JP2003291549A - Method for manufacturing aluminum supporting body for planography impression, aluminum supporting body for planography impression, and planography impression - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an aluminum supporting body for a planography impression, etc., which are excellent in print resistance and performance against fouling. <P>SOLUTION: The aluminum supporting body for the planography impression, the method for manufacturing the same, and the planography impression are characterized in that at least one surface of an aluminum plate is treated in turn by (a) mechanical roughing treatment for mechanically roughing the surface, (b) alkaline etching treatment, (c) desmut treatment, (d) electrolytic roughing treatment in nitric acid aqueous solution, (e) alkaline etching treatment, (f) desmut treatment, (g) electrolytic roughing treatment in hydrochloric acid aqueous solution, (h) alkaline etching treatment, (i) desmut treatment, and (j) anodic oxidation treatment, wherein concentration of abrasive in the mechanical roughing treatment (a), concentration of sodium hydroxide in the alkaline etching treatment (b), etc., concentration of nitric acid and hydrochloric acid in the electrolytic roughing treatment (d), (g), and concentration of sulfuric acid in the anodic oxidation treatment (j) are controlled. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an aluminum support for a lithographic printing plate, an aluminum support for a lithographic printing plate, and a lithographic printing original plate, and particularly to printing with a laser beam based on print data of a computer. Method for producing an aluminum support for a lithographic printing plate, which is suitable as a so-called digital printing plate for directly writing an image to produce a plate, a lithographic printing plate aluminum support obtained by the production method, and the lithographic printing The present invention relates to a lithographic printing original plate in which a plate making layer is formed on a roughened surface of an aluminum support for a plate.

[0002]

2. Description of the Related Art An aluminum support for a lithographic printing plate generally has at least one surface of an aluminum plate mechanically roughened, chemically etched in an acid or alkaline solution, and desmutted in an acidic aqueous solution. , Electrolytic surface-roughening treatment that is electrochemical surface-roughening, anodizing treatment in an acidic aqueous solution, hydrophilic treatment, and pore-sealing treatment in combination with one or more treatments. It is manufactured by

In particular, the electrolytic surface-roughening treatment has been generally used as a surface-roughening method for an aluminum support for a lithographic printing plate because it is easy to obtain uniform unevenness. As the electrolytic graining treatment, electrolytic graining treatment in a hydrochloric acid or nitric acid solution has been mainly performed.

[0004]

It is used as a lithographic printing plate precursor for direct plate making having a plate making layer formed of a photosensitive image forming material for infrared laser, or a lithographic printing plate precursor using a conventional positive or negative type film. As the aluminum support, one having both the number of printed sheets (printing durability) and the stain performance at a high level has been desired. In particular, it is strongly required that the plate making surface does not easily get dirty when printing is performed by mounting it on an offset printing machine, and then printing is paused and left for a long time, and that the number of paid out sheets, which greatly affects the number of damaged sheets, is small. It started to come. However, conventional aluminum supports for lithographic printing plates have not been sufficient in these respects.

The present invention provides an aluminum support for a lithographic printing plate capable of producing an aluminum support for a lithographic printing plate which has both high printing durability and stain resistance at a high level, and a method for producing the same.
Another object of the present invention is to provide a lithographic printing original plate in which a plate-making layer is laminated on the roughened surface that has been roughened on the aluminum support for lithographic printing plates.

[0006]

The invention according to claim 1 uses an abrasive slurry in which (1) an abrasive having an average particle diameter of 1 to 60 μm is suspended on at least one surface of an aluminum plate. Mechanical roughening treatment with a brush to mechanically roughen the surface (a), (2) use an alkaline solution mainly composed of sodium hydroxide, and etch it to an etching amount of ² to 15 g / m ^2. Alkaline etching treatment (b), (3)
Desmut treatment (c) of desmut treatment in an acidic solution,
(4) Electrolysis in a nitric acid solution with a nitric acid concentration of 0.2 to 2 wt% so that the current density is 5 to 50 A / dm ² and the amount of electricity during the anode reaction is 30 to 300 C / dm ² using alternating current. Electrolytic surface-roughening treatment (d) for performing surface-roughening treatment, (5) Alkaline etching treatment for etching using an alkaline solution mainly composed of sodium hydroxide to an etching amount of 0.1 to 6 g / m ^2. (e), (6) Desmutting treatment in acidic solution (f), (7) In a hydrochloric acid solution with a hydrochloric acid concentration of 0.1 to 2% by weight, a current density of 5 to 50 A /
dm ² , electrolytic surface-roughening treatment (g) in which electrolytic surface-roughening treatment is performed so that the amount of electricity at the time of the anode is 3 to 150 C / dm ² .
(8) Alkaline etching treatment using an alkaline solution mainly composed of sodium hydroxide so that the etching amount is 0.001 to 1 g / m ² (h), (9) Desmutting treatment in an acidic solution Treatment (I) and (10) Anodizing treatment to form an anodized film having a thickness of 0.2 μm or more in a sulfuric acid solution having a sulfuric acid concentration of 5% by weight or more
A method for producing an aluminum support for a lithographic printing plate, which is sequentially subjected to (j), wherein in the mechanical roughening treatment (a), the polishing in the abrasive slurry is carried out based on the specific gravity of the abrasive slurry used. Alkaline etching treatment by controlling the material concentration
(b), (e), in (h), controlling the concentration of sodium hydroxide in the alkaline solution based on the specific gravity and conductivity of the alkaline solution used, electrolytic surface roughening treatment (d) , (G), controlling the nitric acid concentration in the nitric acid solution and the hydrochloric acid concentration in the hydrochloric acid solution based on the speed of sound and conductivity in the nitric acid solution or hydrochloric acid solution used, and anodizing treatment (j) Relates to a method for producing an aluminum support for a lithographic printing plate, which comprises controlling the sulfuric acid concentration in the sulfuric acid solution based on the specific gravity and electric conductivity of the sulfuric acid solution used.

The roughened surface of the aluminum support for a lithographic printing plate has a size of 1 by the mechanical roughening treatment (a).
A large wave having unevenness of about 0 to 20 μm is mainly formed, and the electrolytic roughening treatment (d) is roughening treatment in a nitric acid solution to obtain a honeycomb having unevenness of about 0.8 to 6 μm. Pits are mainly formed. Then, by the alkali etching treatment (e), while smoothing the roughened surface,
The size of the honeycomb pit is set to about 6 to 8 μm.
Further, in the electrolytic surface-roughening treatment (g), the electrolytic surface-roughening treatment is performed in a hydrochloric acid solution, whereby a micro wave having facet-like pits and having a diameter of about 0.02 to 0.7 μm is mainly formed. it is conceivable that.

Further, in the above manufacturing method, the concentration of the abrasive in the abrasive slurry used for the mechanical surface roughening treatment (a), the alkali etching treatment (b), the alkali etching treatment (e), and the alkali etching treatment. Concentration of sodium hydroxide in alkaline solution used in (h), electrolytic surface roughening treatment (d) and electrolytic surface roughening treatment (g) in nitric acid solution and hydrochloric acid solution nitric acid concentration and hydrochloric acid concentration, anode By controlling the sulfuric acid concentration in the sulfuric acid solution used for the oxidation treatment (j) with high accuracy, the roughened surface of the lithographic printing plate aluminum support has the large wave, the honeycomb pits, and the fine wave. A roughened surface having a structure in which is overlapped is stably formed, and an anodized film having a suitable pore size distribution is formed on the roughened surface.

In the above manufacturing method, since the composition width of the aluminum plate that can be used as a material is wide, an aluminum plate that does not have strict composition control or contains many impurities, such as the rolled aluminum plate and the recycled aluminum plate, is used. In addition, it is possible to obtain a lithographic printing original plate that has no poor appearance and is excellent in printing durability as well as excellent in stain performance and does not cause stains on the printing paper surface.

According to the second aspect of the present invention, mechanical surface roughening treatment (a), alkali etching treatment (b), (e), (h), electrolytic surface roughening treatment (d), (g), The specific gravity of the abrasive slurry, the specific gravity and conductivity of an alkaline solution, the speed of sound and conductivity in a nitric acid solution or a hydrochloric acid solution, and the specific gravity and conductivity of a sulfuric acid solution are varied in both Width is ± 1
The present invention relates to a method for producing an aluminum support for a lithographic printing plate, which is controlled to be within 0%.

In the method for producing an aluminum support for a lithographic printing plate, the concentration of the abrasive in the abrasive slurry used in the mechanical surface roughening treatment (a), alkali etching treatments (b), (e), Sodium hydroxide concentration in the alkaline solution used in (h), electrolytic surface roughening treatment (d), hydrochloric acid concentration in the hydrochloric acid solution used in (g) and nitric acid concentration in the nitric acid solution,
And the sulfuric acid concentration in the sulfuric acid solution used in the anodizing treatment (j) is stably controlled.

Therefore, the quality of the aluminum support for lithographic printing plates obtained by the above-mentioned manufacturing method and the lithographic printing plate having a plate-making layer formed on the roughened surface of the aluminum support for lithographic printing plates is small.

An invention according to claim 3 relates to an aluminum support for a lithographic printing plate, which is manufactured by the method for manufacturing an aluminum support for a lithographic printing plate according to claim 1 or 2.

The aluminum support for a lithographic printing plate comprises:
Since the large waves, the honeycomb pits, and the small waves are formed in a good balance, the adhesion between the anodized film and the plate-making layer is excellent, and since the stain resistance and the water retention are excellent, after development, The plate-making layer is unlikely to remain in the non-image area, and a printed matter having excellent image quality can be obtained.

The invention according to claim 4 relates to a lithographic printing plate precursor comprising a plate-making layer formed on the roughened surface of the aluminum support for lithographic printing plate according to claim 3.

The printing plate produced by exposing the lithographic printing plate to light is preferable not only because it is excellent in printing durability but also because it is excellent in stain performance and does not cause stains on the printing paper surface.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION 1. Aluminum Plate The aluminum plate used in the present invention is selected from a pure aluminum plate, an aluminum alloy plate containing aluminum as a main component and various trace elements, and a plastic film laminated or vapor-deposited with aluminum.

The form of the aluminum plate is generally an aluminum web continuous in the form of a strip, but in the case of producing a large quantity of a small amount of products, a sheet-shaped aluminum plate preliminarily cut into a predetermined size can also be used.

The trace elements contained in the aluminum alloy plate are, for example, silicon, iron, nickel, manganese,
Copper, magnesium, chromium, zinc, bismuth, titanium,
And vanadium.

When a large amount of silicon is contained, when anodizing treatment is performed after the surface roughening treatment, the anodized film becomes a defect, the water-holding property of the defective portion is deteriorated, and the paper is easily soiled during printing. Further, when a large amount of copper is contained, the area of the portion where the honeycomb pits are not formed is large, which causes a failure in appearance.
Therefore, from the viewpoint of producing uniform honeycomb pits in the electrochemical graining treatment in the nitric acid solution and the hydrochloric acid solution, the amount of the trace elements is 0.001% by weight to
A range of 1.5% by weight is preferred.

As the pure aluminum and aluminum alloy used for the aluminum plate, the aluminum handbook, 4th edition (1990, Japan Light Metal Association) is usually used.
, JIS A 1050 material, JIS A
3103 material, JIS A3005 material, JIS A 1
Known aluminum materials such as 100 materials, JIS A 3004 materials, and alloys in which 5% by weight or less of magnesium is added to these materials for the purpose of increasing tensile strength can be used.

In the present invention, recycled aluminum plate can be used.

1-1 Description of Aluminum Alloy As the aluminum alloy which can be used as the material of the aluminum plate in the present invention, the followings are specifically mentioned.

(1) AL1 Fe as an essential component is O. 2-1% by weight, and Si of 0.
0.05 to 0.20% by weight, 0.006 to 0.40% by weight of Cu, and 0.001 to 0.0% of Mg as an optional component.
An aluminum alloy containing 3% by weight, 0.001 to 0.04% by weight of Ti, and the balance being Al and inevitable impurities.

The aluminum alloy is JlS A 1
It is classified into 050 materials, and in particular, it can be increased in pit diameter and depth in the electrochemical roughening treatment, and is therefore suitable as a support for a lithographic printing plate that places importance on the balance between stain resistance and printing durability.

(2) AL2 0.1 to 0.5% by weight of Fe and 0.02 to 0.10% by weight of Si are contained as essential components, and as optional components,
Cu is 0.005% by weight or less, and Mg is 0.001 to 0.
03 wt%, Ti 0.001-0.04 wt%, Ni
0.002 to 0.005% by weight, V 0.01 to 0, 0
It is an aluminum alloy containing 5% by weight and the balance of Al and inevitable impurities.

The aluminum alloy is JlS A 1
It is an alloy classified into 050 material to J1S A 1070 material, and in particular, by reducing the pit diameter in the electrochemical graining treatment, the stain resistance can be improved, and by combining with non-silicate development, It is possible to produce a lithographic printing plate having a balance between stain resistance and printing durability.

(3) The content of AL3 aluminum is 95-99.4% by weight,
It is an aluminum alloy plate containing 5 or more of the following elements in the following ranges.

Fe: 0.3 to 1% by weight Si: 0.15 to 1% by weight Cu: 0.1 to 1% by weight Mg: 0.1 to 1.5% by weight Mn: 0.1 to 1.5% % By weight Zn: 0.1-0.5% by weight Cr: 0.01-0.1% by weight Ti: 0.03-0.5% by weight Since the aluminum alloy can use a scrap material as a main raw material, Raw material cost is low. Further, the aluminum alloys are aluminum alloys AL1 and A
Excellent mechanical strength compared to L2. Therefore, by using the aluminum alloy AL3, it is possible to manufacture a high-strength lithographic printing plate precursor that is low in raw material cost and excellent in mechanical strength.

(4) AL4 An aluminum alloy containing 0.1 to 1.5% by weight of Mn and / or 0.1 to 1.5% by weight of Mg as an essential component.

The aluminum alloy is excellent in mechanical strength, more stable in roughening treatment than AL3, more uniform in roughening surface and more deep in pits than AL1. Cheap. Therefore, by using the aluminum alloy AL4, the stain resistance and the printing durability are well balanced, the printing durability is particularly excellent, in other words, the printing performance is high, and the high-strength type lithographic printing original plate having excellent mechanical strength is obtained. can get.

1-2 Description of Trace Elements Regarding the trace elements contained in the aluminum alloy,
It is as follows.

Fe: Fe is 0.1 even in new metal.
It is an element contained in about 0.2 wt%, and the amount of solid solution in aluminum is small, and most of it remains as an intermetallic compound.

Fe has the effect of increasing the mechanical strength,
If it exceeds 1.0% by weight, cracks are likely to occur during rolling. On the other hand, it is not realistic to set the Fe content to 0.1% by weight or less.

As the intermetallic compound, A1 ₃ Fe,
A1 ₆ Fe, AlFeSi-based compounds, and AlFeS
A typical example is an iMn-based inclusion.

Si: Si is 0.0 even in new metal.
It is an element contained in an amount of 3 to 0.1% by weight before barley and is also contained in a large amount in scraps of aluminum products and exists as a solid solution in aluminum, an intermetallic compound, and a single precipitate. In addition, when heated in the process of manufacturing the lithographic printing plate support, solid solution Si may be precipitated as simple substance Si.

It is known that when the amount of simple substance Si is excessive, severe ink stain is reduced. It also affects the electrochemical graining properties.

As the intermetallic compound, AlFeSi
Compounds, AlFeSiMn compounds, and Mg ₂ S
i and the like are typical.

Cu: Cu is contained in a very small amount even in new metal. Also, JLS A 2000 system and JIS
It is an element contained in a large amount of scrap of A 4000 series aluminum material, and is relatively easily solid-dissolved in aluminum. Cu is an element that has a great influence on the electrochemical roughening property.

Mg: A very small amount of Mg is contained in the new gold. Also, JLS A 2000 series, 3000 series,
It is an element that is mostly contained in scraps of 5000 series and 7000 series materials. It is one of the main impurity metals contained in scrap materials, especially since it is contained in large amounts in can end materials.

By adding Mg, heat softening resistance and mechanical strength can be improved. It is also known that it forms a solid solution in aluminum relatively easily and forms an intermetallic compound with Si.

Mn: Mn is an element contained in the scrap of JlS A 3000 series material, although it is contained in a very small amount in the new metal. Since it is especially contained in can body materials, it is one of the major impurity metals contained in scrap materials.
Is one.

