Support for lithographic printing plate, Lithographic printing plate precursor, Method for manufacturing a lithographic printing plate

Abstract

The present application provides a support for a lithographic printing plate, a lithographic printing plate precursor, and a method for producing a lithographic printing plate precursor, the support for a lithographic printing plate being capable of obtaining a lithographic printing plate precursor excellent in scratch resistance by being combined with an image recording layer. The support for a lithographic printing plate of the present application is a support for a lithographic printing plate including an aluminum plate and an anodized film of aluminum provided on the aluminum plate, a plurality of convex portions being present on the surface on the side of the anodized film of the support for a lithographic printing plate, the average value of the equivalent circle diameters of the cut surfaces of the convex portions in the positions higher than the position of the average height of the convex portions by 0.5 μm or more being 3.0 to 10.0 μm, and the density of the convex portions having a height higher than the position of the average height of the convex portions by 0.5 μm or more being 3000 to 9000 pieces / mm 2 .

Description

Technical Field

[0001] This invention relates to a support for a lithographic printing plate, a lithographic printing plate master, and a method for manufacturing a lithographic printing plate. Background Technology

[0002] It is known that, from the viewpoint of improving the stain resistance and brush resistance when making lithographic printing plates, the aluminum support used in lithographic printing plates has its surface sanded (roughened) to give it unevenness.

[0003] For example, Patent Document 1 describes "a lithographic printing plate original having an aluminum support and an image recording layer disposed on the aluminum support. In the aforementioned lithographic printing plate original, the aluminum support includes an aluminum plate and an anodized aluminum film disposed on the aluminum plate. The image recording layer is disposed on the anodized film side of the aluminum support. Using a non-contact three-dimensional roughness tester, the density of recesses with a depth of 0.70 μm or more from the center line within a 400 μm × 400 μm range on the surface of the image recording layer side of the aluminum support is measured to be 3000 / mm." 2 above. ".

[0004] Previous technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2019 / 087516 Summary of the Invention

[0007] The technical problem to be solved by the invention

[0008] In recent years, there has been a demand for further improvements in the scratch resistance of lithographic printing plates, including those with supports for lithographic printing plates.

[0009] The inventors studied the original plate of a lithographic printing plate, which includes a support for a lithographic printing plate, as described in Patent Document 1. The results showed that the scratch resistance met the previous slow requirements, but did not meet the current requirements, and further improvement was needed.

[0010] The objective of this invention is to provide a support for a lithographic printing plate that, when combined with an image recording layer, can produce a lithographic printing plate with excellent scratch resistance.

[0011] Furthermore, the objective of this invention is to provide a method for manufacturing a lithographic printing plate and a lithographic printing plate.

[0012] means for solving technical problems

[0013] The inventors have discovered that the above-mentioned problems can be solved by the following structure.

[0014] (1) A support for a lithographic printing plate, comprising an aluminum plate and an anodized aluminum film disposed on the aluminum plate.

[0015] Multiple protrusions exist on the surface of the support for offset printing plates on the side of the anodized film.

[0016] The average equivalent circle diameter of the cut surface of the convex part at a position 0.5 μm higher than the average height of the convex part is 3.0–10.0 μm.

[0017] The density of protrusions with a height 0.5 μm or more above the average height of the protrusion is 3000–9000 per mm. 2 .

[0018] (2) The support for the lithographic printing plate according to (1), wherein,

[0019] The average diameter of the equivalent circle is 3.0–6.5 μm.

[0020] (3) The support for a lithographic printing plate according to (1) or (2), wherein,

[0021] The density is 4000–9000 particles / mm². 2 .

[0022] (4) A support for a lithographic printing plate according to any one of (1) to (3), wherein,

[0023] The ratio of the density to the average value of the equivalent circle diameter is 500 (particles / mm). 2 ) / μm or more.

[0024] (5) A support for a lithographic printing plate according to any one of (1) to (4), wherein,

[0025] The anodic oxide film thickness is 2.0 g / m². 2 above.

[0026] (6) A support for a lithographic printing plate according to any one of (1) to (5), wherein,

[0027] The anodic oxide film thickness is 3.2 g / m². 2 above.

[0028] (7) A support for a lithographic printing plate according to any one of (1) to (6), wherein,

[0029] The actual area Sx and the geometrically measured area S0, obtained by measuring 512×512 points in a 25μm×25μm area on the surface of the anodic oxide film using an atomic force microscope, are obtained by using the approximate three-point method. The surface area ratio ΔS calculated by the following formula (1) is 20% or more.

[0030] ΔS=(Sx-S0) / S0×100(%)...(1).

[0031] (8) A support for a lithographic printing plate according to any one of (1) to (7), wherein,

[0032] Anodized films have micropores.

[0033] The micropores consist of a large-diameter pore section and a small-diameter pore section. The large-diameter pore section extends from the surface of the anodic oxide film to a depth of 10–1000 nm, while the small-diameter pore section is connected to the bottom of the large-diameter pore section and extends from the connection point to a depth of 20–2000 nm.

[0034] The average diameter of the anodic oxide film surface in the large-diameter orifice section is 18–60 nm.

[0035] The average diameter at the connecting position of the small-diameter hole is less than 15 nm.

[0036] (9) A support for a lithographic printing plate according to any one of (1) to (7), wherein,

[0037] Anodized films have micropores.

[0038] The micropores consist of an upper pore section and a lower pore section. The upper pore section extends from the surface of the anodic oxide film in the depth direction, and the lower pore section is connected to the bottom of the upper pore section, extending to a depth of 20–2000 nm from the connection point.

[0039] The average diameter of the upper pores on the surface of the anodic oxide film is 18–60 nm.

[0040] The maximum diameter of the upper aperture is less than 200 nm.

[0041] The average diameter at the connecting position of the lower hole is less than 15 nm.

[0042] The ratio of the maximum diameter of the upper hole to the average diameter of the upper hole at the surface of the anodic oxide film is greater than 1.2.

[0043] (10) The support for a lithographic printing plate according to claim (8) or (9), wherein,

[0044] The density of micropores is 300–2000 per μm. 2 .

[0045] (11) A lithographic printing plate original, comprising a support for the lithographic printing plate and an image recording layer as described in any one of (1) to (10).

[0046] (12) The original lithographic printing plate described in (11) is an on-machine developing type.

[0047] (13) A method for manufacturing a lithographic printing plate, comprising the following steps:

[0048] The original offset printing plate described in (11) is exposed to an image using an infrared laser; and

[0049] The unexposed portion of the image recording layer is removed on a printing press by means of at least one of printing ink and dampening solution.

[0050] Invention Effects

[0051] According to the present invention, a support for a lithographic printing plate can be provided, which can be combined with an image recording layer to obtain a lithographic printing plate with excellent scratch resistance.

[0052] Furthermore, according to the present invention, a method for manufacturing a lithographic printing plate and a lithographic printing plate can be provided. Attached Figure Description

[0053] Figure 1 This is a schematic cross-sectional view of one embodiment of the support for a lithographic printing plate of the present invention.

[0054] Figure 2 This is a diagram illustrating the manner in which the anodized film of the support for the offset printing plate of the present invention is applied.

[0055] Figure 3 This is a diagram used to illustrate the equivalent circle diameter of the cross-section of a convex part.

[0056] Figure 4 This is a schematic cross-sectional view of one embodiment of anodized film.

[0057] Figure 5 This is a schematic cross-sectional view of one embodiment of anodized film.

[0058] Figure 6 This is a graph illustrating an example of an alternating current waveform used in the electrochemical roughening process during the manufacturing of a support for a lithographic printing plate.

[0059] Figure 7 This is a side view illustrating an example of a radial unit in an electrochemical roughening process using alternating current in a method for manufacturing a support for a lithographic printing plate.

[0060] Figure 8 This is a schematic cross-sectional view of one embodiment of using a lithographic printing plate as the original.

[0061] Figure 9 This is a schematic diagram of the anodizing apparatus used in the anodizing process of fabricating a support for a lithographic printing plate. Detailed Implementation

[0062] The present invention will now be described in detail.

[0063] The following description of the constituent elements is based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment.

[0064] In addition, in this specification, the numerical range indicated by “~” refers to the range including the values ​​recorded before and after “~” as the lower and upper limits.

[0065] Furthermore, in this specification, regarding the designation of groups in compounds represented by the formula, unless otherwise specified, the group may contain both unsubstituted and substituted groups, provided that substitution or unsubstituted is not explicitly stated. For example, if the formula contains the statement "R represents alkyl, aryl, or heterocyclic group", it means "R represents unsubstituted alkyl, substituted alkyl, unsubstituted aryl, substituted aryl, unsubstituted heterocyclic, or substituted heterocyclic group".

[0066] The offset printing plate support of the present invention includes an aluminum plate and an anodized aluminum film disposed on the aluminum plate. A plurality of protrusions are present on the surface of the offset printing plate support on the anodized film side. The average equivalent circle diameter of the cut surface of the protrusions located at positions 0.5 μm higher than the average height of the protrusions is 3.0 to 10.0 μm. The density of protrusions having a height of 0.5 μm or more higher than the average height of the protrusions is 3000 to 9000 per mm. 2 .

[0067] Hereinafter, with reference to the accompanying drawings, the support for the lithographic printing plate of the present invention will be described in detail.

[0068] Figure 1 This is a schematic cross-sectional view of one embodiment of the support for a lithographic printing plate of the present invention.

[0069] Figure 1 The lithographic printing plate support 10 shown has a stacked structure consisting of an aluminum plate 12 and an aluminum anodized film 14A (hereinafter also referred to as an anodized film) stacked in sequence. Figure 2 Is with Figure 1An enlarged view of the surface 141A of the aluminum plate 12 opposite to the anodized film 14A (in other words, the surface of the anodized film side of the lithographic printing plate support), showing that multiple protrusions exist on the surface 141A of the anodized film 14A. Figure 2 In the middle, the first protrusion 16A, the second protrusion 16B, and the third protrusion 16C). Additionally, in Figure 2 Although only three protrusions are shown in the figure, the invention is not limited to this figure.

[0070] Below, we will first explain the average value and density of the equivalent circle diameter, which are characteristic points of the present invention.

[0071] In the lithographic printing plate support of the present invention, there are a plurality of protrusions on the surface of the anodic oxide film side of the lithographic printing plate support, and the average value of the equivalent circle diameter of the cutting surface of the protrusion at a position 0.5 μm higher than the average height of the protrusion is 3.0 to 10.0 μm.

[0072] use Figure 2 and 3 To explain more specifically the average value of the equivalent circle diameter mentioned above.

[0073] As mentioned above, such as Figure 2 As shown, the anodized film 14A has multiple protrusions (first protrusion 16A, second protrusion 16B, and third protrusion 16C) on its surface 141A. First, the average height of the protrusion is calculated, and the position P1 of its average height is determined.

[0074] The method for calculating the aforementioned average height is as follows.

[0075] The three-dimensional roughness of the anodic oxide film surface within a 400 μm × 400 μm area was determined using a non-contact three-dimensional roughness tester (VertScan, manufactured by Ryoka Systems Inc.). The apparatus contents and measurement conditions of the VertScan are as follows.

[0076] (1) Device contents

[0077] CCD camera: Sony HR-57

[0078] Objective lenses: ×10

[0079] Lens tube: ×1

[0080] Wavelength filter: 530 white

[0081] (2) Measurement conditions

[0082] Measurement mode: wave

[0083] Field of view: 400μm × 400μm

[0084] Scan range: Start +6μm, End -10μm

[0085] Next, using software (VS Viewer, manufactured by Ryoka Systems Inc.), selecting "Full Interpolation" → "Surface Correction Polynomial" → "Quadratic" → "Particle Analysis," image analysis was performed on the obtained 3D data to determine the location P1 of the average height of the convex portion. Furthermore, the aforementioned average height P1 of the convex portion refers to the average height of all measured data points on the surface of the anodic oxide film within the measurement area.

[0086] Next, as Figure 2 As shown, a position P2 is determined that is 0.5 μm higher than the calculated average height P1.

[0087] Next, calculate the equivalent circle diameter of the cutting surface of the convex portion at position P2. Figure 2 In this configuration, the second protrusion 16B and the third protrusion 16C are located at a position higher than position P2, therefore, as Figure 3 As shown, cross-sections originating from the second protrusion 16B and the third protrusion 16C are observed on the cut surface at position P2. The equivalent circle diameter is calculated from the area of ​​the cut surface of each protrusion, and the calculated values ​​are then arithmetically averaged to obtain the average equivalent circle diameter. Figure 2 In this method, the equivalent circle diameter of the cross-sectional area of ​​the second convex part 16B in position P2 and the equivalent circle diameter of the cross-sectional area of ​​the third convex part 16C in position P2 are calculated and then their arithmetic averages are taken.

[0088] The equivalent circle diameter is the diameter of a circle that has an area equal to the cross-sectional area of ​​each convex part in the cut surface.

[0089] The above measurement involves measuring five locations for each sample, calculating the average value of the equivalent circular diameter of the protrusion at each location, and then calculating the average of the five values. This value is set as the average value of the equivalent circular diameter of the protrusion specified in the lithographic printing plate support of this invention. In this invention, it is acceptable as long as this value is within the above-mentioned range (3.0 to 10.0 μm).

[0090] In the lithographic printing plate support of the present invention, the average value of the equivalent circle diameter is 3.0 to 10.0 μm. From the viewpoint that the lithographic printing plate original including the lithographic printing plate support has better scratch resistance (hereinafter also referred to as "the viewpoint that the effect of the present invention is better"), it is preferred to be 3.0 to 6.5 μm, and more preferably 3.0 to 5.0 μm.

[0091] Furthermore, in the lithographic printing plate support of the present invention, the density of protrusions having a height 0.5 μm or more higher than the average height of the protrusions is 3000 to 9000 per mm. 2 .

[0092] For example, in Figure 2 In this context, the protrusions that have a height of 0.5 μm or more higher than the average height of the protrusions at position P1 correspond to the second protrusion 16B and the third protrusion 16C.

[0093] From the viewpoint of achieving better results with the present invention, the density is preferably 4000 to 9000 particles / mm². 2 More preferably 6000-9000 pieces / mm 2 .

[0094] The method for calculating the density mentioned above is as follows.

[0095] First, following the same steps as the method for calculating the average height described above, three-dimensional data of the surface of the anodized film is obtained. The obtained three-dimensional data is then analyzed using software (SXViewer, manufactured by Ryoka Systems Inc.) to determine the position of the average height of the protrusions. Furthermore, the number of protrusions with a height of 0.5 μm or more above the position of the average height of the protrusions is determined.

[0096] The above measurements were performed on five sites for each sample, and the density of the convex portion at each site was calculated (per unit area (μm²)). 2 The number of protrusions is calculated, and then the average of the five values ​​is taken as the density of the protrusions specified in the support for the offset printing plate of the present invention. In the present invention, as long as the value is within the above range (3000 to 9000 protrusions / mm), it is considered acceptable. 2 That's all.

[0097] The density ratio (density / average equivalent circle diameter) of protrusions having a height 0.5 μm or more higher than the average height of the protrusions relative to the average equivalent circle diameter is not particularly limited, but from the viewpoint of better performance of the present invention, 500 (particles / mm²) is preferred. 2 ) / μm or higher, more preferably 800 to 1500 (particles / mm) 2 ) / μm.

[0098] In the lithographic printing plate support of the present invention, from the viewpoint of further improving the effects of the present invention, the surface area ratio ΔS, calculated by the following formula (1), is preferably 20% or more, more preferably 30% or more, and even more preferably 37% or more, based on the actual area Sx obtained by measuring 512 × 512 points in a 25 μm × 25 μm range on the surface of the anodic oxide film side using an atomic force microscope and measured by the approximate three-point method, and the geometrically measured area S0. There is no particular upper limit to the surface area ratio ΔS, but it is preferably 70% or less, more preferably 60% or less.

[0099] ΔS=(Sx-S0) / S0×100(%)……(1)

[0100] In this invention, the surface area ratio ΔS refers to a value measured in the following manner.

[0101] Specifically, a 1cm square section of a planar printing plate is cut using a support and placed on a horizontal sample stage on a piezoelectric scanner. The cantilever is brought close to the sample surface, and scanning is performed in the XY directions when the atomic force is applied. The sample's unevenness is then obtained through piezoelectric displacement in the Z direction. A piezoelectric scanner capable of scanning 150μm in the XY directions and 10μm in the Z direction is used. A cantilever (OMCL-AC200-TS, manufactured by Olympus Corporation) with a resonant frequency of 130–200kHz and a spring constant of 7–20 N / m is used, and measurements are performed in DFM (Dynamic Force Mode). Furthermore, a reference surface is determined by correcting for minute tilts of the sample using a least-squares approximation of the obtained three-dimensional data.

[0102] Furthermore, regarding the measurement, 512×512 points were measured on a 25×25μm surface. The resolution in the X direction was set to 0.05μm, the resolution in the Y direction was set to 1.9μm, the resolution in the Z direction was set to 1nm, and the scan rate was set to 18μm / see.

