JP2000079774A - Electrolytic treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily apply to an existing AC power source, and improve the stability of electrodes, and also, form a uniform pit by constituting a counter electrode of a main counter electrode and an auxiliary counter electrode, connecting a circuit for the auxiliary counter electrode to a circuit connecting to the main counter electrode in parallel, and at the same time, making a DC current flow to the auxiliary counter electrode. SOLUTION: An auxiliary counter electrode 3 is provided, and at the same time, a DC power source 6 is connected to the auxiliary counter electrode 3, and a current which flows on a main counter electrode 2 is controlled in a manner to be A<B, C<D. For the DC power source 6, the current value is preferably controlled together with an AC power source 5, and also, (the current which is made to flow to the auxiliary counter electrode 3)/(the alternating current)=0.001-0.3 is preferable, and (the current which is made to flow to the auxiliary counter electrode 3)/(the alternating current)=0.01-0.2 is more preferable, and 0.03-0.1 is even more preferable. By this constitution, this method can be easily applied to a device using an already existing AC power source 5 without modifying the power source or the like. Also, the stability of the electrodes can be improved, and also, a uniform pit can be formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for electrolytically treating a material to be treated such as a metal support, and more particularly to an electrolytic treatment for producing a lithographic printing plate support using aluminum or an aluminum alloy as the metal support. About the method.

[0002]

2. Description of the Related Art Generally, in order to use an aluminum plate as a lithographic printing plate substrate, it is necessary that the aluminum plate has appropriate adhesion to a photosensitive material and water retention, and is further uniformly roughened. . The fact that the surface is uniformly roughened requires that the size of the generated pits be appropriately uniform and that such pits be uniformly generated over the entire surface. In addition, the pits have a remarkable effect on printing performance of the printing plate, such as stain resistance, printing durability, and the like, and its quality is an important factor in plate material manufacturing.

[0003] In recent years, it has been an important issue to continuously and stably produce the above-mentioned good quality. There are various methods for surface roughening, but the electrochemical surface roughening method can take a large surface area and can be continuously processed. It is a big method. It is known that electrochemical roughening is performed by using an electrolytic solution mainly composed of hydrochloric acid or nitric acid and repeating an anodic reaction and a cathodic reaction with an alternating current to obtain a uniform roughened surface. 53-67
Japanese Patent Application Laid-Open No. 507/507 discloses a roughening method using a special electrolysis waveform. Japanese Patent Application Laid-Open No. 54-656707 discloses a method for optimizing the setting of the ratio of the amount of electricity between an anode and a cathode.
No. 331 discloses a special power supply waveform and the like.

Further, from the viewpoint of continuous processing, Japanese Patent Application Laid-Open No. 60-67699 discloses a method of suppressing the consumption of graphite electrodes by a current waveform.
Japanese Patent Application Publication No. 18-26018 discloses a method of improving the stability of an electrode by controlling a current value participating in a cathode reaction to be larger than a current value participating in an anodic reaction. Japanese Patent No. 2660582 discloses a method of generating uniform pits. There has been proposed a method which can obtain a uniform roughened surface while obtaining the same.

[0005]

However, the above-mentioned conventional electrolytic treatment methods are all excellent methods, but since they are controlled by a diode, it is impossible to supply a constant current to the auxiliary electrode. In addition, when power supply control is used, it is extremely difficult to add the existing AC power supply. In addition, the circuit of the power supply is complicated, and the investment amount is enormous.

The present invention has been accomplished as a result of intensive studies in view of such circumstances, and has been achieved by an electrolytic solution which is easily added to an existing AC power source, improves the stability of electrodes, and generates uniform pits. It is an object to provide a processing method.

[0007]

According to the present invention, in order to achieve the above object, an alternating current is supplied between an electrolytic treatment solution mainly composed of nitric acid or hydrochloric acid and the treatment solution and a counter electrode. In an AC electrolytic processing method for performing an electrochemical treatment on a material to be processed, the counter electrode is formed by a main counter electrode and an auxiliary counter electrode, and a circuit for the auxiliary counter electrode is connected in parallel to a circuit connected to the main counter electrode, and It is characterized in that a direct current is applied to the opposite electrode.

[0008] The electrolytic treatment method according to claim 1, wherein the main counter electrode is graphite. 2. The method according to claim 1, wherein the current flowing to the auxiliary counter electrode / the current of the alternating current = 0.001 to 0.3.
An electrolytic treatment method, characterized in that:

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the aluminum plate used includes pure aluminum and aluminum alloy. As the aluminum alloy, various materials can be used. For example, an alloy of aluminum such as an alloy of silicon, copper, manganese, magnesium, chromium, zinc, lead, nickel, bismuth, or the like is used. There are various types of aluminum alloys.
In JP-A-8-6635, Fe and Si components are limited, and an intermetallic compound is specified. In addition, Japanese Patent Publication No. 55-288
In Japanese Patent Publication No. 74, the cold rolling ratio and the intermediate blunting are performed, and the voltage application method for electrolytic surface roughening is limited. Tokiko 62-41
304, Japanese Patent Publication No. 46577, Japanese Patent Publication No. 1-4657
8, Japanese Patent Publication No. 1-47545, Japanese Patent Publication No. 1-35910, Japanese Patent Publication No. 63-60823, Japanese Patent Publication No. 63-60824, Japanese Patent Publication No. 4-13417, Japanese Patent Publication No. 4-19290, Japanese Patent Publication No. 4-
19291, Tokiko 4-19293, Tokiko 62-50
540, JP-A-61-272357, JP-A-62-74
060, JP-A-61-201747, JP-A-63-14
3234, JP-A-63-143235, JP-A-63-2
55338, JP-A-1-283350, EP2
72528, U.S. Pat.
0, EP394816, U.S. Pat. No. 5,010,188, West German Patent 3,232,810, U.S. Pat.
No. 239995, U.S. Pat. No. 4,822,715, West German Patent 3507402, U.S. Pat. No. 4,715,903, West German Patent 3507402, EP 289844, U.S. Pat.
9722, 4945004, West German Patent 37140
59, U.S. Pat. Nos. 4,686,083 and 4,861,396, E
Not only the aluminum alloys described in the specifications of P1588941 and the like but also all general ones. As a method for manufacturing a sheet material, a method using continuous casting as well as a method using hot rolling has been recently applied for. For example, in the specification of East German Patent 252799, a plate material performed by a twin roll method is introduced. EP22373
7, U.S. Pat. Nos. 4,802,935 and 4,800,950 each file an application with a limited alloying component. EP 415238 proposes continuous casting, continuous casting + hot rolling.

