WO2019167967A1 - Positive lithographic printing plate precursor and method for manufacturing lithographic printing plate - Google Patents

Positive lithographic printing plate precursor and method for manufacturing lithographic printing plate 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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Prior art keywords
group
printing plate
acid
formula
plate precursor
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Application number
PCT/JP2019/007387
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French (fr)
Japanese (ja)
Inventor
一郎 小山
尚志 佐藤
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富士フイルム株式会社
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Publication of WO2019167967A1 publication Critical patent/WO2019167967A1/en

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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

Provided is a positive lithographic printing plate precursor comprising a support and an image-recording layer formed on the support. The image-recording layer comprises an infrared absorber and a binder polymer that contains at least one constituent unit selected from the group consisting of constituent units represented by formula A1, constituent units represented by formula A2, and constituent units represented by formula A3, and has an acid value attributable to acid groups with a pKa of 9 or less of 2 meq/g to 4 meq/g. Also provided is a method for manufacturing a lithographic printing plate using the positive lithographic printing plate precursor.

Description

ポジ型平版印刷版原版、及び、平版印刷版の作製方法Positive lithographic printing plate precursor and method for preparing lithographic printing plate
　本開示は、ポジ型平版印刷版原版、及び、平版印刷版の作製方法に関する。 The present disclosure relates to a positive planographic printing plate precursor and a method for producing a planographic printing plate.
　従来、種々の感光性組成物が可視画像形成材料や平版印刷版材料として使用されている。特に、平版印刷分野における近年におけるレーザーの発展は目ざましく、特に近赤外から赤外に発光領域を持つ固体レーザー又は半導体レーザーは、高出力、かつ、小型の物が容易に入手できるようになっている。平版印刷の分野においては、コンピュータ等のディジタルデータから直接製版する際の露光光源として、これらのレーザーは非常に有用である。
　赤外線レーザー用ポジ型平版印刷版原版は、アルカリ可溶性のバインダー樹脂と、光を吸収し熱を発生する赤外線吸収剤（例えば、赤外吸収染料（ＩＲ染料））等とを必須成分とする。このＩＲ染料等が、未露光部（画像部）では、バインダー樹脂との相互作用によりバインダー樹脂の現像液に対する溶解性を実質的に低下させる現像抑制剤として働き、露光部（非画像部）では、発生した熱によりＩＲ染料等とバインダー樹脂との相互作用が弱まり、アルカリ現像液に溶解して平版印刷版を形成する。
　従来の平版印刷版の製造に用いられる組成物、平版印刷版原版又はポジ型画像形成要素を提供する方法としては、特許文献１～３に記載のものが知られている。 Conventionally, various photosensitive compositions have been used as visible image forming materials and lithographic printing plate materials. In particular, the development of lasers in the field of lithographic printing has been remarkable in recent years. Particularly, solid lasers or semiconductor lasers having a light emitting region from the near infrared to the infrared can be easily obtained as high-power and small-sized ones. ing. In the field of lithographic printing, these lasers are very useful as an exposure light source for making a plate directly from digital data such as a computer.
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. 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.
As a method for providing a composition, 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.
　特許文献１には、親水性表面を有する支持体上に、赤外線吸収剤及びバインダーポリマーを含む、熱及び／又は光感受性の画像記録層が形成されており、上記画像記録層がサリチル酸基を含む構成単位、及び、スルホンアミド基を含む構成単位を有する平版印刷版原版が記載されている。 In 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.
　特許文献２には、（Ａ）下記一般式（１）で表される構造単位を有するポリマーを含有する樹脂組成物が記載されている。 Patent Document 2 describes (A) a resin composition containing a polymer having a structural unit represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　一般式（１）中、Ｘは４価の連結基を表す。ｎは６～４０の整数を表す。 In general formula (1), X represents a tetravalent linking group. n represents an integer of 6 to 40.
　特許文献３には、
　Ａ）　基板上に第１層を用意する工程、上記第１層は、第１高分子バインダー内に分散された第１輻射線吸収化合物を含む、
　Ｂ）　上記第１層上に第２層を用意する工程、上記第２層は、第２高分子バインダー内に分散された第２輻射線吸収化合物を含む、
　Ｃ）　上記第１層及び第２層を乾燥させた後、上記乾燥された第１層及び第２層からの湿分の除去を抑制する条件下で少なくとも４時間、約４０℃～約９０℃で、上記第１層及び第２層を熱処理する工程
　を含んで成るポジ型画像形成性要素を提供する方法が記載されている。 In 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.
　　特許文献１：国際公開第２０１２／１１０３５９号
　　特許文献２：特開２００４－３２５５０８号公報
　　特許文献３：特表２００９－５２８５６８号公報 Patent Document 1: International Publication No. 2012/110359 Patent Document 2: JP 2004-325508 A Patent Document 3: JP-T 2009-528568
　従来の平版印刷版原版において、ｐＨの低い現像液（例えば、ｐＨ１０以下の現像液など）を用いた場合であっても現像が可能であるという性質（「低ｐＨにおける現像性」ともいう。）が求められていた。
　本発明者らは、鋭意検討した結果、特許文献１に記載の組成物を用いた平版印刷版原版、特許文献２に記載の平版印刷版原版、又は、特許文献３に記載のポジ型画像形成要素を含む平版印刷版原版においては、低ｐＨにおける現像性に改良の余地があることを見出した。 In a conventional lithographic printing plate precursor, 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) is used (also referred to as “developability at low pH”). Was demanded.
As a result of intensive studies, 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.
　本開示の実施形態が解決しようとする課題は、低ｐＨにおける現像性に優れたポジ型平版印刷版原版、及び、上記ポジ型平版印刷版原版を用いた平版印刷版の作製方法を提供することである。 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.
　上記課題を解決するための手段には、以下の態様が含まれる。
＜１＞　支持体と、
　支持体上に形成された画像記録層と、を有し、
　上記画像記録層が、
　下記式Ａ１により表される構成単位、下記式Ａ２により表される構成単位、及び下記式Ａ３により表される構成単位よりなる群から選ばれた少なくとも１種の構成単位を有し、ｐＫａ９以下の酸基による酸価が２ｍｅｑ／ｇ～４ｍｅｑ／ｇであるバインダーポリマー、及び、赤外線吸収剤を含む、
　ポジ型平版印刷版原版。 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.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式Ａ１中、ＬＡは－Ｃ（＝Ｏ）Ｏ－、－Ｃ（＝Ｏ）ＮＲ５－、又はフェニル基を表し、Ｒ５は水素原子又はアルキル基を表し、ＲＡは式Ｂ１により表される基を表し、Ｒ１は水素原子又はアルキル基を表す。
　式Ａ２中、ＲＡは式Ｂ１により表される基を表し、Ｒ２及びＲ３はそれぞれ独立に、水素原子又はアルキル基を表す。
　式Ａ３中、ＲＡは式Ｂ１により表される基を表す。
　式Ｂ１中、Ｌ１は単結合又は二価の連結基を表し、Ｘ１は単結合、エステル結合、アミド結合、ウレタン結合又はウレア結合を表し、Ａは芳香環構造を表し、Ｚはそれぞれ独立に、ｐＫａ９以下の酸基を表し、ｎは１以上の整数を表し、Ｒ４はそれぞれ独立に、－ＯＲ６、アルキル基、ハロゲン原子、－Ｃ（＝Ｏ）Ｒ７、－Ｃ（＝Ｏ）ＯＲ７又はニトロ基を表し、Ｒ６は水素原子又は炭素数１～４のアルキル基を表し、Ｒ７は炭素数１～４のアルキル基を表し、ｍは０以上の整数を表し、ｍ＋ｎはＡにより表される芳香環構造の最大置換基数以下の数を表し、Ａがベンゼン環構造である場合、ｍは１～４の整数であり、＊は他の構造との結合部位を表す。 In Formula A1, L A represents —C (═O) O—, —C (═O) NR 5 —, or a phenyl group, R 5 represents a hydrogen atom or an alkyl group, and R A represents a group represented by Formula B1. R 1 represents a hydrogen atom or an alkyl group.
In Formula A2, R A represents a group represented by Formula B1, and R 2 and R 3 each independently represent a hydrogen atom or an alkyl group.
In Formula A3, R A represents a group represented by Formula B1.
In 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, and Z is independent. Represents an acid group having a pKa of 9 or less, n represents an integer of 1 or more, and R 4 independently represents —OR 6 , an alkyl group, a halogen atom, —C (═O) R 7 , —C (═O ) Represents OR 7 or a nitro group, R 6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 7 represents an alkyl group having 1 to 4 carbon atoms, m represents an integer of 0 or more, and m + n Represents a number equal to or less than the maximum number of substituents of the aromatic ring structure represented by A. When A is a benzene ring structure, m is an integer of 1 to 4, and * represents a binding site with another structure.
＜２＞　上記Ｚにより表される酸基がカルボキシ基又はヒドロキシ基である、上記＜１＞に記載のポジ型平版印刷版原版。
＜３＞　上記Ａにより表される芳香環構造が、ベンゼン環構造、ナフタレン環構造又はピリジン環構造である、上記＜１＞又は＜２＞に記載のポジ型平版印刷版原版。
＜４＞　上記Ａにより表される芳香環構造が、ナフタレン環構造又はピリジン環構造であり、上記ｍが０である、上記＜１＞～＜３＞のいずれか１つに記載のポジ型平版印刷版原版。
＜５＞　上記Ａにより表される芳香環構造が、ベンゼン環構造であり、上記ｍが１である、上記＜１＞～＜３＞のいずれか１つに記載のポジ型平版印刷版原版。
＜６＞　上記Ｚにより表される酸基のｐＫａが２．５～７．５である、上記＜１＞～＜５＞のいずれか１つに記載のポジ型平版印刷版原版。
＜７＞　上記バインダーポリマーの重量平均分子量が８，０００～２０，０００である、上記＜１＞～＜６＞のいずれか１つに記載のポジ型平版印刷版原版。
＜８＞　上記画像記録層が、その他のバインダーポリマーとして、フェノール樹脂、スチレン－アクリロニトリル樹脂、アクリル樹脂、アセタール樹脂、及び、ウレア結合、ウレタン結合又はアミド結合を主鎖に有する樹脂よりなる群から選ばれた少なくとも１種を更に含む、上記＜１＞～＜７＞のいずれか１つに記載のポジ型平版印刷版原版。
＜９＞　上記画像記録層が、下層と上層とを有し、
　上記バインダーポリマーを含む上記画像記録層が、少なくとも上記下層及び上記上層のいずれかである、上記＜１＞～＜８＞のいずれか１つに記載のポジ型平版印刷版原版。
＜１０＞　上記＜１＞～＜９＞のいずれか１つに記載のポジ型平版印刷版原版を画像露光する露光工程、及び、
　露光された上記ポジ型平版印刷版原版をｐＨ１０．０以下の現像液を用いて現像する現像工程、をこの順で含む
　平版印刷版の作製方法。 <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.
<8> 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 positive lithographic printing plate precursor as described in any one of <1> to <7> above, further comprising at least one selected from the above.
<9> 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.
<10> 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.
　本開示の実施形態によれば、低ｐＨにおける現像性に優れたポジ型平版印刷版原版、及び、上記ポジ型平版印刷版原版を用いた平版印刷版の作製方法を提供することができる。 According to the embodiment of the present disclosure, it is possible to provide a positive planographic printing plate precursor excellent in developability at a low pH and a method for producing a planographic printing plate using the positive planographic printing plate precursor.
　以下において、本開示の内容について詳細に説明する。以下に記載する構成要件の説明は、本開示の代表的な実施態様に基づいてなされることがあるが、本開示はそのような実施態様に限定されるものではない。
　なお、本開示において、数値範囲を示す「～」とはその前後に記載される数値を下限値及び上限値として含む意味で使用される。
　本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
　更に、本開示において組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する該当する複数の物質の合計量を意味する。
　また、本開示における基（原子団）の表記において、置換及び無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　本開示において、「（メタ）アクリル」は、アクリル及びメタクリルの両方を包含する概念で用いられる語であり、「（メタ）アクリロイル」は、アクリロイル及びメタクリロイルの両方を包含する概念として用いられる語である。
　本開示において、Ｍｅはメチル基を、Ｅｔはエチル基を、Ｂｕはブチル基をそれぞれ表す
　また、本開示において、式で表される化合物における基の表記に関して、置換又は無置換を記していない場合、その基がさらに置換基を有することが可能な場合には、他に特に規定がない限り、その基は、無置換の基のみならず、置換基を有する基も包含する。例えば、式において、「Ｒはアルキル基、アリール基又は複素環基を表す」との記載があれば、「Ｒは無置換アルキル基、置換アルキル基、無置換アリール基、置換アリール基、無置換複素環基又は置換複素環基を表す」ことを意味する。
　また、本開示中の「工程」の用語は、独立した工程だけではなく、他の工程と明確に区別できない場合であっても、その工程の所期の目的が達成されれば本用語に含まれる。
　また、本開示において、「質量％」と「重量％」とは同義であり、「質量部」と「重量部」とは同義である。
　更に、本開示において、２以上の好ましい態様の組み合わせは、より好ましい態様である。
　また、本開示における重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、特に断りのない限り、ＴＳＫｇｅｌ　ＧＭＨｘＬ、ＴＳＫｇｅｌ　Ｇ４０００ＨｘＬ、ＴＳＫｇｅｌ　Ｇ２０００ＨｘＬ（何れも東ソー（株）製の商品名）のカラムを使用したゲルパーミエーションクロマトグラフィー（ＧＰＣ）分析装置により、溶媒ＴＨＦ（テトラヒドロフラン）、示差屈折計により検出し、標準物質としてポリスチレンを用いて換算した分子量である。
　本開示において、全固形分量とは、組成物における溶剤等の揮発性成分を除いた成分の全質量をいう。
　本開示において、「平版印刷版原版」の用語は、平版印刷版原版だけでなく、捨て版原版を包含する。また、「平版印刷版」の用語は、平版印刷版原版を、必要により、露光、現像などの操作を経て作製された平版印刷版だけでなく、捨て版を包含する。捨て版原版の場合には、必ずしも、露光、現像の操作は必要ない。なお、捨て版とは、例えばカラーの新聞印刷において一部の紙面を単色又は２色で印刷を行う場合に、使用しない版胴に取り付けるための平版印刷版原版である。
　以下、本開示を詳細に説明する。 Hereinafter, the contents of the present disclosure will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.
In the present disclosure, “to” indicating a numerical range is used in a sense including numerical values described before and after the numerical value as a lower limit value and an upper limit value.
In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical description. . Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
Furthermore, in the present disclosure, 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.
In addition, in the notation of groups (atomic groups) in the present disclosure, the notation that does not indicate substitution and non-substitution includes those not having a substituent and those having a substituent. For example, 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).
In the present disclosure, “(meth) acryl” is a term used in a concept including both acryl and methacryl, and “(meth) acryloyl” is a term used as a concept including both acryloyl and methacryloyl. is there.
In the present disclosure, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group. Also, in the present disclosure, regarding the notation of the group in the compound represented by the formula, no substitution or no substitution is described. When 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. For example, in the formula, if there is a description that “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” Represents a heterocyclic group or a substituted heterocyclic group.
In addition, the term “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.
In the present disclosure, “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.
In addition, the 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 molecular weight was detected by a gel permeation chromatography (GPC) analyzer using a solvent THF (tetrahydrofuran) and a differential refractometer and converted using polystyrene as a standard substance.
In the present disclosure, the total solid content means the total mass of components excluding volatile components such as a solvent in the composition.
In the present disclosure, 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.
Hereinafter, the present disclosure will be described in detail.
（ポジ型平版印刷版原版）
　本開示に係るポジ型平版印刷版原版（以下、単に「平版印刷版原版」ともいう。）は、支持体と、支持体上に形成された画像記録層と、を有し、上記画像記録層が、下記式Ａ１により表される構成単位、下記式Ａ２により表される構成単位、及び下記式Ａ３により表される構成単位よりなる群から選ばれた少なくとも１種の構成単位を有し、ｐＫａ９以下の酸基による酸価が２ｍｅｑ／ｇ～４ｍｅｑ／ｇであるバインダーポリマー（以下、「特定バインダーポリマー」ともいう。）、及び、赤外線吸収剤を含む。 (Positive planographic printing plate precursor)
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. 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, and pKa9 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.
　本発明者らは、鋭意検討した結果、本開示に係るポジ型平版印刷版原版は、低ｐＨにおける現像性に優れることを見出した。
　上記効果が得られる理由は定かではないが、下記のように推測される。
　本開示に係る平版印刷版原版は、画像記録層中に特定バインダーポリマーを含有する。この特定バインダーポリマーにおける、ｐＫａ９以下の酸基による酸価が２ｍｅｑ／ｇ～４ｍｅｑ／ｇであることにより、低ｐＨにおける現像性に優れた平版印刷版原版が得られると考えられる。
　また、特定バインダーポリマーは、式Ａ１～式Ａ３のいずれかにより表される構成単位を含むが、これらの構成単位中、式Ｂ１により表される構造において、Ａが多環式芳香環構造であるか、ヘテロ芳香環構造であるか、又は、Ａがベンゼン環構造であり、かつ、置換基であるＲ４を有していることにより、Ｚで表される酸基が現像液で中和された際にＡで表される芳香環構造の凝集性が低下しやすく、バインダーポリマーの分散性が向上しやすいため、低ｐＨにおける現像性に優れると考えられる。
　更に、特定バインダーポリマーにおける上記Ｒ４が特定の構造であることにより、特定バインダーポリマーと赤外線吸収剤との相互作用が強いため、画像部と非画像部の溶解性の差が大きくなりやすく、低ｐＨにおける現像性に優れると考えられる。 As a result of intensive studies, the present inventors have found that the positive planographic printing plate precursor according to the present disclosure is excellent in developability at a low pH.
The reason why the above effect is obtained is not clear, but is estimated as follows.
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.
Further, 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.
Further, since the above R 4 in the specific binder polymer has a specific structure, the interaction between the specific binder polymer and the infrared absorber is strong, so that the difference in solubility between the image portion and the non-image portion is likely to increase, It is considered that the developability at pH is excellent.
　このように、低ｐＨにおける現像性に優れたポジ型平版印刷版原版を使用することにより、現像に低ｐＨの現像液を使用することが可能となるという利点がある。
　具体的には、例えば、ｐＨ１０．０以下の現像液を用いることが可能となる。この、ｐＨ１０．０以下の現像液は、例えば大気中の炭酸化合物等により中和されにくいため保存安定性に優れる、廃液の処理が容易である、等の利点を有している。
　また、本開示に係るポジ型平版印刷版原版は、低ｐＨによる現像が可能であるため、疲労した現像液（既に現像に使用され、ｐＨが低下した現像液）を用いた場合であっても現像性が良好であると考えられる。すなわち、本開示に係るポジ型平版印刷版原版は、現像中の現像液の疲労に強いという性質を有していると考えられる。 Thus, by using a positive planographic printing plate precursor having excellent developability at low pH, there is an advantage that a low pH developer can be used for development.
Specifically, for example, 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.
Further, since 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.
　また、平版印刷版においては、版の印刷可能な枚数（以下、「耐刷性」ともいう。）に優れた平版印刷版が求められている。
　ここで、本発明者らは、本開示に係るポジ型平版印刷版原版によれば、耐刷性に優れた平版印刷版が得られやすいことを見出した。
　上記効果が得られる理由は定かではないが、特定バインダーポリマーが、式Ａ１～式Ａ３のいずれかにより表される構成単位を含むことにより、特定バインダーポリマーと赤外線吸収剤との相互作用が強いため、耐刷性に優れると推測される。
　更に、式Ａ１～式Ａ３のいずれかにより表される構成単位が、Ｘ１としてエステル結合、アミド結合、ウレタン結合又はウレア結合といった水素結合性の強い構造を含む場合には、更に耐刷性が向上しやすいと考えられる。 In addition, there is a demand for a lithographic printing plate excellent in the number of printable plates (hereinafter also referred to as “printing durability”).
Here, 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.
Furthermore, 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.
　また、本発明者らは、本開示に係るポジ型平版印刷版によれば、インキ着肉性に優れた平版印刷版原版が得られやすいことを見出した。
　本開示において、平版印刷版における印刷開始から、印刷部にインキが付着していない領域が存在しなくなるまでの時間が短いことを、インキ着肉性に優れるという。
　上記効果が得られる理由は定かではないが、特定バインダーポリマーに含まれるＺにより表される酸基は、画像記録層中で凝集して存在すると考えられる。そのため、例えば平版印刷版の表面を水拭きにより洗浄した後であっても、画像記録層表面が親水化しにくいため、インキ着肉性に優れると考えられる。 In addition, 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.
In 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 reason why the above effect is obtained is not clear, but it is considered that 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.
　加えて、本発明者らは、本開示に係るポジ型平版印刷版によれば、アブレーションの抑制性に優れた平版印刷版原版が得られやすいことを見出した。
　本開示において、平版印刷版原版の露光時に、加熱により画像記録層に含まれる成分が平版印刷版原版の外に飛散してしまう現象をアブレーションという。
　上記効果が得られる理由は定かではないが、特定バインダーポリマーに含まれるＺにより表される酸基は、上述の通り画像記録層中で凝集していると考えられ、画像記録層中での結束力が強いと考えられる。そのため、露光による加熱においても低分子成分等の被さんが抑制され、アブレーションの抑制性に優れると考えられる。
　以下、本開示に係る平版印刷版原版に含まれる各構成要件の詳細について説明する。 In addition, 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.
In the present disclosure, 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 reason why the above effect is obtained is not clear, but 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.
Hereinafter, details of each component included in the planographic printing plate precursor according to the present disclosure will be described.
＜画像記録層＞
〔特定バインダーポリマー〕
　本開示における画像記録層は、特定バインダーポリマーを含む。
　特定バインダーポリマーは、下記式Ａ１により表される構成単位、下記式Ａ２により表される構成単位、及び下記式Ａ３により表される構成単位よりなる群から選ばれた少なくとも１種の構成単位を有し、ｐＫａ９以下の酸基による酸価が２ｍｅｑ／ｇ～４ｍｅｑ／ｇであるバインダーポリマーである。 <Image recording layer>
[Specific binder polymer]
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. And a binder polymer having an acid value of 2 meq / g to 4 meq / g based on an acid group of pKa 9 or less.
Figure JPOXMLDOC01-appb-C000004
 
