WO2020137919A1 - Composition photosensible, précurseur de plaque d'impression lithographique, procédé de production de plaque d'impression lithographique, et procédé d'impression lithographique - Google Patents

Composition photosensible, précurseur de plaque d'impression lithographique, procédé de production de plaque d'impression lithographique, et procédé d'impression lithographique Download PDF

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Publication number
WO2020137919A1
WO2020137919A1 PCT/JP2019/050198 JP2019050198W WO2020137919A1 WO 2020137919 A1 WO2020137919 A1 WO 2020137919A1 JP 2019050198 W JP2019050198 W JP 2019050198W WO 2020137919 A1 WO2020137919 A1 WO 2020137919A1
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group
polymer
lithographic printing
formula
printing plate
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PCT/JP2019/050198
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English (en)
Japanese (ja)
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洋平 石地
彬 阪口
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富士フイルム株式会社
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Publication of WO2020137919A1 publication Critical patent/WO2020137919A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the present invention relates to a photosensitive composition, a lithographic printing plate precursor, a lithographic printing plate making method, and a lithographic printing method.
  • a lithographic printing plate consists of a lipophilic image area that receives ink during the printing process and a hydrophilic non-image area that receives fountain solution.
  • Lithographic printing utilizes the property that water and oil-based ink repel each other, making the lipophilic image part of the lithographic printing plate the ink receiving part and the hydrophilic non-image part dampening water receiving part (ink non-receiving part). ) Is a method in which a difference in ink adhesion is caused on the surface of the lithographic printing plate, the ink is applied only to the image area, and then the ink is transferred to a printing medium such as paper for printing.
  • image exposure by CTP Computer to Plate
  • the image exposure is performed by directly scanning the lithographic printing plate precursor using a laser or a laser diode without using a lith film.
  • On-press development is a method in which after the image exposure of the lithographic printing plate precursor, the conventional wet development process is not carried out and the lithographic printing plate precursor is directly attached to the printing machine and the non-image part of the image recording layer is removed at the initial stage of the usual printing process. is there.
  • Patent Document 1 describes an imageable element containing a substrate and a thermosensitive imageable composition containing a graft copolymer having a hydrophilic segment and a hydrophobic segment.
  • both developability and printing durability of the obtained lithographic printing plate are important properties, but it is known that both properties have a trade-off relationship.
  • an on-press development type lithographic printing plate precursor for producing a lithographic printing plate by on-press development it is difficult to achieve both on-press developability and printing durability.
  • an ink that cures by irradiation with ultraviolet rays hereinafter, also referred to as “ultraviolet ray curable ink” is increasingly used as a printing ink. UV curable ink has high productivity because it can be dried instantly, and generally it is easy to reduce environmental pollution because it is solvent-free or contains a small amount of solvent.
  • Q represents a single bond or a divalent linking group
  • W represents a divalent group having a Hansen solubility parameter of 18 or more
  • n represents an integer of 1 or more
  • Y represents a hydrogen atom.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom, an alkyl group or an aryl group, and R 1 and R 2 are bonded to each other to form a ring structure with an adjacent nitrogen atom.
  • L is a divalent linking group
  • X is an oxygen atom, a methylene group or NR 4
  • R 4 is a hydrogen atom or an alkyl group.
  • R 01 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group or a cyano group, and Q, W and Y Are respectively synonymous with Q, W and Y in the above formula (1).
  • the polymer is a copolymer derived from a monomer represented by the following formula (M-1) and a monomer represented by the following formula (M-2).
  • R 01 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group or a cyano group
  • Q, W and Y are respectively synonymous with Q, W and Y in the above formula (1).
  • R 02 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group or a cyano group
  • Z is a hydrogen atom
  • a method for producing a lithographic printing plate including: (18) A step of exposing the lithographic printing plate precursor as described in (16) to an image, and supplying at least one selected from a printing ink and a fountain solution to remove an unexposed portion of the image recording layer on a printing machine to obtain a lithographic printing plate.
  • a planographic printing method comprising a step of producing a printing plate and a step of printing with the obtained planographic printing plate.
  • a photosensitive composition having excellent developability and printing durability can be provided. Further, according to the present invention, it is possible to provide a lithographic printing plate precursor excellent in developability and printing durability. Furthermore, according to the present invention, it is possible to provide a method for producing a lithographic printing plate or a lithographic printing method using a lithographic printing plate precursor having excellent developability and printing durability.
  • step is included in this term as long as the intended purpose of the step is achieved, not only when it is an independent step but also when it cannot be clearly distinguished from other steps. ..
  • each component in the composition or each structural unit in the polymer may be used alone or in combination of two or more. Further, each component in the composition, or the amount of each constitutional unit in the polymer, particularly when each component in the composition, or a plurality of substances or constitutional units corresponding to each constitutional unit in the polymer are present, Unless otherwise indicated, it refers to the total amount of the corresponding substances present in the composition or of the respective constituent units present in the polymer.
  • the mass average molecular weight (Mw) and number average molecular weight (Mn) are columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both manufactured by Tosoh Corp.) unless otherwise specified.
  • the molecular weight was detected by a gel permeation chromatography (GPC) analyzer using a THF (tetrahydrofuran) solvent with a differential refractometer and converted using polystyrene as a standard substance.
  • GPC gel permeation chromatography
  • the term “lithographic printing plate precursor” includes not only the lithographic printing plate precursor but also the discarded plate precursor.
  • the term “lithographic printing plate” includes not only a lithographic printing plate precursor prepared by performing operations such as exposure and development, but also a discarded plate, if necessary. In the case of a waste original plate, the operations of exposure and development are not always necessary.
  • the waste plate is a printing plate to be attached to a plate cylinder that is not used when a part of the paper surface is printed in a single color or two colors in color newspaper printing, for example.
  • the photosensitive composition according to the present invention contains a polymer having a group represented by the following formula (1).
  • -Q-[W] n -Y Formula (1) (In the formula (1), Q represents a single bond or a divalent linking group, W represents a divalent group having a Hansen solubility parameter of 18 or more, n represents an integer of 1 or more, and Y represents a hydrogen atom. Or represents a monovalent organic group.)
  • the polymer contained in the photosensitive composition according to the present invention has a group represented by the formula (1) (hereinafter, also referred to as “specific group”).
  • the specific group is characterized by containing a divalent group having a Hansen solubility parameter of 18 or more. Since the specific polymer of the present invention contains a divalent group having a Hansen solubility parameter of 18 or more, while maintaining its affinity with a fountain solution, it has resistance to an ultraviolet curable ink, and thus the specific polymer of the present invention When the specific polymer is used, the effect of the present invention that the developing property (particularly, the on-press developing property) is excellent and the printing durability (particularly, the printing durability when using the ultraviolet curable ink) is excellent. It is thought to be obtained.
  • Q represents a single bond or a divalent linking group.
  • the number of atoms (excluding hydrogen atoms) contained in the divalent linking group represented by Q is preferably 20 or less.
  • the alkylene group may have a substituent (for example, a hydroxy group).
  • the arylene group may have a substituent (for example, an alkyl group).
  • W represents a divalent group having a Hansen solubility parameter of 18 or more.
  • the Hansen solubility parameter is known as a value used to predict the solubility of a substance (particularly a polymer).
  • the Hansen solubility parameter of the divalent group corresponding to W is a value calculated by the following method. First, using a commercially available ChemDraw Professional 16.0 (manufactured by PerkinElmer), the structure of a divalent group corresponding to W is converted into a SMILES (Simplicited Molecular Input Line Entry Syntax) notation, and this is commercially available.
  • the solubility parameter software (Hansen Solubility Parameters in Practice ver. 4.1.07) is used for the calculation.
  • W is preferably a divalent group containing at least one atom selected from a nitrogen atom and an oxygen atom.
  • W is preferably a divalent group containing at least one group selected from an amide group, a hydroxy group and an ester group.
  • the amide group contained in W is a group in which a carbonyl group or a sulfonyl group and a nitrogen atom are bonded to each other, and includes a case where it forms a part of a ring structure as in a lactam.
  • the ester group contained in W is a group in which a carbonyl group and an oxygen atom are bonded to each other, and includes a case where it forms a part of a ring structure as in a lactone.
  • W is preferably selected from divalent groups represented by the following formulas (I) to (IV).
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom, an alkyl group or an aryl group, and R 1 and R 2 are bonded to each other to form a ring structure with an adjacent nitrogen atom.
  • L is a divalent linking group
  • X is an oxygen atom, a methylene group or NR 4
  • R 4 is a hydrogen atom or an alkyl group.
  • n represents a position linked to Q and Y respectively, and when n is 2 or more, it represents a position constituting a repeating unit: a hydrogen atom bonded to a carbon atom bonded to an amide group in formula (I), or a formula In (III) or formula (IV), the hydrogen atom bonded to the carbon atom to which L is bonded may be substituted with a methyl group.
  • the alkyl group represented by R 1 , R 2 or R 3 is an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms.
  • the alkyl group may be linear, branched, or cyclic, and may have a substituent.
  • the substituent include a hydroxy group, a carboxyl group, an amino group and a phenyl group.
  • Specific examples of the alkyl group include a methyl group, an ethyl group and an isopropyl group.
  • the aryl group represented by R 1 , R 2 or R 3 is an aryl group having 6 to 14 carbon atoms, preferably 6 carbon atoms. The aryl group may have a substituent.
  • Examples of the substituent include an alkyl group, an alkoxy group and an alkoxycarbonyl group.
  • Specific examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
  • Examples of the ring structure formed by combining R 1 and R 2 together with the adjacent nitrogen atom include a morpholine structure, a piperidyl structure, and a pyrrolidine structure.
  • the number of atoms (excluding hydrogen atoms) contained in the divalent linking group represented by L is preferably 10 or less.
  • the alkylene group may have a substituent (for example, a hydroxy group).
  • the arylene group may have a substituent (for example, an alkyl group).
  • Such a linking group can be derived from a (meth)acrylic acid ester-based monomer.
  • the alkyl group represented by R 4 is an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group may be linear, branched, or cyclic, and may have a substituent.
  • a hydroxy group etc. are mentioned as a substituent.
  • R 4 is preferably a methyl group.
  • divalent groups represented by W with a Hansen solubility parameter of 18 or more are shown in the table below.
  • the structure shows the structure of a divalent group corresponding to W
  • SMILES shows the SMILES notation of the structure of a divalent group corresponding to W
  • HSP is the divalent group corresponding to W.
  • the solubility parameter is shown.
  • the broken line portion represents the position linked to Q and Y when n is 1 in the formula (1), and the position constituting the repeating unit when n is 2 or more. ..
  • the atom constituting the chain connecting Q and Y of the divalent group corresponding to W has a higher degree of negativeness than the carbon atom.
  • a form in which the carbon atom is bonded to both sides of the atom having a higher degree of negativeness than the carbon atom is used.
  • Treated as a divalent group structure corresponding to W when the atoms constituting the chain connecting Q and Y are composed of carbon atoms and nitrogen atoms, the form of carbon atom-nitrogen atom-carbon atom is treated as a divalent group structure corresponding to W.
  • W is preferably a divalent group having a Hansen solubility parameter value of 18 to 30.
  • n represents an integer of 1 or more. n is preferably 5 to 200, more preferably 10 to 150, and particularly preferably 20 to 100, from the viewpoint of improving printing durability by improving compatibility with other components contained in the photosensitive composition of the present invention. ..
  • Y represents a hydrogen atom or a monovalent organic group.
  • the monovalent organic group represented by Y contributes to improvement in developability.
  • ClogP of Y is preferably 3 or less.
  • ClogP of Y is 3 or less, the hydrophilicity of the terminal of the specific group is kept good, which contributes to the improvement of the developability (in particular, the on-press developability).
  • ClogP of Y is a value calculated by inputting Y in the form of CH 3 —Y into a commercially available ChemDraw Professional 16.0.
  • the content of the group represented by formula (1) in the specific polymer of the present invention is preferably 1 to 50% by mass, more preferably 5 to 45% by mass, and 10 to 10% from the viewpoint of improving developability and printing durability. 40% by weight is particularly preferred.
  • the group represented by formula (1) is bonded to the polymer backbone of the specific polymer of the present invention via Q.
