JP2007055003A - Lithographic printing plate material and its aggregate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithographic printing plate material, even through the lamination of a large number of sheets of which with no slip sheet, a printed matter can be obtained with developing no image defect and its aggregate. <P>SOLUTION: In the lithographic printing plate material, which has an image forming layer on one side of an aluminum plate, the side opposite to the side having the image forming layer thereon of the aluminum plate is a side roughened through an electrochemical roughening process and an anodic oxidizing process under the condition that the arithmetic mean roughness (Ra) of the roughened surface is 0.10-0.30 μm and the amount of the anodically oxidized film of the roughened surface is 1.0-10.0 mg/dm<SP>2</SP>. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a planographic printing plate material using an aluminum plate as a support, and an assembly of the planographic printing plate material.

  In recent years, in a printing plate manufacturing technique for offset printing, a CTP (computer-to-plate) method for recording digital data of an image directly on a photosensitive printing plate with a laser light source has been developed and put into practical use.

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

  Conventionally, when a large number of lithographic printing plate materials are stacked, the image forming layer is scratched, or the plate stacked on the image forming layer is in contact with the image forming layer when left under pressure for a long time. In order to prevent the back side of the sheet from sticking and being unable to be transported by an automatic plate making machine or peeling off the image forming layer, it is common to insert a slip sheet called a slip sheet for each sheet. Has been done.

  As these slip sheets, those in which polyethylene or the like is laminated on one side or both sides in consideration of the influence on the image forming layer are generally used. However, these slip sheets cannot be used as recycled paper. When a large amount of lithographic printing plate material is used, a large amount of slip paper is discharged as industrial waste, which is disadvantageous in terms of resource reuse.

  Further, when a plate setter having a slip sheet removing mechanism is used, there is a problem that the slip sheet may not be removed well and a conveyance failure may occur, which may reduce the efficiency at the time of plate making.

  For this reason, proposals have been made to prevent the image forming layer from being damaged without requiring a slip sheet. For example, a method having a matting agent on a support opposite to the image forming layer (see Patent Document 1), a method of providing a backcoat layer on the surface opposite to the photosensitive layer (see Patent Document 2), an image forming layer And a method for defining the contact angle difference of water on the surface of the back layer (see Patent Document 3), and the like.

However, in these methods, when a large number of lithographic printing plate materials are deposited, there is a problem that image sticking prevention between the image forming layer and the back surface of the support is insufficient and image defects occur after image formation.
JP 2003-63162 A Japanese Patent Laid-Open No. 11-184073 JP 2003-207899 A

  An object of the present invention is to provide a lithographic printing plate material and an assembly of the lithographic printing plate material that can obtain a printed matter without causing image defects even when a large number of sheets are laminated without interleaving paper.

  The object of the present invention is achieved by the following constitution.

(1) In a lithographic printing plate material having an image forming layer on one surface of an aluminum plate, the surface of the aluminum plate opposite to the surface having the image forming layer is subjected to electrochemical roughening treatment and anodization. The rough surface is treated, the arithmetic average roughness (Ra) of the rough surface is 0.10 to 0.30 μm, and the amount of the anodic oxide coating on the rough surface is 1.0 to 10.0 mg / dm. ^2. A lithographic printing plate material characterized in that it is ² .

  (2) The lithographic printing plate material as described in (1) above, wherein the aluminum plate contains 0.1 to 0.4% by mass of Mg.

  (3) The lithographic printing plate material as described in (1) or (2) above, wherein the image forming layer is a heat-sensitive image forming layer.

  (4) The lithographic printing plate material as described in any one of (1) to (3) above, wherein the image forming layer is a photopolymerization type image forming layer.

  (5) The lithographic printing plate material as described in any one of (1) to (4) above, wherein the image forming layer is a layer developable on a printing press.

  (6) An assembly of lithographic printing plate materials as described in (1) to (5) above, which is an assembly of lithographic printing plate materials.

  According to the above configuration of the present invention, it is possible to provide a lithographic printing plate material and an assembly of the lithographic printing plate material that can obtain a printed matter without causing image defects even when a large number of sheets are laminated without interleaving paper.

  Hereinafter, the present invention will be described in detail.

  The present invention relates to a planographic printing plate material having an image forming layer on one surface of an aluminum plate, wherein the surface of the aluminum plate opposite to the surface having the image forming layer is subjected to an electrochemical roughening treatment and an anode. The rough surface is subjected to an oxidation treatment.

  In the present invention, the back surface of the aluminum plate as a support is a rough surface subjected to electrochemical roughening treatment and anodizing treatment, so that even if a large number of sheets are laminated without interleaving, image defects are caused. A lithographic printing plate material from which a printed matter can be obtained without being produced, and an aggregate of the lithographic printing plate material can be provided.

(Aluminum plate)
The planographic printing plate material of the present invention uses an aluminum plate as a support. As the aluminum plate, either a pure aluminum plate or an aluminum alloy plate can be used.

  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.

  Moreover, in this invention, it is more preferable that the aluminum plate contains 0.1-0.4 mass% of Mg. The phrase “containing Mg” means that the aluminum plate contains Mg as its elemental composition.

  The surface opposite to the surface having the image forming layer (hereinafter also referred to as the back surface) of the aluminum plate according to the present invention needs to be a rough surface subjected to electrochemical roughening treatment and anodizing treatment. is there.

(Electrochemical roughening treatment)
Prior to electrochemical roughening, the aluminum plate according to the present invention is preferably subjected to a degreasing treatment in order to remove 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 and desmutted. It is preferable to perform the treatment.

