LITHOGRAPHIC PRINT PLATE SUPPORT, LITHOGRAPHIC PRINT PLATE PRECURSOR AND LITHOGRAPHIC PRINT PLATE PR

专利摘要:
support for lithographic printing plate, and method of producing the same, as well as the original lithographic printing plate The object of the present invention is to provide a support for a lithographic printing plate. the backing has excellent scratch resistance and with the backing, an original lithographic printing plate with excellent print durability when used as a lithographic printing plate and excellent press development capability can be obtained. For this lithographic printing plate holder, which is supplied with an aluminum plate and an anodized aluminum film on it, the micropores in the anodized film extend in the depth direction from the surface, which is on the opposite side of the plate. aluminum. The micropores are configured from a large diameter hole section, which extends from the surface of the anodized film to an average depth of 75 to 120 nm (depth (a)), and a small diameter hole section, which extends connects with the bottom of the hole of the large diameter hole section and extends from the connection position to an average depth of 900 to 2000 nm. the average diameter of the anodized film surface of the large diameter hole section is 10 nm but less than 30 nm, and the average diameter and depth (a) satisfy the ratio (depth (a) / average diameter) = greater than 4.0 to 12.0; and the mean diameter at the connection position of the small diameter pore section is greater than 0 and less than 10 nm.
公开号:BR112015001857B1
申请号:R112015001857-2
申请日:2013-07-26
公开日:2021-09-14
发明作者:Yoshiharu Tagawa；Shinya Kurokawa；Atsushi Matsuura；Yuya Miyagawa；Hirokazu Sawada；Atsuo Nishino
申请人:Fujifilm Corporation；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] The present invention relates to a support for lithographic printing plate, and a method of producing a support for lithographic printing plate, as well as a precursor of the lithographic printing plate. PRIORITIES
[002] Lithographic printing is a printing process that uses the inherent immiscibility that exists between water and oil. The lithographic printing plates used in lithography formed on their surfaces regions that are receptive to water and that repel oil-based inks (hereinafter referred to as "non-image areas"), and regions that repel water but are receptive to oil-based inks (hereafter referred to as "image areas").
[003] An aluminum holder used in a lithographic printing plate (referred to below simply as a "lithographic printing plate holder") is used in order to carry non-image areas on its surface. Therefore, it must have a number of conflicting properties, including, on the one hand, excellent hydrophilicity and water retention and, on the other hand, excellent adhesion to an image recording layer that is provided over it. If the hydrophilicity of the support is too low, the ink is likely to be bound in non-image areas at the time of printing, causing a blanket cylinder to be scummed, which therefore leads to formation of the so-called scumming. Also, if the media's water retention is too low, an obstruction is generated in a shaded area, unless the amount of wetting solution is increased at the time of printing. Thus, the so-called availability of water is reduced.
[004] Several studies have been done to obtain a support for lithographic printing plate that exhibits good properties. For example, patent literature 1 discloses a method of producing a support for lithographic printing plate that includes a first step of anodizing a rough surface of the aluminum plate, followed by treatment to widen the pore, and a subsequent step of re-anodizing under conditions such that the micropore diameter may be smaller than in the anodized film formed in the first step. It has been described that a lithographic printing plate obtained using the lithographic printing plate holder has a longer printing life and excellent on-press developability. LIST OF QUOTES PATENTS LITERATURE
[005] Patent Literature 1: JP 2011 - 245844 A SUMMARY OF THE INVENTION TECHNICAL PROBLEMS
[006] Meanwhile, in recent years, with the growth of the performance requirements for the printing technique, there is a great demand for better performance in terms of the various properties (particularly the print life and the developing capacity in the press) of a lithographic printing plate and a lithographic printing plate precursor obtained using a lithographic printing plate holder. In general, print life has a trade-off relationship with press development capability, and it has been difficult to achieve these properties simultaneously.
[007] The inventors of this invention examined various properties of the lithographic printing plate and the lithographic printing plate precursor obtained using the lithographic printing plate holder specifically described in patent literature 1, and it was found that the revealability in press and print life satisfy moderate and conventional performance requirements, but not current performance requirements, which is not necessarily satisfactory in practical use.
[008] In view of the situation as described above, an object of the invention is to provide a support for a lithographic printing plate that has excellent scratch resistance, and that allows a lithographic printing plate formed therefrom to have a longer printing life and being able to achieve a lithographic printing plate precursor with excellent press development capability. Another object of the invention is to provide a method of producing said support for lithographic printing plate. Another object of the invention is to provide a precursor of the lithographic printing plate. SOLVING THE PROBLEMS
[009] The inventors of the present invention made an intensive study to achieve the objectives and, as a result, found that the aforementioned problems can be solved by controlling the shape of the micropores (particularly the shape of a large diameter portion thereof ) on the anodized film.
[0010] Specifically, the invention provides the following from (1) to (9).
[0011] (1) A support for lithographic printing plate, comprising an aluminum plate and an anodized aluminum film, which is formed on the aluminum plate and which has micropores that extend therein from a surface of the film anodized opposite the aluminum sheet in a depth direction of the anodized film, in which each of the micropores has a large diameter portion extending from the surface of the anodized film to an average depth (depth A) of 75 to 120 nm, and a small diameter portion, which communicates with the underside of the large diameter portion and extends to an average depth of 900 to 2000 nm from a level of communication with the large diameter portion, where an average diameter of the large diameter portion on the surface of the anodized film is at least 10 nm, but less than 30 nm, and the ratio of depth A to average diameter (depth A/average diameter) of the large diameter portion ro is greater than 4.0 but less than 12.0, and where an average diameter of the small diameter portion at the communication level is greater than 0 and less than 10.0 nm.
[0012] (2) Holder for lithographic printing plate according to 1, wherein the small-diameter portion includes a small-diameter first portion and a small-diameter second portion that differ from each other in depth, wherein the first the small diameter portion is greater in average depth than the small diameter second portion, and wherein the anodized film between the underside of the small diameter first portion and the surface of the aluminum sheet has an average thickness of at least 17 nm and a minimum thickness of at least 15 nm.
[0013] (3) Holder for lithographic printing plate according to (1) or (2), wherein the density of the first small diameter portion is 550 to 700 pcs/μm2.
[0014] (4) Holder for lithographic printing plate according to any one of (1) to (3), wherein the difference in average depth between the first small-diameter portion and the second small-diameter portion is 75 at 200 nm.
[0015] (5) Holder for lithographic printing plate according to any one of (1) to (4), wherein the large diameter portion has a diameter that gradually increases from the surface of the anodized film towards the aluminum plate , wherein the average diameter (average diameter of the underside) of the large diameter portion at the communication level is greater than the average diameter (average diameter of the surface layer) of the large diameter portion at the surface of the anodized film; the mean diameter of the bottom is greater than 10 nm but less than 60 nm; and the ratio of depth A to mean bottom diameter (depth A/mean bottom diameter) is at least 1.2, but less than 12.0.
[0016] (6) Holder for lithographic printing plate according to (5), wherein the rate of increase in surface area of the large diameter portion is expressed by equation (A): (Rate of increase in surface area ) = 1 + Pore Density x ((π x (mean diameter of surface layer/2 + mean diameter of bottom/2) x ((mean diameter of bottom/2 - mean diameter of surface layer/2) 2+ Depth A2) 1/2+ π x (average diameter of the bottom/2) 2- π x (average diameter of the surface layer/2) 2)) and the surface area increase rate is 1.9 to 16.0.
[0017] (7) Holder for lithographic printing plate according to any one of 1 to 6, wherein the ratio of the average diameter of the large-diameter portion on the surface of the anodized film to the average diameter of the small-diameter portion on the communication level (average diameter of large diameter portion/average diameter of small diameter portion) is greater than 1.00 but less than 1.50.
[0018] (8) Lithographic printing plate precursor comprising: the lithographic printing plate holder according to any one of 1 to 7; and an image recording layer formed thereon.
[0019] (9) Method of producing the support for lithographic printing plate according to any one of 1 to 7, comprising: a first anodizing treatment step to anodize the aluminum plate; and a second anodizing treatment step to further anodize the aluminum sheet with the anodized film obtained in the first anodizing treatment step. ADVANTAGEOUS EFFECTS OF THE INVENTION
[0020] The present invention can provide a support for lithographic printing plate with excellent scratch resistance, and allow a lithographic printing plate formed therefrom to have a longer printing life and to be able to achieve a precursor of lithographic printing plate with excellent press development capability; a method of producing said lithographic printing plate holder; and a precursor to the lithographic printing plate. Furthermore, a lithographic printing plate using the lithographic printing plate holder, in accordance with the present invention, has properties of substantially equivalent grades to those of the state of the art, in terms of ink scavenging capability in continuous printing and after printing was stopped. At the same time, the support for lithographic printing plate obtained in the present invention exhibits excellent scratch resistance. BRIEF DESCRIPTION OF THE DRAWINGS
[0021] FIG. 1 is a schematic cross-sectional view showing an embodiment of a lithographic printing plate holder of the invention.
[0022] FIG. 2 is a schematic cross-sectional view showing a modification of the embodiment of the lithographic printing plate holder of the invention.
[0023] FIG. 3 includes schematic cross-sectional views showing a substrate and an anodized film in the order of processing steps in a method of producing the lithographic printing plate holder of the invention.
[0024] FIG. 4 is a graph showing an example of an alternating current wave that can be used in the treatment of electrochemical granulation in the method of producing the lithographic printing plate holder of the invention.
[0025] FIG. 5 is a side view showing an example of a radial cell in the electrochemical granulation treatment with alternating current in the method of producing the lithographic printing plate holder of the invention.
[0026] FIG. 6 is a side view that conceptually shows a brush granulation step used in the treatment of mechanical granulation during the production of the lithographic printing plate holder of the invention.
[0027] FIG. 7 is a schematic view of an anodizing apparatus that can be used in anodizing treatment during the production of the lithographic printing plate holder of the invention.
[0028] FIG. 8 is a schematic cross-sectional view showing a preferred embodiment of the lithographic printing plate holder of the invention. DESCRIPTION OF EMBODIMENTS
[0029] The support for lithographic printing plate and the method of production thereof, according to the invention, are described below.
[0030] The support for lithographic printing plate of the invention includes an aluminum plate and an anodized film formed thereon, where each of the micropores in the anodized film has a certain shape so that a large diameter portion having an average diameter larger communicates with a small diameter portion with a smaller average diameter along the depth direction (ie, the film thickness direction). In the present invention, particularly, although print life has been considered to have a relationship of choice with press development capability, these properties can be achieved simultaneously at a higher level by controlling the average diameter and average depth. of large diameter portions with larger average diameter in the micropores.
[0031] FIG. 1(A) is a schematic cross-sectional view showing an embodiment of the lithographic printing plate holder of the invention.
[0032] The lithographic printing plate holder 10, shown in the drawing, has a laminated structure, in which an aluminum plate 12 and an anodized aluminum film 14 (hereinafter referred to simply as "anodized film") are stacked, in this order. The anodized film 14 has micropores 16 which extend from the surface thereof towards the side of the aluminum sheet 12, and each micropore 16 has a large diameter portion 18 and a small diameter portion 20. The term "micropores" is used here to designate one of the pores in the anodized film and not to define the pore size.
[0033] First, the aluminum sheet 12 and the anodized film 14 are described in detail. ALUMINUM PLATE
[0034] The aluminum sheet 12 (aluminum support), used in the invention, is made of a dimensionally stable metal composed mainly of aluminum; ie aluminum or aluminum alloy. Aluminum sheet is selected from pure aluminum sheets, metal alloy sheets composed mainly of aluminum and small amounts of other elements, and plastic or paper films, in which the aluminum (alloy) it is laminated or steam deposited. Furthermore, a composite sheet as described in JP 48-18327 B, in which an aluminum sheet is coupled to a polyethylene terephthalate film can be used.
[0035] In the following description, the above-described sheets made of aluminum or aluminum alloys are collectively referred to as "aluminium sheet"12. Other elements that may be present in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium. The content of other elements in the alloy is not more than 10% by weight. In the invention, the aluminum sheet used is preferably made of pure aluminum, but it may contain small amounts of other elements, as it is difficult to manufacture completely pure aluminum from a casting technology point of view. Aluminum sheet 12, applied to the invention, and as described above, is not specified by its composition, but by conventionally known materials, such as JIS A1050, JIS A1100, JIS A3103 and JIS A3005 materials, which can be used in a manner proper.
The aluminum sheet 12 used in the present invention is treated as it travels continuously, generally in the form of a web, and has a width of about 400 mm to about 2000 mm, and a thickness of about 0 .1 mm to about 0.6 mm. The width and thickness can be changed if necessary based on some considerations such as the size of the printing press, the size of the printing plate and the user's need.
[0037] The aluminum sheet is suitably subjected to substrate surface treatments, which will be described later. ANODIIZED FILM
[0038] Anodized film 14 refers to an anodized aluminum film (alumina film) that is generally formed on a surface of aluminum sheet 12 through anodizing treatment and has micropores 16 that are substantially perpendicular to the surface of the film and are evenly distributed. The micropores 16 extend along the thickness direction of the anodized film 14 from the surface of the anodized film opposite the aluminum sheet 12 (towards the side of the aluminum sheet12).
[0039] Each micropore 16 in the anodized film 14 has the large diameter portion 18 extending from the surface of the anodized film to an average depth of 75 to 120 nm (depth A: See FIG. 1), and the small diameter portion 20 which communicates with the lower part of the large diameter portion 18 and further extends from the communication level (Y communication level: See FIG. 1) to an average depth of 900 to 2000 nm.
[0040] The large diameter portion 18 and the small diameter portion 20 are described in detail below. LARGE DIAMETER PORTION
[0041] Large diameter portions 18 have an average diameter (average aperture size) of 10 nm or more, but less than 30 nm, on the surface of the anodized film 14. At an average diameter within the above range, the lithographic printing plate obtained using the lithographic printing plate holder has a longer printing life, and the lithographic printing plate precursor obtained using the holder has a longer printing life, excellent developing ability in the press and excellent ink scavenging capability in continuous printing and after printing has stopped. In particular, in terms of longer print life, the average diameter is preferably from 10 to 25 nm, preferably from 11 to 15 nm, and primarily from 11 to 13 nm.
[0042] At an average diameter less than 10 nm, an acceptable anchoring effect is not obtained, nor is the print life of the lithographic printing plate improved. At an average diameter of 30 nm or greater, the rough surface is damaged, whereby the print life cannot be improved.
[0043] The average diameter of the large diameter portions 18 is determined as follows: The surface of the anodized film 14 is observed by FE-SEM, at a magnification of 150,000X, to obtain four images (N = 4), in the four resulting images, the diameter of micropores (large diameter portions) within an area of 400 x 600 nm2 is measured, and the average of the measurements is calculated.
[0044] The equivalent circle diameter is used if the shape of the large diameter portion 18 is not circular. The "diameter of equivalent circle" refers to a diameter of a circle, assuming the shape of the opening is the circle with the same projected area as that of the opening.
[0045] The bottom of each large diameter portion 18 is the average depth of 75 to 120 nm from the surface of the anodized film (referred to hereafter as "depth A"). In other words, each large diameter portion 18 is a portion of the pore that extends from the surface of the anodized film, in the depth direction (thickness direction), to a depth of 75 to 120 nm. At an average depth within the above range, the lithographic printing plate obtained using the lithographic printing plate holder has a longer printing life, and the lithographic printing plate precursor obtained using the holder has excellent revealability in the press. In particular, the depth A is preferably 85 and 110 nm, and preferably 85 and 105 nm, since the print life and development capacity in the press are much better.
[0046] At an average depth less than 75 nm, an acceptable anchoring effect is not obtained, and the lithographic printing plate has a shorter print life. At an average depth greater than 120 nm, the lithographic printing plate precursor has little press development capability.
[0047] The average depth is determined as follows: The distance from the surface of the anodized film to the communication level in the cross section of the anodized film is observed by FE-MET at a magnification of 500,000X, the depth of 60 (N = 60) of the micropores (large diameter portions) is measured, and the average of the measurements is calculated. For measuring the cross section of the anodized film, a known method can be adopted (eg the anodized film is cut by the FIB to prepare a thin film (about 50 nm) so that the measurement of the cross section of the anodized film 14).
[0048] The ratio between the depth A, at which the undersides of the large diameter portions 18 are positioned, and the average diameter of the large diameter portions 18 (depth A/average diameter) is greater than 4.0, but less than 12.0. In a ratio within the above range, the lithographic printing plate obtained using the lithographic printing plate holder has a longer printing life, and the lithographic printing plate precursor obtained using the holder has excellent ability to development in the press. In particular, the ratio (depth A/average diameter) is preferably from 5.6 to 10.0 and, primarily, from 6.5 to 9.6, since the print life and development capacity in the presses are much better.
[0049] At a ratio (A depth/average diameter) of 4.0 or less, the lithographic printing plate has little ink scavenging capability in continuous printing and the lithographic printing plate precursor has little press development capability . At a ratio (depth A/average diameter) greater than 12.0, the lithographic printing plate has a shorter print life.
[0050] The shape of the large diameter portions 18 is not particularly limited. Examples of shapes include a substantially straight tubular shape (substantially columnar shape), an inverted cone shape (conical shape), in which the diameter decreases from the surface of the anodized film towards the aluminum sheet 12, and a substantially conical shape (shape). inversely conical), in which the diameter increases from the surface of the anodized film towards the aluminum sheet 12. A substantially straight tubular shape or an inverse conical shape is preferred.
[0051] When the large diameter portions 18 are in a substantially straight tubular shape, the large diameter portions 18 may have a difference of about 1 nm to about 5 nm between the inner diameter and the diameter of the opening in the surface of the anodized film 16.
[0052] The case where a large diameter portion 18a is in a substantially conical shape (inversely conical shape), in which the diameter increases from the surface of the anodized film 14 towards the aluminum sheet 12 is shown in FIG. two.