Figure JPOXMLDOC01-appb-C000004
 
　式Ａ１中、ＬＡは－Ｃ（＝Ｏ）Ｏ－、－Ｃ（＝Ｏ）ＮＲ５－、又はフェニル基を表し、Ｒ５は水素原子又はアルキル基を表し、ＲＡは式Ｂ１により表される基を表し、Ｒ１は水素原子又はアルキル基を表す。
　式Ａ２中、ＲＡは式Ｂ１により表される基を表し、Ｒ２及びＲ３はそれぞれ独立に、水素原子又はアルキル基を表す。
　式Ａ３中、ＲＡは式Ｂ１により表される基を表す。
　式Ｂ１中、Ｌ１は単結合又は二価の連結基を表し、Ｘ１は単結合、エステル結合、アミド結合、ウレタン結合又はウレア結合を表し、Ａは芳香環構造を表し、Ｚはそれぞれ独立に、ｐＫａ９以下の酸基を表し、ｎは１以上の整数を表し、Ｒ４はそれぞれ独立に、－ＯＲ６、アルキル基、ハロゲン原子、－Ｃ（＝Ｏ）Ｒ７、－Ｃ（＝Ｏ）ＯＲ７又はニトロ基を表し、Ｒ６は水素原子又は炭素数１～４のアルキル基を表し、Ｒ７は炭素数１～４のアルキル基を表し、ｍは０以上の整数を表し、ｍ＋ｎはＡにより表される芳香環構造の最大置換基数以下の数を表し、Ａがベンゼン環構造である場合、ｍは１～４の整数であり、＊は他の構造との結合部位を表す。 In Formula A1, L A represents —C (═O) O—, —C (═O) NR 5 —, or a phenyl group, R 5 represents a hydrogen atom or an alkyl group, and R A represents a group represented by Formula B1. R 1 represents a hydrogen atom or an alkyl group.
In Formula A2, R A represents a group represented by Formula B1, and R 2 and R 3 each independently represent a hydrogen atom or an alkyl group.
In Formula A3, R A represents a group represented by Formula B1.
In 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, and Z is independent. Represents an acid group having a pKa of 9 or less, n represents an integer of 1 or more, and R 4 independently represents —OR 6 , an alkyl group, a halogen atom, —C (═O) R 7 , —C (═O ) Represents OR 7 or a nitro group, R 6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 7 represents an alkyl group having 1 to 4 carbon atoms, m represents an integer of 0 or more, and m + n Represents a number equal to or less than the maximum number of substituents of the aromatic ring structure represented by A. When A is a benzene ring structure, m is an integer of 1 to 4, and * represents a binding site with another structure.
－式Ａ１により表される構成単位－
〔ＬＡ〕
　式Ａ１中、ＬＡは－Ｃ（＝Ｏ）Ｏ－、－Ｃ（＝Ｏ）ＮＲ５－、又はフェニル基を表し、－Ｃ（＝Ｏ）Ｏ－又は－Ｃ（＝Ｏ）ＮＲ５－が好ましい。
　ＬＡが－Ｃ（＝Ｏ）Ｏ－であると記載した場合、－Ｃ（＝Ｏ）Ｏ－の炭素原子側が式Ａ１中のＲ１が結合した炭素原子と、酸素原子側が式Ａ１中のＲＡとそれぞれ結合することを意味する。
　また、ＬＡが－Ｃ（＝Ｏ）ＮＲ５－であると記載した場合、－Ｃ（＝Ｏ）ＮＲ５－の炭素原子側が式Ａ１中のＲ１が結合した炭素原子と、窒素原子側が式Ａ１中のＲＡとそれぞれ結合することを意味する。
　式Ａ１中、Ｒ５は水素原子又はアルキル基を表し、水素原子又は炭素数１～４のアルキル基が好ましく、水素原子がより好ましい。
　式Ａ１中、Ｒ１は水素原子又はアルキル基を表し、水素原子又は炭素数１～４のアルキル基が好ましく、水素原子又はメチル基がより好ましく、水素原子が更に好ましい。 —Structural Unit Represented by Formula A1—
[L A]
In Formula A1, 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.
When 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.
Further, L A is -C (= O) NR 5 - when described as being, -C (= O) NR 5 - and the carbon atom to which the carbon atom side is bonded to R 1 in the formula A1, the nitrogen atom-side It means to bind to R A in formula A1.
In formula A1, 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.
In Formula A1, 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.
＜＜式Ｂ１により表される構造＞＞
　式Ａ１中、ＲＡは式Ｂ１により表される基を表す。 << Structure Represented by Formula B1 >>
In Formula A1, R A represents a group represented by Formula B1.
〔Ｌ１〕
　式Ｂ１中、Ｌ１は単結合又は二価の連結基を表し、単結合又はアルキレン基であることが好ましく、現像性の観点から、単結合又は炭素数２～４のアルキレン基がより好ましく、炭素数２のアルキレン基であることが更に好ましい。
　式Ｂ１中、Ｘ１が単結合である場合、Ｌ１も単結合であることが好ましい。
　式Ｂ１中、Ｘ１がエステル結合、アミド結合、ウレタン結合又はウレア結合である場合、Ｌ１はアルキレン基であることが好ましく、炭素数２～４のアルキレン基がより好ましく、炭素数２のアルキレン基であることが更に好ましい。 [L 1 ]
In 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.
In Formula B1, when X 1 is a single bond, L 1 is also preferably a single bond.
In Formula B1, when X 1 is an ester bond, an amide bond, a urethane bond or a urea 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.
〔Ｘ１〕
　式Ｂ１中、Ｘ１は単結合、エステル結合、アミド結合、ウレタン結合又はウレア結合を表し、単結合又はウレア結合であることが好ましく、耐刷性の観点からはウレア結合が更に好ましい。 [X 1 ]
In Formula B1, 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〕
　式Ｂ１中、Ａは芳香環構造を表し、芳香族炭化水素環構造及びヘテロ芳香環構造のいずれであってもよい。
　上記ヘテロ芳香環構造に含まれるヘテロ原子としては、窒素原子、酸素原子、及び、硫黄原子が挙げられるが、窒素原子が好ましい。
　Ａとしては、ベンゼン環構造、ナフタレン環構造、ピリジン環構造、ピリミジン環構造、ピラジン環構造又はピリダジン環構造が好ましく、ベンゼン環構造、ナフタレン環構造又はピリジン環構造がより好ましい。
　Ａは、現像性の観点からはベンゼン環構造が好ましく、耐刷性の観点からはナフタレン環構造又はピリジン環構造が好ましい。 [A]
In formula B1, A represents an aromatic ring structure, and may be either an aromatic hydrocarbon ring structure or a heteroaromatic ring structure.
Examples of 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.
〔Ｚ〕
　式Ｂ１中、Ｚはそれぞれ独立に、ｐＫａ９以下の酸基を表し、カルボキシ基、ヒドロキシ基、又は、スルホ基が好ましく、カルボキシ基又はヒドロキシ基がより好ましい。
　また、Ｚにより表される酸基のｐＫａは、耐刷性の観点から、２．５～７．５であることが好ましい。
　本開示において、酸基のｐＫａはＡＣＤ／ｐＫａ（ＡＣＤ／Ｌａｂｓ社製）のソフトウエアを用いて、式Ａ１～式Ａ２で表される構成単位の導入時に用いられたモノマーの構造式より算出される値である。また、モノマーの決定が困難である場合、又は、式Ａ３により表される構成単位における酸基のｐＫａを算出する場合には、式Ａ１～式Ａ３で表される構成単位において、構成単位の主鎖に結合する部分を水素原子に置き換えた構造から、上述のソフトウェアを用いて算出可能である。 [Z]
In Formula B1, 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.
In the present disclosure, 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. In addition, when it is difficult to determine the monomer, or when calculating the pKa of the acid group in the structural unit represented by the formula A3, the main structural unit in the structural units represented by the formulas A1 to A3. It can be calculated using the above-mentioned software from the structure in which the part bonded to the chain is replaced with a hydrogen atom.
〔ｎ〕
　式Ｂ１中、ｎは１以上の整数を表し、１又は２であることがより好ましく、１であることが更に好ましい。 [N]
In formula B1, n represents an integer of 1 or more, more preferably 1 or 2, and still more preferably 1.
〔Ｒ４〕
　Ｒ４はそれぞれ独立に、水素原子、－ＯＲ６、アルキル基、ハロゲン原子、－Ｃ（＝Ｏ）Ｒ７、－Ｃ（＝Ｏ）ＯＲ７又はニトロ基を表し、ヒドロキシ基、炭素数１～４のアルコキシ基、炭素数１～４のアルキル基、ハロゲン原子又はニトロ基が好ましく、ヒドロキシ基、メチル基、メトキシ基、フッ素原子、塩素原子又はニトロ基、がより好ましく、現像性の観点からは、ニトロ基が更に好ましい。
　Ｒ６は水素原子又は炭素数１～４のアルキル基を表し、水素原子又はメチル基がより好ましい。
　Ｒ７は炭素数１～４のアルキル基を表し、メチル基がより好ましい。
　Ｒ４は、Ａで表される芳香環構造において、Ｚが結合する原子と隣接する原子に結合することが好ましい。 [R 4 ]
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は０以上の整数を表し、Ａがナフタレン環構造又はヘテロ芳香環構造である場合、０又は１であることが好ましく、０であることがより好ましい。
　Ａがベンゼン環構造である場合、ｍは１～４の整数であり、１又は２であることが好ましく、１であることがより好ましい。
　ｎ＋ｍは、Ａにより表される芳香環構造の最大置換基数以下の数を表す。例えば、Ａがベンゼン環構造である場合、ｎ＋ｍは２～４の整数であり、Ａがナフタレン環構造である場合、ｎ＋ｍは１～７の整数であり、Ａがピリジン環構造である場合、ｎ＋ｍは０～４の整数である。 [M]
m represents an integer of 0 or more. When A is a naphthalene ring structure or a heteroaromatic ring structure, m is preferably 0 or 1, and more preferably 0.
When A is a benzene ring structure, m is an integer of 1 to 4, preferably 1 or 2, and more preferably 1.
n + m represents a number equal to or less than the maximum number of substituents of the aromatic ring structure represented by A. For example, when A is a benzene ring structure, n + m is an integer of 2 to 4, when A is a naphthalene ring structure, n + m is an integer of 1 to 7, and when A is a pyridine ring structure, n + m Is an integer from 0 to 4.
〔その他の置換基〕
　Ａにより表される芳香環構造は、上述のＺ及びＲ４以外の置換基を有していてもよい。
　上記置換基としては、例えば、アルケニル基、アルキニル基、アラルキル基、アリール基、ヘテロアリール基、アミノ基、－Ｃ（＝Ｏ）Ｎ（－Ｒ８）Ｒ９、－ＳＲ９、Ｓ（＝Ｏ）Ｒ９、Ｓ（＝Ｏ）２Ｒ９、チオール基、又は、ニトリル基が挙げられるが、これに限定されるものではない。Ｒ８は水素原子又は炭素数１～４のアルキル基を表し、Ｒ９は炭素数１～４のアルキル基を表す。 [Other substituents]
The aromatic ring structure represented by A may have a substituent other than Z and R 4 described above.
Examples of the substituent 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, and R 9 represents an alkyl group having 1 to 4 carbon atoms.
＜＜式Ａ１により表される構成単位の導入方法＞＞
　式Ａ１により表される構成単位は、特定バインダーポリマーの製造時に、例えば下記式Ａ１－Ａにより表される化合物をモノマーとして使用することにより、特定バインダーポリマーに導入することができる。
　式Ａ１－Ａにより表される化合物は、式Ａ１－Ｂにより表される化合物、又は式Ａ１－Ｃにより表される化合物であることが好ましい。 << Method for Introducing Structural Unit Represented by Formula A1 >>
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.
Figure JPOXMLDOC01-appb-C000005
 
Figure JPOXMLDOC01-appb-C000005
 
　上記式Ａ１－Ａ～式Ａ１－Ｃ中、Ｒ１、ＬＡ、ＲＡは、それぞれ上述の式Ａ１中のＲ１、ＬＡ、ＲＡと同義であり、好ましい態様も同様である。 The formula A1-A ~ formula A1-C, R 1, L A, R A is, R 1 in each formula A1 described above, L A, has the same meaning as R A, preferable embodiments thereof are also the same.
　上記式Ａ１－Ａにより表される化合物は、公知の方法により得ることができる。
　例えば、２－メタクリロイルオキシエチルイソシアネート等のイソシアネート基を有する（メタ）アクリレート化合物に、アミノ基を有する化合物を付加する方法（式Ａ１－Ｂに該当する化合物が得られる。）、アクリル酸クロライド等のアクリル酸ハライド化合物に、アミノ基を有する化合物を付加する方法（式Ａ１－Ｃに該当する化合物が得られる。）等が挙げられる。 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).
　以下、式Ａ１により表される構成単位の具体例を示すが、これに限定されるものではない。 Hereinafter, although the specific example of the structural unit represented by Formula A1 is shown, it is not limited to this.
Figure JPOXMLDOC01-appb-C000006
 
Figure JPOXMLDOC01-appb-C000006
 
－式Ａ２により表される構成単位－
　式Ａ２中、ＲＡは上述の式Ａ１におけるＲＡと同義であり、好ましい態様も同様である。
　Ｒ２及びＲ３はそれぞれ独立に、水素原子又はアルキル基を表し、水素原子又は炭素数１～４のアルキル基が好ましく、水素原子又はメチル基がより好ましく、水素原子が更に好ましい。 -Structural unit represented by Formula A2-
In formula A2, 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.
＜＜式Ａ２により表される構成単位の導入方法＞＞
　式Ａ２により表される構成単位は、特定バインダーポリマーの製造時に、例えば式Ａ２－Ａにより表される化合物をモノマーとして使用することにより、特定バインダーポリマーに導入することができる。 << Introduction Method of Structural Unit Represented by Formula A2 >>
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.
Figure JPOXMLDOC01-appb-C000007
 
Figure JPOXMLDOC01-appb-C000007
 
　上記式Ａ２－Ａ中、Ｒ２、Ｒ３、ＲＡは、それぞれ上述の式Ａ２中のＲ２、Ｒ３、ＲＡと同義であり、好ましい態様も同様である。 In the formula A2-A, 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.
　上記式Ａ２により表される化合物は、公知の方法により得ることができる。
　例えば、無水マレイン酸と、対応するアミン又はアニリン化合物とを、酸触媒中で脱水縮合する方法等が挙げられる。 The compound represented by the formula A2 can be obtained by a known method.
For example, 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.
　以下、式Ａ２により表される構成単位の具体例を示すが、これに限定されるものではない。 Hereinafter, although the specific example of the structural unit represented by Formula A2 is shown, it is not limited to this.
Figure JPOXMLDOC01-appb-C000008
 
Figure JPOXMLDOC01-appb-C000008
 
－式Ａ３により表される構成単位－
　式Ａ３中、ＲＡは上述の式Ａ１におけるＲＡと同義であり、好ましい態様も同様である。 —Structural Unit Represented by Formula A3—
In formula A3, R A has the same meaning as R A in formula A1 described above, and the preferred embodiments are also the same.
＜＜式Ａ３により表される構成単位の導入方法＞＞
　式Ａ３により表される構成単位は、特定バインダーポリマーの製造時に、例えば酢酸ビニル化合物をモノマーとして使用し、鹸化して得られた高分子化合物を、ＲＡに相当する構造を有するアルデヒドによりアセタール化することにより、特定バインダーポリマーに導入することができる。 << Introduction Method of Structural Unit Represented by Formula A3 >>
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.
　以下、式Ａ３により表される構成単位の具体例を示すが、これに限定されるものではない。 Hereinafter, although the specific example of the structural unit represented by Formula A3 is shown, it is not limited to this.
Figure JPOXMLDOC01-appb-C000009
 
