JP2007047377A - Photosensitive lithographic printing plate material using fluorine compound having specific chemical structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive lithographic printing plate material which improves the coating property of a coating liquid, physical properties of a coating film and suitability to long-term running by using a compound substituted for a conventional fluorochemical surfactant in a photosensitive lithographic printing plate material. <P>SOLUTION: The photosensitive lithographic printing plate material has a constituent layer containing a fluorine compound on a support, wherein the constituent layer contains as the fluorine compound a fluorine compound represented by the general formula A: Y-(CF<SB>2</SB>)<SB>n</SB>-CF<SB>3</SB>or the general formula B: Z-(CF<SB>2</SB>)<SB>n</SB>-Y. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive lithographic printing plate material used in a so-called computer-to-plate (hereinafter referred to as “CTP”) system, and in particular, a fluorine compound having a specific chemical structure is used. The present invention relates to a photosensitive lithographic printing plate material.

  In recent years, digitization technology that electronically processes, stores, and outputs image information using a computer has become widespread, and in printing plate preparation technology for offset printing, directivity is determined according to digitized image information. A so-called CTP system that scans a high laser beam and directly records it on a photosensitive lithographic printing plate has been developed, and its practical application is progressing.

  Among the lithographic printing plate materials adapted to this CTP system, as a printing plate material that does not require a development treatment with a processing solution containing a special agent (for example, alkali, acid, solvent, etc.) and can be applied to a conventional printing press For example, for a so-called dry CTP method, such as a phase change type printing plate material that does not require development processing at all, or a printing plate material that does development processing at the initial stage of printing on a printing machine and does not require a development process. There are known printing plate materials. As specific examples, for example, ablation types described in JP-A-8-507727, JP-A-6-186750, JP-A-6-199064, JP-A-7-314934, JP-A-10-58636, JP-A-10-244773, and the like. An image is formed on a heat-sensitive image forming layer containing a photothermal conversion agent by image-like heat generation by laser exposure as described in JP, 2001-96710, 2001-138852, 2001-113848, etc. The thing of a system etc. are mentioned.

  Further, as disclosed in JP-A-2002-123000, JP-A-5-142786, JP-A-6-59461, JP-A-9-171254, JP-A-11-65105, and JP-A-11-115144. It is a photosensitive lithographic printing plate material for CTP having a heat-sensitive image forming layer, and a method for obtaining an image by exposing an image with an infrared laser and dissolving and removing an exposed portion that has become alkali-soluble is known.

  On the other hand, as a printing plate material for CTP having a relatively high printing durability, for example, a printing plate material having a photopolymerization type image forming layer described in JP-A No. 2002-107916 and JP-A No. 2003-76010 is used. Are known.

  By the way, as a solvent for the polymerizable composition or the like constituting the image forming layer of the above various printing plate materials, conventionally, a fluorine-based surfactant is generally used (for example, Patent Documents 1, 2, 3, and 4). , 5, 6).

  However, in recent years, there are concerns about the environmental impact of fluorosurfactants having a specific chemical structure with a high accumulation property such as PFOS (perfluorooctane sulfate), which has been used in the past. Therefore, there is a strong demand for the development of new alternative compounds to replace these.

On the other hand, lithographic printing plate materials use coating compounds, coating film properties, and charging characteristics (due to friction between the lithographic printing plate and interleaf and static electricity due to peeling, using alternative compounds that do not have environmental conservation problems as described above. There are demands for improvements in performance as lithographic printing plates.
JP 2002-131829 A JP 11-1225897 A Japanese Patent Laid-Open No. 11-268413 Japanese Patent Laid-Open No. 11-348446 JP 2000-131828 A JP 2002-40637 A

  In view of the above circumstances, the object of the present invention is to provide a coating material for a coating liquid, physical properties of a coating film, suitability for long-term running, etc. in a photosensitive lithographic printing plate material using an alternative compound of a conventional fluorosurfactant. It is an object of the present invention to provide an improved photosensitive lithographic printing plate material.

The above object of the present invention can be achieved by the following constitution.
(1) In a photosensitive lithographic printing plate material having a constituent layer comprising a fluorine compound on a support, the constituent layer is a fluorine compound represented by the following general formula A or general formula B as the fluorine compound. A photosensitive lithographic printing plate material comprising:
General formula _{A: Y- (CF 2) n} -CF 3
(Wherein, Y represents a SO ₃ X, COOX, or PO ₃ X group, X represents a K, Na, Li, or NH ₄ group. N represents a positive integer 2, 3, or 4.)
Formula _{B: Z- (CF 2) n} -Y
(In the formula, Y represents an SO ₃ X, COOX, PO ₃ X group, Z represents an SO ₃ X, COOX, PO ₃ X group, and X represents a K, Na, Li, or NH ₄ group. Represents a positive integer 2, 3, or 4.)
(2) The photosensitive lithographic printing plate material as described in (1), wherein the constituent layer is an image forming layer containing a photothermal conversion agent and an alkali-soluble resin.
(3) The photosensitive lithographic printing plate material as described in (1), wherein the constituent layer is an image forming layer containing an ethylenically unsaturated compound, a photopolymerization initiator, and an alkali-soluble resin.

  According to the present invention, in a photosensitive lithographic printing plate material having a heat-sensitive image forming layer, coating liquid coating properties, coating film physical properties (reduction of fingerprint trace stains and finger press trace pressures), long-term development running suitability (adhesive sludge) Reduction) has been achieved.

  Moreover, in the photosensitive lithographic printing plate material having a photopolymerizable image forming layer, the application property of the coating liquid, the electric resistance property of the printing plate material (releasability of the interleaf), the long-term development running suitability (adhesive sludge reduction), etc. Improvements have been achieved.

  Hereinafter, the present invention, components, and the like will be described in detail.

(Fluorine compound)
In the photosensitive lithographic printing plate material, the present invention is characterized in that the constituent layer of the printing plate material contains a fluorine compound represented by the above general formula A or B.

  Preferred specific examples of the fluorine compound represented by the above general formula A or B are given below, but the present invention is not limited thereto.

  Sodium perfluorobutane sulfonate, potassium perfluorobutane sulfonate, lithium perfluorobutane sulfonate, ammonium perfluorobutane sulfonate, sodium perfluoropropane sulfonate, potassium perfluoropropane sulfonate, lithium perfluoropropane sulfonate, per Ammonium fluoropropanesulfonate, sodium perfluoroethanesulfonate, potassium perfluoroethanesulfonate, lithium perfluoroethanesulfonate, ammonium perfluoroethanesulfonate, sodium perfluoropentanesulfonate, potassium perfluoropentanesulfonate, perfluoro Lithium pentanesulfonate, riamonium perfluoropentanesulfonate, 1,4-perfluorobutanedisulfone Acid soda, potassium 1,4-perfluorobutanedisulfonate, lithium 1,4-perfluorobutanedisulfonate, ammonium 1,4-perfluorobutanedisulfonate, sodium 1,3-perfluoropropanedisulfonate, 1,3 -Potassium perfluoropropane disulfonate, lithium 1,3-perfluoropropane disulfonate, ammonium 1,3-perfluoropropane disulfonate, sodium 1,2-perfluoroethane disulfonate, 1,2-perfluoroethane disulfonic acid Potassium, lithium 1,2-perfluoroethanedisulfonate, ammonium 1,2-perfluoroethanedisulfonate, sodium perfluoropentanoate, potassium perfluoropentanoate, lithium perfluoropentanoate, perfluoropen Ammonium phosphate, sodium perfluoroadipate, potassium perfluoroadipate, lithium perfluoroadipate, ammonium perfluoroadipate, sodium perfluorobutane phosphate, potassium perfluorobutane phosphate, lithium perfluorobutane phosphate, Perfluorobutane ammonium phosphate, 1,4-perfluorobutane diphosphate sodium, potassium perfluorobutane diphosphate, lithium 1,4-perfluorobutane diphosphate, ammonium 1,4-perfluorobutane diphosphate, and the like.

  The above-mentioned fluorine compound according to the present invention may be commercially available or can be produced by a usual synthesis method. Water, alcohol (eg, methanol, ethanol, isobutyl alcohol, etc.), ketones (eg, acetone, methyl ethyl ketone, isobutyl ketone, etc.), aromatic organic solvents (eg, toluene, xylene, etc.) are added to the coating solution. It can be dissolved or dispersed in fine particles. The coating amount is preferably in the range of 1 microgram to 10 grams per square meter.

  The constituent layer to which the fluorine compound according to the present invention is added includes an image forming layer (also referred to as “photosensitive layer”), an image forming layer protective layer, a back coat (also referred to as “BC”) layer, and a BC protective layer. Although it can be added, it is preferably added to the image forming layer and / or the image forming layer protective layer.

<Photosensitive planographic printing plate material having a thermal image forming layer>
The fluorine compound according to the present invention is a photosensitive lithographic printing plate material in which a heat-sensitive image forming layer containing a photothermal conversion dye, a polymerization initiator, a polymerizable compound, a polymer binder and the like is provided on a support. Can be preferably used. That is, the coating layer of the coating liquid, the coating film properties, the long-term development running suitability, etc. are improved by making the image forming layer contain a fluorine compound represented by the above general formula A or B. Can do.

  Hereinafter, components of the photosensitive lithographic printing plate material will be described.

(Image forming layer)
The image forming layer according to the present invention is a layer capable of forming an image by image exposure, and either a negative type or a positive type image forming layer can be used.

  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 that can be decomposed by an acid, a heat-sensitive image forming layer containing a polymerization component, a thermoplastic material, and a thermosetting material. A negative thermal image forming layer such as a thermal image forming layer containing a functional substance is preferably used.

[Positive image-forming layer containing a substance decomposable by acid]
As a positive type image forming layer containing a substance decomposable by the acid, for example, a photoacid generator that generates acid by laser exposure described in JP-A-9-171254 and a photoacid generator that generates acid by the laser exposure are developed and developed. Examples thereof include an image-forming layer comprising an acid-decomposable compound and an infrared absorber that increase the solubility in the liquid.

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]
As the photothermal conversion dye, the following compounds can be used.

  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.

  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.

[Thermal image forming layer containing polymerization component]
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.

