JP2002103840A - Manufacturing method for aluminum substrate for lithographic printing plate, aluminum substrate for lithographic printing plate and original film of lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method for an aluminum substrate for a lithographic printing plate which can reduce sharply the cost of a raw material, enables printing of an image of an excellent image quality and has an excellent printing performance in respect to a severe ink stain and a blanket stain, the aluminum substrate for the lithographic printing plate and an original film for the lithographic printing plate. SOLUTION: The manufacturing method for the aluminum substrate for the lithographic printing plate comprises a surface roughening treatment process wherein an aluminum sheet is subjected to electrochemical surface roughening in an acid water solution constituted mainly of a hydrochloric acid and an aluminum chloride by using an alternating current. In this process, the duty of the alternating current is 0.25-0.5 and the frequency thereof is 30-200 Hz, while the ratio (QC/QA) between the electrical quantity (QA) of the aluminum sheet at an anode and the electrical quantity (QC) thereof at a cathode is 0.95-2.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an aluminum support for a lithographic printing plate, and more particularly to a method for manufacturing an aluminum support for a lithographic printing plate capable of greatly reducing raw material costs and enabling printing with excellent image quality. The present invention relates to a method, an aluminum support for a lithographic printing plate, and a lithographic printing plate precursor. Further, the present invention relates to a method for producing an aluminum support for a lithographic printing plate having excellent printing performance against severe ink stains and blanket stains, an aluminum support for a lithographic printing plate, and a lithographic printing plate precursor.

[0002]

2. Description of the Related Art Generally, an aluminum support for a lithographic printing plate (hereinafter sometimes referred to as "support") is produced by subjecting one or both surfaces of an aluminum plate to a roughening treatment or the like. The lithographic printing plate precursor is produced by providing a photosensitive layer or the like on the support. Usually, in order to improve the abrasion resistance of the lithographic printing plate during printing, the support is often subjected to anodizing treatment on the surface of an aluminum plate after a roughening treatment. In addition, in order to shorten the time of vacuum adhesion during plate making, fine irregularities called mat layers may be provided on the surface of the photosensitive layer. The lithographic printing plate precursor manufactured in this manner is subjected to plate making processes such as image exposure, development, and washing with water, and is made into a lithographic printing plate. Examples of the image exposure method include a method in which a lith film on which an image is printed is brought into close contact with the surface of a support and exposed to light to make a difference between an image area and a non-image area, a method using a laser, or a method of projecting an image. For example, a method of directly writing an image portion or a non-image portion to make a difference between the image portion and the non-image portion is used. In addition, the undissolved portion of the photosensitive layer forms an image portion as an ink receptor by a developing process performed after image exposure, and the portion of the photosensitive layer dissolved and removed has an aluminum surface or an anodized film surface under the layer. It is exposed and forms a non-image area as a water receptor. After the development, a hydrophilization treatment, gumming, and even a burning treatment may be performed as necessary.

[0003] Such a lithographic printing plate is mounted on a cylindrical plate cylinder of a printing press, and by supplying ink and dampening solution to the plate cylinder, the ink adheres to the lipophilic image area, Water adheres to the hydrophilic non-image area. The lithographic printing plate prints an image on paper from the blanket cylinder after transferring the ink in the image area to the blanket cylinder. However, in some cases, the ink adheres to the non-image portion in a dot-like or annular shape, and as a result, there is a problem that a dot-like or annular stain is generated on the paper surface (severe ink stain). .

In order to suppress the occurrence of such severe ink stains and the like, a method of using a new metal or an aluminum alloy material containing a predetermined additive element component for an aluminum plate used for a support may be considered. The material has a disadvantage that its own cost is high. In addition, although it is conceivable to use aluminum scrap generated in an aluminum manufacturing plant and whose alloy component is known, there is an advantage in that the yield of raw materials is improved, but it is not a low-cost raw material. Absent.

To cope with such a problem that the raw material cost is high, Japanese Patent Application Laid-Open No. 7-81260 discloses that a master alloy containing only an aluminum lump having an aluminum content of 99.7% or more and containing a predetermined element is used. And a method of eliminating the need for adding a metal lump have been proposed. Also, JP-A-7-2055
No. 34 proposes a method of reusing a used lithographic printing plate or a lithographic printing plate that has become defective in the course of production as a raw material for an aluminum plate.

However, even with these methods, a purity of 9% is required.
Since 9.7% or more of the aluminum lump itself is not so inexpensive and it is difficult to secure a used lithographic printing plate as a stable raw material, no great effect was obtained.

[0007] In order to solve such a problem, as a raw material, a material whose alloy component is not controlled, that is, a scrap material containing various impurities or a new metal, the market price is low, and many impurities are contained. It is conceivable to use ingots called secondary ingots (reclaimed ingots) containing elements. However, these materials have hardly been used for controlling alloy components, and thus could not be used at all as raw materials for lithographic printing plates requiring high quality surface treatment appearance and printing performance. In particular, since various intermetallic compounds and precipitates are generated due to impurities in these materials, defects in the anodic oxide film are likely to occur, and severe ink stain resistance is significantly inferior. The presence of intermetallic compounds and precipitates everywhere on the surface has caused a problem that causes such as a blanket stain and the like, which deteriorate the printing performance, are likely to occur.

Further, in suppressing the energy consumption of the recycling of used aluminum, it is essential that the low-purity aluminum plate be used as the aluminum support for the lithographic printing plate in order to reduce the energy consumption in the future. It is an issue.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems by comparing a raw material whose alloy component is not controlled, that is, a scrap material containing various impurities or a new ingot. And the market price is low,
High quality lithographic printing that uses raw metal called secondary metal (recycled metal) containing many impurity elements to greatly reduce raw material costs and suppress severe ink stains and blanket stains. An object of the present invention is to provide a method for producing an aluminum support for a plate, an aluminum support for a lithographic printing plate, and a lithographic printing plate precursor.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have arrived at the present invention. That is, the present invention

<1> An aluminum support for a lithographic printing plate including a surface roughening step of electrochemically roughening an aluminum plate using an alternating current in an acidic aqueous solution mainly containing hydrochloric acid and aluminum chloride. In the manufacturing method, the duty of the alternating current in the surface roughening treatment step may be 0.
25 to 0.5, and the frequency of the alternating current is 30 to 2
00 Hz, and the ratio (Q _C / Q _A ) between the quantity of electricity at the anode (Q _A ) and the quantity of electricity at the cathode (Q _C ) of the aluminum plate is:
It is a method for producing an aluminum support for a lithographic printing plate, wherein the aluminum support is 0.95 to 2.5.

<2> The acidic aqueous solution is added in an amount of 5 to 15 g / l so that the aluminum ion becomes 1 to 10 g / l.
<1> The method for producing an aluminum support for a lithographic printing plate according to <1>, characterized by being obtained by adding aluminum chloride to hydrochloric acid.

<3> A method for producing an aluminum support for a lithographic printing plate using an electrolytic device containing the acidic aqueous solution, wherein in the surface-roughening treatment step, a current is passed through the acidic aqueous solution in which an aluminum plate undergoes an anodic reaction. In proportion to the amount, hydrochloric acid and water, based on the concentration of hydrochloric acid and aluminum ions obtained from the conductivity of the acidic aqueous solution and the propagation speed of ultrasonic waves and the temperature, the amount of hydrochloric acid and water added, And producing the aluminum support for a lithographic printing plate according to <2>, wherein the acid aqueous solution is discharged from the electrolysis device in the same amount as the volume of the hydrochloric acid and water added. Is the way.

<4> The aluminum plate has an aluminum (Al) content of 95 to 99.4% by mass,
And iron (Fe), silicon (Si), copper (Cu), magnesium (Mg), manganese (Mn), zinc (Zn),
It is a scrap aluminum material or a secondary metal containing at least five or more of chromium (Cr) and titanium (Ti) in the following ranges, <1> to
<4> A method for producing an aluminum support for a lithographic printing plate. Fe: 0.3 to 1.0 mass% Si: 0.15 to 1.0 mass% Cu: 0.1 to 1.0 mass% Mg: 0.1 to 1.5 mass% Mn: 0.1 to 1.5% by mass Zn: 0.1 to 0.5% by mass Cr: 0.01 to 0.1% by mass Ti: 0.03 to 0.5% by mass

<5> The method for producing an aluminum support for a lithographic printing plate according to <1>, wherein the aluminum plate is mechanically roughened, and / or A first treatment step of performing a chemical etching treatment to dissolve 15 g / m ² and then performing a desmut treatment in an acidic solution; and treating the aluminum plate treated in the first treatment step with hydrochloric acid. The surface roughening process of electrochemically roughening the aluminum plate using an alternating current in an acidic aqueous solution mainly containing aluminum chloride, and the aluminum plate is electrochemically roughened by the roughening process. A second treatment step of subjecting the aluminum plate to the following treatment (1) or (2), and anodizing treatment of the aluminum plate treated in the second treatment step. And anodizing treatment step of applying a method for producing an aluminum support for a lithographic printing plate which comprises a. (1) An etching treatment for chemically etching the aluminum plate in a sulfuric acid aqueous solution at 60 to 90 ° C. for 1 to 10 seconds.
A chemical etching treatment of dissolving in a range of 0.01 to 5 g / m ² is performed, and then a desmutting treatment is performed in an acidic solution.
Etching process for chemically etching in sulfuric acid aqueous solution at 0-90 ° C for 1-10 seconds

<6> Further, the aluminum plate that has been subjected to the anodizing treatment in the anodizing treatment step is
<5 comprising a hydrophilization treatment step of hydrophilizing in an aqueous solution of sodium silicate or polyvinyl phosphonic acid.
<1> A method for producing an aluminum support for a lithographic printing plate.

<7> Further, the aluminum plate that has been subjected to the anodizing treatment in the anodizing step is
It is characterized by including a sealing step of performing sealing processing.
5> is a method for producing an aluminum support for a lithographic printing plate.

<8> The method further comprises a hydrophilizing step of hydrophilizing the aluminum plate subjected to the sealing treatment in the sealing treatment step in an aqueous solution of sodium silicate or polyvinylphosphonic acid. <2> A method for producing an aluminum support for a lithographic printing plate.

<9> An aluminum support for a lithographic printing plate manufactured by the method for manufacturing an aluminum support for a lithographic printing plate according to <1> to <8>.

<10> A lithographic printing plate precursor obtained by forming at least a positive or negative photosensitive layer on the aluminum support for lithographic printing plate of <9>.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

<< Manufacture of aluminum support for lithographic printing plate
Method> In general, aluminum supports for lithographic printing plates
A degreasing process to remove rolling oil adhering to the
Desmutting process to dissolve the smut on the surface of the aluminum plate
Surface treatment, roughening treatment to roughen the surface of the aluminum plate
Process, anodic oxidation to cover the surface of aluminum plate with oxide film
It is manufactured through processing steps and the like. Method for producing the support of the present invention
The method consists of an acidic aqueous solution mainly composed of hydrochloric acid and aluminum chloride.
Aluminum plate electrochemically using alternating current in liquid
The method includes a roughening step of roughening,
The duty of the alternating current in the conversion treatment step is 0.2
5 to 0.5, and the frequency of the alternating current is 30 to 2
00 Hz, the amount of electricity at the anode of the aluminum plate
(Q_A) And the quantity of electricity at the cathode (Q_C) And the ratio (Q _C/ Q_A)But,
0.95 to 2.5. In addition,
As a method for producing a bright support, the roughening treatment step
Besides, mechanical roughening treatment, in acid or alkali aqueous solution
Aluminum combined with chemical etching treatment etc.
And a anodic oxidation process. Further
In addition, the manufacturing method including the surface roughening treatment step of the present invention
May be a continuous method or an intermittent method.
It is preferably used. Manufactured by the manufacturing method of the present invention.
If necessary, the support may be further subjected to a sealing process,
After passing through the hydration treatment step, the undercoat layer, positive or negative feeling
An optical layer and the like are formed to form a lithographic printing plate precursor. Also, photosensitive
A mat layer may be formed on the layer surface as needed.

<Surface roughening step> First, the roughening step in the present invention will be described. The surface roughening step is a step of passing an alternating current using an aluminum plate as an electrode in an acidic aqueous solution to electrochemically roughen the surface of the aluminum plate. different.

In the present invention, the duty of the alternating current is set in the range of 0.25 to 0.5 in the roughening treatment step. Thereby, the surface of the aluminum plate can be uniformly roughened. If the duty of the alternating current is less than 0.25, the aluminum plate surface cannot be uniformly roughened, and if it exceeds 0.5, the aluminum plate surface cannot be uniformly roughened. Also, the duty of the AC current
Is more preferably in the range of 0.3 to 0.4.
The duty in the present invention refers to ta / T where ta is the time during which the anodic reaction of the aluminum plate continues (anode reaction time) in the cycle T of the alternating current.
In particular, on the surface of the aluminum plate during the cathode reaction, in addition to the formation of a smut component mainly composed of aluminum hydroxide, dissolution and destruction of the oxide film occur, and the pitting reaction starts at the time of the next anode reaction of the aluminum plate. Therefore, selection of the duty of the alternating current has a great effect on uniform surface roughening. Further, in the present invention, the frequency of the alternating current in the surface roughening treatment is set to 30 to 200 Hz. This facilitates the manufacture of a device for flowing a large current.
If the frequency is less than 30 Hz, the carbon as the main electrode is significantly dissolved, and if it exceeds 200 Hz, it becomes difficult to manufacture the electrode device. The frequency of the alternating current is 4
More preferably, the frequency is 0 to 120 Hz.

