JP2022117561A - Endless lithographic original plate, method for producing endless lithographic plate, and method for producing endless printed material by using the same - Google Patents

Abstract

To provide an endless lithographic original plate and an endless lithographic plate that have excellent image reproducibility, necessary to obtain high-precision endless printed materials, and to provide a lithographic original plate and an endless lithographic plate that allow easy recycling of a cylindrical support.SOLUTION: An endless lithographic original plate has an endless lithographic plate substrate, having at least a heat-shrunk shrinkable tube around a cylindrical support, and an ink repulsion layer in the stated order, the ink repulsion layer continuously existing on the outermost surface of the endless lithographic original plate.SELECTED DRAWING: None

Description

The present invention relates to an endless lithographic printing plate precursor, a method for producing an endless lithographic printing plate, and a method for producing an endless printed matter using the same.

There are various printing methods such as letterpress printing, intaglio printing, stencil (screen) printing, and lithographic printing, and printing is performed by taking advantage of the characteristics of each method.

Among them, in the field of flexible packaging printing, endless printing is performed in which intermittent patterns and continuous patterns are repeatedly formed on a long medium to be printed. Patent Document 1 discloses a cylindrical letterpress printing plate for endless printing. and intaglio printing plates are described.

On the other hand, lithographic printing is more advantageous than other printing methods in terms of obtaining high-definition printed matter and low total costs including running costs. A cylindrical lithographic printing plate for endless printing is described.

Further, Patent Document 3 describes an endless lithographic printing plate that can be easily removed by providing a heat-shrinkable shrink tube on the surface of the plate cylinder sleeve.

JP 2010-76381 A WO2019/203263 Japanese Patent Application Laid-Open No. 2006-231758

Since the letterpress printing plate and the intaglio printing plate described in Patent Document 1 are inferior to the lithographic printing plate in definition, it is difficult to obtain a high-definition endless printed material. In addition, since a thick resin layer is provided on the heat-shrinkable material of the shrink tube, it is difficult to separate the heat-shrinkable material of the shrink tube and the resin layer from the support, making it difficult to recycle the support. rice field. Furthermore, when the heat-shrinkable shrink tube and the resin layer are easily separated from each other, the support may be damaged when a cutter or the like is used to make a cut from the resin layer side.

Although the lithographic printing plate described in Patent Document 2 can produce a high-definition endless printed material, the support/ink-repellent layer and the support/adhesive layer are strongly bonded by chemical bonding, so the support needs to be recycled. For this purpose, complicated operations such as washing with a solvent and polishing the surface of the support were required.

Although the lithographic printing plate described in Patent Document 3 can produce high-definition endless printed matter, a seam exists between the plate head and the plate bottom because the sheet-fed lithographic printing plate is wrapped around the plate cylinder sleeve. Therefore, it was not possible to obtain an endless print with a continuous pattern.

Therefore, the problem to be solved by the present invention is to provide an endless lithographic printing plate precursor and an endless lithographic printing plate which are excellent in image reproducibility, which are necessary for obtaining high-definition endless printed matter. Another object of the present invention is to provide an endless lithographic printing plate precursor and an endless lithographic printing plate whose cylindrical support can be easily recycled.

In order to solve the above problems, the endless lithographic printing plate precursor of the invention has the following configuration. That is, an endless lithographic printing plate precursor having a heat-shrinkable shrink tube on at least the periphery of a cylindrical support, and an ink-repellent layer in this order, wherein the ink-repellent layer is used for endless lithographic printing. It is an endless lithographic printing plate precursor that continuously exists on the outermost surface of the plate precursor.

According to the present invention, it is possible to obtain an endless lithographic printing plate precursor and an endless lithographic printing plate having excellent image reproducibility, which are necessary for obtaining high-definition endless printed matter. In addition, an endless lithographic printing plate precursor and an endless lithographic printing plate can be obtained in which the cylindrical support can be easily recycled.

FIG. 10 is a diagram showing the difference between intermittent patterns and continuous patterns in endless printing; 1 is a cross-sectional view showing an example of an endless lithographic printing plate having an ink repelling portion and an ink receiving portion on at least the surface of a layer comprising an ink repelling portion and an ink receiving portion; FIG. 1 is a cross-sectional view showing an example of an endless lithographic printing plate having an ink repelling portion and an ink receiving portion on at least the surface of a layer comprising an ink repelling portion and an ink receiving portion; FIG. 1A to 1C are cross-sectional views showing an example of a method for manufacturing an endless printed matter according to the present invention; BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows an example of the manufacturing method of the base material for endless lithographic printing plates which concerns on this invention.

The present invention will be described in detail below.

The endless lithographic printing plate precursor according to the present invention is an endless lithographic printing plate precursor having, in this order, an endless lithographic printing plate substrate having a heat-shrinkable shrink tube on at least the outer periphery of a cylindrical support, and an ink repellent layer. Thus, the ink repellent layer is continuously present on the outermost surface of the endless lithographic printing plate precursor.

Endless printing in the present invention refers to a method of repeatedly printing the same picture or pattern on a long medium to be printed, and by this printing method, patterns of intermittent pictures or continuous pictures are repeatedly formed on the medium to be printed. An endless print is obtained. Further, the endless lithographic printing plate in the present invention refers to a lithographic printing plate for carrying out the above endless printing by a conventionally known lithographic printing method. Further, the endless lithographic printing plate precursor in the present invention refers to the state of the endless lithographic printing plate before plate making.

Here, the difference between intermittent patterns and continuous patterns in the endless printing of the present invention will be described with reference to FIG. FIG. 1 shows an endless lithographic printing plate used for endless printing of intermittent patterns and continuous patterns, and an endless printed material obtained by performing endless printing using the endless lithographic printing plate. The endless lithographic printing plate has an image area 1 to which ink adheres and a non-image area 2 to which ink does not adhere. , image line portions 1 (pictures) are arranged continuously in the printing direction. In the endless printing process, the ink adhering to the image area 1 is transferred directly or via a blanket onto the print medium 3 to form a transfer pattern 4 .

The endless lithographic printing plate described in JP-A-2006-231758 exemplified as Patent Document 3 of the prior art and the endless lithographic printing plate described in Comparative Example 2 described later have a sheet on the outer peripheral surface of the base for the endless lithographic printing plate. This is an endless lithographic printing plate in which a leaf-shaped lithographic printing plate is wound, and an ink-repellent layer-forming composition is filled in the gap between the head and the bottom of the plate and cured to form an ink-repellent portion. For this reason, by arranging the pattern so that the ink repelling part in the gap between the head and the bottom of the block matches the part where the pattern is interrupted in the intermittent pattern, although it is not possible to obtain an endless printed matter of the intermittent pattern, Since it is not possible to form an image line portion in the ink-repellent portion of the rear gap, it is not possible to obtain an endless print of a continuous pattern with no discontinuous portions in the pattern.

On the other hand, in the endless lithographic printing plate precursor of the present invention, the ink repellent layer or the ink receptive layer is provided continuously without gaps in the circumferential direction of the endless lithographic printing plate precursor. Therefore, since an endless lithographic printing plate having continuous image portions without gaps in the circumferential direction can be produced, it is possible to obtain an endless print having a continuous pattern without any discontinuities in the pattern.

First, the endless lithographic printing plate substrate will be described.

Known metals, plastics, and the like, which are dimensionally stable, can be used as the cylindrical support used for the endless lithographic printing plate base material according to the present invention. Specifically, metals such as aluminum, iron, zinc, and copper, alloys based on these metals, plastics such as epoxy resins, phenolic resins, ester resins, vinyl ester resins, amide resins, and imide resins, and these plastics. Examples include fiber-reinforced plastics reinforced with fibers such as glass fibers, carbon fibers, aramid fibers, polyethylene fibers, Zylon fibers, and boron fibers. It is preferable to use an aluminum alloy or a fiber-reinforced plastic because it is lightweight and easy to handle.

The cylindrical support is preferably a plate cylinder of a printing machine in that printing can be performed immediately after making the plate. Above all, the cylindrical support is a plate cylinder sleeve that can be attached and detached from the plate cylinder shaft, so that the series of steps up to the production of the endless lithographic printing plate and the operation of regenerating the support after printing can be performed outside the printing machine. more preferred.

As for the dimensions of the cylindrical support, a suitable diameter and width may be selected for the plate cylinder of the printing machine to be used.

The heat-shrinkable product of the shrink tube in the present invention refers to a shrink tube that is shrunk by heat-treating a heat-shrinkable shrink tube at a temperature below the decomposition temperature. When the heat shrink treatment is performed at a temperature lower than the decomposition temperature of the shrink tube, the molecular structure itself of the shrink tube does not change before and after heating.

Materials for the heat-shrinkable shrink tube and the heat-shrinkable material of the shrink tube include polyester, polyvinyl chloride, polystyrene, polyolefin, and the like, and a single film or composite film of these materials can be used. From the point of view of the coatability to the heat-shrinkable material of the shrink tube and the solvent resistance of the heat-shrinkable material of the shrinkable tube, at least the outermost surface of the ink repellent layer side of the heat-shrinkable shrinkable tube or the heat-shrinkable material of the shrinkable tube is made of polyester. There is preferably one, more preferably polyethylene terephthalate.

The thickness of the heat-shrinkable shrink tube is preferably in the range of 10 to 500 μm. If the thickness is 10 μm or more, it is possible to suppress the breakage and elongation of the film due to the progress of printing, and if it is 500 μm or less, it is possible to suppress variations in the thickness of the film after thermal shrinkage. A range of 30 to 300 μm is more preferred.

In addition, from the viewpoint of suppressing misregistration due to the progress of printing, it is preferable to further have a rubber layer between the cylindrical support and the heat-shrinkable material of the shrink tube, and it is more preferable to have the rubber layer continuously. Types of the rubber layer include urethane rubber, natural rubber, styrene-butadiene rubber, chloroprene rubber, acrylonitrile rubber, butyl rubber, ethylene propylene rubber, silicone rubber, fluororubber, and chlorosulfonated polyethylene rubber. Among them, it is more preferable to use urethane rubber because it is easy to form a tough film and has excellent adhesion to the outer peripheral surface of the cylindrical support and the inner peripheral surface of the heat-shrinkable material of the shrink tube. .

The average thickness of the rubber layer is preferably in the range of 1-500 μm. If the average thickness is 1 μm or more, a gripping force can be obtained between the cylindrical support and the heat condensed product of the shrink tube, so misregistration due to the progress of printing is less likely to occur. 5 μm or more is more preferable. On the other hand, if the thickness is 500 μm or less, variations in the thickness of the rubber layer can be suppressed. 300 μm or less is more preferable.

Next, a method for producing a substrate for an endless lithographic printing plate will be described.

The endless lithographic printing plate substrate of the present invention is produced by placing a heat-shrinkable shrink tube around the outer circumference of a cylindrical support, shrinking the heat-shrinkable shrink tube by heat, and fixing it to the surface of the cylindrical support. be done.

Materials for the heat-shrinkable shrink tube include polyester, polyvinyl chloride, polystyrene, polyolefin, and the like, and single films and composite films of these materials can be used. From the standpoints of coatability and solvent resistance to the heat-shrinkable shrink tube, at least the outermost surface of the heat-shrinkable shrink tube on the ink repellent layer side is preferably polyester, more preferably polyethylene terephthalate. Specific examples of the heat-shrinkable shrink tube whose outermost surface on the ink repellent layer side is polyethylene terephthalate include, but are not limited to, Copalon PTA and Copalon PFT (both manufactured by Gunze Polymer Co., Ltd.).

As for the dimensions of the heat-shrinkable shrink tube, the diameter in the equivalent of a perfect circle is 2 to 100 mm longer than the diameter of the cylindrical support, and the width in the width direction is 10 to 10 mm longer than the width in the width of the cylindrical support. 300 mm long is preferred. When the diameter in the equivalent of a perfect circle is 2 mm or more longer than the diameter of the cylindrical support, it is easy to attach to the cylindrical support. can be suppressed. More preferably, it has a length of 5 to 50 mm. In addition, since the width direction length is longer than the width direction length of the cylindrical support by 10 mm or more, when the heat-shrinkable shrink tube for the excess length is heat-shrunk, both ends of the cylindrical support are wrapped in shape, Since the adhesiveness to the cylindrical support is improved, misregistration due to the progress of printing is less likely to occur. On the other hand, if the length is 300 mm or less, it is possible to suppress variations in the thickness of the heat-shrinkable material of the shrink tube. More preferably, it is 20-200 mm long.

