Waterless lithographic printing plate precursor and method for producing a waterless lithographic printing plate using the same

Abstract

To provide a waterless lithographic original plate that can give a waterless lithographic plate that can be subjected to pattern exposure using a general-purpose exposure machine, causes only a small amount of abrasion dust during exposure, does not require a developing step, and has excellent ink resilience, ink receptivity and print durability.SOLUTION: A waterless lithographic original plate has a metal chelate-containing silicone layer on a support. As measured by X-ray photoelectron spectroscopy, the content of metal chelate-derived metal in the metal chelate-containing silicone layer is 0.2-1.8 atom%.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a waterless lithographic printing plate precursor, a method for producing a waterless lithographic printing plate using the same, and a composition for forming a metal chelate-containing silicone layer.

Background Art

[0002] For printing, there are various methods such as letterpress printing, gravure printing, stencil (screen) printing, and lithographic printing, and printing is performed by taking advantage of the characteristics of each method. Among these, lithographic printing is advantageous compared to other printing methods in terms of obtaining printed matter with high fineness. The printing plate used for lithographic printing (hereinafter referred to as a lithographic printing plate) is roughly classified into those that make the non-image areas ink-repellent by the action of dampening water and those that use silicone or fluororesin as the ink-repellent non-image areas without using dampening water.

[0003] Regarding the technology of obtaining a waterless lithographic printing plate using silicone as a non-image area with ink repellency without going through a developing process, various proposals have been made so far. For example, as a technology using a photocatalyst, a non-developing and dampening-water-free photosensitive lithographic printing plate provided with a layer containing a polyorganosiloxane in which photocatalytic semiconductor particles that are hydrophilicized at least by exposure are dispersed on a support (see, for example, Patent Document 1), or a pattern former having a photocatalyst-containing layer on a substrate, wherein the photocatalyst-containing layer contains silicone containing an epoxy group as an organo group bonded to a silicon atom as a binder and contains a substance whose wettability changes by the action of the photocatalyst, and patterns with different wettabilities are formed on the surface thereof due to the change in the wettability of the silicone by the action of the photocatalyst accompanying pattern exposure (see, for example, Patent Document 2), etc. have been proposed. Also, as a method for manufacturing a printing plate having a first silicone layer and a second silicone layer with different ink film thickness properties on a support, a method of irradiating laser light from the second silicone layer side and ablating the second silicone layer in the portion irradiated with the laser light or the upper part of the second silicone layer and the first silicone layer (see, for example, Patent Document 3), or as a method for manufacturing a printing member having a support and a layer composed of an ink-repellent portion and an ink-receiving portion, a method of irradiating an electron beam or vacuum ultraviolet light to the layer composed of the ink-repellent portion to draw a pattern of the ink-receiving portion (see, for example, Patent Document 4), etc. have been proposed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0005] The lithographic printing plates described in Patent Documents 1 and 2 can be obtained by irradiation with ultraviolet rays. However, since the lithographic printing plate described in Patent Document 1 contains hydrophilic photocatalyst particles at a high density in hydrophobic silicone, aggregation and sedimentation of the photocatalyst particles are likely to occur in the production of the lithographic printing plate original plate, which is a precursor before forming the image areas / non-image areas on the lithographic printing plate, and there were problems with productivity. Although the lithographic printing plate described in Patent Document 2 enables dispersion of the photocatalyst particles, there were problems with ink repellency and printing durability.

[0006] The waterless lithographic printing plate original plate described in Patent Document 3 has a problem that ablation dust is likely to be generated by high-power laser exposure of ultraviolet to infrared rays. The ablation dust recovery device leads to an increase in the size of the device. In addition, the ablation dust that could not be completely collected easily adheres to the surface of the waterless lithographic printing plate, affecting the print quality.

[0007] Since the waterless lithographic printing plate original plate described in Patent Document 4 uses electron beams or vacuum ultraviolet rays, irradiation in a nitrogen atmosphere or under vacuum is required, and an increase in the size of the device is inevitable. Also, since electron beams and vacuum ultraviolet rays are not common in the production of printing plates, a technique that can be drawn by a general-purpose exposure machine has been demanded.

[0008] Therefore, the problem to be solved by the present invention is to provide a waterless lithographic printing plate original plate that enables pattern exposure by a general-purpose exposure machine, generates less ablation dust during exposure, does not require a developing process, and has good ink repellency, ink receptivity, and printing durability, and can obtain a waterless lithographic printing plate.

Means for Solving the Problems

[0009] In order to solve the above problems, the original planographic printing plate of the present invention has a metal chelate-containing silicone layer on a support, and the metal concentration derived from the metal chelate in the metal chelate-containing silicone layer measured by X-ray photoelectron spectroscopy is 0.2 to 1.8 atom%, which is an original planographic printing plate without water.

Effect of the Invention

[0010] The original planographic printing plate without water of the present invention enables pattern exposure by a general-purpose laser that does not require exposure under a nitrogen atmosphere or in a vacuum, and generates less ablation dust during exposure. With the original planographic printing plate of the present invention, a planographic printing plate without water having good ink repellency, ink receptivity, and printing durability can be obtained without going through a developing process.

Embodiments for Carrying Out the Invention

[0011] The original planographic printing plate without water according to the present invention (hereinafter may be abbreviated as "original printing plate") is a precursor before forming an ink-receptive part / ink-repellent part on a planographic printing plate without water (hereinafter may be abbreviated as "printing plate"), and has a metal chelate-containing silicone layer on a support. The support has a function of maintaining the shape of the original printing plate and the printing plate. The metal chelate-containing silicone layer has a function of repelling ink.

[0012] As the material of the support, dimensionally stable metals, plastics, etc. are preferable. Specifically, metals such as aluminum, iron, zinc, and copper, alloys mainly composed of these metals, plastics such as epoxy resin, phenol resin, ester resin, vinyl ester resin, amide resin, and imide resin, and fiber-reinforced plastics containing fibers such as glass fiber, carbon fiber, aramid fiber, polyethylene fiber, zylon fiber, and boron fiber can be mentioned. Aluminum alloys and fiber-reinforced plastics are preferable in terms of being lightweight and easy to handle.

[0013] Examples of the shape of the support include a plate shape, a roll shape, a cylindrical shape, and a columnar shape. When a cylindrical or columnar support is used, a seamless waterless lithographic printing plate original capable of printing a continuous pattern can be obtained. As the shape of the support of the seamless waterless lithographic printing plate original, a cylindrical shape is more preferable in terms of being lighter and easier to handle. In terms of being able to perform printing immediately after producing a printing plate from the printing plate original, the cylindrical support is preferably the plate cylinder of the printing press. In particular, it is more preferable that the cylindrical support is a plate cylinder sleeve that can be detached from the plate cylinder shaft of the printing press, in terms of being able to perform a series of operations such as producing a seamless waterless lithographic printing plate and regenerating the support after printing outside the printing press.

[0014] Regarding the dimensions of the support, when the support is plate-shaped, appropriate dimensions (length, width, thickness, etc.) suitable for the printing press to be used may be selected. When the support is cylindrical, appropriate diameter and width suitable as the plate cylinder of the printing press to be used may be selected.

[0015] The surface of the support may be subjected to surface treatment such as corona discharge treatment or glow discharge treatment, which can enhance the adhesive force between the support and the metal chelate-containing silicone layer. Also, a primer layer (adhesive layer) may be provided between the support and the metal chelate-containing silicone layer. Furthermore, these may be used in combination.

[0016] Next, the metal chelate-containing silicone layer will be described. The metal chelate-containing silicone layer in the present invention refers to a silicone layer containing 3% by mass or more of a metal chelate compound. By containing the metal chelate compound, the ink-receiving property of the exposed portion can be changed by pattern exposure using a general-purpose laser.

[0017] A metal chelate compound refers to a compound having one or more chelate rings with a metal in the molecule. That is, in addition to a metal chelate compound in which all coordinations with a metal are formed by chelate rings, a metal compound having one or more chelate rings and an alkoxide is also included in the metal chelate compound in the present invention. Further, since a chelate ring remains in a compound (multimer) obtained by dealcohol condensation due to moisture in the air or the like, such a compound is also within the scope of the metal chelate compound in the present invention.

[0018] Examples of the compound that forms a chelate ring with a metal include β-diketone compounds, β-ketoester compounds, β-diester compounds, glycols, triethanolamine, and the like. Among these, β-diketone compounds and β-ketoester compounds are preferable in terms of further improving storage stability and ink film formation property of the exposed portion. Examples of the β-diketone compound include acetylacetone, 1,3-diphenyl-1,3-propanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, and the like. Among these, acetylacetone is preferable in terms of increasing the metal concentration in the metal chelate compound obtained by coordination with a metal. As the β-ketoester compound, an alkyl acetoacetate is preferable, and the number of carbon atoms in the alkyl part is preferably 1 to 8. If the number of carbon atoms in the alkyl part is 1 or more, the affinity with the silicone component can be improved. The number of carbon atoms in the alkyl part is more preferably 2 or more. On the other hand, if the number of carbon atoms in the alkyl part is 8 or less, the metal concentration in the metal chelate compound obtained by coordination with a metal can be increased. The number of carbon atoms in the alkyl part is more preferably 6 or less.

[0019] Examples of the metal include aluminum(III), titanium(IV), manganese(II), manganese(III), iron(II), iron(III), cobalt(II), cobalt(III), nickel(II), nickel(IV), copper(I), copper(II), zinc(II), germanium(IV), indium(III), tin(II), tin(IV), zirconium(IV), hafnium(IV), etc. From the viewpoint of further improving the storage stability and the ink build-up property of the exposed portion, metals with a valence of 3 or more are preferable, and among them, aluminum, titanium, and zirconium are more preferable.

