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WO2019013139A1 - Plaque originale d'impression lithographique, procédé de fabrication de plaque d'impression lithographique, composition de coloration, composition durcissable, et matériau de formation d'image - Google Patents

Plaque originale d'impression lithographique, procédé de fabrication de plaque d'impression lithographique, composition de coloration, composition durcissable, et matériau de formation d'image Download PDF

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Publication number
WO2019013139A1
WO2019013139A1 PCT/JP2018/025779 JP2018025779W WO2019013139A1 WO 2019013139 A1 WO2019013139 A1 WO 2019013139A1 JP 2018025779 W JP2018025779 W JP 2018025779W WO 2019013139 A1 WO2019013139 A1 WO 2019013139A1
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WO
WIPO (PCT)
Prior art keywords
group
printing plate
lithographic printing
compound
plate precursor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/025779
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English (en)
Japanese (ja)
Inventor
藤田　明徳
藤牧　一広
啓介 野越
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Fujifilm Corp
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Fujifilm Corp
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Publication of WO2019013139A1 publication Critical patent/WO2019013139A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
    • B41N1/14—Lithographic printing foils
    • 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
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur

Definitions

  • the present disclosure relates to a lithographic printing plate precursor, a method of making a lithographic printing plate, a color forming composition, a curable composition, and an image forming material.
  • a lithographic printing plate comprises an oleophilic image area that receives ink during the printing process and a hydrophilic non-image area that receives dampening water.
  • the lipophilic image area of the lithographic printing plate is an ink receiving area
  • the hydrophilic non-image area is a dampening water receiving area (ink non-receiving area).
  • a lithographic printing plate precursor in which a lipophilic photosensitive resin layer (image recording layer) is provided on a hydrophilic support has hitherto been widely used.
  • PS plate lithographic printing plate precursor
  • a lithographic printing plate is obtained by plate-making by a method of dissolving and removing with a solvent to expose the hydrophilic support surface to form a non-image area.
  • U.S. Pat. No. 5,956,095 comprises a free radically polymerizable component and an initiator composition capable of producing sufficient free radicals to initiate polymerization of said free radically polymerizable component upon exposure to imaging radiation.
  • a radiation sensitive composition comprising a hydrophobic main chain and a polymer binder having a cation covalently linked to the hydrophobic main chain and a salt pendant group comprising a boron containing anion forming a salt with the cation. The thing is described.
  • Patent Document 2 describes an antistatic agent characterized by having a polymerizable functional group composed of a specific compound.
  • Patent Document 1 US Application No. 2008/138741 Specification
  • Patent Document 2 Japanese Patent Application Publication No. 2009-024092
  • a lithographic printing plate excellent in the printable number of plates (hereinafter, also referred to as “printing resistance”) is required.
  • an ink that is cured by irradiation with ultraviolet light (UV) (also referred to as “ultraviolet curable ink”) may be used as the ink in printing.
  • UV curable inks have high productivity because they can be instantaneously dried, generally have a low solvent content, or have no solvent, so environmental pollution is likely to be reduced, they are not dried by heat, or they are heated Since the image can be formed in a short time of drying, it has the advantage of expanding the range of applications such as printing targets.
  • a lithographic printing plate precursor capable of providing a lithographic printing plate excellent in printing durability even when using an ultraviolet curable ink is industrially very useful.
  • the printing durability in the case of using an ultraviolet curable ink is hereinafter also referred to as "UV printing durability".
  • UV printing durability As a result of intensive investigations by the present inventors, in the case of a lithographic printing plate precursor formed using the composition described in Patent Document 1, especially when ultraviolet curable ink is used as the ink, the lithographic printing plate obtained is It has been found that there is a problem that the printing durability is insufficient.
  • Patent Document 2 does not describe or suggest a lithographic printing plate precursor, nor does it describe or suggest a curable composition using an infrared absorber.
  • the problem to be solved by the embodiments of the present invention is to provide a lithographic printing plate precursor from which a lithographic printing plate having excellent printing durability can be obtained even when an ultraviolet-curable ink is used in printing.
  • the problem to be solved by another embodiment of the present invention is to provide a plate making method of a lithographic printing plate which is excellent in printing durability even when an ultraviolet curable ink is used in printing.
  • the problem to be solved by the further embodiment of the present invention is a color forming composition excellent in color forming property, a curable composition excellent in chemical resistance after curing, or an image containing these compositions. It is providing a forming material.
  • ⁇ 1> has an image recording layer on a support, A lithographic printing plate precursor as described above, wherein the image recording layer comprises a compound having a cation moiety having a radical reactive group and an anion moiety containing a boron atom, an infrared absorber, and a radical polymerizable compound.
  • the radical reactive group is a radical polymerizable group or a mercapto group.
  • the lithographic printing plate precursor as described in said ⁇ 1> or ⁇ 2> which is a structure where the said cation part is represented by following formula 1 ⁇ 3>.
  • X represents a group represented by the following Formula 2, a pyridinium group, or an imidazolium group, and Y represents a structure including a radical reactive group.
  • R 5 to R 7 each independently represent an alkyl group or an aryl group, and a plurality of R 5 to R 7 may combine with each other to form a ring; It represents a binding site to Y.
  • R 5 to R 7 each independently represent an alkyl group or an aryl group, and a plurality of R 5 to R 7 may combine with each other to form a ring; It represents a binding site to Y.
  • R 1 to R 4 each independently represent an alkyl group or an aryl group.
  • R 1 to R 4 each independently represent an alkyl group or an aryl group.
  • the image recording layer further contains a radical polymerization initiator ⁇ 8>
  • the radical polymerization initiator is an iodonium salt,
  • the lithographic printing plate precursor as described in said ⁇ 7> containing at least one of a sulfonium salt.
  • ⁇ 9> The lithographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 8> above, wherein the image recording layer further comprises an acid color former.
  • the image recording layer further comprises a polymer particle.
  • the image recording layer further comprises a binder polymer.
  • ⁇ 12> An exposure step of imagewise exposing the lithographic printing plate precursor according to any one of ⁇ 1> to ⁇ 11> above to form an exposed area and an unexposed area, A method for making a lithographic printing plate, comprising an on-press development step of supplying at least one of a printing ink and a dampening solution to remove the unexposed area.
  • An image forming material comprising the color-forming composition as described in ⁇ 13> or the curable composition as described in ⁇ 14>.
  • a lithographic printing plate precursor from which a lithographic printing plate having excellent printing durability can be obtained even when an ultraviolet curable ink is used in printing.
  • a plate making method of a lithographic printing plate which is excellent in printing durability even when an ultraviolet curable ink is used in printing.
  • a color forming composition excellent in color forming property, a curable composition excellent in chemical resistance after curing, or an image forming material comprising these compositions. can do.
  • (meth) acrylic is a term used in a concept including both acrylic and methacrylic
  • (meth) acryloyl is a term used as a concept including both acryloyl and methacryloyl.
  • step in the present specification is not limited to an independent step, and may be referred to as the term if the intended purpose of the step is achieved, even if it can not be clearly distinguished from other steps. included.
  • mass% and “weight%” are synonymous, and “mass part” and “part by weight” are synonymous.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all are trade names manufactured by Tosoh Corporation) unless otherwise noted. It is a molecular weight which is detected using a solvent THF (tetrahydrofuran) and a differential refractometer by a gel permeation chromatography (GPC) analyzer and a polystyrene as a standard substance.
  • the term "planographic printing plate precursor” encompasses not only a lithographic printing plate precursor but also a disposable plate precursor.
  • planographic printing plate includes not only a planographic printing plate prepared by a planographic printing plate precursor through operations such as exposure and development, but also a disposable plate.
  • the operations of exposure and development are not necessarily required.
  • a waste printing plate is a planographic printing plate precursor for attaching to a printing plate cylinder which is not used, for example, in the case of printing a part of the paper with a single color or two colors in newspaper printing of color.
  • a lithographic printing plate precursor according to the present disclosure comprises a compound having an image recording layer on a support, wherein the image recording layer comprises a cation moiety having a radical reactive group and an anion moiety containing a boron atom, an infrared absorber And radically polymerizable compounds. That is, the 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 has a cation moiety having a radical reactive group and a boron atom.
  • the compound which has an anion part containing, an infrared rays absorber, and a radically polymerizable compound are included.
  • a lithographic printing plate precursor according to the present disclosure can provide a lithographic printing plate excellent in printing durability even when using an ultraviolet curable ink in printing. .
  • the detailed mechanism by which the said effect is acquired is unknown, it estimates as follows.
  • a radical compound is generated from the anion portion in the compound having a cation portion having a radical reactive group and an anion portion containing a boron atom.
  • the anion part and the cation part are bonded or electrically attracted to each other, they are considered to be present relatively close to each other in the image recording layer.
  • the radical compound generated from the anion part and the radical reactive group present in the cation part react rapidly, and the reaction (for example, radical polymerization, thiol-ene reaction, etc.) progressed by the radical species is efficiently performed. As a result, it is presumed that the reactant is efficiently generated and the UV printing resistance is improved.
  • a compound that functions as a Lewis acid is also generated from the anion moiety. Therefore, it is considered that a lithographic printing plate having excellent color developability of the image recording layer can be easily obtained by further including in the image recording layer an infrared absorbing agent which develops a color by being decomposed by an acid color former or an acid. Further, as described above, in the lithographic printing plate precursor according to the present disclosure, it is considered that the radical compound and the radical reactive group react rapidly, that is, the generated radical compound is rapidly consumed. The consumption of the radical compound is considered to shift the chemical equilibrium of the reaction to the side where the radical compound is generated, thereby increasing the amount of the compound acting as a Lewis acid.
  • the lithographic printing plate precursor in the case where the image recording layer further includes an infrared color-developing agent or an infrared absorbing agent that develops a color upon being decomposed by an acid, a lithographic printing having excellent color development in the exposed area It is thought that the original plate can be easily obtained.
  • the lithographic printing plate precursor which is excellent in the visibility of an exposure location is obtained.
  • the above-mentioned phenyl radical reacts with the ethylenically unsaturated group present in the cation part in the compound A-1, and the polymerization reaction proceeds. Since the cation part and the anion part in the compound A-1 are bonded or exist at relatively close positions due to the electric attraction even if they are not bonded, when the above reaction proceeds efficiently Conceivable.
  • the image recording layer in the present disclosure is a compound having a cation portion having a radical reactive group and an anion portion containing a boron atom (hereinafter, also referred to as a “specific compound”), an infrared absorber, and a radical polymerizable compound. Including.
