JP2009233912A - Aluminum support body for lithographic printing plate material, its manufacturing method, and lithographic printing plate material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive lithographic printing plate material which enables a superior evenness in image reproduction and to provide a support body which realizes it, and its manufacturing method. <P>SOLUTION: The manufacturing method for the aluminum support body for the lithographic printing plate material includes in the following order: the electrolytic surface roughening process wherein a wound aluminum web is reeled out and transferred to conduct the surface roughening process; the anodizing process wherein the anodizing process is conducted; a hydrophilic process wherein a hydrophilic process is conducted; the drying process wherein drying is conducted; and also characteristically including the flattening process wherein the curling degree is decreased to 1.0 mm or less before the electrolytic surface roughening process. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a lithographic printing plate material, an aluminum support for the lithographic printing plate material used therefor, and a method for producing the same.

  In recent years, CTP recording digital image data directly on a photosensitive printing plate with a laser light source has been developed and is being put to practical use in the technology for producing printing plates for offset printing.

  Among these, in the field of printing that requires a relatively high printing durability, it is known to use a lithographic printing plate material having an aluminum plate as a support and an image forming layer thereon.

  Lithographic printing is a printing method that uses fountain solution and printing ink. At the time of printing, the non-image area of the lithographic printing plate must be hydrophilic, water-retaining, and ink repellent. is there.

  In order to make the non-image part of the lithographic printing plate hydrophilic and water-retaining, the surface of the aluminum plate is roughened to further improve printability and printing durability. A material subjected to an anodizing treatment and a hydrophilization treatment is generally used.

  As the surface shape of the aluminum support subjected to these treatments such as a roughening treatment, various structures are known as follows.

For example, a triple structure having a large wave, a medium wave, and a small wave that define the aperture diameters of the medium wave and the small wave described in JP-A-8-300844, JP-A-11-99758, and JP-A-11-208138 A structure that defines the diameter of a small wave in the described large and small double structure, a double structure that defines the opening diameter described in Japanese Patent No. 2023476, and the smoothness of the surface described in JP-A-8-300843 A double structure in which a factor is defined, a structure in which a ratio of pit diameters to be superimposed in a plurality of electrochemical surface roughening treatments described in JP-A-10-35133 is defined, and a recess having a depth of 3 μm or more present on the surface the number is 60 pieces / mm ² or less, with respect to the position where the frequency has a peak in the amplitude distribution curve of three-dimensional surface roughness curve (peak depth), spreading to the shallow region side of the amplitude distribution curve (width A surface shape (see Patent Document 1) having a ratio (Xa / Xb) of 0.8a to 1.2b (Xa / Xb) of Xa to the deeper region (width) Xb is known.

  Furthermore, it has a surface shape in which the arithmetic mean roughness (Ra) is in the range of 0.40 to 0.60 μm, and the root mean square slope (RΔq) of the roughness curve is in the range of 0.20 to 0.25, A support in which an aluminum plate contains 0.05 to 0.4 mass% of Mg (see Patent Document 2) is known.

  On the other hand, when producing a large amount of a lithographic printing plate material, generally, the aluminum support is unwound from a coiled state and is subjected to the above-described processing while being conveyed, and an image forming layer is provided. . In this case, since the aluminum support has been deformed due to the wound state or the like, there has been a problem that application failure may occur when the image forming layer is provided by application. In order to improve this, a method of providing a planarization process step immediately before the image forming layer coating step is known (see Patent Document 3).

However, in the planographic printing plate material in which the image forming layer is formed on the aluminum support for these planographic printing plate materials, printability and uneven application of the image forming layer are improved, but the image reproducibility is still uneven. In some cases, there is a problem that the uniformity of image reproduction is insufficient.
JP 2004-98456 A JP 2006-305819 A JP 2007-83609 A

  An object of the present invention is to provide a photosensitive lithographic printing plate material excellent in image reproduction uniformity, a support for providing the same, and a method for producing the same.

The object of the present invention is achieved by the following constitution.
1. The wound aluminum web is unwound, conveyed and subjected to an electrolytic surface roughening treatment, an electrolytic surface roughening treatment step, an anodizing treatment step for anodizing treatment, a hydrophilic treatment step for hydrophilic treatment, and drying. A method for producing an aluminum support for a lithographic printing plate material having drying steps in this order, comprising a planarization treatment step of performing a planarization treatment with a curl degree of 1.0 mm or less before the electrolytic surface-roughening treatment step A method for producing an aluminum support for a lithographic printing plate material, comprising:
2. 2. The method for producing an aluminum support for a lithographic printing plate material according to 1, wherein the aluminum web is unwound and has a conveyance speed adjustment step before the planarization treatment step.
3. 3. The method for producing an aluminum support for a lithographic printing plate material according to 1 or 2, wherein the electrolytic surface-roughening treatment is performed in an electrolytic solution containing hydrochloric acid.
An aluminum support for a lithographic printing plate material produced by the method for producing an aluminum support for a lithographic printing plate material according to any one of 4.1 to 3.
5. A lithographic printing plate material comprising an image forming layer on the aluminum support for a lithographic printing plate material described in 5.4.

  With the above configuration of the present invention, a photosensitive lithographic printing plate material excellent in image reproduction uniformity, a support for providing the same, and a method for producing the same can be provided.

  Hereinafter, the present invention will be described in detail.

  The present invention relates to an electrolytic surface-roughening treatment step for unwinding and conveying a wound aluminum web and carrying out an electrolytic surface-roughening treatment, an anodizing treatment step for carrying out an anodizing treatment, and a hydrophilic treatment step for carrying out a hydrophilic treatment. And a method for producing an aluminum support for a lithographic printing plate material having a drying step in this order, wherein the flattening treatment is performed so that the curl degree is 1.0 mm or less before the electrolytic surface-roughening treatment step. It has the characteristic of having a chemical conversion treatment process.

  In the present invention, an aluminum support that provides a photosensitive lithographic printing plate material excellent in image reproduction uniformity can be obtained by performing a planarization treatment before the electrolytic surface roughening treatment.

(Aluminum web)
The aluminum web according to the present invention is a long aluminum plate.

  The aluminum plate is a pure aluminum plate or an aluminum alloy plate.

  Various aluminum alloys can be used, for example, alloys of aluminum and metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, etc. An aluminum plate produced by the method can be used. In addition, a recycled aluminum plate obtained by rolling recycled aluminum ingots such as scrap materials and recycled materials that are becoming popular in recent years can also be used.

  In the present invention, an aluminum plate having an aluminum content of 99.5% by mass or more and a Cu content of 0.005% by mass or less is preferably used.

(Planarization process)
The manufacturing method of the present invention includes a planarization treatment step for performing a planarization treatment for setting the curl degree to 1.0 mm or less before the electrolytic surface-roughening treatment. An aluminum support cut to a size of 800 mm is placed on a horizontal table with the surface on which the image forming layer is provided or the surface on which the image forming layer is provided facing down, and the distance between the aluminum support and the horizontal table is 4 A value obtained by measuring all corners and calculating the average value of the distances of the corners. For the measurement, a scale in increments of 0.1 mm is used.

  The curl degree of the flattened web is preferably 0.5 mm or less, and more preferably 0.

  Hereinafter, the configuration of the present invention will be described with reference to FIG.

  FIG. 1 shows a schematic view of an example of a production apparatus used in the method for producing an aluminum support of the present invention.

  The aluminum web A2 unwound from the wound aluminum web A1 is conveyed by a conveying roller 203 or the like. The aluminum web is processed through a flattening treatment step 100, an electrolytic surface roughening treatment step 1, an anodizing treatment step 2, a hydrophilization treatment step 3, and a drying step 4 through a conveyance speed adjustment step 200 provided as necessary. .

  The manufacturing method of the aluminum support body of this invention has a planarization process process before an electrolytic surface-roughening process process.

  The flattening process according to the present invention is a process in which a curling degree of the aluminum web to be treated is reduced by applying a force for deforming the aluminum web so that the curling degree is 1.0 mm or less.

  As a method for applying a force for deforming the aluminum web, there are a method using a roller leveler using a plurality of rollers, a method using a so-called decurler having a wide pitch between rolls, and the like.

  FIG. 1 shows a method using a roller leveler.

  The aluminum web A3 (the surface having the image forming layer on the upper side) before being flattened is applied with force by the roller 101 and the roller 102 in the flattening step 100.

  The roller shaft of the roller 101 and the roller shaft of the roller 102 are shifted along the transport direction of the aluminum web to be transported. As a result, the aluminum web can be bitten and conveyed alternately by the roller 101 and the roller 102, and the force can be repeatedly applied in the opposite directions by the roller 101 and the roller 102 to reduce the curl of the aluminum web.

  The force applied in the opposite direction can be adjusted by the distance between the axis of the roller 101 and the axis of the roller 102. The distance between the shaft of the roller 101 and the shaft of the roller 102 can be adjusted by moving the position of each bearing (not shown).

  As the material of the roller 101, a metallic roller whose surface is covered with urethane rubber, silicon rubber or the like is preferably used.

  As the material of the roller 102, a metallic roller such as stainless steel is preferably used.

  In the present invention, the curl degree of the flattened aluminum web A4 is 1 mm or less.

  The method for producing an aluminum support for a lithographic printing plate material of the present invention is after unwinding an aluminum web and preferably has a conveyance speed adjustment step before the planarization treatment step. The invention is effective.

  The unwound aluminum web A1 has a portion called a normal accumulator that adjusts the conveyance speed because it is necessary to change the conveyance speed temporarily for cutting, coil switching, etc. during the manufacturing process. .

  The conveyance speed of the aluminum web to be conveyed is adjusted by, for example, the vertical movement of the roller 201.

(Electrolytic roughening process)
Next, the planarized aluminum web A4 is subjected to electrolytic surface roughening.

  In the electrolytic surface roughening step 1, electrolytic treatment is performed through the electrode 18 with the following electrical quantity in the electrolytic solution 12 filled in the electrolytic surface roughening treatment tank 11.

In the electrolytic surface roughening step 1, the current density is preferably from 15~120A / dm ^2, particularly preferably 20~90A / dm ^2.

Preferably the quantity of electricity is 400~2000C / dm ^2, particularly preferably 500~1200C / dm ^2. The frequency is preferably in the range of 40 to 150 Hz.

  The temperature of the electrolytic solution can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C.

  As the electrolytic solution for electrolytic surface roughening treatment according to the present invention, an electrolytic solution containing hydrochloric acid is preferably used. The electrolytic solution containing hydrochloric acid is an aqueous solution containing 1% by mass or more of hydrochloric acid (as HCl), preferably the hydrochloric acid concentration is 5 to 20 g / l, particularly preferably 6 to 15 g / l.

  Nitrate, chloride, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, aluminum ions and the like can be added to the electrolytic solution.

  The aluminum ion concentration in the electrolytic solution is preferably 0.5 to 15 g / l, more preferably 0.7 to 10 g / l, particularly preferably 1 to 5 g / l, most preferably 1 to 2.5 g / l. .

  The electrolyte solution preferably contains acetic acid or boric acid, and the concentration is 1 to 20 g / l, preferably 3 to 15 g / l. The ratio to the hydrochloric acid concentration is preferably 0.5 to 1.5.

