface roughening treatment under specific conditions (No. 1
Electrochemical roughening treatment) in aqueous solution mainly composed of hydrochloric acid
Electrochemical roughening treatment under specific conditions (second electric
Is characterized by the combination of gas-chemical roughening treatment)
The Electrochemical roughening treatment under these specific conditions
Treatment and anodizing treatment, if necessary, mechanical roughening treatment
By performing each surface treatment described in this specification,
The object of the present invention can be achieved. Specific conditions
The electrochemical surface roughening process will be described below. (1) An aqueous solution mainly composed of nitric acid (first electric
Chemical roughening treatment) The aqueous solution mainly composed of nitric acid in the present invention is a normal direct current.
Or used for electrochemical surface roughening using alternating current
1 to 100 g / L nitric acid aqueous solution,
Such as luminium, sodium nitrate, ammonium nitrate
Nitrate ion, aluminum chloride, sodium chloride, chloride
Hydrochloric acid or nitric acid with hydrochloric acid ions such as ammonium
Use by adding one or more compounds from 1 g / L to saturation
Can. In addition, a compound that forms a complex with copper 1
It can also be added at a rate of ˜200 g / L. Nitric acid
The aqueous solution mainly contains iron, copper, manganese, nickel
Aluminum such as ru, titanium, magnesium, silica
The metal contained in the alloy may be dissolved. Hypochlorous acid
An acid or hydrogen peroxide may be added at 1 to 100 g / L. liquid
Aqueous solution containing a temperature of 15 to 90 ° C. and 5 to 15 g / L of nitric acid
Add aluminum salt (aluminum nitrate) to the
This is an aqueous solution containing 3-50 g / L of minium ions.
Are particularly preferred. Addition to aqueous solution mainly composed of nitric acid
Known as things, equipment, power supply, current density, flow rate, temperature
Those used for electrochemical roughening can be used.
The The power source used for electrochemical roughening is AC or DC.
Is used, but alternating current is particularly preferred. Mainly nitric acid
The aluminum plate is formed by electrochemical surface roughening in an aqueous solution.
The amount of electricity involved in the anodic reaction is electrochemical roughening treatment.
10 to 1000 C / dm when²Range of
30-500 C / dm²Is preferred, 45
~ 300C / dm²Is particularly preferred. (2) Aqueous solution mainly composed of hydrochloric acid (second electric
Chemical roughening treatment) The aqueous solution mainly composed of hydrochloric acid as used in the present invention is a normal direct current.
Or used for electrochemical surface roughening using alternating current
Can be used in an aqueous solution of 1-10 g / L hydrochloric acid.
Glasses such as minium, sodium nitrate, ammonium nitrate
Acid ion, aluminum chloride, sodium chloride, chloride
Hydrochloric acid or nitrate with hydrochloric acid ions such as ammonium
Use by adding one or more compounds from 1 g / L to saturation
be able to. Moreover, the compound which forms a complex with copper is 1-
It can also be added at a rate of 200 g / L. Mainly hydrochloric acid
In the aqueous solution to make the body, iron, copper, manganese, nickel,
Aluminum alloys such as titanium, magnesium and silica
The metal contained therein may be dissolved. Hypochlorous acid and
Hydrogen peroxide may be added at 1 to 100 g / L. Hydrochloric acid water
The solution contains a liquid temperature of 15 to 50 ° C. and 1 to 10 g / L of hydrochloric acid.
In the aqueous solution, aluminum salt (aluminum chloride, A
lCl_Three・ 6H₂O) added at a rate of 10-70 g / L
Water solution with an aluminum ion concentration of 1-8 g / L
A liquid is particularly preferable. Such hydrochloric acid aqueous solution
When the surface is subjected to electrochemical surface roughening,
Due to uniform surface shape, low purity aluminum rolling
Plate (aluminum plate or alloy component containing a lot of alloy components)
Even if an aluminum plate not prepared is used,
Uneven processing due to surface treatment does not occur, and a lithographic printing plate
Sometimes excellent printing durability and printing performance (dirt performance)
it can. Here, hydrochloric acid aqueous solution is 1-10 g / L hydrochloric acid.
It is preferable to contain, especially 2 to 6 g / L
preferable. The added aluminum chloride hexahydrate is 10
~ 70 g / L is preferred, and 20-50 g / L
More preferably, it is 35 to 45 g / L.
Is preferred. Hydrochloric acid with aluminum chloride hexahydrate added
The aluminum ion concentration of the aqueous solution is 1-8 g / L.
2-6g / L is more preferable
4 to 5 g / L is particularly preferable. Mainly hydrochloric acid
Additives, equipment, power supply, current density, flow into aqueous solution
For speed and temperature, use for known electrochemical surface roughening
Things can be used. Used for electrochemical roughening
AC or DC is used as the power source.
Good. Electrochemical roughening in aqueous solution mainly composed of hydrochloric acid
The amount of electricity that the aluminum plate takes part in the anodic reaction during
When the electrochemical roughening treatment is completed, 10 to 10
00C / dm²Can be selected from the range of 20 to 80 C / d
m²Is preferably 25-60 C / dm²Is particularly preferred
Yes. (3) Electrochemical roughening Electrochemical roughening is the treatment of aluminum in acidic aqueous solution.
Direct current or alternating current between the nium plate and the opposite electrode
It means that the surface is electrochemically roughened by applying a flow. Book
In the invention, alternating current is particularly preferred.
Any of a phase, a three-phase, etc. may be sufficient. Also, AC and DC
A superimposed current can also be used. Electrolysis tank is well known
Can be used for electrochemical roughening
The electrolytic cell is a well-known table such as a vertical type, flat type, or radial type.
An electrolytic cell used for surface treatment can be used. Electrolytic treatment tank
A plurality may be provided. Also in acid or alkaline aqueous solution
Etching treatment in water, desmutting treatment in acidic aqueous solution
Aluminum plate in acid, acid or neutral salt solution
Repeated electrochemical surface roughening process with the electrode electrolytic process in between.
You may go back and forth. A) Power feeding method to aluminum plate Conductor roll is used as the power supply method to the aluminum plate.
Liquid supply without direct power supply or conductor roll
An electric system (indirect power supply system) can be used. Electrolytic cell
The electrolyte that passes through the interior of the
It can be a real or counter. One in one electrolytic cell
The above AC power supplies can be connected. Indirect power supply method
Is used, Japanese Patent Publication No. 6-37716,
A method using an auxiliary anode described in JP-A-5-42520
The amount of electricity applied to the aluminum plate during the anode and the cathode
It is preferable to adjust the ratio of the amount of electricity. Flow to auxiliary anode
Rectifier elements such as thyristors, diodes, and GTOs
It is particularly preferable to control using a child. JP 6-3
If the method described in Japanese Patent No. 7716 is used,
The electrode facing the carbon electrode of the main electrode where the roughening reaction takes place
The quantity of electricity at the time of anode of the alternating current on the surface of the ruminium plate
The amount of electricity (current value) at the time of the cathode can be easily controlled. Also,
In terms of power supply production, the effect of transformer bias is small and very
Is advantageous. Electrochemical roughening using sine waves
The current value control method is a transformer, variable induction voltage
Adjustable current value for electrolysis using a regulator etc.
This is performed by feeding back to the induction voltage regulator. And
The method for controlling the current value is disclosed in JP-A-55-25812.
System that controls the phase with a thyristor
Can also be used together. Aluminum is used for electrochemical surface roughening.
If the distance between the plate and electrode and the liquid flow rate are not constant, current bias will occur.
Easy to produce, resulting in uneven processing of the aluminum surface
Is not suitable as a support for lithographic printing plates
End up. In order to solve the problem,
1-5mm in the width direction of the aluminum web
Use a liquid supply nozzle with slits for blowing out liquid
be able to. In addition, a plurality of liquid pool chambers are provided.
A valve and a flow meter are installed in the piping connected to the liquid pool chamber.
Adjust the amount of liquid blown out from each slit.
It is particularly preferred that Aluminum web and electrode
The distance of 5-100mm, especially 8-15mm is preferred
Yes. In order to keep this distance constant, Japanese Patent Publication No. 61-3003
The surface described in No. 6 Gazette on the surface on which the running web can slide
The web is run while being pressed against the sliding surface using pressure.
A method is used. Or JP-A-8-300843
Use a roller with a large diameter as described in
The method of keeping the distance of the aluminum plate constant can also be used.
it can. When using the direct feeding method, Japanese Patent Laid-Open No. 58
Conductor roll as described in JP-A-177441
And an apparatus described in JP-A-56-123400
It is preferable to roughen the surface electrochemically. Conda
Kuta rolls are installed on the upper or lower surface of the aluminum web.
Can be installed on the upper surface of the aluminum plate.
And press against the aluminum plate with a nip device
It is particularly preferable to do this. Aluminum plate is a conductor
The length in contact with the rail is 1 to 30 with respect to the aluminum traveling direction.
0 mm is preferable. Conductor across an aluminum plate
The pass roll facing the roll is a rubber roll.
And are preferred. Pressing pressure, rubber roll hardness is arc
Set arbitrarily under conditions that do not generate spots. Kondak
By installing the talol on the upper surface of the aluminum plate,
Dactor roll replacement and inspection work is simplified. Co
The power supply brush is slid against the rotating body at the end of the dactor roll.
It is preferable to use a method of energizing while maintaining the current. Armini
The conductor roll pressed against
Always electrochemical rough surface to prevent spot generation
With the same composition and the same temperature as the electrolyte used
It is preferable to always cool. If foreign matter enters the electrolyte
It is easy to cause an arc spot, so it is used for cooling.
Wrap filter cloth etc. around spray, or upstream of spray tube
Put a fine mesh filter in the pipe.
Is preferred. B) Electrochemical roughening using alternating current The AC power supply waveform used for electrochemical roughening is a sign
Wave, rectangular wave, trapezoidal wave, triangular wave, etc. can be used
However, rectangular or trapezoidal waves are preferred, and trapezoidal waves are particularly preferred.
That's right. The frequency is preferably 0.1 to 500 Hz, 40 to
120 Hz is more preferable, and 45 to 65 Hz is particularly preferable.
That's right. When trapezoidal wave is used, current reaches peak from 0
The time tp until is preferably 0.1 to 2 msec,
0.3-2 msec is particularly preferable. Impedance of power circuit
If tp is less than 0.1 due to
A large power supply voltage is required at the rise of the waveform.
Source equipment costs increase. Greater than 2 msec
And easily affected by trace components in the electrolyte
Roughening is difficult to be performed. Used for electrochemical roughening
The condition of one cycle of AC
The ratio of the reaction time ta to the AC cycle T (in the present invention
It is called “duty”. ) Ta / T is 0.33-
0.66 is preferable, and 0.45-0.55 is more preferable
0.5 is particularly preferable. Aluminum alloy plate surface
Is mainly composed of aluminum hydroxide during the cathode reaction.
Oxide film is generated, and further, dissolution and destruction of the oxide film
May occur. And the dissolution and destruction of the oxide film is
The part where melting or destruction occurs is the next aluminum
Opening of pitting reaction during anodic reaction of alloy plate
The starting point. Therefore, the selection of AC duty is uniform
This is particularly important in that an electrolytic surface roughening treatment is performed. Electricity applied to the aluminum plate facing the main electrode
The amount of electricity is the amount of electricity Qc when the aluminum plate is cathodic.
The ratio Qc / Qa of the amount of electricity Qa during the anode reaction is 0.9
-1.0, preferably 0.92-0.9.
8, particularly preferably 0.94 to 0.96
The When Qc / Qa is within this range, the surface is roughened.
There is no processing unevenness and printing durability is improved when using a lithographic printing plate.
And printing performance (dirt performance). Qc /
If Qa exceeds 1.0, the electrode may be dissolved. this
Electricity ratio control controls the voltage generated by the power supply.
Can be done. Electrolytic surface roughening treatment
Using an AC electrolytic cell with an auxiliary electrode to shunt current
In the case of carrying out, JP-A-60-43500 and JP
As described in the Kaihei 1-52098 publication,
Controlling the current value of the anode current diverted to the auxiliary electrode
Thus, Qc / Qa can be controlled. Current density
Is the peak value of the trapezoidal wave, and the current is on the anode cycle side Ia,
10 to 200 A / dm for both cathode cycle side Ic²
Is preferred. Ia / Ic is in the range of 0.5-3
Is preferred. Electrochemical roughening using alternating current in the present invention
The electrolytic cell used for the vertical type, flat type, radial type, etc.
A known electrolytic cell for surface treatment can be used.
Radial type as described in Kaihei 5-195300
An electrolytic cell or a flat type is particularly preferable. The electrode is carbo
Use the main electrode as the main electrode and ferrite as the auxiliary anode.
Are particularly preferred. Also, multiple AC electrolyzers are arranged in series.
The installed electrolytic surface roughening apparatus can also be used suitably.
The An electrolytic cell having an auxiliary anode has a main electrode.
Can be installed before or after the electrolytic cell, but especially salt
Auxiliary power used in electrochemical surface roughening process mainly composed of acid
Hold the electrolytic cell with the pole in front of the electrolytic cell with the main electrode.
It is preferable to reduce the occurrence of processing unevenness.
Yes. Also, the inlet (liquid level) of the electrolytic cell with the auxiliary electrode and the main
The distance to the inlet (liquid level) of the electrolytic cell with poles is too long
Metal in aluminum plate by chemical dissolution reaction of water and hydrochloric acid
The intermetallic compound dissolves to form deep holes, and the photosensitive layer in that area
It becomes thick and uneven during printing. Therefore alumini
Mainly from the inlet (liquid level) of the electrolytic cell where the aluminum plate has an auxiliary electrode
3 seconds or less to the entrance (liquid level) of the electrolytic cell with electrodes
It is preferable that In the electrolytic surface roughening treatment, 1 or 2 or more
In the above AC electrolytic cell, different polarities in one electrolytic cell
Aluminium between the main poles connected to the power terminals
A break in which alternating current does not flow between the alloy plate and these main electrodes
One or more periods are provided, and the length of the suspension period is 0.001
~ 0.6 seconds, honeycomb pits
It is preferable because it is uniformly formed on the entire surface of the metal plate. Than
Preferably 0.005-0.55 seconds, more preferably
0.01 to 0.5 seconds. 2 or more arranged in series
When using an AC electrolytic cell, one AC electrolytic cell and another
Alternating current flows in the aluminum alloy plate between the flow electrolysis layer
It is preferable to set the time not to be 0.001 to 20 seconds.
More preferably, it is 0.1-15 seconds, More preferably, it is 1-1.
2 seconds. FIG. 2 is a diagram of a flat frame suitably used in the present invention.
Discontinuation of an example of an electrolytic surface-roughening treatment apparatus equipped with a to-type AC electrolytic cell
A surface schematic diagram is shown. In FIG. 2, 2 is an AC electrolytic cell, 4
A, 4B, 4C are main poles, 6A, 6B are transport rollers, 8A
Is an introduction roller, 8B is a discharge roller, and 100 is electrolytic roughing.
It is a surface treatment apparatus. The electrolytic surface roughening treatment apparatus 100 is
Three-phase exchange while transporting the ruminium web W in a substantially horizontal direction
Current (hereinafter also referred to as “three-phase alternating current”) for electrolysis
It is an electrolytic surface roughening apparatus which performs a surface roughening process. The electrolytic surface roughening treatment apparatus 100 is made of aluminum.
It extends along the conveyance direction a of the web web W and the upper surface is opened.
Shallow box-shaped AC electrolytic cell 2 and the vicinity of the bottom surface of AC electrolytic cell 2
The conveyance path of the aluminum web W along the conveyance direction a
Three plate-like shapes arranged parallel to the transport surface T, which is a path
Main electrodes 4A, 4B and 4C, and the inside of the AC electrolytic cell 2
The upstream side with respect to the transport direction a (hereinafter simply “upstream”
"Side". ) And the downstream side with respect to the transport direction a (hereinafter
Below, it is simply called “downstream”. ) Near the end of
Conveys aluminum web W inside AC electrolytic cell 2
Conveying rollers 6A and 6B and the upper side of the AC electrolytic cell 2
Is located on the upstream side of the aluminum web W
An introduction roller 8A to be introduced into the electrolytic cell 2 and AC electrolysis
Located on the downstream side of the tank 2 and inside the AC electrolytic cell 2
The aluminum web W that has passed through the outside of the AC electrolytic cell 2
And a derivation roller 8B. In AC electrolytic cell 2
The acidic aqueous solution mentioned above is stored in the part. Main pole 4
A, 4B and 4C each generate a three-phase AC
Connected to U terminal, V terminal and W terminal of AC power supply Tac
Has been. Therefore, the main poles 4A, 4B and 4C
The applied alternating current is shifted in phase by 120 °. Regarding the operation of the electrolytic surface roughening treatment apparatus 100
This will be described below. Aluminum web W is an introduction roller
8A introduced into the AC electrolytic cell 2
Constant speed along conveyance direction a by la 6A and 6B
It is conveyed by. Inside the AC electrolytic cell 2, aluminum
Umweb W is flat against main poles 4A, 4B and 4C.
