JPH10138654A - Aluminum support for lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve properties of being hard to stain, and printing performance by setting a ratio of specific surface inclining degree or more obtained by measuring specific revolving power by an interatomic force microscope (AFM) to a specific range, and setting hardness obtained by measuring it by a Vickers hardness tester to a specific value. SOLUTION: A ratio of 30 degrees or more of surface inclining degree obtained by measuring at revolving power of 1.9μm by an interatomic force microscope (AFM) is set to 10 to 20% to smooth a surface, and hardness (Hv) obtained by measuring it by a Vickers hardness tester is set to 20 to 100kg/mm<2> to harden the surface. Further, a ratio of 30 degrees or more of surface inclining degree is preferably set to a range of 12 to 18%. Thus, characteristics of excellent stain difficulty, printing performance and plate wear resistance, preferable stain resistance on a halftone part and stain resistance of non-image part on a blanket can be exhibited.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum support for a lithographic printing plate, and more particularly to an aluminum support for a lithographic printing plate which has an optimum surface roughness as a support, is resistant to staining and has excellent printing durability. About the body.

[0002]

2. Description of the Related Art As a support for a lithographic printing plate, an aluminum plate or an aluminum alloy plate (hereinafter, referred to as an aluminum plate) has been widely used. In order to use this aluminum plate as a lithographic printing plate support,
It is necessary that the material has appropriate adhesion to the photosensitive material and water retention, and that the surface is uniformly roughened. Here, the fact that the surface is uniformly roughened means that the generated pits are large and moderately uniform, and that such pits are uniformly distributed over the entire surface. Further, the pits have a remarkable influence on the printing performance of the plate material, such as stain resistance and printing durability, and its quality is an important factor in plate material production.

Therefore, Japanese Patent Application Laid-Open No. Hei 6-24166 discloses that an etching amount of 0.
A chemical etching treatment is performed so as to obtain 5 to 30 g / m ^2, and then 200 to 600 C / d by an alternating waveform current.
A process for performing alternating current electrolysis with an amount of electricity of m ² is described.

Further, as a method of roughening an aluminum plate, there are a mechanical roughening treatment, a chemical etching treatment, an electrochemical roughening treatment, and the like. Roughening treatment, chemical etching treatment,
A method for specifying various conditions in the electrochemical surface roughening treatment is described. According to the above publication, after the mechanical surface roughening treatment, a chemical etching treatment is performed so as to have an etching amount of 0.5 to 30 g / m ^2, and then the electrochemically roughening treatment is performed at an appropriate current density and an electric quantity. After that, the surface is chemically etched in an etching amount of 0.1 to 10 g / m ² , and the corners of the irregularities generated by the electrochemical roughening in the preceding stage are smoothly finished, and anodizing treatment is performed. It has been proposed to do so.

Japanese Patent Application Laid-Open No. Hei 7-137474 describes a brush suitable for mechanical surface roughening treatment. On the other hand, the surface of the roughened aluminum plate is
It has a multilayer structure in which layers composed of pits having different opening diameters and depths overlap. These supports had insufficient blanket stain performance, and had a trade-off relationship with the deterioration of flaw stain performance when trying to improve blanket stain.

[0006]

In the case of an aluminum support for a lithographic printing plate, attention must be paid not only to printing performance but also to handleability, and it is necessary to make the blank cylinder less liable to stain and improve the printing durability. is there. An object of the present invention is to provide an aluminum support for a lithographic printing plate that can satisfy both high-dimensional balance of blank stain performance and scratch stain performance while satisfying characteristics such as stain resistance, printing performance, and printing durability. And

[0007]

SUMMARY OF THE INVENTION According to the present invention, there is provided
An aluminum support for a lithographic printing plate that has been subjected to surface roughening and anodic oxidation, and has a 10% ratio of a surface inclination of 30 ° or more determined from a measurement of a resolution of 1.9 μm by an atomic force microscope (AFM). Ｋ20%, and the hardness obtained from measurement with a Vickers hardness tester is 20 k
achieved by the ^{g / mm 2 ~100kg / mm 2} .

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to a lithographic printing plate support comprising such an aluminum plate, and has a surface inclination of not less than 30 degrees obtained from a measurement of a resolution of 1.9 μm by an atomic force microscope (AFM). 10% to 2
As the range of 0% to smooth the surface, yet hardness was determined from the measurement by Vickers hardness tester (Hv) as ^{20kg / mm 2 ~100kg / mm 2} , to harden the surface. Thus, in the related art, when the surface is smoothed, scratches and stains become severe. However, by increasing the hardness of the surface to the hardness as described above, the ratio of the surface inclination degree of 30 degrees or more is increased. As described above, when the surface is smoothed with 10% to 20%, the effect of preventing the generation of scratches and dirt can be increased.

