JP2006289969A - Base for lithographic printing form plate and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a base for lithographic form plate capable of obtaining a lithographic printing original plate which is excellent in stain resistance and flaw resistance and excellent in balance between sensitivity and plate wear resistance. <P>SOLUTION: An arithmetic mean roughness Ra of a surface is 0.36-0.50 μm and a number of a dent part of ≥4 μm in depth is ≤3.0 pieces per 400 μm SQARE. Based on a data obtained by extracting a component of 0.02-0.2 μm waverlength from three-dimensional data obtained by measuring 512×512 points of 5 μm SQARE on a surface by using an Atomic Force Microscope, an actual area Sx<SP>5(0.02-0.2)</SP>obtained from the approximate three-point method obtained from a geometrical measuring area S<SB>0</SB>, a surface area ratio ΔS<SP>5(0.02-0.2)</SP>obtained from the following formula (1) is featured to be 50-90%. Herein, the formula (1) is ΔS<SP>5(0.02-0.2)</SP>=(Sx<SP>5(0.02-0.2)</SP>-S<SB>0</SB>)/S<SB>0</SB>×100(%). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a lithographic printing plate support and a method for producing the same. More specifically, the present invention relates to a lithographic printing plate support from which a lithographic printing plate precursor having excellent scratch resistance and excellent balance between sensitivity and printing durability can be obtained, and a method for producing the same.

  The lithographic printing method is a printing method that utilizes the fact that water and oil do not essentially mix, and the printing plate surface of the lithographic printing plate used for this is a region that accepts water and repels oil-based ink ( Hereinafter, this region is referred to as “non-image portion”) and a region that repels water and receives oil-based ink (hereinafter, this region is referred to as “image portion”) is formed.

The surface of an aluminum support for a lithographic printing plate used for a lithographic printing plate (hereinafter also referred to simply as “support for a lithographic printing plate”) has hydrophilicity and water retention because it is used to carry a non-image area. Various performances that are contradictory are required, such as excellent adhesion and excellent adhesion to the image recording layer formed thereon. If the surface of the lithographic printing plate support is too low in hydrophilicity, ink will adhere to the non-image area during printing, and the blanket cylinder will be soiled, and so-called background soiling will occur. That is, the dirt resistance is deteriorated.
In addition, a lithographic printing plate precursor may cause scratch-like image loss due to slight contact such as bumping during handling of the printing plate, slight rubbing with the interleaf, and finger contact with the printing plate. At present, it is difficult to handle the plate work. In order to improve the susceptibility to scratches, attempts have been made to lower the friction coefficient by providing a fluorosurfactant or wax agent layer on the surface of the recording layer, but this is not yet a sufficient measure. .

  If the surface smoothness of the lithographic printing plate support is high, the lithographic printing plate from which the recording layer thereon is also highly smooth has excellent scratch resistance, but the surface smoothness of the lithographic printing plate support is excellent. If it is too high, the adhesion between the lithographic printing plate support and the recording layer is inferior, the recording layer is easily peeled off, and the durability (printing durability) is deteriorated when the number of printed sheets is large.

  If there are locally deep recesses on the surface of the lithographic printing plate support, the lithographic printing plate provided with a positive type image recording layer has a problem that locally deep portions of non-image portions are difficult to be developed. . Further, in a lithographic printing plate provided with a negative type image recording layer, there arises a problem that a locally deep portion of the image portion is hardly formed as an image, and sensitivity is lowered.

  Therefore, in order to improve various performances such as stain resistance, scratch resistance, sensitivity, and printing durability, the surface of the lithographic printing plate support is subjected to various roughening treatments to form irregularities. The

  Patent Document 1 discloses a lithographic printing plate support obtained by subjecting an aluminum plate to a surface roughening treatment and an anodizing treatment, and has a medium wave structure with an average opening diameter of 0.5 to 5 μm and an average opening diameter of 0. A support for a lithographic printing plate having a grain-like shape with a surface superimposed with a small wave structure of 0.01 to 0.2 μm is described, and the obtained lithographic printing plate is excellent in printing durability and stain resistance. Are listed.

In Patent Document 2, a mechanical rough rubbed with a rotating brush while supplying abrasive particles having an average particle diameter of 5 to 70 μm and an SiO ₂ content of 60% by mass or more to an aluminum plate. Uses a lithographic printing plate support obtained by surface treatment, etching treatment, and electrolytic surface roughening treatment in an acidic electrolyte solution. There is described a method for obtaining a lithographic printing plate precursor of a laser plate making mold that does not occur.

Patent Document 3 discloses an actual area S _x ⁵⁰ and a geometric measurement area obtained by an approximate three-point method from three-dimensional data obtained by measuring 512 × 512 points of a surface of 50 μm □ using an atomic force microscope. In S ₀ , the surface area ratio ΔS ⁵⁰ obtained by the following formula (11) is ⁵⁰ to 90%, and the data obtained by extracting the component having a wavelength of 0.02 to 0.2 μm from the three-dimensional data. A lithographic printing plate support having a steepness a45 ^{50 (0.02-0.2)} of 5 to 40%, which is an area ratio of a portion having an inclination of 45 ° or more, is described.

ΔS ⁵⁰ = (S _x ⁵⁰ −S ₀ ) / S ₀ × 100 (%) (11)
JP 2003-112484 A JP 2003-1963 A JP 2004-148798 A

A lithographic printing plate produced by using the lithographic printing plate support of the prior art as described above is excellent in both printing durability and stain resistance.
However, the present inventor has found that these conventional lithographic printing plates can improve the scratch resistance without impairing the stain resistance, and have a room for further improving the balance between sensitivity and printing durability.

  Accordingly, an object of the present invention is to provide a lithographic printing plate support capable of obtaining a lithographic printing plate precursor having excellent stain resistance and scratch resistance, and excellent balance between sensitivity and printing durability, and a method for producing the same. And

As a result of intensive studies on the surface shape of a lithographic printing plate support to achieve the above object, the present inventor has maintained _a relatively high arithmetic average roughness Ra, which is a factor indicating the surface shape, and has a depth of 4 μm or more. The obtained lithographic printing plate support was used when the surface area ratio ΔS ^{5 (0.02-0.2)} obtained by using an atomic force microscope was set to a specific range. The lithographic printing plate precursor was found to be excellent in stain resistance and scratch resistance, and excellent in the balance between sensitivity and printing durability, and the present invention was completed.

  That is, the present invention provides the following (1) to (4).

(1) arithmetic mean roughness R _a of the surface is 0.36～0.50Myuemu, the number of depth 4μm or more recesses is not more than 3.0 per 400 [mu] m □, using an atomic force microscope, Real area S _x ⁵ determined by the approximate three-point method based on data obtained by extracting components having a wavelength of 0.02 to 0.2 μm from three-dimensional data obtained by measuring 512 × 512 points on the surface of 5 μm □ ^A lithographic printing plate support having a surface area ratio ΔS ^{5 (0.02-0.2)} of 50 to 90% obtained from the following formula (1) from ^(0.02-0.2) and the geometric measurement area S ₀ .

ΔS ^{5 (0.02-0.2)} = (S _x ^{5 (0.02-0.2)} −S ₀ ) / S ₀ × 100 (%) (1)
(2) A lithographic printing plate precursor having a recording layer of 1.1 to 1.6 g / m ² on the lithographic printing plate support described in (1) above.

A preferred method for producing the above lithographic printing plate support or lithographic printing plate precursor is as follows.
(3) An aluminum plate is subjected to an electrochemical surface roughening treatment in an aqueous solution containing at least nitric acid, an electrochemical surface roughening treatment in an aqueous solution containing hydrochloric acid, and then brought into contact with an alkaline aqueous solution. A manufacturing method in which an alkali etching treatment is performed so that an etching amount becomes 0.01 to 0.08 g / dm ² .
(4) A manufacturing method in which an aluminum plate is subjected to a mechanical surface roughening treatment by rubbing with a rotating brush while supplying at least an abrasive having an average particle size of 5 to 40 μm and an SiO ₂ content of 60% by mass or more.

  As will be described below, according to the present invention, a lithographic printing plate support that can be used as a lithographic printing plate precursor having excellent scratch resistance and a good balance between sensitivity and printing durability, and a method for producing the same are obtained. .

Arithmetic mean roughness R _a of the surface is 0.36～0.50Myuemu, the number of depth 4μm or more recesses is not more than 3.0 per 400 [mu] m □, the surface area ratio ΔS obtained by the following formula (1) ^{5 (0.02-0.2)} is 50 to 90%.

ΔS ^{5 (0.02-0.2)} = (S _x ^{5 (0.02-0.2)} −S ₀ ) / S ₀ × 100 (%) (1)

Arithmetic mean roughness R _a of the surface is an index representing the uneven shape including a large waviness of the surface of the lithographic printing plate support.
The lithographic printing plate support of the present invention has an arithmetic average roughness _Ra of 0.36 to 0.50 μm, preferably 0.36 to 0.45 μm, more preferably 0.36 to 0.42 μm. The arithmetic average roughness R _a as relatively coarse range and 0.36～0.45Myuemu, when a lithographic printing plate precursor by having combined the following characteristics, excellent stain resistance, the scratch resistance, sensitivity Excellent balance of printing durability.
The reason for the excellent scratch resistance is not clear, but when the arithmetic average roughness of the support is within a predetermined range, the surface of the recording layer provided on the support is homogeneous and has a specific roughness. It is considered that the contact is not a line or a surface but a point that is not a line or a surface, and the scratch resistance is excellent at the time of collision with the paper.

In the lithographic printing plate support of the present invention, the number of recesses having a surface depth of 4 μm or more is 3.0 or less per 400 μm □.
Within the above range, there is a problem of a pot-like residual film in the lithographic printing plate provided with the above-described positive-type image recording layer, and a problem of a pot-like white spot in the lithographic printing plate provided with the negative-type image recording layer. Absent. That is, a lithographic printing plate having excellent sensitivity can be obtained.
The number of recesses having a depth of 4 μm or more is preferably 2.5 or less, more preferably 1.5 or less per 400 μm □.

S _x ^{5 (0.02-0.2)} is obtained by extracting a component with a wavelength of 0.02 to 0.2 μm from three-dimensional data obtained by measuring 512 × 512 points of 5 μm □ on the surface using an atomic force microscope. The actual area obtained from the obtained data based on the approximate three-point method, and S ₀ is the geometric measurement area of 5 μm □ on the surface. The surface area ratio ΔS ^{5 (0.02-0.2)} is a factor indicating the degree of increase in the actual area S _x ^{5 (0.02-0.2)} with respect to the geometric measurement area S ₀ .

The lithographic printing plate support of the present invention has a surface area ratio ΔS ^{5 (0.02-0.2)} of 50 to 90%, preferably 60 to 90%, more preferably 60 to 80%.
When the surface area ratio ΔS ^{5 (0.02-0.2)} is in the above range, when a lithographic printing plate precursor is prepared, the contact area with the recording layer described later is sufficiently wide, so that the adhesion with the recording layer is improved. When the number of printed sheets is large, the durability (printing durability) is excellent.

<Measurement method>
(1) Arithmetic mean roughness R _a
Stylus roughness meter (e.g., Sufcom575, (Inc.) Tokyo Ltd. Seimitsu) is determined by calculating the performs two-dimensional roughness measurement, the arithmetic average roughness R _a as defined in ISO4287.
The arithmetic average roughness _Ra is extracted by a reference length l in the direction of the average line, the X-axis is taken in the direction of the extracted portion, the Y-axis is taken in the direction of the vertical magnification, and the roughness curve is expressed as y = f (x) It is a value calculated | required by following formula (2).

  The conditions for the two-dimensional roughness measurement are shown below.

<Measurement conditions>
Cut-off value 0.8mm, tilt correction FLAT-ML, measurement length 3mm, vertical magnification 10,000 times, scanning speed 0.3mm / sec, stylus tip diameter 2μm

(2) Number of recesses with a depth of 4 μm or more The number of recesses with a depth of 4 μm or more is 0.01 μm with a non-contact surface of 400 μm □ using a laser microscope (for example, Micromap 520, manufactured by Ryoka System Co., Ltd.). The three-dimensional data is obtained by scanning with the resolution of, and the number of concave portions having a depth of 4 μm or more is counted in the three-dimensional data.

(3) Surface area ratio ΔS ^{5 (0.02-0.2)}

(I) Measurement of surface shape with atomic force microscope First, the surface shape is measured with an atomic force microscope (AFM) to obtain three-dimensional data (f (x, y)).

The measurement can be performed, for example, under the following conditions. That is, the lithographic printing plate support is cut to a size of 1 cm square, set on a horizontal sample stage on a piezo scanner, the cantilever is approached to the sample surface, and when the region where the atomic force works is reached, XY Scanning in the direction, the unevenness of the sample is captured by the displacement of the piezo in the Z direction. A piezo scanner that can scan 150 μm in the XY direction and 10 μm in the Z direction is used. The cantilever has a resonance frequency of 120 to 400 kHz and a spring constant of 12 to 90 N / m (for example, SI-DF20 and SI-DF40, both manufactured by Seiko Instruments; NCH, manufactured by NANOSENSORS; or AC-160TS, manufactured by Olympus) ) And measure in DFM mode (Dynamic Force Mode). Further, the reference plane is obtained by correcting the slight inclination of the sample by approximating the obtained three-dimensional data by least squares.
When measuring, measure 512 × 512 points of 5 μm square on the surface. The resolution in the XY direction is 0.01 μm, the resolution in the Z direction is 0.15 nm, and the scan speed is 5 μm / sec.

(Ii) Correction of three-dimensional data Next, a component having a wavelength of 0.02 to 0.2 μm is obtained from the three-dimensional data (f (x, y)) based on the measurement of 5 μm □ of the surface obtained in (i) above. Extract. Specifically, the three-dimensional data obtained in (i) above is subjected to fast Fourier transform to obtain a frequency distribution, and then components having a wavelength less than 0.02 μm and components having a wavelength exceeding 0.2 μm are removed, and then Fourier By performing inverse conversion, a component having a wavelength of 0.02 to 0.2 μm is extracted. In the following description, the three-dimensional data obtained by the correction is referred to as (g (x, y)).