Move to row and from main poles 4A, 4B and 4C
AC is applied. Thereby, the aluminum web W
In this case, the anode reaction and the cathode reaction occur alternately.
When the anode reaction is taking place,
When the cathode reaction occurs,
An aluminum oxide film is formed and the surface is roughened.
The The alternating current applied to the main poles 4A, 4B and 4C is
As described above, the phase is shifted by 120 °.
In 4B, it is 120 rather than the phase (U phase) of the main pole 4A.
Anode reaction and cathode reaction with a phase delayed by V (phase V)
Is repeated, and the main pole 4C is 1 more than the main pole 4B.
Anode reaction and cathode reaction in 20 ° phase (W phase)
The response is repeated. Therefore, aluminum web
In W, a single-phase alternating waveform current having the same frequency is applied.
The anode reaction and cathode are three times more frequent than
High speed and power
Even when electrolytic surface roughening is performed at a flow density, the width direction
Chatter marks that are stripes are less likely to occur. FIG. 3 shows a flat frame suitably used in the present invention.
Another example of electrolytic surface-roughening treatment equipment equipped with a to-type AC electrolytic cell
The cross-sectional schematic diagram of is shown. In FIG. 3, the same reference numerals as in FIG.
Indicates the same element as that indicated by the reference numeral in FIG.
10 is an auxiliary electrolytic cell, 12 is an auxiliary electrode, 14A, 14
B is a transport roller, 16A is an introduction roller, 16B is a delivery roller
, 102 is an electrolytic surface-roughening treatment device and Th1, Th
2, Th3 is a thyristor. Electrolytic surface roughening treatment equipment 1
02 is an alternating current provided in the electrolytic surface roughening treatment apparatus 100 described above.
Electrolytic rough surface in which an auxiliary electrolytic cell 10 is disposed in front of the flow electrolytic cell 2
It is a chemical processing apparatus. The auxiliary electrolytic cell 10 has an open top surface.
It is a box shape, and the aluminum web W is carried near the bottom.
A plate-like auxiliary electrode 12 is provided in parallel to the feeding surface T.
Yes. The vicinity of the upstream side wall surface and the downstream side wall surface of the auxiliary electrolytic cell 10
In the vicinity of the aluminum web W, the auxiliary electrode 12
Conveying rollers 14A and 14B that convey above
It is arranged. Also, above the auxiliary electrolytic cell 10
On the upstream side, the aluminum web W is connected to the auxiliary electrolytic cell 10.
An introduction roller 16A to be introduced inside is provided, and auxiliary electrolysis
On the downstream side above the tank 10, there is an inside of the auxiliary electrolytic tank 10.
Derivation of the aluminum web W that has passed through
A roller 16B is provided. Inside the auxiliary electrolytic cell 10
The acidic aqueous solution mentioned above is stored. AC power supply Tac U phase, V phase and W phase
Are connected to the auxiliary electrode 12, respectively, and the U phase, V phase and
Between each of the W phase and the auxiliary electrode 12
Th1, Th2 and Th3 are interposed. Rhino
Listers Th1, Th2, and Th3 are all fired
Current flows from the AC power supply Tac to the auxiliary electrode 12
Connected so that. Therefore, thyristor Th
1, any of Th2 and Th3
Since the anode current flows through the auxiliary electrode 12, the thyristor
By controlling the phase of Th1, Th2 and Th3
The current value of the anode current flowing through the auxiliary electrode 12 is controlled.
And therefore also control the value of Qc / Qa
Can. FIG. 4 shows a radius that is preferably used in the present invention.
Disconnection of an example of an electrolytic surface-roughening treatment apparatus equipped with a water-type AC electrolytic cell
A surface schematic diagram is shown. In FIG. 4, 20 is an AC electrolytic cell, 2
6A and 26B are main electrodes, 34 is an auxiliary electrolytic cell, and 35 is an upstream side.
Guide roller, 36 auxiliary electrode, 22 AC electrolytic cell body,
22A is an opening, 24 is a feed roller, 28A and 28B are
Liquid supply nozzle, 30A is upstream guide roller, 30B is downstream
Side guide roller, 32 is overflow tank, 34A is bottom of auxiliary electrolytic cell
Surface 104 is an electrolytic surface roughening treatment device and Th4 and Th5.
Is a thyristor. Electrolytic surface roughening treatment apparatus 104 is an acid
AC comprising an AC electrolytic cell main body 22 in which an aqueous solution is stored
The electrolytic cell 20 and the AC electrolytic cell main body 22 are accommodated inside, and the water
Arranged rotatably around an axis extending in the plane direction
Move the Minium web W from the left to the right in FIG.
And a feed roller 24 for feeding in the transport direction a.
The In the AC electrolytic cell main body 22, the acidic aqueous solution described above is provided.
Is stored. The inner wall surface of the AC electrolytic cell main body 22
It is formed in a substantially cylindrical shape so as to surround the roller 24,
On the inner wall surface, semi-cylindrical main poles 26A and 26B
Are provided with the feed roller 24 in between. Main pole 26A
And 26B are divided into a plurality of small electrodes,
An insulating spacer is interposed between the small electrodes.
The For example, small electrodes can be formed using graphite or metal.
The spacer can be, for example, vinyl chloride
It can be formed of resin. The spacer thickness is
It is preferable that it is 1-10 mm. In FIG.
Is shown in a simplified manner, whichever of the main poles 26A and 26B
Also in the case of small electrodes divided by spacers
Each is connected to an AC power source Tac. The upper part of the AC electrolytic cell 20 has aluminum.
The web W is introduced into the AC electrolytic cell main body 22 and is led out.
An opening 22A for this purpose is formed. AC electrolytic cell book
In the vicinity of the opening 22A in the body 22, there is an AC electrolytic cell book
A liquid supply nozzle 28A for replenishing the body 22 with an acidic aqueous solution is provided.
It has been. A liquid supply nozzle 28B is also provided separately.
Yes. Near the opening 22A above the AC electrolytic cell 20
The aluminum web W is placed inside the AC electrolytic cell main body 22.
A group of upstream guide rollers 30A for guiding to the
Aluminum surface that has been subjected to electrolytic surface roughening in the tank body 22.
A group of downstream guide rollers 30B for guiding the hub W to the outside;
Is arranged. In the AC electrolytic cell 20, the AC electrolytic cell main
An overflow tank 32 is provided adjacent to the downstream side of the body 22.
The In the overflow tank 32, the above acidic aqueous solution is stored.
It is. The overflow tank 32 overflows from the AC electrolytic cell main body 22.
The acidic aqueous solution temporarily stored in the AC electrolytic cell main body 22
It has a function to keep the level of acidic aqueous solution constant.
To do. In the previous stage (upstream) of the AC electrolytic cell main body 22,
An auxiliary electrolytic cell 34 is provided. The auxiliary electrolytic cell 34
It is shallower than the AC electrolytic cell main body 22 and the bottom surface 34A is flat.
Is formed. On the bottom surface 34A, a cylindrical shape
A plurality of auxiliary electrodes 36 are provided. Auxiliary electrolytic cell 34
The acidic aqueous solution mentioned above is stored inside. Auxiliary power
The pole 36 is made of a highly corrosion-resistant metal such as platinum, ferrite, etc.
It is preferable that it is formed by. Also, the auxiliary electrode 3
6 may be plate-shaped. The auxiliary electrode 36 is an AC power source T
On the side where the main pole 26A in ac is connected, the main pole 26A
Is connected in parallel with the thyristor Th4 in the middle.
However, the auxiliary power from the side of the AC power supply Tac is
It is connected so that a current flows toward the pole 36.
Further, the main electrode 26B in the AC power supply Tac is connected.
The side is also connected to the auxiliary electrode 36 via the thyristor Th5.
It is. The thyristor Th5 is also connected to the AC power supply Ta
The auxiliary electrode 36 from the side to which the main electrode 26B is connected in c
It is connected so that a current flows toward. Sairi
When either of the stars Th4 and Th5 is fired,
An anode current flows through the auxiliary electrode 36. Therefore,
By controlling the phase of irristors Th4 and Th5
The current value of the anode current flowing through the auxiliary electrode 36 is controlled.
And therefore also control the value of Qc / Qa
Can. Regarding the operation of the electrolytic surface roughening treatment apparatus 104
This will be described below. From the left in FIG. 4, aluminum
The alloy plate W is first assisted by the upstream guide roller 35.
Guided into the electrolytic cell 34 and then the upstream guide roller 30
A is guided to the AC electrolytic cell main body 22 by A. And
From the left to the right in FIG.
Sent by the downstream guide roller 30B.
The Inside the AC electrolytic cell main body 22 and the auxiliary electrolytic cell 34
The aluminum web W has the main poles 26A and 2A.
The AC current applied to 6B and the auxiliary electrode 36
Surface of the main electrodes 26A and 26B
Surface is roughened and almost uniform honeycomb pits
Is formed. (4) Recycling of waste liquid used for roughening The liquid (waste liquid) used for each roughening treatment is recycled as much as possible.
Preferably. Caustic melted aluminum ions
In aqueous soda solutions, aluminum and caustic soda are prepared by crystallization.
Can be separated. Aluminum ion
In a dissolved sulfuric acid aqueous solution, nitric acid aqueous solution or hydrochloric acid aqueous solution,
Recovery of sulfuric acid or nitric acid by air dialysis and ion exchange resin
It can be performed. Hydrochloric acid with aluminum ions dissolved
In aqueous solution, it is described in JP2000-282272A.
Recovery by evaporation can also be performed. Book
In the invention, the waste liquid of the electrolyte used in the electrochemical surface roughening treatment
The desmut process (first, second and third desmut process)
It is preferably used for Electrochemical roughening
Desmut treatment performed before treatment or anodizing treatment
Roughening or anodizing after desmutting
It is preferable to use the same type of liquid as
It is particularly preferable to use the resultant solution. By doing so,
The water washing process provided between the desmut treatment and the next process
Can be omitted, simplifying equipment and reducing the amount of waste liquid
It becomes ability. <Chemical etch in aqueous alkali solution
Treatment (second and third alkali etching treatment)> first
1 electrochemical roughening treatment followed by 2nd electrochemical roughening treatment
It is preferable to perform the second alkali etching process before
Yes. This process makes the second electrochemical surface roughening process uniform.
And the surface shape of the aluminum plate is uniform.
A lithographic printing plate with excellent printing durability and printing performance.
The In addition, after the second electrochemical surface roughening treatment, anodization treatment is performed.
It is preferable to perform the third alkali etching process before
Yes. This process produced a second electrochemical surface roughening process.
Removal of smut component (mainly aluminum hydroxide)
In addition, the surface shape of the aluminum plate is uniform and printing durability is high.
And a lithographic printing plate excellent in printing performance. Second Al
Potash etching treatment and third alkali etching treatment
Contact the aluminum alloy plate with an alkaline solution.
Etching is performed. Alkali type, a
A method of contacting the aluminum alloy plate with an alkaline solution;
And the apparatus used for the first alkali etching treatment
The same thing as a case is mentioned. Used in alkaline solutions
As the alkali to be used, the first alkali etching treatment
The same thing as a case is mentioned. Concentration of alkaline solution
Can be determined according to the etching amount,
It is preferable that it is 0.01-80 mass%. Alkali-soluble
The temperature of the liquid is preferably 20 to 90 ° C. processing time
Is preferably 1 to 60 seconds. Second alkali etch
Aluminum plate (electrolytic roughening treatment)
The amount of dissolution of the surface subjected to is preferably 0.001 to 3
0g / m²More preferably, 0.1 to 4 g / m
²And particularly preferably 0.2 to 1.5 g / m. ²so
is there. In the third alkali etching process, aluminum
The amount of dissolution of the nickel plate (surface that has been subjected to electrolytic surface roughening)
Preferably 0.001-30g / m²Is more preferred
Or 0.1-2 g / m²And particularly preferably,
0.1-0.6 g / m ²It is. After the second alkali etching process, the second degassing is performed.
A smut treatment is preferably performed. Second electrochemical rough surface
Can be performed more uniformly. The third al
Do the third desmut process after the potash etching process
Is preferred. Water generated by the third alkali etching process
Oxide can be removed, and the support and photosensitive layer can be
A lithographic printing plate with high adhesion is obtained. Second desmut treatment
And the third desmut process is, for example, the above aluminum
Concentration of phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid 0.5%
˜30 mass% acidic solution (aluminum ion 0.01
Contains -5% by weight. Line by contacting)
Yeah. Method of contacting aluminum alloy plate with acidic solution
Is the same as in the case of the first desmut treatment.
The For the second desmut process and the third desmut process
In an anodic oxidation treatment described later as an acidic solution
It is preferable to use a waste solution of sulfuric acid solution discharged in this manner. Ma
Instead of the waste liquid, the sulfuric acid concentration is 100 to 600 g /
L, the aluminum ion concentration is 1-10 g / L,
A sulfuric acid solution having a liquid temperature of 60 to 90 ° C. can also be used.
The Liquid for second desmut treatment and third desmut treatment
The temperature is preferably 25 to 90 ° C. In addition, the second
The processing time of the smut process and the third desmut process is
It is preferably 1 to 180 seconds. Second desmut treatment
And the acidic solution used for the third desmut treatment is
Aluminum and aluminum alloy components melt
May be. <Anodizing treatment> The surface of the aluminum plate
Anodization is applied to increase the wear resistance. Al
As an electrolyte used for anodizing of minium plates
Whatever forms a porous oxide film
Can also be used. In general, sulfuric acid, phosphoric acid,
Uric acid, chromic acid, or a mixture thereof is used.
The concentration of these electrolytes is appropriately determined according to the type of electrolyte.
It is done. The anodizing treatment conditions vary depending on the electrolyte used.
As a result, it cannot be specified in general, but in general, the concentration of the electrolyte
The temperature is 1 to 80 wt%, the liquid temperature is 5 to 70 ° C., and the current density is 1 to 1.
60A / dm², Voltage 1-100V, electrolysis time 10 seconds
It is appropriate if it is in the range of 300 seconds. The sulfuric acid method is usually direct current
Processing is done with electric current, but alternating current can also be used.
The The amount of anodized film is 1-5g / m²The range is suitable
is there. 1g / m²If it is less, the printing durability is insufficient.
Or scratches on the non-image area of the planographic printing plate
At the same time, ink adheres to the flaws, so-called fouling.
This tends to occur. Also, the amount of anodized film increases
And the oxide film tends to concentrate on the aluminum etch part
So, the etch part and the center part of the aluminum plate
The difference in the amount of oxide film is 1 g / m²Preferred to be
Yes. Regarding anodic oxidation in sulfuric acid aqueous solution,
No. 54-128453, JP-A 48-45303
It is described in detail in each publication. Sulfuric acid concentration 10-300
g / L, aluminum ion concentration 1-25 g / L
In a 50 to 200 g / L sulfuric acid aqueous solution.
Add aluminum sulfate to reduce the aluminum ion concentration
It is especially preferable to set it as 2-10 g / L. Liquid temperature is 30
~ 60 ° C is preferred. When using the DC method, the current density is 1
~ 60A / dm², Especially 5-40A / dm²Is preferred
Yes. When anodizing aluminum sheets continuously
Prevent the current concentration called burning of the aluminum plate
First 5-10A / dm²Anodizing at low current density
And gradually increase the current density in the second half.
0-50A / dm²Until or
It is particularly preferable to set the flow density. Current density is 5
It is preferable to gradually increase in 15 steps. Each step
Each power supply has an independent power supply.
The current density is controlled by the flow value. Power supply method is Konda
A liquid power feeding method that does not use a kuta roller is preferable. JP 20
An example is shown in 01-11698A. The sulfuric acid aqueous solution contains aluminum.