In the present invention, such an aluminum plate is subjected to various surface treatments, transfer, and the like to obtain a printing original plate having uniform unevenness, and a photosensitive layer such as a diazo compound is provided thereon. An excellent photosensitive lithographic printing plate can be obtained. In any case, it is necessary to select an appropriate material. In some cases, degreasing may be performed first. When performing a degreasing treatment, a method using a solvent such as trichlene or a surfactant, or a method using an alkali etching agent such as sodium hydroxide or potassium hydroxide is widely used. Japanese Patent Laid-Open Publication No. 2-026793 describes a degreasing treatment. For example, as a solvent degreasing method, gasoline, kerosene, benzene, solvent naphtha, a method using a petroleum solvent such as normal hexane, tolchlorethylene, methylene chloride,
There is a method using a chlorine-based solvent such as perchlorethylene or 1,1,1-trichloroethane. Examples of the alkali degreasing method include a method using an aqueous solution of a soda salt such as sodium hydroxide, sodium carbonate, sodium bicarbonate, and sodium sulfate, and sodium orthosilicate, sodium metasilicate, sodium disilicate, sodium silicate No. 3, and the like. A method using an aqueous solution of a silicate, sodium monophosphate,
There is a method using an aqueous solution of a phosphate such as sodium tertiary phosphate, sodium diphosphate, sodium tripolyphosphate, sodium pyrophosphate, sodium hexametaphosphate and the like. When the alkali degreasing method is used, the aluminum surface may be dissolved depending on the treatment time and the treatment temperature. Therefore, it is necessary to avoid the dissolution phenomenon in the degreasing treatment. As the degreasing treatment with a surfactant, an aqueous solution of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant is used.
Various commercial products and the like can be used. As a degreasing method, a dipping method, a spraying method, a method in which a liquid is contained in a cloth or the like, and rubbing can be used. In addition, immersion and spraying methods include:
Ultrasound may be used.

In the case of performing pre-polishing, in an electrochemical method, direct polishing is performed in a sulfuric acid solution. In this case, the sulfuric acid concentration is 15% to 80%, and the temperature is 40%.
~ 80 ° C, DC power supply, current density 5
^{A / dm 2 ~50A / dm 2} , as the quantity of electricity, 100
３3000 c / dm ² is appropriate. When mechanically performed, it is preferable to carry out preliminary polishing by a roller made of a nonwoven fabric made of polyamide, polyester, rayon or the like containing an abrasive having an average particle size of 1 to 25 μm. As the conditions for the preliminary polishing, it is necessary to select conditions that can maintain the surface roughness to some extent. The roller diameter is 200 to 1000 mm. In order to maintain a uniform surface quality, vibration is applied in the direction perpendicular to the rolling direction of the original sheet, and in the case of continuous processing, in the direction perpendicular to the line direction, 5 to 2000 times / minute. preferable. In any case, it is important to make the center line surface roughness 0.15 to 0.35 μm and the maximum surface roughness 1 to 3.5 μm by preliminary polishing. That is, it is important that the center line average surface roughness and the maximum surface roughness are not limited to the above-mentioned DC electrolysis and / or pre-polishing by a roller.

[0012] Mechanical roughening also includes transfer, brush,
There are various methods such as liquid honing, and it is important to select in consideration of productivity and the like. Various methods can be used as the transfer method for pressing the uneven surface onto the aluminum plate. That is, the aforementioned JP-A-55-74898,
JP-A-60-36195, JP-A-60-203496
In addition to the above publications, the methods disclosed in JP-A-6-55871, in which transfer is performed several times, and JP-A-6-24168, in which the surface is elastic, can be applied. .

Further, by using electric discharge machining, shot blasting, laser etching, plasma etching, or the like, the transfer is repeatedly performed using a roller having fine irregularities etched thereon, or the uneven surface coated with the fine particles is coated with aluminum. It is also possible to make the aluminum plate come in contact with the plate, apply a plurality of line return pressures thereon, and repeatedly transfer the concavo-convex pattern corresponding to the average diameter of the fine particles to the aluminum plate a plurality of times.

Japanese Patent Application Laid-Open No. 3-08635 and Japanese Patent Application Laid-Open No. 3-06664 disclose methods for imparting fine irregularities to the transfer roller.
No. 04, JP-A-63-065017 and the like are known. Further, fine grooves may be cut on the roller surface from two directions by using a die, a cutting tool, a laser, or the like, so that the surface may be provided with square irregularities. The surface of the roller may be subjected to a known etching process or the like, so that the formed square irregularities are rounded. Of course, quenching, hard chrome plating or the like may be performed to increase the surface hardness.

The surface roughening with a brush includes the surface roughening with a wire brush in addition to the surface roughening with a nylon brush. Japanese Patent Application Laid-Open Nos. 59-21469 and 60-19595 describe a roughening method using high-pressure water.
And JP-A-60-18390. After being prepared by such mechanical roughening, the aluminum surface is chemically treated with an acid or an alkali as required for the purpose of smoothing and equalizing the aluminum plate.
In particular, in the case where electrochemical surface roughening is performed, the surface roughening becomes non-uniform in the case where the surface roughening is performed continuously after transfer. Specific examples of the acid and alkali used in such chemical treatment include a method using an aqueous solution of a soda salt such as phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium sulfate, orthosilicate. Using aqueous solutions of silicates such as sodium silicate, sodium metasilicate, sodium disilicate and sodium silicate, sodium monophosphate, sodium tertiary phosphate, sodium diphosphate, sodium tripolyphosphate, pyrophosphate There is a method using an aqueous solution of a phosphate such as sodium or sodium hexametaphosphate. The processing conditions include a concentration of 0.01% to 50% by weight, a temperature of 20 ° C to 90 ° C, and a time of 5%.
It is selected as appropriate from seconds to 5 minutes. The amount of etching is appropriately selected depending on the material of aluminum and the required quality. JP-A-54-65607, JP-A-55-125
No. 299 proposes a pretreatment for electrochemical surface roughening. JP-A-63-235500, JP-A-63-3
07990, JP-A-1-127388, JP-A-1-16
0690, JP-A-1-136789, JP-A-1-136
788, JP-A-1-178497, JP-A-1-30886
89, JP-A-3-126687, JP-A-3-12690
0, Japanese Patent Application Laid-Open No. 3-173800, etc., include various pre-processing, but the present invention is not limited to these. However, when the aluminum surface is chemically treated with an acid or alkali aqueous solution, an insoluble residue, that is, a smut is generated on the surface. This smut can be removed with phosphoric acid, nitric acid, sulfuric acid, chromic acid or mixtures thereof. In the present invention,
The aluminum surface to be subjected to the electrochemical graining treatment is desirably a clean surface without smut. However, this can be omitted when the electrolytic solution is an acid and has a desmutting effect.

The thus treated aluminum web is subjected to electrochemical treatment and surface roughening. The details of the invention will be described with reference to FIGS. 3 and 4 show a conventional system in which electrochemical processing is performed only with the AC power supply 5. In this case, the current flowing through the main counter electrode 2 is A = B,
C = D, and the main counter electrode deteriorates. Reference numeral 1 denotes a metal web, reference numeral 7 denotes a pass roller, and reference numeral 9 denotes an insulator.