[Photothermal conversion agent]
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.

(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.

  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%.

(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.

  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.

(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.

  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%.

[Thermal image forming layer containing thermoplastic material]
As the heat-sensitive image forming layer containing the thermoplastic material, an image forming layer containing heat-fusible particles or heat-fusible particles is preferable. In particular, an image forming layer used for process-less CTP is preferably used. It is done.

(Hot-melting particles)
The heat-meltable particles that can be used in the image forming layer are particles formed of a material that is low in viscosity when melted and is generally classified as a wax among thermoplastic materials.

  The physical properties are preferably a softening point of 40 ° C. or higher and 120 ° C. or lower, a melting point of 60 ° C. or higher and 150 ° C. or lower, in view of storage stability and ink inking property, a softening point of 40 ° C. or higher and 100 ° C. or lower, and a melting point of 60 ° C. or higher and 120 ° C. or lower. More preferably, it is not higher than ° C.

  Examples of materials that can be used include paraffin wax, polyolefin wax, polyethylene wax, microcrystalline wax, fatty acid ester wax, and fatty acid wax.

  These have a molecular weight of about 800 to 10,000, and in order to facilitate emulsification, these waxes can be oxidized to introduce polar groups such as a hydroxyl group, an ester group, a carboxyl group, an aldehyde group, and a peroxide group.

  Furthermore, in order to lower the softening point and improve workability, these waxes are used, for example, stearamide, linolenamide, laurylamide, myristamide, hardened bovine fatty acid amide, palmitoamide, oleic acid amide, rice sugar fatty acid amide. It is also possible to add coconut fatty acid amides or methylolated products of these fatty acid amides, methylene bisstellaramide, ethylene bisstellaramide and the like. Coumarone-indene resin, rosin-modified phenol resin, terpene-modified phenol resin, xylene resin, ketone resin, acrylic resin, ionomer, and copolymers of these resins can also be used.

  Among these, it is preferable to contain any of polyethylene wax, microcrystalline wax, fatty acid ester wax, and fatty acid wax. Since these materials have a relatively low melting point and a low melt viscosity, high-sensitivity image formation can be performed. Further, since these materials have lubricity, damage when a shearing force is applied to the surface of the printing plate material is reduced, and resistance to printing stains due to scratches or the like is improved.

  These heat-meltable particles are preferably dispersible in water, and the average particle diameter is preferably 0.01 to 10 μm, more preferably 0.05 to 3 μm from the viewpoint of on-press developability. .

  When the average particle size of the heat-meltable particles is larger than 10 μm, the resolution is lowered. In the case of containing two or more kinds of heat-meltable fine particles, the average particle diameter is preferably 0.1 μm or more away from each other.

  In order to disperse these heat-meltable particles in water, it is preferable to use a nonionic surfactant, an anionic surfactant, a cationic surfactant, or a polymer surfactant. By using these compounds, it is possible to stabilize an aqueous dispersion of heat-meltable fine particles, and to obtain a uniform coated product having no failure.

  Preferable examples of the nonionic surfactant include the following. Alkyl polyoxyethylene ether, alkyl polyoxyethylene, polyoxypropylene ether, fatty acid polyoxyethylene ester, fatty acid polyoxyethylene sorbitan ester, fatty acid polyoxyethylene sorbitol ester, polyoxyethylene castor oil, polyoxyethylene adduct of acetylene glycol, Polyoxyethylene adducts such as alkyl polyoxyethylene amines and amides; polyhydric alcohols and alkylol amides such as fatty acid sorbitan esters, fatty acid polyglycerin esters, fatty acid sucrose esters; polyether modified, alkyl aralkyl polyether modified, epoxy poly Silicon-based interfaces such as ether modification, alcohol modification, fluorine modification, amino modification, mercapto modification, epoxy modification, and allyl modification Sex agent; a fluorine-based surfactant such as perfluoroalkyl-ethylene oxide adducts; other lipid systems, biosurfactant, include oligo soap, these at least one can be used.

  Preferred examples of the cationic surfactant include primary amine salts, acylaminoethylamine salts, N-alkyl polyalkylene polyamine salts, fatty acid polyethylene polyamides, amides, and salts thereof, alkylamines such as amine salts, Acylamine salts; alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, alkylpyridium salt, acylaminoethylmethyldiethylammonium salt, acylaminopropyldimethylbenzylammonium salt, acylaminopropyl diethylhydroxyethylammonium salt Quaternary ammonium salts such as acylaminoethyl pyridium salts and diacylaminoethyl ammonium salts or ammonium salts having an amide bond; Esters such as ethylmethylhydroxyethylammonium salt and alkyloxymethylpyridium salt, ammonium salts having an ether bond; alkylimidazolines, 1-hydroxyethyl-2-alkylimidazolines, 1-acylaminoethyl-2-alkylimidazolium salts, etc. Imidazolines, imidazolium salts of amines; amine derivatives such as alkylpolyoxyethyleneamine, N-alkylaminopropylamine, N-acylpolyethylenepolyamine, acylpolyethylenepolyamine, fatty acid triethanolamine ester; other fatty, biosurfactant, oligosoap And at least one of these can be used.

  Examples of anionic surfactants include fatty acid salts, rosin groups, naphthene groups, ether carboxylates, alkenyl succinates, N-acyl sarcosine salts, N-acyl glutamates, primary alkyl sulfates, secondary alkyl sulfates. Carboxylic acid salts such as anealkyl sulfate polyoxyethylene salt, alkylphenyl polyoxyethylene sulfate, monoacylglycerol sulfate, acylaminosulfate ester, sulfate oil, sulfated fatty acid alkyl ester; α-olefin sulfonate, Secondary alkane sulfonate, α-sulfo fatty acid, acyl isethionate, N-acyl-N-methyl taurate, dialkyl sulfosuccinate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonate, petroleum sulfone Acid salt, rig Salts of sulfonic acids such as ninsulfonic acid salts; Salts of phosphoric acid esters such as alkyl phosphates and alkyl polyoxyethylene salts; Silicon-based anionic surfactants modified with sulfonic acid and carboxyl; Perfluoroalkylcarboxylic acid Fluorine surfactants such as salts, perfluoroalkyl sulfonates, perfluoroalkyl phosphates, perfluoroalkyltrimethylammonium salts; other lipids, biosurfactants, oligo soaps, and at least one of these can be used.

  Preferable examples of the polymeric surfactant include poly (meth) acrylic acid, butyl (meth) acrylate-acrylic acid copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, and other polyalkyl ( (Meth) acrylic acid homopolymer or copolymer; vinyl acetate-maleic anhydride copolymer, styrene-maleic anhydride copolymer, α-olefin-maleic anhydride copolymer, diisobutylene-maleic acid copolymer Maleic acid copolymers such as coalescence; Fumaric acid copolymers such as methyl (meth) acrylate-fumaric acid copolymer, vinyl acetate-fumaric acid copolymer; Naphthalenesulfonic acid formalin condensate, Butylnaphthalenesulfonic acid formalin condensation , Aromatic sulfonic acid formalin condensate such as cresol sulfonic acid formalin condensate; poly N- Polyalkylpyridinium salts such as tilvinylpyridinium chloride (including derivatives from copolymers of vinylpyridine and vinyl monomers copolymerized therewith); polyacrylamide, polyvinylpyrrolidone, polyacryloylpyrrolidone, polyvinyl alcohol, polyethylene glycol; poly Examples include block polymers of oxyethylene and polyoxypropylene; cellulose derivatives such as methylcellulose and carboxymethylcellulose; polyoxyalkylene / polysiloxane copolymers; polysaccharide derivatives such as arabic gum and arabinogalactan, and at least one of these can be used. In the specific example of the polymer surfactant, the polymer surfactant having a carboxyl group or a sulfone group may be an alkali salt such as sodium, potassium, or ammonium.

  Further, the composition of the heat-meltable particles may be continuously changed between the inside and the surface layer, or may be coated with a different material. As a coating method, a known microcapsule formation method, a sol-gel method, or the like can be used.

  As content of a heat-meltable particle, 1-90 mass% of the whole layer is preferable, and 5-80 mass% is still more preferable.

(Heat-bonding particles)
Examples of the heat-fusible particles include thermoplastic hydrophobic polymer particles, and there is no specific upper limit for the softening temperature of the thermoplastic hydrophobic polymer particles. It is preferable that the temperature is lower than the decomposition temperature. Moreover, it is preferable that the weight average molecular weight (Mw) of a high molecular weight polymer is the range of 10,000-1,000,000.

  Specific examples of the polymer constituting the thermoplastic hydrophobic polymer particles include, for example, diene (co) polymers such as polypropylene, polybutadiene, polyisoprene, and ethylene-butadiene copolymer, and styrene-butadiene. Synthetic rubbers such as copolymer, methyl methacrylate-butadiene copolymer, acrylonitrile-butadiene copolymer, polymethyl methacrylate, methyl methacrylate- (2-ethylhexyl acrylate) copolymer, methyl methacrylate-methacrylic acid copolymer, Methyl acrylate- (N-methylolacrylamide) copolymer, (meth) acrylic acid ester such as polyacrylonitrile, (meth) acrylic acid (co) polymer, polyvinyl acetate, vinyl acetate-vinyl propionate copolymer, acetic acid Vinyl-ethylene copolymer weight Vinyl ester (co) polymer such as a body, vinyl acetate - (2-ethylhexyl acrylate) copolymers, polyvinyl chloride, polyvinylidene chloride, polystyrene and copolymers thereof. Of these, (meth) acrylic acid esters, (meth) acrylic acid (co) polymers, vinyl ester (co) polymers, polystyrene, and synthetic rubbers are preferably used.

  The thermoplastic hydrophobic polymer particles may be made of a polymer polymer polymerized by any known method such as emulsion polymerization, suspension polymerization, solution polymerization, and gas phase polymerization. As a method for making a polymer polymer polymerized by a solution polymerization method or a gas phase polymerization method into a fine particle, a solution is sprayed in an inert gas in an organic solvent of the polymer polymer and dried to make a fine particle, Examples include a method in which a high molecular polymer is dissolved in an organic solvent immiscible with water, this solution is dispersed in water or an aqueous medium, and the organic solvent is distilled off to form fine particles.