  Next, roughening treatment is performed. Prior to the electrochemical roughening treatment according to the present invention, pre-roughening is performed by mechanical roughening treatment, electrolytic roughening treatment mainly composed of nitric acid, or the like. May be.

The mechanical pre-roughening method is not particularly limited, but a brush polishing method and a honing polishing method are preferable. The roughening by the brush polishing method is, for example, by rotating a rotating brush using a bristle having a diameter of 0.2 to 0.8 mm, and for example, volcanic ash particles having a particle size of 10 to 100 μm on water. While supplying the uniformly dispersed slurry, the brush can be pressed. The roughening by honing polishing is performed by, for example, uniformly dispersing volcanic ash particles having a particle size of 10 to 100 μm in water, injecting pressure from a nozzle, and causing the surface to collide obliquely with the support surface. Can do. Further, for example, abrasive particles having a particle size of 10 to 100 μm are applied to the support surface so as to be present at a density of 2.5 × 10 ³ to 10 × 10 ³ particles / cm ² at intervals of 100 to 200 μm. Roughening can also be performed by laminating the sheets and applying a pressure to transfer the rough surface pattern of the sheet.

After the surface is roughened by the mechanical surface roughening method, it is preferable to immerse in an aqueous solution of acid or alkali in order to remove the abrasive that has digged into the surface of the support, formed aluminum scraps, and the like. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an aqueous alkali solution such as sodium hydroxide. The dissolution amount of aluminum in the support surface, 0.5 to 5 g / m ² is preferred. 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.

  The pre-electrolytic surface roughening treatment mainly composed of nitric acid can be performed by applying a voltage in the range of 1 to 50 volts, but is preferably selected from the range of 10 to 30 volts.

Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 20 to 100 A / dm ^2. The quantity of electricity, may be in the range of 100~1000C / dm ^2, preferably selected from the range of 200~700C / dm ^2. The temperature at which the electrochemical roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of nitric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, aluminum ions, and the like can be added to the electrolytic solution.

  After the electrolytic surface-roughening treatment mainly composed of nitric acid, it is preferably immersed in an acid or alkali aqueous solution in order to remove aluminum scraps on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an alkaline aqueous solution.

The dissolution amount of aluminum in the support surface, 0.5 to 5 g / m ² is preferred. In addition, it is preferable that after the immersion treatment with an alkaline aqueous solution, neutralization treatment is performed by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

  As the electrochemical surface roughening treatment according to the present invention, an AC electrolytic surface roughening treatment in an electrolytic solution mainly composed of hydrochloric acid is preferably used.

  In the AC electrolytic surface roughening treatment in an electrolytic solution mainly composed of hydrochloric acid, the hydrochloric acid concentration is 5 to 20 g / l, preferably 6.5 to 16 g / l. The temperature of the electrolytic solution is 15 to 38 ° C, preferably 18 to 35 ° C.

The aluminum ion concentration in the electrolytic solution is 0.5 to 15 g / l, preferably 0.7 to 10 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 current density is 15 to 120 A / dm ² , preferably 20 to 90 A / dm ² . The quantity of electricity was 100~1000C / dm ^2, preferably 200~700C / dm ^2. The frequency is preferably in the range of 40 to 150 Hz.

  The rough surface according to the present invention needs to have an arithmetic average roughness (Ra) of 0.10 to 0.30 μm.

  The arithmetic average roughness (Ra) in the present invention is defined by ISO4287.

  That is, the arithmetic average roughness (Ra) is obtained by extracting a portion of the measurement length lr from the roughness curve in the direction of the center line, and setting the X axis in the direction of the extracted portion and the Y axis in the direction of the vertical magnification y = Z. When expressed by (x), the value obtained by the following formula is expressed in micrometers (μm).

In order to make the above-mentioned roughness range, it is obtained by adjusting the electrolysis conditions of the above-mentioned electrochemical surface roughening treatment within the above-mentioned range. For example, the aluminum ion concentration in the electrolytic solution is 3 to 10 g / l, the concentration of acetic acid or boric acid in the electrolyte is 7 to 13 g / l, the ratio to the hydrochloric acid concentration is 0.7 to 1.2, the current density is 15 to 90 A / dm ² , and the quantity of electricity is 200 to 700 C / dm. It is preferable to adjust within the range of ² .

  The AC electrolytic treatment may be divided into several stages. For example, the method of changing the current density in multiple stages, the method of changing the AC waveform in multiple stages, the method of changing the frequency in multiple stages, and the acidic electrolyte concentration A multi-step method can be used.

After the electrolytic surface roughening treatment, that is, the electrochemical surface roughening treatment according to the present invention, is performed in an electrolytic solution mainly composed of hydrochloric acid, in order to remove aluminum scraps on the surface, an aqueous solution of acid or alkali is used. It is preferable to immerse. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an aqueous solution of phosphoric acid or sodium hydroxide. The amount of aluminum dissolved on the surface is preferably 0.1 to ² g / m ² . In addition, it is preferable that after the immersion treatment with an alkaline aqueous solution, neutralization treatment is performed by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

  Following the electrochemical surface roughening treatment, an anodizing treatment is performed.

  The method for anodizing treatment is not particularly limited, and a known method can be used. An oxide film is formed on the support by anodization. The anodizing treatment is generally carried out by direct current electrolysis using sulfuric acid or phosphoric acid or a mixed aqueous solution of both as the electrolytic solution.

In the present invention, the anodic oxidation treatment is preferably performed using 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. The amount of electricity is preferably ²⁰ to 200 C / dm2.

Coated amount of the formed anodization film is required to be 1.0~10.0mg / dm ^2, in particular, 2.0~8.0mg / dm ² is preferred.

