JP5715900B2 - Method and apparatus for producing aluminum support for lithographic printing plate - Google Patents

Method and apparatus for producing aluminum support for lithographic printing plate Download PDF

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JP5715900B2
JP5715900B2 JP2011159091A JP2011159091A JP5715900B2 JP 5715900 B2 JP5715900 B2 JP 5715900B2 JP 2011159091 A JP2011159091 A JP 2011159091A JP 2011159091 A JP2011159091 A JP 2011159091A JP 5715900 B2 JP5715900 B2 JP 5715900B2
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aluminum
surface
method
power supply
treatment
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JP2012067382A (en
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雄一 糟谷
雄一 糟谷
堀田 久
久 堀田
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富士フイルム株式会社
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  The present invention relates to a method and an apparatus for producing an aluminum support for a lithographic printing plate, and in particular, the surface of a strip-shaped aluminum web is roughened and washed with water, and further, the feeding roller and the electrolyte solution are opposed to the aluminum web. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for producing an aluminum support for a lithographic printing plate in which the surface of an aluminum web is subjected to electrolytic treatment by energization through an electrode disposed at a position, and particularly to an aluminum support for a lithographic printing plate to be anodized The present invention relates to a manufacturing method and a manufacturing apparatus.

  Conventionally, a support for a lithographic printing plate used for a photosensitive lithographic printing plate is required to have excellent hydrophilicity, water retention, and adhesion to a photosensitive layer in terms of printability. An aluminum plate that has been subjected to a roughening treatment called sharpening is used. Examples of such surface roughening treatment include mechanical surface roughening methods such as various polishing treatments, and electrochemical surface roughening methods in which the support surface is electrolytically treated in an acidic electrolyte such as hydrochloric acid or nitric acid. It has been known.

  An aluminum plate grained by such a method is inferior in printability, printing durability (abrasion resistance), and storage stability as it is, and is further subjected to an anodizing treatment to form an anodized film on the surface. As anodizing treatment, sulfuric acid, phosphoric acid, oxalic acid, chromic acid and the like have been widely known, and an electrolytic solution in which these acids are used alone or in combination is used.

  In this anodizing treatment, the aluminum plate was passed straight through in the longitudinal direction, and the current was passed through the feed roller in the longitudinal direction of the aluminum plate. At the same time, the anodizing treatment was disposed at a position facing the aluminum plate in the electrolyte. The electrode is energized to electrolytically treat the surface of the aluminum plate.

  However, in the method of supplying power via the electrolytic solution, the voltage loss in the electrolytic solution is large and the power cost is increased. In addition, in the method of supplying power with the power supply roll, sparks are generated at the entrance and exit of the aluminum plate to the power supply roller when the aluminum plate contacts and leaves the power supply roller, and the aluminum plate fails. It was.

  Therefore, in Patent Document 1, it is proposed to use a power supply roller including a power supply brush capable of selecting a power supply position in a method of supplying power with a power supply roll. Patent Document 2 proposes an electrolytic processing apparatus in which the center line average roughness of the surface of the power supply roller is set to about 0.1 to 0.8 μm in a method of supplying power with a power supply roll.

JP 7-34299 A JP 7-62599 A

  However, the apparatus of the cited document 1 has a problem that roll durability is low and cost is high because it is a special power supply roller. Further, in the apparatus of Cited Document 2, the aluminum plate is damaged due to the occurrence of a spark due to the flow of a large local current due to the presence of foreign matter or liquid brought in from the previous process between the aluminum plate and the feeding roller. There is a problem.

  The present invention has been made in view of such circumstances, and for lithographic printing plates that can efficiently supply power in anodizing and can prevent sparks from being generated between an aluminum plate and a power supply roller. It aims at providing the manufacturing method and manufacturing apparatus of an aluminum support body.

In order to achieve the above-mentioned object, the present invention roughens the surface of a strip-shaped aluminum web, rinses it with water, and further passes through a feed roller and an electrode disposed at a position facing the electrolyte in the aluminum web. In the method for producing an aluminum support for a lithographic printing plate in which the surface of the aluminum web is anodized by energization, the center line average roughness of the surface of the power supply roller is 0.05 to 1.6 μm, and the power supply the aluminum web surface was washed with water immediately before the roller, and further have a drying step after washing with water, the drying step is conducted roll system, a hot air system, radiation method, infrared drying method, induction heating method, a microwave induction heating method Provided is a method for producing an aluminum support for a lithographic printing plate, which is performed by any of the methods. The present invention can also be applied to electrolytic surface roughening treatment.

In order to achieve the above object, the present invention provides a means for roughening the surface of a strip-shaped aluminum web, a means for washing with water, and a position where the feeding roller and the electrolytic solution are opposed to the aluminum web. And a means for anodizing the surface of the aluminum web by energizing through the formed electrode, and removing water on the surface of the aluminum web immediately before the power supply roller. The means for removing moisture is a means using any one of a conductive roll method, a hot air method, a radiation method, an infrared drying method, an induction heating method, and a microwave induction heating method. An apparatus for producing an aluminum support for a lithographic printing plate is provided. In the present invention, the means for removing moisture (moisture removing means) is not a means for draining excess moisture with a roller, but a means for removing moisture on the aluminum plate by a drying process. . The object of the present invention cannot be achieved by simply draining off excess water.