[0103] The following is a detailed description of the components of the support for offset printing plates.

[0104] [Aluminum Plate]

[0105] The aluminum plate 12 is a dimensionally stable metal with aluminum as its main component, and may contain aluminum or an aluminum alloy. Examples of aluminum plates 12 include pure aluminum plates, alloy plates with aluminum as their main component and containing trace amounts of dissimilar elements, or plastic films or paper made by laminating or vapor-depositing aluminum (alloys).

[0106] Aluminum alloys contain dissimilar elements such as silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium, with the content of dissimilar elements in the alloy being less than 10% by mass. Pure aluminum is preferred for aluminum plate 12; however, from a smelting technology perspective, completely pure aluminum is difficult to manufacture, therefore a small amount of dissimilar elements may be included.

[0107] The composition of the aluminum plate 12 is not limited, and commonly known raw materials (e.g., JIS A1050, JIS A 1100, JIS A 3103 and JIS A 3005) can be appropriately utilized.

[0108] Furthermore, the width of the aluminum plate 12 is preferably around 400–2000 mm, and the thickness is preferably around 0.1–0.6 mm. This width or thickness can be appropriately changed according to the size of the printing press, the size of the printing plate, and the user's needs.

[0109] [Anodized film]

[0110] Anodized film 14A is a film typically produced on the surface of aluminum plate 12 through anodizing treatment, although in Figure 1 and Figure 2 Not shown, but the film preferably has ultrafine micropores that are generally perpendicular to the film surface and uniformly distributed. The micropores extend from the surface of the anodized film 14A along the thickness direction (aluminum plate 12 side).

[0111] In addition, the term "micropore" is a commonly used term to refer to pores in anodized films, and does not specify the size of the pores.

[0112] There is no particular limitation on the amount of anodic oxide film, but from the viewpoint of achieving better results in this invention, 2.0 g / m² is preferred. 2 More preferably 3.2g / m 2 The above is further optimized to 3.4g / m 2 That's all. The upper limit is not specifically restricted, but 5.0 g / m³ is acceptable. 2 The following situations are more common, 4.0g / m 2 The following situations are more common.

[0113] The density of micropores in the anodic oxide film 14A is not particularly limited, but from the viewpoint of achieving better results in this invention, 300 to 2000 pores / μm is preferred. 2 More preferably 500–1200 cells / μm 2 .

[0114] The density of micropores was determined as follows: using a field emission scanning electron microscope (FE-SEM) at 150,000x magnification, N=4 images were observed on the surface of the anodic oxide film 14A. In the four images obtained, the density of micropores at 400×600 nm was measured. 2 The number of micropores within a certain range is the value obtained by calculating the density for each image and averaging it.

[0115] The average diameter (average opening diameter) of the anodic oxide film 14A with micropores is preferably 10–150 nm, more preferably 10–100 nm. From the viewpoint of brush resistance, 15–101 nm is further preferred, particularly 15–60 nm, especially 20–50 nm, and most preferably 25–40 nm. The same effect can be obtained regardless of whether the internal diameter of the micropores is wider or narrower than the surface layer.

[0116] The average diameter of the micropores was as follows: using a field emission scanning electron microscope (FE-SEM) at 150,000x magnification, N=4 images were observed on the surface of the 14A anodic oxide film. In the four images obtained, the diameter of the micropores at 400×600 nm was measured. 2 The value is obtained by averaging the diameter of the micropores within a certain range.

[0117] Additionally, when the shape of the micropore is not circular, the equivalent circle diameter is used. The "equivalent circle diameter" refers to the diameter of a circle when the shape of the opening is assumed to be a circle with a projected area equal to the projected area of ​​the opening.

[0118] There is no particular limitation on the depth of the micropores, but it is preferred to be 10–3000 nm, more preferably 50–2000 nm, and even more preferably 300–1600 nm.

[0119] In addition, the above depth is obtained by taking a cross-sectional photograph (150,000x magnification) of the anodic oxide film 14A, measuring the depth of more than 25 micropores, and averaging the results.

[0120] The shape of the micropores is not particularly limited; they can be generally straight tubular (generally cylindrical), but can also be conical with a diameter that decreases toward the depth direction (thickness direction). Furthermore, as described later, they can be pores with interconnected diameters along the thickness direction.

[0121] Furthermore, there are no particular restrictions on the shape of the bottom of the micropore; it can be curved (convex) or flat.

[0122] The shape of the micropores in the anodic oxide film is not particularly limited, for example, such as Figure 4As shown, the anodic oxide film 14B can be configured to have micropores 20 consisting of large-diameter pores 22 and small-diameter pores 24.

[0123] The micropores 20 in the anodic oxide film 14B are composed of large-diameter pores 22 and small-diameter pores 24. The large-diameter pores 22 extend from the surface of the anodic oxide film 14B to a depth of 10–1000 nm (depth D: reference). Figure 4 The small-diameter hole 24 is connected to the bottom of the large-diameter hole 22 at the position of the connection, and extends further from the connection position to a depth of 20 to 2000 nm.

[0124] The large-diameter hole 22 and the small-diameter hole 24 will be described in detail below.

[0125] The average diameter of the anodic oxide film 14B surface of the large-diameter hole portion 22 is the same as the average diameter of the anodic oxide film 14A surface of the micropores described above, preferably 10 to 100 nm, preferably 18 to 60 nm from the viewpoint of brush resistance, more preferably 20 to 50 nm, and even more preferably 25 to 40 nm.

[0126] The method for determining the average diameter of the anodic oxide film 14B surface of the large-diameter hole 22 is the same as the method for determining the average diameter of the anodic oxide film 14A surface of the micro-hole.

[0127] The bottom of the large-diameter hole 22 is located at a depth of 10 to 1000 nm (or less, also referred to as depth D) from the surface of the anodic oxide film 14B. That is, the large-diameter hole 22 is a hole extending 10 to 1000 nm from the surface of the anodic oxide film 14B along the depth direction (thickness direction). The aforementioned depth is preferably 10 to 200 nm.

[0128] In addition, the above depth is the value obtained by taking a cross-sectional photograph (150,000x magnification) of the anodized film 14B, measuring the depth of more than 25 large-diameter holes 22, and averaging them.

[0129] The shape of the large-diameter hole 22 is not particularly limited. For example, it can be a generally straight tube (generally cylindrical) or a conical shape whose diameter decreases as it moves toward the depth direction (thickness direction). A generally straight tube is preferred.

[0130] like Figure 4 As shown, the small-diameter hole 24 is connected to the bottom of the large-diameter hole 22 and extends further along the depth direction (thickness direction) from the connection position.

[0131] The average diameter at the communication position of the small-diameter hole 24 is smaller than the average diameter of the large-diameter hole, preferably 15 nm or less. More preferably, it is 13 nm or less. There is no particular limitation on the lower limit, but it is usually 5 nm or more.

[0132] The average diameter of the small-diameter aperture 24 is as follows: Using a FE-SEM with a magnification of 150,000x, the surface of the anodic oxide film 14A was observed in N=4 images. In the four images obtained, 50 apertures were measured at 400×600 nm. 2 The diameter of the micropores (small-diameter pores) within the specified range is calculated and averaged. Additionally, if the large-diameter pores are deep, the upper part of the anodic oxide film 14B (the area with the large-diameter pores) can be cut (e.g., by argon gas cutting), and the surface of the anodic oxide film 14B can be observed using the aforementioned FE-SEM to determine the average diameter of the small-diameter pores 24.

[0133] Furthermore, when the shape of the small-diameter hole 24 is not circular, the equivalent diameter of the circle is used. The "equivalent diameter of the circle" refers to the diameter of a circle when the shape of the opening is assumed to be a circle with a projected area equal to the projected area of ​​the opening.

[0134] The bottom of the small-diameter hole 24 is located at a position extending 20 to 2000 nm further along the depth direction from its communication position with the large-diameter hole 22. In other words, the small-diameter hole 24 is a hole that extends further along the depth direction (thickness direction) from its communication position with the large-diameter hole 22, and the depth of the small-diameter hole 24 is 20 to 2000 nm. Preferably, the depth is 500 to 1500 nm.

[0135] In addition, the above depth is the value obtained by taking a cross-sectional photograph (50,000x magnification) of the anodized film 14B, measuring the depth of more than 25 small-diameter holes 24, and averaging them.

[0136] The shape of the small-diameter hole 24 is not particularly limited. For example, it can be a generally straight tube (generally cylindrical) or a conical shape whose diameter decreases with the direction of depth. A generally straight tube is preferred.

[0137] And, for example, such as Figure 5 As shown, the anodic oxide film 14C can be configured to have micropores 30 consisting of an upper pore portion 32 and a lower pore portion 34.

[0138] The micropores 30 in the anodic oxide film 14C are composed of an upper pore portion 32 and a lower pore portion 34. The upper pore portion 32 extends from the surface of the anodic oxide film 14C in the depth direction, and the lower pore portion 34 communicates with the bottom of the upper pore portion 32, extending further to a depth of 20-2000 nm from the communication position. The upper pore portion 32 is composed of a small-diameter upper pore portion 36 and a large-diameter upper pore portion 38. The small-diameter upper pore portion 36 extends from the surface of the anodic oxide film 14C in the depth direction, and the large-diameter upper pore portion 38 communicates with the bottom of the small-diameter upper pore portion 36, extending further in the depth direction.

[0139] The average diameter of the upper hole 32 on the surface of the anodic oxide film 14C is the same as the average diameter on the surface of the microporous anodic oxide film 14A, preferably 10 to 100 nm. From the viewpoint of brush resistance, it is preferably 18 to 60 nm, more preferably 20 to 50 nm, even more preferably 25 to 40 nm, and especially preferably 25 to 40 nm.

[0140] The method for determining the average diameter of the upper pore 32 on the surface of the anodic oxide film 14C is the same as the method for determining the average diameter on the surface of the microporous anodic oxide film 14A.

[0141] There is no particular limitation on the maximum diameter of the upper hole 32, but from the viewpoint of brush resistance, it is preferable to be less than 200 nm, and more preferably 50 to 150 nm.

[0142] Furthermore, there is no particular limitation on the ratio of the maximum diameter of the upper hole portion relative to the average diameter of the upper hole portion 32 on the surface of the anodized film 14C, but from the viewpoint of brush resistance, it is preferable to be 1.2 or more, and more preferably 2.0 to 6.0.

[0143] In addition, such as Figure 5 As shown, the upper hole portion 32 is composed of a small-diameter upper hole portion 36 and a large-diameter upper hole portion 38 with an inner diameter larger than that of the small-diameter upper hole portion 36. Therefore, the maximum diameter of the upper hole portion 32 corresponds to the inner diameter of the large-diameter upper hole portion 38.

[0144] The shape of the upper hole 32 is not limited to Figure 5 The shape can be, for example, one in which the inner diameter gradually increases from the average diameter at the surface of the anodic oxide film 14C towards the depth direction.

[0145] like Figure 5 As shown, the lower hole 34 is connected to the bottom of the upper hole 32 and extends further along the depth direction (thickness direction) from the connection position.

[0146] The average diameter at the communication position of the small-diameter hole 24 is smaller than the average diameter of the large-diameter hole, preferably 15 nm or less. More preferably, it is 13 nm or less. There is no particular limitation on the lower limit, but it is usually 5 nm or more.

[0147] The average diameter of the lower aperture 34 is as follows: Using a FE-SEM with a magnification of 150,000x and N=4 images, the surface of the anodic oxide film 14A was observed. In the four images obtained, 50 apertures were measured at 400×600 nm. 2The diameter of the micropores (small-diameter pores) within the specified range is calculated and averaged. Additionally, if the large-diameter pores are deep, the upper part of the anodic oxide film 14C (the region with the upper pores) can be cut (e.g., by argon gas cutting), and the surface of the anodic oxide film 14C can be observed using the aforementioned FE-SEM to determine the average diameter of the lower pores 34.

[0148] Furthermore, when the shape of the lower hole 34 is not circular, an equivalent circular diameter is used. "Equivalent circular diameter" refers to the diameter of a circle when the shape of the opening is assumed to be a circle with a projected area equal to the projected area of ​​the opening.

[0149] The bottom of the lower hole 34 is located at a position extending 20 to 2000 nm along the depth direction from its communication position with the upper hole 32. In other words, the lower hole 34 is a hole extending further along the depth direction (thickness direction) from its communication position with the upper hole 32, and the depth of the lower hole 34 is 20 to 2000 nm. Preferably, the depth is 500 to 1500 nm.

[0150] In addition, the above depth is the value obtained by taking a cross-sectional photograph (50,000x magnification) of the anodized film 14C, measuring the depth of more than 25 lower holes 34, and averaging them.

[0151] The shape of the lower hole 34 is not particularly limited. For example, it can be a generally straight tube (generally cylindrical) or a cone shape whose diameter decreases with the direction of depth. A generally straight tube shape is preferred.

[0152] [Manufacturing method for support body for offset printing plate]

[0153] The method for manufacturing the offset printing plate support of the present invention is not particularly limited, but from the viewpoint of being able to manufacture an offset printing plate support with high efficiency and specific requirements, it is preferable to include a hydrochloric acid electrolysis treatment step in which an aluminum plate is subjected to alternating electrolysis in a hydrochloric acid treatment solution that may contain sulfuric acid to produce a roughened aluminum plate. In particular, when performing electrolysis treatment in the hydrochloric acid electrolysis treatment step, it is preferable to set a predetermined stop time and perform electrolysis treatment in 10 or more stages. That is, it is preferable to repeatedly perform electrolysis treatment and stop treatment for a predetermined time within a predetermined time, so that the number of electrolysis treatments reaches 10 or more.

[0154] Furthermore, the manufacturing method of the support for the lithographic printing plate of the present invention preferably includes: an anodizing process, wherein after the above-mentioned hydrochloric acid electrolysis process, an anodizing process is performed on the roughened aluminum plate to form an aluminum anodized film on the aluminum plate.

[0155] Furthermore, the manufacturing method of the support for the lithographic printing plate of the present invention preferably includes: a hole enlargement process, wherein after the above-mentioned anodizing process, an etching process is performed on the aluminum plate on which an anodized film is formed, thereby enlarging the diameter of the micropores in the anodized film.

[0156] The following is a detailed description of each of the above-mentioned processes and any arbitrary treatments.

[0157] <Mechanical roughening treatment>

[0158] The method for manufacturing the support for offset printing plates of the present invention can perform mechanical roughening treatment before the hydrochloric acid electrolysis process.

[0159] As mechanical roughening methods, for example, wire brushing can be used to scrape the aluminum surface with a metal wire, ball grinding can be used to abrade the aluminum surface with abrasive balls and abrasives, and brushing can be used to abrade the surface with a nylon brush and abrasives as described in Japanese Patent Application Publication No. 6-135175 and Japanese Patent Publication No. 50-040047.

[0160] <Hydrochloric acid electrolysis process>

[0161] The hydrochloric acid electrolysis process included in the method for manufacturing the support for offset printing plates of the present invention is preferably a process in which an aluminum plate is subjected to an electrolysis process for a predetermined pause time and more than 10 times in a hydrochloric acid treatment solution that may contain sulfuric acid, thereby producing a roughened aluminum plate.

[0162] In this invention, by performing this hydrochloric acid electrolysis treatment and the anodizing treatment described later, the above-mentioned support for offset printing plates can be manufactured efficiently.

[0163] As mentioned above, when performing AC electrolysis, it is preferable to set a stop time and perform AC electrolysis in multiple stages.

[0164] The pause time between each AC electrolysis cycle is preferably 0.3 to 3.0 seconds, more preferably 0.5 to 1.5 seconds.

[0165] The number of alternating current electrolysis cycles is preferably 10 or more, more preferably 12 or more. There is no particular upper limit, but it is usually less than 20 times.

[0166] The hydrochloric acid treatment solution contains hydrochloric acid, and the concentration of hydrochloric acid is preferably 5-30 g / L, more preferably 10-20 g / L.

[0167] The hydrochloric acid treatment solution may contain sulfuric acid. When the hydrochloric acid treatment solution contains sulfuric acid, the concentration of sulfuric acid in the hydrochloric acid treatment solution is preferably 2.0 g / L or less, more preferably 1.5 g / L or less. When the hydrochloric acid treatment solution contains sulfuric acid, there is no particular limitation on the lower limit of the sulfuric acid concentration in the hydrochloric acid treatment solution, and examples of concentrations exceeding 0 g / L are possible.

[0168] The hydrochloric acid treatment solution may contain aluminum ions. When the hydrochloric acid treatment solution contains aluminum ions, the concentration of aluminum ions is preferably 1.0 to 30.0 g / L, more preferably 5.0 to 20.0 g / L.