Figure JPOXMLDOC01-appb-C000009
 
－含有量－
　式Ａ１～式Ａ３で表される構成単位の含有量は、特定バインダーポリマーの全質量に対し、１５質量％以上であることが好ましく、２０質量％以上であることがより好ましく、４０質量％以上であることが更に好ましい。
　また、上記含有量の上限は、特に限定されないが、インキ着肉性の観点から、９５質量％以下であることが好ましく、９０質量％以下であることがより好ましく、８０質量％以下であることが更に好ましい。 -Content-
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.
－その他の構成単位－
　特定バインダーポリマーは、インキ着肉性の観点からその他の構成単位を更に含んでもよい。
　その他の構成単位としては、例えば、（メタ）アクリル酸エステル化合物に由来する構成単位が挙げられる。
　上記（メタ）アクリル酸エステル化合物としては、メタクリル酸メチル、メタクリル酸２－エチルヘキシル、メタクリル酸ベンジル、メタクリルアミド、フェニルアクリルアミド、スチレン、アクリロニトリル等が挙げられる。
　また、その他の構成単位として、国際公開第２０１２／１１０３５９号の段落００３３に記載の構成単位を含んでもよい。 -Other structural units-
The specific binder polymer may further contain other structural units from the viewpoint of ink deposition properties.
Examples of other structural units include structural units derived from (meth) acrylic acid ester compounds.
Examples of the (meth) acrylic acid ester compound include methyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, methacrylamide, phenylacrylamide, styrene, acrylonitrile and the like.
Further, as other structural units, the structural units described in paragraph 0033 of International Publication No. 2012/110359 may be included.
　その他の構成単位は、１種単独で含まれていてもよいし、２種以上を併用してもよい。
　その他の構成単位の含有量は、特定バインダーポリマーの全質量に対し、５質量％～５０質量％であることが好ましく、５質量％～４０質量％であることがより好ましく、５質量％～２０質量％であることが更に好ましい。 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%.
－酸価－
　特定バインダーポリマーのｐＫａ９以下の酸基による酸価は、２ｍｅｑ／ｇ～４ｍｅｑ／ｇであり、低ｐＨにおける現像性の観点から、２．２ｍｅｑ／ｇ～３．８ｍｅｑ／ｇであることが好ましく、２．５ｍｅｑ／ｇ～３．５ｍｅｑ／ｇであることがより好ましい。
　特定バインダーポリマーのｐＫａ９以下の酸基による酸価は、下記方法により測定される。
　容器に、特定バインダーポリマーを約０．５ｇ秤量し、秤量値Ｗ１（ｇ）を記録する。次いで、テトラヒドロフラン（ＴＨＦ）５４ｍＬ及び蒸留水６ｍＬの混合液を添加し、秤量した特定バインダーポリマーを希釈することにより中和度測定用試料１を得る。
　得られた中和度測定用試料１に対し、滴定液として０．１Ｎ（＝０．１ｍｏｌ／Ｌ）水酸化ナトリウム水溶液を用いて滴定を行い、当量点までに要した滴定液量をＦ１（ｍＬ）として記録する。滴定において複数の当量点が得られた場合は、複数の当量点までに要した複数の滴定液量のうちの最大値をＦ１（ｍＬ）とする。Ｆ１（ｍＬ）と水酸化ナトリウム水溶液の規定度（０．１ｍｏｌ／Ｌ）との積が、特定バインダーポリマーに含まれるｐＫａが９以下の酸基（例えば、－ＣＯＯＨ）のミリモル数に相当する。
　「Ｆ１（ｍＬ）」の測定値に基づき、下記の式に従って、酸価（ｍｅｑ／ｇ）を求める。
　Ｆ１（ｍＬ）×水酸化ナトリウム水溶液の規定度（０．１ｍｏｌ／Ｌ）／Ｗ１（ｇ）　＝　特定バインダーポリマーの合計１ｇに含まれる酸基の全ミリモル数（ｍｅｑ／ｇ）×１００ -Acid value-
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. Next, 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.
The obtained neutralization degree measurement sample 1 is titrated with a 0.1N (= 0.1 mol / L) aqueous sodium hydroxide solution as a titrant, and the amount of titrant required up to the equivalence point is F1 ( mL). When a plurality of equivalent points are obtained in the titration, the maximum value among the plurality of titrant liquid amounts required up to the plurality of equivalent points is defined as F1 (mL). 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.
Based on the measured value of “F1 (mL)”, 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
－分子量－
　特定バインダーポリマーの重量平均分子量は、耐刷性及び現像性の観点から、８，０００～２０，０００であることが好ましく、１０，０００～１８，０００であることがより好ましく、１２，０００～１６，０００であることが更に好ましい。
　上記重量平均分子量が８，０００以上であれば耐刷性に優れやすく、２０，０００以下であれば現像性に優れやすい。 -Molecular weight-
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.
－含有量－
　画像記録層は、特定バインダーポリマーを１種単独で含有してもよいし、２種以上を併用してもよい。
　画像記録層における特定バインダーポリマーの含有量は、画像記録層の全質量に対し、４５質量％～９０質量％であることが好ましく、５０質量％～８０質量％であることがより好ましく、６２質量％～７０質量％であることが更に好ましい。 -Content-
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.
〔赤外線吸収剤〕
　本開示における画像記録層は、赤外線吸収剤を含有する。
　赤外線吸収剤としては、赤外光を吸収し熱を発生する染料であれば特に制限はなく、赤外線吸収剤として知られる種々の染料を用いることができる。
　本開示において用いることができる赤外線吸収剤としては、市販の染料及び文献（例えば「染料便覧」有機合成化学協会編集、昭和４５年刊）に記載されている公知のものが利用できる。具体的には、アゾ染料、金属錯塩アゾ染料、ピラゾロンアゾ染料、アントラキノン染料、フタロシアニン染料、カルボニウム染料、キノンイミン染料、メチン染料、シアニン染料、オキソノール染料などの染料が挙げられる。本開示において、これらの染料のうち、赤外光又は近赤外光を少なくとも吸収するものが、赤外光又は近赤外光を発光するレーザーでの利用に適する点で好ましく、シアニン染料が特に好ましい。 [Infrared absorber]
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.
As 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. Specific examples 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. In the present disclosure, among 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.
　そのような赤外光又は近赤外光を少なくとも吸収する染料としては、例えば、特開昭５８－１２５２４６号、特開昭５９－８４３５６号、特開昭５９－２０２８２９号、特開昭６０－７８７８７号等の各公報に記載されているシアニン染料、国際公開第２０１２／１１０３５９号に記載のオキソノール染料、特開昭５８－１７３６９６号、特開昭５８－１８１６９０号、特開昭５８－１９４５９５号等の各公報に記載されているメチン染料、特開昭５８－１１２７９３号、特開昭５８－２２４７９３号、特開昭５９－４８１８７号、特開昭５９－７３９９６号、特開昭６０－５２９４０号、特開昭６０－６３７４４号等の各公報に記載されているナフトキノン染料、特開昭５８－１１２７９２号公報等に記載されているスクワリリウム色素、英国特許４３４，８７５号明細書記載のシアニン染料等を挙げることができる。
　また、染料として米国特許第５，１５６，９３８号明細書記載の近赤外吸収増感剤も好適に用いられ、また、米国特許第３，８８１，９２４号明細書記載の置換されたアリールベンゾ（チオ）ピリリウム塩、特開昭５７－１４２６４５号公報（米国特許第４，３２７，１６９号明細書）記載のトリメチンチアピリリウム塩、特開昭５８－１８１０５１号、同５８－２２０１４３号、同５９－４１３６３号、同５９－８４２４８号、同５９－８４２４９号、同５９－１４６０６３号、同５９－１４６０６１号の各公報に記載されているピリリウム系化合物、特開昭５９－２１６１４６号公報記載のシアニン色素、米国特許第４，２８３，４７５号明細書に記載のペンタメチンチオピリリウム塩等や特公平５－１３５１４号、同５－１９７０２号公報に開示されているピリリウム化合物等が、市販品としては、エポリン社製のＥｐｏｌｉｇｈｔ　ＩＩＩ－１７８、Ｅｐｏｌｉｇｈｔ　ＩＩＩ－１３０、Ｅｐｏｌｉｇｈｔ　ＩＩＩ－１２５等が特に好ましく用いられる。
　また、染料として特に好ましい別の例として米国特許第４，７５６，９９３号明細書中に式（Ｉ）、（ＩＩ）として記載されている近赤外吸収染料を挙げることができる。 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. Methine dyes described in JP-A-58-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59-73996, JP-A-60-52940 Naphthoquinone dyes described in JP-A-60-63744, etc., squarylium dyes described in JP-A-58-112792, etc., It can be exemplified cyanine dyes countries Patent 434,875 Pat described.
Further, near-infrared absorption sensitizers described in US Pat. No. 5,156,938 are also preferably used as dyes, and substituted arylbenzoates described in US Pat. No. 3,881,924 are also preferred. (Thio) pyrylium salt, trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59-41363, 59-84248, 59-84249, 59-146063, 59-146061, pyrylium compounds described in JP-A-59-216146 Cyanine dyes, pentamethine thiopyrylium salts described in US Pat. No. 4,283,475, etc., and Japanese Patent Publication Nos. 5-13514 and 5-19702 Pyrylium compounds disclosed in distribution is, as commercially available products, 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.
　これらの染料のうち特に好ましいものとしては、シアニン色素、フタロシアニン染料、オキソノール染料、スクアリリウム色素、ピリリウム塩、チオピリリウム染料、ニッケルチオレート錯体が挙げられる。更に、下記式（ａ）で示されるシアニン色素は、本開示における画像記録層に使用した場合に、安定性、経済性に優れるため最も好ましい。 Among these dyes, particularly preferred are cyanine dyes, phthalocyanine dyes, oxonol dyes, squarylium dyes, pyrylium salts, thiopyrylium dyes, and nickel thiolate complexes. Furthermore, 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.
Figure JPOXMLDOC01-appb-C000010
 
Figure JPOXMLDOC01-appb-C000010
 
　式（ａ）中、Ｘ１は、水素原子、ハロゲン原子、ジアリールアミノ基（－ＮＰｈ２）、Ｘ２－Ｌ１又は以下に示す基を表す。Ｘ２は、酸素原子又は硫黄原子を示す。Ｌ１は、炭素数１～１２の炭化水素基、ヘテロ原子を有する芳香族環、又はヘテロ原子を含む炭素数１～１２の炭化水素基を示す。なお、ここでヘテロ原子とは、Ｎ、Ｓ、Ｏ、ハロゲン原子、Ｓｅを示す。 In the formula (a), 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. In addition, a hetero atom here shows N, S, O, a halogen atom, and Se.
Figure JPOXMLDOC01-appb-C000011
 
Figure JPOXMLDOC01-appb-C000011
 
　上記式中、Ｘａ-は後述するＺａ-と同様に定義され、Ｒaは、水素原子、アルキル基、アリール基、置換又は無置換のアミノ基、ハロゲン原子より選択される置換基を表す。 In the above formula, 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.
　Ｒ２１及びＲ２２は、それぞれ独立に、炭素数１～１２の炭化水素基を示す。感光層塗布液の保存安定性から、Ｒ２１及びＲ２２は、炭素数２個以上の炭化水素基であることが好ましく、更に、Ｒ２１とＲ２２とは互いに結合し、５員環又は６員環を形成していることが特に好ましい。 R 21 and R 22 each independently represents a hydrocarbon group having 1 to 12 carbon atoms. In view of the storage stability of the photosensitive layer coating solution, 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.
　Ａｒ１、Ａｒ２は、それぞれ同じでも異なっていてもよく、置換基を有していてもよい芳香族炭化水素基を示す。好ましい芳香族炭化水素基としては、ベンゼン環及びナフタレン環が挙げられる。また、好ましい置換基としては、炭素数１２個以下の炭化水素基、ハロゲン原子、炭素数１２個以下のアルコキシ基が挙げられる。
　Ｙ１１、Ｙ１２は、それぞれ同じでも異なっていてもよく、硫黄原子又は炭素数１２個以下のジアルキルメチレン基を示す。Ｒ２３及びＲ２４は、それぞれ同じでも異なっていてもよく、置換基を有していてもよい炭素数２０個以下の炭化水素基を示す。好ましい置換基としては、炭素数１２個以下のアルコキシ基、カルボキシル基、スルホ基が挙げられる。
　Ｒ２５、Ｒ２６、Ｒ２７及びＲ２８は、それぞれ同じでも異なっていてもよく、水素原子又は炭素数１２個以下の炭化水素基を示す。原料の入手性から、好ましくは水素原子である。また、Ｚａ－は、対アニオンを示す。但し、式（ａ）で示されるシアニン色素がその構造内にアニオン性の置換基を有し、電荷の中和が必要ない場合は、Ｚａ－は必要ない。好ましいＺａ－は、感光層塗布液の保存安定性から、ハロゲン化物イオン、過塩素酸イオン、テトラフルオロボレートイオン、ヘキサフルオロホスフェートイオン、及びスルホン酸イオンであり、特に好ましくは、過塩素酸イオン、ヘキサフルオロホスフェートイオン、及びアリールスルホン酸イオンである。 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. Moreover, as a preferable substituent, 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. Hexafluorophosphate ion and aryl sulfonate ion.
　好適に用いることのできる式（ａ）で示されるシアニン色素の具体例としては、特開２００１－１３３９６９号公報の段落００１７～００１９、特開２００２－４０６３８号公報の段落００１２～００３８、特開２００２－２３３６０号公報の段落００１２～００２３に記載されたものを挙げることができる。
　赤外線吸収剤として特に好ましくは、以下に示すシアニン染料Ａである。 Specific examples of 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.
Figure JPOXMLDOC01-appb-C000012
 
Figure JPOXMLDOC01-appb-C000012
 
　本開示に係る画像記録層に赤外線吸収剤を添加する際の添加量としては、感光性樹脂組成物の全固形分に対し、０．０１質量％～５０質量％であることが好ましく、０．１質量％～３０質量％であることがより好ましく、１．０質量％～３０質量％であることが特に好ましい。添加量が０．０１質量％以上であると、高感度となり、また、５０質量％以下であると、層の均一性が良好であり、層の耐久性に優れる。 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. When 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.
〔その他のバインダーポリマー〕
　本開示における画像記録層は、上述の特定バインダーポリマーに加え、その他のバインダーポリマーを更に含んでもよい。
　その他のバインダーポリマーとしては、従来公知のものであれば特に制限はないが、例えば、ポリウレタン樹脂、ポリウレア樹脂、ポリウレタンウレア樹脂、ポリアミド樹脂、ポリイミド樹脂、エポキシ樹脂、ポリアセタール樹脂、アクリル樹脂、メタクリル樹脂、ポリスチレン系樹脂、フェノール樹脂等を挙げることができる。
　これらの中でも、フェノール樹脂、スチレン－アクリロニトリル樹脂、アクリル樹脂、アセタール樹脂、ウレア結合、ウレタン結合又はアミド結合を主鎖に有する樹脂等が好ましく挙げられる。
　また、これら樹脂は、現像性の観点から、親水性基を有していることが好ましく、酸基を有していることがより好ましい。
　その他のバインダーポリマーには、上述の特定バインダーポリマーに該当する成分は含まれないものとする。 [Other binder polymers]
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.
Among these, 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.
In addition, 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.
〔フェノール樹脂〕
　本開示において用いられるその他のバインダーポリマーは、重量平均分子量が２，０００を超えるフェノール樹脂であることが好ましい。重量平均分子量が２，０００を超えるフェノール樹脂は、構造単位としてフェノール、あるいは置換フェノール類を含むフェノール樹脂であり、好ましくはノボラック樹脂である。ノボラック樹脂は、平版印刷版原版において、未露光部において強い水素結合性を生起し、露光部において一部の水素結合が容易に解除されるといった点から、本開示における感光性樹脂組成物に好ましく用いられるアルカリ可溶性樹脂である。
　このノボラック樹脂は、分子内に構造単位としてフェノール類を含むものであれば特に制限はない。
　本開示におけるノボラック樹脂は、フェノール、以下に示される置換フェノール類と、アルデヒド類との縮合反応により得られる樹脂であり、フェノール類としては、具体的には、フェノール、イソプロピルフェノール、ｔ－ブチルフェノール、ｔ－アミルフェノール、ヘキシルフェノール、シクロヘキシルフェノール、３－メチル－４－クロロ－６－ｔ－ブチルフェノール、イソプロピルクレゾール、ｔ－ブチルクレゾール、ｔ－アミルクレゾールが挙げられる。好ましくは、ｔ－ブチルフェノール、ｔ－ブチルクレゾールである。また、アルデヒド類の例としては、ホルムアルデヒド、アセトアルデヒド、アクロレイン、クロトンアルデヒド等の脂肪族及び芳香族アルデヒドが挙げられる。好ましくは、ホルムアルデヒド、アセトアルデヒドである。
　より具体的には、本開示におけるノボラック樹脂しては、例えば、フェノールとホルムアルデヒドとの縮重合体（フェノールホルムアルデヒド樹脂）、ｍ－クレゾールとホルムアルデヒドとの縮重合体（ｍ－クレゾールホルムアルデヒド樹脂）、ｐ－クレゾールとホルムアルデヒドとの縮重合体（ｐ－クレゾールホルムアルデヒド樹脂）、ｍ－／ｐ－混合クレゾールとホルムアルデヒドとの縮重合体（ｍ－／ｐ－混合クレゾールホルムアルデヒド樹脂）、フェノールとクレゾール（ｍ－，ｐ－，又はｍ－／ｐ－混合のいずれでもよい）とホルムアルデヒドとの縮重合体（フェノール／クレゾール（ｍ－，ｐ－，又はｍ－／ｐ－混合のいずれでもよい）混合ホルムアルデヒド樹脂）等が挙げられる。
　また、ノボラック樹脂としては、更に、米国特許第４，１２３，２７９号明細書に記載されているように、ｔ－ブチルフェノールホルムアルデヒド樹脂、オクチルフェノールホルムアルデヒド樹脂のような、炭素数３～８のアルキル基を置換基として有するフェノールとホルムアルデヒドとの縮重合体が挙げられる。
　これらノボラック樹脂の中でも、特に好ましいものとして、フェノールホルムアルデヒド樹脂、フェノール／クレゾール混合ホルムアルデヒド樹脂が挙げられる。 [Phenolic resin]
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 alkali-soluble resin used.
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. Specific examples of 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. Examples of 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. -Condensation polymer of cresol and formaldehyde (p-cresol formaldehyde resin), m- / p-mixed cresol and formaldehyde (m- / p-mixed cresol formaldehyde resin), phenol and cresol (m-, P- or m- / p-mixed) and formaldehyde condensation polymer (phenol / cresol (m-, p-, or m- / p-mixed) mixed formaldehyde resin), etc. Is mentioned.
Further, as the novolak resin, as described in US Pat. No. 4,123,279, 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.
Among these novolak resins, phenol formaldehyde resins and phenol / cresol mixed formaldehyde resins are particularly preferable.
　上記フェノール樹脂の重量平均分子量は、好ましくは２，０００を超え５０，０００以下であり、２，５００～２０，０００であることが更に好ましく、３，０００～１０，０００であることが特に好ましい。また、分散度（重量平均分子量／数平均分子量）は、１．１～１０であることが好ましい。
　上記数平均分子量は、テトラヒドロフラン（ＴＨＦ）を溶剤とした場合のゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定されるポリスチレン換算の数平均分子量である。 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.
〔スチレン－アクリロニトリル樹脂〕
　スチレン－アクリロニトリル樹脂としては、特に限定されず公知の樹脂を使用することができるが、例えば、特開２０１１－２０９３４３号公報の段落００１２～段落００２１に記載の（メタ）アクリロニトリルに由来する構成単位と、スチレンに由来する構成単位とを含むコポリマーが挙げられる。 [Styrene-acrylonitrile resin]
The styrene-acrylonitrile resin is not particularly limited, and a known resin can be used. For example, a structural unit derived from (meth) acrylonitrile described in paragraphs 0012 to 0021 of JP2011-209343A can be used. And a copolymer containing a structural unit derived from styrene.
〔アクリル樹脂〕
　アクリル樹脂としては、特に限定されず公知の樹脂を使用することができるが、例えば、欧州特許第１８２６００１号明細書の段落００１２～段落００３９に記載のアクリル樹脂が挙げられる。 〔acrylic resin〕
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.
〔アセタール樹脂〕
　アセタール樹脂としては、特に限定されず公知の樹脂を使用することができるが、例えば、国際公開第２０１４／１０６５５４号の段落００１２～段落００２１に記載のアセタール樹脂が挙げられる。 [Acetal resin]
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.
〔ウレア結合、ウレタン結合及びアミド結合よりなる群から選ばれた少なくとも一つの結合を主鎖に有する高分子化合物〕
　ウレア結合、ウレタン結合及びアミド結合よりなる群から選ばれた少なくとも一つの結合を主鎖に有する高分子化合物（特定高分子化合物）としては、従来公知のものであれば特に制限はないが、例えば以下のウレア樹脂、ウレタン樹脂及びアミド樹脂が好ましく使用される。
　本開示において、「主鎖」とは樹脂を構成する高分子化合物の分子中で相対的に最も長い結合鎖を表し、「側鎖」とは主鎖から枝分かれしている原子団を表す。 [High molecular compound having at least one bond selected from the group consisting of urea bond, urethane bond and amide bond in the main chain]
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.
In the present disclosure, “main chain” represents a relatively long bond chain in the molecule of the polymer compound constituting the resin, and “side chain” represents an atomic group branched from the main chain.
　特定高分子化合物は、得られる平版印刷版の耐刷性の観点から、ウレア結合、ウレタン結合、アミド結合の少なくともいずれか一つの結合を主鎖に有することが好ましく、ウレア結合、アミド結合のいずれか一つの結合を主鎖に有することがより好ましく、ウレア結合を主鎖に有することが更に好ましい。
また、上記高分子化合物は、ポリウレア樹脂、ポリウレタン樹脂又はポリアミド樹脂であることが好ましく、ポリウレア樹脂、又は、ポリアミド樹脂であることが好ましく、ポリウレア樹脂であることが最も好ましい。 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.
－ウレア結合－
　本開示において、「ウレア結合」は、一般式：－ＮＲ１Ｃ（＝Ｏ）ＮＲ２－で表される。本開示においては、Ｒ１及びＲ２はそれぞれ独立に、水素原子又は炭素数１～１０のアルキル基（メチル基、エチル基、プロピル基、イソプロピル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基等）を表し、好ましくは、水素原子又は炭素数５以下のアルキル基である。
　また、本開示において、主鎖がウレア結合により形成されている高分子化合物をポリウレア樹脂ともいう。 -Urea bond-
In the present disclosure, the “urea bond” is represented by the general formula: —NR 1 C (═O) NR 2 —. In the present disclosure, 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.
In the present disclosure, a polymer compound whose main chain is formed by a urea bond is also referred to as a polyurea resin.
　ウレア結合は、いかなる手段を用いて形成されてもよいが、イソシアネート化合物とアミン化合物との反応で得ることができる。
　また、１，３－ビス（２－アミノエチル）ウレア、１，３－ビス（２－ヒドロキシエチル）ウレア、１，３－ビス（２－ヒドロキシプロピル）ウレア等のように、末端にヒドロキシ基又はアミノ基を有するアルキル基で置換されたウレア化合物を原料として合成してもよい。 The urea bond may be formed by any means, but can be obtained by a reaction between an isocyanate compound and an amine compound.
In addition, 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.
　原料として使用する上記イソシアネート化合物は、分子内にイソシアネート基を２つ以上有するポリイソシアネート化合物であれば特に制限なく使用可能であるが、ジイソシアネート化合物が好ましい。
　ポリイソシアネート化合物として、例えば、１，３－ビス（イソシアナトメチル）シクロヘキサン、ジイソシアン酸イソホロン、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ペンタメチレンジイソシアネート、ヘキサメチレンジイソシアネート、１，３－シクロペンタンジイソシアネート、９Ｈ－フルオレン－２，７－ジイソシアネート、９Ｈ－フルオレン－９－オン－２，７－ジイソシアネート、４，４’－ジフェニルメタンジイソシアナート、１，３－フェニレンジイソシアナート、トリレン－２，４－ジイソシアナート、トリレン－２，６－ジイソシアナート、１，３－ビス（イソシアナトメチル）シクロヘキサン、２，２－ビス（４－イソシアナトフェニル）ヘキサフルオロプロパン、１，５－ジイソシアナトナフタレン等が挙げられる。 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.
Examples of 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. -2,7-diisocyanate, 9H-fluoren-9-one-2,7-diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, tolylene-2,4-diisocyanate, Tolylene-2,6-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 2,2-bis (4-isocyanatophenyl) hexafluoropropane, 1,5-diisocyanate And naphthalene.
　原料として使用する上記アミン化合物としては、分子内にアミノ基を２つ以上有するポリアミン化合物であれば特に制限なく使用可能であるが、ジアミン化合物が好ましい。
　ポリアミン化合物として、例えば、２，７－ジアミノ－９Ｈ－フルオレン、３，６－ジアミノアクリジン、アクリフラビン、アクリジンイエロー、２，２－ビス（４－アミノフェニル）ヘキサフルオロプロパン、４，４’－ジアミノベンゾフェノン、ビス（４－アミノフェニル）スルホン、４，４’－ジアミノジフェニルエーテル、ビス（４－アミノフェニル）スルフィド、１，１－ビス（４－アミノフェニル）シクロヘキサン、４，４’－ジアミノジフェニルメタン、３，３’－ジアミノジフェニルメタン、３，３’－ジアミノベンゾフェノン、４，４’－ジアミノ－３，３’－ジメチルジフェニルメタン、４－（フェニルジアゼニル）ベンゼン－１，３－ジアミン、１，５－ジアミノナフタレン、１，３－フェニレンジアミン、２，４－ジアミノトルエン、２，６－ジアミノトルエン、１，８－ジアミノナフタレン、１，３－ジアミノプロパン、１，３－ジアミノペンタン、２，２－ジメチル－１，３－プロパンジアミン、１，５－ジアミノペンタン、２－メチル－１，５－ジアミノペンタン、１，７－ジアミノヘプタン、Ｎ，Ｎ－ビス（３－アミノプロピル）メチルアミン、１，３－ジアミノ－２－プロパノール、ジエチレングリコールビス（３－アミノプロピル）エーテル、ｍ－キシリレンジアミン、テトラエチレンペンタミン、１，３－ビス（アミノメチル）シクロヘキサン、ベンゾグアナミン、２，４－ジアミノ－１，３，５－トリアジン、２，４－ジアミノ－６－メチル－１，３，５－トリアジン、６－クロロ－２，４－ジアミノピリミジン、２－クロロ－４，６－ジアミノ－１，３，５－トリアジン等が挙げられる。
　また、後述する酸基を有するジアミン化合物Ａも好適に使用することができる。
　これらのポリアミンにホスゲン又はトリホスゲン等を反応させて、ポリイソシアネートを合成し、原料として用いてもよい。 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.
Examples of 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'-diamino-3,3'-dimethyldiphenylmethane, 4- (phenyldiazenyl) benzene-1,3-diamine, 1,5-diaminonaphthalene 1,3-phenylenediamine, 2,4-diaminoto Ruene, 2,6-diaminotoluene, 1,8-diaminonaphthalene, 1,3-diaminopropane, 1,3-diaminopentane, 2,2-dimethyl-1,3-propanediamine, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,7-diaminoheptane, N, N-bis (3-aminopropyl) methylamine, 1,3-diamino-2-propanol, diethylene glycol bis (3-aminopropyl) Ether, m-xylylenediamine, tetraethylenepentamine, 1,3-bis (aminomethyl) cyclohexane, benzoguanamine, 2,4-diamino-1,3,5-triazine, 2,4-diamino-6-methyl- 1,3,5-triazine, 6-chloro-2,4-diaminopyrimidine, 2-chloro-4,6-diamino- , 3,5-triazine.
Moreover, the diamine compound A which has the acid group mentioned later can also be used conveniently.
These polyamines may be reacted with phosgene or triphosgene to synthesize polyisocyanates and used as raw materials.
－ウレタン結合－
　本開示において、「ウレタン結合」は、式：－ＯＣ（＝Ｏ）ＮＲ３－で表される。ここで、Ｒ３は、水素原子又は炭素数１～１０のアルキル基（メチル基、エチル基、プロピル基、イソプロピル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基等）を表し、好ましくは、水素原子又は炭素数５以下のアルキル基であり、更に好ましくは、水素原子又はメチル基である。
　本開示においては、主鎖がウレタン結合により形成されているポリマーをポリウレタン樹脂という。 -Urethane bond-
In the present disclosure, the “urethane bond” is represented by the formula: —OC (═O) NR 3 —. Here, 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.
In the present disclosure, a polymer having a main chain formed by a urethane bond is referred to as a polyurethane resin.
　ウレタン結合は、如何なる手段を用いて形成されてもよいが、イソシアネート化合物とヒドロキシ基を有する化合物との反応により得ることができる。
　原料として用いるイソシアネート化合物は、分子内にイソシアネート基を２つ以上有するポリイソシアネート化合物が好ましく、ジイソシアネート化合物が更に好ましい。ポリイソシアネート化合物としては、上記ウレア結合を形成する原料として挙げたポリイソシアネート化合物を挙げることができる。
　原料として用いるヒドロキシ基を有する化合物としては、ポリオール化合物、アミノアルコール化合物、アミノフェノール化合物、アルキルアミノフェノール化合物等を挙げることができるが、好ましくはポリオール化合物又はアミノアルコール化合物である。
　ポリオール化合物は、分子内に少なくとも２つ以上のヒドロキシ基を有する化合物であり、好ましくはジオール化合物である。又、分子内にエステル結合又はエーテル結合を有していてもよい。ポリオール化合物として、例えば、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、１，７－ヘプタンジオール、１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール、ネオペンチルグリコール、ポリエチレングリコール、ポリテトラメチレングリコール、１，４－シクロヘキサンジメタノール、ペンタエリスリトール、３－メチル－１，５－ペンタンジオール、ポリ（エチレンアジペート）、ポリ（ジエチレンアジペート）、ポリ（プロピレンアジペート）、ポリ（テトラメチレンアジペート）、ポリ（ヘキサメチレンアジペート）、ポリ（ネオペンチレンアジペート）等を挙げることができる。
　また、後述する酸基を有するジオール化合物Ａも好適に用いることができる。
　アミノアルコール化合物は、分子内にアミノ基とヒドロキシ基を有する化合物であり、更に分子内にエーテル結合を有していてもよい。アミノアルコールとして、例えば、アミノエタノール、３－アミノ－１－プロパノール、２－（２－アミノエトキシ）エタノール、２－アミノ－１，３－プロパンジオール、２－アミノ－２－メチル－１，３－プロパンジオール、１，３－ジアミノ－２－プロパノール等を挙げることができる。 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. As a polyisocyanate compound, the polyisocyanate compound mentioned as a raw material which forms the said urea bond can be mentioned.
Examples of 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 | numerator. Examples of 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 (tetramethylene adipate), poly (hexamethylene adipate), poly (neopentylene adipate) and the like.
Moreover, 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.
－アミド結合－
　アミド結合は、いかなる手段を用いて形成されてもよいが、カルボン酸塩化物とアミン化合物との反応で得ることができる。
　アミン化合物としては、上記ウレア結合を形成する原料として挙げたポリアミン化合物を挙げることができ、後述する酸基を有するジアミン化合物Ａも好適に使用することができる。
　カルボン酸塩化合物としては、カルボン酸ハライド化合物、又は、カルボン酸エステル化合物等が挙げられ、例えば、下記ＣＬ－１～ＣＬ－１０等が挙げられる。 -Amide bond-
The amide bond may be formed by any means, but can be obtained by reacting a carboxylic acid chloride with an amine compound.
As 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.
Examples of 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.
Figure JPOXMLDOC01-appb-C000013
 
