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WO2019167967A1 - Plaque originale de plaque d'impression lithographique de type positif, et procédé de fabrication de plaque d'impression lithographique - Google Patents

Plaque originale de plaque d'impression lithographique de type positif, et procédé de fabrication de plaque d'impression lithographique Download PDF

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Publication number
WO2019167967A1
WO2019167967A1 PCT/JP2019/007387 JP2019007387W WO2019167967A1 WO 2019167967 A1 WO2019167967 A1 WO 2019167967A1 JP 2019007387 W JP2019007387 W JP 2019007387W WO 2019167967 A1 WO2019167967 A1 WO 2019167967A1
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WIPO (PCT)
Prior art keywords
group
printing plate
acid
formula
plate precursor
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Application number
PCT/JP2019/007387
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English (en)
Japanese (ja)
Inventor
一郎 小山
尚志 佐藤
Original Assignee
富士フイルム株式会社
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Publication of WO2019167967A1 publication Critical patent/WO2019167967A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/28—Condensation with aldehydes or ketones
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/06—Developable by an alkaline solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/10—Developable by an acidic solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
    • B41C2210/262—Phenolic condensation polymers, e.g. novolacs, resols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
    • B41C2210/266—Polyurethanes; Polyureas

Definitions

  • the present disclosure relates to a positive planographic printing plate precursor and a method for producing a planographic printing plate.
  • the positive type lithographic printing plate precursor for infrared laser contains, as essential components, an alkali-soluble binder resin and an infrared absorbent (for example, infrared absorbing dye (IR dye)) that absorbs light and generates heat.
  • IR dye infrared absorbing dye
  • the IR dye or the like acts as a development inhibitor that substantially reduces the solubility of the binder resin in the developer by interaction with the binder resin in the unexposed area (image area), and in the exposed area (non-image area).
  • the generated heat weakens the interaction between the IR dye and the binder resin and dissolves in an alkaline developer to form a lithographic printing plate.
  • a lithographic printing plate precursor or a positive type image forming element used in the production of a conventional lithographic printing plate those described in Patent Documents 1 to 3 are known.
  • Patent Document 1 a heat and / or light-sensitive image recording layer containing an infrared absorber and a binder polymer is formed on a support having a hydrophilic surface, and the image recording layer contains a salicylic acid group.
  • a lithographic printing plate precursor having a structural unit and a structural unit containing a sulfonamide group is described.
  • Patent Document 2 describes (A) a resin composition containing a polymer having a structural unit represented by the following general formula (1).
  • X represents a tetravalent linking group.
  • n represents an integer of 6 to 40.
  • Patent Document 3 A) preparing a first layer on a substrate, the first layer comprising a first radiation absorbing compound dispersed in a first polymer binder, B) providing a second layer on the first layer, the second layer comprising a second radiation absorbing compound dispersed in a second polymeric binder, C) After drying the first layer and the second layer, at a temperature of about 40 ° C. to about 90 ° C. for at least 4 hours under conditions that inhibit moisture removal from the dried first layer and the second layer.
  • a method of providing a positive imageable element comprising the step of heat treating the first layer and the second layer is described.
  • Patent Document 1 International Publication No. 2012/110359
  • Patent Document 2 JP 2004-325508
  • Patent Document 3 JP-T 2009-528568
  • a property that development is possible even when a developer having a low pH for example, a developer having a pH of 10 or less
  • developerability at low pH also referred to as “developability at low pH”.
  • the inventors of the present invention have developed a lithographic printing plate precursor using the composition described in Patent Document 1, a lithographic printing plate precursor described in Patent Document 2, or a positive image formation described in Patent Document 3. It has been found that there is room for improvement in developability at low pH in a lithographic printing plate precursor containing elements.
  • the problem to be solved by the embodiments of the present disclosure is to provide a positive lithographic printing plate precursor excellent in developability at low pH, and a method for producing a lithographic printing plate using the positive lithographic printing plate precursor. It is.
  • Means for solving the above problems include the following aspects. ⁇ 1> a support; An image recording layer formed on a support, The image recording layer is Having at least one structural unit selected from the group consisting of a structural unit represented by the following formula A1, a structural unit represented by the following formula A2, and a structural unit represented by the following formula A3, and having a pKa of 9 or less
  • a binder polymer having an acid value of 2 meq / g to 4 meq / g by an acid group, and an infrared absorber, Positive lithographic printing plate precursor.
  • L A represents —C ( ⁇ O) O—, —C ( ⁇ O) NR 5 —, or a phenyl group
  • R 5 represents a hydrogen atom or an alkyl group
  • R A represents a group represented by Formula B1.
  • R 1 represents a hydrogen atom or an alkyl group.
  • R A represents a group represented by Formula B1
  • R 2 and R 3 each independently represent a hydrogen atom or an alkyl group.
  • R A represents a group represented by Formula B1.
  • L 1 represents a single bond or a divalent linking group
  • X 1 represents a single bond, an ester bond, an amide bond, a urethane bond, or a urea bond
  • A represents an aromatic ring structure
  • Z is independent.
  • ⁇ 2> The positive planographic printing plate precursor according to ⁇ 1>, wherein the acid group represented by Z is a carboxy group or a hydroxy group.
  • ⁇ 3> The positive lithographic printing plate precursor as described in ⁇ 1> or ⁇ 2> above, wherein the aromatic ring structure represented by A is a benzene ring structure, a naphthalene ring structure or a pyridine ring structure.
  • ⁇ 4> The positive lithographic plate according to any one of ⁇ 1> to ⁇ 3>, wherein the aromatic ring structure represented by A is a naphthalene ring structure or a pyridine ring structure, and m is 0. A printing plate master.
  • ⁇ 5> The positive lithographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 3>, wherein the aromatic ring structure represented by A is a benzene ring structure and m is 1.
  • ⁇ 6> The positive planographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 5> above, wherein the acid group represented by Z has a pKa of 2.5 to 7.5.
  • ⁇ 7> The positive planographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 6> above, wherein the binder polymer has a weight average molecular weight of 8,000 to 20,000.
  • the image recording layer is selected from the group consisting of a phenol resin, a styrene-acrylonitrile resin, an acrylic resin, an acetal resin, and a resin having a urea bond, a urethane bond, or an amide bond in the main chain as the other binder polymer.
  • the image recording layer has a lower layer and an upper layer, The positive lithographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 8>, wherein the image recording layer containing the binder polymer is at least one of the lower layer and the upper layer.
  • An exposure process for exposing the positive lithographic printing plate precursor according to any one of ⁇ 1> to ⁇ 9> above, and A method for producing a lithographic printing plate comprising, in this order, a development step of developing the exposed positive lithographic printing plate precursor using a developer having a pH of 10.0 or less.
  • the amount of each component in the composition is the total amount of the plurality of corresponding substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.
  • the notation that does not indicate substitution and non-substitution includes those not having a substituent and those having a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • (meth) acryl is a term used in a concept including both acryl and methacryl
  • (meth) acryloyl is a term used as a concept including both acryloyl and methacryloyl.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group.
  • the notation of the group in the compound represented by the formula no substitution or no substitution is described.
  • the group can further have a substituent, unless otherwise specified, the group includes not only an unsubstituted group but also a group having a substituent.
  • R represents an alkyl group, an aryl group or a heterocyclic group
  • R is an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, an unsubstituted group
  • process in the present disclosure is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, it is included in this term if the intended purpose of the process is achieved. It is.
  • mass% and wt% are synonymous, and “part by mass” and “part by weight” are synonymous. Furthermore, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
  • weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation) unless otherwise specified.
  • the total solid content means the total mass of components excluding volatile components such as a solvent in the composition.
  • the term “lithographic printing plate precursor” includes not only a lithographic printing plate precursor but also a discarded plate precursor. Further, the term “lithographic printing plate” includes not only a lithographic printing plate prepared by subjecting a lithographic printing plate precursor to operations such as exposure and development, but also a discarded plate. In the case of a discarded original plate, exposure and development operations are not necessarily required. The discarded plate is a lithographic printing plate precursor to be attached to a plate cylinder that is not used when, for example, printing a part of paper in single color or two colors in color newspaper printing.
  • the present disclosure will be described in detail.
  • a positive planographic printing plate precursor (hereinafter, also simply referred to as “lithographic printing plate precursor”) according to the present disclosure has a support and an image recording layer formed on the support, and the image recording layer described above.
  • a binder polymer having an acid value of 2 meq / g to 4 meq / g (hereinafter also referred to as “specific binder polymer”) and an infrared absorber are included.
  • the lithographic printing plate precursor according to the present disclosure contains a specific binder polymer in the image recording layer. It is considered that a lithographic printing plate precursor excellent in developability at a low pH can be obtained when the acid value of acid groups having a pKa of 9 or less in this specific binder polymer is 2 meq / g to 4 meq / g.
  • the specific binder polymer includes a structural unit represented by any one of the formulas A1 to A3, and in these structural units, in the structure represented by the formula B1, A is a polycyclic aromatic ring structure. Or a heteroaromatic ring structure, or A having a benzene ring structure and having R 4 as a substituent, the acid group represented by Z is neutralized with a developer. In this case, the cohesiveness of the aromatic ring structure represented by A tends to be lowered, and the dispersibility of the binder polymer is likely to be improved.
  • a low pH developer can be used for development.
  • a developer having a pH of 10.0 or less can be used.
  • This developer having a pH of 10.0 or less has advantages such as excellent storage stability because it is difficult to be neutralized by, for example, a carbonic acid compound in the air, and easy processing of the waste liquid.