[0169] When the hydrochloric acid treatment solution contains sulfuric acid, the ratio of sulfuric acid content to hydrochloric acid content is preferably 0.1 or less. There is no particular limitation on the lower limit, and examples exceeding 0 are possible.

[0170] There are no particular limitations on the temperature of the hydrochloric acid treatment solution, but it is preferably below 30°C, more preferably below 25°C, and even more preferably below 20°C. There are no particular limitations on the lower limit, but it is preferably above 5°C, and more preferably above 10°C.

[0171] In this invention, the total charge (the total charge participating in the anodic reaction of the aluminum plate at the end of the hydrochloric acid electrolysis treatment) is preferably 400 C / dm. 2 Below, 375C / dm is preferred. 2 The following applies. There is no specific limit to the lower limit of total power consumption, but 50C / dm is preferred. 2 The above is preferred, 100C / dm 2 above.

[0172] The peak current value of the alternating current waveform is preferably 80 A / dm. 2 Below, 70A / dm is preferred. 2 The peak current value is preferably 10 A / dm. 2 The above is preferred, 20A / dm 2 above.

[0173] The alternating current waveform used in hydrochloric acid electrolysis can be a sine wave, a rectangular wave, a trapezoidal wave, or a triangular wave. The preferred frequency is 0.1–250 Hz.

[0174] Figure 6 This is a graph representing an example of an alternating current waveform used in hydrochloric acid electrolysis.

[0175] exist Figure 6In this context, ta represents the anode reaction time, tc represents the cathode reaction time, tp represents the time it takes for the current to reach its peak value from 0, Ia represents the peak current on the anode circulation side, and Ic represents the peak current on the cathode circulation side. In the trapezoidal wave, the time tp for the current to reach its peak value from 0 is preferably 1–10 msec. The preferred conditions for one cycle of AC current used for hydrochloric acid electrolysis are: the ratio of the anode reaction time ta to the cathode reaction time tc (tc / ta) of the aluminum plate is 1–20; the ratio of the charge Qc when the aluminum plate is the anode to the charge Qa when the aluminum plate is the anode (Qc / Qa) is 0.3–20; and the anode reaction time ta is in the range of 5–1000 msec. Regarding current density, the peak current values ​​on both the anode circulation side (Ia) and the cathode circulation side (Ic) of the trapezoidal wave are preferably within the above ranges (80 A / dm²). 2 (Below)

[0176] In hydrochloric acid electrolysis using alternating current, it can be used Figure 7 The apparatus shown.

[0177] Figure 7 This is a side view showing an example of a radial unit in hydrochloric acid electrolysis using alternating current.

[0178] exist Figure 7 In this configuration, 50 is the main electrolytic cell, 51 is the AC power supply, 52 is the radial drum roller, 53a and 53b are the main electrodes, 54 is the electrolyte supply port, 55 is the electrolyte, 56 is the slit, 57 is the electrolyte channel, 58 is the auxiliary anode, 60 is the auxiliary anode tank, and W is the aluminum plate. When using two or more electrolytic cells, the electrolysis conditions can be the same or different.

[0179] An aluminum plate W is rolled onto a radial drum roller 52, which is immersed in the main electrolytic cell 50, and electrolyzed during transport via main electrodes 53a and 53b connected to an AC power supply 51. Electrolyte 55 is supplied from the electrolyte supply port 54 through a slit 56 to the electrolyte channel 57 between the radial drum roller 52 and the main electrodes 53a and 53b. The aluminum plate W, after being treated in the main electrolytic cell 50, is then electrolyzed in an auxiliary anode tank 60. In this auxiliary anode tank 60, an auxiliary anode 58 is positioned opposite the aluminum plate W, and electrolyte 55 is supplied in a manner that flows through the space between the auxiliary anode 58 and the aluminum plate W.

[0180] <Alkali Etching Treatment>

[0181] The method for manufacturing the support for the lithographic printing plate of the present invention preferably involves performing an alkaline etching process after the mechanical roughening process described above, or before or after the hydrochloric acid electrolysis process described above. Alternatively, the alkaline etching process may be omitted.

[0182] In addition, regarding the alkaline etching treatment performed before hydrochloric acid electrolysis, it is performed to remove rolling oil, contaminants, and natural oxide film from the surface of the aluminum plate (rolled aluminum) when mechanical roughening treatment has not been performed, and when mechanical roughening treatment has been performed, it is performed to dissolve the uneven edges generated by mechanical roughening treatment and change the steep unevenness into a smooth wavy surface.

[0183] Without mechanical roughening treatment prior to alkaline etching, the etching amount is preferably 0.1–10 g / m. 2 More preferably 1-5 g / m 2 If the etching amount is 1-10 g / m 2 This can effectively remove rolling oil, contaminants, and natural oxide film from the surface.

[0184] When mechanical roughening is performed before alkaline etching, the etching amount is preferably 3 to 20 g / m. 2 More preferably 5-15 g / m 2 .

[0185] The alkaline etching process, performed immediately after hydrochloric acid electrolysis, aims to dissolve the contaminants formed in the acidic electrolyte and the edges of the unevenness created by the hydrochloric acid electrolysis. The unevenness created by hydrochloric acid electrolysis varies depending on the type of electrolyte, and therefore the optimal etching amount also varies. However, when alkaline etching is performed after hydrochloric acid electrolysis, the etching amount is preferably greater than 0 g / m². 2 And 0.50g / m 2 More preferably, it exceeds 0g / m 2 And 0.30g / m 2 From the perspective of superior brush resistance, it is further preferred to have a brush resistance exceeding 0 g / m 2 And 0.20g / m 2 the following.

[0186] Examples of bases used in alkaline solutions include caustic sodas and alkali metal salts. In particular, aqueous solutions of sodium hydroxide are preferred.

[0187] The concentration of the alkaline solution can be determined according to the etching amount, but is preferably 1-50% by mass, more preferably 10-35% by mass. If aluminum ions are dissolved in the alkaline solution, the concentration of aluminum ions is preferably 0.01-10% by mass, more preferably 3-8% by mass. The temperature of the alkaline solution is preferably 20-90°C. The processing time is preferably 0-120 seconds.

[0188] Methods for bringing an aluminum plate into contact with an alkaline solution include, for example, passing the aluminum plate through a tank containing an alkaline solution, immersing the aluminum plate in a tank containing an alkaline solution, and spraying the alkaline solution onto the surface of the aluminum plate.

[0189] <Decontamination Treatment>

[0190] The method for manufacturing the support for the lithographic printing plate of the present invention preferably involves acid washing (decontamination treatment) after hydrochloric acid electrolysis or alkaline etching to remove corrosive organisms remaining on the surface.

[0191] The acids used are typically nitric acid, sulfuric acid, and hydrochloric acid, but other acids may also be used.

[0192] The above-mentioned decontamination treatment is carried out, for example, by contacting the aluminum plate with an acidic solution containing 0.01% to 5% aluminum ions at a concentration of 0.5% to 30% by mass, such as hydrochloric acid, nitric acid, or sulfuric acid.

[0193] Methods for bringing an aluminum plate into contact with an acidic solution include, for example, passing the aluminum plate through a container filled with an acidic solution, immersing the aluminum plate in a tank filled with an acidic solution, and spraying the acidic solution onto the surface of the aluminum plate.

[0194] The surface condition of the aluminum plate after decontamination treatment will affect the subsequent growth of the natural oxide film. Therefore, the choice of acid, concentration, and temperature conditions should be appropriately selected according to the purpose.

[0195] <Water washing treatment>

[0196] The method for manufacturing the support for offset printing plates of the present invention preferably involves washing with water after each of the above-described processing steps. In particular, the water washing performed at the end of the process can affect the subsequent growth of the natural oxide film, so it is necessary to use pure water, well water, tap water, etc. to wash it thoroughly.

[0197] <Anodizing Process>

[0198] The above-mentioned anodizing process is a process of performing anodizing treatment on the roughened aluminum plate after the above-mentioned hydrochloric acid electrolysis process to form an aluminum anodized film on the aluminum plate.

[0199] Here, the steps of the above-mentioned anodizing process are not particularly limited, and well-known methods can be cited.

[0200] In the anodizing process, aqueous solutions of sulfuric acid, phosphoric acid, and oxalic acid can be used as electrolytic cells. For example, the concentration of sulfuric acid can range from 0.1 to 300 g / L.

[0201] The conditions for anodizing can be appropriately set according to the electrolyte used, but examples include a electrolyte temperature of 5–70°C (preferably 10–60°C) and a current density of 0.5–60 A / dm³. 2 (Preferred 5~60A / dm) 2 The voltage is 1-100V (preferably 5-50V), the electrolysis time is 1-100 seconds (preferably 5-60 seconds), and the film weight is 0.1-5g / m³. 2 (Preferred to be 0.2-3 g / m) 2 ).

[0202] <Bore Enlargement Process>

[0203] The above-mentioned hole enlargement process is an etching process performed on the aluminum plate with the anodic oxide film after the above-mentioned anodizing process, thereby enlarging the diameter of the micropores in the anodic oxide film (hole enlargement process).

[0204] The hole-enlarging process can be performed by contacting the aluminum plate obtained through the above-described anodizing process with an acidic or alkaline aqueous solution. There are no particular limitations on the contact method; for example, immersion and spraying methods can be used.

[0205] In addition, in the above Figure 4 There are no particular limitations on the manufacturing method of the anodized film 14B shown, but a manufacturing method that performs the following steps in sequence is preferred.

[0206] (Hydrochloric acid electrolysis treatment process) The process of performing the above-mentioned hydrochloric acid electrolysis treatment on the aluminum plate.

[0207] (First Anodizing Process) The process of anodizing the roughened aluminum sheet.

[0208] (Pore Enlargement Process) A process in which the aluminum plate with anodized film obtained in the first anodizing process is brought into contact with an acidic or alkaline aqueous solution to enlarge the diameter of the micropores in the anodized film.

[0209] (Second Anodizing Process) A process of anodizing the aluminum sheet obtained in the hole enlargement process.

[0210] The steps for each process can be referenced from well-known methods.

[0211] Furthermore, in Figure 5 The manufacturing method of the anodized film 14C shown is not particularly limited, and a method of performing three anodizing treatments can be cited as an example.

[0212] [Original lithograph version]

[0213] The original lithographic printing plate of the present invention includes the aforementioned support for lithographic printing plates.

[0214] More specifically, Figure 8 The lithographic printing plate original 40 shown has a lithographic printing plate support 42 and an image recording layer 46 disposed on the lithographic printing plate support 42, such as Figure 8 As shown, preferably, an undercoat layer 44 is further provided between the lithographic printing plate support 42 and the image recording layer 46. The undercoat layer 44 is any component.

[0215] The structure of the lithographic printing plate support 42 is as described above, and the anodized film in the lithographic printing plate support 42 is disposed on the image recording layer side.

[0216] The following is a detailed description of the other components, including the original lithographic printing plate.

[0217] [Base Coating]

[0218] The base coating 44 is a layer disposed between the lithographic printing plate support 42 and the image recording layer 46 to improve the adhesion between the two. Alternatively, as mentioned above, the base coating 44 may be a layer provided as needed and may not be included in the lithographic printing plate itself.

[0219] There are no particular restrictions on the structure of the base coating, but from the viewpoint of maintaining brush resistance while suppressing ink adhesion to non-image areas, it is preferable to include polyvinylphosphonic acid.

[0220] Here, as polyvinylphosphonic acid, the substances disclosed in U.S. Patent No. 3,276,868, U.S. Patent No. 4,153,461, and U.S. Patent No. 4,689,272 can be used.

[0221] There are no particular restrictions on the structure of the base coating, but from the viewpoint of good stain resistance and deinking ability during printing pauses, compounds containing a betaine structure are preferred.

[0222] Here, a betaine structure refers to a structure having at least one cation and at least one anion. Furthermore, normally the number of cations is equal to the number of anions, resulting in an overall neutral structure. However, in this invention, even when the number of cations and anions is not equal, a counterion with a required amount is also included in the betaine structure to eliminate charge.

[0223] The betaine structure is preferably any one of the structures represented by formula (1), formula (2) and formula (3) shown below.

[0224] [Chemical Formula 1]

[0225]

[0226] In the formula, A- B represents a structure with an anion. + L represents a structure with cations. 0 * Indicates a linking group. * Indicates the linking site (linkage location).

[0227] A - Preferably, it represents a structure having anions such as carboxylates, sulfonates, phosphonates, and phosphonites, B + Preferably, it represents a structure having cations such as ammonium, phosphorus, iodine and sulfite.

[0228] L 0 This represents a linking group. In formulas (1) and (3), it is represented by L. 0 Examples of divalent linking groups include -CO-, -O-, -NH-, divalent aliphatic groups, divalent aromatic groups, or combinations thereof. In formula (2), L is used as... 0 Examples of trivalent linker groups can be given.

[0229] The linking group is preferably a linking group with 30 or fewer carbon atoms, including the substituents that may be present as described later.

[0230] Specific examples of the linking groups mentioned above include alkylene groups (preferably with 1 to 20 carbon atoms, more preferably with 1 to 10 carbon atoms) and arylene groups such as phenylene and xylene (preferably with 5 to 15 carbon atoms, more preferably with 6 to 10 carbon atoms).

[0231] In addition, these linking groups can further have substituents.

[0232] Examples of substituents include halogen atoms, hydroxyl groups, carboxyl groups, amino groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, monoalkylamino groups, dialkylamino groups, monoarylamino groups, and diarylamino groups.

[0233] From the viewpoint that at least one of the following is superior in terms of brush resistance, stain resistance, ink removal ability during printing pauses, and image visual recognizability, the structure represented by formula (i), formula (ii), or formula (iii) is preferred, and the structure represented by formula (i) is more preferred. * indicates a connecting part.

[0234] [Chemical Formula 2]

[0235]

[0236] In equation (i), R 1 and R 2 Each can independently represent a hydrogen atom, alkyl, alkenyl, alkynyl, aryl, or heterocyclic group, R 1 With R 2They can be connected to each other to form a ring structure.

[0237] The ring structure can contain heteroatoms such as oxygen atoms. Preferably, it is a 5- to 10-membered ring, more preferably a 5- or 6-membered ring.

[0238] R 1 and R 2 The number of carbon atoms in it is preferably 1 to 30, more preferably 1 to 20.

[0239] As R 1 and R 2 Preferably, hydrogen atoms, methyl or ethyl.

[0240] L 1 The linking group is a divalent group, preferably -CO-, -O-, -NH-, a divalent aliphatic group (e.g., alkylene), a divalent aromatic group (e.g., phenylene), or a combination thereof.

[0241] As L 1 Preferably, it is a straight-chain alkylene group with 3 to 5 carbon atoms.

[0242] In equation (i), A - This indicates a structure having an anionic component, preferably a carboxylate, sulfonate, phosphonate, or phosphonite.

[0243] Specifically, the following structures can be cited.

[0244] [Chemical Formula 3]

[0245]

[0246] In equation (i), L is preferred. 1 It is a straight-chain alkylene group with 4 or 5 carbon atoms and A - A combination of sulfonates, preferably L 1 It is a straight-chain alkylene group with 4 carbon atoms and A - It is a combination of sulfonates.

[0247] In equation (ii), L 2 The linking group is a divalent group, preferably -CO-, -O-, -NH-, a divalent aliphatic group (e.g., alkylene), a divalent aromatic group (e.g., phenylene), or a combination thereof.

[0248] B + The structure indicates the presence of a cation, and preferably a structure containing ammonium, phosphonium, iodine, or sulfonium. Among these, a structure containing ammonium or phosphonium is preferred, and a structure containing ammonium is even more preferred.

[0249] Examples of structures having a cation include trimethylammonium, triethylammonium, tributylammonium, benzyldimethylammonium, diethylhexylammonium, (2-hydroxyethyl)dimethylammonium, pyridinium, N-methylimidazolium, N-acridinium, trimethylphosphinium, triethylphosphinium, and triphenylphosphinium.

[0250] In equation (iii), L 3 The linking group is a divalent group, preferably -CO-, -O-, -NH-, a divalent aliphatic group (e.g., alkylene), a divalent aromatic group (e.g., phenylene), or a combination thereof.

[0251] A - The structure represents an anionic form, preferably a carboxylate, sulfonate, phosphonate, or phosphonite, and its details and preferred examples are the same as A in formula (i).

[0252] R 3 ~R 7 Each of the following independently represents a hydrogen atom or a substituent (preferably 1 to 30 carbon atoms): R 3 ~R 7 At least one of them represents a connection part.

[0253] R as a connecting part 3 ~R 7 At least one of them can be transmitted via R 3 ~R 7 At least one of the substituents in the compound is linked to other parts of the compound, or it can be directly bonded to other parts of the compound through a single bond.

