JPH10138653A - Aluminum support for lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide excellent properties of being hard to stain, printing performance and printing plate wear resistance by setting a ratio of specific inclining degree of a surface inclining degree distribution in the case of measuring it at specific revolving power by an interatomic force microscope(AFM) to a specific value. SOLUTION: A ratio of 45 degrees of inclining degree of a surface inclining degree obtained at a revolving power of 0.1μm by an interatomic force microscope(AFM) is preferably 5 to 50% or preferably 10 to 30%. When it is less than 5%, a halftone non-image part is easily contaminated. When it is more than 50%, a non-image part on a blanket is easily contaminated. In this case, a support for a lithographic printing plate having undulations by roughing a surface of the support is preferably grains obtained by superposing large waves at a mean pitch of 5 to 30μm and intermediate waves at a pitch of 0.5 to 3μm of mean diameter in the undulations.

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.

[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, JP-A-6-24166 discloses that
Subsequent to the mechanical roughening treatment, the etching amount is 0.5 to
A chemical etching treatment is performed so as to obtain 30 g / m ^2, and then 200 to 600 C / dm ² is obtained by an alternating waveform current.
^The process of performing AC electrolysis with the quantity of electricity of ² is described.

Further, as a method for 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. Further, Japanese Patent Application Laid-Open No. 7-137474 describes a brush suitable for mechanical surface roughening treatment.

On the other hand, the surface of the roughened aluminum plate has a multilayer structure in which layers composed of undulations in which pits having different opening diameters and depths overlap each other. Specifically, a layer composed of pits having a large average pitch of this undulation (for example, on the order of 10 μm) (sometimes called a large wave)
Is a basic layer, a layer (sometimes called a medium wave) composed of pits on which the average pitch of the undulations is medium (for example, on the order of μm or less), and a fine layer (for example, on the order of 100 mm) It has a multilayer structure in which layers (sometimes called microwaves) composed of pits having a large opening diameter are superimposed. There is also a four-layer structure in which a lower layer is a layer made of pits having an opening diameter even larger than a large wave (sometimes called a super-large wave).

Here, as a technique for defining a lithographic printing plate support based on measurements by an atomic force microscope (AFM),
Japanese Unexamined Patent Publication No. Hei 8-132751 discloses a surface shape of a support that has been subjected to a surface roughening treatment, a desmutting treatment, and an anodic oxidation treatment, with a value for a frequency space of 1 to 10 μm,
A value for a frequency space of 10 to 100 μm is specified, and particularly features from the standpoint of rising at the start of printing, waste paper, and printing durability are described.

[0006]

However, in a technique utilizing the measurement by the AFM as a new technique (for example, Japanese Patent Application Laid-Open No. Hei 8-132751), it is difficult to use a specified lithographic printing plate support. In the surface shape,
Regarding ink stains, particularly stains at halftone dots and stains at non-image areas on a blanket, it has not been specified which gives good effects. The present invention has been made in view of the above circumstances, and has excellent properties such as stain resistance, printing performance, and printing durability.Furthermore, stains in a halftone dot portion and stains in a non-image portion on a blanket have been made. An object of the present invention is to provide an aluminum support for a lithographic printing plate, which exhibits good characteristics against the following.

[0007]

Means for Solving the Problems To achieve the above object, the present invention relates to an aluminum support for a lithographic printing plate in which the surface of an aluminum plate has undulations by roughening, using an atomic force microscope (AFM). , Wherein the ratio of the inclination of the surface inclination distribution at 45 ° or more when measured at a resolution of 0.1 μm is 5% to 50%.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the aluminum support for a lithographic printing plate of the present invention will be described in detail. Atomic Force Microscope used for measurement in the present invention
: AFM) is SP1370 manufactured by Seiko Electronic Industry Co., Ltd.
At 0, the measurement was set on a horizontal sample stand on an aluminum plate sample piezo scanner cut out to a size of 1 cm square,
The cantilever was approached to the surface of the sample, and when it reached a region where atoms work, scanning was performed in the XY directions. At that time, the unevenness of the sample was captured by the displacement of the piezo in the Z direction. The piezo scanner used was capable of scanning XY 150 μm and Z 10 μm. The cantilever is NANOPROBE
12 cantilever SI-DF20
0 to 150 kHz and a spring constant of 12 to 20 N / m in DFM mode (Dynamic Force Mo)
de). Also, by correcting the slight inclination of the sample by least square approximation of the obtained three-dimensional data,
A reference plane was determined.