  Further, in any of the methods, the heat-meltable particles and the heat-fusible particles may be used as a dispersant or a stabilizer, for example, when polymerized or granulated, for example, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, polyethylene A surfactant such as glycol or a water-soluble resin such as polyvinyl alcohol may be used. Further, triethylamine, triethanolamine or the like may be contained.

  The heat-fusible particles are preferably dispersible in water, and the average particle diameter is preferably 0.01 to 10 μm, more preferably 0.1 to 10 μm from the viewpoint of on-press developability and resolution. 3 μm.

  Further, the composition of the heat fusible particles may be continuously changed between the inside and the surface layer, or may be coated with a different material. As a coating method, a known microcapsule formation method, a sol-gel method, or the like can be used.

  As content of the heat-fusible particle | grains in a structural layer, 1-90 mass% of the whole layer is preferable, and 5-80 mass% is still more preferable.

(Water-soluble binder)
Examples of the water-soluble binder that can be used in the image forming layer include polysaccharides, polyethylene oxide, polypropylene oxide, polyvinyl alcohol, polyethylene glycol (PEG), polyvinyl ether, styrene-butadiene copolymer, and methyl methacrylate-butadiene copolymer. Examples thereof include conjugated diene polymer latex, acrylic polymer latex, vinyl polymer latex, polyacrylamide, polyacrylic acid or salts thereof, and resins such as polyvinyl pyrrolidone. Among them, it is preferable to use polyacrylic acid or a salt or polysaccharide thereof that does not deteriorate the printing performance.

  The image forming layer according to the present invention preferably contains lower alcohols such as methanol, ethanol, isopropyl alcohol and butanol in order to improve the coating quality. Moreover, the photothermal conversion raw material mentioned later can be contained.

The dry coating mass of the image forming layer is preferably 0.1 to 1.5 g / m ² , more preferably 0.15 to 1.0 g / m ² .

[Thermal image forming layer containing thermosetting substance]
Examples of the thermal image forming layer containing the thermosetting substance include a thermal image forming layer containing a material that is thermally crosslinked. Among these, in particular, an image forming layer used for so-called processless CTP is preferably used, and examples thereof include a heat-sensitive image forming layer containing a blocked isocyanate compound.

[Blocked isocyanate compound]
The blocked isocyanate compound is obtained by reacting an isocyanate compound with a blocking agent described below.

  The blocked isocyanate compound that can be used in the image forming layer is preferably an aqueous dispersion of a compound as described later.

[Isocyanate compound]
Isocyanate compounds include aromatic polyisocyanates [diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), polyphenylpolymethylene polyisocyanate (crude MDI), naphthalene diisocyanate (NDI), etc.]; aliphatic polyisocyanates [1, 6 -Hexamethylene diisocyanate (HDI), lysine diisocyanate (LDI), etc.]; Alicyclic polyisocyanate [isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, etc.]; [Xylylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), etc.]; , Isocyanurate groups, carbodiimide groups, oxazolidine group-containing modified compounds, etc.); and the urethane prepolymer and the like with these polyisocyanates with terminal isocyanate groups consisting of active hydrogen-containing compound having a molecular weight of 50 to 5,000.

  Further, polyisocyanate compounds described in JP-A-10-72520 can also be preferably used.

  Of the above, tolylene diisocyanate is particularly preferred because of its fast reactivity.

[Blocking agent]
A well-known thing can be used as a blocking agent of an isocyanate group. For example, alcohol blocking agents such as methanol and ethanol, phenol blocking agents such as phenol and cresol, formaldoxime, acetoaldoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, acetoxime, diacetyl monooxime, benzophenone oxime, etc. Oxime blocking agents, acid amid blocking agents such as acetanilide, ε-caprolactam, γ-butyrolactam, active methylene blocking agents such as dimethyl malonate and methyl acetoacetate, mercaptan blocking agents such as butyl mercaptan, succinic acid imide Imide blocking agents such as maleic imide, imidazole blocking agents such as imidazole and 2-methylimidazole, ureas such as urea and thiourea Examples include blocking agents, carbamic acid blocking agents such as phenyl N-phenylcarbamate, amine blocking agents such as diphenylamine and aniline, and imine blocking agents such as ethyleneimine and polyethyleneimine. Among these, it is particularly preferable to use an oxime blocking agent.

  The content of the blocking agent is preferably such that the active hydrogen group in the blocking agent is 1.0 to 1.1 equivalents relative to the isocyanate group of the isocyanate compound. When used in combination with an additive having a hydrogen group, the active hydrogen group, which is the sum of the blocking agent and the other additive having an active hydrogen group, is 1.0 to 1.1 equivalents relative to the isocyanate group. It is preferable to contain. If it is less than 1.0, unreacted isocyanate groups remain, and if it exceeds 1.1, the blocking agent or the like becomes excessive, which is not preferable.

  The dissociation temperature of the blocking agent is preferably 80 to 200 ° C, more preferably 80 to 160 ° C, and more preferably 80 to 130 ° C.

[Polyol]
The blocked isocyanate compound is preferably a polyol adduct obtained by further adding a polyol.

  By containing a polyol, the storage stability of the blocked isocyanate compound can be improved. Further, the image strength when the image is formed by heating is improved, and the printing durability is improved.

  Examples of the polyol include ethylene glycol, propylene glycol, triethylene glycol, glycerin, trimethylol methane, trimethylol propane, pentaerythritol, neopentyl glycol, 1,6-hexylene glycol, butanediol, hexamethylene glycol, xylylene glycol, Polyhydric alcohols such as sorbitol and sucrose, polyether polyols, polytetramethylene ether polyols, polycarbonate polyols, polyhydric alcohols or polyamines obtained by addition polymerization of ethylene oxide or propylene oxide, or both Caprolactone polyols and the above polyhydric alcohols such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, Sebashi Grafting vinyl monomers onto polyester polyols, polybutadiene polyols, acrylic polyols, castor oil, polyether polyols or polyester polyols obtained by reacting with polybasic acids such as acid, fumaric acid, maleic acid, and azelaic acid Examples thereof include polymer polyols and epoxy-modified polyols obtained. Among these, ethylene glycol, propylene glycol, triethylene glycol, glycerin, trimethylol methane, trimethylol propane, pentaerythritol, neopentyl glycol, 1,6-hexylene glycol, butanediol, hexamethylene glycol, xylylene glycol A polyol having a molecular weight of 50 to 5000 such as sorbitol can be preferably used, and a low molecular weight polyol having a molecular weight of about 50 to 500 can be particularly preferably used.

  The preferred content of the polyol is in such a range that the hydroxyl group in the polyol is 0.1 to 0.9 equivalent to the isocyanate group of the isocyanate compound. In this range, the storage stability of the blocked isocyanate compound is particularly good. improves.

[Blocking method]
As a method for blocking an isocyanate compound, for example, the isocyanate compound is heated to about 40 to 120 ° C. in an inert gas atmosphere under anhydrous conditions, and a predetermined amount of the blocking agent is dropped and mixed while stirring, followed by stirring. There is a method of reacting over several hours while continuing. At this time, any solvent can be used. Moreover, a well-known catalyst, for example, an organometallic compound, a tertiary amine, a metal salt etc. can also be used.

  Examples of the organometallic catalyst include stannous catalysts such as stannous octoate, dibutyltin diacetate, and dibutyltin dilaurate; lead-based catalysts such as lead 2-ethylhexanoate; and tertiary amines such as triethylamine, N, N-dimethylcyclohexylamine, triethylenediamine, N, N′-dimethylpiperazine, diazabicyclo (2,2,2) -octane, etc. are examples of metal salt catalysts such as cobalt naphthenate, calcium naphthenate, naphthenic acid. Lead lithium oxide etc. are mentioned. The usage-amount of these catalysts is 0.001-2 mass parts normally with respect to 100 mass parts of polyisocyanate compositions, Preferably it is 0.01-1 mass part.

  In the case where the blocked isocyanate compound is also a compound with a polyol, the blocking agent and the polyol are reacted with the isocyanate compound. After the isocyanate compound and the polyol are reacted first, the remaining isocyanate group and the blocking agent are reacted with each other. In addition, after the isocyanate compound and the blocking agent are reacted first, the remaining isocyanate group and the polyol may be reacted.

  As a preferable average molecular weight of the blocked isocyanate compound, a weight average molecular weight of 500 to 2000 is preferable, and 600 to 1000 is more preferable. Within this range, the balance between reactivity and storage stability becomes good.

[Production of water dispersion]
The blocked isocyanate compound obtained as described above can be made into an aqueous dispersion by, for example, adding a surfactant and water, and vigorously mixing and stirring using a homogenizer or the like.

  Examples of surfactants include anionic surfactants such as sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium dodecyl diphenyl ether disulfonate, sodium succinate dialkyl ester sulfonate, polyoxyethylene alkyl ester, polyoxyethylene alkyl aryl, and the like. Nonionic surfactants such as ethers, or alkylbetaine type salts such as lauryl betaine and stearyl betaine salts, both amino acid types such as lauryl-β-alanine, lauryl di (aminoethyl) glycine and octyldi (aminoethyl) glycine Surfactant etc. can be mentioned. These can be used alone or in combination of two or more. Of these, nonionic surfactants are preferred.

  The solid content of the blocked isocyanate compound aqueous dispersion is preferably 10 to 80% by mass. As addition amount of surfactant, it is preferable that it is 0.01-20 mass% in solid content of an aqueous dispersion.

  When an organic solvent is used for the blocking reaction of the isocyanate compound, the organic solvent can be removed after forming an aqueous dispersion.

  The image forming layer containing an isocyanate compound may further contain a water-soluble material, and examples of the water-soluble material include the following materials.

[Water-soluble polymer compound]
Examples of the water-soluble material contained in the image forming layer include known water-soluble polymer compounds that dissolve in an aqueous solution having a pH of 4 to 10.

  Specific examples include resins such as polysaccharides, polyethylene oxide, polypropylene oxide, polyvinyl alcohol, polyethylene glycol (PEG), polyvinyl ether, polyacrylic acid, polyacrylate, polyacrylamide, and polyvinylpyrrolidone.