1 and 2 show an example of the present invention, in which an auxiliary counter electrode 3 is provided, a DC power supply 6 is connected to the auxiliary counter electrode 3, and the current flowing through the main counter electrode 2 is represented by A. By controlling to <B, C <D, it is characterized in that the main counter electrode 2 can be easily attached to an existing apparatus using the AC power supply 5 without modification of the power supply while preventing deterioration of the main counter electrode 2. It is desirable that the DC power supply 6 controls the current value together with the AC power supply 5, and the current / alternating current of the auxiliary counter electrode 3 is preferably 0.001-0.3, and the current / alternating current of the auxiliary counter electrode 3 is preferably 0.001-0.3. Current = 0.01-0.
2 is more preferable, and 0.03 to 0.1 is further preferable.
The electrode of the main counter electrode 2 is preferably graphite, and preferably has a specific resistance of 5.20 μΩm in terms of the function of the electrode. Further, the maximum particle size is preferably 3 mm or less, and if the particle size is larger than this, the consumption becomes severe. On the other hand, in the auxiliary counter electrode 3, a clad type of platinum and titanium, a plated type, a combination of platinum and tantalum, a combination of iridium oxide and titanium, a ferrite electrode, and the like can be used. In any case, it is important to devise current conditions, electrode materials, and electrolyte concentrations so that the electrodes are not consumed.

Regarding the electrochemical surface roughening, see JP-B-48
-28123 and British Patent 896563. The above-mentioned electrolytic graining uses a sine wave alternating current in the prior art.
The measurement may be performed using a special waveform as described in Japanese Patent Application Laid-Open No. 602/602. JP-A-55-158298, JP-A-56-28898, JP-A-52-58602, JP-A-52-152302, JP-A-54-85802, JP-A-60-190392, and JP-A-58-120531 JP-A-63-176187, JP-A-1-588
9, JP-A-1-280590, JP-A-1-11848
9, JP-A-1-148592, JP-A-1-17849
6, JP-A-1-188315, JP-A-1-15479
7, JP-A-2-235794, JP-A-3-26010
0, JP-A-3-253600, JP-A-4-72079,
The methods described in JP-A-4-72098, JP-A-3-267400 and JP-A-1-141994 can also be applied.

As the frequency, in addition to the above, those proposed for electrolytic capacitors can be used. For example,
U.S. Pat. Nos. 4,276,129 and 4,676,879. Examples of the electrolyte include nitric acid, hydrochloric acid and the like, as well as those described in U.S. Patent Nos. 4,671,859, 466,576, and 466121.
9, 4618405, 462628, 46004
82, 4566960, 4566958, 456
6959, 4416972, 4374710, 4
Electrolyte solutions described in 336113 and 4184932 can also be used. Various proposals have been made for an electrolytic cell and a power source, but are described in US Pat.
-123400, JP-A-57-59770, JP-A-57-53770
-12738, JP-A-53-32821, JP-A-53-328
32822, JP-A-53-32823, JP-A-55-1
22896, JP-A-55-132883, JP-A-62-162
127500 publications, JP-A-1-52100,
JP-A-1-52098, JP-A-60-67700
JP, JP-A 1-230800, JP-A 3-2
No. 57199. In addition to the above-mentioned patents, various proposals have been made. For example, Japanese Patent Application Laid-Open No. 52-586
02, JP-A-52-152302, JP-A-53-127
38, JP-A-53-12739, JP-A-53-3282
1, JP-A-53-32822, JP-A-53-3283
3, JP-A-53-32824, JP-A-53-3282
5, JP-A-54-85802, JP-A-55-12289
6, JP-A-55-132883, JP-B-48-2812
3, JP-B-51-7081, JP-A-52-13383
8, JP-A-52-133840, JP-A-52-1338
44, JP-A-52-133845, JP-A-53-149
135 and those described in JP-A-54-146234 can also be applied.

As described above, the removal of the smut is performed using the same components as the electrolytic solution. If smut removal is performed using a liquid having a component different from that of the electrolytic solution, a water washing step is required after the smut removal step, which not only causes an increase in cost but also affects electrolytic graininess. Further, if the same components are used, even if the temperature and the concentration are changed, the temperature and the concentration can be controlled and controlled in the electrolytic surface roughening step. As a method of removing the smut, there is a method of chemically dissolving or the like. However, the smut may be forcibly removed by causing the liquid to collide with the web at high speed by spraying or the like. In any case, the selection may be made by comprehensively considering the productivity, equipment cost, cell shape for electrolytic surface roughening, and the like. The smut amount is 5% to 7 for each method.
It is important to remove 0%. The amount of smut generated by electrolytic surface roughening is 0.2 g / m ^{2 to} 5
Since it changes by about g / m ^{2, the} amount of smut may be changed within this range in order to remove with desired quality performance.

The thus obtained aluminum plate is optionally treated with an alkali or an acid. An alkali treatment is carried out as in JP-A-56-51388, and a desmut treatment with sulfuric acid is carried out as in JP-A-53-12739. Further, as described in JP-A-53-115302, phosphoric acid treatment,
JP-A-63-176188, JP-A-1-38291, JP-A-1-127389, JP-A-1-188699, JP-A-3-177600, JP-A-3-126891, and JP-A-3-191100 can also be used. it can.

As described above, after roughening and etching are performed by mechanical surface roughening, chemical etching, or electrochemical surface roughening, unevenness is generated.糸 500 μm thread-like fibers are used. If the diameter is less than 5 μm, the tip cannot be shaved. If the diameter exceeds 500 μm, the surface will be scratched and it will be difficult to use it as a lithographic printing plate. Further, it is preferably from 10 to 100 μm, and more preferably from 15 to 50 μm. The diameter is determined from an average value of ten or more enlarged photographs taken with a SEM photograph or the like.
As the material, chemical fibers such as 6-nylon and 6-10 nylon, animal hair, and the like are used. As a binder for bonding the nylon and the like, acrylic, NBR, and the like are used.
Further, in order to improve the productivity, it is necessary to continuously treat the AL plate. In such a case, such a fiber is formed into a roll, and the fiber is rotated at a high speed to cut the convex portion. In the case of a roll, if the hardness of the roll surface is too hard, AI
Since the surface is easily damaged, the roll needs to have a hardness of 60 degrees or less. For the measurement of hardness, SRISO101
(JIS of Japan Rubber Association), conform to JISS6050,
The type of the measuring instrument is a spring type hardness tester Asuka-C type. The peripheral speed of the roll is 50-200
0 m / min is appropriate, and stable operation can be achieved by supplying water for the purpose of preventing heating. This step is performed after roughening and etching by mechanical roughening or chemical etching or electrochemical roughening,
It may be performed after all the steps, or may be performed after one of the roughening and etching steps, and may be changed as needed according to the required quality.

It is preferable to form an anodic oxide film on the surface of the aluminum support thus obtained. As the electrolytic solution, sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, or the like, or an aqueous solution or a non-aqueous solution combining two or more of these, when current is passed using aluminum as an anode,
An anodized film can be formed. The anodizing treatment conditions vary depending on the electrolytic solution used, and thus cannot be determined unconditionally.
~ 80 wt%, liquid temperature 5 ~ 70 ° C, current density 0.5 ~ 60
A / cm ² , voltage 1-100V, electrolysis time 15 seconds-50
Minutes are appropriate. As an electrolytic apparatus, Japanese Patent Application Laid-Open No. 48-26
638, JP-A-47-18739, JP-B-58-245.
17 publications. Also, Japanese Patent Application Laid-Open No.
81133, JP-A-57-47894, JP-A-57-5-5
1289, JP-A-57-51290, JP-A-57-54
300, JP-A-57-136596, JP-A-58-10
7498, JP-A-60-200256, JP-A-62-1
36596, JP-A-63-176494, JP-A-4-14-1
76897, JP-A-4-280997, JP-A-6-20
7299, JP-A-5-32083, JP-A-5-1255
97 and JP-A-5-195291 can also be used. Examples of the processing liquid include JP-A-3-253596, JP-A-62-82089, and JP-A-1
133794, JP-A-54-32424, JP-A-5-324
Of course, the liquids described in Japanese Patent No. 42783 can also be used.