  • the positive planographic printing plate precursor according to the present disclosure can be developed at a low pH, even when a fatigued developer (a developer that has been used for development and has a lowered pH) is used. It is considered that developability is good. That is, the positive planographic printing plate precursor according to the present disclosure is considered to have a property of being resistant to the fatigue of the developing solution during development.
  • lithographic printing plate excellent in the number of printable plates hereinafter also referred to as “printing durability”.
  • the present inventors have found that the lithographic printing plate having excellent printing durability can be easily obtained according to the positive lithographic printing plate precursor according to the present disclosure.
  • the reason why the above effect is obtained is not clear, but because the specific binder polymer contains a structural unit represented by any one of formulas A1 to A3, the interaction between the specific binder polymer and the infrared absorber is strong. It is estimated that the printing durability is excellent.
  • structural units represented by any one of formulas A1 ⁇ formula A3 is an ester bond as X 1, when the amide bond, including the strong structure of hydrogen bonding such as urethane bond or a urea bond further press life It is thought that it is easy to improve.
  • the present inventors have found that the lithographic printing plate precursor excellent in ink deposition property can be easily obtained with the positive lithographic printing plate according to the present disclosure.
  • a short time from the start of printing on a lithographic printing plate to the absence of an area where no ink is attached to the printing portion is said to be excellent in ink deposition.
  • the acid groups represented by Z contained in the specific binder polymer are present in an aggregated state in the image recording layer. For this reason, for example, even after the surface of the lithographic printing plate is washed by wiping with water, the surface of the image recording layer is hardly hydrophilized, so that it is considered that the ink deposition property is excellent.
  • the present inventors have found that according to the positive planographic printing plate according to the present disclosure, it is easy to obtain a planographic printing plate precursor excellent in ablation suppression.
  • a phenomenon in which components contained in the image recording layer are scattered outside the lithographic printing plate precursor by heating during exposure of the lithographic printing plate precursor is called ablation.
  • the acid groups represented by Z contained in the specific binder polymer are considered to be aggregated in the image recording layer as described above, and are bound in the image recording layer. It is considered strong. For this reason, it is considered that the coating of low molecular components and the like is suppressed even during heating by exposure, and the ablation suppression property is excellent.
  • details of each component included in the planographic printing plate precursor according to the present disclosure will be described.
  • the image recording layer in the present disclosure contains a specific binder polymer.
  • the specific binder polymer has at least one structural unit selected from the group consisting of a structural unit represented by the following formula A1, a structural unit represented by the following formula A2, and a structural unit represented by the following formula A3.
  • L A represents —C ( ⁇ O) O—, —C ( ⁇ O) NR 5 —, or a phenyl group
  • R 5 represents a hydrogen atom or an alkyl group
  • R A represents a group represented by Formula B1.
  • R 1 represents a hydrogen atom or an alkyl group.
  • R A represents a group represented by Formula B1
  • R 2 and R 3 each independently represent a hydrogen atom or an alkyl group.
  • R A represents a group represented by Formula B1.
  • L 1 represents a single bond or a divalent linking group
  • X 1 represents a single bond, an ester bond, an amide bond, a urethane bond, or a urea bond
  • A represents an aromatic ring structure
  • Z is independent.
  • L A represents —C ( ⁇ O) O—, —C ( ⁇ O) NR 5 —, or a phenyl group, and represents —C ( ⁇ O) O— or —C ( ⁇ O) NR 5 —. Is preferred.
  • L A is described as —C ( ⁇ O) O—
  • the carbon atom side of —C ( ⁇ O) O— is the carbon atom to which R 1 in Formula A1 is bonded, and the oxygen atom side is in Formula A1. It means to bind to RA respectively.
  • R 5 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom.
  • R 1 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom.
  • R A represents a group represented by Formula B1.
  • L 1 represents a single bond or a divalent linking group, preferably a single bond or an alkylene group, and more preferably a single bond or an alkylene group having 2 to 4 carbon atoms from the viewpoint of developability. More preferably, it is an alkylene group having 2 carbon atoms.
  • L 1 when X 1 is a single bond, L 1 is also preferably a single bond.
  • L 1 is preferably an alkylene group, more preferably an alkylene group having 2 to 4 carbon atoms, and an alkylene group having 2 carbon atoms More preferably, it is a group.
  • X 1 represents a single bond, an ester bond, an amide bond, a urethane bond or a urea bond, preferably a single bond or a urea bond, and more preferably a urea bond from the viewpoint of printing durability.
  • A represents an aromatic ring structure, and may be either an aromatic hydrocarbon ring structure or a heteroaromatic ring structure.
  • the hetero atom contained in the heteroaromatic ring structure include a nitrogen atom, an oxygen atom, and a sulfur atom, and a nitrogen atom is preferable.
  • A is preferably a benzene ring structure, a naphthalene ring structure, a pyridine ring structure, a pyrimidine ring structure, a pyrazine ring structure or a pyridazine ring structure, and more preferably a benzene ring structure, a naphthalene ring structure or a pyridine ring structure.
  • A is preferably a benzene ring structure from the viewpoint of developability, and is preferably a naphthalene ring structure or a pyridine ring structure from the viewpoint of printing durability.
  • each Z independently represents an acid group having a pKa of 9 or less, preferably a carboxy group, a hydroxy group, or a sulfo group, and more preferably a carboxy group or a hydroxy group.
  • the pKa of the acid group represented by Z is preferably 2.5 to 7.5 from the viewpoint of printing durability.
  • the pKa of the acid group is calculated from the structural formula of the monomer used at the time of introduction of the structural units represented by the formulas A1 to A2 using ACD / pKa (ACD / Labs) software. Value.
  • n represents an integer of 1 or more, more preferably 1 or 2, and still more preferably 1.
  • Each R 4 independently represents a hydrogen atom, —OR 6 , an alkyl group, a halogen atom, —C ( ⁇ O) R 7 , —C ( ⁇ O) OR 7 or a nitro group; a hydroxy group; Is preferably an alkoxy group having 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a halogen atom or a nitro group, more preferably a hydroxy group, a methyl group, a methoxy group, a fluorine atom, a chlorine atom or a nitro group, from the viewpoint of developability. More preferred is a nitro group.
  • R 6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a methyl group.
  • R 7 represents an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.
  • R 4 is preferably bonded to an atom adjacent to the atom to which Z is bonded in the aromatic ring structure represented by A.
  • [M] m represents an integer of 0 or more.
  • m is preferably 0 or 1, and more preferably 0.
  • n + m represents a number equal to or less than the maximum number of substituents of the aromatic ring structure represented by A.
  • n + m is an integer of 2 to 4
  • n + m is an integer of 1 to 7
  • n + m Is an integer from 0 to 4.
  • the aromatic ring structure represented by A may have a substituent other than Z and R 4 described above.
  • substituents include an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heteroaryl group, an amino group, —C ( ⁇ O) N (—R 8 ) R 9 , —SR 9 , S ( ⁇ O ) R 9 , S ( ⁇ O) 2 R 9 , a thiol group, or a nitrile group, but is not limited thereto.
  • R 8 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 9 represents an alkyl group having 1 to 4 carbon atoms.
  • the structural unit represented by the formula A1 can be introduced into the specific binder polymer when the specific binder polymer is produced, for example, by using a compound represented by the following formula A1-A as a monomer.
  • the compound represented by Formula A1-A is preferably a compound represented by Formula A1-B or a compound represented by Formula A1-C.
  • the compound represented by the formula A1-A can be obtained by a known method. For example, a method of adding a compound having an amino group to a (meth) acrylate compound having an isocyanate group such as 2-methacryloyloxyethyl isocyanate (a compound corresponding to Formula A1-B can be obtained), acrylic acid chloride, etc. And a method of adding an amino group-containing compound to an acrylic acid halide compound (a compound corresponding to Formula A1-C is obtained).
  • R A has the same meaning as R A in formula A1 described above, and the preferred embodiments are also the same.
  • R 2 and R 3 each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom.
  • the structural unit represented by the formula A2 can be introduced into the specific binder polymer when the specific binder polymer is produced, for example, by using a compound represented by the formula A2-A as a monomer.
  • R 2, R 3, R A is the same meaning as R 2, R 3, R A in the formula A2 described above, preferred embodiment is also the same.
  • the compound represented by the formula A2 can be obtained by a known method.
  • a method in which maleic anhydride and the corresponding amine or aniline compound are subjected to dehydration condensation in an acid catalyst can be used.
  • R A has the same meaning as R A in formula A1 described above, and the preferred embodiments are also the same.
  • the structural unit represented by the formula A3 is acetalized at the time of producing a specific binder polymer, for example, by using a vinyl acetate compound as a monomer, and a polymer compound obtained by saponification with an aldehyde having a structure corresponding to RA . By doing so, it can be introduced into the specific binder polymer.
  • the content of the structural unit represented by Formula A1 to Formula A3 is preferably 15% by mass or more, more preferably 20% by mass or more, and more preferably 40% by mass or more with respect to the total mass of the specific binder polymer. More preferably.
  • the upper limit of the content is not particularly limited, but is preferably 95% by mass or less, more preferably 90% by mass or less, and 80% by mass or less from the viewpoint of ink inking property. Is more preferable.
  • the specific binder polymer may further contain other structural units from the viewpoint of ink deposition properties.
  • other structural units include structural units derived from (meth) acrylic acid ester compounds.
  • the (meth) acrylic acid ester compound include methyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, methacrylamide, phenylacrylamide, styrene, acrylonitrile and the like.
  • the structural units described in paragraph 0033 of International Publication No. 2012/110359 may be included.
