JP2005146299A - Roll for embossing aluminum plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a roll for embossing an aluminum plate capable of obtaining the original plate for a planographic printing plate having excellent printing performance and sensitivity by utilizing an aluminum plate having a rugged structure obtained by being subjected to embossing using the same since the rugged structure in which the height of projecting parts is made uniform and the number of projecting parts is large can be transferred to the aluminum plate owing to the roll. <P>SOLUTION: In the roll for embossing an aluminum plate, the surface of a roll made of steel is provided with a roughened face subjected to electrolytic treatment in an electrolytic solution with the roll as an anode, and the surface thereof is provided with a chromium plated layer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  TECHNICAL FIELD The present invention relates to a rolling steel roll for embossing an aluminum plate surface to provide irregularities, a method for producing the roll, and a method for producing a lithographic printing plate support using the roll.

In order to produce a support for a lithographic printing plate, the surface of an aluminum plate is rolled with a steel roll on which irregularities have been formed in advance to provide irregularities such as embossing. A roll is known (Patent Document 1). A method of rolling at a rolling reduction of 2 to 20% with a steel roll produced by honing (Ra = 0.5 to 1.5 μm, depth of irregularities of 0.6 μm or more is 500 pieces / mm ² or more) (Patent Literature) 2) A method of rolling at a rolling reduction of 2 to 20% with a roll in which unevenness with Ra = 0.5 to 1.5 μm and depth of 0.6 μm or more is 500 pieces / mm ² or more by chemical etching or honing process ( Patent Document 3), rolls with irregularities formed by electric discharge machining (Ra = 0.7 to 1.7 μm, irregularities with a depth of 0.6 μm or more are 500 pieces / mm ² or more), rolled at a reduction rate of 2 to 20% Is described (Patent Document 4).

The surface of the roll for rolling is aligned with the uneven surface of the roll surface (hereinafter sometimes referred to as “the height of the surface of the roll”), which can increase the life of the roll. Known from the prior art. However, in the roll for rolling the aluminum plate of the conventional lithographic printing plate support, the surface of the rolled roll has a high height because a rough surface is formed by hitting an abrasive on the surface by blasting such as air blasting or shot blasting. It was difficult to obtain a roll surface that was uneven, had the desired irregularities sufficient for embossing, and had a sufficiently high height on the roll surface.
Also, in these conventional rolls, the aluminum plate processed by using the roll is digitized into an aluminum support for a lithographic printing plate, particularly a CTP plate (high convergence radiation such as laser light). Printing performance when image information is carried and the lithographic printing plate precursor is scanned and exposed with light to produce an aluminum support for computer-to-plate technology that directly produces a lithographic printing plate without a lithographic film. In particular, it was difficult to obtain an aluminum support excellent in the number of printed sheets and sensitivity.

  On the other hand, in the rolling rolls for processes used for rolling steel sheets, etc., electrolytic treatment is performed using a dull finish roll as an anode in an electrolytic solution, and the number of ridges on the roll surface is increased by 1 to 50% from that before electrolysis. Then, a chrome plating roll for rolling (Patent Document 5) that has been subjected to chrome plating is known.

Further, before or after chrome plating, the surface roughness is R _Z , a chrome plating roll for rolling whose initial roughness is reduced by 5 to 20% (Patent Document 6), and chromic anhydride and sulfuric acid in the etching process. the chromium plating solution used consisting of a roll as an anode, the roughness of the roll surface R _Z, chrome plated roll was chrome-plated after reducing 5-20% than the initial roughness (Patent Document 7), chromium Electrolytic treatment is performed in the plating solution using a bright finish roll as the anode, and the number of roll surfaces indicated by PPI (peak per inch) is increased by 1.3 to 15 times the initial number of peaks, and then the roll is used as the cathode. A chromium plating roll (Patent Document 8) is known in which chromium plating is performed and then the plated roll surface is polished.
Further, in the method for producing a chromium plating roll, after electrolytic treatment using a roll base material as an anode in an electrolytic solution, the roll base material is used as a cathode in a chromium plating bath having an Fe concentration of less than 5 g / dm ^3. A method in which the current density is increased from 0 to 25 to 35 A / dm ² per minute and maintained at the current density for 2 to 3 minutes, and then the current density is lowered and held at ²⁰ to 30 A / dm ² to perform chromium plating ( Patent Document 9) is known.

  Some of these rolls have a steel roll surface that is etched by electrolysis to improve adhesion to the chromium plating layer. However, rolls used for rolling steel sheets have high smoothness. Whether it is a roll for bright steel sheets or a roll for dull steel sheets that has been appropriately roughened, the roll surface after chrome plating is for rolling and finishing cold-rolled steel sheets smoothly. The shape required for the product surface is completely different.

  In addition, as a rolling roll and a rolling roll manufacturing method, manufacturing apparatus, and plating apparatus, JP-A-7-180084 (plating apparatus), JP-A-63-99166 (roll mirror polishing apparatus), JP-A-8-27594 ( Steel plate manufacturing method and rolling chrome plating roll), JP-A-5-65686 (rolling dull roll manufacturing method), JP-A-2003-171799 (batch chrome plating method and apparatus), JP-A-3-47985 Techniques described in various publications such as (Chrome Plating Method) and JP-A-2002-47595 (Chromium Plating Method and Apparatus) are known.

JP 60-36196 A JP-A 62-25094 JP 62-111792 A JP-A-62-218189 Japanese Unexamined Patent Publication No. 64-8293 JP-A-61-202707 JP-A-61-201800 JP-A 1-123094 JP 2001-240994 A

  As a steel roll for rolling an aluminum plate as a support for a lithographic printing plate, the present invention rolls an aluminum plate using a roll having unevenness on the surface of the rolled roll, the Lithographic printing with excellent printing performance, especially the number of prints and sensitivity, if it is used as a support for lithographic printing plates by performing mechanical etching, electrochemical surface roughening, anodizing, sealing, hydrophilization, etc. Knowing that a plate precursor can be obtained, invented an aluminum plate embossing roll.

That is, the present invention provides the following inventions.
(1) An aluminum plate embossing roll having a rough surface electrolytically treated in an electrolytic solution using the roll as an anode on a steel roll surface, and having a chromium plating layer thereon.
(2) The aluminum plate embossing roll according to claim 1, wherein the surface of the steel roll of (1) is mirror-polished in advance.
(3) An aluminum plate embossing roll having a rough surface with an average surface roughness Ra of 0.5 to 2 μm and Sm of 10 to 200 μm on the roll surface after the electrolytic treatment of (1) or (2).

(4) The average surface roughness Ra of the steel roll surface before the electrolytic treatment as an anode in the electrolytic solution according to any one of (1) to (3) is 0.01 to 0.3 μm. An aluminum plate embossing roll.
(5) A method for producing an aluminum support for a lithographic printing plate comprising the step of transferring irregularities to the surface of an aluminum plate, using the roll for embossing an aluminum plate according to any one of (1) to (4).

  The roll for embossing the aluminum plate of the present invention has a rough surface on the roll surface that has been electrolyzed in an electrolytic solution using the roll as an anode. Since the concavo-convex structure on the roll surface with a large number of convex portions and the number of convex portions is transferred to the aluminum plate, if the aluminum plate having this concavo-convex structure is used as a lithographic printing plate support, it has excellent printing performance and sensitivity. A lithographic printing plate precursor is obtained.

As a result of earnest research, the inventors of the present invention do not use blasting, but use an appropriate roughening method to align the height of the convex portions on the roll surface and to increase the number of convex portions on the roll surface. We know that if an aluminum plate is rolled using a roll having a concavo-convex structure to form a lithographic printing plate support, a lithographic printing plate precursor excellent in printing performance, particularly in the number of printed sheets and sensitivity, can be obtained. Invented the roll.
The embossing roll of the present invention can be used for embossing of all metals, and is particularly suitable for embossing of an aluminum plate, and particularly for embossing of an aluminum plate used as a support for a lithographic printing plate. preferable. Most preferably, it is used as an aluminum plate embossing roll of a support for a lithographic printing plate for CTP.

[Aluminum plate embossing roll]
1) Roll material and pretreatment The roll is made of steel, especially forged steel. The roll material used in the present invention is not particularly limited and is generally used as a rolling roll, such as tool steel (SKD), high-speed steel (SKH), high carbon chromium bearing steel (SUJ), carbon, chromium, molybdenum, and vanadium. Any of forged steels containing any of these alloying elements may be used. In order to extend the roll life, high chromium alloy cast iron containing about 10 to 20% by mass of chromium may be used.

The roll used in the present invention is preferably hardened such as quenching or radical nitriding before the electrolytic treatment using the anode.
Preferably, a roll that has been mirror-finished by buffing in advance is subjected to electrolytic treatment as an anode in an electrolytic solution, and then subjected to chromium plating so that the height of the convex portions is uniform and the number of the rolls is large. Rolls can be manufactured.
The rolling roll is polished in advance with a grindstone or the like in order to obtain its cylindricity and parallelism, but when the surface is observed microscopically, streaky irregularities exist. By further mirror-finishing it, streaky irregularities are eliminated, and when the roll surface is etched by subsequent electrolytic treatment, it becomes easy to obtain convex portions having a uniform height. Examples of the mirror finish include grinding with a grindstone, buffing, electrolytic polishing, and the like, and buffing is particularly preferable.

  The average surface roughness Ra of the roll surface before the electrolytic treatment as an anode in the electrolytic solution is 0.01 to 0.3 μm, Rmax is 0.01 to 3 μm, and particularly preferably, Ra is 0.15 to 0.25 μm. , Rmax is preferably 0.05 to 2 μm. It is difficult to obtain a surface having an Ra of less than 0.01 at low cost. When Ra exceeds 0.3 μm, the heights of the convex portions on the roll surface when the roll is subjected to electrolytic treatment are not uniform, and the life of the roll may be shortened. It is difficult to obtain a surface having an Rmax of less than 0.01 at low cost. When Rmax exceeds 3 μm, the heights of the convex portions on the roll surface when the roll is subjected to electrolytic treatment are not uniform, and the life of the roll is shortened.

2) Electrolytic treatment The roll surface is roughened by electrolytic treatment in the electrolytic solution using the roll as an anode. Any electrolyte solution can be used as long as it is an aqueous solution of an acid generally used for roughening a metal, such as nitric acid, hydrochloric acid, sulfuric acid, chromic acid or a mixture thereof. Electrolytic treatment is preferably performed in an anodic electrolytic bath similar to a chromium plating bath described later. It is more preferable to use what is called a Sargent bath, which will be described later, generally used as a hard chromium plating bath.