[0053] The diameter (inner diameter) of the large diameter portions 18a, in a lithographic printing plate holder 100, gradually increases from the surface of the anodized film 14 towards the side of the aluminum plate 12. The shape of the large portions diameter 18a is not particularly limited, as long as the above diameter condition is met, and may generally have a substantially conical shape or a substantially bell shape. The large diameter portions, having the aforementioned structure, allow the resulting lithographic printing plate to have excellent properties in terms of print life, ink scavenging capability in continuous printing and after printing has stopped, and the like.
[0054] In FIG. 2, the average diameter of the large diameter portions 18a on the surface of the anodized film 14 (average diameter of the surface layer) is smaller than the average diameter of the large diameter portions 18a at the level of communication Y with the corresponding small diameter portions 20 (average diameter of the bottom). The size of the mean diameter of the underside is not particularly limited and is preferably larger than 10 nm, but smaller than 60 nm, and preferably 20 to 30 nm. In the middle diameter of the lower part, within the above range, the lithographic printing plate has excellent properties in terms of ink scavenging capability in continuous printing and after printing has stopped, press developing capability, and the like.
[0055] The ratio of depth A to mean bottom diameter (depth A/mean bottom diameter) is not particularly limited and is preferably 1.2 or more, but less than 12.0, and, primarily, from 2.5 to 6.0. At a ratio of depth A to the average diameter of the bottom within the above range, the lithographic printing plate has excellent properties in terms of print life, ink scavenging capability in continuous printing and after printing has stopped , and the like.
[0056] The average diameter of the underside is determined as follows: The cross section of the anodized film 14 is observed by FE-TEM, with a magnification of 500,000X, the diameter of 60 (N = 60) large diameter portions 18a at communication level Y is measured, and the average of the measurements is calculated. For measuring the cross section of anodized film, a known method can be adopted. For example, the anodized film 14 is cut to prepare a thin film (about 50 nm) so that the measurement of the cross section of the anodized film 14 is carried out.
[0057] In FIG. 2, the surface area increase rate of the large diameter portions 18a, expressed by equation (A), is preferably from 1.9 to 16.0 and, primarily, from 2.1 to 11.7. At a surface area increase rate within the above range, the lithographic printing plate has excellent properties in terms of print life, ink scavenging capability in continuous printing and after printing has stopped, or developing capability in continuous printing. press.
[0058] (Rate of increase in surface area) = 1 + Pore Density x ((π x (average diameter of surface layer/2 + average diameter of bottom/2) x ((average diameter of bottom/ 2 - average diameter of surface layer/2) 2+ Depth A2) 1/2+ π x (average diameter of bottom/2) 2- π x (average diameter of surface layer/2) 2)) To a In equation (A) above, an area of 1 µm x 1 µm on the surface of the anodized film is observed first. Equation (A) above expresses what the increase in surface area within the above area is due to the formation of large diameter portions. More specifically, "1" in equation (A) above represents the area of 1 µm x 1 µm on the surface of the anodized film. In equation (A), "π x (average surface layer diameter/2 + average bottom diameter/2) x ((average bottom layer/2 diameter - average surface layer/2 diameter) 2+ Depth A2) 1/2" represents the surface area of the lateral surface of the large-diameter portion, "π x (mean diameter of the bottom/2) 2" represents the area of the underside of a large-diameter portion, and "π x ( mean surface layer diameter/2)2" represents the opening area of a large diameter portion on the surface of the anodized film.
[0059] The shape of the underside of the large diameter portions 18 is not particularly limited and can be curved (convex) or flat. SMALL DIAMETER PORTION
[0060] As shown in FIG. 1, each of the small diameter portions 20 is a portion of the pore that communicates with the underside of the corresponding large diameter portion 18, and extends further from the communication level Y in the depth direction (thickness direction ). A small diameter portion 20 normally communicates with a large diameter portion 18, but two or more small diameter portions 20 can communicate with the underside of a large diameter portion 18.
[0061] The small diameter portions 20 have an average diameter at the communication level greater than 0 and less than 10.0 nm. In particular, the average diameter is preferably not more than 9.5 nm, and preferably not more than 9.0 nm, in terms of press development capacity or ink scavenging capability in printing continuous and after printing has stopped.
[0062] At an average diameter of 10.0 nm or more, the lithographic printing plate obtained, using the lithographic printing plate holder of the invention, has a shorter printing life and the lithographic printing plate precursor has little development capability in the press.
[0063] The average diameter of the small diameter portions 20 is determined as follows: The surface of the anodized film 14 is observed by FE-SEM, with a magnification of 150,000X, to obtain four images (N = 4), in the four resulting images, the diameter of micropores (portions of small diameter) within an area of 400 x 600 nm2 is measured, and the average of the measurements is calculated. When the depth of the large diameter portions is large, the average diameter of the small diameter portions can optionally be determined by cutting the upper region of the anodized film 14 (including the large diameter portions) (e.g., cutting it with gas of argon), and observation of the surface of the anodized film 14 by FE-SEM.
[0064] The equivalent circle diameter is used if the shape of the small diameter portion 20 is not circular. The "diameter of equivalent circle" refers to a diameter of a circle assuming the shape of the opening is the circle with the same projected area as that of the opening.
[0065] The lower part of each small diameter portion 20 is at a distance of 900 to 2000 nm, in the depth direction, from the level of communication with the corresponding large diameter portion 18 (the level corresponding to the aforementioned depth A). In other words, the small diameter portions 20 are portions of the pores, each of which extends further in the depth direction (thickness direction) from the level of communication with the corresponding large diameter portions 18 and the small portions. diameter 20 have an average depth of 900 to 2000 nm. The lower part of each small diameter portion is preferably at a depth of 900 to 1500 nm from the communication level in terms of scratch resistance of the lithographic printing plate holder.
[0066] At an average depth of less than 900 nm, the lithographic printing plate holder has little scratch resistance. An average depth greater than 2000 nm requires extended treatment time and reduces productivity and economic efficiency.
[0067] The average depth is determined by obtaining a cross-sectional image of the anodized film 14 by FE-SEM (at a magnification of 50,000X), measuring the depth of at least 25 small diameter portions and the averaging measurements.
[0068] The ratio between the average diameter of the large diameter portions 18 on the anodized film surface and the average diameter of the small diameter portions 20, at the communication level (large diameter portion diameter/small diameter portion diameter) it is not particularly limited, and is preferably greater than 1.00 to 1.50, but more preferably from 1.10 to 1.40, and most preferably from 1.10 to 1.30. In a ratio within the above range, the lithographic printing plate has a longer print life or excellent in-press development capability.
[0069] The density of the small diameter portions 20 in the cross section of the anodized film 14, at the Y communication level, is not particularly limited, and is preferably from 100 to 5000 pcs/μm2 and, preferably, from 600 to 1200 units /μm2. At a density within the former range, the lithographic printing plate has further improved on-press developability or ink scavenging capability in continuous printing or after printing has stopped.
[0070] The shape of the small diameter portions 20 is not particularly limited. Examples of shapes include a substantially straight tubular shape (substantially columnar shape), and a conical shape, in which the diameter decreases in the depth direction, and a substantially straight tubular shape is preferred. The small diameter portions 20 can extend from the Y communication level towards the aluminum sheet 12 while branching.
[0071] The shape of the underside of the small diameter portions 20 is not particularly limited and can be curved (convex) or flat.
[0072] The inner diameter of the small diameter portions 20 is not particularly limited and may generally be substantially equal to, or smaller or larger than, the diameter at the communication level. There can normally be a difference of about 1 nm to about 10 nm between the inside diameter of the small diameter portions 20 and the opening diameter thereof.
[0073] The thickness of the anodized film between the underside of each small diameter portion 20 and the surface of the aluminum sheet 12 (which corresponds to the thickness X in Fig. 1(A)) is not particularly limited, and preferably has , from 7 to 50 nm and, primarily, from 20 to 30 nm. The portion corresponding to the thickness X of the anodized film is also called the "barrier layer". A thickness X, within the range defined above, leads to greater resistance to microdotted scumming.
[0074] The thickness X value above is an average obtained by measuring the thickness of the anodized film between the bottom of each of at least 50 small diameter portions 20 and the surface of the aluminum sheet 12 and the average arithmetic of measurements.
[0075] One of the preferred embodiments of the anodized film described above is as shown in FIG. 8. A lithographic printing plate holder 110, shown in FIG. 8, has a laminated structure on which the aluminum sheet 12 and an anodized aluminum film 140 are stacked in that order. The anodized film 140 has micropores 160 that extend from the surface of the anodized film toward the side of the aluminum sheet 12, and each of the micropores 160 has a large diameter portion 180 and a small diameter portion 200.
[0076] The large diameter portions 180 have a substantially conical shape (inversely conical shape), in which the diameter increases from the surface of the anodized film 140 towards the side of the aluminum sheet 12, as described above in relation to FIG. 2. The ranges of mean surface layer diameter, mean bottom diameter, ratio (depth A/mean bottom diameter), surface area increase rate, and the like of large diameter portions 180 are as described above.
[0077] Each of the small diameter portions 200 is a portion of the pore that communicates with the underside of the corresponding large diameter portion 180 and further extends from the communication level Y in the depth direction (thickness direction ). Although in FIG. 8, the two small diameter portions 200 communicate with a large diameter portion 180, the invention is not limited to this configuration and one or two or more small diameter portions 200 may (m) communicate with a large diameter portion 180.
[0078] The average diameter of the small diameter portions 200, at the communication level, as well as their preferred range, is defined in the same way as the average diameter of the small diameter portions 20 described above.
[0079] The average depth of the small diameter portions 200, as well as their preferred range, is defined in the same way as the average depth of the small diameter portions 20 described above.
[0080] The ratio between the average diameter of the large diameter portions 180, on the surface of the anodized film, and the average diameter of the small diameter portions 200, at the communication level (large diameter portion diameter/small diameter portion diameter ), as well as its preferred range, is defined in the same way as the ratio described above between the average diameter of the large diameter portions 18 at the anodized film surface and the average diameter of the small diameter portions 20 at the communication level (diameter of the large diameter portion/diameter of the small diameter portion).
[0081] Each of the small diameter portions 200 includes a small diameter first portion 210 and a small diameter second portion 220 differ from each other in average depth.
[0082] The small diameter first portions 210 are greater in average depth than the small diameter second portions 220. In other words, the bottom of each small diameter first portion 210 is positioned closer to the aluminum sheet 12 of the than the bottom of every second portion of small diameter 220.
[0083] The average depths of the first and second small diameter portions 210 and 220 are determined as follows. First, of the small diameter portions, the shorter small diameter portion (hereinafter referred to as "minimum small diameter portion") and the longer small diameter portion ("hereinafter referred to as "maximum small diameter portion") are selected, and a small-diameter portion whose bottom is at a level closer to the bottom of the minimum small-diameter portion is selected as a second small-diameter portion; while a small-diameter portion whose bottom is at a level closest to the bottom of the maximum small diameter portion, is selected as a first small diameter portion. A small diameter portion, the bottom of which is at an intermediate level between the bottom of the minimum small diameter portion and the bottom of the maximum small diameter portion is selected as a first small diameter portion. The depth of at least 25 small diameter portions etro, among the first selected small diameter portions, is measured and the arithmetic mean of the measurements is calculated to thus obtain the average depth of the first small diameter portions. The depth of at least 25 small diameter portions among the selected second small diameter portions is measured and the arithmetic mean of the measurements is thus calculated to obtain the average depth of the second small diameter portions.
[0084] The difference between the average depth of the first small diameter portions 210 and the average depth of the second small diameter portions 220 is not particularly limited and is preferably from 75 to 200 nm and more preferably from 100 to 200 nm, in terms of dot skimming resistance.
[0085] The density of the small diameter portions 200 in the cross section of the anodized film 140, at the Y communication level, is not particularly limited and is preferably from 100 to 5,000 pcs/μm2, and primarily from 600 to 1,200 pcs /μm2. At a density within the former range, the lithographic printing plate has further improved the development capability in the press or the ink scavenging capability in continuous printing and after printing has stopped.
[0086] The density of the first small diameter portions 210 is not particularly limited, and is preferably from 550 to 700 pcs/μm2 and primarily from 550 to 650 units/μm2 in terms of spot skimming resistance.
[0087] The average thickness X of the anodized film between the underside of each first small-diameter portion 210 and the surface of the aluminum sheet 12 is not particularly limited, and is preferably at least 17 nm and primarily , of at least 18 nm, in terms of dot skimming resistance. The upper limit of the average thickness is not particularly limited but is generally up to 30 nm.
[0088] The above average thickness is a value obtained by measuring the thickness of the anodized film between the bottom of each of at least 50 small diameter portions 210 and the first surface of the aluminum sheet 12 and the arithmetic mean of the measurements.
[0089] The minimum thickness of the anodized film between the underside of each first small-diameter portion 210 and the surface of the aluminum sheet 12 is not particularly limited and is preferably at least 15 nm and, primarily, at least 17 nm.
[0090] The shapes of the first and second small diameter portions 210 and 220 are not particularly limited. Examples of shapes include a substantially straight tubular shape (substantially columnar shape). In addition, the inner diameter of the first small diameter portions 210 can be increased to a level between the lower portions of the second small diameter portions 220 and the aluminum sheet 12 (such as, for example, about 1 nm to about 10 nm. nm). METHOD OF PRODUCTION OF THE SUPPORT FOR LITHOGRAPHIC PRINTING PLATE
[0091] A method of producing the support for lithographic printing plate of the invention is described below.
[0092] The production method of the lithographic printing plate holder of the invention is not particularly limited and a production method in which the following steps are carried out in order is preferred.
[0093] (Surface roughness treatment step) Step to carry out the surface roughness treatment on an aluminum plate; (First stage of anodizing treatment) Step to anodize the surface of the aluminum sheet that has been subjected to a roughness treatment; (Treatment step for widening the pore) Step to widen the diameter of the micropores in an anodized film, placing the aluminum plate with the anodized film obtained in the first anodizing treatment step in contact with an aqueous acid or an alkaline solution; (Second anodizing treatment step) Step to anodize the aluminum sheet obtained in the treatment step to enlarge the pores; (Third anodizing treatment step) Step to anodize the aluminum sheet obtained in the second anodizing treatment step; e (Hydrophilizing treatment step) Step to hydrophilize the aluminum sheet obtained in the second or third step of anodizing treatment.
[0094] The respective steps are described in detail below. The surface roughness treatment step, the pore widening treatment step, the hydrophilizing treatment step and the third anodizing treatment step are not essential steps.
[0095] FIG. 3 shows schematic cross-sectional views of the substrate and the anodized film in the order of steps, from the first anodizing treatment step to the third anodizing treatment step. SURFACE ROUGHNESS TREATMENT STAGE
[0096] The surface roughness treatment step is a step in which the surface of the aluminum sheet is subjected to surface roughness treatment including electrochemical granulation treatment. This step is preferably carried out before the first anodizing treatment step to be described below, but it cannot be carried out if the aluminum sheet already has a chosen surface profile.
[0097] Surface roughness treatment may include electrochemical granulation treatment only, or a combination of electrochemical granulation treatment with mechanical granulation treatment and/or chemical granulation treatment.
[0098] In cases where the mechanical granulation treatment is combined with the electrochemical granulation treatment, the mechanical granulation treatment is preferably followed by an electrochemical granulation treatment.
[0099] In the practice of the invention, the electrochemical granulation treatment is preferably carried out in an aqueous solution of nitric acid or hydrochloric acid.
[00100] Mechanical granulation treatment is generally carried out so that the surface of the aluminum sheet can have a surface roughness Ra of 0.35 to 1.0 μm.
[00101] In the invention, the mechanical granulation treatment is not particularly limited by its conditions and can be carried out according to the method described in, for example, JP 50-40047 B. The mechanical granulation treatment can be carried out by granulation with school using a pumice suspension or a transfer system.
[00102] Chemical granulation treatment is also not particularly limited, and can be carried out by any known method.
[00103] Mechanical granulation treatment is preferably followed by a chemical pickling treatment described below.
[00104] The purpose of chemical pickling treatment after mechanical granulation treatment is to smooth the edges of irregularities in the surface of the aluminum sheet so as to prevent the ink from spreading on the edges during printing; to improve the skimming resistance of the lithographic printing plate; and to remove abrasive particles or other unnecessary substances that remain on the surface.
Chemical pickling processes, including pickling with an acid and pickling with a base, are known, and an example of a method that is particularly excellent in terms of pickling efficiency includes chemical pickling treatment using an alkaline solution (also referred to below as "alkaline pickling treatment").
[00106] The alkaline agents that can be used in the alkaline solution are not particularly limited, and illustrative examples of suitable alkaline agents include sodium hydroxide, potassium hydroxide, sodium metasilicate, sodium carbonate, sodium aluminate, and gluconate of sodium.
[00107] Alkaline agents may contain aluminum ions. The alkaline solution has a concentration of preferably at least 0.01% by weight and more preferably at least 3% by weight, but preferably not above 30% by weight and most preferably not above 25 % by weight.
[00108] The temperature of the alkaline solution is preferably room temperature or higher, and more preferably at least 30 °C, preferably not above 80 °C, and most preferably not above 75 °C.
[00109] The amount of pickling is preferably at least 0.1 g/m2, and preferably at least 1 g/m2, but preferably not above 20 g/m2 and preferably not above 10 g/m2.
[00110] The treatment time is preferably from 2 seconds to 5 minutes, depending on the amount of pickling, and primarily from 2 to 10 seconds in order to improve productivity.
[00111] In cases where the mechanical granulation treatment is followed by the alkaline pickling treatment in the invention, the chemical pickling treatment uses an acid solution at a low temperature (also referred to below as "demutting treatment") is preferably carried out to remove substances produced by the alkaline pickling treatment.