Here, if the ratio of the surface inclination of 30 degrees or more is less than 10%, there is a problem that the fouling stain characteristics are deteriorated and the printing durability is also deteriorated. On the other hand, if the content is more than 20%, the characteristics against the burn stain deteriorate. Further, it is more preferable that the ratio of the surface inclination degree of 30 degrees or more is in the range of 12% to 18%. The surface gradient is mainly governed by chemical etching after roughening. As for Vickers hardness, hardness (Hv) is set to 20 kg / mm ² to 10
It is preferable to 0 kg / mm ² but more preferably ^{30kg / mm 2 ~80kg / mm 2} . When the hardness is less than 20 kg / mm ^2, it is very easy to be scratched, and the durability and printing durability are inferior.
If it exceeds m ² , cracks occur in the oxide film.
The Vickers hardness is mainly controlled by the amount of the anodic oxide film. The configuration and measurement principle of the AFM are described in C.I. Binnig, C .; F. Quate and
Ch. Gerber; Phys. Rev .. Lett. 5
6, 930 (1986).

Next, the processing conditions for producing the aluminum support for a lithographic printing plate of the present invention will be described. In the present invention, in particular, it is preferable to use a mechanical surface roughening treatment.However, various conditions of the electrolytic surface roughening treatment and the chemical etching treatment before and after the mechanical surface roughening treatment and a combination thereof are also used. It is preferred to provide certain conditions.

There are methods such as transfer, brush, and liquid honing for the mechanical surface roughening, and they can be used together in consideration of productivity and the like. Various methods can be used as a transfer method for pressing the uneven surface against the aluminum plate.
That is, the above-mentioned JP-A-55-74898 and JP-A-60-
No. 36195, JP-A-60-203496, and Japanese Patent Application No. 4-175, in which transfer is performed several times.
No. 945, and Japanese Patent Application No. 4-204235, in which the surface is elastic, are also applicable. In addition, by using electrical discharge machining, shot blasting, laser etching, plasma etching, etc., transfer can be performed repeatedly using a roll with fine irregularities etched, or the surface with irregularities coated with fine particles can be brought into contact with an aluminum plate. The concave and convex pattern corresponding to the average diameter of the fine particles may be repeatedly transferred to the aluminum plate a plurality of times by applying pressure repeatedly thereon. Japanese Patent Application Laid-Open Nos. Hei 3-8635 and Hei 3
66404 and JP-A-63-65017 are known. Further, fine grooves may be cut on the roll surface from two directions using a dice, a cutting tool, a laser, or the like, so that the surface has square irregularities. The roll surface 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.

When a brush is used, the flexural modulus is 10,
000-40,000 kg / cm ² , preferably 15,
Using brush bristles of 000 to 35,000 kg / cm ² and bristle strength of 500 g or less, preferably 400 g or less, the particle size is further 20 to 80 μm, preferably 30 to
It is preferable to use an abrasive of up to 60 μm. The material of the brush is not particularly limited as long as it has the above-mentioned mechanical strength, and can be appropriately selected from, for example, synthetic resin and metal.
Examples of the synthetic resin include polyamide such as nylon, polyolefin such as polypropylene, polyester such as polyvinyl chloride and polybutylene terephthalate, and polycarbonate. As metal,
Examples include stainless steel and brass. In addition, the material of the abrasive is not limited as long as the material is in the above-mentioned particle size range, and alumina, silica, silicon carbide, silicon nitride, and the like conventionally used for mechanical surface roughening treatment are used. Selected. The mechanical surface-roughening treatment is performed by pressing the roll brush having the bristles on the aluminum plate surface while rotating at high speed, and supplying the abrasive to the roll brush. At this time, the rotation speed of the roll brush, the pressing force, the supply amount of the abrasive, and the like are not particularly limited. As an apparatus suitable for the mechanical surface roughening, for example, an apparatus described in Japanese Patent Publication No. 50-40047 can be mentioned.

After the mechanical roughening treatment, the aluminum surface is chemically etched using an alkaline solution having a pH of 11 or more, preferably pH 13 or more, for the purpose of smoothing and equalizing the aluminum plate. I do. The etching amount is 5 g / m ² or more and 25 g / m ² or less, preferably 8 g / m ² or more and 20 g / m ² or less. The surface gradient of the present invention is mainly affected by the chemical etching treatment. Examples of usable alkaline solutions include aqueous sodium salt solutions such as sodium hydroxide, sodium carbonate, sodium bicarbonate, and sodium sulfate; and silicic acids such as sodium orthosilicate, sodium metasilicate, sodium disilicate, and sodium silicate. Salt aqueous solutions, aqueous solutions of phosphates such as sodium phosphate monobasic, sodium phosphate dibasic, sodium tertiary phosphate, sodium tripolyphosphate, sodium pyrophosphate, sodium hexametaphosphate and the like can be given. The processing conditions include a concentration of the alkaline solution of 0.01% to 50% by weight, a solution temperature of 20 ° C to 90 ° C,
The time is 5 seconds to 5 minutes, and is appropriately selected so that the above-mentioned etching amount is obtained.

When the surface of the aluminum plate is chemically etched with the above alkaline solution, an insoluble residue, ie, a smut, is generated on the surface of the aluminum plate. Therefore, the smut is removed using an acidic solution having the same composition as the acidic solution used for the electrolytic surface roughening treatment described later. Preferred processing conditions are a liquid temperature of 30 to 80 ° C. and a time of 3 seconds to 3 minutes.