  • the image recording layer used in the present disclosure is preferably a negative image recording layer, and more preferably a water-soluble or water-dispersible negative image recording layer.
  • the image recording layer used in the present disclosure preferably further contains a polymerization initiator and a polymerizable compound from the viewpoint of printing durability and photosensitivity.
  • the lithographic printing plate precursor according to the present disclosure is preferably removable from the unexposed area of the image recording layer by at least one of dampening water and printing ink, from the viewpoint of on-press developability.
  • dampening water and printing ink from the viewpoint of on-press developability.
  • the specific compound has a cation moiety having a radical reactive group and an anion moiety containing a boron atom.
  • the cation part and the anion part may be bound or dissociated in the image recording layer.
  • the cation moiety represents a covalently linked atomic group containing a cationic group such as quaternary ammonium group, pyridinium group, imidazolium group and the like.
  • the anion moiety represents a covalently linked atomic group including an anionic structure such as a borate anion structure.
  • the cation moiety is preferably a compound having a cationic group and a radical reactive group.
  • the cationic group is not particularly limited, but is preferably a cationic group having a positive charge on a nitrogen atom from the viewpoint of the thermal stability of the cation moiety, and is preferably a quaternary ammonium group, a pyridinium group, or an imidazo group. More preferably, it is a lithium group, and more preferably a quaternary ammonium group.
  • the radically reactive group is not particularly limited, but is preferably a radically polymerizable group or a mercapto group. From the viewpoint of the polymerization reaction with the radically polymerizable compound, the radically reactive group is preferably a radically polymerizable group. Further, from the viewpoint of suppression of reaction inhibition by oxygen, the radical reactive group is preferably a mercapto group.
  • the radically polymerizable group is preferably a group having an ethylenically unsaturated group from the viewpoint of UV printing resistance, and a (meth) acryloxy group, a (meth) acrylamide group, or a vinylphenyl group is preferable.
  • the cation moiety may have a plurality of radical reactive groups, but preferably has only one radical reactive group.
  • the cation moiety is preferably a structure represented by the following formula 1.
  • X represents a group represented by the following Formula 2, a pyridinium group, or an imidazolium group, and Y represents a structure including a radical reactive group.
  • R 5 to R 7 each independently represent an alkyl group or an aryl group, and a plurality of R 5 to R 7 may combine with each other to form a ring; It represents a binding site to Y.
  • X is preferably a group represented by formula 2.
  • R 5 to R 7 each independently preferably represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and preferably 1 to 4 carbon atoms. It is more preferable that it represents an alkyl group of 6 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group. Further, it is preferable that at least two of R 5 to R 7 represent an alkyl group, and it is more preferable that all three represent an alkyl group.
  • Y represents a structure containing a radical reactive group, and is preferably a structure represented by the following Formula Y-1.
  • L 1 represents a divalent linking group
  • P 1 represents a radical reactive group
  • ⁇ represents a bonding site to X in Formula 1.
  • L 1 is preferably an alkylene group, an arylene group or a group represented by a bond thereof, and is preferably an alkylene group having 2 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms or a bond thereof
  • P 1 represents a radical reactive group, preferably a radical polymerizable group or a mercapto group, and more preferably a radical polymerizable group.
  • a radical reactive group preferably a radical polymerizable group or a mercapto group, and more preferably a radical polymerizable group.
  • a radically polymerizable group a group containing an ethylenically unsaturated group is preferable, and a group containing a terminal ethylenically unsaturated group is more preferable, and a (meth) acryloxy group, a (meth) acrylamide group, or a vinylphenyl group is further added preferable.
  • the molecular weight of the cation moiety is preferably 59 to 1,000, more preferably 90 to 300, and still more preferably 100 to 250.
  • the molecular weight of the cation moiety is determined by arithmetic calculation from the structure determination of the cation moiety.
  • the anion moiety preferably has a negative charge on a boron atom, more preferably a quaternary boron anion, still more preferably a tetraaryl borate anion, and particularly preferably a tetraphenyl borate anion.
  • the tetraphenyl borate anion refers to a quaternary boron anion represented by the following formula.
  • the four aryl groups in the tetraaryl borate anion or the four phenyl groups in the tetraphenyl borate anion may each independently have a substituent, and preferred substituents include a halogen atom, an alkyl group, and a haloalkyl. Groups, alkoxy groups, cyano groups and the like.
  • a haloalkyl group refers to a group in which all hydrogen atoms of an alkyl group are substituted by halogen atoms.
  • the anion moiety is preferably a structure represented by the following formula 3.
  • R 1 to R 4 each independently represent an alkyl group or an aryl group.
  • R 1 to R 4 are each independently preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, methyl Groups or phenyl groups are more preferred, with phenyl groups being particularly preferred.
  • the said alkyl group may be substituted, and a halogen atom, an alkoxy group etc. are mentioned as a preferable substituent.
  • the aryl group may be substituted, and preferred examples of the substituent include a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group and a cyano group.
  • R 1 to R 4 are preferably phenyl groups, more preferably at least three are phenyl groups, and still more preferably all four are phenyl groups.
  • the molecular weight of the specific compound according to the present disclosure is preferably 100 to 1000, more preferably 300 to 800, and still more preferably 400 to 600.
  • the image recording layer in the present disclosure may contain the specific compound singly or in combination of two or more.
  • the content of the specific compound in the present disclosure is preferably 0.001% by mass to 30% by mass, and more preferably 0.01% by mass or more, with respect to the total mass of the image recording layer, from the viewpoint of improving UV printing resistance. It is more preferably 10% by mass, further preferably 0.1% by mass to 5% by mass.
  • the image recording layer in the present disclosure contains an infrared absorber.
  • the infrared absorber has a function of converting the absorbed infrared ray into heat and a function of being excited by the infrared ray to perform electron transfer and / or energy transfer to a polymerization initiator described later.
  • the infrared absorber used in the present disclosure is preferably a dye or a pigment having an absorption maximum at a wavelength of 700 nm to 1,400 nm, more preferably a dye.
  • the dye those described in paragraphs 0082 to 0088 of JP-A-2014-104631 can be used.
  • the average particle diameter of the pigment is preferably 0.01 ⁇ m to 1 ⁇ m, and more preferably 0.01 ⁇ m to 0.5 ⁇ m.
  • known dispersion techniques used for ink production, toner production, etc. can be used. The details are described in "Latest Pigment Application Technology” (CMC Publishing, 1986).
  • the infrared absorber is preferably a compound having a cyanine structure, more preferably a compound having a cyanine structure having an indolenine nucleus, and particularly preferably an electron-attracting group such as a halogen atom at the indolenine nucleus. It is a substituted compound.
  • the infrared absorber an infrared absorber which is decomposed by an acid to develop color is preferably used. Since the compound which acts as a Lewis acid is also generated from the anion part in the specific compound, the image recording layer in the planographic printing plate precursor according to the present disclosure contains an infrared absorbing agent which is colored by decomposition by acid. It is easy to obtain a lithographic printing plate excellent in color development of
  • mother nucleus structures A-1 to A-54, counter anions B-1 to B-10 and counter cations C-1 to C-3 can be mentioned.
  • the present invention is not limited to this.
  • specific examples of the compound represented by the formula 1 include mother nucleus structures A-1 to A-9, A-11 to A-20 and A-22 to A-54, and counter anions B-1 to B-.
  • 10 is a compound in which each of 10 and 10 is combined, and a compound in which each of mother nucleus structures A-10 and A-21 and counter cations C-1 to C-3 is combined.
  • the method for producing the compound represented by the formula 1 is not particularly limited, and the compound can be produced with reference to known methods for producing cyanine dyes. In addition, the method described in WO 2016/027886 can also be suitably used.
  • the infrared absorber may be used alone or in combination of two or more.
  • the content of the infrared absorber is preferably 0.05% by mass to 30% by mass, more preferably 0.1% by mass to 20% by mass, and more preferably 0.2% by mass to 10% by mass with respect to the total mass of the image recording layer. % Is particularly preferred.
  • the image recording layer in the present disclosure contains a radically polymerizable compound.
  • the radically polymerizable compound used in the image recording layer is preferably an addition polymerizable compound (ethylenically unsaturated compound) having at least one ethylenically unsaturated bond.
  • ethylenically unsaturated compound a compound having at least one terminal ethylenic unsaturated bond is preferable, and a compound having two or more terminal ethylenic unsaturated bonds is more preferable.
  • the radically polymerizable compounds can have chemical forms, such as, for example, monomers, prepolymers, ie, dimers, trimers or oligomers, or mixtures thereof.
  • the monomer examples include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid), esters thereof and amides thereof.
  • esters of unsaturated carboxylic acid and polyhydric alcohol compound, and amides of unsaturated carboxylic acid and polyhydric amine compound are used.
  • addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxy group, amino group and mercapto group with monofunctional or polyfunctional isocyanates or epoxies, and monofunctional or monofunctional Dehydration condensation products with polyfunctional carboxylic acids and the like are also suitably used.
  • unsaturated carboxylic acid esters having an electrophilic substituent such as an isocyanate group and an epoxy group, or an addition reaction product of an amide with a monofunctional or polyfunctional alcohol, an amine or a thiol, and a halogen atom are also suitable.
  • substitution products of unsaturated carboxylic acid esters or amides having a leaving substituent such as tosyloxy group and amides with monofunctional or polyfunctional alcohols, amines, and thiols.
  • a compound group in which the above-mentioned unsaturated carboxylic acid is replaced by unsaturated phosphonic acid, styrene, vinyl ether and the like can also be used.
  • monomers of esters of polyhydric alcohol compounds and unsaturated carboxylic acids include, as acrylic acid esters, ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, and the like.
  • examples thereof include trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, ethylene oxide (EO) isocyanurate modified triacrylate, and polyester acrylate oligomer.
  • methacrylic acid ester As methacrylic acid ester, tetramethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, pentaerythritol trimethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] Dimethylmethane, bis [p- (methacryloxyethoxy) phenyl] dimethylmethane and the like.
  • monomers of amides of a polyvalent amine compound and an unsaturated carboxylic acid include methylenebisacrylamide, methylenebismethacrylamide, 1,6-hexamethylenebisacrylamide, 1,6-hexamethylenebismethacrylamide, There are diethylene triamine tris acrylamide, xylylene bis acrylamide, xylylene bis methacrylamide and the like.
  • urethane addition polymerization compounds produced by using an addition reaction of an isocyanate and a hydroxy group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708.
  • Vinyl containing two or more polymerizable vinyl groups in one molecule obtained by adding a hydroxyl group-containing vinyl monomer represented by the following formula (M) to a polyisocyanate compound having two or more isocyanate groups Urethane compounds and the like can be mentioned.
  • CH 2 C (R M4 ) COOCH 2 CH (R M5 ) OH (M)
  • R M4 and R M5 each independently represent a hydrogen atom or a methyl group.
  • Urethane Compounds Having an Oxide-Based Skeleton, U.S. Pat. Nos. 7,153,632, JP-A-8-505,598, JP-A-2007-293221, JP-A-2007-293223, and Urethane Compounds Having a Hydrophilic Group are also suitable.
  • the content of the radically polymerizable compound is preferably 5% by mass to 75% by mass, more preferably 10% by mass to 70% by mass, particularly preferably 15% by mass to 60% by mass, based on the total mass of the image recording layer. It is.