(Iii) Calculation of surface area ratio ΔS ^{5 (0.02-0.2)} Next, using the three-dimensional data (g (x, y)) obtained by correction in (ii) above, three adjacent points are extracted, The total area of the minute triangles formed by the three points is obtained and set as the actual area S _x ^{5 (0.02-0.2)} . The surface area ratio ΔS ^{5 (0.02-0.2)} is obtained by the above formula (1) from the obtained actual area S _x ^{5 (0.02-0.2)} and the geometric measurement area S ₀ .

<Support for lithographic printing plate>
Next, a specific method for producing a lithographic printing plate support to which the present invention is applied will be described.

<Surface treatment>
The support for a lithographic printing plate of the present invention is not particularly limited in its production method, for example, at least on an aluminum plate described later,
1) Mechanical roughening treatment, or
2) Roughening treatment for transferring unevenness to the surface by pressing the uneven surface, or
3) An electrochemical surface roughening treatment is performed in an aqueous solution mainly composed of hydrochloric acid having an electric quantity of 150 C / dm ² or more.
Electrochemistry in which an alternating current is passed in an aqueous solution further containing an acid in any of the above roughening treatments 1) to 3) (hereinafter, these treatments may be collectively referred to as “large wave forming method”). Surface roughening treatment (hereinafter also referred to as “first electrochemical surface roughening treatment”), etching treatment in an alkaline aqueous solution (hereinafter also referred to as “second etching treatment”), and an aqueous solution containing an acid. Electrochemical surface roughening treatment (hereinafter also referred to as “second electrochemical surface roughening treatment”) in which an alternating current is passed, and etching treatment in an alkaline aqueous solution (hereinafter referred to as “third etching treatment”). ) May be applied in this order.

The acid used in the first electrochemical roughening is preferably nitric acid, and the acid used in the second electrochemical roughening is preferably hydrochloric acid.
Further, in the third etching treatment, it is preferable to 0.01~0.08g / dm ² the etching amount, more preferably, to 0.03~0.06g / dm ^2, 0.03~0. More preferably, it is set to 05 g / dm ² . When the etching amount is within this range, the shape of the small wave structure formed by hydrochloric acid electrolysis can be effectively utilized, and the stain resistance and scratch resistance are further improved.
Further, in the second electrochemical graining treatment, the aluminum plate, the sum aluminum plate amount of electricity when the anode is preferably 20C / dm ² or more, more preferably 20~100C / dm ^2, more preferably 30 An electric current is supplied so that it may become -70C / dm < ² >.

Moreover, the manufacturing method of the support body for lithographic printing plates of this invention may be manufactured through various processes other than the above.
Specifically, for example, after the large wave forming method, etching treatment in an alkaline aqueous solution (hereinafter also referred to as “first etching treatment”), desmutting treatment in an acidic aqueous solution (hereinafter also referred to as “first desmutting treatment”). ), First electrochemical roughening treatment, second etching treatment, desmutting treatment in an acidic aqueous solution (hereinafter also referred to as “second desmutting treatment”), second electrochemical roughening treatment, third. Etching treatment, desmutting treatment in an acidic aqueous solution (hereinafter also referred to as “third desmutting treatment”), and anodizing treatment are preferably performed in this order.

  In addition, after the anodizing treatment, it is preferable to further perform a sealing treatment, a hydrophilization treatment, or a sealing treatment and a subsequent hydrophilization treatment.

  Hereinafter, each step of the surface treatment will be described in detail.

<Large wave forming method>
1) Mechanical roughening treatment

  The mechanical roughening treatment is not limited as long as it is a roughening treatment using an abrasive and a brush, but the following mechanical roughening treatment is preferably performed.

Abrasive particles having an average particle size and a particle size distribution in a specific range and having SiO ₂ particles as a main component are rubbed with a rotating brush while being supplied to at least one surface of the aluminum plate. The abrasive particles used in the mechanical roughening treatment preferably have an average particle size in the range of 5 to 50 μm, more preferably in the range of 10 to 40 μm, and particularly preferably in the range of 23 to 35 μm. The content of SiO ₂ in the abrasive particles is desirably 60% by mass or more, preferably 65% by mass to 98% by mass, and particularly preferably 70% by mass to 95% by mass from the viewpoints of hardness and availability. Examples of such abrasive particles include pumice (SiO ₂ content: 73 mass%), silica sand (SiO ₂ content: 95 mass%), and the like. As a commercially available abrasive particle, Pumice (manufactured by PUMEX), silica sand (manufactured by Sanei Silica) and the like can be used. In the present invention, it is particularly preferable to use pumice.

  If the above-mentioned abrasive particles are used in the mechanical surface roughening step, the abrasive particles will not bite into the surface of the aluminum web, and the surface will not be scratched by abrasive particles having a large particle size. Large scratches that lead to so-called bran stains that stain the rubber cylinder of the printing press and spot stains on the printing paper surface do not adhere to the surface of the support.

  The abrasive particles can be used, for example, as a slurry. Examples of the slurry include a suspension in which the abrasive particles are suspended in water at a concentration of about 5 to 50% by mass. In addition to the suspension, a thickener, a dispersant such as a surfactant, and a preservative may be blended.

  The mechanical surface roughening treatment can be performed using, for example, a polishing apparatus including a roller-like brush in which a large number of bristles are implanted on the surface of a cylindrical body as a rotating brush.

  As the polishing apparatus, as shown in FIG. 5, two roller-like brushes 2 disposed above the conveying surface T, which is a virtual surface along the conveying path of the aluminum plate 1 in the present invention, An example of the polishing apparatus includes two pairs of support rollers 4A and 4B provided on the opposite side of the conveying surface T with respect to each of the brushes 2. The support roller 4A is disposed downstream of the roller brush 2 with respect to the transport direction (indicated by an arrow a), and the support roller 4B is upstream of the roller brush 2 with respect to the transport direction a. Is arranged.

  In the polishing apparatus, an abrasive slurry supply tank 6 for supplying the slurry of the abrasive particles is provided on the upstream side of each roller brush 2 above the transport surface T.

  In the polishing apparatus, the number of sets of the roller brush 2 and the support rollers 4A and 4B is not limited to two. As the polishing apparatus, one having only one set of the roller brush 2 and the support rollers 4A and 4B can be used, and one having three or more sets can be used. In the polishing apparatus having only one set of the roller brush 2 and the support rollers 4A and 4B, it is only necessary to provide one abrasive slurry supply tank 6 on the upstream side of the roller brush 2, and the above three sets. In the polishing apparatus having the above, it is only necessary to provide one abrasive slurry supply tank 6 for each set.

  As the roller-like brush 2, a cylinder 2A having an axis parallel to the conveyance surface T and perpendicular to the conveyance direction a, and a side surface of the cylinder 2A are implanted outward along the radial direction. A brush brush with a core having the brush bristles 2 </ b> B may be mentioned.

The brush bristles 2B preferably have a diameter of 0.15 to 1.35 mm and a length in the range of 10 to 100 mm. The brush bristles 2B are preferably planted in the trunk 2A at a flocking density of 30 to 5,000 / cm ² . If a roller-like brush having a diameter and a planting density of the brush bristles 2B within the above range is used, the surface of the aluminum plate is greatly and unevenly damaged so as to lead to so-called bran dirt in the mechanical surface roughening treatment. There is no.

  As brush hair 2B, brush materials such as synthetic resin hair made of synthetic resin such as nylon, propylene and vinyl chloride resin, animal hair such as cow hair, pig hair and horse hair, and hair made of natural fibers such as wool Is mentioned.

  The brush bristles 2B may be planted one by one in the trunk 2A, or may be planted by bundling a plurality, for example, 10 to 5000.

  The rotational speed of the roller brush 2 is preferably about 100 to 1000 rotations / minute, and the rotation direction b is the opposite direction even if it is the same direction as the conveyance direction a of the aluminum web 10 on the polishing surface of the aluminum web 10. It may be.

  In the polishing apparatus, the aluminum web 10 is supported by the supporting rollers 4A and 4B from the lower surface, and is rubbed and roughened by the brush bristles 2B on the upper surface.

2) Roughening treatment for transferring unevenness to the surface by pressing the uneven surface Specifically, in the final rolling step of the aluminum plate described later, the uneven surface is pressed against the aluminum plate by a method such as lamination rolling or transfer. Asperities are formed on the surface.
Above all, along with cold rolling to adjust the final plate thickness or finish cold rolling to finish the surface shape after final plate thickness adjustment, the uneven surface is transferred to the aluminum plate by pressing the uneven surface to the aluminum plate. A method of forming an uneven pattern is preferred. Specifically, the method described in JP-A-6-262203 can be suitably used.

  The transfer is particularly preferably performed in the final cold rolling step of a normal aluminum plate. Rolling for transfer is preferably performed in 1 to 3 passes, and the rolling reduction of each is preferably 1 to 20%, and preferably 5 to 15%.

As a method for obtaining a rolling roll having irregularities on its surface, used for transferring irregularities, for example, a method of subjecting the surface of a steel roll to a surface roughening treatment by air blasting, shot blasting or sand blasting, a grindstone containing abrasive grains, or Examples thereof include a method of polishing with paper, a method of irradiating a laser to generate a dent, a method of chemical surface roughening treatment or electrochemical surface roughening treatment. When a chemical surface roughening treatment or an electrochemical surface roughening treatment is performed, a resist is applied, and then exposure and development are performed to generate a pattern, and etching can be performed so as to form the pattern.
The roughening treatment may be wet or dry, but is preferably dry, and air blast is particularly preferable.
The air blasting is preferably performed at an air pressure of 1 to 10 kg / cm ² . Examples of the grid used for air blasting include alumina, silica sand, and metal powder. Of these, alumina is preferable. The average particle diameter of alumina is preferably 1 to 200 μm, and more preferably 20 to 150 μm. Air blasting is preferably performed twice.
As for the rolling roll which has an unevenness | corrugation on the surface, it is preferable that average surface roughness is 0.3-3 micrometers, and it is more preferable that it is 0.5-1.5 micrometers.
After obtaining the rolling roll having irregularities on the surface by the above-described method, it is preferable to harden by quenching, hard chrome plating or the like in order to prevent surface abrasion. The thickness of the hard chrome plating is preferably 3 to 15 μm.

  For example, JP-A-60-36195, JP-A-2002-251005, JP-A-60-203495, JP-A-55-74898, and JP-A-62-2 The method described in each publication of No. 111792 can be used.

3) Electrochemical surface roughening in an aqueous solution mainly composed of hydrochloric acid with an electric quantity of 150 C / dm ² or more In hydrochloric acid alternating current electrolysis, a large crater-like undulation is generated by increasing the total electric quantity involved in the anodic reaction. In this case, fine irregularities with an average opening diameter of 0.01 to 0.4 μm are formed on the entire surface, overlapping with crater-like undulations with an average opening diameter of 10 to 30 μm.
In order to obtain such a grain, the total amount of electricity involved in the anode reaction of the aluminum plate at the time when the electrolytic reaction is completed is preferably 150 C / dm ² or more, more preferably 250 C / dm ² or more. are more preferable, but preferably not 800C / dm ² or less, more preferably 500C / dm ² or less. The current density at this time is preferably ²⁰ to 100 A / dm ² at the peak value of the current.
Conditions other than the amount of electricity are the same as in the case of an electrochemical roughening treatment mainly composed of hydrochloric acid described later.

<First etching process>
An etching process is a process which melt | dissolves a surface layer by making the aluminum plate mentioned above contact alkaline aqueous solution.

  The first etching process performed before the first electrochemical surface roughening process includes forming a uniform recess by the first electrochemical surface roughening process and rolling the surface of the aluminum plate (rolled aluminum). It is performed for the purpose of removing oil, dirt, natural oxide film and the like.

In the first etching treatment, the etching amount of the surface to be subjected to electrochemical graining treatment later, is preferably from 0.1~12g / m ^2, more in the range of 3 to 10 g / m ² preferable. When the etching amount is within the above range, the rolling oil, dirt, natural oxide film, etc. on the surface are sufficiently removed, and uniform pits are formed in the subsequent electrochemical roughening treatment, and the amount of alkaline aqueous solution used This is economically advantageous because an increase in the amount is avoided.

  Examples of the alkali used in the alkaline aqueous solution include caustic alkali and alkali metal salts. Specifically, examples of caustic alkali include caustic soda and caustic potash. Examples of the alkali metal salt include alkali metal silicates such as sodium metasilicate, sodium silicate, potassium metasilicate, and potassium silicate; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium aluminate and alumina. Alkali metal aluminates such as potassium acid; alkali metal aldones such as sodium gluconate and potassium gluconate; dibasic sodium phosphate, dibasic potassium phosphate, primary sodium phosphate, primary potassium phosphate, etc. An alkali metal hydrogen phosphate is mentioned. Among these, a caustic alkali solution and a solution containing both a caustic alkali and an alkali metal aluminate are preferable from the viewpoint of high etching rate and low cost. In particular, an aqueous solution of caustic soda is preferable.

In the first etching treatment, the concentration of the alkaline aqueous solution is preferably 1 to 50% by mass, and more preferably 10 to 35% by mass.
The alkaline aqueous solution preferably contains aluminum ions. The aluminum ion concentration is preferably 0.01 to 10% by mass, and more preferably 3 to 8% by mass.
The temperature of the aqueous alkali solution is preferably 20 to 90 ° C. The treatment time is preferably 1 to 120 seconds.

  Examples of the method of bringing the aluminum plate into contact with the alkaline aqueous solution include, for example, a method of passing the aluminum plate through a bath containing an alkaline aqueous solution, a method of immersing the aluminum plate in a bath containing an alkaline aqueous solution, and an alkaline aqueous solution of aluminum. The method of spraying on the surface of a board is mentioned.

  Among these, a method of spraying an alkaline aqueous solution onto the surface of the aluminum plate is preferable. Specifically, a method of spraying an etching solution in an amount of 10 to 100 L / min per spray tube from a spray tube having φ2 to 5 mm holes at a pitch of 10 to 50 mm is preferable. It is preferable to provide a plurality of spray tubes.

After the alkali etching process is completed, it is preferable to drain the liquid with a nip roller, and further perform the water washing process for 1 to 10 seconds and then drain the liquid with a nip roller.
The water washing treatment is preferably carried out using an apparatus for washing with a free-falling curtain-like liquid film, and further using a spray tube.

