JP2003103953A - Manufacturing method for aluminum support for lithographic printing plate, aluminum support for lithographic printing plate, and lithographic printing original plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method for an aluminum support of a lithographic printing plate, the wearability and scumming performances of which can coexist with each other at high levels, the aluminum support thereof and a lithographic printing original plate. SOLUTION: The manufacturing method of the aluminum support of the lithographic printing plate comprises a surface roughening process consisting of an alkali etching treatment (1), a desmut treatment (1) and an electrolytically surface-roughening treatment in a nitric acid aqueous solution (1) in a first process, an alkali etching treatment (2), a desmut treatment (2) and an electrolytically surface-roughening treatment in a hydrochloric acid aqueous solution in a second process, an alkali etching treatment (3), a desmut treatment (3) in a third process and an anodic oxidation treatment, which are applied in the order named on at least one side of the aluminum plate, the aluminum support of the lithographic printing plate and the lithographic printing original plate are provided.

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 having an image forming layer formed on the 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 surface-roughening treatment, an electrolytic surface-roughening treatment in a hydrochloric acid or nitric acid aqueous solution has been mainly performed.

[0004]

The lithographic printing plate precursor for direct plate making having an image forming layer formed of a photosensitive image forming material for infrared laser, or a lithographic printing plate precursor using a conventional positive or negative film is used. It has been desired that the aluminum support for printing has a high level of both the number of printed sheets (printing durability) and stain resistance. However, the conventional aluminum support for a lithographic printing plate is not sufficient in this respect. There wasn't.

The present invention is directed to a method for producing an aluminum support for a lithographic printing plate capable of producing an aluminum support for a lithographic printing plate having both high printing durability and stain resistance at a high level, and the lithographic printing produced by the above production method. Aluminum support for plates,
Another object of the present invention is to provide a lithographic printing plate precursor in which an image forming layer is laminated on the roughened surface that has been roughened on the aluminum support for lithographic printing plates.

[0006]

According to a first aspect of the present invention, at least one surface of an aluminum plate is subjected to (1) alkaline etching treatment for etching with an alkaline solution (1), (2) desmut in an acidic solution. Desmutting treatment (1), (3) Electrolytic surface roughening treatment in an aqueous nitric acid solution (1), (4) Alkaline etching treatment with an alkaline solution (2), (5) Acidic Desmutting treatment (2) of desmutting in solution,
(6) Electrolytic surface roughening treatment in an aqueous hydrochloric acid solution (2), (7) Alkaline etching treatment by etching with an alkaline solution (3), (8) Desmut treatment by desmutting in an acidic solution (3) and (9) The present invention relates to a method for producing an aluminum support for a lithographic printing plate, which comprises sequentially performing anodizing treatment for forming an anodized film in an acidic electrolytic solution.

In the above manufacturing method, the surface of the aluminum plate is degreased by etching with an alkaline solution in the alkaline etching treatment (1).
Next, in the electrolytic surface-roughening treatment (1), the surface-roughening treatment is performed in a nitric acid aqueous solution to form honeycomb pits having irregularities with a size of about 0.5 to 2 μm so as to be superimposed on the large waves. By electrolytic surface-roughening treatment in a hydrochloric acid aqueous solution in the surface-roughening treatment (2), facet-like pits having a size of 0.05 to 0.3 μm on a side are mainly formed. it is conceivable that.

Therefore, according to the above manufacturing method, the roughened surface having the structure in which the honeycomb pits and the minute waves are superposed is formed.

In the above-mentioned manufacturing method, since the composition width of the aluminum plate that can be used as a material is wide, even if the composition is not strictly controlled such as a rolled aluminum plate or a recycled aluminum plate or the aluminum plate has many impurities, A lithographic printing plate precursor that does not have a poor appearance and is excellent in printing durability and stain resistance, in other words, does not cause stains on the printing paper surface can be obtained.

The second aspect of the present invention relates to a method for producing an aluminum support for a lithographic printing plate, which comprises at least one of a pore-sealing treatment and a hydrophilizing treatment after the anodizing treatment.

The aluminum support for a lithographic printing plate obtained by the above-mentioned production method has excellent adhesion between the anodized film and the image forming layer, and the image forming layer remains in the non-image area after development. Since it is difficult, printed matter with excellent image quality can be obtained.

According to a third aspect of the present invention, in the electrolytic surface-roughening treatment (1), in an aqueous nitric acid solution containing nitric acid, aluminum ions and ammonium ions, the amount of electricity during the anode reaction of the aluminum plate is 100 ~
The present invention relates to a method for producing an aluminum support for a lithographic printing plate, in which an alternating current is applied to the aluminum plate so as to electrolyze so as to achieve 500 C / dm ² .

According to the above manufacturing method, an aluminum support for a lithographic printing plate having honeycomb pits of uniform size formed on a roughened surface can be obtained.

According to a fourth aspect of the present invention, in the electrolytic surface-roughening treatment (1), in an aqueous nitric acid solution containing nitric acid, aluminum ions and ammonium ions, the amount of electricity during the anode reaction of the aluminum plate is 200 ~
The present invention relates to a method for producing an aluminum support for a lithographic printing plate, in which an alternating current is applied to the aluminum plate so as to electrolyze so as to achieve 500 C / dm ² .

According to the above-mentioned manufacturing method, an aluminum support for a lithographic printing plate in which honeycomb pits of even size are formed on the roughened surface can be obtained.

[0016] The invention according to claim 5, wherein the AC to be applied to the aluminum plate in the electrolytic graining treatment (1), duty is 0 is a percentage of the period T of the anode reaction time t _a of the aluminum plate 0.5 and the rise time t _p from 0 to the peak of the current is 0.5 to 2 mse.
a c, a frequency is 40～70Hz, the ratio Q _c of the electric quantity Q _a of time electricity Q _c and the anode reaction at the time of cathodic reaction
/ Q _a is a process for producing a lithographic printing plate aluminum support is 0.9 to 1.

According to the method for producing an aluminum support for a lithographic printing plate, in the electrolytic surface-roughening treatment (1), it is difficult to be influenced by the trace components in the aqueous nitric acid solution, so that the electrolytic surface-roughening proceeds. Even if the amount of trace components in the aqueous nitric acid solution increases, uniform honeycomb pits can be formed on the surface of the aluminum plate.

In the power supply for generating the alternating current, it is not necessary to generate a high power supply voltage when the power supply voltage rises, so that an inexpensive power supply circuit can be used.

According to a sixth aspect of the present invention, the nitric acid aqueous solution used in the electrolytic surface roughening treatment (1) has a nitric acid concentration of 5 to 15 g / liter and an aluminum ion concentration of 3 to 7 g / liter. And the ammonium ion concentration is 50 to 150 ppm and the liquid temperature is 30 to 80
And a method for producing an aluminum support for a lithographic printing plate which is at 0 ° C.

According to the above-mentioned manufacturing method, particularly uniform honeycomb bits are formed in the electrolytic surface-roughening treatment (1), and therefore, for a planographic printing plate which becomes a support of a planographic printing original plate having particularly excellent tone reproducibility. An aluminum support is obtained.

According to a seventh aspect of the present invention, in the electrolytic surface-roughening treatment (2), an aqueous hydrochloric acid solution containing hydrochloric acid and aluminum ions is used, and the amount of electricity during the anode reaction of the aluminum plate is 25 to 75C. The present invention relates to a method for producing an aluminum support for a lithographic printing plate, which is electrolyzed by alternating current so as to have a density of / dm ² .

According to the above manufacturing method, uniform fine waves are formed on the honeycomb pits formed in the electrolytic surface roughening treatment (2). Therefore, the aluminum for lithographic printing plates obtained by the above manufacturing method is formed. The roughened surface of the plate has excellent wear resistance. Therefore, the lithographic printing plate precursor having the image forming layer formed on the aluminum support for lithographic printing plate,
Particularly excellent in printing durability.

According to an eighth aspect of the present invention, in the alternating current applied to the aluminum plate in the electrolytic surface roughening treatment (2), the duty is 0.5 and the rising time t _p is 0.5 to. 2 msec and frequency is 40 to 150 Hz
And relates to a method for producing an aluminum support for a lithographic printing plate, wherein Q _c / Q _a is 0.9 to 1.

According to the method for producing an aluminum support for a lithographic printing plate, in the electrolytic surface-roughening treatment (2), it is difficult to be influenced by the trace components in the aqueous hydrochloric acid solution, so that the electrolytic surface-roughening proceeds. Even if the amount of the trace components in the hydrochloric acid aqueous solution increases, uniform fine waves can be formed on the surface of the aluminum plate. Therefore, by forming the image forming layer on the roughened surface of the aluminum support for a lithographic printing plate obtained by the above-mentioned production method, a lithographic printing original plate having particularly excellent printing durability can be produced.

Further, in the power supply for generating the alternating current, it is not necessary to generate a high power supply voltage when the power supply voltage rises, so that the power supply can be constructed at low cost.

According to a ninth aspect of the present invention, in the hydrochloric acid aqueous solution, the hydrochloric acid concentration is 2 to 15 g / liter, and the aluminum ion concentration is 3 to 7 g / liter. It relates to a method for producing an aluminum support for a lithographic printing plate.

According to the above-mentioned manufacturing method, particularly uniform microwaves can be formed in the electrolytic surface roughening step (2).
The lithographic printing plate precursor having the image forming layer formed on the roughened surface of the aluminum support for a lithographic printing plate obtained by the above-mentioned production method is more excellent in printing durability than the lithographic printing plate described in claim 7. There is.

According to a tenth aspect of the present invention, in at least one of the electrolytic surface roughening treatments (1) and (2),
The present invention relates to a method for producing an aluminum support for a lithographic printing plate, wherein the nitric acid aqueous solution is circulated along the longitudinal direction of the aluminum plate so that the average relative flow rate of the nitric acid aqueous solution with respect to the aluminum plate is 1 to 1000 m / min.

According to the above manufacturing method, the surface of the aluminum plate can be uniformly electrolytically roughened.

According to the eleventh aspect of the present invention, in the alkali etching treatment (1), a method for producing an aluminum support for a lithographic printing plate is performed so that the dissolution amount of the aluminum plate is ² to 15 g / m ^2. Regarding

According to the above-mentioned manufacturing method, in the alkaline etching treatment (1) prior to the electrolytic surface roughening treatment (1), the aluminum plate is subjected to etching treatment such that the amount of dissolution is within the above range. Not only can the oil film on the surface of the plate during rolling and the aluminum hydroxide film on the surface be effectively removed, but also a uniform large wave is formed on the surface of the aluminum plate.

The invention according to claim 12 relates to a method for producing an aluminum support for a lithographic printing plate, wherein in the alkali etching treatment (1), the aluminum plate is subjected to an etching treatment using an alkali solution containing sodium hydroxide. .

In the above production method, since the surface of the aluminum plate can be effectively degreased in the alkali etching treatment (1), the aluminum support for a lithographic printing plate obtained by the above production method is particularly printing durable. And excellent in stain resistance.

According to a thirteenth aspect of the present invention, the alkaline solution contains sodium hydroxide and aluminum ions in an amount of 3 to 30% by weight and 0.3 to 9% by weight, respectively, and the liquid temperature is 35 to 80 ° C. It relates to a method for producing an aluminum support for a lithographic printing plate.

In the above manufacturing method, since the etching process can be performed in a short time, the length of the etching processing apparatus can be shortened.