  • the image recording layer used in the present disclosure preferably contains a radical polymerization initiator.
  • the radical polymerization initiator used in the image recording layer is a compound which generates radical species by light and / or heat energy, and is a known thermal polymerization initiator, a compound having a small bond dissociation energy, photopolymerization initiation It can be selected appropriately from agents and the like.
  • a radical polymerization initiator an infrared photosensitive polymerization initiator is preferable.
  • radical polymerization initiators include (a) organic halides, (b) carbonyl compounds, (c) azo compounds, (d) organic peroxides, (e) metallocene compounds, (f) azide compounds, (g) ) Hexaarylbiimidazole compounds, (h) organic borate compounds, (i) disulfone compounds, (j) oxime ester compounds, (k) onium salt compounds.
  • organic halide (a) for example, compounds described in paragraphs 0022 to 0023 of JP-A-2008-195018 are preferable.
  • B) As a carbonyl compound, the compound as described in stage 0024 of Unexamined-Japanese-Patent No. 2008-195018 is preferable, for example.
  • the azo compound (c) include the azo compounds described in JP-A-8-108621.
  • the organic peroxide (d) for example, a compound described in paragraph 0025 of JP-A-2008-195018 is preferable.
  • E As a metallocene compound, the compound as described in Paragraph 0026 of Unexamined-Japanese-Patent No.
  • the azide compound (f) examples include compounds such as 2,6-bis (4-azidobenzylidene) -4-methylcyclohexanone.
  • the compound as described in stage 0027 of Unexamined-Japanese-Patent No. 2008-195018 is preferable, for example.
  • the organic borate compound (h) for example, compounds described in paragraph 0028 of JP-A-2008-195018 are preferable.
  • the disulfone compound (i) examples include compounds described in JP-A-61-166544 and JP-A-2002-328465.
  • the oxime ester compound (j) for example, compounds described in paragraphs 0028 to 0030 of JP-A-2008-195018 are preferable.
  • radical polymerization initiators an oxime ester and an onium salt are mentioned as more preferable ones from the viewpoint of curability, and onium salts such as iodonium salts, sulfonium salts and azinium salts are more preferable, iodonium salts and sulfonium salts It is particularly preferred to include at least one of For use in a lithographic printing plate precursor, iodonium salts and sulfonium salts are particularly preferred. Specific examples of iodonium salts and sulfonium salts are shown below, but the present disclosure is not limited thereto.
  • diphenyliodonium salt is preferable, and in particular, diphenyliodonium salt having an electron donating group as a substituent, for example, diphenyliodonium salt substituted with an alkyl group or an alkoxyl group is preferable, and asymmetric diphenyliodonium salt is also preferable. preferable.
  • sulfonium salts are preferably triarylsulfonium salts, particularly preferably triarylsulfonium salts having an electron withdrawing group as a substituent, for example, a triarylsulfonium salt in which at least a part of the group on the aromatic ring is substituted with a halogen atom.
  • triarylsulfonium salts in which the total substitution number of halogen atoms on the aromatic ring is 4 or more are more preferable.
  • triphenylsulfonium hexafluorophosphate
  • triphenylsulfonium benzoyl formate
  • bis (4-chlorophenyl) phenylsulfonium benzoyl formate
  • bis (4-chlorophenyl) -4-methylphenylsulfonium tetrafluoro Borate
  • tris (4-chlorophenyl) sulfonium 3,5-bis (methoxycarbonyl) benzenesulfonate
  • tris (4-chlorophenyl) sulfonium hexafluorophosphate
  • the above iodonium salt and sulfonium salt are replaced with a counter anion such as hexafluorophosphate from the viewpoint of the heat temporal stability of the lithographic printing plate precursor, and a sulfonamide anion structure and ring structure directly bonded to the ring structure as a counter anion And an organic anion having at least one member selected from the group consisting of a sulfoneimide anion structure directly bonded to
  • the heat aging stability of the lithographic printing plate precursor refers to the property that the developability of the lithographic printing plate precursor is excellent even when stored at high temperature (for example, storage at 60 ° C. for 4 days).
  • the sulfonamide anion structure is an anion structure represented by the following formula.
  • each * independently represents a binding site to another structure. Furthermore, it is more preferable that at least one * be directly bonded to the ring structure, and both * be directly bonded to the ring structure.
  • the sulfone imide anion structure is an anion structure represented by the following formula.
  • each * independently represents a binding site to another structure. Furthermore, it is more preferable that at least one * be directly bonded to the ring structure, and both * be directly bonded to the ring structure.
  • the organic anion is one in which a negative charge is present on a nitrogen atom, but it may also be described, for example, by a resonance structure, and may be a structure in which a negative charge is present other than a nitrogen atom.
  • a resonance structure for example, the resonance structure in the sulfoneimide anion is described below as an example.
  • the ring structure in the sulfonamide anion structure directly bonded to the ring structure or the sulfoneimide anion structure directly bonded to the ring structure is not particularly limited, but an aromatic hydrocarbon ring, an alicyclic hydrocarbon ring, a heterocyclic ring, etc. It can be mentioned.
  • the aromatic hydrocarbon ring includes an aromatic hydrocarbon ring having 6 to 20 carbon atoms, and specific examples include benzene, naphthalene, anthraquinone and the like.
  • the alicyclic hydrocarbon ring includes an alicyclic hydrocarbon ring having 3 to 30 carbon atoms.
  • the alicyclic hydrocarbon ring may have an unsaturated bond.
  • the heterocycle is a heterocycle containing at least one hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom.
  • the heterocyclic ring is preferably a 5- to 8-membered ring.
  • the heterocycle may be saturated or unsaturated.
  • the heterocycle is preferably an aromatic heterocycle. Examples of the heterocyclic ring include pyridine ring, pyrimidine ring, pyrroline ring and the like.
  • the organic anion in the present disclosure is preferably an organic anion represented by the following formula I.
  • the organic anion which concerns on this indication can be represented by several resonance structural formula according to an electronic configuration like general anion, in this specification, as shown below, the negative charge on a nitrogen atom is shown. It describes using the resonance structural formula which has.
  • Cy represents an aryl group, a heteroaryl group, or an alicyclic group which may have an unsaturated bond
  • X represents an alkyl group, an aryl group, a heteroaryl group, SO 2 Ra , SOR b , COR c , PO 3 R d , PO (R e ) (R f ), or H.
  • R a , R b , R c , R d , R e and R f each represent a group selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, and H.
  • R a , R b , R c , R d , R e or R f may combine with Cy to form a ring.
  • the aryl group represented by Cy is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms.
  • a phenyl group, a naphthyl group, etc. are mentioned, A phenyl group etc. are preferable.
  • the heteroaryl group represented by Cy is a group formed from a heterocycle containing at least one hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom.
  • the heterocycle is preferably a 5- to 8-membered ring, more preferably a 5- to 6-membered ring.
  • Examples of the heteroaryl group include pyridyl group, pyrimidyl group, pyrrolyl group, furanyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, indolyl group, quinolinyl group, oxadiazolyl group, benzoxazolyl group and the like. .
  • the alicyclic group represented by Cy is a group formed from an alicyclic ring having 3 to 30 carbon atoms, preferably an alicyclic ring having 4 to 9 carbon atoms.
  • the alicyclic ring may be monocyclic or polycyclic.
  • the alicyclic ring may have an unsaturated bond.
  • Examples of the alicyclic group which may have an unsaturated bond include cyclopentanyl group, cyclopentadienyl group, cyclohexenyl group, cyclohexadienyl group, cycloheptanyl group, cycloheptadienyl group, norbornene group and the like It can be mentioned.
  • the above aryl group, heteroaryl group or heteroaryl group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an aryloxy group, an aryl group, a carbonyl group and an alkoxycarbonyl group. , Cyano group, amido group, urea group, urethane group, alkenyl group, allyl group, acryl group, acryl group, methacryl group, acrylamide group, methacrylamide group, a group formed by combining one or more of halogen atoms, etc.
  • the alkyl group represented by X is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 8 carbon atoms. It may be linear or branched.
  • alkyl group examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl and tert-octyl Groups, nonyl groups, decyl groups, dodecyl groups, ethylhexyl groups and the like.
  • the alkyl group is preferably a methyl group, an ethyl group or a tert-butyl group.
  • aryl group and heteroaryl group represented by X in Formula (I) have the same meanings as the aryl group and heteroaryl group represented by Cy in Formula (I), and the preferred range is also the same.
  • the alkyl group, aryl group and heteroaryl group represented by R a , R b , R c , R d , R e and R f in the formula I are the alkyl groups represented by X in the formula (I) It is synonymous with a group, an aryl group, and a heteroaryl group, and its preferable range is also synonymous.
  • the alkoxy group represented by R a , R b , R c , R d , R e and R f in the formula I is preferably an alkoxy group having 1 to 20 carbon atoms, and the alkoxy group having 1 to 16 carbon atoms is preferably More preferred is an alkoxy group having 1 to 12 carbon atoms.
  • the alkyl group, aryl group or heteroaryl group represented by X above may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an aryloxy group, an aryl group and a carbonyl group. , Alkoxycarbonyl group, cyano group, amido group, urea group, urethane group, alkenyl group, allyl group, acryl group, acryl group, methacryl group, acrylamide group, methacrylamide group, halogen atom, or two or more of them are combined Groups and the like.
  • the alkyl group, alkoxy group, aryl group or heteroaryl group represented by Ra , Rb , Rc , Rd , Re , Rf and Rg may have a substituent.
  • substituents include an alkyl group, an alkoxy group, an aryloxy group, an aryl group, a carbonyl group, an alkoxycarbonyl group, a cyano group, an amido group, a urea group, a urethane group, an alkenyl group, an allyl group, an acrylic group and a methacryl group.
  • substituent include groups in which one or two or more of a group, an acrylamide group, a methacrylamide group, and a halogen atom are combined.
  • an alkyl group, a heteroaryl group, SO 2 R a , SOR b , COR c , PO 3 R d , PO (R e ) (R f ) or H is preferable.
  • R a , R b , R c , R d , R e or R f may combine with Cy to form a ring.
  • R a is SO 2 R a
  • R a is H (hydrogen atom)
  • R a is bonded to Cy to form a ring
  • H as R a is eliminated and SO 2 is C y It represents that it combines with.
  • the organic anion in the present disclosure is preferably an organic anion represented by the following formula II.
  • Cy represents an aryl group, a heteroaryl group, an alicyclic group which may have an unsaturated bond
  • R a represents a group consisting of an alkyl group, an alkoxy group, an aryl group, a heteroaryl group
  • H represents a group selected from R a may combine with Cy to form a ring.
  • an aryl group represented by Cy, a heteroaryl group, and an alicyclic group which may have an unsaturated bond are the aryl group represented by Cy in Formula I, a heteroaryl group, and It is synonymous with the alicyclic group which may have an unsaturated bond, and its preferable range is also synonymous.
  • the aryl group, heteroaryl group or heteroaryl group represented by Cy above may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an aryloxy group, an aryl group, a carbonyl Or one or more of a group, alkoxycarbonyl group, cyano group, amido group, urea group, urethane group, alkenyl group, allyl group, acryl group, acryl group, methacryl group, acrylamide group, methacrylamide group, halogen atom And the like.
  • the alkyl group, alkoxy group, aryl group or heteroaryl group represented by R a may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an aryloxy group, an aryl Group, carbonyl group, alkoxycarbonyl group, cyano group, amido group, urea group, urethane group, alkenyl group, allyl group, acryl group, acryl group, methacryl group, acrylamide group, methacrylamide group, halogen atom, one or more of And the like.
  • organic anion in the present disclosure is preferably an organic anion represented by the following Formula III or Formula IV.
  • R 1 to R 10 each independently represent a hydrogen atom or a monovalent substituent.
  • R 11 to R 14 each independently represent a hydrogen atom or a monovalent substituent.
  • the monovalent substituent represented by R 1 to R 10 in the formula III is not particularly limited as long as the effects of the present disclosure are not impaired, and examples thereof include an alkyl group (having 1 to 12 carbon atoms).
  • an alkyl group having 1 to 10 carbon atoms
  • still more preferred is an alkyl group having 1 to 8 carbon atoms.