Figure JPOXMLDOC01-appb-C000013
 
－酸基－
　特定高分子化合物は、現像性の観点から酸基を含むことが好ましい。
　酸基としては、例えば下記（１）～（７）に記載の酸基が好ましく挙げられる。
（１）フェノール性ヒドロキシ基（－Ａｒ－ＯＨ又は－Ａｒ（－ＯＨ）－により表される二価の基）
（２）スルホンアミド基（－ＳＯ２ＮＨ－Ｒ、又は、－ＳＯ２ＮＨ－により表される二価の基）
（３）置換スルホンアミド系酸基（－ＳＯ２ＮＨＣＯＲ、－ＳＯ２ＮＨＳＯ２Ｒ、－ＣＯＮＨＳＯ２Ｒ）（以下「活性イミド基」という。）
（４）カルボキシ基（－ＣＯ２Ｈ）
（５）スルホ基（－ＳＯ３Ｈ）
（６）リン酸基（－ＯＰＯ３Ｈ２）
（７）ホスホン酸基（－ＰＯ３Ｈ２）
　上記（１）～（７）中、Ａｒは、置換基を有していてもよい２価のアリール基を表し、Ｒは、置換基を有していてもよい炭化水素基を表す。 -Acid group-
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.
(1) Phenolic hydroxy group (a divalent group represented by —Ar—OH or —Ar (—OH) —)
(2) Sulfonamide group (a divalent group represented by —SO 2 NH—R or —SO 2 NH—)
(3) Substituted sulfonamide acid group (—SO 2 NHCOR, —SO 2 NHSO 2 R, —CONHSO 2 R) (hereinafter referred to as “active imide group”)
(4) Carboxy group (—CO 2 H)
(5) Sulfo group (—SO 3 H)
(6) Phosphate group (—OPO 3 H 2 )
(7) Phosphonic acid group (—PO 3 H 2 )
In the above (1) to (7), Ar represents a divalent aryl group which may have a substituent, and R represents a hydrocarbon group which may have a substituent.
　上記（１）～（７）より選ばれる酸基を有する特定高分子化合物の中でも、（１）フェノール性ヒドロキシ基、（２）スルホンアミド基又は（３）活性イミド基を有する特定高分子化合物が好ましく、（１）フェノール性ヒドロキシ基又は（２）スルホンアミド基を有する特定高分子化合物が、アルカリ現像液に対する溶解性、膜強度を十分に確保する点から特に好ましい。
　すなわち、特定高分子化合物はフェノール性ヒドロキシ基及びスルホンアミド基の少なくともいずれかを、主鎖及び側鎖の少なくともいずれかに有することが好ましい。
　また、特定化合物としては、スルホンアミド基を主鎖に有するポリウレア樹脂、フェノール性ヒドロキシ基を主鎖に有するポリウレア樹脂、スルホンアミド基を主鎖に有するポリウレタン樹脂、及び、フェノール性ヒドロキシ基を主鎖に有するポリアミド樹脂よりなる群から選ばれた少なくとも１種であることが好ましい。
　本開示において、高分子化合物がフェノール性ヒドロキシ基を主鎖に有するとは、－Ａｒ（－ＯＨ）－により表される二価の基を主鎖に有することをいう。また、高分子化合物がスルホンアミド基を主鎖に有するとは、－ＳＯ２ＮＨ－により表される二価の基を主鎖に有することを意味する。 Among 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.
In the present disclosure, 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. Further, 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.
－フェノール性水酸基を有する構成単位－
　特定高分子化合物は、フェノール性水酸基を有する構成単位を有することが好ましく、下記式ＡＦ－１で表される構成単位を主鎖に有することがより好ましい。 -Units with phenolic hydroxyl groups-
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.
Figure JPOXMLDOC01-appb-C000014
 
Figure JPOXMLDOC01-appb-C000014
 
　式ＡＦ－１中、ＲＡ１は、単結合又は二価の連結基を表す。
　ＲＡ１は単結合、炭素数１～６のアルキレン基又はスルホニル基であることが好ましく、単結合又は炭素数１～５のアルキレン基であることがより好ましく、単結合又はメチレン基であることが更に好ましく、単結合であることが特に好ましい。
　ＲＡ１におけるアルキレン基は直鎖状、分岐鎖状又は環状のいずれであってもよい。また、ＲＡ１におけるアルキレン基は置換されていてもよく、置換基としては炭素数１～４のアルキル基、炭素数６～１２のアリール基、ハロゲン原子が好ましく例示される。また、上記アリール基は更に置換されていてもよく、好ましい置換基としてはヒドロキシ基が挙げられる。
　また、式ＡＦ－１におけるフェノール性水酸基は、－ＮＨ－が結合した位置のオルト位に結合していることが好ましい。上記態様であると、現像性に優れた平版印刷版原版が得られる。
　上記フェノール性水酸基を有する構成単位を形成するジアミン化合物としては、以下のジアミン化合物が好ましく挙げられる。
　下記ジアミン化合物を、酸基を有するジアミン化合物Ａとしてイソシアネート化合物と反応させることにより、特定高分子化合物に酸基を導入することができる。 In Formula AF-1, 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. In addition, 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.
In addition, the phenolic hydroxyl group in the formula AF-1 is preferably bonded to the ortho position where —NH— is bonded. In the above embodiment, 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.
Figure JPOXMLDOC01-appb-C000015
 
Figure JPOXMLDOC01-appb-C000015
 
Figure JPOXMLDOC01-appb-C000016
 
Figure JPOXMLDOC01-appb-C000016
 
　上記ジアミン化合物の中でも、ＤＡＤＨＢ、１，３－ＤＡＰ、ＤＡＭＤＨ、ＰＤＡＢＰ、ＡＨＰＨＦＰ又はＡＨＰＦＬが好ましく、ＤＡＤＨＢがより好ましい。 Among the above diamine compounds, DADHB, 1,3-DAP, DAMDH, PDABP, AHPPHFP or AHPFL are preferable, and DADHB is more preferable.
－スルホンアミド基を有する構成単位－
　特定高分子化合物は、スルホンアミド基を有する構成単位として、下記式ＡＦ－２により表される構成単位を主鎖に有することが好ましい。 -Constituent unit having sulfonamide group-
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.
Figure JPOXMLDOC01-appb-C000017
 
Figure JPOXMLDOC01-appb-C000017
 
　式ＡＦ－２中、ＲＡ２、ＲＡ３及びＲＡ４はそれぞれ独立に、二価の連結基を表し、Ｘは－ＮＨ－又は－Ｏ－により表される二価の基を表し、２つのＸは同一の基を表す。 In formula AF-2, R A2 , R A3 and R A4 each independently represent a divalent linking group, X represents a divalent group represented by —NH— or —O—, and two X Represents the same group.
　式ＡＦ－２におけるＲＡ２及びＲＡ４はそれぞれ独立に、アルキレン基、アリーレン基、二価の飽和脂環式炭化水素基、二価の不飽和脂環式炭化水素基、又は、これらの基が複数個連結した二価の基が好ましく、アルキレン基又はアリーレン基がより好ましい。
　上記アルキレン基としては炭素数１～２０のアルキレン基が好ましく、炭素数２～１５のアルキレン基がより好ましく、炭素数２～８のアルキレン基が更に好ましい。また、上記アルキレン基は炭素鎖中に酸素原子を含んでもよい。アルキレン基が有してもよい置換基としては、アルキル基、アリール基、ハロゲン原子等が挙げられる。
　上記アリーレン基としては、炭素数６～２０のアリーレン基が好ましく、フェニレン基又はナフチレン基がより好ましく、フェニレン基が更に好ましい。上記アリーレン基は環構造中にヘテロ原子を有していてもよく、ヘテロ原子としては酸素原子、窒素原子又は硫黄原子が挙げられる。
　上記二価の飽和脂環式炭化水素基としては炭素数４～１０の二価の飽和脂環式炭化水素基が好ましく、炭素数４～８の二価の飽和脂環式炭化水素基がより好ましく、炭素数６～８の二価の飽和脂環式炭化水素基が更に好ましい。また、上記二価の飽和脂環式炭化水素基が含んでもよい置換基としては、アルキル基、アリール基、ハロゲン原子等が挙げられる。
　上記二価の不飽和脂環式炭化水素基としては、シクロペンテニル基、シクロペンタジエニル基、シクロヘキセニル基、シクロヘキサジエニル基、シクロヘプテニル基等が挙げられる。
　これらの基が複数個連結した二価の基としては、アルキレン基とアリーレン基、又は、アルキレン基と二価の飽和脂環式炭化水素基が複数個結合した基が好ましく、アルキレン基－アリーレン基－アルキレン基、又は、アルキレン基－二価の飽和脂環式炭化水素基－アルキレン基という順に結合した基が好ましい。 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. Examples of 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. Examples of the substituent that the divalent saturated alicyclic hydrocarbon group may include include an alkyl group, an aryl group, and a halogen atom.
Examples of 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.
　式ＡＦ－２におけるＲＡ３は、耐刷性及び耐薬品性の観点から、フェニレン基又は多環式構造を含む二価の連結基であることが好ましく、フェニレン基又は多環式構造からなる二価の連結基であることがより好ましく、多環式構造からなる二価の連結基であることが更に好ましい。
　上記多環式構造としては、ナフタレン誘導体構造、アントラセン誘導体構造、ビフェニル構造、又は、ターフェニル構造であることが好ましく、キサントン構造、アントロン構造、キサンテン構造、ジヒドロアントラセン構造、アントラセン構造、ビフェニル構造、又は、ターフェニル構造であることがより好ましい。耐薬品性、耐刷性、及び、現像性の観点から、キサントン構造、アントロン構造、ビフェニル構造、又は、ナフタレン構造が好ましく、キサントン構造又はアントロン構造がより好ましい。 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.
　上記式ＡＦ－２により表される構成単位を形成するジアミン化合物又はジオール化合物としては、以下の化合物が好ましく挙げられる。
　下記化合物中、Ｚはヒドロキシ基（－ＯＨ）又はアミノ基（－ＮＨ２）を表し、２つのＺは同一の基を表す。
　下記ジアミン化合物又はジオール化合物を、酸基を有するジアミン化合物Ａ又は酸基を有するジオール化合物Ａとしてイソシアネート化合物と反応させる、又は、酸基を有するジアミン化合物Ａをカルボン酸塩化合物と反応させることにより、特定高分子化合物に酸基を導入することができる。 Preferred examples of the diamine compound or diol compound that forms the structural unit represented by the formula AF-2 include the following compounds.
In the following compounds, Z represents a hydroxy group (—OH) or an amino group (—NH 2 ), and two Zs represent the same group.
By reacting the following diamine compound or diol compound with an isocyanate compound as the diamine compound A having an acid group or the diol compound A having an acid group, or by reacting the diamine compound A having an acid group with a carboxylate compound, An acid group can be introduced into the specific polymer compound.
Figure JPOXMLDOC01-appb-C000018
 
Figure JPOXMLDOC01-appb-C000018
 
Figure JPOXMLDOC01-appb-C000019
 
Figure JPOXMLDOC01-appb-C000019
 
Figure JPOXMLDOC01-appb-C000020
 
Figure JPOXMLDOC01-appb-C000020
 
Figure JPOXMLDOC01-appb-C000021
 
Figure JPOXMLDOC01-appb-C000021
 
Figure JPOXMLDOC01-appb-C000022
 
Figure JPOXMLDOC01-appb-C000022
 
－カルボキシ基を有する構成単位－
　特定高分子化合物は、カルボキシ基を有する構成単位を主鎖に有してもよい。
　カルボキシ基を有する構成単位としては、特に限定されず、例えば、アルキレン基、アリーレン基又はそれらを組み合わせた基の炭素原子をカルボキシ基により置換した基が挙げられる。
　上記アルキレン基としては、炭素数２～２０のアルキレン基が好ましく、炭素数４～１０のアルキレン基がより好ましい。
　上記アリーレン基としては、炭素数６～１２のアリーレン基が好ましく、フェニレン基がより好ましい。 -Constitutional unit having a carboxy 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.
　上記カルボキシ基を有する構成単位を形成するジアミン化合物又はジオール化合物としては、以下の化合物が好ましく挙げられる。
　下記化合物中、Ｚはヒドロキシ基（－ＯＨ）又はアミノ基（－ＮＨ２）を表し、２つのＺは同一の基を表す。
　下記ジアミン化合物又はジオール化合物を、上述の酸基を有するジアミン化合物Ａ又は上述の酸基を有するジオール化合物Ａとしてイソシアネート化合物と反応させることにより、特定高分子化合物に酸基を導入することができる。 Preferred examples of the diamine compound or diol compound that forms the structural unit having a carboxy group include the following compounds.
In the following compounds, Z represents a hydroxy group (—OH) or an amino group (—NH 2 ), and two Zs represent the same group.
By reacting the following diamine compound or diol compound with the isocyanate compound as the diamine compound A having the above acid group or the above diol compound A having the acid group, an acid group can be introduced into the specific polymer compound.
Figure JPOXMLDOC01-appb-C000023
 