  • the other structural unit may be contained individually by 1 type, and may use 2 or more types together.
  • the content of other structural units is preferably 5% by mass to 50% by mass, more preferably 5% by mass to 40% by mass with respect to the total mass of the specific binder polymer, and 5% by mass to 20%. More preferably, it is mass%.
  • the acid value due to the acid group of pKa9 or less of the specific binder polymer is 2 meq / g to 4 meq / g, and from the viewpoint of developability at low pH, it is preferably 2.2 meq / g to 3.8 meq / g. More preferably, it is 2.5 meq / g to 3.5 meq / g.
  • the acid value due to the acid group of pKa 9 or less of the specific binder polymer is measured by the following method. About 0.5 g of the specific binder polymer is weighed in a container, and the weighed value W1 (g) is recorded.
  • a mixed solution of 54 mL of tetrahydrofuran (THF) and 6 mL of distilled water is added, and the weighed specific binder polymer is diluted to obtain a sample 1 for measuring the degree of neutralization.
  • F1 (mL) the maximum value among the plurality of titrant liquid amounts required up to the plurality of equivalent points
  • the product of F1 (mL) and the normality of sodium hydroxide aqueous solution (0.1 mol / L) corresponds to the number of millimoles of acid groups (for example, —COOH) having a pKa of 9 or less contained in the specific binder polymer.
  • the acid value (meq / g) is determined according to the following formula.
  • F1 (mL) ⁇ normality of sodium hydroxide aqueous solution (0.1 mol / L) / W1 (g) total number of acid groups contained in 1 g of the specific binder polymer (meq / g) ⁇ 100
  • the weight average molecular weight of the specific binder polymer is preferably 8,000 to 20,000, more preferably 10,000 to 18,000, and more preferably 12,000 to 20,000 from the viewpoint of printing durability and developability. More preferably, it is 16,000. If the weight average molecular weight is 8,000 or more, the printing durability is easily excellent, and if it is 20,000 or less, the developability is easy.
  • the image recording layer may contain a specific binder polymer alone or in combination of two or more.
  • the content of the specific binder polymer in the image recording layer is preferably 45% by mass to 90% by mass, more preferably 50% by mass to 80% by mass, and 62% by mass with respect to the total mass of the image recording layer. More preferably, the content is from 70% to 70% by mass.
  • the image recording layer in the present disclosure contains an infrared absorber.
  • the infrared absorber is not particularly limited as long as it is a dye that absorbs infrared light and generates heat, and various dyes known as infrared absorbers can be used.
  • the infrared absorber that can be used in the present disclosure commercially available dyes and known ones described in literature (for example, “Dye Handbook” edited by Organic Synthetic Chemical Society, published in 1970) can be used.
  • azo dyes include azo dyes, metal complex azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, and oxonol dyes.
  • these dyes those that absorb at least infrared light or near infrared light are preferable in terms of being suitable for use in lasers that emit infrared light or near infrared light, and cyanine dyes are particularly preferred. preferable.
  • Examples of the dye that absorbs at least infrared light or near infrared light include, for example, JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-. Cyanine dyes described in each publication such as 78787, oxonol dyes described in International Publication No. 2012/110359, JP-A-58-173696, JP-A-58-181690, JP-A-58-194595.
  • Epolight III-178 of Eporin Co. Epolight III-130, Epolight III-125 and the like are particularly preferably used.
  • Another particularly preferable example of the dye is a near-infrared absorbing dye described as formulas (I) and (II) in US Pat. No. 4,756,993.
  • cyanine dyes particularly preferred are cyanine dyes, phthalocyanine dyes, oxonol dyes, squarylium dyes, pyrylium salts, thiopyrylium dyes, and nickel thiolate complexes.
  • the cyanine dye represented by the following formula (a) is most preferable because it is excellent in stability and economy when used in the image recording layer in the present disclosure.
  • X 1 represents a hydrogen atom, a halogen atom, a diarylamino group (—NPh 2 ), X 2 -L 1 or a group shown below.
  • X 2 represents an oxygen atom or a sulfur atom.
  • L 1 represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, or a hydrocarbon group having 1 to 12 carbon atoms containing a hetero atom.
  • a hetero atom here shows N, S, O, a halogen atom, and Se.
  • Xa ⁇ is defined in the same manner as Za ⁇ described later, and R a represents a substituent selected from a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, and a halogen atom.
  • R 21 and R 22 each independently represents a hydrocarbon group having 1 to 12 carbon atoms.
  • R 21 and R 22 are preferably hydrocarbon groups having 2 or more carbon atoms, and R 21 and R 22 are bonded to each other to form a 5-membered ring or 6 It is particularly preferable that a member ring is formed.
  • Ar 1 and Ar 2 may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent.
  • Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring.
  • a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned.
  • Y 11 and Y 12 may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms.
  • R 23 and R 24 may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent.
  • Preferable substituents include an alkoxy group having 12 or less carbon atoms, a carboxyl group, and a sulfo group.
  • R 25 , R 26 , R 27 and R 28 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, a hydrogen atom is preferred.
  • Za ⁇ represents a counter anion. However, Za ⁇ is not necessary when the cyanine dye represented by the formula (a) has an anionic substituent in the structure and charge neutralization is not necessary.
  • Preferred Za ⁇ is a halide ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, from the storage stability of the photosensitive layer coating solution.
  • cyanine dyes represented by formula (a) that can be suitably used include paragraphs 0017 to 0019 of JP-A No. 2001-133969, paragraphs 0012 to 0038 of JP-A No. 2002-40638, and JP-A No. 2002. No. 23360, paragraphs 0012 to 0023 can be mentioned.
  • the cyanine dye A shown below is particularly preferable as the infrared absorber.
  • the addition amount when the infrared absorber is added to the image recording layer according to the present disclosure is preferably 0.01% by mass to 50% by mass with respect to the total solid content of the photosensitive resin composition.
  • the content is more preferably 1% by mass to 30% by mass, and particularly preferably 1.0% by mass to 30% by mass.
  • the addition amount is 0.01% by mass or more, high sensitivity is obtained, and when it is 50% by mass or less, the uniformity of the layer is good and the durability of the layer is excellent.
  • the image recording layer in the present disclosure may further contain other binder polymer in addition to the specific binder polymer described above.
  • the other binder polymer is not particularly limited as long as it is a conventionally known binder polymer, for example, polyurethane resin, polyurea resin, polyurethane urea resin, polyamide resin, polyimide resin, epoxy resin, polyacetal resin, acrylic resin, methacrylic resin, Examples thereof include polystyrene resins and phenol resins.
  • a phenol resin, a styrene-acrylonitrile resin, an acrylic resin, an acetal resin, a resin having a urea bond, a urethane bond, or an amide bond in the main chain is preferable.
  • these resins preferably have a hydrophilic group and more preferably have an acid group from the viewpoint of developability.
  • the other binder polymer does not include a component corresponding to the specific binder polymer described above.
  • the other binder polymer used in the present disclosure is preferably a phenol resin having a weight average molecular weight exceeding 2,000.
  • the phenol resin having a weight average molecular weight exceeding 2,000 is a phenol resin containing phenol or substituted phenols as a structural unit, and is preferably a novolac resin.
  • the novolak resin is preferable for the photosensitive resin composition of the present disclosure because it causes strong hydrogen bonding in the unexposed area and part of the hydrogen bonding is easily released in the exposed area in the lithographic printing plate precursor.
  • the novolak resin is not particularly limited as long as it contains phenols as a structural unit in the molecule.
  • the novolak resin in the present disclosure is a resin obtained by a condensation reaction of phenol, a substituted phenol shown below, and an aldehyde.
  • the phenol include phenol, isopropylphenol, t-butylphenol, Examples thereof include t-amylphenol, hexylphenol, cyclohexylphenol, 3-methyl-4-chloro-6-t-butylphenol, isopropylcresol, t-butylcresol, and t-amylresole.
  • T-butylphenol and t-butylcresol are preferable.
  • aldehydes include aliphatic and aromatic aldehydes such as formaldehyde, acetaldehyde, acrolein, and crotonaldehyde. Preferred are formaldehyde and acetaldehyde. More specifically, the novolak resin in the present disclosure includes, for example, a condensation polymer of phenol and formaldehyde (phenol formaldehyde resin), a condensation polymer of m-cresol and formaldehyde (m-cresol formaldehyde resin), p.
  • phenol formaldehyde resin phenol formaldehyde resin
  • m-cresol formaldehyde resin m-cresol formaldehyde resin
  • an alkyl group having 3 to 8 carbon atoms such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin is used.
  • examples thereof include a condensation polymer of phenol and formaldehyde as a substituent.
  • novolak resins phenol formaldehyde resins and phenol / cresol mixed formaldehyde resins are particularly preferable.
  • the weight average molecular weight of the phenol resin is preferably more than 2,000 and not more than 50,000, more preferably 2,500 to 20,000, and particularly preferably 3,000 to 10,000. .
  • the degree of dispersion (weight average molecular weight / number average molecular weight) is preferably 1.1 to 10.
  • the number average molecular weight is a number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.
  • the styrene-acrylonitrile resin is not particularly limited, and a known resin can be used.
  • a structural unit derived from (meth) acrylonitrile described in paragraphs 0012 to 0021 of JP2011-209343A can be used.
  • a copolymer containing a structural unit derived from styrene can be used.
  • the acrylic resin is not particularly limited, and a known resin can be used. Examples thereof include the acrylic resins described in paragraphs 0012 to 0039 of EP 182601.
  • the acetal resin is not particularly limited, and a known resin can be used. Examples thereof include acetal resins described in paragraphs 0012 to 0021 of International Publication No. 2014/106554.
