JP2009142994A - Manufacturing method of aluminum support for lithographic printing plate material, aluminum support for lithographic printing plate material and lithographic printing plate material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive lithographic printing plate material with excellent uniformity of image reproducibility, a support for the photosensitive lithographic printing plate material, and a manufacturing method of the support. <P>SOLUTION: This manufacturing method of the aluminum support for the lithographic printing plate material has an electrolytic surface roughening treatment process which includes the electrolysis process to roughen the surface of a conveyed aluminum web through electrolytic steps with the help of an electrolyte. In addition, the electrolyte contains hydrochloric acid, and the electrolytic surface roughening treatment process has the immersion process to soak the aluminum web in the electrolyte for not less than 6 sec to not more than 10 sec prior to the electrolysis process. <P>COPYRIGHT: (C)2009,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 support for the aluminum plate is roughened on the surface, and the anode is used to improve printability and printing durability. Those subjected to oxidation treatment are generally used.

  Various structures are known as the surface shape of the aluminum support for improving the printability 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.

Further, there is known a method for improving printability by a method in which an electrolytic surface roughening treatment is started in a hydrochloric acid solution within 5 seconds after a specific aluminum plate is immersed in the hydrochloric acid solution, thereby roughening the surface. (See Patent Document 3)
However, in the lithographic printing plate material in which an image forming layer is formed on the aluminum support for these lithographic printing plate materials, there is a case where the image reproducibility may be uneven and the uniformity of image reproduction is insufficient. was there.
JP 2004-98456 A JP 2006-305819 A JP 2003-246159 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. A method for producing an aluminum support for a lithographic printing plate material comprising an electrolytic surface-roughening treatment step comprising an electrolytic step of electrolyzing and roughening the surface of an aluminum web to be conveyed, wherein the electrolytic solution comprises A lithographic plate characterized in that it is an electrolytic solution containing hydrochloric acid, and the electrolytic surface-roughening treatment step comprises an immersion step of immersing the aluminum web in the electrolytic solution for 6 seconds or more and 10 seconds or less before the electrolytic step. A method for producing an aluminum support for a printing plate material.
2. 2. The method for producing an aluminum support for a lithographic printing plate material according to 1, wherein the temperature of the electrolytic solution in the electrolysis step is the same as the temperature of the electrolytic solution in the immersion step.
3. 3. The method for producing an aluminum support for a lithographic printing plate material according to 1 or 2, further comprising a desmut treatment step and an anodization treatment step after the electrolytic surface roughening treatment step.
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 4.3.
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 is a method for producing an aluminum support for a lithographic printing plate material having an electrolytic surface roughening treatment step including an electrolytic step of electrolyzing and roughening the surface of the aluminum web to be conveyed, The electrolytic solution is an electrolytic solution containing hydrochloric acid, and the electrolytic surface-roughening treatment step has an immersion step of immersing the aluminum web in the electrolytic solution for 6 seconds or more and 10 seconds or less before the electrolytic step. Features.

  In the present invention, an aluminum support that provides a photosensitive lithographic printing plate material excellent in image reproduction uniformity by immersing in this electrolyte solution for 6 seconds or more and 10 seconds or less, particularly before electrolysis with a hydrochloric acid electrolyte solution. Obtainable.

(Aluminum plate)
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, the aluminum content of the aluminum plate is preferably 99.5% by mass or more, and an aluminum plate having a Cu content of 0.005% by mass or less is preferably used.

(Electrolytic roughening process)
The configuration of the present invention will be described below 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 method for producing an aluminum support for a lithographic printing plate material of the present invention (hereinafter also simply referred to as an aluminum support) includes an electrolysis step 13 in which an aluminum web A is electrolyzed with an electrolytic solution containing hydrochloric acid to roughen the surface. The electrolytic surface-roughening treatment step 1 is a step before the electrolysis step 13 and includes an immersion step 12 in which the aluminum web is immersed in the electrolytic solution 14 containing hydrochloric acid for 6 seconds to 10 seconds.

  In the method for producing an aluminum support of the present invention, it is preferable to perform a degreasing treatment prior to the electrolytic surface roughening treatment step in order to remove the rolling oil on the surface.

  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 for degreasing. It is preferable to apply a desmutting treatment.

  In the present invention, after the degreasing treatment, since it is immersed in an electrolytic solution containing hydrochloric acid, a desmutting treatment at the time of degreasing with hydrochloric acid is preferable. The hydrochloric acid concentration is preferably 0.1 to 1 g / l.