Of course, a small amount of trace component elements may be dissolved.
It is. Aluminum is eluted in sulfuric acid aqueous solution during anodization
Therefore, sulfuric acid concentration and aluminum for process control
It is necessary to control the muon concentration. Aluminum Io
If the concentration of the aqueous solution is set low, the sulfuric acid aqueous solution that performs anodic oxidation is further changed.
New must be done frequently, waste volume increases and economical
Not only is it an environmental problem. Also al
If the concentration of minium ion is set high, the electrolysis voltage increases.
Power costs are high and not economical. Preferred anodization
As sulfuric acid concentration, aluminum ion concentration, and liquid temperature, (Part 1) Sulfuric acid concentration 100-200 g / L (further 130-180
g / L) Aluminum ion concentration 2-10 g / L (further 3-7
g / L) Liquid temperature 30-40 ° C (more 33-38 ° C) (Part 2) Sulfuric acid concentration 50-125 g / L (further 80-120 g / L
L) Aluminum ion concentration 2-10 g / L (further 3-7
g / L) Liquid temperature 40-70 (further 50-60 ° C) It is. Supply to aluminum plate in anodizing treatment
Electric system is aluminum directly using a conductor roll
A direct power supply method for supplying power to the plate and aluminum through an electrolyte.
There is a liquid power supply system that supplies power to the metal plate. The direct power supply method is
Relatively low speed and low current density with an in-speed of 30 m / min or less
The indirect power supply method uses an anodizing device of 30m /
Used in anodizing equipment with high speed and high current density exceeding min
It is often done. Indirect power supply method is continuous surface treatment technology
2 (General Technology Center, issued on September 30, 1986)
As shown on page 89, Yamakoshi type or straight type tank tray
Iout can be used. High speed and high current density
The spar between the conductor roll and the aluminum web
The direct feed roll method is not possible.
It is profit. Aluminum for both direct power supply and indirect power supply
Energy loss due to voltage drop in the nium web
In order to reduce the number, the anodizing process is separated into two or more.
Power supply tank and oxidation tank or condenser of each electrolyzer
Connect a DC power source between the ductor roll and the oxidation tank.
It is particularly preferred. When using the direct power supply method,
In general, the dactor roll is made of aluminum. B
In order to extend the service life of the service, Japanese Patent Publication No. 61-50138
Industrial pure aluminum as described in the Gazette
After casting using a high temperature homogenization treatment, Al-
Fe-based crystallized material is Al_ThreeImproved corrosion resistance as a single layer of Fe
It is particularly preferable to use those prepared. Anodizing treatment
Since a large current flows in the process, the current flowing in the bus bar
Due to the magnetic field generated by the flow,
The force is working. The result is a web meandering problem
Therefore, it is described in JP-A-57-51290
It is particularly preferable to use such a method. Also, a large current flows through the aluminum plate.
Therefore, the magnetic field due to the current flowing through the aluminum plate itself
The aluminum plate toward the center in the width direction.
-Rents force works. As a result, the aluminum plate is broken.
Because it is easy to produce, the diameter is 100 ~ in the anodizing tank.
A 200 mm pass roller is pulled between 100 and 3000 mm.
Provide a plurality of rolls and wrap at an angle of 1 to 15 degrees.
It is especially preferred to take a method to prevent breakage due to force
That's right. In addition, the anodized film is in the width direction of the aluminum plate.
The amount of production is different, and the amount of production increases as it approaches the etch.
Thickness increases. As a result, the winding machine uses aluminum
The problem arises that the steel plate cannot be wound well. Solve this
To this end, Japanese Patent Publication No. 62-30275 or Japanese Patent Publication No. 5
The liquid flow is agitated by the method described in Japanese Patent Publication No. 5-21840.
And can be solved. If that method is not enough
The aluminum plate winding device is 0.1 to 10 Hz.
The width of the aluminum web with an amplitude of 5-50 mm with a period of
Used in combination with the method of oscillating in the direction and winding up
It is particularly preferred. In the sulfuric acid method, the treatment is usually performed with a direct current.
However, alternating current can be used. Of anodized film
The amount is 1-10g / m²The range of is appropriate. General lithographic
In the case of printing plate materials, the amount of anodized film is 1 to 5 g / m.
²1g / m²If it is less, the printing durability is insufficient.
Or scratches on the non-image area of the planographic printing plate
At the same time, the ink is attached to the scratched area, so-called scratched dirt.
It tends to occur. Also, when the amount of anodized film increases,
Easy to concentrate oxide film on the etched part of aluminum plate
So, the etch part and the center part of the aluminum plate
The difference in the amount of oxide film is 1 g / m²Preferred to be
Yes. For continuous anodizing treatment, the liquid feeding method should be used.
It is common. Positive for energizing the aluminum plate
The poles include lead, iridium oxide, platinum, and ferrite.
Can be used, but it is mainly made of iridium oxide.
Those are particularly preferred. Iridium oxide is heat treated
The substrate is coated. The base material is titanium, tantalum, ni
So-called valve metals such as ob and zirconium are used.
However, titanium or niobium is particularly preferred. The valve gold
The genus has a relatively large electrical resistance, so copper is used as the core material.
It is especially preferred to clad the valve metal around
Yes. When cladding a valve metal on a copper core,
It is difficult to make a complicated shape.
After coating the electrode parts created with iridium oxide
Assembled to the desired structure with bolts and nuts
It is common. In the present invention, the desmut treatment liquid feeding device is provided.
Equipment and concentration adjustment equipment can be simplified and equipment costs can be reduced.
On the other hand, the acid waste liquid generated by anodizing treatment is desmutted.
Used for (first, second and third desmut processing)
preferable. <Hydrophilic treatment> The hydrophilization treatment is a planographic printing plate.
Commonly used in the manufacture of aluminum supports for automobiles
However, the alkali metal treatment can be used.
Treatment with iodate is preferred and is described in detail below.
The After the anodized support is washed with water,
Suppression of dissolution of anodic oxide film in developer, residual film of photosensitive layer components
Suppression, anodized film strength improvement, hydrophilic property of anodized film
For the purpose of improving adhesion to the photosensitive layer, the following
Processing can be performed. One example is anodic oxidation.
Treat the coating with an alkali metal silicate solution
Silicate processing to be performed. In this case, alkali
The concentration of metal silicate is 0.1-30% by weight, preferably
0.5 to 15% by mass and pH at 25 ° C. is 10 to 1
3.5 to 5 ° C, preferably 10-7
0 ° C, more preferably 15 to 50 ° C for 0.5 to 120 seconds
Keep in contact. The method of contact is spraying even in soaking
Can be sprayed by any method.
Yes. Alkali metal silicate aqueous solution has pH lower than 10
And the solution gels, and if it is higher than 13.5, the anodized film dissolves.
It may be solved. Arca used in the present invention
Metallic silicates are sodium silicate, potassium silicate
Or lithium silicate is used. Alkali metal
As a hydroxide used to adjust the pH of aqueous silicate solutions
Is sodium hydroxide, potassium hydroxide, lithium hydroxide
There is. In addition, alkaline earth metal is used for the treatment liquid.
You may add a salt or a Group IVA (Group 4) metal salt
Yes. Alkaline earth metal salts include calcium nitrate, glass
Of strontium acid, magnesium nitrate, barium nitrate
Such as nitrates, sulfates, hydrochlorides, phosphates, acetates,
Water-soluble salts such as oxalate and borate are listed. First
IVA (Group 4) metal salts include titanium tetrachloride and trisalt
Titanium fluoride, potassium titanium fluoride, potassium potassium oxalate
Um, titanium sulfate, titanium tetraiodide, chlorinated zirconium oxide
Um etc. are mentioned. Alkaline earth metal or I
Group VA (Group 4) metal salts may be used alone or in combination of two or more
Can be used. Preferred range of these metal salts
Is 0.01 to 10% by mass, more preferably 0.
It is 05-5.0 mass%. <Sealing treatment> Besides, various sealing treatments are also mentioned.
Generally known as a method for sealing anodized films
Water vapor seal, boiling water (hot water) seal, metal salt seal
Pore (chromate / bichromate seal, nickel acetate seal
Etc.), oil-impregnated sealing, synthetic resin sealing, low-temperature sealing (red blood
Salt or alkaline earth salt)
However, its performance as a printing plate support (adhesion to the photosensitive layer)
Or hydrophilic), high-speed processing, low cost, low pollution, etc.
Water vapor sealing is relatively preferred. An example of how to do this is
For example, it is also described in JP-A-4-176690.
Pressurized or normal pressure water vapor continuously or discontinuously, relative
Humidity 70% or higher, steam temperature 95 ° C or higher, 2 to 180 seconds
For example, a method of bringing it into contact with the anodized film may be mentioned.
As another sealing treatment method, the support is about 80 to 100 ° C.
Immersion or spraying in hot water or alkaline aqueous solution
How to do it, or replace it or continue
It can be dipped or sprayed with an acid solution. Asia
Examples of nitrite contained in the nitric acid solution include, for example,
LiO₂, NaNO₂, KNO₂, Mg (NO₂)₂,
Ca (NO₂)₂, Zn (NO_Three)₂, Al (NO₂)
_Three, Zr (NO₂)_Four, Sn (NO₂)_Three, Cr (NO
₂)_Three, Co (NO₂)₂, Mn (NO₂)₂, Ni
(NO₂)₂And the like, preferably alkaline gold
The genus nitrate is preferred. Use two or more types of nitrite.
You can also The treatment conditions are the state of the support and the alkali.
Since it depends on the type of metal, it cannot be determined uniquely.
However, for example, when sodium nitrite is used, the concentration is
Generally 0.001-10% by weight, more preferably
0.01-2% by weight, bath temperature is generally from room temperature to about 1
Around 00 ° C, more preferably 60-90 ° C, treatment time is
Generally 15 to 300 seconds, more preferably 10 to 18
What is necessary is just to select from each range of 0 second. Nitrite aqueous solution
The pH of the solution is preferably adjusted to 8.0 to 11.0.
In particular, it is particularly preferred that it is prepared at 8.5 to 9.5.
Good. To adjust the pH of nitrous acid aqueous solution to the above range
Is preferably prepared using, for example, an alkaline buffer.
be able to. The alkaline buffer is not limited.
For example, sodium bicarbonate and sodium hydroxide
Mixed aqueous solution, mixture of sodium carbonate and sodium hydroxide
Aqueous solution, mixed water of sodium carbonate and sodium bicarbonate
Solution, mixed aqueous solution of sodium chloride and sodium hydroxide
Solution, aqueous solution of hydrochloric acid and sodium carbonate, sodium tetraborate
Suitable for use with mixed aqueous solutions of lithium and sodium hydroxide
Can be. The alkaline buffer solution is
Also used for alkali metal salts other than um, such as potassium salts
Can be. As described above, silicate processing or
Improves the adhesion with the photosensitive layer after sealing.
Therefore, it is described in JP-A-5-278362.
An acidic aqueous solution treatment and a hydrophilic primer,
No. 4-282737 and Japanese Patent Application No. 6-108678
Described in a booklet (Japanese Patent Laid-Open No. 07-314937)
An organic layer may be provided. Aluminum support for lithographic printing plate of the present invention
In addition to the above process, the manufacturing method of
You can also. <Washing of aluminum plate> Aluminum plate
Treatment in aqueous acid or alkali solution, or abrasive
After mechanically roughening the surface, use chemicals or abrasives.
A cleaning process is provided for the purpose of removing from the surface of the minium plate.
Is the ordinary method. Cleaning is a treatment tank with different types and compositions of chemicals.
Usually, it is installed in the middle of
Time to enter, or from cleaning to entering the next treatment tank
The time is preferably 10 seconds or less, particularly preferably 0.1 to 10 seconds.
Good. If it exceeds 10 seconds, chemical modification of the surface will proceed,
Processing unevenness may occur easily. Also washing process
The distance between the processing tank and the processing tank
Is preferably 15 seconds or less, and particularly preferably 5 seconds or less. 1
If the time exceeds 5 seconds, the chemical modification of the surface proceeds and the next step is uniform.
One roughening process may be difficult to perform. Aluminum
The following method is used to clean the nium plate.
For the purpose of reducing the amount of drainage.
A water washing method using rye ice powder is preferred. (1) Washing with water As a method for cleaning an aluminum support for a lithographic printing plate,
The surface that has been drained with a nip roller is spray tip.
It is common to use a method of washing with water sprayed from
Is. Water goes downstream in the direction of travel of the aluminum plate
Therefore, it is preferable to inject at an angle of 45 to 90 degrees. water
The injection pressure is the pressure immediately before the injection nozzle, usually 0.5 to
5kg / cm²The liquid temperature is preferably 10 to 80 ° C. Traveling
The moving speed of the aluminum plate is 20 to 200 m / mi
n is preferred. Sprayed on aluminum plate
The amount of water produced is 0.1 to 10 L / in one washing process.
m ²It is preferable that the amount of liquid is sprayed. One wash
In the septic tank, at least two on the surface of the aluminum plate, the back
Wash water is sprayed from at least two spray tubes.
One spray tube has a pitch of 50-200mm
5 to 30 spray tips are installed. Spray chip
Spray angle of 10 to 150 degrees, aluminum plate and sp
The spacing of the lace tip injection surface is preferably 10 to 250 mm.
Yes. Spray tip spray cross-sectional shape (spray pattern)
N) are circular, circular, elliptical, square, rectangular, etc.
However, a circle, an oval, or a square or a rectangle is preferable. Flow
Volume distribution (spray water distribution on the surface of aluminum plate
State) has circular distribution, uniform distribution, mountain distribution, etc.
When using multiple spray tips side by side on a spray tube
Has a mountain-shaped distribution that facilitates uniform flow distribution over the entire width.
preferable. Flow distribution is spray pressure, spray tip and al
It varies depending on the distance of the minium plate. Spray particle size is sp
Varies depending on the structure of the rice chip, spray pressure, and spray volume
10 to 10000 μm, especially 100 to 1000 μm
Is preferred. The material of the spray nozzle is a liquid that flows at high speed
It is preferable that it has abrasion resistance. The material is true
Brass, stainless steel, ceramic, etc. are used.
Mick nozzles are particularly preferred. Install spray tip
Spray nozzles in the direction of travel of the aluminum plate
Can be placed at 45-90 degrees, but spray pattern
The centerline of the longer center of the wire is aluminum.
It is preferable to be perpendicular to the direction of travel of the plate.
The cleaning time for passing through the washing process is industrially 10 seconds or less.
Lower is preferred, particularly preferably 0.5 to 5 seconds
Yes. (2) Cleaning using dry ice powder Spray dry ice powder on both sides of the aluminum plate
Japanese Patent Application Laid-Open No. 10-66905 discloses a cleaning method.
Using known shot blasting equipment as described
Can be. The injection nozzle is disclosed in JP-A-10-2890.
No. 1 and JP-A-10-28902
There are known injection nozzles on both sides of the aluminum plate.
Multiple items can be arranged. The spray nozzles are arranged in a horizontal line
The spray pattern on the surface of the aluminum plate
Install diagonally so as to overlap in the width direction of the aluminum plate
It is preferable. The distance between the spray nozzle and the aluminum plate is
1 to 100 mm is preferable, and 10 to 50 mm is particularly preferable.
That's right. Also, a method for producing dry powder ice
Is described in Japanese Utility Model Publication No. 7-38104.
Manufacturing equipment can be used. The gas for injection is GN2.
Gas or air can be used. Powdery
Dry ice has a mean particle size of 1-1000 μm
Is preferably 10 to 100 μm. Per spray nozzle
LCO₂(Liquefied carbon dioxide) supply amount is 0.1-1kg /
min is preferable, and the supply pressure is preferably 1 to 20 MPa.
Good. Cleaning pressure with aluminum plate is 1-20MPa
Is preferred. <Material of pass roll>
Well-known steel or metal that has been treated with
For continuous production lines such as K, electrolytic capacitors and PS plates
Metal rolls, resin rolls, rubber rolls, non-woven fabrics
Can be selected from the above. Roll material, table
The physical property value of the surface is the state of the chemical solution and the aluminum surface at that time
Depending on the corrosion resistance, wear resistance, heat resistance, chemical resistance, etc.