  The transport speed is preferably 5 m / min to 25 m / min, particularly preferably 7 m / min to 20 m / min, relative to the electrolytic solution 12 contained in the electrolytic cell 11.

  The temperature at which the electrolytic surface roughening treatment is performed is preferably 15 ° C to 45 ° C, and particularly preferably 18 ° C to 38 ° C.

  The electrolytic surface roughening treatment is performed as described above. The reason why the lithographic printing plate material according to the present invention is excellent in the uniformity of image reproduction is presumed as follows.

  That is, it is presumed that the curling degree is reduced by the planarization treatment as described above, and the subsequent electrolytic surface roughening treatment is performed extremely uniformly.

  Moreover, in the manufacturing method of the aluminum support body of this invention, it is preferable to perform a degreasing process (not shown) in order to remove the rolling oil of a surface prior to an electrolytic surface-roughening process process.

  As the degreasing treatment, a degreasing treatment using a solvent such as trichlene or thinner, an emulsion degreasing treatment using an emulsion such as kesilon or triethanol, or the like is used. In addition, an alkaline aqueous solution such as caustic soda can be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, dirt and oxide film that cannot be removed only by the degreasing treatment can be removed. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is generated on the surface of the support. In this case, the substrate is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof and desmutted. It is preferable to perform the treatment.

  In the electrolytic surface-roughening treatment step 1 after the desmut treatment, the aluminum web is immersed in the electrolytic solution 12 and the electrolytic surface-roughening of the aluminum web in the subsequent electrolytic step 13 is performed.

  The planarization treatment step may be performed after or before the degreasing treatment, but an embodiment performed before the degreasing treatment is a preferred embodiment.

(Desmut treatment (not shown))
After the electrolytic surface roughening treatment is performed in the electrolytic solution, it is preferably immersed in an acid or alkali aqueous solution in order to remove aluminum scraps on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an alkaline aqueous solution. In this case, the amount of aluminum dissolved on the surface is preferably 0.5 to ² g / m ² . In addition, it is preferable that after the immersion treatment with an alkaline aqueous solution, neutralization treatment is performed by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

(Anodizing process)
Following the electrolytic surface roughening treatment step 1, an anodization treatment is performed in an anodization treatment step 2 to form an anodized film.

The anodizing method is preferably carried out using sulfuric acid or an electrolytic solution mainly composed of sulfuric acid as the electrolytic solution. The concentration of sulfuric acid is preferably 5 to 50% by mass, particularly preferably 10 to 35% by mass. The temperature is preferably 10 to 50 ° C. The treatment voltage is preferably 18 V or more, and more preferably 20 V or more. Current density is preferably 1~30A / dm ^2. Quantity of electricity is preferably from 200~600C / dm ^2.

The formed anodic oxidation coating amount is preferably ² to 6 g / m ² , and preferably 3 to 5 g / m ² . The anodic oxidation coating amount is obtained by, for example, immersing an aluminum plate in a chromic phosphate solution (produced by dissolving 85% phosphoric acid solution: 35 ml, chromium oxide (IV): 20 g in 1 L of water), dissolving the oxide coating, It is calculated | required from the mass change measurement etc. before and after melt | dissolution of the coating. Micropores are generated in the anodized film, and the density of the micropores is preferably 400 to 700 / μm ^{2, and} more preferably 400 to 600 / μm ² .

  The anodized aluminum support may be sealed as necessary. These sealing treatments can be performed using known methods such as hot water treatment, boiling water treatment, water vapor treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, and ammonium acetate treatment.

(Hydrophilic treatment process)
In the manufacturing method of this invention, after performing said process, it has the hydrophilization process process 3 and the drying process 4 following it.

  The hydrophilic treatment step is a step of treating the aluminum support with an aqueous solution containing a hydrophilic material. Examples of hydrophilic materials include polysaccharides, polyethylene oxide, polypropylene oxide, polyvinyl alcohol, polyethylene glycol (PEG), polyvinyl ether, styrene-butadiene copolymer, conjugated diene polymer latex of methyl methacrylate-butadiene copolymer. , Acrylic polymer latex, vinyl polymer latex, water-soluble resin such as polyacrylamide and polyvinylpyrrolidone, and phosphonic acid such as polyvinylphosphonic acid.

  Examples of the hydrophilic treatment include, but are not limited to, a coating method, a spray method, and a dip method. As this process, a dip type is preferable from the viewpoint of cost.

  In the case of a dip type, it is preferable to treat with a 0.1 to 5.0 mass% aqueous solution of a hydrophilic material. The treatment temperature is preferably 10 to 90 ° C, particularly preferably 50 to 90 ° C. The treatment time is preferably 5 to 180 seconds.

  The temperature of the aqueous solution containing polyvinylphosphonic acid is preferably 25 to 90 ° C. in terms of printing durability and prevention of stains, and the treatment time is preferably 5 seconds to 1 minute.

  As the hydrophilic material, polyvinylphosphonic acid is particularly preferably used. That is, as the hydrophilization treatment step 3, a treatment step is preferable with an aqueous solution containing polyvinylphosphonic acid.

  When processing with the aqueous solution containing polyvinylphosphonic acid, it is preferable that polyvinylphosphonic acid exists in the range of 0.05-0.6 mass% with respect to aqueous solution. Furthermore, it is still more preferable to use in 0.1-0.4 mass%. Moreover, when performing by a dip type, it is preferable to process with the 0.1-0.4 mass% aqueous solution of polyvinylphosphonic acid. The treatment temperature is preferably 20 to 90 ° C, particularly preferably 50 to 90 ° C. The treatment time is preferably 10 to 180 seconds.

  The temperature of the aqueous solution containing polyvinylphosphonic acid is preferably 25 to 90 ° C. in terms of printing durability and prevention of stains, and the treatment time is preferably 5 seconds to 1 minute.

  Polyvinylphosphonic acid is a vinyl polymer having a phosphonic acid group, preferably having a number average molecular weight of 5,000 to 40,000, particularly preferably 10,000 to 25,000. In the hydrophilization treatment step 3, a water washing treatment may be performed as necessary.

  The washing treatment is a treatment for removing excess hydrophilic material, and includes a method of spraying washing water and a method of dipping in washing water, and a method of spraying washing water is preferably used. The temperature of the washing water used for the water washing treatment is preferably in the range of 20 ° C to 60 ° C, particularly preferably in the range of 25 ° C to 40 ° C. The time for the water washing treatment is preferably 1 to 30 seconds, and particularly preferably 2 to 20 seconds.

  After the water washing treatment, the drying process 4 is performed.

  The drying process 4 is a process performed after the hydrophilization treatment process 3. In the drying process 4, the aluminum plate is heated by a heating means.

  The aluminum web dried by the air heated by the heating means 41 in the drying unit process 4 is then brought into contact with the rubber roller 6 and conveyed and wound up by the winding unit 7.

  Moreover, when performing an application | coating process, a drying process, and a cutting process continuously, it is used for the application | coating process of an image forming layer instead of the winding part 7. FIG.

(Image forming layer)
The image forming layer according to the present invention is a layer capable of forming an image by image exposure, and any of a negative type and a positive type image forming layer conventionally used as a photosensitive layer of a lithographic printing plate can be used.

  The present invention is effective when the image forming layer according to the present invention is a heat-sensitive image forming layer and a polymerization type image forming layer, and particularly effective in the case of a polymerization type image forming layer.

  As the heat-sensitive image forming layer, a layer that causes a change capable of forming an image by using heat generated by laser exposure is preferably used.

  Examples of the heat-sensitive image forming layer using heat generated by laser exposure include a positive heat-sensitive image forming layer containing a substance decomposable by acid, a heat-sensitive image forming layer containing a polymerization component, and a heat-sensitive image containing a thermoplastic substance. A negative thermal image forming layer such as a forming layer is preferably used.

  The removal of the thermal image forming layer is preferably performed on a printing press. That is, an embodiment in which the heat-sensitive image forming layer is a layer that can be developed on a printing press is preferred.

  “Developable on a printing press” means that the image forming layer in the non-image area can be removed by dampening water and / or printing ink in lithographic printing after exposure.

  As a positive type image forming layer containing a substance decomposable by acid, for example, a photo acid generator that generates acid by laser exposure described in JP-A-9-171254 and a photo acid generator that generates acid by the laser exposure described above, And an image-forming layer comprising an acid-decomposable compound and an infrared absorber that increase solubility in water.

Examples of the photoacid generator include various known compounds and mixtures. For example, diazonium, phosphonium, sulfonium, and iodonium salts such as BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , ClO ₄ ⁻ , organic halogen compounds, orthoquinone-diazide sulfonyl chloride, and organometallic / An organic halogen compound is also an actinic ray-sensitive component that forms or separates an acid upon irradiation with actinic rays, and can be used as a photoacid generator. In principle, all organic halogen compounds known as free radical-forming photoinitiators are compounds that form hydrohalic acid and can be used as photoacid generators. Examples of the above-mentioned compounds forming hydrohalic acid include U.S. Pat. Nos. 3,515,552, 3,536,489 and 3,779,778, and West German Patent 2,243,621. In addition, compounds that generate an acid by photolysis described in West German Patent 2,610,842 can also be used. Further, o-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-50-36209 can be used.

  As the photoacid generator, an organic halogen compound is preferable from the viewpoints of sensitivity in image formation by infrared exposure and storage stability of the image forming material. As the organic halogen compound, triazines having a halogen-substituted alkyl group and oxadiazoles having a halogen-substituted alkyl group are preferable, and s-triazines having a halogen-substituted alkyl group are particularly preferable.

  The content of the photoacid generator can vary widely depending on its chemical properties and the composition or physical properties of the image forming layer, but it is about 0.1 to about 20 with respect to the total mass of the solid content of the image forming layer. The range of mass% is appropriate, and preferably in the range of 0.2 to 10 mass%.

  Specific examples of the acid-decomposing compound are described in JP-A Nos. 48-89003, 51-120714, 53-133429, 55-12995, 55-126236, and 56-17345. Compounds having a C—O—C bond, compounds having a Si—O—C bond described in JP-A-60-37549, JP-A-60-121446, JP-A-60-3625, Other acid-decomposing compounds described in No. 60-10247. Further, compounds having Si-N bonds described in Japanese Patent Application No. 61-16687, carbonates described in Japanese Patent Application No. 61-94603, ortho described in Japanese Patent Application No. 60-251744. Carbonate ester, orthotitanate ester described in Japanese Patent Application No. 61-125473, orthosilicate ester described in Japanese Patent Application No. 61-125474, acetal described in Japanese Patent Application No. 61-155481, and Ketal, compounds having a C—S bond described in Japanese Patent Application No. 61-87769, and the like. Of these, JP-A-53-133429, JP-A-56-17345, and JP-A-60-112446. No. 60-37549 and Japanese Patent Application Nos. 60-251744 and 61-155481. Compounds having a case, a compound having Si-O-C bonds, orthocarbonates, acetals, ketals and silyl ethers are preferable.