  The indirect power supply method that supplies power through the electrolyte solution has a large voltage loss in the electrolyte solution and the power cost is large. In the direct power supply method that supplies power from the power supply roller, the insulating foreign material brought from the previous process between the aluminum web and the power supply roller When a liquid or liquid is present, a large local current flows and a spark occurs, causing a failure in the aluminum web.

  Therefore, the present inventor decided to provide means for removing moisture on the surface of the aluminum web immediately before the power supply roller in the direct power supply method in which power is supplied by the power supply roller.

  According to the present invention, since no liquid is interposed between the power supply roller and the aluminum web, no spark is generated. In addition, since a commonly used power supply roller (metal roller) is used instead of the power supply roller as in the cited document 2, it is possible to supply power efficiently with little voltage drop.

  In the present invention, the center line average roughness of the surface of the power supply roller is set to 0.05 to 1.6 μm.

  In Cited Document 2, if the center line average roughness Ra on the surface of the power supply roller is less than 0.1 μm, the aluminum web slips and is damaged. On the other hand, if it is larger than 0.9 μm, the voltage drop is large, and spark is likely to occur between the power supply roller and the aluminum web. Therefore, the center line average roughness of the surface of the power supply roller is preferably 0.1 to 0.8 μm.

  However, in the present invention, since no liquid is interposed between the power supply roller and the aluminum web, no slip occurs even at 0.05 μm. Further, no spark occurs even at 1.6 μm. For this reason, the center line average roughness of the surface of the power supply roller is preferably 0.05 to 1.6 μm.

  In addition, More preferably, it is 0.10-1.0 micrometer, More preferably, it is 0.15-0.5 micrometer. When Ra is smaller than 0.10 μm, the number of polishing processing steps during the production of the power supply roller increases, which is not preferable. Further, when Ra becomes larger than 1.0 μm, the voltage drop amount starts to increase.

  In the present invention, it is preferable that a pressure roller made of an insulating rubber for pressing the aluminum web is provided on the power feeding roller via the aluminum web.

  By making the aluminum web and the power supply roller come into close contact with a pressure roller made of an insulating rubber, sparks are less likely to occur.

  According to the present invention, a method and an apparatus for manufacturing an aluminum support for a lithographic printing plate capable of efficiently supplying power and preventing sparks from being generated between an aluminum plate and a power supply roller in anodizing treatment. Can be provided.

Overall schematic diagram of an aluminum plate electrolytic treatment apparatus according to the present invention Table showing the conditions and results of the examples

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments listed here.

  The aluminum plate electrolytic treatment apparatus according to the present invention will be described in detail below with reference to the accompanying drawings. FIG. 1 is a cross-sectional view of an aluminum plate electrolytic treatment apparatus 10 according to the present invention. The electrolytic processing apparatus 10 for an aluminum plate has an anodizing bath 12, and an electrolytic solution 14 is supplied to the anodizing bath 12. A front roller 16 is rotatably supported in the electrolyte solution 14 on the left side of the anodizing bath 12, and a rear roller 18 is rotatably supported in the electrolyte solution 14 on the right side of the anodizing bath 12. Has been.

  A power supply roller 20 is rotatably supported above the left side of the front roller 16.

  A belt-like aluminum plate (hereinafter referred to as web) 22 is in contact with the upper portion of the power supply roller 20 in a stretched state. The web 22 in contact with the power supply roller 20 is stretched between the lower part of the front roller 16 and the lower part of the rear roller 18. The web 22 stretched between the lower part of the front roller 16 and the lower part of the rear roller 18 is immersed in the electrolytic solution 14 substantially horizontally. In this case, the web 22 is supplied into the electrolytic solution 14 through the power supply roller 20 and the front roller 16, and the web 22 supplied and immersed in the electrolytic solution 14 is pulled up from the electrolytic solution 14 through the rear roller 18. It is done.

  In the electrolytic solution 14 between the front roller 16 and the rear roller 18, an electrode 24 is disposed substantially parallel to the web 22 stretched between the lower portion of the front roller 16 and the lower portion of the rear roller 18. A cathode of a power source 26 is electrically connected to the electrode 24, and an anode of the power source 26 is electrically connected via a power supply brush 28 that contacts the power supply roller 20. Therefore, when the power supply 26 is in the “on” state, a negative voltage is applied to the electrode 24 and a positive voltage is applied to the web 22 via the power supply roller 20. As the electrode 24 that supplies power to the aluminum plate, an electrode formed of aluminum, lead, iridium oxide, platinum, ferrite, carbon, or the like can be used.

  The operation of the electrolytic processing apparatus for an aluminum plate according to the present invention configured as described above will be described. First, the web 22 is supplied into the electrolytic solution 14 through the power supply roller 20 and the front roller 16, and the web 22 stretched between the lower portion of the front roller 16 and the lower portion of the rear roller 18 is immersed in the electrolytic solution 14. To do. Next, the power supply 26 is turned on, and a positive voltage is applied to the web 22 through the power supply roller 20.