Mn is relatively easy to form a solid solution in aluminum and forms an intermetallic compound with Al, Fe, Si and the like. M
n improves the mechanical strength of the aluminum alloy, but affects the electrochemical roughening property.

Zn: Zn is an element contained in the scrap of JlS A 7000 series material, although it is contained in a very small amount in new metal. Relatively soluble in aluminum. Affects electrochemical drop roughening.

Cr: Cr may be contained in a very small amount even in new ingot, and JlS A 5000 series, 6000
It may be contained in a small amount in the scraps of the system and 7000 series materials.

Ti: Ti is an element usually added as a grain refining agent in an amount of 0.01 to 0.04% by weight. Mainly, it is added in the form of an intermetallic compound with Al or TiB ₂ . The scraps of JLSA 5000 series, 6000 series, and 7000 series materials contain a relatively large amount of impurity metals. When contained in excess, it may affect the electrochemical roughening property.

1-3 Description of Intermetallic Compounds Elements contained in aluminum raw materials and elements added to molten aluminum are partially melted (solid solution) in aluminum when solidified in the casting process, and the rest are metal. It exists as an intermetallic compound or a single crystallized substance / precipitate. The proportion of the element remaining as an intermetallic compound or a single crystallized substance / precipitate is greatly affected by the solidification rate. For example, most of the above elements are solid-solved in the case of rapid suspicion as in the case of roller-type continuous casting, and in the case of a casting method with a slow suspicion rate as in the DC casting method. , Relatively tends to remain as an intermetallic compound or a single crystallized substance / precipitate.

After that, during the heat treatment process such as soaking and annealing, and the hot rolling process, many of the above-mentioned elements re-dissolve in aluminum or change into a more stable intermetallic compound. When it becomes an aluminum plate for a lithographic printing plate of about 0.1 to 0.7 mm, it often exists as an intermetallic compound or a single crystallized substance / precipitate on the surface or inside of the aluminum plate. For example, when the AL1 alloy is used as the aluminum alloy in the case where the aluminum plate is manufactured by the DC casting method, the obtained aluminum plate has a density of about 500-20000 pieces / mm ^{2 and} contains an intermetallic compound. There are crystals or single crystals and precipitates. On the other hand, the aluminum alloy
When the L2 alloy is used, the obtained aluminum plate contains intermetallic compounds or single crystallized substances / precipitates at a density of about 100-10000 / mm ² . AL
When 3 alloy or AL4 alloy is used, the obtained aluminum plate has 5000-50000 pieces / mm ²
There are intermetallic compounds or single crystallized substances / precipitates in the range of.

1-4 Method of Manufacturing Aluminum Plate The aluminum plate is manufactured by DC casting method, continuous casting method, DC casting method.
It can be produced by either a casting method that omits the intermediate annealing treatment and / or the soaking treatment, or a continuous casting method that omits the intermediate annealing treatment.

2. Roughening treatment In the method for producing an aluminum support for a lithographic printing plate according to the present invention, as described in claim 1 of the present specification, (1) mechanical roughening treatment (a) is applied to the aluminum plate. (2) Alkaline etching treatment (b) (3) Desmut treatment (c) (4) Electrolytic surface roughening treatment (d) (5) Alkaline etching treatment (e) (6) Desmut treatment (f) (7) Electrolytic roughening treatment Surface-roughening treatment (g) Roughening treatment consisting of (8) alkali etching treatment (h) and (9) desmutting treatment (i) is performed, and then (10) anodizing treatment (j).

Each of the mechanical surface roughening treatment to the anodic oxidation treatment will be described below.

2-1 Mechanical Roughening Treatment (a) In the mechanical roughening treatment (a), at least one surface of the aluminum plate is rubbed with a roller brush to roughen the surface. Give.

The mechanical surface roughening treatment is preferably performed so that the center line average roughness (Ra) of the roughened surface after the treatment is in the range of 0.3 to 0.6 μm.

The brush graining will be described below.

Prior to the brush graining, if necessary, a degreasing treatment for removing rolling oil adhering to the surface of the aluminum plate can be performed. Examples of the degreasing treatment include treatment with a surfactant, treatment with an organic solvent, and treatment with an alkaline aqueous solution. However, the degreasing treatment can be omitted when the amount of rolling oil adhered is small.

Subsequently, while supplying the abrasive slurry to the surface of the aluminum plate, brush graining is performed using one type or two or more types of roller brushes having different bristles.

The brush graining is described in Japanese Patent Laid-Open No. 6-1.
35175, Japanese Examined Patent Publication No. 40047/1975, a roller-shaped brush is arranged on the upper side of an aluminum plate to be roughened and a supporting roller is arranged on the lower side, and the aluminum plate is moved at a constant speed. It can be carried out by rotating the roller-shaped brush while feeding the abrasive slurry between the roller-shaped brush and the aluminum plate while being conveyed.

The support roller is the roller-shaped brush 1.
Two can be arranged for each book. It is preferable that the pair of support rollers located below the roller brush be arranged such that the shortest distance of the outer surface is smaller than the outer diameter of the roller brush.

At the time of brush graining, it is preferable that the aluminum plate is pressed by the roller brush so as to be pressed between the two support rollers.

The roller-shaped brush used in the present invention has brush bristles formed of nylon, polypropylene, animal hair, steel wire or the like, which are planted on the entire side surface of the cylindrical body with a uniform bristle length and flock distribution. Preferably, a large number of small holes are formed on the entire surface of the body and a bristles of bristles, which are a bunch of bristles, are planted in each of the small holes, and a channel roller type is preferably used.

The bristles have a diameter of 0.05 mm to 0.
It is 8 mm, preferably 0.15 mm to 0.5 mm. The cross-sectional shape of the bristles is preferably circular. Hair diameter is 0.
If it is 05 mm or more, the stain performance in the shadow portion of the obtained lithographic printing plate is good, and if it is 0.8 mm or less, a lithographic printing plate that hardly causes blanket stain is obtained.

The bristle length after flocking of the brush bristles is 10 to 2
00 mm is preferable, and 25-100 mm is particularly preferable. The flocking density when planted in a roller brush is 1c.
The number is preferably 30 to 1,000, and more preferably 50 to 300 per m ² .

The material of the brush bristles is preferably nylon, especially nylon 6, nylon 6.6, nylon 6.1.
Nylon 6/10 is most preferable because it is excellent in tensile strength, wear resistance, dimensional stability due to water absorption, bending strength, heat resistance, and recovery.

The number of roller brushes is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and most preferably 3 or 4. As described in JP-A-6-135175, two or more roller-shaped brushes having different bristles may be combined.

The rotation number of the roller brush is 100 to 50.
A range of 0 rpm is preferred. The roller-shaped brush is preferably rotated (forwardly rotated) in the same direction as the aluminum plate conveying direction.
Some roller brushes may be rotated (reversed) in the same direction as the aluminum plate transport direction. When three roller-shaped brushes are used, the roller-shaped brush located on the most upstream side with respect to the conveying direction of the aluminum plate is rotated forward, the central roller brush is reversed, and the roller-shaped brush is conveyed with respect to the conveying direction of the aluminum plate. It is particularly preferable to rotate the roller brush located on the most downstream side in the forward direction. When four roller-shaped brushes are used, the rotation direction of the four roller-shaped brushes is from the upstream side (hereinafter, simply referred to as “upstream side”) of the aluminum plate conveyance direction to the aluminum plate conveyance direction. Therefore, forward rotation, reverse rotation, forward rotation, and forward rotation are preferable toward the downstream side (hereinafter, simply referred to as “downstream side”).

Further, the roller-shaped brush is set to 0.000 along a direction perpendicular to the conveying direction of the aluminum plate.
By oscillating at a frequency of 1-1 Hz and an amplitude of 10 to 200 mm, an aluminum support for a lithographic printing plate having a surface with no processing unevenness can be obtained.

The pushing amount of the roller brush is such that the power consumption of the motor is 1.0 to 15 kW, and more preferably 2
It is preferable to manage the roller brush based on the load of the motor that rotates the roller brush so that it becomes 10 kW.

In the above-described brush graining, after the thick brush bristles are roughened with the roller-shaped brush, the fine brush bristles are treated with the roller-shaped brush to give hydrophilicity, water retention and adhesion. It is preferable because a lithographic printing plate having both of the above can be obtained. The planographic printing plate,
Since there is no collapse of the shadow part when there is little dampening water,
It has the characteristics that it has a wide water width, is unlikely to cause scumming, and does not deteriorate in adhesion with the plate-making layer.

The abrasive slurry used in the present invention includes silica sand, aluminum hydroxide, alumina powder, volcanic ash,
It is preferable that an abrasive such as pumice powder, carborundum, and hard sand is dispersed in water in such a range that the specific gravity is 1.05 to 1.3. The average particle size of the abrasive is 1 to 60
μm, preferably 5 to 45 μm, and more preferably 15 to 45 μm. The average particle diameter is obtained as a particle diameter at which the cumulative ratio becomes 50% when the cumulative frequency of the ratio of particles of each diameter to the volume of all the abrasives contained in the slurry liquid is taken.

The average particle diameter of the abrasive is determined by, for example, passing the abrasive slurry through a classifying means such as a cyclone, and classifying the abrasive in the abrasive slurry into large particles and small particles. This can be controlled by collecting the abrasive slurry containing mainly the abrasive having the larger diameter and discarding the abrasive slurry containing mainly the abrasive having the smaller particle diameter.

The abrasive concentration in the abrasive slurry is controlled based on the specific gravity of the abrasive slurry. The specific gravity is preferably controlled so that the fluctuation range is within ± 10%.

The specific gravity of the abrasive slurry is, for example,
The specific gravity of the abrasive slurry is measured intermittently or continuously, and when the specific gravity is smaller than the above range, the abrasive slurry is supplemented with fresh abrasive to increase the specific gravity, and the specific gravity is above the range. If it is large, it can be controlled by replenishing the abrasive slurry with water to reduce the specific gravity.

In the brush graining, in order to obtain the center line average roughness (Ra) in the above range, the pressing amount of the roller brush, the number of rotations, the combination of the rotation directions, the number of roller brushes, and Roller brush diameter, brush bristle density, tension applied to the aluminum plate, type of abrasive compounded in the abrasive slurry, average particle size, particle size distribution, and flow rate / direction for spraying the abrasive slurry to the aluminum plate. -It is preferable to select an angle or the like.

2-2 Alkaline Etching Treatment By carrying out an alkaline etching treatment after the mechanical surface roughening treatment (a), the abrasives and aluminum debris which have bitten into the surface of the aluminum plate are removed and then applied. The electrolytic surface roughening treatment can be performed more uniformly and effectively. Also, electrolytic surface roughening treatment (d) and (g)
By performing an alkali etching treatment after the above, the aluminum hydroxide film formed on the surface of the aluminum plate in the electrolytic surface roughening treatment can be removed.

In the alkali etching treatment,
Etching is performed by bringing the aluminum plate into contact with an alkaline solution.

The aluminum plate may be brought into contact with the alkaline solution by, for example, continuously passing through the tank containing the alkaline solution, immersing in the tank containing the alkaline solution, and the alkaline solution. There is a method of spraying on the surface of the aluminum plate.

The amount of dissolution of the aluminum plate in the alkali etching treatment, in other words, the etching amount is ² to 15 g / m ² in the alkali etching treatment (b) that follows the mechanical surface roughening treatment (a). 3 to 10
A range of g / m ² is preferred. In the alkaline etching treatment (e) performed subsequent to the electrolytic surface roughening treatment (d), the etching amount is 0.1 to 6 g / m ² , and the etching amount is 0.1 to 3 g.
The range of / m ² is preferable. Then, in the alkaline etching treatment (h) performed subsequently to the electrolytic surface roughening treatment (g), the etching amount is 0.001 to 1 g / m ² ,
The range of 0.005 to 0.8 g / m ² is preferable.

The alkaline solution contains sodium hydroxide as a main alkaline component. The alkaline solution is preferably a sodium hydroxide solution containing a predetermined amount of aluminum ions.

The concentrations of sodium hydroxide and aluminum ions in the alkaline solution are 20 to 30% by weight and 5 to 9% by weight in the alkali etching treatment (b) and the alkali etching treatment (e), respectively.
Is preferable, and in the alkaline etching treatment (h), the range of 4 to 6% by weight and 0.3 to 0.7% by weight is preferable.

The temperature of the alkali solution is preferably in the range of 40 to 80 ° C. in the alkali etching treatment (b), and 3 in the alkali etching treatment (e).
The range of 0 to 80 ° C is preferable. And in the said alkali etching process (h), the range of 25-80 degreeC is preferable.

In order to stably carry out the alkali etching treatment, it is necessary to control the sodium hydroxide concentration in the alkali solution within a predetermined range. When the alkali solution contains aluminum ions, It is preferable to control the concentration so that it falls within a predetermined range.

The sodium hydroxide concentration and the aluminum ion concentration are controlled based on the specific gravity and electric conductivity of the alkaline solution. The fluctuation range of the specific gravity and conductivity is ±
It is preferable to control so as to be within 10%.

The alkali etching treatment can be carried out by using an etching apparatus which is commonly used for etching aluminum plates. The etching apparatus has a tank for storing an alkaline solution, a method of immersing the aluminum plate in the tank, and a spray nozzle, and the alkaline solution from the spray nozzle toward the aluminum plate. The form of spraying. The etching apparatus may be a batch type or a continuous type.

After the alkali etching treatment is completed, it is preferable to perform draining with a nip roller and washing with spray to prevent the treatment liquid from being brought into the next step.

2-3 Desmut Treatment In the alkali etching treatments (b), (e) and (h), the aluminum plate is treated with an alkali solution, so that smut is generated on the surface.

Therefore, the alkali etching treatment is performed.
After each of the steps (b), (e), and (h), the aluminum plate is brought into contact with an acidic solution for desmutting to remove surface smut.

The desmutting treatment can be carried out by immersing the aluminum plate in an acidic solution or by passing it through an acidic solution. Further, the acidic solution is sprayed by using a spray nozzle. The spray treatment is preferable.

As the acidic solution, as the main acid component,
Examples include solutions containing one or more acids selected from nitric acid, sulfuric acid, hydrochloric acid, and chromic acid. The concentration of the acidic component in the acidic solution is preferably 0.5 to 60% by weight. In the acidic solution, aluminum ions and ions of the trace elements contained in the aluminum alloy forming the aluminum plate are 0.
~ 5 wt% may be dissolved. Specifically, in the desmutting treatment (c) performed after the alkali etching treatment (b), the acid solution is a nitric acid solution containing 5 to 15 g / l of nitric acid or 80 to 300 g / l of sulfuric acid.
A sulfuric acid solution containing liter is preferable, in the desmut treatment (f) performed after the alkali etching treatment (e) and the desmut treatment (I) performed after the alkali etching treatment (h), the acidic solution is sulfuric acid. A sulfuric acid solution containing 80 to 500 g / liter is preferable.

Further, in the desmutting treatments (c) and (f), as the acidic solution, a waste liquid discharged from the electrolytic surface-roughening treatment (d) described later or the anodizing treatment (j) described later may be used. This is preferable because the amount of waste liquid discharged in the electrolytic surface roughening treatment (d) and the anodizing treatment (j) can be reduced. In the desmutting treatment (I), if the waste liquid discharged in the anodizing treatment (j) is used as the acidic solution, not only the amount of waste liquid can be significantly reduced, but also the desmutting treatment (I). Since it is possible to immediately shift to the anodizing treatment without cleaning the aluminum plate later, it is also preferable in that the washing equipment between the desmutting apparatus and the anodizing apparatus can be omitted.

The temperature of the acidic solution ranges from room temperature to 95 in any of the desmut treatments (c), (f), and (I).
The range of ° C is preferable, and the range of 25 to 80 ° C is particularly preferable.

The processing time is preferably 1 to 30 seconds, and particularly 1
-5 seconds is preferred.

After the desmut treatment is completed, it is preferable to drain the treatment liquid with a nip roller and wash it with water by spraying in order to prevent the treatment liquid from being brought into the next process. When the liquid having the composition or the waste liquid discharged in the next step is used, the draining and the water washing can be omitted in order to reduce the amount of the waste liquid.