The anodized coating amount is obtained by, for example, immersing an aluminum plate in a chromic phosphate solution (85% phosphoric acid solution: 35 ml, prepared by dissolving 20 g of chromium (IV) oxide in 1 L of water) to dissolve the oxide film, It is obtained from mass change measurement before and after dissolution of the coating on the plate. 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 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.

The aluminum plate used for the support of the lithographic printing plate material of the present invention can be obtained by processing as described above. That is, a method for producing a lithographic printing plate material having an image forming layer on one surface of an aluminum plate, wherein the surface opposite to the surface having the image forming layer is electrochemically roughened as the aluminum plate. An aluminum plate that is a rough surface subjected to the treatment and anodizing treatment is used, the arithmetic average roughness (Ra) of the rough surface is 0.10 to 0.30 μm, and the amount of the anodized film on the rough surface is 1 A preferred embodiment is a production method characterized by a range of 0.0 to 10.0 mg / dm ² .

(Image forming layer)
The lithographic printing plate material of the present invention has an image forming layer on the side opposite to the surface having the rough surface of the lithographic printing plate material support.

  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 particularly when the image forming layer according to the present invention is a heat-sensitive image forming layer or 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.

  A layer that can be developed on a printing press refers to a layer in which an image forming layer in a non-image area can be removed by dampening water and / or printing ink in lithographic printing after image 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 SnO ₂ doped with Sb (ATO), In ₂ O ₃ doped with Sn (ITO), TiO ₂ , TiO ₂ with reduced TiO ₂ (titanium oxynitride, generally titanium black), etc. Is 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-described infrared absorbers and the like 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, Japanese Patent Application Laid-Open No. 2001-343742 A compound that generates a radical by heat, Japanese Patent Application Laid-Open No. 2002-6482 a compound that generates an acid or radical by heat, Japanese Patent Application Laid-Open No. 2002-116539, Japanese Patent Application Laid-Open No. 2002-148790 A compound that generates an acid or a radical by the heat of heat, JP-A-2002-207293 Japanese Patent Application Laid-Open No. 2002-328465, photo- or thermal polymerization initiator having a polymerizable unsaturated group, Japanese Patent Application Laid-Open No. 2002-268217, an onium salt having a divalent or higher anion as a counter ion, and Japanese Patent Application Laid-Open No. 2002-328465 A compound such as a compound or a compound that generates a radical 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.A. 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, US Pat. Nos. 339,049, 410,201, JP-A-2-150,848, JP-A-2-296,514, etc. Of iodonium salts; 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-trifluoromethylphenyliodonium 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 image forming layer is not particularly limited, but is preferably in the range of 0.1 to 20% by mass in the constituent components of the image forming 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 Lactone adducts, pyrogallol triacrylate, propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate and other polyfunctional acrylic acid esters, 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.

  Furthermore, 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-propanediol and the like, but not limited thereto.

  Diisocyanate compounds 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 (isocyanate) Natomethyl) benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) reaction 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 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-ethylglycidyl (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 in which the carboxyl group, the epoxy group, and the unsaturated group-containing compound are reacted as a unit ratio, and the unit reacted in terms of sensitivity and printing durability is 5 to 50 mole%. 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 Coal 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 diacrylate of diglycidyl ether, 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 ester acid 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 solution (generally an alkaline aqueous solution) described later, 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 an image forming layer containing a polymerization initiator, a polymerizable unsaturated group-containing compound and a photosensitizing dye, and is used for a heat sensitive image forming layer containing the above polymerization component. The same polymerization initiator and polymerizable unsaturated group-containing compound can be used.

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

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

  Examples of the monoalkyl triaryl borate compound include compounds described in JP-A-62-150242 and JP-A-62-143044, and more preferable specific examples include tetra-n-butylammonium n-butyl-tri. Naphthalen-1-yl-borate, tetra-n-butylammonium n-butyl-triphenyl-borate, tetra-n-butylammonium n-butyl-tri- (4-tert-butylphenyl) -borate, tetra-n-butylammonium Examples include n-hexyl root- (3-chloro-4-methylphenyl) -borate and tetra-n-butylammonium n-hexyl root- (3-fluorophenyl) -borate.

  Examples of the iron arene complex compound include compounds described in JP-A-59-219307. More preferred 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- Examples include xylene- (η-cyclopentadienyl) iron hexafluorophosphate, η-benzene- (η-cyclopentadienyl) iron tetrafluoroborate.

  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.

(Photosensitizing dye)
As the sensitizing dye used in the polymerization type image forming layer, a sensitizing dye having an absorption maximum wavelength near the wavelength of the light source to be used is preferably used.

  Compounds that sensitize wavelengths from visible light to near infrared, that is, dyes having an absorption maximum between 350 nm and 1300 nm include, for example, cyanine, phthalocyanine, merocyanine, porphyrin, spiro compounds, ferrocene, fluorene, fulgide, imidazole, and perylene. , Phenazine, phenothiazine, polyene, xanthene, azo compound, diphenylmethane, triphenylmethane, polymethine acridine, coumarin, coumarin derivative, ketocoumarin, quinacridone, indigo, styryl, pyrylium compound, pyromethene compound, pyrazolotriazole compound, benzothiazole compound, barbi Examples thereof include ketoalcohol borate complexes such as tool acid derivatives and thiobarbituric acid derivatives, and further include European Patent No. 568,993 and US Patent No. 4,508. 811 No., 5,227,227 JP, JP 2001-125255, compounds described in JP-A 11-271969 Patent etc. are also used.