  Since a positive voltage is applied to the web 22 through the power supply roller 20 and a negative voltage is applied to the electrode 24, a current flows from the web 22 disposed opposite to the electrode 24 to the electrode 24. The surface of the web 22 is continuously subjected to electrolytic treatment (anodization treatment). The web 22 whose surface has been subjected to electrolytic treatment is pulled up from the electrolytic solution 14 via the rear roller 18.

  By the way, in producing an aluminum support for a lithographic printing plate, generally, before performing the electrolytic treatment with the electrolytic treatment apparatus 10 for the aluminum plate, the aluminum plate is subjected to a roughening treatment, an alkali as a pre-process (pretreatment). Surface treatments such as etching treatment and desmut treatment are performed.

  In addition, the aluminum plate is subjected to surface treatment including at least roughening treatment, anodizing treatment, and specific sealing treatment to obtain an aluminum support for a lithographic printing plate. May be included.

  As the surface treatment, an alkali etching treatment or a desmut treatment is preferably performed before the electrolytic surface roughening treatment, and an alkali etching treatment and a desmut treatment are also preferably performed in this order. Moreover, it is preferable to perform an alkali etching process or a desmut process after an electrolytic roughening process, and it is also preferable to perform an alkali etching process and a desmut process in this order. Further, the alkali etching treatment after the electrolytic surface roughening treatment can be omitted. Moreover, it is also preferable to perform a mechanical surface roughening process before these processes. Moreover, you may perform an electrolytic surface roughening process twice or more. Thereafter, it is also preferable to perform anodizing treatment, sealing treatment, hydrophilization treatment, and the like.

  By such surface treatment, in the anodic oxidation treatment, a large local current flows due to the presence of insulating foreign substances and liquid brought in from the previous process, and a spark occurs, resulting in a failure of the web.

  Therefore, according to the present invention, in the electrolytic processing apparatus 10 for an aluminum plate, a moisture removing means 30 for removing moisture on the surface of the aluminum web is provided immediately before the power supply roller 20. Here, immediately before the power supply roller 20 is after the surface treatment as described above before the anodizing treatment, and the surface treatment as described above is performed between the moisture removing means 30 and the power supply roller 20. It means not.

  In addition, since the surface treatment as described above is performed before the anodic oxidation treatment, it is usually performed to wash the insulating foreign matter or liquid adhering to the aluminum plate with water or the like. However, as shown in FIG. 1, a foreign matter removing means 29 may be provided immediately before the moisture removing means 30. The moisture removing means of the present invention is not a means for draining excess moisture with a roller, but means for removing moisture on the aluminum plate by a drying process. The object of the present invention cannot be achieved by simply draining off excess water. In addition, as shown in FIG. 1, you may have the liquid draining process by the roller 31 in the front stage of the drying process which is the water | moisture-content removal means 30 of this invention.

The foreign matter removing means 29 can use a general method such as a brush method, an underwater immersion method, or a water spray method. A water-washing spray system that is simple to equip and has a foreign matter removing ability is preferred. In this case, it is preferable to use warm water in order to improve detergency and subsequent drying. The temperature is preferably 25 to 80 ° C, more preferably 40 to 80 ° C. Of these, hot air drying is most preferable. The hot air drying can be performed, for example, by applying air at 70 to 180 ° C. with an air volume of 200 to 700 m 2 / min for 1 to 10 seconds. A more preferable temperature is 90 to 140 ° C., an air volume is 300 to 500 m 2 / min, and a more preferable time is 2 to 4 seconds.

  The moisture removing means 30 can use a general method such as a conductive roll method, a hot air method, a radiation method, an infrared drying method, an induction heating method, a microwave induction heating method, etc. A roll method or induction heating method is desirable from the viewpoint of space saving. A hot air system that can simplify the apparatus is also desirable.

  By providing a means for removing moisture on the surface of the aluminum web immediately before the power supply roller as in the present invention, no liquid or foreign matter is interposed between the power supply roller and the aluminum web, so that no spark is generated. In addition, power can be supplied efficiently with little voltage drop.

  In addition, it is preferable that the center line average roughness Ra of the surface of the power supply roller is set to 0.05 to 1.6 μm so that the surface roughness of the power supply roller 20 is not too rough and not too precise. There is a problem that the amount of voltage drop when energizing the aluminum material from the power supply roller when the center line average roughness Ra is too coarse is larger than 1.6 μm, and the current is locally because the amount of voltage drop is large. It is possible to further solve the problem that sparks are generated due to the concentration of heat, and the problem that the amount of heat generation increases due to an increase in the amount of voltage drop and the size of the cooling device increases. Furthermore, the problem that the aluminum material and the power supply roller slip when the center line average roughness Ra of the surface of the power supply roller is too fine with less than 0.05 μm can be solved. In addition, More preferably, it is 0.10-1.0 micrometer, More preferably, it is 0.15-0.5 micrometer. When Ra is smaller than 0.10 μm, the number of polishing processing steps during the production of the power supply roller increases, which is not preferable. Further, when Ra becomes larger than 1.0 μm, the voltage drop amount starts to increase.