2-4 Electrolytic surface roughening treatment As described above, in the first electrolytic surface roughening treatment (d), the electrolytic surface roughening treatment is carried out in the nitric acid solution to obtain the second electrolytic roughening treatment. Electrolytic surface roughening treatment, which is the second electrolytic surface roughening treatment
In (g), electrolytic surface roughening treatment is performed in a hydrochloric acid solution.

(1) Aqueous solution mainly containing nitric acid The concentration of nitric acid in the nitric acid solution used in the electrolytic graining treatment (d) is 0.2 to 2% by weight.

The nitric acid solution further contains 1 g / g of one or more salts selected from nitrates such as aluminum nitrate, sodium nitrate and ammonium nitrate, and hydrochlorides such as aluminum chloride, sodium chloride and ammonium chloride.
It can be added in the range of liter to saturated concentration. The nitric acid solution contains 1 to 20 compounds that form a complex with copper.
It can also be added so as to have a concentration of 0 g / liter. Further, in the nitric acid solution, iron, copper, manganese,
A trace element contained in the aluminum alloy forming the aluminum plate, such as nickel, titanium, magnesium, or silica, may be dissolved. In addition, it may contain hypochlorous acid or hydrogen peroxide at a concentration of 1 to 100 g / liter.

As the nitric acid solution, 5 to 15 g of nitric acid is used.
Particularly preferred is a solution in which an aluminum salt such as aluminum nitrate is added to the dilute nitric acid contained in 1 / liter to adjust the concentration of aluminum ions to 2 to 7 g / liter.

Further, when electrolytic surface roughening treatment is carried out in a nitric acid solution, ammonium ions are produced in the nitric acid solution due to the reduction reaction, so that the ammonium ion concentration in the nitric acid solution becomes 50 to 150 ppm. So that
It is particularly preferable to add ammonium nitrate in advance.

The liquid temperature of the nitric acid solution is preferably 30 to 80 ° C, particularly preferably 35 to 60 ° C.

The nitric acid concentration in the nitric acid solution is controlled based on the speed of sound and the electric conductivity of the nitric acid solution. Specifically, first, the sound velocity and the electric conductivity are measured for a plurality of nitric acid solutions having different nitric acid concentrations, and a calibration curve showing the relationship between the nitric acid concentration and the sound velocity and the electric conductivity is obtained. Next, the sonic velocity and the conductivity of the nitric acid solution actually used in the electrolytic surface roughening treatment (d) are measured, and from the measured values of the sonic velocity and the conductivity and the calibration curve, the nitric acid concentration in the nitric acid solution is measured. Ask for.

The nitric acid concentration is preferably controlled so that the fluctuation range of the sound velocity and the electric conductivity is within ± 10%. The control can be performed by adding concentrated nitric acid or adding water to dilute the nitric acid solution.

(2) In the aqueous solution electrolytic surface roughening treatment (g) mainly containing hydrochloric acid, the hydrochloric acid solution has a hydrochloric acid concentration of 0.1 to 2% by weight, in other words, 1 to 2 hydrochloric acid.
A hydrochloric acid solution containing 0 g / l is used.

In the hydrochloric acid solution, one or more kinds of salts selected from hydrochlorides such as aluminum chloride, sodium chloride and ammonium chloride and nitrates such as aluminum nitrate, sodium nitrate and ammonium nitrate are contained at a concentration of 1 g / liter to a saturated concentration. You may add in the range of.

A compound which forms a complex with copper may be added to the hydrochloric acid solution so as to have a concentration of 1 to 200 g / liter. In the hydrochloric acid solution, iron,
Trace elements contained in the aluminum alloy forming the aluminum plate, such as copper, manganese, nickel, titanium, magnesium, and silicon, may be dissolved. In addition, hypochlorous acid or hydrogen peroxide may be contained at a concentration of 1 to 100 g / liter.

As the hydrochloric acid solution, 2 to 15 g of hydrochloric acid is used.
The aluminum ion concentration is adjusted to 2 by adding aluminum salt such as aluminum chloride to dilute hydrochloric acid containing
A solution adjusted to -15 g / l is particularly preferable.

The liquid temperature of the hydrochloric acid solution is preferably 20 to 50 ° C.

The concentration of hydrochloric acid in the hydrochloric acid solution is controlled based on the speed of sound and the electric conductivity of the hydrochloric acid solution, like the nitric acid solution. Specifically, as in the case of the nitric acid solution, a calibration curve showing the relationship between the hydrochloric acid concentration in the hydrochloric acid solution and the speed of sound and conductivity is obtained, and the speed of sound of the hydrochloric acid solution used in the electrolytic surface roughening treatment (g) and The concentration of hydrochloric acid in the hydrochloric acid solution is determined from the measured value of conductivity and the calibration curve.

It is preferable that the concentration of hydrochloric acid in the hydrochloric acid solution is also controlled so that the fluctuation range of the sound velocity and the electric conductivity is within the range of ± 10%. The control can be performed by adding concentrated hydrochloric acid or adding water to dilute the hydrochloric acid solution.

(3) Conditions for electrolytic surface roughening treatment In both electrolytic roughening treatments (d) and (g), an alternating current is applied.

In the electrolytic surface-roughening treatment (d), the quantity of electricity when the aluminum plate participates in the anode reaction, that is, the quantity of electricity at the time of anode is 30 to 300 C / dm ² , preferably 100 to 250 C / dm ² . The alternating current is applied so that On the other hand, in the electrolytic surface roughening treatment (g), the alternating current is applied so that the amount of electricity at the time of anode is 3 to 150 C / dm ² , and preferably 15 to 50 C / dm ² .

As the alternating current, an alternating current having various waveforms such as a sine wave current, a rectangular wave current, a trapezoidal wave current and a triangular wave current can be used, but a rectangular wave current and a trapezoidal wave current are preferable, and a trapezoidal wave current is preferable. Wave currents are particularly preferred.

The frequency of the alternating current is 0.1 to 500 Hz.
Is preferred.

An example of the trapezoidal wave is shown in FIG. When the trapezoidal wave shown in FIG. 1 is used, the rise time t _p (t _pa or t _pc ) from 0 to the peak of the current is 0.1 to 1
The range of 0 msec is preferable, and the range of 0.5 to 2 msec is particularly preferable. If the rise time t _p is 0.1 or more, the influence of the impedance of the power supply circuit is small,
Since a large power supply voltage is not required at the rising of the current waveform, the power supply circuit can be constructed at low cost. Further, if the rising time t _p is 10 msec or less, the electrolytic surface roughening treatments (1) and (2) are hardly affected by the trace components in the nitric acid solution or the hydrochloric acid solution, so that the uniform rough surface is obtained. Is done.

The condition of one cycle of alternating current used for electrochemical surface roughening is that the anode reaction time t _{a of the} aluminum plate.
But the proportion t _a / T as a percentage of the period T of the alternating current, 0.33
0.66 is preferable, 0.45-0.55 is more preferable, and 0.5 is particularly preferable.

The quantity of electricity applied to the aluminum plate facing the main pole is the quantity of electricity Q _c during the cathode reaction of the aluminum plate.
And the ratio Q _c / Q _{a of the} quantity of electricity Q _a during the anode reaction is 0.9 to
It is preferably in the range of 1. The electric quantity ratio can be controlled by controlling the voltage generated by the power source. Figure 2
When the electrolytic cell shown in (3) is used, the firing angle of the thyristor Th is controlled to adjust the electricity quantity ratio.

In the electrolytic graining treatments (d) and (g),
The current density is a peak value of a trapezoidal wave, and both the anode cycle side I _a and the cathode cycle side I _{c of the current} are 5 to 50 A / dm.
² , preferably 15 to 35 A / dm ² .

In each of the electrolytic surface roughening treatments (d) and (g), a known electrolytic cell such as a vertical type, a flat type or a radial type can be used as the electrolytic cell.

FIG. 2 shows an example of the radial type electrolytic cell.

As shown in FIG. 2, the radial type electrolytic cell 104 has an electrolytic cell 42 in which a nitric acid solution or a hydrochloric acid solution is stored, and is arranged inside the electrolytic cell 42 so as to be rotatable about an axis extending horizontally. It is provided with a feed roller 44 for feeding the aluminum web W, which is a strip-shaped continuous thin plate, in the direction of arrow a, that is, from the left side to the right side in FIG.

The inner wall surface of the electrolytic cell 42 is formed in a substantially cylindrical shape so as to surround the feed roller 44, and the semi-cylindrical counter electrodes 46A and 46B are provided on the inner wall surface so as to sandwich the feed roller 44. There is. The counter electrodes 46A and 46B are divided into a plurality of electrodes, and an insulating spacer is interposed between the respective electrodes. The electrodes can be formed of, for example, graphite or metal, and the spacers can be formed of, for example, vinyl chloride resin. The thickness of the spacer is preferably 1 to 10 mm. Although not shown in FIG. 1, the counter electrodes 46A and 46A are not shown.
In each case of B, each of the electrodes divided by the spacer is connected to the AC power supply AC.

An opening 42A into / from which the aluminum web W is introduced / extracted during the AC electrolytic graining treatment is formed in the upper portion of the electrolytic cell 42. In the vicinity of the opening 42A in the electrolytic cell 42 and between the counter electrode 46A and the main electrode 46B, acidic electrolytic solution replenishing channels 48A and 48B for replenishing the electrolytic cell 42 with the nitric acid solution or the hydrochloric acid solution are provided.

In the vicinity of the opening 42A above the electrolytic bath 42, an upstream guide roller 50B for guiding the aluminum web W into the electrolytic bath 42, and an aluminum plate W electrolytically treated in the electrolytic bath 42 are placed in the electrolytic bath 42. And a group of downstream guide rollers 50A for guiding the outside of the vehicle.

The radial type electrolytic cell 104 includes an electrolytic cell 42.
An overflow tank 52 is provided adjacent to the upstream side of. The overflow tank 52 has a function of temporarily storing the nitric acid solution or the hydrochloric acid solution overflowing from the electrolysis tank 42 and keeping the liquid level of the nitric acid solution in the electrolysis tank 42 constant.

In the radial type electrolytic cell 104, an auxiliary electrolytic cell 54 is further provided adjacent to the upstream side of the electrolytic cell 42.

The auxiliary electrolytic bath 54 is shallower than the electrolytic bath 42, and has a bottom surface 54A formed in a flat shape, and a plurality of rod-shaped auxiliary electrodes 56 are provided on the bottom surface 54A.

The auxiliary electrode 56 is preferably made of a highly corrosion-resistant metal such as platinum or ferrite, or may be plate-shaped.

The auxiliary electrode 56 is connected in parallel to the main pole 46B on the side of the AC power supply AC to which the main pole 46B is connected, and in the middle, the thyristor Th1 is connected to the main pole 46B of the AC power supply AC during ignition. It is connected so that a current flows from the side to the auxiliary electrode 56.

The side of the AC power source AC to which the counter electrode 46A is connected is also connected to the auxiliary electrode 5 via the thyristor Th2.
Connected to 6. The thyristor Th2 is connected so that a current flows from the side of the AC power supply AC toward the auxiliary electrode 56 at the time of ignition.

When either of the thyristors Th1 and Th2 is fired, the anode current flows through the auxiliary electrode 56. Therefore, by controlling the phase of the thyristors Th1 and Th2, the current value of the anode current flowing through the auxiliary electrode 56 can be controlled, and therefore Qc / Qa can also be controlled.

The operation of the radial type electrolytic cell 104 shown in FIG. 2 will be described below.

The aluminum plate W guided from the right side in FIG. 2 to the radial type electrolytic cell 104 along the arrow a is:
First, it is introduced into the auxiliary electrolytic bath 54, and then guided to the electrolytic bath 42 by the upstream guide roller 50. And
It is fed from the right side to the left side in FIG. 1 by the feed roller 44, and the electrolytic cell 4 is fed by the downstream guide roller 50A.
Guided out of 2.

Inside the electrolytic layer 42 and the auxiliary electrolytic cell 54, the aluminum plate W is provided with the counter electrodes 46A and 46B.
The surface on the side facing the counter electrodes 46A and 46B is roughened by the alternating current applied to the electrode and the anode current applied to the auxiliary electrode 56.

Only one electrolytic cell may be used, or two or more electrolytic cells may be used in series. In electrolytic graining treatment (d), 1 to 3 cells are used in series. It is particularly preferable to carry out the electrolytic graining treatment (g) in a single tank. When using two layers of electrolytic cells in the electrolytic surface roughening treatment (d), make the current density and quantity of electricity in the first electrolytic cell higher than the current density and quantity of electricity in the second electrolytic cell. Is particularly preferable. Further, the alternating current having the same waveform may be applied to all the electrolytic cells, or the alternating current having a different waveform may be applied to each electrolytic cell. Which waveform of alternating current is applied to which electrolytic cell can be determined according to the desired pit shape.

A main electrode for applying an alternating current to the aluminum plate is provided inside the electrolytic cell.

In the electrolytic cell, the distance between the aluminum plate transported inside and the main electrode is 5 to 100 m.
It is desirable to dispose the running path of the aluminum plate and the main electrode so that the length is m, preferably 8 to 15 mm.
The main electrode is preferably made of carbon.

The average relative flow velocity of the aluminum plate conveyed in the electrolytic cell and the nitric acid solution or the hydrochloric acid solution flowing in the electrolytic cell is preferably in the range of 1 to 1000 m / min, and in the range of 15 to 300 m / min. Ranges are particularly preferred. As long as the average relative flow velocity is within the above range, the flow direction of the nitric acid solution or the hydrochloric acid solution may be either the same direction as the transport direction of the aluminum plate or the opposite direction.

Further, it is desirable that the distance between the running path of the aluminum plate and the main electrode and the flow rates of the nitric acid solution and the hydrochloric acid solution are kept constant for uniform electrolytic graining.

In the flat type and vertical type electrolytic cells, as described in JP-B-61-30036, a surface on which a traveling aluminum plate is slidable is provided inside and static pressure is applied. The distance can be kept constant by running the aluminum plate while pressing the aluminum plate. Further, in the radial type electrolytic cell, as described in JP-A-8-300843, a roller having a large diameter for conveying the aluminum plate is provided inside and a plurality of rollers are provided so as to surround the roller. By disposing the main electrode on the circumference, the distance between the main electrode and the aluminum plate can be kept constant.

Further, in order to make the flow rates of the nitric acid solution and the hydrochloric acid solution constant, a liquid pool chamber is provided inside the electrolytic cell, and a width of 1 to 5 is set along the width direction of the aluminum plate running inside.
The nitric acid solution and the hydrochloric acid solution may be supplied using a liquid supply nozzle provided with a slit for ejecting a liquid of mm. In addition, a plurality of liquid pool chambers may be provided, and the liquid pool chambers may be connected to each other by a pipe line equipped with a valve and a flow meter, and the amount of liquid discharged from each slit of the liquid supply nozzle may be adjusted.

The power feeding method to the aluminum plate running inside the electrolytic cell is, for example, a direct power feeding method using a conductor roller, a liquid power feeding method not using the conductor roller, or in other words, an indirect power feeding method.

When the indirect power supply method is used in the electrolytic cell, the current value can be controlled by using a transformer and a variable induction voltage regulator.

Further, in addition to the main electrode, an auxiliary anode for applying a direct current is provided inside the electrolytic cell, and the strength of the direct current flowing through the auxiliary electrode is controlled to prevent The ratio between the quantity of electricity and the quantity of electricity at the time of the cathode can be adjusted. The auxiliary electrode can be formed of ferrite or the like.

Methods for controlling the current flowing through the auxiliary anode include Japanese Patent Publication No. 6-37716 and Japanese Patent Publication No. 5-4.
As described in Japanese Patent No. 2520, phase control by a controlled rectifier such as a thyristor and GTO, control by a diode and a variable resistor, and the like can be mentioned.
If the current flowing through the auxiliary anode is controlled by the above method, the influence of the magnetic bias of the transformer can be reduced, and the power supply device can be manufactured at low cost, which is very advantageous in terms of cost.

In the case of using the direct power feeding method, as the conductor roller, as described in JP-A-58-177441, industrial aluminum is used for casting and subjected to high temperature homogenizing treatment for surface portion. It is possible to use a conductor roller in which the corrosion resistance is improved by changing the Al-Fe-based compound of ( _{3) to} a single phase of Al ₃ Fe. Further, as described in JP-A-56-123400, the conductor roller is provided at the introduction part of the aluminum plate in the flat type or vertical type electrolytic cell, or both the introduction part and the extraction part of the aluminum plate. An arranged electrolyzer can be used.