FIG. 1 is a schematic cross-sectional view of an apparatus for washing with a free-fall curtain-like liquid film. As shown in FIG. 1, an apparatus 100 for performing water washing treatment with a free-fall curtain-like liquid film includes a water storage tank 104 that stores water 102, a water supply pipe 106 that supplies water to the water storage tank 104, and a water storage tank. And a rectifying unit 108 for supplying a free-falling curtain-like liquid film from 104 to the aluminum plate 1.
In the apparatus 100, water 102 is supplied to the water supply tank 104 from the water supply pipe 106, and when the water 102 overflows from the water supply tank 104, the water is rectified by the rectifying unit 108, and a free-falling curtain-like liquid film is applied to the aluminum plate 1. Supplied. When the apparatus 100 is used, the liquid amount is preferably 10 to 100 L / min. Moreover, it is preferable that the distance L in which the water 102 between the apparatus 100 and the aluminum 1 exists as a free fall curtain-like liquid film is 20-50 mm. Moreover, it is preferable that the angle (alpha) of an aluminum plate is 30-80 degrees with respect to a horizontal direction.

If an apparatus for washing with a free-fall curtain-like liquid film as shown in FIG. 1 is used, the aluminum plate can be uniformly washed with water, so that the uniformity of the treatment performed before the washing process is improved. Can be improved.
As a specific apparatus for washing with a free-fall curtain-like liquid film, for example, an apparatus described in JP-A-2003-96584 is preferably exemplified.

  Moreover, as a spray tube used for the water-washing process, for example, a spray tube having a plurality of spray tips in the width direction of the aluminum plate in which spray water spreads in a fan shape can be used. The distance between spray tips is preferably 20 to 100 mm, and the amount of liquid per spray tip is preferably 0.5 to 20 L / min. It is preferable to use a plurality of spray tubes.

<First desmut treatment>
After the first etching process, it is preferable to perform pickling (first desmut process) in order to remove dirt (smut) remaining on the surface. The desmut treatment is performed by bringing the aluminum plate into contact with an acidic aqueous solution.

  Examples of the acid used include nitric acid, sulfuric acid, hydrochloric acid, chromic acid, phosphoric acid, hydrofluoric acid, and borohydrofluoric acid. Specifically, for example, the sulfuric acid aqueous solution waste liquid used in the anodizing process described later, the nitric acid aqueous solution waste liquid used in the first electrochemical surface roughening process, and the second electrochemical surface roughening process were used. A waste solution of hydrochloric acid aqueous solution can be suitably used.

  The first desmut treatment is preferably performed using an acidic solution containing 0.5 to 30% by mass of acid and 0.5 to 10% by mass of aluminum ions. For example, the aluminum plate is brought into contact with an acidic solution having a concentration of 0.5 to 30% by mass (containing aluminum ions of 0.01 to 5% by mass) such as hydrochloric acid, nitric acid, and sulfuric acid.

  In the first desmut treatment, the temperature of the acidic solution is preferably 25 to 90 ° C. The treatment time is more preferably 1 to 180 seconds.

Examples of the method of bringing the aluminum plate into contact with the acidic solution include a method in which the aluminum plate is passed through a tank containing the acidic solution, a method in which the aluminum plate is immersed in a tank containing the acidic solution, and the acidic solution being aluminum. The method of spraying on the surface of a board is mentioned.
Among these, a method in which an acidic solution is sprayed on the surface of an aluminum plate is preferable. Specifically, a method in which an acidic solution is sprayed in an amount of 10 to 100 L / min per spray tube from a spray tube having φ2 to 5 mm holes at a pitch of 10 to 50 mm is preferable. It is preferable to provide a plurality of spray tubes.

After the desmutting process is completed, it is preferable to drain the liquid with a nip roller, and further perform the water washing process for 1 to 10 seconds, and then drain the liquid with a nip roller.
The water washing treatment is the same as the water washing treatment after the alkali etching treatment. However, the amount of liquid per spray tip is preferably 1 to 20 L / min.

<First electrochemical roughening treatment>
The first electrochemical surface roughening treatment is a treatment for applying an electrochemical surface roughening by passing an alternating current through an aluminum plate in an acid-containing aqueous solution. The acid added to the aqueous solution is preferably nitric acid. By performing the first electrochemical surface roughening treatment (nitric acid electrolytic surface roughening treatment) using an aqueous solution containing nitric acid, pits having an average opening diameter of 0.5 to 5 μm are formed on the surface of the aluminum plate. The

The nitric acid concentration in the aqueous solution is preferably 1 to 100 g / L. Within the above range, the uniformity of the pits becomes high.
The temperature of the aqueous solution is preferably 20 to 80 ° C, and more preferably 30 to 60 ° C. When the temperature is 20 ° C. or higher, the refrigerator operating cost for cooling does not increase, and the amount of groundwater used for cooling can be suppressed. When it is 80 ° C. or lower, it is easy to ensure the corrosion resistance of the equipment.

  Nitric acid compounds having nitrate ions such as aluminum nitrate, sodium nitrate, and ammonium nitrate, or hydrochloric acid compounds having hydrochloric acid ions such as aluminum chloride, sodium chloride, and ammonium chloride can be added to the aqueous solution. Moreover, the metal contained in aluminum alloys, such as iron, copper, manganese, nickel, titanium, magnesium, a silica, may melt | dissolve in aqueous solution. Hypochlorous acid or hydrogen peroxide may be added at 1 to 100 g / L.

  Furthermore, it is preferable to add aluminum chloride, aluminum nitrate or the like to the aqueous solution so that the aluminum ion concentration is 3 to 50 g / L. When the aluminum ion concentration is within the above range, the pit uniformity is increased. Moreover, the replenishment amount of the aqueous solution does not increase too much.

  Further, by adding and using a compound capable of forming a complex with Cu, uniform graining is possible even for an aluminum plate containing a large amount of Cu. Examples of the compound capable of forming a complex with Cu include ammonia; hydrogen atom of ammonia such as methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, cyclohexylamine, triethanolamine, triisopropanolamine, EDTA (ethylenediaminetetraacetic acid). And amines obtained by substituting with a hydrocarbon group (aliphatic, aromatic, etc.); metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate and the like. In addition, ammonium salts such as ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium phosphate, and ammonium carbonate are also included. The temperature is preferably 10-60 ° C, more preferably 20-50 ° C.

  The concentration control of each component in the aqueous solution is preferably performed using a combination of a multi-component concentration measurement method such as a concentration measurement method, feedforward control and feedback control. This makes it possible to accurately control the concentration of the aqueous solution used as the electrolytic solution.

The multi-component concentration measurement method is, for example, a method of converting to an ultrasonic concentration in an aqueous solution and a conductivity (conductivity) C of the electrolyte, a neutralization titration method, capillary electrophoresis analysis, Examples include tachophoresis (capillary isotachophoresis) and ion chromatography.
The ion chromatograph method is classified into an absorbance detection ion chromatograph, a non-suppressor type electric conductivity detection ion chromatograph, a suppressor type ion chromatograph, and the like depending on the type of detector. Among these, a suppressor type ion chromatograph is preferable from the viewpoint of ensuring measurement stability.

  The first electrochemical surface roughening treatment can be performed according to, for example, the electrochemical grain method (electrolytic grain method) described in Japanese Patent Publication No. 48-28123 and British Patent No. 896,563. This electrolytic grain method uses a sinusoidal alternating current, but it may be performed using a special waveform as described in JP-A-52-58602. Further, the waveform described in JP-A-3-79799 can also be used. JP-A-55-158298, JP-A-56-28898, JP-A-52-58602, JP-A-52-152302, JP-A-54-85802, JP-A-60-190392, JP-A-58-120531, JP-A-63-176187, JP-A-1-5889, JP-A-1-280590, JP-A-1-118489, JP-A-1-148592, and JP-A-1-17896. JP-A-1-188315, JP-A-1-1549797, JP-A-2-235794, JP-A-3-260100, JP-A-3-253600, JP-A-4-72079, JP-A-4-72098, The methods described in JP-A-3-267400 and JP-A-1-141094 can also be applied. In addition to the above, it is also possible to perform electrolysis using an alternating current having a special frequency that has been proposed as a method of manufacturing an electrolytic capacitor. For example, it is described in US Pat. Nos. 4,276,129 and 4,676,879.

Various electrolyzers and power sources have been proposed, including US Pat. No. 4,203,637, JP-A-56-123400, JP-A-57-59770, JP-A-53-12738, JP 53-32821, JP 53-32222, JP 53-32823, JP 55-122896, JP 55-13284, JP 62-127500, JP Those described in JP-A-1-52100, JP-A-1-52098, JP-A-60-67700, JP-A-1-230800, JP-A-3-257199 and the like can be used.
Also, JP-A-52-58602, JP-A-52-152302, JP-A-53-12738, JP-A-53-12739, JP-A-53-32821, JP-A-53-32822, JP 53-32833, JP 53-32824, JP 53-32825, JP 54-85802, JP 55-122896, JP 55-13284, JP 48-28123, JP-B-51-7081, JP-A-52-13338, JP-A-52-133840, JP-A-52-133844, JP-A-52-133845, JP-A-53-149135 And those described in JP-A No. 54-146234 and the like can also be used.

  Moreover, as a power supply device, a commercial alternating current, an inverter control power supply, etc. can be used, for example. In particular, an inverter control power source using an IGBT (Insulated Gate Bipolar Transistor) element changes the voltage with respect to the width and thickness of the aluminum plate, the concentration of each component in the electrolytic solution, etc. When the current density of the plate) is controlled to be constant, this is preferable in terms of excellent followability.

  The waveform of the alternating current used in the first electrochemical surface roughening treatment is not particularly limited, and a sine wave, a rectangular wave, a trapezoidal wave, a triangular wave, or the like is used. The trapezoidal wave refers to that shown in FIG.

The electric amount in the first electrochemical graining treatment, an aluminum plate is amount of electricity when the anode sum is preferably from 1~1000C / dm ^2, and even a 50~300C / dm ² Further preferred. The current density is preferably from 10 to 100 A / dm ^2. Productivity will become more excellent in it being 10 A / dm < ² > or more. When it is 100 A / dm ² or less, the voltage is not high and the power source capacity does not become too large, so that the power source cost can be reduced.

  FIG. 3 is a side view showing an example of a radial type cell used for electrochemical roughening treatment using alternating current in the method for producing a lithographic printing plate support of the present invention.

  One or more AC power supplies can be connected to the electrolytic cell. As shown in FIG. 3, the current ratio between the AC anode and cathode applied to the aluminum plate facing the main electrode is controlled to achieve uniform graining and to dissolve the carbon of the main electrode. In addition, it is preferable to install an auxiliary anode and divert part of the alternating current. In FIG. 3, 11 is an aluminum plate, 12 is a radial drum roller, 13a and 13b are main poles, 14 is an electrolytic treatment liquid, 15 is an electrolytic solution supply port, and 16 is a slit. , 17 is an electrolyte passage, 18 is an auxiliary anode, 19a and 19b are thyristors, 20 is an AC power source, 40 is a main electrolytic cell, and 50 is an auxiliary anode cell. An anodic reaction that acts on the aluminum plate facing the main electrode by diverting a part of the current value as a direct current to an auxiliary anode provided in a tank separate from the two main electrodes via a rectifier or switching element It is possible to control the ratio between the current value for the current and the current value for the cathode reaction. The current ratio (ratio of the total amount of electricity when the aluminum plate is the anode and the total amount of electricity when the aluminum plate is the cathode) is preferably 0.9 to 3, and preferably 0.9 to 1.0. Is more preferable.

  As the electrolytic cell, electrolytic cells used for known surface treatments such as a vertical type, a flat type, and a radial type can be used, but a radial type electrolytic cell as described in JP-A-5-195300 is particularly preferable. . The electrolytic solution passing through the electrolytic cell may be parallel to the traveling direction of the aluminum web or may be a counter.

After the first electrochemical surface roughening treatment is completed, it is preferable to drain the liquid with a nip roller, and further perform the water washing treatment for 1 to 10 seconds and then drain the liquid with a nip roller.
The washing treatment is preferably carried out using a spray tube. As the spray tube used for the water washing treatment, for example, a spray tube having a plurality of spray tips in the width direction of the aluminum plate in which fan water spreads in a fan shape can be used. The interval between spray tips is preferably 20 to 100 mm, and the amount of liquid per spray tip is preferably 1 to 20 L / min. It is preferable to use a plurality of spray tubes.

<Second etching process>
A second etching process performed between the first electrochemical surface roughening process and the second electrochemical surface roughening process includes dissolving the smut generated by the first electrochemical surface roughening process; and In order to dissolve the edge portion of the pit formed by the first electrochemical surface roughening treatment. As a result, the edge portion of the large pit formed by the first electrochemical surface roughening process is melted and the surface becomes smooth, and the ink is less likely to be caught on the edge portion. Therefore, the lithographic printing plate precursor having excellent stain resistance Can be obtained.

The second etching process is basically the same as the first etching process, but the etching amount is preferably 0.1 to 10 g / m ² .

<Second desmut treatment>
After the second etching process, it is preferable to perform pickling (second desmut process) in order to remove dirt (smut) remaining on the surface. The second desmut process can be performed in the same manner as the first desmut process.

<Second electrochemical roughening treatment>
In the second electrochemical surface roughening treatment, an aluminum surface is subjected to an electrochemical surface roughening treatment in which an alternating current is passed in an aqueous solution containing an acid. The acid added to the aqueous solution is preferably hydrochloric acid. By performing the second electrochemical surface roughening treatment (hydrochloric acid electrolytic surface roughening treatment) using an aqueous solution containing hydrochloric acid, pits having an average opening diameter of 0.01 to 0.2 μm are uniformly formed on the entire surface of the aluminum plate. It is formed.

  The second electrochemical roughening treatment is basically the same as that described in the first electrochemical roughening treatment. Hereinafter, differences from the first electrochemical roughening treatment will be mainly described.

The hydrochloric acid concentration in the aqueous solution is preferably 1 to 100 g / L. Within the above range, the uniformity of pits formed on the surface of the aluminum plate increases.
The aqueous solution preferably contains 0.05 to 10 g / L of sulfuric acid or nitric acid. Sulfuric acid and nitric acid form an oxide film by an anodic reaction. Thereby, a uniform uneven surface is obtained.