  Furthermore, in the present invention, as shown in FIG. 1, it is preferable that a pressure roller 32 made of an insulating rubber that pressurizes the aluminum web is provided on the power supply roller 20 via the aluminum web 22. By making the aluminum web and the power supply roller come into close contact with a pressure roller made of an insulating rubber, sparks are less likely to occur.

  In addition, it is also preferable to cool the aluminum web immediately after the power supply roller 20 with an electrolytic solution spray or the like in order to prevent fusing and save power.

  When two or more stages of anodization are performed, sparks are likely to be generated by the oxide film generated in the first stage. Therefore, it is desirable that the second and subsequent stages be an indirect power feeding method in which power is fed through the electrolytic solution.

  Hereinafter, a method for producing a lithographic printing plate support according to the present invention, and preferred embodiments of the lithographic printing plate support and the lithographic printing plate precursor will be described.

<Aluminum plate (rolled aluminum)>
The aluminum plate used for the lithographic printing plate precursor according to the present embodiment is a metal mainly composed of dimensionally stable aluminum, and is made of 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 on a polyethylene terephthalate film can also be used.

  The composition of the aluminum plate used in the present embodiment is not particularly limited, but it is preferable to use a pure aluminum plate. Since completely pure aluminum is difficult to manufacture in terms of scouring techniques, it may be used that contains slightly different elements. For example, known materials described in Aluminum Handbook 4th Edition (Light Metal Association (1990)), specifically, for example, JIS A1050, JIS A1100, JIS A3003, JIS A3004, JIS A3005, international registered alloy 3103A, etc. These aluminum alloy plates can be used as appropriate. In addition, the aluminum content is 99.4 to 95% by mass, and includes an aluminum alloy, scrap aluminum material, or three or more selected from the group consisting of Fe, Si, Cu, Mg, Mn, Zn, Cr and Ti An aluminum plate using a secondary metal can also be used.

  Further, the aluminum content of the aluminum alloy plate is not particularly limited, but the aluminum content may be 95 to 99.4% by mass, and this aluminum plate is made of Fe, Si, Cu, Mg, Mn, Zn It is preferable to contain three or more different elements selected from the group consisting of Cr and Ti in the following ranges (Fe: 0.20 to 1.0 mass%, Si: 0.10 to 1.0 mass%) Cu: 0.03-1.0 mass%, Mg: 0.1-1.5 mass%, Mn: 0.1-1.5 mass%, Zn: 0.03-0.5 mass%, Cr : 0.005-0.1 mass%, Ti: 0.01-0.5 mass%). This is because aluminum crystal grains become finer.

  The aluminum plate may contain elements such as Bi and Ni and inevitable impurities.

  The production method of the aluminum plate may be either a continuous casting method or a DC casting method, and an aluminum plate that omits DC casting method intermediate annealing or soaking treatment may also be used. In the final rolling, it is possible to use an aluminum plate provided with irregularities by lamination rolling or transfer. The aluminum plate used in the present embodiment may be an aluminum web, which is a continuous strip-shaped sheet material or plate material, and is a sheet-like sheet cut to a size corresponding to a planographic printing plate precursor shipped as a product. It may be a sheet.

  The thickness of the aluminum plate used for this embodiment is about 0.05-1 mm normally, and it is preferable that it is 0.1 mm-0.5 mm. This thickness can be appropriately changed according to the size of the printing press, the size of the printing plate, and the user's desire.

  In the method for producing a lithographic printing plate support in the present embodiment, the aluminum plate is subjected to at least a surface treatment including a roughening treatment, an anodizing treatment, and a specific sealing treatment to support the lithographic printing plate. A body is obtained, but this surface treatment may further include various treatments. In the various steps of this embodiment, since the alloy component of the aluminum plate used in the treatment liquid used in the step is eluted, the treatment solution may contain the alloy component of the aluminum plate. It is preferable to add the alloy components before the treatment and use the treatment liquid in a steady state.

  As the surface treatment, an alkali etching treatment or a desmut treatment is preferably performed before the electrolytic surface roughening treatment, and an alkali etching treatment and a desmut treatment are also preferably performed in this order. Moreover, it is preferable to perform an alkali etching process or a desmut process after an electrolytic roughening process, and it is also preferable to perform an alkali etching process and a desmut process in this order. Further, the alkali etching treatment after the electrolytic surface roughening treatment can be omitted. Moreover, it is also preferable to perform a mechanical surface roughening process before these processes. Moreover, you may perform an electrolytic surface roughening process twice or more. Thereafter, it is also preferable to perform anodizing treatment, sealing treatment, hydrophilization treatment, and the like.

  In the present embodiment, the surface treatment is mechanical roughening treatment, alkali etching treatment, desmutting treatment, electrolytic surface roughening treatment, alkali etching treatment and / or desmutting treatment, anodizing treatment, sealing treatment and / or hydrophilicity. Are preferably included in this order, and this embodiment will be described.