[0025] The present invention, in the surface roughening process, the quantity of electricity at the time when the aluminum plate electric quantity at the time when the anode, i.e. an anode time electricity Q _A, a cathode, i.e. the cathode time electricity 0.9 the ratio Q _C / Q _a and Q _C
2.5. Thereby, uniform honeycomb pits can be generated on the surface of the aluminum plate.
The Q _C / Q _A is less than 0.9, it tends to be uneven surface shape, even beyond the 2,5, becomes likely to be non-uniform surface profile. Further, as the Q _C / Q _A, and more preferably in the range of 1.5 to 2.0.

The waveform of the alternating current used in the surface roughening process includes a sine wave, a rectangular wave, a triangular wave, and a trapezoidal wave, and among them, a rectangular wave or a trapezoidal wave is preferable. FIG. 1 shows an example of a trapezoidal wave preferably used in the present invention. FIG.
, The vertical axis represents the current value, the horizontal axis represents time, ta is the anode reaction time, tc is the cathode reaction time, tp and tp 'are the time from when the current value reaches 0 to the peak, I
a is the peak current on the anode cycle side and I
c indicates a peak current on the cathode cycle side. When a trapezoidal wave is used as the waveform of the alternating current, the times tp and tp 'from when the current reaches 0 to the peak are 0.1 to 2
msec is preferable, and 0.3 to 1.5 msec is more preferable. If the times tp and tp 'are less than 0.1 msec, the impedance of the power supply circuit influences, and a large power supply voltage is required at the time of rising of the current waveform, so that the equipment cost of the power supply increases. On the other hand, when the times tp and tp 'exceed 2 msec, the influence of the trace components in the acidic aqueous solution becomes large, making it difficult to perform a uniform roughening treatment.

The current density of the AC current is a peak value of a trapezoidal wave or a rectangular wave,
ap and cathode cycle side Icp are both 10-20.
0 A / dm ² is preferred. In the surface roughening step, the total amount of electricity participating in the anodic reaction of the aluminum plate at the time when the electrochemical surface roughening is completed is 50 to 50%.
800 C / dm ² is preferred.

As the acidic aqueous solution used in the present invention, an acidic aqueous solution mainly containing hydrochloric acid and aluminum chloride (hereinafter sometimes referred to as an “acidic aqueous solution mainly containing hydrochloric acid”).
Is used. The “acidic aqueous solution mainly composed of hydrochloric acid and aluminum chloride” as used in the present invention means that the total amount of hydrochloric acid and aluminum ions is 30% by mass or more based on the total components in the acidic solution, % Is preferably contained. As the acidic aqueous solution mainly containing hydrochloric acid, those used for electrochemical surface-roughening treatment using ordinary direct current or alternating current can be used, for example, chlorides such as aluminum chloride, sodium chloride, and ammonium chloride. One or more of these can be used by adding to 5 to 15 g / l hydrochloric acid until saturation is reached from 1 g / l. In the acidic aqueous solution mainly containing hydrochloric acid, metals contained in aluminum alloys such as iron, copper, manganese, nickel, titanium, magnesium, and silicon may be dissolved. As the acidic aqueous solution mainly composed of hydrochloric acid, it is preferable to use an aqueous solution obtained by adding aluminum chloride to hydrochloric acid having a hydrochloric acid concentration of 5 to 15 g / l so that aluminum ions are 1 to 10 g / l. The aluminum ions increase spontaneously during the electrochemical graining treatment. The liquid temperature at this time is preferably from 10 to 95C, more preferably from 30 to 50C.

As the aluminum plate used in the present invention,
Known materials, such as JIS 105, described in the Aluminum Handbook 4th Edition (1990, Light Metal Association)
0 material, JIS1100 material, JIS3003 material, JIS3
103 material, JIS 3005 material and the like can be used, but in the present invention, particularly, the content of aluminum (Al) is 9
9.4 to 95% by mass, and iron (Fe), silicon (Si), copper (Cu), magnesium (Mg), manganese (Mn), zinc (Zn), chromium (Cr), and titanium It is preferable to use an aluminum alloy, a scrap aluminum material, or an aluminum plate using a secondary metal, including at least five or more of (Ti) in a range described later.

According to the present invention, the content of Al is 95-99.
It is preferred to use a 4% by weight aluminum plate. If the content exceeds 99.4% by mass, the allowable amount of impurities decreases, and the cost reduction effect may decrease. On the other hand, if the content is less than 95% by mass, impurities are contained in large amounts, and problems such as cracks may occur during rolling. A more preferred Al content is 95 to 99% by mass, particularly preferably 95 to 97% by mass.

The Fe content is preferably from 0.3 to 1.0% by mass. Fe is 0.1-0.
Among the elements contained at about 2% by mass, the amount of solid solution in Al is small, and most of them remain as intermetallic compounds. If the Fe content exceeds 1.0% by mass, cracks are likely to occur during rolling, and if it is less than 0.3% by mass, the cost reduction effect is undesirably reduced. A more preferable Fe content is 0.5 to 1.0% by mass.

The Si content is preferably 0.15 to 1.0% by mass. Si is JIS2000, 4000
It is an element contained in a large amount of scrap of 6000 series materials. In addition, 0.03-0.1% by mass of new bullion
It is an element that is contained before and after, and exists as a solid solution in Al or as an intermetallic compound. When heated in the process of manufacturing the support, Si that has been dissolved may precipitate as elemental Si. It is known that elemental Si and FeSi-based intermetallic compounds adversely affect severe ink stain resistance. When the content of Si exceeds 1.0% by mass,
For example, treatment with sulfuric acid described later (desmut treatment process)
In some cases, this cannot be completely removed, and if it is less than 0.15% by mass, the cost reduction effect is reduced. A more preferred Si content is 0.3 to 1.0% by mass.

The Cu content is preferably 0.1 to 1.0% by mass. Cu is an element that is largely contained in scraps of JIS2000-based and 4000-based materials. Relatively A
Easy to dissolve in l. If the Cu content exceeds 1.0% by mass, it may not be possible to completely remove the Cu by, for example, a treatment with sulfuric acid described below. If the Cu content is less than 0.1% by mass, the cost reduction effect is reduced. More preferred C
The content of u is 0.3 to 1.0% by mass.

The Mg content is preferably 0.1 to 1.5% by mass. Mg is JIS2000, 3000
-Based, 5000-based, and 7000-based materials. Particularly, since it is contained in a large amount in the can end material, one of the main impurity metals contained in the scrap material
One. Mg is relatively easily dissolved in Al and forms an intermetallic compound with Si. Mg content of 1.5% by mass
If the amount exceeds 0.1%, for example, it may not be completely removed by the treatment with sulfuric acid described below. More preferred M
The content of g is 0.5 to 1.5% by mass, and more preferably 1.0 to 1.5% by mass.

The Mn content is preferably 0.1 to 1.5% by mass. Mn is an element contained in a large amount of JIS 3000-based material scrap. Especially can body
It is one of the main impurity metals contained in the scrap material because it is contained in a large amount in the material. Mn is also relatively easily dissolved in Al and forms an intermetallic compound with AlFeSi. Mn
If the content exceeds 1.5% by mass, it may not be possible to completely remove this by, for example, treatment with sulfuric acid described below,
If the amount is less than 0.1% by mass, the cost reduction effect is reduced. A more preferred Mn content is 0.5 to 1.5% by mass, and still more preferably 1.0 to 1.5% by mass.

The Zn content is preferably 0.1 to 0.5% by mass. Zn is an element particularly contained in JIS 7000 series scrap. Relatively easy to form a solid solution in Al. If the Zn content exceeds 0.5% by mass, for example, it may not be possible to completely remove the Zn by treatment with sulfuric acid described below, and if it is less than 0.1% by mass, the cost reduction effect is reduced. A more preferred Zn content is 0.1.
3 to 0.5% by mass.

The Cr content is preferably 0.01 to 0.1% by mass. Cr is JIS 5000 series, 6000
Metal is an impurity metal contained in a small amount in scraps of 7000 series and 7000 series. If the Cr content exceeds 0.1% by mass, for example, it may not be possible to completely remove the Cr by treatment with sulfuric acid described below, and if it is less than 0.01% by mass, the cost reduction effect is reduced. A more preferable Cr content is 0.05 to 0.1% by mass.

The content of Ti is preferably 0.03 to 0.5% by mass. Ti is usually used as a crystal refining material.
It is an element added in an amount of from 0.01 to 0.04% by mass. JIS5
000 series, 6000 series, and 7000 series scraps are relatively large as impurity metals. If the Ti content exceeds 0.5% by mass, for example, it may not be possible to completely remove the Ti by treatment with sulfuric acid described below, and if it is less than 0.03% by mass, the cost reduction effect decreases.
A more preferable content of Ti is 0.05 to 0.5% by mass.

The aluminum plate used in the present invention is made of a material containing aluminum at the above-mentioned content (purity) and containing five or more of the eight impurity element groups. The aluminum plate is manufactured by subjecting the above-mentioned raw material to a casting using a conventional method, appropriately performing a rolling process or a heat treatment to a thickness of 0.1 to 0.7 mm, and performing a flatness correction process as necessary. Is done. In addition, as a manufacturing method of the aluminum plate, a DC casting method, a DC casting method,
And / or a method omitting the annealing treatment and a continuous casting method can be used.

As the electrolytic device used in the above-mentioned roughening treatment step, a known electrolytic device such as a vertical type, a flat type and a radial type can be used, and a radial type electrolytic device as described in JP-A-5-195300 can be used. Electrolysis devices are particularly preferred. FIG. 2 is a schematic diagram of a radial electrolytic device used in the present invention. In FIG. 2, the radial type electrolysis apparatus is configured such that an aluminum plate W is wound around a radial drum roller 12 arranged in a main electrolysis tank 10, and electrolytic processing is performed by main electrodes 13 a and 13 b connected to an AC power supply 11 in a conveying process. Is done. The acidic aqueous solution 15 is supplied from a solution supply port 14 through a slit 16 to a solution passage 17 between the radial drum roller 12 and the main poles 13a and 13b. Next, the aluminum plate W treated in the main electrolytic cell 10 is
Is subjected to electrolytic treatment. The auxiliary anode tank 20 has an auxiliary anode 2
1 is disposed to face the aluminum plate W, and the acidic aqueous solution 15 is supplied so as to flow between the auxiliary anode 21 and the aluminum plate W. The auxiliary anode 21 can be selected from a known oxygen generation electrode such as ferrite, iridium oxide, platinum, or a material obtained by cladding or plating platinum on a valve metal such as titanium, niobium, or zirconium. The main poles 13a and 13b are made of carbon, platinum, titanium,
It can be selected from niobium, zirconium, stainless steel and electrodes used for cathodes for fuel cells, but carbon is particularly preferred. As the carbon, commercially available impervious graphite for chemical devices, resin-core graphite, and the like can be used.

The supply direction of the acidic aqueous solution passing through the main electrolytic cell 10 and the auxiliary anode cell 20 may be parallel or counter to the progress of the aluminum plate W. The relative flow rate of the acidic aqueous solution to the aluminum plate is 10 to 1000 c.
m / sec is preferred. One or more AC power supplies can be connected to one electrolytic device. Further, two or more electrolysis devices may be used, and electrolysis conditions in each device may be the same or different. Further, after the electrolytic treatment is completed, it is preferable to perform liquid drainage by a nip roller and water washing by spraying so as not to carry out the treatment liquid to the next step.

Further, in the above-mentioned surface roughening treatment, hydrochloric acid and water are converted into, for example, (i) the conductivity of the acidic aqueous solution and (a) ii) Based on the nitric acid and aluminum ion concentrations obtained from the propagation speed of the ultrasonic wave and (iii) the temperature, add the hydrochloric acid and water while adjusting the addition amount, and add the same amount as the added volume of hydrochloric acid and water. It is preferable to keep the concentration of the acidic aqueous solution constant by successively overflowing and discharging the acidic aqueous solution from the electrolytic device.

Next, the surface treatment steps including a mechanical roughening treatment, a chemical etching treatment in an acid or alkali aqueous solution, a desmutting treatment and the like as appropriate will be described in order. The surface treatment step is performed before the surface roughening step (first processing step) or after the surface roughening step and before the anodic oxidation processing step described below (second processing step). It is performed in. However, the following processing steps are exemplifications, and the present invention is not limited to the contents of the following steps. Each of the following treatments including the surface treatment step is optionally performed.

<Surface treatment step> (Mechanical surface roughening treatment) The mechanical surface roughening treatment in the present invention is a treatment for mechanically roughening the surface of an aluminum plate using a brush or the like. Yes, it is preferable to be performed in the first processing step. The mechanical surface roughening treatment is preferably carried out using a rotating nylon brush roll having a bristle diameter of 0.07 to 0.57 mm and a slurry liquid of an abrasive supplied to the surface of the aluminum plate. Known abrasives can be used as the abrasive used in the mechanical surface roughening treatment step. Examples of the abrasive include quartz sand, quartz described in JP-A-6-135175 and JP-B-50-40047. It is preferable to use aluminum hydroxide or a mixture thereof.

The slurry has a specific gravity of 1.05.
Those in the range of ~ 1.3 are preferred. Examples of a method of supplying the slurry liquid to the surface of the aluminum plate include a method of spraying the slurry liquid, a method of using a wire brush, and a method of transferring the surface shape of a roll having irregularities to an aluminum plate. Also, JP-A-55-074898 and JP-A-61-162351
And the methods described in JP-A-63-104889 and the like. Furthermore, Table 9-
As described in JP-A-509108, a mixture of particles consisting of alumina and quartz is mixed at 95: 5 to 5:95.
A method in which the surface of an aluminum plate is polished with a brush in an aqueous slurry containing a mass ratio in the range described above can also be used. At this time, the average particle size of the mixture is 1 to 40 μm.
m, particularly preferably in the range of 1 to 20 μm.