  • the polymer compound (specific polymer compound) having at least one bond selected from the group consisting of a urea bond, a urethane bond and an amide bond in the main chain is not particularly limited as long as it is a conventionally known compound.
  • the following urea resins, urethane resins and amide resins are preferably used.
  • “main chain” represents a relatively long bond chain in the molecule of the polymer compound constituting the resin
  • “side chain” represents an atomic group branched from the main chain.
  • the specific polymer compound preferably has at least one of a urea bond, a urethane bond, and an amide bond in the main chain from the viewpoint of printing durability of the resulting lithographic printing plate. It is more preferable to have one bond in the main chain, and it is even more preferable to have a urea bond in the main chain.
  • the polymer compound is preferably a polyurea resin, a polyurethane resin, or a polyamide resin, preferably a polyurea resin or a polyamide resin, and most preferably a polyurea resin.
  • the “urea bond” is represented by the general formula: —NR 1 C ( ⁇ O) NR 2 —.
  • R 1 and R 2 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, A cyclohexyl group or the like, preferably a hydrogen atom or an alkyl group having 5 or less carbon atoms.
  • a polymer compound whose main chain is formed by a urea bond is also referred to as a polyurea resin.
  • the urea bond may be formed by any means, but can be obtained by a reaction between an isocyanate compound and an amine compound.
  • a terminal hydroxyl group or a hydroxyl group such as 1,3-bis (2-aminoethyl) urea, 1,3-bis (2-hydroxyethyl) urea, 1,3-bis (2-hydroxypropyl) urea, etc.
  • a urea compound substituted with an alkyl group having an amino group may be synthesized as a raw material.
  • the isocyanate compound used as a raw material can be used without particular limitation as long as it is a polyisocyanate compound having two or more isocyanate groups in the molecule, but a diisocyanate compound is preferred.
  • the polyisocyanate compound include 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,3-cyclopentane diisocyanate, 9H-fluorene.
  • the amine compound used as a raw material can be used without particular limitation as long as it is a polyamine compound having two or more amino groups in the molecule, but a diamine compound is preferred.
  • polyamine compounds include 2,7-diamino-9H-fluorene, 3,6-diaminoacridine, acriflavine, acridine yellow, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4′-diamino Benzophenone, bis (4-aminophenyl) sulfone, 4,4′-diaminodiphenyl ether, bis (4-aminophenyl) sulfide, 1,1-bis (4-aminophenyl) cyclohexane, 4,4′-diaminodiphenylmethane, 3 , 3'-diaminodiphenylmethane, 3,3'-diaminobenzophenone, 4,4
  • the “urethane bond” is represented by the formula: —OC ( ⁇ O) NR 3 —.
  • R 3 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, etc.), preferably Is a hydrogen atom or an alkyl group having 5 or less carbon atoms, more preferably a hydrogen atom or a methyl group.
  • a polymer having a main chain formed by a urethane bond is referred to as a polyurethane resin.
  • the urethane bond may be formed by any means, but can be obtained by a reaction between an isocyanate compound and a compound having a hydroxy group.
  • the isocyanate compound used as a raw material is preferably a polyisocyanate compound having two or more isocyanate groups in the molecule, and more preferably a diisocyanate compound.
  • a polyisocyanate compound the polyisocyanate compound mentioned as a raw material which forms the said urea bond can be mentioned.
  • the compound having a hydroxy group used as a raw material include a polyol compound, an aminoalcohol compound, an aminophenol compound, and an alkylaminophenol compound, and a polyol compound or an aminoalcohol compound is preferable.
  • the polyol compound is a compound having at least two or more hydroxy groups in the molecule, and preferably a diol compound. Moreover, you may have an ester bond or an ether bond in a molecule
  • the polyol compound include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9 -Nonanediol, 1,10-decanediol, neopentyl glycol, polyethylene glycol, polytetramethylene glycol, 1,4-cyclohexanedimethanol, pentaerythritol, 3-methyl-1,5-pentanediol, poly (ethylene adipate) , Poly (diethylene adipate), poly (propylene adipate), poly (
  • the diol compound A which has the acid group mentioned later can also be used suitably.
  • the amino alcohol compound is a compound having an amino group and a hydroxy group in the molecule, and may further have an ether bond in the molecule.
  • Examples of amino alcohols include aminoethanol, 3-amino-1-propanol, 2- (2-aminoethoxy) ethanol, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3- Examples thereof include propanediol and 1,3-diamino-2-propanol.
  • the amide bond may be formed by any means, but can be obtained by reacting a carboxylic acid chloride with an amine compound.
  • an amine compound the polyamine compound mentioned as a raw material which forms the said urea bond can be mentioned,
  • the diamine compound A which has an acid group mentioned later can also be used conveniently.
  • the carboxylate compound include a carboxylic acid halide compound or a carboxylic acid ester compound, and examples thereof include the following CL-1 to CL-10.
  • the specific polymer compound preferably contains an acid group from the viewpoint of developability.
  • Preferred examples of the acid group include the acid groups described in (1) to (7) below.
  • Phenolic hydroxy group a divalent group represented by —Ar—OH or —Ar (—OH) —
  • Sulfonamide group a divalent group represented by —SO 2 NH—R or —SO 2 NH—
  • Substituted sulfonamide acid group (—SO 2 NHCOR, —SO 2 NHSO 2 R, —CONHSO 2 R) (hereinafter referred to as “active imide group”)
  • Carboxy group —CO 2 H)
  • Sulfo group —SO 3 H
  • (6) Phosphate group —OPO 3 H 2 )
  • Phosphonic acid group —PO 3 H 2
  • Ar represents a divalent aryl group which may have a substituent
  • R represents a hydrocarbon group which may have
  • the specific polymer compounds having an acid group selected from the above (1) to (7) (1) a specific polymer compound having a phenolic hydroxy group, (2) a sulfonamide group or (3) an active imide group
  • a specific polymer compound having (1) a phenolic hydroxy group or (2) a sulfonamide group is particularly preferable from the viewpoint of sufficiently ensuring solubility in an alkali developer and film strength. That is, the specific polymer compound preferably has at least one of a phenolic hydroxy group and a sulfonamide group in at least one of the main chain and the side chain.
  • Specific compounds include polyurea resins having sulfonamide groups in the main chain, polyurea resins having phenolic hydroxy groups in the main chain, polyurethane resins having sulfonamide groups in the main chain, and phenolic hydroxy groups in the main chain. It is preferably at least one selected from the group consisting of polyamide resins.
  • the polymer compound having a phenolic hydroxy group in the main chain means having a divalent group represented by —Ar (—OH) — in the main chain.
  • the polymer compound having a sulfonamide group in the main chain means having a divalent group represented by —SO 2 NH— in the main chain.
  • the specific polymer compound preferably has a structural unit having a phenolic hydroxyl group, and more preferably has a structural unit represented by the following formula AF-1 in the main chain.
  • R A1 represents a single bond or a divalent linking group.
  • R A1 is preferably a single bond, an alkylene group having 1 to 6 carbon atoms or a sulfonyl group, more preferably a single bond or an alkylene group having 1 to 5 carbon atoms, and preferably a single bond or a methylene group. More preferably, it is a single bond.
  • the alkylene group in R A1 may be linear, branched or cyclic.
  • the alkylene group in R A1 may be substituted.
  • Preferred examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a halogen atom.
  • the aryl group may be further substituted, and a preferable substituent is a hydroxy group.
  • the phenolic hydroxyl group in the formula AF-1 is preferably bonded to the ortho position where —NH— is bonded.
  • a lithographic printing plate precursor excellent in developability can be obtained.
  • Preferred examples of the diamine compound that forms the structural unit having a phenolic hydroxyl group include the following diamine compounds. By reacting the following diamine compound with an isocyanate compound as diamine compound A having an acid group, an acid group can be introduced into the specific polymer compound.
  • DADHB 1,3-DAP, DAMDH, PDABP, AHPPHFP or AHPFL are preferable, and DADHB is more preferable.
  • the specific polymer compound preferably has a structural unit represented by the following formula AF-2 in the main chain as a structural unit having a sulfonamide group.
  • R A2 , R A3 and R A4 each independently represent a divalent linking group
  • X represents a divalent group represented by —NH— or —O—
  • R A2 and R A4 in Formula AF-2 are each independently an alkylene group, an arylene group, a divalent saturated alicyclic hydrocarbon group, a divalent unsaturated alicyclic hydrocarbon group, or these groups A plurality of connected divalent groups are preferable, and an alkylene group or an arylene group is more preferable.
  • the alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 2 to 15 carbon atoms, and still more preferably an alkylene group having 2 to 8 carbon atoms.
  • the alkylene group may contain an oxygen atom in the carbon chain.
  • the substituent that the alkylene group may have include an alkyl group, an aryl group, and a halogen atom.
  • the arylene group is preferably an arylene group having 6 to 20 carbon atoms, more preferably a phenylene group or a naphthylene group, and further preferably a phenylene group.
  • the arylene group may have a hetero atom in the ring structure, and examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.
  • the divalent saturated alicyclic hydrocarbon group is preferably a divalent saturated alicyclic hydrocarbon group having 4 to 10 carbon atoms, more preferably a divalent saturated alicyclic hydrocarbon group having 4 to 8 carbon atoms.
  • a divalent saturated alicyclic hydrocarbon group having 6 to 8 carbon atoms is more preferable.
  • the substituent that the divalent saturated alicyclic hydrocarbon group may include include an alkyl group, an aryl group, and a halogen atom.