  Of these, polysaccharides, polyacrylic acid, polyacrylates, polyacrylamide, and polyvinylpyrrolidone are preferable.

  As polysaccharides, starches, celluloses, polyuronic acids, pullulan, chitosan, or derivatives thereof can be used, and cellulose derivatives such as methyl cellulose salts, carboxymethyl cellulose salts, and hydroxyethyl cellulose salts are particularly preferable. Carboxymethyl cellulose The sodium salt and ammonium salt are more preferable.

  The polyacrylic acid, polyacrylate, and polyacrylamide preferably have a molecular weight of 3,000 to 1,000,000, and more preferably 5,000 to 500,000.

  Of these, polyacrylates such as sodium polyacrylate are most preferred. The polyacrylate is highly effective as a hydrophilic treatment agent for the hydrophilic layer, and can improve the hydrophilicity of the surface of the hydrophilic layer that appears when the image forming layer is developed on the machine.

[oligosaccharide]
As a water-soluble material, an oligosaccharide can be contained in addition to the water-soluble polymer compound described above.

  Examples of the oligosaccharide include raffinose, trehalose, maltose, galactose, sucrose, and lactose, and trehalose is particularly preferable.

(Image formation-printing)
Image formation for producing a printing plate using the printing plate material of the present invention is preferably performed by heating in image exposure. As the exposure method, exposure with a laser is particularly preferable.

  After exposure, it is processed with a developer and used as a printing plate. As the developer, an alkaline aqueous solution, an organic solvent-containing solution, or the like can be used.

(Alkaline agent)
Examples of the alkaline agent used in the alkaline aqueous solution include sodium silicate, potassium, and ammonium; dibasic sodium phosphate, potassium, and ammonium; sodium bicarbonate, potassium, and ammonium; sodium carbonate, potassium, and ammonium. Sodium bicarbonate, potassium, ammonium; sodium borate, potassium, ammonium; inorganic alkali agents such as sodium hydroxide, potassium, ammonium, and lithium.

  Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-i-propylamine, di-i-propylamine, tri-i-propylamine, butylamine, monoethanolamine, diethanolamine, triethanolamine, Organic alkali agents such as mono-i-propanolamine, di-i-propanolamine, ethyleneimine, ethylenediamine, and pyridine can also be used.

  In addition to the above salts, salts such as sulfosalicylic acid, salicylic acid, sugar alcohols of non-reducing sugars, saccharose, D-sorbit and the like can also be used.

  The organic solvent used in the organic solvent-containing solution is suitably selected from those having a water solubility of about 10% by mass or less, preferably 5% by mass or less.

  For example, 1-phenylethanol, 2-phenylethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 4-phenyl-2-butanol, 2-phenyl-1-butanol, 2-phenoxyethanol, 2- Benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N-phenylethanol Examples thereof include amines and N-phenyldiethanolamine.

  The developer may contain anionic, cationic, nonionic and amphoteric surfactants, pH buffering agents, reducing agents, organic carboxylic acids, and development stabilizers as necessary.

<Photopolymerization type photosensitive lithographic printing plate material>
The fluorine compound according to the present invention is also used in a photosensitive lithographic printing plate material in which an image forming layer containing a spectral sensitizer, a photopolymerization initiator, a polymerizable compound, and a polymer binder is provided on a support. Can be preferably used. That is, when the image forming layer contains the fluorine-based compound represented by the above general formula A or B, the coating solution coating property, interleaf separation property, and long-term development running suitability are improved. can do.

  Hereinafter, components of the photopolymerization type photosensitive lithographic printing plate material will be described.

(Photopolymerizable image forming layer)
The photosensitive lithographic printing plate used in the present invention contains a polymer binder in the photopolymerizable image forming layer. 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.

  A vinyl copolymer obtained by copolymerization of acrylic monomers is preferred. Furthermore, the copolymer composition of the polymer binder 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, in the polymer binder of the present invention, monomers described in the following (1) to (14) can be used as other copolymerization monomers.

  1) Monomers having an aromatic hydroxyl group such as o- (or p-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenyl acrylate, o- (or p-, m-) hydroxy (meta ) Acrylamide etc.

  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.

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

  Furthermore, an unsaturated bond-containing vinyl copolymer obtained by addition-reacting 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. Is also preferred as a polymer binder.

  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.

  These copolymers preferably have a mass average molecular weight of 1 to 200,000 as measured by gel permeation chromatography (GPC), but are not limited to this range.

  The content of the polymer in the image forming layer composition is preferably in the range of 10 to 90% by mass, more preferably in the range of 15 to 70% by mass, and sensitivity to be used in the range of 20 to 50% by mass. This is particularly preferable.

  Further, the acid value of the resin is preferably used in the range of 10 to 150, more preferably in the range of 30 to 120, and the use in the range of 50 to 90 is a viewpoint of balancing the polarity of the entire image forming layer. From this, it is possible to prevent aggregation of the pigment in the image forming layer coating solution.

  These compounds containing an addition-polymerizable ethylenic double bond according to the present invention include general radical-polymerizable monomers and ethylenic monomers that can be addition-polymerized in a molecule generally used for ultraviolet curable resins. Polyfunctional monomers having a plurality of double bonds and polyfunctional oligomers can be used. The compound is not limited, but preferred examples include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydro Furfuryloxyhexanolide acrylate, acrylate of ε-caprolactone adduct of 1,3-dioxane alcohol, monofunctional acrylic acid esters such as 1,3-dioxolane acrylate, or these acrylates as methacrylate, itaconate, crotonate, maleate Methacrylic acid, itaconic acid, crotonic acid, maleic acid esters such as ethylene glycol diacrylate , Triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, dipentylate of hydroxypentylate neopentyl 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, Ε-caprolactone adduct of 3-dioxane diacrylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylol acrylate Difunctional acrylic acid esters such as diglycidyl ether diacrylate of 1,6-hexanediol, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, For example, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol Ε-caprolactone adduct of hexaacrylate, pyrogallol triacrylate Polyfunctional acrylic acid esters such as propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, or these acrylates with methacrylate, itaconate, crotonate, Examples thereof include methacrylic acid, itaconic acid, crotonic acid, and maleic acid ester instead of maleate.

  Prepolymers can also be used as described above. Examples of the prepolymer include compounds as described below, and a prepolymer obtained by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight and imparting photopolymerizability can be preferably used. These prepolymers may be used alone or in combination of two or more, and may be used by mixing with the above-mentioned monomers and / or oligomers.

  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.

  The photosensitive composition of the present invention includes a phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) modified diacrylate, isocyanuric acid EO modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane benzoic acid benzoate. Addition-polymerizable oligomers and prepolymers having monomers such as acid esters, alkylene glycol type acrylic acid-modified, urethane-modified acrylates, and structural units formed from the monomers can be contained.

  Furthermore, examples of the ethylenic monomer that can be used in combination with the present invention include phosphate ester compounds containing at least one (meth) acryloyl group. The compound is not particularly limited as long as it is a compound in which at least part of the hydroxyl group of phosphoric acid is esterified and has a (meth) acryloyl group.

  In addition, JP-A-58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092, 63- 67189, JP-A-1-244891, and the like. Further, “11290 Chemical Products”, Chemical Industry Daily, p. 286-p. 294, “UV / EB Curing Handbook (raw material)”, Kobunshi Publishing Co., p. The compounds described in 11 to 65 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.

  In the present invention, it is preferable to use an addition-polymerizable ethylenic double bond-containing monomer containing a tertiary amino group in the molecule. 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, collectable compounds described in JP-A-1-165613, JP-A-1-203413, and JP-A-1-197213 are preferably used.

  Furthermore, the present invention uses 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 preferred.

  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, Although 2-propanediol etc. are mentioned, it is not limited to this.

  Examples of the diisocyanate compound include butane-1,4-diisocyanate, hexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate, octane-1,8-diisocyanate, 1,3-diisocyanate methyl-cyclohexanone. 2,2,4-trimethylhexane-1,6-diisocyanate, isophorone diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene- Examples include 2,5-diisocyanate, tolylene-2,6-diisocyanate, 1,3-di (isocyanatomethyl) benzene, 1,3-bis (1-isocyanato-1-methylethyl) benzene, and the like. Limited to Not. Compounds 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-di Methacrylate, 2-hydroxypropylene-1-methacrylate-3-acrylate and the like.

  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 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. Shown in
M-1: reaction product of triethanolamine (1 mol), hexane-1,6-diisocyanate (3 mol), 2-hydroxyethyl methacrylate (3 mol) M-2: triethanolamine (1 mol), isophorone Reaction product of diisocyanate (3 mol) and 2-hydroxyethyl acrylate (3 mol) M-3: Nn-butyldiethanolamine (1 mol), 1,3-bis (1-isocyanate-1-methylethyl) Reaction product of benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) M-4: Nn-butyldiethanolamine (1 mol), 1,3-di (isocyanatomethyl) ) Reaction of benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) Product M-5: Reaction product of N-methyldiethanolamine (1 mol), tolylene-2,4-diisocyanate (2 mol), 2-hydroxypropylene-1,3-dimethacrylate (2 mol) Also, acrylates or alkyl acrylates described in JP-A-1-105238 and JP-A-2-127404 can be used.

(Photopolymerization initiator)
The photopolymerizable image forming layer of the photosensitive lithographic printing plate of the present invention contains a photopolymerization initiator composition. Examples of the photopolymerization initiator composition include titanocene compounds, iron arene complex compounds, trihaloalkyl compounds, and monoalkyltriarylborate compounds.

[Titanocene compound]
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- (pyridin-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.

[Iron arene complex compound]
Examples of the iron arene complex compound include compounds described in JP-A-59-219307, and more preferable specific examples include η-benzene- (η-cyclopentadienyl) iron / hexafluorophosphate, η- Cumene- (η-cyclopentadienyl) iron / hexafluorophosphate, η-fluorene- (η-cyclopentadienyl) iron / hexafluorophosphate, η-naphthalene- (η-cyclopentadienyl) iron / hexafluoro Examples include phosphate, η-xylene- (η-cyclopentadienyl) iron / hexafluorophosphate, η-benzene- (η-cyclopentadienyl) iron / tetrafluoroborate, and the like.