  Specific examples of the combination of the photopolymerization initiator and the sensitizing dye include combinations described in JP-A Nos. 2001-125255 and 11-271969.

  The amount of the sensitizing dye added to the image forming layer is preferably such that the reflection density of the plate surface at the exposure light source wavelength is in the range of 0.1 to 1.2. The mass ratio of the dye in the image-forming layer within this range varies greatly depending on the molecular extinction coefficient of each dye and the degree of crystallinity in the image-forming layer, but generally 0.5 mass percent. Often in the range of 10 weight percent.

  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 prevents unnecessary polymerization of an ethylenically unsaturated double bond monomer that can be polymerized during the production or storage of a lithographic printing plate material. In order to do this, a hindered phenol compound, a hindered amine compound, and other polymerization inhibitors may be added.

  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 And 8-triazaspiro [4.5] decane-2,4-dione.

  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-tert-butylphenol), N-nitrosophenylhydroxylamine cerium salt, 2,2,6,6, -tetramethylpiperidine derivatives, etc. It is done.

  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. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition by oxygen, or it may be unevenly distributed on the surface of the photopolymerization layer during the drying process after coating. Also good. 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 that can be preferably used in the present invention, as described above.

(Application)
Examples of the solvent used in preparing the image forming layer coating solution for forming the image forming layer according to 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, methyl Preferred examples include cyclohexanone and the like; esters: ethyl lactate, butyl lactate, diethyl oxalate, methyl benzoate and the like.

  The prepared coating composition (coating liquid for image forming layer) can be coated on a support by a conventionally known method and dried to prepare a photopolymerization planographic 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 image forming 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 a protective layer coating composition, the above-mentioned material can be dissolved in an appropriate solvent to form a coating solution, which is coated on the photopolymerization type image forming 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 applying the protective layer, the known application methods mentioned in the application of the image forming layer coating solution can be suitably used. The drying temperature of the protective layer is preferably lower than the drying temperature of the image forming layer, preferably the difference from the drying temperature of the image forming layer is 10 ° C. or more, more preferably 20 ° C. or more, and the upper limit is about 50 ° C. at most. It is.

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

(Hydrophilic layer)
The surface having the image forming layer of the aluminum plate of the lithographic printing plate material of the present invention preferably has a hydrophilic layer. The hydrophilic layer can be obtained by roughening and anodizing the surface of the aluminum plate. As a roughening method, electrochemical roughening is preferably used.

  Prior to electrochemical roughening, it is preferable to perform a degreasing treatment 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 and desmutted. It is preferable to perform the treatment.

  Next, a surface roughening treatment is performed. Prior to the electrochemical surface roughening treatment, pre-roughening may be performed by mechanical surface roughening treatment, electrolytic surface roughening treatment mainly composed of nitric acid, or the like.

The mechanical pre-roughening method is not particularly limited, but a brush polishing method and a honing polishing method are preferable. The roughening by the brush polishing method is, for example, by rotating a rotating brush using a bristle having a diameter of 0.2 to 0.8 mm, and for example, volcanic ash particles having a particle size of 10 to 100 μm on water. While supplying the uniformly dispersed slurry, the brush can be pressed. The roughening by honing polishing is performed by, for example, uniformly dispersing volcanic ash particles having a particle size of 10 to 100 μm in water, injecting pressure from a nozzle, and causing the surface to collide obliquely with the support surface. Can do. Further, for example, abrasive particles having a particle size of 10 to 100 μm are applied to the support surface so as to be present at a density of 2.5 × 10 ³ to 10 × 10 ³ particles / cm ² at intervals of 100 to 200 μm. Roughening can also be performed by laminating the sheets and applying a pressure to transfer the rough surface pattern of the sheet.

After the surface is roughened by the mechanical surface roughening method, it is preferable to immerse in an aqueous solution of acid or alkali in order to remove the abrasive that has digged into the surface of the support, formed aluminum scraps, and the like. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an aqueous alkali solution such as sodium hydroxide. The dissolution amount of aluminum in the support surface, 0.5 to 5 g / m ² is preferred. 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.

  The pre-electrolytic surface roughening treatment mainly composed of nitric acid can be performed by applying a voltage in the range of 1 to 50 volts, but is preferably selected from the range of 10 to 30 volts.

Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 20 to 100 A / dm ^2. The quantity of electricity, may be in the range of 5000 C / dm ^2, preferably selected from the range of 100~2000c / dm ^2. The temperature at which the electrochemical roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of nitric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, aluminum ions, and the like can be added to the electrolytic solution.

  After the electrolytic surface-roughening treatment mainly composed of nitric acid, it is preferably immersed in an acid or alkali aqueous solution in order to remove aluminum scraps on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an alkaline aqueous solution.

The dissolution amount of aluminum in the support surface, 0.5 to 5 g / m ² is preferred. In addition, it is preferable that after the immersion treatment with an alkaline aqueous solution, neutralization treatment is performed by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

  As the electrochemical surface roughening treatment according to the present invention, an AC electrolytic surface roughening treatment in an electrolytic solution mainly composed of hydrochloric acid is preferably used.

  In the AC electrolytic surface roughening treatment in an electrolytic solution mainly composed of hydrochloric acid, the hydrochloric acid concentration is 5 to 20 g / l, preferably 6.5 to 16 g / l. The temperature of the electrolytic solution is 15 to 38 ° C, preferably 18 to 35 ° C.

The aluminum ion concentration in the electrolytic solution is 0.5 to 15 g / l, preferably 0.7 to 10 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 current density is 15 to 120 A / dm ² , preferably 20 to 90 A / dm ² . The quantity of electricity was 400~2000C / dm ^2, preferably 500~1200C / dm ^2. The frequency is preferably in the range of 40 to 150 Hz.