In the electrolytic cell, the conductor roller can be provided so as to come into contact with the upper surface or the lower surface of the aluminum plate. However, it is provided so as to come into contact with the upper surface of the aluminum plate, and the conductor roller is attached to the aluminum plate by the nip device. It is particularly preferable to press it. The length of contact between the aluminum plate and the conductor roller is preferably 1 mm to 300 mm in the aluminum traveling direction. The pass roller facing the conductor roller with the aluminum plate interposed therebetween is preferably a rubber roller having a rubber body. The pressing pressure of the conductor roller and the hardness of the body of the rubber roller are
It can be arbitrarily set under the condition that an arc spot does not occur at a position where the conductor roller and the aluminum plate are in contact with each other. By installing the conductor roller so that it contacts the upper surface of the aluminum plate, replacement work and inspection work of the conductor roller are simplified. In order to energize the conductor roller, it is preferable to provide a rotating body concentrically at the end of the conductor roller and energize while the power feeding brush slides on the rotating body.

It is preferable that the conductor roller is always cooled with the nitric acid solution or the hydrochloric acid solution in order to prevent the generation of arc spots.

2-5 Anodizing Treatment For the anodizing treatment of the aluminum plate, a sulfuric acid solution containing sulfuric acid as a main acid component is used.

The amount of the anodic oxide film is appropriately in the range of 1 to 5 g / m ² . When the amount of the anodic oxide film is 1 g / m ² or more, sufficient printing durability can be obtained, so that the non-image area of the lithographic printing plate is less likely to be scratched, and therefore the so-called flaw in which the ink adheres to the scratched portion. Hard to get dirty. When the amount of the anodic oxide film is large, the oxide film is likely to concentrate on the edge portion of the aluminum plate, but if the amount of the anodic oxide film is 5 g / m ² or less, such a problem does not occur. However, the difference in the amount of oxide film between the edge portion and the central portion of the aluminum plate is preferably 1 g / m ² or less.

The composition of the aqueous sulfuric acid solution is described in JP-A-54-1.
As described in detail in JP-A-28453 and JP-A-48-45303, the sulfuric acid concentration is 10 to 3
A sulfuric acid aqueous solution having a concentration of 00 g / liter and an aluminum ion concentration of 1 to 25 g / liter is preferable, a sulfuric acid concentration of 80 to 200 g / liter and an aluminum ion concentration of 2 to 10 g / liter are particularly preferable. The liquid temperature is preferably 30 to 60 ° C, particularly 30 to 55 ° C.
Is preferred.

The sulfuric acid concentration and the aluminum ion concentration are controlled by the specific gravity and the electric conductivity. Specifically, it can be controlled by replenishing the sulfuric acid solution with water or replenishing concentrated sulfuric acid while measuring the specific gravity and electric conductivity of the sulfuric acid solution continuously or at regular intervals. The control is preferably performed so that the fluctuation range of the specific gravity and the electric conductivity is within ± 10%.

In the anodizing treatment, a direct current is usually applied to the aluminum plate to perform the anodizing treatment, but an alternating current may be applied.

[0151] When performing anodic oxidation treatment using a direct current, the current density is preferably in the range of 1 to 60 A / dm ^2, in particular in the range of 5 to 40 A / dm ² is preferred. When continuously anodizing an aluminum plate, in order to prevent current concentration called burning of the aluminum plate, anodizing treatment is performed at a low current density of 5 to 10 A / dm ² on the most upstream side, and the downstream side is subjected. It is preferable to gradually increase the current density by increasing the current density to a value of 30 to 50 A / dm ² or higher. Current density is 5
It is preferable to gradually increase the current density in 15 to 15 steps, and by providing an independent power supply device for each step and controlling the current density in each of the power supply devices, the current density can be gradually increased toward the downstream side. . As a method for feeding power to the aluminum plate, a liquid feeding method which will be described later without using a conductor roller is preferable. Japanese Patent Laid-Open No. 2001-
An example is shown in Japanese Patent No. 11698.

As a method of feeding power to the aluminum plate, a direct feeding method and a liquid feeding method can be mentioned as in the case of the electrolytic surface roughening treatment.

The direct power feeding method is disadvantageous in that a spark is generated between the conductor roller and the aluminum web at a high speed and a high current density, so that the line speed is 30 m.
It is often used in anodizing equipment with a relatively low speed and low current density of less than 1 / min.
It is often used in high-speed, high-current-density anodic oxidation equipment that exceeds 0 m / min.

When using the indirect power supply method, use the Yamakoshi type or straight type tank layout as described on page 289 of the continuous surface treatment technology (General Technology Center, issued September 30, 1986). You can

In both the direct power feeding system and the indirect power feeding system, in order to reduce energy loss due to voltage drop in the aluminum web, the anodizing process is divided into two or more, and a power feeding tank and an oxidation tank of each electrolyzer, Alternatively, it is particularly preferable to use a DC power supply connected between the conductor roller and the oxidation tank.

When the direct power feeding method is used, the same conductor roller as the conductor roller described in the above "2-4 Electrolytic surface roughening treatment" can be used as the conductor roller.

Since a large current is passed in the anodizing process, a Lorentz force acts on the aluminum plate by the magnetic field generated by the current flowing through the bus bar. As a result, a problem occurs that the web meanders.
It is particularly preferable to use the method as described in 90.

Since a large current flows through the aluminum plate, the Lorentz force acts toward the center in the width direction of the aluminum plate due to the magnetic field generated by the current flowing through the aluminum plate itself. As a result, the aluminum plate is likely to be broken, so that the diameter of the aluminum plate is 100
It is particularly preferable to adopt a method in which a plurality of 200 mm pass rollers are provided at a pitch of 100 to 3000 mm and are wrapped at an angle of 1 to 15 degrees to prevent breakage due to Lorentz force.

Further, since the amount of anodic oxide film produced increases as it gets closer to the edge of the aluminum plate, and the thickness becomes thicker, there is a problem that the aluminum plate cannot be properly wound in the winding device. The above-mentioned problems are caused by Japanese Patent Publication No. 62-30275 and Japanese Patent Publication No. 55-2.
As described in Japanese Patent No. 1840, this can be solved by stirring the acidic electrolytic solution. When the above problem cannot be sufficiently solved even by stirring the acidic electrolyte, the winding device is oscillated in the width direction of the aluminum plate with an amplitude of 5 to 50 mm at a cycle of 0.1 to 10 Hz. Can solve the problem of plate winding.

As the anode for passing a current through the aluminum plate, lead, iridium oxide, platinum, ferrite or the like can be used, but those mainly containing iridium oxide are particularly preferable. The substrate can be coated with iridium oxide by heat treatment. So-called valve metals such as titanium, tantalum, niobium and zirconium are used as the base material, and titanium or niobium is particularly preferable. Since the valve metal has a relatively large electric resistance, it is particularly preferable to use copper for the core material and clad the valve metal around the core. When clad with a valve metal on a copper core material, it is not possible to make a very complicated shape, so the electrode parts made by dividing into individual parts are coated with iridium oxide, and then the desired structure with bolts, nuts, etc. It is common to assemble so that

2-6 Sealing / Hydrophilic Treatment Anodized aluminum plate has a property of dissolving the anodized film in the developer and suppressing the residual film of the plate-making layer in the non-image area, the strength of the anodized film, For the purpose of improving hydrophilicity and adhesion to the plate-making layer, it is possible to carry out hydrophilic treatment after washing with water.

Examples of the hydrophilic treatment include a silicate treatment in which the anodic oxide film is brought into contact with an aqueous solution of an alkali metal silicate for treatment.

In the silicate treatment, the alkali metal silicate concentration is usually 0.1 to 30% by weight, preferably 0.5 to 15% by weight, and the pH at 25 ° C. is 10 to 1%.
The aluminum plate is added to an aqueous solution of an alkali metal silicate of 3.5 at 5 to 80 ° C, preferably 10 to 70 ° C.
More preferably, it can be carried out by contacting at 15 to 50 ° C. for 0.5 to 120 seconds.

Examples of the method of bringing the aluminum plate into contact with the aqueous solution of the alkali metal silicate include immersion and spraying, but are not limited to these methods.

The pH of the alkali metal silicate aqueous solution is
When it is less than 10, gelling occurs, and when it is more than 13.5, the anodic oxide film is dissolved.

As the alkali metal silicate, sodium silicate, potassium silicate, lithium silicate or the like is used.

For adjusting the pH of the aqueous solution of the alkali metal silicate, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide is used.

The aqueous solution may contain an alkaline earth metal salt or a Group IVB metal salt.

The alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate and barium nitrate, and water-soluble salts such as sulfates, hydrochlorides, phosphates, acetates, oxalates and borates. Examples include salt.

Examples of the Group IVB metal salt include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, potassium titanium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride oxide and the like.

The alkaline earth metal and Group IVB metal salts may be used alone or in combination of two or more.
A preferable blending amount of the alkaline earth metal and the group IVB metal salt is 0.01 to 10% by weight, and a further preferable blending amount is 0.05 to 5% by weight.

The aluminum plate may be subjected to a sealing treatment in addition to the hydrophilic treatment.

The sealing treatment includes steam sealing, boiling water (hot water) sealing, metal salt sealing (chromate / dichromate sealing, nickel acetate sealing, etc.), oil-impregnated sealing. Well-known treatments for sealing the anodized film, such as synthetic resin sealing, low-temperature sealing (using red blood salt, alkaline earth salt, etc.), etc. Water vapor sealing is preferred from the viewpoints of adhesion with (and hydrophilicity with), high-speed treatment, low cost, low pollution, and the like.

As the water vapor sealing, for example, pressurized or normal pressure water vapor may be continuously or discontinuously applied and the relative humidity 70
%, And the vapor temperature is 95 ° C. or higher for about 2 seconds to 180 seconds. A method disclosed in JP-A-4-176690 is used.

Other sealing methods include dipping in hot water or alkaline aqueous solution, hot water or alkaline spraying, dipping in aqueous nitrite solution, and spraying aqueous nitrite solution. The immersion in the nitrite aqueous solution and the spraying treatment may be performed instead of the immersion in the hot water or the alkaline aqueous solution and the spraying treatment, or may be performed subsequent to the treatment.

Examples of the nitrite include I of the periodic table.
Mention may be made of metal nitrites which are the nitrites of the metals of the groups a, IIa, IIb, IIIb, IVb, IVa, VIa, VIIa, VIII, and ammonium nitrite.

Examples of the metal nitrite include LiN
O₂, NaNO₂, KNO₂, Mg (NO₂)₂, Ca (N
O₂)₂ , Zn (NO₂)₂, Al (NO₂)₃, Zr (N
O₂) _Four, Sn (NO₂)₃, Cr (NO₂)₃, Co (NO
₂)₂, Mn (NO₂)₂, Ni (NO₂)₂Etc. are preferred,
Alkali metal nitrate is particularly preferable. More than 2 kinds of nitrite
It can also be used together.

The treatment conditions cannot be uniquely determined because they differ depending on the state of the aluminum plate and the type of nitrite, but when sodium nitrite is used, for example,
The concentration is generally 0.001 to 10% by weight, more preferably 0.01 to 2% by weight. The bath temperature is generally from room temperature to about 100 ° C., more preferably 6
It is 0 to 90 ° C. Processing time is generally 15-300
Seconds, and more preferably 10 to 180 seconds.

The pH of the nitrite aqueous solution is 8.0 to 11.0.
Is preferably adjusted to, and particularly preferably adjusted to 8.5 to 9.5. P of nitrite aqueous solution
In order to prepare H in the above range, it can be preferably prepared using, for example, an alkaline buffer solution. Examples of the alkaline buffer include a mixed aqueous solution of sodium hydrogen carbonate and sodium hydroxide, a mixed aqueous solution of sodium carbonate and sodium hydroxide, a mixed aqueous solution of sodium carbonate and sodium hydrogen carbonate, a mixed aqueous solution of sodium chloride and sodium hydroxide, and hydrochloric acid. A mixed aqueous solution of sodium carbonate and sodium carbonate, a mixed aqueous solution of sodium tetraborate and sodium hydroxide, and the like can be preferably used, but not limited thereto. In addition, an alkali metal salt other than sodium, such as potassium salt, can be used as the above alkaline buffer solution.

After performing at least one of the hydrophilic treatment and the pore-sealing treatment, in order to further improve the adhesion to the plate-making layer, the acidic aqueous solution treatment and hydrophilicity treatment disclosed in JP-A-5-278362 are used. You may undercoat,
JP-A-4-282637 and Japanese Patent Application No. 6-10867.
The organic layer disclosed in the specification of No. 8 may be provided.

After the surface of the support is subjected to the above treatment or undercoating, a back coat is provided on the back surface of the support, if necessary. Such a back coat comprises a metal oxide obtained by hydrolyzing and polycondensing an organic polymer compound described in JP-A-5-45885 and an organic or inorganic metal compound described in Japanese Patent Application No. 4-189448. A coating layer is preferably used. Examples of the organic or inorganic metal compound include Si (OC)
_{H 3) 4, Si (OC} 2 H 5) 4, Si (OC 3 H 7) 4, Si
A silicon alkoxy compound such as (OC ₄ H ₉ ) ₄ is particularly preferable because it is inexpensive and easily available, and a metal oxide coating layer having excellent developer resistance can be easily formed.

2-7 Rinse Treatment In order to remove the chemicals and abrasives used in each of the above treatments from the surface of the aluminum plate, a rinsing step of rinsing the aluminum plate is provided between each treatment. Good.

In the water washing step, the water washing treatment is usually carried out between treatment tanks using chemical liquids of different types and compositions. It is preferable that the time for the aluminum plate to come out of one processing tank and enter the cleaning step and the time for the aluminum plate to enter the next processing tank adjacent to the one cleaning tank be 10 seconds or less. , 0.1-1
0 second is particularly preferred. If the time is 10 seconds or less,
Since the chemical modification of the surface of the aluminum plate does not proceed so much, it is difficult for uneven processing to occur. Further, the passage time of the aluminum plate from the one treatment tank to the next treatment tank is preferably 15 seconds or less, and particularly preferably 5 seconds or less. When the passage time is 15 seconds or less, the chemical modification of the surface of the aluminum plate hardly progresses, and uniform roughening treatment can be performed in the next step.

In the step of washing the aluminum plate with water, the surface drained by the nip roller is generally washed with water from a spray tip in a water washing tank. Water is preferably jetted downstream at an angle of 45 to 90 degrees.

The water injection pressure is preferably 0.5 to ⁵ kg / cm ² immediately before the injection nozzle, and the water temperature is 10 to 80.
C is preferred.

The transport speed of the aluminum plate is 20 to 2
00 m / min is preferable.

The amount of washing water sprayed on the aluminum plate is preferably 0.1 to 10 liters / m ² per washing step.

In the water washing tank, it is preferable to spray the washing water on the front surface and the back surface of the aluminum plate from at least two spray pipes. It is preferable to install 5 to 30 spray tips at a pitch of 50 mm to 200 mm in one spray tube. The spray angle of the spray tip is preferably 10 to 150 degrees, and the distance between the aluminum plate and the spray tip jetting surface is preferably 10 to 250 mm. The cross-sectional shape (spray pattern) of the spray of the spray tip includes an annular shape, a circular shape, an elliptical shape, a square shape, a rectangular shape, and the like, and a circular / inert circular shape or a square / rectangular shape is preferable. The flow rate distribution (state of water distribution of spray on the surface of the aluminum plate) has an annular distribution, a uniform distribution, a mountain-shaped distribution, etc., but when using multiple spray tips arranged side by side in the spray pipe, a uniform flow distribution over the entire width. A mountain-shaped distribution that facilitates The flow rate distribution changes with the spray pressure and the distance between the spray tip and the aluminum plate. The particle size of the spray varies depending on the structure of the spray tip, the spray pressure, and the spray amount, but a range of 10 μm to 10000 μm is preferable,
Particularly, the range of 100 μm to 1000 μm is preferable. It is preferable that the material of the spray nozzle has abrasion resistance against a liquid flowing at a high speed, and brass, stainless steel, ceramic or the like is used, but a ceramic nozzle is particularly preferable.

The spray nozzle provided with the spray tip can be arranged at an angle of 45 to 90 ° with respect to the traveling direction of the aluminum plate. It is preferable to make it perpendicular to the traveling direction of the aluminum plate.