[0020] Examples of the metal chelate compound include aluminum chelate compounds such as aluminum trisacetylacetonate, di-methoxyaluminum monoacetylacetonate, di-ethoxyaluminum monoacetylacetonate, di-n-propoxyaluminum monoacetylacetonate, di-iso-propoxyaluminum monoacetylacetonate, di-n-butoxyaluminum monoacetylacetonate, di-sec-butoxyaluminum monoacetylacetonate, di-tert-butoxyaluminum monoacetylacetonate, aluminum trisethylacetoacetate, di-methoxyaluminum monoethylacetoacetate, di-ethoxyaluminum monoethylacetoacetate, di-n-propoxyaluminum monoethylacetoacetate, di-iso-propoxyaluminum monoethylacetoacetate, di-n-butoxyaluminum monoethylacetoacetate, di-sec-butoxyaluminum monoethylacetoacetate, di-tert-butoxyaluminum monoethylacetoacetate; titanium chelate compounds such as titanium tetraacetylacetonate, di-methoxytitanium bisacetylacetonate, di-ethoxytitanium bisacetylacetonate, di-n-propoxytitanium bisacetylacetonate, di-iso-propoxytitanium bisacetylacetonate, di-n-butoxytitanium bisacetylacetonate, di-sec-butoxytitanium bisacetylacetonate, di-tert-butoxytitanium bisacetylacetonate, titanium tetraethylacetoacetate, di-methoxytitanium bisethylacetoacetate, di-ethoxytitanium bisethylacetoacetate, di-n-propoxytitanium bisethylacetoacetate, di-iso-propoxytitanium bisethylacetoacetate, di-n-butoxytitanium bisethylacetoacetate, di-sec-butoxytitanium bisethylacetoacetate, di-tert-butoxytitanium bisethylacetoacetate; zirconium chelate compounds such as zirconium tetraacetylacetonate, di-methoxyzirconium bisacetylacetonate, di-ethoxyzirconium bisacetylacetonate,Examples of zirconium chelate compounds include di-n-propoxyzirconium bis(acetylacetonate), di-iso-propoxyzirconium bis(acetylacetonate), di-n-butoxyzirconium bis(acetylacetonate), di-sec-butoxyzirconium bis(acetylacetonate), di-tert-butoxyzirconium bis(acetylacetonate), zirconium tetraethyl acetoacetate, di-methoxyzirconium bis(ethyl acetoacetate), di-ethoxyzirconium bis(ethyl acetoacetate), di-n-propoxyzirconium bis(ethyl acetoacetate), di-iso-propoxyzirconium bis(ethyl acetoacetate), di-n-butoxyzirconium bis(ethyl acetoacetate), di-sec-butoxyzirconium bis(ethyl acetoacetate), di-tert-butoxyzirconium bis(ethyl acetoacetate), etc. Two or more of these may be included.

[0021] The metal concentration derived from the metal chelate compound in the metal chelate-containing silicone layer measured by X-ray photoelectron spectroscopy is 0.2 to 1.8 atom%. When the metal concentration derived from the metal chelate compound is less than 0.2 atom%, that is, when the metal chelate compound is insufficient, it becomes difficult to obtain the effect of changing the ink receptivity of the exposed portion, resulting in insufficient ink receptivity. The metal concentration derived from the metal chelate compound is more preferably 0.4 atom% or more, and even more preferably 0.6 atom% or more. On the other hand, when the metal concentration derived from the metal chelate compound exceeds 1.8 atom%, that is, when the metal chelate compound is excessive, the ink repellency and printing resistance become insufficient due to an increase in the surface energy and embrittlement of the metal chelate-containing silicone layer. The metal concentration derived from the metal chelate compound is more preferably 1.6 atom% or less, and even more preferably 1.4 atom% or less. The metal concentration derived from the metal chelate compound can be within the above range, for example, by adjusting the content of each component of the metal chelate-containing silicone layer to the preferred range described later.

[0022] As the metal chelate-containing silicone layer, a layer containing a metal chelate compound can be used in an addition reaction type, a condensation reaction type, an addition reaction-condensation reaction combined type silicone layer, etc. that have been disclosed as an ink-repellent layer for a waterless lithographic printing plate.

[0023] Examples of the addition reaction type, condensation reaction type, and addition reaction-condensation reaction combined type silicone layers include, for example, the layers exemplified as diorganosiloxane unit-containing layers in JP-A No. 2021-66175, the layers exemplified as silicone rubber layers in WO 2019 / 203261, the layers exemplified as the first silicone layer in WO 2019 / 203263, and the like.

[0024] In the present invention, the element concentrations in the metal chelate-containing silicone layer are preferably silicon: 15.5 to 24.5 atom%, oxygen: 25.0 to 28.5 atom%, carbon: 50.0 to 57.0 atom%, and metal derived from the metal chelate compound: 0.2 to 1.8 atom%, and the ink receptivity, ink repellency, and printing durability can be further improved. The element concentrations can be made within the above ranges, for example, by adjusting the content of each constituent component of the metal chelate-containing silicone layer to a preferable range described later.

[0025] The element concentrations in the metal chelate-containing silicone layer can be measured by X-ray photoelectron spectroscopy.

[0026] The average thickness of the metal chelate-containing silicone layer is preferably 5 μm or more. By setting the average thickness of the metal chelate-containing silicone layer to 5 μm or more, the ink repellency, scratch resistance, and printing durability of the printing plate can be further improved. On the other hand, the average thickness of the metal chelate-containing silicone layer is preferably 30 μm or less. The average thickness of the metal chelate-containing silicone layer can be determined by cross-sectional TEM observation. More specifically, a sample is prepared from the original plate of the waterless 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 2,000 times. In the TEM photograph of the vertical cross-section, the thickness is measured at 10 randomly selected points from the metal chelate-containing silicone layer, and the average thickness can be obtained by calculating the number average value thereof.

[0027] The original plate of the waterless lithographic printing plate of the present invention preferably further has a metal chelate-free silicone layer on the metal chelate-containing silicone layer. By having the metal chelate-free silicone layer, the ink repellency can be further improved. The metal chelate-free silicone layer in the present invention refers to a silicone layer having a metal chelate compound content of less than 3% by mass.

[0028] As the metal chelate-free silicone layer, the above-described addition reaction type, condensation reaction type, addition reaction-condensation reaction combined type ink-repellent silicone layer, etc., which have been disclosed as an ink-repellent layer for waterless lithographic printing plates, can be used.

[0029] In the metal chelate-free silicone layer, the elemental concentration ratio is preferably silicon: 22 to 26 atom%, oxygen: 24 to 28 atom%, carbon: 48 to 52 atom%, and the ink repellency can be further improved. Further, the ratio of the oxygen concentration to the silicon concentration (oxygen concentration / silicon concentration) in the metal chelate-free silicone layer is preferably 0.9 to 1.2, and the ink repellency can be further improved. The elemental concentration can be set within the above range, for example, by adjusting the content of each constituent component of the metal chelate-free silicone layer to a preferred range described later.

[0030] The elemental concentration in the metal chelate-free silicone layer can be measured in the same manner as the elemental concentration in the metal chelate-containing silicone layer. Further, by dividing the obtained oxygen concentration value by the silicon concentration value, the ratio of oxygen concentration to silicon concentration (oxygen concentration / silicon concentration) can be calculated.

[0031] The average thickness of the metal chelate-free silicone layer is preferably 0.1 μm or more. By setting the average thickness of the metal chelate-free silicone layer to 0.1 μm or more, the ink repellency can be further improved. More preferably, it is 0.2 μm or more. On the other hand, the average thickness of the metal chelate-free silicone layer is preferably 30 μm or less. The average thickness of the metal chelate-free silicone layer can be determined in the same manner as the average thickness of the metal chelate-containing silicone layer.

[0032] The original plate for waterless lithographic printing of the present invention may have a primer layer between the support and the metal chelate-containing silicone layer, and the adhesiveness, plate inspection property, scratch resistance, printing durability, etc. can be improved.

[0033] Examples of the primer layer used in the original plate for waterless lithographic printing of the present invention include primer layers described as heat insulating layers in, for example, JP-A-2004-199016, JP-A-2004-334025, JP-A-2006-276385, etc.

[0034] The average film thickness of the primer layer is preferably 0.2 to 30 μm.

[0035] The original plate for waterless lithographic printing according to the present invention may have a cover film and / or a backing paper on the metal chelate-containing silicone layer or the metal chelate-free silicone rubber layer, and can protect the surface of the lower silicone layer.

[0036] As the cover film, a film having a thickness of 100 μm or less is preferable. Specifically, films such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, and cellophane can be mentioned.

[0037] The laminated paper preferably has a basis weight of 30 to 90 g / m 2 . Examples of the laminated paper preferably used include, for example, information recording base paper of 40 g / m 2 (manufactured by Nagoya Pulp Co., Ltd.), metal laminated paper of 30 g / m 2 (manufactured by Nagoya Pulp Co., Ltd.), unbleached kraft paper of 50 g / m 2 (manufactured by Chugoku Pulp Industry Co., Ltd.), NIP paper of 52 g / m 2 (manufactured by Chugoku Pulp Industry Co., Ltd.), pure white roll paper of 45 g / m 2 (manufactured by Oji Paper Co., Ltd.), Kurupak of 73 g / m 2 (manufactured by Oji Paper Co., Ltd.), etc.

[0038] Next, the method for manufacturing a printing plate original according to the present invention will be described.

[0039] The method for manufacturing a printing plate original according to the present invention includes at least (1) a step of continuously applying a composition for forming a metal chelate-containing silicone layer on a support, and (2) a step of curing the coating film obtained in step (1) to form a metal chelate-containing silicone layer preferably having. Further, in the method for manufacturing a printing plate original having a metal chelate-free silicone layer, before or after the step (2), (3) a step of continuously applying a composition for forming a metal chelate-free silicone layer on the coating film obtained in step (1) or the metal chelate-containing silicone layer obtained in step (2), and (4) a step of curing the coating film obtained in step (3) to form a metal chelate-free silicone layer preferably having.

[0040] When there is a primer layer between the support and the composition for forming a metal chelate-containing silicone layer, it is preferable to form a primer layer by applying a composition for forming a primer layer on the support and drying / curing it under heating or non-heating prior to step (1).

[0041] Examples of the method for applying the composition for forming the primer layer include methods using a slit die coater, a gravure coater, a roll coater, a wire bar coater, etc. Among these, slit die coater application is preferred.

[0042] When heating, examples of the heating device include a hot air dryer, an infrared dryer, etc. The heating temperature is preferably 50 to 200 °C, and the heating time is preferably 30 seconds to 10 minutes.

[0043] In step (1), it is preferable to apply the composition for forming the metal chelate-containing silicone layer to the entire surface of the support. When there is a primer layer between the support and the composition for forming the metal chelate-containing silicone layer, it is preferable to apply the composition for forming the metal chelate-containing silicone layer on the primer layer formed on the support. When applying, it is preferable to remove as much moisture adhering to the surface of the support or the primer layer as possible in terms of improving the adhesiveness.

[0044] Examples of the method for applying the composition for forming the metal chelate-containing silicone layer include the methods exemplified as the method for applying the composition for forming the primer layer, and slit die coater application is preferred.

[0045] In step (2), it is preferable to cure by heating. The preferred mode of the heating conditions is the same as those of the heating conditions of the primer layer.