[Monoalkyl aryl borate compound]
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- Trinaphthalen-1-yl-borate, tetra-n-butylammonium / n-butyl-triphenyl-borate, tetra-n-butylammonium / n-butyl-tri- (4-tert-butylphenyl) -borate, tetra -N-butylammonium · n-hexyl-tri- (3-chloro-4-methylphenyl) -borate, tetra-n-butylammonium · n-hexyl-tri- (3-fluorophenyl) -borate, etc. .

[Trihaloalkyl compounds]
The photosensitive lithographic printing plate of the present invention itself contains a compound containing a photodegradable trihaloalkyl group known as a free radical forming photoinitiator for a photopolymerizable mixture. As this type of combination initiator, compounds containing chlorine and bromine as halogen are particularly suitable. The trihaloalkyl group is preferably a trihalomethyl group, and is preferably bonded to an aromatic carbocycle or a heterocycle directly or via a continuously conjugated chain. Preferred are those having a triazine ring having two trihalomethyl groups as a mother nucleus, particularly described in EP-A-137,452, DE-A-2,118,259 and 2243621 Compounds are preferred. These compounds exhibit strong light absorption in the near ultraviolet region, for example, 350 to 400 nm. Combination initiators that do not absorb themselves or absorb very little light in the spectral region of the copying light, for example trihalomethyltriazines containing substituents with short electronic systems or aliphatic substituents that allow mesomeries; Is also appropriate. Likewise suitable are compounds having different basic skeletons and absorbing light in the short-wave ultraviolet region, such as phenyl trihalomethyl sulfone or phenyl trihalomethyl ketone, such as phenyl tribromomethyl sulfone.

  In addition, any photopolymerization initiator can be used in combination. For example, J. et al. 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 a photopolymerization initiator that can be used in combination. 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, 61-9621 and JP-A-60-60104 Triazine derivatives; organic peroxides described in JP-A-59-1504 and JP-A-61-243807; JP-B-43-23684, JP-A-44-6413, JP-A-44-6413, JP-A-47-1604, and US patents Diazonium compounds described in US Pat. No. 3,567,453; organic azide compounds described in US Pat. Nos. 2,848,328 and 2,852,379 and 2,940,853; O-quinonediazides described in JP-A Nos. 13109, 38-18015 and 45-9610; JP-B-55-39162, JP-A-59-14023 and “Macromolecules”, Vol. 10, 1307 Various onium compounds described on page 1977; azo compounds described in JP-A-59-142205 Compound: JP-A-1-54440, European Patents 109,851, 126,712 and “Journal of Imaging Science (J. Imag. Sci.)”, Vol. 30, 174 (1986) (Oxo) sulfonium organoboron complexes described in JP-A-5-213861 and JP-A-5-255347; "Coordination Chemistry Review", 84, 85-277 (1988) And transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701; 2,4,5-triarylimidazole dimer described in JP-A-3-209477; carbon tetrabromide, JP Organohalogen compounds described in 59-107344 And the like can be given.

[Spectral sensitizing dye]
When laser light is used as the light source, a spectral sensitizing dye is preferably added to the image forming layer. It is preferable to use a dye having an absorption maximum wavelength in the vicinity of the wavelength of the light source.

  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.

  Further, when recording is performed using a semiconductor laser having a light emission wavelength in the range of 380 nm to 430 nm, that is, a so-called violet laser as a laser beam of the light source, it is desirable to include a dye having an absorption maximum between 350 nm and 450 nm. The dye having an absorption maximum between 350 nm and 450 nm is not particularly limited in terms of structure, but cyanine, phthalocyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, Polyene, azo compound, diphenylmethane, triphenylmethane, polymethine acridine, coumarin, coumarin derivative, ketocoumarin, quinacridone, indigo, styryl, pyrylium compound, pyromethene compound, pyrazolotriazole compound, benzothiazole compound, barbituric acid derivative, thiobarbitur tool Any dye group such as an acid derivative and a keto alcohol borate complex can be used as long as the absorption maximum satisfies the requirement. Specifically, JP-A No. 2002-296664, JP-A No. 2002-268239, JP-A No. 2002-268238, JP-A No. 2002-268204, JP-A No. 2002-221790, JP-A No. 2002-202598, JP-A No. 2001-042524, JP-A No. 2000 are disclosed. Although the dyes described in JP-A-309724, JP-A-2000-258910, JP-A-2000-206690, JP-A-2000-147663, JP-A-2000-098605 and the like can be used, the present invention is not limited thereto.

  Although the compounding quantity of these polymerization initiators is not specifically limited, Preferably, it is 0.1-20 mass parts with respect to 100 polymerization parts of compound which can be addition-polymerized or bridge | crosslinked. The mixing ratio of the photopolymerization initiator and the sensitizing dye is preferably in the range of 1: 100 to 100: 1 in terms of molar ratio. Specific examples include D-1 to D-8.

(Oxygen barrier layer)
The photosensitive lithographic printing plate of the present invention preferably has an oxygen barrier layer. For the oxygen barrier layer, a water-soluble polymer capable of forming a film having low oxygen permeability is used. Specifically, it contains polyvinyl alcohol and polyvinyl pyrrolidone. 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.

  In the photosensitive lithographic printing plate of the present invention, the peeling force between the image forming layer and the oxygen blocking layer is preferably 35 g / 10 mm or more, more preferably 50 g / 10 mm or more, and further preferably 75 g / 10 mm or more. Preferred examples of the composition of the oxygen barrier layer include those described in JP-A-10-10742.

  The oxygen barrier layer can further contain a surfactant, a matting agent and the like as required. The oxygen barrier layer composition is dissolved in a suitable solvent, applied onto the image forming layer and dried to form an oxygen barrier layer. The main component of the coating solvent is particularly preferably water or alcohols such as methanol, ethanol, i-propanol.

The dry mass of the oxygen barrier layer is preferably 0.7 to 2.0 mg / m ² , particularly preferably 1.3 to 2.0 mg / m ² .

<Common components>
(Support)
The support that can be used in the photosensitive lithographic printing plate of the present invention is preferably an aluminum plate. In this case, a pure aluminum plate, an aluminum alloy plate, or the like may be used.

  Various aluminum alloys can be used as the support, such as alloys of aluminum and metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, etc. Aluminum plates manufactured by various rolling methods 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.

  The support that can be used in the photosensitive lithographic printing plate of the present invention is preferably subjected to a degreasing treatment in order to remove rolling oil on the surface prior to roughening (graining treatment). 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.

  Examples of the roughening method include a mechanical method and a method of etching by electrolysis.

The mechanical roughening method used 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 electrochemical surface roughening method is not particularly limited, but a method of electrochemical surface roughening in an acidic electrolyte is preferable. As the acidic electrolytic solution, an acidic electrolytic solution usually used in an electrochemical surface roughening method can be used, but a hydrochloric acid-based or nitric acid-based electrolytic solution is preferably used. As the electrochemical surface roughening method, for example, methods described in Japanese Patent Publication No. 48-28123, British Patent No. 896,563 and Japanese Patent Laid-Open No. 53-67507 can be used. This roughening method can be generally 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 50 to 150 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 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.

When electrochemical surface roughening is performed using a nitric acid-based electrolyte as the electrolyte, it can be generally performed by applying a voltage in the range of 1 to 50 volts, but is selected from the range of 10 to 30 volts. Is preferred. 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, and the like can be added to the electrolytic solution.

When a hydrochloric acid-based electrolyte is used as the electrolyte, it can be generally applied by applying a voltage in the range of 1 to 50 volts, but is preferably selected from the range of 2 to 30 volts. Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 50 to 150 A / dm ^2. The quantity of electricity, may be in the range of 5000 C / dm ^2, preferably 100~2000c / dm ^2, and more and more preferably selected from the range of 200~1000c / 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 hydrochloric 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, and the like can be added to the electrolytic solution.

After the surface is roughened by the electrochemical surface roughening method, 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.

  The mechanical surface roughening method and the electrochemical surface roughening method may each be used alone for roughening, or the mechanical surface roughening treatment method followed by the electrochemical surface roughening method may be used for roughening. You may face it.

Following the roughening treatment, an anodic oxidation treatment can be performed. There is no restriction | limiting in particular in the method of the anodizing process which can be used in this invention, A well-known method can be used. By performing the anodizing treatment, an oxide film is formed on the support. For the anodizing treatment, a method of electrolyzing an aqueous solution containing sulfuric acid and / or phosphoric acid at a concentration of 10 to 50% as an electrolytic solution at a current density of 1 to 10 A / dm ² is preferably used. The method of electrolyzing at high current density in sulfuric acid described in Japanese Patent No. 1,412,768, the method of electrolyzing using phosphoric acid described in Japanese Patent No. 3,511,661, chromic acid, Examples thereof include a method using a solution containing one or more acids, malonic acids and the like. The formed anodic oxidation coating amount 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.

  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 this invention, after performing these processes, the process which coat | covers a support body surface with polyvinylphosphonic acid can be performed. The coating 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 0.01 to 35% aqueous solution, and a 0.1 to 5% aqueous solution is particularly preferable. The treatment temperature is preferably 20 ° C. or higher and 90 ° C. or lower, and more preferably 40 ° C. or higher and 80 ° C. or lower. If it is lower than 20 ° C., printing stains are bad, and if it is higher than 90 ° C., printing durability is deteriorated.

  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 a drying temperature, 20-95 degreeC is preferable.

The amount of polyvinylphosphonic acid applied to the surface of the aluminum support of the present invention is preferably 3 to ²⁰ mg / m2. Particularly, 4 to 15 mg / m ² is preferable. If it is less than 3 mg / m ² , printing stains in the non-image area will occur, and if it exceeds 20 mg, the printing durability will deteriorate.

  Various concentrations of polyvinylphosphonic acid aqueous solution concentration, treatment temperature, and treatment time can be combined to obtain a desired coating amount.

  The surface phosphorus atom concentration (atm%) in the state where the surface of the aluminum support of the present invention is coated with polyvinyl sulfonic acid is preferably 3 to 15 atm%. Especially preferably, it is 5-9 atm%.

(Matting agent)
Further, in order to prevent scratches when the printing plate of the present invention is mounted on a laser recording device or a printing machine, a matting agent having an average particle size of 1 μm or more and less than 20 μm is applied to the protective layer of the photosensitive lithographic printing plate of the present invention. It is preferable to contain.