  • the specific polymer of the present invention is preferably a polymer containing a repeating unit derived from a monomer represented by the following formula (M-1).
  • R 01 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group or a cyano group
  • Q, W and Y are respectively synonymous with Q, W and Y in the above formula (1).
  • the alkyl group represented by R 01 , the alkoxycarbonyl group, the alkylcarbonyl group, or the alkyl group contained in the amide group is an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms.
  • the alkyl group may be linear, branched, or cyclic, and may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aryl group and the like. Specific examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, a benzyl group and the like.
  • the aryl group represented by R 01 or the aryloxycarbonyl group or the aryl group contained in the arylcarbonyl group is an aryl group having 6 to 10, preferably 6 carbon atoms.
  • the aryl group may have a substituent. Examples of the substituent include an alkoxy group, an alkoxycarbonyl group and an alkyl group. Specific examples of the aryl group include a phenyl group and a tolyl group.
  • Examples of the polymer containing a repeating unit derived from the monomer represented by the formula (M-1) include a homopolymer containing a repeating unit derived from the monomer represented by the formula (M-1).
  • the polymer containing a repeating unit derived from the monomer represented by the formula (M-1) includes a repeating unit derived from the monomer represented by the formula (M-1) and a polymer represented by the formula (M-1). And a repeating unit derived from a copolymerizable monomer.
  • Examples of the monomer copolymerizable with the monomer represented by the formula (M-1) include styrene compounds, (meth)acrylate compounds, (meth)acrylonitrile compounds, (meth)acrylamide compounds, vinyl halide compounds, vinyl ester compounds.
  • Preferred are monofunctional ethylenically unsaturated compounds such as vinyl ether compounds and ⁇ -olefin compounds.
  • a monomer represented by the following formula (M-2) is preferable.
  • R 02 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group or a cyano group
  • Z is a hydrogen atom.
  • the alkyl group represented by R 02 , the alkoxycarbonyl group, the alkylcarbonyl group or the alkyl group contained in the amide group is an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms.
  • the alkyl group may be linear, branched, or cyclic, and may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aryl group and the like. Specific examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, a benzyl group and the like.
  • the aryl group represented by R 01 or the aryloxycarbonyl group or the aryl group contained in the arylcarbonyl group is an aryl group having 6 to 10, preferably 6 carbon atoms.
  • the aryl group may have a substituent. Examples of the substituent include an alkoxy group, an alkoxycarbonyl group and an alkyl group. Specific examples of the aryl group include a phenyl group and a tolyl group.
  • the alkyl group represented by Z or the alkylcarbonyloxy group, the alkoxy group, the alkylcarbonyl group or the alkyl group contained in the alkylcarbonyl group has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. It is an alkyl group.
  • the alkyl group may be linear, branched, or cyclic, and may have a substituent. Examples of the substituent include a hydroxy group and an aryl group. Specific examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, a benzyl group and the like.
  • the aryl group represented by Z or the aryl group contained in the arylcarbonyloxy group or the arylcarbonyl group is an aryl group having 6 to 10, preferably 6 carbon atoms.
  • the aryl group may have a substituent. Examples of the substituent include an alkoxy group, an alkoxycarbonyl group and an alkyl group. Specific examples of the aryl group include a phenyl group and a tolyl group.
  • monomer copolymerizable with the monomer represented by the formula (M-1) include styrene, methyl methacrylate, acrylonitrile, methacrylonitrile, N,N-dimethyl(meth)acrylamide, acryloylmorpholine.
  • the ratio of the repeating unit derived from the monomer represented by the formula (M-1) to the repeating unit derived from the monomer copolymerizable with the monomer represented by the formula (M-1) in the above copolymer Is such that the amount of the repeating unit derived from the monomer represented by the formula (M-1) is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and 10 to 30% by mass based on the copolymer. % Is more preferable.
  • the specific polymer of the present invention is preferably a graft polymer having a group represented by the formula (1) as a branch component.
  • the number n of repeating units corresponding to W in formula (1) may be 2 or more.
  • the number n of repeating units is preferably 5 to 200, more preferably 10 to 150, and particularly preferably 20 to 100.
  • the specific polymer of the present invention can be synthesized by a known method.
  • one or more monomers represented by the above formula (M-1) may be polymerized, or one or more monomers represented by the above formula (M-1) and the above formula (M-1) may be polymerized.
  • a copolymerizable monomer for example, one or more monomers represented by the following formula (M-2) may be polymerized.
  • the specific polymer of the present invention may contain a polymerizable group.
  • the polymerizable group may be contained in the group represented by the formula (1) or may be contained in a part other than the group represented by the formula (1). By containing a polymerizable group, printing durability can be further improved.
  • the polymerizable group is not particularly limited and may be a cationically polymerizable group or a radically polymerizable group. From the viewpoint of reactivity, radically polymerizable groups are preferred. From the viewpoint of reactivity, the polymerizable group is preferably an ethylenically unsaturated group, specifically, a styryl group, a (meth)acryloxy group, a (meth)acrylamide group is preferable, and a (meth)acryloxy group is particularly preferable. ..
  • the method of introducing the polymerizable group into the specific polymer includes a method of introducing the polymerizable group by remaining a polyfunctional monomer added during the polymer synthesis and a method of introducing the polymer group by a polymer reaction after the polymer synthesis.
  • the method of introducing by reaction is preferable. This is because introducing a polymerizable group after polymer synthesis allows more active polymerizable groups to be present on the surface of the polymer, and therefore the reactivity with the matrix increases and it is easier to form a strong crosslink with the matrix. This is because
  • the introduction of a polymerizable group into a polymer by a polymer reaction is specifically performed by, for example, adding a compound having an epoxy group and a polymerizable group (for example, glycidyl) to a polymer having a constitutional unit having a carboxy group such as methacrylic acid introduced therein.
  • a compound having an epoxy group and a polymerizable group for example, glycidyl
  • a compound having an isocyanate group and a polymerizable group for example, 2-isocyanatoethyl methacrylate
  • a polymerizable group for example, 2-isocyanatoethyl methacrylate
  • a structural unit having a carboxy group such as methacrylic acid, or a structural unit having a group having the active hydrogen (hereinafter, collectively referred to as "structural unit before reaction")
  • the polymerizable group is Adjusting the reaction rate of the compound having an epoxy group and a polymerizable group, or the compound having an isocyanate group and a polymerizable group, with respect to these structural units after being introduced (also referred to as "the structural unit after the reaction”).
  • the structural unit having a carboxy group, the structural unit having a group having active hydrogen, or the like can be left in the specific polymer.
  • the constitutional unit before the reaction is a constitutional unit having a hydrophilic structure
  • the constitution in which the specific polymer has a hydrophilic structure (an ionic group such as a carboxy group or an amino group) by lowering the reaction rate is obtained.
  • a unit can be contained, and the developability and the like of the lithographic printing plate precursor can be further improved.
  • the reaction rate is, for example, preferably 10 to 100%, more preferably 30 to 70%.
  • the introduction of the polymerizable group into the polymer is carried out by a method of reacting a compound having a carboxy group and a polymerizable group with a polymer having a constitutional unit having an epoxy group such as glycidyl (meth)acrylate introduced therein.
  • the content of the constituent unit having a polymerizable group in the specific polymer is preferably 1 to 50% by mass, and preferably 5 to 45% by mass, with respect to the specific polymer, from the viewpoint of printing durability when an ultraviolet curable ink is used. Is more preferable, 10 to 40% by mass is further preferable, and 10 to 35% by mass is particularly preferable.
  • the polymerizable group value of the specific polymer (the amount of the polymerizable group per 1 g of the specific polymer) is preferably 0.01 to 2.0 mol/g, more preferably 0.1 to 1.0 mol/g.
  • the polymerizable group value is measured by the iodometric titration method.
  • the specific polymer of the present invention may have a crosslinked structure. Since the specific polymer has a cross-linking structure, the hardness of the specific polymer itself is improved, so that the strength of the image area is improved and even when an ultraviolet curable ink that deteriorates the printing plate more easily than other inks is used. It is considered that the printing durability is further improved.
  • the cross-linking structure is not particularly limited and is preferably a structural unit obtained by polymerizing a polyfunctional ethylenically unsaturated compound or a structural unit in which one or more kinds of reactive groups form a covalent bond inside the polymer.
  • the functional number of the polyfunctional ethylenically unsaturated compound is preferably 2 to 15, more preferably 3 to 10, and more preferably 4 to 10 from the viewpoint of printing durability and on-press development property when an ultraviolet curable ink is used. Is more preferable, and 5 to 10 is particularly preferable.
  • the constitutional unit having a crosslinked structure is preferably a bifunctional to 15-functional branched unit from the viewpoint of printing durability and on-press developability when an ultraviolet curable ink is used.
  • the n-functional branching unit refers to a branching unit having n molecular chains, in other words, a structural unit having an n-functional branching point (crosslinking structure).
  • the ethylenically unsaturated group in the polyfunctional ethylenically unsaturated compound is not particularly limited, and examples thereof include (meth)acryloxy group, (meth)acrylamide group, aromatic vinyl group, and maleimide group.
  • the polyfunctional ethylenically unsaturated compound is preferably a polyfunctional (meth)acrylate compound, a polyfunctional (meth)acrylamide compound, or a polyfunctional aromatic vinyl compound.
  • polyfunctional (meth)acrylate compound examples include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, 1,4-butanediol diacrylate, 1,6 -Hexanediol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tricyclodecane dimethylol diacrylate, ditrimethylol propane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol triacrylate, dipentaerythritol hexa Examples thereof include acrylate and triacrylate of tris( ⁇ -hydroxyethyl)isocyanurate.
  • polyfunctional (meth)acrylate compounds examples include N,N'-methylenebisacrylamide, N-[tris(3-acrylamidopropoxymethyl)methyl]acrylamide, and the like.
  • polyfunctional aromatic vinyl compound examples include divinylbenzene and the like.
  • the carbon number of the branching unit is not particularly limited and is preferably 8 to 100, more preferably 8 to 70.
  • the content of the structural unit having a crosslinked structure in the specific polymer is preferably 1 to 50% by mass with respect to the specific polymer from the viewpoint of printing durability and on-press development property when an ultraviolet curable ink is used. Is more preferably from 45 to 45% by mass, further preferably from 10 to 40% by mass, particularly preferably from 10 to 35% by mass.
  • the specific polymer of the present invention is not limited to the following specific examples.
  • the content of each structural unit (subscript in the lower right of the bracket) is a mass ratio, and the content of the divalent linking group corresponding to W in the group represented by the above formula (1) is added to the lower right of the bracket.
  • the letter represents an integer (repeating number) corresponding to n in the group represented by the formula (1).
  • W(HSP) represents the Hansen solubility parameter of the divalent linking group corresponding to W.
  • Y(ClogP) represents ClogP of a monovalent organic group corresponding to Y.
  • the content of the specific polymer in the photosensitive composition of the present invention is from 10 to 90% by mass based on the photosensitive composition from the viewpoint of printing durability and on-press developability when an ultraviolet curable ink is used. Is preferred, 20 to 80 mass% is more preferred, 30 to 70 mass% is still more preferred, and 35 to 65 mass% is particularly preferred.
  • the photosensitive composition of the present invention preferably 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 absorbing agent is preferably a dye having an absorption maximum at a wavelength of 750 to 1,400 nm.
  • dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, and metal thiolate complex dyes.
  • dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, and metal thiolate complex dyes.
  • cyanine dyes Preferred among these dyes are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Furthermore, cyanine dyes and indolenine cyanine dyes are more preferred. Of these, cyanine dyes are particularly preferable.
  • cyanine dyes include compounds described in paragraphs 0017 to 0019 of JP 2001-133969 A, paragraphs 0016 to 0021 of JP 2002-023360 A, and paragraphs 0012 to 0037 of JP 2002-040638 A.
  • the compounds described in paragraphs 0008 to 0009 of JP-A-5-5005 and paragraphs 0022 to 0025 of JP-A 2001-222101 can also be preferably used.
  • the compounds described in paragraphs 0072 to 0076 of JP-A 2008-195018 are preferable.
  • the infrared absorbers may be used alone or in combination of two or more. Further, a pigment and a dye may be used together as an infrared absorber.