  After the desmut treatment, in the electrolytic surface roughening treatment step 1, the aluminum web is immersed in the electrolytic solution in the dipping step 12 according to the present invention, and the aluminum web is subsequently electrolyzed in the electrolytic step 13.

(Immersion process)
The electrolytic solution containing hydrochloric acid according to the present invention is an aqueous solution containing 0.5 mass% or more of hydrochloric acid (as HCl), preferably the hydrochloric acid concentration is 5 to 20 g / l, particularly preferably 6 ~ 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 20 g / l, more preferably 1.0 to 15 g / l, and most preferably 5.0 to 13 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 dipping in the dipping process 12 is performed in contact with the electrolytic solution 14 by transporting the aluminum web in the electrolytic solution 14 contained in the roughening treatment tank 11.

  The transport speed is preferably 5 m / min to 50 m / min, particularly preferably 10 m / min to 25 m / min, relative to the electrolytic solution contained in the electrolytic cell 11.

  That is, in the present invention, it is preferable to immerse the aluminum web A in the range of 10 m / min to 25 m / min for 6 seconds to 10 seconds.

  As temperature to immerse, 15 to 35 degreeC is preferable, and 18 to 38 degreeC is especially preferable.

(Electrolysis process)
In the electrolysis step 13, an electrolytic treatment is performed through the electrode 15 with the following electric quantity in the above-described electrolytic solution 14.

In the electrolysis step 13, 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.

  The dipping process and the electrolysis process may be performed in one tank by filling an electrolytic solution in one tank and transporting the aluminum web in the tank. Moreover, you may process by dividing | segmenting the tank for immersion processes, and the tank for electrolytic processes separately. In the present invention, the former embodiment is preferably used. When performing in the same tank, it is preferable that the temperature of the electrolytic solution in the dipping step and the temperature of the electrolytic solution in the electrolytic step are the same.

(Desmutting process)
After the electrolytic surface roughening treatment is performed in an electrolytic solution containing hydrochloric acid, it is preferably immersed in an aqueous solution of acid or alkali 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. Further, after the immersion treatment with an alkaline aqueous solution, it is preferable to carry out a neutralization treatment by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof. Among these, it is preferable to use an aqueous solution of phosphoric acid. The amount of aluminum dissolved on the surface at this time is preferably 0.05 to 0.3 g / m ² . In the present invention, it is preferable to have the desmut treatment step 16 after the electrolytic surface-roughening treatment step.

(Anodizing process)
Following the electrolytic surface-roughening treatment step 1, it is preferable to perform an anodizing 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 18V or more, and more preferably 20V or more. Current density is preferably 1~30A / dm ^2. Quantity of electricity is preferably from 200~600C / dm ^2.

Coated amount of the formed anodization film is preferably from 2 to 6 g / m ^2, preferably 2.5~5.0g / 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, it is preferable to have the hydrophilic treatment process 3 and the subsequent drying process 4 after performing said process.

  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. from the viewpoint of printing durability and prevention of stains, and the treatment time is preferably 6 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. from the viewpoint of printing durability and prevention of stains, and the treatment time is preferably 6 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 50,000, particularly preferably 10,000 to 40,000. 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, it is preferable to go through a drying step.

  A drying process is a process performed after a hydrophilic treatment process, and in a drying process, an aluminum plate is heated with a heating means.

  In the drying step 4, the heating means 41 heats and dries.

  The aluminum web is roughened in an electrolytic surface-roughening treatment step 1 and, if necessary, anodized in an anodizing step 2, further hydrophilized in a hydrophilic treatment step 3, and heated in a drying step 4. .

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

  Moreover, when performing an application | coating process, a drying process, and a cutting process continuously, it uses for the application | coating process of an image forming layer instead of the winding process 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 used in the present invention 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 the 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.

  Examples of the heat-sensitive image forming layer containing the above polymerization component include (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. Examples thereof include a heat-sensitive image forming layer.

((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 —CY 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) CY ₃ — (C═O) —X—R 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, examples of the compound that can be used in combination include a phosphoric ester compound containing at least one (meth) acryloyl group. 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, compounds described on 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 the above 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 thermal image forming layer may contain a polymerization inhibitor as necessary.

  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 polymerization inhibitor described above, other polymerization inhibitors may be added to the thermal 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.