The support for a lithographic printing plate material of the present invention is obtained by adjusting the electrolysis conditions for the electrochemical surface roughening treatment within the above range. For example, the aluminum ion concentration in the electrolytic solution is 3 to 3. 10 g / l, the concentration of acetic acid or boric acid in the electrolyte is 7 to 13 g / l, the ratio to the hydrochloric acid concentration is 0.7 to 1.2, the current density is 15 to 90 A / dm ² , and the quantity of electricity is 500 to 1200 C. It is preferable to adjust within the range of / dm ² .

In particular, the first half electrolysis at a current density of 40 A / dm ² or more, and the second half electrolysis at a current density of 35 A / dm ² or less, the first half electricity quantity> the latter half electricity condition, and the first half The rough surface according to the present invention can be obtained by electrolytic surface roughening under conditions of two-bath electrolysis using an electrolytic solution having a high hydrochloric acid concentration and an electrolytic solution having a high acetic acid concentration or a high boric acid concentration in the latter half.

  The AC electrolytic treatment may be divided into several stages. For example, the method of changing the current density in multiple stages, the method of changing the AC waveform in multiple stages, the method of changing the frequency in multiple stages, and the acidic electrolyte concentration A multi-step method can be used.

After the electrolytic surface roughening treatment, that is, the electrochemical surface roughening treatment, in the electrolyte mainly composed of hydrochloric acid, it may be immersed in an acid or alkali aqueous solution in order to remove aluminum scraps on the surface. preferable. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an aqueous solution of phosphoric acid or sodium hydroxide. The amount of aluminum dissolved on the surface is preferably 0.1 to ² g / m ² . In addition, it is preferable that after the immersion treatment with an alkaline aqueous solution, neutralization treatment is performed by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

  Following the electrochemical surface roughening treatment, it is preferable to perform anodization treatment.

The method for anodizing treatment is not particularly limited, and a known method can be used. An oxide film is formed on the support by anodization. The anodizing treatment is generally carried out by direct current electrolysis using sulfuric acid or phosphoric acid or a mixed aqueous solution of both as the electrolytic solution. In the present invention, the anodic oxidation treatment is preferably performed using 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 100 to 500 C / dm ^2.

The amount of anodic oxidation coating formed is suitably 1 to 50 mg / dm ² , preferably 10 to 40 mg / dm ² . The anodized coating amount is obtained by, for example, immersing an aluminum plate in a chromic phosphate solution (85% phosphoric acid solution: 35 ml, prepared by dissolving 20 g of chromium (IV) oxide in 1 L of water) to dissolve the oxide film, It is obtained from mass change measurement before and after dissolution of the coating on the plate. 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 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.

  Furthermore, in the present invention, it is preferable to perform a hydrophilic treatment after performing these treatments. Hydrophilization treatment is not particularly limited, but a water-soluble resin such as polyvinylphosphonic acid, a polymer and copolymer having a sulfonic acid group in the side chain, polyacrylic acid, a water-soluble metal salt (for example, zinc borate) or Undercoat with yellow dye or amine salt can be used. Furthermore, a sol-gel treated substrate in which a functional group capable of causing an addition reaction by a radical as disclosed in JP-A-5-304358 is covalently used. Preferably, the support surface is hydrophilized with polyvinylphosphonic acid. The treatment is not limited to a coating method, a spray method, a dip method, or the like, but a dip method is suitable for making the equipment inexpensive. In the case of a dip type, it is preferable to treat polyvinylphosphonic acid with a 0.05 to 3% aqueous solution. The treatment temperature is preferably 20 to 90 ° C., and the treatment time is preferably 10 to 180 seconds. After the treatment, it is preferable to perform a squeegee treatment or a water washing treatment in order to remove the excessively laminated polyvinylphosphonic acid. Furthermore, it is preferable to perform a drying process. As drying temperature, 90-250 degreeC is preferable.

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

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

  In the case of batch exposure, the photopolymerization mold may be overlaid with a mask material in which a negative pattern of a desired exposure image is formed of a light-shielding material.

  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 a printing method in which the lithographic printing plate material according to any one of claims 7 to 7 is subjected to image exposure with a laser beam to form an image, and then printed.

  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.

  When development processing is necessary, a method of developing the lithographic printing plate material using an automatic processor is a preferred embodiment.

  Printing can be performed using a general lithographic printing machine.

  In recent years, in the printing industry, from the viewpoint of environmental protection, inks that do not use petroleum-based volatile organic compounds (VOC) have been developed and are widely used as printing inks. This is particularly noticeable when the printing inks are used.

That is, in the present invention, the lithographic printing plate material according to any one of claims 3 to 6 is subjected to image exposure with a laser beam to form an image, and then a printing ink containing no petroleum-based volatile organic compound (VOC) is used. The printing method characterized by printing is a preferred embodiment. As environmentally friendly printing inks, soybean oil ink “Naturalis 100” manufactured by Dainippon Ink & Chemicals, Inc., VOC zero ink “TK” manufactured by Toyo Ink Co., Ltd. Hi-Echo NV ”, process ink“ Soiselbo ”manufactured by Tokyo Ink, Inc.

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

Example 1
(Preparation of supports 1 to 16)
An aluminum plate having a thickness of 0.3 mm (described in Table 1) was immersed in a 3% aqueous sodium hydroxide solution maintained at 50 ° C., degreased for 30 seconds, and then washed with water.