  • the content of the infrared absorbing dye in the photosensitive composition is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0% by mass based on the photosensitive composition.
  • the photosensitive composition of the present invention preferably contains a polymerization initiator, and more preferably contains a polymerization initiator and a polymerizable compound.
  • the polymerization initiator is a compound that generates a polymerization initiation species such as a radical or a cation by the energy of light, heat or both, and is a known thermal polymerization initiator, a compound having a bond with a small bond dissociation energy, a photopolymerization initiator. It can be appropriately selected and used from the following.
  • As the polymerization initiator an infrared-sensitive polymerization initiator is preferable.
  • a radical polymerization initiator is preferable as the polymerization initiator. Two or more radical polymerization initiators may be used in combination.
  • the radical polymerization initiator may be either an electron-accepting polymerization initiator or an electron-donating polymerization initiator.
  • Electrode-accepting polymerization initiator examples include organic halides, carbonyl compounds, azo compounds, organic peroxides, metallocene compounds, azide compounds, hexaarylbiimidazole compounds, disulfone compounds, oxime ester compounds, and onium salt compounds. are listed.
  • the organic halide for example, the compounds described in paragraphs 0022 to 0023 of JP-A-2008-195018 are preferable.
  • the carbonyl compound for example, compounds described in paragraph 0024 of JP-A-2008-195018 are preferable.
  • the azo compound include the azo compounds described in JP-A-8-108621.
  • the organic peroxide for example, the compounds described in paragraph 0025 of JP-A-2008-195018 are preferable.
  • the metallocene compound for example, the compounds described in paragraph 0026 of JP-A-2008-195018 are preferable.
  • the azide compound include compounds such as 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone.
  • the compounds described in paragraph 0027 of JP-A-2008-195018 are preferable.
  • the disulfone compound include compounds described in JP-A Nos. 61-166544 and 2002-328465.
  • the oxime ester compound for example, compounds described in paragraphs 0028 to 0030 of JP-A-2008-195018 are preferable.
  • onium salts such as iodonium salts, sulfonium salts and azinium salts.
  • iodonium salts and sulfonium salts Particularly preferred are iodonium salts and sulfonium salts. Specific examples of the iodonium salt and the sulfonium salt are shown below, but the present invention is not limited thereto.
  • a diphenyliodonium salt is preferable, and in particular, having an electron-donating group as a substituent, for example, a diphenyliodonium salt substituted with an alkyl group or an alkoxyl group is preferable, and an asymmetric diphenyliodonium salt is preferable. preferable.
  • diphenyliodonium hexafluorophosphate
  • 4-methoxyphenyl-4-(2-methylpropyl)phenyliodonium hexafluorophosphate
  • 4-(2-methylpropyl)phenyl-p-tolyliodonium hexa Fluorophosphate
  • 4-hexyloxyphenyl-2,4,6-trimethoxyphenyliodonium hexafluorophosphate
  • 4-hexyloxyphenyl-2,4-diethoxyphenyliodonium tetrafluoroborate
  • 4-octyloxy Phenyl-2,4,6-trimethoxyphenyliodonium 1-perfluorobutanesulfonate
  • 4-octyloxyphenyl-2,4,6-trimethoxyphenyliodonium hexafluorophosphate
  • Iodonium hexafluorophosphat
  • a triarylsulfonium salt is preferable, and particularly, a compound 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 is preferable.
  • 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 electron-accepting polymerization initiators may be used alone or in combination of two or more.
  • the content of the electron-accepting polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and 0.8 to 20% by mass with respect to the photosensitive composition. % Is more preferable.
  • the electron-donating polymerization initiator contributes to improving the printing durability of the lithographic printing plate.
  • Examples of the electron-donating polymerization initiator include the following five types.
  • X is preferably a hydrogen atom, a carboxy group, a trimethylsilyl group or a benzyl group.
  • Sulfur-containing compound A compound in which the nitrogen atom of the above aminoacetic acid compound is replaced with a sulfur atom can generate an active radical by the same action.
  • Sulfur-containing compound A compound in which the nitrogen atom of the above aminoacetic acid compound is replaced with a sulfur atom can generate an active radical by the same action.
  • phenylthioacetic acid which may have a substituent on the phenyl group.
  • Tin-containing compound The above-mentioned aminoacetic acid compound in which the nitrogen atom is replaced by a tin atom can generate an active radical by the same action.
  • Sulfinates An active radical can be generated by oxidation. Specific examples include sodium arylsulfin and the like.
  • borate compounds are preferred.
  • the borate compound is preferably a tetraarylborate compound or a monoalkyltriarylborate compound, more preferably a tetraarylborate compound from the viewpoint of compound stability, and a tetraaryl having one or more aryl groups having an electron-withdrawing group.
  • Borate compounds are particularly preferred.
  • the electron-withdrawing group is preferably a group having a positive Hammett's rule ⁇ value, and more preferably a group having a Hammett's rule ⁇ value of 0 to 1.2. For Hammett's ⁇ value ( ⁇ p value and ⁇ m value), see Hansch, C. et al.
  • the electron-withdrawing group is preferably a halogen atom, a trifluoromethyl group or a cyano group, more preferably a fluorine atom, a chlorine atom, a trifluoromethyl group or a cyano group.
  • the counter cation contained in the borate compound is preferably an alkali metal ion or a tetraalkylammonium ion, more preferably a sodium ion, a potassium ion or a tetrabutylammonium ion.
  • the counter cation may be an iodonium cation or the like in the onium salt described in the electron-accepting polymerization initiator, or a dye structure in the infrared absorber.
  • iodonium borate described in paragraph 0048 of Japanese Patent No. 5129242 is also preferably mentioned.
  • borate compound examples include compounds represented by the following formula I.
  • R 1 , R 2 , R 3 and R 4 each independently represent an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a cycloalkyl group or a heterocyclyl group, or R 1 , R 2 Two or more of 2 , R 3 and R 4 are combined to form a heterocycle containing a boron atom described in Formula I as a ring member, and Z + represents a cation.
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and 2 carbon atoms.
  • Is preferably an alkynyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a heterocyclyl group having 5 to 10 total atoms of carbon, oxygen, sulfur, and nitrogen, and an alkyl group having 1 to 12 carbon atoms.
  • an aryl group having 6 to 10 carbon atoms is more preferable.
  • heterocyclyl group examples include a pyridyl ring, a pyrimidine ring, a triazole ring and the like.
  • the alkyl group, the aryl group, the alkenyl group, the alkynyl group, the cycloalkyl group, or the heterocyclyl group may have a substituent.
  • Preferred examples of the substituent include the electron-withdrawing group in the aryl group having the above-mentioned electron-withdrawing group.
  • at least three of R 1 , R 2 , R 3, and R 4 are preferably aryl groups, at least three are aryl groups, and one is more preferably an alkyl group, and all four are aryl.
  • Z + represents a monovalent cation or a polyvalent cation, and a monovalent cation is preferable.
  • Z + is preferably an alkali metal ion or a tetraalkylammonium ion, more preferably a sodium ion, a potassium ion or a tetrabutylammonium ion.
  • R 1 , R 2 , R 3 and R 4 may be an iodonium cation or the like in the onium salt described in the electron-accepting polymerization initiator, or may be a dye structure in the infrared absorber.
  • X c + represents a counter cation in the borate compound, preferably an alkali metal ion or a tetraalkylammonium ion, more preferably an alkali metal ion or a tetrabutylammonium ion.
  • Bu represents an n-butyl group.
  • the electron-donating polymerization initiators may be used alone or in combination of two or more.
  • the content of the electron-donating polymerization initiator is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, and still more preferably 0.1 to 20% by mass, based on the photosensitive composition. ..
  • the polymerizable compound may be, for example, a radically polymerizable compound or a cationically polymerizable compound, and is an addition polymerizable compound having at least one ethylenically unsaturated bond (ethylenically unsaturated compound). It is preferable.
  • ethylenically unsaturated compound a compound having at least one terminal ethylenically unsaturated bond is preferable, and a compound having two or more terminal ethylenically unsaturated bonds is more preferable.
  • the polymerizable compound may have a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer or an oligomer, or a mixture thereof.
  • Examples of monomers include unsaturated carboxylic acids (eg acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid) and their esters and amides.
  • esters of unsaturated carboxylic acid and polyhydric alcohol compound and amides of unsaturated carboxylic acid and polyhydric amine compound are used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy, and a monofunctional or A dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used.
  • a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group with a monofunctional or polyfunctional alcohol, amine, or thiol is also suitable.
  • a compound group in which the above unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, styrene, vinyl ether or the like can be used.
  • JP-T-2006-508380 JP-A-2002-287344, JP-A-2008-256850, JP-A-2001-342222, JP-A-9-179296, and JP-A-9-179297.
  • the monomer of an ester of a polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, There are trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, isocyanuric acid ethylene oxide (EO) modified triacrylate, polyester acrylate oligomer and the like.
  • acrylic acid esters such as ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate,
  • EO isocyanuric acid ethylene oxide
  • 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] Examples include dimethyl methane and bis[p-(methacryloxyethoxy)phenyl]dimethyl methane.
  • amide monomer of a polyvalent amine compound and an unsaturated carboxylic acid examples include methylenebisacrylamide, methylenebismethacrylamide, 1,6-hexamethylenebisacrylamide, 1,6-hexamethylenebismethacrylamide, Examples include diethylenetriamine tris acrylamide, xylylene bis acrylamide, and xylylene bis methacrylamide.
  • a urethane-based addition-polymerizable compound produced by addition reaction of isocyanate and hydroxy group is also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708.
  • Examples thereof include urethane compounds.
  • R M4 and R M5 each independently represent a hydrogen atom or a methyl group.
  • urethane acrylates described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-A-2003-344997, and JP-A-2006-65210, Ethylene oxide described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, JP-B-62-39418, JP-A-2000-250211, and JP-A-2007-94138.
  • the content of the polymerizable compound is preferably 5 to 75% by mass, more preferably 10 to 70% by mass, and particularly preferably 15 to 60% by mass, based on the photosensitive composition.
  • the photosensitive composition of the present invention When the photosensitive composition of the present invention is applied to the image recording layer of a lithographic printing plate precursor, the photosensitive composition is a binder polymer, a chain transfer agent, polymer particles, a low molecular weight hydrophilic compound, an oil sensitizer, an acid colorant. , A colorant, and other components can be appropriately contained.
  • the binder polymer is a polymer that functions as a binder for the image recording layer, and is preferably a polymer having a film-forming property, and (meth)acrylic resin, polyvinyl acetal resin, polyurethane resin and the like are preferable.
  • the binder polymer does not include a polymer corresponding to the specific polymer of the present invention.
  • binder polymer a known binder polymer used in the image recording layer of the lithographic printing plate precursor can be preferably used.
  • the binder polymer used in the on-press development type lithographic printing plate precursor (hereinafter, also referred to as binder polymer for on-press development) will be described in detail.
  • the binder polymer for on-press development is preferably a binder polymer having an alkylene oxide chain.
  • the binder polymer having an alkylene oxide chain may have a poly(alkylene oxide) moiety in the main chain or in a side chain.
  • it may be a graft polymer having poly(alkylene oxide) in the side chain, or a block copolymer of a block composed of a poly(alkylene oxide)-containing repeating unit and a block composed of a (alkylene oxide)-free repeating unit.
  • a polyurethane resin is preferred when it has a poly(alkylene oxide) moiety in the main chain.
  • (meth)acrylic resin When the main chain polymer has a poly(alkylene oxide) moiety in its side chain, (meth)acrylic resin, polyvinyl acetal resin, polyurethane resin, polyurea resin, polyimide resin, polyamide resin, epoxy resin, polystyrene resin, novolac type Phenolic resins, polyester resins, synthetic rubbers and natural rubbers are mentioned, and (meth)acrylic resins are particularly preferable.
  • 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, still more preferably 2 to 50. When the number of repetitions of the alkylene oxide is 120 or less, deterioration of both printing durability due to abrasion and printing durability due to ink acceptability is suppressed, which is preferable.
  • the poly(alkylene oxide) moiety is preferably contained in a structure represented by the following formula (AO) as a side chain of the binder polymer, and represented by the following formula (AO) as a side chain of the (meth)acrylic resin. More preferably, it is contained in a structure of
  • 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 an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group.