The nylon brush preferably has a low water absorption. For example, nylon bristle 200T (6,10-nylon, softening point: 180 ° C., manufactured by Toray Industries, Inc.)
Melting point: 212-214 ° C, specific gravity: 1.08-1.09,
Moisture percentage: 1.4 to 1. 1 at 20 ° C and 65% relative humidity.
8, 2.2 ° C at 20 ° C and 100% relative humidity.
8. Dry tensile strength: 4.5-6 g / d, dry tensile elongation: 20-35%, boiling water shrinkage: 1-4%, dry tensile resistance: 39-45 g / d, Young's modulus (dry) : 380
440 kg / mm ² ).

(Chemical Etching Treatment in Alkaline Aqueous Solution (Alkali Etching Treatment)) The alkali etching treatment in the present invention refers to a treatment for chemically etching the surface of an aluminum plate in an alkaline aqueous solution. It is preferable to carry out in each of the processing step and the second processing step. The concentration of the alkaline aqueous solution is 1 to 3
0% by mass is preferable, and the alkaline aqueous solution may contain 0.5 to 10% by mass of the alloy component contained in the aluminum plate as well as aluminum. Examples of the alkaline aqueous solution include sodium hydroxide (caustic soda).
An aqueous solution mainly composed of In the present invention, "mainly" means that the main component in the aqueous solution is contained in an amount of 30% by mass or more, preferably 50% by mass or more based on all components.

The alkali etching treatment is preferably carried out at a liquid temperature of the alkaline aqueous solution of from room temperature to 95 ° C. for 1 to 120 seconds. When mixing a chemical etching liquid in an alkaline aqueous solution for the first time, it is preferable to prepare a treatment liquid using liquid sodium hydroxide (caustic soda) and sodium aluminate (sodium aluminate). . After the completion of the alkali etching treatment, it is preferable to perform liquid removal by a nip roller and water washing by spraying so as not to carry out the treatment liquid to the next step.

(Etching Treatment in Acidic Aqueous Solution (Acid Etching Treatment)) The acidic etching treatment in the present invention refers to a treatment for chemically etching an aluminum plate in an acidic aqueous solution. It is preferably applied, and is also preferably applied after the alkali etching treatment. After performing the alkali etching treatment on the aluminum plate, and then performing the acid etching treatment,
The intermetallic compound containing silica or elemental Si on the surface of the aluminum plate can be removed, and defects of the anodic oxide film generated in the subsequent anodic oxidation step can be eliminated.

As the acid which can be used in the above-mentioned acidic etching treatment, phosphoric acid, nitric acid, sulfuric acid, chromic acid, hydrochloric acid, or a mixed acid containing two or more of these acids can be used, and a sulfuric acid aqueous solution is particularly preferable. The concentration of the acidic aqueous solution is 3
The amount is preferably from 00 to 500 g / l, and the acidic aqueous solution may contain not only aluminum but also alloy components contained in an aluminum plate.

In the above-described acidic etching treatment, the solution temperature is set to 60 to
The treatment is preferably performed at 90 ° C., preferably 70 to 80 ° C., for 1 to 10 seconds. At this time, the dissolution amount of the aluminum plate is preferably 0.001 to 0.2 g / m ² . Also,
It is preferable that the acid concentration, for example, the sulfuric acid concentration and the aluminum concentration be selected from a range that does not crystallize at room temperature. Particularly preferred aluminum ion concentration is 0.1 to 15 g / l.
And particularly preferably 5 to 15 g / l. After the completion of the acidic etching treatment, it is preferable to perform liquid drainage with a nip roller and water washing with a spray in order to prevent the treatment liquid from being taken out to the next step.

(Desmut Treatment in Acidic Solution) When a chemical etching treatment is performed using an aqueous alkali solution, smut is generally formed on the surface of the aluminum plate. It is preferable to perform a so-called desmut treatment in which the smut is dissolved in an acidic solution containing hydrochloric acid or a mixed acid composed of two or more of these acids. The desmutting treatment is preferably performed as appropriate in the first and second treatment steps, and is more preferably performed after the alkali etching treatment or the like. The concentration of the acidic aqueous solution is 1 to 300 g / l.
Is preferred. Further, in the acidic aqueous solution, not only aluminum but also the alloy component contained in the aluminum plate is 0.1%.
~ 15 g / l may be dissolved.

In the desmut treatment, the temperature of the acidic solution is preferably from 20 to 95 ° C., more preferably from 30 to 70 ° C. Further, the processing time is preferably 1 to 120 seconds,
2 to 60 seconds is more preferred. After the end of the desmutting treatment, it is preferable to perform draining with a nip roller and washing with water to prevent the treatment liquid from being carried out to the next step. As the desmut treatment liquid (acid solution), it is preferable to use the waste liquid of the acidic aqueous solution used in the surface roughening step in terms of reducing the amount of the waste liquid.

As a first treatment step performed before the above-described roughening treatment step in the present invention, the mechanical roughening treatment on the aluminum plate and / or the dissolution amount of the aluminum plate is reduced to 0%. It is preferable to perform desmutting treatment in the above-mentioned acidic solution after performing alkali etching treatment so as to be 0.01 to 5 g / m ² . In addition, after the above-described surface roughening treatment step, the second treatment step to be performed before the anodizing treatment step to be described later is as follows.
An acidic etching treatment is performed in a sulfuric acid aqueous solution at 90 ° C. for 1 to 10 seconds, or an alkali etching treatment is performed by dissolving an aluminum plate in an alkaline aqueous solution in an amount of 0.01 to 5 g / m ^2. It is preferable to perform a desmutting process or an acidic etching process in a sulfuric acid aqueous solution at 60 to 90 ° C. for 1 to 10 seconds. When the aluminum plate is subjected to an alkali etching treatment, the liquid temperature is 60 to 90 ° C. and 1 to 1 to remove the intermetallic compound containing silica or the elemental Si on the surface of the aluminum plate.
It is preferable to perform the above acidic etching treatment under the condition of 10 seconds. As described above, the acidic etching treatment can eliminate defects in the anodized film generated in the subsequent anodizing treatment step, and as a result, a dot-like ink is formed on a non-image portion called a dust stain during printing. The trouble of sticking can be improved.

<Anodic Oxidation Step> In the method for producing a support of the present invention, the surface roughening step or the second
After the treatment step, it is preferable to carry out anodizing treatment in order to increase the abrasion resistance of the aluminum plate surface (anodizing treatment step). The anodic oxidation treatment referred to in the present invention is a treatment in which an aluminum plate is immersed in an electrolytic solution as an anode and an anodic oxide film is formed on the surface of the aluminum plate by passing an electric current.

As the electrolytic solution used for the anodic oxidation treatment of the aluminum plate, any electrolytic solution capable of forming a porous oxide film can be used. Generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixture thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte. Since the conditions of the anodizing treatment vary depending on the electrolytic solution used, they cannot be specified unconditionally. 1 to 60 A / dm ² ,
It is appropriate that the voltage is in the range of 1 to 100 V and the electrolysis time is in the range of 10 to 300 seconds.

The sulfuric acid method using a sulfuric acid aqueous solution as an electrolytic solution is usually performed using a direct current, but may be performed using an alternating current. The amount of the anodic oxide film formed is 1 to 1
0 g / m ^2, is suitable particularly from 1.1~5g / m ^2. When the amount is less than 1 g / m ² , the printing durability becomes insufficient, and the non-image area of the lithographic printing plate is liable to be scratched. It is easy to occur. If the amount of the anodic oxide film is too large, the anodic oxide film tends to concentrate on the aluminum edge. Therefore, the difference in the amount of anodic oxide coating between the edge portion and the center portion of the aluminum plate is 1 g
/ M ² or less.

In the above anodic oxidation treatment, it is preferable to use sulfuric acid as an electrolytic solution.
And JP-A-48-45303. The sulfuric acid aqueous solution has a sulfuric acid concentration of 10 to 10.
300 g / l, aluminum ion concentration of 1 to 25 g /
1 and more preferably 50 to 200 g / l of an aqueous sulfuric acid solution to add aluminum sulfate to an aluminum ion concentration of 2 to 10 g / l. The liquid temperature is preferably 30 to 60C. When a DC method using a DC current is used, the current density is 1 to 60 A / d.
m ² is preferable, and 5 to 40 A / dm ² is more preferable.

When anodizing treatment is continuously performed on an aluminum plate (aluminum sheet), the concentration of the aluminum plate is set to 5 to 10 in order to prevent current concentration called burning of the aluminum plate.
Anodizing is performed at a low current density of A / dm ^{2, and} the current density is gradually increased toward the second half to increase the current density to 30 to 50 A / d.
It is preferable to set the current density so as to reach m ² or more. At this time, the current density is 5
It is preferable to gradually increase in 15 steps. It is preferable that an independent power supply is provided for each step, and the current density is controlled by the current value of the power supply. As a power supply method, a liquid power supply method using no conductor roller is preferable. In general, iridium oxide or lead can be used for the anode, and aluminum is used for the cathode. An example of an apparatus used for the anodizing treatment is described in Japanese Patent Application No. 11-178624.

A trace component element contained in the aluminum plate may be dissolved in the sulfuric acid aqueous solution. Further, since aluminum is eluted in the aqueous sulfuric acid solution during the anodizing treatment, it is necessary to control the sulfuric acid concentration and the aluminum ion concentration in order to control the process. If the aluminum ion concentration is set low, the sulfuric acid aqueous solution that undergoes anodic oxidation must be renewed frequently, increasing the amount of waste liquid, which is not economical and has environmental problems. On the other hand, when the aluminum ion concentration is set to be high, the electrolysis voltage is increased, the electric power cost is increased, and it is not economical. Preferred combinations of the sulfuric acid concentration, aluminum ion concentration, and liquid temperature for anodic oxidation include (i) a sulfuric acid concentration of 100 to 20.
0 g / l, more preferably 130 to 180 g / l, aluminum ion concentration of 2 to 10 g / l, more preferably 3 to 7 g / l, liquid temperature of 30 to 40 ° C, more preferably 33 to 38 ° C, ii) a sulfuric acid concentration of 50 to 125 g / l,
More preferably 80 to 120 g / l, aluminum ion concentration is 2 to 10 g / l, more preferably 3 to 7 g / l.
1, the liquid temperature is 40 to 70 ° C, more preferably 50 to 60 ° C
It is.

<Hydrophilic treatment step> After the aluminum plate has been subjected to anodizing treatment in the anodizing treatment step, it is preferable to subject the aluminum plate surface to a hydrophilizing treatment in the hydrophilizing treatment step, if necessary. The hydrophilization treatment is described in US Pat. Nos. 2,714,066 and 3,318.
It is preferable to use the alkali metal silicate (for example, an aqueous solution of sodium silicate) disclosed in the specifications of No. 1461, No. 3280734 and No. 3902732. In this method, the support is immersed in an aqueous solution of sodium silicate or subjected to electrolytic treatment in the aqueous solution. Another preferred method is JP-B-36
-22063, and potassium fluoride zirconate disclosed in U.S. Pat. Nos. 3,276,868, 4,153,461, and 46892.
For example, a method of treating with polyvinyl phosphonic acid disclosed in the specification of Japanese Patent No. 72 is used. Among these, it is preferable to perform the hydrophilic treatment using an aqueous solution of sodium silicate and polyvinyl phosphonic acid.

<Sealing Treatment Step> In the present invention, after the anodic oxidation treatment in the above anodic oxidation treatment step, a sealing treatment is performed to close a hole called a micropore formed in the anodic oxide film. preferable. Such a sealing treatment is performed by immersion in hot water and a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath, or the like. It is preferable to perform the above-mentioned hydrophilic treatment after the sealing treatment step. Examples of the inorganic salts include silicates, borates, phosphates, and nitrates, and examples of the organic salts include carboxylate.

<Production Apparatus Available for Production Method of the Present Invention>
Hereinafter, a manufacturing apparatus that can be used in the method for manufacturing an aluminum support for a lithographic printing plate of the present invention will be described. In the production process of the support of the present invention, (1) the rolled and coiled aluminum plate is fed out from a feeding device composed of a multi-axis turret, and (2) each of the above-mentioned processes (mechanical roughening) Treatment, alkali etching treatment, acid etching treatment, desmutting treatment, electrochemical surface roughening treatment, anodizing treatment, sealing treatment, and hydrophilic treatment), and then drying the aluminum plate, and (3) aluminum plate Is preferably wound in a coil shape by a winding device composed of the above-mentioned multi-axis turret, or it is preferable to correct the flatness of the aluminum plate and then cut it into a predetermined length for integration. Also, if necessary, a step of forming (undercoat layer, photosensitive layer, mat layer) in the above process and performing a drying treatment is provided, and the lithographic printing plate precursor is wound into a coil by the winding device. Is also good.

Further, the manufacturing method of the present invention includes a step of continuously inspecting the defect using an apparatus for inspecting a defect on the surface of an aluminum plate, and applying a label of a mark to an edge portion of the found defect. It is preferable to have one or more steps. Further, in the manufacturing method of the present invention, in the feeding step of the aluminum plate, and in the winding step, even when the traveling of the aluminum plate is stopped when replacing the aluminum coil, the traveling speed of the aluminum plate in each of the above steps is reduced. It is preferable to provide a reservoir device for keeping the temperature constant, and it is preferable to provide a step of joining the aluminum plate by ultrasonic or arc welding after the step of feeding the aluminum coil.

The manufacturing apparatus used in the manufacturing method of the present invention includes:
It is preferable to have one or more devices for detecting the traveling position of the aluminum plate and correcting the traveling position. Further, it is preferable that the manufacturing apparatus has one or more driving devices for controlling the tension of the aluminum plate and controlling the traveling speed, and one or more dancer roll devices for controlling the tension.
In addition, the tracking device records whether or not the state of each process is a desired condition. Before the aluminum coil is wound, a label is attached to the edge of the aluminum web, and the condition after the label is the desired condition. It is also preferable that the determination can be made later.