Specific electrolytic treatment conditions are as follows:
Liquid temperature 20-70 degreeC, Preferably it is 40-60 degreeC.
Power supply waveform Although direct current or alternating current is used, direct current is preferable. The ripple component contained in the direct current is more preferably 5% or less.
Current density 20-80 A / dm ² , preferably 25-60 A / dm ²
Amount of electricity 1000~30000 C / dm ^2, and preferably is 5000~25000C / dm ^2, particularly preferably 8000~20000C / dm ^2.

It is preferable that the average surface roughness Ra of the roll surface after electrolytic treatment is 0.5 to 2.0 μm and Sm is 10 to 200 μm as a rolling method of the aluminum plate for an aluminum support for a lithographic printing plate.
When Ra is less than 0.5, sufficient unevenness cannot be transferred, and when an aluminum support for a lithographic printing plate is produced using this aluminum plate, a lithographic printing plate with inferior shinyness is produced. When a roll surface with an Ra of more than 2.0 is made by electrolytic treatment, the heights of the convex portions are not uniform. Therefore, when an aluminum support for a lithographic printing plate is produced using this aluminum plate, the lithographic printing is inferior in sensitivity. It becomes a version. If the roller is less than 10, it is difficult to obtain sufficient Ra on the rolled aluminum plate. If the Sm exceeds 200, a sufficient number of printed sheets cannot be obtained when an aluminum support for a lithographic printing plate is produced.
Rmax of the roll surface after electrolytic treatment is preferably 5 to 25 μm (particularly 7 to 15 μm), and Δa is preferably 5 to 25 degrees (particularly 8 to 20 degrees).
Ra, Rmax, Sm (R _Sm ) and Δa can be measured according to ISO4287. Two-dimensional roughness measurement is performed with a stylus type roughness meter (for example, sufcom 575, manufactured by Tokyo Seimitsu Co., Ltd.), the arithmetic average roughness Ra specified in ISO 4287 is measured five times, and the average value is defined as the average roughness. . The maximum height Rmax (Ry) for the reference length, the average interval of irregularities (average value in the reference length) Sm, and the average slope gradient Δa were also measured in the same manner.

  By making the heights of the convex portions uniform, the life of the rolling roll can be extended. Furthermore, when used for imparting irregularities in the cold rolling process of an aluminum support used for a lithographic printing plate, the depth of the concave portions of the aluminum plate provided with irregularities becomes uniform and locally deep concave portions. Therefore, a lithographic printing plate using this aluminum plate is a sensitive lithographic printing plate. The effect is particularly remarkable when a lithographic printing plate for CTP is produced.

3) Chromium plating Chromium plating bath is made of chromic anhydride (chromium trioxide) and a small amount of sulfuric acid, fluoride, silica fluoride, etc. is added to the bath. A lead alloy can be exemplified.
As a specific bath composition,
Chromic acid 150-400 g / L, preferably 200-350 g / L.
Sulfuric acid 1-5 g / L, preferably 2-4 g / L.
Iron 7 g / L or less, preferably 0.01 to 5 g / L,
However, it is most preferable to use a so-called Sargent bath composed of chromic anhydride and sulfuric acid generally used as a hard chromium plating bath.

The same bath may be used for the electrolytic treatment as the anode in the electrolytic solution and the hard chromium plating bath, but when the electrolytic treatment is carried out as the anode in the electrolytic solution, the iron content will melt and the better the iron content, the better the plating Is not obtained, it is preferable to use another bath. When another bath is used, since the roll moves in the air, the activity of the roll surface falls, and good plating cannot be obtained. Therefore, a current density of 20 to 80 A immediately before chromium plating is used for the purpose of activating the surface. A / dm ² at 10-60 seconds reverse electrolytic treatment (etching) it is preferable to.

The plating conditions are
Liquid temperature 20-70 degreeC, Preferably it is 40-60 degreeC.
Current density 20 to 80 A / dm ² , preferably 25 to 60 A / dm ² .
Power supply waveform Although direct current or alternating current is used, direct current is preferable. The ripple component contained in the direct current is more preferably 5% or less. A method is preferred in which the current is gradually increased from a low current density to a high current density over 1 to 1000 seconds, and then a constant current is maintained. By doing so, it becomes easy to attach plating uniformly.

  The hard chrome plating thickness is preferably 1 to 15 μm, and most preferably 3 to 9 μm. If the thickness is less than 1 μm, sufficient wear resistance cannot be obtained, and if it exceeds 15 μm, the surface is smoothed by plating, so that the effect of imparting unevenness by electrolytic treatment using a roll as an anode does not appear.

It is preferable that the average surface roughness Ra of the roll surface after the hard chrome plating treatment is 0.5 to 2 μm and Sm is 10 to 200 μm. When Ra is less than 0.5, sufficient unevenness cannot be transferred, and when an aluminum support for a lithographic printing plate is produced using this aluminum plate, a lithographic printing plate with inferior shinyness is produced. When a roll surface with an Ra of more than 2.0 is made by electrolytic treatment, the heights of the convex portions are not uniform. Therefore, when an aluminum support for a lithographic printing plate is produced using this aluminum plate, the lithographic printing is inferior in sensitivity. It becomes a version. If the roller is less than 10, it is difficult to obtain sufficient Ra on the rolled aluminum plate. If the Sm exceeds 200, a sufficient number of printed sheets cannot be obtained when an aluminum support for a lithographic printing plate is produced.
Rmax of the roll surface after the hard chrome plating treatment is preferably 5 to 25 μm (particularly 7 to 15 μm), and Δa is preferably 5 to 25 degrees (particularly 8 to 20 degrees).

The convex portions after electrolytic treatment using the roll surface as an anode or after hard chrome plating according to the present invention are preferably uniformly dispersed when the surface is projected onto the plane from directly above. The number is preferably 10 to 1000 in an area of 400 μm square, and particularly preferably 50 to 500.
In view of wear resistance, the hardness of the roll surface is preferably 700 to 1000 in terms of Hv. Moreover, it is preferable that the hardness after hard chrome plating is 800-1200 in Hv.

4) Preferred use of roll The rolling roll of the present invention is preferably used for imparting irregularities to the surface of an aluminum plate, and particularly used for imparting irregularities to the surface of an aluminum plate in order to obtain an aluminum plate for a lithographic printing plate. It is preferable. Among them, it is most preferable to use it for providing irregularities on the surface of the aluminum plate in order to obtain an aluminum plate for a lithographic printing plate for CTP.
The preferred rolling reduction when embossing an aluminum plate for use as an aluminum support for a lithographic printing plate using the roll of the present invention is 0.5 to 20%, more preferably 1 to 8%, 1 to 5% is most preferable. Rolling for transfer may be performed in 1 to 3 passes.

  The surface shape of the aluminum plate on which the concavo-convex pattern was formed by the rolling rolls described in the present invention is defined by Ra, 0.4 to 1.0 μm, Sm, 30 to 150 μm, Rmax, 1 to 10 μm, Δa, 1 to 1 It is preferably in the range of 10 degrees.

[Aluminum support]
<Aluminum plate (rolled aluminum)>
In the present invention, an aluminum plate used as a substrate for a lithographic printing plate support is made of a metal whose main component is dimensionally stable aluminum, that is, aluminum or an aluminum alloy. In addition to a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, or a plastic film or paper on which aluminum or an aluminum alloy is laminated or vapor-deposited can also be used. Furthermore, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 can also be used.

  In the following description, various substrates made of aluminum or an aluminum alloy mentioned above or various substrates having a layer made of aluminum or an aluminum alloy are collectively used as an aluminum plate. The foreign elements that may be contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium, and the content of the foreign elements in the alloy is 10% by mass or less. It is.

  In the present invention, it is preferable to use a pure aluminum plate. However, it is difficult to produce completely pure aluminum in terms of refining technology, so it may contain a slightly different foreign element. Thus, the composition of the aluminum plate used in the present invention is not specified, and aluminum alloy plates such as JIS A1050, JIS A1100, JIS A3005, and internationally registered alloy 3103A, which are conventionally publicly known materials, are known. Can be used as appropriate.

  The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, and more preferably 0.2 mm to 0.3 mm. This thickness can be appropriately changed according to the size of the printing press, the size of the printing plate, the user's desires, and the like.

  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 a soaking treatment, 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 the 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. Moreover, 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 present invention, in the final rolling step or the like of the aluminum plate as described above, the unevenness is formed by press rolling, transfer or the like using the aluminum embossing roll of the present invention.
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 surface of the aluminum plate by pressing the uneven surface to the aluminum plate. A method of forming an uneven pattern is preferred. By making the aluminum surface uneven with the final cold rolling and simplifying the process, a large cost reduction can be achieved. As such a method, specifically, a method described in JP-A-6-262203 can be used.

By using an aluminum plate having a concavo-convex pattern on the surface, it is possible to obtain a concavo-convex pattern having a uniform average pitch and depth than the concavo-convex pattern formed by the brush and the abrasive, thereby improving the stain resistance. Further, the amount of dampening water on the printing press can be easily adjusted (excellent in shinyness) while reducing energy consumed in the subsequent alkali etching treatment and roughening treatment. Further, in the first alkali etching process described later, the etching amount can be reduced to about 10 g / m ² or less, and the cost can be reduced. Further, when an aluminum plate having a concavo-convex pattern is used, the surface area of the obtained lithographic printing plate support is increased, so that the printing durability is more excellent.

The transfer is particularly preferably performed in the final cold rolling step of a normal aluminum plate.
Further, it is more preferable that the unevenness formed by the transfer is formed on both surfaces of the aluminum plate. Thereby, since the elongation rate of the aluminum plate of a surface and a back surface can be adjusted to the same grade, an aluminum plate with sufficient flatness can be obtained.

The aluminum plate used in the present invention is a continuous belt-like sheet material or plate material. That is, it may be an aluminum web or a sheet-like sheet cut to a size corresponding to a planographic printing plate precursor shipped as a product.
Since scratches on the surface of the aluminum plate may become defects when processed into a lithographic printing plate support, it is possible to generate scratches at the stage prior to the surface treatment process for making a lithographic printing plate support It is necessary to suppress as much as possible. For that purpose, it is preferable that the package has a stable form and is not easily damaged during transportation.
In the case of an aluminum web, for example, the packing form of aluminum is, for example, laying a hardboard and felt on an iron pallet, applying cardboard donut plates to both ends of the product, wrapping the whole with a polytube, and inserting a wooden donut into the inner diameter of the coil Then, a felt is applied to the outer periphery of the coil, the band is squeezed with a band, and the display is performed on the outer periphery. Moreover, a polyethylene film can be used as the packaging material, and a needle felt or a hard board can be used as the cushioning material. There are various other forms, but the present invention is not limited to this method as long as it is stable and can be transported without being damaged.