  • y is preferably 2 to 70, more preferably 2 to 50.
  • R 1 is preferably a hydrogen atom or a methyl group, and 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 a polymer reaction. Examples of the polymer having an ethylenically unsaturated bond in the main chain of the molecule include poly-1,4-butadiene and poly-1,4-isoprene.
  • polymers having an ethylenically unsaturated bond in the side chain of the molecule include a polymer of an ester or amide of acrylic acid or methacrylic acid, wherein the residue of the ester or amide (R of —COOR or —CONHR) is Mention may be made of polymers having ethylenically unsaturated bonds.
  • amide residue include —CH 2 CH ⁇ CH 2 , —CH 2 CH 2 —Y (wherein Y represents a cyclohexene residue) and —CH 2 CH 2 —OCO—CH ⁇ CH 2. Are listed.
  • the crosslinkable binder polymer has, for example, free radicals (polymerization initiation radicals or growing radicals during the polymerization process of the polymerizable compound) added to its crosslinkable functional group to directly or between the polymers to form a polymerization chain of the polymerizable compound.
  • free radicals polymerization initiation radicals or growing radicals during the polymerization process of the polymerizable compound
  • polymerization initiation radicals or growing radicals during the polymerization process of the polymerizable compound Through addition polymerization through the formation of crosslinks between the polymer molecules to cure.
  • an atom in the polymer for example, a hydrogen atom on a carbon atom adjacent to the functional crosslinking group
  • a free radical is abstracted by a free radical to generate a polymer radical, which is bonded to each other to form a crosslink between polymer molecules. It forms and hardens.
  • the content of the crosslinkable group in the binder polymer is preferably 0 per 1 g of the binder polymer from the viewpoint of good sensitivity and good storage stability. 0.1 mmol to 10.0 mmol, more preferably 1.0 mmol to 7.0 mmol, and particularly preferably 2.0 mmol to 5.5 mmol.
  • (1) to (11) are shown below as specific examples of the binder polymer for on-machine development, but the present invention is not limited to these.
  • the numerical value shown together with each repeating unit represents the molar percentage of the above repeating unit.
  • the numerical value written together with the repeating unit of the side chain indicates the repeating number of the above repeating site. Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group.
  • the mass average molecular weight (Mw) in terms of polystyrene by the GPC method is preferably 2,000 or more, more preferably 5,000 or more, still more preferably 10,000 to 300,000.
  • hydrophilic polymers such as polyacrylic acid and polyvinyl alcohol described in JP-A-2008-195018 can be used in combination. Also, a lipophilic polymer and a hydrophilic polymer can be used in combination.
  • the binder polymer may be present in the image recording layer as a polymer that functions as a binder for each component, or may be present in the form of particles.
  • the average primary particle size is preferably 1,000 nm or less, more preferably 10 to 500 nm, and further preferably 50 to 300 nm.
  • the binder polymers may be used alone or in combination of two or more.
  • the binder polymer can be contained in the image recording layer in any amount.
  • the content of the binder polymer can be appropriately selected depending on the application of the image recording layer, etc., but is preferably 1 to 90% by mass, more preferably 5 to 80% by mass, based on the total mass of the image recording layer.
  • the chain transfer agent contributes to improving the printing durability of the lithographic printing plate.
  • the chain transfer agent is preferably a thiol compound, more preferably a thiol having 7 or more carbon atoms from the viewpoint of boiling point (difficult to volatilize), and further preferably a compound having a mercapto group on the 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 agents may be used alone or in combination of two or more.
  • the content of the chain transfer agent is preferably 0.01 to 50% by mass, more preferably 0.05 to 40% by mass, and further preferably 0.1 to 30% by mass based on the total solid content of the image recording layer.
  • the polymer particles are preferably polymer particles capable of converting the image recording layer to hydrophobic when heat is applied.
  • the polymer particles are at least one selected from hydrophobic thermoplastic polymer particles, thermoreactive polymer particles, polymer particles having a polymerizable group, microcapsules containing a hydrophobic compound, and microgel (crosslinked polymer particles). Is preferred. Among them, polymer particles having a polymerizable group and microgel are preferable.
  • the hydrophobic thermoplastic polymer particles As the hydrophobic thermoplastic polymer particles, Research Disclosure No. of January 1992 is used. 33303, JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, JP-A-9-171250, European Patent No. 931647, and the like, the hydrophobic thermoplastic polymer particles are preferable. Are listed in. Specific examples of the polymer constituting the hydrophobic thermoplastic polymer particles include ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinylcarbazole, and polyalkylene structure.
  • Homopolymers or copolymers of monomers such as acrylates or methacrylates with or mixtures thereof.
  • Preferred are polystyrene, a copolymer containing styrene and acrylonitrile, and polymethylmethacrylate.
  • the volume average particle diameter of the hydrophobic thermoplastic polymer particles is preferably 0.01 to 2.0 ⁇ m.
  • the heat-reactive polymer particles include polymer particles having a heat-reactive group.
  • the polymer particles having a heat-reactive group form a hydrophobized region due to cross-linking due to a heat reaction and a change in a functional group at that time.
  • the heat-reactive group in the polymer particle having a heat-reactive group may be a functional group that performs any reaction as long as a chemical bond is formed, and a polymerizable group is preferable.
  • a polymerizable group examples thereof include an ethylenically unsaturated group (eg, acryloyl group, methacryloyl group, vinyl group, allyl group, etc.) that undergoes radical polymerization reaction, a cationically polymerizable group (eg, vinyl group, vinyloxy group, epoxy group, oxetanyl group).
  • an isocyanato group or a block thereof which carries out an addition reaction an epoxy group, a vinyloxy group and a functional group having an active hydrogen atom which is a reaction partner thereof (for example, an amino group, a hydroxy group, a carboxy group, etc.), a condensation reaction
  • a carboxy group to be carried out and a hydroxy group or amino group as a reaction partner an acid anhydride for carrying out a ring-opening addition reaction and an amino group or hydroxy group as a reaction partner.
  • microcapsules examples include those encapsulating all or part of the constituent components of the image recording layer in microcapsules, as described in JP 2001-277740 A and JP 2001-277742 A.
  • the constituent components of the image recording layer can be contained outside the microcapsules.
  • the hydrophobic constituent components are encapsulated in the microcapsules and the hydrophilic constituent components are contained outside the microcapsules.
  • the microgel may contain a part of the components of the image recording layer on at least one of the inside and the surface thereof.
  • a radically polymerizable group is provided on the surface to form a reactive microgel is preferable from the viewpoint of image forming sensitivity and printing durability.
  • a known method can be used to microencapsulate the components of the image recording layer into a microcapsule or a microgel.
  • the average particle size of the microcapsules or microgels is preferably 0.01 to 3.0 ⁇ m, more preferably 0.05 to 2.0 ⁇ m, and particularly preferably 0.10 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 to 90% by mass with respect to the total mass of the image recording layer.
  • the low-molecular weight hydrophilic compound contributes to the improvement of the on-press developability of the lithographic printing plate precursor without reducing the printing durability of the lithographic printing plate.
  • 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, even more preferably a compound having a molecular weight of less than 500.
  • the low-molecular hydrophilic compound for example, as the water-soluble organic compound, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycols such as tripropylene glycol and ether or ester derivatives thereof, glycerin, Polyols such as pentaerythritol and tris(2-hydroxyethyl)isocyanurate, organic amines such as triethanolamine, diethanolamine and monoethanolamine and salts thereof, organic sulfones such as alkylsulfonic acid, toluenesulfonic acid and benzenesulfonic acid Acids and salts thereof, organic sulfamic acids such as alkylsulfamic acids and salts thereof, organic sulfuric acids such as alkyl sulfuric acid and alkyl ether sulfuric acid and salts thereof, organic phosphonic acids such as phenylphosphonic acid and salts thereof, tartaric acid, oxa
  • 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, and sodium n-octyl sulfonate; ,8,11-Trioxapentadecane-1-sulfonate, sodium 5,8,11-trioxaheptadecane-1-sulfonate, 13-ethyl-5,8,11-trioxaheptadecane-1-sulfone Alkyl sulfonates containing ethylene oxide chains such as sodium acidate, sodium 5,8,11,14-tetraoxatetracosane-1-sulfonate; sodium benzenesulfonate, sodium p-toluenesulfonate, p-hydroxybenzenesul
  • organic sulfates include sulfates of polyethylene oxide alkyl, alkenyl, alkynyl, aryl or heterocyclic monoethers.
  • 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 JP2007-276454A.
  • the betaines are preferably compounds in which the number of carbon atoms of the hydrocarbon substituent on the nitrogen atom is 1 to 5, and specific examples include trimethylammonium acetate, dimethylpropylammonium acetate and 3-hydroxy-4-trimethylammonium.
  • Obutyrate, 4-(1-pyridinio)butyrate, 1-hydroxyethyl-1-imidazolioacetate, trimethylammonium methanesulfonate, dimethylpropylammonium methanesulfonate, 3-trimethylammonio-1-propanesulfonate, 3 -(1-pyridinio)-1-propane sulfonate and the like can be mentioned.
  • the low molecular weight hydrophilic compound Since the low molecular weight hydrophilic compound has a small hydrophobic structure and has almost no surface activity, dampening water permeates into the exposed area (image area) of the image recording layer and reduces the hydrophobicity and film strength of the image area. It is possible to maintain good ink acceptability and printing durability of the image recording layer.
  • the low molecular weight hydrophilic compounds may be used alone or in combination of two or more.
  • the content of the low molecular weight hydrophilic compound is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and further preferably 2 to 10% by mass, based on the total solid content of the image recording layer.
  • the oil sensitizer contributes to the improvement of the ink receptivity (hereinafter, also simply referred to as "receptivity") of the lithographic printing plate.
  • examples of the oil sensitizer include phosphonium compounds, nitrogen-containing low molecular weight compounds, and ammonium group-containing polymers.
  • these compounds function as a surface coating agent for the inorganic layered compound, and have a function of suppressing a decrease in inking property during printing by the inorganic layered compound. Have.
  • oil sensitizer 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 preferable.
  • nitrogen-containing low molecular weight compounds examples include amine salts and quaternary ammonium salts. Further, imidazolinium salts, benzimidazolinium salts, pyridinium salts, and quinolinium salts are also included. Of these, quaternary ammonium salts and pyridinium salts are preferable.
  • tetramethylammonium hexafluorophosphate
  • tetrabutylammonium hexafluorophosphate
  • dodecyltrimethylammonium p-toluenesulfonate
  • benzyltriethylammonium hexafluorophosphate
  • benzyldimethyloctylammonium hexafluorophosphate.
  • Fert, benzyldimethyldodecyl ammonium hexafluorophosphate, compounds described in paragraphs 0021 to 0037 of JP 2008-284858 A, paragraphs 0030 to 0057 of JP 2009-90645 A, and the like.
  • the ammonium group-containing polymer may have an ammonium group in its structure, and a polymer containing 5 to 80 mol% of a (meth)acrylate having an ammonium group in its side chain as a copolymerization component is preferable. Specific examples thereof include the polymers described in paragraphs 0089 to 0105 of JP 2009-208458 A.
  • the ammonium salt-containing polymer preferably has a reduced specific viscosity (unit: ml/g) in the range of 5 to 120, which is determined according to the measuring method described in JP-A-2009-208458, and preferably in the range of 10 to 110. Those having a range of 15 to 100 are particularly preferable.
  • Mw mass average molecular weight
  • the content of the oil sensitizer is preferably 0.01 to 30.0% by mass, more preferably 0.1 to 15.0% by mass, and more preferably 1 to 10% by mass, based on the total mass of the image recording layer. More preferable.
  • the acid color former means a compound having a property of developing a color by heating while receiving an electron-accepting compound (for example, a proton of an acid or the like).
  • an electron-accepting compound for example, a proton of an acid or the like.
  • a colorless lactone which has a partial skeleton such as lactone, lactam, sultone, spiropyran, ester, amide, etc., and these partial skeletons are rapidly ring-opened or cleaved when contacted with an electron accepting compound Compounds are preferred.