  • the alkyl group may be linear or branched, alkoxy group (alkoxy group)
  • the alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 8 carbon atoms, and the alkyl group may be linear or branched.
  • aryloxy groups (the aryl group in the aryloxy group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and 6 to 10 carbon atoms.
  • An aryl group is more preferable)
  • an aryl group (an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 15 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable), a carbonyl group And the alkoxycarbonyl group
  • the alkyl group in the alkoxy group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 8 carbon atoms.
  • It may be linear or branched), cyano group, amido group, urea group, urethane group, alkenyl group (preferably, alkenyl group having 2 to 15, more preferably 2 to 6 carbon atoms), allyl group, acrylic Group, methacryl group, acrylamide group, methacrylamide group, halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom) Be mentioned include groups composed by combining the two or more kinds. The group mentioned as the monovalent substituent may be further substituted by another group.
  • a hydrogen atom and the above-mentioned monovalent substituent are preferable, and an alkyl group, a halogen group and an alkoxycarbonyl group are more preferable.
  • an alkyl group (an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, carbon
  • the alkyl group is more preferably an alkyl group of 1 to 8.
  • the alkyl group may be linear or branched, or an alkoxy group (the alkyl group in the alkoxy group is preferably an alkyl group having 1 to 12 carbon atoms, 1 to 12 carbon atoms).
  • An alkyl group of 10 is more preferable, and an alkyl group having 1 to 8 carbon atoms is further preferable.
  • the alkyl group may be linear or branched, and an aryloxy group (an aryl group in the aryloxy group has 6 carbon atoms)
  • An aryl group of -20 is preferable, an aryl group having 6 to 15 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is still more preferable, an aryl group (an aryl group having 6 to 20 carbon atoms) Group is preferable, an aryl group having 6 to 15 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is still more preferable, an aryl group (an aryl group having 6 to 20 carbon atoms is preferable, 6 to 15 carbon atoms).
  • the aryl group is more preferably an aryl group having 6 to 10 carbon atoms.
  • a carbonyl group or an alkoxycarbonyl group (the alkyl group in the alkoxy group is preferably an alkyl group having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms).
  • the alkyl group is more preferably an alkyl group having 1 to 8 carbon atoms, which may be linear or branched), cyano group, amido group, urea group, urethane group, alkenyl group (preferably Is an alkenyl group having a carbon number of 2 to 15, more preferably 2 to 6), an allyl group, an acryl group, a methacryl group, an acrylamide group, methacrylamide De group, a halogen atom (such as fluorine atom, chlorine atom, bromine atom or iodine atom) one or more are combined comprising group can be mentioned.
  • the group mentioned as the monovalent substituent may be further substituted by another group.
  • a hydrogen atom and the above-mentioned monovalent substituent are preferable, and an alkyl group, a halogen group and an alkoxycarbonyl group are more preferable.
  • Formula III Also included in Formula III are those comprising more than one sulfoneimide anion structure via any of R 1 -R 10 .
  • organic anion examples include a phenyl group, Me represents a methyl group, and Et represents an ethyl group.
  • the radical polymerization initiator may be used alone or in combination of two or more.
  • the content of the radical polymerization initiator is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, particularly preferably 0.8% by mass, with respect to the total mass of the image recording layer. It is mass% to 20 mass%.
  • the image recording layer used in the present disclosure preferably contains an acid color former.
  • the “acid color former” used in the present disclosure means a compound having a property of developing a color by heating in a state where an electron accepting compound (for example, a proton such as an acid) is received.
  • an acid color developing agent particularly, it has a partial skeleton such as lactone, lactam, sultone, spiropyran, ester, amide and the like, and is a colorless which rapidly opens or cleaves the partial skeleton when contacted with an electron accepting compound. Compounds are preferred.
  • acid-coloring agents examples include: 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide (referred to as "crystal violet lactone"), 3,3-bis (4- Dimethylaminophenyl) phthalide, 3- (4-dimethylaminophenyl) -3- (4-diethylamino-2-methylphenyl) -6-dimethylaminophthalide, 3- (4-dimethylaminophenyl) -3- (1 , 2-Dimethylindol-3-yl) phthalide, 3- (4-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindole-3) -Yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-biphenyl (9-E
  • the acid color former used in the present disclosure is preferably at least one compound selected from the group consisting of spiropyran compounds, spirooxazine compounds, spirolactone compounds and spirolactam compounds.
  • the hue of the dye after color development is preferably green, blue or black from the viewpoint of visibility.
  • an acid color developing agent such as ETAC, RED 500, RED 520, CVL, S-205, BLACK 305, BLACK 400, BLACK 100, BLACK 500, H-7001, GREEN 300, NIRBLACK 78, BLUE 220, H.
  • the acid color formers may be used alone or in combination of two or more.
  • the content of the acid color former is preferably 0.01% by mass to 30% by mass, more preferably 0.05% by mass to 25% by mass, particularly preferably 0.1% by mass, based on the total mass of the image recording layer. % To 20% by mass.
  • the image recording layer may contain polymer particles.
  • the polymer particles are preferably polymer particles that can convert the image recording layer to hydrophobic when heat is applied.
  • the polymer particles are at least one selected from hydrophobic thermoplastic polymer particles, heat-reactive polymer particles, polymer particles having a polymerizable group, microcapsules containing a hydrophobic compound, and microgel (crosslinked polymer particles). Is preferred. Among them, polymer particles and microgels having a polymerizable group are preferable.
  • hydrophobic thermoplastic polymer particles for example, Research Disclosure No. 1 of January 1992. No. 33,303, hydrophobic thermoplastic polymer particles described in JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, JP-A-9-171250 and EP931647 are suitable. Can be mentioned.
  • polymer constituting the hydrophobic thermoplastic polymer particles include ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, polyalkylene structure And homopolymers or copolymers of monomers such as acrylates or methacrylates or mixtures thereof.
  • polystyrene, a copolymer containing styrene and acrylonitrile, and polymethyl methacrylate can be mentioned.
  • the average particle size of the hydrophobic thermoplastic polymer particles is preferably 0.01 ⁇ m to 2.0 ⁇ m.
  • the thermally reactive polymer particles include polymer particles having a thermally reactive group.
  • the polymer particles having a thermally reactive group form a hydrophobized region by crosslinking due to thermal reaction and functional group change at that time.
  • the thermally reactive group in the polymer particle having a thermally reactive group may be a functional group which carries out any reaction as long as a chemical bond is formed, and a polymerizable group is preferred.
  • a polymerizable group examples thereof include ethylenically unsaturated groups (for example, acryloyl group, methacryloyl group, vinyl group, allyl group etc.) which undergo radical polymerization reaction, cationically polymerizable groups (for example, vinyl group, vinyloxy group, epoxy group, oxetanyl group) Etc.), isocyanato group to perform addition reaction or a block thereof, epoxy group, vinyloxy group and functional group having active hydrogen atom (such as amino group, hydroxy group, carboxy group etc.) which is a reaction partner thereof, condensation reaction Preferred examples include a carboxy group to be carried out and a hydroxy group or amino group which is a reaction partner, an acid anhydride which performs a ring-opening addition reaction, an amino group or
  • microcapsules examples include those in which all or part of the components of the image recording layer are encapsulated in microcapsules, as described in JP-A-2001-277740 and JP-A-2001-277742.
  • the components of the image recording layer can also be contained outside the microcapsules.
  • a hydrophobic component is encapsulated in the microcapsule and a hydrophilic component is contained outside the microcapsule.
  • the microgel can contain some of the components of the image recording layer on at least one of its interior and surface.
  • a reactive microgel is obtained by having a radically polymerizable group on the surface is preferable from the viewpoint of image formation sensitivity and printing durability.
  • the average particle diameter of the microcapsules or microgel is preferably 0.01 ⁇ m to 3.0 ⁇ m, more preferably 0.05 ⁇ m to 2.0 ⁇ m, and particularly preferably 0.10 ⁇ m to 1.0 ⁇ m. Within this range, good resolution and stability over time can be obtained.
  • the content of the polymer particles is preferably 5% by mass to 90% by mass with respect to the total mass of the image recording layer.
  • the image recording layer used in the present disclosure preferably contains a binder polymer.
  • a binder polymer As a binder polymer, (meth) acrylic resin, polyvinyl acetal resin, and a polyurethane resin are preferable.
  • (meth) acrylic includes “acrylic” and "methacrylic”.
  • binder polymer known binder polymers used in the image recording layer of a lithographic printing plate precursor can be suitably used.
  • a binder polymer (hereinafter, also referred to as a binder polymer for on-press development) used for an on-press development type lithographic printing plate precursor will be described in detail.
  • a binder polymer for on-press development a binder polymer having an alkylene oxide chain is preferable.
  • the binder polymer having an alkylene oxide chain may have a poly (alkylene oxide) moiety in the main chain or in the side chain.
  • it may be a graft polymer having a poly (alkylene oxide) in a side chain, or a block copolymer of a block constituted by a poly (alkylene oxide) -containing repeating unit and a block constituted by a (alkylene oxide) non-containing repeating unit.
  • a polyurethane resin is preferred.
  • the polymer of the main chain when having a poly (alkylene oxide) moiety in the side chain includes (meth) acrylic resin, polyvinyl acetal resin, polyurethane resin, polyurea resin, polyimide resin, polyamide resin, epoxy resin, polystyrene resin, novolac type Phenol resins, polyester resins, synthetic rubbers and natural rubbers may be mentioned, and (meth) acrylic resins are particularly preferred.
  • alkylene oxide an alkylene oxide having 2 to 6 carbon atoms is preferable, and ethylene oxide or propylene oxide is particularly preferable.
  • the number of repeating alkylene oxides in the poly (alkylene oxide) moiety is preferably 2 to 120, more preferably 2 to 70, and still more preferably 2 to 50. If the number of repetitions of the alkylene oxide is 120 or less, it is preferable because deterioration in both printing durability due to abrasion and printing durability due to ink receptivity is suppressed.
  • the poly (alkylene oxide) moiety is preferably contained as a side chain of the binder polymer in a structure represented by the following formula (AO), and as a side chain of a (meth) acrylic resin, it is represented by the following formula (AO) More preferably, it is contained in the following structure.
  • y represents 2 to 120
  • R 1 represents a hydrogen atom or an alkyl group
  • R 2 represents a hydrogen atom or a monovalent organic group.
  • the monovalent organic group is preferably an alkyl group having a carbon number of 1 to 6, and is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group And n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, cyclopentyl and cyclohexyl.
  • y is preferably 2 to 70, and more preferably 2 to 50.
  • R 1 is preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom.
  • R 2 is particularly preferably a hydrogen atom or a methyl group.
  • the binder polymer may have crosslinkability in order to improve the film strength of the image area.
  • a crosslinkable functional group such as an ethylenically unsaturated bond may be introduced into the main chain or side chain of the polymer.
  • the crosslinkable functional group may be introduced by copolymerization or may be introduced by a polymer reaction.
  • Examples of polymers having an ethylenically unsaturated bond in the main chain of the molecule include poly-1,4-butadiene, poly-1,4-isoprene and the like.
  • An example of a polymer having an ethylenically unsaturated bond in the side chain of the molecule is a polymer of an ester or amide of acrylic acid or methacrylic acid, and the residue of ester or amide (R of -COOR or -CONHR) is Mention may be made of polymers having ethylenically unsaturated bonds.
  • free radicals polymerization initiating radicals or propagating radicals in the polymerization process of the polymerizable compound
  • Addition polymerization is performed to form crosslinks between polymer molecules and cure.
  • an atom in the polymer for example, a hydrogen atom on a carbon atom adjacent to a functional crosslinking group