Figure JPOXMLDOC01-appb-C000023
 
－活性イミド基を有する構成単位－
　特定高分子化合物は、活性イミド基を有する構成単位を主鎖に有することが好ましい。
　活性イミド基を有する構成単位としては、特に限定されず、例えば、アルキレン基の炭素原子を活性イミド基により置換した基が挙げられる。
　上記アルキレン基としては、炭素数２～２０のアルキレン基が好ましく、炭素数４～１０のアルキレン基がより好ましい。
　縮合後に主鎖となる炭素鎖中に活性イミド基を有するジアミン化合物又はジオール化合物を、上述の酸基を有するジアミン化合物Ａ又は上述の酸基を有するジオール化合物Ａとしてイソシアネート化合物と反応させることにより、特定高分子化合物に酸基を導入することができる。 -Constituent unit having an active imide 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.
By reacting the diamine compound or diol compound having an active imide group in the carbon chain that becomes the main chain after condensation with the isocyanate compound as the diamine compound A having the above acid group or the diol compound A having the above acid group, Acid groups can be introduced into specific polymer compounds.
－アルキレンオキシ基を有する構成単位－
　本開示に用いられる特定高分子化合物は、アルキレンオキシ基を更に主鎖に有することが好ましい。
　上記態様によれば、得られる平版印刷版の画像形成性に優れ、得られる平版印刷版の耐刷性に優れた平版印刷版原版が得られる。
　上記アルキレンオキシ基としては、炭素数２～１０のアルキレンオキシ基が好ましく、炭素数２～８のアルキレンオキシ基がより好ましく、炭素数２～４のアルキレンオキシ基が更に好ましく、エチレンオキシ基、又は、プロピレンオキシ基が特に好ましい。
　また、上記アルキレンオキシ基は、ポリアルキレンオキシ基であってもよい。
　ポリアルキレンオキシ基としては、繰り返し数２～５０のポリアルキレンオキシ基が好ましく、繰り返し数２～４０のポリアルキレンオキシ基がより好ましく、繰り返し数２～３０のポリアルキレンオキシ基が更に好ましい。
　ポリアルキレンオキシ基の構成繰り返し単位の好ましい炭素数は、上記アルキレンオキシ基の好ましい炭素数と同様である。 -Constituent units having an alkyleneoxy group-
The specific polymer compound used in the present disclosure preferably further has an alkyleneoxy group in the main chain.
According to the said aspect, 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.
－重量平均分子量－
　特定高分子化合物の重量平均分子量は、得られる平版印刷版の耐刷性の観点から、１０，０００～３００，０００であることが好ましく、２０，０００～３００，０００であることがより好ましく、５０，０００～３００，０００であることが更に好ましい。 -Weight average molecular weight-
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.
〔含有量〕
　その他のバインダーポリマーは、１種単独で含有しても、２種以上を含有してもよい。
　上記感光性樹脂組成物中におけるその他のバインダーポリマーの含有量は、全固形分質量に対し、１０質量％～９５質量％であることが好ましく、２０質量％～９０質量％であることがより好ましく、３０質量％～８５質量％であることが更に好ましい。なお、感光性樹脂組成物の全固形分質量とは、溶剤などの揮発性成分を除いた量を表す。 〔Content〕
Other 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.
　以下に、本開示において使用される、上記高分子化合物の具体例を示すが、本開示は、これらに限定されるものではない。なお、下記式中、括弧の右下の数値は構成単位の含有モル比を表す。また、下記式は、炭化水素の炭素原子及び水素原子を省略した形での記載としている。 Hereinafter, specific examples of the polymer compound used in the present disclosure will be shown, but the present disclosure is not limited thereto. In the following formula, the numerical value at the lower right of the parenthesis represents the molar ratio of constituent units. Moreover, the following formula is described in a form in which carbon atoms and hydrogen atoms of hydrocarbons are omitted.
Figure JPOXMLDOC01-appb-C000024
 
Figure JPOXMLDOC01-appb-C000024
 
　上記ＰＵ－４中、a：b：c＝4：1：5（モル比）である。 In the above PU-4, a: b: c = 4: 1: 5 (molar ratio).
　その他のバインダーポリマーは、１種単独で使用しても、２種以上を併用してもよい。
　その他のバインダーポリマーとして、フェノール樹脂と、スチレン－アクリロニトリル樹脂、アクリル樹脂、アセタール樹脂、及び、特定高分子化合物よりなる群から選ばれた少なくとも１種の樹脂と、を併用することが好ましい。
　その他のバインダーポリマーの含有量は、耐刷性の観点から、画像記録層の全質量に対して、１質量％～９０質量％が好ましく、３質量％～７０質量％がより好ましく、５質量％～５０質量％が特に好ましい。 Other binder polymers may be used alone or in combination of two or more.
As 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.
　上記画像記録層には、所望により他の成分を含有してもよい。
　他の成分としては、公知の添加剤を用いることができる。
　以下、上記画像記録層における任意成分である、酸発生剤、酸増殖剤、及び、その他の添加剤について説明する。 The image recording layer may contain other components as desired.
As other components, known additives can be used.
Hereinafter, the acid generator, the acid proliferating agent, and other additives, which are optional components in the image recording layer, will be described.
〔酸発生剤〕
　本開示に係る画像記録層は、得られる平版印刷版原版における感度向上の観点から、酸発生剤を含有することが好ましい。
　本開示において酸発生剤とは、光又は熱により酸を発生する化合物であり、赤外線の照射や、１００℃以上の加熱によって分解し酸を発生する化合物を指す。発生する酸としては、スルホン酸、塩酸等のｐＫａが２以下の強酸であることが好ましい。この酸発生剤から発生した酸によって、平版印刷版原版における露光部画像記録層への現像液の浸透性が高くなり、画像記録層のアルカリ水溶液に対する溶解性がより向上するものである。
　上記画像記録層において好適に用いられる酸発生剤としては、国際公開第２０１６／０４７３９２号の段落０１１６から段落０１３０に記載の酸発生剤が挙げられる。
　中でも、感度と安定性の観点から、酸発生剤としてオニウム塩化合物を用いることが好ましい。以下、オニウム塩化合物について説明する。
　本開示において好適に用い得るオニウム塩化合物としては、赤外線露光、及び、露光により赤外線吸収剤から発生する熱エネルギーにより分解して酸を発生する化合物として知られる化合物を挙げることができる。本開示に好適なオニウム塩化合物としては、感度の観点から、公知の熱重合開始剤や結合解離エネルギーの小さな結合を有する、以下に述べるオニウム塩構造を有するものを挙げることができる。
　本開示において好適に用いられるオニウム塩としては、公知のジアゾニウム塩、ヨードニウム塩、スルホニウム塩、アンモニウム塩、ピリジニウム塩、アジニウム塩等が挙げられ、中でも、トリアリールスルホニウム、又は、ジアリールヨードニウムのスルホン酸塩、カルボン酸塩、ＢＦ４ －、ＰＦ６ －、ＣｌＯ４ －などが好ましい。
　本開示において酸発生剤として用い得るオニウム塩としては、下記式ＩＩＩ～Ｖで表されるオニウム塩が挙げられる。 [Acid generator]
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.
In the present disclosure, 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.
Examples of 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.
Among these, from the viewpoint of sensitivity and stability, it is preferable to use an onium salt compound as the acid generator. Hereinafter, 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.
Figure JPOXMLDOC01-appb-C000025
 
Figure JPOXMLDOC01-appb-C000025
 
　上記式ＩＩＩ中、Ａｒ１１とＡｒ１２は、それぞれ独立に、置換基を有していてもよい炭素数２０個以下のアリール基を示す。このアリール基が置換基を有する場合の好ましい置換基としては、ハロゲン原子、ニトロ基、炭素数１２個以下のアルキル基、炭素数１２個以下のアルコキシ基、又は炭素数１２個以下のアリールオキシ基が挙げられる。Ｚ１１－はハロゲン化物イオン、過塩素酸イオン、テトラフルオロボレートイオン、ヘキサフルオロホスフェートイオン、スルホン酸イオン、及び、ペルフルオロアルキルスルホン酸イオン等フッ素原子を有するスルホン酸イオンよりなる群から選択される対イオンを表し、好ましくは、過塩素酸イオン、ヘキサフルオロホスフェートイオン、アリールスルホン酸イオン、及びペルフルオロアルキルスルホン酸である。
　上記式ＩＶ中、Ａｒ２１は、置換基を有していてもよい炭素数１～２０のアリール基を示す。好ましい置換基としては、ハロゲン原子、ニトロ基、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、炭素数１～１２のアリールオキシ基、炭素数１～１２のアルキルアミノ基、炭素数２～１２のジアルキルアミノ基、炭素数６～１２のアリールアミノ基又は、ジアリールアミノ基（２つのアリール基の炭素数が、それぞれ独立に、６～１２）が挙げられる。Ｚ２１－はＺ１１－と同義の対イオンを表す。
　上記式Ｖ中、Ｒ３１、Ｒ３２及びＲ３３は、それぞれ同じでも異なっていてもよく、置換基を有していてもよい炭素数１～２０の炭化水素基を示す。好ましい置換基としては、ハロゲン原子、ニトロ基、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、又は炭素数１～１２のアリールオキシ基が挙げられる。Ｚ３１－はＺ１１－と同義の対イオンを表す。 In the above formula III, 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. Represents an ion, preferably a perchlorate ion, a hexafluorophosphate ion, an aryl sulfonate ion, and a perfluoroalkyl sulfonic acid.
In the above formula IV, 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- .
In the above formula V, 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. Preferable 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- .
　上記画像記録層において、好適に用いることのできるオニウム塩の具体例は、国際公開第２０１６／０４７３９２号の段落０１２１～段落０１２４に記載された化合物と同様である。 Specific examples of 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.
　また、上記式ＩＩＩ～式Ｖで表される化合物の別の例としては、特開２００８－１９５０１８号公報の段落００３６～００４５において、ラジカル重合開始剤の例として記載の化合物を、本開示に係る酸発生剤として好適に用いることができる。 Further, as another example of the compound represented by the above formula III to formula V, 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.
　本開示に用いうる酸発生剤のより好ましい例として、下記化合物（ＰＡＧ－１）～（ＰＡＧ－５）が挙げられる。 More preferable examples of the acid generator that can be used in the present disclosure include the following compounds (PAG-1) to (PAG-5).
Figure JPOXMLDOC01-appb-C000026
 