After forming the anodic oxide film as described above,
In order to optimize the adhesion between each support and the photosensitive composition, after etching the anodic oxide film, steam and
There is a sealing device for a support which is subjected to sealing treatment with hot water to give a photosensitive printing plate having good aging stability, good developability and no stain on the non-image area. The post-treatment of film formation may be performed by such an apparatus. Also, JP-A-4-4194, JP-A-5-2024
96, JP-A-5-179482, and the like, and the sealing treatment may be performed by an apparatus or method.

Other examples include potassium fluoride zirconate treatment described in US Pat. No. 2,946,638 and phosphomolybdate treatment described in US Pat. No. 3,012,247, British Patent No. 1108559. Alkyl titanate treatment, German Patent No. 109
No. 1433, polyacrylic acid treatment, German Patent No. 1134093 and British Patent No. 1
No. 2304747, polyvinylphosphonic acid treatment, JP-B-44-6409, phosphonic acid treatment, U.S. Pat. No. 3,307,951, phytic acid treatment, JP-A-58. -16
No. 893 or JP-A-58-18291, and treatment with a salt of a lipophilic organic polymer compound with a divalent metal, as described in US Pat. No. 3,860,426. An undercoat layer of hydrophilic cellulose (for example, carboxymethylcellulose, etc.) containing a water-soluble metal salt (for example, zinc acetate, etc.);
No. 101651, a water-soluble polymer having a sulfonic acid group which has been subjected to a hydrophilizing treatment by undercoating, a phosphate described in JP-A-62-19494, and a phosphate described in JP-A-62-19494. Water-soluble epoxy compound described in JP-A-03-03692, JP-A-62-097
No. 892, phosphoric acid-modified starch,
No. 056498, a diamine compound described in JP-A-63-130391, an inorganic or organic acid of an amino acid described in JP-A-63-130391, an organic phosphonic acid containing a carboxyl group or a hydroxyl group described in JP-A-63-145092, Compounds having an amino group and a phosphonic acid group described in JP-A-63-165183, specific carboxylic acid derivatives described in JP-A-2-316290, JP-A-1-27259
Patent No. 4, JP-A-3-2615
No. 92, one amino group and oxygen acid group 1 of phosphorus
Compounds having a single bond, phosphates described in JP-A-3-215095, aliphatic or aromatic phosphonic acids such as phenylphosphonic acid described in JP-A-5-246171, and JP-A-1-307745. Compounds containing an S atom, such as thiosalicylic acid described in JP-A-4-28.
Undercoating, such as a compound having an oxygen acid group of phosphorus, described in JP-A-2637, and coloring with an acid dye described in JP-A-60-64352 can also be performed.

The support of the present invention preferably has the following characteristics. Regarding the features of the grain shape When the AL plate grained in the roughening step is used as a lithographic printing plate support, the following properties are desired. Center line surface roughness (JIS-BO601-1970)
1.0 μm is desirable, and more preferably 0.4 to 0.1 μm.
8 μm is preferred. The average surface roughness of the surface of the photosensitive layer after development is preferably 0.35 μm or more. Further, the relative load length at a position 1.5 μm lower than the cutting level 50% of the load curve in the surface roughness meter is preferably 90% or more. The center line surface roughness after electrochemical roughening, chemical etching, and desmutting is the same as the center line surface roughness after mechanical roughening, chemical etching, and desmutting. Preferably, it is 0.9-1.5 times.

According to the physical properties measured by an atomic force microscope (AFM), when the inclination of the surface inclination distribution is 30 degrees, 5
The ratio of -40% and 45 degrees or more is preferably 5 to 50%.
The following range is preferable for the root mean square surface roughness. 1.5 ≤ R _ms (10 to 100 m) / R _ms (1 to 10 m) ≤ 3.
0 0.2 ≦ R _ms (1 to 10 μm) ≦ 0.4 μm 0.4 ≦ R _ms (10 to 100 μm) ≦ 1.0 μm In terms of the comparison area, 1.1 to 1.6 is preferable.

The undulation of the aluminum plate is preferably a grain in which a large wave having an average pitch of 5 to 30 μm and a grain of 0.5 to 3 μm are superimposed, and in particular, 0.5 to 2 μm is uniformly formed on the entire surface. It is particularly preferable that the pit density is 1 × 10 ⁵ to 1 × 10 ⁷ / mm ² . In addition, when the opening diameter is plotted on the horizontal axis and the cumulative frequency (%) is drawn on the vertical axis, the opening diameter corresponding to 5% and 95% of the cumulative frequency curve is preferably 0.8 μm or more and 15 μm or less. The arithmetic mean of the pore sizes is 0.
Preferably, the portion A of the surface, which is between 5 and 5 μm and has no pores or only pores with a maximum of 0.5 μm, is less than 30% of the surface area. The support of the present invention may be provided with a photosensitive layer as exemplified below to form a photosensitive lithographic printing plate.

[1] A case where a photosensitive layer containing a novolak resin of a mixture of o-naphthoquinonediazidosulfonic acid ester and phenol / cresol is provided. The o-quinonediazide compound is an o-naphthoquinonediazide compound, for example, U.S. Pat. No. 2,766,118.
No. 2,767,092, No. 2,772,97
No. 2, No. 2,859,112, No. 3,102,8
09, 3,106,465 and 3,635
No. 709, No. 3,647,443, and many other publications, and these can be suitably used. Of these, o-naphthoginonediazidosulfonic acid ester or o-naphthoquinonediazidocarboxylic acid ester of an aromatic hydroxy compound, and o-naphthoquinonediazidosulfonic acid amide or o-naphthoquinonediazidecarboxylic acid amide of an aromatic amino compound And, in particular, U.S. Pat.
U.S. Pat. No. 4,028,1 which is obtained by subjecting a condensate of pyrogallol and acetone to an ester reaction with o-naphthoquinonediazidosulfonic acid described in US Pat.
No. 11, a polyester having a hydroxy group at a terminal, obtained by subjecting an o-naphthoquinonediazidesulfonic acid or an o-naphthoquinonediazidecarboxylic acid to an ester reaction, described in British Patent No. 1,494,043. A homopolymer of p-hydroxystyrene or a copolymer thereof with another copolymerizable monomer as described, which is subjected to an ester reaction with o-naphthoquinonediazidosulfonic acid or o-naphthoquinonediazidocarboxylic acid; Copolymers of p-aminostyrene and other copolymerizable monomers, as described in U.S. Pat. No. 3,759,711, may be treated with o-naphthoquinonediazidesulfonic acid or o-naphthoquinonediazidecarboxylic acid. Is very excellent.