  Hereinafter, mechanical roughening treatment, first alkali etching treatment, first desmutting treatment, electrolytic surface roughening treatment, second alkali etching treatment, second desmutting treatment, anodizing treatment, sealing treatment, and hydrophilic treatment, respectively. Will be described in detail. In the present specification, the process performed before the electrolytic surface-roughening process is referred to with an ordinal number “first”, and the process performed after the electrolytic surface-roughening process is referred to with an ordinal number “second”. There is a case.

<Mechanical roughening>
The mechanical surface roughening treatment is preferably performed before the electrolytic surface roughening treatment. In general, the mechanical surface roughening treatment is a roller-like brush in which a large number of brush bristles such as synthetic resin bristles made of synthetic resin such as nylon (trade name), propylene, and vinyl chloride resin are implanted on the surface of a cylindrical body. Is used 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. The length of the bristle in the roller brush can be appropriately determined according to the outer diameter of the roller brush and the diameter of the trunk, but is generally 10 to 100 mm.

  A well-known thing can be used for the abrasive | polishing agent used for this embodiment. For example, abrasives such as pumicestone, silica sand, aluminum hydroxide, alumina powder, volcanic ash, carborundum, and gold sand can be used, or a mixture thereof. Among them, pumiston and silica sand are preferable, but silica sand is particularly preferable in terms of excellent roughening efficiency because it is harder and less likely to break than pamiston. The average particle diameter of the abrasive is preferably 3 to 50 μm, and more preferably 6 to 45 μm in terms of excellent surface roughening efficiency and a narrow graining pitch. When using pumiston as an abrasive, the average particle size is particularly preferably 40 to 45 μm, and when using silica sand as the abrasive, the average particle size is particularly preferably 20 to 25 μm. For example, the abrasive is suspended in water and used as a polishing slurry. In addition to the abrasive, the polishing slurry liquid can contain a thickener, a dispersant (for example, a surfactant), an antiseptic, and the like. The average particle diameter is the particle diameter at which the cumulative ratio is 50% when the cumulative distribution of the ratio of the abrasive particles of each particle diameter is taken with respect to the volume of the total abrasive contained in the polishing slurry liquid. Say. Further, in the mechanical surface roughening treatment, first, before performing brush graining, a degreasing treatment for removing rolling oil on the surface of the aluminum plate, for example, a surfactant, an organic solvent, an alkaline aqueous solution, if desired. The degreasing process by etc. may be performed.

<First alkali etching treatment>
In the first alkali etching treatment, etching is performed by bringing the aluminum plate into contact with an alkali solution. The first alkali etching treatment is performed for the purpose of removing rolling oil, dirt, and natural oxide film on the surface of the aluminum plate (rolled aluminum) when mechanical roughening treatment is not performed. When the roughening treatment is performed, it is performed for the purpose of obtaining a surface having smooth undulations by dissolving the uneven edge portions generated by the mechanical roughening treatment. Examples of the method of bringing the aluminum plate into contact with an alkaline solution include, for example, a method of passing an aluminum plate into a bath containing an alkaline solution, a method of immersing an aluminum plate in a bath containing an alkaline solution, and an alkaline solution containing aluminum. The method of spraying on the surface of a board is mentioned.

The etching amount is preferably 1 to 15 g / m 2 for the surface subjected to the electrolytic surface roughening treatment in the next step, and 0.1 to 5 g / m for the surface not subjected to the electrolytic surface roughening treatment. 2 (about 10 to 40% of the surface to be subjected to electrolytic surface roughening treatment) is preferable. If the etching amount is in the above range, the rolling oil (oils and fats), dirt, and natural oxide film on the surface of the aluminum plate (rolled aluminum) are completely removed if mechanical roughening treatment is not performed. Therefore, when a planographic printing plate is used, water retention in the non-image area is excellent, and so-called blank stain (blanket stain) caused by ink adhering to the non-image area does not occur. In addition, when the mechanical surface roughening process is performed, the uneven edge portions generated by the mechanical surface roughening process are sufficiently dissolved.

  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 alkali metal salts include alkali metal silicates such as sodium silicate, 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, tribasic sodium phosphate, tertiary 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.

  Although the density | concentration of an alkaline solution can be determined according to the etching amount, it is preferable that it is 1-50 mass%, and it is more preferable that it is 10-35 mass%. When aluminum ions are dissolved in the alkaline solution, the concentration of aluminum ions is preferably 0.01 to 10% by mass, and more preferably 3 to 8% by mass.

The temperature of the alkaline solution is preferably 20 to 90 ° C. The treatment time is preferably 1 to 120 seconds. The amount of the etching treatment is preferably for 1 to 15 g / m 2 dissolution, it is more preferable to 3~12g / m 2 dissolution. The first alkaline etching treatment can be performed using an etching tank that is usually used for etching the aluminum plate. As the etching tank, either a batch type or a continuous type can be used. Moreover, when spraying an alkali solution on the surface of an aluminum plate and performing a 1st alkali etching process, a spray apparatus can be used.