The invention according to claim 14 relates to a method for producing an aluminum support for a lithographic printing plate, wherein in the desmut treatment (1), an aqueous solution of sulfuric acid or an aqueous solution of nitric acid is used as the acidic solution.

In the above manufacturing method, since the sulfuric acid aqueous solution or the nitric acid aqueous solution is used in the desmutting treatment which is carried out subsequent to the alkali etching treatment (1), the surface of the aluminum plate is subjected to the alkali etching treatment (1). It is possible to effectively remove smut, which is a black to dark gray precipitate that has occurred.

According to a fifteenth aspect of the present invention, in the desmut treatment (1), an aluminum support for a lithographic printing plate is used, wherein the acidic solution is a waste liquid in the electrolytic surface roughening treatment (1) or the anodizing treatment. A method of manufacturing a body.

According to the manufacturing method, since the waste liquid generated in the electrolytic surface roughening treatment (1) or the anodizing treatment is reused in the desmut treatment, the amount of waste liquid generated can be greatly reduced.

According to the sixteenth aspect of the present invention, in the desmut treatment (1), the aluminum plate is a sulfuric acid aqueous solution containing 80 to 350 g / liter of sulfuric acid at a liquid temperature of 25 to 80 ° C. or 5 to 15 g of nitric acid. Per liter of a nitric acid aqueous solution containing a liquid temperature of 25 to 80 ° C. for 1 to 10 seconds.

According to the manufacturing method, the smut can be removed particularly effectively in the alkali etching treatment (1).

According to a seventeenth aspect of the present invention, there is provided an aluminum support for a lithographic printing plate, which is subjected to the etching treatment in the alkali etching treatment (2) so that a dissolution amount of the aluminum plate is 0.1 to 10 g / m ² . It relates to a manufacturing method.

In the above-mentioned manufacturing method, the electrolytic surface roughening treatment (1) is followed by the alkaline etching treatment (2).
Thus, the aluminum hydroxide coating film formed on the surface of the aluminum plate by the electrolytic surface roughening treatment (1) is effectively removed, but the honeycomb pits remain.

The invention according to claim 18 relates to a method for producing an aluminum support for a lithographic printing plate, wherein in the alkali etching treatment (2), the aluminum plate is subjected to an etching treatment using an alkali solution containing sodium hydroxide. .

Since the alkaline solution contains sodium hydroxide, it is inexpensive and has a high etching rate. Therefore, according to the manufacturing method, the time required for the alkaline etching treatment (2) and the alkaline It is preferable because the total length of the etching apparatus used for the etching process (2) can be shortened.

According to a nineteenth aspect of the present invention, the alkaline solution contains sodium hydroxide and aluminum ions in an amount of 3 to 30% by weight and 0.3 to 9% by weight, respectively, and the liquid temperature is 35 to 80 ° C. It relates to a method for producing an aluminum support for a lithographic printing plate.

Since the alkaline solution has a particularly high etching rate, the time required for the alkaline etching treatment (2) and the total length of the etching apparatus used for the alkaline etching treatment (2) can be particularly shortened, which is preferable.

The twentieth aspect of the present invention relates to a method for producing an aluminum support for a lithographic printing plate, wherein an aqueous solution of sulfuric acid is used as the acidic solution in the desmut treatment (2).

According to the above-mentioned manufacturing method, since the aqueous solution of sulfuric acid or the aqueous solution of nitric acid is used in the desmutting treatment which follows the alkali etching treatment (2), the surface of the aluminum plate is treated in the alkali etching treatment (2). The smut generated in the can be removed efficiently.

In the desmutting treatment (2), the aluminum plate is treated with a sulfuric acid aqueous solution containing sulfuric acid at 80 to 350 g / liter at a liquid temperature of 25 to 80 ° C. for 1 to 10 seconds. The present invention relates to a method for producing an aluminum support for a lithographic printing plate.

The manufacturing method is characterized in that the smut generated on the surface of the aluminum plate in the alkali etching treatment (2) can be effectively removed.

The invention as set forth in claim 22 relates to a method for producing an aluminum support for a lithographic printing plate, wherein in the desmut treatment (2), a waste liquid in the anodizing treatment is used as the acidic solution.

According to the above manufacturing method, since the waste liquid generated in the anodizing treatment is reused in the desmutting treatment, the amount of waste liquid generated from the whole manufacturing apparatus used in the manufacturing method can be greatly reduced. .

The invention according to claim 23 is an aluminum support for a lithographic printing plate, which is subjected to an etching treatment in the alkali etching treatment (3) so that the dissolution amount of the aluminum plate is 0.05 to 1 g / m ² . It relates to a manufacturing method.

In the above manufacturing method, an alkaline etching treatment (3) is carried out subsequent to the electrolytic surface roughening treatment (2).
As a result, the aluminum hydroxide film formed on the surface of the aluminum plate by the electrolytic surface roughening treatment (2) is effectively removed, but the microwave remains.

The invention according to claim 24 relates to a method for producing an aluminum support for a lithographic printing plate, which comprises subjecting the aluminum plate to an etching treatment with an alkaline solution containing sodium hydroxide in the alkaline etching treatment (3). .

Since the alkaline solution contains sodium hydroxide, it is inexpensive and has a high etching rate. Therefore, according to the manufacturing method, the time required for the alkali etching treatment (3) and the alkali It is preferable because the total length of the etching apparatus used for the etching process (3) can be shortened.

According to a twenty-fifth aspect of the invention, the alkaline solution used in the alkaline etching treatment (3) contains sodium hydroxide and aluminum ions in an amount of 3 to 30% by weight and 0.3 to 9% by weight, respectively. Then
It relates to a method for producing an aluminum support for a lithographic printing plate having a liquid temperature of 25 to 80 ° C.

Since the alkaline solution has a particularly high etching rate, the time required for the alkaline etching treatment (3) and the total length of the etching apparatus used for the alkaline etching treatment (3) can be particularly shortened, which is preferable.

The invention as set forth in claim 26 relates to a method for producing an aluminum support for a lithographic printing plate, wherein an aqueous solution of sulfuric acid is used as the acidic solution in the desmut treatment (3).

According to the above-mentioned manufacturing method, since the sulfuric acid aqueous solution or the nitric acid aqueous solution is used in the desmutting treatment (3) which follows the alkali etching treatment (3), the aluminum is used in the alkali etching treatment (3). The smut generated on the surface of the plate can be removed efficiently.

The invention according to claim 27 is the desmut treatment (3), wherein the aluminum plate is treated with a sulfuric acid aqueous solution containing 80 to 350 g / liter of sulfuric acid at a liquid temperature of 25 to 80 ° C. for 1 to 10 seconds. The present invention relates to a method for producing an aluminum support for a lithographic printing plate.

The manufacturing method is characterized in that the smut generated on the surface of the aluminum plate in the alkali etching treatment (3) can be effectively removed.

The invention as set forth in claim 28 relates to a method for producing an aluminum support for a lithographic printing plate, wherein in the desmutting treatment (3), a waste liquid in the anodizing treatment is used as the acidic solution.

In the above-mentioned manufacturing method, the desmut treatment (3) can be immediately performed without rinsing the aluminum plate with water. Therefore, the desmut treatment apparatus for performing the desmut treatment (3) and the anodization treatment can be performed. It is not necessary to provide a water washing device with the anodizing device for performing the treatment.

According to a twenty-ninth aspect of the invention, in the anodizing treatment, the acidic electrolyte contains sulfuric acid and aluminum ions, and the concentration of sulfuric acid is 80 to 200 g /
The present invention relates to a method for producing an aluminum support for a lithographic printing plate, which comprises electrolytically treating with a direct current at a liquid temperature of 25 to 80 ° C. using a sulfuric acid aqueous solution of liter.

In the above manufacturing method, the smut generated in the alkali etching treatment (3) can be removed particularly effectively.

The invention as defined in claim 30 is defined by claim 1 and claim 2.
9. An aluminum support for a lithographic printing plate produced by the method according to any one of 8 above.

In the aluminum support for a lithographic printing plate, honeycomb pits and minute waves are formed so as to be superposed on a large wave uniformly formed on the surface. Therefore, the aluminum support for a lithographic printing plate is used as a support. The lithographic printing plate having a high level of printing durability and stain resistance is suitable as a so-called digital printing plate.

A thirty-first aspect of the present invention relates to a lithographic printing original plate comprising a positive or negative image forming layer provided on the roughened surface of the lithographic printing plate aluminum support of the twenty-ninth aspect.

The lithographic printing original plate has both a high level of printing durability and stain resistance, and is suitable as a digital printing plate.

[0072]

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.

As the trace element, for example, silicon,
Iron, nickel, manganese, copper, magnesium, chromium,
Examples include zinc, bismuth, titanium, and vanadium.

For example, when a large amount of silicon is contained, many defects occur in the anodized film when the anodizing treatment is performed after the roughening treatment. Since the water-retaining property of the defective portion is inferior, the printing paper is liable to get dirty during printing. In addition, when a large amount of copper is contained, the area of the portion where the honeycomb pits are not formed is large, which causes an appearance failure. Therefore, from the viewpoint of forming uniform honeycomb pits in the electrochemical graining treatment in a nitric acid aqueous solution and a hydrochloric acid aqueous solution, the amount of the trace elements is 0.001% by weight to 1.5% by weight. preferable.

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 Specific examples of the aluminum alloy that can be used as the material for the aluminum plate in the present invention include the following.

(1) AL1 Fe as 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 based on JlS A 1
It is classified into 050 materials, and in particular, since it can increase the pit diameter and the depth in the electrochemical roughening treatment, it is 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 C is contained as an optional component.
u is 0.005 wt% or less, Mg is 0.001 to 0.0
3 wt%, Ti 0.001 to 0.04 wt%, Ni 0.002 to 0.005 wt%, V 0.01 to O, 05
It is an aluminum alloy containing 50% by weight and the balance being Al and inevitable impurities.

The aluminum alloy is based on 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 it can be combined with a non-silicate developer. By
It is possible to produce a lithographic printing plate having a balance between stain resistance and printing durability.

(3) AL3 Al is 95-99.4% by weight, and among the following elements,
It is an A1 alloy plate containing five or more kinds 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 % 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 type lithographic printing original plate which 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 mechanical strength is high. Is obtained.

1-2 Explanation of trace elements The trace elements are 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.
This element is contained in an amount of about 3 to 0.1% by weight, 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, the 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 the new metal, 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 refiner 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 Compound When the elements contained in the aluminum raw material and the elements added to the molten aluminum are solidified in the casting process, some of them are solid-solved in the aluminum, and the rest are intermetallic compounds, Or it exists as 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 intermetallic compounds or single crystallized substances
It easily remains as a 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 Manufacturing Method of 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 of the present invention, as described in claim 1 of the present specification, (1) an alkali etching treatment of etching with an alkali solution (1), (2 ) Desmutting treatment in acidic solution (1), (3) Electrolytic graining treatment in electrolytic nitric acid solution (1), (4) Alkaline etching treatment in alkaline solution (2) ), (5) Desmutting treatment in which desmutting is performed in an acidic solution (2),
(6) Electrolytic surface roughening treatment in an aqueous hydrochloric acid solution (2), (7) Alkaline etching treatment by etching with an alkaline solution (3), (8) Desmut treatment by desmutting in an acidic solution (3) and (9) Anodizing treatment for forming an anodized film in an acidic electrolytic solution is sequentially performed to roughen the aluminum plate.

Each of the above processes will be described below.