When measuring the undulation of the large waves, the average surface roughness, and the inclination, four measurement fields of 50 μm square, ie, 1
The measurement was performed on a 00 μm square. Resolution in X and Y directions is 0.1
μm, resolution in the Z direction is 1 nm, scan speed is 25 μm
m / sec. The pitch of the undulation of the large wave was calculated by performing frequency analysis on the three-dimensional data. The average roughness is
Center line average roughness R defined in JIS B0601
This is a three-dimensional extension of a. The surface gradient is calculated by extracting three adjacent points from the three-dimensional data, calculating the angle between a small triangle formed by the three points and the reference plane for all data, obtaining a gradient distribution curve, and calculating the gradient from this. A ratio of 45 degrees or more was issued.

In the present invention, the ratio of the surface inclination measured by AFM of 45 degrees or more is preferably 5% to 50%, more preferably 10% to 30%. If it is less than 5%, the non-image portion is likely to be stained on the halftone dot, and if it is more than 50%, the non-image portion is easily stained on the blanket. That is, if the ratio of the portion having a surface inclination of 45 degrees or more to the total surface area is larger than 50%, the surface of the aluminum plate has many steep portions, and as a result, the ink tends to catch on the non-image portion, and The blanket part corresponding to the part is easily stained with ink. If the ratio of the portion having a surface inclination of 45 degrees or more to the total surface area is smaller than 5%, the water retention of the non-dot image portion deteriorates, and the non-dot image portion is easily stained. Here, in the present invention, the optimum value is realized mainly by the amount of aluminum dissolved in the second chemical etching process for the ratio of the surface inclination of 45 degrees or more when measured at a resolution of 0.1 μm by AFM. I do. In the present invention, the average surface roughness determined by AFM measurement is preferably from 0.35 to 1.0 μm, more preferably from 0.35 to 1.0 μm.
0.8 μm. If it is smaller than 0.35 μm, the non-image area is apt to be stained. AFM
The configuration and measurement principle of C.I. Binnig,
C. F. Quart and Ch. Gerber; P
hys. Rev .. Lett. 56,930 (1986)
Can be referred to.

Here, in a lithographic printing plate support in which the surface of an aluminum plate has undulations due to surface roughening, the undulations are caused by large waves having an average pitch of 5 μm to 30 μm and pits having an average diameter of 0.5 μm to 3 μm. It is preferable that the grain is superimposed with medium waves. When the undulation of the large waves is smaller than 5 μm, the gloss of the surface of the planographic printing plate becomes conspicuous, and the plate inspection property deteriorates. If the undulation of the large waves is greater than 30 μm, the number of printed sheets tends to decrease. The average diameter is 0.
5 μm or more and 3 μm or less honeycomb pit, preferably,
It is preferable that the particles having an average diameter of 0.5 μm or more and 2 μm or less are uniformly formed over the entire surface. If the pit diameter is smaller than 0.5 μm or larger than 3 μm, the contamination performance of the blanket deteriorates. The pit density is 1 × 10
It is preferable that ⁵ to 6 × 10 ⁶ pits / mm ² pits are uniformly formed over the entire surface. If the honeycomb pits are not uniformly formed on the entire surface, the stain performance with a special ink such as gold ink deteriorates. The optimum number of pits and the amount of electricity for generating the honeycomb pits vary depending on the honeycomb pit diameter, but an optimum value can be obtained for each. JP-A-56-470 after electrochemical surface roughening
As described in 41, by chemically etching in an alkaline aqueous solution, the smut component generated by electrochemical surface roughening and the corner portion of the honeycomb pit are dissolved, and the printing with a good stain performance is performed. You can get a version.