  • a free radical is extracted by a free radical to generate a polymer radical, which combines with one another to form a crosslink between polymer molecules. It forms and cures.
  • the content of the crosslinkable group in the binder polymer is preferably 0 per gram of the binder polymer from the viewpoint of good sensitivity and good storage stability. 1 mmol to 10.0 mmol, more preferably 1.0 mmol to 7.0 mmol, particularly preferably 2.0 mmol to 5.5 mmol.
  • the binder polymer for on-press development is shown below, but the present disclosure is not limited thereto.
  • the numerical values shown in parallel with each repeating unit represent the mole percentage of the above-mentioned repeating unit.
  • the numerical value added to the repeating unit of the side chain indicates the number of repetition of the above repeating site.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Ph represents a phenyl group.
  • the binder polymer preferably has a weight average molecular weight (Mw) of 2,000 or more, more preferably 5,000 or more, and 10,000 to 300,000 as the polystyrene conversion value by GPC method. It is further preferred that
  • hydrophilic polymers such as polyacrylic acid and polyvinyl alcohol described in JP-A-2008-195018 can be used in combination. Also, lipophilic polymers and hydrophilic polymers can be used in combination.
  • the binder polymer may be present in the image recording layer as a polymer functioning as a binder for each component or may be present in the form of particles.
  • the average primary particle size is preferably 10 nm to 1,000 nm, more preferably 20 nm to 300 nm, still more preferably 30 nm to 120 nm.
  • one binder polymer may be used alone, or two or more binder polymers may be used in combination.
  • the binder polymer can be contained in any amount in the image recording layer.
  • the content of the binder polymer can be appropriately selected depending on the application of the image recording layer and the like, but is preferably 1% by mass to 90% by mass, and more preferably 5% by mass to 80% by mass with respect to the total mass of the image recording layer.
  • the image recording layer used in the present disclosure may contain an electron donated polymerization initiator.
  • the compound applicable to the above-mentioned specific compound shall not be contained in an electron donor type polymerization initiator.
  • the electron donating polymerization initiator contributes to the improvement of printing durability in a lithographic printing plate.
  • an electron donor type polymerization initiator the following five types are mentioned, for example.
  • Alkyl or arylate complex It is thought that a carbon-hetero bond is oxidatively cleaved to generate an active radical. Specifically, borate compounds and the like can be mentioned.
  • (Ii) Aminoacetic acid compound It is believed that oxidation breaks up the C—X bond on the carbon adjacent to nitrogen to generate an active radical.
  • X a hydrogen atom, a carboxy group, a trimethylsilyl group or a benzyl group is preferable.
  • N-phenylglycines a phenyl group may have a substituent
  • N-phenyliminodiacetic acid a phenyl group may have a substituent
  • Be (Iii) Sulfur-containing compounds Those in which the nitrogen atom of the above-mentioned aminoacetic acid compound is replaced by a sulfur atom can generate an active radical by the same action.
  • Tin-containing compounds those in which the nitrogen atom of the above-mentioned aminoacetic acid compound is replaced by a tin atom can generate active radicals by the same action.
  • Sulfinates Oxidation can generate active radicals. Specifically, sodium arylsulfine and the like can be mentioned.
  • the image recording layer preferably contains a borate compound.
  • a borate compound a tetraaryl borate compound or a monoalkyl triaryl borate compound is preferable, and from the viewpoint of the stability of the compound, a tetraaryl borate compound is more preferable, and a tetraaryl borate compound having one or more aryl groups having an electron attractive group. Particularly preferred are aryl borate compounds.
  • a group having a positive Hammett's ⁇ value is preferable, and a group having a Hammett's ⁇ value of 0 to 1.2 is more preferable.
  • a halogen atom, a trifluoromethyl group or a cyano group is preferable, and a fluorine atom, a chlorine atom, a trifluoromethyl group or a cyano group is more preferable.
  • an alkali metal ion or a tetraalkyl ammonium ion is preferable, and a sodium ion, a potassium ion, or a tetrabutyl ammonium ion is more preferable.
  • X c + represents a monovalent cation, and is preferably an alkali metal ion or a tetraalkylammonium ion, and more preferably an alkali metal ion or a tetrabutylammonium ion.
  • Bu represents an n-butyl group.
  • the electron donating polymerization initiator may be added alone or in combination of two or more.
  • the content of the electron donating polymerization initiator is preferably 0.01% by mass to 30% by mass, more preferably 0.05% by mass to 25% by mass, based on the total mass of the image recording layer, and 0.1% by mass It is more preferable that the content be up to 20% by mass.
  • the image recording layer used in the present disclosure may contain a chain transfer agent.
  • the chain transfer agent contributes to the improvement of printing durability in a lithographic printing plate.
  • the chain transfer agent is preferably a thiol compound, more preferably a thiol having a carbon number of 7 or more from the viewpoint of boiling point (poor volatility), and still more preferably a compound having a mercapto group on an aromatic ring (aromatic thiol compound).
  • the thiol compound is preferably a monofunctional thiol compound.
  • chain transfer agent examples include the following compounds.
  • the chain transfer agent may be used alone or in combination of two or more.
  • the content of the chain transfer agent is preferably 0.01% by mass to 50% by mass, more preferably 0.05% by mass to 40% by mass, and still more preferably 0.1% by mass to 30% by mass with respect to the total mass of the image recording layer. % Is more preferred.
  • the image recording layer may contain a low molecular weight hydrophilic compound in order to improve the on-press developability while suppressing the deterioration of the printing durability.
  • the low molecular weight hydrophilic compound is preferably a compound having a molecular weight of less than 1,000, more preferably a compound having a molecular weight of less than 800, and still more preferably a compound having a molecular weight of less than 500.
  • hydrophilic compounds for example, as water-soluble organic compounds, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like, ethers or ester derivatives thereof, glycerin, Polyols such as pentaerythritol, tris (2-hydroxyethyl) isocyanurate, organic amines such as triethanolamine, diethanolamine and monoethanolamine and salts thereof, organic sulfones such as alkyl sulfonic acid, toluene sulfonic acid and benzene sulfonic acid Acids and salts thereof, organic sulfamic acids such as alkyl sulfamic acids and salts thereof, organic sulfuric acids such as alkyl sulfuric acids and alkyl ether sulfuric acids and salts thereof, phenyl phosphonic acid Organic phosphonic acids and salts thereof, tartaric acid
  • the low molecular weight hydrophilic compound preferably contains at least one selected from polyols, organic sulfates, organic sulfonates and betaines.
  • organic sulfonates include alkyl sulfonates such as sodium n-butyl sulfonate, sodium n-hexyl sulfonate, sodium 2-ethylhexyl sulfonate, sodium cyclohexyl sulfonate, sodium n-octyl sulfonate; , 8,11-Trioxapentadecane-1-sulfonic acid sodium, 5,8,11-trioxaheptadecane-1-sulfonic acid sodium, 13-ethyl-5,8,11-trioxaheptadecane-1-sulfone Alkyl sulfonates containing ethylene oxide chains such as sodium acid sodium and sodium 5,8,11,14-tetraoxatetracosan-1-sulphonate; sodium benzene sulphonate, sodium p-toluene sulphonate, p-hydroxy benzene sulphide
  • Organic sulfates include sulfates of alkyl, alkenyl, alkynyl, aryl or heterocyclic monoethers of polyethylene oxide.
  • the number of ethylene oxide units is preferably 1 to 4, and the salt is preferably a sodium salt, potassium salt or lithium salt. Specific examples thereof include the compounds described in paragraphs 0034 to 0038 of JP-A-2007-276454.
  • Preferred betaines are compounds having 1 to 5 carbon atoms in the hydrocarbon substituent to the nitrogen atom, and specific examples thereof include trimethyl ammonium acetate, dimethyl propyl ammonium acetate, 3-hydroxy-4-trimethyl ammonium Obtilate, 4- (1-pyridinio) butyrate, 1-hydroxyethyl-1-imidazolioacetate, trimethylammonium methanesulfonate, dimethylpropylammonium methanesulfonate, 3-trimethylammonio-1-propanesulfonate, 3 And-(1-pyridinio) -1-propanesulfonate and the like.
  • the low molecular weight hydrophilic compound has a small hydrophobic part structure and hardly has a surfactant activity, and dampening water penetrates the exposed part (image part) of the image recording layer to reduce the hydrophobicity and the film strength of the image part. And the ink receptivity and the printing durability of the image recording layer can be well maintained.
  • the content of the low molecular weight hydrophilic compound is preferably 0.5% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and more preferably 2% by mass to 10% by mass with respect to the total mass of the image recording layer. Is more preferred. In this range, good on-press developability and press life can be obtained.
  • the low molecular weight hydrophilic compounds may be used alone or in combination of two or more.
  • the image recording layer may contain a sensitizing agent such as a phosphonium compound, a nitrogen-containing low molecular weight compound, or an ammonium group-containing polymer in order to improve the receptivity.
  • a sensitizing agent such as a phosphonium compound, a nitrogen-containing low molecular weight compound, or an ammonium group-containing polymer
  • these compounds function as a surface coating agent for the inorganic stratiform compound and can suppress the decrease in the receptivity during printing by the inorganic stratiform compound.
  • a sensitizing agent it is preferable to use a phosphonium compound, a nitrogen-containing low molecular weight compound, and an ammonium group-containing polymer in combination, and to use a phosphonium compound, a quaternary ammonium salt, and an ammonium group-containing polymer in combination. Is more preferred.
  • the nitrogen-containing low molecular weight compounds include amine salts and quaternary ammonium salts. Also, imidazolinium salts, benzimidazolinium salts, pyridinium salts, quinolinium salts can be mentioned. Among them, quaternary ammonium salts and pyridinium salts are preferred.
  • the ammonium group-containing polymer may have an ammonium group in its structure, and is preferably a polymer containing 5 mol% to 80 mol% of a (meth) acrylate having an ammonium group in a side chain as a copolymerization component.
  • Specific examples include the polymers described in paragraphs 0089 to 0105 of JP-A-2009-208458.
  • the ammonium salt-containing polymer preferably has a reduced specific viscosity (unit: ml / g) value of 5 to 120, preferably 10 to 110, which is determined according to the measurement method described in JP-A 2009-208458. Are more preferred, and those in the range of 15 to 100 are particularly preferred.
  • Mw weight average molecular weight
  • the content of the sensitizing agent is preferably 0.01% by mass to 30.0% by mass, and more preferably 0.1% by mass to 15.0% by mass, with respect to the total mass of the image recording layer. % To 10% by mass is more preferable.
  • the image recording layer may contain, as other components, surfactants, polymerization inhibitors, higher fatty acid derivatives, plasticizers, inorganic particles, inorganic layered compounds, and the like. Specifically, the description in paragraphs [0114] to [0159] of JP-A-2008-284817 can be referred to.
  • the image recording layer in the lithographic printing plate precursor according to the present disclosure is, for example, dispersed or dissolved in a known solvent and applied as described in paragraphs 0142 to 0143 of JP-A-2008-195018.
  • the solution can be prepared, coated on a support by a known method such as bar coating, and dried.
  • the coating amount (solid content) of the image recording layer after coating and drying varies depending on the application, but generally 0.3 g / m 2 to 3.0 g / m 2 is preferable. Within this range, good sensitivity and good film properties of the image recording layer can be obtained.
  • the solid content is the total amount of components excluding volatile components such as a solvent in the composition.
  • the lithographic printing plate precursor according to the present disclosure preferably has a subbing layer (sometimes referred to as an intermediate layer) between the image recording layer and the support.
  • the undercoat layer strengthens the adhesion between the support and the image recording layer in the exposed area and facilitates the peeling of the image recording layer from the support in the unexposed area. Contribute to improving In addition, in the case of infrared laser exposure, the undercoat layer functions as a heat insulating layer, which also has an effect of preventing the heat generated by the exposure from being diffused to the support to reduce the sensitivity.
  • Examples of the compound used for the undercoat layer include polymers having an adsorptive group capable of adsorbing to the surface of the support and a hydrophilic group. In order to improve the adhesion to the image recording layer, polymers having an adsorptive group and a hydrophilic group, and further having a crosslinkable group are preferred.