[0046] In step (3), it is preferable to apply the composition for forming the metal chelate-free silicone layer to the entire surface of the metal chelate-containing silicone layer. As the composition for forming the metal chelate-free silicone layer, a composition obtained by removing the metal chelate compound from the composition for forming the metal chelate-containing silicone layer described later is preferred. Examples of the application method include the methods exemplified as the method for applying the composition for forming the primer layer, and slit die coater application is preferred.

[0047] In step (4), it is preferably cured by heating. A preferred embodiment of the heating conditions is the same as those for the primer layer.

[0048] Next, a composition for forming a metal chelate-containing silicone layer, which is preferably used in the method for producing a printing plate original according to the present invention, will be described. The composition for forming a metal chelate-containing silicone layer according to the present invention contains a polysiloxane having two or more silanol groups or vinyl groups in the molecule, a crosslinking agent having three or more functional groups reactive with the silanol group or the vinyl group in the molecule, and a metal chelate compound having one or more chelate rings in the molecule.

[0049] Examples of the metal chelate compound include those exemplified in the printing plate original, and preferred embodiments thereof are the same as those in the printing plate original.

[0050] The content of the metal chelate compound in the composition for forming a metal chelate-containing silicone layer is preferably 3% by mass or more in the total solid content, so that the metal concentration derived from the metal chelate can be easily adjusted to the above-mentioned preferred range, and the ink receptivity of the exposed area can be further improved. More preferably, it is 7% by mass or more, and still more preferably, it is 10% by mass or more. On the other hand, the content of the metal chelate compound is preferably 38% by mass or less in the total solid content, so that the metal concentration derived from the metal chelate can be easily adjusted to the above-mentioned preferred range, and the ink repellency and printing resistance of the unexposed area can be further improved. More preferably, it is 34% by mass or less, and still more preferably, it is 30% by mass or less.

[0051] Here, the total solid content of the composition for forming a metal chelate-containing silicone layer represents all components excluding the solvent from the components of the composition for forming a metal chelate-containing silicone layer.

[0052] A composition for forming a metal chelate-containing silicone layer, which contains a metal chelate compound, a polysiloxane having two or more vinyl groups in the molecule, and a crosslinking agent having three or more functional groups reactive with vinyl groups in the molecule, is an addition reaction type composition for forming a metal chelate-containing silicone layer. It preferably contains a siloxane compound having three or more SiH groups in the molecule as the crosslinking agent and a reaction catalyst. Further, it may contain a reaction inhibitor or a silane coupling agent.

[0053] A composition for forming a metal chelate-containing silicone layer, which contains a metal chelate compound, a polysiloxane having two or more silanol groups in the molecule, and a crosslinking agent having three or more functional groups reactive with silanol groups in the molecule, is a condensation reaction type composition for forming a metal chelate-containing silicone layer. It preferably contains a silane coupling agent having three or more hydrolyzable groups in the molecule as the crosslinking agent and a reaction catalyst.

[0054] A composition for forming a metal chelate-containing silicone layer, which contains a metal chelate compound, a polysiloxane having two or more silanol groups in the molecule, a silane coupling agent having three or more functional groups reactive with silanol groups in the molecule and having one or more vinyl groups in the molecule, and a crosslinking agent having three or more functional groups reactive with vinyl groups in the molecule, is a composition for forming a metal chelate-containing silicone layer of the addition reaction-condensation reaction combined type. It preferably contains a siloxane compound having three or more SiH groups in the molecule as the crosslinking agent and a reaction catalyst. Further, it may contain a reaction inhibitor or a silane coupling agent other than the above.

[0055] First, the composition for forming a metal chelate-containing silicone layer of the addition reaction type will be described.

[0056] Examples of polysiloxanes having two or more vinyl groups in the molecule include diorganopolysiloxanes having vinyl groups at both ends of the molecule, organovinylpolysiloxanes, organovinylsiloxane-diorganosiloxane copolymers, and polysiloxanes having two or more diorganovinylsiloxy groups in the molecule. Two or more of these may be contained. Among these, diorganopolysiloxanes having vinyl groups at both ends of the molecule and organovinylsiloxane-diorganosiloxane copolymers are preferred.

[0057] The diorganopolysiloxanes having vinyl groups at both ends of the molecule and organovinylsiloxane-diorganosiloxane copolymers may have any molecular structure, linear, cyclic, branched, or network. Also, the organic groups bonded to the silicon atoms may be the same or different in each repeating unit, and each is a monovalent organic group not containing an aliphatic unsaturated bond. Examples of the monovalent organic group not containing an aliphatic unsaturated bond include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, and heptyl group; aryl groups such as phenyl group, tolyl group, xylyl group, and naphthyl group; aralkyl groups such as benzyl group and phenethyl group; and halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group, and 3,3,3-trifluoropropyl group.

[0058] It is preferable that 50 mol% or more of the monovalent organic group not containing an aliphatic unsaturated bond is a methyl group in terms of further improving the ink repellency. Also, the weight average molecular weight of the polysiloxane having two or more vinyl groups in the molecule is preferably 30,000 or more in terms of further improving the printing resistance and scratch resistance, and preferably 300,000 or less in terms of improving the coatability. The weight average molecular weight is a polystyrene conversion value measured using GPC.

[0059] The content rate of polysiloxane having two or more vinyl groups in the composition for forming a metal chelate-containing silicone layer is preferably 60% by mass or more in the total solid content, and the element concentration can be easily adjusted to the above-mentioned preferable range, and the ink repellency can be further improved. More preferably, it is 65% by mass or more, and still more preferably, it is 70% by mass or more. On the other hand, the content rate of polysiloxane having two or more vinyl groups in the molecule is preferably 95% by mass or less in the total solid content in terms of more easily adjusting the element concentration to the above-mentioned preferable range and further improving the ink anchoring property of the metal chelate-containing silicone layer. More preferably, it is 90% by mass or less, and still more preferably, it is 85% by mass or less.

[0060] Examples of the siloxane compound having three or more SiH groups in the molecule include organohydrogenpolysiloxane, organohydrogensiloxane-diorganosiloxane copolymer, and a compound having three or more diorganohydrogensiloxy groups in the molecule. Two or more of these may be contained. Among these, organohydrogenpolysiloxane and organohydrogensiloxane-diorganosiloxane copolymer are preferable. The number of SiH groups in the molecule is preferably 5 or more, and more preferably 6 or more, in order to improve the curability of the metal chelate-containing silicone layer.

[0061] The organohydrogenpolysiloxane and the organohydrogensiloxane-diorganosiloxane copolymer may have any molecular structure of linear, cyclic, branched, or network. Also, the organic groups bonded to the silicon atoms may be the same or different in each repeating unit, and each is a monovalent organic group not containing an aliphatic unsaturated bond. Examples of the monovalent organic group not containing an aliphatic unsaturated bond include the groups exemplified in the diorganopolysiloxane having vinyl groups at both ends of the molecule and the organovinylsiloxane-diorganosiloxane copolymer.

[0062] In the composition for forming a metal chelate-containing silicone layer, the content of the siloxane compound having three or more SiH groups in the molecule is preferably 0.5% by mass or more in the total solid content, the elemental concentration can be easily adjusted to the above-mentioned preferred range, and the curability of the metal chelate-containing silicone layer can be improved. More preferably, it is 1% by mass or more. On the other hand, the content of the siloxane compound having three or more SiH groups in the molecule is preferably 10% by mass or less in the total solid content, the elemental concentration can be easily adjusted to the above-mentioned preferred range, and the ink repellency can be further improved. More preferably, it is 5% by mass or less.

[0063] As the reaction catalyst, those containing platinum and rhodium are preferred. Examples of the reaction catalyst containing platinum include platinum alone, those obtained by supporting solid platinum on a carrier (such as alumina, silica, carbon black, etc.), chloroplatinic acid, platinum-olefin complex, platinum-vinylsilane complex, platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-phosphite complex, platinum-acetylacetone complex, platinum-alkyl acetoacetate complex, platinum-dialkyl malonate complex, platinum-hydrocarbon complex described in U.S. Patent No. 3,159,601 and U.S. Patent No. 3,159,662, platinum alcoholate catalyst described in U.S. Patent No. 3,220,972, etc. Examples of the reaction catalyst other than the platinum compound include RhCl(PPh3)3, RhCl3, RhAl2O3, RuCl3, IrCl3, FeCl3, AlCl3, PdCl2·2H2O, NiCl2, TiCl4, etc. These may be contained in two or more kinds.

[0064] The content of the reaction catalyst in the composition for forming a metal chelate-containing silicone layer is preferably 0.001% by mass or more and 0.1% by mass or less in the total solid content.

[0065] As the reaction inhibitor, an amine compound or an acetylene compound is preferred. For example, pyridine, picoline, 2,2'-dipyridyl, 2-butanone oxime, acetylene alcohol, acetylene silane, etc. may be mentioned. Examples of the acetylene alcohol include 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, etc. Two or more of these may be contained. By containing these reaction inhibitors, the pot life of the composition for forming a metal chelate-containing silicone layer is improved.

[0066] The content of the reaction inhibitor in the composition for forming a metal chelate-containing silicone layer is preferably 0.1 part by mass or more and 15 parts by mass or less in the total solid content.

[0067] As the silane coupling agent, vinyltriacetoxysilane and vinyltris(methylethylketoximino)silane are preferred.

[0068] The content ratio of the silane coupling agent in the composition for forming a metal chelate-containing silicone layer is preferably 1% by mass or more and 5% by mass or less in the total solid content.

[0069] Next, the composition for forming a condensation reaction type metal chelate-containing silicone layer will be described.

[0070] Examples of the polysiloxane having two or more silanol groups in the molecule include diorganopolysiloxane having silanol groups at both ends of the molecule.

[0071] The diorganopolysiloxane having silanol groups at both molecular ends may have any molecular structure of linear, cyclic, branched, or network. Further, the organic groups bonded to silicon atoms may be the same or different in each repeating unit, and each is a monovalent organic group not containing an aliphatic unsaturated bond. Examples of the monovalent organic group not containing an aliphatic unsaturated bond include the groups exemplified in the diorganopolysiloxane having vinyl groups at both molecular ends and the organovinylsiloxane-diorganosiloxane copolymer.

[0072] It is preferable that 50 mol% or more of the monovalent organic group not containing an aliphatic unsaturated bond is a methyl group in terms of further improving ink repellency. Further, the weight average molecular weight of the polysiloxane having two or more silanol groups in the molecule is preferably 30,000 or more in terms of further improving printing resistance and scratch resistance, and preferably 300,000 or less in terms of improving coatability. The weight average molecular weight is a polystyrene conversion value measured using GPC.