  The content of the acid-decomposing compound is preferably from 5 to 70% by mass, particularly preferably from 10 to 50% by mass, based on the total solid content of the composition forming the image forming layer. The acid decomposition compound may be used alone or in combination of two or more.

  The heat-sensitive image forming layer is preferably a mode including a photothermal conversion material that converts exposure light into heat. As the photothermal conversion material, the following photoconversion dyes and other photothermal conversion materials are used.

[Photothermal conversion dye]
The following can be used as the photothermal conversion dye.

  General infrared absorbing dyes such as cyanine dyes, croconium dyes, polymethine dyes, azurenium dyes, squalium dyes, thiopyrylium dyes, naphthoquinone dyes, anthraquinone dyes, organic compounds such as phthalocyanine dyes and naphthalocyanine dyes , Azo-based, thioamide-based, dithiol-based, and indoaniline-based organometallic complexes. Specifically, JP-A-63-139191, JP-A-64-33547, JP-A-1-160683, JP-A-1-280750, JP-A-1-293342, JP-A-2-2074, Kaihei 3-26593, JP-A-3-30991, JP-A-3-34891, JP-A-3-36093, JP-A-3-36094, JP-A-3-36095, JP-A-3-42281, JP-A-3-42281 Examples thereof include compounds described in JP-A-3-97589, JP-A-3-103476, and the like. These can be used alone or in combination of two or more.

  JP-A-11-240270, JP-A-11-265062, JP-A-2000-309174, JP-A-2002-49147, JP-A-2001-162965, JP-A-2002-144750, JP-A-2001-219667. The compounds described in (1) can also be preferably used.

[Other photothermal conversion materials]
In addition to the photothermal conversion dye, other photothermal conversion materials can be used in combination.

  Examples of the photothermal conversion material preferably used include carbon, graphite, metal, metal oxide and the like.

  As carbon, furnace black or acetylene black is particularly preferable. The particle size (d50) is preferably 100 nm or less, and more preferably 50 nm or less.

  As the graphite, fine particles having a particle size of 0.5 μm or less, preferably 100 nm or less, more preferably 50 nm or less can be used.

  As the metal, any metal can be used as long as the particle diameter is 0.5 μm or less, preferably 100 nm or less, more preferably 50 nm or less. The shape may be any shape such as a spherical shape, a piece shape, or a needle shape. Colloidal metal fine particles (Ag, Au, etc.) are particularly preferable.

  As the metal oxide, a material that is black in the visible light region, or a material that has conductivity or is a semiconductor can be used.

Examples of the former include black iron oxide (Fe ₃ O ₄ ) and black composite metal oxides containing two or more metals.

Examples of the latter include Sb-doped SnO ₂ (ATO), Sn-added In ₂ O ₃ (ITO), TiO ₂ , and TiO ₂ reduced TiO (titanium oxynitride, generally titanium black). Can be mentioned.

Further, it can also be used those obtained by coating the core material _{(BaSO 4, TiO 2, 9Al} 2 O 3 · 2B 2 O, K 2 O · nTiO 2 , etc.) in these metal oxides.

  These particle sizes are 0.5 μm or less, preferably 100 nm or less, and more preferably 50 nm or less.

  Of these photothermal conversion materials, a black composite metal oxide containing two or more metals is more preferable.

  Specifically, it is a composite metal oxide composed of two or more metals selected from Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sb, and Ba. These are disclosed by methods disclosed in JP-A-8-27393, JP-A-9-25126, JP-A-9-237570, JP-A-9-241529, JP-A-10-231441, and the like. Can be manufactured.

  The composite metal oxide is particularly preferably a Cu-Cr-Mn-based or Cu-Fe-Mn-based composite metal oxide. In the case of a Cu—Cr—Mn system, it is preferable to perform the treatment disclosed in JP-A-8-27393 in order to reduce elution of hexavalent chromium. These composite metal oxides are colored with respect to the amount added, that is, they have good photothermal conversion efficiency.

  These composite metal oxides preferably have an average primary particle size of 1 μm or less, and more preferably have an average primary particle size in the range of 0.01 to 0.5 μm. When the average primary particle diameter is 1 μm or less, the photothermal conversion ability with respect to the addition amount becomes better, and when the average primary particle diameter is within the range of 0.01 to 0.5 μm, the photothermal conversion ability with respect to the addition amount is obtained. Better.

  However, the photothermal conversion ability with respect to the addition amount is greatly affected by the degree of dispersion of the particles, and the better the dispersion, the better.

  Therefore, it is preferable to disperse these composite metal oxide particles by a known method separately before adding them to the layer coating solution to prepare a dispersion (paste). An average primary particle size of less than 0.01 is not preferable because dispersion becomes difficult. A dispersing agent can be appropriately used for the dispersion. The addition amount of the dispersant is preferably 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass with respect to the composite metal oxide particles.

  This image forming layer may appropriately contain a binder as necessary.

  Moreover, as a positive type image forming layer, a layer containing an O-naphthoquinonediazide compound can be preferably used.

  The light-to-heat conversion material may be contained in the image forming layer, or a layer adjacent to the image forming layer may be provided and contained in this adjacent layer.

  The thermosensitive image forming layer containing a polymerization component contains, for example, (a) a photothermal conversion material having absorption in the wavelength range of 700 nm to 1300 nm, (b) a polymerization initiator, and (c) a polymerizable unsaturated group-containing compound. A thermal image forming layer is mentioned.

((A) Photothermal conversion material having absorption in the wavelength range of 700 nm to 1300 nm)
As the photothermal conversion material having absorption in the wavelength range of 700 nm to 1300 nm, the above infrared absorbers can be used, preferably cyanine dyes, squarylium dyes, oxonol dyes, pyrylium dyes, thiopyrylium dyes, polymethine dyes, Oil-soluble phthalocyanine dyes, triarylamine dyes, thiazolium dyes, oxazolium dyes, polyaniline dyes, polypyrrole dyes, and polythiophene dyes are used.

  In addition, pigments such as carbon black, titanium black, iron oxide powder and colloidal silver can also be preferably used. From the viewpoints of absorption coefficient, photothermal conversion efficiency, price, etc., cyanine dyes are particularly preferable as the dyes, and carbon black is particularly preferable as the pigments.

The addition amount of the photothermal conversion material having absorption in the wavelength range from 700 nm to 1300 nm in the image forming layer varies depending on the extinction coefficient of the photothermal conversion material, but the reflection density of the lithographic printing plate material at the exposure wavelength is 0.3 to It is preferable to add an amount in the range of 3.0. More preferably, the addition amount is such that the concentration is in the range of 0.5 to 2.0. For example, in the case of the cyanine dyes mentioned in the above preferred specific examples, an amount of about 10 to 100 mg / m ² is added to the image forming layer in order to obtain the concentration.

  These photothermal conversion materials may be contained in the image forming layer in the same manner as described above, or an adjacent layer adjacent to the image forming layer may be provided and contained in this adjacent layer.

((B) Polymerization initiator)
The polymerization initiator is a compound capable of initiating polymerization of a compound having a polymerizable unsaturated group by laser exposure. Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo, diazo compounds, halogen compounds, and photoreductive dyes as described in Chapter 5 of “Light Sensitive Systems” by J. Kosar Etc. More specific compounds are disclosed in British Patent 1,459,563.

  That is, the following can be used as the polymerization initiator.

  Benzoin derivatives such as benzoin methyl ether, benzoin-i-propyl ether, α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4′-bis (dimethyl) Benzophenone derivatives such as amino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-i-propylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methylacridone, N-butylacridone and the like In addition to α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone and uranyl compounds, JP-B-59-1281, JP-A-61-9621 and JP-A-60-60104 Triazine derivatives described in Japanese Patent Publication No. JP-A-59-1504 and JP-A-61-243807; JP-B Nos. 43-23684, 44-6413, 44-6413 No. 47-1604 and U.S. Pat. No. 3,567,453; diazonium compounds; U.S. Pat. Nos. 2,848,328, 2,852,379 and 2,940,853 O-quinonediazides described in JP-B-36-22062, JP-A-37-13109, JP-A-38-18015 and JP-A-45-9610; JP-B-55-39162, JP-A-59-14023 No. and “Macromolecules”, Vol. 10, p. 1307 (1977) Various onium compounds; azo compounds described in JP-A-59-142205; JP-A-1-54440, European Patents 109,851, 126,712 and “Journal of Imaging Science (J. Imag) Sci.)], 30, 174 (1986); (oxo) sulfonium organoboron complexes described in Japanese Patent Application Nos. 4-56831 and 4-89535; Nos. 152396 and 61-151197; “Coordination Chemistry Review” 84, 85-277 (1988), and ruthenium described in JP-A-2-182701. Contains transition metals Transition metal complexes; triarylimidazole dimer of JP-A 3-209477 JP; carbon tetrabromide, organic halogen compounds in JP 59-107344 JP like.

  Further, examples of the polymerization initiator include compounds capable of generating radicals described in JP-A-2002-537419, JP-A-2001-175006, JP-A-2002-278057, JP-A-2003-5363. In addition, an onium salt having two or more cation moieties in one molecule, an N-nitrosamine compound described in JP-A-2001-133966, described in JP-A-2003-76010, JP-A-2001-343742 generates a radical by heat, JP-A-2002-6482 generates an acid or a radical by heat, JP-A-2002-116539, borate compound, JP-A-2002-148790 Japanese Patent Application Laid-Open No. 2002-207 No. 93, a photo- or thermal polymerization initiator having a polymerizable unsaturated group, JP-A No. 2002-268217, an onium salt having a divalent or higher anion as a counter ion, and JP-A No. 2002-328465 specific structure A compound such as a sulfonylsulfone compound or a compound that generates radicals by heat described in JP-A-2002-341519 can also be used.

  Of these, onium salt compounds and polyhalogen compounds are preferred.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. 18, 387 (1974), T .; S. Diazonium salts described in Bal etal, Polymer, 21, 423 (1980); ammonium salts described in US Pat. Nos. 4,069,055, 4,069,056, 4,027,992, and the like; D. C. Necker et al., Macromolecules, 17, 2468 (1984), C.I. S. Wenetal, Teh, Proc. Conf. Rad. CuringASIA, p478 Tokyo, Oct (1988), U.S. Pat. Nos. 4,069,055, 4,069,056, etc .; V. Crivello et al., Macromolecules, 10 (6), 1307 (1977), Chem. &Amp;; Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Pat. Nos. 339,049, 410,201, JP-A-2-150848, JP-A-2-296514, and the like; J. et al. V. Crivello et al., Polymer J .; 17, 73 (1985), J. Am. V. Crivello et al. J. et al. Org. Chem. 43, 3055 (1978); R. Wattal, J. et al. PolymerSci. , Polymer Chem. Ed. , 22, 1789 (1984), J. Am. V. Crivello et al., Polymer Bull. 14, 279 (1985), J. Am. V. Crivello et al., Macromolecules, 14 (5), 1141 (1981), J. MoI. V. Crivello et al. PolymerSci. , Polymer Chem. Ed. 17, 2877 (1979), European Patent Nos. 370,693, 3,902,114, 233,567, 297,443, 297,442, US Pat. No. 4,933,377 No. 161,811, No. 410,201, No. 339,049, No. 4,760,013, No. 4,734,444, No. 2,833,827, Yasukuni Patent No. 2, Sulfonium salts described in Nos. 904, 626, 3,604, 580, 3,604, 581, etc .; V. Crivello et al., Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al. PolymerSci. , Polymer Chem. Ed. , 17, 1047 (1979), etc .; C.I. S. Wenetal, Teh, Proc. Conf. Rad. CuringASIA, p478 Tokyo, Oct (1988), and the like.