2-1 Electrolytic surface roughening treatment As described above, in the first electrolytic surface roughening treatment (1), the electrolytic surface roughening treatment is carried out in an aqueous nitric acid solution, and the second electrolytic roughening treatment is performed. In the electrolytic graining treatment (2), which is the electrolytic graining treatment of the second time, the electrolytic graining treatment is performed in an aqueous hydrochloric acid solution.

A. Electrolytic surface roughening treatment (1) In the electrolytic surface roughening treatment (1), as the nitric acid aqueous solution, a nitric acid aqueous solution used for a usual electrochemical surface roughening treatment using direct current or alternating current can be used.

The nitric acid aqueous solution contains 1 to 10 nitric acid.
Aqueous nitric acid solution containing 0 g / liter, aluminum nitrate,
An example is one in which one or more kinds of salts selected from nitrates such as sodium nitrate and ammonium nitrate and hydrochlorides such as aluminum chloride, sodium chloride and ammonium chloride are added in the range of 1 g / liter to a saturated concentration. A compound that forms a complex with copper may be added to the aqueous nitric acid solution at a concentration of 1 to 200 g / liter. Further, in the nitric acid aqueous solution, iron,
Trace elements contained in the aluminum alloy forming the aluminum plate, such as copper, manganese, nickel, titanium, magnesium, and 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 aqueous solution, nitric acid of 2 to 15 is used.
A solution in which an aluminum salt such as aluminum nitrate is added to dilute nitric acid containing g / l to adjust the concentration of aluminum ions to 2 to 7 g / l is particularly preferable.

When electrolytic surface roughening treatment is carried out in an aqueous nitric acid solution, a reduction reaction produces ammonium ions in the aqueous nitric acid solution.
It is particularly preferable to add ammonium nitrate in advance so that the ammonium ion concentration becomes 50 to 150 ppm.

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

B. Electrolytic surface roughening treatment (2) In the electrolytic surface roughening treatment (2), as the hydrochloric acid aqueous solution, a hydrochloric acid aqueous solution used for usual electrochemical surface roughening treatment using direct current or alternating current can be used.

The hydrochloric acid aqueous solution has a hydrochloric acid concentration of 1 to
1 g / liter of one or more salts selected from hydrochloric acid salts such as aluminum chloride, sodium chloride and ammonium chloride, and nitrate salts such as aluminum nitrate, sodium nitrate and ammonium nitrate in 100 g / liter hydrochloric acid aqueous solution
The thing added in the range of liter-saturation concentration can be mentioned. A compound that forms a complex with copper may be added to the aqueous hydrochloric acid solution so as to have a concentration of 1 to 200 g / liter. In the hydrochloric acid aqueous 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 aqueous solution, hydrochloric acid may be used in an amount of 2 to 15
A solution in which an aluminum salt such as aluminum chloride is added to diluted hydrochloric acid containing g / liter, more preferably 2 to 10 g / liter to adjust the concentration of aluminum ions to 3 to 7 g / liter is particularly preferable.

The liquid temperature of the aqueous hydrochloric acid solution is preferably 20 to 50 ° C., particularly preferably 30 to 40 ° C.

C. Conditions for electrolytic surface roughening treatment In either of the electrolytic surface roughening treatments (1) and (2), either alternating current or direct current may be applied, but alternating current is preferably applied. It is preferable that the alternating current is applied so that the amount of electricity that the aluminum plate takes in the anodic reaction during the electrolytic surface roughening treatment is 20 to 500 C / dm ² . And, in the electrolytic surface roughening treatment (1), the range of 100 to 500 C / dm ² is more preferable,
The range of 200 to 500 C / dm ² is particularly preferable. In the electrolytic surface roughening treatment (2), 25 to 75 C / dm ² is more preferable, and 40 to 60 C / dm ² is particularly preferable.

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

The frequency of the alternating current is 0.1 to 500 Hz.
However, in the electrolytic surface roughening treatment (1), 4 is preferable.
The range of 0 to 70 Hz is particularly preferable, and in the electrolytic surface roughening treatment (2), 40 to 150 Hz is particularly preferable.

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, in both of the electrolytic surface roughening treatments (1) and (2), it is difficult to be influenced by the trace components in the nitric acid aqueous solution or the hydrochloric acid aqueous solution. 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.
There proportion duty = 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 especially preferable.

The quantity of electricity applied to the aluminum plate facing the main electrode is the ratio Q _c / Q _{a of the} quantity of electricity Q _c when the aluminum plate undergoes a cathode reaction and the quantity of electricity Q _a when it undergoes an anodic reaction.
Is preferably in the range of 0.9 to 1. The electric quantity ratio Q _c / Q _a can be controlled by adjusting the voltage generated by the power source, and when the electrolytic cell shown in FIG. 2 is used,
It can be controlled by adjusting the firing angle of the thyristor Th.

The current density is the peak value of the trapezoidal wave, and
Hard cycle side I_a, Cathode cycle side I_cBoth 10
~ 200A / dm²The range is preferably 30 to 70 A /
dm ²Range of uniform honeycomb pits and microwaves
Particularly preferred for forming.

In each of the electrolytic surface roughening treatments (1) and (2), a known electrolytic cell such as a vertical type, a flat type or a radial type can be used as the electrolytic cell. 1 electrolyzer
Although only the tanks may be used or two or more tanks may be used in series, it is particularly preferable to use 1 to 3 tanks in series in the electrolytic surface roughening treatment (1). It is particularly preferable that the chemical treatment (2) is performed in one tank. When two layers of electrolytic cells are used in the electrolytic surface roughening treatment (1), the current density and the amount of electricity in the first electrolytic cell are made higher than the current density and the amount of electricity in the second electrolytic cell. Is particularly preferable.

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

In the electrolytic cell, the distance between the aluminum plate conveyed 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 between the aluminum plate transported in the electrolytic cell and the aqueous nitric acid solution or aqueous 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 range, the flow direction of the nitric acid aqueous solution or the hydrochloric acid aqueous solution may be either the same direction as the aluminum plate transport direction 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 aqueous solution and the hydrochloric acid aqueous solution are kept constant for uniform electrolytic graining.

In the flat type and vertical type electrolytic cells, as described in Japanese Patent Publication No. 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 aqueous solution and the hydrochloric acid aqueous solution constant, a liquid pool chamber is provided inside the electrolytic cell, and a 1-5 mm wide liquid is blown out along the width direction of the aluminum plate running inside. The nitric acid aqueous solution and the hydrochloric acid aqueous solution may be supplied using a liquid supply nozzle provided with a slit. 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.

[0130] As a power feeding method for the aluminum plate running inside the electrolytic cell, there are, for example, a direct power feeding method using a conductor roller, a liquid power feeding method not using the conductor roller, 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.

In addition to the main electrode, an auxiliary anode for applying a direct current is provided inside the electrolytic cell, and by controlling the strength of the direct current flowing through the auxiliary electrode, the anode applied to the aluminum plate can be controlled. 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.

As a method for controlling the intensity of the direct current flowing through the auxiliary anode, a controlled rectifier such as a thyristor or a GTO is used as described in JP-B-6-37716 and JP-B-5-42520. Examples include phase control and control with a diode and a variable resistor. 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 cast and subjected to a high temperature homogenizing treatment to obtain a 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. 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 with respect to the traveling direction of the aluminum plate.
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 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. It is preferable to use a method of energizing the end portion of the conductor roller while sliding the power feeding brush on the rotating body.

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

2-2 Alkaline Etching Treatment As described above, in the production method of the present invention, an alkaline etching treatment is performed before the electrolytic surface roughening treatment (1), and further, the electrolytic surface roughening treatment (1) is performed. ) And (2), the alkali etching treatment is also performed.

By performing the alkali etching treatment before the electrolytic graining treatment (1), the aluminum plate is degreased and at the same time a large wave is formed on the surface.

Then, after the electrolytic surface-roughening treatments (1) and (2), an alkali etching treatment is performed, so that the hydroxylation generated on the surface of the aluminum plate by the electrolytic surface-roughening treatments (1) and (2) is performed. The aluminum coating is removed.

In the alkali etching process,
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 1 in the first alkali etching treatment (1).
Is preferably in the range of 5 g / m ^2, in particular in the range of 3 to 10 g / m ² is preferred. In the electrolytic graining treatment (1) to the subsequent alkali etching treatment carried out (2), the etching amount is preferably in the range of 0.1 to 10 g / m ^2, particularly from 0.2~3.5g / m ² Is preferred. Then, in the alkaline etching treatment (3) that follows the electrolytic surface roughening treatment (2), the etching amount is 0.05 to
The range of 1 g / m ² is preferable, and especially 0.1-0.8 g / m ^2.
A range of m ² is preferred.

Examples of the alkaline solution include solutions of caustic and alkali metal salts.

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

Examples of the alkali metal salt include alkali metal silicates such as sodium metasilicate, sodium silicate, potassium metasilicate and potassium silicate, alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium aluminate and potassium aluminate. Alkali metal aluminates such as and the like, alkali metal aldonates such as sodium gluconate and potassium gluconate, and alkali metal hydrogen phosphates such as sodium diphosphate, potassium diphosphate, sodium triphosphate, and potassium triphosphate. Salt etc. are mentioned. As the alkali solution, a caustic alkali solution and a solution of the caustic alkali and an alkali metal aluminate are particularly preferable from the viewpoint of high etching rate and low cost.

As the alkaline solution, a sodium hydroxide solution containing a predetermined amount of aluminum ions is particularly preferable.

The concentrations of sodium hydroxide and aluminum ions in the sodium hydroxide solution were 3 to 30% by weight and 0.3 to 9% by weight in the alkali etching treatment (1) and the alkali etching treatment (2), respectively. A weight% range is preferred. In the alkali etching treatment (1), a particularly preferable range of the concentrations of the sodium hydroxide and aluminum ions is
20-30 wt% and 5-9 wt% respectively,
In the alkali etching treatment (2), the amounts are 3 to 7% by weight and 0.3 to 7% by weight, respectively. In the alkali etching treatment (3), the concentrations of sodium hydroxide and aluminum ions are preferably in the ranges of 3 to 30% by weight and 0.3 to 0.9% by weight, respectively.

The liquid temperature of the alkaline solution is preferably in the range of 35 to 80 ° C. in any of the alkaline etching treatments (1), (2) and (3).

The alkali etching treatment can be carried out by using an etching apparatus usually used for the etching treatment of an aluminum plate. 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 water by spraying so as not to bring the treatment liquid into the next step.

2-3 Desmut treatment In the alkali etching treatments (1) to (3), since the aluminum plate is treated with an alkaline solution, trace elements are changed to hydroxides and the like, and the surface of the aluminum plate is treated. Precipitation occurs and smut is generated.

Therefore, every time the alkali etching treatments (1) to (3) are completed, the aluminum plate is brought into contact with an acidic solution and desmutted to remove smut on the surface.

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

As an acidic solution, the main acid component is
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.

As the acidic solution, an aqueous solution of sulfuric acid containing sulfuric acid as a main acid component and an aqueous solution of nitric acid containing nitric acid as a main acid component are preferable. Particularly, in the desmut treatment (1), sulfuric acid of 80 to Contains 200 g / liter, aqueous sulfuric acid solution having a liquid temperature of 25 to 85 ° C., and nitric acid 5 to 15 g / liter, and has a liquid temperature of 25 to 5
A 0 ° C. aqueous nitric acid solution is preferred. In the desmutting treatments (2) and (3), a sulfuric acid aqueous solution containing sulfuric acid at 80 to 350 g / liter and having a liquid temperature of 25 to 80 ° C. is preferable.