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

Next, an AC sine waveform was used in an electrolyte solution having a hydrochloric acid concentration of 11 g / L, an acetic acid concentration of 15 g / L, a dissolved aluminum concentration of 8 g / L, and a temperature of 30 ° C. Electrolytic roughening treatment was performed. Subsequently, an electrolytic surface-roughening treatment was performed on the image forming layer side at a current density of 55 A / dm ² for 18 seconds and washed with water.
After electrolytic surface roughening, it was immersed in a 75 g / l phosphoric acid aqueous solution maintained at 55 ° C. for 12 seconds, desmutted, and washed with water.

Next, using a direct current power source, an anodizing treatment on the side opposite to the image forming layer was performed 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. under the conditions shown in Table 1. It was. Subsequently, the anodization treatment on the image forming layer side was performed at a current density of 5 A / dm ² at 80 seconds, and washed with water.

  Further, a 0.2% aqueous solution of polyvinylphosphonic acid was subjected to a dip treatment at 60 ° C. for 40 seconds, then washed with distilled water, and dried with hot air at 150 ° C. for 30 seconds to prepare Supports 1-16.

Table 1 shows the arithmetic average roughness (Ra) and the amount of the anodic oxide film on the opposite side of the support from the image forming layer. The arithmetic average roughness (Ra) on the image forming layer side was 0.55 μm, and the amount of the anodized film was 30 mg / dm ² .

(Measurement of arithmetic average roughness (Ra))
Two-dimensional roughness measurement was performed with a contact-type roughness meter (SE1700α, manufactured by Kosaka Laboratory), the arithmetic average roughness (Ra) defined in ISO 4287 was measured five times, and the average value was used. Two-dimensional roughness measurement was performed under the following conditions. Cutoff 0.8 mm, measurement length 4 mm, scanning speed 0.1 mm / sec, stylus tip total 2 μm.

Aluminum plate 1: material, Al: 99.3% or more, Na: 0.003%, Mg: 0.20%, Si: 0.08%, Ti: 0.006%, Mn: 0.004%, Fe : 0.32%, Ni: 0.004%, Cu: 0.002%, Zn: 0.015%, Ga: 0.007% contained Aluminum plate 2: Material, Al: 99.5% or more, Na : 0.006%, Mg: 0.03%, Si: 0.04%, Ti: 0.03%, Mn: 0.004%, Fe: 0.32%, Ni: 0.004%, Cu: Contains 0.006%, Zn: 0.005%, Ga: 0.01% Aluminum plate 3: material, Al: 99.3% or more, Na: 0.003%, Mg: 0.50%, Si: 0.08%, Ti: 0.006%, Mn: 0.004%, Fe: 0.12%, Ni: 0.004%, u: 0.002%, Zn: 0.015%, Ga: containing 0.007% (FD-YAG laser light source (532 nm) Preparation of the corresponding photopolymerizable planographic printing plate material 1 to 16)
A photopolymerizable photosensitive layer coating solution having the following composition was coated on the supports 1 to 16 with a wire bar so as to be 1.6 g / m ² when dried, and dried at 95 ° C. for 1.5 minutes.

Thereafter, a protective layer coating solution having the following composition is further applied onto the photosensitive layer with an applicator so as to be 1.7 g / m ² when dried, and dried at 75 ° C. for 1.5 minutes to protect the photosensitive layer. A photopolymerization type photosensitive lithographic printing plate material having a layer was prepared.

(Photopolymerizable photosensitive layer coating solution)
Polymer binder B-1 (below) 40.0 parts Sensitizing dyes D-1 and D-2 (below) 1: 1 (mass) 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: manufactured by Mikuni Dye Co., Ltd.) 4.0 parts Fluorosurfactant (F178K: manufactured by Dainippon Ink & Chemicals, Inc.) 0.5 part Methyl ethyl ketone 80 parts Cyclohexanone 820 parts Synthesis of polymer binder 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)
With respect to the photopolymerization type photosensitive lithographic printing plate material thus prepared, 2400 dpi (1 dpi is 2.54 cm per inch) using a CTP exposure apparatus (Tigercat: manufactured by ECRM) equipped with an FD-YAG laser light source. An image of 175 lines was exposed at 150 μJ / cm ² at a resolution of (representing the number of dots). The exposed image includes a solid image and a 50% halftone dot 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 (PHW32-V: manufactured by Technigraph) equipped with GW-3 (Mitsubishi Chemical Co., Ltd. diluted twice), lithographic printing plates 1 to 16 were obtained.

  At this time, the heating unit was set so that the plate surface temperature was 105 ° C. and the plate staying time was 15 seconds.

  The plate was inserted into the heating unit of the self-machine after the exposure was completed within 30 seconds.

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

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

(Post-development image defect evaluation by deposition)
The applied lithographic printing plate material was cut into 730 mm × 600 mm, 400 sheets were stacked without sandwiching the interleaving paper, and left for 3 days in an environment of 25 ° C. and 55% and in a light-shielded state. Thereafter, the 400th planographic printing plate material from the top was subjected to the above-mentioned image formation, and the image defect state after development was evaluated as one index for preventing image defect occurrence. The evaluation results are shown in Table 2.

  A: Good with no image defects.

  B: A 50% halftone image is good, but a defect is observed in the solid image.

  C: A defect is recognized in both the 50% dot image and the solid image.

(Evaluation of printing durability by deposition)
The applied lithographic printing plate material is cut into 730 mm x 600 mm, 50 sheets are stacked without sandwiching the interleaf, one piece of cardboard with a thickness of about 0.5 mm is placed on the top and bottom, and the four corners are taped. Wrapped with kraft paper. This was further packaged with a cardboard case and taped, and then allowed to stand in an environment of 40 ° C. and 80% for 3 days. Thereafter, the above lithographic printing plate material from the top was subjected to the above printing after the above image formation. The number of printed sheets in which image defects occurred in a solid image or a 50% halftone dot image was measured, printing durability was evaluated, and this was used as one index for preventing image defects. The evaluation results are shown in Table 2.