Select with consideration. Hard chrome plating on metal rolls
Is commonly used. Natural rubber in rubber rolls,
Isoprene rubber, styrene butadiene rubber, butadiene
Rubber, butyl rubber, chloroprene rubber, chlorosulfo
Polyethylene, nitrile rubber, acrylic rubber, epi
Chlorhydrin rubber, urethane rubber, polysulfide rubber,
A small amount of additive was added to them, not to mention raw rubber
Things can be used. Rubber roll hardness is 60 ~
90 is particularly preferred. The planographic printing plate of the present invention described in detail above
According to the method for manufacturing an aluminum support for an automobile, a low purity aluminum
Luminium alloy plate (aluminum plate with many alloy components
Or an aluminum plate with no alloy components prepared)
For lithographic printing plates with uniform surface irregularities
An aluminum support can be obtained. In addition, the present invention
Obtained by the manufacturing method of aluminum support for lithographic printing plates
The lithographic printing plate aluminum support will be described later.
If a lithographic printing plate precursor is provided with a photosensitive layer,
When using a lithographic printing plate, the printing performance is excellent, and
Excellent printing durability. Aluminum for lithographic printing plates obtained in the present invention
A planographic printing plate using a film support and a method for producing the same
And explain. <Undercoat layer> In the present invention,
Aluminum support for lithographic printing plate of the present invention obtained as described above
Before providing the photosensitive layer on the body, if necessary, for example,
Inorganic subbing layers such as water-soluble metal salts such as zinc borate,
An organic subbing layer may be provided. As an organic compound used in an organic undercoat layer
For example, carboxymethylcellulose; dextri
Gum arabic; polymer having sulfonic acid groups in the side chain
And copolymers; polyacrylic acid; 2-aminoethyl phosphate
Phosphonic acids having an amino group such as sulfonic acid; substituents
Phenylphosphonic acid, naphthylphos
Phosphonic acid, alkylphosphonic acid, glycerophosphonic acid, meso
Organics such as tylenediphosphonic acid and ethylenediphosphonic acid
Phosphonic acid; optionally substituted phenyl phosphorus
Acid, naphthyl phosphate, alkyl phosphate, glycerophosphate
Organophosphoric acid such as phenyl which may have a substituent
Phosphinic acid, naphthylphosphinic acid, alkylphosphine
Organic phosphines such as phosphoric acid and glycerophosphinic acid
Acid; amino acids such as glycine and β-alanine;
Has hydroxyl group such as hydrochloride of tanolamine
Amine hydrochloride; yellow dye. These are alone
It may be used in a mixture of two or more. The organic subbing layer is made of water or methanol,
Organic solvents such as tanol, methyl ethyl ketone, or
A solution in which the above organic compound is dissolved in the mixed solvent.
Applied on an aluminum plate and dried.
It is. The concentration of the solution in which the organic compound is dissolved is 0.
It is preferable that it is 005-10 mass%. Application method
There is no particular limitation, and bar coater coating, spin coating,
Use any method such as spray coating or curtain coating.
be able to. The coating amount after drying of the organic undercoat layer is 2 to 2
00mg / m²Is preferably 5 to 100 mg /
m²It is more preferable that Within the above range, printing durability
The property becomes better. <Photosensitive layer> Lithographic printing obtained by the present invention
Planographic printing is provided by providing a photosensitive layer on an aluminum support for printing plates.
A plate original is obtained. The photosensitive layer is not particularly limited, but examples
For example, a visible light exposure type plate making layer exposed to normal visible light, red
Made by laser exposure type to expose with laser light such as external laser light
A plate layer is mentioned. Above all, draw directly with laser,
Against alkaline developer by heat generated by photothermal conversion
A positive-type image-forming layer whose solubility changes, Drawing directly with a laser and using heat generated by photothermal conversion
A photosensitive layer whose solubility in an alkaline developer changes,
The following A layer and B layer are laminated in sequence, and light is absorbed by the B layer.
A photosensitive layer containing a compound to be heated, Layer A: at least one of monomers (a-1) to (a-3)
5 containing at least 10 mol% of a copolymer as a copolymer component
Layer containing 0% by mass or more B layer: Soluble in aqueous alkali solution with phenolic hydroxyl group
Containing 50% by mass or more of functional resin Drawing directly with a laser and using heat generated by photothermal conversion
Negative type image with different solubility in alkaline developer
Forming layer, Direct writing with laser using radical addition polymerization reaction
Effective image forming layer, Positive photosensitive image forming layer, Negative photosensitive image forming layer, Is preferred. Hereinafter, the photosensitive layer will be described. (1) Visible light exposure type plate making layer Visible light exposure type plate making layer is made of photosensitive resin and, if necessary,
Can be formed by a composition containing colorants etc.
The As photosensitive resin, it dissolves in developer when exposed to light.
BODY type photosensitive resin that dissolves in developer when exposed to light
Examples include negative photosensitive resins that cannot be understood. Positive feeling
Examples of the photosensitive resin include quinonediazide compounds,
Diazide compounds such as phtoquinone diazide compounds and
Enol novolac resin, cresol-novolak resin
Combinations with phenolic resins such as Ne
Examples of ga-type photosensitive resins include diazo resins (for example,
For example, aromatic diazonium salts and formaldehyde
A condensate with aldehydes), an inorganic acid salt of the diazo resin,
A diazo compound such as an organic acid salt of the diazo resin;
) Acrylate resin, polyamide resin, polyurethane
Combination with binders such as resin, (meth) acrelane
Vinyl polymer such as resin and polystyrene resin,
(Meth) acrylic acid ester, vinyl heavy such as styrene
Compound, benzoin derivative, benzophenone derivative
And photopolymerization initiators such as thioxanthone derivatives
A combination is mentioned. As the colorant, in addition to ordinary dyes, exposure
Exposure color development color that develops by
Can be used with an exposure decolorizing dye that becomes completely colorless.
Yes. Examples of exposure coloring dyes include leuco dyes.
I can get lost. As the exposure decoloring dye, for example, triphenyl
Rumethane dye, diphenylmethane dye, oxazine
Dyes, xanthene dyes, iminonaphthoquinone colors
And azomethine dyes and anthraquinone dyes
It is. The visible light exposure type plate-making layer is, for example, the above-mentioned photosensitive layer.
Photosensitive resin solution containing photosensitive resin and the above colorant in a solvent
Form by applying and then drying
Can do. As a solvent used for the photosensitive resin solution,
The photosensitive resin can be dissolved and at room temperature
And a solvent having a certain degree of volatility. Specifically
For example, alcohol solvents, ketone solvents, esthetics
Solvent, ether solvent, glycol ether solvent
Agent, amide solvent, and carbonate ester solvent.
Examples of alcohol solvents include ethanol and pro
Examples include panol and butanol. As a ketone solvent
For example, acetone, methyl ethyl ketone, methyl
Propyl ketone, methyl isopropyl ketone, diethyl
Ketones. Examples of ester solvents include
Ethyl acetate, propyl acetate, methyl formate, ethyl formate
Le. Examples of ether solvents include
Examples include trahydrofuran and dioxane. Glico
Examples of the ruether solvent include ethyl cellosol
Bu, methyl cellosolve, butyl cellosolve
The Examples of amide solvents include dimethylforma
And dimethylacetamide. Carbonated beauty treatment salon
Examples of such solvents include ethylene carbonate and propylene carbonate.
Len, diethyl carbonate, dibutyl carbonate. The method for applying the photosensitive resin solution is not particularly limited.
Rotating coating method, wire bar coating method, dip coating
Method, air knife coating method, roll coating method, blade coating
Conventionally known methods such as the method can be used. (2) Laser exposure type plate making layer As a laser exposure type plate making layer, for example, a laser beam is irradiated.
Negative type laser engraving layer where the part remains
Positive type laser engraving layer, laser light from which the irradiated part is removed
The main component is a photopolymerization laser plate making layer that photopolymerizes when irradiated with
As mentioned. The negative type laser plate making layer is composed of (A) heat or light.
Acid precursor that generates acid upon decomposition by (B) acid precursor
Acid crosslinkability that crosslinks with acid generated by decomposition of body (A)
Compound, (C) alkali-soluble resin, (D) infrared absorption
And (E) phenolic hydroxyl group-containing compound
Negative type laser engraving dissolved or suspended in various solvents
It can form using a layer formation liquid. Examples of the acid precursor (A) include imino.
Like phosphate compounds, ultraviolet light, visible light or
Examples include compounds that decompose by heat to generate sulfonic acid
It is done. Besides, photocationic polymerization initiator, photoradical
Commonly used as polymerization initiators, photochromic agents, etc.
A compound can also be used as an acid precursor (A).
Examples of the acid crosslinkable compound (B) include alkoxy compounds.
Has at least one of til group and hydroxyl group
Aromatic compound, N-hydroxymethyl group, N-al
Has a coxymethyl group or an N-acyloxymethyl group
Compounds and epoxy compounds. Alkali soluble
Examples of the functional resin (C) include novolac resin and poly
(Hydroxystyrene) etc. in the side chain hydroxyaryl
Examples thereof include a polymer having a group. As the infrared absorber (D), for example, a wave
A dye that absorbs infrared light having a length of 760 to 1200 nm, and
Pigments. Specifically, for example, black pigment, red
Color pigment, metal powder pigment, phthalocyanine pigment; the wavelength
Azo dyes, anthraquinone dyes, dyes that absorb infrared rays
Examples include talocyanine dyes and cyanine dyes. Feno
Examples of the hydroxyl group-containing compound (E) include, for example, general
formula (R¹-X)_n-Ar- (OH)_m (Wherein R¹Is an alkyl group having 6 to 32 carbon atoms or
A rukenyl group, wherein X is a single bond, O, S, COO or
Is CONH, Ar is an aromatic hydrocarbon group, alicyclic
A hydrocarbon group or a heterocyclic group, and n and m are
Each is a natural number of 1-8. )
It is done. Such compounds include, for example, nonylf
Examples include alkylphenols such as enol. Ne
In addition to the above components, the ga-type laser plate-making layer forming solution can be used.
A plasticizer etc. can also be mix | blended. The body type laser plate making layer can be (F) alkali-capable.
Soluble polymers, (G) alkaline dissolution inhibitors, and (H)
Dissolve or suspend the infrared absorber in a suitable solvent
Can be formed using a positive type laser plate-making layer forming liquid.
Yes. Examples of the alkali-soluble polymer (F) include:
Phenol resin, cresol resin, novolac resin,
Logariol resin, poly (hydroxystyrene), etc.
Phenolic polymers with enolic hydroxyl groups;
At least some monomer units have sulfonamide groups
A sulfonamide group-containing polymer which is a polymer; N-
(P-Toluenesulfonyl) (meth) acrylamide group
Homopolymerization of monomers having an active imide group such as
Examples include active imide group-containing polymers obtained by copolymerization
It is done. Examples of the alkali dissolution inhibitor (G) include
React with alkali-soluble polymer (F) by heating
Low alkali solubility of alkali-soluble polymer (F)
Compounds to be reduced. Specifically, for example,
Lufone compounds, ammonium salts, sulfonium salts, amino acids
Compound. With alkali-soluble polymer (F)
Alkali dissolution inhibitor (G) combinations include Al
Novolac resin and alkali as potassium soluble polymer (F)
It is a kind of sulfone compound as a re-dissolution inhibitor (G)
A combination of cyanine dyes is preferable. Infrared
As the absorbent (H), for example, squarylium dye,
Pyrylium pigment, carbon black, insoluble azo dye,
Wavelength of 750-1200 nm for anthraquinone dyes
Has an absorption region in the infrared region, and has a light / heat conversion ability
Element, dye and pigment. The photopolymerization type laser plate making layer is composed of (I) molecular terminal
A vinyl polymerizable compound having an ethylenically unsaturated bond
Formed using the contained photopolymerization type laser plate-making layer forming liquid
be able to. Necessary for photopolymerization laser plate making solution
(J) photopolymerization initiator, (K) sensitizer, etc.
Can be combined. As vinyl polymerizable compound (I)
For example, (meth) acrylic acid, itaconic acid, male
Ethylenically unsaturated carboxylic acids such as acids and aliphatic polyvalent acids
Ethylenically unsaturated carboxylic acid, ester with rucol
Acid polyvalent ester; ethylenically unsaturated carboxylic acid and many
Methylenebis (meth) acrylamid composed of a polyvalent amine
Do; ethylene such as xylylene (meth) acrylamide
Unsaturated carboxylic polyvalent amides. Vinyl heavy
Other compatible compounds (I) include styrene, α-medium.
Aromatic vinyl compounds such as chilled styrene;
Ethyl such as methyl laurate and ethyl (meth) acrylate
Unsaturated carboxylic acid monoesters. Light weight
As the initiator (J), photopolymerization of vinyl monomers
A commonly used photopolymerization initiator can be used. Increase
Examples of the sensitizer (K) include titanocene compounds, tri
Azine compounds, benzophenone compounds, benzoimida
Zole compounds, cyanine dyes, merocyanine dyes, key
Santen dye and coumarin dye are listed. The above-mentioned negative type laser plate making layer forming liquid, positive
Type laser plate making liquid and photopolymerization type laser plate making layer formation
Solvent used in the liquid, and negative type laser plate making
Composition liquid, positive type laser plate making liquid and photopolymerization laser
For the method of applying the plate making layer forming solution, the photosensitive resin solution is used.
The solvents and coating methods mentioned for the liquid can be used.
Yes. When forming a photopolymerization type laser plate making layer
Silane compounds in water, alcohol or carbohydrate
Partially decomposable silane compounds obtained by partial decomposition with acid
Using any reactive functional group silicone compound,
Roughening the roughened surface of the aluminum support for lithographic printing plates
The support and the photopolymerization type laser plate-making layer are obtained after staking.
This is preferable because the adhesiveness is improved. (3) Direct drawing with a laser, and photothermal conversion.
Solubility in alkaline developer changes due to heat generated
The photosensitive layer to be converted is formed by sequentially laminating the following A layer and B layer.
A photosensitive layer containing a compound that absorbs light and generates heat,
Briefly described below. Layer A: at least one of monomers (a-1) to (a-3)
5 containing at least 10 mol% of a copolymer as a copolymer component
Layer containing 0% by mass or more B layer: Soluble in aqueous alkali solution with phenolic hydroxyl group
Containing 50% by mass or more of functional resin The layer A is composed of the following monomer (a-1) 1 molecule:
In which at least one hydrogen atom is bonded on the nitrogen atom.
Monomer having a sulfonamide group, (a-2) 1 minute
A monomer having an active imino group represented by the following formula:
-(A-3) Acrylic acid having phenolic hydroxyl group
Amide, methacrylamide, acrylic acid ester, methacrylate
Selected from ylates and hydroxystyrene
At least one of the monomers
50% by mass or more of a copolymer containing 10% by mol or more
Layer. [0110] [Chemical 1] [0111] Layer B is an alcohol having a phenolic hydroxyl group.
A layer containing 50% by mass or more of a potassium aqueous solution-soluble resin
The The photosensitive layer is formed by sequentially laminating an A layer and a B layer.
And at least the B layer having phenolic hydroxyl groups
Layer B containing 50% by mass or more of a Lucari aqueous solution-soluble resin
And a photosensitive layer containing a compound that absorbs light and generates heat.
The Details are described in JP-A-11-218914.
It is. <Backcoat> Do not dissolve aluminum during development.
Comb, scratches due to rubbing of photosensitive layer and aluminum plate
For the purpose of soot, organic materials described in JP-A-6-32115
Thickness 0.01 including polymer compound and surfactant
It is known to provide a backcoat layer of ~ 8 μm
The However, actively controlling this thickness
Thus, the thickness of the printing plate precursor can be corrected. As the main component of this back coat layer,
Saturated copolymer polyester tree having a glass transition point of 20 ° C or higher
Fats, phenoxy resins, polyvinyl acetal resins and
At least selected from the group of vinylidene chloride copolymer resins
A kind of resin is used. Saturated copolymer polyester resin
Consists of a dicarboxylic acid unit and a diol unit.
The Polyester dicarboxylic acid units used in the present invention
Knit phthalic acid, terephthalic acid, isophthalic acid
Acid, tetrabromophthalic acid, tetrachlorophthalic acid, etc.