The time of the washing process is 1 per washing process.
0 seconds or less is industrially preferable, and 0.5 second to 5 seconds is particularly preferable.

2-8 Material of Pass Roller A pass roller for carrying or supporting the aluminum plate can be provided in the treatment tank and the water washing tank for carrying out the above respective treatments.

As the pass roller, a metal roller, a resin roller, a rubber roller, a non-woven cloth roller or the like having a surface plated or lined for use in a continuous production line such as a steel line, a plating line, an electrolytic capacitor production line, a PS plate production line, etc. Can be used.

The material of the pass roller and the physical property value of the surface are
It is selected in consideration of the required corrosion resistance, abrasion resistance, heat resistance, chemical resistance, etc. according to the chemical solution used for the treatment and the surface condition of the aluminum plate.

A hard chrome plated roller is generally used as the metal roller.

As the rubber roller, natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, butyl rubber, chloroprene rubber, chlorosulfonated polyethylene, nitrile rubber, acrylic rubber, epicrawler hydrin rubber, urethane rubber, polysulfide rubber, fluorine It is possible to use a roller having a cylinder made of rubber such as rubber, and a material obtained by adding a trace amount of additives to the rubber. It is particularly preferable that the hardness of the body of the rubber roller is 60 to 90.

When the aluminum web is wet and slippery, it is particularly preferable to use a non-woven fabric roller which is unlikely to slip even when the aluminum web is wet, when controlling the transport speed of the aluminum web. When a rubber roller is used at the location, it is particularly preferable to provide the roller with a motor for auxiliary driving.

3. Plate making layer 3-1 For the purpose of eliminating dissolution of aluminum during development of the back coat layer and eliminating scratches due to rubbing between the plate making layer and the aluminum support for lithographic printing plates,
As described in JP-A-6-32115, a thickness of 0.01-8 containing an organic polymer compound and a surfactant.
A μm back coat layer can be provided.

As the main component of this back coat layer, at least one resin selected from the group consisting of a saturated copolymerized polyester resin, a phenoxy resin, a polyvinyl acetal resin and a vinylidene chloride copolymerized resin having a glass transition point of 20 ° C. or higher is used. To be

The saturated copolyester resin is composed of a dicarboxylic acid unit and a diol unit.

Examples of the dicarboxylic acid unit of the polyester used in the present invention include aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, tetrabromophthalic acid and tetrachlorophthalic acid, and adipic acid, azelaic acid, succinic acid, Oxalic acid, suberic acid, sebacic acid,
Examples thereof include malonic acid and saturated aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid.

The back coat layer further comprises a dye or pigment for coloring, a silane coupling agent for improving adhesion to an aluminum support, a diazo resin containing a diazonium salt, an organic phosphonic acid, an organic phosphoric acid and a cation. Waxes, higher fatty acids, higher fatty acid amides, silicone compounds composed of dimethylsiloxane, modified dimethylsiloxane, polyethylene powder and the like, which are usually used as a slip agent, are appropriately added.

Various methods can be applied for coating the back surface of the aluminum support with the back coating layer. As such a method, for example, a method of applying and drying a solution or emulsion dispersion of the resin, a method of adhering the resin previously formed into a film shape to an aluminum support with an adhesive or heat, and a melt extruder Examples of the method include forming a molten film of the resin and attaching it to a support. The most preferable method for securing the above coating amount is a method of applying a solution or emulsion dispersion of the resin and drying. Is.

3-2 Plate Making Layer (1) Visible Light Exposure Type Plate Making Layer The visible light exposure type plate making layer can be formed of a composition containing a photosensitive resin and, if necessary, a colorant and the like.

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

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

On the other hand, as the negative photosensitive resin, a diazo resin such as a condensation product of an aromatic diazonium salt and an aldehyde such as formaldehyde, an inorganic acid salt of the diazo resin,
And a diazo compound such as an organic acid salt of the diazo resin,
Combination with a binder such as (meth) acrylate resin, polyamide resin, and polyurethane, and (meth)
Examples include combinations of vinyl polymers such as acrylate resins and polystyrene resins, vinyl polymerizable compounds such as (meth) acrylic acid esters and styrene, and photopolymerization initiators such as benzoin derivatives, benzophenone derivatives, and thioxanthone derivatives.

As the colorant, in addition to usual dyes,
It is possible to use an exposed coloring dye that develops color upon exposure, and an exposure decolorizable dye that becomes almost or completely colorless upon exposure. Examples of the light-exposure coloring dyes include leuco dyes. On the other hand, examples of the exposure decolorizable dyes include triphenylmethane dyes, diphenylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.

The visible light exposure type plate making layer can be formed by applying a photosensitive resin solution containing the photosensitive resin and the colorant in a solvent and drying.

Examples of the solvent used for the photosensitive resin solution include a solvent which dissolves the photosensitive resin and has some volatility at room temperature. Specific examples thereof include alcohol solvents and ketones. Examples thereof include system solvents, ester solvents, ether solvents, glycol ether solvents, amide solvents, and carbonate ester solvents.

As the alcohol solvent, ethanol,
Propanol, butanol, etc. are mentioned. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, and diethyl ketone. Examples of the ester solvent include ethyl acetate, propyl acetate, methyl formate, ethyl formate and the like. Examples of the ether solvent include tetrahydrofuran and dioxane, and examples of the glycol ether solvent include ethyl cellosolve, methyl cellosolve, and butyl cellosolve.
Examples of the amide solvent include dimethylformamide and dimethylacetamide. Examples of the carbonate ester solvent include ethylene carbonate, propylene carbonate, diethyl carbonate, dibutyl carbonate and the like. (2) Laser exposure type plate making layer As the laser exposure type plate making layer, a negative type laser plate making layer in which a portion irradiated with laser light remains after exposure and development, and a positive type laser plate making in which a portion irradiated with laser light is removed layer,
The main examples thereof include a photopolymerization type laser plate making layer which undergoes photopolymerization when irradiated with a laser beam.

A. Negative Laser Plate Making Layer The negative type laser plate making layer is (A) an acid precursor which decomposes by heat or light to generate an acid, (B) an acid precursor (A) which is decomposed and cross-linked by an acid. The acid-crosslinkable compound (C), the alkali-soluble resin (D), the infrared absorber (D), and the compound (E) containing a phenolic hydroxyl group can be dissolved or suspended in an appropriate solvent to form a negative laser plate-making layer forming liquid. .

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

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

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

As the infrared absorber (D), 760 nm
Dyes and pigments that absorb infrared rays of up to 1200 nm are listed, and specifically, black pigments, red pigments, metal halide pigments, phthalocyanine pigments, and azo dyes, anthraquinone dyes, phthalocyanine dyes that absorb infrared rays of the above wavelengths, Examples include cyanine dyes.

As the phenolic hydroxyl group-containing compound (E), a compound of the general formula (R ₁ -X) _n -Ar- (OH) _m (R ₁ is
It is a C6-C32 alkyl group or alkenyl group, X is an end bond, O, S, COO, or CONH, Ar is an aromatic hydrocarbon group, an alicyclic hydrocarbon group,
Alternatively, it is a heterocyclic group, and both n and m are natural numbers of 1 to 3. ). The compound shown by these is mentioned. Specific examples of the compound include alkylphenols such as nonylphenol.

Further, a plasticizer and the like can be added to the negative type laser plate making layer forming liquid.

B. Positive type laser plate making layer The positive type laser plate making layer is a positive type laser plate in which (F) an alkali-soluble polymer, (G) an alkali dissolution inhibitor and (H) an infrared absorbing agent are dissolved or suspended in an appropriate solvent. It can be formed by a plate-making layer forming liquid.

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

Examples of the alkali dissolution inhibitor (G) include compounds that react with the alkali-soluble polymer (F) by heating or the like to reduce the alkali-solubility of the alkali-soluble polymer (F). Examples thereof include sulfone compounds, ammonium salts, sulfonium salts, and amide compounds. For example, alkali-soluble polymer (F)
When the above novolac resin is used as, the cyanine dye, which is one of the sulfone compounds, is preferable as the alkali dissolution inhibitor (G).

Examples of the infrared absorbent (H) include squarylium dyes, pyrylium dyes, carbon black, insoluble azo dyes, anthraquinone dyes, and the like, 750 to 120.
Examples include dyes, dyes, and pigments having an absorption region in the infrared region of 0 nm and having a light / heat conversion ability.

C. Photopolymerizable Laser Plate-Making Layer The photopolymerizable laser plate-making layer can be formed with a photopolymerizable laser plate-making layer forming liquid containing (I) a vinyl polymerizable compound having an ethylenically unsaturated bond at the molecular end. If necessary, the photopolymerization laser plate-making layer forming liquid may contain (J) a photopolymerization initiator and (K) a sensitizer.

Examples of the vinyl polymerizable compound (I) include an ethylenically unsaturated carboxylic acid polyester which is an ester of an ethylenically unsaturated carboxylic acid such as (meth) acrylic acid, itaconic acid and maleic acid and an aliphatic polyhydric alcohol. Valent ester,
Examples thereof include ethylenically unsaturated carboxylic acid polyvalent amides such as methylenebis (meth) acrylamide and xylylene (meth) acrylamide, which are composed of the ethylenically unsaturated carboxylic acid and polyvalent amine.

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

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

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

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

When forming the photopolymerizable laser plate-making layer, a silicone compound having a reactive functional group such as a partially decomposed silane compound obtained by partially decomposing a silane compound with water, alcohol or carboxylic acid. It is preferable to pretreat the roughened surface of the lithographic printing plate support in order to improve the adhesion between the lithographic printing plate support and the photopolymerizable laser plate making layer.

3-3 Coating Method The photosensitive resin solution, the negative type laser plate making layer forming liquid, the positive type laser plate making layer forming liquid, and the photopolymerization type laser plate making layer forming liquid were applied to the aluminum support for a lithographic printing plate. As a method for applying to the surface to be surfaced, conventionally known methods such as a method using a coating rod, a method using an extrusion type coater and a method using a slide bead coater can be used, and the method can be performed according to known conditions.

As an apparatus for drying an aluminum plate after coating the photosensitive resin solution, the negative type laser plate making layer forming liquid, the positive type laser plate making layer forming liquid and the photopolymerization type laser plate making layer forming liquid, there is disclosed in Japanese Patent Laid-Open No. Hei 6 (1999) -58242. -63487,
Arrange a pass roll in the drying device, an arch type dryer that dries while conveying it with the pass roll, an air dryer that supplies air from the top and bottom with a nozzle and dries while floating the web, radiant heat from a medium heated to a high temperature There are a radiant heat dryer for drying and a roller dryer for heating a roller and drying it by conduction heat transfer due to contact with the roller.

[0231]

EXAMPLES The present invention will be described more specifically below with reference to examples. <1. Preparation of lithographic printing plate support> Samples 1-1 to 1-under the conditions shown in Tables 1 to 4 according to the procedure described below.
14 and Samples 2-1 to 2-14 were produced. After each treatment, water washing treatment was performed, and after each treatment and water washing treatment, drainage was performed by a nip roller. However, in the other treatment performed subsequent to the one treatment, when the same treatment liquid as that used in the one treatment is used, washing with water is performed between the one treatment and the other treatment. Omitted.

[0232]

[Table 1]

[0233]

[Table 2]

[0234]

[Table 3]

[0235]

[Table 4] (1) Mechanical surface roughening treatment (a) While supplying abrasive slurry containing pumice having an average particle diameter of 12 μm as an abrasive from the spray tube to the surface of the aluminum plate, mechanical roughening is performed by a rotating roller brush. I made a face.

The material of the brush bristles in the roller-shaped brush was nylon 6.10. The brush bristles have a diameter of 30.
Holes were punched in a 0 mm stainless steel tube and hair was densely planted. Three roller brushes were used. Two support rollers were provided for each of the roller brushes. The diameter of the supporting roller is 200 mm, and the distance is 300 m.
It was m. The bristle diameter was 0.5 mm and the bristle length was 300 mm.

With respect to the pushing amount of the roller-shaped brush, the increase amount of the load of the drive motor for rotating the roller-shaped brush with respect to the load of the drive motor before the pressing of the roller-shaped brush becomes constant, and after the roughening. The aluminum plate was controlled so that the average surface roughness was 0.4 to 0.5 μm. The oscillation amplitude was 100 mm.

In the mechanical surface roughening treatment, the abrasive slurry is sampled at regular time intervals to measure the specific gravity, and the abrasive is replenished so that the fluctuation range of the specific gravity is within ± 10%. To control the concentration of the abrasive.

(2) Alkaline etching treatment (b) From the spray tube, the aluminum plate after the mechanical surface roughening treatment had the NaOH concentration shown in Tables 1 to 4 and contained 7.5% by weight of aluminum ions. Alkali solution was sprayed, and alkali etching treatment was performed so that the amount of aluminum dissolved on the roughened surface became the value shown in Table 1 or Table 2.

Regarding the control of the concentration of the alkali solution, the alkali solution supplied to the spray tube is sampled at regular time intervals to measure the specific gravity and the conductivity, and the fluctuation range of the specific gravity and the conductivity is measured. Was carried out by replenishing the alkaline solution with water or sodium hydroxide so as to be within ± 10%.

(3) Desmutting treatment (c) Desmutting treatment was performed using an acidic solution having the composition and liquid temperature shown in Tables 1 to 4.

(4) Electrolytic surface roughening treatment (d) In a nitric acid solution having the composition and the liquid temperature shown in Tables 1 to 4, FIG.
The electrolytic cell shown in FIG. 2 was used to apply the trapezoidal wave current having the waveform shown in FIG. The frequency of the trapezoidal wave current was 60 Hz, and the amount of electricity and the current density during the anode reaction of the aluminum plate were as shown in Tables 1 to 4. The AC duty (ta / T) was 0.5, and the rise times tpa and tpc were 0.3 msec. The ratio Qc / Qa of the total amount of electricity Qa during the anode reaction and the total amount of electricity Qc during the cathode reaction of the aluminum plate in the portion facing the main electrode of carbon was 0.95. As the amount of electricity applied to the aluminum plate, the total amount of electricity applied to the aluminum plate while the aluminum plate passed through the electrolytic cell and the amount of electricity subjected to the anode reaction of the aluminum plate was shown.

The concentration of nitric acid in the nitric acid solution was measured by measuring the sound velocity and the conductivity of the nitric acid solution at regular time intervals, and the concentration of nitric acid was adjusted so that the fluctuation range between the sound velocity and the conductivity was within ± 10%. Alternatively, water was added to control.

(5) Alkaline etching treatment (e) From the spray tube, the aluminum plate after the mechanical surface roughening treatment had the NaOH concentration shown in Tables 1 to 4 and contained 7.5% by weight of aluminum ions. Alkali solution was sprayed and alkali etching treatment was performed so that the aluminum dissolution amount on the roughened surface became the values shown in Tables 1 to 4.

The concentration of sodium hydroxide in the alkaline solution was controlled by the same method as in the alkaline etching treatment (d).

(6) Desmutting treatment (f) Desmutting treatment was carried out using an acidic solution having the composition and liquid temperature shown in Tables 1 to 4.

(7) Electrolytic surface roughening treatment (g) Using the electrolytic cell shown in FIG. 2 in an aqueous hydrochloric acid solution having the composition and liquid temperature shown in Tables 1 to 4, the trapezoidal wave current having the waveform shown in FIG. 1 is used. Was applied to carry out electrolytic surface roughening treatment. The frequency of the trapezoidal wave current was 60 Hz, and the amount of electricity and the current density during the anode reaction of the aluminum plate were as shown in Tables 1 to 4. The AC duty (ta / T) was 0.5, and the rise times tpa and tpc were 0.5 msec. The ratio Qc / Qa of the total amount of electricity Qa during the anode reaction and the total amount of electricity Qc during the cathode reaction of the aluminum plate in the portion facing the main electrode of carbon was 0.95.
As the amount of electricity applied to the aluminum plate, the total amount of electricity applied to the aluminum plate while the aluminum plate passed through the electrolytic cell and the amount of electricity subjected to the anode reaction of the aluminum plate was shown.

Regarding the concentration of hydrochloric acid in the hydrochloric acid solution, the sonic velocity and the conductivity of the hydrochloric acid solution are measured at regular time intervals, and concentrated hydrochloric acid is adjusted so that the fluctuation range between the sonic velocity and the conductivity is within ± 10%. Alternatively, water was added to control.