It is preferable that the aluminum plate is charged together with the interleaving paper and adsorbed to each other, and then cut and / or slit to a predetermined length. Also, based on the information on the label attached to the edge of the aluminum plate, after cutting to a predetermined length or before cutting,
It is preferable that the non-defective part and the defective part are separated by using the label as a mark, and only the non-defective part is integrated.

In each step including the above-mentioned feeding step and the like, it is important to set an optimum tension under each condition depending on the size (thickness, width) of the aluminum plate, the aluminum material, or the traveling speed of the aluminum web. . Therefore, it is preferable to provide a plurality of tension control devices for feedback-controlling the signal from the tension sensing device using a driving device for the purpose of tension cutting and traveling speed control and a dancer roll for the purpose of tension control. The driving device generally uses a control method combining a DC motor and a main driving roller. The main drive roller is made of general rubber, but in the step where the aluminum web is in a wet state, a roller made by laminating a nonwoven fabric can be used. In general, rubber or metal is used for each pass roller, but in places where slippage easily occurs with the aluminum web, in order to prevent this slip, a motor or reduction gear is connected to each pass roller, and the signal from the main drive unit is used. It is also possible to provide an auxiliary driving device such as controlling the rotation at a constant speed.

As described in JP-A-10-114046, an aluminum support for a lithographic printing plate can be used.
The difference (R ¹ −R ² ) between the average surface roughness (R ¹ ) in the rolling direction as the arithmetic average surface roughness (Ra) and the average surface roughness (R ² ) in the direction perpendicular to the rolling direction is as described above. The average surface roughness (R ¹ ) in the rolling direction is within 30%, the average curvature in the rolling direction is within 1.5 × 10 ⁻³ mm ⁻¹ , and the curvature distribution in the width direction is 1.5 × 10 3. ^-3 mm ^-1 within, it is preferred rolling direction and the direction perpendicular curvature is within 1.0 × 10 ^-3 mm ^-1. The aluminum support for a lithographic printing plate manufactured by performing the above-mentioned surface roughening treatment has a roll diameter of 20 m.
It is preferable to perform correction using a correction roll having a m-80 mm and a rubber hardness of 50 to 95 degrees. Thereby, even in the automatic transporting step of the lithographic printing press, it is possible to supply an aluminum coil-shaped plate having a flatness which does not cause exposure deviation of the lithographic printing plate precursor. JP-A-9-194093
Japanese Patent Application Laid-Open Publication No. 2000-214,1992 describes a web curl measuring method and apparatus, a curl correcting method and apparatus, and a web cutting apparatus.

In continuously manufacturing an aluminum support for a lithographic printing plate, it is electrically monitored whether each step is operating under appropriate conditions, and the state of each step is adjusted to a desired condition by a tracking device. By recording whether or not, before the aluminum coil is wound, a label is attached to the edge portion of the aluminum web, and whether or not the desired condition after the label can be determined later, At the time of cutting, the quality of that part can be determined at the time of stacking.

The apparatus for treating an aluminum plate used in the above-mentioned roughening treatment step measures at least one of the temperature, specific gravity, electric conductivity and ultrasonic wave propagation velocity of the liquid, obtains the composition of the liquid, and provides feedback. It is preferable that the liquid concentration is controlled to be constant by control and / or feedforward control. Components contained in the aluminum plate, including aluminum ions, dissolve in the acidic aqueous solution in the processing apparatus as the surface treatment of the aluminum plate proceeds. Therefore, in order to keep the aluminum ion concentration and the acid or alkali concentration constant, it is preferable to keep the liquid composition constant by intermittently adding water and acid or water and alkali. The concentration of the acid or alkali added here is 10 to
98% by mass is preferred.

In order to control the concentration of the acid or alkali, for example, the following method is preferable. First, the conductivity, specific gravity, or ultrasonic wave propagation speed of each component liquid in the concentration range that is to be used in advance is measured for each temperature to create a data table. Then, the concentration is measured by referring to the data table of the non-measurement liquid in which the conductivity, the specific gravity or the propagation speed of the ultrasonic wave and the temperature data of the liquid to be measured are prepared in advance. A method for measuring the propagation time of ultrasonic waves with high accuracy and high stability is disclosed in
-235721. A concentration measuring system utilizing the propagation speed of the ultrasonic wave is disclosed in Japanese Patent Application Laid-Open No. 58-77665. A method of preparing a data table showing a correlation between a plurality of physical quantity data for each liquid component and measuring the concentration of the multi-component liquid with reference to the data table is disclosed in Japanese Patent Laid-Open No. 1955/1992.
No. 9 discloses this.

When the above-described method for measuring the concentration using the propagation speed of the ultrasonic wave is applied to the step of roughening the aluminum support for a lithographic printing plate by combining the conductivity and temperature values of the liquid to be measured, the process management becomes difficult. Since it can be performed accurately in real time, it is possible to manufacture products of a certain quality, which leads to an increase in the yield. In addition to the combination of temperature and ultrasonic wave propagation speed and conductivity, a data table is created for each concentration and temperature with each physical quantity such as temperature and specific gravity, temperature and conductivity, temperature and conductivity and specific gravity, etc. If the method of measuring the concentration of the multi-component liquid with reference to the data table is applied to the step of roughening the aluminum support for a lithographic printing plate, the same effect as described above can be obtained. Further, the specific gravity and the temperature are measured, and the slurry concentration of the object to be measured is determined with reference to a data table created in advance, so that the slurry concentration can be measured quickly and accurately.

Since the above-mentioned ultrasonic wave propagation velocity measurement is easily affected by bubbles in the liquid, it is more preferable that the measurement is performed in a pipe which is vertically arranged and has a flow velocity from the bottom to the top. The measurement of the propagation speed of the ultrasonic waves is preferably performed within a pressure range of 1 to 10 kg / cm ² in the pipe, and the frequency of the ultrasonic waves is preferably 0.5 to 3 MHz. In addition, the above specific gravity, conductivity, the measurement of the propagation speed of the ultrasonic wave is easily affected by the temperature, in the heat insulation state,
In addition, it is preferable that the measurement be performed in a pipe whose temperature fluctuation is controlled within ± 0.3 ° C. Furthermore, since it is preferable to measure the conductivity and specific gravity, or the conductivity and the propagation speed of the ultrasonic wave, at the same temperature, it is particularly preferable to measure the same in the same pipe or in the same pipe flow. Since the pressure fluctuation during the measurement leads to a temperature fluctuation, it is preferable that the pressure be as low as possible. It is also preferable that the flow velocity distribution in the pipe to be measured is as small as possible. Further, since the above measurement is easily affected by slurry, dust, and bubbles, it is preferable to measure the liquid that has passed through a filter, a deaerator, or the like.

<< Aluminum support for lithographic printing plate >><Undercoatlayer> The aluminum support for a lithographic printing plate produced by the production method of the present invention may be used, if necessary, before coating a photosensitive layer on the surface thereof. May be provided with an organic undercoat layer. Examples of the organic compound used in the organic undercoat layer include carboxymethylcellulose, dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, and phenylphosphonic acid which may have a substituent, Organic phosphonic acids such as naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, and optionally substituted phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid, and glycerophosphoric acid Organic phosphoric acid, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, organic phosphinic acid such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and triethanolamine Has a hydroxyl group such as hydrochloride -Alanine, and hydrochlorides of amines,
These may be used in combination of two or more.

The organic undercoat layer can be provided, for example, by the following method. (A) a method in which a solution obtained by dissolving the above organic compound in water or an organic solvent such as methanol, ethanol, or methyl ethyl ketone, or a mixed solvent thereof is coated on the support of the present invention and dried, b) water, or an organic solvent such as methanol, ethanol and methyl ethyl ketone, or a solution obtained by dissolving the organic compound in a mixed solvent thereof, by immersing the support of the present invention to adsorb the organic compound, The organic undercoat layer can be provided by a method of washing and drying with water or the like to provide an organic undercoat layer.

In the method (a), 0.005 to 10
% By weight of the organic compound solution can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used. In the method (b), the concentration of the organic solvent solution is 0.01 to 20% by mass, preferably 0.05 to 5% by mass.
The immersion temperature is 20 to 90 ° C., preferably 25 to 5 ° C.
0 ° C., and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute. The solution used for this is ammonia,
Basic substances such as triethylamine and potassium hydroxide,
Adjust the pH with an acidic substance such as hydrochloric acid, phosphoric acid, etc.
It can also be used in the range of H1-12. In addition, a yellow dye can be added to improve the tone reproducibility of the photosensitive lithographic printing plate. The coating amount of the organic undercoat layer after drying is suitably from ² to 200 mg / m ² , and preferably from 5 to 100 mg / m ² . The above coating amount is 2
If it is less than mg / m ² , sufficient printing durability may not be obtained. In addition, the same may occur even when the amount exceeds 200 mg / m ² .

<Backcoat layer> When the lithographic printing plate precursor is overlaid on the back surface (the side on which the photosensitive layer is not provided) of the lithographic printing plate precursor using the support obtained by the production method of the present invention. A coating layer made of an organic polymer compound (hereinafter, sometimes referred to as a “backcoat layer”) may be provided as necessary so that the photosensitive layer is not damaged. The main component of the back coat layer has a glass transition point of 20
It is preferable to use at least one resin selected from the group consisting of a saturated copolymerized polyester resin, a phenoxy resin, a polyvinyl acetal resin and a vinylidene chloride copolymerized resin at a temperature of not lower than ° C.

The saturated copolyester resin comprises a dicarboxylic acid unit and a diol unit. The dicarboxylic acid unit of the polyester used in the present invention includes aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, tetrabromophthalic acid, and tetrachlorophthalic acid; adipic acid, azelaic acid, succinic acid, oxalic acid, and suberic acid And saturated aliphatic dicarboxylic acids such as sebacic acid, malonic acid and 1,4-cyclohexanedicarboxylic acid.

The back coat layer further includes a dye or pigment for coloring, a silane coupling agent, a diazo resin composed of a diazonium salt, an organic phosphonic acid, an organic phosphonic acid for improving the adhesion to the support of the present invention. Phosphoric acid, a cationic polymer, and the like, as well as a wax generally used as a slipping agent, a higher fatty acid, a higher fatty acid amide, a silicone compound composed of dimethylsiloxane, a modified dimethylsiloxane, a polyethylene powder, and the like may be appropriately added. The thickness of the back coat layer is basically even without interleaving paper,
It is sufficient that the photosensitive layer has a thickness that does not easily damage the photosensitive layer described below.
The range of 01 to 8 μm is preferred. The thickness is 0.01 μm
If it is less than 10, it is difficult to prevent the photosensitive layer from being scratched when handling the lithographic printing plates in an overlapping manner. In addition, the thickness is 8 μm.
During printing, the back coat layer swells due to chemicals used around the lithographic printing plate precursor during printing, causing the thickness to fluctuate,
The printing pressure may change to deteriorate the printing characteristics.

Various methods can be applied as a method of coating the back coat layer on the back surface of the support of the present invention. For example, the above-mentioned components for the back coat layer are dissolved in an appropriate solvent and applied as a solution, or an emulsified dispersion is applied and dried. The method of bonding to the support of the present invention, a method of forming a molten coating with a melt extruder and bonding the support to the support of the present invention, and the like, the most preferable in securing the coating amount described above, This is a method in which the back coat component is dissolved in an appropriate solvent, made into a solution, applied, and dried. The solvent used herein is described in JP-A-62-152739.
Organic solvents such as those described in JP-A No. 195/1992 can be used alone or as a mixture. Further, in the production of the lithographic printing plate precursor, either the back coat layer on the back surface or the photosensitive composition layer on the front surface may be coated on the support first,
Alternatively, both may be applied simultaneously.

<< Lithographic printing plate precursor >> The support of the present invention includes:
The lithographic printing plate precursor according to the invention can be prepared by providing the following photosensitive layers. The lithographic printing plate precursor is subjected to exposure, development, and the like, and an image is formed on the lithographic printing plate precursor so as to be ready for printing.

<[I] When a photosensitive layer containing a novolak resin of a mixture of o-naphthoquinonediazidosulfonic acid ester and phenol / cresol is provided> The support of the present invention comprises o-naphthoquinonediazidosulfonic acid ester and phenol / cresol. A photosensitive layer containing a mixed novolak resin can be provided. The o-quinonediazide compound is an o-naphthoquinonediazide compound. For example, U.S. Pat. Nos. 2,766,118, 2,767,092, and 2,772.
No. 2,972, No. 2,859,112, No. 3,102,809, No. 3,10
No. 6,465, 3,635,709, 3,647,443, and many other publications, and these are preferably used. it can. Further, among these, o-naphthoquinonediazidosulfonic 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 preferred. Preferred, especially US Pat.
No. 5,0709, U.S. Pat. No. 4,028,5,709, which is obtained by subjecting a condensate of pyrogallol and acetone to an ester reaction with o-naphthoquinonediazidosulfonic acid.
No. 111, which is obtained by subjecting a polyester having a terminal hydroxy group to an ester reaction with o-naphthoquinonediazidesulfonic acid or o-naphthoquinonediazidecarboxylic acid, and British Patent No. 1,494,043.
O-naphthoquinonediazide sulfonic acid, a homopolymer of p-hydroxystyrene or a copolymer thereof with another copolymerizable monomer as described in
Or, an ester reaction of o-naphthoquinonediazidocarboxylic acid, or a copolymer of p-aminostyrene and another copolymerizable monomer as described in US Pat. No. 3,759,711. Those obtained by subjecting o-naphthoquinonediazidesulfonic acid or o-naphthoquinonediazidocarboxylic acid to an amide reaction are very excellent.