The acids that can be used in the acid solution are not particularly limited and illustrative examples of these include sulfuric acid, nitric acid and hydrochloric acid. The acid solution preferably has a concentration of 1 to 50% by weight. The acid solution preferably has a temperature of 20 to 80°C. When the concentration and temperature of the acid solution are within the above defined ranges, the lithographic printing plate obtained using the lithographic printing plate holder of the invention has greater resistance to dot skimming.
[00113] In the practice of the invention, the treatment of surface roughness is a treatment in which the electrochemical granulation treatment is carried out after the mechanical granulation treatment and chemical pickling treatment are carried out if necessary, but even in cases where the treatment Electrochemical granulation treatment is carried out without carrying out mechanical granulation treatment, the electrochemical granulation treatment can be preceded by a chemical pickling treatment using an aqueous alkaline solution such as sodium hydroxide. In this way, impurities and the like, which are present around the surface of the aluminum sheet, can be removed.
[00114] The electrochemical granulation treatment easily forms fine irregularities (pits) on the surface of the aluminum plate and is therefore suitable for preparing a lithographic printing plate with excellent print quality.
[00115] The electrochemical granulation treatment is carried out in an aqueous solution containing nitric acid or hydrochloric acid as its main doe Ingredient using direct or alternating current.
[00116] The electrochemical granulation treatment is preferably followed by a chemical pickling treatment described below. Coal and intermetallic compounds are present on the surface of the aluminum sheet that has undergone an electrochemical granulation treatment. In the chemical pickling treatment that is carried out after the electrochemical granulation treatment, it is preferable that the chemical pickling treatment, using an alkaline solution (alkaline pickling treatment), is first carried out in order to remove particularly the soot with high efficiency. . Chemical pickling treatment conditions, using an alkaline solution, preferably include a treatment temperature of 20 to 80°C and a treatment time of 1 to 60 seconds. It is desirable that the alkaline solution contain aluminum ions.
[00117] In order to remove substances generated by the chemical pickling treatment, which uses an alkaline solution after the electrochemical granulation treatment, it is preferable to carry out a chemical pickling treatment using an acid solution at a low temperature (treatment of demuting).
[00118] Even in cases where the electrochemical granulation treatment is not followed by the alkaline pickling treatment, it is preferable that the demutting treatment be carried out to efficiently remove the soot.
[00119] In the practice of the invention, the chemical pickling treatment described above is not particularly limited and can be carried out by dipping, bathing, coating or other processes.
[00120] FIRST STAGE OF ANODIIZING TREATMENT The first stage of anodizing treatment is a step in which an anodized aluminum film, which has micropores that extend in the direction of the depth (thickness direction) of the film, is formed on the surface of the film. aluminum sheet by anodizing treatment on the aluminum sheet which has been subjected to the surface roughness treatment described above. As shown in FIG. 3(A), as a result of the first anodizing treatment, an anodized aluminum film 14a with micropores 16a is formed on a surface of the aluminum sheet 12.
[00121] The first anodizing treatment can be carried out by a method known in the art, but the production conditions must be properly regulated so that said micropores 16 can finally be formed.
[00122] More specifically, the average diameter (average opening diameter) of the micropores 16a formed in the first stage of anodizing treatment is usually from about 4 nm to about 14 nm and preferably from 5 to 10 nm. At an average aperture diameter within the above range, the micropores 16 with the shapes specified above are easily formed and the resulting lithographic printing plate and lithographic printing plate precursor have much better properties.
[00123] The 16a micropores generally have a depth of about 65 nm to about 110 nm and preferably 75 to 95 nm. At a depth within the above range, the micropores 16 with the shapes specified above are easily formed and the resulting lithographic printing plate and lithographic printing plate precursor have much better properties.
[00124] The density of micropores 16a is not particularly limited and is preferably from 50 to 4000 pcs/μm2 and preferably from 100 to 3000 pcs/μm2. With a micropore density within the above range, the resulting lithographic printing plate has a longer print life and excellent ink scavenging capability after printing has stopped, and the lithographic printing plate precursor has excellent developing capability in the press.
[00125] The anodized film obtained by the first stage of anodizing treatment has a thickness, preferably, from 75 to 120 nm and, preferably, from 85 to 105 nm. At a film thickness within the above range, the lithographic printing plate using the lithographic printing plate holder, obtained after this step, has a longer print life, excellent ink scavenging ability after printing has stopped, excellent dot skimming resistance, and excellent white spotting resistance, and the precursor of lithographic printing plate has excellent press development capability.
[00126] In addition, the film obtained anodized by the first stage of anodizing treatment has a coating weight, preferably from 0.18 to 0.29 g/m2 and, primarily, from 0.2 to 0.25 g/ m2. With a coating weight within the above range, the lithographic printing plate using the lithographic printing plate holder, obtained after the previous steps, has a longer print life, excellent ink scavenging ability after printing has stopped , excellent dot skimming resistance, and excellent white spotting resistance, and the precursor of lithographic printing plate has excellent press development capability.
[00127] In the first stage of anodizing treatment, acidic aqueous solutions, such as sulfuric acid, phosphoric acid and oxalic acid, can be used mainly for the electrolytic bath. Optionally, an aqueous solution or a non-aqueous solution containing chromic acid, sulfamic acid, benzene sulphonic acid or a combination of two or more of these can be used. The anodized film can be formed on the surface of the aluminum sheet by passing direct current or alternating current through an aluminum sheet in said electrolytic bath.
[00128] The electrolytic bath may contain aluminum ions. The aluminum ion content is not particularly limited and is preferably from 1 to 10 g/l.
[00129] Anodizing treatment conditions are suitably adjusted depending on the electrolyte solution employed. However, the following conditions are generally suitable: an electrolyte concentration of 1 to 80% by weight (preferably 5 to 20% by weight), a solution temperature between 5 and 70 °C (preferably 10 to 60 °C), a current density of 0.5 to 60 A/dm2 (preferably 5 to 50 A/dm2), a voltage of 1 to 100 V (preferably 5 to 50 V), and an electrolysis time from 1 to 100 seconds (preferably, from 5 to 60 seconds).
[00130] Of these anodizing treatment methods, the preferred method is that described in GB 1412768, which involves anodic oxidation to sulfuric acid at a high current density. TREATMENT STAGE TO ENLARGE THE PORE
[00131] The pore widening treatment step is a step to widen the diameter of the micropores (pore size) present in the anodized film formed through the first anodizing treatment step (pore widening treatment step) described above. As shown in FIG. 3(B), the pore widening treatment increases the diameter of micropores 16a to form an anodized film 14b containing micropores 16b with a larger average diameter.
[00132] The pore widening treatment preferably increases the mean diameter of micropores 16b within a range of 10 nm or more, but less than 30 nm. The micropores 16b correspond to the large diameter portions 18 described above.
[00133] The average depth of the micropores 16b, from the surface of the film, is preferably adjusted by this treatment so that it is approximately the same as the depth A.
[00134] The treatment for widening the pores is carried out by contacting the aluminum plate, obtained through the first step of anodizing treatment described above, with an acidic or alkaline aqueous solution. Examples of contact methods include, but are not limited to, immersion and spraying. Of these, immersion is preferred.
[00135] When the pore widening treatment step is carried out with an alkaline aqueous solution, it is preferable to use an aqueous solution of at least one base selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide. The alkaline aqueous solution preferably has a concentration of 0.1 to 5% by weight.
[00136] The aluminum sheet is suitably placed in contact with the aqueous alkaline solution at 10 °C to 70 °C (preferably from 20 °C to 50 °C) for 1 to 300 seconds (preferably from 1 to 50 seconds), after the aqueous alkaline solution is adjusted to a pH of 11 to 13.
[00137] The alkaline treatment solution may contain metallic salts of weak polyvalent acids such as carbonates, borates and phosphates.
[00138] When the treatment step for pore widening is carried out with an acidic aqueous solution, it is preferable to use an aqueous solution of an inorganic acid, such as sulfuric acid, phosphoric acid, nitric acid or hydrochloric acid, or a mixture of them. The acidic aqueous solution preferably has a concentration of from 1 to 80% by weight and, preferably, from 5 to 50% by weight.
[00139] The aluminum sheet is properly placed in contact with the acidic aqueous solution at 5°C to 70°C (preferably from 10°C to 60°C) for 1 to 300 seconds (preferably from 1 to 150 seconds).
[00140] The alkaline or acidic aqueous solution may contain aluminum ions. The aluminum ion content is not particularly limited and is preferably from 1 to 10 g/l. SECOND STAGE OF ANODIZATION TREATMENT
[00141] The second stage of anodizing treatment is a stage in which the micropores, which extend in the depth direction (thickness direction) of the film, are formed by means of the anodizing treatment on the aluminum sheet that has been subjected to pore widening treatment described above. As shown in FIG. 3(C), an anodized film 14c containing micropores 16c extending in the depth direction of the film is formed by the second stage of anodizing treatment.
[00142] The second stage of anodizing treatment forms new pores, which communicate with the lower parts of the micropores 16b with the larger average diameter, have a smaller average diameter than that of the micropores 16b (which correspond to the large diameter portions 18) and extend from the communication level in the depth direction. The pores correspond to the small diameter portions 20 described above.
[00143] In the second stage of anodizing treatment, the treatment is carried out so that the newly formed pores have an average diameter greater than 0 and less than 10 nm, and an average depth from the level of communication with the large diameter portions 18 within the range specified above. The electrolytic bath used for the treatment is the same as the one used in the first stage of anodizing treatment, and the treatment conditions are considered adequate for the materials used.
[00144] The anodizing treatment conditions are suitably adjusted depending on the electrolyte solution employed. However, the following conditions are generally suitable: an electrolyte concentration of 1 to 80% by weight (preferably 5 to 20% by weight), a solution temperature between 5 and 70 °C (preferably 10 to 60 °C), a current density of 0.5 to 60 A/dm2 (preferably 1 to 30 A/dm2), a voltage of 1 to 100 V (preferably 5 to 50 V), and a time of electrolysis from 1 to 100 seconds (preferably 5 to 60 seconds).
[00145] The film obtained by the second stage of anodizing treatment generally has a thickness of 900 to 2000 nm and preferably 900 to 1500 nm. At a film thickness within the above range, the lithographic printing plate using the lithographic printing plate holder, obtained after the previous steps, has a longer print life and excellent ink scavenging ability after printing has stopped , and the precursor of lithographic printing plate has excellent press development capability.
[00146] The film obtained by the second stage of anodizing treatment generally has a coating weight of from 2.2 to 5.4 g/m2 and preferably from 2.2 to 4.0 g/m2. With a coating weight within the above range, the lithographic printing plate using the lithographic printing plate holder, obtained after the previous steps, has a longer print life and excellent ink scavenging capability after printing has stopped and the precursor of lithographic printing plate has excellent press development capability.
[00147] The ratio between the thickness of the anodized film, obtained by the first anodizing treatment step (film thickness 1), and that of the anodized film obtained by the second anodizing treatment step (film thickness 2) (film thickness) 1/film thickness 2) is preferably from 0.01 to 0.15 and preferably from 0.02 to 0.10. At a ratio within the above range, the lithographic printing plate holder has excellent scratch resistance.
[00148] In order to obtain the shape of the small diameter portions described above, the applied voltage can be increased step by step, or continuously, during treatment in the second step of anodizing treatment. By increasing the applied tension, the diameter of the formed pores is increased.
[00149] The thickness of the anodized film between the lower parts of the resulting small diameter portions and the aluminum sheet tends to increase by increasing the voltage applied in the second stage of anodizing treatment. In cases where the anodized film between the lower parts of the small diameter portions and an aluminum sheet has a predetermined thickness as a result of the above treatment, the third anodizing treatment step to be described below cannot be performed. THIRD STAGE OF ANODIZATION TREATMENT
[00150] The third anodizing treatment step is a step in which the aluminum sheet, which has undergone the second anodizing treatment, is anodized again to mainly increase the thickness of the anodized film located between the lower parts of the small diameter portions and an aluminum plate (thickness of the barrier layer). As shown in FIG. 3(D), thickness X reaches a predetermined value as a result of the third step of anodizing treatment.
[00151] As described above, in cases where the micropores already have the desired shapes, at the end of the second stage of anodizing treatment, the third stage of anodizing treatment cannot be performed.
[00152] The anodizing treatment conditions in the third anodizing treatment step are appropriately adjusted according to the electrolyte solution employed, but the treatment is generally carried out at a higher voltage than that applied in the second anodizing treatment step.
[00153] The type of electrolyte solution used is not particularly limited and any of the electrolyte solutions described above can be used. By using, for example, an aqueous solution containing boric acid as the electrolytic bath, the thickness X can be efficiently increased without changing the shape of the small diameter portions obtained by the second anodizing treatment.
[00154] The film obtained by the third stage of anodizing treatment generally has a coating weight from 0.13 to 0.65 g/m2 and preferably from 0.26 to 0.52 g/m2. With a coating weight within the above range, the lithographic printing plate using the lithographic printing plate holder, obtained after the previous steps, has a longer print life, excellent ink scavenging ability after printing has stopped , excellent dot skimming resistance, and excellent white spotting resistance, and the precursor of lithographic printing plate has excellent press development capability.
[00155] The micropores can extend further towards the aluminum sheet as a result of the third stage of anodizing treatment. HYDROFILIZATION TREATMENT STAGE
[00156] The method of production of the support for lithographic printing plate of the invention may have a hydrophilization treatment step, in which the hydrophilization treatment is carried out after the second or third step of anodizing treatment described above. The hydrophilization treatment can be carried out by means of a known method, which is described in paragraphs [0109] to [0114] of JP 2005-254638 A.
[00157] It is preferable to carry out the hydrophilizing treatment by a method in which the aluminum sheet is immersed in an aqueous solution of an alkali metal silicate, such as sodium silicate or potassium silicate, or is coated with a polymer of hydrophilic vinyl or a hydrophilic compound so as to form a hydrophilic undercoat.
[00158] The hydrophilization treatment with an aqueous solution of an alkali metal silicate, such as sodium silicate or potassium silicate, can be carried out according to the processes and procedures described in US 2,714,066 and US 3,181,461 .
[00159] The support for lithographic printing plate of the invention is preferably obtained by submitting said aluminum plate to the treatments shown in the following Embodiment A or B, in this order, Embodiment A being used primarily in terms of print life. Washing with water is desirably carried out between the respective treatments. However, in cases where solutions of the same compositions are used in the two steps (treatments) carried out consecutively, washing with water can be excluded.
[00160] EMBODIMENT A (2) chemical pickling treatment in an aqueous alkaline solution (first alkaline pickling treatment); (3) chemical pickling treatment in an acidic aqueous solution (first demutting treatment); (4) electrochemical granulation treatment in an aqueous solution based on nitric acid (first electrochemical granulation treatment); (5) chemical pickling treatment in an aqueous alkaline solution (second alkaline pickling treatment); (6) chemical pickling treatment in an acidic aqueous solution (second demutting treatment); (7) electrochemical granulation treatment in an aqueous solution based on hydrochloric acid (second electrochemical granulation treatment); (8) chemical pickling treatment in an aqueous alkaline solution (third alkaline pickling treatment); (9) chemical pickling treatment in an acidic aqueous solution (third demutting treatment); (10) anodizing treatments (first anodizing treatment, pore widening treatment, second anodizing treatment, third anodizing treatment, and); and (11) hydrophilization treatment.
[00161] EMBODIMENT B (2) chemical pickling treatment in an aqueous alkaline solution (first alkaline pickling treatment); (3) chemical pickling treatment in an acidic aqueous solution (first demutting treatment); (12) electrochemical granulation treatment in an aqueous solution based on hydrochloric acid; (5) chemical pickling treatment in an aqueous alkaline solution (second alkaline pickling treatment); (6) chemical pickling treatment in an acidic aqueous solution (second demutting treatment); (10) anodizing treatments (first anodizing treatment, pore widening treatment, second anodizing treatment, third anodizing treatment, and); and (11) hydrophilization treatment.
[00162] Treatment (2) in Embodiments A and B, above, may optionally be preceded by mechanical granulation treatment (1). Preferably, treatment (1) is not included in any of the embodiments in terms of print life, and so on.
[00163] Mechanical granulation treatment, electrochemical granulation treatment, chemical pickling treatment, anodizing treatment and hydrophilizing treatment in (1) to (12), described above, can be carried out by the same methods and conditions of treatment described above, but the methods and conditions of treatment described below are preferably used to carry out such treatments.
[00164] The mechanical granulation treatment is preferably carried out through the use of a roller with a rotating nylon brush with a bristle diameter from 0.2 to 1.61 mm and a paste (slurry) applied to the surface of the plate. aluminum.
[00165] Known abrasives can be used and illustrative examples, which can be preferably used, include silica sand, quartz, aluminum hydroxide and a mixture thereof.
[00166] The paste has a specific gravity of 1.05 to 1.3. A technique that involves spraying the slurry, a technique that involves the use of a wire brush, or a technique in which the surface shape of a textured grinding roller is transferred to the aluminum plate can be used.
[00167] The alkaline aqueous solution, which can be used in the aqueous alkaline solution in the chemical pickling treatment, has a concentration preferably of 1 to 30% by weight and may contain aluminum and alloying ingredients present in the aluminum alloy in a amount from 0 to 10% by weight.
[00168] An aqueous solution mainly composed of sodium hydroxide is preferably used in the alkaline aqueous solution. The chemical pickling treatment is preferably carried out at a solution temperature ranging from room temperature to 95°C, for a period of 1 to 120 seconds.
[00169] After the end of the pickling treatment, the treatment solution is removed with calender rollers (nip-rollers) and washing by spraying with water, preferably, in order to prevent the treatment solution from being taken to the subsequent step.
[00170] In the first alkaline pickling treatment, the aluminum sheet is dissolved in an amount, preferably from 0.5 to 30 g/m2, preferably from 1.0 to 20 g/m2, and primarily, from 3, 0 to 15 g/m2.
[00171] In the second alkaline pickling treatment, the aluminum sheet is dissolved in an amount, preferably from 0.001 to 30 g/m2, preferably from 0.1 to 4 g/m2, and primarily from 0.2 to 1.5 g/m2.
[00172] In the third alkaline pickling treatment, the aluminum sheet is dissolved in an amount, preferably from 0.001 to 30 g/m2, preferably from 0.01 to 0.8 g/m2, and primarily from 0. 02 to 0.3 g/m2.
[00173] In the treatment of chemical pickling in an acidic aqueous solution (from the first to the third desmutting treatments), phosphoric acid, nitric acid, sulfuric acid, chromic acid, hydrochloric acid or a mixed acid containing two or more of these is advantageously used .
[00174] The acidic aqueous solution preferably has a concentration of 0.5 to 60% by weight.
[00175] Aluminum and alloying ingredients present in the aluminum alloy can dissolve in the acidic aqueous solution in an amount of 0 to 5% by weight.