Aromatic dicarboxylic acids; adipic acid, azelaic acid, co
Succinic acid, oxalic acid, suberic acid, sebacic acid, malon
Saturated fats such as acid and 1,4-cyclohexanedicarboxylic acid
Examples thereof include aliphatic dicarboxylic acids. Back coat layer
In addition, dyes and pigments for coloring, aluminum supports
Diazo coupling agent, diazo for improving adhesion
Diazo resin composed of nium salt, organic phosphonic acid, organic resin
Acids and cationic polymers, and even slip agents
Commonly used waxes, higher fatty acids, higher fatty acid acids
A silicone compound consisting of dimethylsiloxane,
Modified dimethylsiloxane, polyethylene powder, etc.
Added. [0114] The back coat layer was placed on the back of the aluminum support.
Various methods can be applied to coat the surface. For example, appropriate
Apply a solution in a suitable solvent or an emulsified dispersion
Drying method, for example, a pre-formed film
A method of bonding to an aluminum support with adhesive or heat and
A melt film is formed by a melt extruder and bonded to a support.
The above method can be used.
The most preferable method is to apply the solution and dry it.
It is. As the solvent used here, JP-A-62-2
An organic solvent as described in Japanese Patent No. 251739
Used alone or in combination. <Matte layer> Provided as described above.
If necessary, a vacuum baking frame was used on the surface of the photosensitive layer.
The vacuuming time for contact exposure is shortened, and
A mat layer is provided to prevent injuries. Specifically,
Kaisho 50-125805, Shoko 57-6582,
As described in each publication of JP-A-61-28986
Method for providing a mat layer, Japanese Patent Publication No. 62-62337
The method of heat-sealing solid powder as described in
And so on. Long aluminum plate that runs continuously
Before applying the matte layer to the
Adjust the temperature to
After moistening, aluminum droplets can be removed with an electrostatic coating device.
Apply on the surface of the plate. Next, the wet equipment provided again
The surface is re-wetted with a stand and then dried with a drying device.
The average diameter of the mat layer used in the present invention is 100 μm or less.
If the average diameter is larger than this,
Contact between the photosensitive layer and the backcoat layer when storing repeatedly
Increases area, reduces slipperiness, photosensitive layer and back coating
The surface of both layers is easily rubbed. Average height of matte layer
The thickness is preferably 10 μm or less, more preferably 2 to 8 μm.
m. If the average height is higher than this range, it will be difficult to attach fine lines.
The highlight dots are also reduced, which is preferable for tone reproduction.
Absent. If the average height is 2 μm or less, the vacuum adhesion is insufficient.
Causes bokeh. The coating amount of the mat layer is 5 to 200 mg
/ M²Is more preferable, and more preferably 20 to 150 mg /
m²It is. If the coating amount is larger than this range,
The contact area with the backcoat layer increases and causes scratches.
If it is smaller than this, the vacuum adhesion is insufficient. <Coating> Photosensitive layer and back coat layer
As a system condition for applying the coating, a known photosensitive layer is applied.
Many methods and conditions are available. That is, coating
A method using a hood and an extrusion type coater
The method using the slide bead coater is used.
it can. Also, the conditions for application are the same as those described in the known patent.
Available. As a method for applying the photosensitive composition, Japanese Patent Publication No. 5
JP-A-8-4589, JP-A-59-123568
Using a coating rod described in
And JP-A-4-244265.
Using an extrusion coater, or
Japanese Patent Publication No. 1-57629, Japanese Patent Application No. 8-288656
The slide bead coater described in the gazette
The method used can be used. <Drying> After roughening treatment or photosensitive layer,
Of the aluminum plate after applying the coating layer and backcoat layer
Describes the drying method conditions. Special drying methods
In the drying apparatus described in Kaihei 6-63487
Place a roll and wrap the web on the roll
Arch-type dryer, from the top and bottom of the web to the nozzle
One that dries while raising the web by supplying more air
Using various media at high temperature without using the formula or hot air
Heating and drying by the secondary heat, or low
The roll is heated using various media and the roll contacts the web
There is a method of drying by conduction heat transfer. The planographic printing plate precursor thus obtained
If necessary, cut it into an appropriate size, expose it, and
A lithographic printing plate can be obtained by imaging and plate making. OK
A lithographic printing plate provided with a visible light exposure type plate making layer (photosensitive plate making layer)
In the case of the original plate, remove the transparent film on which the printed image is formed.
It is exposed by irradiating normal visible light repeatedly,
Thereafter, the plate can be made by development. Leh
In the case of a lithographic printing plate precursor provided with the exposure type plate making layer,
By directly writing a print image by irradiating seed laser light
Plate making by exposing to light and then developing.
it can. <Exposure> The exposure method is disclosed in JP-A-9-6881.
No. 0, Japanese Patent Application Laid-Open No. 11-218914, Japanese Patent Application No. 20
No. 00-378507 and Japanese Patent Application No. 2001-17
Well-known people including those described in the specification of 3968
The law can be used. <Developer> Developer and replenisher used in the present invention
Are disclosed in JP-A-9-68810 and JP-A-11-2.
No. 18914, Japanese Patent Application No. 2000-378507
And in Japanese Patent Application No. 2001-173968
Known ones can be used. Kay
An alkaline aqueous solution containing an acid and no silicic acid,
An alkaline aqueous solution containing saccharides can be used. Ingredients
Physically, it was developed as an alkaline aqueous solution containing silicic acid.
The main components of the liquid and replenisher are silicic acid, phosphoric acid, carbonic acid, boron
Acids, phenols, sugars, oximes and fluorinated amines
Contains at least one compound selected from rucols
And the pH is in the range higher than 12.0 and lower than 13.0
Alkaline aqueous solution. Of these, phenols,
Weaks such as sugars, oximes and fluorinated alcohols
As an acidic substance, dissociation index (pKa) is 10.0-1.
3.2 are preferred. Details are disclosed in JP-A-9-68810.
It is described in the gazette. Also, alkali containing silicic acid
As an aqueous solution, alkaline agent is sodium silicate, silica
Silicates such as potassium acid are preferred. The reason is Kay
Silicon oxide SiO, a component of acid salts₂And alkali metal acids
Chemical M₂Developability can be adjusted by O ratio and density
For example, Japanese Patent Laid-Open No. 54-62004
As described in Japanese Patent Publication No.57-7427
An effective alkali metal silicate is used. Details are special
It is described in Kaihei 11-218914. Ma
In addition, an alkaline aqueous solution that does not contain silicic acid and contains saccharides
Is known as an organic material with a buffering action.
It is composed mainly of a compound and a base, and substantially contains silicon dioxide.
It is necessary to use an alkaline developer that does not have. The present invention
In the following, such a developer is referred to as “non-silicate development”.
It is called “liquid”. Here, “substantially” means unavoidable.
Presence of trace amounts of silicon dioxide as pure and by-product
It means to allow. In the development process,
By applying a silicate developer,
A good lithographic printing plate that is expressed and has no defects in the image area is obtained.
Can. As an alkaline aqueous solution, in particular, pH 1
The thing of 2.5-13.5 is preferable. The non-silicated
As described above, the image liquid is composed of an organic compound having a buffering action and
It is mainly composed of a base. Details are disclosed in JP 2000
-378507. Further, the development method and the processing after development are also special.
Japanese Laid-Open Patent Publication No. 9-68810, Japanese Patent Laid-Open No. 11-218914
No. 2000, Japanese Patent Application No. 2000-378507, and Japanese Patent Application No. 2000-378507
What is described in the specification of Japanese Patent Application No. 2001-173968
First, a known one can be used. [0122] The present invention will be described in detail with reference to the following examples.
However, the present invention is not limited to these. 1. Production of aluminum support for lithographic printing plates (Examples 1-1 to 1-17 and Comparative Examples 1-1 to 1-1-
3) As shown in Table 2, each aluminum having the composition shown in Table 1
Each surface treatment is applied to the lithographic alloy plate and each lithographic printing plate
A ruminium support was obtained. The surface treatment shown in Table 2
Mechanical surface roughening treatment, first alkali etching treatment,
Smut treatment, 1st electrochemical roughening treatment (nitric acid aqueous solution
Solution), second alkali etching treatment, second desmutting treatment
2nd electrochemical surface roughening treatment (hydrochloric acid aqueous solution) 3rd
Lukari etching treatment, third desmut treatment, anodizing
Treatment, sealing treatment and hydrophilization treatment in this order
It was done. Comparative Example 1-3 is the second electrochemical
Surface roughening treatment (hydrochloric acid aqueous solution), the following (7) hydrochloric acid concentration
Instead of 5 g / L aqueous solution, hydrochloric acid concentration 0.5 g / L
Each surface treatment shown in Table 2 was performed except that an aqueous solution was used.
It was. Details of each process are as follows. Each engineer
After the roughening treatment, a water washing treatment was performed. Roughening treatment
After rinsing with water, drain the liquid with a nip roller.
It was. In addition, processing using the same type of liquid is performed continuously.
In some cases, washing with water during the process was omitted. (1) Mechanical surface roughening treatment Abrasive A (pumice crushed, average of particles contained in it)
Abrasives classified so that the particle size is 40 μm), and
Abrasive B (silica sand is used, the particles contained in it
Abrasive material classified so that the average particle size becomes 20 μm) and water
And a suspension (specific gravity 1.12) as a polishing slurry liquid,
While supplying to the surface of the aluminum plate with a spray tube,
Mechanical rough surface by rotating nylon roller brush
Made. Nylon brush material is 6 · 10 nylon
No. 3 brush with a hair length of 50 mm was used. Niro
N-brush has a hole in a stainless steel tube of Φ300mm
And planted so as to be dense. Use 3 rotating brushes
It was. Of the two support rollers (Φ200mm) at the bottom of the brush
The distance was 300 mm. Brush roller turns the brush
The load of the drive motor that rotates the brush roller
Control and roughen the load before pressing against the metal plate
The average surface roughness of the rear aluminum plate is 0.45 to 0.5.
It was pressed down to 5 μm. The direction of brush rotation is
The moving direction of the aluminum plate was the same. (2) First alkali etching treatment Aluminum plate, NaOH 27wt%, aluminum
An aqueous solution containing 6.5 wt% of ions, sprayed at 70 ° C
The aluminum plate is etched by spraying from the tube.
It was. The surface of the surface to be electrochemically roughened in a later process
The dissolution amount of the minium plate was as shown in Table 2. (3) First desmut process The acidic aqueous solution used for desmut treatment is the following treatment solution.
It was off. Treatment liquid A: Glass used in the next electrochemical roughening step
Acid effluent was used. The liquid temperature was 35 ° C. Desma
Spray solution is sprayed with spray and desmutted for 2 seconds
Went. Treatment liquid B: waste liquid generated in the anodizing process (sulfurization)
Aluminum ion 5g / L in acid 100g / L aqueous solution
Dissolve) and perform desmut treatment at 35 ° C for 2 seconds
It was. (4) First electrochemical roughening treatment (nitric acid water
solution) Alkaline nitrate is added to an aqueous solution with a liquid temperature of 50 ° C and a nitric acid concentration of 9.5 g / L.
Add aluminum to make aluminum ion concentration 5g / L
The electrolyte solution adjusted to was used. Generate trapezoidal alternating current
An electrochemical surface roughening treatment was performed using a power source. That exchange
The frequency of the flowing current is 60Hz, reaching the peak from zero.
The time Tp until the start was 0.8 msec. Exchange
The duty (ta / T) was 0.5. Current density is alternating
60A during anode reaction of aluminum plate at the peak of flow
/ Dm²And the aluminum plate is charged during the anode reaction.
The ratio of the total amount of electricity to the total amount of electricity during the cathode reaction is 0.
95. The amount of electricity applied to the aluminum plate is
Table 2 shows the total amount of electricity during the anode reaction of the minium plate.
Indicated. The electrolytic treatment tank is the radial type shown in FIG.
The tank was used. (5) Second alkali etching treatment Aluminum plate, NaOH 27wt%, aluminum
Aqueous solution containing 6.5 wt% ions, sprayed at 45 ° C
The aluminum plate is etched by spraying from the tube.
It was. The surface of the surface to be electrochemically roughened in a later process
The dissolution amount of the minium plate was as shown in Table 2. (6) Second desmut process The acidic aqueous solution used for desmut treatment is the following treatment solution.
It was off. Treatment liquid A: salt used in the next electrochemical roughening step
Acid effluent was used. The liquid temperature was 30 ° C. Desma
Spray solution is sprayed with spray and desmutted for 2 seconds
Went. Treatment liquid B: Nitric acid used in the electrochemical roughening step
The waste liquid was used. The liquid temperature was 30 ° C. Desma
The spray solution is sprayed and sprayed for 2 seconds.
went. Treatment liquid C: waste liquid generated in the anodizing treatment process
Aluminum ion 5g / L in acid 100g / L aqueous solution
Dissolve) for 2 seconds at a liquid temperature of 30 ° C.
It was. (7) Second electrochemical roughening treatment (hydrochloric acid water
solution) Aluminum chloride was added to an aqueous solution with a liquid temperature of 35 ° C and a hydrochloric acid concentration of 5 g / L.
Add 40g / L of Ni to adjust the aluminum ion concentration
The electrolytic solution adjusted to 4.5 g / L was used. Trapezoidal wave AC
Electrochemical roughening using a power source that generates flow
It was. Is the frequency of the alternating current 50Hz, zero current?
The time Tp to reach the peak is 0.8 msec.
It was. The duty cycle (ta / T) of alternating current was 0.5.
The current density is at the peak of alternating current, and the aluminum plate anode
50A / dm during reaction²The aluminum plate is
Sum of electricity during cathode reaction and sum of electricity during cathode reaction
The ratio was 0.95. Electricity applied to aluminum plate
The amount is the total amount of electricity during the anode reaction of the aluminum plate
And shown in Table 2. The electrolytic treatment tank is a radial type as shown in FIG.
One tank was used. At the inlet (liquid level) of the auxiliary electrolytic cell 34
To the inlet (liquid level) of the AC electrolytic cell 20
The passing time was 2 seconds. (8) Third alkali etching treatment Aluminum plate, NaOH 27wt%, aluminum
Aqueous solution containing 6.5 wt% ions, sprayed at 45 ° C
The aluminum plate is etched by spraying from the tube.
It was. Surface electrochemically roughened in step (7) above
The amount of aluminum plate dissolved is as shown in Table 2.
It was. (9) Third desmut process The acidic aqueous solution used for desmut treatment is the following treatment solution.
It was off. Treatment liquid A: Waste liquid generated in the next anodizing process
(5 g of aluminum ion in 170 g / L aqueous solution of sulfuric acid
/ L dissolution) for 4 seconds at a liquid temperature of 35 ° C.
Went. Treatment liquid B: Waste liquid generated in the next anodizing process
(5 g of aluminum ion in 170 g / L aqueous solution of sulfuric acid
/ L dissolution) and desmutting for 4 seconds at a liquid temperature of 70 ° C.
Went. Treatment liquid C: Waste liquid generated in the next anodizing process
(5 g of aluminum ion in 100 g / L aqueous solution of sulfuric acid
/ L dissolution) for 4 seconds at a liquid temperature of 35 ° C.
Went. (10) Anodizing treatment Next, this plate is anodized under any of the following conditions:
It was. Condition A: Aluminum sulfate is added to 170 g / L of sulfuric acid.
Use an electrolyte with an aluminum ion concentration of 5 g / L
Liquid temperature 33 ° C, current density 10A / dm²2.4g
/ M²The direct current anodic oxide film was provided. Condition B: Aluminum sulfate is added to 100 g / L of sulfuric acid.
Use an electrolyte with an aluminum ion concentration of 5 g / L
Liquid temperature 50 ° C., current density 10 A / dm²3g / m
²The direct current anodic oxide film was provided. (11) Sealing treatment In a vapor chamber saturated at 100 ° C and 1 atm
Steam sealed for 10 seconds. (12) Hydrophilization treatment Hydrophilic treatment was performed under any of the following conditions. Condition A: 7% aqueous solution of sodium silicate at 25 ° C.
Soaked for 2 seconds. Condition B: Sodium silicate 2.5 mass% aqueous solution at 70 ° C.