On the surface of the roughened aluminum plate,
An anodic oxide film is formed. For example, sulfuric acid concentration of 50-30
An anodized film can be formed at 0 g / l in a solution having an aluminum concentration of 5% by weight or less by using an aluminum plate as an anode and conducting electricity. The solution contains phosphoric acid, chromic acid,
Oxalic acid, sulfamic acid, benzenesulfonic acid and the like may be blended. The amount of the formed oxide film is 1.8 to 4.
0 g / m ^2, it is preferred that particularly 2.1~3.0g / m ^2. The Vickers hardness of the present invention is mainly governed by the thickness of the oxide film. The anodizing treatment conditions vary depending on the electrolytic solution to be used, and thus cannot be determined unconditionally. In general, however, the concentration of the electrolytic solution is 1 to 80% by weight,
~ 70 ° C, current density 0.5 ~ 60A / cm ² , voltage 1 ~
The range is 100 V, the electrolysis time is 15 seconds to 50 minutes, and the amount is adjusted so as to have the above-mentioned coating amount. As an electrolytic device,
These are introduced in JP-A-48-26638, JP-A-47-18739 and JP-B-58-24517. Also, JP-A-54-81133 and JP-A-57-4789.
4, JP-A-57-51289, JP-A-57-5129
0, JP-A-57-54300, JP-A-57-13659
6, JP-A-58-107498, JP-A-60-2002
56, JP-A-62-136596, JP-A-63-176
494, JP-A-4-176897, JP-A-4-2809
97, JP-A-6-207299, JP-A-5-2437
7, JP-A-5-32083, JP-A-5-125597,
The methods described in JP-A-5-195291 and the like can also be used.

Here, the aluminum plate used in the present invention 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, or bismuth, is used. There are various types of aluminum alloys.
In JP-6635, Fe and Si components are limited, and an intermetallic compound is specified. In addition, Japanese Patent Publication No. 55-2887
In Japanese Patent Publication No. 4, the cold rolling ratio and the intermediate dulling are performed, and the voltage application method for electrolytic surface roughening is limited. Tokiko Sho 62-413
04, Japanese Patent Publication No. 46577, Japanese Patent Publication No. 46578,
Tokiko 1-47545, Tokiko 1-35910, Tokiko 63-60823, Tokiko 63-60824, Tokiko 4
-13417, 4-19290, 4-19
No. 291, Tokuhei 4-19293, Tokiko 62-5054
0, JP-A-61-272357, JP-A-62-7406
0, JP-A-61-201747, JP-A-63-14432
34, JP-A-63-143235, JP-A-63-255
338, JP-A-1-283350, EP272
528, U.S. Patent Nos. 4,902,353 and 4,818,300;
EP394816, U.S. Pat. No. 5,019,188, West German Patent 3,232,810, U.S. Pat.
9995, U.S. Pat. No. 4,822,715, West German Patent 35
07402, U.S. Pat. No. 4,715,903, West German Patent 3
507402, EP289844, US Patent 50097
22, 495,004, West German Patent 371405
9, U.S. Pat. Nos. 4,686,083 and 4,861,396, EP
It includes not only the aluminum alloys described in the specifications of the 158941 specification, 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. EP 223737,
In each of U.S. Pat. Nos. 4,802,935 and 4,800,950, an application is made with a limited amount of a minor alloy component. E
P415238 proposes continuous casting, continuous casting + hot rolling. In the present invention, an excellent photosensitive lithographic printing plate is obtained by performing various surface treatments, transfer, and the like on such an aluminum plate to form a printing original plate having uniform unevenness, and providing a photosensitive layer such as a diazo compound thereon. Becomes In any case, it is necessary to select an appropriate material.

Next, as a treatment for such an aluminum plate, it is preferable to perform a mechanical surface roughening treatment first, but before this, a pretreatment may be performed as required. . This pretreatment is typically performed by removing the rolling oil on the aluminum plate surface using a solvent such as trichlene or a surfactant, or cleaning the aluminum plate surface using an alkali etching agent such as sodium hydroxide or potassium hydroxide. This is the exposure of the aluminum plate surface. Specifically, as a solvent degreasing method, gasoline, kerosene, benzene, solvent naphtha, a method using a petroleum solvent such as normal hexane, trichloroethylene, methylene chloride, perchlorethylene,
There is a method using a chlorine-based solvent such as 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 phosphate monobasic, sodium phosphate tribasic,
There is a method using an aqueous solution of a phosphate such as 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, and various commercially available products can be used. As the degreasing method, a dipping method, a spraying method, a method of rubbing a liquid or the like with a liquid or the like can be used. Ultrasonic waves may be used for the dipping or spraying method. Regarding the degreasing treatment, see, for example, JP-A-2-2679.
No. 3 publication can be referred to.