[00176] The chemical pickling treatment is preferably carried out at a solution temperature from room temperature to 95 °C for a treatment time of 1 to 120 seconds. After the end of the demutting treatment, removal of the treatment solution with calender rollers and spray washing with water are preferably carried out in order to prevent the treatment solution from being carried forward to the subsequent step.
[00177] The aqueous solution that can be used in the treatment of electrochemical granulation is now described.
[00178] An aqueous solution, which is used in conventional electrochemical granulation treatment involving the use of alternating current or direct current, can be used for the aqueous solution based on nitric acid used in the first electrochemical granulation treatment. The aqueous solution to be used can be prepared by adding, to an aqueous solution having a nitric acid concentration of 1 to 100 g/l, of at least one nitrate compound containing nitrate ions, such as nitrate. aluminum, sodium nitrate or ammonium nitrate, or at least a chlorine compound containing chloride ions such as aluminum chloride, sodium chloride or ammonium chloride in a range of 1 g/L to saturation.
[00179] The metals that are present in the aluminum alloy, such as iron, copper, manganese, nickel, titanium, magnesium and silicon can also be dissolved in the aqueous solution based on nitric acid.
[00180] More specifically, the use is preferably made of a solution in which aluminum chloride or aluminum nitrate is included, so that an aqueous solution of 0.5 to 2% by weight of nitric acid can contain 3 at 50 g/L of aluminum ions.
[00181] The temperature is preferably from 10 to 90 °C and preferably from 40 to 80 °C.
[00182] An aqueous solution, which is used in the treatment of conventional electrochemical granulation involving the use of alternating current or direct current, can be used for the aqueous solution based on hydrochloric acid used in the second treatment of electrochemical granulation. The aqueous solution to be used can be prepared by adding, to an aqueous solution having a hydrochloric acid concentration of 1 to 100 g/l, of at least one nitrate compound containing nitrate ions, such as nitrate. aluminum, sodium nitrate or ammonium nitrate, or at least a chlorine compound containing chloride ions such as aluminum chloride, sodium chloride or ammonium chloride in a range of 1 g/L to saturation.
[00183] The metals that are present in the aluminum alloy, such as iron, copper, manganese, nickel, titanium, magnesium and silicon can also be dissolved in the aqueous solution based on hydrochloric acid.
[00184] More specifically, the use is preferably made of a solution in which aluminum chloride or aluminum nitrate is included, so that an aqueous solution of 0.5 to 2% by weight of hydrochloric acid may contain 3 at 50 g/L of aluminum ions.
[00185] The temperature is preferably from 10 to 60 °C and, primarily, from 20 to 50 °C. Hypochlorous acid can be added to the aqueous solution.
[00186] On the other hand, an aqueous solution, which is used in the treatment of conventional electrochemical granulation involving the use of alternating current or direct current, can be used for the aqueous solution based on hydrochloric acid used in the treatment of electrochemical granulation in aqueous hydrochloric acid solution in embodiment B. To an aqueous solution to be used can be prepared by adding 0 to 30 g/L of sulfuric acid to an aqueous solution having a hydrochloric acid concentration of 1 to 100 g/ L. The aqueous solution can be prepared by adding to this solution at least one nitrate compound containing nitrate ions, such as aluminum nitrate, sodium nitrate or ammonium nitrate, or at least one chlorine compound, containing chloride ions such as aluminum chloride, sodium chloride or ammonium chloride in a range of 1 g/L to saturation.
[00187] The metals that are present in the aluminum alloy, such as iron, copper, manganese, nickel, titanium, magnesium and silicon can also be dissolved in the aqueous solution based on hydrochloric acid.
[00188] More specifically, the use is preferably made of a solution in which aluminum chloride or aluminum nitrate is included, so that an aqueous solution of 0.5 to 2% by weight of nitric acid can contain 3 at 50 g/L of aluminum ions.
[00189] The temperature is preferably from 10 to 60 °C and preferably from 20 to 50 °C. Hypochlorous acid can be added to the aqueous solution.
[00190] A sinusoidal, square, trapezoidal or triangular waveform can be used as an AC power source waveform for treating electrochemical granulation. The frequency is preferably from 0.1 to 250 Hz.
[00191] FIG. 4 is a graph showing an example of an alternating current waveform that can be used to carry out the electrochemical granulation treatment in the production method of the lithographic printing plate holder of the invention.
[00192] In FIG. 4, "ta" represents the anodic reaction time, "tc" the cathodic reaction time, "tp" the time required for the current to peak from zero, "Ia" the peak current on the cycle side anode, and "Ic" the peak current on the side of the cathode cycle. In trapezoidal waveform it is preferable for time tp until current peaks from zero to 1 to 10 ms. Under the influence of the impedance in the electrical circuit, a time tp less than 1 ms, a large power source voltage at the leading edge of the current waveform is required, thus increasing the cost of the power source equipment. At a time tp greater than 10 ms, the treatment tends to be affected by the trace components in the electrolyte solution, making it difficult to achieve uniform granulation. An alternating current cycle, which can be used in the preferred treatment of electrochemical granulation, satisfies the following conditions: the ratio of the cathodic reaction time tc to the anodic reaction time ta (tc/ta) in the aluminum sheet is 1 to 20; the ratio between the amount of electricity Qc, when the aluminum sheet serves as an anode, and the amount of energy Qa, when it serves as an anode, (Qc/Qa) is from 0.3 to 20; and the anodic reaction time ta is from 5 to 1000 ms. The tc/ta ratio is primarily from 2.5 to 15. The Qc/Qa ratio is primarily from 2.5 to 15. The current density as a peak value in the trapezoidal waveform is preferably from 10 to 200 A/dm2 for both the Ia values on the anode cycle side and the Ic value on the cathode cycle side. The Ic/Ia ratio is preferably in the range 0.3 to 20. The total amount of energy supplied to the anodic reaction of the aluminum sheet until the end of the electrochemical granulation treatment is preferably from 25 to 1000 C/ dm2.
[00193] In the practice of the invention, any known electrolytic cell that is used in surface treatment, including vertical, flat and radial type electrolytic cells, can be used to perform the electrochemical granulation treatment using alternating current. A type of radial electrolytic cell, such as that described in JP 5-195300 A, is especially preferred.
[00194] An apparatus shown in FIG. 5 can be used for the treatment of electrochemical granulation using alternating current.
[00195] FIG. 5 is a side view of a radial electrolytic cell that can be used in the treatment of electrochemical granulation with alternating current in the method of producing the lithographic printing plate holder of the invention.
[00196] FIG. 5 shows the main electrolytic cell 50, an AC power source 51, a radial drum roller 52, main electrodes 53a and 53b, a solution feed inlet 54, an electrolytic solution 55, a slit 56, an electrolyte solution channel 57, auxiliary anodes 58, an auxiliary anode cell 60 and an aluminum plate W. When two or more electrolytic cells are used, electrolysis can be carried out under the same or different conditions.
[00197] The aluminum plate W is wound around the radial drum roller 52 which will be immersed in the electrolytic solution within the main electrolytic cell 50 and undergoes electrolysis by the main electrodes 53a and 53b connected to the AC power source 51 as it passes. . Electrolyte solution 55 is fed from solution feed inlet 54 through slit 56 to electrolyte solution channel 57 between radial drum roller 52 and main electrodes 53a and 53b. The aluminum plate W treated in the main electrolytic cell 50 then undergoes electrolysis in the auxiliary anode cell 60. In the auxiliary anode cell 60, the auxiliary anodes 58 are disposed in a face-to-face relationship with the aluminum plate W of so that the electrolytic solution 55 flows through the space between the auxiliary anodes 58 and the aluminum plate W.
[00198] On the other hand, electrochemical granulation treatments (first and second electrochemical granulation treatments) can be performed by a method in which the aluminum sheet is electrochemically granulated by applying direct current between the aluminum sheet and the electrodes opposite the same. DRYING STAGE
[00199] After the lithographic printing plate support is obtained by the steps described above, a treatment for drying the surface of the support for the lithographic printing plate (drying step) is preferably carried out before providing a layer of image recording to be described later.
[00200] The drying is carried out, preferably, after the support, which has undergone the last surface treatment, is rinsed with water and the water is removed with calender rollers. Specific conditions are not particularly limited, but the surface of the lithographic printing plate holder is preferably dried by means of hot air (50 to 200°C) or natural air. PRECURSOR OF LITHOGRAPHIC PRINTING PLATE
[00201] The precursor of the lithographic printing plate of the invention can be obtained by forming an image recording layer, such as a photosensitive layer or a thermosensitive layer exemplified below, on the support for the lithographic printing plate of the invention. The type of image recording layer is not particularly limited, but the conventional positive type, conventional negative type, photopolymer type (photosensitive composition of the photopolymer type), thermal positive type, thermal negative type and the untreated type with press development ( on-press developable nontreatment) as described in paragraphs [0042] to [0198] of JP 2003-1956 a are preferably used.
[00202] A preferred image recording layer is described in detail below. IMAGE RECORDING LAYER
[00203] An example of the image recording layer that can be used preferably in the precursor of the lithographic printing plate of the invention includes one that can be removed by printing ink and/or wetting solution. More specifically, the image recording layer is preferably one which includes an infrared absorber, a polymerization initiator and a polymerizable compound and which is capable of recording upon exposure to infrared light. Furthermore, the image recording layer can be one that includes thermoplastic polymer particles and an infrared absorber and is capable of recording by exposure to infrared light, or it can also include a polyglycerol compound.
[00204] In the forerunner of the lithographic printing plate of the invention, irradiation with infrared light cures the exposed portions of the image recording layer to form the hydrophobic (lipophilic) regions, whereas at the beginning of printing, the unexposed portions are readily removed from the support by the dampening solution, paint or an emulsion of paint and dampening solution.
[00205] The constituents of the image recording layer are described below. FIRST CONFIGURATION: IMAGE RECORDING LAYER INCLUDING INFRARED ABSORBER, POLYMERIZATION INITIATOR AND POLYMERIZABLE COMPOUND CAPABLE OF RECORDING BY EXPOSURE TO INFRARED LIGHT INFRARED ABSORBER
[00206] In cases where an image is formed on the precursor of the lithographic printing plate of the invention, by using an infrared laser emitting laser at 760 to 1,200 nm as the light source, an infrared absorber is commonly used.
[00207] The infrared absorber has the function of converting the absorbed infrared light into heat and, as being excited by the infrared light, making the transfer of electrons/energy to the polymerization initiator (radical generator) to be described below.
[00208] The infrared absorber that can be used in the invention is a dye or pigment that has an absorption maximum in the wavelength range of 760 to 1200 nm.
Dyes that can be used include commercial dyes and known dyes that are mentioned in the technical literature, such as "Senryo Binran" (Handbook of Dyes) (The Society of Synthetic Organic Chemistry, Japan, 1970).
Illustrative examples of suitable dyes include azo dyes, metal complexes of azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, aquarium dyes, pyrylthiolate salts and metal complexes. For example, the dyes described in paragraphs [0096] to [0107] of JP 2009-255434 A can be used to advantage.
[00211] On the other hand, the pigments described, for example, in paragraphs [0108] to [0112] of document JP 2009-255434 A can be used. POLYMERIZATION INITIATOR
[00212] Examples of polymerization initiators that can be used are compounds that generate a radical under light or heat energy or both, and initiate or promote the polymerization of a compound that has a polymerizable unsaturated group. In the invention, compounds which generate a radical under the action of heat (thermal radical generators) are preferably used.
[00213] Known thermal polymerization initiators are compounds which have a bond with low bond dissociation energy and photopolymerization initiators can be used as polymerization initiator.
[00214] For example, the polymerization initiators described in paragraphs [0115] to [0141] of JP 2009-255434 A can be used.
[00215] Onium salts can be used as polymerization initiators, and oxime ester compounds, diazonium salts, sulphonium salts, and iodonium salts are preferred in terms of reactivity and stability.
[00216] These polymerization initiators can be added in an amount of 0.1 to 50% by weight, preferably 0.5 to 30% by weight and preferably 1 to 20% by weight relative to the total solids which make up the image recording layer. Excellent sensitivity and high skim resistance on non-image areas during printing are achieved when the polymerization initiator content is within the range defined above. POLYMERIZABLE COMPOUND
[00217] Polymerizable compounds are addition polymerizable compounds that have at least one ethylenically unsaturated double bond, and are selected from compounds with at least one, and preferably two or more, end-bonds ethylenically unsaturated. In the present invention, use can be made of any addition polymerizable compound known in the state of the art, without special limitation.
[00218] For example, the polymerizable compounds described in paragraphs [0142] to [0163] of JP 2009-255434 A can be used.
[00219] The urethane-type addition polymerizable compounds, produced through the addition reaction between an isocyanate group and a hydroxyl group, are also suitable. Specific examples include vinylurethane compounds having two or more polymerizable vinyl groups in the molecule, which are obtained by adding a hydroxyl group-containing vinyl monomer of general formula (A) below to polyisocyanate compounds having two or more groups of isocyanate in the molecule mentioned in JP 4841708 B:
[00220] CH2 = C(R4)COOCH2CH(R5)OH (A) (wherein R4and R5are H or CH3).
[00221] The polymerizable compound is used in an amount, preferably, from 5 to 80% by weight, and primarily from 25 to 75% by weight with respect to the non-volatile ingredients of the image recording layer. These polymerizable addition compounds can be used alone or in combination with two or more of these. BINDING POLYMER
[00222] In the practice of the invention, a binder polymer can be used in the image recording layer in order to improve the film forming properties of the image recording layer.
[00223] Conventionally known binder polymers can be used without any particular limitation, and there is a preference to use those polymers that have film-forming properties. Examples of such polymer binders include acrylic resins, polyvinyl acetal resins, polyurethane resins, polyurea resins, polyimide resins, polyamide resins, epoxy resins, methacrylate resins, polystyrene resins, phenolic type resins novolac, polyester resins, synthetic rubbers and natural rubbers.
[00224] The cross-linking ability can be transmitted to the binder polymer in order to increase the film strength in the image areas. To impart this cross-linking ability to the binder polymer, a cross-linkable functional group, such as an ethylenically unsaturated bond, can be introduced into the main chain or side chain of the polymer. Crosslinkable functional groups can be introduced by copolymerization.
[00225] The binder polymers described in paragraphs [0165] to [0172] of JP 2009-255434 A, can also be used.
[00226] The binder polymer content is from 5 to 90% by weight, preferably from 5 to 80% by weight and primarily from 10 to 70% by weight based on the total solids in the image recording layer. High strength in image areas and good imaging properties are obtained when the binder polymer content is within the range defined above.
[00227] The polymerizable compound and the binder polymer are preferably used in a weight ratio of 0.5/1 to 4/1. SURFACE-ACTIVE
[00228] A surface-active agent is preferably used in the image recording layer, in order to promote the development ability in the press at the beginning of printing, and to improve the condition of the coating surface.
[00229] Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and fluorinated surfactants.
[00230] For example, the surfactants disclosed in paragraphs [0175] to [0179] of JP 2009-255.434 A can be used.
[00231] A single surfactant or a combination of two or more surfactants can be used.
[00232] The surfactant content is preferably from 0.001 to 10% by weight, and preferably from 0.01 to 5% by weight relative to the total solids in the image recording layer.
[00233] Various other compounds besides those mentioned above can optionally be added to the image recording layer. For example, the compounds disclosed in paragraphs [0181] to [0190] of JP 2009-255434 A, such as dyes, printing agents, polymerization inhibitors, higher fatty acid derivatives, plasticizers, fine inorganic particles and compounds low molecular weight hydrophilics can be used.
[00234] An embodiment other than the one described above is also possible, in which a photosensitive composition of the photopolymer type containing an addition polymerizable compound, a photopolymerization initiator and a binder polymer can be used to prepare the image recording layer.
Preferred addition polymerizable compounds include compounds containing an ethylenically unsaturated bond which are addition polymerizable. Compounds containing ethylenically unsaturated bonds are those compounds which have an ethylenically unsaturated terminal bond.
[00236] The light curing initiator can be any one of several light curing initiators or any other system of two or more light curing initiators (photoinitiating system) that is suitably selected according to the wavelength of the light source to be used . SECOND CONFIGURATION: IMAGE RECORDING LAYER INCLUDING THERMOPLASTIC POLYMER PARTICLES AND INFRARED ABSORBER CAPABLE OF RECORDING BY EXPOSURE TO INFRARED LIGHT THERMOPLASTIC POLYMER PARTICLES
[00237] The thermoplastic polymer particles have an average particle size preferably from 45 nm to 63 nm, preferably from 45 nm to 60 nm, more preferably from 45 nm to 59 nm, particularly preferably from 45 nm to 55 nm and, primarily, from 48 nm to 52 nm. In the present description, the particle size is the particle diameter that is determined by photon correlation spectrometry, which is also known as quasi-elastic light scattering or dynamic light scattering. This method is useful for measuring particle size. The measured particle size values matched well with the particle size as determined by transmission electron microscopy (TEM) as reported by Stanley D. Duke et al. in "Calibration of Spherical Particles by Light Scattering" in Technical Note-002B, May 15, 2000 (revised January 3, 2000 from an article published in the journal Particulate Science and Technology 7, pp. 223 - 228 ( 1989)).
[00238] The amount of thermoplastic polymer particles contained in the image recording layer is preferably from 70% by weight to 85% by weight and primarily from 75% by weight to 85% by weight. The weight percentage of the thermoplastic polymer particles is determined relative to the weight of all ingredients in the image recording layer.
Preferred examples of thermoplastic polymer particles include polyethylene, poly(vinyl chloride), polymethyl(meth)acrylate, polyethyl(meth)acrylate, polyvinylidene chloride, poly(meth)acrylonitrile, polyvinylcarbazole, polystyrene and copolymers of the same. According to a preferred embodiment, the thermoplastic polymer particles include polystyrene or a derivative thereof, a mixture of polystyrene and poly(meth)acrylonitrile, or derivatives thereof, or a copolymer of polystyrene and poly(meth)acrylonitrile , or derivatives thereof. The copolymer can include at least 50% by weight of polystyrene and preferably at least 65% by weight of polystyrene. In order to obtain acceptable resistance to organic chemicals such as hydrocarbons, the thermoplastic polymer particles preferably comprise at least 5% by weight of nitrogen-containing units, as described in EP 1 219 416, and primarily at least 30% by weight of nitrogen-containing units such as (meth)acrylonitrile. According to the most preferred embodiment, the thermoplastic polymer particles essentially consist of styrene and acrylonitrile units in a weight ratio between 1:1 and 5:1 (styrene:acrylonitrile), for example, in a ratio of 2 :1.
[00240] The thermoplastic polymer particles preferably have a weight average molecular weight of 5,000 to 1,000,000 g/mol.
[00241] (INFRARED ABSORBER)
[00242] The concentration of the infrared absorber in the image recording layer is preferably at least 6% by weight, and preferably at least 8% by weight relative to the weight of all ingredients in the recording layer. Image. Preferred IR absorbing compounds are cyanine dyes or pigments such as merocyanine, indoaniline, oxonol, pyrilium, squaryl such as carbon black. Examples of suitable infrared absorbers are described, for example, in EP 8 233 27, EP 978376, EP 1 029 667, EP 1 053 868, EP 1 093 934, WO 97/39894 and WO 00/29214. Preferred compounds are the following cyanine dyes.
[00243] Chemical Formula 1