  • the compound used for the undercoat layer may be a low molecular weight compound or a polymer. The compounds used in the undercoat layer may be used as a mixture of two or more, if necessary.
  • the compound used for the undercoat layer is a polymer
  • a copolymer of a monomer having an adsorptive group, a monomer having a hydrophilic group and a monomer having a crosslinkable group is preferred.
  • adsorptive groups capable of adsorbing to the surface of a support include phenolic hydroxy group, carboxy group, -PO 3 H 2 , -OPO 3 H 2 , -CONHSO 2- , -SO 2 NHSO 2- , -COCH 2 COCH 3 Is preferred.
  • the hydrophilic group is preferably a sulfo group or a salt thereof, or a salt of a carboxy group.
  • the polymer may have a crosslinkable group introduced by salt formation of a polar substituent of the polymer and a compound having a pair charge with the polar substituent and a compound having an ethylenically unsaturated bond, or Other monomers, preferably hydrophilic monomers, may be further copolymerized.
  • the phosphorus compound which has a heavy bond reactive group is mentioned suitably.
  • Crosslinkable groups (preferably, ethylenically unsaturated bond groups) described in JP 2005-238816, JP 2005-125749, JP 2006-239867, and JP 2006-215263, and a support Low molecular weight or high molecular weight compounds having a functional group that interacts with the surface and a hydrophilic group are also preferably used.
  • More preferable examples include polymer polymers having an adsorptive group, a hydrophilic group and a crosslinkable group which can be adsorbed on the surface of a support as described in JP-A-2005-125749 and JP-A-2006-188038.
  • the content of the ethylenically unsaturated bonding group in the polymer used for the undercoat layer is preferably 0.1 mmol to 10.0 mmol, more preferably 0.2 mmol to 5.5 mmol, per 1 g of the polymer.
  • the weight average molecular weight (Mw) of the polymer used for the undercoat layer is preferably 5,000 or more, and more preferably 10,000 to 300,000.
  • the undercoat layer has a chelating agent, a secondary or tertiary amine, a polymerization inhibitor, an amino group or a functional group having a polymerization inhibiting ability and a support surface in order to prevent soiling over time.
  • DABCO 1,4-diazabicyclo [2.2.2] octane
  • 2,3,5,6-tetrahydroxy-p-quinone chloranil
  • sulfophthalic acid hydroxy It may contain ethyl ethylenediamine triacetic acid, dihydroxyethyl ethylenediamine diacetic acid, hydroxyethyl imino diacetic acid, and the like.
  • the subbing layer is applied in a known manner.
  • the coating amount (solid content) of the undercoat layer is preferably 0.1 mg / m 2 to 100 mg / m 2, and more preferably 1 mg / m 2 to 30 mg / m 2 .
  • the lithographic printing plate precursor according to the present disclosure preferably has a protective layer (sometimes referred to as an overcoat layer) on the image recording layer.
  • the protective layer has a function of preventing the generation of a scratch in the image recording layer and a function of preventing ablation during high-intensity laser exposure, in addition to the function of suppressing the image formation inhibition reaction by oxygen blocking.
  • the protective layer having such properties is described, for example, in US Pat. No. 3,458,311 and JP-B-55-49729.
  • a water-soluble polymer or a water-insoluble polymer can be appropriately selected and used, and two or more types can be mixed and used as needed. it can.
  • polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, a water-soluble cellulose derivative, poly (meth) acrylonitrile and the like can be mentioned.
  • the modified polyvinyl alcohol an acid modified polyvinyl alcohol having a carboxy group or a sulfo group is preferably used.
  • modified polyvinyl alcohols described in JP-A-2005-250216 and JP-A-2006-259137 can be mentioned.
  • the protective layer preferably contains an inorganic stratiform compound to enhance the oxygen barrier property.
  • the inorganic stratiform compound is a particle having a thin tabular shape, and, for example, a mica group such as natural mica and synthetic mica, talc represented by the formula: 3MgO.4SiO.H 2 O, teniolite, montmorillonite, saponite, hekto Light, zirconium phosphate and the like can be mentioned.
  • the inorganic layered compound preferably used is a mica compound.
  • A is any of K, Na and Ca
  • B and C are It is any of Fe (II), Fe (III), Mn, Al, Mg and V, and D is Si or Al.
  • micas such as natural micas and synthetic micas.
  • natural micas include muscovite, soda mica, phlogopite, biotite and phlogopite.
  • Non-swelling micas such as fluorine phlogopite KMg 3 (AlSi 3 O 10 ) F 2 and potassium tetrasilicon mica KMg 2.5 Si 4 O 10 ) F 2 as synthetic micas, and Na tetrasilylic mica NaMg 2.
  • the lattice layer lacks positive charge, and in order to compensate for it, cations such as Li + , Na + , Ca 2+ and Mg 2+ are adsorbed between the layers. The cations intervening between these layers are called exchangeable cations and can be exchanged with various cations.
  • the bond between the layered crystal lattices is weak because the ion radius is small, and the layer swells significantly with water. In this state, shearing readily cleaves to form a stable sol in water. Swellable synthetic mica is strong in this tendency and is particularly preferably used.
  • the aspect ratio is preferably 20 or more, more preferably 100 or more, and particularly preferably 200 or more.
  • the aspect ratio is the ratio of the major axis to the thickness of the particle, and can be measured, for example, from a projection of the particle by a micrograph. The larger the aspect ratio, the greater the effect obtained.
  • the average major axis of the particle diameter of the mica compound is preferably 0.3 ⁇ m to 20 ⁇ m, more preferably 0.5 ⁇ m to 10 ⁇ m, and particularly preferably 1 ⁇ m to 5 ⁇ m.
  • the average thickness of the particles is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and particularly preferably 0.01 ⁇ m or less.
  • the thickness is about 1 nm to 50 nm
  • the surface size (long diameter) is about 1 ⁇ m to 20 ⁇ m.
  • the content of the inorganic stratiform compound is preferably 1% by mass to 60% by mass, and more preferably 3% by mass to 50% by mass, with respect to the total solid content of the protective layer. Even when using a plurality of types of inorganic stratiform compounds in combination, it is preferable that the total amount of the inorganic stratiform compounds has the above content. Within the above range, the oxygen barrier property is improved, and good sensitivity can be obtained. In addition, it is possible to prevent the deterioration of the inking property.
  • the protective layer may contain known additives such as a plasticizer for imparting flexibility, a surfactant for improving the coatability, and inorganic particles for controlling the slipperiness of the surface. Further, the oil-receptive agent described in the image recording layer may be contained in the protective layer.
  • the protective layer is applied in a known manner.
  • the coating amount of the protective layer (solid content) is preferably from 0.01g / m 2 ⁇ 10g / m 2, more preferably 0.02g / m 2 ⁇ 3g / m 2, 0.02g / m 2 ⁇ 1g / m 2 is particularly preferred.
  • the support of the lithographic printing plate precursor according to the present disclosure can be appropriately selected from known supports for lithographic printing plate precursors.
  • a support having a hydrophilic surface is preferred.
  • the aluminum plate surface-roughened by a well-known method and anodized is preferable.
  • the aluminum plate may further be subjected to micropore enlargement treatment or sealing treatment of the anodized film described in JP-A-2001-253181 and JP-A-2001-322365 as required, US Pat. No.
  • the support is, if necessary, an organic polymer compound described in JP-A-5-45885, an alkoxy compound of silicon described in JP-A-6-35174, etc. on the side opposite to the image recording layer. And may have a back coat layer containing
  • a lithographic printing plate can be produced by imagewise exposing the lithographic printing plate precursor according to the present disclosure and performing development processing.
  • the plate-making method of a lithographic printing plate according to the present disclosure comprises: exposing the lithographic printing plate precursor according to the present disclosure image-wise to form an exposed area and an unexposed area; and at least printing ink and dampening water
  • An on-machine development step of supplying one to remove the unexposed area is included in this order.
  • preferred embodiments of the respective steps of the lithographic printing plate making method according to the present disclosure and the lithographic printing method according to the present disclosure will be described in order.
  • the lithographic printing plate precursor according to the present disclosure can also be developed by a developer.
  • the plate making method of a lithographic printing plate according to the present disclosure preferably includes an exposing step of imagewise exposing the lithographic printing plate precursor according to the present disclosure to form an exposed area and an unexposed area.
  • the lithographic printing plate precursor according to the present disclosure is preferably imagewise exposed by laser exposure through a transparent original having a line image, halftone dot image or the like or by laser light scanning with digital data.
  • the wavelength of the light source is preferably 750 nm to 1,400 nm.
  • a solid state laser and a semiconductor laser emitting infrared rays are preferable.
  • the output is preferably 100 mW or more, the exposure time per pixel is preferably within 20 microseconds, and the amount of irradiation energy is 10 mJ / cm 2 to 300 mJ / cm 2. preferable.
  • the exposure mechanism may be any of an inner drum system, an outer drum system, and a flat bed system. Image exposure can be performed by a conventional method using a platesetter or the like.
  • the lithographic printing plate precursor may be mounted on a printing press and then imagewise exposed on the printing press.
  • the method for making a lithographic printing plate according to the present disclosure preferably includes an on-press development step of supplying at least one of printing ink and dampening water to remove the unexposed area.
  • the method for making a lithographic printing plate according to the present disclosure may be carried out by a method of developing with a developer (developer processing method).
  • developer processing method The on-press development method will be described below.
  • On-press development method an imagewise exposed lithographic printing plate precursor is supplied with an oil-based ink and an aqueous component on a printing press, and the image recording layer in the non-image area is removed to prepare a lithographic printing plate Is preferred. That is, the lithographic printing plate precursor is imagewise exposed and then mounted as it is without any development processing, or the lithographic printing plate precursor is mounted on a printing machine and then imagewise exposed on the printing press and then When an oil-based ink and an aqueous component are supplied and printed, an uncured image recording layer is formed by the supplied oil ink and / or the aqueous component in the non-image area at an early stage of printing.
  • the image recording layer cured by the exposure forms an oil-based ink receiving portion having a lipophilic surface.
  • An oil-based ink or an aqueous component may be supplied first to the printing plate, but the oil-based ink is first supplied in that the aqueous component is prevented from being contaminated by the removed components of the image recording layer. Is preferred.
  • the lithographic printing plate precursor is developed on the press on a printing press and used as it is for printing a large number of sheets.
  • an oil-based ink and an aqueous component the printing ink and dampening water for normal lithographic printing are used suitably.
  • the planographic printing method includes a printing step of supplying a printing ink to the planographic printing plate developed on-press in the above-described on-press development step to print a recording medium.
  • the printing ink is not particularly limited, and various known inks can be used as desired.
  • oil-based ink is mentioned preferably.
  • UV-curable inks are preferably mentioned.
  • dampening water may be supplied as necessary.
  • the printing process may be performed continuously to the on-press development process without stopping the printing machine. There is no restriction
  • the entire surface of the plate precursor may be heated.
  • Such heating accelerates the image forming reaction in the image recording layer, and may provide advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity.
  • Heating before development is preferably performed under mild conditions of 150 ° C. or less. According to the above aspect, it is possible to prevent problems such as curing of the non-image area. It is preferable to use very strong conditions for heating after development, and a range of 100 ° C. to 500 ° C. is preferable. Within the above range, a sufficient image enhancing action can be obtained, and problems such as deterioration of the support and thermal decomposition of the image portion can be suppressed.
  • the color forming composition includes a compound (specific compound) having a cation portion having a radical reactive group and an anion portion containing a boron atom, and an acid color agent.