  Examples of the matting agent preferably used include inorganic fine particles having a new Mohs hardness of 5 or more and organic matting agents. Examples of inorganic fine particles having a new Mohs hardness of 5 or more include metal oxide particles (silica, alumina, titania, zirconia, iron oxide, chromium oxide, etc.), metal carbide particles (silicon carbide, etc.), boron nitride particles, diamond particles, etc. Is mentioned.

  Examples of the organic matting agent include starch described in U.S. Pat. No. 2,322,037 and the like, and starch described in Belgian Patent 625,451 and British Patent 981,198. Derivatives, polyvinyl alcohol described in JP-B No. 44-3643, etc., polystyrene or polymethacrylate described in Swiss Patent No. 330,158, etc., described in US Pat. No. 3,079,257, etc. Polyacrylonitrile, polycarbonates described in US Pat. No. 3,022,169 and the like can be mentioned.

The addition amount of these matting agents is preferably 0.1 g or more and less than 10 g per 1 m ² .

  In addition, in the case of aqueous solution coating, a nonionic surfactant can be mainly added to the protective layer according to the present invention for the purpose of ensuring the uniformity of coating. Specific examples of such nonionic surfactants include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether, polyoxyethylene dodecyl ether and the like. .

  The proportion of the surfactant in the total solid in the protective layer is preferably 0.05 to 5% by mass, more preferably 1 to 3% by mass.

Dry coating amount of the protective layer is preferably from 0.05 to 1.5 g / m ^2, more preferred range is 0.1~0.7g / m ^2. Within this range, it is possible to satisfactorily prevent stains, prevent scratches, prevent fingerprint marks, and reduce ablation residue without impairing the removal of the protective layer on the printing press.

(Application)
The above-mentioned image forming layer coating solution can be coated on a support by a conventionally known method and dried to prepare a photosensitive lithographic printing plate material.

  Examples of coating methods for the coating liquid include air doctor coater method, blade coater method, wire bar method, knife coater method, dip coater method, reverse roll coater method, gravure coater method, cast coating method, curtain coater method and extrusion coater method. I can list them.

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

(Image exposure)
As the light source for recording an image on the photosensitive lithographic printing plate material of the present invention, various light sources can be used in accordance with the photosensitive wavelength region of the material, but the use of a laser light source is preferred.

  The printing plate can be obtained by irradiating a printing plate material from a surface having an image forming layer with laser light according to image data to form an image.

  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.

  As a laser light source for exposing the photosensitive lithographic printing plate of the present invention, a laser light source having an emission wavelength in the infrared and / or near infrared region, that is, a wavelength range of 700 to 1500 nm can be used. Specifically, a YAG laser, a semiconductor laser, or the like can be preferably used. As the light source, a laser light source having an emission wavelength in the ultraviolet and visible short wavelength region can also be used. Specifically, for example, a He—Cd laser (441 nm), a combination of Cr: LiSAF and SHG crystal (430 nm) as a solid laser, KNbO 3, a ring resonator (430 nm), and AlGaInN (350 nm to 450 nm) as a semiconductor laser system. ), AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 400 to 410 nm), and the like.

  General laser scanning methods that can be used in the present invention include cylindrical outer surface scanning, cylindrical inner surface scanning, and planar scanning. In the cylindrical outer surface scanning, laser exposure is performed while rotating a drum around which the recording material is wound, and the rotation of the drum is the main scanning and the movement of the laser light is the sub scanning.

  In cylindrical inner surface scanning, a recording material is fixed to the inner surface of the drum, a laser beam is irradiated from the inside, and a main scanning is performed in the circumferential direction by rotating a part or all of the optical system. Sub scanning is performed in the axial direction by linearly moving all of them in parallel with the drum axis.

  In plane scanning, a laser beam main scan is performed by combining a polygon mirror, a galvanometer mirror, and an fθ lens, and a sub-scan is performed by moving a recording medium. Cylindrical outer surface scanning and cylindrical inner surface scanning are easier to increase the accuracy of the optical system and are suitable for high-density recording. In order to effectively use the energy of the laser beam, the cylindrical outer surface scanning that can simply design the optical system and can shorten the distance between the light source and the recording material is particularly preferable.

In the present invention, image exposure is preferably performed with a plate surface energy (energy on the plate material) of 10 mJ / cm ² or more, and the upper limit is 500 mJ / cm ² . More preferably, it is 10-300 mJ / cm < ² >. For this energy measurement, for example, a laser power meter PDGDO-3W manufactured by OphirOptics can be used.

(Automatic processor)
It is advantageous to use an automatic processor for developing the photosensitive lithographic printing plate material. The automatic developing machine is preferably provided with a mechanism for automatically replenishing the required amount of the developing replenisher to the developing bath, and preferably provided with a mechanism for discharging the developer exceeding a certain amount, preferably the developing bath. Is provided with a mechanism for automatically replenishing the required amount of water, preferably a mechanism for detecting plate passing is provided, preferably a mechanism for estimating the processing area of the plate based on detection of plate passing. Preferably, a mechanism for controlling the replenishment amount and / or replenishment timing of the replenisher and / or water to be replenished based on the detection of the printing plate and / or the estimation of the processing area is provided. Is provided with a mechanism for controlling the temperature of the developer, preferably a mechanism for detecting the pH and / or conductivity of the developer, preferably based on the pH and / or conductivity of the developer. Trying to replenish The amount of replenisher supplied and / or water and / or mechanism for controlling the replenishment timing is given that. The developer concentrate preferably has a function of once diluting and stirring with water. When there is a rinsing step after the development step, the rinsing water after use can be used as dilution water for the concentrate of the development concentrate.

  The automatic processor may have a pretreatment unit that immerses the plate in the pretreatment liquid before the development step. The pretreatment unit is preferably provided with a mechanism for spraying the pretreatment liquid on the plate surface, and preferably provided with a mechanism for controlling the temperature of the pretreatment liquid to an arbitrary temperature of 25 to 55 ° C. Is provided with a mechanism for rubbing the plate surface with a roller-like brush. Water or the like is used as the pretreatment liquid.

(Post-processing)
The lithographic printing plate developed with an alkaline developer is post-treated with a washing water, a rinse solution containing a surfactant, a finisher or a protective gum solution mainly composed of gum arabic or starch derivatives. These treatments can be used in various combinations. For example, the treatment with a rinsing solution containing development->washing-> surfactant or the development->washing-> finisher solution is preferable because of less fatigue of the rinse solution and the finisher solution. Furthermore, a countercurrent multistage process using a rinse liquid or a finisher liquid is also a preferred embodiment.

  These post-processing are generally performed using an automatic developing machine including a developing unit and a post-processing unit. As the post-treatment liquid, a method of spraying from a spray nozzle or a method of immersing and conveying in a treatment tank filled with the treatment liquid is used. A method is also known in which a fixed amount of a small amount of washing water is supplied to the plate surface after development, and the waste liquid is reused as dilution water for the developer stock solution. In such automatic processing, processing can be performed while each replenisher is replenished with each replenisher according to the processing amount, operating time, and the like. In addition, a so-called disposable treatment method in which treatment is performed with a substantially unused post-treatment liquid is also applicable. The lithographic printing plate obtained by such processing is loaded on an offset printing machine and used for printing a large number of sheets.

(Gum solution)
It is preferable to add an acid or a buffer to the gum solution in order to remove alkali components from the developer. In addition, a hydrophilic polymer compound, a chelating agent, a lubricant, a preservative, a solubilizer, and the like can be added. . When the gum solution contains a hydrophilic polymer compound, a function as a protective agent for preventing scratches and stains on the developed plate is also added.

(Washing water before development)
A cleaning solution (pretreatment solution) used in a pretreatment unit such as a washing step before development is usually water, but the following additives can be added as necessary.

  As the chelating agent, a compound that forms a chelate compound by coordination with a metal ion is used. Ethylenediaminetetraacetic acid, its potassium salt, sodium salt, ethylenediamine disuccinic acid, its potassium salt, sodium salt, triethylenetetramine hexaacetic acid, its potassium salt, sodium salt, diethylenetriaminepentaacetic acid, its potassium salt, sodium salt, hydroxyethylethylenediamine Triacetic acid, its potassium salt, sodium salt, nitrilotriacetic acid, its potassium salt, sodium salt, 1-hydroxyethane-1,1-diphosphonic acid, its potassium salt, sodium salt, aminotri (methylenephosphonic acid), its potassium salt Sodium salt, phosphonoalkanetricarboxylic acid, ethylenediamine disuccinic acid, potassium salt thereof, sodium salt and the like. Those chelating agents having an organic amine salt instead of the potassium salt and sodium salt are also effective. The addition amount of the chelating agent is suitably in the range of 0 to 3.0% by mass.

  As the surfactant, any of anionic, nonionic, cationic and amphoteric surfactants can be used, and anionic or nonionic surfactants are preferred. The type of the preferred surfactant varies depending on the composition of the overcoat layer and the image forming layer, and generally serves as a dissolution accelerator for the overcoat layer material and preferably has a low solubility for the components of the image forming layer. Examples of anionic surfactants include fatty acid salts, abichenates, hydroxyalkanesulfonates, alkanesulfonates, dialkylsulfosuccinates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylphenoxypolyoxyethylenepropylsulfonate Salts, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium, N-alkyl sulfosuccinic acid monoamide disodium salts, petroleum sulfonates, sulfated castor oil, sulfated beef oil, fatty acid alkyl esters Sulfate esters, alkyl sulfate esters, polyoxyethylene alkyl ether sulfate esters, fatty acid monoglyceride sulfate esters, polyoxyethylene styrylphenyl ester Tersulfate ester salts, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts, polyoxyethylene alkyl phenyl ether phosphate ester salts, partially saponified styrene-maleic anhydride copolymers, olefin-maleic anhydride copolymers And partially saponified products, naphthalenesulfonate formalin condensates, and the like. Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid esters, sorbitan fatty acids. Partial esters, pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, iethylene glycol fatty acid esters, polyiglycerin fatty acid partial esters, polyoxyethylene Castor oil, polyoxyethylene glycerin fatty acid partial ester, fatty acid diethanolamide, N, N-bis-hydroxyalkyla Emissions, polyoxyethylene alkylamine, triethanolamine fatty acid esters, trialkylamine oxides and the like. A preferable addition amount of the surfactant is 0 to 10% by mass. Further, an antifoaming agent can be used in combination with the surfactant.