  Of the onium salts mentioned above, iodonium salts and sulfonium salts are particularly preferably used.

  Preferred examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, methyldiphenylsulfonium tetrafluoroborate, dimethylphenylsulfonium hexafluorophosphate, 4-butoxyphenyldiphenylsulfonium tetrafluoroborate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, Tri (4-phenoxyphenyl) sulfonium hexafluorophosphate, di (4-ethoxyphenyl) methylsulfonium hexafluoroarsenate, 4-acetonylphenyldiphenylsulfonium tetrafluoroborate, 4-thiomethoxyphenyldiphenylsulfonium hexafluorophosphate, di ( Methoxysulfonylphenyl) methylsulfonium Xafluoroantimonate, di (nitrophenyl) phenylsulfonium hexafluoroantimonate, di (carbomethoxyphenyl) methylsulfonium hexafluorophosphate, 4-acetamidophenyldiphenylsulfonium tetrafluoroborate, dimethylnaphthylsulfonium hexafluorophosphate, trifluoromethyldiphenyl Sulfonium tetrafluoroborate, p- (phenylthiophenyl) diphenylsulfonium hexafluoroantimonate, 10-methylphenoxathinium hexafluorophosphate, 5-methylthiantrenium hexafluorophosphate, 10-phenyl-9,9-dimethylthio Xanthenium hexafluorophosphate, triphenylsulfonium tetra Scan can be given (pentafluorophenyl) borate.

  Preferred examples of the iodonium salt include diphenyliodonium iodide, diphenyliodonium hexafluoroantimonate, 4-chlorophenyliodonium tetrafluoroborate, di (4-chlorophenyl) iodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium trioxide. Fluoroacetate, 4-trifluoromethylphenyl iodonium tetrafluoroborate, diphenyliodonium hexafluoroazenate, ditolyliodonium hexafluorophosphate, di (4-methoxyphenyl) iodonium hexafluoroantimonate, di (4-methoxyphenyl) iodonium chloride , (4-Methylphenyl) phenyliodonium teto Fluoroborate, di (2,4-dimethylphenyl) iodonium hexafluoroantimonate, di (4-tert-butylphenyl) iodonium hexafluoroantimonate, 2,2'-diphenyliodonium hexafluorophosphate, tricumyldiphenyliodonium tetrakis (Pentafluorophenyl) borate and the like can be mentioned.

  The polyhalogen compound is a compound having a trihalogenmethyl group, a dihalogenmethyl group or a dihalomethylene group, and particularly preferably a halogen compound represented by the following general formula (1) and a compound in which the above group is substituted with an oxadiazole ring. Used. Among these, a halogen compound represented by the following general formula (2) is particularly preferably used.

Formula ^{(1) R 1 -C (Y} ) 2 - (C = O) -R 2
In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an iminosulfonyl group, or a cyano group. R ² represents a monovalent substituent. R ¹ and R ² may be bonded to form a ring. Y represents a halogen atom.

Formula (2) C (Y) ₃ — (C═O) —XR ³
In the formula, R ³ represents a monovalent substituent. X represents —O— or —NR ⁴ —. R ⁴ represents a hydrogen atom or an alkyl group. R ³ and R ⁴ may be bonded to form a ring. Y represents a halogen atom. Among these, those having a polyhalogenacetylamide group are particularly preferably used.

  A compound in which a polyhalogenmethyl group is substituted with an oxadiazole ring is also preferably used.

  The amount of the polymerization initiator added to the photosensitive layer is not particularly limited, but is preferably in the range of 0.1 to 20% by mass in the constituent components of the photosensitive layer. Furthermore, Preferably it is 0.8-15 mass%.

((C) Polymerizable unsaturated group-containing compound)
A polymerizable unsaturated group-containing compound is a compound having a polymerizable unsaturated group in the molecule, and is an addition polymerization in a molecule generally used for general radical polymerizable monomers and UV curable resins. Polyfunctional monomers having a plurality of possible ethylenic double bonds and polyfunctional oligomers can be used.

  These polymerizable ethylenic double bond-containing compounds are not particularly limited, but preferred examples include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxy. Monofunctional acrylic acid esters such as ethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, ε-caprolactone adduct of 1,3-dioxane alcohol, 1,3-dioxolane acrylate, or Methacrylic acid, itaconic acid, crotonic acid, maleic acid, etc. in which these acrylates are replaced with methacrylate, itaconate, crotonate, and maleate. Tel, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, hydroxypivalate neo Diacrylate of pentyl glycol, diacrylate of neopentyl glycol adipate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl- 5-ethyl-1,3-dioxane diacrylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylo Difunctional acrylic acid esters such as ε-caprolactone adduct of diacrylate, diglycidyl ether diacrylate of 1,6-hexanediol, or methacrylic acid, itacon in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate Acids, crotonic acid, maleic esters such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate, ε-cap of dipentaerythritol hexaacrylate Lactonic acid adducts such as lactone adducts, pyrogallol triacrylate, propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, or these acrylates Examples thereof include methacrylic acid, itaconic acid, crotonic acid, and maleic acid ester instead of methacrylate, itaconate, crotonate, and maleate.

  Prepolymers can also be used as described above. A prepolymer may use together 1 type, or 2 or more types, and may mix and use the above-mentioned monomer and / or oligomer.

  Examples of prepolymers include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, pimelic acid, Polybasic acids such as sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, trimethylol Polyester obtained by introducing (meth) acrylic acid into a polyester obtained by combining polyhydric alcohols such as propane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Chlorates such as bisphenol A, epichlorohydrin, (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as phenol novolac, epichlorohydrin, (meth) acrylic acid, such as ethylene glycol, adipine Acid / tolylene diisocyanate / 2-hydroxyethyl acrylate, polyethylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate, hydroxyethylphthalyl methacrylate / xylene diisocyanate, 1,2-polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate , Trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate In addition, urethane acrylates in which (meth) acrylic acid is introduced into urethane resin, for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, etc., and (meth) acryloyl in oil-modified alkyd resins Examples thereof include prepolymers such as alkyd-modified acrylates having introduced groups and spirane resin acrylates.

  This image forming layer includes phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) modified diacrylate, isocyanuric acid EO modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane acrylate benzoate, It can contain addition-polymerizable oligomers and prepolymers having monomers such as alkylene glycol type acrylic acid-modified, urethane-modified acrylate and the like and structural units formed from the monomers.

  Furthermore, as a compound that can be used in combination, a phosphate ester compound containing at least one (meth) acryloyl group can be mentioned. The compound is a compound in which at least a part of the hydroxyl group of phosphoric acid is esterified.

  In addition, JP-A-58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092, 63- No. 67189, JP-A-1-244891, and the like. Further, “11290 Chemical Products”, Chemical Industry Daily, pages 286 to 294, “UV / EB Curing” The compounds described in "Handbook (raw material)", Kobunshi Shuppankai, pages 11 to 65, and the like can also be suitably used in the present invention. Of these, compounds having two or more acrylic groups or methacryl groups in the molecule are preferred in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferred.

  An addition-polymerizable ethylenic double bond-containing monomer containing a tertiary amino group in the molecule can also be preferably used. Although there is no particular limitation on the structure, a tertiary amine compound having a hydroxyl group modified with glycidyl methacrylate, methacrylic acid chloride, acrylic acid chloride or the like is preferably used. Specifically, polymerizable compounds described in JP-A-1-165613, JP-A-1-203413, and JP-A-1-197213 are preferably used.

  Further, in the present invention, a reaction product of a polyhydric alcohol containing a tertiary amino group in the molecule, a diisocyanate compound, and a compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule is also preferably used. . In particular, a compound having a tertiary amino group and an amide bond is preferably used.

  Examples of the polyhydric alcohol containing a tertiary amino group in the molecule include triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-tert-butyldiethanolamine, N, N-di (hydroxyethyl) aniline, N, N, N ′, N′-tetra-2-hydroxypropylethylenediamine, p-tolyldiethanolamine, N, N, N ′, N′-tetra-2-hydroxyethylethylenediamine, N, N-bis (2-hydroxypropyl) aniline, allyldiethanolamine, 3- (dimethylamino) -1,2-propanediol, 3-diethylamino-1,2-propanediol, N, N-di (n-propyl) Amino-2,3-propanediol, N, N-di iso- propyl) amino-2,3-propanediol, 3- (N-methyl--N- benzylamino) -1,2-propane diol, and the like, but is not limited thereto.

  Examples of the diisocyanate compound include butane-1,4-diisocyanate, hexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate, octane-1,8-diisocyanate, 1,3-diisocyanate methyl-cyclohexanone. 2,2,4-trimethylhexane-1,6-diisocyanate, isophorone diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene- 2,5-diisocyanate, tolylene-2,6-diisocyanate, 1,3-di (isocyanatomethyl) benzene, 1,3-bis (1-isocyanato-1-methylethyl) benzene, and the like. In Not a constant.

  Examples of the compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropylene-1,3- Examples include dimethacrylate and 2-hydroxypropylene-1-methacrylate-3-acrylate.

  These reactions can be carried out in the same manner as a method for synthesizing urethane acrylate by a reaction of a normal diol compound, diisocyanate compound, and hydroxyl group-containing acrylate compound.

Specific examples of these reaction products of polyhydric alcohols containing tertiary amino groups in the molecule, diisocyanate compounds, and compounds containing ethylenic double bonds capable of addition polymerization with hydroxyl groups in the molecule are shown below. .
M-1: reaction product of triethanolamine (1 mol), hexane-1,6-diisocyanate (3 mol), 2-hydroxyethyl methacrylate (3 mol) M-2: triethanolamine (1 mol), isophorone Reaction product of diisocyanate (3 mol) and 2-hydroxyethyl acrylate (3 mol) M-3: Nn-butyldiethanolamine (1 mol), 1,3-bis (1-isocyanate-1-methylethyl) Reaction product of benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) M-4: Nn-butyldiethanolamine (1 mol), 1,3-di (isocyanatomethyl) ) Reaction of benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) Product M-5: Reaction product M-6 of N-methyldiethanolamine (1 mol), tolylene-2,4-diisocyanate (2 mol), 2-hydroxypropylene-1,3-dimethacrylate (2 mol): Reaction product M-7 of triethanolamine (1 mol), 1,3-bis (1-isocyanato-1-methylethyl) benzene (3 mol), 2-hydroxyethyl methacrylate (3 mol): ethylenediaminetetraethanol (1 mol), reaction product of 1,3-bis (1-isocyanato-1-methylethyl) benzene (4 mol), 2-hydroxyethyl methacrylate (4 mol). An acrylate or an alkyl acrylate described in JP-A-2-127404 can be used.