[0254] As a result of R 3 ~R 7 Examples of substituents include halogen atoms, alkyl groups (including cycloalkyl and bicycloalkyl), alkenyl groups (including cycloalkenyl and bicycloalkenyl), alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, aryloxy groups, silyloxy groups, heterocyclic groups, acyloxy groups, carbamoyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, amino groups (including aniline groups), acylamino groups, aminocarbonylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, aminosulfonylamino groups, alkyl and arylsulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups, heterocyclic thio groups, aminosulfonyl groups, sulfonyl groups, alkyl and arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl and heterocyclic azo groups, imide groups, phosphinyl groups, oxophosphinyl groups, oxophosphinyloxy groups, oxophosphinylamino groups, and silylalkyl groups.

[0255] The above-mentioned compounds are preferably polymers containing repeating units having a betaine structure (hereinafter also referred to as "specific polymers"). As repeating units having a betaine structure, repeating units represented by formula (A1) are preferred.

[0256] [Chemical Formula 4]

[0257]

[0258] In the formula, R 101 ~R 103 Each of these can be used independently to represent a hydrogen atom, an alkyl group, or a halogen atom. The letter L represents a single bond or a divalent linking group.

[0259] Examples of divalent linking groups include -CO-, -O-, -NH-, divalent aliphatic groups, divalent aromatic groups, or combinations thereof.

[0260] The following are specific examples of L that include the above combinations. Additionally, in the examples below, the left side is bonded to the main chain, and the right side is bonded to X.

[0261] L1: -CO-O- divalent aliphatic group-

[0262] L2: -CO-O- divalent aromatic group-

[0263] L3: -CO-NH- divalent aliphatic group-

[0264] L4: -CO-NH- divalent aromatic group-

[0265] L5: -CO- divalent aliphatic group-

[0266] L6: -CO- divalent aromatic group-

[0267] L7: -CO- divalent aliphatic group -CO-O- divalent aliphatic group -

[0268] L8: -CO- divalent aliphatic group -O-CO- divalent aliphatic group -

[0269] L9: -CO- divalent aromatic group -CO-O- divalent aliphatic group

[0270] L10: -CO- divalent aromatic group -O-CO- divalent aliphatic group

[0271] L11: -CO- divalent aliphatic group -CO-O- divalent aromatic group -

[0272] L12: -CO- divalent aliphatic group -O-CO- divalent aromatic group

[0273] L13: -CO- divalent aromatic group -CO-O- divalent aromatic group -

[0274] L14: -CO- divalent aromatic group -O-CO- divalent aromatic group-

[0275] L15: -CO-O- divalent aromatic group -O-CO-NH- divalent aliphatic group

[0276] L16: -CO-O- divalent aliphatic group -O-CO-NH- divalent aliphatic group -

[0277] Examples of divalent aliphatic groups include alkylene, alkenylene, and ynylene.

[0278] Examples of divalent aromatic groups include aryl groups, with phenylene or naphthylene being preferred.

[0279] X represents the betaine structure. X is preferably the structure represented by formula (i), formula (ii) or formula (iii) as described above.

[0280] In particular, in equation (A1), L is preferably L1 or L3, X is the structure represented by equation (i), and A in equation (i) - It is a combination of sulfonate groups.

[0281] The content of repeating units with betaine structures in a particular polymer is not particularly limited, and is usually 20-95% by mass, preferably 50-95% by mass, and more preferably 60-90% by mass, relative to all repeating units constituting the particular polymer.

[0282] Certain polymers may contain repeating units other than those with the betaine structure described above.

[0283] Certain polymers may contain repeating units that have structures (hereinafter also referred to as "interacting structures") that interact with the surface of a support for lithographic printing plates.

[0284] Examples of interacting structures include carboxylic acid structures, carboxylate structures, sulfonic acid structures, sulfonate structures, phosphonic acid structures, phosphonate structures, phosphate ester structures, phosphate ester salt structures, β-diketone structures, and phenolic hydroxyl groups. For example, structures represented by the formulas shown below can be cited. Preferably, carboxylic acid structures, carboxylate structures, sulfonic acid structures, sulfonate structures, phosphonic acid structures, phosphonate structures, phosphate ester structures, or phosphate ester salt structures are used.

[0285] [Chemical Formula 5]

[0286] -SO3M2 -OSO3M2

[0287] In the above formula, R 11 ~R 13 Each of the following groups independently represents a hydrogen atom, alkyl, aryl, alkynyl, or alkenyl group. M, M1, and M2 independently represent a hydrogen atom, a metal atom (e.g., alkali metal atoms such as Na and Li), or an ammonium group. B represents a boron atom.

[0288] The repeating unit with the interaction structure is preferably the repeating unit represented by equation (A2).

[0289] [Chemical Formula 6]

[0290]

[0291] In the formula, R 201 ~R 203 Each of the following can be independently represented: hydrogen atom, alkyl group (preferably 1 to 6 carbon atoms) or halogen atom.

[0292] L represents a single bond or a divalent linking group. Examples of divalent linking groups include -CO-, -O-, -NH-, divalent aliphatic groups, divalent aromatic groups, or combinations thereof.

[0293] As a specific example of L including combinations, examples identical to the above formula (A1) and L17 and L18 below can be given.

[0294] L17: -CO-NH-

[0295] L18: -CO-O-

[0296] Among L1 to L18, L1 to L4, L17, or L18 are preferred.

[0297] Q represents the interaction structure, and the preferred method is the same as described above.

[0298] There is no particular limitation on the content of repeating units with interacting structures in a specific polymer, but it is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, relative to all repeating units constituting the specific polymer.

[0299] Certain polymers may contain repeating units with reactive groups that have free radical polymerization properties.

[0300] Examples of free radical polymerizable reactive groups include unsaturated groups capable of addition polymerization (e.g., (meth)acryloyl, (meth)acrylamido, (meth)acrylonitrile, allyl, vinyl, ethoxy, and alkynyl) and functional groups capable of chain transfer (such as mercapto).

[0301] A specific polymer containing repeating units with free radical polymerizable reactive groups can be obtained by introducing free radical polymerizable reactive groups using the method described in Japanese Patent Application Publication No. 2001-312068. By using the specific polymer containing repeating units with free radical polymerizable reactive groups, excellent developability is exhibited in the unexposed area, and the penetration of the developer is suppressed by polymerization in the exposed area, further improving the adhesion and bonding between the lithographic printing plate support and the image recording layer.

[0302] There is no particular limitation on the content of repeating units with free radical polymerizable reactive groups in a specific polymer, but it is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, relative to all repeating units constituting the specific polymer.

[0303] The content of the compound having the above-mentioned betaine structure in the base coating 44 is not particularly limited, but it is preferably 80% by mass or more, more preferably 90% by mass or more, relative to the total mass of the base coating. As an upper limit, 100% by mass can be cited as an example.

[0304] Furthermore, the above description refers to a base coating containing a compound having a betaine structure, but the base coating may also be in the form of containing other compounds.

[0305] For example, the base coating can be in the form of a compound containing hydrophilic groups. Examples of hydrophilic groups include carboxylic acid groups and sulfonic acid groups.

[0306] Compounds with hydrophilic groups can also have reactive groups that can polymerize on free radicals.

[0307] [Image recording layer]

[0308] As the image recording layer 46, it is preferably an image recording layer that can be removed using printing ink and / or dampening solution.

[0309] The components of the image recording layer 46 will be described below.

[0310] <Infrared absorber>

[0311] The image recording layer 46 preferably contains an infrared absorber.

[0312] Infrared absorbers preferably exhibit maximum absorption in the wavelength region of 750–1400 nm. In particular, in on-machine developing type lithographic printing plates, on-machine development is sometimes performed on a printing press under white light. Therefore, by using an infrared absorber that is not easily affected by white light and has maximum absorption in the wavelength region of 750–1400 nm, it is possible to obtain lithographic printing plate primary plates with excellent developability.

[0313] Dyes or pigments are preferred as infrared absorbers.

[0314] As for dyes, examples include commercially available dyes and well-known dyes listed in documents such as "Dye Handbook" (The Society of Synthetic Organic Chemistry, Japan, 1970).

[0315] Specifically, examples of dyes include anthocyanins, squaric acid pigments, pyranonium salts, nickel thiol complexes, and indocyanine pigments. Among these, anthocyanins or indocyanine pigments are preferred, anthocyanins are more preferred, and anthocyanins represented by the following formula (a) are even more preferred.

[0316] Equation (a)

[0317] [Chemical Formula 7]

[0318]

[0319] In equation (a), X 1 Represents hydrogen atom, halogen atom, -N(R) 9 (R) 10 -X 2 -L 1 Or the groups shown below.

[0320] [Chemical Formula 8]

[0321]

[0322] R 9 and R 10 Each can independently represent an aromatic hydrocarbon group, alkyl group, or hydrogen atom, R 9 With R 10 They can bond with each other to form a ring. Among them, phenyl is preferred.

[0323] X 2 L represents an oxygen atom or a sulfur atom. 1 It indicates a hydrocarbon group with 1 to 12 carbon atoms that can contain heteroatoms (N, S, O, halogen atoms, Se).

[0324] About X a - , in conjunction with Z as described later a - Defined in the same way, R a It represents a hydrogen atom, alkyl group, aryl group, amino group, or halogen atom.

[0325] R 1 and R 2 Each group independently represents a hydrocarbon group having 1 to 12 carbon atoms. Furthermore, R... 1 With R 2They can bond together to form rings, and when forming rings, it is preferable to form 5-membered rings or 6-membered rings.

[0326] Ar 1 and Ar 2 Each can be independently represented as an aromatic hydrocarbon group that may have a substituent (e.g., alkyl). As aromatic hydrocarbon groups, benzene ring groups or naphthyl ring groups are preferred.

[0327] Y 1 and Y 2 Each can be used independently to represent a dialkylmethylene group having 12 or fewer sulfur or carbon atoms.

[0328] R 3 and R 4 Each can be independently represented as a hydrocarbon group having 20 or fewer carbon atoms that may have a substituent (e.g., alkoxy).

[0329] R 5 R 6 R 7 and R 8 Each can be used independently to represent a hydrocarbon group with 12 or fewer hydrogen or carbon atoms.

[0330] Furthermore, Za - This indicates an anionic counteractor. Specifically, the anthocyanin represented by formula (a) has an anionic substituent within its structure, thus eliminating the need for Za without neutralizing the charge. - As Za - Examples of suitable ions include halide ions, perchlorate ions, tetrafluoroborate ions, hexafluorophosphate ions, and sulfonate ions, with perchlorate ions, hexafluorophosphate ions, or arylsulfonate ions being preferred.

[0331] The aforementioned infrared absorbing dye may be used in isolation, or in combination with two or more dyes, or in combination with infrared absorbers other than pigments or other infrared absorbing dyes. As a pigment, compounds described in paragraphs

[0072] to

[0076] of Japanese Patent Application Publication No. 2008-195018 are preferred.

[0332] The content of the infrared absorber is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, relative to the total mass of the image recording layer.

[0333] <Polymerization initiator>

[0334] The image recording layer 46 preferably contains a polymerization initiator.

[0335] As polymerization initiators, compounds that generate free radicals through light, heat, or both are preferred and initiate the polymerization of compounds having polymerizable unsaturated groups (so-called free radical polymerization initiators). Examples of polymerization initiators include photopolymerization initiators and thermal polymerization initiators.

[0336] Specifically, the polymerization initiator described in paragraphs

[0115] to

[0141] of Japanese Patent Application Publication No. 2009-255434 can be used as the polymerization initiator.

[0337] In addition, from the viewpoint of reactivity and stability, oxime ester compounds or onium salts such as diazonium salts, iodonium salts and sulfonium salts are preferred as polymerization initiators.

[0338] The content of the polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, relative to the total mass of the image recording layer.

[0339] <Polymerizing compounds>

[0340] The image recording layer 46 preferably contains a polymeric compound.

[0341] As a polymerizable compound, an addition polymerizable compound having at least one olefinic unsaturated bond is preferred. More preferably, a compound having at least one (preferably two) terminal olefinic unsaturated bonds is preferred. Even more preferred are so-called free radical polymerizable compounds.

[0342] As a polymerizable compound, for example, the polymerizable compounds illustrated in paragraphs

[0142] to

[0163] of Japanese Patent Application Publication No. 2009-255434 can be used.

[0343] Furthermore, it is preferable to use urethane-based addition polymerizable compounds manufactured by the addition reaction of isocyanates with hydroxyl groups. Specific examples include the polyisocyanate compound having two or more isocyanate groups in one molecule, as described in Japanese Patent Publication No. 48-041708, and the vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule, which is formed by the addition of a vinyl monomer containing hydroxyl groups represented by the following formula (A).

[0344] CH2=C(R 4 )COOCH2CH(R 5 )OH (A)

[0345] (where R) 4 and R 5 (This represents H or CH3.)

[0346] The content of the polymeric compound is preferably 3 to 80% by mass, more preferably 10 to 75% by mass, relative to the total mass of the image recording layer.

[0347] <Adhesive Polymers>

[0348] The image recording layer 46 preferably contains an adhesive polymer.

[0349] As adhesive polymers, well-known adhesive polymers can be cited. Specifically, examples of adhesive polymers include acrylic resins, polyvinyl acetal resins, polyurethane resins, polyurea resins, polyimide resins, polyamide resins, epoxy resins, methacrylic resins, polystyrene resins, phenolic varnish-type phenolic resins, polyester resins, synthetic rubbers, and natural rubbers.

[0350] To improve the strength of the coating in the imaging section, the adhesive polymer can be cross-linked. To achieve cross-linking in the adhesive polymer, cross-linking functional groups, such as olefinic unsaturated bonds, are introduced into the main chain or side chains of the polymer. These cross-linking functional groups can be introduced through copolymerization.

[0351] As an adhesive polymer, for example, the adhesive polymer disclosed in paragraphs

[0165] to

[0172] of Japanese Patent Application Publication No. 2009-255434 can be used.

[0352] The content of the adhesive polymer relative to the total mass of the image recording layer is preferably 5 to 90% by mass, more preferably 5 to 70% by mass.

[0353] <surfactants>

[0354] The image recording layer 46 may contain a surfactant to promote on-machine developability at the start of printing and improve the coating surface.

[0355] Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorinated surfactants.

[0356] As a surfactant, for example, the surfactant disclosed in paragraphs

[0175] to

[0179] of Japanese Patent Application Publication No. 2009-255434 can be used.

[0357] The surfactant content is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, relative to the total mass of the image recording layer.

[0358] <Coloring agent>

[0359] The image recording layer 46 preferably contains a colorant, and more preferably contains an acid colorant.

[0360] The term "color-developing agent" used in this invention refers to a compound that exhibits the property of developing or decolorizing upon stimulation by light, acid, or the like, thereby changing the color of the image recording layer. Furthermore, "acid color-developing agent" refers to a compound that exhibits the property of developing or decolorizing upon heating in a state where it has received protons from an electron-accepting compound (e.g., an acid). As acid color-developing agents, those having partial skeletons such as lactones, lactams, sulopentalides, spiropyrans, esters, and amides are particularly preferred; these partial skeletons are preferably colorless compounds that rapidly undergo ring-opening or cleave upon contact with an electron-accepting compound.

[0361] Examples of such acidic colorants include 3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide (called "crystal violet lactone"), 3,3-bis(4-dimethylaminophenyl)phthalide, 3-(4-dimethylaminophenyl)-3-(4-diethylamino-2-tolyl)-6-dimethylaminophthalide, 3-(4-dimethylaminophenyl)-3-(1,2-dimethylindol-3-yl)phthalide, and 3-(4-dimethylaminophenyl)-3-(2-methylindol-3-yl)phthalide. 3,3-Bis(1,2-dimethylindol-3-yl)-5-dimethylaminophthalide, 3,3-Bis(1,2-dimethylindol-3-yl)-6-dimethylaminophthalide, 3,3-Bis(9-ethylcarbazole-3-yl)-6-dimethylaminophthalide, 3,3-Bis(2-phenylindol-3-yl)-6-dimethylaminophthalide, 3-(4-dimethylaminophenyl)-3-(1-methylpyrrole-3-yl)-6-dimethylaminophthalide,

[0362] 3,3-Bis[1,1-bis(4-dimethylaminophenyl)vinyl-2-yl]4,5,6,7-tetrachlorophthalide, 3,3-bis[1,1-bis(4-pyrrolidinephenyl)vinyl-2-yl]-4,5,6,7-tetrabromophthalide, 3,3-bis[1-(4-dimethylaminophenyl)-1-(4-methoxyphenyl)vinyl-2-yl]-4,5,6,7-tetrachlorophthalide, 3,3-bis[1-(4-pyrrolidinephenyl)-1-(4-methoxyphenyl)vinyl-2-yl]-4,5,6,7-tetrachlorophthalide, 3-[1,1-bis(1-ethyl Phthalate derivatives include: [-2-methylindo-3-yl)vinyl-2-yl]-3-(4-diethylaminophenyl)phthalide, [3-[1,1-di(1-ethyl-2-methylindo-3-yl)vinyl-2-yl]-3-(4-N-ethyl-N-phenylaminophenyl)phthalide, [3-(2-ethoxy-4-diethylaminophenyl)-3-(1-n-octyl-2-methylindo-3-yl)phthalide, [3,3-bis(1-n-octyl-2-methylindo-3-yl)phthalide, [3-(2-methyl-4-diethylaminophenyl)-3-(1-n-octyl-2-methylindo-3-yl)phthalide, etc.]