Next, the above-described mechanical surface roughening treatment is performed, and further, the aluminum plate obtained by such a treatment is subjected to electrolytic surface roughening treatment. In the electrolytic surface roughening treatment in the present invention, it is preferable to perform first and second electrolytic treatments using an alternating waveform current in an acidic solution before and after the cathodic electrolytic treatment.
By the cathodic electrolysis, smut is generated on the surface of the aluminum plate, and hydrogen gas is generated, so that more uniform electrolytic surface roughening is possible. First, the first and second electrolytic surface roughening treatments using an alternating waveform current in an acidic solution will be described. In this electrolytic surface roughening treatment, the first treatment and the second treatment may be performed under the same conditions, or may be different in the range of preferable processing conditions. This electrolytic surface roughening treatment can be performed, for example, according to the electrochemical graining method described in JP-B-48-28123 and British Patent 896563. This electrolytic graining uses a sine-wave alternating current, but may use a special waveform as described in JP-A-52-58602. Also, JP-A-3-7979
The waveform described in Japanese Patent Publication No. 9 can also be used. 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-1-5889, JP-A-1-28059
0, JP-A-1-118489, JP-A-1-14859
2, JP-A-1-178496, JP-A-1-18831
5, JP-A-1-154797, JP-A-2-23579
4, JP-A-3-260100, JP-A-3-25360
0, JP-A-4-72079, JP-A-4-72098, JP-A-3-267400, and JP-A-1-141094 can also be applied. As the frequency, in addition to the above, those proposed for an electrolytic capacitor can be used. For example, U.S. Pat.
No. 76879.

Examples of the acidic solution as an electrolytic solution include nitric acid, hydrochloric acid and the like, as well as US Pat.
4661219, 4618405, 46262
8, 4600482, 4566960, 4566
958, 4566959, 4416972, 43
Electrolyte solutions described in each of 74710, 4336113, and 4184932 can also be used. The concentration of the acidic solution is 0.
The content is preferably 5 to 2.5% by weight, but considering the use in the above-mentioned smut removal treatment, 0.7 to 2.0% by weight is particularly preferred. The liquid temperature is 20 to 80 ° C, especially 30 to 60 ° C.
C is preferred.

Various electrolytic cells and power sources have been proposed, but are disclosed in US Pat.
123400, JP-A-57-59770, JP-A-53-570
12738, JP-A-53-32821, JP-A-53-3283
2822, JP-A-53-32823, JP-A-55-12
2896, JP-A-55-132883, JP-A-62-1
27500, JP-A-1-52100, JP-A-1-520
98, JP-A-60-67700, JP-A-1-23080
And JP-A-3-257199. In addition to the above-mentioned patents, various proposals have been made. For example, JP-A-52-58602, JP-A-52-1
52302, JP-A-53-12738, JP-A-53-1
2739, JP-A-53-32821, JP-A-53-32
822, JP-A-53-32833, JP-A-53-328
24, JP-A-53-32825, JP-A-54-8580
2, JP-A-55-122896, JP-A-55-1328
84, JP-B-48-28123, JP-B-51-708
1, JP-A-52-133838, JP-A-52-1338
40, JP-A-52-133844, JP-A-52-133
845, JP-A-53-149135, JP-A-54-14
Of course, those described in JP-A-6234 can be applied.

In this electrolytic treatment, the anode electricity amount is 50 to 400
C / dm ^2, preferably at 70~200C / dm ^2. When the anode charge is less than 50 C / dm ² , fine pits are not uniformly generated, while when it exceeds 400 C / dm ² , the pits become too large.

During the first and second electrolytic surface roughening treatments, the aluminum plate is subjected to a cathodic electrolytic treatment. By this cathodic electrolysis, a smut is generated on the surface of the aluminum plate, and a hydrogen gas is generated so that a more uniform electrolytic surface roughening can be achieved. This cathodic electrolysis is carried out in an acidic solution at a cathodic electricity of 3 to 80 C / dm ² , preferably 5 to 30 C / dm ² .
/ Dm ² . Cathode in the amount of electricity is less than 3C / dm ^2, insufficient smut adhesion amount, whereas if it exceeds 80C / dm ^2, not desirable smut adhering amount is excessive. Further, the electrolytic solution may be the same as or different from the solution used in the first and second electrolytic surface roughening treatments.

After the second electrolytic surface roughening treatment, the aluminum plate is subjected to a second chemical etching treatment using an alkaline solution having a pH of 11 or more. The alkaline solution having a pH of 11 or more used in the second chemical etching treatment may be the same as or different from the alkaline solution used in the first chemical etching treatment. However, unlike the first chemical etching treatment, the etching amount is 0.1 to 8 g / m ² , preferably 0.2 to 8 g / m ² .
3.0 g / m ² . Etching amount is 0.1 g / m ²
If it is less than 10%, the pit ends obtained by the electrolytic treatment cannot be smoothed, while if it exceeds 8 g / m ² , the pits disappear.

Since a smut is generated by the above-mentioned chemical etching, the smut is removed from the aluminum plate using a solution mainly containing sulfuric acid. Here, the solution mainly composed of sulfuric acid means not only a sulfuric acid alone solution but also phosphoric acid, nitric acid,
It is a mixed solution obtained by appropriately mixing chromic acid, hydrochloric acid and the like.
For the removal of the smut using a solution mainly containing sulfuric acid, for example, JP-A-53-12739 can be referred to. Further, alkali treatment may be combined, and for example, JP-A-56-51388 can be referred to. Further, JP-A-60-8091, JP-A-63-176
188, JP-A-1-38291, JP-A-1-12738
9, JP-A-1-188699, JP-A-3-17760
0, JP-A-3-126891, JP-A-3-191100
The methods described in each publication can be used in combination.