  Moreover, a colorant can also be used for the said heat-sensitive image forming layer, and a conventionally well-known thing can be used conveniently as a colorant including a commercially available thing. 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 on 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 according to the present invention is a polymerization initiator, an image forming layer containing a polymerizable unsaturated group-containing compound, and a polymerization initiator used for a heat sensitive image forming layer containing the above polymerization component, The thing similar to the polymerizable unsaturated 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 the titanocene compound 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-bi -2,3,4,5,6-pentafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,3,5,6-tetrafluorophenyl, bis (methylcyclopentadienyl) -Ti -Bis-2,6-difluorophenyl (IRGACURE 727L: manufactured by Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium (IRGACURE 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 monoalkyltriaryl 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 used in the present invention includes unnecessary polymerization of an ethylenically unsaturated double bond monomer that can be polymerized during the production or storage of a photosensitive lithographic printing plate material. In order to prevent this, a hindered phenol compound, a hindered amine compound 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 used in the present invention in the same manner as described above.

(Application)
Examples of the solvent used when preparing the coating solution for the image forming layer of the present invention 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.

  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 according to the present invention. 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 photosensitive lithographic printing plate material of the present invention is subjected to image formation by image exposure, subjected to development treatment 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.

  In the present invention, it is preferable to perform image exposure with laser light to form an image.

  That is, a preferred embodiment is an image forming method in which the photosensitive lithographic printing plate material according to any one of claims 9 to 12 is subjected to image exposure with a laser beam 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 (Production of Supports 1 to 10)
Support 1
A long aluminum plate 1 having a thickness of 0.3 mm and a width of 730 mm (described in Table 1 with the content of components other than aluminum) is immersed in a 1.5% aqueous sodium hydroxide solution maintained at 55 ° C. and degreased for 20 seconds. After the treatment, it was washed with water. This degreased aluminum plate was neutralized by immersing in a 0.1% aqueous hydrochloric acid solution maintained at 25 ° C. for 10 seconds, and then washed with water.

Next, after carrying out an immersion treatment for 6 seconds while transporting 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., an AC sine waveform is used. Then, the substrate was transported under an electrode at a current density of 80 A / dm ² for 12.5 seconds to perform electrolytic surface roughening, and then washed with water. In addition, the immersion process and the electrolysis process were performed in the same tank filled with the solution containing hydrochloric acid used in the immersion process.

After the electrolytic surface roughening, it was immersed in a 75 g / l phosphoric acid aqueous solution maintained at 50 ° C. for 19 seconds, desmutted, and washed with water. The aluminum dissolution amount on the surface at this time was 0.1 g / m ² .

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.

  Next, it is dried at a plate surface temperature of 75 ° C. in a drying process having an infrared heater, and after coating with a nitrile rubber roller having a diameter of 340 mm for adjusting tension, the following lithographic printing plate material coating liquid is applied. The support body 1 used for the process to perform was produced.

Support 2-7
In the production of the support 1, the supports 2 to 7 were produced in the same manner as the production of the support 1 except that the aluminum plate shown in Table 2 was used and the immersion time in the dipping process was changed to the time shown in Table 2. .

Supports 8-10
In the production of the support 1, an aluminum plate shown in Table 2 was used, and a nitric acid solution having a nitric acid concentration of 10 g / l, a dissolved aluminum concentration of 8.5 g / l, and a temperature of 30 ° C. was used as the acidic solution. Supports 8 to 10 were prepared in the same manner as the support 1 except that the times shown in Table 2 were used. That is, the immersion process and the electrolysis process were performed in the same tank filled with the solution containing nitric acid used in the immersion process.

<Evaluation>
Next, using the following lithographic printing plate material coating liquids A to E, a photosensitive layer was coated on each of the above supports 1 to 10, respectively, and the obtained lithographic printing plate material was subjected to 50% flat netting by the following image forming method. An image is formed, and printing is performed by the following printing method. The halftone dot area (%) of the printed matter is measured at 385 points with a width of 20 mm and a length of 50 mm, and the maximum dot area (%) and the minimum dot area (%) ) Difference. The results are shown in Table 2. The smaller the difference between the maximum dot area (%) and the minimum dot area (%), the better the image reproduction uniformity.

(Preparation of photopolymer type planographic printing plate material for FD-YAG laser light source (532 nm))
A coating solution A having the following composition was applied to the supports 1 to 8 with a wire bar so that the coating liquid A was 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 600 mm through an interleaf feeder.

(Coating liquid A)
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 2-fold), a lithographic printing plate was 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 solution _{(SiO 2: 26%, K} 2 O: 13.5%) 40.0g / 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)
The lithographic printing plate produced by exposure and development is coated with printing paper (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.), and the 1000th sheet was sampled.

(Preparation of photopolymer type lithographic printing plate material for violet light source)
A coating liquid B having the following composition was applied to the supports 1 to 8 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 600 mm through an interleaf feeder.