<Roughening of the aluminum plate with unevenness transferred>
The aluminum plate to which the unevenness has been transferred is then roughened (alkali etching treatment, desmutting treatment, electrochemical roughening treatment, anodizing treatment, hydrophilization treatment, sealing treatment treatment), and coated with a photosensitive layer. Thus, an aluminum support for a lithographic printing plate is produced.

A preferred roughening embodiment is as follows.
1) Surface roughening embodiment 1
Aluminum plates in order
(1) Chemically etched
(2) Electrochemical roughening treatment in an aqueous solution mainly composed of nitric acid.
(3) Chemically etched
(4) Electrochemical roughening treatment in an aqueous solution mainly composed of hydrochloric acid.
(5) Chemically etched
(6) A method of anodizing.

2) Surface roughening embodiment 2
Aluminum plates in order
(1) Chemically etched
(2) Electrochemical roughening treatment in an aqueous solution mainly composed of nitric acid.
(3) Chemically etched
(4) A method of anodizing.

3) Surface roughening embodiment 3
Aluminum plates in order
(1) Chemically etched
(2) Electrochemical roughening treatment in an aqueous solution mainly composed of hydrochloric acid.
(3) Chemically etched
(4) A method of anodizing.

4) Roughening embodiment 4
Aluminum plates in order
(1) Chemically etched
(2) Electrochemical roughening treatment in an aqueous solution mainly composed of hydrochloric acid.
(3) Chemically etched
(4) Electrochemical roughening treatment in an aqueous solution mainly composed of nitric acid.
(5) Chemically etched
(6) A method of anodizing.

5) Roughening embodiment 5
Aluminum plates in order
(1) Chemically etched
(2) Electrochemical roughening treatment in an aqueous solution mainly composed of hydrochloric acid.
(3) Chemically etched
(4) Electrochemical roughening treatment in an aqueous solution mainly composed of hydrochloric acid.
(5) Chemically etched
(6) A method of anodizing.

It is more preferable to perform a hydrophilic treatment, a sealing treatment, a hydrophilic treatment and a sealing treatment after the anodizing treatment, and it is particularly preferable to perform a sealing treatment or a sealing treatment and a hydrophilic treatment.
After the chemical etching treatment, desmut treatment is preferably performed in an acidic aqueous solution.

<Mechanical roughening>
In the manufacturing method of this invention, it does not need to perform the mechanical surface roughening process using the rotating brush and abrasive | polishing agent which are demonstrated below to the aluminum plate which has an uneven | corrugated pattern on the above-mentioned surface.
When a mechanical surface roughening process using a brush and an abrasive is performed, the surface area can be increased by the subsequent brush grain process even when the surface area is small due to the concavo-convex pattern formed by transfer, and appropriate water retention can be achieved. it can. On the other hand, when the conventional method is performed only with a brush and an abrasive, the problem that sharp irregularities are formed, the remaining film tends to remain, and the stain easily remains at the edge can be solved. Further, the amount of subsequent alkali etching can be reduced, which is advantageous in terms of cost.

Hereinafter, the brush grain method used suitably as a mechanical roughening process is demonstrated.
The brush grain method generally uses a roller-shaped brush in which a large number of brush hairs such as synthetic resin hair made of synthetic resin such as nylon (trade name), propylene, and vinyl chloride resin are implanted on the surface of a cylindrical body. This is carried out by rubbing one or both of the surfaces of the aluminum plate while spraying a slurry liquid containing an abrasive on a rotating roller brush. Instead of the roller brush and the slurry liquid, a polishing roller which is a roller having a polishing layer on the surface can be used.

When a roller brush is used, the flexural modulus is preferably 10,000 to 40,000 kg / cm ² , more preferably 15,000 to 35,000 kg / cm ² , and the bristle strength is preferably Brush hair that is 500 g or less, more preferably 400 g or less is used. The diameter of the brush bristles is generally 0.2 to 0.9 mm. The length of the brush bristles can be appropriately determined according to the outer diameter of the roller brush and the diameter of the body, but is generally 10 to 100 mm.
It is preferable to use a plurality of nylon brushes, specifically, 3 or more are more preferable, and 4 or more are particularly preferable. By adjusting the number of brushes, the wavelength component of the recess formed on the aluminum plate surface can be adjusted.

  The load of the drive motor that rotates the brush is preferably 1 kW plus or more, more preferably 2 kW plus or more, and particularly preferably 8 kW plus or more with respect to the load before the brush roller is pressed against the aluminum plate. By adjusting the load, the depth of the recess formed on the surface of the aluminum plate can be adjusted. The number of rotations of the brush is preferably 100 or more, and particularly preferably 200 or more.

A well-known thing can be used for an abrasive | polishing agent. For example, abrasives such as pumice stone (pumice stone), silica sand, aluminum hydroxide, alumina powder, silicon carbide, silicon nitride, volcanic ash, carborundum, and gold sand; a mixture thereof can be used. Of these, pumiston and silica sand are preferable. Quartz sand is harder and less fragile than Pamiston, so it has excellent roughening efficiency. In addition, aluminum hydroxide is suitable when an excessive load is applied and the particles are damaged, so that it is not desired to generate deep recesses locally.
The median diameter of the abrasive is preferably 2 to 100 μm, and more preferably 20 to 60 μm, from the viewpoints of excellent surface roughening efficiency and narrowing the graining pitch. By adjusting the median diameter of the abrasive, the depth of the recess formed on the surface of the aluminum plate can be adjusted.

For example, the abrasive is suspended in water and used as a slurry. In addition to the abrasive, the slurry liquid may contain a thickener, a dispersant (for example, a surfactant), a preservative, and the like. The specific gravity of the slurry liquid is preferably 0.5-2.
As an apparatus suitable for the mechanical surface roughening treatment, for example, an apparatus described in Japanese Patent Publication No. 50-40047 can be given.

  As for details of an apparatus for performing a mechanical surface roughening process using a brush and an abrasive, those described in JP-A-2002-2111159 can be used by the applicant of the present application.

  In the present invention, when an aluminum plate having a concavo-convex pattern formed on the surface by transfer is further mechanically roughened using a rotating brush and an abrasive, the amount of increase in Ra is 0.3 or less. It is preferable that it is 0.2 or less and 0.1 or less.

<Surface treatment>
In the method for producing a lithographic printing plate support of the present invention, a roughening treatment and an anodic oxidation treatment (in the present invention, both are referred to as a surface treatment) are performed on the above-described aluminum plate having a concavo-convex pattern formed thereon. To obtain a lithographic printing plate support.
The roughening treatment is preferably performed according to the roughening embodiments 1 to 5, for example, etching treatment in an alkaline aqueous solution (first), desmutting treatment in an acidic aqueous solution (first), nitric acid or Electrochemical roughening treatment in aqueous solution containing hydrochloric acid, etching treatment in alkaline aqueous solution (second), desmut treatment in acidic aqueous solution (second), electrochemical in aqueous solution containing hydrochloric acid A roughening treatment, an etching treatment in an alkaline aqueous solution (third), a desmut treatment in an acidic aqueous solution (third), and an anodizing treatment are exemplified.
In the method for producing a lithographic printing plate support of the present invention, various steps other than those described above may be included.

It is also preferable to perform a hydrophilic treatment after the anodizing treatment.
Hereinafter, each step of the surface treatment will be described in detail.

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

The first alkaline etching treatment performed before the first electrolytic treatment is to form a uniform recess in the first electrolytic treatment, and to remove rolling oil, dirt, natural oxide film, etc. on the surface of the aluminum plate (rolled aluminum). This is done for the purpose of removal.
In the first alkali etching treatment, the etching amount is preferably 0.1 g / m ² or more, more preferably 0.5 g / m ² or more, and further preferably 1 g / m ² or more. Further, it is preferably 10 g / m ² or less, more preferably 8 g / m ² or less, and further preferably 5 g / m ² or less. When the lower limit of the etching amount is within the above range, uniform pits can be generated in the first electrolytic treatment, and further, processing unevenness can be prevented. When the upper limit of the etching amount is in the above range, the amount of the alkaline aqueous solution used is reduced, which is economically advantageous.

  Examples of the alkali used in the alkaline 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 alkali etching treatment, the concentration of the alkaline solution is preferably 30 g / L or more, more preferably 300 g / L or more, and preferably 500 g / L or less, 450 g / L. The following is more preferable.
The alkaline solution preferably contains aluminum ions. The aluminum ion concentration is preferably 1 g / L or more, more preferably 50 g / L or more, and preferably 200 g / L or less, more preferably 150 g / L or less. Such an alkaline solution can be prepared using, for example, water, a 48 mass% sodium hydroxide aqueous solution, and sodium aluminate.

In the first alkali etching treatment, the temperature of the alkaline solution is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, and preferably 80 ° C. or lower, and 75 ° C. or lower. Is more preferable.
In the first alkali etching treatment, the treatment time is preferably 1 second or longer, more preferably 2 seconds or longer, more preferably 30 seconds or shorter, and more preferably 15 seconds or shorter. preferable.

When the aluminum plate is continuously etched, the aluminum ion concentration in the alkaline solution increases and the etching amount of the aluminum plate varies. Therefore, the composition management of the etching solution is preferably performed as follows.
That is, a matrix of conductivity, specific gravity, and temperature, or a matrix of conductivity, ultrasonic propagation velocity, and temperature corresponding to the matrix of caustic soda concentration and aluminum ion concentration is prepared in advance, and the conductivity and specific gravity are prepared. The liquid composition is measured according to the temperature and temperature, or the electrical conductivity, the ultrasonic wave propagation speed, and the temperature, and caustic soda and water are added so that the control target value of the liquid composition is reached. Then, the amount of the etching solution increased by adding caustic soda and water is overflowed from the circulation tank, thereby keeping the amount of the solution constant. As caustic soda to be added, 40 to 60% by mass for industrial use can be used.
As the conductivity meter and the specific gravity meter, it is preferable to use those that are temperature-compensated. As the hydrometer, it is preferable to use a differential pressure type.

  Examples of the method of bringing the aluminum plate into contact with the alkaline solution include, for example, a method in which the aluminum plate is passed through a tank containing the alkaline solution, a method in which the aluminum plate is immersed in a tank containing the alkaline solution, The method of spraying on the surface of a board is mentioned.