[0363] 4,4-bis-dimethylaminobenzopropanol benzyl ether, N-halophenyl-leuco-auramine, N-2,4,5-trichlorophenylleuco-auramine, rhodamine-B-aniline lactone, rhodamine-(4-nitroaniline) lactone, rhodamine-B-(4-chloroaniline) lactone, 3,7-bis(diethylamino)-10-benzoylbenzoxazine, benzoyl colorless methylene blue, 4-nitrobenzoylmethylene blue,

[0364] 3,6-Dimethoxyfluorane, 3-Dimethylamino-7-methoxyfluorane, 3-Diethylamino-6-methoxyfluorane, 3-Diethylamino-7-methoxyfluorane, 3-Diethylamino-7-chlorofluorane, 3-Diethylamino-6-methyl-7-chlorofluorane, 3-Diethylamino-6,7-dimethylfluorane, 3-N-cyclohexyl-N-n-butylamino-7-methylfluorane, 3-Diethylamino-7-dibenzylaminofluorane, 3-Diethylamino-7-octylaminofluorane, 3-Diethylamino-7-di-n-hexylaminofluorane, 3-Diethylamino-7-anilinefluorane, 3- Diethylamino-7-(2'-fluorophenylamino)fluorane, 3-diethylamino-7-(2'-chlorophenylamino)fluorane, 3-diethylamino-7-(3'-chlorophenylamino)fluorane, 3-diethylamino-7-(2',3'-dichlorophenylamino)fluorane, 3-diethylamino-7-(3'-trifluoromethylphenylamino)fluorane, 3-di-n-butylamino-7-(2'-fluorophenylamino)fluorane, 3-di-n-butylamino-7-(2'-chlorophenylamino)fluorane, 3-N-isopentyl-N-ethylamino-7-(2'-chlorophenylamino)fluorane,

[0365] 3-N-hexyl-N-ethylamino-7-(2'-chlorophenylamino)fluorane, 3-diethylamino-6-chloro-7-anilinefluorane, 3-di-n-butylamino-6-chloro-7-anilinefluorane, 3-diethylamino-6-methoxy-7-anilinefluorane, 3-di-n-butylamino-6-ethoxy-7-anilinefluorane, 3-pyrrolidine-6-methyl-7-anilinefluorane, 3-hydropyridyl-6-methyl-7-anilinefluorane, 3-morpholinyl- 6-Methyl-7-anilinefluorane, 3-dimethylamino-6-methyl-7-anilinefluorane, 3-diethylamino-6-methyl-7-anilinefluorane, 3-di-n-butylamino-6-methyl-7-anilinefluorane, 3-di-n-pentanamino-6-methyl-7-anilinefluorane, 3-N-ethyl-N-methylamino-6-methyl-7-anilinefluorane, 3-N-n-propyl-N-methylamino-6-methyl-7-anilinefluorane, 3-N-n-propyl-N- Ethylamino-6-methyl-7-anilinefluorane, 3-N-n-butyl-N-methylamino-6-methyl-7-anilinefluorane, 3-N-n-butyl-N-ethylamino-6-methyl-7-anilinefluorane, 3-N-isobutyl-N-methylamino-6-methyl-7-anilinefluorane, 3-N-isobutyl-N-ethylamino-6-methyl-7-anilinefluorane, 3-N-isopentyl-N-ethylamino-6-methyl-7-anilinefluorane, 3-N-n-hexyl 3-N-Cyclohexyl-N-ethylamino-6-methyl-7-anilinefluorane, 3-N-Cyclohexyl-N-n-propylamino-6-methyl-7-anilinefluorane, 3-N-Cyclohexyl-N-n-butyl-6-methyl-7-anilinefluorane, 3-N-Cyclohexyl-N-n-hexylamino-6-methyl-7-anilinefluorane, 3-N-Cyclohexyl-N-n-octylamino-6-methyl-7-anilinefluorane,

[0366] 3-N-(2'-methoxyethyl)-N-methylamino-6-methyl-7-anilinefluorane, 3-N-(2'-methoxyethyl)-N-ethylamino-6-methyl-7-anilinefluorane, 3-N-(2'-methoxyethyl)-N-isobutylamino-6-methyl-7-anilinefluorane, 3-N-(2'-ethoxyethyl)-N-methylamino-6-methyl-7-phenylaminofluorane, 3-N-(2'-ethoxyethyl)-N-ethylamino 3-N-(3'-methoxypropyl)-N-methylamino-6-methyl-7-anilinefluorane, 3-N-(3'-methoxypropyl)-N-ethylamino-6-methyl-7-anilinefluorane, 3-N-(3'-ethoxypropyl)-N-methylamino-6-methyl-7-anilinefluorane, 3-N-(3'-ethoxypropyl)-N-ethylamino-6-methyl-7-anilinefluorane, 3-N-( 2'-Tetrahydrofurfuryl)-N-ethylamino-6-methyl-7-anilinefluorane, 3-N-(4'-tolyl)-N-ethylamino-6-methyl-7-anilinefluorane, 3-diethylamino-6-ethyl-7-anilinefluorane, 3-diethylamino-6-methyl-7-(3'-tolylamino)fluorane, 3-diethylamino-6-methyl-7-(2',6'-ditolylamino)fluorane, 3-di-n-butylamino-6-methyl-7 Fluoranes such as -(2',6'-dimethylamino)fluorane, 3-di-n-butylamino-7-(2',6'-dimethylamino)fluorane, 2,2-bis[4'-(3-N-cyclohexyl-N-methylamino-6-methylfluorane)-7-ylaminophenyl]propane, 3-[4'-(4-phenylaminophenyl)aminophenyl]amino-6-methyl-7-chlorofluorane, 3-[4'-(dimethylaminophenyl)]amino-5,7-dimethylfluorane, etc.

[0367] 3-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalide, 3-(2-n-propoxycarbonylamino-4-di-n-propanaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalide, 3-(2-methylamino-4-di-n-propanaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalide, 3-(2-methyl-4-di-n-hexaneaminophenyl)-3-(1-n-octyl-2- 3-Methylindole-3-yl)-4,7-diazaphthalide, 3,3-bis(2-ethoxy-4-diethylaminophenyl)-4-diazaphthalide, 3,3-bis(1-n-octyl-2-methylindole-3-yl)-4-diazaphthalide, 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-diazaphthalide, 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-octyl-2-methylindole-3-yl)-4 or 7-diazaphthalide, 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)-4 or 7-azaphthalide, 3-(2-hexyloxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)-4 or 7-azaphthalide, 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-phenylindole-3-yl)-4 or 7-azaphthalide, 3-(2-butoxy-4-diethylaminophenyl)-3-(1-ethyl-2-phenyl) Phthalate derivatives including indole-3-yl)-4 or 7-azaphthalide, 3-methyl-spiro-dinaphthopiperan, 3-ethyl-spiro-dinaphthopiperan, 3-phenyl-spiro-dinaphthopiperan, 3-benzyl-spiro-dinaphthopiperan, 3-methyl-naphtho-(3-methoxybenzo)spiropiperan, 3-propyl-spiro-dibenzopiperan-3,6-bis(dimethylamino)fluorene-9-spiro-3'-(6'-dimethylamino)phthalide, and 3,6-bis(diethylamino)fluorene-9-spiro-3'-(6'-dimethylamino)phthalide.

[0368] In addition, there are 2'-anilino-6'-(N-ethyl-N-isopentyl)amino-3'-methylspiro[isobenzofuran-1(3H),9'-(9H)xanton]-3-one, 2'-anilino-6'-(N-ethyl-N-(4-tolyl))amino-3'-methylspiro[isobenzofuran-1(3H),9'-(9H)xanton]-3-one, 3'-N,N-dibenzylamino-6'-N,N-diethylaminospiro[isobenzofuran-1(3H),9'-(9H)xanton]-3-one, 2'-(N-methyl-N-phenyl)amino-6'-(N-ethyl-N-(4-tolyl))aminospiro[isobenzofuran-1(3H),9'-(9H)xanton]-3-one, etc.

[0369] From the viewpoint of color development, the color-developing agent used in this invention is preferably selected from at least one compound selected from spiropyran compounds, spiroxazine compounds, spironolactone compounds, and spironolactam compounds.

[0370] From a visibility point of view, the preferred hue of the pigment after color development is green, blue, or black.

[0371] Furthermore, from the viewpoint of color development and visual recognizability of the exposed part, the aforementioned acid colorant is preferably a colorless pigment.

[0372] As for the aforementioned colorless pigment, there are no particular restrictions as long as it has a colorless structure, but it is preferred to have a spiro structure, and more preferably to have a spironolactone ring structure.

[0373] Furthermore, from the viewpoint of color development and visual recognizability of the exposed portion, the colorless pigment described above is preferably a colorless pigment having a phthaloyl structure or a fluorane structure.

[0374] Furthermore, from the viewpoint of color development and visual recognizability of the exposed portion, the aforementioned colorless pigment having a phthaloyl or fluorane structure is preferably a compound represented by any one of the following formulas (Le-1) to (Le-3), and more preferably a compound represented by the following formula (Le-2).

[0375] [Chemical Formula 9]

[0376]

[0377] In formulas (Le-1) to (Le-3), ERG independently represents an electron-donating group, X1 to X4 independently represent a hydrogen atom, a halogen atom, or a dialkylaniline group, and X5 to X 10 Each of the following groups independently represents a hydrogen atom, a halogen atom, or a monovalent organic group. Y1 and Y2 independently represent C or N. When Y1 is N, X1 does not exist. When Y2 is N, X4 does not exist. Ra1 represents a hydrogen atom, an alkyl group, or an alkoxy group. Rb1 to Rb4 independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.

[0378] From the viewpoint of colorimetry and visual recognizability of the exposed portion, the electron-donating group in the ERG of formulas (Le-1) to (Le-3) is preferably amino, alkylamino, arylamino, heteroarylamino, dialkylamino, monoalkyl monoarylamino, monoalkyl monoheteroarylamino, diarylamino, diheteroarylamino, monoaryl monoheteroarylamino, alkoxy, aryloxy, heteroaryloxy, or alkyl. More preferably, it is amino, alkylamino, arylamino, heteroarylamino, dialkylamino, monoalkyl monoarylamino, monoalkyl monoheteroarylamino, diarylamino, diheteroarylamino, monoaryl monoheteroarylamino, alkoxy, or aryloxy. Even more preferably, it is monoalkyl monoarylamino, diarylamino, diheteroarylamino, or monoaryl monoheteroarylamino, and especially preferably monoalkyl monoarylamino.

[0379] Furthermore, from the viewpoint of color development and visual recognizability of the exposed portion, the electron-donating group in the aforementioned ERG is preferably a disubstituted amino group having an aryl group with a substituent at at least one ortho position or a heteroaryl group with a substituent at at least one ortho position. More preferably, it is a disubstituted amino group having a phenyl group with a substituent at at least one ortho position and an electron-donating group at the para position. Even more preferably, it is an amino group having a phenyl group with a substituent at at least one ortho position and an electron-donating group at the para position and an aryl group or a heteroaryl group with an electron-donating group. Particularly preferred is an amino group having a phenyl group with a substituent at at least one ortho position and an electron-donating group at the para position and an aryl group or a heteroaryl group with an electron-donating group.

[0380] In addition, in this invention, the adjacent position in aryl or heteroaryl groups other than phenyl refers to the bonding position (e.g., position 2, etc.) adjacent to the aforementioned position 1 when the bonding position of the aryl or heteroaryl group with other structures is set to position 1.

[0381] Furthermore, from the viewpoint of color development and visual recognizability of the exposed portion, the electron-donating groups of the aforementioned aryl or heteroaryl groups are preferably amino, alkylamino, arylamino, heteroarylamino, dialkylamino, monoalkylmonoarylamino, monoalkylmonoheteroarylamino, diarylamino, diheteroarylamino, monoarylmonoheteroarylamino, alkoxy, aryloxy, heteroaryloxy, or alkyl, more preferably alkoxy, aryloxy, heteroaryloxy, or alkyl, and even more preferably alkoxy.

[0382] From the viewpoint of color development and visual recognizability of the exposed part, X1 to X4 in formulas (Le-1) to (Le-3) are each preferably hydrogen atoms or chlorine atoms, and more preferably hydrogen atoms.

[0383] From the perspective of color development and visual recognizability of the exposed area, X5 to X in formula (Le-2) or formula (Le-3) 10The atom is preferably hydrogen, halogen, alkyl, aryl, amino, alkylamino, arylamino, heteroarylamino, dialkylamino, monoalkylmonoarylamino, monoalkylmonoheteroarylamino, diarylamino, diheteroarylamino, monoarylmonoheteroarylamino, hydroxyl, alkoxy, aryloxy, heteroaryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, or cyano, more preferably hydrogen, halogen, alkyl, aryl, alkoxy, or aryloxy, even more preferably hydrogen, halogen, alkyl, or aryl, and especially preferably hydrogen.

[0384] From the viewpoint of color development and visual recognizability of the exposed part, Y1 and Y2 in formulas (Le-1) to (Le-3) are preferably at least one of them as C, and more preferably both Y1 and Y2 are C.

[0385] From the viewpoint of color development and visual recognizability of the exposed part, Ra1 in formulas (Le-1) to (Le-3) is preferably alkyl or alkoxy, more preferably alkoxy, and even more preferably methoxy.

[0386] From the viewpoint of color development and visual recognizability of the exposed part, Rb1 to Rb4 in formulas (Le-1) to (Le-3) are each preferably hydrogen atoms or alkyl groups, more preferably alkyl groups, and even more preferably methyl groups.

[0387] Furthermore, from the viewpoint of color development and visual recognizability of the exposed portion, the aforementioned colorless pigment having a phthaloyl or fluorane structure is more preferably a compound represented by any one of the following formulas (Le-4) to (Le-6), and even more preferably a compound represented by the following formula (Le-5).

[0388] [Chemical Formula 10]

[0389]

[0390] In formulas (Le-4) to (Le-6), ERG independently represents an electron-donating group, X1 to X4 independently represent a hydrogen atom, a halogen atom, or a dialkylaniline group, Y1 and Y2 independently represent C or N, X1 is absent when Y1 is N, X4 is absent when Y2 is N, Ra1 represents a hydrogen atom, an alkyl group, or an alkoxy group, and Rb1 to Rb4 independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.

[0391] The ERG, X1 to X4, Y1, Y2, Ra1 and Rb1 to Rb4 in equations (Le-4) to (Le-6) have the same meaning as the ERG, X1 to X4, Y1, Y2, Ra1 and Rb1 to Rb4 in equations (Le-1) to (Le-3), and the preferred methods are also the same.

[0392] Furthermore, from the viewpoint of color development and visual recognizability of the exposed portion, the aforementioned colorless pigment having a phthaloyl or fluorane structure is more preferably a compound represented by any one of the following formulas (Le-7) to (Le-9), and especially preferably a compound represented by the following formula (Le-8).

[0393] [Chemical Formula 11]

[0394]

[0395] In formulas (Le-7) to (Le-9), X1 to X4 independently represent hydrogen atoms, halogen atoms, or dialkylaniline groups, respectively; Y1 and Y2 independently represent C or N, respectively; when Y1 is N, X1 does not exist; when Y2 is N, X4 does not exist; Ra1 to Ra4 independently represent hydrogen atoms, alkyl groups, or alkoxy groups, respectively; Rb1 to Rb4 independently represent hydrogen atoms, alkyl groups, aryl groups, or heteroaryl groups, respectively; and Rc1 and Rc2 independently represent aryl groups or heteroaryl groups, respectively.

[0396] The meanings of X1 to X4, Y1 and Y2 in equations (Le-7) to (Le-9) are the same as those of X1 to X4, Y1 and Y2 in equations (Le-1) to (Le-3), and the preferred methods are also the same.

[0397] From the viewpoint of color development and visual recognizability of the exposed part, Ra1 to Ra4 in formula (Le-7) or formula (Le-9) are each preferably alkyl or alkoxy, more preferably alkoxy, and even more preferably methoxy.

[0398] From the viewpoint of color development and visual recognizability of the exposed part, Rb1 to Rb4 in formulas (Le-7) to (Le-9) are each preferably aryl groups substituted with hydrogen atoms, alkyl groups or alkoxy groups, more preferably alkyl groups, and even more preferably methyl groups.

[0399] From the viewpoint of color development and visual recognizability of the exposed part, Rc1 and Rc2 in formula (Le-8) are preferably phenyl or alkylphenyl, and more preferably phenyl.