  5-80 mass% is preferable with respect to an image forming layer layer, and, as for the addition amount of the unsaturated group containing compound which can superpose | polymerize, it is more preferable that it is 15-60 mass%.

  The heat-sensitive image forming layer containing a polymerization component preferably contains an alkali-soluble polymer compound.

  The alkali-soluble polymer compound is a polymer compound having an acid value, and specifically, copolymers having various structures as described below can be preferably used.

  As the above-mentioned copolymer, acrylic polymer, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, other natural resins, etc. are used. I can do it. Two or more of these may be used in combination.

  Among these, a polymer having a carboxy group and a hydroxyl group is preferably used, and a polymer having a carboxy group is particularly preferably used.

  Of these, vinyl copolymer obtained by copolymerization of acrylic monomers is preferably used. Furthermore, the copolymer composition is preferably a copolymer of (a) a carboxyl group-containing monomer, (b) a methacrylic acid alkyl ester, or an acrylic acid alkyl ester.

  Specific examples of the carboxyl group-containing monomer include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like. In addition, carboxylic acids such as phthalic acid and 2-hydroxymethacrylate half ester are also preferable.

  Specific examples of alkyl methacrylates and alkyl esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate. , Decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, acrylic In addition to unsubstituted alkyl esters such as decyl acid, undecyl acrylate and dodecyl acrylate, cyclic alkyl esters such as cyclohexyl methacrylate and cyclohexyl acrylate Substituted alkyl esters such as benzyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate, benzyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, and glycidyl acrylate Also mentioned.

  Furthermore, what used the monomer as described in following (1)-(14) as another copolymerization monomer can also be used.

  1) Monomers having an aromatic hydroxyl group, such as o- (or p-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenyl acrylate and the like.

  2) Monomers having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl methacrylate , 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.

  3) A monomer having an aminosulfonyl group, such as m- (or p-) aminosulfonylphenyl methacrylate, m- (or p-) aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p -Aminosulfonylphenyl) acrylamide and the like.

  4) Monomers having a sulfonamide group, such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.

  5) Acrylamide or methacrylamides such as acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N- Phenylacrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like.

  6) Monomers containing fluorinated alkyl groups such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N- Butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.

  7) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and the like.

  8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate and the like.

  9) Styrenes such as styrene, methyl styrene, chloromethyl styrene and the like.

  10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

  11) Olefins such as ethylene, propylene, i-butylene, butadiene, isoprene and the like.

  12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.

  13) Monomers having a cyano group, such as acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o- (or m-, p-) cyanostyrene.

  14) A monomer having an amino group, such as N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N, N-dimethylacrylamide, acryloylmorpholine, Ni-propylacrylamide, N, N-diethylacrylamide and the like.

  Furthermore, other monomers that can be copolymerized with these monomers may be copolymerized.

  Also, an unsaturated bond-containing vinyl copolymer obtained by addition reaction of a compound having a (meth) acryloyl group and an epoxy group in the molecule to a carboxyl group present in the molecule of the vinyl copolymer. Are also preferably used.

  Specific examples of the compound containing both an unsaturated bond and an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, and an epoxy group-containing unsaturated compound described in JP-A No. 11-271969.

  Among these alkali-soluble polymer compounds, compounds having an acid value of 30 to 200 are preferable, and those having a mass average molecular weight of 15,000 to 500,000 are more preferable.

  Among these, those having a polymerizable unsaturated group are preferred, and those having a polymerizable unsaturated group-containing unit of 5 to 50% with respect to the repeating units of the whole polymer compound are particularly preferred.

  As the alkali-soluble polymer compound having a polymerizable unsaturated group, a known method can be used without limitation.

  Examples thereof include a method of reacting a glycidyl group with a carboxyl group, a method of reacting an isocyanate group with a hydroxyl group, and the like.

  Specifically, for example, allyl glycidyl ether, glycidyl (meth) acrylate, α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl are used as the copolymer having a monomer unit having a carboxyl group. Aliphatic epoxy group-containing unsaturated compounds such as glycidyl ether, monoalkyl monoglycidyl itaconate, monoalkyl monoglycidyl fumarate, monoalkyl monoglycidyl maleate, or 3,4-epoxycyclohexylmethyl (meth) acrylate It is a reaction product obtained by reacting an alicyclic epoxy group or unsaturated group-containing compound such as the above with the carboxyl group. In the present invention, it is preferable that the mole percentage of the reaction of the carboxyl group, the epoxy group, and the unsaturated group-containing compound is a unit ratio, and the unit reacted in terms of sensitivity and printing durability is 5 to 50 mol%. Especially preferably, it is 10-30 mol%.

  The reaction of the copolymer having a monomer unit having a carboxyl group with the epoxy group and unsaturated group-containing compound can be carried out, for example, at a temperature of about 80 to 120 ° C. for about 1 to 50 hours. As a synthesis method of the reaction product, it can be synthesized by a generally known polymerization method. R. Sorenson, T.W. W. It can be synthesized according to the literature described in Campbell, the methods described in JP-A Nos. 10-315598 and 11-271963, and the like.

  The amount of the alkali-soluble polymer compound added is preferably 10 to 90% by mass and more preferably 15 to 70% by mass with respect to the image forming layer. Most preferably, it is 20-50 mass%.

  Moreover, the copolymer which has at least 1 sort (s) of the monomer of the following (1)-(17) as a copolymer as a copolymer which has a monomer unit which has the said carboxyl group is mentioned.

(1) a monomer having an aromatic hydroxyl group,
(2) a monomer having an aliphatic hydroxyl group,
(3) a monomer having an aminosulfonyl group,
(4) a monomer having a sulfonamide group,
(5) α, β-unsaturated carboxylic acids,
(6) substituted or unsubstituted alkyl acrylate,
(7) substituted or unsubstituted alkyl methacrylate,
(8) Acrylamide or methacrylamides,
(9) a monomer containing an alkyl fluoride group,
(10) vinyl ethers,
(11) vinyl esters,
(12) Styrenes,
(13) vinyl ketones,
(14) olefins,
(15) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, etc.
(16) a monomer having a cyano group,
(17) A monomer having an amino group.

  Specific examples of the compound include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide. Acrylate, acrylate of ε-caprolactone adduct of 1,3-dioxane alcohol, monofunctional acrylic ester such as 1,3-dioxolane acrylate, or methacrylic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, Itaconic acid, crotonic acid, maleic acid ester; for example, ethylene glycol diacrylate, triethylene glycol Cole diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, hydroxypivalate, neopentyl glycol diacrylate, neopentyl glycol adipate di Acrylate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, Tricyclodecane dimethylol acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, 1,6-hexanediol Difunctional acrylates such as diglycidyl ether diacrylate, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate; Acrylates, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ε- of dipentaerythritol hexaacrylate Caprolactone adduct, pyrogallol triacrylate, propionic acid Polyfunctional acrylic acid esters such as pentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, and their EO-modified products, or these acrylates as methacrylate, itaconate, crotonate And methacrylic acid, itaconic acid, crotonic acid, maleic acid ester, etc., instead of maleate.

(Polymer binder)
The heat-sensitive image forming layer can further contain a polymer binder.

  Examples of the polymer binder include acrylic polymer, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, and other natural resins. Can be used. Two or more of these may be used in combination.

(Polymerization inhibitor)
The heat-sensitive image forming layer can contain a polymerization inhibitor as required.

  Examples of the polymerization inhibitor include hindered amine compounds having a piperidine skeleton having a base constant (pKb) of 7 to 14.

  The addition amount of the polymerization inhibitor is preferably about 0.001 to 10% by mass, particularly preferably 0.01 to 10% by mass, and more preferably 0.1 to 5% by mass with respect to the polymerizable unsaturated group-containing compound. Is preferred.

  In addition to the above-described polymerization inhibitors, other polymerization inhibitors may be added to the heat-sensitive image forming layer. Other polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol) 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine cerium salt, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5) -Methylbenzyl) -4-methylphenyl acrylate and the like.

  In addition, a colorant can also be used in the heat-sensitive image forming layer, and conventionally known ones can be suitably used as the colorant, including commercially available ones. Examples include those described in the revised new edition “Pigment Handbook”, edited by Japan Pigment Technology Association (Seikodo Shinkosha), Color Index Handbook, and the like.

  Examples of the pigment include black pigment, yellow pigment, red pigment, brown pigment, purple pigment, blue pigment, green pigment, fluorescent pigment, and metal powder pigment. Specifically, inorganic pigments (titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and lead, zinc, barium and calcium chromates) and organic pigments (azo-based, thioindigo) , Anthraquinone, anthanthrone, and triphendioxazine pigments, vat dye pigments, phthalocyanine pigments and derivatives thereof, quinacridone pigments, and the like.

  Among these, it is preferable to select and use a pigment having substantially no absorption in the absorption wavelength region of the spectral sensitizing dye corresponding to the exposure laser to be used. In this case, an integrating sphere at the laser wavelength to be used is used. It is preferable that the reflection absorption of the used pigment is 0.05 or less. Moreover, as an addition amount of a pigment, 0.1-10 mass% is preferable with respect to solid content of the said composition, More preferably, it is 0.2-5 mass%.

  It is preferable to provide a protective layer above the thermal image forming layer. The protective layer (oxygen barrier layer) is preferably highly soluble in a developer (described below, generally an alkaline aqueous solution) described below, and specifically includes a layer mainly composed of polyvinyl alcohol and polyvinyl pyrrolidone. it can. Polyvinyl alcohol has an effect of suppressing permeation of oxygen, and polyvinyl pyrrolidone has an effect of ensuring adhesiveness with an adjacent image forming layer.

  In addition to the above two polymers, polysaccharides, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate, sodium alginate as required Water-soluble polymers such as polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, and water-soluble polyamide can also be used in combination.

  The polymerization type image forming layer is an image forming layer containing a polymerization initiator and a polymerizable unsaturated group-containing compound. The polymerization initiator used in the heat-sensitive image forming layer containing the above-described polymerization components, polymerizable unsaturated The same compounds as the group-containing compound can be used.

  As the photopolymerization initiator used for the polymerization type image forming layer, titanocene compounds, monoalkyltriarylborate compounds, iron allene complex compounds, bisimidazole compounds, trihaloalkyl compounds and the like are preferably used.

  Examples of titanocene compounds include compounds described in JP-A-63-41483 and JP-A-2-291. More preferred specific examples include bis (cyclopentadienyl) -Ti-di-chloride, bis (Cyclopentadienyl) -Ti-bis-phenyl, bis (cyclopentadienyl) -Ti-bis-2,3,4,5,6-pentafluorophenyl, bis (cyclopentadienyl) -Ti-bis -2,3,5,6-tetrafluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4,6-trifluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,6 -Difluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4-difluorophenyl, bis (methylcyclopentadienyl) -Ti-bis 2,3,4,5,6-pentafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,3,5,6-tetrafluorophenyl, bis (methylcyclopentadienyl) -Ti- Bis-2,6-difluorophenyl (IRUGACURE 727L: manufactured by Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,6-difluoro-3- (py-1-yl) phenyl) titanium (IRUGACURE 784: Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,4,6-trifluoro-3- (pyridin-1-yl) phenyl) titanium bis (cyclopentadienyl) -bis (2,4 , 6-trifluoro-3- (2-5-dimethylpy-1-yl) phenyl) titanium and the like. It is.