<First desmut treatment>
In the first desmutting treatment, for example, the aluminum plate is brought into contact with an acidic solution (containing aluminum ions of 0.01 to 5% by mass) having a concentration of 0.5 to 30% by mass such as hydrochloric acid, nitric acid, and sulfuric acid. Do. 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 into a bath containing the acidic solution, a method of immersing the aluminum plate in a bath containing the acidic solution, The method of spraying on the surface of a board is mentioned. In the first desmutting treatment, as an acidic solution, an aqueous solution mainly containing nitric acid or an aqueous solution mainly containing hydrochloric acid discharged in an electrolytic surface-roughening treatment described later, or sulfuric acid discharged in an anodic oxidation treatment described later It is preferable to use a waste liquid of an aqueous solution mainly composed of. The liquid temperature of the first desmut treatment is preferably 25 to 90 ° C. Moreover, it is preferable that the processing time of a 1st desmut process is 1-180 second. Aluminum and aluminum alloy components may be dissolved in the acidic solution used for the first desmut treatment.

<Electrolytic roughening treatment>
The electrolytic surface roughening treatment is a treatment for roughening the surface of the aluminum plate by electrolysis using aluminum as an anode in an acidic aqueous solution.

  The acidic aqueous solution used in the present embodiment is not particularly limited, but an aqueous solution mainly containing nitric acid and an aqueous solution mainly containing hydrochloric acid are preferable. The aqueous solution mainly composed of nitric acid preferably has a nitric acid concentration of 5 to 15 g / L, more preferably 7 to 13 g / L, and preferably an aluminum ion concentration of 3 to 15 g / L. 3 to 7 g / L is more preferable. The concentration of aluminum ions in an aqueous solution mainly composed of nitric acid can be adjusted by adding aluminum nitrate to an aqueous nitric acid solution having a nitric acid concentration. The aqueous solution mainly composed of hydrochloric acid preferably has a hydrochloric acid concentration of 5 to 15 g / L, more preferably 5 to 10 g / L, and preferably an aluminum ion concentration of 3 to 15 g / L. 3 to 7 g / L is more preferable. The concentration of aluminum ions in the aqueous solution mainly containing hydrochloric acid can be adjusted by adding aluminum chloride to the aqueous hydrochloric acid solution having the above hydrochloric acid concentration. Further, an aqueous solution mainly composed of nitric acid and an aqueous solution mainly composed of hydrochloric acid can contain ions such as Fe, Si, Cu, Mg, Mn, Zn, Cr, Ti, and inevitable impurities. The liquid temperature of the aqueous solution mainly composed of nitric acid is preferably 30 to 70 ° C, and more preferably 40 to 60 ° C. The liquid temperature of the aqueous solution mainly composed of hydrochloric acid is preferably 25 to 50 ° C, more preferably 30 to 45 ° C.

  Moreover, in this embodiment, you may contain a corrosion inhibitor in electrolyte solution. As the corrosion inhibitor, a passive film-forming corrosion inhibitor, a film-forming corrosion inhibitor, an adsorption-type corrosion inhibitor, a vaporizable corrosion inhibitor, a precipitation-forming corrosion inhibitor, etc. can be used. It is preferred to use a forming type corrosion inhibitor. Moreover, it is preferable that the density | concentration of a corrosion inhibitor is 0.001g / L-100g / L.

  As the electrolytic surface-roughening treatment method, alternating current or direct current is used. In the present invention, it is preferable to use alternating current. The alternating current used for the electrolytic surface roughening treatment is not particularly limited, and for example, a sine wave (sine wave) current, a rectangular wave current, a triangular wave current, or a trapezoidal wave current can be used. Among these, a sine wave current and a trapezoid wave current are preferable. In the present embodiment, alternating current may be any of single phase, two phases, three phases, etc. However, it is preferable to use two or more phases because the surface roughening efficiency is excellent. Also, a current in which alternating current and direct current are superimposed can be used. The AC frequency is not particularly limited, but is preferably 40 to 120 Hz, more preferably 40 to 80 Hz, and still more preferably 50 to 60 Hz.

  Further, the ratio Qc / Qa between the amount of electricity when the aluminum plate becomes the anode, that is, the amount of electricity Qa during the anode, and the amount of electricity when the aluminum plate becomes the cathode, ie, the amount of electricity Qc during the cathode, is 0.9 to 1. If it is, it is preferable because uniform honeycomb pits can be formed on the surface of the aluminum plate, and more preferably 0.95 to 0.99. When the electrolytic surface treatment is performed using an AC electrolytic cell having an auxiliary electrode for diverting the anode current of the main electrode, Qc / Qa is controlled by controlling the current value of the anode current diverted to the auxiliary electrode. Can be controlled.

  The duty of the alternating current is not particularly limited, but is preferably 0.33 to 0.66 from the viewpoint of uniformly roughening the surface of the aluminum plate and manufacturing the power supply device. More preferably, it is -0.6. In the present embodiment, “duty” refers to ta / T, where T is the AC period and ta is the time during which the aluminum plate undergoes an anodic reaction (anode reaction time). On the surface of the aluminum plate, an oxide film mainly composed of aluminum hydroxide may be formed during the cathode reaction, and the oxide film may be dissolved or broken. When the oxide film dissolves or breaks, the portion where the dissolution or breakage occurs becomes the starting point of the pitting reaction during the anode reaction of the next aluminum plate. Therefore, the selection of the AC duty is particularly important in that uniform electrolytic surface roughening is performed.