Figure JPOXMLDOC01-appb-C000026
 
　これらの酸発生剤を本開示における画像記録層中に含有させる場合、これらの化合物は単独で使用してもよく、また２種以上を組み合わせて使用してもよい。
　酸発生剤の含有量は、画像記録層の全質量に対し、０．０１質量％～５０質量％であることが好ましく、０．１質量％～４０質量％がより好ましく、０．５質量％～３０質量％が更に好ましい。含有量が上記範囲において、酸発生剤添加の効果である感度の向上が見られると共に、非画像部における残膜の発生が抑制される。 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. When 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.
〔酸増殖剤〕
　本開示における画像記録層は、酸増殖剤を含有してもよい。本開示における酸増殖剤とは、比較的に強い酸の残基で置換された化合物であって、酸触媒の存在下で容易に脱離して新たに酸を発生する化合物である。すなわち、酸触媒反応によって分解し、再び酸を発生する。１反応で１つ以上の酸が増えており、反応の進行に伴って加速的に酸濃度が増加することにより、飛躍的に感度が向上する。この発生する酸の強度は、酸解離定数（ｐＫａ）として３以下であることが好ましく、２以下であることがより好ましい。酸解離定数として３以下であれば、酸触媒による脱離反応を引き起こしやすい。
　このような酸触媒に使用される酸としては、ジクロロ酢酸、トリクロロ酢酸、メタンスルホン酸、エタンスルホン酸、ベンゼンスルホン酸、ｐ－トルエンスルホン酸、ナフタレンスルホン酸、フェニルスルホン酸等が挙げられる。 [Acid multiplication agent]
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.
　使用可能な酸増殖剤は、国際公開第２０１６／０４７３９２号の段落０１３３～段落０１３５に記載されたものと同様である。 Usable acid proliferating agents are the same as those described in paragraphs 0133 to 0135 of International Publication No. 2016/047392.
　これらの酸増殖剤を画像記録層中に添加する場合の含有量としては、画像記録層の全質量に対し、０．０１質量％～２０質量％が好ましく、０．０１質量％～１０質量％がより好ましく、０．１質量％～５質量％が更に好ましい。酸増殖剤の含有量が上記範囲において、酸増殖剤を添加する効果が充分に得られ、感度向上が達成されるともに、画像部の膜強度低下が抑制される。 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. When 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.
〔その他の添加剤〕
　本開示における画像記録層は、その他の添加剤として、現像促進剤、界面活性剤、焼き出し剤、着色剤、可塑剤、ワックス剤等を含んでもよい。 [Other additives]
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.
－現像促進剤－
　本開示における画像記録層には、感度を向上させる目的で、酸無水物類、フェノール類、有機酸類を添加してもよい。
　酸無水物類としては環状酸無水物が好ましく、具体的に環状酸無水物としては、米国特許第４，１１５，１２８号明細書に記載されている無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、３，６－エンドオキシテトラヒドロ無水フタル酸、テトラクロロ無水フタル酸、無水マレイン酸、クロロ無水マレイン酸、α－フェニル無水マレイン酸、無水コハク酸、無水ピロメリット酸などが使用できる。非環状の酸無水物としては、無水酢酸などが挙げられる。
　フェノール類としては、ビスフェノールＡ、２，２’－ビスヒドロキシスルホン、ｐ－ニトロフェノール、ｐ－エトキシフェノール、２，４，４’－トリヒドロキシベンゾフェノン、２，３，４－トリヒドロキシベンゾフェノン、４－ヒドロキシベンゾフェノン、４，４’，４”－トリヒドロキシトリフェニルメタン、４，４’，３”，４”－テトラヒドロキシ－３，５，３’，５’－テトラメチルトリフェニルメタンなどが挙げられる。
　有機酸類としては、特開昭６０－８８９４２号公報、特開平２－９６７５５号公報などに記載されており、具体的には、ｐ－トルエンスルホン酸、ドデシルベンゼンスルホン酸、ｐ－トルエンスルフィン酸、エチル硫酸、フェニルホスホン酸、フェニルホスフィン酸、リン酸フェニル、リン酸ジフェニル、安息香酸、イソフタル酸、アジピン酸、ｐ－トルイル酸、３，４－ジメトキシ安息香酸、フタル酸、テレフタル酸、４－シクロヘキセン－１，２－ジカルボン酸、エルカ酸、ラウリン酸、ｎ－ウンデカン酸、アスコルビン酸などが挙げられる。上記の酸無水物、フェノール類及び有機酸類の画像記録層の全質量に占める割合は、０．０５質量％～２０質量％が好ましく、０．１質量％～１５質量％がより好ましく、０．１質量％～１０質量％が特に好ましい。 -Development accelerator-
For the purpose of improving sensitivity, acid anhydrides, phenols, and organic acids may be added to the image recording layer in the present disclosure.
As the 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, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. Examples of acyclic acid anhydrides include acetic anhydride.
Examples of 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. .
Examples of the organic acids are described in JP-A-60-88942 and JP-A-2-96755. Specifically, 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.
－界面活性剤－
　本開示における画像記録層には、塗布性を良化するため、また、現像条件に対する処理の安定性を広げるため、特開昭６２－２５１７４０号公報や特開平３－２０８５１４号公報に記載されているような非イオン界面活性剤、特開昭５９－１２１０４４号公報、特開平４－１３１４９号公報に記載されているような両性界面活性剤、特開昭６２－１７０９５０号公報、特開平１１－２８８０９３号公報、特開２００３－５７８２０号公報に記載されているようなフッ素含有のモノマー共重合体を添加することができる。
　非イオン界面活性剤の具体例としては、ソルビタントリステアレート、ソルビタンモノパルミテート、ソルビタントリオレート、ステアリン酸モノグリセリド、ポリオキシエチレンノニルフェニルエーテル等が挙げられる。
　両性活性剤の具体例としては、アルキルジ（アミノエチル）グリシン、アルキルポリアミノエチルグリシン塩酸塩、２－アルキル－Ｎ－カルボキシエチル－Ｎ－ヒドロキシエチルイミダゾリニウムベタインやＮ－テトラデシル－Ｎ，Ｎ－ベタイン型（例えば、商品名「アモーゲンＫ」：第一工業製薬（株）製）等が挙げられる。
　界面活性剤の画像記録層の全質量に占める割合は、０．０１質量％～１５質量％が好ましく、０．０１質量％～５質量％がより好ましく、０．０５質量％～２．０質量％が更に好ましい。 -Surfactant-
The image recording layer in the present disclosure is described in Japanese Patent Application Laid-Open No. 62-251740 and Japanese Patent Application Laid-Open No. 3-208514 in order to improve the coating properties and to expand the processing stability against development conditions. 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.
Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether and the like.
Specific examples of 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.
－焼出し剤／着色剤－
　上記画像記録層には、露光による加熱後直ちに可視像を得るための焼出し剤や、画像着色剤としての染料や顔料を加えることができる。
　焼出し剤及び着色剤としては、例えば、特開２００９－２２９９１７号公報の段落０１２２～０１２３に詳細に記載され、ここに記載の化合物を本開示においても適用しうる。
　これらの染料は、画像記録層の全質量に対し、０．０１質量％～１０質量％の割合で添加することが好ましく、０．１質量％～３質量％の割合で添加することがより好ましい。 -Bakeout agent / colorant-
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. .
－可塑剤－
　上記画像記録層には、塗膜の柔軟性等を付与するために可塑剤を添加してもよい。例えば、ブチルフタリル、ポリエチレングリコール、クエン酸トリブチル、フタル酸ジエチル、フタル酸ジブチル、フタル酸ジヘキシル、フタル酸ジオクチル、リン酸トリクレジル、リン酸トリブチル、リン酸トリオクチル、オレイン酸テトラヒドロフルフリル、アクリル酸又はメタクリル酸のオリゴマー及びポリマー等が用いられる。
　これらの可塑剤は、画像記録層の全質量に対し、０．５質量％～１０質量％の割合で添加することが好ましく、１．０質量％～５質量％の割合で添加することがより好ましい。 -Plasticizer-
A plasticizer may be added to the image recording layer in order to impart flexibility and the like of the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid These oligomers and polymers are used.
These 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.
－ワックス剤－
　上記画像記録層には、傷に対する抵抗性を付与する目的で、表面の静摩擦係数を低下させる化合物を添加することもできる。具体的には、米国特許第６，１１７，９１３号明細書、特開２００３－１４９７９９号公報、特開２００３－３０２７５０号公報、又は、特開２００４－１２７７０号公報に記載されているような、長鎖アルキルカルボン酸のエステルを有する化合物などを挙げることができる。
　添加量として好ましいのは、画像記録層の全質量中に占める割合が、０．１質量％～１０質量％であることが好ましく、０．５質量％～５質量％であることがより好ましい。 -Wax agent-
In the image recording layer, for the purpose of imparting resistance to scratches, a compound that lowers the static friction coefficient of the surface can be added. Specifically, as described in US Pat. No. 6,117,913, JP-A No. 2003-149799, JP-A No. 2003-302750, or JP-A No. 2004-12770, 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.
〔各成分の組成比〕
　上記画像記録層における各成分の含有量は、上記画像記録層の全質量に対して、特定バインダーポリマーの含有量は、５０質量％～７０質量％であることが好ましく、赤外線吸収剤の含有量は０．０１質量％～５０質量％であることが好ましく、上記その他のバインダーポリマーの含有量は１質量％～９０質量％であることが好ましく、酸発生剤の含有量は０質量％～３０質量％であることが好ましく、酸増殖剤の含有量は０質量％～２０質量％であることが好ましく、現像促進剤の含有量は０質量％～２０質量％であることが好ましく、界面活性剤の含有量は０質量％～５質量％であることが好ましく、焼き出し剤／着色剤の含有量は０質量％～１０質量％であることが好ましく、可塑剤の含有量は０質量％～１０質量％であることが好ましく、ワックス剤の含有量は０質量％～１０質量％であることが好ましい。 [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, and 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, and 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.
＜下層及び上層＞
　また、上記画像記録層は、下層と上層とを有し、上記バインダーポリマーを含む前記画像記録層が、少なくとも前記下層及び前記上層のいずれかであることが好ましい。
　下層及び上層は、２つの層を分離して形成することが好ましい
　以下、上層及び下層を有する画像記録層を、「二層構造の画像記録層」ともいい、二層構造の画像記録層を有する平版印刷版原版を「二層構造の平版印刷版原版」ともいう。
　２つの層を分離して形成する方法としては、例えば、下層に含まれる成分と、上層に含まれる成分との溶剤溶解性の差を利用する方法、又は、上層を塗布した後、急速に溶剤を乾燥、除去する方法等が挙げられる。後者の方法を併用することにより、層間の分離が一層良好に行われることになるため好ましい。
　上記バインダーポリマーを含む上記画像記録層は、少なくとも上記下層及び上記上層のいずれかであればよいが、耐刷性の観点から、少なくとも下層であることが好ましい。
　以下、これらの方法について詳述するが、２つの層を分離して塗布する方法はこれらに限定されるものではない。 <Lower layer and upper layer>
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. Hereinafter, 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”.
As a method for forming the two layers separately, for example, a method using a difference in solvent solubility between a component contained in the lower layer and a component contained in the upper layer, or after applying the upper layer, a solvent is rapidly used. The method of drying and removing this etc. is mentioned. Use of the latter method in combination is preferable because separation between layers can be performed more satisfactorily.
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.
Hereinafter, although these methods are explained in full detail, the method of isolate | separating and apply | coating two layers is not limited to these.
　下層に含まれる成分と上層に含まれる成分との溶剤溶解性の差を利用する方法としては、上層用塗布液を塗布する際に、下層に含まれる成分のいずれもが不溶な溶剤系を用いるものである。これにより、二層塗布を行っても、各層を明確に分離して塗膜にすることが可能になる。例えば、下層成分として、上層成分であるアルカリ可溶性樹脂を溶解するメチルエチルケトンや１－メトキシ－２－プロパノール等の溶剤に不溶な成分を選択し、上記下層成分を溶解する溶剤系を用いて下層を塗布、乾燥し、その後、アルカリ可溶性樹脂を主体とする上層をメチルエチルケトンや１－メトキシ－２－プロパノール等で溶解し、塗布、乾燥することにより二層化が可能になる。 As a method of utilizing the difference in solvent solubility between the component contained in the lower layer and the component contained in the upper layer, 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 | coating, it becomes possible to isolate | separate each layer clearly and to make a coating film. For example, as the lower layer component, 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. After drying, 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.
　次に、２層目（上層）を塗布後に、極めて速く溶剤を乾燥させる方法としては、ウェブの走行方向に対してほぼ直角に設置したスリットノズルより高圧エアーを吹きつけることや、蒸気等の加熱媒体を内部に供給されたロール（加熱ロール）よりウェブの下面から伝導熱として熱エネルギーを与えること、あるいはそれらを組み合わせることにより達成できる。 Next, after applying the second layer (upper layer), as a method of drying the solvent very quickly, 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.
　本開示に係る平版印刷版原版の支持体上に塗布される下層成分の乾燥後の塗布量は、０．５ｇ／ｍ２～４．０ｇ／ｍ２の範囲にあることが好ましく、０．６ｇ／ｍ２～２．５ｇ／ｍ２の範囲にあることがより好ましい。０．５ｇ／ｍ２以上であると、耐刷性に優れ、４．０ｇ／ｍ２以下であると、画像再現性及び感度に優れる。
　また、上層成分の乾燥後の塗布量は、０．０５ｇ／ｍ２～１．０ｇ／ｍ２の範囲にあることが好ましく、０．０８ｇ／ｍ２～０．７ｇ／ｍ２の範囲であることがより好ましい。０．０５ｇ／ｍ２以上であると、現像ラチチュード、及び、耐傷性に優れ、１．０ｇ／ｍ２以下であると、感度に優れる。
　下層及び上層を合わせた乾燥後の塗布量としては、０．６ｇ／ｍ２～４．０ｇ／ｍ２の範囲にあることが好ましく、０．７ｇ／ｍ２～２．５ｇ／ｍ２の範囲にあることがより好ましい。０．６ｇ／ｍ２以上であると、耐刷性に優れ、４．０ｇ／ｍ２以下であると、画像再現性及び感度に優れる。 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.
＜支持体＞
　本開示に係る平版印刷版原版に使用される支持体としては、必要な強度と耐久性を備えた寸度的に安定な板状物であれば特に制限はなく、例えば、紙、プラスチック（例えば、ポリエチレン、ポリプロピレン、ポリスチレン等）がラミネートされた紙、金属板（例えば、アルミニウム、亜鉛、銅等）、プラスチックフィルム（例えば、二酢酸セルロース、三酢酸セルロース、プロピオン酸セルロース、酪酸セルロース、酢酸酪酸セルロース、硝酸セルロース、ポリエチレンテレフタレート、ポリエチレン、ポリスチレン、ポリプロピレン、ポリカーボネート、ポリビニルアセタール等）、上記の如き金属がラミネート若しくは蒸着された紙、又は、プラスチックフィルム等が挙げられる。 <Support>
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. For example, 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.
　上記支持体としては、ポリエステルフィルム又はアルミニウム板が好ましく、その中でも寸度安定性がよく、比較的安価であるアルミニウム板は特に好ましい。好適なアルミニウム板は、純アルミニウム板及びアルミニウムを主成分とし、微量の異元素を含む合金板であり、更にアルミニウムがラミネート又は蒸着されたプラスチックフィルムでもよい。アルミニウム合金に含まれる異元素には、ケイ素、鉄、マンガン、銅、マグネシウム、クロム、亜鉛、ビスマス、ニッケル、チタンなどがある。合金中の異元素の含有量は１０質量％以下であることが好ましい。 As the above-mentioned support, 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. Examples of 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.
　本開示において特に好適なアルミニウムは、純アルミニウムであるが、完全に純粋なアルミニウムは精錬技術上製造が困難であるので、僅かに異元素を含有するものでもよい。
　このように本開示に適用されるアルミニウム板は、その組成が特定されるものではなく、従来より公知公用の素材のアルミニウム板を適宜に利用することができる。本開示において用いられるアルミニウム板の厚みは、０．１ｍｍ～０．６ｍｍであることが好ましく、０．１５ｍｍ～０．４ｍｍであることがより好ましく、０．２ｍｍ～０．３ｍｍであることが特に好ましい。 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.
　このようなアルミニウム板には、必要に応じて粗面化処理、陽極酸化処理などの表面処理を行ってもよい。アルミニウム支持体の表面処理については、例えば、特開２００９－１７５１９５号公報の段落０１６７～０１６９に詳細に記載されるような、界面活性剤、有機溶剤又はアルカリ性水溶液などによる脱脂処理、表面の粗面化処理、陽極酸化処理などが適宜、施される。
　陽極酸化処理を施されたアルミニウム表面は、必要により親水化処理が施される。
　親水化処理としては、２００９－１７５１９５号公報の段落０１６９に開示されているような、アルカリ金属シリケート（例えばケイ酸ナトリウム水溶液）法、フッ化ジルコン酸カリウムあるいは、ポリビニルホスホン酸で処理する方法などが用いられる。
　また、特開２０１１－２４５８４４号公報に記載された支持体も好ましく用いられる。 Such an aluminum plate may be subjected to a surface treatment such as a roughening treatment or an anodizing treatment as necessary. As for 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.
Examples of the hydrophilization treatment 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.
＜下塗層＞
　本開示に係る平版印刷版原版は、必要に応じて、支持体と画像記録層との間に、下塗層を設けることができる。
　下塗層成分としては、種々の有機化合物が用いられ、例えば、カルボキシメチルセルロース、デキストリン等のアミノ基を有するホスホン酸類、有機ホスホン酸、有機リン酸、有機ホスフィン酸、アミノ酸類、並びに、ヒドロキシ基を有するアミンの塩酸塩等が好ましく挙げられる。また、これら下塗層成分は、１種単独で用いても、２種以上混合して用いてもよい。下塗層に使用される化合物の詳細、下塗層の形成方法は、特開２００９－１７５１９５号公報の段落０１７１～０１７２に記載され、これらの記載は本開示にも適用される。
　下塗層の被覆量は、２ｍｇ／ｍ２～２００ｍｇ／ｍ２であることが好ましく、５ｍｇ／ｍ２～１００ｍｇ／ｍ２であることがより好ましい。被覆量が上記範囲であると、十分な耐刷性能が得られる。 <Undercoat layer>
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.
As an undercoat layer component, various organic compounds are used. For example, 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 . When the coating amount is in the above range, sufficient printing durability can be obtained.
＜バックコート層＞
　本開示に係る平版印刷版原版における上記支持体の上記画像記録層が設けられた側とは反対の面には、必要に応じてバックコート層が設けられることが好ましい。かかるバックコート層としては、特開平５－４５８８５号公報記載の有機高分子化合物及び特開平６－３５１７４号公報記載の有機又は無機金属化合物を加水分解及び重縮合させて得られる金属酸化物からなる被覆層が好ましく用いられる。これらの被覆層のうち、Ｓｉ（ＯＣＨ３）４、Ｓｉ（ＯＣ２Ｈ５）４、Ｓｉ（ＯＣ３Ｈ７）４、Ｓｉ（ＯＣ４Ｈ９）４などのケイ素のアルコキシ化合物が安価で入手し易く、それから得られる金属酸化物の被覆層が耐現像液に優れており特に好ましい。 <Back coat layer>
In the planographic printing plate precursor according to the present disclosure, 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. Such 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. Among these coating layers, 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.
（平版印刷版の作製方法）
　本開示に係る平版印刷版の作製方法は、上記平版印刷版原版を画像露光する露光工程、及び、現像液を用いて現像する現像工程、をこの順で含む。
　上記現像液としては、現像性及び廃液処理の容易性の観点から、ｐＨ１０以下の現像液であることが好ましい。
　以下、本開示に係る平版印刷版の作製方法の各工程について詳細に説明する。 (Preparation method of lithographic printing plate)
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.
Hereinafter, each step of the method for producing a lithographic printing plate according to the present disclosure will be described in detail.
＜露光工程＞
　本開示に係る平版印刷版の作製方法は、本開示に係る平版印刷版原版を画像露光する露光工程を含む。
　本開示に係る平版印刷版原版の画像露光に用いられる活性光線の光源としては、近赤外から赤外領域に発光波長を持つ光源が好ましく、固体レーザー、半導体レーザーがより好ましい。中でも、本開示においては、波長７５０ｎｍ～１，４００ｎｍの赤外線を放射する固体レーザー又は半導体レーザーにより画像露光されることが特に好ましい。
　レーザーの出力は、１００ｍＷ以上が好ましく、露光時間を短縮するため、マルチビームレーザデバイスを用いることが好ましい。また、１画素あたりの露光時間は２０μ秒以内であることが好ましい。
　平版印刷版原版に照射されるエネルギーは、１０ｍＪ／ｃｍ２～３００ｍＪ／ｃｍ２であることが好ましい。上記範囲であると、硬化が十分に進行し、また、レーザーアブレーションを抑制し、画像が損傷を防ぐことができる。 <Exposure process>
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.
As the actinic ray light source used for image exposure of 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. In particular, in the present disclosure, it is particularly preferable to perform image exposure with a solid laser or a semiconductor laser that emits infrared rays having a wavelength of 750 nm to 1,400 nm.
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 μsec.
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.
　本開示における露光は、光源の光ビームをオーバーラップさせて露光することができる。オーバーラップとは、副走査ピッチ幅がビーム径より小さいことをいう。オーバーラップは、例えば、ビーム径をビーム強度の半値幅（ＦＷＨＭ）で表したとき、ＦＷＨＭ／副走査ピッチ幅（オーバーラップ係数）で定量的に表現することができる。本開示ではこのオーバーラップ係数が、０．１以上であることが好ましい。 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. In the present disclosure, the overlap coefficient is preferably 0.1 or more.
　本開示において使用することができる露光装置の光源の走査方式は、特に限定はなく、円筒外面走査方式、円筒内面走査方式、平面走査方式などを用いることができる。また、光源のチャンネルは単チャンネルでもマルチチャンネルでもよいが、円筒外面方式の場合にはマルチチャンネルが好ましく用いられる。 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.
＜現像工程＞
　本開示に係る平版印刷版の作製方法は、現像液を用いて現像する現像工程を含む。
　現像工程に使用される現像液は、ｐＨ１０以下の水溶液が好ましく、ｐＨ２～ｐＨ９の水溶液がより好ましい。
　上記現像液は、処理性の観点から、界面活性剤を含むことが好ましい。
　上記現像液に用いられる界面活性剤は、アニオン性、ノニオン性、カチオン性、及び、両性の界面活性剤のいずれも用いることができるが、既述のように、アニオン性、ノニオン性の界面活性剤が好ましい。
　本開示において現像液に用いられるアニオン性、ノニオン性、カチオン性、及び、両性界面活性剤としては、特開２０１３－１３４３４１号公報の段落０１２８～０１３１に記載の物を使用することができる。 <Development process>
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.
As the surfactant used in the developer, any of anionic, nonionic, cationic and amphoteric surfactants can be used. As described above, anionic and nonionic surfactants are used. Agents are preferred.
As 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.
　また、水に対する安定な溶解性あるいは混濁性の観点から、上記界面活性剤のＨＬＢ値が、６以上であることが好ましく、８以上であることがより好ましい。
　上記現像液に用いられる界面活性剤としては、アニオン性界面活性剤及びノニオン界面活性剤が好ましく、スルホン酸又はスルホン酸塩を含有するアニオン性界面活性剤及び、芳香環とエチレンオキサイド鎖を有するノニオン界面活性剤が特に好ましい。
　界面活性剤は、単独又は組み合わせて使用することができる。
　界面活性剤の現像液中における含有量は、０．０１質量％～１０質量％が好ましく、０．０１質量％～５質量％がより好ましい。 Moreover, from the viewpoint of stable solubility or turbidity in water, the HLB value of the surfactant is preferably 6 or more, and more preferably 8 or more.
As the surfactant used in the developer, 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.
　上記現像液をｐＨ１０以下に保つためには、緩衝剤として炭酸イオン、炭酸水素イオンが存在することで、現像液を長期間使用してもｐＨの変動を抑制でき、ｐＨの変動による現像性低下、現像カス発生等を抑制できる。炭酸イオン、炭酸水素イオンを現像液中に存在させるには、炭酸塩と炭酸水素塩を現像液に加えてもよいし、炭酸塩又は炭酸水素塩を加えた後にｐＨを調整することで、炭酸イオンと炭酸水素イオンを発生させてもよい。炭酸塩及び炭酸水素塩は、特に限定されないが、アルカリ金属塩であることが好ましい。アルカリ金属としては、リチウム、ナトリウム、カリウムが挙げられ、ナトリウムが特に好ましい。これらは単独でも、二種以上を組み合わせて用いてもよい。 In order to keep the developer at a pH of 10 or less, the presence of carbonate ions and hydrogen carbonate ions as buffering agents can suppress pH fluctuations even when the developer is used for a long period of time. The generation of development residue can be suppressed. In order to allow carbonate ions and hydrogen carbonate ions to be present in the developer, 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.
　炭酸塩及び炭酸水素塩の総量は、現像液の全質量に対して、０．３質量％～２０質量％が好ましく、０．５質量％～１０質量％がより好ましく、１質量％～５質量％が特に好ましい。総量が０．３質量％以上であると現像性、処理能力が低下せず、２０質量％以下であると沈殿や結晶を生成し難くなり、更に現像液の廃液処理時、中和の際にゲル化し難くなり、廃液処理に支障をきたさない。 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. When 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.
　また、アルカリ濃度の微少な調整、非画像部画像記録層の溶解を補助する目的で、補足的に他のアルカリ剤、例えば有機アルカリ剤を併用してもよい。有機アルカリ剤としては、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノイソプロピルアミン、ジイソプロピルアミン、トリイソプロピルアミン、ｎ－ブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、エチレンイミン、エチレンジアミン、ピリジン、テトラメチルアンモニウムヒドロキシド等を挙げることができる。これらの他のアルカリ剤は、単独又は２種以上を組み合わせて用いられる。
　上記現像液には上記の他に、湿潤剤、防腐剤、キレート化合物、消泡剤、有機酸、有機溶剤、無機酸、無機塩などを含有することができる。ただし、水溶性高分子化合物を添加すると、特に現像液が疲労した際に版面がベトツキやすくなるため、添加しないことが好ましい。 Further, for the purpose of assisting the fine adjustment of the alkali concentration and the dissolution of the non-image area image recording layer, another alkali agent such as an organic alkali agent may be supplementarily used together. Examples of 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. These other alkaline agents are used alone or in combination of two or more.
In addition to the above, the developer may contain a wetting agent, preservative, chelate compound, antifoaming agent, organic acid, organic solvent, inorganic acid, inorganic salt, and the like. However, when a water-soluble polymer compound is added, the plate surface tends to become sticky especially when the developer is fatigued, so it is preferable not to add it.
　湿潤剤としては、特開２０１３－１３４３４１号公報の段落０１４１に記載の湿潤剤を好適に用いることができる。湿潤剤は単独で用いてもよいが、２種以上併用してもよい。湿潤剤は、現像剤の全質量に対し、０．１質量％～５質量％の量で使用されることが好ましい。 As the wetting agent, 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.
　防腐剤としては、特開２０１３－１３４３４１号公報の段落０１４２に記載の防腐剤を好適に用いることができる。種々のカビ、殺菌に対して効力のあるように２種以上の防腐剤を併用することが好ましい。防腐剤の添加量は、細菌、カビ、酵母等に対して、安定に効力を発揮する量であって、細菌、カビ、酵母の種類によっても異なるが、現像液の全質量に対して、０．０１質量％～４質量％の範囲が好ましい。 As the preservative, 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.
　キレート化合物としては、特開２０１３－１３４３４１号公報の段落０１４３に記載のキレート化合物を好適に用いることができる。キレート剤は現像液組成中に安定に存在し、印刷性を阻害しないものが選ばれる。添加量は、現像液の全質量に対して、０．００１質量％～１．０質量％が好適である。 As the chelate compound, 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.
　消泡剤としては、特開２０１３－１３４３４１号公報の段落０１４４に記載の消泡剤を好適に用いることができる。消泡剤の含有量は、現像液の全重量に対して、０．００１質量％～１．０質量％の範囲が好適である。 As the antifoaming agent, 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.
　有機酸としては、特開２０１３－１３４３４１号公報の段落０１４５に記載の消泡剤を好適に用いることができる。有機酸の含有量は、現像液の全質量に対して、０．０１質量％～０．５質量％が好ましい。 As the organic acid, 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.
　有機溶剤としては、例えば、脂肪族炭化水素類（ヘキサン、ヘプタン、“アイソパーＥ、Ｈ、Ｇ”（エッソ化学（株）製）、ガソリン、若しくは、灯油等）、芳香族炭化水素類（トルエン、キシレン等）、又は、ハロゲン化炭化水素（メチレンジクロライド、エチレンジクロライド、トリクレン、モノクロルベンゼン等）や、極性溶剤が挙げられる。 Examples of the organic solvent 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.
　極性溶剤としては、アルコール類（メタノール、エタノール、プロパノール、イソプロパノール、ベンジルアルコール、エチレングリコールモノメチルエーテル、２－エトキシエタノール等）、ケトン類（メチルエチルケトン、シクロヘキサノン等）、エステル類（酢酸エチル、乳酸メチル、プロピレングリコールモノメチルエーテルアセテート等）、その他（トリエチルホスフェート、トリクレジルホスフェート、Ｎ－フェニルエタノールアミン、Ｎ－フェニルジエタノールアミン等）等が挙げられる。 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.).
　また、上記有機溶剤が水に不溶な場合は、界面活性剤等を用いて水に可溶化して使用することも可能である。現像液が有機溶剤を含有する場合は、安全性、引火性の観点から、溶剤の濃度は４０質量％未満が好ましい。 Further, when the organic solvent is insoluble in water, it can be used after being solubilized in water using a surfactant or the like. When the developer contains an organic solvent, the concentration of the solvent is preferably less than 40% by mass from the viewpoint of safety and flammability.
　無機酸及び無機塩としては、リン酸、メタリン酸、第一リン酸アンモニウム、第二リン酸アンモニウム、第一リン酸ナトリウム、第二リン酸ナトリウム、第一リン酸カリウム、第二リン酸カリウム、トリポリリン酸ナトリウム、ピロリン酸カリウム、ヘキサメタリン酸ナトリウム、硝酸マグネシウム、硝酸ナトリウム、硝酸カリウム、硝酸アンモニウム、硫酸ナトリウム、硫酸カリウム、硫酸アンモニウム、亜硫酸ナトリウム、亜硫酸アンモニウム、硫酸水素ナトリウム、硫酸ニッケルなどが挙げられる。無機塩の含有量は、現像液の全質量に対し、０．０１質量％～０．５質量％が好ましい。 Examples of 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.
　現像の温度は、現像可能であれば特に制限はないが、６０℃以下であることが好ましく、１５℃～４０℃であることがより好ましい。自動現像機を用いる現像処理においては、処理量に応じて現像液が疲労してくることがあるので、補充液又は新鮮な現像液を用いて処理能力を回復させてもよい。現像及び現像後の処理の一例としては、アルカリ現像を行い、後水洗工程でアルカリを除去し、ガム引き工程でガム処理を行い、乾燥工程で乾燥する方法が例示できる。また、他の例としては、炭酸イオン、炭酸水素イオン及び界面活性剤を含有する水溶液を用いることにより、前水洗、現像及びガム引きを同時に行う方法が好ましく例示できる。よって、前水洗工程は特に行わなくともよく、一液を用いるだけで、更には一浴で前水洗、現像及びガム引きを行ったのち、乾燥工程を行うことが好ましい。現像の後は、スクイズローラ等を用いて余剰の現像液を除去してから乾燥を行うことが好ましい。 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. In the development processing using an automatic developing machine, 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. As another example, 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.
　現像工程は、擦り部材を備えた自動処理機により好適に実施することができる。自動処理機としては、例えば、画像露光後の平版印刷版原版を搬送しながら擦り処理を行う、特開平２－２２００６１号公報、特開昭６０－５９３５１号公報に記載の自動処理機や、シリンダー上にセットされた画像露光後の平版印刷版原版を、シリンダーを回転させながら擦り処理を行う、米国特許第５１４８７４６号、同５５６８７６８号、英国特許２２９７７１９号の各明細書に記載の自動処理機等が挙げられる。中でも、擦り部材として、回転ブラシロールを用いる自動処理機が特に好ましい。 The developing process can be preferably carried out by an automatic processor equipped with a rubbing member. As the 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, The automatic processing machine described in each specification of US Pat. Nos. 5,148,746, 5,568,768 and British Patent 2,297,719, etc., which rubs the lithographic printing plate precursor after image exposure set on the surface while rotating the cylinder, etc. Is mentioned. Among these, an automatic processor using a rotating brush roll as the rubbing member is particularly preferable.
　本開示において使用する回転ブラシロールは、画像部の傷つき難さ、更には、平版印刷版原版の支持体における腰の強さ等を考慮して適宜選択することができる。回転ブラシロールとしては、ブラシ素材をプラスチック又は金属のロールに植え付けて形成された公知のものが使用できる。例えば、特開昭５８－１５９５３３号公報、特開平３－１００５５４号公報に記載のものや、実公昭６２－１６７２５３号公報に記載されているような、ブラシ素材を列状に植え込んだ金属又はプラスチックの溝型材を芯となるプラスチック又は金属のロールに隙間なく放射状に巻き付けたブラシロールが使用できる。
　ブラシ素材としては、プラスチック繊維（例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル系、ナイロン６．６、ナイロン６．１０等のポリアミド系、ポリアクリロニトリル、ポリ（メタ）アクリル酸アルキル等のポリアクリル系、ポリプロピレン、ポリスチレン等のポリオレフィン系の合成繊維）を使用することができ、例えば、繊維の毛の直径は２０μｍ～４００μｍ、毛の長さは５ｍｍ～３０ｍｍのものが好適に使用できる。
　回転ブラシロールの外径は３０ｍｍ～２００ｍｍが好ましく、版面を擦るブラシの先端の周速は０．１ｍ／ｓｅｃ～５ｍ／ｓｅｃが好ましい。回転ブラシロールは、複数本用いることが好ましい。 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. As the rotating brush roll, a known one formed by planting a brush material on a plastic or metal roll can be used. For example, as described in Japanese Patent Application Laid-Open No. 58-159533, Japanese Patent Application Laid-Open No. 3-100534, or as disclosed in Japanese Utility Model Publication No. 62-167253, metal or plastic in which brush materials are implanted in rows. 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.
Examples of 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). Polyolefin-based synthetic fibers such as polypropylene and polystyrene), for example, fiber diameters of 20 to 400 μm and hair lengths of 5 to 30 mm can be suitably used.
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.
　回転ブラシロールの回転方向は、平版印刷版原版の搬送方向に対し、同一方向であっても、逆方向であってもよいが、２本以上の回転ブラシロールを使用する場合は、少なくとも１本の回転ブラシロールが同一方向に回転し、少なくとも１本の回転ブラシロールが逆方向に回転することが好ましい。これにより、非画像部の画像記録層の除去が更に確実となる。更に、回転ブラシロールをブラシロールの回転軸方向に揺動させることも効果的である。 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.
　現像工程の後、連続的又は不連続的に乾燥工程を設けることが好ましい。乾燥は熱風、赤外線、遠赤外線等によって行う。
　本開示に係る平版印刷版の作製方法において好適に用いられる自動処理機としては、現像部と乾燥部とを有する装置が用いられ、平版印刷版原版に対して、現像槽で、現像とガム引きとが行われ、その後、乾燥部で乾燥されて平版印刷版が得られる。 It is preferable to provide a drying step continuously or discontinuously after the development step. Drying is performed by hot air, infrared rays, far infrared rays, or the like.
As 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.
　また、耐刷性等の向上を目的として、現像後の印刷版を非常に強い条件で加熱することもできる。加熱温度は、２００℃～５００℃の範囲であることが好ましい。
　このようにして得られた平版印刷版は、オフセット印刷機に掛けられ、多数枚の印刷に好適に用いられる。 Further, for the purpose of improving printing durability, 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.
　以下、実施例により本開示を詳細に説明するが、本開示はこれらに限定されるものではない。なお、本実施例において、「％」、「部」とは、特に断りのない限り、それぞれ「質量％」、「質量部」を意味する。なお、高分子化合物において、特別に規定したもの以外は、分子量は重量平均分子量（Ｍｗ）である。また、重量平均分子量（Ｍｗ）は、ゲル浸透クロマトグラフィー（ＧＰＣ）法によるポリスチレン換算値として測定した値である。
　更に、後述する酸価の単位は、ｍｅｑ／ｇである。 Hereinafter, the present disclosure will be described in detail by way of examples, but the present disclosure is not limited thereto. In this example, “%” and “part” mean “% by mass” and “part by mass”, respectively, unless otherwise specified. In the polymer compound, the molecular weight is a weight average molecular weight (Mw) except for those specifically defined. Moreover, a weight average molecular weight (Mw) is the value measured as a polystyrene conversion value by a gel permeation chromatography (GPC) method.
Furthermore, the unit of the acid value described later is meq / g.
＜特定バインダーポリマーの合成＞
〔モノマーＭ－１～Ｍ－１９の合成〕
－モノマーＭ－１の合成－
　三口フラスコにアセトン：１００ｇと２－イソシアナトエチルメタクリレート（カレンズＭＯＩ、昭和電工（株）製）：１５．５ｇを秤量し、内温が５℃になるよう氷冷した。ここに５－アミノサリチル酸：１５．３ｇを少しずつ添加し、室温に昇温した。そのまま３時間撹拌し、得られた沈殿物をろ取、水洗してＭ－１を得た。 <Synthesis of specific binder polymer>
[Synthesis of Monomers M-1 to M-19]
-Synthesis of Monomer M-1-
In a three-necked flask, acetone: 100 g and 2-isocyanatoethyl methacrylate (Karenz MOI, manufactured by Showa Denko KK): 15.5 g were weighed and cooled with ice so that the internal temperature became 5 ° C. To this, 15.3 g of 5-aminosalicylic acid was added little by little, and the temperature was raised to room temperature. The resulting mixture was stirred for 3 hours, and the resulting precipitate was collected by filtration and washed with water to obtain M-1.
－モノマーＭ－５の合成－
　三口フラスコにアセトニトリル：１００ｇとメタクリル酸無水物：１５．４ｇを秤量し、内温が５℃になるよう氷冷した。ここに５－アミノサリチル酸：１５．３ｇを少しずつ添加した。さらに、水酸化ナトリウム水溶液（水酸化ナトリウム：４ｇと純水：１０ｇの混合液）を少しずつ滴下した。室温に昇温し３時間撹拌した。１Ｎ（１ｍｏｌ／Ｌ）塩酸水を添加し、液のｐＨを４に調整した後、得られた沈殿物をろ取、水洗してＭ－５を得た。 -Synthesis of Monomer M-5-
A three-necked flask was weighed with 100 g of acetonitrile and 15.4 g of methacrylic anhydride, and cooled with ice so that the internal temperature became 5 ° C. To this, 15.3 g of 5-aminosalicylic acid was added little by little. Further, an aqueous sodium hydroxide solution (mixed solution of sodium hydroxide: 4 g and pure water: 10 g) was added dropwise little by little. The mixture was warmed to room temperature and stirred for 3 hours. 1N (1 mol / L) aqueous hydrochloric acid was added to adjust the pH of the solution to 4, and the resulting precipitate was collected by filtration and washed with water to obtain M-5.
－モノマーＭ－１９の合成－
　ディーンスターク管と還流管を取り付けた三口フラスコにトルエン：１００ｇと無水マレイン酸：９．８ｇを秤量し、室温で溶解した。ここにジクロロアミノフェノール１７．８ｇとトシル酸一水和物：１０ｍｇを添加し、脱水条件下１００℃で６時間反応させた。反応後、トルエンを留去し、得られた固形物を水洗し、ろ取し、更に水洗してＭ－１９を得た。 -Synthesis of Monomer M-19-
Toluene: 100 g and maleic anhydride: 9.8 g were weighed and dissolved at room temperature in a three-necked flask equipped with a Dean-Stark tube and a reflux tube. To this, 17.8 g of dichloroaminophenol and 10 mg of tosylic acid monohydrate were added and reacted at 100 ° C. for 6 hours under dehydrating conditions. After the reaction, toluene was distilled off, and the resulting solid was washed with water, collected by filtration, and further washed with water to obtain M-19.
Figure JPOXMLDOC01-appb-C000027
 