  • the specific compound and the acid color former in the color forming composition have the same meaning as the specific compound and the acid color former in the image recording layer of the above-mentioned lithographic printing plate precursor, and the preferred embodiments are also the same.
  • the color forming composition preferably contains an infrared absorber, and more preferably contains an infrared absorber which is decomposed by an acid to form a color.
  • the infrared absorber in the color forming composition has the same meaning as the infrared absorber in the image recording layer of the above-mentioned lithographic printing plate precursor, and the preferred embodiments are also the same.
  • the color forming composition according to the present disclosure is a group consisting of a radically polymerizable compound, a radical polymerization initiator, a polymer particle, a binder polymer, a chain transfer agent, a low molecular weight hydrophilic compound, a sensitizing agent, and a known solvent. And at least one selected from the group consisting of Preferred embodiments of these compounds are the same as the preferred embodiments of the respective compounds in the above-mentioned lithographic printing plate precursor.
  • the content of each component contained in the color forming composition according to the present disclosure corresponds to the amount obtained by replacing the content of each component contained in the image recording layer of the above-mentioned lithographic printing plate precursor with the solid content in the color forming composition. .
  • a lithographic printing plate precursor can be obtained by using the color forming composition according to the present disclosure.
  • the photosensitive resin composition according to the present disclosure is also suitably used in the fields of image forming materials, 3D modeling and the like.
  • the curable composition which concerns on this indication contains the compound (specific compound) which has a cation part which has a radically reactive group, and the anion part containing a boron atom, an infrared rays absorber, and a radically polymerizable compound.
  • the specific compound, the infrared absorber and the radically polymerizable compound in the curable composition are the same as the specific compound, the infrared absorber and the radically polymerizable compound in the image recording layer of the above-mentioned planographic printing plate precursor, and the preferred embodiments are also the same.
  • the curable composition preferably further contains a radical polymerization initiator.
  • the radical polymerization initiator in the curable composition has the same meaning as the infrared absorber in the image recording layer of the above-mentioned lithographic printing plate precursor, and the preferred embodiments are also the same.
  • the curable composition according to the present disclosure comprises at least at least one selected from the group consisting of polymer particles, binder polymers, acid color formers, chain transfer agents, low molecular weight hydrophilic compounds, oil sensitizers, and known solvents. One type may be further contained. Preferred embodiments of these compounds are the same as the preferred embodiments of the respective compounds in the above-mentioned lithographic printing plate precursor.
  • the content of each component contained in the curable composition according to the present disclosure is the amount obtained by replacing the content of each component contained in the image recording layer of the above-mentioned lithographic printing plate precursor with the solid content in the curable composition. Equivalent to.
  • a lithographic printing plate precursor can be obtained by using the curable composition according to the present disclosure.
  • the curable composition according to the present disclosure is also suitably used in the fields of image forming materials, 3D modeling and the like.
  • the image forming material according to the present disclosure includes the curable composition according to the present disclosure or the color forming composition according to the present disclosure.
  • the image forming material according to the present disclosure preferably contains the curable composition according to the present disclosure or the color forming composition according to the present disclosure as an image recording layer.
  • the image forming material according to the present disclosure preferably includes at least one of a subbing layer, a protective layer, and a support.
  • the undercoat layer, the protective layer and the support in the image forming material according to the present disclosure are the same as the undercoat layer, the protective layer and the support in the lithographic printing plate precursor according to the present disclosure, and preferred embodiments are also the same. .
  • % and “parts” mean “% by mass” and “parts by mass” unless otherwise noted.
  • the molecular weight is a weight average molecular weight (Mw)
  • the ratio of the constituent repeating units is a molar percentage, except as specially specified.
  • a weight average molecular weight (Mw) is a value measured as a polystyrene conversion value by gel permeation chromatography (GPC) method.
  • the etching amount of the grained surface was about 3 g / m 2 .
  • the electrolytic solution was a 1 mass% nitric acid aqueous solution (containing 0.5 mass% of aluminum ion), and the liquid temperature was 50 ° C.
  • the AC power supply waveform is electrochemically roughened with a carbon electrode as a counter electrode, using a trapezoidal rectangular wave AC with a time TP of 0.8 ms for the current value to reach a peak and a duty ratio of 1: 1.
  • Ferrite was used for the auxiliary anode.
  • the current density was 30 A / dm 2 at the peak value of the current, and 5% of the current flowing from the power supply was diverted to the auxiliary anode.
  • the amount of electricity in nitric acid electrolysis was 175 C / dm 2 when the aluminum plate was an anode. After that, it was rinsed with a spray.
  • nitric acid electrolysis is carried out using a 0.5 mass% aqueous solution of hydrochloric acid (containing 0.5 mass% of aluminum ion) and an electrolytic solution with a liquid temperature of 50 ° C. under the condition that the aluminum plate has an electric quantity of 50 C / dm 2 at the anode.
  • Electrochemical roughening treatment was carried out in the same manner as in the above, followed by washing with spray.
  • using a 15% by weight aqueous solution of sulfuric acid (containing 0.5% by weight of aluminum ion) as an electrolytic solution form a direct current anodic oxide film of 2.5 g / m 2 at a current density of 15 A / dm 2 It dried and the support body A was produced.
  • the average pore diameter (surface average pore diameter) in the surface layer of the anodized film was 10 nm.
  • the measurement of the pore diameter in the surface layer of the anodized film uses an ultra-high resolution SEM (S-900 manufactured by Hitachi, Ltd.), and uses a deposition process or the like to impart conductivity at a relatively low acceleration voltage of 12 V.
  • the surface was observed at a magnification of 150,000 times without application, and 50 pores were randomly extracted to obtain an average value.
  • the standard error was less than ⁇ 10%.
  • support A was subjected to a silicate treatment at 60 ° C. for 10 seconds using a 2.5 mass% aqueous solution of sodium silicate No. 3 for 10 seconds, and washed to prepare support B. .
  • the adhesion amount of Si was 10 mg / m 2 .
  • the center line average roughness (Ra) of the support B was measured using a needle with a diameter of 2 ⁇ m and found to be 0.51 ⁇ m.
  • a support C was produced in the same manner as the support A, except that, in the preparation of the support A, the electrolytic solution for forming the direct current anodic oxide film was changed to a 22% by mass aqueous phosphoric acid solution. It was 25 nm when the average pore diameter (surface average pore diameter) in the surface layer of the anodic oxide film was measured by the same method as the above.
  • a lithographic printing plate precursor was produced using the support C described above.
  • undercoat layer coating solution (1) having the following composition was applied onto the support A so that the dry coating amount would be 20 mg / m 2 to form an undercoat layer.
  • reaction solution was returned to room temperature (25 ° C., hereinafter the same), and then 175 parts of 30% by mass aqueous sodium hydroxide solution was added to adjust the pH to 8.3. Next, 0.152 parts of 4-OH-TEMPO was added, and the temperature was raised to 53.degree. 66.0 parts of methacrylic anhydride were added and stirred at 53 ° C. for 3 hours. After returning to room temperature, the reaction solution was transferred to a stainless beaker, and 1,800 parts of MTBE were added. After vigorously stirring, the mixture was allowed to stand and the upper layer was discarded.
  • Blemmer PME 4000 methoxy polyethylene glycol methacrylate (the number of repeating oxyethylene units: 90)
  • VA-046B 2,2'-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate
  • an image recording layer coating solution (1) having the following composition was bar-coated on the undercoat layer, dried in an oven at 70 ° C. for 60 seconds, and dried at a coating amount of 0.6 g / m 2 A recording layer was formed to prepare a lithographic printing plate precursor C.
  • the following image recording layer coating solution corresponds to the curable composition according to the present disclosure and the color forming composition according to the present disclosure.
  • Infrared absorber (D-4) (compound of the following structure): 0.018 parts Radical polymerization initiator I-5-j-1 (compound of the following structure): 0.160 parts Identification described in Table 1 Compound: Amount described in Table 1-Polymer particle water dispersion (1) (22 mass%): 10.0 parts-Radically polymerizable compound SR-399 (made by Sartmar): 1.50 parts-Acid color former: 2′-anilino-6 ′-(N-ethyl-N-isopentylamino) -3′-methylspiro [phthalide-3,9′-xanthene] (S-205, manufactured by Fukui Yamada Chemical Industry Co., Ltd.): 0 .080 parts mercapto-3-triazole: 0.2 parts Byk 336 (manufactured by Byk Chemie): 0.4 parts Klucel M (manufactured by Hercules): 4.8 parts ELVACITE 4026 (
  • the radical polymerization initiator I-5-j-1 is a compound having the following anion part I-5 and the following cation part j-1.
  • Me represents a methyl group
  • Et represents an ethyl group.
  • composition of the image recording layer coating solution (1) The details of the abbreviations described in the composition of the image recording layer coating solution (1) are as follows.
  • ⁇ SR-399 Dipentaerythritol pentaacrylate
  • Byk 336 Modified dimethylpolysiloxane copolymer (25 mass% xylene / methoxypropyl acetate solution)
  • Klucel M hydroxypropyl cellulose (2% by mass aqueous solution)
  • ELVACITE 4026 Highly branched polymethyl methacrylate (10% by weight 2-pig)
  • the preparation method of the polymer particle water dispersion (1) used for the said image recording layer coating liquid (1) is shown below.
  • the particle size distribution of the polymer particles had a maximum at a particle size of 150 nm.
  • the particle size distribution is obtained by taking an electron micrograph of the polymer particles, measuring a total of 5,000 particle sizes on the photograph, and on a logarithmic scale between 0 and the maximum value of the obtained particle size measurements. The frequency of occurrence of each particle size was divided into 50 and plotted. With respect to non-spherical particles, the particle diameter value of spherical particles having the same particle area as the particle area in the photograph is taken as the particle diameter.
  • the measurement was performed by a SCE (regular reflection light removal) method using a spectrophotometer CM2600d manufactured by Konica Minolta Co., Ltd. and operation software CM-S100W.
  • the coloring property was evaluated by the difference ⁇ L * between the L * value of the exposed area and the L * value of the unexposed area, using the L * value (brightness) of the L * a * b * color system.
  • Table 2 shows the values of ⁇ L * .
  • the larger the value of ⁇ L * the better the color developability, and the better the plate detectability of the lithographic printing plate by color development.
  • the lithographic printing plate precursor prepared as described above was exposed (magnification energy: 110 mJ / cm 2) at an output of 27 W, an external drum rotation speed of 450 rpm, and a resolution of 2,400 dpi using Magnus 800 Quantum manufactured by Kodak equipped with an infrared semiconductor laser. Equivalent).
  • the exposed image included a solid image and an AM screen (Amplitude Modulation Screen) chart of 3% halftone dots.
  • the obtained exposed lithographic printing plate precursor was mounted on a cylinder of a Kiku-size (939 mm ⁇ 636 mm) Heidelberg printing machine SX-74 without development processing.
  • a dampening water circulation tank with a capacity of 100 L containing a non-woven fabric filter and a temperature control device was connected to this printing press.
  • Dampening water S-Z1 (Fuji Film Co., Ltd. product) 80L of dampening water of 2.0% is charged into a circulation device, and T & K UV OFS K-HS black ink GE-M (trade Co., Ltd.
  • the planographic printing plate precursors according to Examples 1 to 5 were also excellent in color development as compared with the planographic printing plate precursors according to Comparative Example 1 and Comparative Example 2.