[0073] The content of the polysiloxane having two or more silanol groups in the molecule in the composition for forming a metal chelate-containing silicone layer is preferably 60% by mass or more in the total solid content, so that the element concentration can be easily adjusted to the above-mentioned preferable range and the ink repellency can be further improved. More preferably 65% by mass or more, and still more preferably 70% by mass or more. On the other hand, the content of the polysiloxane having two or more silanol groups in the molecule is preferably 95% by mass or less in the total solid content in terms of easily adjusting the element concentration to the above-mentioned preferable range and further improving the ink film formation property of the metal chelate-containing silicone layer. More preferably 90% by mass or less, and still more preferably 85% by mass or less.

[0074] Examples of the crosslinking agent having three or more functional groups reactive with silanol groups in the molecule include silane coupling agents, and examples of the silane coupling agents include the silane coupling agents exemplified in the composition for forming an addition reaction type metal chelate-containing silicone layer.

[0075] The content rate of the silane coupling agent in the composition for forming a metal chelate-containing silicone layer is preferably 0.5 mass% or more in the total solid content, and the curability and the adhesiveness to the underlying layer can be improved. More preferably, it is 1 mass% or more. On the other hand, the content rate of the silane coupling agent in the composition for forming a metal chelate-containing silicone layer is preferably 10 mass% or less in the total solid content, and the ink repellency can be further improved. More preferably, it is 5 mass% or less.

[0076] Examples of the reaction catalyst include organic carboxylic acids, acids, alkalis, amines, metal alkoxides, metal diketeneates, and organic acid salts of metals such as tin, lead, zinc, iron, cobalt, calcium, and manganese. More specifically, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, zinc octylate, iron octylate, etc. can be mentioned. Two or more of these may be contained.

[0077] The content rate of the reaction catalyst in the composition for forming a metal chelate-containing silicone layer is preferably 0.01 mass% or more and 1 mass% or less in the total solid content.

[0078] Next, the composition for forming a metal chelate-containing silicone layer of the addition reaction-condensation reaction type will be described.

[0079] Examples of the polysiloxane having two or more silanol groups in the molecule include the polysiloxanes exemplified in the composition for forming a metal chelate-containing silicone layer of the condensation reaction type. The preferable range of the content rate of the polysiloxane having two or more silanol groups in the molecule in the composition for forming a metal chelate-containing silicone layer is the same as that of the composition for forming a metal chelate-containing silicone layer of the condensation reaction type.

[0080] Examples of the crosslinking agent having three or more functional groups reactive with silanol groups in the molecule include silane coupling agents. Examples of the silane coupling agents include the silane coupling agents exemplified in the composition for forming an addition reaction type metal chelate-containing silicone layer. The preferable range of the content rate of the crosslinking agent having three or more functional groups reactive with silanol groups in the molecule in the composition for forming a metal chelate-containing silicone layer is the same as that of the composition for forming a condensation reaction type metal chelate-containing silicone layer.

[0081] Examples of the silane coupling agent having one or more vinyl groups in the molecule include the silane coupling agents exemplified in the composition for forming an addition reaction type metal chelate-containing silicone layer.

[0082] The content rate of the silane coupling agent having one or more vinyl groups in the molecule in the composition for forming a metal chelate-containing silicone layer is preferably 1 mass% or more and 5 mass% or less in the total solid content.

[0083] Examples of the siloxane compound having three or more SiH groups in the molecule include the above-mentioned siloxane compounds exemplified in the composition for forming an addition reaction type metal chelate-containing silicone layer. The preferable range of the content rate of the siloxane compound having three or more SiH groups in the molecule in the composition for forming a metal chelate-containing silicone layer is the same as that of the composition for forming an addition reaction type metal chelate-containing silicone layer.

[0084] Examples of the reaction catalyst include the reaction catalysts exemplified in the composition for forming an addition reaction type metal chelate-containing silicone layer. The preferable range of the content rate of the reaction catalyst in the composition for forming a metal chelate-containing silicone layer is the same as that of the composition for forming an addition reaction type metal chelate-containing silicone layer.

[0085] Examples of the reaction inhibitor include the reaction inhibitors exemplified in the composition for forming an addition reaction type metal chelate-containing silicone layer. The preferable range of the content of the reaction inhibitor in the composition for forming a metal chelate-containing silicone layer is the same as that of the composition for forming an addition reaction type metal chelate-containing silicone layer.

[0086] In addition, the composition for forming a metal chelate-containing silicone layer may contain a liquid having a surface tension of 30 mN / m or less at 25°C, and the ink repellency can be further improved. Examples of the liquid having a surface tension of 30 mN / m or less at 25°C include the liquids described in International Publication No. 2016 / 076286 and the like.

[0087] In addition, the composition for forming a metal chelate-containing silicone layer may contain known reinforcing agents such as silica particles and silicone resins having functional groups such as vinyl groups, SiH groups, and silanol groups, and the rubber strength can be improved.

[0088] The composition for forming a metal chelate-containing silicone layer preferably contains a solvent, which can improve the coating property, solubility, and compatibility of the metal chelate compound.

[0089] Examples of the solvent include aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbons, and chain or cyclic ether compounds. From the viewpoint of improving the solubility, compatibility, and coatability of the silicone component, it is preferable to contain an aliphatic hydrocarbon solvent and / or an alicyclic hydrocarbon solvent. On the other hand, from the viewpoint of improving the solubility and compatibility of the metal chelate compound, it is preferable to contain an aromatic hydrocarbon solvent. That is, from the viewpoint that both the silicone component and the metal chelate compound can be dissolved or made compatible with each other and have excellent coatability, it is preferable to use a mixed solvent of an aliphatic hydrocarbon solvent and / or an alicyclic hydrocarbon solvent and an aromatic hydrocarbon solvent. From the viewpoint of improving the coatability, the proportion of the aromatic hydrocarbon solvent in the mixed solvent is preferably 30% by volume or less, more preferably 25% by volume or less. Further, from the viewpoint of improving safety and handleability, the boiling point of the above solvent at 1 atm is preferably 60°C or higher, more preferably 80°C or higher. On the other hand, from the viewpoint of improving the drying property of the coating liquid, the boiling point of the above solvent at 1 atm is preferably 160°C or lower, more preferably 140°C or lower. Examples of such solvents include linear or branched aliphatic hydrocarbon solvents having 6 to 9 carbon atoms, and alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, and trimethylcyclohexane, and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and diethylbenzene. Two or more of these may be contained. Commercially available solvents represented as follows may also be used.

[0090] Mixtures of aliphatic hydrocarbon solvents: For example, Maru Sol 8 (manufactured by Maruzen Petrochemical Co., Ltd.), "Isopar" (registered trademark) C, "Isopar" (registered trademark) E (both manufactured by ExxonMobil Chemical Co., Ltd.), IP Solvent 1016 (manufactured by Idemitsu Kosan Co., Ltd.), "Isosol" (registered trademark) 200 (manufactured by JX Nippon Oil & Energy Corporation), etc., and are available from each company.

[0091] Mixture of alicyclic hydrocarbon solvents: For example, "EXXSOL" (registered trademark) DSP80 / 100, "EXXSOL" DSP100 / 140, "EXXSOL" DSP145 / 160 (all manufactured by ExxonMobil Chemical Company), CS volatile oil (manufactured by JX Nippon Oil & Energy Corporation), etc., and are available from each company.

[0092] The following describes a specific method for preparing the composition for forming a metal chelate-containing silicone layer, but it is not limited thereto.

[0093] For example, a solvent, a siloxane compound having two or more vinyl groups in the molecule, and a liquid having a surface tension of 30 mN / m or less at 25°C are charged into a container, stirred until the components are uniform, and then the moisture in the solution is removed by blowing dry nitrogen. Next, a reaction catalyst and a reaction inhibitor are added and stirred until the components are uniform, and then a siloxane compound having three or more SiH groups in the molecule and a silane coupling agent are added and stirred until the components are uniform. Finally, a metal chelate compound is added and stirred until the components are uniform to obtain a composition for forming a metal chelate-containing silicone layer.

[0094] Examples of the composition for forming a primer layer include the compositions described as the composition for forming a heat insulating layer in, for example, JP-A-2004-199016, JP-A-2004-334025, JP-A-2006-276385, etc.

[0095] Next, a method for manufacturing a lithographic printing plate from the lithographic printing plate original plate will be described. The method for manufacturing a lithographic printing plate according to the present invention exposes the lithographic printing plate original plate according to the present invention from the side of the metal chelate-containing silicone layer or the metal chelate-free silicone layer with active energy rays to form an ink-receiving part.

[0096] When a cover film or laminated paper is provided on the metal chelate-containing silicone layer or the metal chelate-free silicone layer of the lithographic printing plate original plate, it is preferably removed in advance.

[0097] By exposing the metal chelate-containing silicone layer or the metal chelate-free silicone layer of the above-described lithographic printing plate original plate in a pattern by active energy rays from the side of the metal chelate-containing silicone layer or the metal chelate-free silicone layer, the metal chelate-containing silicone layer or the metal chelate-free silicone layer in the exposed portion changes in ink receptivity. The peak wavelength of the active energy rays is preferably 200 to 600 nm. If the peak wavelength is 200 nm or more, exposure in a nitrogen atmosphere or under vacuum becomes unnecessary, and exposure can be performed in the atmosphere. On the other hand, if the peak wavelength is 600 nm or less, the ink receptivity of the exposed portion can be further improved. The peak wavelength is more preferably 400 nm or less. From the point that a mask for plate making becomes unnecessary, it is preferable to directly draw a pattern of the ink-receptive portion using a laser drawing apparatus having a wavelength of 200 to 600 nm or the like.

[0098] Examples of the active energy ray exposure apparatus having a wavelength of 200 to 600 nm include a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and an excimer lamp, which are included in the range of a peak wavelength of 200 to 600 nm. Examples of the excimer lamp having a wavelength of 200 to 600 nm include rare gas excimer lamps and rare gas halogen excimer lamps such as KrBr (207 nm), KrCl (222 nm), KrF (248 nm), XeI (253 nm), HgXe (254 nm), Cl2 (259 nm), XeBr (283 nm), XeCl (308 nm), I2 (342 nm), XeF (352 nm), HgI (443 nm), HgBr (503 nm), and HgCl (558 nm). Among these, ultraviolet excimer lamps having a wavelength of 200 to 400 nm such as KrBr (207 nm), KrCl (222 nm), KrF (248 nm), XeI (253 nm), HgXe (254 nm), Cl2 (259 nm), XeBr (283 nm), XeCl (308 nm), I2 (342 nm), and XeF (352 nm) are more preferable in terms of improving the productivity of the lithographic printing plate.