These o-quinonediazide compounds can be used alone, but are preferably used in combination with an alkali-soluble resin. Suitable alkali-soluble resins include novolak-type phenol resins, and specifically include phenol formaldehyde resin, o-cresol formaldehyde resin, m-cresol formaldehyde resin, and the like. No. 4,028, U.S. Pat.
As described in JP-A-111, a condensate of formaldehyde with phenol or cresol substituted with an alkyl group having 3 to 8 carbon atoms, such as a t-butylphenol formaldehyde resin, is used in combination with the phenol resin described above. Then, an o-naphthoquinonediazide is more preferable in order to form a visible image by exposure.
Compounds such as 4-sulfonyl chloride, inorganic anion salts of p-diazodiphenylamine, trihalomethyloxadiazole compounds, and trihalomethyloxadiazole compounds having a benzofuran ring are added. On the other hand, a triphenylmethane dye such as Victoria Blue BOH, Crystal Violet, or Oil Blue is used as a colorant for an image. Also, Japanese Patent Application Laid-Open No. Sho 62-29324
The dye described in JP-A No. 7 is particularly preferred.

Further, as a sensitizing agent, JP-B-57-23
No. 253, a phenol substituted with an alkyl group having 3 to 15 carbon atoms, for example, t-butylphenol, N-octylphenol, a novolak resin obtained by condensing t-butylphenol with formaldehyde, or such a novolak resin. O-naphthoquinonediazide-4- or -5-sulfonic acid ester of a novolak resin (for example, described in JP-A-61-242446).

Further, in order to improve the developing property, a nonionic surfactant as described in JP-A No. 62-251740 can be further contained. The above composition is dissolved in a solvent that dissolves each of the above components, and coated on a support. As the solvent used here, ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, lactic acid There are methyl, ethyl lactate, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol, isopropanol, diethylene glycol dimethyl ether, and the like. Mix and use.

The photosensitive composition comprising these components is provided in a solid content of 0.5 to 3.0 g / m ² . [2] When a photosensitive layer containing a diazo resin and a water-insoluble and lipophilic photomolecular compound is provided. Examples of the diazo resin include, for example, a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde, hexafluorophosphate, tetrafluoroborate, an inorganic salt of a diazo resin which is a reaction product of this organic solvent soluble, and US Pat. No. 3,300,309, the condensate and a sulfonic acid such as P
-Toluenesulfonic acid or a salt thereof, phosphinic acids such as benzenephosphinic acid or a salt thereof, and a hydroxyl group-containing compound such as 2,4-dihydroxybenzophenone or 2-hydroxy-4-methoxybenzophenone-
Organic solvent-soluble diazo resin organic acid salts, which are reaction products such as 5-sulfonic acid or salts thereof, and the like.

In the present invention, other diazo resins that can be suitably used include carboxyl groups, sulfonic groups,
It is a cocondensate containing, as a structural unit, an aromatic compound having at least one organic group among a sulfinic acid group, an oxygen acid group of phosphorus, and a hydroxyl group, and a diazonium compound, preferably an aromatic diazonium compound. The aromatic ring preferably includes a phenyl group and a naphthyl group.

The aromatic compound containing at least one of the above-mentioned carboxyl group, sulfonic acid group, sulfinic acid group, oxygen acid group of phosphorus, and hydroxyl group includes various ones. 4-methoxybenzoic acid, 3-chlorobenzoic acid, 2,4-dimethoxybenzoic acid, p-phenoxybenzoic acid, 4-anilinobenzoic acid, phenoxyacetic acid, phenylacetic acid, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid Acids, benzenesulfonic acid, p-toluenesulfinic acid, 1-naphthalenesulfonic acid, phenylphosphoric acid, and phenylphosphonic acid. Examples of the aromatic diazonium compound constituting the constitutional unit of the aforementioned co-condensed diazo resin include, for example, JP-B-49-48001.
Although diazonium salts such as those described in JP-A No. 2-2,086 can be used, diphenylamine-4-diazonium salts are particularly preferred.

Diphenylamine-4-diazonium salts are derived from 4-aminodiphenylamines, and such 4-aminediphenylamines include 4-aminodiphenylamine, 4-amino-3-methoxydiphenylamine, -Amino-2-methoxydiphenylamine, 4'-amino-2-methoxydiphenylamine, 4'-amino-4-methoxydiphenylamine, 4-amino-3-methyldiphenylamine, 4-amino-3-ethoxydiphenylamine, 4-amino- 3
-Β-hydroxyethoxydiphenylamine, 4-amino-diphenylamine-2-sulfonic acid, 4-amino-
Examples thereof include difunylamine-2-carboxylic acid and 4-amino-diphenylamine-2′-carboxylic acid, and particularly preferable are 3-methoxy-4-amino-4-diphenylamine and 4-aminodiphenylamine.

As a diazo resin other than a cocondensation diazo resin with an aromatic compound having an acid group, Japanese Patent Application Laid-Open No.
559, JP-A-3-163551 and JP-A-3-25
The diazo resin condensed with an aldehyde containing an acid group or an acetal compound thereof described in each of 3857 can also be preferably used. The counter anion of the diazo resin includes an anion that forms a salt with the diazo resin stably and makes the resin soluble in an organic solvent. These include organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids and sulfonic acids such as phenylphosphoric acid, and typical examples are fluoroalkanesulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid. , Laurylsulfonic acid, dioctylsulfosuccinic acid, dicyclohexylsulfosuccinic acid, camphor-sulfonic acid, tolyloxy-3-propanesulfosic acid, nonylphenoxy-3-propanesulfonic acid, nonylphenoxy-4-butanesulfonic acid, dibutylphenoxy-3-acid Propanesulfonic acid, diamylphenoxy-3-propanesulfonic acid, dinonylphenoxy-3-propanesulfonic acid, dibutylphenoxy-4-butanesulfonic acid, dinonylphenoxy-4-butanesulfonic acid, benzenesulfonic acid, toluenes Fonic acid, mesitylenesulfonic acid, p-chlorobenzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, p-acetylbenzenesulfonic acid, 5-nitro-o-toluenesulfonic acid 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-chloro-5-nitrobenzenesulfonic acid, butylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, Butoxybenzenesulfonic acid, dodecyloxybenzenesulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, isopropylnaphthalenesulfonic acid, butylnabutalenesulfonic acid, hexylnaphthalene Fonic acid, octylnaphthalenesulfonic acid, butoxynaphthalenesulfonic acid, dodecyloxynaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, dioctylnaphthalenesulfonic acid, triisopropylnaphthalenesulfonic acid, tributylnaphthalenesulfonic acid, 1-naphthol-5-sulfonic acid, naphthalene -1-sulfonic acid, naphthalene-2-sulfonic acid,
Aliphatic and aromatic sulfonic acids such as 1,8-dinitronaphthalene-3,6-disulfonic acid and dimethyl-5-sulfoisophthalate, 2,2 ′, 4,4′-tetrahydroxybenzophenone, Hydroxyl-containing aromatic compounds such as 2,3-trihydrooxybenzophenone and 2,2'4-trihydroxybenzophenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid,
HC10 _4, HI0 perhalogen acids such as _4, and the like, but not limited thereto. Of these, particularly preferred are butyl naphthalene sulfonic acid, dibutyl naphthalene sulfonic acid, hexafluorophosphoric acid,
Hydroxy-4-methoxybenzophenone-5-sulfonic acid, dodecylbenzenesulfonic acid.