The time TP until the current value in alternating current reaches a positive or negative peak from zero is preferably 0.5 to 6 msec in the case of a trapezoidal wave current. The amount of electricity from the start to the end of the electrolytic surface roughening treatment is preferably 10 to 1000 C / dm 2 as the total when the aluminum plate is an anode. The peak current Iap on the anode cycle side and the peak current Icp on the cathode cycle side in alternating current are preferably 20 to 100 A / dm 2 , respectively. Icp / Iap is preferably 0.9 to 1.5.

<Second alkali etching treatment>
In the second alkali etching treatment, etching is performed by bringing the aluminum plate into contact with an alkaline solution. Examples of the type of alkali, the method of bringing the aluminum plate into contact with the alkaline solution, and the apparatus used therefor are the same as those in the case of the first alkaline etching treatment. The etching amount is preferably 0.001 to 1 g / m 2 for the surface subjected to the electrolytic surface roughening treatment. Examples of the alkali used in the alkaline solution include the same as in the case of the first alkali etching treatment. The concentration of the alkaline solution can be determined according to the etching amount, but is preferably 0.01 to 80% by mass. The temperature of the alkaline solution is preferably 20 to 90 ° C. The treatment time is preferably 1 to 60 seconds. In the second desmutting process to be described later, when an acidic solution containing 100 g / L or more of sulfuric acid and having a liquid temperature of 60 ° C. or higher is used, the second alkali etching process can be omitted.

<Second desmut treatment>
In the second desmutting treatment, for example, the aluminum plate is contacted with an acidic solution having a concentration of 0.5 to 30% by mass (containing 0.01 to 5% by mass of aluminum ions) such as phosphoric acid, hydrochloric acid, nitric acid, and sulfuric acid. To do. The method for bringing the aluminum plate into contact with the acidic solution may be the same as in the case of the first desmut treatment. In the second desmutting treatment, it is preferable to use a waste solution of a sulfuric acid solution discharged in an anodic oxidation treatment described later as the acidic solution. Further, instead of the waste liquid, a sulfuric acid solution having a sulfuric acid concentration of 100 to 600 g / L, an aluminum ion concentration of 1 to 10 g / L, and a liquid temperature of 60 to 90 ° C. can be used. The liquid temperature of the second desmut treatment is preferably 25 to 90 ° C. Moreover, it is preferable that the processing time of a 2nd desmut process is 1-180 second. Aluminum and aluminum alloy components may be dissolved in the acidic solution used for the second desmut treatment.

<Anodizing treatment>
The aluminum plate treated as described above is preferably further subjected to an anodizing treatment. Hereinafter, the anodizing treatment according to the present invention will be described.

The anodizing treatment is a treatment for forming an anodized film (Al 2 O 3 ) on the surface of an aluminum plate by flowing a direct current, a pulsating flow or an alternating current through the aluminum plate in an electrolyte solution capable of forming an anodized film. It is.

  The electrolyte used in this embodiment is not particularly limited as long as it can form a porous anodic oxide film, but sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfone, and the like. Examples thereof include an aqueous solution or a non-aqueous solution such as an acid or an amidosulfonic acid, or a combination of two or more thereof, and a sulfuric acid solution is particularly preferable.

  The sulfuric acid concentration in the electrolytic solution is preferably 10 to 300 g / L (1 to 30% by mass), and the aluminum ion concentration is 1 to 25 g / L (0.1 to 2.5% by mass). It is preferable that it is 2-10 g / L (0.2-1 mass%). Such an electrolytic solution can be prepared, for example, by adding aluminum to dilute sulfuric acid having a sulfuric acid concentration of 50 to 200 g / L.

  Moreover, in this embodiment, the component normally contained at least in an aluminum plate, an electrode, tap water, groundwater, etc. may be contained in electrolyte solution. Furthermore, the 2nd, 3rd component 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.

  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. In addition, when anodizing is performed in an electrolytic solution containing sulfuric acid, direct current or alternating current is applied to the aluminum plate.

From the viewpoint of printing durability of a lithographic printing plate, the amount of anodized film is preferably 1.0 to 5.0 g / m 2, and more preferably 1.5 to 4.0 g / m 2. Moreover, it is preferable that the difference of the amount of anodic oxide films between the center part and edge vicinity of an aluminum plate is 1 g / m < 2 > or less.

  In the anodic oxide film production step, controlling the flow rate in the tank 12 for producing the anodic oxide film is important for cooling the interface and producing a uniform film. Therefore, the flow rate is preferably adjusted to 1 to 250 cm / sec, more preferably 5 to 100 cm / sec.

  Since control of the temperature of the electrolyte solution 14 or the concentration of sulfuric acid or the like is difficult to perform on-line direct measurement, it is controlled by electric conductivity and specific gravity. In this case, for example, an anodic oxide film can be formed by energizing an aluminum plate as an anode in a solution having a sulfuric acid concentration of 50 to 300 g / l and an aluminum concentration of 5% by weight or less.