As for the heating conditions for the heat-shrinkable shrink tube, it is preferable to heat within the temperature range of 60 to 180° C. for 1 second to 30 minutes. When a rubber layer is provided between the cylindrical support and the heat-shrinkable material of the shrink tube, the rubber layer is obtained by coating the surface of the cylindrical support with the rubber layer-forming composition and drying the solvent. After that, the heat-shrinkable shrink tube is placed on the outer periphery of the rubber layer, and the heat-shrinkable shrink tube is shrunk by heat and fixed to the surface of the rubber layer. Examples of the method for applying the rubber layer-forming composition to the surface of the cylindrical support include, but are not limited to, dipping, spraying, cylindrical slit die coating, and the like. For the purpose of accelerating the drying of the solvent, it is preferable to heat for 30 seconds to 10 minutes within the temperature range of 50 to 180° C. using a known hot air drying device or infrared drying device.

Next, the endless lithographic printing plate precursor will be described.

The endless lithographic printing plate precursor according to the present invention is an endless lithographic printing plate precursor having the aforementioned endless lithographic printing plate substrate and an ink-repellent layer in this order, and the ink-repellent layer is the outermost surface of the endless lithographic printing plate precursor. exist continuously. The ink-repellent layer and the ink-receiving layer such as the photosensitive layer and the heat-sensitive layer, which will be described later, are continuously present in the circumferential direction of the endless lithographic printing plate precursor, so that patterns of intermittent or continuous patterns can be formed on the endless lithographic printing plate. Since it can be formed, it becomes possible to perform endless printing in which a pattern of intermittent patterns or continuous patterns is repeatedly formed on a long medium to be printed.

As the ink repellent layer, a silicone layer or a fluororesin layer that has been proposed as an ink repellent layer for a waterless lithographic printing plate can be used. A hydrophilic layer proposed as an ink-repellent layer for wet lithographic printing plates also falls under the category of the ink-repellent layer in the present invention.

For the purpose of improving the adhesive strength between the heat-shrinkable material/ink-repellent layer of the shrink tube and the heat-shrinkable material/ink-repellent layer of the shrink tube, which will be described later, It is preferred to further provide an adhesive layer continuously between the material/inking layers.

Examples of the adhesive layer include adhesive layers described as heat insulating layers in JP-A-2004-199016, JP-A-2004-334025, and JP-A-2006-276385, but are not limited to these.

The average thickness of the adhesive layer is preferably 0.1 μm or more from the viewpoint of improving the scratch resistance and printing durability of the printing plate, and is preferably 30 μm or less from the viewpoint that the diluting solvent is easily volatilized and productivity is excellent. 0.2 to 20 μm is more preferable.

The form of the endless lithographic printing plate precursor according to the invention includes (1) a form having an endless lithographic printing plate substrate and an ink repellent layer in this order, and (2) an endless lithographic printing plate substrate, an ink repellent layer, and an ink. (3) A form having an endless lithographic printing plate substrate, an ink receiving layer, and an ink repelling layer in this order.

(1) Form having a substrate for an endless lithographic printing plate and an ink repellent layer in this order As the ink repellent layer, conventionally known addition reaction type ink repellent layers disclosed as ink repellent layers for waterless lithographic printing plate precursors, A condensation reaction type or an addition reaction-condensation reaction type ink repellent silicone layer can be used.

The average elastic modulus of the ink-repellent silicone layer is preferably 0.001 to 10 MPa. When the pressure is 0.001 MPa or more, the printing durability is improved, and when the pressure is 10 MPa or less, the ink repellency is further improved, which is preferable. 0.01 to 5 MPa is more preferred, and 0.1 to 3 MPa is even more preferred.

The elastic modulus of the ink-repellent silicone layer of the endless lithographic printing plate and the ink-receiving part described later is analyzed by the force volume method using an atomic force microscope, which is analyzed with a very small load using a sharp-tipped probe. is preferred. By using a silicon or silicon nitride probe with a tip radius of curvature of 5 to 20 nm and analyzing with a load of 1 to 20 nN, the elastic modulus of each part can be accurately measured, excluding the influence of the underlying layer and support. can do. In the force volume method, the probe (cantilever) is vertically moved, and the probe is scanned two-dimensionally while repeating a series of operations of pressing against the layer surface and releasing it. At that time, since the force curve is acquired for each cycle, the mapping of the mechanical properties such as the elastic modulus can be examined by the analysis. The average elastic modulus is the arithmetic mean value of each elastic modulus obtained at 4096 measurement points (vertical: 64 points x horizontal: 64 points) in a measurement range of 25 μm ² (vertical: 5 μm x horizontal: 5 μm). It can be obtained by calculating.

In the present invention, the ink-repellent silicone layer preferably contains diorganosiloxane units. The inclusion of diorganosiloxane units in the ink-repellent silicone layer is preferable because the ink repellency can be improved. The content of diorganosiloxane units in the ink-repellent silicone layer is preferably 90% by mass or more, more preferably 92% by mass or more, and even more preferably 94% by mass or more. If the diorganosiloxane unit in the ink repellent silicone layer is 90% by mass or more, the ink repellency can be further improved, which is preferable. The content of diorganosiloxane units in the ink-repellent silicone layer can be measured by a combination of analysis by FT-IR-ATR and time-of-flight secondary ion mass spectrometry (TOF-SIMS). can.

Also, the diorganosiloxane units in the ink-repellent silicone layer can be confirmed by FT-IR-ATR analysis. In FT-IR-ATR analysis, the diorganosiloxane unit shows signals in absorption bands around 1256, 1085 and 790 cm ⁻¹ .

In the present invention, the concentration of elements in the ink-repellent silicone layer is preferably in the range of silicon: 22 to 26 atom %, oxygen: 24 to 28 atom %, carbon: 48 to 52 atom %. It is preferable because the ink repellency is further improved. The ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) in the ink-repellent silicone layer is preferably in the range of 0.9 to 1.2. It is preferable because it further improves.

Element concentrations in the ink-repellent silicone layer can be determined by analysis with X-ray photoelectron spectroscopy. Further, by dividing the obtained oxygen concentration value by the silicon concentration value, the ratio of the oxygen concentration to the silicon concentration (oxygen concentration/silicon concentration) can be calculated.

The silicon concentration in the ink-repellent silicone layer is preferably 25 to 50% by mass. If the silicon concentration in the ink-repellent silicone layer is 25% by mass or more, it is preferable for further improving the ink repellency, 30% by mass or more is more preferable, and 35% by mass or more is even more preferable. In addition, if the silicon concentration is 50% by mass or less, it is preferable for further improving the ink repellency of the ink-repellent portion and printing durability, it is more preferably 45% by mass or less, and even more preferably 40% by mass or less. The silicon concentration in the ink-repellent silicone layer can be determined by elemental analysis using the aforementioned X-ray photoelectron spectroscopy.

The average film thickness of the ink-repellent silicone layer is preferably 4 to 30 μm. When the average thickness of the ink-repellent silicone layer is 4 μm or more, the endless lithographic printing plate has sufficient ink repellency, scratch resistance, and printing durability. The average film thickness of the ink-repellent silicone layer can be determined by cross-sectional TEM observation. More specifically, a sample is prepared from an endless lithographic printing plate by the ultra-thin section method, and TEM observation is performed under the conditions of an acceleration voltage of 100 kV and a magnification of 2000 times. In a TEM photograph of a vertical section, the film thickness is measured at 10 locations randomly selected from the ink-repellent silicone layer, and the average film thickness is calculated to obtain the average film thickness.

Silicone rubber is preferable as the ink-repellent silicone layer in the present invention. The silicone rubber in the present invention refers to a layer of which 60% by mass or more is composed of a crosslinked siloxane compound. The content of the crosslinked siloxane compound in the ink-repellent silicone layer is measured by a combination of analysis by FT-IR-ATR and time-of-flight secondary ion mass spectrometry (TOF-SIMS). be able to.

From the viewpoint of improving the productivity of the endless lithographic printing plate, it is preferable to have a vinyl group in the ink-repellent silicone layer. An ink-repellent silicone layer having vinyl groups can be obtained by including vinyl groups in excess of the total number of SiH groups in the total solid content of the composition for forming an ink-repellent silicone layer, which will be described later. The vinyl group concentration in the ink-repellent silicone layer is preferably 0.5 to 15 mass %. When the vinyl group concentration in the ink-repellent silicone layer is 0.5% by mass or more, the productivity of the endless lithographic printing plate is improved, and when it is 15% by mass or less, a decrease in ink repellency can be suppressed, which is preferable. 1 to 12% by mass is more preferable, and 1.5 to 10% by mass is even more preferable. The presence of vinyl groups in the ink-repellent silicone layer can be confirmed by analyzing the ink-repellent silicone layer by the FT-IR-ATR method.

(2) Form having a substrate for endless lithographic printing plate, an ink repellent layer, and an ink receiving layer in this order As the ink repellent layer, ink repellent silicone that has been proposed as an ink repellent layer for waterless lithographic printing plates has been used so far. The ink-repellent silicone layer exemplified in the embodiment having the above-mentioned (1) substrate for endless lithographic printing plate and the ink-repellent layer in this order can be used. An ink receptive silicone layer as described in 203263 can be used.

As another form of (2), as the ink repellent layer, a known hydrophilic layer that has hitherto been proposed as an ink repellent layer for a wet lithographic printing plate can be used. can use known ink-receiving layers that have been proposed as photosensitive layers and heat-sensitive layers for wet lithographic printing plates.

(3) Form having a substrate for endless lithographic printing plate, ink receptive layer, and ink repellent layer in this order The ink receptive layer has been proposed as a photosensitive layer or heat-sensitive layer for waterless lithographic printing plates. An ink-receiving layer can be used, and as the ink-repellent layer, an ink-repellent silicone layer that has been proposed as an ink-repellent layer for a waterless lithographic printing plate, or the aforementioned (1) substrate for an endless lithographic printing plate can be used. The ink-repellent silicone layer exemplified in the embodiment having the material and the ink-repellent layer in this order can be used.

Next, a method for producing an endless lithographic printing plate precursor will be described.

The method for producing an endless lithographic printing plate precursor according to the present invention includes a step of forming a seamless and continuous ink repellent layer on the outer peripheral surface of the endless lithographic printing plate base material. A seamless and continuous ink-repellent layer can be formed by applying the composition for forming an ink-repellent layer, which will be described later, on the outer peripheral surface of the endless lithographic printing plate base material by applying a coating method such as a dipping method, a spraying method, a cylindrical slit die coating method, or the like. It can be formed by coating continuously without heating, drying and curing with or without heating. In the case of forming a seamless continuous rubber layer, an adhesive layer, an ink-receiving layer, etc., each layer-forming composition can be applied by dipping, spraying, or in a cylinder in the same manner as in the method for forming the ink-repellent layer. It can be formed by seamlessly and continuously coating using a coating method such as a slit die coating method, and drying and curing with or without heating.

(1) A method for producing an endless lithographic printing plate precursor having an endless lithographic printing plate substrate and an ink-repellent layer in this order An ink-repellent silicone layer is formed on the surface of the endless lithographic printing plate substrate obtained by the aforementioned production method. A base material for an endless lithographic printing plate and an ink-repellent silicone layer are formed by coating the forming composition continuously without a seam, drying and curing with or without heating to form an ink-repellent silicone layer. An endless lithographic printing plate precursor having in this order is produced.

Specific examples of the composition for forming an ink-repellent silicone layer used in the present invention are shown below, but are not limited thereto.

The addition reaction type composition for forming an ink-repellent silicone layer used in the present invention includes a siloxane compound having two or more vinyl groups in the molecule, a siloxane compound having three or more SiH groups in the molecule, and a reaction It preferably contains a catalyst. Furthermore, a reaction inhibitor and a silane coupling agent may be included.

Examples of siloxane compounds having two or more vinyl groups in the molecule include diorganopolysiloxanes, organovinylpolysiloxanes, organovinylsiloxane-diorganosiloxane copolymers, and intramolecular vinyl groups having vinyl groups at both ends of the molecule. Examples include compounds having two or more diorganovinylsiloxy groups. Among them, preferred are diorganopolysiloxanes and organovinylsiloxane/diorganosiloxane copolymers having vinyl groups at both ends of the molecule. You may contain 2 or more types of these.

Diorganopolysiloxanes and organovinylsiloxane/diorganosiloxane copolymers having vinyl groups at both molecular ends have linear, cyclic, branched, or network molecular structures. Also, the organic groups bonded to the silicon atom may be the same or different, and each represents a monovalent organic group containing no aliphatic unsaturation. Examples of monovalent organic groups containing no aliphatic unsaturated bonds include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl; phenyl, tolyl, xylyl, aryl groups such as naphthyl group; aralkyl groups such as benzyl group and phenethyl group; halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group;

From the viewpoint of the ink repellency of the endless lithographic printing plate, it is preferable that 50 mol % or more of all the monovalent organic groups containing no aliphatic unsaturated bonds are methyl groups. Further, the weight average molecular weight of the siloxane compound having two or more vinyl groups in the molecule is preferably 30,000 or more from the viewpoint of improving printing durability and scratch resistance, and 300 from the viewpoint of improving coatability. ,000 or less is preferred. The weight average molecular weight can be obtained by measuring in terms of polystyrene using GPC.