  Examples of the monoalkyl triaryl borate compound include compounds described in JP-A-62-154024 and JP-A-62-143044, and more preferable specific examples include tetra-n-butylammonium n-butyl. -Trinaphthalen-1-yl-borate, tetra-n-butylammonium n-butyl-triphenyl-borate, tetra-n-butylammonium n-butyl-tri- (4-tert-butylphenyl) -borate, tetra- Examples include n-butylammonium n-hexyl-tri- (3-chloro-4-methylphenyl) -borate and tetra-n-butylammonium n-hexyl-tri- (3-fluorophenyl) -borate.

  Examples of the iron allene complex compound include compounds described in JP-A-59-219307, and more preferable specific examples include η-benzene- (η-cyclopentadienyl) iron hexafluorophosphate, η- Cumene- (η-cyclopentadienyl) iron hexafluorophosphate, η-fluorene- (η-cyclopentadienyl) iron hexafluorophosphate, η-naphthalene- (η-cyclopentadienyl) iron hexafluorophosphate, η -Xylene- (η-cyclopentadienyl) iron hexafluorophosphate, η-benzene- (η-cyclopentadienyl) iron tetrafluoroborate and the like.

  Examples of the bisimidazole compound include 2,4,5,2 ′, 4 ′, 5′-hexaphenylbisimidazole, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-. Tetraphenylbisimidazole, 2,2'-bis (2-bromophenyl) -4,5,4 ', 5'-tetraphenylbisimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,5 , 4 ', 5'-tetraphenylbisimidazole, 2,2'-bis (2-chlorophenyl) -4,5,4', 5'-tetrakis (3-methoxyphenyl) bisimidazole, 2,2'-bis (2-Chlorophenyl) -4,5,4 ', 5'-tetrakis (3,4,5-trimethoxyphenyl) -bisimidazole, 2,5,2', 5'-tetrakis (2-chlorophenyl)- , 4'-bis (3,4-dimethoxyphenyl) bisimidazole, 2,2'-bis (2,6-dichlorophenyl) -4,5,4 ', 5'-tetraphenylbisimidazole, 2,2'- Bis (2-nitrophenyl) -4,5,4 ', 5'-tetraphenylbisimidazole, 2,2'-di-o-tolyl-4,5,4', 5'-tetraphenylbisimidazole, 2 , 2'-bis (2-ethoxyphenyl) -4,5,4 ', 5'-tetraphenylbisimidazole and 2,2'-bis (2,6-difluorophenyl) -4,5,4', 5 '-Tetraphenylbisimidazole is mentioned.

  As the trihaloalkyl compound, the above-mentioned trihaloalkyl compound can be used.

  In addition, any photopolymerization initiator can be used in the same manner as described above.

  Examples of the polymerization initiator include coumarin derivatives B-1 to B-22 in JP-A-8-129258, coumarin derivatives D-1 to D-32 in JP-A 2003-211901, and JP-A 2002-363206. No. 1 to 21 Coumarin Derivatives, JP-A No. 2002-363207 No. 1 to 40 Coumarin Derivatives, JP-A No. 2002-363208 No. 1 to 34 Coumarin Derivatives, JP-A No. 2002-363209 No. 1 56 coumarin derivatives and the like can also be preferably used.

  The polymerization type image forming layer can contain the above-mentioned polymer binder as a polymer binder.

(Various additives)
In addition to the components described above, the polymerization type image forming layer is used to prevent unnecessary polymerization of the polymerizable ethylenically unsaturated double bond monomer during the production or storage of the photosensitive lithographic printing plate material. , Hindered phenolic compounds, hindered amine compounds and other polymerization inhibitors may be added.

  Examples of hindered phenol compounds include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4 '-Butylidenebis (3-methyl-6-tert-butylphenol), tetrakis- [methylene-3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3 '-Bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl)- 4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphene Acrylate, etc., preferably 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate having a (meth) acrylate group, 2- [ And 1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate.

  Examples of hindered amine compounds include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1- [ 2- [3- (3,5-di-tert-butyl-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy]- 2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1, 3,8-triazaspiro [4.5] decane-2,4-dione and the like.

  Other polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol) Hindered amines such as 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine primary cerium salt, 2,2,6,6-tetramethylpiperidine derivatives, and the like. .

  The addition amount of the polymerization inhibitor is preferably about 0.01% to about 5% with respect to the mass of the total solid content of the composition. Also, if necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide are added to prevent polymerization inhibition by oxygen, or unevenly distributed on the surface of the photopolymerizable photosensitive layer during the drying process after coating. You may let them. The amount of the higher fatty acid derivative added is preferably about 0.5% to about 10% of the total composition.

  In addition to the components described above, a colorant can also be used in the polymerization type image forming layer in the same manner as described above.

(Application)
Examples of the solvent used in preparing the coating solution for the image forming layer include alcohols: sec-butanol, isobutanol, n-hexanol, benzyl alcohol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,5. -Pentanediol, etc .; ethers: propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, etc .; ketones, aldehydes: diacetone alcohol, cyclohexanone, methylcyclohexanone, etc .; esters: ethyl lactate, butyl lactate , Diethyl oxalate, methyl benzoate and the like are preferable.

  The prepared coating composition (image forming layer coating solution) can be coated on a support by a conventionally known method and dried to produce a photopolymerizable photosensitive lithographic printing plate material. Examples of coating methods for the coating liquid include air doctor coater method, blade coater method, wire bar method, knife coater method, dip coater method, reverse roll coater method, gravure coater method, cast coating method, curtain coater method and extrusion coater method. Can be mentioned.

  The drying temperature of the photosensitive layer is preferably in the range of 60 to 160 ° C, more preferably in the range of 80 to 140 ° C, and particularly preferably in the range of 90 to 120 ° C.

(Protective layer)
It is preferable to provide a protective layer on the upper side of the image forming layer. The protective layer (oxygen barrier layer) is preferably highly soluble in a developer (generally an alkaline aqueous solution).

  The material constituting the protective layer is preferably polyvinyl alcohol, polysaccharide, polyvinyl pyrrolidone, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate , Sodium alginate, polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, water-soluble polyamide and the like. These compounds can be used alone or in combination of two or more as a protective layer coating composition. A particularly preferred compound is polyvinyl alcohol.

  In order to prepare the protective layer coating composition, the above-mentioned material can be dissolved in a suitable solvent to form a coating solution, which is coated on the photopolymerizable photosensitive layer according to the present invention and dried. Thus, a protective layer can be formed. The thickness of the protective layer is preferably from 0.1 to 5.0 μm, particularly preferably from 0.5 to 3.0 μm. The protective layer can further contain a surfactant, a matting agent and the like as required.

  As the method for coating the protective layer, the known coating methods mentioned above for coating the photosensitive layer can be suitably used. The drying temperature of the protective layer is preferably lower than the drying temperature of the photosensitive layer, preferably the difference from the photosensitive layer drying temperature is 10 ° C. or more, more preferably 20 ° C. or more, and the upper limit is about 50 ° C. at most. .

  Moreover, it is preferable that the drying temperature of a protective layer is lower than the glass transition temperature (Tg) of the binder which a photosensitive layer contains. The difference between the drying temperature of the protective layer and the glass transition temperature (Tg) of the binder contained in the photosensitive layer is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, and the upper limit is about 60 ° C. at most.

(Platemaking-Printing)
The lithographic printing plate material is subjected to image formation by image exposure, subjected to development processing as necessary, and subjected to printing.

  Examples of light sources for image exposure include lasers, light emitting diodes, xenon lamps, xenon flash lamps, halogen lamps, carbon arc lamps, metal halide lamps, tungsten lamps, high pressure mercury lamps, and electrodeless light sources.

  In the case of batch exposure, a mask material in which a negative pattern of a desired exposure image is formed of a light-shielding material may be superimposed on the photopolymerizable photosensitive layer and exposed.

  When using an array-type light source such as a light-emitting diode array, or when controlling exposure of a light source such as a halogen lamp, metal halide lamp, or tungsten lamp with an optical shutter material such as liquid crystal or PLZT, digital Exposure is possible and preferable. In this case, direct writing can be performed without using a mask material.

  Laser exposure is suitable for direct writing without using a mask material because light exposure can be performed in the form of a beam according to image data. When a laser is used as a light source, it is easy to reduce the exposure area to a very small size, and high-resolution image formation is possible.

  The lithographic printing plate material is preferably subjected to image exposure with laser light to form an image.

  Laser scanning methods include cylindrical outer surface scanning, cylindrical inner surface scanning, and planar scanning. In the cylindrical outer surface scanning, laser exposure is performed while rotating a drum around which the recording material is wound, and the rotation of the drum is the main scanning and the movement of the laser light is the sub scanning. In cylindrical inner surface scanning, a recording material is fixed to the inner surface of the drum, a laser beam is irradiated from the inside, and a main scanning is performed in the circumferential direction by rotating a part or all of the optical system. Sub scanning is performed in the axial direction by linearly moving all of them in parallel with the drum axis. In plane scanning, a laser beam main scan is performed by combining a polygon mirror, a galvanometer mirror, and an fθ lens, and a sub-scan is performed by moving a recording medium. Cylindrical outer surface scanning and cylindrical inner surface scanning are easier to increase the accuracy of the optical system and are suitable for high-density recording.

  In the case where development processing is required, a method of developing the photosensitive lithographic printing plate material using an automatic processor is an embodiment.

  Printing can be performed using a general lithographic printing machine.

  In recent years, the printing industry has been screaming for environmental conservation, and in printing inks, inks that do not use petroleum-based volatile organic compounds (VOC) have been developed and are becoming popular. This is particularly noticeable when the printing inks are used. Examples of environmentally friendly printing inks include soybean oil ink “Naturalis 100” manufactured by Dainippon Ink & Chemicals, Inc., VOC zero ink “TK Hi-Echo NV” manufactured by Toyo Ink, and process ink “Soyselbo” manufactured by Tokyo Ink. It is done.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to this. In the examples, “parts” represents “parts by mass” unless otherwise specified.

Example 1
(Preparation of supports 1-5)
A rolled aluminum web having a thickness of 0.3 mm and a width of 1030 mm (material 1052, Al: 99.3% or more, Na: 0.003%, Mg: 0.20%, Si: 0.08%, Ti: 0.06%, Mn: 0.004%, Fe: 0.32%, Ni: 0.004%, Cu: 0.002%, Zn: 0.015%, Ga: 0.007%, Cr: 0 .001%) was processed using the apparatus shown in FIG.

  In the flattening process, the shaft of the roller 101 is moved by 10 mm to the aluminum web side from the position where the aluminum web is brought into contact with the roller and conveyed horizontally, and the shaft of the roller 102 is moved by 10 mm to the aluminum web side. The web was flattened.

  Subsequently, it was immersed in 3% sodium hydroxide aqueous solution kept at 55 ° C., degreased for 20 seconds, and then washed with water. This degreased aluminum plate was neutralized by immersing it in a 5% nitric acid aqueous solution kept at 25 ° C. for 10 seconds, and then washed with water.