  Among these, a method in which an alkali solution is sprayed on the surface of an 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-falling 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 fall curtain-like liquid film from 104 to the aluminum plate 1.
In the apparatus 100, water 102 is supplied from a water supply pipe 106 to a water supply tank 104, and when the water 102 overflows from the water supply tank 104, the water is rectified by a 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 Japanese Patent Application Laid-Open No. 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 alkali etching treatment, pickling (first desmutting treatment) is preferably performed in order to remove dirt (smut) remaining on the surface. The desmut treatment is performed by bringing an aluminum plate into contact with an acidic solution.

Examples of the acid used include nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, and borohydrofluoric acid.
In the first desmut process performed after the first alkali etching process, when nitric acid electrolysis is subsequently performed as the first electrolysis process, it is preferable to use the overflow waste liquid of the electrolyte used for nitric acid electrolysis.

  In the composition management of the desmut treatment liquid, as in the case of the alkali etching treatment, the method is managed by the conductivity and temperature corresponding to the matrix of the acidic solution concentration and the aluminum ion concentration, and is managed by the conductivity, specific gravity and temperature. And a method of managing the electric conductivity, the ultrasonic wave propagation speed, and the temperature can be selected and used.

  In the first desmutting treatment, it is preferable to use an acidic solution containing 1 to 400 g / L of acid and 0.1 to 5 g / L of aluminum ions.

  The temperature of the acidic solution is preferably 20 ° C. or more, more preferably 30 ° C. or more, and preferably 70 ° C. or less, more preferably 60 ° C. or less.

  In the first desmutting treatment, the treatment time is preferably 1 second or longer, more preferably 4 seconds or longer, and preferably 60 seconds or shorter, more preferably 40 seconds or shorter. .

Examples of the method of bringing the aluminum plate into contact with the acidic solution include, for example, a method of passing the aluminum plate through a bath containing the acidic solution, a method of immersing the aluminum plate in a bath containing the acidic solution, and an acidic solution containing 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 of spraying an etching solution in an amount of 10 to 100 L / min per spray tube from a spray tube having holes of φ2 to 5 mm 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.
In the first desmutting process, when using the overflow waste liquid of the electrolyte used in the subsequent nitric acid electrolysis as the desmutting process, the surface of the aluminum plate is not subjected to the draining and washing with a nip roller after the desmutting process. It is preferable to handle the aluminum plate up to the nitric acid electrolysis step while spraying a desmut treatment solution as necessary so that it does not dry.

<First electrolytic treatment>
The first electrolytic treatment is an electrochemical surface roughening treatment in an aqueous solution containing nitric acid or hydrochloric acid, which is first performed.
When the first electrolytic treatment and the second electrolytic treatment are carried out as shown in the roughened embodiments 1, 4 and 5, it is possible to form a grain shape with a highly uniform uneven structure on the surface of the aluminum plate. Further, the stain resistance and the printing durability can be made excellent.
In addition, it is preferable that the average roughness of the aluminum plate surface after a 1st electrolytic process is 0.45-0.85 micrometer.
In roughening embodiments 2 and 3, electrolytic roughening using nitric acid or hydrochloric acid is performed. In the roughening embodiment 4, nitric acid electrolysis is performed after hydrochloric acid electrolysis, and in the roughening embodiment 5, hydrochloric acid electrolysis is performed twice. In the following, the roughened embodiment 1 will be mainly described, but in other embodiments, the respective conditions can be changed according to the characteristics of the embodiments.

(Electrochemical roughening treatment in aqueous solution containing nitric acid)
A suitable uneven structure can be formed on the surface of the aluminum plate by electrochemical surface roughening treatment (nitric acid electrolysis) in an aqueous solution containing nitric acid. In the present invention, when the aluminum plate contains a relatively large amount of Cu, a relatively large and uniform recess is formed in nitric acid electrolysis. As a result, the lithographic printing plate using the lithographic printing plate support obtained by the present invention has excellent printing durability.

An aqueous solution containing nitric acid can be used for an ordinary electrochemical surface roughening treatment using direct current or alternating current, and an aqueous solution of nitric acid having a concentration of 1 to 100 g / L, aluminum nitrate, sodium nitrate, ammonium nitrate, etc. At least one of the nitrate compounds having the nitrate ion can be added and used in the range from 1 g / L to saturation. Moreover, the metal contained in aluminum alloys, such as iron, copper, manganese, nickel, titanium, magnesium, a silica, may melt | dissolve in the aqueous solution containing nitric acid. Hypochlorous acid or hydrogen peroxide may be added at 1 to 100 g / L.
Specifically, a solution prepared by dissolving aluminum nitrate in an aqueous nitric acid solution having a nitric acid concentration of 5 to 15 g / L and adjusting the aluminum ion concentration to 3 to 7 g / L is preferable.

  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 of the aqueous solution containing nitric acid is preferably 30 ° C or higher, and preferably 55 ° C or lower.

Pits having an average opening diameter of 1 to 10 μm can be formed by nitric acid electrolysis. However, when the amount of electricity is relatively large, the electrolytic reaction is concentrated, and honeycomb pits exceeding 10 μm are also generated.
To obtain such a grain, the total amount of electricity furnished to anode reaction on the aluminum plate up until the electrolysis reaction is completed is preferably at 150C / dm ² or more, at 170C / dm ² or more more preferably, but preferably not 600C / dm ² or less, more preferably 500C / dm ² or less. The current density at this time is preferably from 20 to 100 A / dm ² at the peak value of the current in the case of using the alternating current, preferably in the case of using a DC is 20 to 100 A / dm ^2.

When the following pre-electrolysis is performed before nitric acid electrolysis, a more uniform recess is formed in nitric acid electrolysis.
Pre-electrolysis is a process of forming the starting point of pit formation during nitric acid electrolysis. By performing slight electrolysis using hydrochloric acid that is hardly affected by the material of the aluminum plate and has very high corrosive properties, pits can be formed uniformly on the surface.
In the pre-electrolysis, the hydrochloric acid concentration is preferably 1 to 15 g / L, and the amount of electricity at the time of anode is preferably 30 to 70 C / m ² .
After pre-electrolysis, it is preferable to perform alkali etching to remove smut. The amount of aluminum dissolved in the alkali etching is preferably 0.2 to 0.6 g / m ² .

(Electrochemical roughening treatment in aqueous solution containing hydrochloric acid)
As the aqueous solution containing hydrochloric acid, those used for electrochemical surface roughening treatment using ordinary direct current or alternating current can be used. One or more of hydrochloric acid or nitric acid compounds having nitrate ions such as sodium nitrate and ammonium nitrate and hydrochloric acid ions such as aluminum chloride, sodium chloride and ammonium chloride can be added to 1 g / L to saturation. Moreover, the compound which forms the above-mentioned copper and a complex can also be added in the ratio of 1-200 g / L. In the aqueous solution containing hydrochloric acid, a metal contained in an aluminum alloy such as iron, copper, manganese, nickel, titanium, magnesium, or silica may be dissolved. Hypochlorous acid or hydrogen peroxide may be added at 1 to 100 g / L.

The aqueous hydrochloric acid is preferably 2 to 10 g / L of hydrochloric acid, and an aluminum salt (aluminum chloride, AlCl ₃ .6H ₂ O) is added at a rate of 27 to 63 g / L to the aqueous solution containing hydrochloric acid to adjust the aluminum ion concentration to 3 to 3. Particularly preferred is an aqueous solution of 7 g / L, preferably 4 to 6 / L. When an electrochemical surface roughening treatment is performed using such an aqueous hydrochloric acid solution, the surface shape by the surface roughening treatment becomes uniform, and a low purity aluminum rolled plate or a high purity aluminum rolled plate can be used. Further, the processing unevenness due to the roughening treatment does not occur, and it is possible to achieve both excellent printing durability and stain resistance when a lithographic printing plate is used.

  The temperature of the aqueous solution containing hydrochloric acid is preferably 25 ° C. or higher, more preferably 30 ° C. or higher, more preferably 55 ° C. or lower, and even more preferably 40 ° C. or lower.

  As the additive, apparatus, power source, current density, flow rate, and temperature in the aqueous solution containing hydrochloric acid, those used for known electrochemical surface roughening can be used. AC or DC is used as the power source used for electrochemical roughening, but AC is particularly preferable.

Since hydrochloric acid has a strong aluminum dissolving power, it is possible to form fine irregularities on the surface with only slight electrolysis. The fine irregularities have an average opening diameter of 0.01 to 0.4 μm and are uniformly generated on the entire surface of the aluminum plate.
Further, as the amount of electricity is increased, pits having an average opening diameter of 1 to 15 μm having pits having an average opening diameter of 0.01 to 0.4 μm on the surface are generated. 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 10 C / dm ² or more, and more preferably 50 C / dm ² or more. Is more preferable, and more preferably 100 C / dm ² or more. But preferably not more 2000C / dm ² or less, more preferably 600C / dm ² or less.

In the first hydrochloric acid electrolysis, it is possible to simultaneously form a large crater-like swell by increasing the total amount of electricity involved in the anodic reaction to 150 to 2000 C / dm ² . Even in this case, pits with an average opening diameter of 1 to 15 μm having fine irregularities with an average opening diameter of 0.01 to 0.4 μm on the surface are generated. The current density at this time is preferably ²⁰ to 100 A / dm ² at the peak value of the current.

  When hydrochloric acid is electrolyzed on an aluminum plate with a large amount of electricity as described above, large waviness and fine irregularities can be formed at the same time, and the large waviness is made more uniform by the second alkali etching process described later, thereby improving stain resistance. Can be made.

  The first electrolytic treatment using an aqueous solution containing nitric acid or hydrochloric acid follows, for example, the electrochemical grain method (electrolytic grain method) described in Japanese Patent Publication No. 48-28123 and British Patent No. 896,563. be able to. 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-52-133638, 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.

When the aluminum plate is continuously subjected to electrolytic surface roughening, the aluminum ion concentration in the alkaline solution increases, and the uneven shape of the aluminum plate formed by the first electrolytic treatment varies. Therefore, the composition management of the nitric acid electrolytic solution or hydrochloric acid electrolytic solution is preferably performed as follows.
That is, a matrix of conductivity, specific gravity, and temperature, or a matrix of conductivity, ultrasonic propagation velocity, and temperature corresponding to a matrix of nitric acid concentration or hydrochloric acid concentration and aluminum ion concentration is prepared in advance. The liquid composition is measured by the degree, specific gravity, and temperature, or the electrical conductivity, the ultrasonic wave propagation speed, and the temperature, and nitric acid or hydrochloric acid and water are added so as to obtain a control target value of the liquid composition. Then, the amount of the electrolyte increased by adding nitric acid or hydrochloric acid and water is overflowed from the circulation tank, and the amount of the electrolyte is kept constant. As nitric acid to be added, 30 to 70% by mass of industrial grade can be used. As hydrochloric acid to add, the industrial thing of 30-40 mass% can be used.
As the conductivity meter and the specific gravity meter, it is preferable to use those that are temperature-compensated. As the hydrometer, it is preferable to use a differential pressure type.
Samples taken from the electrolyte for use in measurement of the liquid composition are used for measurement after being controlled at a constant temperature (for example, 40 ± 0.5 ° C.) using a heat exchanger different from the electrolyte. However, it is preferable in that the accuracy of measurement is increased.