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 an apparatus for sealing a support which gives a photosensitive printing plate which is sealed with hot water, has good stability over time, has good developability, and has 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, Japanese Patent Application No. 4-33
952, Japanese Patent Application No. 4-33951, Japanese Patent Application No. 3-31524
5 The sealing treatment may be performed by an apparatus or a method described in the specification of each item.

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-3-21509
Patent No. 5, 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.

In the present invention, the measurement by the AFM is performed after a series of roughening processes are completed. The measurement by the AFM is performed by, for example, SP137 manufactured by Seiko Electronic Industry Co., Ltd.
00 can be performed. The measurement procedure is first 1c
An aluminum plate sample cut to the size of m square is set on a horizontal sample stage on a piezo scanner, the cantilever is approached to the sample surface, and when it reaches the region where the atomic force acts, it is scanned in the XY directions. Then, the displacement of the piezo scanner in the Z direction is captured by the unevenness of the sample. A piezo scanner that can scan XY 150 μm and Z 10 μm is used. The cantilever is SI-DF20 manufactured by NANOPROBE, and has a resonance frequency of 120 to 150 kHz.
A spring constant of 12 to 20 N / m is used. For example, the measurement is performed in four fields of 120 μm square, that is, in the range of 240 μm square, and the resolution at that time is 1.9 μm in the XY directions,
The Z direction is 1 nm, and the scanning speed is 60 μm / sec.
Performed in DFM mode (Dynamic Force Mode) as c.

After the measurement by AFM is completed, a photosensitive lithographic printing plate can be prepared by providing a photosensitive layer as exemplified below. [I] A case where a photosensitive layer containing a novolak resin of o-naphthoquinonediazidesulfonic acid ester and a mixture of phenol and 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. Among these, o-naphthoquinonediazidesulfonic 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 are particularly preferable. In particular, US 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, it is even more preferable. Further, to form a visible image by exposure, o-naphthoquinonediazide-4-sulfonyl chloride, inorganic anion salt of p-diazodiphenylamine, trihalomethyloxadiazole compound, trihalomethyloxadiazole compound having a benzofuran ring, etc. Compounds and the like are added. On the other hand, a triphenylmethane dye such as Victoria Bull-BOH, crystal violet, oil blue, or the like is used as a colorant for an image. Also, Japanese Patent Application Laid-Open No. 62-2932
The dye described in JP-B-47 is particularly preferred. Further, a phenol substituted with an alkyl group having 3 to 15 carbon atoms such as t-butyl phenol, N-type as described in JP-B-57-23253 is used as a sensitizer.
Octylphenol, a novolak resin obtained by condensing t-butylphenol with formaldehyde, or o-naphthoquinonediazide-4 of such a novolak resin
-Or -5-sulfonic acid ester (for example, see
1-2242446). Further, in order to improve the developability, a nonionic surfactant as described in JP-A-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 Methyl, ethyl lactate, dimethyl sulfoxide, dimethylacetamide,
Examples include dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol, isopropanol, and diethylene glycol dimethyl ether. These solvents are used alone or in combination. The photosensitive composition comprising these components has a solid content of 0.1%.
5 to 3.0 g / m ^{2 is} provided.

[II] When a photosensitive layer containing a diazo resin and a water-insoluble and lipophilic photomolecular compound is provided. As the diazo resin, for example, a diazo resin inorganic salt which is a reaction product of a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde with hexafluorophosphate, tetrafluoroborate, and an organic solvent, 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 a carboxyl group, a sulfonic acid group, a sulfinic acid group,
It is a cocondensate containing, as a structural unit, an aromatic compound having at least one organic group of an oxygen acid group and a hydroxyl group of phosphorus and a diazonium compound, preferably an aromatic diazonium compound. The aromatic ring preferably includes a phenyl group and a naphthyl group. As 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, various compounds can be mentioned, but 4-methoxy is preferable. Benzoic 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, benzene Sulfonic 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-amino-diphenylamines, and such 4-amine-diphenylamines include 4-aminodiphenylamine, 4-amino-3-methoxydiphenylamine, 4-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-diphenylamine-2-carboxylic acid, 4-
Examples thereof include amino-diphenylamine-2′-carboxylic acid, and particularly preferably, 3-methoxy-4-amino-4.
-Diphenylamine and 4-aminodiphenylamine. Further, as a diazo resin other than a co-condensation diazo resin with an aromatic compound having an acid group, JP-A-4-18559.
, JP-A-3-163551 and JP-A-3-253
The diazo resin condensed with an aldehyde containing an acid group or an acetal compound thereof described in each of the publications of 857 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, camphorsulfonic acid, tolyloxy-3-propanesulfonic acid, nonylphenoxy-3-propanesulfonic acid, nonylphenoxy-4-butanesulfonic acid, dibutylphenoxy-3-propanesulfonic acid 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, isopropylnaphthalensulfonic acid, butylnaphthalenesulfonic 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-dinitro-naphthalene-3,6-disulfonic acid, 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,
HClO _4, HIO ₄ perhalogen acids such as including but not limited to this. 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 arbitrarily determined 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 having aliphatic hydroxyl groups, and methacrylic esters, for example, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate,
4-hydroxybutyl methacrylate (3) unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride and itaconic acid; (4) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, (Substituted) alkyl acrylates such as hexyl acrylate, cyclohexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate and N-dimethylaminoethyl acrylate;