The above o-quinonediazide compound can be used alone, but is 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. 4,028,1.
As described in the specification of Patent No. 11, when a condensate of phenol or cresol substituted with an alkyl group having 3 to 8 carbon atoms, such as t-butylphenol formaldehyde resin, and a condensate of formaldehyde are used together with the phenol resin. More preferred. Further, in order to form a visible image by exposure, for example, o-naphthoquinonediazide-
Compounds such as 4-sulfonyl chloride, an inorganic anion salt of p-diazodiphenylamine, a trihalomethyloxadiazole compound, and a trihalomethyloxadiazole compound having a benzofuran ring are added.

On the other hand, an image coloring agent may be used in the photosensitive layer. Victoria Blue-
Triphenylmethane dyes such as BOH, crystal violet and oil blue are used. In addition, Japanese Unexamined Patent Publication
The dyes described in JP-A-2-293247 are particularly preferred. Further, as a sensitizer, Japanese Patent Publication No. 57-2325
No. 3 phenol substituted with an alkyl group having 3 to 15 carbon atoms, for example, t-butylphenol, n-octylphenol, a novolak resin obtained by condensing t-butylphenol with formaldehyde,
Alternatively, an o-naphthoquinonediazide-4- or -5-sulfonic acid ester of such a novolak resin (for example, described in JP-A-61-242446) can be contained. Further, in order to improve the developability, a nonionic surfactant as described in JP-A-62-251740 can be further contained. The composition described above can be dissolved in a solvent that dissolves the above components and applied on the support of the present invention. The solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate,
-Methoxy-2-propanol, 1-methoxy-2-propyl acetate, methyl lactate, ethyl lactate, dimethylsulfoxide, dimethylacetamide, dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol,
Examples thereof include methanol, ethanol, isopropanol, and diethylene glycol dimethyl ether. These solvents are preferably used alone or in combination. The photosensitive composition comprising these components is preferably provided on the support of the present invention at a solid content of 0.5 to 3.0 g / m ² .

<[II] When a photosensitive layer containing a diazo resin and a water-insoluble and lipophilic polymer compound is provided> The support of the present invention comprises a photosensitive layer containing a diazo resin and a water-insoluble and lipophilic polymer compound. Layers can also be provided. Examples of the diazo resin include, for example, a diazo resin inorganic salt which is an organic solvent-soluble reaction product of p-diazodiphenylamine and formaldehyde, or a condensate of acetaldehyde, hexafluorophosphate, and tetrafluoroborate. Also, as described in U.S. Pat. No. 3,300,309, the above condensate and a sulfonic acid such as P-toluenesulfonic acid or a salt thereof, a phosphinic acid such as benzenephosphinic acid or a salt thereof, a hydroxyl group Containing compounds, for example, organic solvent-soluble diazo resin organic acid salts, which are reaction products with 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid or a salt 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, an aromatic compound having at least one organic group among oxyacid groups and hydroxyl groups of phosphorus, and diazonium. It is a co-condensate containing a compound, preferably an aromatic diazonium compound, as a structural unit. The aromatic ring preferably includes a phenyl group and a naphthyl group. As the aromatic compound having 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-methoxybenzoic acid is preferable. 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, benzenesulfone Acids, p-toluenesulfinic acid, 1-naphthalenesulfonic acid, phenylphosphoric acid, and phenylphosphonic acid.

The aromatic diazonium compound constituting the constitutional unit of the above-mentioned co-condensation diazo resin includes, for example, Japanese Patent Publication No. Sho 49-4.
Although diazonium salts such as those described in JP-A-8001 can be used, diphenylamine-4 is particularly preferred.
-Diazonium salts are preferred. Diphenylamine-4
-Diazonium salts are derived from 4-amino-diphenylamines, such 4-amine-diphenylamines being 4-aminodiphenylamine,
-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-amino-diphenylamine-2'-carboxylic acid and the like, and particularly preferably, 3-methoxy-4-amino-4-diphenylamine, 4-amino Diphenylamine.

Further, diazo resins other than the co-condensed diazo resin with an aromatic compound having an acid group are disclosed in
The diazo resin condensed with an aldehyde having an acid group or an acetal compound thereof described in JP-A-8559, JP-A-3-163551 and JP-A-3-253857 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, and organic phosphoric acids and sulfonic acids such as phenylphosphoric acid. Alkanesulfonic 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, diamylphenoxy-
3-propanesulfonic acid, dinonylphenoxy-3-propanesulfonic acid, dibutylphenoxy-4-butanesulfonic acid, dinonylphenoxy-4-butanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, p-chlorobenzene Sulfonic acid, 2,
5-dichlorobenzenesulfonic acid, sulfosalcylic 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, hexylnaphthalenesulfonic acid, octylnaphthalenesulfonic acid, butoxynaphthalenesulfonic acid, dodecyloxynaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, dioctylnaphthalenesulfonic acid, triisopropylnaphthalene Sulfonic acid, tributylnaphthalenesulfonic acid, 1-naphthol-5-sulfonic acid, naphthalene-1-sulfonic acid,
Aliphatic and aromatic sulfonic acids such as naphthalene-2-sulfonic acid, 1,8-dinitro-naphthalene-3,6-disulfonic acid and dimethyl-5-sulfoisophthalate;
2,2 ′, 4,4′-tetrahydroxybenzophenone,
1,2,3-trihydrooxybenzophenone, 2,
Hydroxy group-containing aromatic compounds such as 2′4-trihydroxybenzophenone; halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid; and perhalogen acids such as HClO ₄ and HIO _4. It is not something that can be done. Among these, particularly preferred are butylnaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, hexafluorophosphoric acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and dodecylbenzenesulfonic acid.

The molecular weight of the diazo resin used in the present invention can be obtained as an arbitrary value by variously changing the molar ratio of each monomer and the condensation conditions.
In order to effectively serve the intended use of the present invention, those having a molecular weight of about 400 to 100,000, preferably about 8
Those having a size of from 00 to 8,000 are 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, such as N- (4-hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) ) Methacrylamide, o-, m-, p-hydroxystyrene, o-, m
-, P-hydroxyphenyl-acrylate or methacrylate.

(2) Acrylic esters and methacrylic esters having an aliphatic hydroxyl group, for example, 2-
They are hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 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, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl Acrylate,
(Substituted) alkyl acrylates such as 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 and N-dimethylaminoethyl methacrylate.

(6) Acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N Acrylamide or methacrylamide such as -nitrophenylacrylamide and N-ethyl-N-phenylacrylamide.

(7) Ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether,
Vinyl ethers such as octyl vinyl ether and phenyl vinyl ether.

(8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.

(9) Styrenes such as styrene, α-methylstyrene and chloromethylstyrene.

(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.

(12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like.

(13) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-aceketyl methacrylamide, N-propionyl methacrylamide, and N- (p-chlorobenzoyl) methacrylamide.

(14) N (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-amino) sulfonylphenylmethacrylamide, N- (1- (3-amino Sulfonyl) naphthyl) methacrylamide, N- (2
-Aminosulfonylethyl) methacrylamides such as methacrylamide, and acrylamides having the same substituents as described above, and o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, Unsaturated sulfonamides such as methacrylic esters such as 1- (3-aminosulfonylnaphthyl) methacrylate and acrylic esters having the same substituents as described above.

(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 US Pat. No. 3,751,257 and polyvinyl acetal resins such as polyvinyl formal resin and polyvinyl butyral resin.

(17) JP-B-54-19773 in which polyurethane is solubilized with alkali, JP-A-57-90474
No. 7, 60-182437, 62-58242
Nos. 62-123452 and 62-123453
No. 63-113450, JP-A-2-14642
Is a polymer compound described in the above item.

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 above copolymer.

In the photosensitive composition used in the photosensitive layer in the present invention, a dye can be further used for the purpose of obtaining a visible image by exposure and a visible image after development. Examples of the dye include Victoria Pure-BOH
[Hodogaya Chemical Co., Ltd.], Oil Blue # 603 [Orient Chemical Co., Ltd.], Patent Pure Blue [Sumitomo Mikuni Chemical Co., Ltd.], Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Violet, Methyl Green, Erythrosin B, Basic Fuchsin ,
Malachite green, oil red, m-cresol purple, rhodamine B, auramine, 4-p-diethylaminophenyliminaphthoquinone, triphenylmethane series represented by cyano-p-diethylaminophenylacetanilide, diphenylmethane series, oxazine series,
Xanthenic, iminonaphthoquinone, azomethine or anthraquinone dyes are mentioned as examples of color changing agents that change from colored to colorless or different colored tones.

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-anilinonaphthylmethane, p, p ', p "
-Primary or secondary arylamine dyes represented by triaminotriphenylmethane. Particularly preferably, triphenylmethane-based and diphenylmethane-based dyes are effectively used, more preferably triphenylmethane-based dyes, and particularly, Victoria Pure Blue BO
H.

Various additives can be further added to the photosensitive composition used in the photosensitive layer 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,
Oligomers and polymers of trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid, of which tricresyl phosphate is particularly preferred), and a sensitizing agent for improving the liposensitivity of the image area (for example, No. 55-527, a half-esterified product of a styrene-maleic anhydride copolymer with an alcohol, a novolak resin such as a pt-butylphenol-formaldehyde resin, and p-hydroxystyrene 5
0% fatty acid ester, etc.), stabilizers {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 a photosensitive layer containing the above-mentioned photosensitive composition on the support of the present invention, a predetermined amount of a photosensitive diazo resin, a lipophilic polymer compound and, if necessary, various additives are appropriately added. Solvents (e.g., 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,
The composition may be dissolved in methyl lactate, ethyl lactate, ethylene dichloride, dimethyl sulfoxide, water or a mixture thereof to prepare a coating solution of the photosensitive composition, which may be coated on a support and dried. 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, methyl lactate and the like, and a low boiling solvent such as methanol and methyl ethyl ketone.

When the photosensitive composition is coated on the support of the present invention, the solid concentration of the photosensitive composition is preferably in the range of 1 to 50% by mass. In this case, the coating amount of the photosensitive composition may be approximately 0.2 to 10 g / m ² (dry mass), more preferably 0.5 to 3 g / m ² (dry mass).
g / m ² .

<Negative Infrared Laser Recording Material> When the lithographic printing plate precursor of the present invention is to be used as a negative lithographic printing plate precursor that can be exposed to an infrared laser, the photosensitive layer can be formed by a useful negative photosensitive material for an infrared laser. Should be provided.
As the negative photosensitive material for infrared laser, (A) a compound which decomposes by light or heat to generate an acid, (B)
A crosslinking agent that is crosslinked by an acid, (C) an alkali-soluble resin, (D) an infrared absorber, (E) a general formula (R ¹ —X) _n —
Compound represented by Ar- (OH) _m ｛R ¹ : C 6-3
2, an alkyl group or an alkenyl group, X: a single bond, O,
S, COO, or CONH, Ar: an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a heterocyclic group, n = 1 to 3,
Compositions consisting of m = 1-3% are useful.

The negative type lithographic printing plate precursor has a drawback that fingerprints are likely to be formed after development and the strength of an image portion is weak. However, such a drawback can be solved by forming a photosensitive layer with the above constituents. Hereinafter, the components of the negative type lithographic printing plate precursor will be described in detail.

The compound (A) which decomposes by light or heat to generate an acid is exemplified by iminosulfonate described in Japanese Patent Application No. 3-140109 and the like. Compounds that generate sulfonic acid include irradiation with a wavelength of 200 to 500 nm, or 100
Compounds that generate an acid when heated at a temperature of not less than ° C are exemplified. Suitable acid generators include a cationic photopolymerization initiator,
An initiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, and the like can be used. These acid generators are preferably added in an amount of 0.01 to 50% by mass based on the total solid content of the image recording material.

Examples of the crosslinking agent (B) for crosslinking with an acid include (i) an aromatic compound substituted with an alkoxymethyl group or a hydroxyl group, (ii) an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-alkoxymethyl group. A compound having an acyloxymethyl group, and (iii) an epoxy compound.

The above (C) alkali-soluble resin includes:
Novolak resins and polymers having a hydroxyaryl group in the side chain are exemplified.

Examples of the composition comprising the infrared absorbent (D) include commercially available dyes such as azo dyes, anthraquinone dyes, and phthalocyanine dyes which effectively absorb infrared rays of 760 to 1200 nm, and black pigments described in Color Index. Red pigments, metal powder pigments, and phthalocyanine pigments are exemplified. Further, it is preferable to add an image colorant such as oil yellow or oil blue # 603 in order to improve the visibility of the image. Further, in order to improve the flexibility of the coating film, a plasticizer such as polyethylene glycol or phthalic ester can be added.

[Positive Infrared Laser Recording Material] When the lithographic printing plate precursor according to the invention is to be used as a positive lithographic printing plate precursor capable of being exposed to an infrared laser, the photosensitive layer is formed of a useful positive photosensitive material for an infrared laser. It is good to provide. Examples of the positive photosensitive material for an infrared laser include (A) an alkali-soluble polymer, (B) a compound that is compatible with the alkali-soluble polymer and reduces alkali solubility, and (C) a compound that absorbs an infrared laser. The positive photosensitive material for an infrared laser is useful. By using the above-mentioned positive photosensitive material for infrared laser, it is possible to eliminate the lack of solubility in the alkali developing solution in the non-image area, and it is also hard to be damaged and has excellent suitability for alkali development in the image area. It can be a good lithographic printing plate precursor.