  • the divalent unsaturated alicyclic hydrocarbon group include a cyclopentenyl group, a cyclopentadienyl group, a cyclohexenyl group, a cyclohexadienyl group, and a cycloheptenyl group.
  • the divalent group in which a plurality of these groups are linked is preferably an alkylene group and an arylene group, or a group in which an alkylene group and a divalent saturated alicyclic hydrocarbon group are bonded, and an alkylene group-arylene group.
  • a group bonded in the order of -alkylene group or alkylene group-divalent saturated alicyclic hydrocarbon group-alkylene group is preferable.
  • R A3 in Formula AF-2 is preferably a divalent linking group containing a phenylene group or a polycyclic structure from the viewpoint of printing durability and chemical resistance, and is preferably a divalent linking group comprising a phenylene group or a polycyclic structure.
  • a valent linking group is more preferable, and a divalent linking group having a polycyclic structure is still more preferable.
  • the polycyclic structure is preferably a naphthalene derivative structure, an anthracene derivative structure, a biphenyl structure, or a terphenyl structure, and a xanthone structure, anthrone structure, xanthene structure, dihydroanthracene structure, anthracene structure, biphenyl structure, or The terphenyl structure is more preferable. From the viewpoint of chemical resistance, printing durability, and developability, a xanthone structure, anthrone structure, biphenyl structure, or naphthalene structure is preferable, and a xanthone structure or anthrone structure is more preferable.
  • Preferred examples of the diamine compound or diol compound that forms the structural unit represented by the formula AF-2 include the following compounds.
  • Z represents a hydroxy group (—OH) or an amino group (—NH 2 ), and two Zs represent the same group.
  • the specific polymer compound may have a structural unit having a carboxy group in the main chain.
  • the structural unit having a carboxy group is not particularly limited, and examples thereof include a group in which a carbon atom of an alkylene group, an arylene group, or a combination thereof is substituted with a carboxy group.
  • the alkylene group is preferably an alkylene group having 2 to 20 carbon atoms, and more preferably an alkylene group having 4 to 10 carbon atoms.
  • the arylene group is preferably an arylene group having 6 to 12 carbon atoms, and more preferably a phenylene group.
  • Preferred examples of the diamine compound or diol compound that forms the structural unit having a carboxy group include the following compounds.
  • Z represents a hydroxy group (—OH) or an amino group (—NH 2 ), and two Zs represent the same group.
  • the specific polymer compound preferably has a structural unit having an active imide group in the main chain.
  • the structural unit having an active imide group is not particularly limited, and examples thereof include a group in which a carbon atom of an alkylene group is substituted with an active imide group.
  • the alkylene group is preferably an alkylene group having 2 to 20 carbon atoms, and more preferably an alkylene group having 4 to 10 carbon atoms.
  • Acid groups can be introduced into specific polymer compounds.
  • the specific polymer compound used in the present disclosure preferably further has an alkyleneoxy group in the main chain.
  • the lithographic printing plate precursor excellent in the image forming property of the obtained lithographic printing plate and excellent in printing durability of the obtained lithographic printing plate is obtained.
  • the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 10 carbon atoms, more preferably an alkyleneoxy group having 2 to 8 carbon atoms, still more preferably an alkyleneoxy group having 2 to 4 carbon atoms, an ethyleneoxy group, or A propyleneoxy group is particularly preferred.
  • the alkyleneoxy group may be a polyalkyleneoxy group.
  • the polyalkyleneoxy group is preferably a polyalkyleneoxy group having 2 to 50 repeats, more preferably a polyalkyleneoxy group having 2 to 40 repeats, and still more preferably a polyalkyleneoxy group having 2 to 30 repeats.
  • the preferable carbon number of the structural repeating unit of the polyalkyleneoxy group is the same as the preferable carbon number of the alkyleneoxy group.
  • the weight average molecular weight of the specific polymer compound is preferably 10,000 to 300,000, more preferably 20,000 to 300,000, from the viewpoint of printing durability of the resulting lithographic printing plate, More preferably, it is 50,000 to 300,000.
  • binder polymers may be contained singly or in combination of two or more.
  • the content of the other binder polymer in the photosensitive resin composition is preferably 10% by mass to 95% by mass and more preferably 20% by mass to 90% by mass with respect to the total solid mass. More preferably, the content is 30% by mass to 85% by mass.
  • the total solid mass of the photosensitive resin composition represents an amount excluding volatile components such as a solvent.
  • the numerical value at the lower right of the parenthesis represents the molar ratio of constituent units.
  • the following formula is described in a form in which carbon atoms and hydrogen atoms of hydrocarbons are omitted.
  • binder polymers may be used alone or in combination of two or more.
  • another binder polymer it is preferable to use a phenol resin in combination with at least one resin selected from the group consisting of a styrene-acrylonitrile resin, an acrylic resin, an acetal resin, and a specific polymer compound.
  • the content of the other binder polymer is preferably 1% by mass to 90% by mass, more preferably 3% by mass to 70% by mass, and more preferably 5% by mass with respect to the total mass of the image recording layer from the viewpoint of printing durability. ⁇ 50% by weight is particularly preferred.
  • the image recording layer may contain other components as desired.
  • known additives can be used.
  • the acid generator, the acid proliferating agent, and other additives, which are optional components in the image recording layer, will be described.
  • the image recording layer according to the present disclosure preferably contains an acid generator from the viewpoint of improving sensitivity in the obtained lithographic printing plate precursor.
  • the acid generator is a compound that generates an acid by light or heat, and refers to a compound that decomposes by irradiation with infrared rays or heating at 100 ° C. or more to generate an acid.
  • the acid generated is preferably a strong acid having a pKa of 2 or less, such as sulfonic acid and hydrochloric acid.
  • the acid generated from the acid generator increases the permeability of the developer into the exposed portion image recording layer in the lithographic printing plate precursor, and further improves the solubility of the image recording layer in an alkaline aqueous solution.
  • the acid generator suitably used in the image recording layer include the acid generators described in paragraphs 0116 to 0130 of International Publication No. 2016/047392.
  • an onium salt compound as the acid generator.
  • the onium salt compound will be described.
  • Examples of onium salt compounds that can be suitably used in the present disclosure include compounds that are known as compounds that generate an acid by being decomposed by infrared energy and thermal energy generated from an infrared absorber upon exposure.
  • Examples of the onium salt compound suitable for the present disclosure include known thermal polymerization initiators and compounds having an onium salt structure described below having a bond with small bond dissociation energy from the viewpoint of sensitivity.
  • Examples of onium salts suitably used in the present disclosure include known diazonium salts, iodonium salts, sulfonium salts, ammonium salts, pyridinium salts, azinium salts, and the like. Among them, triarylsulfonium or diaryliodonium sulfonate , Carboxylate, BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ and the like are preferable.
  • Examples of onium salts that can be used as an acid generator in the present disclosure include onium salts represented by the following formulas III to V.
  • Ar 11 and Ar 12 each independently represent an aryl group having 20 or less carbon atoms which may have a substituent.
  • Preferred substituents when this aryl group has a substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. Is mentioned.
  • Z 11- is a pair selected from the group consisting of halide ions, perchlorate ions, tetrafluoroborate ions, hexafluorophosphate ions, sulfonate ions, and sulfonate ions having fluorine atoms, such as perfluoroalkylsulfonate ions.
  • Ar 21 represents an aryl group having 1 to 20 carbon atoms which may have a substituent.
  • Preferred substituents include a halogen atom, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, an alkylamino group having 1 to 12 carbon atoms, Examples thereof include a dialkylamino group having 2 to 12 carbon atoms, an arylamino group having 6 to 12 carbon atoms, and a diarylamino group (the carbon numbers of the two aryl groups are each independently 6 to 12).
  • Z 21- represents a counter ion having the same meaning as Z 11- .
  • R 31 , R 32 and R 33 may be the same or different and each represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • substituents include a halogen atom, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryloxy group having 1 to 12 carbon atoms.
  • Z 31- represents a counter ion having the same meaning as Z 11- .
  • onium salts that can be suitably used in the image recording layer are the same as the compounds described in paragraphs 0121 to 0124 of International Publication No. 2016/047392.
  • the compound described as an example of the radical polymerization initiator in paragraphs 0036 to 0045 of JP-A-2008-195018 is related to the present disclosure. It can be suitably used as an acid generator.
  • More preferable examples of the acid generator that can be used in the present disclosure include the following compounds (PAG-1) to (PAG-5).
  • these acid generators When these acid generators are contained in the image recording layer in the present disclosure, these compounds may be used alone or in combination of two or more.
  • the content of the acid generator is preferably 0.01% by mass to 50% by mass, more preferably 0.1% by mass to 40% by mass, and more preferably 0.5% by mass with respect to the total mass of the image recording layer. More preferably, it is 30% by mass.
  • the content is in the above range, an improvement in sensitivity, which is an effect of addition of an acid generator, is observed, and generation of a residual film in a non-image area is suppressed.
  • the image recording layer in the present disclosure may contain an acid proliferating agent.
  • the acid proliferating agent in the present disclosure is a compound substituted with a relatively strong acid residue, and is a compound that is easily eliminated in the presence of an acid catalyst to newly generate an acid. That is, it decomposes by an acid catalytic reaction and generates an acid again.
  • One or more acids are increased in one reaction, and the sensitivity is dramatically improved by increasing the acid concentration at an accelerated rate as the reaction proceeds.
  • the strength of the acid generated is preferably 3 or less, more preferably 2 or less, as an acid dissociation constant (pKa). If the acid dissociation constant is 3 or less, the elimination reaction by the acid catalyst is likely to occur.