The aluminum ion concentration in the aqueous solution is preferably 3 to 50 g / L. Within the above range, the uniformity of the pits becomes high. Moreover, the replenishment amount of the aqueous solution does not increase too much.
The AC power supply wave used for the second electrochemical surface roughening treatment is not particularly limited, and a sine wave, a rectangular wave, a trapezoidal wave, a triangular wave, or the like is used.

Quantity of electricity in the second electrochemical graining treatment, an aluminum plate is amount of electricity when the anode sum, is preferably 20C / dm ² or more, more preferably 20~100C / dm ^2, further preferably 30~70C / dm ^2.

<Third etching process>
The third etching process performed after the second electrochemical roughening process is formed by dissolving the smut generated by the second electrochemical roughening process and by the second electrochemical roughening process. It is performed for the purpose of dissolving the edge portion of the formed pit.

The third etching treatment is basically the same as the first etching treatment, the etching amount is preferably from 0.01~0.08g / m ^2, in 0.03~0.06g / m ² More preferably, it is 0.03-0.05 g / m ² .

  When the etching amount is in the above range, the shape of the small wave structure formed by hydrochloric acid electrolysis can be effectively utilized. For this reason, stain resistance and scratch resistance are further improved.

<Third desmut treatment>
After the third etching process, it is preferable to perform pickling (third desmut process) in order to remove dirt (smut) remaining on the surface. The third desmut process is basically the same as the first desmut process.

In the third desmutting treatment, when the same type of electrolyte as that used in the subsequent anodizing treatment is used as the desmutting treatment, it is possible to omit the draining and washing with a nip roller after the desmutting treatment.
The third desmut treatment is preferably performed in an electrolytic cell in which an aluminum plate is subjected to a cathode reaction treatment in an anodizing treatment apparatus used for anodizing treatment described later. If it does in this way, since it becomes unnecessary to provide an independent desmut processing tank for the 3rd desmut processing, equipment cost can be reduced.

<Anodizing treatment>
The aluminum plate treated as described above is further subjected to anodizing treatment. The anodizing treatment can be performed by a method conventionally used in this field. In this case, for example, in a solution having a sulfuric acid concentration of 50 to 300 g / L and an aluminum concentration of 5% by mass or less, an aluminum plate can be energized as an anode to form an anodized film. As a solution used for the anodizing treatment, sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, amidosulfonic acid and the like can be used alone or in combination of two or more.

  Under the present circumstances, the component normally contained at least in an aluminum plate, an electrode, tap water, groundwater, etc. may be contained in electrolyte solution. Furthermore, the second and third components may be added. Examples of the second and third components herein include metal ions such as Na, K, Mg, Li, Ca, Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn; Cation such as ammonium ion; anion such as nitrate ion, carbonate ion, chloride ion, phosphate ion, fluoride ion, sulfite ion, titanate ion, silicate ion, borate ion, etc., 0 to 10,000 ppm It may be contained at a concentration of about.

The conditions for anodizing treatment vary depending on the electrolyte used, and thus cannot be determined unconditionally. In general, however, the electrolyte concentration is 1 to 80% by mass, the solution temperature is 5 to 70 ° C., and the current density is 0.5. ˜60 A / dm ² , voltage 1 to 100 V, and electrolysis time 15 seconds to 50 minutes are appropriate and adjusted so as to obtain a desired anodic oxide film amount.

  Further, JP-A-54-81133, JP-A-57-47894, JP-A-57-51289, JP-A-57-51290, JP-A-57-54300, JP-A-57-136596, JP-A-58-107498, JP-A-60-200366, JP-A-62-136696, JP-A-63-176494, JP-A-4-17697, JP-A-4-280997, JP-A-6-280997 The methods described in JP-A-207299, JP-A-5-24377, JP-A-5-32083, JP-A-5-125597, JP-A-5-195291 and the like can also be used.

  Of these, as described in JP-A-54-12853 and JP-A-48-45303, it is preferable to use a sulfuric acid solution as the electrolytic solution. The sulfuric acid concentration in the electrolytic solution is preferably 10 to 300 g / L (1 to 30% by mass), more preferably 50 to 200 g / L (5 to 20% by mass), and the aluminum ion concentration. Is preferably 1 to 25 g / L (0.1 to 2.5% by mass), more preferably 2 to 10 g / L (0.2 to 1% by mass). Such an electrolytic solution can be prepared, for example, by adding aluminum sulfate or the like to dilute sulfuric acid having a sulfuric acid concentration of 50 to 200 g / L.

  The composition management of the electrolyte is conducted using the same method as in the case of nitric acid electrolysis described above, and the conductivity, specific gravity and temperature, or conductivity and ultrasonic wave propagation corresponding to the matrix of sulfuric acid concentration and aluminum ion concentration. It is preferable to control by speed and temperature.

  The liquid temperature of the electrolytic solution is preferably 25 to 55 ° C, and more preferably 30 to 50 ° C.

When anodizing is performed in an electrolytic solution containing sulfuric acid, direct current may be applied between the aluminum plate and the counter electrode, or alternating current may be applied.
When a direct current is applied to the aluminum plate, the current density is preferably from 1 to 60 A / dm ^2, and more preferably 5 to 40 A / dm ^2.
In the case of continuous anodizing treatment, at the beginning of anodizing treatment, so as not to cause so-called “burn” (part where the film becomes thicker than the surrounding area) due to current concentration on a part of the aluminum plate, It is preferable to increase the current density to 30 to 50 A / dm ² or higher as the anodic oxidation process proceeds with a current flowing at a low current density of 5 to 10 A / m ² .
Specifically, it is preferable that the current distribution of the DC power supply is set so that the current of the downstream DC power supply is equal to or greater than the current of the upstream DC power supply. By using such current distribution, so-called burning is less likely to occur, and as a result, high-speed anodization can be performed.

When the anodizing process is continuously performed, it is preferable to perform the liquid feeding method in which the aluminum plate is fed with an electrolyte.
By performing anodizing treatment under such conditions, a porous film having many pores called micropores can be obtained. Usually, the average pore diameter is about 5 to 50 nm, and the average pore density is 300. ˜800 / μm ² or so.

The amount of the anodized film is preferably 1 to 5 g / m ² . When it is 1 g / m ² or more, the plate is hardly damaged. If it is 5 g / m ² or less, a large amount of electric power is not required for production, which is economically advantageous. The amount of the anodized film is more preferably 1.5 to 4 g / m ² . Moreover, it is preferable to carry out so that the difference in the amount of the anodized film between the center portion of the aluminum plate and the vicinity of the edge portion is 1 g / m ² or less.
Moreover, it is preferable that the quantity of the anodic oxide film of the back surface of the surface which performed the electrochemical roughening process is 0.1-1 g / m < ² >. When it is 0.1 g / m ² or more, the back surface is less likely to be scratched, and the image recording layer that comes into contact with the back surface is less likely to be scratched as a lithographic printing plate precursor. When it is 1 g / m ² or less, it is economically advantageous.

As electrolysis apparatuses used for anodizing treatment, those described in JP-A-48-26638, JP-A-47-18739, JP-B-58-24517, JP-A-2001-11698, etc. Can be used.
Among these, the apparatus shown in FIG. 4 is preferably used. FIG. 4 is a schematic view showing an example of an apparatus for anodizing the surface of an aluminum plate.

  In the anodizing apparatus 410 shown in FIG. 4, in order to energize the aluminum plate 416 via the electrolytic solution, a power feeding tank 412 is provided on the upstream side in the traveling direction of the aluminum plate 416, and an anodizing treatment tank 414 is provided on the downstream side. It is installed. The aluminum plate 416 is conveyed by the pass rollers 422 and 428 as indicated by arrows in FIG. In the feed tank 412 into which the aluminum plate 416 is first introduced, an anode 420 connected to the positive electrode of the DC power supply 434 is installed, and the aluminum plate 416 serves as a cathode. Therefore, a cathode reaction occurs in the aluminum plate 416.

In the anodizing tank 414 into which the aluminum plate 416 is subsequently introduced, a cathode 430 connected to the negative electrode of the DC power source 434 is installed, and the aluminum plate 416 serves as an anode. Therefore, an anodic reaction occurs in the aluminum plate 416, and an anodic oxide film is formed on the surface of the aluminum plate 416.
The distance between the aluminum plate 416 and the cathode 430 is preferably 50 to 200 mm. Aluminum is used as the cathode 430. The cathode 430 is preferably not an electrode having a large area but an electrode divided into a plurality of pieces in the traveling direction of the aluminum plate 416 so that hydrogen gas generated by the anode reaction can be easily released from the system. .

  Between the power supply tank 412 and the anodizing tank 414, it is preferable to provide a tank called an intermediate tank 413 in which the electrolytic solution does not accumulate as shown in FIG. By providing the intermediate tank 413, current can be prevented from bypassing from the anode 420 to the cathode 430 without passing through the aluminum plate 416. It is preferable to reduce the bypass current as much as possible by installing a nip roller 424 in the intermediate tank 413 to drain the liquid. The electrolyte discharged by draining is discharged out of the anodizing apparatus 410 from the drain port 442.

  The electrolyte solution 418 stored in the power supply tank 412 has a higher temperature and / or higher concentration than the electrolyte solution 426 stored in the anodizing tank 414 in order to reduce voltage loss. In addition, the composition, temperature, and the like of the electrolytic solutions 418 and 426 are determined from the formation efficiency of the anodized film, the micropore shape of the anodized film, the hardness of the anodized film, the voltage, the cost of the electrolytic solution, and the like.

  Electrolyte is ejected from the liquid supply nozzles 436 and 438 and supplied to the power supply tank 412 and the anodizing treatment tank 414. For the purpose of keeping the distribution of the electrolyte constant and preventing local current concentration of the aluminum plate 416 in the anodizing tank 414, the liquid supply nozzles 436 and 438 are provided with slits, and the liquid flow to be ejected in the width direction. It has a constant structure.

  In the anodizing bath 414, a shielding plate 440 is provided on the opposite side of the aluminum plate 416 from the anode 430, and current flows to the opposite side of the surface of the aluminum plate 416 where the anodized film is to be formed. Deter. The distance between the aluminum plate 416 and the shielding plate 440 is preferably 5 to 30 mm. It is preferable to use a plurality of DC power supplies 434 and connect the positive electrode sides in common. Thereby, the current distribution in the anodizing bath 414 can be controlled.

<Sealing treatment>
In this invention, you may perform the sealing process which seals the micropore which exists in an anodic oxide film as needed. By performing the sealing treatment, the developability (sensitivity) of the lithographic printing plate precursor can be improved.
It is well known that the anodized film is a porous film having pores called pores in a direction substantially perpendicular to the film surface. In the present invention, it is preferable to subject the anodizing treatment to a sealing treatment with a high sealing ratio. The sealing rate is preferably 50% or more, more preferably 70% or more, and still more preferably 90% or more. Here, the “sealing rate” is defined by the following formula.

  Sealing rate = (surface area before sealing−surface area after sealing) / surface area before sealing × 100%

  The surface area can be measured using, for example, a simple BET surface area measuring device (for example, QUANTASORB (manufactured by Kantha Sorb), manufactured by Yuasa Ionics).

  The sealing treatment is not particularly limited, and a conventionally known method can be used. For example, hydrothermal treatment, boiling water treatment, steam treatment, dichromate treatment, nitrite treatment, ammonium acetate salt treatment, electrodeposition sealing treatment, and the like described in JP-B 36-22063. Zirconate treatment, treatment with an aqueous solution containing a phosphate and an inorganic fluorine compound described in JP-A-9-244227, treatment with an aqueous solution containing a sugar described in JP-A-9-134002 , Treatment with an aqueous solution containing titanium and fluorine described in JP-A-2000-81704 and JP-A-2000-89466, alkali metal silica described in US Pat. No. 3,181,461, etc. Examples include acid salt treatment.

  An example of a suitable sealing treatment is an alkali metal silicate treatment. The alkali metal silicate treatment is performed using an alkali metal silicate aqueous solution having a pH of 10 to 13 at 25 ° C. without causing gelation of the liquid and dissolution of the anodized film. Processing conditions such as temperature and processing time can be selected as appropriate. Suitable alkali metal silicates include, for example, sodium silicate, potassium silicate, and lithium silicate. Moreover, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. can be mix | blended in order to adjust pH of alkali metal silicate aqueous solution high.

Furthermore, you may mix | blend an alkaline-earth metal salt and / or a group 4 (Group IVA) metal salt with alkali metal silicate aqueous solution as needed. Examples of the alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, and barium nitrate; sulfates, hydrochlorides, phosphates, acetates, oxalates, and boric acids of alkaline earth metals. Examples thereof include water-soluble salts such as salts. Examples of the Group 4 (Group IVA) metal salt include titanium tetrachloride, titanium trichloride, potassium fluoride titanium, potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride. And zirconium tetrachloride. Alkaline earth metal salts and Group 4 (Group IVA) metal salts can be used alone or in combination of two or more.
The concentration of the alkali metal silicate aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.05 to 5.0% by mass.

Another example of a suitable sealing treatment is a fluorinated zirconic acid treatment. The fluorinated zirconate treatment is performed using a fluorinated zirconate salt such as sodium fluorinated zirconate or potassium fluorinated zirconate. Among these, it is preferable to use sodium fluorinated zirconate. Thereby, the developability (sensitivity) of the lithographic printing plate precursor becomes excellent. The concentration of the fluorinated zirconic acid solution used for the fluorinated zirconic acid treatment is preferably 0.01 to 2% by mass, and more preferably 0.1 to 0.3% by mass.
The fluorinated zirconate solution preferably contains sodium dihydrogen phosphate. The concentration of sodium dihydrogen phosphate is preferably 0.01 to 3% by mass, and more preferably 0.1 to 0.3% by mass.
The fluorinated zirconate solution may contain aluminum ions. In that case, the aluminum ion concentration of the fluorinated zirconate solution is preferably 1 to 500 mg / L.

The temperature for the sealing treatment is preferably 20 to 90 ° C, and more preferably 50 to 80 ° C.
The sealing treatment time (immersion time in the solution) is preferably 1 to 20 seconds, and more preferably 5 to 15 seconds.

  In addition, after performing a sealing treatment as necessary, a polymer or copolymer having the above-mentioned alkali metal silicate treatment, polyvinylphosphonic acid, polyacrylic acid, sulfo group or the like in the side chain, JP-A-11-231509 A surface treatment such as a treatment of immersing or coating in a solution containing an organic compound having an amino group and a group selected from the group consisting of a phosphine group, a phosphone group, and a phosphoric acid group or a salt thereof described in the publication be able to.