If the content of the siloxane compound having two or more vinyl groups in the molecule is 60% by mass or more in the total solid content contained in the composition for forming an ink-repellent silicone layer, the ink-repellent silicone layer will have sufficient ink repellency. It is preferably 70% by mass or more, and even more preferably 80% by mass or more, in terms of improving the properties. Moreover, from the viewpoint of ensuring the curability of the ink-repellent silicone layer, the content is preferably 99% by mass or less.

Here, the total solid content in the composition for forming an ink-repellent silicone layer refers to the components remaining after the composition for forming an ink-repellent silicone layer has been applied and dried (removed volatile components).

Examples of siloxane compounds having 3 or more SiH groups in the molecule include organohydropolysiloxanes, organohydrosiloxane-diorganosiloxane copolymers, and compounds having 3 or more diorganohydroxy groups in the molecule. be done. Among them, organohydropolysiloxanes and organohydrosiloxane-diorganosiloxane copolymers are preferred. You may contain 2 or more types of these. The number of SiH groups in the molecule is preferably 5 or more, more preferably 6 or more, in order to improve the curability of the ink-repellent silicone layer.

Organohydropolysiloxanes and organohydrosiloxane-diorganosiloxane copolymers have linear, cyclic, branched or network molecular structures. Also, the organic groups bonded to the silicon atom may be the same or different, and each represents a monovalent organic group containing no aliphatic unsaturation. Examples of monovalent organic groups containing no aliphatic unsaturated bonds include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl; phenyl, tolyl, xylyl, aryl groups such as naphthyl group; aralkyl groups such as benzyl group and phenethyl group; halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group;

If the content of the siloxane compound having 3 or more SiH groups in the molecule is 0.5% by mass or more based on the total solid content in the composition for forming the ink-repellent silicone layer, the ink-repellent silicone layer is formed. is preferable for improving the curability of the resin, and 1% by mass or more is more preferable. Also, 10% by mass or less is preferable for improving ink repellency, and 5% by mass or less is more preferable.

The concentration of H groups derived from SiH groups in the total solid content of the composition for forming an ink-repellent silicone layer according to the present invention is preferably 0.001 to 0.04% by mass. A concentration of H groups derived from SiH groups in the total solid content of the ink-repellent silicone layer-forming composition of 0.001% by mass or more is preferable for improving the curability of the ink-repellent silicone layer. In addition, if the concentration of H groups derived from SiH groups in the total solid content of the composition for forming an ink-repellent silicone layer is 0.04% by mass or less, the ink repellency of the ink-repellent silicone layer can be improved. is preferred.

In terms of the relationship between the concentration of H groups derived from SiH groups in the total solid content of the composition for forming an ink-repellent silicone layer and the average elastic modulus of the ink-repellent silicone layer, the ink-repellent silicone layer When the concentration of H groups derived from SiH groups in the total solid content of the forming composition is 0.001% by mass, the average elastic modulus is approximately 0.001 MPa. When the concentration of H groups derived from SiH groups in the total solid content of the composition for forming an ink-repellent silicone layer is 0.04% by mass, the average elastic modulus is approximately 10 MPa.

As the reaction catalyst, a known hydrosilylation reaction catalyst can be used, but it is preferable to contain platinum or rhodium from the viewpoint of high reactivity. Specifically, simple platinum, solid platinum supported on a carrier (alumina, silica, carbon black, etc.), chloroplatinic acid, platinum-olefin complex, platinum-vinylsilane complex, platinum-vinylsiloxane complex, platinum-phosphine complexes, platinum-phosphite complexes, platinum-acetylacetone complexes, platinum-acetoacetate alkyl ester complexes, platinum-malonic acid dialkyl ester complexes, also described in Ashby et al., US Pat. No. 3,159,601 and US Pat. and platinum alcoholate catalysts described in Lamoreaux et al., US Pat. No. 3,220,972. Examples of catalysts other than platinum compounds include RhCl( _PPh3 ) ₃ , _{RhCl3 , RhAl2O3 , RuCl3} , _IrCl3 , FeCl3, _{AlCl3 , PdCl2.2H2O} , _NiCl2 , TiCl ₄ and the like. These reaction catalysts may be used alone or in combination of two or more.

The content of the reaction catalyst is preferably 0.0001% by mass or more based on the total solid content of the composition for forming an ink-repellent silicone layer from the viewpoint of improving the curability of the ink-repellent silicone layer, and is preferably 0.001%. % or more by mass is more preferable. In order to improve the pot life of the composition for forming an ink-repellent silicone layer, it is preferably 1% by mass or less, and 0.1% by mass or less, based on the total solid content of the composition for forming an ink-repellent silicone layer. is more preferred.

As the reaction inhibitor, those known as hydrosilylation reaction inhibitors or reaction retarders can be used. Preferred are amine compounds and acetylene compounds, and more preferred are pyridine, picoline, 2,2'-dipyridyl, 2-butanone oxime, acetylene alcohol, and acetylene silane. Acetylene alcohols include, for example, 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, 1-ethynyl-1-hexanol, 3,5-dimethyl-1-hexyn-3- ol, 3-methyl-1-pentyn-3-ol, and the like. You may contain 2 or more types of these. By containing these reaction inhibitors, the pot life of the composition for forming an ink-repellent silicone layer is improved.

The content of the reaction inhibitor is 0.01 parts by mass or more per 100 parts by mass of the total solid content in the composition for forming an ink-repellent silicone layer. It is preferable in terms of improvement, and 0.1 parts by mass or more is more preferable. In order to ensure the curability of the ink-repellent silicone layer, it is preferably 20 parts by mass or less, and 15 parts by mass or less based on 100 parts by mass of the total solid content in the ink-repellent silicone layer-forming composition. more preferred.

Silane coupling agents include methyltriacetoxysilane, ethyltriacetoxysilane, phenyltriacetoxysilane, toluyltriacetoxysilane, xylyltriacetoxysilane, methyltris(methylethylketoximino)silane, ethyltris(methylethylketoximino)silane, phenyltris (methylethylketoximino)silane, toluyltris(methylethylketoximino)silane, xylyltris(methylethylketoximino)silane, vinyltriacetoxysilane, allyltriacetoxysilane, 3-acryloxypropyltriacetoxysilane, 3-methacryloxypropyltriacetoxysilane silane, vinyltris(methylethylketoximino)silane, allyltris(methylethylketoximino)silane, 3-acryloxypropyltris(methylethylketoximino)silane, 3-methacryloxypropyltris(methylethylketoximino)silane, and the like, but these is not limited to Among them, vinyltriacetoxysilane and vinyltris(methylethylketoximide) improve the reactivity with siloxane compounds having 3 or more SiH groups in the molecule and the adhesiveness with the lower layer, and suppress the decrease in ink repellency. n) Silane is preferred.

If the content of the silane coupling agent is 0.5% by mass or more in the total solid content of the composition for forming an ink-repellent silicone layer, the adhesiveness (vs. lower layer adhesiveness), and 1% by mass or more is more preferable. In addition, it is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of improving ink repellency.

The condensation reaction type ink-repellent silicone layer-forming composition used in the present invention preferably contains a siloxane compound having two or more silanol groups in the molecule and a silane coupling compound. Furthermore, a reaction catalyst may be included.

Examples of siloxane compounds having two or more silanol groups in the molecule include diorganopolysiloxanes having silanol groups at both ends of the molecule.

A diorganopolysiloxane having silanol groups at both ends of the molecule has a linear, cyclic, branched, or network molecular structure. Also, the organic groups bonded to the silicon atom may be the same or different, and each represents a monovalent organic group containing no aliphatic unsaturation. Examples of monovalent organic groups containing no aliphatic unsaturated bonds include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl; phenyl, tolyl, xylyl, aryl groups such as naphthyl group; aralkyl groups such as benzyl group and phenethyl group; halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group;

From the viewpoint of the ink repellency of the endless lithographic printing plate, it is preferable that 50 mol % or more of all the monovalent organic groups containing no aliphatic unsaturated bonds are methyl groups. Further, the weight average molecular weight of the siloxane compound having two or more silanol groups in the molecule is preferably 30,000 or more from the viewpoint of improving printing durability and scratch resistance, and 300 from the viewpoint of improving coatability. ,000 or less is preferred. The weight average molecular weight can be obtained by measuring in terms of polystyrene using GPC.

If the content of the siloxane compound having two or more silanol groups in the molecule is 60% by mass or more in the total solid content contained in the ink-repellent silicone layer-forming composition, the ink repellency in the ink-repellent silicone layer is high. It is preferably 70% by mass or more, and even more preferably 80% by mass or more, in terms of improving the properties. Moreover, from the viewpoint of ensuring the curability of the ink-repellent silicone layer, the content is preferably 99% by mass or less.

Examples of the silane coupling agent include the silane coupling agents exemplified in the addition reaction type composition for forming an ink-repellent silicone layer.

The content of the silane coupling agent is preferably 0.5% by mass or more based on the total solids contained in the composition for forming an ink-repellent silicone layer from the viewpoint of improving curability and adhesion to the lower layer, and is preferably 1% by mass. The above is more preferable. In addition, it is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of improving ink repellency.

Examples of reaction catalysts include organic carboxylic acids, acids, alkalis, amines, metal alkoxides, metal diketenates, organic acid salts of metals such as tin, lead, zinc, iron, cobalt, calcium and manganese. Specific examples include dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, zinc octylate, and iron octylate. You may contain 2 or more types of these.

The content of the reaction catalyst is preferably 0.01% by mass or more and 1% by mass or less based on the total solid content of the composition for forming an ink-repellent silicone layer. If it is 0.01% by mass or more, the curability of the ink-repellent silicone layer and adhesion to the lower layer will be good, and if it is 1% by mass or less, the stability of the composition for forming an ink-repellent silicone layer will be good. .

The addition reaction-condensation reaction combined type composition for forming an ink-repellent silicone layer used in the present invention includes a siloxane compound having two or more silanol groups in the molecule and one or more vinyl groups in the molecule. It preferably contains a silane coupling agent, a siloxane compound having 3 or more SiH groups in the molecule, and a reaction catalyst. Furthermore, a reaction inhibitor may be included.

Examples of the siloxane compound having two or more silanol groups in the molecule include the siloxane compounds exemplified in the condensation reaction type composition for forming an ink-repellent silicone layer.

If the content of the siloxane compound having two or more silanol groups in the molecule is 60% by mass or more in the total solid content contained in the ink-repellent silicone layer-forming composition, the ink repellency in the ink-repellent silicone layer is high. It is preferably 70% by mass or more, and even more preferably 80% by mass or more, in terms of improving the properties. Moreover, from the viewpoint of ensuring the curability of the ink-repellent silicone layer, the content is preferably 99% by mass or less.

As the silane coupling agent having one or more vinyl groups in the molecule, among the silane coupling agents exemplified in the addition reaction type composition for forming an ink-repellent silicone layer, one or more vinyl groups in the molecule can be used. A silane coupling agent having a group can be mentioned.

The content of the silane coupling agent having one or more vinyl groups in the molecule is 0.5% by mass or more based on the total solid content of the composition for forming an ink-repellent silicone layer. It is preferable in terms of improving the properties, and 1% by mass or more is more preferable. In addition, it is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of improving ink repellency.

Examples of the siloxane compound having 3 or more SiH groups in the molecule include the siloxane compounds exemplified in the addition reaction type composition for forming an ink-repellent silicone layer.

If the content of the siloxane compound having 3 or more SiH groups in the molecule is 0.5% by mass or more based on the total solid content in the composition for forming the ink-repellent silicone layer, the ink-repellent silicone layer is formed. is preferable for improving the curability of the resin, and 1% by mass or more is more preferable. Also, 10% by mass or less is preferable for improving ink repellency, and 5% by mass or less is more preferable.

Examples of the reaction catalyst include the reaction catalysts exemplified in the addition reaction type composition for forming an ink-repellent silicone layer.

The content of the reaction catalyst is preferably 0.0001% by mass or more based on the total solid content of the composition for forming an ink-repellent silicone layer from the viewpoint of improving the curability of the ink-repellent silicone layer, and is preferably 0.001%. % or more by mass is more preferable. In order to improve the pot life of the composition for forming an ink-repellent silicone layer, it is preferably 1% by mass or less, and 0.1% by mass or less, based on the total solid content of the composition for forming an ink-repellent silicone layer. is more preferred.