The AC power supply wave used for the electrochemical surface roughening treatment is not particularly limited, and a sine wave (sine wave), a rectangular wave, a trapezoidal wave, a triangular wave or the like is used, and a sine wave, a rectangular wave or a trapezoidal wave is preferable. A trapezoidal wave is particularly preferred. In the case of the first hydrochloric acid electrolysis, a sine wave is particularly preferable in that pits having an average diameter of 1 μm or more are easily generated. The sine wave refers to that shown in FIG.
A trapezoidal wave means what was shown in FIG. In this trapezoidal wave, the time (TP) until the current reaches a peak from zero is preferably 0.5 to 3 msec. When TP exceeds 3 msec, especially when an aqueous solution containing nitric acid is used, it becomes susceptible to the influence of trace components in the electrolytic solution typified by ammonium ions and the like that spontaneously increase by electrolytic treatment, and uniform graining. Is difficult to be performed. As a result, the stain resistance tends to decrease when a lithographic printing plate is obtained.

A duty ratio of alternating current (ta / T, ratio of anode reaction time in one cycle) can be 1: 2 to 2: 1. However, as described in JP-A-5-195300 In the indirect power feeding method in which no conductor roll is used for aluminum, a duty ratio of 1: 1 is preferable.
An AC frequency of 0.1 to 120 Hz can be used, but 50 to 70 Hz is preferable in terms of equipment. When the frequency is lower than 50 Hz, the carbon electrode of the main electrode is easily dissolved, and when the frequency is higher than 70 Hz, it is easily affected by an inductance component on the power supply circuit, and the power supply cost is increased.

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. On the aluminum plate facing the main electrode, the ratio of the amount of electricity involved in the anodic reaction and the cathodic reaction (the amount of electricity at the time of cathode / the amount of electricity at the time of anode) is preferably 0.3 to 0.95.

  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.

  In addition, in the electrochemical surface roughening treatment using direct current, an electrolytic solution used for the electrochemical surface roughening treatment using normal direct current can be used. Specifically, the same electrolyte solution used for the electrochemical surface roughening treatment using the alternating current can be used.

The DC power source wave used for the electrochemical surface roughening treatment is not particularly limited as long as the current does not change in polarity, and a comb wave, continuous DC, commercial AC that is full-wave rectified with a thyristor, etc. can be used. Smoothed continuous direct current is preferred.
The electrochemical surface roughening treatment using direct current can be performed by any of a batch method, a semi-continuous method, and a continuous method, but is preferably performed by a continuous method.

The apparatus used for the electrochemical surface roughening treatment using direct current applies a direct current voltage between anodes and cathodes arranged alternately, and passes through the aluminum plate at a distance from the anode and the cathode. If it can be made, it will not be specifically limited.
For example, the apparatus which has one electrolytic cell shown by FIG. 6 is mentioned. In FIG. 6, the aluminum plate 61 passes through an electrolytic tank 65 filled with an electrolytic solution 64. A DC voltage is applied between the anodes 62 and the cathodes 63 arranged alternately in the electrolytic cell 65. In the electrolytic bath 65, the electrolytic solution 64 is supplied from the liquid supply nozzle 66 and discharged through the drainage pipe 67.
Moreover, the apparatus whose tank of the anode 62 shown in FIG. 7 and the tank of the cathode 63 are separate electrolytic cells is also mentioned. In FIG. 7, the aluminum plate 61 passes through a plurality of electrolytic cells 65 filled with the electrolytic solution 64. In each electrolytic cell 65, anodes 62 or cathodes 63 are alternately arranged. A DC voltage is applied between the anodes 62 and the cathodes 63 arranged alternately. In each electrolytic tank 65, the electrolytic solution 64 is supplied from the liquid supply pipe 68 and is discharged through the drainage pipe 67.

An electrode is not specifically limited, The conventionally well-known electrode used for an electrochemical roughening process can be used.
As the anode, for example, a valve metal such as titanium, tantalum, or niobium is plated or clad with a platinum group metal; the valve metal is coated with an oxide of a platinum group metal or sintered. Aluminium; stainless steel. Among these, a valve metal obtained by cladding platinum is preferable. The life of the anode can be further extended by a method such as water-cooling by passing water through the electrode.
As the cathode, for example, a metal that does not dissolve when the electrode potential is negative can be selected and used from the Boolean Bay diagram. Among these, carbon is preferable.

  The arrangement of the electrodes can be appropriately selected according to the wave structure. Also, by changing the length of the aluminum plate between the anode and the cathode in the traveling direction, changing the passage speed of the aluminum plate, returning the flow rate of the electrolyte, liquid temperature, liquid composition, current density, etc. Can be adjusted. In addition, as in the apparatus shown in FIG. 7, when the anode tank and the cathode tank are separate electrolytic cells, the electrolysis conditions of each treatment tank can be changed.

In the measurement of the average opening diameter of the recesses generated by the first electrolytic treatment, for example, the surface of the support was photographed at a magnification of 2000 times or 50000 times from directly above using an electron microscope. Extracting at least 50 pits each having a ring shape around the pits generated in step (b), reading the diameters to obtain the opening diameter, and calculating the average opening diameter.
In addition, in order to suppress variation in measurement, it is possible to perform equivalent circle diameter measurement using commercially available image analysis software. In this case, the electron micrograph is captured by a scanner, digitized, and binarized by software, and then an equivalent circle diameter is obtained.
As a result of measurement by the present inventor, the result of visual measurement and the result of digital processing showed almost the same value.

After the first electrolytic 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 alkali etching treatment>
The second alkaline etching process performed between the first electrolytic process and the second electrolytic process involves dissolving the smut generated by the first electrolytic process and removing the edge portion of the pit formed by the first electrolytic process. It is performed for the purpose of dissolving. As a result, the edge part of the large pit formed by the first electrolytic treatment solution is melted and the surface becomes smooth, and it is difficult to catch the ink on the edge part. Can do.
Since the second alkali etching process is basically the same as the first alkali etching process, only different points will be described below.

In the second alkali etching treatment, the etching amount is preferably at 0.05 g / m ² or more, more preferably 0.1 g / m ² or more, and it is at 4g / m ² or less Preferably, it is 3.5 g / m ² or less. When the etching amount is 0.05 g / m ² or more, in the non-image portion of the lithographic printing plate, the edge portion of the pit generated by the first electrolytic treatment becomes smooth and the ink is not easily caught, so that the stain resistance is excellent. . On the other hand, when the etching amount is 4 g / m ² or less, the unevenness generated by the first electrolytic treatment becomes large, so that the printing durability is excellent.

In the second alkali etching treatment, the concentration of the alkaline solution is preferably 30 g / L or more, more preferably 300 g / L or more, and preferably 500 g / L or less, 450 g / L. The following is more preferable.
The alkaline solution preferably contains aluminum ions. The aluminum ion concentration is preferably 1 g / L or more, more preferably 50 g / L or more, and preferably 200 g / L or less, more preferably 150 g / L or less.

<Second desmut treatment>
After performing the second alkali etching treatment, it is preferable to perform pickling (second desmut treatment) 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.

In the second desmut treatment, nitric acid or sulfuric acid is preferably used.
In the second desmutting treatment, it is preferable to use an acidic solution containing 1 to 400 g / L of acid and 0.1 to 8 g / L of aluminum ions.
When using sulfuric acid, specifically, use a solution prepared by dissolving aluminum sulfate in an aqueous sulfuric acid solution having a sulfuric acid concentration of 100 to 350 g / L so that the aluminum ion concentration is 0.1 to 5 g / L. Can do. Moreover, the overflow waste liquid of the electrolyte solution used for the anodizing process mentioned later can also be used.
In the second desmut treatment, the treatment time is preferably 1 second or more, more preferably 4 seconds or more, and preferably 60 seconds or less, more preferably 20 seconds or less. .
In the second desmut treatment, the temperature of the acid aqueous solution is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, and preferably 70 ° C. or lower, preferably 60 ° C. or lower. More preferred.

<Second electrolytic treatment>
For example, in the roughening embodiments 1 and 5, the second electrolytic treatment is an electrochemical roughening treatment using alternating current or direct current in an aqueous solution containing hydrochloric acid. In the present invention, by combining the first electrolytic treatment described above and the second electrolytic treatment, a complicated uneven structure can be formed on the surface of the aluminum plate, and as a result, the printing durability is excellent. can do. Moreover, a 2nd electrolysis process produces | generates a recessed part with an average diameter of 0.01-0.4 micrometer on the aluminum surface smoothed by the 2nd alkali etching. Thereby, printing durability can be improved.

The second hydrochloric acid electrolysis performed after the first electrolytic treatment is basically the same as described in the first hydrochloric acid electrolysis.
The total amount of electricity that the aluminum plate participates in the anodic reaction by electrochemical surface roughening in an aqueous solution containing hydrochloric acid in the second hydrochloric acid electrolysis is 10 to 10 when the electrochemical surface roughening treatment is completed. can be selected from the range of 200C / dm ^2, preferably ^{10~100C / dm 2, 50~80C / dm} 2 are particularly preferred.

  When the first hydrochloric acid electrolysis is performed as the first electrolysis treatment, the total amount of electricity Q1 involved in the anodic reaction at the time when the electrolysis reaction in the first hydrochloric acid electrolysis is completed, and the electrolysis reaction in the second hydrochloric acid electrolysis is completed. It is preferable that the quantity of electricity Q2 involved in the anodic reaction at the time is larger than the sum total (Q1> Q2). As a result, the surface area of the aluminum plate is increased by the pits having an average opening diameter of 1 to 15 μm generated by the first hydrochloric acid electrolysis, and the adhesiveness with the image recording layer provided thereon is improved and the printing durability is excellent.

<Third alkali etching treatment>
The third alkali etching treatment performed after the second electrolytic treatment is performed for the purpose of dissolving the smut generated by the second electrolytic treatment and dissolving the edge portion of the pit formed by the second electrolytic treatment. Is called. Since the third alkali etching process is basically the same as the first alkali etching process, only different points will be described below.