  After the sealing treatment, it is preferable to perform a hydrophilic treatment described later.

<Hydrophilic treatment>
A hydrophilization treatment may be performed after the anodizing treatment or the sealing treatment. Examples of the hydrophilization treatment include treatment with potassium fluorozirconate described in US Pat. No. 2,946,638 and phosphomolybdate described in US Pat. No. 3,201,247. Treatment, alkyl titanate treatment described in British Patent 1,108,559, polyacrylic acid treatment described in German Patent 1,091,433, German Patent 1,134, No. 093 and British Patent No. 1,230,447, polyvinylphosphonic acid treatment, Japanese Patent Publication No. 44-6409, phosphonic acid treatment, US Pat. No. 3,307,951 Phytic acid treatment described in the specification of JP, No. 58-16893 and JP-A No. 58-18291 Treatment with a salt of a molecular compound and a divalent metal, as described in US Pat. No. 3,860,426, hydrophilic cellulose (eg, zinc acetate) containing a water-soluble metal salt (eg, zinc acetate) Carboxymethyl cellulose) is provided with a primer layer, and a water-soluble polymer having a sulfo group described in JP-A-59-101651.

Further, phosphates described in JP-A No. 62-019494, water-soluble epoxy compounds described in JP-A No. 62-033692, and JP-A No. 62-097892 Phosphoric acid modified starch, diamine compounds described in JP-A-63-056498, inorganic or organic acids of amino acids described in JP-A-63-130391, JP-A-63-145092 Organic phosphonic acids containing a carboxy group or hydroxy group, compounds having an amino group and a phosphonic acid group described in JP-A-63-165183, and JP-A-2-316290 Specific carboxylic acid derivatives, phosphate esters described in JP-A-3-215095, JP-A-3-261592 Compounds having one amino group and one oxygen acid group of phosphorus described in the publication, phosphoric esters described in JP-A-3-215095, and JP-A-5-246171 Aliphatic or aromatic phosphonic acids such as phenylphosphonic acid, compounds containing S atoms such as thiosalicylic acid described in JP-A-1-307745, phosphorus described in JP-A-4-282737 Examples of the treatment include undercoating using a compound having a group of oxygen acids.
Further, coloring with an acid dye described in JP-A-60-64352 can also be performed.

  Hydrophilicity can also be achieved by soaking in an aqueous solution of an alkali metal silicate such as sodium silicate or potassium silicate, or by applying a hydrophilic vinyl polymer or hydrophilic compound to form a hydrophilic primer layer. It is preferable to carry out the treatment.

Hydrophilization treatment with an aqueous solution of an alkali metal silicate such as sodium silicate and potassium silicate is described in US Pat. No. 2,714,066 and US Pat. No. 3,181,461. It can be performed according to methods and procedures.
Examples of the alkali metal silicate include sodium silicate, potassium silicate, and lithium silicate. The aqueous solution of alkali metal silicate may contain an appropriate amount of sodium hydroxide, potassium hydroxide, lithium hydroxide or the like.
The aqueous solution of alkali metal silicate may contain an alkaline earth metal salt or a Group 4 (Group IVA) metal salt. Examples of the alkaline earth metal salt include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, and barium nitrate; sulfates; hydrochlorides; phosphates; acetates; oxalates; Examples of the Group 4 (Group IVA) metal salt include titanium tetrachloride, titanium trichloride, potassium fluoride titanium, potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride. And zirconium tetrachloride. These alkaline earth metal salts and Group 4 (Group IVA) metal salts are used alone or in combination of two or more.

The amount of Si adsorbed by the alkali metal silicate treatment can be measured with a fluorescent X-ray analyzer, and the amount of adsorption is preferably about 1.0 to 15.0 mg / m ² .
By this alkali metal silicate treatment, the effect of improving the dissolution resistance to the alkaline developer on the surface of the lithographic printing plate support is obtained, the dissolution of the aluminum component into the developer is suppressed, and the developer fatigue It is possible to reduce the occurrence of development residue due to the above.

The hydrophilization treatment by forming a hydrophilic undercoat layer can also be performed according to the conditions and procedures described in JP-A Nos. 59-101651 and 60-149491.
Examples of the hydrophilic vinyl polymer used in this method include polyvinyl sulfonic acid, sulfo group-containing vinyl polymerizable compounds such as p-styrene sulfonic acid having a sulfo group, and ordinary vinyl polymerization such as (meth) acrylic acid alkyl ester. And a copolymer with a functional compound. Examples of hydrophilic compounds that may be used in this method include, -NH ₂ group, compounds having at least one selected from the group consisting of -COOH group and sulfo group.

<Dry>
After obtaining the lithographic printing plate support as described above, it is preferable to dry the surface of the lithographic printing plate support before providing the image recording layer. Drying is preferably performed after the final treatment of the surface treatment, after washing with water and draining with a nip roller.
The drying temperature is preferably 70 ° C or higher, more preferably 80 ° C or higher, preferably 110 ° C or lower, more preferably 100 ° C or lower.
The drying time is preferably 1 second or longer, more preferably 2 seconds or longer, more preferably 20 seconds or shorter, and even more preferably 15 seconds.

<Aluminum plate (rolled aluminum)>
Next, the aluminum plate used for the lithographic printing plate support of the present invention will be described. A known aluminum plate can be used for the support for the lithographic printing plate of the present invention, and it is a metal mainly composed of aluminum that is dimensionally stable, and is a pure aluminum plate made of aluminum or an aluminum alloy. In addition, an alloy plate containing aluminum as a main component and containing a small amount of foreign elements can also be used.

  In the present specification, various substrates made of the above-described aluminum or aluminum alloy are generically used as an aluminum plate. The foreign elements that may be contained in the aluminum alloy include silicon, iron, copper, manganese, magnesium, chromium, zinc, bismuth, nickel, titanium, etc., and the content of the foreign elements in the alloy is 10% by mass or less. It is.

  Thus, the composition of the aluminum plate used in the support for a lithographic printing plate to which the present invention is applied is not specified. For example, it is described in the aluminum handbook 4th edition (1990, published by Light Metal Association). Conventionally known materials such as JIS A1050, JIS A1100, JIS A1070, JIS A3004 containing Mn, and international registered alloy 3103A can be appropriately used. For the purpose of increasing the tensile strength, an Al—Mg alloy or an Al—Mn—Mg alloy (JIS A3005) in which 0.1% by mass or more of magnesium is added to these aluminum alloys can also be used. Furthermore, an Al—Zr alloy or an Al—Si alloy containing Zr or Si can also be used. Furthermore, an Al—Mg—Si based alloy can also be used.

Moreover, the aluminum plate obtained by rolling the UBC (Used Beverage Can) ingot which melt | dissolved the used aluminum beverage can can also be used.
In this aluminum plate, the Cu content is preferably 0.00% by mass or more, more preferably 0.01% by mass or more, and more preferably 0.02% by mass or more, and 0.15% by mass. % Or less, more preferably 0.11% by mass or less, and even more preferably 0.03% by mass or less. Particularly preferred are Si: 0.07 to 0.09 mass%, Fe: 0.20 to 0.29 mass%, Cu: 0.03 mass% or less, Mn: 0.01 mass% or less, Mg: 0 0.01% by mass or less, Cr: 0.01% by mass or less, Zn: 0.01% by mass or less, Ti: 0.02% by mass or less, and Al: 99.5% by mass or more.

  Regarding the JIS 1050 material, the techniques proposed by the applicant of the present application are disclosed in Japanese Patent Application Laid-Open Nos. 59-153861, 61-51395, 62-146694, 60-215725, and 60-215725. JP 60-215726, JP 60-215727, JP 60-216728, JP 61-272367, JP 58-11759, JP 58-42493, JP 58- 221254, JP-A-62-148295, JP-A-4-254545, JP-A-4-165541, JP-B-3-68939, JP-A-3-234594, JP-B-1-47545, and JP-A-62. It is described in each publication of -140894. In addition, techniques described in Japanese Patent Publication No. 1-35910 and Japanese Patent Publication No. 55-28874 are also known.

  Regarding the JIS1070 material, the techniques proposed by the applicant of the present application are disclosed in JP-A-7-81264, JP-A-7-305133, JP-A-8-49034, JP-A-8-73974, JP-A-8-108659 and It is described in JP-A-8-92679.

  Regarding Al-Mg alloys, the techniques proposed by the applicant of the present application are disclosed in Japanese Patent Publication Nos. Sho 62-5080, Sho 63-60823, Shoko 3-61753, JP Sho 60-20396, JP-A-60-203497, JP-B-3-11635, JP-A-61-274993, JP-A-62-23794, JP-A-63-47347, JP-A-63-47348, JP-A-63-47349. JP-A 64-1293, JP-A 63-135294, JP-A 63-87288, JP-B 4-73392, JP-B 7-100844, JP-A 62-149856, JP-B JP-A-4-73394, JP-A-62-181191, JP-B-5-76530, JP-A-63-30294, and JP-B-6-37116. Also described in JP-A-2-215599, JP-A-61-201747, and the like.

  With regard to Al—Mn alloys, techniques proposed by the applicant of the present application are described in Japanese Patent Application Laid-Open Nos. 60-230951, 1-306288, and 2-293189. In addition, JP-B-54-42284, JP-B-4-19290, JP-B-4-19291, JP-B-4-19292, JP-A-61-35995, JP-A-64-51992, JP-A-4-19592, No. 226394, US Pat. No. 5,009,722, US Pat. No. 5,028,276 and the like.

  With regard to the Al—Mn—Mg alloy, techniques proposed by the applicant of the present application are described in Japanese Patent Application Laid-Open Nos. 62-86143 and 3-2222796. JP-B 63-60824, JP-A 60-63346, JP-A 60-63347, JP-A-1-293350, European Patent No. 223,737, US Pat. No. 4,818, No. 300, British Patent No. 1,222,777, etc.

  Regarding the Al—Zr alloy, the technique proposed by the applicant of the present application is described in Japanese Patent Publication No. 63-15978 and Japanese Patent Application Laid-Open No. 61-51395. Also described in JP-A-63-143234 and JP-A-63-143235.

  The Al—Mg—Si alloy is described in British Patent 1,421,710.

  In order to use an aluminum alloy as a plate material, for example, the following method can be employed. First, a molten aluminum alloy adjusted to a predetermined alloy component content is subjected to a cleaning process and cast according to a conventional method. In the cleaning process, in order to remove unnecessary gas such as hydrogen in the molten metal, flux treatment, degassing process using argon gas, chlorine gas, etc., so-called rigid media filter such as ceramic tube filter, ceramic foam filter, A filtering process using a filter that uses alumina flakes, alumina balls or the like as a filter medium, a glass cloth filter, or a combination of a degassing process and a filtering process is performed.

  These cleaning treatments are preferably performed in order to prevent defects caused by foreign matters such as non-metallic inclusions and oxides in the molten metal and defects caused by gas dissolved in the molten metal. Regarding filtering of the molten metal, JP-A-6-57432, JP-A-3-162530, JP-A-5-140659, JP-A-4-231425, JP-A-4-276031, JP-A-5-311261, JP-A-5-311261 6-136466 and the like. Further, the degassing of the molten metal is described in JP-A-5-51659, Japanese Utility Model Laid-Open No. 5-49148, and the like. The applicant of the present application has also proposed a technique relating to degassing of molten metal in Japanese Patent Application Laid-Open No. 7-40017.

Next, casting is performed using the molten metal that has been subjected to the cleaning treatment as described above. Regarding the casting method, there are a method using a solid mold typified by a DC casting method and a method using a driving mold typified by a continuous casting method.
In DC casting, solidification occurs at a cooling rate of 0.5 to 30 ° C./second. When the temperature is less than 1 ° C., many coarse intermetallic compounds may be formed. When DC casting is performed, an ingot having a thickness of 300 to 800 mm can be manufactured. The ingot is chamfered as necessary according to a conventional method, and usually 1 to 30 mm, preferably 1 to 10 mm, of the surface layer is cut. Before and after that, soaking treatment is performed as necessary. When performing the soaking process, heat treatment is performed at 450 to 620 ° C. for 1 to 48 hours so that the intermetallic compound does not become coarse. If the heat treatment is shorter than 1 hour, the effect of soaking may be insufficient. In addition, when soaking is not performed, there is an advantage that the cost can be reduced.

  Then, hot rolling and cold rolling are performed to obtain a rolled aluminum plate. An appropriate starting temperature for hot rolling is 350 to 500 ° C. An intermediate annealing treatment may be performed before or after hot rolling or in the middle thereof. The conditions for the intermediate annealing treatment are heating at 280 to 600 ° C. for 2 to 20 hours, preferably 350 to 500 ° C. for 2 to 10 hours using a batch annealing furnace, or 400 to 600 ° C. using a continuous annealing furnace. Heating is performed for 6 minutes or less, preferably 450 to 550 ° C. for 2 minutes or less. The crystal structure can be made finer by heating at a heating rate of 10 to 200 ° C./second using a continuous annealing furnace.

  The flatness of the aluminum plate finished to a predetermined thickness, for example, 0.1 to 0.5 mm by the above steps may be further improved by a correction device such as a roller leveler or a tension leveler. The flatness may be improved after the aluminum plate is cut into a sheet shape, but in order to improve productivity, it is preferably performed in a continuous coil state. Further, a slitter line may be used for processing into a predetermined plate width. Moreover, in order to prevent generation | occurrence | production of the damage | wound by friction between aluminum plates, you may provide a thin oil film on the surface of an aluminum plate. As the oil film, a volatile or non-volatile film is appropriately used as necessary.

  On the other hand, as the continuous casting method, a twin roll method (hunter method), a method using a cooling roll typified by the 3C method, a double belt method (Hazley method), a cooling belt or a cooling block typified by Al-Swiss Caster II type The method using is industrially performed. When the continuous casting method is used, it solidifies at a cooling rate of 100 to 1000 ° C./second. Since the continuous casting method generally has a higher cooling rate than the DC casting method, it has a feature that the solid solubility of the alloy component in the aluminum matrix can be increased. Regarding the continuous casting method, the techniques proposed by the applicant of the present application are disclosed in JP-A-3-79798, JP-A-5-201166, JP-A-5-156414, JP-A-6-262203, and JP-A-6-122949. JP-A-6-210406 and JP-A-6-26308.