Examples of the reaction inhibitor include the reaction inhibitors exemplified in the addition reaction type composition for forming an ink-repellent silicone layer.

The content of the reaction inhibitor is 0.01 parts by mass or more per 100 parts by mass of the total solid content in the composition for forming an ink-repellent silicone layer, and the pot life of the composition for forming an ink-repellent silicone layer is maintained. It is preferable in terms of improvement, and 0.1 parts by mass or more is more preferable. In order to ensure the curability of the ink-repellent silicone layer, it is preferably 20 parts by mass or less, and 15 parts by mass or less based on 100 parts by mass of the total solid content in the ink-repellent silicone layer-forming composition. more preferred.

For the purpose of further improving the ink repellency of the addition reaction type, condensation reaction type, and addition reaction-condensation reaction combined type ink repellent silicone layer, a composition for forming an ink repellent silicone layer was added to the surface of the ink repellent silicone layer at 25°C. It may contain a liquid with a tension of 30 mN/m or less. If the surface tension of the liquid is 30 mN/m or less, the liquid having a surface tension of 30 mN/m or less at 25° C. appears on the surface of the ink-repellent silicone layer, and the ink repellency is improved because the ink is removed. and the scumming start temperature can be raised. For improving the ink repellency, the liquid preferably has a surface tension of 22 mN/m or less at 25° C., more preferably 21 mN/m or less. The surface tension can be measured by a known Wilhelmy method using a platinum plate (also called plate method or vertical plate method).

A liquid having a surface tension of 30 mN/m or less at 25° C. preferably exhibits a mass reduction of 0 to 0.5% by mass after standing at 150° C. for 24 hours under an atmosphere of 1 atmospheric pressure. If the weight loss after standing at 150 ° C. for 24 hours in an atmosphere of 1 atm is 0 to 0.5% by mass, the ink is difficult to volatilize during the production and storage of the endless lithographic printing plate precursor and the endless lithographic printing plate. It is difficult to lose the effect of resilience.

The content of the liquid having a surface tension of 30 mN/m or less at 25° C. is preferably 5 to 40 mass % of the total solid content in the composition for forming an ink-repellent silicone layer. When the amount is 5% by mass or more, the ink repellency is remarkably improved, and when the amount is 40% by mass or less, sufficient strength of the ink-repellent silicone layer can be ensured, so that printing durability can be maintained.

The liquid having a surface tension of 30 mN/m or less at 25° C. is preferably a silicone compound, more preferably a silicone oil. The silicone oil referred to in the present invention refers to a polysiloxane component that does not participate in cross-linking of the ink-repellent silicone layer. Specifically, polydimethylsiloxane with a trimethylsilyl group at the molecular chain end, cyclic polydimethylsiloxane, dimethylsiloxane-methylphenylsiloxane copolymer with a trimethylsilyl group at the molecular chain end, dimethylsiloxane-diphenylsiloxane copolymer with a trimethylsilyl group at the molecular chain end, etc. , alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, epoxy polyether-modified silicone oil, phenol-modified silicone oil , carboxy-modified silicone oil, mercapto-modified silicone oil, amide-modified silicone oil, carvana-modified silicone oil, higher fatty acid-modified silicone oil, etc. be done.

The molecular weight of the liquid having a surface tension of 30 mN/m or less at 25° C. is preferably a weight average molecular weight of 200 to 100,000. If the weight-average molecular weight is 200 or more, volatilization of the liquid having a surface tension of 30 mN/m or less at 25° C. is suppressed during the production or storage of the endless lithographic printing plate, and if it is 100,000 or less, the ink repellency is good. Bleeding out from the silicone layer is suppressed. 1,000 to 10,000 is more preferred. The weight average molecular weight can be obtained by measuring in terms of polystyrene using GPC.

In addition, the addition reaction type, condensation reaction type, and addition reaction-condensation reaction combination type composition for forming an ink-repellent silicone layer may contain silica particles, vinyl groups, SiH groups, and silanol groups for the purpose of improving rubber strength. It may contain a known reinforcing agent such as a silicone resin having a functional group such as.

Further, the addition reaction type, condensation reaction type, and addition reaction-condensation reaction combined type composition for forming an ink-repellent silicone layer may contain a solvent for the purpose of improving coatability.

Solvents include, for example, aliphatic, alicyclic, aromatic hydrocarbons, halogenated hydrocarbons, chain or cyclic ether compounds, and the like. Among them, aliphatic or alicyclic hydrocarbons are preferable from the viewpoint of improving economy and safety. In order to improve the solubility of the solids contained in the ink-repellent silicone layer-forming composition, the solubility parameter of the solvent is preferably 16.4 (MPa) ^1/2 or less, more preferably 15.4 (MPa). ^1/2 or less is more preferable, and 14.4 (MPa) ^1/2 or less is even more preferable. Solubility parameters can be calculated using the Fedors estimation method. In addition, the boiling point at 1 atm is preferably 60° C. or higher, more preferably 80° C. or higher, from the viewpoint of improving safety and handleability. On the other hand, the boiling point at 1 atm is preferably 150° C. or lower, more preferably 120° C. or lower, from the viewpoint of improving the drying property of the composition for forming an ink-repellent silicone layer. Specific examples of such solvents include linear or branched aliphatic hydrocarbons having 6 to 9 carbon atoms, and alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, and trimethylcyclohexane. etc. can be mentioned. Two or more of these solvents may be mixed and used, or a commercially available solvent in which these solvents are mixed in advance, represented by the following, may be used.

Mixtures of branched aliphatic hydrocarbons: For example, Marcazol 8 (manufactured by Maruzen Petrochemical Co., Ltd.), "Isopar" (registered trademark) C, "Isopar" (registered trademark) E (both manufactured by ExxonMobil Chemical), Examples include IP Solvent 1016 (manufactured by Idemitsu Kosan Co., Ltd.) and "ISOSOL" (registered trademark) 200 (manufactured by JX Nippon Oil & Energy Corporation), which are available from each company.

Mixtures of alicyclic hydrocarbons: Examples include Exsol DSP80/100, Exsol DSP100/140, Exsol D30 (all manufactured by Exxon Mobil Chemicals), and CS gasoline (manufactured by JX Nippon Oil & Energy Corporation). , available from each company.

In addition, a solvent other than the above-mentioned solvents can be mixed and used, but from the viewpoint of improving the solubility of the composition for forming an ink-repellent silicone layer, the above-mentioned solvent is contained in the total solvent in an amount of 80% by volume or more. is preferred, and it is more preferred that the content is 90% by volume or more.

A specific method for preparing the composition for forming an ink-repellent silicone layer will be described below, but the method is not limited to this.

For example, a solvent in a container, a siloxane compound having two or more vinyl groups in the molecule, a siloxane compound having three or more SiH groups in the molecule, a liquid having a surface tension of 30 mN/m or less at 25°C, and a reaction An inhibitor and a silane coupling agent are added and stirred until the ingredients are uniform. Furthermore, the composition for forming an ink-repellent silicone layer can be obtained by adding a reaction catalyst and stirring until the ingredients become uniform.

From the viewpoint of maintaining curability, it is preferable to add the reaction catalyst immediately before the composition for forming the ink-repellent silicone layer is applied.

When applying the composition for forming an ink-repellent silicone layer, it is preferable to remove as much water as possible from the surface of the endless lithographic printing plate base material and the surface of the adhesive layer in order to improve the adhesiveness.

The method of applying the composition for forming an ink-repellent silicone layer includes, but is not limited to, a dipping method, a spraying method, a cylindrical slit die coating method, and the like. For the purpose of accelerating curing, it is preferable to heat for 30 seconds to 10 minutes within the temperature range of 50 to 180° C. using a known hot air drying device or infrared drying device.

(2) A method for producing an endless lithographic printing plate precursor having, in this order, an endless lithographic printing plate substrate, an ink repellent layer, and an ink-receiving layer Continuously and seamlessly applying and curing a repellent silicone layer-forming composition, and then seamlessly and continuously applying and curing an ink-receptive silicone layer-forming composition to the surface of the ink-repellent silicone layer. , an endless lithographic printing plate precursor having an ink receptive layer consisting of an endless lithographic printing plate substrate, an ink repellent silicone layer and an ink receptive silicone layer in this order is produced. Examples of methods for applying the ink-repellent silicone layer-forming composition and ink-receptive silicone layer-forming composition include, but are not limited to, dipping, spraying, cylindrical slit die coating, and the like. In order to accelerate curing, it is preferable to use a known hot air drying device or infrared drying device to heat the composition within a temperature range of 50 to 180° C. for 30 seconds to 10 minutes.

Further, as another form of (2), the surface of the endless lithographic printing plate substrate obtained by the above-described production method is continuously and seamlessly coated with a hydrophilic layer-forming composition, cured, and then hydrophilic. A composition for forming a photosensitive layer or a composition for forming a heat-sensitive layer is continuously and seamlessly applied to the surface of the layer and cured to form a substrate for an endless lithographic printing plate, a hydrophilic layer, a photosensitive layer or a heat-sensitive layer in this order. An endless lithographic printing plate precursor having Examples of the coating method for the hydrophilic layer-forming composition, the photosensitive layer-forming composition, or the heat-sensitive layer-forming composition include, but are not limited to, a dipping method, a spraying method, a cylindrical slit die coating method, and the like. In order to accelerate curing, it is preferable to use a known hot air drying device or infrared drying device to heat the composition within a temperature range of 50 to 180° C. for 30 seconds to 10 minutes.

(3) A method for producing an endless lithographic printing plate precursor having an endless lithographic printing plate substrate, an ink-receptive layer, and an ink-repellent layer in this order The surface of the endless lithographic printing plate substrate obtained by the above-described production method is exposed After seamlessly and continuously coating and curing the layer-forming composition or the thermosensitive layer-forming composition, the ink-repellent silicone layer-forming composition is seamlessly and continuously applied to the surface of the photosensitive layer or the thermosensitive layer, By curing, an endless lithographic printing plate precursor having an endless lithographic printing plate substrate, a photosensitive layer or a heat-sensitive layer, and an ink-repellent silicone layer in this order is produced. Examples of methods for applying the composition for forming the photosensitive layer, the composition for forming the heat-sensitive layer, and the composition for forming the ink-repellent silicone layer include, but are not limited to, dipping, spraying, cylindrical slit die coating, and the like. In order to accelerate curing, it is preferable to use a known hot air drying device or infrared drying device to heat the composition within a temperature range of 50 to 180° C. for 30 seconds to 10 minutes.

In the endless lithographic printing plate precursors exemplified in (1) to (3) above, when an adhesive layer is provided on the endless lithographic printing plate substrate, a composition for forming an adhesive layer on the endless lithographic printing plate substrate can be applied seamlessly and continuously, dried and cured with or without heating to form an adhesive layer on the endless lithographic printing plate substrate.

Examples of the method for applying the adhesive layer-forming composition include a dipping method, a spraying method, a cylindrical slit die coating method, and the like, but are not limited to these. In order to accelerate curing, it is preferable to use a known hot air drying device or infrared drying device to heat the composition within a temperature range of 50 to 180° C. for 30 seconds to 10 minutes.

Next, a method for producing an endless lithographic printing plate will be described.

An endless planographic printing plate can be produced by the following two methods from an endless planographic printing plate precursor having an endless planographic printing plate substrate and an ink-repellent silicone layer in this order.

As the first production method, the method described in International Publication No. WO 2019/203261 can be mentioned. This is a method of discharging a composition in a pattern.

As a second production method, an ink-repellent silicone layer of the endless lithographic printing plate precursor is pattern-irradiated with active energy rays to change the irradiated area to ink receptivity.

The endless lithographic printing plate obtained by this method has ink-repellent areas and ink-receiving areas on at least the surface of the ink-repellent silicone layer. Here, the surface refers to a region formed in the direction of the endless lithographic printing plate substrate from the surface layer of the layer composed of the ink repellent portion and the ink receiving portion that does not face the endless lithographic printing plate substrate.