  • Examples of the acid used for such an acid catalyst include dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, and phenylsulfonic acid.
  • Usable acid proliferating agents are the same as those described in paragraphs 0133 to 0135 of International Publication No. 2016/047392.
  • the content in the case of adding these acid proliferating agents to the image recording layer is preferably 0.01% by mass to 20% by mass, and preferably 0.01% by mass to 10% by mass with respect to the total mass of the image recording layer. Is more preferable, and 0.1 to 5% by mass is even more preferable.
  • the content of the acid proliferating agent is within the above range, the effect of adding the acid proliferating agent is sufficiently obtained, sensitivity is improved, and a decrease in film strength in the image area is suppressed.
  • the image recording layer in the present disclosure may contain a development accelerator, a surfactant, a print-out agent, a colorant, a plasticizer, a wax agent and the like as other additives.
  • acid anhydrides for the purpose of improving sensitivity, acid anhydrides, phenols, and organic acids may be added to the image recording layer in the present disclosure.
  • acid anhydrides cyclic acid anhydrides are preferable.
  • Specific examples of the cyclic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, and hexahydro anhydride described in US Pat. No. 4,115,128.
  • Phthalic acid, 3,6-endooxytetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, ⁇ -phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used.
  • Examples of acyclic acid anhydrides include acetic anhydride.
  • phenols include bisphenol A, 2,2′-bishydroxysulfone, p-nitrophenol, p-ethoxyphenol, 2,4,4′-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4- Hydroxybenzophenone, 4,4 ′, 4 ′′ -trihydroxytriphenylmethane, 4,4 ′, 3 ′′, 4 ′′ -tetrahydroxy-3,5,3 ′, 5′-tetramethyltriphenylmethane, etc. .
  • organic acids are described in JP-A-60-88942 and JP-A-2-96755.
  • p-toluenesulfonic acid dodecylbenzenesulfonic acid, p-toluenesulfinic acid, Ethyl sulfuric acid, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene Examples include -1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid and the like.
  • the proportion of the acid anhydride, phenols and organic acids in the total mass of the image recording layer is preferably 0.05% by mass to 20% by mass, more preferably 0.1% by mass to 15% by mass, and 1% by mass to 10% by mass is particularly preferable.
  • Nonionic surfactants such as those described in JP-A-59-121044, JP-A-4-13149, amphoteric surfactants, JP-A-62-170950, JP-A-11- A fluorine-containing monomer copolymer as described in Japanese Patent No. 288093 and Japanese Patent Application Laid-Open No. 2003-57820 can be added.
  • nonionic surfactant examples include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether and the like.
  • amphoteric activators include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine. Type (for example, trade name “Amorgen K” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
  • the ratio of the surfactant to the total mass of the image recording layer is preferably 0.01% by mass to 15% by mass, more preferably 0.01% by mass to 5% by mass, and 0.05% by mass to 2.0% by mass. % Is more preferable.
  • a printing agent for obtaining a visible image immediately after heating by exposure or a dye or pigment as an image coloring agent can be added to the image recording layer.
  • the printing-out agent and the colorant are described in detail in, for example, paragraphs 0122 to 0123 of JP-A-2009-229917, and the compounds described therein can be applied to the present disclosure.
  • These dyes are preferably added in a proportion of 0.01% by mass to 10% by mass and more preferably in a proportion of 0.1% by mass to 3% by mass with respect to the total mass of the image recording layer. .
  • plasticizer may be added to the image recording layer in order to impart flexibility and the like of the coating film.
  • plasticizers are preferably added in a proportion of 0.5 to 10% by mass, more preferably in a proportion of 1.0 to 5% by mass with respect to the total mass of the image recording layer. preferable.
  • a compound that lowers the static friction coefficient of the surface can be added.
  • a compound having an ester of a long-chain alkyl carboxylic acid can be exemplified.
  • the addition amount is preferably 0.1% by mass to 10% by mass and more preferably 0.5% by mass to 5% by mass with respect to the total mass of the image recording layer.
  • composition ratio of each component The content of each component in the image recording layer is preferably 50% by mass to 70% by mass with respect to the total mass of the image recording layer, and the content of the infrared absorber. Is preferably 0.01% by mass to 50% by mass, the content of the other binder polymer is preferably 1% by mass to 90% by mass, and the content of the acid generator is 0% by mass to 30% by mass.
  • the content of the acid proliferating agent is preferably 0% by mass to 20% by mass
  • the content of the development accelerator is preferably 0% by mass to 20% by mass
  • the surface activity is preferably
  • the content of the agent is preferably 0% by mass to 5% by mass
  • the content of the bake-out agent / colorant is preferably 0% by mass to 10% by mass
  • the content of the plasticizer is 0% by mass.
  • ⁇ 10% by mass is preferred Ku, it is preferable that the content of the wax agent is 0 to 10% by weight.
  • the image recording layer has a lower layer and an upper layer, and the image recording layer containing the binder polymer is preferably at least one of the lower layer and the upper layer.
  • the lower layer and the upper layer are preferably formed by separating the two layers.
  • the image recording layer having the upper layer and the lower layer is also referred to as a “two-layer image recording layer” and has a two-layer image recording layer.
  • the planographic printing plate precursor is also referred to as a “two-layer planographic printing plate precursor”.
  • the image recording layer containing the binder polymer may be at least one of the lower layer and the upper layer, but is preferably at least the lower layer from the viewpoint of printing durability.
  • a solvent system in which any of the components contained in the lower layer is insoluble is used when the upper layer coating solution is applied. Is. Thereby, even if it carries out 2 layer application
  • a component insoluble in a solvent such as methyl ethyl ketone or 1-methoxy-2-propanol that dissolves the alkali-soluble resin as the upper layer component is selected, and the lower layer is applied using a solvent system that dissolves the lower layer component.
  • the upper layer mainly composed of the alkali-soluble resin is dissolved in methyl ethyl ketone, 1-methoxy-2-propanol, or the like, and applied and dried, whereby two layers can be formed.
  • high-pressure air is blown from a slit nozzle installed substantially perpendicular to the web traveling direction, or heating such as steam is performed.
  • This can be achieved by applying thermal energy as conduction heat from the lower surface of the web from a roll (heating roll) supplied inside the medium, or by combining them.
  • the coating amount after drying of the lower layer component applied on the support of the lithographic printing plate precursor according to the present disclosure is preferably in the range of 0.5 g / m 2 to 4.0 g / m 2 , and 0.6 g More preferably, it is in the range of / m 2 to 2.5 g / m 2 . When it is 0.5 g / m 2 or more, printing durability is excellent, and when it is 4.0 g / m 2 or less, image reproducibility and sensitivity are excellent.
  • the coating amount after drying of the upper layer component is preferably in the range of 0.05g / m 2 ⁇ 1.0g / m 2, in the range of 0.08g / m 2 ⁇ 0.7g / m 2 It is more preferable. If it is 0.05 g / m 2 or more, development latitude, and excellent scratch resistance, if it is 1.0 g / m 2 or less, excellent sensitivity.
  • the coating amount after drying combining the lower layer and the upper layer is preferably in the range of 0.6 g / m 2 to 4.0 g / m 2 , and in the range of 0.7 g / m 2 to 2.5 g / m 2 . More preferably. When it is 0.6 g / m 2 or more, printing durability is excellent, and when it is 4.0 g / m 2 or less, image reproducibility and sensitivity are excellent.
  • the support used in the lithographic printing plate precursor according to the present disclosure is not particularly limited as long as it is a dimensionally stable plate having the required strength and durability.
  • paper plastic (for example, , Polyethylene, polypropylene, polystyrene, etc., laminated paper, metal plates (eg, aluminum, zinc, copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate) , Cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), paper on which a metal as described above is laminated or vapor-deposited, or a plastic film.
  • plastic for example, Polyethylene, polypropylene, polystyrene, etc., laminated paper, metal plates (eg, aluminum, zinc, copper, etc.), plastic films (eg, cellulose diacetate, cellulose
  • a polyester film or an aluminum plate is preferable, and among them, an aluminum plate that has good dimensional stability and is relatively inexpensive is particularly preferable.
  • a suitable aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, and may be a plastic film on which aluminum is laminated or vapor-deposited.
  • foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium.
  • the content of foreign elements in the alloy is preferably 10% by mass or less.
  • Particularly suitable aluminum in the present disclosure is pure aluminum. However, since completely pure aluminum is difficult to manufacture by refining technology, it may contain slightly different elements. Thus, the composition of the aluminum plate applied to the present disclosure is not specified, and an aluminum plate made of a publicly known material can be appropriately used.
  • the thickness of the aluminum plate used in the present disclosure is preferably 0.1 mm to 0.6 mm, more preferably 0.15 mm to 0.4 mm, and particularly preferably 0.2 mm to 0.3 mm. preferable.
  • Such an aluminum plate may be subjected to a surface treatment such as a roughening treatment or an anodizing treatment as necessary.
  • a surface treatment such as a roughening treatment or an anodizing treatment as necessary.
  • the surface treatment of the aluminum support for example, degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution, or the like, as described in detail in paragraphs 0167 to 0169 of JP-A-2009-175195, Anodizing treatment, anodizing treatment or the like is appropriately performed.
  • the anodized aluminum surface is subjected to a hydrophilic treatment as necessary.
  • hydrophilization treatment examples include an alkali metal silicate (for example, sodium silicate aqueous solution) method, a method of treating with potassium zirconate fluoride or polyvinylphosphonic acid, as disclosed in paragraph 0169 of 2009-175195. Used.
  • a support described in JP 2011-245844 A is also preferably used.