Examples of the (A) alkali-soluble polymer include (i) a phenolic resin, a cresol resin, a novolak resin, and a pyrogallol resin, which are typically represented by a phenolic hydroxyl group-containing polymer compound; and (ii) a polymer having a sulfonamide group. A compound obtained by copolymerizing a monomer alone or with another polymerizable monomer, (iii) N- (p-
Compounds having an active imide group in the molecule typified by toluenesulfonyl) methacrylamide and N- (p-toluenesulfonyl) acrylamide are preferred. Examples of the component (B) include compounds that interact with the component (A), such as a sulfone compound, an ammonium salt, a sulfonium salt, and an amide compound. For example, the above (A)
When the component is a novolak resin, a cyanine dye is suitable as the component (B).

As the component (C), 750 to 120
A material having an absorption region in the infrared region of 0 nm and having a light / heat conversion capability is preferred. Those having such a function include squarylium dyes, pyrylium salt dyes, carbon black, insoluble azo dyes, and anthraquinone dyes. These pigments preferably have a size in the range of 0.01 μm to 10 μm.
Methyl ethyl ketone or the like is dissolved in an organic solvent, and the mass after drying on an aluminum plate is 1 to 3 g / m ^2.
Is applied and dried so that

[Photopolymerizable Photopolymer Laser Recording Material] In the case of producing a negative type lithographic printing plate precursor that can be exposed to an infrared laser, a photopolymerizable photopolymer photosensitive material is further useful as a material for a photosensitive layer that can be exposed to laser. Materials. In the case of using the photopolymerizable photopolymer photosensitive material, before coating the photosensitive layer, Japanese Patent Application Laid-Open Publication No. HEI 3-3-1605 discloses a method of improving the adhesion between the support of the present invention and the photosensitive layer. No. 56177, JP-A-8-320
It is preferable to provide an adhesive layer containing a silicone compound having a reactive functional group described in JP-A-551-551. That is, a silane compound such as ethylene tetramethoxy silane or ethylene tetraethoxy silane is dissolved in a solvent such as methanol or ethanol at a ratio of 1 to 20% by mass, and is dissolved under an acid catalyst such as hydrochloric acid, nitric acid, phosphoric acid, and sulfonic acid. For hydrolysis. Then, a -Si-O-Si- bond is formed to form a sol, which can be provided as an adhesive layer on the support of the present invention. At this time, the viscosity is 0.2 mPa · s by dissolving the silane compound in a suitable solvent such as methanol.
(0.2 centipoise) to 2000 mPa · s (20 poise).
It is preferably 0 mg / m ² . A photosensitive layer having a polymerizable compound having an addition-polymerizable unsaturated bond (compound having a terminal ethylenic photopolymerizable group), which is a photopolymerizable photopolymer photosensitive material, can be provided on the surface of the adhesive layer.
The photosensitive layer may contain a photopolymerization initiator, an organic polymer binder, a coloring agent, a plasticizer, a thermal polymerization inhibitor, and the like.

Examples of the compound having a terminal ethylenically unsaturated bond include esters of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound (eg, acrylate, methacrylate, itaconate, and maleate), and the like. An amide of a saturated carboxylic acid and an aliphatic polyamine compound (methylenebisacrylamide, xylylenebisacrylamide, etc.) is exemplified. As the photopolymerization initiator, a titanocene compound, a triazine-based, a benzophenone-based, or a benzimidazole-based sensitizer can be used. Further, a sensitizer such as a cyanine dye, a merocyanine dye, a xanthene dye, and a coumarin dye may be used. By providing a photosensitive layer having a coating amount of 1 to 3 g / m ² after drying the photosensitive composition having such a composition on the surface of the support of the present invention,
A negative type lithographic printing plate that can be exposed to infrared laser can be produced.

[Photocrosslinking Photopolymer Type Laser Recording Material] A photocrosslinking photopolymer may be used as the material for the photosensitive layer. As the photocrosslinkable photopolymer,
For example, polyester compounds disclosed in JP-A-52-96696 and polyvinyl cinnamate-based resins described in British Patent No. 1,112,277 are preferable, and a polyester compound having a maleimide group in a side chain is preferred. 62-785
No. 44 is more preferable.

[Sulfonate-type infrared laser recording material] Further, as the material for the photosensitive layer, a sulfonate-type infrared laser recording material may be used. As the above-mentioned sulfonate-type infrared laser recording material, for example, sulfonate compounds disclosed in JP-A-270480, JP-A-2704872, and the like can be used. In addition, photosensitive materials that generate sulfonic acid by the heat generated by infrared laser irradiation and are solubilized in water, and photosensitive materials whose surface polarity changes by irradiating infrared laser with solidifying styrene sulfonic acid ester with sol-gel, Japanese Patent Application No. 9-89816, Japanese Patent Application No. 10-22406, Japanese Patent Application No. 10-027655.
A photosensitive material whose hydrophobic surface changes to hydrophilic by laser exposure described in the specification can be used. In order to further improve the characteristics of the photosensitive layer composed of a polymer compound capable of generating a sulfonic acid group by the above heat, it is preferable to use the following methods in combination. Examples of such a method include (1) a method using in combination with an acid or base generator described in Japanese Patent Application No. 10-7062, and (2) a specific method described in Japanese Patent Application No. 9-340358. Method of providing an intermediate layer, (3) Japanese Patent Application No. 9-248
No. 994, JP-A-10-43921, and (5) Japanese Patent Application No. 10-43921, (4) a method of forming a specific layer structure described in Japanese Patent Application No. 10-43921, and (5) a method of forming a specific layer structure described in Japanese Patent Application No. 10-43921. 1
Examples of the method include the method used in the mode of modifying the surface of solid particles described in JP-A No. 15354.

Other examples of the composition for changing the hydrophilicity / hydrophobicity of the photosensitive layer by utilizing heat generated by laser exposure include, for example, We described in US Pat. No. 2,764,085.
a composition comprising an rner complex which changes to hydrophobic by heat, a specific saccharide described in JP-B-46-27219, a composition which changes to hydrophilic by exposure to a melamine formaldehyde resin or the like; -63704, a composition which is made hydrophobic by heat mode exposure, a composition comprising a polymer which is dehydrated / hydrophobicized by heat, such as a phthalylhydrazide polymer described in US Pat. No. 4,081,572, 3-5810
JP-A No. 0-103760, a composition having a tetrazolium salt structure, which is made hydrophilic by heat, a composition which is made hydrophobic by exposure to a sulfonic acid-modified polymer described in JP-A-60-132760, Examples of the composition include an imide precursor polymer described in JP-A-64-3543, which is hydrophobized by exposure, and a composition formed from a fluorocarbon polymer described in JP-A-51-74706, which is hydrophilized by exposure. Can be.

Further, a composition comprising a hydrophobic crystalline polymer which is made hydrophilic by exposure described in JP-A-3-197190 or a side group insolubilized by heat described in JP-A-7-186562 is disclosed. Comprising a polymer which changes into hydrophilic and a photothermal conversion agent;
A composition comprising a three-dimensionally cross-linked hydrophilic binder containing microcapsules described in JP-A-1849 and hydrophobized by exposure, or valence isomerization or proton transfer isomerization described in JP-A-8-3463. The composition described in JP-B-60-228 includes a composition, a composition that causes a phase structure change (compatibilization) in a layer by heat described in JP-A-8-141819 and changes the hydrophilicity / hydrophobicity, and a composition described in JP-B-60-228. Compositions whose surface morphology and surface hydrophilicity / hydrophobicity are changed by heat can be given.

As another preferred example of the photosensitive layer material, a composition for changing the adhesiveness between the photosensitive layer and the support by so-called heat mode exposure utilizing heat generated by high power and high density laser light is used. You can give things. Specifically, a composition comprising a heat-fusible or heat-reactive substance described in JP-B-44-22957 can be used.

[Electrophotographic photosensitive resin-based laser recording material] As the photosensitive layer of the lithographic printing plate precursor according to the present invention, for example, a ZnO photosensitive layer disclosed in US Pat. No. 3,001,872 is provided. And JP-A-56-16
A photosensitive layer using an electrophotographic photosensitive resin described in JP-A No. 1550, JP-A-60-186847, JP-A-61-238063 or the like may be provided. The coating amount of the photosensitive layer provided on the support of the present invention may be about 0.1 to about 7 g / m ² in terms of dry mass after coating,
Preferably, it is 0.5 to 4 g / m ² .

The basic patent of the electrophotographic method is disclosed in Japanese Patent Publication No. 37-17162, and in addition, Japanese Patent Application Laid-Open No. 56-107246 and Japanese Patent Publication No. 59-36259.
The method disclosed in each gazette such as the gazette can be used. The electrophotographic photosensitive resin is mainly composed of a photoconductive compound and a binder. For the purpose of improving sensitivity and obtaining a desired photosensitive wavelength, known pigments, dyes, chemical sensitizers, and other necessary additives are used. Can be used.

The planographic printing plate precursor according to the invention includes
To increase the adhesion between the light-sensitive support and the photosensitive layer, or after development
To prevent the photosensitive layer from remaining on the
Provide an intermediate layer as necessary to prevent
You may. In order to improve the adhesion, generally
In the interlayer, a diazo resin or a phosphor adsorbing to aluminum, for example, is used.
Use acid compounds, amino compounds, carboxylic acid compounds, etc.
Is preferred. Also, make sure that the photosensitive layer does not remain after development.
To provide an intermediate layer using a highly soluble substance
Preferably, a polymer having good solubility or a water-soluble polymer
It is preferred to use a mer. Further prevention of halation
To do so, include a dye or UV absorber in the intermediate layer
Is preferred. The thickness of the intermediate layer is arbitrary,
Thickness that causes a uniform bond formation reaction with the upper photosensitive layer when
Must. Usually about 1-100m with dry solid
g / m ^TwoIs preferable, and 5 to 40 mg / m^TwoGasa
More preferred.

Further, a mat layer composed of protrusions provided independently of each other may be provided on the applied photosensitive layer. The purpose of providing the mat layer is to improve the vacuum adhesion between the negative image film and the photosensitive lithographic printing plate in the contact exposure, thereby shortening the evacuation time and further crushing the fine halftone dots at the time of exposure due to poor adhesion. Is to prevent. As a method for coating the mat layer, see
Japanese Patent Application Laid-Open No. 58-1826 discloses a method for heat-sealing powdered solid powder described in JP-A-12974.
A method of spraying and drying polymer-containing water described in Japanese Patent Publication No. 36 can be selected as appropriate, but the matte layer itself is dissolved in an aqueous alkali developer containing substantially no organic solvent or removed by this. Possible ones are preferred.

<< Lithographic printing plate >> The lithographic printing plate precursor in which the photosensitive layer is provided on the support of the present invention is exposed to an infrared laser or the like and developed with an alkali developer or the like to form a lithographic printing plate. . The light source used for exposure is 700-1
A 200 nm infrared laser can be used.
In recent years, in the plate making / printing industry, automatic developing machines for printing plate materials have been widely used in order to rationalize and standardize plate making operations, and it is preferable to use the automatic developing machine also in the method of the present invention. The development of the exposed lithographic printing plate precursor according to the present invention includes a developing solution containing an alkali silicate as a main component such as sodium silicate and potassium silicate described in JP-A-54-62004, A developer described in JP-A-8-305039, which contains a non-reducing sugar such as saccharose or trehalose which does not have an aldehyde group or a ketone group and does not show a reducing property as a main component, can be used. Furthermore, an alkali agent such as potassium hydroxide, a development stabilizer such as a polyethylene glycol adduct of a sugar alcohol disclosed in JP-A-6-282079, a reducing agent such as hydroquinone, and a hard water such as ethylenediamine. Softener, nonionic,
Anionic or amphoteric surfactant, or Japanese Patent Publication 3
For example, a polyoxyethylene / polyoxypropylene block polymerization type surfactant disclosed in JP-A-54339 can be added. In the case of alkali silicate,
The molar ratio of SiO ₂ / M ₂ O (M represents an alkali metal)
Is preferably in the range of 0.3 to 3.0. By this development processing, Si can be attached to the surface. Further, it is also possible to measure the amount of Si element present on the surface by ESCA. Further, C, Al, O, S,
The amounts of Si and Ca were measured, and their element ratios (atom.%)
Is calculated as The Si amount is 1 to 25 aotm.
%, Especially 5 to 20 aotm. %.
If the Si content is in this range, it is effective in preventing halation at the time of irradiating infrared laser light.

On the other hand, in the case of the developer containing the above-mentioned non-reducing sugar as a main component, it is necessary to previously hydrophilize the surface of the aluminum support by silicate treatment or the like. Even in this case, the amount of Si adhering to the surface after development is 1 to 25 at.
om. % Is preferred. In the above, the development is preferably carried out using an automatic developing machine. By adding a replenisher having a higher alkali strength than the developer to the developer, the development can be stably performed for a long time. This replenisher contains:
A surfactant such as an anionic surfactant can be added to disperse the developed residue and increase the ink affinity of the printed image area. Further, if necessary, an antifoaming agent and a water softener can be added.

The surface of the developed lithographic printing plate precursor is
It is preferable to carry out a post-treatment with a rinsing solution having a surfactant or a desensitizing solution containing arabic gum or a starch derivative. When using an aqueous solution containing 5 to 15% by mass of arabic gum or a starch derivative at a solid content concentration, the wet application amount is 1 to
The surface after development is protected to 10 ml / m ² .
Further, the coating amount after drying is preferably from 1 to 5 g / m ² . Furthermore, when higher printing durability is required,
It is preferable to perform a burning treatment described in JP-B-61-2518. Also, as the application method,
For example, the surface conditioning liquid disclosed in Japanese Patent Publication No. 55-28062 may be applied with a sponge or absorbent cotton, or may be applied with an automatic coater. When a surface conditioning liquid is used, generally, 0.3 to 0.8 g / m ² (dry mass) is appropriate.