Figure JPOXMLDOC01-appb-C000027
 
〔特定バインダーポリマー１～２４、２６～４０の合成〕
三口フラスコ中にジメチルスルホキシド：６４．００ｇを秤量し、窒素気流下７５℃に加熱した。この溶液中に、Ｍ－１：７．７０ｇ、メタクリル酸メチル：２．３０ｇ、Ｖ－６０１（商品名、和光純薬工業（株）製）：０．７９ｇ、ジメチルスルホキシド：１６．００ｇから成る混合溶液を２時間かけて滴下した。滴下終了後、更に２時間反応を続けた。反応後、良く撹拌した水：２０００ｇに注ぐと固体が析出した。析出した固体をろ過し、水洗後減圧下にて乾燥して、特定バインダーポリマー１を得た。
　特定バインダーポリマー２～２４、２６～４０についても、下記表１又は表２に記載のモノマーを使用することにより合成可能した。 [Synthesis of Specific Binder Polymers 1-24, 26-40]
In a three-necked flask, 64.00 g of dimethyl sulfoxide was weighed and heated to 75 ° C. under a nitrogen stream. In this solution, M-1: 7.70 g, methyl methacrylate: 2.30 g, V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.): 0.79 g, dimethyl sulfoxide: 16.00 g The mixed solution was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 2 hours. After the reaction, a solid was precipitated when poured into 2000 g of well stirred water. The precipitated solid was filtered, washed with water and dried under reduced pressure to obtain a specific binder polymer 1.
Specific binder polymers 2 to 24 and 26 to 40 could also be synthesized by using the monomers shown in Table 1 or Table 2 below.
〔特定バインダーポリマー２５の合成〕
　三口フラスコにポリビニルアルコール（重合度５０、ケン化度５０モル％）：６．２５ｇと、水１５０ｍｌ中を秤量し、７０℃に加熱して溶解させた。溶解後に溶液に、濃硫酸０．１ｇを添加した。次いで、２－ヒドロキシ－１－ナフトアルデヒド：３．０ｇを添加し、６時間撹拌を続けた。反応液をよく撹拌した水１０００ｇに加え、沈殿物をろ取し、水、メタノールで十分に洗浄した後、減圧乾燥することにより、特定バインダーポリマー２５を得た。
　得られる特定バインダーポリマー２５は、上述の具体例におけるＡ３－１により表される構成単位を有するポリマーである。 [Synthesis of Specific Binder Polymer 25]
In a three-necked flask, polyvinyl alcohol (polymerization degree 50, saponification degree 50 mol%): 6.25 g and 150 ml of water were weighed and dissolved by heating to 70 ° C. After dissolution, 0.1 g of concentrated sulfuric acid was added to the solution. Next, 3.0 g of 2-hydroxy-1-naphthaldehyde was added and stirring was continued for 6 hours. The reaction liquid was added to 1000 g of well-stirred water, and the precipitate was collected by filtration, washed thoroughly with water and methanol, and then dried under reduced pressure to obtain a specific binder polymer 25.
The obtained specific binder polymer 25 is a polymer having a structural unit represented by A3-1 in the above specific example.
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000029
　表１又は表２中、「式Ａ１～式Ａ３中の構造」の欄には、それぞれ式Ａ１～式Ａ３のいずれかにより表される構成単位において、該当する式中のＡ、Ｒ４及びＺに該当する構造を記載した。Ａの欄の「Ｐｈ」の記載はベンゼン環を、「ｎａｐｈ」の記載はナフタレン環を、「ｐｙｒ」の記載はピリジン環を、それぞれ表している。
　また、「特定バインダーポリマーの酸価」の欄には、上述の方法により測定した「ｐＫａ９以下の酸基による酸価」を記載した。 In Table 1 or Table 2, 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. In the column A, “Ph” represents a benzene ring, “naph” represents a naphthalene ring, and “pyr” represents a pyridine ring.
In the column of “acid value of specific binder polymer”, “acid value by acid group of pKa 9 or less” measured by the above-described method is described.
＜その他のバインダーポリマーの合成＞
　その他のバインダーポリマーとして、下記ポリマー１～ポリマー４を合成した。
　ポリマー１：スチレン／アクリロニトリル／メタクリル酸＝６／１／２（モル比）、重量平均分子量は、２０，０００
　ポリマー２：メタクリル酸メチル／メタクリル酸＝８／２（モル比）、重量平均分子量４０，０００
　ポリマー３：下記構造のポリマー、ａ／ｂ／ｃ／ｄ＝３／３／３／１（モル比）、重量平均分子量は１２０，０００
　ポリマー４：下記構造のポリマー、ａ／ｂ／ｃ＝４／１／５（モル比）、重量平均分子量は２８，０００ <Synthesis of other binder polymers>
The following polymers 1 to 4 were synthesized as other binder polymers.
Polymer 1: Styrene / acrylonitrile / methacrylic acid = 6/1/2 (molar ratio), weight average molecular weight is 20,000
Polymer 2: Methyl methacrylate / methacrylic acid = 8/2 (molar ratio), weight average molecular weight 40,000
Polymer 3: a polymer having the following structure, a / b / c / d = 3/3/3/1 (molar ratio), weight average molecular weight of 120,000
Polymer 4: Polymer having the following structure, a / b / c = 4/1/5 (molar ratio), weight average molecular weight 28,000
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
〔ポリマー１の合成〕
　三口フラスコ中に１―メトキシー２―プロパノール：６４．００ｇ、スチレン：１５．９６ｇを秤量し、窒素気流下７５℃に加熱した。この溶液中に、アクリロニトリル：１．３９ｇ、メタクリル酸：４．２３ｇ、Ｖ－６０１（商品名、和光純薬工業（株）製）：０．７９ｇ、１―メトキシー２―プロパノール：１６．００ｇから成る混合溶液を２時間かけて滴下した。滴下終了後、更に２時間反応を続けた。反応後、良く攪拌した水：２０００ｇに注ぐと固体が析出した。析出した固体をろ過し、水洗後減圧下にて乾燥して、ポリマー１を得た。 [Synthesis of Polymer 1]
In a three-necked flask, 1-methoxy-2-propanol: 64.00 g and styrene: 15.96 g were weighed and heated to 75 ° C. under a nitrogen stream. In this solution, acrylonitrile: 1.39 g, methacrylic acid: 4.23 g, V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.): 0.79 g, 1-methoxy-2-propanol: 16.00 g The resulting mixed solution was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 2 hours. After the reaction, a solid was precipitated when poured into 2000 g of well stirred water. The precipitated solid was filtered, washed with water and dried under reduced pressure to obtain polymer 1.
〔ポリマー２の合成〕
三口フラスコ中に１―メトキシー２―プロパノール：６４．００ｇを秤量し、窒素気流下７５℃に加熱した。この溶液中に、メタクリル酸メチル：１８．５２ｇ、メタクリル酸：４．００ｇ、Ｖ－６０１（商品名、和光純薬工業（株）製）：０．８０ｇ、１―メトキシー２―プロパノール：１６．００ｇから成る混合溶液を２時間かけて滴下した。滴下終了後、更に２時間反応を続けた。反応後、良く攪拌した水：２０００ｇに注ぐと固体が析出した。析出した固体をろ過し、水洗後減圧下にて乾燥して、ポリマー２を得た。 [Synthesis of Polymer 2]
In a three-necked flask, 64.00 g of 1-methoxy-2-propanol was weighed and heated to 75 ° C. under a nitrogen stream. In this solution, methyl methacrylate: 18.52 g, methacrylic acid: 4.00 g, V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.): 0.80 g, 1-methoxy-2-propanol: 16. A mixed solution consisting of 00 g was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 2 hours. After the reaction, a solid was precipitated when poured into 2000 g of well stirred water. The precipitated solid was filtered, washed with water and dried under reduced pressure to obtain polymer 2.
〔ポリマー３の合成〕
　米国特許第６，５４１，１８１号明細書の記載を参考に合成した。 [Synthesis of Polymer 3]
Synthesis was carried out with reference to the description in US Pat. No. 6,541,181.
〔ポリマー４の合成〕
　三口フラスコ中にメチルエチルケトン：１５０ｇ、２，２－ジメチロールプロピオン酸：１２．９ｇ、ジフェニルメタン－４，４’－ジイソシアネート：１４．５ｇ、及び２，４－トリレンジイソシアネート：２．５３ｇを秤量し、６５℃に加熱した。そこにネオスタン（登録商標）Ｕ－６００（日東化成（株）製、無機ビスマス触媒；以下、単に「Ｕ－６００」ともいう）０．６７ｇを添加し、３時間反応させた。反応後、良く攪拌した水：２０００ｇに注ぐと固体が析出した。析出した固体をろ過し、水洗後減圧下にて乾燥して、ポリマー４を得た。 [Synthesis of Polymer 4]
In a three-necked flask, 150 g of methyl ethyl ketone, 2,2-dimethylolpropionic acid: 12.9 g, diphenylmethane-4,4′-diisocyanate: 14.5 g, and 2,4-tolylene diisocyanate: 2.53 g were weighed. Heated to 65 ° C. Thereto, 0.67 g of Neostan (registered trademark) U-600 (manufactured by Nitto Kasei Co., Ltd., inorganic bismuth catalyst; hereinafter also simply referred to as “U-600”) was added and reacted for 3 hours. After the reaction, a solid was precipitated when poured into 2000 g of well stirred water. The precipitated solid was filtered, washed with water and dried under reduced pressure to obtain polymer 4.
（実施例１～４１、及び、比較例１～４）
＜支持体の作製＞
　国際公開第２０１５／１５２２０９号の段落０２２４～０２９７と同様の方法により支持体を製造した。全ての実施例及び比較例にてこの支持体を使用した。 (Examples 1-41 and Comparative Examples 1-4)
<Production of support>
A support was produced in the same manner as in paragraphs 0224 to 0297 of WO2015 / 152209. This support was used in all examples and comparative examples.
＜下塗層の形成＞
　上記支持体上に、以下に示す下塗り層塗布液１を塗布した後、８０℃で１５秒間乾燥し、下塗層を設けた。乾燥後の被覆量は、１５ｍｇ／ｍ2であった。 <Formation of undercoat layer>
After applying the undercoat layer coating solution 1 shown below on the support, it was dried at 80 ° C. for 15 seconds to provide an undercoat layer. The coating amount after drying was 15 mg / m 2 .
〔下塗層塗布液１〕
　・重量平均分子量２．８万の下記共重合体：０．３部
　・メタノール：１００部
　・水：１部 [Undercoat layer coating solution 1]
-The following copolymer having a weight average molecular weight of 28,000: 0.3 parts-Methanol: 100 parts-Water: 1 part
Figure JPOXMLDOC01-appb-C000031
 