In the desmutting process (1),
As the acidic solution, a waste liquid discharged by the electrolytic surface-roughening treatment (1) described later or the anodizing treatment described later can be used, and in the desmut treatments (2) and (3), the acidic solution is It is also possible to use the waste liquid discharged by the anodizing treatment.

In the desmutting treatment, if the waste liquid discharged from the electrolytic surface roughening treatment (1) or the anodizing treatment is reused as the acidic solution, not only the amount of the waste liquid can be greatly reduced but also the desmutting treatment (2 ) After that, since it is possible to immediately shift to the anodizing treatment without cleaning the aluminum plate, it is preferable in that the cleaning equipment between the desmutting apparatus and the anodizing apparatus can be omitted.

The liquid temperature of the acidic solution is room temperature to 95 ° C. in both the desmut treatments (1) and (2).
Is preferable, and a range of 25 to 80 ° C. is particularly preferable.

The processing time is preferably 1 to 30 seconds, and particularly 1
-10 seconds is preferable.

After the desmut treatment is completed, it is preferable to drain the treatment liquid by the nip roller and wash it with water by spraying so as not to bring the treatment liquid to 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 Anodizing Treatment As the acidic electrolytic solution used for the anodizing treatment of the aluminum plate, an acidic solution containing sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixture thereof as a main acid component is generally used. However, the acidic solution is not limited as long as it is a solution capable of forming a porous oxide film by anodizing treatment.

The treatment conditions for anodic oxidation vary depending on the composition of the acidic electrolytic solution used, and therefore cannot be generally specified.
Generally, the concentration of the acid component is 1 to 80% by weight, the liquid temperature is 5 to 70 ° C., and the current density is 1 to 60 A /
dm ² , the voltage is 1 to 100 V, and the processing time is suitably in the range of 10 seconds to 300 seconds.

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.

When a sulfuric acid aqueous solution is used as the acidic electrolytic solution, a direct current is usually applied to the aluminum plate to perform anodizing treatment, but an alternating current may be applied to perform the anodizing treatment.

The sulfuric acid aqueous 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 solution having a concentration of 00 g / liter is preferable, and an aqueous sulfuric acid solution having a sulfuric acid concentration of 80 to 200 g / liter is particularly preferable. The liquid temperature is preferably 30 to 60 ° C., particularly 30 to 5
A range of 5 ° C is preferred.

[0166] 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 supplying power to the aluminum plate, there are a direct supply method and a liquid supply method, 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.
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 method and the indirect power feeding method, in order to reduce energy loss due to voltage drop in the aluminum web, the anodizing process is divided into two or more steps, and a 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 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, a 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 the anodic oxide coating is increased 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 and 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

2-5 Sealing Treatment / Hydrophilic Treatment The aluminum plate subjected to anodizing treatment suppresses the dissolution of the anodized film in the developing solution, the suppression of the residual film of the image forming layer in the non-image area, and the strength of the anodized film. For the purpose of improving the hydrophilicity, the adhesion to the photosensitive layer, and the like, a hydrophilizing treatment can be performed after the water washing treatment.

Examples of the hydrophilic treatment include a silicate treatment in which the anodized 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 contacting the aluminum plate with the aqueous solution of the alkali metal silicate include, but are not limited to, immersion and spraying.

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

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

To adjust 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, titanium potassium 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 anodic oxide film, such as synthetic resin sealing, low-temperature sealing (using red blood salt, alkaline earth salt, etc.), etc., can be used as a printing plate support (photosensitive layer). 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 is continuously or discontinuously applied and the relative humidity is 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 an alkaline aqueous solution, hot water or alkaline spraying, dipping in an aqueous nitrite solution, and spraying an 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 depend 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
To adjust H to the above range, for example, an alkaline buffer solution or the like can be used. 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,
A mixed aqueous solution of hydrochloric acid 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 improve the adhesion to the photosensitive layer, the acidic aqueous solution treatment and hydrophilic undercoating disclosed in JP-A-5-278362 are used. Alternatively, an organic layer disclosed in Japanese Patent Application Laid-Open No. 4-282637 or Japanese Patent Application No. 6-108678 may be provided.

After subjecting the roughened surface of the aluminum support for a lithographic printing plate to these treatments, a back coat is provided, if necessary, on the back surface which is the surface opposite to the roughened surface. . As such a back coat, JP-A-5-4
Organic polymer compounds described in Japanese Patent No. 5885 and Japanese Patent Application No.
A coating layer made of a metal oxide obtained by hydrolyzing and polycondensing an organic or inorganic metal compound described in JP-A-189448 is preferably used. Examples of the organic or inorganic metal compound include Si (OCH ₃ ) ₄ and Si (OC ₂ H ₅ )
Silicon alkoxy compounds such as ₄ , Si (OC ₃ H ₇ ) ₄ and Si (OC ₄ H ₉ ) ₄ are particularly preferable because they are inexpensive and easily available and can form a coating layer excellent in developer resistance.

2-6 Rinsing Treatment In order to remove the chemical solution used in the above treatment from the surface of the aluminum plate, a rinsing step of rinsing the aluminum plate may be provided between the treatments.

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 onto the aluminum plate is preferably 0.1 to 10 liters / m ² per washing step.

In the water washing tank, it is preferable to inject the washing water onto 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.

[0205] The time of the water washing treatment is industrially preferably 10 seconds or less, and particularly preferably 0.5 seconds to 5 seconds.

2-7 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 each of the above 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, epichlorohydrin rubber, urethane rubber, polysulfide rubber, fluororubber It is possible to use a roller having a cylinder made of rubbers such as the above, and those obtained by adding a slight amount of additives to the rubbers. It is particularly preferable that the hardness of the body of the rubber roller is 60 to 90.

Further, when controlling the conveying speed of the aluminum web at a place where the aluminum plate is wet and slippery, it is particularly preferable to use a non-woven fabric roller which hardly slips even when the aluminum web is wet. When a rubber roller is used at the location, it is particularly preferable to provide the roller with a motor for auxiliary driving.

2-8 Others Prior to the alkali etching treatment (1), a mechanical roughening treatment for mechanically roughening the surface of the aluminum plate to be roughened can be performed.

In the mechanical roughening treatment, a brush polishing method of rubbing with a brush roller while supplying slurry of an abrasive to the roughened surface of the aluminum plate, and a non-woven fabric in which particles of the abrasive are fixed Roller polishing method of rubbing with a graining roller fixed to the side surface of a cylindrical body, but is not limited thereto.

3. Image forming layer 3-1 Prevents the aluminum support for lithographic printing plates from being dissolved in a developing solution during development of the back coat layer, and scratches due to rubbing between the image forming layer and the aluminum support for lithographic printing plates described later. For the purpose of eliminating the above, as described in JP-A-6-32115, before forming an image forming layer described later, the surface opposite to the roughened surface of the aluminum support for a lithographic printing plate, that is, A back coat layer containing an organic polymer compound and a surfactant and having a thickness of 0.01 to 8 μm can be provided on the back surface.

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 as the main component of this back coat layer. 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, Examples thereof include oxalic acid, suberic acid, sebacic acid, malonic acid, and saturated aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid.

The back coat layer further includes 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 cationic agent. Waxes that are usually used as polymers, etc.
Higher fatty acids, higher fatty acid amides, silicone compounds composed of dimethylsiloxane, modified dimethylsiloxane, polyethylene powder and the like are appropriately added.

Various methods can be applied to coat 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 Image Forming Layer The image forming layer is laminated on the roughened surface of the aluminum support for a lithographic printing plate manufactured by the manufacturing method of the present invention, and is exposed to light or heat, visible light or laser light. It is a layer having a function of forming a printed image by exposing with.

As the image forming layer, a positive type image forming layer for forming a positive type print image by the exposure and development, and a negative type image forming layer for forming a negative type print image by the exposure and development. Is mentioned.

Further, depending on the exposure method, the image forming layer includes a visible light exposure image forming layer which is exposed to visible light and a laser light exposure type image forming layer which is exposed to laser light or directly draws a printed image. Can be divided into

Further, the image forming layer can be divided into a light-sensitive layer and a heat-sensitive layer, depending on whether it is sensed by light or heat.

The visible light exposure image forming layer and the laser light exposure type image forming layer will be described below. (1) Visible light exposure type image forming layer The visible light exposure type image forming layer can be formed from 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 image forming layer can be formed by applying a photosensitive resin solution in which the photosensitive resin and the colorant are mixed 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 a certain degree of 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 image forming layer As the laser exposure type image forming layer, a negative type laser image forming layer in which a portion irradiated with laser light remains after exposure and development, and a positive portion in which a portion irradiated with laser light is removed. Type laser image forming layers, and photopolymerization type laser image forming layers that photopolymerize when irradiated with a laser beam.

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

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).

The acid-crosslinkable compound (B) is 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 novolac resins and polymers having a hydroxyaryl group in the side chain such as poly (hydroxystyrene).

As the infrared absorbent (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.

In the negative type laser image forming layer forming liquid,
Further, a plasticizer and the like can be added.

B. Positive type laser image forming layer The positive type laser image forming layer is a positive type in which (F) an alkali-soluble polymer, (G) an alkali dissolution inhibitor, and (H) an infrared absorber are dissolved or suspended in an appropriate solvent. Type laser image forming layer forming liquid.

As the alkali-soluble polymer (F), for example, phenol resin, cresol resin, novolac resin, pyrogallol resin, and phenol type 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 Image Forming Layer The photopolymerizable laser image forming layer can be formed by a photopolymerizable laser image forming layer forming liquid containing (I) a vinyl polymerizable compound having an ethylenically unsaturated bond at the molecular end. If necessary, the photopolymerization type laser image forming 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.

Examples of the vinyl polymerizable compound (I) include aromatic vinyl compounds such as styrene and α-methylstyrene, and ethylenically unsaturated carboxylates 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 image forming layer forming liquid, the positive type laser image forming layer forming liquid, or the photopolymerization type laser image forming layer forming liquid, and the negative type laser image forming layer forming liquid, positive Type laser image forming layer forming liquid,
The method for applying the photopolymerizable laser image forming layer forming liquid is the same as the solvent and the applying method described in “(1) Visible light exposure type image forming layer”.

When forming the photopolymerizable laser image forming layer, a silicone 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 with a compound because the adhesion between the lithographic printing plate support and the photopolymerizable laser image forming layer is improved.

3-3 Coating Method The photosensitive resin solution, the negative type laser image forming layer forming solution,
As a method of applying the positive type laser image forming layer forming liquid and the photopolymerization type laser image forming layer forming liquid to the roughened surface of the aluminum support for the lithographic printing plate, a method using a coating rod, an extrusion type coater , Using a slide bead coater, etc.
A conventionally known method can be used and the method can be performed according to known conditions.

As an apparatus for drying an aluminum plate after applying the photosensitive resin solution, the negative type laser image forming layer forming solution, the positive type laser image forming layer forming solution, and the photopolymerization type laser image forming layer forming solution, Japanese Patent Application Laid-Open No. 6-63487 discloses an arch-type dryer in which a pass roll is arranged in a drying device and is dried while being conveyed by the pass roll, and an air dryer is provided in which air is supplied from above and below by a nozzle and a web is floated and dried. There are a radiant heat dryer that dries with radiant heat from a medium heated to a high temperature, and a roller drier that heats a roller and dries by conduction heat transfer due to contact with the roller.