Next, an electrolytic rough surface for 15 seconds at a current density of 60 A / dm ² using an AC sine waveform in an acidic solution having a hydrochloric acid concentration of 11 g / l, an acetic acid concentration of 10 g / l, a dissolved aluminum concentration of 8.5 g / l, and a temperature of 30 ° C. After performing the chemical conversion treatment, it was washed with water.

After electrolytic surface roughening, it was immersed in a 100 g / l phosphoric acid aqueous solution kept at 55 ° C. for 10 seconds, desmutted, and washed with water. Next, using a DC power source, an anodizing treatment was performed at a current density of 5 A / dm ² and a coating mass of 30 mg / dm ² in a sulfuric acid aqueous solution having a concentration of 200 g / l, a dissolved aluminum concentration of 1.5 g / l and a temperature of 25 ° C. , Washed with water.

  Subsequently, a post-treatment with a 2 g / l polyvinylphosphonic acid solution kept at 75 ° C. was performed for 20 seconds and washed with water.

  Ion exchange water was used for the washing water after the anodizing treatment, the diluted water of the polyvinylphosphonic acid solution, and the washing water after the treatment with the polyvinylphosphonic acid solution.

  Subsequently, the support body 1 used for the process of coating the coating liquid for the following lithographic printing plate materials was produced through the drying process which has an infrared heater, and the cooling process by cooling air.

  Further, the support 2 with the 8 mm bite, the support 3 with the 5 mm bite, and the support with the 2 mm bite each for the distance of the axis of the roller 101 of the flattening treatment and the aluminum web side of the axis of the roller 102. A body 4 and a support 5 that was not subjected to the planarization process were prepared.

  Table 1 shows the curl degree of each support after the planarization treatment.

(Preparation of photopolymer type planographic printing plate materials 1 to 5 corresponding to FD-YAG laser light source (532 nm))
A photopolymerizable photosensitive layer coating solution having the following composition was coated on the supports 1 to 5 with a wire bar so as to be 1.5 g / m ² when dried, and dried at 95 ° C. for 1.5 minutes. Thereafter, a protective layer coating solution having the following composition was further coated on the photosensitive layer with a die coater so as to be 2.0 g / m ² when dried, and dried at 75 ° C. for 1.5 minutes. Subsequently, a photopolymerizable photosensitive lithographic printing plate material having a protective layer on the photosensitive layer was produced through a step of cutting to a length of 800 mm through an interleaf feeder.

(Photopolymerizable photosensitive layer coating solution)
Polymer binder B-1 (below) 40.0 parts Sensitizing dyes D-1 and D-2 1: 1 (below) 3.0 parts Photopolymerization initiator η-cumene- (η-cyclopentadienyl) ) Iron hexafluorophosphate 4.0 parts addition-polymerizable ethylenically unsaturated double bond-containing monomer M-3 (above) 40.0 parts addition-polymerizable ethylenically unsaturated double bond-containing monomer NK Ester 4G (polyethylene glycol dimethacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) 15.0 parts Hindered amine compound (LS-770: manufactured by Sankyo Co., Ltd.) 0.1 part Trihaloalkyl compound E-1 (below) 1.0 part Phthalocyanine pigment (MHI454) 4.0 parts fluorine surfactant (F178K: made by Dainippon Ink & Chemicals, Inc.) 0.5 parts methyl ethyl ketone 80 parts cyclohexanone 820 parts (polymer bond) Synthesis of wood B-1)
In a three-necked flask under a nitrogen stream, methyl methacrylate (125 parts: 1.25 mol), ethyl methacrylate (12 parts: 0.10 mol), methacrylic acid (63 parts: 0.73 mol), cyclohexanone (240 parts), Isopropyl alcohol (160 parts) and α, α′-azobisisobutyronitrile (5 parts) were added and reacted in an oil bath at 80 ° C. in a nitrogen stream for 6 hours to obtain a polymer. Thereafter, 4 parts of triethylbenzylammonium chloride and glycidyl methacrylate (52 parts: 0.73 mol) were added to the polymer and reacted at a temperature of 25 ° C. for 3 hours to obtain a polymer binder B-1. The weight average molecular weight was about 55,000 (GPC: polystyrene conversion).

(Protective layer coating solution)
Polyvinyl alcohol (GL-05: Nippon Synthetic Chemical Co., Ltd.) 84 parts Polyvinylpyrrolidone (K-30: ISP Japan Co., Ltd.) 15 parts Surfactant (Surfinol 465: Nissin Chemical Industry Co., Ltd.) 0.5 part Water 900 (Image formation)
A CTP exposure apparatus (Tigercat) equipped with an FD-YAG laser light source was prepared by allowing the photopolymerizable photosensitive lithographic printing plate material thus prepared to stand in a dark room at a temperature of 23 ° C. and a relative humidity of 50% for one day. : Manufactured by ECRM), an image of 175 lines was exposed at 150 μJ / cm ² at a resolution of 2400 dpi (dpi represents the number of dots per inch, that is, 2.54 cm).

  The exposed image is a 50% flat mesh image. Next, before development, a heating device part, a pre-washing part for removing the protective layer, a developing part filled with the following developer composition, a washing part for removing the developer adhering to the plate surface, a gum solution for protecting the image line part ( Developed with a CTP automatic developing machine (Raptor Polymer: manufactured by Glunz & Jensen) equipped with GW-3 (Mitsubishi Chemical Co., Ltd. diluted twice), lithographic printing plates 1 to 5 were obtained.

  At this time, the heating unit was set so that the plate surface temperature was 105 ° C. and the plate staying time was 15 seconds. The plate was inserted into the heating unit of the self-machine after the exposure was completed within 30 seconds.

Developer composition (aqueous solution containing the following additives)
Potassium silicate aqueous solution (SiO ₂ : 26%, K ₂ O: 13.5%) 40.0 g / L
Potassium hydroxide 4.0g / L
Ethylenediaminetetraacetic acid 0.5g / L
Polyoxyethylene (13) naphthyl ether sulfonate 20.0 g / L
1 L with water. The pH was 12.3.

(Printing method)
A lithographic printing plate produced by exposure and development is coated with a printing machine (DAIYA1F-1: manufactured by Mitsubishi Heavy Industries), printing ink (soybean oil ink Naturalis 100: manufactured by Dainippon Ink and Chemicals), and dampening water. Printing was performed using (H liquid SG-51 concentration 1.5%: manufactured by Tokyo Ink Co., Ltd.).

(Uniformity of image reproduction)
Linear correction was performed by the above exposure method, and a 50% flat mesh image was reproduced on the plate surface. The above printing is performed, and 50% halftone dots of the 1000th printed material are randomly measured with a halftone dot area measuring device (X-rite Dot model: manufactured by CCD5 centurfax ltd), and the maximum halftone dot area of the measured values at 20 points is measured. The difference between (%) and the minimum dot area (%) was determined. The smaller the difference between the maximum halftone dot area (%) and the minimum halftone dot area (%), the better the image reproduction uniformity. The results of the evaluation are shown in Table 2.

  It can be seen from Table 2 that the photosensitive lithographic printing plate material using the support produced by the production method of the present invention is excellent in image reproduction uniformity.

(Preparation of photopolymer type lithographic printing plate materials 6 to 10 compatible with violet light sources)
A photopolymerizable photosensitive layer coating solution having the following composition was coated on the supports 1 to 5 with a wire bar so as to be 1.5 g / m ² when dried, and dried at 95 ° C. for 1.5 minutes. Thereafter, a protective layer coating solution having the following composition was further coated on the photosensitive layer with a die coater so as to be 2.0 g / m ² when dried, and dried at 75 ° C. for 1.5 minutes. Subsequently, a photopolymerizable photosensitive lithographic printing plate material having a protective layer on the photosensitive layer was produced through a step of cutting to a length of 800 mm through an interleaf feeder.

(Photopolymerizable photosensitive layer coating solution)
30% propylene glycol methyl ether solution of a copolymer (molecular weight 36000) having a weight ratio of 25:75 of methacrylic acid and methyl methacrylate 100.0 parts 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenylbiimidazole 3.0 parts Sensitizing dye D-3 and D-4 1: 1 (below) 4.0 parts Addition-polymerizable ethylenically unsaturated double bond-containing monomer M-3 (Above) 40.0 parts addition-polymerizable ethylenically unsaturated double bond-containing monomer NK ester 3G (polyethylene glycol dimethacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) 7.0 parts Compound C- having a cationically polymerizable group 1 (below) 8.0 parts hindered amine compound (LS-770: Sankyo Co., Ltd.) 0.1 part trihaloalkyl compound E-1 (above) 5.0 parts phthalocyanine face (MHI454: manufactured by Mikuni Dye Co., Ltd.) 3.5 parts Fluorine-based surfactant (F-178K; manufactured by Dainippon Ink and Co., Ltd.) 0.5 part Siloxane-based surfactant (BYK337; manufactured by BYK Chemie) 0.9 part Methyl ethyl ketone 80 820 parts of propylene glycol methyl ether

(Protective layer coating solution)
Polyvinyl alcohol (Cell Ball 103: manufactured by Celaneas) 85.0 parts Vinylpyrrolidone / vinyl acetate copolymer (Rubitec VA64W: manufactured by BASF)
15.0 parts Surfinol 465 (Air Products) 0.2 parts Water 900 parts (image formation)
The photopolymerizable photosensitive lithographic printing plate material thus produced was left in a dark room for 1 day in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and was equipped with a light source equipped with a laser of 408 nm and 30 mW output. Using a plate setter (NewsCTP: manufactured by ECRM), an image of 175 lines was exposed at 50 μJ / cm ² at a resolution of 2400 dpi (where dpi represents the number of dots per inch, that is, 2.54 cm). The exposed image is a 50% flat mesh image.

Next, before development, a heating unit, a pre-water washing part for removing the protective layer, a developing part filled with the developer composition, a water washing part for removing the developer adhering to the plate surface, a gum solution for protecting the image area ( The lithographic printing plates 6 to 10 were obtained by developing with a CTP automatic developing machine (Raptor Polymer: Glunz & Jensen) equipped with GW-3 (Mitsubishi Chemical Co., Ltd. diluted 2-fold). At this time, the heating unit was set so that the plate surface temperature was 105 ° C. and the plate staying time was 15 seconds. The plate was inserted into the heating unit of the self-machine after the exposure was completed within 30 seconds.
(Uniformity of image reproduction)
Evaluation was performed in the same manner as described above. The results are shown in Table 3.

  It can be seen from Table 3 that the photosensitive lithographic printing plate material using the support produced by the production method of the present invention is excellent in image reproduction uniformity.

(Preparation of photopolymer type lithographic printing plate materials 11-15 for infrared laser light source (830 nm))
A photosensitive layer coating solution having the following composition was coated on the supports 1 to 5 with a wire bar so as to be 1.5 g / m ² when dried, and dried at 95 ° C. for 1.5 minutes. Thereafter, a protective layer coating solution having the following composition was further coated on the photosensitive layer with a die coater so as to be 2.0 g / m ² when dried, and dried at 75 ° C. for 1.5 minutes. Next, a photosensitive lithographic printing plate material having a protective layer on the photosensitive layer was prepared through a slip sheet feeding device and a step of cutting to a length of 800 mm.