  When continuous casting is performed, for example, if a method using a cooling roll such as a Hunter method is used, a cast plate having a thickness of 1 to 10 mm can be directly cast continuously, and the hot rolling step is omitted. The advantage of being able to In addition, when a method using a cooling belt such as the Husley method is used, a cast plate having a thickness of 10 to 50 mm can be cast. Generally, a hot rolling roll is arranged immediately after casting and continuously rolled. Thus, a continuous cast and rolled plate having a thickness of 1 to 10 mm is obtained.

  These continuous cast and rolled plates are subjected to processes such as cold rolling, intermediate annealing, improvement of flatness, slits, and the like in the same manner as described for DC casting. Finished to a thickness of 5 mm. Regarding the intermediate annealing condition and the cold rolling condition when using the continuous casting method, the techniques proposed by the applicant of the present application are disclosed in JP-A-6-220593, JP-A-6-210308, JP-A-7-54111, It is described in JP-A-8-92709.

  The aluminum plate used in the present invention is preferably subjected to H18 tempering as defined in JIS.

Various characteristics described below are desired for the aluminum plate thus manufactured.
The strength of the aluminum plate is preferably such that the 0.2% proof stress is 120 MPa or more in order to obtain the stiffness required for a lithographic printing plate support. Further, in order to obtain a certain level of waist strength even when performing a burning treatment, the 0.2% yield strength after heat treatment at 270 ° C. for 3 to 10 minutes is preferably 80 MPa or more, and 100 MPa or more. It is more preferable that In particular, when the waist strength is required for an aluminum plate, an aluminum material added with Mg or Mn can be used, but if the waist is strengthened, the ease of fitting to the plate cylinder of a printing press becomes inferior. Depending on the application, the material and the amount of trace components added are appropriately selected. With regard to these, techniques proposed by the applicant of the present application are described in Japanese Patent Application Laid-Open Nos. 7-126820 and 62-140894.
The aluminum plate preferably has a tensile strength of 160 ± 15 N / mm ² , a 0.2% proof stress of 140 ± 15 MPa, and an elongation specified by JIS Z2241 and Z2201 of 1 to 10%.

  The crystal structure of the aluminum plate may cause poor surface quality when the surface of the aluminum plate is subjected to chemical or electrochemical surface roughening. It is preferably not too coarse. The crystal structure on the surface of the aluminum plate preferably has a width of 200 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, and the length of the crystal structure is 5000 μm or less. Is preferably 1000 μm or less, and more preferably 500 μm or less. With regard to these, techniques proposed by the applicant of the present application are described in Japanese Patent Laid-Open Nos. 6-218495, 7-39906, and 7-124609.

  The alloy component distribution of the aluminum plate, when chemical surface roughening treatment or electrochemical surface roughening treatment is performed, poor surface quality occurs due to non-uniform distribution of the alloy component on the surface of the aluminum plate. Therefore, it is preferable that the surface is not very uneven. With regard to these, the techniques proposed by the applicant of the present application are described in Japanese Patent Laid-Open Nos. 6-48058, 5-301478, and 7-132689.

  In the intermetallic compound of the aluminum plate, the size and density of the intermetallic compound may affect the chemical roughening treatment or the electrochemical roughening treatment. With regard to these, techniques proposed by the applicant of the present application are described in Japanese Patent Laid-Open Nos. 7-138687 and 4-254545.

[Lithographic printing plate precursor]
Moreover, the lithographic printing plate precursor of the present invention can be obtained by providing a recording layer capable of recording, developing, and printing images / prints on the lithographic printing plate support described above. A photosensitive / thermosensitive composition is used for the recording layer.
Examples of the photosensitive composition suitably used in the present invention include a thermal positive photosensitive composition containing an alkali-soluble polymer compound and a photothermal conversion substance (hereinafter, this composition and an image recording layer using the same). ), A thermal negative photosensitive composition containing a curable compound and a photothermal conversion substance (hereinafter also referred to as “thermal negative type”), a photopolymerizable photosensitive composition (hereinafter referred to as “thermal positive type”). , Also referred to as “photopolymer type”), a negative photosensitive composition containing a diazo resin or a photocrosslinking resin (hereinafter also referred to as “conventional negative type”), and a positive photosensitive composition containing a quinonediazide compound. Product (hereinafter also referred to as “conventional positive type”), a photosensitive composition that does not require a special development step (hereinafter referred to as “the conventional positive type”). Referred to as "non-treatment type".) It can be mentioned as, in particular, thermal positive type, thermal negative type, non-treatment type is preferred. Hereinafter, these suitable photosensitive compositions will be described.

The lithographic printing plate precursor according to the invention preferably has a recording layer of 1.1 to 1.6 g / m ² on the above lithographic printing plate support. More preferably, has a recording layer of 1.1~1.5g / m ^2, more preferably it has a recording layer of 1.1~1.4g / m ^2. The recording layer is measured by mass change per unit area after coating and drying.
When the recording layer in this range is provided on the support having the specific surface shape of the present invention, scratch resistance is further improved.

<Thermal positive type>
<Photosensitive layer>
The thermal positive type photosensitive composition contains an alkali-soluble polymer compound and a photothermal conversion substance. In the thermal positive type image recording layer, the photothermal conversion substance converts the energy of light such as infrared lasers into heat, which effectively eliminates the interaction that reduces the alkali solubility of alkali-soluble polymer compounds. To do.

Examples of the alkali-soluble polymer compound include a resin containing an acidic group in the molecule and a mixture of two or more thereof. In particular, a phenolic hydroxy group, sulfonamide group (in -SO ₂ NH-R (wherein, R represents a hydrocarbon group.)), Active imino group _{(-SO 2 NHCOR, -SO 2 NHSO} 2 R, -CONHSO A resin having an acidic group such as ₂ R (wherein R has the same meaning as described above) is preferable in terms of solubility in an alkali developer.
In particular, a resin having a phenolic hydroxy group is preferable in that it has excellent image-forming properties when exposed to light such as an infrared laser, and examples thereof include phenol-formaldehyde resins, m-cresol-formaldehyde resins, p-cresol-formaldehyde resins, m- / p-mixed cresol-formaldehyde resin, phenol / cresol (any of m-, p- and m- / p-mixed) mixed-formaldehyde resin (phenol-cresol-formaldehyde co-condensation resin) and other novolak resins Are preferable.
Furthermore, a polymer compound described in JP-A No. 2001-305722 (particularly [0023] to [0042]), and a repetition represented by the general formula (1) described in JP-A No. 2001-215893 Preferred examples also include polymer compounds containing units and polymer compounds described in JP-A No. 2002-311570 (particularly [0107]).

  Preferable examples of the photothermal conversion substance include pigments or dyes having a light absorption region in the infrared region having a wavelength of 700 to 1200 nm from the viewpoint of recording sensitivity. Examples of the dye include azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes (for example, , Nickel thiolate complex). Among these, cyanine dyes are preferable, and cyanine dyes represented by the general formula (I) described in JP 2001-305722 A are particularly preferable.

The thermal positive type photosensitive composition can contain a dissolution inhibitor. As the dissolution inhibitor, for example, a dissolution inhibitor as described in JP-A-2001-305722, [0053] to [0055] is preferably exemplified.
In addition, in the thermal positive type photosensitive composition, as a additive, a sensitivity modifier, a printing agent for obtaining a visible image immediately after heating by exposure, a compound such as a dye as an image colorant, a coating property In addition, it is preferable to include a surfactant for improving the processing stability. For these, compounds described in JP-A-2001-305722, [0056] to [0060] are preferable.
The photosensitive composition described in detail by Unexamined-Japanese-Patent No. 2001-305722 is preferably used also in respects other than the above.

Further, the thermal positive type image recording layer is not limited to a single layer but may have a two-layer structure.
As an image recording layer having a two-layer structure (multilayer image recording layer), a lower layer (hereinafter referred to as “A layer”) having excellent printing durability and solvent resistance is provided on the side close to the support, and a positive layer is provided thereon. A type provided with a layer having excellent image formability (hereinafter referred to as “B layer”) is preferable. This type has high sensitivity and can realize a wide development latitude. The B layer generally contains a photothermal conversion substance. Preferred examples of the photothermal conversion substance include the dyes described above.
As the resin used for the A layer, a polymer having a monomer having a sulfonamide group, an active imino group, a phenolic hydroxy group or the like as a copolymerization component is preferably used because it has excellent printing durability and solvent resistance. . As the resin used for the B layer, an alkaline aqueous solution-soluble resin having a phenolic hydroxy group is preferably exemplified.
In addition to the resin, the composition used for the A layer and the B layer can contain various additives as necessary. Specifically, various additives as described in [0062] to [0085] of JP-A-2002-3233769 are preferably used. Further, the additives described in [0053] to [0060] of JP-A-2001-305722 described above are also preferably used.
About each component which comprises A layer and B layer, and its content, it is preferable to make it describe in Unexamined-Japanese-Patent No. 11-218914.

<Intermediate layer>
An intermediate layer is preferably provided between the thermal positive type image recording layer and the support. As the component contained in the intermediate layer, various organic compounds described in [0068] of JP-A No. 2001-305722 are preferably exemplified.

<Others>
As a method for producing a thermal positive type image recording layer and a plate making method, methods described in detail in JP-A No. 2001-305722 can be used.

<Thermal negative type>
The thermal negative photosensitive composition contains a curable compound and a photothermal conversion substance. The thermal negative type image recording layer is a negative photosensitive layer in which a portion irradiated with light such as an infrared laser is cured to form an image portion.
<Polymerized layer>
As one of the thermal negative type image recording layers, a polymerization type image recording layer (polymerization layer) is preferably exemplified. The polymerization layer contains a photothermal conversion substance, a radical generator, a radical polymerizable compound that is a curable compound, and a binder polymer. In the polymerization layer, infrared light absorbed by the photothermal conversion substance is converted into heat, the radical generator is decomposed by this heat to generate radicals, and the radical polymerizable compound is polymerized in a chain by the generated radicals and cured. .

As a photothermal conversion substance, the photothermal conversion substance used for the thermal positive type mentioned above is mentioned, for example. Specific examples of particularly preferred cyanine dyes include those described in JP-A-2001-133969, [0017] to [0019].
Preferable examples of the radical generator include onium salts. In particular, onium salts described in JP-A-2001-133969, [0030] to [0033] are preferable.
Examples of the radically polymerizable compound include compounds having at least one terminal ethylenically unsaturated bond, preferably two or more.
As the binder polymer, a linear organic polymer is preferably exemplified. Preferable examples include linear organic polymers that are soluble or swellable in water or weak alkaline water. Among them, a (meth) acrylic resin having an unsaturated group such as an allyl group or an acryloyl group or a benzyl group and a carboxy group in the side chain is preferable in that it has an excellent balance of film strength, sensitivity, and developability. .
As the radical polymerizable compound and the binder polymer, those described in detail in [0036] to [0060] of JP-A No. 2001-133969 can be used.

  The additive described in [0061] to [0068] of JP-A No. 2001-133969 is contained in the thermal negative photosensitive composition (for example, a surfactant for improving coatability). Is preferred.

  As a method for producing the polymerization layer and a plate making method, methods described in detail in JP-A No. 2001-133969 can be used.

<Acid cross-linked layer>
Further, as one of the thermal negative type image recording layers, an acid cross-linked image recording layer (acid cross-linked layer) is also preferably exemplified. The acid crosslinking layer comprises a photothermal conversion substance, a thermal acid generator, a compound that crosslinks with an acid that is a curable compound (crosslinking agent), and an alkali-soluble polymer compound that can react with the crosslinking agent in the presence of an acid. contains. In the acid cross-linking layer, infrared light absorbed by the light-to-heat conversion substance is converted into heat, and the thermal acid generator is decomposed by this heat to generate an acid, and the generated acid reacts with the cross-linking agent and the alkali-soluble polymer compound. And harden.

Examples of the photothermal conversion substance include the same substances as those used for the polymerization layer.
Examples of the thermal acid generator include thermal decomposition compounds such as photoinitiators for photopolymerization, photochromic agents for dyes, and acid generators used in microresists.
Examples of the crosslinking agent include an aromatic compound substituted with a hydroxymethyl group or an alkoxymethyl group; a compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group; and an epoxy compound.
Examples of the alkali-soluble polymer compound include a novolak resin and a polymer having a hydroxyaryl group in the side chain.

<Photopolymer type>
The photopolymerization type photosensitive composition contains an addition polymerizable compound, a photopolymerization initiator, and a polymer binder.
As the addition polymerizable compound, an ethylenically unsaturated bond-containing compound capable of addition polymerization is preferably exemplified. The ethylenically unsaturated bond-containing compound is a compound having a terminal ethylenically unsaturated bond. Specifically, for example, it has a chemical form such as a monomer, a prepolymer, and a mixture thereof. Examples of monomers include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, maleic acid) and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds. Is mentioned.
Moreover, as an addition polymerizable compound, a urethane type addition polymerizable compound is also preferably exemplified.

As the photopolymerization initiator, various photopolymerization initiators or a combination system (photoinitiation system) of two or more photopolymerization initiators can be appropriately selected depending on the wavelength of the light source to be used. For example, the initiation system described in JP-A-2001-22079, [0021] to [0023] is preferable.
The polymer binder not only functions as a film forming agent for the photopolymerization type photosensitive composition, but is soluble or swellable in alkaline water because the image recording layer needs to be dissolved in an alkaline developer. An organic high molecular polymer is used. As such an organic polymer, those described in JP-A-2001-22079, [0036] to [0063] are preferably exemplified.

  In the photopolymer type photopolymerization type photosensitive composition, additives described in JP-A-2001-22079, [0079] to [0088] (for example, a surfactant for improving coatability) , Colorants, plasticizers, thermal polymerization inhibitors).

Further, it is preferable to provide an oxygen-blocking protective layer on the photopolymer type image recording layer in order to prevent the action of inhibiting the polymerization of oxygen. Examples of the polymer contained in the oxygen barrier protective layer include polyvinyl alcohol and copolymers thereof.
Furthermore, it is also preferable to provide an intermediate layer or an adhesive layer as described in [0124] to [0165] of JP-A-2001-228608.