[0252]

EXAMPLES The present invention will be described more specifically below with reference to examples.

(Examples 1-1 to 1-36, Comparative Example 1)

[0254]

[Table 1]

[0255]

[Table 2]

[0256]

[Table 3]

[0257]

[Table 4]

[0258]

[Table 5]

[0259]

[Table 6]

[0260]

[Table 7]

[0261]

[Table 8] The aluminum plate shown in Tables 1 to 4 was subjected to surface roughening treatment according to the following procedure. The treatment was performed according to the conditions shown in Tables 1 to 8 as described below. 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.

(1) Alkaline etching treatment (1) An aluminum plate was sprayed with an alkali solution containing 26% by weight of NaOH and 7.5% by weight of aluminum ions at a liquid temperature of 70 ° C. from a spray tube to give a rough surface. The alkali etching treatment was performed so that the amount of aluminum dissolved in the activated surface became the value shown in Tables 1 to 4.

(2) Desmutting treatment (1) Next, desmutting treatment was performed according to the conditions shown in Tables 1 to 4. Table 1 shows the types and temperature of the acidic solutions used.
4 and Table 5.

(3) Electrolytic surface roughening treatment (1) Liquid temperature 5 in which 16 g of 68% nitric acid, 63 g of aluminum nitrate and 0.4 g of ammonium nitrate were added to 1 liter of water.
In a nitric acid aqueous solution at 0 ° C., a trapezoidal wave current was applied to carry out electrolytic surface roughening treatment. The amount of electricity during the anode reaction of the aluminum plate, the frequency of the trapezoidal wave current, and the rising time T _p were as shown in Tables 1 to 4. AC duty (t _a
/ T) was 0.5.

The current density is 50 A / dm ² at the peak value of the current when the aluminum plate undergoes the anode reaction,
Aluminum plate at a portion opposite to the main electrodes of the carbon ratio Q _c / Q _a of the electric amount sum Q _c when total amount of electricity Q _a and the cathode reaction at the time of anodic reaction 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.

(4) Alkaline etching treatment (2) NaOH 26% by weight and aluminum ion 7.5% by weight
An alkaline solution containing and was sprayed onto the aluminum plate after the electrolytic surface roughening treatment from a spray tube to perform an alkaline etching treatment. The amount of dissolution of the aluminum plate on the roughened surface was as shown in Tables 1 to 4.

(5) Desmutting process (2) Next, a desmutting process was performed. The acidic aqueous solutions used for the desmutting treatment are shown in Tables 1 to 4 and 5.

(6) Electrolytic surface roughening treatment (2) Electrolytic roughening was performed by applying a trapezoidal wave current in a hydrochloric acid aqueous solution at a liquid temperature of 35 ° C in which 21 g of 35% hydrochloric acid and 40 g of aluminum chloride were added to 1 liter of water. Surface treatment was performed.

The frequency of the trapezoidal wave current and the rising time T _p are as shown in Tables 1 to 4. The trapezoid had a current duty (t _a / T) of 0.5.

The current density is 50 A / dm ² at the peak value of the current when the aluminum plate undergoes the anode reaction,
The ratio Q _c / Q _a of the sum Q _c amount of electricity when the sum and the cathode reaction of the electric quantity Q _a of time the aluminum plate anode reaction 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 amount of electricity is
The results are shown in Tables 1 to 4.

(7) Alkaline Etching Treatment (3) Alkali etching treatment was carried out by spraying the above-mentioned aluminum plate with the alkaline solution E3-1 or E3-2 having the composition and liquid temperature shown in Table 6 through a spray tube. Tables 1 to 4 show which of the alkaline solutions was used and the amount of aluminum dissolved in the roughened surface.

(8) Desmutting process (3) Next, a desmutting process was performed. In the desmutting treatment, acidic solutions of the types shown in Tables 1 to 4 were used. Table 5 shows specific types of the acidic solution and liquid temperatures.

(9) Anodizing Treatment, Sealing Treatment, Hydrophilization Treatment Next, this plate was subjected to anodizing treatment under the conditions shown in Table 1 and Table 2. Table 7 shows the composition and the liquid temperature of the acidic electrolytic solution A1 and the acidic electrolytic solution A2 used in the anodizing treatment.

The aluminum plate after the anodizing treatment was subjected to either one or both of a pore-sealing treatment and a hydrophilizing treatment. Tables 1 to 4 show which of the sealing treatment and the hydrophilic treatment was performed.

The sealing treatment was carried out by treating in a saturated steam chamber at 100 ° C. and 1 atm for 10 seconds.

The hydrophilic treatment was carried out according to any one of the conditions S1 to S3 as shown in Tables 1 to 4. The conditions S1 to S3 are shown in Table 8.

(Example 2) (Example 2-1) The following undercoat liquid was applied to the aluminum support for lithographic printing plates prepared in Example 1-1 to Example 1-36, and the solution was applied at 80 ° C for 30 minutes. Dry for seconds. The coating amount after drying was 30 mg / m ² .

The composition of the undercoat liquid is as follows.   a) Aminoethylphosphonic acid ... 0.10 g   b) Phenylphosphonic acid: 0.15 g   c) β-alanine 0.10 g   d) Methanol ... 40g   e) Pure water ... 60g It was the street.

Next, a photosensitive layer forming liquid A, which will be described later, was applied to the aluminum support for lithographic printing plates at various coating amounts, and dried at 110 ° C. for 1 minute to form a photosensitive layer. A photosensitive lithographic printing original plate was obtained.

The composition of the photosensitive layer forming liquid A is as follows:   a) 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-a Esterified product with seton resin (described in Example 1 of US Pat. No. 3,635,709) What has been done) 0.45g   b) Cresol-formaldehyde novolac resin (meta / para ratio = 6: 4, heavy Weight average molecular weight 3,000, number average molecular weight 1,100, 0.7% unreacted cresol )… 1.1g   c) m-cresol-formaldehyde novolac resin (weight average molecular weight 1,700 , Number average molecular weight 600, containing 1% of unreacted cresol) ... 0.3 g   d) N- (P-aminosulfonylphenyl) acrylamido-normal butyrua Crylate-diethylene glycol monomethyl ether methacrylate copolymer (Mole ratio of each monomer = 40:40:20, weight average molecular weight 40,000, number average) Molecular weight 20,000) 0.2 g   e) P-normal octylphenol-formaldehyde resin (U.S. Pat. Described in the specification of No. 3,279) ... 0.021 g   f) Naphthoquinone-1,2-diazide-4-sulfonic acid chloride                                                         … 0.01 g   g) Tetrahydrophthalic anhydride ... 0.1 g   h) Benzoic acid: 0.02 g   i) 4- [p-N, N-bis (ethoxycarbonylmethyl) aminophenyl]- 2,6-bis (trichloromethyl) -S-triazine ... 0.01 g   j) 4- [PN- (P-hydroxybenzoyl) aminophenyl] -2,6- Bis (trichloromethyl) -S-triazine ... 0.02 g   k) 2-trichloromethyl-5- (4-hydroxystyryl) -1,3,4-o Xadiazole ... 0.01 g   l) Victoria Pure Blue BOH counter anion to 1-naphthalene sulfonic acid Substituted dye: 0.02g   m) 30 parts 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   n) Megafac F177 (Dainippon Ink & Chemicals Co., Ltd. fluorinated surfactant ) 20% by weight methyl isobutyl ketone solution) ... 0.02 g   o) Methyl ethyl ketone ... 15g   p) 1-methoxy-2-propanol ... 10 g It was the street.

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 photosensitive layer coated with the photosensitive layer forming liquid A and dried. Was electrostatically sprayed to provide a mat layer.

The lithographic printing plate precursor thus obtained was placed in a vacuum baking frame,
Through transparent positive film, 3kw from 1m distance
After exposure for 50 seconds with a metal halide lamp of No. 3, a molar ratio of silicon and sodium of Si was used as a developing solution.
5.2 of sodium silicate having O ₂ / Na ₂ O of 1.74
Fuji Photo Film Co., Ltd. FR-3 (1: 7) charged with 6% aqueous solution (pH = 12.7) and Fuji Photo Film Co., Ltd. automatic processor Stablon 9
Processed through 00D.

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. The planographic printing plate had good printing durability and stain resistance.

(Example 2-2) Examples 1-1 to 1
-36 on the aluminum support for lithographic printing plate,
The following photosensitive layer forming liquid was applied at a coating amount of ² g / m ² and dried to form a photosensitive layer.

The composition of the photosensitive layer forming liquid is   a) 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-a Seton resin esterified product weight average molecular weight 2500)                                                         ... 40 parts by weight   b) Phenol formaldehyde resin (weight average molecular weight 10,000, trinuclear or more) Ingredients 90%) 75 parts by weight   c) Acrylic polymer I ... 35 parts by weight   d) 2- (p-butoxyphenyl) -4,6-bis (trichloromethyl) -s- Triazine: 3 parts by weight   e) Oil Blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.) ... 1.5 parts by weight Megafac F-176 (Fluorine surfactant manufactured by Dainippon Ink and Chemicals, Inc.)                                                         … 0.3 parts by weight   f) Methyl ethyl ketone: 1000 parts by weight   g) Propylene glycol monomethyl ether ... 1000 parts by weight Met.

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 give acrylic polymer I 1
10.4 g (yield 95%, Mw 52,000) was obtained.

A mat-forming resin liquid was sprayed onto the photosensitive layer to form a mat layer.

As the matte layer forming resin liquid, a 12% aqueous solution was used in which a part of the methyl methacrylate / ethyl acrylate / acrylic acid (charge ratio 65:20:15) copolymer was a sodium salt.

For spraying the mat-forming resin liquid, a rotary atomizing electrostatic coating machine was used, and the atomizing head rotation speed was 25,000 rp.
m, flow rate of resin liquid 40 ml / min, voltage applied to atomizing head -90 kV, ambient temperature during application 25 ° C, relative humidity 50%
It went on condition of. 2.5 seconds after the matting resin solution was sprayed, steam was sprayed to moisten the coated surface, and after 3 seconds, warm air with a temperature of 60 ° C. and a humidity of 10% was sprayed for 5 seconds to dry.

The lithographic printing original plate prepared by the above procedure was irradiated with a metal halide lamp of 3 kW from a distance of 1 m through the original film and exposed for 60 seconds.

Next, a commercially available automatic processor PS-900D (manufactured by Fuji Photo Film Co., Ltd.) having an immersion type developing tank was charged with 20 liters of the developing solution a and the developing replenishing solution a and kept at 30 ° C. did. The second bath of PS-900D contained 8 liters of tap water, and the third bath contained 8 parts of finishing liquid prepared by diluting the following finishing gum liquid with water 1: 1.
I prepared liters. The PS-900D was passed through the exposed lithographic printing plate described above and developed.

The pH of developer a is about 12.4 and the composition is a) D-saccharose 4.8% by weight b) sodium hydroxide 0.34% by weight c) sodium carbonate 0.70% by weight d) Tetrabutylammonium bromide 0.03% by weight e) Water 94.7% by weight. The developer replenisher a has a pH of about 13.0 and has a composition of a) D-sucrose 9.7% by weight b) sodium hydroxide 1.5% by weight c) sodium carbonate 1.0% by weight d. ) Tetrabutylammonium bromide 0.07 wt% e) Water The rest was as it was.