  • acid color formers examples include 3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide (referred to as “crystal violet lactone”) and 3,3-bis(4-dimethylaminophenyl).
  • the acid color former is preferably at least one compound selected from spiropyran compounds, spirooxazine compounds, spirolactone compounds, and spirolactam compounds.
  • the hue of the dye after coloring is preferably green, blue or black from the viewpoint of visibility.
  • the acid colorant such as ETAC, RED500, RED520, CVL, S-205, BLACK305, BLACK400, BLACK100, BLACK500, H-7001, GREEN300, NIRBLACK78, BLUE220, H. -3035, BLUE203, ATP, H-1046, H-2114 (above, Fukui Yamada Chemical Co., Ltd.), ORANGE-DCF, Vermilion-DCF, PINK-DCF, RED-DCF, BLMB, CVL, GREEN-DCF.
  • TH-107 above, Hodogaya Chemical Co., Ltd.
  • Examples include -118, Red-40, Red-8 (all manufactured by Yamamoto Kasei Co., Ltd.), and crystal violet lactone (manufactured by Tokyo Chemical Industry Co., Ltd.).
  • ETAC, S-205, BLACK305, BLACK400, BLACK100, BLACK500, H-7001, GREEN300, NIRBLACK78, H-3035, ATP, H-1046, H-2114, GREEN-DCF, Blue-63, GN-169 and crystal violet lactone are preferable because the formed film has good visible light absorption.
  • the acid colorants may be used alone or in combination of two or more.
  • the colorant is used for the purpose of coloring an image and includes a dye having a large absorption in the visible light region. Specifically, Oil Yellow #101, Oil Yellow #103, Oil Pink #312, Oil Green BG, Oil Blue BOS, Oil Blue #603, Oil Black BY, Oil Black BS, Oil Black T-505 (above Orient Chem. Kogyo Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Ethyl Violet 6HNAPS, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI52015) and JP-A-SHO.
  • 62-293247 can be mentioned. Further, pigments such as phthalocyanine-based pigments, azo-based pigments, carbon black and titanium oxide can also be preferably used.
  • the inclusion of the colorant facilitates the distinction between the image area and the non-image area after the image is formed.
  • the addition amount of the colorant is preferably 0.005 to 10% by mass based on the total mass of the image recording layer.
  • ⁇ Other ingredients> Other components include a surfactant, a polymerization inhibitor, a higher fatty acid derivative, a plasticizer, inorganic particles, an inorganic layered compound and the like. Specifically, the description in paragraphs 0114 to 0159 of JP 2008-284817 A can be referred to.
  • the lithographic printing plate precursor according to the invention has an image recording layer containing the photosensitive composition of the invention on a support.
  • the image recording layer contains an infrared absorber, a polymerizable compound, a polymerization initiator, and at least one of a binder polymer and polymer particles.
  • the image recording layer preferably further contains a chain transfer agent.
  • the image recording layer contains an infrared absorbing agent and a binder polymer.
  • necessary coating components are dispersed or dissolved in a known solvent (coating solvent) to prepare a coating liquid, It can be formed by coating the coating liquid on a support by a known method such as bar coater coating and drying.
  • the coating amount (solid content) of the image recording layer after coating and drying varies depending on the use, but from the viewpoint of obtaining good sensitivity and good film characteristics of the image recording layer, it is about 0.3 to 3.0 g/m 2. Is preferred.
  • the support in the lithographic printing plate precursor according to the invention can be appropriately selected and used from known lithographic printing plate precursor supports.
  • a support having a hydrophilic surface hydrophilic support
  • the hydrophilic surface preferably has a contact angle with water of less than 10°, more preferably less than 5°.
  • the contact angle with water is measured by using a fully automatic contact angle meter (model number: DM-701, manufactured by Kyowa Interface Science Co., Ltd.) under an atmosphere temperature of 25° C. and a relative humidity of 50%. 1 ⁇ L of deionized water is dropped on the surface of, and the contact angle is measured 5 times by the ⁇ /2 method, and the arithmetic mean value of the obtained values is used.
  • the hydrophilic support an aluminum plate which has been roughened by a known method and subjected to anodization is preferable.
  • the aluminum plate may further include an enlargement treatment and a sealing treatment of micropores of an anodized film described in JP 2001-253181 A and JP 2001-322365 A, and US Pat. No. 066, No. 3,181,461, No. 3,280,734, and No. 3,902,734, surface hydrophilization treatment with an alkali metal silicate, US A surface hydrophilization treatment using polyvinylphosphonic acid or the like as described in the respective specifications of Patents 3,276,868, 4,153,461 and 4,689,272 is appropriately selected. You may go.
  • the center line average roughness of the support is preferably 0.10 to 1.2 ⁇ m.
  • the support may have an organic polymer compound described in JP-A-5-45885 or a silicon alkoxy compound described in JP-A-6-35174 on the surface opposite to the image recording layer. You may have the backcoat layer containing.
  • the lithographic printing plate precursor according to the invention preferably has an undercoat layer (also referred to as an intermediate layer) between the image recording layer and the support.
  • the undercoat layer enhances 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, so that the developability is maintained without impairing printing durability. Contribute to improving.
  • the undercoat layer functions as a heat insulating layer, so that it also has an effect of preventing heat generated by the exposure from diffusing into the support and lowering the sensitivity.
  • the compound used for the undercoat layer includes a polymer having an adsorptive group and a hydrophilic group capable of being adsorbed on the surface of the support.
  • a polymer having an adsorptive group and a hydrophilic group and further having a crosslinkable group in order to improve the adhesion to the image recording layer is preferable.
  • the compound used in 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 in 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 preferable.
  • the adsorptive group that can be adsorbed on the surface of the support include a phenolic hydroxy group, a carboxy group, —PO 3 H 2 , —OPO 3 H 2 , —CONHSO 2 —, —SO 2 NHSO 2 —, and —COCH 2 COCH 3 Is preferred.
  • the hydrophilic group a sulfo group or a salt thereof, or a salt of a carboxy group is preferable.
  • the polymer may have a polar substituent of the polymer and a crosslinkable group introduced by salt formation with a compound having an ethylenically unsaturated bond and a substituent having a charge opposite to the polar substituent, and Other monomers, preferably hydrophilic monomers, may be further copolymerized.
  • Preferable examples are phosphorus compounds having a heavy bond reactive group.
  • Crosslinkable groups preferably ethylenically unsaturated bond groups
  • a low-molecular or high-molecular compound having a functional group that interacts with the surface and a hydrophilic group is also preferably used.
  • high molecular polymers having an adsorptive group, a hydrophilic group and a crosslinkable group capable of being adsorbed on the surface of the support described in JP-A-2005-125749 and JP-A-2006-188038.
  • the content of the ethylenically unsaturated bond group in the polymer used for the undercoat layer is preferably 0.1 to 10.0 mmol, more preferably 0.2 to 5.5 mmol, per 1 g of the polymer.
  • the weight average molecular weight (Mw) of the polymer used in the undercoat layer is preferably 5,000 or more, more preferably 10,000 to 300,000.
  • the undercoat layer is, in addition to the above-mentioned compound for the undercoat layer, a chelating agent, a secondary or tertiary amine, a polymerization inhibitor, an amino group or a functional group having a polymerization inhibition ability and a support surface in order to prevent stains over time.
  • a compound having a group that interacts with eg, 1,4-diazabicyclo[2.2.2]octane (DABCO), 2,3,5,6-tetrahydroxy-p-quinone, chloranil, sulfophthalic acid, hydroxy
  • DABCO 1,4-diazabicyclo[2.2.2]octane
  • 2,3,5,6-tetrahydroxy-p-quinone chloranil
  • sulfophthalic acid hydroxy
  • Ethylethylenediaminetriacetic acid dihydroxyethylethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, etc.
  • the undercoat layer is applied by a known method.
  • the coating amount (solid content) of the undercoat layer is preferably 0.1 ⁇ 100mg / m 2, and more preferably 1 ⁇ 30mg / m 2.
  • the lithographic printing plate precursor according to the invention preferably has a protective layer (also referred to as an overcoat layer) on the image recording layer.
  • the protective layer has a function of suppressing an image formation inhibiting reaction by blocking oxygen, and also a function of preventing the occurrence of scratches in the image recording layer and a function of preventing ablation during exposure to a high-illuminance laser.
  • the protective layer having such characteristics is described in, for example, 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 if necessary, two or more types can be mixed and used. it can.
  • Specific examples include polyvinyl alcohol, modified polyvinyl alcohol, polyvinylpyrrolidone, water-soluble cellulose derivatives, poly(meth)acrylonitrile, and the like.
  • the modified polyvinyl alcohol acid modified polyvinyl alcohol having a carboxy group or a sulfo group is preferably used. Specific examples thereof include the modified polyvinyl alcohols described in JP-A-2005-250216 and JP-A-2006-259137.
  • the protective layer preferably contains an inorganic stratiform compound in order to enhance the oxygen barrier property.
  • the inorganic layered compound is particles having a thin tabular shape, and includes, for example, mica groups such as natural mica and synthetic mica, talc represented by the formula: 3MgO.4SiO.H 2 O, teniolite, montmorillonite, saponite, and hector. Examples thereof include light and zirconium phosphate.
  • the inorganic layered compound preferably used is a mica compound.
  • mica compound examples include compounds represented by the formula: A(B,C) 2-5 D 4 O 10 (OH,F,O) 2 [wherein A is any of K, Na and Ca, and B and C are It is any one of Fe(II), Fe(III), Mn, Al, Mg, and V, and D is Si or Al. ]
  • Mica groups such as natural mica and synthetic mica represented by
  • examples of natural mica include muscovite, soda mica, phlogopite, biotite and ledocite.
  • Synthetic mica includes non-swelling mica such as fluorophlogopite KMg 3 (AlSi 3 O 10 )F 2 and potassium tetrasilicon mica KMg 2.5 Si 4 O 10 )F 2 ; and Na tetrasilylic mica NaMg 2.
  • the lattice layer is deficient in positive charge, and cations such as Li + , Na + , Ca 2+ , and Mg 2+ are adsorbed between the layers to compensate for it.
  • the cations existing between these layers are called exchangeable cations and can exchange with various cations.
  • the ionic radius is small, so that the bond between the layered crystal lattices is weak and the layer swells greatly with water.
  • shear is applied in that state, it is easily cleaved to form a stable sol in water.
  • Swelling synthetic mica has such a strong tendency that it 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 view of the particle with a micrograph. The larger the aspect ratio, the greater the effect obtained.
  • the average major axis thereof is preferably 0.3 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m, and particularly preferably 1 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.
  • a preferable embodiment has a thickness of about 1 to 50 nm and a surface size (major axis) of about 1 to 20 ⁇ m.
  • the content of the inorganic layered compound is preferably 0 to 60% by mass, more preferably 3 to 50% by mass based on the total solid content of the protective layer. Even when a plurality of types of inorganic layered compounds are used in combination, the total amount of the inorganic layered compounds is preferably the above content. Within the above range, the oxygen barrier property is improved and good sensitivity is obtained. In addition, it is possible to prevent a decrease in inking property.
  • the protective layer may contain known additives such as a plasticizer for imparting flexibility, a surfactant for improving coating properties, and inorganic particles for controlling surface slipperiness. Further, the protective layer may contain the oil-sensitizing agent described in the image recording layer.
  • the protective layer is applied by a known method.
  • the coating amount of the protective layer (solid content) is preferably 0.01 ⁇ 10g / m 2, more preferably 0.02 ⁇ 3g / m 2, particularly preferably 0.02 ⁇ 1g / m 2.
  • a lithographic printing plate can be produced by subjecting the lithographic printing plate precursor of the invention to imagewise exposure and development.
  • One embodiment of the method for producing a lithographic printing plate of the present invention is a step of exposing the lithographic printing plate precursor of the present invention to an image to form an exposed portion and an unexposed portion (exposure step), and a printing ink and a dampening solution.
  • the step (on-press development step) of supplying at least one of water to remove the unexposed portion is included in this order.
  • One embodiment of the lithographic printing method of the present invention is selected from a step of exposing the lithographic printing plate precursor of the present invention to an image to form an exposed portion and an unexposed portion (exposure step), a printing ink and a fountain solution.