Figure JPOXMLDOC01-appb-C000031
 
　上記化学式中、括弧の添字は各構成単位の含有量（質量％）を表す。 In the above chemical formula, the parentheses indicate the content (% by mass) of each structural unit.
＜単層画像記録層の形成＞
　上記のように得られた下塗層を設けた支持体に、下記組成の画像記録層形成用塗布液組成物Ａを、ワイヤーバーで塗布したのち、１５０℃の乾燥オーブンで４０秒間乾燥して単層の画像記録層を設けることにより、ポジ型平版印刷版原版を得た。乾燥後の画像形成層の量は、１．２ｇ／ｍ２であった。 <Formation of single-layer image recording layer>
After applying the coating liquid composition A for forming an image recording layer having the following composition to the support provided with the undercoat layer obtained as described above with a wire bar, it was dried in a drying oven at 150 ° C. for 40 seconds. A positive lithographic printing plate precursor was obtained by providing a single image recording layer. The amount of the image forming layer after drying was 1.2 g / m 2 .
〔画像記録層形成用塗布液組成物Ａ〕
・特定バインダーポリマー：表３に記載の化合物、表３に記載の量
・ノボラック樹脂：ノボラック樹脂（ｍ－クレゾール／ｐ－クレゾール／フェノール＝３／２／５、Ｍｗ８，０００）、表３に記載の量
・その他のバインダーポリマー：表３に記載の化合物、０．２部
・ＩＲ色素（１）：０．０４５部
・メガファックＦ－７８０：０．０３部
・メチルエチルケトン：１５．０部
・１－メトキシ－２－プロパノール：３０．０部
・１－（４－メチルベンジル）－１－フェニルピペリジニウムの５－ベンゾイル－４－ヒドロキシ－２－メトキシベンゼンスルホン酸塩：０．０１部 [Coating liquid composition A for forming image recording layer]
Specific binder polymer: Compound described in Table 3, amount described in Table 3. Novolak resin: Novolak resin (m-cresol / p-cresol / phenol = 3/2/5, Mw 8,000), described in Table 3. Amount of other binder polymer: 0.2 part of the compound described in Table 3, IR dye (1): 0.045 part Megafac F-780: 0.03 part, methyl ethyl ketone: 15.0 parts, 1 -Methoxy-2-propanol: 30.0 parts 1- (4-Methylbenzyl) -1-phenylpiperidinium 5-benzoyl-4-hydroxy-2-methoxybenzenesulfonate: 0.01 parts
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
＜現像性の評価＞
　得られた平版印刷版原版をＣｒｅｏ社製Ｔｒｅｎｄｓｅｔｔｅｒ　ＶＸにて露光エネルギーを変えてテストパターンを画像状に描き込みを行った。その後、現像液１を仕込んだ現像浴に浸漬させ、現像温度３０℃で非画像部の現像に要する時間を測定した。マクベス濃度計により測定した画像濃度が、支持体の画像濃度と同等となった浸漬時間を非画像部現像時間とした。非画像部現像時間が短いほど、現像性が良好である。
　非画像部現像時間（秒）を表３に記載した。 <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.
〔現像液１：ｐＨ＝９．７〕
・水：８９６４部
・炭酸ナトリウム：２００部
・炭酸水素ナトリウム：１００部
・ニューコールＢ４ＳＮ　（商品名、ポリオキシエチレンナフチルエーテル硫酸塩、日本乳化剤（株）製）：３００部
・エチレンジアミンテトラアセテート４ナトリウム塩：８０部 [Developer 1: pH = 9.7]
-Water: 8964 parts-Sodium carbonate: 200 parts-Sodium bicarbonate: 100 parts-New Coal B4SN (trade name, polyoxyethylene naphthyl ether sulfate, manufactured by Nippon Emulsifier Co., Ltd.): 300 parts-Ethylenediaminetetraacetate 4 sodium Salt: 80 parts
＜耐刷性の評価＞
　得られた平版印刷版原版をＣｒｅｏ社製Ｔｒｅｎｄｓｅｔｔｅｒにて、ビーム強度９W、ドラム回転速度１５０ｒｐｍで、テストパターンを画像状に描き込みを行った。その後、現像液１を仕込んだ富士フイルム（株）製ＰＳプロセッサーＬＰ９４０Ｈを用い、現像温度３０℃、現像時間：各実施例又は比較例における上述の非画像部現像時間（秒）＋２秒の条件で現像を行った。これを、小森コーポレーション（株）製印刷機リスロンを用いて連続して印刷した。インキとしては、東洋インキ（株）製特練墨インキを使用した。この際、どれだけの枚数が充分なインキ濃度を保って印刷できるかを目視にて測定し、耐刷性を評価した。
　耐刷性は、下記相対耐刷性を指標として評価した。表３中の数値は下記相対耐刷性（％）の値である。
　相対耐刷性（％）＝各実施例又は比較例における上記印刷枚数／実施例１４における上記印刷枚数×１００ <Evaluation of printing durability>
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. At this time, the number of sheets that can be printed while maintaining a sufficient ink density was measured visually to evaluate the printing durability.
Printing durability was evaluated using the following relative printing durability as an index. The numerical values in Table 3 are the following relative printing durability (%) values.
Relative printing durability (%) = number of printed sheets in each example or comparative example / number of printed sheets in example 14 × 100
＜インキ着肉性（着肉性）の評価＞
　上記耐刷性の評価と同様の条件下において、５０，０００枚印刷を行った時点での版面清浄作業後、更に水拭きを行い、印刷を再開した。印刷再開から画像部にインキが供給され、安定な印物が得られるまでの刷りだし枚数によりインキ着肉性を評価した。上記枚数が少ないほどインキ着肉性に優れる。 <Evaluation of ink fillability>
Under the same conditions as in the evaluation of the printing durability, after the plate surface cleaning operation at the time when 50,000 sheets were printed, further wiping was performed, and printing was resumed. From the restart of printing, ink was supplied to the image area, and ink inking property was evaluated by the number of printed sheets until a stable printed matter was obtained. The smaller the number of sheets, the better the ink deposition property.
＜アブレーション抑制性の評価＞
　平版印刷版原版の表面に、透明な０．１ｍｍ厚さのポリエチレンテレフタレートフイルム（富士フイルム（株）製）を密着させた状態にし、現像性の評価と同様の条件下において全面露光した。露光後にポリエチレンテレフタレートフイルムを外して目視し、表面の汚れ具合を観察した。汚れが認められなかったものをＡ、汚れが若干認められたものをＢ、フイルムを通して向こう側を透かして見えない程度まで汚れたものをＣとして、それぞれ判定した。
　汚れが少ないほどアブレーション抑制性に優れているといえ、評価はＡ又はＢが好ましく、Ａがより好ましい。 <Ablation suppression evaluation>
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, and 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.
　評価結果を、まとめて表３に示す。 Table 3 summarizes the evaluation results.
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033
　特定バインダーポリマーの欄に記載した、比較用１～比較用４のポリマーは、下記表４に記載のモノマーを用いて、特定バインダーポリマー１と同様の方法により合成したポリマーである。 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.
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
　表４中、比較用Ｍ－１～Ｍ－３の詳細は下記の通りである。 In Table 4, the details of comparative M-1 to M-3 are as follows.
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
（実施例４２～４６、及び、比較例５～８）
＜下層及び上層からなる画像記録層の形成＞
　実施例１で得られた下塗層を設けた支持体に、下記組成の下層形成用塗布液組成物Ｂを、ワイヤーバーで塗布したのち、１５０℃の乾燥オーブンで４０秒間乾燥して塗布量を１．０ｇ／ｍ２となるようにし、下層を設けた。下層を設けた後、下記組成の上層形成用塗布液組成物Ｃをワイヤーバーで塗布し上層を設けた。塗布後１５０℃、４０秒間の乾燥を行い、下層と上層を合わせた塗布量が１．２ｇ／ｍ２となる平版印刷版原版を得た。 (Examples 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. After providing the lower layer, the upper layer forming coating liquid composition C having the following composition was applied with a wire bar to provide the upper layer. After coating, 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.
－下層形成用塗布液組成物Ｂ－
・メタクリル酸メチル／メタクリル酸の８０モル％／２０モル％共重合体、重量平均分子量４０，０００：３．５部
・各実施例又は比較例における上層形成用塗布液組成物Ｃと同様の特定バインダーポリマー：０．５部
・ノボラック樹脂（ｍ－クレゾール／ｐ－クレゾール／フェノール＝３／２／５、Ｍｗ８，０００）：０．１部
・ＩＲ色素（１）：０．０４５部
・メガファックＦ－７８０：０．０７部
・メチルエチルケトン：３０．０部
・１－メトキシ－２－プロパノール：１５．０部
・γ－ブチロラクトン：１５．０部
・４，４’－ビスヒドロキシフェニルスルホン：０．３部
・テトラヒドロフタル酸：０．４部
・ｐ－トルエンスルホン酸：０．０２部
・３－メトキシ－４－ジアゾジフェニルアミンヘキサフルオロホスフェート ０．０６部
・エチルバイオレットの対イオンを６－ヒドロキシナフタレンスルホン酸に変えたもの：０．１５部 -Coating liquid composition B for lower layer formation-
-80 mol% / 20 mol% copolymer of methyl methacrylate / methacrylic acid, weight average molecular weight 40,000: 3.5 parts-Specificity similar to coating liquid composition C for upper layer formation in each example or comparative example Binder polymer: 0.5 parts Novolac resin (m-cresol / p-cresol / phenol = 3/2/5, Mw 8,000): 0.1 part IR dye (1): 0.045 part F-780: 0.07 parts, methyl ethyl ketone: 30.0 parts, 1-methoxy-2-propanol: 15.0 parts, γ-butyrolactone: 15.0 parts, 4,4'-bishydroxyphenyl sulfone: 0. 3 parts 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
－上層形成用塗布液組成物Ｃ－
・特定バインダーポリマー：表５～表７に記載の化合物、表５～表７に記載の量
・ノボラック樹脂：ノボラック樹脂（ｍ－クレゾール／ｐ－クレゾール／フェノール＝３／２／５、Ｍｗ８，０００）、表５～表７に記載の量
・その他のバインダーポリマー：表５～表７に記載の化合物、０．２部
・ＩＲ色素（１）：０．０４５部
・メガファックＦ－７８０：０．０３部
・メチルエチルケトン：１５．０部
・１－メトキシ－２－プロパノール：３０．０部
・１－（４－メチルベンジル）－１－フェニルピペリジニウムの５－ベンゾイル－４－ヒドロキシ－２－メトキシベンゼンスルホン酸塩：０．０１部 -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. Novolac resin: novolac resin (m-cresol / p-cresol / phenol = 3/2/5, Mw 8,000 ), Amounts listed in Tables 5 to 7; other binder polymers: compounds listed in Tables 5 to 7, 0.2 parts IR dye (1): 0.045 parts Megafac F-780: 0 0.03 part methyl ethyl ketone: 15.0 parts 1-methoxy-2-propanol: 30.0 parts 1- (4-methylbenzyl) -1-phenylpiperidinium 5-benzoyl-4-hydroxy-2- Methoxybenzene sulfonate: 0.01 part
　実施例４２、及び、比較例５においては、実施例１と同様にして評価した。評価結果を表５に示す。
　実施例４３～４４、及び、比較例６～７においては、現像液１の代わりに下記現像液２を用いた以外は、実施例１と同様にして評価した。評価結果を表６に示す。
　実施例４５、及び、比較例８においては、現像液１の代わりに下記現像液３を用いた以外は、実施例１と同様にして評価した。評価結果を表７に示す。
　実施例４６においては、下層形成用塗布液組成物Ｂ及び上層形成用塗布液組成物ＣにおけるＩＲ色素（１）を、下記ＩＲ色素（２）に変更し、現像液１の代わりに下記現像液３を用いた以外は、実施例１と同様にして評価した。評価結果を表７に示す。 In 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.
In Examples 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.
In 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.
In 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.
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
－現像液２：ｐＨ＝１０．２－
　脱イオン水：６４１．２５部
　塩化カルシウム二水和物：３．７５部
　アクリル酸－マレイン酸共重合体（モル比４０：６０）のナトリウム塩４０％水溶液：２５．０部
　ぺレックスＮＢＬ（アルキルナフタレンスルホン酸ナトリウム、花王（株）製）：１４０．０部
　ベンジルアルコール：３０．０部
　２－（２－アミノエトキシ）エタノール：７５．０部
　トリイソプロパノールアミン：３０．０部
　コハク酸：５．０部 -Developer 2: pH = 10.2-
Deionized water: 641.25 parts Calcium chloride dihydrate: 3.75 parts Sodium salt 40% aqueous solution of acrylic acid-maleic acid copolymer (molar ratio 40:60): 25.0 parts Perex NBL (alkyl) Sodium naphthalenesulfonate, manufactured by Kao Corporation): 140.0 parts benzyl alcohol: 30.0 parts 2- (2-aminoethoxy) ethanol: 75.0 parts triisopropanolamine: 30.0 parts Succinic acid: 5. 0 copies
－現像液３：ｐＨ＝７．０－
　水：８９部
　Ｗ－１（下記化合物）：２．４部
　Ｗ－２（下記化合物）：２．４部
　エマレックス７１０（日本エマルジョン（株）製）：１．０部
　フェノキシプロパノール：１．０部
　オクタノール：０．６部
　Ｎ－（２－ヒドロキシエチル）モルホリン：１．０部
　トリエタノールアミン：０．５部
　グルコン酸ナトリウム：１．０部
　クエン酸三ナトリウム：０．５部
　エチレンジアミンテトラアセテート四ナトリウム塩：０．０５部
　ポリスチレンスルホン酸（Ｖｅｒｓａ　ＴＬ７７（３０％溶液）、Ａｌｃｏ　ｃｈｅｍｉｃａｌ社製）：１．０部
　上記組成の現像液に、リン酸を添加し、ｐＨを７．０に調整し、現像液３とした。 -Developer 3: pH = 7.0-
Water: 89 parts W-1 (the following compound): 2.4 parts W-2 (the following compound): 2.4 parts Emalex 710 (manufactured by Nippon Emulsion Co., Ltd.): 1.0 part Phenoxypropanol: 1.0 Part Octanol: 0.6 part N- (2-hydroxyethyl) morpholine: 1.0 part Triethanolamine: 0.5 part Sodium gluconate: 1.0 part Trisodium citrate: 0.5 part Ethylenediaminetetraacetate tetra Sodium salt: 0.05 part Polystyrene sulfonic acid (Versa TL77 (30% solution), manufactured by Alco chemical): 1.0 part Phosphoric acid is added to the developer having the above composition to adjust the pH to 7.0. Developer 3 was obtained.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-T000038
Figure JPOXMLDOC01-appb-T000038
Figure JPOXMLDOC01-appb-T000039
Figure JPOXMLDOC01-appb-T000039
Figure JPOXMLDOC01-appb-T000040
Figure JPOXMLDOC01-appb-T000040
　表１～表７の記載から、本開示に係る平版印刷版原版は、低ｐＨにおける現像性に優れた平版印刷版が得られる。
　また、本開示に係る平版印刷版原版は、耐刷性、インキ着肉性及びアブレーション抑制性にも優れた平版印刷版が得られることがわかる。
　更に、本開示に係る平版印刷版原版は、耐傷性にも優れることがわかる。 From the descriptions in Tables 1 to 7, 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.
　２０１８年２月２８日に出願された日本国特許出願第２０１８－０３５２０２号の開示は、その全体が参照により本明細書に取り込まれる。
　本明細書に記載された全ての文献、特許出願、及び、技術規格は、個々の文献、特許出願、及び、技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 The disclosure of Japanese Patent Application No. 2018-035202 filed on February 28, 2018 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described in this specification are the same as if each document, patent application, and technical standard were specifically and individually stated to be incorporated by reference. Which is incorporated herein by reference.

Claims (10)

  1. 　支持体と、
    　支持体上に形成された画像記録層と、を有し、
    　前記画像記録層が、
    　下記式Ａ１により表される構成単位、下記式Ａ２により表される構成単位、及び下記式Ａ３により表される構成単位よりなる群から選ばれた少なくとも１種の構成単位を有し、ｐＫａ９以下の酸基による酸価が２ｍｅｑ／ｇ～４ｍｅｑ／ｇであるバインダーポリマー、及び、赤外線吸収剤を含む、
    　ポジ型平版印刷版原版。
    Figure JPOXMLDOC01-appb-C000001
    　式Ａ１中、ＬＡは－Ｃ（＝Ｏ）Ｏ－、－Ｃ（＝Ｏ）ＮＲ５－、又はフェニル基を表し、Ｒ５は水素原子又はアルキル基を表し、ＲＡは式Ｂ１により表される基を表し、Ｒ１は水素原子又はアルキル基を表す。
    　式Ａ２中、ＲＡは式Ｂ１により表される基を表し、Ｒ２及びＲ３はそれぞれ独立に、水素原子又はアルキル基を表す。
    　式Ａ３中、ＲＡは式Ｂ１により表される基を表す。
    　式Ｂ１中、Ｌ１は単結合又は二価の連結基を表し、Ｘ１は単結合、エステル結合、アミド結合、ウレタン結合又はウレア結合を表し、Ａは芳香環構造を表し、Ｚはそれぞれ独立に、ｐＫａ９以下の酸基を表し、ｎは１以上の整数を表し、Ｒ４はそれぞれ独立に、－ＯＲ６、アルキル基、ハロゲン原子、－Ｃ（＝Ｏ）Ｒ７、－Ｃ（＝Ｏ）ＯＲ７又はニトロ基を表し、Ｒ６は水素原子又は炭素数１～４のアルキル基を表し、Ｒ７は炭素数１～４のアルキル基を表し、ｍは０以上の整数を表し、ｍ＋ｎはＡにより表される芳香環構造の最大置換基数以下の数を表し、Ａがベンゼン環構造である場合、ｍは１～４の整数であり、＊は他の構造との結合部位を表す。     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.
    Figure JPOXMLDOC01-appb-C000001
    In Formula A1, L A represents —C (═O) O—, —C (═O) NR 5 —, or a phenyl group, R 5 represents a hydrogen atom or an alkyl group, and R A represents a group represented by Formula B1. R 1 represents a hydrogen atom or an alkyl group.
    In Formula A2, R A represents a group represented by Formula B1, and R 2 and R 3 each independently represent a hydrogen atom or an alkyl group.
    In Formula A3, R A represents a group represented by Formula B1.
    In 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, and Z is independent. Represents an acid group having a pKa of 9 or less, n represents an integer of 1 or more, and R 4 independently represents —OR 6 , an alkyl group, a halogen atom, —C (═O) R 7 , —C (═O ) Represents OR 7 or a nitro group, R 6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 7 represents an alkyl group having 1 to 4 carbon atoms, m represents an integer of 0 or more, and m + n Represents a number equal to or less than the maximum number of substituents of the aromatic ring structure represented by A. When A is a benzene ring structure, m is an integer of 1 to 4, and * represents a binding site with another structure.
  2. 　前記Ｚにより表される酸基がカルボキシ基又はヒドロキシ基である、請求項１に記載のポジ型平版印刷版原版。 The positive lithographic printing plate precursor according to claim 1, wherein the acid group represented by Z is a carboxy group or a hydroxy group.
  3. 　前記Ａにより表される芳香環構造が、ベンゼン環構造、ナフタレン環構造又はピリジン環構造である、請求項１又は請求項２に記載のポジ型平版印刷版原版。 The positive lithographic printing plate precursor according to claim 1 or 2, wherein the aromatic ring structure represented by A is a benzene ring structure, a naphthalene ring structure or a pyridine ring structure.
  4. 　前記Ａにより表される芳香環構造が、ナフタレン環構造又はピリジン環構造であり、前記ｍが０である、請求項１～請求項３のいずれか１項に記載のポジ型平版印刷版原版。 The positive lithographic printing plate precursor as claimed in any one of Claims 1 to 3, wherein the aromatic ring structure represented by A is a naphthalene ring structure or a pyridine ring structure, and the m is 0.
  5. 　前記Ａにより表される芳香環構造が、ベンゼン環構造であり、前記ｍが１である、請求項１～請求項３のいずれか１項に記載のポジ型平版印刷版原版。 The positive lithographic printing plate precursor as claimed in any one of claims 1 to 3, wherein the aromatic ring structure represented by A is a benzene ring structure and the m is 1.
  6. 　前記Ｚにより表される酸基のｐＫａが２．５～７．５である、請求項１～請求項５のいずれか１項に記載のポジ型平版印刷版原版。 The positive planographic printing plate precursor according to any one of claims 1 to 5, wherein the acid group represented by Z has a pKa of 2.5 to 7.5.
  7. 　前記バインダーポリマーの重量平均分子量が８，０００～２０，０００である、請求項１～請求項６のいずれか１項に記載のポジ型平版印刷版原版。 The positive planographic printing plate precursor according to any one of claims 1 to 6, wherein the binder polymer has a weight average molecular weight of 8,000 to 20,000.
  8. 　前記画像記録層が、その他のバインダーポリマーとして、フェノール樹脂、スチレン－アクリロニトリル樹脂、アクリル樹脂、アセタール樹脂、及び、ウレア結合、ウレタン結合又はアミド結合を主鎖に有する樹脂よりなる群から選ばれた少なくとも１種を更に含む、請求項１～請求項７のいずれか１項に記載のポジ型平版印刷版原版。 The image recording layer is at least 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 positive planographic printing plate precursor according to any one of claims 1 to 7, further comprising one kind.
  9. 　前記画像記録層が、下層と上層とを有し、
    　前記バインダーポリマーを含む前記画像記録層が、少なくとも前記下層及び前記上層のいずれかである、請求項１～請求項８のいずれか１項に記載のポジ型平版印刷版原版。     The image recording layer has a lower layer and an upper layer,
    The positive planographic printing plate precursor according to any one of claims 1 to 8, wherein the image recording layer containing the binder polymer is at least one of the lower layer and the upper layer.
  10. 　請求項１～請求項９のいずれか１項に記載のポジ型平版印刷版原版を画像露光する露光工程、及び、
    　露光された前記ポジ型平版印刷版原版をｐＨ１０．０以下の現像液を用いて現像する現像工程、をこの順で含む
    　平版印刷版の作製方法。     An exposure process for image exposure of the positive planographic printing plate precursor according to any one of claims 1 to 9, and
    A method for producing a lithographic printing plate, comprising a development step of developing the exposed positive lithographic printing plate precursor using a developer having a pH of 10.0 or less in this order.
PCT/JP2019/007387 2018-02-28 2019-02-26 Positive lithographic printing plate precursor and method for manufacturing lithographic printing plate WO2019167967A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000035663A (en) * 1998-07-21 2000-02-02 Konica Corp Photosensitive composition and photosensitive lithographic printing plate
JP2001215693A (en) * 2000-02-01 2001-08-10 Konica Corp Image forming material and method of producing the same
JP2006153980A (en) * 2004-11-25 2006-06-15 Fuji Photo Film Co Ltd Lithographic printing original plate
JP2007321104A (en) * 2006-06-02 2007-12-13 Okamoto Kagaku Kogyo Kk Original plate for lithographic printing plate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000035663A (en) * 1998-07-21 2000-02-02 Konica Corp Photosensitive composition and photosensitive lithographic printing plate
JP2001215693A (en) * 2000-02-01 2001-08-10 Konica Corp Image forming material and method of producing the same
JP2006153980A (en) * 2004-11-25 2006-06-15 Fuji Photo Film Co Ltd Lithographic printing original plate
JP2007321104A (en) * 2006-06-02 2007-12-13 Okamoto Kagaku Kogyo Kk Original plate for lithographic printing plate

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