  An experiment was conducted using a JIS A1050 aluminum web having a thickness of 0.15 mm and a width of 1000 mm subjected to roughening treatment and chemical dissolution treatment as pretreatment. The amount of power supplied to the power supply roller was 5000A. In addition, 15% sulfuric acid at 40 ° C. was supplied as an electrolytic solution into the anodizing tank.

As shown in the table of FIG. 2, an experiment was conducted on the presence or absence of a water washing step and a drying step in front of the power supply roller. The drying process was carried out by applying 120 ° C. air at a flow rate of 400 m 2 / min for 3 seconds. At this time, the number of sparks generated (pieces / m 2 ), the amount of voltage drop, and the presence or absence of slips were examined. In addition, the comparative example 7 showed the result about the indirect power supply system instead of the electrolytic treatment apparatus (direct power supply system) of the aluminum plate of FIG. 1 for reference.

  As shown in the table of FIG. 2, since there is a drying process for removing the moisture on the surface of the aluminum web immediately before the power supply roller, no liquid or foreign matter is interposed between the power supply roller and the aluminum web, so that no spark is generated. It becomes like this. In addition, power can be supplied efficiently with little voltage drop. In particular, it can be seen that by setting the center line average roughness of the surface of the power supply roller to 0.05 to 1.6 μm, the voltage drop is small and no spark occurs without slipping.

  DESCRIPTION OF SYMBOLS 10 ... Electrolytic treatment apparatus of aluminum material, 12 ... Anodizing tank, 14 ... Electrolyte, 20 ... Feed roller, 22 ... Aluminum material (web), 24 ... Electrode, 28 ... Feed brush, 29 ... Removal means, such as foreign substances, 30 ... Moisture removal means, 31 ... Roller

Claims (5)

  1. The surface of the aluminum web is roughened, washed with water, and then the surface of the aluminum web is anodized by applying current to the aluminum web through a power supply roller and an electrode disposed at an opposite position in the electrolyte. In the method for producing an aluminum support for a lithographic printing plate to be processed,
    The center line average roughness of the surface of the feed roller is 0.05~1.6Myuemu, aluminum web surface was washed with water immediately before the feed roller, and further have a drying step after washing with water,
    The method for producing an aluminum support for a lithographic printing plate , wherein the drying step is performed by any one of a conductive roll method, a hot air method, a radiation method, an infrared drying method, an induction heating method, and a microwave induction heating method. .
  2.   2. The method for producing an aluminum support for a lithographic printing plate according to claim 1, wherein a center line average roughness of a surface of the power supply roller is 0.10 to 1.0 μm.
  3. The means for roughening the surface of the strip-shaped aluminum web, the means for washing with water, and the aluminum web by energizing the aluminum web through a power supply roller and an electrode disposed at an opposite position in the electrolyte. In an apparatus for producing an aluminum support for a lithographic printing plate comprising means for anodizing the surface,
    The center line average roughness of the surface of the power supply roller is 0.05 to 1.6 μm, and the surface of the aluminum web is washed immediately before the power supply roller, and further includes means for removing water after the water washing ,
    The means for removing moisture is a means using any one of a conductive roll method, a hot air method, a radiation method, an infrared drying method, an induction heating method, and a microwave induction heating method . Aluminum support manufacturing equipment.
  4.   The apparatus for producing an aluminum support for a lithographic printing plate according to claim 3, wherein the center line average roughness of the surface of the power supply roller is set to 0.10 to 1.0 µm.
  5.   5. The aluminum support for a lithographic printing plate according to claim 3, wherein a pressure roller made of an insulating rubber for pressing the aluminum web is provided on the power supply roller via the aluminum web. manufacturing device.
JP2011159091A 2010-08-27 2011-07-20 Method and apparatus for producing aluminum support for lithographic printing plate Expired - Fee Related JP5715900B2 (en)

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JPH0635215B2 (en) * 1986-09-04 1994-05-11 富士写真フイルム株式会社 Method of manufacturing a lithographic printing plate support
JP3271336B2 (en) * 1992-11-10 2002-04-02 カシオ計算機株式会社 Anodic oxidation apparatus of the conductive film
JPH06235089A (en) * 1993-02-10 1994-08-23 Fuji Photo Film Co Ltd Anodic oxidation treatment device for base for lithographic printing plate
JPH0762599A (en) * 1993-08-20 1995-03-07 Fuji Photo Film Co Ltd Electrolytic device of conductive plate material
JP4060519B2 (en) * 2000-08-15 2008-03-12 富士フイルム株式会社 Planographic printing plate manufacturing apparatus and manufacturing method
JP2002067521A (en) * 2000-08-28 2002-03-08 Fuji Photo Film Co Ltd Aluminum support for lithographic printing plate and its manufacturing method
JP2003103955A (en) * 2001-09-28 2003-04-09 Fuji Photo Film Co Ltd Manufacturing method for support for lithographic printing plate
JP4410714B2 (en) * 2004-08-13 2010-02-03 富士フイルム株式会社 Method for producing support for lithographic printing plate
JP4019086B2 (en) * 2005-04-07 2007-12-05 株式会社熊防メタル Method for forming surface of aluminum or aluminum alloy to suppress electrification
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