(Coating solution B)
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 ( Developed with a CTP automatic developing machine (Raptor Polymer: manufactured by Glunz & Jensen) equipped with GW-3 (Mitsubishi Chemical Co., Ltd. diluted 2-fold), a lithographic printing plate was 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.

(Printing method)
The lithographic printing plate produced by exposure and development is coated with printing paper (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.), and the 1000th sheet was sampled.

(Preparation of photopolymer type lithographic printing plate material for infrared laser light source (830 nm))
A coating liquid C having the following composition was coated on the supports 1 to 8 with a wire bar so that the coating liquid C had a dry weight of 1.5 g / m ² 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 photosensitive lithographic printing plate material having a protective layer on the photosensitive layer was prepared through a slip sheet supplying device and a step of cutting to a length of 600 mm.

(Coating liquid C)
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 ( Developed with a CTP automatic developing machine (Raptor Polymer: manufactured by Glunz & Jensen) equipped with GW-3 (Mitsubishi Chemical Co., Ltd. diluted 2-fold), a lithographic printing plate was obtained. 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.

(Printing method)
The lithographic printing plate produced by exposure and development is coated with printing paper (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.), and the 1000th sheet was sampled.

(Preparation of positive lithographic printing plate material for infrared laser light source (830 nm))
To the support 8, it was coated with a wire bar so that the coating solution D having the following composition to dry 1.5 g / m ^2, and dried for 1.5 minutes at 95 ° C.. Next, a photosensitive lithographic printing plate material was prepared through a slip sheet feeding device and a step of cutting to a length of 600 mm.

(Coating solution D)
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 ( Developed with a CTP automatic developing machine (Raptor Polymer: manufactured by Glunz & Jensen) equipped with GW-3 (Mitsubishi Chemical Co., Ltd. diluted 2-fold), a lithographic printing plate was obtained.

  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.

(Printing method)
The lithographic printing plate produced by exposure and development is coated with printing paper (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.), and the 1000th sheet was sampled.

(Preparation of on-machine development type planographic printing plate material for infrared laser light source (830 nm))
(Preparation of hydrophilic layer)
A material having the following composition was sufficiently stirred and mixed using a homogenizer, followed by filtration to prepare a hydrophilic layer coating solution having a solid content of 15% by mass. The coating liquid for the hydrophilic layer is applied onto the supports 1 to 8 using a wire bar so that the weight after drying is 2.0 g / m ^2, and dried at 100 ° C. for 1.5 minutes. The aluminum support on which the hydrophilic layer was coated 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 coating solution E was applied using a wire bar and dried. Next, after passing through a slip-sheet supply device, a process of cutting to 600 mm length was performed, and then an aging treatment was performed to obtain a photosensitive lithographic printing plate sample.

Image forming layer: Amount with drying 1.50 g / m ² , Drying condition 55 ° C./3 minutes Aging condition: 40 ° C./24 hours (Coating solution E)
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 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 subjected to image exposure at 2400 dpi (dpi represents the number of dots per inch, that is, 2.54 cm) of 175 lines at 220 mJ / cm ² to obtain a lithographic printing plate. 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 H liquid SG-51 concentration 1.5% (manufactured by Tokyo Ink Co., Ltd.), and the 1000th sheet was sampled.

  From Table 2, it is understood that the lithographic printing plate material using the support produced by the method for producing an aluminum support 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 of this invention is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrolytic roughening process 2 Anodizing process 3 Hydrophilization process 4 Drying process 6 Rubber roller 7 Winding process 11 Roughening process tank 12 Immersion process 13 Electrolytic process 14 Electrolytic solution 15 Electrode 16 Desmutting process 21 Anodizing Treatment tank 31 Hydrophilization treatment tank 41 Heating means A Aluminum web

Claims (5)

A method for producing an aluminum support for a lithographic printing plate material comprising an electrolytic surface-roughening treatment step comprising an electrolytic step of electrolyzing and roughening the surface of an aluminum web to be conveyed, wherein the electrolytic solution comprises A lithographic plate characterized in that it is an electrolytic solution containing hydrochloric acid, and the electrolytic surface-roughening treatment step comprises an immersion step of immersing the aluminum web in the electrolytic solution for 6 seconds or more and 10 seconds or less before the electrolytic step. A method for producing an aluminum support for a printing plate material. The method for producing an aluminum support for a lithographic printing plate material according to claim 1, wherein the temperature of the electrolytic solution in the electrolysis step is the same as the temperature of the electrolytic solution in the immersion step. 3. The method for producing an aluminum support for a lithographic printing plate material according to claim 1, further comprising a desmut treatment step and an anodization treatment step after the electrolytic surface roughening treatment step. 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 claim 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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