In the third alkali etching treatment, the etching amount is preferably at 0.05 g / m ² or more, more preferably 0.1 g / m ² or more, is 0.3 g / m ² or less Of 0.25 g / m ² or less is more preferable. When the etching amount is 0.05 g / m ² or more, in the non-image portion of the lithographic printing plate, the edge portion of the pit generated by the second hydrochloric acid electrolysis becomes smooth and the ink is not easily caught, so that the stain resistance is excellent. . On the other hand, when the etching amount is 0.3 g / m ² or less, the unevenness generated by the first hydrochloric acid electrolysis and the second hydrochloric acid electrolysis becomes large, so that the printing durability is excellent.

In the third alkali etching treatment, the concentration of the alkaline solution is preferably 30 g / L or more, and in order not to make the unevenness generated by the hydrochloric acid alternating current electrolysis in the previous stage too small, the concentration is 100 g / L or less. It is preferable that it is 70 g / L or less.
The alkaline solution preferably contains aluminum ions. The aluminum ion concentration is preferably 1 g / L or more, more preferably 3 g / L or more, preferably 50 g / L or less, more preferably 8 g / L or less. Such an alkaline solution can be prepared using, for example, water, a 48 mass% sodium hydroxide aqueous solution, and sodium aluminate.

In the third alkali etching treatment, the temperature of the alkali solution is preferably 25 ° C or higher, more preferably 30 ° C or higher, and preferably 60 ° C or lower, and 50 ° C or lower. Is more preferable.
In the third alkali etching treatment, the treatment time is preferably 1 second or longer, more preferably 2 seconds or longer, more preferably 30 seconds or shorter, and more preferably 10 seconds or shorter. preferable.

<Third desmut treatment>
After the third alkali etching treatment, it is preferable to perform pickling (third desmut treatment) in order to remove dirt (smut) remaining on the surface. Since the third desmut process is basically the same as the first desmut process, only the differences will be described below.
In the third desmutting process, the same type of liquid as that used in the subsequent anodizing process (for example, sulfuric acid) is used, which eliminates the water washing step between the third desmutting process and the anodizing process. It is preferable in that it can be performed.
In the third desmutting treatment, it is preferable to use an acidic solution containing 5 to 400 g / L acid and 0.5 to 8 g / L aluminum ions. When sulfuric acid is used, specifically, a solution prepared by dissolving aluminum sulfate in a sulfuric acid aqueous solution having a sulfuric acid concentration of 100 to 350 g / L to adjust the aluminum ion concentration to 1 to 5 g / L is preferable.
In the third desmut treatment, the treatment time is preferably 1 second or longer, more preferably 4 seconds or longer, more preferably 60 seconds or shorter, and more preferably 15 seconds or shorter. .
In the third desmut process, when the same type of liquid as the electrolyte used in the subsequent anodizing process is used as the desmut process liquid, the draining with a nip roller and the water washing process can be omitted after the desmut process.

<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 anodized film can be formed by energizing an aluminum plate as an anode. 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. ˜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 the anodizing treatment, so that current is concentrated on a part of the aluminum plate and so-called “burning” (part where the film becomes thicker than the surroundings) does not occur. 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 such 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 treatment is continuously performed, it is preferable that the anodizing process is performed by a liquid power feeding method in which power is supplied to the aluminum plate through an electrolytic solution.
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 . If it is less than 1 g / m ² , the plate is likely to be scratched. On the other hand, if it exceeds 5 g / m ² , a large amount of electric power is required for production, which is economically disadvantageous. 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.

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 continuously 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 on 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 an electrode divided into a plurality of pieces in the traveling direction of the aluminum plate 416 in order to make it easy for hydrogen gas generated by the anode reaction to escape 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 after the anodizing treatment, it is possible to obtain a lithographic printing plate precursor having a higher developability (sensitivity).

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 particularly preferable that the porous coating is subjected to a sealing treatment with a high sealing rate. The sealing rate is 50% or more, more preferably 70% or more, and more preferably 90% or more. Here, the sealing rate (%) is defined by the following formula.
Sealing rate = 100 × (surface area of unsealed hole−surface area after sealing) ÷ (surface area of unsealed hole)
The surface area is a value measured using QUANTASORB (Kantasorb, manufactured by Yuasa Ionics Co., Ltd.) which is a simple BET method.
The anodized aluminum plate is then subjected to a sealing treatment and a hydrophilization treatment to provide a more preferable aluminum support for a lithographic printing plate.

  Sealing treatment includes hot water treatment, boiling water treatment, steam treatment, dichromate treatment, nitrite treatment, ammonium acetate salt treatment, electrodeposition sealing treatment, sodium silicate treatment, nitrite treatment, ammonium acetate treatment It can carry out according to well-known methods, such as. A fluorinated zirconic acid treatment as disclosed in Japanese Patent Publication No. 36-22063 can also be used. Sealing treatment may be carried out by the apparatus and method described in JP-B-56-12518, JP-A-4-4194, JP-A-5-20296, JP-A-5-179482, and the like. Or the method of processing with the aqueous solution containing the phosphate and inorganic fluorine compound which are indicated by Unexamined-Japanese-Patent No. 9-244227 can be used. Moreover, the method of processing with the aqueous solution containing the saccharide | sugar disclosed by Unexamined-Japanese-Patent No. 9-134002 can also be used. In addition, the method of processing with the aqueous solution containing titanium and fluorine described in Japanese Patent Application Nos. 10-252078 and 10-253411 can be used. Moreover, you may perform the process using an alkali metal silicate, In that case, the method currently disclosed by US Patent 3,181,461 etc. can be used. It can carry out using well-known methods, such as.

  In the alkali metal silicate treatment, 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 is used. Sealing treatment can be performed by appropriately selecting treatment conditions such as temperature and treatment time. Suitable alkali metal silicates include sodium silicate, potassium silicate, lithium silicate and the like. Further, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like can be blended in order to adjust the pH of the alkali metal silicate aqueous solution to a high level.

  Furthermore, you may mix | blend an alkaline-earth metal salt or a group IVB metal salt with alkali metal silicate aqueous solution as needed. The alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, and barium nitrate, and sulfates, hydrochlorides, phosphates, acetates, oxalates, and boric acids of these alkaline earth metals. Water-soluble salts such as salts can be mentioned. Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, potassium titanium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride, and the like. be able to. The alkaline earth metal salt or Group IVB metal salt can be used alone or in combination of two or more. A preferable use amount range of these metal salts is 0.01 to 10% by mass, and a more preferable range is 0.05 to 5.0% by mass.

The sealing treatment is preferably performed using a fluorinated zirconate such as sodium fluorinated zirconate or potassium fluorinated zirconate, and more preferably using an aqueous solution containing sodium fluorinated zirconate. By using fluorinated zirconate, an aluminum support for a printing plate having excellent developability (sensitivity) during exposure and development can be obtained. The preferable density | concentration at that time is 0.01-2 mass%, and 0.05-0.5 mass% is more preferable.
More preferably, sodium dihydrogen phosphate is added to the aqueous solution of the fluorinated zirconate. The preferable density | concentration at that time is 0.01-3 mass%, and 0.05-2 mass% is especially preferable.
The preferable temperature of the sealing treatment is preferably 20 to 80 ° C, more preferably 30 to 50 ° C.
A preferable treatment time (immersion time in an aqueous solution) of the sealing treatment is preferably 1 to 20 seconds, and more preferably 5 to 15 seconds.

  In addition, if necessary, after sealing treatment, treatment with an aqueous alkali silicate solution such as sodium silicate, polymer or copolymer having polyvinylphosphonic acid, polyacrylic acid or sulfonic acid group in the side chain, or JP-A-11-231509 (A) A treatment of immersing in a solution containing an amino group and (b) an organic compound having a group selected from a phosphine group, a phosphone group and a phosphate group, or a salt thereof, or undercoating the solution Surface treatment such as treatment can be performed.

  The hydrophilic binder polymer used in the hydrophilic layer of the present invention is a synthetic homopolymer or copolymer such as polyvinyl alcohol, poly (meth) acrylic acid, poly (meth) acrylamide, poly (meth) acrylic acid hydroxyethyl, polyvinyl. Methyl ether or natural polymers such as gelatin, polysaccharides such as dextran, pullulan, cellulose, gum arabic, alginic acid.

<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 fluorinated zirconate 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 subbing 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 Phosphate-modified starch, diamine compounds described in JP-A-63-056498, amino acid inorganic or organic acids described in JP-A-63-130391, JP-A-63-145092 Organic phosphonic acids containing carboxy group or hydroxy group, compounds having amino group and 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, and 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, a sulfo group-containing vinyl polymerizable compound 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 more, more preferably 2 seconds or more, preferably 20 seconds or less, and more preferably 15 seconds.

<Management of liquid composition>
In the present invention, it is preferable to manage the composition of various processing solutions used for the surface treatment described above by the method described in JP-A-2001-121837. Prepare a large number of treatment liquid samples of various concentrations in advance, measure the ultrasonic wave propagation speed at each of the two liquid temperatures, create a matrix-like data table, It is preferable to measure the propagation speed of the light in real time and control the concentration based on the measurement. In particular, in the desmutting treatment, when an electrolytic solution having a sulfuric acid concentration of 250 g / L or more is used, it is preferable to control the concentration by the method described above.
In addition, it is preferable that each electrolyte solution used for an electrolytic roughening process and an anodic oxidation process is 100 ppm or less of Cu concentration. If the Cu concentration is too high, Cu is deposited on the aluminum plate when the line is stopped, and Cu deposited when the line is operated again may be transferred to a pass roll, which may cause processing unevenness.
It is more preferable to perform a known hydrophilic treatment after the sealing treatment.

[Lithographic printing plate precursor]
The lithographic printing plate support obtained by the present invention can be provided with an image recording layer to form the lithographic printing plate precursor of the present invention. A photosensitive composition is used for the image 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”), negative photosensitive composition containing diazo resin or photocrosslinking resin (hereinafter also referred to as “conventional negative type”), and positive photosensitive composition containing 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”). As the referred to as "non-treatment type".), And the like. Hereinafter, these suitable photosensitive compositions will be described.

<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, the polymer compound described in JP-A No. 2001-305722 (particularly [0023] to [0042]), and the 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 may contain a dissolution inhibitor. As the dissolution inhibitor, for example, dissolution inhibitors described in JP-A-2001-305722, [0053] to [0055] are 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 in Japanese Patent Application Laid-Open No. 2001-305722 is also preferably used in other respects.

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 in 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 JP-A-2002-3233769, [0062] to [0085] 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 light-to-heat 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].
Preferred 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 radical 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. Preferred 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.