2 and 3 are cross-sectional views showing an example of an endless lithographic printing plate having an ink-repellent portion and an ink-receiving portion on at least the surface of an ink-repellent silicone layer. In both FIGS. 2 and 3, a heat-shrink tube 6 and an ink-repellent silicone layer 7 are provided in this order on a cylindrical support 5. At least the surface of the layer has an ink-repellent portion 8 and ink adhesion. It has a meat portion 9 . In FIG. 2, the ink-receiving portion 9 is formed in a portion of the depth direction from the surface layer of the surface of the shrink tube that does not face the heat-shrinkable material 6, and in FIG. An ink-receiving portion 9 is formed from the surface of the shrink tube that does not face the heat-shrinkable material 6 to the surface of the shrink tube that faces the heat-shrinkable material. 2 and 3 show an example in which the ink-repellent silicone layer 7 is directly provided on the heat-shrinkable material 6 of the shrink tube. An adhesive layer may be provided between the heat-shrinkable material 6 of the shrink tube and the ink-repellent silicone layer 7 for the purpose of enhancing the adhesive strength of the shrink tube. 2 and 3 show an example in which the heat-shrink tube 6 is directly provided on the cylindrical support 5. A rubber layer may be provided between the heat shrinkable material 6 of the shrink tube.

In the present invention, the ink-receiving portion refers to a portion to which ink adheres when the ink is spread on the surface of the endless lithographic printing plate, and the ink-repellent portion refers to the portion where the ink is applied to the surface of the printing member. It refers to the part where ink does not adhere (ink repels) when unfolded. The ink-receiving portion may be formed partially in the depth direction from the surface of the shrink tube that does not face the heat-shrinkable product, or the surface of the shrink tube that does not face the heat-shrinkable product may face the support. The ink-receiving portion may be formed up to the surface layer of the surface to be coated.

The average elastic modulus of the ink-receiving portion is preferably 60 MPa or higher, more preferably 100 MPa or higher, still more preferably 150 MPa or higher, and even more preferably 200 MPa or higher. The average elastic modulus of the ink-receiving portion in the present invention is preferably 10000 MPa or less, more preferably 6000 MPa or less, still more preferably 2000 MPa or less, and even more preferably 1000 MPa or less. When the pressure is 60 MPa or more, the ink receptivity is further improved, which is preferable.

The difference between the average elastic modulus of the ink-receiving portion and the ink-repellent silicone layer is preferably 50 MPa or more, more preferably 100 MPa or more, even more preferably 150 MPa or more, and even more preferably 200 MPa or more. . In the present invention, the difference between the average elastic modulus of the ink-receiving portion and the average elastic modulus of the ink-repellent silicone layer is preferably 10,000 MPa or less, more preferably 6,000 MPa or less, even more preferably 2,000 MPa or less, and even more preferably 1,500 MPa. . If the difference between the average elastic modulus of the ink-receiving portion and the average elastic modulus of the ink-repellent silicone layer is within the above range, both the ink-repellent property and the ink-receiving property of the endless lithographic printing plate can be further improved. It is preferable because it can be done.

In the present invention, the ink-receiving portion preferably contains a silsesquioxane structure and/or a glass structure. It is preferable that the ink-receiving part contains a silsesquioxane structure and/or a glass structure, because the ink receptivity is further improved.

The silsesquioxane structure and glass structure in the ink-receiving portion can be confirmed by FT-IR-ATR analysis. In FT-IR-ATR analysis, the silsesquioxane structure and glass structure show signals in absorption bands around 1271, 1133 and 995 cm ⁻¹ .

In the present invention, the element concentration ratio of the ink-receiving portion is preferably in the range of silicon: 23 to 33 atom %, oxygen: 30 to 67 atom %, carbon: 0 to 47 atom %. If silicon: 23 atom % or more, oxygen: 30 atom % or more, carbon: 47 atom % or less, the ink receptivity is further improved, and if silicon: 33 atom % or less, oxygen: 67 atom % or less, and carbon: 0 atom % or more, a tough film is obtained. is obtained, and the printing durability is improved. The ratio of oxygen concentration to silicon concentration (oxygen concentration/silicon concentration) in the ink-receiving portion is preferably within the range of 1.3 to 2.0. If it is 1.3 or more, the ink receptivity will further improve, and if it is 2.0 or less, a tough film will be obtained and printing durability will be improved, so it is preferable.

The element concentration in the ink-receiving portion can be measured by analysis using X-ray photoelectron spectroscopy. Further, by dividing the obtained oxygen concentration value by the silicon concentration value, the ratio of the oxygen concentration to the silicon concentration (oxygen concentration/silicon concentration) can be calculated.

In the present invention, 12 microliters of dimethylsilicone oil having a liquid viscosity of 20 centistokes is brought into contact with the surface of the ink-receiving portion, and the spot diameter after 10 minutes has passed is preferably 20 to 37 mm. In the present invention, the spot diameter at 10 minutes after contact means the length of the longest diameter in the spot shape of dimethyl silicone oil at 10 minutes after contact. For example, if the spot shape of the dimethyl silicone oil at 10 minutes after contact is a perfect circle, the diameter of the circle is the diameter of the spot, and if it is elliptical, the major axis is the major axis. This evaluation represents the degree of penetration (swelling) of dimethylsilicone oil into the contact layer. When dimethyl silicone oil comes into contact with the ink-repellent portion, it quickly permeates the layer, so that the dimethyl silicone oil does not spread easily, resulting in a smaller spot diameter after the passage of time. On the other hand, when dimethylsilicone oil comes into contact with the ink-receiving portion, the permeation into the layer is greatly suppressed, so the dimethylsilicone oil tends to wet and spread, resulting in a large spot diameter after the passage of time. If the spot diameter after 10 minutes has passed is 20 mm or more, good ink receptivity can be obtained, 22 mm or more is more preferable, and 24 mm or more is even more preferable. Also, if the spot diameter after 10 minutes has passed is 37 mm or less, the printing durability is good, and 35 mm or less is more preferable, and 33 mm or less is even more preferable.

Commercially available dimethyl silicone oils having a liquid viscosity of 20 centistokes include KF-96-20cs (manufactured by Shin-Etsu Chemical Co., Ltd.), DOWSIL (registered trademark) SH200 Fluid 20CS (manufactured by Dow Corning Toray Co., Ltd.), WACKER (registered trademark) SILICONE FLUID AK 20 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), Element 14 (registered trademark) PDMS 20-JC (manufactured by Momentive Performance Materials Japan LLC), DMS-T12 (manufactured by GELEST Inc. ), etc., and even when evaluated using any of these dimethyl silicone oils, equivalent values of spot diameters after the passage of time can be obtained.

Examples of active energy rays include electron beams and ultraviolet rays with a wavelength of 125 to 260 nm. The wavelength of ultraviolet rays is more preferably 125 nm to 200 nm. Here, the ultraviolet rays having a wavelength of 125 to 260 nm refer to ultraviolet rays having a peak wavelength at a wavelength of 125 to 260 nm. When the ink-repellent portion is irradiated with an electron beam or ultraviolet rays having a wavelength of 125 to 260 nm, at least the surface of the ink-repellent silicone layer in the irradiated portion changes to a structure containing a silsesquioxane structure and/or a glass structure, thereby causing ink repulsion. property changes to ink receptivity.

Among them, it is preferable to directly draw the pattern of the ink-receiving portion by using an electron beam lithography device, an ultraviolet laser lithography device with a wavelength of 125 to 260 nm, or the like, because a mask for plate making is unnecessary.

As for the electron beam irradiation apparatus, a scanning beam system of a scanning type and a non-scanning area beam system can be mentioned, and any of these systems can be suitably used. Generally, the scanning beam method is used for high energy devices of 300 keV or more, and the area beam method is often used for low energy devices of 300 keV or less.

The electron beam drawing apparatus includes a spot beam system, a variable shaped beam (rectangular beam) system, a character projection system, and the like, and any of these systems can be suitably used. Also, these methods may be combined. The greatest advantage of the spot beam method is that ultra-high-definition (several tens to several hundred nm) patterning can be performed, but on the other hand, it has the disadvantage of low productivity (throughput) of printing members. In the manufacture of printing materials, even at a high resolution of 4000 dpi, the minimum dot size is about 6 μm. sufficient, which can increase the productivity of endless lithographic printing plates.

The electron beam dose is preferably 100 to 3000 kGy, more preferably 500 to 2000 kGy. If it is 100 kGy or more, the ink receptivity of the electron beam irradiated portion is further improved, and if it is 3000 kGy or less, it is preferable because productivity and printing durability are excellent.

The acceleration voltage of the electron beam is preferably 50-150 kV, more preferably 75-125 kGy. If it is 50 kGy or more, it is preferable because it is excellent in productivity. This is preferable because damage to the object or the adhesive layer can be suppressed.

Examples of the ultraviolet irradiation device with a wavelength of 125 to 260 nm include high-pressure mercury lamps, low-pressure mercury lamps, excimer lamps, and the like, in which the peak wavelength of irradiation light falls within the range of 125 to 260 nm. Among these, low-pressure mercury lamps and excimer lamps are preferred. As excimer lamps with a wavelength of 125 to 260 nm, Ar ₂ (126 nm), Kr ₂ (146 nm), F ₂ (153 nm), ArBr (165 nm), Xe ₂ (172 nm), ArCl (175 nm), ArF (193 nm), KrBr (207 nm), KrCl (222 nm), KrF (248 nm), XeI (253 nm), HgXe (254 nm), _Cl2 (259 nm) and other rare gas excimer lamps and rare gas halogen excimer lamps, but are not limited to these. . Among them, Ar ₂ (126 nm), Kr ₂ (146 nm), F ₂ (153 nm), ArBr (165 nm), Xe ₂ (172 nm), ArCl (175 nm), ArF are preferred in terms of improving the productivity of endless lithographic printing plates. It is more preferable to use a vacuum ultraviolet excimer lamp with a wavelength of 125 to 200 nm such as (193 nm).

Examples of ultraviolet lasers with a wavelength of 125 to 260 nm include the third harmonic of alexandrite laser (252 nm), the fifth harmonic of Nd: YAG laser (213 nm), the fifth harmonic of Nd: _YVO4 laser (213 nm), and the Nd: solid-state lasers such as the fifth harmonic (211 nm) of YLF lasers; gas lasers such as F2 lasers ₍ 157 nm), ArF lasers (193 nm), KCl lasers (222 nm), and KrF lasers (248 nm); is not limited to Among them, it is more preferable to use a vacuum ultraviolet laser having a wavelength of 125 to ₂₀₀ nm, such as F2 laser (157 nm) or ArF laser (193 nm), from the viewpoint of improving the productivity of the endless lithographic printing plate.

The exposure amount of ultraviolet rays having a wavelength of 125 to 260 nm is preferably 300 to 3000 mJ/cm ² and more preferably 500 to 2000 mJ/cm ² . If it is 300 mJ/cm ² or more, the ink receptivity of the UV-irradiated portion is further improved, and if it is 3000 mJ/cm ² or less, it is preferable because productivity and printing durability are excellent.

Irradiation with electron beams or ultraviolet rays having a wavelength of 125 to 200 nm is preferably carried out in nitrogen gas or in a vacuum from the viewpoints of suppressing ozone generation and suppressing energy loss of irradiation rays due to oxygen and the like.

A method for producing an endless lithographic printing plate from an endless lithographic printing plate precursor having an endless lithographic printing plate substrate, an ink-repellent silicone layer, and an ink-receptive silicone layer in this order is described in WO 2019/203263. method can be mentioned. Specifically, a high-output laser is pattern-radiated from the ink receptive silicone layer side of the endless lithographic printing plate precursor to expose the ink repellent silicone layer in the irradiated areas.

As a method for producing an endless lithographic printing plate from an endless lithographic printing plate precursor having an endless lithographic printing plate substrate, a hydrophilic layer, a photosensitive layer or a heat-sensitive layer in this order, pattern exposure is performed from the side of the photosensitive layer or the heat-sensitive layer, A method of developing using water or a liquid containing water as a main component or a developing solution can be used.

As a method for producing an endless lithographic printing plate from an endless lithographic printing plate precursor having, in this order, an endless lithographic printing plate substrate, a photosensitive layer or a heat-sensitive layer, and an ink-repellent silicone layer, pattern exposure is performed from the ink-repellent silicone layer side. and development using water or a liquid containing water as a main component or a developing solution.

Next, a method for manufacturing endless printed matter will be described.

The method for producing an endless printed matter according to the present invention uses the endless lithographic printing plate, ink, and print medium according to the present invention. Further, when the endless planographic printing plate is a wet plate, the endless planographic printing plate, fountain solution, ink, and printing medium are used. Specifically, it preferably includes a step of applying ink to the surface of the ink-receiving portion of the endless lithographic printing plate and a step of transferring the ink directly or via a blanket to the printing medium.

One embodiment of the method for producing an endless printed matter according to the present invention will be described with reference to FIG. Although an example using the blanket cylinder 13 will be described below, the present invention is not limited to this. may be transferred directly to the print medium 14 after the ink is applied. Further, although an example in which ink is supplied from above the print medium 14 will be described below, ink may be supplied from below the print medium 14 .