  • exposure step a step of supplying at least one of them to remove the image recording layer in the non-image area on a printing machine to produce a lithographic printing plate (on-press development step), and a step of printing with the obtained lithographic printing plate (printing step) including.
  • Another embodiment of the lithographic printing method of the present invention is a step of exposing the lithographic printing plate precursor of the present invention to an image to form an exposed portion and an unexposed portion (exposure step), and a pH of 2 or more and 11 or less.
  • the method includes a step of supplying a developing solution to remove the unexposed portion (developing step), and a step of printing with the obtained lithographic printing plate (printing step).
  • developing step a developing solution to remove the unexposed portion
  • printing step a step of printing with the obtained lithographic printing plate
  • the method for producing a lithographic printing plate of the present invention preferably includes an exposure step of image-exposing the lithographic printing plate precursor of the present invention to form an exposed portion and an unexposed portion.
  • the lithographic printing plate precursor according to the invention is preferably exposed imagewise by laser exposure through a transparent original image having a line image, a halftone image or the like, or imagewise by laser light scanning with digital data.
  • the wavelength of the light source is preferably 750 to 1,400 nm.
  • solid-state lasers and semiconductor lasers that emit infrared rays are suitable.
  • the output is preferably 100 mW or more, the exposure time per pixel is preferably 20 microseconds or less, and the irradiation energy amount is preferably 10 to 300 mJ/cm 2 . Further, it is preferable to use a multi-beam laser device in order to shorten the exposure time.
  • the exposure mechanism may be any of an inner drum system, an outer drum system, a flat bed system, and the like. Image exposure can be performed by a conventional method using a platesetter or the like. In the case of on-press development, the lithographic printing plate precursor may be mounted on the printing machine and then imagewise exposed on the printing machine.
  • the method for producing the lithographic printing plate of the invention is preferably a method (on-press development method) including an on-press development step of supplying at least one of printing ink and dampening water to remove the unexposed portion.
  • the method for producing the lithographic printing plate of the present invention may be performed by a method of developing with a developing solution (developing solution processing method).
  • the method for producing a lithographic printing plate of the present invention includes a developing step of supplying a developing solution having a pH of 2 to 11 to remove the unexposed portion.
  • the image-exposed lithographic printing plate precursor is supplied with an oil-based ink and an aqueous component on the printing machine, and the image recording layer in the non-image area is removed to prepare a lithographic printing plate. Is preferred.
  • the uncured image-recording layer may be formed in the non-image area at the initial stage of printing by one or both of the supplied oil-based ink and the water-based component. It is dissolved or dispersed and removed, and the hydrophilic surface is exposed at that portion.
  • the image recording layer cured by the exposure forms an oil-based ink receiving area having a lipophilic surface.
  • the oil-based ink or the aqueous component may be initially supplied to the plate surface, the oil-based ink is first supplied in order to prevent the aqueous component from being contaminated by the removed components of the image recording layer. It is preferable.
  • the lithographic printing plate precursor is on-press developed on the printing machine and used as it is for printing a large number of sheets.
  • a printing ink including an ultraviolet-curable ink
  • a fountain solution for ordinary lithographic printing are preferably used.
  • a lithographic printing plate can be prepared by a developing treatment using a developer by appropriately selecting a binder polymer or the like which is a constituent component of the image recording layer.
  • the development process using a developer is performed using a developer having a pH of 2 to 11 which may contain at least one compound selected from a surfactant and a water-soluble polymer compound (also referred to as a simple development process). Including.
  • a developing solution and a gum solution treatment step can be carried out at the same time by incorporating a water-soluble polymer compound into the developing solution. Therefore, the post-water washing step is not particularly required, and the development step and the gum solution treatment can be carried out in one solution and the drying step can be carried out. Therefore, the development process using a developing solution is preferably a method of preparing a lithographic printing plate including a step of developing a planographic printing plate precursor after image exposure with a developing solution having a pH of 2 to 11. After the development treatment, it is preferable to remove excess developer using a squeeze roller before drying.
  • Performing development and gum solution treatment in one step with one solution means that development treatment and gum solution treatment are performed in one step with one solution rather than performing development treatment and gum solution treatment as separate steps.
  • the development processing can be suitably carried out by an automatic development processor equipped with a developer supply means and a rubbing member.
  • An automatic development processor using a rotating brush roll as the rubbing member is particularly preferable. Two or more rotating brush rolls are preferable.
  • the automatic development processor is provided with a means for removing excess developer such as a squeeze roller and a drying means such as a warm air device after the development means.
  • the automatic development processor may be provided with a pre-heating means for heat-treating the lithographic printing plate precursor after image exposure, before the development processing means.
  • the processing in such an automatic development processor is advantageous in that it is freed from dealing with the development debris originating in the protective layer/image recording layer which occurs in the case of so-called on-machine development processing.
  • a development processing method for example, a method in which an aqueous solution is contained in sponge or absorbent cotton, processing is performed while rubbing the entire plate surface, and after completion of processing, drying is preferable.
  • the protective layer is removed by the pre-water washing step, then development is performed with a high pH alkaline developer, then the alkali is removed by the post-water washing step, the gum treatment is performed in the gumming step, and the drying step is performed.
  • the simple development process development and gumming can be simultaneously performed with one liquid. Therefore, the post-water washing step and the gum treatment step can be omitted, and it is preferable to perform the development step and gumming (gum solution treatment) with one liquid, and then perform the drying step if necessary. Further, it is preferable to perform the removal of the protective layer, the development and the gumming simultaneously with one liquid without performing the pre-water washing step. After development and gumming, it is preferable to remove excess developer using a squeeze roller and then dry.
  • a method of dipping once in the developing solution or a method of dipping twice or more may be used.
  • the method of immersing the developer once or twice is preferable.
  • the exposed lithographic printing plate precursor may be passed through a developing solution tank in which the developing solution is stored, or the developing solution may be sprayed onto the plate surface of the exposed lithographic printing plate precursor from a spray or the like.
  • the same developing solution or a developing solution and a developing solution (fatigue solution) in which the components of the image recording layer are dissolved or dispersed by the developing treatment are used twice.
  • it is referred to as a developing treatment with one liquid (one-liquid treatment).
  • a rubbing member is preferably used in the development process, and a rubbing member such as a brush is preferably installed in the developing bath for removing the non-image portion of the image recording layer.
  • the development treatment is carried out according to a conventional method, preferably at a temperature of 0 to 60° C., more preferably 15 to 40° C., for example, by dipping the exposed lithographic printing plate precursor in a developer and rubbing with a brush. It can be performed by drawing up the treatment liquid charged in the tank with a pump, spraying it with a spray nozzle, and rubbing it with a brush.
  • the development processing can be performed a plurality of times in succession.
  • the developing solution becomes fatigued due to an increase in the processing amount. Therefore, it is preferable to recover the processing ability by using a replenishing solution or a fresh developing solution.
  • a gum coater or an automatic developing machine conventionally known for PS plates (Presensitized Plates) and CTPs (Computer to Plates) can also be used.
  • an automatic developing machine for example, a method in which a developer charged in a developing tank or a developer charged in an external tank is pumped up and sprayed from a spray nozzle to be processed, in a tank filled with the developer Either a method in which a printing plate is dipped and conveyed by a submerged guide roll or the like for processing, or a so-called disposable processing method in which a necessary amount of substantially unused developer is supplied for processing can be applied. ..
  • a rubbing mechanism such as a brush or a molton.
  • a rubbing mechanism such as a brush or a molton.
  • commercially available automatic developing machines (Clean Out Unit C85/C125, Clean-Out Unit+C85/120, FCF 85V, FCF 125V, FCF News (manufactured by Glunz & Jensen), Azura CX85, Azura CaX125, AzuraCaX125, AzCaz125, AzCaz125, AzCaz125Az. (Manufactured by the same company), or a device in which a laser exposure section and an automatic developing section are integrally incorporated can be used.
  • the pH of the developer is preferably 2 to 11, more preferably 5 to 9, and even more preferably 7 to 9. From the viewpoint of developability and dispersibility of the image recording layer, it is more advantageous to set the pH value higher, but it is more effective to set the pH value lower for printability, especially for suppressing stains. is there.
  • the pH is a value measured at 25° C. using a pH meter (model number: HM-31, manufactured by Toa DKK Co., Ltd.).
  • the developer may contain a surfactant such as an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant.
  • the developer preferably contains at least one selected from anionic surfactants and amphoteric surfactants, from the viewpoint of stain resistance of the blank.
  • the developer preferably contains a nonionic surfactant, and more preferably contains a nonionic surfactant and at least one selected from anionic surfactants and amphoteric surfactants.
  • R 1 represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group, which may have a substituent.
  • an alkyl group having 1 to 20 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, Preferred examples thereof include an octyl group, a decyl group, a dodecyl group, a hexadecyl group and a stearyl group.
  • the cycloalkyl group may be monocyclic or polycyclic.
  • the monocyclic type is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms, and more preferably a cyclopropyl group, a cyclopentyl group, a cyclohexyl group or a cyclooctyl group.
  • Preferable examples of the polycyclic type include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an ⁇ -pinel group, and a tricyclodecanyl group.
  • alkenyl group for example, an alkenyl group having 2 to 20 carbon atoms is preferable, and specifically, a vinyl group, an allyl group, a butenyl group, a cyclohexenyl group and the like can be preferably mentioned.
  • the aralkyl group is preferably, for example, an aralkyl group having a carbon number of 7 to 12, and specific examples thereof include a benzyl group, a phenethyl group and a naphthylmethyl group.
  • the aryl group is preferably, for example, an aryl group having 6 to 15 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a dimethylphenyl group, a 2,4,6-trimethylphenyl group, a naphthyl group and an anthryl group. Preferred examples thereof include a group and a 9,10-dimethoxyanthryl group.
  • a monovalent non-metal atomic group is used, and preferable examples thereof include a halogen atom (F, Cl, Br or I), a hydroxy group, an alkoxy group, an aryloxy group, an acyl group, an amide group, an ester.
  • a halogen atom F, Cl, Br or I
  • a hydroxy group an alkoxy group, an aryloxy group, an acyl group, an amide group, an ester.
  • acyloxy group carboxy group, carboxylate anion group, sulfonate anion group and the like.
  • alkoxy group in the substituent examples include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, a pentyloxy group, a hexyloxy group, a dodecyloxy group, a stearyloxy group, a methoxyethoxy group, and a poly( An ethyleneoxy) group, a poly(propyleneoxy) group and the like are preferably those having 1 to 40 carbon atoms, more preferably 1 to 20 carbon atoms.
  • the aryloxy group has 6 to 18 carbon atoms such as phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyloxy group, bromophenyloxy group, and naphthyloxy group.
  • the following are listed.
  • Examples of the acyl group include those having 2 to 24 carbon atoms such as acetyl group, propanoyl group, butanoyl group, benzoyl group and naphthoyl group.
  • Examples of the amide group include those having 2 to 24 carbon atoms such as acetamide group, propionic acid amide group, dodecanoic acid amide group, palmitic acid amide group, stearic acid amide group, benzoic acid amide group and naphthoic acid amide group.
  • Examples of the acyloxy group include those having 2 to 20 carbon atoms such as acetoxy group, propanoyloxy group, benzoyloxy group and naphthoyloxy group.
  • ester group examples include those having 1 to 24 carbon atoms such as methyl ester group, ethyl ester group, propyl ester group, hexyl ester group, octyl ester group, dodecyl ester group and stearyl ester group.
  • the substituent may be a combination of two or more of the above substituents.
  • X 1 represents a sulfonate group, a sulfuric acid monoester group, a carboxylate group or a phosphate group.
  • Y 1 is a single bond, —C n H 2n —, —C nm H 2 (nm) OC m H 2m —, —O—(CH 2 CH 2 O) n —, —O— ⁇ CH.
  • the compounds represented by the formula (I) are preferable from the viewpoint of scratch resistance.