(Photosensitive layer coating solution)
Polymer binder B-1 (above) 40.0 parts Infrared absorber D-5 (below) 2.5 parts N-phenylglycine benzyl ester 4.0 parts Addition polymerizable ethylenically unsaturated double bond-containing single Polymer M-3 (above) 40.0 parts Addition-polymerizable ethylenically unsaturated double bond-containing monomer NK ester 4G (polyethylene glycol dimethacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) 7.0 parts Cationic polymerizable group Compound C-1 (previously) 8.0 parts Hindered amine compound (LS-770: manufactured by Sankyo Co., Ltd.) 0.1 part Trihaloalkyl compound E-1 (previously) 5.0 parts Phthalocyanine pigment (MHI454: Gokoku Dye Company) 7.0 parts Fluorosurfactant (F178K: manufactured by Dainippon Ink & Chemicals, Inc.) 0.5 part Methyl ethyl ketone 80 parts Cyclohexanone 820 parts

(Protective layer coating solution)
Polyvinyl alcohol (Cell Ball 103: manufactured by Celaneas) 85.0 parts Vinylpyrrolidone / vinyl acetate copolymer (Rubitec VA64W: manufactured by BASF)
15.0 parts Surfinol 465 (Air Products) 0.2 parts Water 900 parts (image formation)
A plate setter (Trend Setter 3244: manufactured by Creo) equipped with a light source of 830 nm was used for the photosensitive lithographic printing plate material thus prepared, which was left in a dark room for one day in an environment of a temperature of 23 ° C. and a relative humidity of 50%. ) Was used to expose an image of 175 lines at a resolution of 2400 dpi (dpi represents the number of dots per inch or 2.54 cm) at 150 mJ / cm ² . The exposed image is a 50% flat mesh image.

  Next, before development, a heating unit, a pre-water washing part for removing the protective layer, a developing part filled with the developer composition, a water washing part for removing the developer adhering to the plate surface, a gum solution for protecting the image area ( Development processing was performed with a CTP automatic developing machine (Raptor Polymer: manufactured by Glunz & Jensen) equipped with GW-3 (Mitsubishi Chemical Co., Ltd. diluted 2-fold) to obtain lithographic printing plates 11-15. At this time, the heating unit was set so that the plate surface temperature was 115 ° C. and the plate staying time was 15 seconds. The plate was inserted into the heating unit of the self-machine after the exposure was completed within 30 seconds.

(Uniformity of image reproduction)
Evaluation was performed in the same manner as described above. The results are shown in Table 4.

  It can be seen from Table 4 that the photosensitive lithographic printing plate material using the support produced by the production method of the present invention is excellent in image reproduction uniformity.

(Preparation of positive lithographic printing plate materials 16 to 20 compatible with infrared laser light source (830 nm))
A photosensitive layer coating solution having the following composition was coated on the supports 1 to 5 with a wire bar so as to be 1.3 g / m ² when dried, and dried at 95 ° C. for 1.5 minutes. Next, a photosensitive lithographic printing plate material was prepared through a step of cutting to a length of 800 mm through an interleaf feeder.

(Photosensitive layer coating solution)
Novolak resin (m-cresol / p-cresol = 60/40, weight average molecular weight 7,000, containing 0.5% by mass of unreacted cresol) 1.0 part Infrared absorber D-5 (above) 0.1 part Tetrahydro Phthalic anhydride 0.05 parts p-Toluenesulfonic acid 0.002 parts Ethyl violet counter ion converted to 6-hydroxy-β-naphthalenesulfonic acid 0.02 parts Fluorosurfactant (F178K: Dainippon Ink and Chemicals, Inc.) (Manufactured by Kogyo) 0.5 parts methyl ethyl ketone 12 parts (image formation)
A plate setter (Trend Setter 3244: manufactured by Creo) equipped with a light source of 830 nm was used for the photosensitive lithographic printing plate material thus prepared, which was left in a dark room for one day in an environment of a temperature of 23 ° C. and a relative humidity of 50%. ) Was used to expose an image of 175 lines at a resolution of 2400 dpi (dpi represents the number of dots per inch or 2.54 cm) at 150 mJ / cm ² . The exposed image is a 50% flat mesh image. Next, before development, a heating device part, a pre-washing part for removing the protective layer, a developing part filled with the following developer composition, a washing part for removing the developer adhering to the plate surface, a gum solution for protecting the image line part ( Development processing was performed with a CTP automatic developing machine (Raptor Polymer: manufactured by Glunz & Jensen) equipped with GW-3 (Mitsubishi Chemical Co., Ltd. diluted 2-fold) to obtain lithographic printing plates 16-20.

  At this time, heating of the heating unit was turned off, and the pre-rinsing unit for removing the protective layer did not supply water. The plate was inserted into the self-machine after the exposure was completed within 30 seconds.

Developer composition (aqueous solution containing the following additives)
Potassium salt consisting of D-sorbite / potassium oxide K ₂ O in combination of non-reducing sugar and base 50.0 g / L
Olfin AK-02 (manufactured by Nissin Chemical) 0.15 g / L
C ₁₂ H ₂₅ N (CH ₂ CH ₂ COONa) ₂ 1.0 g / L
1 L with water.

(Uniformity of image reproduction)
Evaluation was performed in the same manner as described above. The results are shown in Table 5.

  It can be seen from Table 5 that the photosensitive lithographic printing plate material using the support produced by the production method of the present invention is excellent in image reproduction uniformity.

(Preparation of on-machine development type planographic printing plate materials 21 to 25 compatible with infrared laser light source (830 nm))
(Preparation of hydrophilic layer)
A material having the following composition was sufficiently stirred and mixed using a homogenizer and then filtered to prepare a hydrophilic layer coating solution having a solid content of 15% by mass. A hydrophilic layer coating solution is applied onto the supports 1 to 5 using a wire bar so that the weight after drying is 2.0 g / m ² , dried at 100 ° C. for 3 minutes, and hydrophilic. The aluminum support coated with the layer was wound up. Next, an aging treatment at 60 ° C. for 24 hours was performed.

(Hydrophilic layer)
Metal oxide particles having photothermal conversion function Black iron oxide particles: ABL-207 (manufactured by Titanium Industry Co., Ltd., octahedral shape, average particle size: 0.2 μm, specific surface area: 6.7 m ^{2 /} g, Hc: 9.95 kA / M, σs: 85.7 Am ^{2 /} kg, σr / σs: 0.112) 12.50 parts Colloidal silica (alkaline) SNOWTEX-XS (Nissan Chemical Co., Ltd., solid content 20% by mass) 60.62 parts 10% by mass aqueous solution of trisodium phosphate / 12 water (reagent manufactured by Kanto Chemical Co., Inc.)
1.13 parts 10% by mass aqueous solution of water-soluble chitosan Fronac S (manufactured by Kyowa Technos)
2.50 parts Surfactant: 1% by weight aqueous solution of Surfynol 465 (Air Products)
1.25 parts Pure water 22.00 parts Next, the aluminum support on which the wound hydrophilic layer was coated was fed out, and the following image forming layer coating solution was applied using a wire bar and dried. Next, after passing through a slip-sheet supply device, a step of cutting to 800 mm length was performed, and then an aging treatment was performed to obtain a photosensitive lithographic printing plate sample.

Image forming layer: Drying amount 1.50 g / m ² , Drying condition 55 ° C./3 minutes Aging condition: 40 ° C./24 hours (Image forming layer coating solution)
Aqueous polyurethane resin: Takelac W-615 (manufactured by Mitsui Takeda Chemical Co., Ltd.) Solid content 35% by mass: 17.1 parts Aqueous block isocyanate: Takenate XWB-72-N67 (manufactured by Mitsui Takeda Chemical Co., Ltd.) 45% by mass solid content: 7. 1 part Sodium polyacrylate: aqueous solution of Aqualic DL522 (manufactured by Nippon Shokubai Co., Ltd.), solid content 10% by mass: 5.0 parts Photothermal conversion dye: ethanol solution of ADS830AT (manufactured by American Dye Source), 1% by mass: 30 0.0 part pure water: 40.8 parts (image formation)
A plate setter (Trend Setter 3244: manufactured by Creo) equipped with a light source of 830 nm is used for the photosensitive lithographic printing plate material thus prepared, which is left in a dark room for one day in an environment having a temperature of 23 ° C. and a relative humidity of 50%. ) Was subjected to image exposure at 220 mJ / cm ² for 2400 dpi (dpi represents the number of dots per inch, that is, 2.54 cm) to obtain lithographic printing plates 21 to 25. The exposed image is a 50% flat mesh image.

(Printing method)
After exposure, it is attached to the plate cylinder of a printing machine (DAIYA1F-1: manufactured by Mitsubishi Heavy Industries) as it is, coated paper, printing ink (soybean oil ink Naturalis 100: manufactured by Dainippon Ink and Chemicals), and dampening water ( Printing was performed using liquid H SG-51 concentration 1.5%: manufactured by Tokyo Ink Co., Ltd.

(Uniformity of image reproduction)
Evaluation was performed in the same manner as described above. The results are shown in Table 6.

  It can be seen from Table 6 that the photosensitive lithographic printing plate material using the support produced by the production method of the present invention is excellent in image reproduction uniformity.

The schematic of the example of the manufacturing apparatus used for the manufacturing method of the aluminum support body for lithographic printing plate materials of this invention is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrolytic surface roughening process 2 Anodizing process 3 Hydrophilization process 4 Drying process 6 Rubber roller 7 Winding part 11 Electric field roughening tank 12 Electrolyte 13 Electrolysis process 13
18 Electrode 21 Anodizing treatment tank 31 Hydrophilization treatment tank 41 Heating means 100 Planarization treatment process 101 Roller 102 Roller 200 Conveying speed adjustment process A1 Rolled aluminum web A2 Unrolled aluminum web A3 Before flattening treatment Aluminum web A4 roughened aluminum web

Claims (5)

The wound aluminum web is unwound, conveyed and subjected to an electrolytic surface roughening treatment, an electrolytic surface roughening treatment step, an anodizing treatment step for anodizing treatment, a hydrophilic treatment step for hydrophilic treatment, and drying. A method for producing an aluminum support for a lithographic printing plate material having drying steps in this order, comprising a planarization treatment step of performing a planarization treatment with a curl degree of 1.0 mm or less before the electrolytic surface-roughening treatment step A method for producing an aluminum support for a lithographic printing plate material, comprising: 2. The method for producing an aluminum support for a lithographic printing plate material according to claim 1, further comprising a conveyance speed adjusting step after the aluminum web is unwound and before the flattening treatment step. 3. The method for producing an aluminum support for a lithographic printing plate material according to claim 1, wherein the electrolytic surface roughening treatment is performed in an electrolytic solution containing hydrochloric acid. An aluminum support for a lithographic printing plate material produced by the method for producing an aluminum support for a lithographic printing plate material according to any one of claims 1 to 3. A lithographic printing plate material comprising an image forming layer on the aluminum support for a lithographic printing plate material according to claim 4.

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