First, ink is supplied to the ink roller 10 . The ink supplied to the ink roller 10 adheres to the ink receiving portion of the endless planographic printing plate 12 at the point of contact with the endless planographic printing plate 12 . The ink adhering to the ink receiving surface of the endless lithographic printing plate 12 is transferred to the surface of the blanket cylinder 13 at the point of contact with the blanket cylinder 13 . The ink deposited on the blanket cylinder 13 is transferred to the print medium 14 at the point of contact with the print medium 14 placed on the impression cylinder 15 . A printed matter is obtained by drying the print medium 14 after the ink transfer, if necessary. Further, when the endless lithographic printing plate is a wet lithographic printing plate, dampening water is supplied to the dampening water roller 11 before supplying the ink to the ink roller 10 . The dampening water supplied to the dampening water roller 11 adheres to the surface of the ink repellent portion (hydrophilic layer exposed portion) of the endless planographic printing plate 12 at the point of contact with the endless planographic printing plate 12 . The subsequent method of supplying ink to the ink roller 10 is the same as the method described above. The rotation speed of the ink roller, dampening water roller, endless lithographic printing plate, and each cylinder is not particularly limited, and can be appropriately set according to the quality required for the printed matter, the properties of the ink, and the like.

As the printing press used for producing the endless printed matter according to the present invention, there are known direct printing presses and offset printing presses. , offset presses are preferred. An offset printing press consists of a feeder section, a printing section and a delivery section. The printing section has at least an ink supply section, a plate cylinder, a blanket cylinder and an impression cylinder.

As the offset printing press, an offset printing press equipped with a cooling mechanism for the rocking roller and/or the plate cylinder is preferable from the viewpoint of improving the scumming resistance.

In the case of printing using an oil-soluble or water-soluble oxidative polymerization type ink, a printed matter is obtained by drying and/or hardening the ink transferred to the printing medium by natural drying or heat treatment.

On the other hand, in the case of printing using oil-soluble or water-soluble active energy ray-curable ink, the ink transferred to the printing medium is instantly cured by the active energy ray from the active energy ray irradiation device, and the printed matter is obtained. preferred because it is

Active energy rays include visible rays, ultraviolet rays (UV), electron rays (EB), X-rays, particle rays, and the like, but ultraviolet rays and electron rays are preferred from the viewpoint of ease of handling of the radiation source.

When curing with ultraviolet rays, ultraviolet irradiation devices such as high ^- pressure mercury lamps, xenon lamps, metal halide lamps, and LEDs are preferably used. Curing at a conveying speed of 50 to 150 m/min is preferable from the standpoint of productivity. In particular, when using a print medium containing a plastic film or metal as the print medium, the print medium tends to expand and contract due to the heat generated by the active energy rays. LED-UV) can be preferably used.

When curing with an electron beam, an electron beam irradiation apparatus having an energy beam of 100 to 500 eV is preferably used.

Inks that can be preferably used in the present invention include, but are not limited to, the inks described below.

<Ink-1> Oil-soluble oxidative polymerization type ink As the oil-soluble oxidative polymerization type ink, for example, known inks that can be washed with an oil-based washing liquid disclosed in JP-A-48-004107, JP-A-01-306482, etc. and an oil-soluble oxidative polymerization type ink. In addition, the solvent component disclosed in JP-A-2005-336301, JP-A-2005-126579, JP-A-2011-144295, JP-A-2012-224823, etc. can be used as a conventional mineral oil (petroleum) component. Oil-soluble oxidative polymerization inks include soybean oil ink, vegetable oil ink, non-VOC ink, etc., in which soybean oil is replaced with a vegetable oil component.

<Ink-2> Water-soluble oxidative polymerization type ink As the water-soluble oxidative polymerization type ink, for example, known inks that can be washed with water or a water-based washing liquid disclosed in Japanese Patent Application Laid-Open No. 2009-57461, Japanese Patent No. 4522094, etc. A water-soluble oxidative polymerization type ink is mentioned.

<Ink-3> Oil-soluble active energy ray-curable ink As the oil-soluble active energy ray-curable ink, for example, it is possible to wash with an oil-based cleaning liquid disclosed in Japanese Patent No. 5158274, Japanese Patent Application Laid-Open No. 2012-211230, etc. A known active energy ray-curable ink can be used. Active energy ray-curable inks also include high-sensitivity UV inks used in power-saving (reduced lighting) UV printing and LED-UV printing.

<Ink-4> Water-soluble active energy ray-curable ink Water-soluble active energy ray-curable ink includes, for example, JP-A-2017-52817, WO 2017/047817, WO 2017/090663, etc. known water-soluble active energy ray-curable inks that can be washed with water or a water-based washing liquid disclosed in .

Among the above inks, oil-soluble or water-soluble active energy ray-curable inks cure instantly by irradiation with active energy rays after being transferred to the printing medium, so the back side can be printed and post-processed immediately. It is preferable because it has merits not found in the oxidative polymerization type ink. However, unlike conventional oxidative polymerization inks, active energy ray-curable inks do not contain any scumming-preventing components, or contain only a very small amount, so they tend to cause scumming during printing. have. Since the endless lithographic printing plate of the present invention has high ink repellency, oil-soluble active energy ray-curable ink and water-soluble active energy ray-curable ink can be preferably used. In addition, when cleaning the ink adhering to various rollers, blankets, printing materials, etc. of the printing press, oil-soluble ink such as oil-soluble oxidative polymerization type ink and oil-soluble active energy ray-curable ink is highly volatile and harmful. The use of organic solvents imposes a heavy burden on the human body and the environment. On the other hand, water-soluble inks such as water-soluble oxidative polymerization inks and water-soluble active energy ray-curable inks can be washed with water alone or with a washing liquid containing water as the main component. It is preferable in that it is not necessary to use a harmful organic solvent because of its high viscosity, and that the burden on the human body and the environment can be remarkably suppressed. In particular, water-soluble active energy ray-curable ink can be used more preferably.

Print media include papers such as woodfree paper, art paper, coated paper, cast paper, synthetic paper, newsprint, metals such as aluminum and aluminum alloys, iron, steel, zinc and copper, polyethylene terephthalate, polyethylene, Plastic films such as polyester, polyamide, polyimide, polystyrene, polypropylene, polycarbonate, and polyvinyl acetal, or composites of these papers, metals, and plastic films (metal vapor-deposited or laminated paper, plastic films, and plastic films paper or metal laminated, paper laminated metal or plastic film), and the like, but are not limited to these.

Among them, in the method for producing an endless printed matter according to the present invention, synthetic paper, metals, plastic films, metal vapor-deposited or laminated paper or plastic film, and plastic film whose printing surface is composed of metal or plastic film It is suitable for printing on non-absorbent print media such as paper or metal laminated to the ink.

Among the above, the printing surface of the printing medium, such as synthetic paper, plastic films, plastic film-laminated paper, or metal, whose printing surface is made of plastic film, should be coated with a primer resin to improve adhesion. coating, or surface treatment such as corona discharge treatment or plasma treatment.

As for the shape of the print medium, it is preferable to use a roll-shaped long print medium. By printing by the roll-to-roll method using the endless lithographic printing plate of the present invention and a roll-shaped long print medium, it is possible to mass-produce high-definition endless printed materials with seamless picture patterns.

The thickness of the ink coating film (ink cured film) on the print medium is preferably 0.1 to 50 μm. By keeping the thickness of the ink coating film within the above range, the ink cost can be reduced while maintaining good print quality.

Next, a method for regenerating a cylindrical support from an endless lithographic printing plate will be described.

Since the endless lithographic printing plate according to the present invention has the heat-shrinkable material of the shrink tube on the surface of the cylindrical support, the endless lithographic printing plate after printing can be easily formed into a cylindrical shape simply by peeling off the heat-shrinkable material of the shrink tube. The support can be regenerated, and complicated operations such as washing with a solvent and polishing the surface of the cylindrical support are unnecessary.

EXAMPLES The present invention will be described in more detail below with reference to examples.

<Preparation of substrate for endless lithographic printing plate>
A substrate for an endless lithographic printing plate was produced by the following method.

Description will be made with reference to FIG. The plate cylinder sleeve 16 (diameter: 268 mm, width direction length: 1100 mm) covered with the heat-shrinkable shrink tube 17 before heating is placed in an oven heated to 120° C. and heated for 5 minutes. A substrate for an endless lithographic printing plate having a shrink tube (a heat-shrinkable product of the heat-shrinkable shrink tube 17) 18 fixed to the plate cylinder sleeve 16 was obtained.

Evaluation in each example and comparative example was performed by the following methods.

<Evaluation method in each example/comparative example>
(1) Evaluation of heat-shrinkable shrink tube/heat-shrinkable material of shrink tube (1-1) Attachability of heat-shrinkable shrink tube The easiness of attaching the heat-shrinkable shrink tube to the plate cylinder sleeve was evaluated. The ease of attachment of the heat-shrinkable shrink tube was rated as follows.
A: Easy to install because there is a large difference between the outer diameter of the plate cylinder sleeve and the equivalent inner diameter of the heat-shrinkable shrink tube (installation time: less than 1 minute)
B: Installation is difficult due to the large difference between the outer diameter of the plate cylinder sleeve and the inner diameter of the heat-shrinkable shrink tube equivalent to a perfect circle (installation time: 1 minute or longer).

(1-2) Thickness unevenness of the heat-shrinkable material of the shrink tube The thickness of the heat-shrinkable material of the heat-shrinkable material of the shrink tube peeled off from the base material for the endless lithographic printing plate was measured using a thickness measuring device: Digimicro MH-15M (manufactured by Nikon Corporation). It was measured. The thickness unevenness was evaluated by measuring the thickness at 10 arbitrary points. The thickness unevenness of the heat-shrinkable shrink tube was rated as follows.
A: The difference between the maximum thickness and the minimum thickness is less than 5 μm B: The difference between the maximum thickness and the minimum thickness is less than 5 to 10 μm C: The difference between the maximum thickness and the minimum thickness is more than 10 μm.

(1-3) Solvent resistance of heat-shrinkable product of shrink tube The surface of the endless lithographic printing plate substrate was contacted with methyl ethyl ketone, which is a solvent component in the adhesive layer-forming composition described later, at room temperature for 5 minutes. The solvent resistance of the heat-shrinkable shrink tube was visually evaluated. The solvent resistance of the heat-shrinkable shrink tube was evaluated as follows.
A: No dissolution of the heat-shrinkable material of the shrink tube due to contact with methyl ethyl ketone B: Dissolution of the heat-shrinkable material of the shrink tube due to contact with methyl ethyl ketone.

(2) Evaluation of printed matter The endless lithographic printing plate obtained by the method described in each example and comparative example was mounted on the plate cylinder shaft of an EB offset printing machine: OFFSET CI/8 (manufactured by COMEXI), and the following is shown. 10,000 m printing was performed under the conditions.

<Print conditions>
Ink roller: #8000 (manufactured by Meiwa Rubber Industry Co., Ltd.)
Cylindrical blanket: EPDM blanket (manufactured by Kinyo Co., Ltd.)
Water-soluble EB ink: Offset EB ink F type FE1908 process 4 colors (manufactured by Samsung Ink Co., Ltd.)
Fountain water: Purified water (used only in Example 13, which prints using a lithographic printing plate with endless water)
Ink component non-absorbent print medium: “EMBRET” (registered trademark) PTM-12 (rolled biaxially stretched PET film, thickness: 12 μm, printing surface: easy adhesion treatment, manufactured by Unitika Ltd.)
Plate surface temperature: 25-28°C
Print speed: 100 m/min.

<Ink curing conditions>
EB irradiation dose: 40 kGy
EB irradiation atmosphere: in a nitrogen atmosphere.

(2-1) Possibility of endless printing By visually evaluating the printed material, the propriety of endless printing of intermittent patterns and continuous patterns was evaluated. The rating for the possibility of endless printing was as follows.
A: Endless printing is possible (the seam of the pattern is not confirmed on the printed matter)
B: Endless printing is not possible (seams of the pattern are observed on the printed matter).

(2-2) Register Misregistration A portion of the print for checking the registration accuracy (draft marks) cut out from the print at about 10,000 m from the start of printing was observed with an optical microscope, and the circumferential misregistration was measured. The marks for misregistration were as follows.
A: Misregistration of 0.2 mm or less B: Misregistration of more than 0.2 mm.

(2-3) Image reproducibility Cut out the printed matter from around 5,000 m from the start of printing, place it on OK “Top Coat” (registered trademark) + which is a layer of 5 sheets, and visually inspect the halftone dot portion with a loupe with a magnification of 50 times. Observed. Image reproducibility was rated as follows.
A: Reproduce halftone dots of 175 lpi (resolution: 2400 dpi) for AM screening at 1 to 99%.