[0099] As the active energy ray laser with a wavelength of 200 to 600 nm, there are the fifth harmonic (213 nm) of Nd:YAG laser or Nd:YVO4 laser, the fourth harmonic (266 nm) of Nd:YAG laser or Nd:YVO4 laser, the third harmonic (355 nm) of Nd:YAG laser or Nd:YVO4 laser, the second harmonic (532 nm) of Nd:YAG laser or Nd:YVO4 laser, the third harmonic (231 nm) of ruby laser, the second harmonic (347 nm) of ruby laser, the third harmonic (252 nm) of alexandrite laser, the second harmonic (378 nm) of alexandrite laser and other solid lasers, and KrBr laser (207 nm), KrCl laser (222 nm), KrF laser (248 nm), XeI laser (253 nm), HgXe laser (254 nm), Cl2 laser (259 nm), XeBr laser (283 nm), XeCl laser (308 nm), I2 laser (342 nm), XeF laser (352 nm), HgI laser (443 nm), HgBr laser (503 nm), HgCl laser (558 nm) and other rare gas excimer lasers and rare gas halogen excimer lasers. Among these, in terms of improving the productivity of the lithographic printing plate, the ultraviolet lasers with a wavelength of 200 to 400 nm such as the fifth harmonic (213 nm) of Nd:YAG laser or Nd:YVO4 laser, the fourth harmonic (266 nm) of Nd:YAG laser or Nd:YVO4 laser, the third harmonic (355 nm) of Nd:YAG laser or Nd:YVO4 laser, the third harmonic (231 nm) of ruby laser, the second harmonic (347 nm) of ruby laser, the third harmonic (252 nm) of alexandrite laser, the second harmonic (378 nm) of alexandrite laser, KrBr laser (207 nm), KrCl laser (222 nm), KrF laser (248 nm), XeI laser (253 nm), HgXe laser (254 nm), Cl2 laser (259 nm), XeBr laser (283 nm), XeCl laser (308 nm), I2 laser (342 nm), XeF laser (352 nm) are more preferable.

[0100] As the oscillation method of the active energy ray laser, a pulse oscillation method is preferable. Also, as the pulse width of the pulse laser, a pulse laser with any pulse width of nanosecond, picosecond, or femtosecond can be used. Among these, a nanosecond pulse laser, which has a relatively small heat load and is less affected by ablation due to multiphoton absorption, is preferable.

[0101] Note that the laser in the present invention refers to an electromagnetic wave amplified in a resonator.

[0102] The exposure amount of the active energy ray with a wavelength of 200 to 600 nm is preferably 2 J / cm 2 or more, and more preferably 3 J / cm 2 or more, in terms of further improving the ink adhesion property of the exposed portion. On the other hand, the exposure amount is preferably 8 J / cm 2 or less, more preferably 7 J / cm 2 or less, and even more preferably 6 J / cm 2 or less, in terms of further suppressing the ablation dust in the exposed portion.

[0103] Note that the exposure amount E in the present invention is obtained by the following formula, and the irradiation energy [W] can be measured using a commercially available power meter or the like. <Method for obtaining exposure amount E> E = W ÷ S × T [J / cm 2 W: Irradiation energy [W] S: Irradiation area [cm 2 T: Irradiation time [sec].

[0104] When storing the obtained lithographic printing plate by stacking, it is preferable to laminate a separator paper between the lithographic printing plates, which can protect the surface of the uppermost layer of the lithographic printing plate.

[0105] Next, a method for manufacturing a printed matter will be described.

[0106] ​​As a method for manufacturing a printed matter, it is preferable to use the above-described waterless lithographic printing plate, ink, and printing medium. Specifically, it preferably includes a step of attaching ink to the surface of the ink-receiving part of the waterless lithographic printing plate, and a step of transferring the ink attached to the surface of the ink-receiving part to the printing medium directly or via a blanket.

[0107] As the printing machine, a known direct printing machine or offset printing machine can be used. However, an offset printing machine is preferable in that more printed matters can be obtained by suppressing damage to the waterless lithographic printing plate during printing.

[0108] As the offset printing machine, an offset printing machine equipped with a cooling mechanism for a rocking roller and / or a plate cylinder is preferable in terms of improving stain resistance.

[0109] As the ink, known oxidation polymerization type ink or active energy ray curable ink can be used. However, the active energy ray curable ink is more preferable in that it can be transferred to the next process immediately after printing due to quick drying. Also, the ink may be oil-soluble or water-soluble, but water-soluble is preferable in terms of reducing the load on workers and the environment. Water-soluble active energy ray curable ink is even more preferable.

[0110] As the active energy ray, those exemplified in the method for manufacturing a lithographic printing plate are preferable.

[0111] Examples of the water-soluble active energy ray curable ink preferably used in the present invention include known water-soluble active energy ray curable inks that can be washed with water or an aqueous cleaning liquid disclosed in, for example, JP-A-2017-52817, WO 2017 / 047817, WO 2017 / 090663, etc.

[0112] Examples of printable media include papers such as high-quality paper, art paper, coated paper, cast paper, synthetic paper, newsprint; metals such as aluminum, aluminum alloys, iron, steel, zinc, copper; plastic films such as polyethylene terephthalate, polyethylene, polyester, polyamide, polyimide, polystyrene, polypropylene, polycarbonate, polyvinyl acetal; or composites of these papers, metals, and plastic films (papers or plastic films with metal vapor deposition or lamination, papers or metals with laminated plastic films, metals or plastic films with laminated papers).

[0113] Among these, in the method for manufacturing a printed matter according to the present invention, it is suitable for printing on ink component non-absorbent printable media such as synthetic paper, metals, plastic films, papers or plastic films with metal vapor deposition or lamination, papers or metals with laminated plastic films, etc., whose printable surface is composed of metal or plastic film.

[0114] Among the above, the printable surface of printable media such as synthetic paper, plastic films, papers or metals with laminated plastic films, etc., whose printable surface is composed of plastic film, may be subjected to surface treatment such as application of a primer resin, corona discharge treatment, plasma treatment, etc. from the viewpoint of improving adhesiveness.

[0115] As the shape of the printable media, it is preferable to use a roll-shaped long printable media. By printing by the roll-to-roll method using the waterless lithographic printing plate of the present invention and the roll-shaped long printable media, it is possible to mass-produce a high-definition printed matter with seamless pattern.

[0116] The waterless lithographic printing plate of the present invention does not require a developing process and does not need to use pretreatment chemicals, post-treatment chemicals, etc. used in the conventional developing process. Therefore, there is no adhesion or penetration of pretreatment chemicals or post-treatment chemicals to the waterless lithographic printing plate, and there is no transfer of these chemicals from the waterless lithographic printing plate to the printed matter in the printing process. Thus, it can be particularly preferably used for printing food packaging applications with strict requirements for chemical content.

Examples

[0117] Hereinafter, the present invention will be described in more detail with reference to examples.

[0118] The evaluation in each example and comparative example was carried out by the following method.

[0119] (1) Evaluation of waterless lithographic printing plate (1-1) Element concentration in the metal chelate-containing silicone layer and the metal chelate-free silicone layer For the metal chelate-containing silicone layer and the metal chelate-free silicone layer of the waterless lithographic printing plate original obtained in each example and comparative example, the elemental concentration (atom%) was calculated from the area ratio of each elemental spectrum detected by X-ray photoelectron spectroscopy. The analysis conditions and analysis conditions are shown below. [Analysis conditions] Analyzer: ESCAsystem ULVAC-PHI5700 (manufactured by ULVAC-PHI) Vacuum degree: 5.0×10 -7 Torr or less X-ray source: Mg ray source Acceleration voltage: 15 kV Integration times: 6 times Measurement step: 0.125 eV Scan: Narrow scan X-ray incident angle: 45 degrees [Analysis conditions] Data analysis software: PHI MultiPak (manufactured by ULVAC-PHI) Smoothing correction: Point9 Background correction: OFF SET.

[0120] (1-2)Average Etching Amount of Exposed Area For 5 points each of the exposed area and unexposed area randomly selected from the waterless lithographic printing plates obtained in each example and comparative example, the height difference between the exposed area and the unexposed area was calculated from the height information of the exposed area and the unexposed area measured by a 3D measurement laser microscope, and the etching amount of the exposed area was obtained. The average value of the 5-point etching amount obtained was taken as the average etching amount of the exposed area (μm), and the ease of generation of ablation dust was evaluated based on the average etching amount of the exposed area. It can be said that the smaller the average etching amount of the exposed area, the less ablation dust is generated during exposure. The analysis conditions and analysis conditions are shown below. [Analysis Conditions] Analysis apparatus: LEXT OLS4100 (manufactured by Olympus Corporation) Analysis mode: High-precision mode Laser wavelength: 405 nm Laser spot diameter: 200 nm Objective lens magnification: 50 times Measurement range: 259×259 [μm]. [Analysis Conditions] Image analysis software: OLS4100 (manufactured by Olympus Corporation) Noise correction: Removal of sawtooth surface noise.

[0121] (2) Printing Evaluation (2-1) Ink Repellency / Ink Adhesion The waterless lithographic printing plates obtained in each example and comparative example were mounted on the plate cylinder of an EB offset printing press: OFFSET CI / 8 (manufactured by COMEXI) (for Examples 44 and 45, the plate cylinder shaft), and a commercially available waterless lithographic printing plate original: Toray Waterless CTP Lithographic Plate TAC-VG5 was used as a reference to perform printing under the following printing conditions. [Printing 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 Red (manufactured by Samsung Ink Co., Ltd.) Ink component non-absorbent printing 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 Printing speed: 100 m / min Ink supply amount: Three levels where the solid part reflection density of the printed matter printed with TAC-VG5 is in the range of (1) 1.20 ± 0.02, (2) 1.50 ± 0.02, (3) 1.80 ± 0.02 [Ink curing conditions] EB irradiation dose: 40 kGy EB irradiation atmosphere: Nitrogen atmosphere.

[0122] The printed matter at the 500 m point from the start of printing, printed at the above three levels with different ink supply amounts, was stacked in 5 sheets and placed on coated paper: OK "Top Coat" (registered trademark) + (manufactured by Oji Paper Co., Ltd.). The reflection density of the white solid part and the solid part was measured with a spectral density colorimeter: Exact Advance (manufactured by X-Rite).

[0123] The ink repellency was evaluated by the reflection density of the white solid part. The lower the reflection density of the white solid part, the better the ink repellency. The ink film formation property was evaluated by the reflection density of the solid part. The higher the reflection density of the solid part is equal to or higher than that of the solid part of TAC-VG5, the better the ink film formation property.