For 5 seconds. Thereafter, it was dried. 2. Table of aluminum supports for lithographic printing plates
Surface shape evaluation Each lithographic printing plate aluminum obtained in each example and comparative example
Double the surface shape of the Ni support using a scanning electron microscope
Honeycomb pits observed on the surface and observed at a rate of 2000 times
Was evaluated for uniformity. The results are shown in Table 2. Evaluation
Indicates that the uniformity of the irregularities on the surface is good,
What was non-uniform was represented as “x”. 3. Electrode roughening treatment of electrodes
Dissolution 1st electrochemical surface roughening treatment or 2nd electrochemical surface roughening
In the treatment, dissolution of the electrode was confirmed. The electrode is dissolved
`` None '' when the electrode is not dissolved
The case where it was solved was expressed as “Yes”. [0137] [Table 2][0138] [Table 3] 4. Production of lithographic printing plates and evaluation of dirt performance
(Examples 2-1 to 2-11) (Example 2-1) Planographic printing plate produced in Example 1-11
Using the aluminum support for coating, apply the following photosensitive layer
After drying and exposure processing, develop with the following developer.
It was. When this lithographic printing plate is used for printing, the stain performance is
It was a good printing plate. An undercoat layer was formed in advance. Undercoat
The bottom layer is coated with an undercoat solution of the following composition at 80 ° C for 30 seconds
Dried. The coating amount after drying is 30 mg / m²Met.   <Undercoat liquid>     Aminoethylphosphonic acid 0.10g     Phenylphosphonic acid 0.15g     β-Alanine 0.10g     40g of methanol     60g of pure water Apply the following amount of photosensitive solution on the substrate thus prepared.
Apply with change and dry at 110 ° C for 1 minute to feel positive
A photolithographic printing plate was obtained. [0141]   <Photosensitive solution>     1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol Esterified product with seton resin (Example of US Pat. No. 3,635,709) 1) 0.45g     Cresol-formaldehyde novolak resin (meta, para ratio; 6 to 4, heavy Weight average molecular weight: 3,000, number average molecular weight: 1,100, unreacted cresol: 1.1g)     m-cresol-formaldehyde novolak resin (weight average molecular weight 1,7 00, number average molecular weight 600, 1% of unreacted cresol)                                                 0.3g     Poly [N- (P-aminosulfonylphenyl) acrylamide-co-norma Butyl acrylate-co-diethylene glycol monomethyl ether methacrylate Rate] (The molar ratio of each monomer is 40:40:20, weight average molecular weight 40, 000, number average molecular weight 20,000) 0.2 g [0142]     P-normal octylphenol-formaldehyde resin (US Pat. No. 4, No. 123,279) 0.02 g     Naphthoquinone-1,2-diazide-4-sulfonic acid chloride                                               0.01g     Tetrahydrophthalic anhydride 0.1g     Benzoic acid 0.02g     4- [p-N, N-bis (ethoxycarbonylmethyl) aminophenyl]- 2,6-bis (trichloromethyl) -S-triazine                                               0.01g     4- [PN- (P-hydroxybenzoyl) aminophenyl] -2,6- Bis (trichloromethyl) -S-triazine 0.02g     2-Trichloromethyl-5- (4-hydroxystyryl) -1,3,4-o Oxadiazole 0.01g     The counter anion of Victoria Pure Blue BOH is changed to 1-naphthalenesulfonic acid 0.02g of dye [0143]     MODIPER F-200 (Fluorosurfactant manufactured by NOF Corporation, 30% by mass (Methyl ethyl ketone and methyl isobutyl ketone mixed solvent solution)                                               0.06g     MegaFuck F177 (Fluorine surfactant manufactured by Dainippon Ink & Chemicals, Inc.) , 20 mass% methyl isobutyl ketone solution) 0.02 g     Methyl ethyl ketone 15g     1-methoxy-2-propanol 10g On the photosensitive layer coated in this way,
Based on the method described in Example 1 of JP 61-28986 A
And (methyl methacrylate / ethyl acrylate /
Copolymer aqueous solution of sodium acrylate = 68/20/12)
A mat layer was provided by electrostatic spraying of the liquid. This
The photosensitive lithographic printing plate made in the
From the distance of 1m through the transparent positive film, 3
50 seconds exposure with kw metal halide lamp
After that, as the developer, SiO₂/ Na₂The molar ratio of O is
1.74 sodium silicate 5.26% aqueous solution (pH
= 12.7) Fuji Photo Film as rinse solution
Fuji Photo Film with FR-3 (1: 7) manufactured by KK
Processed through an automatic processor Stablon 900D manufactured by Mu Co., Ltd.
did. Printing evaluation of this positive photosensitive lithographic printing plate
did. The press is dampened with Heidelberg SOR-M
Water is EU-3 (1: 100) manufactured by Fuji Photo Film Co., Ltd.
10% isopropanol added to the ink
Mark Five New Ink manufactured by Toyo Ink Co., Ltd. was used. (Example 2-2) Examples 1-1 to 1-9,
Aluminum for lithographic printing plates produced in 1-12 to 1-17
Using the film support, apply and dry the following photosensitive layer to expose
After the processing, development processing was performed using the following developer. these
Marks with good smearing performance when printed using a lithographic printing plate
It was a printing plate. A coating solution having the following composition was applied at a dry weight of 2 g / m.²When
It was provided on the support.     1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol Seton resin esterified product (weight average molecular weight 2,500) 40 parts by mass     Phenol formaldehyde resin (weight average molecular weight 10,000, trinuclear or less Top component 90%) 75 parts by mass     Acrylic polymer I 35 parts by mass     2- (p-butoxyphenyl) -4,6-bis (trichloromethyl) -s- 3 parts by weight of triazine     Oil blue # 603 (made by Orient Chemical Co., Ltd.) 1.5 parts by mass     MegaFuck F-176 (Dainippon Ink & Chemicals, Inc. fluorine-based surfactant) Agent) 0.3 parts by mass     1000 parts by mass of methyl ethyl ketone     1000 parts by mass of propylene glycol monomethyl ether The acrylic polymer I was synthesized by the following method.
did. N- (p-toluenesulfonyl) methacrylami
60.3 g, acrylonitrile 10.0 g and ethyl
46.0 g of acrylate is dimethylformamide 23
Dissolved in 2.6 g, 2,2'-azobis under nitrogen flow
(2,4-dimethylvaleronitrile) 0.224g
It was used as a combined initiator and stirred at 65 ° C. for 7 hours. Anti
The reaction solution was allowed to cool and then re-precipitated in 5 liters of water. Precipitate
Acrylic polymer by filtering and drying the polymer
110.4 g of I (yield 95%, Mw 52,000)
Obtained. Further, the following mat forming resin solution is sprayed.
Thus, a mat layer was formed. As a mat layer forming resin solution,
Chill methacrylate / ethyl acrylate / acrylic acid
(Feeding mass ratio 65:20:15) Part of the copolymer is natto
Prepare 12% aqueous solution in the form of a lithium salt.
Atomizing head rotation speed of 25,000 rpm with a cloth machine, feeding of resin liquid
The amount is 40 ml / min, the applied voltage to the atomizing head is -90 kV,
The ambient temperature during application is 25 ° C and the relative humidity is 50%.
After 2.5 seconds from the cloth, spray the surface with water to moisten it.
After 3 seconds of wetting, the temperature is 60 ° C and the humidity is 10%.
Sprayed for 5 seconds to dry. The original plate is added to the PS plate thus prepared.
3 kW metal halide la from a distance of 1 m through Lum
Using the amplifier, exposure was performed for 60 seconds. [0150]   <Developer and development processing>   <Developer a (pH about 12.4)>     D-saccharose 4.8% by mass     Sodium hydroxide 0.34% by mass     Sodium carbonate 0.70% by mass     Tetrabutylammonium bromide 0.03% by mass     94.13% by weight of water   <Development replenisher a (pH about 13.0)>     D-sucrose 9.7% by mass     Sodium hydroxide 1.5% by mass     Sodium carbonate 1.0% by mass     Tetrabutylammonium bromide 0.07% by mass     87.73% by mass of water   <Finishing gum solution>     Gum arabic 1.8% by mass     Enzyme-modified potato starch 18.3% by mass     Enzyme-modified onion starch 3.7% by mass     Phosphorylated waxy onion starch 1.8% by mass     Dioctylsulfosuccinate sodium salt 0.91% by mass     Primary ammonium phosphate 0.27% by mass     Phosphoric acid (85%) 0.37% by mass     EDTA-tetrasodium salt 0.27% by mass     Ethylene glycol 1.8% by mass     Benzyl alcohol 2.3% by mass     Sodium dehydroacetate 0.04% by mass     Emulsion type silicon antifoaming agent 0.02% by mass     Water 68.42% by mass   <Rinse solution>     Sodium dodecyl diphenyl ether disulfonate (40% by weight aqueous solution)                                                           6.7% by mass     Sodium hexametaphosphate 0.8% by mass     Benzyl alcohol 1.5% by mass     Polyoxyethylene (12 mol addition of ethylene oxide) Nonylphenyl A Tell 1.5% by mass     Sodium dioctyl sulfosuccinate 1.4% by mass     Phosphoric acid (85% by mass) 5.2% by mass     Sodium hydroxide 2.0% by mass     Silicon antifoaming agent 0.01% by mass     80.89% by mass of water Next, a commercially available automatic development having an immersion type developing tank.
PS-900D (Fuji Photo Film Co., Ltd.) development
The tank is charged with 20 liters of each developer and kept at 30 ° C.
Warm up. 8 liters of tap water for the second bath of PS-900D
In the third bath, finishing solution: water = 1: 1 dilution
8 liters of the finished finishing solution was charged. Like this
Pass the exposed PS plate through the prepared PS-900D.
And developed. (Example 2-3) Prepared in Example 1-10
Using an aluminum support for lithographic printing plates,
Apply and dry the light layer, and after exposure processing, use the following developer
And developed. When printing using this planographic printing plate
The printing plate had good filter stain performance. The aluminum plate was copolymerized with the following composition A.
Apply 1% aqueous solution of the body with a roll coater and dry
To form an undercoat layer. The coating amount after drying is 0.0
5g / m²It was hot. <Composition A> Methyl methacrylate / ethyl acrylate / 2-acrylic
Sodium rilamido-2-methylpropanesulfonate
(50:30:20 molar ratio) copolymer (average molecular weight of about 6
0,000) Apply a solution of the following composition on this undercoat layer and dry it.
Thus, a photosensitive lithographic printing plate was obtained. This is used as a sample.     2-hydroxyethyl methacrylate copolymer (US Pat. No. 4,123,2) (Described in Example 1 in No. 76) 0.87 g     2-Methoxy of condensate of p-diazodiphenylamine and paraformaldehyde Ci-4-hydroxy-5-benzoylbenzenesulfonate 0.1 g     Oil Bull-# 603 (Blue dye from Orient Chemical Co., Ltd.)                                                         0.03g     6g of methanol     2-methoxyethanol 6g The dry coating amount of the photosensitive layer is 2.0 g / m.²It was hot. The transparent negative original is adhered in a vacuum and the 3 kW medium
Expose for 60 seconds from a distance of 1m with a Talhalide lamp.
Immerse in the developer for 1 minute, and lightly wipe the surface of the photosensitive layer with a sponge
By rubbing and developing, a commercially available desensitized gum solution was applied.   <Developer>     Sodium sulfite 5g     Benzyl alcohol 30g     Sodium carbonate 5g     Isopropyl naphthalene sulfonate sodium 12g     1000g of pure water Example 2-4 Examples 1-1 to 1-9,
Aluminum for lithographic printing plates produced in 1-12 to 1-17
Using the film support, apply and dry the following photosensitive layer to expose
After the processing, development processing was performed using the following developer. these
Marks with good smearing performance when printed using a lithographic printing plate
It was a printing plate. <Preparation of carbon black dispersion>
Disperse the composition by volume ratio with glass beads for 10 minutes
A carbon black dispersion was obtained.     1 part by mass of carbon black     Copolymer of benzyl methacrylate and methacrylic acid (molar ratio 72:28, heavy (Weight average molecular weight 70,000) 1.6 parts by mass     1.6 parts by mass of cyclohexanone     Methoxypropyl acetate 3.8 parts by mass <Preparation of negative photosensitive lithographic printing plate>
The following photosensitive solution was applied to the aluminum plate obtained and 1
Dry at 00 ° C for 2 minutes to obtain a negative photosensitive lithographic printing plate
It was. Weight after drying is 2.0 g / m²Met. [0158]   <Photosensitive solution>     Carbon black dispersion 10g     Hexafluorophosphoric acid, a condensate of 4-diazodiphenylamine and formaldehyde 0.5g salt     Methacrylic acid, 2-hydroxyethyl acrylate, benzyl methacrylate And acrylonitrile radical copolymer (molar ratio 15: 30: 40: 15, heavy Weight average molecular weight 100,000) 5g     Malic acid 0.05g     FC-430 (U.S. 3M fluorine-based surfactant) 0.05 g     1-methoxy-2-propanol 80g     15g ethyl lactate     5g of water The obtained negative photosensitive lithographic printing plate was exposed to the plate.
Fuji Photo after exposure with YAG laser adjusted to 2W power
Film Co., Ltd. developer, DN-3C (1: 1), gum
Processing through an automatic processor charged with liquid FN-2 (1: 1)
As a result, a negative image was obtained. This lithographic printing plate
Printed with a Heidel SOR-KZ machine. (Example 2-5) Examples 1-1 to 1-9,
Aluminum for lithographic printing plates produced in 1-12 to 1-17
Using the film support, apply and dry the following photosensitive layer to expose
After the processing, development processing was performed using the following developer. these
Marks with good smearing performance when printed using a lithographic printing plate
It was a printing plate. Apply the following undercoat liquid to the aluminum support.
Apply with Yarber and use a warm air dryer at 90 ° C.
Dry for 30 seconds. The coating amount after drying is 20mg / m²In
It was. [0162]   <Undercoat liquid>     Methacryloyloxyethylphosphonic acid 0.2g     Molar ratio of methyl acrylate to styrene sulfonic acid sodium salt 75:15 Copolymer of 0.2g     Calcium nitrate 0.2g     Methanol 20g     Ion exchange water 80g <Formation of Recording Layer> The following recording layer coating solution <P-
2> on the support on which the undercoat layer is formed,
And dried at 120 ° C for 45 seconds with a hot air dryer.
To form a recording layer, and the following overcoat layer
Apply the coating solution using a slide hopper and dry with hot air
Dry lithographic printing plate precursor at 120 ° C for 75 seconds
[PS-1] was obtained. In addition, the coating amount of the recording layer is 2.0 g
/ M²The coating amount of the overcoat layer is 2.3 g /
m²Met. The red color used for the preparation of the recording layer coating solution
The structure of the external line absorbent and the like is as shown below. Also,
Polymer (PB-2) is methacrylic acid, N-isopropyl
Co-polymerization of pyracrylamide and ethyl methacrylate
After synthesizing the compound, 1,2-epoxy-3-methacrylo
By reacting with yloxymethylcyclohexane
Synthesized. The composition molar ratio is 15: 30: 20: 35
The weight average molecular weight was 120,000. [0164]   <Recording layer coating solution [P-2]>   Titanocene type radical generator (CGI-784, Ciba Specialty Ke Micals Co., Ltd.) 0.1g     Polymerizable compound (RM-2) 0.60 g     Polymerizable compound (RM-3) 0.20 g     Visible light absorber (VR-1) 0.10 g     Polymer (PB-2) 1.20 g     Copper phthalocyanine pigment 0.04g     Polymerization inhibitor (Cuperon Al, manufactured by Wako Pure Chemical Industries, Ltd.) 0.005g     Fluorosurfactant (Megafac KF309, Dainippon Ink & Chemicals, Inc. ) Made) 0.03g     Methyl ethyl ketone 10g     γ-butyrolactone 5g     7g of methanol     1-methoxy-2-propanol 5g Polymerizable compound RM-2 [Chemical 2] Polymerizable compound RM-3 [Chemical 3] Visible light absorber VR-1 [Formula 4] Polymer PB-2 [Chemical formula 5] [0169]   <Coating liquid for overcoat layer>     Polyvinyl alcohol (saponification degree 98.5 mol%, polymerization degree 500)                                                         3.0g     Nonionic surfactant (EMAREX NP-10 Nippon Emulsion Co., Ltd. ( 0.05g)     Ion exchange water 96.95g <Evaluation of Developer Composition> Fuji Photo Film
Development processing tank of automatic processor (LP-850P2)
The developer composition (V-2) having the following composition was charged into 30:
Incubated at 0 ° C. Tap water is supplied to the second bath of the automatic processor.