(3) Ease of recycling of plate cylinder sleeve The ease of recycling of the plate cylinder sleeve from the endless lithographic printing plate after printing was evaluated. The ease of reproduction of the plate cylinder sleeve was rated as follows.
A: The plate cylinder sleeve can be easily recycled (the plate cylinder sleeve can be recycled simply by peeling off the heat-shrinkable material from the shrink tube).
B: The recycling of the plate cylinder sleeve is somewhat complicated (the plate cylinder sleeve can be recycled by peeling off the heat-shrinkable material of the shrink tube after removing the sheet-fed lithographic printing plate and the double-sided tape).
C: Difficult to recycle the plate cylinder sleeve (After swelling the adhesive layer by contacting the outer peripheral surface of the endless lithographic printing plate with N,N-dimethylformamide for 30 minutes, each layer formed on the outer peripheral surface of the plate cylinder sleeve After wiping with a cloth soaked in N,N-dimethylformamide until the residue is gone, the sleeve can be regenerated by drying the solvent remaining on the outer peripheral surface of the sleeve).

[Example 1]
Copalon PTF (material: PET, thickness: 10 μm, perfect circle equivalent diameter: 300 mm, width direction length 1200 mm (manufactured by Gunze Kobunshi Co., Ltd.)) is used as a heat-shrinkable shrink tube, and endless lithographic printing is performed by the method described above. A plate substrate was obtained. Using a cylindrical slit die coater (manufactured by Toray Engineering Co., Ltd.), the following composition for forming an adhesive layer was applied to the surface of the resulting endless lithographic printing plate substrate, and heated at 150°C for 5 minutes to obtain an average An adhesive layer having a thickness of 10 μm was provided.

<Composition for Forming Adhesive Layer>
The following components (a-1), (b-1) and (c-1) were put into a container and stirred and mixed until the components were uniform. The component (d-1) was added to the resulting mixture and stirred for 5 minutes to obtain a composition for forming an adhesive layer.
(a-1) Methyl ethyl ketone: 900.0 parts by mass (b-1) Epoxy resin: "jER" (registered trademark) 1007 (manufactured by Mitsubishi Chemical Corporation): 90.0 parts by mass (c-1) Hexamethylene diisocyanate : 10.0 parts by mass (d-1) Dibutyltin diacetate: 0.1 parts by mass.

Next, using a cylindrical slit die coater, the following composition-1 for forming an ink-repellent silicone layer was applied onto the adhesive layer and heated at 150° C. for 5 minutes to form an ink-repellent silicone layer having an average thickness of 20.0 μm. was provided to obtain an endless lithographic printing plate precursor.

<Composition for forming an ink-repellent silicone layer-1>
The following components (a-2), (b-2) and (c-2) were put into a container and stirred and mixed until the components were uniform. Dry nitrogen was bubbled through the resulting solution for 20 minutes to remove moisture in the solution. Component (d-2) was added to the resulting solution and mixed with stirring for 10 minutes. Ink-repellent silicone layer-forming composition-1 was obtained by adding component (e-2) immediately before coating and mixing with stirring.
(a-2) Isoparaffin-based solvent: "Isopar" (registered trademark) E (manufactured by ExxonMobil Chemical): 295.00 parts by mass (b-2) A siloxane compound having two or more vinyl groups in the molecule (both Terminal dimethylvinylsiloxy-polydimethylsiloxane): DMS-V35 (manufactured by GELES Inc., weight average molecular weight: 49,500, number of vinyl groups in the molecule: 2.0): 91.00 parts by mass (c-2) molecule A siloxane compound having three or more SiH groups within (both terminal trimethylsiloxy-methylhydrosiloxane-dimethylsiloxane copolymer): HMS-301 (manufactured by GELES Inc., weight average molecular weight: 1,950, H derived from SiH groups Group concentration: 0.41% by mass, number of SiH groups in molecule: 8.0): 6.0 parts by mass (d-2) vinyltris(methylethylketoximino)silane: 3.0 parts by mass (e-2) reaction Catalyst (platinum mixture): XC94-C4326 (manufactured by Momentive Performance Materials Japan LLC, solid content concentration: 1% by mass): 5.0 parts by mass.

Using an F2 excimer laser lithography device ₍ wavelength: 157 nm), the ink-repellent silicone layer of the endless lithographic printing plate precursor was subjected to UV exposure in vacuum at an exposure amount of 300 mJ/cm ₂ , thereby forming an endless lithographic printing plate. Obtained.

[Example 2]
Same as Example 1 except that the heat-shrinkable shrink tube was changed to Copalon PTF (material: PET, thickness: 80 μm, perfect circle equivalent diameter: 300 mm, width direction length 1200 mm (manufactured by Gunze Polymer Co., Ltd.)). An endless lithographic printing plate was obtained by the method of

[Example 3]
Same as Example 1 except that the heat-shrinkable shrink tube was changed to Copalon PTF (material: PET, thickness: 300 μm, perfect circle equivalent diameter: 300 mm, width direction length 1200 mm (manufactured by Gunze Polymer Co., Ltd.)). An endless lithographic printing plate was obtained by the method of

[Example 4]
Same as Example 1 except that the heat-shrinkable shrink tube was changed to Copalon PTF (material: PET, thickness: 500 μm, perfect circle equivalent diameter: 300 mm, width direction length 1200 mm (manufactured by Gunze Polymer Co., Ltd.)). An endless lithographic printing plate was obtained by the method of

[Example 5]
Same as Example 1 except that the heat-shrinkable shrink tube was changed to Copalon PTF (material: PET, thickness: 80 μm, perfect circle equivalent diameter: 270 mm, width direction length 1200 mm (manufactured by Gunze Polymer Co., Ltd.)). An endless lithographic printing plate was obtained by the method of

[Example 6]
Same as Example 1 except that the heat-shrinkable shrink tube was changed to Copalon PTF (material: PET, thickness: 80 μm, perfect circle equivalent diameter: 360 mm, width direction length 1200 mm (manufactured by Gunze Polymer Co., Ltd.)). An endless lithographic printing plate was obtained by the method of

[Example 7]
Same as Example 1 except that the heat-shrinkable shrink tube was changed to Copalon PTF (material: PET, thickness: 80 μm, perfect circle equivalent diameter: 300 mm, width direction length 1110 mm (manufactured by Gunze Polymer Co., Ltd.)). An endless lithographic printing plate was obtained by the method of

[Example 8]
Same as Example 1 except that the heat-shrinkable shrink tube was changed to Copalon PTF (material: PET, thickness: 80 μm, perfect circle equivalent diameter: 300 mm, width direction length 1400 mm (manufactured by Gunze Polymer Co., Ltd.)). An endless lithographic printing plate was obtained by the method of

[Example 9]
A cylindrical slit die coater is used to coat the surface of the plate cylinder sleeve with the following rubber layer forming composition, which is then heated at 150° C. for 5 minutes to form a rubber layer with an average thickness of 10 μm. An endless lithographic printing plate was prepared in the same manner as in Example 1 except that PTF (material: PET, thickness: 10 μm, equivalent perfect circle diameter: 300 mm, width direction length: 1100 mm (manufactured by Gunze Kobunshi Co., Ltd.)) was used. got

<Composition for forming rubber layer>
The following components (a-3) and (b-3) were charged into a container and mixed with stirring until the components became uniform to obtain a composition for forming a rubber layer.
(a-3) N,N-dimethylformamide: 666.7 parts by mass (b-3) Polyurethane solution: "Samplen" (registered trademark) LQ-909L (solid concentration: 30% by mass, solvent: N,N- Dimethylformamide, manufactured by Sanyo Chemical Industries, Ltd.): 333.3 parts by mass.

[Example 10]
Same as Example 1 except that the heat-shrinkable shrink tube was changed to Copalon PX (material: polystyrene, thickness: 80 μm, perfect circle equivalent diameter: 300 mm, width direction length 1200 mm (manufactured by Gunze Polymer Co., Ltd.)). An endless lithographic printing plate substrate was obtained by the method.

[Example 11]
Using a cylindrical slit die coater, the following ink-repellent silicone layer-forming composition-2 was applied to the surface of the endless lithographic printing plate substrate provided with an adhesive layer obtained in the same manner as in Example 2, By heating at 150° C. for 5 minutes, an ink-repellent silicone layer having an average thickness of 20 μm was provided to obtain an endless lithographic printing plate precursor.

<Composition for forming an ink-repellent silicone layer-2>
The following components (a-4), (b-4), (c-4) and (d-4) were put into a container and stirred and mixed until the components were uniform. Dry nitrogen was bubbled through the resulting solution for 20 minutes to remove moisture in the solution. Component (e-4) was added to the resulting solution and mixed with stirring for 10 minutes. Ink-repellent silicone layer-forming composition-2 was obtained by adding component (f-4) immediately before coating and mixing with stirring.
(a-4) “Isopar” (registered trademark) E: 895.0 parts by mass (b-4) a siloxane compound having two or more vinyl groups in the molecule (both ends trimethylsiloxy-vinylmethylsiloxane-dimethylsiloxane copolymer ): VDT-954 (manufactured by GELEST Inc., weight average molecular weight: 225,000, vinyl group concentration: 4.29% by mass, number of vinyl groups in the molecule: 357.2): 62.0 parts by mass (c-4 ) Liquid with a surface tension of 30 mN / m or less at 25 ° C.: KF-96-50cs (dimethyl silicone oil, weight average molecular weight: 3,780, surface tension at 25 ° C.: 20.8 mN / m, 1 atmospheric pressure environment Mass reduction rate after heating at 150° C. for 24 hours: 0.1% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.): 20.0 parts by mass (d-4) Siloxane compound having 3 or more SiH groups in the molecule (Both ends trimethylsiloxy-methylhydrosiloxane-dimethylsiloxane copolymer): HMS-064 (manufactured by GELEST Inc., weight average molecular weight: 55,000, H group concentration derived from SiH group: 0.08 mass%, intramolecular SiH groups: 44.4): 15.0 parts by mass (e-4) Vinyltris(methylethylketoximino)silane: 3.0 parts by mass (f-4) XC94-C4326: 5.0 parts by mass.

Next, the following ink-receiving layer-forming composition-1 was applied onto the ink-repellent silicone layer using a sub-femto inkjet processing device (manufactured by SIJ Technology Co., Ltd.) under the conditions of a droplet volume of 2 femtoliters. and heated at 150° C. for 5 minutes to obtain an endless lithographic printing plate.

<Composition for forming an ink-receiving layer-1>
The following components (a-5), (b-5), (c-5) and (d-5) were put into a container and stirred and mixed until the components were uniform. Dry nitrogen was bubbled through the resulting solution for 20 minutes to remove moisture in the solution. Immediately before coating, the component (e-5) was added and mixed with stirring to obtain a composition-1 for forming an ink receiving layer.
(a-5) “Isopar” (registered trademark) C: 95.0 parts by mass (b-5) VDT-954: 70.0 parts by mass (c-5) HMS-993: 30.0 parts by mass (d- 5) 2-methyl-3-butyn-2-ol: 1.5 parts by mass (e-5) XC94-C4326: 3.5 parts by mass.

[Example 12]
Using a cylindrical slit die coater, the following composition-3 for forming an ink-repellent silicone layer was applied to the surface of the endless lithographic printing plate substrate provided with an adhesive layer obtained in the same manner as in Example 2, An ink repellent silicone layer having an average thickness of 20 μm was formed by heating at 150° C. for 5 minutes.

<Composition for forming an ink-repellent silicone layer-3>
The following components (a-6), (b-6) and (c-6) were put into a container and stirred and mixed until the components were uniform. Dry nitrogen was bubbled through the resulting solution for 20 minutes to remove moisture in the solution. Component (d-6) was added to the resulting solution and mixed with stirring for 10 minutes. Ink-repellent silicone layer-forming composition-3 was obtained by adding component (e-6) immediately before coating and mixing with stirring.
(a-6) “Isopar” (registered trademark) E: 895.0 parts by mass (b-6) VDT-954: 82.0 parts by mass (c-6) Siloxane having 3 or more SiH groups in the molecule Compound (both ends trimethylsiloxy-methylhydrosiloxane-dimethylsiloxane copolymer): HMS-064 (manufactured by GELEST Inc., weight average molecular weight: 55,000, H group concentration derived from SiH group: 0.08 mass%, intramolecular of SiH groups: 44.4): 15.0 parts by mass (d-6) vinyltris(methylethylketoximino)silane: 3.0 parts by mass (e-6) XC94-C4326: 5.0 parts by mass.