[00244] The image recording layer may contain still other ingredients. Examples of Additional Ingredients include binders, polymer particles such as matting agents and spacers, surfactants such as perfluorinated surfactants, silicon or titanium dioxide particles, development inhibitors, development accelerators, dyes and other known ingredients . In particular, the addition of dyes such as dyes or pigments which provide a visible color to the image recording layer and which remain in exposed areas of the image recording layer after the processing step is advantageous. Thus, areas of the image that are not removed during the processing step form a visible image on the printing plate, and evaluation of the printing plate already developed at this stage becomes feasible. Typical examples of such contrast dyes are amino-substituted tri- or diarylmethane dyes, for example, crystal violet, methyl violet, victoria pure blue, flexoblau 630, basonylblau 640, auramine, and malachite green. The dyes which are discussed in depth in the detailed description of EP 400706 are also suitable contrast dyes.
[00245] A hydrophilic resin can be added to the image recording layer to improve the press developability and film strength of the image recording layer. A hydrophilic resin, which is not three-dimensionally crosslinked, is preferred in terms of press developability.
Preferred hydrophilic resins include those having hydrophilic groups, such as hydroxyl, carboxyl, hydroxyethyl, hydroxypropyl, amino, aminoethyl, aminopropyl and carboxymethyl groups.
[00247] Specific examples of hydrophilic resin include gum arabic, casein, gelatin, soy gum, starch and its derivatives, cellulose derivatives such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, carboxymethylcellulose, and the salts derived therefrom, acetate of cellulose, alginic acid, and the alkali metal salts thereof, alkaline earth metal salts or ammonium salts, water soluble urethane resins, water soluble polyester resins, maleic acid - vinyl acetate copolymers, copolymers of styrene - maleic acid, polyacrylic acids and the salts derived therefrom, polymethacrylic acids and the salts derived therefrom, hydroxyethyl methacrylate homopolymers and copolymers, hydroxyethyl acrylate homopolymers and copolymers, hydroxypropyl methacrylate homopolymers and copolymers, homopolymers and hydroxypropyl acrylate copolymers, hydroxybutyl methacrylate homopolymers and copolymers, homopolymer and copolymers of hydroxybutyl acrylate, polyethylene oxides, poly(propylene oxides), polyvinyl alcohols (PVAs), hydrolyzed polyvinyl acetates having a degree of hydrolysis of at least 60% and preferably at least 80% , polyvinyl formal, polyvinyl butyral, polyvinylpyrrolidone, acrylamide homopolymers and copolymers, methacrylamide homopolymers and copolymers, N-methylolacrylamide homopolymers and copolymers, and 2-acrylamide-2-methylpropanesulfonic acid and the salts derived therefrom.
[00248] The hydrophilic resin is preferably added to the image recording layer in an amount of 2 to 40% by weight and more preferably 3 to 30% by weight of the solids in the image recording layer. Excellent on-press developability and longer print life are achieved when the add-on amount is within this range.
[00249] A surfactant, such as the fluorinated surfactant described in JP 62-170950 A, can be added to the image recording layer-forming coating liquid in order to enhance the properties of coating and have a good coating surface. The amount of addition is preferably from 0.01 to 1% by weight of the image recording layer solids.
[00250] The image recording layer, containing the ingredients described above, can be exposed imagewise directly to heat, for example, by a thermal printhead or indirectly by infrared light, preferably near infrared light. Infrared light is converted to heat by the infrared absorber as described above. The thermosensitive lithographic printing plate precursor used in the present invention is preferably not sensitive to visible light. Primarily, the image recording layer is not sensitive to ambient light (ie, visible light (400 to 750 nm) and near UV light (300 to 400 nm) at an intensity and exposure time that match normal conditions work), so materials are handled without the need for safe ambient light. FORMATION OF THE IMAGE RECORDING LAYER
[00251] The image recording layer is formed by dispersing or dissolving the necessary ingredients described above in a solvent so as to prepare a coating liquid and therefore apply the prepared coating liquid to the support. Examples of the solvent that can be used include, but are not limited to, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate , 1 methoxy-2-propyl acetate and water.
[00252] These solvents can be used alone or as mixtures of two or more of them. The coating liquid preferably has a solids concentration of 1 to 50% by weight.
[00253] The image recording layer coating weight (in terms of solids) on the lithographic printing plate holder, obtained after coating and drying, varies depending on the intended application; although an amount of 0.3 to 3.0 g/m2 is generally preferred. If the image recording layer coating weight is within this range, the image recording layer films have good sensitivity and good properties.
[00254] Examples of suitable coating methods include rod coating, spin coating, spray coating, curtain coating, dip coating, air blade coating, blade coating and roller coating. UNDERLAYER
[00255] In the forerunner of the lithographic printing plate of the invention, it is desirable that a sublayer be provided between the image recording layer and the support for the lithographic printing plate.
[00256] The sublayer preferably contains a polymer with an adsorbable group to the substrate, a polymerizable group and a hydrophilic group.
[00257] An example of the polymer with an adsorbable group to the substrate, a polymerizable group and a hydrophilic group includes a polymeric subcoat resin obtained by copolymerizing a monomer containing an adsorbable group, a monomer containing a hydrophilic group, and a monomer containing a polymerizable reactive group (crosslinkable group).
[00258] The monomers described in paragraphs [0197] to [0210] of JP 2009-255434 A, for example, can be used for the polymeric subcoat resin.
[00259] An embodiment in which the surface of the support is subjected to a predetermined treatment to form the undercoat (in particular, a hydrophilic undercoat) is also preferred.
[00260] For example, the surface of aluminum oxide can be silicized by treating the surface with a sodium silicate solution at an elevated temperature of, for example, 95 °C. Alternatively, a phosphate treatment can be applied which involves treating the surface of the aluminum oxide with a phosphate solution which may further contain an inorganic fluoride. In addition, the surface of the aluminum oxide can be washed with an organic acid and/or salt thereof, for example, carboxylic acids, hydrocarboxylic acids, sulfonic acids or phosphonic acids or salts derived therefrom, for example, succinates, phosphates, phosphonates, sulfates and sulfonates. Citric acid or citrate is preferred. This treatment can be carried out at room temperature or at a slightly elevated temperature from about 30°C to about 50°C. An even more interesting treatment involves washing the surface of the aluminum oxide with a bicarbonate solution. In addition, aluminum oxide surface can be treated with polyvinyl phosphonic acid, polyvinyl-methyl phosphonic acid, polyvinyl alcohol phosphoric acid esters, polyvinyl sulfonic acid, polyvinyl benzenesulfonic acid, polyvinyl alcohol sulfuric acid esters, and acetals of polyvinyl alcohols formed by reaction with a sulphonated aliphatic aldehyde. It is further evident that one or more of these post-treatments can be carried out alone or in combination. More detailed descriptions of these treatments are given in GB 1084070, DE 4423140, DE 4417907, EP 659909, EP 537633, DE 4001466, EP 292801, EP 291760 and US 4,458,005.
[00261] Another embodiment of the sublayer includes a cross-linked hydrophilic layer obtained from a cross-linked hydrophilic binder with a hardener, such as formaldehyde, glyoxal, polyisocyanate, or hydrolyzed tetra-alkyl orthosilicate. The thickness of the crosslinked hydrophilic layer can range from 0.2 to 25 µm and is preferably from 1 to 10 µm. The hydrophilic binder for use in the crosslinked hydrophilic layer is, for example, a hydrophilic (co)polymer such as the homopolymers and copolymers of vinyl alcohol, acrylamide, methylol acrylamide, methylol-methacrylamide, acrylic acid, methacrylic acid and hydroxyethyl acrylate, hydroxyethyl methacrylate, or maleic anhydride/vinyl methyl ether copolymers. The hydrophilicity of the (co)polymer or mixture of (co)polymers used is preferably equal to or greater than the hydrophilicity of the hydrolyzed polyvinyl acetate to at least an extent of 60% by weight, preferably 80% by Weight. The amount of hardener, in particular tetraalkyl orthosilicate, is preferably at least 0.2 parts by weight, more preferably 0.5 to 5 parts by weight, and preferably 1 to 3 parts by weight. weight, per part by weight of the hydrophilic binder.
[00262] Various known methods can be used to apply the coating liquid forming the undercoat to the support, containing the constituents of the undercoat. Examples of suitable application methods include rod coating, spin coating, spray coating, curtain coating, dip coating, air blade coating, blade coating and roller coating.
[00263] The weight of the coating (solids) of the undercoat is preferably from 0.1 to 100 mg/m2 and preferably from 1 to 50 mg/m2. PROTECTIVE LAYER
[00264] In the forerunner of the lithographic printing plate of the invention, the image recording layer may optionally have a protective layer formed over it in order to prevent scratches and other damage to the image recording layer, to serve as a barrier of oxygen, and to avoid ablation during exposure with a high-intensity laser.
[00265] The protective layer has been well studied and is described in detail, for example, in documents US 3,4583.11 and JP 55-49729 B.
[00266] Examples of materials that can be used in the protective layer include those described, for example, in paragraphs [0213] and [0227] of JP 2009-255434 A (for example, water-soluble polymeric compounds and layered inorganic compounds ).
[00267] The protective layer-forming coating liquid, then prepared, is applied over the image recording layer provided on the support and dried to form the protective layer. The coating solvent can be suitably chosen together with the binder, but distilled water and purified water are preferably used in cases where a water-soluble polymer is used. Examples of the coating method used to form the protective layer include, but are not limited to, blade coating, air blade coating, emboss coating, roller coating, spray coating, dip coating and bar coating.
[00268] The weight of the coating after drying the protective layer is preferably from 0.01 to 10 g/m2, preferably from 0.02 to 3 g/m2, and primarily from 0.02 to 1 g/m m2.
[00269] The precursor of the lithographic printing plate of the invention having the image recording layer as described above, features excellent ink scavenging ability after printing has stopped, longer print life, excellent strength to dot skimming and excellent resistance to white spot formation on the lithographic printing plate formed therefrom, and exhibits better press development capability in the case of a press development type. EXAMPLES
[00270] EXAMPLE A PRODUCTION OF SUPPORT FOR LITHOGRAPHIC PRINTING PLATE
[00271] The aluminum alloy plates of the composition shown in Table A, with a thickness of 0.3 mm, were subjected to treatments (a) to (n), described below, for the production of supports for printing plate lithographic. The washing treatment was carried out between every two treatment steps and the remaining water after the washing treatment was removed with calender rollers.
[00272] Table A presents the composition of the aluminum alloy sheets used in Examples 1 to 30 and Comparative Examples 1 to 22 which will be described below. In Table A, the values in the ingredient columns are given in percent by weight, Al being the balance.
[00273] TABLE 1 Table A