  It can be seen from Table 2 that the planographic printing plate material of the present invention is excellent in preventing image defects when deposited without interleaving the interleaving paper.

Example 2
(Preparation of photopolymerization planographic printing plate materials 17 to 32 corresponding to violet light source)
A photopolymerization type photosensitive layer coating solution having the following composition was coated on the supports 1 to 16 with a wire bar so as to be 1.9 g / m ² when dried, and dried at 95 ° C. for 1.5 minutes.

Thereafter, a protective layer coating solution having the above composition is further applied onto the photosensitive layer with an applicator so as to be 1.7 g / m ² when dried, and dried at 75 ° C. for 1.5 minutes to protect the photosensitive layer. A photopolymerization type photosensitive lithographic printing plate material having a layer was prepared.

(Photopolymerization type photosensitive layer coating solution)
Polymer binder B-1 (above) 40.0 parts Photopolymerization initiator η-cumene- (η-cyclopentadienyl) iron hexafluorophosphate 3.0 parts Sensitizing dyes D-3 and D-4 (below) ) 1: 1 (mass) 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 Monomer NK ester 4G (polyethylene glycol dimethacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) 7.0 parts Compound C-1 having a group capable of cationic polymerization (described below) 8.0 parts Hindered amine compound (LS-770: manufactured by Sankyo) 0.1 part trihaloalkyl compound E-1 (previously described) 5.0 parts phthalocyanine pigment (MHI454: manufactured by Mikuni Dye Co., Ltd.) 7.0 parts fluorine-based surfactant (F178K: manufactured by Dainippon Ink & Chemicals, Inc.) 0.5 Methyl ethyl ketone 80 parts Cyclohexanone 820 parts

(Image formation)
About the photopolymerization type photosensitive lithographic printing plate material thus produced, 2400 dpi (dpi) using a plate setter (Tiger Cat: a modified product manufactured by ECRM) equipped with a light source having a laser of 408 nm and 30 mW output. An image of 175 lines was exposed at 50 μJ / cm ² at a resolution of 1 inch (representing the number of dots per inch).

  The exposed image includes a solid image and a 50% halftone dot image. Next, before development, a heating unit, a pre-water washing part for removing the protective layer, a developing part filled with the developer composition, a water washing part for removing the developer adhering to the plate surface, a gum solution for protecting the image area ( Development processing was performed with a CTP automatic developing machine (PHW32-V: manufactured by Technigraph) equipped with GW-3: manufactured by Mitsubishi Chemical Co., Ltd. twice to obtain lithographic printing plates 17 to 32. 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.

(Evaluation of post-development image defects by deposition, evaluation of printing durability by deposition)
Evaluation was performed in the same manner as described above. The results are shown in Table 3.

  It can be seen from Table 3 that the planographic printing plate material of the present invention is excellent in image defect prevention property due to the deposition sandwiching the interleaving paper.

Example 3
(Preparation of photopolymerization planographic printing plate materials 33 to 48 corresponding to infrared laser light source (830 nm))
A photosensitive layer coating solution having the following composition was coated on the supports 1 to 16 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 above composition is further applied onto the photosensitive layer with an applicator so as to be 1.7 g / m ² when dried, and dried at 75 ° C. for 1.5 minutes to protect the photosensitive layer. A photosensitive lithographic printing plate material having a layer was prepared.

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

(Image formation)
About the photosensitive lithographic printing plate material thus produced, a plate setter (Trend Setter 3244: manufactured by Creo) equipped with a light source of 830 nm was used, and 2400 dpi (dpi is the number of dots per inch, that is, 2.54 cm). An image of 175 lines was exposed at 150 mJ / cm ² with a resolution of (represented).

  The exposed image includes a solid image and a 50% halftone dot 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 (PHW32-V: manufactured by Technigraph) equipped with GW-3 (Mitsubishi Chemical Co., Ltd. diluted 2 times), lithographic printing plates 33 to 48 were 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.

(Evaluation of post-development image defects by deposition, evaluation of printing durability by deposition)
Evaluation was performed in the same manner as described above. The results are shown in Table 4.

  It can be seen from Table 4 that the planographic printing plate material of the present invention is excellent in image defect prevention property due to the deposition sandwiching the interleaving paper.

Example 4
(Preparation of positive type lithographic printing plate materials 49 to 64 corresponding to infrared laser light source (830 nm))
A photosensitive layer coating solution having the following composition is applied to the supports 1 to 16 with a wire bar so as to be 1.5 g / m ² when dried, and then dried at 95 ° C. for 1.5 minutes. Produced.

(Photosensitive layer coating solution)
Novolak resin (m-cresol / p-cresol = 60/40, weight average molecular weight 7,000, containing 0.5% by mass of unreacted cresol) 1.0 part Infrared absorber D-5 (above) 0.1 part Tetrahydro Phthalic anhydride 0.05 parts p-Toluenesulfonic acid 0.002 parts Ethyl violet counter ion converted to 6-hydroxy-β-naphthalenesulfonic acid 0.02 parts Fluorosurfactant (F178K: Dainippon Ink and Chemicals, Inc.) (Manufactured by Kogyo) 0.5 parts methyl ethyl ketone 12 parts (image formation)
About the photosensitive lithographic printing plate material thus produced, a plate setter (Trend Setter 3244: manufactured by Creo) equipped with a light source of 830 nm was used, and 2400 dpi (dpi is the number of dots per inch, that is, 2.54 cm). An image of 175 lines was exposed at 150 mJ / cm ² with a resolution of (represented).