(8) Alkaline etching treatment (h) The aluminum plate after the mechanical surface roughening treatment was sprayed with an alkaline solution having the NaOH concentration shown in Tables 1 to 4 on the roughened surface from a spray tube. Table 1 shows the amount of aluminum dissolved
Alternatively, alkali etching treatment was performed so that the values shown in Table 2 were obtained.

The concentration of sodium hydroxide in the alkaline solution was controlled by the same method as the alkaline etching treatment (d).

(9) Desmutting treatment (I) Desmutting treatment was carried out using an acidic solution having the composition and liquid temperature shown in Tables 1 to 4.

(10) Anodizing sulfuric acid samples 1-1 to 1-14 and samples 2-1 to 2-1
2-14 is anodized by applying direct current in a sulfuric acid solution having a sulfuric acid concentration of 10% by weight and a liquid temperature of 30 ° C. to form an anodized film so that the surface coating amount becomes 2.6 g / m ^2. did.
The sulfuric acid solution used for the anodizing treatment is sampled at regular intervals to measure the specific gravity and the electric conductivity, and concentrated sulfuric acid or water is replenished so that the fluctuation range of the specific gravity and the electric conductivity is within ± 10%. Then, the sulfuric acid concentration in the sulfuric acid solution was controlled.

Sample 3 was prepared according to the same procedure as in Samples 1-1 to 1-14 except that the concentrations of the abrasive slurry, alkali solution, nitric acid solution, hydrochloric acid solution and sulfuric acid solution were not controlled. 1-3-14 were produced.

<2. Preparation and Evaluation of Lithographic Printing Plate> (Example A, Comparative Example A) Samples 1-1 to 1-14 and samples 2-1 to 2-14, which were anodized,
It was dipped in a 1 wt% sodium silicate solution having a liquid temperature of 20 ° C. for 7 seconds to form a 4 g / m 2 silicate film on the surface. In the following, the above samples are referred to as 1-1A to 1-14, respectively.
A and 2-1A to 2-14A.

A plate-making layer was formed on the above-mentioned sample on which the silicate film had been formed, according to the plate-making layer formation examples 1 to 10, and the plate-making and printing were carried out to obtain printing durability, the number of wiped sheets, stains on non-image areas, and stains after leaving. , And the presence or absence of defective inking due to deposits on the blanket rolls were evaluated. The results are shown in Table 5.

[0256]

[Table 5] (Example B, Comparative Example B) A plate-making layer was formed according to the plate-making layer forming examples 1 to 10 without any post-treatment on the anodized samples 1-1 to 2-14, and When printing, printing durability, number of paid sheets, non-image area stain,
The stains after standing and the presence or absence of defective inking due to deposits on the blanket roller were evaluated. The results are shown in Table 6.

[0257]

[Table 6] (Comparative Examples 3-1A to 3-14A) Samples 3-1A to 3-14A were post-treated according to the same procedures and conditions as those described in the above "Example A, Comparative Example A" to form a plate-making layer, After plate making and printing, printing durability, the number of printed sheets, stains on non-image areas, stains after leaving, and presence or absence of inking defects due to deposits on the blanket roller were evaluated. The results are shown in Table 7.

[0258]

[Table 7] The following procedures evaluated the printing durability, the number of paid-out sheets, the stains on the non-image area, the stains after leaving, and the defective inking.

Printing durability: Evaluation was made by the number of sheets of printing paper through which rubbing of ink and scumming on the printing paper surface were clearly observed. When the number of passed sheets was 50,000 or less, it was evaluated as "poor", and when the number of passed sheets was more than 50,000, it was evaluated as "good".

-Payment number: The number of printed matter on which the ink is not printed on the non-image area is visually observed to check how many times the printed matter does not occur after the start of printing. Those having a large number of printed materials were evaluated as "poor".

Stain on non-image area: At the time of printing, the state of dirt on the non-image area of the printed matter in a squeezed water condition was visually observed, and the one with less stain was evaluated as "good", and the stain Those with a large number were evaluated as “poor”.

Staining after leaving: After printing 10,000 sheets, leaving the plate as it is for 1 hour, and then visually observing the stain on the non-image part when printing is restarted,
It was evaluated in four grades of "very good", "good", "somewhat bad", and "poor".

Defects in ink thickness: "very good", "good", "slightly bad", and "poor", based on the difficulty of occurrence of inking defects due to deposits on the blanket rollers of the offset rotary printing press. It was evaluated on a 4-point scale.

(Plate-making layer forming example 1) Samples 1-1 to 1-14 and samples 2-1 to 2-, which have been subjected to the respective post-treatments
The undercoating liquid having the following composition was applied to 14 and dried at 80 ° C. for 30 seconds. The coating amount after drying was 30 mg / m 2.

[Undercoat liquid] Aminoethylphosphonic acid 0.10 g Phenylphosphonic acid 0.15g β-alanine 0.10 g 40 g of methanol 60 g of pure water.

Next, a photosensitive layer forming liquid A having the following composition was coated on the aluminum support for a lithographic printing plate in various coating amounts and dried at 110 ° C. for 1 minute to prepare a positive photosensitive lithographic plate. I got the original printing plate.

[0267]   [Photosensitive layer forming liquid A] 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetate Esterification with a resin (described in Example 1 of US Pat. No. 3,635,709) That is) 0.45g Cresol-formaldehyde novolac resin (meta / para ratio = 6: 4, weight flat Average molecular weight of 3,000, number average molecular weight of 1,100, and 0.7% of unreacted cresol)  1.1 g m-cresol-formaldehyde novolak resin (weight average molecular weight 1,700, number Average molecular weight 600, containing 1% of unreacted cresol) ... 0.3 g N- (P-aminosulfonylphenyl) acrylamide-normal butyl acryl Rate-diethylene glycol monomethyl ether methacrylate copolymer (each Charged molar ratio of monomer = 40: 40: 20, weight average molecular weight 40,000, number average molecule 20,000) 0.2 g P-normal octylphenol-formaldehyde resin (US Pat. No. 4,123,27 What is described in the specification No. 9) ... 0.021 g Naphthoquinone-1,2-diazide-4-sulfonic acid chloride                                                         … 0.01 g Tetrahydrophthalic anhydride: 0.1 g Benzoic acid: 0.02g 4- [p-N, N-bis (ethoxycarbonylmethyl) aminophenyl] -2, 6-bis (trichloromethyl) -S-triazine ... 0.01 g 4- [PN- (P-hydroxybenzoyl) aminophenyl] -2,6-bis (Trichloromethyl) -S-triazine ... 0.02 g 2-Trichloromethyl-5- (4-hydroxystyryl) -1,3,4-oxa Diazole ... 0.01g Substitute counter anion of Victoria Pure Blue BOH with 1-naphthalene sulfonic acid Dye ... 0.02g Contains 30% by weight of MODIPER F-200 (a fluorinated surfactant manufactured by NOF CORPORATION) Methyl ethyl ketone and methyl isobutyl ketone mixed solvent solution           … 0.06g Megafac F177 (Dainippon Ink and Chemicals Co., Ltd. fluorinated surfactant) Methyl isobutyl ketone solution containing 20% by weight) ... 0.02 g Methyl ethyl ketone ... 15g 1-methoxy-2-propanol ... 10 g The one having the composition of was used.

An aqueous solution of a copolymer obtained by copolymerizing methyl methacrylate, ethyl acrylate and sodium acrylate at a charge molar ratio of 68/20/12 on the plate making layer coated with the photosensitive layer forming liquid A and dried. Was electrostatically sprayed to provide a mat layer.

The obtained photosensitive lithographic printing plate precursor was passed through a transparent positive film in a vacuum baking frame and exposed for 50 seconds from a distance of 1 m by a metal halide lamp of 3 kw. Then, a mole of SiO2 / Na2O was used as a developing solution. A 5.26% aqueous solution of sodium silicate with a ratio of 1.74 (pH =
12.7) as a rinsing liquid by Fuji Photo Film Co., Ltd.
Processing was carried out by passing through an automatic processor Stablon 900D manufactured by Fuji Photo Film Co., Ltd. charged with FR-3 (1: 7) manufactured by FR.

The printing performance of the obtained lithographic printing plate was evaluated. Heidelberg SOR-M is used as the printing machine, and Fuji Photo Film Co., Ltd. EU- is used as the dampening water.
3 (1: 100) to which 10% of isopropanol was added was used, and printing was performed using Mark Five New Ink manufactured by Toyo Ink Co., Ltd. as the ink.

(Plate-making layer forming example 2) Samples 1-1 to 1-14 and samples 2-1 to 2-which have been subjected to each of the above-mentioned post-treatments.
The following coating liquid was applied to 14 at a coating amount of 2 g / m 2 and dried to form a base layer.

[0272]   [Coating liquid] 1,2-diazonaphthoquinone-5-sulfonyl chloride Pyrogallol-acetone resin esterification product (Weight average molecular weight 2500) 40 parts by weight Phenol formaldehyde resin (Weight average molecular weight 10,000, 90% of trinuclear or more components) 75 parts by weight Acrylic Polymer I 35 parts by weight 2- (p-butoxyphenyl) -4,6-bis (trichloro) (Methyl) -s-triazine 3 parts by weight Oil blue # 603 (Orient Chemical Co., Ltd.) 1.5 parts by weight Mega Fuck F-176 (Dainippon Ink and Chemicals, Inc. Fluorine-based surfactant) 0.3 parts by weight Methyl ethyl ketone 1000 parts by weight Propylene glycol monomethyl ether 1000 parts by weight The one having the composition of was used.

The acrylic polymer I was synthesized by the following procedure.

60.3 g of N- (p-toluenesulfonyl) methacrylamide, 10.0 g of acrylonitrile and 46.0 g of ethyl acrylate were dissolved in 232.6 g of dimethylformamide, and 2,2'-azobis (2,2) was obtained under a nitrogen stream. 4-dimethylvaleronitrile) 0.224 g
Was used as a polymerization initiator, and the mixture was stirred at 65 ° C. for 7 hours. The reaction solution was allowed to cool and then reprecipitated in 5 liters of water. The precipitated polymer was collected by filtration and dried to obtain 110.4 g of acrylic polymer I (yield 95%, Mw 52,000).

Further, the following mat forming resin liquid was sprayed to form a mat layer. A 12% aqueous solution of methyl methacrylate / ethyl acrylate / acrylic acid (preparation weight ratio 65:20:15) copolymer as a part of sodium salt was prepared as a mat layer forming resin liquid, and a rotary atomizing electrostatic coating machine was prepared. The atomizing head rotation speed is 25,000 rpm, the resin liquid feed rate is 40 ml / min, and the voltage applied to the atomizing head is -90 kV.
The ambient temperature at the time of application is 25 ° C., the relative humidity is 50%, steam is sprayed on the application surface 2.5 seconds after application to moisten, and 3 seconds after moistening, warm air with temperature 60 ° C. and humidity 10% is applied. Sprayed for 5 seconds to dry.

The lithographic printing original plate thus prepared was exposed through a document film for 60 seconds from a distance of 1 m using a 3 kW metal halide lamp.

[Developer a (pH about 12.4)] D-sucrose 4.8% by weight Sodium hydroxide 0.34% by weight Sodium carbonate 0.70% by weight Tetrabutylammonium bromide 0.03% by weight Water 94.7% by weight The one having the composition of was used. [Development replenisher a (pH about 13.0)] D-sucrose 9.7% by weight Sodium hydroxide 1.5% by weight Sodium carbonate 1.0% by weight Tetrabutylammonium bromide 0.07% by weight Water balance The one having the composition of was used.

[0278]   [Finishing gum solution] Gum arabic 1.8% by weight Enzyme-modified potato starch 18.3% by weight Enzyme-modified starch syrup starch 3.7% by weight Phosphorylated waxy corn starch starch 1.8% by weight Sodium salt of dioctyl sulfosuccinate 0.91% by weight Ammonium monophosphate 0.27% by weight Phosphoric acid (85%) 0.37% by weight EDTA-tetrasodium salt 0.27% by weight Ethylene glycol 1.8% by weight Benzyl alcohol 2.3% by weight Sodium dehydroacetate 0.04% by weight Emulsion type antifoaming agent 0.02% by weight Water 68.4% by weight The one having the composition of was used.

[0279]   [Rinse solution] Sodium dodecyl diphenyl ether disulfonate (40% by weight aqueous solution)                            … 6.7 wt% Sodium hexametaphosphate: 0.8% by weight Benzyl alcohol: 1.5% by weight Polyoxyethylene (addition of 12 mol of ethylene oxide) nonyl phenyl ether                            … 1.5% by weight Sodium dioctyl sulfosuccinate: 1.4% by weight Phosphoric acid (85% by weight) ... 5.2% by weight Sodium hydroxide: 2.0% by weight Silicon antifoaming agent: 0.01% by weight Water ... 80.89% by weight The one having the composition of was used.

Next, 20 liters of each of the above developing solutions was placed in a developing tank of a commercially available automatic developing machine PS-900D (manufactured by Fuji Photo Film Co., Ltd.) having an immersion type developing tank and kept at 30 ° C. The second bath of PS-900D was charged with 8 liters of tap water, and the third bath was charged with 8 liters of a finishing liquid: water = 1: 1 diluted. This PS
The exposed lithographic printing plate was passed through -900D and developed.

The planographic printing plate after development was evaluated for printing performance in the same procedure as in Plate-making layer formation example 1.

(Plate-making layer forming example 3) Samples 1-1 to 1-14 and samples 2-1 to 2- which have been subjected to the above respective post-treatments
A 14% aqueous solution of a copolymer having the following composition A was applied to 14 by a roll coater and dried to form an undercoat layer. The coating amount after drying was 0.05 g / m 2.

[Composition A] Methyl methacrylate / ethyl acrylate / 2-acrylamido-2-methylpropane sulfonate (molar ratio of charge = 50: 30: 2)
0) copolymer (average molecular weight of about 60,000).

A photosensitive layer-forming liquid having the following composition was applied onto the undercoat layer and dried to obtain a photosensitive lithographic printing original plate. This is used as a sample.

[0285]   [Photosensitive layer forming liquid] 2-hydroxyethylmethacrylate copolymer (US Pat. No. 4,123,276) What is described in Example 1. ) ... 0.87g 2-Methoxy-a condensate of p-diazodiphenylamine and paraformaldehyde 4-hydroxy-5-benzoylbenzenesulfonate                                   ... 0.1g "Oil Bull- # 603" (blue dye from Orient Chemical Industry Co., Ltd.)                                   … 0.03 g Methanol ... 6g 2-methoxyethanol: 6g The one having the composition of was used.

The dry coating amount of the plate-making layer was 2.0 g / m ² .

A transparent negative original image was vacuum-contacted to the lithographic printing plate precursor and a metal halide lamp of 3 kW was used to measure 60 m from a distance of 1 m.
After exposure for 2 seconds, the plate was immersed in a developer having the following composition for 1 minute, the surface of the plate-making layer was lightly rubbed with a sponge to develop, and a commercially available desensitizing gum solution was applied.

[0288] The one having the composition of was used.

Printing was carried out using this lithographic printing plate in the same manner as in Plate-making layer formation example 1.

(Plate Making Layer Formation Example 4) [Preparation of Carbon Black Dispersion] Carbon Black 1 part by weight Copolymer of benzyl methacrylate and methacrylic acid (charge molar ratio 72:28, weight average molecular weight 70,000) 1.6 parts by weight Parts cyclohexanone 1.6 parts by weight methoxypropyl acetate 3.8 parts by weight of a composition dispersed by glass beads for 10 minutes,
A carbon black dispersion was obtained.

[Preparation of negative photosensitive lithographic printing plate precursor] The following photosensitive layer forming liquid was applied to each of the post-treated Samples 1-1 to 1-14 and Samples 2-1 to 2-14, It was dried at 100 ° C. for 2 minutes to obtain a negative photosensitive lithographic printing original plate. The coating amount after drying was 2.0 g / m 2.

[0292]   [Photosensitive layer forming liquid]   As the photosensitive layer forming liquid, 10 g of the carbon black dispersion Hexafluorophosphate of a condensation product of 4-diazodiphenylamine and formaldehyde                                   0.5 g Methacrylic acid, 2-hydroxyethyl acrylate, benzyl methacrylate Acrylonitrile radical copolymer (molar ratio of charged monomers 15:30:40: 15, weight average molecular weight 100,000) 5g Malic acid 0.05g FC-430 (Fluorine-based surfactant manufactured by 3M Company, USA)                                         0.05 g 1-Methoxy-2-propanol 80g Ethyl lactate 15g 5 g of water The one having the composition of was used.