  • R A1 to R A10 each independently represent a hydrogen atom or an alkyl group
  • nA represents an integer of 1 to 3
  • X A1 and X A2 each represent Independently, it represents a sulfonate group, a sulfuric acid monoester group, a carboxylate group, or a phosphate group
  • Y A1 and Y A2 each independently represent a single bond, —CnH 2n —, —C n ⁇ m H 2(n ⁇ m ) OC m H 2m ⁇ , —O—(CH 2 CH 2 O) n —, —O— ⁇ CH 2 CH(CH 3 )O ⁇ n ⁇ , —O— ⁇ CH(CH 3 )CH 2 O ⁇ n -, - O- (CH 2 CH 2 CH 2 O) n -, - CO-NH-, or a divalent linking group formed by combining two or more satisfies n ⁇ 1 and
  • the total carbon number of R A1 to R A5 and Y 1A , or R A6 to R A10 and Y A2 in the compound represented by the formula (IA) or the formula (IB) is 25 or less. Is preferable and 4 to 20 is more preferable.
  • the structure of the above-mentioned alkyl group may be linear or branched.
  • X A1 and X A2 in the compound represented by the formula (IA) or the formula (IB) are preferably a sulfonate group or a carboxylate group.
  • the salt structure of X A1 and X A2 is preferably an alkali metal salt because it has particularly good solubility in an aqueous solvent. Among them, sodium salt or potassium salt is particularly preferable.
  • the description in paragraphs 0019 to 0037 of JP-A-2007-206348 can be referred to.
  • the anionic surfactant the compounds described in paragraphs 0023 to 0028 of JP-A-2006-65321 can also be preferably used.
  • amphoteric surfactant used in the developer is not particularly limited, but amine oxides such as alkyldimethylamine oxide, alkyl betaines, fatty acid amide propyl betaine, betaines such as alkyl imidazole, and amino acids such as alkylamino fatty acid sodium. Can be mentioned.
  • alkyldimethylamine oxide which may have a substituent alkylcarboxybetaine which may have a substituent
  • alkylsulfobetaine which may have a substituent
  • Specific examples thereof include the compound represented by the formula (2) in paragraph 0256 of JP-A 2008-203359, the formula (I), the formula (II), and the formula (II) in paragraph 0028 of JP-A 2008-276166.
  • Examples thereof include compounds represented by VI) and the compounds described in paragraphs 0022 to 0029 of JP-A-2009-47927.
  • the zwitterionic surfactant used in the developer is preferably a compound represented by the following general formula (1) or a compound represented by the general formula (2).
  • R 1 and R 11 each independently represent an alkyl group having 8 to 20 carbon atoms or an alkyl group having a linking group having 8 to 20 carbon atoms.
  • R 2 , R 3 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group or a group containing an ethylene oxide structure.
  • R 4 and R 14 each independently represent a single bond or an alkylene group. Further, two groups out of R 1 , R 2 , R 3 and R 4 may be bonded to each other to form a ring structure, and two groups out of R 11 , R 12 , R 13 and R 14 are mutually connected. They may combine with each other to form a ring structure.
  • the solubility is improved by mixing an organic solvent such as an alcohol, which aids dissolution, with water as a dissolution aid, but the solubility is improved, but if the total carbon number becomes too large, the surfactant within the proper mixing range. Can not be dissolved. Therefore, the total number of carbon atoms of R 1 to R 4 or R 11 to R 14 is preferably 10 to 40, more preferably 12 to 30.
  • the alkyl group having a linking group represented by R 1 or R 11 represents a structure having a linking group between the alkyl groups. That is, when there is one linking group, it can be represented by "-alkylene group-linking group-alkyl group".
  • the linking group include an ester bond, a carbonyl bond and an amide bond. Although there may be two or more linking groups, one is preferable, and an amide bond is particularly preferable.
  • the total number of carbon atoms of the alkylene group bonded to the linking group is preferably 1-5.
  • the alkylene group may be linear or branched, but a linear alkylene group is preferable.
  • the alkyl group bonded to the linking group preferably has 3 to 19 carbon atoms and may be linear or branched, but is preferably linear alkyl.
  • R 2 or R 12 is an alkyl group, it preferably has 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms. It may be linear or branched, but is preferably a linear alkyl group.
  • R 3 or R 13 is an alkyl group, it preferably has 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms. It may be linear or branched, but is preferably a linear alkyl group.
  • Examples of the group containing an ethylene oxide structure represented by R 3 or R 13 include a group represented by —R a (CH 2 CH 2 O) n R b .
  • R a represents a single bond, an oxygen atom or a divalent organic group (preferably having a carbon number of 10 or less)
  • R b represents a hydrogen atom or an organic group (preferably having a carbon number of 10 or less)
  • n is 1 Represents an integer of -10.
  • R 4 and R 14 are alkylene groups, it preferably has 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms. It may be linear or branched, but is preferably a linear alkylene group.
  • the compound represented by the general formula (1) or the compound represented by the general formula (2) preferably has an amide bond, and more preferably has an amide bond as a linking group of R 1 or R 11 . Representative examples of the compound represented by the general formula (1) or the compound represented by the general formula (2) are shown below, but the present invention is not limited thereto.
  • the compound represented by the general formula (1) or (2) can be synthesized according to a known method. Moreover, a commercial item can also be used. Examples of commercially available compounds represented by the general formula (1) include Softenzoline LPB, Softofazoline LPB-R, Vista MAP manufactured by Kawaken Fine Chemical Co., Ltd., Takesurf C-157L manufactured by Takemoto Yushi Co., Ltd., and the like. Examples of the compound represented by the general formula (2) include Softenzoline LAO manufactured by Kawaken Fine Chemical Co., Ltd., and Amogen AOL manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. The zwitterionic surfactant may be used alone or in combination of two or more kinds in the developer.
  • Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, Propylene glycol monofatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid partial ester, polyoxyethylene glycerin fatty acid partial ester , Polyoxyethylene diglycerin, fatty acid diethanolamide, N,N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamine, triethanolamine fatty acid ester, trialkylamine oxide, polyoxyethylene alkylphenyl ether And polyoxyethylene-polyoxypropylene block copolymers. Further
  • nonionic surfactant examples include nonionic aromatic ether-based surfactants represented by the following formula (N1).
  • X N represents an aromatic group which may have a substituent
  • Y N represents a single bond or an alkylene group having 1 to 10 carbon atoms
  • a 1 and A 2 are groups different from each other.
  • nB and mB each independently represent an integer of 0 to 100, provided that nB and mB are the same.
  • examples of the aromatic group of X N include a phenyl group, a naphthyl group, and an anthranyl group. These aromatic groups may have a substituent. Examples of the substituent include an organic group having 1 to 100 carbon atoms. In the formula, when both A and B are present, they may be random or block copolymers.
  • organic group having 1 to 100 carbon atoms include aliphatic hydrocarbon groups and aromatic hydrocarbon groups which may be saturated or unsaturated and may be linear or branched, for example, alkyl group, alkenyl group, alkynyl group, In addition to aryl groups and aralkyl groups, alkoxy groups, aryloxy groups, N-alkylamino groups, N,N-dialkylamino groups, N-arylamino groups, N,N-diarylamino groups, N-alkyl-N- Arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N,N-dialkylcarbamoyloxy group, N,N-diarylcarbamoyloxy group, N-alkyl-N-aryl Rucarbamoyloxy group, acylamino group, N-alkylacylamin
  • the cationic surfactant is not particularly limited, and conventionally known ones can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, alkylimidazolinium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives and the like.
  • the surfactants may be used alone or in combination of two or more.
  • the content of the surfactant is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, further preferably 3 to 15% by mass, and particularly preferably 5 to 10% by mass, based on the total mass of the developer. .. Within the above range, the scratch resistance to stains is excellent, the dispersibility of development residue is excellent, and the ink receptivity of the resulting lithographic printing plate is excellent.
  • the developer may contain a water-soluble polymer compound from the viewpoint of adjusting the viscosity of the developer and protecting the plate surface of the lithographic printing plate obtained.
  • a water-soluble polymer compound soybean polysaccharide, modified starch, gum arabic, dextrin, fibrin derivative (for example, carboxymethylcellulose, carboxyethylcellulose, methylcellulose, etc.) and its modified product, pullulan, polyvinyl alcohol and its derivative, polyvinylpyrrolidone , Polyacrylamide and acrylamide copolymers, vinyl methyl ether/maleic anhydride copolymers, vinyl acetate/maleic anhydride copolymers, styrene/maleic anhydride copolymers, etc. it can.
  • soybean polysaccharides conventionally known ones can be used.
  • Soya Five manufactured by Fuji Oil Co., Ltd.
  • What can be preferably used is one in which the viscosity of a 10 mass% aqueous solution is in the range of 1 to 100 mPa ⁇ s.
  • starch represented by the following formula (III) is preferable.
  • any starch such as corn, potato, tapioca, rice and wheat can be used.
  • the modification of these starches can be carried out by, for example, decomposing the starch with an acid or an enzyme in the range of 5 to 30 glucose residues per molecule, and further adding oxypropylene in an alkali.
  • the degree of etherification (degree of substitution) is in the range of 0.05 to 1.2 per glucose unit, n represents an integer of 3 to 30, and m represents an integer of 1 to 3.
  • soybean polysaccharide modified starch, gum arabic, dextrin, carboxymethyl cellulose, polyvinyl alcohol and the like are particularly preferable.
  • Two or more water-soluble polymer compounds can be used in combination.
  • the content of the water-soluble polymer compound is preferably 3% by mass or less, more preferably 1% by mass or less, based on the total mass of the developer. ..
  • the viscosity of the developing solution is appropriate, and it is possible to suppress the accumulation of developing debris and the like on the roller member of the automatic developing machine.
  • the developer used in the present invention may contain a wetting agent, a preservative, a chelate compound, a defoaming agent, an organic acid, an organic solvent, an inorganic acid, an inorganic salt, etc., in addition to the above.
  • ethylene glycol, propylene glycol, triethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, diglycerin, etc. are preferably used.
  • the wetting agents may be used alone or in combination of two or more.
  • the content of the wetting agent is preferably 0.1 to 5 mass% with respect to the total mass of the developer.
  • Preservatives include phenol or its derivatives, formalin, imidazole derivative, sodium dehydroacetate, 4-isothiazolin-3-one derivative, benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, benztriazole derivative.
  • the amount of the preservative added is such that it exerts a stable effect on bacteria, molds, yeasts, etc. and varies depending on the types of bacteria, molds, yeasts, etc. 01 to 4 mass% is preferable. Further, it is preferable to use two or more kinds of preservatives together so that they are effective against various molds and sterilizations.
  • the chelate compound examples include ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; diethylenetriaminepentaacetic acid, its potassium salt, its sodium salt; triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt, and hydroxyethylethylenediaminetriacetic acid.
  • organic phosphonic acids organic phosphonic acids.
  • Organic amine salts are also effective in place of the sodium and potassium chelates.
  • the chelating agent is preferably one that stably exists in the treatment liquid composition and does not impair the printability.
  • the content of the chelating agent is preferably 0.001 to 1.0 mass% with respect to the total mass of the developer.
  • the defoaming agent a general silicone-based self-emulsifying type, emulsifying type, nonionic compound having a HLB (Hydrophilic-Lipophilic Balance) of 5 or less can be used. Silicone defoamers are preferred.
  • the silicone surfactant is regarded as an antifoaming agent.
  • the content of the defoaming agent is preferably 0.001 to 1.0 mass% with respect to the total mass of the developer.
  • organic acid examples include citric acid, acetic acid, oxalic acid, malonic acid, salicylic acid, caprylic acid, tartaric acid, malic acid, lactic acid, levulinic acid, p-toluenesulfonic acid, xylenesulfonic acid, phytic acid and organic phosphonic acid. ..
  • the organic acid can also be used in the form of its alkali metal salt or ammonium salt.
  • the content of the organic acid is preferably 0.01 to 0.5 mass% with respect to the total mass of the developer.
  • organic solvent examples include aliphatic hydrocarbons (hexane, heptane, "Isopar E, H, G” (manufactured by Esso Chemical Co., Ltd.), etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated compounds. Hydrocarbons (methylene dichloride, ethylene dichloride, trichlene, monochlorobenzene, etc.), polar solvents and the like can be mentioned.
  • alcohols methanol, ethanol, propanol, isopropanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether
  • Propylene glycol monomethyl ether polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, etc.
  • Ketones acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
  • esters ethyl acetate
  • the concentration of the solvent in the developer is preferably less than 40% by mass.