The molecular weight of the diazo resin used in the present invention can be obtained as desired by changing the molar ratio of each monomer and the condensation conditions, but it is effective for the intended use of the present invention. To provide a molecular weight of about 400
~ 100,000, preferably about 800-8,
000 is suitable. Examples of the water-insoluble and lipophilic high molecular compound include copolymers having a molecular weight of usually from 100,000 to 200,000, having monomers shown in the following (1) to (15) as structural units. (1) Acrylamides, methacrylamides, acrylates, methacrylates and hydroxystyrenes having an aromatic hydroxyl group, for example, N- (4-
Hydroxyphenyl) acrylamide or N- (4-
(Hydroxyphenyl) methacrylamide, o-, m-,
p-hydroxystyrene, o-, m-, p-hydroxyphenyl-acrylate or methacrylate. (2) Acrylic esters and methacrylic esters having an aliphatic hydroxyl group, for example, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, (3) acrylic acid, methacrylic acid, maleic anhydride (4) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, benzyl acrylate, Acrylic acid-2-
(Substituted) alkyl acrylates such as chloroethyl, glycidyl acrylate and N-dimethylaminoethyl acrylate. (5) methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, glycidyl methacrylate, N
(Substituted) alkyl methacrylates such as -dimethylaminoethyl methacrylate, (6) acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N Acrylamide or methacrylamides such as -hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide, (7) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether , Vinyl ethers such as butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether; (8) vinyl Vinyl esters such as acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate; (9) styrenes such as styrene, α-methyl styrene and chloromethyl styrene; (10) methyl vinyl ketone, ethyl vinyl ketone, and propyl vinyl Vinyl ketones such as ketone and phenyl vinyl ketone; (11) olefins such as ethylene, propylene, isobutylene, butadiene and isoprene; (12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile and methacrylonitrile (13) unsaturated imides such as maleimide, N-acryloyl acrylamide, N-aceketyl methacrylamide, N-propionyl methacrylamide, N- (p-chlorobenzoyl) methacrylamide, and (14) N (o- (Aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-amino) sulfonylphenylmethacrylamide, N- (1- (3-aminosulfonyl) naphthyl) methacrylamide, N- ( Methacrylamides such as 2-aminosulfonylethyl) methacrylamide, and acrylamides having the same substituents as described above, and o-aminosulfonylphenylbutmethacrylate, m-aminosulfonylphenylmethacrylate, and p-aminosulfonylphenylmethacrylate , 1
Unsaturated sulfonamides such as methacrylates such as-(3-aminosulfonylnaphthyl) methacrylate and acrylates having the same substituents as described above (15) N- (2- (methacryloyloxy) monoethyl) Unsaturated monomers having a crosslinkable group in the side chain, such as -2,3-dimethylmaleimide and vinyl cinnamate; Further, a monomer copolymerizable with the above monomer may be copolymerized. (16) Phenol resins described in U.S. Pat. No. 3,751,257 and polyvinyl acetal resins such as polyvinyl formal resins and polyvinyl butyral resins. (17) Tokiko Sho 54 made of alkali-soluble polyurethane
-19773, JP-A-57-904747 and JP-A-57-904747.
-182437, 62-58242, 62-1
No. 23452, No. 62-123453, No. 63-11
No. 3450, and a polymer compound described in JP-A-2-14642.

If necessary, a polyvinyl butyral resin, a polyurethane resin, a polyamide resin, an epoxy resin, a nopolak resin, a natural resin, or the like may be added to the above copolymer. In the photosensitive composition used for the support of the present invention, a dye can be further used for the purpose of obtaining a visible image by exposure and a visible image after development.

Examples of the pigment include Victoria Pure-BOH (manufactured by Hodogaya Chemical Co., Ltd.) and Oil Bull- #
603 (manufactured by Orient Chemical Co., Ltd.), patent pure- (manufactured by Sumitomo Mikuni Chemical Co., Ltd.), crystal violet,
Brilliant green, ethyl violet, methyl violet, methyl green, erythrosin B, basic fuchsin, malachite green, oil red, m
-Cresol purple, rhodamine B, auramine, 4
Triphenylmethane, diphenylmethane represented by -p-diethylaminophenyliminaphthoquinone, cyano-p-diethylaminophenylacetanilide and the like;
Oxazine, xanthene, iminonaphthoquinone,
The azomethine-based or anthraquinone-based dye is mentioned as an example of a color-changing agent that changes from colored to colorless or a different colored tone.

On the other hand, examples of the color changing agent which changes from colorless to colored include leuco dyes and, for example, triphenylamine, diphenylamine, o-chloroaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p '-Bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p, p',
p "-tris-dimethylaminotriphenylmethane,
p, p-bis-dimethylaminodiphenylmethylimine, p, p, p "-triamino-o-methyltriphenylmethane, p, p-bis-dimethylaminodiphenyl-
Primary or secondary arylamine dyes represented by 4-anilinonaphthylmethane and p, p, p "-triaminotriphenylmethane are preferred. Particularly preferred are:
Triphenylmethane-based and diphenylmethane-based dyes are effectively used, more preferably triphenylmethane-based dyes, and particularly Victoria Pure-BOH.

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

In order to provide the above-mentioned photosensitive composition on a support, a predetermined amount of a photosensitive diazo resin, a lipophilic polymer compound, and, if necessary, various additives are added to a suitable solvent (methyl cellosolve, ethyl Cellosolve, dimethoxyethane, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethylformamide, dimethylacetamide, cyclohexanone, dioxane,
Tetrahydrofuran, methyl lactate, ethyl lactate, ethylene dichloride, dimethyl sulfoxide, water, or a mixture thereof) to prepare a coating solution of the photosensitive composition, and then apply the solution on a support and dry it.

The solvent used may be a single solvent.
Cellosolve, 1-methoxy-2-propanol, lactate
High boiling solvents such as chill, methanol and methyl ethyl
Even better is a mixture with a low boiling point solvent such as a ketone.
Good. The solid content concentration of the photosensitive composition at the time of application is 1 to
It is desirable that the content be in the range of 50% by weight. In this case, feeling
The coating amount of the light-sensitive composition is approximately 0.2 to 10 g / m.
^Two(Dry weight), and more preferably,
0.5-3g / m^TwoIt is good to

[3] A case where a photosensitive layer containing the photodimerizable photosensitive composition and the photopolymerizable photosensitive composition is provided. The photodimerization type photosensitive composition includes a maleimide group or a cinnamyl group, a cinnamoyl group, a cinnamylidene group, a polymer having a cinnamylidene acetyl group or a chalcone group in a side chain, or a main chain, and a maleimide group in a side chain. Examples of the polymer having the compound include JP-A-52-988 (corresponding to U.S. Pat. No. 4,079,041) and German Patent No. 2,6.
26,769, EP 21,019
And European Patent No. 3,552, and Dee Angelbandute Macromolecule Chemie
(Die Angewandte Makromolekulare Chemie) 115 (1
983), pages 163 to 181 and JP-A-49-128991 and JP-A-49-12891.
No. 992, No. 49-128993, No. 50-5376
No. 50-5377, No. 50-5379, No. 50
No.-5378, No.50-5380, No.53-5298
Nos. 53-5299, 53-5300, 50
No. -50107, No. 51-47940, No. 52-13
No. 907, No. 50-45076, No. 52-12170
Nos. 0, 50-10884 and 50-45087, German Patent Nos. 2,349,948 and 2,61.
No. 6,276, and the like.