Here, the aluminum plate used as the support 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. Aluminum alloys are various, but as a plate material for offset printing, for example,
In Japanese Patent Publication No. 58-6635, Fe and Si components are limited, and an intermetallic compound is specified. In addition, Tokiko Sho 55
In Japanese Patent No. 28874, the cold rolling ratio and the intermediate dulling are performed to limit the voltage application method for electrolytic surface roughening. JP-B-62-41304, JP-B 1-46-577, JP-B-1-
46578, Tokiko 1-47545, Tokiko 1-359
10, JP-B-63-60823, JP-B-63-6082
4, Japanese Patent 4-13417, Japanese Patent 4-19290, Japanese Patent 4-19291, Japanese Patent 4-19293, Japanese Sho 6
2-50540, JP-A-61-272357, JP-A-6-272357
2-74060, JP-A-61-201747, JP-A-61-201747
3-143234, JP-A-63-143235, JP-A-63-255338, JP-A-1-283350, EP272528, U.S. Pat.
818300, EP394816, U.S. Pat.
88, West German Patent 3232810, US Patent 4352
30, EP 239995, US Pat. No. 4,822,715, West German Patent 3,507,402, US Pat. No. 4,715,903,
West German Patent 3507402, EP 289844, U.S. Pat. Nos. 5,097,722 and 4,945,004, West German Patent 3714059, U.S. Pat.
It includes not only the aluminum alloys described in the specifications of 396 and EP1588941, but also all general alloys. 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. EP2
23737, U.S. Pat.
In each of the specifications of No. 0, an application is made in a form in which a trace alloy component is limited. EP 415238 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.

The following processing is performed on the aluminum plate as described above. First, before the mechanical surface roughening treatment, a pretreatment may be performed as necessary. 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, the solvent degreasing method includes gasoline, kerosene,
There are methods using petroleum solvents such as benzene, solvent naphtha and normal hexane, and methods using chlorine solvents such as trichloroethylene, methylene chloride, perchlorethylene and 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; sodium orthosilicate, sodium metasilicate, sodium disilicate, sodium silicate, and the like. A method using an aqueous solution of a silicate, a method using an aqueous solution of a phosphate such as sodium phosphate monobasic, sodium phosphate tribasic, sodium phosphate dibasic, sodium tripolyphosphate, sodium pyrophosphate, sodium hexametaphosphate, and the like can be given. 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. For the degreasing treatment, for example, JP-A-2-26793 can be referred to.

Next, a mechanical roughening process is performed. 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.
As a transfer method of pressing the uneven surface to the aluminum plate,
Various methods can be used. That is, in addition to the above-mentioned JP-A-55-74898, JP-A-60-36195 and JP-A-60-203496, Japanese Patent Application No. 4-175945, which is characterized in that transfer is performed several times. Japanese Patent Application No. Hei 4-20423, characterized in that the paper and the surface are elastic.
No. 5 is 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. As a method for imparting fine irregularities to the transfer roll,
JP-A-3-8635, JP-A-3-66404, JP-A-63-65017 and the like 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 surface 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 6 g / m ² or more and 15 g / m ² or less. If the etching amount is less than 5 g / m ² , the unevenness formed by the mechanical surface roughening treatment cannot be smoothed, and uniform pits cannot be generated in the subsequent electrolytic treatment. On the other hand, if the etching amount exceeds 25 g / m ² , the irregularities disappear.
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. Aqueous salt solution, sodium phosphate monobasic,
Aqueous phosphate solutions such as sodium diphosphate, tertiary sodium phosphate, sodium tripolyphosphate, sodium pyrophosphate, sodium hexametaphosphate and the like can be mentioned. The treatment conditions are as follows: the concentration of the alkaline solution is 0.01%.
５０50% by weight, liquid temperature 20 ° C.-90 ° C., time 5 seconds-5 minutes, and are appropriately selected so as to achieve the above-mentioned etching amount.

When the surface of the aluminum plate is chemically etched with the above alkaline solution, an insoluble residue, that is, 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.

Next, the aluminum plate thus treated 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. In addition, Japanese Unexamined Patent Publication No.
The waveform described in JP-A-79999 can also be used. Also, JP-A-55-158298 and JP-A-56-2
8898, JP-A-52-58602, JP-A-52-15
2302, JP-A-54-85802, JP-A-60-19
0392, JP-A-58-120531, JP-A-63-1
76187, JP-A-1-58889, JP-A-1-18989
280590, JP-A-1-118489, JP-A-1-1-1
48592, JP-A-1-178496, JP-A-1-18
8315, JP-A-1-154797, JP-A-2-235
794, JP-A-3-260100, JP-A-3-2536
00, JP-A-4-72079, JP-A-4-72098,
The methods described in JP-A-3-267400 and JP-A-1-140994 can also be applied. As the frequency,
In addition to the above, those proposed for electrolytic capacitors can also be used. For example, US Pat.
676879.