[00274] (a) Mechanical granulation treatment (brush granulation)
[00275] Mechanical granulation treatment was carried out with brushes with rotating bristle bundles of an apparatus as shown in FIG. 6, while an abrasive slurry in the form of a suspension of pumice stone (specific gravity 1.1 g/cm3) is fed onto the surface of the aluminum sheet. FIG. 6 shows an aluminum sheet 1, roller-type brushes (brushes with bristle bundles in Examples) 2 and 4, an abrasive paste 3, and support rollers 5, 6, 7 and 8.
[00276] The mechanical granulation treatment was carried out using an abrasive having an average diameter of 30 μm with four rotating brushes at 250 rpm. The bristle brushes were made of 6/10 nylon and had a bristle diameter of 0.3 mm and a bristle length of 50 mm. Each brush was constructed with a 300 mm diameter stainless steel cylinder, in which holes were formed and the bristles were neatly arranged. Two support rollers (200 mm in diameter) were provided below each brush with bristle bundles and spaced 300 mm apart. The brushes with bristle bundles were pressed against the aluminum plate until the load on the drive motor, which rotates the brushes, was greater than 10 kW than before the brushes with bristle bundles were pressed against the plate . The direction the brushes were rotated was the same direction the aluminum sheet was moved.
[00277] (b) Alkaline pickling treatment
[00278] The chemical pickling treatment was carried out using a spray line to spray the aluminum sheet obtained, as described above, with an aqueous solution having a sodium hydroxide concentration at 26% by weight, a concentration of aluminum ions at 6.5% by weight, and a temperature of 70 °C. The plate was then washed by spraying with water. The amount of dissolved aluminum was 10 g/m2.
[00279] (c) Demutting treatment in acidic aqueous solution
[00280] Then, the desmutting treatment was carried out in an aqueous solution of nitric acid. Nitric acid, used in the subsequent electrochemical granulation treatment step, was used in the aqueous solution of nitric acid in the desmutting treatment. The temperature of the solution was 35 °C. The demuting treatment was carried out by spraying the plate with the demuting solution for 3 seconds.
[00281] (d) Electrochemical granulation treatment
[00282] The electrochemical granulation treatment was consecutively carried out by electrolysis of nitric acid using an AC voltage of 60 Hz. Aluminum nitrate was added to an aqueous solution containing 10.4 g/L of nitric acid at a temperature of 35 °C to prepare an electrolyte solution with an adjusted aluminum ion concentration of 4.5 g/L, and the electrolyte solution was used in the electrochemical granulation treatment. The waveform of the AC power source is shown in FIG. 4. The electrochemical granulation treatment was carried out using an alternating current of a trapezoidal waveform, with a time tp, until the current reached a peak from zero of 0.8 ms and a duty ratio of 1:1 , and using a carbon electrode as the counter electrode. Ferrite was used for the auxiliary anodes. An electrolytic cell, of the type shown in FIG. 5, was used. The current density, as a peak current value, was 30 A/dm2. Of the current flowing from the power source, 5% was diverted to the auxiliary anodes. The amount of electricity (C/dm2), as the total amount of energy when the aluminum sheet serves as an anode, was 185 C/dm2. The substrate was then spray washed with water.
[00283] (e) Alkaline pickling treatment
[00284] The chemical pickling treatment was carried out using a spray line to spray the aluminum sheet obtained, as described above, with an aqueous solution having a concentration of sodium hydroxide at 5% by weight, a concentration of aluminum ions at 0.5% by weight, and a temperature of 50°C. The plate was then washed by spraying with water. The amount of dissolved aluminum was 0.5 g/m2.
[00285] (f) Demutting treatment in acidic aqueous solution
[00286] Then, the desmutting treatment was carried out in an aqueous solution of sulfuric acid. The aqueous solution of sulfuric acid used in the demuting treatment was a solution having a sulfuric acid concentration of 170 g/L and an aluminum ion concentration of 5 g/L. The temperature of the solution was 60°C. The demuting treatment was carried out by spraying the plate with the demuting solution for 3 seconds.
[00287] (g) Electrochemical granulation treatment
[00288] The electrochemical granulation treatment was consecutively performed by electrolysis of hydrochloric acid using an AC voltage of 60 Hz. Aluminum chloride was added to an aqueous solution containing 6.2 g/L of hydrochloric acid at a temperature of 35 °C to prepare an electrolyte solution with an adjusted aluminum ion concentration of 4.5 g/L, and the electrolyte solution was used in the electrochemical granulation treatment. The waveform of the AC power source is shown in FIG. 4. The electrochemical granulation treatment was carried out using an alternating current of a trapezoidal waveform, with a time tp, until the current reached a peak from zero of 0.8 ms and a duty ratio of 1:1 , and using a carbon electrode as the counter electrode. Ferrite was used for the auxiliary anodes. An electrolytic cell, of the type shown in FIG. 5, was used. The current density at peak current was 25 A/dm2. The amount of electricity (C/dm2) in the hydrochloric acid electrolysis, which is the total amount of electricity when the aluminum plate serves as an anode, was 63 C/dm2. The substrate was then spray washed with water.
[00289] (h) Alkaline pickling treatment
[00290] The chemical pickling treatment was carried out using a spray line to spray the aluminum sheet obtained, as described above, with an aqueous solution having a concentration of sodium hydroxide at 5% by weight, a concentration of aluminum ions at 0.5% by weight, and a temperature of 50°C. The plate was then washed by spraying with water. The amount of dissolved aluminum was 0.1 g/m2.
[00291] (i) Treatment of demutting in acidic aqueous solution
[00292] Then, the desmutting treatment was carried out in an aqueous solution of sulfuric acid. More specifically, an aqueous sulfuric acid solution for use in the anodizing treatment step (aqueous solution containing 170 g/L of sulfuric acid and 5 g/L of aluminum ions dissolved therein) was used to carry out the demutting treatment to a solution temperature of 35 °C for 4 seconds. The desmutting treatment was carried out by spraying the sheet with the desmutting solution for 3 seconds
[00293] (j) First anodizing treatment
[00294] The first anodizing treatment was performed by DC electrolysis using a structure anodizing apparatus, as shown in FIG. 7. The anodizing treatment was carried out under the conditions shown in Table 1 in order to form the anodized film with a specified film thickness. The electrolyte solution used is an aqueous solution containing the ingredients shown in Table 1.
[00295] In an anodizing apparatus 610, an aluminum plate 616 is transported, as shown by the arrows in FIG. 7. Aluminum sheet 616 is positively (+) charged by an electrode of power source 620 in a cell of power source 612 containing an electrolyte solution 618. Aluminum sheet 616 is then transported upwards by disposed roller 622 in the power source cell 612, turned down by calender rolls 624 and conveyed to an electrolytic cell 614, containing an electrolytic solution 626, to be then turned in a horizontal direction by a roller 628. Then the aluminum sheet 616 is negatively (-) charged by an electrolytic electrode 630 to form an anodized film on the surface of the sheet. The aluminum sheet 616, emerging from the electrolytic cell 614, is then transported to the section for the subsequent step. In anodizing apparatus 610, roll 622, calender rolls 624 and roll 628 constitute direction-changing means, and aluminum sheet 616 is transported from power source cell 612 to electrolytic cell 614, mountain-shaped and an inverted U-shape by means of these rollers 622, 624 and 628. Power source electrode 620 and electrolytic electrode 630 are connected to a DC power source 634.
[00296] (k) Treatment for pore enlargement
[00297] The pore widening treatment was carried out by immersing the anodized aluminum sheet in an aqueous solution having a sodium hydroxide concentration at 5% by weight, a concentration of aluminum ions at 0.5% by weight, and a temperature of 35°C under the conditions shown in Table 1. The substrate was then spray washed with water.
[00298] (l) Second anodizing treatment
[00299] The second anodizing treatment was performed by DC electrolysis using a structure anodizing apparatus, as shown in FIG. 7. The anodizing treatment was carried out under the conditions shown in Table 1 in order to form the anodized film with a specified film thickness.
[00300] The electrolytic solution used is an aqueous solution containing the ingredients shown in Table 1.
[00301] (m) Third anodizing treatment
[00302] The third anodizing treatment was performed by DC electrolysis using a structure anodizing apparatus, as shown in FIG. 7. The anodizing treatment was carried out under the conditions shown in Table 1 in order to form the anodized film with a specified film thickness.
[00303] The electrolytic solution used is an aqueous solution containing the ingredients shown in Table 1.
[00304] (n) In order to ensure hydrophilicity in non-imaging areas, the silicate treatment was carried out by immersing the sheet in an aqueous solution containing 2.5% by weight of sodium silicate No. 3 to 50 °C for 7 seconds. The amount of silicon deposited was 8.5 mg/m2. The substrate was then spray washed with water.
[00305] The average diameter on the surface of the anodized film of the large diameter portions in the anodized film containing the micropores, obtained after the second step of anodizing treatment (or the third step of anodizing treatment) (average diameter of the surface layer), the average diameter of the large diameter portions at the communicating level (average diameter of the lower part), the average diameter of the small diameter portions at the communicating level (diameter of the small diameter portion), the average depths of the large diameter portions and of small diameter portions, the thickness of the anodized film between the undersides of the small diameter portions and the surface of the aluminum sheet (thickness of the barrier layer), the shapes of the large diameter portions and the small diameter portions, the density of small-diameter parts and the ratio (diameter of small-diameter portion/diameter of large-diameter portion) are shown in Table 2.
[00306] As for the thickness of the barrier layer, the average and the minimum value are shown. The average was obtained by measuring the thickness of the anodized film between the lower parts of the small diameter portions and the surface of the aluminum sheet, and by calculating the arithmetic mean of the measurements. In Examples 13 to 15 and 26 to 30, the average was obtained by measuring the thickness of the anodized film between the undersides of the first small diameter portions and the surface of the aluminum sheet at 50 locations, and by calculating the arithmetic average of the measurements .
[00307] The average diameters of the micropores (average diameter of the large diameter portions and the small diameter portions) were determined as follows: The anodized film, which shows the opening surfaces of the large diameter portions and those of the portions of small diameter, was observed by FE-SEM, with a magnification of 150,000X, to obtain four images (N = 4), in the four resulting images, the diameter of the micropores (large diameter portions and small diameter portions) was measured within an area of 400 x 600 nm2 and the average of the measurements was calculated. When measuring the diameter of the small diameter portions was difficult due to the great depth of the large diameter portions, the upper portion of the anodized film was cut to determine the various diameters.
[00308] The average depth of the large diameter portions was determined as follows: The cross section of the support (anodized film) was observed by FE-TEM, with a magnification of 500,000X; in the resulting image, the depth of 60 arbitrarily selected micropores (N = 60) from the surface of the communication level was measured, and the measurements were averaged. The average depth of the small diameter portions was determined as follows: The cross section of the support (anodized film) was observed by FE-SEM (at a magnification of 50,000X); in the resulting image, the depth of 25 arbitrarily selected micropores was measured, and the measurements were averaged.
[00309] The electrolytic solution used in each step is an aqueous solution containing the ingredients shown in Table 1. In Table 1, the hyphen (-) indicates that the treatment in question was not carried out. In Table 1, "Conc." refers to a concentration (g/L) of each of the ingredients shown in the "Solution" column.
[00310] In Table 2, the "density of the communicating portion" refers to a density of the small diameter portions in the cross section of the anodized film at the communication level. The "surface area increase rate" is a value obtained from equation (A) described above.
[00311] In Examples 13 to 15 and 26 to 30, the column "mean depth (nm)" of the small diameter portions in Table 2 shows the average depth of the second small diameter portions on the left and that of the first small diameter portions on the right.
[00312] In Examples 13 to 15 and 26 to 30, the column "communicating portion density" of the small diameter portions in Table 2 shows the density of the first small diameter portions in parentheses along with the density of the small diameter portions.
[00313] In Examples 13 to 15 and 26 to 30, the average diameter of the first small diameter portions at a position between the bottoms of the second small diameter portions and the bottoms of the first small diameter portions was about 12 nm.
[00314] TABLE 2 Table 1 (Part 1)