  The exposed image includes a solid image and a 50% halftone dot image. Next, before development, a heating device part, a pre-washing part for removing the protective layer, a developing part filled with the following developer composition, a washing part for removing the developer adhering to the plate surface, a gum solution for protecting the image line part ( Development processing was performed with a CTP automatic developing machine (PHW32-V: manufactured by Technigraph) equipped with GW-3: manufactured by Mitsubishi Chemical Co., Ltd. twice to obtain lithographic printing plates 49 to 64. 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
Antifoaming agent Orphin 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.

(Evaluation of post-development image defects by deposition, evaluation of printing durability by deposition)
Evaluation was performed in the same manner as described above. The results are shown in Table 5.

  From Table 5, it can be seen that the planographic printing plate material of the present invention is excellent in image defect prevention property due to the deposition sandwiching the interleaving paper.

Example 5
(Preparation of on-machine development type lithographic printing plate material 65-80 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, and then filtered to prepare a hydrophilic layer coating solution having a solid content of 15% by mass.

The hydrophilic layer coating solution was applied onto the supports 1 to 16 using a wire bar so that the applied amount after drying was 2.0 g / m ² and dried at 100 ° C. for 3 minutes. 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, [sigma] s: 85.7 Am < ² > / kg, [sigma] r / [sigma] s: 0.112) 12.50 parts Colloidal silica (alkaline) Snowtex-XS (Nissan Chemical Co., Ltd., solid content 20 mass%) 60.62 10% by weight aqueous solution of trisodium phosphate / 12 water (reagent manufactured by Kanto Chemical Co., Inc.)
1.13 parts 10% by weight 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 following image forming layer coating solution was applied using a wire bar, dried, and then subjected to an aging treatment to obtain a 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 (image forming layer coating solution)
Aqueous polyurethane resin: Takelac W-615 (manufactured by Mitsui Takeda Chemical Co., Ltd.) Solid content 35% by mass: 17.1 parts Aqueous block isocyanate: Takenate XWB-72-N67 (manufactured by Mitsui Takeda Chemical Co., Ltd.) 45% by mass solid content: 7. 1 part Sodium polyacrylate: aqueous solution of Aqualic DL522 (manufactured by Nippon Shokubai Co., Ltd.), solid content: 10% by mass: 5.0 parts Photothermal conversion dye: ethanol solution of ADS830AT (manufactured by American DyeSource), 1% by mass: 30.0 Part pure water: 40.8 parts (image formation)
About the photosensitive lithographic printing plate material thus produced, a plate setter (Trend Setter 3244: manufactured by Creo) equipped with a light source of 830 nm was used, and 2400 dpi (dpi is the number of dots per inch, that is, 2.54 cm). The image of the 175 line of (represented) was exposed at 220 mJ / cm ² to obtain lithographic printing plates 65-80. The exposed image includes a solid image and a 50% halftone dot image.

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

(Defect evaluation by deposition)
The applied lithographic printing plate material was cut into 730 mm × 600 mm, 400 sheets were stacked without sandwiching the interleaving paper, and left for 3 days in an environment of 25 ° C. and 55% and in a light-shielded state. Thereafter, the 400th planographic printing plate material from the top was subjected to the above exposure / printing, and the image defect state of the 1000th printed sheet was evaluated and used as one index of image defect prevention. The evaluation results are shown in Table 6.

  A: Good with no image defects.

  B: A 50% halftone image is good, but a defect is observed in the solid image.

  C: A defect is recognized in both the 50% dot image and the solid image.

(Evaluation of printing durability by deposition)
The applied lithographic printing plate material is cut into 730 mm x 600 mm, 50 sheets are stacked without sandwiching the interleaf, one piece of cardboard with a thickness of about 0.5 mm is placed on the top and bottom, and the four corners are taped. Wrapped with kraft paper. This was further packaged with a cardboard case and taped, and then allowed to stand in an environment of 40 ° C. and 80% for 3 days. Thereafter, the above exposure / printing was performed on the 50th planographic printing plate material from the top. The number of printed sheets in which image defects occurred in a solid image or a 50% halftone dot image was measured, printing durability was evaluated, and used as one index for image defect prevention. The evaluation results are shown in Table 6.

  It can be seen from Table 6 that the lithographic printing plate material of the present invention is excellent in preventing image defects due to the deposition sandwiching the interleaving paper.

Claims (6)

In a lithographic printing plate material having an image forming layer on one surface of the aluminum plate, the surface of the aluminum plate opposite to the surface having the image forming layer is subjected to electrochemical roughening treatment and anodizing treatment. The arithmetic average roughness (Ra) of the rough surface is 0.10 to 0.30 μm, and the anodic oxide coating amount of the rough surface is 1.0 to 10.0 mg / dm ² . A lithographic printing plate material characterized by that. The lithographic printing plate material according to claim 1, wherein the aluminum plate contains 0.1 to 0.4 mass% of Mg. The lithographic printing plate material according to claim 1, wherein the image forming layer is a heat-sensitive image forming layer. The lithographic printing plate material according to any one of claims 1 to 3, wherein the image forming layer is a photopolymerization type image forming layer. The lithographic printing plate material according to claim 1, wherein the image forming layer is a layer that can be developed on a printing press. An assembly of lithographic printing plate materials according to claim 1, which is an assembly of lithographic printing plate materials according to claim 1.