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 , more preferably 0.5 to 1.5 g / m ^2
2 If the etching amount is less than 0.1 g / m ² , the pit end 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.

Next, an anodic oxide film is formed on the surface of the aluminum plate. For example, a sulfuric acid concentration of 50 to 300 g /
In step (1), an anodized film can be formed in a solution having an aluminum concentration of 5% by weight or less by using an aluminum plate as an anode. Phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid and the like may be added to the solution. The amount of the oxide film formed is 1.0 to 5.0 g /
m ² , particularly preferably 1.5 to 4.0 g / m ² . The anodizing treatment conditions vary depending on the electrolytic solution to be used, and thus cannot be determined unconditionally. The range is 5 to 60 A / cm ² , the voltage is 1 to 100 V, and the electrolysis time is 15 seconds to 50 minutes. As an electrolysis apparatus, Japanese Patent Application Laid-Open No. 48-266
38, JP-A-47-18739, JP-B-58-2451.
It is introduced in 7 publications. Also, Japanese Patent Application Laid-Open No. 54-8 / 1979
1133, JP-A-57-47894, JP-A-57-51
289, JP-A-57-51290, JP-A-57-543
00, JP-A-57-136596, JP-A-58-107
498, JP-A-60-200256, JP-A-62-13
6596, JP-A-63-176494, JP-A-4-17
6897, JP-A-4-280997, JP-A-6-207
299, JP-A-5-24377, JP-A-5-3208
3, JP-A-5-125597, JP-A-5-195291
The methods described in each publication 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 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.

After confirming that the value measured by AFM satisfies the above relationship, 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. Thereafter, water washing by spraying was performed. (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 (d) was removed, and the edge of the generated bit was dissolved to smooth the edge. 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 ions) at a liquid temperature of 35 ° C., a DC voltage, a current density of 2 A / dm ² and an anodized film amount of 2.4 g.
/ M ² . Thereafter, water washing by spraying was performed.

When the surface of the treated aluminum plate was observed by FESEM manufactured by Hitachi, Ltd., the average diameter was 0.5 to 0.5 mm.
3.0 μm honeycomb pits were formed. The average surface roughness and surface gradient distribution obtained by AFM are as shown in Table 1. The intermediate layer and the photosensitive layer were applied to this aluminum plate and dried to prepare a negative PS plate having a dry film thickness of 2.0 g / m ² . When printing was performed using this PS plate, the evaluation results in Table 1 were obtained.

[0047]

[Table 1]

When the surface of the surface-treated aluminum plate is analyzed by an atomic force microscope (AFM), the undulations show a large wave having an average pitch of 5 μm to 30 μm and an average diameter of 0.5 μm.
The grain was superimposed with a medium wave of 3 μm or more and 3 μm or less.
As summarized in Table 1, the average surface roughness Ra determined by measurement with an atomic force microscope is 0.35 μm or more and 1.0 μm or less, and the slope of the surface gradient distribution determined by measurement with an atomic force microscope. When the ratio (a45) of 45 ° or more (a45) is 5% or more and 50% or less, it is understood that the printing plate support is good.

[0049]

As described above, the aluminum support for a lithographic printing plate according to the present invention is manufactured by using an atomic force microscope (AFM).
By setting the ratio of the inclination of the surface inclination distribution of 45 degrees or more when measured at a resolution of 0.1 μm to 5% to 50%, various characteristics such as stain resistance, printing performance, and printing durability are improved. Excellent characteristics can be exhibited with respect to stains on halftone dots and stains on non-image portions on a blanket.

Claims (1)

[Claims] 1. An aluminum support for a lithographic printing plate having an uneven surface due to roughening of an aluminum plate, wherein the surface gradient distribution is measured by an atomic force microscope (AFM) at a resolution of 0.1 μm. The aluminum support for a lithographic printing plate, wherein the ratio of the inclination of 45 ° or more is 5% to 50%.