The obtained negative type photosensitive lithographic printing plate precursor was exposed with a YAG laser adjusted to a plate surface output of 2 W, and then developed by Fuji Photo Film Co., Ltd., DN-3C (1: 1),
When processed through an automatic processor equipped with gum solution FN-2 (1: 1), a negative image was obtained. This lithographic printing plate was printed on a Heidel SOR-KZ machine.

(Plate-making layer forming example 5) Samples 1-1 to 1-14 and samples 2-1 to 2-which have been subjected to the above respective post-treatments.
The following undercoat liquid was applied to 14 with a wire bar and dried at 90 ° C. for 30 seconds using a warm air dryer. The coating amount after drying was 20 mg / m 2.

[0295]   <Undercoat liquid>   ・ Methacryloyloxyethylphosphonic acid 0.2 g   ・ Mole ratio of methyl acrylate and sodium styrenesulfonate 75 : Copolymer of 15 0.2 g   ・ Calcium nitrate 0.2g   ・ Methanol 20g   -Ion-exchanged water 80g. The one having the composition of was used.

[Formation of Recording Layer] The following recording layer coating solution [P-1] was coated on the support having the undercoat layer formed thereon with a wire bar and the mixture was dried at 120 ° C. for 45 seconds in a warm air dryer. A recording layer is formed by drying, and the following overcoat layer coating solution is applied using a slide hopper and dried at 120 ° C. for 75 seconds with a hot air dryer to obtain a lithographic printing original plate [P-1]. Got The coating amount of the recording layer coating liquid [P-1] was 2.0 g / m @ 2, and the coating amount of the overcoat layer coating liquid was 2.3 g / m @ 2. <Coating liquid for recording layer [P-1]>-Titanocene type radical generator 0.1 g (CGI-784, manufactured by Ciba Specialty Chemicals Co., Ltd.)-Polymerizable compound (RM-2) 0.60 g-Polymerization Functional compound (RM-3) 0.20 g-Visible light absorber (VR-1) 0.10 g-Polymer (PB-1) 1.20 g-Copper phthalocyanine pigment 0.04 g-Polymerization inhibitor 0.005 g (cuperon Al , Wako Pure Chemical Industries, Ltd.-Fluorosurfactant 0.03 g (Megafuck KF309, Dainippon Ink and Chemicals, Inc.)-Methyl ethyl ketone 10 g-γ-butyrolactone 5 g-Methanol 7 g-1-Methoxy-2 -Propanol having a composition of 5 g was used.

The polymerizable compound RM-2 and the polymerizable compound RM-3 used for preparing the recording layer coating liquid [P-1] were used.
The visible light absorber VR-1 has the following structure.

[0298]

[Chemical 1]

[0299]

[Chemical 2]

[0300]

[Chemical 3] Moreover, the polymer (PB-1) was synthesized by synthesizing a copolymer of methacrylic acid, N-isopropylacrylamide and ethyl methacrylate, and then reacting it with 1,2-epoxy-3-methacryloyloxymethylcyclohexane. The composition molar ratio is 15:30:20:
35 and the weight average molecular weight was 120,000. The structural formula of the polymer PB-1 is as follows.

[0301]

[Chemical 4] <Coating liquid for overcoat layer> -Polyvinyl alcohol 3.0 g (saponification degree 98.5 mol%, polymerization degree 500) -Nonionic surfactant 0.05 g (EMEREX NP-10 manufactured by Nippon Emulsion Co., Ltd.) ) -Ion-exchanged water having a composition of 96.95 g was used.

[Evaluation of developer composition] An automatic processor (LP-850P2) manufactured by Fuji Photo Film Co., Ltd. was charged with the developer composition (V-2) having the following composition in a development tank, and
It was kept warm at ℃. The second bath of the automatic processor was charged with tap water, and the third bath was charged with FP-2W (manufactured by Fuji Photo Film Co., Ltd.): Water = 1: 1 diluted finishing gum solution. The pH of the developer was 8.1.

[0303]   <Developer composition [V-2]>   ・ Sodium hydrogen carbonate 26g   ・ Ethylene glycol mononaphthyl ether                 Sodium monosulfate salt 30g   ・ Ethylene glycol monododecyl ether 20g   ・ Sodium sulfite 3g   ・ Ethylenediaminetetraacetic acid tetrasodium 1g   ・ Water 920g The one having the composition of was used.

Next, 20 lithographic printing original plates [P-1] having a size of 1030 × 800 mm were used, using a 30 mW semiconductor laser emitting a 405 nm violet light, and a laser beam diameter of 12 μm.
m, the plate surface energy was 50 μJ / cm 2, and scanning exposure was performed, and development processing was performed using the above-mentioned automatic developing machine. After treatment,
The automatic developer was left for 3 days. Then, one lithographic printing original plate [P-1] was similarly laser-exposed and subsequently developed. The lithographic printing plate [P-1] thus obtained was printed using a printer Lithrone manufactured by Komori Corporation.

(Example 6 of plate-making layer formation) Samples 1-1 to 1-14 and samples 2-1 to 2- which have been subjected to the above-mentioned respective post-treatments.
The following undercoat liquid was applied to 14 with a wire bar and dried at 90 ° C. for 30 seconds using a warm air dryer. The coating amount after drying was 20 mg / m 2.

[0306]   <Undercoat liquid>   ・ 4-diazo-3methoxydiphenylamine and formaldehyde Condensation product of dibutylnaphthalene sulfonate 0.3g   -Magnesium salt of 2-aminoethylphosphonic acid 0.1 g   ・ Calcium chloride 0.2g   ・ Methanol 20g   ・ Ion-exchanged water 80g The one having the composition of was used.

[Formation of Recording Layer] The following coating solution for recording layer was applied onto the support having the undercoat layer formed thereon with a wire bar and dried at 120 ° C. for 45 seconds in a warm air dryer to form a recording layer. Then, the planographic printing original plate [P-2] of Example 1 was obtained. The coating amount after drying was 2.0 g / m 2.

[0308]   <Coating liquid for recording layer [P-2]>   -Onium salt (KO-1) 0.25g   -Polymerizable compound (RM-1) 0.60 g   ・ Infrared absorber (IR-1) 0.06g   ・ Polymer (PB-2) 1.40 g   ・ Victoria Pure Blue Naphthalene Sulfonate 0.04g   ・ N-allyl stearic acid amide 0.01 g   ・ Polymerization inhibitor 0.005g     (Irganox 1010, manufactured by Ciba Specialty Chemicals Co., Ltd.)   ・ Fluorosurfactant 0.03g   (Megafuck KF309, manufactured by Dainippon Ink and Chemicals, Inc.)   ・ Methyl ethyl ketone 10g   ・ Γ-Butyrolactone 5 g   ・ Methanol 7g   ・ 1-Methoxy-3-propanol 5 g The one having the composition of was used.

The structures of the onium salt KO-1, the polymerizable compound RM-1, and the infrared absorber IR-1 are as follows:
It is as shown below.

[0310]

[Chemical 5]

[0311]

[Chemical 6]

[0312]

[Chemical 7] The polymer (PB-2) is reacted with 3-chloro-2-hydroxypropyl methacrylate in the presence of a base and potassium iodide after synthesizing a copolymer of methacrylic acid, N-acryloylmorpholine and benzyl methacrylate. It was synthesized by The composition molar ratio is
15: 30: 10: 45 with a weight average molecular weight of 10
It was good. The structural formula is as follows

[0313]

[Chemical 8] [Evaluation of Developer Composition] Plate material feeding device (SA-L800
0), an exposure apparatus (Luxel T-9000CTP),
Conveyor (T-9000 Conveyor), automatic developing machine (LP-1310H), stocker (ST-116)
0) Fuji Photo Film Co., Ltd. CTP output system was used. A developer composition (V-1) having the following composition was placed in a development processing tank of an automatic processor and kept at 30 ° C. Tap water was charged in the second bath of the automatic processor, and FP-2W (manufactured by Fuji Photo Film Co., Ltd.): water = in the third bath.
A finishing gum solution diluted 1: 1 was charged. The pH of the developing solution was 8.0.

[0314]   <Developer composition [V-1]>   ・ Potassium hydrogen carbonate 20g   ・ Sodium dibutylnaphthalene sulfonate 30g   ・ Ethylene glycol mononaphthyl ether 20g   ・ Sodium sulfite 3g   ・ Hydroxyethanediphosphonate potassium 2g   ・ Silicone SA730 0.1g     (Toshiba Silicone Co., Ltd. surfactant)   ・ Water 924.9g The one having the composition of was used.

Next, lithographic printing original plate [P-2] size 10
30 pieces of 30 × 800 mm are loaded in the plate material supply device,
Exposure and development processing were carried out continuously and fully automatically and discharged to the stocker. After the processing, the automatic developing solution was left as it was for 3 days. After standing, one lithographic printing original plate [P-2] was loaded in a plate material supplying device, continuously and fully automatically exposed and developed, and discharged to a stocker. The obtained planographic printing plate [P-
2] was printed using a printing machine Lithrone manufactured by Komori Corporation.

(Plate-making layer forming example 7) Samples 1-1 to 1-14 and samples 2-1 to 2- which have been subjected to the respective post-treatments
The undercoating liquid having the following composition was applied to 14 and dried at 80 ° C. for 15 seconds to form a coating film. The coating amount of the coating film after drying was 15 mg / m 2. <Undercoat composition> 0.3 g of a polymer compound represented by the following chemical formula

[0317]

[Chemical 9] -The thing which has a composition of 100 g of methanol and 1 g of water was used.

[Formation of plate-making layer] Further, a photosensitive layer coating solution 1 having the following composition was prepared, and the photosensitive layer coating solution 1 was applied to the surface of the aluminum support for a lithographic printing plate on the side coated with the undercoating solution. A bar coater was used so that the coating amount after drying (plate coating layer coating amount) would be 1.0 g / m @ 2, and the plate was dried to form a plate-making layer to obtain a lithographic printing original plate.

[0319]   <1 composition of photosensitive layer coating liquid>   ・ Capric acid 0.03 g   -Copolymer 1 0.75 g   M, p-cresol novolac (m / p ratio = 6/4, weight average molecular weight 3,5 00, containing 0.5% by mass of unreacted cresol)                               0.25 g   -P-toluenesulfonic acid 0.003 g   ・ Tetrahydrophthalic anhydride 0.03 g   ・ 0.017 g of cyanine dye A represented by the following structural formula

[0320]

[Chemical 10] -Dye 0.015 g in which the counter ion of Victoria Pure Blue BOH is 1-naphthalene sulfonate anion-Fluorosurfactant (Megafuck F-177, Dainippon Ink and Chemicals, Inc.) 0.05 g-γ-butyl A lactone having a composition of 10 g, methyl ethyl ketone 10 g, and 1-methoxy-2-propanol 1 g was used.

<Copolymer 1> In a 500 mL three-necked flask equipped with a stirrer, a condenser and a dropping funnel, 31.0 g (0.36 mol) of methacrylic acid and 39.39 of ethyl chloroformate were added. 1 g (0.36 mol) and 200 mL of acetonitrile were added, and the mixture was stirred while cooling with an ice water bath. 36.4 g of triethylamine was added to this mixture.
(0.36 mol) was added dropwise by a dropping funnel over about 1 hour. After completion of the dropping, remove the ice-water bath and let it stand at room temperature for 3
The mixture was stirred for 0 minutes.

To this reaction mixture, 51.7 g (0.30 mol) of p-aminobenzenesulfonamide was added, and the mixture was stirred for 1 hour while warming to 70 ° C. in an oil bath. After completion of the reaction, this mixture was added to 1 L of water while stirring the water, and the mixture obtained for 30 minutes was stirred. The mixture was filtered to obtain a precipitate, which was slurried with 500 mL of water, and the slurry was filtered, and the obtained solid was dried to give a white solid of N- (p-aminosulfonylphenyl) methacrylamide. Was obtained (yield 46.9 g).

Next, 4.61 g of N- (p-aminosulfonylphenyl) methacrylamide was placed in a 20 mL three-necked flask equipped with a stirrer, a condenser and a dropping funnel.
(0.0192 mol), ethyl methacrylate 2.94
g (0.0258 mol), acrylonitrile 0.80
g (0.015 mol) and 20 g of N, N-dimethylacetamide were added, and the mixture was stirred while heating to 65 ° C. with a hot water bath. To this mixture was added 0.15 g of "V-65" (manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred for 2 hours under a nitrogen stream while maintaining the temperature at 65 ° C. The reaction mixture was further charged with N- (p-aminosulfonylphenyl) methacrylamide 4.61 g, ethyl methacrylate 2.94.
g, acrylonitrile 0.80 g, N, N-dimethylacetamide and "V-65" 0.15 g 2
It dripped with the dropping funnel over time. After the dropping was completed, the obtained mixture was further stirred at 65 ° C. for 2 hours. After the reaction was completed, 40 g of methanol was added to the mixture and cooled, and the resulting mixture was added to 2 L of water while stirring the water, and 3
After stirring the mixture for 0 minutes, the precipitate was taken out by filtration and dried to obtain 15 g of a specific copolymer 1 as a white solid.

The weight average molecular weight of the specific copolymer 1 thus obtained was measured by gel permeation chromatography and found to be 53,000 (polystyrene standard).

The lithographic printing original plate obtained as described above had an output of 500 mW, a wavelength of 830 nm and a beam diameter of 17 μm.
Using a (1 / e2) semiconductor laser, the main operating speed is 5 m
After exposure for 1 second / second, development was carried out for 30 seconds using a PS plate developer DP-4 (1: 8) water dilution solution manufactured by Fuji Photo Film Co., Ltd.

Using this printing plate, planographic offset printing was performed.

(Plate-making layer forming example 8) Samples 1-1 to 1-14 and samples 2-1 to 2-which have been subjected to the above respective post-treatments.
The undercoating liquid having the following composition was applied to 14 and dried at 80 ° C. for 15 seconds to form a coating film. The coating amount of the coating film after drying was 15 mg / m 2.

<Undercoating liquid composition> -Polymer compound having the following structure: 0.3 g

[0329]

[Chemical 11] -The thing which has a composition of 100 g of methanol and 1 g of water was used.

[Formation of plate-making layer] A photosensitive layer coating solution 1 having the following composition was prepared, and the photosensitive layer coating solution 1 was applied to a bar on a lithographic printing plate aluminum support on which an undercoat layer was formed by coating the above-mentioned undercoating solution. Using a coater, the applied amount after drying is 1.0
Apply to g / m2 and dry to form a plate-making layer.
A lithographic printing original plate was obtained.

[0331]   <1 composition of photosensitive layer coating liquid>   ・ Capric acid 0.03 g   -Copolymer II 0.75 g   M, p-cresol novolac (m / p ratio = 6/4, weight average molecular weight 3,5 00, containing 0.5% by mass of unreacted cresol)                              0.25 g   -P-toluenesulfonic acid 0.003 g ・ Tetrahydrophthalic anhydride 0.03 g ・ 0.017 g of cyanine dye A represented by the following structural formula

[0332]

[Chemical 12] -Victoria Pure Blue BOH counter ion to 1-naphthalene sulfonate anion 0.015 g-Fluorine-based surfactant (MegaFac F-177, Dainippon Ink and Chemicals, Inc.) 0.05 g-γ-butyl lactone 10 g Methyl ethyl ketone 10 g 1-Methoxy-2-propanol 1 g <Copolymer II> In a 500 mL three-necked flask equipped with a stirrer, a condenser and a dropping funnel, methacrylic acid 3 was added.
1.0 g (0.36 mol), ethyl chloroformate 39.
lg (0.36 mol) and acetonitrile 200 m
L was added and the mixture was stirred while cooling with an ice-water bath. 36.4 g (0.36 mo) of triethylamine was added to this mixture.
1) was dripped with the dropping funnel over about 1 hour. After completion of dropping, the ice water bath was removed, and the mixture was stirred at room temperature for 30 minutes.