  In the thermal negative photosensitive composition, an additive described in JP-A-2001-133969, [0061] to [0068] (for example, a surfactant for improving coatability) is contained. 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 cross-linking layer comprises a photothermal conversion substance, a thermal acid generator, a compound that cross-links with an acid that is a curable compound (cross-linking agent), and an alkali-soluble polymer compound that can react with the cross-linking agent in the presence of an acid. contains. In the acid cross-linking layer, infrared light absorbed by the photothermal conversion substance is converted into heat, the heat 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 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-type photosensitive composition contains a diazo resin or a photocrosslinking resin. Among them, preferred is a photosensitive composition containing a diazo resin and an alkali-soluble or swellable polymer compound (binder).
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. Organic solvent-soluble diazo resin inorganic salts which are reaction products 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 coating properties.

  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 converted into a lithographic printing plate by various treatment methods according to the image recording layer.
Examples of the actinic ray 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 any of thermal positive type, thermal negative type, conventional negative type, conventional positive type, and photopolymer type, after exposure, it is 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. Production of rolls (Example 1)
The following processing was performed using a roll in which tool steel (SKD11) was quenched to make Hv750.
(1) Buffing treatment A buffing treatment was performed to remove traces of the grindstone that polished the roll surface. The surface roughness Ra was 0.2 μm, and Rmax was 1 μm.
(2) Degreasing treatment of roll It was immersed in a degreasing tank having a liquid temperature of 30 ° C. for 30 seconds, and the oil on the surface was removed with a degreasing solution. Thereafter, it was washed with water and air was blown to remove moisture.

(3) Electrolytic treatment using the roll as an anode in the electrolytic solution In a electrolytic solution having a temperature of 50 ° C. containing 300 g / L of chromic acid, 2 g / L of sulfuric acid, and 1 g / L of iron, a continuous direct current is applied to An electrolytic treatment was performed using a roll as an anode at a current density of 30 A / dm ² as an anode. The current waveform used was a three-phase full-wave rectified direct current with a ripple component of 5% or less through a filter circuit. The amount of electricity was changed as shown in Table 1, and rolls of Examples 1-1, 1-2, and 1-2 were produced. The counter electrode was lead. The roll was placed vertically in the electrolytic solution, and a lead electrode was arranged in a cylindrical shape so as to surround the periphery. The roll shaft was masked with vinyl chloride so as not to be electrolyzed.
(4) Hard chrome plating treatment Next, a continuous DC current is applied in an electrolytic solution containing chromic acid 300 g / L, sulfuric acid 2 g / L, and iron 1 g / L, and the temperature is 50 ° C. It was subjected to a plating treatment at 60A / dm ^2. The current waveform used for plating was a three-phase full-wave rectification and a direct current with a ripple component of 5% or less through a filter circuit. The plating treatment time was set so that the plating thickness was 6 μm for all rolls. The counter electrode was lead. The roll was placed vertically in the electrolytic solution, and a lead electrode was arranged in a cylindrical shape so as to surround the periphery. The shaft portion of the roll was masked with vinyl chloride so as not to be plated.

When the roll surface profile was observed by the replica method, the heights of the convex portions on the roll surface were uniform and good.
2. Evaluation of Roll Cross-Section Profile Cross-sectional profile data of the roll obtained in Example 1-2 and the roll obtained in Comparative Example 2 described later are shown in FIGS. The measurement used the Ryoka System Co., Ltd. micromap 520, measured the unevenness | corrugation located in the cross section of the longitudinal direction of the roll of Example 1-2, and described it on the chart.

(Example 2)
The aluminum plate having the composition shown in Table 2 was rolled using the roll of Example 1-2, and irregularities were imparted to the aluminum plate surface.

The thickness of this aluminum plate was 0.3 mm, and Ra was 0.65 μm, Rmax 5.7 μm, Sm 70 μm, and Δa 7.5 degrees.
In the measurement of Examples and Comparative Examples, two-dimensional roughness measurement is performed with a stylus type roughness meter (SUFCOM 575, manufactured by Tokyo Seimitsu Co., Ltd.), and arithmetic average roughness Ra specified in ISO 4287 is measured five times. The average value is defined as the average roughness. The maximum height Rmax (Ry) for the reference length, the average interval of irregularities (average value in the reference length) Sm, and the average slope gradient Δa were also measured in the same manner.
<Measurement conditions>
Cut-off value 0.8 mm, tilt correction FLAT-ML, measurement length 3 mm, vertical magnification 10000 times, scanning speed 0.3 mm / sec, stylus tip diameter 2 μm.

3. Preparation of lithographic printing plate support <Surface treatment>
<1> Etching Treatment in Alkaline Aqueous Solution An aluminum plate was etched by spraying an aluminum plate with 370 g / L of NaOH, 100 g / L of aluminum ions and 60 ° C. aqueous solution containing it from a spray tube. The amount of dissolution of the aluminum plate on the surface to be electrochemically roughened in the subsequent step was 3 g / m ² .
Thereafter, the liquid was drained with a nip roller, washed with water, and further drained with a nip roller.
In this water washing treatment, water washing was performed using an apparatus for washing with a free-fall curtain liquid film, and then water washing treatment was performed for 5 seconds with water blown out in a fan shape from a spray tip attached to the spray tube.

<2> Desmutting in acidic aqueous solution Next, desmutting was performed.
The waste liquid of nitric acid used for electrochemical roughening in the next step was used. The liquid temperature was 35 ° C. The desmutting solution was sprayed and sprayed for 5 seconds.
Thereafter, the nip roller was not used to drain the liquid, and the aluminum plate was handled with the nitric acid attached until the next step. After passing through the desmut treatment tank, the handling time in a state where nitric acid was adhered was 25 seconds.

<3> Electrochemical roughening treatment in nitric acid aqueous solution Electrolysis in which aluminum nitrate was added to an aqueous solution having a liquid temperature of 35 ° C. and a nitric acid concentration of 10.4 g / L to adjust the aluminum ion concentration to 4.5 g / L The liquid was used.
Immediately before the electrochemical surface roughening treatment, an electrolytic solution having the same composition and temperature as the nitric acid electrolytic solution used for the electrochemical surface roughening treatment was sprayed onto the aluminum plate.
An electrochemical surface roughening treatment was performed using a power source that generates an alternating current. The frequency of the alternating current was 60 Hz, and the time Tp from the current zero to the peak was 1.2 msec. The duty cycle (ta / T) of alternating current was 0.5.
The current density at the time of the alternating current peak was 60 A / dm ² during the anode reaction of the aluminum plate. The ratio of the total amount of electricity during the anode reaction of the aluminum plate to the total amount of electricity during the cathode reaction was 0.95. The amount of electricity applied to the aluminum plate was 215 C / dm ^{2 as} the total amount of electricity during the anode reaction of the aluminum plate.
Two electrolytic treatment tanks of the radial type shown in FIG. 3 were used.
The relative speed of the aluminum plate and the electrolytic solution was 1.5 m / sec (1-2 m / sec) on average in the electrolytic cell.
Then, the liquid was drained with a nip roller, washed with water, and then washed with water sprayed out in a fan shape from a spray tip attached to the spray tube for 5 seconds. Further, the liquid was removed with a nip roller.

<4> Etching treatment in alkaline aqueous solution An aluminum plate was etched for 7 seconds by spraying an aqueous solution containing NaOH of 370 g / L and aluminum ions of 100 g / L at a temperature of 64 ° C. from a spray tube, and the aluminum plate was etched. . The amount of dissolution of the aluminum plate on the surface to be electrochemically roughened in the subsequent step was 3 g / m ² .
Thereafter, the liquid was drained with a nip roller, washed with water, and further drained with a nip roller.
In this water washing treatment, water washing was performed using an apparatus for washing with a free-fall curtain liquid film, and then water washing treatment was performed for 5 seconds with water blown out in a fan shape from a spray tip attached to the spray tube. Further, the liquid was removed with a nip roller.

<5> Desmutting in acidic aqueous solution Next, desmutting was performed.
Desmutting was performed for 10 seconds at a liquid temperature of 35 ° C. using aluminum ion 2 g / L dissolved in 300 g / L sulfuric acid aqueous solution.
Then, the liquid was drained with a nip roller, and then washed with water for 5 seconds with water blown out in a fan shape from a spray tip attached to the spray tube. Further, the liquid was removed with a nip roller.

<6> Electrochemical roughening treatment in hydrochloric acid aqueous solution Use an electrolytic solution in which aluminum chloride is adjusted to 5 g / L by adding aluminum chloride to an aqueous solution with a liquid temperature of 35 ° C and hydrochloric acid concentration of 5 g / L. It was.
Electrochemical roughening treatment was performed using a power source that generates trapezoidal alternating current. The frequency of the alternating current was 60 Hz, and the time Tp until reaching the peak from zero of the alternating current was 0.8. The duty (ta / T) of alternating current was 0.5.
The current density was 50 A / dm ² during the anode reaction of the aluminum plate at the peak of alternating current, and the ratio of the total amount of electricity during the anode reaction and the total amount of electricity during the cathode reaction of the aluminum plate was 0.95. The amount of electricity applied to the aluminum plate was 65 C / dm ^{2 as} the total amount of electricity during the anode reaction of the aluminum plate.
As the electrolytic treatment tank, one radial type tank shown in FIG. 3 was used.
The relative speed of the aluminum plate and the electrolytic solution was 1.5 m / sec on average in the electrolytic cell.
Thereafter, the liquid was drained with a nip roller, washed with water, and further drained with a nip roller.

<7> Etching treatment in alkaline aqueous solution An aluminum plate is dissolved in an aqueous solution containing NaOH 50 g / L and aluminum ions 5 g / L, and 35 ° C. is sprayed from a spray tube to dissolve the aluminum plate 0.2 g / m ^2. Went.
Thereafter, the liquid was drained with a nip roller, washed with water, and further drained with a nip roller.
In this water washing treatment, water washing was performed using an apparatus for washing with a free-fall curtain liquid film, and then water washing treatment was performed for 5 seconds with water blown out in a fan shape from a spray tip attached to the spray tube. Further, the liquid was removed with a nip roller.

<8> Desmutting treatment in acidic aqueous solution Next, desmutting treatment was performed. As the acidic aqueous solution used for the desmutting treatment, the desmutting treatment was performed at a liquid temperature of 35 ° C. for 5 seconds using the waste liquid generated in the next anodizing treatment step (dissolving 5 g / L of aluminum ions in 170 g / L aqueous solution of sulfuric acid).
Then, the liquid was drained with a nip roller. No water washing treatment was performed until the anodization after draining with the nip roller.