The composition of the finishing gum solution is as follows:   a) Gum arabic 1.8% by weight   b) Enzyme-modified potato starch 18.3% by weight   c) Enzyme-modified corn starch starch 3.7% by weight   d) Phosphorylated waxy corn starch starch 1.8% by weight   e) Dioctyl sulfosuccinate sodium salt 0.91% by weight   f) Ammonium monophosphate 0.27% by weight   g) Phosphoric acid (85%) 0.37% by weight   h) EDTA-tetrasodium salt 0.27% by weight   i) ethylene glycol 1.8% by weight   j) Benzyl alcohol 2.3% by weight   k) Sodium dehydroacetate 0.04% by weight   l) Emulsion type silicone defoamer 0.02% by weight   m) Water 68.4% by weight It was the street.

The rinse solution is   a) Sodium dodecyl diphenyl ether disulfonate (40% by weight aqueous solution) ... 6.7% by weight   b) Sodium hexametaphosphate: 0.8% by weight   c) Benzyl alcohol: 1.5% by weight   d) Polyoxyethylene (addition of 12 mol of ethylene oxide) nonylphenyl ether Tell… 1.5% by weight   e) Dioctyl sodium sulfosuccinate: 1.4% by weight   f) Phosphoric acid (85% by weight) ... 5.2% by weight   g) Sodium hydroxide: 2.0% by weight   h) Silicon antifoaming agent: 0.01% by weight   i) Water ... 80.89% by weight Had a composition of.

The lithographic printing plate after development was evaluated for printing performance in the same procedure as in Example 2-1, and it was found that it had good printing durability and printing performance.

Example 2-3 Example 1-1 to Example 1
-36 on the aluminum support for lithographic printing plate,
A 1% aqueous solution of a copolymer A (copolymer of methyl methacrylate / ethyl acrylate / 2-acrylamido-2-methylpropanesulfonate (charge molar ratio = 50: 30: 20) (average molecular weight about 60,000)) It was applied with a roll coater and dried to form an undercoat layer. The coating amount after drying was 0.05 g / m ² .

The following photosensitive layer forming liquid was applied onto this undercoat layer and dried to obtain a photosensitive lithographic printing plate.

The composition of the photosensitive layer forming liquid is   a) 2-hydroxyethyl methacrylate copolymer (US Pat. No. 4,123,276) As described in Example 1 therein. ) ... 0.87g   b) 2-Methoxy of the condensate of p-diazodiphenylamine and paraformaldehyde Si-4-hydroxy-5-benzoylbenzenesulfonate ... 0.1 g   c) Oil Bull- # 603 (Orient Chemical Co., Ltd., blue dye)                                                       … 0.03 g   d) Methanol ... 6g   e) 2-methoxyethanol: 6 g It was the street.

The dry coating amount of the photosensitive layer was 2.0 g / m ² .

A transparent negative original image was vacuum-adhered to the lithographic printing original plate, and a metal halide lamp of 3 kW was used to measure 60 m from a distance of 1 m.
It was exposed for a second, immersed in the following developer for 1 minute, lightly rubbed the surface of the photosensitive layer with a sponge to develop, and coated with a commercially available desensitizing gum solution.

The composition of the developer is:   a) Sodium sulfite ... 5g   b) Benzyl alcohol ... 30g   c) Sodium carbonate ... 5g   d) Sodium isopropylnaphthalene sulfonate 12g   e) Pure water ... 1000g Met.

The printing performance of this lithographic printing plate was evaluated by the same procedure as in Example 2-1, and it was found to be a good printing plate.

Example 2-4 Preparation of Carbon Black Dispersion The following raw materials were dispersed with glass beads for 10 minutes to prepare a carbon black dispersion.

A) Carbon black: 1 part by weight b) Copolymer of benzyl methacrylate and methacrylic acid (molar ratio of 72:28, weight average molecular weight 70,000): 1.6 parts by weight c) Cyclohexanone: 1.6 parts by weight Part d) Methoxypropyl acetate ... 3.8 parts by weight Preparation of negative type photosensitive lithographic printing plate precursor The following photosensitive layer forming liquid was added to the aluminum support for lithographic printing plate prepared in Example 1-1 to Example 1-36. Apply
It was dried at 100 ° C. for 2 minutes to obtain a negative photosensitive lithographic printing plate. The coating amount after drying was 2.0 g / m ² .

As the photosensitive layer forming liquid,   a) The carbon black dispersion: 10 g   b) of 4-diazodiphenylamine and formaldehyde Hexafluorophosphate of condensate ... 0.5g   c) Methacrylic acid, 2-hydroxyethyl acrylate and benzyl methacrylate And acrylonitrile radical copolymer (molar ratio of monomer charge 15: 30: 4) 0:15, weight average molecular weight 100,000) ... 5 g   d) Malic acid: 0.05 g   e) FC-430 (fluorine-based surfactant manufactured by 3M Company, USA) ... 0.05 g   f) 1-methoxy-2-propanol ... 80g   h) Ethyl lactate ... 15g   i) Water: 5g The one having the composition of was used.

The obtained lithographic printing original plate 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), gum solution FN-.
When processed through an automatic processor equipped with 2 (1: 1), a negative image was obtained. When this lithographic printing plate was used for printing on a Heidel SOR-KZ machine, good printed matter was obtained.

(Example 2-5) Formation of Undercoat Layer The following undercoat liquid was applied to the aluminum support for lithographic printing plates prepared in Example 1-1 to Example 1-36 with a wire bar, and the mixture was heated. It dried at 90 degreeC for 30 second using the air dryer. The coating amount after drying was 20 mg / m ² .

The undercoat liquid is     -Methacryloyloxyethylphosphonic acid ... 0.2 g     ・ Mole ratio of methyl acrylate and styrene sulfonic acid sodium salt 7 Copolymer of 5:15 ... 0.2 g     ・ Calcium nitrate ... 0.2g     ・ Methanol: 20g     ・ Ion-exchanged water… 80g Had a composition of.

Formation of Image Forming Layer On the support having the undercoat layer formed thereon, the following image forming layer coating liquid P-1 was applied with a wire bar and dried at 120 ° C. for 45 seconds with a warm air dryer. To form a recording layer, and further, the following coating solution for overcoat layer was 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. The coating amount of the image forming 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 .

The composition of the coating solution P-1 for image forming layer is as follows:   ・ Titanocene type radical generator (CGI-784, Ciba Specialty K Micals Co., Ltd.) ... 0.1 g   -Polymerizable compound (RM-2) ... 0.6 g   -Polymerizable compound (RM-3) ... 0.2 g   ・ Visible light absorber (VR-1) ... 0.10 g   -Polymer (PB-1) ... 1.20 g   ・ Copper phthalocyanine pigment ... 0.04g   ・ Polymerization inhibitor (Cuperon Al, manufactured by Wako Pure Chemical Industries, Ltd.) ... 0.005 g   ・ Fluorosurfactant (Megafuck KF309, Dainippon Ink and Chemicals, Inc. )) ... 0.03g   ・ Methyl ethyl ketone ... 10g   .Gamma.-butyrolactone ... 5 g   ・ Methanol: 7 g   ・ 1-Methoxy-2-propanol ... 5 g It was the street.

The polymerizable compound RM-2, the polymerizable compound RM-3, and the visible light absorber VR-1 used for the preparation of the coating liquid P-1 for the image forming layer have the following structures. .

[0313]

[Chemical 1]

[0314]

[Chemical 2]

[0315]

[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.

[0316]

[Chemical 4] The coating liquid for the overcoat layer is: polyvinyl alcohol (saponification degree: 98.5 mol%, polymerization degree: 500) 3 g Nonionic surfactant (EMEREX NP-10 manufactured by Nippon Emulsion Co., Ltd.) ... 0.05 g-Ion-exchanged water ... It had a composition of 96.95 g.

Evaluation of planographic printing plate Automatic developing machine (LP-850P, manufactured by Fuji Photo Film Co., Ltd.)
The developing solution V-2 was charged into the developing treatment tank of 2) and kept at 30 ° C. The second bath of the automatic processor was charged with tap water, and the third bath was charged with a finishing gum solution in which FP-2W (manufactured by Fuji Photo Film Co., Ltd.) was diluted 1: 1 with water. . The pH of the developer was 8.1.

The developing solution V-2 is   ・ Sodium hydrogen carbonate ... 26g   ・ Ethylene glycol mononaphthyl ether monosulfate sodium salt                                                 ... 30g   ・ Ethylene glycol monododecyl ether ... 20g   ・ Sodium sulfite ... 3g   ・ Ethylenediaminetetraacetic acid tetrasodium ... 1g   ・ Water… 920g Had a composition of.

Next, 20 lithographic printing original plates P-1 each having a size of 1030 × 800 mm were used, using a 30 mW semiconductor laser emitting 405 nm violet light, and a laser beam diameter of 1
Scanning exposure was performed under the exposure conditions of ² μm and plate surface energy of 50 μJ / cm ² , and development processing was performed using the above-mentioned automatic developing machine.
After the processing, the automatic developing solution was left as it was for 3 days. Then, one lithographic printing original plate P-1 was similarly laser-exposed and subsequently developed. Obtained planographic printing plate P-1
Was printed using a printing machine Lithrone manufactured by Komori Corporation. After the start of printing, it was visually evaluated how many sheets of printed material with sufficient ink could be obtained. In addition, the state of stains on the non-image area at that time was visually observed. As a result, 70,000 good prints were obtained from the planographic printing plate processed before leaving the automatic developing machine and from the planographic printing plate processed after standing. Further, no stain was observed in the non-image area of the obtained printed matter.

(Example 2-6) Formation of Undercoat Layer The following undercoat liquid was applied with a wire bar to the aluminum support for lithographic printing plates produced in Example 1-1 to Example 1-36, and warm air was applied. It dried at 90 degreeC for 30 second (s) using the dry dryer. The coating amount after drying was 20 mg / m ² .

As the undercoating 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 Image Forming Layer On the aluminum support for a lithographic printing plate on which the undercoat layer has been formed, an image forming layer coating solution P-2 described later is applied with a wire bar, and heated with a hot air dryer to give 120. An image forming layer was formed by drying at 45 ° C. for 45 seconds to obtain a lithographic printing original plate P-2. The coating amount after drying was 2.0 g / m ² .

The composition of the coating liquid P-2 for image forming layer is   -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 It was the street.

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.

[0325]

[Chemical 5]

[0326]

[Chemical 6]

[0327]

[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

[0328]

[Chemical 8] Evaluation plate material supply device (SA-L8000) for lithographic printing original plate P-2, exposure device (Lux)
el T-9000CTP), conveyor (T-9000)
Conveyor), automatic processor (LP-1310)
H), a stocker (ST-1160) Fuji Photo Film Co., Ltd. CTP output system was used. The developer composition V-1 was charged into the development processing tank of an automatic developing machine,
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 developing solution was 8.0.

The composition of the developer composition V-1 is as follows:   ・ Potassium bicarbonate ... 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 It was the street.

Next, 30 lithographic printing original plates P-2 each having a size of 1030 × 800 mm were loaded in a plate material supplying device, exposed and developed continuously in a fully automatic manner, and discharged to a stocker. After the processing, the automatic developing solution was left as it was for 3 days. After being left standing, one plate of the planographic printing original plate P-2 was loaded into the plate material supplying device, and was continuously exposed and developed in a fully automatic manner and discharged to a stocker. Obtained planographic printing plate P-2
Was printed using a printing machine Lithrone manufactured by Komori Corporation. At this time, after the start of printing, it was visually evaluated how many sheets of printed matter with sufficient ink could be obtained. In addition, the state of stains on the non-image area at that time was visually observed.