To this reaction mixture, 51.7 g (0.30 mol) of p-aminobenzenesulfonamide was added, and the mixture was stirred for 1 hour while warming to 70 ° C. in an oil bath. After completion of the reaction, this mixture was added to 1 L of water while stirring the water, and the mixture obtained for 30 minutes was stirred. The mixture was filtered to obtain a precipitate, which was slurried with 500 mL of water, and the slurry was filtered, and the obtained solid was dried to give a white solid of N- (p-aminosulfonylphenyl) methacrylamide. Was obtained (yield 46.9 g).

Next, 4.61 g of N- (p-aminosulfonylphenyl) methacrylamide was placed in a 20 mL three-necked flask equipped with a stirrer, a condenser and a dropping funnel.
(0.0192 mol), ethyl methacrylate 2.94
g (0.0258 mol), acrylonitrile 0.80
g (0.015 mol) and 20 g of N, N-dimethylacetamide were added, and the mixture was stirred while heating to 65 ° C. with a hot water bath. To this mixture was added 0.15 g of "V-65" (manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred for 2 hours under a nitrogen stream while maintaining the temperature at 65 ° C. The reaction mixture was further charged with N- (p-aminosulfonylphenyl) methacrylamide 4.61 g, ethyl methacrylate 2.94.
g, acrylonitrile 0.80 g, N, N-dimethylacetamide and "V-65" 0.15 g 2
It dripped with the dropping funnel over time. After the dropping was completed, the obtained mixture was further stirred at 65 ° C. for 2 hours. After the reaction was completed, 40 g of methanol was added to the mixture and cooled, and the resulting mixture was added to 2 L of water while stirring the water, and 3
After stirring the mixture for 0 minutes, the precipitate was taken out by filtration and dried to obtain 15 g of a specific copolymer 1 as a white solid.

The weight average molecular weight of the specific copolymer 1 thus obtained was measured by gel permeation chromatography and found to be 53,000 (polystyrene standard).

The lithographic printing plate precursor obtained as described above had an output of 500 mW, a wavelength of 830 nm and a beam diameter of 17 μm.
Using a (1 / e2) semiconductor laser, the main operating speed is 5 m
After exposure for 1 / sec, development was performed using a non-silicate developer having the following composition.

[Developer (non-silicate developer)] 1 L of a 45% aqueous solution of a potassium salt of D-sorbit / potassium oxide (K2O), which is a combination of a non-reducing sugar and a base, and an amphoteric surfactant Pionein C-158G. 20 g (manufactured by Takemoto Yushi Co., Ltd.) and 2.0 g of antifoaming agent Olfine AK-02 (manufactured by Nisshin Chemical Co., Ltd.) were added to prepare a concentrated solution. This concentrated solution was diluted 9 times with water to obtain a developing solution. The electric conductivity of this developing solution 1 is 45 mS / cm.

Lithographic offset printing was performed using this printing plate.

(Plate-making layer forming example 9) [Synthesis of component (A) component copolymer] (1) Synthesis example 1 (copolymer 1) Methacrylic acid 31 was added to a 500 ml three-necked flask equipped with a stirrer, a cooling tube and a dropping funnel. 0.0 g (0.36 mol), ethyl chloroformate 39.1 g (0.36 mol) and 200 ml of acetonitrile were added, and the mixture was stirred while cooling with an ice-water bath. To this mixture, 36.4 g (0.36 mol) of triethylamine was added dropwise with a dropping funnel over about 1 hour. After the dropping was completed, the ice-water bath was removed, and the mixture was stirred at room temperature for 30 minutes.

To this reaction mixture was added 51.7 g (0.30 mol) of p-aminobenzenesulfonamide, and the mixture was stirred for 1 hour while warming to 70 ° C. in an oil bath. After completion of the reaction, this mixture was put into 1 liter of water while stirring the water, and the resulting mixture was stirred for 30 minutes. The mixture was filtered to remove the precipitate, which was washed with water (500 m).
After slurrying with l, the slurry was filtered, and the obtained solid was dried to obtain a white solid of N- (p-aminosulfonylphenyl) methacrylamide (yield 46.9 g).

Next, in a 100 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel, 5.04 g (0.0%) of N- (p-aminosulfonylphenyl) methacrylamide was obtained.
210 mol), 2.05 g of ethyl methacrylate (0.0
180 mol), acrylonitrile 1.11 g (0.02
1 mol) and 20 g of N, N-dimethylacetamide were added, and the mixture was stirred while heating to 65 ° C. in a hot water bath. Add "V-65" to this mixture (manufactured by Wako Pure Chemical Industries, Ltd.)
0.15 g was added and the mixture was stirred under a nitrogen stream for 2 hours while maintaining the temperature at 65 ° C. Further N- (p-
Aminosulfonylphenyl) methacrylamide 5.04
g, 2.05 g of ethyl methacrylate, 1.11 g of acrylonitrile, 20 g of N, N-dimethylacetamide and 0.15 g of "V-65" were added dropwise by a dropping funnel over 2 hours. After the dropping was completed, the obtained mixture was further stirred at 65 ° C. for 2 hours. After the reaction, methanol 40
g was added to the mixture, cooled, and the resulting mixture was added to 2 liters of water while stirring this water, the mixture was stirred for 30 minutes, the precipitate was taken out by filtration, and dried to obtain 15 g of a white solid. Got The weight average molecular weight (polystyrene standard) of this copolymer 1 was measured by gel permeation chromatography to be 53.0
It was 0.

(2) Synthesis Example 2 (Copolymer 2) In the polymerization reaction of Synthesis Example 1, 5.04 g (0.02 g) of N- (p-aminosulfonylphenyl) methacrylamide was prepared.
Polymerization reaction was performed in the same manner as in Synthesis Example 1 except that 10 mol) was changed to 3.72 g (0.0210 mol) of N- (p-hydroxyphenyl) methacrylamide, and the weight average molecular weight (polystyrene standard) was 47,000. Copolymer 2 of was obtained.

[Application of Undercoat Liquid] Samples 1-1 to 1-14 and Samples 2-1 to 2-which have been subjected to each of the above-mentioned post-treatments.
The following undercoat liquid was applied to 14 and the coating film was dried at 90 ° C. for 1 minute. The coating amount of the coating film after drying was 10 mg / m 2.

<Undercoating liquid> β-alanine 0.5 g Methanol 95 g Water 5 g [Formation of image forming layer] Photosensitive layer forming liquid A1 was applied to the above-mentioned lithographic printing plate aluminum support and dried at 100 ° C. for 2 minutes. To form a layer (A). The coating amount after drying is 1.
It was 4 g / m @ 2. Further, the photosensitive layer forming liquid B1 was applied and dried at 100 ° C. for 2 minutes to form a layer (B) to obtain a lithographic printing original plate. Photosensitive layer forming liquids A1 and B after drying
The total coating amount of No. 1 was 2.0 g / m ² .

[0345]   <Photosensitive layer forming liquid A1> Copolymer 1 0.75 g Cyanine dye A 0.04g p-toluenesulfonic acid 0.002 g Tetrahydrophthalic anhydride 0.05g Victoria Pure Blue (The counter anion of BOH is 1-naphthalene Dye substituted with sulfonate anion) 0.015 g Fluorine-based surfactant (MegaFac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) ) 0.02g γ-Butyl lactone 8g Methyl ethyl ketone 7g 1-methoxy-2-propanol 7 g.

[0346]   <Photosensitive layer forming liquid B1> m, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight 4000)                                 0.25g Cyanine dye A 0.05g N-dodecyl stearate 0.02g Fluorine-based surfactant (MegaFac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) ) 0.05 g Methyl ethyl ketone 7g 1-methoxy-2-propanol 7 g.

[Evaluation of Performance of Lithographic Printing Plate] The printing performance of the lithographic printing plate prepared as described above was evaluated.

Output of the obtained lithographic printing original plate was 500 m.
After exposure with a semiconductor laser having a wavelength of 830 nm and a beam diameter of 17 μm (1 / e2) at a main scanning speed of 5 m / sec, a developing solution manufactured by Fuji Photo Film Co., Ltd., DP-4, and a rinse solution FR-3 are used. An automatic processor equipped with (1: 7) (manufactured by Fuji Photo Film Co., Ltd .: “PS Processor 900V
R "). At that time, DP-4 used was diluted 1: 8.

This lithographic printing plate was printed on high-quality paper with a Heidel KOR-D machine manufactured by Heidelberg.

(Formation Layer Forming Example 10) [Formation of Undercoat Layer] Sample 1 which has been subjected to each of the above-mentioned post-treatments
The following undercoat liquid was applied to 1-1 to 14 and Samples 2-1 to 2-14 and dried to form an undercoat layer.

[0351]   <Undercoat liquid>   ・ The following compound 0.3g

[0352]

[Chemical 13] -Methanol 100g-Water 1g.

[Formation of Heat-Sensitive Layer] The following coating solution for lower layer was applied to the obtained substrate so that the coating amount was 0.85 g / m 2, and then PERFECT OV manufactured by TABAI was used.
Wind Control is set to 7 in EN PH200 and dried at 140 ° C. for 50 seconds, and then a heat-sensitive layer coating solution is applied at a coating amount of 0.15 g / m 2 and then dried at 120 ° C. for 1 minute. , The lithographic printing original plate was obtained.

[0354]   [Coating liquid for lower layer]   -N- (4-aminosulfonylphenyl) methacrylamide / acrylonitri / Methyl methacrylate 36/34/30: weight average molecular weight 50,000)     1.896 g-cresol novolac (m / p = 6/4 weight average molecular weight 4 500, residual monomer 0.8 wt%) 0.237 g   ・ Cyanine dye A (the following structure) 0.109 g   * 4,4'- bishydroxy phenyl sulfone 0.063g   ・ Tetrahydrophthalic anhydride 0.190 g   -P-toluenesulfonic acid 0.008 g   -Change the counterion of ethyl violet to 6-hydroxynaphthalene sulfone Eat stuff 0.05g   ・ Fluorosurfactant (MegaFac F176, manufactured by Dainippon Ink and Co., Ltd.) ) 0.035g   ・ Methyl ethyl ketone 26.6g   ・ 1-Methoxy-2-propanol 13.6 g   * Γ-butyrolactone 13.8 g   [Coating liquid for heat sensitive layer]   -M, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight 450 0, containing 0.8% by weight of unreacted cresol) 0.237 g   ・ Cyanine dye A (the above structure) 0.047 g   ・ Dodecyl stearate 0.060g   ・ 3-Methoxy-4-diazodiphenylamine hexafluorophosphate                                               0.030g   ・ Fluorosurfactant (MegaFac F176, Dainippon Ink and Chemicals, Inc.) Made) 0.110g   ・ Fluorosurfactant [Megafac MCF-312 (30%), Dainippon In Ki Industrial Co., Ltd.] 0.120 g   ・ Methyl ethyl ketone 15.1 g   -1-Methoxy-2-propanol 7.7 g.

The lithographic printing original plate 1 thus obtained was made by Creo Co.
A test pattern was image-wise drawn with a bend setter at a beam intensity of 9 w and a drum rotation speed of 150 rpm.

For the lithographic printing original plate on which writing has been performed,
Upon development, a non-silicate developer having the following composition was used for development.

[Developer (Non-Silicate Developer)] One liter of a 45% aqueous solution of a potassium salt of D-sorbit / potassium oxide in which a non-reducing sugar and a base are combined is added to an amphoteric surfactant Pionein C-158G (Takemoto Yushi-Seiya). (stock)
20 g of antifoaming agent Olfine AK-02 (manufactured by Nisshin Chemical Co., Ltd.) was added to prepare a concentrated solution. This concentrated solution was diluted 9 times with water to obtain a developing solution. The electric conductivity of this developing solution 1 is 45 mS / cm.

Offset printing was performed using this printing plate.

[0359]

As described above, according to the present invention,
A method for producing an aluminum support for a lithographic printing plate, which provides an aluminum support for a lithographic printing plate having a high level of both printing durability and stain performance, an aluminum support for a lithographic printing plate produced by the production method, and Provided is a lithographic printing original plate in which a plate making layer is laminated on a roughened surface of an aluminum support for a lithographic printing plate.

[Brief description of drawings]

FIG. 1 is an electrolytic roughening treatment (d) in an example.
It is a waveform diagram which shows the waveform of the trapezoidal wave current applied by (g).

FIG. 2 is an electrolytic graining treatment (d) in an example.
It is sectional drawing which shows the outline of a structure of the electrolysis cell used by (g).

[Explanation of symbols]

40 electrolyzer 42 Electrolyzer body 44 feed roller 46A Main pole 46B Main pole 48A liquid supply nozzle 48B liquid supply nozzle 54 Auxiliary electrolyzer 56 Auxiliary anode Th thyristor

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C25D 11/08 C25D 11/08 11/16 301 11/16 301 C25F 3/04 C25F 3/04 B D 7 / 00 7/00 V G03F 7/00 503 G03F 7/00 503 7/09 501 501 7/09 501 F Term (reference) 2H025 AA12 AB03 AC08 DA20 DA36 2H096 AA06 CA03 EA04 EA23 2H114 AA04 DA04 EA02 EA08 GA03 GA09 GA06 GA06 4K057 WA05 WB05 WC10 WD05 WE22 WG10 WK01 WL05 WL10 WN10

Claims (4)

[Claims] 1. A mechanically roughened surface, which is mechanically roughened by a brush, using (1) an abrasive slurry in which an abrasive having an average particle size of 1 to 60 μm is suspended on at least one surface of an aluminum plate. Surface treatment (a), (2) Using alkaline solution mainly composed of sodium hydroxide, etching amount is 2 to 15
Alkaline etching treatment to achieve g / m ² (b), (3) Desmutting treatment in acidic solution (c), (4) Nitric acid solution with nitric acid concentration of 0.2 to 2% by weight And the current density is 5 to 50 A / d using alternating current.
m ² , the amount of electricity during the anode reaction is 30 to 300 C / dm ²
Electrolytic surface roughening treatment so that
(d), (5) Alkaline etching treatment in which an alkaline solution mainly composed of sodium hydroxide is used so that the etching amount becomes 0.1 to 6 g / m ² (e), (6) in an acidic solution Desmut processing Desmut processing (f), (7)
Electrolytic surface roughening treatment in a hydrochloric acid solution with a hydrochloric acid concentration of 0.1 to 2 wt% so that the current density is 5 to 50 A / dm ² and the amount of electricity at the anode is 3 to 150 C / dm ^2. Electrolytic surface roughening treatment (g), (8) Using an alkaline solution mainly composed of sodium hydroxide, the etching amount is 0.0
Alkaline etching treatment (h) for etching to ¹ to 1 g / m ² , (9) Desmutting treatment (I) for desmutting in acidic solution, and (10) Sulfuric acid solution with sulfuric acid concentration of 5% by weight or more A method for producing an aluminum support for a lithographic printing plate, which comprises sequentially performing anodizing treatment (j) for forming an anodized film having a thickness of 0.2 μm or more, wherein the mechanical roughening treatment (a) comprises , Controlling the concentration of the abrasive in the abrasive slurry based on the specific gravity of the abrasive slurry used, in the alkali etching treatment (b), (e), (h), the specific gravity of the alkaline solution used And controlling the concentration of sodium hydroxide in the alkaline solution based on the conductivity, in the electrolytic surface roughening treatment (d), (g), in the nitric acid solution or hydrochloric acid solution used sonic velocity and conductivity. The nitric acid concentration in the nitric acid solution and the hydrochloric acid based on A planographic printing plate characterized by controlling the concentration of hydrochloric acid in the liquid, and in the anodizing treatment (j), controlling the concentration of sulfuric acid in the sulfuric acid solution based on the specific gravity and conductivity of the sulfuric acid solution used. For manufacturing aluminum support for automobile. 2. Mechanical surface roughening treatment (a), alkali etching treatment (b), (e), (h), electrolytic surface roughening treatment (d), (g),
The specific gravity of the abrasive slurry, the specific gravity and conductivity of an alkaline solution, the speed of sound and conductivity in a nitric acid solution or a hydrochloric acid solution, and the specific gravity and conductivity of a sulfuric acid solution are varied in both The method for producing an aluminum support for a lithographic printing plate according to claim 1, wherein the width is controlled to be within ± 10%. 3. An aluminum support for a lithographic printing plate, which is produced by the method for producing an aluminum support for a lithographic printing plate according to claim 1. 4. A lithographic printing original plate comprising a plate-making layer formed on the roughened surface of the lithographic printing plate aluminum support according to claim 3.