In order to make these polymers soluble or swellable in alkaline water, they are dissociated in carboxylic acid / sulfonic acid, phosphoric acid, phosphonic acid, their alkali metal salts and ammonium salts, and in alkaline water. pK
It is useful that a contains 6 to 12 acid groups in the polymer. If necessary, monomer 13 having the above acid group
A type and a monomer having a maleimide group can be copolymerized.

The acid value of the maleimide polymer having an acid group is preferably in the range of 30 to 300. Among the polymers having such an acid value, Die Angewandte Makromolekul
copolymers of N- [2- (methacryloyloxy) ethyl] -2,3-dimethylmaleimide and methacrylic acid or acrylic acid, as described on pages 71 to 91 of Chem. Useful.
Furthermore, by synthesizing the vinyl monomer of the third component at the time of synthesizing the copolymer, a multi-component copolymer suitable for the purpose can be easily synthesized. For example, by using an alkyl methacrylate or an alkyl acrylate whose homopolymer has a glass transition point of room temperature or lower as the vinyl monomer of the third component, flexibility can be given to the copolymer.

As a photocrosslinkable polymer having a cinnamyl group, a cinnamoyl group, a cinnamylidene group, a cinnamylidene acetyl group or a chalcone group in a side chain or a main chain, US Pat. 7
There are photosensitive polyesters described in JP-A-09-496 and JP-A-828-455. The followings are examples of those obtained by solubilizing these photocrosslinkable polymers with alkaline water.

That is, there can be mentioned a photosensitive polymer as described in JP-A-60-191244. Further, Japanese Patent Application Laid-Open Nos. Sho 62-175729 and
Examples thereof include photosensitive polymers described in JP-A-2-175730, JP-A-63-25543, JP-A-63-218944, and JP-A-63-218945.

A sensitizer can be used in the photosensitive layer containing these compounds. Examples of the sensitizer include benzophenone derivatives,. Examples include benzuanthrone derivatives, quinones, aromatic nitro compounds, naphthothiazoline derivatives, benzothiazoline derivatives, thioxanthones, naphthothiazole derivatives, ketocoumarin compounds, benzothiazole derivatives, naphthofuranone compounds, beryllium salts, and thiavirylium salts. In such a photosensitive layer, chlorinated polyethylene, chlorinated polypropylene, alkyl acrylate, alkyl acrylate, acrylonitrile, vinyl chloride,
Styrene, a binder with at least one kind of monomer such as butadiene, a binder such as polyamide, methylcellulose, polyvinyl formal, polyvinyl butyral, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, and dibutyl phthalate And plasticizers such as dialkyl phthalate such as dihexyl phthalate, oligoethylene glycol alkyl ester and phosphate ester. Further, for the purpose of coloring the photosensitive layer, a dye or a pigment or a printing agent such as p
It is also preferable to add an H support agent or the like.

Examples of the photopolymerizable photosensitive composition include unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyamine compounds. And the like. Examples of photopolymerization initiators include vicinal polytaketaldonyl compounds, α-carbonyl compounds, acyloin ethers, α-
Acyloin compound substituted at the hydrocarbon position, polynuclear quinone compound, triallylimidazole dimer / p
A combination of -aminophenyl ketone, a benzothiazole compound, a trihalomethyl-s-triazine compound,
Acridine and phenazine compounds, oxadiazole compounds and the like are included. Together with these, the polymer capable of forming a film in an alkali water-soluble or swellable form is benzyl (meth) acrylate / (meth) acrylic acid / necessary. Other addition polymerizable vinyl monomer copolymers, methacrylic acid / methyl methacrylate (or methacrylic acid ester) copolymers, and maleic anhydride copolymers added with pentaerythritol triacrylate by half esterification according to And acidic vinyl copolymers.

[4] Electrophotographic Photosensitive Layer For example, a ZnO photosensitive layer disclosed in US Pat. No. 3,001,872 can be used. Also,
JP-A-56-161550, JP-A-60-18684
No. 7, JP-A-61-238063, etc., a photosensitive layer using an electrophotographic photosensitive member may be used.

[0053] The amount of the photosensitive layer provided on the support, by dry weight after application, drug 0.1 to about 7 g / m ^2, preferably in the range of 0.5-4 g / m ^2. In the method for producing a lithographic printing plate support according to the method of the present invention, in order to increase the adhesion between the support and the photosensitive layer, to prevent the photosensitive layer from remaining after development, or to prevent halation. An intermediate layer may be provided if necessary.

In order to improve the adhesion, the intermediate layer is generally
Diazo resins and phosphoric acid compounds that adsorb to aluminum, for example,
It is composed of an amino compound, a carboxylic acid compound and the like.
The intermediate layer made of a substance having high solubility so that the photosensitive layer does not remain after development is generally made of a polymer having good solubility or a water-soluble polymer. In order to further prevent halation, the intermediate layer generally contains a dye or a UV absorber. The thickness of the intermediate layer is arbitrary, and must be a thickness capable of performing a uniform bond-forming reaction with the upper photosensitive layer upon exposure. Usually, a dry solid has a good coating ratio of about 1 to 100 mg / m ² , and 5 to 40 mg / m ² is particularly good.

On the coated photosensitive layer, a mat layer composed of protrusions provided independently of each other can be provided. The purpose of the mat layer is to improve the vacuum adhesion between the negative image film and the photosensitive lithographic printing plate in contact exposure, thereby shortening the vacuuming time and preventing the collapse of minute dots during exposure due to poor adhesion. That is.

As a method for applying the mat layer, see
Japanese Patent Application Laid-Open No. 58-18263 discloses a method for thermally fusing powdered solid powder described in JP-A-12974.
There is a method of spraying and drying the polymer-containing water described in Japanese Patent Publication No. 6 (1994), and any method may be used, but the mat layer itself is dissolved in an aqueous alkaline developer substantially free of an organic solvent, or Is desirable.

After the photosensitive lithographic printing plate prepared as described above is exposed to an image, a resin image is formed by a process including development by a conventional method. For example, in the case of a photosensitive lithographic printing plate having the photosensitive layer of the above [1], after image exposure, exposure is carried out by developing with an aqueous alkali solution as described in US Pat. No. 4,259,434. The part is removed to obtain a lithographic printing plate. In the case of a photosensitive lithographic printing plate having a photosensitive layer of [2], after image exposure,
Using a developing solution as described in U.S. Pat. No. 4,186,006, the unexposed portion of the photosensitive layer is removed by development to obtain a lithographic printing plate. Also, JP-A-59-84
No. 241, JP-A-570-192952, and JP-A-62-24263, using an aqueous alkaline developer composition used for developing a positive-working lithographic printing plate. You can also.