<9> Anodizing treatment Next, this plate was anodized under the following conditions.
Aluminum sulfate was added to 170 g / L of sulfuric acid to adjust the aluminum ion concentration to 5 g / L, and the current density applied to the aluminum plate in the electrolytic treatment tank using the electrolytic solution, 33 ° C. A direct current anodic oxide coating of 2.4 g / m ² was provided under the condition that the average current density was 15 A / dm ² .

<10> Hydrophilization treatment Hydrophilic treatment was performed by immersing in an aqueous solution containing 2.5% sodium silicate at 20 ° C. for 10 seconds. The amount of Si on the surface of the aluminum plate measured with a fluorescent X-ray analyzer was 3.5 mg / m ² . Thereafter, the liquid was drained with a nip roller, washed with water, and further drained with a nip roller.
Then, 90 degreeC wind was blown for 10 seconds and it dried.

  When the surface shape of the aluminum plate was observed with a scanning electron microscope at a magnification of 50000 times, fine irregularities having a diameter of 0.1 μm were uniformly and densely formed on the surface. Further, when observed with a scanning electron microscope at a magnification of 2000, irregularities having a diameter of 1 to 5 μm were formed on the surface of the aluminum plate. The fine irregularities having a diameter of 0.1 μm were generated by being superimposed on the irregularities having a diameter of 1 to 5 μm.

4). Preparation of a lithographic printing plate precursor A thermal positive type image recording layer was applied and dried on each of the lithographic printing plate supports obtained as described above to prepare and print a lithographic printing plate precursor. Before providing the image recording layer, an undercoat layer was provided as described later.
The obtained lithographic printing plate was a good printing plate excellent in sensitivity, number of printed sheets (printing durability), resistance to stains and resistance to entanglement.

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

Furthermore, a heat-sensitive layer coating solution having the following composition was prepared, and the coating amount after drying the heat-sensitive layer coating solution (heat-sensitive layer coating amount) on a lithographic printing plate support provided with an undercoat layer was 1.8 g / m. ² was applied 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 (Defenser F-780F, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30% by mass) 0.0045 g (solid content conversion)
・ Fluorosurfactant (Defenser F-781F, manufactured by Dainippon Ink & Chemicals, Inc., solid content: 100% by mass) 0.035 g
・ Methyl ethyl ketone 12g

(Example 3)
After the anodizing treatment of <9> described in Example 2, the seal is immersed for 10 seconds in a liquid containing 1% by mass of sodium dihydrogen phosphate and 0.1% by mass of sodium zirconate fluoride at a liquid temperature of 40 ° C. Hole processing was performed. The liquid was drained with a nip roll, then washed with water, and further drained with a nip roll.
Thereafter, <10> hydrophilization treatment described in Example 2 was performed. Then, 90 degreeC wind was blown for 10 seconds and it dried.
The same photosensitive layer as in Example 2 was applied to this aluminum plate and dried to prepare and print a lithographic printing plate precursor. A lithographic printing plate having good printing performance showing the number of printed sheets (printing durability), stain resistance and entanglement similar to that of Example 2, but having developability (sensitivity) prepared in Example 2. It was better than the original plate.

Example 4
Except that the rolls of Example 1-1 and Example 1-3 were used, the aluminum plate was provided with irregularities in the same manner as in Example 2, and then the surface was roughened and the photosensitive layer was applied. Was produced and printed. This printing plate was a good planographic printing plate showing the same printing performance as in Example 2.

(Example 5)
A rolling roll was prepared in the same manner as in Example 1-2 except that the buffing treatment in Example 1 was not performed, and thereafter, using this roll, irregularities were imparted to the aluminum plate in the same manner as in Example 2, and further continued. A roughening treatment was performed, a photosensitive layer was applied, and a lithographic printing original plate was prepared. This original plate was exposed and developed for printing as a printing plate. Although this printing plate was a printing plate showing good printing performance showing resistance to dirt and entanglement similar to Example 2, the developability and the number of printed sheets were inferior to those of Example 2.

(Comparative Example 1)
By air blasting using # 128 mesh alumina as a grid material, the grid is projected twice to roughen the surface, Ra is 1.7 μm, and then the surface is repolished to Ra of 1.3 μm. Thereafter, as in the example, the aluminum plate was provided with irregularities using a rolling roll which was hard-chrome plated to a thickness of 6 μm. Ra of the aluminum plate was 1.2 μm, Rmax 15 μm, Sm 90 μm, and Δa 8 deg.
Further, a surface roughening treatment was performed in the same manner as in Example 2, a photosensitive layer was applied, and a lithographic printing original plate was produced. This original plate was exposed and developed in the same manner as in Example 2 and printed as a printing plate.
This printing plate was a printing plate showing good printing performance showing the same resistance to dirt and entanglement as in Example 2, but the developability and the number of printed sheets were inferior to those in Example 2.

4). Evaluation of planographic printing plate precursor The printing durability and stain resistance of the planographic printing plate were evaluated by the following methods.
(1) Printing durability (number of printed sheets)
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 alkali 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 B 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 40,000 or more. ○: The number of printed sheets is 30,000 or more and less than 40,000. △: The number of printed sheets is 20,000 or more and less than 30,000. ×: The number of printed sheets is less than 20,000.

(2) Sensitivity Using a TrendSetter 3244 manufactured by CREO equipped with a semiconductor laser having an output of 500 mW, a wavelength of 830 nm, a beam diameter of 17 μm (1 / e ² ), and a lithographic printing plate precursor, a main scanning speed of 5 m / sec and a plate surface energy amount of 140 mJ / cm Imagewise exposure at ² . To evaluate the sensitivity, were prepared samples was exposed by changing the plate surface energy amount to 45~180mJ / cm ² to 5mJ / cm ² every other.
The development processing was performed using an automatic processor PS900NP (Fuji Photo Film Co., Ltd.) filled with the developer B having the following composition under conditions of a development temperature of 25 ° C. and 12 seconds. After completion of the development treatment, a lithographic printing plate in which plate making was completed was obtained through a water washing step and treatment with a gum (GU-7 (1: 1)). Sensitivity was defined as the minimum exposure amount at which an image could be formed after development processing from a sample in which the plate surface energy amount was changed.
The results are shown in Table 1. In Table 2, the evaluation was as follows.
◎: weight Energy (mJ / cm ^2), it is less than 50mJ / cm ² ○: less than the amount of energy ^{100mJ / cm 2, 50mJ / cm} 2 or more △: energy 150 mJ / cm less than ^2, 100mJ / cm ² or more ×: The amount of energy 150mJ / cm ² or more

(3) Dirt resistance (resistance to dirt)
Using the planographic printing plate obtained in the same manner as in the above (1) Evaluation of printing durability, printing was performed with DIC-GEOS (s) red ink on a Mitsubishi diamond F2 printer (manufactured by Mitsubishi Heavy Industries). The dirt on the blanket after printing 10,000 sheets was visually evaluated.
The results are shown in Table 2. In Table 2, the evaluation was as follows.
A: The blanket is hardly dirty B: The blanket is slightly dirty BC: The blanket is dirty but within an acceptable range C: The blanket is dirty and the printed matter is clearly dirty

(4) Difficult to see Depending on the type of ink, when the amount of dampening water is reduced, the ink adheres to the shadow part (halftone dot part having a high image area ratio), that is, to the non-image part (hereinafter, referred to as “ink”). This phenomenon is called “ink entanglement”, and the difficulty of this phenomenon is called “entanglement difficulty”). The lithographic printing plate obtained in the same manner as in the above (1) evaluation of printing durability was used with a DIC-GEOS (H) ink manufactured by Dainippon Ink & Chemicals, Inc. on a SOR-M printing machine manufactured by Heidelberg. By reducing the amount of fountain solution, the entanglement of the ink in the mesh portion was evaluated in three stages. The results are shown in Table 3.
A is excellent in difficulty in entanglement of ink. AB is slightly entangled in ink. B indicates that entanglement in ink was observed.

It is typical sectional drawing of the apparatus which performs a water washing process with the free-fall curtain-like liquid film used for the water washing process in the manufacturing method of the support body for lithographic printing plates of this invention. It is a graph which shows an example of the alternating waveform current waveform figure used for the electrochemical roughening process in the manufacturing method of the support body for lithographic printing plates of this 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 graph which shows an example of the sine waveform figure used for the electrochemical roughening process in the manufacturing method of the support body for lithographic printing plates of this invention. It is a side view which shows an example of the apparatus used for the electrochemical roughening process using the direct current | flow in the manufacturing method of the support body for lithographic printing plates of this invention. It is a side view which shows another example of the apparatus used for the electrochemical roughening process using the direct current | flow in the manufacturing method of the support body for lithographic printing plates of this invention. It is the cross-sectional profile data of the roll obtained in Example 1-2. It is a cross-sectional profile data of the roll obtained in Comparative Example 1.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Aluminum plate 11 Aluminum plate 12 Radial drum roller 13a, 13b Main electrode 14 Electrolytic process liquid 15 Electrolyte supply port 16 Slit 17 Electrolyte passage 18 Auxiliary anode 19a, 19b Thyristor 20 AC power supply 40 Main electrolytic cell 50 Auxiliary anode tank 61 Aluminum Plate 62 Anode 63 Cathode 64 Electrolyte 65 Electrolysis tank 66 Supply nozzle 67 Drain pipe 68 Supply pipe 100 Apparatus for washing with free falling curtain-like liquid film 102 Water 104 Water storage tank 106 Water supply cylinder 108 Rectification part 410 Anodizing Processing device 412 Power supply tank 413 Intermediate tank 414 Anodizing treatment 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 nozzle 440 Shielding 442 drainage ports

Claims (5)

  An aluminum plate embossing roll having a rough surface obtained by electrolytic treatment in an electrolytic solution using the roll as an anode on a steel roll surface, and further having a chromium plating layer thereon.   The aluminum plate embossing roll according to claim 1, wherein the steel roll surface is mirror-polished in advance.   The roll for embossing of an aluminum plate according to claim 1 or 2, wherein the surface of the roll after the electrolytic treatment has a rough surface having an average surface roughness Ra of 0.5 to 2 µm and Sm of 10 to 200 µm.   The aluminum plate embossing according to any one of claims 1 to 3, wherein an average surface roughness Ra of a steel roll surface before being subjected to electrolytic treatment as an anode in the electrolytic solution is 0.01 to 0.3 µm. Rolls.   A method for producing an aluminum support for a lithographic printing plate comprising a step of transferring irregularities on the surface of an aluminum plate with the aluminum plate embossing roll.

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