(5) (substituted) alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate, (6) acrylamide, methacryl Amide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamides such as N-phenylacrylamide; Vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether,
Vinyl ethers such as propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether; (8) vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate; (9) styrene, α-methylstyrene, chloro Styrenes such as methylstyrene, (10) vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone;

(11) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene;
2) N-vinyl pyrrolidone, N-vinyl carbazole,
4-vinylpyridine, acrylonitrile, methacrylonitrile, etc. (13) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-aceketyl methacrylamide, N-propionyl methacrylamide, N- (p-chlorobenzoyl) methacrylamide , (14) N (o-aminosulfonylphenyl) methacrylamide, N- (m-
Aminosulfonylphenyl) methacrylamide, N-
(P-amino) sulfonylphenyl methacrylamide,
Methacrylamides such as N- (1- (3-aminosulfonyl) naphthyl) methacrylamide, N- (2-aminosulfonylethyl) methacrylamide, and acrylamides having the same substituents as described above; Methacrylic esters such as aminosulfonylphenylphmethacrylate, m-aminosulfonylphenylmethacrylate, p-aminosulfonylphenylmethacrylate, 1- (3-aminosulfonylnaphthyl) methacrylate, and acrylic esters having the same substituents as described above Unsaturated sulfonamides such as (15) unsaturated monomers having a crosslinkable group in the side chain, such as N- (2- (methacryloyloxy) -ethyl) -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
Polymer compounds described in JP-A No. 3450 and JP-A-2-14642. If necessary, a polyvinyl butyral resin, a polyurethane resin, a polyamide resin, an epoxy resin, a novolak resin, a natural resin, or the like may be added to the copolymer.

The photosensitive composition used for the support of the present invention may further contain a dye for the purpose of obtaining a visible image by exposure and a visible image after development. Examples of the pigment include Victoria Pureable-BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue # 603 (manufactured by Orient Chemical Industries), Patent Pure Blue (manufactured by Sumitomo Sangoku Chemical Co., Ltd.), crystal violet, brilliant green, ethyl violet, Trimethyl represented by methyl violet, methyl green, erythrosin B, basic fuchsin, malachite green, oil red, m-cresol purple, rhodamine B, auramine, 4-p-diethylaminophenyliminaphthoquinone, cyano-p-diethylaminophenylacetanilide and the like Color tone of phenylmethane, diphenylmethane, oxazine, xanthene, iminonaphthoquinone, azomethine or anthraquinone dyes from colored to colorless or different It mentioned as examples of discoloring agents changing. On the other hand, examples of the color changing agent that 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-4-
Primary or secondary spherical arylamine dyes represented by anilinonaphthylmethane and p, p ', p "-triaminotriphenylmethane. Triphenylmethane dyes and diphenylmethane dyes are particularly preferred. It is effectively used, and is more preferably a triphenylmethane dye, particularly Victoria Pure Blue BOH.

Various additives can be further added to the photosensitive composition used in 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, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers and polymers of acrylic acid or methacrylic acid, of which tricresyl phosphate is particularly preferred), and a feeling for improving the oil sensitivity of the image area. Fatty agent (for example, JP-A-55-
No. 527, a half-esterified product of a styrene-maleic anhydride copolymer with an alcohol, a novolak resin such as pt-butylphenol-formaldehyde resin, a 50% fatty acid ester of p-hydroxystyrene, etc.), a stabilizer {for example, Phosphoric acid, phosphorous acid, organic acids (citric acid, oxalic acid, dipicolinic 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, but is more preferably a mixture of a high boiling solvent such as methyl cellosolve, 1-methoxy-2-propanol and methyl lactate and a low boiling solvent such as methanol and methyl ethyl ketone. The solid concentration of the photosensitive composition at the time of application is desirably in the range of 1 to 50% by weight. In this case, the coating amount of the photosensitive composition may be about 0.2 to 10 g / m ² (dry weight), more preferably 0.5 to 3 g / m ² .

[III] When a photosensitive layer containing a photodimerizable photosensitive composition and a photopolymerizable photosensitive composition is provided. As the photodimerizable photosensitive composition, a maleimide group, a cinnamyl group, a cinnamoyl group, a cinnamylidene group, Polymers having a cinnamylidene acetyl group or chalcone group in the side chain or main chain are mentioned. As a polymer having a maleimide group in the side chain, JP-A-52-988 (corresponding to US Pat. No. 4,079,041) ) Gazette and German Patent No. 2,6
26,769, EP 21,019
And EP 3,552, and 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, carboxylic acid / sulfonic acid, phosphoric acid, phosphonic acid, their alkali metal salts and ammonium salts, and pKa that dissociates in alkaline water are 6%. It is useful to use the polymer containing from 12 to 12 acid groups in the polymer. If necessary, the above 13 kinds of monomers having an acid group 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 Makromoleku
lare Chemie) 128 (1984), pp. 71-91, a copolymer of N- [2- (methacryloyloxy) ethyl] -2,3-dimethylmaleimide and methacrylic acid or acrylic acid. 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.