[0400] Furthermore, from the viewpoint of color development and visual recognizability of the exposed portion, Rc1 and Rc2 in formula (Le-8) are each preferably aryl groups having a substituent at at least one ortho position or heteroaryl groups having a substituent at at least one ortho position, more preferably aryl groups having a substituent at at least one ortho position, even more preferably phenyl groups having a substituent at at least one ortho position, and particularly preferably phenyl groups having a substituent at at least one ortho position and an electron-donating group at the para position. Examples of the substituents in Rc1 and Rc2 described later can be cited.

[0401] Furthermore, in formula (Le-8), from the viewpoint of color development and visual recognizability of the exposed part, it is preferable that X1 to X4 are hydrogen atoms and Y1 and Y2 are C atoms.

[0402] Furthermore, in formula (Le-8), from the viewpoint of color development and visual recognizability of the exposed portion, Rb1 and Rb2 are each preferably aryl groups substituted with alkyl or alkoxy groups.

[0403] Furthermore, in formula (Le-8), from the viewpoint of color development and visual recognizability of the exposed portion, Rb1 and Rb2 are each preferably aryl or heteroaryl, more preferably aryl, even more preferably aryl having an electron-donating group, and especially preferably phenyl having an electron-donating group at the para position.

[0404] Furthermore, from the viewpoint of colorimetry and visual recognizability of the exposed portion, the electron-donating groups in Rb1, Rb2, Rc1, and Rc2 are preferably amino, alkylamino, arylamino, heteroarylamino, dialkylamino, monoalkylmonoarylamino, monoalkylmonoheteroarylamino, diarylamino, diheteroarylamino, monoarylmonoheteroarylamino, alkoxy, aryloxy, heteroaryloxy, or alkyl, more preferably alkoxy, aryloxy, heteroaryloxy, or alkyl, and even more preferably alkoxy.

[0405] Furthermore, from the viewpoint of color development and visual recognizability of the exposed portion, it is preferable to use a compound represented by the following formula (Le-10) as the acid colorant.

[0406] [Chemical Formula 12]

[0407]

[0408] In formula (Le-10), Ar1 independently represents aryl or heteroaryl, and Ar2 independently represents aryl with substituents at at least one ortho position, or heteroaryl with substituents at at least one ortho position.

[0409] Ar1 in formula (Le-10) has the same meaning as Rb1 and Rb2 in formulas (Le-7) to (Le-9), and the preferred method is also the same.

[0410] Ar2 in equation (Le-10) has the same meaning as Rc1 and Rc2 in equations (Le-7) to (Le-9), and the preferred method is also the same.

[0411] Furthermore, from the viewpoint of color development and visual recognizability of the exposed portion, it is preferable to use a compound represented by the following formula (Le-11) as the acid colorant.

[0412] [Chemical Formula 13]

[0413]

[0414] In formula (Le-11), ERG independently represents electron-donating groups, n11 represents an integer from 1 to 5, X1 to X4 independently represent hydrogen atoms, halogen atoms or dialkylaniline groups, Y1 and Y2 independently represent C or N, X1 does not exist when Y1 is N, X4 does not exist when Y2 is N, and Rb2 and Rb4 independently represent hydrogen atoms, alkyl, aryl or heteroaryl groups.

[0415] In formula (Le-11), ERG, X1~X4, Y1, Y2, Rb2 and Rb4 have the same meaning as ERG, X1~X4, Y1, Y2, Rb2 and Rb4 in formulas (Le-1) to (Le-3), and the preferred methods are also the same.

[0416] In formula (Le-11), n11 is preferably an integer from 1 to 3, and more preferably 1 or 2.

[0417] The alkyl groups in formulas (Le-1) to (Le-9) and (Le-11) can be straight-chain, branched, or have a cyclic structure.

[0418] Furthermore, the number of carbon atoms of the alkyl group in formulas (Le-1) to (Le-9) and (Le-11) is preferably 1 to 20, more preferably 1 to 8, even more preferably 1 to 4, and especially preferably 1 or 2.

[0419] The number of carbon atoms in the aryl group in formulas (Le-1) to (Le-11) is preferably 6 to 20, more preferably 6 to 10, and even more preferably 6 to 8.

[0420] As aryl groups in formulas (Le-1) to (Le-11), examples include phenyl, naphthyl, anthracene, and phenanthrene groups, which may have substituents.

[0421] As for the heteroaryl groups in formulas (Le-1) to (Le-11), examples include those that can have substituents, such as furanyl, pyridyl, pyrimidinyl, pyrazolyl, and phenylthioyl.

[0422] Furthermore, the monovalent organic groups, alkyl, aryl, heteroaryl, dialkylaniline, alkylamino, and alkoxy groups in formulas (Le-1) to (Le-10) can have substituents. Examples of substituents include alkyl, aryl, heteroaryl, halogen atoms, amino, alkylamino, arylamino, heteroarylamino, dialkylamino, monoalkylmonoarylamino, monoalkylmonoheteroarylamino, diarylamino, diheteroarylamino, monoarylmonoheteroarylamino, hydroxyl, alkoxy, aryloxy, heteroaryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, and cyano. Moreover, these substituents can be further substituted by these substituents.

[0423] The following compounds are examples of colorless pigments having a phthalide or fluorane structure that are preferred for use. Additionally, Me represents a methyl group.

[0424] [Chemical Formula 14]

[0425]

[0426] [Chemical Formula 15]

[0427]

[0428] [Chemical Formula 16]

[0429]

[0430] [Chemical Formula 17]

[0431]

[0432] [Chemical Formula 18]

[0433]

[0434] [Chemical Formula 19]

[0435]

[0436] [Chemical Formula 20]

[0437]

[0438] As a color-developing agent, commercially available products can also be used, including ETAC, RED500, RED520, CVL, S-205, BLACK305, BLACK400, BLACK100, BLACK500, H-7001, GREEN300, NIRBLACK78, BLUE220, H-3035, BLUE203, ATP, H-1046, H-2114 (all manufactured by Fukui Yamada Chemical Co., Ltd.), ORANGE-DCF, Vermilion-DCF, PINK-DCF, RED-DCF, BLMB, CVL, GREEN-DCF, and TH-107 (all manufactured by HODOGAYA CHEMICAL). ODB, ODB-2, ODB-4, ODB-250, ODB-BlackXV, Blue-63, Blue-502, GN-169, GN-2, Green-118, Red-40, Red-8 (all manufactured by YAMAMOTO CHEMI CALS INC.), and crystal violet lactone (manufactured by Tokyo Chemical Industry Co., Ltd.) are among the commercially available products. Among these, films formed from ETAC, S-205, BLACK305, BLACK400, BLACK100, BLACK500, H-7001, GREEN300, NIRBLACK78, H-3035, ATP, H-1046, H-2114, GREEN-DCF, Blue-63, GN-169, and crystal violet lactone exhibit good visible light absorption and are therefore preferred.

[0439] These colorants can be used alone or in combination with two or more ingredients.

[0440] The content of the colorant is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, relative to the total mass of the image recording layer.

[0441] As needed, the image recording layer 46 may also contain other compounds besides those described above.

[0442] Other compounds include colorants, printing agents, polymerization inhibitors, higher fatty acid derivatives, plasticizers, inorganic microparticles and low molecular weight hydrophilic compounds disclosed in Japanese Patent Application Publication No. 2009-255434, paragraphs

[0181] to

[0190] .

[0443] As a polymerization inhibitor, known polymerization inhibitors such as phenothiazine can be used.

[0444] Furthermore, other compounds include hydrophobic precursors (which can convert the image recording layer into hydrophobic particles when heated), low molecular weight hydrophilic compounds, sensitizers (e.g., phosphonium compounds, nitrogen-containing low molecular weight compounds, ammonium-containing polymers), and chain transfer agents disclosed in Japanese Patent Application Publication No. 2012-187907, paragraphs

[0191] to

[0217] .

[0445] [Other layers]

[0446] The original lithographic printing plate of the present invention may include other layers besides the lithographic printing plate support 42, the base coating layer 44 and the image recording layer 46 described above.

[0447] For example, a protective layer may be included on the image recording layer 46 as needed to prevent scratches, oxygen barriers, and ablation during high-intensity laser exposure.

[0448] Materials used in the protective layer include, for example, those described in paragraphs

[0213] to

[0227] of Japanese Patent Application Publication No. 2009-255434 (water-soluble polymers, inorganic layered compounds, etc.).

[0449] [Method for manufacturing the original lithographic printing plate]

[0450] The method for manufacturing the original lithographic printing plate of the present invention described above is preferably a manufacturing method that performs the following steps sequentially after the method for manufacturing the support body for the lithographic printing plate of the present invention described above.

[0451] (Primer Coating Forming Process) The process of forming a primer coating on a support for offset printing plates.

[0452] (Image recording layer formation process) The process of forming an image recording layer on the primer layer.

[0453] The steps for each process are described in detail below.

[0454] <Undercoat Formation Process>

[0455] The base coating forming process is the process of forming a base coating on a support for a lithographic printing plate.

[0456] There are no particular limitations on the manufacturing method of the base coating. For example, a method can be described as applying a base coating forming liquid containing a specified compound (e.g., a compound having a betaine structure) onto an anodized film of a lithographic printing plate support.

[0457] Preferably, the coating liquid used to form the primer layer contains a solvent. Examples of solvents include water or organic solvents.

[0458] Various known methods can be cited as methods for applying coating liquids used to form primer layers. For example, bar coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, doctor blade coating, and roller coating can be cited.

[0459] The preferred coating weight (solid content) for the primer layer is 0.1–100 mg / m³. 2 .

[0460] <Image Recording Layer Formation Process>

[0461] The image recording layer formation process is the process of forming an image recording layer on a base layer.

[0462] There are no particular limitations on the method of forming the image recording layer. For example, a method can be described by coating an image recording layer forming coating liquid containing specified components (such as infrared absorbers, polymerization initiators, polymerizable compounds, etc.) onto a base layer.

[0463] Preferably, the coating solution used to form the image recording layer contains a solvent. Examples of solvents include water or organic solvents.

[0464] Regarding the coating method for forming an image recording layer, an example of a coating method for forming an undercoat layer can be given.

[0465] The coating amount (solid content) of the image recording layer varies depending on the application, but is generally preferred to be 0.3–3.0 g / m². 2 .

[0466] Furthermore, when a protective layer is provided on the image recording layer, there are no particular limitations on the method of manufacturing the protective layer. For example, a method of applying a protective layer forming coating liquid containing specified components onto the image recording layer can be cited.

[0467] Furthermore, in the above Figure 8 The method of using the base coat 44 is described, but as mentioned above, the base coat may not be included in the original lithographic printing plate.

[0468] Without applying a base coating, an image recording layer can be formed by performing a hydrophilic treatment on the support for lithographic printing plates.

[0469] As a hydrophilization treatment, known methods disclosed in paragraphs

[0109] to

[0114] of Japanese Patent Application Publication No. 2005-254638 can be cited. Among these, the hydrophilization treatment is preferably performed by immersion in an aqueous solution of alkali metal silicates such as sodium silicate and potassium silicate, or by coating a hydrophilic vinyl polymer or hydrophilic compound to form a hydrophilic base coating.

[0470] The hydrophilization treatment using aqueous solutions of alkali metal silicates such as sodium silicate and potassium silicate can be carried out according to the methods and steps described in U.S. Patent No. 2,714,066 and U.S. Patent No. 3,181,461.

[0471] [Methods for manufacturing offset printing plates]

[0472] Next, the method for manufacturing a lithographic printing plate using a lithographic printing plate master is described.

[0473] The manufacturing method of lithographic printing plates typically includes: an exposure process, in which the original lithographic printing plate is exposed in an image-like manner (image exposure) to form exposed and unexposed areas; and a process of removing the unexposed areas of the original lithographic printing plate that has been exposed in an image-like manner.

[0474] More specifically, one method of manufacturing a lithographic printing plate includes: an exposure step in which the original lithographic printing plate is exposed in an image-like manner (image exposure) to form exposed and unexposed areas; and a removal step in which the unexposed areas of the original lithographic printing plate are removed using a developing solution with a pH of 2 to 12.

[0475] Furthermore, another method for manufacturing a lithographic printing plate can be described as follows: an exposure step in which the original lithographic printing plate is exposed in an image-like manner (image exposure) to form an exposed portion and an unexposed portion; and an on-machine developing step in which at least one of printing ink and dampening solution is supplied to remove the unexposed portion of the original lithographic printing plate that has been exposed in an image-like manner on the printing press.

[0476] The following is a detailed description of these methods.

[0477] The method for manufacturing a lithographic printing plate includes a step of exposing the aforementioned lithographic printing plate original in an image-like manner (image exposure) (especially, an image exposure step using infrared laser). Regarding image exposure, for example, it can be performed using laser exposure through a transparent original image having a line image or a halftone image, or by scanning a laser beam based on digital data.

[0478] The wavelength of the light source is preferably 750–1400 nm. In the case of a light source that emits light with a wavelength of 750–1400 nm, it is preferable to use an image recording layer containing an infrared absorber that is an absorbing pigment in this wavelength region.

[0479] Examples of light sources that emit wavelengths of 750–1400 nm include solid-state lasers and semiconductor lasers that emit infrared radiation. For infrared lasers, the output power is preferably 100 mW or higher, the exposure time per pixel is preferably less than 20 microseconds, and the irradiation energy is preferably 10–300 mJ / cm².2 Furthermore, to shorten the exposure time, a multi-beam laser device is preferred. The exposure mechanism can be any of the following: internal drum, external drum, or flat panel type.

[0480] Regarding image exposure, it can be performed using conventional methods such as a plate-making machine. Alternatively, in the case of the on-machine development method described later, the image exposure of the lithographic printing plate can be performed on the printing press after the original lithographic printing plate is mounted on the printing press.

[0481] For lithographic printing plates that have been exposed to an image, development is performed by removing the unexposed areas using a developer with a pH of 2 to 12 (developer treatment method) or by removing the unexposed areas on the printing press using at least one of printing ink and dampening solution (on-machine development method).

[0482] <Developer treatment method>

[0483] In the developing process, the original lithographic printing plate that has been exposed to an image is treated with a developing solution with a pH of 2 to 14 to remove the image recording layer of the unexposed areas and produce a lithographic printing plate.

[0484] As a developer, it is preferable to have a compound (specific compound) having at least one acid group and at least one carboxyl group selected from phosphate group, phosphonic acid group and hypophosphonic acid group and having a pH of 5 to 10.

[0485] As a method of developing, in the case of manual processing, for example, one can rub the entire lithographic printing plate original while thoroughly soaking it in developer solution with a sponge or cotton wool, and then dry it thoroughly after processing. In the case of immersion processing, for example, one can immerse the lithographic printing plate original in a large vat or deep tank containing developer solution for about 60 seconds and stir it, and then dry it thoroughly while rubbing it with cotton wool or a sponge.

[0486] In the developing process, it is preferable to use a device that simplifies the structure and the process.

[0487] In the traditional developing process, the protective layer is removed by a pre-washing step, followed by development with an alkaline developer, then the alkali is removed by a post-washing step, the adhesive is applied by a coating step, and finally the product is dried by a drying step.

[0488] Furthermore, it is possible to simultaneously perform development and coating with a single solution. As the adhesive, polymers are preferred, and water-soluble polymers and surfactants are more preferred.

[0489] Furthermore, it is preferable to perform the protective layer removal, development, and coating simultaneously using a single solution without a pre-washing process. Also, it is preferable to remove any remaining developer solution using a squeeze roller after development and coating, followed by drying.

[0490] This process can be a single immersion in the developer solution or a immersion twice or more. Preferably, the method involves immersion once or twice in the developer solution.

[0491] Regarding immersion, the exposed lithographic printing plate can be inserted into a developing solution tank containing developing solution, or developing solution can be sprayed onto the surface of the exposed lithographic printing plate using a sprayer or similar device.

[0492] In addition, even when immersing in the developer solution more than twice, when the same developer solution is used or when immersing in the developer solution (fatigue solution) and the components of the image recording layer that are dissolved or dispersed by the developing process are used more than twice, it is called developing with 1 solution (1 solution processing).

[0493] Furthermore, in the developing process, friction components are preferably used, and friction components such as brushes are preferably provided in the developing bath for removing the non-image portion of the image recording layer.

[0494] Regarding the developing process, conventional methods can be used, preferably at a temperature of 0–60°C, more preferably 15–40°C, for example, immersing the exposed lithographic printing plate in the developing solution and wiping it with a brush, or pumping the developing solution from an external tank and spraying it from a nozzle while wiping it with a brush. These developing processes can also be performed multiple times consecutively. For example, after pumping the developing solution from an external tank and spraying it from a nozzle while wiping it with a brush, the developing solution can be sprayed from the nozzle again and wiped with a brush. When using an automatic developing machine, the developing solution becomes fatigued as the processing volume increases; therefore, it is preferable to use replenishment solution or fresh developing solution to restore processing capacity.