As a result, 60,000 good prints were obtained from both the printing plate processed before leaving the automatic developing machine and the printing plate processed after standing. No stain was found on the non-image area of the obtained printed matter.

(Example 2-7) Formation of Undercoat Layer An undercoat liquid having the following composition was applied to the aluminum support for lithographic printing plates prepared in Example 1-1 to Example 1-36,
It was 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 represented by the following chemical formula: 0.3 g

[0333]

[Chemical 9] -Methanol ... 100 g-Water ... 1 g was used.

Formation of Photosensitive Layer Further, a photosensitive layer coating solution 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 with a bar coater. Using,
The coating amount after drying (photosensitive layer coating amount) was 1.0 g / m ^2, and the coating was dried to form a photosensitive layer to obtain a lithographic printing plate.

The composition of the photosensitive layer coating solution is as follows:   ・ Capric acid: 0.03 g   -Copolymer I ... 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   ・ Cyanine dye A represented by the following structural formula: 0.017 g

[0336]

[Chemical 10] -Dyestuff in which the counter ion of Victoria Pure Blue BOH is substituted with 1-naphthalenesulfonic acid anion ... 0.015 g-Fluorosurfactant (Megafuck F-177, manufactured by Dainippon Ink and Chemicals, Inc.) ... 0.05 g-γ -Butyl lactone ... 10 g. Methyl ethyl ketone ... 10 g. 1-Methoxy-2-propanol ... 1 g.

The copolymer I was synthesized as follows.

A 500 mL three-necked flask equipped with a stirrer, a condenser and a dropping funnel was charged with methacrylic acid 31.
0 g (0.36 mol), ethyl chloroformate 39. lg
(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 (0.36 mol) of triethylamine was added to this mixture.
Was dropped by a 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 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
After slurrying in mL, the resulting slurry is filtered,
The remaining solid was dried to obtain a white solid of N- (p-aminosulfonylphenyl) methacrylamide (yield 46.
9g).

Next, in a 20 mL three-necked flask equipped with a stirrer, a condenser and a dropping funnel, the N- (p
-Aminosulfonylphenyl) methacrylamide 4.6
1 g (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 charged, and the mixture was stirred while heating to 65 ° C with a hot water bath. Add "V-6 to this mixture.
5 "(manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred for 2 hours under a nitrogen stream while maintaining the temperature at 65 ° C.

The reaction mixture was further mixed with the N- (p-
Aminosulfonylphenyl) methacrylamide 4.61
g, 2.94 g of ethyl methacrylate, 0.80 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 resulting mixture was further stirred at 65 ° C. for 2 hours.

After the completion of the reaction, 40 g of methanol was added to the mixture to cool it, and the mixture was added while stirring 2 liters of water. After stirring for 30 minutes, the precipitate was collected by filtration and dried to give 15 g of white. A solid copolymer I was obtained.

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

The lithographic printing plate obtained as described above,
Output 500mW, wavelength 830nm, beam diameter 17μm
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.

When this printing plate was printed, it was a good printing plate.

(Example 2-8) Formation of Undercoat Layer The undercoat liquid having the following composition was applied to the aluminum support for lithographic printing plates produced in Example 1-1 to Example 1-36,
It was 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 .

The composition of the undercoat liquid composition is   ・ Polymer compound having the following structure: 0.3 g

[0348]

[Chemical 11] ・ Methanol: 100 g ・ Water: 1 g

Formation of Photosensitive Layer A photosensitive layer coating solution having the following composition was prepared and applied onto the above lithographic printing plate aluminum support using a bar coater so that the coating amount after drying was 1.0 g / m ² . A photosensitive layer was formed by drying to obtain a lithographic printing original plate.

The composition of the photosensitive layer coating solution is as follows:   ・ 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   ・ Cyanine dye A represented by the following structural formula: 0.017 g

[0351]

[Chemical 12] -Dyestuff in which the counter ion of Victoria Pure Blue BOH is substituted with 1-naphthalene sulfonate anion ... 0.015 g-Fluorosurfactant (Megafuck F-177, manufactured by Dainippon Ink and Chemicals, Inc.)-0.05 g-γ -Butyl lactone ... 10 g. Methyl ethyl ketone ... 10 g. 1-Methoxy-2-propanol ... 1 g.

The copolymer II was synthesized by the following procedure.

A 500 mL three-necked flask equipped with a stirrer, a condenser and a dropping funnel was charged with methacrylic acid 31.
0 g (0.36 mol), ethyl chloroformate 39. lg
(0.36 mol) and 200 mL of acetonitrile were charged, 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.

51.7 g (0.30 mol) of p-aminobenzenesulfonamide was added to this reaction mixture, and the mixture was stirred for 1 hour while warming to 70 ° C. in an oil bath. After completion of the reaction, the mixture was added while stirring 1 liter of water and stirred for 30 minutes. The precipitate was filtered from this mixture, 500 mL of water was added to the obtained precipitate to prepare a slurry, which was filtered, and the obtained solid was dried to obtain N- (p-aminosulfonylphenyl) methacryl. A white solid of amide 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 charged, and the mixture was stirred while heating to 65 ° C. in a hot water bath. Add "V-65" to this mixture.
0.15 g (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred under a nitrogen stream for 2 hours while maintaining the temperature at 65 ° C. To this reaction mixture was further added 4.61 g of N- (p-aminosulfonylphenyl) methacrylamide, 2.94 g of ethyl methacrylate, 0.80 g of acrylonitrile, N, N-.
Dimethylacetamide 20 g, and "V-65" 0.
15 g of the mixture was added dropwise by the dropping funnel over 2 hours.

After completion of dropping, the 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. The mixture was added while stirring 2 liters of water, and the mixture was stirred for 30 minutes, and then the precipitate was collected by filtration and dried to obtain 15 g of a white solid copolymer II.

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

The lithographic printing plate obtained as described above had an output of 500 mW, a wavelength of 830 nm and a beam diameter of 17 μm (1
/ E @ 2) of a semiconductor laser at a main operation speed of 5 m / sec, and then developed with 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 (K ₂ O) in which a non-reducing sugar and a base are combined is added to an amphoteric surfactant Pionin C. A concentrated solution was prepared by adding 20 g of -158G (manufactured by Takemoto Yushi Co., Ltd.) and 2.0 g of antifoaming agent Olfine AK-02 (manufactured by Nissin Chemical Co., Ltd.). 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.

When printing was carried out using this printing plate, it was a good printing plate.

Example 2-9 Synthesis of Copolymer (1) Synthesis Example 1 (Copolymer 1) 31.0 g of methacrylic acid (0.36 g) was added to a 500 ml three-necked flask equipped with a stirrer, a cooling tube and a dropping funnel. Mol), 39.1 g (0.36 mol) of ethyl chloroformate 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, 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 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 then washed with water (500 m).
After slurrying with l, this 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
, And the mixture was stirred while heating to 65 ° C. with a hot water bath. Add "V-65" to this mixture (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.

To the reaction mixture was further added 5.04 of N- (p-aminosulfonylphenyl) methacrylamide.
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 is completed, the temperature is further increased to 65 ° C for 2
The resulting mixture was stirred for time. After the reaction was completed, 40 g of methanol was added to the mixture and cooled, and the resulting mixture was mixed with water 2
This water was added to a liter with stirring, the mixture was stirred for 30 minutes, and the precipitate was collected by filtration and dried to give 1
5 g of white solid copolymer 1 was obtained. When the weight average molecular weight (polystyrene standard) of this copolymer 1 was measured by gel permeation chromatography, it was 5
It was 3,000.

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

Application of Undercoat Liquid The following undercoat liquid was applied to the aluminum support for lithographic printing plates prepared in Example 1-1 to Example 1-36, and the coating film was dried at 90 ° C. for 1 minute. The coating amount of the coating film after drying is 10 m
It was g / m ² .

The composition of the undercoat liquid is as follows:   .Beta.-alanine ... 0.5 g   ・ Methanol: 95g   ・ Water: 5g It was the street.

Formation of Image Forming Layer The above-mentioned aluminum support for lithographic printing plates was coated with a photosensitive layer forming liquid A1 described below and dried at 100 ° C. for 2 minutes,
The (A) layer was formed. The applied amount after drying is 1.4 g / m ^2.
Met. Further, a photosensitive layer forming liquid B1 described below was applied and dried at 100 ° C. for 2 minutes to form a layer (B), thereby obtaining 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 .

The composition of the photosensitive layer forming liquid A1 is   -Copolymer 1 ... 0.75 g   ・ Cyanine dye A ... 0.04g   ・ P-toluenesulfonic acid: 0.002 g   ・ Tetrahydrophthalic anhydride: 0.05 g   ・ Victoria pure blue (counter anion of BOH is 1-naphthalene sulfonic acid Dye substituted with anion) 0.015 g   ・ Fluorosurfactant (MegaFac F-177, Dainippon Ink and Chemicals, Inc. ) Made ... 0.02g   ・ Γ-Butyl lactone: 8 g   ・ Methyl ethyl ketone ... 7g   ・ 1-Methoxy-2-propanol: 7 g It was the street.

The composition of the photosensitive layer forming liquid B1 is   m, p-cresol novolac (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, Dainippon Ink and Chemicals, Inc.) Made) 0.05 g   Methyl ethyl ketone 7g   1-methoxy-2-propanol 7g It was the street.

Performance evaluation of lithographic printing original plate The printing performance of the lithographic printing original plate prepared as described above was evaluated.

Output of the obtained lithographic printing plate precursor is 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.

When this lithographic printing plate was printed on high-quality paper with a Heidel KOR-D machine manufactured by Heidelberg, it was found to be a good printing plate.

(Example 2-10) Formation of Undercoat Layer The following undercoat liquid was applied to the aluminum support for lithographic printing plates prepared in Example 1-1 to Example 1-36 and dried to form an undercoat layer. Formed.

The composition of the undercoating liquid is   ・ The following compounds: 0.3 g   ・ Methanol: 100g   ・ Water: 1g Had a composition of.

Formation of Heat Sensitive Layer The following lower layer coating solution was applied to the obtained substrate at a coating amount of 0.
After coating so as to be 85 g / m ² , it is Win with PERFECT OPEN PH200 manufactured by TABAI.
d Control is set to 7 and dried at 140 ° C. for 50 seconds, and then the coating liquid for heat-sensitive layer is applied at 0.15 g
/ M ² and then dried at 120 ° C for 1 minute to obtain a lithographic printing original plate.

The composition of the lower layer coating solution is as follows:   -N- (4-aminosulfonylphenyl) methacrylamide / acrylonitri Le / methyl methacrylate = 36/34/30 (molar ratio charged), weight average molecular weight 50000) 1.896g   ・ Cresol novolac (m / p = 6/4 weight average molecular weight 4500, residual molybdenum Nomer 0.8wt%) 0.237g   ・ Cyanine dye A (the following structure) 0.109 g

[0378]

[Chemical 13] -4,4'- bishydroxyphenyl sulfone 0.063g-tetrahydrophthalic anhydride 0.190g-p-toluenesulfonic acid 0.008g-Ethyl violet counter ion substituted with 6-hydroxynaphthalene sulfone 05g-Fluorosurfactant (Megafuck F176, manufactured by Dainippon Ink and Chemicals Co., Ltd.) 0.035g-Methyl ethyl ketone 26.6g-1-Methoxy-2-propanol 13.6g-γ-butyrolactone 13.8g As follows: Met.