<Conventional negative type>
The conventional negative photosensitive composition contains a diazo resin or a photocrosslinking resin. Among these, a photosensitive composition containing a diazo resin and an alkali-soluble or swellable polymer compound (binder) is preferable.
Examples of the diazo resin include condensates of aromatic diazonium salts and active carbonyl group-containing compounds such as formaldehyde; condensates of p-diazophenylamines and formaldehyde with hexafluorophosphate or tetrafluoroborate. An organic solvent-soluble diazo resin inorganic salt which is a reaction product of In particular, a high molecular weight diazo compound containing 20 mol% or more of a hexamer described in JP-A-59-78340 is preferable.
Examples of the binder include a copolymer containing acrylic acid, methacrylic acid, crotonic acid, or maleic acid as an essential component. Specifically, multi-component copolymers of monomers such as 2-hydroxyethyl (meth) acrylate, (meth) acrylonitrile, and (meth) acrylic acid as described in JP-A-50-118802, Examples thereof include multi-component copolymers composed of alkyl acrylate, (meth) acrylonitrile and unsaturated carboxylic acid as described in JP-A-56-4144.

  The conventional negative type photosensitive composition has, as additives, the bake-out agent, dye, and flexibility and abrasion resistance described in JP-A-7-281425, [0014] to [0015]. It is preferable to contain a plasticizer for imparting, a compound such as a development accelerator, and a surfactant for improving coatability.

  Under the conventional negative type photosensitive layer, an intermediate layer containing a polymer compound having a component having an acid group and a component having an onium group as described in JP-A-2000-105462 is provided. Is preferred.

<Conventional positive type>
The conventional positive-type photosensitive composition contains a quinonediazide compound. Among these, a photosensitive composition containing an o-quinonediazide compound and an alkali-soluble polymer compound is preferable.
Examples of the o-quinonediazide compound include esters of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and phenol-formaldehyde resin or cresol-formaldehyde resin, described in US Pat. No. 3,635,709. And esters of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and pyrogallol-acetone resin.
Examples of the alkali-soluble polymer compound include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde co-condensation resin, polyhydroxystyrene, N- (4-hydroxyphenyl) methacrylamide copolymer, A carboxy group-containing polymer described in JP-A-7-36184, an acrylic resin containing a phenolic hydroxy group as described in JP-A-51-34711, and described in JP-A-2-866 Examples thereof include acrylic resins having a sulfonamide group and urethane resins.

  Conventional positive type photosensitive compositions include compounds such as sensitivity modifiers, printing agents, dyes and the like described in JP-A-7-92660, [0024] to [0027] as additives. It is preferable to contain a surfactant for improving the coating property as described in [0031] of Kaihei 7-92660.

  Under the conventional positive type photosensitive layer, it is preferable to provide an intermediate layer similar to the intermediate layer suitably used for the above-described conventional negative type.

<Non-treatment type>
Examples of the non-processing type photosensitive composition include a thermoplastic fine particle polymer type, a microcapsule type, and a sulfonic acid-generating polymer-containing type. These are all heat-sensitive types containing a photothermal conversion substance. The photothermal conversion substance is preferably the same dye as that used in the above-described thermal positive type.

The thermoplastic fine particle polymer type photosensitive composition is obtained by dispersing a hydrophobic and heat-meltable fine particle polymer in a hydrophilic polymer matrix. In the image recording layer of the thermoplastic fine particle polymer type, the hydrophobic fine particle polymer is melted by heat generated by exposure and is fused to form a hydrophobic region, that is, an image portion.
As the fine particle polymer, those in which fine particles melt and coalesce with heat are preferable, and those having a hydrophilic surface and capable of being dispersed in a hydrophilic component such as dampening water are more preferable. Specifically, Research Disclosure No. 33303 (January 1992), JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, and JP-A-9-171250, and European Patent Application Publication No. 931,647. Preferred examples thereof include thermoplastic fine particle polymers. Of these, polystyrene and polymethyl methacrylate are preferred. Examples of the fine particle polymer having a hydrophilic surface include those in which the polymer itself is hydrophilic; those in which a hydrophilic compound such as polyvinyl alcohol and polyethylene glycol is adsorbed on the surface of the fine particle polymer to make the surface hydrophilic.
The fine particle polymer preferably has a reactive functional group.

  As a microcapsule type photosensitive composition, a compound having a heat-reactive functional group as described in JP-A No. 2000-118160 or JP-A No. 2001-277740 is included. A microcapsule type is preferable.

  Examples of the sulfonic acid generating polymer used in the sulfonic acid generating polymer-containing photosensitive composition include sulfonic acid ester groups, disulfone groups, and sec- or tert-sulfonamides described in JP-A No. 10-282672. Examples thereof include polymers having a group in the side chain.

  By incorporating a hydrophilic resin into the unprocessed photosensitive composition, not only on-press developability is improved, but also the film strength of the photosensitive layer itself is improved. Examples of the hydrophilic resin include those having a hydrophilic group such as hydroxy group, carboxy group, hydroxyethyl group, hydroxypropyl group, amino group, aminoethyl group, aminopropyl group, carboxymethyl group, and hydrophilic sol-gel conversion system. A binder resin is preferred.

  The unprocessed type image recording layer does not require a special development step and can be developed on a printing press. As a method for producing an unprocessed image recording layer and a plate-making printing method, methods described in detail in JP-A No. 2002-178655 can be used.

<Back coat>
In this way, the backside of the lithographic printing plate precursor of the present invention obtained by providing various image recording layers on the lithographic printing plate support obtained by the present invention, if necessary, is an image in the case of overlapping. In order to prevent the recording layer from being damaged, a coating layer made of an organic polymer compound can be provided.

[Plate making method (lithographic printing plate production method)]
The lithographic printing plate precursor using the lithographic printing plate support obtained by the present invention is made into a lithographic printing plate by various treatment methods according to the image recording layer.
Examples of the active light source used for image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, and a chemical lamp. Examples of the laser beam include a helium-neon laser (He-Ne laser), an argon laser, a krypton laser, a helium-cadmium laser, a KrF excimer laser, a semiconductor laser, a YAG laser, and a YAG-SHG laser.

After the above exposure, if the image recording layer is one of a thermal positive type, a thermal negative type, a conventional negative type, a conventional positive type, and a photopolymer type, it is exposed and then developed using a developer to obtain a lithographic printing plate. It is preferable to obtain.
The developer is preferably an alkaline developer, and more preferably an alkaline aqueous solution substantially free of an organic solvent.
Moreover, the developing solution which does not contain alkali metal silicate substantially is also preferable. As a method of developing using a developer substantially not containing an alkali metal silicate, a method described in detail in JP-A No. 11-109637 can be used.
A developer containing an alkali metal silicate can also be used.

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

1. Preparation of lithographic printing plate support (Examples 1-15, Comparative Examples 1-5)
According to the method described below, lithographic printing plate supports of Examples and Comparative Examples were obtained.
<Manufacture of aluminum plates>
Si: 0.06 mass%, Fe: 0.30 mass%, Cu: 0.005 mass%, Mn: 0.001 mass%, Mg: 0.001 mass%, Zn: 0.001 mass%, Ti: Containing 0.03% by mass, the balance is prepared using Al and an inevitable impurity aluminum alloy, and after performing the molten metal treatment and filtration, an ingot having a thickness of 500 mm and a width of 1200 mm is obtained by a DC casting method. Produced. After the surface was shaved with a chamfering machine with an average thickness of 10 mm, the temperature was kept constant at 550 ° C. for about 5 hours, and when the temperature dropped to 400 ° C., rolling with a thickness of 2.7 mm using a hot rolling mill A board was used. Furthermore, after performing heat processing using a continuous annealing machine at 500 degreeC, it finished by cold rolling to 0.24 mm in thickness, and obtained the aluminum plate of JIS1050 material.
After making this aluminum plate into width 1030mm, it used for the surface treatment shown below.

(Examples 1-13, Comparative Examples 2-5)
<Surface treatment>
In the surface treatment, the following various treatments (a) to (j) were continuously performed. After each treatment and washing with water, the liquid was removed with a nip roller.

(A) Mechanical roughening treatment (brush grain)
Using an apparatus as schematically shown in FIG. 5, an aqueous suspension (specific gravity 1.1 g / cm ³ ) of an abrasive (pumice, average particle size 30 μm, SiO ₂ content: 73 mass%) is polished. While supplying the slurry liquid to the surface of the aluminum plate, a mechanical surface roughening treatment was performed with a rotating roller-shaped nylon brush. In FIG. 5, 1 is an aluminum plate, 2 is a roller-like brush (in this embodiment, No. 3 nylon brush, bundled brush).
The material of the nylon brush was 6 · 10 nylon, the hair length was 50 mm, and the hair diameter was 0.3 mm. The nylon brush was planted so as to be dense by making a hole in a stainless steel cylinder having a diameter of 400 mm. Although only two rotating brushes are shown in FIG. 5, three are actually used. The distance between the two support rollers (φ200 mm) at the bottom of the brush was 300 mm. The brush roller was pressed until the load of the drive motor for rotating the brush became 10 kW plus with respect to the load before the brush roller was pressed against the aluminum plate. The direction of rotation of the brush was the same as the direction of movement of the aluminum plate at the point where the brush and the plate contacted. The rotation speed of the brush was 150 rpm.

(B) First etching treatment The aluminum plate obtained above was subjected to an etching treatment by spraying using an aqueous solution having a caustic soda concentration of 26 mass%, an aluminum ion concentration of 5 mass%, and a temperature of 60 ° C. The etching amount was 10 g / m ² .
Then, water washing by spraying was performed.

(C) First desmut treatment An aqueous solution having a sulfuric acid concentration of 1% by mass, an aluminum ion concentration of 4.5 g / L, and a temperature of 35 ° C. is sprayed on an aluminum plate from a spray tube to perform desmut treatment for 10 seconds. did. In the first desmut treatment, the waste solution of the solution used in the first electrochemical surface roughening treatment was used.

(D) First electrochemical roughening treatment (first electrolytic treatment)
An alternating current having a frequency of 60 Hz and a rectangular waveform was continuously passed through the aluminum plate to perform an electrochemical surface roughening treatment. The electrolytic solution at this time was a 1% by mass aqueous solution of nitric acid (containing 4.5% by mass of aluminum ions and 80 ppm of ammonium ions) at a liquid temperature of 35 ° C. Ferrite was used for the auxiliary anode. The electrolytic cell used was the one shown in FIG. The total amount of electricity when the aluminum plate was an anode was 220 C / dm ² . Further, the current density during the anode reaction of the aluminum plate at the peak of alternating current was 25 A / dm ² . Then, water washing by spraying was performed.

(E) Second etching treatment The aluminum plate obtained above is subjected to an etching treatment by spraying using an aqueous solution having a caustic soda concentration of 26% by mass, an aluminum ion concentration of 5% by mass and a temperature of 60 ° C., and using the previous AC current. The smut component mainly composed of aluminum hydroxide generated during the electrochemical surface roughening treatment was removed, and the edge portion of the generated pit was dissolved to smooth the edge portion. The etching amount was 0.2 g / dm ² .
Then, water washing by spraying was performed.

(F) Second desmut treatment An aqueous solution having a sulfuric acid concentration of 30% by mass, an aluminum ion concentration of 1% by mass, and a temperature of 35 ° C. was sprayed from a spray tube on the aluminum plate to perform desmut treatment for 10 seconds, and then washed with water by spraying.

(G) Second electrochemical roughening treatment (second electrolytic treatment)
An alternating current having a frequency of 60 Hz and a rectangular waveform was continuously passed through the aluminum plate to perform an electrochemical surface roughening treatment. The electrolytic solution at this time was a hydrochloric acid 5 g / L aqueous solution (containing 4.5 mass% of aluminum ions) at a temperature of 35 ° C. Ferrite was used for the auxiliary anode. The electrolytic cell used was the one shown in FIG. The total amount of electricity when the aluminum plate was an anode was as shown in Table 1. Further, the current density during the anode reaction of the aluminum plate at the peak of alternating current was 25 A / dm ² .
Then, water washing by spraying was performed.

(H) Third etching treatment The aluminum plate was subjected to an etching treatment by spraying at 60 ° C. using an aqueous solution having a caustic soda concentration of 26 mass% and an aluminum ion concentration of 5 mass%, the aluminum plate was dissolved, and the previous stage AC was used. The smut component mainly composed of aluminum hydroxide generated during the electrochemical surface roughening treatment was removed, and the edge portion of the generated pit was dissolved to smooth the edge portion. The etching amount was as shown in Table 1.
Then, water washing by spraying was performed.

(I) Third desmut treatment An aqueous solution having a sulfuric acid concentration of 30% by mass, an aluminum ion concentration of 1% by mass and a temperature of 35 ° C. was sprayed from a spray tube on the aluminum plate to perform desmut treatment for 10 seconds, and then washed with water by spraying.

(J) Anodizing treatment Anodizing treatment was performed using an anodizing apparatus having the structure shown in FIG. 4 to obtain a lithographic printing plate support of Example 1. Sulfuric acid was used as the electrolytic solution supplied to the anodizing treatment. All electrolytes had a sulfuric acid concentration of 15% by mass (including 1% by mass of aluminum ions) and a temperature of 35 ° C. Then, water washing by spraying was performed. The final oxide film amount was 2.4 g / m ² .

(Example 14)
Surface treatment similar to the above was performed except that the following (a-1) treatment was performed instead of the above (a).
(A-1) Concavity and convexity transfer treatment (transfer grain)
An ingot is manufactured by DC casting and rolled to produce an aluminum rolled plate. In the final cold rolling process, a rolling roll having irregularities on the surface is pressed against the aluminum rolled plate to transfer the irregularities, and irregularities are formed on the surface. An aluminum plate having a thickness of 0.3 mm and a width of 1060 mm was obtained. As a rolling roll having irregularities on its surface, air blasting using alumina with an average particle size of 80 μm as a grid is performed twice to form irregularities on the surface of the steel roll, and then the surface is hardened by hard chrome plating. What was obtained was used.