[0124] (2-2) Print durability Printing was carried out up to a maximum of 100,000 m under the above printing conditions (VG5 solid part reflection density: 1.50 ± 0.05). The printed matter every 5,000 m was sampled, and the presence or absence of ground contamination where unintended streaks were formed in the non-image part was evaluated. The limit printing length where good printed matter was continuously obtained was evaluated as the print durability. The longer the limit printing length, the better the print durability.

[0125] In Comparative Examples 3, 4, and 9, since good printed matter could not be obtained from the initial stage of printing, the limit printing length where printed matter of the same quality as in the initial stage of printing was continuously obtained was evaluated as the print durability.

[0126] [Example 1] On an aluminum alloy plate with a thickness of 0.24 mm, the following composition for forming a primer layer was applied using a slit coater (manufactured by Toray Engineering Co., Ltd.), and heated at 180°C for 2 minutes to provide a primer layer with an average thickness of 10 μm.

[0127] <Composition for forming primer layer> The following components (a-1), (b-1) and (c-1) were put into a container and stirred and mixed until the component (c-1) was dissolved. The components (d-1) and (e-1) were put into the obtained solution and stirred and mixed until the components were uniform to obtain the composition for forming a primer layer. (a-1) N,N-dimethylformamide: 270.00 parts by mass (b-1) Methyl ethyl ketone: 210.00 parts by mass (c-1) Epoxy resin: “jER” (registered trademark) 1010 (manufactured by Mitsubishi Chemical Corporation): 35.00 parts by mass (d-1) Polyurethane: “Sampleen” (registered trademark) LQ-T1331D (manufactured by Sanyo Chemical Industries, Ltd., solid content concentration: 20% by mass): 265.00 parts by mass (e-1) Crosslinking agent: “Duránate” (registered trademark) MF-B60B (manufactured by Asahi Kasei Corporation, HDI-based blocked isocyanate, solid content concentration: 60% by mass (solvent: n-butyl acetate / n-butanol)): 20.00 parts by mass.

[0128] Next, using a slit coater, the following composition -1 for forming a metal chelate-containing silicone layer was applied onto the primer layer and heated at 100°C for 1 minute to provide a metal chelate-containing silicone layer (first layer) with an average thickness of 20 μm, thereby obtaining an original lithographic printing plate without water.

[0129] <Composition -1 for forming metal chelate-containing silicone layer> The following components (f-1), (g-1), and (h-1) were charged into a container and stirred and mixed until the component (h-1) was dissolved. Components (i-1) and (j-1) were charged into the resulting solution, stirred and mixed for 10 minutes, then component (k-1) was charged and stirred and mixed for 10 minutes. Finally, component (l-1) was charged and stirred and mixed for 10 minutes to obtain a composition-1 for forming a metal chelate-containing silicone layer. (f-1) Naphthenic solvent: "Exxsol" (registered trademark) DSP100 / 140 (manufactured by ExxonMobil Chemical Company): 240.00 parts by mass (g-1) Aromatic hydrocarbon solvent: Toluene: 60.00 parts by mass (h-1) A siloxane compound having two or more vinyl groups in the molecule (both ends dimethylvinylsiloxy-polydimethylsiloxane): DMS-V42 (manufactured by Gelest Inc., weight average molecular weight: 72,000, number of vinyl groups in the molecule: 2.0): 87.47 parts by mass (i-1) Reaction catalyst (platinum mixture): XC94-C4326 (manufactured by Momentive Performance Materials Japan LLC, solid content concentration: 1% by mass): 3.00 parts by mass (j-1) Reaction inhibitor: 2-Methyl-3-butyn-2-ol: 0.20 parts by mass (k-1) A siloxane compound having three or more SiH groups in the molecule (both ends trimethylsiloxy-polymethylhydrosiloxane): HMS-993 (manufactured by Gelest Inc., weight average molecular weight: 2,250, number of SiH groups in the molecule: 34.8): 2.50 parts by mass (l-1) Metal chelate compound: AL-A(W) (manufactured by Kawaken Fine Chemicals Co., Ltd., aluminum trisacetylacetonate): 12.37 parts by mass.

[0130] Using a solid pulse laser with a wavelength of 355 nm: 3-Axis UV Laser Marker MD-U1000C (manufactured by Keyence Corporation), on the metal chelate-containing silicone layer of the above-described waterless lithographic printing plate original, exposure was performed in the air at an exposure amount of 5 J / cm 2 to perform pattern drawing, thereby obtaining a waterless lithographic printing plate.

[0131] [Example 2] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 1, except that the component (l-1) of the composition for forming the metal chelate-containing silicone layer-1 was changed to 15.81 parts by mass of (l-2) metal chelate compound: ALCH-TR (manufactured by Kawaken Fine Chemicals Co., Ltd., aluminum trisethylacetoacetate).

[0132] [Example 3] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 1, except that the component (l-1) of the composition for forming the metal chelate-containing silicone layer-1 was changed to 10.47 parts by mass of (l-3) metal chelate compound: ALCH (manufactured by Kawaken Fine Chemicals Co., Ltd., di-iso-propoxide aluminum monoethylacetoacetate).

[0133] [Example 4] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 1, except that the component (l-1) of the composition for forming the metal chelate-containing silicone layer-1 was changed to 16.95 parts by mass of the compound obtained by removing the solvent from (l-4) metal chelate compound: "Organix" (registered trademark) TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd., titanium tetraacetylacetonate / 2-propanol = 65 / 35 mass% solution) by dry nitrogen blowing.

[0134] [Example 5] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 1, except that the component (l-1) of the composition for forming the metal chelate-containing silicone layer-1 was changed to 14.97 parts by mass of the compound obtained by removing the solvent from (l-5) metal chelate compound: "Organix" (registered trademark) TC-150 (manufactured by Matsumoto Fine Chemical Co., Ltd., di-n-butoxide titanium bisacetylacetonate / n-butanol = 73 / 27 mass% solution) by dry nitrogen blowing.

[0135] [Example 6] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 1, except that the component (l-1) of the composition for forming the metal chelate-containing silicone layer-1 was changed to 16.19 parts by mass of a (l-6) metal chelate compound: "ORGATIX" (registered trademark) TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd., di-iso-propoxide titanium bisethylacetoacetate).

[0136] [Example 7] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 1, except that the component (l-1) of the composition for forming the metal chelate-containing silicone layer-1 was changed to 18.61 parts by mass of a (l-7) metal chelate compound: "ORGATIX" (registered trademark) ZC-162 (manufactured by Matsumoto Fine Chemical Co., Ltd., zirconium tetraacetylacetonate).

[0137] [Example 8] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 1, except that the component (l-1) of the composition for forming the metal chelate-containing silicone layer-1 was changed to 18.91 parts by mass of a compound obtained by removing the solvent from a (l-8) metal chelate compound: "ORGATIX" (registered trademark) ZC-580 (manufactured by Matsumoto Fine Chemical Co., Ltd., solution of di-n-butoxide zirconium bisethylacetoacetate / n-butanol = 70 / 30% by mass) by dry nitrogen blowing.

[0138] [Example 9] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 5, except that the addition amount of DMS-V42, which is the component (h-1) of the composition for forming the metal chelate-containing silicone layer, was changed to 94.47 parts by mass, and the addition amount of the compound obtained by removing the solvent from "ORGATIX" (registered trademark) TC-150, which is the component (l-5), was changed to 4.49 parts by mass by dry nitrogen blowing.

[0139] [Example 10] The addition amount of DMS-V42, which is the (h-1) component of the composition for forming the metal chelate-containing silicone layer, was changed to 93.47 parts by mass, and the addition amount of the compound obtained by removing the solvent from “ORGATICS” (registered trademark) TC-150, which is the (l-5) component, by dry nitrogen blowing was changed to 5.99 parts by mass. Otherwise, in the same manner as in Example 5, an original waterless lithographic printing plate and a waterless lithographic printing plate were obtained.

[0140] [Example 11] The addition amount of DMS-V42, which is the (h-1) component of the composition for forming the metal chelate-containing silicone layer, was changed to 91.47 parts by mass, and the addition amount of the compound obtained by removing the solvent from “ORGATICS” (registered trademark) TC-150, which is the (l-5) component, by dry nitrogen blowing was changed to 8.98 parts by mass. Otherwise, in the same manner as in Example 5, an original waterless lithographic printing plate and a waterless lithographic printing plate were obtained.

[0141] [Example 12] The addition amount of DMS-V42, which is the (h-1) component of the composition for forming the metal chelate-containing silicone layer, was changed to 82.47 parts by mass, and the addition amount of the compound obtained by removing the solvent from “ORGATICS” (registered trademark) TC-150, which is the (l-5) component, by dry nitrogen blowing was changed to 22.45 parts by mass. Otherwise, in the same manner as in Example 5, an original waterless lithographic printing plate and a waterless lithographic printing plate were obtained.

[0142] [Example 13] The addition amount of DMS-V42, which is the (h-1) component of the composition for forming the metal chelate-containing silicone layer, was changed to 77.47 parts by mass, and the addition amount of the compound obtained by removing the solvent from “ORGATICS” (registered trademark) TC-150, which is the (l-5) component, by dry nitrogen blowing was changed to 29.94 parts by mass. Otherwise, in the same manner as in Example 5, an original waterless lithographic printing plate and a waterless lithographic printing plate were obtained.

[0143] [Example 14] The addition amount of DMS-V42, which is the (h-1) component of the composition for forming the metal chelate-containing silicone layer, was changed to 74.47 parts by mass, and the addition amount of the compound obtained by removing the solvent from “ORGATICS” (registered trademark) TC-150, which is the (l-5) component, by dry nitrogen blowing was changed to 34.43 parts by mass. Otherwise, in the same manner as in Example 5, an original waterless lithographic printing plate and a waterless lithographic printing plate were obtained.

[0144] [Example 15] The addition amount of DMS-V42, which is the (h-1) component of the composition for forming the metal chelate-containing silicone layer, was changed to 72.47 parts by mass, and the addition amount of the compound obtained by removing the solvent from “ORGATICS” (registered trademark) TC-150, which is the (l-5) component, by dry nitrogen blowing was changed to 37.42 parts by mass. Otherwise, in the same manner as in Example 5, an original waterless lithographic printing plate and a waterless lithographic printing plate were obtained.

[0145] [Example 16] The average thickness of the metal chelate-containing silicone layer was changed to 10 μm. Otherwise, in the same manner as in Example 14, an original waterless lithographic printing plate and a waterless lithographic printing plate were obtained.