  • the lithographic printing plate precursor according to the present disclosure can be provided with an undercoat layer between the support and the image recording layer, if necessary.
  • an undercoat layer component various organic compounds are used.
  • phosphonic acids having amino groups such as carboxymethylcellulose and dextrin
  • organic phosphonic acids, organic phosphoric acids, organic phosphinic acids, amino acids, and hydroxy groups Preferred examples thereof include hydrochlorides of amines and the like.
  • These undercoat layer components may be used singly or in combination of two or more. Details of the compounds used for the undercoat layer and the method for forming the undercoat layer are described in paragraphs 0171 to 0172 of JP-A-2009-175195, and these descriptions also apply to the present disclosure.
  • the coverage of the undercoat layer is preferably 2 mg / m 2 to 200 mg / m 2 , more preferably 5 mg / m 2 to 100 mg / m 2 .
  • the coating amount is in the above range, sufficient printing durability can be obtained.
  • a back coat layer is preferably provided on the surface of the support opposite to the side on which the image recording layer is provided, if necessary.
  • a back coat layer comprises a metal oxide obtained by hydrolysis and polycondensation of an organic polymer compound described in JP-A-5-45885 and an organic or inorganic metal compound described in JP-A-6-35174.
  • a coating layer is preferably used.
  • silicon alkoxy compounds such as Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 , Si (OC 3 H 7 ) 4 , Si (OC 4 H 9 ) 4 are available at a low price.
  • the coating layer of the metal oxide obtained therefrom is particularly preferable because of its excellent developer resistance.
  • the method for producing a lithographic printing plate according to the present disclosure includes an exposure process for image exposure of the lithographic printing plate precursor and a development process for developing using a developer in this order.
  • the developer is preferably a developer having a pH of 10 or less from the viewpoint of developability and ease of waste liquid treatment.
  • the method for producing a lithographic printing plate according to the present disclosure includes an exposure step of performing image exposure on the lithographic printing plate precursor according to the present disclosure.
  • a light source having an emission wavelength from the near infrared to the infrared region is preferable, and a solid laser or a semiconductor laser is more preferable.
  • the laser output is preferably 100 mW or more, and a multi-beam laser device is preferably used in order to shorten the exposure time.
  • the exposure time per pixel is preferably within 20 ⁇ sec.
  • the energy applied to the lithographic printing plate precursor is preferably 10 mJ / cm 2 to 300 mJ / cm 2 . When it is in the above range, curing can proceed sufficiently, laser ablation can be suppressed, and damage to the image can be prevented.
  • the exposure in the present disclosure can be performed by overlapping the light beams of the light sources.
  • Overlap means that the sub-scanning pitch width is smaller than the beam diameter.
  • the overlap can be expressed quantitatively by FWHM / sub-scanning pitch width (overlap coefficient), for example, when the beam diameter is expressed by the full width at half maximum (FWHM) of the beam intensity.
  • the overlap coefficient is preferably 0.1 or more.
  • the light source scanning method of the exposure apparatus that can be used in the present disclosure is not particularly limited, and a cylindrical outer surface scanning method, a cylindrical inner surface scanning method, a planar scanning method, and the like can be used.
  • the channel of the light source may be a single channel or a multi-channel, but in the case of a cylindrical outer surface system, a multi-channel is preferably used.
  • the method for producing a lithographic printing plate according to the present disclosure includes a development step of developing using a developer.
  • the developer used in the development step is preferably an aqueous solution having a pH of 10 or less, more preferably an aqueous solution having a pH of 2 to 9.
  • the developer preferably contains a surfactant from the viewpoint of processability.
  • any of anionic, nonionic, cationic and amphoteric surfactants can be used.
  • anionic and nonionic surfactants are used. Agents are preferred.
  • the anionic, nonionic, cationic, and amphoteric surfactants used in the developer in the present disclosure those described in paragraphs 0128 to 0131 of JP2013-134341A can be used.
  • the HLB value of the surfactant is preferably 6 or more, and more preferably 8 or more.
  • anionic surfactants and nonionic surfactants are preferable, anionic surfactants containing sulfonic acid or sulfonates, and nonions having aromatic rings and ethylene oxide chains. Surfactants are particularly preferred. Surfactants can be used alone or in combination.
  • the content of the surfactant in the developer is preferably 0.01% by mass to 10% by mass, and more preferably 0.01% by mass to 5% by mass.
  • carbonate and hydrogen carbonate may be added to the developer, or by adjusting the pH after adding carbonate or bicarbonate, Ions and bicarbonate ions may be generated.
  • the carbonate and bicarbonate are not particularly limited, but are preferably alkali metal salts. Examples of the alkali metal include lithium, sodium, and potassium, and sodium is particularly preferable. These may be used alone or in combination of two or more.
  • the total amount of carbonate and bicarbonate is preferably 0.3% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass with respect to the total mass of the developer, and 1% by mass to 5% by mass. % Is particularly preferred.
  • the total amount is 0.3% by mass or more, developability and processing capacity do not deteriorate, and when it is 20% by mass or less, it becomes difficult to form precipitates and crystals. It becomes difficult to gel and does not interfere with waste liquid treatment.
  • another alkali agent such as an organic alkali agent may be supplementarily used together.
  • the organic alkaline agent include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, Examples thereof include diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, tetramethylammonium hydroxide and the like.
  • the developer may contain a wetting agent, preservative, chelate compound, antifoaming agent, organic acid, organic solvent, inorganic acid, inorganic salt, and the like.
  • a wetting agent preservative, chelate compound, antifoaming agent, organic acid, organic solvent, inorganic acid, inorganic salt, and the like.
  • the wetting agent described in paragraph 0141 of JP2013-134341A can be suitably used.
  • the wetting agent may be used alone or in combination of two or more.
  • the wetting agent is preferably used in an amount of 0.1% by mass to 5% by mass with respect to the total mass of the developer.
  • the preservative described in paragraph 0142 of JP2013-134341A can be suitably used. It is preferable to use two or more kinds of preservatives in combination so as to be effective against various molds and sterilization.
  • the addition amount of the preservative is an amount that exhibits a stable effect on bacteria, fungi, yeast, etc., and varies depending on the type of bacteria, fungi, yeast, etc., but is 0 with respect to the total mass of the developer. A range of 0.01% to 4% by mass is preferable.
  • a chelate compound described in paragraph 0143 of JP2013-134341A can be suitably used.
  • a chelating agent is selected that is stably present in the developer composition and does not impair the printability.
  • the addition amount is preferably 0.001% by mass to 1.0% by mass with respect to the total mass of the developer.
  • the antifoaming agent described in paragraph 0144 of JP2013-134341A can be suitably used.
  • the content of the antifoaming agent is preferably in the range of 0.001% by mass to 1.0% by mass with respect to the total weight of the developer.
  • an antifoaming agent described in paragraph 0145 of JP2013-134341A can be suitably used.
  • the content of the organic acid is preferably 0.01% by mass to 0.5% by mass with respect to the total mass of the developer.
  • organic solvent examples include aliphatic hydrocarbons (hexane, heptane, “Isopar E, H, G” (Esso Chemical Co., Ltd.), gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, Xylene, etc.), halogenated hydrocarbons (methylene dichloride, ethylene dichloride, trichlene, monochlorobenzene, etc.) and polar solvents.
  • aliphatic hydrocarbons hexane, heptane, “Isopar E, H, G” (Esso Chemical Co., Ltd.)
  • gasoline kerosene, etc.
  • aromatic hydrocarbons toluene, Xylene, etc.
  • halogenated hydrocarbons methylene dichloride, ethylene dichloride, trichlene, monochlorobenzene, etc.
  • polar solvents examples include polar solvents.
  • Polar solvents include alcohols (methanol, ethanol, propanol, isopropanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, etc.), ketones (methyl ethyl ketone, cyclohexanone, etc.), esters (ethyl acetate, methyl lactate, propylene) Glycol monomethyl ether acetate, etc.) and others (triethyl phosphate, tricresyl phosphate, N-phenylethanolamine, N-phenyldiethanolamine, etc.).
  • the organic solvent when it is insoluble in water, it can be used after being solubilized in water using a surfactant or the like.
  • the concentration of the solvent is preferably less than 40% by mass from the viewpoint of safety and flammability.
  • inorganic acids and inorganic salts include phosphoric acid, metaphosphoric acid, primary ammonium phosphate, secondary ammonium phosphate, primary sodium phosphate, secondary sodium phosphate, primary potassium phosphate, secondary potassium phosphate, Examples include sodium tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, magnesium nitrate, sodium nitrate, potassium nitrate, ammonium nitrate, sodium sulfate, potassium sulfate, ammonium sulfate, sodium sulfite, ammonium sulfite, sodium hydrogen sulfate, nickel sulfate and the like.
  • the content of the inorganic salt is preferably 0.01% by mass to 0.5% by mass with respect to the total mass of the developer.
  • the development temperature is not particularly limited as long as development is possible, but it is preferably 60 ° C. or lower, more preferably 15 ° C. to 40 ° C.
  • the developing solution may be fatigued depending on the processing amount. Therefore, the processing capability may be restored using a replenishing solution or a fresh developing solution.
  • An example of development and post-development processing is a method in which alkali development is performed, alkali is removed in a post-water washing step, gumming is performed in a gumming step, and drying is performed in a drying step.
  • a method in which pre-water washing, development and gumming are simultaneously performed by using an aqueous solution containing carbonate ions, hydrogen carbonate ions and a surfactant can be preferably exemplified. Therefore, the pre-water washing step is not particularly required, and it is preferable to perform the drying step after performing pre-water washing, development and gumming in one bath only by using one liquid. After development, it is preferable to dry after removing excess developer using a squeeze roller or the like.