FP-2W (Fuji Photo Film)
(Made by Co., Ltd.): Finishing gum solution diluted with water = 1: 1
Was charged. The pH of the developer was 8.1. [0171]   <Developer Composition [V-2]>     Sodium bicarbonate 26g     Sodium salt of ethylene glycol mononaphthyl ether monosulfate                                                   30g     Ethylene glycol monododecyl ether 20g     Sodium sulfite 3g     Ethylenediaminetetraacetic acid 4sodium 1g     920 g of water Next, the planographic printing plate precursor [PS-1] size
20 sheets of 1030 x 800 mm emit 405 nm purple light
Using a 30 mW semiconductor laser and a laser beam diameter of 12
μm, plate surface energy 50 μJ / cm²Running under different exposure conditions
It was exposed to light and developed using the above self-machine. processing
Thereafter, the automatic developer was left as it was for 3 days. Left
After that, one lithographic printing plate precursor [PS-1]
Exposure followed by development processing. The resulting lithographic printing plate [P
S-1] is a printing press manufactured by Komori Corporation.
Printed using Ron. At this time, after printing starts,
Visually check how many sheets of printed material can be obtained
Evaluated. In addition, the stain state of the non-image part at that time
Was visually observed. As a result, before leaving the self-machine,
70,000 print plates processed and processed after being left alone
A good printed sheet was obtained. In addition, of the obtained printed matter
No stain was observed in the non-image area. (Example 2-6) Examples 1-1 to 1-9,
Aluminum for lithographic printing plates produced in 1-12 to 1-17
Using the film support, apply and dry the following photosensitive layer to expose
After the processing, development processing was performed using the following developer. these
Marks with good smearing performance when printed using a lithographic printing plate
It was a printing plate. <Undercoat> Next, the aluminum support.
Apply the following undercoat liquid to the wire bar with hot air drying
It dried for 30 second at 90 degreeC using the apparatus. Clothing after drying
The amount is 20mg / m²Met. [0175]   <Undercoat liquid>     Didia of condensate of 4-diazo-3methoxydiphenylamine and formaldehyde Butyl naphthalene sulfonate 0.3g     Magnesium salt of 2-aminoethylphosphonic acid 0.1 g     Calcium chloride 0.2g     Methanol 20g     Ion exchange water 80g <Formation of recording layer> The following recording layer coating solution was added
Apply with a wire bar on a support with an undercoat layer
And dry for 45 seconds at 120 ° C in a hot air dryer.
A recording layer was formed to obtain a lithographic printing plate precursor [PS-2]. Dry
The coating amount after drying is 2.0 g / m²Met. The recording layer
The structure of the infrared absorber used to prepare the coating solution is as follows:
As shown in The polymer (PB-1)
Tacrylic acid, N-acryloylmorpholine and benzy
After synthesizing a copolymer of dimethacrylate,
2-hydroxypropyl methacrylate, base and
By reacting in the presence of potassium iodide.
It was. The composition molar ratio is 15: 30: 10: 45,
The weight average molecular weight was 100,000. [0177]   <Recording layer coating solution [P-1]>     Onium salt (KO-1) 0.25g     Polymerizable compound (RM-1) 0.60 g     Infrared absorber (IR-1) 0.06 g     Polymer (PB-1) 1.40 g     Victoria Pure Blue Naphthalenesulfonate 0.04g     N-allyl stearamide 0.01 g     Polymerization inhibitor (Irganox 1010, Ciba Specialty Chemicals 0.005g     Fluorosurfactant (Megafac KF309, Dainippon Ink & Chemicals, Inc. ) Made) 0.03g     Methyl ethyl ketone 10g     γ-butyrolactone 5g     7g of methanol     1-methoxy-3-propanol 5g Onium salt KO-1 [Chemical 6] Polymerizable compound RM-1 [Chemical 7] Infrared absorber IR-1 [Chemical 8] Polymer PB-1 [Chemical 9] <Evaluation of Developer Composition> Plate Material Feeder (S
A-L8000), exposure apparatus (Luxel T-900)
0CTP), conveyor (T-9000 Conveyo)
r), automatic processor (LP-1310H), stocker
Fuji Photo Film Co., Ltd. C (ST-1160)
A TP output system was used. Development tank of automatic processor
The developer composition (V-1) having the following composition was charged into
Incubated at 0 ° C. Tap water is supplied to the second bath of the automatic processor.
FP-2W (Fuji Photo Film)
(Made by Co., Ltd.): Finishing gum solution diluted with water = 1: 1
Was charged. The pH of the developer was 8.0. [0183]   <Developer Composition [V-1]>     20g potassium bicarbonate     Sodium dibutylnaphthalenesulfonate 30g     Ethylene glycol mononaphthyl ether 20g     Sodium sulfite 3g     Hydroxyethane diphosphonate potassium 2g     Silicone SA730 (Surfactant manufactured by Toshiba Silicone Co., Ltd.)                                                     0.1g     924.9 g of water Next, the planographic printing plate precursor [PS-2] size
Load 30 sheets of 1030x800mm into the plate material supply device
Fully automatic, continuous exposure, development processing, stocker
Discharged. After processing, leave the automatic developer for 3 days
did. After leaving, one lithographic printing plate precursor [PS-2]
Is loaded in the plate material supply device, fully automatically and continuously,
Developed and discharged to stocker. Lithographic printing obtained
Version [PS-2] printed by Komori Corporation
Printing was performed using a Lithlon machine. At this time, after printing starts,
How many sheets can be obtained with ink on the minute
Was visually evaluated. Also, the non-image area is dirty at that time
The state of was observed visually. As a result, leave the self-machine
The previously processed printing plate is the same as the printing plate processed after being left unattended.
As a result, 60,000 good prints were obtained. Also obtained
No stain was observed on the non-image area of the printed material. (Example 2-7) Examples 1-1 to 1-9,
Aluminum for lithographic printing plates produced in 1-12 to 1-17
Using the film support, apply and dry the following photosensitive layer to expose
After the processing, development processing was performed using the following developer. these
Marks with good smearing performance when printed using a lithographic printing plate
It was a printing plate. An undercoat solution having the following composition was applied, and 1 at 80 ° C.
The film was dried for 5 seconds to form a coating film. Coating of the coating after drying
The amount is 15mg / m²Met. <Undercoat liquid composition> The following polymer compound 0.3g Methanol 100g 1g of water [0188] Embedded image <Formation of photosensitive layer> Further, a photosensitive layer having the following composition:
A coating liquid 1 was prepared and applied to an undercoated aluminum support.
This photosensitive layer coating solution 1 was dried using a bar coater.
Coating amount (photosensitive layer coating amount) is 1.0 g / m²Paint to be
It was clothed and dried to form a photosensitive layer, and a lithographic printing plate was obtained. [0190]   <Photosensitive layer coating solution 1 composition>     Capric acid 0.03g     0.75 g of specific copolymer 1 described later     m, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight 3,5 00, containing 0.5% by mass of unreacted cresol) 0.25g     p-Toluenesulfonic acid 0.003g     Tetrahydrophthalic anhydride 0.03g     0.017 g of cyanine dye A represented by the following structural formula [0191] Embedded image [0192]     The counter ion of Victoria Pure Blue BOH was replaced with 1-naphthalenesulfonic acid anion. 0.015g of dye turned on     Fluorosurfactant (Megafac F-177, manufactured by Dainippon Ink & Chemicals, Inc. ) 0.05g     γ-Butyllactone 10g     Methyl ethyl ketone 10g     1-methoxy-2-propanol 1g <Specific copolymer 1> Stirrer, cooling pipe
And a 500 mL three-necked flask with a dropping funnel
In addition, 31.0 g (0.36 mol) of methacrylic acid,
Ethyl loformate 39. lg (0.36 mol) and a
Put 200 mL of cetonitrile and cool with ice water bath
The mixture was stirred. Triethylamine to this mixture
36.4 g (0.36 mol) was added dropwise over about 1 hour.
The solution was dripped with a filter. After the dripping is finished, remove the ice water bath,
The mixture was stirred for 30 minutes at room temperature. To this reaction mixture, p-aminobenzenes was added.
Add 51.7 g (0.30 mol) of lufonamide and add oil
Stir the mixture for 1 hour while warming to 70 ° C in a bath
It was. After completion of the reaction, the mixture is poured into 1 L of water.
And stir the mixture obtained for 30 minutes.
did. The mixture is filtered to remove the precipitate,
After slurrying with 500 mL of water, the slurry is filtered
The solid obtained is dried to give N- (p-amino
Nosulfonylphenyl) methacrylamide white solid
Obtained (yield 46.9 g). Next, a stirrer, a cooling pipe, and a dropping batter are used.
N- (p
-Aminosulfonylphenyl) methacrylamide 4.6
1 g (0.0192 mol), ethyl methacrylate2.
94 g (0.0258 mol), acrylonitrile 0.
80 g (0.015 mol) and N, N-dimethyla
Add 20 g of cetamide and heat to 65 ° C in a hot water bath.
While stirring the mixture. This mixture is shown below
Add "V-65" (Wako Pure Chemical Industries, Ltd.) 0.15g, 65
Stir the mixture for 2 hours under nitrogen flow while keeping at ℃
did. This reaction mixture is further mixed with N- (p-aminosulfonate.
Ruphenyl) methacrylamide 4.61 g, methacryl
2.94 g of ethyl acid, 0.80 g of acrylonitrile,
N, N-dimethylacetamide and the following “V-65”
Drop 0.15 g of mixture with dropping funnel over 2 hours
I gave it. After completion of the dropwise addition, the obtained mixture was further heated at 65 ° C.
Stir for 2 hours. After completion of the reaction, 40 g of methanol was added.
Add to the mixture, cool, and add the resulting mixture to 2 L of water.
Stir in the water and stir the mixture for 30 minutes.
After that, the precipitate is removed by filtration and dried.
15 g of the specific copolymer 1 as a white solid was obtained. Obtained
The weight average molecular weight of the specific copolymer 1 obtained
5 as measured by chromatography.
3,000 (polystyrene standard). Azo polymerization initiator V-65 Embedded image The lithographic printing plate obtained as described above is discharged.
Power 500mW, wavelength 830nm, beam diameter 17μm (1
/ E²) Main operating speed 5m / sec
After the exposure at, current version for PS plate made by Fuji Photo Film Co., Ltd.
Development for 30 seconds using image liquid DP-4 (1: 8) water dilution
did. (Example 2-8) Examples 1-1 to 1-9,
Aluminum for lithographic printing plates produced in 1-12 to 1-17
Using the film support, apply and dry the following photosensitive layer to expose
After the processing, development processing was performed using the following developer. these
Marks with good smearing performance when printed using a lithographic printing plate
It was a printing plate. An undercoat solution having the following composition was applied, and 1 at 80 ° C.
The film was dried for 5 seconds to form a coating film. Coating of the coating after drying
The amount is 15mg / m²Met. <Undercoat liquid composition> The following polymer compound 0.3g Methanol 100g 1g of water [0201] Embedded image <Formation of photosensitive layer> Further, a photosensitive layer having the following composition:
A coating liquid 1 was prepared and applied to an undercoated aluminum support.
This photosensitive layer coating solution 1 was dried using a bar coater.
Coating amount (photosensitive layer coating amount) is 1.0 g / m²Paint to be
It was clothed and dried to form a photosensitive layer, and a lithographic printing plate was obtained. [0203]   <Photosensitive layer coating solution 1 composition>     Capric acid 0.03g     0.75 g of specific copolymer 1 described later     m, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight 3,5 00, containing 0.5% by mass of unreacted cresol) 0.25g     p-Toluenesulfonic acid 0.003g     Tetrahydrophthalic anhydride 0.03g     0.017 g of cyanine dye A represented by the following structural formula [0204] Embedded image[0205]     The counter ion of Victoria Pure Blue BOH was replaced with 1-naphthalenesulfonic acid anion. 0.015g of dye turned on     Fluorosurfactant (Megafac F-177, manufactured by Dainippon Ink & Chemicals, Inc. ) 0.05g     γ-Butyllactone 10g     Methyl ethyl ketone 10g     1-methoxy-2-propanol 1g <Specific copolymer 1> Stirrer, cooling pipe
And a 500 mL three-necked flask with a dropping funnel
In addition, 31.0 g (0.36 mol) of methacrylic acid,
Ethyl loformate 39. lg (0.36 mol) and a
Put 200 mL of cetonitrile and cool with ice water bath
The mixture was stirred. Triethylamine to this mixture
36.4 g (0.36 mol) was added dropwise over about 1 hour.
The solution was dripped with a filter. After the dripping is finished, remove the ice water bath,
The mixture was stirred for 30 minutes at room temperature. To this reaction mixture, p-aminobenzenes was added.
Add 51.7 g (0.30 mol) of lufonamide and add oil
Stir the mixture for 1 hour while warming to 70 ° C in a bath
It was. After completion of the reaction, the mixture is poured into 1 L of water.
And stir the mixture obtained for 30 minutes.
did. The mixture is filtered to remove the precipitate,
After slurrying with 500 mL of water, the slurry is filtered
The solid obtained is dried to give N- (p-amino
Nosulfonylphenyl) methacrylamide white solid
Obtained (yield 46.9 g). Next, a stirrer, a cooling pipe, and a dropping batter are used.
N- (p
-Aminosulfonylphenyl) methacrylamide 4.6
1 g (0.0192 mol), ethyl methacrylate2.
94 g (0.0258 mol), acrylonitrile 0.
80 g (0.015 mol) and N, N-dimethyla
Add 20 g of cetamide and heat to 65 ° C in a hot water bath.
While stirring the mixture. To this mixture, the above "V-
65 ”(manufactured by Wako Pure Chemical Industries, Ltd.) 0.15 g was added and kept at 65 ° C.
However, the mixture was stirred for 2 hours under a stream of nitrogen.
This reaction mixture is further subjected to N- (p-aminosulfonylphenol).
Nyl) methacrylamide 4.61 g, methacrylic acid ethyl
2.94 g, acrylonitrile 0.80 g, N, N-
Dimethylacetamide and the above “V-65” 0.15
The mixture of g was dropped with a dropping funnel over 2 hours.
After completion of the dropwise addition, the obtained mixture is further heated at 65 ° C. for 2 hours.
I scrambled. After completion of the reaction, 40 g of methanol was mixed into the mixture
Add, cool, and pour the resulting mixture into 2 L of water.
After stirring, stir the mixture for 30 minutes,
By removing the precipitate by filtration and drying, 15
g of a specific copolymer 1 of white solid was obtained. Specific obtained
Gel Permeation of Weight Average Molecular Weight of Copolymer 1
As measured by chromatography, 53,000.
0 (polystyrene standard). [0209] The lithographic printing plate obtained as described above was put out.
Power 500mW, wavelength 830nm, beam diameter 17μm (1
/ E²) Main operating speed 5m / sec
Using a non-silicate developer with the following composition:
Developed. <Developer (non-silicate developer)> Non-reducing
D-Sorbit / Kariu oxide combining sugar and base
(K₂1 liter of 45% aqueous potassium salt solution comprising O)
And amphoteric surfactant Pionein C-158G (Takemoto Oil)
20g made by Fat Co., Ltd. and anti-foaming agent Olphine AK-02
2.0 g of Shin Chemical Co., Ltd.) was added to prepare a concentrated solution
It was. A solution obtained by diluting this concentrated solution 9 times with water is used as a developer.
It was. The conductivity of the developer 1 is 45 mS / cm. (Example 2-9) Examples 1-1 to 1-9,
Aluminum for lithographic printing plates produced in 1-12 to 1-17
Using the film support, apply and dry the following photosensitive layer to expose
After the processing, development processing was performed using the following developer. these
Marks with good smearing performance when printed using a lithographic printing plate
It was a printing plate. <Synthesis of (A) Component Copolymer> Synthesis Example 1 (Copolymer 1) 500m with stirrer, cooling pipe and dropping funnel
l 31.0 g of methacrylic acid (0.36 g
Mol), 39.1 g (0.36 mol) of ethyl chloroformate
200ml of acetonitrile and cool with ice water bath
While stirring the mixture. Trieti to this mixture
Lumine 36.4g (0.36mol) over about 1 hour
It dropped by the dropping funnel. After completion of dripping, take an ice water bath
Leaving and stirring the mixture at room temperature for 30 minutes. To this reaction mixture, p-aminobenzenes was added.