[0146] [Example 17] The average thickness of the metal chelate-containing silicone layer was changed to 5 μm. Otherwise, in the same manner as in Example 14, an original waterless lithographic printing plate and a waterless lithographic printing plate were obtained.

[0147] [Example 18] The average thickness of the metal chelate-containing silicone layer was changed to 2.5 μm. Otherwise, in the same manner as in Example 14, an original waterless lithographic printing plate and a waterless lithographic printing plate were obtained.

[0148] [Example 19] On the metal chelate-containing silicone layer of the waterless lithographic printing plate precursor described in Example 17, using a slit coater, the following composition for forming a metal chelate-free silicone layer -1 was applied and heated at 100°C for 1 minute. A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 17, except that a metal chelate-free silicone layer (second layer) with an average thickness of 0.125 μm was provided.

[0149] <Composition for forming a metal chelate-free silicone layer -1> The following components (f-2) and (h-2) were put into a container and stirred and mixed until the component (h-2) was dissolved. The resulting solution was bubbled with dry nitrogen for 20 minutes to remove the moisture in the solution. Immediately before coating, the component (k-2) was added and stirred and mixed for 30 minutes to obtain the composition for forming a metal chelate-free silicone layer -1. (f-2) Isoparaffinic solvent: “Isopar” (registered trademark) C (manufactured by ExxonMobil Chemical Company): 900.00 parts by mass (h-2) Siloxane compound having two or more silanol groups in the molecule (both-terminal silanol-polydimethylsiloxane): DMS-S45 (manufactured by Gelest Inc., weight average molecular weight: 110,000, number of silanol groups in the molecule: 2.0): 96.00 parts by mass (k-2) Crosslinking agent: Vinyltris(methylethylketoximino)silane: 4.00 parts by mass.

[0150] [Example 20] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 19, except that the average thickness of the metal chelate-free silicone layer was changed to 0.25 μm.

[0151] [Example 21] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 19, except that the average thickness of the metal chelate-free silicone layer was changed to 0.5 μm.

[0152] [Example 22] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 19, except that the average thickness of the metal chelate-free silicone layer was changed to 1 μm.

[0153] [Example 23] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 19, except that the average thickness of the metal chelate-free silicone layer was changed to 2 μm.

[0154] [Example 24] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 21, except that the component (l-5) of the composition for forming the metal chelate-containing silicone layer was changed to 28.46 parts by mass of (l-1) AL-A(W).

[0155] [Example 25] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 21, except that the component (l-5) of the composition for forming the metal chelate-containing silicone layer was changed to 36.37 parts by mass of (l-2) ALCH-TR.

[0156] [Example 26] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 21, except that the component (l-5) of the composition for forming the metal chelate-containing silicone layer was changed to 24.07 parts by mass of (l-3) ALCH.

[0157] [Example 27] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 21, except that the component (l-5) of the composition for forming the metal chelate-containing silicone layer was changed to 38.99 parts by mass of the compound obtained by removing the solvent from (l-4) "Organix" (registered trademark) TC-401 by dry nitrogen blowing.

[0158] [Example 28] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 21, except that the component (l-5) of the composition for forming the metal chelate-containing silicone layer was changed to 37.24 parts by mass of "(ORGATICS)" (registered trademark) TC-750.

[0159] [Example 29] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 21, except that the component (l-5) of the composition for forming the metal chelate-containing silicone layer was changed to 42.80 parts by mass of "(ORGATICS)" (registered trademark) ZC-162.

[0160] [Example 30] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 21, except that the component (l-5) of the composition for forming the metal chelate-containing silicone layer was changed to 43.50 parts by mass of the compound obtained by removing the solvent from "(ORGATICS)" (registered trademark) ZC-580 by dry nitrogen blowing.

[0161] [Example 31] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 21, except that the laser exposure amount was changed to 3 J / cm 2 .

[0162] [Example 32] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 21, except that the laser exposure amount was changed to 4 J / cm 2 .

[0163] [Example 33] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 21, except that the laser exposure amount was changed to 6 J / cm 2 .

[0164] [Example 34] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 21, except that the laser exposure amount was changed to 7 J / cm 2A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 21, except that it was changed to

[0165] [Example 35] The laser exposure amount was changed to 8 J / cm 2 A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 21, except that it was changed to

[0166] [Example 36] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 21, except that the composition for forming the metal chelate-containing silicone layer was changed to the following composition for forming a metal chelate-containing silicone layer - 2.

[0167] [Composition for forming metal chelate-containing silicone layer - 2] The following components (f-1), (g-1) and (h-3) were put into a container and stirred and mixed until the component (h-3) was dissolved. The obtained solution was bubbled with dry nitrogen for 20 minutes to remove the moisture in the solution. Immediately before coating, the component (k-2) was added and stirred and mixed for 30 minutes, and then immediately the component (l-5) was added and stirred and mixed for 10 minutes to obtain a composition for forming a metal chelate-containing silicone layer - 2. (f-1) "Exol" (registered trademark) DSP100 / 140: 240.00 parts by mass (g-1) Toluene: 60.00 parts by mass (h-3) A siloxane compound having two or more silanol groups in the molecule (both-terminal silanol-polydimethylsiloxane): DMS-S42 (manufactured by Gelest Inc., weight average molecular weight: 77,000, number of silanol groups in the molecule: 2.0): 75.99 parts by mass (k-2) Crosslinking agent: Vinyltris(methylethylketoximino)silane: 4.00 parts by mass (l-5) A compound obtained by removing the solvent from "Organix" (registered trademark) TC-150 by dry nitrogen blowing: 34.43 parts by mass.

[0168] [Example 37] Solid pulsed laser with a wavelength of 266 nm: “AONano” (registered trademark) 266-3-20-V (manufactured by Advanced Optowave Corporation), from the side of the metal chelate-free silicone layer of the original planographic printing plate without water, with an exposure dose of 2 J / cm 2 In the same manner as in Example 21, except that pattern drawing was performed in the air at an exposure dose of 2 J / cm

[0169] [Example 38] The laser exposure dose was changed to 3 J / cm 2 In the same manner as in Example 37, except for the change, an original planographic printing plate without water and a planographic printing plate without water were obtained.

[0170] [Example 39] The laser exposure dose was changed to 4 J / cm 2 In the same manner as in Example 37, except for the change, an original planographic printing plate without water and a planographic printing plate without water were obtained.

[0171] [Example 40] The laser exposure dose was changed to 5 J / cm 2 In the same manner as in Example 37, except for the change, an original planographic printing plate without water and a planographic printing plate without water were obtained.

[0172] [Example 41] The laser exposure dose was changed to 6 J / cm 2 In the same manner as in Example 37, except for the change, an original planographic printing plate without water and a planographic printing plate without water were obtained.

[0173] [Example 42] The laser exposure dose was changed to 7 J / cm 2 In the same manner as in Example 37, except for the change, an original planographic printing plate without water and a planographic printing plate without water were obtained.

[0174] [Example 43] Using a solid pulsed laser with a wavelength of 266 nm, from the side of the metal chelate-free silicone layer of the original planographic printing plate without water, with an exposure dose of 4 J / cm in the air2 A seamless waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 36, except that pattern drawing was performed at 2 .

[0175] [Example 44] The primer layer-forming composition was applied to the outer peripheral surface of a plate cylinder sleeve made of an aluminum alloy using a cylindrical slit coater (manufactured by Toray Engineering Co., Ltd.), and heated at 180 °C for 10 minutes to provide a continuous primer layer with an average thickness of 10 μm and no seams.

[0176] Next, the composition for forming a metal chelate-containing silicone layer used in Example 14 was applied to the outer peripheral surface of the primer layer using a cylindrical slit coater, and heated at 100 °C for 5 minutes to provide a continuous metal chelate-containing silicone layer with an average thickness of 5 μm and no seams.

[0177] Next, the composition - 1 for forming a metal chelate-free silicone layer was applied to the outer peripheral surface of the metal chelate-containing silicone layer using a cylindrical slit coater, and heated at 100 °C for 5 minutes to provide a continuous metal chelate-free silicone layer with an average thickness of 0.5 μm and no seams, thereby obtaining a seamless waterless lithographic printing plate precursor.

[0178] Using a solid pulse laser with a wavelength of 355 nm, from the side of the metal chelate-free silicone layer of the above seamless waterless lithographic printing plate precursor, the exposure amount in the air was: 5 J / cm 2 Pattern drawing was performed to obtain a seamless waterless lithographic printing plate.

[0179] [Example 45] Using a solid pulse laser with a wavelength of 266 nm, from the side of the metal chelate-free silicone layer of the seamless waterless lithographic printing plate precursor, the exposure amount in the air was: 4 J / cm 2 A seamless waterless lithographic printing plate precursor and a seamless waterless lithographic printing plate were obtained in the same manner as in Example 44, except that pattern drawing was performed at 2 .

[0180] [Comparative Example 1] The amount of DMS-V42, which is the component (h-1) of the composition for forming the metal chelate-containing silicone layer-1, was changed to 97.47 parts by mass, and a waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 1 except that the component (l-1), which is a metal chelate compound, was not added.

[0181] [Comparative Example 2] A waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 1 except that the composition for forming the metal chelate-containing silicone layer-1 was changed to the following composition for forming a metal chelate-free silicone layer-2.

[0182] [Composition for forming a metal chelate-free silicone layer-2] The following components (f-1), (g-1) and (h-3) were charged into a container and stirred and mixed until the component (h-3) was dissolved. The obtained solution was bubbled with dry nitrogen for 20 minutes to remove moisture in the solution. Immediately before coating, the component (k-2) was charged and stirred and mixed for 30 minutes, and then immediately the component (l-5) was charged and stirred and mixed for 10 minutes to obtain a composition for forming a metal chelate-containing silicone layer-2. (f-1) "Exol" (registered trademark) DSP100 / 140: 240.00 parts by mass (g-1) Toluene: 60.00 parts by mass (h-3) DMS-S42: 98.66 parts by mass (k-2) Vinyltris(methylethylketoximino)silane: 4.00 parts by mass (l-5) Compound obtained by removing the solvent from "Organix" (registered trademark) TC-150 by dry nitrogen blowing: 0.50 parts by mass.

[0183] [Comparative Example 3] The amount of DMS-V42, which is the (h-1) component of the composition for forming the metal chelate-containing silicone layer, was changed to 96.13 parts by mass, and the amount of the compound obtained by removing the solvent from “Organix” (registered trademark) TC-150, which is the (l-5) component, by dry nitrogen blowing was changed to 2.00 parts by mass. Otherwise, a waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 5.