[00315] TABLE 3 Table 1 (Part 2)


[00316] TABLE 4 Table 2 (Part 1)


[00317] TABLE 5 Table . 2 (Part 2)


[00318] In Examples 1 to 30, micropores having the specified mean diameter and mean depth were formed in the anodized aluminum film. PRODUCTION OF THE PRECURSOR OF THE LITHOGRAPHIC PRINT PLATE (PART 1)
[00319] An undercoating solution of the composition indicated below was applied on each support for lithographic printing plate, manufactured as described above, with a coating weight after drying of 28 mg/m2, to thereby form a underlayer.
[00320] UNDERLAYER COATING LIQUID * Compound of sublayer (1) of the structure shown below - 0.18 g * Hydroxyethyl iminodiacetic acid - 0.10 g * Methanol - 55.24 g * Water - 6.15 g
[00321] Chemical Formula 2
Subcoating Compound (1)
[00322] Then, an image recording layer forming coating liquid was applied over the then formed sublayer, through the bar coating, and dried in an oven at 100 °C for 60 seconds to form an image recording layer. picture having a coating weight after drying of 1.3 g/m2.
[00323] The coating liquid forming the image recording layer was obtained by mixing, with stirring, the photosensitive solution with the microgel solution immediately before use. PHOTOSENSITIVE SOLUTION * Binder polymer (1) (from the structure below) - 0.24 g * Infrared absorber (1) (from the structure below) - 0.030 g * Polymerization initiator radical (1) (from the structure below) - 0.162 g * Polymerizable compound, tris(acryloyloxyethyl) isocyanurate (NK Ester A-9300 available from Shin-Nakamura Chemical Corporation) - 0.192 g * Low molecular weight hydrophilic compound, tris (2-hydroxyethyl) isocyanurate - 0.062 g * Low molecular weight hydrophilic compound (1) (from the structure below) - 0.052 g * Ink receptivity amplifier * Phosphonium Compound (1) (from the structure below) - 0.055 g * Ink receptivity amplifier Benzyl-dimethyl-octyl ammonium salt • PF6 - 0.018 g Betaine derivative (C-1), 0.010 g * Fluorinated surfactant (1) (weight average molecular weight, 10,000) (of the structure below) - 0.008 g * Methyl ethyl ketone - 1.091 g * 1-methoxy-2-propanol - 8.609 g
[00324] MICROGEL SOLUTION * Microgel (1) - 2.640 g * Distilled water - 2.425 g
[00325] The binder polymer (1), the infrared absorber (1), the polymerization initiator radical (1), the phosphonium compound (1), the low molecular weight hydrophilic compound (1) and the fluorinated surfactant ( 1) have the structures represented by the following formulas:
[00326] Chemical Formula 3
Binder polymer (1)
[00327] Chemical Formula 4