[0495] In the developing process of this invention, conventionally known coating machines and automatic developing machines for PS plates (Presensitized Plates) and CTP (Computer-to-Plate) can also be used. When using an automatic developing machine, for example, any of the following methods can be applied: pumping developing solution injected into a developing tank or an external tank and spraying it from a nozzle for processing; immersing and conveying the printing plate in a tank filled with developing solution via guide rollers or the like for processing; or a so-called one-time processing method that supplies each plate with the required amount of substantially unused developing solution. In any of these methods, a brush-based or double-sided wiping mechanism is more preferred. For example, commercially available automatic developing machines (Clean Out Unit C85 / C125, Clean-Out Unit+C85 / 120, FCF 85V, FCF 125V, FCF News (manufactured by Glunz & Jensen)) and Azura CX85, Azura CX125, Azura CX150 (manufactured by AGFA GRAPHICS) can be used. Furthermore, devices that integrate the laser exposure unit and the automatic developing machine into a single unit can also be used.

[0496] <In-machine development method>

[0497] In the on-machine development method, the lithographic printing plate original exposed to the image is used to produce a lithographic printing plate by supplying printing ink and dampening solution on the printing press to remove the image recording layer of the non-image area.

[0498] That is, if the lithographic printing plate is directly mounted on the printing press after image exposure without any developing solution treatment, or if the lithographic printing plate is mounted on the printing press and then image exposure is performed, followed by the supply of printing ink and dampening solution and printing, then in the initial stage of printing, in the non-image section, the image recording layer in the unexposed area is dissolved or dispersed and removed by the supplied printing ink and / or dampening solution, thereby exposing the hydrophilic surface to that area. On the other hand, in the exposure section, the image recording layer cured by exposure forms an oily ink receiving section with an oleophilic surface. The compound initially supplied to the plate can be either printing ink or dampening solution, but from the viewpoint of preventing contamination of the image recording layer components from which dampening solution has been removed, it is preferable to supply printing ink first.

[0499] Thus, the lithographic printing plate is developed on the printing press and directly used in multiple printings. Specifically, as one aspect of the printing method of the present invention, a printing method can be described as follows: an exposure step, in which the lithographic printing plate is exposed in an image-like manner to form exposed and unexposed portions; and a printing step, in which at least one of printing ink and dampening solution is supplied to remove the unexposed portions of the lithographic printing plate that has been exposed in an image-like manner on the printing press, and printing is performed.

[0500] In the method for manufacturing a lithographic printing plate from the lithographic printing plate original involved in this invention, regardless of the development method, the entire surface of the lithographic printing plate original can be heated as needed before image exposure, during image exposure, or during the period from image exposure to development.

[0501] Example

[0502] The features of the present invention will be further described in detail below with examples and comparative examples. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention is not to be interpreted as limited by the specific examples shown below.

[0503] [Manufacturing of Supports for Offset Printing Plates]

[0504] A support for a lithographic printing plate was manufactured by performing the following treatment on an aluminum plate (aluminum alloy plate) of material 1S with a thickness of 0.3 mm. In addition, a water washing process was performed between all processing steps, and the liquid was drained by clamping rollers after the water washing process.

[0505] [Example 1]

[0506] <First Alkali Etching Treatment>

[0507] Etching was performed on an aluminum plate by spraying an aqueous solution of caustic soda (26% by mass) and aluminum ions (6.5% by mass) using a sprayer at 70°C. This was followed by a spray-based water wash. The aluminum dissolution rate on the surface after electrochemical roughening was 5 g / m². 2 .

[0508] <First decontamination treatment using acidic aqueous solution>

[0509] Next, an acidic aqueous solution was used for decontamination. Specifically, the acidic aqueous solution was sprayed onto the aluminum plate using a sprayer and the decontamination was carried out for 3 seconds. The acidic aqueous solution used for decontamination was a 150 g / L sulfuric acid solution at a temperature of 30°C.

[0510] <Electrochemical roughening treatment>

[0511] Next, an electrochemical roughening treatment was performed using an electrolyte solution with a hydrochloric acid concentration of 10 g / L, an aluminum ion concentration of 15 g / L, and a sulfuric acid concentration of 1.0 g / L, and using alternating current. The electrolyte temperature was maintained at 15°C. The aluminum ion concentration was adjusted by adding aluminum chloride.

[0512] The alternating current waveform is a symmetrical sine wave with positive and negative phases, and a frequency of 50 Hz. The ratio of the anode reaction time to the cathode reaction time in one cycle of the alternating current is 1:1. The current density, expressed as the peak current of the alternating current waveform, is 35 A / dm³. 2 Furthermore, the electrical charge, calculated as the total charge generated by the aluminum plate participating in the anode reaction, is 350 C / dm. 2 Regarding the electrolysis process, it was performed 10 times with a 1-second pause. A carbon electrode was used as the counter electrode on the aluminum plate. Then, a water washing process was carried out.

[0513] <Second Alkali Etching Treatment>

[0514] At 45°C, an aqueous solution of caustic soda (5% by mass) and aluminum ions (0.5% by mass) was sprayed onto an electrochemically roughened aluminum plate using a sprayer, followed by etching. The dissolved aluminum content on the electrochemically roughened surface was 0.1 g / m². 2 Then, it underwent a water washing process.

[0515] <Second decontamination treatment using acidic aqueous solution>

[0516] Next, a decontamination treatment was performed using an acidic aqueous solution. Specifically, the acidic aqueous solution was sprayed onto the aluminum plate using a sprayer and the decontamination was performed for 3 seconds. The acidic aqueous solution used for the decontamination treatment had a sulfuric acid concentration of 170 g / L and an aluminum ion concentration of 5 g / L. The solution temperature was 35°C.

[0517] <Stage 1 Anodizing Treatment>

[0518] Using based Figure 9 The DC electrolytic anodizing apparatus shown in the diagram used an electrolyte containing sulfuric acid for the first stage of anodizing. The sulfuric acid concentration in the electrolyte was 1 g / L, the electrolyte temperature was 40°C, and the current density was 20 A / dm³. 2 The membrane thickness is 100μm.

[0519] In addition, Figure 9 In the anodizing apparatus 610 shown, the aluminum plate 616 is as follows: Figure 6The aluminum plate 616 is conveyed as indicated by the middle arrow. In the power supply tank 612 containing electrolyte 618, the aluminum plate 616 is charged (+) by the power supply electrode 620. Furthermore, the aluminum plate 616 is conveyed upwards in the power supply tank 612 by roller 622, then downwards by clamping roller 624, and finally conveyed to the electrolytic treatment tank 614 containing electrolyte 626, and then horizontally by roller 628. Next, the aluminum plate 616 is charged (-) by the electrolytic electrode 630, thereby forming an anodized film on its surface. The aluminum plate 616, leaving the electrolytic treatment tank 614, is then conveyed to the subsequent process. In the anodizing apparatus 610, a direction-changing mechanism is formed by rollers 622, 624, and 628. In the space between the power supply tank 612 and the electrolytic treatment tank 614, aluminum plates 616 are conveyed in a mountain-shaped and inverted U-shaped manner via rollers 622, 624, and 628. The power supply electrode 620 and the electrolytic electrode 630 are connected to a DC power supply 634. A tank wall 632 is disposed between the power supply tank 612 and the electrolytic treatment tank 614.

[0520] <Hole Enlargement Treatment (PW Treatment)>

[0521] The aluminum plate that had undergone the above anodizing treatment was immersed in an aqueous solution of caustic soda at 35°C with a concentration of 5% by mass and an aluminum ion concentration of 0.5% by mass for 4 seconds, and then subjected to a pore-enlarging treatment. It was then subjected to a water wash using a sprayer.

[0522] <Stage 2 Anodizing Treatment (2AD)>

[0523] Using based Figure 9 The DC electrolytic anodizing apparatus shown uses an electrolyte containing sulfuric acid for the second stage of anodizing. The sulfuric acid concentration in the electrolyte is 1 g / L, the electrolyte temperature is 25°C, and the current density is 40 A / dm³. 2 .

[0524] <Examples 2-22, Comparative Examples 1-6>

[0525] Except for changing the manufacturing conditions in Example 1 to those described in Table 1, a support for a lithographic printing plate was manufactured following the same steps as in Example 1.

[0526] Furthermore, regarding Examples 19 and 20, in the <second stage of anodizing treatment>, a method based on... Figure 9 The DC electrolytic anodizing apparatus shown in the diagram, after performing a second-stage anodizing treatment (2AD) using an electrolyte containing phosphoric acid, further utilizes a method based on... Figure 9 The DC electrolytic anodizing apparatus shown uses an electrolyte containing sulfuric acid to perform the third stage of anodizing treatment (3AD).

[0527] In the second AD of Examples 19 and 20, the phosphoric acid concentration in the electrolyte was 100 g / L, the electrolyte temperature was 30°C, and the current density was 8 A / dm³. 2 The processing time is shown in Table 1.

[0528] Furthermore, in the third AD of Examples 19 and 20, the sulfuric acid concentration in the electrolyte was 1 g / L, the electrolyte temperature was 40°C, and the current density was 35 A / dm³. 2 The processing time is shown in Table 1.

[0529] Table 1 shows the "First Alkali Etching Treatment (g / m)" 2 The column “) indicates the amount of aluminum dissolved in the first alkaline etching treatment (g / m³)”. 2 ).

[0530] In Table 1, the "Solution Temperature (°C)" column under "Electrochemical Roughening Treatment" indicates the solution temperature (°C) of the electrolyte during the electrochemical roughening treatment.

[0531] In Table 1, the "Number of Electrolysis" column under "Electrochemical Roughening Treatment" indicates how many electrolysis treatments were performed with a 1-second pause interval during the electrochemical roughening treatment.

[0532] Table 1 shows the "Second Alkali Etching Treatment (g / m)" 2 The column “) indicates the amount of aluminum dissolved in the second alkaline etching treatment (g / m³)”. 2 ).

[0533] In Table 1, the "Immersion Time (seconds)" column under "PW Treatment" indicates how many seconds the anodized aluminum plate undergoing PW treatment is immersed in a caustic soda solution.

[0534] In Table 1, the "Processing Time (seconds)" column under "2nd AD" indicates the processing time (seconds) for the 2nd AD.

[0535] In Table 1, the "Processing Time (seconds)" column under "3rd AD" indicates the processing time (seconds) for the 3rd AD.

[0536] [Table 1]

[0537]

[0538] For the support body used in the fabricated lithographic printing plate, the average value of the equivalent circle diameter of the cut surface of the protrusion, the density of the protrusion, and the value of the surface area ratio ΔS were determined using the method described above. These results are shown in Table 3 below.

[0539] Furthermore, for the fabricated aluminum support, the average diameter of the large-diameter pores on the surface of the microporous anodic oxide film, the average diameter at the connecting position of the small-diameter pores, and the depths of the large-diameter and small-diameter pores were measured using the method described above. These results are shown in Table 3 below.

[0540] Furthermore, regarding Examples 19 and 20, the "Average Diameter" and "Depth" in the "Large Diameter Hole" column represent the average diameter and depth at the surface of the anodic oxide film of the "Upper Hole," respectively, while the "Internal Diameter" column represents the maximum diameter within the Upper Hole. Also, regarding Examples 19 and 20, the "Average Diameter" and "Depth" in the "Small Diameter Hole" column represent the average diameter and depth at the point where the "Lower Hole" connects to the Upper Hole, respectively.

[0541] For the anodized film surface of each of the lithographic printing plate supports produced above, a base coating is formed using any one of the base coating liquids 1 to 2 described later, and an image recording layer is formed on the formed base coating using any one of the image recording layer coating liquids 1 to 3 described later, thus producing a lithographic printing plate master.

[0542] The combinations of the primer coating solution and the image recording layer coating solution used are shown in Table 2 below. As shown in Table 2 below, in the cases of formulations B to C, a protective layer is further formed on the image recording layer using a protective layer coating solution.

[0543] The formulations used in the various embodiments and comparative examples are shown in Table 3 below.

[0544] The “Primer Coating Liquid” column in Table 2 indicates the type of primer coating liquid used, with “1” indicating primer coating liquid 1.

[0545] The “Image Recording Layer Coating Solution” column in Table 2 indicates the type of image recording layer coating solution used. “1” indicates image recording layer coating solution 1, “2” indicates image recording layer coating solution 2, and “3” indicates image recording layer coating solution 3.

[0546] The “Protective Coating Liquid” column in Table 2 indicates the type of protective coating liquid used. “1” indicates protective coating liquid 1, “2” indicates protective coating liquid 2, and “-” indicates that no protective coating liquid was used.

[0547] The formation steps of each layer will be described in detail later.

[0548] [Table 2]

[0549] Primer coating liquid Image recording layer coating liquid Protective coating liquid Prescription A 1 1 - Prescription B 1 2 1 Prescription C 1 3 2

[0550] [Formation of the base coating]

[0551] For the anodized film surface of each of the above-mentioned offset printing plate supports, the dry coating amount is 0.1 g / m². 2 The primer coating liquid 1 is applied in a manner that forms the primer coating.

[0552] (Primer coating liquid 1)

[0553] The following components were mixed to prepare the primer coating liquid 1.

[0554] • Compound for primer coating (P-1 below, 11% aqueous solution by mass): 0.10502 parts by mass

[0555] Sodium gluconate: 0.07000 parts by weight

[0556] Surfactant (EMALEX 710, manufactured by NIHON EMULSION Co., Ltd.): 0.00159 parts by weight

[0557] • Preservative (manufactured by Biohope L, K·I Chemical Industry Co., LTD.): 0.00149 parts by weight

[0558] Water: 2.87190 parts by weight

[0559] P-1 (and below, refer to the structural formula)

[0560] [Chemical Formula 21]

[0561] (P-1)

[0562]

[0563] [Formation of image recording layers]

[0564] Regarding image recording layer coating liquid 1, image recording layer coating liquid 1 is bar-coated onto the base coating of the lithographic printing plate support, on which the base coating has been formed. Then, it is dried at 50°C for 60 seconds to form a dry coating weight of 0.9 g / m². 2 The image recording layer was used to obtain the original lithographic printing plate.

[0565] Furthermore, regarding image recording layer coating solutions 2 to 3, any one of image recording layer coating solutions 2 to 3 is applied by bar coating onto the base coating of the lithographic printing plate support, on which the base coating has been formed. Then, it is dried at 120°C for 40 seconds to form a dry coating weight of 1.0 g / m². 2 The image recording layer was used to obtain the original lithographic printing plate.

[0566] (Image recording layer coating solution 1)

[0567] The following components were mixed to prepare image recording layer coating solution 1.

[0568] • Polymer dispersion: 0.675 parts by weight

[0569] Hydroxypropyl methylcellulose: 0.400 parts by weight

[0570] Monomer 1: 0.036 parts by weight

[0571] Monomer 2: 0.115 parts by weight

[0572] Monomer 3: 0.087 parts by weight

[0573] • IR (infrared) pigment: 0.028 parts by weight

[0574] Surfactant: 0.045 parts by weight

[0575] ·Iodized salt 1:0.073 parts by weight

[0576] ·Iodized salt 2: 0.053 parts by weight

[0577] • Colorless pigment: 0.040 parts by weight

[0578] ·Phenothiazine: 0.005 parts by weight

[0579] ·1-Propanol: 2.6 parts by weight

[0580] ·2-Butanone: 3.5 parts by weight

[0581] ·1-Methoxy-2-propanol: 0.92 parts by weight

[0582] ·δ-Butyrolactone: 0.10 parts by weight

[0583] Water: 1.16 parts by weight

[0584] Polymer dispersion: A polymer dispersion was prepared according to Example 10 of EP1,765,593. The solvent was n-propanol / water at a mass ratio of 80:20, and the dispersion was used as a dispersion with a solid content concentration of 23.5% by mass.

[0585] Hydroxypropyl methylcellulose: Used as a 5% aqueous solution with a solids concentration. 30% of the OH groups in hydroxypropyl methylcellulose are methoxylated, and 10% are hydroxypropyloxylated. Furthermore, the viscosity of a 2% by mass aqueous solution at 20°C is 5 mPa-sec.

[0586] Monomer 1

[0587] [Chemical Formula 22]

[0588]

[0589] Monomer 2

[0590] [Chemical Formula 23]

[0591]

[0592] Monomer 3

[0593] [Chemical Formula 24]

[0594]

[0595] IR pigment

[0596] [Chemical Formula 25]

[0597]

[0598] Surfactant: BYK (registered trademark) 302 of Byk Chemie was used as a 25% by mass solution of 1-methoxy-2-propanol.

[0599] iodized salt 1

[0600] [Chemical Formula 26]

[0601]

[0602] iodized salt 2

[0603] [Chemical Formula 27]

[0604]

[0605] Colorless pigment

[0606] [Chemical Formula 28]

[0607]

[0608] phenothiazine

[0609] [Chemical Formula 29]

[0610]

[0611] (Image recording layer coating solution 2)

[0612] The following components were mixed to prepare image recording layer coating solution 2.