On the other hand, the composition of the heat-sensitive layer coating solution is   -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 It was the street.

The lithographic printing original plate 1 thus obtained was manufactured by Creo Co.
A test pattern was drawn with a redsetter at a beam intensity of 9w and a drum rotation speed of 150 rpm.

For the planographic printing original plate on which the drawing was performed,
Upon development, the following non-silicate developer was used for development.

As the non-silicate developer, 1 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 Co., Ltd. )
(Manufactured by Nippon Shinyaku 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, and the concentrated solution was diluted 9 times with water. The conductivity of the non-silicate developer is 45 mS / cm.

The printing performance of this lithographic printing plate was evaluated according to the same procedure as in Example 2-9, and it was found to be a good printing plate.

[0384]

As described above, according to the present invention,
A method for producing an aluminum support for a lithographic printing plate, which gives an aluminum support for a lithographic printing plate having a high level of printing durability and stain resistance, and an aluminum support for a lithographic printing plate produced by the production method, and There is provided a lithographic printing original plate in which an image forming layer is laminated on the roughened surface of the lithographic printing plate aluminum support.

[Brief description of drawings]

FIG. 1 is a waveform diagram showing an example of a trapezoidal wave current waveform that can be applied in an electrolytic graining treatment in a method for manufacturing an aluminum support for a lithographic printing plate according to the present invention.

FIG. 2 is an example of an electrolytic cell that can be used in an electrolytic graining treatment in the method for producing an aluminum support for a lithographic printing plate according to the present invention.

[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 front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C25D 11/16 301 C25D 11/16 301 C25F 3/04 C25F 3/04 D G03F 7/00 503 G03F 7 / 00 503 7/09 501 7/09 501 (72) Inventor Akio Uesugi 4000 Kawajiri, Yoshiji-cho, Haibara-gun, Shizuoka Prefecture F-term in Fuji Shashin Film Co., Ltd. (reference) 2H025 AA12 AB03 AC01 AC08 AD01 AD03 DA18 DA20 EA01 FA03 FA17 2H096 AA07 BA01 BA09 CA01 CA03 CA20 EA02 EA04 GA09 2H114 AA04 AA14 AA24 BA02 BA10 DA04 DA08 DA09 DA10 DA11 DA64. WB05 WE22 WM03 WM04 WN10

Claims (31)

[Claims] 1. At least one surface of an aluminum plate is subjected to (1) alkaline etching treatment (1) for etching with an alkaline solution, (2) desmutting treatment for desmutting in an acid solution (1), (3) nitric acid aqueous solution. Electrolytic surface roughening treatment (1), (4) Alkaline etching treatment by etching with alkaline solution (2), (5) Desmut treatment (2) by desmutting treatment in acidic solution, ( 6) Electrolytic surface roughening treatment in an aqueous hydrochloric acid solution (2), (7) Alkaline etching treatment in which an alkaline solution is used for etching (3), (8) Desmut treatment in an acidic solution (desmut treatment ( 3) and (9) An aluminum support for a lithographic printing plate, which is characterized by sequentially performing anodizing treatment for forming an anodized film in an acidic electrolyte to form a roughened surface. The method of production. 2. The method for producing an aluminum support for a lithographic printing plate according to claim 1, wherein at least one of sealing treatment and hydrophilic treatment is performed after the anodizing treatment. 3. In the electrolytic surface-roughening treatment (1), in an aqueous nitric acid solution containing nitric acid, aluminum ions and ammonium ions, the amount of electricity during the anode reaction of the aluminum plate is 100 to 500 C / dm ^2.
The method for producing an aluminum support for a lithographic printing plate according to claim 1 or 2, wherein an alternating current is applied to the aluminum plate so as to perform electrolysis. 4. In the electrolytic surface-roughening treatment (1), the amount of electricity during the anode reaction of the aluminum plate is 200 to 500 C / dm ^{2 in} a nitric acid aqueous solution containing nitric acid, aluminum ions and ammonium ions.
The method for producing an aluminum support for a lithographic printing plate according to claim 3, wherein an alternating current is applied to the aluminum plate so as to electrolyze the aluminum plate. 5. AC to be applied to the aluminum plate in the electrolytic graining treatment (1) is a percentage of the period T of the anode reaction time t _a of the aluminum plate duty
Is 0.5, the rise time t _p until the current reaches the peak from 0 is 0.5 to 2 msec, and the frequency is 4
A 0～70Hz, the ratio of the electric quantity Q _a of time electricity Q _c and the anode reaction at the time of cathodic reaction Q _c / Q _a is a lithographic printing plate as claimed in claim 3 or 4 is 0.9 to 1 Method for manufacturing aluminum support. 6. The nitric acid aqueous solution used in the electrolytic surface-roughening treatment (1) has a nitric acid concentration of 5 to 15 g / liter, an aluminum ion concentration of 3 to 7 g / liter, and an ammonium ion concentration. Is 50-150
ppm and the liquid temperature is 30 to 80 ° C. 6.
The method for producing an aluminum support for a lithographic printing plate according to any one of 1. 7. In the electrolytic surface-roughening treatment (2), an aqueous hydrochloric acid solution containing hydrochloric acid and aluminum ions is used so that the amount of electricity during the anode reaction of the aluminum plate is 25 to 75 C / dm ^2. The method for producing an aluminum support for a lithographic printing plate according to any one of claims 1 to 6, wherein alternating current electrolysis is performed. 8. The alternating current applied to the aluminum plate in the electrolytic surface-roughening treatment (2) has a duty of 0.5.
The aluminum for lithographic printing plate according to claim 7, wherein the rising time t _p is 0.5 to 2 msec, the frequency is 40 to 150 Hz, and the Q _c / Q _a is 0.9 to 1. A method for manufacturing a support. 9. The hydrochloric acid aqueous solution has a hydrochloric acid concentration of 2 to 1.
It is 5 g / liter, and the concentration of aluminum ions is 3
The method for producing an aluminum support for a lithographic printing plate according to claim 7 or 8, which is an aqueous hydrochloric acid solution having a liquid temperature of 20 to 50 ° C of -7 g / liter. 10. In at least one of the electrolytic surface roughening treatments (1) and (2), an average relative flow velocity of the nitric acid aqueous solution to the aluminum plate is 1 to 100.
The method for producing an aluminum support for a lithographic printing plate according to claim 1, wherein the nitric acid aqueous solution is circulated along the longitudinal direction of the aluminum plate so as to be 0 m / min. 11. In the alkali etching treatment (1), the dissolution amount of the aluminum plate is ² to 15 g / m ^2.
The method for producing an aluminum support for a lithographic printing plate according to any one of claims 1 to 10, wherein the aluminum support is etched so that 12. The method for producing an aluminum support for a lithographic printing plate according to claim 11, wherein in the alkali etching treatment (1), the aluminum plate is subjected to an etching treatment using an alkali solution containing sodium hydroxide. 13. The alkaline solution contains sodium hydroxide and aluminum ions in an amount of 3 to 30% by weight and 0.3 to 9% by weight, respectively, and has a liquid temperature of 35 to 80 ° C.
13. The method for producing an aluminum support for a lithographic printing plate according to claim 12. 14. The method for producing an aluminum support for a lithographic printing plate according to claim 1, wherein an aqueous sulfuric acid solution or an aqueous nitric acid solution is used as the acidic solution in the desmutting treatment (1). 15. The waste liquid from the electrolytic surface roughening treatment (1) or the anodizing treatment is used as the acidic solution in the desmutting treatment (1).
14. The method for producing an aluminum support for a lithographic printing plate according to any one of items 1 to 13. 16. In the desmutting treatment (1), the aluminum plate is heated at a liquid temperature of sulfuric acid of 80 to 350 g / l at a liquid temperature of 25 to 80 ° C. or nitric acid at a liquid temperature of 5 to 15 g / l. 25-80 ° C
The method for producing an aluminum support for a lithographic printing plate according to any one of claims 1 to 13, wherein the treatment is performed with the nitric acid aqueous solution for 1 to 10 seconds. 17. In the alkali etching treatment (2), the dissolution amount of the aluminum plate is 0.1 to 10 g /
method for producing an aluminum support for a lithographic printing plate according to any one of claims 1 to 16 for etching so as to m ^2. 18. The method for producing an aluminum support for a lithographic printing plate according to claim 17, wherein in the alkaline etching treatment (2), the aluminum plate is subjected to an etching treatment using an alkaline solution containing sodium hydroxide. 19. The alkaline solution contains sodium hydroxide and aluminum ions in an amount of 3 to 30% by weight and 0.3 to 9% by weight, respectively, and has a liquid temperature of 35 to 80 ° C.
19. The method for producing an aluminum support for a lithographic printing plate according to claim 18. 20. The sulfuric acid aqueous solution is used as the acidic solution in the desmutting treatment (2).
20. A method for producing an aluminum support for a lithographic printing plate according to any one of items 1 to 19. 21. In the desmutting treatment (2), the aluminum plate is treated with a sulfuric acid aqueous solution containing sulfuric acid at 80 to 350 g / liter at a liquid temperature of 25 to 80 ° C. for 1 to 1;
The method for producing an aluminum support for a lithographic printing plate according to claim 20, wherein the treatment is performed for 0 seconds. 22. The method for producing an aluminum support for a lithographic printing plate according to claim 20, wherein in the desmutting treatment (2), a waste liquid from the anodizing treatment is used as the acidic solution. 23. In the alkali etching treatment (3), the dissolution amount of the aluminum plate is 0.05 to 1 g /
method for producing an aluminum support for a lithographic printing plate according to any one of claims 1 to 22 for etching so as to m ^2. 24. The method for producing an aluminum support for a lithographic printing plate according to claim 23, wherein in the alkali etching treatment (3), the aluminum plate is subjected to etching treatment using an alkali solution containing sodium hydroxide. 25. The alkaline solution used in the alkaline etching treatment (3) contains sodium hydroxide and aluminum ions in an amount of 3 to 30% by weight and 0.3 to 9% by weight, respectively, and has a liquid temperature of 25 to 30%. The method for producing an aluminum support for a lithographic printing plate according to claim 24, which has a temperature of 80 ° C. 26. A sulfuric acid aqueous solution is used as the acidic solution in the desmutting treatment (3).
25. A method for producing an aluminum support for a lithographic printing plate according to any one of 25 to 25. 27. In the desmutting treatment (3), the aluminum plate is treated with a sulfuric acid aqueous solution containing sulfuric acid at 80 to 350 g / liter at a liquid temperature of 25 to 80 ° C. for 1 to 1;
The method for producing an aluminum support for a lithographic printing plate according to claim 26, wherein the treatment is carried out for 0 seconds. 28. The method for producing an aluminum support for a lithographic printing plate according to claim 26, wherein in the desmutting treatment (3), a waste liquid from the anodizing treatment is used as the acidic solution. 29. In the anodizing treatment, the acidic electrolyte contains sulfuric acid and aluminum ions,
The aluminum support for a lithographic printing plate according to any one of claims 1 to 27, wherein electrolytic treatment is carried out by direct current at a liquid temperature of 25 to 80 ° C using a sulfuric acid aqueous solution having a sulfuric acid concentration of 80 to 200 g / liter. Body manufacturing method. 30. An aluminum support for a lithographic printing plate, which is manufactured by the method according to any one of claims 1 to 29. 31. A lithographic printing original plate comprising a positive or negative image forming layer provided on the roughened surface of the aluminum support for lithographic printing plates according to claim 30.