  • the inorganic acid and the inorganic salt phosphoric acid, metaphosphoric acid, monobasic ammonium phosphate, dibasic ammonium phosphate, monobasic sodium phosphate, dibasic sodium phosphate, monobasic potassium phosphate, dibasic potassium phosphate, Examples thereof include sodium tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, magnesium nitrate, sodium nitrate, potassium nitrate, ammonium nitrate, sodium sulfate, potassium sulfate, ammonium sulfate, sodium sulfite, ammonium sulfite, sodium hydrogensulfate and nickel sulfate.
  • the content of the inorganic salt is preferably 0.01 to 0.5 mass% with respect to the total mass of the developer.
  • the developer is prepared by dissolving or dispersing each of the above components in water, if necessary.
  • the solid concentration of the developer is preferably 2 to 25% by mass. It is also possible to prepare a concentrated solution as a developer and dilute it with water before use.
  • the developer is preferably an aqueous developer.
  • the developer preferably contains an alcohol compound from the viewpoint of dispersibility of development residue.
  • the alcohol compound include methanol, ethanol, propanol, isopropanol, benzyl alcohol and the like. Of these, benzyl alcohol is preferable.
  • the content of the alcohol compound is preferably 0.01 to 5% by mass, more preferably 0.1 to 2% by mass, and more preferably 0.2 to 1 with respect to the total mass of the developing solution, from the viewpoint of dispersibility of developing residue. Mass% is particularly preferred.
  • the planographic printing method of the present invention includes a printing step of supplying printing ink to the planographic printing plate developed in the on-press development step or the development step to print.
  • the printing ink is not particularly limited, and various known inks can be used as desired.
  • the printing ink is preferably an oil-based ink or an ultraviolet curable ink, more preferably an ultraviolet curable ink.
  • dampening water may be supplied as needed.
  • the printing process may be performed continuously with the on-press development process without stopping the printing press.
  • the molecular weight is a mass average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) method, and the ratio of repeating units is a molar percentage, except for those specifically specified.
  • Mw mass average molecular weight
  • GPC gel permeation chromatography
  • Synthesis Example 1 Synthesis of Polymer G-15
  • Macromonomer MM-1 was synthesized according to the following synthesis scheme.
  • P-Chloromethylstyrene (7.84 g), potassium iodide (15.8 g), 4-OH-TEMPO (0.15 g) and acetonitrile (28 g) were added to a three-necked flask, and the mixture was stirred under an air atmosphere, 2-Ethyloxazoline (200.25g) was added. The temperature was raised to 80° C. and stirring was continued for 24 hours. Next, the reaction solution was cooled to room temperature, sodium carbonate (50 g) and water (30 g) were added, the reaction solution was heated to 80° C., and further stirred for 24 hours.
  • Polymer G-15 was synthesized according to the following synthesis scheme.
  • the aluminum plate was etched by immersing it in a 25 mass% sodium hydroxide aqueous solution at 45°C for 9 seconds, washed with water, further immersed in a 20 mass% nitric acid aqueous solution at 60°C for 20 seconds, and washed with water.
  • the etching amount of the grained surface was about 3 g/m 2 .
  • the electrolytic solution was a 1% by mass nitric acid aqueous solution (containing 0.5% by mass of aluminum ions), and the solution temperature was 50°C.
  • the AC power supply waveform uses a trapezoidal rectangular wave alternating current with a time TP of 0.8 ms from when the current value reaches a peak to 0.8 ms, a duty ratio of 1:1, and an electrochemical surface roughening treatment using a carbon electrode as a counter electrode. I went. 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 source was shunted to the auxiliary anode. The quantity of electricity in nitric acid electrolysis was 175 C/dm 2 when the aluminum plate was the anode. Then, washing with water was performed by spraying.
  • the aluminum plate is treated with nitric acid under conditions of an electric quantity of 50 C/dm 2 when the anode is an anode.
  • Electrochemical surface roughening treatment was performed in the same manner as electrolysis, and then water washing by spraying was performed.
  • a 15 mass% sulfuric acid aqueous solution (containing 0.5 mass% of aluminum ions) having a liquid temperature of 54° C. as an electrolytic solution on an aluminum plate, a direct current anodic oxide film of 2.5 g/m 2 at a current density of 15 A/dm 2.
  • the average pore diameter (surface average pore diameter) in the surface layer of the anodized film was 10 nm.
  • an ultra-high resolution SEM S-900 manufactured by Hitachi, Ltd.
  • a vapor deposition process for imparting conductivity with a relatively low acceleration voltage of 12 V was performed.
  • 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 ⁇ 10% or less.
  • the support A was subjected to silicate treatment for 7 seconds at 50° C. using 2.5% by mass aqueous solution of sodium silicate No. 3, and then washed with water by spraying. Body B was produced. The amount of Si attached was 11 mg/m 2 .
  • a support C was prepared in the same manner as the preparation of the support A except that the electrolytic solution at the time of forming the DC anodic oxide film was changed to a 22 mass% phosphoric acid aqueous solution.
  • the average pore diameter (surface average pore diameter) in the surface layer of the anodized film was 25 nm as measured by the same method as above.
  • the support C was subjected to a silicate treatment with a 2.5% by mass aqueous solution of sodium silicate No. 3 at 60° C. for 10 seconds, and then washed with water to form a support D. It was made. The amount of Si attached was 10 mg/m 2 .
  • the center line average roughness (Ra) of the support D was measured with a needle having a diameter of 2 ⁇ m and found to be 0.52 ⁇ m.
  • undercoat layer coating solution having the following composition was prepared.
  • a protective layer coating solution having the following composition was prepared.
  • (Protective layer coating liquid) -Inorganic layered compound dispersion liquid (1) (below): 1.5 parts by mass-Polyvinyl alcohol (CKS50, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., modified with sulfonic acid, saponification degree 99 mol% or more, polymerization degree 300) 6 parts by mass %
  • Aqueous solution 0.55 parts by mass polyvinyl alcohol (PVA-405, manufactured by Kuraray Co., Ltd., saponification degree 81.5 mol%, polymerization degree 500) 6% by mass aqueous solution: 0.03 parts by mass, surfactant (poly Oxyethylene lauryl ether, Emarex (registered trademark) 710, manufactured by Nippon Emulsion Co., Ltd.) 1% by mass aqueous solution: 0.86 parts by mass/ion-exchanged water: 6.0 parts by mass
  • surfactant poly Oxyethylene lauryl ether, Emare
  • the method for preparing the inorganic layered compound dispersion liquid (1) used in the coating liquid for the protective layer is shown below.
  • Preparation of coating liquid (1) for image recording layer An image recording layer coating solution (1) having the following composition was prepared. Preparation of the coating liquid (1) for the image recording layer is carried out by mixing the photosensitive liquid containing a component other than the specific polymer (or the comparative polymer) and the liquid containing the specific polymer (or the comparative polymer) immediately before coating and stirring. I went by.
  • Preparation of coating liquid for image recording layer (2) An image recording layer coating solution (2) having the following composition was prepared. Preparation of the coating liquid (2) for the image recording layer is carried out by mixing the photosensitive liquid containing a component other than the specific polymer (or the comparative polymer) and the liquid containing the specific polymer (or the comparative polymer) with each other immediately before coating and stirring. I went by.
  • the compounds used in the coating solutions (1) and (2) for the image recording layer are as follows.
  • Binder polymer B-1 compound having the following structure
  • Infrared absorbing agents K-1 to K-3 compounds having the following structures
  • Polymerization initiators I-1 to I-3 compounds having the following structures
  • Polymerization initiator R-1 compound having the following structure
  • T-1 tris(2-hydroxyethyl) isocyanurate
  • T-2 compound having the following structure
  • T-3 hydroxypropyl cellulose (Klucel M, manufactured by Hercules)
  • Sensitizer C-1 Compound having the following structure
  • C-2 Benzyldimethyloctylammonium.PF 6 salt
  • C-3 Compound having the following structure
  • Fluorosurfactant (1) Compound W-1 having the following structure
  • W (HSP) and Y (ClogP) are shown below.
  • the content of each structural unit (subscript in the lower right of the bracket) is a mass ratio
  • the divalent linking group corresponding to W in the group represented by the formula (1) according to the present invention is ethyleneoxy.
  • a group (—CH 2 CH 2 O—).
  • W(HSP) represents the Hansen solubility parameter of the ethyleneoxy group.
  • Y(ClogP) represents ClogP of a monovalent organic group corresponding to Y.
  • Examples 1-27 and Comparative Examples 1-4 Preparation of lithographic printing plate precursor>
  • the planographic printing plate precursors of Examples 1 to 27 and Comparative Examples 1 to 4 were prepared by the following methods.
  • the undercoat layer coating solution was applied so that the dry coating amount was 20 mg/m 2 , to form an undercoat layer.
  • the coating solution (1) for image recording layer was bar-coated on the undercoat layer, and oven-dried at 120° C. for 40 seconds to form an image recording layer having a dry coating amount of 1.0 g/m 2 .
  • the above-mentioned coating solution for protective layer was bar-coated on the image recording layer, followed by oven drying at 120°C for 60 seconds.
  • a protective layer having a dry coating amount of 0.15 g/m 2 was formed.
  • lithographic printing plate precursor was subjected to a Kodak Magnus 800 Quantum equipped with an infrared semiconductor laser under conditions of an output of 27 W, an external drum rotation number of 450 rpm (revolutions per minute), and a resolution of 2,400 dpi (dot per inch, 1 inch is 2.54 cm). Exposure (irradiation energy 110 mJ/cm 2 equivalent). The exposed image includes a solid image and an AM screen (Amplitude Modulation Screen) 3% halftone dot chart.
  • AM screen Amplitude Modulation Screen
  • the lithographic printing plate precursor containing the specific polymer of the present invention contains the comparative polymer in which the Hansen solubility parameter of the divalent group corresponding to W in the formula (1) is 17.4. It is understood that both the printing durability and the developability when using the ultraviolet curable ink are superior to those of the lithographic printing plate precursor of Comparative Example.
  • Examples 28-47 and Comparative Examples 5-8 ⁇ Preparation of lithographic printing plate precursor>
  • the planographic printing plate precursors of Examples 28 to 47 and Comparative Examples 5 to 8 were prepared by the following methods.
  • the undercoat layer coating solution was applied so that the dry coating amount was 20 mg/m 2 , to form an undercoat layer.
  • the coating solution (2) for image recording layer was bar-coated on the undercoat layer, and oven-dried at 70° C. for 60 seconds to form an image recording layer having a dry coating amount of 0.6 g/m 2 .
  • the above-mentioned protective layer coating solution was bar-coated on the image recording layer and oven-dried at 120°C for 60 seconds.
  • a protective layer having a dry coating amount of 0.15 g/m 2 was formed.
  • the lithographic printing plate precursor containing the specific polymer of the present invention contains the comparative polymer in which the divalent group corresponding to W in the formula (1) has a Hansen solubility parameter of 17.4. It is understood that both the printing durability and the developability when using the ultraviolet curable ink are superior to those of the lithographic printing plate precursor of Comparative Example.
  • a photosensitive composition having excellent developability and printing durability can be provided. Further, according to the present invention, it is possible to provide a lithographic printing plate precursor excellent in developability and printing durability. Furthermore, according to the present invention, it is possible to provide a method for producing a lithographic printing plate or a lithographic printing method using a lithographic printing plate precursor having excellent developability and printing durability.

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Abstract

La présente invention concerne : une composition photosensible contenant un polymère ayant un groupe représenté par une formule spécifique (1); un précurseur de plaque d'impression lithographique ayant une couche d'enregistrement d'image contenant la composition photosensible sur un support; un procédé de production d'une plaque d'impression lithographique; et un procédé d'impression lithographique.
PCT/JP2019/050198 2018-12-27 2019-12-20 Composition photosensible, précurseur de plaque d'impression lithographique, procédé de production de plaque d'impression lithographique, et procédé d'impression lithographique WO2020137919A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2023032868A1 (fr) 2021-08-31 2023-03-09 富士フイルム株式会社 Précurseur de plaque d'impression lithographique de type à développement sur machine et procédé de fabrication de plaque d'impression

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