  Examples of preservatives include phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benzisothiazolin-3-one, benzotriazole derivatives, amiding anidine derivatives, quaternary ammonium salts, pyrozine, There are derivatives such as quinoline and guanidine, diazine, triazole derivatives, oxazole and oxazine derivatives.

  In the cleaning method, it is preferable to use the cleaning liquid used for pre-development cleaning by adjusting the temperature, and the temperature is preferably in the range of 10 to 60 ° C. As a cleaning method, known processing liquid supply techniques such as spraying, dipping, and coating can be used, and processing promoting means such as a brush, a drawing roll, and a submerged shower in the dip processing can be used as appropriate.

  The development treatment may be performed immediately after completion of the pre-development washing step, or the development treatment may be carried out after drying before the pre-development washing step. After the development step, known post-treatments such as washing with water, rinsing and gumming can be performed. The pre-development rinse water that has been used once or more can be reused in post-development rinse water, rinse solution, or gum solution.

(Printing method as processless printing plate material)
The planographic printing plate of the present invention can be used as a printing plate material that is subjected to normal development as described above, but can also be used as a so-called processless printing plate material. Below, the printing method in the case of using the said printing plate as a processless printing plate material is demonstrated.

  The lithographic printing plate material of the present invention has a structure having an image forming layer on a support having a hydrophilic layer, and after image formation is performed by the above image exposure, printing can be performed without performing development processing. It has the characteristics that can. That is, after forming an image on the printing plate material of the present invention using a thermal head or a thermal laser, it is preferable to perform development with dampening water or dampening water and printing ink on a lithographic printing machine, and perform printing. is there. The above-mentioned printing plate material after image formation is directly attached to the plate cylinder of the printing press, or image formation is performed after the printing plate material is attached to the printing plate cylinder, and the water supply roller and / or Alternatively, the ink supply roller is brought into contact with the printing plate material to supply dampening water and / or ink, and the non-image portion of the image forming layer is removed with dampening water or dampening water and printing ink, and the printing plate and Is possible. The removal of the non-image portion of these image forming layers can be performed by a normal printing sequence using a PS plate, and is performed by so-called on-press development processing.

  In the printing method using the processless printing plate material according to the present invention, general dampening water and process ink can be used as described below.

(Dampening water)
The fountain solution used in the present invention is preferably combined with a plurality of the following.
(A) pH adjuster (b) Auxiliary agent for improving wettability (c) Water-soluble polymer compound (d) Odor masking agent (e) Preservative (f) Chelating agent (g) Colorant (h) Antirust agent (i) Antifoaming agent The dampening solution of the present invention may contain alcohols in order to adjust the surface tension and viscosity to improve printability. Examples of the alcohol that can be added include methyl alcohol, ethyl alcohol, propyl alcohol, and isopropyl alcohol.

  The balance is water as a component of the fountain solution composition according to the present invention. The fountain solution composition is generally concentrated and commercialized when it is usually commercialized. Accordingly, a concentrated fountain solution composition can be obtained as an aqueous solution in which the above various components are dissolved using water, preferably demineralized water, that is, pure water. When such a concentrated solution is used, it is diluted about 10 to 200 times with tap water, well water, etc. during normal use to obtain a fountain solution composition during use.

  The dampening water according to the present invention can be used in either a dampening water supply system or a continuous water supply dampening water supply apparatus, but is particularly preferably used in a continuous water supply dampening water supply apparatus. It can also be used in printing presses such as Mitsubishi Diamatic Dumpner, Comorimatic, Darleng Dampner and Heidelberg Alcolor Dumpner.

(ink)
The ink that can be used in the printing according to the present invention may be any ink that can be used for lithographic printing. Specifically, rosin-modified phenolic resin and vegetable oil (linseed oil, tung oil, soybean oil, etc.) , Oil-based inks composed of components such as petroleum solvents, pigments, oxidation polymerization catalysts (cobalt, manganese, lead, iron, zinc, etc.) and radiation ultraviolet rays composed of components such as acrylic oligomers, acrylic monomers, photopolymerization initiators, and pigments Further, it is a curable ink, and a hybrid ink having both oil-based ink properties and UV ink properties can also be used.

  The radiation curable ink that can be used in the present invention comprises at least a polymerizable compound. In addition, a coloring material can be added for the purpose of obtaining visible image quality.

  As the color material, a color material that can be dissolved or dispersed in the main component of the polymerizable compound, that is, various dyes and pigments can be used.

  When adding a pigment, since the dispersibility has a great influence on the degree of coloration, the pigment is appropriately dispersed. For the dispersion of the pigment, a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, a paint shaker, or the like can be used. Further, it is possible to add a dispersant when dispersing the pigment. As the dispersant, it is preferable to use a polymer dispersant. Examples of the polymer dispersant include Solsperse series manufactured by Zeneca. Moreover, it is also possible to use a synergist according to various pigments as a dispersion aid. These dispersants and dispersion aids are preferably added in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the pigment. Although the dispersion medium is a solvent or a polymerizable compound, the radiation curable ink used in the present invention is preferably solventless because it reacts and cures immediately after ink landing. If the solvent remains in the cured image, the solvent resistance deteriorates and the VOC of the remaining solvent arises. Therefore, it is preferable in view of dispersibility that the dispersion medium is not a solvent but a polymerizable compound, and among them, a monomer having the lowest viscosity is selected.

  For the dispersion, it is preferable that the average particle diameter is 0.08 to 0.5 μm, and the pigment, the dispersant, and the dispersion medium are selected so that the maximum particle diameter is 0.3 to 10 μm, preferably 0.3 to 3 μm. Set dispersion conditions and filtration conditions. By controlling the particle size, clogging of the head nozzle can be suppressed, and ink storage stability, ink transparency, and curing sensitivity can be maintained.

  The colorant is preferably added in an amount of 0.1% to 10% by weight of the total ink.

Examples are shown below specifically, but the embodiments of the present invention are not limited thereto. In the examples, “parts” represents “parts by mass” unless otherwise specified.
(Example of photosensitive lithographic printing plate material having thermal image forming layer)
Example 1
An aluminum plate made of material 1S having a thickness of 0.30 mm was used with a No. 8 nylon brush and an aqueous suspension of 800 mesh Pamiston, and its surface was grained and washed thoroughly with water. After being immersed in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds for etching, washed with running water, neutralized with a 20% aqueous nitric acid solution, and then washed with water. This was subjected to an electrolytic surface roughening treatment in a 1% nitric acid aqueous solution with a anodic electricity quantity of 300 coulomb / dm ² using a sinusoidal alternating current under the condition of VA = 12.7V. When the surface roughness was measured, it was 0.45 μm (Ra indication). Next, after dipping in a 30% H ₂ SO ₄ aqueous solution and desmutting at 55 ° C. for 2 minutes, a cathode was placed on the grained surface in 33 ° C., 20% H ₂ SO ₄ aqueous solution to obtain a current density. When anodized at 5 A / dm ² for 50 seconds, the thickness was 2 g / m ² . On the aluminum plate thus treated, the following photosensitive solution A was applied so that the dry coating mass was 2.0 g / m ² and dried at 100 ° C. for 1 minute to form an image forming layer (photosensitive layer). A photosensitive lithographic printing plate was formed.

(Photosensitive solution)
Resin: Condensed novolak resin of LB6564-Bakelite Phenol cresol (charged mass ratio: 4/6) and formalin 89 parts by mass Infrared absorbing dye (Dye 1) 4 parts by mass Crystal violet dye (Hodogaya Chemical) 0.9 part by mass acid-decomposing compound A 5 parts by mass 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) 1,3,5-triazine 1 part by mass fluorine compound; perfluorobutanesulfonic acid 0.1 parts by mass of soda
(Solid content 0.1% by mass)
Solvent: 1000 parts by mass of 1-methoxypropan-2-ol

  For Examples 2 to 13 and Comparative Examples 1 and 2, photosensitive lithographic printing was performed in the same manner as in Example 1 except that the fluorine-based compound used in Example 1 and the addition amount were changed as shown in Table 1. A plate was made.

(Evaluation of coatability of image forming layer)
The image forming layer (photosensitive layer) coating film was visually evaluated.
A: Uniform film surface B: Film surface with unevenness (circular or ellipse density unevenness).

  The results are shown in Table 2.

(Evaluation of plate making / printing)
The obtained photosensitive lithographic printing plate was subjected to the following exposure and development. In developer running, long-term development evaluation was performed.

(exposure)
Using a Creos plate setter Trendsetter 3244F, exposure was performed at an output of 9.0 W, a rotation speed of 150 rpm, and a resolution of 2400 dpi (where dpi represents the number of dots per inch, that is, 2.54 cm). The manuscript data in which 85 to 99% of the pattern and the solid portion were included was used.

  After exposure, the exposed portion to be a non-image portion and the solid portion to be the image portion (unexposed portion) were strongly pressed with the thumb of the hand, and then developed with an automatic processor within 2 to 20 seconds. . After printing, the development state after pressing the thumb of the non-image area on the developed plate and the degree of sag (film reduction) after development of the portion pressed with the thumb of the solid part was visually observed. The results are shown in Table 2.

  Next, long-term development running was performed under the following conditions while replenishing with the following development replenisher.

  Subsequently, printing evaluation was performed under the following printing conditions. The results are shown in Table 2.

(Developer)
A Potassium silicate (Nippon Chemical Industry potassium silicate aqueous solution) 7 parts by weight Caustic potash (flakes) 3 parts by weight Water 1000 parts by weight The pH of the developer was 12.9.

(Development replenisher)
A Potassium silicate (Nippon Chemical Industry potassium silicate aqueous solution) 7 parts by weight Caustic potash (flakes) 4.5 parts by weight water 1000 parts by weight The pH of the developer was 13.1.