Add 51.7 g (0.30 mol) of lufonamide, oil bath
The mixture was stirred for 1 hour while warming to 70 ° C.
After the reaction, the mixture is poured into 1 liter of water.
Stir while stirring and stir the resulting mixture for 30 minutes
I did. The mixture is filtered to remove the precipitate,
After slurrying with 500 ml of water, the slurry is filtered.
The resulting solid is dried to give N- (p-a
Minosulfonylphenyl) methacrylamide white solid
Was obtained (yield 46.9 g). Next, a stirrer, a cooling pipe and a dropping funnel.
Into a 100 ml three-necked flask equipped with
Nosulfonylphenyl) methacrylamide 5.04 g
(0.0210 mol), ethyl methacrylate 2.05 g
(0.0180 mol), 1.11 g of acrylonitrile
(0.021 mol) and N, N-dimethylacetami
Add 20g and mix while heating to 65 ° C in a hot water bath.
Stir the compound. To this mixture, the above "V-65"
Add 0.15 g (Wako Pure Chemical Industries, Ltd.) and keep it at 65 ° C.
The mixture was stirred for 2 hours under a nitrogen stream. This reaction
Further N- (p-aminosulfonylphenyl) to the mixture
Methacrylamide 5.04 g, ethyl methacrylate 2.
05 g, acrylonitrile 1.11 g, N, N-dimethyl
20 g of rubacetamide and the above “V-65” 0.15
The mixture of g was dropped with a dropping funnel over 2 hours.
After completion of the dropwise addition, the mixture obtained at 65 ° C. for 2 hours is stirred.
I got it. After completion of the reaction, 40 g of methanol is added to the mixture.
Cool, and mix the resulting mixture into 2 liters of water.
While stirring, the mixture was stirred for 30 minutes.
After that, the precipitate is removed by filtration and dried.
15 g of a white solid was obtained. Gel permeation chroma
The weight average molecular weight of copolymer 1 by
(Polystyrene standard) measured was 53,000.
there were. Synthesis Example 2 (Copolymer 2) In the polymerization reaction of Synthesis Example 1, N- (p-aminosulfo
Nylphenyl) methacrylamide 5.04 g (0.02
10 moles) N- (p-hydroxyphenyl) methacrylate
Except for changing to 3.72 g (0.0210 mol) of Luamide
Is a polymerization reaction in the same manner as in Synthesis Example 1, and the weight average molecular weight is
(Polystyrene standard) 47,000 copolymer 2 is obtained.
It was. <Production of substrate> Aluminum having a thickness of 0.3 mm
Um plate (material 1050) washed with trichlorethylene
After degreasing, nylon brush and 400 mesh Pami
Use a suspension of water, grain this surface, and wash well with water.
Washed. This plate is 25% sodium hydroxide water at 45 ° C.
Etch by immersing in solution for 9 seconds, rinse with water,
The sample was immersed in 20% nitric acid for 20 seconds and washed with water. Sand at this time
The amount of etching on the sharpened surface is about 3 g / m²Met. Next
In addition, the current density was 15 A / d using 7% sulfuric acid as an electrolyte.
m²3g / m²After providing a direct current anodized film of
And dried, and further, the following undercoat liquid was applied to form a coating film.
Dried for 1 minute at 0 ° C. The coating amount after drying is 10mg
/ M²Met. <Undercoat liquid> β-Alanine 0.5g Methanol 95g 5g of water The following photosensitive solution A1 was applied to the obtained substrate.
And dried at 100 ° C. for 2 minutes to form layer A. Dry
The subsequent coating amount is 1.4 g / m²Met. Then the following
Apply Photosensitive Solution B1 and dry at 100 ° C. for 2 minutes.
And a lithographic printing plate was obtained. Total coating of photosensitive solution after drying
The amount of cloth is 2.0 g / m²Met. [0219]   <Photosensitive solution A1>     0.75 g of copolymer 1     Cyanine dye A 0.04g     0.002 g of p-toluenesulfonic acid     Tetrahydrophthalic anhydride 0.05g     Victoria Pure Blue (BOH counter anion is 1-naphthalenesulfonic acid Anion dye) 0.015 g     Fluorosurfactant (Megafac F-177, Dainippon Ink & Chemicals, Inc. ) Made) 0.02g     γ-Butyllactone 8g     7g of methyl ethyl ketone   1-methoxy-2-propanol 7g   <Photosensitive solution B1>     m, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight 4,0 00) 0.25g     Cyanine dye A 0.05g     N-dodecyl stearate 0.02 g     Fluorosurfactant (Megafac F-177, Dainippon Ink & Chemicals, Inc. 0.05g)     7g of methyl ethyl ketone     1-methoxy-2-propanol 7g The obtained lithographic printing plate was printed with an output of 500 mW,
Wavelength 830 nm, beam diameter 17 μm (1 / e²) Semiconductor
After exposure at a main scanning speed of 5 m / sec using a body laser,
Fuji Photo Film Co., Ltd. Developer, DP-4, Rinse solution
Automatic processor (Fuji Photo Film) equipped with FR-3 (1: 7)
Irum Co., Ltd .: “PS processor 900VR”)
And developed. At that time, DP-4 was diluted 1: 8
A thing was used. This printed version is made by Heidelberg
Printed on fine paper with a Dell KOR-D machine. (Example 2-10) Examples 1-1 to 1-
9, Aluminum for planographic printing plates manufactured in 1-12 to 1-17
The following photosensitive layer is applied and dried using a nium support,
After the exposure processing, development processing was performed using the following developer. this
Stain performance is good when printed using these planographic printing plates
Printing plate. An undercoat layer was formed in advance. Undercoat
The bottom layer is coated with an undercoat solution having the following composition at 80 ° C. for 30 seconds.
Dried. The coating amount after drying is 30 mg / m²Met. <Undercoat liquid> The following compound 0.3g Methanol 100g 1g of water [0223] Embedded image <Formation of heat-sensitive layer>
The coating amount of the layer coating solution is 0.85 g / m²Apply to be
After that, TABIAI, PERFECT OVEN
  Set Wind Control to 7 on PH200.
And then dried at 140 degrees for 50 seconds, and then coated for the heat sensitive layer
Application amount of liquid is 0.15 g / m²I applied so that
That is, it was dried at 120 degrees for 1 minute to obtain a lithographic printing plate precursor. [0225]   <Coating liquid for lower layer>     N- (4-aminosulfonylphenyl) methacrylamide / acrylonitrile / Methyl methacrylate (36/34/30: weight average molecular weight 50,000)                                                   1.896g     Cresol novolak (m / p = 6/4, weight average molecular weight 4,500, remaining Monomer 0.8wt%) 0.237g     Cyanine dye A (the following structure) 0.109 g     4,4'-Bizhydroxyphenylsulfone 0.063 g     Tetrahydrophthalic anhydride 0.190g     p-Toluenesulfonic acid 0.008g     Change the counterion of ethyl violet to 6-hydroxynaphthalene sulfone Food 0.05g     Fluorosurfactant (Megafac F176, manufactured by Dainippon Ink Industries, Ltd.) 0.035g     Methyl ethyl ketone 26.6g     13.6 g of 1-methoxy-2-propanol     γ-butyrolactone 13.8 g [0226] Embedded image[0227]   <Coating solution for heat-sensitive layer>     m, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight     4500, containing 0.8% by weight of unreacted cresol) 0.237 g     Cyanine dye A (above structure) 0.047g     0.060 g dodecyl stearate     3-methoxy-4-diazodiphenylamine hexafluorophosphate                                                       0.030g     Fluorosurfactant (Megafac F176, Dainippon Ink & Chemicals, Inc. 0.110g     Fluorosurfactant [Megafac MCF-312 (30%), Dainippon Inn Manufactured by Ki Kogyo Co., Ltd.] 0.120 g     Methyl ethyl ketone 15.1 g     1-methoxy-2-propanol 7.7 g The obtained lithographic printing plate precursor was converted to Creo T
Beam strength 9w with drum setter, drum rotation
Draw a test pattern in an image at a speed of 150 rpm
Went. For written lithographic printing plate precursor,
When developing, use a non-silicate developer with the following composition.
I imaged it. <Developer (non-silicate developer)> Non-reducing sugar and base
Combined D-sorbite / potassium oxide (K₂O)
1 liter of 45% aqueous potassium salt solution
Surfactant Pionein C-158G (manufactured by Takemoto Yushi Co., Ltd.)
20 g and antifoaming agent Orphin AK-02 (Nisshin Chemical Co., Ltd.)
2.0 g) was added to prepare a concentrated solution. This concentrate
A developer was prepared by diluting 9 times with water. This developer
The conductivity of 1 is 45 mS / cm. (Example 2-11) Examples 1-1 to 1-
9, Aluminum for planographic printing plates manufactured in 1-12 to 1-17
The following photosensitive layer is applied and dried using a nium support,
After the exposure processing, development processing was performed using the following developer. this
Stain performance is good when printed using these planographic printing plates
Printing plate. The following undercoat liquid was applied, and the coating film was heated to 1 ° C. at 80 ° C.
The substrate was obtained by drying for 5 seconds. The coating amount after drying is 15
mg / m²Met. <Composition of undercoat liquid> 0.3 g of the following copolymer having a molecular weight of 28,000 Methanol 100g 1g of water [0232] Embedded image The following coating solution for forming a photosensitive layer was applied to the obtained substrate.
1 coating amount is 1.8 g / m²Apply and dry
It was.   <Composition of photosensitive layer coating solution 1>     m, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight 8,0 00, 1.0 g containing 0.5% by mass of unreacted cresol     Cyanine dye A (the following structure) 0.1g     Tetrahydrophthalic anhydride 0.05g     p-Toluenesulfuric acid 0.002 g     6-Hydroxy-β-naphthalene sulfone as the counterion of ethyl violet 0.02g of acidified     Fluorosurfactant (Megafac F-177, Dainippon Ink & Chemicals, Inc. 0.05g)     Methyl ethyl ketone 12g [0234] Embedded image A lithographic printing plate is made from Creo plate setter.
Using Trendsetter 3244F (rotation speed:
150 rpm) exposure and development processing. Immersion type developer tank
Commercially available automatic processor LP-900H (Fuji Photo
Rum Co., Ltd.) developed processing tank
20 liters of image processing liquid C (pH about 13) is charged, 30
Incubated at 0 ° C. In the second bath of LP-900H, tap water
8 liters, FP-2W (Fuji Phil
Mu): Water = 1: 1 diluted finishing gum
8 liters of liquid was charged. [0236]   <Composition of alkali developing solution C>     SiO₂・ K₂O (K₂O / SiO₂= 1.1 (molar ratio)) 4.0% by mass     Citric acid 0.5% by mass     Polyethylene glycol (weight average molecular weight = 1,000) 0.5% by mass     95.0% by weight of water Aluminum support for planographic printing plate of the present invention
According to the manufacturing method, aluminum alloy plate aluminum
Electrochemical rough surface in hydrochloric acid aqueous solution regardless of
Hydrochloric acid aqueous solution with a specific composition used for hydrochloric acid treatment
Solution and in aqueous nitric acid and aqueous hydrochloric acid
AC aluminum used for electrochemical surface roughening
The ratio of the amount of electricity Qa at the time of anode of the plate to the amount of electricity Qc at the time of cathode, Q
If c / Qa is 0.9 to 1.0, the honeycomb honeycomb on the surface
Aluminum support for lithographic printing plates with extremely uniform
(Examples 1-1 to 1-1)
7). Therefore, beverage cans can be scrapped and recycled
When using an aluminum alloy plate obtained by
1-16) Even on the surface, the honeycomb pits are extremely uniform
An aluminum support for a lithographic printing plate can be obtained.
Also, the production of an aluminum support for a lithographic printing plate according to the present invention
Aluminum support for lithographic printing plate obtained by the method
Has a conventional type visible light exposure type plate making layer.
Case (Example 2-2, 2-3) and laser plate making
When a layer is provided (Examples 2-4 to 2-11)
However, when using a lithographic printing plate, printing durability and printing
Excellent performance (dirt performance). In contrast, lithographic printing plate aluminum
In the production of supports, aqueous nitric acid and aqueous hydrochloric acid
AC aluminium used for electrochemical surface roughening
The quantity of electricity Qa at the time of anode and the quantity of electricity Qc at the time of cathode
If the ratio, Qc / Qa is less than 0.9, the resulting lithographic stamp
There is no honeycomb pit on the surface of the aluminum support for printing plates.
It is uniform (Comparative Example 1-1), and Qc / Qa is 1.
If it exceeds 0, the electrode in electrochemical roughening treatment
Dissolve (Comparative Example 1-2). Electricity in aqueous hydrochloric acid is also possible.
Hydrochloric acid used for aerochemical roughening treatment has a specific composition
If it is not a hydrochloric acid aqueous solution containing
The honeycomb pits on the surface of the luminium support are not uniform.
(Comparative Example 1-3). [0239] According to the present invention, the aluminum for a lithographic printing plate is used.
Low-purity aluminum that has not been used for
Um rolled plate (aluminum plate containing a lot of alloy components or
Using an aluminum plate that has not been prepared with alloy components
And no unevenness due to the roughening process
Printing durability and printing performance (stain performance) when used as a printing plate
Of aluminum support for lithographic printing plates
Can provide the law.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a waveform diagram showing an example of a trapezoidal wave AC power supply waveform preferably used for electrochemical roughening of the present invention. FIG. 2 is a cross-sectional view showing an example of an electrolytic surface roughening apparatus equipped with a flat AC electrolytic cell used in the present invention. FIG. 3 is a cross-sectional view showing another example of an electrolytic surface roughening apparatus equipped with a flat AC electrolytic cell used in the present invention. FIG. 4 is a cross-sectional view showing an example of an electrolytic surface roughening apparatus provided with a radial AC electrolytic cell used in the present invention. FIG. 5 is a side view showing the concept of a brush graining process used for mechanical roughening treatment in the present invention. [Explanation of Symbols] 2, 20 AC electrolytic cells 4A, 4B, 4C, 26A, 26B Main poles 6A, 6B, 14A, 14B Conveying rollers 8A, 16A Introducing rollers 8B, 16B Deriving rollers 10, 34 Auxiliary electrolytic cells 12, 36 Auxiliary electrode 22 AC electrolytic cell main body 22A Opening 24 Feed rollers 28A, 28B Supply nozzle 30A Upstream guide roller 30B Downstream guide roller 32 Overflow tank 34A Bottom surface 35 of auxiliary electrolyzer upstream guide roller 51 Aluminum alloy plate 52, 54 Roller-like brush 53 Polishing slurry liquids 55, 56, 57, 58 Support rollers 100, 102, 104 Electrolytic surface roughening processing apparatus a Transport direction T Transport surface Tac Power supply Th1, Th2, Th3, Th4, Th5 Thyristor W Aluminum web ta Anode reaction time tb Cathode reaction time tc Current peaked from 0 Time Ia anode cycle side of the peak current Ic cathode cycle side Peak currents of up to

─────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme code (reference) C25F 3/04 C25F 3/04 D G03F 7/00 503 G03F 7/00 503 7/09 501 7/09 501 (72) Inventor Akio Uesugi 4000 Kawajiri, Yoshida-cho, Kashihara-gun, Shizuoka Pref. Fuji Photo Shin-Film Co., Ltd. F-term (reference) 2H025 AA12 AB03 DA18 2H096 AA06 CA01 CA03 2H114 AA04 AA14 AA23 BA01 DA04 DA06 DA09 EA03 EA04 GA08 GA09

Claims (1)

Claims: 1. Aluminum plates in order: 1) The ratio of the amount of electricity Qa at the time of anode and the amount of electricity Qc at the time of cathode of an alternating current aluminum plate in a nitric acid aqueous solution, Qc / Qa is 0. Surface roughening electrochemically under the conditions of 9 to 1.0, 2) Aluminum chloride hexahydrate was added at a rate of 10 to 70 g / L to an aqueous solution containing 1 to 10 g / L of hydrochloric acid, and aluminum was added. In a hydrochloric acid aqueous solution having an ion concentration of 1 to 8 g / L, the ratio of the amount of electricity Qa at the time of anode of the alternating current aluminum plate to the amount of electricity Qc at the time of cathode, under the condition that Qc / Qa is 0.9 to 1.0 3) A method for producing an aluminum support for a lithographic printing plate, characterized by electrochemically roughening the surface and 3) anodizing.