US Pat. No. 3,030,208 and US Pat. No. 3,030,208 are examples of the optically overseas 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. Application 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, JP-A-60-191
Photopolymers such as those described in JP-A-244-244 can be mentioned. Further, Japanese Patent Application Laid-Open No. 62-17572
9, JP-A-62-175730, JP-A-63-25
No. 443, JP-A-63-218944 and JP-A-63-218944.
And the photosensitive polymer described in each publication of JP-A-218945. A sensitizer can be used in the photosensitive layer containing these compounds. Examples of such a sensitizer include benzophenone derivatives, benzanthrone derivatives, quinones, aromatic nitro compounds, naphthothiazoline derivatives, and benzothiazoline derivatives. Thioxanthones, naphthothiazole derivatives, ketocoumarin compounds, benzothiazole derivatives, naphthofuranone compounds, beryllium salts, thiavirylium salts, and the like.
In such a photosensitive layer, if necessary, chlorinated polyethylene, chlorinated polypropylene, polyacrylate alkyl ester, acrylate alkyl ester, acrylonitrile, vinyl chloride, styrene, a copolymer with at least one of monomers such as butadiene, Binders such as polyamide, methyl cellulose, polyvinyl formal, polyvinyl butyral, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, dibutyl phthalate,
Plasticizers such as dialkyl phthalate such as dihexyl phthalate, oligoethylene glycol alkyl ester, and phosphate ester can be used.
Further, for the purpose of coloring the photosensitive layer, a dye or a pigment, or a substance to which a pH supporting agent or the like is added as a printing-out agent is also preferable.

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.

[IV] 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 and JP-A-60-186847
And a photosensitive layer using an electrophotographic photoreceptor described in JP-A-61-238063 or the like.
The amount of the photosensitive layer provided on the support is about 0.1 to about 7 g / m ² , preferably 0.5 to 4 g, by dry weight after coating.
/ M ² .

In the method for producing a support for a lithographic printing plate according to 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. For the purpose of the above, an intermediate layer may be provided as necessary. In order to improve the adhesion, the intermediate layer is generally made of a diazo resin or a phosphoric acid compound, an amino compound, a carboxylic acid compound or the like which adsorbs to aluminum, for example. 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, about 1-100 mg / m ^{2 as} a dry solid
Is good, 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.
Japanese Patent Application Laid-Open No. 55-12974 discloses a method of applying a mat layer.
JP-A-58-182636, a method of spraying and drying polymer-containing water described in JP-A-58-182636, and the like. It is desirable that the mat layer itself be dissolved in an aqueous alkaline developer containing substantially no organic solvent, or be removable by this.

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 [I], after exposing the image, it is exposed to light by developing with an aqueous alkali solution as described in US Pat. No. 4,259,434. A part of the lithographic printing plate is obtained by removing the portion, and in the case of a photosensitive lithographic printing plate having the photosensitive layer of [II], after image exposure, the lithographic printing plate is described in US Pat. No. 4,186,006. With a developing solution as described above, the photosensitive layer in the unexposed area is removed by development to obtain a lithographic printing plate. Also, Japanese Unexamined Patent Publication No.
No. 84241, JP-A-57-192952, and JP-A-62-24263, which use an aqueous alkaline developer composition used for developing a positive-working lithographic printing plate. You can also.

[0045]

The present invention can be further clarified by the following examples under the following conditions. However, the present invention is not limited by these examples. Implementation Conditions Continuous processing was performed using a JIS1050 aluminum plate having a thickness of 0.3 mm and a width of 1030 mm. (A) While supplying a suspension of an abrasive (aluminum hydroxide) having a specific gravity of 1.12 and water as a polishing slurry to the surface of an aluminum plate, mechanically roughening is performed with a rotating roller-shaped nylon brush. Was. The nylon brush was made of 6.10 nylon, had a bristle length of 50 mm, and had a bristle diameter as shown in Table 1. Nylon brush is φ3
A hole was made in a 00 mm stainless steel cylinder and the hair was planted so as to be dense. Three rotating brushes were used. The distance between the two support rollers (φ200mm) below the brush is 300mm
Met. The brush roller was pressed until the load of the drive motor for rotating the brush became 7 kW in addition to the load before pressing the brush roller against the aluminum plate. Or, no mechanical roughening was performed. The direction of rotation of the brush was the same as the direction of movement of the aluminum plate. (B) Next, the aluminum plate was subjected to a sodium hydroxide concentration of 26% by weight, an aluminum ion concentration of 6.5% by weight, and a liquid temperature of 75 °.
The aluminum plate was dissolved by 10 g / m ² by performing an etching treatment by spraying with C. Thereafter, washing with water was performed by spraying. (C) Desmut treatment with a 1% by weight nitric acid aqueous solution (containing 0.5% by weight of aluminum ion) at a liquid temperature of 30 ° C. was carried out by spraying, and then water washing was carried out by spraying. (D) Electrochemical surface roughening treatment was continuously performed using an AC voltage having a frequency of 60 Hz. At this time, the electrolytic solution was a 1% by weight nitric acid aqueous solution (containing 0.5% by weight of aluminum ion and 0.007% by weight of ammonium ion), and the solution temperature was 35 °.
C. In the AC power supply waveform, the time TP until the current value reaches a peak from zero is 2 msec, and the duty ratio is 1:
1. Using a trapezoidal rectangular wave alternating current, electrochemical surface roughening treatment was performed using a carbon electrode as a counter electrode. The quantity of electricity was as shown in Table 1 as the sum of the quantity of electricity when the aluminum plate was the anode. (E) The aluminum plate was spray-etched at a caustic soda concentration of 26% by weight and an aluminum ion concentration of 6.5% by weight, and the aluminum plate was dissolved in the amount shown in Table 1 and electrochemically treated using the preceding alternating current. The smut component mainly composed of aluminum hydroxide generated during the roughening was removed, and the edge portion of the generated bit was dissolved to smooth the edge portion. Then, it was washed with water by spraying. (F) A spray desmutting treatment was performed with a 25% by weight aqueous solution of sulfuric acid (containing 0.5% by weight of aluminum ion) at a liquid temperature of 60 ° C., and then, washing with a spray was performed. (G) An aqueous solution of 15% by weight of sulfuric acid (containing 0.5% by weight of aluminum ion) at a liquid temperature of 35 ° C. A) Using a DC voltage, a current density of 2 A / dm ² and an amount of anodic oxide film of 2.
Anodizing treatment was performed to 4 g / m ² . Thereafter, water washing by spraying was performed.