The microgel (1) was synthesized in the following manner. MICROGEL SYNTHESIS (1)
[00329] For the oil phase component, 10g of a trimethylolpropane adduct with xylene diisocyanate (Takenate D-110N available from Takeda Mitsui Chemicals, Inc.), 3.15g of pentaerythritol triacrylate (SR444 available from Nippon Kayaku Co. , Ltd.) and 0.1 g of Pionin A-41C (available from Takemoto Oil & Fat Co., Ltd.) were dissolved in 17 g of ethyl acetate. For the aqueous phase component, 40 g of a 4% by weight aqueous solution of PVA-205 was prepared. The oil phase component and the water phase component were mixed and emulsified in a homogenizer at 12,000 rpm for 10 minutes. 25 g of distilled water was added to the resulting emulsion and the mixture was stirred at room temperature for 30 minutes, then at 50°C for 3 hours. The microgel solution thus obtained was diluted with distilled water so as to have a concentration of 15% by weight of solids and be used as the microgel (1). By the light scattering method, the average microgel particle size measured was 0.2 µm.
[00330] Then, a protective layer-forming coating liquid, with its composition indicated below, was applied over the image recording layer, then formed, through the bar coating and dried in an oven at 120 °C during 60 seconds to form a protective layer with a coating weight after drying of 0.15 g/m2, thus obtaining a precursor of the lithographic printing plate. PROTECTIVE LAYER COATING LIQUID * Dispersion of a lamellar inorganic compound (1) - 1.5 g * Aqueous solution of polyvinyl alcohol at 6% by weight (CKS50; modified with sulfonic acid; degree of saponification of at least 99 mol%; degree of polymerization, 300; available from Nippon Synthetic Chemical Industry Co., Ltd.) - 0.55 g * Aqueous solution of polyvinyl alcohol at 6% by weight (PVA-405; saponification grade 81.5 mol %; degree of polymerization, 500; available from Kuraray Co., Ltd.) - 0.03 g * 1% by weight aqueous surfactant solution (EMALEX 710 available from Nihon Emulsion Co., Ltd.) - 8.60 g * Deionized water (ion exchanged water) - 6.0 g
The dispersion of an inorganic lamellar compound (1) was prepared in the following manner. PREPARATION OF INORGANIC LAMELAR COMPOUND DISPERSION (1)
An amount of 6.4 g of Somasif ME-100 synthetic mica (available from Co-Op Chemical Co., Ltd.) was added to 193.6 g of deionized water and dispersed in the water with a homogenizer to a size particle average (as measured by a laser diffraction method) of 3 µm. The resulting dispersed particles had an aspect ratio of at least 100. EVALUATION OF THE PRECURSOR OF THE LITHOGRAPHIC PRINTING PLATE PRESS DEVELOPMENT CAPACITY (On-Press Developability)
[00333] The resulting lithographic printing plate precursor was exposed by FUJIFILM Corporation's Luxel PLATESETTER T-6000III equipped with an infrared semiconductor laser at an outer drum rotational speed of 1000 rpm, a laser power of 70% and a resolution 2400 dpi. The exposed image was adjusted to contain a solid image and a 50% halftone chart of an FM screen with 20 µm dots.
[00334] The resulting lithographic printing plate precursor after exposure was mounted without the developing process on the plate cylinder of a Lithrone 26 printing press available from Komori Corporation. Ecolity-2 (FUJIFILM Corporation)/spread water solution (a volume ratio of) 2/98 and G-Values (N) black ink were used (Dainippon Ink & Chemicals, Inc.). Wetting solution and ink were provided in the initial process of standard automatic printing on the Lithrone 26 to perform development on the press, and printing was performed with 100 sheets of Tokubishi art paper (76.5 kg) at a printing rate 10,000 sheets per hour.
[00335] On-press development capacity was evaluated as the number of sheets of printing paper required to reach the state where no ink is transferred to halftone non-image areas after the completion of press development of the unexposed areas of the 50% halftone diagram. On-press developability was rated excellent, "A" (when the number of wasted sheets was up to 15), "B" (when the number of wasted sheets was 16 to 19), "C" (when the number of wasted sheets was 20 to 30) and "D" (when the number of wasted sheets was 31 or more). The results are shown in Table 3. CAPACITY TO DISPOSE OF INK AFTER PRINTING HAS BEEN STOPPED
[00336] Once good prints were obtained after the end of development in the press, printing was stopped and the printing plate was left to rest on the printing press for 1 hour in a room at a temperature of 25 °C and with a humidity of 50%. Then, printing was resumed and the ink scavenging capability, after printing was stopped, was evaluated as the required number of wasted printing paper sheets to obtain smudge-free printing. The ink scavenging capability after printing was stopped was rated excellent, "A" (when the number of wasted sheets was up to 75), "B" (when the number of wasted sheets was 76 to 300) and "C" (when the number of wasted sheets was 301 or more). The results are shown in Table 3. PRINT LIFETIME
[00337] The development in the press was carried out on the same type of printing machine with the same procedure as above, and the printing continued ahead. Print life was evaluated by the number of prints when the decrease in density of a solid image became visually recognizable. Print life was rated "D" when the number of prints was less than 30,000, "C" when the number of prints was at least 30,000 but less than 35,000, "B" when the number of impressions was at least 35,000 but less than 37,500, and "A" when the number of impressions was 37,500 or more. The results are shown in Table 3. It is necessary for the evaluation of the results in Table 3 that "D" or "C" are not included. CAPACITY TO DISPOSE OF INK IN CONTINUOUS PRINTING
[00338] Since good prints were obtained after the end of press development, Fushion-EZ(S) ink (Dainippon Ink & Chemicals, Inc.), to which varnish was added, was applied to non- image of the lithographic printing plate. Then, printing was resumed and the ink scavenging capability in continuous printing was evaluated as the number of sheets of printing paper needed to obtain a smudge-free print. Ink scavenging capability in continuous printing was rated excellent, "A" (when the number of wasted sheets was up to 10), "B" (when the number of wasted sheets was greater than 10 but less than 20) , "C" (when the number of wasted sheets was greater than 20 but less than 30) and "D" (when the number of wasted sheets was greater than 30). The results are shown in Table 3. RISK RESISTANCE
[00339] The surface of the resulting lithographic printing plate support was subjected to a scratch test to assess the scratch resistance of the lithographic printing plate support.
The scratch test was performed using a continuous loading-type scratch strength tester (SB-53 manufactured by Shinto Scientific Co., Ltd.) which moves a continuous loading-type scratch strength tester. sapphire with a diameter of 0.4 mm at a displacement speed of 10 cm/s and a load of 100 g.
[00341] As a result, the support on which the scratches caused by the needle do not reach the surface of the aluminum alloy sheet (base) was classified as "A", that is, it has excellent scratch resistance, and the support on which the scratches reached the surface of the plate was rated "B". The lithographic printing plate holder with excellent scratch resistance at a load of 100g can eliminate the transfer of the streaks to the image recording layer when the lithographic printing plate precursor prepared from it is mounted on the cylinder plate or superimposed on another, thus reducing skimming in non-image areas. Scratch resistance is required to be rated "A" for practical use. MICROPOINTS (POINT FOAMING)
[00342] The resulting lithographic printing plate precursor was conditioned in a humid environment, together with an intercalating sheet, at 25 °C and 70% RH for 1 hour, wrapped with aluminum kraft paper and heated in an oven set to 60 °C for 10 days.
[00343] Then, the temperature was lowered until room temperature was reached. Press development was carried out on the same type of printing machine with the same procedure as described above, and 500 prints were made. The 500° print was visually checked and the number of print spots per 80 cm2 (dot skimming) with a size of at least 20 mm was counted.
[00344] Spot skimming was rated "E" when the number of spots was at least 200, "D" when the number of spots was at least 150 but less than 200, " C", when the number of spots was at least 100 but less than 150, "B" when the number of spots was at least 50 but less than 100, "A" when the number of spots was at least 30 but less than 50, and "AA" when the number of spots was less than 30.
[00345] Preferably, spot skimming resistance should not be rated "E" for practical use.
[00346] TABLE 6 Table 3 (Part 1)


[00347] TABLE 7 Table 3 (Part 2)


[00348] Table 3 revealed that, in the lithographic printing plates and in the lithographic printing plate precursors (Examples 1 to 30) obtained using the supports for lithographic printing plate, in which each one has an anodized aluminum film where micropores were formed with specified average diameters and average depths, the print life, the ink scavenging capability after printing was stopped, the press developing capability, the ink scavenging capability in continuous printing, the strength scratch resistance and spot skimming resistance were excellent.
[00349] The large diameter portions that make up the micropores obtained in Examples 1 to 6, 8 to 22 and 24 to 30 had an inversely conical shape (conical shape) such that the diameter increased from the surface of the anodized film towards the side of the aluminum sheet (ie, the mean diameter of the underside was greater than the mean diameter of the surface layer). The large diameter portions making up the micropores obtained in Examples 7 and 23 had a substantially straight tubular shape.
[00350] It was confirmed, from the comparison between Examples 1 and 2, that the average depth of the large diameter portions from 85 to 105 nm, provided even better effects.
[00351] It was confirmed, from the comparison between Examples 1 and 5, that the average diameter of the large diameter portions from 11 to 13 nm provided even better effects.
[00352] On the other hand, the results revealed that Comparative Examples 1 to 22, which did not meet the ratio between mean diameter and mean depth of the invention, were less effective than Examples 1 to 30.
[00353] In particular, the results revealed that Comparative Examples 9 to 12 corresponding to Examples 1, 2, 3 and 16 of Patent Literature 1 were worse as to the print life of Examples 1 to 30 described above.
[00354] The support for lithographic printing plate obtained in Examples 13 to 15 and 26 to 30 were evaluated for edge burn (burning the edges), as described below.
[00355] The results of the edge burn evaluation in Examples 13 to 15 and 26 to 30 were "A" and therefore good. EDGE BURN EVALUATION
[00356] In evaluating the edge burn, the oxygen intensity towards the width of the support, including the opposite edges, was measured in EPMA, a portion that has a higher oxygen intensity of at least 10% than in the central portion, which was defined as an edge-burned portion, and the length of the edge-burned portion toward the width was calculated.
[00357] Edge burn with a length toward width of less than 5 mm was rated "A" and one with a length of at least 5 mm was rated "B."
[00358] EXAMPLE B PRODUCTION OF THE PRECURSOR OF THE LITHOGRAPHIC PRINT PLATE (PART 2)
[00359] Each of the supports for lithographic printing plates (Examples 1 and 3, 5 and 16, and Comparative Examples 1 to 3 and 15), produced as described above, was subjected to post-treatment with a solution containing 4 g/ L of polyvinylphosphonic acid at 40°C for 10 seconds, washed with demineralized water at 20°C for 2 seconds and dried.
[00360] Next, an image recording layer forming coating liquid was applied onto the then formed substrate by bar coating and dried in an oven at 50°C for 60 seconds to form an image recording layer. picture having a coating weight after drying of 0.91 g/m2. SAN IMAGE RECORDING LAYER COATING LIQUID (styrene/acrylonitrile copolymer (50/50 molar ratio)) - 0.70 g Infrared Absorber (2) (from structure below) - 0.10 g PVA 205 (available by Kuraray Co., Ltd.) - 0.10 g Aqueous solution containing 20% by weight of Megaface F-177 (available from Dainippon Ink & Chemicals, Inc.; fluorinated surfactant) - 0.05 g
[00361] The structure of the infrared absorber (2) is shown below.
[00362] Chemical Formula 5

[00363] The evaluations described above were carried out for the resulting lithographic printing plate precursors. The results are shown in Table 4. Examples and Comparative Examples, using the lithographic printing plate holders produced in Examples 1 to 3, 5 and 16 and Comparative Examples 1 to 3 and 15, are shown as EX 1B to EX 3B , EX 5B and EX 16B and CE 1B to CE 3B and CE 15B in Table 4 below, respectively.
[00364] TABLE 8 Table 4

[00365] It has also been confirmed that in the examples using the image recording layer composed of different ingredients, the print life, the ink scavenging capability after printing has been stopped, the press development capability, the print capacity of ink elimination in continuous printing, scratch resistance and dot-skimming resistance were excellent.
[00366] LIST OF REFERENCE SIGNS 1.12 aluminum plate 2, 4 rotating brush 3, abrasive paste 5, 6, 7, 8 support rollers t anodic reaction time tc cathodic reaction time tp a period of time necessary for that the current peaks from zero Ia peak current on the anode cycle side Ic peak current on the cathode cycle side 10, 100 holder for lithographic printing plate 12 aluminum plate 14, 14a, 14b, 14c anodized film 16, 16a, 16b, 16c micropores 18, 18a large diameter portion 20 small diameter portion 50 main electrolytic cell 51 AC power source 52 Radial drum roller 53a, 53b main electrode 54 electrolyte solution feed inlet 55 electrolyte solution 56 auxiliary anode 60 auxiliary anode cell W Aluminum plate 610 anodizing apparatus 612 power source cell 614 electrolytic cell 616 aluminum plate 618, 626 electrolyte solution 620 power source electrode 622, 628 rollers 624 calender roll 630 electrolytic electrode 632 cell wall 634 DC power source

权利要求:
Claims (9)
[0001]
1. Lithographic printing plate support CHARACTERIZED by the fact that it comprises an aluminum plate and an anodized aluminum film, which is formed on the aluminum plate and has micropores that extend therein from an opposite anodized film surface to the aluminum sheet in a depth direction of the anodized film, wherein each of the micropores has a large diameter portion extending from the surface of the anodized film to an average depth (depth A) of 75 to 120 nm, and a portion of small diameter, which communicates with a lower part of the large diameter portion and extends to an average depth of 900 to 2000 nm from a level of communication with the large diameter portion, where an average diameter of the large diameter portion. large diameter on the surface of the anodized film is at least 10 nm, but less than 30 nm, and a ratio of the depth A to the average diameter (depth A/average diameter) of the portion. Large-diameter portion is greater than 4.0, but maximum 12.0, and where an average diameter of the small-diameter portion at the communication level is greater than 0, but less than 10.0 nm.
[0002]
2. Support for lithographic printing plate, according to claim 1, CHARACTERIZED by the fact that the small diameter portion includes a small diameter first portion and a small diameter second portion that differ from each other in average depth, in that the small-diameter first portion is greater in average depth than the small-diameter second portion, and wherein the anodized film between the underside of the small-diameter first portion and a surface of the aluminum sheet has an average thickness of, at least 17 nm and a minimum thickness of at least 15 nm.
[0003]
3. Support for lithographic printing plate, according to claim 2, CHARACTERIZED by the fact that a density of the first portion of small diameter is from 550 to 700 pcs/μm2.
[0004]
4. Lithographic printing plate support, according to claim 2 or 3, CHARACTERIZED by the fact that a difference in average depth between the first small-diameter portion and the second small-diameter portion is 75 to 200 nm.
[0005]
5. Support for lithographic printing plate, according to any one of claims 1 to 4, CHARACTERIZED by the fact that the large diameter portion has a diameter that gradually increases from the surface of the anodized film towards the aluminum plate, in which an average diameter (average diameter of the underside) of the large diameter portion, at the communication level, is greater than an average diameter (average diameter of the surface layer) of the large diameter portion at the surface of the anodized film; the mean diameter of the bottom is greater than 10 nm but less than 60 nm; and the ratio of depth A to mean bottom diameter (depth A/mean bottom diameter) is at least 1.2 but less than 12.0.
[0006]
6. Lithographic printing plate support, according to claim 5, CHARACTERIZED by the fact that a rate of increase in the surface area of the large diameter portion is expressed by equation (A): (Rate of increase in surface area ) = 1 + Pore Density x ((π x (mean diameter of surface layer/2 + mean diameter of bottom/2) x ((mean diameter of bottom/2 - mean diameter of surface layer/2) 2+ Depth A2) 1/2+ π x (average diameter of the bottom/2) 2- π x (average diameter of the surface layer/2) 2)) and the surface area increase rate is 1.9 to 16.0.
[0007]
7. Support for lithographic printing plate, according to any one of claims 1 to 6, CHARACTERIZED by the fact that a ratio between the average diameter of the large-diameter portion on the surface of the anodized film and the average diameter of the small-diameter portion at the communication level (average diameter of large diameter portion/average diameter of small diameter portion) is greater than 1.00, but maximum 1.50.
[0008]
8. Precursor of lithographic printing plate CHARACTERIZED by the fact that it comprises: the support for lithographic printing plate, as defined in any one of claims 1 to 7; and an image recording layer formed thereon.
[0009]
9. Method of production of lithographic printing plate support for production of lithographic printing plate support, as defined in any one of claims 1 to 7, CHARACTERIZED by the fact that it comprises: a first anodizing treatment step to anodize the aluminum plate; and a second anodizing treatment step to further anodize the aluminum sheet having the anodized film obtained in the first anodizing treatment step.

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JP5813063B2|2015-11-17|

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WO2014017640A1|2014-01-30|

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法律状态:
2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-02-11| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-07-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-09-14| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/07/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2012-167777|2012-07-27|

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JP2012167777|2012-07-27|

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JP2012-210628|2012-09-25|

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JP2012210628|2012-09-25|

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JP2013-054293|2013-03-15|

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JP2013054293|2013-03-15|

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PCT/JP2013/070348|WO2014017640A1|2012-07-27|2013-07-26|Support for lithographic printing plate and manufacturing method therefor, as well as original lithographic printing plate|

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