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  • Materials For Photolithography (AREA)

Abstract

L'invention concerne une plaque originale d'impression lithographique, un procédé de fabrication de plaque d'impression lithographique, une composition de coloration, une composition durcissable, et un matériau de formation d'image. Ladite plaque originale d'impression lithographique possède une couche d'enregistrement d'image sur un corps de support. Ladite couche d'enregistrement d'image contient : un composé qui possède une partie cation ayant un groupe réactif par voie radicalaire, et une partie anion contenant un atome de bore ; un agent d'absorption dans l'infrarouge ; et un composé polymérisable par voie radicalaire.
PCT/JP2018/025779 2017-07-13 2018-07-06 Plaque originale d'impression lithographique, procédé de fabrication de plaque d'impression lithographique, composition de coloration, composition durcissable, et matériau de formation d'image Ceased WO2019013139A1 (fr)

Applications Claiming Priority (2)

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JP2017-137247 2017-07-13
JP2017137247 2017-07-13

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WO2019013139A1 true WO2019013139A1 (fr) 2019-01-17

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PCT/JP2018/025779 Ceased WO2019013139A1 (fr) 2017-07-13 2018-07-06 Plaque originale d'impression lithographique, procédé de fabrication de plaque d'impression lithographique, composition de coloration, composition durcissable, et matériau de formation d'image

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113474178A (zh) * 2019-01-31 2021-10-01 富士胶片株式会社 平版印刷版原版、平版印刷版的制作方法及平版印刷方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002207293A (ja) * 2001-01-12 2002-07-26 Fuji Photo Film Co Ltd 平版印刷版原版
JP2007256445A (ja) * 2006-03-22 2007-10-04 Mitsubishi Paper Mills Ltd 光重合性組成物および感光性平版印刷版材料
EP2072570A1 (fr) * 2007-12-20 2009-06-24 Agfa Graphics N.V. Précurseur de plaque d'impression lithographique
JP2009537458A (ja) * 2006-05-17 2009-10-29 アメリカン・ダイ・ソース・インコーポレーテッド 平版印刷版コーティング用新規材料、それを含有する平版印刷版およびコーティング、調製方法ならびに使用
WO2013145949A1 (fr) * 2012-03-29 2013-10-03 富士フイルム株式会社 Plaque originale pour plaque d'impression lithographique, et son procédé d'impression

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002207293A (ja) * 2001-01-12 2002-07-26 Fuji Photo Film Co Ltd 平版印刷版原版
JP2007256445A (ja) * 2006-03-22 2007-10-04 Mitsubishi Paper Mills Ltd 光重合性組成物および感光性平版印刷版材料
JP2009537458A (ja) * 2006-05-17 2009-10-29 アメリカン・ダイ・ソース・インコーポレーテッド 平版印刷版コーティング用新規材料、それを含有する平版印刷版およびコーティング、調製方法ならびに使用
EP2072570A1 (fr) * 2007-12-20 2009-06-24 Agfa Graphics N.V. Précurseur de plaque d'impression lithographique
WO2013145949A1 (fr) * 2012-03-29 2013-10-03 富士フイルム株式会社 Plaque originale pour plaque d'impression lithographique, et son procédé d'impression

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113474178A (zh) * 2019-01-31 2021-10-01 富士胶片株式会社 平版印刷版原版、平版印刷版的制作方法及平版印刷方法
CN113474178B (zh) * 2019-01-31 2023-09-15 富士胶片株式会社 平版印刷版原版、平版印刷版的制作方法及平版印刷方法
US11803124B2 (en) 2019-01-31 2023-10-31 Fujifilm Corporation Planographic printing plate precursor, method of preparing planographic printing plate, and planographic printing method

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