As described above, the lithographic printing plate precursor of the present invention is subjected to processing including development by a conventional method after image exposure, and a resin image is formed to form a lithographic printing plate. For example, in the case of a photosensitive lithographic printing plate precursor having the photosensitive layer of the above [I], after image exposure, US Pat. No. 4,259,434.
The exposed portion is removed by developing with an alkaline aqueous solution as described in the specification, a lithographic printing plate is obtained, and in the case of the lithographic printing plate precursor having the photosensitive layer of the above (II), the image After exposure, the unexposed portion of the photosensitive layer is removed by development with a developing solution as described in U.S. Pat. No. 4,186,006 to obtain a lithographic printing plate.
Also, JP-A-59-84241 and JP-A-57-1
An aqueous alkaline developer composition used for developing a positive-working lithographic printing plate precursor as described in JP-A-92952 and JP-A-62-24263 can also be used.

[0137]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

[Examples 1 to 5 and Comparative Examples 1 and 2] JIS1050- manufactured without intermediate annealing and soaking heat treatment
The following processes were performed using the H18 aluminum rolled plate, and the aluminum support for lithographic printing plates of Examples 1-5 and Comparative Examples 1-2 was manufactured. After completion of each treatment, the substrate was washed with water and drained with a nip roller. The water washing was performed by spraying water from a spray tube.

(1) Mechanical Roughening Treatment A suspension of silica sand (abrasive, average particle size 25 μm) having a specific gravity of 1.12 and water is supplied as a polishing slurry liquid to the surface of an aluminum plate by a spray tube. Meanwhile, mechanical roughening was performed using a brush roller with a rotating nylon brush. The nylon brush material used is nylon-
6,10, hair length 50mm, hair diameter 0.48m
m. The above-mentioned nylon brush is made by drilling holes in a stainless steel cylinder having a diameter of 300 mm and planting the hairs densely. Also, three nylon brushes were used for the brush roller, and the distance between two support rollers (φ200 mm) provided at the lower part of the brush was 300 mm. The brush roller manages the load of the drive motor for rotating the brush with respect to the load before the nylon brush is pressed against the aluminum plate, and the average surface roughness (Ra) of the aluminum plate after the surface roughening is set to 0. It was pressed down to 45 μm. The direction of rotation of the brush was the same as the direction of movement of the aluminum plate. Thereafter, the aluminum plate was washed with water. The concentration of the abrasive is determined by referring to a table created in advance from the relationship between the abrasive concentration, the temperature, and the specific gravity, obtaining the abrasive concentration from the temperature and the specific gravity, and adding water and the abrasive by feedback control to be constant. Kept. When the abrasive was pulverized and the particle size was reduced, the surface shape of the roughened aluminum plate was changed. Therefore, the abrasive having a small particle size was sequentially discharged out of the system by a cyclone. The particle size of the abrasive was in the range of 1-35 μm.

(2) Etching treatment in an alkaline aqueous solution: An aqueous solution containing 27% by mass of NaOH and 6.5% by mass of aluminum ions and having a liquid temperature of 70 ° C. was sprayed on an aluminum plate by a spray tube to form the aluminum plate. The plate was subjected to an alkali etching treatment. The amount of dissolution on the side surface of the aluminum plate on which the electrochemical surface roughening treatment is performed later is 8 g / m ² , and the amount of dissolution on the back surface is 2 g.
/ M ² . The concentration of the etching solution used for the alkali etching treatment is determined by referring to a table created in advance from the relationship between the NaOH concentration, the aluminum ion concentration, the temperature, the specific gravity, and the conductivity of the solution, and the temperature, specific gravity, and The concentration of the etching solution was determined from the conductivity, and water and a 48% by mass NaOH aqueous solution were added by feedback control to keep the concentration constant. Thereafter, a water washing treatment was performed.

(3) Desmut treatment: Next, the liquid temperature is 35 ° C.
Was sprayed onto an aluminum plate using a spray, and a desmutting treatment was performed for 10 seconds. As the acidic aqueous solution used for the desmut, an overflow waste liquid from an electrolytic device used in the next step was used. Then, several spray tubes for spraying the desmut treatment liquid were installed to prevent the surface of the aluminum plate from drying until the next step.

(4) Electrochemical surface roughening treatment in an acidic aqueous solution mainly composed of hydrochloric acid: continuous treatment using the alternating current of trapezoidal wave shown in FIG. 1 and two electrolytic devices shown in FIG. Was subjected to an electrochemical surface roughening treatment. As the acidic aqueous solution,
Aluminum chloride was added to 7.5 g / l of hydrochloric acid to make aluminum ions 4.5 g / l, and the liquid temperature was 35 ° C. Further, the alternating current is measured for the times tp and t until the current value reaches a peak from zero.
p ′ was 1 msec, and the carbon electrode was used as a counter electrode.
The current density at the peak of the alternating current was 50 A / dm ² both when the aluminum plate was the anode and when the cathode was the cathode. Further, Table 1 shows the ratio (Q _C / Q _A ) of the amount of electricity at the anode (Q _A ) to the amount of electricity at the cathode (Q _C ) of the alternating current, the duty, the frequency, and the sum of the amount of electricity at the anode. It was as follows.
Thereafter, a water washing treatment was performed by spraying. To control the concentration of an acidic aqueous solution mainly composed of hydrochloric acid, a 35 mass% hydrochloric acid stock solution and water are added in proportion to the amount of electricity supplied, and an acidic aqueous solution having the same volume as the added volume of hydrochloric acid and water (containing mainly hydrochloric acid). The acidic aqueous solution was sequentially overflowed from the circulation tank and discharged outside the circulation tank system. In addition, with reference to a table created in advance from the relationship between the hydrochloric acid concentration, the aluminum ion concentration, the temperature, the conductivity of the liquid, and the ultrasonic propagation speed of the liquid, the temperature, conductivity,
The concentration of the acidic aqueous solution was determined from the ultrasonic wave propagation speed, and the concentration was kept constant by controlling the sequential addition of the hydrochloric acid stock solution and water.

(5) Etching treatment in alkaline aqueous solution: NaOH 5% by mass, aluminum ion 0.5%
An aqueous solution having a liquid temperature of 45 ° C. containing 50% by mass was sprayed on an aluminum plate using a spray to perform an alkali etching treatment. Table 1 shows the amount of each aluminum plate dissolved. Note that, in Example 3, the alkali etching treatment was not performed. The concentration of the etching solution is determined by referring to a table created in advance from the relationship between the NaOH concentration, the aluminum ion concentration, the temperature, the specific gravity, and the conductivity of the solution, obtaining the etching solution concentration from the temperature, the specific gravity, and the conductivity. And a 48% by weight aqueous NaOH solution were added to keep the concentration constant. Thereafter, a water washing treatment was performed.

(6) Etching treatment in acidic aqueous solution:
Next, sulfuric acid was used as an acidic etching solution under the conditions shown in Table 1, and this was sprayed onto an aluminum plate from a spray tube to perform an acidic etching treatment. The concentration of the acidic etching solution is determined by referring to a table created in advance from the relationship between the sulfuric acid concentration, the aluminum ion concentration, the temperature, the specific gravity, and the conductivity of the solution. Water and 98 by control
% By weight sulfuric acid was added and kept constant. Thereafter, a water washing treatment was performed.

(7) Anodizing treatment: sulfuric acid concentration at a liquid temperature of 35 ° C.
15 mass% aqueous solution (0.5 quality aluminum ion)
%) As an anodizing solution and reduce the DC voltage.
Used, current density 2A / dm ^TwoAnd the amount of anodic oxide coating is 2.
4g / m^TwoAnodizing treatment was performed so that Sun
The concentration of the extreme oxidation treatment solution is determined in advance by the sulfuric acid concentration and aluminum
Created from the relationship between ON concentration, temperature, specific gravity, and liquid conductivity.
Check the temperature, specific gravity and conductivity to
Find the concentration and use feedback control to control the water and 50 mass
% Sulfuric acid was added and kept constant. Then spray
Therefore, washing with water was performed, and Examples 1 to 5 and Comparative Examples 1 to 5 were performed.
An aluminum support for planographic printing plate No. 2 was prepared.

(8) Preparation of a lithographic printing plate: The aluminum support for a lithographic printing plate subjected to the above-mentioned treatment was dried, and an undercoat layer and a dry film thickness of 2.0 g / m ² were formed on the roughened surface. Examples 1 to 5 and Comparative Example 1
~ 2 positive planographic printing plate precursors were prepared. These lithographic printing plate precursors were subjected to processes such as exposure and development to form lithographic printing plates. The planographic printing plates in Examples 1 to 5 shown in Table 1 were observed with a SEM photograph at a magnification of 750 times,
The honeycomb-shaped pits have a uniformly formed surface shape, and the honeycomb-shaped pits have a pitch of 0.1 to 0.1 mm.
It was found that fine unevenness of 5 μm was generated by overlapping. Further, the lithographic printing plates in Examples 1 to 5 were good printing plates having excellent adhesion to the photosensitive layer. Further, no processing unevenness called streak caused by a difference in crystal orientation between aluminum crystal grains was observed. On the other hand, when the lithographic printing plate of Comparative Example 1 was observed with the same SEM photograph as above, the pit shape was not uniform. Also,
During the evaluation described below, the blanket cylinder of the printing press was easily stained. Although the lithographic printing plate in Comparative Example 2 has a uniform surface shape, the portion corresponding to the non-image portion of the printed matter is spot-like in comparison with the lithographic printing plate in each Example in the evaluation described below. It was easy.

<< Evaluation >> Examples 1 to 5 and Comparative Example 1
Printing was performed using the lithographic printing plate prepared in No. 2 to No. 2.
The degree of stain on the surface of each lithographic printing plate after printing was visually observed, and the stain resistance was evaluated according to the following criteria.
Table 1 shows the results. [Criterion] A: Very little ink adhered to the non-image area. C: The non-image portion was significantly stained by the attached ink.

Example 6 In Example 1, the aluminum support for a lithographic printing plate obtained after the anodizing treatment was further immersed in boiling distilled water to perform a sealing treatment. Then, for the purpose of hydrophilic treatment, sodium silicate was immersed in an aqueous solution of 2.5 mass% at a liquid temperature of 70 ° C. for 14 seconds, then washed with water by spraying and dried, and the aluminum support for a lithographic printing plate of Example 6 was used. Was prepared. The concentration of the liquid used in the above-mentioned hydrophilization treatment is determined by referring to a table created in advance from the relationship between the sodium silicate concentration, the temperature, and the conductivity of the liquid, to determine the liquid concentration by the temperature and the conductivity, and to determine the concentration of the water by feedback control. No. 3 sodium silicate stock solution was added and kept constant. An undercoat layer and a negative photosensitive layer were applied to the aluminum support for a lithographic printing plate prepared as described above and dried to prepare a positive lithographic printing plate precursor of Example 6. The lithographic printing plate precursor was subjected to processes such as exposure and development to obtain a lithographic printing plate. When this was used and evaluated under the same conditions as in Example 1, a good printing plate was obtained.
Table 1 shows the results.

Example 7 In Example 1, the aluminum support for a lithographic printing plate obtained after the anodic oxidation treatment was subjected to 2.5% by mass of sodium silicate and 70 ° C. for the purpose of further hydrophilizing. It was immersed in an aqueous solution for 5 seconds, washed with water by spraying, and dried to prepare an aluminum support for a lithographic printing plate of Example 7. An undercoat layer and a negative photosensitive layer were applied to the lithographic printing plate aluminum support, and then dried to prepare a negative lithographic printing plate precursor of Example 7. The lithographic printing plate precursor was subjected to processes such as exposure and development to obtain a negative type lithographic printing plate. When this was used and evaluated under the same conditions as in Example 1, a good printing plate was obtained.
Table 1 shows the results.

[Example 8] In Example 1, 1.5 mass% of polyvinylphosphonic acid was added to the aluminum support for a lithographic printing plate obtained after the anodizing treatment, in order to further hydrophilize the solution, and It was immersed in an aqueous solution at 70 ° C. for 5 seconds, washed with water by spraying, and dried to produce an aluminum support for a lithographic printing plate of Example 8. The concentration of the liquid used in the hydrophilization treatment is determined by referring to a table created in advance from the relationship between the concentration of polyvinylphosphonic acid, the temperature, and the conductivity of the liquid, obtaining the liquid concentration from the temperature and conductivity, and performing feedback control. And a stock solution of polyvinyl phosphonic acid were added to keep the concentration constant. An undercoat layer and a negative photosensitive layer are applied to the lithographic printing plate aluminum support and dried,
The negative planographic printing plate precursor in Example 8 was produced. The lithographic printing plate precursor was subjected to processes such as exposure and development to obtain a lithographic printing plate. When this was used and evaluated under the same conditions as in Example 1, a good printing plate was obtained. Table 1 shows the results.

[Example 9] An aluminum plate used in Example 9 was produced from five types of molten aluminum alloys containing alloy components of compositions A to E shown in Table 2. The aluminum plate was manufactured as follows. First, a molten aluminum alloy was subjected to a molten metal treatment including degassing and filtration, and a 500-mm-thick ingot was produced by a DC casting method. After the surface of the ingot was chamfered to 10 mm, the ingot was heated, hot rolling was started at 400 ° C. without performing a soaking treatment, and the plate was rolled to a thickness of 4 mm. Next, the thickness was reduced to 1.5 mm by cold rolling, intermediate annealing was performed, and then finished to 0.24 mm by cold rolling again to correct the flatness, and then used in Examples 9-1 to 9-5. An aluminum plate was produced. In compositions A to D, the Al purity and all impurity elements are within a predetermined range, and are within a preferable range for the present invention. The composition E is based on Al purity and Fe, Si, Mn, M
The five types of impurity elements, g and Zn, have compositions within a predetermined range, which is a preferable range for the present invention.