(Development conditions)
Automatic developing machine: Raptor85 (manufactured by Glunz & Jensen) was used, and finishing liquid (gum liquid): FP-2W (manufactured by Fuji Photo Film Co., Ltd.) was used.

(Development replenishment conditions)
Photosensitive lithographic printing plate (1003 × 800 mm; average image area ratio: 35%) It was set so that 180 ml of development replenisher was replenished as processing fatigue for each sheet processing. Further, replenishment was performed with the air fatigue when not used at night (for 12 hours) being 500 ml and the air fatigue when not being used in the day being 100 ml per hour.

(Development running conditions)
Development processing was carried out for 1 month at a rate of 100 plates / day. The development process was stopped on the second day of the week (Saturday and Sunday) in the same manner as at night. In this case, the amount of air fatigue was 500 ml / holiday.

(Evaluation of developer running solution)
The sludge on a roller and sludge adhesion to the tank wall surface were observed visually. The results are shown in Table 1.
A: Sludge is smooth and there is no aggregation, adhesion to a roller or a wall.
B: Sludge is sticky, and agglomeration, adhesion to rollers and walls are observed.

(Printing conditions)
A lithographic printing plate obtained by exposure and development as described above was prepared using a printing press: DAIYA1, F-1 (manufactured by Mitsubishi Heavy Industries, Ltd.), printing ink: soybean oil ink (Naturalis 100 (Naturalith)) (large Nippon Ink Chemical Co., Ltd.), fountain solution: H liquid SG-51 concentration 1.5% (manufactured by Tokyo Ink Co., Ltd.), printing paper: Mucoat 4, 6 size, 90 kg (Hokuetsu Paper Co., Ltd.) Manufactured), printing speed: printed at 8000 sheets / hour, evaluated as follows, and the results are shown in Table 2.

(Evaluation of printed matter)
The printed material at the time of printing about 1,000 sheets, especially the ink-imprinted state of the mark (image area and non-image area) pressed by the thumb on the plate, and the overall finished quality were visually observed, and the results are shown in Table 2. Indicated.

From Table 2, the photosensitive lithographic printing plate and thermal CTP of the present invention have good coatability, there is no sludge generation, which is a problem in long-term running of development processing, and there are troubles due to fingers in handling such as handling. It can be seen that there is no photosensitive lithographic printing plate.
(Example of photosensitive lithographic printing plate having photopolymerizable image forming layer)
Example 14
(Binder synthesis)
(Synthesis of acrylic copolymer 1)
In a three-necked flask under a nitrogen stream, 30 parts of methacrylic acid, 50 parts of methyl methacrylate, 20 parts of ethyl methacrylate, 500 parts of isopropyl alcohol and 3 parts of α, α′-azobisisobutyronitrile are placed in a nitrogen stream. The reaction was carried out in an oil bath at 0 ° C. for 6 hours. Then, after refluxing for 1 hour at the boiling point of isopropyl alcohol, 3 parts of triethylammonium chloride and 25 parts of glycidyl methacrylate were added and reacted for 3 hours. Subsequently, the solvent was distilled off under reduced pressure to obtain an acrylic copolymer 1 having a resin content of 90% by mass. The mass average molecular weight measured using GPC was about 54,000, the acid value was 80 mg KOH / g, and the glass transition temperature (Tg) measured using DSC (differential thermal analysis) was about 85 ° C.

(Production of support)
An aluminum plate (material 1050, tempered H16) having a thickness of 0.3 mm was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by dipping in a 10% aqueous hydrochloric acid solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, the aluminum plate was subjected to electrolytic surface roughening with an alternating current for 60 seconds under conditions of 25 ° C. and a current density of 100 A / dm ^{2 in} a 0.3% by mass nitric acid aqueous solution, and then kept at 60 ° C. Desmutting treatment was performed for 10 seconds in a 5% aqueous sodium hydroxide solution. The surface-roughened aluminum plate subjected to desmut treatment was anodized in a 15% sulfuric acid solution at 25 ° C., a current density of 10 A / dm ² , and a voltage of 15 V for 1 minute. Further, after the anodic acid value treatment, a surface treatment was performed for 20 seconds in a 65 ° C. polyvinyl phosphonic acid aqueous solution to prepare a support 1. The dry weight of polyvinylphosphonic acid was 10 mg / m ² , and the center line average roughness (Ra) of the surface was 0.65 μm.

(Preparation of photosensitive lithographic printing plate)
On the above support, a photopolymerizable image forming layer (photosensitive layer) coating solution 1 having the following composition was applied with a wire bar so that the drying rate became 1.5 g / m ² and dried at 95 ° C. for 1.5 minutes. A photopolymerized image forming layer-coated sample was obtained.

(Photopolymerizable image forming layer coating solution 1)
Addition-polymerizable ethylenic double bond-containing monomer 1 25.0 parts (Nn-butyldiethanolamine (1 mol), 1,3-bis (1-isocyanate-
1-methylethyl) benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) reaction product)
Addition-polymerizable ethylenic double bond-containing monomer 2 NK ester 4G
(Polyethylene glycol dimethacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) 25.0 parts polymerization initiator (I-1) 4.0 parts trihaloalkyl compound (Cl-1) 2.0 part photosensitizing dye (D-1) 0 parts acrylic copolymer 1 40.0 parts N-phenylglycine benzyl ester 4.0 parts phthalocyanine pigment (MHI454: manufactured by Gokoku Dye) 6.0 parts 2-t-butyl-6- (3-t-butyl -2-hydroxy-5-methylbenzyl)
Methyl phenyl acrylate (Sumilyzer GS: manufactured by Sumitomo 3M) 0.5 parts Fluoro Compound 1 0.32 parts
(Solid content 0.3% by mass)
Methyl ethyl ketone 80 parts Cyclohexanone 820 parts On the photopolymerizable image-forming layer coating sample, an oxygen barrier layer coating solution having the following composition was coated with an applicator so as to be 1.8 g / m ² when dried. It was dried for 1 minute to prepare a photosensitive lithographic printing plate having an oxygen blocking layer on the image forming layer.

(Oxygen barrier layer coating solution 1)
Polyvinyl alcohol (GL-05: manufactured by Nippon Synthetic Chemical Co., Ltd.) 70 parts Polyvinylpyrrolidone (K-30: manufactured by BASF) 30 parts Surfactant (Surfinol 465: manufactured by Nissin Chemical Industry Co., Ltd.) 0.5 part Water 900 parts

  In Examples 15 to 26 and Comparative Examples 5 and 6, the photosensitive lithographic plate was prepared in the same manner as in Example 1 except that the fluorine-based compound used in Example 14 and the addition amount were changed as shown in Table 3. A printing plate was prepared.

Next, 300 sheets of the photosensitive lithographic printing plate, 1003 mm * 800 mm, were sandwiched with the following paper (interleaf) on the surface of the photosensitive film for each sheet, and stored at room temperature for 1 month.
Paper: High-quality paper, Kimmari, 44.5 kg (made by Hokuetsu)
(Interleaf peelability)
One month later, 300 sheets of plate with an automatic interleaving machine (apparatus that peels the interleaving paper one by one from the photosensitive lithographic printing plate by applying a rubber sucker sucked with a vacuum pump to the interleaving paper) The slip paper was peeled off. The results are shown in Table 4.

(Image formation)
The prepared photosensitive lithographic printing plate is an image with a resolution of 2400 dpi, exposure energy: 50 μJ / cm ² , using a plate setter (Tigercat: a modified product manufactured by ECRM) equipped with a light source having a laser of 405 ± 5 nm and 30 mW. Exposure (exposure pattern used 175 LPI 50% square dots) (LPI represents 1 inch, that is, the number of lines per 2.54 cm) was performed.

  Next, a pre-water washing part that heat-treats at 100 ° C. for 10 seconds and removes the oxygen blocking layer before development, a development part filled with a developer having the following composition, a water washing part that removes the developer adhering to the plate surface, and an image line part Using an automatic developing machine equipped with a gum solution for protection (GW-3: a product obtained by diluting Mitsubishi Chemical Co., Ltd.), development processing was performed under the following development conditions to obtain a lithographic printing plate. The time during which the photosensitive lithographic printing plate is in contact with the developer is defined as the development time, and the development time using the automatic processor is 20 seconds.

(Developer)
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.

(Development replenisher)
Potassium silicate aqueous solution (SiO ₂ : 26%, K ₂ O: 13.5%) 40.0 g / L
Potassium hydroxide 10.0g / L
Ethylenediaminetetraacetic acid 0.5g / L
Polyoxyethylene (13) naphthyl ether sulfonate 20.0 g / L
1 L with water. The pH was 12.9.

(Replenishment conditions)
Same as Example 1.

  Thereafter, development running was performed in the same manner as in Example 1 to evaluate the development running solution. Further, as in Example 1, printing was performed for evaluation. The results are shown in Table 4.

  From Table 4, the photosensitive lithographic printing plate of the present invention, the photopolymer CTP has good coatability, no sludge generation that becomes a problem in long-term running of development processing, and good peelability of the interleaf after storage, It can be seen that it is a photosensitive lithographic printing plate without trouble with an automatic paper stripper.

Claims (3)

In the photosensitive lithographic printing plate material having a constituent layer comprising a fluorine compound on a support, the constituent layer contains a fluorine compound represented by the following general formula A or general formula B as the fluorine compound. A photosensitive lithographic printing plate material characterized by
General formula _{A: Y- (CF 2) n} -CF 3
(Wherein, Y represents a SO ₃ X, COOX, or PO ₃ X group, X represents a K, Na, Li, or NH ₄ group. N represents a positive integer 2, 3, or 4.)
Formula _{B: Z- (CF 2) n} -Y
(In the formula, Y represents an SO ₃ X, COOX, PO ₃ X group, Z represents an SO ₃ X, COOX, PO ₃ X group, and X represents a K, Na, Li, or NH ₄ group. Represents a positive integer 2, 3, or 4.) The photosensitive lithographic printing plate material according to claim 1, wherein the constituent layer is an image forming layer containing a photothermal conversion agent and an alkali-soluble resin. The photosensitive lithographic printing plate material according to claim 1, wherein the constituent layer is an image forming layer containing an ethylenically unsaturated compound, a photopolymerization initiator, and an alkali-soluble resin.