Next, the ink-receptive silicone layer-forming composition-1 was applied to the surface of the ink-repellent silicone layer using a cylindrical slit die coater, and heated at 150° C. for 5 minutes to give an average film thickness of 0.5. An ink receptive silicone layer of 4 μm was provided to obtain an endless lithographic printing plate precursor.

Laser irradiation energy density: 150 mJ/cm ² , pulse repetition frequency: 10 Hz, laser irradiation area atmosphere: Pattern irradiation was performed in a nitrogen atmosphere to ablate the entire ink-receiving silicone layer and the upper portion of the ink-repellent silicone layer in the laser-irradiated areas to obtain an endless lithographic printing plate.

[Example 13]
Using a cylindrical slit die coater, the following composition for forming a hydrophilic layer was applied to the surface of the endless lithographic printing plate base material provided with an adhesive layer obtained in the same manner as in Example 2, followed by drying at 150°C for 5 minutes. A hydrophilic layer having an average film thickness of 3 μm was formed by heating for 1 minute. The hydrophilic layer-forming composition was obtained by stirring and mixing the following components at room temperature.

<Composition for forming hydrophilic layer>
(a-7) Hydrophilic polymer obtained from Synthesis Example 1 below: 10 parts by mass (b-7) N-Hydroxyethylxylylenediamine: 1 part by mass (c-7) Purified water: 100 parts by mass.

<Synthesis Example 1>
Vinyl acetate: 60 g, methyl acrylate: 40 g, benzoyl peroxide: 0.5 g as a polymerization initiator were weighed, and these were added to partially saponified polyvinyl alcohol: 3 g and NaCl: 10 g as a dispersion stabilizer. Water: 300 ml dispersed inside. The resulting dispersion was stirred at 65° C. for 6 hours to carry out suspension polymerization. 8.6 g of the obtained copolymer was added to a saponification reaction solution consisting of 200 g of methanol, 10 g of water, and 40 ml of 5N NaOH, suspended with stirring, and subjected to a saponification reaction at 25° C. for 1 hour. After that, the temperature was raised to 65° C., and the saponification reaction was further carried out for 5 hours. The obtained saponification reaction product was thoroughly washed with methanol and then freeze-dried to obtain a hydrophilic polymer.

Next, on the surface of the hydrophilic layer, the following ink receptive thermosensitive layer forming composition-1 was applied using a cylindrical slit die coater, and heated at 70° C. for 5 minutes to adhere the ink to an average film thickness of 3 μm. A fleshy heat-sensitive layer was provided to obtain an endless lithographic printing plate precursor. The ink receptive heat-sensitive layer-forming composition-1 was obtained by stirring and mixing the following components at room temperature.

<Composition for Forming Ink Receptive Thermosensitive Layer-1>
(a-8) "KAYASORB" IR-820B (infrared absorbing dye, manufactured by Nippon Kayaku Co., Ltd.): 5 parts by mass (b-8) "Aluminum chelate" D (aluminum monoacetylacetonate bisethylacetoacetate, river Ken Fine Chemical Co., Ltd.): 20 parts by mass (c-8) “epoxy ester” 80 MFA (epoxy acrylate, manufactured by Kyoeisha Chemical Co., Ltd.): 40 parts by mass
(d-8) Polyvinyl alcohol AL-06 (manufactured by Nippon Synthetic Chemical Co., Ltd.): 10 parts by weight (e-8) Polyurethane emulsion "Superflex" R-5100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 40 parts by weight Part (f-8) “Cataloid” SI-30 (aqueous dispersion of colloidal silica fine particles having an average particle size of 0.01 to 0.014 μm, manufactured by Catalysts and Chemicals Co., Ltd.): 10 parts by mass (g-8) pure water : 700 parts by mass (h-8) Ethylene glycol monoethyl ether: 200 parts by mass.

The resulting endless lithographic printing plate precursor was subjected to pattern exposure using a semiconductor laser (wavelength: 808 nm) from the ink receptive heat-sensitive layer side under conditions of a laser irradiation energy density of 200 mJ/cm ² , and then cotton soaked with water. By wiping the surface with , an endless lithographic printing plate was obtained in which the ink receptive heat-sensitive layer in the unexposed areas was removed and the underlying ink repellent hydrophilic layer was exposed.

[Example 14]
Using a cylindrical slit die coater, the following ink-receivable thermosensitive layer-forming composition-2 was applied to the surface of the endless lithographic printing plate substrate provided with an adhesive layer obtained in the same manner as in Example 2. and 150° C. for 5 minutes to form an ink receptive thermosensitive layer having an average thickness of 1 μm. The ink receptive heat-sensitive layer-forming composition-2 was obtained by stirring and mixing the following components at room temperature.

<Composition for Forming Ink Receptive Thermosensitive Layer-2>
(a-9) Phenol-formaldehyde novolak resin: "Sumilite Resin" (registered trademark) PR53195 (manufactured by Sumitomo Bakelite Co., Ltd.): 45.0 parts by weight (b-9) Polyurethane solution: "Nipporan" (registered trademark) 5196 (manufactured by Nippon Polyurethane Co., Ltd., solid content concentration: 30% by weight): 62.5 parts by weight (c-9) Infrared absorbing dye: "PROJET" 825LDI (manufactured by Avecia Co., Ltd.): 12.0 parts by weight (d -9) Titanium di-n-butoxybis (acetylacetonate) solution: "Nasem" (registered trademark) titanium (manufactured by Nippon Kagaku Sangyo Co., Ltd., solid content concentration: 73% by weight): 28.5 parts by weight (e- 9) Polyoxypropylenediamine/glycidyl methacrylate/3-glycidoxypropyltrimethoxysilane = 1/3/1 mol reactant (solid concentration: 50% by weight): 22.5 parts by weight (f-9) tetrahydrofuran : 717.0 parts by weight (g-9) Ethanol: 112.5 parts by weight.

Next, the ink-repellent silicone layer-forming composition-4 was applied to the surface of the ink receptive heat-sensitive layer using a cylindrical slit die coater and heated at 150° C. for 5 minutes to give an average film thickness of 3 μm. An ink-repellent silicone layer was provided to obtain an endless lithographic printing plate precursor.

<Composition for forming ink-repellent silicone layer-4>
The following components (a-10), (b-10), and (c-10) were put into a container and stirred and mixed until the components became uniform. Dry nitrogen was bubbled through the resulting solution for 20 minutes to remove moisture in the solution. Components (d-10), (e-10), and (f-10) were added to the resulting solution and stirred and mixed for 10 minutes, then component (g-10) was added and stirred and mixed for another 10 minutes. did. Immediately before coating, the component (h-10) was added and mixed by stirring to obtain an ink-repellent silicone layer-forming composition-4.
(a-10) "Isopar" (registered trademark) E: 894.05 parts by weight (b-10) "DMS"-V35: 73.68 parts by weight (c-10) KF-96-50cs: 20.00 parts by weight Part (d-10) SiH group-containing compound (both ends trimethylsiloxy-methylhydrosiloxane-dimethylsiloxane copolymer): "HMS"-301 (manufactured by GELES Inc., weight average molecular weight: 1,960, SiH group equivalent: 245, Number of SiH groups in the molecule: 8): 2.27 parts by weight (e-10) vinyltris(methylethylketoximino)silane: 1.00 parts by weight (f-10) phenyltriacetoxysilane: 3.00 parts by weight (g -10) Reaction inhibitor: γ-picoline: 1.00 parts by weight (h-10) XC94-C4326: 5.00 parts by weight.

The ink-repellent silicone layer side of the resulting endless lithographic printing plate precursor was pattern-exposed using a semiconductor laser (wavelength: 808 nm) under the conditions of a laser irradiation energy density of 200 mJ/cm ² , and then a cotton pad soaked with water. An endless lithographic printing plate was obtained by wiping the surface to remove the ink repellent silicone layer in the exposed areas.

[Comparative Example 1]
An endless lithographic printing plate was obtained in the same manner as in Example 1, except that the heat-shrinkable shrink tube was not provided.

[Comparative Example 2]
Double-sided tape: 777 (manufactured by Teraoka Seisakusho Co., Ltd.) was attached to the surface of the endless lithographic printing plate substrate, and then a sheet-shaped waterless lithographic printing plate precursor: TAC-VT4 (manufactured by Toray Industries, Inc.) was applied. The waterless lithographic printing plate was wound and fixed. The ink-repellent silicone layer-forming composition-1 was filled in the gap (about 0.5 mm) between the plate head and plate bottom of the wound sheet-like waterless lithographic printing plate and heated at 150° C. for 5 minutes. to obtain an endless lithographic printing plate precursor.

Table 1 shows the evaluation results of Examples 1-14 and Comparative Examples 1-2. In the endless planographic printing plate substrate obtained in Example 10, the heat-shrinkable product of the shrink tube was remarkably dissolved by methyl ethyl ketone, which is the solvent component of the adhesive layer-forming composition. did not. For this reason, in Table 1, the columns of "(2) Evaluation of printed matter" and "(3) Recyclability of plate cylinder sleeve" in Example 10 are left blank. In addition, in Comparative Example 1, since no shrink tube was used, the column of "(1) Evaluation of shrink tube" in Table 1 is left blank.

REFERENCE SIGNS LIST 1 image area 2 non-image area 3 print medium 4 transfer pattern 5 cylindrical support 6 heat-shrinkable shrink tube 7 ink-repellent silicone layer 8 ink-repellent area 9 ink-receiving area 10 ink roller 11 dampening water Roller 12 Endless lithographic printing plate 13 Blanket cylinder 14 Medium to be printed 15 Impression cylinder 16 Plate cylinder sleeve 17 Heat-shrinkable shrink tube before heating 18 Shrink tube after heating (heat-shrinkable product of heat-shrinkable shrink tube 13)

Claims (20)

An endless lithographic printing plate precursor having a heat-shrinkable shrink tube on at least the periphery of a cylindrical support, and an ink-repellent layer in this order, wherein the ink-repellent layer is the endless lithographic printing plate precursor. An endless lithographic printing plate precursor that exists continuously on the outermost surface of the The endless lithographic printing plate precursor according to Claim 1, wherein the outermost surface of the heat-shrinkable shrink tube on the side of the ink repellent layer is polyethylene terephthalate. The endless lithographic printing plate precursor according to claim 1 or 2, wherein the heat-shrinkable shrink tube has an average thickness of 10 to 500 µm. The endless lithographic printing plate precursor according to any one of claims 1 to 3, further comprising an adhesive layer continuously between the heat-shrinkable shrink tube and the ink repellent layer. The endless lithographic printing plate precursor according to any one of claims 1 to 4, further comprising a rubber layer between the cylindrical support and the heat-shrinkable shrink tube. The endless lithographic printing plate precursor according to any one of Claims 1 to 5, wherein the cylindrical support is a plate cylinder of a printing machine. The endless lithographic printing plate precursor according to claim 6, wherein the plate cylinder is a sleeve that can be attached to and detached from a plate cylinder shaft of a printing press. The endless lithographic printing plate precursor according to claim 6 or 7, wherein the printing machine is an offset printing machine. The endless lithographic printing plate precursor as claimed in any one of Claims 1 to 8, which has an ink receptive layer continuously on the ink repellent layer. The endless lithographic printing plate precursor according to any one of claims 1 to 8, further comprising an ink-receiving layer continuously between the heat-shrinkable shrink tube and the ink-repellent layer. A method for producing an endless lithographic printing plate, wherein the composition for forming an ink-receiving portion is discharged in a pattern onto the ink-repellent layer of the endless lithographic printing plate precursor according to any one of claims 1 to 8. A method for producing an endless lithographic printing plate, wherein the ink-repellent layer of the endless lithographic printing plate precursor according to any one of claims 1 to 8 is pattern-irradiated with active energy rays. A method for producing an endless lithographic printing plate, wherein the inking layer of the endless lithographic printing plate precursor according to claim 9 is pattern-irradiated with a high-output laser to expose the ink repellent layer in the irradiated area. A method for producing an endless lithographic printing plate, comprising subjecting the inking layer of the endless lithographic printing plate precursor according to claim 9 to pattern exposure and development. A method for producing an endless lithographic printing plate, comprising subjecting the ink repellent layer of the endless lithographic printing plate precursor according to claim 10 to pattern exposure and development. A method for producing an endless printed matter using the endless lithographic printing plate, ink, and medium to be printed according to any one of claims 11 to 15. A method for producing an endless printed matter using the endless lithographic printing plate, ink, fountain solution, and printing medium according to any one of claims 11 to 15. 18. The method for producing an endless printed matter according to claim 16 or 17, wherein said ink is electron beam curable ink. The method for producing an endless printed matter according to any one of claims 16 to 18, wherein the print medium is a film. 20. The method for producing an endless printed product according to claim 19, wherein the printed product is printed by a roll-to-roll method.

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