[0046]

[Table 1]

In accordance with the above-described processing steps, the ratio (indicated as a30) of the surface inclination degree of 30 degrees or more obtained from the measurement of the 1.9 μm resolution by the AFM and the hardness obtained from the measurement by the Vickers hardness tester are changed. Table 2 shows the results of a comparative experiment of blanc stains and scratch stains performed on a plurality of samples.

[0048]

[Table 2]

Here, the ratio (a3) of the surface inclination degree of 30 degrees or more obtained from the measurement of the resolution of 1.9 μm by the AFM.
0) is set to 22%, the etching amount is 5 g / m ² , and when the a30 is set to 15%, the etching amount is 1
It becomes 5 g / m ² . In addition, Vickers hardness is 18kg /
When the anodic oxidation treatment is performed so that the Vickers hardness becomes 50 mm ² , the amount of the anodic oxide film becomes 1.5 g / m ² .
When the anodic oxidation treatment is performed so as to be kg / mm ² , the amount of the anodic oxide film becomes 3.0 g / m ² .

For the determination of scratches and stains, the lithographic printing plates of the respective Examples and Comparative Examples were treated in the order of plate making, exposure, development, gumming, and printing. Then, a scratch was made by a scratch tester, and after printing, a printed matter was evaluated. HEIDON scratching Intersity TESTER H
Using EIDEN-18, a 0.4 mmk sapphire needle was used.
The printed matter was evaluated on the basis of the following criteria using the load of a scratch tester at the time when scratches and stains were clearly generated. Evaluation Scratched stain generation load (g) × 2, 5, 10 △ 30, 50, 70 ○ 100, 150 ◎ 200, 250

As can be seen from Table 2, when the ratio (a30) at which the surface gradient is 30 ° or more is reduced, the scumming property is improved, but the scratching property is deteriorated. (Comparative Example-1 →
Comparative Example-2) In Comparative Example-3, heretofore, the Vickers hardness was not set to a large value because cracks occurred in the anodic oxide film if the Vickers hardness was too high.
By setting the ratio to / mm ² , scratches and dirt can be improved without causing film cracking. However, there is no improvement with respect to blanc staining. On the other hand, in the embodiment of the present invention,
A30 in Comparative Example-3 was changed to 12 to 18%. On an extension of the conventional common sense, such changes are expected to worsen the fouling,
As can be seen from Table 2, while the scumming was improved, the scumming was further improved, and a3 shown in Comparative Example-3 was obtained.
It is clear that an unexpected improvement is obtained, where the value of 0 is even better than 22%. In particular, Example 4 or 5
As described above, the surface is smoothed by setting a30 to 12 and 15%, and the hardness of the surface is increased to 50 kg / mm ² as described above. be able to.

[0052]

As described above, the lithographic printing plate of the present invention has a surface inclination of 30 degrees or more obtained from AFM measurement of 1.9 μm (indicated as a30).
Is in the range of 10% to 20%, and the hardness determined by measurement with a Vickers hardness tester is 20 kg / mm ² to 1
By setting the pressure at 00 kg / mm ² , the stain resistance, printing performance,
This is a lithographic printing plate that achieves both a high level of blank stain performance and scratch stain performance while satisfying various properties such as printing durability.

Claims (1)

[Claims] 1. An aluminum support for a lithographic printing plate which has been subjected to surface roughening and anodic oxidation, and has a surface inclination of 30 ° or more obtained from a measurement of a resolution of 1.9 μm by an atomic force microscope (AFM). 10%
-20% and the hardness determined by measurement with a Vickers hardness tester is 20 kg / mm ² -100 kg
/ Mm ² , the aluminum support for a lithographic printing plate.