(Example 15)
Surface treatment similar to the above was performed except that the following (a-2) and (b ′) treatments were performed instead of the above (a) and (b).
(A-2) Electrochemical roughening treatment (hydrochloric acid electrolysis treatment)
An electrochemical surface roughening treatment was continuously performed using an alternating voltage of 60 Hz. The liquid temperature was 35 ° C. The AC power supply waveform is the waveform shown in FIG. 2, the time TP until the current value reaches the peak from zero is 0.8 msec, the duty ratio is 1: 1, the trapezoidal rectangular wave AC is used, with the carbon electrode as the counter electrode An electrochemical roughening treatment was performed. Ferrite was used for the auxiliary anode. The electrolytic cell shown in FIG. 3 was used.
The current density was 25 A / dm ^{2 as} an average value of current.
The electrolytic solution used for hydrochloric acid electrolysis was an aqueous solution containing 0.5% by mass of hydrochloric acid (10 g / L) (containing 0.5% by mass of aluminum ions), and was performed for 16 seconds. The amount of electricity in hydrochloric acid electrolysis was 400 C / dm ^{2 as} the total amount of electricity when the aluminum plate was the anode.
Then, water washing by spraying was performed.

(B ′) First Etching Treatment The aluminum plate obtained above was subjected to an etching treatment by spraying using an aqueous solution having a caustic soda concentration of 26 mass%, an aluminum ion concentration of 5 mass%, and a temperature of 60 ° C. The etching amount was 3 g / m ² .
Then, water washing by spraying was performed.

(Comparative Example 1)
The lithographic printing plate support of Comparative Example 1 was obtained by repeating the surface treatment performed in Example 1 except that the treatment (a) was not performed.

2. Calculation of surface shape factor of lithographic printing plate support For the surface of the lithographic printing plate support obtained above, the arithmetic average roughness _Ra , the number of recesses having _a depth of 4 μm or more, and the surface area The ratio ΔS ^{5 (0.02-0.2)} (AFM specific surface area) was determined. The results are shown in Table 1.

(A) Measurement of arithmetic mean roughness R _a First, stylus roughness meter (e.g., Sufcom575, (Inc.) Tokyo Ltd. Seimitsu) performs a two-dimensional roughness measurement, the arithmetic average roughness as defined in ISO4287 _Ra was measured.
The conditions for the two-dimensional roughness measurement were as follows.
<Measurement conditions>
Cut-off value 0.8mm, tilt correction FLAT-ML, measurement length 3mm, vertical magnification 10,000 times, scanning speed 0.3mm / sec, stylus tip diameter 2μm

(B) Number of recesses with a depth of 4 μm or more The number of recesses with a depth of 4 μm or more is 0.01 μm resolution with a laser microscope (Micromap 520, manufactured by Ryoka System Co., Ltd.) without contacting 400 μm □ on the surface. The three-dimensional data was obtained by scanning with, and the number of recesses having a depth of 4 μm or more was counted in this three-dimensional data.
The measurement was performed at five locations and the average was obtained. The results are shown in Table 1.

(C) Measurement of surface area ratio ΔS ^{5 (0.02-0.2)} First, the surface shape was measured using an atomic force microscope (SPA300 / SPI3800N manufactured by Seiko Instruments Inc.) to obtain three-dimensional data (f (x, y)). .
The planographic printing plate support is cut to a size of 1 cm square, set on a horizontal sample stage on a piezo scanner, the cantilever is approached to the sample surface, and when it reaches the region where the atomic force is applied, it moves in the XY direction. Scanning was performed, and the unevenness of the sample was captured by the displacement of the piezo in the Z direction. A piezo scanner that can scan 150 μm in the XY direction and 10 μm in the Z direction was used. A cantilever having a resonance frequency of 120 to 400 kHz and a spring constant of 12 to 90 N / m (SI-DF20, manufactured by Seiko Instruments Inc.) was used and measured in a DFM mode (Dynamic Force Mode). Further, the reference plane was obtained by correcting a slight inclination of the sample by approximating the obtained three-dimensional data by least square approximation.
At the time of measurement, 512 × 512 points of 5 μm □ on the surface were measured. The resolution in the XY direction was 0.01 μm, the resolution in the Z direction was 0.15 nm, and the scan speed was 5 μm / sec.
Next, components having a wavelength of 0.02 μm or more and 0.2 μm or less were extracted from the obtained three-dimensional data (f (x, y)). Extraction of components having a wavelength of 0.02 μm or more and 0.2 μm or less is performed by fast Fourier transforming three-dimensional data (f (x, y)) to obtain a frequency distribution, and then components having a wavelength of less than 0.02 μm and 0.2 μm. After removing super components, the inverse Fourier transform was performed.
Then, using the three-dimensional data (g (x, y)) obtained by extraction, three adjacent points are extracted, the sum of the areas of the minute triangles formed by the three points is obtained, and the actual area S _x ^{5 (0.02-0.2)} . The surface area ratio ΔS ^{5 (0.02-0.2)} was determined by the following formula (1) from the obtained real area S _x ^{5 (0.02-0.2)} and the geometric measurement area S ₀ .

ΔS ^{5 (0.02-0.2)} = [(S _x ^{5 (0.02-0.2)} −S ₀ ) / S ₀ ] × 100 (%) (1)

(D) Measurement of recording layer thickness A recording layer, which will be described later, is applied to a lithographic printing plate support, dried and then cut into an area of 1 dm ² , the mass is measured, and then the solvent (MEK, γ-BL) The recording layer was removed and dried to measure the mass, and the mass of the recording layer per area of the support was calculated from the decrease in mass. The results are shown in Table 1.

3. Preparation of lithographic printing plate precursor A lithographic printing plate precursor was obtained by providing each lithographic printing plate support obtained above with a thermal positive type image recording layer as follows. Before providing the image recording layer, an undercoat layer was provided as described later.
On the lithographic printing plate support, an undercoat solution having the following composition was applied and dried at 80 ° C. for 15 seconds to form a coating film of an undercoat layer. The coating amount of the coating film after drying was 15 mg / m ² .

<Undercoat liquid composition>
・ The following polymer compound 0.3g
・ Methanol 100g
・ Water 1g

  Further, a heat-sensitive layer coating solution having the following composition was prepared, and the coating amount (heat-sensitive layer coating amount) after drying this heat-sensitive layer coating solution on a lithographic printing plate support provided with an undercoat layer is a value shown in Table 1. And dried to form a heat sensitive layer (thermal positive type image recording layer) to obtain a lithographic printing plate precursor.

<Thermosensitive layer coating solution composition>
Novolak resin (m-cresol / p-cresol = 60/40, mass average molecular weight 7,000, containing 0.5% by mass of unreacted cresol) 0.90 g
-Ethyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (molar ratio 35/35/30) 0.10 g
-Cyanine dye A 0.1 g represented by the following structural formula
・ Tetrahydrophthalic anhydride 0.05g
・ 0.002 g of p-toluenesulfonic acid
-Ethyl violet counter ion with 6-hydroxy-β-naphthalenesulfonic acid 0.02 g
・ Fluorosurfactant (Megafac F-780F, manufactured by Dainippon Ink & Chemicals, Inc., solid content: 30% by mass) 0.0045 g (solid content conversion)
・ Fluorosurfactant (Megafac F-781F, manufactured by Dainippon Ink & Chemicals, Inc., solid content: 100% by mass) 0.035 g
・ Methyl ethyl ketone 12g

4). Evaluation of planographic printing plate precursor The printing durability, stain resistance, and scratch resistance of the planographic printing plate precursor were evaluated by the following methods.
(A) Printing durability The resulting lithographic printing plate precursor was imaged using a TrendSetter manufactured by Creo at a drum rotation speed of 150 rpm and a beam intensity of 10 W.
Thereafter, using a PS processor 940H manufactured by Fuji Photo Film Co., Ltd. charged with an alkaline developer having the following composition, the solution was maintained at 30 ° C. and developed for 20 seconds to obtain a lithographic printing plate.

<Alkali developer composition>
・ D-Sorbit 2.5% by mass
-Sodium hydroxide 0.85 mass%
・ Polyethylene glycol lauryl ether (mass average molecular weight 1,000)
0.5% by mass
・ Water 96.15% by mass

The resulting lithographic printing plate was printed on a Lithrone printing machine manufactured by Komori Corporation using DIC-GEOS (N) black ink manufactured by Dainippon Ink & Chemicals, Inc. The printing durability was evaluated based on the number of printed sheets when visually recognized. The number of printed sheets is preferably 40,000 or more.
The results are shown in Table 2.

(B) Stain resistance Using a planographic printing plate obtained in the same manner as in the case of (A) Evaluation of printing durability, DIC-GEOS (s) is used with a Mitsubishi diamond type F2 printing machine (manufactured by Mitsubishi Heavy Industries, Ltd.). Printing was carried out using red ink, and the blanket stain after printing 10,000 sheets was visually evaluated.
The results are shown in Table 1. The meanings of the symbols in Table 1 are as follows, and the evaluation was made on a 7-point scale.
“Excellent 1”: The blanket is almost unclean “Excellent 2”: Intermediate between Excellent 1 and Excellent 2 “Excellent 3”: Blanket is slightly dirty “Yes 4”: Intermediate between Excellent 3 and Excellent 4 “ "5": Blanket is dirty but within the allowable range "No 6": Between intermediate 5 and 7 "No 7": Blanket is dirty on the entire surface

(C) Scratch resistance (difficulty to scratch, transport test evaluation in a slip-less packaging form))
The prepared infrared photosensitive lithographic printing plate precursor was cut into 1030 mm × 800 mm, and 30 sheets were prepared for each without inserting slip sheets. The 30 sheets were stacked, one each of 0.5 mm thick cardboard was placed on the top and bottom, the four corners were taped, and then wrapped with aluminum kraft paper. This was further packaged with a cardboard case and taped to make an interleaf-free packaging form. This was placed on a pallet, transported 2000 km by truck, then opened, and Fuji Photo Film Co., Ltd.'s automatic developing machine LP-940HII was loaded with Fuji Photo Film Co., Ltd. developer DT-2 at 1: 8. Charged and developed. The developed sample was evaluated for missing image areas due to transportation.
“Excellent 1” indicates that the image area is completely absent, “impossible 7” indicates that the support is almost visible and the color of the heat-sensitive layer is hardly visible, and the intermediate levels are “excellent 2” and “excellent” in order. It was expressed as “3”, “Yes 4”, “Yes 5”, and “No 6”, and was given a 7-level evaluation.
The results are shown in Table 2.
(D) Sensitivity The non-image portion of the lithographic printing plate obtained in the same manner as in the evaluation of printing durability was observed using a 20 × magnifier, and the remaining state of the image recording layer was evaluated in 7 stages. .
The results are shown in Table 2. The meanings of the symbols in the table are as follows.
“Excellent 1”: No image recording layer remains “Excellent 2”: Intermediate between Excellent 1 and Excellent 2 “Excellent 3”: Almost no image recording layer remains, and there is no practical problem at all “Yes 4” : Intermediate between excellent 3 and possible 4 “possible 5”: image recording layer remains but is at an acceptable level “impossible 6”: intermediate between acceptable 5 and impossible 7 “impossible 7”: image recording layer is in a pop-like shape There are many problems in practical use.

It is typical sectional drawing of the apparatus which performs the water washing process with the free-fall curtain-like liquid film used for the water washing process in the manufacturing method of the lithographic printing plate support of this invention. It is a graph which shows an example of the waveform of alternating current used for the 2nd electrochemical roughening process in the manufacturing method of the support for lithographic printing plates of the present invention. It is a side view which shows an example of the radial type cell in the electrochemical roughening process using alternating current in the manufacturing method of the support body for lithographic printing plates of this invention. It is the schematic of the anodizing apparatus used for the anodizing process in the manufacturing method of the support body for lithographic printing plates of this invention. It is a side view which shows the concept of the process of the mechanical roughening process in the manufacturing method of the support body for lithographic printing plates of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Aluminum plate 2 Roller-like brush 2A Body 2B Brush bristle 4A, 4B Support roller 6 Polishing slurry supply tank T Conveying surface Arrow a Conveying direction Arrow b Rotating direction 11 Aluminum plate 12 Radial drum roller 13a, 13b Main electrode 14 Electrolytic treatment liquid 15 Electrolyte supply port 16 Slit 17 Electrolyte passage 18 Auxiliary anode 19a, 19b Thyristor 20 AC power supply 40 Main electrolytic tank 50 Auxiliary anode tank 100 Water washing apparatus with free fall curtain liquid film 102 Water 104 Water storage tank 106 Water supply cylinder 108 Rectifying unit 410 Anodizing device 412 Power supply tank 413 Intermediate tank 414 Anodizing tank 416 Aluminum plate 418, 426 Electrolyte 420 Anode 422, 428 Pass roller 424 Nip roller 430 Cathode 434 DC power supply 436, 438 Supply liquid Zur 440 shield plate 442 drain port

Claims (4)

Arithmetic mean roughness R _a of the surface is 0.36～0.50Myuemu,
The number of recesses having a depth of 4 μm or more is 3.0 or less per 400 μm □,
Approximate three-point method based on data obtained by extracting components with a wavelength of 0.02 to 0.2 μm from three-dimensional data obtained by measuring 512 × 512 points on the surface of 5 μm □ using an atomic force microscope A planographic ^plate in which the surface area ratio ΔS ^{5 (0.02-0.2)} obtained by the following formula (1 ⁾ is 50 to 90% from the actual area S _x ^{5 (0.02-0.2)} obtained by the equation (1) and the geometric measurement area S ₀ Support for printing plate.
ΔS ^{5 (0.02-0.2)} = (S _x ^{5 (0.02-0.2)} −S ₀ ) / S ₀ × 100 (%) (1) A lithographic printing plate precursor having a recording layer of 1.1 to 1.6 g / m ² on the lithographic printing plate support according to claim 1. The aluminum plate is subjected to an electrochemical surface roughening treatment in an aqueous solution containing at least nitric acid, an electrochemical surface roughening treatment in an aqueous solution containing hydrochloric acid, and then brought into contact with an alkaline aqueous solution to reduce the etching amount. method of manufacturing a lithographic printing plate support according to claim 1, alkali etching treatment so that 0.01~0.08g / dm ^2. The lithographic printing plate according to claim 1, wherein the aluminum plate is subjected to a mechanical surface roughening treatment by rubbing with a rotating brush while supplying at least an abrasive having an average particle size of 5 to 40 µm and an SiO ₂ content of 60 mass% or more. For producing a support for an automobile.

Images