[0184] [Comparative Example 4] The amount of DMS-V42, which is the (h-1) component of the composition for forming the metal chelate-containing silicone layer, was changed to 67.47 parts by mass, and the amount of the compound obtained by removing the solvent from “Organix” (registered trademark) TC-150, which is the (l-5) component, by dry nitrogen blowing was changed to 44.91 parts by mass. Otherwise, a waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 5.

[0185] [Comparative Example 5] The (l-1), which is the metal chelate component of the composition for forming the metal chelate-containing silicone layer-1, was changed to (m-1) metal alkoxide: “Organix” (registered trademark) AL-3001 (manufactured by Matsumoto Fine Chemical Co., Ltd., aluminum tri-sec-butoxide): 9.40 parts by mass. Otherwise, a waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 1.

[0186] [Comparative Example 6] The (l-1), which is the metal chelate component of the composition for forming the metal chelate-containing silicone layer-1, was changed to (m-2) metal alkoxide: “Organix” (registered trademark) TA-21 (manufactured by Matsumoto Fine Chemical Co., Ltd., titanium tri-n-butoxide): 12.99 parts by mass. Otherwise, a waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 1.

[0187] [Comparative Example 7] Except that the metal chelate component (l-1) of the composition for forming a metal chelate-containing silicone layer-1 was changed to 14.64 parts by mass of a compound obtained by removing the solvent from (m-3) metal alkoxide: “Organics” (registered trademark) ZA-65 (manufactured by Matsumoto Fine Chemical Co., Ltd., solution of zirconium tetra-n-butoxide / n-butanol = 87 / 13% by mass) by blowing dry nitrogen, a waterless lithographic printing plate precursor and a waterless lithographic printing plate were obtained in the same manner as in Example 1.

[0188] [Comparative Example 8] The following composition for forming a metal chelate-free silicone layer-3 was prepared.

[0189] [Composition for Forming a Metal Chelate-Free Silicone Layer-3] The following components (f-3), (h-4), (i-2), (k-3) and (n-1) were put into a container and stirred and mixed until the components were uniform. The resulting mixture was passed twice through a high-pressure valve type homogenizer: Ekonizer Lab 02 (manufactured by Maruwan Kikai Kogyo Co., Ltd.) to obtain a composition for forming a metal chelate-free silicone layer-3. (f-3) 2-Butanone: 900.00 parts by mass (h-4) Both ends silanol-polydimethylsiloxane: YF3802 (manufactured by Momentive Performance Materials Japan LLC, weight average molecular weight: 125,000, number of silanol groups in the molecule: 2.0): 60.00 parts by mass (i-2) Dibutyltin diacetate: 0.10 parts by mass (k-3) Methyltriacetoxysilane: 4.00 parts by mass (n-1) Photocatalyst particles: AMT-600 (anatase type photocatalytic titanium oxide particles, X-ray particle size: 30 nm, manufactured by Teika Co., Ltd.): 30.00 parts by mass.

[0190] Even in the composition for forming a metal chelate-free silicone layer immediately after dispersion, the photocatalyst particles rapidly aggregated / sedimented and a coating film could not be formed.

[0191] [Comparative Example 9] The composition for forming a metal chelate-containing silicone layer - 1 was changed to the following composition for forming a metal chelate-free silicone layer - 4, and the heating conditions after coating were changed to 120 °C for 2 minutes, and the average thickness of the metal chelate-free silicone layer after heating was changed to 1 μm. Otherwise, in the same manner as in Example 1, an original waterless lithographic printing plate and a waterless lithographic printing plate were obtained.

[0192] <Composition for forming a metal chelate-free ink-repellent silicone layer - 4> The following components (f-4), (g-2), (h-5), (i-3), (k-4) and (n-2) were charged into a container and stirred and mixed until the components were uniform to obtain a composition for forming a metal chelate-free ink-repellent silicone layer - 4. (f-4) 1,4-dioxane: 5.00 parts by mass (g-2) 2-propanol: 5.00 parts by mass (h-5) Both-terminal carbinol-modified polydimethylsiloxane: X-22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd., weight-average molecular weight: 1,000, number of carbinol groups in the molecule: 2.0): 9.00 parts by mass (i-3) Reaction catalyst: dibutyltin dilaurate: 0.05 parts by mass (k-4) Crosslinking agent: Coronate L (manufactured by Tosoh Corporation, trimethylolpropane / tolylene diisocyanate trimer adduct, solid content concentration: 75% by mass (solvent: ethyl acetate)): 1.00 parts by mass (n-2) Photocatalyst particles: ST-01 (manufactured by Ishihara Sangyo Co., Ltd., anatase-type photocatalytic titanium oxide particles, X-ray particle size: 7 nm): 1.00 parts by mass.

[0193] [Comparative Example 10] On the metal chelate-free silicone layer of Comparative Example 1, the following composition for forming a metal chelate-free silicone layer - 5 was applied and heated at 100 °C for 80 seconds to provide a metal chelate-free silicone layer (second layer) with an average thickness of 0.4 μm, thereby obtaining an original waterless lithographic printing plate.

[0194] <Composition for forming a metal chelate-free silicone layer - 5> The following components (f-2), (h-6), (i-1) and (j-1) were charged into a container and stirred and mixed until the components were uniform. The resulting solution was bubbled with dry nitrogen for 20 minutes to remove the moisture in the solution. Immediately before coating, the component (k-1) was added and stirred and mixed to obtain a composition-5 for forming a metal chelate-free silicone layer. (f-2) Isoparaffinic solvent: “Isopar” (registered trademark) C (manufactured by ExxonMobil Chemical Company): 895.0 parts by mass (h-6) Siloxane compound having 3 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): 70.0 parts by mass (i-1) XC94-C4326: 3.5 parts by mass (j-1) 2-Methyl-3-butyn-2-ol: 1.5 parts by mass (k-1) HMS-993: 30.0 parts by mass.

[0195] From the second layer side of the obtained waterless lithographic printing plate original plate, using an ArF excimer pulse laser with a wavelength of 193 nm: Excimer Laser MLI series (manufactured by Mlase), the exposure amount in the air: 75 mJ / cm 2 , the pulse repetition frequency: 10 Hz, laser exposure was performed under these conditions, and the second layer and the upper part of the first layer of the laser exposure part were ablated to obtain a waterless lithographic printing plate.

[0196] [Comparative Example 11] Except that the laser exposure amount was changed to 150 mJ / cm 2 , a waterless lithographic printing plate original plate and a waterless lithographic printing plate were obtained in the same manner as in Comparative Example 10.

[0197] For Examples 1 to 45 and Comparative Examples 1 to 11, the element concentrations in each layer are shown in Tables 1 to 3. Also, the evaluation results are shown in Tables 4 to 6.

[0198]

Table 1

[0199]

Table 2

[0200]

Table 3

[0201]

Table 4

[0202]

Table 5

[0203]

Table 6

Claims

1. An original lithographic printing plate precursor without water, having a metal chelate-containing silicone layer on a support, wherein the metal concentration derived from the metal chelate in the metal chelate-containing silicone layer measured by X-ray photoelectron spectroscopy is 0.2 to 1.8 atom%.

2. The original lithographic printing plate precursor without water according to claim 1, wherein the metal chelate includes a chelate ring formed from a β-diketone compound and / or a β-ketoester compound and a metal.

3. The original lithographic printing plate precursor without water according to claim 2, wherein the β-diketone compound includes acetylacetone.

4. The original lithographic printing plate precursor without water according to claim 2, wherein the β-ketoester compound includes an alkyl acetoacetate, and the alkyl has 2 to 8 carbon atoms.

5. The original lithographic printing plate precursor without water according to any one of claims 1 to 4, wherein the metal includes aluminum, titanium and / or zirconium.

6. The original lithographic printing plate precursor without water according to any one of claims 1 to 5, wherein the silicon concentration in the metal chelate-containing silicone layer measured by X-ray photoelectron spectroscopy is 15.5 to 24.5 atom%, the oxygen concentration is 25.0 to 28.5 atom%, and the carbon concentration is 50.0 to 57.0 atom%.

7. The original lithographic printing plate precursor without water according to any one of claims 1 to 6, wherein the average thickness of the metal chelate-containing silicone layer is 5 μm or more.

8. The original lithographic printing plate precursor without water according to any one of claims 1 to 7, further having a metal chelate-free silicone layer on the metal chelate-containing silicone layer.

9. The original lithographic printing plate precursor without water according to claim 8, wherein the silicon concentration in the metal chelate-free silicone layer measured by X-ray photoelectron spectroscopy is 22 to 26 atom%, the oxygen concentration is 24 to 28 atom%, and the carbon concentration is 48 to 52 atom%.

10. The original lithographic printing plate precursor without water according to claim 8 or 9, wherein the average thickness of the metal chelate-free silicone layer is 0.1 μm or more.

11. The original lithographic printing plate precursor without water according to any one of claims 1 to 10, wherein the support is cylindrical.

12. A method for manufacturing a lithographic printing plate without water, which comprises exposing the side of the metal chelate-containing silicone layer or the metal chelate-free silicone layer of the original lithographic printing plate precursor without water according to any one of claims 1 to 11 with active energy rays to form an ink-receptive part.

13. The method for producing a waterless lithographic printing plate precursor according to claim 12, wherein the peak wavelength of the active energy ray is 200 to 600 nm.

14. The method for producing a waterless lithographic printing plate according to claim 12 or 13, wherein the active energy ray is a pulsed laser.

15. The exposure amount of the pulsed laser is 2 to 8 J / cm ２ The method for producing a waterless lithographic printing plate according to claim 14, wherein the exposure amount is as described above.

16. At least (1) A step of continuously applying a composition for forming a metal chelate-containing silicone layer, which contains a polysiloxane having two or more silanol groups or vinyl groups in the molecule, a crosslinking agent having three or more functional groups reactive with the silanol group or the vinyl group in the molecule, and a metal chelate compound having one or more chelate rings in the molecule, and the content of the metal chelate compound is 4 to 60% by mass in the total solid content, and (2) A step of curing the coating film obtained in step (1) to form a metal chelate-containing silicone layer The method for producing a waterless lithographic printing plate precursor according to any one of claims 1 to 11, comprising:

17. Before or after step (2), (3) A step of continuously applying a composition for forming a metal chelate-free silicone layer on the coating film obtained in step (1) or the metal chelate-containing silicone layer obtained in step (2), and (4) A step of curing the coating film obtained in step (3) to form a metal chelate-free silicone layer The method for producing a waterless lithographic printing plate precursor according to claim 16, comprising:

Images