[0058]

Examples 1 to 5 Using a device described in Japanese Patent Publication No. Sho 50-40047, a JIS1050 aluminum plate was brushed with 6-10 nylon bundles having a diameter of about 0.2 mm at a rotation speed of 200 rpm and an average of 30 μm A1203. And S
Mechanical graining was performed using a slurry liquid prepared by adjusting the iO 2 -containing abrasive to a volume specific gravity of 20%. The measured average surface roughness was 0.45 μm. Thereafter, the etching time was adjusted by adjusting the treatment time so that the dissolved amount was 5 g / m ² at a concentration of caustic soda of 20% and a temperature of 50 ° C. Thereafter, the substrate was washed with water, treated with sulfuric acid 20% at a temperature of 60 ° C. for 20 seconds, and smut removed (desmutted). Thereafter, using the apparatus of FIG. 1, while maintaining the temperature at 35 ° C., 19 g /
An electrolytic solution was prepared with 1 l of hydrochloric acid and an aluminum concentration of 6 g / l, and the circulation amount was set so that the flow rate became 0.3 m / sec. The power source was set so that the amount of anode electricity of aluminum was 350 c / dm ² and the current density was 20 A / dm ² at a frequency of an AC waveform of 60 Hz, and the main counter electrode was graphite. The DC power supply was set such that the current flowing in the auxiliary counter electrode / current of the alternating current became as shown in Table 1. Thereafter, the film was washed with water, and the etching time was adjusted so that the amount of dissolution was 0.8 g / m ² at a caustic soda concentration of 10% and a temperature of 40 ° C., and was subjected to an etching treatment. After washing with water, sulfuric acid 15%, aluminum 10g / l, temperature 4
At 0 ° C., an anodic oxide film was formed. (Examples 1 to 5)

[0059]

[Table 1] [Comparative Example 1] A JIS 1050 aluminum plate was brushed with 6-10 nylon bundles of about 0.2 mm in diameter using an apparatus described in Japanese Patent Publication No. 50-40047 at a rotational speed of 200 rpm and A1203 and Si having an average of 30 µm were used.
Mechanical graining was performed using a slurry liquid prepared by adjusting an O 2 -containing abrasive to a volume specific gravity of 20%. The measured average surface roughness was 0.45 μm. Thereafter, the etching time was adjusted by adjusting the treatment time so that the dissolved amount was 5 g / m ² at a concentration of caustic soda of 20% and a temperature of 50 ° C. Thereafter, the substrate was washed with water, treated with sulfuric acid 20% at a temperature of 60 ° C. for 20 seconds, and smut removed (desmutted). Thereafter, using the apparatus of FIG. 3, while maintaining the temperature at 35 ° C., 19 g /
An electrolytic solution was prepared with 1 l of hydrochloric acid and an aluminum concentration of 6 g / l, and the circulation amount was set so that the flow rate became 0.3 m / sec. The power source was set so that the amount of anode electricity of aluminum was 350 c / dm ² and the current density was 20 A / dm ² at a frequency of an AC waveform of 60 Hz, and the main counter electrode was graphite. After that, it was washed with water, the concentration of caustic soda was 10%, and the temperature was 40.
The etching time was adjusted by adjusting the processing time so that the amount of dissolution at 0.8 ° C. was 0.8 g / m ² . Then, wash with water and add sulfuric acid 15
%, Aluminum at 10 g / l, and a temperature of 40 ° C., to form an anodic oxide film.

[0060]

Comparative Examples 2 and 3 A JIS 1050 aluminum plate was brushed by using a device described in Japanese Patent Publication No. Sho 50-40047 and a brush roll obtained by bundling 6-10 nylon having a diameter of about 0.2 mm at 200 rpm and A1203 having an average of 30 μm. And S
Mechanical graining was performed using a slurry liquid prepared by adjusting the iO 2 -containing abrasive to a volume specific gravity of 20%. The measured average surface roughness was 0.45 μm. Thereafter, the etching time was adjusted by adjusting the treatment time so that the dissolved amount was 5 g / m ² at a concentration of caustic soda of 20% and a temperature of 50 ° C. Thereafter, the substrate was washed with water, treated with sulfuric acid 20% at a temperature of 60 ° C. for 20 seconds, and smut removed (desmutted). Thereafter, using the apparatus of FIG. 1, while maintaining the temperature at 35 ° C., 19 g /
An electrolytic solution was prepared with 1 l of hydrochloric acid and an aluminum concentration of 6 g / l, and the circulation amount was set so that the flow rate became 0.3 m / sec. The power source was set so that the amount of anode electricity of aluminum was 350 c / dm ² and the current density was 20 A / dm ² at a frequency of an AC waveform of 60 Hz, and the main counter electrode was graphite. The DC power supply was set so that the current flowing in the auxiliary counter electrode / current of the alternating current was as shown in Table 2. Thereafter, the film was washed with water, and the etching time was adjusted so that the amount of dissolution was 0.8 g / m ² at a caustic soda concentration of 10% and a temperature of 40 ° C., and was subjected to an etching treatment. After washing with water, sulfuric acid 15%, aluminum 10g / l, temperature 4
At 0 ° C., an anodic oxide film was formed. (Comparative Examples 2 and 3)

[0061]

[Table 2] For the example and the comparative example, the operation was continuously performed for 20 hours, and the consumption of the main counter electrode was examined, and the printing performance was confirmed by coating the photosensitive layer. The results are shown in the table below.

[0062]

[Table 3]

[0063]

As described above, according to the electrolytic processing method according to the present invention, it is possible to easily apply an existing AC power supply, improve the stability of the electrodes, and generate uniform pits. .

[Brief description of the drawings]

FIG. 1 is an explanatory view showing an electrolytic processing apparatus according to an embodiment of the present invention.

FIG. 2 is an explanatory view of an electrode portion of the electrolytic processing apparatus of FIG.

FIG. 3 is an explanatory diagram showing a conventional electrolytic processing apparatus that performs an electrochemical process using only an AC power supply.

FIG. 4 is an explanatory view of an electrode portion of the electrolytic processing apparatus of FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Metal web 2 ... Main counter electrode 3 ... Auxiliary counter electrode 4 ... Electrolyte 5 ... AC power supply 6 ... DC power supply

Claims (3)

[Claims] An AC electrolytic treatment method for performing an electrochemical treatment on a material to be treated by supplying an alternating current between the treatment solution and a counter electrode in an electrolytic treatment solution mainly containing nitric acid or hydrochloric acid, An electrolytic processing method, wherein the counter electrode is formed by a main counter electrode and an auxiliary counter electrode, and a circuit connected to the main counter electrode is connected in parallel with a circuit for the auxiliary counter electrode, and a direct current is passed through the auxiliary counter electrode. 2. The method according to claim 1, wherein said main counter electrode is graphite. 3. The electrolytic processing method according to claim 1, wherein the current A flowing through the auxiliary counter electrode and the current B of the alternating current are A / B = 0.001 to 0.3.