[0613] • Infrared absorber (IR-2): 0.0400 parts by weight

[0614] • Colorant (S-22): 0.0200 parts by weight

[0615] • Colorant (S-16): 0.0200 parts by weight

[0616] • Electron-accepting polymerization initiator (Int-1): 0.1090 parts by weight

[0617] • Electron-donating polymerization initiator (TPB): 0.0250 parts by weight

[0618] • Polymerizable compound (M-4 below): 0.4714 parts by mass

[0619] • Anionic surfactant (A-1): 0.0400 parts by weight

[0620] Fluorinated surfactant (W-1): 0.0042 parts by weight

[0621] ·2-Butanone: 4.3551 parts by weight

[0622] ·1-Methoxy-2-propanol: 3.9260 parts by weight

[0623] Methanol: 2.6947 parts by weight

[0624] • Polymer particle R: 2.3256 parts by mass

[0625] [Chemical Formula 30]

[0626] IR-2

[0627]

[0628] [Chemical Formula 31]

[0629]

[0630] [Chemical Formula 32]

[0631]

[0632] [Chemical Formula 33]

[0633]

[0634] The HOMO level of the electron-accepting polymerization initiator (Int-1) is -6.70 eV. The LUMO level of the electron-accepting polymerization initiator (Int-1) is -3.08 eV.

[0635] [Chemical Formula 34]

[0636]

[0637] [Chemical Formula 35]

[0638] A-1

[0639]

[0640] [Chemical Formula 36]

[0641] W-1

[0642]

[0643] [Synthetic method of polymeric compound (M-4)]

[0644] A mixed solution of Takenate D-160N (4.7 parts by mass of polyisocyanate trimethylolpropane adduct, manufactured by Mitsui Chemicals, Inc.), ARONIX M-403 (manufactured by TOAGOSEI CO., LTD., with the NCO value of Takenate D-160N and the hydroxyl value of ARONIX M-403 in a 1:1 ratio), tert-butylbenzoquinone (0.02 parts by mass), and methyl ethyl ketone (11.5 parts by mass) was heated to 65°C. NEOSTANN U-600 (0.11 parts by mass of bismuth-based polycondensation catalyst, manufactured by NITTOKASEI CO., LTD.) was added to the reaction solution, and the mixture was heated at 65°C for 4 hours. The reaction solution was cooled to room temperature (25°C), and methyl ethyl ketone was added, thereby synthesizing a 50% by mass solution of urethane acrylate (M-4).

[0645] [Preparation of polymer particles R]

[0646] -Preparation of oil phase components-

[0647] The oil phase composition was obtained by mixing 6.66 g of WANNATE (registered trademark) PM-200 (a polyfunctional isocyanate compound manufactured by Wanhua Chemical Co., Ltd.), 5.46 g of a 50% by mass ethyl acetate solution of Takenate (registered trademark) D-116N (an adduct of trimethylolpropane (TMP), m-phenylenedimethyl diisocyanate (XDI) and polyethylene glycol monomethyl ether (EO90) (structure below): manufactured by Mitsui Chemicals, Inc.), 11.24 g of a 65% by mass ethyl acetate solution of SR399 (dipentaerythritol pentaacrylate: manufactured by Sartomer Company, Inc.), 14.47 g of ethyl acetate, and 0.45 g of PIONIN (registered trademark) A-41-C (manufactured by Takemoto Oil & Fat Co., Ltd.), and stirring at room temperature (25°C) for 15 minutes.

[0648] [Chemical Formula 37]

[0649]

[0650] -Preparation of Aqueous Phase Components-

[0651] 47.2g of distilled water was prepared as the aqueous phase component.

[0652] -Microencapsulation process-

[0653] An emulsion was obtained by adding an aqueous component to the oil phase and mixing the mixture, then emulsifying the resulting mixture at 12,000 rpm for 16 minutes using a homogenizer.

[0654] 16.8 g of distilled water was added to the obtained emulsion, and the resulting liquid was stirred at room temperature for 180 minutes.

[0655] Next, the stirred liquid was heated to 45°C and stirred for 5 hours while maintaining the temperature at 45°C, thereby removing ethyl acetate from the liquid by distillation. The concentration of the solid component was adjusted to 20% by mass with distilled water, thus obtaining an aqueous dispersion of polymer particles R. The volume average particle size of polymer particles R was measured using a laser diffraction / scattering particle size distribution measuring device LA-920 (manufactured by HORIBA, Ltd.), and was found to be 165 nm.

[0656] (Image recording layer coating solution 3)

[0657] The following components were mixed to prepare image recording layer coating solution 3.

[0658] • Infrared absorber (IR-1): 0.0120 parts by weight

[0659] • Infrared absorber (IR-2): 0.0250 parts by weight

[0660] • Colorant (S-22): 0.0200 parts by weight

[0661] • Colorant (S-16): 0.0200 parts by weight

[0662] • Electron-accepting polymerization initiator (Int-1): 0.1090 parts by weight

[0663] • Electron-donating polymerization initiator (TPB): 0.0250 parts by weight

[0664] • Polymerizable compound (M-4): 0.4714 parts by mass

[0665] • Anionic surfactant (A-1): 0.0400 parts by weight

[0666] Fluorinated surfactant (W-1): 0.0042 parts by weight

[0667] ·2-Butanone: 4.3551 parts by weight

[0668] ·1-Methoxy-2-propanol: 3.6383 parts by weight

[0669] Methanol: 2.6947 parts by weight

[0670] • Polymer particle R: 2.6163 parts by mass

[0671] [Chemical Formula 38]

[0672] IR-1

[0673]

[0674] [Formation of the protective layer]

[0675] Protective coating solution 1 or 2 is applied to the image recording layer of an aluminum support on which the image recording layer is formed, and then dried at 120°C for 60 seconds to form a dry coating with a coating weight of 0.80 g / m². 2 The protective layer.

[0676] (Protective coating liquid 1)

[0677] The following components were mixed to prepare protective coating liquid 1.

[0678] Inorganic layered compound dispersion (1) [below]: 0.5625 parts by weight

[0679] • Hydrophilic polymer (1) (20% aqueous solution): 0.0825 parts by weight

[0680] [Chemical Formula 39]

[0681]

[0682] METOLOSE SM04 (methylcellulose, manufactured by Shin-Etsu Chemical Co., Ltd., degree of methoxy substitution = 1.8): 0.0125 parts by weight

[0683] • RAPISOL A-80 (anionic surfactant, manufactured by NOF CORPORATION, 80% aqueous solution): 0.007 parts by weight

[0684] • Ion-exchanged water: 4.3355 parts by weight

[0685] The following shows the preparation method of the inorganic layered compound dispersion (1) used in the above protective coating liquid.

[0686] Preparation of Inorganic Layered Compound Dispersion (1) -

[0687] 6.4 parts by mass of synthetic mica (SOMASIF ME-100, manufactured by Co-op Chemical Co., Ltd.) were added to 193.6 parts by mass of ion-exchanged water, and dispersed using a homogenizer until the volume average particle size (laser scattering method) was 3 μm. The aspect ratio of the obtained dispersed particles was greater than 100.

[0688] (Protective coating liquid 2)

[0689] The following components were mixed to prepare protective coating liquid 2.

[0690] Inorganic layered compound dispersion (1) [above]: 0.5625 parts by mass

[0691] • The above hydrophilic polymer (1) (20% aqueous solution): 0.0825 parts by weight

[0692] • METOLOSE SM04 (methylcellulose, manufactured by Shin-Etsu Chemical Co., Ltd., degree of methoxy substitution = 1.8): 0.0250 parts by weight

[0693] • RAPISOL A-80 (anionic surfactant, manufactured by NOF CORPORATION, 80% aqueous solution): 0.007 parts by weight

[0694] • Ion-exchanged water: 4.3300 parts by weight

[0695] [Evaluation Method]

[0696] Scratch resistance

[0697] The scratch resistance was evaluated using a surface properties tester, TRIBOGEAR TYPE: 18LFW (manufactured by Shinto Scientific Co., Ltd.). For the aforementioned lithograph master, a 0.1mm sapphire needle was used at a surface properties of 5g / m². 2 The scale starts from 10g / m 2 Up to 90g / m 2 The load was varied, and the lithographic printing plate was scanned at a scanning speed of 20 mm / s to induce scratches. The scratched lithographic printing plate was then used for on-machine development and printing. The load at which scratch contamination occurred on the 100th sheet of paper at the start of printing was evaluated.

[0698] 10: Even at 90g / m 2 It will not produce scratches or contamination under heavy loads.

[0699] 9: At 90g / m 2 Scratches and contamination caused by load

[0700] 8: At 85g / m 2 Scratches and contamination caused by load

[0701] 7: At 75 or 80 g / m 2 Scratches and contamination caused by load

[0702] 6: At 65 or 70 g / m 2 Scratches and contamination caused by load

[0703] 5: At 55 or 60 g / m 2 Scratches and contamination caused by load

[0704] 4: At 45 or 50 g / m 2 Scratches and contamination caused by load

[0705] 3: At 35 or 40 g / m 2 Scratches and contamination caused by load

[0706] 2: At 25 or 30 g / m 2 Scratches and contamination caused by load

[0707] 1: At 20g / m 2 Scratching and contamination will occur under the following loads.

[0708] <Oil-based detergent scrub resistance>

[0709] The original lithographic printing plate was exposed using a Luxel PLATESETTER T-6000III manufactured by Fujifilm Corporation, which is equipped with an infrared semiconductor laser, at an outer drum speed of 1000 rpm, laser output of 70%, and a resolution of 2400 dpi. The exposed image includes a solid image and a 50% dot plot with 20 μm FM (Frequency Modulation) halftone screening.

[0710] The obtained exposed lithographic printing plate was not developed, but instead mounted on the plate cylinder of a Lithrone 26 printing press manufactured by KOMORI Corporation. After on-machine development using a dampening solution of Ecolity-2 (manufactured by Fujifilm Corporation) / tap water = 2 / 98 (volume ratio) and Values-G(N) black ink (manufactured by Dainippon Ink and Chemicals, Inc.), the dampening solution and ink were supplied via the standard automatic printing start-up method of the Lithrone 26. Printing was then performed on Tokubishi Art (76.5 kg) paper at a printing speed of 10,000 sheets per hour. As the number of prints increased, the image recording layer gradually wore down, resulting in a decrease in ink density on the printed material. The number of prints at which the density of the solid image began to thin out visually was used as the baseline print count.

[0711] Next, a process was set up in which the printing plate was wiped with a cleaning agent (manufactured by Fujifilm Corporation, MultiCleaner) every 5,000 prints. Otherwise, using the same method as described above, the number of prints at which the density of the solid image began to thin out when observed with the naked eye was determined. The obtained number of prints was set as the evaluation print count, and its value is shown in the table described later.

[0712] In Table 3, the "Equivalent Circle Diameter" column represents the average value of the equivalent circle diameter of the cut surface of the convex at a position 0.5 μm higher than the average height of the convex.

[0713] Table 3 shows the "density of protrusions (numbers / mm)". 2 The column “) indicates the density (numbers / mm²) of protrusions that are at least 0.5 μm higher than the average height of the protrusions. 2 ).

[0714] [Table 3]

[0715]

[0716] As shown in Table 3 above, it was confirmed that the desired effect can be obtained in the case of the lithographic printing plate support of the present invention.

[0717] The comparison of Examples 1 to 3 confirmed that the effect was better when the average equivalent circle diameter was 3.0 to 6.5 μm.

[0718] A comparison of Examples 4-6 confirmed that the density of the protrusions was 4000-9000 per mm. 2 In certain situations, the effect is even better.

[0719] Based on the results of Examples 12-15, it was confirmed that the film content was 3.2 g / m³. 2 In the above situations, the effect is even better.

[0720] Comparison of Examples 2, 16-18 confirmed that when the average diameter of the micropores on the surface of the anodic oxide film is 25-40 nm, the balance between scratch resistance and brush resistance is excellent.

[0721] A comparison of Examples 9 and 10 confirmed that the amount of alkali etched in the second step was 0.20 g / m. 2 Excellent brush resistance is observed in the following conditions.

[0722] Symbol Explanation

[0723] ta - Anode reaction time, tc - Cathode reaction time, tp - Time from 0 to peak current, Ia - Peak current on the anode circulation side, Ic - Peak current on the cathode circulation side, 10 - Support for lithographic printing plate, 12 - Aluminum plate, 14A, 14B, 14C - Anodized film, 16A - First protrusion, 16B - Second protrusion, 16C - Third protrusion, 20, 30 - Micropores, 22 - Large diameter hole, 24 - Small diameter hole, 32 - Upper hole, 34 - Lower hole, 36 - Small diameter upper hole, 38 - Large diameter upper hole, 40 - Original lithographic printing plate 42-Support for lithographic printing plate, 44-Base coating, 46-Image recording layer, 50-Main electrolytic cell, 51-AC power supply, 52-Radial drum roller, 53a, 53b-Main electrode, 54-Electrolyte supply port, 55-Electrolyte, 56-Auxiliary anode, 60-Auxiliary anode tank, W-Aluminum plate, 610-Anodizing treatment device, 612-Power supply tank, 614-Electrolytic treatment tank, 616-Aluminum plate, 618, 626-Electrolyte, 620-Power supply electrode, 622, 628-Roller, 624-Roller, 630-Electrolytic electrode, 632-Tank wall, 634-DC power supply.

Claims

1. A support for a lithographic printing plate, comprising an aluminum plate and an anodized aluminum film disposed on the aluminum plate. On the surface of the support for the offset printing plate, there are multiple protrusions on the side of the anodized film. The average equivalent circle diameter of the cut surface of the protrusion at a position 0.5 μm higher than the average height of the protrusion is 3.0 μm to 10.0 μm. The density of protrusions having a height at least 0.5 μm higher than the average height of the protrusions is 3000 per mm. 2 ~9000 pieces / mm 2 .

2. The support for a lithographic printing plate according to claim 1, wherein, The average diameter of the equivalent circle is 3.0 μm to 6.5 μm.

3. The support for a lithographic printing plate according to claim 1 or 2, wherein, The density is 4000 particles / mm². 2 ~9000 pieces / mm 2 .

4. The support for a lithographic printing plate according to claim 1 or 2, wherein, The ratio of the density to the average value of the equivalent circle diameter is 500 (particles / mm). 2 ) / μm or more.

5. The support for a lithographic printing plate according to claim 1 or 2, wherein, The anodic oxide film thickness is 2.0 g / m³. 2 above.

6. The support for a lithographic printing plate according to claim 1 or 2, wherein, The anodic oxide film thickness is 3.2 g / m³. 2 above.

7. The support for a lithographic printing plate according to claim 1 or 2, wherein, The actual area Sx and the geometrically measured area S0, obtained by measuring 512 × 512 points in a 25 μm × 25 μm area on the surface of the anodic oxide film using an atomic force microscope, are calculated using the approximate three-point method. The surface area ratio ΔS, calculated by the following formula (1), is 20% or more. ΔS=(Sx-S0) / S0×100(%) (1).

8. The support for a lithographic printing plate according to claim 1 or 2, wherein, The anodic oxide film has micropores. The micropores consist of a large-diameter pore portion and a small-diameter pore portion. The large-diameter pore portion extends from the surface of the anodic oxide film to a depth of 10 nm to 1000 nm. The small-diameter pore portion is connected to the bottom of the large-diameter pore portion and extends from the connection point to a depth of 20 nm to 2000 nm. The average diameter of the anodic oxide film surface in the large-diameter orifice is 18 nm to 60 nm. The average diameter at the connecting position of the small-diameter hole is less than 15 nm.

9. The support for a lithographic printing plate according to claim 1 or 2, wherein, The anodic oxide film has micropores. The micropores consist of an upper pore portion and a lower pore portion. The upper pore portion extends from the surface of the anodic oxide film in the depth direction, and the lower pore portion communicates with the bottom of the upper pore portion, extending from the communication position to a depth of 20 nm to 2000 nm. The average diameter of the upper pores on the surface of the anodic oxide film is 18 nm to 60 nm. The maximum diameter of the upper hole is less than 200 nm. The average diameter at the communicating position of the lower hole is less than 15 nm. The ratio of the maximum diameter of the upper hole to the average diameter of the upper hole at the surface of the anodic oxide film is 1.2 or more.

10. The support for a lithographic printing plate according to claim 8, wherein, The density of the micropores is 300 per μm. 2 ~2000 / μm 2 .

11. A lithographic printing plate original, comprising a lithographic printing plate support and an image recording layer as described in claim 1 or 2.

12. The lithographic printing plate original according to claim 11, which is an on-machine developing type.

13. A method for manufacturing a lithographic printing plate, comprising the following steps: Image exposure of the original offset printing plate as described in claim 11 is performed using infrared laser; and The unexposed portion of the image recording layer is removed on a printing press by using at least one of printing ink and dampening solution.

Images