  • the developing process can be preferably carried out by an automatic processor equipped with a rubbing member.
  • an automatic processor for example, an automatic processor described in JP-A-2-220061 and JP-A-60-59351, which performs rubbing while conveying a lithographic printing plate precursor after image exposure,
  • an automatic processor using a rotating brush roll as the rubbing member is particularly preferable.
  • the rotating brush roll used in the present disclosure can be appropriately selected in consideration of the difficulty of scratching the image area and the strength of the waist of the lithographic printing plate precursor.
  • a known one formed by planting a brush material on a plastic or metal roll can be used.
  • metal or plastic in which brush materials are implanted in rows can be used.
  • a brush roll in which the groove mold material is radially wound around a plastic or metal roll as a core without any gap can be used.
  • brush materials include plastic fibers (for example, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as nylon 6.6 and nylon 6.10, polyacrylics such as polyacrylonitrile and poly (meth) acrylate).
  • plastic fibers for example, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as nylon 6.6 and nylon 6.10, polyacrylics such as polyacrylonitrile and poly (meth) acrylate.
  • Polyolefin-based synthetic fibers such as polypropylene and polystyrene
  • the outer diameter of the rotating brush roll is preferably 30 mm to 200 mm, and the peripheral speed at the tip of the brush rubbing the plate surface is preferably 0.1 m / sec to 5 m / sec. It is preferable to use a plurality of rotating brush rolls.
  • the rotating direction of the rotating brush roll may be the same or opposite to the conveying direction of the lithographic printing plate precursor. However, when two or more rotating brush rolls are used, at least one rotating brush roll is used. It is preferred that the rotating brush rolls rotate in the same direction and at least one rotating brush roll rotates in the opposite direction. This further ensures the removal of the image recording layer in the non-image area. It is also effective to swing the rotating brush roll in the direction of the rotation axis of the brush roll.
  • a drying step continuously or discontinuously after the development step. Drying is performed by hot air, infrared rays, far infrared rays, or the like.
  • an automatic processor suitably used in the method for preparing a lithographic printing plate according to the present disclosure, an apparatus having a developing unit and a drying unit is used, and the lithographic printing plate precursor is developed and gummed in a developing tank. And then dried in a drying section to obtain a lithographic printing plate.
  • the developed printing plate can be heated under very strong conditions.
  • the heating temperature is preferably in the range of 200 ° C to 500 ° C.
  • the lithographic printing plate obtained in this way is applied to an offset printing machine and is suitably used for printing a large number of sheets.
  • the molecular weight is a weight average molecular weight (Mw) except for those specifically defined.
  • Mw is the value measured as a polystyrene conversion value by a gel permeation chromatography (GPC) method.
  • GPC gel permeation chromatography
  • the unit of the acid value described later is meq / g.
  • the column “Structure in Formula A1 to Formula A3” includes A, R 4 and Z in the corresponding formula in the structural unit represented by any of Formula A1 to Formula A3, respectively.
  • the structure corresponding to is described.
  • “Ph” represents a benzene ring
  • “naph” represents a naphthalene ring
  • “pyr” represents a pyridine ring.
  • “acid value of specific binder polymer” “acid value by acid group of pKa 9 or less” measured by the above-described method is described.
  • ⁇ Development evaluation> The obtained lithographic printing plate precursor was drawn into a test pattern in the form of an image by changing the exposure energy with a Trendsetter VX manufactured by Creo. Thereafter, the film was immersed in a developing bath charged with the developer 1, and the time required for developing the non-image area at a developing temperature of 30 ° C. was measured.
  • the immersion time when the image density measured by the Macbeth densitometer was equivalent to the image density of the support was defined as the non-image area development time. The shorter the non-image area development time, the better the developability.
  • the non-image area development time (seconds) is shown in Table 3.
  • the obtained lithographic printing plate precursor was drawn into a test pattern in an image with a Trend setter manufactured by Creo at a beam intensity of 9 W and a drum rotation speed of 150 rpm. Thereafter, using a PS processor LP940H manufactured by Fuji Film Co., Ltd., in which developer 1 was charged, development temperature 30 ° C., development time: under the conditions of the above-mentioned non-image part development time (seconds) +2 seconds in each example or comparative example Developed. This was continuously printed using a printer Lithron manufactured by Komori Corporation. As the ink, Toyo Ink Co., Ltd. special training ink was used.
  • a transparent polyethylene terephthalate film (manufactured by Fuji Film Co., Ltd.) having a thickness of 0.1 mm was brought into close contact with the surface of the lithographic printing plate precursor, and the entire surface was exposed under the same conditions as in the evaluation of developability. After the exposure, the polyethylene terephthalate film was removed and visually observed, and the surface contamination was observed.
  • the case where dirt was not recognized was judged as A
  • the case where dirt was slightly recognized was judged as B
  • the case where dirt was stained to the extent that it could not be seen through the film was judged as C. It can be said that the smaller the dirt, the better the ablation suppression property, and the evaluation is preferably A or B, more preferably A.
  • the polymers of Comparative 1 to Comparative 4 described in the specific binder polymer column are polymers synthesized by the same method as that of the specific binder polymer 1 using the monomers shown in Table 4 below.
  • Example 42 to 46 and Comparative Examples 5 to 8) ⁇ Formation of image recording layer comprising lower layer and upper layer>
  • a coating liquid composition B for forming a lower layer having the following composition was applied to a support provided with an undercoat layer obtained in Example 1 with a wire bar, and then dried in a drying oven at 150 ° C. for 40 seconds. 1.0 g / m 2 and a lower layer was provided.
  • the upper layer forming coating liquid composition C having the following composition was applied with a wire bar to provide the upper layer.
  • drying was performed at 150 ° C. for 40 seconds to obtain a lithographic printing plate precursor having a total coating amount of 1.2 g / m 2 for the lower layer and the upper layer.
  • Tetrahydrophthalic acid 0.4 parts p-Toluenesulfonic acid: 0.02 parts 3-methoxy-4-diazodiphenylamine hexafluorophosphate 0.06 parts -The counter ion of ethyl violet is changed to 6-hydroxynaphthalenesulfonic acid: 0.15 parts
  • -Coating liquid composition C for upper layer formation Specific binder polymer: compounds described in Table 5 to Table 7, amounts described in Table 5 to Table 7.
  • Example 42 and Comparative Example 5 evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 5.
  • Example 43 to 44 and Comparative Examples 6 to 7 evaluation was made in the same manner as in Example 1 except that the following developer 2 was used instead of developer 1. The evaluation results are shown in Table 6.
  • Example 45 and Comparative Example 8 evaluation was performed in the same manner as in Example 1 except that the following developer 3 was used instead of developer 1. Table 7 shows the evaluation results.
  • Example 46 the IR dye (1) in the coating liquid composition B for forming the lower layer and the coating liquid composition C for forming the upper layer is changed to the following IR dye (2). Evaluation was performed in the same manner as in Example 1 except that 3 was used. Table 7 shows the evaluation results.
  • the planographic printing plate precursor according to the present disclosure provides a planographic printing plate excellent in developability at low pH. It can also be seen that the lithographic printing plate precursor according to the present disclosure provides a lithographic printing plate that is excellent in printing durability, ink deposition, and ablation suppression. Furthermore, it can be seen that the lithographic printing plate precursor according to the present disclosure is also excellent in scratch resistance.

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Abstract

L'invention concerne une plaque originale de plaque d'impression lithographique de type positif, et un procédé de fabrication de plaque d'impression lithographique mettant en œuvre ladite plaque originale de plaque d'impression lithographique de type positif. La plaque originale de plaque d'impression lithographique de type positif de l'invention possède un corps de support et une couche d'enregistrement d'image formée sur ce support. Ladite couche d'enregistrement d'image comprend au moins une sorte d'unité structurale choisie dans un groupe constitué d'une unité structurale représentée par la formule (A1), d'une unité structurale représentée par la formule (A2) et d'une unité structurale représentée par la formule (A3). Enfin, la plaque originale de plaque d'impression lithographique de type positif de l'invention contient un polymère de liaison présentant un indice d'acide compris entre ２ｍｅｑ／ｇ et ４ｍｅｑ／ｇ sous l'effet d'un groupe acide de valeur pKa inférieure ou égale à 9, et un agent d'absorption dans l'infrarouge.
PCT/JP2019/007387 2018-02-28 2019-02-26 Plaque originale de plaque d'impression lithographique de type positif, et procédé de fabrication de plaque d'impression lithographique WO2019167967A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000035663A (ja) * 1998-07-21 2000-02-02 Konica Corp 感光性組成物及び感光性平版印刷版
JP2001215693A (ja) * 2000-02-01 2001-08-10 Konica Corp 画像形成材料及びその製造方法
JP2006153980A (ja) * 2004-11-25 2006-06-15 Fuji Photo Film Co Ltd 平版印刷版原版
JP2007321104A (ja) * 2006-06-02 2007-12-13 Okamoto Kagaku Kogyo Kk 平版印刷版用原版

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000035663A (ja) * 1998-07-21 2000-02-02 Konica Corp 感光性組成物及び感光性平版印刷版
JP2001215693A (ja) * 2000-02-01 2001-08-10 Konica Corp 画像形成材料及びその製造方法
JP2006153980A (ja) * 2004-11-25 2006-06-15 Fuji Photo Film Co Ltd 平版印刷版原版
JP2007321104A (ja) * 2006-06-02 2007-12-13 Okamoto Kagaku Kogyo Kk 平版印刷版用原版

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