The aluminum plate having the composition shown in Table 2 was treated in the same manner as in Example 1 to prepare five types of aluminum supports for planographic printing plates of Example 9. Drying the obtained lithographic printing plate aluminum support,
An undercoat layer and a photosensitive layer were applied to the roughened surface, and then dried to prepare a positive planographic printing plate precursor having a dry film thickness of 2.0 g / m ² . The lithographic printing plate precursor was subjected to processes such as exposure and development to obtain a lithographic printing plate. When this was used and evaluated under the same conditions as in Example 1, a good printing plate was obtained. Table 1 shows the results. Moreover, 5 in Example 9
The lithographic printing plates of this type had a uniform surface shape when observed with a SEM photograph at a magnification of 750. In the honeycomb-shaped pits, fine irregularities having a pitch of 0.1 to 0.5 [mu] m overlapped and occurred. Further, the printing plate was a good printing plate in which the non-image portion was not stained in a dot-like manner in the above evaluation. Further, no processing unevenness called streak due to a difference in crystal orientation between aluminum crystal grains was observed.

Example 10 An aluminum support for a lithographic printing plate according to Example 10 was manufactured by performing the following processes using a JIS1050-H18 rolled aluminum plate manufactured without intermediate annealing and soaking. did. After washing with water after the completion of each treatment, the liquid was drained with a nip roller. Washing was performed by spraying water from a spray tube.

(1) Etching treatment in an alkaline aqueous solution: an aqueous solution containing 27% by mass of NaOH and 6.5% by mass of aluminum ions and having a liquid temperature of 70 ° C. was sprayed onto an aluminum plate with a spray tube to form the aluminum plate. The plate was subjected to an alkali etching treatment. The amount of dissolution on the side of the aluminum plate that is to be subjected to electrochemical surface roughening later is 6 g / m ² , and the amount of dissolution on the back is 2 g.
/ M ² . The concentration of the etching solution used for the alkali etching treatment is determined by referring to a table created in advance from the relationship between the NaOH concentration, the aluminum ion concentration, the temperature, the specific gravity, and the conductivity of the solution, and the temperature, specific gravity, and The concentration of the etching solution was determined from the conductivity, and water and a 48% by mass NaOH aqueous solution were added by feedback control to keep the concentration constant. Thereafter, a water washing treatment was performed.

(2) Desmut treatment: Next, the liquid temperature was 35
An acidic aqueous solution mainly composed of hydrochloric acid at 0 ° C. was sprayed on the aluminum plate by spraying to perform a desmutting treatment for 10 seconds. As the acidic aqueous solution used for the desmut treatment, overflow waste liquid from a circulation tank used in the next step was used.

(3) Electrochemical surface-roughening treatment in an aqueous hydrochloric acid solution: The electrochemical current roughening treatment was carried out continuously using the trapezoidal alternating current shown in FIG. 1 and two electrolytic devices shown in FIG. A roughening treatment was performed. As an acidic aqueous solution, 7.5 g of HCl /
1 g of hydrochloric acid to which aluminum chloride was added to make 4.5 g / l of aluminum ion was used.
° C. In the alternating current, the times tp and tp 'until the current value reaches a peak from zero were 1 msec, and the carbon electrode was used as a counter electrode. The current density at the peak of the alternating current was 50 A / dm ² both when the aluminum plate was the anode and when the cathode was the cathode. Furthermore, the ratio of anode time electricity of alternating current and (Q _A) a cathode time electricity and (Q _C) (Q _C /
Q _A) is 1.9, duty of the alternating current is 0.33, the frequency is 42 Hz, the aluminum plate the total amount of electricity during the anode was 200C / dm ^2. Thereafter, a water washing treatment was performed by spraying. To control the concentration of an acidic aqueous solution mainly composed of hydrochloric acid, a 35 mass% hydrochloric acid stock solution and water are added in proportion to the amount of electricity supplied, and an acidic aqueous solution (aqueous hydrochloric acid solution) having the same volume as the added volume of hydrochloric acid and water is added. This was performed by sequentially overflowing the circulation tank and discharging it to the outside of the circulation tank system. In addition, with reference to a table created in advance from the relationship between hydrochloric acid concentration, aluminum ion concentration, temperature, conductivity of the liquid, and ultrasonic propagation speed of the liquid, the temperature, conductivity, The concentration of the acidic aqueous solution was determined from the ultrasonic wave propagation velocity, and the concentration was kept constant by controlling the addition amounts of the hydrochloric acid stock solution and water sequentially.

(4) Etching treatment in alkaline aqueous solution: NaOH 5% by mass, aluminum ion 0.5%
An aqueous solution containing a mass% of 45 ° C. was used as an etching solution and sprayed onto an aluminum plate using a spray to perform an alkali etching treatment. The dissolution amount of the aluminum plate was 0.1 g / l. The concentration of the etching solution is determined by referring to a table created in advance from the relationship between the NaOH concentration, the aluminum ion concentration, the temperature, the specific gravity, and the conductivity of the solution, obtaining the etching solution concentration from the temperature, the specific gravity, and the conductivity. And 48% by mass
Aqueous NaOH was added and kept constant. Thereafter, a water washing treatment was performed.

(5) Etching treatment in acidic aqueous solution:
Next, the solution temperature was 70 ° C., and the sulfuric acid concentration was 300 g /
A sulfuric acid aqueous solution containing 1 g / l of aluminum ion was used as an acidic etching solution, and this was sprayed onto an aluminum plate from a spray tube to perform an acidic etching treatment for 60 seconds. The concentration of the acidic etching solution is obtained by referring to a table created in advance from the relationship between the sulfuric acid concentration, the aluminum ion concentration, the temperature, the specific gravity, and the conductivity of the solution, obtaining the acidic etching solution concentration from the temperature, the specific gravity, and the conductivity, and performing feedback. Water and 50% by weight sulfuric acid were added under control and kept constant. Thereafter, a water washing treatment was performed.

(6) Anodizing treatment: An aqueous solution having a sulfuric acid concentration of 10% by mass (containing 0.5% by mass of aluminum ions) at a liquid temperature of 35 ° C. was used as an anodizing treatment solution, and a DC voltage was applied to the solution. Anodizing treatment was performed at a density of 2 A / dm ² and an anodized film amount of 2.4 g / m ² . The concentration of the anodizing solution is determined by referring to a table created in advance from the relationship between the sulfuric acid concentration, the aluminum ion concentration, the temperature, the specific gravity, and the conductivity of the solution, and the solution concentration is determined from the temperature, the specific gravity, and the conductivity, and feedback control By water and 5
0% by weight sulfuric acid was added and kept constant. Thereafter, the aluminum plate was washed with water by spraying to prepare an aluminum support for a lithographic printing plate of Example 10.

(7) Preparation of a lithographic printing plate: The aluminum support for a lithographic printing plate which has been treated as described above is dried, and an undercoat layer and a dry film thickness of 2.0 g are formed on the roughened surface.
/ M ² of the photosensitive layer was applied and dried to produce a positive lithographic printing plate precursor in Example 10. This lithographic printing plate precursor was subjected to processes such as exposure and development to obtain a lithographic printing plate. Observation with a SEM photograph at a magnification of 750 times showed that the pits on the honeycomb having a diameter of 4 to 10 μm had a uniformly formed surface shape, and the pitch was 0.1 to 0.5 μm in the honeycomb pits. It was found that the fine irregularities were generated by overlapping. In addition, it was a good printing plate having excellent adhesion to the photosensitive layer. Further, no processing unevenness called streak caused by a difference in crystal orientation between aluminum crystal grains was observed.

[0161]

[Table 1]

[0162]

[Table 2]

From the above Table 1, it can be seen that the planographic printing plates of Examples 1 to 10 are good printing plates with less occurrence of stains even after printing 5,000 sheets. On the other hand, Comparative Examples 1 and 2
The planographic printing plate No. was conspicuous and was not a good printing plate.

According to the method for producing an aluminum support for a lithographic printing plate, the aluminum support for a lithographic printing plate, and the lithographic printing plate precursor of the present invention, uniform surface roughening is performed using an aluminum plate having a low purity. It is also possible to improve the easiness of smearing during printing due to defects in the anodic oxide film.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a trapezoidal wave of an alternating current preferably used in the present invention.

FIG. 2 is a schematic view of a radial electrolytic device used in the present invention.

[Explanation of symbols]

 Reference Signs List 10 main electrolytic cell 11 AC power supply 12 radial drum roller 13a, 13b main electrode 14 solution supply port 15 acidic aqueous solution 20 auxiliary anode tank 21 auxiliary anode W aluminum plate

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C25F 3/04 C25F 3/04 DA G03F 7/00 503 G03F 7/00 503 7/09 501 7/09 501 // C22C 21/00 C22C 21/00 M (72) Inventor Hirokazu Sawada 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Inside Fujisha Shin Film Co., Ltd. (72) Akio Uesugi 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Address Fujisha Shin Film Co., Ltd. F-term (reference) 2H025 AB03 AD01 AD03 DA17 DA18 DA20 DA36 2H096 AA06 CA01 CA03 2H114 AA04 AA14 AA22 AA23 BA01 DA04 DA78 EA02 EA09 FA04 GA03 GA06 GA08 GA09

Claims (10)

[Claims] 1. Production of an aluminum support for a lithographic printing plate including a surface roughening treatment step of electrochemically roughening an aluminum plate using an alternating current in an acidic aqueous solution mainly composed of hydrochloric acid and aluminum chloride. A method, wherein the duty of the alternating current in the roughening step is
Is 0.25 to 0.5, and the frequency of the alternating current is 3
A 0～200Hz, anode electricity quantity of the aluminum plate (Q _A) and cathode time electricity (Q _C) and the ratio of (Q _C / Q _A)
Is from 0.95 to 2.5, a method for producing an aluminum support for a lithographic printing plate. 2. The method according to claim 1, wherein the acidic aqueous solution is obtained by adding aluminum chloride to a 5 to 15 g / l hydrochloric acid aqueous solution so that aluminum ions are 1 to 10 g / l. A method for producing an aluminum support for a lithographic printing plate according to claim 1. 3. A method for producing an aluminum support for a lithographic printing plate using an electrolytic device containing the acidic aqueous solution, wherein the amount of electricity in the acidic aqueous solution causing an aluminum plate to undergo an anodic reaction in the surface roughening step. The proportion of hydrochloric acid and water is adjusted in proportion to the concentrations of hydrochloric acid and aluminum ions, which are determined from the conductivity of the acidic aqueous solution, the propagation speed of ultrasonic waves, and the temperature, and the amount of the hydrochloric acid and water is adjusted. 3. The aluminum support for a lithographic printing plate according to claim 2, wherein the acidic aqueous solution having the same volume as the added volume of the hydrochloric acid and water is discharged from the electrolytic device. Production method. 4. The aluminum plate according to claim 1, wherein a content of aluminum (Al) is 95 to 99.4 mass%, and iron (Fe), silicon (Si), copper (Cu), magnesium (Mg), It is a scrap aluminum material or a secondary metal containing at least five kinds of manganese (Mn), zinc (Zn), chromium (Cr), and titanium (Ti) in the following ranges. Claim 1 to
4. The method for producing an aluminum support for a lithographic printing plate according to any one of the above items 3. Fe: 0.3 to 1.0 mass% Si: 0.15 to 1.0 mass% Cu: 0.1 to 1.0 mass% Mg: 0.1 to 1.5 mass% Mn: 0.1 to 1.5% by mass Zn: 0.1 to 0.5% by mass Cr: 0.01 to 0.1% by mass Ti: 0.03 to 0.5% by mass 5. The method for producing an aluminum support for a lithographic printing plate according to claim 1, wherein the aluminum plate is mechanically roughened, and / or the aluminum plate is washed with an aqueous alkali solution in an alkaline aqueous solution. ~ 1
A first etching step of performing a chemical etching treatment to dissolve 5 g / m ² , and then performing a desmutting treatment in an acidic solution; and treating the aluminum plate treated in the first treatment process with hydrochloric acid. The surface roughening step of electrochemically roughening the aluminum plate using an alternating current in an acidic aqueous solution mainly containing aluminum chloride, and the aluminum sheet is electrochemically roughened by the roughening step. A second treatment step of subjecting the aluminum plate to a treatment shown in the following (1) or (2); and an anodic oxidation treatment step of subjecting the aluminum plate treated in the second treatment step to an anodization treatment. A method for producing an aluminum support for a lithographic printing plate, comprising: (1) An etching treatment for chemically etching the aluminum plate in a sulfuric acid aqueous solution at 60 to 90 ° C. for 1 to 10 seconds.
A chemical etching treatment of dissolving in a range of 0.01 to 5 g / m ² is performed, and then a desmutting treatment is performed in an acidic solution.
Etching process for chemically etching in sulfuric acid aqueous solution at 0-90 ° C for 1-10 seconds 6. The method according to claim 1, further comprising the step of hydrophilizing the aluminum plate, which has been subjected to the anodizing treatment in the anodizing treatment step, in an aqueous solution of sodium silicate or polyvinyl phosphonic acid. 6. The method for producing an aluminum support for a lithographic printing plate according to 5. 7. The method according to claim 5, further comprising the step of sealing the aluminum plate that has been anodized by the anodizing step.
3. The method for producing an aluminum support for a lithographic printing plate according to item 1. 8. The method according to claim 7, further comprising the step of hydrophilizing the aluminum plate subjected to the sealing treatment in the sealing treatment step in an aqueous solution of sodium silicate or polyvinyl phosphonic acid. 3. The method for producing an aluminum support for a lithographic printing plate according to 1. 9. An aluminum support for a lithographic printing plate manufactured by the method for manufacturing an aluminum support for a lithographic printing plate according to claim 1. 10. A lithographic printing plate precursor obtained by forming at least a positive or negative photosensitive layer on the lithographic printing plate aluminum support according to claim 9. Description: